Aluminum secondary battery having a high-capacity and high-rate capable cathode and manufacturing method

Patent metadata

Field	Value
Publication number	US-10629948-B2
Application number	US-201715449976-A
Country	US
Kind code	B2
Filing date	Mar 5, 2017
Priority date	Mar 5, 2017
Publication date	Apr 21, 2020
Grant date	Apr 21, 2020

Abstract

Provided is an 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 recompressed exfoliated graphite or carbon material that is oriented in such a manner that the layer has a graphite edge plane in direct contact with the electrolyte and facing the separator. Typically, this graphite edge plane is substantially parallel to the separator layer plane. Such an aluminum battery delivers a high energy density, high power density, and long cycle life.

First claim

We claim:

1. An aluminum secondary battery comprising an anode, a cathode, a 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 layer of recompressed exfoliated graphite or carbon material that is oriented in such a manner that said layer has a graphite edge plane in direct contact with said electrolyte and facing said separator, wherein said layer of recompressed exfoliated graphite or carbon material has a physical density from 0.5 to 1.8 g/cm 3 .

2. The aluminum secondary battery of claim 1 , wherein said exfoliated carbon or graphite material in said cathode active layer is selected from a thermally exfoliated product of meso-phase pitch, meso-phase carbon, meso carbon micro-beads (MCMB), coke particles, expanded graphite flakes, artificial graphite particles, natural graphite particles, highly oriented pyrolytic graphite, soft carbon particles, hard carbon particles, multi-walled carbon nanotubes, carbon nano-fibers, carbon fibers, graphite nano-fibers, graphite fibers, carbonized polymer fibers, or a combination thereof.

3. The aluminum secondary battery of claim 1 , wherein said layer of recompressed exfoliated graphite or carbon material has a physical density from 1.1 to 1.8 g/cm 3 and has pores having a pore size from 2 nm to 5 nm.

4. The aluminum secondary battery of claim 1 , wherein said layer of recompressed exfoliated graphite or carbon material has a specific surface area from 20 m 2 /g to 1,500 m 2 /g.

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 recompressed exfoliated graphite or carbon material.

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 layer of recompressed exfoliated graphite or carbon material 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 layer of recompressed exfoliated graphite or carbon material further comprises an electrically conductive binder material which bonds said exfoliated carbon or graphite material 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 200 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 100 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 200 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 a layer of recompressed exfoliated carbon or graphite material, including compressing exfoliated graphite or carbon using a wet compression or dry compression to align constituent graphite flakes of said exfoliated graphite or carbon; and
(c) 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 layer of recompressed exfoliated carbon or graphite material is oriented in such a manner that said layer has a graphite edge plane in direct contact with said electrolyte and facing or contacting said separator.

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 said electrolyte contains an aqueous electrolyte, an organic electrolyte, a molten salt electrolyte, or an ionic liquid.

22. The method of claim 19 , wherein providing a cathode contains subjecting a carbon or graphite material to an expansion treatment selected from an oxidation, fluorination, bromination, chlorination, nitrogenation, intercalation, combined oxidation-intercalation, combined fluorination-intercalation, combined bromination-intercalation, combined chlorination-intercalation, or combined nitrogenation-intercalation, followed by thermal exfoliation at a temperature from 100° C. to 2,500° C.

23. The method of claim 19 , wherein said wet compression includes compressing or pressing a suspension of exfoliated graphite or carbon dispersed in a liquid electrolyte for an aluminum cell.

24. An aluminum secondary battery comprising an anode, a cathode, a porous

Assignees

• Global Graphene Group Inc

Inventors

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

Classifications

• H01M2004/021

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

• H01M10/054 Primary

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

• H01M4/463

  Aluminium based · CPC title

• H01M10/0566

  Liquid materials · CPC title

• H01M4/587

  for inserting or intercalating light metals · CPC title