腈基功能化有机硅电解液添加剂对LiFePO4电池低温性能的影响

doi:10.7503/cjcu20180773

摘要/Abstract

摘要：

合成了一种腈基功能化有机硅化合物3-氰乙基-二乙氧基-甲基硅烷(DESCN), 并对其化学结构和电化学窗口进行了表征. 采用恒流充放电、扫描电子显微镜(SEM)、 X射线光电子能谱(XPS)及电化学阻抗谱(EIS)等方法研究了DESCN添加剂对LiFePO₄电池低温性能的影响. 结果表明, DESCN化合物能够在电极表面参与形成更薄、更均匀且致密的固体电解质界面(SEI)膜, 抑制电解液副反应的发生, 减小界面膜阻抗, 有利于低温下电极/电解液界面的Li⁺扩散和电荷转移, 从而提高LiFePO₄电池的低温性能.

关键词: 有机硅, 腈基, 电解液添加剂, 低温性能, 锂离子电池

Abstract:

A nitrile group functionalized organosilicon compound, 3-(diethoxy-methyl-silanyl)-propionitrile(DESCN) was synthesized and its chemical structure and electrochemical window were characterized. The effects of DESCN on the low-temperature performance of LiFePO₄ cell were investigated by charge-discharge cycling test, scanning electron microscopy(SEM), X-ray photoelectron spectroscopy(XPS) and electrochemical impedance spectroscopy(EIS) and so on. It is revealed that adding 2%DESCN could improve the low-temperature performance of LiFePO₄ cell. At -20 ℃, the cell exhibits a high discharge capacity of 73 mA·h/g and are stable after 50 cycles. DESCN involved in the formation of stable solid electrolyte interface(SEI) film to inhibit electrolyte decomposition and decrease the battery resistance, which facilitate Li⁺ diffusion and electron transportation at electrode/electrolyte interface at low-temperature.

Key words: Organosilicon, Nitrile group, Electrolyte additive, Low-temperature performance, Lithium-ion battery

中图分类号:

O646

TrendMD:

赵欣悦, 汪靖伦, 闫晓丹, 张灵志. 腈基功能化有机硅电解液添加剂对LiFePO₄电池低温性能的影响. 高等学校化学学报, 2019, 40(6): 1258.

ZHAO Xinyue,WANG Jinglun,YAN Xiaodan,ZHANG Lingzhi. Effect of Nitrile Group Functionalized Organosilicon as Electrolyte Additive on Low-temperature Performance of LiFePO₄ Battery^†. Chem. J. Chinese Universities, 2019, 40(6): 1258.

图/表 11

Fig.1 Chemical structure of DESCN 1H NMR(400 MHz, CDCl3), δ: 3.78(q, 4H, —OCH2CH3), 2.38(t, 2H, —CH2CH2CN), 1.21(t, 6H, —OCH2CH3), 0.98(t, 2H, —CH2CH2CN), 0.18(s, 3H, —SiCH3); 13C NMR(100 MHz, CDCl3), δ: 120.9, 50.3, 10.9, 9.6, -6.0; 29Si NMR(79.5 MHz, CDCl3), δ: -9.14.

Table 1 Physical and chemical properties of DESCN compound

ε^a	η^b/(mPa·s)	σ^c/(mS·cm^-1)	$E cathodic d$ /V	$E anodic e$ /V	$T g f$ / ℃
14.7	1.64	1.27	0	6.3	-128

Table 1 Physical and chemical properties of DESCN compound

ε^a	η^b/(mPa·s)	σ^c/(mS·cm^-1)	$E cathodic d$ /V	$E anodic e$ /V	$T g f$ / ℃
14.7	1.64	1.27	0	6.3	-128

Fig.2 Charge-discharge curves of LiFePO4/Li cells at 25 ℃(A) and -20 ℃(B)

Fig.3 Cycling performance of LiFePO4/Li cells at 25 ℃(A) and -20 ℃(B)

Fig.4 dQ/dV curves of LiFePO4 electrode in the electrolytes without and with 2%DESCN at 25 ℃(A) and -20 ℃(B)

Fig.5 Nyquist plots of the LiFePO4 electrode at 25 ℃(A) and -20 ℃(B) Inset: R0: Electrolyte/electrode resistance; Rf and Cf: SEI film resistance and related capacitance; Rc and Cd: charge-transfer resistance and related capacitance; Ri and Ci: electronic resistance and related capacitance; ZW: Warburg diffusion impedance.

Fig.6 SEM images of surface morphology of LiFePO4 electrode (A) Original; (B) cycled in electrolyte without DESCN at -20 ℃; (C) cycled in electrolyte with 2% DESCN at -20 ℃.

Fig.7 EDS spectra of surface of LiFePO4 electrode after low temperature cycling

Table 2 Element contents of the electrode surface

Electrode	C(%)	O(%)	P(%)	Fe(%)
Before cycling	15.73	59.45	13.51	11.30
Without DESCN after cycling	19.35	58.89	12.16	9.60
With 2%DESCN after cycling	18.64	57.00	13.12	11.25

Fig.8 N1s(A) and Si2p(B) XPS spectra of LiFePO4 electrodes cycled in the electrolyte containing 2%DESCN

Fig.9 C1s(A, C) and O1s(B, D) XPS spectra of LiFePO4 electrodes cycled at low temperature (A, B) Without DESCN; (C, D) 2%DESCN.

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腈基功能化有机硅电解液添加剂对LiFePO₄电池低温性能的影响

Effect of Nitrile Group Functionalized Organosilicon as Electrolyte Additive on Low-temperature Performance of LiFePO₄ Battery^†

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