Alkali metal battery having an integral 3D graphene-carbon-metal hybrid foam-based electrode

1. An alkali metal battery having an anode, a cathode, an electrolyte in ionic contact with said anode and said cathode, and an optional porous separator electronically separating said anode and said cathode, wherein said anode comprises an integral 3D graphene-carbon-metal hybrid foam comprised of multiple pores, pore walls, and a lithium-attracting metal or sodium-attracting metal residing in said pores or deposited on said pore walls; wherein said lithium-attracting metal is selected from the group consisting of Au, Ag, Mg, Zn, Ti, Na, K, Al, Fe, Mn, Co, Ni, Sn, V, Cr, and an alloy thereof for a lithium metal battery, or said sodium-attracting metal is selected from the group consisting of Au, Ag, Mg, Zn, Ti, Li, K, Al, Fe, Mn, Co, Ni, Sn, V, Cr, and an alloy thereof for a sodium metal battery, and is in an amount of 0.1% to 90% of the total hybrid foam weight, and said pore walls comprise single-layer or few-layer graphene sheets chemically bonded by a carbon material having a carbon material-to-graphene weight ratio from 1/200 to 1/2, wherein said few-layer graphene sheets have 2-10 layers of stacked graphene planes having an inter-plane spacing d 002 from 0.3354 nm to 0.40 nm as measured by X-ray diffraction and said single-layer or few-layer graphene sheets comprise a pristine graphene material having essentially zero % of non-carbon elements, or a non-pristine graphene material having 0.001% to 25% by weight of non-carbon elements wherein said non-pristine graphene is selected from graphene oxide, reduced graphene oxide, graphene fluoride, graphene chloride, graphene bromide, graphene iodide, hydrogenated graphene, nitrogenated graphene, doped graphene, chemically functionalized graphene, or a combination thereof; wherein said integral 3D graphene-carbon-metal hybrid foam is pre-loaded with lithium or sodium before said battery is made, or said anode further comprises a lithium source or a sodium source.

2. The alkali metal battery of claim 1 , further comprising an additional separate, discrete anode current collector in contact with said anode, and/or a separate, discrete cathode current collector in contact with said cathode.

3. The alkali metal battery of claim 1 , wherein said cathode comprises an integral 3D graphene-carbon hybrid foam composed of multiple pores and pore walls, wherein said pore walls contain single-layer or few-layer graphene sheets chemically bonded by a carbon material having a carbon material-to-graphene weight ratio from 1/200 to 1/2, wherein said few-layer graphene sheets have 2-10 layers of stacked graphene planes having an inter-plane spacing d 002 from 0.3354 nm to 0.40 nm as measured by X-ray diffraction and said single-layer or few-layer graphene sheets contain a pristine graphene material having essentially zero % of non-carbon elements, or a non-pristine graphene material having 0.001% to 25% by weight of non-carbon elements wherein said non-pristine graphene is selected from graphene oxide, reduced graphene oxide, graphene fluoride, graphene chloride, graphene bromide, graphene iodide, hydrogenated graphene, nitrogenated graphene, doped graphene, chemically functionalized graphene, or a combination thereof.

4. The alkali metal battery of claim 1 , wherein said 3D graphene-carbon hybrid foam, when measured without said metal, has a density from 0.005 to 1.7 g/cm 3 , a specific surface area from 50 to 3,200 m 2 /g, a thermal conductivity of at least 200 W/mK per unit of specific gravity, and/or an electrical conductivity no less than 2,000 S/cm per unit of specific gravity.

5. The alkali metal battery of claim 1 , wherein said pore walls contain a pristine graphene and said 3D graphene-carbon hybrid foam, when measured without said metal, has a density from 0.1 to 1.7 g/cm 3 , an average pore size from 2 nm to 50 nm, and a specific surface area from 300 m 2 /g to 3,200 m 2 /g.

6. The alkali metal battery of claim 1 , wherein said pore walls contain a non-pristine graphene material and wherein said foam contains a content of non-carbon elements in the range of 0.01% to 20% by weight and said non-carbon elements include an element selected from oxygen, fluorine, chlorine, bromine, iodine, nitrogen, hydrogen, or boron.

7. The alkali metal battery of claim 1 , wherein said battery is in a continuous-length filament, wire, or sheet form having a thickness or diameter from 200 nm to 10 cm.

8. The alkali metal battery of claim 1 , wherein said graphene-carbon hybrid foam, when measured without said metal, has an oxygen content or non-carbon content less than 1% by weight, and said pore walls have an inter-graphene spacing less than 0.35 nm, a thermal conductivity of at least 250 W/mK per unit of specific gravity, and/or an electrical conductivity no less than 2,500 S/cm per unit of specific gravity.

9. The alkali metal battery of claim 1 , wherein said graphene-carbon hybrid foam, when measured without said metal, has an oxygen content or non-carbon content less than 0.01% by weight and said pore walls contain stacked graphene planes having an inter-graphene spacing less than 0.34 nm, a thermal conductivity of at least 300 W/mK per unit of specific gravity, and/or an electrical conductivity no less than 3,000 S/cm per unit of specific gravity.

10. The alkali metal battery of claim 1 , wherein said graphene-carbon hybrid foam, when measured without said metal, has an oxygen content or non-carbon content no greater than 0.01% by weight and said pore walls contain stacked graphene planes having an inter-graphene spacing less than 0.336 nm, a thermal conductivity of at least 350 W/mK per unit of specific gravity, and/or an electrical conductivity no less than 3,500 S/cm per unit of specific gravity.

11. The alkali metal battery of claim 1 , wherein said graphene-carbon hybrid foam, when measured without said metal, has pore walls containing stacked graphene planes having an inter-graphene spacing less than 0.336 nm, a thermal conductivity greater than 400 W/mK per unit of specific gravity, and/or an electrical conductivity greater than 4,000 S/cm per unit of specific gravity.

12. The alkali metal battery of claim 1 , wherein the pore walls contain stacked graphene planes having an inter-graphene spacing less than 0.337 nm and a mosaic spread value less than 1.0.

13. The alkali metal battery of claim 1 , wherein said pore walls contain a 3D network of interconnected graphene planes.

14. The alkali metal battery of claim 1 , wherein said foam, when measured without said metal, has a physical density higher than 0.8 g/cm 3 and a specific surface area greater than 800 m 2 /g.

15. The alkali metal battery of claim 1 , wherein said foam, when measured without said metal, has a physical density higher than 1.0 g/cm 3 and a specific surface area greater than 500 m 2 /g.

16. The alkali metal battery of claim 1 , wherein said lithium source is selected from foil, particles, or filaments of lithium metal or lithium alloy having no less than 80% by weight of lithium element in said lithium alloy; or wherein said sodium source is selected from foil, particles, or filaments of sodium metal or sodium alloy having no less than 80% by weight of sodium element in said sodium alloy.

17. An alkali metal battery electrode containing an integral 3D graphene-carbon-metal hybrid foam composed of multiple pores, pore walls, and a lithium-attracting metal or sodium-attracting metal residing in said pores or deposited on said pore walls; wherein said lithium-attracting metal is selected from Au, Ag, Mg, Zn, Ti, Na, K, Al, Fe, Mn, Co, Ni, Sn, V, Cr, or an alloy thereof for a lithium metal battery, or said sodium-attracting metal is selected from Au, Ag, Mg, Zn, Ti, Li, K, Al, Fe, Mn, Co, Ni, Sn, V, Cr, or an alloy thereof for a sodium metal battery, and is in an amount of 0.1% to 90% of the total hybrid foam weight, and said pore walls contain single-layer or few-layer graphene sheets chemically bonded by a carbon material having a carbon material-to-graphene weight ratio from 1/200 to 1/2, wherein said few-layer graphene sheets have 2-10 layers of stacked graphene planes having an inter-plane spacing d 002 from 0.3354 nm to 0.40 nm as measured by X-ray diffraction and said single-layer or few-layer graphene sheets contain a pristine graphene material having essentially zero % of non-carbon elements, or a non-pristine graphene material having 0.001% to 25% by weight of non-carbon elements wherein said non-pristine graphene is selected from graphene oxide, reduced graphene oxide, graphene fluoride, graphene chloride, graphene bromide, graphene iodide, hydrogenated graphene, nitrogenated graphene, doped graphene, chemically functionalized graphene, or a combination thereof; wherein said integral 3D graphene-carbon-metal hybrid foam is pre-loaded with lithium or sodium before said electrode is made, or said electrode further comprises a lithium source or a sodium source.

18. An alkali metal battery having a cathode, an anode comprising the electrode of claim 17 , a porous separator electronically separating said anode and said cathode, and/or an electrolyte in ionic contact with said anode and said cathode, wherein a weight ratio of said pre-loaded lithium to said lithium-attracting metal or a weight ratio of said pre-loaded sodium to said sodium-attracting metal is from 1/100 to 100/1.

19. A process for producing the alkali metal battery electrode containing an integral 3D graphene-carbon-metal hybrid foam of claim 17 , said process comprising:

(a) mixing multiple particles of a graphitic material and multiple particles of a solid polymer carrier material to form a mixture in an impacting chamber of an energy impacting apparatus;

(b) operating said energy impacting apparatus with a frequency and an intensity for a length of time sufficient for peeling off graphene sheets from said graphitic material and transferring said graphene sheets to surfaces of said solid polymer carrier material particles to produce graphene-coated or graphene-embedded polymer particles inside said impacting chamber;

(c) recovering said graphene-coated or graphene-embedded polymer particles from said impacting chamber;

(d) mixing said graphene-coated or graphene-embedded polymer particles with said lithium-attracting metal, or a precursor to said metal, to form a mixture;

(e) consolidating said mixture into a sheet, film, rod, or filament structure;

(f) pyrolyzing said structure to thermally convert said polymer into pores and carbon or graphite that bonds said graphene sheets to form a sheet, film, rod, or filament of said integral 3D graphene-carbon-metal hybrid foam; and

(g) adding said pre-loaded lithium or sodium.

20. A process for producing the alkali metal battery electrode containing an integral 3D graphene-carbon-metal hybrid foam of claim 17 , said process comprising:

(A) mixing multiple particles of a graphitic material, multiple particles of a solid polymer carrier material, and milling media particles to form a mixture in an impacting chamber of an energy impacting apparatus;

(B) operating said energy impacting apparatus with a frequency and an intensity for a length of time sufficient for said milling media particles to impact said graphitic material particles, peeling off graphene sheets from said graphitic material particles and transferring said graphene sheets to surfaces of said solid polymer carrier material particles to produce graphene-coated or graphene-embedded polymer particles inside said impacting chamber;

(C) recovering said graphene-coated or graphene-embedded polymer particles from said impacting chamber;

(D) mixing said graphene-coated or graphene-embedded polymer particles with said lithium-attracting metal, or a precursor to said metal, to form a mixture;

(E) consolidating said mixture into a sheet, film, rod, or filament structure; and

(F) pyrolyzing said structure to thermally convert said polymer into pores and carbon or graphite that bonds said graphene sheets to form a sheet, film, rod, or filament of said integral 3D graphene-carbon-metal hybrid foam; and

(G) adding said pre-loaded lithium or sodium.

21. The process of claim 19 , wherein said step (e) of consolidating said mixture is conducted in a roll-to-roll manner to form a roll of sheet, film, or filament which is pyrolyzed to form a sheet, film, or filament of said integral 3D graphene-carbon-metal hybrid foam.

22. A process for producing an alkali metal battery, said process comprising steps of laminating an anode layer, a separator/electrolyte layer, and a cathode layer, wherein said anode layer comprises the electrode of claim 17 .

23. An alkali metal battery electrode containing an integral 3D graphene-carbon-metal hybrid foam composed of multiple pores, pore walls, and a lithium-attracting metal or sodium-attracting metal residing in said pores or deposited on said pore walls; wherein said lithium-attracting metal is selected from Au, Ag, Mg, Na, K, V, Cr, or an alloy thereof for a lithium metal battery, or said sodium-attracting metal is selected from Au, Ag, Mg, Li, K, V, Cr, or an alloy thereof for a sodium metal battery, and is in an amount of 0.1% to 90% of the total hybrid foam weight, and said pore walls contain single-layer or few-layer graphene sheets chemically bonded by a carbon material having a carbon material-to-graphene weight ratio from 1/200 to 1/2, wherein said few-layer graphene sheets have 2-10 layers of stacked graphene planes having an inter-plane spacing d 002 from 0.3354 nm to 0.40 nm as measured by X-ray diffraction and said single-layer or few-layer graphene sheets contain a pristine graphene material having essentially zero % of non-carbon elements, or a non-pristine graphene material having 0.001% to 25% by weight of non-carbon elements wherein said non-pristine graphene is selected from the group consisting of graphene oxide, reduced graphene oxide, graphene fluoride, graphene chloride, graphene bromide, graphene iodide, hydrogenated graphene, nitrogenated graphene, doped graphene, chemically functionalized graphene, and combination thereof.