All-solid lithium ion secondary battery

Patent metadata

Field	Value
Publication number	US-9413033-B2
Application number	US-201314030358-A
Country	US
Kind code	B2
Filing date	Sep 18, 2013
Priority date	Sep 19, 2012
Publication date	Aug 9, 2016
Grant date	Aug 9, 2016

Abstract

To provide an all-solid lithium ion secondary battery having a high voltage, a small internal resistance, and a discharge capacity close to a theoretical capacity and being able to be produced at low cost, and therefore, even in the case of collective sintering, generation of an inactive material due to interface reaction at the interface between an electrode active material and a solid electrolyte is reduced. An all-solid lithium ion secondary battery including a positive electrode layer, a negative electrode layer, and a solid electrolyte layer disposed between the positive electrode layer and the negative electrode layer, wherein an electrode active material included in the positive electrode layer is a phosphate having an olivine structure; and a solid electrolyte crystal included in the solid electrolyte layer includes polyphosphoric acid and the content of Li 2 O is 16 mol % to 25 mol % in terms of mol % on an oxide basis.

First claim

What is claimed is:

1. An all-solid lithium ion secondary battery comprising a positive electrode layer, a negative electrode layer, and a solid electrolyte layer disposed between the positive electrode layer and the negative electrode layer, wherein
an electrode active material included in the positive electrode layer is a phosphate having an olivine structure;
a solid electrolyte crystal included in the solid electrolyte layer is polyphosphate-containing NASICON-type Li 1+x M y Zr 2−y Si z P 3−z O 12+a , and a content of Li 2 O is 16 mol % to 25 mol % in terms of mol % on an oxide basis,
where M is at least one selected from Al, La, Sr, Mg, Y, Ba, Zn, Sc, and Ca, x is 0.1 to 1.2, y is 0.1 to 1.1, z is 0.1 to 1.0, and a is −1.0 to 1.0.

2. The all-solid lithium ion secondary battery according to claim 1 , wherein a solid electrolyte crystal included in the solid electrolyte layer is NASICON-type Li 1+x M y Zr 2−y Si z P 3−z O 12+a ,
where M is at least one selected from Mg, Ca, and Sr, x is 0.1 to 1.2, y is 0.1 to 0.55, z is 0.1 to 1.0, and a is −1.0 to 1.0.

3. The all-solid lithium ion secondary battery according to claim 1 , wherein an electrode active material included in the positive electrode layer, an electrode active material included in the negative electrode layer, and a solid electrolyte crystal included in the solid electrolyte layer have crystal structures differing from each other.

4. The all-solid lithium ion secondary battery according to claim 1 , wherein an electrode active material included in the positive electrode layer is Li n M′PO 4 ,
where M′ is at least one selected from Fe, Co, Mn, Ni, Al, Mg, Ca, Ti, and Zr and n is 0.7 to 1.5.

5. The all-solid lithium ion secondary battery according to claim 1 , wherein an electrode active material included in the negative electrode layer is Li 4 Ti 5 O 12 , anatase-type TiO 2 , or NASICON-type Li 1+x Ti 2−x (PO 4 ) 3 .

6. The all-solid lithium ion secondary battery according to claim 1 , wherein at least one of the positive electrode layer, the negative electrode layer, and the solid electrolyte layer includes 2 to 15% by weight of a lithium ion conductive glass.

7. The all solid lithium ion secondary battery according to claim 1 , wherein
at least one of the positive electrode layer, the negative electrode layer and the solid electrolyte layer contains 2 to 15% by weight of glass comprising Li 2 O, Al 2 O 3 and P 2 O 5 .

8. The all-solid lithium ion secondary battery according to claim 7 , wherein an electrode active material included in the positive electrode layer, an electrode active material included in the negative electrode layer, and a solid electrolyte crystal included in the solid electrolyte layer have crystal structures differing from each other.

9. The all-solid lithium ion secondary battery according to claim 7 , wherein an electrode active material included in the positive electrode layer is Li n M′PO 4 , where M′ is at least one selected from Fe, Co, Mn, Ni, Al, Mg, Ca, Ti, and Zr and n is 0.7 to 1.5.

10. The all-solid lithium ion secondary battery according to claim 7 , wherein an electrode active material included in the negative electrode layer is Li 4 Ti 5 O 12 , anatase-type TiO 2 , or NASICON-type Li 1+x Ti 2−x (PO 4 ) 3 .

11. The all-solid lithium ion secondary battery according to claim 7 , wherein at least one of the positive electrode layer and the negative electrode layer includes acetylene black.

12. The all-solid lithium ion secondary battery according to claim 1 , wherein at least one of the positive electrode layer and the negative electrode layer includes acetylene black.

13. An all-solid lithium ion secondary battery comprising a positive electrode layer, a negative electrode layer, and a solid electrolyte layer disposed between the positive electrode layer and the negative electrode layer, wherein
an electrode active material included in the positive electrode layer is a phosphate having an olivine structure;
a solid electrolyte crystal included in the solid electrolyte layer is polyphosphate-containing NASICON-type Li 1+x M y Zr 2−y Si z P 3−z O 12+a , and a content of Li 2 O is 16 mol % to 25 mol % in terms of mol % on an oxide basis,
where M is at least one selected from Mg, Ca, and Sr, R is at least one selected from Ge, Ti, and Zr, x is 0.1 to 1.2, y is 0.1 to 0.55, z is 0.1 to 1.0, and a is −1.0 to 1.0.

14. The all-solid lithium ion secondary battery according to claim 13 , wherein an electrode active material included in the positive electrode layer, an electrode active material included in the negative electrode layer, and a solid electrolyte crystal included in the solid electrolyte layer have crystal structures differing from each other.

15. The all-solid lithium ion secondary battery according to claim 13 , wherein an electrode active material included in the positive electrode layer is Li n M′PO 4 ,
where M′ is at least one selected from Fe, Co, Mn, Ni, Al, Mg, Ca, Ti, and Zr and n is 0.7 to 1.5.

16. The all-solid lithium ion secondary battery according to claim 13 , wherein an electrode active material included in the negative electrode layer is Li 4 Ti 5 O 12 , anatase-type TiO 2 , or NASICON-type Li 1+x Ti 2−x (PO 4 ) 3 .

17. The all-solid lithium ion secondary battery according to claim 13 , wherein at least one of the positive electrode layer, the negative electrode layer, and the solid electrolyte layer includes 2 to 15% by weight of a lithium ion conductive glass.

18. The all-solid lithium ion secondary battery according to claim 13 , wherein at least one of the positive electrode layer and the negative electrode layer includes acetylene black.

19. The all-solid lithium ion secondary battery according to claim 13 , wherein at least one of the positive electrode layer, the negative electrode layer and the solid electrolyte layer contains 2 to 15% by weight of glass comprising Li 2 O, Al 2 O 3 and P 2 O 5 .

20. The all-solid lithium ion secondary battery according to claim 19 , wherein an electrode active material included in the positive electrode layer, an electrode active material included in the negative electrode layer, and a solid electrolyte crystal included in the solid electrolyte layer have crystal structures differing from each other.

21. The all-solid lithium ion secondary battery according to claim 19 , wherein an electrode active material included in the positive electrode layer is Li n M′PO 4 , where M′ is at least one selected from Fe, Co, Mn, Ni, Al, Mg, Ca, Ti, and Zr and n is 0.7 to 1.5.

22. The all-solid lithium ion secondary battery according to claim 19 , wherein an electrode active material included in the negative electrode layer is Li 4 Ti 5 O 12 , anatase-type TiO 2 , or NASICON-type Li 1+x Ti 2−x (PO 4 ) 3 .

23. The all-solid lithium ion secondary battery according to claim 19 , wherein at least one of the positive electrode layer and the negative electrode layer includes acetylene black.

Assignees

• Ohara Kk

Inventors

• Ogasa Kazuhito

Classifications

• H01M4/5825

  Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines · CPC title

• H01M4/485

  of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy (H01M4/505, H01M4/525 take precedence) · CPC title

• H01M10/0562 Primary

  Solid materials · CPC title

• H01M2300/0071

  Oxides · CPC title

• H01M10/0525

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