WO2007069543A1

WO2007069543A1 - Ion conductor

Info

Publication number: WO2007069543A1
Application number: PCT/JP2006/324539
Authority: WO
Inventors: Meiten Koh; Akiyoshi Yamauchi; Kouji Yokotani
Original assignee: Daikin Industries, Ltd.
Priority date: 2005-12-14
Filing date: 2006-12-08
Publication date: 2007-06-21
Also published as: CN101331556B; JP4631689B2; JP2007165150A; KR20080080629A; KR101001415B1; CN101331556A

Abstract

Disclosed is an ion conductor which has high ion conductivity near room temperature, while having low viscosity, incombustibility and excellent oxidation resistance. The ion conductor satisfies the characteristics required for polymer electrolytes for lithium secondary batteries, capacitors and solar cells. Specifically disclosed is an ion conductor containing an ion conductive compound (I) having a cyclic carbonate group and an ether group in a side chain, and an electrolyte salt (II). This ion conductor is characterized in that the ion conductive compound (I) is an amorphous fluorine-containing polyether compound having a fluoroether group in a side chain or a crosslinked product thereof.

Description

Specification

Ionic conductor

Technical field

[0001] The present invention relates to an ionic conductor comprising an amorphous fluorine-containing polyether compound having a fluorine-containing ether group in a side chain. Powerful ion conductors are useful as lithium secondary batteries, solar cells, and polymer electrolytes for capacitors.

Background art

[0002] Lithium secondary batteries, solar cells, and capacitor electrolytes are currently mainly organic molecules, but they are more advanced in the direction of polymer electrolytes due to the avoidance of electrolyte solution leakage. Development is progressing.

[0003] As such a polymer electrolyte, a polymer gel type that combines a polymer containing an ethylene oxide (EO) moiety with an electrolyte salt (metal salt) and an organic solvent. Things are known.

[0004] However, the EO-electrolyte salt ion conductor has a high viscosity, so the dissociated ions move smoothly! /, Kana! /, And the electrolyte salt dissolves in multiple phases. Because it is a crystalline polymer, its ionic conductivity is affected by the phase change, particularly the melting of the EO crystalline phase, so the ionic conductivity is low at room temperature1, and the crystallization rate is slow. There is an essential problem that the conductivity changes with time.

[0005] In order to reduce the viscosity and increase the ionic conductivity near room temperature, various attempts have been made to increase the amorphousness by changing the type of polyether. As a result, although the temperature dependence has become considerably small, the ionic conductivity has not improved so much and it is quite possible to reach a practical level.

[0006] As an attempt to lower the viscosity, it has also been proposed to introduce a bulky CF group into EO. The

Three

For example, in JP-A-8-22270,

[0007] [Chemical 1]

→ 0-CH ₂ -CH— Units,

[0008] [Chemical 2]

^ (OCH ₂ CH ₂ ^ ~ An ionic conductor consisting of a fluorine-containing polyether compound combined with a unit, an alkali metal salt, and an organic solvent has been proposed!

[0009] Further, in Japanese Patent Laid-Open No. 9-48832,

[0010] [Chemical 3]

CF ₃

CH ₂ = CRCOO ^ O-CH ₂ ~ CH— OHr CRC-CH ₂

A combination of a ditalylate containing a fluorine-containing polyether (wherein n is 10 to 20) and a combination of a metal salt and an organic solvent is disclosed.

[0011] Further, JP-A-11-53937 proposes the use of a copolymer of a fluorephrine unit and an alkyl butyl ether or alkyl allyl ether unit having a carbonate bond.

[0012] Further, the use of a compound containing a polyfluoroether unit in the main chain as an ionic conductor is described in JP-A-2003-257240.

[0013] However, since the compounds having fluorine-containing ether units described in these patent documents are insufficient in reducing the viscosity, they do not become large ions until they are gelled with an organic solvent. Conductivity can be obtained.

[0014] On the other hand, it has also been proposed to introduce a carbonate unit into the polymer main chain, or to introduce an ester portion of acrylate into the side chain as a carbonate, and to copolymerize it with an EO-containing non-fluorinated acrylate (special feature). (Kaihei 6—223842). Furthermore, it has also been proposed to copolymerize butyl carbonate and EO-containing non-fluorinated acrylate (Japanese Patent Laid-Open No. 10-6).

No. 0210, JP-A-10-67849).

However, these are insufficient in terms of heat resistance, oxidation resistance, and ion conductivity. Disclosure of the invention

[0015] The present invention can achieve higher ionic conductivity than such a conventional one. An object is to provide an on-conductor.

[0016] The present inventors have disclosed that an amorphous fluorine-containing polyether compound having an essential structural unit having a cyclic carbonate group in the side chain and further having a structural unit having an ether unit in the side chain is an organic solvent. The present inventors have found that the ionic conductivity can be increased without using the nitrile, and have completed the present invention.

[0017] That is, the present invention includes an ion conductive compound (I) and an electrolyte salt (Π),

The ion conductive compound (I) is represented by the formula (I):

One (Ml) — (M2) One (M3) One (I)

[Wherein the structural unit Ml is represented by the formula (1):

[0018] [Chemical 4]

CX ¹ X ² -CX

o o o

(Wherein X ¹ , X ² and X ³ are the same or different, and all are H, CH, F or CF; n is 0

Carbonate group-containing structural unit represented by 3 3 or 1);

Structural unit M2 is represented by formula (2):

[0019] [Chemical 5]

—Cx ⁴ x-c X ⁶ ) —

I

(C = 0) „(2)

I

O-f ¹

(Wherein X ⁴ , X ⁵ and X ⁶ are the same or different, and all are H, CH, F or CF; Rf ¹

3 3 is a fluorine-containing polyether group; _n is a fluorine-containing polyether group-containing structural unit represented by 0 or 1);

Structural unit M3 has the formula (3): [0020] [Chemical 6]

~~ C H 2-~ C R

I

(C = O) _u Q (3)

I 11

O ~ CH ₂ CH ₂ O ^ —— (C ^ R ² (wherein R ¹ is H, CH, F or CF; R ² may contain a fluorine atom and is etherified)

3 3

A structural unit containing an ethyleneoxide moiety represented by the following formula (1): an alkyl group having 1-20 carbon atoms; n is 0 or l; m is an integer of 1-50; p is 0 or 1) , Excluding unit M2)

And

The structural unit Ml 0.. 1 to 90 mol ^_0/0, the structural unit M2 99.9 mol% and a structural unit M3 comprises 99.9 mole ^_0/0, and the sum is 10 the structural units M2 and the structural unit M3 99.9 mol%], which is an amorphous fluorine-containing polyether compound or a cross-linked product thereof.

BEST MODE FOR CARRYING OUT THE INVENTION

The ionic conductor of the present invention comprises a specific polymer ion conductive compound (I) and an electrolyte salt (II).

[0022] The specific polymer ion conductive compound (I) used in the present invention has the formula (I):

One (Ml) — (M2) One (M3) One (I)

[Wherein the structural unit Ml is represented by the formula (1):

[0023] [Chemical 7]

X ¹ X ² — CX ³

(c = o) „

OICH ₂ — J j (1)

o o o

(Wherein X ¹ , X ² and X ³ are the same or different and all are H, CH, F or CF; n is 0

3 3 Or a carbonate group-containing structural unit represented by 1);

Structural unit M2 is represented by formula (2):

[0024] [Chemical 8]

—Cxx ⁵ -cx ⁶ h-

I

(C = 0) _n (2)

I

O-R f ¹

(Wherein X ⁴ , X ⁵ and X ⁶ are the same or different and all are H, CH, F or CF; Rf ¹

Structural unit M3 has the formula (3):

[0025] [Chemical 9]

~~ CH-~ CR ^l j ~~

((3)

(Wherein R ¹ is H, CH, F or CF; R ² may contain a fluorine atom and may be etherified.

3 3

A structural unit containing an ethyleneoxide moiety represented by the formula (1): an alkyl group having 1 to 20 carbon atoms; n is 0 or l; m is an integer of 1 to 50; p is 0 or 1) , Excluding unit M2)

And

The structural unit Ml 0.. 1 to 90 mol ^_0/0, the structural units M2 0 to 99. 9 mol% and structural units M3 0 to 99. 9 moles comprise ^_0/0, and the structural units M2 and the structural unit M3 A total of 10 to 99.9 mol%] is an amorphous fluorine-containing polyether compound (IA).

[0026] The fluorine content of the amorphous fluorine-containing polyether compound (IA) is preferably 3 to 76% by weight, more preferably 5 to 50% by weight.

[0027] The carbonate group-containing structural unit Ml is a unit responsible for ionic conductivity, and is contained in an amount of 0.1 to 90 mol% in the fluorine-containing polyether compound. 1 mol% or more, further 10 mol% or more, particularly 20 mol% or more Ability to improve acid resistance is also preferable. The upper limit is appropriate 80 mol% is preferred because it provides a good viscosity and acid resistance, and 50 mol% is preferred because the viscosity can be lowered and the acid resistance can be improved.

[0028] In the formula (1), X ¹ , X ² and X ³ are the same or different, and all are H, CH, F or

3 is CF, and X ¹ and X ² are H and X ³ is H or CH.

3 3

Containing structural unit, or fluorine system where X ¹ and X ² are H and X ³ force or CF

Three

It may be a carbonate group-containing structural unit.

[0029] In the formula (1),! /, N may be 0, that is, a butyl ether structural unit, or n = 1, that is, a (meth) atallyloyl structural unit. In the case of a butyl ether structural unit, the (meth) atallyloyl structural unit, which is preferable in that hydrolysis is unlikely to occur, is preferable in that the dielectric constant can be improved by introducing a c = o group.

[0030] Specific examples of the carbonate group-containing structural unit Ml include the following.

[0031] [Chemical 10]

C H To — (: C H

c I = o

I

O-C H

O O o o o o

C H C F

c- CH ₉ — C-

I

c = o c = o

I

O- CH. O -CH

o o o o o o

c c o ————

CH,-CHCH ₂ — CFF

O c

O -CH O-C H

O O O O

O O

C H C F

-C H C -C H C

O -CH O-CH

O O O O

O O

[0032] The fluorine-containing polyether compound (IA) includes structural units M2 and M3 in addition to the structural unit Ml. The structural units M2 and M3 may be only one or both.

[0033] Equation (2):

[Chemical 11] cx * x

O 2

R

(Wherein X X X c o c I——Rf and n are as defined above)

= X

By introducing the structural unit M2, the amorphous nature of the compound increases and the viscosity of the compound can be lowered.

In the formula (2), Rf ¹ is preferably represented by the formula (2a):

-R ^a -Rf ³ -X (2a)

(Where Rf ³ is one (OCFCFCF) —, one (CFCFCFO)-,-(OCFZ'CF

2 2 2 nl 2 2 2 nl 2 (CFZ'CF O) (OCF CFZ ¹ ) One (CF CFZ'O) (OCFZ nl 2 nl 2 nl 2 nl

² )--(CFZ ² 0)-(OCHCFCF)--(CHCFCFO)-(OC nl nl 2 2 2 nl 2 2 2 nl

F CF CH) CFCFCHO) OCHCHCF) CHCHC

2 2 2 nl 2 2 2 nl 2 2 2 nl 2 2

FO)-,-(OCF CH CH) CFCHCHO) OCF CF CF CF

2 nl 2 2 2 nl 2 2 2 nl 2 2 2

) ― ― (CF CFCFCFO) ― (OCFZ ² CH) ― ― (CHCFZ ² 0) ―

2 nl 2 2 2 2 nl 2 nl 2 nl

(OCH (CH) CF CF) CH (CH) CFCFO) OCF CF CH (CH

3 2 2 nl 3 2 2 nl 2 2

)) ― — (CFCFCH (CH) O) — (OCZ ³ ) — and — (CZ ³ 0) — (where

3 nl 2 2 3 nl 2 nl 2 nl

; nl is an integer of 1 3

A fluorine-containing ether unit containing at least one kind selected from the group force; X is a hydrogen atom, a halogen atom or a fluorine-containing alkyl group optionally containing a crosslinkable functional group having 120 carbon atoms; R ^a is A group represented by an alkylene group containing a bond or a fluorine atom; provided that R ^a —Rf ³ —X does not contain an O—O bond).

[0035] ― Rf ³ is one (OCFZ'CF) (OCF CF CF) (OCH CF

2 nl 2 2 2 nl 2 2

CF) ― ― (OCFZ ² ) ― ― (OCZ ³ )-,-(CFZ'CF O) ― ― (CFCFCF

2 nl nl 2 nl 2 nl 2 2

O)--(CHCFCFO)--(CFZ ² 0)-and-(CZ ³ 0)-Force, etc.

2 nl 2 2 2 nl nl 2 nl

One (OCFZtF) is preferred to be one or more repeating units.

2 (OCFCFCF) (OCHCFCF)-,-(CFZ'CF O) C nl 2 2 2 nl 2 2 2 nl 2 nl

FCFCFO) — and one (CHCFCFO) — selected from one or more

2 2 2 nl 2 2 2 nl Repeating unit, or even one (OCFZiCF) —, one (OCF CF CF) —, one (CFZ'CF

2 nl 2 2 2 nl 2

O) — and — (CFCFCFO) — Force One or more repeats selected nl 2 2 2 nl

Is preferred.

[0036] Since the fluoroether group tends to lower the dielectric constant, nl is preferably small.

[0037] For example, — (OCF CF) —, — (OCF CF CF) —, — (OC

2 2 2 2 2

F) —, one (OCH CF CF) —, one (OCF (CF) CF) one, one (OCF (CF)) —, one (C (

2 2 2 2 3 2 3

CF) O) —, — (OCFHCF) one,-(OCFH) one,-(CF CF O) one,-(CF CF C

3 2 2 2 2 2 2

F O) —, One (CF O) One, One (CH CF CF O) One, One (CF (CF) CF O) One, One (CF (C

2 2 2 2 2 3 2

F) 0) —, one (OC (CF)), one (CFHCF O), one (CFHO) —, etc.

3 3 2 2

Especially (OCF CF)-,-(OCF CF CF) —, — (OCF) One, one (OCH CF CF)

2 2 2 2 2 2 2 2 2 One, one (OCF (CF) CF) one, one (OCF (CF)) —, one (CF CF O) one, one (CF CF C

3 2 3 2 2 2 2

2 2 2 2 2 3 2

F) 0) — and the like are also preferable because they have excellent thermal stability and oxidation resistance and can be easily synthesized.

Three

[0038] Further, X is a group represented by a hydrogen atom, a halogen atom or a fluorine-containing alkyl group optionally containing a crosslinkable functional group having 1 to 20 carbon atoms. Preferred specific examples include H, 1 CH, F, 1 CF, 1 CH OH, 1 CH = CH, 1 CH CH = CH, 1 COOC

3 3 2 2 2 2

H, 1 COOH, 1 CONH, 1 CON (CH),

3 2 3 1 2 1

[0039] [Chemical 12] CH ₃ ― ― p, One CH ₂ OCH ₂ — CH—

, 1 ― and then t ™ ΐ 'and M and Jrl-\ \. z

O o

CH ₂ — O— C— OCH ₃ , then H — — C ^— C rl ^ H>

o o

-C-0-NHCH ₂ CH = CH ₂ > 1 CH ₂ -O— CCF CH ₂ , 1 C≡N, 1 CH NH

twenty two

Etc. Among these, H, -CH, F, -CF are excellent in improving the dielectric constant.

3 3 and other groups that do not have a crosslinkable group; because of their excellent crosslinkability — CH OH, -CO

2 OCH, 1 COOH, 1 CONH, 1 CON (CH), 1 C≡N,

3 2 3 2

[0040] [Chemical 13]

O

— CH ₂ OCH ₂ — CH— CH ₂ , — CH ₂ — O— C— OCH ₃ ,

No

O O

-CH ₂ -0-C-CH = CH ₂ , — CH ₂ — 0— C— CF = CH ₂ is preferred.

[0041] R ^a in the formula (2a) is a linking group that binds Rf ³ to a vinyl ether structural unit or a (meth) attalyloyl structural unit, and may be a bond or may have a fluorine atom. O !, an alkylene group, for example, a fluorine atom having 1 to 4 carbon atoms! /, May! /, An alkylene group.

[0042] Specific examples of R ^a include a bond, -CH-, -CH CH-, -CH (CH)-,

2 2 2 3

— CH CH CH—, one CH CH CH CH One and other alkylene groups; CF—, one CF C

2 2 2 2 2 2 2 2 2

F-one, CF (CF) -one, -CH CF CF CH-, one-CH CH CF CF CH CH-one, etc.

2 3 2 2 2 2 2 2 2 2 2 2 and the like.

[0043] Examples of preferable Rf ¹ in the formula (2) include, for example,

— (CFCFO) -CH (nl = integer between l and 40),

-CH ― O -CF CF H,

2 2 2

-CH ― o -CF CF F,

2 2 2

-CH ― o -CF CF CF,

2 2 2 3

-CH ― o -CF CF CF-H,

2 2 2 2

-CH ― o -CF CF CF-F,

2 2 2 2

-CH ― o -CF CF CF-CF,

2 2 2 2 3

-CH ― o -CF H,

twenty two

-CH ― o -CF F,

twenty two

-CH -0 -CF CF, §S) 4 () OK CFCF〇CF II

(), OK CFCF〇CH II 0 () OK CFCF〇: H II

(), OK CFCFCF〇CF II

(), OK CFCFCF〇cn Il

(), OK CFCFCF OK II

CH CF CFn-I CF ₃ CF ₃

CF ₃ -iCF ₂ CF ₂ 0) ~ c FCF ₂ O-^ CF—

(Wherein n2 is an integer of 0 to 2) and the like.

In addition, Rf ¹ represented by the formula (2-1) is easy to synthesize, is inexpensive in cost, and has a branched CF

The introduction of 3 is preferred in that the viscosity can be reduced.

[0046] Further, n may be n = 0 (a butyl ether structural unit) or n = l (a (meth) attaylroyl structural unit) as in the formula (1).

[0047] The structural unit M3 having an ethylene oxide moiety is represented by the formula (3):

[0048] [Chemical 15]

, ~~~ ^)

O ~ (: CH ₂ CHO

3 3

An alkyl group having 1 to 20 carbon atoms which may contain an integer; n is 0 or l; m is an integer of 1 to 50; p is 0 or 1).

In formula (3), R ¹ may be any of H, CH, F, or CF. N is the formula (1) and

3 3

Similarly, n = 0 (a butyl ether structural unit) or n = 1 (a (meth) atalyloyl structural unit) may be used.

[0050] The terminal group R ² may contain a fluorine atom, may contain an ether bond, or may contain carbon atoms.

1 to 20 alkyl groups.

[0051] Specific examples include one CH, -CF, -CF CF, one CH CF, and one CF CF H.

3 3 2 3 2 3 2 2 and the like, and -CF, -CF CF, -CH CF,

3 2 3 2 3

CF CFH is preferred.

twenty two

[0052] A feature of the structural unit M3 is that it contains an ethylene oxide (EO) moiety, and provides a function of transferring an electrolyte salt to the fluorine-containing polyether compound (IA). The number of repetitions m is preferably 1 or more, more preferably 2 or more from the viewpoint of improving ion conductivity, and 50 or less, more preferably 20 or less, and particularly preferably 10 or less from the viewpoint of decreasing the viscosity. [0053] Preferable specific examples of the structural unit M3 include the following.

[0054] [Chemical 16]

C H C Η

■

Ο C Η C Η Ο C H

C Η

CH

o,, (, ρ 'XJ'

,

o CH ^ CH ₂ OC Η

C F

C H C

H C H O C Η

[0055] [Chemical 17]

oc =

c

F

C F

I

— FC H

I

H ₂ CH, O 18]

†

H c c o ————

= F

H C

C = o) „c o C F

I · ... C 3 ί

o

c = o) „o

OICH ₂ CH, O c

(Where n is 0 or l; m is 1 50)

[0057] Either one of the structural units M2 and M3 may be contained in the amorphous fluorine-containing polyether compound (IA) used in the present invention. When only one of them is contained, its content is 99.9 mol% or less, preferably 90 mol% or less, more preferably 80 mol% or less, from the viewpoint of improving the dielectric constant. The lower limit is 10 mol ^0, preferably 30 mol ^0, more preferably 50 mol% from the viewpoint of giving a more appropriate viscosity.

[0058] When both structural units are used, the total amount is 99.9 mol% or less, preferably 90 mol% or less, more preferably 80 mol% or less, from the viewpoint of improving the dielectric constant. From the point of giving viscosity, the content may be adjusted to 10 mol% or more, preferably 30 mol% or more, more preferably 50 mol% or more. The ratio of M2 and M3 (mol%) is a wide range depending on the physical properties and characteristics (e.g. mole ^_0/0 ratio M2ZM3 0.1 / 99.9 to 99.9 / 0.1 range preferred tool also limit is preferably 10Z90, further Is 20Ζ80, the lower limit is 90、10, and even 80 好 20 is preferred).

[0059] The amorphous fluorine-containing polyether compound (ΙΑ) used in the present invention may contain other structural units in addition to the structural units Μ1 to Μ3.

[0060] Examples of other structural units include, but are not limited to, the forces exemplified below.

[0061] (i) Atallate monomer or metatalylate monomer other than structural units Ml, 、 2 and Μ3. These may or may not have crosslinkable functional groups.

[0062] Specific examples include the following.

[0063] [Chemical 19]

CH ₂ = CH COO CH ₃ ,

CH ₂ = CH COO C ₂ H ₅ , CH ₂ = CHC OONH ₂ ,

O

/ \

CHCOO-CH ₂ CHCH ₂

[0064] (B) Styrene or a derivative thereof.

[0065] Examples include the following.

[0066] [Chemical 20]

[0067] These other structural units consist of ionic conduction of the amorphous fluorine-containing polyether compound (IA). In a range that does not impair the properties, low viscosity, and oxidation resistance.

[0068] The number average molecular weight of the amorphous fluorine-containing polyether compound (IA) is 500 or more, more preferably 1000 or more, particularly 1500 or more because it is likely to become amorphous if the viscosity is lowered. Preferable <, upper limit up to 100000, further up to 80000, especially 50000 power.

[0069] The amorphous fluorine-containing polyether compound (ΙΑ) used in the present invention can be produced by copolymerizing the monomers giving the above Μ1 to Μ3 by a conventional method.

[0070] In the present invention, the ion conductive compound (I) may be a crosslinked product! The cross-linked product can be produced by introducing a cross-linkable functional group into the amorphous fluorine-containing polyether compound (ΙΑ) and, if necessary, cross-linking using a cross-linking agent. By using a cross-linked product, the mechanical strength of the ion conductor is greatly improved.

[0071] Examples of the crosslinkable functional group include a bur group, an acryl group, a glycidyl group, an epoxy group, a hydroxyl group, a carboxyl group, an allyloyl group, a cyano group, an alkoxysilyl group, and the like.

It may be introduced into R ² of formula (3). In addition, a method of post-modification by reacting a compound having a crosslinkable functional group can be employed.

[0072] The cross-linking agent may be appropriately selected from polyfunctional compounds having two or more cross-linkable functional groups in one molecule.

[0073] Specific examples of the crosslinking agent include, for example,

[0074] [Chemical 21]

H _2- ~ O

XO ~ fCH ₂ "^ mOX, CH _z -OX

CH ₂ -OX,

S i (OC ₂ H ₅ ) ₄ ,

O II

(Where X is — CH ₂ — CH = CH ₂ , -C-CH = CH ₂ ,

O

II

— C— CF = CH ₂ , — CH ₂ — CH— CH ₂ , H; n 1 1 is an integer from 1 to 8)

\ /

O

[0075] [Chemical Formula 22] [Chemical Formula 22]

CH ₂ -OX, CH ₃

O O

(Where X is — C— CH = CH ₂ , -C-CF = CH ₂ , — CH ₂ — CH— CH ₂ }

\ /

O

Is preferred.

[0076] As it is, JP 2002-100405, JP 9 48832, JP 2002-2

A cross-linking agent described in, for example, 79826 can also be used.

[0077] Cross-linking may be performed by a known cross-linking system suitable for a combination of a cross-linkable functional group and a cross-linking agent. Yes.

Next, the electrolyte (II) which is one component of the ionic conductor of the present invention will be described.

[0079] Examples of the electrolyte (i) usable in the present invention include conventionally known metal salts, ionic liquids, inorganic polymer type salts, organic polymer type salts and the like.

[0080] These electrolytes are particularly suitable compounds depending on the intended use of the ionic conductor. Next, suitable electrolytes are exemplified for each application, but are not limited to the illustrated specific examples. In other applications, the following exemplified electrolytes can be appropriately used.

[0081] First, the metal salt for the solid electrolyte of the lithium secondary battery includes boron-on type, oxygen-on type, nitrogen-on type, carbon-on type, and phosphorus-on type. Various organic metal salts can be used, and oxygen ion type and nitrogen ion type are preferable.

[0082] Specific examples of the oxygen ion type include CF SO Li, C F SO Li, C F SO Li, CH

3 3 4 9 3 8 17 3

SO Li, C H SO Li, LiSO C F SO Li, CF CO Li, C H CO Li, Li C O, etc.

3 3 6 5 3 3 2 4 3 3 2 6 5 2 2 4 4 It is particularly preferable to use CF SO Li, C F SO Li, or C F SO SO Li.

3 3 4 9 3 8 17 3

[0083] Nitrogen-on types include (CF SO) NLi (TFSl), (C F SO) NLi (BETI), (C

3 2 2 2 5 2 2

F SO) (C F SO) NLi ゝ (CF SO) (C F SO) NLi ゝ (CF CO) NLi ゝ (CF CO) (

3 2 4 9 2 3 2 8 17 2 3 2 3

CF CO) NLi, ((CF) CHOSO) NLi, (C F CH OSO) NLi, etc.

3 2 3 2 2 2 2 5 2 2 2

In particular, it is preferable to use (CF SO) NLi (TFSI), (C F SO) NLi (BETI)

3 2 2 2 5 2 2

[0084] As the inorganic metal salt, LiPF, LiBF, LiAsF, LiCIO and the like can be used.

6 4 6 4

Further, it is preferable to use LiPF or LiBF.

6 4

[0085] For a solid electrolyte of a capacitor, as an organic metal salt, Et NBF (Et is ethylene).

4 4

The same applies below), Et NCIO, Et NPF, Et NAsF, Et NCF SO, Et N (CF SO) N

4 4 4 6 4 6 4 3 3 4 3 2 2

Et NC F SO is particularly preferable, Et NBF, Et NPF is preferably used

4 4 9 3 4 4 4 6

[0086] Inorganic metal salts include LiPF, LiBF, LiAsF, LiCIO, NaPF, NaBF, NaAsF

6 4 6 4 6 4

NaCIO, KPF, KBF, KAsF, KCIO, etc. can be used, especially LiPF, L

6 4 6 4 6 4 6 It is preferable to use iBF, NaPF, or NaBF.

4 6 4

[0087] As a solid electrolyte for a dye-sensitized solar cell, R ^la R ^2a R ^{3 4a} NI (R ^{la to} R ^4a are the same Or an alkyl group having 1 to 3 carbon atoms), Lil, Nal, KI,

[0088] [Chemical 23]

Etc. can be exemplified.

[0089] When an ionic liquid is used as the electrolyte (II), an organic or inorganic cation and a polyalkylimidazolium cation are used as solid electrolytes for lithium secondary batteries, capacitors, and dye-sensitized solar cells. Examples include salts with alkylpyridium cation, tetraalkylammonium cation and tetraalkylphosphonium cation, with 1,3 dialkylimidazolium salt being particularly preferred! /.

[0090] Examples of polyalkylimidazolium cations include 1,3-dialkylimidazolium cations such as 1-ethyl-3-methylimidazolium cation (ΕΜΙ +) and 1-butyl-3-methylimidazolium cation (ΒΜΙ +); 1, Trialkyl imidazolium cations such as 2 dimethyl 3 propyl imidazolium cation (DMPI +) are preferred!

[0091] Preferred inorganic ions include, for example, A1C1-, BF-, PF-, AsF-, and Γ.

4 4 6 6

For example, CH COO—, CF COO—, C F COO—, CF SO—, C F S

3 3 3 7 3 3 4 9

O-, (CF SO) N-, (C F SO) N-, and the like.

3 3 2 2 2 5 2 2

[0092] Specific examples are EMIA1C1, EMIBF, EMIPF, EMIAsF, ΕΜΠ, EMICH C

4 4 6 6 3

00, EMICF COO, EMIC F COO, EMICF SO, EMIC F SO, EMI (CF S

3 3 7 3 3 4 9 3 3

O) N, EMI (C F SO) N, BMIAICI, BMIBF, BMIPF, BMIAsF, ΒΜΠ, B

2 2 2 5 2 2 4 4 6 6

MICH COO, BMICF COO, BMIC F COO, BMICF SO, BMIC F SO, B

3 3 3 7 3 3 4 9 3

MI (CF SO) N, BMI (C F SO) N, DMPIAICI, DMPIBF, DMPIPF, DM

3 2 2 2 5 2 2 4 4 6

PIAsF, DMPII, DMPICH COO, DMPICF COO, DMPIC F COO, DMPIC

6 3 3 3 7

Examples include F SO, DMPIC F SO, DMPI (CF SO) N, DMPI (C F SO) N

3 3 4 9 3 3 2 2 2 5 2 2

wear.

[0093] Oxides such as cocoons, cocoons, and DMPII are particularly suitable for solid electrolytes in dye-sensitized solar cells. [0094] The amount of electrolyte (Π) depends on the required current density, application, type of electrolyte, etc. Ion conductivity compound (1) 0.1 parts by mass or more per 100 parts by mass, Is preferably 1 part by mass or more, particularly 2 parts by mass or more, 200 parts by mass or less, more preferably 100 parts by mass or less, and particularly preferably 50 parts by mass or less.

In the present invention, the electrolyte (Π) is retained by being impregnated or dissolved in the amorphous fluorine-containing polyether compound (ΙΑ) constituting the ion conductive compound (I).

[0096] As a method of holding the electrolyte (Π) in the ion conductive compound (I), a method of kneading the ion conductive compound (I) and the electrolyte (Π); dissolving the electrolyte (Π) in a solvent A method of mixing the ion-conducting compound (I) into the solution and then distilling off the solvent; a method of heating and melting the ion-conducting compound (I) and kneading the electrolyte (soot) therein can be employed.

[0097] In the ionic conductor of the present invention, the amorphous fluorine-containing polyether compound (ΙΑ) is solid but has a low viscosity, so that the ionic conductivity is high as it is. However, if it is necessary to further improve the ionic conductivity, an aprotic organic solvent (III) is added to form a gel (plasticized) gel electrolyte.

[0098] Examples of the organic solvent (III) used in the gel electrolyte include ethylene carbonate, propylene power carbonate, butylene carbonate, y butyrolatatane, 1,2-dimethoxyethane, tetrahydrofuran, 2-methyltetrahydrofuran, 1,3 dioxolane, 4-Methyl-1,3- dioxolane, methyl formate, methyl acetate, methyl propionate, dimethyl carbonate, ethyl methyl carbonate, jetyl carbonate, acetonitrile, dimethyl sulfoxide, methyl pyrrolidone, etc., especially dielectric constant and oxidation resistance From the standpoint of improving the properties and electrochemical stability, ethylene carbonate, propylene carbonate, jetino carbonate, ブ -butylate ratatone, 1,2 dimethoxyethane, 1,3 dioxolane, and acetonitrile are preferred.

[0099] The organic solvent (III) is preferably used in such an amount that the solid content in the ionic conductor is 10% by mass or more, more preferably 50% by mass or more, and particularly 100% by mass.

[0100] The ionic conductor of the present invention may contain other additives as necessary. Examples of other additives include metal oxides and glass.

[0101] The ionic conductor of the present invention has a high ion conductivity and excellent oxidation resistance and mechanical strength. Therefore, it is particularly useful as a polymer electrolyte for lithium secondary batteries, a polymer electrolyte for capacitors, and a polymer electrolyte for solar cells (particularly dye-sensitized solar cells). It can also be used as electrolytes for various sensors, electrolytes for electochromic elements, and ion conductors used for various electrolysis.

Example

Next, the present invention will be described based on examples and comparative examples, but the present invention is not limited to only powerful examples.

[0103] The measurement methods employed in the present invention are as follows.

[0104] Solid state NMR: AC-300 manufactured by BRUKER was used.

[0105] ¹⁹ F-NMR:

Measurement conditions: 282MHz (Trichlorofluorofluoromethane = Oppm)

NMR:

Measurement conditions: 300MHz (tetramethylsilane = Oppm)

[0106] IR:

Measure at room temperature with a Perkin Elmer Fourier transform infrared spectrophotometer 1760X.

[0107] TGA:

The pyrolysis temperature (Td and Td) is TGZDTA— manufactured by Seiko Instruments Inc.

0.1 1.0

Calculate from the data when the temperature is increased from room temperature to 20 ° CZmin using 6200.

[0108] Ionic conductivity:

Measure the ionic conductivity at room temperature using the AC four-terminal method. Toyo Tech as impedance measuring device - using SI1280B force Co., frequency 10 ⁴ Hz to: perform measurements in the range of LC ^ Hz.

[0109] Withstand voltage:

Place in a three-electrode voltage measurement cell (working electrode, counter electrode: platinum, reference electrode: Li. HS cell manufactured by Hosen Co., Ltd.) and perform potential scanning with a potentiostat at 50 mV Zsec. The range that did not flow is the withstand voltage (V).

[0110] Synthesis Example 1

A 100 ml glass four-necked flask equipped with a stirrer has a cyclic carbonate group in the side chain. Monomer (ml— 1) with

[0111] [C24]

H

C C C o ——————

= O

CH ₂ -ooo

5.9g, a monomer having a fluorine-containing ether group in the side chain (m2—l):

[0112] [Chemical 25]

CH ₂ = C

C = o

OCH ₂ C FOC F ₂ CFOC ₃ F ₇

I I

CF ₃ CF ₃

16.5 g and 0.24 g of azoisobuty-mouth-tolyl as a polymerization initiator were dissolved in 50 g of benzo-tolyl. After substituting with vacuum nitrogen three times in an ice bath, the temperature was raised to 75 ° C and stirred for 8 hours. Then, it reprecipitated with methanol and vacuum-dried at 80 ° C. for 16 hours to obtain 15.2 g of a copolymer. This copolymer was confirmed by solid state NMR analysis and IR analysis to be a copolymer of (ml-1) Z (m2-1) of 50/50 (mol%). The fluorine content calculated from the composition was 44% by mass.

[0113] Further, TGA and DSC measurement results in air showed that Td = 100 ° C, Td = 227 ° C

0.1 1.0

And Tg = 114. C.

[0114] Example 1

A supersaturated amount of LiN (SO C F) as an electrolyte was dissolved in a mixture of 2 g of the copolymer obtained in Synthesis Example 1 and 0.2 g of propylene carbonate, and left standing in a 6 ml sample bottle. -After

2 2 5 2 A transparent polymer phase was deposited on the upper layer, and a solid was deposited on the lower layer. The upper layer was taken out, after a rectangular film was made created C, was measured for ionic conductivity was 3.8X10- ⁵ SZcm.

H

[0115] Example 2

c c c o I I I

In a mixture of 2 g of the copolymer obtained in Synthesis Example 1 and 0.5 g of acetonitrile, trimethylmethylammonium tetrafluoroborate (TEMABF) as an electrolyte was dissolved in a supersaturated amount.

Four

Left overnight in 1 sample bottle. After one night, a transparent polymer mixture phase was deposited on the upper layer and a solid was deposited on the lower layer. When the upper layer was taken out and the withstand voltage was measured, it was 4.5V.

[0116] Synthesis Example 2

Monomer with a cyclic carbonate group in the side chain in a 100 ml glass four-necked flask equipped with a stirrer (ml— 1):

[0117] [Chemical 26]

CH ₃

I

CH ₂ = C

I

C = o

I

O-CH,

o

3.7g and a monomer having a fluorine-containing ether group in the side chain (m2—l)

[0118] [Chemical 27]

H

= O

CH ₂ CF OC F, C FOC ₃ F

I I

CF, CF ₃

11. Og and monomer with ethylene glycol unit in the side chain (m3— 1)

[0119] [Chemical 28] CH ₃

I

CH ₂ = C

I

c = o

I

O (CH ₂ CH ₂ O) ₃ -C ₂ H

4. 9 g and 0.19 g of azoisobuty-mouth-tolyl as a polymerization initiator were dissolved in 50 g of benzo-tolyl. After substituting with vacuum nitrogen three times in an ice bath, the temperature was raised to 75 ° C and stirred for 8 hours. Then, it was reprecipitated with methanol and vacuum-dried at 80 ° C for 16 hours to obtain 13.7 g of a copolymer. This copolymer was a solid NMR analysis and IR analysis, - it was confirmed that a copolymer of (ml l) / (m2- l ) / (m3- l) is 33Z33Z34 (mol ^_0/0). The fluorine content calculated from this compositional strength was 33% by mass.

[0120] Furthermore, as a result of TGA and DSC measurements in air, Td = 81 ° C, Td = 206 ° C and

0.1 1.0

And Tg = 84 ° C.

[0121] Example 3

A supersaturated amount of LiN (SO 2 C 3 F 4) as an electrolyte was dissolved in a mixture of 2 g of the copolymer obtained in Synthesis Example 2 and 0.2 g of propylene carbonate, and left standing in a 6 ml sample bottle. -After

2 2 5 2

A transparent polymer phase was deposited on the upper layer, and a solid was deposited on the lower layer. The upper layer was taken out, after producing a rectangular film was measured for ionic conductivity, 2. a 4 X 10- ⁵ SZcm.

[0122] Example 4

A supersaturated amount of TEMA BF as an electrolyte was dissolved in a mixture of 2 g of the copolymer obtained in Synthesis Example 2 and 0.5 g of acetonitrile, and left in a 6 ml sample bottle. -After dredging,

Four

A solid polymer precipitates in the bright polymer mixture phase. When the upper layer was taken out and the withstand voltage was measured, it was 4.5 V.

Industrial applicability

[0123] The polymer ionic conductor of the present invention itself has high ionic conductivity even near room temperature, is nonflammable with low viscosity, and has excellent acid resistance, and is a secondary lithium ion. It can satisfy the characteristics required as a polymer electrolyte for batteries, capacitors and solar cells.

Claims

Claims comprising an ion conductive compound (I) and an electrolyte salt (II), wherein the ion conductive compound (I) is represented by the formula (I): one (Ml) — (M2) one (M3) one (I [Wherein the structural unit Ml is represented by the formula (1):

[Chemical 1]

o

Carbonate group-containing structural unit represented by 3 3 or 1);

The structural unit M2 has the formula (2):

[Chemical 2]

—Cx ⁴ x ⁵ -c ⁶ —

I

(C = 0) „(2)

I

O- f ¹

Structural unit M3 has the formula (3):

[Chemical 3]

I

(C— O) o i 3

I II

O ~ 6CH ₂ CH ₂ O ^ —— ^ C ^ rR ² (Wherein R ¹ is H, CH, F or CF; R ² may contain a fluorine atom and may be etherified.

3 3

And

The structural unit Ml 0.. 1 to 90 mol ^_0/0, the structural unit M2 99.9 mol% and a structural unit M3 comprises 99.9 mole ^_0/0, and the sum is 10 the structural units M2 and the structural unit M3 99.9 mol%], an ionic conductor which is an amorphous fluorine-containing polyether compound or a cross-linked product thereof.

[2] In the structural unit Ml, X ¹ and X ² are H and X ³ is H or CH in the formula (1)

3. The ionic conductor according to claim 1, which is a non-fluorinated carbonate group-containing structural unit.

[3] The structural unit Ml is the formula (1), wherein X ¹ and X ² are H and X ³ force or CF

3. The ion conductor according to claim 1, which is a fluorine-containing carbonate group-containing structural unit.

[4] The structural unit M2 is represented by the formula (2), and Rf ¹ is represented by the formula (2a):

-R ^a -Rf ³ -X (2a)

(Where Rf ³ is one (OCFCFCF) —, one (CFCFCFO)-,-(OCFZ'CF

2 2 2 nl 2 2 2 nl 2

) One, — (CFZ'CF O) One, (OCF CFZ ¹ ) One, One (CF CFZ'O) One, (OCFZ

) ―, — (CFZO) —, — (OCHCFCF) ―, — (CHCFCFO) —, — (OC nl nl 2 2 2 nl 2 2 2 nl

F CF CH) One, one (CFCFCHO) —, One (OCHCHCF) —, One (CHCHC

2 2 2 nl 2 2 2 nl 2 2 2 nl 2 2

F O)-,-(OCF CH CH) One, one (CFCHCHO) —, One (OCF CF CF CF

2 nl 2 2 2 nl 2 2 2 nl 2 2 2

) ―, — (CF CFCFCFO) —, — (OCFZ ² CH) ―, — (CHCFZ ² 0) —, —

2 nl 2 2 2 2 nl 2 nl 2 nl

(OCH (CH) CF CF), One (CH (CH) CF CF O), One (OCF CF CH (CH

3 2 2 nl 3 2 2 nl 2 2

)) ―, — (CFCFCH (CH) O) —, — (OCZ ³ ) — and — (CZ ³ 0) — (where

3 nl 2 2 3 nl 2 nl 2 nl

Nl is an integer from 1 to 3

A fluorine-containing ether unit containing at least one selected from the group force; and X is a fluorine atom which may contain a hydrogen atom, a halogen atom or a crosslinkable functional group having 1 to 20 carbon atoms. An alkyl group; R ^a may contain ^a bond or a fluorine atom, but may be an alkylene group; provided that R ^a —Rf ³ —X does not contain an O—O bond) 4. The ionic conductor according to any one of items 1 to 3 in the range.

[5] The ionic conductor according to any one of claims 1 to 4, further comprising an organic solvent (III).

[6] The polymer electrolyte having ionic conductor power according to any one of claims 1 to 5.