CN101033323A - Polymer gel electrolyte and polymer secondary battery using the same - Google Patents
Polymer gel electrolyte and polymer secondary battery using the same Download PDFInfo
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- CN101033323A CN101033323A CNA2007100862639A CN200710086263A CN101033323A CN 101033323 A CN101033323 A CN 101033323A CN A2007100862639 A CNA2007100862639 A CN A2007100862639A CN 200710086263 A CN200710086263 A CN 200710086263A CN 101033323 A CN101033323 A CN 101033323A
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Abstract
A polymer gel electrolyte, comprising a polymer gel including an aprotic organic solvent, a carrier salt and a sulfur-containing organic compound having at least one -O-SO2- in its chemical structure, for instance, a straight-chain sulfonic acid ester or a cyclic sulfonic acid ester, and a lithium polymer secondary battery using the polymer gel electrolyte and having improved rate performance and cycle performance.
Description
CROSS-REFERENCE TO RELATED APPLICATION
The application is based on formerly Japanese patent application No.2006-64049 (March 9 2006 applying date) and No.2006-346345 (December 22 2006 applying date), and requires its preference, and it is introduced among the application as a reference in full.
Technical field
The polymer secondary battery that the present invention relates to contain the gel-form solid polymer electrolyte of aprotic solvent, support salt and organic compounds containing sulfur and use this gel-form solid polymer electrolyte.
Background technology
Lithium polymer battery because of can slimming, the degree of freedom height selected of shape, do not use electrolytic solution, therefore do not have the possibility of electrolytic solution leakage, receive publicity as the power supply of portable machine etc.Recently,, require energy density increase etc., also require to improve battery behavior thus along with the increase of portable machine function.
Wherein, as the important techniques problem, can enumerate and improve security, improvement high temperature preservation characteristics, improvement cycle characteristics etc.Wherein, about cycle characteristics,, polymer materials of being used for gel electrolyte etc. is improved by being studied.For example, JP-A-2002-100406 has proposed by mixing the improvement of physics crosslinking polymer and chemically crosslinked type gel electrolyte.JP-A-2003-257490 has also proposed to improve the impregnation of pre-gelled solution by baffle surface is carried out modification.
In addition, counter electrode material, shape, create conditions, the material of electrolytic solution etc. also proposed various schemes.
Lithium polymer battery is compared the problem of multiplying power property is arranged (レ one ト characteristic) and cycle characteristics difference with the battery of general use liquid electrolyte.Therefore, to positive pole, negative pole, electrolytic solution, electrolysis additive, dividing plate that adapts with polymer gel and the battery that uses them, study in design and manufacture view.
Problem of the present invention is to provide gel-form solid polymer electrolyte and polymer secondary battery is provided, described gel-form solid polymer electrolyte can realize improving multiplying power property, the cycle characteristics of polymer battery, perhaps can prevent cell expansion that repeated charge causes etc.
Summary of the invention
The present invention is for containing non-proton organic solvent, support salt and have at least 1-O-SO in chemical structure
2-the gel-form solid polymer electrolyte of organic compounds containing sulfur.
Above-mentioned gel-form solid polymer electrolyte, wherein organic compounds containing sulfur is the chain sulphonate.
Above-mentioned gel-form solid polymer electrolyte, the organic compounds containing sulfur that wherein has ring texture are one of any in the following Chemical formula 1,2.
In Chemical formula 1, X represents to have the alkylidene group or the Sauerstoffatom of side chain.Y represents to have the alkylidene group of side chain, the alkylidene group that nothing replaces.Z represents methylene radical or singly-bound.
In Chemical formula 2, n is one of any in 0,1,2, R
1～R
6Be independently selected from hydrogen atom or carbonatoms respectively and be more than 1～alkyl below 12, carbonatoms is more than 3～cycloalkyl below 6, carbonatoms be more than 6～aryl below 12.
Chemical formula 1
Above-mentioned gel-form solid polymer electrolyte, the organic compounds containing sulfur that wherein has ring texture is 1,3-N-morpholinopropanesulfonic acid lactone or 1, in the 4-butyl sultone at least a kind.
Above-mentioned gel-form solid polymer electrolyte, the organic compounds containing sulfur that wherein has ring texture are at least a kind of cyclic disulfonic acid esters that is selected from methylene-sulfonic acid methylene radical ester, methylene-sulfonic acid ethylidene ester and the methylene-sulfonic acid propylidene ester.
Above-mentioned gel-form solid polymer electrolyte, wherein, with respect to non-proton organic solvent with support salt to add up to 100 mass parts, the content of organic compounds containing sulfur be 0.005 mass parts above～below 10 mass parts.
Above-mentioned gel-form solid polymer electrolyte, it contains the vinylene carbonate or derivatives thereof.
Above-mentioned gel-form solid polymer electrolyte, wherein above-mentioned solvent contain the non-proton organic compound more than a kind that is selected from cyclic carbonates, linear carbonate class, aliphatic carboxylic acid esters,'s class, gamma lactone class, ring-type ethers, chain ethers and their fluorine-containing derivant.
Above-mentioned gel-form solid polymer electrolyte contains and is selected from LiPF
6, LiBF
4, LiAsF
6, LiSbF
6, LiClO
4, LiAlCl
4And LiN (CnF
2n+1SO
2) (CmF
2m+1SO
2) material more than at least a kind in (n, m are natural numbers) is as supporting salt.
Above-mentioned gel-form solid polymer electrolyte, the polymkeric substance that wherein constitutes polymer gel are any one in polyacrylic ester, polyethylene oxide and the poly(propylene oxide).
A kind of polymer secondary battery, it has above-mentioned gel-form solid polymer electrolyte, positive pole and negative pole, and described positive pole contains lithium-contained composite oxide as positive active material, and described negative pole contains can absorb, emit the material of lithium as negative electrode active material.
Gel-form solid polymer electrolyte of the present invention contains organic compounds containing sulfurs such as sulphonate, therefore can suppress to discharge and recharge the generation of the gas that causes, and can improve multiplying power property, cycle characteristics.
It is also indeterminate that polymer gel of the present invention improves the reason of aforesaid characteristic, but infer that generally this is by initial stage charging, the epithelium that is formed in negative terminal surface by organic compounds containing sulfurs such as sulphonates plays the effect that the exchange that makes negative electrode active material and electronics becomes smooth etc.
According to the present invention, when in non-protonic solvent, using the gel-form solid polymer electrolyte contain sulphonate etc. to make secondary cell, the capacity sustainment rate that can obtain in the cycle characteristics is good, and the expansion of battery suppress the effect excellence and also can suppress to preserve in the polymer secondary battery of the excellence that raises of resistance.By being applied in the secondary cell with the outer dress of the flexible membrane that contains tinsel and synthetic resin film, can suppress the cell expansion that resistance raises, the gas generation causes, for example not only in small-sized portable machine purposes, in large-scale polymer secondary battery such as automobile purposes, also can obtain big effect.
In addition, the use in the past is considered to be not suitable as in the lithium polymer battery of flaky graphite as negative material of negative material, produces the effect of gas in the time of also can obtaining to suppress to discharge and recharge.
Description of drawings
Describe the present invention with reference to the accompanying drawings, wherein identical numeral relates to components identical.
Fig. 1 is the figure of the positive electrode structure of explanation lithium polymer battery of the present invention.
Fig. 2 is the figure of the negative pole structure of explanation lithium polymer battery of the present invention.
Fig. 3 is the sectional view of cell device (Electricity pond key element) structure after explanation lithium polymer battery of the present invention is reeled.
Fig. 4 is the figure that explanation lithium polymer battery of the present invention is adorned operation outward.
Embodiment
Gel-form solid polymer electrolyte of the present invention contains non-proton organic solvent, supports salt and have at least 1-O-SO in chemical structure
2-organic compounds containing sulfur.
In the present invention, in chemical structure, has at least 1-O-SO
2-organic compounds containing sulfur refer at-O-SO
2Among-the R, except R is alkyl, alkylidene group, O also with the compound of R bonding.
Can enumerate cyclic ester and derivative thereof in chain monoesters, chain diester, lactide and the sultone equimolecular particularly.
Gel-form solid polymer electrolyte of the present invention is made of polymkeric substance, and described polymkeric substance contains non-proton organic solvent, supports salt and have at least 1-O-SO in chemical structure
2-organic compounds containing sulfur and polymer gel.
Gel-form solid polymer electrolyte of the present invention can by with polymkeric substance such as polyacrylonitrile, polyethylene oxide, poly(propylene oxide), poly(vinylidene fluoride) and non-proton organic solvent, support salt and in chemical structure, have at least 1-O-SO
2-mixing such as organic compounds containing sulfur and make.
In addition, also can utilize following method manufacturing, will have polymerizable monomer and non-proton organic solvent, the support salt of polymerizability functional group and in chemical structure, have at least 1-O-SO
2-organic compounds containing sulfur etc. mix with polymerization starter, undertaken crosslinkedly by heat or light etc., make the method for polymkeric substance.
The preferred especially as latter is described to be mixed polymerizable monomer with required composition, with mixture scene (in situ) polymerization in the packaging container outside battery.
As in chemical structure, having at least 1-O-SO
2-organic compounds containing sulfur, can enumerate the single sulphonate of chain sulphonate, ring-type, cyclic disulfonic acid ester.
As the chain sulphonate, can enumerate methyl mesylate, ethyl methane sulfonate, busulfan (tetramethylene-two (methanesulfonates) etc.
As the single sulphonate of ring-type, can enumerate the ring molecule lactone as 1,3-N-morpholinopropanesulfonic acid lactone, 1,4-butyl sultone, α-trifluoromethyl-γ-sultone, β-trifluoromethyl-γ-sultone, γ-trifluoromethyl-γ-sultone, Alpha-Methyl-γ-sultone, α, β-two (trifluoromethyl)-γ-sultone, α, α-two (trifluoromethyl)-γ-sultone, α-11 fluorine amyl group-γ-sultone, α-seven fluoropropyls-γ-sultone etc.
As cyclic disulfonic acid ester, can enumerate methylene-sulfonic acid methylene radical ester, methylene-sulfonic acid ethylidene ester, methylene-sulfonic acid propylidene ester etc.
In these compounds, can enumerate 1 expression of following compound methylene-sulfonic acid methylene radical ester, compound 2 expressions methylene-sulfonic acid ethylidene ester, compound 3～compound 9 isocyclic compounds and compound 10 1, the 3-N-morpholinopropanesulfonic acid lactone.
Compound 1
Compound 6
Compound 2
Compound 7
Compound 3
Compound 8
Compound 4
Compound 9
Compound 5
Compound 10
It is generally acknowledged that organic compounds containing sulfurs such as cyclic disulfonic acid ester of the present invention form epithelium on the electrode of lithium-ion secondary cell.That is to say, form epithelium before can be in the polymer gel contained decomposition such as non-proton organic solvent such as sulfonate compound, therefore the decomposition of non-proton organic solvent is suppressed, and can expect to suppress by decomposing cell expansion that the gas that produces causes, improving multiplying power property.
In addition, when positive pole contains lithium manganese composite oxides such as lithium manganate, can prevent that the manganese of stripping is adsorbed on negative terminal surface in the gel.Its result it is generally acknowledged that multiplying power property reduction, the raising cycle characteristics to suppressing to be caused by the resistance rising is effective.
In addition, with respect to non-proton organic solvent with support salt to add up to 100 mass parts, that the concentration of the organic compounds containing sulfur in the gel-form solid polymer electrolyte of the present invention is preferably 0.005 mass parts is above～below 10 mass parts.
More preferably more than 0.01 mass parts, more preferably more than 0.05 mass parts.Can improve battery behavior thus.In addition, if more than 10 mass parts, then the moving resistance of lithium ion increases.More preferably below 5 mass parts.
Have again, also can add multiple organic compounds containing sulfur.For example, can in compound 1～compound 9, add the sultone compound of compound 10.In addition, also can add the vinylene carbonate compound.Thus, the stability of the epithelium that forms in negative terminal surface significantly improves, suppress the decomposition of non-proton organic solvent greatly, perhaps significantly prevented the characteristic degradation that the moisture of inside battery causes, can seek the expansion that improves cycle characteristics, suppresses battery, the rising that suppresses internal resistance.
Further, with respect to non-proton organic solvent, support salt to add up to 100 mass parts, the addition of preferred vinylene carbonate and derivative thereof be 0.1 quality % above～below the 3.0 quality %.
As operable polymerizable monomer in the manufacturing of polymer gel, can enumerate 1 molecule and have the monomer of 2 above polymerizable functional groups or oligopolymer etc.Particularly, as the gelation composition, can enumerate ethylene glycol bisthioglycolate (methyl) acrylate, glycol ether two (methyl) acrylate, triglycol two (methyl) acrylate, Tetraglycol 99 two (methyl) acrylate, two (methyl) vinylformic acid propylidene ester, two (methyl) vinylformic acid dipropylene ester, two (methyl) vinylformic acid Sanya propyl diester, 1,3-butyleneglycol two (methyl) acrylate, 1,4-butyleneglycol two (methyl) acrylate, 1,2 officials such as 6-hexylene glycol two (methyl) acrylate energy (methyl) acrylate; 3 officials such as trimethylolpropane tris (methyl) acrylate, tetramethylolmethane three (methyl) acrylate energy (methyl) acrylate; 4 officials such as ditrimethylolpropane four (methyl) acrylate, tetramethylolmethane four (methyl) acrylate energy (methyl) acrylate etc.In addition, can also enumerate monomers such as ammonia ester (methyl) acrylate, these multipolymers oligopolymer or with the multipolymer oligopolymer of vinyl cyanide.Can also use in addition in the softening agent such as can being dissolved in poly(vinylidene fluoride), polyethylene oxide, polyacrylonitrile and the polymkeric substance of gelation.
Be noted that (methyl) acrylate is meant any one in acrylate, the methacrylic ester, perhaps contains both materials.
Above-mentioned monomer, oligopolymer or polymkeric substance can use separately, perhaps multiple mixing is used, but the composition that also can mix other gelation use.
As non-proton organic solvent, mixing more than a kind or 2 kinds of following non-proton organic solvent can be used: propylene carbonate (PC), carbonic acid ethylidene ester (EC), carbonic acid butylidene ester (BC), vinylene carbonate cyclic carbonates such as (VC); Methylcarbonate (DMC), diethyl carbonate (DEC), ethylmethyl carbonate (EMC), dipropyl carbonate linear carbonate classes such as (DPC); Aliphatic carboxylic acid esters,'s classes such as methyl-formiate, methyl acetate, ethyl propionate; Gamma lactone classes such as gamma-butyrolactone; 1,2-Ethoxyethane (DEE), oxyethyl group methoxy base ethane chain ethers such as (EME); Ring-type ethers such as tetrahydrofuran (THF), 2-methyltetrahydrofuran; Dimethyl sulfoxide (DMSO), 1,3-dioxolane, methane amide, ethanamide, dimethyl formamide, dioxolane, acetonitrile, propyl group formonitrile HCN, Nitromethane 99Min., ethyl Monoethylene Glycol (MEG) dme, phosphotriester, trimethoxy-methane, dioxolane derivatives, tetramethylene sulfone, methyl sulfolane, 1,3-dimethyl-2-imidazolone, 3-methyl-2- oxazolidone, propylene carbonate ester derivative, tetrahydrofuran derivatives, ether, phenylmethylether, N-Methyl pyrrolidone, alpha-fluorocarboxylate ester etc.
As supporting salt, can enumerate LiPF
6, LiAsF
6, LiAlCl
4, LiClO
4, LiBF
4, LiSbF
6, LiCF
3SO
3, LiC
4F
9CO
3, LiC (CF
3SO
2)
3, LiN (CF
3SO
2)
2, LiN (C
2F
5SO
2)
2, LiB
10Cl
10, lower aliphatic carboxylic acid lithium, chloroborane lithium, tetraphenyl lithium tetraborate, LiCl, LiBr, LiI, LiSCN, LiCl, acid imide etc.These support the densitometer of the concentration of salt in gel-form solid polymer electrolyte with lithium salts, can be 0.5mol/l～1.5mol/l.If concentration is greater than 1.5mol/l, then the characteristic of polymer dielectric reduces, and concentration is less than 0.5mol/l hour, and specific conductivity reduces.
Gel-form solid polymer electrolyte of the present invention can be by to containing polymerizability material, non-proton organic solvent, support salt and have at least 1-O-SO in chemical structure
2-the composition of organic compounds containing sulfur in add polymerization starter, by heating or irradiates light and polymerization obtains.As polymerization starter, can enumerate bitter almond oil camphor class, peroxide.The preferred peroxidation trimethylacetic acid tert-butyl ester.
Gel-form solid polymer electrolyte of the present invention can be used for lighium polymer secondary battery.At this moment, positive pole is to be coated with positive electrode active material layer on the current collector that comprises metal such as aluminium foil, and dry and compression, moulding obtain, and negative pole is to be coated with negative electrode active material on the current collector that comprises metal such as Copper Foil, and dry and compression, moulding obtain.Dividing plate can use non-woven fabrics, polyolefin micro porous polyolefin membrane etc.
Can by make dividing plate between positive pole and negative pole with positive pole and the stacked layered product of making of negative pole, perhaps by dividing plate behind reel between positive pole and the negative pole anodal and negative pole, make the coiling body of flat ground moulding, layered product or coiling body be contained in comprise metal jar exterior body or comprise in the exterior body of flexible exterior material, inject the preceding polymer gel formation composition of polyreaction afterwards, make lithium polymer battery by polymerized in-situ then.
Also can in advance polymer gel be formed and accommodate in the battery exterior body, carry out polymerization afterwards with composition.Perhaps also can be on anode electrode, negative electrode or dividing plate the coated polymeric gel electrolyte, form coating layer after, assembled battery again.
In addition, when making lithium polymer battery,, can use the material more than a kind or 2 kinds in the material that is selected from for example lithium metal, lithium alloy and can absorbs, emit lithium as negative electrode active material.
As the material that absorbs, emits lithium ion, can use the carbon material, metal oxide, the metal that absorb and emit lithium.
As carbon material, can enumerate carbon materials such as graphite, decolorizing carbon, diamond-like-carbon, carbon nanotube.Preferred especially graphite material or decolorizing carbon.Graphite material electroconductibility height particularly, with the cementability and the voltage flatness excellence of the current collector that comprises metal such as copper, owing to form by high treatment temp, therefore contained impurity is few, helps to improve the negative pole performance, so is preferred.
In addition,, can use in silicon oxide, stannic oxide, Indium sesquioxide, zinc oxide, phosphoric acid, the boric acid any one, perhaps use their mixture, especially preferably contain silicon oxide as metal oxide.The structure optimization metamict.
This is because silicon oxide is stable, can not react with other compound, also because amorphous structure can not produce the deterioration that crystal boundary, the such ununiformity of flaw cause.As film, can use methods such as vapour deposition method, CVD method, sputtering method.
As metallic substance, can enumerate lithium, lithium alloy.As lithium alloy, constitute by the alloy more than 2 yuan or 3 yuan of metals such as Al, Si, Sn, In, Ag, Ba, Ca, Pd, Pt, Zn, La and lithium.The preferred especially amorphous of lithium metal or lithium alloy.This is because amorphous structure is difficult to produce the deterioration that is caused by crystal boundary, the such ununiformity of flaw.
Lithium metal or lithium alloy can form with suitable modes such as the liquation type of cooling, liquid quench mode, atomizing type, vacuum evaporation mode, sputter mode, plasma CVD mode, optical cvd mode, hot CVD mode, sol-gel modes.
In addition, as positive active material, can enumerate for example LiCoO
2, LiNiO
2, LiMn
2O
4Deng lithium-contained composite oxide, the transition metal of these lithium-contained composite oxides part also can be replaced by other element.
In addition, also can use the lithium-contained composite oxide that more than metallic lithium plate potential 4.5V, has Ping Qu.As lithium-contained composite oxide, can enumerate spinel type lithium manganese complex oxide, olivine-type lithium-contained composite oxide, inverse spinel structure lithium-contained composite oxide etc.The compound that lithium-contained composite oxide can be represented for following general formula.
Li
a(M
xMn
2-x)O
4
In the formula, 0＜x＜2,0＜a＜1.2.M is at least a kind that is selected among Ni, Co, Fe, Cr and the Cu.
Positive pole among the present invention can followingly obtain: these active substances with conductive materials such as carbon black, poly(vinylidene fluoride) tackiness agent dispersion millings in N-N-methyl-2-2-pyrrolidone N-(NMP) equal solvent such as (PVDF), are coated on it on matrixes such as aluminium foil.
When using lithium manganese composite oxide as positive active material, total amount 100 mass parts with respect to non-proton organic solvent and support salt, that the amount of the organic compounds containing sulfur in the gel-form solid polymer electrolyte is preferably 0.1 mass parts is above～below 3.0 mass parts, and be preferably especially 0.5 mass parts above～below 1.0 mass parts.When being lower than 0.1 mass parts, can not fully form epithelium at electrode surface, cycle characteristics, multiplying power property to improve effect little.If surpass 3.0 mass parts, then resistance increases, the multiplying power property variation.
In addition, when using the lithium cobalt composite oxide as positive active material, with respect to non-proton organic solvent with support total amount 100 mass parts of salt, that the amount of the organic compounds containing sulfur in the gel-form solid polymer electrolyte is preferably 0.5 mass parts is above～below 5.0 mass parts.When being lower than 0.5 mass parts, can not fully form epithelium at electrode surface, cycle characteristics, multiplying power property to improve effect little.If surpass 5.0 mass parts, then resistance increases, the multiplying power property variation.
In addition,, porous membrane, non-woven fabrics of polyolefine such as polyethylene, polypropylene or fluoro-resin etc. can be used, lamination porous membrane not of the same race or non-woven fabrics can be used and the dividing plate of the laminar structure that obtains as dividing plate.
With reference to the accompanying drawings, be that example illustrates polymer battery of the present invention with the lighium polymer secondary battery.
Fig. 1 is the figure of the positive electrode structure of explanation lithium polymer battery of the present invention, Fig. 2 is the figure of the negative pole structure of explanation lithium polymer battery of the present invention, Fig. 3 is the sectional view of explanation lithium polymer battery of the present invention battery element structure behind coiling, and Fig. 4 is the figure that explanation lithium polymer battery of the present invention is adorned operation outward.
Embodiment 1-1
The making of testing battery
With Fig. 1 the anodal making is described.With 85 quality %LiMn
2O
4, 7 quality % mix as the acetylene black, 8 quality % of the conduction subsidiary material poly(vinylidene fluoride) as tackiness agent, add N-Methyl pyrrolidone in this mixture, further mix, and make anode sizing agent.Is the two sides of the aluminium foil 2 of 20 μ m with scraping the skill in using a kitchen knife in cookery with the thickness that it is coated on as current collector, makes the thickness after the roller process reach 160 μ m, forms positive active material coating part 3.In addition, uncoated 4 of the positive active material that is not coated with positive active material on any one face is set at both ends, uncoated 4 of a positive active material is provided with anodal conductive foil 6 therein, be adjacent setting and only on single face, be coated with positive active material single spreading portion 5, make anodal 1.
Below, the making of negative pole is described with Fig. 2.90 quality % flaky graphites, 10 quality % are mixed as the poly(vinylidene fluoride) of tackiness agent, add N-Methyl pyrrolidone, further mix, make cathode size.It is coated on as the thickness of current collector is Copper Foil 8 two sides of 10 μ m, makes the thickness after the roller process reach 120 μ m, forms negative electrode active material coating part 9.In addition, the negative electrode active material single spreading portion 10 of single spreading only is set on an end face at both ends and is not coated with the non-coating part 11 of negative electrode active material of negative electrode active material, negative pole conductive foil 12 is installed, make negative pole 7.
Utilize Fig. 3 that the making of cell device is described.Dividing plate 13 weldings of 2 polyethylene microporous films that comprise thickness 12 μ m, void content 35% and the partial fixing that cuts off are reeled on the volume core of wind2, import the positive pole 1 made in advance and the top of negative pole 7.Positive pole 1 is a tip side with the opposition side of the connection section of anodal conductive foil 6, negative pole 7 is a tip side with the connection section side of negative pole conductive foil 12, between 2 dividing plates, dispose negative pole respectively, on dividing plate the configuration anode electrode, by reeling, form cell device around volume core rotation.
As shown in Figure 4, this cell device is contained in the outer dress film of coinging, draws anodal conductive foil 6 and negative pole conductive foil 12, the edge contraction of film will be adorned outward, keep polymer gel and form the fluid injection part 14 of using composition, carry out thermal welding, make battery 15.
Gel-form solid polymer electrolyte forms and is prepared as follows with composition: in 30 quality % carbonic acid ethylidene esters (EC) and 58 quality % diethyl carbonates (DEC), with respect to the LiPF that contains as lithium salts
6Electrolytic solution 100 mass parts of 12 quality %, add 1 mass parts 1,3-N-morpholinopropanesulfonic acid lactone, 3.8 mass parts are as triethylene glycol diacrylate, the 1 mass parts Viscoat 295 of gelating agent, behind the thorough mixing, mix with the peroxidation trimethylacetic acid tert-butyl ester of 0.5 mass parts as polymerization starter.
Then, battery 14 is installed in the reliever, after the absorption gas inside, uses composition, carry out vacuum impregnation, obtain the lighium polymer secondary battery 15 of sample 1-1 from the 14 injection of polymer gel electrolytes formation of fluid injection portion.
1. multiplying power property test method
At 20 ℃, the gained lighium polymer secondary battery is carried out constant current charge after cell voltage is 4.2V with charging current 0.2C, reach 6.5 hours with constant-potential charge until total charging time.With the discharge of the discharging current of 0.2C, be 3.0V then until cell voltage, loading capacity at this moment as initial capacity.
Multiplying power property for the gained lithium polymer battery, with charging to cell voltage is that to be discharged to cell voltage with 0.2C be 3.0V for the battery of 4.2V, the gained loading capacity as 100, with the likening to of loading capacity that obtains with the discharge of the discharge-rate of 1.0C be multiplying power property, be shown in Table 1 with percentage.
2. round-robin test
Cycling condition, charging: carry out with the 1C charging current that constant current charge is supreme rations the power supply that to press be 4.2V, under constant voltage, carry out total charging time afterwards and be 2.5 hours charging.Discharge:, discharge under the condition of electric current: 1C at lower voltage limit 3.0V.All implement at 20 degree.The capacity sustainment rate is illustrated in table 1 with the 100th round-robin loading capacity (1C) with respect to the ratio of the 1st round-robin loading capacity (1C).
In addition, the battery volume after the initial charge as 1.0, with its with circulation after the ratio of battery volume be shown in Table 1.
Embodiment 1-2
Except adding 0.05 mass parts 1, outside the 3-N-morpholinopropanesulfonic acid lactone and embodiment 1-1 similarly make the test cell of sample 1-2, estimate equally with embodiment 1-1.It the results are shown in table 1.
Embodiment 1-3
Except adding 0.5 mass parts 1, outside the 3-N-morpholinopropanesulfonic acid lactone and embodiment 1-1 similarly make the test cell of sample 1-3, estimate equally with embodiment 1-1.It the results are shown in table 1.
Embodiment 1-4
Except adding 0.1 mass parts 1, outside the 3-N-morpholinopropanesulfonic acid lactone and embodiment 1-1 similarly make the test cell of sample 1-4, estimate equally with embodiment 1-1.It the results are shown in table 1.
Embodiment 1-5
Except adding 2.0 mass parts 1, outside the 3-N-morpholinopropanesulfonic acid lactone and embodiment 1-1 similarly make the test cell of sample 1-5, estimate equally with embodiment 1-1.It the results are shown in table 1.
Embodiment 1-6
Except adding 3.0 mass parts 1, outside the 3-N-morpholinopropanesulfonic acid lactone and embodiment 1-1 similarly make the test cell of sample 1-6, estimate equally with embodiment 1-1.It the results are shown in table 1.
Embodiment 1-7
Except adding 4.0 mass parts 1, outside the 3-N-morpholinopropanesulfonic acid lactone and embodiment 1-1 similarly make the test cell of sample 1-7, estimate equally with embodiment 1-1.It the results are shown in table 1.
Embodiment 1-8
Except adding 5.0 mass parts 1, outside the 3-N-morpholinopropanesulfonic acid lactone and embodiment 1-1 similarly make the test cell of sample 1-8, estimate equally with embodiment 1-1.It the results are shown in table 1.
Embodiment 1-9
Except adding 10 mass parts 1, outside the 3-N-morpholinopropanesulfonic acid lactone and embodiment 1-1 same, make the test cell of sample 1-9, estimate equally with embodiment 1-1.It the results are shown in table 1.
Comparative example 1-1
Except not adding 1, outside the 3-N-morpholinopropanesulfonic acid lactone and embodiment 1-1 similarly make the test cell of duplicate 1-1, estimate equally with embodiment 1-1.It the results are shown in table 1.
Comparative example 1-2
Except adding 12.0 mass parts 1, outside the 3-N-morpholinopropanesulfonic acid lactone and embodiment 1-1 similarly make the test cell of duplicate 1-2, estimate equally with embodiment 1-1.It the results are shown in table 1.
Table 1
| Specimen coding | 1,3-N-morpholinopropanesulfonic acid lactone (mass parts) | Multiplying power property (%) | Capacity sustainment rate (%) | Volume change (%) |
| Embodiment 1-1 | 1.0 | 95 | 91 | 1.0 |
| Embodiment 1-2 | 0.05 | 65 | 50 | 4.0 |
| Embodiment 1-3 | 0.5 | 93 | 89 | 1.0 |
| Embodiment 1-4 | 0.1 | 91 | 85 | 1.1 |
| Embodiment 1-5 | 2.0 | 83 | 70 | 3.0 |
| Embodiment 1-6 | 3.0 | 80 | 64 | 5.0 |
| Embodiment 1-7 | 4.0 | 60 | 45 | 5.0 |
| Embodiment 1-8 | 5.0 | 54 | 40 | 5.0 |
| Embodiment 1-9 | 10.0 | 48 | 33 | 7.0 |
| Comparative example 1-1 | 0 | 40 | 5 | 20 |
| Comparative example 1-2 | 12.0 | 35 | 3 | 25.0 |
Embodiment 1-10
The preparation of methylene-sulfonic acid methylene radical ester
Silver carbonate 213.94g (0.772mol) and acetonitrile 749ml are packed in the reaction flask, below 40 ℃ to the acetonitrile 491ml solution that wherein drips methylenedisulfonyl chlorine 77.93g (0.366mol).
, filter after 24 hours 25 ℃ of stirrings,, obtain the acetonitrile solution of 991.35g methylsulfonic acid silver salt with the acetonitrile washing.Contain 126.28g (0.324mol) methylsulfonic acid silver salt.In the acetonitrile solution 991.35g of this methylsulfonic acid silver salt, add methylene iodide 207.44g (0.771mol), under refluxing, stirred 24 hours.Filter, wash, concentrate, obtain the yellow pasty sludge of 89.11g with acetonitrile.Add 3 methylene dichloride 100ml and carry out stripping.With after the decolouring of the dichloromethane solution of stripping, filtering, be concentrated into about 5ml with gac, the crystallization that filtration is separated out 50 ℃ of dryings, obtains white, needle-shaped crystals 4.19g.Fusing point: 146～147 ℃.In addition, by
1H-NMR confirms as compound 1 methylene-sulfonic acid methylene radical ester.
The making of test cell
Replace 1 with 1 mass parts methylene-sulfonic acid methylene radical ester, the 3-N-morpholinopropanesulfonic acid lactone, in addition the same with embodiment 1-1, the test cell of making sample 1-10 is estimated equally with embodiment 1-1.It the results are shown in table 2.
Embodiment 1-11
Add 0.05 mass parts methylene-sulfonic acid methylene radical ester and replace 1, the 3-N-morpholinopropanesulfonic acid lactone, in addition the same with embodiment 1-1, the test cell of making sample 1-11 is estimated equally with embodiment 1-1.It the results are shown in table 2.
Embodiment 1-12
Add 0.5 mass parts methylene-sulfonic acid methylene radical ester and replace 1, the 3-N-morpholinopropanesulfonic acid lactone, in addition the same with embodiment 1-1, the test cell of making sample 1-12 is estimated equally with embodiment 1-1.It the results are shown in table 2.
Embodiment 1-13
Add 0.1 mass parts methylene-sulfonic acid methylene radical ester and replace 1, the 3-N-morpholinopropanesulfonic acid lactone, in addition the same with embodiment 1-1, the test cell of making sample 1-13 is estimated equally with embodiment 1-1.It the results are shown in table 2.
Embodiment 1-14
Add 2.0 mass parts methylene-sulfonic acid methylene radical esters and replace 1, the 3-N-morpholinopropanesulfonic acid lactone, in addition the same with embodiment 1-1, the test cell of making sample 1-14 is estimated equally with embodiment 1-1.It the results are shown in table 2.
Embodiment 1-15
Add 3.0 mass parts methylene-sulfonic acid methylene radical esters and replace 1, the 3-N-morpholinopropanesulfonic acid lactone, in addition the same with embodiment 1-1, the test cell of making sample 1-15 is estimated equally with embodiment 1-1.It the results are shown in table 2.
Embodiment 1-16
Add 4.0 mass parts methylene-sulfonic acid methylene radical esters and replace 1, the 3-N-morpholinopropanesulfonic acid lactone, in addition the same with embodiment 1-1, the test cell of making sample 1-16 is estimated equally with embodiment 1-1.It the results are shown in table 2.
Embodiment 1-17
Add 5.0 mass parts methylene-sulfonic acid methylene radical esters and replace 1, the 3-N-morpholinopropanesulfonic acid lactone, in addition the same with embodiment 1-1, the test cell of making sample 1-17 is estimated equally with embodiment 1-1.It the results are shown in table 2.
Embodiment 1-18
Add 10.0 mass parts methylene-sulfonic acid methylene radical esters and replace 1, the 3-N-morpholinopropanesulfonic acid lactone, in addition the same with embodiment 1-1, the test cell of making sample 1-18 is estimated equally with embodiment 1-1.It the results are shown in table 2.
Comparative example 1-3
Add 12.0 mass parts methylene-sulfonic acid methylene radical esters and replace 1, the 3-N-morpholinopropanesulfonic acid lactone, in addition the same with embodiment 1-1, the test cell of making duplicate 1-3 is estimated equally with embodiment 1-1.It the results are shown in table 2.
Table 2
| Specimen coding | Methylene-sulfonic acid methylene radical ester (mass parts) | Multiplying power property (%) | Capacity sustainment rate (%) | Volume change (%) |
| Embodiment 1-10 | 1.0 | 95 | 94 | 0.7 |
| Embodiment 1-11 | 0.05 | 66 | 57 | 7.0 |
| Embodiment 1-12 | 0.5 | 93 | 91 | 0.8 |
| Embodiment 1-13 | 0.1 | 91 | 88 | 1.0 |
| Embodiment 1-14 | 2.0 | 87 | 86 | 1.5 |
| Embodiment 1-15 | 3.0 | 80 | 83 | 2.4 |
| Embodiment 1-16 | 4.0 | 60 | 51 | 4.0 |
| Embodiment 1-17 | 5.0 | 54 | 48 | 4.0 |
| Embodiment 1-18 | 10.0 | 48 | 41 | 7.0 |
| Comparative example 1-1 | 0 | 40 | 5 | 20 |
| Comparative example 1-3 | 12.0 | 48 | 13 | 16 |
Embodiment 1-19
With the LiCoO of 87 quality % as positive active material
2, 5 quality % mix as the poly(vinylidene fluoride) of tackiness agent as the conduction acetylene black of subsidiary material and 8 quality %, in this mixture, add N-Methyl pyrrolidone, further mix, make anode sizing agent, in addition, the same with embodiment 1-1, make positive pole, in addition, the gel-form solid polymer electrolyte of putting down in writing in embodiment 1-1 forms with further adding vinylene carbonate 0.5 mass parts in the composition, makes the polymer secondary battery of sample 1-19, in addition, estimate equally with embodiment 1-1, it the results are shown in table 3.
Embodiment 1-20
Make 1, the use level of 3-N-morpholinopropanesulfonic acid lactone is 0.5 mass parts, and is in addition the same with embodiment 1-19, makes the test cell of sample 1-20, estimates equally with embodiment 1-1.It the results are shown in table 3.
Embodiment 1-21
Make 1, the use level of 3-N-morpholinopropanesulfonic acid lactone is 2.5 mass parts, and is in addition the same with embodiment 1-19, makes the test cell of sample 1-21, estimates equally with embodiment 1-1.It the results are shown in table 3.
Embodiment 1-22
Make 1, the use level of 3-N-morpholinopropanesulfonic acid lactone is 3.5 mass parts, and is in addition the same with embodiment 1-19, makes the test cell of sample 1-22, estimates equally with embodiment 1-1.It the results are shown in table 3.
Embodiment 1-23
Make 1, the use level of 3-N-morpholinopropanesulfonic acid lactone is 5.0 mass parts, and is in addition the same with embodiment 1-19, makes the test cell of sample 1-23, estimates equally with embodiment 1-1.It the results are shown in table 3.
Embodiment 1-24
Make 1, the use level of 3-N-morpholinopropanesulfonic acid lactone is 10.0 mass parts, and is in addition the same with embodiment 1-19, makes the test cell of sample 1-24, estimate the same with embodiment 1-1.It the results are shown in table 3.
Embodiment 1-25
Do not add vinylene carbonate, make 1, the addition of 3-N-morpholinopropanesulfonic acid lactone is 0.3 mass parts, and is in addition the same with embodiment 1-19, makes the test cell of sample 1-25, estimates equally with embodiment 1-1.It the results are shown in table 3.
Embodiment 1-26
Do not add vinylene carbonate, make 1, the addition of 3-N-morpholinopropanesulfonic acid lactone is 6.0 mass parts, and is in addition the same with embodiment 1-19, makes the test cell of sample 1-26, estimates equally with embodiment 1-1.It the results are shown in table 3.
Embodiment 1-27
Do not add vinylene carbonate, make 1, the addition of 3-N-morpholinopropanesulfonic acid lactone is 8.0 mass parts, and is in addition the same with embodiment 1-19, makes the test cell of sample 1-27, estimates equally with embodiment 1-1.It the results are shown in table 3.
Comparative example 1-4
Vinylene carbonate and 1,3-N-morpholinopropanesulfonic acid lactone all do not add, and be in addition the same with embodiment 1-19, makes the test cell of duplicate 1-4, estimates equally with embodiment 1-1, and it the results are shown in table 3.
Comparative example 1-5
Do not add vinylene carbonate, make 1, the addition of 3-N-morpholinopropanesulfonic acid lactone is 12.0 mass parts, in addition and embodiment 1-19 same, make the test cell of control sample 1-5, estimate equally with embodiment 1-1, it the results are shown in table 3.
Table 3
| Specimen coding | 1,3-N-morpholinopropanesulfonic acid lactone (mass parts) | Multiplying power property (%) | Capacity sustainment rate (%) | Volume change (%) |
| Embodiment 1-19 | 1.0 | 95 | 90 | 1.0 |
| Embodiment 1-20 | 0.5 | 97 | 91 | 0.8 |
| Embodiment 1-21 | 2.5 | 93 | 87 | 1.3 |
| Embodiment 1-22 | 3.5 | 91 | 80 | 1.5 |
| Embodiment 1-23 | 5.0 | 90 | 76 | 1.7 |
| Embodiment 1-24 | 10.0 | 90 | 76 | 1.7 |
| Embodiment 1-25 | 0.3 | 87 | 83 | 1.4 |
| Embodiment 1-26 | 6.0 | 51 | 51 | 6.0 |
| Embodiment 1-27 | 8.0 | 23 | 43 | 7.4 |
| Comparative example 1-4 | 0 | 41 | 7 | 23 |
| Comparative example 1-5 | 12.0 | 10 | 10 | 20 |
Embodiment 1-28～1-33
Make 1, the addition of 3-N-morpholinopropanesulfonic acid lactone is 1 mass parts, makes the addition of vinylene carbonate as shown in table 4, between 0.05～8.0 mass parts, change, make the test cell of sample 1-27～1-33, estimate equally with embodiment 1-1, it the results are shown in table 4.
Table 4
| Test number | Vinylene carbonate (mass parts) | Multiplying power property (%) | Capacity sustainment rate (%) | Volume change (%) |
| Embodiment 1-28 | 0.1 | 93 | 90 | 1.3 |
| Embodiment 1-29 | 2.0 | 90 | 93 | 1.5 |
| Embodiment 1-30 | 3.0 | 80 | 80 | 5.0 |
| Embodiment 1-31 | 0.05 | 65 | 50 | 4.0 |
| Embodiment 1-32 | 4.0 | 60 | 45 | 5.0 |
| Embodiment 1-33 | 8.0 | 54 | 40 | 5.0 |
Embodiment 2-1
Test cell to the sample 1-10 that makes in embodiment 1-10 carries out 500 round-robin round-robin tests, the evaluation method that replaces embodiment 1-1, carry out 500 circulations of the round-robin test the same, equally the volume change after the capacity sustainment rate after 500 circulations and 500 circulations is estimated with embodiment 1-1.It the results are shown in table 5.
Embodiment 2-2
The preparation of methylene-sulfonic acid ethylidene ester
In stream of nitrogen gas, under-34～-40 ℃, stirring condition, with 20 fens anhydrous ethylene glycol (6.21g of clockwise; 100mmol) 1,2-glycol dimethyl ether (DME) (1000ml) drips methylenedisulfonyl chlorine (21.33g in the solution; 100mmol) 1,2-glycol dimethyl ether (140ml) solution.Afterwards, in stream of nitrogen gas, under-11～-20 ℃ condition, in reaction solution, stir triethylamine (20.27g; 200mmol) 1, behind 2-glycol dimethyl ether (140ml) solution, down continued the stirring reaction liquid 1 hour at 25 ℃.Decompression is injected frozen water with residue after heating up in a steamer and desolvating, and stirs after 10 minutes, filters out the white crystals of separating out, and after will filtering polymers and washing with frozen water, at 50 ℃ of drying under reduced pressure, obtains the methylene-sulfonic acid ethylidene ester 10.86g (53.71mmol as compound 2 thus; 53.7%).Fusing point is 168～170 ℃.
Add methylene-sulfonic acid ethylidene ester 1 mass parts and replace methylene-sulfonic acid methylene radical ester, in addition the same with embodiment 1-10, the test cell of making sample 2-2 is estimated equally with embodiment 2-1.It the results are shown in table 5.
Embodiment 2-3
Except that methylene-sulfonic acid methylene radical ester 1 mass parts, also add vinylene carbonate 1 mass parts, in addition the same with embodiment 1-10, the test cell of making sample 2-3 is estimated equally with embodiment 2-1.It the results are shown in table 5.
Embodiment 2-4
Except that methylene-sulfonic acid methylene radical ester 1 mass parts, also add 1,3-N-morpholinopropanesulfonic acid lactone 1 mass parts, in addition the same with embodiment 1-10, the test cell of making sample 2-4 is estimated equally with embodiment 2-1.It the results are shown in table 5.
Embodiment 2-5
Except that methylene-sulfonic acid methylene radical ester 1 mass parts, also add vinylene carbonate 1 mass parts and 1,3-N-morpholinopropanesulfonic acid lactone 1 mass parts, in addition the same with embodiment 1-10, the test cell of making sample 2-4 is estimated equally with embodiment 2-1.It the results are shown in table 5.
Table 5
| Specimen coding | Additive | The addition mass parts | 500 circulation back capacity sustainment rates (%) | 500 circulation back volume changes (%) |
| Embodiment 2-1 | Methylene-sulfonic acid methylene radical ester | 1 | 85 | 3.2 |
| Embodiment 2-2 | Methylene-sulfonic acid ethylidene ester | 1 | 80 | 3.4 |
| Embodiment 2-3 | Methylene-sulfonic acid methylene radical ester vinylene carbonate | 1 1 | 91 | 3.4 |
| Embodiment 2-4 | Methylene-sulfonic acid methylene radical ester 1, the 3-N-morpholinopropanesulfonic acid lactone | 1 1 | 89 | 3.5 |
| Embodiment 2-5 | Methylene-sulfonic acid methylene radical ester vinylene carbonate 1, the 3-N-morpholinopropanesulfonic acid lactone | 1 1 1 | 92 | 3.8 |
Embodiment 3-1
As non-proton organic solvent, use propylene carbonate (PC) 19 quality %, carbonic acid ethylidene ester (EC) 21 quality % and diethyl carbonate (DEC) 48 quality % to replace carbonic acid ethylidene ester (EC) 30 quality % and diethyl carbonate (DEC) 58 quality %, use decolorizing carbon to replace flaky graphite simultaneously as negative electrode active material, in addition, the same with embodiment 1-6, make the test cell of sample 3-1, estimate equally with embodiment 2-1.It the results are shown in table 6.
Embodiment 3-2
Add 1 mass parts methylene-sulfonic acid ethylidene ester and replace methylene-sulfonic acid methylene radical ester, in addition the same with embodiment 1-10, the test cell of making sample 3-2 is estimated equally with embodiment 2-1.It the results are shown in table 6.
Table 6
| Specimen coding | Additive | The addition mass parts | Capacity sustainment rate (%) after 500 circulations | Volume change (%) after 50 circulations |
| Embodiment 3-1 | Methylene-sulfonic acid methylene radical ester | 1 | 86 | 3.2 |
| Embodiment 3-2 | Methylene-sulfonic acid ethylidene ester | 1 | 81 | 3.4 |
Embodiment 4-1
Make the test cell the same, be determined at the secondary cell dc resistance of the preservation state that is full of under the electricity condition with sample 3-1.
At first, with the secondary cell made 20 ℃ the same with embodiment 1-1, carry out constant current charge to reaching 4.2V with 0.2C, carry out constant-potential charge afterwards and reach 6.5 hours until total charging time.Afterwards, carry out the constant current discharge until reaching 3.0V with 0.2C.The loading capacity of this moment as initial capacity, the resistance of measuring this moment as initial resistance.
Afterwards, carry out charging in 2.5 hours, to assigned voltage, under 20 ℃, 45 ℃, 60 ℃ condition, placed 90 days with constant-current constant-voltage.
After the discharge, discharge until reaching 3.0V with 0.2C at 20 ℃, carry out constant current charge with 1C after, carry out constant-potential charge and reach 2.5 hours until total charging time.Afterwards, carry out constant current discharge until reaching 3.0V with 0.2C, carry out constant current charge with 1C again after, carry out constant-potential charge and reach 2.5 hours until total charging time.Resistance when measuring charging, it the results are shown in table 7.
Embodiment 4-2
Add 1 mass parts methylene-sulfonic acid ethylidene ester and replace methylene-sulfonic acid methylene radical ester, in addition the same with embodiment 4-1, the test cell of making sample 4-2 is estimated equally with embodiment 4-1.It the results are shown in table 7.
Table 7
| Specimen coding | Resistance rate of rise after 90 days (20 ℃ of preservations) | Resistance rate of rise after 90 days (45 ℃ of preservations) | Resistance rate of rise after 90 days (60 ℃ of preservations) |
| Embodiment 4-1 | 1.0 | 1.0 | 1.02 |
| Embodiment 4-2 | 1.02 | 1.06 | 1.14 |
Use the multiplying power property of polymer battery of gel-form solid polymer electrolyte of the present invention good, simultaneously, even charge and discharge cycles repeatedly after, capability retention is also high, the expansion of battery exterior body is few.In addition, the rising of the resistivity after the preservation is also few, not only can be used in the small portable machine with in the battery, also can be used in the large-sized battery of automobile etc.
Claims (11)
1. a gel-form solid polymer electrolyte is characterized in that containing non-proton organic solvent, supports to have at least 1-O-SO in salt and the chemical structure
2-organic compounds containing sulfur.
2. the described gel-form solid polymer electrolyte of claim 1 is characterized in that organic compounds containing sulfur is the chain sulphonate.
3. the described gel-form solid polymer electrolyte of claim 1 is characterized in that organic compounds containing sulfur is any at least a kind of organic compounds containing sulfur with ring texture in the following Chemical formula 1,2,
Chemical formula 1
Chemical formula 2
In Chemical formula 1, X represents to have the alkylidene group or the Sauerstoffatom of side chain, and Y represents to have the alkylidene group of side chain, the alkylidene group that nothing replaces, and Z represents methylene radical or singly-bound;
In Chemical formula 2, n is one of any in 0,1,2, R
1～R
6Be independently selected from hydrogen atom or carbonatoms respectively and be more than 1～alkyl below 12, carbonatoms is more than 3～cycloalkyl below 6, carbonatoms be more than 6～aryl below 12.
4. the described gel-form solid polymer electrolyte of claim 3, wherein, the organic compounds containing sulfur with ring texture is 1,3-N-morpholinopropanesulfonic acid lactone or 1, in the 4-butyl sultone at least a kind.
5. the described gel-form solid polymer electrolyte of claim 3 is characterized in that, the organic compounds containing sulfur with ring texture is at least a kind the cyclic disulfonic acid ester that is selected from methylene-sulfonic acid methylene radical ester, methylene-sulfonic acid ethylidene ester and the methylene-sulfonic acid propylidene ester.
6. power requires 1 described gel-form solid polymer electrolyte, it is characterized in that, with respect to non-proton organic solvent, support salt to add up to 100 mass parts, the content of organic compounds containing sulfur be 0.005 mass parts above～below 10 mass parts.
7. the described gel-form solid polymer electrolyte of claim 1 is characterized in that containing the vinylene carbonate or derivatives thereof.
8. the described gel-form solid polymer electrolyte of claim 1 is characterized in that above-mentioned non-proton organic solvent contains at least a kind that is selected from cyclic carbonates, linear carbonate class, aliphatic carboxylic acid esters,'s class, gamma lactone class, ring-type ethers, chain ethers and their fluorine-containing derivant.
9. the described gel-form solid polymer electrolyte of claim 1 is characterized in that, contains to be selected from LiPF
6, LiBF
4, LiAsF
6, LiSbF
6, LiClO
4, LiAlCl
4And LiN (CnF
2n+1SO
2) (CmF
2m+1SO
2) in any at least a kind of material as supporting salt, wherein, n, m are natural numbers.
10. the described gel-form solid polymer electrolyte of claim 1 is characterized in that, the polymkeric substance that constitutes polymer gel is any at least a kind that is selected from polyacrylic ester, polyethylene oxide and the poly(propylene oxide).
11. polymer secondary battery, it is characterized in that, have the described gel-form solid polymer electrolyte of claim 1, positive pole and negative pole, described positive pole contains lithium-contained composite oxide as positive active material, and described negative pole contains can absorb, emit the material of lithium as negative electrode active material.
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| CN102464648A (en) * | 2010-11-03 | 2012-05-23 | 中国科学院福建物质结构研究所 | Method for refining and purifying methylene methanedisulfonate |
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Free format text: CORRECT: ADDRESS; FROM: SENDAI CITY, MIYAGI, JAPAN TO: KANAGAWA, JAPAN |
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| TA01 | Transfer of patent application right |
Effective date of registration: 20100903 Address after: Kanagawa Applicant after: NEC Energy Components Co., Ltd. Address before: Sendai City, Miyagi Prefecture, Japan Applicant before: NEC Tokin Corp. |
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Application publication date: 20070912 |