WO2001047055A1 - Polymer solid electrolyte lithium ion secondary cell - Google Patents

Abstract

A polymer solid electrolyte lithium ion secondary cell comprising a positive electrode and a negative electrode for a lithium ion secondary cell and, arranged between the electrodes, a separator and a polymer solid electrolyte, wherein said polymer solid electrolyte is prepared by providing a liquid crosslinking composition for the solid electrolyte comprising a crosslinkable material, an electrolytic solvent and a lithium salt electrolyte and containing the crosslinkable material in an amount of 10 wt% of the composition, injecting the composition into a sealable cell container having a built-in unit comprising the electrodes and the separator, and gelating the composition through effecting a crosslinking reaction. The cell can be produced by the use of a process similar to that for the production of a cell using a conventional electrolyte, without the need for special facilities, and the polymer solid electrolyte used is excellent in safety and cell characteristics.

Description

 Specification

 FIELD OF THE INVENTION Field of the Invention

 The present invention relates to a polymer solid electrolyte lithium ion secondary battery, and more particularly, to a rechargeable secondary battery having a cylindrical, square, or sheet-like shape, wherein a liquid electrolyte is formed by a polymer. Lithium ion secondary battery using a polymer solid electrolyte with improved current load characteristics, especially current load characteristics at low temperatures, and a method for producing the same, and liquid crosslinkability for the above solid electrolyte Related to the composition.

 Conventional technology

 Lithium-ion rechargeable batteries are small and lightweight rechargeable batteries that have a large storage capacity per unit volume or unit weight, so they can be used in portable electronic devices, mobile phones, notebook computers, personal computers, personal digital assistants (PDAs), It is used in portable MD devices, video cameras, digital cameras, etc., and is an indispensable power source for various portable devices that are small, lightweight and have relatively high power consumption.

 By the way, in the current lithium ion secondary battery, The electrolyte is a liquid electrolyte in which a lithium electrolyte salt is dissolved in a solvent mainly composed of propylene carbonate, ethylene carbonate, etc., that is, an electrolyte (an organic solvent-based electrolyte using an organic solvent as a medium is an organic electrolyte or non-aqueous solution). Most of these use electrolytes, which are simply called “electrolytes” here.

 However, batteries using such electrolytes are subject to the danger of electrolyte leakage and heat generation during use / charge / discharge of the electrolyte itself; misuse (short-circuit or use of multiple batteries and partial Heat generation due to exposure to high temperatures in the operating environment; or internal pressure rise due to temperature rise caused by soldering etc. when assembling the device (vapor pressure due to the solvent in the electrolyte or There is a safety problem such as liquid leakage, rupture, and danger of ignition caused by gas generation due to decomposition. Solidification of the electrolyte, that is, development of solid electrolyte is being actively conducted.

Generally, polymer materials are used for solid electrolytes. Various polymer materials have been studied, including polymer materials having a styrene chain, but the ion conductivity, which is the most basic property of these materials, is significantly inferior to that of liquid electrolytes, and has reached a practical level. Not.

 Therefore, recently, the development of polymer gel-type polymer solid electrolytes in which the liquid electrolyte is made of a polymer material in a gel state has been activated, and at present, ion conductivity close to that of the liquid electrolyte may be obtained. Yes, some applications are being put to practical use. However, most of the batteries that use solid electrolytes that are currently being put into practical use are sheet-shaped (thin) batteries that have recently emerged in recent years. Liquid electrolytes are still used for batteries.

 The reason is that a mass production line for cylindrical and prismatic batteries using liquid electrolyte has already been completed. In order to use the same solid electrolyte used for sheet batteries, new facilities must be installed, renewed, This is because capital investment such as layout change is required, which leads to an increase in production costs.

 In other words, batteries using liquid electrolytes are produced by a simple operation of simply injecting the electrolyte solution in the final step into a sealed container for batteries in which all parts such as electrodes have been assembled. In the current case, a new process of forming a polymer solid electrolyte must be incorporated into the existing production line, and investment for new equipment, securing of installation locations, and There are many problems such as maintenance of production, and it is very difficult to change liquid electrolyte (electrolyte) to solid electrolyte.

 In the production of sheet-shaped thin batteries, the following methods are currently used.

(1) After forming the positive and negative electrodes, a specific polymer that swells without dissolving in the electrolytic solution is applied to this electrode surface or a separator or nonwoven fabric inserted between the positive and negative electrodes by any method, such as a solvent or The liquefied material is formed by forming a solution, emulsion, and powder purgin using a dispersion medium, or by heating and melting, and then dried or solidified. Not only by drying, but also by forming a film in which the polymer particles are integrated) and then swelling by immersion in an electrolyte consisting of an electrolyte salt and an electrolyte solvent to form a gel How to make it;

 (2) An electrolyte containing a cross-linkable monomer or oligomer is applied to the electrode surface or a separator or non-woven fabric inserted between the positive electrode and the negative electrode, and the polymer is cross-linked by heating or radiation such as ultraviolet rays. A method in which both the positive and negative electrodes are bonded together with a separator or nonwoven fabric sandwiched between them, or a method in which, after bonding, the polymer is crosslinked by heating to form a gel.

 However, any method requires dedicated equipment for each process such as application, solidification, bonding, and swelling.

 In addition, the polymer used in the method (1) swells with the electrolytic solution, but must not be dissolved in the electrolytic solution. It is necessary to use a solvent to form a solution, emulsion, disposable, or heat and melt) to make it liquid, and to do so, it must be a non-crosslinked polymer. Therefore, the polymers that can be used at present are limited to polytetrafluorovinylidene-based polymers and polyacrylonitrile-based polymers. It is difficult to keep the quality constant, the amount of polymer forming the gel increases, and it is difficult to obtain good ionic conductivity. Further, it is advantageous in the process to swell the polymer after winding or laminating the electrode, separator or nonwoven fabric, but in this case, the electrolyte is not sufficiently distributed to the entire polymer, and the swelling is incomplete. It has many problems, such as being prone to swelling and taking a long time to swell.

 On the other hand, in the method (2), the application is a method in which an electrolyte containing low-molecular monomers, oligomers, etc. is used, and the entire components containing the electrolyte are gelled at a time by crosslinking. There is no need to use any means such as natural swelling, so it looks ideal at first glance. However, since the solution containing the electrolyte solvent is applied, the electrolyte solvent is liable to volatilize during coating and crosslinking, and a low boiling electrolyte solvent cannot be used.

Low-boiling-point electrolyte solvents are important solvents for obtaining good ionic conductivity, especially at low temperatures, and are used in conventional batteries such as cylindrical and square batteries that use liquid electrolytes. In order to obtain good properties, especially at low temperatures, low-boiling electrolyte solvents such as dimethyl carbonate, methylethyl carbonate, getyl carbonate, and propion Methyl acid, dimethoxetane and the like are appropriately used. However, as described above, the sheet-type battery manufactured by the method (2) has a serious problem that these low-boiling-point electrolyte solvents cannot be used, and it is difficult to obtain good characteristics.

 Therefore, ethylene carbonate and propylene carbonate must be mainly used as the electrolyte solvent. However, ethylene carbonate has a high melting point (36 ° C) and cannot be used alone, but propylene carbonate (melting point: 149 ° C) must be used alone or as a mixture with ethylene carbonate. Les ,. When propylene carbonate is used, propylene carbonate decomposes graphite, so that graphite-based carbon materials cannot be used for the negative electrode, and usable carbon materials are amorphous carbon such as hard carbon. Limited to materials.

 In addition, the graphitic carbon material has an excellent property that the voltage at the time of discharge is easily maintained at a constant value, but cannot be used in the battery according to the method (2).

 In addition, although the ionic conductivity of the polymer gel type solid electrolyte described above is approaching the ionic conductivity of the liquid electrolyte, it is still inferior, and batteries using the polymer gel type solid electrolyte are relatively large. It cannot be used for applications that require a discharge current, and can only maintain insufficient performance to replace batteries using conventional liquid electrolytes.

 The main reason is that in order to form a gel, it must contain a relatively large amount of a polymer that does not contribute to ionic conductivity. In order to improve the ionic conductivity of this polymer gel-type solid electrolyte, studies have been made on both the polymer content and the polymer structure, such as reducing the amount of polymer components in the gel and using high dielectric constant polymers. However, we have not yet reached a satisfactory level.

 Disclosure of the invention

The present inventors have made it possible to manufacture a polymer solid electrolyte lithium-ion secondary battery by the same process as that for manufacturing a battery using a conventional electrolytic solution without requiring special new equipment, and to achieve safety and characteristics. The company has developed a solid electrolyte with a high level of performance, and has been conducting intensive research to produce a polymer solid electrolyte lithium-ion secondary battery that reaches a practical level. Forms a solid A liquid cross-linkable composition containing a cross-linkable material for a solid electrolyte is used, and this is used as a sealable container or case for an existing lithium-ion secondary battery using a liquid electrolyte (hereinafter referred to as “ It is found that if the above-mentioned cross-linkable material is cross-linked and the above-mentioned cross-linkable material is cross-linked, gelation of the system occurs due to formation of a polymer solid, and a desired polymer solid electrolyte can be obtained, leading to the completion of the present invention. Was.

 That is, the present invention relates to a polymer solid electrolyte lithium ion secondary battery comprising a positive electrode and a negative electrode for a lithium ion secondary battery, a separator disposed between the two electrodes, and a polymer solid electrolyte, Polymer solid electrolytes

 (1) Crosslinkable material

 (2) electrolyte solvent and

 (3) Lithium electrolyte salt

A liquid cross-linkable composition for a solid electrolyte (hereinafter referred to as a “liquid composition”) in which the amount of the cross-linkable material (1) is 10% by weight or less based on the total amount of the fibrous material; And a lithium ion secondary battery which is a polymer solid electrolyte which is a polymer solid electrolyte that is injected into a sealable battery container incorporating a unit including a separator and is gelled by crosslinking.

 Detailed description of the invention

 (1) Crosslinkable material

 The crosslinkable material (1) in the present invention may be any crosslinkable material as long as it can form a polymer solid, and specific examples include the following five combinations (a to e). .

 a. Epoxy resin and its crosslinking agent (Epoxy combination)

 b. Polyisocyanate compound and poly- or urethane-prepolymer and its crosslinking agent (isocyanate-based combination)

 c. (Meth) acrylic monomer and radical polymerization initiator (acrylic monomer combination)

 d. Epoxy group-containing radical copolymer and cationic polymerization initiator (polymer combination)

e. Combination of oxetane ring-containing polymer and cationic polymerization initiator Limmer combination).

 In this specification, “(meth) acryl” means acryl or methacryl, and “(meth) acrylate” means acrylate or methacrylate.

 Hereinafter, preferred embodiments of the combinations a to e of the crosslinkable materials will be described in detail.

 a. Epoxy combination

 The epoxy resin used here preferably has the formula [1]:

(CH ₂ CH-CH ₂ 0) a-R _1- (OCH ₂ CH ₂ CN) b

 \ / [1]

o (wherein, a is a number of 2-5 and b is 1-4, provided that a + b is Ru 3-6 der; and R _t is the molecular weight of 250 having three to six hydroxyl groups in the molecule Is the residue obtained by removing all hydroxyl groups from less than

And a cyanoethylated epoxy resin represented by the formula:

 The cyanoethylated epoxy resin [1] has the formula [2]:

One (OH) _{a + b} [2]

 (Wherein, R, a and b are as defined above)

I) a reaction of adding a mole of epichlorohydrin to the polyol compound represented by the formula (1) to obtain a partially glycidyl etherified compound, and then adding b moles of acrylonitrile to the remaining hydroxyl groups (cyanoethylation); or ii) It can be produced by first performing an addition reaction of b mole of atarilonitrile and then glycidyl etherifying the remaining hydroxyl groups. Any of these addition reactions can be carried out according to a known method. For example, the addition reaction may be carried out in water or a non-reactive solvent, if necessary, in the presence of an alkali catalyst or the like. The partially glycidyl etherified compound of i) itself is generally commercially available as an "epoxy resin" and can be used after being subjected to cyanoethylation.

Examples of the polyol compound [2] include glycerin, erythritol, pentaerythritol, xylitol, sorbitol, diglycerin, triglycerin, Examples include inositol and mannitol.

 As described above, a polyol compound having 3 to 6 hydroxyl groups is used as the polyol compound [2] serving as the skeleton of the cyanoethylated epoxy resin [1]. When the number of hydroxyl groups in the polyol compound is more than 6, the concentration of cyanoethyl groups and epoxy groups can be increased, and it is easy to increase the crosslink density with a high dielectric constant, which is advantageous in terms of ionic conductivity. The viscosity of the liquid composition containing the same increases, and the infiltration between the electrode and the separator during injection into a closed container decreases. Conversely, if the number of hydroxyl groups is less than 3, the gelling property will decrease due to the decrease in crosslink density, and the amount of the polymer component must be increased in order to form the gel. Causes a decrease in

 The crosslinking agent used with the epoxy resin is preferably of the formula [3]:

H ₂ N-CH ₂ CH _2- (NH-CH ₂ CH ₂ ) c-NH ₂ [3]

 (Where c is a number from 0 to 4)

 A polyethylene polyamine represented by, for example, ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, etc., and a formula [4]:

(R ₃ ) e ₄ (R ₅ ) &

 I I I [4]

(R ₂ ) dN-CH ₂ CH _2- (N-CH ₂ CH ₂ ) fN- (R ₆ ) h

(Wherein R ₂ , R ₃ , R ₄ , R ₅ and R ₆ are each H or _CH ₂ CH ₂ CN; d, e, g and h are each a number from 0 to 2, and d + e is 2 , G + h

2; and f is a number from 0 to 4. However, at least two of R _{2 to} R ₆ are H and at least one is one CH ₂ CH ₂ CN)

And at least one compound selected from the group consisting of partially cyanoethylated polyethylene polyamines represented by 1.

The partially cyanoethylated polyethylene polyamine [4] can be produced by subjecting the polyethylene polyamine [3] to an addition reaction of a predetermined mole of acrylonitrile. The addition reaction is usually carried out in a non-reactive solvent, if necessary, in the absence of a catalyst at room temperature to 8 It can be easily performed at a temperature of about 0 ° C.

 The higher the molecular weight (the number of carbon atoms) of polyethylene polyamine [3], the greater the number of crosslink points, which tends to be advantageous in gelling properties. However, when f is 5 or more, the viscosity of the liquid composition increases, and An excessive increase in the cyanone conversion rate leads to an improvement in ion conductivity due to an increase in the dielectric constant. In some cases may lead to a decrease in performance. Therefore, it is preferable that the cross-linking agent is appropriately selected in consideration of the balance with the type of the epoxy resin, the gelling property, the ionic conductivity, and the like.

 The mixing ratio of the cyanoethylated epoxy resin to the crosslinking agent is 1: 0.about.1 centered on the value calculated from the equivalent of the cyanoethylated epoxy resin and the active hydrogen equivalent of the crosslinking agent.

It is preferred to be in the range of about 8 to 2.0, and outside this range, the gelling property tends to decrease.

 b. Isocyanate combination

 Examples of the polyisocyanate compound used in this combination include 2,4- or 2,6-tolylene diisocyanate or a mixture thereof, 4,4'-diphenylmethanediisocyanate, isophorone Diisocyanate, 1,6-hexamethylene diisocyanate, 2,4,6-trimethyl / lehexamethylene diisocyanate, xylylene diisocyanate, and crude diphenyl methane diisocyanate At least one polyisocyanate selected from the group consisting of:

The urethane prepolymer used in place of or in addition to the above polyisocyanate compound is a polyisomers having an equivalent ratio of a polyol having a molecular weight of less than 400 and an excess of, for example, NCO / OH = 1.2 to 2.0. This is a urethane prepolymer containing an isocyanate group, which is obtained by reacting a cyanate (which is appropriately selected from the above polyisocyanate compounds). Here, when the molecular weight of the polyol is 400 or more, the gelling property tends to decrease. On the other hand, if the NCO / OH equivalent ratio is less than 1.2, a decrease in the infiltration property at the time of injection and a decrease in the gelling property due to an increase in viscosity are caused, and if it exceeds 2.0, unreacted polyisocyanate remains. This corresponds to the case where the above-mentioned polyisocyanate compound and the urethane prepolymer are used in combination, and the meaning is not significant. No.

 Examples of the polyol include ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, trimethyi monopropane, glycerin, polyglycerin and the like, and ethylene oxide or propylene oxide adducts thereof. Use at least one of

 The reaction between the polyol and the polyisocyanate can be carried out in the absence of a catalyst or in the presence of a small amount of a catalyst (for example, metal salts such as Sn, Bi, Fe, Pb, or dibutyltin dilaurate) in the absence of a solvent or as necessary. The reaction can be carried out in a non-reactive dehydrating solvent at a temperature from room temperature to about 100 ° C.

 If the polyisocyanate compound is used alone without using such a urethane prepolymer, some of the polyisocyanate compounds have a relatively high vapor pressure, which may be unfavorable for environmental health. However, in this case, it is desirable to use urethane prepolymer as described above.

 Examples of the crosslinking agent used in the isocyanate combination include the following. i) A polyol compound having a molecular weight of less than 400 and a hydroxyl value of 400 or more.

 ii) Polyoxyethylene polyol or polyoxypropylene polyol having a molecular weight of less than 800, obtained by adding ethylene oxide or propylene oxide to a polyol having 2 to 6 hydroxyl groups in the molecule.

 Examples of the polyol include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, glycerin, diglycerin, triglycerin, 1,1,1-trimethylolpropane, erythritol, pentaerythritol, and dipentaerythritol. And xylitol, mannitol, inositol, sorbitol and the like.

 Usually, the above addition reaction may be carried out in the presence of an alkali catalyst while heating or pressurizing while partially or completely adding ethylene oxide or propylene oxide. Thus, the desired polyoxyalkylene polyol is produced. Many varieties of polyoxyalkylene polyols are commercially available.

iii) by two or more amine-like amino groups and Z or imino groups in the molecule A poly N-hydroxyalkylated compound obtained by adding ethylene oxide and Z or propylene oxide to a compound containing active hydrogen atoms or ammonia.

Examples of the active hydrogen atom-containing compound include polyalkylene polyamines such as ethylenediamine, dimethylenetriamine, triethylenetetramine, tetraethylenepentamine, and pentaethylenehexamine; 1,3-propanediamine, 1,4-butanediamine, 6 - to Arukanjiami emissions such as Kisanjiamin; Monomechiruamin, Monoechiruamin, monoisopropyl § Min, mono _n

— Monoalkylamines such as butylamine; polyethyleneimines.

 The above addition reaction may be carried out usually at normal pressure to under pressure, at normal temperature or under heating, using no catalyst or a small amount of an alkali catalyst.

 Specific examples of the obtained poly N-hydroxyalkylated compound include N, N′-tetrahydroxyxethylethylenediamine, N, N′-tetrahydroxyisopropene pinoleethylenediamine, Ν, Ν ′, N "1-pentahydroxyisopropinolegetylenetriamine, N, N,, N", Ν '"-Hexahydroxyxenotinoletrietylenetetramine, triethanolamine, triisopropanololamine, polydimethylamine Droxyisopropyl polyethyleneimine and the like, and some of these are commercially available.

 iv) Ethylene oxide and Z or propylene oxide, with at least one active hydrogen atom remaining in an active hydrogen-containing compound or ammonia containing three or more amine amino and Z or imino groups in the molecule. To obtain a mono- or poly-N-cyanoethylated poly (N-hydroxyalkylated) compound obtained by subjecting the remaining active hydrogen atoms to cyanoethylation with acrylonitrile.

Examples of the active hydrogen atom-containing compound include ethylenediamine, methylethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, hexamethylenediamine, and polyethyleneimine. The above-mentioned N-hydroxyalkylation is usually carried out at normal pressure to pressure and at normal temperature to heating using a catalyst or a trace amount of an alkali catalyst, and the above-mentioned cyanoethylation is usually carried out without a catalyst and without solvent. If necessary, the reaction may be carried out in a non-reactive solvent at a temperature from room temperature to about 60 ° C. The order of the N-hydroxyalkylation and the cyanoethylation may be reversed.

 V) A partially cyanoethylated poly (N-hydroxyalkylated compound) obtained by partially dehydrating the hydroxyl groups of the poly (N-hydroxyalkylated compound) obtained in (iii) above with acrylonitrile.

 The above-mentioned cyanoethylation may be usually carried out using an alkali catalyst in a solvent-free or non-reactive solvent at a temperature from room temperature to about 60 ° C. In addition, lithium hydroxide can be used as the alkali catalyst, and when used in the lithium battery of the present invention, there is no problem in terms of contamination of the alkaline catalyst or a neutralized product thereof and residual impurities.

 vi) A hydroxyl-containing radical copolymer obtained by copolymerizing a radical-polymerizable monomer having a hydroxyl group with another radical-polymerizable monomer.

 The radical polymerizable monomer having a hydroxyl group is a partial (meth) acrylate of a polyhydroxy compound in which at least one hydroxyl group remains in the molecule. The polyhydroxy compound includes a high hydroxyl value polyhydroxy compound having a hydroxyl value of 400 or more having 2 to 6 hydroxyl groups in a molecule, for example, ethylene glycol, diethylene glycol, propylene glycol / di, dipropylene glycol, glycerin, Diglycerin, triglycerin, erythritol, pentaerythritol, dipentaerythritol, xylitol, sonoreitol, or adducts of these ethylene oxides or propylene oxides.

 The other radically polymerizable monomer is represented by the formula [5]:

CH ₂ = CR ₈ [5]

(Wherein R ₇ is H or CH ₃ ; and R ₈ is one CN, one COOCH ₃ , -COO C. H ₅ , — COO (CH. CHQ O) ^ 3 CH ₃ , one COO (CH. CH. 〇) _L to ₃ C. H ₅ , -COO (CH ₂ CH (CH ₃ ) 0) ₁ ^ 3 CH ₃ , -COO (CH ₂ CH (CH ₃ ) O) _t

~ ₃ C ₂ H _5, one OC_〇_CH _3, or _OCOC ₂ H ₅₎

A bull or (meth) acrylic monomer represented by

 The weight ratio of the radical polymerizable monomer having a hydroxyl group to another radical polymerizable monomer is preferably from 1:10 to 1: 1.

 Copolymerization is usually carried out using a radical polymerization initiator (eg, benzoyl peroxide, N, N'-azobisisobutyronitrile), in a solvent at a temperature of about 60 to 80 ° C. I just need. At this time, chain transfer agents such as mercaptans and hydroxyl group-containing mercaptans can be used for controlling the molecular weight. Particularly, when hydroxyl group-containing mercaptans (for example, mercaptoethanol) are used, the hydroxyl group of the copolymerized polymer can be improved. It is also a source of base introduction.

 Thus, in the isocyanate-based combination (b), the crosslinking agents (i) to (vi) can be used. Particularly, in the polyoxyalkylene polyol (ii), those having a molecular weight of less than 800 and less than 2 hydroxyl groups, or a molecular weight of less than 2 If the number is 800 or more, the gelling property is low, and if the number of hydroxyl groups exceeds 6, the viscosity increases and the penetration between the electrode Z separators decreases.

 Furthermore, when the polyoxyalkylene polyol (ii) is used, the reactivity of the polyisocyanate compound or urethane prepolymer (hereinafter referred to as “isocyanate component”) with NCO is relatively low. It may be necessary to increase the temperature or extend the time, but this can be dealt with to some extent by adding or increasing the amount of the urethane crosslinking catalyst separately. On the other hand, for the following reasons, the use of the crosslinking agents iii), iv) and v) is preferred.

As described later, since the amount of the crosslinkable material (constituting the polymer component) of the isocyanate-based combination (b) is reduced (10% by weight or less), NCO of the isocyanate component and OH of the crosslinking agent are reduced. In many cases, the lithium electrolyte salt acts as a negative catalyst in the cross-linking reaction with water, and it tends to be difficult to gel with a simple hydroxyl group such as polyoxyalkylene polyol (ii), whereas the cross-linking of (iii) to (V) In the agent, the hydroxyl group due to the N-hydroxyalkyl group and NCO exhibit excellent crosslinking reactivity, that is, great effectiveness. The mono- or poly-N-cyanoethylated poly-N-hydroxyalkylated compound of (iv) can be obtained by leaving the hydroxyl group by N-hydroxyalkylation in the poly-N-hydroxyalkylated compound (iii). It has a cyanoethyl group and improves ionic conductivity due to higher dielectric constant compared to poly N-hydroxyalkylated compound (iii), and electrolyte solvent and lithium electrolyte salt (actually, lithium electrolyte salt This improves the retention of the electrolyte dissolved in the solvent (electrolyte), and has the effect of preventing the separation of the electrolyte from the gel and bleeding. However, since the cyanoethyl group is non-reactive with NCO, the crosslink density decreases and the gelling property decreases accordingly, so the necessity of the cyanoethyl group and its content are determined in consideration of the overall balance. On the other hand, when the hydroxyl group-containing radical copolymer (vi) is used, although the viscosity slightly increases, a good gel can be formed even at a lower polymer concentration, which is advantageous in this respect. Further, when the polymerization ratio of the radical polymerizable monomer having a hydroxyl group is larger than the above range, the gelling property is improved accordingly, but the viscosity is increased, and conversely, when the polymerization ratio is less, the gelling property is reduced.

 In such an isocyanate-based combination (b), the mixing ratio of the isocyanate component to the crosslinking agent is 0.8 to 1.2: 1 equivalent centering on the value calculated from the NCO equivalent of the isocyanate component and the hydroxyl group equivalent of the crosslinking agent. It should be in the range of the ratio.

 c. Monomer combination

 The (meth) acrylic monomer used in this combination has the formula [6]:

9

CH ₂ = C-COOR ₁₀ [6]

(Wherein R ₉ is H or CH ₃ ; and is an alkyl having 1 to 4 carbon atoms). An alkyl (meth) acrylate and / or a formula [7]:

CH ₂ = C— COO— (— R ₁₃ [7] (Wherein, R _lt is H or CH _3; R ₁₂ one CH ₂ CH ₂ 0_ or a _{CH 2 CH (CH 3) -O-} ; R 13 is CH ₃ or C ₂ H _5; and i is 1 To 3), and an alkoxy mono- or polyalkyl (meth) acrylate which is represented by the formula [8]:

CH ₂ = C-COO-R ₁₅ -OOC-C = CH ₂ [8]

Wherein R ₁₄ and R ₁₆ are each H or CH ₃ ; and ₅ is one (CH ₂

₂ . One)

And mono- or polyoxyalkylene di (meth) acrylates as essential components.

 The radical polymerization initiator used in the monomer combination (c) is not particularly limited, and is usually a thermal polymerization initiator such as benzoyl peroxide, lauroyl peroxide, methyl ethyl ketone peroxide, N, N '. —Azobisisobutyronitrile (AIBN), N, N '—Azobisvaleronitrinore can be used. The amount to be used may usually be selected in the range of 0.1 to 5% by weight based on the total amount of the liquid composition.

 d. Polymer combination

 The epoxy group-containing radical copolymer used herein is a copolymer of a (meth) acrylic monomer having an epoxy group and another radically polymerizable monomer.

 The above (meth) acrylic monomer having an epoxy group has the formula:

R ₁₇

CH ₂ = C- COOR ₁₈

(Wherein R ₁₇ is H or CH ₃ ; and R ₁₈ H ₂

Is)

At least one of the (meth) acrylates [ie, 3,4-epoxycyclohexylmethyl (meth) acrylate or glycidyl (meth) acrylate].

 The other radically polymerizable monomers have the formula:

k 19

H ₂ = one: R ₂₀

(Where R ₁₉ is H or CH ₃ ; and R ₂ is _COOCH ₃ , one C〇OC ₂ H ₅ , one C〇〇C ₃ H ₇ , one CO〇C ₄ H ₉ , -COO (CH ₂ CH ₂ O) ^ ₃ CH ₃ ,

-COO (CH ₂ CH ₂₀ ) ₃ C ₂ H ₅ ,

-COO (CH ₂ CH (CH ₃ ) O) ₃ CH ₃ ,

-COO (CH ₂ CH (CH ₃ ) O)

One OCOCH ₃ or one OCOC ₂ H ₅ )

A bull or (meth) acrylic monomer represented by

 The weight ratio between the (meth) acrylic monomer having an epoxy group and the other radically polymerizable monomer is preferably 1:10 to 1: 1.

As the cationic polymerization initiator used in the polymer system combination, For example various Oniumu salt (for the Anmoniumu, Hosuhoniumu, Anoresoniumu, Suchibo two © beam, Suruhoyuu arm, cations such as Yodoniumu one BF _4, _PF _6, one S bF ₆ , A CF ₃ So ₃ , a C 1 O _4, etc.) can be used. However, even if these onium salts are not used in the present invention, the lithium electrolyte salt (3) hexafluorophosphate is not required. The use of lithium and Z or lithium tetrafluoroborate is advantageous in that it can act as the cationic polymerization initiator in addition to the action of the original lithium electrolyte salt. Of course, as part of the cationic polymerization initiator, It is also possible to use lithium fluorophosphate and z or lithium tetrafluoroborate in combination.

 e. Oxetane polymer combination

 The oxetane ring-containing polymer used in this combination is a polymer having a plurality of oxetane rings in the polymer structure, and does not matter the skeletal structure of the polymer, and can be easily obtained by simple radical polymerization.

 That is, a radical polymerizable monomer having an oxetane ring (hereinafter, referred to as “oxetane polymerizable monomer”) and a radical polymerizable monomer having an epoxy group as needed (hereinafter, referred to as “epoxy polymerizable monomer”), It is produced by radical polymerization of another radical polymerizable monomer, and usually has a molecular weight of 1000 or more. If the molecular weight is less than 1000, the amount of polymer required to form a gel tends to be large. The upper limit of the molecular weight is not particularly limited, but it is appropriate to keep the upper limit at about 100,000, preferably about 500,000 in order to maintain the liquid state (solution state) of the liquid composition described later.

 The above radical polymerization is usually carried out by a radical polymerization initiator [eg, N, N'_azobisisobutyronitrile, dimethyl N, N, monoazobis (2-methylpropionate), benzoyl peroxide, lauroyl peroxide, etc.] The polymerization can be carried out using a molecular weight modifier such as mercaptans, and the resulting polymer has a relatively large molecular weight, and the solution polymerization is carried out in a solvent at a temperature of about 60 to 80 ° C. Is preferred. As the solvent, it is preferable to use cyclic carbonates, chain carbonates, and low molecular carboxylic esters exemplified in the electrolyte solution solvent (3) described later.

Examples of the oxetane polymerizable monomer include a compound represented by the formula:

(Wherein, R _{2 x} is H or CH _3; and R _{2 2} is H or § alkyl of 1 to 6 carbon atoms)

(Meth) acrylic monomer represented by Specific of (meth) acrylic monomer Examples are (3-oxetanyl) methyl (meth) atalylate, (3-methyl-13-oxetanyl) methyl (meth) atalylate, (3-ethyl-13-oxetaninole) methyl (meth) atalylate, (3 —Butyl-3-oxetanyl) methyl (meth) atalylate, (3-hexyl-1-oxetanyl) methyl (meth) acrylate, etc. Use at least one of these.

 The amount used is usually selected in the range of 5 to 50%, preferably 10 to 30%, based on the total amount of the monomers when the above-mentioned epoxy polymerization monomer is not used. If it is less than 5%, the amount of polymer required for gelation increases, and if it exceeds 50%, the electrolyte tends to separate (bleed) from the gel.

 The epoxy polymerizable monomer used as needed includes, for example, a compound represented by the formula:

¾5

CH ₂ = C—COOR ₂₆

(Where R ₂₅ is H or CH ₃ ; and R ₂₆ is

Is)

(Meta) acrylates, specifically, 3,4-epoxycyclohexylmethyl (meth) acrylate, glycidyl (meth) acrylate, and at least one of these is used. The amount used is usually such that the proportion of the epoxy polymerizable monomer in the total amount of the oxetane polymerizable monomer is 90% or less, and the total amount of both monomers is 5 to 50%, preferably 10 to 30% in the total amount of the monomer. What is necessary is just to choose.

 The other radically polymerizable monomers described above have the formula:

 23 ΙΪ2—R24

(Wherein, R ₂ 3 is H or CH _3; and R _{2 4} one COOCH _3, one COOC ₂ H _5, one COOC H _7, one C_〇_OC ₄ H _9, one COO (CH ₂ CH ₂ ^ ~ 3 CH ₃ , -COO (CH ₂ CH ₂ O) ^ C ₂ H ₅ , -COO (CH ₂ CH (CH ₃ ) O) ^ CH ₃ -COO (CH ₂ CH (CH ₃ ) 0) ₁ ^ C ₂ H ₅ , — 〇COCH ₃ , or one OCOC ₂ H ₅ )

A butyl or (meth) acrylic monomer represented by

 In addition, monomers other than the above monomers can be used, but the electrolyte solvent used

If the affinity with (3) is low, the electrolyte may separate (bleed) from the gel. The oxetane ring-containing polymer thus produced may be used alone, or the oxetane ring-containing polymer, the above-mentioned radical polymerizable monomer having an epoxy group and another radical polymerizable monomer may be used as described above. An epoxy group-containing polymer having a molecular weight of 10,000 or more obtained by radical copolymerization under the same conditions as described above may be used in combination.

Examples of the cationic polymerization initiator in the oxetane polymer series combination include various dominates (for example, _BF ₄ , 1 PF ₆ , and cations of cations such as ammonium, phosphonium, arsonium, stibodium, sulfonium, and odonium). Anionic salts such as SbF ₆ , —CF ₃ S〇 ₃ , and C 10 ₄ ) can be used. However, in the present invention, hexafluorofluoride, which is a lithium electrolyte salt (3), can be used without using these hondium salts. Use of lithium phosphate and / or lithium tetrafluoroborate is advantageous in that it can act as the cationic polymerization initiator in addition to the action of the original lithium electrolyte salt. The use of a cationic polymerization initiator is an extra component for the electrolyte, which leads to a decrease in ionic conductivity, and also complicates the production process and increases costs.

 Naturally, it is also possible to use lithium hexafluorophosphate and lithium tetrafluoroborate together with the hondium salt as a part of the cationic polymerization initiator.

In the present invention, the amount of the crosslinkable material (1) is usually 10% by weight or less, preferably 7% by weight or less, more preferably 5% by weight based on the total amount of the crosslinkable composition. / ₀ or less. The lower limit of the amount of the crosslinkable material (1) is not limited as long as crosslinking of the crosslinkable composition is possible. Force is preferably 0.5% by weight or more.

In particular, when an oxetane polymer yarn is used as the crosslinkable material (1), the amount of the oxetane ring-containing polymer is 5% by weight based on the total amount of the crosslinkable composition. / ₀ or less Is preferred.

 (2) Electrolyte solvent

 Examples of the electrolyte solvent (2) in the present invention include cyclic carbonates (ethylene carbonate, propylene carbonate, butylene carbonate and the like); and chain carbonates (dimethyl carbonate, getyl carbonate, methyl ethyl ester, methyl carbonate). Cyclic esters (ratatanes) (γ-butyrolactone, γ-valerolatatatone, etc.); Cyclic ethers (tetrahydrofuran, methyltetrahydrofuran, etc.); small molecules Carboxylic esters (ethyl acetate, propyl acetate, butyl acetate, methyl propionate, ethyl propionate, propyl propionate, methyl butyrate, butyl butyrate, etc.); linear ethers (dimethoxetane, methoxyethoxyxetane) ); A compound containing a cyanoethyl group (meth At least one selected from the group consisting of methyl-2-ethyl cyanoethyl ether, ethyl '2-cyanoethyl ether, bis-2-cyanoethyl ether, methyl carbonate-2-cyanoethyl, and propionic acid 2-cyanoethyl. Use one type. In particular, it is preferable to use a mixture of a cyclic carbonate and a low molecular weight carboxylic acid ester in a mixture of a cyclic carbonate and a high dielectric constant solvent of the cyclic ester, and further to use a cyclic carbonate such as ethylene carbonate and carbonate. Propylene, chain carbonates such as dimethyl carbonate, getyl carbonate, methyl carbonate and methyl carboxylate, and low molecular weight carboxylate esters, among which the total number of carbon atoms constituting the molecule is ester chain ester having 4 to 6 carbon atoms, It is preferable to use a mixture of propyl acetate, butyl acetate, methyl propionate, ethyl propionate, propyl propionate, and methyl butyrate. Of these, propyl acetate and propionic acid, which are chain esters having 5 carbon atoms, are preferred. The use of ethyl or methyl butyrate is preferred. In addition, the mixing ratio is set such that cyclic carbonates / chain carbonates / low molecular weight carboxylate esters = 10 to 50: 0 to 50:50 to 90 (weight ratio), and It is preferable to set the low molecular carboxylic acid ester to 50% or more of the whole solvent.

If the total number of carbon atoms constituting the molecule is less than 4 in the low-molecular carboxylic acid esters described above, the boiling point of the solvent is too low, and when a battery is used, the problem that the internal pressure of the battery increases at high temperatures tends to occur. When the total number of carbon atoms is 7 or more, the ionic conductivity decreases. Therefore, battery characteristics tend to decrease.

 (3) Lithium electrolyte salt

Although the lithium electrolyte salt (3) in the present invention is not particularly limited, an anion (acid) having excellent solubility in the electrolyte solvent (2), high ionic conductivity and high resistance to oxidation to reduction potential is used. What is comprised by group) is preferable. For example, lithium perchlorate, lithium tetrafluoroborate, lithium hexafluorophosphate, lithium trifluoromethanesulfonate and the like are used, and at least one of these is used. The concentration used is usually 1 mol / dm ³ before and after is applied.

 Polymer solid electrolyte lithium ion secondary battery

 The polymer solid electrolyte lithium ion secondary battery according to the present invention comprises the above-mentioned crosslinkable material (1) (a combination of a to e), an electrolyte solvent (2) and a lithium electrolyte salt (3) as components. It is characterized in that a low-viscosity liquid composition obtained by mixing and dissolving is used as a crosslinkable composition for a solid electrolyte, and can be produced according to the following procedure.

 First, the proportion of the crosslinkable material (1) in the total amount of the liquid composition was 10%.

(% By weight, the same applies hereinafter) In other words, the amount of the polymer component in the solid electrolyte to be formed is set to a value as low as possible to maintain the ion conductivity stably.

 Next, within the time limit of the pot life of the liquid composition (the time during which injection and the like can be performed by maintaining the liquid state), a unit such as an electrode and a separator for a lithium ion secondary battery is removed. After pouring into a sealed container and allowing it to penetrate into the gap between the electrode and the separator, the temperature is from room temperature to about 100 ° C. The crosslinkable material is easily gelled at room temperature or under heat at a temperature of about 100 ° C), and the desired polymer solid electrolyte lithium-ion secondary battery is obtained by forming a polymer solid electrolyte. .

When a crosslinkable material of the isocyanate-based combination b is used, a urethane crosslinking catalyst (for example, a metal salt such as Sn, Bi, Fe, or Pb; stannous octaate, cyanide) may be used, if necessary. However, when the liquid composition is injected, if a urethane cross-linking catalyst is applied or mixed in advance to the electrode or separator, the urethane cross-linking catalyst can be added to the liquid composition. Can reduce the amount of compound As a result, the bot life can be greatly extended, and after injection, the urethane cross-linking catalyst spontaneously elutes from the electrode / separator, contributing to the promotion of gelation.

 In this way, it is possible to obtain a polymer solid electrolyte lithium ion secondary battery having excellent characteristics and stability without requiring new equipment in the same process as conventional battery production. In the conventional polymer gel-type polymer solid electrolyte, it is important to reduce the amount of polymer components that do not contribute to ionic conductivity.However, even if the crosslink density is increased unnecessarily, the gel retention of the electrolyte can be maintained. The electrolyte solution is easily separated by the decrease, and the structure of the polymer constituting the gel itself is also very important. However, the present invention solves these problems by using a crosslinkable material (1). I can say

 The crosslinkable material (1) used in the present invention can be used in addition to a lithium ion secondary battery, a lithium battery, a lithium secondary battery, an electric double layer capacitor, by changing an electrolyte solvent and a lithium electrolyte salt. It can also be used as a polymer gel-type polymer solid electrolyte for chemical condensers, electoric chromic devices, and the like.

 Example

 Next, the present invention will be described more specifically with reference to Production Examples and Examples.

 Production Example 1

 Production of cyanoethylated epoxy resin:

 In a 100-Om 1 three-necked flask, “EVI SY S G E—6” manufactured by Sovitonore's polyglycidizole

OJ) Take 360 g and 2% NaOH aqueous solution 180 g, and add acrylonitrile 210 g dropwise over about 2 hours while heating to about 40 ° C. During this time, the temperature is maintained at 40 to 42 ° C. After completion of the dropwise addition, the mixture is heated and stirred at the same temperature for 5 hours to carry out a cyanoethylation reaction. Then, water-cool to about 30 ° C, add 300 g of dichloromethane, continue stirring for a while, stop stirring, and allow to stand. If left for about 10 to 20 minutes, it separates into two layers, so only the upper layer is removed. Thereafter, 30 Om1 of ion-exchanged water was added, and the mixture was washed with stirring water, stirring was stopped and the mixture was allowed to stand.The water washing process of removing the upper layer was repeated at least six times in total, and dichloromethane was distilled off under reduced pressure. Stir under heating and reduced pressure while introducing dry nitrogen gas at 0 ° C, and remove the water to obtain a cyanoethylated epoxy resin. (Cyanoethylated sorbitol polyglycidyl ether) is obtained. This cyanoethylated epoxy resin exhibited a light yellow-brown transparent viscous liquid, and a clear absorption peak of a single CN group was confirmed by an infrared absorption spectrum. The measurement result of the epoxy equivalent was 236.

 Production Example 2

 Production of urethane prepolymer A:

 In a 1000 ml three-necked flask previously sufficiently dried with dry nitrogen gas, 406.8 g of tolylene diisocyanate (a mixture of 2,4-tolylene diisocyanate / 2,6-tolylene diisocyanate = 80:20) was added. Then, 400 g of a mixed solvent of ethylene carbonate / getyl carbonate (1Z1, weight ratio) previously dehydrated with a molecular sieve is charged and stirred and mixed. Next, 193.2 g of a dried molecular sieve of polyoxypropylene polyol having a hydroxyl value of 225 obtained by adding propylene oxide to glycerin was added, and the mixture was gradually heated from room temperature to 70 ° C under the introduction of dry nitrogen gas. Heating and stirring are continued for another hour, and the temperature is further reduced to 40 ° C and the reaction is performed overnight to obtain a urethane prepolymer.

 This urethane prepolymer A (solution) was a colorless and transparent viscous liquid, and a clear absorption spectrum of NC〇 group was confirmed by infrared absorption spectrum. The result of quantitative analysis of the NCO group was 9.806%, which almost coincided with the calculated value of 9.887%.

 Production Example 3

 Production of Epoxy-Containing Radical Copolymer A:

177.3 g of methyl methacrylate previously dehydrated with a molecular sieve, and 3,4-epoxycyclohexyl methacrylate previously dehydrated with a molecular sieve in a 1000 ml three-necked flask previously dried sufficiently with dry nitrogen gas. 59. lg, 722.1 g of a mixed solvent of ethylene carbonate / getyl carbonate (1: 1, weight ratio) previously dehydrated with a molecular sieve, 3.9 g of azobisisosopuchi-mouthed trinole previously dried under reduced pressure, and lauryl mercaptan 0.4 g, and stirred at 70-75 ° C while introducing dry nitrogen gas.Continue heating and stirring for 6 hours, then lower the temperature to 40 ° C and react overnight to obtain epoxy group-containing radicals. Obtain copolymer A (solution). This copolymer was a pale yellow, transparent, low-viscosity liquid, and a clear absorption spectrum of an epoxy group was confirmed by an infrared absorption spectrum. When the epoxy equivalent was measured, it was found to be 732, which was almost the same as the calculated value of 728.5.

 Production Example 4

 Production of urethane prepolymer B:

 The “mixed solvent of ethylene carbonate / getyl carbonate (lZl, weight ratio) previously dehydrated with a molecular sieve” used in Production Example 2 (production of urethane pre-borima-A) was replaced with “carbonate previously dehydrated with a molecular sieve. Ethylene / “propylene carbonate”

(1/1, by weight ratio), and the other steps are the same as in Production Example 2 to obtain urethane prepolymer B.

 This urethane prepolymer B (solution) was a colorless and transparent viscous liquid, and a clear absorption spectrum of NCO groups was confirmed by an infrared absorption spectrum. The quantitative analysis result of the NCII group was 9.822%, which was almost in agreement with the calculated value of 9.887%.

 Production Example 5

 Production of Epoxy Group-Containing Radical Copolymer B:

CH ₂ = CHCOO {CH ₂ CH (CH ₃ ) 〇} ₂ CH ₃ 177.3 g, previously dehydrated with a molecular sieve, in a 1000 ml three-necked flask that has been thoroughly dried with dry nitrogen gas. 59.1 g of dehydrated 3,4-epoxycyclohexylmethyl acrylate, 709.2 g of a mixed solvent of 50 parts by weight of ethylene carbonate and 50 parts by weight of propylene carbonate previously dehydrated by molecular sieve, and vacuum drying in advance Take 3.9 g of N, N'-azobisisobutyronitrile and 0.4 g of laurino remel kabutane, stir at 70 to 75 ° C while introducing dry nitrogen gas, and heat and stir for 6 hours. Subsequently, the reaction is further performed overnight at a temperature of 40 ° C. to obtain an epoxy group-containing radical copolymer B (solution).

 This epoxy-group-containing radical copolymer (B) is a pale yellow, transparent, low-viscosity liquid. As a result of infrared absorption spectrum measurement, a clear epoxy group absorption spectrum was confirmed. As a result of the measurement, it was found that the calculated value of 724 was ^ (straight) which is almost the same as the calculated value of 728.5.

Example 1 (Use crosslinkable material of epoxy combination _a )

 In a glove box filled with dry nitrogen gas, 10 g of the cyanoethylated epoxy resin obtained in Production Example 1 and ethylene glycol dicarbonate in which lithium hexafluorophosphate was dissolved in a monolayer concentration (1/1, weight ratio) 143.7 g of a mixed solvent solution of above is mixed, and then 2.5 g of pentaethylenehexamine is added and mixed to prepare a liquid composition. The polymer concentration in the liquid composition is [(10 + 2.5) /15.6.2] × 100 = 8.0%.

 Next, a sealed container (diameter: 18 mm, total length: 65 Omm, cylindrical type, commonly called type 18650) incorporating units such as electrodes for lithium ion secondary batteries and separators prepared in advance is prepared. Then, 4.86 g of the above-mentioned liquid composition was injected, impregnated in a vacuum, sealed, and heated at 70 ° C. for 10 hours to perform gelation, thereby preparing a polymer solid electrolyte lithium ion secondary battery.

 The 18650 type used above is made of a lithium-cobalt-based material for the positive electrode, a carbon-based material for the negative electrode, and a polyolefin-based separator, and is a very common type with a capacity of 160 OmAH. .

 Example 2

 (Use cross-linkable material of isocyanate combination b)

 5.0 g of the urethane prevolima-A (60% solution) obtained in Production Example 2 and tetra-N-hydroxypropylethylenediamine, a poly-N-hydroxypropyl compound (Sanyo Chemical Co., Ltd.) ), Manufactured by "Newpole NP-300") with a mixed solvent of ethylene carbonate / getyl carbonate (1Z1, weight ratio). /. A mixture of 1.4 g of the solution and 53.6 g of a mixed solvent solution of ethylene carbonate and getyl carbonate (1/1, by weight) in which lithium hexafluorophosphate was dissolved at a molar concentration was used as a urethane crosslinking catalyst. 0.1 g of a 10% getyl carbonate solution of stannous octate (Neostan U-28, manufactured by Nitto Kasei Co., Ltd.) is added and mixed to prepare a liquid composition (polymer concentration 6. Four%) .

Next, in Example 1, except that the injection amount of the liquid composition was 4.69 g and the heating conditions for gelation were 70 ° C for 30 minutes, the polymer solid electrolyte lithium ion secondary ion was used under the same conditions as in Example 1. Create batteries 2δ Example 3

 (Use crosslinkable material of monomer combination c)

 2-Methoxyxylatari I 5.0 g, trioxypropylene glycol diacrylate 4.0 g, formula:

CH ₂ = CH— COO— (CH ₂ CH ₂ O) ₉ OC-CH = CH ₂

A mixture of 1.0 g of diacrylate of a 9-mer polyoxyethylene glycol and 1.O g of benzoyl peroxide shown in, and then ethylene carbonate obtained by dissolving lithium hexafluorophosphate to 1 molar concentration Add 137.6 g of a mixed solvent solution of dimethyl alcohol / getyl carbonate (1/1, weight ratio) and mix to prepare a liquid composition (polymer concentration: 7.4%).

 Next, in Example 1, except that the injection amount of the liquid composition was 4.96 g and the heating conditions for gelation were 70 ° C for 30 minutes, the polymer solid electrolyte lithium ion secondary ion was used under the same conditions as in Example 1. Create a battery.

 Example 4

 (Use crosslinkable material of polymer combination d)

 Mix 16 g of the epoxy group-containing radical copolymer A obtained in Production Example 3 and 84 g of a mixed solvent of ethylene carbonate Z getyl carbonate (1/1, by weight) in which lithium hexafluorophosphate is dissolved at a 1 molar concentration. To prepare a liquid composition (polymer concentration: 4.0%).

 Next, in Example 1, except that the injection amount of the liquid composition was 3.73 g and the heating conditions for gelation were 70 ° C for 1 hour, the polymer solid electrolyte lithium ion secondary ion was used under the same conditions as in Example 1. Create a battery.

 In this example, lithium hexafluorophosphate was used as the lithium electrolytic salt, and no separate cationic polymerization initiator was used.

 Example 5

 (Sheet-type battery using cross-linkable material of individual combination b)

In a gas box filled with dry nitrogen gas, tetra N-hydroxypropyl ethylenediamine, a poly N-hydroxy pill compound (manufactured by Sanyo Chemical Co., Ltd., "New-Poly NP-300") Ethylene carbonate Z propylene carbonate (1/1, (Weight ratio) in a mixed solvent of 1.4 g of a 60% solution of lithium hexafluorophosphate in a molar concentration of 1.4% in a mixed solvent of ethylene carbonate and propylene carbonate (lZl, weight ratio). g, and uniformly mixed. Further, the urethane prepolymer B5.Og obtained in Production Example 4 was added and mixed. Then, stannous otatoate (Nitto Kasei Co., Ltd. 0.1 g of a 10% solution of U-28 ") in getyl carbonate is mixed and mixed to prepare a liquid composition (polymer concentration: 5.0%).

 Next, 4.17 g of the above liquid composition was poured into a bag-like container made of an aluminum laminate film into which a sheet-like electrode for a lithium ion secondary battery and a unit made of a nonwoven fabric were prepared in advance. After performing vacuum impregnation, it is sealed and heated at 70 ° C. for 1 hour to perform gelation, thereby producing a sheet-shaped polymer solid electrolyte lithium ion battery.

 The unit of the sheet-shaped lithium ion secondary battery used above had a structure in which the positive electrode was sandwiched between the negative electrodes from both sides of the positive electrode through a nonwoven fabric, and the positive electrode was made of an active material mainly composed of lithium cobalt oxide on both sides of an aluminum foil. The size of the negative electrode is 68 mm x 84 mm.The negative electrode is a copper-based material coated on one side with a carbon-based material.The size is 70 mm x 86 mm.The nonwoven fabric is made of polyester fine fiber. This unit is a 0 / m thick product, and this unit is incorporated in a bag-shaped aluminum laminate film (polyethylene inside, polypropylene outside) with a heat-sealed periphery. The battery capacity is 30 OmAH .

 Example 6

 (Sheet battery using crosslinkable material of polymer combination d)

 Mixed solvent solution of 12.0 g of the epoxy group-containing radical copolymer B obtained in Production Example 5 and ethylene carbonate / propylene carbonate (1/1, by weight) in which lithium hexafluorophosphate was dissolved at a 1 molar concentration. Mix 88.0 g to prepare a liquid composition (polymer concentration: 3.0%).

 Next, in Example 5, a sheet-like polymer was prepared under the same conditions as in Example 5, except that the injection amount of the liquid composition was 4.05 g and the heating conditions for gelling were 70 ° C for 1 hour. Create a solid-state lithium-ion secondary battery.

Note that, in Example 6, as in Example 4, hexafluorophosphoric acid was added to the lithium electrolyte salt. Lithium is used and no separate cationic polymerization initiator is used.

 Table 1 below shows the results of the charge / discharge repetitive test (3 cycles and 10 cycles) using the lithium ion secondary batteries prepared in Examples 1 to 6.

 The charge and discharge conditions in each cycle were fixed at 0.2 C (32 OmA in Examples 1 to 4 and 6 OmA in Examples 3 to 4) until the charge reached 4.2 V. After current charging, after reaching 4.2 V, constant voltage charging at the same voltage for 8 hours, each discharge is 0.2 C (Examples 1-4 are 32 OmA, Examples 3-4 are 6 OmA ) Is constant current discharge until the voltage reaches 2.75 V.

 Note: The unit of charge and discharge is mAH, efficiency is discharge

 bX 100 (unit:%). Production Example 6

 Of oxetane ring-containing polymer

In a 1 000 ml three-necked flask previously dried sufficiently with dry nitrogen gas, 108 g of methyl methacrylate previously dehydrated with a molecular sieve, and (3-ethyl-3-oxetanyl) methyl previously dehydrated with a molecular sieve 36 g of atalylate, previously dehydrated with a molecular sieve, and vacuum-distilled under reduced pressure to a mixture of 432 g of heated normal ethylene carbonate, mixed with dimethyl N, N'-azobis (2-methylpropionate) 0.25 g, and the mixture is stirred at 70 ° C while introducing dry nitrogen gas. Then, the mixture is heated and stirred for 12 hours to perform radical polymerization. Next, lower the temperature to 40-50 ° C, After drying with a molecular sieve and adding 378 g of ethyl propionate distilled under reduced pressure, the mixture is stirred and dissolved until the whole becomes uniform to obtain a 15% solution of the oxetane ring-containing polymer.

The polymer first solution is a colorless transparent viscous liquid, infrared absorption spectrum results of the measurement, _c Example 7 was confirmed to have a characteristic absorption clear Okisetan ring wavenumber 9 8 0 Bruno cm

 (Preparation of liquid composition A)

 In a glove box filled with dry nitrogen gas, 10 g of the solution of the oxetane ring-containing polymer obtained in Production Example 6 and ethylene carbonate / getyl carbonate dimethyl carbonate dissolved in lithium hexafluorophosphate at a 1 molar concentration (dimethyl carbonate) A liquid composition A is prepared by mixing and dissolving 40 g of a mixed solvent solution of 107 10/40 (weight ratio). The polymer concentration in the liquid composition A is 3.0%.

 This liquid yarn A was heated and crosslinked at 70 ° C., and the gelling property, the state of the gel, and the ion conductivity (lO ^ SZcm) were evaluated. The gelation and gel state were visually observed; the ion conductivity was determined by injecting the liquid composition into a closed cell incorporating a gold-plated electrode, heating at 70 ° C for 5 hours in a closed state, and then cooling. The specimen was used for measurement, and the measurement was performed using an LCZ meter at a frequency of 1 KHz and a measurement temperature of 20 ° C or 120 ° C. The results are shown in Table 2 below.

 Example 8

 (Preparation of liquid composition B)

 In the same manner as in Example 7, 10 g of the solution of the oxetane ring-containing polymer obtained in Production Example 6, and ethylene carbonate / dimethyl carbonate Z-ethyl propionate (15) in which lithium hexafluorophosphate was dissolved at a 1.3 molar concentration. 40 g of a mixed solvent solution (weight ratio: Z157770) is mixed and dissolved to prepare a liquid composition B (polymer concentration: 3.0%). As in Example 7, the liquid composition B is prepared. Next, the gelation property, gel state and ion conductivity were evaluated, and the results are shown in Table 2 below. In Table 2, in the evaluation of gelability

"〇" indicates that the gel is formed.

Gelling properties 〇 〇

 Transparent and electrolyte transparent and electrolyte

Genore Noh

 No bleed No bleed

Ionic conductivity

 (10— / cm)

 20 ° C 8.855 8.904

 20C 3.925 3.930

 Comparative example

 Formula:

2.5 g of a low-molecular alicyclic epoxy compound represented by the following formula (“CELLOXIDE 2021 Ρ”, manufactured by Daicel Industries, Ltd.): ethylene carbonate prepared by dissolving lithium hexafluorophosphate in a 1.0 molar concentration Z dimethyl carbonate Z Dissolve it in 47.5 g of a mixed solvent solution of ethyl propionate (15 to 15/70, weight ratio) to prepare Liquid Composition C (low-molecular alicyclic epoxy compound concentration 5%).

 In the same manner as in Example 7, this liquid composition C was polymerized by heating at 70 ° C., and the gelling property, the gel state, and the ionic conductivity were evaluated. The results are shown in Table 3 below.

 Comparative Examples 2 and 3

 A liquid composition DE was prepared in the same manner as in Comparative Example 1, except that the concentration of the low molecular weight alicyclic epoxy compound was changed to 6% (Comparative Example 2) or 8% (Comparative Example 3), respectively. Table 3 below shows the evaluation results of the chemical properties, gel state and ionic conductivity. Comparative Example 4

 Formula:

3 g of an oxetane ring-containing compound (“XDO” manufactured by Ube Industries, Ltd.) Lithium hexafluorophosphate was dissolved in 47 g of a mixed solvent solution of ethylene carbonate / dimethyl Z-ethyl propionate (15/15/70, weight ratio) dissolved in 1.0 molar concentration, and the liquid composition F ( Prepare a low-molecular-weight oxetane ring-containing compound at a concentration of 6%).

 In the same manner as in Example 7, this liquid composition F was heated and polymerized at 70 ° C., and the gelling property, the gel state, and the ionic conductivity were evaluated. The results are shown in Table 3 below.

 Comparative Examples 5 and 6

 In Comparative Example 4, except that the concentration of the low-molecular-weight oxetane ring-containing compound was 8% (Comparative Example 5) or 10% (Comparative Example 6), liquid compositions G and H were prepared in the same manner, Table 3 below shows the evaluation results of the gelling property, gel state, and ionic conductivity. In Table 3, “X” indicates that the liquid state is not gelled, and “〇” indicates that the gelled state. Table 3

 From the results in Table 3, when the low-molecular alicyclic epoxy compound or the low-molecular oxetane ring-containing compound [monomer] is simply polymerized and gelled, the polymer content is about 5% (the monomer content is 100% polymer). (The monomer content is assumed to be the polymer content), gelation does not occur (Comparative Examples 1 and 4), and gelation occurs at about 6% or more, but liquid components bleed, and It can be seen that no gel could be formed and good results could not be obtained with ionic conductivity.

Example 9 (Preparation of lithium ion secondary battery A) Inject the liquid composition A of Example 7 (1.85 g) into a bag made of aluminum laminated film with a lithium ion battery electrode and a nonwoven fabric unit prepared in advance and vacuum impregnation. After sealing, heat at Ί0 ° C for 19 hours to perform gelation by cross-linking, and create a thin polymer solid electrolyte lithium ion secondary battery A.

 The unit of the thin lithium ion secondary battery used above has a structure in which a positive electrode and a negative electrode are wound via a nonwoven fabric, and the positive electrode is coated with an active material mainly composed of lithium cobalt oxide on both surfaces of an aluminum foil. The size is 50 x 8 Omm, the negative electrode is a copper foil coated with a carbon-based material, the size is 52 x 110 mm, and the non-woven fabric is 20 μm made of polyester fine fiber. This unit is a thick product in which a bag-like aluminum laminating film (inner surface: polyethylene, outer surface: polypropylene) is heat-sealed. The capacity of the battery was 180 mAH, and six identical batteries (No .: 6) were created.

 Example 10

 (Preparation of lithium ion secondary battery B)

 As in Example 9, using the liquid composition B of Example 8, thin polymer solid electrolyte lithium ion secondary batteries B (six) were prepared.

 Using the thin polymer-solid electrolyte lithium ion secondary batteries A and B prepared in Examples 9 and 10, the results of the charge / discharge repetition test and the load characteristics at normal temperature and the load characteristics at low temperature are shown in the following table, respectively. Shown in 4 and 5.

 The conditions of the charge / discharge repetition test are as follows. The charge / discharge cycle is repeated at 1 C (180 mA) for both charge and discharge, and the capacity at the initial 1 cycle and the capacity and retention after 10 cycles are shown. The load characteristics at room temperature are as follows: charge: 0.2 C (36 mA), discharge: 0.2 C, 1 C, 2 C (360 mA), discharge capacity and 0.2 C discharge capacity Shows the retention. The load characteristics at low temperatures were measured by measuring the 0.5 C (90 mA) discharge capacity at both 20 ° C and 0.5 C (90 mA) discharge capacity at room temperature. It is.

All charging is performed until the constant current reaches 4.2 V, and all discharging is performed until the constant current reaches 2.75 V. Table 4

 No.

 ■ 、 ■--,-,,-1 2 3 4 5 6 Yu [ίReturn test

 • Initial 1 cycle (mAH) 182.7 186.3 184.0 182.6 182.7 78.0

• 10 cycles (mAH) 174. 4 179. 7 176. 3 173. 9 174. 5 170. 4 Same retention rate (%) 96. 0 96. δ 95. 8 95. 2 95. δ 94.7 Normal temperature load Characteristic

 -0.2C capacity (mAH) 200.2 199.5 5198.7 199.4 4200.9

-1C capacity (mAH) 187.6 190. 4 188. 4 188. 3 187. 7 187.0 0 Retention rate (%) 96. 0 95. 1 94. 4 94. 8 94. 1 93. 1

-2C capacity (mAH) 172 L. 4 174. 3 170. δ 168. 6 168. 5 168. 8 Same retention (%) 88. 2 87. 1 85. 5 84. 9 84. 5 84. 0 Low temperature Load characteristics (0.5C)

 -Room temperature capacity (mAH) 190.8 194.1 182.6 6193.0 193.0

--20 ° C capacity (mAH) 94.5 97.6 99.6 90.0 98.6.97.1 Same retention rate (%) 49.5 50.3 51.δ49.3 51.1 50. Three

, Ν. ·,

 1 2 3 4 5 6 Repeated charge / discharge test Ο

 ■ Initial 1 cycle (mAH) 182.2 186.0 183.8 8189.1 187.6 186.7

■ 10 cycles (mAH) 174.2 178.4 47.3 2 184.6 181.0 0 179.5 Same retention rate (%) 95.6 95.9 94.2 97.6 96.5 96.1 Normal temperature load Characteristic

 ■ 0.2C capacity (mAH) 196.7 7200. 0 199.7 7200. 7 200.3

• 1 C capacity (mAH) 187.7 190. 5 189. 4 191.3 191. 6 190. 8 Retention rate (%) 95. 4 95. 3 94. 8 95. 3 95. 0 95.3

-2C capacity (mAH) 173.6 67.8 4 173.5 5179.80 180.5 179.2 Same retention rate (%) 88.3 89.2 86.9 89.6 89.5 89.5 Low temperature load Characteristics (0.5C)

 -Room temperature capacity (mAH) 190.4 193.4 4192.8 194.2 2194.4 193.4

--20 ° C capacity (mAH) 1 13. 7 1 18. 2 120. 9 1 19. 0 1 16. 6 1 13.7 Retention rate (%) 59. 7 61. 1 62. 7 61. 3 60.0 58.8

Claims

The scope of the claims

 1. A polymer solid electrolyte comprising a positive electrode and a negative electrode for a lithium ion secondary battery, a separator disposed between the two electrodes, and a polymer solid electrolyte, wherein the polymer solid electrolyte comprises:

 (1) Crosslinkable material

 (2) electrolyte solvent and

 (3) Lithium electrolyte salt

Wherein the amount of the crosslinkable material (1) is 10% by weight in the total amount of the composition. / ₀ or less, a liquid crosslinkable composition for a solid electrolyte is injected into a sealable battery container incorporating a unit including the electrode and a separator, and gelled by crosslinking.Polymer as a solid electrolyte Electrolyte lithium ion secondary battery.

 2. Crosslinkable material (1) Force

 a. a combination of an epoxy resin and its crosslinking agent,

 b. a combination of at least one compound selected from the group consisting of a polyisocyanate compound and a urethane prepolymer, and a crosslinking agent thereof;

 c. Combination of (meth) acrylic monomer and radical polymerization initiator,

 d. a combination of an epoxy group-containing radical copolymer and a cationic polymerization initiator, and

 e. Combination of oxetane ring-containing polymer and cationic polymerization initiator

The polymer solid electrolyte lithium ion secondary battery according to claim 1, which is at least one kind of crosslinkable material selected from the group consisting of:

 3. The crosslinkable material (1) comprises the combination a, wherein the epoxy resin has the formula:

(CH ₂ CH-CH ₂ 0) a-R _x- (OCH ₂ CH ₂ CN) b

O (where a is a number from 2 to 5 and b is a number from 1 to 4, wherein a + b is from 3 to 6; and has a molecular weight of less than 250 having 3 to 6 hydroxyl groups in the molecule. This is a residue that removes all hydroxyl groups from a polyol compound.) Including a cyanoethylated epoxy resin represented by

 The crosslinking agent has the formula:

H ₂ N-CH _: CH _2- (NH-CH ₂ CH ₂ ) c-NH ₂

 (Where c is a number from 0 to 4)

And a polyethyleneboramine represented by the formula:

( ₃ ) e R ₄ ( ₅ ) g

(R ₂ ) dN-CH ₂ CH _2- (N-CH ₂ CH ₂ ) fN- (R ₆ ) h

(Wherein, R ₂ , R _{; (} , R ₄ , R ₅ and R ₆ (R to R ₆ ) are each H or —CH ₂ CH ₂ CN; d, e, g and h are each 0 to 2, d + e is 2, g + h is 2; and ί is 0 to 4, provided that at least two of R _{2 to} R ₆ are H and at least one is CH ₂ CH ₂ CN.

3. The polymer solid electrolyte lithium ion secondary battery according to claim 2, which is at least one compound selected from the group consisting of partially cyanoethylated polyethylene polyamines represented by:

 4. The crosslinkable material (1) comprises the combination b, wherein the polyisocyanate compound is

2, 4 or 2, 6 tolylene diisocyanate or a mixture thereof, 4, 4'-diphenylmethane diisocyanate, isophorone diisocyanate, 1, 6-hexamethylene diisocyanate 3. The compound according to claim 2, wherein the compound is at least one compound selected from the group consisting of 2,4,6 trimethylhexamethylene diisocyanate, xylylene diisocyanate, and a diphenylmethane diisocyanate of the cloud type. Polymer-solid electrolyte lithium ion secondary battery.

 5. The crosslinkable material (1) comprises the combination b, wherein the urethane prepolymer is an isocyanate group-containing ゥ ethane prepomer obtained by reacting a polyol having a molecular weight of less than 400 with an excess of polyisocyanate in excess of the equivalent. Yes,

Crosslinking agents, polymer primary solids electrolyte lithium ion secondary battery of claim 2 wherein said molecule less weight 400 polyol, yet hydroxyl value ⁴ 00 or more polyol compounds.

6. The crosslinkable material (1) is composed of the combination b, and the crosslinker has 2 to 6 A polyoxyethylene polyol or a polyoxypropylene polyol having a molecular weight of less than 800, which is obtained by adding ethylene oxide or propylene oxide to a polyol having a hydroxyl group, according to any one of claims 2, 4, and 5. The polymer solid electrolyte lithium ion secondary battery described in the above.

 7. The crosslinkable material (1) comprises the combination b, wherein the crosslinking agent has at least one

Poly N-hydroxyalkylated compound obtained by adding ethylene oxide and Z or propylene oxide to a compound containing an active hydrogen atom by two amine amino and / or imino groups or ammonia The polymer solid electrolyte lithium ion secondary battery according to any one of claims 2, 4, and 5, wherein

 8. The crosslinkable material (1) comprises the combination b, and the crosslinking agent has at least one molecule in the molecule.

Compounds containing three or more amine-based amino and / or Z or imino groups containing an active hydrogen atom or ammonia and adding ethylene oxide and Z or propylene oxide to N to leave at least one active hydrogen atom 6. A mono- or poly-N-cyanoethylated poly-N-hydroxyalkylated compound obtained by hydroxyalkylation followed by cyanoethylation of remaining active hydrogen atoms, according to any one of claims 2, 4 and 5. Polymer solid electrolyte lithium ion secondary battery.

 9. The crosslinkable material (1) comprises the combination b, wherein the crosslinking agent is a partial cyanoethylation obtained by partially cyanoethylating a part of the hydroxyl groups of the poly (N-hydroxyalkylated compound) according to claim 7. The polymer solid electrolyte lithium ion secondary battery according to any one of claims 2, 4 and 5, wherein the lithium ion secondary battery is a poly N-hydroxyalkylated compound.

 10. The crosslinkable material (1) is composed of the combination b, and the crosslinking agent is a hydroxyl group-containing radical copolymer obtained by copolymerizing a radical polymerizable monomer having a hydroxyl group with another radical polymerizable monomer. The polymer solid electrolyte lithium-ion secondary battery according to any one of claims 2, 4, and 5.

 11. The lithium polymer solid electrolyte according to claim 10, wherein the radically polymerizable monomer having a hydroxyl group is a part (meth) acrylate of a polyhydroxy compound in which at least one hydroxyl group remains in the molecule. Ion secondary battery.

12. The polymer according to claim 11, wherein the polyhydroxy compound is a high hydroxyl value polyhydroxy compound having a hydroxyl value of 400 or more having 2 to 6 hydroxyl groups in a molecule. One solid electrolyte lithium ion secondary battery.

 1 3. The high hydroxyl value polyhydroxy compound is selected from the group consisting of ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, glycerin, diglycerin, triglycerin, erythritol, pentaerythritol, dipentaerythritol, xylitol and sorbitol. 13. The polymer solid electrolyte lithium ion secondary battery according to claim 12, which is at least one selected from the group consisting of:

 14. Other radically polymerizable monomers have the formula:

R ₇ > H ₂ 1 R ₀

(Where R ₇ is H or CH ₃ ; and R ₈ is one of CN COOCH or COO C ₂ H ₅ — COO (CH ₂ 〇 〜 to ₃ CH ₃ — CO〇 (CH ₂ CH ₂ 〇) to C ₂ H ₅ — COO (CH ₂

₃ CH ₃ — CO◦ (CH ₂ CH (CH ₃ ) O) 3C ₂ H ₅ OCOCH ₃ , or one OCOC ₂ H ₅

The polymer-solid electrolyte lithium ion secondary battery according to any one of claims 10 to 13, wherein the polymer-based or (meth) acrylic monomer is represented by the following formula:

 15. The polymer solid electrolyte lithium ion secondary battery according to any one of claims 10 to 14, wherein the weight ratio of the radical polymerizable monomer having a hydroxyl group to the other radical polymerizable mono is 11011.

 1 6. The cross-linkable material (1) is composed of the combination b, and the cross-linkable material is preliminarily coated or mixed with a urethane cross-linking catalyst on an electrode or a separator. 2. The polymer solid electrolyte lithium ion secondary battery according to claim 1.

1 7. The crosslinkable material (1) comprises the combination c, and the (meth) acrylic monomer has the formula: R ₉

CH ₂ = C—COOR ₁₀

Wherein R ₉ is H or CH ₃ ; and is an alkyl having 1 to 4 carbon atoms, and an alkyl (meth) acrylate represented by the formula:

R]]

 I

CH ₂ = C—COO— (R, ₂ ) i—R, 3

(Wherein is H or CH ₃ ; R ₁₂ is one CH ₂ CH ₂ 〇 one or one CH ₂ CH (CH ₃ ) -0-; R ₁₃ is CH ₃ or C ₂ H ₅ ; and i is 1-3. At least one (meth) acrylate which is selected from the group consisting of alkoxy mono- or polyalkyl (meth) acrylates represented by the formula:

^ 1 4 | 6

CH ₂ = C-COO-R ₁₅ -OOC-C = CH ₂

Wherein R ₁₄ and R ₁₆ are each H or CH ₃ ; and R ₁₅ is

-(CH ₂ CH ₂ 0) ₁ ^ ₂₀ -or one {CH ₂ CHiCH O} ^ ₂ . One)

3. The polymer solid electrolyte lithium ion secondary battery according to claim 2, wherein the mono- or polyoxyalkylene di (meth) acrylate is represented by the following formula:

 1 8. The crosslinkable material (1) is composed of the combination d, and the epoxy group-containing radical copolymer is a copolymer of an epoxy group-containing (meth) acrylic monomer and another radical polymerizable monomer. hand,

The above (meth) acrylic monomer having an epoxy group has the formula: R 1 7

CH ₂ = C COOR _ls

Wherein R ₁₇ is H or CH ₃ ; and R ₁₈ is H ₂

Is)

3. The polymer solid electrolyte lithium ion secondary battery according to claim 2, which is at least one kind of (meth) acrylate which is represented by the following formula.

 1 9. Other radically polymerizable monomers have the formula:

H ₂ — One Iv ₂₀

(Wherein, R ₁₉ is H or CH _3;. And R ₂ _COOCH ₃ _COOC ₂ H ₅ one CO_〇_C _{3 H 7 COOC 4 H 9 COO} (CH 2 CH 2 0) DOO ₃ CH ₃ CO O CF ^ CF ^ O) ^ ₃ C ₂ H ₅ COO (CH ₂ CH CH O) ^ ₃ CH ₃ C 00 (CH ₂ CH (CH ₃ ) 0) ₁ ^ ₃ C ₂ H ₅ —OCOCH ₃ , or one OCOC ₂ H ₅ )

19. The polymer-solid electrolyte lithium ion secondary battery according to claim 18, which is a bullet-based or (meth) acrylic-based monomer represented by:

 20. The polymer solid electrolyte lithium ion secondary battery according to claim 18 or 19, wherein the weight ratio between the (meth) acrylic monomer having an epoxy group and the other radically polymerizable monomer is 1: 101: 1. battery.

2 1. The polymer-solid electrolyte lithium ion 2 according to claim 2, wherein the crosslinkable material (1) comprises a combination d, and the cationic polymerization initiator is an ionic salt. Next battery.

22. Claims 2 and 18 to 20 wherein lithium hexafluorophosphate and Z or lithium tetrafluoroborate used as the lithium electrolyte salt (3) are used as part or all of the cationic polymerization initiator. The polymer solid electrolyte lithium ion secondary battery according to any one of the above.

 23. The polymer-solid electrolyte lithium ion secondary ion according to claim 2, wherein the crosslinkable material (1) is a combination of e-carbon and the amount of the oxetane ring-containing polymer is 5% by weight or less based on the total amount of the composition. battery.

 24. The oxetane ring-containing polymer is a polymer having a molecular weight of 1000 or more obtained by radical copolymerization of a radical polymerizable monomer having an oxetane ring with another radical polymerizable monomer. 2. The polymer solid electrolyte lithium ion secondary battery according to 1.

 25. The polymer solid electrolyte lithium ion secondary battery according to claim 24, wherein the amount of the radical polymerizable monomer having an oxetane ring is 5 to 50% by weight based on the total amount of the monomer.

 26. The oxetane ring-containing polymer has a molecular weight of 1000 or more obtained by radical copolymerization of a radical polymerizable monomer having an oxetane ring and a radical polymerizable monomer having an epoxy group with another radical polymerizable monomer. 24. The polymer solid electrolyte lithium ion secondary battery according to claim 23, which is a polymer.

 27. The proportion of the radical polymerizable monomer having an epoxy group in the total amount of the radical polymerizable monomer having an oxetane ring and the radical polymerizable monomer having an epoxy group is 90% by weight or less, and the total amount of both monomers is However, the total weight of the monomer is 5 to 50 weight. /. 27. The polymer solid electrolyte lithium ion secondary battery according to claim 26, wherein

 28. An epoxy group-containing polymer having a molecular weight of 1000 or more obtained by radical copolymerization of a radical polymerizable monomer having an epoxy group with another radical polymerizable monomer, in combination with the oxetane ring-containing polymer. One of 2 3 to 2 7

(The polymer-solid electrolyte lithium ion secondary battery of this description.

29. The radical polymerizable monomer having an oxetane ring has the formula:

(Wherein, R ₂ is H or CH _3; and R _{2 2} is H or § alkyl of 1 to 6 carbon atoms)

The polymer solid electrolyte lithium ion secondary battery according to any one of claims 24 to 27, which is a (meth) acrylic monomer represented by the following formula:

 30. Other radically polymerizable monomers have the formula:

I

Shi Roshi R24

(Wherein, R ₂ is H or CH _3; and R _{2 4} is -COOCH _3, one COOC ₂ H _5, one COOC ₃ H _7, one CO_〇_C _{4 H 9, -COO (CH 2} CH 2 O) ^

— COO (CH ₂ CH ₂ 0) ₃ C ₂ H ₅ , COO (CH ₂

_{3 CH 3, - COO (CH} 2 CH (CH 3) _{〇) 1 ~ 3 C 2 H 5} , _OCOCH 3, or an OCOC ₂ H _s)

The polymer-solid electrolyte lithium ion secondary battery according to any one of claims 24 to 29, which is a bullet-based or (meth) acrylic-based monomer represented by the following formula:

 3 1. A radical polymerizable monomer having an epoxy group has the formula:

 ¾5

CH ₂ = C—COOR ₂₆

Wherein R ₇ -is H or CH; and R is

Is)

The polymer solid electrolyte lithium ion secondary battery according to any one of claims 26 to 30, which is a (meth) acrylate represented by the following formula:

32. The method according to any one of claims 23 to 31, wherein the cationic polymerization initiator is an onium salt. 4. The polymer solid electrolyte lithium ion secondary battery according to any one of the above.

 33. The electrolytic solution solvent is a mixture of at least one selected from the group consisting of cyclic carbonates, chain carbonates and cyclic carboxylic acid esters, and low molecular chain carboxylic acid esters. The volima solid electrolyte lithium ion secondary battery according to any one of claims 23 to 32.

 34. Any one of claims 23 to 33, wherein lithium hexafluorophosphate and / or lithium tetrafluoroborate used as a lithium electrolyte salt (3) is used for part or all of the cationic polymerization initiator. The polymer-solid electrolyte lithium-ion secondary battery according to 1.

 35. Crosslinkable composition for liquid solid electrolyte is

 Oxetane ring-containing polymer,

 Electrolyte solvent, and

 At least one lithium electrolyte salt selected from the group consisting of lithium hexafluorophosphate and lithium tetrafluoroborate

35. The polymer solid electrolyte lithium ion secondary battery according to claim 34, comprising a power.

 36. (1) Oxetane ring-containing polymer,

 (2) a cationic polymerization initiator,

 (3) electrolyte solvent, and

 (4) Lithium electrolyte salt

A liquid crosslinkable composition for a solid electrolyte, wherein the amount of the oxetane ring-containing polymer (1) is 5% by weight or less based on the total amount of the composition.

 37. Oxetane ring-containing polymers,

 Electrolyte solvent, and

 At least one lithium electrolyte salt selected from the group consisting of lithium hexafluorophosphate and lithium tetrafluoroborate

A liquid crosslinkable composition for a solid electrolyte, wherein the amount of the oxetane ring-containing polymer is 5% by weight or less based on the total amount of the composition.

38. (1) Oxetane ring-containing polymer,-(2) Cationic polymerization initiator, (3) electrolyte solvent, and

 (4) Lithium electrolyte salt

A liquid cross-linkable composition for a solid electrolyte in which the amount of the oxetane ring-containing polymer (1) is 5% by weight or less based on the total amount of the composition; A polymer-solid electrolyte lithium, which is injected into a sealable battery container incorporating a unit including a separator disposed between both electrodes, and gelled by crosslinking to form a polymer solid electrolyte. Manufacturing method for ion secondary batteries.