Effect of Dual-functional Electrolyte Additive on High Temperature and High Voltage Performance of Li-ion Battery

doi:10.15541/jim20210653

Abstract

Abstract:

Development and application of power lithium-ion batteries are strictly restricted by their high temperature and high voltage performance, such as capacity degradation and gas swelling, which are related to not only the modified electrode material and battery design but also the electrolyte. Herein, tetravinylsilane (TVS) was applied as electrolyte additive to improve storage and cycling performances of LiNi_0.6Co_0.2Mn_0.2O₂ (NCM622)/graphite pouch cell at high cutoff voltage (4.4 V) and high temperature (45-60 ℃). The capacity retention rate of the cell after 400 cycles (2.8-4.4 V) at 1C (1C=1.1 Ah) with mass fraction 0.5% TVS in the electrolyte is as high as 92%, compared with 82% for its counterpart without TVS. On the one hand, TVS is preferentially oxidized under high voltage, contributing to the formation of a high-temperature resistant CEI (cathode electrolyte interphase) film on the surface of NCM622 particles, which effectively inhibits generation of internal cracks in NCM622 particles and dissolution of transition metal ions. On the other hand, TVS can also be preferentially reduced and polymerized, thus forming a stable SEI film on the surface of graphite anode, which inhibits the side reaction between the electrolyte and the negative electrode.

Key words: high temperature, lithium-ion pouch cell, electrolyte additive, cycle stability, transition metal dissolution

CLC Number:

TM911

JIANG Yiyi, SHEN Min, SONG Banxia, LI Nan, DING Xianghuan, GUO Leyi, MA Guoqiang. Effect of Dual-functional Electrolyte Additive on High Temperature and High Voltage Performance of Li-ion Battery[J]. Journal of Inorganic Materials, 2022, 37(7): 710-716.

Figures/Tables 12

Fig. 1 Schematic procedure for preparing the symmetric cell

Fig. 2 LSV curves of (a) oxidation and (b) reduction of electrolytes with and without TVS

Fig. S1 CV curves of NMC622 electrodes with and without TVS in electrolytes (a) 1st cycle; (b) 2nd cycle

Fig. 3 (a) Gas swelling rates and ACR change rates, (b) K values and capacity recovery rates, (c) charge and discharge curves of pouch cells with and without TVS in electrolytes after storage at 60 ℃ for 14 d

Table 1 Uess fractions of Ni, Co and Mn ions deposited on anodes from pouch cell with and without TVS in electrolyte stored at cutoff potential of 4.4 V and temperature of 60 ℃ for 14 d

Sample	Ni/(×10^-4, %)	Co/(×10^-4, %)	Mn/(×10^-4, %)
Base	90	21	130
TVS	35	4	69

Table S1 Gas composition and contents of pouch cells with and without TVS in electrolytes stored at cutoff potential of 4.4 V and temperature of 60 ℃ for 14 d

Sample	CO/µL	CH₄/µL	CO₂/µL	C₂H₄/µL	H₂/µL
Base	393.3	253.2	209.3	67.0	17.6
TVS	9.2	4.8	2.2	1.1	0.2

Fig. 4 Cycling performance of pouch cells with and without TVS in electrolytes at 45 ℃ (a) Discharge capacity and (b) ΔV vs cycle number; EIS plots of (c) pouch full cells, (d) graphite/graphite symmetric cells and (e) NCM622/NCM622 symmetric cells before and after 100 cycles

Fig. S2 Cycling performance of pouch cells with and without TVS in electrolytes at 45 ℃ (a) Differential capacity (dQ/dV) versus potential of Base; (b) Differential capacity (dQ/dV) versus potential of TVS

Table S2 Fitted EIS results before and after 100 cycles of pouch full cells and corresponding symmetric cells with and without TVS in electrolytes

Sample	Full cell			Anode symmetric cell			Cathode symmetric cell
Sample	R_s/mΩ	R_sei/mΩ	R_ct/mΩ	R_s/mΩ	R_sei/mΩ	R_ct/mΩ	R_s/mΩ	R_sei/mΩ	R_ct/mΩ
Base-before cycle	16.2	7.5	14.2	3.4	4.7	23.2	2.6	116.1	21.2
Base-after cycle	46.7	9.1	19.3	4.2	17.1	26.5	2.7	144.3	26.7
TVS-before cycle	16.4	8.9	25.8	4.5	20.5	43.3	2.1	86.1	18.2
TVS-after cycle	38.5	10.2	25.4	4.8	22.6	43.8	2.2	100.4	18.1

Fig. 5 SEM images of cathodes from pouch cells (a) without and (b) with TVS in electrolytes after 100 cycles; (c) XPS spectra of cathodes from pouch cells without and with TVS in electrolytes after 10 cycles

Fig. S3 SEM images of anodes from pouch cells (a) without and (b) with TVS in electrolytes after 100 cycles; (c) Si2p XPS spectra of anode from pouch cell with TVS in electrolyte after 10 cycles

Fig. S4 Working mechanism of TVS additive on cathode and anode of NCM622/graphite pouch cell

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