All solid state lithium ion rechargeable batteries using NASICON structured electrolyte

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1 Lithium-Ion Batteries (国外专著)

C hapter 1S ynopsis of the Lithium-Ion Battery MarketsR alph J. B rodd1.1 IntroductionR esearch and development of the lithium-ion (Li-Ion) battery system began in the early 1980s at Asahi Chemicals 1and was first commercialized in 1990 by Sony Corp. for the Kyocera cellular phone in the 14,500 and 20,500 cell sizes. 2The fol-lowing year Sony introduced the 18,650 cell in its camcorder. (The nomenclature for cells size: the first two numbers indicate the cell diameter in millimeters and the last three are the cell length in tenths of millimeters.) Since its introduction, the Li-Ion market has grown to about $4 billion in 2005.T he higher volumetric and gravimetric energy storage capability are key charac-teristics of the Li-Ion battery system compared to the conventional sealed nickel–cadmium (Ni–Cd), nickel-metal hydride (Ni-MH), and valve-regulated lead acid (VRLA) battery systems (Fig. 1.1 ). For a given cell size, larger values of Wh/l and Wh/kg translate into smaller and lighter cells. These characteristics became the enabling technology for the proliferation of portable battery-powered electronic devices, especially notebook computers and mobile phone applications.S afety of the system has been a watchword for Li-Ion batteries. They have the ability to self-destruct if abused. Manufacturers are careful to ensure that the cells are safe in normal operations. In addition, cell designs incorporate features such as devices that shut off current flow when an abuse condition arises. The United Nations 3as well as the transportation agency in each country have requirements for testing to ensure a safe product for shipping.T able 1.1 shows the advantages and disadvantages of the Li-Ion and Li-Ion polymer rechargeable batteries.R.J. BroddB roddarp of Nevada, Inc ,2161 Fountain Springs Drive ,H enderson ,N V 89074 , USAr alph.brodd@M. Yoshio et al. (eds.), Lithium-lon Batteries, 1 DOI 10.1007/978-0-387-34445-4_1, © Springer Science + Business Media LLC 20092 R.J. Brodd1.2 Present Market for Li-Ion CellsLithium ion cells serve the small-sealed rechargeable battery market and compete mainly with the Ni–Cd and Ni-MH cells for the various applications. The Li-Ion cells are available in cylindrical and prismatic format as well as flat plate constructions. The cylindrical and prismatic constructions use a spiral-wrap cell core where the cell case maintains pressure to hold and maintain compression on the anode, sepa-rator, and cathode. The lighter-weight polymer constructions utilize the adhesivenature of a polymer/laminate-based electrolyte to bond the anode to the cathode.F ig. 1.1 E nergy density (Wh/l) and specific energy (Wh/kg) for the major small-sealed recharge-able battery systems A dvantages D isadvantages • C hemistry with the highest energy (Wh/g) and lightest weight (Wh/kg) •Relatively expensive • No memory effect • Lightest weight • Good cycle life • R equires protection circuitry for safety and toprevent overcharge and overdischarge• High energy efficiency • Nominal 3-h charge • Good high-rate capability• Not tolerant of overcharge and overdischarge• Thermal runaway concernsA dded advantages and disadvantages of Li-Ion polymer/laminate cells • Flexible footprint • Limited high rate capability •Plasticized electrolyte •More expensive • Internal bonding of anode • Poor low-temperature performance• Cathode and separator T able 1.1 A dvantages and disadvantages of Li-ion and Li-ion polymer rechargeable cells1 Synopsis of the Lithium-Ion Battery Markets 3 As a result, it does not need outside pressure to hold the electrodes in contact with each other. A light-weight polymer-aluminum laminate pouch can substitute for a heavier metal cell enclosure. All three constructions employ the same chemistries.T he sales of Li-Ion cells are shown in Table 1.2 .4The Li-Ion market is very competitive. The data for the competing Ni–Cd and Ni-MH cells are included for comparison purposes. The market growth for Li-Ion is spectacular and driven by the proliferation of portable electronic devices such as notebook computers and cellular phone applications. In 15 years between 1991 and 2006 the sales and production of Li-Ion batteries experienced double-digit growth. The slower growth period, around 2000, occurred when cell production in China and Korea began to ramp up and may not have been included in the database.I n 1995, an 18,650 cell sold for $8, while in 2006 the same size cell with 2.6 Ah sold for about $4. Over this period the energy density of the cell more than doubled, while the price fell by 50%. The cell producers accomplished the performance improvements through engineering improvements in cell design, new carbon mate-rials for the anode, and automated high-speed production to reduce the cost. The Li-Ion market is expected to continue growing as new technology is introduced and new applications develop.T he major cell manufacturers are listed in Table 1.3 .The Japanese manufacturers (Sanyo, Sony, and Matsushita) have a clear lead but the Chinese manufacturers (BYD, Lishen) and Korean manufacturers (Samsung and LG Chemical) are challenging. There are no major Li-Ion manufacturers in the United States (or in Europe), evenC ell typeY ear1991 1992 1994 1996 1998 2000 2002 2004 2005 2006aN i–Cd 1,535 1,823 2,060 1,695 1,394 1,204 935 1,006 935 939 N i-MH 39 100 746 863 848 1,245 667 767 726 891 L i-Ion 110 152 1,292 1,900 2,805 2,458 4,019 3,899 3,790 L am Li-Ion 00002187 299 487 547 657 T able 1.2W orldwide Sales (Million of Dollars) 4a EstimatedA pplicationC ell typeN i-Cd N i-MH C y Li-Ion P r Li-Ion L am Li-IonC ellular 50 898.16 125.85 N otebook 22 422.68 16.34 2.50 M ovie 2467.98 11.91D igital still camera 56 18.88 48.17 0.94 P ower tools 575 53 20.14 0.08A udio 80 35 6.99 31.02 45.63 G ames 26.82 14.4 C onsumer 45 300C ordless phones 190 83O thers 330 178 22.854 28.98 14.42 T able 1.32005 Worldwide cell demand (Millions of Cells) 44 R.J. Brodd though they constitute large markets for devices powered by Li-Ion batteries.5 Activity in the United States is limited to several companies that supply the niche medical and military markets.1.3 Market CharacteristicsT he unit cell production for 2005 by product application is given in Table 1.4 . Cellular phone applications dominate the unit cell production. The thin, rectangular polymer/laminate cell construction has found favor in the cellular phone market and now accounts for about 13%, with the rest being the prismatic cell sizes. Notebook computers are second followed by cameras.T he period from its introduction in 1991–2002 was a time for establishing the fundamental base for materials and manufacturing processing. During this period, the processing of the materials, cell designs, and production equipment reached a high level of sophistication. The fundamental underpinning of the technology pro-vided a sound basis for future expansion during the next decade. Problems were identified and methods to solve the problems were developed. From a cell engineer-ing viewpoint, the maximum capacity of an 18,650 cell would be 2.5–2.6 Ah with the materials that were available in 2002. Increase in cell capacity and energy stor-age while maintaining safety would require new materials.S tarting in 2003, a shift in the market applications began to occur, as depicted in Fig. 1.2 .6In one segment basically the drive to increase capacity and performance for the competitive notebook and cellular phone applications continues. This requires the development and introduction of higher capacity, higher p erformance anode and cathode materials. Several new high-capacity, safer compositions suchas LiMn0.3C o0.3N i0.5O2and LiMn0.5N i0.5O2cathodes were developed and are in theprocess of being put into production. In the same line, new anode materials have been developed, based on nanostructured lithium alloy anodes. These materials can drive the 18,650 cell capacity over 2.6 Ah and could approach 3.0 Ah in the future.M anufacturers P ercentage of totalS anyo 27.50S ony 13.30S amsung 10.88M atsushita 10.07B YD 7.53L G Chemical 6.45L ishen 4.52N EC 3.60M axell 3.26O thers 12.89T able 1.4M ajor Li-ion cell manufacturers, 2005 41 Synopsis of the Lithium-Ion Battery Markets 5The other segment consists of applications that do not require a significant increase in energy storage capability but emphasize lower cost and higher power for new applications such as automotive and power tools. These applications also require new cathode and anode materials to meet the market demands for low cost with high-rate performance. An example of a new material is the LiFePO 4cathode materials introduced in the market in 2003 by Valence Technology and followed byA123, which emphasized power tool applications. 7–91.4 Consumer Electronics Cellular telephones and notebook computer applications drove the market and will continue to dominate cell usage. The Bluetooth and 3G mobile phones should expand the market coupled with expansion as people shift to higher performance devices. The market for portable cellular phone and notebook computers is reaching saturation in the United States and Europe where it is expected to grow in parallel with the gross national product. Large growth areas for cellular phones and note-book computers are in Asia, especially the Chinese and Indian markets.M ovie cameras account for about 25% of cell usage. Often cameras are used intermittently and may sit on the shelf for an extended period before use. The shelf life of the Li-Ion is significantly better than Ni–Cd and Ni-MH cells, the previous battery systems for movie cameras. Digital still cameras are next. They are in the process of transitioning to Li-Ion from alkaline primary and Ni-MH cells. Most primary cells lack the high pulse current required for camera operation. Only the primary Li–FeS 2system gives fully satisfactory performance for digital still camera operation. Notebook computer and cellular phone users have learned to recharge their batteries on a regular basis so that the device gives the expected service. In addition, many mobile phones have a built-in camera and could slow the development of the digital camera market.F ig. 1.2 A split develops in the Li-ion market6 R.J. Brodd 1.5 Hand Power ToolsT he power tool market is dominated by the Ni–Cd system. In terms of cell volumes it is the third largest. However, it is heavy and has a short run time compared to Li-Ion. Previously, Li-Ion cells could not meet the very high rate capability of theNi–Cd. Recently, Li-Ion cells with excellent high-rate LiMn2O4or LiFePO4cathodematerials were introduced for power tool applications. They are about a third smaller and half the weight of the older Ni–Cd. The phosphate cathode cells have a significantly greater safety characteristic as the cells do not go into thermal runaway until heated to over 600°C. The greater safety, coupled with the superior high-rate capability of the nanostructured phosphate materials, make them ideal for this application. This market segment is price-sensitive. Because the Ni-MH has poor low temperature and poorer very high rate performance, it has not made a signifi-cant inroad against Ni–Cd. The introduction of Li-Ion–powered tools by DeWalt and Milwaukee Tool offers a growth opportunity for Li-Ion cells.1.6 Uninterruptible Power Sources, Stationary Energy Storage T he uninterruptible power source market is about $ 6–10 billion annually and is growing roughly with the gross national product. This market is dominated by lead acid batteries. The technology is slowly shifting from the flooded to the valve-regulated lead acid technology. The valve-regulated lead acid cells are sealed and do not vent hydrogen and acid vapors on charge or stand, but they are more expen-sive to produce. The main competition to the lead acid is costly pocket plate Ni–Cd, but it has an exceptionally long life. It is not unusual for Ni–Cd to have an opera-tional life of 15 years or more in this application. Increased emphasis on environ-mental controls has made lead acid and Ni–Cd vulnerable for penetration by the environmentally acceptable, higher-cost Li-Ion batteries.T his market is very price-sensitive and the cost of Li-Ion cells will need to reach $0.30/Wh to penetrate this market. The new lower-cost manganese and phosphate cathode materials could reach this cost goal. It should be noted that several large lead acid battery companies in this market recently have entered into agreements with Li-Ion producers to supply cells and batteries for evaluation purposes. This could be an indication that the more traditional lead acid producers are positioning themselves to supply Li-Ion as an alternative for lead batteries.1.7 TransportationT here are many emerging market opportunities for Li-Ion cells in transportation. The motive power market is viewed as the largest future growth opportunity for Li-Ion batteries. Once in place, the transportation market will dwarf the present1 Synopsis of the Lithium-Ion Battery Markets 7 portable device market. The Segway Transporter has shifted from Ni-MH to Li-Ion batteries. The Toyota Prius will shift from Ni-MH to Li-Ion in the next model rede-sign. These, along with the emerging boating motors for freshwater lakes, have set the stage for penetration into this huge market area. Europe is in the process of banning gasoline motors on all lakes. Several U.S. lakes now bar gasoline-powered boats, as well. Boaters must shift to electric drive and batteries to operate on the lakes. These presently use lead acid batteries. The smaller, lighter, Li-Ion battery is already marketed in Europe for this application.T he introduction of the Tesla electric vehicle in 2007 with a 200 + mile range should set the stage for the transition to electric propulsion. The new cathode and anode systems also offer the potential to replace the present lead acid SLI (starting-lighting-ignition) battery on gasoline-powered vehicles.R eferences1.A. Y oshino ,T he Chemical Industry ,146,870 (1995)2.T. N agaura and K. T azawa ,P rogress in Batteries and Battery Materials ,10,218 (1991)3. R. J. Brodd, Factors affecting U.S. production decisions: Why are there no volume lithium ionbattery manufacturers in the United States? ATP Working Paper 05-01, June, 20054. R ecommendations on the Transport of Dangerous Goods, Manual of Tests and Criteria, Thirdrevised edition, United Nations, New York and Geneva, 20025. H. Takeshita, 23rd International Seminar on Primary and Secondary Batteries, Ft. Lauderdale,FL, March 20066. R. J. Brodd, Keynote Lecture, IMLB 11, Monterey CA, June, 20027. Valence Technology, Inc., Form 10-K, June 30, 20038.S.-Y. C hung ,J. T. B loking ,and Y.-M. C hiang ,N ature Materials ,1,123 (2002)9.A. K. P adhi ,K. S. N anjundaswamy ,and J. B. G oodenough ,J ournal of Electrochemistry Society144,1188 (1997)。

亚磷酸三苯酯_一种锂离子电池电解液稳定剂

第33卷第1期赵季飞等:亚磷酸三苯酯)))一种锂离子电池电解液稳定剂化学试剂,2011,33(1),69~71亚磷酸三苯酯)))一种锂离子电池电解液稳定剂赵季飞,李冰川,苏建军,廖红英,王磊,付呈琳,孟蓉*(北京化学试剂研究所,北京 102607)摘要:以标题化合物为锂离子电池电解液添加剂,提高了锂离子电池电解液在贮存和高温条件下的色度稳定性。

通过测定不同亚磷酸三苯酯添加量下电解液的色度及电导率,得出亚磷酸三苯酯的最佳添加量为012%。

电化学测试结果表明,亚磷酸三苯酯的添加不影响锂离子电池的充放电及循环性能。

关键词:锂离子电池电解液;品质控制;稳定剂;亚磷酸三苯酯中图分类号:O 627151 文献标识码:A 文章编号:0258-3283(2011)01-0069-03收稿日期:2010-07-17作者简介:赵季飞(1983-),女,山东莱阳人,硕士,工程师,主要从事锂离子电池电解液的研发与生产工作。

联系作者:孟蓉,E-m ai:l 136********@s ohu.co m 。

电解液作为锂离子电池的重要组成部分,其稳定的性能是锂离子电池工作的重要保证。

锂离子电池电解液在运输和贮存的过程中,尤其在高温贮存过程中,容易变色。

一般情况下,锂离子电池电解液在50e 环境下,存放24h 即会色泽变深,导致电解液品质发生变化,影响锂离子电池各项性能的发挥。

在高温条件下,电解质六氟磷酸锂(L i P F 6)可分解成五氟化磷(PF 5),而PF 5引起碳酸乙烯酯、碳酸二甲酯或电解液中质子溶剂杂质等的聚合,生成可溶性单聚物、二聚物、齐聚物[1-7],随着聚合物中共轭体系的增加,聚合物光谱红移显现成色基团,导致电解液色度增大。

随着聚合度的增加,电解液颜色越来越深。

亚磷酸酯类化合物具有还原性,可作为抗氧剂应用于锂离子电池电解液中,推测亚磷酸三苯酯在锂离子电池电解液中的作用机理如下:亚磷酸三苯酯[TPP(i)]作用于PF 5催化下的溶剂聚合反应,可阻断链式聚合过程,使PF 5对聚合反应的催化作用失效,从而稳定了电解液的色度。

锂离子蓄电池电解液研究进展

收稿日期:2002211213 作者简介:高阳(1978—),男,安徽省人,硕士,主要研究方向为锂离子蓄电池。

Biography :GAO Yang (1978—),male ,master.锂离子蓄电池电解液研究进展高　阳1,　谢晓华2,　解晶莹3,　刘庆国1(1.北京科技大学固体电解质研究室,北京100083;　2.哈尔滨工程大学化工学院,黑龙江哈尔滨100051;3.中国科学院微系统与信息技术研究所,上海200050)摘要:锂离子蓄电池电解液及其添加剂的研究日益受到研究者的重视。

电解液作为锂离子蓄电池重要组成部分对电池性能影响很大。

综述了现阶段锂离子蓄电池电解液的溶剂、锂盐、低温性能以及热稳定性方面的研究状况。

添加剂是有效改善锂离子蓄电池电解液性能的手段,概述了目前添加剂几个主要方面———SEI 成膜添加剂、电导率提高添加剂、电池安全保护添加剂的研究进展。

关键词:锂离子蓄电池;电解液;添加剂中图分类号:TM 912.9 文献标识码:B 文章编号:10022087X (2003)0520479205Recent development of electrolyte s in lithium 2ion rechargeable batterie sG AO Yang 1,XIE Xiao 2hua 2,XIE Jing 2ying 3,L IU Qing 2guo 1(1.L aboratory on Soli d S tate Ionics ,Beiji ng U niversity of Science and Technology ,Beiji ng 100083,Chi na ;2.Instit ute of Chemical Technology ,Harbi n Engi neeri ng U niversity ,Harbi n Heilongjiang 150001,Chi na ;3.S hanghai Instit ute of Microsystem &Inf ormation technology ,Chi nese Academy of Sciences ,S hanghai 200050,Chi na )Abstract :Great importance is attached to the lithium 2ion rechargeable battery electrolyte and additive.Elec 2trolyte ,as an important part of lithium 2ion rechargeable battery ,will influence battery performances.Recent re 2search status on solvents ,lithium salt ,low temperature performance and thermal stability of electrolyte was re 2viewed.An additive is an effective means to improve the lithium 2ion rechargeable battery electrolyte.Present progress of the additives of lithium 2ion rechargeable battery electrolyte was stated ,such as the additive of SEI formation ,the additive of conductivity improvement ,the additive of battery protection.K ey w ords :lithium 2ion battery ;electrolyte ;additive 自从1859年G aston Plante 发明铅酸蓄电池以来,研究开发高比能量、长循环寿命的蓄电池一直是化学电源界探寻的目标。

太阳能控制器说明书

使用说明书1.本控制器为12V/24V 自动适应，首次安装时，请确保电池有足够的电压，以便控制器能够识别为正确的电池类型。

2.将控制器尽量靠近电池安装，以避免电线过长造成压降，影响正常电压判断。

3.本控制器适用于各种铅酸电池（包括开口，密封，胶体等），锂离子电池，磷酸铁锂电池。

4.本控制器只能使用光伏板作为充电源，请勿使用直流或其他电源作为充电源。

6.本控制器运行的时候会发热，请注意将控制器安装在平整，通风良好的表面。

1.采用工业级主控芯片。

2.红外遥控设置，LED 显示，断电记忆功能，IP68防护等级。

3.完整的四阶段PWM 充电管理。

4.内置过流/短路保护，开路保护，反接保护，均为自恢复型，不损伤控制器。

5.双MOS 防倒灌电路，超低发热量。

1.将蓄电池正负极按图示接入控制器，控制器将会自动检测蓄电池电压，并依据检测到的电池电压进行系统类型识别。

2.将负载正负极按图示接入控制器，注意不要反接。

3.将太阳能板按图示接入控制器。

注意：请严格按照以上顺序进行接入，否则可能会损坏控制器。

拆卸顺序与接线顺序相反。

1.控制器通电后，控制器首先对电池电压类型进行识别，如果电池电压低于18V ，则识别为12V 系统，如果高于18V ，则识别为24V 系统。

2.识别完系统电压后，用户可将遥控器对准红外接收口，按下想要的电池类型，此时蓝灯闪烁，设置即完成，无需重启。

3.本控制器支持3种电池类型，分别是：12V 铅酸电池（包括免维护型，开口型，胶体型等）11.1V 锂离子电池（3串，即3*3.7V ，包括容量型和动力型）12.8V 磷酸铁锂电池（4串，即4*3.2V ）如果是24V 系统，则分别对应：24V 铅酸电池（包括免维护型，开口型，胶体型等）22.2V 锂离子电池（6串，即6*3.7V ，包括容量型和动力型）25.6V 磷酸铁锂电池（8串，即8*3.2V ）4.设置完电池类型后，再选择负载的工作模式，其中系统（24H ）为负载常开模式，即负载输出一直通电（除非低电保护），光控（D2D ）表示负载为白天关闭，晚上打开，1-13则表示负载为晚上打开后，延时1-13小时后关闭，其中后2种模式一种用于太阳能照明系统，能够实现无人自动值守和控制。

Installation Recharging Instruction说明书

邮编：516121As shown in picture one:1. If you would like to wear the body-pack at your waist, please first fix one side of the hook into one of the holes in the middle of the system, stretch the hook to the width of the body-pack and then fix the other side of the hook into the corresponding hole. Take care that the body-pack is not scratched by the hook.2. For recharging, please plug the adaptor into power supply and insert DC port to one of the DC female socket of the charger. The indicator of the charger will light, which means the charger is working. The body-pack can be put inside the charger for recharging.3. As shown in the picture, the body-pack hook should be placed inside the gap of the charger. Make sure you have put them in correct direction and gently press down to make sure they are well connected. The indicator lights red when recharging and turns green when it is fully recharged.4. If several units need recharging at the same time, please connect the charger units by metal connecting sheets and screws, and connect the chargers with DC connecting bars. 10 groups of chargers (20pcs of body- pack units) can be recharged at the same time.pic 1Transmitter Receiver①. Power on/off Switch:Turn on the power supply, the power indicator LED ② will light. The system willautomatically set up the same frequency as last operating channel for the transmitter or receiver.②. Power Supply and Charging Indicator:When the transmitter or receiver battery power is full, it will turn green; When the power is lower than one segment, it will turn red; When there’s no signal for receiver, the green light will flicker;When there’s normal signal for receiver, the indicator lights green permanently; When recharging, it will light red;When battery is fully charged, the red light will turn green.(Remark: It should be recharged while the system is powered off)③. SET Setting Buttons:A. Mute: The microphone signal mute for transmitter(short press the button for mute or cancelling mute).Function Buttons Instructiontime and do not recharge for a long time.Do not set the system in the charger for a long period of time (over one month), as there may affect the service life of charger and system.If the system is not in use for a long time, please remember to maintain thebattery at regular period. Generally, please recharge the battery at least once per two months so as to avoid battery damage.For any technical question regarding operation, service or accessories, please contact your local distributor.The recharging time is about 4 hours. After recharging, please shut off power in Frequency Range:50Hz-12KHzTransmit Frequency Response:780-850MHZ Number of Channels: 100Operating range:≥100m(the maximum in open area can be 300m)Transmit Power:≤10dBmReceiving Sensitivity:-120dBm S/N Ratio:≥60dBPlaytime: Approx. 12hrsRecharging Period: Approx. 4hrsBattery Specification: 3.7V/950mAh polymer lithium-ion batteryTROUBLE No soundPower indicator does not light Extreme loudsound or sound distortionLoud noise or no signal Transmitter/Receiverautomatically power off-no signalPOSSIBLE REASONThe microphone or headset is not plugged completelyThe battery of transmitter is running out of power or in low power The receiver is set at low volumeThe battery is running out ofpower or in low powerVolume of input sound is too highVolume of headphone is too highWeak signal or interferenceLow battery powerSOLUTIONPull out the microphone or headset and replugReplace or recharge thebattery Volume up the receiver Replace or recharge the batteryAdjust the distance between microphone sound capturing and sound sourceAdjust the headphone volume to a proper levelDo not get too far away from transmitter(<100m) or adjust the channelReplace or recharge the batteryTroubleshooting Dear Valued Cus omer:t Thank you for purchasing Takstar WTG-900 wireless tour guide system. In order to achieve best performance of this system, please read the instruction manual carefully.Takstar WTG-900 supports wireless talkback function, the mode of tour guide or talkback can be switched according to your using requirement. It is widely used for travelling,meeting, museum visiting, coaching, education and other wireless synchronous translation.● ● 10 sets of systems can be used at the same time without mutual interference ● More than 100m long operation range, the maximum in open area can be 300m ● Supports wireless talkback function, switch the mode of tour guide or talkback according to your using requirements● LCD-display indicates the battery level, receiving signal strength as well as the current channel to control the working state anytime● Adopts intelligent AGC audio signal processing technology for high sound capture capability and high quality sound reproduction● Powered by high capacity lithium-ion battery, playtime is more than 12hrs ● Light and durable aluminum alloy construction● Supplied with special charger and portable aluminum case for convenient outdoor using780-850MHz UHF frequency band guarantees interference-free reception Product FeaturesCG-12 Charger 1pc DC Connecting Bar 1pc Aluminum Case 1pc Metal Connecting Sheet 1pc CG-12 Charger 10pcs Screw1pcPower Adaptor 1pc WTG-900 Transmitter 1set WTG-900 Receiver19setsDC Connecting Bar9pcsAluminum CaseCharger Package: Kraft BoxWTG-900R Receiver1pc Single-side Clip-on Headset (L)1pc Single-side Clip-on Headset (R)1pc Sponge Earpads 5pcs Li-ion Battery (inlay)1pc Hanging Strap 1pc Bodypack Hook1pcWTG-900T Transmitter 1pc Headworn Microphone1pc Single-side Clip-on Headset (L)1pc Single-side Clip-on Headset (R)1pcSponge Earpads 5pcs Windscreen5pcs Lavalier Microphone1pc Li-ion Battery (inlay) 1pc Bodypack Hook 1pcHanging Strap 1pc User Manual1pcTransmitterSingle-side Clip-on headsetReceiverHeadworn Microphone Package: Kraft Box Package: Kraft BoxAB356785678A BC599756C4656789A B8107三、充电操作方法：将配备的电源适配器插入AC电源插座，再把DC头插入充电座或充电箱，此时，充电座或充电箱电源指示灯会常亮，说明工作正常。

PEO基聚合物复合电解质的制备及性能研究

山东化工SHANDONG CHEMICAL INDUSTRY・44・2021年第50卷PEO基聚合物复合电解质的制备及性能研究梁文珂，王彦#，诸静，于俊荣，胡祖明(东华大学材料科学与工程学院东华大学纤维材料改性国家重点实验室，上海201620)摘要:将不同含量的单宁酸加入到聚环氧乙烷(PEO)和双三氟甲磺酰胺亚胺锂(LiCFSI)体系中，采用流延法来制备聚合物电解质膜’在氢键的作用下破坏PEO的结晶度来提高聚合物电解质的离子电导率°通过X射线衍射、差示扫描量热仪、热重分析仪、力学性能、表面形貌以及交流阻抗法等对聚合物电解质膜进行表征’结果表明，随着单宁酸(TA)含量的增加，结晶度下降，断裂伸长率提高，最高达到了675%,热力学性能也有很大的改善°室温下，当单宁酸含量为1%时,拉伸强度达到0固2MPg,离子电导率最大达到了3.4X10-5^^cm o 关键词：聚环氧乙烷;双三氟甲磺酰胺亚胺锂;氢键;聚合物电解质中图分类号:TQ151%0646.1文献标识码：A文章编号：1008-021X(2021)03-0044-03Sthdy on Preraration and Performancc of PEO-baseS Polymer Composite ElectrolyteLiang Wenke,Wang Yan*,Zhu Jing,Yu Junrong,Hu Zuming(State Key Laboratory for Modification of Chemical FiCers and Polymer Materials,Colleae of Materials Science and Engineering,Donghua University,Shanghai201620,China)Abstract:DiOerent contents of tannic acid were added to polyethylene oxide(PEO)and lithium bis(miUuowmethane )uooonamide)imide(LiTFSC))y)tem,and thepooymeeeoecteooytemembeanewa)peepaeed byca)tingmethod.Theionic conductieityoothepooymeeeoecteooytei impeoeed byde)teoyingthecey)ta o inityooPEO theough theaction oohydeogen bond).The polymer electrolyte membrane was characterized by X-ray dCfraction,d/ferential scanning ca/rimeter,thermog/vioemic anayaee,mechanicaHpeopeeties,sueoacemoephoogy,and ACimpedancemethod.Theeesu tsshowed thatwith theinceeaseoothe tannin content,theceystainitydeceeased,theeongation atbeeak inceeased,up to675%,and thetheemodynamicpeopeeties weeeasogeeatyimpeoeed.Ateoom tempeeatuee,when thetannicacid contentis1%,thetensiesteength eeaches0.22MPa, and the maxioum ionic conductivity reaches3.4x105S/cm.Key words:polyethylene oxiUe%lithium bisOiCuo/methane su/onamide ioide%hydrogen bond%polymer electrolyte锂离子电池作为储能装置的代表，因为其化学稳定性、循环寿命长和能量密度高等优势，比其他类型的电池如锌c电池、铅酸电池等有更广泛的应用［1］。

电动车电池英语

电动车电池英语Electric Vehicle BatteryElectric vehicle (EV) batteries are an essential component of electric cars and are responsible for storing and providing the energy needed to power the vehicle. These batteries are rechargeable and typically use lithium-ion technology, although other types of batteries such as nickel-metal hydride and solid-state batteries are also being developed for use in EVs.The lithium-ion battery is the most common type of battery used in electric vehicles due to its high energy density, long lifespan, and relatively light weight. These batteries are made up of several cells, each containing a positive and negative electrode, an electrolyte, and a separator. When the battery is charged, lithium ions move from the positive electrode through the electrolyte to the negative electrode, and when the battery is discharged, the ions move in the opposite direction.In addition to lithium-ion batteries, nickel-metal hydride (NiMH) batteries have also been used in electric vehicles, although they are less common due to their lower energy density and heavier weight. NiMH batteries are also rechargeable anduse a hydrogen-absorbing alloy for the negative electrode and nickel oxyhydroxide for the positive electrode.Solid-state batteries are a newer technology that is currently being developed for use in electric vehicles. These batteries use a solid electrolyte instead of the liquid or gel electrolyte found in lithium-ion batteries, which can potentially offer higher energy density, faster charging times, and improved safety.One of the key considerations in the design and development of electric vehicle batteries is their energy density, which measures the amount of energy that can be stored in a given volume or weight of the battery. Higher energy density allows for longer driving ranges and lighter weight, which are both important factors for electric vehicle performance and efficiency.In addition to energy density, the lifespan and durability of electric vehicle batteries are also important considerations. Over time, the capacity of a battery to hold a charge decreases, which can affect the driving range of the vehicle. Battery management systems and charging protocols are used to optimize the lifespan of EV batteries and ensure they operate at their peak performance for as long as possible.Charging infrastructure is another important consideration for electric vehicle batteries. The availability of charging stations and the time it takes to recharge an EV battery can have a significant impact on the adoption and use of electric vehicles. Fast-charging technology is being developed to reduce charging times and make electric vehicles more convenient for drivers.Overall, electric vehicle batteries are a critical component of electric cars and play a key role in the performance, range, and usability of these vehicles. As technology continues to advance, the development of more efficient, longer-lasting, and faster-charging batteries will be essential for the widespread adoption of electric vehicles.电动车电池电动车（EV）电池是电动汽车的重要组成部分，负责存储和提供车辆所需的能源。

阿特拉斯·科普柯 STwrench A 万能扳手说明书

AInterchangeable end fittings with patented recognition technology for PSET selection. Full traceability of various applications.BOptional advanced electronic gyroscope for precise angle measurement.CLow clearance compact head to get better accessibility and stability of operation.DBright LED headlight in front of the smartHEAD to illuminate dark spaces.EThe communication interfaces are USB or Wi-Fi thanks to the radio module. It is also possible to have communication with Power Focus via Wi-Fi or Bluetooth. Barcode module can be added to improve traceability and automatically startthe tests.FEasy-to-read display that can beread at angles of up to 180°.GFour signal lights forimproved operator feedback visible at 360°. Three special LED signals guide the operator for accurate tightening and measuring control.HErgonomic vibrating handle to ensure precise use.FeaturesABD FGHE C147.5 - 1 344 m m30 - 1 000 N m UNLIKE ANY OTHERCritical fastening duties are among themost essential tightening operations within industry today. So whether you are in thebusiness of assembling cars or trucks, tractors or harvesters, trains or planes, you need to be in control when it comes to production and quality assurance.That is where the Atlas Copco STwrench comes in. The STwrench provides a whole new approach to manual assembly applications. Naturally, it provides the accuracy, durability and ergonomics that are the hallmarks of the Atlas Copco product range. But the construction of the tool itself is entirely different.This is far from your standard transduce r i zed hand-held nutrunner. Unlike any other Atlas Copco tool, you can build the STwrench to meet your exact requirements. Due to its truly modular design, you have the freedom to create a tool that suitsThe STwrench implements a patented residual torque/angle measurement algorithm to measure the torque left on the joints by the tools inproduction. The STwrench residual torque/angle algorithm makes the residual torque check operator independent.Furthermore, as the residual point is detected in realyour applications perfectly. So you get outstanding Atlas Copco performance, but with greater flexibility than ever before.Use the STwrench for production to get full traceability of the entire tightening oper a tion including torque control, angle control and yield control. Or build your wrench to just tighten your joint with high torque accuracy.Use the STWrench for quality control to checkresidual torque, to perform joint analysis, including joint behaviour and stiffness, to set the correcttightening parameters for production and to test the reproducibility of joint stiffness on the benches.Build your own STwrench and create theultimate wrench for your specific requirements.Residual Torque/Angle Algorithmtime, buzzer, LEDs and vibration alert the operator to stop, avoiding overtorqueing.BUILD TO FITDeciding on the degree of control andconnectivity is the next step in creating your STwrench system. Establish what is right for you. Critical fastening duties are demanding, Atlas Copco believes in keeping both control and connectivity simple.Be in control. The STwrench controller puts you in charge. Menus, parameters and alarms are more manageable, with easy-to-use, text based software. Simply use the five navigation buttons for anytightening activity. Built-in LED signals immediately alert you to deviations from the preset program.Decrease downtime. Get fast access to the programmed data you need with Atlas Copco’spatented Rapid Backup Unit (RBU). The RBU transfers critical data to the hardware unit and serves as back-up for programming and configuration. If you need to change hardware, just connect the RBU on to the new hardware, switch on the unit and you are ready. All programming and network config u rations are transferred in seconds.Accessorize. Add the right accessories to yourSTwrench controller. Choose the wireless module to support wireless transmission of critical data. Add the barcode reader to easily scan barcode labels on assembly components for ease of traceability. Or select the correct PSet or Job. Manage up to four levels of barcodes for better error proofing.Get connected. It’s easy to connect your STwrench to the control systems you have in place. Standard fieldbus I/O, TCP/IP or Ethernet connectivity lets you decide between wired or wireless communications. Communications with ToolsNet, Torque Supervisor and Power Focus are easy with the wide variety of formats.Program and customize. Use ToolsTalk BLM to program the STwrench. You can export the latest 5000 results into an excel file or save the latest 10 traces. View and zoom the tightening trace for accurate analysis.STwrench RBU Production(8059 0930 91)STwrench Battery(8059 0930 86)smartHEAD A400 – 400 Nm(8059 0930 60)Reversible ratchet 14 x 18 – 3/4 in(4620 0082 00)THE SMARTHEADThe SmartHEAD really lives up to itsname. The smartHEAD has a built-in memorychip to store calibration values that areautomatically recognized by the STwrenchcontroller. They come in 21 different versionsfrom 15 Nm up to 1000 Nm, with or withoutangle reading. The smartHEAD is fast toexchange, this makes STwrench easy toupgrade and Service.The transducer and the gyroscope are locatedin the front part of the smartHEAD to be lessdependent from bending effects, a coefficientis stored after calibration to compensate anyremaining bending effect. The smartHEADhas a patented mechanism to recognize theend fitting tool connected, this allows toautomatically start the associated program.Choose your smartHEAD fitting yourapplication, connect it and you are ready to go.IRC Modules. Two different IRC moduleswith two different wireless technologies.No extra software isneeded. Simply plug in the new module to activatecommunication to the Power Focus, QATnode or different systems on the internet.QATnode P. The QATnode P makes it possible to print out a ticket result on a STAR DP8340 that is a 40 column serial printer. The layout of the ticket is fully configurable via TT BLM.OPTIONS AND ACCESSORIESQA TnodeThree different models ofQATnodes provide customized solutions to meet individual customer needs. The STwrench Modules can be connected to the QATnodes with WiFi via access point in real time – or via IrDa when not mounted on the cradle.With this module, theSTwrench is able to handle four different bar codes that activate or control the process. It also enables traceability. Simply plug in the module to activate the function.The battery charger fullyrecharges a STwrench battery in just four hours. The charger can be mounted horizontally on a wall, the battery screws into the charger.The lithium ion battery provides 16 hours of working time. If wireless communication is used, the working time is 10 hours.Connect the STwrench to the Power Focus using a standard Tensor SL cable. The STwrench cable box supplies power to the wrench and handles the communication between the wrench and the Power Focus.Battery charger Battery Cable boxBar code modulePower Focus 4000 is the control system for the STwrench. The Power Focus 4000 is available in one model with two versions, PF 4000 Compact and PF 4000 Graph. Power Focus 4000 or Focus 4000 is used in combination with the STwrench for line integration via digital I/O or fieldBus. This makes it possible to use Atlas CopcoQuality Integration Fastening (QIF) accessories, such as stack light, operator panel, mini display and other Atlas Copco standard QIF components.QATnode I/O. Inaddition to the QATnode P functionality, there are also 6 digital inputs and 5 digital outputs. Each of these are fully configurable and make it possible to enable or disable the wrench, select a PSet or JOB, as well as send out an OK or NOK.QATnode ing QATnode T function-ality, the STwrench can also send data to the ToolsNet server.• Lightweight and ergonomic all purpose manual torque wrench.• Tailored to your exact requirements.• Modular and cost-effective – only invest in what you need.• Easy to integrate, use, service and upgrade.• Joint analysis and quality control.• Quick and easy residual torque checks during production when traceability and error proofing are required.• Joint analysis when advanced functionality such as trace export,• Difficult access or limited space applications.• For immediate temporary backup on the line and assembly of special production.• Repair stations that need greater flexibility and a wider torque range.WHY YOU SHOULD INVESTThere are many reasons to invest in the STwrench. It could be the ergonomic lightweight design. Maybe you feel that its modularity guarantees that you’ll get just the right tool for your job – at the right cost. Maybe The agility and accessibility is what is appealing to you. Any way, this tool will easily find its place in your applications and have them run fast, easy and correct.Product Benefits:Benefits in quality assurance:Benefits in production:• Reliable, always up-to-date programming strategies and backup.• Smart accessories for error proofing and traceability, including wireless module, barcode reader, and Power Focus or Focus Interface Module.zoom and yield point detection are required.• Accurate residual torque checks communication using a reliablepaperless interface to the quality system.• Accurate and afford a ble tube-nut tightening.• When you need the same error proofing, traceability and quality as an electric tool.For all types of applications*End fitting has to be ordered separately, please see Industrial Power Tools Catalogue 9837 3000 01*Dimension Z is 50.5 mm when the STwrench battery short HD is installed (and Dimension K decreases by 45.5 mm). **Dimension J is the standard arm (measured at the center of the end-fitting tool); these data are used to calculate the torque correction coefficient when anextension is used. This dimension is calculated for the standard Atlas Copco end-fitting tools; if a different end-fitting tool is used, this measure must be recalculated.Refer to the “Appendix A – Calculating Torque and Angle Correction Coefficients” for further details. ***For STwrench Heavy Duty, both the feature “IRDA Port” and “Shock Indicator” arenot available.Functionality overviewTypeAB H L g Ordering No. mm mm mm mm Open end 9 x 12722517.5404620 0001 00822517.5394620 0002 00926 5.517.5384620 0003 001026 5.517.5424620 0004 001126 5.517.5414620 0005 001230717.5434620 0006 001330717.5484620 0007 001435817.5524620 0008 001535817.5514620 0009 0016388.517.5584620 0010 0017388.517.5604620 0011 001842920714620 0012 001942920744620 0013 00Open end 4 x 1813307251284620 0049 0014358251294620 0050 0015358251324620 0051 0016389251404620 0052 0017389251364620 0053 00184210251474620 0054 00194210251474620 0055 00215011251714620 0056 00225011251654620 0057 00245312251674620 0058 00276013302194620 0059 00306614302454620 0060 0032661432.52464620 0061 0034661432.52394620 0062 00B ALLHStandard end fitting tools with TAGTypeHexB H W L gOrdering No.mm mm mm mm mm Flared end 9 x 121022127.117.5574620 0028 001122.5128.617.5554620 0029 001223.512917.5594620 0030 001325.2121017.5554620 0031 001427131117.5604620 0032 001630131317.5654620 0033 001731.5131417.5654620 0034 0018331514.817.5744620 0035 001934.51515.819804620 0036 002137.51516.219884620 0037 002239151719924620 0038 002442151819754620 0039 00TypeAH L gOrdering No.mm mm mm mm Blank end 9 x12for making up specials 8 x 1414.58304620 0048 00Blank end 14 x1811 x 2521.521984620 0084 00Blank end 21 x2613 x 3030132204620 0085 00ALHBLWLHStandard end fitting tools with TAGTypeHexB H L g Ordering No. mm mm mm mm Ring end 9 x 12713817.5374620 0014 00814.2817.5404620 0015 001017.2917.5444620 0016 001118.5917.5414620 0017 0012201217.5494620 0018 001321.51217.5564620 0019 0014231217.5524620 0020 001524.21217.5524620 0021 001625.71317.5544620 0022 001727.21317.5594620 0023 001828.51317.5564620 0024 001930.31317.5654620 0025 0021331517.5714620 0026 002234.51517.5744620 0027 00Ring end 14 x 181321.511251274620 0063 00142311251234620 0064 001524.211251284620 0065 001625.712251334620 0066 001727.212251354620 0067 001828.512251344620 0068 001930.512251384620 0069 00213315251444620 0070 002234.515251454620 0071 002437.515251534620 0072 002741.517251624620 0073 00304519251824620 0074 003247.519251814620 0075 003450.519282104620 0076 00365319282034620 0077 00415920302404620 0078 00BLHTypeHexB H L gOrdering No.in mm mm mm Reversible ratchet 9 x 121/42214.517.5624620 0043 003/8332417.51364620 0044 001/23328.317.51474620 0045 00Reversible ratchet 14 x 181/24326.2253024620 0081 00*3/45030.7254674620 0082 00Reversible ratchet 21 x 263/4693062.513504620 0086 00BLHThe TAG placed on the ratchet defines the Pset. NOTE: Since several sockets could be used, it is recom -mended to hold the socket in such a way that it is not possible to remove it (e.g. using a pin).* The maximum torque which can be applied with 4620 0081 00 is 300 Nm.Standard end fitting tools without TAGTypeAB H L g Ordering No. mm mm mm mm Open end 9 x 12722517.5408059 0975 ********.5398059 0975 01926 5.517.5388059 0975 021026 5.517.5428059 0975 031126 5.517.5418059 0975 041230717.5438059 0975 051330717.5488059 0975 061435817.5528059 0975 071535817.5518059 0975 *******.517.5588059 0975 *******.517.5608059 0975 101842920718059 0975 111942920748059 0975 12Open end 14 x 1813307251288059 0976 0014358251298059 0976 0115358251328059 0976 0216389251408059 0976 0317389251368059 0976 04184210251478059 0976 05194210251478059 0976 06215011251718059 0976 07225011251658059 0976 08245312251678059 0976 09276013302198059 0976 10306614302458059 0976 1132661432.52468059 0976 1234661432.52398059 0976 13B ALHTypeHexB H W L gOrdering No.mm mm mm mm mm Flared end 9 x 121022127.117.5578059 0975 271122.5128.617.5558059 0975 281223.512917.5598059 0975 291325.2121017.5558059 0975 301427131117.5608059 0975 311630131317.5658059 0975 321731.5131417.5658059 0975 3318331514.817.5748059 0975 341934.51515.819808059 0975 352137.51516.219888059 0975 362239151719928059 0975 372442151819758059 0975 38B L WH TypeHexB H L g Ordering No. in mm mm mm Reversible ratchet 9 x 121/42214.517.5628059 0975 423/8332417.51368059 0975 431/23328.317.51478059 0975 44Reversible ratchet 14 x 181/24326.2 253028059 0976 32*3/45030.7254678059 0976 33Reversible ratchet 21 x 263/4693062.513508059 0976 38B LHStandard end fitting tools without TAGTypeHexB H L g Ordering No. mm mm mm mm Ring end 9 x 12713817.5378059 0975 13814.2817.5408059 0975 141017.2917.5448059 0975 151118.5917.5418059 0975 1612201217.5498059 0975 171321.51217.5568059 0975 1814231217.5528059 0975 191524.21217.5528059 0975 201625.71317.5548059 0975 211727.21317.5598059 0975 221828.51317.5568059 0975 231930.31317.5658059 0975 2421331517.5718059 0975 252234.51517.5748059 0975 26Ring end 14 x 181321.511 251278059 0976 14142311251238059 0976 151524.211251288059 0976 161625.712251338059 0976 171727.212251358059 0976 181828.512251348059 0976 191930.512251388059 0976 20213315251448059 0976 212234.515251458059 0976 222437.515251538059 0976 232741.517251628059 0976 24304519251828059 0976 253247.519251818059 0976 263450.519282108059 0976 27365319282038059 0976 28415920302408059 0976 29B L H TypeHex B H L g Ordering No. in mm mm mm Bits holder 9 x 121/4141017.5508059 0975 455/161612.517.5478059 0975 46Bits holder 14 x 185/161612.5251128059 0976 34BLHTypeHex B H L g Ordering No. in mm mm mm Fixed square 9 x 121/4221417.5718059 0975 393/8221417.5768059 0975 401/2221417.5828059 0975 41Fixed square 14 x 181/23018252038059 0976 303/44025253968059 0976 31BLHTypeA H L gOrdering No.mm mm mm mm Blank end 9 x 12for making up specials 8 x 1414.58308059 0975 47Blank end 14 x 1811 x 2521.521988059 0976 35Blank end 21 x 2613 x 3030132208059 0976 36ALHL* The maximum torque which can be applied with 8059 0976 32 is 300 Nm.ECO DESIGN STwrenchAtlas Copco BLMVia Guglielmo Pepe, 11 Paderno Dugnano (MI) - Italy 9 8 3 3 1 9 0 9 0 1 2 0 1 5 : 1–E N ©A t l a s C o p c o B L M , M i l a n , I t a l y . P r o d u c t i o n : A t l a s C o p c o B L M . 2 0 2 0。

Panasonic Toughbook H1 Field 手持平板电脑说明书

Safety (Canada) • IT Equipment EMI (US) • IT Equipment EMI (EU) • IT Equipment EMS (EU) • Industrial EMI (EU) • Radio (US) • Radio (Canada) • SAR (US)
The first MIL-STD-810G and IP65 certified
handheld tablet PC1.
Windows®. Life without Walls™. Panasonic recommends Windows.
H1 The NEW Panasonic Toughbook Field.
Setup, Diagnostics, PC Information Viewer, Online Reference Manual, Adobe® Reader, Keyboard Button Manager, Hard Disk Data Erase Utility, Recovery DVD
■ The First MIL-STD-810G and IP65 Certified Handheld Tablet PC1
■ 6-foot Drop Rating1
■ Sunlight-viewable 10.4" Dual-touch Display
■ Designed for Vehicle Use
integrated features
H1 Field Base H1 Field Pro • 2MP camera with dual LED light • 2D barcode reader (1D and 2D capable) H1 Field Elite • 2MP camera with dual LED light • 2D barcode reader (1D and 2D capable) • Insertable SmartCard reader • 13.56MHz Contactless RFID and SmartCard reader

Flexible all-solid-state high-power supercapacitor fabricated with nitrogen-doped carbon nanofiber

This journal is ª The Royal Society of Chemistry 2013
Received 14th July 2013 Accepted 15th August 2013 DOI: 10.1039/c3ee42366b /ees
Broader context
The ever-growing requirements of portable and exible electronic devices spark the intense interests in developing next-generation low-cost, pliable, and sustainable supercapacitor systems with high power densities, long-term life span, and operation security. We engineered and fabricated a exible all-solid-state supercapacitor using the nitrogen-doped carbon nanober as the electrode materials via a low-cost, eco-friendly, and highly scalable hydrothermal method with pyrolyzed bacterial cellulose (p-BC) and aqueous ammonia. The exible device exhibits a maximum power density of 390.53 kW kgÀ1 and long life span with $95.9% of the initial specic capacitance aer 5000 cycles. Therefore, this device holds signicant prospect for commercial applications.

A review of lithium and non-lithium based solid state batteries

ReviewA review of lithium and non-lithium based solid state batteries Joo Gon Kim a,1,Byungrak Son a,**,1,Santanu Mukherjee b,1,Nicholas Schuppert b, Alex Bates b,Osung Kwon c,Moon Jong Choi a,Hyun Yeol Chung d,Sam Park b,*a Wellness Convergence Research Center,DGIST,333Techno Jungang-daero,Hyeongpung-Myeon,Dalseong-Gun,Daegu711-873,Republic of Koreab Department of Mechanical Engineering,University of Louisville,KY40292,USAc College of Liberal Education,Keimyung University,Daegu704-701,Republic of Koread Department of Information and Communication Engineering,Yeungnam University,Gyeongbuk712-749,Republic of Koreah i g h l i g h t sA comprehensive review of all aspects of solid state batteries:design,materials.Tabular representations to underscore the characteristics of solid state batteries.Solid state electrolytes to overcome the safety issues of liquid electrolytes.a r t i c l e i n f oArticle history:Received13October2014 Received in revised form17January2015Accepted9February2015 Available online16February2015Keywords:Solid state batteriesSolid electrolytesLithium based batteriesLithiation/delithiationSolid electrodes a b s t r a c tConventional lithium-ion liquid-electrolyte batteries are widely used in portable electronic equipment such as laptop computers,cell phones,and electric vehicles;however,they have several drawbacks, including expensive sealing agents and inherent hazards ofﬁre and leakages.All solid state batteries utilize solid state electrolytes to overcome the safety issues of liquid electrolytes.Drawbacks for all-solid state lithium-ion batteries include high resistance at ambient temperatures and design intricacies.This paper is a comprehensive review of all aspects of solid state batteries:their design,the materials used, and a detailed literature review of various important advances made in research.The paper exhaustively studies lithium based solid state batteries,as they are the most prevalent,but also considers non-lithium based systems.Non-lithium based solid state batteries are attaining widespread commercial applica-tions,as are also lithium based polymeric solid state electrolytes.Tabular representations and schematic diagrams are provided to underscore the unique characteristics of solid state batteries and their capacity to occupy a niche in the alternative energy sector.©2015Elsevier B.V.All rights reserved.1.Introduction and backgroundThe advent of solid state batteries must be understood in the context of the challenges faced by modern storage systems,espe-cially Li-ion batteries.Existing Li-ion batteries,apart from the storage and active components,contain considerable quantities of auxiliary materials and cooling equipment[1].Loss of battery quality due to continuous charging and discharging cycles,ﬂam-mability,dissolution of the electrolyte,and from vehicle to grid utilization has been another important concern.Solid state batteries are being extensively studied and researched with a view to solving these problems[1,2].Conventional batteries,e.g.,the Li-ion battery,usually consist of a liquid electrolyte,which helps transport Li ions to and from the cathode and anode[3e5].How-ever,this increases the chance of leakage of the electrolyte if any holes are present;this is one of the main drawbacks of the con-ventional Li-ion battery.Another problem inherent in the liquid electrolyte battery is the formation of dendrites of Li,which make it prone to explosion[5,6].In order to surmount these problems,a solid electrolyte can be positioned between the electrodes.This is the principle underlying the solid state battery[3,4].The advantage of this type of battery is a reduction in the net weight and volume of the battery,greater energy output,and easy transfer of Li ions, which affords better efﬁciency[3,5].Solid state batteries also exhibit some advantages over the other commonly known energy*Corresponding author.**Corresponding author.E-mail addresses:brson@dgist.ac.kr(B.Son),Sam.Park@(S.Park). 1These authors contributed equally to thiswork.Contents lists available at ScienceDirect Journal of Power Sourcesjournal h omepage:www.elsevier.co m/lo cate/jp owsour/10.1016/j.jpowsour.2015.02.0540378-7753/©2015Elsevier B.V.All rights reserved.Journal of Power Sources282(2015)299e322storage devices,capacitors[7,8].The advantages lie in the very small self-discharge of the solid state batteries,minimal wear and tear,and yield of a more uniform output voltage[7,8].In recent decades,solid state batteries,especially solid state lithium ion batteries,have been widely used[9e13].Ideally,a solid state electrolyte should have high cation conductivity,with good me-chanical properties and good chemical stability that cannot be easily reduced by the metal itself[9,14].Moreover,owing to rapidly growing microelectronics and integrated optoelectronics circuits, there is an increasing demand for new,lightweight batteries with high-cycle life and high energy density.In a commercial lithium ion battery,the liquid electrolyte carries the risk of explosion andﬁre; moreover,the separators and packaging limit the size of the bat-teries.All these factors have contributed to the development of all-solid state batteries[14e16].However,solid state batteries also present challenges,such as their relatively lower power density, high ionic resistance at room temperatures,and manufacturing cost[3,15].The atomic layer deposition(ALD)technique is an important method applied in the manufacture of solid state thin ﬁlm electrolytes[17e20],but it is rather costly and indeed forms the bulk of the cost of the battery[3,21].2.Solid state batteriesA solid state battery is similar to a liquid electrolyte battery except in that it primarily employs a solid electrolyte.The parts of the solid state Li ion battery include the anode,cathode and the solid electrolyte[22,23].The anode is attached to copper foil,which helps improve the electrical conductivity of the battery.[22].Dur-ing the charging cycle,there is movement of the Li ions of the LiCoO2crystal toward the electrolyte interface[22,24].As a result, the Li ions cross over to the carbon layers in the anode through the electrolyte.During the discharging cycle,the reverse process takes place,and the Li ions travel via the electrolyte toward the LiCoO2 particles[22,23,25].Solid state batteries can overcome some of the inherent problems of liquid electrolyte batteries,being less haz-ardous and having a lessﬂammable electrolyte-electrode system and better storage capacity.In theﬁeld of power supply for cardiac pacemakers with low-power requirements,all solid state batteries are well established because of safety,lifetime,and achievable energy density[26,27].As mentioned in a book,all solid state battery is one of new type of batteries with excellent safety and high energy density[28].Substitution of liquid electrolyte by a solid allows simpliﬁcation of the cell structure,and many restrictions in terms of architecture and safety are eliminated[29,30].Solid state electrolytes are being intensively researched as the key which present safety advantages over present liquid Li-ion technology [31e33].The non-ﬂammability of their solid electrolytes offers a fundamental solution to safety concerns and remarkable environ-mental compatibility[34e38].Also the solid state electrolytes tend to last longer,as they un-dergo less wear and tear during operation,are more proof against shocks and vibrations,and can operate within a larger temperature range,up to about200 C.However,they have several disadvan-tages as well[6].Solid state electrolytes,and consequently batte-ries,are not suitable for use in low and ambient temperature conditions,and the power and current output is generally less [39,40].This is because of the large resistance of the solid oxide at room temperature to ionic conductivity,whereas this does not occur at elevated temperatures.In addition,at ambient or room temperature,the stress created at the electrode-electrolyte inter-face due to continuous contact with the solid electrolyte tends to reduce the longevity of the battery[6,41].Fig.1is a schematic di-agram of a lithium based solid state battery.The curved arrows indicate the movement of the Li ions during the charging and the discharging process,respectively.The electrons produced due to the reaction are used to drive a load in the external circuit.The set of cathode and anode materials and their corresponding suitable electrolytes are also given in Fig.1,marked with matching colors(in the web version).2.1.Structure of solid state batteries2.1.1.CathodeThe cathode in the solid state battery is important,as it supplies the battery with the necessary ions during the charging process and vice versa during the discharging process.The cathode must be structurally stable during this process.It is important that the ionic conductivity of the cathode be good,as the charging and dis-charging process involves the transference of ions across it [6,24,42].Commonly used cathode materials for lithium based solid state batteries are lithium metal oxides,as they exhibit most of the above necessary properties.Lithium cobalt oxide(LCO),which has the stoichiometric structure LiCoO2,is a widely used lithium metal based oxide.LCO exhibits a layered structure that is suitable for the lithiation/delithiation process,and it has a relatively high speciﬁc energy of about150mAh gÀ1,which makes it a preferred cathode material[6,24,43].LCO exhibits an octahedral arrangement with a layer of lithium atoms between oxygen and cobalt[44,45].How-ever,it is relatively costly to manufacture,especially with the use of cobalt[45].Lithium manganese oxide(LiMn2O4)is another mate-rial used in the cathode of solid state batteries[46,47].This com-pound produces very little resistance to the passage of lithium ions during the lithiation and delithiation process,thanks to its spinel based structure,which makes it suitable for use[6].LiMn2O4has its drawbacks too,notably phase change during the ion transfer pro-cess,which hinders stability,and a lower capacity than LCO. LiFePO4,another lithium based phosphate,has the advantage of being less hazardous and less expensive to produce than the other lithium based oxide materials[6,48].Moreover,LiFePO4has an olivine based structure(a one-dimensional chain of lithium ions), which greatly assists the transfer of ions and provides less resis-tance to the path of ion transfer[6,24].On the other hand,phos-phorus has a high self-discharge rate,which reduces the longevity of this material.Apart from these lithium based oxides,vanadium based oxides have also been tested,as they exhibit similar layered structures that help during the lithiation/delithiation process.However,they produce low output voltages and sometimes they lack longevity, which has limited their use as cathode materials in solid state batteries[6,49,50].In fact,the overall performance of a solid state battery is still limited by the performance of cathode materials,as its speciﬁc capacity is generally lower[14].The application of nanoparticles to the typical cathode,such as LiCoO2,can produce better properties,but they will react more strongly with the elec-trolyte at high temperature and lead to more safety issues than using such materials in the micrometer range[14,51].Coating the nanoparticles with a stabilizing layer can reduce this problem,but it also reduces the lithiation/delithiation rate of the cathode.2.1.2.AnodeMaterials that can store Li/Liþto great capacity are usually potentially good anode materials.This is because the anode is where the lithiation takes place during the charging process.Pure lithium metal has been tried as an anode material.Unemoto et al. have used lithium anodes in lithium sulfur battery systems with room temperature ionic lithium(RTIL)liquid fused with silica nanoparticle solid state electrolyte and they were able to achieve a discharge capacity of690mAh gÀ1after45cycles of operation[52]. Cai et al.have used lithium metal anode with a LiMn2O4cathodeJ.G.Kim et al./Journal of Power Sources282(2015)299e322 300system and have obtained a 91.39%capacity retention after 1000cycles of use at room temperature conditions [53].Taib et al.have incorporated lithium anodes in solid state cells having biopolymer (chitosan)based solid state electrolyte and have obtained a stable discharge capacity of 160mAh g À1up to 50cycles of operation [54].However pure lithium metal anodes have their drawbacks.An important problem associated with lithium anodes is their inability to be used in high temperature operations,because of the lithium metal's very high sensitivity to elevated temperature conditions [55,56].Accelerating rate calorimeter (ARC)results have shown that,as the number of cell cycles of operation rises,there is a considerable increase in the self-heating of the Li anodes because of the increase in the surface area of the anodes due to the lithiation process [56].According to Sacken et al.,the primary reason for this failure is that the structural integrity and morphology of Li cannot be manipulated properly [56].Therefore,several safety issues need to be kept in mind when using Li anodes.Another drawback of the dendrite formation effect is the development of non-uniform cur-rent density across the cell,which in turn leads to local temperature gradients throughout the cell surface [57].This makes it dif ﬁcult to integrate the cell,especially in miniature devices,as the tempera-ture gradient becomes hazardous [57].Also,this dendrite forma-tion steadily depletes the amount of lithium necessary for the cell cycling process and may even result in the short circuit of the cell [57].Apart from uncombined metallic lithium,lithium based metal oxides such as lithium titanate (LTO)have also been used.The stoichiometry of lithium titanate is Li 4T 5O 12.The main advantage of LTO is its octahedral structure,which can easily integrate lithium ions within it during the lithiation process [58e 60].Also,LTO does not undergo much structural change during the lithiation/deli-thiation process and is relatively stable,which makes it suitable for use.However,LTO has a rather low speci ﬁc energy of 175mAh g À1,which sometimes limits its usage to areas where low power output is required [41,59].Carbon and carbon based materials are commonly used anode materials in solid state batteries [61,62].Graphite too is quite widely used as an anode material in solid state batteries,yielding several advantages,such as having a layered structure that can incorporate the lithium ions during the lithiation/delithiation process,its ability to withstand large numbers of charging and discharging cycles,and relative ease of manufacture [62,63].Graphite can also easily be doped with other materials to improve its capacity.The major problem with graphite is its rather low capacity.Soft carbon is another material used.It bene ﬁts from having a disordered structure that is favorable toward incorporating Li ions [58,63].Therefore,at present,graphitic carbons are commonly used for the anode of the commercial lithium battery because they have a higher speci ﬁc charge and more negative redox potential than most metal oxides or polymers;further,they demonstrate better cycling performance than lithium alloy,thanks to high structural stability and less volumetric expansion in the lithiation reaction [14].Fig.2is a schematic representation of the different solid state battery systems with their applications and respective capacities.Metallic alloy-based anodic systems have also been studied,notably Sn,Pb,Sb,Al,and Zn along with their alloy systems [4].The principle behind their use is the ability of the alloy atoms to store multiple lithium atoms in the host crystal lattice.One of the best-known tin-based anodes is Li 4.4Sn,which is the ﬁnal phase after lithiation.A theoretical maximum gravimetric capacity of 959.5mAh g À1has been calculated for this system [5].However,the primary problem with these tin-based anodes is that they suffer from large volume changes (and consequently large stresses)dur-ing the lithiation process,fracture takes place quickly,and hence their longevity is rather short [5].Silicon-and carbon-based com-posite anodes have been tested.Carbon is used to reduce the large volume expansion experienced by the Si anode during lithiation [5].Wang et al.reported a gravimetric capacity of 794mAh g À1of Si/C composite anode systems after about 20cycles of operation [5,64].Anodes in solid state battery systems tend to be subjected to large quantities of stress,which take its toll on their longevity.Several groups have studied the development of stress and its distribution in solid state battery anodes during operation.Mukhopadhyay and Sheldon have shown that stress in the Li-based anode due to the lithiation/delithiation process arises mainly from a change in lattice dimensions [65].Unalloyed metallic Li being relatively soft,these problems are magni ﬁed compared to anodic alloys.Some of the processes that lead to disintegration areplasticFig.1.A schematic representation of a representative lithium based solid state battery,showing the direction of ion movement and some of the possible anode,electrolyte,and cathode combinations.J.G.Kim et al./Journal of Power Sources 282(2015)299e 322301deformation,fragmentation,and fracturing [62,65].Another factor is that the lithiation/delithiation results in a reduction in elastic modulus along the basal planes and there is a consequent increase in elastic modulus perpendicular to the basal planes.These unequal expansions and reductions of the Li-based anodes further make their integration dif ﬁcult [66].As a result of the stresses and me-chanical changes,the energy necessary for the phase trans-formation is reduced,as is the ability of the Li anode to operate at elevated temperatures [65].This leads to a number of losses during the running of the cell,especially hysteresis losses during the lithiation/delithiation process,which serve to decrease the overall output of the cell [65,67].Huang et al.have developed a compre-hensive mechanics model for understanding the stress generated during lithiation in solid state lithium ion battery anodes [68].They determined that the important factors are plastic deformation of the electrode and also stress due to Li rich and poor phases formed during the lithiation process [68].During the delithiation process,however,tensile hoop stress is created,which results in contraction of the sample.Fig.3illustrates the stress induced in a Si nano-particle and its consequent cracking due to the lithiation process taking place.Silicon nanowires have been developed as lithium ion battery anodes,as they tend to contain less stress due to thelithiation/delithiation process [69].Sethuraman et al.have studied the development of stress in silicon anodes in-situ due to the electric potential in the cell during its performance [67].They re-ported that the Si anodes undergo cyclically varying tensile and compressive stresses of magnitudes sometimes as high as 1.5GPa [67].Based on the thermodynamic considerations obtained from the Larche-Cahn chemical potential theory,the authors demon-strated the existence of electrical potential-based stress in the anodic silicon and found the ratio of potential change to stress to be 62mV GPa À1[67].2.1.3.Con ﬁguration of electrodesVarious electrode and electrolytic con ﬁgurations have been tested for solid state battery systems.For example,one of the ﬁrst new designs from the usual coin cell strategy was plastic-based LiPON electrolyte or PLiON,which provided a great deal of ﬂexi-bility and ease of use [70].Some other con ﬁgurations that have been tried are the cylindrical,prismatic,and ﬂat.These have been considered to be the most versatile con ﬁgurations,leading to op-timum surface area contact between the anode/electrolyte and the cathode/electrolyte [70].Another important factor is the dendrite formation in the Li anodes,owing to its close proximity totheFig.2.The capacities of different types of batteries and their respective applications [41,159].The diagram shows that thin ﬁlm Li ion based solid state batteries provide some of the best properties in terms of both energy density andcapacity.Fig.3.Part (a)shows a TEM image of lithiation and consequent cracking of the Si nanoparticle.As can be seen from the image,the crystalline Si nanoparticle (c-Si)shares a common interface with the tungsten electrode on side and a Li counter electrode.During the lithiation process,as seen in part (b)the Si particle has cracked and the Li envelopes it quickly and even enters the particle forming a core shell of pure Si with an external amorphous LixSi.Thus it can be understood how lithiation causes cracks due to induced stress [355,356].J.G.Kim et al./Journal of Power Sources 282(2015)299e 322302electrolyte and the consequent electrical reaction.Scrosati et al. were able to solve this problem by doping the Li anodes with other metals(Co,Ta);this conﬁguration was called the“rocking-chair”technology[71].Short circuiting due to dendrite formation is a practical problem which has been described by Nishi[72].Ac-cording to him,dendrite formation causes the problem of short circuiting by penetrating into the electrodes and causing poor cycle performance[72].According to Song et al.,the presence of long interconnect and channels allow paths for the dendrites to grow and proceed[73].These,consequently lead to the reduction of cell efﬁciency and ultimately internal short circuiting.Therefore they have recommended the application of non-porous polymer mem-branes to prevent the growth of these dendrites[73].The choice of the electrode/electrolyte conﬁguration is,therefore,very important to the proper functioning of the cell,and its optimization is abso-lutely essential.Further,“thickﬁlm technology”has been studied by several groups.This basically involves the deposition of layers of composite materials from their precursor solvents;these compos-ite materials are further ground and compacted with a polymeric binder to produce the necessary electrode.Kim et al.have used thickﬁlm technology to develop electrodes for microbatteries, which were deposited on metallic current collectors[74].A poly-meric gel electrolyte consisting of PVDF-LiPF6-propylene carbonate (PC)-ethylene carbonate(EC)was used to complete the cell[74]. Vapor deposition technology to deposit thinﬁlm electrodes has been studied by Fleischauer et al.[75].They were able to deposit porous silicon thinﬁlms having a very high aspect ratio,which were approximately500nm in height.This resulted in a form of3D microstructure for the thinﬁlm batteries[75].Teixidor et al.have demonstrated the formation of carbon pillars as microelectrodes for thinﬁlm lithium ion batteries[76].For this purpose,litho-graphic patterning coupled with thermal decomposition of cross-linked photoresists was used.The photoresist acted as the solvent and the curing of the dispersion was done by UV light[76].Inter-digitated conﬁguration cells were studied and modeled by Zadine et al.[77].They usedﬁnite element analysis(FEA)for modeling and were able to study the rate constraints of the electrochemical processes,especially those due to collector resistance with this technique[77].Composite ceramic electrodes,an important class of solid state electrodes,have been developed and studied by a number of groups.Mizuno et al.have prepared composite ceramic electrodes by thorough grinding of the precursor materials LiCoO2and Li2S.P2S5.[78].Theﬁnal step in the design of the composite ceramic electrode involved the pressing together of the Li based positive electrode,the In foil negative electrode and the electrolyte which were then held together by stainless steel current collectors.The authors have reported a discharge capacity of75mAh gÀ1at a cut off voltage of1.5V[78].Wei and coworkers have developed a metal oxide electrode for application in all solid state sodium recharge-able batteries[79].A22m m thick P2Na2/3[Fe1/2Mn1/2]O2cathode and52m m thick Na2Ti3O7$La0.8Sr0.2MnO3composite anode pre-pared by solid state reactions was used,yielding a capacity of 152mAh gÀ1at350 C[79].Delaizir et al.have studied the process of spark plasma sintering to develop ceramic electrodes for all solid state batteries[80].They have developed monoclinic Li3V2(PO4)3as both the anode and the cathode.Non uniform sized precursor materials were used to perform the sintering so as to achieve the highest degree of compactness.The authors have mentioned that the compactness of the electrolyte is important in controlling the electrical conduc-tivity;an optimal ionic conductivity of2.8*10À4S cmÀ1was ob-tained[80].They have demonstrated rather promising surface capacity of2.2mAh cmÀ2for a cut off potential of2.45V[80].Electrode architecture is another important factor while designing the solid state battery.To have a better interface between electrodes and solid electrolyte,Soo et al.have developed rubbery block copolymer type electrode systems[81].They have used these electrodes in Li based solid state battery systems and good cycling properties have been noticed under room temperature conditions [81].Zhang et al.have developed columnar nanostructured tin oxide electrodes for Li ion rechargeable batteries[82].These tin oxides are essentially columnar grains with a coating of nano-particles,20nm in diameter[82].A reversible capacity of 460m Ah gÀ1is obtained under ambient conditions at a current density of0.3mA cmÀ2[82].Li et al.have studied mesoporous anode systems which were made of Co3O4[83].These mesoporous systems demonstrated a capacity of700mAh gÀ1after20cycles of operation which has been considered to be a reasonable result[83].To facilitate electrochemical reactions,several approaches have been researched to have a good solid e solid contacts between electrode and electrolyte[35,36,84e90].The achievement of close contacts and the increase contact areas are important aspects to have an effective charge e transfer reaction as explained by Tasu-misago et al.[84].Using nanocomposites by a ball milling process, the surface coating of active material particles with thinﬁlms associated with a pulsed laser deposition(PLD)techniques,and using supercooled liquid of glass electrolyte have been established to have a favorable contact at the interface between electrode and electrolyte which leads to a good performance of all solid state batteries[36,84,85,89e92].2.1.4.ElectrolyteAs the performance of a solid state battery depends on the diffusion of ions within the electrolyte,solid electrolytes are required to have high ionic conductivity and very low electronic conductivity and should exhibit a high degree of chemical stability [14,93].Crystalline materials such as lithium halides,lithium nitride,oxy-salts,and sulﬁdes have been found to be good as solid electrolytes.The most favorable features of the solid electrolyte are that there is no corrosive or explosive leakage and the chance of internal short circuit is less,and hence it is safer[14,94].Solid electrolytes should have a sufﬁcient number of mobile ions to enable conduction to proceed smoothly.Solid state electrolytes should therefore have enough vacancies in their crystal lattice to permit the ions to move,and the overall activation energy must be low[94,95].Different types of solid state electrolytes have been employed, based on their conﬁgurations and electrode/electrolyte materials setups.Therefore,solid state electrolytes are broadly classiﬁed into two types,bulk solid state electrolytes and thinﬁlm solid state electrolytes.The primary distinction is on the degree of thickness of the electrolyte;thickness of bulk solid state electrolytes are usually in the range of several hundred micrometers,whereas that of thin ﬁlm solid state electrolytes are in the range of hundreds of nano-meters to several microns.Another primary area of difference be-tween the two is the way they are fabricated:bulk solid state electrolytes are usually prepared by techniques such as mechanical milling,sintering and compaction,annealing and heat treatment whereas thinﬁlm solid state electrolytes are fabricated by pulsed laser deposition,spark plasma sintering,CVD etc.a)Bulk solid state electrolytes(electrolytes at the macroscale)Among the most commonly used solid state electrolytes are the solid polymeric electrolytes(SPE)[96].The main aim while devel-oping SPEs is to obtain ionic conductivities as high as those of liquid electrolytes[96].If the polymer is obtained by complexing it with an inorganic salt,then it has a low lattice energy,which makes the resultant SPE more stable[96].Frequently used polymer e inorganicJ.G.Kim et al./Journal of Power Sources282(2015)299e322303。

solid-state reacted Li4Ti5O12 for lithium ion batteries

Effects of the starting materials and mechanochemical activation on the properties of solid-state reacted Li 4Ti 5O 12for lithium ion batteriesChang-Hoon Hong a ,Alﬁan Noviyanto a ,Ji Heon Ryu b ,Jaemyung Kim c ,Dang-Hyok Yoon a ,*aSchool of Materials Science and Engineering,Yeungnam University,Gyeongsan 712-749,Republic of KoreabGraduate School of Knowledge-Based Technology &Energy,Korea Polytechnic University,Siheung 429-793,Republic of KoreacEnergy Development Team,Corporate R&D Center,Samsung SDI,Yongin 446-577,Republic of KoreaReceived 13April 2011;received in revised form 30June 2011;accepted 5July 2011AbstractLi 4Ti 5O 12was synthesized by a solid-state reaction between Li 2CO 3and TiO 2for applications in lithium ion batteries.The effects of the TiO 2phase and mechanochemical activation on the Li 4Ti 5O 12particles as well as the corresponding electrochemical properties were investigated.Rutile TiO 2was more desirable in acquiring high purity Li 4Ti 5O 12than anatase due to the anatase to rutile phase transformation,which was found to be more rigid in the solid-state reaction than the intact rutile phase.Mechanochemical activation of the starting materials was effective in decreasing the reaction temperature and particle size as well as increasing the Li 4Ti 5O 12content.The speciﬁc capacity depended signiﬁcantly on the Li 4Ti 5O 12content,whereas the rate capability improved with decreasing particle size due to the enhanced contact area and reduced diffusion path.Overall,a 200nm-sized Li 4Ti 5O 12powder with a speciﬁc capacity of 165mAh/g could be synthesized by optimizing the milling method and starting materials.#2011Elsevier Ltd and Techna Group S.r.l.All rights reserved.Keywords:E.Batteries;Solid-state reaction;Mechanochemical activation;Li 4Ti 5O 12;Electrochemical properties1.IntroductionLi 4Ti 5O 12is a promising anode material for high power Li-ion batteries owing to its good cycle performance and little structural change during the Li +intercalation and de-intercalation process with a theoretical capacity of 175mAh/g [1–5].Since it shows a ﬂat Li insertion potential of 1.55V versus Li/Li +,which is higher than the reduction potentials of common electrolyte solvents,it does not form a solid electrolyte interface during operation [2,6].These properties can be a great merit for electric and/or hybrid vehicle applications of Li-ion batteries,which demand high power operation and long-term stability [7,8].To produce high rate Li-ion batteries,a very ﬁne active material is more desirable than a coarse one due to its shorter Li +diffusion path and greater electrode–electrolyte contact area for Li +intercalation and de-intercalation [9–11].On theother hand,the properties of the particles depend signiﬁcantly on the synthetic process and starting materials,which lead to ﬁnal products with range of sizes and morphologies.Therefore,considerable effort is being made to enhance the electro-chemical performance of batteries by optimizing the electrode materials,including the utilization of various synthetic methods,doping and coating with other materials [12–18].Generally,a spinel-type Li 4Ti 5O 12is synthesized by an economic solid-state reaction using TiO 2and Li 2CO 3,which generally results in a signiﬁcant amount of agglomeration and a coarse particle size.This is why wet chemical methods,such as hydrothermal and coprecipitation,have been attempted despite their high cost [19–22].The synthesis of ﬁne ceramic powders through a solid-state reaction with the aid of an advanced high energy mill was reported recently [23,24].Compared to a conventional ball mill,the modern high energy mill shows much higher milling efﬁciency owing to its high speed rotor turning at up to several thousand rotations per minute.Their high energy input along with the use of small grinding media enables the achievement of very small particle sizes in a very short processing time/locate/ceramintAvailable online at Ceramics International xxx (2011)xxx–xxx*Corresponding author.Tel.:+82538102561;fax:+82538104628.E-mail address:dhyoon@ynu.ac.kr (D.-H.Yoon).0272-8842/$36.00#2011Elsevier Ltd and Techna Group S.r.l.All rights reserved.doi:10.1016/j.ceramint.2011.07.007[24,25].The mechanochemical activation by heavy milling is the key process in the solid-state synthesis of nano-sized ceramic powders,for example BaTiO 3[23,24],which alters the physicochemical properties of the starting materials.Finely milled starting materials enhance the solid-state reaction due to their high activity and decrease the reaction temperature and ﬁnal particle size.To the best of the authors’knowledge,there are no reports on the effectofmechanochemical activation for the startingmaterials on the formation of Li 4Ti 5O 12powder.With this background,this study compared the effects of milling methods (ball milling and high energy milling)on the properties of Li 4Ti 5O 12powder and the corresponding electrochemical properties.In addition,the effects of two different starting TiO 2phases,i.e.,anatase-and rutile-phased TiO 2,were also examined.2.Experimental procedure2.1.Starting materialsCommercial Li 2CO 3and TiO 2powders were used as Li-and Ti-precursors for Li 4Ti 5O 12synthesis,respectively,where two different types of TiO 2powders,i.e.,anatase-and rutile-phase,were used to examine the phase effects.Table 1lists the characteristics of the starting materials,including the manu-facturer,mean particle size and purity.2.2.Synthesis of the spinel Li 4Ti 5O 12To synthesize 100g of Li 4Ti 5O 12powder,32.19g of Li 2CO 3and 86.98g of TiO 2,which correspond to a Li/Ti stoichiometric ratio of 4/5,were mixed with 200g of de-ionized water after adding 2wt.%of the ammonium salt of polycarboxylic acid (Cerasperse 5468-CF,San Nopco,Korea)with respect to the ceramic powder,as a dispersant.Formulated mixtures contain-ing 2different TiO 2powders were exposed to high energy milling (MiniCer,Netzsch,Germany)for 3h at a rotor speed of 3000rpm with 0.4mm ZrO 2beads.The mixtures with the same formulation were also ball-milled for 24h using 5mm ZrO 2balls for comparison.The four types of slurries were dried after milling at 1008C in a rotary evaporator for uniform mixing.The dried powders are named AB,AH,RB and RH depending on the TiO 2type and milling method,where A and R stand for anatase-and rutile-TiO 2,and B and H for ball-milled and high energy-milled,respectively.Each dried powder was heat-treated at 700,800and 9008C for 3h in air at a heating rate of 38C/min.2.3.Characterization of the particlesThe dispersion stability of the particles associated with wet milling was examined by measuring the zeta potentials of the starting materials using an electroacoustic-type zeta potential analyzer (Zeta Probe,Colloidal Dynamics,USA)with and without a dispersant after adjusting the pH of the slurry using NH 4OH and HCl.The morphologies of the starting materials before and after milling were characterized by scanning electron microscopy (SEM:S-4800,Hitachi using 15kV and 10m A with the working distance of 5–8mm,Hitachi).The thermal decomposition behavior of 4different combinations were examined by thermogravimetric analysis (TGA:SDT Q600,TA Instruments,USA)in a ﬂowing air atmosphere at temperatures ranging from room temperature to 10008C with a heating rate of 58C/min.Room temperature XRD (RT-XRD:X’Pert-PRO MPD,Panalytical using Cu K a line,40kV and 30mA)and Rietveld reﬁnement were performed for quanti-tative phase veriﬁcation after heat treatment.In addition,high temperature XRD (HT-XRD:D/MAX-RB,Rigaku using Cu K a line,40kV and 300mA)was performed for the AH combination to conﬁrm in situ the phases generated during heat treatment.For the measurements,the samples were heat-treated from room temperature to 8008C in 1008C steps and held at each measurement temperature for 3min.2.4.Electrochemical testingTo evaluate the electrochemical properties,an electrode paste composed of 80wt.%Li 4Ti 5O 12,10wt.%Denka black and 10wt.%poly(vinylidene ﬂuoride)(PVdF,KF1300)was mixed and dispersed.The paste was then screen-printed on Al foil to form an electrode.The electrode plate was then pressed to enhance the interparticle contact and to ensure a better adhesion to the current collector.Coin-type half-cells (CR2032)were assembled with the composite electrode,Li foil as a counter electrode,and polyethylene ﬁlm as a separator.The electrolyte used was 1.3M LiPF 6dissolved in a mixture of ethylene carbonate and ethylmethyl carbonate with a volume ratio of 1/2.The cell assembly was performed in a glove box ﬁlled with Ar gas,and the electrode was dried under vacuum at 1208C to remove the moisture before ﬁlling the electrolyte.The galvanostatic charge–discharge measurements were performed in a potential range of 1.0–2.5V (versus Li/Li +)at different current conditions of 0.1C (17.5mA/g)–4.0C (700mA/g).The cells were charged and discharged for three cycles at each current density at 258C.3.Results and discussion3.1.Starting materials and their dispersion stabilitySince a solid-state reaction occurs at the contact points of the starting materials,the use of very ﬁne and uniformly dispersedTable 1Characteristics of the starting materials used in this study.Materials ManufacturerD 50(m m)PurityNote Li 2CO 3New Well,Korea3.80>99.9Broad size distribution TiO 2(anatase)Hang Zhou Wan Jing,China0.08>99.0Highlyagglomerated TiO 2(rutile)Toho Titanium,Japan0.78>99.93.5wt.%anatase TiO 2containedC.-H.Hong et al./Ceramics International xxx (2011)xxx –xxx2Li 2CO 3and TiO 2is very important for enhancing the reaction rate and decreasing the processing temperature.According to the SEM images of the starting materials shown in Fig.1,Li 2CO 3and rutile TiO 2have a relatively large particle size of 3.80and 0.78m m,respectively,whereas anatase TiO 2has a very ﬁne primary particle size of approximately 80nm,even though it exists in a highly agglomerated state.Therefore,efﬁcient milling of the starting materials to obtain ﬁne and highly dispersed particles appears to be necessary.Although the agglomerated and coarse particles can be broken down by shear force during wet milling,in the absence of long-term dispersion stability,agglomeration will occur again when the shear is removed.The dispersion stability can be achieved by electrostatic and steric mechanisms,which prevent the particles from approaching each other using electrostatic repulsive force and hindrance by the adsorption of polymeric molecules on the particle surface,respectively.To check the stability,the zeta potentials of the starting materials were measured in water with and without a dispersant as a function of pH (Fig.2).Li 2CO 3shows a high zeta potential of approximately +100mV regardless the presence of a dis-persant.The pH of the Li 2CO 3slurry remained high despite the addition of HCl because CO 32Àacts as a buffer [26].The iso-electric points (IEPs)of anatase and rutile TiO 2without a dispersant were pH =6.0and 6.1,respectively,whereas those with a dispersant decreased to pH =3.4and 2.9because of the anionic nature of Cerasperse 5468CF.Since the pH of the mixed Li 2CO 3and TiO 2slurries with the dispersant are approximately 9–10for both TiO 2phases,there is a large difference in zeta potential between Li 2CO 3and TiO 2,suggesting an efﬁcient electrostatic repulsion and attraction forces between the same and different types of particles in this pH region,respectively.Moreover,steric repulsion by a polymeric dispersant as well as heterocoagulation [27]between Li 2CO 3and TiO 2by different surface charges are expected.3.2.Effects of milling on solid-state reactionFig.3shows SEM images of the starting materials after 2types of milling for different combinations.The AB combina-tion still showed coarse Li 2CO 3particles with agglomerated anatase-phased TiO 2after 24h of ball milling,whereas AH showed ﬁnely milled and uniform particles after 3h of high energy milling.A similar trend was observed with RB and RH,even though the overall particle sizes were coarser than AB and AH due to the initial large particle size of rutile TiO 2.ThisFig.1.SEM images of the starting materials:(a)Li 2CO 3,(b)anatase TiO 2,and (c)rutile TiO 2.-100-5050100150Z e t a p o t e n t i a l (m V )Slurry pHFig.2.Zeta potential behavior of the starting materials as a function of the slurry pH.C.-H.Hong et al./Ceramics International xxx (2011)xxx –xxx3efﬁcient milling for the starting materials using a high energy mill is expected to decrease the reaction temperature further due to homogeneous mixing and mechanochemical activation.Fig.4shows the TGA results at a heating rate of 58C/min in air for 4different combinations,showing drastic weightloss between 300and 7008C.AB,AH and RH show similar weight loss behavior with a total loss of >18.4%,while RB shows 16.7%loss at temperatures 100–2008C higher than the other samples.This difference in temperature for weight loss can be explained by the effects of the different TiO 2phase and milling method.Regarding the effect of TiO 2phase,anatase with a lower theoretical density (3.90g/cm 3)and ﬁner particle size can have higher activity for a solid-state reaction owing to its looser structure and shorter diffusion path than rutile with a higher density (4.23g/cm 3)and coarser particle size.A comparison of the RB and RH combination showed that mechanochemical activation by high energy milling also decreases the reaction temperature.On the other hand,the effect of mechanochemical activation for ﬁne anatase TiO 2on the temperature decrease was smaller than that for rutile,which can be explained by the high initial activity of ﬁne anatase TiO 2before milling.The solid-state reaction between Li 2CO 3and TiO 2is explained by Eq.(1):2Li 2CO 3þ5TiO 2!Li 4Ti 5O 12þ2CO 2(1)where 16.1%of the weight loss is expected due to CO 2evolution.RB shows similar weight loss of 16.7%,whereas the others show >18.0%because of the larger amount of adsorbed water on the ﬁneparticles.Fig.3.SEM images of the starting materials after two types of milling (A:anatase TiO 2+Li 2CO 3,R:rutile TiO 2+Li 2CO 3,B:24h of ball milling,H:3h of high energy milling).W e i g h t (%)Temperature (ºC)Fig.4.TGA results for the 4different combinations,showing the effect of mechanochemical activation by high energy milling for the rutile-phase TiO 2and Li 2CO 3combination.C.-H.Hong et al./Ceramics International xxx (2011)xxx –xxx43.3.XRD results and the phase transformation of TiO 2Fig.5shows XRD patterns of 4different samples heat-treated at (a)7008C and (b)8008C for 3h in air.Although most reports used heat treatment at !8008C for !12h for Li 4Ti 5O 12formation [3–6,13–18,28,29],the samples were kept at the target temperature for only 3h to examine the effects of mechanochemical activation and starting materials.According to Fig.5(a),the high energy-milled powder showed clearer Li 4Ti 5O 12peaks than the ball-milled samples.On the other hand,virtually no XRD peaks for Li 4Ti 5O 12were found for the samples prepared with rutile TiO 2,regardless of the types of milling,whereas the peaks for the intermediate Li 2TiO 3compound were found.Moreover,AH prepared with anatase TiO 2contained rutile-phase TiO 2,which was not observed with AB at 7008C,indicating an anatase-to rutile TiO 2phase transformation in the AH sample.The effectiveness of high energy milling on solid-state reaction of Li 4Ti 5O 12can still be found at 8008C from the relatively higher Li 4Ti 5O 12peak heights,i.e.,higher crystallinity,of the high energy-milled samples than those ball-milled,as shown in Fig.5(b).The peaks for transformed rutile TiO 2were observed in both AB and AH at 27.582u .The lower temperature for the anatase-to rutile TiO 2transformation in the AH sample than the AB sample wasattributed to the effect of mechanochemical activation.Although Li 4Ti 5O 12peaks are only were found when anatase TiO 2was used because of the phase transformation.In addition,the peaks for Li 2TiO 3were also observed in the AB sample due to the poor activity of the starting materials after heat treatment at 8008C.Although the XRD patterns are not shown,the rutile TiO 2that formed from anatase still remained after heat treatment at 9008C.The rutile TiO 2transformed from anatase appears to be more rigid than the intact rutile TiO 2,which hinders the formation of Li 4Ti 5O 12even at 9008C.HT-XRD was performed from room temperature to 8008C in 1008C steps for AH combination to observe this anatase-to rutile TiO 2transformation in situ,as shown in Fig.6.The starting materials were maintained up to 5008C,whereas an intermediate phase of Li 2TiO 3and the onset of rutile TiO 2at 27.582u was observed at 6008C.This transformed rutile TiO 2remained at 8008C,even though Li 2TiO 3had already transformed to Li 4Ti 5O 12at this temperature.The typical reported temperature for the anatase-to rutile TiO 2transformation is higher than 7008C [30–33].Therefore,a supplementary test between pure anatase TiO 2and the AH combination was performed to conﬁrm the phase transforma-tion.According to the XRD patterns in Fig.7(a),the anatase-to rutile TiO 2phase transformation begins from 9008C,and rutile TiO 2becomes a major phase at 10008C.On the other hand,this transformation temperature decreases to 6008C when anatase TiO 2is mixed with Li 2CO 3,as shown in Fig.7(b).This decrease in TiO 2transformation temperature can be explained by the catalytic effect of Li 2CO 3and the mechanochemical activation by high energy milling.3.4.Li 4Ti 5O 12properties and the results of Rietveld simulationFig.8shows SEM images of the Li 4Ti 5O 12powders synthesized at 800and 9008C for 4different combinations.The mean particle size of the AB,AH,RB and RH samples at 8008C were 271,204,349and 276nm,respectively.The particle size of Li 4Ti 5O 12prepared with anatase TiO 2and high energy milling was smaller than that prepared with rutile one and ball milling.Although the overall particle size increased,the same trend was observed for the samples heat-treated atI n t e n s i t y (a .u .)2θ (degree)I n t e n s i t y (a .u .)2θ (degree)Fig.5.XRD patterns of the samples after heat treatment at (a)700and (c)8008C using 4different powder samples.2θ (deg ree )Fig.6.HT-XRD patterns of the AH combination.C.-H.Hong et al./Ceramics International xxx (2011)xxx –xxx59008C.In addition,more polygonal shaped particles withledges,indicating higher crystallinity,were observed in the samples prepared by high energy milling than those by ball milling.From these observations,it can be concluded that ﬁne starting materials are favorable for acquiring ﬁne Li 4Ti 5O 12particles with high crystallinity,which can be achieved by the mechanochemical activation of TiO 2and Li 2CO 3.Table 2summarizes the phase content calculated by a Rietveld simulation for 4different combinations after heat treatment at 700,800and 9008C.Although the characteristic XRD peaks for rutile TiO 2cannot be observed for the RH and RB samples after the 8008C treatment,as shown in Fig.5(b),the simulation revealed the existence of a small amount of this phase.According to this table,a larger amount of Li 4Ti 5O 12was found for the samples prepared with anatase TiO 2and high energy milling than those prepared with rutile and ball milling at the initial Li 4Ti 5O 12formation temperature of 7008C.This was attributed to the loose anatase TiO 2structure and high activity of the starting materials as a result of mechanochemical activation.However,after 800and 9008C treatments,the content of Li 4Ti 5O 12in the samples prepared with rutile-phased TiO 2was higher than those prepared with anatase,which is the opposite trend from that observed at 7008C.On the other hand,the effect of high energy milling was maintained over the entire temperature ranges.This appears to be the result of the anatase to rutile phase transformation,where the transformed rutile phase is more rigid than the intact rutile TiO 2,which hinders the formation of Li 4Ti 5O 12,as indicated by the XRD patterns in Fig.5.3.5.Electrochemical propertiesFig.9(a)and (b)shows the charge/discharge proﬁles in the third cycle at 0.1C for Li 4Ti 5O 12electrodes prepared with anatase-and rutile TiO 2,respectively.According to Fig.9(a),the discharge capacity of Li 4Ti 5O 12electrodes prepared with anatase TiO 2depends signiﬁcantly on the milling method and heat treatment temperature.For example,the speciﬁc capacity of the AB sample after the 8008C treatment was 102.4mAh/g,whereas the AH sample shows the highest value of 165.3mAh/g after treatment at the same temperature.The capacity of the 9008C treated samples was higher the AB sample,but slightly lower for the AH sample compared to that of the 8008C treated samples.On the other hand,the samples prepared with rutile TiO 2showed a high speciﬁc capacity of 160.6–165.1mAh/g regardless of the temperature and milling method,as shown in Fig.9(b).When the results shown in Fig.9were compared with the phase contents in Table 2,a strong correlation was found between the speciﬁc capacity and Li 4Ti 5O 12content.Since Li 4Ti 5O 12is the main phase that can participate in charge storage among the many phases shown in Table 2,higher Li 4Ti 5O 12content of the ﬁnal product is desirable for increasing the speciﬁc capacity.Fig.10shows the rate performance of a half-cell with Li 4Ti 5O 12electrodes at different C -rates.The C -rates were varied in the order of 0.1–0.2–0.5–1.0–2.0–4.0–0.1C with 3cycles at each rate and a rest time of 10min after each measurement.Although all samples showed good cyclability at each C -rate along with the complete capacity recovery to the50403020I n t e n s i t y (a .u .)2θ (degree)504030202θ (degree)I n t e n s i t y (a .u .)Fig.7.XRD patterns showing the anatase-to rutile-TiO 2transition temperature at different conditions.C.-H.Hong et al./Ceramics International xxx (2011)xxx –xxx6initial value at the ﬁnal 0.1C ,the rate capability depends on the type of samples.The rate capability of the electrodes prepared with Li 4Ti 5O 12heat-treated at 8008C appears to be better than those treated at 9008C,regardless the types of starting materials and milling methods,as shown in Fig.11.The RH sample after heat treatment at 8008C showed the best rate capability at 4C ,according to Fig.11.Although the AB sample treated at 8008C showed the second highest rate capability,it showed the lowest speciﬁc capacity of 102.4mAh/g,as shown in Fig.9.Therefore,no correlation between the speciﬁc capacity and rate capability is expected.A small Li 4Ti 5O 12particle size appears to be the main factor for achieving a high rate capability by promoting the Li +intercalation and de-intercalation process through the short diffusion path and enhanced contact area between Li 4Ti 5O 12and theelectrolyte.Fig.8.SEM images of Li 4Ti 5O 12particles after heat treatment at 800and 9008C for the different combinations.C.-H.Hong et al./Ceramics International xxx (2011)xxx –xxx7Table 2Phase content based on a Rietveld simulation as a function of the temperature for different starting materials and milling methods.The abbreviation for each sample is shown in parenthesis.Starting materialsMilling methodPhaseContents (wt.%)7008C8008C9008CLi 2CO 3+anatase TiO 2Ball milling (AB)Rutile TiO 2–17.17.6Anatase TiO 244.5––Li 2TiO 331.2 1.60.8Li 4Ti 5O 1224.481.391.7High energy milling (AH)Rutile TiO 2 6.2 3.1 1.8Anatase TiO 223.4––Li 2TiO 316.70.4–Li 4Ti 5O 1253.896.598.2Li 2CO 3+rutile TiO 2Ball milling (RB)Rutile TiO 258.3 2.60.8Anatase TiO 2–––Li 2TiO 341.70.3–Li 4Ti 5O 12–97.199.2High energy milling (RH)Rutile TiO 252.5 1.2–Anatase TiO 2–0.3–Li 2TiO 334.7––Li 4Ti 5O 1212.898.5100V o l t a g e (V ) (v s . L i /L i +)Specfic capacity (mAh/g)V o l t a g e (V ) (v s . L i /L i +)Specfic capacity (mAh/g)Fig.9.V oltage proﬁles for charge and discharge of the Li 4Ti 5O 12electrodes at the third cycle with a charging/discharging rate of 0.1C .(a)S p e c i f i c c a p a c i t y (m A h /g )Cycle number(b)S p e c i f i c c a p a c i t y (m A h /g )Cycle numberFig.10.Rate capabilities of the Li 4Ti 5O 12electrodes prepared using different starting materials and milling methods at different charge–discharge rates.C.-H.Hong et al./Ceramics International xxx (2011)xxx –xxx84.ConclusionsLi 4Ti 5O 12was synthesized by the solid-state reaction between Li 2CO 3and 2different TiO 2phases for Li-ion battery applications.The following conclusions were made:1.Heterocoagulated Li 2CO 3and TiO 2particles with high dispersion stability and uniform distribution could be produced during wet milling due to the large difference in zeta potential and different surface charges of the particles.2.Mechanochemical activation by high energy milling of the starting materials was more effective in decreasing the reaction temperature and particle size as well as increasing the Li 4Ti 5O 12content of the ﬁnal powder than those prepared by conventional ball milling.3.An anatase-to rutile TiO 2phase transformation was observed at approximately 7008C,which is lower than the reported values,due to the catalytic effect of Li 2CO 3when anatase TiO 2was used as the starting material.Moreover,this transformed rutile phase was found to react more slowly in a solid-state reaction than the intact rutile TiO 2.Therefore,the utilization of rutile TiO 2as a starting phase would be desirable in enhancing the Li 4Ti 5O 12content,which is the key factor for increasing the speciﬁc capacity.4.The speciﬁc capacities of Li 4Ti 5O 12prepared from anatase TiO 2depend signiﬁcantly on the milling method and heat treatment temperature,whereas those from rutile TiO 2showed a uniform capacity of 160.6–165.1mAh/g,regard-less the change in the main parameters owing to their high Li 4Ti 5O 12content.5.The rate capability of the half cell depended signiﬁcantly on the Li 4Ti 5O 12size,where smaller particles showed higher rate capability due to the short diffusion path and large contact area between the active material and electrolyte.AcknowledgementsThis study was supported by the Industrial Core Technology Program funded by The Ministry of the Knowledge Economy,Republic of Korea (Project No.10035302).References[1]K.M.Colbow,J.R.Dahn,R.R.Haering,Structure and electrochemistry ofthe spinel oxides LiTi 2O 4and Li 4/3Ti 5/3O 4,J.Power Sources 26(1989)397–402.[2]K.Zaghib,M.Armand,M.Gauthier,Electrochemistry of anodes insolid-state Li-ion polymer batteries,J.Electrochem.Soc.145(1998)3135–3140.[3]A.Guerﬁ,S.Se´vigny,gace ´,P.Hovington,K.Kinoshita,K.Zaghib,Nano-particle Li 4Ti 5O 12spinel as electrode for electrochemical genera-tors,J.Power Sources 119–121(2003)88–94.[4]G.Wang,J.Xu,M.Wen,R.Cai,R.Ran,Z.Shao,Inﬂuence of high-energyball milling of precursor on the morphology and electrochemical perfor-mance of Li 4Ti 5O 12–ball-milling time,Solid State Ionics 179(2008)946–950.[5]A.Guerﬁ,P.Charest,K.Kinoshita,M.Perrier,K.Zaghib,Nano elec-tronically conductive titanium-spinel as lithium ion storage negative electrode,J.Power Sources 126(2004)163–168.[6]K.Hsiao,S.Liao,J.Chen,Microstructure effect on the electrochemicalproperty of Li 4Ti 5O 12as an anode material for lithium-ion batteries,Electrochim.Acta 53(2008)7242–7247.[7]R.F.Nelson,Power requirements for batteries in hybrid electric vehicles,J.Power Sources 91(2000)2–26.[8]B.Scrosati,Challenge of portable power,Nature 373(1995)557–558.[9]G.G.Amatucci,F.Badway,A.D.Pasquier,T.Zheng,An asymmetrichybrid nonaqueous energy storage cell,J.Electrochem.Soc.148(2001)A930–A939.[10]L.Kavan,J.Procha´zka,T.Spitler,M.Kalva ´c ˇ,M.Zukalova ´,T.Drezen,M.Gra¨tzel,Li insertion into Li 4Ti 5O 12–charge capability vs.particle size in thin-ﬁlm electrodes,J.Electrochem.Soc.150(2003)A1000–A1007.[11]J.L.Allen,T.R.Jow,J.Wolfenstine,Low temperature performance ofnanophase Li 4Ti 5O 12,J.Power Sources 159(2006)1340–1345.[12]P.Kubiak,A.Garcia,M.Womes,L.Aldon,J.Olivier-Fourcade,P.E.Lippens,J.C.Jumas,Phase transition in the spinel Li 4Ti 5O 12induced by lithium insertion inﬂuence of the substitutions Ti/V ,Ti/Mn.Ti/Fe,J.Power Sources 119–121(2003)626–630.[13]S.Huang,Z.Wen,X.Zhu,Z.Gu,Preparation and electrochemicalperformance of Ag doped Li 4Ti 5O 12,mun.6(2004)1093–1097.[14]H.E.Park,I.W.Seong,W.Y .Yoon,Electrochemical behaviors of wax-coated Li powder/Li 4Ti 5O 12cells,J.Power Sources 189(2009)499–502.[15]G.J.Wang,J.Gao,L.J.Fu,N.H.Zhao,Y .P.Wu,T.Takamura,Preparationand characteristic of carbon-coated Li 4Ti 5O 12anode material,J.Power Sources 174(2007)1109–1112.[16]S.Huang,Z.Wen,Z.Zhu,Z.Lin,Effects of dopant on the electrochemicalperformance of Li 4Ti 5O 12as electrode materials for lithium ion batteries,J.Power Sources 165(2007)408–412.C a p a c i t y r a t i o (%)C-rateC a p a c i t y r a t i o (%)C-rateFig.11.Normalized capacity as a function of the C -rate for Li 4Ti 5O 12electrodes prepared by (a)ball milling and (b)high energy milling.C.-H.Hong et al./Ceramics International xxx (2011)xxx –xxx9。

卤化物固态电解质英语

卤化物固态电解质英语Halide Solid-State Electrolytes: A Breakthrough in Energy Storage.Solid-state electrolytes have revolutionized the field of energy storage, and halide solid-state electrolytes are at the forefront of this revolution. These electrolytes, composed of halide ions (such as fluorine, chlorine, bromine, and iodine), offer significant advantages over traditional liquid electrolytes in terms of safety, efficiency, and performance. In this article, we delve into the world of halide solid-state electrolytes, exploring their properties, applications, and the potential they hold for the future of energy storage.Properties of Halide Solid-State Electrolytes.Halide solid-state electrolytes exhibit several remarkable properties that make them ideal for use in energy storage devices. First and foremost, they possesshigh ionic conductivity, which enables fast and efficient charge transfer within the solid-state matrix. This high conductivity is attributed to the mobile nature of halide ions, which facilitate the movement of charge carriers without the need for a liquid medium.Another key property of halide solid-state electrolytes is their high mechanical strength. Unlike liquid electrolytes, which can leak or spill, solid-state electrolytes provide robust physical barriers that protect the battery components from external damage and internal short-circuiting. This enhanced safety feature is crucialin ensuring the reliability and durability of energy storage systems.Moreover, halide solid-state electrolytes exhibit excellent chemical stability, resisting degradation even under extreme conditions. This stability is crucial in maintaining the performance and lifespan of batteries, asit prevents the formation of harmful by-products that can compromise battery efficiency.Applications of Halide Solid-State Electrolytes.The unique properties of halide solid-stateelectrolytes make them ideal for a wide range of energy storage applications. One of the most promising areas is in the development of solid-state batteries, which offer significant advantages over traditional lithium-ion batteries. Solid-state batteries with halide electrolytes can achieve higher energy densities, faster charging speeds, and improved safety features, making them suitable for a wide range of applications, including electric vehicles, smartphones, and wearable technology.Beyond solid-state batteries, halide solid-state electrolytes also find applications in fuel cells and supercapacitors. In fuel cells, they enable efficient hydrogen storage and conversion, leading to improved fuel efficiency and reduced emissions. In supercapacitors, they provide high power density and rapid charge-discharge capabilities, making them suitable for applications that require rapid energy delivery, such as electric vehiclesand grid-scale energy storage systems.Future Prospects.The future of halide solid-state electrolytes looks bright, with continuous research and development leading to improved performance and expanded applications. One of the key areas of research is in enhancing the ionicconductivity of these electrolytes, which could further improve the energy density and charging speeds of solid-state batteries. Additionally, exploring new material combinations and synthetic techniques could lead to the development of even more stable and efficient halide solid-state electrolytes.Another exciting direction is the integration of halide solid-state electrolytes with other advanced battery technologies, such as lithium-air batteries and lithium-sulfur batteries. These batteries offer even higher energy densities but face challenges in terms of stability and safety. The use of halide solid-state electrolytes could help address these challenges, enabling the realization of next-generation batteries with unprecedented performance.Overall, halide solid-state electrolytes hold tremendous potential for revolutionizing the field of energy storage. As research continues to advance, we can expect to see even more innovative applications and technologies emerge, driving the transition towards a more sustainable and efficient energy future.。

多线锂电池的工作原理

多线锂电池的工作原理Lithium-ion batteries, also known as Li-ion batteries, are a type of rechargeabloble battery commonly used in portable electronics. 锂离子电池，也被称为锂电池，是一种常用于便携电子设备中的可充电电池。

They work by allowing lithium ions to move between the positive and negative electrodes of the battery, which causes a flow of electrons through the circuit, generating electrical energy. 它们通过允许锂离子在电池的正负极之间移动，从而使电子在电路中流动，产生电能。

This transfer of ions and electrons is what powers the device that the battery is connected to. 这种离子和电子的转移就是给电池连接的设备供电的原因。

One of the main components of a lithium-ion battery is the electrolyte, which is typically a liquid or gel substance that allows ions to flow between the positive and negative electrodes. 锂离子电池的主要组成部分之一是电解质，它通常是一种液体或凝胶物质，可以让离子在正负极之间流动。

The separator, which is a thin, permeable membrane, physically keeps the positive and negative electrodes apart while allowing the ions to pass through. 隔膜是一种薄的、可渗透的膜，它在物理上将正负极分开，同时允许离子通过。

复合固态电解质英文

复合固态电解质英文The Development of Composite Solid-State ElectrolytesIntroductionComposite solid-state electrolytes (CSSEs) have emerged as a promising solution to the challenges posed by traditional electrolytes in energy storage devices, such as lithium-ion batteries. CSSEs offer several advantages, including improved stability, enhanced safety, and increased ion conductivity. This article aims to explore the development of CSSEs and their potential applications in various fields.1. Fundamentals of Composite Solid-State Electrolytes1.1 Definition and CompositionCSSEs are materials that consist of a solid matrix and dispersed ionic conductive phases. The solid matrix provides mechanical strength, while the ionic conductive phases facilitate the movement of ions. The composition of CSSEs can vary, but typically involves a combination of inorganic and organic components.1.2 Ion Conduction MechanismThe ion conduction mechanism in CSSEs can be attributed to two primary factors: the presence of mobile ions in the matrix and the formation of low-energy pathways for ion transportation. The former occurs due to the introduction of ionic species within the solid matrix, while the latter is achieved by optimizing the microstructure of the CSSEs.2. Advancements in CSSEs2.1 Solid-State Composite Electrolytes for Lithium-Ion BatteriesCSSEs have demonstrated significant potential in the field of lithium-ion batteries. Traditional liquid electrolytes can pose safety hazards due to their flammable nature, limiting their applications in certain industries. CSSEs offer improved safety features and exhibit excellent compatibility with various electrode materials, enhancing the overall performance and stability of lithium-ion batteries.2.2 Composite Electrolytes for Solid-State Lithium Metal BatteriesOne of the challenges in developing solid-state lithium metal batteries lies in the formation of a stable and highly conductive interface between the lithium metal anode and the electrolyte. CSSEs can provide an effective solution to this issue by acting as a protective layer and facilitating stable lithium ion transport. The use of CSSEs in solid-state lithium metal batteries has shown great potential for enhancing the energy density and cycling stability of these batteries.2.3 Composite Solid-State Electrolytes for Sodium-Ion BatteriesWhile lithium-ion batteries dominate the market, there is a growing interest in sodium-ion batteries as an alternative, due to the abundance and lower cost of sodium. CSSEs offer a viable avenue for improving the performance of sodium-ion batteries by providing enhanced ion conductivity and addressing issues related to sodium electrode passivation.3. Challenges and Future Perspectives3.1 Interface StabilityThe interface stability between CSSEs and electrode materials remains a critical challenge. To ensure long-term stability and prevent interface reactions, strategies such as interfacial engineering and the use of protective coatings need to be further explored.3.2 Optimization of Ionic ConductivityWhile CSSEs have displayed promising ionic conductivity, further optimization is necessary to achieve levels comparable to traditional liquid electrolytes. Enhancing the microstructure and understanding the effect of various factors, such as the composition and porosity of the CSSEs, can contribute to improving their ion conduction properties.3.3 Scalability and Cost-EffectivenessThe scalability and cost-effectiveness of CSSEs must be addressed to enable large-scale production for commercial applications. Research efforts should focus on developing cost-effective synthesis methods and improving the performance-to-price ratio of CSSEs.ConclusionComposite solid-state electrolytes (CSSEs) offer a promising solution for improving the performance, safety, and stability of energy storage devices. They have demonstrated significant potential for application in lithium-ion batteries, solid-state lithium metal batteries, and sodium-ion batteries. However, challenges regarding interface stability, ionic conductivity optimization, scalability, and cost-effectiveness must be overcome. Continued research efforts and advancements in CSSE technology will becrucial in unlocking the full potential of these materials for future energy storage applications.。

凝固态碳电池英文

凝固态碳电池英文Solid-State Carbon Batteries: A Promising Technologyfor Electric Vehicles and Beyond.Solid-state batteries are a promising new technology that has the potential to revolutionize the way we power our electric vehicles and other devices. Unlike conventional batteries, which use liquid electrolytes,solid-state batteries use solid electrolytes, which are typically made of ceramic or polymer materials. This solid-state design offers a number of advantages over traditional batteries, including:Higher energy density: Solid-state batteries can store more energy than conventional batteries, which means that they can power electric vehicles for longer distances on a single charge.Faster charging: Solid-state batteries can be charged much faster than conventional batteries, which makes themideal for use in electric vehicles that need to be recharged quickly.Improved safety: Solid-state batteries are less likely to catch fire or explode than conventional batteries, which makes them safer for use in electric vehicles and other devices.Longer lifespan: Solid-state batteries have a longer lifespan than conventional batteries, which means that they can last for many years without needing to be replaced.Solid-state batteries are still in the early stages of development, but they have the potential to revolutionize the way we power our electric vehicles and other devices. With their higher energy density, faster charging, improved safety, and longer lifespan, solid-state batteries are poised to become the next generation of battery technology.How Do Solid-State Carbon Batteries Work?Solid-state carbon batteries use a solid electrolyteinstead of a liquid electrolyte. The solid electrolyte is typically made of a ceramic or polymer material, and it allows ions to move between the positive and negative electrodes of the battery.The positive electrode of a solid-state carbon battery is typically made of a carbon material, such as graphite or carbon nanotubes. The negative electrode is typically made of a metal, such as lithium or sodium.When the battery is charged, lithium ions move from the negative electrode to the positive electrode. This creates an electrical current, which can be used to power an electric vehicle or other device.When the battery is discharged, the lithium ions move back from the positive electrode to the negative electrode. This reverses the electrical current, and it creates energy that can be used to power an electric vehicle or other device.Advantages of Solid-State Carbon Batteries.Solid-state carbon batteries offer a number of advantages over conventional batteries, including:Higher energy density: Solid-state carbon batteriescan store more energy than conventional batteries, which means that they can power electric vehicles for longer distances on a single charge.Faster charging: Solid-state carbon batteries can be charged much faster than conventional batteries, which makes them ideal for use in electric vehicles that need to be recharged quickly.Improved safety: Solid-state carbon batteries are less likely to catch fire or explode than conventional batteries, which makes them safer for use in electric vehicles and other devices.Longer lifespan: Solid-state carbon batteries have a longer lifespan than conventional batteries, which meansthat they can last for many years without needing to bereplaced.Challenges of Solid-State Carbon Batteries.Solid-state carbon batteries are still in the early stages of development, and they face a number of challenges, including:High cost: Solid-state carbon batteries are currently more expensive to manufacture than conventional batteries.Low production volume: Solid-state carbon batteriesare not yet being produced in large volumes, which makes them difficult to find and purchase.Limited availability: Solid-state carbon batteries are not yet widely available, which makes them difficult tofind and purchase.Conclusion.Solid-state carbon batteries are a promising newtechnology that has the potential to revolutionize the way we power our electric vehicles and other devices. Withtheir higher energy density, faster charging, improved safety, and longer lifespan, solid-state carbon batteries are poised to become the next generation of battery technology.However, solid-state carbon batteries are still in the early stages of development, and they face a number of challenges, including high cost, low production volume, and limited availability. These challenges will need to be overcome before solid-state carbon batteries can be widely adopted.。

欧赛新能源科技有限公司 IFM6.4-15E2(6.4V1.5AH)规格书说明书

IFM6.4-15E2(6.4V1.5AH)规格书1．Scope（适用范围）Continuous the table 13.〃Performance And Test Conditions (3.4 Appearance8.Other Chemical ReactionAny other items which are not covered in this specification shall be agreed by both parties.本说明书未包括事项应由双方协议确定No.Charging voltageBalance voltage for single cellBalance current for single cellCurrent consumption for single cell Maximal continuous Discharging current Maximal continuous Charging currentOver charge detection voltageOver charge detection delay time Over charge release voltage Over discharge detection voltageOver discharge detection delay time Over discharge release voltage Over current detection voltage Over current detection current Detection delay time Release condition Detection conditionDetection delay time Release condition 7Resistance Protection circuitryOperating Temperature Range Storage Temperature RangeDimensions: L48.5*8mmProtection Circuit Module Specifications For 6.4V LiFePO4 Battery PackModel:PCM-Li02S8-021（2S）Test itemCriterion1Voltage150±20mV DC:7.3V CC/CV3.85±0.025V 2.5A 3.75±0.05V 6.7ms—13.9ms2Current≤20μA 2.5A 3Over charge Protection Exterior short circuit0.73S—1.35S Cut load 4Over discharge protection 2.23±0.08V 68mS—138mS 2.23±0.1V 5Over current protection200-500us 7.5±1A ≤50mΩ8Temperature-40～+85℃-40～+125℃Cut load 6Short protectionO’CELL NEW ENERGY TECHNOLOGY CO., LTDModel: Lithium Ion batteries Revised date: JAN 18, 2010 Ref.No:S460CLP85MATERIAL SAFETY DATA SHEET1. PRODUCT & COMPANY INDENTIFICATIONPRODUCT NAME：Lithium Ion BatteryMODEL/SIZE：All Lithium Iron Phosphate BatteryMANUFACTURER：O’CELL NEW ENERGY TECHNOLOGY CO., LTDADDRESS：O’CELL Technology Industrial Park, Xiaoting, Yichang, Hubei, ChinaTELEPHONE：86-717-63448482. COMPOSITION/INFORMATION ON INGREDIENTSCAS RN Approximate percent of total weight LiFeO433%Carbon(Graphite) 7440-11-0 18%Electrolyte( LiPF6/EC/DMC/EMC) 21324-40-3/96-49-1/616-38-6/623-53-0 13%Aluminum 7429-90-5 4%Copper 7440-50-8 10% Hexafluoropropylene-Vinylidine-Fluoride Copolymer 9011-17-0 4%PP/PE/PET 3%3. HAZARDS/HEALTH IDENTIFICATIONEmergency Overview (including Signs and Symptoms, Route(s) of Entry, etc.):Intact batteries present no specific hazards.Acute Health Hazards (e.g., Inhalation, Eye Contact, Skin Contact, Ingestion, etc.):Burning batteries: AVOID inhalation of toxic fumes. Burning batteries emit toxic fumes, which are irritating to the lungs.Leaking batteries: AVOID exposure to leaking electrolyte, it can cause severe irritation and/or damage to the skin, mucous membrane or eyes.Chronic Health Effects (e.g., Carcinogenicity, Teratology, Reproduction, Mutagenicity, etc.):Cobalt: Suspected human carcinogenic agent.Medical Conditions Generally Aggravated by Exposure: None.4. FIRST-AID MEASURESInhalation: If battery is burning, leave the area immediately. If exposed to fumes, seek medicalattention promptly.Skin Contact: If battery electrolyte leaks on to the skin flush the affected area for at least 15 minuteswith clean water. DO NOT attempt to neutralize. Seek medical attention promptly.5. FIRE-FIGHTING AND EXPLOSION HAZARD DATAFlammable Properties: N/AFlashpoint: Method:Autoignition Temperature:Flammable Limits: N/ALower flammable limit: Upper flammable limit:Hazardous Combustion Products: Burning batteries may emit acrid smoke irritating fumes, and toxic fumes of fluoride.Extinguishing Media: Carbon dioxide (CO2) or dry chemical fire extinguisher, 10-B:C.Fire Fighting Instructions:Personnel: Fight the fire in a defensive mode, while exiting the area. When using a CO2 fire extinguisher, DOO’CELL NEW ENERGY TECHNOLOGY CO., LTDModel: Lithium Ion batteries Revised date: JAN 18, 2010 Ref.No:S460CLP85NOT re-enter the area until it has been thoroughly ventilated (i.e., purged) of the CO2 extinguishing agent. Firefighters: Use a self-contained breathing apparatus (SCBA).6. ACCIDENTAL RELEASE MEASURESSmall Spill: If batteries show signs of leaking, AVOID skin or eye contact with the material leaking from the battery. Use chemical resistant rubber gloves and non-flammable absorbent materials for clean-up. Coordinate disposition with the Installation Environmental Office.7. HANDLING&STORAGEHandling: Recharge batteries IAW methods specified in applicable technical manuals.DO NOT:· Overcharge this battery.· Abuse, mutilate or short circuit the battery.Storage: Gain approval for storage areas from the Installation Fire Department. Store batteries in a cool (i.e., <130°F), dry and well ventilated area.DO NOT:· Store batteries in direct sunlight or under hot conditions.· Smoke and keep batteries away from open flame or heat.· Store batteries in the same stacks with hazardous materials.· Store batteries in office areas, or other areas where personnel congregate.Work/Hygienic Practices: Thoroughly wash hands after cleaning-up a battery spill (i.e., leaking orventing batteries). NO eating, drinking or smoking in battery storage areas.8. PERSONAL PROTECTIONPersonal protective equipment:Respiration protection: Self-contained breathing apparatusEye protection: Safety glassesSkin protection: Rubber gloves9. PHYSICAL & CHEMICAL PROPERTIESBoiling Point @ 760 mm Hg (°C): NAVapor Pressure (mm Hg @ 25°C): NAVapor Density (Air = 1): NADensity (grams/cc): NAPercent Volatile by Volume (%): NAEvaporation Rate (Butyl Acetate = 1): NAPhysical State: NASolubility in Water (% by Weight): NAPH: NAAppearance and Odo r: geometric solid object10. STABILITY &REACTIVITYStable or unstable: StableIncompatibility (Materials to avoid) : NAHazardous decomposition products: NADecomposition temperature (0°F): NAHazardous polymerization: Will Not OccurCondition to Avoid: Avoid electrical shortingWatt Hour: 0.5 Wh marked outside of the battery case (as per attachment).11. TOXICOLOGICAL INFORMATIONAcute toxicity: None欧赛新能源科技有限公司O’CELL NEW ENERGY TECHNOLOGY CO., LTD Model: Lithium Ion batteries Revised date: JAN 18, 2010 Ref.No:S460CLP85Page 3 of 312. ECOLOGICAL INFORMATIONNA13. DISPOSAL CONSIDERATIONLithium Ion rechargeable cells and batteries contain no toxic metals, only naturally occurring trace elements. Lithium Cells and batteries are exempted from hazardous waste standards under the Universal WasteRegulations, therefore, it is advisable to consult with local state or federal authorities as disposal regulations may vary dependent on location..14. TRANSPORT INFORMATIONLithium Ion rechargeable batteries are regulated during shipment by the Dept. of Transportation (USDOT) and United Nation's (International) requirements. Each battery is the type proven to meet the requirements of each test in the UN Manual of Tests and Criteria, Part III, subsection 38.3 may be shipped without designation as "Class 9" hazardous material, all other marking, labelling, packaging, and unit volumes are met. For specific details, please visit http:/ the International Air Transport association (IATA) 53rd edition 2012,, Dangerous Goods Transportation, or 49 CFR Transportation regulations for further details to your shipping situation.Those lithium batteries comply with section II of PI965, the Watt-Hour was more than100Wh, and each carton is less than 35KGS. Handle with care,Flammability hazard exists if the package is damaged.An in any event of package is damaged pls follow the special procedures.The UN classification number: UN3480Production of MSDS prooving UN manual of Tests and Criteria, part III, subsection 38.3 is met on MSDS IATA DGR: Special Provision A48,A154,A16415. REGULATORY INFORMATIONNone16. OTHER INFORMATIONThe information contained herein is furnished without warranty of any kind. Users should consider this data only as a supplement to other information gathered by them and must make independent determinations of thesuitability and completeness of information from all sources to assure proper use and disposal of these materials and the safety and health of employees and customers.。

锂电池发展简史

图 1 锂离子电池原理示意图
料时 , 欧洲、美国和日本的研究者沿着两条路径摸索前进 : 一是转向具有层状结构、后来被称作嵌入化合物 ( in terca latio n com pound , 简称 IC ) 的电极材料; 二是转向以二氧化锰为代表的过渡金属氧化物。前者令嵌入化合物进入锂电池设计者的视野, 为锂二次电池研发奠定了坚实的基础 ; 后者直接导致日本三洋公司取得锂原电池商业制造的巨大成功, 锂电池终于从概念变成了商品。 1 . 2 L i/ ( CF ) n 体系: 初见端倪 1970 年, 日本松下电器公司与美国军方几乎同时独立合成出新型正极材料 ∀ ∀ ∀ 碳氟化物。松下电器成功制备了分子表达式为 ( CFx ) n ( 0 . 5# x # 1) 的结晶碳氟化物 , 将它作为锂原电池正极。美国军方研究人员设计了 ( Cx F ) n ( x = 3 . 5∀ 7 . 5) |无机锂盐 + 有机溶剂 |L i( M eta l) 电化学体系空探索。
1
锂电池概念与锂原电池发展 ( 1960∀ 1970)
1960∀ 1970年代的石油危机迫使人们去寻找新的替代能源, 同时军事、航空、医药等领域也对电源提出新的要求。当时的电池已不能满足高能量密度电源的需要。由于在所有金属中锂比重很小 ( M = 6 . 94g /m o , l = 0 . 53g / cm 3 ) 、电极电势极低 (- 3 . 04V 相对标准氢电极 ) , 它是能量密度很大的金属, 锂电池体系理论上能获得最大的能量密度, 因此它顺理成章地进入了电池设计者的视野。与其他碱金属相比较 , 锂金属在室温下与水反应速度比较慢 , 但要让锂金属应用在电池体系中, 非水电解质的引入是关键的一步。 1 . 1 L i/CuC l2 体系: 首次尝试 1958年 , H arris 提出采用有机电解质作为锂金属原电池的电解质

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All solid state lithium ion rechargeable batteries using NASICON structured electrolyte J.K.Feng1,2,B.G.Yan1,3,J.C.Liu3,i1and L.Li*1NASICON(Sodium super ionic conductor)structured Li1?5Al0?5Ge1?5(PO4)3(LAGP)solid electrolyte is synthesized through a solid state reaction.The total conductivity of the LAGP electrolyte is761025S cm21with a potential window larger than6V.All solid state lithium batteries are fabricated using LiMn2O4as a cathode,LAGP as an electrolyte and lithium metal as an anode.The LiMn2O4/LAGP/Li cell can deliver a capacity of about80mAh g21in the first discharge cycle and increases gradually with charge/discharge cycles,indicating that LAGP can be used as a promising electrolyte for lithium rechargeable batteries.Keywords:Lithium ion batteries,Thin film batteries,Solid electrolyte,Sputtering depositionThis paper is part of a special issue on Functional Materials for Device and Energy ApplicationsIntroductionLi ion batteries have been widely used in almost all types of electronic products and more recently in electronic vehicles.The current state-of-the-art Li-ion batteries consist of cathode and anode electrode separated by a thin membrane with organic liquid electrolyte.Many types of structures of cathode materials are used,such as LiCoO2,LiMn x Ni y Co(1-x-y)O2,1LiMn2O4,2LiFePO4,3–5 but only graphite is commercially used as the anode material although a lot of other types of anode are being studied.One of most noticeable anodes is lithium titanate.6,7Although LiFePO4is commonly recognized to be the safest cathode,possible growth dendrite and other defects from copper and aluminium substrates may cause short circuits.Therefore the only way to design hazard free Li ion rechargeable batteries is completely replace currently used polymer separator and organic electrolyte by inﬂammable ionic conductor. All solid state Li ion rechargeable batteries with inorganic ceramics as the solid electrolytes have attract-ed growing interests in recent years since the solid electrolytes possess many advantages including high safety,high reliability,and wide potential windows.To fabricate all solid state batteries,solid electrolytes with high Li ionic conductivities,wide potential window and high stability with both the cathode and anode materials are essential.Several kinds of solid electrolytes with high ionic conductivity and good electrochemical ability have been studied,such as LiPON,sulphide glass, Li1z x M x Ti2-x(PO4)3,Li-V-Si-O and Li-La-Ti-O et al.8–14 Some of these electrolytes show low stability when contacted with cathodes or anodes,and some of them are moisture sensitive.15NASICON structured Li1?5Al0?5Ge1?5(PO4)3(LAGP) has been reported to have a conductivity as high as 1023–y1025S cm21with an electrochemical potential window of about6V.It is also known that LAGP is electrochemically stable when contacted with Li metal. Therefore LAGP is a promising solid state electrolyte for all solid state Li batteries.16–22However,only little research has been reported using LAGP as the electro-lyte for the Li metal batteries.In the present study,all solid state Li batteries using LiMn2O4as a cathode,LAGP as an electrolyte and Li metal as an anode are fabricated.Electrochemical properties of the all solid state batteries are investigated. The results show that LAGP can be a good electrolyte for the all solid state Li batteries.ExperimentalLAGP was synthesised through a typical solid state method as reported before.16,20,21In a typical process, Li2CO3(99%),GeO2(99%),Al2O3(99%)and NH4H2PO4 (98%)of analytical grade(all from Aldrich,USA)in a stoichiometric ratio were thoroughly mixed by ball milling for48h and then heated in a platinum crucible at700u C for2h to release the volatile compounds.The powder was reground and ball milled again for another 24h,after which the powder was heated to1350u C with a heating rate of1u C min21and homogenised at1350u C for1h.The melted LAGP was quickly cooled to500u C and held for2h at500u C,followed by cooling down to room temperature.The as synthesised LAGP was then crystallized at850u C for10h.Finally the sintered LAGP was shaped to pellets of8mm diameter and1mm in thickness.The structures of the as synthesised LAGP pellets were measured using Shimadzu XRD-6000X-ray dif-fraction with Cu Ka radiation(l51?5406A˚),at a scan rate of2deg/min.Surface morphologies of the LAGP1Materials Science Group,Department of Mechanical Engineering,National University of Singapore,Singapore1175762School of Materials Science and Engineering,Shandong University,China3Institute of Advanced Shaping and Surface Engineering,HunanUniversity,China*Corresponding author,email luli@.sgß2013W.S.Maney&Son Ltd.Received15April2013;accepted25April2013DOI10.1179/1753555713Y.0000000085Materials Technology2013VOL28NO5 276pellets before and after coating LiMn 2O 4were char-acterized with a Hitachi S-4100ﬁeld emission scanning (FE-SEM)electron microscopy.Ionic conductivity was measured using AC impedance (Solartron1287electrochemical interface combined with a Solartron1260frequency response analyser)in the frequency range between 1021and 106Hz based on Chowdari et al.11To study the ionic conductivity of the LAGP electrolyte,the LAGP powder was pressed into a pellet of 1mm thickness and 50mm 2area at 10MPa,and the pellets were then sintered at 850u C for 10h.Pt was coated on both sides of the LAGP electrolyte pellet,followed by heating the Pt coated specimens to 400u C for half an hour.The Pt coated pellets in the form as Pt/LAGP/Pt were assembled into a cell using stainless steel (SS)as a current collector to test the AC impedance.All solid state battery was prepared by deposition of a 300nm thick LiMn 2O 4layer on the LAGP pellet by radio frequency (rf)magnetron sputtering at 600u C.The sputtering was carried out in an Ar/O 2(9:1)atmosphere at a working pressure of 1?4Pa and a sputtering power of 100W.A Pt ﬁlm was sputtered on the LiMn 2O 4surface as a positive current collector.A Li metal foil was directly pressed onto the LAGP pellet,forming a LiMn 2O 4/LAGP/Li all solid state cell in the glove box.The battery performance of the Li/LAGP/LiMn 2O 4cells was characterised by galvano-static cycling between 2and 4?5V and cyclic voltam-metry (CV)at a scanning rate of 0?1mV s 21with a Solartron 1287and 1256two-terminal cell test system with a Lab-made cell.Results and discussionFigure 1shows the XRD pattern of as prepared LAGP.Although 25%percentage of Ge 4z ion is replaced by Al 3z ion,the XRD diffraction can be indexed as pure NASICON structure LiGe 2(PO 4)3(JCPDS41-0034)since ionic radii of Ge 4z (0?053nm)and Al 3z (0?050nm)are similar,which is similar with those reported before.16–21Sharp diffraction peaks of the NASICON structure indicate a good crystallinity after crystallization at 850u C.The scanning electron micro-graphs of the as synthesised pellet are shown in Fig.2.It can be seen that the as synthesised LAGP was wellcompacted together without appearance of porosity and cracks and no clear crystalline grain can be observed.This type of morphology was observed before.16To measure the conductivity of the as-prepared LAGP,AC impedance measurement was performed using a Pt/LAGP/Pt electrode.Typical impedance spectrum of the LAGP electrolyte pellet is shown in Fig.3.The spectrum is composed of only one semicircle in the high frequency range and a straight line in the low frequency range,which is well known due to the bulk resistance and the Warburg resistance.No second semicircle due to the grain boundary resistance is observed,indicating extremely low grain boundary resistance of the LAGP electrolyte.It is known that the LAGP will form a glass-ceramic structure during fast cooling.16,20The lower grain boundary resistance will greatly facilitate the Li ions transportation during the charge and discharge processes.The total ionic conductivity can be calculated from s ~L tot where R tot is the total resistance which is equal to sum of bulk resistance,R b and grain boundary resistance,R gb of the samples,L is the thickness of the electrolyte pellet,S is the cross sectional area of the electrolyte.The R tot can be obtained from the right intercept of the semicircle with the real axis ray.If R tot is taken to be 2700V ,S is 50mm 2,and L is 1mm,the total conductivity,s is 761025S cm 21which is a little lower than thebest1XRD spectrum of as preparedLAGP2Surface morphology of as preparedLAGP3AC impedance of LAGP pelletFeng et al.Solid state lithium ion rechargeable batteriesMaterials Technology 2013VOL28NO5277reported data 16,20but higher than that of the widely used LiPON.8Figure 4shows the cyclic voltammetry (CV)spectrum of the solid electrolyte (Pt/LAGP/Li)measured at room temperature with a scan rate of 0?1mV s 21in the voltage range from 20?4to 6V.Figure 4reveals that the Li metal can reversibly be deposited and dissolved between 20?4and 0?6V.No other reactions are observed even at 6V,indicating that LAGP can work at least up to 6V potential while for most of cathode materials the highest potential is only up to 5V.The result is also consistent with previous reports.16,17The high ionic conductivity and high potential window make the LAGP be a promising electrolyte for the all solid state Li batteries.Figure 5shows the surface morphology of the LiMn 2O 4layer deposited on the LAGP pellet.The cathode ﬁlm appears smooth,dense,and free of cracks and pin holes.The grain diameter is about 40nm.The insert in Fig.5shows the LAGP pellets before (white)and after (black)deposition of the cathode,showing that the LAGP electrolyte is fully covered by black LiMn 2O 4.As shown in Fig.6,a pure LAGP phase (Fig.6a )can be seen before LiMn 2O 4deposition.After deposition a new diffraction peak at 2h 518?6u C appears and the diffraction can be indexed to be the spinel LiMn 2O 4(111)diffraction.23The week LiMn 2O 4diffraction peakis due to thin LiMn 2O 4ﬁlm character.There is no distinguished change in the diffraction from the LAGP pellet,implying that the LAGP structure is stable and no reaction with LiMn 2O 4at the present deposition conditions.To test the electrochemical performance of the LiMn 2O 4/LAGP/Li cell,CV measurement was carried out between 2and 4?5V.Figure 7shows a typical CV curve of the LiMn 2O 4/LAGP/Li cell at a scan rate of 0?1mV s 21.From Fig.7,two separated pairs of peaks can clearly be seen,which are resulted from the typical lithium intercalation and de-intercalation feature of LiMn 2O 4.The slightly large separated distance between anodic and catholic peaks is mainly due to large polarization caused by the relatively lower conductivity of the LAGP compared with the liquid electrolytes as well as low conductivity of the cathode material since there is no conductive additive is used as the traditional bulk Li ion rechargeable batteries.It is also noted that the pairs of anodic and cathodic peaks are week and broad which are resulted from large polarization.Figure 8gives the 150typical charge/discharge curves of the LiMn 2O 4/LAGP/Li cell at a constant currentof4Potential window of LAGPpellet5SEM of LiMn 2O 4deposited on LAGP pellet with insertshowing overview of LAGP pellets before (white)and after (black)LiMn 2O 4deposition6XRD spectra of LAGP pellets a before and b afterLiMn 2O 4deposition7CV curve of LiMn 2O 4/LAGP/Li cell at scan rate of0?1mV s 21Feng et al.Solid state lithium ion rechargeable batteries278Materials Technology 2013VOL28NO525mA g 21in a potential range from 2to 4?5V due to the fact that polarization was very high resulting in large drop in discharge voltage and increase in charge voltage.The voltage proﬁles show an expected potential plateau for LiMn 2O 4with the ﬁrst charge capacity of 80mAh g 21which is due to the well known lithium intercalation and de-intercalation reaction of LiMn 2O 4.23–25The subse-quent cycles show a similar shape with an increased capacity as well as coulombic efﬁciency.We ascribe the increased capacity to be caused by activation and reduction in impedance between the electrode layers and electrolyte.When a Li metal foil is pressed directly onto the electrolyte,interface impedance is high due to the formation of solid interface ﬁlm (such as Li 2O).25,26In addition,the Li metal foil is also unable to fully contact with the electrolyte.With cycling,the impedance layer may be broken and the contact area between the Li metal and the electrolyte may also increase.After 150charge/discharge cycles,the capacity increases from 80to 115mAh g 21,which is also reported in other papers.24The charge/discharge spectra of the LiMn 2O 4/LAGP/Li full cell are almost similar during cycling demonstrating that the LiMn 2O 4/LAGP/Li cell has a good cyclability.The reason for the high capacity retention in the current study may be contributed reduced Mn 2z disslovation when the solid electrolyte is used.27,28ConclusionsNASICON structured LAGP was prepared and tested as the electrolyte for all solid state lithium batteries.The results show that LAGP has a 6V potential window and an ionic conductivity of 7?561025S cm 21.For the ﬁrst time,a LiMn 2O 4/LAGP/Li cell was constructed andtested.The cell showed an 80mAh g 21ﬁrst charge capacity and 115mAh g 21after 150cycles,suggesting that LAGP can be used as a promising 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