JP2003229022A - High polymer solid electrolyte and its manufacturing method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a high polymer solid electrolyte having an excellent safety, stability with age, and displaying a high ion conductivity of 10<SP>-3</SP>S/cm or more, which is excellent in moldability and is simply manufactured in a condition wherein impurities are lessened as far as possible. <P>SOLUTION: After uniformly mixing a salt monomer precursor having ionic interaction and one or more kinds of polymerizable monomer having good compatibility with the salt monomer precursor together with other constituents at room temperature or lower temperatures, the salt monomer precursor is converted to a salt monomer by heating the mixture at room temperature or higher temperatures, or by action of active ray, and a copolymerized polymer with a specific structure forming a matrix is produced by copolymerizing reaction of the salt monomer and the copolymerizable monomer. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polymer solid electrolyte, and more specifically, it exhibits high ionic conductivity by mainly containing a lithium metal compound as a charge carrier in a polymer matrix, In addition, in the process of preparing a solid polymer electrolyte having excellent stability and stability over time without liquid leakage, and excellent moldability, salt monomers that are difficult to purify in high purity by a conventional method due to high hygroscopicity, etc. Without synthesizing and purifying, the precursor of the salt monomer is mixed with other components of the solid polymer electrolyte at room temperature or below room temperature, and then heated at room temperature or above room temperature to obtain the desired product. The present invention relates to a polymer solid electrolyte and a method for producing the same, wherein a salt monomer is formed inside the polymer solid electrolyte.

[0002]

2. Description of the Related Art In recent years, there has been a demand for portable information devices such as mobile phones, PDAs, and notebook computers, portable devices such as MD players, MP3 players, and digital cameras that are frequently used outdoors, or the aging society in the future. With the spread of portable medical devices and PHS type assistive devices, which are expected to increase, demand for lighter, smaller volume, cheaper, safer, and higher-power secondary batteries is increasing. Polymer solid electrolytes have been attracting attention as secondary battery materials for power supplies that meet these requirements.

Conventionally, as an electrolyte for secondary batteries, generally,
A liquid electrolyte in which an ionic compound is dissolved in an organic solvent that is relatively stable electrochemically has been used. However, in this case, since the fluid contains a fluid liquid inside the battery, it has been overcharged or physically damaged due to long-term use, when the battery itself was externally heated for some reason, or due to equipment failure. In this case, there has always been a risk that the electrolytic solution, which may damage the human body or damage the equipment used, leaks from the inside of the battery to the outside.

Therefore, various methods have been used so far.
Attempts have been made to prevent the electrolyte from leaking to the outside. One of them is a method in which the electrolytic solution contains or is impregnated with a polymer compound and the entire electrolytic solution is made into a gel. The gelling method includes a method of physically gelling by interaction between polymers and a method of directly linking polymers by covalent bond using a cross-linking agent. In general, the former is often called a physical gel and the latter is often called a chemical gel. Since these are flexible, they are easy to mold, and many are relatively lightweight, which is a great design advantage for small devices that can secure only a small space for secondary batteries. . However, since it contains a relatively large amount of organic solvent, there are many cases where the morphological stability in the high temperature region is insufficient, and for example, in an unexpected event, liquid leakage occurs when exposed to high temperature conditions for a long time, or There was also an example in which the pressure in the battery container was damaged due to an increase in internal pressure.

On the other hand, so-called "all solid electrolytes" containing no organic solvent have been actively developed. An example is a mixture of various lithium salts and polyethylene oxide. In this case, the damages such as liquid leakage as described above are almost overcome, but the battery characteristics are poor in the low temperature region because there is no liquid portion, and the system cannot develop a predetermined conductivity unless the temperature is relatively high. There are many.
This is a fatal drawback for various portable devices that are often exposed to relatively low temperature conditions in the human activity area.

On the other hand, in order to overcome the drawbacks found in gel-type electrolytes and all-solid-state electrolytes, an ionic compound that has fluidity at room temperature, a so-called "normal temperature molten salt", is combined with any polymer compound to form an electrolyte. Attempts to use it have also been made. However, many of them use relatively dangerous compounds such as aluminum halide compounds, which poses a serious problem from the viewpoint of safety. In addition, since it has been difficult to secure a wide potential window for the imidazolium type compound which has been conventionally studied, it has a drawback that it is often difficult to apply it to a lithium battery or the like for the purpose of increasing the capacity.

[0007] Further, since the room temperature molten salt often takes the form of a liquid or a paste at room temperature and the vapor pressure thereof is extremely low in many cases, refining by an ordinary method inevitably involves great difficulty. . However, on the other hand, since the vapor pressure is extremely low, it is a viscous liquid in some cases, and the electric conductivity is relatively high, most of the various conditions that should be satisfied as a solid electrolyte constituent if the difficulty of purification can be cleared. It is certain that it is a rare material that satisfies all requirements.

On the other hand, solid electrolytes containing inorganic compounds as a base polymer have been actively developed recently, and some of them have been reported to have a relatively high conductivity near room temperature. However, none of them has been able to overcome the drawback that molding is difficult because of poor flexibility, and it cannot be denied that they are the biggest obstacles to commercialization.

[0009]

[Problems to be Solved by the Invention] As described above,
Various types of solid electrolytes have been proposed so far for secondary battery applications, and the development competition for the next-generation solid electrolytes is becoming fierce every year. Although there are advantages and disadvantages in all modes, it is not possible to unequivocally discuss superiority or inferiority, but research on gel electrolytes has been actively conducted so far because of its excellent moldability and relatively high conductivity. . However, if even the conductivity problem can be solved, a more stable / safer all-solid-state electrolyte would be preferable.

Here, once again, when the problems in each system are sorted out, in the case of a gelled solid electrolyte, there is a risk of liquid leakage and ignition due to the inclusion of a relatively large amount of solvent,
Stability over time (whether there is no solid-liquid separation due to partial crystallization of the gel skeleton), etc. In the case of an all-solid electrolyte,
The deterioration of electrical conductivity at low temperature, moldability, etc. may be mentioned.

When the room temperature molten salt is applied as one of the constituents of the solid electrolyte, it is further difficult to synthesize and purify the constituents. Further, depending on the combination of chemical species as raw materials constituting the polymer solid electrolyte, the compatibility of the high molecular weight component and other components contained in the polymer solid electrolyte, or the compatibility of the metal salt and other components. As described above, the compatibility between the constituent components is not good, which may cause a large problem in production. In this case, improvement of the compatibility between the constituent components of the solid polymer electrolyte is also an important issue.

Therefore, the main object of the present invention is to exhibit a high ionic conductivity of 10 ^-3 S / cm or more even near room temperature, and to be excellent in flexibility, mechanical strength, flexibility and stability over time. It is intended to obtain a polymer solid electrolyte which is sufficiently safe in the human activity area as easily as possible and in a state where impurities are as small as possible.

[0013]

Means for Solving the Problems As a result of intensive studies to achieve the above object, the present inventors have found that when a salt monomer having an ionic interaction is uniformly dispersed in a polymer matrix. In addition, instead of directly using the salt monomer itself, a highly purified salt monomer precursor is uniformly dispersed in the system and then converted into a salt monomer by the action of heat energy or actinic rays. According to the above, it was found that a solid polymer electrolyte having a more uniform internal structure and a low content of impurities and water can be obtained, and further studies were conducted to complete the present invention.

That is, the present invention provides a polymer solid electrolyte comprising a copolymerized polymer having a specific structure, which comprises a salt monomer component having an ionic interaction and one or more kinds of polymerizable monomer components, a metal salt, and a plasticizer. Wherein the copolymer having a specific structure comprises a salt monomer precursor and one or more kinds of polymerizable monomers having good compatibility with the salt monomer precursor, together with other components, at room temperature or a temperature of room temperature or lower. After uniformly mixing with, heated at room temperature or room temperature or higher, or by the action of actinic rays, the salt monomer precursor is converted into a salt monomer, and at the same time produced by the copolymerization reaction of the salt monomer and the polymerizable monomer. It is a polymer solid electrolyte characterized by being a product and a method for producing the same.

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention does not directly use the salt monomer having an ionic interaction itself, but preliminarily highly purifies the precursor of the salt monomer and uniformly mixes it in the system containing the polymerizable monomer. After that, the main point is to obtain a polymer solid electrolyte having a more homogeneous internal structure and a low content of impurities and water by converting this into a salt monomer and copolymerizing it.

According to this method, even if the solid salt monomer does not have good compatibility with the other components of the solid electrolyte, the salt monomer precursor has a relatively low polarity.
In many cases, the compatibility with other constituent components is good, and the salt monomer component can be uniformly dispersed in the system. This salt monomer precursor is a compound that does not undergo chemical or physical changes at room temperature or lower and can exist stably, but is converted to the desired salt monomer by being treated with heat energy or actinic rays. At the same time, due to the action of the polymerizable functional group, it is stably immobilized in the polymer matrix by a covalent bond.

By uniformly coexisting the alkali metal salt or alkaline earth metal salt and the plasticizer in the polymer solid electrolyte, the mobility of the chemical species functioning as a charge carrier is not significantly lowered, A solid polymer electrolyte that can exhibit high ionic conductivity, is free from liquid leakage, and is excellent in safety, stability over time, and moldability is realized.

Such a salt monomer precursor is represented by the general formula [I] and comprises a nitrogen-containing compound having a polymerizable functional group and an organic acid ester having a polymerizable functional group. Examples thereof include those represented by the general formula [II], which are composed of a sulfur-containing compound having a polymerizable functional group and an organic acid ester having a polymerizable functional group, and a mixture thereof may be used.

[0019]

[Chemical 3]

In the general formula [I], X₁, X₂Is R₃as well as
R₂-P₂P combination of₁, P₂Each is heavy
Ac represents a substituent containing a compatible functional group, represented by the general formula [I].
When a compound is converted into a salt monomer, ionic interactions
R represents a functional group directly involved in₁, R₂, R₃，
R_Four, R_FiveAre an alkyl group, an alkenyl group, and aral, respectively.
Kill group, aralkenyl group, alkoxyalkyl group, acyl group
Ruoxyalkyl group, sulfoalkyl group, aryl group,
Alternatively, it comprises an aromatic heterocyclic residue or the like. X₂, R_Four, R_Five
Any one or more of them are covalently bonded to each other.
May be linked together to form a ring structure. Well
X₂-N, R_Four-N, R_Five-N of the covalent bond
If either one is a double bond instead of a single bond,
R_Four, R_FiveThere is no one of them. Also, P₁-R₁
And P₂-R₂Are linked by multiple covalent bonds
Well, P₂Is R₂Besides R₃, R_Four, R_FiveAt the same time covalent bond
It may be connected by. Also, P₁Or
R₁Is P₂, R₂, R₃, R_Four, R _FiveOne or more parts of
It may be linked by one or more covalent bonds.
Similarly P₂Or R₂Is P₁, R₁One or more parts of
It may be linked by one or more covalent bonds.
However, in any case, P is connected by these interconnections.₁And P₂
The polymerizability of is not impaired. Such salt monomer precursor
May be any one kind or a mixture of plural kinds.
Yes.

[0021]

[Chemical 4]

In the general formula [II], X ₃ and X ₄ are a combination of R ₈ and R ₇ -P ₄ , P ₃ and P ₄ are substituents each containing a polymerizable functional group, and Ac is a general formula [II]. II] represents a functional group directly involved in ionic interaction when the compound represented by the formula [II] is converted to a salt monomer, and R ₆ , R ₇ , R ₈ and
Each R ₉ is composed of an alkyl group, an alkenyl group, an aralkyl group, an aralkenyl group, an alkoxyalkyl group, an acyloxyalkyl group, a sulfoalkyl group, an aryl group, an aromatic heterocyclic residue or the like. X ₄ and R ₉ may be linked to each other by a covalent bond to form a cyclic structure. When the covalent bond represented by X ₄ -S is not a single bond but a double bond, R ₉ does not exist. Also,
P ₃ -R ₆ and P ₄ -R ₇ may be linked by a plurality of covalent bonds, P ₄ is may be covalently linked at the same time as other R _8, R ₉ of R _7. Further, P ₃ or R ₆ may be linked to one or more sites of P ₄ , R ₇ , R ₈ and R ₉ by one or more covalent bonds. Similarly, P ₄ or R ₇ may be linked to one or more sites of P ₃ and R ₆ by one or more covalent bonds. However, in any case, the polymerizability of P ₃ and P ₄ is not hindered by their mutual connection. Any one kind or a plurality of kinds of such salt monomer precursors may be mixed.

The molar ratio of the cation precursor site converted to the cation constituting the salt monomer and the anion precursor site converted to the anion is preferably in the range of 50/1 to 1/50, and further, It is preferably 10/1 to 1/1, but is not particularly limited to this range.

These salt monomer precursors are stable compounds that do not undergo any chemical or physical changes at room temperature or below, but are stable at room temperature or above room temperature, or by actinic rays. By the treatment, it is converted into a salt monomer having a structure represented by the general formula [III] or the general formula [IV].

[0025]

[Chemical 5]

The compound of the general formula [III] is composed of an alkyl quaternary ammonium cation having a polymerizable functional group or a nitrogen-containing heterocyclic cation, and an organic acid anion having a polymerizable functional group. ^- represents an ionic functional groups directly involved in ionic interactions.

[0027]

[Chemical 6]

The compound of the general formula [IV] is composed of a sulfonium cation having a polymerizable functional group and an organic acid anion having a polymerizable functional group, and Ac ⁻ is directly involved in ionic interaction. Represents an ionic functional group involved.

[0029] Incidentally, the ionic functional group Ac directly involved in ionic interactions ^- as, for example, a carboxyl group, but sulfoxyl group can be mentioned as an example,
The present invention is not limited to these specific examples. Further, the molar ratio of the cation site and the anion site constituting the salt monomer, that is, the cation / anion ratio is preferably in the range of 10/1 to 1/10, and further 1 /
It is preferably 1, but not particularly limited to this range. If this ratio is not 1/1, it is sufficient if the charge balance is achieved with other components of the solid polymer electrolyte such as metal salts.

When the molar ratio of the cation and the anion constituting the salt monomer is not 1/1, in order to balance the charge, a high molecular weight chemical species or a low molecular weight chemical species having no polymerizable functional group or various metal salts Etc. are preferably added. However, in this case, in order to avoid a decrease in the transport number of the cationic carrier (for example, lithium ions) in the electrolyte, the mobility of the anionic carrier is low,
Alternatively, it is preferable that the concentration of anionic species having a relatively high mobility (halogen anion, etc.) contained in the electrolyte is low. Although any chemical species satisfying this condition can be put to practical use, in order to obtain good results in electrical characteristics such as electric conductivity, anionic chemicals with particularly high mobility are required. It is desirable that the species, that is, the halogen anion concentration is 500 ppm or less. In the case of a conventional solid electrolyte using a room temperature molten salt, a metal acid anion such as AlCl ^{4 −} may be used as a counter anion, but in this case, the halogen ion has only a low concentration immediately after the preparation of the polymer solid electrolyte. Even if it was not contained, there were many cases in which it decomposed due to moisture absorption from the atmosphere to generate a large amount of halogen anions in the system during long-term use, resulting in deterioration of battery characteristics. The polymer solid electrolyte developed by the present inventors is characterized by using a salt monomer, but in the process of synthesizing a salt monomer, the counter anion is exchanged with a counter anion having a polymerizable functional group,
Alternatively, since the counter ion can be exchanged at the same time as the counter cation, it is easy to reduce the content of the halogen anion having high mobility.

As the polymerization reaction of the salt monomer formed by being converted by the action of heat energy or actinic ray and the polymerizable monomer, various known methods such as radical polymerization, ionic polymerization, coordination polymerization, polycondensation, addition polymerization, etc. However, radical polymerization, coordination polymerization, polycondensation, and addition polymerization are preferable because of the simplicity of the polymerization operation, but are not particularly limited thereto.

As a method for converting the salt monomer precursor used in the present invention into a salt monomer, use of heat energy or actinic light can be mentioned. A method of alkylating an amine or thioether by heating at room temperature or higher is available. Most preferred. In particular, when an alkyl or aryl sulfonic acid ester is used as the organic acid ester and a trialkylamine or an alkylarylamine is used as the amine, the alkylation reaction proceeds at a good yield, and the alkyl ester is uniformly dispersed in the reaction system. A salt monomer is produced. Further, at this time, when the polymerization reaction by the polymerizable functional group is simultaneously performed in parallel, the salt monomer is solidified while being uniformly dispersed in the system, so that a solid polymer electrolyte having a uniform internal composition can be obtained. The precursors and the reaction modes listed above are not limited to the above and are not particularly limited as long as the polarity can be changed.

The one or more kinds of polymerizable monomers having a good compatibility with the salt monomer precursor used in the present invention are polymers for controlling plasticity, moldability and thermal stability of the polymer solid electrolyte. It is added for the purpose of adjusting the viscosity of the uncured undiluted solution of the solid electrolyte, and preferably has no ionic dissociative group. As the polymerizable monomer for this purpose, when radically copolymerizing with the salt monomer,
A carboxylic acid ester, a sulfonic acid ester, or an aromatic compound having a carbon-carbon double bond is preferable, and further, an acrylic acid ester, a methacrylic acid ester, a sulfonic acid ester, an acrylamide, a methacrylamide, a sulfonamide, or a substitution. An aryl compound represented by a styrene derivative having a group is preferable, but it is not particularly limited as long as it is a chemical species that can be copolymerized with the salt monomer. Further, as long as there is no problem in battery characteristics, the compound may be the same as any of the salt monomer precursor compounds shown in the above general formulas [I] and [II].

The compatibility of the salt monomer precursor and the polymerizable monomer is determined by the form of a transparent and uniform solution or paste in the state of an uncured undiluted solution immediately after mixing the salt monomer precursor, the polymerizable monomer, and other constituent components. Is most preferred. However, when the solid polymer electrolyte is actually produced, it is transparent as long as it can maintain its shape sufficiently stably in the state of emulsification, emulsion, colloid, coacervate, etc. within the finite time range which is inevitably required. Not only the polymerizable monomer that can form a uniform solution, various polymerizable monomers can be applied.

The metal salt used in the present invention is Li
PF ₆ , LiClO ₄ , LiCF ₃ SO ₃ , LiAsF ₆ , LiB
F ₄ , LiN (CF ₃ SO ₃ ) ₂ , C ₄ F ₉ SO ₃ Li, LiC
(CF ₃ SO ₂ ) ₃ and LiF may be mentioned, and these may be used alone or in admixture of two or more.

As the plasticizer used in the present invention, propylene carbonate (PC), ethylene carbonate (EC), dimethyl carbonate, diethyl carbonate, ethylmethyl carbonate, dimethoxyethane, tetrahydrofuran, dioxane, dimethyl sulfoxide, dimethylformamide, dimethylacetamide. And the like. These may be used alone or in combination of two or more. However, in order to realize the characteristics of the all solid polymer electrolyte, it is desirable that the addition amount of the plasticizer is 30 wt% or less with respect to the entire polymer solid electrolyte.

[0037]

EXAMPLES The present invention will be specifically described below based on examples, but the present invention is not limited thereto.

Example 1 Precursor A-1 of Salt Monomer A: Synthesis of p-Styrenesulfonic Acid Methyl Ester 20.3 g (100 mmo) of styrenesulfonyl chloride
l) is homogeneously dissolved in 200 ml of anhydrous methanol.
To this, 19.5 g of a 28 wt% sodium methoxide / methanol solution was slowly added dropwise at room temperature with stirring, and the reaction proceeded quantitatively. After the reaction solution was diluted with distilled water, the product was extracted with chloroform, washed with an aqueous sodium hydrogen carbonate solution and distilled water, and the recovered chloroform phase was concentrated under reduced pressure to recover a crude product. The crude product was purified by vacuum distillation according to a conventional method to obtain a pale yellow and transparent liquid product: styrenesulfonic acid methyl ester.

Precursor A-2 of Salt Monomer A: Synthesis of p-Diethylaminomethylstyrene Diethylamine 7.3
1 g (100 mmol), potassium carbonate 7.60 g (55
mmol), 100 ml of special grade ethanol, and 5 ml of distilled water were gently stirred at room temperature, and 15.3 g (100 mmol) of chloromethylstyrene / diluted grade of special grade ethanol was slowly added dropwise. After the dropping,
The stirring was slightly increased and the mixture was stirred overnight at room temperature. After the reaction solution was filtered to remove insoluble matter, the filtrate was acidified with hydrochloric acid and toluene was added for liquid separation operation to collect only the aqueous phase. The aqueous phase was made basic with a 5N sodium hydroxide aqueous solution, toluene was added to perform liquid separation operation, and the toluene phase was recovered.
After the toluene phase was dried over anhydrous sodium sulfate overnight, the solvent was distilled off under reduced pressure to obtain a product: p-diethylaminomethylstyrene.

Preparation of Polymer Solid Electrolyte The above salt monomer precursor A-1: 0.01119 g, precursor A-2: 0.0114 g, ethylene glycol dimethacrylate 0.0119 g, and methyl acrylate 0.1.
0897 ml of (1M) LiPF ₆ [EC / PC] solution 0.
744 ml was mixed at room temperature and dissolved uniformly. After sufficiently degassing this solution, heat treatment was performed at 50 ° C./30 min. Immediately after the treatment, 0.167 ml of a 240 mM benzoyl peroxide [EC / PC] solution was added and stirred to uniformly dissolve the solution.
After heating for 0 minutes, a pale yellow transparent gel-like polymer electrolyte was obtained.

Conductivity Evaluation of Polymer Solid Electrolyte The conductivity of the polymer electrolyte obtained above was measured by an AC impedance method. The frequency range at the time of measurement was 50 Hz to 30 MHz, and the voltage was 0.5 V. As a result of the measurement, the electric conductivity at room temperature (20 ° C) is 4.75 x 1
It was 0 ^-3 S / cm. This pale yellow transparent gel-like solid did not show discoloration / decomposition or the like even after 2 months.

Example 2 Preparation of Polymer Solid Electrolyte The above salt monomer precursor A-1: 0.6443 g, precursor A-2: 0.6152 g, ethylene glycol dimethacrylate 0.0991 g, dimethylacrylamide 0.1.
02 ml, ethylene carbonate / propylene carbonate [1 mol / 1 mol] mixed solvent 0.150 ml, and lithium perchlorate powder 0.2128 g were mixed at room temperature and stirred for a while to be uniformly dissolved. Subsequent to this, 240 mM benzoyl peroxide [EC / PC] solution 0.167 m
1 was added and stirred to dissolve uniformly. After thoroughly degassing this solution, it was heated at 80 ° C. for 100 minutes to obtain a colorless, transparent and flexible solid polymer electrolyte.

Conductivity Evaluation of Polymer Solid Electrolyte The conductivity of the obtained polymer electrolyte was measured in the same manner as in Example 1. As a result, the conductivity was 5.81 × 10 ⁻³ S /
In cm, discoloration / decomposition etc. were not observed even after 2 months.

[Comparative Example 1] Synthesis of salt monomer A Salt monomer precursor A-1 obtained in Example: 3.965
g (20 mmol), and A-2: 3.786 g (20
(mmol) was uniformly mixed, and heated and stirred at 50 ° C./60 min. The reaction proceeded quantitatively. Tetrahydrofuran was added to the obtained viscous product to loosen it, and a white solid substance was collected. This was purified by recrystallization and salt monomer A
Got

[Preparation of Polymer Solid Electrolyte] In Example 1, when the polymer solid electrolyte was prepared, the salt monomer A obtained above was used instead of the salt monomer precursors A-1 and A-2. The salt monomer A used was LiPF.
₆ Solubility in [EC / PC] solution was low, and a uniform solution was not obtained.

[0046]

According to the present invention, 10 ^-3 S even at room temperature
/ Cm or more, to express a high ionic conductivity, excellent in flexibility, mechanical strength, flexibility, stability over time, to produce a solid polymer electrolyte easily and in a state with as few impurities as possible Is possible.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) // H01M 10/40 H01M 10/40 BF term (reference) 4J011 PA06 PA26 PA30 PA35 PA37 PA45 PB23 PB27 PC02 PC08 4J100 AB07P AB07Q AL02R AL03R AL62R AM15R AM19R BA32P BA55Q CA04 CA05 EA03 FA18 JA43 5G301 CA08 CA16 CA30 CD01 5H029 AJ06 AM16 CJ02 DJ09 HJ01 HJ02

Claims (9)

[Claims] 1. A polymer solid electrolyte comprising a copolymerized polymer having a specific structure, comprising a salt monomer component having ionic interaction and one or more polymerizable monomer components, a metal salt, and a plasticizer. , A copolymer having a specific structure, a salt monomer precursor, and one or more polymerizable monomers having good compatibility with the salt monomer precursor, together with other constituents, at room temperature or at a temperature of room temperature or less After mixing, the salt monomer precursor is converted into a salt monomer by heating at room temperature or a temperature higher than room temperature, or by the action of actinic rays, and at the same time, it is produced by a copolymerization reaction of the salt monomer and a polymerizable monomer. A solid polymer electrolyte characterized by: 2. The salt monomer precursor is represented by the general formula [I] and is composed of a nitrogen-containing compound having a polymerizable functional group and an organic acid ester having a polymerizable functional group. The polymer solid electrolyte according to claim 1. [Chemical 1] Wherein, X _1, X ₂ is a combination of R ₃ and R ₂ -P _2, substituents containing respectively P _1, P ₂ polymerizable functional group, A
c represents a functional group directly involved in ionic interaction when the compound represented by the general formula [I] is converted into a salt monomer, and R ₁ , R ₂ , R ₃ , R ₄ , R ₅ Are each an alkyl group, an alkenyl group, an aralkyl group, an aralkenyl group, an alkoxyalkyl group, an acyloxyalkyl group, a sulfoalkyl group, an aryl group, or an aromatic heterocyclic residue. Any one or more of X ₂ , R ₄ and R ₅ may be mutually linked by a covalent bond to form a cyclic structure. _{Further, X 2 -N, R 4 -N} , R 5 -
When one of the covalent bonds represented by N is a double bond instead of a single bond, then one of R ₄ and R ₅ does not exist. Also, P ₁ -R ₁ and P ₂ -R ₂ may also be connected by a plurality of covalent bonds, P ₂ Other R ₂ R _3,
It may be linked by a covalent bond at the same time as R ₄ and R ₅ . Further, P ₁ or R ₁ is P ₂ , R ₂ , R ₃ , R ₄ ,
It may be linked to one or more sites of R ₅ by one or more covalent bonds. Similarly, P ₂ or R ₂ is P
_It may be linked to one or more sites of ₁ , R ₁ by one or more covalent bonds. However, in any case, the polymerizability of P ₁ and P ₂ is not hindered by their mutual connection. Any one kind or a plurality of kinds of such salt monomer precursors may be mixed. 3. The salt monomer precursor is represented by the general formula [II] and comprises a sulfur-containing compound having a polymerizable functional group and an organic acid ester having a polymerizable functional group. The polymer solid electrolyte according to claim 1. [Chemical 2] Wherein, X _3, X ₄ is a combination of R ₈ and R ₇ -P _4, substituents containing P _3, P ₄ are each polymerizable functional group, A
c represents a functional group directly involved in ionic interaction when the compound represented by the general formula [II] is converted into a salt monomer, and R ₆ , R ₇ , R ₈ and R ₉ are each an alkyl group. A group, an alkenyl group, an aralkyl group, an aralkenyl group, an alkoxyalkyl group, an acyloxyalkyl group, a sulfoalkyl group, an aryl group, or an aromatic heterocyclic residue. X ₄ and R ₉ may be linked to each other by a covalent bond to form a cyclic structure. In addition, when the covalent bond represented by X ₄ -S is not a single bond but a double bond, R ₉
Does not exist. In addition, P ₃ -R ₆ and P ₄ -R ₇ may be linked by a plurality of covalent bonds, and P ₄ is R ₇ as well as R ₇ .
_It may be linked by a covalent bond at the same time as ₈ and R ₉ . Further, P ₃ or R ₆ is 1 of P ₄ , R ₇ , R ₈ and R ₉ .
It may be linked to one or more sites by one or more covalent bonds. Similarly, P ₄ or R ₇ may be linked to one or more sites of P ₃ and R ₆ by one or more covalent bonds. However, in any case, the polymerizability of P ₃ and P ₄ is not hindered by their mutual connection. Any one kind or a plurality of kinds of such salt monomer precursors may be mixed. 4. The salt monomer precursor is a mixture of a compound represented by the general formula [I] and a compound represented by the general formula [II], wherein the salt monomer precursor is a mixture. Polymer solid electrolyte. 5. A halogen ion, ie, F ⁻ , contained as a counter anion of the cation contained in the salt monomer.
5. The solid polymer electrolyte according to claim 1, wherein the amount of Cl ⁻ , Br ⁻ , or I ⁻ is 500 ppm or less with respect to the total solid polymer electrolyte. 6. The polymer according to claim 1, wherein the polymerizable monomer having a good compatibility with the salt monomer precursor has no ionic dissociative group. Solid electrolyte. 7. The metal salt according to claim 1, wherein the metal salt is an alkali metal salt or an alkaline earth metal salt, or a mixture of two or more thereof. Polymer solid electrolyte. 8. A method for producing a polymer solid electrolyte comprising a copolymerized polymer having a specific structure, comprising a salt monomer component having ionic interaction and one or more polymerizable monomer components, a metal salt, and a plasticizer. Where the salt monomer precursor and one or more polymerizable monomers having good compatibility with the salt monomer precursor are uniformly mixed at room temperature or at a temperature of room temperature or less with other components, Alternatively, the salt monomer precursor is converted into a salt monomer by heating at room temperature or higher, or by the action of actinic rays, and a copolymerization polymer having a specific structure is produced by a polymerization reaction between the salt monomer and a polymerizable monomer. A method for producing a polymer solid electrolyte, comprising: 9. The salt monomer precursor is a nitrogen-containing compound represented by the general formula [I] and having a polymerizable functional group, or
Characterized by comprising a sulfur-containing compound represented by the general formula [II] having a polymerizable functional group, and an organic acid ester having a polymerizable functional group, or a mixture thereof. The method for producing a polymer solid electrolyte according to claim 8.