SILICON-BASED ENERGY STORAGE DEVICES WITH PHOSPHAZENE CONTAINING ELECTROLYTE ADDITIVES

• US 20200136185A1
• Filed: 10/28/2019
• Published: 04/30/2020
• Est. Priority Date: 10/30/2018
• Status: Active Grant

• Current Assignee: Enevate Corp.
• Original Assignee: Enevate Corp.
• Inventors: Ji, Liwen, Park, Benjamin Yong
• Granted Patent: US 11,522,223 B2
• Time in Patent Office: Days
• CPC Class Codes: C07F 9/65815 n = 3
• CPC Class Codes: C07F 9/65817 n = 4
• CPC Class Codes: C07F 9/6596 having atoms other than oxygen, sulfur, selenium, tellurium, nitrogen or phosphorus as ring hetero atoms
• CPC Class Codes: H01M 10/0525 Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
• CPC Class Codes: H01M 10/0567 characterised by the additives
• CPC Class Codes: H01M 10/0568 characterised by the solutes
• CPC Class Codes: H01M 10/0569 characterised by the solvents
• CPC Class Codes: H01M 2004/027 Negative electrodes
• CPC Class Codes: H01M 2300/0034 Fluorinated solvents
• CPC Class Codes: H01M 2300/0037 Mixture of solvents
• CPC Class Codes: H01M 4/386 Silicon or alloys based on silicon
• CPC Class Codes: H01M 4/625 Carbon or graphite
• CPC Class Codes: Y02E 60/10 Energy storage using batteries

Abstract

Electrolytes and electrolyte additives for energy storage devices comprising phosphazene based compounds 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 comprising at least two electrolyte co-solvents, wherein at least one electrolyte co-solvent comprises a phosphazene based compound.

Claims

1. An energy storage device comprising:

a first electrode;

a second electrode;

a separator between the first electrode and the second electrode; and

an electrolyte system comprising;

a phosphazene based compound;

a linear carbonate;

a cyclic carbonate; and

a Li-containing salt;

wherein at least one of the first electrode and the second electrode is a Si-base electrode.

2. The energy storage device of claim 1, wherein the phosphazene based compound is selected from formulae (A), (B), (C), or combinations thereof:

3. The energy storage device of claim 1, wherein the phosphazene based compound is selected from the group consisting of Hexakis(1H,1H-trifluoroethoxy)phosphazene (H3FPZ);

Hexakis(1H,1H-pentafluoropropoxy)phosphazene (H5FPZ);

Hexakis(1H,1H-perfluorobutoxy)phosphazene;

Hexakis(1H,1H-nonafluoropentoxy)phosphazene;

Hexakis(1H,1H-perfluorohexyloxy)phosphazene;

Hexakis(1H,1H-perfluoroheptoxy)phosphazene;

Hexakis(1H,1H-perfluorooctyloxy)phosphazene;

Hexakis(1H,1H-perfluorononyloxy)phosphazene;

Hexakis(hexafluoroisopropoxy)phosphazene;

Hexakis(2-fluoropropoxy)phosphazene;

Hexakis(1H, 1H,2H-difluoroethoxy)phosphazene;

Hexakis(2,2-difluoropropoxy)phosphazene;

Hexakis(2-fluoropropoxy)phosphazene;

Hexakis(3,3,3-trifluoro-2,2-dimethylpropoxy)phosphazene;

Hexakis(1H,1H,3H-tetrafluoropropoxy)phosphazene;

Hexakis(2,2,3,4,4,4-hexafluorobutoxy)phosphazene;

Hexakis(1H,1H,4H-perfluorobutoxy)phosphazene;

Hexakis(1H,1H,5H-octafluoropentoxy)phosphazene;

Hexakis(1H,1H,7H-perfluoroheptoxy)phosphazene;

Hexakis(3,3,3-trifluoropropoxy)phosphazene;

Hexakis(1H,1H,2H,2H-heptafluoropentoxy)phosphazene;

Hexakis(3,4,4,4-tetrafluoro-3 (trifluoromethyl)butoxy)phosphazene;

Hexakis(1H, 1H,2H,2H-perfluorohexyloxy)phosphazene;

Hexakis(3,3-bis(trifluoromethyl)-4,4,4-trifluorobutoxy)phosphazene;

Hexakis(3,3,3-trifluoro-2,2-dimethylpropoxy)phosphazene;

Hexakis(2-(2,2,2-Trifluoroethoxy)ethoxy)phosphazene or Hexakis[1H,1H-perfluoro(2,5-dimethyl-3,6-dioxanonanoxy)]phosphazene;

Hexakis(4,4,4-trifluorobutoxy)phosphazene;

Hexakis(4,4,5,5,5-pentafluoropentoxy)phosphazene;

Hexakis(4,4,5,5,6,6,6-heptafluorohexoxy)phosphazene;

Hexakis(3-fluoropropoxy)phosphazene;

Hexaallyloxyphosphazene (HALPZ);

2-methyl-2-prop-2-enyl-4,4,6,6-tetrakis(2,2,2-trifluoroethoxy)-1,3,5-triaza-2λ

5,4λ

5,6λ

5-triphosphacyclohexa-1,3,5-triene;

hexa(methacryloylethylenedioxy)cyclotriphosphazene;

Hexakis-(diethylamino)-cyclotriphosphazatrien;

Hexakis-(diethylamino)-cyclotriphosphazatrien;

Hexakis(allylamino)cyclotriphosphazene;

Hexa-pyrrolidin-1-yl-2λ

5,4λ

5,6λ

5-cyclotriphosphazene;

Apholate;

Methyl apholate;

2,4,4,6,6-pentakis(aziridin-1-yl)-N,N-dimethyl-1,3,5-triaza-2λ

5,4λ

5,6λ

5-triphosphacyclohexa-1,3,5-trien-2-amine;

2,4,4,6,6-pentakis(aziridin-1-yl)-N-methyl-1,3,5-triaza-2λ

5,4λ

5,6λ

5-triphosphacyclohexa-1,3,5-trien-2-amine;

2,2,4,4-tetrakis(aziridin-1-yl)-1,3,5,7,11-pentaza-2λ

5,4λ

5,6λ

5-triphosphaspiro[5.5]undeca-1(6),2,4-triene;

2,2,4,4,6-pentakis(aziridin-1-yl)-6-piperidin-1-yl-1,3,5-triaza-2λ

5,4λ

5,6λ

5-triphosphacyclohexa-1,3,5-triene;

Fotretamine;

4-[(2R)-2,4,4,6-tetrakis(aziridin-1-yl)-6-morpholin-4-yl-1,3,5-triaza-2,1,3,5,2,4,6-Triazatriphosphorine;

2,2,4,4-tetra(aziridin-1-yl)-6,6-di(piperidin-1-yl)-1,3,5,2λ

⁵,4λ

⁵,6λ

⁵-triazatriphosphinine;

(6S)-2,2,4,6-tetrakis(aziridin-1-yl)-4,6-di(piperidin-1-yl)-1,3,5-triaza-2λ

5,4λ

5,6λ

5-triphosphacyclohexa-1,3,5-triene;

2,2,4,4-tetrakis(aziridin-1-yl)-6,6-dipyrrolidin-1-yl-1,3,5-triaza-2λ

5,4λ

5,6λ

5-triphosphacyclohexa-1,3,5-triene;

4,4′

-(4,4,6,6-tetra(aziridin-1-yl)-1,3,5,2λ

⁵,4λ

⁵,6λ

⁵-triazatriphosphinine-2,2-diyl)dimorpholine;

2,2,4,4,6,6-hexahydro-4,6-bis(dimethylamino)-2,2,4,6-tetrakis(1-aziridinyl)-1,3,5,2,4,6-Triazatriphosphorine;

4,4,6,6-tetra(aziridin-1-yl)-N,N,N′

,N′

-tetramethyl-1,3,5,2λ

⁵,4λ

⁵,6λ

⁵-triazatriphosphinine-2,2-diamine;

2,4,4,6,6-penta(aziridin-1-yl)-N,N-dimethyl-1,3,5,2λ

⁵,4λ

⁵,6λ

⁵-triazatriphosphinin-2-amine;

Ethyl 2-[[4,4,6,6-tetrakis(aziridin-1-yl)-2-[(2-ethoxy-2-oxoethyl)amino]-1,3,5-triaza-2λ

5,4λ

5,6λ

5-triphosphacyclohexa-1,3,5-trien-2-yl]amino]acetate;

(4R,6S)-4,6-bis(aziridin-1-yl)-2-N,2-N′

,4-N,6-N-tetramethyl-1,3,5-triaza-2λ

5,4λ

5,6λ

5-triphosphacyclohexa-1,3,5-triene-2,2,4,6-tetramine;

2,2,4,4,6,6-hexakis-methylsulfanyl-2λ

5, 4λ

5, 6λ

5-cyclotriphosphazene;

hexaazido cyclotriphosphazene;

2,2,4,4,6,6,8,8-Octakis(dimethylamino)-1,3,5,7,2,4,6,8-tetrazatetraphosphocine;

2,2,4,4,6,6,8,8-octakis(aziridin-1-yl)-1,3,5,7-tetraza-2λ

5,4λ

5,6λ

5,λ

5-tetraphosphacycloocta-1,3,5,7-tetraene;

2,2,4,4,6,6,8,8-octapyrrolidin-1-yl-1,3,5,7-tetraza-2;

2,2,4,4,6,6,8,8-Octa-1-pyrrolidinyl-1,3,5,7,2,4,6,8-tetraphosphazene;

2,2,4,4,6,6,8,8-octakis(piperidin-1-yl)-1,3,5,7-tetraza-2,4,6,8-tetraphosphacycloocta-1,3,5,7-tetraene;

Octamorpholinocyclotetraphosphazene;

(6R,8S)-6,8-bis(aziridin-1-yl)-2-N,2-N′

,4-N,4-N′

,6-N, 8-N-hexamethyl-1,3,5,7-tetraza-2λ

5,4λ

5,6λ

5,8λ

5-tetraphosphacycloocta-1,3,5,7-tetraene-2,2,4,4,6,8-hexamine;

4,8-Bis(1-aziridinyl)-N2,N2,N4,N6,N6,N8-hexamethyl-1,3,5,7,2λ

5,4λ

5,6λ

5,8λ

5-tetrazatetraphosphocine-2,2,4,6,6,8-hexamine;

(4S,8R)-4,8-bis(aziridin-1-yl)-2-N,2-N,2-N′

,2-N′

,4-N,4-N,6-N,6-N,6-N′

,6-N′

,8-N,8-N-dodecamethyl-1,3,5,7-tetraza-2λ

5,4λ

5,6λ

5,8λ

5-tetraphosphacycloocta-1,3,5,7-tetraene-2,2,4,6,6,8-hexamine; and

2,2,4,4,6,6,8,8-octakis(2,2,2-trifluoroethoxy)-1,3,5,7-tetraza-2λ

5,4λ

5,6λ

5,8λ

5-tetraphosphacycloocta-1,3,5,7-tetraene, or a combination thereof.

4. The energy storage device of claim 3, wherein the phosphazene based compound is selected from the group consisting of H3FPZ, H5FPZ and HALPZ, or a combination thereof, at a concentration of about 10% or less.

5. The energy storage device of claim 1, wherein the linear carbonate is selected from the group consisting of ethyl methyl carbonate (EMC), dimethyl carbonate (DMC), and diethyl carbonate (DEC).

6. The energy storage device of claim 1, wherein the cyclic carbonate is selected from the group consisting of fluoroethylene carbonate (FEC), di-fluoroethylene carbonate (DiFEC), Trifluoropropylene carbonate (TFPC), ethylene carbonate (EC), vinyl carbonate (VC), and propylene carbonate (PC).

7. The energy storage device of claim 1, wherein the cyclic carbonate is a fluorine containing cyclic carbonate.

8. The energy storage device of claim 7, wherein the fluorine containing cyclic carbonate is FEC at a concentration of about 5% or more.

9. The energy storage device of claim 1, wherein the electrolyte is substantially free of non-fluorine containing cyclic carbonate.

10. The energy storage device of claim 1, wherein the Li-containing salt is a fluorinated Li salt.

11. The energy storage device of claim 1, wherein the Li-containing salt has a concentration of about 1 M or more.

12. The energy storage device of claim 1, wherein the Si-based electrode is an anode.

13. The energy storage device of claim 12, wherein the anode is a Si-dominant anode.

14. The energy storage device of claim 12, wherein the anode comprises:

greater than 0% and less than about 99% by weight of Si particles, and

greater than 0% and less than about 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.

15. The energy storage device of claim 14, wherein the anode comprises greater than 0% and less than about 90% by weight of Si particles.