Non-aqueous lithium-type power storage element

Patent metadata

Field	Value
Publication number	US-10242809-B2
Application number	US-201415037102-A
Country	US
Kind code	B2
Filing date	Nov 18, 2014
Priority date	Nov 19, 2013
Publication date	Mar 26, 2019
Grant date	Mar 26, 2019

Abstract

A non-aqueous lithium-type power storage element comprising an electrode laminate body and a non-aqueous electrolyte being housed in an external body, the electrode laminate body having a negative electrode body, a positive electrode body and a separator.

First claim

What is claimed is:

1. A non-aqueous lithium-type power storage element comprising an electrode laminate body comprising a negative electrode body, a positive electrode body and a separator, and a non-aqueous electrolyte, housed in an external body, wherein
the negative electrode body comprises a negative current collector, and a negative electrode active material layer that includes a negative electrode active material and that is provided on one or both surfaces of the negative current collector, the negative electrode active material (i) including a carbon material that can occlude and release lithium ions, and (ii) having a specific surface area of 262 m 2 /g or more as measured by the BET method,
the positive electrode body comprises a positive current collector, and a positive electrode active material layer that includes a positive electrode active material and that is provided on one or both surfaces of the positive current collector, the positive electrode active material including activated carbon,
the non-aqueous electrolyte contains a lithium salt at 0.5 mol/L or greater based on the total amount of the non-aqueous electrolyte,
the negative electrode active material layer includes at least one type of sulfur compound selected from the group consisting of sulfonic acid derivatives represented by the following formulas (1) and (2), and sulfurous acid derivatives represented by the following formulas (3) and (4), the total amount of sulfonic acid derivatives and sulfurous acid derivatives being 2.6×10 −6 mol/g to 2,000×10 −6 mol/g per unit weight of the negative electrode active material:

wherein in formula (1), R 1 represents a C1-24 alkyl group, a C1-24 mono or polyhydroxyalkyl group or its lithium alkoxide, a C2-24 alkenyl group, a C2-24 mono or polyhydroxyalkenyl group or its lithium alkoxide, a C3-6 cycloalkyl group, or an aryl group, and X 1 represents hydrogen, lithium or a C1-12 alkyl group;

wherein in formula (2), R 2 represents a C1-24 alkyl group, a C1-24 mono or polyhydroxyalkyl group or its lithium alkoxide, a C2-24 alkenyl group, a C2-24 mono or polyhydroxyalkenyl group, a C3-6 cycloalkyl group, or an aryl group, and X 2 and X 3 each independently represent hydrogen, lithium or a C1-12 alkyl group;

wherein in formula (3), R 3 represents a C1-24 alkyl group, a C1-24 mono or polyhydroxyalkyl group or its lithium alkoxide, a C2-24 alkenyl group, a C2-24 mono or polyhydroxyalkenyl group or its lithium alkoxide, a C3-6 cycloalkyl group, or an aryl group, and X 4 represents hydrogen, lithium or a C1-12 alkyl group; and

wherein in formula (4), R 4 represents a C1-24 alkyl group, a C1-24 mono or polyhydroxyalkyl group or its lithium alkoxide, a C2-24 alkenyl group, a C2-24 mono or polyhydroxyalkenyl group or its lithium alkoxide, a C3-6 cycloalkyl group, or an aryl group, and X 5 and X 6 each independently represent hydrogen, lithium or a C1-12 alkyl group,
the negative electrode active material layer further includes at least one compound selected from the group consisting of
(i) CH 3 O—X 7 , wherein X 7 represents —(COO) n Li (where n is 0 or 1), and
(ii) C 2 H 5 O—X 8 , wherein X 8 represents —(COO) n Li (where n is 0 or 1), at 7.8×10 −4 mol/g or less per unit weight of the negative electrode active material,
the non-aqueous electrolyte contains at least one type of sultone compound represented by each of the following formulas (9) to (11), at 0.25 wt % to 20 wt % with respect to the total non-aqueous electrolyte:

wherein in formula (9), R 1 -R 6 each independently represent hydrogen, a halogen atom or a C1-12 alkyl group optionally including a halogen atom, and n is an integer of 0 to 3;

wherein in formula (10), R 1 -R 4 each independently represent hydrogen, a halogen atom or a C1-12 alkyl group optionally including a halogen atom, and n is an integer of 0 to 3;

wherein in formula (11), R 1 -R 6 each independently represent hydrogen, a halogen atom or a C1-6 alkyl group optionally including a halogen atom,
the product of the electrostatic capacity F (F) and the internal resistance R (Ω) of the non-aqueous lithium-type power storage element RF (ΩF) is no greater than 2.4, and
the gas quantity generated when the non-aqueous lithium-type power storage element has been stored for 2 months at a cell voltage of 4.0 V and in an environmental temperature of 60° C., is no greater than 13×10 −3 cc/F at 25° C.

2. A non-aqueous lithium-type power storage element according to claim 1 , wherein
the compound represented by formula (9) is 1,3-propane sultone, 2,4-butane sultone, 1,4-butane sultone, 1,3-butane sultone or 2,4-pentane sultone,
the compound represented by formula (10) is 1,3-propene sultone or 1,4-butene sultone, and
the compound represented by formula (11) is 1,5,2,4-dioxadithiepane 2,2,4,4-tetraoxide (cyclodisone).

3. A non-aqueous lithium-type power storage element according to claim 1 , wherein the non-aqueous electrolyte further contains at least one compound selected from the group consisting of
(i) phosphazenes represented by the following formula (12):

wherein in formula (12), X represents fluorine or an alkoxy or aryloxy group,
(ii) acyclic fluoroethers represented by the following formula (13):
R 1 —O—R 2   (13),

wherein R 1 and R 2 each independently represent a C2-6 fluorinated alkyl group,
(iii) fluorine-containing cyclic carbonates, and
(iv) vinylene carbonate.

4. A non-aqueous lithium-type power storage element according to claim 1 , wherein the lithium salt is LiPF 6 .

5. A non-aqueous lithium-type power storage element according to claim 1 , wherein the negative electrode active material satisfies the inequalities 0.010≤Vm1≤0.250, 0.001≤Vm2≤0.200 and 1.5≤Vm1/Vm2≤20.0, where Vm1 (cc/g) is the mesopore volume due to pores with diameters of between 20 angstrom and 500 angstrom, inclusive, as calculated by the BJH method, and Vm2 (cc/g) is the micropore volume due to pores with diameters of smaller than 20 angstrom as calculated by the MP method.

6. A non-aqueous lithium-type power storage element according to claim 1 , wherein the negative electrode active material is a composite porous carbon material obtained by coating a surface of the activated carbon with a carbonaceous material.

7. A non-aqueous lithium-type power storage element according to claim 1 , wherein
the sulfur compound is selected from among sulfonic acid derivatives represented by formula (1) and formula (2), and
in formula (1), R 1 represents a C1-24 alkyl group, C2-24 alkenyl group, C3-6 cycloalkyl group or aryl group, and X 1 represents hydrogen, lithium or a C1-12 alkyl group, and
in formula (2), R 2 represents a C1-24 alkyl group, C2-24 alkenyl group, C3-6 cycloalkyl group or aryl group, and X 2 and X 3 each independently represent hydrogen, lithium or a C1-12 alkyl group.

8. A non-aqueous lithium-type power storage element

Assignees

• Asahi Chemical Ind

Inventors

• Okada Nobuhiro
• Yamahata Yusuke
• Niimura Kensuke
• Kimura Yuima
• Saito Osamu

Classifications

• H01G11/64

  characterised by additives · CPC title

• H01G11/24

  characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor · CPC title

• H01G11/34 Primary

  characterised by carbonisation or activation of carbon · CPC title

• H01G11/30

  characterised by their material · CPC title

• H01M10/0413

  Large-sized flat cells or batteries for motive or stationary systems with plate-like electrodes · CPC title