Potassium 2-thienyl tri-fluoroborate as a functional electrolyte additive enables stable interfaces for Li/LiFe0.3Mn0.7PO4batteries

Shuai Li; Ruilin Tang; Chuan Hu; Xiaobin Niu; Liping Wang

doi:10.1016/j.jcis.2023.05.007

Potassium 2-thienyl tri-fluoroborate as a functional electrolyte additive enables stable interfaces for Li/LiFe_0.3Mn_0.7PO₄batteries

J Colloid Interface Sci. 2023 Sep 15:646:150-158. doi: 10.1016/j.jcis.2023.05.007. Epub 2023 May 6.

Authors

Shuai Li¹, Ruilin Tang¹, Chuan Hu¹, Xiaobin Niu¹, Liping Wang²

Affiliations

¹ School of Materials and Energy, University of Electronic Science and Technology of China, Chengdu 611731, China.
² School of Materials and Energy, University of Electronic Science and Technology of China, Chengdu 611731, China. Electronic address: lipingwang@uestc.edu.cn.

PMID: 37187048
DOI: 10.1016/j.jcis.2023.05.007

Abstract

As a promising cathode material for high-performance lithium-ion batteries, olivine LiFe_1-xMn_xPO₄ (0 < x < 1, LFMP) combines the high safety of LiFePO₄ and the high energy density of LiMnPO₄. During the charge-discharge process, poor interface stability of active materials leads to capacity decay, which prevents its commercial application. Here, to stabilize the interface, a new electrolyte additive potassium 2-thienyl tri-fluoroborate (2-TFBP) is developed to boost the performance of LiFe_0.3Mn_0.7PO₄ at 4.5 V vs. Li/Li⁺. Specifically, after 200 cycles, the capacity retention remains at 83.78% in the electrolyte containing 0.2% 2-TFBP while the capacity retention without 2-TFBP addition is only 53.94%. Based on the comprehensive measurements results, the improved cyclic performance is attributed to that 2-TFBP has a higher highest occupied molecular orbit (HOMO) energy and its thiophene group can be electropolymerized above 4.4 V vs. Li/Li⁺ for generating uniform cathode electrolyte interphase (CEI) with poly-thiophene, which can stable materials structure and suppress the decomposition of electrolytes. Meanwhile, 2-TFBP both promotes the deposition/exfoliation of Li⁺ at anode-electrolyte interfaces and regulates Li deposition by K⁺ cations through the electrostatic mechanism. This work presents that 2-TFBP has a great application prospect as a functional additive for high-voltage and high-energy-density lithium metal batteries.

Keywords: Electrolyte design; Interfacial stability; LiFe(1-x)Mn(x)PO(4) (0 < x < 1); Lithium-metal batteries.