Positive electrode material for lithium secondary battery

Patent metadata

Field	Value
Publication number	US-10403893-B2
Application number	US-201414913234-A
Country	US
Kind code	B2
Filing date	Aug 21, 2014
Priority date	Aug 21, 2013
Publication date	Sep 3, 2019
Grant date	Sep 3, 2019

Abstract

A positive electrode material is used to produce a positive electrode of a lithium secondary battery, the positive electrode material being a composite lithium material that includes a first lithium compound and a second lithium compound. For instance, the first lithium compound is in the form of particles and comprises at least one compound selected from a layered lithium compound and a spinel-type lithium compound. Preferably, the second lithium compound comprises at least one compound selected from a lithium-containing phosphate compound and a lithium-containing silicate compound. An amorphous carbon material layer and/or graphene-structured carbon material layer is present on the entire surface of the first lithium compound and the second lithium compound. The second lithium compound forms a thin-film layer on part or the entirety of the carbon material layer present on the surface of the first lithium compound particles.

First claim

The invention claimed is:

1. A positive electrode material being a composite lithium material comprising:
a first lithium compound in the form of particles, the first lithium compound comprising a layered lithium compound, a spinel-type lithium compound, or a combination thereof, wherein the first lithium compound forms a core;
a first carbon material layer present on an entire surface of the first lithium compound particles, wherein the first carbon material layer forms a first shell on the core;
a second lithium compound forming a thin-film layer on part or the entirety of a surface of the first carbon material layer, the second lithium compound comprising a lithium-containing phosphate compound, a lithium-containing silicate compound, or a combination thereof, wherein the second lithium compound thin-film layer forms a second shell on the first shell; and
a second carbon material layer present on an entire surface of the thin film layer of the second lithium compound, wherein the second carbon material layer forms a third shell on the second shell,
wherein the carbon material of the first and second carbon material layers is independently selected from amorphous carbon material, graphene-structured carbon material, or a combination thereof; and
wherein the first and second lithium compounds are not in direct physical contact.

2. The positive electrode material according to claim 1 , wherein the first lithium compound comprises an α-layered Li(Ni α /Mn β /Co γ )O 2 , wherein α+β+γ=1, a spinel-type Li(Ni δ /Mn ε )O 4 , wherein δ+ε=2, or a combination thereof.

3. The positive electrode material according to claim 1 , further comprising a compound that includes an element selected from the elements of groups 3 to 6 of the periodic table, or an oxide thereof, or an aluminum halide compound, said compound being present on the surface of the particles of the first lithium compound.

4. The positive electrode material according to claim 3 , wherein the element selected from the elements of groups 3 to 6 of the periodic table is aluminum, molybdenum, titanium, zirconium, or sulfur.

5. The positive electrode material according to claim 3 , wherein the aluminum halide compound is aluminum fluoride.

6. The positive electrode material according to claim 1 , wherein the second lithium compound comprises olivine-type Li(Fe ζ /Co η /Mn θ )PO 4 , wherein ζ+η+θ=1, Li(Fe ι /Co κ /Mn λ )SiO 4 , wherein ι+κ+λ=1, or a combination thereof.

7. The positive electrode material according to claim 1 , further comprising a conductive carbon material, wherein the second carbon material layer and a surface layer of the conductive carbon material are fusion-bonded.

8. The positive electrode material according to claim 7 , wherein the conductive carbon material comprises at least one conductive carbon material selected from conductive carbon powders and conductive carbon fibers.

9. The positive electrode material according to claim 8 , wherein the conductive carbon powder comprises at least one powder selected from acetylene black, ketjen black, and a powder that partially includes a graphite crystal.

10. The positive electrode material according to claim 8 , wherein the conductive carbon fiber comprises at least one fiber selected from carbon fibers, graphite fibers, vapor-grown carbon fibers, carbon nanofibers, and carbon nanotubes.

11. A positive electrode comprising a positive electrode material as defined in claim 1 and a current collector.

12. The positive electrode of claim 11 , further comprising a binder.

13. The positive electrode of claim 12 , wherein the binder is selected from fluorine-containing resins, thermoplastic resins, acrylic resin materials, styrene-butadiene-based materials, and combinations thereof.

14. A lithium secondary battery comprising at least one positive electrode as defined in claim 11 , at least one negative electrode and at least one electrolyte, optionally further comprising at least one separator in between stacked positive and negative electrodes, and an electrolyte solution in which the positive and negative electrodes are immersed.

15. The lithium secondary battery according to claim 14 , wherein the negative electrode comprises a material selected from artificial graphite, a composite negative electrode material that includes metallic silicon, a composite of a silicon oxide/metallic silicon powder coated with conductive carbon and a graphitic powder coated with conductive carbon.

16. The lithium secondary battery according to claim 14 , wherein the separator is selected from a synthetic resin film, and a separator formed of fibers or inorganic fibers, or wherein the separator is selected from a polyethylene film, a polypropylene film, a polyethylene woven fabric, a polyethylene nonwoven fabric, a polypropylene woven fabric, a polypropylene nonwoven fabric, a separator formed of glass fibers, a separator formed of cellulose fibers, and a separator formed of polyethylene terephthalate fibers.

17. The lithium secondary battery according to claim 14 , wherein the electrolyte is a non-aqueous electrolyte solution which includes a non-aqueous solvent and at least one lithium salt, or an ion-conductive polymer.

18. The lithium secondary battery according to claim 17 , wherein the non-aqueous solvent is an alkyl carbonate or a mixture of alkyl carbonates.

19. The lithium secondary battery according to claim 18 , wherein the non-aqueous solvent is selected from ethylene carbonate (EC), propylene carbonate (PC), diethyl carbonate (DEC), dimethyl carbonate (DMC), methylethyl carbonate (MEC), and combinations thereof.

20. The lithium secondary battery according to claim 17 , wherein the lithium salt is selected from lithium hexafluorophosphate (LiPF 6 ), lithium tetrafluoroborate (LiBF 4 ), and lithium trifluoromethanesulfonate (LiSO 3 CF 4 ).

21. A method for the manufacture of a positive electrode material as defined in claim 1 , comprising the steps of:
a) providing particles of the first lithium compound;
b) forming the first carbon material layer on the entire surface of the particles provided in (a), to provide carbon-coated particles;
c) forming a thin film layer of the second lithium compound on part or the entirety of the carbon-coated particles provided in step (b); and
d) coating an entire surface of the thin film layer of the second lithium compound with the second carbon material layer, to provide the positive electrode material.

22. The method of claim 21 , further comprising mixing the material of step (d) with a conductive carbon material, and fusion bonding the conductive carbon material and the second carbon material layer.

23. The method of claim 21 , further comprising mixing the particle provided in step (a) with a compound comprising an element selected from the elements of groups 3 to 6 in the periodic table, or an oxide thereof, or an aluminum halide compound.

24. The positive electrode of claim 13 , wherein the binder is a fluorine-containing resin selected from the group consisting of polytetrafluoroethylene, polyvinylidene fluoride, and fluororubber, and combinations thereof.

25. The positive electrode of claim 13 , wherein the binder is a thermoplastic resin selected from the group consisting of polypropylene and polyethylene, and combinations thereof.

26. The positive electrode material according to claim 1 , wherein the average particle size of the first lithium compou

Assignees

• Hydro Quebec
• Sei Corp

Inventors

• Sawai Takehiko
• Saito Shinji
• Urao Kazunori
• Hanai Kazuma
• Zaghib Karim
• Guerfi Abdelbast
• Dontigny Martin

Classifications

• C01P2004/80

  Particles consisting of a mixture of two or more inorganic phases · CPC title

• H01M4/1391

  of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx · CPC title

• H01M10/0568

  characterised by the solutes · CPC title

• C01B25/45

  containing plural metal, or metal and ammonium · CPC title

• H01M10/0525

  Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries · CPC title