JP4155245B2 - battery - Google Patents

Description

The present invention relates to a battery containing an ion conductive polymer solid electrolyte , an electrolyte, and an organic solvent . More specifically, the present invention is a solid polymer electrolyte having an organic polymer as a structural material, and exhibits high ionic conductivity by containing an alkali metal ion-based conductive carrier such as lithium ion. The present invention also relates to a battery containing a solid polymer electrolyte excellent in film formability, flexibility and mechanical strength, an electrolyte, and an organic solvent .

  When an all-solid battery is formed using a solid electrolyte, the leakage of contents in the battery, which is one of the problems of the conventional battery, is eliminated, and the safety and reliability of the battery are improved. In addition, the battery can be thinned and stacked. For this reason, solid electrolytes are attracting attention as materials for electrochemical devices such as batteries.

  By the way, the characteristics required for a solid electrolyte are generally (a) high ionic conductivity and no electronic conductivity, (b) excellent film formability so as to be thinly formed, (c ) It is excellent in flexibility.

  Further, the types of solid electrolytes are roughly divided into two types, those made of inorganic materials and those made of organic materials. Among these, solid electrolytes made of inorganic materials have relatively high ionic conductivity, but because they are crystalline, they have poor mechanical strength and are difficult to process into flexible films. This is a significant disadvantage when applied.

  In contrast, a polymer solid electrolyte made of an organic polymer can be formed into a flexible thin film, and the formed thin film has excellent mechanical properties due to the inherent flexibility of the polymer. It becomes possible to grant. Therefore, a thin film made of a polymer solid electrolyte can be flexibly adapted to a volume change generated in an ion-electron exchange reaction process between an electrode and a polymer solid electrolyte, as compared with an inorganic solid electrolyte. For these reasons, polymer solid electrolytes are regarded as promising as solid electrolyte materials for high energy density batteries, particularly thin high energy density batteries.

  Up to now, as such a polymer solid electrolyte, polyethylene oxide having a polyether structure of the following formula [hereinafter abbreviated as PEO]

とＬｉ塩やＮａ塩等のアルカリ金属塩との複合体が、比較的高いアルカリ金属イオン導電性を示すものとして知られている。また、この複合体をはじめとして種々の高分子固体電解質について、イオン導電機構や分子構造等の理論的研究、あるいは電池等の電気化学デバイスへの応用研究が活発に進められている。

A complex of Li and an alkali metal salt such as Na salt is known to exhibit relatively high alkali metal ion conductivity. In addition, theoretical research on ionic conduction mechanisms, molecular structures, etc., and applied research to electrochemical devices such as batteries have been actively promoted for various polymer solid electrolytes including this composite.

  By the way, the ionic conduction in the polymer solid electrolyte is that the alkali metal ions in the polymer matrix selectively ionize in the amorphous part in the polymer matrix and interact with the coordinating atoms in the polymer. Is considered to be achieved by diffusion movement along the electric field. For example, in a composite film composed of PEO and an alkali metal salt, when alkali metal ions interact with oxygen in the ether bond portion having a high dielectric constant in the PEO main chain, ion conduction is caused by segmental movement of the molecular chain due to heat. It is considered. Therefore, in order to improve the ionic conductivity of the polymer solid electrolyte, it is considered effective to suppress the crystallinity of the polymer solid electrolyte.

  However, the conventional polymer solid electrolyte has a problem that when it is attempted to improve the ionic conductivity by suppressing the crystallinity, the film formability and flexibility are lowered. In addition, there is a problem that the ionic conductivity in the vicinity of room temperature is small as compared with a solid electrolyte generally made of an inorganic material.

For example, in the case of a composite film of PEO and an alkali metal salt, when the molecular weight of the PEO is about 10,000, the film formability is excellent, and the ion conductivity is 10 ⁻³ to 10 ⁻⁴ S / cm at 100 ° C. or higher. Has a relatively high value of the degree. However, since this composite film is crystalline, the conductivity rapidly decreases at a temperature of 60 ° C. or less, and exhibits a very low value of about 10 ⁻⁷ S / cm or less at room temperature. For this reason, it cannot be incorporated as a normal battery material in which room temperature is used.

Therefore, the formula (i)

（式中、ｎは任意の整数である）に示すようにＰＥＯの末端水酸基にジイソシアネートを反応させてウレタン架橋を形成させたり、あるいはエステル架橋を形成させることによって複合体膜の結晶性を抑制させる試みがなされている。この架橋構造は無定形高分子のイオン導電率を大きく低下させることなく機械的特性を向上させるための手段として有効である。しかしながら、このような手段でも十分な成果を得られるには至っていない。

(In the formula, n is an arbitrary integer) As shown in the formula, urethane is formed by reacting a diisocyanate with the terminal hydroxyl group of PEO, or the crystallinity of the composite film is suppressed by forming an ester bridge. Attempts have been made. This cross-linked structure is effective as a means for improving mechanical properties without greatly reducing the ionic conductivity of the amorphous polymer. However, sufficient results have not yet been obtained by such means.

  On the other hand, the ion conductivity near room temperature can be improved by setting the molecular weight of PEO, which is an organic polymer constituting the composite film, to 10,000 or less, but in this case, the film formability is significantly reduced, Filming becomes difficult.

  In addition, when the content concentration of the alkali metal salt is increased in order to improve the ionic conductivity, the glass transition point Tg of the composite film also increases, and the ionic conductivity decreases instead. Thus, an increase in the density of the carrier body and an increase in conductivity cannot be achieved simultaneously.

  Examples of other polymer solid electrolytes include compounds similar to the above-mentioned complex composed of PEO and an alkali metal salt, and represented by the formula (ii)

（式中、ＲはＨ又はＣＨ₃ であり、ｋ及びｎはそれぞれ任意の整数である）で表されるように、側鎖にＰＥＯ構造を有するアクリル系又はメタクリル系の有機高分子が知られている。また、式(iii)

(Wherein R is H or CH ₃ , and k and n are each an arbitrary integer), an acrylic or methacrylic organic polymer having a PEO structure in the side chain is known. ing. And the formula (iii)

（式中、ｋ及びｎはそれぞれ任意の整数である）で表されるように、側鎖にＰＥＯ構造を有し、主鎖が（−Ｐ＝Ｎ−）_k からなるポリホスファゼン系の有機高分子や、式(iv)

(Wherein k and n are each an arbitrary integer), a polyphosphazene-based organic polymer having a PEO structure in the side chain and a main chain of (-P = N-) _k. Numerator, formula (iv)

（式中、ｋ及びｎはそれぞれ任意の整数である）で表されるように、側鎖にＰＥＯ構造を有し、主鎖が（−ＳｉＯ−）_k からなるシロキサン系の有機高分子が知られている。

(Wherein k and n are each an arbitrary integer), a siloxane-based organic polymer having a PEO structure in the side chain and a main chain of (—SiO—) _k is known. It has been.

The ionic conductivity of the polymer solid electrolyte composed of these organic polymer and alkali metal salt is about 10 ⁻⁵ S / cm, which is slightly improved compared to the composite film composed of PEO and alkali metal salt. However, it is still insufficient for practical use, and the film formability and flexibility are not sufficient. Therefore, a battery using a conventional solid polymer electrolyte that has practically sufficient battery performance has not been obtained.

On the other hand, in addition to the organic polymer and metal salt as described above, a polymer solid electrolyte containing an organic solvent capable of dissolving the metal salt has been developed. In this solid polymer electrolyte, the organic polymer has a gel swollen in an organic solvent, without using an organic solvent so far solid polymer electrolyte very high compared to the quality to 10 ^-3 S / cm A degree of conductivity can be obtained.

  As for the organic polymer constituting the solid polymer electrolyte containing the organic solvent in this way, in addition to using the organic polymer such as PEO and formulas (ii) to (iv) described above, these are irradiated with active radiation. Attempts have been made to use those crosslinked by light irradiation, electron beam irradiation, heating or the like. Furthermore, an attempt has been made to use a cross-linking agent obtained by converting an organic polymer into a fluororubber-based cross-linked body, an acrylonitrile-butadiene-based cross-linked body, or a urethane cross-linked body. When the organic polymer is cross-linked in this way, even if the organic polymer swells and becomes gelled due to the inclusion of the organic solvent, it suppresses the seepage of the organic solvent when pressure is applied to the solid polymer electrolyte. And mechanical strength can be improved.

  However, even in a polymer solid electrolyte containing an organic solvent, its conductivity is lower than that of an electrolytic solution composed of a normal organic solvent and a metal salt, and it is desired to further improve the conductivity. It has been desired to improve the mechanical strength.

The present invention is intended to solve such problems of the prior art, has high ionic conductivity comparable to an electrolyte even near room temperature, and has excellent film formability, flexibility and mechanical strength. It aims at obtaining the battery containing the new organic polymer crosslinked body which has .

In order to solve the above problems and achieve the object of the present invention, in the battery of the present invention, organic polymers having a carbonate group as a functional group are cross-linked with each other, or are cross-linked with another monomer. It is characterized by comprising a crosslinked organic polymer , an electrolyte, and an organic solvent in which the electrolyte is soluble .

According to the present invention, there is provided a battery containing a new crosslinked organic polymer having a high ionic conductivity comparable to an electrolytic solution even near room temperature and having excellent film formability, flexibility and mechanical strength. Can be obtained.

  The present inventors have found that an organic polymer having a carbonate group as a functional group can contain carrier ions at a higher density than conventional organic polymers, and is difficult to crystallize even at low temperatures. It has been found that sufficient segmental motion can be ensured by maintaining a fixed state, and electron conduction does not occur. Then, when an organic polymer having a carbonate group is used as a structural material and an electrolyte such as a metal salt is contained therein to form a solid polymer electrolyte, a specific amount of an organic solvent is further contained, and an organic solvent is added with the organic solvent. When the polymer is swollen, it has been found that high ionic conductivity comparable to that of the conventional electrolyte can be obtained without impairing the film formability, and the present invention has been completed. Further, in this case, it has been found that by cross-linking organic polymers to each other, a large amount of organic solvent can be contained in the polymer solid electrolyte, thereby further improving ionic conductivity. The preferred embodiment has been completed.

  That is, the present invention comprises an organic polymer having a carbonate group as a functional group, an electrolyte, and an organic solvent in which the electrolyte is soluble, and contains 500 parts by weight or less of the organic solvent with respect to 100 parts by weight of the organic polymer. A solid polymer electrolyte is provided. In this case, a polymer solid electrolyte in which organic polymers are cross-linked with each other is provided.

  Hereinafter, the present invention will be described in detail. In the polymer solid electrolyte of the present invention, an organic polymer having a carbonate group as a functional group in the main chain or side chain is used as the organic polymer serving as the structural material. Here, as an organic polymer having a carbonate group in the main chain, for example, the following formula (1)

（式中、Ｒ¹ 及びＲ² は独立的に水素又は低級アルキルであり、ｎは任意の整数である）で表される、ビニレンカーボネート系モノマーの単独重合体であるポリビニレンカーボネート（ＰＶｎＣ）を使用することができる。ここで式（１）における置換基Ｒ¹ 及びＲ² の低級アルキルとしては、炭素数１〜３の低級アルキルが好ましい。また低級アルキルは直鎖状でも分岐状でもよい。

(In the formula, R ¹ and R ² are independently hydrogen or lower alkyl, n represents any of integers) represented by a homopolymer of vinylene carbonate based monomer poly vinylene carbonate (PVnC) Can be used. Here, the lower alkyl of the substituents R ¹ and R ² in the formula (1) is preferably a lower alkyl having 1 to 3 carbon atoms. The lower alkyl may be linear or branched.

The average molecular weight of the organic polymer of the formula (1) varies depending on the kind of the polymerized vinylene carbonate monomer, but if the average molecular weight is too low, it does not solidify and the film formability is lowered, making it difficult to form a film. Further, even if the average molecular weight is too high, it is difficult to dissolve in a solvent and it is difficult to form a film, and flexibility and conductivity are also lowered. Accordingly, the average molecular weight is preferably in the range of 3 × 10 ^{3 to} 5 × 10 ⁵ .

  In the present invention, for the purpose of further improving the physical properties and chemical properties of the organic polymer represented by the formula (1), for example, the flexibility of the polymer solid electrolyte is further improved, For the purpose of increasing the degree of cross-linking when a cross-linked molecule is used, a monomer unit copolymerizable with a vinylene carbonate monomer can be introduced into the organic polymer of the formula (1). As such a copolymer, for example, the formula (2)

（式中、Ｒ¹ 及びＲ² は独立的に水素又は低級アルキルであり、Ｘはビニレンカーボネート系モノマーと共重合可能なモノマーからなるモノマーユニットであり、ｍ及びｎは独立的に任意の整数である。）で表される、ビニレンカーボネート系モノマーとそれと共重合可能なモノマーとの共重合体を使用することができる。ここで、式中のＸとしては、ビニル系モノマーユニットであることが好ましい。このようなビニル系モノマーユニットを構成するビニル系モノマーとしては、一種類のモノマーを使用してもよいが、２種類以上のモノマーを併用してもよい。このようなビニル系モノマーの具体例としては、例えば、ＣＨ₂＝ＣＨＣＯＯＨ、ＣＨ₂＝ＣＨＣＯＯＭ（ここでＭは金属イオンである）、ＣＨ₂＝ＣＨＣＯＯＲ（ここでＲはアルキル基である）、ＣＨ₂＝ＣＨＣＯＯ（ＣＨ₂ＣＨ₂Ｏ）_nＣＨ₃（ここでｎは１〜２３の整数である）、ＣＨ₂＝ＣＨＣＯＯ（ＣＨ₂ＣＨ₂Ｏ）_nＨ（ここでｎは１〜２３の整数である）、アクリル酸グリシジルなどのアクリル系モノマー、及びこれらの一部置換体であるメタクリル系モノマー、ＣＨ₂＝Ｃ［ＣＯＯ（ＣＨ₂ＣＨ₂Ｏ）_nＣＨ₃］₂（ここでｎは１〜２３の整数である）、ＣＨ₂＝ＣＨ（Ｃ₆Ｈ₅）、ＣＨ₂＝ＣＨＣＮ、ＣＨ₂＝ＣＨ（ＯＨ）、ＣＨ₂＝ＣＨＣＯＮＨ₂、ビニルピロリドンなどを好ましく例示することができる。

(Wherein R ¹ and R ² are independently hydrogen or lower alkyl, X is a monomer unit composed of a monomer copolymerizable with vinylene carbonate monomer, and m and n are independently any integers. A copolymer of a vinylene carbonate monomer and a monomer copolymerizable therewith can be used. Here, X in the formula is preferably a vinyl monomer unit. As a vinyl monomer constituting such a vinyl monomer unit, one type of monomer may be used, or two or more types of monomers may be used in combination. Specific examples of such vinyl monomers include, for example, CH ₂ = CHCOOH, CH ₂ = CHCOOM (where M is a metal ion), CH ₂ = CHCOOR (where R is an alkyl group), CH ₂ = CHCOO (CH ₂ CH ₂ O) _n CH ₃ (where n is an integer from 1 to 23), CH ₂ = CHCOO (CH ₂ CH ₂ O) _n H (where n is an integer from 1 to 23) in a), the acrylic monomer, and methacrylic monomer, which is part of these substitution _{products, CH 2 = C [COO (} CH 2 CH 2 O) n CH 3] 2 ( wherein n, such as glycidyl acrylate 1 to 23 of an _{integer), CH 2 = CH (C} 6 H 5), CH 2 = CHCN, CH 2 = CH (OH), CH 2 = CHCONH 2, can be preferably exemplified such as vinylpyrrolidone.

The organic polymer of the formula (2) contains one or more other monomer units in addition to the vinylene carbonate monomer unit in order to control the physical and chemical properties of the organic polymer. As a method for controlling the physical and chemical properties in this case, the characteristics of each monomer unit may be expressed to a desired degree by changing the composition ratio of these monomer units.

  For example, when a methacrylic monomer having a polyether structure as a side chain is used as a monomer to be copolymerized with a vinylene carbonate monomer and the content of the methacrylic monomer is increased, the crystallinity of the organic polymer is reduced. On the contrary, the flexibility increases, and the mechanical strength when swollen with an organic solvent increases.

  Further, when a monomer having a hydroxyl group in a part of the side chain is used as a monomer to be copolymerized with the vinylene carbonate monomer, the hydroxyl group acts as a crosslinking site when the organic polymer is crosslinked. Therefore, the higher the content of such a monomer, the higher the degree of crosslinking, and further the mechanical strength of the polymer solid electrolyte increases.

  However, the proportion of the vinylene carbonate monomer units in the organic polymer of formula (2) is preferably 50 mol% or more, more preferably 90 mol% or more. When the proportion of the vinylene carbonate monomer unit is less than 50 mol%, the ionic conductivity is greatly lowered, and it is difficult to dissolve in an organic solvent, so that the film formability is lowered.

  Like the organic polymer of the formula (1) or the formula (2), the organic polymer having a carbonate group as a functional group in the main chain includes a vinylene carbonate monomer and, if necessary, one or more other monomers. It can be easily obtained by polymerization by a conventional method such as radical polymerization or photopolymerization.

  On the other hand, the organic polymer having a carbonate group in the side chain among the organic polymers used in the present invention includes, for example, the following formula (3):

（式中、Ｒ¹ 、Ｒ² 及びＲ³ は独立的に水素又は置換もしくは非置換のアルキル基であり、ｊは０〜３の整数であり、ｋは任意の整数である）で表される、エチレンカーボネート系モノマーの単独重合体（ポリビニルエチレンカーボネート：ＰＶＥＣ）を使用することができる。ここで、Ｒ¹ 、Ｒ² 及びＲ³ は、それぞれ水素又は置換もしくは非置換のアルキル基とすることができるが、このアルキル基としては、エーテル基、エステル基、カルボニル基、カルボキシル基、水酸基等を有することができる。また、式（３）においてｊ＝０とし、エチレンカーボネート基が直接主鎖に結合するようにしてもよく、あるいはｊ＝１〜３とし、エチレンカーボネート基が低級メチレン鎖を介して主鎖に結合するようにしてもよい。

Wherein R ¹ , R ² and R ³ are independently hydrogen or a substituted or unsubstituted alkyl group, j is an integer of 0 to 3, and k is an arbitrary integer. A homopolymer of an ethylene carbonate monomer (polyvinylethylene carbonate: PVEC) can be used. Here, R ¹ , R ² and R ³ can each be hydrogen or a substituted or unsubstituted alkyl group. Examples of the alkyl group include an ether group, an ester group, a carbonyl group, a carboxyl group, a hydroxyl group, and the like. Can have. Further, in formula (3), j = 0 may be set so that the ethylene carbonate group is directly bonded to the main chain, or j = 1 to 3 and the ethylene carbonate group is bonded to the main chain via a lower methylene chain. You may make it do.

The average molecular weight of the organic polymer of the formula (3) varies depending on the structure of the monomer unit. Furthermore, since flexibility also falls, it is usually preferable to set it within the range of 5 × 10 ^{3 to} 5 × 10 ⁵ .

  The method for producing the organic polymer of the formula (3) can be obtained by a conventional method, for example, it can be easily obtained by polymerizing vinyl ethylene carbonate by a radical polymerization method, a photopolymerization method or the like.

  As the organic polymer having a carbonate group in the side chain among the organic polymers used in the present invention, another monomer unit copolymerizable with the constituent monomer is introduced into the organic polymer represented by the following formula (3). Copolymers can also be used.

  As such a copolymer, for example, the following formula (4):

（式中、Ｒ¹ 、Ｒ² 及びＲ³ は独立的に水素又は置換もしくは非置換のアルキルであり、ｊは０〜３の整数であり、ｋ及びｍは独立的に任意の整数であり、Ｘはエチレンカーボネート系モノマーと共重合可能なモノマーからなるモノマーユニットである）で表される有機高分子を使用することができる。

Wherein R ¹ , R ² and R ³ are independently hydrogen or substituted or unsubstituted alkyl, j is an integer from 0 to 3, k and m are independently any integer, X is a monomer unit composed of a monomer copolymerizable with an ethylene carbonate monomer).

  Here, X is composed of a monomer unit copolymerizable with the ethylene carbonate monomer of the formula (3), and such a monomer unit includes various vinyls similar to the copolymer of the formula (2). It can be formed from a system monomer. Further, the constitutional ratio of each monomer unit is determined according to the degree to which the characteristics of each monomer unit should be manifested in accordance with the desired physical and chemical properties, similarly to the copolymer of the formula (2). For example, also in the copolymer of the formula (4), when a methacrylic monomer having a polyether structure as a side chain is contained as a monomer other than the ethylene carbonate monomer, and the content of the methacrylic monomer is increased. The crystallinity of the organic polymer is lowered, the flexibility is increased, and the mechanical strength when swollen with an organic solvent is increased. In addition, when a monomer having a hydroxyl group is included in a part of the side chain, the hydroxyl group acts as a crosslinking site when the organic polymer is crosslinked. Therefore, the degree of crosslinking increases as the monomer content increases. As a result, the mechanical strength of the solid polymer electrolyte increases. However, the proportion of the ethylene carbonate monomer unit in the copolymer of the formula (4) is preferably 50 mol% or more, more preferably 90 mol% or more. When the proportion of the ethylene carbonate monomer unit is less than 50 mol%, the ionic conductivity is greatly lowered, the solubility of the metal salt is also greatly lowered, and it is difficult to dissolve in an organic solvent, so that the film formability is lowered.

  The method for producing the organic polymer of formula (4) can be obtained by a conventional method, and can be easily obtained by copolymerizing an ethylene carbonate monomer and another monomer by, for example, radical polymerization or photopolymerization. it can.

Further, as the organic polymer having a carbonate group as a functional group used in the present invention, not only the organic polymers of the above formulas (1) to (4) are used alone, but also compatible with them. A polymer blend obtained by blending these polymers can also be used. As such other polymers, PEO and the polymers represented by the above formulas (i) to (iv) can be used. The blend ratio can be appropriately selected according to the required conductivity.

  In the present invention, it is preferable to crosslink the organic polymers as described above. As a result, it is possible to prevent the organic solvent from bleeding when pressure is applied to the solid polymer electrolyte, and it is possible to swell the organic polymer with more organic solvent and to improve the conductivity. In addition, the mechanical strength can be improved.

  Although there is no restriction | limiting in particular about the crosslinking method, For example, it can bridge | crosslink by active radiation irradiation, light irradiation, electron beam irradiation, and heating. In this case, photopolymerization initiators such as trimethylsilylbenzophenone, benzoin and 2-methylbenzoin, and polymerization initiators such as benzoyl peroxide, methyl ethyl ketone and azobisisobutyronitrile can be used as necessary. As a crosslinking agent, a polyfunctional monomer having a plurality of vinyl groups, toluene-2,4-diisocyanate, 4,4′-diphenylmethane diisocyanate, or the like can be used.

  Especially, it is preferable to use the polyfunctional monomer which has a some vinyl group as a crosslinking agent. As a result, even when the cross-linked organic polymer has a hydroxyl group, all of the hydroxyl groups act as cross-linking sites after cross-linking, preventing unreacted hydroxyl groups from remaining in the cross-linked organic polymer. it can. Therefore, even if this polymer solid electrolyte is incorporated into a lithium-based battery, unnecessary reaction does not occur and it can be used electrochemically stably. Furthermore, in the production of a crosslinked organic polymer swollen with an electrolytic solution by using a polyfunctional monomer having a plurality of vinyl groups, synthesis of the crosslinked organic polymer and swelling by the electrolytic solution are performed. It can be easily performed in one step.

  As such a polyfunctional monomer having a plurality of vinyl groups, for example, the following formula (7):

（式中、Ｒ¹ 及びＲ² は独立的に水素又はメチル基であり、ｍ＝１〜９の整数であり、Ｃ_mＨ_2m は直鎖状でもよく分岐状でもよく、ｎ＝０〜９の整数である。さらに（ＯＣ_mＨ_2m)_nの一部は次式（８）

(Wherein R ¹ and R ² are independently hydrogen or a methyl group, m is an integer of 1 to 9, C _m H _2m may be linear or branched, and n = 0 to 9 In addition, a part of (OC _m H _2m ) _n is represented by the following formula (8):

で置換されていてもよい。）のジアクリル又はジメタクリル系モノマーをあげることができ、特に、上記式（７）においてｍ＝２である、次式（７ａ）

May be substituted. ) Diacrylate or dimethacrylic monomer, and in particular, m = 2 in the above formula (7), the following formula (7a)

のポリエチレングリコールジアクリレート、又はポリエチレングリコールジメタクリレートを好ましくあげることができる。

The polyethylene glycol diacrylate or polyethylene glycol dimethacrylate can be preferably mentioned.

  In addition, when the organic polymer is cross-linked using the cross-linking agent in this way, if the use ratio of the cross-linking agent is too large, the carbonate group characteristic of the organic polymer used in the present invention is changed from the organic polymer after cross-linking. The property derived from is lost, and the ionic conductivity is lowered, which is not preferable. Therefore, when a polyfunctional monomer having a plurality of vinyl groups such as diacrylic or dimethacrylic monomers is used as a cross-linking agent, the use ratio has a plurality of vinyl groups that will constitute a cross-linked product. Multiple vinyl groups for the total of multifunctional monomer units, carbonate monomer units (vinylene carbonate monomer units or monomer units having ethylene carbonate groups in the side chain), and other monomer units copolymerized with carbonate monomers It is preferable that the ratio of the polyfunctional monomer unit having ≦ 50 mol%.

On the other hand, as an electrolyte contained in the polymer solid electrolyte of the present invention, a metal salt used in a conventional polymer solid electrolyte can be used. Examples of such metal salts include 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.

  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. In this case, a single species may be used as the metal salt, or a plurality of types of salts may be used simultaneously.

  The preferred concentration of the metal salt varies depending on the type of the metal salt and the type of organic polymer or organic solvent contained in the polymer solid electrolyte together with the metal salt, even if the ratio of the metal salt to the organic solvent is too low. Even if it is too high, the conductivity is lowered, but it is usually preferable that the metal salt is contained in an amount of about 0.2 to 2 mol with respect to 1 liter of the organic solvent, and 0.5 to 1.5 mol. Is more preferable.

  Moreover, as the organic solvent to be contained in the solid polymer electrolyte of the present invention, the above-mentioned electrolyte can be dissolved, and those compatible with the organic polymer can be appropriately used. Alternatively, those having at least one nitrogen atom are particularly preferable. Examples of such an organic solvent include ethylene carbonate, propylene carbonate, dimethyl carbonate, butylene carbonate, diethyl carbonate, dimethoxyethane, tetrahydrofuran, dioxolane, γ-butyrolactone, sulfolane, dimethylformamide, and the like. These may be used alone or in combination.

  Increasing the use ratio of the organic solvent in the polymer solid electrolyte is preferable because the electrical conductivity can be improved. However, if the amount is too large, the mechanical strength is lowered, and the film formability is also lowered to form a film. Therefore, in the present invention, the maximum amount of the solid polymer electrolyte containing the organic solvent can be present as a film, and the organic solvent is contained in an amount of 500 parts by weight or less with respect to 100 parts by weight of the organic polymer. . The preferred use ratio of the organic solvent varies depending on the type of electrolyte to be used, the type of organic solvent, the type of organic polymer used as the structural material, the presence or absence of crosslinking, etc., but the lower limit is determined from the organic solvent, the electrolyte, and the organic polymer. It is preferable to determine that the electrical conductivity of the polymer solid electrolyte is approximately the same order as the electrical conductivity of the electrolyte solution composed of the organic solvent and the electrolyte, and usually the use ratio indicating a conductivity of 1 mS / cm or more. It is preferable that Further, the upper limit of the use ratio is preferably an amount that can maintain sufficient mechanical strength when a polymer solid electrolyte containing an organic solvent is formed into a film and incorporated in a battery or the like. More specifically, for example, when the homopolymer of the vinylene carbonate monomer of formula (1) is used as the organic polymer, the organic solvent is used in an amount of 10 to 200 parts by weight with respect to 100 parts by weight of the organic polymer. It is preferable to set it as 50 to 100 parts by weight. When the copolymer (formula (2)) is used, the organic solvent is preferably 10 to 400 parts by weight, more preferably 50 to 300 parts by weight with respect to 100 parts by weight of the organic polymer. . Furthermore, when using the crosslinked body, it is preferable to set it as 10-500 weight part with respect to 100 weight part of organic polymers, and it is more preferable to set it as 50-300 weight part.

  Moreover, when using the homopolymer of the carbonate-type monomer of the above-mentioned formula (3) as the organic polymer, the organic solvent is preferably 10 to 200 parts by weight with respect to 100 parts by weight of the organic polymer. It is more preferable to set it to -100 weight part. Moreover, when using the copolymer (Formula (4)), it is preferable that it is 10-400 weight part with respect to 100 weight part of organic polymers, and it is more preferable to set it as 30-300 weight part. . Furthermore, when using the crosslinked body, it is preferable to make an organic solvent into 10-500 weight part with respect to 100 weight part of organic polymers, and it is more preferable to set it as 30-300 weight part.

  There is no restriction | limiting in particular as a manufacturing method of the polymer solid electrolyte of this invention containing the above organic polymers, electrolyte, and an organic solvent, It can form in arbitrary forms with a various method. For example, in general, a polymer solid electrolyte is often used in the form of a film, and as a film forming method for this purpose, the above-mentioned organic polymer and electrolyte are dissolved in an organic solvent, and this solution is used as a flat substrate. The film can be formed by a casting method in which the film is obtained by spreading the film and evaporating the solvent. In this case, the degree of evaporation of the solvent is not performed until the solvent completely disappears from the solution on the substrate, but not so much that the polymer solid electrolyte formed on the substrate can maintain a film-like form. Is evaporated to remain in the solid polymer electrolyte.

  Alternatively, after completely evaporating the solvent from the solution on the substrate to form a polymer solid electrolyte film not containing an organic solvent, the resulting polymer solid electrolyte film is swollen by immersing it in an organic solvent, and then Excess organic solvent may be wiped off. In this case, the organic solvent used for preparing the solution spread on the substrate is not only a preferable organic solvent to be included in the polymer solid electrolyte of the present invention as described above, but also a cast solvent having an appropriate polarity. Can be widely used. Further, the amount of the organic solvent used for swelling can be controlled by immersing the polymer solid electrolyte formed on the film in the organic solvent, wiping off the excess organic solvent, and the like. Moreover, you may make the organic solvent used for immersion contain a metal salt as needed.

  When a polymer solid electrolyte is formed by the casting method as described above, there are no particular restrictions on the amount of organic solvent used and the mixing order of the organic polymer, electrolyte and organic solvent, etc. Absent.

  In addition, when the polymer solid electrolyte contains a crosslinked product as an organic polymer, the above-described casting method may be one that has already undergone a crosslinking reaction as the organic polymer. Alternatively, the polymer solid electrolyte may be formed into a film. Sometimes, a solution in which the uncrosslinked organic polymer, the electrolyte, and the organic solvent have a predetermined concentration is prepared, and this solution may be subjected to a crosslinking reaction in a nitrogen atmosphere.

  The polymer solid electrolyte of the present invention can be used as various electrochemical device materials including high energy density batteries such as lithium batteries.

  The organic polymer having a carbonate group as a functional group contained in the solid polymer electrolyte of the present invention as a structural material has good film formability and flexibility even when a metal salt serving as a carrier ion is contained at a high concentration. Since the mechanical strength can be maintained, the polymer solid electrolyte composed of the organic polymer and the electrolyte exhibits high conductivity. In the present invention, the polymer solid electrolyte further contains an organic solvent. Since the organic polymer is swollen, the polymer solid electrolyte exhibits extremely high conductivity. Therefore, according to the polymer solid electrolyte of the present invention, it is possible to simultaneously realize high ionic conductivity and good film formability, flexibility and mechanical strength.

  In particular, the use of a crosslinked product as the organic polymer can increase the amount of organic solvent that can be contained in the polymer solid electrolyte without greatly reducing the film formability and mechanical strength. It can swell more. Therefore, it is possible to further increase the conductivity.

  Next, the present invention will be specifically described based on examples. Here, in each Example, unless otherwise specified, organic polymers were synthesized as follows to produce polymer solid electrolyte films, and their ionic conductivity and tensile strength were evaluated.

1. Synthesis of Organic Polymer An organic polymer used for the polymer solid electrolyte of the example was synthesized as follows.

1-A. Synthesis of polyvinylene carbonate (PVnC) 10 g of vinylene carbonate (VnC) purified by sodium borohydride (NaBH ₄ ) in a glass container for sealed tube for about 20 ml, and azo Bisisobutyronitrile (AIBN) 4 mg was added. This container was connected to a nitrogen purge apparatus, and after the contents were cooled and solidified in a dry ice-methanol bath, the operations of deaeration, nitrogen introduction and melting were repeated three times under high vacuum, and finally the tube was sealed under high vacuum. .

  This vessel was subjected to a polymerization reaction for 24 hours in a shaking thermostat set at 80 ° C. During this polymerization reaction, the viscosity of the reaction solution increased and the whole solidified.

  The reaction was cooled to room temperature and then opened, and the resulting solid was dissolved in dimethylformamide (DMF), and the solution was poured into 5 volumes of methanol with stirring. As a result, a white fibrous solid was obtained. The solid was filtered off and washed thoroughly with methanol. The obtained white solid was purified by repeating the reprecipitation operation 2 to 3 times using a DMF-methanol mixed solvent, and the resulting polymer was dried under reduced pressure. As a result, the desired organic polymer was obtained with a yield of about 40%.

This organic polymer could be identified as polyvinylene carbonate by ¹ H-NMR in FT-IR and CDCl ₃ . Moreover, when the average molecular weight of this organic polymer was measured by gel permeation chromatography (GPC), it was about 3 × 10 ^{3 to} 5 × 10 ⁵ .

1-B. Synthesis of polyvinylethylene carbonate (PVEC)
i) Synthesis of vinyl ethylene carbonate (VEC) 190 g of m-chloroperbenzoic acid was dissolved in 500 ml of dichloromethane, cooled with ice, and 1,3-butadiene was bubbled for about 2 hours while stirring the solution. It was dissolved in the solution and reacted. Then, 3,4-epoxy-1-butene was obtained by stirring overnight at room temperature. Next, an aqueous sodium hydrogen carbonate solution was added thereto, and the mixture was vigorously stirred to perform hydrolysis. After separating the aqueous phase, water was further added to extract the organic phase and concentrated. The obtained oily residue was distilled under reduced pressure to obtain 1-butene-3,4-diol. This was transesterified with ethyl chlorocarbonate in dichloromethane to obtain the desired VEC. The structure of the obtained VEC was confirmed by boiling point (106 ° C./6.5 mmHg), FT-IR, ¹ H-NMR.

ii) Synthesis of polyvinyl ethylene carbonate (PVEC) 10 g of vinyl ethylene carbonate (VEC) and 4 mg of azobisisobutyronitrile (AIBN) were added to a sealed glass container for about 20 ml. This container was connected to a nitrogen purge apparatus, and after the contents were cooled and solidified in a dry ice-methanol bath, the operations of deaeration, nitrogen introduction and melting were repeated three times under high vacuum, and finally the tube was sealed under high vacuum. .

  This vessel was subjected to a polymerization reaction for 24 hours in a shaking thermostat set at 80 ° C. During this polymerization reaction, the viscosity of the reaction solution increased and the whole solidified.

  The reaction was cooled to room temperature and then opened, and the resulting solid was dissolved in dimethylformamide (DMF), and the solution was poured into 5 volumes of methanol with stirring. As a result, a white fibrous solid was obtained. The solid was filtered off and washed thoroughly with methanol. The obtained white solid was purified by repeating the reprecipitation operation 2 to 3 times using a DMF-methanol mixed solvent, and the resulting polymer was dried under reduced pressure. As a result, the desired organic polymer was obtained with a yield of about 40%.

This organic polymer was identified and confirmed by ¹ H-NMR in FT-IR and CDCl ₃ . The melting point was 140-150 ° C. Moreover, when the average molecular weight of this organic polymer was measured by gel permeation chromatography (GPC), it was about 1 × 10 ³ to 1 × 10 ⁵ .

1-C. Synthesis of poly (ethylene carbonate) methacrylate (PECMA)
i) Synthesis of ethylene carbonate methacrylate (ECMA) Aqueous sodium hydrogen carbonate solution was added to epoxy methacrylate and stirred vigorously for hydrolysis. The aqueous phase was separated and more water was added to extract the organic phase and concentrated. The obtained oily residue was distilled under reduced pressure to obtain ethylene diol methacrylate. This was dissolved in 200 ml of dichloromethane, and 3 times equivalent of triphosgene (Cl ₃ CO) ₂ CO was added little by little with vigorous stirring, followed by further stirring at 20 ° C. for 96 hours. This was concentrated with an evaporator, and the residual oil was distilled under reduced pressure. This gave the expected ECMA. The structure of the obtained ECMA was confirmed by FT-IR and ¹ H-NMR. The yield was about 50%.

ii) Synthesis of poly (ethylene carbonate) methacrylate (PECMA) 10 g of (ethylene carbonate) methacrylate (ECMA) and 4 mg of azobisisobutyronitrile (AIBN) were added to a sealed glass container for about 20 ml. This container was connected to a nitrogen purge apparatus, and after the contents were cooled and solidified in a dry ice-methanol bath, the operations of deaeration, nitrogen introduction and melting were repeated three times under high vacuum, and finally the tube was sealed under high vacuum. .

  This vessel was subjected to a polymerization reaction for 24 hours in a shaking thermostat set at 80 ° C. During this polymerization reaction, the viscosity of the reaction solution increased and the whole solidified.

  The reaction was cooled to room temperature and then opened, and the resulting solid was dissolved in dimethylformamide (DMF), and the solution was poured into 5 volumes of methanol with stirring. As a result, a white fibrous solid was obtained. The solid was filtered off and washed thoroughly with methanol. The obtained white solid was purified by repeating the reprecipitation operation 2 to 3 times using a DMF-methanol mixed solvent, and the resulting polymer was dried under reduced pressure. As a result, the desired organic polymer was obtained with a yield of about 40%.

This organic polymer was identified and confirmed by ¹ H-NMR in FT-IR and CDCl ₃ .

1-D. And vinylene carbonate copolymers vinylene carbonate in a glass vessel sealed tube for synthesis about 20ml of (VNC) 10 g, methoxy polyethylene glycol methacrylate as a methacrylate monomer having a polyether structure as a side chain (CH ₂ = CCH ₃ (COO (CH ₂ CH ₂ O) ₄ CH ₃ ): PEM4), or hydroxyethyl methacrylate having a hydroxyl group at the end of the side chain (CH ₂ = CCH ₃ (COOCH ₂ CH ₂ OH): HEMA), Add according to the predetermined monomer composition ratio (mol%) shown in the examples described later, and further add azobisisobutyronitrile (AIBN) in an amount of 0.2 to 1.0 mol% based on the total number of moles of monomers charged. Stir to a homogeneous solution. This container was connected to a nitrogen purge apparatus, and after the contents were cooled and solidified in a dry ice-methanol bath, the operations of deaeration, nitrogen introduction and melting were repeated three times under high vacuum, and finally the tube was sealed under high vacuum. .

  The vessel was subjected to a polymerization reaction for 24 hours in a shaking thermostat set at 60 ° C. During this polymerization reaction, the viscosity of the reaction solution increased and the whole solidified.

  The reaction was cooled to room temperature and then opened, and the resulting solid was dissolved in dimethylformamide (DMF), and the solution was poured into 5 volumes of methanol with stirring. As a result, a white fibrous solid was obtained. The solid was filtered off and washed thoroughly with methanol. The obtained white solid was purified by repeating the reprecipitation operation 2 to 3 times using a DMF-methanol mixed solvent, and the resulting polymer was dried under reduced pressure. As a result, the desired organic polymer was obtained with a yield of about 40%.

When the monomer composition of this organic polymer was identified by ¹ H-NMR in CDCl ₃ , it was found that it was in accordance with the amount of each monomer charged at the time of synthesis.

1-E. Synthesis of vinyl ethylene carbonate copolymer In the synthesis of vinylene carbonate copolymer 1-D. Above, vinyl ethylene carbonate (VEC) is used instead of vinylene carbonate (VnC). The copolymer of was obtained.

Synthesis of 1-F. (Ethylene carbonate) methacrylate copolymer In the synthesis of vinylene carbonate copolymer of 1-D. Above, by using ethylene carbonate methacrylate (ECMA) instead of vinylene carbonate (VnC). The expected copolymer was obtained.

2. Preparation of polymer electrolyte membrane
2-A. Preparation of Uncrosslinked Polymer Solid Electrolyte Film The organic polymer obtained in 1 above is added to sufficiently dehydrated DMF, and sufficiently stirred to obtain a uniform solution. A filter having a pore size of 0.45 μm Was passed through to remove insoluble matter, and the resulting solution was used to form a film by the casting method as follows. That is, the solution was transferred to a Teflon petri dish with a smooth bottom surface, the solvent was evaporated in a thermostat set at 40 to 60 ° C. under a nitrogen atmosphere, and the solvent was completely removed under vacuum heating, and dried. A film-like polymer film was obtained.

Next, as shown in the examples below, the electrolyte ₄ and the like LiClO in an organic solvent such as propylene carbonate (PC) by a predetermined concentration dissolved to prepare an electrolytic solution, obtained above film-like into the solution The solid polymer electrolyte was dipped to swell the solid polymer electrolyte. The polymer solid electrolyte was taken out of the solution and the excess solution was wiped off to obtain a polymer solid electrolyte film in which the organic polymer was swollen with the organic solvent.

  The polymer solid electrolyte thus obtained was a colorless to light yellow film rich in flexibility. Regarding the thickness of this film, it can be suitably prepared to a predetermined thickness depending on the purpose, but here, a film having a thickness of 50 to 150 μm was prepared in order to evaluate the conductivity as described later.

2-B. Production of Crosslinked Polymer Solid Electrolyte Film An uncrosslinked polymer solid electrolyte film is produced according to 2-A. Above, and irradiated with an electron beam with an acceleration voltage of 250 kV and an electron dose of 8 Mrad in an inert gas atmosphere. To crosslink.

  The thus obtained crosslinked polymer solid electrolyte film was a colorless to light yellow film rich in flexibility. Regarding the thickness of this film, it can be suitably prepared to a predetermined thickness depending on the purpose, but here, a film having a thickness of 50 to 150 μm was prepared in order to evaluate the conductivity as described later.

3. Evaluation of Ionic Conductivity The ionic conductivity of the obtained polymer solid electrolyte film was evaluated as follows. That is, a polymer solid electrolyte film was pressure-bonded with a platinum electrode or a lithium metal electrode so that each contact of the electrode / film / electrode was sufficiently maintained to prepare an evaluation cell. Thereafter, a temperature-variable thermostat was set to a predetermined temperature, an evaluation cell was placed therein, and the evaluation cell was allowed to stand at that temperature for about 1 hour. Then, the conductivity was analytically calculated from the semicircular arc portion obtained by the constant voltage complex impedance method (AC amplitude voltage 30 to 100 mV, AC frequency band 10 ⁻² to 10 ⁷ Hz). In this case, by changing the electrode to platinum or lithium metal and changing the electrode area, the pseudo semicircular arc component was attributed to the resistance portion contributing to ionic conduction in the polymer solid electrolyte.

4). Evaluation of tensile strength Cut the polymer solid electrolyte film into a strip of 10mm x 40mm x 150μm thickness to make a test piece, and measure its tensile strength using a general-purpose Instron tester and similar tester did. In this case, one of the chucks for gripping the test piece is fixed to the strain gauge, and the other is continuously pulled by moving it up and down at a constant speed electrically. When the test piece breaks, the ultimate stress indicated on the strain gauge is determined by the tensile strength ( kgf / cm ² ).

Examples 1-5
An uncrosslinked polymer solid electrolyte film made of polyvinylene carbonate (PVnC) was produced. In this case, the concentration of LiClO ₄ in the electrolytic solution (LiClO ₄ / propylene carbonate (PC)) was changed as shown in FIG. 1 (0.2, 0.5, 1.0, 1.5, 2.0 M). At this time, the amount of the electrolytic solution used for swelling the organic polymer composed of PVnC (hereinafter, abbreviated as swelling amount) was set such that the weight ratio with respect to PVnC was 100% by weight.

  The electrical conductivity at 25 ° C. of the obtained film was determined. The result is shown in FIG.

Examples 6-10
An uncrosslinked polymer solid electrolyte film made of polyvinyl ethylene carbonate (PVEC) was produced. In this case, the concentration of LiClO ₄ in the electrolytic solution (LiClO ₄ / propylene carbonate (PC)) was changed as shown in FIG. 1 (0.2, 0.5, 1.0, 1.5, 2.0 M). The swelling amount of the electrolytic solution at this time was such that the weight ratio with respect to PVnC was 100% by weight.

  The electrical conductivity at 25 ° C. of the obtained film was determined. The result is shown in FIG.

Examples 11-15
An uncrosslinked polymer solid electrolyte film made of poly (ethylene carbonate) methacrylate (PECMA) was produced. In this case, the concentration of LiClO ₄ in the electrolytic solution (LiClO ₄ / propylene carbonate (PC)) was changed as shown in FIG. 1 (0.2, 0.5, 1.0, 1.5, 2.0 M). The swelling amount of the electrolytic solution at this time was such that the weight ratio with respect to PVnC was 100% by weight.

  The electrical conductivity at 25 ° C. of the obtained film was determined. The result is shown in FIG.

From the results of Examples 1 to 15 shown in FIG. 1, in the uncrosslinked polymer solid electrolyte film of the example, the conductivity was around 1M in LiClO ₄ concentration in the electrolytic solution (LiClO ₄ / propylene carbonate (PC)). It can be seen that the conductivity is maintained at a high value without a significant decrease in the range of 0.2 to 2.0M.

Examples 16-18
Uncrosslinked polymer solid electrolyte films made of polyvinylene carbonate (PVnC), polyvinyl ethylene carbonate (PVEC), or poly (ethylene carbonate) methacrylate (PECMA) were produced. In this case, 1M-LiBF ₄ / propylene carbonate (PC) was used as the electrolytic solution. In addition, the swelling amount of the electrolytic solution at this time was such that the weight ratio with respect to PVnC, PVEC, or PECMA was 100% by weight.

  The electrical conductivity at 25 ° C. of the obtained film was determined. The result is shown in FIG.

Examples 19-21
Uncrosslinked polymer solid electrolyte films made of polyvinylene carbonate (PVnC), polyvinyl ethylene carbonate (PVEC), or poly (ethylene carbonate) methacrylate (PECMA) were produced. In this case, 1M-LiPF ₆ / propylene carbonate (PC) was used as the electrolytic solution. In addition, the swelling amount of the electrolytic solution at this time was such that the weight ratio with respect to PVnC, PVEC, or PECMA was 100% by weight.

  The electrical conductivity at 25 ° C. of the obtained film was determined. The result is shown in FIG.

From the results of Examples 16 to 21 shown in FIG. 2, in the uncrosslinked polymer solid electrolyte film of the example, 1M-LiPF was used even when 1M-LiBF ₄ / propylene carbonate (PC) was used as the electrolyte. _It can be seen that even when ₆ / propylene carbonate (PC) is used, high conductivity can be obtained.

Examples 3, 22-27
An uncrosslinked polymer solid electrolyte film made of polyvinylene carbonate (PVnC) was produced. In this case, 1M-LiClO ₄ / propylene carbonate (PC) was used as the electrolytic solution. Further, as shown in FIG. 3, the swelling amount of the electrolytic solution at this time was such that the weight ratio with respect to PVnC was 10, 30, 50, 100, 150, 200, 300% by weight.

The conductivity and tensile strength at 25 ° C. of the obtained film were determined. The result is shown in FIG. In FIG. 3, ● indicates a tensile strength of 3 kgf / cm ² or more, ▲ indicates a tensile strength of 0.2 kgf / cm ² or more and less than 3 kgf / cm ² , and × indicates that the polymer solid electrolyte cannot be formed into a film and is in an adhesive gel state It shows what became.

Example 8, 28-33
An uncrosslinked polymer solid electrolyte film made of polyvinyl ethylene carbonate (PVEC) was produced. In this case, 1M-LiClO ₄ / propylene carbonate (PC) was used as the electrolytic solution. Moreover, as shown in FIG. 3, the swelling amount of the electrolyte solution at this time was such that the weight ratio with respect to PVEC was 10, 30, 50, 100, 150, 200, 300% by weight.

  The conductivity and tensile strength at 25 ° C. of the obtained film were determined. The result is shown in FIG.

Examples 13, 34-39
An uncrosslinked polymer solid electrolyte film made of poly (ethylene carbonate) methacrylate (PECMA) was produced. In this case, using 1M-LiClO ₄ / propylene carbonate (PC) as the electrolyte. Moreover, as shown in FIG. 3, the swelling amount of the electrolyte solution at this time was such that the weight ratio with respect to PECMA was 10, 30, 50, 100, 150, 200, 300% by weight.

  The conductivity and tensile strength at 25 ° C. of the obtained film were determined. The result is shown in FIG.

From the results of the examples shown in FIG. 3, in the uncrosslinked polymer solid electrolyte films of these examples, the ratio of the electrolyte solution to the organic polymer (that is, the amount of swelling) should be about 150% by weight or less. the possible formation of the solid polymer electrolyte in film form, it can be seen that the further tensile strength by reducing the amount of swelling is increased to 3 kgf / cm ² or more. In this case, the conductivity tends to decrease by decreasing the swelling amount, but it is understood that a high conductivity can be obtained at least when the swelling amount is 10% by weight or more.

Examples 40-42
Each of the uncrosslinked solid polymer electrolyte films of Examples 3, 8, and 13 was subjected to a crosslinking reaction by irradiating an electron beam with an acceleration voltage of 250 kV and an electron dose of 8 Mrad in an inert gas atmosphere. PVnC), polyvinylethylene carbonate (PVEC) or poly (ethylene carbonate) methacrylate (PECMA) as a structural material, and a polymer using 1M-LiClO ₄ / propylene carbonate (PC) as an electrolyte solution with a swelling amount of 100% by weight A solid electrolyte film was prepared. And the electrical conductivity of the obtained polymer solid electrolyte film was calculated | required. The result is shown in FIG.

Examples 43-45
Each of the uncrosslinked polymer solid electrolyte films of Examples 16 to 18 was subjected to a crosslinking reaction by irradiating an electron beam with an acceleration voltage of 250 kV and an electron dose of 8 Mrad in an inert gas atmosphere, and polyvinylene carbonate (PVnC). , A polymer solid electrolyte using a crosslinked material of polyvinylethylene carbonate (PVEC) or poly (ethylene carbonate) methacrylate (PECMA) as a structural material, and using 1M-LiBF ₄ / propylene carbonate (PC) as an electrolyte solution with a swelling amount of 100% by weight A film was prepared. And the electrical conductivity of the obtained polymer solid electrolyte film was calculated | required. The result is shown in FIG.

Examples 46-48
Each of the uncrosslinked polymer solid electrolyte films of Examples 19 to 21 was subjected to a crosslinking reaction by irradiating an electron beam with an acceleration voltage of 250 kV and an electron dose of 8 Mrad in an inert gas atmosphere, and polyvinylene carbonate (PVnC). , A solid polymer electrolyte using a crosslinked material of polyvinylethylene carbonate (PVEC) or poly (ethylene carbonate) methacrylate (PECMA) as a structural material and using 1M-LiPF ₆ / propylene carbonate (PC) as an electrolyte solution with a swelling amount of 100% by weight A film was prepared. And the electrical conductivity of the obtained polymer solid electrolyte film was calculated | required. The result is shown in FIG.

  From the results of Examples 40 to 48 shown in FIG. 4, the polymer solid electrolyte film using the crosslinked body as the organic polymer has a slightly lower conductivity than that using the corresponding uncrosslinked organic polymer. Although it shows a tendency to decrease, it does not significantly decrease, and it can be seen that the conductivity is still high.

Examples 40, 49-54
Each of the uncrosslinked polymer solid electrolyte films of Examples 3 and 22 to 27 was irradiated with an electron beam having an acceleration voltage of 250 kV and an electron dose of 8 Mrad in an inert gas atmosphere, and a polyvinylene carbonate ( the crosslinked product of the PVnC) a structural member, producing a polymer solid electrolyte film 1M-LiClO ₄ / propylene carbonate as an electrolyte solution (PC) were used amount of swelling 10,30,50,100,150,200,300 wt% did.

The conductivity and tensile strength at 25 ° C. of the obtained film were determined. The result is shown in FIG. In FIG. 5, ● indicates a tensile strength of 3 kgf / cm ² or more, ▲ indicates a tensile strength of 0.2 kgf / cm ² or more and less than 3 kgf / cm ² , and × indicates that the polymer solid electrolyte cannot be formed into a film and is in a sticky gel state It shows what became.

Examples 41, 55-60
Each of the uncrosslinked polymer solid electrolyte films of Examples 8 and 28 to 33 was irradiated with an electron beam having an acceleration voltage of 250 kV and an electron dose of 8 Mrad in an inert gas atmosphere, and a polyvinylethylene carbonate ( PVEC) is used as a structural material, and a solid polymer electrolyte film using 1M-LiClO ₄ / propylene carbonate (PC) as an electrolyte solution with a swelling amount of 10, 30, 50, 100, 150, 200, 300% by weight is prepared. did.

  The conductivity and tensile strength at 25 ° C. of the obtained film were determined. The result is shown in FIG.

Examples 42, 61-66
Each of the uncrosslinked solid polymer electrolyte films of Examples 13 and 34 to 39 was irradiated with an electron beam having an acceleration voltage of 250 kV and an electron dose of 8 Mrad in an inert gas atmosphere, and a poly (ethylene carbonate) ) Polymer solid electrolyte using a cross-linked product of methacrylate (PECMA) as a structural material and using 1M-LiClO ₄ / propylene carbonate (PC) as an electrolyte solution with a swelling amount of 10, 30, 50, 100, 150, 200, 300% by weight A film was prepared.

  And the electrical conductivity and tensile strength in 25 degreeC of this film were calculated | required. The result is shown in FIG.

  From the results of the examples shown in FIG. 5, in the polymer solid electrolyte films of the crosslinked bodies of these examples, even if the use ratio (that is, the amount of swelling) of the electrolyte solution to the organic polymer is increased to 300% by weight. It can be seen that the polymer solid electrolyte can be formed into a film, and higher electrical conductivity can be achieved in a range in which the swelling amount is larger than the corresponding uncrosslinked polymer solid electrolyte film.

Examples 67-69
A polymer solid electrolyte film made of a copolymer of polyvinylene carbonate (PVnC) and methoxypolyethylene glycol methacrylate (CH ₂ ═CCH ₃ (COO (CH ₂ CH ₂ O) ₄ CH ₃ ): PEM4) was produced. In this case, the composition ratio of the copolymerization monomer (PVnC: PEM4) was changed to 95: 5, 80:20, or 60:40 as shown in FIG. Further, 1M-LiClO ₄ / propylene carbonate (PC) was used as the electrolyte solution with a swelling amount of 200% by weight.

The conductivity and tensile strength at 25 ° C. of the obtained film were determined. The result is shown in FIG. In FIG. 6, ● indicates a tensile strength of 3 kgf / cm ² or more, ▲ indicates a tensile strength of 0.2 kgf / cm ² or more and less than 3 kgf / cm ² , and × indicates that the polymer solid electrolyte cannot be formed into a film and is in an adhesive gel state It shows what became.

Examples 70-72
A polymer solid electrolyte film made of a copolymer of polyvinylethylene carbonate (PVEC) and methoxypolyethylene glycol methacrylate (CH ₂ ═CCH ₃ (COO (CH ₂ CH ₂ O) ₄ CH ₃ ): PEM4) was produced. In this case, the composition ratio (PVEC: PEM4) of the copolymerization monomer was changed to 95: 5, 80:20, or 60:40 as shown in FIG. As the electrolytic solution was used 1M-LiClO ₄ / swelling amount 200% by weight of propylene carbonate (PC).

  The conductivity and tensile strength at 25 ° C. of the obtained film were determined. The result is shown in FIG.

Examples 73-75
A polymer solid electrolyte film made of a copolymer of poly (ethylene carbonate) methacrylate (PECMA) and methoxypolyethylene glycol methacrylate (CH ₂ ═CCH ₃ (COO (CH ₂ CH ₂ O) ₄ CH ₃ ): PEM4) is produced. did. In this case, the composition ratio of the copolymerization monomer (PECMA: PEM4) was changed to 95: 5, 80:20, or 60:40 as shown in FIG. As the electrolytic solution was used 1M-LiClO ₄ / swelling amount 200% by weight of propylene carbonate (PC).

  The conductivity and tensile strength at 25 ° C. of the obtained film were determined. The result is shown in FIG.

  From the results of Examples 67 to 75 shown in FIG. 6, in the polymer solid electrolyte film made of the copolymer of Example, the ratio of PEM4 used as the copolymerization monomer is within the range of about 40 mol% or less. It can be seen that high conductivity can be obtained.

Examples 76-78, 79-81
A polymer solid electrolyte film made of an uncrosslinked copolymer of polyvinylene carbonate (PVnC) and hydroxyethyl methacrylate (CH ₂ ═CCH ₃ (COOCH ₂ CH ₂ OH): HEMA) was prepared (Examples 76 to 76). 78). In this case, the composition ratio (PVnC: HEMA) of the copolymerization monomer was changed to 95: 5, 80:20, or 60:40 as shown in FIG. Further, 1M-LiClO ₄ / propylene carbonate (PC) was used as the electrolyte solution with a swelling amount of 200% by weight.

  Furthermore, 0.5-2 equivalent of toluene-2,4-diisocyanate is added to each of the obtained films with respect to the HEMA unit, and the resultant is crosslinked by heating at 100 ° C. for 24 hours to form a polymer solid electrolyte film comprising a crosslinked product. (Examples 79 to 81) were obtained.

The electrical conductivity and tensile strength at 25 ° C. of the obtained uncrosslinked and crosslinked films were determined. The results are shown in FIGS. 7 and 8, ● indicates a tensile strength of 3 kgf / cm ² or more, ▲ indicates a tensile strength of 0.2 kgf / cm ² or more and less than 3 kgf / cm ² , and × indicates that the polymer solid electrolyte cannot be formed into a film and is sticky The gel state is shown.

  From the results shown in FIGS. 7 and 8, the tensile strength is improved by crosslinking the polymer solid electrolyte film made of the PVnC-HEMA copolymer, and at this time, the ionic conductivity is maintained at substantially the same value. I understand that. Therefore, it can be seen that the mechanical strength of the film can be improved without impairing the ionic conductivity by constituting the polymer solid electrolyte film from the crosslinked body.

Examples 82-84, 85-87
A solid polymer electrolyte film made of an uncrosslinked copolymer of polyvinylethylene carbonate (PVEC) and hydroxyethyl methacrylate (CH ₂ ═CCH ₃ (COOCH ₂ CH ₂ OH): HEMA) was produced (Examples 82 to 84). In this case, the composition ratio (PVEC: HEMA) of the copolymerization monomer was changed to 95: 5, 80:20, or 60:40 as shown in FIG. Further, 1M-LiClO ₄ / propylene carbonate (PC) was used as the electrolyte solution with a swelling amount of 200% by weight.

  Furthermore, 0.5-2 equivalent of toluene-2,4-diisocyanate is added to each of the obtained films with respect to the HEMA unit, and the resultant is crosslinked by heating at 100 ° C. for 24 hours to form a polymer solid electrolyte film comprising a crosslinked product. (Examples 85-87).

  The electrical conductivity and tensile strength at 25 ° C. of the obtained uncrosslinked and crosslinked films were determined. The results are shown in FIGS.

  From the results of FIGS. 7 and 8, the solid polymer electrolyte film made of a PVEC-HEMA copolymer is also cross-linked, whereby the tensile strength is improved. At this time, the ionic conductivity is maintained at substantially the same value. I understand that. Therefore, it can be understood that the mechanical strength of the film can be improved without impairing the ionic conductivity by constituting the polymer solid electrolyte film from the crosslinked body.

Examples 88-90, 91-93
A polymer solid electrolyte film comprising an uncrosslinked copolymer of poly (ethylene carbonate) methacrylate (PECMA) and hydroxyethyl methacrylate (CH ₂ ═CCH ₃ (COOCH ₂ CH ₂ OH): HEMA) was produced (implementation) Examples 88-90). In this case, the composition ratio (PECMA: HEMA) of the copolymerization monomer was changed to 95: 5, 80:20, or 60:40 as shown in FIG. Further, 1M-LiClO ₄ / propylene carbonate (PC) was used as the electrolyte solution with a swelling amount of 200% by weight.

  Furthermore, 0.5-2 equivalents of toluene-2,4-diisocyanate was added to each of the obtained films with respect to the HEMA unit, and the resultant was crosslinked by heating at 100 ° C. for 24 hours to form a polymer solid electrolyte film comprising a crosslinked product. (Examples 91-93) were obtained.

  The electrical conductivity and tensile strength at 25 ° C. of the obtained uncrosslinked and crosslinked films were determined. The results are shown in FIGS.

  From the results of FIGS. 7 and 8, the solid polymer electrolyte film made of the PECMA-HEMA copolymer is also cross-linked to improve the tensile strength, and at this time, the ionic conductivity is maintained at substantially the same value. I understand that. Therefore, it can be understood that the mechanical strength of the film can be improved without impairing the ionic conductivity by constituting the polymer solid electrolyte film from the crosslinked body.

Examples 94-102
A polymer solid electrolyte film in which vinylene carbonate (VnC) was crosslinked with a divinyl monomer was produced. In this case, vinylene carbonate (VnC) and formula (7a)

で示されるジビニルモノマーを以下の表１に示す仕込比（ mol％）になるように調整し、さらに電解液として１Ｍ−ＬｉＣｌＯ₄ ／プロピレンカーボネート（ＰＣ）を総仕込みモノマーの重量に対して２５０ｗｔ％になるように加えた。得られた溶液にアゾビスイソブチロニトリル（ＡＩＢＮ）を総仕込みモノマーのモル数に対して０．２〜１．０ｍｍｏｌ加え、窒素で数分間バブリングした。この溶液を底面平滑なテフロンシャーレ内に注ぎ込み、これを窒素を充満した密封容器に入れ、７５℃に設定した恒温槽内にて１２時間重合させた。これにより電解液が膨潤した高分子固体電解質フィルムを得た。

Is adjusted so that the charging ratio (mol%) shown in Table 1 below is obtained, and 1M-LiClO ₄ / propylene carbonate (PC) is further added as an electrolytic solution at 250 wt% with respect to the weight of the total charged monomers. It was added to become. To the obtained solution, azobisisobutyronitrile (AIBN) was added in an amount of 0.2 to 1.0 mmol based on the total number of moles of monomers, and was bubbled with nitrogen for several minutes. This solution was poured into a Teflon petri dish having a smooth bottom surface, placed in a sealed container filled with nitrogen, and polymerized in a thermostat set at 75 ° C. for 12 hours. As a result, a polymer solid electrolyte film in which the electrolyte was swollen was obtained.

  The electrical conductivity at 25 ° C. of the obtained polymer solid electrolyte film was determined. The results are shown in FIGS. From these results, it is understood that high ionic conductivity is maintained when the mechanical strength is improved by forming a polymer solid electrolyte film from a crosslinked product of divinyl monomer.

実施例１０３〜１０７
ビニレンカーボネート（ＶｎＣ）を種々の多官能性モノマーで架橋した高分子固体電解質フィルムを作製した。この場合、ビニレンカーボネート（ＶｎＣ）と式（７ｂ）（略号ＤＭＡ−Ｈ）、

Examples 103-107
Polymeric solid electrolyte films in which vinylene carbonate (VnC) was crosslinked with various polyfunctional monomers were prepared. In this case, vinylene carbonate (VnC) and formula (7b) (abbreviation DMA-H),

式（７ｃ）（略号ＤＭＡ−ＮＰ）、

Formula (7c) (abbreviation DMA-NP),

式（７ｄ）（略号ＤＭＡ−３Ｐ）、

Formula (7d) (abbreviation DMA-3P),

式（７ｅ）（略号ＤＭＡ−４ＥＰ）、

Formula (7e) (abbreviation DMA-4EP),

のジビニルモノマー及び式（９ａ）（略号ＴＭＡ−Ｐ）

Divinyl monomer of formula (9a) (abbreviation TMA-P)

のトリビニルモノマーを以下の表２に示す仕込比（ mol％）になるように調整し、さらに電解液として１Ｍ−ＬｉＣｌＯ₄ ／プロピレンカーボネート（ＰＣ）を総仕込みモノマーの重量に対して２５０ｗｔ％になるように加えた。得られた溶液にアゾビスイソブチロニトリル（ＡＩＢＮ）を総仕込みモノマーのモル数に対して０．２〜１．０ｍｍｏｌ加え、窒素で数分間バブリングした。この溶液を底面平滑なテフロンシャーレ内に注ぎ込み、これを窒素を充満した密封容器に入れ、７５℃に設定した恒温槽内にて１２時間重合させた。これにより電解液が膨潤した高分子固体電解質フィルムを得た。

The trivinyl monomer was adjusted so as to have a charging ratio (mol%) shown in Table 2 below, and 1M-LiClO ₄ / propylene carbonate (PC) as an electrolytic solution was adjusted to 250 wt% with respect to the total charged monomer weight. It was added to become. To the obtained solution, azobisisobutyronitrile (AIBN) was added in an amount of 0.2 to 1.0 mmol based on the total number of moles of monomers, and was bubbled with nitrogen for several minutes. This solution was poured into a Teflon petri dish having a smooth bottom surface, placed in a sealed container filled with nitrogen, and polymerized in a thermostat set at 75 ° C. for 12 hours. As a result, a polymer solid electrolyte film in which the electrolyte was swollen was obtained.

  The electrical conductivity at 25 ° C. of the obtained polymer solid electrolyte film was determined. The result is shown in FIG. From these results, it can be seen that high ionic conductivity is maintained when the mechanical strength is improved by constituting a polymer solid electrolyte film from a crosslinked product of a polyfunctional monomer.

実施例１０８〜１１１
ビニルエチレンカーボネート（ＶＥＣ）又はエチレンカーボネートメタクリレート（ＥＣＭＡ）とジビニルモノマーで架橋した高分子固体電解質フィルムを作製した。この場合、ビニルエチレンカーボネート（ＶＥＣ）又はエチレンカーボネートメタクリレート（ＥＣＭＡ）と、式（７ａ）で示されるジビニルモノマーを以下の表３に示す仕込比（ mol％）になるように調整し、さらに電解液として１Ｍ−ＬｉＣｌＯ₄ ／プロピレンカーボネート（ＰＣ）を総仕込みモノマーの重量に対して２５０ｗｔ％になるように加えた。得られた溶液にアゾビスイソブチロニトリル（ＡＩＢＮ）を総仕込みモノマーのモル数に対して０．２〜１．０ｍｍｏｌ加え、窒素で数分間バブリングした。この溶液を底面平滑なテフロンシャーレ内に注ぎ込み、これを窒素を充満した密封容器に入れ、７５℃に設定した恒温槽内にて１２時間重合させた。これにより電解液が膨潤した高分子固体電解質フィルムを得た。

Examples 108-111
A polymer solid electrolyte film crosslinked with vinyl ethylene carbonate (VEC) or ethylene carbonate methacrylate (ECMA) and a divinyl monomer was prepared. In this case, vinyl ethylene carbonate (VEC) or ethylene carbonate methacrylate (ECMA) and the divinyl monomer represented by the formula (7a) are adjusted so as to have a charging ratio (mol%) shown in Table 3 below, and further an electrolyte solution 1M-LiClO ₄ / propylene carbonate (PC) was added so as to be 250 wt% based on the weight of the total charged monomers. To the obtained solution, azobisisobutyronitrile (AIBN) was added in an amount of 0.2 to 1.0 mmol based on the total number of moles of monomers, and was bubbled with nitrogen for several minutes. This solution was poured into a Teflon petri dish having a smooth bottom surface, placed in a sealed container filled with nitrogen, and polymerized in a thermostat set at 75 ° C. for 12 hours. As a result, a polymer solid electrolyte film in which the electrolyte was swollen was obtained.

  The electrical conductivity at 25 ° C. of the obtained polymer solid electrolyte film was determined. The result is shown in FIG. From these results, it is understood that high ionic conductivity is maintained when the mechanical strength is improved by forming a polymer solid electrolyte film from a crosslinked product of divinyl monomer.

It is a related figure of the electrolyte concentration of the polymer solid electrolyte film of an Example, the kind of organic polymer, and electrical conductivity. It is a related figure of the kind of organic polymer of the polymer solid electrolyte film of an Example, the kind of electrolyte, and electrical conductivity. It is a relationship figure of the swelling amount of the electrolyte solution of the polymer solid electrolyte film of an Example, the kind of organic polymer, and electrical conductivity. It is a related figure of the kind of organic polymer (crosslinked body) of the polymer solid electrolyte film of an Example, the kind of electrolyte, and electrical conductivity. It is a relationship figure of the swelling amount of the electrolyte solution of the polymer solid electrolyte film of an Example, the kind of organic polymer (crosslinked body), and electrical conductivity. It is a related figure of the structural ratio of the copolymerization monomer of the organic polymer (copolymer) of the polymer solid electrolyte film of an Example, and electrical conductivity. It is a related figure of the structural ratio of the copolymerization monomer of the organic polymer (copolymer) of the polymer solid electrolyte film of an Example, and electrical conductivity. It is a related figure of the structural ratio of the copolymerization monomer of the organic polymer (crosslinked body of a copolymer) of the polymer solid electrolyte film of an Example, and electrical conductivity. It is a related figure of the ratio of the divinyl monomer in the organic polymer (crosslinked body) of the polymer solid electrolyte film of an Example, and electrical conductivity. It is a related figure of the structure and electrical conductivity of the divinyl monomer in the organic polymer (crosslinked body) of the polymer solid electrolyte film of an Example. It is the figure which showed the electrical conductivity of the organic polymer (crosslinked body) of the polymer solid electrolyte film of an Example. It is the figure which showed the electrical conductivity of the organic polymer (crosslinked body) of the polymer solid electrolyte film of an Example.

Claims (16)

A battery comprising an organic polymer crosslinked body in which organic polymers having a carbonate group as a functional group are mutually crosslinked , an electrolyte, and an organic solvent in which the electrolyte is soluble ,
The organic polymer is represented by the following formula (1)

(In the formula, R ¹ and R ² are independently hydrogen or a lower alkyl group, and n is an arbitrary integer.) A vinylene carbonate monomer homopolymer having a unit .
battery. The battery according to claim 1, wherein the organic polymer has an average molecular weight of 3 × 10 ^{3 to} 5 × 10 ⁵ . The battery according to claim 1 or 2 wherein the organic solvent is contained 10 to 200 parts by weight based on the organic polymer 100 parts by weight. A battery comprising an organic polymer crosslinked body in which organic polymers having a carbonate group as a functional group are mutually crosslinked, an electrolyte, and an organic solvent in which the electrolyte is soluble,
The organic polymer is represented by the following formula (2)

(Wherein R ¹ and R ² are independently hydrogen or a lower alkyl group, X is a monomer unit copolymerizable with a vinylene carbonate monomer, and m and n are independently any integer. And a copolymer of vinylene carbonate monomer and other monomers having a unit of
battery. The proportion of vinylene carbonate based monomer unit is battery according to claim 4, wherein at least 50 mol% of the organic polymer. Claim 4 or 5 batteries according organic solvent is contained 10 to 400 parts by weight based on the organic polymer 100 parts by weight. A battery comprising an organic polymer crosslinked body in which organic polymers having a carbonate group as a functional group are mutually crosslinked, an electrolyte, and an organic solvent in which the electrolyte is soluble,
The organic polymer has a carbonate group in a side chain;
The organic polymer is represented by the following formula (3)

(Wherein R ¹ , R ² and R ³ are each independently hydrogen or an alkyl group, j is an integer of 0 to 3, and k is an arbitrary integer). Consisting of a homopolymer of
Battery . The battery according to claim 7, wherein the organic polymer has an average molecular weight of 5 × 10 ^{3 to} 5 × 10 ⁵ . The battery according to claim 7 or 8, wherein the organic solvent is contained 10 to 200 parts by weight based on the organic polymer 100 parts by weight. A battery comprising an organic polymer crosslinked body in which organic polymers having a carbonate group as a functional group are mutually crosslinked, an electrolyte, and an organic solvent in which the electrolyte is soluble,
The organic polymer has a carbonate group in a side chain;
The organic polymer is represented by the following formula (4)

Wherein R ¹ , R ² and R ³ are independently hydrogen or an alkyl group, X is a monomer unit copolymerizable with a carbonate-based monomer, j is an integer of 0 to 3, k and m is independently an arbitrary integer.) and comprises a copolymer of a carbonate monomer and another monomer.
Battery . The proportion of the carbonate-based monomer unit in the organic polymer battery according to claim 10, wherein at least 50 mol%. Claim 10 or 11 cell, wherein the organic solvent is contained 10 to 400 parts by weight based on the organic polymer 100 parts by weight. A battery comprising a crosslinked organic polymer, an electrolyte, and an organic solvent in which the electrolyte is soluble,
In the crosslinked organic polymer, an organic polymer having a carbonate group as a functional group is represented by the following formula (7):

(Wherein R ¹ and R ² are independently hydrogen or a methyl group, m is an integer of 1 to 9, C _m H _2m may be linear or branched, and n = 0 to 9 Furthermore, a part of (OC _m H _2m ) _n is represented by the following formula (8):

May be substituted. ) Of diacrylic or dimethacrylic monomers ,
The polymer is represented by the following formula (1)

(In the formula, R ¹ and R ² are independently hydrogen or a lower alkyl group, and n is an arbitrary integer.) A vinylene carbonate monomer homopolymer having a unit.
Battery . A battery comprising a crosslinked organic polymer, an electrolyte, and an organic solvent in which the electrolyte is soluble,
In the crosslinked organic polymer, an organic polymer having a carbonate group as a functional group is represented by the following formula (7):

(Wherein R ¹ and R ² are independently hydrogen or a methyl group, m is an integer of 1 to 9, C _m H _2m may be linear or branched, and n = 0 to 9 Furthermore, a part of (OC _m H _2m ) _n is represented by the following formula (8):

May be substituted. ) Of diacrylic or dimethacrylic monomers ,
The organic polymer is represented by the following formula (2)

(Wherein R ¹ and R ² are independently hydrogen or a lower alkyl group, X is a monomer unit copolymerizable with a vinylene carbonate monomer, and m and n are independently any integer. And a copolymer of vinylene carbonate monomer and other monomers having a unit of
Battery . A battery comprising a crosslinked organic polymer, an electrolyte, and an organic solvent in which the electrolyte is soluble,
In the crosslinked organic polymer, an organic polymer having a carbonate group as a functional group is represented by the following formula (7):

(In the formula, R ¹ and R ² are independently hydrogen or a methyl group, an integer of _m = 1~9, C m H _2m may be a well-branched be linear, n = 0 to 9 Furthermore, a part of (OC _m H _2m ) _n is represented by the following formula (8):

May be substituted. ) Of diacrylic or dimethacrylic monomers ,
The organic polymer has a carbonate group in a side chain;
The organic polymer is represented by the following formula (3)

(Wherein R ¹ , R ² and R ³ are each independently hydrogen or an alkyl group, j is an integer of 0 to 3, and k is an arbitrary integer). Consisting of a homopolymer of
Battery . A battery comprising a crosslinked organic polymer, an electrolyte, and an organic solvent in which the electrolyte is soluble,
In the crosslinked organic polymer, an organic polymer having a carbonate group as a functional group is represented by the following formula (7):

(Wherein R ¹ and R ² are independently hydrogen or a methyl group, m is an integer of 1 to 9, C _m H _2m may be linear or branched, and n = 0 to 9 Furthermore, a part of (OC _m H _2m ) _n is represented by the following formula (8):

May be substituted. ) Of diacrylic or dimethacrylic monomers ,
The organic polymer has a carbonate group in a side chain;
The organic polymer is represented by the following formula (4)

Wherein R ¹ , R ² and R ³ are independently hydrogen or an alkyl group, X is a monomer unit copolymerizable with a carbonate-based monomer, j is an integer of 0 to 3, k and m is independently an arbitrary integer.) and comprises a copolymer of a carbonate monomer and another monomer.
Battery .

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