Engineering Electronic Radial Effects for Fast Li~+ Transport in Solid-State Electrolytes

Jiadong Shen ¹Gilseob Kim ¹Jong-woan Chung ¹Sunjae Kwon ¹Wootack Chung ¹Dahye Yoon ¹Xiwen Zhang ²Lei Shen ³Junjie Chen ⁴Jun Liu ⁵Yong-Mook Kang⁶

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作者信息

1. Department of Materials Science and Engineering, Korea University, Seoul, Republic of Korea
2. Department of Mechanical Engineering, National University of Singapore, Singapore, Singapore||School of Mechanical Engineering, Southeast University, Nanjing, China
3. Department of Mechanical Engineering, National University of Singapore, Singapore, Singapore
4. Department of Mechanical and Aerospace Engineering, The Hong Kong University of Science and Technology, Singapore, Hong Kong SAR, China
5. Department of Materials Science and Engineering, South China University of Technology, Guangzhou, Guangdong, China
6. Department of Materials Science and Engineering, Korea University, Seoul, Republic of Korea||KU-KIST Graduate School of Converging Science and Technology, Korea University, Seoul, Republic of Korea||Department of Battery-Smart Factory, Korea University, Seoul, Republic of Korea
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Abstract

Achieving high Li~+ conductivity, near-unity transference numbers, and stable interfaces in solid-state electrolytes remains amajor challenge for lithium-metal batteries. Here we introduce a radial-effect design principle: relativistic expansion and spin–orbit coupling of 5d orbitals enhance s–d/p–d hybridization, weaken Li–anion interactions, and lower migration barriers. An entropybased descriptor, S_d, trained and validated with machine learning across >10,000 oxides, sulfides, and halides captures this effect. Machine-learning-guided high-throughput screening flags monoclinic HfO_2,whose 5d~2 radial expansion lowersmigration barriers by ∼45% vs Sc_2O_3 or Y_2O_3. Guided by this insight,we employmillisecond flash-Joule heating to convert HfO_2 into nanosized single crystals, then embed them in a Li-conductive binder to create sc-HfO_2@LCB, whose radial coupling yields interconnected Li~+ pathways (1.23 mS cm~(-1), 30℃; t_(Li+) = 0.82, 25℃) and a 4.8 V electrochemical window. Operando Raman/XANES confirms faster Li+ transport. Consequently, 2 Ah LiNi_(0.9)Co_(0.05)Mn_(0.05)O_2‖Li pouch cells deliver ∼472 Wh kg~(-1) (stack-level), maintain superior rate capability over hundreds of cycles, and survive 150℃ hot-plate tests. These results establish radial-effect engineering as a sophisticated strategy for high-performance, thermally resilient solid-state batteries.

Key words

entropy-based descriptor/Flash Joule Heating/machine-learning/radial-effect engineering/s-d/p-d hybridizations

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出版年

2026

Advanced Materials

ISSN：0935-9648

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