4.5 V Li-ion battery with a carbonate ester-based electrolyte

doi:10.19799/j.cnki.2095-4239.2020.0045

Abstract

Abstract:

LiNi_0.5Mn_1.5O₄ (LNMO) spinel is a cathode material with a voltage plateau of 4.7 V versus Li. An LNMO cell shows an operation voltage that is 1.3 and 0.9 V higher than that of a LiFePO₄ and NCM cell, respectively. The LNMO cell has the advantages of higher specific energy and lower cost and can meet the long range per charge and low cost requirements of electric vehicles in the post-subsidy era after 2020. The high operating voltage is undoubtedly a great advantage; however, the extremely high cut-off voltage (4.9 V vs. Li⁺) is also a huge obstacle in its commercialization. The widely used carbonate ester-based electrolytes are considered unsuitable owing to the intrinsic thermodynamic tendency of these carbonates to decompose at potentials well below the thermodynamic threshold required for the reversible reactions of these high-voltage systems. Alternatives such as fluoride carbonate, thiophene, and ionic liquids were introduced to replace the carbonate solvent used as the electrolyte in present commercial lithium-ion batteries. However, full battery data have not been reported with respect to optimum cycle performance and a sufficiently high coulombic efficiency for practical batteries. In this study, LiNi_0.5Mn_1.5O₄/graphite full cells are demonstrated using an electrolyte that is based on carbonate esters. The side reactions between the electrolyte and interface are inhibited by modifying the interface of lithium nickel-manganate cathode materials to improve the efficiency and cycling performance of the full cells. However, there is still a gap between commercial applications. The side reactions are further inhibited using the GDY electrolyte to improve the efficiency and cycling performance of the full cells. The full cells show superior electrochemical performance compared to that of the reported full cells that use high-voltage-resistant solvents. The capacity retention rate of the full cells can reach 88.02% and the coulombic efficiency can reach 99.93% at 1C and 25 ℃ after 1000 cycles. The capacity retention rate of the full cells can reach 93.88% and the coulombic efficiency is 99.80% at 1C and 55 ℃ after 300 cycles. This performance has already met the requirements of EV applications. In addition, the inhibition effect of material modification and electrolyte optimization on the side reactions between the electrolyte and interface is demonstrated by comparing the median polarization voltage and impedance during cycling. These results indicate that LiNi_0.5Mn_1.5O₄/graphite full cells, which are based on carbonate ester electrolytes, with a working voltage of 4.5 V can be commercialized.

Key words: lithium ion battery, LiNi_0.5Mn_1.5O₄, carbonate, graphite, high temperature

CLC Number:

TM 911

ZHAN Yuanjie, WU Yida, MA Xiaowei, LIANG Haicong, HUANG Xuejie. 4.5 V Li-ion battery with a carbonate ester-based electrolyte[J]. Energy Storage Science and Technology, 2020, 9(2): 319-330.

Figures/Tables 10

Fig.1

Fig.2

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Fig.6

Table 1

The electrochemical properties of the reported full cells using the high-voltage resistant solvent"

名称	电解液	电化学性能 [比容量，容量保持率（倍率，循环次数，效率），测试温度]
LNMO/graphite^[30]	1 mol/L LiPF₆-FEC/HF-DEC	约119 mA·h/g（C/10），约87.0%（C/3，50周，约99.8%），25 ℃
LNMO/graphite^[24]	1 mol/L LiPF₆-FEC/F-EMC/F-EPE	约125 mA·h/g（C/10），约89.9%（C/3，100周，＞99.5%），25 ℃ 约122 mA·h/g（C/10），约66.93%（C/3，100周，＞99.5%），55℃
LNMO/graphite^[31]	1 mol/L LiPF₆-F-AEC/F-EMC/F-EPE+2%TFP-PC-E	约114 mA·h/g（C/10），约51.66%（C/3，100周，~98.6%），55 ℃
LNMO/graphite^[32]	1 mol/L LiPF₆-FEC/DMC/EMC/HFPM	1.434 mA·h/g（C/2），82%（C/2，200周，＞99.6%），25 ℃
LNMO/graphite^[33]	1 mol/L LiPF₆-FEC/PFE	约118 mA·h/g（C/10），57.1%（1 C，200周，约99.6%），30 ℃
LNMO/MCMB^[34]	3 mol/L LiFSI-SL	约111 mA·h/g（C/2），69%（C/2，1000周，约99.8%），30 ℃
LNMO/MCMB^[35]	1 mol/L LiPF₆-FEC/DMC/EMC/TTE	120 mA·h/g（1C），93%（1C，35周，/）25 ℃
LNMO/MCMB^[36]	1 mol/L LiDFOB-SL + 5 wt% TMSP	110 mA·h/g（C/2），80.5%（C/2，300周，98.3%），25 ℃ 119 mA·h/g（C/2），81.9%（C/2，100周，94.7%），55 ℃
LNMO/LTO^[37]	0.7 mol/L LiTFSI-Pyr14TFSI	90 mA·h/g（C/2），47%（C/2，50周，约96%），40 ℃ 105 mA·h/g（C/2），71.8%（C/2，50周，约95%），60 ℃
LNMO/LTO^[16]	1 mol/L LiPF₆-TMS/EMC	约85 mA·h/g（2C），90.58%（2C，1000周，/）25 ℃
LNMO/Mo₆S₈ ^[20]	1 mol/L LiBF₄-EMIBF₄	约100 mA·h/g（C/6），约66.7%（C/2，40~80周，/），30 ℃
NMC442/graphite^[38]	1 mol/L LiPF₆-FEC/TFEC+2% PES +0.5% MMDS	约175 mA·h/g（C/2.4），约56%（C/2.4，800周，约99.6%），40 ℃
NMC532/graphite^[39]	1 mol/L LiPF₆-DFEC/FMES	约190 mA·h/g（C/10），78.94%（C/3，500周，≥99.9%），25 ℃
NMO/graphite（本文）	1mol/L LiPF₆-EC/DMC+1% TMSP+2% LODFB	116.9 mA·h/g（C/5），88.02%（1C，1000周，约99.93%），25 ℃ 119.7 mA·h/g（C/5），93.88%（1C，300周，约99.80%），55 ℃

Table 1

Fig.7

Fig.8

Fig.9

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