Preparation and properties of polyvinylidene fluoride/polyvinylidene fluoride sulfonate lithium/lithium salt composite solid electrolyte

doi:10.19799/j.cnki.2095-4239.2021.0160

Abstract

Abstract:

Single-ion polymer electrolytes were recently developed and used in solid-state batteries. In single-ion polymer electrolytes, anions are attached to the main chain of polymers, and only lithium ions are allowed to pass through into the electrolyte. As a result, the single-ion polymer electrolytes had a high lithium-ion migration number, which will be beneficial in reducing the concentration polarization of lithium batteries. However, the low ion conductivity of single-ion polymer electrolytes limits their application in lithium batteries. In the present work, chlorosulfonic acid, polyvinylidene fluoride (PVDF), and lithium hydroxide were used to prepare sulfonated polyvinylidene fluoride (SPVDF) and polyvinylidene fluoride sulfonate lithium (SPVDFLi). The chemical structures of PVDF and SPVDF were confirmed by the 1H nuclear magnetic resonance spectra. A series of single-ion polymer electrolytes (SIPEx) were prepared by a solvent casting method from PVDF and SPVDFLi mixture solution. To improve the electrolyte's ion conductivity, PVDF/SPVDFLi/LiTFSI composite electrolytes (SPVDFLi/LiTFSI-y) were created by varying the amount of LiTFSI in the SIPE. The ion conductivity of SIPEs increased by increasing the content of SPVDFLi. The ion conductivity of PVDF/SPVDFLi/LiTFSI composite electrolytes further increased by increasing the content of LiTFSI, SPVDFLi/LiTFSI-40 showed the conductivity of 1.41×10^-4 S/cm at 25 ℃, the steady voltage of up to 4.84 V, and the capacity retention rate of is 99.1% after 50 cycles at 0.2 C, because of its high conductivity, high lithium-ion migration number, and high efficiency in inhibiting the growth of lithium dendrites SPVDFLi, the excellent lithium-ion battery assembled with SPVDFLi/LiTFSI-40. These findings suggest that the PVDF/SPVDFLi/LiTFSI composite electrolytes will be used to create high-performance solid-state lithium-ion batteries.

Key words: polymer composite electrolytes, polyvinylidene fluoride sulfonate lithium, conductivity, lithium-ion migration number

CLC Number:

TM 912

Yue SU, Xuhua LIU, Fanglei ZENG, Yurong REN, Bencai LIN. Preparation and properties of polyvinylidene fluoride/polyvinylidene fluoride sulfonate lithium/lithium salt composite solid electrolyte[J]. Energy Storage Science and Technology, 2021, 10(6): 2069-2076.

Figures/Tables 8

Fig. 1

Fig. 2

Fig. 3

Table 1

Lithium ion migration number of various SPEs"

样品	I₀/mA	I_SS/mA	R₀/Ω	R_SS/Ω	$t L i +$
SPVDFLi-60	0.26	0.21	410	420	0.78
SPDVDFLi/LiTFSI-40	0.95	0.62	75	88	0.68
PVDF/LiTFSI	3.30	1.70	650	700	0.47

Table 1

Table 2

Fig. 4

Fig. 5

Fig. 6

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样品	拉伸强度/MPa	杨氏模量/MPa	断裂伸长率/%
SPVDFLi-60	2.3±0.3	13.7±0.6	23.0±0.2
SPVDFLi/LiTFSI-10	3.1±0.5	29.5±0.2	25.8±0.5
SPVDFLi/LiTFSI-20	4.0±0.2	14.8±0.9	33.7±0.4
SPVDFLi/LiTFSI-30	3.0±0.1	12.7±0.4	35.1±0.7
SPVDFLi/LiTFSI-40	4.2±0.2	16.5±0.3	56.5±0.1
PVDF/LiTFSI	8.0±0.4	55.2±0.2	35.8±0.2

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