WO2001047055A1 - Cellule secondaire aux ions de lithium a electrolyte polymere solide - Google Patents

Cellule secondaire aux ions de lithium a electrolyte polymere solide Download PDF

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Publication number
WO2001047055A1
WO2001047055A1 PCT/JP2000/008973 JP0008973W WO0147055A1 WO 2001047055 A1 WO2001047055 A1 WO 2001047055A1 JP 0008973 W JP0008973 W JP 0008973W WO 0147055 A1 WO0147055 A1 WO 0147055A1
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Prior art keywords
solid electrolyte
polymer
ion secondary
secondary battery
lithium ion
Prior art date
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PCT/JP2000/008973
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English (en)
Japanese (ja)
Inventor
Yuji Yamamichi
Hitoshi Moriiizumi
Toshiharu Takabatake
Satoshi Nishikawa
Shinji Bessho
Katsumi Tanino
Satoshi Fujiki
Masahiro Kadosaki
Takashi Terasawa
Original Assignee
Sunstar Giken Kabushiki Kaisha
Toyama Prefecture
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Priority claimed from JP36088899A external-priority patent/JP4597294B2/ja
Priority claimed from JP2000303703A external-priority patent/JP4911813B2/ja
Application filed by Sunstar Giken Kabushiki Kaisha, Toyama Prefecture filed Critical Sunstar Giken Kabushiki Kaisha
Publication of WO2001047055A1 publication Critical patent/WO2001047055A1/fr

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0085—Immobilising or gelification of electrolyte
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • 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 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.
  • PDAs personal digital assistants
  • 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).
  • electrolytes which are simply called “electrolytes” here.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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;
  • 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.
  • any method requires dedicated equipment for each process such as application, solidification, bonding, and swelling.
  • 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.
  • 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.
  • 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.
  • any means such as natural swelling, so it looks ideal at first glance.
  • 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.
  • low-boiling electrolyte solvents such as dimethyl carbonate, methylethyl carbonate, getyl carbonate, and propion Methyl acid, dimethoxetane and the like are appropriately used.
  • 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.
  • ethylene carbonate and propylene carbonate must be mainly used as the electrolyte solvent.
  • 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 ,.
  • propylene carbonate 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.
  • 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).
  • 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.
  • 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.
  • 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
  • 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;
  • 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.
  • 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). .
  • Epoxy resin and its crosslinking agent (Epoxy combination)
  • (meth) acryl means acryl or methacryl
  • (meth) acrylate means acrylate or methacrylate
  • the epoxy resin used here preferably has the formula [1]:
  • 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
  • the cyanoethylated epoxy resin [1] has the formula [2]:
  • polyol compound [2] examples include glycerin, erythritol, pentaerythritol, xylitol, sorbitol, diglycerin, triglycerin, Examples include inositol and mannitol.
  • 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].
  • 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.
  • 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.
  • the crosslinking agent used with the epoxy resin is preferably of the formula [3]:
  • a polyethylene polyamine represented by, for example, ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, etc., and a formula [4]:
  • 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
  • R 2 to R 6 are H and at least one is one CH 2 CH 2 CN)
  • 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.
  • f the molecular weight of polyethylene polyamine
  • 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.
  • polyisocyanate compound used in this combination examples 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:
  • 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).
  • the molecular weight of the polyol is 400 or more, the gelling property tends to decrease.
  • polyol examples include ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, trimethyi monopropane, glycerin, polyglycerin and the like, and ethylene oxide or propylene oxide adducts thereof.
  • 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.
  • a catalyst for example, metal salts such as Sn, Bi, Fe, Pb, or dibutyltin dilaurate
  • the reaction can be carried out in a non-reactive dehydrating solvent at a temperature from room temperature to about 100 ° C.
  • 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.
  • crosslinking agent used in the isocyanate combination examples include the following. i) A polyol compound having a molecular weight of less than 400 and a hydroxyl value of 400 or more.
  • polyol examples 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.
  • 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.
  • an alkali catalyst while heating or pressurizing while partially or completely adding ethylene oxide or propylene oxide.
  • the desired polyoxyalkylene polyol is produced.
  • Many varieties of polyoxyalkylene polyols are commercially available.
  • 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.
  • poly N-hydroxyalkylated compound examples include N, N′-tetrahydroxyxethylethylenediamine, N, N′-tetrahydroxyisopropene pinoleethylenediamine, ⁇ , ⁇ ′, N "1-pentahydroxyisopropinolegetylenetriamine, N, N,, N", ⁇ '"-Hexahydroxyxenotinoletrietylenetetramine, triethanolamine, triisopropanololamine, polydimethylamine Droxyisopropyl polyethyleneimine and the like, and some of these are commercially available.
  • 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.
  • 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.
  • 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.
  • 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, recitol, or adducts of these ethylene oxides or propylene oxides.
  • the other radically polymerizable monomer is represented by the formula [5]:
  • 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. ⁇ ) 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
  • 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.
  • a radical polymerization initiator eg, benzoyl peroxide, N, N'-azobisisobutyronitrile
  • chain transfer agents such as mercaptans and hydroxyl group-containing mercaptans can be used for controlling the molecular weight.
  • hydroxyl group-containing mercaptans for example, mercaptoethanol
  • the hydroxyl group of the copolymerized polymer can be improved. It is also a source of base introduction.
  • the crosslinking agents (i) to (vi) can be used.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • the hydroxyl group-containing radical copolymer (vi) when used, although the viscosity slightly increases, a good gel can be formed even at a lower polymer concentration, which is advantageous in this respect.
  • 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.
  • 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.
  • the (meth) acrylic monomer used in this combination has the formula [6]:
  • R 9 is H or CH 3 ; and is an alkyl having 1 to 4 carbon atoms.
  • 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]:
  • R 14 and R 16 are each H or CH 3 ; and 5 is one (CH 2 2 .
  • R 14 and R 16 are each H or CH 3 ; and 5 is one (CH 2 2 .
  • 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.
  • 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:
  • 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:
  • R 19 is H or CH 3 ; and R 2 is _COOCH 3 , one C ⁇ OC 2 H 5 , one C ⁇ C 3 H 7 , one CO ⁇ C 4 H 9 , -COO (CH 2 CH 2 O) ⁇ 3 CH 3 ,
  • 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.
  • cationic polymerization initiator used in the polymer system combination
  • 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.
  • the lithium electrolyte salt (3) hexafluorophosphate is not required.
  • 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.
  • cationic polymerization initiator it is also possible to use lithium fluorophosphate and z or lithium tetrafluoroborate in 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.
  • 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.
  • 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:
  • 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:
  • (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.
  • 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_ ⁇ _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 , — ⁇ COCH 3 , or one OCOC 2 H 5 )
  • 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 ⁇ 3 , and C 10 4
  • hexafluorofluoride which is a lithium electrolyte salt (3), can be used without using these hondium salts.
  • lithium phosphate and / or lithium tetrafluoroborate are 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.
  • 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.
  • 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.
  • 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) ( ⁇ -butyrolactone, ⁇ -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-cyano
  • 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.
  • 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.
  • the total number of carbon atoms is 7 or more, the ionic conductivity decreases. Therefore, battery characteristics tend to decrease.
  • 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.
  • 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.
  • 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.
  • 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.
  • the proportion of the crosslinkable material (1) in the total amount of the liquid composition was 10%.
  • 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.
  • a unit such as an electrode and a separator for a lithium ion secondary battery is removed.
  • 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. .
  • a urethane crosslinking catalyst for example, a metal salt such as Sn, Bi, Fe, or Pb; stannous octaate, cyanide
  • 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.
  • 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.
  • This urethane prepolymer A (solution) was a colorless and transparent viscous liquid, and a clear absorption spectrum of NC ⁇ 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%.
  • 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%.
  • CH 2 CHCOO ⁇ CH 2 CH (CH 3 ) ⁇ 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.
  • a clear epoxy group absorption spectrum was confirmed.
  • 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 )
  • 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. .
  • 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%) .
  • Example 3 the polymer solid electrolyte lithium ion secondary ion was used under the same conditions as in Example 1. Create batteries 2 ⁇ Example 3
  • 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 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.
  • lithium hexafluorophosphate was used as the lithium electrolytic salt, and no separate cationic polymerization initiator was used.
  • 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%).
  • 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 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.
  • Example 6 hexafluorophosphoric acid was added to the lithium electrolyte salt. Lithium is used and no separate cationic polymerization initiator is used.
  • Table 1 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.
  • each cycle was 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.
  • 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.
  • 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
  • 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 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
  • Liquid Composition C low-molecular alicyclic epoxy compound concentration 5%
  • 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.
  • 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
  • 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.
  • 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 ⁇ 0 ° 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
  • the non-woven fabric is 20 ⁇ m 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.
  • 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.

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Abstract

L'invention concerne une cellule secondaire aux ions de lithium à électrolyte polymère solide comprenant des électrodes positive et négative pour ce type de cellule et, entre les électrodes, un séparateur et un électrolyte polymère solide, ledit électrolyte étant fourni dans les conditions suivantes: composition liquide de réticulation à base de matériau réticulable, solvant électrolytique et électrolyte au sel de lithium, avec matériau réticulable représentant 10 %, en poids, de la composition; injection de la composition dans l'enceinte de la cellule à fermeture hermétique contenant une unité intégrée dans laquelle se trouvent les électrodes et le séparateur, et gélification de la composition par réticulation. On peut établir la cellule selon un procédé similaire à celui qui permet d'élaborer une cellule par le biais d'un électrolyte classique, sans recourir à des moyens spéciaux, et l'électrolyte polymère solide utilisé présente d'excellentes caractéristiques quant à la sécurité et en termes de cellule.
PCT/JP2000/008973 1999-12-20 2000-12-19 Cellule secondaire aux ions de lithium a electrolyte polymere solide WO2001047055A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP11/360888 1999-12-20
JP36088899A JP4597294B2 (ja) 1999-12-20 1999-12-20 ポリマー固体電解質リチウムイオン２次電池
JP2000/303703 2000-10-03
JP2000303703A JP4911813B2 (ja) 2000-10-03 2000-10-03 固体電解質用架橋性組成物、ポリマー固体電解質リチウムイオン２次電池及びポリマー固体電解質リチウムイオン２次電池の製造法

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2500975A4 (fr) * 2009-11-13 2013-08-07 Nec Energy Devices Ltd Electrolyte sous forme de gel pour batterie secondaire au lithium-ion, et batterie secondaire au lithium-ion comprenant cet électrolyte
CN112701348A (zh) * 2020-12-28 2021-04-23 南方科技大学 聚合物固态电解质、全固态锂电池及其制备方法

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JPH09278840A (ja) * 1996-04-10 1997-10-28 Showa Highpolymer Co Ltd 固体電解質が形成可能な組成物
EP0822608A2 (fr) * 1996-07-30 1998-02-04 Samsung Electronics Co., Ltd. Electrolyte solide polymère et pile rechargeable au lithium contenant cet électrolyte
JPH10134635A (ja) * 1996-11-05 1998-05-22 Daiwa Kagaku Kogyo Kk 有機固形電解質
JPH11121036A (ja) * 1997-10-15 1999-04-30 Toyama Pref Gov リチウムイオン２次電池の固体電解質用エポキシ系組成物
US5958997A (en) * 1996-08-19 1999-09-28 Korea Research Institute Of Chemical Technology Composition for and a method for producing a polymeric ion conductive membrane
JP2001035251A (ja) * 1999-07-21 2001-02-09 Nippon Synthetic Chem Ind Co Ltd:The 高分子固体電解質及びそれを用いた電気化学素子
JP2001035250A (ja) * 1999-07-21 2001-02-09 Hitachi Chem Co Ltd 高分子固体電解質、高分子固体電解質の製造法、電気化学的デバイス
JP2001043896A (ja) * 1999-07-29 2001-02-16 Hitachi Chem Co Ltd 高分子固体電解質の製造法、高分子固体電解質及び電気化学的デバイス

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH09278840A (ja) * 1996-04-10 1997-10-28 Showa Highpolymer Co Ltd 固体電解質が形成可能な組成物
EP0822608A2 (fr) * 1996-07-30 1998-02-04 Samsung Electronics Co., Ltd. Electrolyte solide polymère et pile rechargeable au lithium contenant cet électrolyte
US5958997A (en) * 1996-08-19 1999-09-28 Korea Research Institute Of Chemical Technology Composition for and a method for producing a polymeric ion conductive membrane
JPH10134635A (ja) * 1996-11-05 1998-05-22 Daiwa Kagaku Kogyo Kk 有機固形電解質
JPH11121036A (ja) * 1997-10-15 1999-04-30 Toyama Pref Gov リチウムイオン２次電池の固体電解質用エポキシ系組成物
JP2001035251A (ja) * 1999-07-21 2001-02-09 Nippon Synthetic Chem Ind Co Ltd:The 高分子固体電解質及びそれを用いた電気化学素子
JP2001035250A (ja) * 1999-07-21 2001-02-09 Hitachi Chem Co Ltd 高分子固体電解質、高分子固体電解質の製造法、電気化学的デバイス
JP2001043896A (ja) * 1999-07-29 2001-02-16 Hitachi Chem Co Ltd 高分子固体電解質の製造法、高分子固体電解質及び電気化学的デバイス

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2500975A4 (fr) * 2009-11-13 2013-08-07 Nec Energy Devices Ltd Electrolyte sous forme de gel pour batterie secondaire au lithium-ion, et batterie secondaire au lithium-ion comprenant cet électrolyte
CN112701348A (zh) * 2020-12-28 2021-04-23 南方科技大学 聚合物固态电解质、全固态锂电池及其制备方法
CN112701348B (zh) * 2020-12-28 2024-01-12 南方科技大学 聚合物固态电解质、全固态锂电池及其制备方法

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