JP2021118180A - Polymer electrolyte composition and all solid lithium ion secondary battery - Google Patents

Abstract

To provide a polymer electrolyte composition having excellent moldability and capable of obtaining a battery having good cycle characteristics.SOLUTION: There is provided a polymer electrolyte composition comprising a polymer (P) of a monomer composition containing a monomer (m1) represented by the general formula 1 and/or a monomer (m2) represented by the general formula 2 and a monomer (m3) represented by the general formula 3 and a lithium salt, wherein the total weight ratio of the monomer (m1) and the monomer (m2) in the monomer composition is 10 to 60 wt.% based on the weight of the monomer composition, the weight ratio of the monomer (m3) in the monomer composition is 40 to 90 wt.% based on the weight of the monomer composition, the weight ratio of the polymer (P) is 70 to 90 wt.% based on the weight of the polymer electrolyte composition and the weight ratio of the lithium salt is 10 to 30 wt.% based on the weight of the polymer electrolyte composition.SELECTED DRAWING: None

Description

The present invention relates to a polymer electrolyte composition and an all-solid-state lithium ion secondary battery using the same.

In recent years, there has been an urgent need to reduce carbon dioxide emissions for environmental protection. In the automobile industry, expectations are high for the reduction of carbon dioxide emissions by introducing electric vehicles (EVs) and hybrid electric vehicles (HEVs), and the development of secondary batteries for driving motors, which holds the key to their practical application, is enthusiastic. It is done. As a secondary battery, attention is focused on a lithium ion battery that can achieve high energy density and high output density.

Among them, as a solid battery, there is no possibility that the organic solvent will volatilize, and gas will be generated inside the battery due to the progress of the decomposition reaction of the organic solvent, which is a side reaction during charging and discharging, to expand the battery. A lithium ion secondary battery using an electrolyte is being studied.
Regarding solid electrolytes, polymer electrolyte compositions that exhibit sufficient ionic conductivity to start a battery by adding an electrolyte to a polymer compound having a carbonate structure or a pyrrolidone structure have been reported (Patent Documents 1 and 2). ..

Japanese Unexamined Patent Publication No. 10-67849 Japanese Unexamined Patent Publication No. 2018-85331

However, polymers having a carbonate structure or a pyrrolidone structure often form crystals locally, and are hard and brittle, so that there is a problem in moldability. In addition, since it cannot follow the expansion and contraction of the electrode due to repeated charging and discharging, there is also a problem that the battery capacity is significantly reduced during long-term use. In response to these, it has been desired to develop a polymer electrolyte composition capable of obtaining a battery having excellent moldability and good cycle characteristics.

The present invention is a polymer electrolyte composition capable of obtaining a battery having excellent moldability and good cycle characteristics, and is an all-solid-state lithium ion secondary battery using the polymer electrolyte composition.

The present inventors have arrived at the present invention as a result of diligent studies to solve these problems. That is, the present invention is the following invention.
Monomer composition containing the monomer (m1) represented by the general formula 1 and / or the monomer (m2) represented by the general formula 2 and the monomer (m3) represented by the general formula 3. A polymer electrolyte composition containing a polymer (P) of a product and a lithium salt.
The total weight ratio of the (m1) and the (m2) in the monomer composition is 10 to 60% by weight based on the weight of the monomer composition.
The weight ratio of the (m3) in the monomer composition is 40 to 90% by weight based on the weight of the monomer composition.
The weight ratio of (P) is 70 to 90% by weight based on the weight of the polymer electrolyte composition.
A polymer electrolyte composition in which the weight ratio of the lithium salt is 10 to 30% by weight based on the weight of the polymer electrolyte composition.

［一般式１中、Ｒ^１は水素原子又はメチル基を表す。］

[In general formula 1, R ¹ represents a hydrogen atom or a methyl group. ]

［一般式２中、Ｒ^２は水素原子又はメチル基を表し、Ｘ^２は炭素数１〜２のアルキレン基を表す。］

[In the general formula 2, R ² represents a hydrogen atom or a methyl group, and X ² represents an alkylene group having 1 to 2 carbon atoms. ]

［一般式３中、Ｒ^３は水素原子又はメチル基を表し、Ｒ^４は水素原子又は炭素数１〜１２の飽和アルキル基を表す。］

[In the general formula 3, R ³ represents a hydrogen atom or a methyl group, and R ⁴ represents a hydrogen atom or a saturated alkyl group having 1 to 12 carbon atoms. ]

The polymer electrolyte composition of the present invention has excellent moldability, and a battery having good cycle characteristics can be obtained.

Hereinafter, the present invention will be described in detail.
In the present specification, "(meth) acrylic acid" means "acrylic acid or methacrylic acid", and "(meth) acryloyl group" means "acryloyl group or methacrylic acid group".

The present invention includes a monomer (m1) represented by the general formula 1 and / or a monomer (m2) represented by the general formula 2 and a monomer (m3) represented by the general formula 3. It is a polymer electrolyte composition containing a polymer (P) of a monomer composition and a lithium salt.

In the general formula 1, R ¹ represents a hydrogen atom or a methyl group.
Examples of the monomer (m1) represented by the general formula 1 include vinylpyrrolidone and α-methylvinylpyrrolidone.

In the general formula 2, R ² represents a hydrogen atom or a methyl group, and X ¹ represents an alkylene group having 1 to 2 carbon atoms.
Examples of the monomer (m2) represented by the general formula 2 include (2-oxo-1,3-dioxolan-4-yl) methyl acrylate and (2-oxo-1,3-dioxolan-4-yl) methyl. Examples thereof include methacrylate, (2-oxo-1,3-dioxolane-4-yl) ethyl acrylate and (2-oxo-1,3-dioxolan-4-yl) ethyl methacrylate.

In the general formula 3, R ³ represents a hydrogen atom or a methyl group, and R ⁴ represents a hydrogen atom or a saturated alkyl group having 1 to 12 carbon atoms.
Examples of the monomer (m3) represented by the general formula 3 include (meth) acrylic acid, 2-ethylhexyl methacrylate, -2-ethylhexyl acrylate, dodecyl methacrylate, butyl methacrylate, methyl methacrylate, and isobornyl methacrylate. Can be mentioned.

The combination of the monomer (m1) and / or (m2) and (m3) in the monomer composition includes the monomer (m1) and the monomer (m1) from the viewpoint of ionic conductivity. Of m3), a combination in which R ⁴ is a saturated alkyl group having 4 to 12 carbon atoms is preferable, and R ^{4 of the} monomer (m2) and the monomer (m3) is a hydrogen atom. A combination with some is preferred.

The polymer electrolyte composition of the present invention contains a polymer (P) of a monomer composition containing the monomer (m1) and / or the monomer (m2) and the monomer (m3). ..
The total weight ratio of the (m1) and the (m2) in the monomer composition is 10 to 60% by weight based on the weight of the monomer composition. When the total weight ratio of the (m1) and the (m2) in the monomer composition is less than 10% by weight based on the weight of the monomer composition, the ionic conductivity of the polymer (P) becomes high. It deteriorates, and when it exceeds 60% by weight, the moldability of the polymer (P) deteriorates. From the viewpoint of moldability, the total weight ratio of the (m1) and the (m2) in the monomer composition is preferably 20 to 50% by weight based on the weight of the monomer composition.

The weight ratio of the (m3) in the monomer composition is 40 to 90% by weight based on the weight of the monomer composition. When the weight ratio of the (m3) in the monomer composition is less than 40% by weight based on the weight of the monomer composition, the polymer (P) becomes hard and the ionic conductivity deteriorates, and 90 If it exceeds% by weight, the lithium salt described later is partially precipitated and the ionic conductivity of the polymer (P) deteriorates.
From the viewpoint of ionic conductivity, the weight ratio of the (m3) in the monomer composition is preferably 50 to 80% by weight based on the weight of the monomer composition.

From the viewpoint of ionic conductivity, the monomer composition preferably further contains a sulfonate (m4) having a vinyl group. Examples of the (m4) include sodium styrene sulfonate, lithium styrene sulfonate, sodium 2-sulfoethyl methacrylate and the like.
From the viewpoint of ionic conductivity, the weight ratio of the (m4) in the monomer composition is preferably 1% by weight or less, preferably 0.5% by weight or less, based on the weight of the monomer composition. More preferably.

The monomer composition may contain monomers other than the monomers (m1), (m2), (m3) and (m4) as long as the physical properties are not impaired. From the viewpoint of ionic conductivity and moldability, the weight ratio of the monomers other than the monomers (m1), (m2), (m3) and (m4) in the monomer composition is the monomer composition. It is preferably 5% by weight or less based on the weight of the object.
The monomers other than the monomers (m1), (m2), (m3) and (m4) are not particularly limited as long as they are polymerizable, but specifically 1,6-hexanediol. Examples thereof include dimethacrylate and trimethylolpropane triacrylate.

The absolute molecular weight of the polymer (P) contained in the polymer electrolyte composition of the present invention is preferably 15,000 to 100,000 from the viewpoint of strength and flexibility of the polymer electrolyte composition.
For the measurement of the absolute molecular weight, for example, a multi-angle light scattering detector (MALS) of gel permeation chromatography (GPC) or a static light scattering (SLS) can be used. In the present application, the absolute molecular weight was measured using SLS. The measurement conditions for the absolute molecular weight are as follows.
The solvent used in this measurement is not particularly limited as long as it dissolves the polymer (P). The refractive index concentration gradient (dn / dc) of each sample can be measured using the differential refractive index measurement DRM-3000 attached to DLS-8000DLS.
Equipment: DLS-8000DSL [manufactured by Otsuka Electronics Co., Ltd.]
Measurement mode: SLS
Measurement cell: Cylindrical cell Measurement temperature: 25 ° C
Number of samples: 4 (difference in concentration)

The weight ratio of the polymer (P) contained in the polymer electrolyte composition of the present invention is 70 to 90% by weight based on the weight of the polymer electrolyte composition. If the weight ratio of the polymer (P) contained in the polymer electrolyte composition is less than 70% by weight based on the weight of the polymer electrolyte composition, the moldability of the polymer electrolyte composition deteriorates. If it exceeds 90% by weight, the ionic conductivity of the polymer electrolyte composition deteriorates.
From the viewpoint of moldability and ionic conductivity, the weight ratio of the polymer (P) contained in the polymer electrolyte composition is preferably 75 to 85% by weight.

The polymer (P) is a polymerization initiator known for the monomer composition {azo-based initiator [2,2'-azobis (2-methylpropionitrile), 2,2'-azobis (2,). 4-Dimethylvaleronitrile), 2,2'-azobis (2-methylbutyronitrile), etc.], peroxide-based initiators (benzoyl peroxide, di-t-butyl peroxide, lauryl peroxide, etc.), etc.} It can be produced by polymerization by a known polymerization method (lumpy polymerization, solution polymerization, emulsion polymerization, suspension polymerization, etc.).
The amount of the polymerization initiator used is preferably 0.01 to 5% by weight, more preferably 0.05 to 2% by weight, based on the total weight of the monomers, from the viewpoint of adjusting the absolute molecular weight to a preferable range. It is preferably 0.1 to 1.5% by weight, and the polymerization temperature and the polymerization time are adjusted according to the type of the polymerization initiator and the like, but the polymerization temperature is preferably −5 to 150 ° C. (more preferably 30). ~ 120 ° C.), the reaction time is preferably 0.1 to 50 hours (more preferably 2 to 24 hours).

Solvents used in the case of solution polymerization include, for example, esters (2 to 8 carbon atoms, such as ethyl acetate and butyl acetate), alcohols (1 to 8 carbon atoms, such as methanol, ethanol and octanol), and hydrocarbons (carbon numbers 1 to 8). Examples thereof include 4 to 8, for example, n-butane, cyclohexane and toluene), amides (for example, N, N-dimethylformamide) and ketones (for example, methyl ethyl ketone having 3 to 9 carbon atoms), and the absolute molecular weight is adjusted to a preferable range. From the viewpoint, the amount used is preferably 5 to 900% by weight, more preferably 10 to 400% by weight, still more preferably 30 to 300% by weight based on the total weight of the monomers. The monomer concentration is preferably 10 to 95% by weight, more preferably 20 to 90% by weight, still more preferably 30 to 80% by weight.

Examples of the dispersion medium in emulsification polymerization and suspension polymerization include water, alcohol (for example, ethanol), ester (for example, ethyl propionate), and light naphtha, and examples of emulsifier include higher fatty acid (10 to 24 carbon atoms) metal salt. (For example, sodium oleate and sodium stearate), higher alcohol (10 to 24 carbon atoms) sulfate ester metal salt (for example, sodium lauryl sulfate), tetramethyldecindiol ethoxylated, sodium sulfoethyl methacrylate, dimethylaminomethyl methacrylate, etc. Can be mentioned. Further, polyvinyl alcohol, polyvinylpyrrolidone and the like may be added as stabilizers.

The monomer concentration of the solution or dispersion is preferably 5 to 95% by weight, more preferably 10 to 90% by weight, even more preferably 15 to 85% by weight, and the amount of the polymerization initiator used is based on the total weight of the monomers. It is preferably 0.01 to 5% by weight, more preferably 0.05 to 2% by weight.
For polymerization, known chain transfer agents such as mercapto compounds (dodecyl mercaptan, n-butyl mercaptan, etc.) and / or halogenated hydrocarbons (carbon tetrachloride, carbon tetrabromide, benzyl chloride, etc.) can be used. ..

The polymer electrolyte composition of the present invention contains a lithium salt.
Examples of the lithium salt include LiSCN, LiN (CN) ₂ , LiClO ₄ , LiBF ₄ , LiAsF ₆ , LiPF ₆ , LiCF ₃ SO ₃ , Li (CF ₃ SO ₂ ) ₂ N, Li (CF ₃ SO ₂ ) ₃ C. , LiSbF ₆ , Li (FSO ₂ ) ₂ N, LiC ₄ F ₉ SO ₃ , LiN (SO ₂ CF ₂ CF ₃ ) ₂ , LiPF ₃ (CF ₂ CF ₃ ) ₃ , LiPF ₃ (C ₂ F ₅ ) ₃ , Examples thereof include LiPF ₃ (CF ₃ ) ₃ , LiCl, LiF, LiBr, LiI, LiB (C ₂ O ₄ ) ₂ , lithium difluoro (oxalate) borate and lithium bis (oxalate) borate.
The lithium salt may be one kind or a mixture of two or more kinds.

The weight ratio of the lithium salt contained in the polymer electrolyte composition is 10 to 30% by weight based on the weight of the polymer electrolyte composition. If the weight ratio of the lithium salt contained in the polymer electrolyte composition is less than 10% by weight based on the weight of the polymer electrolyte composition, the polymer electrolyte composition does not conduct ionic conduction, and 30% by weight is used. If it exceeds, salt is partially precipitated and the battery reaction on the facing surface becomes non-uniform.
From the viewpoint of ionic conductivity, the weight ratio of the lithium salt contained in the polymer electrolyte composition is preferably 15 to 25% by weight based on the weight of the polymer electrolyte composition.

The polymer electrolyte composition of the present invention further contains additives such as plasticizers, stabilizers, antioxidants and mold release agents used in known polymer compounds within a range not contrary to the object of the present invention. It may be.

The glass transition temperature of the polymer electrolyte composition of the present invention is preferably -60 to 20 ° C, more preferably -50 to 0 ° C. When the glass transition temperature of the polymer electrolyte composition is in the above range, the balance between moldability and flexibility of the polymer electrolyte composition is good. The glass transition temperature of the polymer electrolyte composition can be adjusted by the weight ratio of the lithium salt contained in the polymer electrolyte composition.

For the measurement of the glass transition temperature of the polymer electrolyte composition and the polymer (P), for example, differential scanning calorimetry (DSC) can be used. In the present application, the measurement was carried out by the method (DSC method) specified in ASTM D3418-82. The measurement conditions are described below.
Equipment: Q2000 [manufactured by TA-Instruments]
Sample pan: Aluminum Measurement atmosphere: Nitrogen 50 mL / min
Temperature program:
(1) Raise to 50 ° C at 10 ° C / min (2) Hold at 50 ° C for 10 minutes (3) Cool to -80 ° C at 10 ° C / min (4) Hold at -80 ° C for 10 minutes (5) 10 ° C Heat up to 50 ° C at / min From the differential scanning calorific value curve obtained by the above measurement, draw a graph with the vertical axis representing the amount of heat absorbed and the horizontal axis representing the temperature, and extend the baseline on the low temperature side of the graph to the high temperature side. The temperature at the intersection of the straight line and the tangent line drawn at the point where the slope of the curve of the stepwise change portion of the glass transition is maximized was defined as the glass transition temperature.

The method for producing the polymer electrolyte composition of the present invention is not particularly limited, and for example, an organic solvent capable of dissolving both the polymer (P) and the lithium salt and the polymer (P) and the lithium salt can be used. After mixing in a predetermined ratio, it can be obtained by removing the solvent if necessary.
The mixing is preferably carried out by a conventionally known method, for example, a mixer such as a homomixer, a homodisper, a wave blower, a homogenizer, a disperser, a paint conditioner, a ball mill, a magnetic stirrer, or a mechanical stirrer.

The organic solvent capable of dissolving both the polymer (P) and the lithium salt is not particularly limited, but for example, N, N-dimethylacetamide, N, N-dimethylformamide, N-methyl-2-pyrrolidone and the like. Aprotonic polar solvents such as N-alkylpyrrolidones, dimethylsulfoxide, 1,3-dimethyl-2-imidazolidinone, ester solvents such as γ-butyrolactone and butyl acetate, carbonate solvents such as ethylene carbonate and propylene carbonate. , Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, alkylene glycol monoalkyl ether such as propylene glycol monoethyl ether, alcohol solvent such as isopropyl alcohol, water and a mixture thereof are preferably used. Among them, the aprotic polar solvent has the highest solubility and is preferable.

The polymer electrolyte composition of the present invention is particularly preferably used as a polymer electrolyte composition molded body. The polymer electrolyte composition molded body may be in various forms depending on the intended use, such as a film shape, a plate shape, a fibrous shape, a hollow thread shape, a particle shape, a lump shape, a microporous shape, and a foam shape.

The all-solid-state lithium-ion secondary battery of the present invention has the polymer electrolyte composition interposed between the positive electrode and the negative electrode.
In the all-solid-state lithium-ion secondary battery of the present invention, a positive electrode, a polymer electrolyte composition, and a negative electrode are laminated in a battery outer container (laminated container, etc.), and a current extraction terminal connected to a current collector is provided on the outside of the container. It can be obtained by a method of sealing the battery outer container in the state of being put out in the above.

In the all-solid-state lithium ion secondary battery of the present invention, the polymer electrolyte composition may be formed into a film and used.
In the all-solid-state lithium ion secondary battery, the film of the polymer electrolyte composition arranged between the positive electrode and the negative electrode may be referred to as a separator.

Next, the present invention will be specifically described with reference to Examples, but the present invention is not limited to the Examples as long as the gist of the present invention is not deviated. Unless otherwise specified, parts mean parts by weight and% means% by weight.

<Production Example 1: Synthesis of polymer (P-1)>
300 parts of toluene was charged as a polymerization solvent into a four-necked flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel and a nitrogen gas introduction tube, and the temperature was raised to 75 ° C. Next, 30 parts of N-vinylpyrrolidone (hereinafter abbreviated as VP), 65 parts of 2-ethylhexyl methacrylate (hereinafter abbreviated as EHMA), 4.5 parts of acrylic acid and 1,6-hexanediol dimethacrylate (hereinafter abbreviated as HDMA). A monomer compound containing 0.5 part and an initiator solution in which 0.03 part of 2,2'-azobis (2,4-dimethylvaleronitrile) was dissolved in 5 parts of toluene were added to nitrogen in four mouths of corben. Radical polymerization was carried out by continuously dropping the solution with a dropping funnel over 2 hours while stirring. After completion of the dropping, the temperature was raised to 75 ° C. and the reaction was continued for 1 hour. Next, an initiator solution prepared by dissolving 0.01 part of 2,2'-azobis (2,4-dimethylvaleronitrile) in 1 part of toluene was added with a dropping funnel, and the reaction was continued for 3 hours to continue the polymer (P-1). ) Was obtained. A toluene solution of the obtained polymer (P-1) was added dropwise to methanol / ion-exchanged water (1/1 volume ratio) and reprecipitation was carried out to obtain a white lumpy polymer (P-1). The absolute molecular weight of the obtained polymer (P-1) measured by a light scattering method in a methanol solution was 69000, and the glass transition temperature was −25 ° C.

<Production Examples 2, 3 and 21-27: Synthesis of Polymers (P-2) (P-3) and Polymers (P-21)-(P-27)>
In Production Example 1, the polymers (P-2), (P-3) and the polymers (P-21) to (P-27) were similarly prepared except that the composition of the monomer compounding solution was changed as shown in Table 1. Obtained. The absolute molecular weight and glass transition temperature of each are shown in Table 1.

<Production Examples 4 to 20: Synthesis of Polymers (P-4) to (P-20)>
In Production Example 1, the polymers (P-4) to (P-4) to (P-4) to ( A DMF solution of P-20) was obtained. The obtained DMF solution was added dropwise to acetone and reprecipitated to obtain polymers (P-4) to (P-20). The absolute molecular weight and glass transition temperature of each are shown in Table 1.

The monomers in Table 1 are shown below.
VP: N-vinylpyrrolidone PCMA: (2-oxo-1,3-dioxolan-4-yl) methyl methacrylate EHMA: 2-ethylhexyl methacrylate EHA: 2-ethylhexyl acrylate DMA: dodecyl methacrylate BMA: butyl methacrylate MMA: methyl methacrylate Acrylate AA: Acrylic acid MAA: Namethacrylate NaSS: Sodium styrene sulfonate LiSS: Lithium styrene sulfonate NaSEMA: 2-Sulfoethyl methacrylate Sodium HDMA: 1,6-hexanediol dimethacrylate TMPTA: Trimethylol propanetriacrylate

<Example 1>
20 parts of the polymer (P-1) and 3.7 parts of lithium bis (sulfonyl) imide (hereinafter abbreviated as LiFSI) are dissolved in 76.3 parts of acetone to prepare an acetone solution of the polymer electrolyte composition (D-1). Made. The acetone solution was cast and then deacetoneed to give a film of polymer electrolyte composition. The film became a pale yellow transparent film, and the glass transition temperature was -9 ° C., and the ionic conductivity was 4.6 × 10 ^-3 mS / cm. The ionic conductivity was measured by the method described later.

<Examples 2, 15 to 20 and Comparative Examples 1, 8>
In Example 1, the polymer electrolyte compositions (D-2), (D-22) to (D-26), (D-28) were similarly modified except that the polymer and the lithium salt were changed as shown in Table 2. , (D-3) and (D-27) were prepared. The glass transition temperature and ionic conductivity of the film cast with the acetone solution are shown in Table 2.

<Examples 3 to 14 and Comparative Examples 2 to 7>
In Example 1, the polymer and the lithium salt were changed as shown in Table 2, and the solvent was changed to methanol. In the same manner, the methanol solutions of the polymer electrolyte compositions (D-4) to (D-21) were prepared. did. The methanol solution was cast and then demethanolized to give a film of polymer electrolyte composition. The glass transition temperature and ionic conductivity of the film are shown in Table 2.

<Evaluation of moldability>
The films obtained in Examples 1 to 19 and Comparative Examples 1 to 8 were visually inspected and evaluated as to whether they were uniform as a whole.

<Measurement of ionic conductivity>
The ionic conductivity of the obtained film was measured by the following method.
Both sides of the obtained film were sputtered with platinum at 20 mV for 60 seconds using a sputtering device "JFC-1600 (manufactured by JEOL)" to obtain ion blocking electrodes. Next, a cell made of molded electrodes was connected to the AC impedance device "Solartron 1260", and impedance measurement was performed in the range of 10 μHz to 10 MHz. Next, a Bode diagram was created, and the ionic conductivity was calculated from | Z | in the plateau region seen after 1 Hz.

<Example 21>
100 parts of acetone solution (solid content concentration 20%) of polymer electrolyte composition (D-1), 60 parts of lithium-nickel-cobalt-aluminum composite oxide (NCA) as active material particles, and acetylene black as conductive aid. 20 parts of [Denka Black manufactured by Denka Kagaku Kogyo Co., Ltd.] are put into a special container of a rotating / revolving mixer Awatori Rentaro [manufactured by Shinky Co., Ltd.], and mixing is performed at a stirring speed of 2000 rpm for 5 minutes using the same mixer. A slurry was obtained. The obtained slurry is coated on an aluminum current collector foil with a film applicator so that the slurry thickness becomes 100 μm, dried in a dryer at 60 ° C. for 10 minutes, and pressed with a press [SA-302: Tester Sangyo Co., Ltd.] ], Pressing was performed at 2 MPa to obtain an electrode having a thickness of 76 μm.
An acetone solution of the polymer electrolyte composition (D-1) used in Example 1 was further applied onto the obtained electrode and dried in a dryer at 60 ° C. for 10 minutes to form an electrolyte layer having a thickness of 10 μm. .. An all-solid-state lithium-ion secondary battery (C-1) was prepared by placing lithium and a copper current collector foil on the counter electrode.

<Examples 22 to 40 and Comparative Examples 9 to 16>
In Example 21, all-solid-state lithium-ion secondary batteries (C-2) to (C-28) were prepared in the same manner except that the solution of the polymer electrolyte composition was changed as shown in Table 3.

<Charge / discharge test: Evaluation of cycle characteristics>
Charge / discharge test for all-solid-state lithium-ion secondary batteries (C-1) to (C-20) at 45 ° C. using the charge / discharge measuring device "HJ-SD8" [manufactured by Hokuto Denko Co., Ltd.] by the following method. Was done.
The battery was charged to 4.2 V by the constant current constant voltage method (0.01C), paused for 10 minutes, and then discharged to 2.6 V by the constant current method (0.01C).
This cycle was repeated 20 times, and the percentage of the ratio of the discharge capacities taken out in each of the 1st and 20th cycles (100 × 20th discharge capacity / 1st discharge capacity) was taken as the cycle characteristic. The results are shown in Table 3.

The polymer electrolyte composition of the present invention and the all-solid-state lithium ion secondary battery using the same are useful for mobile phones, personal computers, hybrid vehicles and electric vehicles.

Claims (3)

Monomer composition containing the monomer (m1) represented by the general formula 1 and / or the monomer (m2) represented by the general formula 2 and the monomer (m3) represented by the general formula 3. A polymer electrolyte composition containing a polymer (P) of a product and a lithium salt.
The total weight ratio of the (m1) and the (m2) in the monomer composition is 10 to 60% by weight based on the weight of the monomer composition.
The weight ratio of the (m3) in the monomer composition is 40 to 90% by weight based on the weight of the monomer composition.
The weight ratio of (P) is 70 to 90% by weight based on the weight of the polymer electrolyte composition.
A polymer electrolyte composition in which the weight ratio of the lithium salt is 10 to 30% by weight based on the weight of the polymer electrolyte composition.

[In general formula 1, R ¹ represents a hydrogen atom or a methyl group. ]

[In the general formula 2, R ² represents a hydrogen atom or a methyl group, and X ² represents an alkylene group having 1 to 2 carbon atoms. ]

[In the general formula 3, R ³ represents a hydrogen atom or a methyl group, and R ⁴ represents a hydrogen atom or a saturated alkyl group having 1 to 12 carbon atoms. ] The polymer electrolyte composition according to claim 1, wherein the monomer composition further contains a sulfonate (m4) having a vinyl group. An all-solid-state lithium-ion secondary battery having the polymer electrolyte composition according to claim 1 or 2, which is interposed between the positive electrode and the negative electrode.