Boroxine Crystalline Covalent Organic Frameworks Based Single-ion Quasi-solid-state Conductor in Lithium-ion Battery

Hao-Min Wu; Wen-Can Ma; Yi-Feng Cai; Xin Huang; Jun-Heng Li; Xi Kai; Qiu-Hong Zhang; Xu-Dong Jia

doi:10.1007/s10118-025-3260-7

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Boroxine Crystalline Covalent Organic Frameworks Based Single-ion Quasi-solid-state Conductor in Lithium-ion Battery

RESEARCH ARTICLE | Updated：2024-12-31

- Boroxine Crystalline Covalent Organic Frameworks Based Single-ion Quasi-solid-state Conductor in Lithium-ion Battery
- Chinese Journal of Polymer Science Vol. 43, Issue 1, Pages: 177-187(2025)
- Affiliations：
  
  a.Key Laboratory of High-Performance Polymer Material and Technology of MOE, Department of Polymer Science and Engineering, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing 210023, China
  b.Institute of Chemical Industry of Forest Products, Chinese Academy of Forestry Department, Nanjing 210018, China
  c.School of Chemistry and Chemical Engineering, Frontiers Science Center for Transformative Molecules, Shanghai Jiao Tong University, Shanghai 200240, China
  d.Executive in Low Carbon Management Division of QHSE Department, Sinochem Holdings Corporation Ltd, Central Tower, Chemsunny World Trade Center, Beijing 100031, China
  e.State Key Laboratory of Coordination Chemistry, Nanjing University, Nanjing 210023, China
- Author bio：
  
  chemzqh@nju.edu.cn (Q.H.Z.)
  jiaxd@nju.edu.cn (X.D.J.)
- Funds：
- DOI：10.1007/s10118-025-3260-7
  CLC：
- Received：01 August 2024，
  
  Revised：2024-10-23，
  
  Accepted：28 October 2024，
  
  Online First：25 December 2024，
  
  Published：01 January 2025
- Accepted：
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Wu, H. M.; Ma, W. C.; Cai, Y. F.; Huang, X.; Li, J. H.; Kai, X.; Zhang, Q. H.; Jia, X. D. Boroxine crystalline covalent organic frameworks based single-ion quasi-solid-state conductor in lithium-ion battery. Chinese J. Polym. Sci. 2025, 43, 177–187

Hao-Min Wu, Wen-Can Ma, Yi-Feng Cai, et al. Boroxine Crystalline Covalent Organic Frameworks Based Single-ion Quasi-solid-state Conductor in Lithium-ion Battery[J]. Chinese Journal of Polymer Science, 2025, 43(1): 177-187.
Wu, H. M.; Ma, W. C.; Cai, Y. F.; Huang, X.; Li, J. H.; Kai, X.; Zhang, Q. H.; Jia, X. D. Boroxine crystalline covalent organic frameworks based single-ion quasi-solid-state conductor in lithium-ion battery. Chinese J. Polym. Sci. 2025, 43, 177–187 DOI： 10.1007/s10118-025-3260-7.

Hao-Min Wu, Wen-Can Ma, Yi-Feng Cai, et al. Boroxine Crystalline Covalent Organic Frameworks Based Single-ion Quasi-solid-state Conductor in Lithium-ion Battery[J]. Chinese Journal of Polymer Science, 2025, 43(1): 177-187. DOI： 10.1007/s10118-025-3260-7.

摘要

We first proposed and prepared a series of SIQSSEs based on the boroxine COF-5. Both COF-N-S-TFSILi and COF-N-S-SPSILi possessed high lithium transference numbers (LTNs) and high ionic conductivities at room temperature simultaneously. The SIQSSE COF-N-S-TFSILi also achieved an ideal battery performance.

Abstract

Solid-state electrolytes are considered to be the vital part of the next-generation solid-state batteries (SSBs)

due to their high safety and long operation life span. However

the two major factors that impede the expected performance of batteries are: the easy formation of lithium dendrites due to the concentration gradient of anions

and the low ionic conductivity at room temperature

which prevents reaching ideal electrochemical performance. Single-ion quasi-solid-state electroly

tes (SIQSSEs) could provide higher safety and energy density

owing to absence of anion concentration gradient and solvent

as well as good lithium-ion transport ability. The porous covalent organic frameworks (COFs) are beneficial for con-structing appropriate lithium-ion transport pathway

due to the ordered 1D channel. In addition

the boroxine COFs (COF-5) offers strong ability of withdrawing anion part of lithium salt. Last but not the least

boron atom could play the role of coordinate site due to its electron deficiency. These advantages afford an opportunity to obtain a SIQSSE with high ionic conductivity and high lithium transference number (LTN) simultaneously. The COF-5 based SIQSSEs delivered a high ionic conductivity of 6.3×10

−4

S·cm

−1

with a high LTN of 0.92 and a wide electrochemical stable window (ESW) of 4.7 V at room temperature. The LiFePO

(LFP)/Li cells

which was assembled with COF-5 based SIQSSE

exhibited outstanding long cycle stability

high initial capacity and favorable rate performance. The results indicated COFs could be an ideal material for single-ion solid-state electrolytes in next-generation batteries.

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