Composite cathode and lithium-ion battery comprising same, and method for producing said composite cathode

Patent metadata

Field	Value
Publication number	US-10971752-B2
Application number	US-201715625250-A
Country	US
Kind code	B2
Filing date	Jun 16, 2017
Priority date	Dec 18, 2014
Publication date	Apr 6, 2021
Grant date	Apr 6, 2021

Abstract

A composite cathode is provided which includes a collector, an active cathode material, a binder, a solid inorganic lithium-ion conductor and a liquid electrolyte. The solid inorganic lithium ion conductor is present in the composite cathode in a higher volume and weight proportion than the liquid electrolyte. A method for forming the composite cathode is also provided, and a lithium ion battery is provided which includes a composite cathode having a collector, an active cathode material, a binder, a solid inorganic lithium ion conductor and a liquid electrolyte.

First claim

What is claimed is:

1. A composite cathode comprising:
a collector,
an active cathode material,
a binder,
a solid inorganic lithium ion conductor, and
a liquid electrolyte,
wherein the binder is selected from the group consisting of polyvinylidene fluoride, copolymer of polyvinylidene fluoride and hexafluoro-propylene, polyethylene oxide, copolymer of styrene and butadiene, cellulose, cellulose derivatives, and mixtures thereof,
wherein the solid inorganic lithium ion conductor is selected from the group consisting of perovskite, glass formers, garnet, and mixtures thereof,
wherein the solid inorganic lithium ion conductor is present in the composite cathode in a higher volume fraction and weight fraction than the liquid electrolyte,
wherein the solid inorganic lithium ion conductor is present at 20 to 40 wt % in the composite cathode in relation to the active cathode material,
wherein 0.1 to 6 wt % of carbon-containing compounds or carbon are included in the active cathode material,
wherein the composite cathode has a porosity of 5% to 25%, based on a volume without the liquid electrolyte, and wherein the porosity is filled with the liquid electrolyte to an extent of more than 90%, and
wherein the porosity is achieved by calendering.

2. The composite cathode according to claim 1 , wherein the composite cathode has interconnected pores and the pores comprise the solid inorganic lithium ion conductor and the liquid electrolyte.

3. The composite cathode according to claim 1 , wherein the porosity is filled with the liquid electrolyte to an extent of more than 95%.

4. The composite cathode according to claim 1 , wherein the porosity is completely filled with the liquid electrolyte.

5. The composite cathode according to claim 1 , wherein the active cathode material and the solid inorganic lithium ion conductor each comprise particles, wherein the particles of the active cathode material has a greater average particle size D50 than the particles of the solid inorganic lithium ion conductor.

6. The composite cathode according to claim 5 , wherein the particles of the active cathode material has a 5 to 1000 times greater average particle size D50 than the particles of the solid inorganic lithium ion conductor.

7. The composite cathode according to claim 1 , wherein the active cathode material comprises secondary particles having the particle size D50 of more than 3 μm to 75 μm.

8. The composite cathode according to claim 1 , wherein the solid inorganic lithium ion conductor comprises particles having the particle size D50 of more than 0.05 μm to 5 μm.

9. The composite cathode according to claim 1 , wherein the active cathode material is selected from the group consisting of lithium transition-metal oxides, layered oxides, spinels, olivine compounds, silicate compounds, high-energy lithium nickel cobalt manganese oxide, and mixtures thereof.

10. The composite cathode according to claim 1 , wherein the solid inorganic lithium ion conductor has a lithium-ion conductivity of at least 10 −5 S/cm.

11. The composite cathode according to claim 1 , wherein the liquid electrolyte comprises organic carbonates and a conducting salt.

12. The composite cathode according to claim 11 , wherein the conducting salt is LiPF 6 or LiBF 4 .

13. A lithium ion battery comprising:
electrodes,
a separator, and
an electrolyte,
wherein one of the electrodes is a composite cathode according to claim 1 .

14. A method for producing a composite cathode having a collector, an active cathode material, a binder, a solid inorganic lithium ion conductor, and a liquid electrolyte, wherein
the binder is selected from the group consisting of polyvinylidene fluoride, copolymer of polyvinylidene fluoride and hexafluoro-propylene, polyethylene oxide, copolymer of styrene and butadiene, cellulose, cellulose derivatives, and mixtures thereof,
the solid inorganic lithium ion conductor is selected from the group consisting of perovskite, glass formers, garnet, and mixtures thereof,
the solid inorganic lithium ion conductor is present in the composite cathode in a higher volume fraction and weight fraction than the liquid electrolyte,
the solid inorganic lithium ion conductor is present at 20 to 40 wt % in the composite cathode in relation to the active cathode material,
0.1 to 6 wt % of carbon-containing compounds or carbon are included in the active cathode material, and
the composite cathode has a porosity of 5% to 25%, based on a volume without the liquid electrolyte, and wherein the porosity is filled with the liquid electrolyte to an extent of more than 90%, the method comprising the steps of:
combining at least the active cathode material, the binder in solution with a solvent, and the solid inorganic lithium ion conductor to form a homogeneous slurry; applying the slurry to the collector;
stripping off the solvent under reduced pressure and/or elevated temperature, forming a porosity in the slurry;
adjusting the porosity by calendering; and
filling up the porosity with the liquid electrolyte.

Assignees

• Bayerische Motoren Werke Ag

Inventors

• Woehrle Thomas
• Lupart Saskia
• Tsiouvaras Nikolaos
• Ogihara Hideki

Classifications

• H01M4/62

  Selection of inactive substances as ingredients for active masses, e.g. binders, fillers · CPC title

• H01M10/0525 Primary

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

• Y02E60/10

  Energy storage using batteries · 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

• H01M4/622

  being polymers · CPC title