Optimizing <i>f</i> ‐ <i>d</i> Hybridization Descriptor in Rare‐Earth Oxides for Efficient Sulfur Catalysis in all Solid‐State Lithium–Sulfur Batteries
Abstract
ABSTRACT All‐solid‐state lithium–sulfur batteries (ASSLSBs) offer high theoretical energy density and intrinsic safety, yet their development is hindered by sluggish sulfur redox kinetics at the solid–solid interfaces due to the weak orbital overlap and discontinuous electronic coupling at these regions. Here, we propose rare‐earth oxide catalysts that accelerate the sulfur reduction reaction (SRR) in ASSLSBs by strengthening the f‐d‐p hybridization at catalyst‐sulfur‐electrolyte interfaces. We first define a hybridization‐strength factor, I f‐d , derived from the electron densities of occupied 4 f and unoccupied 5 d states, which quantifies interfacial hybridization and directly correlates with the metal‐sulfur coupling strength. Catalysts with higher I f‐d exhibit lower activation energy ( E a ) and the overpotential ( η ) during SRR, validating its role as a structure‐activity descriptor for catalyst screening and design. Guided by this descriptor, the screened Lu 2 O 3 catalyst minimizes kinetic barriers (0.088 eV), and thus enabling stable cycling for over 20 000 cycles at 5 C, and an ultra‐high areal capacity of 14.48 mAh cm −2 at room temperature, among the highest performances reported for ASSLSBs. This work fills the mechanistic gap between interfacial orbital interactions and battery performance and paves the way toward catalyst design for high‐energy, long‐life ASSLSBs.
Article Details
Authors (12)
Mingyang Jiang
Shenzhen Geim Graphene Center, Shenzhen Key Laboratory for Graphene-Based Materials, Tsinghua Shenzhen International Graduate School
Jiwei Shi
Nanoyang Group, Tianjin Key Laboratory of Advanced Carbon and Electrochemical Energy Storage, State Key Laboratory of Chemical Engineering and Low-Carbon Technology, School of Chemical Engineering and Technology, National Industry-Education Platform for Energy Storage, and Collaborative Innovation Center of Chemical Science and Engineering (Tianjin)
Junjie Wang
State Key Laboratory of Quantum Functional Materials, School of Physical Science and Technology
Zhonghao Hu
Nanoyang Group, Tianjin Key Laboratory of Advanced Carbon and Electrochemical Energy Storage, State Key Laboratory of Chemical Engineering and Low-Carbon Technology, School of Chemical Engineering and Technology, National Industry-Education Platform for Energy Storage, and Collaborative Innovation Center of Chemical Science and Engineering (Tianjin)
Chuannan Geng
Nanoyang Group, Tianjin Key Laboratory of Advanced Carbon and Electrochemical Energy Storage, State Key Laboratory of Chemical Engineering and Low-Carbon Technology, School of Chemical Engineering and Technology, National Industry-Education Platform for Energy Storage, and Collaborative Innovation Center of Chemical Science and Engineering (Tianjin)
Qiang Li
Bohan Zhang
Yun Cao
Key Laboratory of Evolution and Marine Biodiversity (Ministry of Education) and Institute of Evolution and Marine Biodiversity, Ocean University of China, Qingdao, China.
Chenxiang Xie
Nanoyang Group Tianjin Key Laboratory of Advanced Carbon and Electrochemical Energy Storage State Key Laboratory of Chemical Engineering and Low‐Carbon Technology School of Chemical Engineering and Technology National Industry‐Education Platform for Energy Storage and Collaborative Innovation Center of Chemical Science and Engineering Tianjin University Tianjin China
Yufei Zhao
State Key Laboratory of Chemical Resource Engineering
Jiaqi Lan
Shenzhen All-Solid-State Lithium Battery Electrolyte Engineering Research Center, Key Laboratory of Electrocatalytic Materials and Green Hydrogen Technology of Guangdong Higher Education Institutes, Shenzhen Key Laboratory for Graphene-Based Materials, Institute of Materials Research, Tsinghua Shenzhen International Graduate School
Wei Lv