Positive electrode material comprising a solid electrolyte for solid-state rechargeable lithium ion battery with a high thermal stability

Patent metadata

Field	Value
Publication number	US-12401030-B2
Application number	US-202017431731-A
Country	US
Kind code	B2
Filing date	Feb 19, 2020
Priority date	Feb 20, 2019
Publication date	Aug 26, 2025
Grant date	Aug 26, 2025

Abstract

A catholyte destined to be used in a lithium ion solid-state battery, said catholyte comprising: (i) a solid electrolyte powder having a formula: Li (3.5+L+x) Si (0.5+s−x) P (0.5+p−x) Ge 2x O 4+a , wherein −0.10≤L≤0.10, −0.10≤s≤0.10, −0.10≤p≤0.10, −0.40≤a≤0.40, and 0.00≤x≤0.30, and (ii) a positive electrode active material powder having a formula: Li 1+k M′ 1−k O 2 where M′=Ni 1−x′−y−z′ Mn x′ Co y′ A z′ with −0.05≤k≤0.05, 0≤x′≤0.40, 0.05≤y′≤0.40, and 0≤z′≤0.05, wherein A is a doping element which is different to Li, M′ and O, said positive active material powder comprising particles having a layered R-3m crystal structure, said catholyte having a D99≤50 μm and an ionic conductivity of at least 1.0×10 −6 S/m.

First claim

The invention claimed is:

1. A catholyte configured for use in a lithium ion solid-state battery, said catholyte comprising:
i. a solid electrolyte powder, wherein a formula for the solid electrolyte powder consists of Li (3.5+L+x) Si (0.5+s−x) P (0.5+p−x) Ge 2x O 4+a , wherein −0.10≤L≤0.10, −0.10≤s≤0.10, −0.10≤p≤0.10, −0.40≤a≤0.40, and 0.00≤x≤0.30, and
ii. a positive electrode active material powder, wherein a formula for the positive electrode active material powder is Li 1+k M′ 1-k O 2 where M′=Ni 1-x′y′z′ Mn x′ Co y′ A z′ with −0.05≤k≤0.05, 0≤x′≤0.40, 0.05≤y′≤0.40, and 0≤z′≤0.05, wherein A is a doping element which is different to Li, M′ and O, said positive active material powder comprising particles having a layered R-3m crystal structure,
wherein said catholyte has a D99, wherein 30 μm≤D99≤50 μm and an ionic conductivity of at least 1.0×10 −6 S/m.

2. The catholyte according to claim 1 , wherein A comprises one or more of Al, Ca, W, B, Si, Ti, Mg or Zr.

3. The catholyte according to claim 1 , wherein the catholyte has a solid electrolyte:positive electrode active material weight ratio greater than or equal to 10:90 and less than or equal to 50:50.

4. The catholyte according to claim 1 , wherein the positive electrode active material powder comprises particles having a monolithic or polycrystalline morphology.

5. The catholyte according to claim 1 having an ionic conductivity of at least 1.0×10 −5 S/m.

6. A solid state battery comprising the catholyte according to claim 1 , a solid-state electrolyte, and a Li metal anode.

7. A process for making the catholyte according to claim 1 , comprising the steps of:
mixing the solid electrolyte powder having the formula: Li (3.5+L+x) Si (0.5+s−x) P (0.5+p−x) Ge 2x O 4+a , with the positive electrode active material powder having the formula: Li 1+k M′ 1-k O 2 where M′=Ni 1-x′-y′-z′ Mn x′ Co y′ A z′ with −0.05≤k≤0.05, 0≤x′≤0.40, 0.05≤y′≤0.40, and 0≤z′≤0.05, so as to obtain a mixture,
heating the mixture in an oxidizing atmosphere at a temperature of at least 600° C. and at most 800° C., thereby obtaining the catholyte according to claim 1 .

8. The process according to claim 7 , wherein the solid electrolyte powder and the positive electrode active material powder are mixed together in a solid electrolyte:positive electrode active material weight ratio superior or equal to 10:90 and inferior or equal to 50:50.

9. The process according to claim 7 , wherein the step of heating the mixture is performed during at least 1 hour and at most 20 hours.

10. The process according to claim 7 , wherein the step of heating the mixture is performed in an atmosphere comprising at least 15 vol % of oxygen.

Assignees

• Umicore Nv
• Umicore Korea Ltd
• Postech Acad Ind Found

Inventors

• Kang Byoungwoo
• Woo Seung-Jun

Classifications

• H01M50/431

  Inorganic material · CPC title

• H01M4/1391

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

• H01M4/62

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

• H01M10/052

  Li-accumulators · CPC title

• H01M2300/0068

  inorganic · CPC title