锂离子电池三元正极材料LiNi0.5Co0.2Mn0.3O2(NCM523)制备及改性
合集下载
相关主题
- 1、下载文档前请自行甄别文档内容的完整性，平台不提供额外的编辑、内容补充、找答案等附加服务。
- 2、"仅部分预览"的文档,不可在线预览部分如存在完整性等问题,可反馈申请退款(可完整预览的文档不适用该条件!)。
- 3、如文档侵犯您的权益，请联系客服反馈,我们会尽快为您处理(人工客服工作时间：9:00-18:30)。
2015 年 10 月 22 日
万方数据
万方数据
长沙矿冶研究院硕士学位论文
论文题目：锂离子电池三元正极材料 LiNi0.5Co0.2Mn0.3O2(NCM523)制备及改性
作 者 姓 名 ：龚诚
指 导 教 师：习小明教授单位：长沙矿冶研究院 指 导 教 师：周友元教授单位：长沙矿冶研究院 论文提交日期：2015 年 6 月 13 日 学位授予单位：长沙矿冶研究院
(2) Sr(OH)2·8H2O was used as doped agent during the process of high compacted density NCM523 preparation under the best conditions thatlithium and metal ratio was 1.08, and the optimal sintering conditions was 960℃ and 9 hours.The impacts of the Sr mixed amount on the structure, morphology, density, compaction density and electrochemical properties of materials were studied. The compaction density was 3.72 g/cm3when the doped amount of Sr was 1300 ppm in the high compacted density NCM523 cathod materials. The fist discharge specific capacity was 150.0 mAh/g and the volume energy density was 558 mAh/cm3 under an 1C current density between 2.8~4.2V at 25℃. The capacity retention ratewas 95.7% after 100 cycles.
（1）进行高温固相烧结制备高压实型 NCM523 正极材料，考察了配锂量、烧结 温度、烧结时间对材料结构、形貌、真密度、压实密度和电化学性能的影响，确定了 配锂 1.08、960℃烧结 9h 的最优合成条件。在此条件下合成的高压实型 NCM523 正极 材料制作压实密度达 3.72g/cm3，电化学综合性能最好。实效电池在 2.8~4.2V 范围内， 25℃、1C 倍率条件下首次放电比容量为 153 mAh/g，体积比能量密度达 569.2 mAh/cm3， 100 周循环后容量保持率为 95.1%。
万方数据
万方数据
原创性声明
本人声明，所呈交的学位论文是本人在导师指导下进行的研究工作及 取得的研究成果。尽我所知，除了论文中特别加以标注和致谢的地方外， 论文中不包含其他人已经发表或撰写过的研究成果，也不包含为获得长沙 矿冶研究院或其他单位的学位或证书而使用过的材料。与我共同工作的同 志对本研究所作的贡献均已在论文中作了明确的说明。
万方数据
万方数据
摘要
LiNi1-x-yCoxMnyO2 三元正极材料集成了钴酸锂、镍酸锂、锰酸锂等材料的优点， 合成难度低、能量密度高、循环稳定性好、成本较低、安全性好，已成功地广泛应用 在数码产品中，下一步希望将其应用于动力电池领域。但是其制作压实密度≤3.4g/cm3， 与钴酸锂 4.10g/cm3 的制作压实相差很大；提高电压上限后，循环稳定性差，经过数 十周充放电循环后比容量迅速衰减。这些不足制约了三元锂离子电池朝大功率、高能 量密度方向的发展，需要进行优化改性。本文查阅了三元正极材料发展情况，选择 NCM523 正极材料作为研究对象，以 Ni0.5Co0.2Mn0.3(OH)2 前驱体和 Li2CO3 为原料，通 过调节高温固相烧结工艺及进行 Sr 掺杂，制备出两种高压实型 NCM523 正极材料； 通过 Al 掺杂、包覆改性，制备出高电压型 NCM523 正极材料。
中图分类号 UDC
密
级公开
单 位 代 码 82603
长沙矿冶研究院
硕士学位论文
论文题目：锂离子电池三元正极材料 LiNi0.5Co0.2Mn0.3O2(NCM523)制备及改性
论文编号： 826033201500001 作 者： 龚诚 导师姓名： 习小明教授 副导师姓名： 周友元教授 专业名称： 材料学
（2）在配锂 1.08、950℃烧结 9h 过程中添加 Sr(OH)2·8H2O，考察了掺 Sr 量对材 料结构、形貌、真密度、压实密度和电化学性能的影响。掺 Sr 量 1300ppm 合成的高 压实型 NCM523 正极材料制作压实密度达 3.72g/cm3，实效电池在 2.8~4.2V 范围内， 25℃、1C 倍率条件下首次放电比容量为 150 mAh/g，体积比能量密度达 558mAh/cm3， 100 周循环后容量保持率为 95.70%。
(3) Nanometer-Al2O3 was used as doped agent during the process of NCM523 pHale Waihona Puke epa-II万方数据
ration under the conditions of lithium and metal ratio was 1.04, 930℃ and 6 hours. When the Al3+ was doped, the stability of the layer structure under high voltage has been improved. And the impacts of the doped amount of Al on the structure, morphology and electrochemical properties of materials were studied. The corrosion resistance and cycle stability were improved when Al coated on the surface of the best Al doped sample. The surface Al coated sample of 500 ppm was improved obviously under high voltage, the first discharge specific capacity was 186.4 mAh/g under 0.1C and the capacity retention ratewas 80.6% after 45 cycles under 1C between 3.0~4.43V at 25℃.The full batteryfirst discharge specific capacity was175 mAh/g under an 1C current density between 3.00~4.35V at 25℃. The capacity fadedwas6.8% after 100 cycles. KEY WORDSLithiumion batteries; high temperature solid-phase sintering;high compacted density;high voltage; ion doping;surface coating.
(1) Ni0.5Co0.2Mn0.3(OH)2 precursor was choosed to prepare high compacted density NCM523. The impacts of lithium content, sintering temperature and sintering time on the structure, morphology, density, compaction density and electrochemical properties of materials were studied. The best lithium and metal ratio was 1.08, and the optimal sintering conditions was 960℃ and 9 hours.The compaction density of the high compacted density NCM523 materials synthesized under this condition was 3.72 g/cm3, and the electrochemical performance was best. The first discharge specific capacity was 153.0 mAh/g and the volume energy density was 569.2 mAh/cm3 under an 1C current density between 2.8~4.2V at 25℃. The capacity retention ratewas 95.1% after 100 cycles.
关键词 锂离子电池；高温固相烧结；高压实；高电压；离子掺杂；表面包覆
I
万方数据
Abstract
LiNi1-x-yCoxMnyO2cathode material which has integrated with the advantages of lithium cobalt oxides, lithium nickel oxides, and lithium manganese oxides, such as low difficulty of synthesis, high energy density, good cycle stability, low cost and good safety.It has been successfully applied to electronics, and want to be used in the power battery next .But the produced compaction density is only 3.4 g/cm3, which less than the lithium cobalt oxides is4.10 g/cm3.Whenelevatedthe voltage limit, the cycle stability and specific capacitywere bad after several cycles.These disadvantages were limited the development of ternary lithium ion battery in the direction of the high power and high energy density, and need to be optimized modification.NCM523 was choosed to study the development situation of LiNi1-x-yCoxMnyO2 cathode materials in this paper. Two types of high compacted densityNCM523 cathode materials were prepared by adjusted the high temperature solid-phase sintering process and Sr doped. The high voltage NCM523 was preparedby Al doped and coated modification.
（3）在配锂 1.04、930℃烧结 6h 过程中加入纳米 Al2O3，进行 Al3+掺杂改性，改 善材料高电压条件下层状结构的稳定性，考察了掺 Al 量对材料结构、形貌和电化学 性能的影响。选取最佳的掺 Al 样品再进行表面 Al 包覆处理，改善材料表面抗腐蚀性， 提高循环稳定性。在其表面湿法包覆 Al 500ppm 后，组装的扣式电池在 3.00~4.43V 范 围内，25℃、0.1C 倍率首次放电比容量提升至 186.4 mAh/g，1C 倍率循环 45 周后容 量保持率达到 80.6%，高电压条件下电化学性能得到显著的优化。组装成实效电池后， 在 3.00~4.35V 电压范围内，25℃、1C 倍率测试条件下，首次放电比容量为 175mAh/g， 100 周循环后的容量衰减 6.8%。
作者签名：日期：年月日
关于学位论文使用授权说明
本人了解长沙矿冶研究院有关保留、使用学位论文的规定，即：长沙 矿冶研究院有权保留学位论文，允许学位论文被查阅和借阅，可以公布学 位论文的全部或部分内容，可以采用复印、缩印或其它手段保存学位论文， 可根据国家或湖南省有关部门规定送交学位论文。
（保密的论文在年解密后适用本授权规定） 作者签名：导师签名日期：年月日
万方数据
万方数据
长沙矿冶研究院硕士学位论文
论文题目：锂离子电池三元正极材料 LiNi0.5Co0.2Mn0.3O2(NCM523)制备及改性
作 者 姓 名 ：龚诚
指 导 教 师：习小明教授单位：长沙矿冶研究院 指 导 教 师：周友元教授单位：长沙矿冶研究院 论文提交日期：2015 年 6 月 13 日 学位授予单位：长沙矿冶研究院
(2) Sr(OH)2·8H2O was used as doped agent during the process of high compacted density NCM523 preparation under the best conditions thatlithium and metal ratio was 1.08, and the optimal sintering conditions was 960℃ and 9 hours.The impacts of the Sr mixed amount on the structure, morphology, density, compaction density and electrochemical properties of materials were studied. The compaction density was 3.72 g/cm3when the doped amount of Sr was 1300 ppm in the high compacted density NCM523 cathod materials. The fist discharge specific capacity was 150.0 mAh/g and the volume energy density was 558 mAh/cm3 under an 1C current density between 2.8~4.2V at 25℃. The capacity retention ratewas 95.7% after 100 cycles.
（1）进行高温固相烧结制备高压实型 NCM523 正极材料，考察了配锂量、烧结 温度、烧结时间对材料结构、形貌、真密度、压实密度和电化学性能的影响，确定了 配锂 1.08、960℃烧结 9h 的最优合成条件。在此条件下合成的高压实型 NCM523 正极 材料制作压实密度达 3.72g/cm3，电化学综合性能最好。实效电池在 2.8~4.2V 范围内， 25℃、1C 倍率条件下首次放电比容量为 153 mAh/g，体积比能量密度达 569.2 mAh/cm3， 100 周循环后容量保持率为 95.1%。
万方数据
万方数据
原创性声明
本人声明，所呈交的学位论文是本人在导师指导下进行的研究工作及 取得的研究成果。尽我所知，除了论文中特别加以标注和致谢的地方外， 论文中不包含其他人已经发表或撰写过的研究成果，也不包含为获得长沙 矿冶研究院或其他单位的学位或证书而使用过的材料。与我共同工作的同 志对本研究所作的贡献均已在论文中作了明确的说明。
万方数据
万方数据
摘要
LiNi1-x-yCoxMnyO2 三元正极材料集成了钴酸锂、镍酸锂、锰酸锂等材料的优点， 合成难度低、能量密度高、循环稳定性好、成本较低、安全性好，已成功地广泛应用 在数码产品中，下一步希望将其应用于动力电池领域。但是其制作压实密度≤3.4g/cm3， 与钴酸锂 4.10g/cm3 的制作压实相差很大；提高电压上限后，循环稳定性差，经过数 十周充放电循环后比容量迅速衰减。这些不足制约了三元锂离子电池朝大功率、高能 量密度方向的发展，需要进行优化改性。本文查阅了三元正极材料发展情况，选择 NCM523 正极材料作为研究对象，以 Ni0.5Co0.2Mn0.3(OH)2 前驱体和 Li2CO3 为原料，通 过调节高温固相烧结工艺及进行 Sr 掺杂，制备出两种高压实型 NCM523 正极材料； 通过 Al 掺杂、包覆改性，制备出高电压型 NCM523 正极材料。
中图分类号 UDC
密
级公开
单 位 代 码 82603
长沙矿冶研究院
硕士学位论文
论文题目：锂离子电池三元正极材料 LiNi0.5Co0.2Mn0.3O2(NCM523)制备及改性
论文编号： 826033201500001 作 者： 龚诚 导师姓名： 习小明教授 副导师姓名： 周友元教授 专业名称： 材料学
（2）在配锂 1.08、950℃烧结 9h 过程中添加 Sr(OH)2·8H2O，考察了掺 Sr 量对材 料结构、形貌、真密度、压实密度和电化学性能的影响。掺 Sr 量 1300ppm 合成的高 压实型 NCM523 正极材料制作压实密度达 3.72g/cm3，实效电池在 2.8~4.2V 范围内， 25℃、1C 倍率条件下首次放电比容量为 150 mAh/g，体积比能量密度达 558mAh/cm3， 100 周循环后容量保持率为 95.70%。
(3) Nanometer-Al2O3 was used as doped agent during the process of NCM523 pHale Waihona Puke epa-II万方数据
ration under the conditions of lithium and metal ratio was 1.04, 930℃ and 6 hours. When the Al3+ was doped, the stability of the layer structure under high voltage has been improved. And the impacts of the doped amount of Al on the structure, morphology and electrochemical properties of materials were studied. The corrosion resistance and cycle stability were improved when Al coated on the surface of the best Al doped sample. The surface Al coated sample of 500 ppm was improved obviously under high voltage, the first discharge specific capacity was 186.4 mAh/g under 0.1C and the capacity retention ratewas 80.6% after 45 cycles under 1C between 3.0~4.43V at 25℃.The full batteryfirst discharge specific capacity was175 mAh/g under an 1C current density between 3.00~4.35V at 25℃. The capacity fadedwas6.8% after 100 cycles. KEY WORDSLithiumion batteries; high temperature solid-phase sintering;high compacted density;high voltage; ion doping;surface coating.
(1) Ni0.5Co0.2Mn0.3(OH)2 precursor was choosed to prepare high compacted density NCM523. The impacts of lithium content, sintering temperature and sintering time on the structure, morphology, density, compaction density and electrochemical properties of materials were studied. The best lithium and metal ratio was 1.08, and the optimal sintering conditions was 960℃ and 9 hours.The compaction density of the high compacted density NCM523 materials synthesized under this condition was 3.72 g/cm3, and the electrochemical performance was best. The first discharge specific capacity was 153.0 mAh/g and the volume energy density was 569.2 mAh/cm3 under an 1C current density between 2.8~4.2V at 25℃. The capacity retention ratewas 95.1% after 100 cycles.
关键词 锂离子电池；高温固相烧结；高压实；高电压；离子掺杂；表面包覆
I
万方数据
Abstract
LiNi1-x-yCoxMnyO2cathode material which has integrated with the advantages of lithium cobalt oxides, lithium nickel oxides, and lithium manganese oxides, such as low difficulty of synthesis, high energy density, good cycle stability, low cost and good safety.It has been successfully applied to electronics, and want to be used in the power battery next .But the produced compaction density is only 3.4 g/cm3, which less than the lithium cobalt oxides is4.10 g/cm3.Whenelevatedthe voltage limit, the cycle stability and specific capacitywere bad after several cycles.These disadvantages were limited the development of ternary lithium ion battery in the direction of the high power and high energy density, and need to be optimized modification.NCM523 was choosed to study the development situation of LiNi1-x-yCoxMnyO2 cathode materials in this paper. Two types of high compacted densityNCM523 cathode materials were prepared by adjusted the high temperature solid-phase sintering process and Sr doped. The high voltage NCM523 was preparedby Al doped and coated modification.
（3）在配锂 1.04、930℃烧结 6h 过程中加入纳米 Al2O3，进行 Al3+掺杂改性，改 善材料高电压条件下层状结构的稳定性，考察了掺 Al 量对材料结构、形貌和电化学 性能的影响。选取最佳的掺 Al 样品再进行表面 Al 包覆处理，改善材料表面抗腐蚀性， 提高循环稳定性。在其表面湿法包覆 Al 500ppm 后，组装的扣式电池在 3.00~4.43V 范 围内，25℃、0.1C 倍率首次放电比容量提升至 186.4 mAh/g，1C 倍率循环 45 周后容 量保持率达到 80.6%，高电压条件下电化学性能得到显著的优化。组装成实效电池后， 在 3.00~4.35V 电压范围内，25℃、1C 倍率测试条件下，首次放电比容量为 175mAh/g， 100 周循环后的容量衰减 6.8%。
作者签名：日期：年月日
关于学位论文使用授权说明
本人了解长沙矿冶研究院有关保留、使用学位论文的规定，即：长沙 矿冶研究院有权保留学位论文，允许学位论文被查阅和借阅，可以公布学 位论文的全部或部分内容，可以采用复印、缩印或其它手段保存学位论文， 可根据国家或湖南省有关部门规定送交学位论文。
（保密的论文在年解密后适用本授权规定） 作者签名：导师签名日期：年月日