Abstract
The effects of fluoroethylene carbonate (FEC) as co-solvent on the electrochemical performance of high voltage cathode material Li2CoPO4F are investigated. Compared with traditional carbonate based electrolyte (1 mol·L-1 LiPF6 EC/DMC (1:1, m:m)), the FEC/DMC based electrolyte can significantly improved the electrochemical performance of Li2CoPO4F. After 100 cycles between 3V and 5.4 V at 1 C rate, the capacity retention of Li2CoPO4F electrode in 1 mol·L-1 LiPF6 EC/DMC (1:1, m:m) was 52.6 % , while that in the EC/DMC based electrolyte was only 14.5 %. Possible functional mechanisms of FEC improving the electrochemical performance of Li2CoPO4F were studied by LSV, EIS, SEM and XPS measurements. It was shown that compared with the traditional EC/DMC based electrolyte, the FEC/DMC based electrolyte exhibited higher stability at high voltage, which suppressed the side reactions at electrode/electrolyte interface when charged to high voltage, and improved the structure stability of Li2CoPO4F during cycling, thus, significantly enhanced the electrochemical performance of Li2CoPO4F.
Graphical Abstract
Keywords
lithium ion battery, high voltage electrolytes; fluoroethylene carbonate; Li2CoPO4F
Publication Date
2018-06-28
Online Available Date
2017-06-09
Revised Date
2017-06-06
Received Date
2017-05-11
Recommended Citation
Zhi-gang WANG, Wei-min ZHAO, Hong-chun WANG, Min LIN, Zheng-liang GONG, Yong YANG.
Influences of FEC-based Electrolyte on Electrochemical Performance of High Voltage Cathode Material Li2CoPO4F[J]. Journal of Electrochemistry,
2018
,
24(3): 216-226.
DOI: 10.13208/j.electrochem.170509
Available at:
https://jelectrochem.xmu.edu.cn/journal/vol24/iss3/3
References
[1] Yu J G, Rosso K M, Zhang J G. Ab initio study of lithium transition metal fluorophosphate cathodes for rechargeable batteries[J]. Journal of Materials Chemistry A, 2011, 21(32): 12054-12058.
[2] Schoiber J, Berge R J F, Yada C, et al. A Two-step synthesis for Li2CoPO4F as high-voltage cathode material[J].Journal of The Electrochemical Society, 2015, 162(14): A2679-A2683.
[3] Truong Q D, Devarajiu M K, Ganbe Y, et al. Structural analysis and electrochemical performance of Li2CoPO4F cathode materials[J]. Electrochimica Acta, 2014, 127: 245-251.
[4] Fedotov S S, Kabanov A A, KabanovaC N A, et al. Crystal structure and Li-ion transport in Li2CoPO4F high-voltage cathode material for Li-ion batteries[J]. The Journal of Physical Chemistry C, 2017, 121(6): 3194-3202.
[5] Amaresh S, Karthikeyan K, Kim K J, et al. Facile synthesis of ZrO2 coated Li2CoPO4F cathode materials for lithium secondary batteries with improved electrochemical properties[J]. Journal of Power Sources, 2013, 244: 395-402.
[6] Wu X B, Gong Z L,Tan S, et al. Sol-gel synthesis of Li2CoPO4F/C nanocomposite as a high power cathode material for lithium ion batteries[J]. Journal of Power Sources, 2012, 220: 122-129.
[7] Wu X B, Wang S H, Li X C, et al. Promoting long-term cycling performance of high-voltage Li2CoPO4F by the stabilization of electrode/electrolyte interface[J]. Journal of Materials Chemistry A, 2014, 2(4): 1006-1013.
[8] Wang D Y, Xiao J, Xu W, et al. Preparation and electrochemical investigation of Li2CoPO4F cathode material for lithium-ion batteries[J]. Journal of Power Sources, 2011, 196(4): 2241-2245.
[9] Khasanova N R, Drozhzhin O A, Fedotov S S, et al. Synthesis and electrochemical performance of Li2Co1-xMxPO4F (M = Fe, Mn) cathode materials[J]. Beilstein Journal of Nanotechnology, 2013, 4: 860-867.
[10] Wang L, Ma Y L, Qu Y T, et al. Influence of fluoroethylene carbonate as co-solvent on the high-voltage performance of LiNi1/3Co1/3Mn1/3O2 cathode for lithium-ion batteries[J]. Electrochimica Acta, 2016, 191: 8-15.
[11] Sharabi R, Markevich E, Fridman K, et al. Electrolyte solution for the improved cycling performance of LiCoPO4/C composite cathodes[J]. Electrochemistry Communications 2013, 28: 20-23.
[12] Wu Y P(吴宇平). Li-ion batteries: Application and practices[M]. Beijing: Chemical Industry Press(化学工业出版社), 2004: 213-214.
[13] Xu W, Chen X L, Ding F, et al. Reinvestigation on the state-of-the-art nonaqueous carbonate electrolytes for 5 V Li-ion battery applications[J]. Journal of Power Sources, 2012, 213: 304-316.
[14] Kiyoshi K. Anodic oxidation of nonaqueous electrolytes on cathode materials and current collectors for rechargeable lithium batteries[J]. Journal of Power Sources, 1999, 81: 123-129.
[15] Luo Y, Lu T L, Zhang Y X, et al. Enhanced electrochemical performance of LiNi0.5Mn1.5O4 cathode using an electrolyte with 3-(1,1,2,2-tetrafluoroethoxy)-1,1,2,2-tetrafluoropropane[J]. Journal of Power Sources, 2016, 323: 134-141.
[16] Wu X W, Li X H, Wang Z X, et al. Comprehensive reinvestigation on the initial coulombic efficiency and capacity fading mechanism of LiNi0.5Mn1.5O4 at low rate and elevated temperature[J]. Journal of Solid State Electrochemistry, 2013, 17(4): 1029-1038.
[17] Khasanova N R, Gavrilov A N, Antipov E V, et al. Structural transformation of Li2CoPO4F upon Li-deintercalation[J]. Journal of Power Sources, 2011, 196(1): 355-360.
[18] Okumura T, Shikano M, Yamaguchi Y, et al. Structural changes in Li2CoPO4F during lithium-ion battery reactions[J]. Chemistry of Materials, 2015, 27(8): 2839-2847.
[19] Yan G C, Li X H, Wang Z X, et al. Tris(trimethylsilyl)-phosphate: A film-forming additive for high voltage cathode material in lithium-ion batteries[J]. Journal of Power Sources, 2014, 248: 1306-1311.
[20] Zheng X Y, Huang T, Pan Y, et al. High-voltage performance of LiNi1/3Co1/3Mn1/3O2/graphite batteries with di-(methylsulfonyl) methane as a new sulfone-based electrolyte additive[J]. Journal of Power Sources, 2015, 293: 196-202.
[21] Li Y, Lian F, Ma L L, et al. Fluoroethylene carbonate as electrolyte additive for improving the electrochemical performances of high-capacity Li1.16[Mn0.75Ni0.25]0.84O2 material[J]. Electrochimica Acta, 2015, 168: 261-270.
[22] Wang C Y, Yu L, Fan W Z, et al. 3,3'-(Ethylenedioxy)dipropiononitrile as an electrolyte additive for 4.5 V LiNi1/3Co1/3Mn1/3O2/graphite cells[J]. ACS Applied Materials & Interfaces, 2017, 9(11): 9630-9639.
[23] Martha S K, Nanda J, Veith G M, et al. Surface studies of high voltage lithium rich composition: Li1.2Mn0.525Ni0.175Co0.1O2 [J]. Journal of Power Sources, 2012, 216: 179-186.
[24] Xu M Q, Zhou L, Dong Q N, et al. Development of novel lithium borate additives for designed surface modification of high voltage LiNi0.5Mn1.5O4 cathodes[J]. Energy & Environmental Science, 2016, 8(4): 1308-1319.
[25] Markevich E, Sharabi R, Gottlieb H, et al. Reasons for capacity fading of LiCoPO4 cathodes in LiPF6 containing electrolyte solutions [J]. Electrochemistry Communications, 2012, 15(1): 22-25.