Silicon-based energy storage devices with LiPO
Electrolytes and electrolyte additives for energy storage devices comprising lithium difluorophosphate (LiPO 2 F 2 ) and an electrolyte additive are disclosed. The energy storage device comprises a first electrode and a second electrode, wherein at least one of the first electrode and the second electrode is a Si-based electrode, a separator between the first electrode and the second electrode, an electrolyte, a lithium-containing salt comprising LiPO 2 F 2 , and at least one electrolyte additive compound.
1 . An energy storage device comprising:
a first electrode and a second electrode, wherein one or both of the first electrode and the second electrode is a Si-based electrode;
a separator between the first electrode and the second electrode;
an electrolyte;
a lithium-containing salt comprising lithium difluorophosphate (LiPO 2 F 2 ); and
at least one electrolyte additive;
where said at least one electrolyte additive is selected from the group consisting of allyl cyclohexyl carbonate; N-(allyloxycarbonyloxy)succinimide; 2,2,3,3,3-pentafluoropropyl 2,2,2-trifluoroethyl carbonate; ethyl propargyl carbonate; 3-trimethylsiloxy-1-propyne; glycidyl propargyl ether; 1-fluoroethyl propagyl carbonate; 1-(prop-2-yn-1-yl)-2,5-dihydro-1H-pyrrole-2,5-dione; 2,2-difluoroethyl propargyl carbonate; 2,2,3,3,3-pentafluoropropyl propargyl carbonate; vinylboronic acid MIDA ester; isopropenylboronic acid MIDA ester; cyclopropylboronic acid MIDA ester; 2-cyclobutyl-6-methyl-1,3,6,2-dioxazaborocane-4,8-dione; 2-cyclopentyl-6-methyl-1,3,6,2-dioxazaborocane-4,8-dione; 2-cyclohexyl-6-methyl-1,3,6,2-dioxazaborocane-4,8-dione; 2-ethynyl-6-methyl-1,3,6,2-dioxazaborocane-4,8-dione; 2-butyl-6-methyl-1,3,6,2-dioxazaborocane-4,8-dione; isopropenylboronic anhydride pyridine complex; trivinylboroxin; thiophene-2-boronic acid pinacol ester; 4-methylthiophene-3-boronic acid pinacol ester; 3-(5,5-dimethyl-1,3,2-dioxaborinan-2-yl)pyridine; 3-cyano-1-propylboronic acid pinacol ester; allylboronic acid pinacol ester; 2-vinyl-4,4,5,5-tetramethyl-1,3,2-dioxaborolane; 2-isopropenyl-4,4,5,5-tetramethyl-1,3,2-dioxaborolane; cyclopropylboronic acid pinacol ester; cyclohexylboronic acid pinacol ester; pyridine-3-boronic acid 1,3-propanediol ester; 2,5-difluoropyridine-4-boronic acid, pinacol ester; 2,6-difluoropyridine-3,5-diboronic acid, pinacol ester; tris(2H-hexafluoroisopropyl) borate; boric acid tris-(2-oxo-[1,3]dioxolan4-ylmethyl) ester; tris(prop-2-enyl) borate; triallyl phosphite; diallyl hydrogen phosphate; dimethyl vinyl phosphate; bis(ethenyl) phosphate; tris(ethenyl) phosphate; bis(ethenyl) ethyl phosphate; tris(2,3-epoxypropyl) isocyanurate; 1,3,5-triallyl-1,3,5-triazine-2,4,6(1H,3H,5H)-trione; tris[2-(acryloyloxy)ethyl]isocyanurate; vinyltrisopropenoxysilane; vinyl tris(trimethylsiloxy)silane; 1,5-diethenyl-3-[(ethenyldimethylsilyl)oxy]-1,1,3,5,5-pentamethylpentanetrisiloxane; and 4-(tert-butyldimethylsilyloxy)-1-butyne.
2 . The energy storage device of claim 1 , wherein the second electrode is a Si-dominant electrode.
3 . The energy storage device of claim 1 , wherein the second electrode comprises a self-supporting composite material film.
4 . The energy storage device of claim 3 , wherein the composite material film comprises:
greater than 0% and less than 90% by weight of silicon particles, and
greater than 0% and less than 90% by weight of one or more types of carbon phases, wherein at least one of the one or more types of carbon phases is a substantially continuous phase that holds the composite material film together such that the silicon particles are distributed throughout the composite material film.
5 . The energy storage device of claim 1 , wherein the electrolyte further comprises fluoroethylene carbonate (FEC).
6 . The energy storage device of claim 5 , wherein the electrolyte is substantially free of non-fluorine containing cyclic carbonate.
7 . A method of forming an energy storage device, the method comprising: forming an energy storage device comprising a cathode, an electrolyte, and a Si-based anode, wherein said electrolyte contains a lithium-containing salt comprising
lithium difluorophosphate (LiPO 2 F 2 ); and
at least one electrolyte additive; wherein said one or both of said cathode and said anode is formed using, at least, the following steps:
an electrode material is mixed to create a slurry;
said slurry is coated on metal foil; and
the coated metal foil is dried; and
where said at least one electrolyte additive is selected from the group consisting of allyl cyclohexyl carbonate; N-(allyloxycarbonyloxy)succinimide; 2,2,3,3,3-pentafluoropropyl 2,2,2-trifluoroethyl carbonate; ethyl propargyl carbonate; 3-trimethylsiloxy-1-propyne; glycidyl propargyl ether; 1-fluoroethyl propagyl carbonate; 1-(prop-2-yn-1-yl)-2,5-dihydro-1H-pyrrole-2,5-dione; 2,2-difluoroethyl propargyl carbonate; 2,2,3,3,3-pentafluoropropyl propargyl carbonate; vinylboronic acid MIDA ester; isopropenylboronic acid MIDA ester; cyclopropylboronic acid MIDA ester; 2-cyclobutyl-6-methyl-1,3,6,2-dioxazaborocane-4,8-dione; 2-cyclopentyl-6-methyl-1,3,6,2-dioxazaborocane-4,8-dione; 2-cyclohexyl-6-methyl-1,3,6,2-dioxazaborocane-4,8-dione; 2-ethynyl-6-methyl-1,3,6,2-dioxazaborocane-4,8-dione; 2-butyl-6-methyl-1,3,6,2-dioxazaborocane-4,8-dione; isopropenylboronic anhydride pyridine complex; trivinylboroxin; thiophene-2-boronic acid pinacol ester; 4-methylthiophene-3-boronic acid pinacol ester; 3-(5,5-dimethyl-1,3,2-dioxaborinan-2-yl)pyridine; 3-cyano-1-propylboronic acid pinacol ester; allylboronic acid pinacol ester; 2-vinyl-4,4,5,5-tetramethyl-1,3,2-dioxaborolane; 2-isopropenyl-4,4,5,5-tetramethyl-1,3,2-dioxaborolane; cyclopropylboronic acid pinacol ester; cyclohexylboronic acid pinacol ester; pyridine-3-boronic acid 1,3-propanediol ester; 2,5-difluoropyridine-4-boronic acid, pinacol ester; 2,6-difluoropyridine-3,5-diboronic acid, pinacol ester; tris(2H-hexafluoroisopropyl) borate; boric acid tris-(2-oxo-[1,3]dioxolan4-ylmethyl) ester; tris(prop-2-enyl) borate; triallyl phosphite; diallyl hydrogen phosphate; dimethyl vinyl phosphate; bis(ethenyl) phosphate; tris(ethenyl) phosphate; bis(ethenyl) ethyl phosphate; tris(2,3-epoxypropyl) isocyanurate; 1,3,5-triallyl-1,3,5-triazine-2,4,6(1H,3H,5H)-trione; tris[2-(acryloyloxy)ethyl]isocyanurate; vinyltrisopropenoxysilane; vinyl tris(trimethylsiloxy) silane; 1,5-diethenyl-3-[(ethenyldimethylsilyl)oxy]-1,1,3,5,5-pentamethylpentanetrisiloxane; and 4-(tert-butyldimethylsilyloxy)-1-butyne.
8 . The method of claim 7 , wherein the Si-based anode is a Si-dominant anode.
9 . The method of claim 7 , wherein the Si-based anode comprises a self-supporting composite material film.
10 . The method of claim 9 , wherein the composite material film comprises:
greater than 0% and less than 90% by weight of silicon particles, and
greater than 0% and less than 90% by weight of one or more types of carbon phases, wherein at least one of the one or more types of carbon phases is a substantially continuous phase that holds the composite material film together such that the silicon particles are distributed throughout the composite material film.
11 . The method of claim 7 , wherein the electrolyte further comprises fluoroethylene carbonate (FEC).
12 . The method of claim 11 , wherein the electrolyte is substantially free of non-fluorine containing cyclic carbonate.