Composite membrane, and lithium battery including the composite membrane

Patent metadata

Field	Value
Publication number	US-11532852-B2
Application number	US-202016743489-A
Country	US
Kind code	B2
Filing date	Jan 15, 2020
Priority date	Jan 24, 2019
Publication date	Dec 20, 2022
Grant date	Dec 20, 2022

Abstract

A composite membrane includes: an organic layer including a plurality of through holes; and ion conductive inorganic particles disposed in the plurality of through holes, wherein the ion conductive inorganic particles each include at least one recess, at least one protrusion, or a combination thereof on a surface thereof, and wherein the surface of the ion conductive inorganic particles which comprises the at least one recess, the at least one protrusion, or the combination thereof faces a surface of the organic layer.

First claim

What is claimed is:

1. A composite membrane comprising:
an organic layer comprising a plurality of through holes; and
a plurality of ion conductive inorganic particles disposed in the plurality of through holes,
wherein a surface of each ion conductive inorganic particle of the plurality of ion conductive inorganic particles comprises at least one protrusion, and
wherein the surface comprising the at least one protrusion faces a surface of the organic layer.

2. The composite membrane of claim 1 , wherein the composite membrane has a first surface and a second surface, and the plurality of ion conductive inorganic particles are exposed at each of the first surface and the second surface, and wherein the first surface is located at a side of the composite membrane which is opposite to the second surface, and
the at least one protrusion has a continuous or discontinuous structure extending from the first surface to the second surface.

3. The composite membrane of claim 1 , wherein each of the ion conductive inorganic particles has a porous surface structure.

4. The composite membrane of claim 1 , wherein the surface of each ion conductive inorganic particle of the plurality of ion conductive inorganic particles further comprises at least one recess, and wherein a length of the at least one recess and a length of the at least one protrusion are each independently about 10 percent to about 50 percent of an average particle diameter of the plurality of ion conductive inorganic particles.

5. The composite membrane of claim 1 , wherein each of the plurality of ion conductive inorganic particles comprises a plurality of protrusions and optionally, further comprises a plurality of recesses.

6. The composite membrane of claim 5 , wherein each recess of the plurality of recesses and each protrusion of the plurality of protrusions has an identical shape or a different shape.

7. The composite membrane of claim 1 , wherein the surface of each ion conductive inorganic particle of the plurality of ion conductive inorganic particles further comprises at least one recess, wherein an occupation area of the at least one recess is about 5 percent to about 30 percent of a total surface area of each ion conductive inorganic particle of the plurality of ion conductive inorganic particles comprising the at least one recess.

8. The composite membrane of claim 1 , wherein an occupation area of the at least one protrusion is about 5 percent to about 50 percent of a total surface area of each of the plurality of ion conductive inorganic particles comprising the at least one protrusion.

9. The composite membrane of claim 1 , wherein
at least one surface of the composite membrane comprises a sea-island structure in which the plurality of ion conductive inorganic particles are discontinuously disposed in the organic layer, or
a cross-section of the composite membrane comprises a structure in which the plurality of ion conductive inorganic particles are alternately aligned with regions of the organic layer.

10. The composite membrane of claim 1 , wherein the plurality of ion conductive inorganic particles embedded in the organic layer are disposed in the form of a monolayer.

11. The composite membrane of claim 1 , wherein the organic layer comprises a polymer comprising a homopolymer, a block copolymer, a random copolymer, or a combination thereof.

12. The composite membrane of claim 1 , wherein an amount of the plurality of ion conductive inorganic particles is about 10 parts by weight to about 90 parts by weight based on 100 parts by weight of the composite membrane.

13. The composite membrane of claim 1 , wherein the plurality of ion conductive inorganic particles have an average particle diameter of about 1 micrometer to about 500 micrometers.

14. The composite membrane of claim 1 , wherein the plurality of ion conductive inorganic particles comprises a glassy active metal ion conductor, an amorphous active metal ion conductor, a ceramic active metal ion conductor, a glass-ceramic active metal ion conductor, or a combination thereof.

15. The composite membrane of claim 1 , wherein the plurality of ion conductive inorganic particles comprises Li 1+x+y Al x Ti 2−x Si y P 3−y O 12 wherein 0<x<2 and 0≤y<3, BaTiO 3 , Pb(Zr 1−x Ti x )O 3 wherein 0≤x≤1, Pb 1−x La x Zr 1−y Ti y O 3 wherein 0≤x<1 and 0≤y<1, Pb(Mg 3 Nb 2/3 )O 3 —PbTiO 3 , HfO 2 , SrTiO 3 , SnO 2 , CeO 2 , Na 2 O, MgO, NiO, CaO, BaO, ZnO, ZrO 2 , Y 2 O 3 , Al 2 O 3 , TiO 2 , SiO 2 , SiC, Li 3 PO 4 , Li x Ti y (PO 4 ) 3 wherein 0<x<2 and 0<y<3, Li x Al y Ti z (PO 4 ) 3 wherein 0<x<2, 0<y<1, and 0<z<3, Li 1+x+y (Al a Ga 1−a ) x (Ti b Ge 1−b ) 2−x Si y P 3−y O 12 wherein 0≤x≤1, 0≤y≤1, 0≤a≤1, and 0≤b≤1, Li x La y TiO 3 wherein 0<x<2 and 0<y<3, Li x Ge y P z S w wherein 0<x<4, 0<y<1, 0<z<1, and 0<w<5, Li x N y wherein 0<x<4 and 0<y<2, Li x Si y S z wherein 0<x<3, 0<y<2, and 0<z<4, Li x P y S z wherein 0<x<3, 0<y<3, and 0<z<7, Li 2 O, LiF, LiOH, Li 2 CO 3 , LiAlO 2 , a Li 2 O—Al 2 O 3 —SiO 2 —P 2 O 5 —TiO 2 —GeO 2 ceramic, a garnet ceramic, Li 3+x La 3 M 2 O 12 wherein M is Te, Nb, or Zr, and x is an integer from 1 to 10, or a combination thereof.

16. The composite membrane of claim 1 , wherein the organic layer comprises a polymer having a water permeability of about 0.001 gram of water per square meter per day to about 1 gram of water per square meter per day and an oxygen permeability of about 10 −3 cm 3 /m 2 day to about 1,000 cm 3 /m 2 day.

17. The composite membrane of claim 1 , wherein the organic layer comprises:
a polymerization product of a polyfunctional monomer; or
a polymerization product of a polyfunctional monomer and a polythiol having 3 or 4 thiol groups,
wherein the polyfunctional monomer comprises a polyfunctional acryl monomer, a polyfunctional vinyl monomer, or a combination thereof.

18. The composite membrane of claim 1 , wherein an area of the plurality of ion conductive inorganic particles exposed at a surface of the composite membrane is about 30 percent to about 80 percent, based on a total surface area of the composite membrane.

19. A lithium battery comprising:
an anode,
a cathode, and
the composite membrane according to claim 1 between the cathode and the anode.

20. The lithium battery of claim 19 , wherein the lithium battery is an all-solid battery or a lithium-air battery.

Assignees

• Samsung Electronics Co Ltd

Inventors

• Choi Kyounghwan
• Choi Wonsung

Classifications

• H01M2300/0091

  in the form of mixtures · CPC title

• H01M10/056

  characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes · CPC title

• H01M50/414

  Synthetic resins, e.g. thermoplastics or thermosetting resins · CPC title

• Y02E60/10

  Energy storage using batteries · CPC title

• H01M10/0562 Primary

  Solid materials · CPC title