Silicon-based energy storage devices with fluorinated electrolyte formulations
Electrolytes and electrolyte additives for energy storage devices comprising fluorinated electrolyte additive compounds are disclosed. The energy storage device comprises a first electrode and a second electrode, where 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, and at least one electrolyte additive selected from a linear carbonate, a cyclic carbonate, a linear carboxylic ester, a linear ether, a linear acetate, a sulfone, a linear anhydride, a cyclic anhydride, a phosphate, a phosphite, a phosphorus-containing compound, a phosphazene, a cyclic phosphazene, a nitrogen-containing compound, a silicon-containing compound, a sulfur-containing compound, a Li salt compound, a metal salt compound, fluorine salt compound, or combinations thereof, which may be partially or fully fluorinated and may be optionally substituted.
1 . An energy storage device comprising:
a first electrode and a second electrode, where 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;
a fluorinated electrolyte; and
at least one fluorinated electrolyte additive compound;
wherein the fluorinated electrolyte additive compound is selected from the group consisting of formulae (E), (H), (I), (M)-(O) and (Q):
wherein each individual R 1 , R 2 , R 3 , R 4 , or R 5 group are the same or different and are selected from —F, —H, alkyl, fluoro-alkyl, alkylene, alkoxy, alkenyl, alkenylene, alkynyl, alkynylene, cycloalkyl, cycloalkylene, aryl, arylene, heteroaryl, heteroalkyl, heteroalkylene, heterocycloalkyl, and heterocycloalkylene, each of which is optionally substituted; and
R x and R y are —H, alkyl, fluoro-alkyl, alkylene, alkoxy, alkenyl, alkenylene, alkynyl, or alkynylene, each of which is optionally substituted; or
R x and R y may together make a cyclic structure; and
wherein the compounds are substituted such that they contain at least one fluorine atom.
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 . The energy storage device of claim 1 , wherein the electrolyte additive compound is an additive chemical compound comprising two or more of any of above formulae (E), (H), (I), (M)-(O) and (Q), which are the same or different, and are joined either by direct bonding, by connection through an alkylene moiety or by connection through an —O-group.
8 . The energy storage device of claim 1 , wherein the electrolyte additive is selected from the group consisting of 1,1,1,2,2,3,3,4,4-nonafluoro-4-methoxybutane; 2-(difluoro(methoxy)methyl)-1,1,1,2,3,3,3-heptafluoropropane; 3,4-difluorofuran-2,5-dione (DFMA) (CAS: 669-78-3); 3,3-difluorodihydrofuran-2,5-dione (CAS: 79802-73-6); tris (trifluoromethylsulfanyl) phosphine (CAS: 674-90-8); tris(trifluoromethylsulfanyl)phosphine oxide (CAS: 57368-29-3); pentakis(2,2,2-trifluoroethoxy)-λ5-phosphane (CAS: 71181-76-5); pentakis(2,2,3,3-tetrafluoropropoxy) phosphorane; 1,3,5-tris (3,3-difluoroprop-2-enyl)-1,3,5-triazinane-2,4,6-trione (CAS: 71113-20-7), 2,4,6,8-tetramethyl-2,4,6,8-tetra(3,3,3-trifluoropropyl)cyclotrisiloxane (CAS: 2374-14-3); [2-[[methyl-[3-prop-2-enoyloxy-2,2-bis(prop-2-enoyloxymethyl)propoxy]-(3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl)silyl]oxymethyl]-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl]prop-2-enoate (CAS No. 94237-12-4); and 1,3,3-tetramethyl-1,3-bis (3,3,4,4,5,5,6,6,6-nonafluorohex-1-en-1-yl)disiloxane (CAS: 1374104-96-7).
9 . A method of forming an energy storage device, the method comprising:
forming an energy storage device comprising a cathode, a fluorinated electrolyte, and an anode, wherein said one or both of said cathode and said anode contain one or more fluorinated electrolyte additive compounds;
wherein said one or both of said cathode and said anode is formed using, at least, the following steps:
said electrode material is mixed to create a slurry;
said one or more fluorinated electrolyte additive compounds is added to said slurry;
said slurry is coated on metal foil; and
the coated metal foil is dried; and
wherein the fluorinated electrolyte additive compound is selected from the group consisting of formulae (E), (H), (I), (M)-(O) and (Q):
wherein each individual R 1 , R 2 , R 3 , R 4 , or R 5 group are the same or different and are selected from —F, —H, alkyl, fluoro-alkyl, alkylene, alkoxy, alkenyl, alkenylene, alkynyl, alkynylene, cycloalkyl, cycloalkylene, aryl, arylene, heteroaryl, heteroalkyl, heteroalkylene, heterocycloalkyl, and heterocycloalkylene, each of which is optionally substituted; and
R x and R y are —H, alkyl, fluoro-alkyl, alkylene, alkoxy, alkenyl, alkenylene, alkynyl, or alkynylene, each of which is optionally substituted; or
R x and R y may together make a cyclic structure; and
wherein the compounds are substituted such that they contain at least one fluorine atom.
10 . The method of claim 9 , wherein the second electrode is a Si-dominant electrode.
11 . The method of claim 9 , wherein the second electrode comprises a self-supporting composite material film.
12 . The method of claim 11 , 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.
13 . The method of claim 9 , wherein the electrolyte further comprises fluoroethylene carbonate (FEC).
14 . The method of claim 13 , wherein the electrolyte is substantially free of non-fluorine containing cyclic carbonate.
15 . The method of claim 9 , wherein the electrolyte additive compound is an additive chemical compound comprising two or more of any of above formulae (E), (H), (I), (M)-(O) and (Q), which are the same or different, and are joined either by direct bonding, by connection through an alkylene moiety or by connection through an —O— group.