全固体電池向け固体電解質-電極材間における焼結時の反応メカニズム解明と反応抑止に成功~低コストプロセスで製造する全固体電池実現に前進~

2025-09-08 九州大学

九州大学大学院総合理工学研究院の渡邉賢准教授とデンソー所属(当時博士課程)の林真大らは、酸化物系全固体電池の実用化を妨げてきた電解質-電極材間の高温焼結反応メカニズムを解明し、その抑止に成功した。全固体電池用電解質Li₇La₃Zr₂O₁₂(LLZ)は高いイオン伝導率を持つが、接合に必要な高温条件下で三元系正極材NMC622(LiNi₀.₆Mn₀.₂Co₀.₂O₂)と反応し性能を損なう課題があった。放射光などによる分析の結果、反応の起点は電極材中のNiやCoが低価数化し、リチウムとの位置交換を誘発することにあると判明。これに基づき、価数維持と自己反応防止層形成を両立させた独自電極材を合成、低温焼結可能なLLZと組み合わせることで反応を抑制し、繰り返し充放電可能な全固体電池を実証した。本成果は「Advanced Science」に掲載され、低コストプロセスによる全固体電池量産化への道を拓くと期待される。

全固体電池向け固体電解質-電極材間における焼結時の反応メカニズム解明と反応抑止に成功~低コストプロセスで製造する全固体電池実現に前進~
図1 従来電極材と独自電極材における焼結時の現象を模式化したイメージ図

<関連情報>

バルク型全固体電池製造のためのCo焼結における高Ni正極材料(NMC622)とLi7La3Zr2O12間の反応抑制:新規手法とそのメカニズム Reaction Suppression Between a High-Ni Cathode Material (NMC622) and Li7La3Zr2O12 on Co-Sintering for Manufacturing Bulk-Type All-Solid-State Batteries: A New Method and Its Mechanism

Naohiro Hayashi, Ken Watanabe
Advanced Science  Published: 29 August 2025
DOI:https://doi.org/10.1002/advs.202512219

Abstract

Co-sintering cathode materials with Li7La3Zr2O12 (LLZ) is a promising strategy for fabricating bulk-type all-solid-state batteries (ASSBs). However, preventing reactions between different materials, which is difficult with high-capacity cathode materials such as LiNi0.6Mn0.2Co0.2O2 (NMC622), is a pre-requisite for applying this strategy. To overcome this issue, Li1+xNi0.6Mn0.2Co0.2O2 (x = 0.01–0.2), which intentionally deviates from the stoichiometric NMC622 composition, is synthesized here. The formation of impurity phases in the co-sintering process can be controlled by adjusting the co-sintering temperature and x. Impurity phases are not formed on co-sintering with x = 0.075 at 800 °C because reduced cation mixing in NMC622 and the presence of a self-formed Li2CO3 layer on the particle surface, ensured by adjusting x, effectively suppresses reactions. Furthermore, good results are observed at sintering temperatures where the proportions of Ni2+ and Co2+, which promote cation mixing, are low. This study clarifies relevant reaction mechanisms using various analytical methods (such as temperature-rise X-ray absorption fine structure analysis and scanning transmission electron microscopy-electron energy loss spectroscopy), and confirms the repetitive operation of bulk-type ASSBs assembled using co-sintered Li1+xNi0.6Mn0.2Co0.2O2 (x = 0.075)/LLZ electrolyte systems. The method reported herein can be potentially adopted for cost-effective and high-energy-capacity ASSB production.

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