CA2319460A1 - Lithium storage battery - Google Patents

Lithium storage battery Download PDF

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Publication number
CA2319460A1
CA2319460A1 CA002319460A CA2319460A CA2319460A1 CA 2319460 A1 CA2319460 A1 CA 2319460A1 CA 002319460 A CA002319460 A CA 002319460A CA 2319460 A CA2319460 A CA 2319460A CA 2319460 A1 CA2319460 A1 CA 2319460A1
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CA
Canada
Prior art keywords
secondary battery
lithium secondary
lithium
positive electrode
layer
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CA002319460A
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French (fr)
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CA2319460C (en
Inventor
Nobuhiro Ota
Shosaku Yamanaka
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Sumitomo Electric Industries Ltd
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Individual
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Publication of CA2319460C publication Critical patent/CA2319460C/en
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Expired - Fee Related legal-status Critical Current

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
    • H01M10/0562—Solid materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/621—Binders
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/621—Binders
    • H01M4/622—Binders being polymers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M6/00—Primary cells; Manufacture thereof
    • H01M6/14—Cells with non-aqueous electrolyte
    • H01M6/18—Cells with non-aqueous electrolyte with solid electrolyte
    • H01M6/187—Solid electrolyte characterised by the form
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0065—Solid electrolytes
    • H01M2300/0068—Solid electrolytes inorganic
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0088—Composites
    • H01M2300/0094—Composites in the form of layered products, e.g. coatings
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/40—Alloys based on alkali metals
    • H01M4/405—Alloys based on lithium
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/46—Separators, membranes or diaphragms characterised by their combination with electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M6/00—Primary cells; Manufacture thereof
    • H01M6/14—Cells with non-aqueous electrolyte
    • H01M6/18—Cells with non-aqueous electrolyte with solid electrolyte
    • H01M6/182—Cells with non-aqueous electrolyte with solid electrolyte with halogenide as solid electrolyte
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
    • Y02T10/00—Road transport of goods or passengers
    • Y02T10/60—Other road transportation technologies with climate change mitigation effect
    • Y02T10/70—Energy storage systems for electromobility, e.g. batteries

Abstract

A lithium storage battery having a high energy density and preferred electrical charge/discharge performance is produced to prevent a short circuit that may be caused by dendrite produced from the negative electrode. The lithium storage battery comprises an electrolyte layer, a positive electrode, and a negative electrode consisting of a lithium-containing material. The electrolyte layer consists of an inorganic solid electrolyte, and a positive electrode contains an organic polymer.
Preferably, the electrolyte layer contains at least one element chosen from a group that consists of oxygen, sulfur, nitrogen, sulfide and oxynitride. Preferably, the lithium ion conductivity of the organic electrolytic solution of the positive electrode is lower than that of the inorganic solid electrolyte of the electrolyte layer.

Claims (33)

1. A lithium secondary battery comprising an electrolytic layer, a positive electrode, and a negative electrode that is made of a lithium-containing material, in which battery:
(a) the electrolytic layer is made of an inorganic solid electrolyte; and (b) the positive electrode contains an organic high polymer.
2. The lithium secondary battery as defined in claim 1, wherein the electrolytic layer has a lithium-ion conductivity of 1 X 10-5 S/cm or more at 25 °C.
3. The lithium secondary battery as defined in claim 1, wherein the electrolytic layer has a lithium-ion conductivity of 5 X 10-5 S/cm or more at 25 °C.
4. The lithium secondary battery as defined in claim 1, wherein the electrolytic layer is made of an amorphous body.
5. The lithium secondary battery as defined in claim 1, wherein the electrolytic layer contains at least one type selected from the group consisting of oxygen, nitrogen, sulfide, and oxynitride.
6. The lithium secondary battery as defined in claim 5, wherein:
(a) the sulfide is composed of at least one type selected from the group consisting of Li2S, a compound between Li2S and SiS2, a compound between Li2S
and GeS2, and a compound between Li2S and Ga2S3; and (b) the oxynitride is composed of at least one type selected from the group consisting of Li3PO4-x N2x/3, Li4SiO4-x N2x/3, Li4GeO4-x N2x/3 (where 0 < X <
4), and LigBO3-x N2x/3 (where 0 < X < 3).
7. The lithium secondary battery as defined in claim 1, wherein the electrolytic layer contains:
(a) an Li constituent not less than 30 atm. % and not more than 65 atm. %;
(b) at least one type of element selected from the group consisting of sulfur, silicon, boron, germanium, and gallium; and (c) sulfur.
8. The lithium secondary battery as defined in claim 7, wherein the electrolytic layer contains at least one element selected from the group consisting of oxygen and nitrogen.
9. The lithium secondary battery as defined in claim 1, wherein the electrolytic layer has a thickness not less than 50 nm and not more than 50 µm.
10. The lithium secondary battery as defined in claim 1, wherein the electrolytic layer consists of two layers that are a positive electrode-side layer and a negative electrode-side layer.
11. The lithium secondary battery as defined in claim 10, wherein:
(a) the negative electrode-side layer is a film made of a lithium ion-conductive compound containing sulfide; and (b) the positive electrode-side layer is a film made of a lithium ion-conductive compound containing oxide.
12. The lithium secondary battery as defined in claim 10, wherein:
(a) the electrolytic layer consisting of two layers has a total thickness not less than 2 µm and not more than 22 µm; and (b) the positive electrode-side layer has a thickness not less than 0.1 µm and not more than 2 µm.
13. The lithium secondary battery as defined in claim 10, wherein:
(a) the negative electrode-side layer contains lithium sulfide and silicon sulfide; and (b) the positive electrode-side layer contains at least one type selected from the group consisting of a phosphate compound and a titanate compound.
14. The lithium secondary battery as defined in claim 10, wherein the positive electrode-side layer contains:
(a) an Li constituent not less than 30 atm.% and not more than 50 atm. %;
(b) phosphorus; and (c) at least one element selected from the group consisting of oxygen and nitrogen.
15. The lithium secondary battery as defined in claim 10, wherein the positive electrode-side layer has a thickness not less than 1% and not more than 50% of the thickness of the negative electrode-side layer.
16. The lithium secondary battery as defined in claim 10, wherein the positive electrode-side layer has a thickness not less than 10 nm and not more than 25 µm.
17. The lithium secondary battery as defined in claim 10, wherein:
(a) the positive electrode contains inorganic solid electrolytic particles having lithium-ion conductivity; and (b) the inorganic solid electrolytic particles have an ionic conductivity of S/cm or more.
18. The lithium secondary battery as defined in claim 1, wherein the organic high polymer contained in the positive electrode is a disulfide-family high polymer containing polyaniline.
19. The lithium secondary battery as defined in claim 1, wherein the organic high polymer contained in the positive electrode contains one type of lithium salt selected from the group consisting of LiPF6 and LiCF3SO3.
20. The lithium secondary battery as defined in claim 1, wherein the positive electrode contains an organic electrolysis solution.
21. The lithium secondary battery as defined in claim 20, wherein the organic electrolysis solution contained in the positive electrode has a lithium ion-conductivity lower than that of the inorganic solid electrolyte that constitutes the electrolytic layer.
22. The lithium secondary battery as defined in claim 20, wherein the organic electrolysis solution contained in the positive electrode:
(a) comes into contact with the lithium-containing material that constitutes the negative electrode; and (b) thereby reduces the ionic conductivity of the organic electrolysis solution in the vicinity of the contact portion to a value lower than that of the inorganic solid electrolyte.
23. The lithium secondary battery as defined in claim 20, wherein the organic solvent contained in the organic electrolysis solution contained in the positive electrode:
(a) comes into contact with the lithium-containing material that constitutes the negative electrode; and (b) thereby gasifies in the vicinity of the contact portion.
24. The lithium secondary battery as defined in claim 20, wherein the organic solvent contained in the organic electrolysis solution contained in the positive electrode:
(a) comes into contact with the lithium-containing material that constitutes the negative electrode; and (b) thereby solidifies in the vicinity of the contact portion.
25. The lithium secondary battery as defined in claim 20, wherein the organic solvent contained in the organic electrolysis solution contained in the positive electrode:
(a) comes into contact with the lithium-containing material that constitutes the negative electrode; and (b) thereby increases the viscosity of the organic electrolysis solution in the vicinity of the contact portion.
26. The lithium secondary battery as defined in claim 20, wherein the organic solvent contained in the organic electrolysis solution contained in the positive electrode contains a sulfolane-family compound.
27. The lithium secondary battery as defined in claim 20, wherein the organic solvent contained in the organic electrolysis solution contained in the positive electrode contains a chain carboxylic ester family.
28. The lithium secondary battery as defined in claim 20, wherein the organic solvent contained in the organic electrolysis solution contained in the positive electrode contains at least one type of compound selected from the group consisting of compounds having a nitrile group and compounds having olefinic linkage.
29. The lithium secondary battery as defined in claim 1, wherein the negative electrode has a surface roughness not less than 0.01 µm and not more than 5 µm in the value of Rmax.
30. The lithium secondary battery as defined in claim 1, wherein the negative electrode:
(a) has at its electrolytic-layer side a layer of a metal that forms an alloy or intermetallic compound with lithium; and (b) has a multilayer or a graded structure in composition.
31. The lithium secondary battery as defined in claim 1, wherein the negative electrode:
(a) has no oxide layer on its surface; and (b) has a sulfide or nitride layer on its surface.
32. The lithium secondary battery as defined in claim 1, wherein the electrolytic layer is formed directly on the surface of the negative electrode without the medium of an oxide layer.
33. The lithium secondary battery as defined in claim 1, wherein:
(a) the positive and negative electrodes are each provided with a collector;
and (b) the electrolytic layer is formed directly on the negative electrode-side collector without providing a lithium-containing material as the negative electrode.
CA002319460A 1998-12-03 1999-11-29 Lithium storage battery Expired - Fee Related CA2319460C (en)

Applications Claiming Priority (7)

Application Number Priority Date Filing Date Title
JP10/344593 1998-12-03
JP34459398 1998-12-03
JP773699 1999-01-14
JP11/7736 1999-01-14
JP11/78733 1999-03-24
JP7873399 1999-03-24
PCT/JP1999/006668 WO2000033409A1 (en) 1998-12-03 1999-11-29 Lithium storage battery

Publications (2)

Publication Number Publication Date
CA2319460A1 true CA2319460A1 (en) 2000-06-08
CA2319460C CA2319460C (en) 2010-02-02

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CA002319460A Expired - Fee Related CA2319460C (en) 1998-12-03 1999-11-29 Lithium storage battery

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US (1) US6365300B1 (en)
EP (1) EP1052718B1 (en)
CA (1) CA2319460C (en)
DE (1) DE69936706T2 (en)
WO (1) WO2000033409A1 (en)

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