Graphitic carbon-based cathode for aluminum secondary battery and manufacturing method

Patent metadata

Field	Value
Publication number	US-10553873-B2
Application number	US-201715454053-A
Country	US
Kind code	B2
Filing date	Mar 9, 2017
Priority date	Mar 9, 2017
Publication date	Feb 4, 2020
Grant date	Feb 4, 2020

Abstract

Provided is aluminum secondary battery comprising an anode, a cathode, a porous separator electronically separating the anode and the cathode, and an electrolyte in ionic contact with the anode and the cathode to support reversible deposition and dissolution of aluminum at the anode, wherein the anode contains aluminum metal or an aluminum metal alloy as an anode active material and the cathode comprises a layer of graphitic carbon particles or fibers, preferably selected from meso-phase carbon particles, meso carbon micro-beads (MCMB), coke particles or needles, soft carbon particles, hard carbon particles, amorphous graphite containing graphite micro-crystallites, multi-walled carbon nanotubes, carbon nano-fibers, carbon fibers, graphite nano-fibers, graphite fibers, or a combination thereof.

First claim

We claim:

1. An aluminum secondary battery comprising an anode, a cathode, an optional porous separator electronically separating said anode and said cathode, and an electrolyte in ionic contact with said anode and said cathode to support reversible deposition and dissolution of aluminum at said anode, wherein said anode contains aluminum metal or an aluminum metal alloy as an anode active material and said cathode comprises a cathode active layer of graphitic carbon particles or fibers as a cathode active material that intercalates/de-intercalates aluminum ions or aluminum-containing ions, wherein said graphitic carbon particles or fibers are coated with a protective layer that is permeable to aluminum ions or ions dissolved in said electrolyte and said protective layer prevents or reduces exfoliation of graphitic planes in said graphitic carbon particles or fibers when the aluminum secondary battery is charged and discharged, wherein said protective layer contains a material selected from reduced graphene oxide, an ion-conducting polymer, an electrically conductive polymer, or a combination thereof.

2. The aluminum secondary battery of claim 1 , wherein said graphitic carbon particles or fibers are selected from meso-phase carbon particles, meso carbon micro-beads (MCMB), coke particles or needles, soft carbon particles, hard carbon particles, amorphous graphite containing graphite micro-crystallites, multi-walled carbon nanotubes, carbon nano-fibers, carbon fibers, graphite nano-fibers, graphite fibers, or a combination thereof.

3. The aluminum secondary battery of claim 2 , wherein said meso-phase carbon particles, meso carbon micro-beads (MCMB), coke particles or needles, soft carbon particles, hard carbon particles, carbon nano-fibers, carbon fibers, graphite nano-fibers, or graphite fibers have a surface that is chemically treated to remove a layer of hard carbon or amorphous carbon therefrom.

4. The aluminum secondary battery of claim 1 , wherein said graphitic carbon is selected from needle coke, carbon nano-fiber, carbon fiber, graphite nano-fiber, graphite fiber, multi-walled carbon nanotube, or a combination thereof and said graphitic carbon has a length shorter than 10 μm.

5. The aluminum secondary battery of claim 1 , further comprising an anode current collector supporting said aluminum metal or aluminum metal alloy or further comprising a cathode current collector supporting said layer of graphitic carbon particles or fibers.

6. The aluminum secondary battery of claim 5 , wherein said anode current collector contains an integrated nano-structure of electrically conductive nanometer-scaled filaments that are interconnected to form a porous network of electron-conducting paths comprising interconnected pores, wherein said filaments have a transverse dimension less than 500 nm.

7. The aluminum secondary battery of claim 6 , wherein said filaments comprise an electrically conductive material selected from the group consisting of electro-spun nano fibers, vapor-grown carbon or graphite nano fibers, carbon or graphite whiskers, carbon nano-tubes, nano-scaled graphene platelets, metal nano wires, and combinations thereof.

8. The aluminum secondary battery of claim 1 , wherein said electrolyte is selected from an aqueous electrolyte, organic electrolyte, molten salt electrolyte, ionic liquid electrolyte, or a combination thereof.

9. The aluminum secondary battery of claim 1 , wherein said electrolyte contains AlF 3 , AlCl 3 , AlBr 3 , AlI 3 , AlF x Cl (3-x) , AlBr x Cl (3-x) , AlI x Cl (3-x) , or a combination thereof, wherein x is from 0.01 to 2.0.

10. The aluminum secondary battery of claim 1 , wherein said electrolyte contains an ionic liquid that contains an aluminum salt mixed with an organic chloride selected from n-butyl-pyridinium-chloride (BuPyCl), 1-methyl-3-ethylimidazolium-chloride (MEICl), 2-dimethyl-3-propylimidazolium-chloride, 1,4-dimethyl-1,2,4-triazolium chloride (DMTC), or a mixture thereof.

11. The aluminum secondary battery of claim 1 , wherein the electrolyte also supports reversible intercalation and de-intercalation of ions at the cathode, wherein said ions include cations, anions, or both.

12. The aluminum secondary battery of claim 1 , wherein said cathode active layer of graphitic carbon fibers operates as a cathode current collector to collect electrons during a discharge of said aluminum secondary battery and wherein said battery contains no separate or additional cathode current collector.

13. The aluminum secondary battery of claim 1 , wherein said cathode active layer of graphitic carbon particles or fibers further comprises an electrically conductive binder material which bonds said graphitic carbon particles or fibers together to form a cathode electrode layer.

14. The aluminum secondary battery of claim 13 , wherein said electrically conductive binder material comprises coal tar pitch, petroleum pitch, meso-phase pitch, a conducting polymer, a polymeric carbon, or a derivative thereof.

15. The aluminum secondary battery of claim 1 , wherein said battery has an average discharge voltage no less than 1.5 volt and a cathode specific capacity greater than 100 mAh/g based on a total cathode active layer weight.

16. The aluminum secondary battery of claim 1 , wherein said battery has an average discharge voltage no less than 1.5 volt and a cathode specific capacity greater than 150 mAh/g based on a total cathode active layer weight.

17. The aluminum secondary battery of claim 1 , wherein said battery has an average discharge voltage no less than 2.0 volts and a cathode specific capacity greater than 120 mAh/g based on a total cathode active layer weight.

18. The aluminum secondary battery of claim 1 , wherein said battery has an average discharge voltage no less than 2.0 volts and a cathode specific capacity greater than 150 mAh/g based on a total cathode active layer weight.

19. A method of manufacturing an aluminum secondary battery, comprising:
(a) providing an anode containing aluminum metal or an aluminum alloy;
(b) providing a cathode containing graphitic carbon particles or fibers;
(c) coating said graphitic carbon particles or fibers with a protective layer that is permeable to aluminum ions or ions dissolved in said electrolyte and said protective layer prevents or reduces exfoliation of graphitic planes in said graphitic carbon particles or fibers when the aluminum secondary battery is charged and discharged, wherein said protective layer contains a material selected from reduced graphene oxide, an ion-conducting polymer, an electrically conductive polymer, or a combination thereof; and
(d) providing a porous separator electronically separating said anode and said cathode and an electrolyte capable of supporting reversible deposition and dissolution of aluminum at the anode and reversible adsorption/desorption and/or intercalation/de-intercalation of ions at the cathode;
wherein said graphitic carbon particles or fibers are selected from meso-phase carbon particles, meso carbon micro-beads (MCMB), coke particles or needles, soft carbon particles, hard carbon particles, amorphous graphite containing graphite micro-crystallites, multi-walled carbon nanotubes, carbon nano-fibers, carbon fibers, graphite nano-fibers, graphite fibers, or a combination thereof.

20. The method of claim 19 , further including providing a porous network of electrically conductive nano-filaments to support said aluminum metal or aluminum alloy at the anode.

21. The method of claim 19 , wherein

Assignees

• Nanotek Instruments Inc
• Global Graphene Group Inc

Inventors

• Su Yu-Sheng
• Zhamu Aruna
• He Hui
• Pan Baofei
• Jang Bor Z

Classifications

• H01M2300/0045

  Room temperature molten salts comprising at least one organic ion · CPC title

• H01M10/054

  Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium · CPC title

• H01M4/587 Primary

  for inserting or intercalating light metals · CPC title

• H01M4/38

  of elements or alloys · CPC title

• H01M2300/002

  Inorganic electrolyte · CPC title