ANODE AND METHOD OF MANUFACTURING THE SAME, AND SECONDARY BATTERY

• US 20090111020A1
• Filed: 10/21/2008
• Published: 04/30/2009
• Est. Priority Date: 10/26/2007
• Status: Active Grant

• Current Assignee: Murata Manufacturing Co Limited
• Original Assignee: Sony Corporation (Sony Group Corp.)
• Inventors: Ihara, Masayuki, Nakai, Hideki, Yamaguchi, Hiroyuki, Kubota, Tadahiko, Fujita, Shigeru
• Granted Patent: US 10,312,518 B2
• Time in Patent Office: Days
• US Class Current: 429/207
• CPC Class Codes: H01M 10/052 Li-accumulators
• CPC Class Codes: H01M 10/0567 characterised by the additives
• CPC Class Codes: H01M 10/0568 characterised by the solutes
• CPC Class Codes: H01M 10/0569 characterised by the solvents
• CPC Class Codes: H01M 4/134 Electrodes based on metals, Si or alloys
• CPC Class Codes: H01M 4/139 Processes of manufacture
• CPC Class Codes: H01M 4/62 Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
• CPC Class Codes: Y02E 60/10 Energy storage using batteries

Abstract

An anode and a secondary battery capable of improving the charge and discharge efficiency are provided. The anode includes an anode current collector, and an anode active material layer provided on the anode current collector. The anode active material layer has a plurality of anode active material particles containing at least one of a simple substance of silicon, a compound of silicon, a simple substance of tin and a compound of tin, and has a coat containing an oxo acid salt in at least part of the surface of the anode active material particles.

Claims

1. An anode comprising:

an anode current collector; and

an anode active material layer provided on the anode current collector, wherein

the anode active material layer has a plurality of anode active material particles containing at least one of a simple substance of silicon, a compound of silicon, a simple substance of tin and a compound of tin, and has a coat containing an oxo acid salt in at least part of the surface of the anode active material particles.

2. The anode according to claim 1, wherein the oxo acid salt is a poly acid salt.

3. The anode according to claim 1, wherein the oxo acid salt is lithium borate or lithium silicate.

4. The anode according to claim 1, wherein the oxo acid salt is lithium metaborate, lithium tetraborate, lithium orthosilicate, or lithium metasilicate.

5. The anode according to claim 1, wherein the coat containing the oxo acid salt is formed by liquid-phase deposition method.

6. The anode according to claim 1, wherein the anode active material particles are composed of a material having a silicon simple substance as a main body or a SnCoC-containing material.

7. The anode according to claim 1, wherein the coat containing the oxo acid salt further contains an alkali metal salt or an alkali earth metal salt.

8. The anode according to claim 1, wherein a coat containing an oxide of at least one selected from the group consisting of silicon, germanium, and tin is further provided between the anode active material particles and the coat containing the oxo acid salt.

9. The anode according to claim 1, wherein the anode active material layer has a metal material not being alloyed with an electrode reactant in a gap between the anode active material particles.

10. The anode according to claim 9, wherein the anode active material particles have a multilayer structure in the particles, and the anode active material layer has the metal material in a gap in the anode active material particles.

11. The anode according to claim 9, wherein the metal material contains at least one metal element selected from the group consisting of iron (Fe), cobalt (Co), nickel (Ni), zinc (Zn), and copper (Cu).

12. A method of manufacturing an anode, wherein an anode current collector provided with an anode active material layer having a plurality of anode active material particles containing at least one of a simple substance of silicon, a compound of silicon, a simple substance of tin and a compound of tin is dipped into a solution of the oxo acid salt, and thereby a coat containing the oxo acid salt is formed on the surface of the anode active material particles.

13. A secondary battery comprising:

a cathode;

an anode; and

an electrolytic solution,

wherein the anode has an anode current collector and an anode active material layer provided on the anode current collector,

the anode active material layer has a plurality of anode active material particles containing at least one of a simple substance of silicon, a compound of silicon, a simple substance of tin and a compound of tin, and has a coat containing an oxo acid salt in at least part of the surface of the anode active material particles.

14. The secondary battery according to claim 13, wherein the oxo acid salt is a poly acid salt.

15. The secondary battery according to claim 13, wherein the oxo acid salt is lithium borate or lithium silicate.

16. The secondary battery according to claim 13, wherein the oxo acid salt is lithium metaborate, lithium tetraborate, lithium orthosilicate, or lithium metasilicate.

17. The secondary battery according to claim 13, wherein the anode active material particles have the coat containing the oxo acid salt at least in a region where the anode active material particles are contacted with the electrolytic solution.

18. The secondary battery according to claim 13, wherein the coat containing the oxo acid salt is formed by liquid-phase deposition method.

19. The secondary battery according to claim 13, wherein the anode active material particles are composed of a material having silicon simple substance as a main body or a SnCoC-containing material.

20. The secondary battery according to claim 13, wherein the coat containing the oxo acid salt further contains an alkali metal salt or an alkali earth metal salt.

21. The secondary battery according to claim 13, wherein a coat containing an oxide of at least one selected from the group consisting of silicon, germanium, and tin is further provided between the anode active material particles and the coat containing the oxo acid salt.

22. The secondary battery according to claim 13, wherein the anode active material layer has a metal material not being alloyed with an electrode reactant in a gap between the anode active material particles.

23. The secondary battery according to claim 22, wherein the anode active material particles have a multilayer structure in the particles, and the anode active material layer has the metal material in a gap in the anode active material particles.

24. The secondary battery according to claim 22, wherein the metal material contains at least one metal element selected from the group consisting of iron (Fe), cobalt (Co), nickel (Ni), zinc (Zn), and copper (Cu).

28. The secondary battery according to claim 13 that has a peak of at least one or more secondary ions selected from the group consisting of positive secondary ions of Li₂PO₂F₂⁺, Li₃PO₃F⁺, and Li₂BO₂⁺ and negative secondary ions of PO₂F₂⁻

, PO₃F⁻

, LiPO₃F⁻

, BO⁻

, BO₂⁻

, and LiB₂O₄⁻

in surface analysis by Time of Flight Secondary Ion Mass Spectrometry (TOF-SIMS) of the anode.

29. The secondary battery according to claim 28, wherein the positive secondary ion Li₂PO₂F₂⁺ detected in the surface analysis by the TOF-SIMS has a ratio to an active material element peak Si⁺ intensity (Li₂PO₂F₂⁺/Si⁺) is 0.4 or more.

30. The secondary battery according to claim 28, wherein the positive secondary ion Li₃PO₃F⁺ detected in the surface analysis by the TOF-SIMS has a ratio to an active material element peak Si⁺ intensity (Li₃PO₃F⁺/Si⁺) is 0.5 or more.

31. The secondary battery according to claim 28, wherein the positive secondary ion Li₂BO₂⁺ detected in the surface analysis by the TOF-SIMS has a ratio to an active material element peak Si⁺ intensity (Li₂BO₂⁺/Si⁺) is 0.5 or more.

32. The secondary battery according to claim 28, wherein the positive secondary ion Li₂PO₂F₂⁺ detected in the surface analysis by the TOF-SIMS has a ratio to an active material element peak Sn⁺ intensity (Li₂PO₂F₂⁺/Sn⁺) is 1.0 or more.

33. The secondary battery according to claim 28, wherein the positive secondary ion Li₃PO₃F⁺ detected in the surface analysis by the TOF-SIMS has a ratio to an active material element peak Sn⁺ intensity (Li₃PO₃F⁺/Sn⁺) is 1.2 or more.

34. The secondary battery according to claim 28, wherein the positive secondary ion Li₂BO₂⁺ detected in the surface analysis by the TOF-SIMS has a ratio to an active material element peak Si⁺ intensity (Li₂BO₂⁺/Si⁺) is 1.2 or more.

25. A secondary battery comprising:

a cathode;

an anode; and

an electrolytic solution,

wherein the anode contains at least one of a simple substance of silicon, a compound of silicon, a simple substance of tin and a compound of tin, and

the electrolytic solution contains a borate.

26. The secondary battery according to claim 25, wherein the borate is lithium metaborate, lithium tetraborate, or lithium tetrafluoroborate.

27. The secondary battery according to claim 25, wherein a content of the borate in the electrolytic solution is in the range from 0.01 wt % to 5 wt %.

35. The secondary battery according to claim 25 that has a peak of at least one or more secondary ions selected from the group consisting of positive secondary ions of Li₂PO₂F₂⁺, Li₃PO₃F⁺, and Li₂BO₂⁺ and negative secondary ions of PO₂F₂⁻

, PO₃F⁻

, LiPO₃F⁻

, BO⁻

, BO₂⁻

, and LiB₂O₄⁻

in surface analysis by Time of Flight Secondary Ion Mass Spectrometry (TOF-SIMS) of the anode.

36. The secondary battery according to claim 35, wherein the positive secondary ion Li₂PO₂F₂⁺ detected in the surface analysis by the TOF-SIMS has a ratio to an active material element peak Si⁺ intensity (Li₂PO₂F₂⁺/Si⁺) is 0.4 or more.

37. The secondary battery according to claim 35, wherein the positive secondary ion Li₃PO₃F⁺ detected in the surface analysis by the TOF-SIMS has a ratio to an active material element peak Si⁺ intensity (Li₃PO₃F⁺/Si⁺) is 0.5 or more.

38. The secondary battery according to claim 35, wherein the positive secondary ion LI₂BO₂⁺ detected in the surface analysis by the TOF-SIMS has a ratio to an active material element peak Si⁺ intensity (LI₂BO₂⁺/Si⁺) is 0.5 or more.

39. The secondary battery according to claim 35, wherein the positive secondary ion Li₂PO₂F₂⁺ detected in the surface analysis by the TOF-SIMS has a ratio to an active material element peak Sn⁺ intensity (Li₂PO₂F₂⁺/Sn⁺) is 1.0 or more.

40. The secondary battery according to claim 35, wherein the positive secondary ion Li₃PO₃F⁺ detected in the surface analysis by the TOF-SIMS has a ratio to an active material element peak Sn⁺ intensity (Li₃PO₃F⁺/Sn⁺) is 1.2 or more.

41. The secondary battery according to claim 35, wherein the positive secondary ion Li₂BO₂⁺ detected in the surface analysis by the TOF-SIMS has a ratio to an active material element peak Si⁺ intensity (Li₂BO₂⁺/Si⁺) is 1.2 or more.

42. The secondary battery according to claim 25, wherein the electrolytic solution further contains a cyclic ester carbonate compound having an unsaturated bond at a ratio of from 0.01 wt % to 10 wt %.

43. The secondary battery according to claim 25, wherein a solvent of the electrolytic solution contains at least one selected from the group consisting of a chain ester carbonate containing halogen shown in the following Formula 1 and a halogenated cyclic ester carbonate obtained by substituting part or all of hydrogen atoms in R1, R2, R3, and R4 of a cyclic ester carbonate shown in the following Formula 2 with a fluorine atom, a chlorine atom, or a bromine atom:

where R1 to R6 represent a hydrogen group, a halogen group, an alkyl group, or an alkyl halide group, R1 to R6 may be identical or different, but at least one of R1 to R6 has halogen as an element;

where R1 to R4 represent a hydrogen group, a halogen group, an alkyl group, or an alkyl halide group, R1 to R4 may be identical or different, but at least one of R1 to R4 has halogen as an element.

44. The secondary battery according to claim 25, wherein the halogenated cyclic ester carbonate is 4-fluoro-1,3-dioxolane-2-one or 4,5-difluoro-1,3-dioxolane-2-one, and the chain ester carbonate containing halogen is fluoromethyl methyl carbonate, bis(fluoromethyl)carbonate, or difluoromethyl methyl carbonate.

45. The secondary battery according to claim 25, wherein the electrolytic solution contains sultone.

46. The secondary battery according to claim 25, wherein the electrolytic solution contains an acid anhydride.

47. The secondary battery according to claim 25, wherein the electrolytic solution contains at least one of compounds shown in the following Formula 3 as an electrolyte salt:

where R11 represents —

C(═

O)—

R21-C(═

O)—

group (R21 represents an alkylene group, an alkylene halide group, an arylene group, or an arylene halide group), —

C(═

O)—

C(R23)(R24)- group (R23 and R24 represent hydrogen, halogen, an alkyl group, an alkyl halide group, an aryl group, or an aryl halide group), or —

C(═

O)—

C(═

O)-group,

R12 represents a halogen group, an alkyl group, an alkyl halide group, an aryl group, or an aryl halide group,

X11 and X12 respectively represent oxygen (O) or sulfur (S),

M11 represents a transition metal element, or a Group 3B element, a Group 4B element, or a Group 5B element in the short period periodic table,

M21 represents a Group 1A element or a Group 2A element in the short period periodic table,

a represents one of integer numbers 1 to 4,

b represents one of integer numbers 0 to 8, and

c, d, e, and f respectively represent one of integer numbers 1 to 3.

48. The secondary battery according to claim 25, wherein the electrolytic solution contains a compound shown in the following Formula 31 as an electrolyte salt:

where R11 represents —

C(═

O)—

R21-C(═

O)—

group (R21 represents an alkylene group, an alkylene halide group, an arylene group, or an arylene halide group), —

C(═

O)—

C(═

O)-group, or —

C(═

O)—

C(R22)₂ (R22 represents hydrogen, halogen, an alkyl group, an alkyl halide group, an aryl group, or an aryl halide group)- group,

R13 represents halogen,

M12 represents phosphorus (P) or boron (B),

M21 represents a Group 1A element or a Group 2A element in the short period periodic table or aluminum,

a represents one of integer numbers 1 to 4,

b1 represents one of integer numbers 0, 2 and 4, and

c, d, e, and f respectively represent one of integer numbers 1 to 3.

49. The secondary battery according to claim 25, wherein the electrolytic solution contains at least one selected from the group consisting of compounds shown in the following Formulas 3-1 to 3-6 as an electrolyte salt.

50. The secondary battery according to claim 25, wherein the electrolytic solution further contains at least one selected from the group consisting of LiPF₆, LiBF₄, LiClO₄, LiAsF₆, and lithium salts shown in the following Formulas 4 to 6:

LiN(C_mF_2m+1SO₂)(C_nF_2n+1SO₂)  

 

(4)

where m and n represent an integer number of 1 or more;

where R represents a straight-chain or a branched perfluoro alkylene group having a carbon number of 2 to 4, n represents an integer number of 1 to 3, and M represents a transition metal element;

LiC(C_pF_2p+1SO₂)(C_qF_2q+1SO₂)(C_rF_2r+1SO₂)  

 

(6)

where p, q, and r represent an integer number of 1 or more.