IP Library › Granted Patent US 12,261,270
Granted Patent B2
US 12,261,270 · App. 18/147,417 · Granted Mar 25, 2025

Liquid-type room-temperature fluoride ion batteries

Inventors: Qingmin Xu (Dublin, OH); Christopher J. Brooks (Dublin, OH); Kaoru Omichi (Tochigi, JP); Ryan K. McKenney (Upper Arlington, OH); Simon Jones (Whittier, CA); Victoria Davis (Santa Clarita, CA); Stephen Munoz (Pasadena, CA); Jeongmin Kim (Pasadena, CA); Keith Billings (Yorba Linda, CA); Thomas Miller, III (South Pasadena, CA); Robert H. Grubbs (South Pasadena, CA); William Wolf (Pasadena, CA); Nam Hawn Chou (Dublin, OH)
Assignees: Honda Motor Co., Ltd.; California Institute of Technology
H01M10/0569H01M4/366H01M4/38H01M4/381H01M4/582H01M4/62H01M10/05H01M10/0568H01M10/36
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Quick Facts
Patent No.
US 12,261,270
App. No.
18/147,417
Granted
Mar 25, 2025
Kind
B2
Abstract

The present disclosure relates to fluoride ion batteries and structures of metal based electrode materials for various fluoride ion batteries. The structures of the metal based electrode materials comprise one or more shells or interfaces, enabling the electrodes to operate at room temperature with a liquid electrolyte.

Claims (44)

1. A fluoride ion battery comprising:

an anode containing an alkali earth metal, a rare earth metal, or a combination thereof, and having an outer solid electrolyte interphase layer;

a cathode comprising an electrochemically active structure having a core and a shell at least partially surrounding the core, wherein the shell comprises a shell material comprising one or more organic molecules having one or more functional groups; and

a liquid electrolyte comprising fluoride ions between the anode and the cathode.

2. The fluoride ion battery of claim 1 , wherein the liquid electrolyte comprises bis(2-methoxyethyl) ether, bis(2,2,2-trifluoroethyl) ether, N,N,N-trimethyl-N-neopentylammonium fluoride, N,N-dimethyl-N,N-dineopentylammonium fluoride, propionitrile, or a combination thereof.

3. The fluoride ion battery of claim 1 , wherein the core has at least one dimension less than or equal to about 25 nm.

4. The fluoride ion battery of claim 1 , wherein the core comprises a transition metal selected from the group consisting of copper, iron, lead, bismuth, cobalt, alloys thereof, fluorides thereof, and combinations thereof.

5. The fluoride ion battery of claim 1 , wherein the alkali earth metal is calcium, and the rare earth metal is selected from cerium and lanthanum.

6. The fluoride ion battery of claim 1 , wherein the outer solid electrolyte interphase layer is covalently attached to the anode, the outer solid electrolyte interphase layer comprising CF 3 (CF 2 ) 5 CH 2 , CF 3 (CF 2 ) 2 CH 2 , para-tert-butylphenyl, para-methoxyphenyl, para-(dimethylamino) phenyl, para-nitrophenyl, para-trifluoromethylphenyl, or a combination thereof.

7. The fluoride ion battery of claim 1 , wherein the outer solid electrolyte interphase layer comprises 1H,1H,2H,2H-perfluorooctyltriethoxysilane; 3, 3, 4, 4, 5, 5, 6, 6, 6-nonafluorohex-1-ene; 4-tert-butylbenzene diazonium salt; 4-methoxybenzene diazonium salt; 4-(dimethylamino) benzene diazonium salt; 4-nitrobenzene diazonium salt; 4-trifluoromethylbenzene diazonium salt, or a combination thereof.

8. The fluoride ion battery of claim 1 , wherein the one or more functional groups are selected from the group consisting of: —COOH, —NH 2 , —COH, —OH, —SH, —PO 3 H, —SO 3 H, —CN, —NC, —R 2 P, —COO − , —COO—OOCR, ene-diol, —C≡N, —N≡N + (BF4 − ), -Sac, —SR, —SSR, —CSSH, —S 2 O 3 − Na + , —SeH, —SeSeR, —R 2 P═O, —PO 3 2− /—P(O)(OH) 2 , —PO 4 2− , —N≡C, —HC═CH 2 , —C≡CH, —SiH 3 , —SiCl 3 , —OCH 2 CH 3 , formula (I), formula (II), formula (III), an alkane, an alkyne, an alkene, an aromatic ring, and combinations thereof,

wherein formula (I) is:

formula (II) is:

and formula (III) is:

wherein R′ and R″ are each independently an organic chain, a partially or fully fluorinated organic chain, or an aromatic group, a partially or fully fluorinated aromatic group.

9. The fluoride ion battery of claim 8 , wherein R′ and R″ are selected from (CF 2 ) n CF 3 , (CH 2 CF 2 )nCF 3 , (CF 2 CH 2 O) n CF 3 ,

10. A fluoride ion battery comprising:

an anode containing an alkali earth metal, a rare earth metal, or a combination thereof, and having an outer solid electrolyte interphase layer;

a cathode comprising an electrochemically active structure having a core and a shell at least partially surrounding the core, wherein the shell comprises a shell material comprising an organic molecule; and

a liquid electrolyte comprising fluoride ions between the anode and the cathode.

11. The fluoride ion battery of claim 10 , wherein the liquid electrolyte comprises bis(2-methoxyethyl) ether, bis(2,2,2-trifluoroethyl) ether, N,N,N-trimethyl-N-neopentylammonium fluoride, N,N-dimethyl-N,N-dineopentylammonium fluoride, propionitrile, or a combination thereof.

12. The fluoride ion battery of claim 10 , wherein the core has at least one dimension less than or equal to about 25 nm.

13. The fluoride ion battery of claim 10 , wherein the core comprises a transition metal selected from the group consisting of copper, iron, lead, bismuth, cobalt, alloys thereof, fluorides thereof, and combinations thereof.

14. The fluoride ion battery of claim 10 , wherein the alkali earth metal is calcium, and the rare earth metal is selected from cerium and lanthanum.

15. The fluoride ion battery of claim 10 , wherein the outer solid electrolyte interphase layer is covalently attached to the anode, the outer solid electrolyte interphase layer comprising CF 3 (CF 2 ) 5 CH 2 , CF 3 (CF 2 ) 2 CH 2 , para-tert-butylphenyl, para-methoxyphenyl, para-(dimethylamino) phenyl, para-nitrophenyl, para-trifluoromethylphenyl, or a combination thereof.

16. The fluoride ion battery of claim 10 , wherein the outer solid electrolyte interphase layer comprises 1H,1H,2H,2H-perfluorooctyltriethoxysilane; 3, 3, 4, 4, 5, 5, 6, 6, 6-nonafluorohex-1-ene; 4-tert-butylbenzene diazonium salt; 4-methoxybenzene diazonium salt; 4-(dimethylamino) benzene diazonium salt; 4-nitrobenzene diazonium salt; 4-trifluoromethylbenzene diazonium salt, or a combination thereof.

17. The fluoride ion battery of claim 10 , wherein the organic molecule is an organic surfactant selected from the group consisting of: oleylamine; oleic acid; tris (trimethylsilyl) silane; 3, 3, 4, 4, 5, 5, 6, 6, 7, 7, 8, 8, 9, 9, 10, 10, 10-heptadecafluorodecanethiol; 2-(trifluoromethoxy)-benzenethiol; P-[12-(2, 3, 4, 5, 6-pentafluorophenoxy) dodecyl]-phosphonic acid; P-(3, 3, 4, 4, 5, 5, 6, 6, 7, 7, 8, 8, 9, 9, 10, 10, 10-heptadecafluorodecyl)-phosphonic acid; pentafluorobenzylphosphonic acid; perfluorododecanoic acid; and combinations thereof.

18. The fluoride ion battery of claim 10 , wherein the organic molecule is an organic surfactant comprising one or more functional groups selected from the group consisting of:—COOH, —NH 2 , —COH, —OH, —SH, —PO 3 H, —SO 3 H, —CN, —NC, —R 2 P, —COO − , —COO—OOCR, ene-diol, —C≡N, —N≡N + (BF 4 − ), -Sac, —SR, —SSR, —CSSH, —S 2 O 3 − Na + , —SeH, —SeSeR, —R 2 P═O, —PO 3 2− /—P(O)(OH) 2 , —PO 4 2− , —N≡C, —HC═CH 2 , —C≡CH, —SiH 3 , —SiCl 3 , —OCH 2 CH 3 , formula (I), formula (II), formula (III), an alkane, an alkyne, an alkene, an aromatic ring, and combinations thereof,

wherein formula (I) is:

formula (II) is:

and formula (III) is:

wherein R′ and R″ are each independently an organic chain, a partially or fully fluorinated organic chain, or an aromatic group, a partially or fully fluorinated aromatic group.

19. The fluoride ion battery of claim 18 , wherein R′ and R″ are selected from (CF 2 ) n CF 3 , (CH 2 CF 2 ) n CF 3 , (CF 2 CH 2 O) n CF 3 ,

20. A fluoride ion battery comprising:

an anode containing an alkali earth metal, a rare earth metal, or a combination thereof, and having an outer solid electrolyte interphase layer;

a cathode comprising an electrochemically active structure having a core and a shell at least partially surrounding the core, wherein the shell comprises a polymer or an oligomer; and

a liquid electrolyte comprising fluoride ions between the anode and the cathode.

21. The fluoride ion battery of claim 20 , wherein the liquid electrolyte comprises bis(2-methoxyethyl) ether, bis(2,2,2-trifluoroethyl) ether, N,N,N-trimethyl-N-neopentylammonium fluoride, N,N-dimethyl-N,N-dineopentylammonium fluoride, propionitrile, or a combination thereof.

22. The fluoride ion battery of claim 20 , wherein the core has at least one dimension less than or equal to about 25 nm.

23. The fluoride ion battery of claim 20 , wherein the core comprises a transition metal selected from the group consisting of copper, iron, lead, bismuth, cobalt, alloys thereof, fluorides thereof, and combinations thereof.

24. The fluoride ion battery of claim 20 , wherein the alkali earth metal is calcium, and the rare earth metal is selected from cerium and lanthanum.

25. The fluoride ion battery of claim 20 , wherein the outer solid electrolyte interphase layer is covalently attached to the anode, the outer solid electrolyte interphase layer comprising CF 3 (CF 2 ) 5 CH 2 , CF 3 (CF 2 ) 2 CH 2 , para-tert-butylphenyl, para-methoxyphenyl, para-(dimethylamino) phenyl, para-nitrophenyl, para-trifluoromethylphenyl, or a combination thereof.

26. The fluoride ion battery of claim 20 , wherein the outer solid electrolyte interphase layer comprises 1H,1H,2H,2H-perfluorooctyltriethoxysilane; 3, 3, 4, 4, 5, 5, 6, 6, 6-nonafluorohex-1-ene; 4-tert-butylbenzene diazonium salt; 4-methoxybenzene diazonium salt; 4-(dimethylamino) benzene diazonium salt; 4-nitrobenzene diazonium salt; 4-trifluoromethylbenzene diazonium salt, or a combination thereof.

27. The fluoride ion battery of claim 20 , wherein the shell comprises a polymer selected from the group consisting of polyvinylpyrrolidone, poly (methyl methacrylate), and combinations thereof.

Assignments (2)
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Dec 29, 2022
From: XU, QINGMIN; BROOKS, CHRISTOPHER J.; OMICHI, KAORU; MCKENNEY, RYAN K.; CHOU, NAM HAWN
To: HONDA MOTOR CO., LTD.
Reel/Frame 062233/0646 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Dec 29, 2022
From: JONES, SIMON; KIM, JEONGMIN; BILLINGS, KEITH; MILLER, THOMAS, III; GRUBBS, ROBERT H.; DAVIS, VICTORIA; MUNOZ, STEPHEN; WOLF, WILLIAM
To: CALIFORNIA INSTITUTE OF TECHNOLOGY
Reel/Frame 062233/0736 →
Continuity (21)
Division 16703654 · Dec 4, 2019
Continuation In Part 15844079 · Dec 15, 2017
Continuation In Part 16445022 · Jun 18, 2019
Continuation In Part 16013739 · Jun 20, 2018
Continuation In Part 15844079 · Dec 15, 2017
Continuation In Part 16444854 · Jun 18, 2019
Continuation In Part 16013739 · Jun 20, 2018
Continuation In Part 15844079 · Dec 15, 2017
Continuation In Part 15228876 · Aug 4, 2016
Continuation In Part 16702327 · Dec 3, 2019
Continuation In Part 16444854 · Jun 18, 2019
Provisional Application 62453295 · Feb 1, 2017
Provisional Application 62434611 · Dec 15, 2016
Provisional Application 62687653 · Jun 20, 2018
Provisional Application 62775748 · Dec 5, 2018
Provisional Application 62676693 · May 25, 2018
Provisional Application 62863114 · Jun 18, 2019
Provisional Application 62200998 · Aug 4, 2015
Provisional Application 62776978 · Dec 7, 2018
Provisional Application 62775690 · Dec 5, 2018
Related Publication 20230135901A1 · May 4, 2023
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