所属专题: 锂离子电池
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蒋志敏, 王莉, 沈旻, 陈慧闯, 马国强, 何向明. 锂离子电池正极界面修饰用电解液添加剂[J]. 化学进展, 2019, 31(5): 699-713.
Zhimin Jiang, Li Wang, Min Shen, Huichuang Chen, Guoqiang Ma, Xiangming He. Electrolyte Additives for Interfacial Modification of Cathodes in Lithium-Ion Battery[J]. Progress in Chemistry, 2019, 31(5): 699-713.
提高电压是提高锂离子电池比能量的重要途径之一。例如,LiNi0.5Mn1.5O4(4.7 V)、LiNiPO4(5.1 V)和富锂锰基等电极材料在较高的充电截止电压下表现出较高的能量密度和较低的成本,具有很好的应用前景。另外,提高LiCoO2和三元电池体系的充电截止电压是提升电池能量密度的简单有效措施。但是,当电池充电截止电压提高时,不仅会造成电解液在正极/电解液界面的氧化分解,还会加速正极中金属阳离子在电解液中的溶解,造成电池循环性能和安全性下降。采用不同的正极界面修饰用电解液添加剂,既可以有效钝化正极/电解液界面,抑制电解液的分解,还可以有效抑制正极结构的破坏。本文从添加剂的分子结构出发,介绍了磺酸酯、硼酸酯、磷酸酯、氟代碳酸酯、腈类、酸酐和锂盐等添加剂在正极界面的相关研究成果,并对不同添加剂的作用机理进行了详细的解释和归纳;另外,介绍了添加剂的联用技术在不同电池体系中的最新研究成果;最后,对新型正极界面修饰用电解液添加剂的开发进行了展望。
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Electrolyte additive | Oxidation potential (V vs. Li+/Li) | Additive effect | ref | ||
---|---|---|---|---|---|
Main action mechanism | Interface film component | Reported battery chemistry and the mechanism of the additives | |||
FEC | 6.44(PF6-) | Film formation | PEO-like polymer, carbonate | LiNi0.5Mn1.5O4/graphite: Participate in the formation of protective surface film on cathode; enhance voltage stability at elevated temperature. | 15 |
FEMC | 6.26(PF6-) | Film formation | Metal fluorides, C-F containing species | LiNi0.5Mn1.5O4/Li and LiNi0.5Mn1.5O4/Li4Ti5O12: Increase oxidation stsbility in high-voltage; enhance cycling performance. | 15 |
VC | 4.85[ | Film formation | Ploy(VC) | LiCoO2/Li: Form effective passivation layers at the surface of both electrodes; not suitable for the condition of high voltage. | 11 |
ADN | 6.9[ | Metal ions absorbing | -CN containing species | LiCoO2/MCMB: Improve resistance to aluminum; form a stable solid electrolyte interface especially to cathode of LiCoO2. | 72 |
SUN | 6.8[ | Metal ions absorbing | -CN containing species | Li[Li0.2Mn0.56Ni0.16Co0.08]O2/Li: Form a more dense and stabe interface; suppress the decomposition of LiPF6,EC and DMC; enhance capacity performance. | 72 |
BP | 4.5[ | Overcharge protection | Oligomers having 6-12 benzene rings | LiCoO2/graphite: Have lower oxidation potential than solvents; form a thick interfacial film on cathode. | 73 |
HFiP | 4.2[ | Film formation | CF3-,CF3-CR2- species | Li[Li0.2Mn0.56Ni0.16Co0.08]O2/Li: Form a more stable SEI layer; have more stable solid electrolyte impedance and smaller charge transfer resistance. | 74 |
TMSP | 4.1[ | Film formation and electrolyte stabilizer | Si-O,P-O species | LiNi0.5Mn1.5O4/graphite: Alleviate the decomposition of LiPF6 by hydrolysis; eliminate HF promoting Mn/Ni dissolution from the cathode. | 75 |
TMSB | 3.76[ | Film formation and electrolyte stabilizer | Si-O,B-O species | LiMn2O4/Li: Show excellent capacity retention at high temperature; reduce the content of HF. | 48 |
MMDS | 4.6[ | Film formation | Li2SO3,ROSO2Li, sulfide component | LiNi0.5Co0.2Mn0.3O2/graphite: Increase capacity retention; improve the conductivity of CEI; suppress the solvent decompdsition at high voltage. | 76 |
SA | 4.4[ | Film formation | Hydrocarbons,Li2CO3 | LiNi0.5Mn1.5O4/Li: Improve high voltage stability; form a modified protective layer. | 64 |
TB | 4.3[ | Film formation and electrolyte stabilizer | Metal oxide, B-O species | LiNi1/3Co1/3Mn1/3O2/Li: Improve cyclic stability and rate capability; form a stable and low impedance film. | 50 |
LiBOB | 4.2[ | Film formation and electrolyte stabilizer | Li oxalate, oxalate species | LiNi0.5Mn1.5O4/Li: React with water traces and suppress the formation of POF3; improve high voltage and high temperature stability. | 74 |
LiDFOB | 4.35[ | Film formation and electrolyte stabilizer | B containing polycarbonate | Li1.2Ni0.15Mn0.55Co0.1O2/ Li: Reduces both cell capacity loss and impedance rise; inhibits electrolyte oxidation; reduces dissolution of metal ions. | 77 |
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