Composition for addition to electrolyte solutions containing silyl group-containing compound, electrolyte solution for nonaqueous electricity storage devices containing said composition, and lithium ion secondary battery containing said electrolyte solution

Patent metadata

Field	Value
Publication number	US-2016248121-A1
Application number	US-201415025837-A
Country	US
Kind code	A1
Filing date	Dec 5, 2014
Priority date	Dec 25, 2013
Publication date	Aug 25, 2016
Grant date	—

Abstract

The present invention addresses the problem of providing a composition for addition to electrolyte solutions, which improves storage stability of a silyl group-containing compound that is a useful additive for lithium ion secondary batteries. The description of this application sets forth a composition for addition to electrolyte solutions, which contains one or more silyl group-containing compounds (compound (a)) and one or more basic compounds and/or silicon compounds (compound (b)).

First claim

1 . An addition composition for an electrolytic solution comprising:
(a) a silyl group-containing compound (A), wherein at least one hydrogen atom of an acid selected from the group consisting of a protonic acid having phosphorus atom and/or boron atom, a sulfonic acid, and a carboxylic acid is substituted with a silyl group represented by following general formula (A1):

[wherein, R a1 , R a2 , and R a3 each independently represent a hydrocarbon group having 1 to 20 carbon atoms, which may be substituted]; and
(b) at least one basic compound (B) selected from the group consisting of a Lewis base and a compound represented by general formula Q + Y − [wherein, Q + represents a quaternary ammonium group, a quaternary phosphonium group, an alkali metal, or an alkaline earth metal, and Y − represents an alkoxy group, or an aryloxy group.], and/or at least one silicon compound (C) represented by following general formula (C):

[wherein, R c1 , R c2 , and R c3 each independently represent a hydrocarbon group having 1 to 20 carbon atoms, which may be substituted, or an alkoxy group having 1 to 20 carbon atoms, which may be substituted, and X 1 is a group represented by general formula OR 1 (wherein, R 1 represents a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, which may be substituted, a silyl group having 1 to 20 carbon atoms, SO 2 CH 3 , or SO 2 CF 3 .), or a halogen atom.]; and
wherein the addition composition contains 1 ppm by mass or more and 100% by mass or less of the basic compound (B) and/or the silicon compound (C), relative to 100% by mass of the silyl group-containing compound (A).

2 . The addition composition for the electrolytic solution according to claim 1 , comprising 10 ppm by mass or more and 50% by mass or less of the basic compound (B) and/or the silicon compound (C), relative to 100% by mass of the silyl group-containing compound (A).

3 . The addition composition for the electrolytic solution according to claim 1 , wherein the silyl group-containing compound (A) comprises at least one selected from the group consisting the compounds represented by general formulae (A2) to (A4):

[wherein, M 1 is a phosphorus atom or a boron atom, m is an integer of 1 to 20, n is 0 or 1 when M 1 is a phosphorus atom, n is 0 when M 1 is a boron atom, R a1 , R a2 , and R a3 are as defined in general formula (A1), and R a4 and R a5 each independently represent a group selected from the group consisting of an OH group, an OLi group, a hydrocarbon group having 1 to 20 carbon atoms, which may be substituted, an alkoxy group having 1 to 20 carbon atoms, which may be substituted, and a siloxy group having 1 to 20 carbon atoms.],

[wherein, M 2 is a phosphorus atom or a boron atom, j is an integer of 2 to 20, k is 0 or 1 when M 2 is a phosphorus atom, k is 0 when M 2 is a boron atom, and R a6 represents a group selected from the group consisting of an OH group, an OLi group, a hydrocarbon group having 1 to 20 carbon atoms, which may be substituted, an alkoxy group having 1 to 20 carbon atoms, which may be substituted, and a siloxy group having 1 to 20 carbon atoms, and a group represented by general formula OP(O) l (R a7 R a8 ) (wherein, 1 is 0 or 1, and R a7 and R a8 each independently represent an OH group, an OLi group, a hydrocarbon group having 1 to 20 carbon atoms, which may be substituted, an alkoxy group having 1 to 20 carbon atoms, which may be substituted, and a siloxy group having 1 to 20 carbon atoms.).],

[wherein, R a1 , R a2 , and R a3 are as defined in general formula (A1), and R a9 represents a hydrocarbon group having 1 to 20 carbon atoms, which may be substituted.].

4 . The addition composition for the electrolytic solution according to claim 1 , wherein the Lewis base is a nitrogen-containing organic Lewis base.

5 . An electrolytic solution for a non-aqueous storage device comprising a non-aqueous solvent, a lithium salt, and the addition composition for the electrolytic solution according to claim 1 .

6 . The electrolytic solution for the non-aqueous storage device according to claim 5 , comprising 0.01% by mass or more and 10% by mass or less of the silyl group-containing compound (A), relative to 100% by mass of the electrolytic solution for the non-aqueous storage device.

7 . The electrolytic solution for the non-aqueous storage device according to claim 5 , wherein the lithium salt is at least one selected from the group consisting of LiPF 6 , LiBF 4 , LiClO 4 , LiAsF 6 , Li 2 SiF 6 , LiOSO 2 C k F 2k+1 [wherein, k is an integer of 0 to 8], LiN(SO 2 C k F 2k+1 ) 2 [wherein, k is an integer of 0 to 8], and LiPF n (C k F 2k+1 ) 6-n [wherein, n is an integer of 1 to 5, and k is an integer of 1 to 8].

8 . The electrolytic solution for the non-aqueous storage device according to claim 5 , further comprising at least one selected from the group consisting of lithium difluorophosphate and lithium monofluorophosphate.

9 . The electrolytic solution for the non-aqueous storage device according to claim 5 , wherein the non-aqueous solvent comprises a cyclic carbonate and/or a linear carbonate.

10 . A lithium-ion secondary battery comprising a positive electrode containing a positive electrode active material, a negative electrode containing a negative electrode active material, and the electrolytic solution for the non-aqueous storage device according to claim 5 .

11 . The lithium-ion secondary battery according to claim 10 , wherein the positive electrode active material has a discharge capacity of 10 mAh/g or more at a potential of 4.1 V (vs Li/Li + ) or more.

12 . The lithium-ion secondary battery according to claim 11 , wherein the positive electrode active material is at least one selected from the group consisting of:
an oxide represented by following formula (E1):
LiMn 2-x Ma x O 4   (E1)

[wherein, Ma represents at least one selected from the group consisting of transition metals, and x is a number within the range of 0.2≦x≦0.7];
an oxide represented by following formula (E2):
LiMn 1-u Me u O 2   (E2)

[wherein, Me represents at least one selected from the group consisting of transition metals, except for Mn, and u is a number within the range of 0.1≦u≦0.9];
a composite oxide represented by following formula (E3):
z Li 2 McO 3 -(1- z )LiMdO 2   (E3)

[wherein, Mc and Md each independently represent at least one selected from the group consisting of transition metals, and z is a number within the range of 0.1≦z≦0.9];
a compound represented by following formula (E4):
LiMb 1-y Fe y PO 4   (E4)

[wherein, Mb represents at least one selected from the group consisting of Mn and Co, and y is a number within the range of 0≦y≦0.9]; and
a compound represented by following formula (E5):
Li 2 MfPO 4 F  (E5)

[wherein, Mf represents at least one selected from the group consisting of transition metals].

13 . The lithium-ion secondary battery according to claim 10 , wherein positive electrode potential based on lithium is 4.1 V (vs Li/Li + ) or more, when the battery is fully charg

Assignees

• Asahi Chemical Ind

Inventors

• Uematsu Nobuyuki
• Ozaki Fumiaki
• Nakamura Ayaka

Classifications

• H01M4/625

  Carbon or graphite · CPC title

• H01M10/0569

  characterised by the solvents · CPC title

• H01M4/0404

  by coating on electrode collectors · CPC title

• H01M4/525

  of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy · CPC title

• H01M2004/027

  Negative electrodes · CPC title