Secondary battery

• US 4,668,595 A
• Filed: 05/09/1986
• Issued: 05/26/1987
• Est. Priority Date: 05/10/1985
• Status: Expired

• Current Assignee: Asahi Kasei Kogyo Kabushiki Kaisha (Asahi Kasei Corporation)
• Original Assignee: Asahi Kasei Kogyo Kabushiki Kaisha (Asahi Kasei Corporation)
• Inventors: Yoshino, Akira, Nakajima, Takayuki, Sanechika, Kenichi
• Primary Examiner(s): Skapars, Anthony
• Application Number:
  US06/861,423
• Time in Patent Office: 382 Days
• Field of Search: 429/194, 429/196, 429/197, 429/198, 429/211.8, 429/212, 252/182.1, 423/594, 423/593
• US Class Current: 429/231.1
• CPC Class Codes: H01M 10/05 Accumulators with non-aqueous electrolyte H01M10/39 takes precedence
• CPC Class Codes: H01M 4/36 Selection of substances as active materials, active masses, active liquids
• CPC Class Codes: H01M 4/485 of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy H01M4/505, H01M4/525 take precedence
• CPC Class Codes: H01M 4/583 Carbonaceous material, e.g. graphite-intercalation compounds or CFx
• CPC Class Codes: H01M 4/587 for inserting or intercalating light metals
• CPC Class Codes: Y02E 60/10 Energy storage using batteries

Abstract

This invention provides a secondary battery in a nonaqueous type using a substance indicated in I below and/or a substance indicated in II below as an active material for either of positive and negative electrodes:

I: a composite oxide possessing a layer structure and represented by the general formula:

A.sub.x M.sub.y N.sub.z O.sub.2

wherein A stands for at least one alkali metal, M for a transition metal, N for at least one member selected from the group consisting of Al, In, and Sn, and x, y, and z respectively for the number falling in a specific range,

II: an n-doped carbonaceous material which has a BET-method specific surface area, and a crystal thickness, Lc, in the X-ray diffraction and a true density, ρ, both having the values falling in a specific range.

The secondary battery of this invention is small and light, excels in cyclicity and self-discharging property, and possesses a high energy density.

Claims

1. A secondary battery comprising positive and negative electrodes, a separator, and a nonaqueous electrolyte, wherein said secondary battery is characterized by having as an active material for either of said positive and negative electrodes:

I;

a composite oxide possessing a layer structure and represented by the general formula;

space="preserve" listing-type="equation">A.sub.x M.sub.y N.sub.z O.sub.2

wherein A is at least one member selected from the group consisting of alkali metals, M is a transition metal, N is at least one member selected from the group consisting of Al, In, and Sn, and x, y, and z satisfy the expression, 0.05≦

x≦

1.10, 0.85≦

y≦

1.00, and 0.001≦

z≦

0.10, respectively, and

II;

an n-doped carbonaceous material which has a BET-method specific surface area, A (m² /g), being in the range of 0.2<

A<

100 and a crystal thickness, Lc (Å

), based on X-ray diffraction and a true density, ρ

(g/cm³), which satisfies the conditions, 1.70<

ρ

<

2.18 and 10<

Lc<

120ρ

-189.

2. A secondary battery according to claim 1, wherein said A is at least one member selected from the group consisting of lithium, sodium, and potassium.

3. A secondary battery according to claim 1, wherein said M is at least one member selected from the group consisting of Ni and Co.

4. A secondary battery according to claim 1, wherein said N is Sn.

5. A secondary battery according to claim 1, wherein the carbonaceous material is carbon fibers of the vapor-phase growth method and/or the comminuted product thereof.

6. A secondary battery according to claim 1, wherein the carbonaceous material is a fired carbonization product of pitch.

7. A secondary battery according to claim 1, wherein the carbonaceous material is a fired carbonization product of a polymer of acrylonitrile.

8. A secondary battery according to claim 1, wherein the carbonaceous material is needle coke.

9. A secondary battery according to claim 1, wherein the active material is formed by using an organic polymer dissolved and/or dispersed in a solvent as a binder.

10. A secondary battery according to claim 9, wherein the organic polymer has a specific dielectric constant greater than 4.5 at 25°

C. and 1 KHz of frequency.

11. A secondary battery according to claim 9, wherein the organic polymer is at least one polymer or copolymer selected from the group consisting of acrylonitrile, methacrylonitrile, vinyl fluoride, and vinylidene fluoride.

12. A secondary battery according to claim 1, wherein the separator is a polyolefin type microporous membrane.

13. A secondary battery according to claim 1, wherein cyclic carbonate is used as a solvent for the nonaqueous electrolyte.

14. A secondary battery according to claim 13, wherein the cyclic carbonate is at least one member selected from the group consisting of propylene carbonate, ethylene carbonate, and vinylene carbonate.

15. A secondary battery according to claim 1, wherein either of the positive and negative electrodes includes carbon as a conductor aid in a concentration of 1 to 30 parts by weight based on 100 parts by weight of the composite oxide as the active material.

16. A secondary battery according to claim 15, wherein the carbon is at least one member selected from the group consisting of graphite and carbon black.

17. A secondary battery according to claim 15, wherein the carbon is a mixture of carbon having an average particle diameter of 0.1-10μ

and carbon having an average particle diameter of 0.01-0.08μ

.

18. A secondary battery according to claim 1, wherein the positive electrode is

a composite oxide possessing a layer structure and represented by the general formula:

space="preserve" listing-type="equation">A.sub.x M.sub.y N.sub.z O.sub.2

wherein A is at least one member selected from the group consisting of alkali metals, M is a transition metal, N is at least one member selected from the group consisting of Al, In, and Sn, and x, y, and z satisfy the expression, 0.05≦

x≦

1.10, 0.85≦

y≦

1.00, and 0.001≦

z≦

0.10, respectively.

19. A secondary battery according to claim 1, wherein the negative electrode is

an n-doped carbonaceous material which has a BET-method specific surface area, A (m² /g), being in the range of 0.1<

A<

100 and a crystal thickness, Lc (Å

), based on X-ray diffraction and a true density, ρ

(g/cm³), satisfying the conditions, 1.70<

ρ

<

2.18 and 10<

Lc<

120ρ

-189.

20. A secondary battery according to claim 1, wherein the positive electrode is

a composite oxide possessing a layer structure and represented by the general formula:

space="preserve" listing-type="equation">A.sub.x M.sub.y N.sub.z O.sub.2

wherein A is at least one member selected from the group consisting of alkali metal, M is a transition metal, N is at least one member selected from the group consisting of Al, In, and Sn, and x, y, and z satisfy the expressions, 0.05≦

x≦

1.10, 0.85 <

y≦

1.00, and 0.001≦

2≦

0.10, respectively and, the negative electrode is

an n-doped carbonaceous material which has a BET-method specific surface area, A (m² /g), being in the range of 0.1<

A<

100 and a crystal thickness, Lc (Å

), based on X-ray diffraction and a true density, ρ

(g/cm³), satisfying the conditions, 1.70<

ρ

<

2.18 and 10<

Lc<

120ρ

-189.