All-solid-state battery

Patent metadata

Field	Value
Publication number	US-11588172-B2
Application number	US-201715792737-A
Country	US
Kind code	B2
Filing date	Oct 24, 2017
Priority date	Oct 26, 2016
Publication date	Feb 21, 2023
Grant date	Feb 21, 2023

Abstract

An all-solid-state battery includes a pair of electrode layers consisting of first and second electrode layers, and a solid-state electrolyte layer positioned between the pair of electrode layers, wherein the first electrode layer contains an electrode active material having an olivine-type crystalline structure, the solid-state electrolyte layer contains a solid-state electrolyte having a NASICON-type crystalline structure, and the solid-state electrolyte layer in the vicinity of the first electrode layer is expressed by a composition formula Li x A y Co z M′ a M″ b P 3 O c . The all-solid-state battery can improve the long-term cycle stability.

First claim

We claim:

1. An all-solid-state battery constituted by a sintered multilayer body comprising:
a pair of electrode layers consisting of first and second electrode layers, and a solid-state electrolyte layer positioned between the pair of electrode layers;
wherein:
the first electrode layer contains an electrode active material having an olivine-type crystalline structure;
the solid-state electrolyte layer contains a solid-state electrolyte having a NASICON-type crystalline structure which constitutes a primary phase throughout an entire portion of the solid-state electrolyte layer;
a composition of the solid-state electrolyte layer in a vicinity of the first electrode layer is expressed as a whole by formula (1):
Li x A y CO z M′ a M″ b P 3 O c   (1)

wherein 1.0≤x≤2.0; 0≤y≤0.4; 0.05≤z≤0.8; 0.2≤a≤0.7; 1.3≤b≤1.7; 12.0≤c≤13.5; 9−3a−4b x+2y+2z; 1.8≤x+2y+2z≤2.8; A represents at least one bivalent metal element selected from the group consisting of Mg, Ca, and Ni; M′ is at least one trivalent metal element selected from the group consisting of Al, Y, and Ga; and M″ is a 1st M″ which is Ge; and the vicinity of the first electrode layer refers to an area within 5 μm from an interface between the solid-state electrolyte layer and the first electrode layer wherein a thickness of the solid-state electrolyte layer exceeds 5 μm;
a composition of the solid-state electrolyte layer in a non-vicinity area other than the vicinity is expressed as a whole by formula (1) except that M″ is a 2nd M″ which is Ti; and
the first electrode layer contains a solid-state electrolyte which is expressed as a whole by formula (1) except that M″ is the 2nd M″.

2. The all-solid-state battery according to claim 1 , wherein 0<y≤0.4, and A as mentioned above is Mg.

3. The all-solid-state battery according to claim 2 , wherein the electrode active material of the second electrode layer, having an olivine-type crystalline structure, is LiCoPO 4 .

4. The all-solid-state battery according to claim 2 , wherein the solid-state electrolyte layer at least in the vicinity of the first electrode layer is constituted by a primary phase having a NASICON-type crystalline structure and secondary phases of crystalline structures different from that of the primary phase, and a ratio of X-ray diffraction peak intensities I sub /(I main +I sub ) is 2 to 40%, where I sub indicates the total sum of the main diffraction peak intensities of the respective secondary phases, while I main indicates the main diffraction peak intensity of the primary phase.

5. The all-solid-state battery according to claim 2 , wherein both of the first and second electrode layers have an electrode active material having an olivine-type crystalline structure, wherein a composition of the solid-state electrolyte layer at least in a vicinity of the second electrode layer is expressed as a whole by Li x A y Co z M′ a M″ b P 3 O c wherein x, y, z, a, b, c, A, M′ and M″ are the same as those defined in composition formula (1), and the vicinity of the second electrode layer refers to (A′) an area within 5 μm from an interface between the solid-state electrolyte layer and the second electrode layer when a thickness of the solid-state electrolyte layer exceeds 5 μm, or (B′) the entire solid-state electrolyte layer when the thickness of the solid-state electrolyte layer is 5 μm or less.

6. The all-solid-state battery according to claim 5 , wherein both of the first and second electrode layers contain a common electrode active material.

7. The all-solid-state battery according to claim 1 , wherein the electrode active material of the second electrode layer, having an olivine-type crystalline structure, is LiCoPO 4 .

8. The all-solid-state battery according to claim 7 , wherein the solid-state electrolyte layer at least in the vicinity of the first electrode layer is constituted by a primary phase having a NASICON-type crystalline structure and secondary phases of crystalline structures different from that of the primary phase, and a ratio of X-ray diffraction peak intensities I sub /(I main +I sub ) is 2 to 40%, where I sub indicates the total sum of the main diffraction peak intensities of the respective secondary phases, while I main indicates the main diffraction peak intensity of the primary phase.

9. The all-solid-state battery according to claim 7 , wherein both of the first and second electrode layers have an electrode active material having an olivine-type crystalline structure, wherein a composition of the solid-state electrolyte layer at least in a vicinity of the second electrode layer is expressed as a whole by Li x A y Co z M′ a M″ b P 3 O c wherein x, y, z, a, b, c, A, M′ and M″ are the same as those defined in composition formula (1), and the vicinity of the second electrode layer refers to (A′) an area within 5 μm from an interface between the solid-state electrolyte layer and the second electrode layer when a thickness of the solid-state electrolyte layer exceeds 5 μm, or (B′) the entire solid-state electrolyte layer when the thickness of the solid-state electrolyte layer is 5 μm or less.

10. The all-solid-state battery according to claim 9 , wherein both of the first and second electrode layers contain a common electrode active material.

11. The all-solid-state battery according to claim 1 , wherein the solid-state electrolyte layer at least in the vicinity of the first electrode layer is constituted by a primary phase having a NASICON-type crystalline structure and secondary phases of crystalline structures different from that of the primary phase, and a ratio of X-ray diffraction peak intensities I sub /(I main +I sub ) is 2 to 40%, where I sub indicates the total sum of the main diffraction peak intensities of the respective secondary phases, while I main indicates the main diffraction peak intensity of the primary phase.

12. The all-solid-state battery according to claim 11 , wherein the secondary phases contain segregated particles and the largest segregated particle diameter is 5 μm or less.

13. The all-solid-state battery according to claim 12 , wherein both of the first and second electrode layers have an electrode active material having an olivine-type crystalline structure, wherein a composition of the solid-state electrolyte layer at least in a vicinity of the second electrode layer is expressed as a whole by Li x A y Co z M′ a M″ b P 3 O c wherein x, y, z, a, b, c, A, M′ and M″ are the same as those defined in composition formula (1), and the vicinity of the second electrode layer refers to (A′) an area within 5 μm from an interface between the solid-state electrolyte layer and the second electrode layer when a thickness of the solid-state electrolyte layer exceeds 5 μm, or (B′) the entire solid-state electrolyte layer when the thickness of the solid-state electrolyte layer is 5 μm or less.

14. The all-solid-state battery according to claim 11 , wherein the secondary phase is at least one type selected from the group that includes GeO 2 , A 1 PO 4 , and LiCoPO 4 .

15. The all-solid-state battery according to claim 14 , wherein both of the first and second electrode layers have an electrode active material having an olivine-type crystalline structure, wherein a composition of the solid-state electrolyte layer at least in a vicinity of the second electrode layer is expressed as a whole by Li x A y Co z M′ a M″ b P 3 O c wherein x, y, z, a, b, c, A, M′ and M″ are the same as those defined in composition formula (1), and the vicinity of the second electrode layer refers to (A′) an area within 5 μm from an interface between the solid-state electrolyte layer and the second electrode

Assignees

• Taiyo Yuden Kk

Inventors

• Ito Daigo
• Fukushima Takeyuki
• Somei Hidenori
• Ogata Yoichiro
• Kawamura Chie

Classifications

• H01M4/525

  of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy · CPC title

• H01M4/5825 Primary

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

• H01M10/0525 Primary

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

• H01M2004/028

  Positive electrodes · CPC title

• H01M10/052

  Li-accumulators · CPC title