Phosphorus containing electrolytes

Abstract

The present disclosure is directed to phosphorus based thermal runaway inhibiting (TRI) materials, the synthesis thereof and an electrochemical cell electrolyte containing the phosphorus based materials.

Description

FIELD

This disclosure is directed towards phosphorus based thermal runaway inhibiting (TRI) materials, electrolytes containing the materials, and electrical energy storage device containing the electrolytes.

BACKGROUND

Despite the recent progress and improvements in safety of the lithium ion batteries (such as PTC, CID, shutdown separators), chemical shuttles, cathode additives etc. used in portable electronics, there are still safety concerns associated with the high energy density large scale batteries for electric vehicles and consumer applications. Flame retardant additives are added to the electrolyte to prevent or delay the onset of thermal runaway in the battery due mechanical, electrical or thermal abuse.

However, there are still safety challenges such as flammability of lithium-ion batteries under abuse conditions or even normal conditions. U.S. Pat. No. 5,830,600 to Narang et al. and U.S. Pat. No. 8,795,903 to Smart et al. teach the use of flame retardant electrolyte compositions containing select phosphate-based non-aqueous solvents. Therefore, there is a need to incorporate novel multi-functional TRI additives to improve the safety of high energy lithium ion batteries and lithium metal anode batteries.

SUMMARY

This disclosure is directed towards phosphorus based thermal runaway inhibiting (TRI) materials, electrolytes containing the materials, and electrochemical cells containing the electrolytes.

In accordance with one aspect of the present disclosure, there is provided an electrolyte for use in an electrical storage device, the electrolyte includes an aprotic organic solvent, an alkali metal salt, an additive and TRI compound that contains at least one phosphorus moiety.

In accordance with another aspect of the present disclosure, there is provided an electrolyte in an electrical energy storage device, the electrolyte includes an aprotic organic solvent, an alkali metal salt, an additive and a TRI compound that contains at least one phosphorus moiety, wherein the organic solvent is open-chain or cyclic carbonates, carboxylic acid esters, nitrites, ethers, sulfones, sulfoxides, ketones, lactones, dioxolanes, glymes, crown ethers, siloxanes, phosphoric acid esters, phosphates, phosphites, mono- or polyphosphazenes or mixtures thereof.

In accordance with another aspect of the present disclosure, there is provided an electrolyte in an electrical energy storage device, the electrolyte includes an aprotic organic solvent, an alkali metal salt, an additive and the TRI compound that contains at least one phosphorus moiety, wherein the cation of the alkali metal salt is lithium, sodium, aluminum or magnesium.

In accordance with another aspect of the present disclosure, there is provided an electrolyte in an electrical energy storage device, the electrolyte including an aprotic organic solvent, an alkali metal salt, an additive and a TRI compound that contains at least one phosphorus moiety, wherein the additive contains sulfur-containing compounds, phosphorus-containing compounds, boron-containing compounds, silicon-containing compounds, compounds containing at least one unsaturated carbon-carbon bond, carboxylic acid anhydrides or mixtures thereof.

These and other aspects of the present disclosure will become apparent upon a review of the following detailed description and the claims appended thereto.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a graph of room temperature cycle life comparison between a Comparative Example 0 electrolyte and Electrolyte 2 containing a phosphorus based thermal runaway inhibiting (TRI) materials;

FIG. 2 is a photograph of a nail penetration setup; and

FIG. 3 is a pair of photographs of punctured cells containing commercial electrolyte (EC:EMC 3:7 1M LiPF₆) of Comparative Example 01 and electrolyte of Example 11 containing NMC532 pouch cells.

DETAILED DESCRIPTION

This disclosure is directed phosphorus based thermal runaway inhibiting (TRI) materials, electrolytes containing the materials, and electrochemical cells containing the electrolytes.

In an embodiment, an electrical energy storage device electrolyte includes a) an aprotic organic solvent system; b) an alkali metal salt; and c) a phosphorus based TRI materials.

In an embodiment, an electrical energy storage device electrolyte includes a) an aprotic organic solvent system; b) an alkali metal salt; c) an additive; and d) a phosphorus based TRI materials.

In an embodiment, the molecular structures of a phosphorus based TRI materials are depicted below:

wherein:

A is oxygen or sulfur;

Ph is a phenyl group;

L is oxygen or sulfur;

x and y are either 1 or 2, but must sum to equal 3;

R is a phenyl ring with at least one of the hydrogen atoms on the ring substituted with a halogen, methyl, methoxy, silyl, amide, perfluorinated alkyl, silane, sulfoxide, azo, ether or thioether group or combination thereof.

In an embodiment, the phosphorous containing TRI material is present in an amount of from about 0.01 wt. % to about 60 wt. %.

In an embodiment, an electrolyte includes a TRI phosphorus compound, an alkali metal, such as lithium, an additive and an aprotic solvent for use in an electrochemical cell. The ionic liquid contains an organic cation and an inorganic/organic anion, with suitable organic cations including N-alkyl-N-alkyl-pyrrolidinium, N-alkyl-N-alkyl-pyridnium, N-alkyl-N-alkyl-sulfonium, N-alkyl-N-alkyl-ammonium, N-alkyl-N-alkyl-piperdinium or the like, and suitable anions including tetrafluoroborate, hexafluorophosphate, bis(trifluoromethylsulfonyl)imide, bis(pentafluoroethylsulfonyl)imide, trifluoroacetate or the like. The polymer in the electrolyte includes poly(ethylene glycol) derivatives, with varying molecular weights ranging from about 150 g/mol to about 10,000,000 g/mol. Suitable aprotic solvents include carbonates, ethers, acetamides, acetonitrile, symmetric sulfones, 1,3-dioxolanes, dimethoxyethanes, glymes, siloxanes and their blends. The alkali metal salt can be LiBF₄, LiNO₃, LiPF₆, LiAsF₆, lithium bis(trifluoromethylsulfonyl)imide (LiTFSI), lithium bis(pentafluoroethylsulfonyl)imide, lithium trifluoroacetate, or a similar compound.

In an embodiment, the electrolyte includes a lithium salt in addition to the ionic liquid. A variety of lithium salts may be used, including, for example, Li[CF₃CO₂]; Li[C₂F₅CO₂]; Li[ClO₄]; Li[BF₄]; Li[AsF₆]; Li[PF₆]; Li[PF₂(C₂O₄)₂]; Li[PF₄C₂O₄]; Li[CF₃SO₃]; Li[N(CP₃SO₂)₂]; Li[C(CF₃SO₂)₃]; Li[N(SO₂C₂F₅)₂]; lithium alkyl fluorophosphates; Li[B(C₂O₄)₂]; Li[BF₂C₂O₄]; Li₂[B₁₂Z_12−jH_j]; Li₂[B₁₀X_10−j′H_j′]; or a mixture of any two or more thereof, wherein Z is independent at each occurrence a halogen, j is an integer from 0 to 12 and j′ is an integer from 1 to 10.

In an embodiment of the present electrolyte, such as a formulation for a lithium ion battery, aprotic solvents are combined with the present ionic liquids to decrease the viscosity and increase the conductivity of the electrolyte. The most appropriate aprotic solvents lack exchangeable protons, including cyclic carbonic acid esters, linear carbonic acid esters, phosphoric acid esters, oligoether substituted siloxanes/silanes, cyclic ethers, chain ethers, lactone compounds, chain esters, nitrile compounds, amide compounds, sulfone compounds, siloxanes, phosphoric acid esters, phosphates, phosphites, mono- or polyphosphazenes and the like. These solvents may be used singly, or at least two of them in admixture. Examples of aprotic solvents or carriers for forming the electrolyte systems include but are not limited to dimethyl carbonate, ethyl methyl carbonate, diethyl carbonate, methyl propyl carbonate, ethyl propyl carbonate, dipropyl carbonate, bis(trifluoroethyl) carbonate, bis(pentafluoropropyl) carbonate, trifluoroethyl methyl carbonate, pentafluoroethyl methyl carbonate, heptafluoropropyl methyl carbonate, perfluorobutyl methyl carbonate, trifluoroethyl ethyl carbonate, pentafluoroethyl ethyl carbonate, heptafluoropropyl ethyl carbonate, perfluorobutyl ethyl carbonate, etc., fluorinated oligomers, methyl propionate, ethyl propionate, butyl propionate, dimethoxyethane, triglyme, dimethylvinylene carbonate, tetraethyleneglycol, dimethyl ether, polyethylene glycols, triphenyl phosphate, tributyl phosphate, hexafluorocyclotriphosphazene, 2-Ethoxy-2,4,4,6,6-pentafluoro-1,3,5,2-5,4-5,6-5 triazatriphosphinine, triphenyl phosphite, sulfolane, dimethyl sulfoxide, ethyl methyl sulfone, ethylvinyl sulfone, allyl methyl sulfone, divinyl sulfone, fluorophynelmethyl sulfone and gamma-butyrolactone.

In some embodiments, the electrolytes further include an additive to protect the electrodes from degradation. Thus, electrolytes of the present technology may include an additive that is reduced or polymerized on the surface of a negative electrode to form a passivation film on the surface of the negative electrode. Likewise, electrolytes can include an additive that can be oxidized or polymerized on the surface of the positive electrode to form a passivation film on the surface of the positive electrode. In some embodiments, electrolytes of the present technology further include mixtures of the two types of additives.

In some embodiments, an additive is a substituted or unsubstituted linear, branched or cyclic hydrocarbon including at least one oxygen atom and at least one aryl, alkenyl or alkynyl group. The passivating film formed from such additives may also be formed from a substituted aryl compound or a substituted or unsubstituted heteroaryl compound where the additive includes at least one oxygen atom.

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-triallyloxy-1,3,5-triazine, 1,3,5-triacryloylhexahydro-1,3,5-triazine, 1,2-divinyl furoate, 1,3-butadiene carbonate, 1-vinylazetidin-2-one, 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 vinylaminocyclohexanol, 2-vinylaminocyclopropanone, 2-vinyloxetane, 2-vinyloxy-cyclopropanone, 3-(N-vinylamino)cyclohexanone, 3,5-divinyl furoate, 3-vinylazetidin-2-one, 3 vinylaziridin-2-one, 3-vinylcyclobutanone, 3-vinylcyclopentanone, 3-vinyloxaziridine, 3-vinyloxetane, 3-vinylpyrrolidin-2-one, 2-vinyl-1,3-dioxolane, acrolein diethyl acetal, acrolein dimethyl acetal, 4,4-divinyl-3-dioxolan-2-one, 4-vinyltetrahydropyran, 5-vinylpiperidin-3-one, allylglycidyl ether, butadiene monoxide, butyl-vinyl-ether, dihydropyran-3-one, divinyl butyl carbonate, divinyl carbonate, divinyl crotonate, divinyl ether, divinyl ethylene carbonate, divinyl ethylene silicate, divinyl ethylene sulfate, divinyl ethylene sulfite, divinyl methoxypyrazine, divinyl methylphosphate, divinyl propylene carbonate, ethyl phosphate, methoxy-o-terphenyl, methyl phosphate, oxetan-2-yl-vinylamine, oxiranylvinylamine, vinyl carbonate, 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, vinylcylopropanone, vinylethylene oxide, β-vinyl-γ-butyrolactone or a mixture of any two or more thereof. In some embodiments, the additive may be a cyclotriphosphazene that is substituted with F, alkyloxy, alkenyloxy, aryloxy, methoxy, allyloxy groups or combinations thereof. For example, the additive may be a (divinyl)-(methoxy)(trifluoro)cyclotriphosphazene, (trivinyl)(difluoro)(methoxy)cyclotriphosphazene, (vinyl)(methoxy)(tetrafluoro)cyclotriphosphazene, (aryloxy)(tetrafluoro)(methoxy)cyclotriphosphazene or (diaryloxy)(trifluoro)(methoxy)cyclotriphosphazene compounds or a mixture of two or more such compounds. In some embodiments, the additive is vinyl ethylene carbonate, vinyl carbonate, or 1,2-diphenyl ether, or a mixture of any two or more such compounds.

Other representative additives include compounds with phenyl, naphthyl, anthracenyl, pyrrolyl, oxazolyl, furanyl, indolyl, carbazolyl, imidazolyl, thiophenyl, fluorinated carbonates, sultone, sulfide, anhydride, silane, siloxy, phosphate or phosphite groups. For example, additives may be phenyl trifluoromethyl sulfide, fluoroethylene carbonate, 1,3,2-dioxathiolane 2,2-dioxide, 1-propene 1,3-sultone, 1,3-propanesultone, 1,3-dioxolan-2-one, 4-[(2,2,2-trifluoroethoxy)methyl], 1,3-dioxolan-2-one, 4-[[2,2,2-trifluoro-1-(trifluoromethyl)ethoxy]methyl]-, methyl 2,2,2-trifluoroethyl carbonate, nonafluorohexyltriethoxysilane, octamethyltrisiloxane, methyltris(trimethylsiloxy)silane, tetrakis(trimethylsiloxy)silane, (tridecafluoro-1,1,2,2-tetrahydrooctyl)triethoxysilane, tris(1H,1H-heptafluorobutyl)phosphate, 3,3,3-trifluoropropyltris(3,3,3-trifluoropropyldimethylsiloxy)silane, (3,3,3-trifluoropropyl)trimethoxysilane, trimethylsilyl trifluoromethanesulfonate, tris(trimethylsilyl) borate, tripropyl phosphate, bis(trimethylsilylmethyl)benzylamine, phenyltris(trimethylsiloxy)silane, 1,3-bis(trifluoropropyl)tetramethyldisiloxane, triphenyl phosphate, tris(trimethylsilyl)phosphate, tris(1H,1H,5H-octafluoropentyl)phosphate, triphenyl phosphite, trilauryl trithiophosphite, tris(2,4-di-tert-butylphenyl) phosphite, tri-p-tolyl phosphite, tris(2,2,3,3,3-pentafluoropropyl)phosphate, succinic anhydride, 1,5,2,4-dioxadithiane 2,2,4,4-tetraoxide, tripropyl trithiophosphate, aryloxpyrrole, aryloxy ethylene sulfate, aryloxy pyrazine, aryloxy-carbazole trivinylphosphate, aryloxy-ethyl-2-furoate, aryloxy-o-terphenyl, aryloxy-pyridazine, butyl-aryloxy-ether, divinyl diphenyl ether, (tetrahydrofuran-2-yl)-vinylamine, divinyl methoxybipyridine, methoxy-4-vinylbiphenyl, vinyl methoxy carbazole, vinyl methoxy piperidine, vinyl methoxypyrazine, vinyl methyl carbonate-allylanisole, vinyl pyridazine, 1-divinylimidazole, 3-vinyltetrahydrofuran, divinyl furan, divinyl methoxy furan, divinylpyrazine, vinyl methoxy imidazole, vinylmethoxy pyrrole, vinyl-tetrahydrofuran, 2,4-divinyl isooxazole, 3,4 divinyl-1-methyl pyrrole, aryloxyoxetane, aryloxy-phenyl carbonate, aryloxy-piperidine, aryloxy-tetrahydrofuran, 2-aryl-cyclopropanone, 2-diaryloxy-furoate, 4-allylanisole, aryloxy-carbazole, aryloxy-2-furoate, aryloxy-crotonate, aryloxy-cyclobutane, aryloxy-cyclopentanone, aryloxy-cyclopropanone, aryloxy-cycolophosphazene, aryloxy-ethylene silicate, aryloxy-ethylene sulfate, aryloxy-ethylene sulfite, aryloxy-imidazole, aryloxy-methacrylate, aryloxy-phosphate, aryloxy-pyrrole, aryloxyquinoline, diaryloxycyclotriphosphazene, diaryloxy ethylene carbonate, diaryloxy furan, diaryloxy methyl phosphate, diaryloxy-butyl carbonate, diaryloxy-crotonate, diaryloxy-diphenyl ether, diaryloxy-ethyl silicate, diaryloxy-ethylene silicate, diaryloxy-ethylene sulfate, diaryloxyethylene sulfite, diaryloxy-phenyl carbonate, diaryloxy-propylene carbonate, 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, vinyl methoxyquinoline, pyridazine, vinyl pyridazine, quinoline, vinyl quinoline, pyridine, vinyl pyridine, indole, vinyl indole, triethanolamine, 1,3-dimethyl butadiene, butadiene, vinyl ethylene carbonate, vinyl carbonate, imidazole, vinyl imidazole, piperidine, vinyl piperidine, pyrimidine, vinyl pyrimidine, pyrazine, vinyl pyrazine, isoquinoline, vinyl isoquinoline, quinoxaline, vinyl quinoxaline, biphenyl, 1,2-diphenyl ether, 1,2-diphenylethane, o terphenyl, N-methyl pyrrole, naphthalene or a mixture of any two or more such compounds.

In an embodiment, the electrolyte of the present technology includes an aprotic gel polymer carrier/solvent. Suitable gel polymer carrier/solvents include polyethers, polyethylene oxides, polyimides, polyphosphazines, polyacrylonitriles, polysiloxanes, polyether grafted polysiloxanes, derivatives of the foregoing, copolymers of the foregoing, cross-linked and network structures of the foregoing, blends of the foregoing and the like, to which is added a suitable ionic electrolyte salt. Other gel-polymer carrier/solvents include those prepared from polymer matrices derived from polypropylene oxides, polysiloxanes, sulfonated polyimides, perfluorinated membranes (Nafion resins), divinyl polyethylene glycols, polyethylene glycol-bis-(methyl acrylates), polyethylene glycol-bis(methyl methacrylates), derivatives of the foregoing, copolymers of the foregoing and cross-linked and network structures of the foregoing.

The phosphorus based TRI materials have high solubility in organic solvents. Electrolyte solutions containing these phosphorous TRI material have high ionic conductivity and are suitable for use as an electrolytic solution for electrochemical devices. Examples of electrochemical devices are electric double-layer capacitor, secondary batteries, solar cells of the pigment sensitizer type, electrochromic devices and condensers, and this list is not limitative. Especially suitable as electrochemical devices are electric double-layer capacitor and secondary batteries, such as a lithium ion battery.

In an embodiment, an electrochemical device is provided that includes a cathode, an anode and an electrolyte including an ionic liquid as described herein. In one embodiment, the electrochemical device is a lithium secondary battery. In some embodiments, the secondary battery is a lithium battery, a lithium-ion battery, a lithium-sulfur battery, a lithium-air battery, a sodium ion battery or a magnesium battery. In some embodiments, the electrochemical device is an electrochemical cell, such as a capacitor. In some embodiments, the capacitor is an asymmetric capacitor or supercapacitor. In some embodiments, the electrochemical cell is a primary cell. In some embodiments, the primary cell is a lithium/MnO₂ battery or Li/poly(carbon monofluoride) battery. In some embodiments, the electrochemical cell is a solar cell.

Suitable cathodes include those such as, but not limited to, a lithium metal oxide, spinel, olivine, carbon-coated olivine, LiFePO₄, LiCoO₂, LiNiO₂, LiNi_1xCo_yMet_zO₂, LiMn_0.5Ni_0.5O₂, LiMn_0.3Co_0.3Ni_0.3O₂, LiMn₂O₄, LiFeO₂, Li_1+x′Ni_αMn_βCo_γMet′_δO_2−z′F_z′, A_n′B₂(XO₄)₃ (NASICON), vanadium oxide, lithium peroxide, sulfur, polysulfide, a lithium carbon monofluoride (also known as LiCFx) or mixtures of any two or more thereof, where Met is Al, Mg, Ti, B, Ga, Si, Mn or Co; Met′ is Mg, Zn, Al, Ga, B, Zr or Ti; A is Li, Ag, Cu, Na, Mn, Fe, Co, Ni, Cu or Zn; B is Ti, V, Cr, Fe or Zr; X is P, S, Si, W or Mo; and wherein 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≤h′≤3. According to some embodiments, the spinel is a spinel manganese oxide with the formula of Li_1+xMn_2−zMet′″_yO_4−mX′_n, wherein Met′″ is Al, Mg, Ti, B, Ga, Si, Ni or Co; X′ is S or F; and wherein 0≤x≤0.3, 0≤y≤0.5, 0≤z≤0.5, 0≤m≤0.5 and 0≤n≤0.5. In other embodiments, the olivine has a formula of Li_1+xFe_1zMet″_yPO_4−mX′_n, wherein Met″ is Al, Mg, Ti, B, Ga, Si, Ni, Mn or Co; X′ is S or F; and wherein 0≤x≤0.3, 0 0≤y≤0.5, 0≤z≤0.5, 0≤m≤0.5 and 0≤n≤0.5.

Suitable anodes include those such as lithium metal, graphitic materials, amorphous carbon, Li₄Ti₅O₁₂, tin alloys, silicon alloys, intermetallic compounds or mixtures of any two or more such materials. Suitable graphitic materials include natural graphite, artificial graphite, graphitized meso-carbon microbeads (MCMB) and graphite fibers, as well as any amorphous carbon materials. In some embodiments, the anode and cathode are separated from each other by a porous separator.

The separator for the lithium battery often is a microporous polymer film. Examples of polymers for forming films include: nylon, cellulose, nitrocellulose, polysulfone, polyacrylonitrile, polyvinylidene fluoride, polypropylene, polyethylene, polybutene, or co-polymers or blends of any two or more such polymers. In some instances, the separator is an electron beam-treated micro-porous polyolefin separator. The electron treatment can improve the deformation temperature of the separator and can accordingly enhance the high temperature performance of the separator. Additionally, or alternatively, the separator can be a shut-down separator. The shut-down separator can have a trigger temperature above about 130° C. to permit the electrochemical cells to operate at temperatures up to about 130° C.

The disclosure will be further illustrated with reference to the following specific examples. It is understood that these examples are given by way of illustration and are not meant to limit the disclosure or the claims to follow.

Example A

Electrolyte formulations were prepared in a dry argon filled glovebox by combining all the electrolyte components in a vial and stirring for 24 hours to ensure complete dissolution of the salts. The phosphorous based TRI material is added as a co-solvent to a base electrolyte formulation comprising a 3:7 by weight mixture of ethylene carbonate, “EC”, and ethyl methyl carbonate, “EMC”, with 1 M lithium hexafluorophosphate, “LiPF6”, dissolved therein. The electrolyte formulations prepared are summarized in Table A.

TABLE A
Electrolyte formulations.
		Phosphorous based TRI material
Electrolyte	Base	Co-solvent (18 wt. %)
Com-	1M Li PF6;	NONE
parative	EC:EMC;
Example	3:7 w/w
0
1	1.2M Li PF6; EC:EMC; 3:7 w/w
2	1.2M Li PF6; EC:EMC; 3:7 w/w
3	1.2M Li PF6; EC:EMC; 3:7 w/w

Example B

The electrolyte formulations prepared are used as the electrolyte in nine 5 Ah Li-ion polymer pouch cells comprising Lithium cobalt oxide cathode active material and graphite as the anode active material. Each electrolyte is filled in three cells. In each cell 14.3 g of electrolyte formulation is added and allowed to soak in the cell for 1 hour prior to vacuum sealing and testing. The cells were then charged to 4.2 V and discharged to 3.0 V at a C/15 rate. The results averages are summarized in Table B.

TABLE B
5Ah Cell initial discharge results. Averages of three.
		Discharge Capacity
Electrolyte	iCL (%)	(mAh)
Comparative	7.8	5866
Example 0
2	7.0	5659
3	6.8	5686

Initial capacity loss, “iCL” is a metric of cell performance measuring how much lithium is consumed during the initial charge-discharge cycle and formation of the solid-electrolyte-interface, “SEI”, on the anode surface. It is the aim of cell and electrolyte design for the iCL to be minimized. In this example, the addition of a fluorinated phosphate ester in Electrolyte 2 improves the iCL. Electrolyte 3 provides further improves the iCL with additional fluorination on the phosphate ester. The measured discharge capacities reaching or going above the rated capacity of the cell demonstrate good wetting of the electrodes and separator.

Example C

The electrolyte formulations prepared are used as the electrolyte in nine 200 mAh 403520 Li-ion polymer pouch cells comprising Lithium NMC622 cathode active material and graphite as the anode active material. Each electrolyte is filled in three cells. In each cell 1.1 g of electrolyte formulation is added and allowed to soak in the cell for 1 hour prior to vacuum sealing and testing. The cells were then charged to 4.35 V and discharged to 3.0 V at a C/15 rate. The results averages are summarized in Table C.

TABLE C
5Ah Cell initial discharge results. Averages of three.
		Discharge Capacity
Electrolyte	iCL (%)	(mAh)
Comparative	14.9	196
Example 0
2	14.6	183
3	13.9	196

In this example, the addition of a fluorinated phosphate ester in Electrolyte 2 improves the iCL. Electrolyte 3 provides further improves the iCL with additional fluorination on the phosphate ester. The measured discharge capacities reaching or going above the rated capacity of the cell demonstrate good wetting of the electrodes and separator. The same pattern with respect to incorporating modified phosphates into Li-ion electrolyte formulations is observed independent of cell chemistry.

Example D

The electrolyte formulations prepared are used as the electrolyte in two 40 Ah Li-ion polymer pouch cells comprising Lithium NMC622 cathode active material and graphite as the anode active material. In each cell 170 g of electrolyte formulation is added. The cells are subjected to a wetting procedure where the pressure in increased and decreased repeatedly over the course of 70 minutes. The cells are then vacuum sealed and ready for electrochemical testing after a 10 hour wait period. The cells are then charged to 4.2 V and discharged to 3.0 V at a C/15 rate for formation and then by C/2 discharge and charge for 500 cycles at room temperature. The results of this cycling test are summarized in FIG. 1.

In FIG. 1, it is shown that Electrolyte 2 demonstrates a performance comparable to that of the Comparable Example electrolyte even in large format cells.

Example E

Electrolyte formulations were prepared in a dry argon filled glovebox by combining all the electrolyte components in a vial and stirring for 24 hours to ensure complete dissolution of the salts. The phosphorous based TRI material is added as a cosolvent to a base electrolyte formulation comprising a 3:7 by weight mixture of ethylene carbonate, “EC”, and ethyl methyl carbonate, “EMC”, with 1 M lithium hexafluorophosphate, “LiPF₆”, dissolved therein. The electrolyte formulations prepared are summarized in Table E.

TABLE E
Electrolyte formulations.
		Phosphorous based TRI material
Electrolyte	Base	Co-solvent (20 wt. %)
Com-	1M Li PF6;	NONE
parative	EC:EMC;
Example	3:7 w/w
0
4	1.2M Li PF6; EC:EMC; 3:7 w/w
5	1.2M Li PF6; EC:EMC; 3:7 w/w
3	1.2M Li PF6; EC:EMC; 3:7 w/w

Example F

The viscosity of the electrolyte formulations were measured at 25.0° C. with a Brookfield Ametek DV2T viscometer attached to a PolyScience Circulating Bath. This experimental set-up allows for viscosity to be measured at a precise temperature. The viscosity results are summarized in Table F.

TABLE F
Viscosities of electrolyte formulations
Electrolyte Viscosity at 25.0° C. (cP)
Comparative 3.2
Example 0
4           5.9
5           6.5
6           5.7

Viscosity is an important measurement of the transport properties of an electrolyte formulation that influences electrochemical performance. In Table E it is demonstrated that modifying phosphate esters with a single fluorophenyl group instead of two, a lower viscosity electrolyte formulation is achieved. Additionally, using phenyl groups with two fluorines over one achieves an even lower overall viscosity in the electrolyte formulation.

Example G—Synthesis of 4-Fluorophenyl-Diphenyl Phosphate

Reagent	MW	Equiv	Mol	Mass (g)	Density	Volume (mL)	Conc	Yield (calc)
diphenylchlorophosphate	268.63	1.00	1.787	480.0	1.296	370.4
4-fluorophenol	112.10	1.00	1.787	200.3		#DIV/0!
triethylamine	101.19	1.00	1.787	180.8	0.723	250.1
DCM				850.4	1.326	641.3	80%
4-fluorophenyl-DPP	344.23	1.00	0.000					615.1
triethylamine-HCl	137.65	1.00						245.96

To a 2 L 3-neck flask equipped with a mechanical stirrer, water-cooled condenser, thermocouple, N2 inlet and addition funnel was dissolved 4-fluorophenol (TCI) in DCM (200 mL). Note: only one-third of the calculated amount of solvent was used in this reaction and only small amounts of solvent were used to rinse residual reagents into the reaction mixture.

Triethylamine was added portionwise and the mixture stirred for 20 min. An exotherm to 39° C. was observed.

While stirring at RT, diphenylchlorophosphate (AK Science) was slowly added by addition funnel over 2 h and an exotherm was observed with a temperature range of 36-55° C. As the reaction proceeded, the pale mixture slowly turned colorless as a white solid ppt (triethylamine-HCl) formed and addition became complete. The mixture slowly returned to RT and stirred for 6 h.

DI water (2×300 mL) was added and the mixture was poured into a separatory funnel. The organic phase was extracted into DCM, separated, dried over MgSO4, filtered and the solvent stripped by rotary evaporation. Yield: pale oil, 615.1 g, (>99%).

The crude oil (>615 g) was slurried in DCM (400 mL) and common silica gel (100 g) for 2 h. The oil was collected by vacuum filtration. The silica gel was washed with DCM (4×100 mL) and the solvent was stripped by rotary evaporation and pumped under high vacuum for 2 h. Yield: pale oil, 603.0 g, (98%).

FTIR: 948, 1176, 1487 cm-1; Karl Fischer: 11.8 ppm; Density=1.4245 g/mL.

H NMR: (CDCl3) δ ppm 7.36-7.20 (m, 12H), 7.02 (t, 2H). F NMR: (CDCl3) δ ppm −116.92(s). P NMR: (CDCl3) δ ppm −17.47(s).

Example H—Nail Penetration Test

Nail penetration tests were conducted on 5 Ah NMC 532-Graphite and LCO-Graphite polymer pouch cells at 100% SOC. Table H1 summarizes the electrolyte composition, TRI material molecular structure and corresponding weight percentage in the base electrolyte (EC:EMC 3:7 w/w %) solvents.

FIG. 2 depicts the nail penetration setup and FIG. 3 depicts photographs of punctured cells. The tests were conducted according USCAR specifications, using a 3 mm sharp nail with a displacement rate of 8 mm/s. The cells were clamped during the test to maintain a consistent stack pressure. The cell skin temperature and voltage were recorded. Peak temperature measured during the nail penetration tests are compared in Table H2. The peak temperature results demonstrate that the electrolyte formulations comprising the phosphorous based TRI material overcome the thermal runaway challenges presented by state of the art electrolyte formulations, as exemplified by the Comparative Examples.

TABLE H1
TRI molecular structure and corresponding weight percentage in the base
electrolyte (EC:EMC 3:7 w/w %) solvents
Electrolyte	Base	TRI and (wt. % in base)
Comparative	1M Li PF6; EC:EMC;	NONE
Example 01	3:7 w/w
Comparative Example 02	1.2M Li PF6; EC:EMC; 3:7 w/w	Ionic liquid Pyr14 TFSI (18.5%)
Comparative Example 03	1.2M Li PF6; EC:EMC; 3:7 w/w	Cyclophosphazene (18%)
Example 04	1.2M Li PF6; EC:EMC; 3:7 w/w	Triphenyl phosphate (TPP) (40%)
Example 11	1.2M Li PF6; EC:EMC; 3:7 w/w	4-Fluoro phenyl di-phenyl phosphate (TPP-F) (40.3%)
Example 21	1.2M Li PF6; EC:EMC; 3:7 w/w	4-Fluoro phenyl di-phenyl phosphate (TPP-F) (18.3%)
Example 24	1.2M Li PF6; EC:EMC; 3:7 w/w	3,5-Di-fluoro phenyl di-phenyl phosphate (TPP-3,5F) (19.1%)
Example 13	1.2M Li PF6; EC:EMC; 3:7 w/w	Heptafluoropropyl di-phenyl phosphate (C3F7-DPP) (40.2%)

TABLE H2
Cell chemistry and capacity and peak temperature measured during the
nail penetration tests for variety of TRI compounds.
	Cell				Average
Cell	Capacity				Peak T
Chemistry	(Ah)	Electrolyte	TRI	TRI wt %	(° C.)
NMC532-	5	Comparative	None	0.0	593
Graphite		Electrolyte 01
NMC532-	5	Electrolyte 10	TPP	40.6	162
Graphite
NMC532-	5	Electrolyte 11	TPP-F	40.3	52
Graphite
LCO-	4.8	Comparative	None	0.0	745
Graphite		Electrolyte 01
LCO-	4.8	Electrolyte 21	TPP-F	18.3	69
Graphite
LCO-	4.8	Comparative	Pyr14	18.5	703
Graphite		Electrolyte 02	TFSI
LCO-	4.8	Comparative	Cyclophosphazene	18.0	578
Graphite		Electrolyte 03
LCO-	5	Electrolyte 21	TPP-F	18.3	100
Graphite
LCO-	5	Electrolyte 24	TPP-3,5F	19.1	107
Graphite
LCO-	5	Electrolyte 13	C3F7-	40.2	72
Graphite			DPP

Although various embodiments have been depicted and described in detail herein, it will be apparent to those skilled in the relevant art that various modifications, additions, substitutions, and the like can be made without departing from the spirit of the disclosure and these are therefore considered to be within the scope of the disclosure as defined in the claims which follow.

Claims

1. An electrical energy storage device electrolyte comprising: a) an aprotic organic solvent system;b) an alkali metal salt; andc) at least one of the following phosphate based compounds in an amount of from 0.01 wt. % to 60 wt. % of the electrolyte

2. The electrolyte of claim 1, wherein the aprotic organic solvent comprises an open-chain or cyclic carbonate, carboxylic acid ester, nitrite, ether, sulfone, ketone, lactone, dioxolane, glyme, crown ether, siloxane, phosphoric acid ester, phosphite, mono- or polyphosphazene or mixtures thereof.

3. The electrolyte of claim 1, wherein the cation of the alkali metal salt comprises lithium, sodium, aluminum or magnesium.

4. The electrolyte of claim 1, further comprising an additive.

5. The electrolyte of claim 4, wherein the additive comprises a sulfur-containing compound, phosphorus-containing compound, boron-containing compound, silicon-containing compound, fluorine-containing compound, nitrogen-containing compound, compound containing at least one unsaturated carbon-carbon bond, carboxylic acid anhydride or the mixtures thereof.

6. The electrolyte of claim 1, wherein the additive comprises a concentration in the electrolyte of from about 0.01 wt. % to about 5 wt. %.

7. The electrolyte of claim 1, further comprising an ionic liquid.

8. The electrolyte of claim 7, wherein the ionic liquid comprises an organic cation comprising N-alkyl-N-alkyl-pyrrolidinium, N-alkyl-N-alkyl-pyridnium, N-alkyl-N-alkyl-sulfonium, N-alkyl-N-alkyl-ammonium, or N-alkyl-N-alkyl-piperdinium.

9. The electrolyte of claim 7, wherein the ionic liquid comprises an anion comprising tetrafluoroborate, hexafluorophosphate, bis(trifluoromethylsulfonyl)imide, bis(pentafluoroethylsulfonyl)imide, or trifluoroacetate.

10. An electrical energy storage device comprising: a cathode;an anode; andan electrolyte according to claim 1.

11. The device of claim 10, wherein the cathode comprises a lithium metal oxide, spinel, olivine, carbon-coated olivine, LiFePO4, LiCoO2, LiNiO2, LiNi1xCoyMetzO2, LiMn0.5Ni0.5O2, LiMn0.3Co0.3Ni0.3O2, LiMn2O4, LiFeO2, Li1+x′NiαMnβCoγMet′δO2−z′Fz′, An′B2(XO4)3 (NASICON), vanadium oxide, lithium peroxide, sulfur, polysulfide, a lithium carbon monofluoride or mixtures of any two or more thereof, where Met is Al, Mg, Ti, B, Ga, Si, Mn or Co; Met′ is Mg, Zn, Al, Ga, B, Zr or Ti; A is Li, Ag, Cu, Na, Mn, Fe, Co, Ni, Cu or Zn; B is Ti, V, Cr, Fe or Zr; X is P, S, Si, W or Mo; and wherein 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≤h′≤3.

12. The device of claim 10, wherein the anode comprises lithium metal, graphitic material, amorphous carbon, Li4Ti5O12, tin alloy, silicon alloy, intermetallic compound or mixtures thereof.

13. The device of claim 10, wherein the device comprises a lithium battery, lithium-ion battery, lithium-sulfur battery, lithium-air battery, sodium ion battery, magnesium battery, electrochemical cell, capacitor, lithium/MnO2 battery, Li/poly(carbon monofluoride) battery, or solar cell.

14. The device of claim 10, further comprising a porous separator separating the anode and cathode from each other.

15. The device of claim 14, wherein the porous separator comprises an electron beam-treated micro-porous polyolefin separator or a microporous polymer film comprising nylon, cellulose, nitrocellulose, polysulfone, polyacrylonitrile, polyvinylidene fluoride, polypropylene, polyethylene, polybutene, or co-polymers or blends of any two or more such polymers.

16. The device of claim 10, wherein the aprotic organic solvent comprises an open-chain or cyclic carbonate, carboxylic acid ester, nitrite, ether, sulfone, ketone, lactone, dioxolane, glyme, crown ether, siloxane, phosphoric acid ester, phosphite, mono- or polyphosphazene or mixtures thereof.

17. The device of claim 10, wherein the cation of the alkali metal salt comprises lithium, sodium, aluminum or magnesium.

18. The device of claim 10, wherein the electrolyte further comprises an additive.

19. The device of claim 18, wherein the additive comprises a sulfur-containing compound, phosphorus-containing compound, boron-containing compound, silicon-containing compound, fluorine-containing compound, nitrogen-containing compound, compound containing at least one unsaturated carbon-carbon bond, carboxylic acid anhydride or the mixtures thereof.

20. The device of claim 10, further comprising an ionic liquid.

21. The device of claim 20, wherein the ionic liquid comprises an organic cation comprising N-alkyl-N-alkyl-pyrrolidinium, N-alkyl-N-alkyl-pyridnium, N-alkyl-N-alkyl-sulfonium, N-alkyl-N-alkyl-ammonium, or N-alkyl-N-alkyl-piperdinium.

22. The device of claim 20, wherein the ionic liquid comprises an anion comprising tetrafluoroborate, hexafluorophosphate, bis(trifluoromethylsulfonyl)imide, bis(pentafluoroethylsulfonyl)imide, or trifluoroacetate.