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

1. An aluminum secondary battery comprising an anode, a 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 a graphite or carbon material subjected to a constrained thermal expansion treatment having expanded inter-graphene planar spaces with an inter-planar spacing d 002 from 1.0 nm to 3.0 nm as measured by X-ray diffraction and an optional 0-30% by weight of a conductive additive based on a total weight of the cathode active layer, wherein said constrained thermal expansion treatment is a heat treatment under a constant volume condition or under a uniaxial compression, wherein said conductive additive is selected from a carbon or graphite material having un-expanded inter-graphene planar spaces with an inter-planar spacing d 002 from 0.33 nm to 0.36 nm.

2. The aluminum secondary battery of claim 1 , wherein said graphite or carbon material in said cathode active layer is selected from 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, carbon aerogel, carbon xerogel, or a combination thereof, wherein said graphite or carbon material has an inter-planar spacing d 002 from 0.27 nm to 0.42 nm prior to a chemical or physical expansion treatment and the inter-planar spacingd 002 is increased to from 1.0 nm to 2.0 nm after said chemical or physical expansion treatment.

3. The aluminum secondary battery of claim 1 , wherein said carbon or graphite material is selected from graphite foam or graphene foam having pores and pore walls, wherein said pore walls contain a stack of bonded graphene planes having an expanded inter-planar spacing d 002 from 1.0 nm to 1.5 nm.

4. The aluminum secondary battery of claim 3 , wherein said stack contains from 2 to 100 graphene planes.

5. The aluminum secondary battery of claim 1 , wherein said inter-planar spacing d 002 is from 1.0 nm to 1.2 nm.

6. The aluminum secondary battery of claim 1 , wherein said inter-planar spacing d 002 is from 1.2 nm to 2.0 nm.

7. 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 cathode active layer of graphite or carbon material.

8. The aluminum secondary battery of claim 7 , 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.

9. The aluminum secondary battery of claim 8 , 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.

10. The aluminum secondary battery of claim 2 , wherein said graphite or carbon material is subjected to said chemical or physical expansion treatment including an oxidation, fluorination, bromination, chlorination, nitrogenation, intercalation, combined oxidation-intercalation, combined fluorination-intercalation, combined bromination-intercalation, combined chlorination-intercalation, or combined nitrogenation-intercalation of said graphite or carbon material prior to said constrained thermal expansion treatment.

11. The aluminum secondary battery of claim 1 , wherein said carbon or graphite material contains a non-carbon element selected from oxygen, fluorine, chlorine, bromine, iodine, nitrogen, hydrogen, or boron.

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

13. 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.

14. 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.

15. 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.

16. The aluminum secondary battery of claim 1 , wherein said cathode active layer of carbon or graphite 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.

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

18. The aluminum secondary battery of claim 17 , 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.

19. 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.

20. 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 300 mAh/g based on a total cathode active layer weight.

21. 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.

22. 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.

23. A cathode active layer for an aluminum secondary battery, said cathode active layer comprises a graphite or carbon material subjected to a constrained thermal expansion treatment having expanded inter-graphene planar spaces with an inter-planar spacing d 002 from 1.0 nm to 3.0 nm as measured by X-ray diffraction, wherein said constrained thermal expansion treatment is a heat treatment under a constant volume condition or under a uniaxial compression, wherein said cathode layer comprises less than 30% by weight of an original graphite having no expanded inter-graphene planar spaces and having an inter-planar spacing d 002 from 0.334 nm to 0.34 nm.

24. The cathode active layer of claim 23 , wherein said carbon or graphite material is selected from 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, carbon aerogel, carbon xerogel, or a combination thereof, wherein said carbon or graphite material has an inter-planar spacing d 002 from 0.27 nm to 0.42 nm prior to a chemical or physical expansion treatment and the inter-planar spacing d 002 is increased to from 1.0 nm to 2.0 nm after said expansion treatment.

25. The cathode active layer of claim 23 , wherein said carbon or graphite material is selected from graphite foam or graphene foam having pores and pore walls, wherein said pore walls contain a stack of bonded graphene planes having an expanded inter-planar spacing d 002 from 1.0 nm to 1.5 nm.

26. The cathode active layer of claim 25 , wherein said stack contains from 2 to 100 graphene planes.

27. A method of manufacturing an aluminum secondary battery, comprising:

(a) providing an anode containing aluminum or an aluminum alloy;

(b) providing a cathode containing a carbon or graphite material subjected to a constrained thermal expansion treatment having expanded inter-planar spaces, d 002 from 1.0 nm to 3.0 nm, wherein said constrained thermal expansion treatment is a heat treatment under a constant volume condition or under a uniaxial compression; and

(c) providing 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.

28. The method of claim 27 , further including providing a porous network of electrically conductive nano-filaments to support said aluminum or aluminum alloy.

29. The method of claim 27 , wherein said carbon or graphite material contains a graphite foam or graphene foam having pore walls composed of multiple graphene planes having inter-planar spacing from 1.0 nm to 2.0 nm.

30. The method of claim 27 , wherein said electrolyte contains an aqueous electrolyte, an organic electrolyte, a molten salt electrolyte, or an ionic liquid.

31. The method of claim 27 , 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.