Chemical Industry and Engineering Progress ›› 2024, Vol. 43 ›› Issue (9): 4767-4778.DOI: 10.16085/j.issn.1000-6613.2024-0442
• Invited review •
GAO Yuli(), WANG Hongqiu, HUANG Gexing, XIAN Nanying, SHI Xiaoyu
Received:
2024-03-18
Revised:
2024-04-24
Online:
2024-09-30
Published:
2024-09-15
Contact:
GAO Yuli
通讯作者:
高玉李
作者简介:
高玉李(1987—),女,博士,高级工程师,研究方向为固态电池战略信息。E-mail:gaoyuli@petrochina.com.cn。
CLC Number:
GAO Yuli, WANG Hongqiu, HUANG Gexing, XIAN Nanying, SHI Xiaoyu. Research progress and the industrialization of all-solid-state battery[J]. Chemical Industry and Engineering Progress, 2024, 43(9): 4767-4778.
高玉李, 王红秋, 黄格省, 鲜楠莹, 师晓玉. 全固态锂电池的产业化和技术研究进展[J]. 化工进展, 2024, 43(9): 4767-4778.
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URL: https://hgjz.cip.com.cn/EN/10.16085/j.issn.1000-6613.2024-0442
国家 | 典型代表 公司 | 种类 | 电解质组成 | 离子电导率 /S·cm-1 | 电池:正极||电解质||负极 | 倍率 | 放电容量 /mAh·g-1 | 循环寿命 |
---|---|---|---|---|---|---|---|---|
日本 | 丰田 | 硫化物电解质 | LGPS[ | 1.2×10-2 | LCO | 120 | — | |
含有Li、P、S、I、Br元素的电解质[ | 5×10-3 | — | — | — | — | |||
由15LiBr+10LiI+75(0.75Li2S+0.25P2S5)组成,具有PS43-结构的电解质[ | 3.2×10-3 | — | — | — | — | |||
Li9.54Si1.74P1.44S11.7Cl0.3[ | 2.5×10-2 | LNO-LCO | 18C | >120 | 循环500次,放电容量保持率75%(100℃) | |||
Li2S-P2S5-LiCl[ | 3.2×10-3 | — | — | — | — | |||
本田 | 硫化物电解质 | Li2S+P2S5+LiBH4[ | 3.3×10-2 | NCM811 | — | 170 | — | |
硫化物电解质+有机电解质 | LGPS+PVDF-HFP+LiClO4[ | — | NCM622 | 0.5C | — | 循环500次,放电容量保持率90%(55℃) | ||
韩国 | LG新能源 | 硫化物电解质+纯硅负极 | Li6PS5Cl[ | — | NCM811 | 1C | >1250 | 循环500次以上,放电容量保持率80%(25℃) |
三星 | 硫化物电解质+银碳负极 | Li6PS5Cl[ | — | LiNi0.9Co0.05Mn0.05O2 | 0.5C | 146 | 循环1000次,放电容量保持率89%(60℃) | |
美国 | Solid Power | 硫化物电解质 | Li3PS4+LiBH4[ | 8.2×10-3 | — | — | — | — |
硫化物电解质 | Li4SbS4I[ | 5.25×10-4 | — | — | — | — | ||
中国 | 中科固能 | 硫化物电解质 | Li6.8Si0.8As0.2S5I[ | 1.04×10-2 | Ti2S | 电流密度 2.44mA/cm2 | — | 62500次(30 ℃) |
卤化物+硫化物 | Li3InCl6+Li6PS5Cl[ | — | NCM90-Li3InCl6 | 20C | 循环30000次,放电容量保持率大于70% | |||
恩力动力 | 硫化物 | Li5.5S4.5PCl1 .5[ | 1.10×10-2 | — | — | — | — | |
硫化物+复合负极 | Li6PS5Cl[ | — | NCM811 | 0.3C | — | 循环108次,放电容量保持率80%(50 ℃) |
国家 | 典型代表 公司 | 种类 | 电解质组成 | 离子电导率 /S·cm-1 | 电池:正极||电解质||负极 | 倍率 | 放电容量 /mAh·g-1 | 循环寿命 |
---|---|---|---|---|---|---|---|---|
日本 | 丰田 | 硫化物电解质 | LGPS[ | 1.2×10-2 | LCO | 120 | — | |
含有Li、P、S、I、Br元素的电解质[ | 5×10-3 | — | — | — | — | |||
由15LiBr+10LiI+75(0.75Li2S+0.25P2S5)组成,具有PS43-结构的电解质[ | 3.2×10-3 | — | — | — | — | |||
Li9.54Si1.74P1.44S11.7Cl0.3[ | 2.5×10-2 | LNO-LCO | 18C | >120 | 循环500次,放电容量保持率75%(100℃) | |||
Li2S-P2S5-LiCl[ | 3.2×10-3 | — | — | — | — | |||
本田 | 硫化物电解质 | Li2S+P2S5+LiBH4[ | 3.3×10-2 | NCM811 | — | 170 | — | |
硫化物电解质+有机电解质 | LGPS+PVDF-HFP+LiClO4[ | — | NCM622 | 0.5C | — | 循环500次,放电容量保持率90%(55℃) | ||
韩国 | LG新能源 | 硫化物电解质+纯硅负极 | Li6PS5Cl[ | — | NCM811 | 1C | >1250 | 循环500次以上,放电容量保持率80%(25℃) |
三星 | 硫化物电解质+银碳负极 | Li6PS5Cl[ | — | LiNi0.9Co0.05Mn0.05O2 | 0.5C | 146 | 循环1000次,放电容量保持率89%(60℃) | |
美国 | Solid Power | 硫化物电解质 | Li3PS4+LiBH4[ | 8.2×10-3 | — | — | — | — |
硫化物电解质 | Li4SbS4I[ | 5.25×10-4 | — | — | — | — | ||
中国 | 中科固能 | 硫化物电解质 | Li6.8Si0.8As0.2S5I[ | 1.04×10-2 | Ti2S | 电流密度 2.44mA/cm2 | — | 62500次(30 ℃) |
卤化物+硫化物 | Li3InCl6+Li6PS5Cl[ | — | NCM90-Li3InCl6 | 20C | 循环30000次,放电容量保持率大于70% | |||
恩力动力 | 硫化物 | Li5.5S4.5PCl1 .5[ | 1.10×10-2 | — | — | — | — | |
硫化物+复合负极 | Li6PS5Cl[ | — | NCM811 | 0.3C | — | 循环108次,放电容量保持率80%(50 ℃) |
难点及解决方案 | 效果 | 电池:正极 | 电流密度 /mA·cm-2 | 初始放电容量 /mAh·g-1 | 循环寿命 | |
---|---|---|---|---|---|---|
水氧稳定性差 | ||||||
开发新材料 | 由Li2S、P2S5和LiCl制备[ | H2S产生量降低67% | — | — | — | — |
材料涂覆 | 在电极-电解质层叠体四周涂覆氮化硅、氧化铝或氧化硅绝缘膜以阻隔湿气[ | 湿气透过率降低2个数量级 | — | — | — | — |
无机有机复合材料 | 制备硫化物-PVDF-HFP复合电解质[ | 获得稳定的循环性能 | Li金属 | 0.2 | 154 | 1000h(室温) |
制备硫化物-疏水聚苯乙烯复合电解质[ | H2S产生量降低约73% | — | 0.11 | — | 2000h(室温) | |
界面问题 | ||||||
增强界面接触 | 减小阴极和电解质的粒径:将Li2S粒径从100μm以上研磨到约10μm[ | 初始放电容量提高25% | Li2S | 0.064 | 1000 | — |
湿法涂层:Li6PS5Cl和碳纤维(VGCF)涂覆在阴极上[ | 获得稳定的循环性能 | 0.13 | 115 | 循环15次,容量保持率为95%(室温) | ||
黏合剂:Li5.4PS4.4Cl1.6与PTFE混合[ | 获得稳定的循环性能 | LiNi0.5Co0.2Mn0.3O2||Li5.4PS4.4Cl1.6- | 0.05C | 135.3 | 循环150次,容量保持率为80.2%(60℃) | |
构建缓冲层提高化学/电化学稳定性 | LLSTO缓冲层[ | 获得稳定的循环性能 | 107 | 循环850次,容量保持率91.5%(室温) | ||
LNO缓冲层[ | LNO可以抑制LGPS与LCO的界面反应 | LCO-LNO | 0.13 | 125.8 | 循环100次,容量保持率72%(室温) | |
构建缓冲层改善空间电荷效应 | LNO缓冲层[ | 初始放电容量提高10% | NCM811-LNO | 0.5C | 130 | 循环50次,容量保持率77.9%(35℃) |
难点及解决方案 | 效果 | 电池:正极 | 电流密度 /mA·cm-2 | 初始放电容量 /mAh·g-1 | 循环寿命 | |
---|---|---|---|---|---|---|
水氧稳定性差 | ||||||
开发新材料 | 由Li2S、P2S5和LiCl制备[ | H2S产生量降低67% | — | — | — | — |
材料涂覆 | 在电极-电解质层叠体四周涂覆氮化硅、氧化铝或氧化硅绝缘膜以阻隔湿气[ | 湿气透过率降低2个数量级 | — | — | — | — |
无机有机复合材料 | 制备硫化物-PVDF-HFP复合电解质[ | 获得稳定的循环性能 | Li金属 | 0.2 | 154 | 1000h(室温) |
制备硫化物-疏水聚苯乙烯复合电解质[ | H2S产生量降低约73% | — | 0.11 | — | 2000h(室温) | |
界面问题 | ||||||
增强界面接触 | 减小阴极和电解质的粒径:将Li2S粒径从100μm以上研磨到约10μm[ | 初始放电容量提高25% | Li2S | 0.064 | 1000 | — |
湿法涂层:Li6PS5Cl和碳纤维(VGCF)涂覆在阴极上[ | 获得稳定的循环性能 | 0.13 | 115 | 循环15次,容量保持率为95%(室温) | ||
黏合剂:Li5.4PS4.4Cl1.6与PTFE混合[ | 获得稳定的循环性能 | LiNi0.5Co0.2Mn0.3O2||Li5.4PS4.4Cl1.6- | 0.05C | 135.3 | 循环150次,容量保持率为80.2%(60℃) | |
构建缓冲层提高化学/电化学稳定性 | LLSTO缓冲层[ | 获得稳定的循环性能 | 107 | 循环850次,容量保持率91.5%(室温) | ||
LNO缓冲层[ | LNO可以抑制LGPS与LCO的界面反应 | LCO-LNO | 0.13 | 125.8 | 循环100次,容量保持率72%(室温) | |
构建缓冲层改善空间电荷效应 | LNO缓冲层[ | 初始放电容量提高10% | NCM811-LNO | 0.5C | 130 | 循环50次,容量保持率77.9%(35℃) |
难点及解决方案 | 效果 |
---|---|
界面阻抗高:构建界面修饰层 | |
Al2O3层[ | 界面电阻降低99% |
镁金属层[ | 界面电阻降低93% |
锗金属层[ | 界面电阻降低87% |
加工性能差:与聚合物复合 | |
在绝缘性纤维状多孔基材中填充固体电解质[ | 制备面积大于1cm2的电解质片 |
烧结温度高:引入助剂 | |
Al2O3[ | 烧结温度降低到1000℃以下 |
Li3ClO[ | 烧结温度降低到1000℃以下 |
难点及解决方案 | 效果 |
---|---|
界面阻抗高:构建界面修饰层 | |
Al2O3层[ | 界面电阻降低99% |
镁金属层[ | 界面电阻降低93% |
锗金属层[ | 界面电阻降低87% |
加工性能差:与聚合物复合 | |
在绝缘性纤维状多孔基材中填充固体电解质[ | 制备面积大于1cm2的电解质片 |
烧结温度高:引入助剂 | |
Al2O3[ | 烧结温度降低到1000℃以下 |
Li3ClO[ | 烧结温度降低到1000℃以下 |
难点及解决方案 | 效果 | 电池:正极 | 倍率 | 初始放电容量 /mAh·g-1 | 循环寿命 | |
---|---|---|---|---|---|---|
室温离子电导率低 | ||||||
聚合物与无填料制备复合电解质 | PEO与GDC复合[ | 离子电导率超过10-4S/cm | Li | 0.05~ 0.2mA/cm | 160 (0.1mA/cm) | 800h(35℃) |
PEGDA、LLAZO和锂盐复合[ | 离子电导率提高一个数量级,达4.9×10-4S/cm | LiFePO4 | 1C | 120 | 循环250次,容量保持率为89%(35℃) | |
交联改性 | 金属烷氧基封端PEO进行原位交联,生成Al—O纳米团簇交联PEO-增塑剂固体电解质(ACCE)[ | 离子电导率达1.41×10-3S/cm | LiFePO4/ACCE/Li | 1C | 148 | 循环1000次,容量保持率为98.3%(30℃) |
共混改性 | 聚丙烯腈和聚碳酸丙烯酯共混[ | 离子电导率提高97%,达8.35×10-4S/cm | 磷酸铁锂 Li金属 | 0.5C | — | 310次(25℃) |
电化学窗口窄 | ||||||
有机+无机复合电解质 | PEO和LLZO复合[ | 电化学窗口达5.7V | — | — | — | — |
PEO和LGPS复合[ | 电化学窗口达5.7V | — | — | — | — | |
热稳定性差和安全性低 | ||||||
开发新型本征阻燃聚合物 | 硫化丁腈橡胶+TAC,制备阻燃固态聚合物电解质[ | TAC的三嗪环点燃时会释放惰性阻燃气体,有效抑制聚合物电解质的燃烧 | — | — | — | — |
引入阻燃剂 | 添加DBDPE阻燃剂[ | 电池在火焰测试中仍能正常工作 | — | 1C | 131 | 300次(0.5C、60℃) |
难点及解决方案 | 效果 | 电池:正极 | 倍率 | 初始放电容量 /mAh·g-1 | 循环寿命 | |
---|---|---|---|---|---|---|
室温离子电导率低 | ||||||
聚合物与无填料制备复合电解质 | PEO与GDC复合[ | 离子电导率超过10-4S/cm | Li | 0.05~ 0.2mA/cm | 160 (0.1mA/cm) | 800h(35℃) |
PEGDA、LLAZO和锂盐复合[ | 离子电导率提高一个数量级,达4.9×10-4S/cm | LiFePO4 | 1C | 120 | 循环250次,容量保持率为89%(35℃) | |
交联改性 | 金属烷氧基封端PEO进行原位交联,生成Al—O纳米团簇交联PEO-增塑剂固体电解质(ACCE)[ | 离子电导率达1.41×10-3S/cm | LiFePO4/ACCE/Li | 1C | 148 | 循环1000次,容量保持率为98.3%(30℃) |
共混改性 | 聚丙烯腈和聚碳酸丙烯酯共混[ | 离子电导率提高97%,达8.35×10-4S/cm | 磷酸铁锂 Li金属 | 0.5C | — | 310次(25℃) |
电化学窗口窄 | ||||||
有机+无机复合电解质 | PEO和LLZO复合[ | 电化学窗口达5.7V | — | — | — | — |
PEO和LGPS复合[ | 电化学窗口达5.7V | — | — | — | — | |
热稳定性差和安全性低 | ||||||
开发新型本征阻燃聚合物 | 硫化丁腈橡胶+TAC,制备阻燃固态聚合物电解质[ | TAC的三嗪环点燃时会释放惰性阻燃气体,有效抑制聚合物电解质的燃烧 | — | — | — | — |
引入阻燃剂 | 添加DBDPE阻燃剂[ | 电池在火焰测试中仍能正常工作 | — | 1C | 131 | 300次(0.5C、60℃) |
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