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随着对能源存储设备输出和安全性能等方面需求的不断提升, 全固态电池展示了替代传统液态锂离子电池占据新能源市场的潜力. 石榴石型Li7La3Zr2O12固体电解质具有高离子导率且对于锂金属稳定, 是最受人瞩目的固体电解质材料之一. 但是, 固-固界面不良接触导致的巨大界面电阻以及由于锂的不均匀沉积和分解导致的锂枝晶生长等问题严重阻碍了全固态电池的发展. 本综述针对石榴石型全固态电池突出的界面问题, 详细论述了Li7La3Zr2O12表面碳酸锂问题的研究现状; 讨论了锂金属负极和固态电解质的界面浸润性以及锂枝晶生长问题, 给出了构建理想界面的关键因素; 阐述了优化正极与石榴石型固体电解质界面的具体方法以及改善界面润湿性的思路. 本文还展望了未来石榴石型全固态锂离子电池可能的发展方向, 为全固态锂离子电池的发展和应用提供了借鉴.With the increasing demand for storage devices with higher energy output and better safety performance, all-solid-state batteries show their potential to replace the traditional liquid-based Li-ion batteries in the future storage market. Garnet-type Li7La3Zr2O12 is one of the most attractive solid electrolyte materials because of its high ionic conductivity and stability to lithium metal. However, the large interfacial resistance originating from the insufficient solid-solid contact and the penetration of the lithium dendrite due to the inhomogeneous dissolution and deposition of lithium, hinder the all-solid-state batteries from developing. Focusing on the main interfacial problems in garnet-type all-solid battery, this review provides a fundamental understanding of the Li2CO3 issues in Li7La3Zr2O12 solid electrolyte and addresses the key factors influencing Li/ Li7La3Zr2O12/cathode interfacial wettability and the growth of Li dendrite, thus giving the key factors of constructing ideal interfaces. Finally, the possible research direction of garnet-type all-solid-state battery in the future is also prospected, which provides a guidance for developing and using all-solid-state batteries.
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Keywords:
- Li7La3Zr2O12 /
- all-solid-state battery /
- interface modification /
- characterization technology
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图 2 (a) 利用铂金坩埚代替传统Al2O3坩埚可以有效减少暴露空气后LLZO表面碳酸锂的形成[34]; (b) 利用快速热脉冲的处理方法可以有效去除碳酸锂, 并且使得锂损失最小化[48]; (c) 通过添加LiF, Li3PO4等疏水添加剂, 或者在表面制造缺锂层, 都可以有效抑制碳酸锂的形成[33,51]; (d) 通过快速酸处理可以除去表面碳酸锂, 得到稳定接触的界面[52]
Fig. 2. (a) Using Pt crucible instead of alumina crucible can effectively reduce the Li2CO3 formation on LLZO after exposed to air[34]; (b) the rapid thermal pulsing treatment can effectively remove the Li2CO3 impurity and minimize Li loss[48]; (c) adding inorganic additives such as LiF and Li3PO4, or creating Li-deficient compounds on the surface can eliminate Li2CO3 contaminants[33,51]; (d) improving Li/LLZO interface contact by removing Li2CO3 via rapid acid treatment[52].
图 3 (a) 利用Ge作为界面缓冲材料优化Li/LLZO界面[5]; (b) 中子深度分析装置示意图及LLZO原位探测结果[58]; (c) 利用MoS2作为界面缓冲材料优化Li/LLZO界面, 和界面转化反应及极化原理示意图[61]
Fig. 3. (a) Using Ge as buffer layer to modify Li/LLZO interface[5]; (b) schematic of the experimental set-up for operando Neutron depth profiling and the results for LLZO cell[58]; (c) schematic diagram of the conversion reaction and the chemical evolution of the MoS2-coating layer in the polarization process[61].
图 4 (a) 利用添加Nb缓冲层可以有效改善激光脉冲沉积过程中LiCoO2/LLZO界面稳定性[70]; (b) 利用快速热退火的方法将V2O5电极材料制备到LLZO片上[72]; (c) 利用Li2.3-xC0.7+xB0.3-xO3与碳酸锂反应生成LCBO改善LiCoO2/LLZO界面示意图以及全固态电池在常温下的循环特性[73]
Fig. 4. (a) Using Nb as buffer layer can modify the stability of LiCoO2/LLZO interface during Pulsed Laser Deposition (PLD) process[70]; (b) using rapid thermal annealing to melt V2O5 cathode onto LLZO pellet[72]; (c) schematics of the interphase-engineered all-ceramic cathode/electrolyte by using the reaction of Li2.3-xC0.7+xB0.3-xO3 with Li2CO3. The all sold battery can cycle well over 100 times at room temperature[73].
表 1 计算得到的在298.15 K下LLZO发生水合以及碳酸化反应所需的吉布斯自由能, 其中, 前4项是反应过程中有Li+/H+交换作用对应的能量, 后2项为直接反应对应的能量[37]
Table 1. Calculated Gibbs free energy for the hydration and carbonation of LLZO at 298.15 K. The first 4 reactions involve Li+/H+ ion exchange and the last 2 reactions assume direct hydration and carbonation of LLZO[37].
LLZO与空气中的水和二氧
化碳可能的反应过程吉布斯自由能
ΔG/kJ·mol–1Li56La24Zr16O96+H2O(g) →
Li55HLa24Zr16O96+LiOH–33 LiOH+1/2 CO2(g) →
1/2 Li2CO3+1/2 H2O(g)–33.6 Li56La24Zr16O96+CO2(g) →
Li54La24Zr16O95+Li2CO3+21.5 Li2O+CO2(g)→Li2CO3 –147.6 Li56La24Zr16O96+H2O(g) →
Li54La24Zr16O95+2 LiOH+82.8 Li56La24Zr16O96+CO2(g) →
Li54La24Zr16O95+Li2CO3+15.6 -
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