CN101800334A - Gel polymer electrolyte, lithium battery comprising gel polymer electrolyte, method for preparing gel polymer electrolyte, and method for preparing lithium battery - Google Patents
Gel polymer electrolyte, lithium battery comprising gel polymer electrolyte, method for preparing gel polymer electrolyte, and method for preparing lithium battery Download PDFInfo
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- CN101800334A CN101800334A CN200910258446A CN200910258446A CN101800334A CN 101800334 A CN101800334 A CN 101800334A CN 200910258446 A CN200910258446 A CN 200910258446A CN 200910258446 A CN200910258446 A CN 200910258446A CN 101800334 A CN101800334 A CN 101800334A
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Abstract
The invention relates to a polymer electrolyte, Li-ion battery containing the same and the manufacturing method of the electrolyte and the Li-ion battery. The polymer electrolyte including: a lithium salt; an organic solvent; a fluorine compound; and a polymer of a monomer represented by Formula 1 below. Formula 1 H 2 C=C-(OR) n -OCH=CH 2 In Formula 1, R is a C2-C10 alkylene group, and n is in a range of about 1 to about 1000.
Description
Technical field
One or more illustrative embodiments relate to polymer dielectric, comprise the lithium battery of described polymer dielectric, prepare the method for described polymer dielectric and the method for preparing described lithium battery.
Background technology
Flexible electronic device such as Electronic Paper have obtained a large amount of public attentions.Described flexible electronic device provides power by secondary cell.The secondary cell that uses in the flexible electronic device should be flexible, and the electrolyte that uses in the secondary cell should seepage.Therefore, electrolyte can be polymer dielectric.
Flexible electronic device can be by Film forming method or print process preparation.Since thin film deposition be complicated and manufacturing cost higher, therefore be extensive use of printing.Therefore, secondary cell can use the print process preparation, and the polymer dielectric that comprises in the secondary cell also can use the print process preparation.
By to the electrolyte irradiation UV light, electron beam or the heat that comprise monomer and initator, use photocuring method or thermal curing method that polymer dielectric is cured.Yet the solidification equipment that is used to carry out photocuring or hot curing can not be suitable for print process.Therefore, still need to develop the method for preparing polymer dielectric that need not independent solidification equipment applicable to print process.
Summary of the invention
One or more illustrative embodiments comprise polymer dielectric.
One or more illustrative embodiments comprise the lithium battery that comprises this polymer dielectric.
One or more illustrative embodiments comprise the method for preparing this polymer dielectric.
One or more illustrative embodiments comprise the method for preparing this lithium battery.
In order to realize above-mentioned and/or other aspects, one or more illustrative embodiments can comprise gel polymer electrolyte, and described polymer dielectric comprises: first lithium salts; Organic solvent; Fluorine compounds; With polymer of monomers shown in the following formula 1:
H
2C＝C-(OR)
n-OCH＝CH
2
Wherein R is that C2-C10 alkylidene and n are about 1 to about 1000.
In order to realize above-mentioned and/or other aspects, one or more illustrative embodiments can comprise lithium battery, and described lithium battery comprises positive pole, negative pole and described gel polymer electrolyte.
In order to realize above-mentioned and/or other aspects, one or more exemplary implementation methods can comprise the method for preparing gel polymer electrolyte, and described method comprises: preparation comprises first solution of fluorine compounds and organic solvent; Preparation comprises second solution of monomer shown in the following formula 1 and organic solvent; Mix described first solution and second solution, wherein said first solution or second solution also comprise first lithium salts:
H
2C＝C-(OR)
n-OCH＝CH
2
Wherein R is the C2-C10 alkylidene, and n is about 1 to about 1000.
In order to realize above-mentioned and/or other aspects, one or more illustrative embodiments can comprise the method for preparing lithium battery, and described method comprises: preparation comprises first solution of fluorine compounds and organic solvent; Preparation comprises second solution of monomer shown in the following formula 1 and organic solvent; Described first solution and second solution are coated with respectively or are printed onto on the electrode, and to form gel polymer electrolyte, wherein said gel polymer electrolyte also comprises first lithium salts:
H
2C＝C-(OR)
n-OCH＝CH
2
Wherein R is the C2-C10 alkylidene, and n is about 1 to about 1000.
Additional aspects of the present invention and/or advantage will partly be set forth in the following description and partly will be apparent from specification, perhaps can know by putting into practice the present invention.
Description of drawings
The description of the following illustrative embodiments of Kao Lving in conjunction with the drawings, these of this instruction and/or other aspects and advantage will become obviously and be more readily understood, wherein:
Fig. 1 is the schematic diagram according to the lithium battery of illustrative embodiments.
Embodiment
Illustrative embodiments to this instruction is elaborated now, and the example illustrates that in the accompanying drawings wherein identical Reference numeral is represented components identical all the time.Illustrative embodiments is described so that the each side of this instruction to be described below with reference to accompanying drawing.
Below will describe gel polymer electrolyte, comprise the lithium battery of described gel polymer electrolyte, prepare the method for described gel polymer electrolyte and the method for the described lithium battery of preparation.According to illustrative embodiments, gel polymer electrolyte comprises: polymer of monomers shown in first lithium salts, organic solvent, fluorine compounds and the following formula 1:
H
2C＝C-(OR)
n-OCH＝CH
2
In formula 1, R is the C2-C10 alkylidene, and n is about 1 to about 1000.
Residual moisture reaction in fluorine compounds and the organic solvent is to produce Bronsted acid or lewis acid.Yet, first lithium salts usually not with organic solvent in the residual moisture reaction produce Bronsted acid or lewis acid.That is to say that first lithium salts is nonactive for residual moisture.
Polymer of monomers shown in the formula 1 can be according to following method preparation.At first, very small amount of residual moisture reacts to produce Bronsted acid or lewis acid in fluorine compounds and the organic solvent.Bronsted acid that produces or lewis acid play the work of polymerization initiator in order to cause cationic polymerization by the carbocation of activation formula 1 monomer.Thus, produce crosslinked polymer by cationic polymerization based on polyvinylether.Because multiple cross-linking reaction takes place to form the matrix based on the polymer of polyvinylether in two functional groups of formula 1 monomer.
In polymerization process before the full solidification, can be included in the electrolyte solution that comprises first lithium salts, organic solvent and fluorine compounds based on the polymer of polyvinylether.As a result, polymer is flooded to obtain gel polymer electrolyte by electrolyte solution.
In charging and discharge process, gel polymer electrolyte can suppress the irreversible reaction between negative active core-shell material and the electrolyte solution and can play the effect of the supporter that is used for active material and electrode structure.Therefore, the lithium battery that comprises described gel polymer electrolyte can have excellent charging and flash-over characteristic.
Yet if polymer solidifies fast before polymer is by the organic solvent dipping, organic solvent can't suitably be impregnated in the polymer.As a result, cured polymer can be separated with organic solvent.For example, if the polymer that separates is attached to electrode surface, organic solvent can't contact with electrode surface, and electrode can not move suitably thus.
Owing to, therefore do not need solidification equipment or initator by preparing gel polymer electrolyte by the Bronsted acid of fluorine compounds generation and the reaction between lewis acid and the monomer.In addition, can adjust rate of polymerization by the quantity and/or the type of control fluorine compounds.
The polymerization of monomer shown in the formula 1 can at room temperature be carried out.Yet polymerization can be carried out to the temperature range between the boiling point of organic solvent in the first lithium salts temperature of precipitation.For example, the temperature of polymerization can be 10 to 40 ℃.
Fluorine compounds can be the organic compound of fluoridizing, second lithium salts that comprises fluorine or its mixture.The organic compound of fluoridizing can be following formula 2 to one of compound shown in the formula 8, but is not limited thereto.The organic compound of fluoridizing can be by with electrolyte solution in residual moisture reaction produce Bronsted acid or lewis acidic any compound.
Formula 2 formulas 3 formulas 4 formulas 5
Formula 6 formulas 7 formulas 8
In formula 2 to 8, R
1To R
3Can be independently of one another be hydrogen atom or C1 to C10 alkyl unsubstituted or that replaced by fluorine atom.R
4To R
9Can be independently of one another be fluorine atom or C1 to C10 alkyl unsubstituted or that replaced by fluorine atom, wherein R
4To R
9In at least one be fluorine atom.
Second lithium salts that comprises fluorine can be LiBF
4, LiPF
6, LiAsF
6, LiSbF
6, LiPF
3(CF
2CF
3)
3Or its any mixture, but be not limited thereto.In this, second lithium salts can be by with electrolyte solution in residual moisture reaction produce Bronsted acid or lewis acidic any lithium salts.
For example, if electrolyte solution contains second lithium salts of high concentration, the Bronsted acid or the lewis acidic amount that produce by the reaction between the residual moisture in second lithium salts and the organic solvent can increase sharply.Therefore, the rate of polymerization that causes by Bronsted acid or lewis acid can increase sharply.As a result, because second lithium salts is once beginning with the monomer mixed polymerization, the completely crued polymer that therefore comprises the repetitive of described monomer can separate (flooding deficiently) with electrolyte solution.
First lithium salts can be LiCF
3CO
2, LiN (COCF
3)
2, LiN (COCF
2CF
3)
2, LiCF
3SO
3, LiCF
3CF
2SO
3, LiC
4F
9SO
3, LiN (CF
3SO
2)
2, LiN (C
2F
5SO
2)
2, wherein p and q are the LiN (C of integer
pF
2p+1SO
2) (C
qF
2q+1SO
2), difluoro (oxalic acid) lithium borate (LiFOB), two (oxalic acid) lithium borate (LiBOB), (malonic acid oxalic acid) lithium borate (LiMOB) or its any mixture, but be not limited thereto.In this, first lithium salts can be not by with electrolyte solution in the residual moisture reaction produce Bronsted acid or lewis acidic any lithium salts.
For example, first lithium salts can comprise or not comprise fluorine.Even first lithium salts comprises fluorine, first lithium salts does not produce Bronsted acid or lewis acid yet.For example, first lithium salts can be wherein fluorine atom and carbon atom bonding and not with the lithium salts of reaction of moisture.On the other hand, second lithium salts is by producing Bronsted acid or lewis acidic lithium salts with reaction of moisture.
In gel polymer electrolyte, based on the total weight of gel polymer electrolyte, the amount of fluorine compounds can be about 0.1 to 30 weight %.For example, based on the total weight of gel polymer electrolyte, fluorine compounds can be about 0.5 to 20 weight %.
In gel polymer electrolyte, based on the total weight of gel polymer electrolyte, the amount of polymer can be about 0.1 to 30 weight %.For example, based on the total weight of gel polymer electrolyte, polymer can be about 0.5 to 20 weight %.Yet the amount of polymer is not limited thereto, and can be appropriate amount arbitrarily, is suitable as long as comprise the charging and the flash-over characteristic of the lithium battery of this gel polymer electrolyte.
The concentration of first lithium salts can be about 0.01M to about 2.0M.The concentration of first lithium salts can be suitable for preparing gel polymer electrolyte.Yet in some respects, the concentration of first lithium salts also can be about 0.5M to about 2M.
Organic solvent can be high dielectric constant solvent, low boiling point solvent or its mixture.High dielectric constant solvent can have about 30 to about 100 dielectric constant and low boiling point solvent can have about 77 to about 150 ℃ boiling point.Yet organic solvent is not limited thereto, and can use any suitable organic solvent.
High dielectric constant solvent can be cyclic carbonate, as the ethylene carbonate of fluoridizing, ethylene carbonate, propene carbonate and butylene; Gamma-butyrolacton; And/or its any mixture, but be not limited thereto.Low boiling point solvent can be: linear carbonate, as dimethyl carbonate, methyl ethyl carbonate, diethyl carbonate and dipropyl carbonate; Dimethoxy-ethane; Diethoxyethane; Aliphatic ester derivatives; And/or its any mixture, but be not limited thereto.
In the mixture of high dielectric constant solvent and low boiling point solvent, the volume ratio of high dielectric constant solvent and low boiling point solvent can be about 1: 1 to about 1: 9.When volume ratio was in this scope, the battery that comprises described organic solvent can have excellent discharge capacity and charge/discharge cycle life-span.
Lithium battery according to illustrative embodiments can comprise positive pole, negative pole and described gel polymer electrolyte.This lithium battery can be according to following method preparation.
Blended anode active material, electric conducting material, adhesive and solvent are with the preparation anode active material composition.Directly be coated on the aluminium collector body anode active material composition also dry then with the preparation positive plate.Perhaps, with anode active material composition curtain coating on independent carrier, then the film lamination that will peel off from this carrier on the aluminium collector body with the preparation positive plate.Perhaps, the form with the electrode ink that comprises excessive solvent prepares anode active material composition.Use ink jet printing method or gravure processes printing ink with the preparation positive plate then.Print process is not limited thereto, and is the normally used method that is fit to arbitrarily in coating or printing operation.
Positive electrode active materials can be the metal oxide that contains lithium arbitrarily usually used in this field.For example, positive electrode active materials can be LiCoO
2, LiMn
xO
2x(x=1,2), LiNi
1-xMn
xO
2(0＜x＜1), LiNi
1-x-yCo
xMn
yO
2(0≤x≤0.5,0≤y≤0.5), LiFePO
4Deng.
For example, electric conducting material can be carbon black.Adhesive can be vinylidene/hexafluoropropylene copolymer, Kynoar, polyacrylonitrile, polymethyl methacrylate, polytetrafluoroethylene, perhaps its any mixture, polyimides, polyamidoimide; styrene butadiene rubber polymeric, acrylate rubber, perhaps sodium carboxymethylcellulose.Solvent can be N-methyl pyrrolidone, acetone, water etc.Positive electrode active materials, electric conducting material, normally used in the amount of adhesive and solvent such as the lithium battery.
Similarly, mix negative active core-shell material, electric conducting material, adhesive and solvent with preparation negative electrode active material feed composition.The negative electrode active material feed composition directly is coated on the copper collector with the preparation negative plate.Perhaps, with negative active core-shell material curtain coating on independent carrier, then the negative active core-shell material film lamination that will peel off from carrier on copper collector with the preparation negative plate.Perhaps, the form with the electrode ink that comprises excessive solvent prepares the negative electrode active material feed composition.Use ink jet printing method or photogravure method printing ink with the preparation negative plate then.Print process is not limited thereto, and can be the normally used method that is fit to arbitrarily in coating or printing operation.
Negative active core-shell material, electric conducting material, normally used in the amount of adhesive and solvent such as the lithium battery.Negative active core-shell material can be: graphite material such as graphite particle; Can with the metal of lithium alloyage, as the silicon particulate; Graphite/silicon compound; Transition metal oxide such as Li
4Ti
5O
12Deng, but be not limited thereto.Also can use the negative active core-shell material that is fit to arbitrarily usually used in this field.For example, graphite particle can be native graphite, Delanium etc.The diameter of graphite particle can be about 5 to about 30 μ m.The diameter of silicon particulate can be about 50nm to about 10 μ m.Graphite particle and silicon particulate can use normally used method that is fit to arbitrarily in this area such as mechanical lapping to mix with preparation graphite/silicon compound.
The electric conducting material that uses in the negative electrode active material feed composition, adhesive and solvent can with anode active material composition in use identical.By can in battery lead plate, forming the hole to anode active material composition and negative electrode active material feed composition interpolation plasticizer.
Then, the preparation barrier film separates positive pole and negative pole.Can use the normally used barrier film that is fit to arbitrarily in the lithium battery field.Particularly, barrier film can have lower resistance and the excellent electrolyte-impregnated performance to the migration of the ion in the electrolyte.For example, barrier film can be by glass fibre, polyester, and polyethylene, polypropylene, fluoropolymer such as polytetrafluoroethylene (PTFE), perhaps its combination in any forms.Barrier film can be non-woven or form of fabric.More specifically, can use the reeled barrier film that forms by for example polyethylene or polyacrylic material.In lithium ion polymer battery, can use barrier film with excellent organic bath saturating machine.
Barrier film can be according to following method preparation.The mixed polymerization resin, filler and solvent prepare the barrier film composition.Directly be coated on the electrode barrier film composition also dry then to form the barrier film film.Perhaps, with barrier film composition curtain coating and drying on carrier, will be pressed on the electrode from the membrane layer that carrier is peeled off then.
Fluoropolymer resin is not particularly limited, and can be the material that is fit to arbitrarily of the adhesive that can be used as battery lead plate.For example, can use vinylidene/hexafluoropropylene copolymer, Kynoar, polyacrylonitrile, polymethyl methacrylate, perhaps its any mixture.Can use the vinylidene/hexafluoropropylene copolymer that contains about 8 to 25 weight % hexafluoropropylenes.
Then, preparation electrolyte.Gel polymer electrolyte according to illustrative embodiments can be used for lithium battery.For example, gel polymer electrolyte can comprise polymer of monomers shown in first lithium salts, organic solvent, fluorine compounds and the following formula 1.
H
2C＝C-(OR
1)
n-OCH＝CH
2
Wherein R is the C2-C10 alkylidene, and n is about 1 to about 1000.
Barrier film is inserted between positive plate and the negative plate to form battery structure (electrode assemblie).In battery structure coiling or folding and the cylindrical battery shell of packing into, prismatic battery shell or lamination putamina.Second electrolyte solution that will comprise first electrolyte solution of fluorine compounds and organic solvent and comprise formula I monomer and organic solvent injects battery case in proper order with the preparation lithium ion polymer battery.Polymerization by carrying out when first electrolyte solution and second electrolyte solution mix can prepare gel polymer electrolyte, and wherein polymer is flooded by organic solvent.In this, first electrolyte solution or second electrolyte solution can further comprise first lithium salts.
Perhaps, in lithium battery, can use coating or printing operation on positive plate and/or negative plate, to form gel polymer electrolyte.For example, first electrolyte solution and second electrolyte solution are coated with or are printed on simultaneously or in proper order on negative plate and/or the positive plate to form gel polymer electrolyte.Barrier film is inserted between positive plate and the negative plate to form battery structure.Battery structure reeled or folding and the cylindrical battery shell of packing into, prismatic battery shell or lamination putamina in the preparation lithium ion polymer battery.
Fig. 1 is the schematic diagram according to the lithium battery 1 of execution mode.With reference to Fig. 1, lithium battery 1 comprises positive pole 3, negative pole 2 and barrier film 4.With positive pole 3, negative pole 2 and barrier film 4 are reeled or are folding, are contained in then in the battery case 5.Inject first and second electrolyte solutions to battery case 5, use 6 sealings of cap (cap) assembly then, to finish the preparation of lithium battery 1.That battery case 5 can have is cylindrical, the form of rectangle or bag.Lithium battery 1 can be lithium ion battery.
Lithium ion polymer battery can be flexible battery.For example, lithium ion polymer battery can be crooked easily.
According to another illustrative embodiments, the method for preparing gel polymer electrolyte can comprise: preparation comprises first solution of fluorine compounds and organic solvent; Preparation comprises second solution of monomer shown in the formula 1 and organic solvent; With mixing first solution and second solution, wherein first solution or second solution also comprise first lithium salts.
In preparing the method for gel polymer electrolyte, fluorine compounds can by with organic solvent in residual moisture reaction produce Bronsted acid or lewis acid.First lithium salts can be inactive with respect to residual moisture.By mixing first solution and second solution, fluorine compounds and organic solvent reaction are to produce Bronsted acid or lewis acid.The cationic polymerization of monomer that causes formula 1 by Bronsted acid or lewis acid is to obtain polymer.
Polymer is flooded to form gel by electrolyte solution.For example, before the polymer full solidification, polymer can be flooded by electrolyte solution.Yet after the polymer full solidification, organic solvent can not be impregnated in the polymer usually.
The polymerization of the monomer of formula 1 can at room temperature be carried out.In certain aspects, polymerization can be carried out to the temperature range of the boiling point of organic solvent in the first lithium salts temperature of precipitation.For example, this temperature can be 10 to 40 ℃.
In addition, because therefore Bronsted acid or lewis acid initiated polymerization by being produced by the reaction between the residual moisture in fluorine compounds and the organic solvent do not need independent polymerization initiator, as heat or UV light.Therefore, gel polymer electrolyte can simply and effectively prepare.
In preparing the method for gel polymer electrolyte, when first solution and the mixing of second solution, according to the amount and the type scalable rate of polymerization that produce Bronsted acid or lewis acidic fluorine compounds.A spot of Bronsted acid or the lewis acidic rate of polymerization that causes reduce, and a large amount of Bronsted acids or lewis acid cause rate of polymerization to increase.Therefore, can select suitable generation Bronsted acid or lewis acidic fluorine compounds for required rate of polymerization.For some fluorine compounds, even also can produce a large amount of Bronsted acids or lewis acid on a small quantity.Similarly, for some fluorine compounds, even also can produce a spot of Bronsted acid or lewis acid in a large number.
In preparing the method for gel polymer electrolyte, the method for mixing first solution and second solution without limits.For example, can first solution be mixed with second solution by first solution and second solution are coated with or are being printed on positive plate and/or the negative plate simultaneously or in proper order.
Fluorine compounds can be the organic compound of fluoridizing, and comprise second lithium salts of fluorine, or its mixture.The organic compound of fluoridizing can be following formula 2 to one of compound shown in the formula 8, but is not limited thereto.The organic compound of fluoridizing can be by with electrolyte solution in residual moisture reaction produce Bronsted acid or lewis acidic any compound.
Formula 2 formulas 3 formulas 4 formulas 5
Formula 6 formulas 7 formulas 8
In formula 2 to 8, R
1To R
3Can be independently of one another be hydrogen atom or C1 to C10 alkyl unsubstituted or that replaced by fluorine atom.R
4To R
9Can be independently of one another be fluorine atom or C1 to C10 alkyl unsubstituted or that replaced by fluorine atom.R
4To R
9In at least one be fluorine atom.
Second lithium salts that comprises fluorine can be LiBF
4, LiPF
6, LiAsF
6, LiSbF
6, LiPF
3(CF
2CF
3)
3Or its any mixture, but be not limited thereto.In this, second lithium salts can be by with electrolyte solution in residual moisture reaction produce Bronsted acid or lewis acidic any lithium salts.
First lithium salts does not produce Bronsted acid or lewis acid when being exposed to moisture.For example, first lithium salts is nonactive with respect to very small amount of moisture in the organic solvent.In other words, first lithium salts does not produce and forms Bronsted acid or lewis acidic hydrogen ion.
For example, first lithium salts can be LiCl, LiI, LiAlO
2, LiAlCl
4, LiClO
4, LiCF
3CO
2, LiN (COCF
3)
2, LiN (COCF
2CF
3)
2, LiCF
3SO
3, LiCF
3CF
2SO
3, LiC
4F
9SO
3, LiN (CF
3SO
2)
2, LiN (C
2F
5SO
2)
2, wherein p and q are the LiN (C of integer
pF
2p+1SO
2) (C
qF
2q+1SO
2), difluoro (oxalic acid) lithium borate (LiFOB), two (oxalic acid) lithium borate (LiBOB), (malonic acid oxalic acid) lithium borate (LiMOB) or its any mixture, but be not limited thereto.Can also use when not producing Bronsted acid or lewis acidic any lithium salts when residual moisture in the electrolyte solution mixes.
In preparing the method for gel polymer electrolyte, based on the total weight of first and second electrolyte solutions, the amount of fluorine compounds can be about 0.1 to about 30 weight %.If the amount of fluorine compounds in above-mentioned scope, the cationic polymerization speed of the monomer of adjustable type 1 suitably.That is to say that the amount of above-mentioned fluorine compounds is suitable for preparing gel polymer electrolyte.For example, based on the total weight of first and second electrolyte solutions, the amount of fluorine compounds can be about 0.5 to about 20 weight %.
In preparing the method for gel polymer electrolyte, based on the total weight of first and second electrolyte solutions, the amount of the monomer of formula 1 can be about 0.1 to about 30 weight %.That is to say that the amount of the monomer of above-mentioned formula 1 expression is suitable for preparing the gel polymer electrolyte that comprises gel polymer electrolyte.For example, based on the total weight of first and second electrolyte solutions, the amount of the monomer of formula 1 expression can be about 0.5 to about 20 weight %.Yet the amount of the monomer of formula 1 expression is not limited thereto, and is enough as long as comprise the charging and the flash-over characteristic of the lithium battery of this gel polymer electrolyte.
In preparing the method for gel polymer electrolyte, the molecular weight of monomer shown in the formula 1 can be about 100 to about 1000 scope.Molecular weight at the monomer of above-mentioned scope is suitable for preparing gel polymer electrolyte.
The method for preparing lithium battery according to another illustrative embodiments can comprise: preparation comprises first solution of fluorine compounds and organic solvent, and preparation comprises second solution of monomer shown in the formula 1 and organic solvent; And with first solution and second solution coat or be printed on the electrode to form gel polymer electrolyte, wherein this gel polymer electrolyte also comprises first lithium salts.
In preparing the method for lithium battery, forming gel polymer electrolyte can be by being coated with or printing first and second solution and carry out simultaneously or in proper order.In preparing the method for lithium battery, fluorine compounds can by with organic solvent in residual moisture reaction produce Bronsted acid or lewis acid, first lithium salts can be inactive with respect to residual moisture.
In preparing the method for lithium battery, by simultaneously or order with first solution and second solution coat or be printed on the electrode, the reaction of the fluorine compounds that contain in first solution and the residual moisture in the organic solvent with the cationic polymerization of monomer that produces Bronsted acid or lewis acid and cause the formula 1 that contains in second solution by Bronsted acid or lewis acid to obtain polymer.
In polymerization process before the polymer full solidification, polymer can involved first lithium salts, the electrolyte solution dipping of organic solvent and fluorine compounds, and it is included in first solution and/or second solution.In addition, owing to cause the cationic polymerization of the monomer of formula 1 by Bronsted acid or lewis acid, so do not need independent polymerization initiator.Therefore, gel polymer electrolyte can prepare easily and effectively.
In preparing the method for lithium battery, the cationic polymerization of the monomer of formula 1 can carry out in the said temperature scope.Owing to use rubbing method or print process at room temperature to prepare gel polymer electrolyte, and do not need to use solidification equipment and initator, therefore can prepare lithium battery simply,
In preparing the method for lithium battery, fluorine compounds can be the organic compound of fluoridizing, and comprise second lithium salts of fluorine, perhaps its mixture.In preparing the method for lithium battery, the organic compound of fluoridizing can be one of compound shown in the following formula 2 to 8, but is not limited thereto.The organic compound of fluoridizing can be by with electrolyte solution in residual moisture reaction produce Bronsted acid or lewis acidic any compound.
Formula 2 formulas 3 formulas 4 formulas 5
Formula 6 formulas 7 formulas 8
In formula 2 to 8, R
1To R
3Can be independently of one another be hydrogen atom or C1 to C10 alkyl unsubstituted or that replaced by fluorine atom, R
4To R
9Can be independently of one another be fluorine atom or C1 to C10 alkyl unsubstituted or that replaced by fluorine atom, wherein R
4To R
9In at least one be fluorine atom.
Second lithium salts that comprises fluorine can be LiBF
4, LiPF
6, LiAsF
6, LiSbF
6, LiPF
3(CF
2CF
3)
3Or its any mixture, but be not limited thereto.In this, second lithium salts can be by with electrolyte solution in residual moisture reaction produce Bronsted acid or lewis acidic any lithium salts.
First lithium salts does not produce Bronsted acid or lewis acid when mixing with moisture.For example, first lithium salts is nonactive with respect to very small amount of moisture in the organic solvent.In other words, first lithium salts does not produce and forms Bronsted acid or lewis acidic hydrogen ion.
For example, first lithium salts can be LiCF
3CO
2, LiN (COCF
3)
2, LiN (COCF
2CF
3)
2, LiCF
3SO
3, LiCF
3CF
2SO
3, LiC
4F
9SO
3, LiN (CF
3SO
2)
2, LiN (C
2F
5SO
2)
2, wherein p and q are the LiN (C of integer
pF
2p+1SO
2) (C
qF
2q+1SO
2), dichloro (oxalic acid) lithium borate (LiFOB), two (oxalic acid) lithium borate (LiBOB), (malonic acid oxalic acid) lithium borate (LiMOB) or its any mixture, but be not limited thereto.Also can use when not producing Bronsted acid or lewis acidic any lithium salts when residual moisture in the electrolyte solution mixes.
Hereinafter, be described more specifically this instruction with reference to the following example.Following embodiment only is an illustrative purposes, and is not used in the scope that limits this instruction.
The preparation of composite anode active material
(SPEX 8000M) with the 3g average grain diameter is the graphite particle (C1SR, Japan) of 25 μ m and the silicon particulate that the 1.5g average grain diameter is 100nm (spherical (Spherical Type), Nanostructured﹠amp to use high energy ball mill; Amorphous Materials, Inc. U.S.A.) grinds 60 minutes negative active core-shell materials with preparation graphite/silicon compound form.
Comprise the preparation of the lithium battery of composite anode active material
In agate mortar, the negative active core-shell material of 70 weight portions according to preparation embodiment 1 preparation mixed with the preparation slurry with the graphite based conducting material (SFG6, Timcal Inc.) of 15 weight portions and the solution that is dissolved in 5 weight % Kynoar (PVdF) in the N-methyl pyrrolidone that comprises of 30 weight portions.Use scraper that slurry is coated on the copper collector that thickness is 15 μ m to thickness and be about 60 μ m, in 100 ℃ convection oven dry 2 hours, under vacuum 120 ℃ further dry 2 hours, with the preparation negative plate.
Under 20 ℃, use this negative plate, lithium metal pair electrode and polypropylene diaphragm (Celgard 3510) preparation CR-2016 standard coinage battery, add first electrolyte solution and second electrolyte solution in proper order to it.
By the 1.3M LiN (SO in the mixture that is dissolved in 3: 7 ethylene carbonate of volume ratio (EC) and diethyl carbonate (DEC) to 50 weight portions
2C
2F
5)
2Add 20 weight portion carbonic acid fluorinated ethylene esters (FEC) preparation, first electrolyte solution in the solution.By the 1.3M LiN (SO in the mixture that is dissolved in 3: 7 ethylene carbonate of volume ratio (EC) and diethyl carbonate (DEC) to 50 weight portions
2C
2F
5)
2Solution adds 3 weight portion diethylene glycol divinyl ethers (DEGDVE) preparation, second electrolyte solution.
Embodiment 2
Prepare CR-2016 standard coinage battery according to the mode identical, replace the 3 weight portion diethylene glycol divinyl ethers (DEGDVE) except in second electrolyte solution, using 2 weight portion triethylene glycol divinyl ether (TEGDVE) with embodiment 1.
Embodiment 3
Prepare CR-2016 standard coinage battery according to the mode identical with embodiment 1, except in second electrolyte solution, using 2 weight portion polyethylene glycol divinyl ether (PEGDVE, Aldrich, Inc.U.S.A., molecular weight: 240) replace 3 weight portion diethylene glycol divinyl ethers (DEGDVE) in addition.
Embodiment 4
Prepare CR-2016 standard coinage battery according to the mode identical with embodiment 1, except in second electrolyte solution, using 1 weight portion 1,4-butanediol divinyl ether (1,4-BDDVE) replace 3 weight portion diethylene glycol divinyl ethers (DEGDVE) in addition.
Comparative Examples 1
Prepare CR-2016 standard coinage battery according to the mode identical, except in second electrolyte solution, not using diethylene glycol divinyl ether (DEGDVE) with embodiment 1.
Comparative Examples 2
Prepare CR-2016 standard coinage battery according to the mode identical, except in first electrolyte solution, not using carbonic acid fluorinated ethylene ester (FEC) with embodiment 1.
Comparative Examples 3
Prepare CR-2016 standard coinage battery according to the mode identical, except in first electrolyte solution, using LiPF with embodiment 1
6Replace LiN (SO
2C
2F
5)
2In addition.
Comprise the preparation of the lithium battery of transition metal oxide positive electrode active materials (1)
Embodiment 5
With 80 weight portion average grain diameters is the LiFePO of 200nm
4(Phostech Lithium, U.S.A.), it is the solution of 5 weight % that 10 weight portion graphite based conducting materials (Super-P, Timcal Inc.) and 10 weight portion Kynoar (PVdF) are dissolved in the N-methyl pyrrolidone with the preparation solid content.(Dimatix, Inc. are that printing is the positive plate of 8 μ m with preparation thickness repeatedly on the aluminium collector body of 15 μ m at thickness with solution U.S.A.) to use ink-jet printer.
Use this positive plate, lithium metal pair electrode and polypropylene diaphragm (Celgard 3510) preparation CR-2016 standard coinage battery.Add first electrolyte solution and second electrolyte solution at 20 ℃ in proper order to it
By the 1.3M LiN (SO in the mixture that is dissolved in 3: 7 ethylene carbonate of volume ratio (EC) and diethyl carbonate (DEC) to 50 weight portions
2C
2F
5)
2Solution adds 0.5M LiBF
4Prepare first electrolyte solution.By the 1.3M LiN (SO in the mixture that is dissolved in 3: 7 ethylene carbonate of volume ratio (EC) and diethyl carbonate (DEC) to 50 weight portions
2C
2F
5)
2Solution adds 2.5 weight portion diethylene glycol divinyl ethers (DEGDVE) preparation, second electrolyte solution.
Embodiment 6
Prepare CR-2016 standard coinage battery according to the mode identical, replace the 2.5 weight portion diethylene glycol divinyl ethers (DEGDVE) except in second electrolyte solution, using 5 weight portion diethylene glycol divinyl ethers (DEGDVE) with embodiment 5.
Embodiment 7
Prepare CR-2016 standard coinage battery according to the mode identical, replace the 2.5 weight portion diethylene glycol divinyl ethers (DEGDVE) except in second electrolyte solution, using 10 weight portion diethylene glycol divinyl ethers (DEGDVE) with embodiment 5.
Embodiment 8
Prepare CR-2016 standard coinage battery according to the mode identical, replace the 2.5 weight portion diethylene glycol divinyl ethers (DEGDVE) except in second electrolyte solution, using 10 weight portion triethylene glycol divinyl ether (TEGDVE) with embodiment 5.
Comparative Examples 4
Prepare CR-2016 standard coinage battery according to the mode identical, except in second electrolyte solution, not adding diethylene glycol divinyl ether (DEGDVE) with embodiment 5.
Comprise the preparation of the lithium battery of transition metal oxide negative active core-shell material (2)
Embodiment 9
With 80 weight portion average grain diameters is the Li of 100nm
4Ti
5O
12(nGimat Co., U.S.A.), it is the solution of 5 weight % that 10 weight portion graphite based conducting materials (Super-P, Timcal Inc.) and 10 weight portion Kynoar (PVdF) are dissolved in the N-methyl pyrrolidone with the preparation solid content.(Dimatix, Inc. are that printing is the negative plate of 4 μ m with preparation thickness repeatedly on the aluminium collector body of 15 μ m at thickness with solution U.S.A.) to use ink-jet printer.
Use this negative plate, lithium metal pair electrode and polypropylene diaphragm (Celgard 3510) preparation CR-2016 standard coinage battery.Under 20 ℃, add first electrolyte solution and second electrolyte solution in proper order to it.
By the 1.3M LiN (SO in the mixture that is dissolved in 3: 7 ethylene carbonate of volume ratio (EC) and diethyl carbonate (DEC) to 50 weight portions
2C
2F
5)
2Solution adds 0.5M LiBF
4Prepare first electrolyte solution.By the 1.3M LiN (SO in the mixture that is dissolved in 3: 7 ethylene carbonate of volume ratio (EC) and diethyl carbonate (DEC) to 50 weight portions
2C
2F
5)
2Solution adds 2.5 weight portion diethylene glycol divinyl ethers (DEGDVE) preparation, second electrolyte solution.
Embodiment 10
Prepare CR-2016 standard coinage battery according to the mode identical, replace the 2.5 weight portion diethylene glycol divinyl ethers (DEGDVE) except in second electrolyte solution, using 5 weight portion diethylene glycol divinyl ethers (DEGDVE) with embodiment 9.
Embodiment 11
Prepare CR-2016 standard coinage battery according to the mode identical, replace the 2.5 weight portion diethylene glycol divinyl ethers (DEGDVE) except in second electrolyte solution, using 10 weight portion diethylene glycol divinyl ethers (DEGDVE) with embodiment 9.
Embodiment 12
Prepare CR-2016 standard coinage battery according to the mode identical, replace the 2.5 weight portion diethylene glycol divinyl ethers (DEGDVE) except in second electrolyte solution, using 10 weight portion triethylene glycol divinyl ether (TEGDVE) with embodiment 9.
Comparative Examples 5
Prepare CR-2016 standard coinage battery according to the mode identical, except in second electrolyte solution, not adding diethylene glycol divinyl ether (DEGDVE) with embodiment 9.
The fluorine compounds that comprise in the gel polymer electrolyte according to the lithium battery of embodiment 1 to 12 preparation and the amount of polymer are shown in the following table 1.
Table 1
| The state of polymer dielectric | The amount of fluorine compounds [weight %] | The amount of polymer [weight %] | |
| |
Gel | ??16.7 | ??3 |
| Embodiment 2 | Gel | ??16.7 | ??2 |
| The state of polymer dielectric | The amount of fluorine compounds [weight %] | The amount of polymer [weight %] | |
| Embodiment 3 | Gel | ??16.7 | ??2 |
| Embodiment 4 | Gel | ??16.7 | ??1 |
| Embodiment 5 | Gel | ??4.5 | ??2.5 |
| Embodiment 6 | Gel | ??4.5 | ??5 |
| Embodiment 7 | Gel | ??4.5 | ??10 |
| Embodiment 8 | Gel | ??4.5 | ??10 |
| Embodiment 9 | Gel | ??4.5 | ??2.5 |
| Embodiment 10 | Gel | ??4.5 | ??5 |
| Embodiment 11 | Gel | ??4.5 | ??10 |
| Embodiment 12 | Gel | ??4.5 | ??10 |
| Comparative Examples 1 | Liquid | ??16.7 | ??0 |
| Comparative Examples 2 | Liquid | ??0 | ??0 |
| Comparative Examples 3 | Polymer (polymer of liquid+separation) | Immeasurability | Immeasurability |
| Comparative Examples 4 | Liquid | ??4.5 | ??0 |
| Comparative Examples 5 | Liquid | ??4.5 | ??0 |
Estimate embodiment 1: the charge/discharge test
To reach 0.001V (with respect to Li) with the current charges of 10mA/g until its voltage according to the coin battery of embodiment 1 to 4 and Comparative Examples 1 to 3 preparation.Coin battery was placed 10 minutes, reached 1.5V (with respect to Li) with identical current discharge until its voltage then.This process triplicate.Then, this coin battery for current charges and the discharge of the 4th to 47 circulation with 200mA/g, is circulated with current charges and the discharge of 100mA/g for the 48th to 50 time.Measure starting efficiency, capability retention and the average efficiency under 200mA/g the results are shown in the following table 2.
Estimate embodiment 2: the charge/discharge test
To reach 4.1V (with respect to Li) with the current charges of 15mA/g until its voltage according to the coin battery of embodiment 5 to 8 and Comparative Examples 4 preparations.Coin battery was placed 10 minutes, reached 2.7V (with respect to Li) with identical current discharge until its voltage then.This process repeats 50 times.Measure starting efficiency, capability retention and the average efficiency under 15mA/g the results are shown in the following table 2.
Estimate embodiment 3: the charge/discharge test
To reach 1.1V (with respect to Li) with the current charges of 15mA/g until its voltage according to the coin battery of embodiment 9 to 12 and Comparative Examples 5 preparations.Coin battery was placed 10 minutes, reached 2.0V (with respect to Li) with identical current discharge until its voltage then.This process repeats 50 times.Measure starting efficiency, capability retention and the average efficiency under 15mA/g, the results are shown in the following table 2.
Be shown in the following table 2 according to the state of the polymer dielectric of the lithium battery of embodiment 1 to 12 and Comparative Examples 1 to 5 preparation and charging and flash-over characteristic.In table 2, use following equation 1 to 4 to calculate starting efficiency, capability retention and in the average efficiency under the 200mA/g (embodiment 1 to 4 and Comparative Examples 1 to 3) and starting efficiency, capability retention and the average efficiency under 15mA/g (embodiment 5 to 12 and Comparative Examples 4 to 5).
The charging capacity of the discharge capacity of the starting efficiency=circulation first time/circulation first time
Equation 2
The discharge capacity of the discharge capacity of capability retention=the 50th of the 50th the circulation time circulation/circulation first time
Equation 3
The mean value of the average efficiency under 20mA/g=each cyclic discharge capacity/charging capacity
Equation 4
The mean value of the average efficiency under 15mA/g=each cyclic discharge capacity/charging capacity
Table 2
| The state of polymer dielectric | Starting efficiency [%] | The capability retention [%] of the 50th circulation | Average efficiency [%] | |
| |
Gel | ??68.40 | ??86.58 | ??98.89 |
| Embodiment 2 | Gel | ??68.47 | ??88.18 | ??98.95 |
| Embodiment 3 | Gel | ??68.52 | ??84.00 | ??98.92 |
| Embodiment 4 | Gel | ??68.19 | ??86.85 | ??98.88 |
| Embodiment 5 | Gel | ??97.14 | ??96.61 | ??99.71 |
| Embodiment 6 | Gel | ??99.70 | ??98.09 | ??99.95 |
| Embodiment 7 | Gel | ??99.64 | ??98.80 | ??99.90 |
| Embodiment 8 | Gel | ??99.53 | ??98.29 | ??99.93 |
| Embodiment 9 | Gel | ??64.65 | ??60.55 | ??96.24 |
| The state of polymer dielectric | Starting efficiency [%] | The capability retention [%] of the 50th circulation | Average efficiency [%] | |
| Embodiment 10 | Gel | ??68.08 | ??63.38 | ??96.35 |
| Embodiment 11 | Gel | ??69.39 | ??82.41 | ??96.78 |
| Embodiment 12 | Gel | ??68.68 | ??87.10 | ??95.55 |
| Comparative Examples 1 | Liquid | ??67.56 | ??80.43 | ??98.40 |
| Comparative Examples 2 | Liquid | ??67.49 | ??76.52 | ??98.58 |
| Comparative Examples 3 | Polymer (polymer of liquid+separation) | Immeasurability | Immeasurability | Immeasurability |
| Comparative Examples 4 | Liquid | ??98.25 | ??62.65 | ??98.78 |
| Comparative Examples 5 | Liquid | ??65.02 | ??56.97 | ??95.18 |
As shown in table 1, and compare with 2 coin battery according to Comparative Examples 1, have better starting efficiency, capability retention and average efficiency according to the coin battery of embodiment 1 to 4.According to Comparative Examples 3, polymerization is carried out rapidly when first electrolyte solution mixes with second electrolyte solution, makes to form the solid polymer that separates with organic solvent, rather than comprises the gel polymer electrolyte of the gel polymer that is impregnated with organic solvent.Therefore, the charge/discharge test is impossible.
Charging and flash-over characteristic according to the coin battery of embodiment 1-4 improve by forming gel polymer electrolyte, and its inhibition has the composite anode active material of uneven surface and the irreversible reaction between the electrolyte solution.In charging and discharge process, gelatin polymer plays the effect of the carrier of active material and electrode structure.
With compare according to the coin battery of Comparative Examples 4, have better starting efficiency, capability retention and average efficiency according to the coin battery of embodiment 5 to 8.Particularly, capability retention obviously improves.
As mentioned above, one or more according to above-mentioned execution mode, by at room temperature mix with electrolyte in the residual moisture reaction monomer that produces Bronsted acid or lewis acidic fluorine compounds and comprise vinyl can prepare gel polymer electrolyte simply, and do not need solidification equipment.The lithium battery that comprises this gel polymer electrolyte has excellent charging and flash-over characteristic, as initial efficient and capability retention.
Although illustrated and set forth some illustrative embodiments, those skilled in the art will know under the situation that does not break away from principle of the present invention and spirit, can change in these illustrative embodiments, scope of the present invention is limited by claim and equivalent thereof.
Claims (37)
1. polymer dielectric comprises:
Lithium salts;
Organic solvent;
Fluorine compounds; With
Polymer of monomers shown in the following formula 1:
Formula 1
H
2C＝C-(OR
1)
n-OCH＝CH
2
Wherein R is that C2-C10 alkylidene and n are about 1 to about 1000.
2. the polymer dielectric of claim 1, wherein:
These fluorine compounds by with this organic solvent in the reaction of residual moisture produce Bronsted acid or lewis acid; With
This lithium salts is nonactive with respect to the residual moisture in this organic solvent.
3. the polymer dielectric of claim 1, wherein this polymer is by by the prepared in reaction between the monomer of the Bronsted acid of reaction generation between these fluorine compounds and this organic solvent residue moisture or lewis acid and formula 1.
4. the polymer dielectric of claim 1, the wherein electrolyte solution of involved this lithium salts of this polymer, this organic solvent and these fluorine compounds dipping.
5. the polymer dielectric of claim 1, wherein these fluorine compounds comprise at least a compound that is selected from the organic compound of fluoridizing and comprises the lithium salts of fluorine.
6. the polymer dielectric of claim 5, wherein this organic compound of fluoridizing comprises and is selected from following at least a compound:
Formula 2 formulas 3 formulas 4 formulas 5
Formula 6 formulas 7 formulas 8
R
1To R
3Be hydrogen atom or C1 to C10 alkyl unsubstituted or that replaced by fluorine atom independently of one another,
R
4To R
9Independently of one another for fluorine atom or C1 to C10 alkyl unsubstituted or that replaced by fluorine atom and
R
4To R
9In at least one be fluorine atom.
7. the polymer dielectric of claim 5, wherein this lithium salts that comprises fluorine comprises and is selected from LiBF
4, LiPF
6, LiAsF
6, LiSbF
6And LiPF
3(CF
2CF
3)
3At least a compound.
8. the polymer dielectric of claim 1, wherein this lithium salts comprises and is selected from LiCF
3CO
2, LiN (COCF
3)
2, LiN (COCF
2CF
3)
2, LiCF
3SO
3, LiCF
3CF
2SO
3, LiC
4F
9SO
3, LiN (CF
3SO
2)
2, LiN (C
2F
5SO
2)
2, LiN (C
pF
2p+1SO
2) (C
qF
2q+1SO
2) (wherein p and q are integers), difluoro (oxalic acid) lithium borate (LiFOB), at least a compound of two (oxalic acid) lithium borate (LiBOB) and (malonic acid oxalic acid) lithium borate (LiMOB).
9. the polymer dielectric of claim 1, wherein based on the total weight of this polymer dielectric, the amount of these fluorine compounds is about 0.1 to about 30 weight %.
10. the polymer dielectric of claim 1, wherein based on the total weight of this polymer dielectric, the amount of these fluorine compounds is about 0.5 to about 20 weight %.
11. the polymer dielectric of claim 1, wherein based on the total weight of this polymer dielectric, the amount of this polymer is about 0.1 to about 30 weight %.
12. the polymer dielectric of claim 1, wherein based on the total weight of this gel polymer electrolyte, the amount of this polymer is about 0.5 to about 20 weight %.
13. the polymer dielectric of claim 1, wherein this polymer dielectric is a gel polymer electrolyte.
14. lithium battery comprises:
Anodal;
Negative pole; With
The polymer dielectric of claim 1.
15. prepare the method for polymer dielectric, described method comprises:
Preparation comprises first solution of fluorine compounds and organic solvent;
Preparation comprises second solution of monomer shown in the following formula 1 and organic solvent; With
This first solution and second solution are mixed with the formation polymer dielectric,
Wherein this first solution or second solution also comprise first lithium salts:
Formula 1
H
2C＝C-(OR)
n-OCH＝CH
2
Wherein R is the C2-C10 alkyl, and n is about 1 to about 1000.
16. the method for claim 15, wherein: these fluorine compounds by with this organic solvent in residual moisture reaction produce Bronsted acid or lewis acid; With
This lithium salts is nonactive with respect to described residual moisture.
17. the method for claim 15 is wherein mixed this first and second solution and is comprised:
Monomer polymerization shown in the formula 1 is become gelatin polymer; With
To comprise this lithium salts, the electrolyte solution of this organic solvent and these fluorine compounds floods this gelatin polymer to form polymer dielectric.
18. the method for claim 17, wherein this polymerization is at room temperature carried out.
19. the method for claim 15, wherein these fluorine compounds comprise the organic compound fluoridized and comprise at least a in the lithium salts of fluorine.
20. the method for claim 19, wherein this organic compound of fluoridizing comprises and is selected from following at least a compound:
Formula 2 formulas 3 formulas 4 formulas 5
Formula 6 formulas 7 formulas 8
R
1To R
3Be hydrogen atom or C1 to C10 alkyl unsubstituted or that replaced by fluorine atom independently of one another,
R
4To R
9Independently of one another for fluorine atom or C1 to C10 alkyl unsubstituted or that replaced by fluorine atom and
R
4To R
9In at least one be fluorine atom.
21. the method for claim 19, wherein this lithium salts that comprises fluorine comprises and is selected from LiBF
4, LiPF
6, LiAsF
6, LiSbF
6, and LiPF
3(CF
2CF
3)
3At least a compound.
22. the polymer dielectric of claim 15, wherein this lithium salts comprises and is selected from LiCF
3CO
2, LiN (COCF
3)
2, LiN (COCF
2CF
3)
2, LiCF
3SO
3, LiCF
3CF
2SO
3, LiC
4F
9SO
3, LiN (CF
3SO
2)
2, LiN (C
2F
5SO
2)
2, LiN (C
pF
2p+1SO
2) (C
qF
2q+1SO
2) (wherein p and q are integers), difluoro (oxalic acid) lithium borate (LiFOB), at least a compound of two (oxalic acid) lithium borate (LiBOB) and (malonic acid oxalic acid) lithium borate (LiMOB).
23. the method for claim 15, wherein based on the total weight of this first solution and second solution, the amount of these fluorine compounds is about 0.1 to about 30 weight %.
24. the method for claim 15, wherein based on the total weight of this first solution and second solution, the amount of these fluorine compounds is about 0.5 to about 20 weight %.
25. the method for claim 15, wherein based on the total weight of this first solution and second solution, the amount of monomer shown in the formula 1 is about 0.1 to about 30 weight %.
26. the method for claim 15, wherein based on the total weight of this first solution and second solution, the amount of monomer shown in the formula 1 is about 0.5 to about 20 weight %.
27. the method for claim 15, the molecular weight of monomer shown in its Chinese style 1 is about 100 to about 1000.
28. the method for claim 15, wherein this polymer dielectric is a gel polymer electrolyte.
29. prepare the method for lithium battery, described method comprises:
Preparation comprises first solution of fluorine compounds and organic solvent;
Preparation comprises second solution of monomer shown in the following formula 1 and organic solvent; With
This first solution and second solution are coated on the electrode forming polymer dielectric on this electrode,
Wherein this polymer dielectric also comprises first lithium salts:
Formula 1
H
2C＝C-(OR)
n-OCH＝CH
2
Wherein R is the C2-C10 alkylidene, and n is about 1 to about 1000.
30. the method for claim 29 applies wherein that this first solution and second solution comprise simultaneously or sequentially with this first solution and second solution coat or be printed onto on the electrode.
31. the method for claim 29, wherein:
Applying this first solution and second solution comprises residual moisture reaction in these fluorine compounds and this organic solvent to produce Bronsted acid or lewis acid; With
This lithium salts is nonactive with respect to this organic solvent residue moisture.
32. the method for claim 29 wherein applies this first solution and second solution and comprises:
Monomer polymerization shown in the formula 1 is become gelatin polymer; With
With comprising this lithium salts, the electrolyte solution of this organic solvent and these fluorine compounds floods this gelatin polymer to form polymer dielectric.
33. the method for claim 32, wherein this polymerization is at room temperature carried out.
34. the method for claim 29, wherein these fluorine compounds comprise at least a of organic compound of fluoridizing and the lithium salts that comprises fluorine.
35. the method for claim 34, wherein this organic compound of fluoridizing comprises and is selected from following at least a compound:
Formula 2 formulas 3 formulas 4 formulas 5
Formula 6 formulas 7 formulas 8
R
1To R
3Be hydrogen atom or C1 to C10 alkyl unsubstituted or that replaced by fluorine atom independently of one another,
R
4To R
9Independently of one another for fluorine atom or C1 to C10 alkyl unsubstituted or that replaced by fluorine atom and
R
4To R
9In at least one be fluorine atom.
36. the method for claim 34, wherein this lithium salts that comprises fluorine comprises and is selected from LiBF
4, LiPF
6, LiAsF
6, LiSbF
6, and LiPF
3(CF
2CF
3)
3At least a compound.
37. the polymer dielectric of claim 29, wherein this lithium salts comprises and is selected from LiCF
3CO
2, LiN (COCF
3)
2, LiN (COCF
2CF
3)
2, LiCF
3SO
3, LiCF
3CF
2SO
3, LiC
4F
9SO
3, LiN (CF
3SO
2)
2, LiN (C
2F
5SO
2)
2, LiN (C
pF
2p+1SO
2) (C
qF
2q+1SO
2) (wherein p and q are integers), difluoro (oxalic acid) lithium borate (LiFOB), at least a compound of two (oxalic acid) lithium borate (LiBOB) and (malonic acid oxalic acid) lithium borate (LiMOB).
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| KR20080121285 | 2008-12-02 | ||
| KR102289/09 | 2009-10-27 | ||
| KR1020090102289A KR101669218B1 (en) | 2008-11-10 | 2009-10-27 | Gel polymer electrolyte, Lithium battery comprising gel polymer electrolyte, method for preparing gel polymer electrolyte, and method for preparing lithium battery |
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| CN107078342A (en) * | 2014-10-02 | 2017-08-18 | 株式会社Lg化学 | Gel polymer electrolyte and the lithium secondary battery including the gel polymer electrolyte |
| CN109994770A (en) * | 2017-12-14 | 2019-07-09 | 纳米及先进材料研发院有限公司 | The method of persursor material and manufacture lithium ion battery for lithium ion battery |
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| US9601804B2 (en) | 2008-11-10 | 2017-03-21 | Samsung Electronics Co., Ltd. | Gel polymer electrolyte, lithium battery including gel polymer electrolyte, and method of preparing gel polymer electrolyte |
| DE102012022976A1 (en) * | 2012-11-26 | 2014-05-28 | Ewe-Forschungszentrum Für Energietechnologie E. V. | Use of conductive polymers in battery electrodes |
| CN113839096B (en) * | 2021-08-20 | 2024-02-27 | 深圳市本征方程石墨烯技术股份有限公司 | Preparation method of electrolyte, lithium ion battery and preparation method of lithium ion battery |
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| US20040126665A1 (en) * | 2002-12-26 | 2004-07-01 | Luying Sun | Gel polymer electrolyte battery and method of producing the same |
| CN1749351A (en) * | 2005-06-30 | 2006-03-22 | 同济大学 | Transparent non-water proton conductive material of side group type azacyclic polymer and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107078342A (en) * | 2014-10-02 | 2017-08-18 | 株式会社Lg化学 | Gel polymer electrolyte and the lithium secondary battery including the gel polymer electrolyte |
| CN107078342B (en) * | 2014-10-02 | 2019-10-15 | 株式会社Lg化学 | Gel polymer electrolyte and lithium secondary battery including the gel polymer electrolyte |
| US10476104B2 (en) | 2014-10-02 | 2019-11-12 | Lg Chem, Ltd. | Gel polymer electrolyte and lithium secondary battery comprising the same |
| CN109994770A (en) * | 2017-12-14 | 2019-07-09 | 纳米及先进材料研发院有限公司 | The method of persursor material and manufacture lithium ion battery for lithium ion battery |
| CN109994770B (en) * | 2017-12-14 | 2021-11-30 | 纳米及先进材料研发院有限公司 | Precursor material for lithium ion battery and method for manufacturing lithium ion battery |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101800334B (en) | 2014-04-09 |
| JP5638224B2 (en) | 2014-12-10 |
| KR20100052407A (en) | 2010-05-19 |
| KR101669218B1 (en) | 2016-11-10 |
| JP2010114087A (en) | 2010-05-20 |
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