Lithium ion battery, solid electrolyte and method of preparing the same

Patent metadata

Field	Value
Publication number	US-9893379-B2
Application number	US-201615242228-A
Country	US
Kind code	B2
Filing date	Aug 19, 2016
Priority date	Mar 28, 2014
Publication date	Feb 13, 2018
Grant date	Feb 13, 2018

Abstract

A solid electrolyte contains an internal component and an external component coated on a surface of the internal component. The internal component is represented by a formula Li 1+x M x Zr 2−x (PO 4 ) 3 , M is one or more elements selected from a group consisting of Al, La, Cr, Ga, Y, and In, and 0.05≦x≦0.4. The external component contains a plastic deformable material and has a conductivity of about 10 −7 S/cm to about 10 −5 S/cm. A method of preparing the solid electrolyte and a lithium ion battery including the solid electrolyte are also provided.

First claim

What is claimed is:

1. A solid electrolyte comprising:
an internal component represented by a formula Li 1+x M x Zr 2−x (PO 4 ) 3 , M being one or more elements selected from the group consisting of Al, La, Cr, Ga, Y, and In, and 0.05≦x≦0.4; and
an external component coated on a surface of the internal component, the external component comprising a plastic deformable material and having a conductivity of about 10 −7 S/cm to about 10 −5 S/cm.

2. The solid electrolyte of claim 1 , wherein the external component is represented by a formula Li 3−3y B y PO 4 , and 0≦y<1.

3. The solid electrolyte of claim 2 , wherein the external component is selected from the group consisting of: Li 3 PO 4 , Li 0.18 B 0.94 PO 4 , Li 0.15 B 0.95 PO 4 , Li 0.12 B 0.96 PO 4 , Li 0.09 B 0.97 PO 4 , Li 0.06 B 0.98 PO 4 , and combinations thereof.

4. The solid electrolyte of claim 1 , wherein the content of the external component is about 0.5 wt % to about 10 wt %, based on the total weight of the solid electrolyte.

5. The solid electrolyte of claim 1 , wherein the internal component is selected from the group consisting of Li 1.1 Y 0.1 Zr 1.9 (PO 4 ) 3 , Li 1.3 Y 0.3 Zr 1.7 (PO 4 ) 3 , Li 1.4 Y 0.4 Zr 1.6 (PO 4 ) 3 , Li 1.1 Al 0.1 Zr 1.9 (PO 4 ) 3 , Li 1.3 Al 0.3 Zr 1.7 (PO 4 ) 3 , Li 1.05 La 0.05 Zr 1.95 (PO 4 ) 3 , Li 1.1 Cr 0.1 Zr 1.9 (PO 4 ) 3 , Li 1.1 Ga 0.1 Zr 1.9 (PO 4 ) 3 , Li 1.1 In 0.1 Zr 1.9 (PO 4 ) 3 , and combinations thereof.

6. The solid electrolyte of claim 1 , wherein the internal component has an average particle size of about 0.5 μm to about 10 μm, and the external component has an average particle size of about 10 nm to about 30 nm.

7. A method for preparing a solid electrolyte, comprising:
providing an internal component represented by a formula Li 1+x M x Zr 2−x (PO 4 ) 3 , M being one or more elements selected from a group consisting of Al, La, Cr, Ga, Y, and In, and 0.05x≦0.4; and
providing an external component on a surface of the internal component to form a composite, the external component comprising a plastic deformable material and having a conductivity of about 10 −7 S/cm to about 10 −5 S/cm.

8. The method of claim 7 , wherein providing an internal component comprises:
mixing ZrO 2 , M 2 O 3 , NH 4 H 2 PO 4 and a lithium source compound to form a mixture; and
subjecting the mixture to a first calcination.

9. The method of claim 8 , wherein the mixing is performed by ball milling, and the first calcination is performed at a temperature of about 750° C. to about 950° C. for about 4 hours to about 16 hours.

10. The method of claim 8 , wherein providing an internal component further comprises cooling a product obtained from the first calcination.

11. The method of claim 8 , wherein the amount of the lithium source compound is about 105 wt % to about 120 wt % of the stoichiometric amount.

12. The method of claim 7 , wherein providing an external component on a surface of the internal component comprises:
mixing the internal component and raw materials of the external component in water to form a slurry; and
bringing the pH value of the slurry to about 8 to about 11, such that the external component is coated on the surface of the internal component to form the composite.

13. The method of claim 12 , wherein raw materials of the external component comprise LiOH and NH 4 H 2 PO 4 .

14. The method of claim 13 , wherein raw materials of the external component further comprise H 3 BO 3 .

15. The method of claim 12 , further comprising drying the composite.

16. The method of claim 7 , further comprising molding the composite, wherein the molding is performed by compression molding.

17. The method of claim 16 , further comprising subjecting a product obtained from the molding to a second calcination.

18. The method of claim 17 , wherein the second calcination comprises:
increasing the temperature of the product to about 900° C. to about 1200° C. with a heating rate of about 2° C./min to about 10° C./min, and
keeping the product at about 900° C. to about 1200° C. for about 8 hours to about 24 hours.

19. The method of claim 7 , wherein the internal component has an average particle size of about 0.5 μm to about 10 μm, and the external component has an average particle size of about 10 nm to about 30 nm.

20. A lithium ion battery comprising:
a cathode;
an anode; and
a solid electrolyte disposed between the cathode and the anode, wherein the solid electrolyte comprises:
an internal component represented by a formula Li 1+x M x Zr 2−x (PO 4 ) 3 , M being one or more elements selected from the group consisting of Al, La, Cr, Ga, Y, and In, and 0.05≦x≦0.4; and
an external component coated on a surface of the internal component, the external component comprising a plastic deformable material and having a conductivity of about 10 −7 S/cm to about 10 −5 S/cm.

Assignees

• Byd Co Ltd

Inventors

• Yi Guangui
• Ma Yongjun
• Guo Zizhu

Classifications

• H01M10/0525

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

• H01M10/0562 Primary

  Solid materials · CPC title

• Y02T10/7011

  Cross-Sectional Technologies · mapped topic

• B28B3/00

  Producing shaped articles from the material by using presses (shaping on moving conveyors B28B5/00); Presses specially adapted therefor (presses in general B30B) · CPC title

• C04B2235/3286

  Gallium oxides, gallates, indium oxides, indates, thallium oxides, thallates or oxide forming salts thereof, e.g. zinc gallate · CPC title