Modified ionic liquids containing cyclic phosphorus moiety

Abstract

To provide a phosphorus-modified ionic liquid compound, synthesis thereof, and an electrochemical cell electrolyte containing the cyclic phosphorus-modified ionic liquid compound.SOLUTION: An ionic liquid compound comprises anions and cations. The cations have at least one cyclic phosphorus moiety. According to one aspect, an electrolyte for use in an electrical storage device is provided which comprises an aprotic organic solvent, a metal salt, a passivating additive, and an ionic liquid compound having at least one cyclic phosphorus moiety.SELECTED DRAWING: None

Description

[Technical field]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS This application was filed on March 19, 2019, and is incorporated herein by reference in its entirety. This application claims the benefit of the filing date of U.S. Provisional Patent Application No. 62 / 820,609, which is incorporated herein by reference.

[0002] The present disclosure relates to ionic liquids in which the cation comprises a cyclic phosphorus moiety, and electrochemical methods comprising the ionic liquids. This relates to electrolytes for batteries. [Background technology]

[0003] Recent advances in the synthesis and electrochemical analysis of room-temperature ionic liquids (ILs) have highlighted the potential of this unique species. This study establishes the potential of this class of material as an electrolyte for next-generation lithium-ion batteries. It is an organic salt with a melting point below 100°C, and is generally composed of bulky cations and inorganic anions. The large cation size leads to charge delocalization and screening, As a result, the lattice energy is reduced, thereby lowering the melting point or glass transition temperature. They have negligible vapor pressure, non-flammability, good room temperature ionic conductivity, a wide electrochemical window, and favorable They have inherent physicochemical properties, including favorable chemical and thermal stability. It would be desirable to provide an IL-based electrolyte for lithium batteries.

[0004] However, there are concerns over the flammability of lithium-ion batteries, even under normal or misuse conditions. Safety issues remain. Chi-Cheung Su et al. However, the present invention teaches the use of electrolyte compositions containing ionic liquids or moieties containing cyclic phosphorus moieties. There is no mention of the use of ionic liquids covalently bonded to lithium ions. In order to impart flame retardant properties to lithium batteries, it is necessary to incorporate new ionic liquids. To extract more capacity from the i-ion cathode, the operating voltage needs to be increased. However, current generation electrolytes are not stable above 4.2V. Summary of the Invention

[0005] The present disclosure provides a compound comprising an anion and a cation, the cation binding to at least one cyclic phosphorus moiety. The present invention relates to an ionic liquid having the following properties.

[0006] According to one aspect of the present disclosure, there is provided an electrolyte for use in an electricity storage device, the electrolyte comprising: An ionic liquid comprising an organic solvent, a metal salt, a passivation additive, and at least one cyclic phosphorus moiety. An electrolyte is provided that includes a soluble ion exchange compound.

[0007] According to another aspect of the present disclosure, there is provided an electrolyte in an electrical energy storage device, the electrolyte comprising: aprotic organic solvent; a metal salt; a passivation additive; and at least one cyclic phosphorus moiety. and an ionic liquid compound containing an organic solvent, the organic solvent being an open-chain or cyclic carbonate, carboxylic acid, Acid esters, nitrites, ethers, sulfones, sulfoxides, ketones, lactones, di Xolane, glyme, crown ether, siloxane, phosphate ester, phosphate, phosphat The polymer may be a sphite, a mono- or polyphosphazene, or a mixture thereof.

[0008] According to another aspect of the present disclosure, there is provided an electrolyte in an electrical energy storage device, the electrolyte comprising: aprotic organic solvent; a metal salt; a passivation additive; and at least one cyclic phosphorus moiety. The ionic liquid compound includes a metal salt having a cation of lithium, sodium, or aluminum. The metal salt is an alkali metal salt or an alkaline earth metal salt. could be.

[0009] According to another aspect of the present disclosure, there is provided an electrolyte in an electrical energy storage device, the electrolyte comprising: aprotic organic solvent; a metal salt; a passivation additive; and at least one cyclic phosphorus moiety. and an ionic liquid compound containing a sulfur-containing compound, a phosphorus-containing compound, compounds, boron-containing compounds, silicon-containing compounds, compounds containing at least one unsaturated carbon-carbon bond The compounds include compounds containing carboxylic acids, carboxylic acid anhydrides or mixtures thereof.

[0010] These and other aspects of the disclosure will become apparent upon consideration of the following detailed description and appended claims. It will become clear by doing so. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0011] The present disclosure provides a method for preparing a compound comprising at least one cation and at least one anion, Another cation is covalently bonded to at least one cyclic phosphorus moiety in the ionic liquid compound. Pertaining to things.

[0012] In one embodiment, the electrolyte of the electrical energy storage device comprises: a) an aprotic organic solvent system; b) a metal salt; c) a passivation additive; and d) at least one cation and at least one The present invention relates to ionic liquid compounds that include two anions, where at least one cation is at least one of the cations. It is covalently bonded to at least one cyclic phosphorus moiety.

[0013] In one embodiment, the ionic liquid compound comprises an anion; and a cyclic phosphorus moiety according to Formula A or B. containing a cation bound to [ka] During the ceremony, CAT + are pyrrolidinium, piperzinium, azepanium, onium, sulfonium Nitrogen, phosphonium, imidazolium, pyridine, or a ring member having nitrogen, oxygen, silicon or a 5- or 6-membered heterocyclic ring having 1 to 3 heteroatoms, including sulfur; R and R1 are independently hydrogen, C1-C8 alkyl, perfluoroalkyl, alkoxy, yl, alkoxy, aryl, alkynyl, alkylsiloxy, phenyl, benzyl, silyl alkyl, thioether, sulfoxide, azo, amino or silane groups, or hydrogen atom may be optionally substituted with a halide, alkyl, alkenyl, alkoxy, or a Aryl, alkynyl, alkylsiloxy, phenyl, benzyl, silyl, thioether, further substituted with sulfoxide, azo, amino or silane; X is (a) a linker, and is a C1-C8 alkyl, alkenyl, alkynyl, or alkynyl group. koxy, ester, carbonyl, phenyl, thioether, sulfoxide, azo or aryl any of the carbon or hydrogen atoms may be optionally further substituted with a halide. (b) an O, S, N, or C bonded to the linker; or (c) an O bonded to the linker. , S, N, or C.

[0014] Suitable anions (A - ) include halides (e.g., Cl, Br) , nitrates (e.g., NO3), phosphates (e.g., PF6, TFOP), imides (e.g. TFSI, BETI), borate (e.g. BOB, BF4), aluminate , arsenide, cyanide, thiocyanate, nitrite, benzoate, carbonate, Lorate, chlorite, chromate, sulfate, sulfite, silicate, thioxa Ruthenates, chalcogenides, pnictogenides, crystallo genide), oxalate, acetate, formate, or hydroxide. , but not limited to these.

[0015] The present disclosure relates to methods for synthesizing cations based on cyclic phosphorus moieties, and to the synthesis of such functionalized cations. The present invention further includes the use of the compounds in ionic liquids for electrochemical cells. It provides the electrolyte with great thermal stability.

[0016] Suitable electrolyte metal salts include alkali metal salts or alkaline earth metal salts. In one embodiment, the cation of the alkali metal salt comprises lithium or sodium. In the form, the cation of the metal salt includes aluminum or magnesium.

[0017] In some embodiments, the electrolyte includes a lithium salt in addition to the ionic liquid. For example, Li[CF3CO2];Li[C2F5CO2];Li[ClO4];Li[BF4]; Li[AsF6];Li[PF6];Li[PF2(C2O4)2];Li[PF4C2 O4];Li[CF3SO3];Li[N(CP3SO2)2];Li[C(CF3SO 2)3];Li[N(SO2C2F5)2];Lithium alkyl fluorophosphate;Li[ B(C2O4)2];Li[BF2C2O4];Li2[B 12 Z 12-j H j Li 2[B 10 X 10-j’ H j’ or a mixture of any two or more thereof; Lithium salts can be used, where Z is an independent halogen at each occurrence. where j is an integer from 0 to 12, and j' is an integer from 1 to 10.

[0018] In some applications of the electrolyte, such as in lithium-ion batteries, aprotic solvents The combination of a solvent with the ionic liquid reduces the viscosity of the electrolyte and improves its conductivity. Suitable aprotic solvents are those that lack an exchangeable proton and are cyclic carbonates, linear carbonates, etc. Ster, phosphate ester, oligoether substituted siloxane / silane, cyclic ether, linear Ethers, lactone compounds, linear esters, nitrile compounds, amide compounds, sulfonated compounds Compounds, siloxanes, phosphoric acid esters, phosphates, phosphites, mono- or polyphosphides These solvents are used alone or in combination of at least two or more. It is possible.

[0019] Suitable aprotic organic solvents include open-chain or cyclic carbonates, carboxylic acid esters, Nitrites, ethers, sulfones, ketones, lactones, dioxolanes, grims, crowns Ethers, siloxanes, phosphate esters, phosphites, mono- or polyphosphazenes or mixtures thereof.

[0020] Examples of aprotic solvents or carriers for forming the electrolyte system include, but are not limited to, , dimethyl carbonate, ethyl methyl carbonate, diethyl carbonate, methyl Propyl carbonate, ethyl propyl carbonate, dipropyl carbonate, bis(t (trifluoroethyl) carbonate, bis(pentafluoropropyl) carbonate, tri Fluoroethyl methyl carbonate, pentafluoroethyl methyl carbonate, hepta Fluoropropyl methyl carbonate, perfluorobutyl methyl carbonate, trifluoro Fluoroethyl ethyl carbonate, pentafluoroethyl ethyl carbonate, heptaf Perfluoropropyl ethyl carbonate, perfluorobutyl ethyl carbonate, etc. oligomers, methyl propionate, ethyl propionate, butyl propionate, Dimethoxyethane, triglyme, dimethylvinylene carbonate, tetraethylene glycol Coal, Dimethyl Ether, Polyethylene Glycol, Triphenyl Phosphate, Tri Butyl phosphate, Hexafluorocyclotriphosphazene, 2-ethoxy-2,4, 4,6,6-Pentafluoro-1,3,5,2-5,4-5,6-5 Triazatriphosph finine, triphenyl phosphite, sulfolane, dimethyl sulfoxide, ethyl methyl Sulfone, ethyl vinyl sulfone, allyl methyl sulfone, divinyl sulfone, fluoro These include phenylmethylsulfone, and gamma-butyrolactone.

[0021] In some embodiments, the electrolyte further comprises an additive to protect the electrodes from degradation. Therefore, the electrolyte of the present technology is reduced or polymerized on the surface of the negative electrode, The electrolyte may also contain additives that form a passivation film on the surface of the positive electrode. or may contain an additive that can be polymerized to form a passivation film on the surface of the positive electrode. In some embodiments, the electrolyte of the present technology further comprises a mixture of two types of additives. include.

[0022] In some embodiments, the additive comprises at least one oxygen atom and at least one Substituted or unsubstituted straight chain, branched or cyclic carbonyl groups, including aryl, alkenyl or alkynyl groups. The passivation film formed from such an additive also has a structure in which the additive is at least one Substituted aryl compounds or substituted or unsubstituted heteroaryl compounds containing one oxygen atom Alternatively, two additives may be used in combination. In some such embodiments, one ion and the other additive passivate the anode surface. In particular, the catalyst may be selected to prevent or reduce reduction of metal ions at the anode.

[0023] Suitable passivation additives include sulfur-containing compounds, phosphorus-containing compounds, and boron-containing compounds. , silicon-containing compounds, fluorine-containing compounds, nitrogen-containing compounds, at least one unsaturated carbon -carbon bond-containing compounds, carboxylic acid anhydrides or mixtures thereof.

[0024] Representative additives include glyoxal bis(diallyl acetal), tetra(ethylene glycol) divinyl ether, 1,3,5-triallyl-1,3,5-triazine-2 ,4,6(1H,3H,5H)-trione, 1,3,5,7-tetravinyl-1,3,5 ,7-Tetramethylcyclotetrasiloxane, 2,4,6-Triaryloxy-1,3, 5-Triazine, 1,3,5-triacryloylhexahydro-1,3,5-triazine , 1,2-divinylfuroate, 1,3-butadiene carbonate, 1-vinylazetidin 1-vinylaziridin-2-one, 1-vinylpiperidin-2-one, 1 -Vinylpyrrolidin-2-one, 2,4-divinyl-1,3-dioxane, 2-amino- 3-Vinylcyclohexanone, 2-Amino-3-vinylcyclopropanone, 2-Amino-4 -vinylcyclobutanone, 2-amino-5-vinylcyclopentanone, 2-aryloxy cyclopropanone, 2-vinyl-[1,2]oxazetidine, 2-vinylaminocyclo Hexanol, 2-vinylaminocyclopropanone, 2-vinyloxetane, 2-vinyl Oxy-cyclopropanone, 3-(N-vinylamino)cyclohexanone, 3,5-divinyl Nylfuroate, 3-vinylazetidin-2-one, 3-vinylaziridin-2-one, 3 -vinylcyclobutanone, 3-vinylcyclopentanone, 3-vinyloxaziridine, 3 -Vinyloxetane, 3-vinylpyrrolidin-2-one, 2-vinyl-1,3-dioxo Ran, acrolein diethyl acetal, acrolein dimethyl acetal, 4,4-di Vinyl-3-dioxolan-2-one, 4-vinyltetrahydropyran, 5-vinylpiperidine Lysin-3-one, Allyl glycidyl ether, Butadiene monoxide, Butyl-vinyl Divinyl ether, dihydropyran-3-one, divinyl butyl carbonate, divinyl carbamazepine divinyl ethylene carbonate, Divinylethylene silicate, divinylethylene sulfate, divinylethylene sulfide Fite, divinyl methoxypyrazine, divinyl methyl phosphate, divinyl propylene Carbonate, ethyl phosphate, methoxy-o-terphenyl, methyl phosphate , oxetan-2-yl-vinylamine, oxiranylvinylamine, vinylcarbonate Vinyl crotonate, vinyl cyclopentanone, vinyl ethyl 2-furoate, Vinyl ethylene carbonate, vinyl ethylene silicate, vinyl ethylene sulfate, Vinyl ethylene sulfite, vinyl methacrylate, vinyl phosphate, vinyl-2 -furoate, vinylcyclopropanone, vinyl ethylene oxide, β-vinyl-γ-butanone In some embodiments, the compound may be tyrolactone, tyrolactone, or a mixture of any two or more thereof. The additives are F, alkyloxy, alkenyloxy, aryloxy, methoxy, and a The aryloxy group may be a cyclotriphosphazene substituted with an alkyloxy group or a combination thereof. For example, the additive may be (divinyl)-(methoxy)(trifluoro)cyclotriphosphatase. (trivinyl)(difluoro)(methoxy)cyclotriphosphazene, (vinyl)( Methoxy)(tetrafluoro)cyclotriphosphazene, (aryloxy)(tetrafluoro (diaryloxy)(trifluoro)cyclotriphosphazene, b) (Methoxy)cyclotriphosphazene compounds, or mixtures of two or more of such compounds. In some embodiments, the additive may be vinyl ethylene carbonate, vinyl diphenyl carbonate, or 1,2-diphenyl ether, or any 2 of such compounds It is a mixture of more than one.

[0025] Other typical additives include phenyl, naphthyl, anthracenyl, pyrrolyl, oxy Sazolyl, furanyl, indolyl, carbazolyl, imidazolyl, thiophenyl, fluorine Carbonate, sultone, sulfide, anhydride, silane, siloxy, phosphate or Examples of additives include compounds having a phosphite group. Methyl sulfide, fluoroethylene carbonate, 1,3,2-dioxathiolane 2, 2-dioxide, 1-propene 1,3-sultone, 1,3-propane sultone, 1,3- Dioxolan-2-one, 4-[(2,2,2-trifluoroethoxy)methyl], 1, 3-Dioxolan-2-one, 4-[[2,2,2-trifluoro-1-(trifluoro Methyl)ethoxy]methyl]-, methyl 2,2,2-trifluoroethyl carbonate, Nonafluorohexyltriethoxysilane, Octamethyltrisiloxane, Methyltris (Trimethylsiloxy)silane, Tetrakis(trimethylsiloxy)silane, (Trideca Fluoro-1,1,2,2-tetrahydrooctyl)triethoxysilane, Tris(1H 1H-heptafluorobutyl)phosphate, 3,3,3-trifluoropropyl triphosphate Silane (3,3,3-trifluoropropyldimethylsiloxy)silane, (3,3,3-trifluoropropyldimethylsiloxy)silane Fluoropropyl)trimethoxysilane, trimethylsilyltrifluoromethanesulfonate phosphate, tris(trimethylsilyl)borate, tripropyl phosphate, bis(trimethylsilyl)borate (Thiylsilylmethyl)benzylamine, Phenyltris(trimethylsiloxy)silane, 1 ,3-Bis(trifluoropropyl)tetramethyldisiloxane, triphenylphospha phosphate, tris(trimethylsilyl)phosphate, tris(1H,1H,5H-octaphenyl Phosphate, triphenyl phosphite, trilauryl trithiophos Phite, tris(2,4-di-tert-butylphenyl)phosphite, tri-p- Tolyl phosphite, tris(2,2,3,3,3-pentafluoropropyl)phospha ester, succinic anhydride, 1,5,2,4-dioxadithiane 2,2,4,4-tetraoxy , tripropyl trithiophosphate, aryloxypyrrole, aryloxyethy Rensulfate, aryloxypyrazine, aryloxy-carbazole trivinyl Phosphate, aryloxy-ethyl-2-furoate, aryloxy-o-terf Phenyl, aryloxy-pyridazine, butyl-aryloxy-ether, divinyldi Phenyl ether, (tetrahydrofuran-2-yl)-vinylamine, divinylmeth Sibipyridine, Methoxy-4-vinylbiphenyl, Vinylmethoxycarbazole, Vinyl Methoxypiperidine, vinyl methoxypyrazine, vinyl methyl carbonate-aryl , vinylpyridazine, 1-divinylimidazole, 3-vinyltetrahydrofuran, Divinylfuran, divinylmethoxyfuran, divinylpyrazine, vinylmethoxyimidazo vinyl methoxypyrrole, vinyl tetrahydrofuran, 2,4-divinyl isopropyl alcohol xazole, 3,4-divinyl-1-methylpyrrole, aryloxyoxetane, aryl Aryloxy-phenyl carbonate, aryloxy-piperidine, aryloxy-tetraacetate Hydrofuran, 2-aryl-cyclopropanone, 2-diaryloxy-furoate , 4-arylanisole, aryloxy-carbazole, aryloxy-2-floor aryloxy-crotonate, aryloxy-cyclobutane, aryloxy -Cyclopentanone, aryloxy-cyclopropanone, aryloxy-cyclophos phazene, aryloxy-ethylene silicate, aryloxy-ethylene sulfur , aryloxy-ethylene sulfite, aryloxy-imidazole, aryl Oxymethacrylate, aryloxyphosphate, aryloxypyrrole, aryl Diaryloxyquinoline, diaryloxycyclotriphosphazene, diaryloxyethylene Diaryloxycarbonate, diaryloxyfuran, diaryloxymethylphosphate, Diaryloxy-butyl carbonate, diaryloxy-crotonate, diaryloxy Diphenyl ether, diaryloxy-ethyl silicate, diaryloxy-ethyl Diaryloxyethylene silicate, diaryloxy-ethylene sulfate, diaryloxyethylene Diaryloxy-phenylcarbonate, Diaryloxy-propyl diphenyl carbonate, diphenyl diaryloxy silicate, Diphenyl divinyl silicate, diphenyl ether, diphenyl silicate, divinyl Methoxydiphenyl ether, divinyl phenyl carbonate, methoxycarbazole, or 2,4-dimethyl-6-hydroxy-pyrimidine, vinylmethoxyquinoline, pyridinium azine, vinylpyridazine, quinoline, vinylquinoline, pyridine, vinylpyridine, Dole, vinylindole, triethanolamine, 1,3-dimethylbutadiene, buta Diene, vinyl ethylene carbonate, vinyl carbonate, imidazole, vinyl imine Dazole, piperidine, vinylpiperidine, pyrimidine, vinylpyrimidine, pyrazine, Vinylpyrazine, isoquinoline, vinylisoquinoline, quinoxaline, vinylquinoxalin benzene, biphenyl, 1,2-diphenyl ether, 1,2-diphenylethane, ophthalmidine nyl, N-methylpyrrole, naphthalene, or a mixture of any two or more of such compounds It can be a thing.

[0026] In one embodiment, the electrolyte of the present technology comprises an aprotic gel polymer carrier / solvent. Suitable gel polymer carriers / solvents include polyethers, polyethylene oxides, polyimides, and the like. Polyphosphazine, polyacrylonitrile, polysiloxane, polyether graft Polysiloxanes, derivatives of the above, copolymers of the above, crosslinked Suitable ionic electrolytes include bridge and network structures, blends of the foregoing, etc. Salt is added. Other gel polymer carriers / solvents include polypropylene oxide, poly Siloxane, sulfonated polyimide, perfluorinated membrane (Nafion resin), divinylpolyether Polyethylene glycol, polyethylene glycol-bis-(methyl acrylate), polyethylene ethylene glycol-bis(methyl methacrylate), derivatives of the above, and the above Copolymers of the above, as well as polymer matrices derived from crosslinking and network structures of the above. Examples include those prepared from cocos.

[0027] Functional ionic liquids and salt-containing electrolytes have high electrical conductivity and solubility in organic solvents. It is suitable for use as an electrolyte for chemical devices. An example of an electrochemical device is an electric double layer capacitor. secondary batteries, dye-sensitized solar cells, electrochromic devices and capacitors. This list is not limiting. Particularly suitable electrochemical devices are dual-electrochemical devices. layer capacitors and secondary batteries, such as lithium ion batteries.

[0028] In yet another aspect, a cathode, an anode, and an electrode comprising an ionic liquid as described herein. In one embodiment, the electrochemical device comprises a lithium secondary battery. In some embodiments, the secondary battery is a lithium battery, a lithium ion battery, or the like. , lithium-sulfur battery, lithium-air battery, sodium-ion battery or magnesium battery In some embodiments, the electrochemical device is an electrochemical battery, such as a capacitor. In some embodiments, the capacitor is an asymmetric capacitor or a supercapacitor. In some embodiments, the electrochemical cell is a primary cell. So the primary battery is a Lithium / MnO2 battery or a Li / poly(carbon monofluoride) battery. In some embodiments, the electrochemical cell is a solar cell.

[0029] Suitable cathodes include, but are not limited to, lithium metal oxides, spinels, cans, etc. Lithosite, carbon-coated olivine, LiFePO4, LiCoO2, LiNiO2, LiNi x Co y Met z O2, LiMn 0.5 Ni 0.5 O2, LiMn 0.3 Co 0.3 Ni 0.3 O2, LiMn2O4, LiFeO2, Li 1+x’ Ni α Mn β Co γ Met' δ O 2-z’ F z’ , A n’ B2(XO4) 3( NASICON), vanadium oxide, Lithium oxide, sulfur, polysulfides, lithium carbon monofluoride (also known as LiCFx) or a mixture of any two or more thereof, where Met is Al, Mg, T i, B, Ga, Si, Mn or Co; Met' is Mg, Zn, Al, Ga, B, Zr or Ti, and A is Li, Ag, Cu, Na, Mn, Fe, Co, Ni, Cu or is Zn, B is Ti, V, Cr, Fe or Zr, and X is P, S, Si, W or is Mo, 0≦x≦0.3, 0≦y≦0.5, 0≦z≦0.5, 0≦x'≦0.4, 0≦α≦1, 0≦β≦1, 0≦γ≦1, 0≦δ≦0.4, 0≦z'≦0.4, and 0≦n According to some embodiments, the spinel is Li 1+x Mn 2-z Met ''' y O 4-m X' n wherein Me″ is a spinel manganese oxide having the formula ' is Al, Mg, Ti, B, Ga, Si, Ni or Co, and X' is S or F. 0≦x≦0.3, 0≦y≦0.5, 0≦z≦0.5, 0≦m≦0.5, and 0≦n≦ In another embodiment, the olivine is Li 1+x Fe 1z Met'' y PO 4-m X' n where Met″ is Al, Mg, Ti, B, Ga, Si, N i, Mn or Co, X' is S or F, 0≦x≦0.3, 0 0≦y≦0. 5, 0≦z≦0.5, 0≦m≦0.5 and 0≦n≦0.5.

[0030] Suitable anodes include lithium metal, graphite materials, amorphous carbon, Li4Ti5O 12 ,vinegar Zinc alloys, silicon alloys, intermetallic compounds, or mixtures of any two or more of such materials. Suitable graphite materials include natural graphite, synthetic graphite, graphitized mesocarbon micrographite, and graphitized graphite. Examples include robeads (MCMB) and graphite fibers, as well as any amorphous carbon material. In some embodiments, the anode and cathode are separated from each other by a porous separator. can be.

[0031] Lithium battery separators are often microporous polymer membranes. Examples of polymers for forming the polymer include nylon, cellulose, nitrocellulose, poly Sulfone, polyacrylonitrile, polyvinylidene fluoride, polypropylene, polyethylene polybutene, polybutene, or a copolymer or blend of any two or more of such polymers. In some examples, the separator may include an electron beam treated microporous The separator is a polyolefin separator. The deformation temperature of the separator is improved by electronic processing. Therefore, the performance of the separator at high temperatures can be improved. Alternatively or additionally, the separator may be a shutdown separator. The separator is designed to withstand temperatures up to about 130°C so that the electrochemical cell can operate at temperatures up to about 130°C. The trigger temperature may exceed

[0032] Example – Synthesis of Pyr12O-DOP PF6: [ka] Step 1: A 100 mL three-neck round-bottom flask equipped with a stir bar, thermocouple, water-cooled condenser, and nitrogen inlet. In a RBF, 18 mL of 2-chloro-1,3,2-tetrahydrofuran (THF) was added. The flask was placed in an ice-water bath, and the inside of the flask was cooled to room temperature. The temperature was kept below 4° C. Then, 5 ml of triethylamine (Et3N) in THF was added The flask was added with stirring in an ice-water bath to 1-(2-hydroxyethyl) Ethyl)pyrrolidine was added to the mixture and the exotherm was monitored to 20°C. Some white solid formed while stirring in the water bath for 30 min. The mixture was allowed to warm to room temperature. The mixture was slowly heated at 40° C. and stirred for 4 hours. The by-product was filtered off, and the filtrate was The mixture was concentrated using an evaporator. Process 2: Quaternization The filtrate was then added to a RBF containing 10 mL of dichloromethane (DCM). methyl iodide in DCM was added to the flask via pipette. The reaction mixture became cloudy and A yellow oil was formed. The mixture was stirred at room temperature overnight. The DCM layer was decanted and the remaining yellow oil was The colored oil was washed twice with DCM. The oil was concentrated on a rotary evaporator. The following proton NMR (DMSO, 500 MHz) peaks were recorded for the oil:

number

number

[0033] Although various embodiments have been illustrated and described in detail herein, it is to be understood that the present disclosure is not limited to the above-described embodiments. Various modifications, additions, substitutions, etc. may be made without departing from the spirit and scope of the present invention, and therefore these are subject to the following characteristics: It will be apparent to one skilled in the art that the present invention is considered to be within the scope of the disclosure defined in the claims. Wax. One embodiment of the present invention will be described below, but the present invention is not limited thereto. [Invention 1] An ionic liquid compound, anion; and Cation attached to a cyclic phosphorus moiety according to formula A or B Including, [C1] JPEG2025016696000005.jpg4477 During the ceremony, CAT + are pyrrolidinium, piperzinium, azepanium, onium, imidazolium pyridine, or 1-3 heterocyclic rings containing nitrogen, oxygen, silicon or sulfur as ring members A 5- or 6-membered heterocyclic ring having a cyclic atom; R and R1 are independently hydrogen, C1-C8 alkyl, perfluoroalkyl, alkoxy, yl, alkoxy, aryl, alkynyl, alkylsiloxy, phenyl, benzyl, silyl alkyl, thioether, sulfoxide, azo, amino or silane groups, or hydrogen atom may be optionally substituted with a halide, alkyl, alkenyl, alkoxy, or a Aryl, alkynyl, alkylsiloxy, phenyl, benzyl, silyl, thioether, further substituted with sulfoxide, azo, amino or silane; X is (a) a linker, and is a C1-C8 alkylene, alkenylene, or alkynylene. , alkyleneoxy, ester, carbonyl, phenyl, thioether, sulfoxide, azo or aryl groups, in which either the carbon or hydrogen atoms are optionally halogenated (b) a linker further substituted with O or S; or (c) a linker bonded to the linker is O or S, A - are halides, nitrates, phosphates, imides, borates, aluminates , arsenide, cyanide, thiocyanate, nitrite, benzoate, carbonate, Lorate, chlorite, chromate, sulfate, sulfite, silicate, thioxa Ruthenates, chalcogenides, pnictogenides, crystallo genide), oxalate, acetate, formate or hydroxide be, Ionic liquid compounds. [Invention 2] The anion is a halide, an aluminate, an arsenide, a cyanide, a thiocyanate, , nitrite, benzoate, chlorate, chlorite, chromate, sulfate, sa sulphite, silicate, thiosulphate, oxalate, acetate, formate, The compounds according to invention 1, including hydroxides, nitrates, phosphates, imides, or borates. Compound. [Invention 3] The compound according to claim 1, wherein the onium is a sulfonium or a phosphonium. [Invention 4] 1. An electrolyte for an electrical energy storage device, comprising: a) aprotic organic solvent systems; b) metal salts; c) passivation additives; and d) The ionic liquid compound according to invention 1 14. An electrolyte for an electrical energy storage device comprising: [Invention 5] The anion is a halide, an aluminate, an arsenide, a cyanide, a thiocyanate, , nitrite, benzoate, chlorate, chlorite, chromate, sulfate, sa sulphite, silicate, thiosulphate, oxalate, acetate, formate, The electrode according to invention 4, which includes a hydroxide, a nitrate, a phosphate, an imide, or a borate. Desolation. [Invention 6] The aprotic organic solvent is an open-chain or cyclic carbonate, a carboxylic acid ester, a nitrile, Light, ether, sulfone, ketone, lactone, dioxolane, grim, crown ace ter, siloxane, phosphate ester, phosphite, mono- or polyphosphazene or The electrolyte according to invention 4, comprising a mixture thereof. [Invention 7] 5. The electrolyte according to claim 4, wherein the metal salt comprises an alkali metal salt or an alkaline earth metal salt. [Invention 8] The cation of the alkali metal salt comprises lithium or sodium. Electrolytes. [Invention 9] The electrode according to claim 4, wherein the cation of the metal salt contains aluminum or magnesium. Desolation. [Invention 10] The passivation additive may be a sulfur-containing compound, a phosphorus-containing compound, a boron-containing compound, a silicon-containing compound, containing compounds, fluorine-containing compounds, nitrogen-containing compounds, compounds with at least one unsaturated carbon-carbon bond The electrolytic method according to claim 4, comprising a compound containing a carboxylic acid anhydride or a mixture thereof. quality.

Claims

[Claim 1] The invention described in this specification.

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