Metal halide cathode with enriched conductive additive

Patent metadata

Field	Value
Publication number	US-11824199-B2
Application number	US-202016932458-A
Country	US
Kind code	B2
Filing date	Jul 17, 2020
Priority date	Jul 17, 2020
Publication date	Nov 21, 2023
Grant date	Nov 21, 2023

Abstract

A rechargeable metal halide battery shows increased metal halide utilization with the introduction of electronegative heteroatom-enriched conductive additives into a metal halide cathode incorporated into an electrically conductive material. The electronegative heteroatom-enriched conductive additives include nitrogen-doped carbon, such as nitrogen-doped single layer graphene, and oxygen-enriched carbon, such as acid-treated carbon black. The modified batteries utilize 20-30% more metal halide than unmodified batteries resulting in enhanced specific capacity and energy density.

First claim

We claim:

1. A battery, comprising:
an anode comprising a stable solid electrolyte interphase (SEI) layer;
an electrolyte comprising at least one ion-conducting salt and at least one solvent; and
a cathode comprising a stable SEI layer and a metal halide incorporated into an electrically conductive material that is comprised of or includes an electronegative heteroatom-enriched carbon,
wherein the electrolyte is in contact with the anode, the cathode, and an oxidizing gas, wherein contact of the oxidizing gas and the electrolyte forms the stable SEI layers on the anode and the cathode.

2. The battery of claim 1 , wherein the electronegative heteroatom is selected from the group consisting of fluorine, chlorine, oxygen, and nitrogen.

3. The battery of claim 1 , wherein the electronegative heteroatom-enriched carbon is comprised of or includes nitrogen-doped carbon.

4. The battery of claim 3 , wherein the electrically conductive material is 100% nitrogen-doped carbon.

5. The battery of claim 3 , wherein the nitrogen-doped (N-doped) carbon is selected from the group consisting of N-doped carbon black, N-doped graphene, N-doped carbon nanotubes, N-doped carbon dots, and combinations thereof.

6. The battery of claim 3 , wherein the electrically conductive material comprises nitrogen doped carbon in a weight percentage greater than zero and less than 100% of the total weight of the electrically conductive material.

7. The battery of claim 1 , wherein the electronegative heteroatom-enriched carbon comprises oxygen-enriched carbon.

8. The battery of claim 7 , wherein the oxygen-enriched carbon has an oxygen to carbon ratio between 0.015 and 0.045.

9. The battery of claim 7 , wherein the oxygen-enriched carbon is formed by acid treatment of carbon with an inorganic acid and/or an organic acid.

10. The battery of claim 9 , wherein the inorganic acid is selected from the group consisting of hydrogen fluoride (HF), hydrogen chloride (HCl), hydrogen bromide (HBr), hydrogen iodide (HI), perchloric acid (HClO 4 ), sulfuric acid (H 2 SO 4 ), nitric acid (HNO 3 ), and combinations thereof.

11. The battery of claim 9 , wherein the organic acid is selected from the group consisting of oxalic acid (C 2 H 2 O 4 ), citric acid (C 6 H 8 O 7 ), succinic acid (C 4 H 6 O 4 ), tartaric acid (C 4 H 6 O 6 ), malic acid (C 4 H 6 O 5 ) butyric acid (C 4 H 8 O 2 ), and combinations thereof.

12. The battery of claim 1 , wherein the electrically conductive material comprises a porous carbon material selected from the group consisting of carbon black, carbon nanotubes, carbon nanofibers, carbon dots, activated carbon, amorphous carbon, graphite, graphene, graphene oxide, and combinations thereof.

13. The battery of claim 12 , wherein the electronegative heteroatom-enriched carbon is formed by treating the electrically conductive material with a procedure selected from the group consisting of chemical treatment with oxidizing agents, plasma treatment, ozone treatment, chemical vapor deposition, pyrolysis, and combinations thereof.

14. The battery of claim 12 , wherein the porous carbon material is in the form of particles, powders, paper, foam, fibers, sheets, discs, rods, and/or foils.

15. The battery of claim 1 , wherein the metal halide in the cathode is 40% to 90% of the total weight of the cathode.

16. The battery of claim 1 , wherein the metal halide comprises (i) a metal ion selected from the group consisting of Li + , Mg + , Zn + , Na + , and combinations thereof; and (ii) a halide ion selected from the group consisting of I − , Br − , Cl − , F − , and combinations thereof.

17. The battery of claim 1 , wherein the electrolyte comprises at least one lithium salt as the at least one ion-conducting salt, and the at least one solvent comprises at least one nitrile and/or at least one heterocyclic compound.

18. The battery of claim 1 , wherein the anode comprises at least one alkali metal and/or at least one alkaline earth metal.

19. The battery of claim 1 , wherein the oxidizing gas is selected from the group consisting of oxygen, air, nitric oxide, nitrogen dioxide, and combinations thereof.

20. A battery, comprising:
an anode comprising a solid electrolyte interphase (SEI) layer;
an electrolyte comprising at least one ion-conducting salt and at least one solvent; and
a cathode comprising an SEI layer and a metal halide incorporated into an electrically conductive material that is comprised of or includes nitrogen-doped carbon,
wherein the electrolyte is in contact with the anode, the cathode, and an oxidizing gas, wherein contact of the oxidizing gas with the electrolyte forms the SEI layers on the anode and the cathode.

21. The battery of claim 20 , wherein the electrically conductive material is 100% nitrogen-doped carbon.

22. The battery of claim 20 , wherein the nitrogen-doped (N-doped) carbon is selected from the group consisting of N-doped carbon black, N-doped graphene, N-doped carbon nanotubes, N-doped carbon dots, and combinations thereof.

23. The battery of claim 20 , wherein the electrically conductive material comprises a porous carbon material selected from the group consisting of carbon black, carbon nanotubes, carbon nanofibers, carbon dots, activated carbon, amorphous carbon, graphite, graphene, graphene oxide, and combinations thereof.

24. The battery of claim 23 , wherein the porous carbon material is in the form of particles, powders, paper, foam, fibers, sheets, discs, rods, and/or foils.

25. The battery of claim 20 , wherein the metal halide in the cathode is 40% to 90% of the total weight of the cathode.

26. The battery of claim 20 , wherein the metal halide comprises (i) a metal ion selected from the group consisting of Li + , Mg + , Zn + , Na + , and combinations thereof; and (ii) a halide ion selected from the group consisting of I − , Br − , Cl − , F − , and combinations thereof.

27. The battery of claim 20 , wherein the electrolyte comprises at least one lithium salt as the ion-conducting salt, and the at least one solvent comprises at least one nitrile and/or at least one heterocyclic compound.

28. The battery of claim 20 , wherein the anode comprises at least one alkali metal and/or at least one alkaline earth metal.

29. The battery of claim 20 , wherein the oxidizing gas is selected from the group consisting of oxygen, air, nitric oxide, nitrogen dioxide, and combinations thereof.

30. The battery of claim 20 , wherein the electrically conductive material comprises nitrogen doped carbon in a weight percentage greater than zero and less than 100% of the total weight of the electrically conductive material.

Assignees

• IBM
• Daimler Ag

Inventors

• Kim Jangwoo
• Fong Anthony
• Glossmann Tobias
• Na Young-Hye
• Giammona Maxwell
• Lee Eunseok

Classifications

• H01M4/625 Primary

  Carbon or graphite · CPC title

• H01M4/582

  Halogenides · CPC title

• H01M10/0525 Primary

  Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries · CPC title

• H01M4/136

  Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy · CPC title

• H01M2004/021

  Physical characteristics, e.g. porosity, surface area · CPC title