Method of producing deformable quasi-solid electrode material for alkali metal batteries

Patent metadata

Field	Value
Publication number	US-9960451-B1
Application number	US-201715604606-A
Country	US
Kind code	B1
Filing date	May 24, 2017
Priority date	May 24, 2017
Publication date	May 1, 2018
Grant date	May 1, 2018

Abstract

A method of preparing an alkali metal cell having a quasi-solid electrode, the method comprising: (a) combining a quantity of an active material, a quantity of an electrolyte, and a conductive additive to form a deformable and electrically conductive electrode material, wherein the conductive additive, containing conductive filaments, forms a 3D network of electron-conducting pathways; (b) forming the electrode material into a quasi-solid electrode, wherein the forming step includes deforming the electrode material into an electrode shape without interrupting the 3D network of electron-conducting pathways such that the electrode maintains an electrical conductivity no less than 10 −6 S/cm; (c) forming a second electrode; and (d) forming an alkali metal cell by combining the quasi-solid electrode and the second electrode having an ion-conducting separator disposed between the two electrodes.

First claim

We claim:

1. A method of preparing an alkali metal cell having a quasi-solid electrode, the method comprising:
a) combining a quantity of an active material, a quantity of an electrolyte, and a conductive additive to form a deformable and electrically conductive electrode material, wherein said conductive additive, containing conductive filaments, forms a 3D network of electron-conducting pathways;
b) forming the electrode material into a quasi-solid electrode, wherein said forming includes deforming the electrode material into an electrode shape without interrupting said 3D network of electron-conducting pathways such that the electrode maintains an electrical conductivity no less than 10 −6 S/cm;
c) forming a second electrode; and
d) forming an alkali metal cell by combining the quasi-solid electrode and the second electrode.

2. The method of claim 1 , wherein said electrolyte is a quasi-solid electrolyte containing a lithium salt or sodium salt dissolved in a liquid solvent with a salt concentration from 2.5 M to 14 M.

3. The method of claim 1 , wherein said electrolyte is a quasi-solid electrolyte containing a lithium salt or sodium salt dissolved in a liquid solvent with a salt concentration from 3.0 M to 11 M.

4. The method of claim 1 , wherein said conductive filaments are selected from carbon fibers, graphite fibers, carbon nanofibers, graphite nanofibers, carbon nanotubes, needle coke, carbon whiskers, conductive polymer fibers, conductive material-coated fibers, metal nanowires, metal fibers, metal wires, graphene sheets, expanded graphite platelets, a combination thereof, or a combination thereof with non-filamentary conductive particles.

5. The method of claim 1 , wherein said electrode maintains an electrical conductivity from about 10 −5 S/cm to about 300 S/cm.

6. The method of claim 1 , wherein said deformable electrode material has an apparent viscosity of no less than about 10,000 Pa-s at an apparent shear rate of 1,000 s −1 .

7. The method of claim 1 , wherein said deformable electrode material has an apparent viscosity of no less than about 100,000 Pa-s at an apparent shear rate of 1,000 s −1 .

8. The method of claim 1 , wherein the quantity of the active material is about 20% to about 95% by volume of the electrode material.

9. The method of claim 1 , wherein the quantity of the active material is about 35% to about 85% by volume of the electrode material.

10. The method of claim 1 , wherein the quantity of the active material is about 50% to about 75% by volume of the electrode material.

11. The method of claim 1 , wherein said step of combining includes dispersing said conductive filaments into a liquid solvent to form a homogeneous suspension prior to adding said active material in said suspension and prior to dissolving a lithium salt or sodium salt in said liquid solvent of said suspension.

12. The method of claim 1 , wherein said steps of combining and forming the electrode material into a quasi-solid electrode include dissolving a lithium salt or sodium salt in a liquid solvent to form an electrolyte having a first salt concentration and subsequently removing portion of said liquid solvent to increase the salt concentration to obtain a quasi-solid electrolyte having a second salt concentration higher than the first concentration and higher than 2.5 M.

13. The method of claim 12 , wherein said removing does not cause precipitation or crystallization of said salt and said electrolyte is in a supersaturated state.

14. The method of claim 12 , wherein said liquid solvent contains a mixture of at least a first liquid solvent and a second liquid solvent and the first liquid solvent is more volatile than the second liquid solvent and wherein said removing portion of said liquid solvent includes removing said first liquid solvent.

15. The method of claim 1 , wherein said alkali metal cell is a lithium metal cell or lithium-ion cell and said active material is an anode active material selected from the group consisting of:
(a) particles of lithium metal or a lithium metal alloy;
(b) natural graphite particles, artificial graphite particles, meso-carbon microbeads (MCMB), carbon particles, needle coke, carbon nanotubes, carbon nanofibers, carbon fibers, and graphite fibers;
(c) 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);
(d) 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;
(e) oxides, carbides, nitrides, sulfides, phosphides, selenides, and tellurides of Si, Ge, Sn, Pb, Sb, Bi, Zn, Al, Fe, Ni, Co, Ti, Mn, or Cd, and their mixtures or composites;
(f) pre-lithiated versions thereof;
(g) pre-lithiated graphene sheets; and
combinations thereof.

16. The method of claim 15 , wherein said pre-lithiated graphene sheets are selected from pre-lithiated 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.

17. The method of claim 1 , wherein said alkali metal cell is a sodium metal cell or sodium-ion cell and said active material is an anode active material containing an alkali intercalation compound selected from petroleum coke, 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 (x=0.2 to 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.

18. The method of claim 1 , wherein said alkali metal cell is a sodium metal cell or sodium-ion cell and said active material is an anode active material selected from the group consisting of:
a) particles of sodium metal or a sodium metal alloy;
b) natural graphite particles, artificial graphite particles, meso-carbon microbeads (MCMB), carbon particles, needle coke, carbon nanotubes, carbon nanofibers, carbon fibers, and graphite fibers;
c) sodium-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;
d) sodium-containing alloys or intermetallic compounds of Si, Ge, Sn, Pb, Sb, Bi, Zn, Al, Ti, Co, Ni, Mn, Cd, and their mixtures;
e) sodium-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;
f) sodium salts;
g) graphene sheets pre-loaded with sodium ions; and combinations thereof.

19. The method of claim 1 , wherein said alkali metal cell is a lithium metal cell or lithium-ion cell and said active material is a cathode active material containing a lithium intercalation compound selected from the group consisting of lithium cobalt oxide, doped lithium cobalt oxide, lithium nickel oxide, doped lithium nickel oxide, lithium manganese oxide, doped lithium manganese oxide, lithium vanadium oxide, doped lithium vanadium oxid

Assignees

• Nanotek Instruments Inc

Inventors

• Zhamu Aruna
• Jang Bor Z

Classifications

• H01M10/0585 Primary

  of accumulators having only flat construction elements, i.e. flat positive electrodes, flat negative electrodes and flat separators · CPC title

• H01M4/5815

  Sulfides · CPC title

• H01M2300/0065

  Solid electrolytes · 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

• H01M4/502

  for non-aqueous cells (H01M4/505 takes precedence) · CPC title