Method of producing anode or cathode particulates for alkali metal batteries

Patent metadata

Field	Value
Publication number	US-10797313-B2
Application number	US-201715832078-A
Country	US
Kind code	B2
Filing date	Dec 5, 2017
Priority date	Dec 5, 2017
Publication date	Oct 6, 2020
Grant date	Oct 6, 2020

Abstract

Provided is method of producing anode or cathode particulates for an alkali metal battery. The method comprises: (a) preparing a slurry containing particles of an anode or cathode active material, an electron-conducting material, and an electrolyte containing a lithium salt or sodium salt and an optional polymer dissolved in a liquid solvent; and (b) conducting a particulate-forming means to convert the slurry into multiple anode or cathode particulates, wherein an anode or a cathode particulate is composed of (i) particles of the active material, (ii) the electron-conducting material, and (iii) an electrolyte, wherein the electron-conducting material forms a 3D network of electron-conducting pathways and the electrolyte forms a 3D network of lithium ion- or sodium ion-conducting channels and wherein the anode particulate or cathode particulate has a dimension from 10 nm to 100 μm and an electrical conductivity from about 10 −6 S/cm to about 300 S/cm.

First claim

We claim:

1. A method of producing anode particulates or cathode particulates for use in an alkali metal battery, said method comprising:
(a) preparing a slurry containing particles of an anode or cathode active material capable of reversibly absorbing and desorbing lithium ions or sodium ions, an electron-conducting material, and an electrolyte containing a lithium salt or sodium salt and an optional polymer dissolved in a liquid solvent; and
(b) conducting a particulate-forming means to convert said slurry into multiple anode particulates or cathode particulates, wherein an anode particulate or a cathode particulate is composed of (i) particles of said anode or cathode active material, (ii) said electron-conducting material, and (iii) said electrolyte, wherein said electron-conducting material forms a three dimensional network of electron-conducting pathways in electronic contact with said anode or cathode active material and said electrolyte forms a three dimensional network of lithium ion- or sodium ion-conducting channels in ionic contact with said anode or cathode active material and wherein said anode particulate or cathode particulate has a dimension from 10 nm to 300 μm and an electrical conductivity from about 10 −7 S/cm to about 300 S/cm.

2. The method of claim 1 , wherein said particulate-forming means is selected from pan-coating method, air-suspension coating method, centrifugal extrusion, vibration nozzle method, spray-drying, interfacial polycondensation or interfacial cross-linking, in situ polymerization, matrix polymerization, or a combination thereof.

3. The method 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.

4. The method of claim 3 , wherein said prelithiated graphene sheets are selected from prelithiated versions of pristine graphene, graphene oxide, reduced graphene oxide, graphene fluoride, graphene chloride, graphene bromide, graphene iodide, hydrogenated graphene, nitrogenated graphene, boron-doped graphene, nitrogen-doped graphene, chemically functionalized graphene, a physically or chemically activated or etched version thereof, or a combination thereof.

5. The method 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;
(e) graphene sheets pre-loaded with sodium or potassium;
(f) and combinations thereof.

6. The method 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.

7. The method 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.

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

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

10. The method of claim 1 , wherein said conducting material contains an electron-conducting polymer selected from polyaniline, polypyrrole, polythiophene, polyfuran, a bi-cyclic polymer, a sulfonated derivative thereof, or a combination thereof.

11. The method of claim 1 , wherein said electrolyte has a lithium ion conductivity or sodium ion conductivity from 10 −7 S/cm to 0.05 S/cm at room temperature.

12. The method of claim 1 , wherein said electrolyte is selected from an aqueous electrolyte, an organic liquid electrolyte, an ionic liquid electrolyte, a polymer gel electrolyte, a polymer electrolyte, an inorganic solid state electrolyte, a quasi-solid electrolyte, or a combination thereof.

13. The method 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 nanofiber, a graphitic nanofiber, a conductive polymer fiber, a metal nanowire, a metal-coated fiber, a graphene sheet, an expanded graphite platelet, carbon black, acetylene black, needle coke, or a combination thereof.

14. The method of claim 1 , wherein said cathode active material contains a sodium intercalation compound or a potassium intercalation compound 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 0.1≤x≤1.0.

15. The method of claim 1 , wherein said cathode active material comprises an alkali metal intercalation compound or alkali metal-absorbing compound selected from an inorganic material, an organic or polymeric material, a metal oxide/phosphate/sulfide, or a combination thereof.

16. The method of c

Assignees

• Nanotek Instruments Inc
• Global Graphene Group Inc

Inventors

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

Classifications

• H01M10/39

  working at high temperature · CPC title

• H01M2300/0037

  Mixture of solvents · CPC title

• H01M4/40 Primary

  Alloys based on alkali metals · CPC title

• H01M4/13 Primary

  Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof · CPC title

• H01M4/583

  Carbonaceous material, e.g. graphite-intercalation compounds or CFx · CPC title