•  
  •  
 

Corresponding Author

Yu-liang CAO(ylcao@whu.edu.cn)

Abstract

Lithium-ion batteries (LIBs) have emerged as the most widely used energy storage devices owing to their high energy density and excellent cycling stability. However, safety issues have become a critical obstacle for the large-scale applications of LIBs in the energy storage systems and electric vehicles (EVs). Currently, LIBs use a low flash- and boiling-point organic carbonate as the electrolyte, which is extremely likely to cause firing or explosion. Although some flame-retardant additives can inhibit the combustion of electrolyte to a certain extent, it brings little effect in practical application. Therefore, the development of nonflammable electrolytes is an essential solution to eliminate the safety hazards of LIBs. The phosphorus-based electrolytes seem to be a good choice for flame-retardant or nonflammable electrolytes because of their low viscosity, high solubility, and low cost. In this paper, the problems and solutions of phosphate-based solvents as a safe electrolyte for LIBs are reviewed. Firstly, the feasibility and existing problems of phosphate ester as a solvent of electrolyte are introduced, and then the flame-retardant mechanism, flame-retardant or nonflammable phosphorus-based electrolytes are described by classifications, with emphasis on the electrochemical compatibility of such an electrolyte and its countermeasures. On this basis, we prospect the future research directions in high safety phosphorus-based electrolytes.

Graphical Abstract

Keywords

lithium-ion battery, phosphorus-based solvent, electrolyte, safety, non-flammable solvent

Publication Date

2020-10-28

Online Available Date

2020-09-17

Revised Date

2020-08-28

Received Date

2020-06-29

References

[1] Kalhoff J, Eshetu G G, Bresser D, et al. Safer electrolytes for lithium-ion batteries: State of the art and perspectives[J]. ChemSusChem, 2015,8(13):2154-2175.
URL pmid: 26075350

[2] Wu X K, Song K F, Zhang X Y, et al. Safety issues in lithium ion batteries: Materials and cell design[J]. Frontiers in Energy Research, 2019,7:65.

[3] Selman J R, Al Hallaj S, Uchida I, et al. Cooperative research on safety fundamentals of lithium batteries[J]. Journal of Power Sources, 2001, 97-98:726-732.

[4] Fang S H, Qu L, Luo D, et al. Novel mixtures of ether-fun-ctionalized ionic liquids and non-flammable methylperfluorobutylether as safe electrolytes for lithium metal batteries[J]. RSC Advances, 2015,5(43):33897-33904.

[5] Fan X L, Chen L, Borodin O, et al. Non-flammable electrolyte enables Li-metal batteries with aggressive cathode chemistries[J]. Nature Nanotechnology, 2018,13(8):715-722.
doi: 10.1038/s41565-018-0183-2 URL pmid: 30013215

[6] Dalavi S, Xu M Q, Ravdel B, et al. Nonflammable electrolytes for lithium-ion batteries containing dimethylmethylphosphonate[J]. Journal of the Electrochemical Society, 2010,157(10):A1113-A1120.

[7] Xiang H F, Jin Q Y, Chen C H, et al. Dimethyl methylpho-sphonate-based nonflammable electrolyte and high safety lithium-ion batteries[J]. Journal of Power Sources, 2007,174(1):335-341.

[8] Wang X M, Yasukawa E, Kasuya S. Nonflammable trimethyl phosphate solvent-containing electrolytes for lithium-ion batteries: I. Fundamental properties[J]. Journal of The Electrochemical Society, 2001,148(10):A1058-A1065.

[9] Xu K, Ding M S, Zhang S S, et al. An attempt to formulate nonflammable lithium ion electrolytes with alkyl phosphates and phosphazenes[J]. Journal of The Electrochemical Society, 2002,149(5):A622-A626.

[10] Feng J K, Ma P, Yang H X, et al. Understanding the interactions of phosphonate-based flame-retarding additives with graphitic anode for lithium ion batteries[J]. Electro-chimica Acta, 2013,114:688-692.

[11] Hyung Y E, Vissers D R, Amine K. Flame-retardant additives for lithium-ion batteries[J]. Journal of Power Sour-ces, 2003, 119-121:383-387.

[12] Xu K, Zhang S S, Allen J L, et al. Nonflammable electrolytes for Li-ion batteries based on a fluorinated phosphate[J]. Journal of The Electrochemical Society, 2002,149(8):A1079-A1082.

[13] Xu K, Zhang S S, Allen J L, et al. Evaluation of fluorinated alkyl phosphates as flame retardants in electrolytes for Li-ion batteries: II. Performance in cell[J]. Journal of The Electrochemical Society, 2003,150(2):A170-A175.

[14] Zhang S S, Xu K, Jow T R. Tris(2,2,2-trifluoroethyl) phosphite as a co-solvent for nonflammable electrolytes in Li-ion batteries[J]. Journal of Power Sources, 2003,113(1):166-172.

[15] Zeng Z Q, Jiang X Y, Wu B B, et al. Bis(2,2,2-trifluoroethyl) methylphosphonate: An novel flame-retardant additive for safe lithium-ion battery[J]. Electrochimica Acta, 2014,129:300-304.

[16] Zhu X M, Jiang X Y, Ai X P, et al. Bis(2,2,2-Trifluoroethyl) ethylphosphonate as novel high-efficient flame retardant additive for safer lithium-ion battery[J]. Electro-chimica Acta, 2015,165:67-71.

[17] Wu B B, Pei F, Wu Y, et al. An electrochemically compatible and flame-retardant electrolyte additive for safe lithium ion batteries[J]. Journal of Power Sources, 2013,227:106-110.

[18] Nakagawa H, Ochida M, Domi Y, et al. Electrochemical Raman study of edge plane graphite negative-electrodes in electrolytes containing trialkyl phosphoric ester[J]. Journal of Power Sources, 2012,212:148-153.

[19] Feng J K, Sun X J, Ai X P, et al. Dimethyl methyl phosphate: A new nonflammable electrolyte solvent for lithium-ion batteries[J]. Journal of Power Sources, 2008,184(2):570-573.

[20] Wang X M, Yamada C, Naito H, et al. High-concentration trimethyl phosphate-based nonflammable electrolytes with improved charge-discharge performance of a graphite anode for lithium-ion cells[J]. Journal of The Electrochemical Society, 2006,153(1):A135-A139.

[21] Zeng Z Q, Jiang X Y, Li R, et al. A safer sodium-ion battery based on nonflammable organic phosphate electrolyte[J]. Advanced Science, 2016,3(9):1600066.
URL pmid: 27711263

[22] Zeng Z Q, Wu B B, Xiao L F, et al. Safer lithium ion batteries based on nonflammable electrolyte[J]. Journal of Power Sources, 2015,279:6-12.

[23] Zeng Z Q, Liu X W, Jiang X Y, et al. Enabling an intrinsically safe and high-energy-density 4.5 V-class Li-ion battery with nonflammable electrolyte[J]. InfoMat, 2020, DOI: 10.1002/inf2.12089.

[24] Jiang X Y, Liu X M, Zeng Z Q, et al. A bifunctional fluorophosphate electrolyte for safer sodium-ion batteries[J]. iScience, 2018,10:114-122.
URL pmid: 30513393

[25] Jiang X Y, Zeng Z Q, Xiao L F, et al. An all-phosphate and zero-strain sodium-ion battery based on Na3V2(PO4)3 cathode, NaTi2(PO4)3 anode, and trimethyl phosphate electrolyte with intrinsic safety and long lifespan[J]. ACS Applied Materials & Interfaces, 2017,9(50):43733-43738.

[26] Liu X W, Jiang X Y, Zhong F P, et al. High-safety symmetric sodium-ion batteries based on nonflammable phosphate electrolyte and double Na3V2(PO4)3 electrodes[J]. ACS Applied Materials & Interfaces, 2019,11(31):27833-27838.
URL pmid: 31287282

[27] Wang J H, Yamada Y, Sodeyama K, et al. Fire-extinguishing organic electrolytes for safe batteries[J]. Nature Energy, 2018,3(1):22-29.

[28] Chen S R, Zheng J M, Mei D H, et al. High-voltage lithium-metal batteries enabled by localized high-concentration electrolytes[J]. Advanced Materials, 2018,30(21):1706102.

[29] Suo L M, Borodin O, Gao T, et al. “Water-in-salt” electrolyte enables high-voltage aqueous lithium-ion chemistries[J]. Science, 2015,350(6263):938-943.
URL pmid: 26586759

[30] Yamada Y, Furukawa K, Sodeyama K, et al. Unusual stability of acetonitrile-based superconcentrated electrolytes for fast-charging lithium-ion batteries[J]. Journal of the American Chemical Society, 2014,136(13):5039-5046.
doi: 10.1021/ja412807w URL pmid: 24654781

[31] Yamada Y, Koyama Y, Abe T, et al. Correlation between charge-discharge behavior of graphite and solvation structure of the lithium ion in propylene carbonate-containing electrolytes[J]. The Journal of Physical Chemistry C, 2009,113(20):8948-8953.

[32] Suo L M, Hu Y S, Li H, et al. A new class of solvent-in-salt electrolyte for high-energy rechargeable metallic lithium batteries[J]. Nature Communications, 2013,4:2513-2519.
doi: 10.1038/ncomms3513 URL pmid: 24085110

[33] Xiao L F, Zeng Z Q, Liu X W, et al. Stable Li metal anode with “ion-solvent-coordinated” nonflammable electrolyte for safe Li metal batteries[J]. ACS Energy Letters, 2019,4(2):483-488.

[34] Zeng Z Q, Murugesan V, Han K S, et al. Non-flammable electrolytes with high salt-to-solvent ratios for Li-ion and Li-metal batteries[J]. Nature Energy, 2018,3(8):674-681.

[35] Liu X W, Shen X H, Zhong F P, et al. Enabling electrochemical compatibility of non-flammable phosphate electrolytes for lithium-ion batteries by tuning their molar ratios of salt to solvent[J]. Chemical Communications, 2020,56(48):6559-6562.
doi: 10.1039/d0cc02940h URL pmid: 32396155

[36] Jiang X Y, Liu X W, Zeng Z Q, et al. A nonflammable Na+-based dual-carbon battery with low-cost, high voltage, and long cycle life[J]. Advanced Energy Materials, 2018,8(36):1802176.

[37] Liu X W, Jiang X Y, Zeng Z Q, et al. High capacity and cycle-stable hard carbon anode for nonflammable sodium-ion batteries[J]. ACS Applied Materials & Interfaces, 2018,10(44):38141-38150.
URL pmid: 30335351

[38] Shiga T, Kato Y, Kondo H, et al. Self-extinguishing electrolytes using fluorinated alkyl phosphates for lithium batteries[J]. Journal of Materials Chemistry A, 2017,5(10):5156-5162.

[39] Takada K, Yamada Y, Yamada A. Optimized nonflammable concentrated electrolytes by introducing a low-dielectric diluent[J]. ACS Applied Materials & Interfaces, 2019,11(39):35770-35776.
doi: 10.1021/acsami.9b12709 URL pmid: 31498585

[40] Chen S R, Zheng J M, Yu L, et al. High-efficiency lithium metal batteries with fire-retardant electrolytes[J]. Joule, 2018,2(8):1548-1558.

[41] Cao X, Xu Y B, Zhang L C, et al. Nonflammable electrolytes for lithium ion batteries enabled by ultraconformal passivation interphases[J]. ACS Energy Letters, 2019,4(10):2529-2534.

[42] Yang H J, Guo C, Chen J H, et al. An Intrinsic flame-retardant organic electrolyte for safe lithium-sulfur batteries[J]. Angewandte Chemie International Edition, 2019,58(3):791-795.
URL pmid: 30426649

[43] Chen J H, Yang H J, Zhang X, et al. Highly reversible lithium-metal anode and lithium-sulfur batteries enabled by an intrinsic safe electrolyte[J]. ACS Applied Materials & Interfaces, 2019,11(36):33419-33427.
URL pmid: 31423761

Download

Share

COinS
 
 

To view the content in your browser, please download Adobe Reader or, alternately,
you may Download the file to your hard drive.

NOTE: The latest versions of Adobe Reader do not support viewing PDF files within Firefox on Mac OS and if you are using a modern (Intel) Mac, there is no official plugin for viewing PDF files within the browser window.