Ion conducting batteries with solid state electrolyte materials

Patent metadata

Field	Value
Publication number	US-10622666-B2
Application number	US-201414222306-A
Country	US
Kind code	B2
Filing date	Mar 21, 2014
Priority date	Mar 21, 2013
Publication date	Apr 14, 2020
Grant date	Apr 14, 2020

Abstract

Solid-state, ion-conducting batteries with an ion-conducting, solid-state electrolyte. The solid-state electrolyte has at least one porous region (e.g., porous layer) and a dense region (e.g., dense layer). The batteries are, for example, lithium-ion, sodium-ion, or magnesium-ion conducting solid-state batteries. The ion-conducting, solid-state electrolyte is, for example, a lithium-garnet material.

First claim

What is claimed is:

1. A solid-state, ion-conducting battery comprising:
a cathode comprising a cathode material or an anode comprising an anode material;
a solid-state electrolyte (SSE) material comprising a porous region of sintered particles having a plurality of pores, and a dense region having a thickness of 1 to 100 microns that is too thin to be self-supporting, wherein the cathode material or the anode material is disposed on at least a portion of the porous region, particles of the porous region are fused into the dense region and the dense region is free of the cathode material and the anode material, and
a current collector disposed on at least a portion of the cathode material or the anode material,
wherein the dense region is supported by the porous region and the porous region of the SSE material that has the cathode material disposed thereon has a dimension of 20 μm to 200 μm and/or the porous region of the SSE material that has the anode material disposed thereon has a dimension of 20 μm to 200 μm.

2. The solid-state, ion-conducting battery of claim 1 , wherein the cathode material is a lithium-containing material, a sodium-containing cathode material, or a magnesium-containing cathode material.

3. The solid-state, ion-conducting battery of claim 2 , wherein
the lithium-containing electrode material is a lithium-containing, ion-conducting cathode material selected from LiCoO 2 , LiFePO 4 , Li 2 MMn 3 O 8 , wherein M is selected from Fe, Co, and combinations thereof,
the sodium-containing cathode material is a sodium-containing, ion-conducting cathode material is selected from Na 2 V 2 O 5 , P 2 —Na 2/3 Fe 1/2 Mn 1/2 O 2 , Na 3 V 2 (PO 4 ) 3 , NaMn 1/3 CO 1/3 Ni 1/3 PO 4 , and Na 2/3 Fe 1/2 Mn 1/2 O 2 @graphene composite, and
the magnesium-containing cathode material is a magnesium-containing, ion-conducting cathode material and is a doped manganese oxide.

4. The solid-state, ion-conducting battery of claim 1 , wherein the cathode material comprises a conducting carbon material, and the cathode material, optionally, further comprises an organic or gel ion-conducting electrolyte.

5. The solid-state, ion-conducting battery of claim 1 , wherein the anode material is a lithium-containing anode material, a sodium-containing anode material, or a magnesium-containing anode material.

6. The solid-state, ion-conducting battery of claim 5 , wherein
the lithium-containing anode material is lithium metal,
the sodium-containing anode material is sodium metal or an ion-conducting, sodium-containing anode material selected from Na 2 CsH 4 O 4 and Na 0.66 Li 0.22 Ti 0.78 O 2 , and
the magnesium-containing anode material is magnesium metal.

7. The solid-state, ion-conducting battery of claim 1 , wherein the SSE material is a lithium-containing SSE material, a sodium-containing SSE material, or a magnesium-containing SSE material.

8. The solid-state, ion-conducting battery of claim 7 , wherein the lithium-containing SSE material is a Li-garnet SSE material.

9. The solid-state, ion-conducting battery of claim 8 , wherein the Li-garnet SSE material is cation-doped Li 5 La3M 1 2 O 12 , where M 1 is Nb, Zr, Ta, or combinations thereof, cation-doped Li 6 La 2 BaTa 2 O 12 , cation-doped Li 7 La 3 Zf 2 O 12 , and cation-doped Li 6 BaY 2 M 1 2 O 12 , where cation dopants are barium, yttrium, zinc, or combinations thereof.

10. The solid-state, ion-conducting battery of claim 8 , wherein said Li-garnet SSE material is Li 5 La 3 Nb 2 O 12 , Li 5 La 3 Ta 2 O 12 , Li 7 La 3 Zf 2 O 12 , Li 6 La 2 SrNb 2 O 12 , Li 6 La 2 BaNb 2 O 12 , Li 6 La 2 SrTa 2 O 12 , Li 6 La 2 BaTa 2 O 12 , Li 7 Y 3 Zf 2 O 12 , Li 6.4 Y 3 Zr 1.4 Ta 0.6 O 12 , Li 6.5 La 2.5 Ba 0.5 TaZrO 12 , Li 6 BaY 2 M 1 2 O 12 , Li 7 Y 3 Zf 2 O 12 , Li 6.75 BaLa 2 Nb 1.75 Zn 0.25 SO 12 , or Li 6.75 BaLa 2 Ta 1.75 Zn 0.25 O 12 .

11. The solid-state, ion-conducting battery of claim 1 , wherein the ion-conducting cathode material, the ion-conducting anode material, the SSE material, and the current collector form a cell, and the solid-state, ion-conducting battery comprises a plurality of the cells, each adjacent pair of the cells is separated by a bipolar plate.

12. The solid-state, ion-conducting battery of claim 1 , wherein the dense region is thinner than the porous region.

13. The solid-state, ion-conducting battery of claim 1 , wherein the dense region is laminated in a green state onto the porous region followed by sintering.

14. The solid-state, ion-conducting battery of claim 1 , wherein the dense region has a thickness of 1 to 50 microns.

15. The solid-state, ion-conducting battery of claim 1 , wherein the porous region and the dense region each comprise a cast or pressed surface.

16. The solid-state, ion-conducting battery of claim 1 , wherein the porous region and the dense region each comprise a tape-cast surface.

17. The solid-state, ion-conducting battery of claim 1 , wherein the porous region on one side of the dense region is layered and is multi-layered wherein a first layer has a porosity different from a second layer.

18. The solid-state, ion-conducting battery of claim 1 , wherein the cathode comprises a first material and an electronic-conducting material, wherein
the first material is selected from the group consisting of lithium-containing material, sodium-containing cathode material, magnesium-containing cathode material, and a polysulfide or an organic sulfide wherein
the lithium-containing material is selected from the group consisting of lithium nickel manganese cobalt oxides, lithium manganese oxides and lithium iron phosphates,
the sodium-containing material is selected from the group consisting of Na 2 V 2 O 5 , P 2 —Na 2/3 Fe 1/2 Mn 1/2 O 2 , Na 3 V 2 (PO 4 ) 3 , NaMn 1/3 Co 1/3 Ni 1/3 PO 4 , and Na 2/3 Fe 1/2 Mn 1/2 O 1/2 @graphene composite, and
the magnesium-containing material is a doped manganese oxide, and
the electronic-conducting material is an electrically conducting carbon material.

19. The solid state ion-conducting battery of claim 18 , wherein
the doped manganese oxide is Mg x MnO 2 .yH 2 O,
the lithium nickel manganese cobalt oxides are selected from the group consisting of materials having the formula LiNi x Mn y Co z O 2 , where x+y+z=1, LiCo 2 , LiNi 1/3 Co 1/3 Mn 1/3 O 2 , LiNi 0.5 Co 0.2 Mn 0.3 O 2 ,
the lithium manganese oxides are selected from the group consisting of LiMn 2 O 4 and LiNi 0.5 Mn 1.5 O 4 ,
the lithium iron phosphates are selected from the group consisting of LiFePO 4 , LiMnPO 4 , and LiCoPO 4 , and Li 2 MMn 3 O 8 , where M is selected from Fe and Co,
the polysulfide or organic sulfide are selected from the group consisting of copolymerized sulfur and carbyne polysulfide and
the electrically conducting carbon material is graphene or carbon black.

20. The solid-state, ion-conducting battery of claim 1 , wherein
the anode material is a metallic form of an ion conducted in the SSE during operation of the solid-state, ion conducting battery, and the anode material at least partially fills at least one pore of the porous region,
wherein the metal is selected from the group consisting of lithium, sodium and magnesium, and
when the metal is lithium, the lithium conformally coats the at least one pore.

21. The solid-state, ion-conducting batter of claim 20 , wherein the anode further comprises an electronic conducting phase selected from the group consisting of graphite, hard carbon, porous hollow carbon spheres and tubes, tin, tin alloy, tin/carbon, tin/cobalt al

Assignees

• Univ Maryland

Inventors

• Wachsman Eric D
• Hu Liangbing
• Thangadurai Venkataraman

Classifications

• H01M4/661

  Metal or alloys, e.g. alloy coatings (H01M4/669 take precedence) · CPC title

• H01M2300/0071

  Oxides · CPC title

• H01M4/0414

  by screen printing · CPC title

• H01M10/054

  Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium · CPC title

• H01M4/0407

  by coating on an electrolyte layer · CPC title