CN100481603C - Lithium polymer secondary cell and manufacturing method thereof - Google Patents

Lithium polymer secondary cell and manufacturing method thereof Download PDF

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CN100481603C
CN100481603C CNB028182421A CN02818242A CN100481603C CN 100481603 C CN100481603 C CN 100481603C CN B028182421 A CNB028182421 A CN B028182421A CN 02818242 A CN02818242 A CN 02818242A CN 100481603 C CN100481603 C CN 100481603C
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precursor solution
lithium
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battery
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CN1555591A (en
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虎太直人
西岛主明
西村直人
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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
    • 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

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Abstract

The present invention relates to a lithium polymer secondary cell manufacturing method for manufacturing a lithium polymer secondary cell having a polymer electrolyte layer of lithium ion-conductive polymer gel between the positive and negative electrodes, comprising a step of preparing a precursor solution containing at least one kind of polymerizable monomer, a lithium salt, nonaqueous organic solvent, and 500-10,000 ppm of photopolymerization initiator initiating a polymerization reaction by ultraviolet irradiation and a step of forming a polymer electrolyte layer of a lithium ion-conductive polymer gel by impregnating a substrate for preparing a polymer electrolyte with the precursor solution and polymerizing the polymerizable monomer by irradiating the polymerizable monomer with ultraviolet radiation with illuminance of over 30 mW/cm<2> for 0.1 to 20 seconds. By optimizing the concentration of the photopolymerization initiator and the ultraviolet radiation illuminance, the cell characteristics and productivity of the lithium polymer secondary cell can be improved.

Description

The manufacture method of lighium polymer secondary battery
Technical field
The present invention relates to lighium polymer secondary battery and manufacture method thereof.The present invention is after comprising irradiation ultraviolet radiation in more detail, the manufacture method of the lighium polymer secondary battery of formation lithium-ion-conducting polymer gel operation and the lighium polymer secondary battery that obtains with this method thereof.
Background technology
Lithium secondary battery, theoretical energy density be than other battery height very, and can miniaturization, so at the power supply of palmtronic etc. and be studied widely and developing., along with the high performance of palmtronic etc., need more lightweight, thin typeization.And, for the equipment of mobile phone etc., require battery that reliability, the fail safe of very many charging discharging cycles are repeatedly arranged.
Lithium secondary battery up to now is that the electrolyte that lithium salts is dissolved in the organic solvent is being used as the electrolyte between positive pole and negative pole.Therefore, in order to keep reliability, using the jar of iron or aluminium as exterior material to liquid leakage etc.Therefore, the weight of lithium secondary battery and thickness have been subjected to the weight of metal can of its exterior material and the restriction of thickness.
Therefore, the secondary cell of developing the lighium polymer that does not use liquid electrolyte in vogue now.Lighium polymer secondary battery is to use the battery of the polymer solid electrolyte of lithium-ion-conducting polymer or lithium-ion-conducting gel formation.Because electrolyte is a solid, so the encapsulation of battery is easy, exterior material can use very light, thin elements such as aluminium lamination press mold.Therefore, can reach lightweight, the thin typeization of battery.
Obtain the method for above-mentioned polymer solid electrolyte, can enumerate at polymerizable monomer and contain lithium and arbitrarily behind the organic solvent, the crosslinked method that obtains.As crosslinked method such as following:
(1) with crosslinked method such as the ionization radioactive ray of electron ray etc. (spy opens flat 5-No. 290885 communiques),
(2) combination is easy to cause the thermal polymerization and the polymerizable compound of heat polymerization, the method for thermal polymerization (spy opens flat 11-No. 147989 communiques),
(3) use contains in the useful X-CO-Y[formula; X can have substituent aryl, Y that substituent phosphono can be arranged] represent that the active ray polymeric compositions of the active ray polymerization initiator of structure carries out crosslinked method (this method polymerism is good, even few initator also can carry out polymerization completely) (spy opens flat 10-No. 204109 communiques) etc.
During (1) method, electron ray is because transmittance is good, so also form polymer solid electrolyte in electrode interior.In the time of can being to use electron ray, need polymerization in inert gas atmosphere.In air during polymerization, airborne oxygen is owing to the effect of electron ray is decomposed, and these are as the polymerization inhibitor of polymerization reaction and have an effect.In addition, electron ray is also big for the influence of people's health, around the electron ray generating means screening arrangement must be set.Therefore, with easy device, it is difficult making battery safely.
During (2) method, thermal polymerization is to need for a long time, be difficult so shorten manufacturing time.In addition, because the gelatinous polymer solid electrolyte that thermal polymerization obtains, when battery was assembled, the possibility that takes place at internal short-circuit of battery compared with the polymerization with ultraviolet irradiation, and it is high that incidence is wanted.
During (3) method, though, when electrolyte forms, can utilize the such active ray of ultraviolet ray, need the time of several minutes irradiation ultraviolet radiations, therefore, in the irradiation, form the temperature rising of the precursor solution that electrolyte uses.The decomposition of lithium salts and the volatilization of low boiling point solvent may take place in its result in the precursor solution, these decomposition and volatilization influence the characteristic of battery.In addition, do not consider the relation of ultraviolet illumination and battery behavior yet.
Open the manufacture method of disclosed lighium polymer secondary battery in 2001-No. 210380 communiques the spy, contain the following stated, gel precursors solution irradiation ultraviolet radiation with the polymerizable monomer of general formula (1) expression makes the polymer monomer polymerization form the operation of lithium-ion-conducting gel., this method exists the ultraviolet irradiation classification long, the problem of productivity ratio aspect.In addition, do not consider the relation of ultraviolet illumination, polymerization initiator amount and battery behavior yet.
Summary of the invention
The present invention, in view of the problem of above-mentioned existence, its purpose is to provide polymerization time short, battery behavior high and stable, particularly high capacity characteristic, the good lighium polymer secondary battery of cyclophysis.
According to the present invention, between positive pole and negative pole, have in the manufacture method of lighium polymer secondary battery of the polyelectrolyte floor that constitutes by the lithium-ion-conducting polymer gel, in order to form the lithium-ion-conducting polymer gel, comprise the operation that forms precursor solution, this precursor solution contains at least a polymerizable monomer and lithium salts, non-aqueous organic solvent, by 500～10 of ultraviolet irradiation initiated polymerization, the Photoepolymerizationinitiater initiater of 000ppm; With
Form the polyelectrolyte floor operation, precursor solution is contained in the matrix that is immersed in polymer dielectric formation usefulness, compare 30mW/cm 0.1～20 second scope internal radiation 2The ultraviolet ray of stronger illumination makes its polymerization, forms the polyelectrolyte floor that is made of the lithium-ion-conducting polymer gel.
According to the present invention, can obtain having the polymer dielectric of required form stability in manufacturing process.The present invention can make precursor solution polymerization in the short time, so can improve productivity.In addition, because the time of ultraviolet irradiation is short, thus can suppress the rising of precursor solution temperature, and the volatilization of solvent.
Description of drawings
Fig. 1 is the essential structure figure of battery of the present invention.
Fig. 2 is the Photoepolymerizationinitiater initiater concentration of embodiment 1 and comparative example 1 and the graph of a relation of load characteristic.
Fig. 3 is the ultraviolet illumination of embodiment 1 and 2 and the graph of a relation of load characteristic.
Fig. 4 is embodiment 3 and the polymerization of comparative example 5,6 and the graph of a relation of load characteristic.
Fig. 5 is the kind of Photoepolymerizationinitiater initiater of embodiment 4～8 and the graph of a relation of load characteristic.
Fig. 6 is the electrolyte composition of embodiment 2,9 and the graph of a relation of cyclophysis.
Fig. 7 is the kind of negative electrode active material of embodiment 9,10 and the graph of a relation of cyclophysis
Fig. 8 be embodiment 10,11 heat treated have or not graph of a relation with cyclophysis
Embodiment
At first, represented to make, between positive pole and negative pole, used the essential structure of the lighium polymer secondary battery of lithium-ion-conducting polymer gel with method of the present invention at Fig. 1.The 1st, electrode terminal.The 2nd, polyelectrolyte floor, it is the precursor solution that will contain at least a polymerizable monomer and lithium salts, non-aqueous organic solvent, the Photoepolymerizationinitiater initiater by the ultraviolet irradiation initiated polymerization, contain and be immersed on the matrix, compare 30mW/cm 0.1～20 second scope internal radiation 2The ultraviolet ray of stronger illumination obtains its polymerization.The 3rd, anodal.The 4th, positive electrode collector.The 5th, negative electrode collector.The 6th, negative pole.The 7th, for the aluminium lamination pressurizing resin film system exterior material that battery is disconnected with outer air bound.
Precursor solution preferably uses by the scope internal radiation at 0.1～20 second and compares 30mW/cm 2The ultraviolet ray of stronger illumination makes it can be crosslinked, and then, on productivity, particularly preferably be 10 seconds with interior can be crosslinked.Ultraviolet intensity is 30～1000mW/cm preferably 2Scope.
The addition of Photoepolymerizationinitiater initiater, the reaction of the decomposition of initiator when suppressing abundant electricity etc., preferred few as far as possible interpolation the, but too after a little while, can not cause sufficient polymerization reaction, monomer that might remained unreacted.From above, the addition of Photoepolymerizationinitiater initiater, preferably the total amount for polymerizable monomer, lithium salts, non-aqueous organic solvent is 500～10, in the scope of 000ppm.When being lower than 500ppm, curing reaction in 20 seconds is difficult, so it is undesirable, surpass 10 in addition, during 000ppm, though also possibility solidification, but the molecular weight of the polymer that generates is low, the maintenance of non-aqueous organic solvent is difficult, and its result produces bad influence to battery behavior, is unfavorable.In addition, when initiator concentration was high, the hold facility of liquid descended sometimes.
The polymerizable monomer that in above-mentioned precursor solution, contains, preferably have polyether segment and, form polymer be three-dimensional cross-linked structure have multifunctional position like that.The terminal hydroxyl that its typical monomer is a PPG is with acrylic acid or methacrylic acid (being referred to as (methyl) acrylic acid) esterification.As is known, PPG be polyalcohol with ethylene glycol, glycerol, trimethylolpropane etc. as initial substance, addition polymerization oxirane and/or expoxy propane obtain above it again.Particularly, when the ionic conductivity polymer gel contained organic electrolyte, the polymer of poly-(methyl) acrylate of trifunctional PPG formed three-dimensional crosslinking structure easily, and guarantor's fluidity of electrolyte is good, so be preferred.And then, by the polyfunctional poly ethoxylated polyhydric alcohol is gathered the polymerization individually of (methyl) acrylate, perhaps with poly-(methyl) acrylate combination of the PPG of simple function, the polymer that copolymerization obtains, except reducing unreacted functional group, give the hardness of raising to the ionic conductivity polymer gel, so be preferred with the adaptation of electrode interface.
As polymerizable monomer, can enumerate with the represented monomer of following general formula (1).
Figure C02818242D00081
(R 1Be hydrogen atom or methyl, A 1, A 2And A 3Identical or different, represent from the ethylene oxide unit more than 3 (EO) the divalent base of perhaps above-mentioned ethylene oxide unit and propylene oxide units (PO), the number of PO and EO is in the scope of PO/EO=0～5, mean molecule quantity is 6,000～10,000 scope).
A 1, A 2And A 3Normally identical on the method for making of polymerizable monomer.In addition, the mean molecule quantity of the polymerizable monomer of above-mentioned general formula (1), preferably 7,500～9,000.
Be contained in the lithium salts in the above-mentioned precursor solution, can enumerate the organic salt of the inorganic salts, trifluoromethanesulfonic acid lithium, lithium halide, lithium difluoro methylsulfonyl imines etc. of lithium perchlorate, boron lithium fluoride, lithium hexafluoro phosphate, arsenic hexafluoride lithium, chlorination lithium aluminate etc., can use more than at least a in these.
The non-aqueous organic solvent that contains in above-mentioned precursor solution can be enumerated,
The cyclic carbonates of propene carbonate, ethylene carbonate, butylene etc.,
The linear carbonate class of diethyl carbonate, dimethyl carbonate, methyl ethyl carbonate etc.,
The lactone of γ-butyrolactone, γ-valerolactone, 6-valerolactone etc.,
The ring-type ethers that the tetrahydrochysene fluorine is muttered, 2-methyl tetrahydrochysene fluorine is muttered etc.,
The ethers of dioxolanes, ether, dimethoxy-ethane, diethoxyethane, methoxy ethoxy ethane etc.,
The ester class of dimethyl sulfoxide (DMSO), sulfolane, methyl sulfolane, acetonitrile, methyl formate, methyl acetate, ethyl acetate etc.,
The glyme class of methyl diethylene glycol dimethyl ether, ethyl diethylene glycol dimethyl ether etc.,
The alcohols of ethylene glycol, methyl Cellosolve, glycerol etc.,
The nitrile of acetonitrile, propionitrile, methoxyacetonitrile, 3-methoxypropionitrile etc.,
N-methylformamide, N-ethyl-formamide, N, N-dimethyl formamide, N, N-diethylformamide, N-methylacetamide, N-ethyl acetamide, N, the amide-type of N-dimethylacetylamide, N-methyl pyrrolidone etc.,
The sulfolane class of sulfolane, 3-methyl sulfolane etc.,
The phosphoric acid ester of trimethyl phosphate, triethyl phosphate etc.These solvents can use a kind of or make up more than two kinds and use.
The weight ratio of the combined amount of polymerizable monomer, lithium salts and non-aqueous organic solvent, the preferably scope of 30:70～2:98.Lithium-ion-conducting polymeric gel in that the precursor solution of this scope obtains has sufficient mechanical, and battery behavior is also good, so be preferred.The amount of polymerizable monomer is during greater than 30wt%, though can obtain having the lithium-ion-conducting polymeric gel of the hardness of abundant mechanical strength, the characteristic of battery significantly degenerates.In addition, when polymerizable monomer was less than 2wt%, though can solidify, mechanical strength was insufficient, battery behavior, and particularly cyclophysis degenerates.
In addition, contain the amount of the polymerizable monomer in the precursor solution of non-aqueous organic solvent, when very few, the solidification difficulty hinders lithium-ion-conducting in the time of too much, so the ratio of volume preferably 1～50.
When containing moisture in the non-aqueous organic solvent, produce the side reaction of moisture and solvent during battery charging and discharging, the efficient of battery itself and cycle lie descend, and problems such as gas occur producing.Therefore, preferably to reduce moisture in the non-aqueous organic solvent with doing one's utmost.Can use molecular sieve, alkali metal, alkaline-earth metal or activated aluminum etc. to dewater in case of necessity.As the amount of moisture that is contained in the non-aqueous organic solvent, preferably 1, below the 000ppm, more preferably below the 100ppm.
Be contained in the Photoepolymerizationinitiater initiater in the above-mentioned precursor solution, can enumerate phosphine oxide system, acetophenone system, Benzophenone system, α-hydroxy-ketone system, michler's ketone system, benzyl system, benzoin system, benzoin ether system, benzyl dimethyl ketal system etc.These can use a kind of, also can make up two or more uses.Wherein, the phosphine oxide series initiators is reactive high, and is good with the intermiscibility of polymerizable monomer and non-aqueous organic solvent, so be preferred.As phosphine oxide series initiators preferably (1) 2,4,6-trimethylbenzene formyl diphenyl phosphine oxide, (2) two (2,6-dimethoxy benzoyl)-2,4,4-trimethyl-amyl group phosphine oxide or (3) two (2,4,6-trimethylbenzene formyl)-phenyl phosphine oxide.
In addition, precursor solution and then contain thermal polymerization preferably, after ultraviolet irradiation or simultaneously heat treated precursor solution.Among the present invention, compare 30mW/cm by the irradiation of short time 2The ultraviolet ray of stronger illumination can obtain polymer dielectric., see on a macro scale,, on microcosmic, also have non-reacted parts though the ultraviolet irradiation time is abundant.Therefore, behind the adding thermal polymerization, reduce inner unreacted polymerizable monomer, unreacted initator, can reduce bad influence battery behavior by heat treated.Its result has obtained the effect that battery performance improves.
As thermal polymerization, for preferably 40～80 ℃ of the decomposition temperatures that obtain 10 hour half-life.When decomposition temperature was lower than 40 ℃, the compound instability of thermal polymerization during greater than 80 ℃, caused the deterioration and the decomposition of electrolyte and lithium salts easily in heat treated, so be not desirable.In addition, as the thermal polymerization that causes the heat cross-linking reaction, can enumerate diacyl peroxide system, peroxy esters system, peroxide two carbonic esters system, azo-compound system etc.(1) t-butyl peroxy neodecanoic acid ester wherein, (2) toluoyl benzoyl peroxide, (3) 3,5,5-trimethyl acetyl peroxide or (4) t-butyl peroxy valerate are because rate characteristic descends, the deterioration of cyclophysis is few, so be preferred.
As the addition of thermal polymerization, preferably the least possible, the inhibition of the decomposition of initiator reaction when suppressing to discharge and recharge is good, but too after a little while, can not fully cause polymerization reaction, and residual have a unreacted polymerizable monomer.From with last, the addition of thermal polymerization is 1～5 for the total amount that contains polymerizable monomer, lithium salts, non-aqueous organic solvent, and the scope of 000ppm is preferred, wherein, particularly preferably is 50～1,000ppm.These thermal polymerizations can use a kind of or be used in combination more than 2 kinds.
In addition, to positive pole and/or the different precursor solutions of forming of negative pole difference impregnation, 30mW/cm is compared in the scope irradiation in 0.1～20 second 2The ultraviolet ray of stronger illumination makes it carry out polymerization reaction respectively, can make to have positive pole and/or the negative pole of forming different polymer dielectrics.
Each difference that contains the precursor solution that is immersed in positive pole and/or negative pole can be enumerated the composition of kind, concentration, the electrolyte of polymer monomer, the kind that additive-free, lithium salts is arranged, concentration etc.
For example, set the concentration of the polymerizable monomer of side of the positive electrode and negative side respectively, use than the low precursor solution of negative side polymer monomer concentration, can improve load characteristic at side of the positive electrode.Perhaps, use the precursor solution contain propene carbonate can prevent the oxidation of polymer dielectric and the deterioration that causes at side of the positive electrode, use the precursor solution contain ethylene carbonate in negative side, the reaction that can suppress to decompose etc. can be carried out the adding and the disengaging of lithium expeditiously.And then, be the ethylene carbonate of the poor performance when negative side makes it to have low temperature, the deterioration of the battery behavior in the time of can preventing low temperature.In addition, at the vinylene carbonate of the negative side adding that contains ethylene carbonate,, can improve cyclophysis owing to generate surperficial tunicle easily as the low-molecular-weight crosslinking agent.And then, by using the precursor solution higher also can improve load characteristic than negative side lithium salt at side of the positive electrode.
Such polyelectrolyte floor can reduce ionic conductivity than the polymer dielectric that is contained in side of the positive electrode and negative side.By such formation, can improve the mechanical strength of polyelectrolyte floor, so the use of polyelectrolyte floor becomes easily, can suppress the generation of internal short-circuit of battery.
The positive pole that is used for lighium polymer secondary battery of the present invention has no particular limits.For example, as positive active material can be transition metal oxide or lithium transition-metal oxide powder and, to wherein hybrid conductive agent, binding agent and form behind the solid electrolyte arbitrarily.Can enumerate vanadium oxide V as transition metal oxide 2O 5, chromium oxide Cr 3O 8Deng.Can enumerate lithium acid cobalt (Li as lithium transition-metal oxide xCoO 2: 0＜x＜2), lithium acid nickel (Li xNiO 2: 0＜x＜2), lithium acid nickel/cobalt composite oxide (Li x(Ni 1-yCo y) O 2: 0＜x＜2,0＜y＜1), lithium acid manganese (Li xMn 2O 4: 0＜x＜2, Li xMnO 2: 0＜x＜2), lithium acid vanadium LiV 2O 5, LiVO 2, lithium acid tungsten LiWO 3, lithium acid molybdenum LiMoO 3Deng.
Conductive agent can use acetylene black, powdered graphite etc. material with carbon element and, metal dust, conductivity pottery.Binding agent can use polyolefin polymer of fluorine based polymer, polyethylene, polypropylene of polytetrafluoroethylene, Kynoar etc. etc. etc.
The mixing ratio of conductive agent and binding agent, preferably for lithium transition-metal oxide 100 weight portions, conductive agent is that 1～50 weight portion, binding agent are 1～30 weight portions.When conductive agent was less than 1 weight portion, the resistance of electrode or polarization became big, as the capacity minimizing of electrode, so can not constitute the lighium polymer secondary battery in the application, during greater than 50 weight portions, the amount of the lithium transition metal compound in the electrode reduces, capacity diminishes, and also is unfavorable.When binding agent is less than 1 weight portion, loses cohesive force and can not constitute electrode, during greater than 30 weight, the resistance of electrode or polarization become big, and the amount of the lithium metal oxide in the electrode reduces, and capacity diminishes, can not be practical, and also be unfavorable.
The mixture (hereinafter referred to as positive electrode) that will contain positive active material, conductive agent, binding agent and solid electrolyte as required is crimped on the collector body, the solvent that perhaps is dissolved in N-methyl-2-pyrrolidones etc. makes being coated on the collector body after the drying of slurries shape, make the mixture of its impregnation polymerizable monomer, lithium salts, Photoepolymerizationinitiater initiater, non-aqueous organic solvent, constitute the positive pole that contains polymer dielectric by polymerization.Perhaps also can blended anode material and, its polymerization to be constituted behind the polymerizable monomer, lithium salts, Photoepolymerizationinitiater initiater, non-aqueous organic solvent anodal.Can use the electric conductor of metal forming, wire-mesh screen, metal nonwoven fabrics etc. as collector body.
In addition, be used for the negative pole of polymer lithium secondary battery of the present invention, have no particular limits.For example, hybrid conductive agent, binding agent and solid electrolyte and form in negative electrode active material.But the kind according to negative electrode active material is not used conductive agent, binding agent and solid electrolyte sometimes.Can use the lithium alloy of lithium metal, lithium aluminium etc. or can add as negative electrode active material to break away from the lithium ion material, for example the electroconductive polymer of polyacetylene, polythiophene, poly etc., thermally decomposed carbon, catalyst have gas-phase decomposition down the graphite material, the adding that can carry out lithium ion of thermally decomposed carbon, the carbon that burns till by pitch, coke, tar etc., carbon that the macromolecule that burns till cellulose, phenolic resins etc. obtains, native graphite, Delanium, expanded graphite etc. break away from the WO of reaction 2, Mo 2The material of O etc. separately or these complex.
Wherein, thermally decomposed carbon, catalyst have gas-phase decomposition down the material with carbon element of thermally decomposed carbon, the carbon that burns till by pitch, coke, tar etc., carbon that the macromolecule that burns till cellulose, phenolic resins etc. obtains, native graphite, Delanium, expanded graphite etc., be preferred.As preferred material with carbon element, can enumerate the graphite particle of noncrystalline matter carbon attached to the surface.The surface attachment of graphite particle the material with carbon element of noncrystalline matter carbon, its surface has the rerum natura of noncrystalline matter carbon.Can suppress the decomposition of organic solvent in the polymer dielectric, improve the reliability of battery.By these, can provide lighium polymer secondary battery with good battery behavior.As the method for adhering to, the oil that graphite particle can be immersed in the coal measures mink cell focus of tar, pitch etc. or heavy oil etc. is in the mink cell focus, after taking-up, with the above temperature heating and decomposition mink cell focus of carburizing temperature, pulverizes the method for this material with carbon element in case of necessity.By with amorphous carbon attached to the surface, can be suppressed at when charging significantly, the decomposition reaction of ionic conductivity polymer that causes at negative pole and electrolyte, lithium salts improves discharging and recharging cycle lie, in addition, also can suppress because the generation gas that this decomposition reaction causes.
In addition, above-mentioned material with carbon element is with the pore relevant with specific area of BET method mensuration, owing to stopped up to a certain degree adhering to of noncrystalline matter carbon.Specific area is preferably less than 5m 2/ g.Specific area is greater than 5m 2During/g, also become greatly, cause these decomposition reaction easily, so be unfavorable with the contact area of ionic conductivity polymer or electrolyte.
Negative electrode active material, as required, be crimped on the collector body with the mixture (hereinafter referred to as negative material) of conductive agent, binding agent, the solvent that perhaps is dissolved in N-methyl-2-pyrrolidones etc. makes being coated on the collector body after the drying of slurries shape, make the mixture of its impregnation polymerizable monomer, lithium salts, Photoepolymerizationinitiater initiater, non-aqueous organic solvent, make these polymerizations constitute the negative pole that contains polymer dielectric.Perhaps also can mix negative material and, make its polymerization behind the polymerizable monomer, lithium salts, Photoepolymerizationinitiater initiater, non-aqueous organic solvent.Can use the electric conductor of metal forming, wire-mesh screen, metal nonwoven fabrics etc. as collector body.
The matrix that constitutes polyelectrolyte floor can use polymer fiber or micro-porous film dividing plate.Polymer fiber or micro-porous film dividing plate preferably have air permeability 1～500sec/cm 3The material of rerum natura.Air permeability is lower than at 1 o'clock, can not obtain sufficient ionic conduction degree, and is insufficient greater than 500 o'clock mechanical strengths, causes the short circuit of battery easily.And then the weight ratio of ionic conductivity polymer gel and polymer fiber or micro-porous film dividing plate is suitable in the scope of 91:9～50:50.The weight rate of ionic conductivity polymer gel can not obtain full intensity greater than 91 o'clock, was lower than at 50 o'clock, can not obtain sufficient ionic conduction degree.As polymer fiber, can enumerate nonwoven fabrics.
Being configured in that polyelectrolyte floor between positive pole and negative pole there is no need is the simple layer structure, also can have multi-ply construction in these polyelectrolyte floors.In addition, for prevent between positive pole and polyelectrolyte floor or negative pole and polyelectrolyte floor solvent diffusion, in order to improve the adaptation at each polyelectrolyte floor interface, also can handle on the surface of polyelectrolyte floor.Polyelectrolyte floor and composition anodal, negative pole will meet its each characteristic, and different compositions is also passable.
Lighium polymer secondary battery among the present invention, be with above-mentioned positive pole and collector body, and negative pole and collector body be combined on the outer electrode respectively, and then, clamp above-mentioned polyelectrolyte floor betwixt and constitute.
When positive pole and/or negative pole contain polymer dielectric, can obtain battery with following method.Positive pole and/or negative pole, the perhaps polyelectrolyte floor that is disposed therebetween, be by after precursor solution being contained the polymer fiber or micro-porous film partition that is immersed in positive pole and/or negative pole, formation matrix, the polymerization reaction of the electromagnetic wave irradiation by radioactive ray, ultraviolet ray etc. and arbitrarily the heated polymerizable cross-linking reaction of heat treated etc. obtain.Battery can constitute by the following method, and positive pole, matrix and negative pole is overlapping, then contains the method that is immersed in polymerization behind the precursor solution; Positive pole, matrix and negative pole contained respectively be immersed in polymerization behind the precursor solution, with the overlapping method of positive pole, matrix and negative pole that obtains; Positive pole or negative pole are overlapped on the matrix, and then polymerization behind the impregnation precursor solution contains polymerization behind the precursor solution, the method that both are overlapping of being immersed in other negative pole or positive pole.
The shape of lighium polymer secondary battery of the present invention can be enumerated cylinder type, button type, square, sheet etc., but has no particular limits.In addition, can enumerate metal, aluminium lamination pressurizing resin film etc. as exterior material.When using the battery of aluminium lamination pressurizing resin film production sheet, by can packaged battery with the heat fusing or the hot pressing of aluminium lamination pressurizing resin film.These battery manufacturing process for the immersion of anti-sealing, preferably carries out in the inert gas atmosphere of argon gas etc. or dry air.
Embodiment
Below specifically describe the present invention with embodiment, but the present invention is not subjected to these any restriction.In addition, the maximum output wavelength of using during the ultraviolet irradiation in following examples and the comparative example is 365nm.The positive pole and the negative pole that contain polymer dielectric are called anodal layer and negative electrode layer.
Embodiment 1
With LiBF 4Be dissolved in the electrolyte that is adjusted to 1M in the mixed solvent (containing ratio of ethylene carbonate is 35 volume %) of ethylene carbonate and γ-butyrolactone and, the mean molecule quantity as the copolymer that contains oxirane and expoxy propane of polymerizable monomer represented with following general formula (1) is 7,500～9,000 triacrylate monomer, be adjusted into weight ratio 95:5, and then dissolving is as 2 of polymerization initiator, 4,6-trimethylbenzene formyl diphenyl phosphine oxide 3 obtains precursor solution behind the 000ppm.
Figure C02818242D00161
(R 1Be hydrogen atom or methyl A 1, A 2And A 3Identical or different, expression is from the divalent base of the ethylene oxide unit more than three (EO) or above-mentioned ethylene oxide unit and propylene oxide units (PO), and the number of PO and EO is in PO/EO=0～5 scopes)
After the nonwoven fabrics (matrix) of thickness 25 μ m is gone up impregnated precursor solution, is under reduced pressure placed 15 minutes, irradiation illumination 200mW/cm 210 seconds of ultraviolet ray, make polyelectrolyte floor.
LiCoO at average grain diameter 7 μ m 2Mix in the powder as Kynoar (PVDF) the 7 weight % of binding material and, as the acetylene black 5 weight % of the average grain diameter 2 μ m of electric conducting material, add the pastel that N-methyl-2-pyrrolidones (NMP) back mixed dissolution obtains, the thickness that this pastel is coated in as collector body is on the rolling aluminum foil of 20 μ m, obtains positive pole after drying and the extruding.This electrode surface area is 7.84cm 2, thickness is 80 μ m.
The specific area of measuring with the BET method with X line wide-angle diffraction method (d002)=0.337nm, (Lc)=100nm, (La)=100nm is 10m 2In the Delanium powder of/g, mixing is as Kynoar (PVDF) the 9 weight % of binding material, add N-methyl-2-pyrrolidones (NMP) back mixed dissolution and obtain pastel, the thickness that this pastel is coated in as collector body is on the rolled copper foil of 20 μ m, obtains negative pole after drying and the extruding.This electrode surface area is 9cm 2, thickness is 80 μ m.
Under reduced pressure place on 5 minutes the positive pole and inject precursor solution, this precursor solution be used to make the identical of above-mentioned polyelectrolyte floor, place after 15 minutes irradiation 200mW/cm 210 seconds of ultraviolet ray make anodal layer.The thickness of anodal layer is 80 μ m.Negative electrode layer also with the same making of anodal layer, the thickness of the negative electrode layer that obtains is 85 μ m.
Fit anodal layer and polyelectrolyte floor and negative electrode layer are clipped in the middle of two pieces of aluminium lamination pressurizing resin films, heat fusing and make the battery of sheet.
Comparative example 1
By being 12 except Photoepolymerizationinitiater initiater concentration, beyond the 000ppm, other methods identical with embodiment 1 are made battery.
Comparative example 2
Except Photoepolymerizationinitiater initiater concentration is 400ppm, make polyelectrolyte floor under other and the embodiment 1 identical condition, but precursor solution there is not full solidification, residual a part of liquid can not be made battery.
Comparative example 3
Except Photoepolymerizationinitiater initiater concentration is 15, beyond the 000ppm, make polyelectrolyte floor under other and the embodiment 1 identical condition.Though precursor solution solidifies, the mechanical strength of the polyelectrolyte floor that obtains is insufficient, can not make battery.
The battery of embodiment 1 and comparative example 1 with till deciding electric current 2.3mA and being charged to cell voltage and reaching 4.1V, is reached behind the 4.1V and to decide under the voltage charging 12 hours.Then, decide under the electric current discharge till 2.75V at 2.3mA, 5mA, 10mA, 20mA.The result who discharges and recharges test with this understanding is illustrated among Fig. 2.
As can be seen from Figure 2, even embodiment 1 current value height and discharge capacity is also high is compared the rising of comparative example 1 along with current value with it, discharge capacity descends.Find out when Photoepolymerizationinitiater initiater concentration is too high, the load characteristic of battery is had harmful effect thus.
Embodiment 2
For positive pole before the precursor solution impregnation and negative pole, be to use identical with embodiment 1.
With LiPF 6Be dissolved in the electrolyte that is adjusted to 1M in the mixed solvent (containing ratio of ethylene carbonate is 35 volume %) of ethylene carbonate and γ-butyrolactone and, be 7 as the mean molecule quantity that contains oxirane and epoxy propane copolymer of polymerizable monomer, 500～9,000 triacrylate monomer, be adjusted into weight ratio 95: 5, and then dissolving is as 2 of Photoepolymerizationinitiater initiater, 4,6-trimethylbenzene formyl diphenyl phosphine oxide 3 obtains precursor solution behind the 000ppm.After the nonwoven fabrics (matrix) of thickness 25 μ m is gone up impregnated precursor solution, is under reduced pressure placed 15 minutes, irradiation illumination 30mW/cm 220 seconds of ultraviolet ray, make polyelectrolyte floor.
Under reduced pressure, place and inject the precursor solution identical on 5 minutes the positive pole, and then after placing 15 minutes, shine illumination 30mW/cm with embodiment 1 210 seconds of ultraviolet ray, make anodal layer.The anodal layer thickness that obtains is 80 μ m.Negative electrode layer also with the same making of anodal layer, the thickness of negative electrode layer is 85 μ m.
Fit anodal layer and polyelectrolyte floor and negative electrode layer are clipped in the middle of two pieces of aluminium lamination pressurizing resin films, heat fusing and make the battery of sheet.
Comparative example 4
Except irradiation illumination 20mW/cm 2Ultraviolet ray beyond, other and embodiment 2 make polyelectrolyte floor in the same manner, even but behind the irradiation ultraviolet radiation, because the solidification of precursor solution is incomplete, so can not make battery.
To be charged to cell voltage be 4.1V to decide electric current 2.3mA with the battery of embodiment 2, reaches behind the 4.1V to decide under the voltage charging 12 hours.Then, decide under the electric current discharge till 2.75V at 2.3mA, 5mA, 10mA, 20mA.Discharging and recharging the result who discharges and recharges the embodiment 1 of test under the result of embodiment 2 of test and the similarity condition with this understanding is illustrated among Fig. 3.Thus, the battery of embodiment 2 has also shown the result much at one with embodiment 1 as can be seen, when making the good lithium ion battery of load characteristic, as long as ultraviolet illumination is 30mW/cm 2More than just can.In addition, the upper limit of ultraviolet illumination is the restriction that is subjected to the power of UV lamp, still, and when using among the present invention, as long as can obtain 6000mW/cm 2Illumination just can.
Embodiment 3
For positive pole before the precursor solution impregnation and negative pole, be to use identical with embodiment 1.
With LiBF 4Be dissolved in the electrolyte that is adjusted to 1mol in the mixed solvent (containing ratio of ethylene carbonate is 35 volume %) of ethylene carbonate and γ-butyrolactone and, be 7 as the mean molecule quantity of above-mentioned general formula (1) expression of polymerizable monomer, 500～9,000 triacrylate monomer, be adjusted to weight ratio 93:7, and then dissolving is as 2 of Photoepolymerizationinitiater initiater, 4,6-trimethylbenzene formyl diphenyl phosphine oxide 3 obtains precursor solution behind the 000ppm.After the nonwoven fabrics (matrix) of thickness 25 μ m is gone up impregnated precursor solution, is under reduced pressure placed 15 minutes, irradiation illumination 200mW/cm 220 seconds of ultraviolet ray, make polyelectrolyte floor.
Under reduced pressure place and inject above-mentioned precursor solution on 5 minutes the positive pole, and then after placing 15 minutes, irradiation illumination 200mW/cm 220 seconds of ultraviolet ray, make anodal layer.The anodal layer thickness that obtains is 80 μ m.Negative electrode layer also with the same making of anodal layer, the thickness of negative electrode layer is 85 μ m.
Fit anodal layer and polyelectrolyte floor and negative electrode layer are clipped in the middle of two pieces of aluminium lamination pressurizing resin films, heat fusing and make the battery of sheet.
Comparative example 5
For positive pole before the precursor solution impregnation and negative pole, be to use identical with embodiment 1.
The electrolyte that embodiment 2 is used and, the mean molecule quantity of above-mentioned general formula (1) expression of polymerizable monomer is 7,500～9,000 triacrylate monomer is adjusted to weight ratio 93:7, and then the t-butyl peroxy of dissolving as thermal polymerization obtains precursor solution behind the ester 500ppm the new last of the ten Heavenly stems.After the nonwoven fabrics (matrix) of thickness 25 μ m is gone up impregnated precursor solution, under reduced pressure placed 15 minutes,, make polyelectrolyte floor 60 ℃ of heating 24 hours down.
Under reduced pressure place and inject above-mentioned precursor solution on 5 minutes the positive pole, and then after placing 15 minutes,, make anodal layer 60 ℃ of heating 24 hours down.The anodal layer thickness that obtains is 80 μ m.Negative electrode layer also with the same making of anodal layer, the thickness of negative electrode layer is 85 μ m.
Fit anodal layer and polyelectrolyte floor and negative electrode layer are clipped in the middle of two pieces of aluminium lamination pressurizing resin films, heat fusing and make the battery of sheet.
Comparative example 6
For positive pole before the precursor solution impregnation and negative pole, be to use identical with embodiment 1.
Will with the precursor solution casting film of comparative example 5 identical uses to area 12.25cm 2Glass substrate on, keep at interval with the pad of 25 μ m, carry behind the glass plate fixing above it.Then, the electron ray of irradiation accelerating voltage 250kV, 8Mrad is made polyelectrolyte floor in inert gas atmosphere.The thickness of the polyelectrolyte floor that obtains is 50 μ m.
Under reduced pressure place the above-mentioned precursor solution that injects comparative example 5 preparations on 5 minutes the positive pole, places after 15 minutes, the electron ray of irradiation accelerating voltage 250kV, 8Mrad in inert gas atmosphere is made anodal layer.The anodal layer thickness that obtains is 80 μ m.Negative electrode layer also with the same making of anodal layer, the thickness of negative electrode layer is 85 μ m.
Fit anodal layer and polyelectrolyte floor and negative electrode layer are clipped in the middle of two pieces of aluminium lamination pressurizing resin films, behind the heat fusing, carry out 24 hours heat treated and make the battery of sheet under 60 ℃.
The battery of embodiment 3, comparative example 5,6 with till deciding electric current 2.3mA and being charged to cell voltage and reaching 4.1V, is reached behind the 4.1V and to decide under the voltage charging 12 hours.Then, decide under the electric current discharge till 2.75V at 2.3mA, 5mA, 10mA, 20mA.The result who discharges and recharges test with this understanding is illustrated among Fig. 4.In the test, the battery of comparative example 5 has 2 short circuits in 50.The battery of embodiment 3 and comparative example 6 does not all have short circuit.From these as can be seen, using thermal polymerization is heat treated and when solidifying, mechanical strength is low, causes short circuit easily.In addition, from the result of the test that discharges and recharges of Fig. 4, the battery of embodiment 3 shown with high current value and high discharge capacity, and in contrast to this, comparative example 5,6, discharge capacity descended significantly when current value was high.From as can be seen above, the polymerization of manufacture method of the present invention and heat or electron ray is good on load characteristic relatively.
Embodiment 4
For positive pole before the precursor solution impregnation and negative pole, be to use identical with embodiment 1.
With LiBF 4Be dissolved in the electrolyte that is adjusted to 1.75M in the mixed solvent (containing ratio of ethylene carbonate is 35 volume %) of ethylene carbonate and γ-butyrolactone and, be 7 as the mean molecule quantity of above-mentioned general formula (1) expression of polymerizable monomer, 500～9,000 triacrylate monomer, be adjusted to weight ratio 93:7, and then dissolving is as 2 of Photoepolymerizationinitiater initiater, 4,6-trimethylbenzene formyl diphenyl phosphine oxide 3 obtains precursor solution behind the 000ppm.After the nonwoven fabrics (matrix) of thickness 25 μ m is gone up impregnated precursor solution, is under reduced pressure placed 15 minutes, irradiation illumination 200mW/cm 220 seconds of ultraviolet ray, make polyelectrolyte floor.
Under reduced pressure place and inject above-mentioned precursor solution on 5 minutes the positive pole, and then after placing 15 minutes, irradiation illumination 200mW/cm 220 seconds of ultraviolet ray, make anodal layer.The anodal layer thickness that obtains is 80 μ m.Negative electrode layer also with the same making of anodal layer, the thickness of negative electrode layer is 85 μ m.
Fit anodal layer and polyelectrolyte floor and negative electrode layer are clipped in the middle of two pieces of aluminium lamination pressurizing resin films, heat fusing and make the battery of sheet.
Embodiment 5～8
By except use two (2 as Photoepolymerizationinitiater initiater, 4,6-trimethylbenzene formyl)-phenyl phosphine oxide beyond, other methods identical with embodiment 4 are made battery and are obtained embodiment 5, similarly use two (2 as Photoepolymerizationinitiater initiater, 6-dimethoxy benzoyl)-2,4,4-tri-methyl-amyl phosphine oxide is made battery and is obtained embodiment 6.
By except use 1-hydroxyl-cyclohexyl-phenyl ketone as Photoepolymerizationinitiater initiater, other methods identical with embodiment 4 are made battery and are obtained embodiment 7, similarly use 2-2-dimethoxy-2-phenyl acetophenone to make battery as Photoepolymerizationinitiater initiater and obtain embodiment 8.
The battery of embodiment 4～8 with till deciding electric current 2.3mA and being charged to cell voltage and reaching 4.1V, is reached behind the 4.1V and to decide under the voltage charging 12 hours.Then, decide under the electric current discharge till 2.75V at 2.3mA, 5mA, 10mA, 20mA.The result who discharges and recharges test with this understanding is illustrated among Fig. 5.As can be seen from Figure 5, the discharge capacity height of embodiment 4,5,6 low current value, even current value uprises, discharge capacity also descends hardly.From as can be seen above, when making the good battery of load characteristic, it is good using the initator of phosphine oxide system.
Embodiment 9
For positive pole before the precursor solution impregnation and negative pole, be to use identical with embodiment 1.
With LiBF 4Be dissolved in the electrolyte that is adjusted to 2M in the mixed solvent (containing ratio of ethylene carbonate is 35 volume %) of ethylene carbonate and γ-butyrolactone and, molecular weight is 7,500～9, the polymerizable monomer of the PPG acrylate of 000 trifunctional, be adjusted to weight ratio 97:3, and then dissolving is as 2 of Photoepolymerizationinitiater initiater, 4,6-trimethylbenzene formyl diphenyl phosphine oxide 3 obtains precursor solution behind the 000ppm.After the nonwoven fabrics (matrix) of thickness 25 μ m is gone up impregnated precursor solution, is under reduced pressure placed 15 minutes, irradiation illumination 200mW/cm 220 seconds of ultraviolet ray, make polyelectrolyte floor.
Under reduced pressure place and inject above-mentioned precursor solution on 5 minutes the positive pole, and then after placing 15 minutes, irradiation illumination 200mW/cm 220 seconds of ultraviolet ray, make anodal layer.The anodal layer thickness that obtains is 80 μ m.
With LiBF 4Be dissolved in the electrolyte that is adjusted to 1M in the mixed solvent (containing ratio of ethylene carbonate is 35 volume %) of ethylene carbonate and γ-butyrolactone and, as polymerizable monomer, molecular weight is 7,500～9, the PPG acrylate of 000 trifunctional and molecular weight are 220～300 monofunctional polyethers polyalcohol acrylates, be adjusted to weight ratio 95:3.5:1.5, and then dissolving is as 2 of Photoepolymerizationinitiater initiater, 4,6-trimethylbenzene formyl diphenyl phosphine oxide 3 obtains precursor solution behind 000ppm and the vinylene carbonate 3 weight % as the low-molecular-weight crosslinking agent.Under reduced pressure place and inject above-mentioned precursor solution on the negative pole after 5 minutes, place after 15 minutes, irradiation illumination 200mW/cm 220 seconds of ultraviolet ray, make negative electrode layer.The negative electrode layer thickness that obtains is 85 μ m.
Fit anodal layer and polyelectrolyte floor and negative electrode layer are clipped in the middle of two pieces of aluminium lamination pressurizing resin films, heat fusing and make the battery of sheet.
The battery of embodiment 9 and embodiment 2 with till deciding electric current 2.3mA and being charged to cell voltage and reaching 4.1V, is reached behind the 4.1V and to decide under the voltage charging 12 hours.Then, decide under the electric current discharge till 2.75V at 2.3mA.Discharge and recharge repeatedly with this understanding, the result who carries out the cyclophysis evaluation is illustrated among Fig. 6.As can be seen from Figure 6, the battery of embodiment 2 is along with the increase of periodicity, and discharge capacity reduces, and compares with it, even the battery periodicity of embodiment 9 increases, discharge capacity also reduces hardly.Like this, in manufacture method of the present invention, can make anodal layer and negative electrode layer carry out polymerization reaction respectively, anodal layer and the negative electrode layer and the polyelectrolyte floor of the combination of life cycle characteristic good are made lighium polymer secondary battery.
In addition, among the embodiment, specifically understand the present invention, but the present invention is not limited, can uses best combination according to various purposes.
Embodiment 10
By using the specific area of measuring with the BET method of X line wide-angle diffraction method (d002)=0.336nm, (Lc)=100nm, (La)=97nm except negative electrode active material is 2m 2Outside the surperficial noncrystalline matter graphite of/g, average grain diameter 10 μ m, other methods identical with embodiment 1 are made negative electrode layer.
Use all identically with embodiment 9 except above-mentioned negative electrode layer, the making battery uses the same method.
The battery that obtains with till deciding electric current 2.3mA and being charged to cell voltage and reaching 4.iV, is reached behind the 4.1V and to decide under the voltage charging 12 hours.Then, decide under the electric current discharge till 2.75V at 2.3mA.Discharge and recharge repeatedly with this understanding, carry out periodic test.Fig. 7 has represented the cyclophysis result of embodiment 9 in the lump in order to compare with embodiment 10.As can be seen from Figure 7, compare with embodiment 9, the capacity that discharges in any periodicity of the battery of embodiment 10 all is high.By on negative electrode active material, using surperficial noncrystalline matter graphite, can suppress side reaction, battery that can the fabrication cycle characteristic good.
Embodiment 11
For positive pole before the precursor solution impregnation and negative pole, be to use identical with embodiment 10.
With LiBF 4Be dissolved in the electrolyte that is adjusted to 2M in the mixed solvent (containing ratio of ethylene carbonate is 35 volume %) of ethylene carbonate and γ-butyrolactone and, be 7 as the molecular weight of polymerizable monomer, 500～9,000 trifunctional PPG acrylate, be adjusted to weight ratio 93:7, and then dissolving is as 2 of Photoepolymerizationinitiater initiater, 4,6-trimethylbenzene formyl diphenyl phosphine oxide 3 obtains precursor solution behind 000ppm and the t-butyl peroxy neodecanoic acid ester 200ppm as thermal polymerization.After the nonwoven fabrics (matrix) of thickness 25 μ m is gone up impregnated precursor solution, is under reduced pressure placed 15 minutes, irradiation illumination 200mW/cm 220 seconds of ultraviolet ray, make polyelectrolyte floor.
Under reduced pressure place and inject above-mentioned precursor solution on 5 minutes the positive pole, and then after placing 15 minutes, irradiation illumination 200mW/cm 220 seconds of ultraviolet ray, make anodal layer.The anodal layer thickness that obtains is 80 μ m.
With LiBF 4Be dissolved in the electrolyte that is adjusted to 1M in the mixed solvent (containing ratio of ethylene carbonate is 35 volume %) of ethylene carbonate and γ-butyrolactone and, as polymerizable monomer, molecular weight is 7,500～9,000 trifunctional PPG acrylate and molecular weight are 220～300 monofunctional polyethers polyalcohol acrylates, be adjusted to weight ratio 95:3.5:1.5, and then dissolving is as 2 of Photoepolymerizationinitiater initiater, 4,6-trimethylbenzene formyl diphenyl phosphine oxide 3,000ppm and as the t-butyl peroxy neodecanoic acid ester 200ppm of thermal polymerization, obtain precursor solution behind the vinylene carbonate 3 weight % as the low-molecular-weight crosslinking agent.Under reduced pressure place on the negative pole after 5 minutes, inject above-mentioned precursor solution and place after 15 minutes, irradiation illumination 200mW/cm 220 seconds of ultraviolet ray, make negative electrode layer.The negative electrode layer thickness that obtains is 85 μ m.
With positive pole layer and polyelectrolyte floor and negative electrode layer, be clipped in the middle of two pieces of aluminium lamination pressurizing resin films, behind the heat fusing, 60 ℃ of following heat treated 72 hours, the battery of making sheet.
The battery of embodiment 11 with till deciding electric current 2.3mA and being charged to cell voltage and reaching 4.1V, is reached behind the 4.1V and to decide under the voltage charging 12 hours.Then, decide under the electric current discharge till 2.75V at 2.3mA.Discharge and recharge repeatedly with this understanding, carry out periodic test.Fig. 8 has represented the periodic test result of embodiment 10 in the lump in order to compare with embodiment 11.As can be seen from Figure 8, even the periodicity of the battery of embodiment 11 increases, discharge capacity also is high.From finding out here, after ultraviolet irradiation, the unreacted portion that trace exists can be reduced by heating, can improve battery behavior.
According to the present invention, the manufacture method of lighium polymer secondary battery is provided, it is to comprise the operation that obtains polyelectrolyte floor, in the lighium polymer secondary battery of the polyelectrolyte floor that use lithium-ion-conducting polymer gel constitutes between positive pole and negative pole, the Photoepolymerizationinitiater initiater 500～10 that will contain at least a polymerizable monomer and lithium salts, non-aqueous organic solvent, usefulness ultraviolet irradiation initiated polymerization, the precursor solution of 000ppm contains on the matrix that is immersed in the formation polymer dielectric, again with wavelength 350～400nm irradiation illumination 30mW/cm 2In above 0.1～20 second of intensive ultraviolet, make its curing.In addition, in this way, can provide productivity height and then load characteristic, the good lighium polymer secondary battery of cyclophysis.
In addition, as Photoepolymerizationinitiater initiater, use phosphine oxide system, particularly 2,4,6-trimethylbenzene formyl diphenyl phosphine oxide, two (2,6-dimethoxy benzoyl)-2,4,4-trimethyl-amyl group phosphine oxide or two (2,4,6-trimethylbenzene formyl)-and phenyl phosphine oxide, can provide battery behavior better lighium polymer secondary battery.
Negative electrode active material is a material with carbon element, by at the noncrystalline matter carbon of the surface attachment of graphite particle, can suppress the side reaction with polymer dielectric, provides battery behavior better lighium polymer secondary battery.

Claims (8)

1. the manufacture method of lighium polymer secondary battery between positive pole and negative pole, has in the manufacture method of lighium polymer secondary battery of the polyelectrolyte floor that is made of the lithium-ion-conducting polymer gel,
In order to form the lithium-ion-conducting polymer gel, comprise the operation that forms precursor solution, this precursor solution contains the represented polymerizable monomer of at least a following general formula (1) and lithium salts, non-aqueous organic solvent, by 500～10 of ultraviolet irradiation initiated polymerization, the Photoepolymerizationinitiater initiater of 000ppm, 1～5, the thermal polymerization of 000ppm, and the weight ratio of the combined amount of polymerizable monomer, lithium salts and non-aqueous organic solvent is 30:70～2:98;
Form the operation of polyelectrolyte floor, precursor solution is contained in the matrix that is immersed in polymer dielectric formation usefulness, by carrying out comparing 30mW/cm 0.1～20 second scope internal radiation 2The ultraviolet polymerization of stronger illumination and utilize the polymerization of heat treated, form the polyelectrolyte floor that constitutes by the lithium-ion-conducting polymer gel and
Formation contains the operation of the positive pole and/or the negative pole of polymer dielectric, at positive pole and/or negative pole impregnation precursor solution, compares 30mW/cm by the scope internal radiation at 0.1～20 second 2The ultraviolet ray of stronger illumination makes its polymerization and forms,
Be to have different compositions wherein to the anodal precursor solution that impregnation is used with negative pole, use the precursor solution higher at side of the positive electrode than negative side salinity, to contain the precursor solution that is immersed in anodal and negative pole and carry out polymerization reaction respectively, form the positive pole and the negative pole that contain polymer dielectric
Figure C02818242C00021
In general formula (1), R 1Be hydrogen atom or methyl, A 1, A 2And A 3Identical or different, represent from the ethylene oxide unit more than 3 (EO), the divalent base of perhaps above-mentioned ethylene oxide unit and propylene oxide units (PO), the number of PO and EO is in the scope of PO/EO=0～5.
2. manufacture method according to claim 1, wherein the weight ratio of the combined amount of polymerizable monomer, lithium salts and non-aqueous organic solvent is 7:93～2:98.
3. manufacture method according to claim 1, wherein Photoepolymerizationinitiater initiater is that phosphine oxide is a polymerization initiator, thermal polymerization is diacyl peroxide system, peroxy esters system or peroxide two carbonic ester based compounds.
4. manufacture method according to claim 3, wherein phosphine oxide is that polymerization initiator is from (1) 2,4,6-trimethylbenzene formyl diphenyl phosphine oxide, (2) two (2,6-dimethoxy benzoyl)-2,4,4-trimethyl-amyl group phosphine oxide or (3) two (2,4,6-trimethylbenzene formyl)-select in the group that phenyl phosphine oxide constitutes at least a.
5. manufacture method according to claim 3 is for the decomposition temperature of 10 hour half-life obtaining thermal polymerization is 40～80 ℃.
6. manufacture method according to claim 3, wherein the thermopolymer initator is from (1) t-butyl peroxy neodecanoic acid ester, (2) toluoyl benzoyl peroxide, (3) 3, that selects in the group that 5,5-trimethyl acetyl peroxide or (4) t-butyl peroxy valerate constitute is at least a.
7. manufacture method according to claim 1, wherein negative pole contains negative electrode active material, is to constitute at the material with carbon element of the noncrystalline matter carbon of the surface attachment of graphite particle.
8. manufacture method according to claim 1, precursor solution and then contain thermal polymerization wherein, after ultraviolet irradiation or simultaneously heat treated precursor solution.
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