Fluorine chemistry in lithium-ion and sodium-ion batteries

Abstract

As the peculiar element in the Periodic Table of Elements, fluorine gas owns the highest standard electrode potential of 2.87 V vs. F^-, and a fluorine atom has the maximum electronegativity. Benefiting from the prominent property, fluorine plays an important role in the development of lithium-ion batteries (LIBs) and sodium-ion batteries (SIBs) in terms of cathode materials (transition metal fluorides, fluorinated polyanionic compounds), electrolytes, and interfaces. In cathode materials, the highly electronegative renders enhanced ionic character of transition metal fluorine bonds and correspondingly high working potential in electrolytes; fluorinated electrolytes possess good antioxidant ability and flame retardance, which can significantly improve the thermal safety of a battery. On an electrode-electrolyte interface, the fluorine-rich inorganic component (such as LiF and NaF) is essential for the formation of a robust and stable solid electrolyte interface on anodes. Despite the remarkable advances achieved in fluorinated cathodes, electrolytes, and interfaces, there is still a lack of comprehensive understanding of the function of fluorides in LIBs and SIBs. Accordingly, this review briefly summarized the recent progress of fluorine-based electrodes, electrolytes, and interfaces and highlighted the correlation between the composition, property, and function to reveal the fluorine chemistry in LIBs and SIBs. This review will provide guidance for the rational design and targeted regulation of fluorine-dominated high-performance electrode materials, functionalized electrolytes, and consolidated interfaces.

Keywords

Fluorine chemistry / lithium/sodium ion batteries / cathode materials / electrolytes / interfaces

References

[1] Ullah N,Yuan A.Recent advancement and structural engineering in transition metal dichalcogenides for alkali metal ions batteries.Materials2023;16:2559 PMCID:PMC10095088

[2] Li H,Maier J.Reversible formation and decomposition of LiF clusters using transition metal fluorides as precursors and their application in rechargeable Li batteries.Adv Mater2003;15:736-9

[3] Arai H,Sakurai Y.Cathode performance and voltage estimation of metal trihalides.J Power Sources1997;68:716-9

[4] Barker J,Swoyer JL.Electrochemical insertion properties of the novel lithium vanadium fluorophosphate, LiVPO₄F.J Electrochem Soc2003;150:A1394

[5] Tripathi R,Ellis BL.Scalable synthesis of tavorite LiFeSO₄F and NaFeSO₄F cathode materials.Angew Chem Int Ed2010;49:8738-42

[6] Xu ZL,Park KY.Tailoring sodium intercalation in graphite for high energy and power sodium ion batteries.Nat Commun2019;10:2598 PMCID:PMC6565630

[7] von Aspern N, Röschenthaler GV, Winter M, Cekic-Laskovic I. Fluorine and lithium: ideal partners for high-performance rechargeable battery electrolytes.Angew Chem Int Ed2019;58:15978-6000

[8] Tan J,Dong P,Ye M.A growing appreciation for the role of LiF in the solid electrolyte interphase.Adv Energy Mater2021;11:2100046

[9] Sun L,Feng W.Metal fluoride cathode materials for lithium rechargeable batteries: focus on iron fluorides.Small Methods2023;7:e2201152

[10] Lemoine K,Leblanc M,Tarascon JM.Fluorinated materials as positive electrodes for Li- and Na-ion batteries.Chem Rev2022;122:14405-39

[11] Li T,Ai XP,Yang HX.LiF/Fe nanocomposite as a lithium-rich and high capacity conversion cathode material for Li-ion batteries.J Power Sources2012;217:54-8

[12] Badway F,Pereira N.Carbon metal fluoride nanocomposites: high-capacity reversible metal fluoride conversion materials as rechargeable positive electrodes for Li batteries.J Electrochem Soc2003;150:A1318

[13] Liu S,Xie K,Xu J.A facile one-step hydrothermal synthesis of α-Fe₂O₃ nanoplates imbedded in graphene networks with high-rate lithium storage and long cycle life.J Mater Chem A2014;2:13942-8

[14] Wang F,Chernova NA.Conversion reaction mechanisms in lithium ion batteries: study of the binary metal fluoride electrodes.J Am Chem Soc2011;133:18828-36

[15] Yamakawa N,Grey CP.Investigation of the conversion reaction mechanisms for binary copper(II) compounds by solid-state NMR spectroscopy and X-ray diffraction.Chem Mater2009;21:3162-76

[16] Hua X,Du L.Comprehensive study of the CuF₂ conversion reaction mechanism in a lithium ion battery.J Phys Chem C2014;118:15169-84

[17] Seo JK,Takahara K.Revisiting the conversion reaction voltage and the reversibility of the CuF₂ electrode in Li-ion batteries.Nano Res2017;10:4232-44

[18] Wang F,Seo DH.Ternary metal fluorides as high-energy cathodes with low cycling hysteresis.Nat Commun2015;6:6668 PMCID:PMC4389236

[19] Liu L,Zhou M.A comparison among FeF₃·3H₂O, FeF₃·0.33H₂O and FeF₃ cathode materials for lithium ion batteries: structural, electrochemical, and mechanism studies.J Power Sources2013;238:501-515

[20] Amatucci GG.Fluoride based electrode materials for advanced energy storage devices.J Fluor Chem2007;128:243-62

[21] Li L,Gao P.Origins of large voltage hysteresis in high-energy-density metal fluoride lithium-ion battery conversion electrodes.J Am Chem Soc2016;138:2838-48

[22] Hua X,Castillo-Martínez E.Revisiting metal fluorides as lithium-ion battery cathodes.Nat Mater2021;20:841-50

[23] Yang Y,Shen L.Self-assembled FeF₃ nanocrystals clusters confined in carbon nanocages for high-performance Li-ion battery cathode.J Alloy Compd2021;873:159799

[24] Santos-Ortiz R,Schmid S.Microstructure and electronic band structure of pulsed laser deposited iron fluoride thin film for battery electrodes.ACS Appl Mater Interfaces2013;5:2387-91

[25] Huang Q,Ren X.Fading mechanisms and voltage hysteresis in FeF₂-NiF₂ solid solution cathodes for lithium and lithium-ion batteries.Small2019;15:e1804670

[26] Li H,Maier J.Li-storage via heterogeneous reaction in selected binary metal fluorides and oxides.J Electrochem Soc2004;151:A1878

[27] Zhou J,Zhang X,Chen X.Carbon-nanotube-encapsulated FeF₂ nanorods for high-performance lithium-ion cathode materials.ACS Appl Mater Interfaces2014;6:21223-9

[28] Xiao AW,Capone I.Understanding the conversion mechanism and performance of monodisperse FeF₂ nanocrystal cathodes.Nat Mater2020;19:644-54

[29] Li C,Gu L.An FeF₃·0.5H₂O polytype: a microporous framework compound with intersecting tunnels for Li and Na batteries.J Am Chem Soc2013;135:11425-8

[30] Li Z,Li C,Zhang W.Hydrogen-bonding-mediated structural stability and electrochemical performance of iron fluoride cathode materials.J Mater Chem A2015;3:16222-8

[31] Conte DE,Sougrati MT,Stievano L.Operando mössbauer spectroscopy investigation of the electrochemical reaction with lithium in bronze-type FeF₃·0.33H₂O.J Phys Chem C2016;120:23933-43

[32] Li C,Tsukimoto S,Maier J.Low-temperature ionic-liquid-based synthesis of nanostructured iron-based fluoride cathodes for lithium batteries.Adv Mater2010;22:3650-4

[33] Zhang R,Wang X.Iron fluoride packaged into 3D order mesoporous carbons as high-performance sodium-ion battery cathode material.J Electrochem Soc2018;165:A89

[34] Rao R,Varadaraju U.Facile synthesis and lithium reversible insertion on iron hydrated trifluorides FeF₃·0.5H₂O.Mater Lett2016;170:130-4

[35] Jiang M,Shen Y,Fu Y.New iron-based fluoride cathode material synthesized by non-aqueous ionic liquid for rechargeable sodium ion batteries.Electrochim Acta2015;186:7-15

[36] Liu Y,Shen Q.Advanced characterizations and measurements for sodium-ion batteries with NASICON-type cathode materials.eScience2022;2:10-31

[37] Wang H,Zhang H.A green and scalable synthesis of Na₃Fe₂(PO₄)P₂O₇/rGO cathode for high-rate and long-life sodium-ion batteries.Small Methods2021;5:e2100372

[38] Yuan T,Zhang J.3D graphene decorated Na₄Fe₃(PO₄)₂(P₂O₇) microspheres as low-cost and high-performance cathode materials for sodium-ion batteries.Nano Energy2019;56:160-8

[39] Pu X,Yuan T.Na₄Fe₃(PO₄)₂P₂O₇/C nanospheres as low-cost, high-performance cathode material for sodium-ion batteries.Energy Stor Mater2019;22:330-6

[40] Sharma L,Alshareef HN.Fluorophosphates: next generation cathode materials for rechargeable batteries.Adv Energy Mater2020;10:2001449

[41] Reddy M,Chowdari B.Long-term cycling studies on 4V-cathode, lithium vanadium fluorophosphate.J Power Sources2010;195:5768-74

[42] Ellis BL,Davis LJ,Nazar LF.Structure and electrochemistry of two-electron redox couples in lithium metal fluorophosphates based on the tavorite structure.Chem Mater2011;23:5138-48

[43] Recham N,Jumas J,Armand M.Ionothermal synthesis of Li-based fluorophosphates electrodes.Chem Mater2010;22:1142-8

[44] Prabu M,Selvasekarapandian S,Chowdari B.Synthesis, impedance and electrochemical studies of lithium iron fluorophosphate, LiFePO₄F cathode.Electrochim Acta2012;85:572-8

[45] Rangaswamy P,Mahadevan MK.Comprehensive electrochemical studies of tavorite LiTiPO₄F/C electrode for rechargeable lithium ion battery.Chem Select2016;1:1472-83

[46] Nagahama M,Okada S.High voltage performances of Li₂NiPO₄F cathode with dinitrile-based electrolytes.J Electrochem Soc2010;157:A748

[47] Wang D,Xu W.Preparation and electrochemical investigation of Li₂CoPO₄F cathode material for lithium-ion batteries.J Power Sources2011;196:2241-5

[48] Amaresh S,Kim K.Facile synthesis of ZrO₂ coated Li₂CoPO₄F cathode materials for lithium secondary batteries with improved electrochemical properties.J Power Sources2013;244:395-402

[49] Xu M,Sun QQ.A 3D porous interconnected NaVPO₄F/C network: preparation and performance for Na-ion batteries.RSC Adv2015;5:40065-9

[50] Recham N,Dupont L,Armand M.Ionothermal synthesis of sodium-based fluorophosphate cathode materials.J Electrochem Soc2009;156:A993

[51] Pu X,Zhao D.Recent progress in rechargeable sodium-ion batteries: toward high-power applications.Small2019;15:e1805427

[52] Zou H,Wu X,Yang Y.Spray-drying synthesis of pure Na₂CoPO₄F as cathode material for sodium ion batteries.ECS Electrochem Lett2015;4:A53

[53] Wu L,Zhang X,Zhu X.Synthesis of carbon-coated Na₂MnPO₄F hollow spheres as a potential cathode material for Na-ion batteries.J Power Sources2018;374:40-7

[54] Hu F.Superior performance of carbon modified Na₃V₂(PO₄)₂F₃ cathode material for sodium-ion batteries.Inorg Chem Commun2021;129:108653

[55] Gover R,Burns P.The electrochemical insertion properties of sodium vanadium fluorophosphate, Na₃V₂(PO₄)₂F₃.Solid State Ion2006;177:1495-500

[56] Law M.NaVPO4F with high cycling stability as a promising cathode for sodium-ion battery.Energy Stor Mater2018;10:102-13

[57] Fang Y,Chen Z,Cao Y.Recent advances in sodium-ion battery materials.Electrochem Energy Rev2018;1:294-323

[58] Wu J,Sun X,Zhang B.The multiple effects of potassium doping on LiVPO₄F/C composite cathode material for lithium ion batteries.J Power Sources2018;396:155-63

[59] Ati M,Boulineau S.Understanding and promoting the rapid preparation of the triplite-phase of LiFeSO₄F for use as a large-potential Fe cathode.J Am Chem Soc2012;134:18380-7

[60] Tripathi R,Islam MS.Alkali-ion conduction paths in LiFeSO₄F and NaFeSO₄F tavorite-type cathode materials.Chem Mater2011;23:2278-84

[61] Recham N,Dupont L.A 3.6 V lithium-based fluorosulphate insertion positive electrode for lithium-ion batteries.Nat Mater2010;9:68-74

[62] Kim M,Lee W,Kang B.New class of 3.7 V Fe-based positive electrode materials for Na-ion battery based on cation-disordered polyanion framework.Chem Mater2018;30:6346-52

[63] Barpanda P,Recham N.Structural, transport, and electrochemical investigation of novel AMSO₄F (A = Na, Li; M = Fe, Co, Ni, Mn) metal fluorosulphates prepared using low temperature synthesis routes.Inorg Chem2010;49:7401-13

[64] Heo J,Hwang I.Amorphous iron fluorosulfate as a high-capacity cathode utilizing combined intercalation and conversion reactions with unexpectedly high reversibility.Nat Energy2023;8:30-9

[65] Lu W,Chen Z,Pan Y.A new co-solvent for wide temperature lithium ion battery electrolytes: 2,2,2-Trifluoroethyl n-caproate.J Power Sources2015;274:676-84

[66] Yang Y,Wang N.Fluorinated carboxylate ester-based electrolyte for lithium ion batteries operated at low temperature.Chem Commun2020;56:9640-3

[67] Hess S,Wachtler M.Flammability of Li-ion battery electrolytes: flash point and self-extinguishing time measurements.J Electrochem Soc2015;162:A3084

[68] Shiga T,Kondo H.Self-extinguishing electrolytes using fluorinated alkyl phosphates for lithium batteries.J Mater Chem A2017;5:5156-62

[69] Chen L,Chen H.High-stable nonflammable electrolyte regulated by coordination-number rule for all-climate and safer lithium-ion batteries.Energy Stor Mater2023;55:836-46

[70] He M,Feng Z.High voltage LiNi_0.5Mn_0.3Co_0.2O₂/graphite cell cycled at 4.6 V with a FEC/HFDEC-based electrolyte.Adv Energy Mater2017;7:1700109

[71] Lu W,Chen ZX,Zheng CM.Preparation and characterization of trifluoroethyl aliphatic carboxylates as co-solvents for the carbonate-based electrolyte of lithium-ion batteries.J Fluorine Chem2014;161:110-9

[72] Fan X,Ji X.Highly fluorinated interphases enable high-voltage Li-metal batteries.Chem2018;4:174-85

[73] Luo Y,Zhang Y,Xie J.Enhanced electrochemical performance of LiNi_0.5Mn_1.5O₄ cathode using an electrolyte with 3-(1,1,2,2-tetrafluoroethoxy)-1,1,2,2-tetrafluoropropane.J Power Sources2016;323:134-41

[74] Gu W,Dong Q.Trimethoxyboroxine as an electrolyte additive to enhance the 4.5 V cycling performance of a Ni-rich layered oxide cathode.eScience2022;2:486-93

[75] He Z,Huang F.Fluorinated Solvents for lithium metal batteries.Acta Phys Chim Sin2022;38:2205005

[76] Chen J,Li Q.Electrolyte design for LiF-rich solid-electrolyte interfaces to enable high-performance microsized alloy anodes for batteries.Nat Energy2020;5:386-97

[77] Chen L,Ai X,Chen Z.Toward wide-temperature electrolyte for lithium-ion batteries.Battery Energy2022;1:20210006

[78] Lu W,Pan Y,Zheng C.Effects of carbon-chain length of trifluoroacetate co-solvents for lithium-ion battery electrolytes using at low temperature.J Fluor Chem2013;156:136-43

[79] Liu Y,Gu W,Chen L.Surface passivation of lithium metal via in situ polymerization.Acta Physico Chimica Sinica2021;37:2004058

[80] Ma X,Hu Y,Yan F.Ionic liquid/poly(ionic liquid)-based electrolytes for lithium batteries.Ind Chem Mater2023;1:39-59

[81] Goodenough JB.Challenges for rechargeable Li batteries.Chem Mater2010;22:587-603

[82] Choudhury S.Lithium fluoride additives for stable cycling of lithium batteries at high current densities.Adv Elect Mater2016;2:1500246

[83] Zhang XQ,Xu R.Columnar lithium metal anodes.Angew Chem Int Ed2017;56:14207-11

[84] Zhao J,Shi F.Surface fluorination of reactive battery anode materials for enhanced stability.J Am Chem Soc2017;139:11550-8

[85] Lee J,Jin HS.Tuning two interfaces with fluoroethylene carbonate electrolytes for high-performance Li/LCO batteries.ACS Omega2019;4:3220-7 PMCID:PMC6648377

[86] Zhang XQ,Chen X,Zhang Q.Fluoroethylene carbonate additives to render uniform Li deposits in lithium metal batteries.Adv Funct Mater2017;27:1605989

[87] Chen Y,Chen L.“One stone two birds” design for hollow spherical Na₄Fe₃(PO₄)₂P₂O₇/C cathode enabled high-performance sodium-ion batteries from iron rust.EcoMat2023;5:e12393

[88] Wen Y,Luo B.Long-term cycling performance of nitrogen-doped hollow carbon nanospheres as anode materials for sodium-ion batteries.Eur J Inorg Chem2016;2016:2051-5

[89] Veith GM,Sacci RL,Baldwin JK.Determination of the solid electrolyte interphase structure grown on a silicon electrode using a fluoroethylene carbonate additive.Sci Rep2017;7:6326 PMCID:PMC5524684

[90] Choi N,Lee KY,Kim H.Effect of fluoroethylene carbonate additive on interfacial properties of silicon thin-film electrode.J Power Sources2006;161:1254-9

[91] He M,Hobold GM,Gallant BM.The intrinsic behavior of lithium fluoride in solid electrolyte interphases on lithium.Proc Natl Acad Sci USA2020;117:73-9 PMCID:PMC6955333

[92] Miao R,Feng X,Wang J.Novel dual-salts electrolyte solution for dendrite-free lithium-metal based rechargeable batteries with high cycle reversibility.J Power Sources2014;271:291-7

[93] Yang G,Liu S,Wang Z.LiFSI to improve lithium deposition in carbonate electrolyte.Energy Stor Mater2019;23:350-7

[94] Yamada Y,Ko S,Yamada A.Advances and issues in developing salt-concentrated battery electrolytes.Nat Energy2019;4:269-80

[95] Wang J,Sodeyama K.Fire-extinguishing organic electrolytes for safe batteries.Nat Energy2018;3:22-9

[96] Piao N,Xu H.Countersolvent electrolytes for lithium-metal batteries.Adv Energy Mater2020;10:1903568