Alkali Metal-Sulfur Batteries Having High Volumetric and Gravimetric Energy Densities

Patent metadata

Field	Value
Publication number	US-2017207484-A1
Application number	US-201614998523-A
Country	US
Kind code	A1
Filing date	Jan 15, 2016
Priority date	Jan 15, 2016
Publication date	Jul 20, 2017
Grant date	—

Abstract

Provided is an alkali metal-sulfur battery, comprising: (a) an anode; (b) a cathode having (i) a cathode active material slurry comprising a cathode active material dispersed in an electrolyte and (ii) a conductive porous structure acting as a 3D cathode current collector having at least 70% by volume of pores and wherein cathode active material slurry is disposed in pores of the conductive porous structure, wherein the cathode active material is selected from sulfur, lithium polysulfide, sodium polysulfide, sulfur-polymer composite, sulfur-carbon composite, sulfur-graphene composite, or a combination thereof; and (c) a separator disposed between the anode and the cathode; wherein the cathode thickness-to-cathode current collector thickness ratio is from 0.8/1 to 1/0.8, and/or the cathode active material constitutes an electrode active material loading greater than 15 mg/cm 2 , and the 3D porous cathode current collector has a thickness no less than 200 μm (preferably thicker than 500 μm).

First claim

1 . An alkali metal-sulfur battery, comprising:
(A) an anode having (i) an anode active material slurry comprising an anode active material and an optional conductive additive dispersed in a first liquid or gel electrolyte and (ii) a conductive porous structure acting as a 3D anode current collector wherein said conductive porous structure has at least 70% by volume of pores and wherein said anode active material slurry is disposed in pores of said conductive porous structure; (B) a cathode having (i) a cathode active material slurry comprising a cathode active material and an optional conductive additive dispersed in a second liquid or gel electrolyte, the same as or different than said first liquid or gel electrolyte, and (ii) a conductive porous structure acting as a 3D cathode current collector wherein said conductive porous structure has at least 70% by volume of pores and wherein cathode active material slurry is disposed in pores of said conductive porous structure, wherein said cathode active material is selected from sulfur bonded to pore walls of said cathode current collector, sulfur bonded to or confined by a carbon or graphite material, sulfur bonded to or confined by a polymer, sulfur-carbon compound, metal sulfide M x S y , wherein x is an integer from 1 to 3 and y is an integer from 1 to 10, and M is a metal element selected from Li, Na, K, Mg, Ca, a transition metal, a metal from groups 13 to 17 of the periodic table, or a combination thereof; and (C) a separator disposed between said anode and said cathode;
wherein an anode thickness-to-anode current collector thickness ratio is from 0.8/1 to 1/0.8 and/or a cathode thickness-to-cathode current collector thickness ratio is from 0.8/1 to 1/0.8, said 3D porous anode current collector or cathode current collector has a thickness no less than 200 μm, and wherein said cathode active material constitutes an electrode active material loading greater than 10 mg/cm 2 , and/or said anode active material and said cathode active material combined exceeds 40% by weight of said battery cell weight.

2 . An alkali metal-sulfur battery, comprising:
(a) an anode having an anode active material coated on or in physical contact with an anode current collector wherein said anode active material is in ionic contact with a first electrolyte; (b) a cathode having (i) a cathode active material slurry comprising a cathode active material and an optional conductive additive dispersed in a second liquid or gel electrolyte, the same as or different than said first liquid or gel electrolyte, and (ii) a conductive porous structure acting as a 3D cathode current collector wherein said conductive porous structure has at least 70% by volume of pores and wherein cathode active material slurry is disposed in pores of said conductive porous structure, wherein said cathode active material is selected from sulfur, lithium polysulfide, sodium polysulfide, sulfur-polymer composite, organo-sulfides, sulfur-carbon composite, sulfur-graphene composite, or a combination thereof; and (c) a separator disposed between said anode and said cathode;
wherein a cathode thickness-to-cathode current collector thickness ratio is from 0.8/1 to 1/0.8, and/or said cathode active material constitutes an electrode active material loading greater than 15 mg/cm 2 , and said 3D cathode current collector has a thickness no less than 200 μm.

3 . The alkali metal-sulfur battery of claim 2 , wherein said anode current collector contains a porous foamed structure.

4 . The alkali metal-sulfur battery of claim 2 , wherein said cathode active material is supported by a functional material or nano-structured material selected from the group consisting of:
(a) A nano-structured or porous disordered carbon material selected from particles of a soft carbon, hard carbon, polymeric carbon or carbonized resin, meso-phase carbon, coke, carbonized pitch, carbon black, activated carbon, nano-cellular carbon foam or partially graphitized carbon; (b) A nano graphene platelet selected from a single-layer graphene sheet or multi-layer graphene platelet; (c) A carbon nanotube selected from a single-walled carbon nanotube or multi-walled carbon nanotube; (d) A carbon nano-fiber, nano-wire, metal oxide nano-wire or fiber, conductive polymer nano-fiber, or a combination thereof; (e) A carbonyl-containing organic or polymeric molecule; (f) A functional material containing a carbonyl, carboxylic, or amine group to reversibly capture sulfur;
and combinations thereof.

5 . The alkali metal-sulfur battery of claim 2 , wherein said anode active material contains an alkali ion source selected from an alkali metal, an alkali metal alloy, a mixture of alkali metal or alkali metal alloy with an alkali intercalation compound, an alkali element-containing compound, or a combination thereof.

6 . The alkali metal-sulfur battery of claim 1 , wherein 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, natural graphite, artificial graphite, lithium or sodium titanate, 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.

7 . The alkali metal-sulfur battery of claim 1 , wherein said anode active material contains an alkali intercalation compound or alkali-containing compound selected from the following groups of materials:
(A) Lithium- or 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; (B) Lithium- or sodium-containing alloys or intermetallic compounds of Si, Ge, Sn, Pb, Sb, Bi, Zn, Al, Ti, Co, Ni, Mn, Cd, and their mixtures; (C) Lithium- or 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; (D) Lithium or sodium salts; and (E) Graphene sheets pre-loaded with lithium or sodium.

8 . The alkali metal-sulfur battery of claim 7 , wherein said the graphene sheets pre-loaded with lithium or sodium are selected from pre-sodiated or 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.

9 . The alkali metal-sulfur battery of claim 2 , wherein said first electrolyte is a gel electrolyte or solid-state electrolyte.

10 . The alkali metal-sulfur battery of claim 1 , wherein said first or second liquid or gel electrolyte is selected from aqueous electrolyte, an organic electrolyte, ionic liquid electrolyte, mixture of an organic electrolyte and an ionic electrolyte, or a mixture thereof with a polymer.

11 . The alkali metal-sulfur battery of claim 10 , wherein said aqueous electrolyte contains a sodium salt or a potassium salt dissolved in water or a mixture of water and alcohol.

12 . alkali metal-ion battery of claim 11 , wherein said sodium salt or lithium salt is selected from Na 2 SO 4 , Li 2 SO 4 , a mixture thereof, NaOH, LiOH, NaCl, LiCl, NaF, LiF,

Assignees

• Zhamu Aruna
• Jang Bor Z

Inventors

• Zhamu Aruna
• Jang Bor Z

Classifications

• H01M4/1397

  of electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy · CPC title

• H01M2004/027

  Negative electrodes · CPC title

• D04H1/728

  by electro-spinning {(electro-spinning methods and apparatus D01D5/0007)} · CPC title

• H01M4/625

  Carbon or graphite · CPC title

• H01M4/1393

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