Effect of LiTFSI and LiFSI on Cycling Performance of Lithium Metal Batteries Using Thermoplastic Polyurethane/Halloysite Nanotubes Solid Electrolyte

doi:10.1007/s40195-021-01191-8

Abstract

Abstract:

All-solid-state lithium batteries (ASSLB) are promising candidates for next-generation energy storage devices. Nevertheless, the large-scale commercial application of high energy density ASSLB with the polymer electrolyte still faces challenges. In this study, a thin solid polymer composite electrolyte (SPCE) is prepared through a facile and cost-effective strategy with an infiltration of thermoplastic polyurethane (TPU), lithium salt (LiTFSI or LiFSI), and halloysite nanotubes (HNTs) in a porous framework of polyethylene separator (PE) (TPU-HNTs-LiTFSI-PE or TPU-HNTs-LiFSI-PE). The composition, electrochemical performance, and especially the effect of anions (TFSI^- and FSI^-) on cycling performance are investigated. The results reveal that the flexible TPU-HNTs-LiTFSI-PE and TPU-HNTs-LiFSI-PE with a thickness of 34 μm exhibit wide electrochemical windows of 4.9 and 5.1 V (vs. Li⁺/Li) at 60 ℃, respectively. Reduction in FSI^- tends to form more LiF and sulfur compounds at the interface between TPU-HNTs-LiFSI-PE and Li metal anode, thus enhancing the interfacial stability. As a result, cell composed of TPU-HNTs-LiFSI-PE exhibits a smaller increase in interfacial resistance of solid electrolyte interphase (SEI) with a distinct decrease in charge-transfer resistance during cycling. Li|Li symmetric cell with TPU-HNTs-LiFSI-PE could keep its stable overpotential profile for nearly 1300 h with a low hysteresis of approximately 39 mV at a current density of 0.1 mA cm^-2, while a sudden voltage rise with internal cell impedance-surge signals was observed within 600 h for cell composed of TPU-HNTs-LiTFSI-PE. The initial capacities of NCM|TPU-HNTs-LiTFSI-PE|Li and NCM|TPU-HNTs-LiFSI-PE|Li cells were 149 and 114 mAh g^-1, with capacity retention rates of 83.52% and 89.99% after 300 cycles at 0.5 C, respectively. This study provides a valuable guideline for designing flexible SPCE, which shows great application prospect in the practice of ASSLB.

Key words: Solid polymer composite electrolyte, Lithium metal anode, Thermoplastic polyurethane, Halloysite nanotubes, Cycling performance

Zhichuan Shen, Jiawei Zhong, Wenhao Xie, Jinbiao Chen, Xi Ke, Jianmin Ma, Zhicong Shi. Effect of LiTFSI and LiFSI on Cycling Performance of Lithium Metal Batteries Using Thermoplastic Polyurethane/Halloysite Nanotubes Solid Electrolyte[J]. Acta Metallurgica Sinica (English Letters), 2021, 34(3): 359-372.

Figures/Tables 13

Scheme 1 Schematic illustration of the fabrication process of SPCE

Fig. 1 SEM images under different magnifications of a, b PE separator, c, d SPCE and e, f digital photographs of flexible SPCE with a thickness of 34 μm

Fig. 2 FTIR spectra of a LiFSI and LiTFSI, b HNTs, TPU, and PE at 4000-500 cm-1, c TPU-HNTs-LiFSI-PE, TPU-HNTs-LiTFSI-PE, and TPU at 1800-700 cm-1. XPS spectra on C 1s of d TPU-HNTs-PE, e TPU-HNTs-LiTFSI-PE, and f TPU-HNTs-LiFSI-PE

Table 1 Binding energy of C 1s of TPU-HNTs-PE, TPU-HNTs-LiTFSI-PE and TPU-HNTs-LiFSI-PE in the XPS spectra in Fig. 2

Material	BE (eV)
Material	C-C	C-O	C = O	CF₃	Li
TPU-HNTs-PE	284.75	286.16	288.69	-	-
TPU-HNTs-LiTFSI-PE	284.78	286.25	288.89	292.44	56.58
TPU-HNTs-LiFSI-PE	284.81	286.33	289.12	-	55.85

Fig. 3 a EIS curves of TPU-HNTs-LiTFSI-PE and TPU-HNTs-LiFSI-PE at 30-90 ℃. b Temperature-dependent ionic conductivity for TPU-HNTs-LiTFSI-PE and TPU-HNTs-LiFSI-PE. c, d Chronoamperometry profiles and AC impedance spectra of lithium symmetric cell with TPU-HNTs-LiTFSI-PE and TPU-HNTs-LiFSI-PE before and after polarization

Fig. 4 a Voltage profiles of Lithium symmetric cells using TPU-HNTs-LiTFSI-PE or TPU-HNTs-LiFSI-PE at a current density of 0.1 mA cm-2 with a restricted specific capacity of 0.1 mAh cm-2 at 60 ℃. b EIS curves, c Rsf and Rct variation of lithium symmetric cells using TPU-HNTs-LiTFSI-PE and TPU-HNTs-LiFSI-PE after 100, 200, 300, 400, and 500 h

Fig. 5 XPS spectra of a, b C 1s, c, d F 1s, and e, f S 2p on the surface of lithium metal anode after cycling of lithium symmetric cells using TPU-HNTs-LiTFSI-PE and TPU-HNTs-LiFSI-PE

Table 2 Binding energy of C 1s, F 1s, and S 2p on lithium metal anode after cycling of lithium symmetric cells using TPU-HNTs-LiTFSI-PE and TPU-HNTs-LiFSI-PE

Material	BE (eV)
	C 1s			F 1s		S 2p
	C-C-O	C-O-CO₂-Li	Li₂CO₃	CF₃	LiF	R-SO₃	-SO₂-	Li_xSO_y
TPU-HNTs-LiTFSI-PE	284.75	286.33	289.66	688.45	684.56	-	168.59	-
TPU-HNTs-LiFSI-PE	284.81	286.27	288.96	687.39	684.51	170.48	169.31	166.46

Fig. 8 XPS spectra of a, b C 1s, c, d F 1s, and e, f S 2p on the surface of lithium metal anode of NCM|TPU-HNTs-LiTFSI-PE|Li and NCM|TPU-HNTs-LiFSI-PE|Li batteries after cycling

Table 3 Binding energy of C 1s, F 1s, and S 2p on the surface of lithium metal anode in cycled NCM|TPU-HNTs-LiTFSI-PE|Li and NCM|TPU-HNTs-LiFSI-PE|Li batteries

Material	BE (eV)
	C 1s				F 1s		S 2p
	C-C-O	-CO₂-Li	Li₂CO₃	CF₃	CF₃	LiF	R-SO₃	SO₂CF₃
TPU-HNTs-LiTFSI-PE	284.79	286.23	288.84	292.41	688.41	-	169.72	168.52
TPU-HNTs-LiFSI-PE	284.80	286.34	289.09	-	687.49	684.81	170.73	169.55

Fig. 9 a, b Rate performance and c, d voltage profiles of NCM|TPU-HNTs-LiTFSI-PE|Li and NCM|TPU-HNTs-LiFSI-PE|Li batteries at various current densities at 60 ℃

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