Sodium-ion battery containing a high-capacity graphitic anode and manufacturing method

Patent metadata

Field	Value
Publication number	US-12374691-B2
Application number	US-202217650969-A
Country	US
Kind code	B2
Filing date	Feb 14, 2022
Priority date	Feb 14, 2022
Publication date	Jul 29, 2025
Grant date	Jul 29, 2025

Abstract

A rechargeable sodium-ion cell, comprising an anode, a cathode, a separator that electronically isolates the anode from the cathode, and an electrolyte in ionic contact with the anode active and the cathode, wherein the anode comprises a graphite or carbon material having expanded inter-graphene planar spaces with an inter-planar spacing d 002 from 0.43 nm to 3.0 nm, as measured by X-ray diffraction, and the expanded inter-graphene planar spaces store sodium ions to a specific capacity no less than 150 mAh/g when the cell is in a charged state. Also provided is a method of producing such an anode and sodium-ion cell.

First claim

The invention claimed is:

1. A rechargeable sodium-ion cell, comprising an anode, a cathode, and
an electrolyte in ionic contact with the anode and the cathode, wherein the anode comprises a graphite or carbon material having expanded inter-graphene planar spaces with an inter-planar spacing d 002 from 0.43 nm to 3.0 nm, as measured by X-ray diffraction, and the expanded inter-graphene planar spaces store sodium ions to a specific capacity no less than 150 mAh/g when the cell is in a charged state,
wherein said carbon or graphite material contains a non-carbon element selected from fluorine, chlorine, bromine, iodine, nitrogen, hydrogen, or boron.

2. The rechargeable sodium-ion cell of claim 1 , wherein the expanded inter-graphene planar spaces have an inter-planar spacing d 002 from 0.50 nm to 2.0 nm.

3. The rechargeable sodium-ion cell of claim 1 , wherein said carbon or graphite material in said anode 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, 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, 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 a value from 0.43 nm to 3.0 nm after said expansion treatment.

4. The rechargeable sodium-ion cell of claim 3 , 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 0.6 nm to 1.5 nm.

5. The rechargeable sodium-ion cell of claim 4 , wherein said stack contains from 2 to 100 graphene planes.

6. The rechargeable sodium-ion cell of claim 1 , wherein said inter-planar spacing d 002 is from 1.2 nm to 2.0 nm.

7. The rechargeable alkali metal-sulfur cell of claim 3 , wherein said expansion treatment includes a procedure selected from 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.

8. An anode for a rechargeable sodium-ion cell, wherein said anode comprises a graphite or carbon material having expanded inter-graphene planar spaces with an inter-planar spacing d 002 from 0.43 nm to 3.0 nm, as measured by X-ray diffraction, and the expanded inter-graphene planar spaces store sodium ions to a specific capacity no less than 150 mAh/g when the cell is in a charged state;
wherein said carbon or graphite material contains a non-carbon element selected from fluorine, chlorine, bromine, iodine, nitrogen, hydrogen, or boron.

9. The anode of claim 8 , wherein said carbon or graphite material in said anode 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, 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, 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 0.43 nm to 2.0 nm after said expansion treatment.

10. The anode of claim 8 , 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 0.45 nm to 1.5 nm.

11. The anode of claim 10 , wherein said stack contains from 2 to 100 graphene planes.

12. The rechargeable sodium-ion cell of claim 1 , wherein said electrolyte is selected from solid polymer electrolyte, polymer gel electrolyte, composite electrolyte, ionic liquid electrolyte, non-aqueous organic liquid electrolyte, soft matter phase electrolyte, inorganic solid-state electrolyte, or a combination thereof.

13. The rechargeable sodium-ion cell of claim 1 , wherein said electrolyte contains a salt selected from an ionic liquid salt, sodium perchlorate (NaClO 4 ), potassium perchlorate (KClO 4 ), sodium hexafluorophosphate (NaPF 6 ), potassium hexafluorophosphate (KPF 6 ), sodium borofluoride (NaBF 4 ), potassium borofluoride (KBF 4 ), sodium hexafluoroarsenide, potassium hexafluoroarsenide, sodium trifluoro-metasulfonate (NaCF 3 SO 3 ), potassium trifluoro-metasulfonate (KCF 3 SO 3 ), bis-trifluoromethyl sulfonylimide sodium (NaN(CF 3 SO 2 ) 2 ), sodium trifluoromethanesulfonimide (NaTFSI), bis-trifluoromethyl sulfonylimide potassium (KN(CF 3 SO 2 ) 2 ), a combination thereof, or a combination thereof with lithium perchlorate (LiClO 4 ), lithium hexafluorophosphate (LiPF 6 ), lithium borofluoride (LiBF 4 ), lithium hexafluoroarsenide (LiAsF 6 ), lithium trifluoro-metasulfonate (LiCF 3 SO 3 ), bis-trifluoromethyl sulfonylimide lithium (LiN(CF 3 SO 2 ) 2 , Lithium bis(oxalato)borate (LiBOB), lithium oxalyldifluoroborate (LiBF 2 C 2 O 4 ), lithium oxalyldifluoroborate (LiBF 2 C 2 O 4 ), Lithium nitrate (LiNO 3 ), Li-Fluoroalkyl-Phosphates (LiPF3(CF 2 CF 3 ) 3 ), or lithium bisperfluoroethysulfonylimide (LiBETI).

14. The rechargeable sodium-ion cell of claim 13 , wherein said electrolyte comprises a solvent selected from ethylene carbonate (EC), dimethyl carbonate (DMC), methylethyl carbonate (MEC), diethyl carbonate (DEC), ethyl propionate, methyl propionate, propylene carbonate (PC), gamma.-butyrolactone (γ-BL), acetonitrile (AN), ethyl acetate (EA), propyl formate (PF), methyl formate (MF), toluene, xylene or methyl acetate (MA), fluoroethylene carbonate (FEC), vinylene carbonate (VC), allyl ethyl carbonate (AEC), 1,3-dioxolane (DOL), 1,2-dimethoxyethane (DME), tetraethylene glycol dimethylether (TEGDME), Poly(ethylene glycol) dimethyl ether (PEGDME), diethylene glycol dibutyl ether (DEGDBE), 2-ethoxyethyl ether (EEE), sulfone, sulfolane, a room temperature ionic liquid, or a combination thereof.

15. The rechargeable sodium-ion cell of claim 1 , wherein the cathode comprises a cathode active material selected from NaFePO 4 , Na (1-x) K x PO 4 , KFePO 4 , Na 0.7 FePO 4 , Na 1.5 VOPO 4 F 0.5 , Na 3 V 2 (PO 4 ) 3 , Na 3 V 2 (PO 4 ) 2 F 3 , Na 2 FePO 4 F, NaFeF 3 , NaVPO 4 F, KVPO 4 F, Na 3 V 2 (PO 4 ) 2 F 3 , Na 1.5 VOPO 4 F 0.5 , Na 3 V 2 (PO 4 ) 3 , NaV 6 O 15 , Na x VO 2 , Na 0.33 V 2 O 5 , Na x CoO 2 , Na 2/3 [Ni 1/3 Mn 2/3 ]O 2 , Na x (Fe 1/2 Mn 1/2 )O 2 , Na x MnO 2 , λ-MnO 2 , Na x K (1-x) MnO 2 , Na 0.44 MnO 2 , Na 0.44 MnO 2 /C, Na 4 Mn 9 O 18 , NaFe 2 Mn(PO 4 ) 3 , Na 2 Ti 3 O 7 , Ni 1/3 Mn 1/3 Co 1/3 O 2 , Cu 0.56 Ni 0.44 HCF, NiHCF, Na x MnO 2 , NaCrO 2 , KCrO 2 , Na 3 Ti 2 (PO 4 ) 3 , NiCo 2 O 4 , Ni 3 S 2 /FeS 2 , Sb 2 O 4 , Na 4 Fe(CN) 6 /C, NaV 1-x Cr x PO 4 F, Se z S y , y/z=0.01 to 100, Se, sodium polysulfide, sulfur, Alluaudites, or a combination thereof, wherein x is from 0.1 to 1.0.

16. The rechargeable sodium-ion cell of claim 1 , wherein the cathode comprises a cathode active material selected from a Na-based layered oxide, a polya

Assignees

• Global Graphene Group Inc
• Honeycomb Battery Company

Inventors

• Jang Bor Z

Classifications

• H01M10/054 Primary

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

• H01M2004/027

  Negative electrodes · CPC title

• H01M4/587 Primary

  for inserting or intercalating light metals · CPC title

• H01M10/0569

  characterised by the solvents · CPC title

• H01M4/133

  Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx · CPC title