Non-aqueous lithium-type electricity storage element

Patent metadata

Field	Value
Publication number	US-11824203-B2
Application number	US-201816646213-A
Country	US
Kind code	B2
Filing date	Nov 13, 2018
Priority date	Nov 14, 2017
Publication date	Nov 21, 2023
Grant date	Nov 21, 2023

Abstract

Provided is a non-aqueous lithium-type electricity storage element which includes a positive electrode current collector having a positive electrode active material layer disposed thereon, wherein, in a solid-state 7Li-NMR spectrum of the positive electrode active material layer, a signal area ratio a/b, which is the ratio of a signal area ratio of component A having a signal at least at −2 to 2.5 ppm to a signal area of component B having a signal at −6 to −2.5 ppm is 1.5 to 20.0.

First claim

The invention claimed is:

1. A non-aqueous lithium-type electricity storage element comprising a positive electrode, a negative electrode, a separator and a non-aqueous electrolytic solution containing lithium ions,
wherein the negative electrode has a negative electrode current collector, and a negative electrode active material layer containing a negative electrode active material, disposed on one or both sides of the negative electrode current collector, the negative electrode active material contains a carbon material capable of intercalating and releasing lithium ions,
the positive electrode has a positive electrode current collector, and a positive electrode active material layer containing a positive electrode active material, disposed on one or both sides of the positive electrode current collector, the positive electrode active material contains an activated carbon, and
the positive electrode active material layer contains a component A having a signal in a range of −2 to 2.5 ppm and a component B having a signal in a range of −6 to −2.5 ppm in a solid-state 7 Li-NMR spectrum of the positive electrode active material layer, and has a signal area ratio a/b of 1.5 to 20.0 when a signal area of the component A is a, and a signal area of the component B is b, and the component B is derived from active sites interacting with lithium ions on a surface of the activated carbon, and
the positive electrode active material layer contains a lithium compound other than the positive electrode active material, and a mean particle diameter of the lithium compound satisfies the expression 0.1 μm≤X 1 ≤10 μm, where X 1 is the mean particle diameter of the lithium compound.

2. The non-aqueous lithium-type electricity storage element according to claim 1 , wherein the positive electrode active material further contains a transition metal oxide capable of intercalating and releasing lithium ions.

3. The non-aqueous lithium-type electricity storage element according to claim 2 ,
wherein the transition metal oxide contains at least one lithium transition metal oxide selected from the group consisting of the following formulae:
Li x1 CoO 2 wherein, in the formula, x1 satisfies 0≤x1≤2,
Li x1 NiO 2 wherein, in the formula, x1 satisfies 0≤x1≤2,
Li x1 Ni y M 1 (1-y) O 2 wherein, in the formula, M 1 is at least one element selected from the group consisting of Co, Mn, Al, Fe, Mg and Ti, x1 satisfies 0≤x1≤2, and y satisfies 0.2<y<0.97,
Li x1 Ni 1/3 Co 1/3 Mn 1/3 O 2 wherein, in the formula, x1 satisfies 0≤x1≤2,
Li x1 MnO 2 wherein, in the formula, x1 satisfies 0≤x1≤2,
α-Li x1 FeO 2 wherein, in the formula, x1 satisfies 0≤x1≤2,
Li x1 VO 2 wherein, in the formula, x1 satisfies 0≤x1≤2,
Li x1 CrO 2 wherein, in the formula, x1 satisfies 0≤x1≤2,
Li x1 Mn 2 O 4 wherein, in the formula, x1 satisfies 0≤x1≤2,
Li x1 M 2 y Mn (2-y) O 4 wherein, in the formula, M 2 is at least one element selected from the group consisting of Co, Ni, Al, Fe, Mg and Ti, x1 satisfies 0≤x1≤2, and y satisfies 0.2<y<0.97,
Li x1 Ni a Co b Al (1-a-b) O 2 wherein, in the formula, x1 satisfies 0≤x1≤2, a satisfies 0.2<a<0.97 and b satisfies 0.2<b<0.97,
Li x1 Ni c Co d Mn (1-c-d) O 2 wherein, in the formula, x1 satisfies 0≤x1≤2, c satisfies 0.2<c<0.97, and d satisfies 0.2<d<0.97,
Li x1 M 3 PO 4 wherein, in the formula, M 3 is at least one element selected from the group consisting of Co, Ni, Fe, Mn and Cu, and x1 satisfies 0≤x1≤2, and
Li z V 2 (PO 4 ) 3 wherein, in the formula, z satisfies 0≤z≤3.

4. The non-aqueous lithium-type electricity storage element according to claim 2 , wherein the activated carbon has a mean particle diameter of 2 μm or greater and 20 μm or less, and the transition metal oxide has a mean particle diameter of 0.1 μm or greater and 20 μm or less.

5. The non-aqueous lithium-type electricity storage element according to claim 2 , wherein the positive electrode contains a carbon material containing the activated carbon, and the lithium transition metal oxide, and when a weight proportion of the carbon material in the positive electrode active material layer is A 1 , and a weight proportion of the lithium transition metal oxide is A 2 , A 2 /A 1 is 0.1 or greater and 2.5 or less.

6. The non-aqueous lithium-type electricity storage element according to claim 1 , wherein the positive electrode contains one or more selected from the group consisting of lithium carbonate, sodium carbonate, potassium carbonate, rubidium carbonate, and cesium carbonate in an amount of 1% by weight or greater and 50% by weight or less relative to a total amount of the positive electrode active material.

7. The non-aqueous lithium-type electricity storage element according to claim 1 , wherein the positive electrode current collector and the negative electrode current collector are nonporous metal foils.

8. The non-aqueous lithium-type electricity storage element according to claim 1 , wherein the negative electrode contains at least two types of the negative electrode active materials.

9. The non-aqueous lithium-type electricity storage element according to claim 8 , wherein at least one of the negative electrode active material has a mean particle diameter of 1 μm or greater and 15 μm or less.

10. The non-aqueous lithium-type electricity storage element according to claim 1 , wherein when a basis weight of the positive electrode active material layer of the positive electrode is C 1 (g/m 2 ) and a basis weight of the negative electrode active material layer of the negative electrode is C 2 (g/m 2 ), C 1 /C 2 is 0.35 or greater and 5.80 or less.

11. The non-aqueous lithium-type electricity storage element according to claim 1 , wherein when a thickness of the positive electrode active material layer of the positive electrode is D 1 (μm) and a thickness of the negative electrode active material layer of the negative electrode is D 2 (μm), D 1 /D 2 is 0.30 or greater and 5.00 or less.

12. The non-aqueous lithium-type electricity storage element according to claim 1 , wherein an element concentration of sulfur (S) on the surface of the negative electrode active material layer detected by X-ray photoelectron spectroscopy (XPS), is 0.5 atomic % or greater, and a peak having 162 eV to 166 eV is present in a S2p spectrum of the surface of the positive electrode active material layer, obtained by X-ray photoelectron spectroscopy (XPS).

13. The non-aqueous lithium-type electricity storage element according to claim 1 , wherein the non-aqueous electrolytic solution contains as additives:
one or more sulfur-containing compounds (X) selected from the group consisting of a thiophene compound represented by formula (1):

wherein, in formula (1), R 1 , R 2 , R 3 , and R 4 each independently represent a hydrogen atom, a halogen atom, a formyl group, an acetyl group, a nitrile group, an acetyl group, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms or an alkyl ester having 1 to 6 carbon atoms, and
one or more sulfur-containing compounds (Y) selected from the group consisting of a cyclic sulfate compound represented by formula (2-1):

wherein, in formula (2-1), R 5 , R 6 , R 7 , and R 8 each represent at least one selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group having 1 to 12 carbon atoms, and a halogenated alkyl group having 1 to 12 carbon atoms, may be the same or different from each other; and n

Assignees

• Asahi Chemical Ind

Inventors

• Kimura Yuima
• Umetsu Kazuteru
• Hirakawa Yuichiro
• Morita Hitoshi
• Okada Nobuhiro

Classifications

• H01M4/663 Primary

  containing carbon or carbonaceous materials as conductive part, e.g. graphite, carbon fibres · CPC title

• H01M4/131

  Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx · CPC title

• H01M4/366

  as layered products · CPC title

• H01M4/505

  of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy · CPC title

• 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