JP5996196B2 - Polymer solid electrolyte and polymer solid electrolyte film - Google Patents

Description

  The present invention relates to an ion conductive polymer solid electrolyte. More specifically, the present invention relates to a polymer solid electrolyte having a polymer as a structural material, exhibiting high ionic conductivity, and excellent in film formability and flexibility.

  When an all-solid battery is configured using a solid electrolyte, the leakage of the contents (electrolytic solution) in the battery, which is one of the problems of the conventional battery, is eliminated, and the safety of the battery is improved. In addition, since the battery can be thinned and stacked, the solid electrolyte is attracting attention as an electrochemical device material including a battery.

Known types of solid electrolytes include those made of inorganic materials and those made of organic materials (polymers).
When solid electrolytes made of inorganic materials have relatively high ionic conductivity, but they are crystalline, they have poor mechanical strength and are difficult to process into flexible films. This is a significant disadvantage.
On the other hand, a solid electrolyte made of an organic material can be formed into a flexible thin film, and gives excellent mechanical properties based on the inherent flexibility of the polymer to the formed thin film. Is possible. As a result, a thin film made of a polymer solid electrolyte can be flexibly adapted to volume changes that occur in the process of ion-electron exchange reaction between an electrode and a polymer solid electrolyte, compared to inorganic solid electrolytes. It is considered promising as a solid electrolyte material for batteries having a high energy density.

As polymer solid electrolytes known so far, Non-Patent Document 1 discloses a polyethylene oxide (PEO) -metal salt complex, and Patent Document 1 discloses a polymer having a polyether bond such as PEO. An ion conductive polymer composition containing a seed or two or more alkali metal salts is described.
However, a material having PEO as a constituent element has a problem in that the movement of ions near room temperature is suppressed due to the expression of crystallinity derived from the structure of PEO, and the ionic conductivity is lowered.

As an example of applying a polymer having no crystallinity, Patent Document 2 and Patent Document 3 include a polyalkylene carbonate and a high salt composed of one or more metal salts selected from Group I and Group II of the periodic table. Molecular solid electrolytes are described.
However, these composites have a problem that the ionic conductivity is as low as 10 ⁻⁷ to 10 ⁻⁵ s / cm, which is not sufficient for application to battery devices.

As an example in which the ionic conductivity of a polymer solid electrolyte containing a polyalkylene carbonate and a metal salt is improved, Patent Document 4 discloses a polyalkylene carbonate having a side chain having a structure in which a substituent is bonded via an ether bond, and A polymer solid electrolyte containing a metal salt is described.
However, polyalkylene carbonates having a side chain having a structure in which a hydrocarbon group or an aromatic hydrocarbon group is bonded via an ether bond are obtained by copolymerization of a glycidyl ether compound and carbon dioxide. The glycidyl ether compound has a low reactivity, requires a high reaction temperature to obtain a polycarbonate, and has problems from the viewpoint of energy consumption and production cost.

JP 2004-352757 A JP 62-30147 A JP 62-30148 A JP 2010-287563 A

British Polymer Journal, UK, 1975, No. 7, p. 319

  The present invention is intended to solve such problems of the prior art, and provides a new polymer solid electrolyte having high ionic conductivity near room temperature and excellent film forming properties and flexibility. The purpose is to obtain.

  As a result of intensive studies to solve the above problems, the inventors have found that a polymer solid electrolyte containing a polycarbonate having a specific structure and a metal salt has high ionic conductivity even near room temperature, and completed the present invention. It came to do.

Specifically, the present invention relates to the following aspects.
Item 1.
Formula (1):

（式中、Ｒ^１およびＲ^２は、同一または異なっていてもよく、水素原子、アルキル基、アルコキシ基、アルカノイル基、カルバモイル基、シアノ基またはグリコール単位より構成される基を示す。ただし、Ｒ¹およびＲ²のいずれか一方はグリコール単位より構成される基である。）で表されるエポキシドと二酸化炭素との共重合体であるポリカーボネートおよび金属塩を含む、高分子固体電解質。
項２．
前記グリコール単位がエチレングリコール単位である、項１に記載の高分子固体電解質。
項３．
金属塩がアルカリ金属塩である、項１または２に記載の高分子固体電解質。
項４．
金属塩の含有量が、ポリカーボネートの構成繰返し単位［Ｏ−ＣＯ−Ｏユニット］に対する金属塩イオンのモル比（［金属塩イオン］／［Ｏ−ＣＯ−Ｏユニット］）として、０．０５〜０．９である、項１〜３のいずれか１項に記載の高分子固体電解質。
項５．
項１〜４のいずれか１項に記載の高分子固体電解質から得られる高分子固体電解質フィルム。
項６．
項１〜４のいずれか１項に記載の高分子固体電解質を溶媒に溶解させ、キャスト法によりフィルム化することを特徴とする高分子固体電解質フィルムの製造方法。

(In the formula, R ¹ and R ² may be the same or different and each represents a hydrogen atom, an alkyl group, an alkoxy group, an alkanoyl group, a carbamoyl group, a cyano group, or a group composed of a glycol unit. ¹ or R ^{2 is} a group composed of glycol units.) A solid polymer electrolyte comprising a polycarbonate and a metal salt that are a copolymer of an epoxide and carbon dioxide.
Item 2.
Item 2. The polymer solid electrolyte according to Item 1, wherein the glycol unit is an ethylene glycol unit.
Item 3.
Item 3. The solid polymer electrolyte according to Item 1 or 2, wherein the metal salt is an alkali metal salt.
Item 4.
The metal salt content is 0.05 to 0 as the molar ratio of metal salt ion to the structural repeating unit [O-CO-O unit] of the polycarbonate ([metal salt ion] / [O-CO-O unit]). Item 9. The polymer solid electrolyte according to any one of Items 1 to 3, which is .9.
Item 5.
Item 5. A polymer solid electrolyte film obtained from the polymer solid electrolyte according to any one of items 1 to 4.
Item 6.
Item 5. A method for producing a polymer solid electrolyte film, comprising dissolving the polymer solid electrolyte according to any one of Items 1 to 4 in a solvent and forming the film by a casting method.

  According to the present invention, it is possible to obtain a new polymer solid electrolyte having high ionic conductivity even near room temperature and excellent film forming properties, and a polymer solid electrolyte film excellent in flexibility.

  The polymer solid electrolyte of the present invention includes a polycarbonate having a specific structure and a metal salt. Examples of the polycarbonate used in the polymer solid electrolyte of the present invention include formula (1):

（式中、Ｒ^１およびＲ^２は、同一または異なっていてもよく、水素原子、アルキル基、アルコキシ基、アルカノイル基、カルバモイル基、シアノ基またはグリコール単位より構成される基を示す。ただし、Ｒ¹およびＲ²のいずれか一方はグリコール単位より構成される基である。）で表されるエポキシドと二酸化炭素とを触媒の存在下で重合して得られる共重合体が挙げられる。

(In the formula, R ¹ and R ² may be the same or different and each represents a hydrogen atom, an alkyl group, an alkoxy group, an alkanoyl group, a carbamoyl group, a cyano group, or a group composed of a glycol unit. ^One of R ¹ and R ^{2 is} a group composed of glycol units.) And a copolymer obtained by polymerizing epoxide represented by (2) and carbon dioxide in the presence of a catalyst.

As the epoxide represented by the formula (1), (i) ^one of R ¹ and R ² is a group composed of glycol units, and the other is a hydrogen atom, a methyl group, an ethyl group, or n-butyl. A group and an alkyl group such as n-decyl group, an alkoxy group such as methoxy group and ethoxy group, an alkanoyl group such as methanoyl group and ethanoyl group, a carbamoyl group or a cyano group, (ii) both R ¹ and R ² Are groups composed of glycol units which may be the same or different.

  In this specification, the glycol unit means two hydrogen atoms from a diol compound in which each of two carbon atoms of a substituted or unsubstituted linear or branched aliphatic hydrocarbon is substituted with one hydroxyl group. Means a divalent residue extracted. Although it does not specifically limit as a diol compound which originates a glycol unit, For example, ethylene glycol, propylene glycol, butylene glycol etc. are mentioned. Among these, an ethylene glycol unit is preferable from the viewpoint of increasing ion conductivity among these.

Examples of the substituent on the glycol unit include alkyl groups such as methyl group, ethyl group, n-butyl group and n-decyl group, alkoxy groups such as methoxy group and ethoxy group, alkanoyl groups such as methanoyl group and ethanoyl group, carbamoyl Group or a cyano group.
In the epoxide represented by the formula (1), the repeating number n of the glycol unit is preferably 1 to 50 times, more preferably 1 to 30 times, and further preferably 1 to 15 times from the viewpoint of high reactivity.

  The epoxide represented by (i) is, for example, a method of reacting epichlorohydrin with glycols such as ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, triethylene glycol monomethyl ether as shown in the following formula (Journal) of Organic Chemistry 1983, 48, p. 1117).

  Specific examples of the epoxide represented by (i) include 2- (2- (2-methoxyethoxy) ethoxy) methyloxirane and 2- (2- (2- (2-methoxyethoxy) ethoxy) ethoxy) methyl. Examples include oxirane.

As the epoxide represented by (ii), for example, 1,4-dichloro-2,3-epoxybutane is used in place of epichlorohydrin, and R ¹ and R ² are unsubstituted. It can manufacture by introduce | transducing group comprised from the ethylene glycol unit of this.

  Specific examples of the epoxide represented by (ii) include 2,3-bis ((2- (2-methoxyethoxy) ethoxy) methyl) oxirane and 2,3-bis ((2- (2- (2 -Methoxyethoxy) ethoxy) ethoxy) methyl) oxirane and the like.

  On the other hand, carbon dioxide is introduced into the reaction vessel as a gas and used for the copolymerization reaction. The pressure of carbon dioxide in the reaction vessel is preferably 0.01 to 6 MPa, and more preferably 0.1 to 3.0 MPa.

  The molar ratio of epoxide to carbon dioxide used in the reaction is typically 1: 0.1 to 1:10, but is preferably 1: 0.5 to 1: 3.0, more preferably 1: 1. 0 to 1: 2.0.

  In addition, when manufacturing the polycarbonate used for this invention, you may add the following general epoxide as a monomer.

  The general epoxide is not particularly limited, and examples thereof include ethylene oxide, propylene oxide, 1-butene oxide, 2-butene oxide, isobutylene oxide, 1-pentene oxide, 2-pentene oxide and 1-hexene oxide. 1-octene oxide, 1-dodecene oxide, cyclopentene oxide, cyclohexene oxide, styrene oxide, vinylcyclohexane oxide, 3-phenylpropylene oxide, 3,3,3-trifluoropropylene oxide, 3-naphthylpropylene oxide, 3- Examples include phenoxypropylene oxide, 3-naphthoxypropylene oxide, butadiene monoxide, 3-vinyloxypropylene oxide, and 3-trimethylsilyloxypropylene oxide. That. Among these, ethylene oxide and propylene oxide are particularly preferable from the viewpoint of high reactivity.

  The amount of the general epoxide used is not particularly limited, but can generally be 20 mol or less with respect to 1 mol of the epoxide represented by the formula (1), and is 10 mol or less. Is preferable, and it is more preferable that it is 5 mol or less.

  As the catalyst used in the polymerization, for example, the following formula (2) having a specific substituent as described in JP 2010-1443 A:

または下記式（３）：

Or the following formula (3):

（式中、Ｒ^３およびＲ^４は、同一でも異なっていてもよく、互いに独立して、水素原子、置換もしくは非置換のアルキル基、置換もしくは非置換の芳香族基、または置換もしくは非置換の芳香族複素環基であるか、または２個のＲ^３もしくは２個のＲ^４が互いに結合して置換もしくは非置換の飽和もしくは不飽和の脂肪族環を形成してもよく、Ｒ^５、Ｒ^６およびＲ^７はそれぞれ独立して水素原子、置換もしくは非置換のアルキル基、置換もしくは非置換のアルケニル基、置換もしくは非置換の芳香族基、置換もしくは非置換の芳香族複素環基、置換もしくは非置換のアルコキシ基、置換もしくは非置換のアシル基、置換もしくは非置換のアルコキシカルボニル基、置換もしくは非置換の芳香族オキシカルボニル基、置換もしくは非置換のアラルキルオキシカルボニル基であるか、または隣り合う炭素原子上のＲ^６とＲ^７とが互いに結合して置換もしくは非置換の脂肪族環または芳香環を形成してもよく、ＺはＦ⁻、Ｃｌ⁻、Ｂｒ⁻、Ｉ⁻、Ｎ_３ ⁻、ＣＦ₃ＳＯ₃ ^-、ｐ−ＣＨ₃Ｃ₆Ｈ₄ＳＯ₃ ^-、ＢＦ₄ ^-、ＮＯ₂ ^-、ＮＯ₃ ^-、ＯＨ^-、ＰＦ₆ ^-、ＢＰｈ₄ ^-、ＳｂＦ₆ ^-、ＣｌＯ₄ ^-、ＯＴｆ^-、ＯＴｓ^-、脂肪族カルボキシラート、芳香族カルボキシラート、アルコキシドおよび芳香族オキシドからなる群より選択されるアニオン性配位子である。）で表されるコバルト錯体を用いることができる。

(In the formula, R ³ and R ⁴ may be the same or different, and independently of each other, a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aromatic group, or a substituted or unsubstituted group; It may be an aromatic heterocyclic group, or two R ³ or two R ⁴ may be bonded to each other to form a substituted or unsubstituted saturated or unsaturated aliphatic ring, and R ⁵ , R ⁶ and R ⁷ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aromatic group, a substituted or unsubstituted aromatic heterocyclic group, substituted or unsubstituted Unsubstituted alkoxy group, substituted or unsubstituted acyl group, substituted or unsubstituted alkoxycarbonyl group, substituted or unsubstituted aromatic oxycarbonyl group, substituted or unsubstituted May form an aralkyloxycarbonyl an either group, or R ⁶ and R ⁷ on adjacent carbon atoms are bonded to each other substituted or unsubstituted aliphatic or aromatic ring, Z is F ^-, Cl ⁻ , Br ⁻ , I ⁻ , N ₃ ⁻ , CF ₃ SO ₃ ⁻ , p-CH ₃ C ₆ H ₄ SO ₃ ⁻ , BF ₄ ⁻ , NO ₂ ⁻ , NO ₃ ⁻ , OH ⁻ , PF ₆ ⁻ , BPh ₄ ⁻ , SbF ₆ ⁻ , ClO ₄ ⁻ , OTf ⁻ , OTs ⁻ , an anionic ligand selected from the group consisting of aliphatic carboxylates, aromatic carboxylates, alkoxides and aromatic oxides. Cobalt complexes can be used.

  The use ratio of the catalyst is preferably 0.05 mol or less, and more preferably 0.01 mol or less, relative to 1 mol of the epoxide. Moreover, since reaction time becomes long, it is preferable that it is 0.00001 mol or more, and it is more preferable that it is 0.00002 mol or more.

In the polymerization, a cocatalyst can be further used. The co-catalyst used is bis (triphenylphosphoranylidene) ammonium chloride (PPNCl), piperidine, bis (triphenylphosphoranylidene) ammonium fluoride (PPNF), bis (triphenylphosphoranylidene) ammonium Pentafluorobenzoate (PPNOBzF ₅ ), tetra-n-butylammonium chloride (nBu ₄ NCl), tetra-n-butylammonium bromide (nBu ₄ NBr), tetra-n-butylammonium iodide (nBu ₄ NI), tetra- n- butylammonium acetate (nBu ₄ nOAc), tetra -n- butylammonium nitrate _(nBu 4 _NO 3), triethylphosphine _(Et 3 P), tri -n- butyl phosphine _(nBu 3 P , Triphenylphosphine (Ph ₃ P), pyridine, 4-methylpyridine, 4-formyl pyridine, 4- (N, N- dimethylamino) pyridine, N- methylimidazole, N- ethylimidazole, etc. N- propyl imidazole PNCCl, PPNF, PPNOBzF ₅ and nBu ₄ NCl are preferable, and PNCCl and PPNF are more preferable from the viewpoint of high reaction activity.

  The proportion of the cocatalyst used as necessary is preferably 0.1 to 10 mol, more preferably 0.3 to 5 mol, relative to 1 mol of the catalyst, Even more preferably, it is ˜1.5 mol.

  In the said polymerization, a solvent can be used as needed. The solvent used is not particularly limited as long as it does not react with the epoxide, carbon dioxide, catalyst and cocatalyst used. For example, hydrocarbons, ethers, esters, ketones, halogenated hydrocarbons Etc. Specifically, hexane, benzene, toluene, xylene, cyclohexane, 1,2-dimethoxyethane, dibutyl ether, tetrahydrofuran, 1,4-dioxane, methyl acetate, ethyl acetate, propyl acetate, methyl ethyl ketone, methyl isobutyl ketone, diethyl ketone , Methylene chloride, chloroform, dichloroethane, trichloroethane, chlorobenzene and the like. Among them, ethers and halogenated hydrocarbons are preferable because of high solubility, and 1,2-dimethoxyethane and methylene chloride are particularly preferable. These solvents may be used alone or in combination of two or more.

  When using a solvent, it is preferable that it is 50-10000 mass parts with respect to 100 mass parts of said epoxides, and it is more preferable that it is 100-5000 mass parts.

  The polymerization can be carried out using a known polymerization reactor that can be pressurized, for example, an autoclave. The polymerization reaction temperature is preferably 0 ° C. to 100 ° C., preferably 10 ° C. to 90 ° C., from the viewpoint of suppressing the production reaction of the cyclic carbonate as a by-product and from the viewpoint of shortening the reaction time. More preferably, it is 20 to 60 degreeC.

Although reaction time changes with reaction conditions, it is 1 to 100 hours normally.
The polymerization is preferably carried out in an inert atmosphere in order to eliminate the influence of oxygen and the like.

  The polycarbonate thus obtained can be isolated by concentrating and drying by a conventional method after completion of the reaction. Moreover, you may further refine | purify the said polycarbonate using well-known means, such as column chromatography.

  The molecular weight of the polycarbonate obtained by the polymerization is, for example, 1,000 to 2,000,000, preferably 2, in a typical number average molecular weight (Mn) measured by gel permeation chromatography (GPC; polystyrene conversion). It is 000-1,000,000, More preferably, it is 3,000-100,000.

As the metal salt constituting the polymer solid electrolyte of the present invention, alkali metal salts used in conventional polymer solid electrolytes can be preferably used. The alkali metal salts, _{e.g., LiBr, LiCl, LiI, LiSCN} , LiBF 4, LiAsF 6, LiClO 4, CH 3 COOLi, CF 3 COOLi, LiCF 3 SO 3, LiPF 6, LiN (CF 3 SO 2) 2, Lithium salts such as LiC (CF ₃ SO ₂ ) ₃ can be used. Among these, LiN (CF ₃ SO ₂ ) ₂ (lithium bistrifluoromethanesulfonylimide: LiTFSI) is preferable from the viewpoint of excellent compatibility with the polycarbonate obtained by the polymerization and high ion conductivity.

  Moreover, as a metal salt, the salt of the above-mentioned lithium salt anion and alkali metals other than lithium, for example, potassium, sodium, etc. can also be used.

  The content of the metal salt constituting the polymer solid electrolyte varies depending on the metal salt used and the type of polycarbonate, but usually the moles of metal salt ions relative to all the structural repeating units [O-CO-O unit] of the polycarbonate. The ratio ([metal salt ion] / [O—CO—O unit]) is preferably 0.05 to 0.9, more preferably 0.1 to 0.5. If this ratio is less than 0.05, the electrical conductivity is lowered, and if it is more than 0.9, the film formability of the polymer solid electrolyte may be lowered due to precipitation of a metal salt.

  There is no restriction | limiting in particular as a method to manufacture the polymer solid electrolyte of this invention containing a polycarbonate and a metal salt, The polymer solid electrolyte of arbitrary shapes can be obtained by various methods.

  For example, in general, a polymer solid electrolyte is often used in the form of a film. As a film forming method for this purpose, the above polycarbonate and metal salt are uniformly dissolved in a solvent, and then the solution is flattened. The film can be formed by a casting method in which a film is obtained by casting the film and evaporating the solvent. In this case, the solvent can be appropriately selected from solvents that can dissolve both the polycarbonate and the metal salt according to the use of the polymer solid electrolyte. In general, an organic solvent having an appropriate polarity such as acetonitrile, dimethylformamide or tetrahydrofuran can be used.

  As the usage-amount of the said solvent, it is preferable that it is 100-10000 mass parts with respect to 100 mass parts of said polycarbonates, and it is more preferable that it is 250-2500 mass parts.

  Examples are shown below, but the present invention is not limited thereto.

  In addition, the number average molecular weight (Mn) and molecular weight distribution (Mw / Mn) of the polycarbonate obtained in this example are gel permeation chromatography (high performance liquid chromatography system DG660B / PU713 / UV702 / RI631A manufactured by GL Sciences Inc.). Was measured in tetrahydrofuran (THF) at 40 ° C. and calculated based on standard polystyrene.

The ¹ H-NMR spectrum of the polycarbonate obtained in this example was measured using JNM-JNM-ECP500 (500 MHz).

  The ionic conductivity (σ) of the solid polymer electrolyte film prepared in this example was measured for complex impedance using a solartron SI 1260 manufactured by Toyo Technica Co., Ltd.

（式中、Ｒはバルク抵抗値、ｄは試料の厚さ、Ａは電極の面積である。）に基づきイオン伝導度（σ）を算出した。

(Wherein, R is the bulk resistance value, d is the thickness of the sample, and A is the area of the electrode), and the ionic conductivity (σ) was calculated.

  In the measurement of the complex impedance, charge and discharge of the electric double layer, electrode reaction, and the like occur simultaneously with ion migration along the potential gradient, and thus show frequency dependence. This frequency dependence was plotted on a plane (Cole-Cole plot) with the real part as the horizontal axis and the imaginary part as the vertical axis (Cole-Cole plot), and an equivalent circuit value (resistance value) explaining the locus was obtained.

  Epoxides having glycol units were synthesized according to the method described in a previous report (Journal of Organic Chemistry 1983, 48, p. 1117).

  Moreover, following formula (4):

で表されるコバルトサレン錯体（４）は、ＵＳ−Ｂ２−７６７４８７３（ｐ．６）記載の方法に従って合成した。

The cobalt salen complex (4) represented by the above was synthesized according to the method described in US-B2-7677483 (p.6).

[Synthesis Example 1]
A 500 mL-volume stainless steel autoclave was charged with 0.407 g (0.5 mmol) of cobalt-salen complex (4) and 0.287 g (0.5 mmol) of PPNCl and replaced with a nitrogen atmosphere, and then 2- (2- (2- Methoxyethoxy) ethoxy) methyloxirane (MEEMO) 88.1 g (0.5 mol) was added, carbon dioxide was injected to 0.7 MPa, and the mixture was stirred at 25 ° C. for 24 hours while keeping the pressure constant. After returning to normal pressure, the contents were dissolved in methylene chloride, washed twice with 1M hydrochloric acid, volatiles were concentrated, and the residue was washed twice with diethyl ether. Then, it vacuum-dried at 80 degreeC for 5 hours, and obtained 97g of colorless rubber-like polymers (yield 90%).

M _n = 72,400, M _w / M _n = 2.03
¹ H-NMR (CDCl ₃ ) δ 5.03 (br, 1H, CH), 4.50-4.25 (br, 2H, CH ₂ CH), 3.70-3.61 (m, 8H, CH _{2 CH 2 O), 3.54-3.43 (} m, 2H, CH 2 OCH 2 CH 2), 3.37 (s, 3H, CH 2 CH 2 OCH 3) ppm.

[Example 1]
(1) Preparation of solid polymer electrolyte film In a 50 mL eggplant-shaped flask, 1.0 g of the polycarbonate obtained in Synthesis Example 1 and 0.13 g of LiTFSI ([metal salt ion] / [O—CO—O unit] = 0.10 mol / mol) and 10 mL of acetonitrile were charged and dissolved to obtain a uniform solution.
A slide glass (width: 26 mm, length: 76 mm, thickness: 1 mm) was prepared as an insulating substrate and washed with acetone. Then, using a UV-ozone treatment device (manufactured by Sen Special Light Source Co., Ltd., trade name: tabletop optical surface treatment device PL16-110), the slide glass was subjected to surface treatment to obtain a test slide glass.

  Next, a rectangular (10 mm × 50 mm) pattern was formed on the test slide glass using a masking tape, and the acetonitrile solution was poured. After evaporating acetonitrile at room temperature, the masking tape was removed, and the solid polymer electrolyte film was prepared by drying at 110 ° C. for 8 hours.

(2) Preparation of aluminum laminate measurement cell After affixing Au foil (positive electrode and lead wire) and Cu foil (cathode and lead wire) on PP laminate film, solid polymer electrolyte film and Li foil in this order on the positive electrode After overlapping, the PP laminate film was closed. Next, after the PP laminate film was sandwiched between the aluminum laminate films, sealing was performed while deaeration, thereby producing an aluminum laminate measurement cell.

(3) Evaluation of ion conductivity (σ) Ion conductivity (σ) was measured using the obtained aluminum laminate measurement cell. In addition, measurement temperature is 25 degreeC, 40 degreeC, 60 degreeC, and 80 degreeC.

[Example 2]
In Example 1, instead of LiTFSI 0.13 g ([metal ion] / [O—CO—O unit] = 0.10 mol / mol), LiTFSI 0.22 g ([metal ion] / [O—CO—O] A solid polymer electrolyte film was prepared in the same manner as in Example 1 except that [unit] = 0.17 mol / mol) was used.
Next, an aluminum laminate measurement cell was prepared in the same manner as in Example 1, and the ionic conductivity (σ) was measured.

[Comparative Example 1]
In Example 1, ion conductivity was measured in the same manner as in Example 1 except that polyethylene carbonate (manufactured by EMPWER MATERIALS, trade name QPAC25) was used instead of the polycarbonate obtained in this example.

[Comparative Example 2]
In Example 1, ion conductivity was measured in the same manner as in Example 1 except that polypropylene carbonate (product name: QPAC40, manufactured by EMPWER MATERIALS) was used instead of the polycarbonate obtained in this example. The results are shown in Table 1.

  From the results shown in Table 1, it can be seen that the ionic conductivity of the solid polymer electrolyte using the polymer obtained in Synthesis Example 1 is excellent.

According to the present invention, it is possible to obtain a polymer solid electrolyte having high ionic conductivity even near room temperature and having excellent film forming properties and flexibility.
The polymer solid electrolyte of the present invention can be used as a material for various electrochemical devices including a battery having a high energy density such as a lithium battery.

Claims (5)

Formula (1):

(In the formula, R ¹ and R ² may be the same or different and each represents a hydrogen atom, an alkyl group, an alkoxy group, an alkanoyl group, a carbamoyl group, a cyano group, or a group composed of a glycol unit. ^One of R ¹ and R ^{2 is} a group composed of glycol units , except for those having a glycol unit repeating number n of 1 ) . look containing polycarbonate and metal salts is, the content of the metal salt, the molar ratio of metal salt ions to the polycarbonate constituent repeating units [O-CO-O units ([metal salt ions] / [O-CO- Polymer unit electrolyte which is 0.05-0.9 as O unit]) .   The solid polymer electrolyte according to claim 1, wherein the glycol unit is an ethylene glycol unit.   The polymer solid electrolyte according to claim 1 or 2, wherein the metal salt is an alkali metal salt. The polymer solid electrolyte film obtained from the polymer solid electrolyte of any one of Claims 1-3 . A method for producing a solid polymer electrolyte film, comprising dissolving the solid polymer electrolyte according to any one of claims 1 to 3 in a solvent and forming the film by a casting method.