NONAQUEOUS ELECTROLYTE SOLUTION AND NONAQUEOUS ELECTROLYTE BATTERY USING SAME

• US 20130130128A1
• Filed: 08/02/2011
• Published: 05/23/2013
• Est. Priority Date: 08/05/2010
• Status: Active Grant

• Current Assignee: FUJIFILM Wako Pure Chemical Corporation (Fujifilm Holdings Corporation)
• Original Assignee: WAKO Pure Chemical Industries Limited (Fujifilm Holdings Corporation)
• Inventors: Watahiki, Tsutomu, Okamoto, Kuniaki, Sumino, Motoshige, Ohkubo, Kouki, Ikeda, Tatsuko
• Granted Patent: US 9,257,720 B2
• Time in Patent Office: Days
• US Class Current: 429/338
• CPC Class Codes: H01M 10/0525 Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
• CPC Class Codes: H01M 10/056 characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
• CPC Class Codes: H01M 10/0566 Liquid materials
• CPC Class Codes: H01M 10/0567 characterised by the additives
• CPC Class Codes: H01M 10/0569 characterised by the solvents
• CPC Class Codes: H01M 2300/0025 Organic electrolyte
• CPC Class Codes: H01M 2300/0028 characterised by the solvent
• CPC Class Codes: Y02E 60/10 Energy storage using batteries
• CPC Class Codes: Y02T 10/70 Energy storage systems for electromobility, e.g. batteries

Abstract

[PROBLEM]

To provide: a novel non-aqueous electrolytic solution which uses a methylenebissulfonate derivative, reduced initial irreversible capacity of a battery, and further improves battery characteristics such as cycle characteristics, electric capacity and storage characteristics; a method for producing the non-aqueous electrolytic solution; and a battery which uses the electrolytic solution.

[SOLUTION]

The present invention related to the following <1> to <3>.

<1> A non-aqueous electrolytic solution comprising the following (1) to (3).

• • (1) a non-aqueous solvent comprising at least one selected from a cyclic carbonate ester, a straight chained carbonate ester and a cyclic carboxylic acid ester,
  • (2) a lithium salt which may be dissolved in the non-aqueous solvent, as an electrolyte salt,
  • (3) a methylenebissulfonate derivative represented by the general formula [1]:

<2> A method for producing a non-aqueous electrolytic solution, characterized by dissolving a lithium salt in a non-aqueous solvent, and then dissolving the methylenebissulfonate derivative.

<3> A non-aqueous electrolytic solution battery provided with (i) the non-aqueous electrolytic solution according to the above <1>, (ii) a negative electrode, (iii) a positive electrode and (iv) a separator.

Claims

1. A non-aqueous electrolytic solution comprising the following (1) to (3).

(1) a non-aqueous solvent comprising at least one selected from a cyclic carbonate ester, a straight chained carbonate ester and a cyclic carboxylic acid ester,

(2) a lithium salt which may be dissolved in the non-aqueous solvent, as an electrolyte salt,

(3) a methylenebissulfonate derivative represented by the following general formula [1]:

2. The non-aqueous electrolytic solution according to claim 1, further comprising at least one selected from a negative electrode film forming agent and a blister inhibitor.

3. The non-aqueous electrolytic solution according to claim 1, characterized by comprising the methylenebissulfonate derivative represented by the general formula [I], in a range of 0.01 to 1% by weight, in the non-aqueous electrolytic solution.

4. The non-aqueous electrolytic solution according to claim 1, wherein the non-aqueous solvent is the one comprising at least one cyclic carbonate ester selected from ethylene carbonate and propylene carbonate.

5. The non-aqueous electrolytic solution according to claim 4, wherein ratio of the methylenebissulfonate derivative/the cyclic carbonate ester (weight ratio) is in a range of 0.001 to 0.05.

6. The non-aqueous electrolytic solution according to claim 1, wherein the lithium salt is at least one lithium salt selected from the group of LiPF₆, LiBF₄, LiN(CF₃SO₂)₂, LiN(C₂F₆SO₂)₂, bis[oxalate-O,O′

]lithium borate and difluoro[oxalate-O,O′

]lithium borate.

7. The non-aqueous electrolytic solution according to claim 2, wherein the negative electrode film forming agent is at least one selected from the group consisting of a vinylene carbonate derivative represented by the following general formula [2], a cyclic carbonate ester represented by the general formula [3], a compound represented by the general formula [4], a compound represented by the general formula [4′

] and a compound represented by the general formula [5].

8. The non-aqueous electrolytic solution according to claim 2, wherein the blister inhibitor is at least one selected from the group consisting of γ

-butyrolactone, γ

-valerolactone, γ

-caprolactone, ε

-caprolactone and a cyclic phosphazene derivative represented by the following general formula [6];

11. A non-aqueous electrolytic solution battery provided with (i) the non-aqueous electrolytic solution according to claim 1, (ii) a negative electrode, (iii) a positive electrode and (iv) a separator.

12. The non-aqueous electrolytic solution battery according to claim 11, provided with the following (i) to (iv):

(i) the non-aqueous electrolytic solution according to claim 1;

(ii) the negative electrode being able to store and discharge lithium, comprising at least one negative electrode active material selected from the following (a) to (d), as a main component;

(a) a carbon material having a d value of a lattice plane (002 plane) of 0.340 nm or smaller, in X-ray diffraction,

(b) an oxide of one or more kinds of metal selected from Sn, Si, Pb and Al,

(c) an alloy of one or more kinds of metal selected from Sn, Si, Pb and Al, and lithium,

(d) a lithium-titanium oxide,

(iii) a positive electrode comprising at least one oxide selected from the following (e) to (h) and/or a polyanion compound, as a main component of a positive electrode active material;

(e) lithium cobaltate,

(f) a lithium-manganese complex oxide having a spinel structure,

(g) a lithium transition metal complex oxide having a lamella structure containing manganese, nickel and cobalt,

(h) a lithium-containing olivine-type phosphate salt,

(iv) a separator having polyethylene as a main component.

9. A method for producing a non-aqueous electrolytic solution, characterized by dissolving a lithium salt, as an electrolyte salt, in a non-aqueous solvent, and then by dissolving a methylenebissulfonate derivative represented by the following general formula [1].

10. The method for producing the non-aqueous electrolytic solution according to claim 9, wherein the non-aqueous solvent is the one comprising at least one cyclic carbonate ester and “

Other non-aqueous solvent”

.