Anode particulates or cathode particulates and alkali metal batteries

Patent metadata

Field	Value
Publication number	US-10873083-B2
Application number	US-201815860151-A
Country	US
Kind code	B2
Filing date	Jan 2, 2018
Priority date	Nov 30, 2017
Publication date	Dec 22, 2020
Grant date	Dec 22, 2020

Abstract

Provided is an anode particulate, having a dimension from 10 nm to 300 μm, for use in an alkali metal battery, the particulate comprising (i) an anode active material capable of reversibly absorbing/desorbing lithium or sodium ions, (ii) an electron-conducting material, and (iii) a lithium or sodium salt with an optional polymer or its monomer, but without a liquid solvent, for an electrolyte, wherein the electron-conducting material forms a 3D network of electron-conducting pathways in electronic contact with the anode active material and the lithium or sodium salt is in physical contact with the anode active material (so that the salt, when later impregnated with a liquid solvent, becomes an electrolyte forming a 3D network of lithium or sodium ion-conducting channels in ionic contact with the anode active material). The particulate can be of any shape, but preferably spherical or ellipsoidal in shape. Also provided is a cathode particulate.

First claim

We claim:

1. An anode particulate having a dimension from 10 nm to 300 μm for use in an alkali metal battery, said particulate comprising (i) an anode active material capable of reversibly absorbing and desorbing lithium ions or sodium ions, (ii) an electron-conducting material, and (iii) a lithium salt or sodium salt with an optional polymer or its monomer, but without a liquid solvent, for an electrolyte, wherein said electron-conducting material forms a 3D network of electron-conducting pathways in electronic contact with said anode active material and said lithium salt or sodium salt, when forming into an electrolyte, forms a 3D network of lithium ion- or sodium ion-conducting channels in ionic contact with said anode active material and wherein said anode particulate has an electrical conductivity from about 10 −6 S/cm to about 300 S/cm.

2. The anode particulate of claim 1 , wherein said alkali metal battery is a lithium-ion battery and said anode active material is selected from the group consisting of:
(a) particles of natural graphite, artificial graphite, mesocarbon microbeads (MCMB), needle coke, carbon particles, carbon fibers, carbon nanotubes, and carbon nanofibers;
(b) silicon (Si), germanium (Ge), tin (Sn), lead (Pb), antimony (Sb), bismuth (Bi), zinc (Zn), aluminum (Al), nickel (Ni), cobalt (Co), manganese (Mn), titanium (Ti), iron (Fe), and cadmium (Cd);
(c) alloys or intermetallic compounds of Si, Ge, Sn, Pb, Sb, Bi, Zn, Al, or Cd with other elements, wherein said alloys or compounds are stoichiometric or non-stoichiometric;
(d) oxides, carbides, nitrides, sulfides, phosphides, selenides, and tellurides of Si, Ge, Sn, Nb, Mo, Pb, Sb, Bi, Zn, Al, Fe, Ni, Co, Ti, Mn, or Cd, and their mixtures or composites;
(e) prelithiated versions thereof;
(f) prelithiated graphene sheets; and
combinations thereof.

3. The anode particulate of claim 1 , wherein the alkali metal battery is a sodium-ion battery and said anode active material contains an alkali intercalation compound selected from the following groups of materials:
(a) sodium- or potassium-doped silicon (Si), germanium (Ge), tin (Sn), lead (Pb), antimony (Sb), bismuth (Bi), zinc (Zn), aluminum (Al), titanium (Ti), cobalt (Co), nickel (Ni), manganese (Mn), cadmium (Cd), and mixtures thereof;
(b) sodium- or potassium-containing alloys or intermetallic compounds of Si, Ge, Sn, Pb, Sb, Bi, Zn, Al, Ti, Co, Ni, Mn, Cd, and their mixtures;
(c) sodium- or potassium-containing oxides, carbides, nitrides, sulfides, phosphides, selenides, tellurides, or antimonides of Si, Ge, Sn, Pb, Sb, Bi, Zn, Al, Fe, Ti, Co, Ni, Mn, Cd, and mixtures or composites thereof;
(d) sodium or potassium salts; and
(e) graphene sheets pre-loaded with sodium or potassium.

4. The anode particulate of claim 1 , wherein said alkali metal battery is a sodium-ion battery and said anode active material contains an alkali intercalation compound selected from petroleum coke, carbon black, amorphous carbon, activated carbon, hard carbon, soft carbon, templated carbon, hollow carbon nanowires, hollow carbon sphere, titanates, NaTi 2 (PO 4 ) 3 , Na 2 Ti 3 O 7 , Na 2 C 8 H 4 O 4 , Na 2 TP, Na x TiO 2 (0.2≤x≤1.0), Na 2 C 8 H 4 O 4 , carboxylate based materials, C 8 H 4 Na 2 O 4 , C 8 H 6 O 4 , C 8 H 5 NaO 4 , C 8 Na 2 F 4 O 4 , C 10 H 2 Na 4 O 8 , C 14 H 4 O 6 , C 14 H 4 Na 4 O 8 , or a combination thereof.

5. The anode particulate of claim 1 , wherein said anode active material contains a prelithiated Si, prelithiated Ge, prelithiated Sn, prelithiated SnO x , prelithiated SiO x , prelithiated iron oxide, prelithiated VO 2 , prelithiated Co 3 O 4 , prelithiated Ni 3 O 4 , prelithiated Mn 3 O 4 , or a combination thereof, wherein 1≤x≤2.

6. The anode particulate of claim 1 , wherein said anode active material is in a form of nanoparticle, nanowire, nanofiber, nanotube, nanosheet, nanobelt, nanoribbon, nanodisc, nanoplatelet, or nanohorn having a thickness or diameter from 0.5 nm to 100 nm.

7. The anode particulate of claim 1 , wherein said anode active material is coated with a layer of carbon, a conducting polymer, or a graphene sheet.

8. The anode particulate of claim 1 , wherein said electron-conducting polymer is selected from polyaniline, polypyrrole, polythiophene, polyfuran, a bi-cyclic polymer, a sulfonated derivative thereof, or a combination thereof.

9. The anode particulate of claim 1 , wherein said lithium salt is selected from lithium carbonate (Li 2 CO 3 ), lithium fluoride (LiF), lithium chloride (LiCl), lithium bromide (LiBr), lithium iodide (LiI), 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-Fluoro alkyl-Phosphates (LiPF 3 (CF 2 CF 3 ) 3 ), lithium bisperfluoro-ethysulfonylimide (LiBETI), lithium bis(trifluoromethanesulphonyl)imide, lithium bis(fluorosulphonyl)imide, lithium trifluoromethanesulfonimide (LiTFSI), an ionic liquid lithium salt, or a combination thereof.

10. The anode particulate of claim 1 , wherein said sodium salt is selected from sodium perchlorate (NaClO 4 ), sodium hexafluorophosphate (NaPF 6 ), sodium borofluoride (NaBF 4 ), sodium hexafluoroarsenide, sodium trifluoro-metasulfonate (NaCF 3 SO 3 ), bis-trifluoromethyl sulfonylimide sodium (NaN(CF 3 SO 2 ) 2 ), sodium trifluoromethanesulfonimide (NaTFSI), bis-trifluoromethyl sulfonylimide sodium (NaN(CF 3 SO 2 ) 2 ), or a combination thereof.

11. The anode particulate of claim 1 , further comprising a resin binder.

12. The anode particulate of claim 1 , wherein said electrolyte has a lithium ion conductivity or sodium ion conductivity no less than 10 −7 S/cm at room temperature.

13. The anode particulate of claim 1 , wherein said polymer contains a lithium ion-conducting or sodium ion-conducting polymer selected from poly(ethylene oxide) (PEO), Polypropylene oxide (PPO), poly(acrylonitrile) (PAN), poly(methyl methacrylate) (PMMA), poly(vinylidene fluoride) (PVdF), Poly bis-methoxy ethoxyethoxide-phosphazenex, Polyvinyl chloride, Polydimethylsiloxane, poly(vinylidene fluoride)-hexafluoropropylene (PVDF-HFP), a sulfonated polymer, or a combination thereof.

14. The anode particulate of claim 3 , wherein said sulfonated polymer is selected from the group consisting of poly(perfluoro sulfonic acid), sulfonated polytetrafluoroethylene, sulfonated perfluoroalkoxy derivatives of polytetrafluoroethylene, sulfonated polysulfone, sulfonated poly(ether ketone), sulfonated poly (ether ether ketone), sulfonated polystyrene, sulfonated polyimide, sulfonated styrene-butadiene copolymers, sulfonated poly chloro-trifluoroethylene (PCTFE), sulfonated perfluoroethylene-propylene copolymer (FEP), sulfonated ethylene-chlorotrifluoroethylene copolymer (ECTFE), sulfonated polyvinylidenefluoride (PVDF), sulfonated copolymers of polyvinylidenefluoride with hexafluoropropene and tetrafluoroethylene, sulfonated copolymers of ethylene and tetrafluoroethylene (ETFE), sulfonated polybenzimidazole (PBI), sulfonated polyaniline, sulfonated polypyrrole, sulfonated polythiophene, sulfonated polyfuran, a sulfonated bi-cyclic polymer, their chemical derivatives, copolymers, blends and combinations thereof.

15. The anode particulate of claim 1 , wherein said electron-conducting material is selected from a conducting polymer, a carbon fiber or graphite fiber, a carbon nanotube, a carbon nanofi

Assignees

• Global Graphene Group Inc

Inventors

• Zhamu Aruna
• He Hui
• Pan Baofei
• Jang Bor Z

Classifications

• H01M4/505

  of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy · CPC title

• H01M4/625

  Carbon or graphite · CPC title

• H01M4/5825

  Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines · CPC title

• H01M4/626

  Metals · CPC title

• H01M4/525

  of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy · CPC title