Nonaqueous lithium-type power storage element

Patent metadata

Field	Value
Publication number	US-10396361-B2
Application number	US-201716069963-A
Country	US
Kind code	B2
Filing date	Jan 20, 2017
Priority date	Jan 22, 2016
Publication date	Aug 27, 2019
Grant date	Aug 27, 2019

Abstract

The disclosure provides a nonaqueous lithium power storage element containing a positive electrode, a negative electrode, a separator and a lithium ion-containing nonaqueous electrolytic solution.

First claim

The invention claimed is:

1. A nonaqueous lithium power storage element comprising a positive electrode, a negative electrode, a separator and a lithium ion-containing nonaqueous electrolytic solution, wherein
the negative electrode has a negative electrode power collector, and a negative electrode active material layer containing a negative electrode active material, provided on one or both sides of the negative electrode power collector,
the positive electrode has a positive electrode power collector, and a positive electrode active material layer containing a positive electrode active material, provided on one or both sides of the positive electrode power collector,
in the solid 7 Li-NMR spectrum of the positive electrode active material layer, the relationship 1.04≤b/a≤5.56 is satisfied, where “a” is the peak area from −40 ppm to 40 ppm obtained by measuring with a repeated latency of 10 seconds, and “b” is the peak area from −40 ppm to 40 ppm obtained by measuring with a repeated latency of 3,000 seconds,
the positive electrode active material layer contains a lithium compound other than the positive electrode active material,
the positive electrode active material is an activated carbon, and
the lithium compound is at least one selected from the group consisting of lithium carbonate, lithium oxide and lithium hydroxide.

2. The nonaqueous lithium power storage element according to claim 1 , wherein the amount of lithium in the positive electrode, as calculated by the peak area from −40 ppm to 40 ppm in the solid 7 Li-NMR spectrum of the positive electrode active material layer, is 1 mmol/g to 30 mmol/g per unit weight of the positive electrode active material layer.

3. The nonaqueous lithium power storage element according to claim 2 , wherein
the positive electrode contains one or more compounds selected from the group consisting of compounds represented by the following formulas (1) to (3):
LiX 1 —OR 1 O—X 2 Li  (1)

wherein, in formula (1), R 1 is an alkylene group of 1 to 4 carbon atoms or a halogenated alkylene group of 1 to 4 carbon atoms, and X 1 and X 2 respectively and independently represent —(COO) n (where n is 0 or 1),
LiX 1 —OR 1 O—X 2 R 2   (2)

wherein, in formula (2), R 1 is an alkylene group of 1 to 4 carbon atoms or a halogenated alkylene group of 1 to 4 carbon atoms, R 2 is hydrogen, an alkyl group of 1 to 10 carbon atoms, a mono- or polyhydroxyalkyl group of 1 to 10 carbon atoms, an alkenyl group of 2 to 10 carbon atoms, a mono- or polyhydroxyalkenyl group of 2 to 10 carbon atoms, a cycloalkyl group of 3 to 6 carbon atoms, or an aryl group, and X 1 and X 2 respectively and independently represent —(COO) n (where n is 0 or 1), and
R 2 X 1 —OR 1 O—X 2 R 3   (3)

wherein, in formula (3), R 1 is an alkylene group of 1 to 4 carbon atoms or a halogenated alkylene group of 1 to 4 carbon atoms, R 2 and R 3 respectively and independently represent hydrogen, an alkyl group of 1 to 10 carbon atoms, a polyhydroxyalkyl group of 1 to 10 carbon atoms, an alkenyl group of 2 to 10 carbon atoms, a mono- or polyhydroxyalkenyl group of 2 to 10 carbon atoms, a cycloalkyl group of 3 to 6 carbon atoms or an aryl group, and X 1 and X 2 respectively and independently represent —(COO) n (where n is 0 or 1), in an amount of 1.60×10 −4 mol/g to 300×10 −4 mol/g per unit weight of the positive electrode active material layer.

4. The nonaqueous lithium power storage element according to claim 1 , wherein the mean particle diameter X 1 of the lithium compound is 0.1 μm to 10 μm.

5. The nonaqueous lithium power storage element according to claim 4 , wherein 2 μm≤Y 1 ≤20 μm and X 1 <Y 1 are satisfied, where Y 1 is the mean particle diameter of the positive electrode active material, and the content ratio of the lithium compound in the positive electrode is 1 weight % to 50 weight % based on the total weight of the positive electrode active material layer.

6. The nonaqueous lithium power storage element according to claim 1 , wherein the content ratio of the lithium compound in the positive electrode is 1weight % to 20 weight % based on the total weight of the positive electrode active material layer.

7. The nonaqueous lithium power storage element according to claim 1 , wherein the mean distance between the centers of gravity of voids of the negative electrode active material layer, as obtained by SEM of a cross-section of the negative electrode active material layer, is 1 μm to 10 μm.

8. The nonaqueous lithium power storage element according to claim 7 , wherein r p /r a is 0.10 to 1.10, where r p is the mean distance between the centers of gravity of the voids and r a is the mean particle diameter of the negative electrode active material.

9. The nonaqueous lithium power storage element according to claim 1 , wherein
the negative electrode active material contains a graphite-based carbon material,
the negative electrode active material layer intercalates lithium ion, and
in the solid 7 Li-NMR spectrum of the negative electrode active material layer, in the spectral range of −10 ppm to 35 ppm, the maximum value of the peaks is between 4 ppm to 30 ppm, and the amount of lithium as calculated by the peak area from 4 ppm to 30 ppm is 0.10 mmol/g to 10.0 mmol/g per unit weight of the negative electrode active material layer.

10. The nonaqueous lithium power storage element according to claim 1 , wherein the BET specific surface area per unit volume of the negative electrode active material layer is 1 m 2 /cc to 50 m 2 /cc.

11. The nonaqueous lithium power storage element according to claim 1 , wherein the mean pore size of the negative electrode active material layer is 2 nm to 20 nm.

12. The nonaqueous lithium power storage element according to claim 1 , wherein the mean particle diameter of the negative electrode active material is 1 μm to 10 μm.

13. The nonaqueous lithium power storage element according to claim 1 , wherein the negative electrode active material contains a composite carbon material comprising a graphite material and a carbonaceous material.

14. The nonaqueous lithium power storage element according to claim 1 , wherein the doping amount of lithium ion in the negative electrode active material is 50 mAh/g to 700 mAh/g per unit weight of the negative electrode active material.

15. The nonaqueous lithium power storage element according to claim 1 , wherein the BET specific surface area of the negative electrode active material is 1 m 2 /g to 50 m 2 /g.

16. The nonaqueous lithium power storage element according to claim 1 , wherein the doping amount of lithium ion in the negative electrode active material is 530 mAh/g to 2,500 mAh/g per unit weight of the negative electrode active material.

17. The nonaqueous lithium power storage element according to claim 1 , wherein the BET specific surface area of the negative electrode active material is 100 m 2 /g to 1,500 m 2 /g.

18. The nonaqueous lithium power storage element according to claim 1 , wherein the activated carbon satisfies 0.3 <V 1 ≤0.8 and 0.5≤V 2 ≤1.0, where V 1 (cc/g) is the mesopore volume due to pores with diameters of 20 Å to 500 Å as calculated by the BJH method, and V 2 (cc/g) is the micropore volume due to pores with diameters of smaller than 20 Å as calculated by the MP method, and has a specific surface area of 1,500 m 2 /g to 3,000 m 2 /g, as measured by the BET method.

19. The nonaqueous lithium power storage element according to claim 1 , wherein the activated carbon satisfies 0.8 <V 1 ≤2.5 and 0.8<V

Assignees

• Asahi Chemical Ind

Inventors

• Kamijo Takeshi
• Kusuzaka Keita
• Umetsu Kazuteru
• Murakami Kimiya
• Okada Nobuhiro

Classifications

• H01G11/46

  Metal oxides · CPC title

• Y02E60/13

  Energy storage using capacitors · CPC title

• H01M10/0585

  of accumulators having only flat construction elements, i.e. flat positive electrodes, flat negative electrodes and flat separators · CPC title

• H01M10/0567

  characterised by the additives · CPC title

• H01M4/1393

  of electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx · CPC title