锂离子电池的碳导电添加剂
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(electrolyte retention and lithium ion transport rate in the electrode pores 电解液的保持和在电极孔中锂离子的传送速率)
- electrolyte absorption 电解液的吸收 - control of electrode pore structure电极多孔结构的控制
1. Introduction (介绍）
• Why carbon materials as conductive matrix? 为什么碳材料可以作为导电体
• Role of the carbon conductive matrix,碳导电体的作用 2. Graphite as conductive additive 石墨作为导电添加剂 3. Carbon black as conductive additive 碳黑作为导电添加剂
CIBF2005, April 3rd, 2005
Graphite conductive additives-positive electrode 正极石墨导电剂 球面电阻Pellet resistivity of LiCoO2
1.4 1.2 电阻 [W cm] 1.0
KS6 KS15 SFG15 MX15
r [W*cm]
1 Resistivity level of the electrode material电极的导电
Percolation curve 渗透曲线
Slope 斜率 Ultimate resistivity level最终的电阻率
0.1
5
10
15
vol.% C
Limits for thin film electrodes, but suitable for material comparisons 对薄膜电极有局限性,但适用材料的比较
Raw purified graphite (min. 99 % C)初纯石墨
conditioning, grinding, classifying, mechanical/chemical treatment, 处理,研磨,分类,机械/化学处理
Final graphite product产品
CIBF2005, April 3rd, 2005
Graphite ore矿石
crushing, grinding, Flotation,粉碎,研磨,浮选
Raw material mix初混物 Graphitization石墨化
Raw graphite (max. 98 % C)初产品
thermal/chemical Purification热/化学纯化
Graphite manufacturing process石墨生产过程 Synthetic graphite合成石墨 Graphitization process石墨化过程 TIMREX® Coke
Temperature [1000°C] 1
2
3
0
50
100
150
200
TIMREX® Graphite
KS-type SFG-type T-type SLM-type SLX-type NP-type
1 M LiPF6 in EC/DMC 1:1 (w:w) 10 % PVDF binder
0
2
4
6
8
10
12
14
16
2
18
20
Specific BET Surface Area [m /g]
CIBF2005, April 3rd, 2005
Graphite manufacturing process石墨生产过程 Primary synthetic graphite原生石墨
Carbon precursor 碳前体
selection, crushing Mixing,筛选,粉碎,和混合
Natural graphite天然石墨
Crystallite size [nm]晶体尺寸
CIBF2005, April 3rd, 2005
Graphite material properties石墨性能
Surface表面
Purity纯度
Crystallinity晶体
Particle size/ Particle shape 颗粒尺寸/颗粒形状
2. Energy density optimization能量密度的最优化 • electrode density (compaction properties)电极密度(压实性) • electrolyte and polymer binder content (polymer/electrolyte absorption) • electrochemical and chemical side reactions (surface area)
U I
Cathode bar
I
B
0.8
0.6 0.4
0.2
0.0 4 5 6 7 8 9 10
Leabharlann Baidu
石墨含量 [%]
CIBF2005, April 3rd, 2005
Graphite conductive additives - negative electrode 负极石墨导电剂 Graphite additives in the negative electrode石墨在负极中
400
Specific charge [mAh/g]
350 300 250 200 150 100 0
MCMB/SFG6
Li insertion + Li de-insertion 20 40 60
+
MCMB
Electrolyte: 1 M LiPF6 in EC/DMC (1:1) Binder: 10 % PVDF
4. Graphite or carbon black? 选择石墨还是碳黑
5. Conclusions 结论
CIBF2005, April 3rd, 2005
Carbon conductive additives 碳导电添加剂
1. primary synthetic and natural graphite powders原生合成和天然石墨粉 (Xylene density: 2.230-2.267 g cm-3, 二甲苯密度 graphite interlayer distance石墨层距 c/2: 0.3354-0.3360 nm) 2. conductive carbon blacks 导电碳黑
CIBF2005, April 3rd, 2005
Influence of the carbon conductive additive 碳导电剂的影响
1. Electrode impedance optimization电极电阻的最优化
Increase of the ionic conductivity增加离子导电性
1.4 1.2
[V] Potential vs. Li/Li
+
1.0 0.8 0.6
10 mm
0.4 0.2 0.0
0
100
200
300
400
1 M LiPF6 in EC/DMC 1:1 (w:w) 10 % PVDF binder
Specific Charge [mAh/g Carbon]
CIBF2005, April 3rd, 2005
CIBF2005, April 3rd, 2005
Influence of the carbon conductive additive 碳导电剂的影响
1. Electrode impedance optimization电阻的最优化 Increase of the electronic conductivity增加导电性 (mathematically described by the Percolation Theory or the Effective Medium Theory渗透理论的数学描述)
Carbon Conductive Additives for Lithium Ion Batteries 锂离子电池的碳导电添加剂
Michael E. Spahr, Ye Bing
CIBF2005, April 3rd, 2005
Carbon conductive additives for lithium ion batteries Outline 大纲
Graphite porosity
10 8 Vads. [[cm3]] 6 4 2 0 0.0 0.2 0.4 0.6 0.8 1.0 Pressure [p/760 Torr]
N2-adsorption N2-desorption
Type III-isotherme III 型等温线
(Brunauer, Emmett, Teller)
80
100
Cycle number
CIBF2005, April 3rd, 2005
Graphite conductive additives-negative electrode 负极石墨导电剂 Double function intercalation host双重功效嵌入主体
TIMREX® SFG44
mesoporous material 间孔材料 Total graphite surface area 石墨表面积 • geometrical surface area • porosity
几何表面积 多孔性
• surface roughness
• surface defects
表面缺陷 表面粗糙度
Graphite conductive additives-negative electrode 负极石墨导电剂
Influence of the specific BET surface area比表面积的影响
26 24 22 20 18 16 14 12 10 8 6 4 2 0
Irreversible Capacity [%]
c=1.0072 nm
Rombohedral
l=0.1421 nm B c/2=.03354 nm
A
B
C
A
a=0.246 nm Hexagonal
CIBF2005, April 3rd, 2005
Graphite material properties石墨性能
Graphite texture
石墨质地
电化学和化学副反应 电解质和高分子粘接剂的含量
3. Electrode manufacturing process (slurry preparation)电极生产过程(制浆) - dispersibility in the liquid media分散在液体介质中 - viscosity control of the slurry (solvent absorption)浆料的粘度控制
Advantages of carbon additives in electrochemical applications 碳导电添加剂在电化学应用中的优点
electrical conductivity 导电性 thermal conductivity (graphite in particular) 导热性(特别是石墨) non-toxic and environmentally begnin无毒环境友好 chemically inert化学稳定性 available in high quantity and purity高纯度 low weight 低重量 relatively low production costs 相对低的制造成本
Texture/ Porosity质地/多孔性
Properties性能
CIBF2005, April 3rd, 2005
Graphite material properties石墨性能 Graphite crystal structure石墨的晶体结构
Basal Plane Surface
A
A
Prismatic Surface
TIMREX® SFG44
Polycrystalline particles 多晶颗粒
Isotropic properties 各向同性
1 mm CIBF2005, April 3rd, 2005
Anisotropic properties 各向异性
Graphite material properties石墨性能
- electrolyte absorption 电解液的吸收 - control of electrode pore structure电极多孔结构的控制
1. Introduction (介绍）
• Why carbon materials as conductive matrix? 为什么碳材料可以作为导电体
• Role of the carbon conductive matrix,碳导电体的作用 2. Graphite as conductive additive 石墨作为导电添加剂 3. Carbon black as conductive additive 碳黑作为导电添加剂
CIBF2005, April 3rd, 2005
Graphite conductive additives-positive electrode 正极石墨导电剂 球面电阻Pellet resistivity of LiCoO2
1.4 1.2 电阻 [W cm] 1.0
KS6 KS15 SFG15 MX15
r [W*cm]
1 Resistivity level of the electrode material电极的导电
Percolation curve 渗透曲线
Slope 斜率 Ultimate resistivity level最终的电阻率
0.1
5
10
15
vol.% C
Limits for thin film electrodes, but suitable for material comparisons 对薄膜电极有局限性,但适用材料的比较
Raw purified graphite (min. 99 % C)初纯石墨
conditioning, grinding, classifying, mechanical/chemical treatment, 处理,研磨,分类,机械/化学处理
Final graphite product产品
CIBF2005, April 3rd, 2005
Graphite ore矿石
crushing, grinding, Flotation,粉碎,研磨,浮选
Raw material mix初混物 Graphitization石墨化
Raw graphite (max. 98 % C)初产品
thermal/chemical Purification热/化学纯化
Graphite manufacturing process石墨生产过程 Synthetic graphite合成石墨 Graphitization process石墨化过程 TIMREX® Coke
Temperature [1000°C] 1
2
3
0
50
100
150
200
TIMREX® Graphite
KS-type SFG-type T-type SLM-type SLX-type NP-type
1 M LiPF6 in EC/DMC 1:1 (w:w) 10 % PVDF binder
0
2
4
6
8
10
12
14
16
2
18
20
Specific BET Surface Area [m /g]
CIBF2005, April 3rd, 2005
Graphite manufacturing process石墨生产过程 Primary synthetic graphite原生石墨
Carbon precursor 碳前体
selection, crushing Mixing,筛选,粉碎,和混合
Natural graphite天然石墨
Crystallite size [nm]晶体尺寸
CIBF2005, April 3rd, 2005
Graphite material properties石墨性能
Surface表面
Purity纯度
Crystallinity晶体
Particle size/ Particle shape 颗粒尺寸/颗粒形状
2. Energy density optimization能量密度的最优化 • electrode density (compaction properties)电极密度(压实性) • electrolyte and polymer binder content (polymer/electrolyte absorption) • electrochemical and chemical side reactions (surface area)
U I
Cathode bar
I
B
0.8
0.6 0.4
0.2
0.0 4 5 6 7 8 9 10
Leabharlann Baidu
石墨含量 [%]
CIBF2005, April 3rd, 2005
Graphite conductive additives - negative electrode 负极石墨导电剂 Graphite additives in the negative electrode石墨在负极中
400
Specific charge [mAh/g]
350 300 250 200 150 100 0
MCMB/SFG6
Li insertion + Li de-insertion 20 40 60
+
MCMB
Electrolyte: 1 M LiPF6 in EC/DMC (1:1) Binder: 10 % PVDF
4. Graphite or carbon black? 选择石墨还是碳黑
5. Conclusions 结论
CIBF2005, April 3rd, 2005
Carbon conductive additives 碳导电添加剂
1. primary synthetic and natural graphite powders原生合成和天然石墨粉 (Xylene density: 2.230-2.267 g cm-3, 二甲苯密度 graphite interlayer distance石墨层距 c/2: 0.3354-0.3360 nm) 2. conductive carbon blacks 导电碳黑
CIBF2005, April 3rd, 2005
Influence of the carbon conductive additive 碳导电剂的影响
1. Electrode impedance optimization电极电阻的最优化
Increase of the ionic conductivity增加离子导电性
1.4 1.2
[V] Potential vs. Li/Li
+
1.0 0.8 0.6
10 mm
0.4 0.2 0.0
0
100
200
300
400
1 M LiPF6 in EC/DMC 1:1 (w:w) 10 % PVDF binder
Specific Charge [mAh/g Carbon]
CIBF2005, April 3rd, 2005
CIBF2005, April 3rd, 2005
Influence of the carbon conductive additive 碳导电剂的影响
1. Electrode impedance optimization电阻的最优化 Increase of the electronic conductivity增加导电性 (mathematically described by the Percolation Theory or the Effective Medium Theory渗透理论的数学描述)
Carbon Conductive Additives for Lithium Ion Batteries 锂离子电池的碳导电添加剂
Michael E. Spahr, Ye Bing
CIBF2005, April 3rd, 2005
Carbon conductive additives for lithium ion batteries Outline 大纲
Graphite porosity
10 8 Vads. [[cm3]] 6 4 2 0 0.0 0.2 0.4 0.6 0.8 1.0 Pressure [p/760 Torr]
N2-adsorption N2-desorption
Type III-isotherme III 型等温线
(Brunauer, Emmett, Teller)
80
100
Cycle number
CIBF2005, April 3rd, 2005
Graphite conductive additives-negative electrode 负极石墨导电剂 Double function intercalation host双重功效嵌入主体
TIMREX® SFG44
mesoporous material 间孔材料 Total graphite surface area 石墨表面积 • geometrical surface area • porosity
几何表面积 多孔性
• surface roughness
• surface defects
表面缺陷 表面粗糙度
Graphite conductive additives-negative electrode 负极石墨导电剂
Influence of the specific BET surface area比表面积的影响
26 24 22 20 18 16 14 12 10 8 6 4 2 0
Irreversible Capacity [%]
c=1.0072 nm
Rombohedral
l=0.1421 nm B c/2=.03354 nm
A
B
C
A
a=0.246 nm Hexagonal
CIBF2005, April 3rd, 2005
Graphite material properties石墨性能
Graphite texture
石墨质地
电化学和化学副反应 电解质和高分子粘接剂的含量
3. Electrode manufacturing process (slurry preparation)电极生产过程(制浆) - dispersibility in the liquid media分散在液体介质中 - viscosity control of the slurry (solvent absorption)浆料的粘度控制
Advantages of carbon additives in electrochemical applications 碳导电添加剂在电化学应用中的优点
electrical conductivity 导电性 thermal conductivity (graphite in particular) 导热性(特别是石墨) non-toxic and environmentally begnin无毒环境友好 chemically inert化学稳定性 available in high quantity and purity高纯度 low weight 低重量 relatively low production costs 相对低的制造成本
Texture/ Porosity质地/多孔性
Properties性能
CIBF2005, April 3rd, 2005
Graphite material properties石墨性能 Graphite crystal structure石墨的晶体结构
Basal Plane Surface
A
A
Prismatic Surface
TIMREX® SFG44
Polycrystalline particles 多晶颗粒
Isotropic properties 各向同性
1 mm CIBF2005, April 3rd, 2005
Anisotropic properties 各向异性
Graphite material properties石墨性能