Process for producing alkali metal or alkali-ion batteries having high volumetric and gravimetric energy densities

Patent metadata

Field	Value
Publication number	US-9564656-B1
Application number	US-201514756509-A
Country	US
Kind code	B1
Filing date	Sep 14, 2015
Priority date	Sep 14, 2015
Publication date	Feb 7, 2017
Grant date	Feb 7, 2017

Abstract

Provided is a process for producing an alkali metal battery, comprising: (A) Preparing an anode material suspension and a cathode active material suspension; (B) Assembling a porous cell framework composed of a first conductive foam structure, a second conductive foam structure, and a porous separator disposed between said first and said second conductive foam structure; and (C) Injecting the anode suspension into pores of the first conductive foam structure to form an anode and injecting cathode suspension into pores of the second conductive foam structure to form a cathode, wherein the anode active material has a material mass loading no less than 20 mg/cm 2 or the cathode active material has a material mass loading no less than 15 mg/cm 2 for an organic or polymer material or no less than 40 mg/cm 2 for an inorganic material. The resulting batteries exhibit exceptional gravimetric and volumetric energy densities and long cycle life.

First claim

The invention claimed is:

1. A process for producing an alkali metal battery, wherein said alkali metal is selected from sodium (Na), potassium (K), a combination of Na and K, a combination of Na and/or K with lithium (Li) and said alkali metal does not include lithium alone; said process comprising:
(A) preparing a first suspension of an anode active material and an optional conductive additive dispersed in a first liquid electrolyte and a second suspension of a cathode active material and an optional conductive additive dispersed in a second liquid electrolyte;
(B) assembling a porous cell framework composed of a first conductive foam structure as an anode current collector, a second conductive foam structure as a cathode current collector, and a porous separator disposed between said first and said second conductive foam structure; wherein said first and/or second conductive foam structure has a thickness no less than 100 μm and at least 80% by volume of pores; and
(C) injecting said first suspension into pores of said first conductive foam structure to form an anode and injecting said second suspension into pores of said second conductive foam structure to form a cathode to an extent that said anode active material has a material mass loading no less than 20 mg/cm 2 in said anode or said cathode active material has a material mass loading no less than 15 mg/cm 2 for an organic or polymer material or no less than 40 mg/cm 2 for an inorganic and non-polymer material in said cathode;

wherein said anode current collector, said separator, and said cathode current collector are assembled in a protective housing before or after said injecting of first suspension and/or said injecting of second suspension.

2. The process of claim 1 , wherein said cathode active material is a sodium or potassium intercalation compound or sodium- or potassium-absorbing compound selected from an inorganic material, an organic or polymeric material, a metal oxide/phosphate/sulfide, or a combination thereof.

3. The process of claim 2 , wherein said metal oxide/phosphate/sulfide is selected from a sodium cobalt oxide, sodium nickel oxide, sodium manganese oxide, sodium vanadium oxide, sodium-mixed metal oxide, sodium/potassium-transition metal oxide, sodium iron phosphate, sodium/potassium iron phosphate, sodium manganese phosphate, sodium/potassium manganese phosphate, sodium vanadium phosphate, sodium/potassium vanadium phosphate, sodium mixed metal phosphate, transition metal sulfide, or a combination thereof.

4. The process of claim 2 , wherein said inorganic material is selected from sulfur, sulfur compound, lithium polysulfide, transition metal dichalcogenide, a transition metal trichalcogenide, or a combination thereof.

5. The process of claim 2 , wherein said inorganic material is selected from TiS 2 , TaS 2 , MoS 2 , NbSe 3 , MnO 2 , CoO 2 , an iron oxide, a vanadium oxide, or a combination thereof.

6. The process of claim 1 , wherein said cathode active material contains a sodium intercalation compound or a potassium intercalation compound selected from NaFePO 4 , KFePO 4 , Na (1-x) K x PO 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, Alluaudites, or a combination thereof, wherein x is from 0.1 to 1.0.

7. The process of claim 1 , wherein said cathode active material is selected from a functional material or nano-structured material having an alkali metal ion-capturing functional group or alkali metal ion-storing surface in direct contact with said electrolyte.

8. The process of claim 7 , wherein said functional group reversibly reacts with an alkali metal ion, forms a redox pair with an alkali metal ion, or forms a chemical complex with an alkali metal ion.

9. The process of claim 7 , wherein said functional material or nano-structured material is 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; and combinations thereof.

10. The process of claim 7 , wherein said functional material or nano-structured material is selected from the group consisting of Poly(2,5-dihydroxy-1,4-benzoquinone-3,6-methylene), Na x C 6 O 6 (x=1-3), Na 2 (C 6 H 2 O 4 ), Na 2 C 8 H 4 O 4 or Na terephthalate, Na 2 C 6 H 4 O 4 or Na trans-trans-muconate), 3,4,9,10-perylenetetracarboxylicacid-dianhydride or PTCDA, sulfide polymer, PTCDA, 1,4,5,8-naphthalene-tetracarboxylicacid-dianhydride or NTCDA, Benzene-1,2,4,5-tetracarboxylic dianhydride, 1,4,5,8-tetrahydroxy anthraquinon, Tetrahydroxy-p-benzoquinone, and combinations thereof.

11. The process of claim 7 , wherein said functional material or nano-structured material has a specific surface area of at least 500 m 2 /g.

12. The process of claim 7 , wherein said functional material or nano-structured material has a specific surface area of at least 1,000 m 2 /g.

13. The process of claim 7 , wherein said functional material or nano-structured has a functional group selected from —COOH, ═O, —NH 2 , —OR, or —COOR, where R is a hydrocarbon radical.

14. The process of claim 1 , wherein said anode 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.

15. The process of claim 14 , wherein the alkali intercalation compound or alkali-containing compound is 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 ions or potassium ions.

16. The process of claim 15 , wherein said graphene sheets pre-loaded with sodium ions or potassium ions are selected from pre-sodiated or pre-potassiated versions of pristine graphene, g

Assignees

• Zhamu Aruna
• Jang Bor Z
• Nanotek Instruments Inc

Inventors

• Zhamu Aruna
• 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

• H01M10/049 Primary

  Processes for forming or storing electrodes in the battery container · CPC title

• H01M4/5835

  Comprising fluorine or fluoride salts · CPC title

• H01M4/60

  of organic compounds · CPC title

• H01M4/663

  containing carbon or carbonaceous materials as conductive part, e.g. graphite, carbon fibres · CPC title