CN102443236B - Polymer electrolyte membrane, preparation method thereof and polymer lithium-ion battery - Google Patents
Polymer electrolyte membrane, preparation method thereof and polymer lithium-ion battery Download PDFInfo
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Abstract
The invention provides a preparation method of a polymer electrolyte membrane, which comprises the following steps: modification: dissolving monomers into a first solvent in the inert gas atmosphere, adding nano particles, adding initiators, mixing well to obtain mixed solution, initiating the mixed solution for polymerization, and precipitating and drying the solution prepared via polymerization to obtain polymer particles modified by the nano particles; and film preparation: dissolving the polymer particles modified by the nano particles into a second solvent to obtain polymer solution, and preparing the polymer electrolyte membrane with the polymer solution. The polymer electrolyte membrane prepared by the preparation method contains a polymer matrix, and the polymer matrix is doped with the nano particles. The invention also relates to a polymer lithium-ion battery adopting the polymer electrolyte membrane. The comprehensive performance of the polymer electrolyte membrane prepared by the preparation method can be improved significantly.
Description
Technical field
The present invention relates to lithium ion battery field, in particular, relate to a kind of polymer dielectric film and preparation method thereof and contain the polymer Li-ion battery of this polymer dielectric film.
Background technology
The advantages such as lithium ion battery is little with its high working voltage, high-energy-density, volume, memory-less effect, life-span are long, become the main energy sources of present stage development.Lithium ion battery has occupied dominant position in mobile electronic terminal device fields such as mobile phone, notebook computer, portable digital equipments at present, and also obtained application more and more widely at numerous areas such as electromobile, space technology, PDA, bluetooth earphone and military and national defense, also more and more higher to the requirement of its performance.
At present, both at home and abroad most of what adopt is liquid electrolyte to lithium ion battery, although liquid lithium ionic cell has good high-rate charge-discharge capability and low-temperature performance, it also has some unfavorable factors, for example: the phenomenon of leakage, the shortcoming such as security is not good enough.In recent years, on the higher solid lithium-ion battery of those skilled in the art's research direction steering safety, and developed on this basis polymer Li-ion battery of new generation.Compared with traditional liquid lithium ionic cell, polymer Li-ion battery except having kept high-voltage, high-energy-density, have extended cycle life, the advantage such as environmental protection and memory-less effect, also overcome the safety issue such as leakage, even blast on fire that liquid lithium ion battery exists; And, because polymer Li-ion battery has material softness, configuration design is more flexible, be easy to the advantages such as slimming and arbitrary shape, more and more develop into the desirable energy of communication electric field.
In polymer Li-ion battery, polymer dielectric film is the key material of polymer Li-ion battery, as barrier film and the ionogen of lithium ion battery, polymer dielectric film should possess higher conductivity at room temperature, good electrode interface stability, the wider characteristic such as electrochemical window and good mechanical property.At present, polymer dielectric film can be divided into two types: pure solid polymer electrolyte membrane and gel-type polymer electrolyte film.The ionic conductivity of existing pure solid polymer electrolyte membrane is lower, and maximum is 10
-5-10
-4scm
-1the order of magnitude, can not meet the requirement of lithium ion battery to ionic conductivity.And the ionic conductivity of existing gel-type polymer electrolyte film can reach 10
-3scm
-1more than the order of magnitude, but but there is poor mechanical property.
Strengthen theory according to macromolecular material, in macromolecular material, add some inorganic materials, can effectively strengthen the mechanical property of macromolecular material.In prior art, disclose the physical strength of adding silicon-dioxide inorganic nano additive and improve polymer dielectric film in polymer dielectric film, but because nano SiO 2 particle is just simply filled and is adsorbed in the hole of gel electrolyte membrane, only depend on each other physical action, aspect raising physical strength, effect is limited, and nano SiO 2 particle is difficult to disperse in dielectric film, easily pile up, cause ionic conductivity to reduce.
CN101409365 discloses and has adopted the method for blend to prepare P (MMA-AN-VAc) the base gel polymer electrolyte of doped with nanometer particle.Take P (MMA-AN-VAc) polymkeric substance that synthesizes as basis, add nanoparticle, with P (MMA-AN-VAc) the polymer phase ratio that does not add nanoparticle, the gel electrolyte of prepared doped with nanometer particle has higher ionic conductivity, better physical strength, electrochemistry and thermodynamic stability.But, because nanoparticle has higher surfactivity, very easily reunite, be difficult for being scattered in P (MMA-AN-VAc) polymkeric substance, cause the ununiformity of polymer dielectric, thereby affect the performance of polymer dielectric, for example: the raising of ionic conductivity is limited, nanoparticle is 3.48 × 10 before adding
-3scm
-1, after interpolation, be 5.0 × 10
-3scm
-1, and the raising of mechanical property is also limited.
CN1622385 discloses a kind of all-solid-state composite polymer electrolyte that contains solid acid and preparation method thereof, and it is made up of polyoxyethylene, lithium salts and solid acid, and solid acid is
or
equally, in the time using solid acid particularly to use nanoscale solids acid, because its surface has higher surface energy, very easily reunite, performance tool to polymer dielectric has a great impact, and the Room-temperature-conductivity of Polymer Electrolyte of preparing is lower, only can reach 2 × 10
-5scm
-1, and lithium ion transference number is also lower.
Summary of the invention
The present invention is intended to over-all properties, especially ionic conductivity and the poor technical problem of mechanical property of the prepared polymer dielectric film of preparation method of the polymer dielectric film that solves prior art.
In order to solve the problems of the technologies described above, the invention provides a kind of preparation method of polymer dielectric film, comprise the steps:
Modification: under inert gas atmosphere, monomer is dissolved in the first solvent, add nanoparticle, add again initiator to mix and obtain mixing solutions, by described mixing solutions initiated polymerization, again the solution of polyreaction gained precipitated, be dried, obtain nanometer particle-modified polymer beads;
Masking: described nanometer particle-modified polymer beads is dissolved in the second solvent, obtains polymers soln, then adopt polymers soln to make described polymer dielectric film.
The present invention also provides a kind of polymer dielectric film, adopts method as above to make, and described polymer dielectric film comprises polymeric matrix, in described polymeric matrix doped with nanoparticle.
The present invention further provides a kind of polymer Li-ion battery, having comprised: positive pole, negative pole and the polymer dielectric film between described positive pole and negative pole, wherein, described polymer dielectric film has been polymer dielectric film as above.
The present invention compared with prior art, there is following beneficial effect: preparation method of the present invention is by being scattered in nanoparticle in monomer, again described monomer initiated polymerization is obtained to nanometer particle-modified polymer beads, thereby nanoparticle is disperseed well and be fixed in polymeric matrix, having solved nanoparticle in prior art easily reunites, the problem of bad dispersibility, the overall performance of prepared polymer dielectric film is improved significantly, wherein, prepared gel polymer electrolyte film has splendid absorbent and physical strength, the ionic conductivity of the gel polymer electrolyte obtaining after imbibition is high, transference number of ions is high, electrochemical stability is good, be applied to polymer Li-ion battery, can lithium ion battery specific storage and first charge-discharge efficiency significantly improve, ionic conductivity and the lithium ion transference number of prepared full solid state polymer electrolyte film are significantly improved, and preparation technology of the present invention is simple, be conducive to make polymer Li-ion battery, be suitable for suitability for industrialized production.
Accompanying drawing explanation
Fig. 1 is the graphic representation of the pick up of embodiment 1-4 and the prepared gel polymer electrolyte film of comparative example 1-2.
Fig. 2 is the decomposition voltage graphic representation of the prepared gel polymer electrolyte film of embodiment 1.
Embodiment
In the process of the present inventor's performance impact to polymer dielectric film at research nanoparticle, find that polymerization in position prepared in the process of polymkeric substance, in advance monomer is dissolved in appropriate solvent, and add nanoparticle, then initiated polymerization, nanoparticle is dispersed in polymkeric substance, prepare nanometer particle-modified polymer beads, then this nanometer particle-modified polymer beads is dissolved in to film forming solvent, due to the bonding force of polymer beads inside, make nanoparticle can in film forming solvent, keep satisfactory stability and dispersed uniformly, add the stirring action while dissolving, effectively avoid the reunion of nanoparticle, and make the quantum size effect of nanoparticle and surface effects bring into play better in the polymer dielectric film of follow-up preparation, prepared polymer dielectric film has the fabulous microvoid structure being cross-linked with each other, higher ionic conductivity and good physical strength, the performance of the polymer dielectric obtaining after the gel polymer electrolyte film Electolyte-absorptive wherein, making has significantly lifting.Further, the present inventor studies while finding that the nanoparticle adopting is sodium aluminum fluoride, because sodium aluminum fluoride has good electroconductibility, can participate in ionic conduction, thereby over-all properties, the especially ionic conductivity of adding the prepared polymer dielectric film of sodium aluminum fluoride are higher compared to adding other existing nanoparticle.
According to above-mentioned research, the invention provides a kind of preparation method of gel polymer electrolyte film of polymer Li-ion battery, comprise the steps:
In this step, described monomer can use any known to making the polymer monomer of gel polymer electrolyte film, be preferably methyl methacrylate (MMA), vinyl cyanide (AN), maleic anhydride (MAh), two or more arbitrary combination in the monomers such as vinyl-acetic ester (VAc), more preferably, described monomer is methyl methacrylate (MMA), the combination of vinyl cyanide (AN) and maleic anhydride (MAh), and MMA: AN: MAh (mass ratio)=(0.5-3): (9-6): (0.5-1), or described monomer is selected from methyl methacrylate (MMA), the combination of vinyl cyanide (AN) and vinyl-acetic ester (VAc), and MMA: AN: VAc=(0.5-3): (9-6): (0.5-1).
The preferred hexafluoro lithium aluminate of described nanoparticle (Li
3alF
6), hexafluoro sodium aluminate (Na
3alF
6), potassium hexafluoroaluminate (K
3alF
6), one or more in aluminium nitride (AlN), five kinds of nanoparticles of boron nitride (BN), more preferably, described nanoparticle is hexafluoro lithium aluminate (Li
3alF
6), hexafluoro sodium aluminate (Na
3alF
6), potassium hexafluoroaluminate (K
3alF
6) in one or more.Take the monomer of 100 weight parts as benchmark, the addition of described nanoparticle is 1-25 weight part, and preferably, the addition of nanoparticle is 5-20 weight part.
Described the first solvent is one or more the arbitrary combination in acetonitrile, acetone, N-N dimethyl formamide, tetrahydrofuran (THF); Take the monomer of 100 weight parts as benchmark, the addition of described the first solvent is 300-1900 weight part; Described the first solvent mainly plays the effect of dissolved monomer and dispersing nanometer particle.
Described initiator can use the initiator that can cause above-mentioned monomer polymerization known in those skilled in the art, preferably at least one in Diisopropyl azodicarboxylate (AIBN), benzoyl peroxide (BPO), take the monomer of 100 weight parts as benchmark, the addition of described initiator is 0.05-5 weight part, and preferably the addition of initiator is 0.07-2 weight part.
In order to make monomer and the nanoparticle dispersion effect in solution better, adopt mechanical stirring or magnetic agitation, the equipment of described mechanical stirring or magnetic agitation is conventionally known to one of skill in the art, for example: described mechanical stirring can adopt conventional chemical reaction mechanical stirrer to carry out; Preferably use magnetic stirring apparatus, when use, open after magnetic stirring apparatus, because instrument base is magnetic, in mixing solutions, put into magneton, thereby can under magneticaction, the rotation by magneton stir the mixing solutions that obtains mixing to mixing solutions.
In this step, described initiated polymerization belongs to thermal-initiated polymerization, it should be noted that, if adopt a step intensification polymerization, heat up and can cause too soon polymerization incomplete, point two step intensification polymerization meetings make polymerization effect better, thereby, in this step, the condition of initiated polymerization is that mixing solutions is first warming up to 30-60 ℃ of prepolymerization 4-8h gradually, then continues to be warming up to 60-80 ℃ and make mixed solution thermopolymerization 1-3h; The intermediate processing of the solution of polyreaction gained is to adopt liquid straight-chain paraffin to precipitate, for example: adopt normal hexane, octane to precipitate.
In this step, described the second solvent can be same with the first solvent phase, also can be not identical; The second solvent mainly plays the effect of dissolving or dispersed polymeres particle, and, during due to masking, need polymers soln to there is certain curtain coating, after film makes, require again this solvent to volatilize, thereby require the second solvent to there is preferably volatile performance and ductility, the solvent that possesses above-mentioned performance in prior art all can be used as the second solvent in the present invention, preferably, the second solvent is one or more the arbitrary combination in acetonitrile, acetone, N-N dimethyl formamide, tetrahydrofuran (THF).
In described polymers soln, described nanometer particle-modified polymer beads adds as the case may be, the polymers soln that is suitable for making polymer dielectric film to make is as the criterion, in general, take the second solvent of 100 weight parts as benchmark, the content of described nanometer particle-modified polymer beads is 0.1-4 weight part.
In this step, the effect of stirring at the 50-80 ℃ temperature that is to raise can make nanometer particle-modified polymer beads softening, and can improve the solubleness of nanometer particle-modified polymer beads in solvent, form the pourable film making solution of thickness, be conducive to follow-up masking.In step, in the time that nanometer particle-modified polymer beads is dissolved in the second solvent, due to the bonding force of polymer beads inside and the quantum size effect of nanoparticle and surface effects, the nanoparticle that makes to be doped in polymer beads still can keep satisfactory stability and dispersed uniformly in the second solvent, there will not be and reunites and disperse inhomogeneous phenomenon.
This step is conventional steps, the method that adopts polymers soln to make polymer dielectric film has been conventionally known to one of skill in the art, for example: can be by resulting polymers solution casting on the similar smooth templates such as tetrafluoroethylene template, aluminum foil plate or sheet glass, and the thickness of fixing film is 60-110 μ m, after solvent volatilizees completely, obtaining thickness is the gel polymer electrolyte film of 60-110 μ m.
By above-mentioned steps 1-3, the gel polymer electrolyte film making, described gel polymer electrolyte film comprises polymeric matrix, in described polymeric matrix doped with nanoparticle; The preferred hexafluoro lithium aluminate of described nanoparticle (Li
3alF
6), hexafluoro sodium aluminate (Na
3alF
6), potassium hexafluoroaluminate (K
3alF
6), one or more in aluminium nitride (AlN), five kinds of nanoparticles of boron nitride (BN), more preferably, described nanoparticle is hexafluoro lithium aluminate (Li
3alF
6), hexafluoro sodium aluminate (Na
3alF
6), potassium hexafluoroaluminate (K
3alF
6) in one or more.The median size of described nanoparticle is 1-200nm, the nanoparticle that preferably median size is 1-25nm.Take the monomer of 100 weight parts as benchmark, the addition of described nanoparticle is 1-25 weight part, and preferably, the addition of nanoparticle is 5-20 weight part.
The present invention also provides a kind of preparation method of full solid state polymer electrolyte film of polymer Li-ion battery, comprises the steps:
In this step, described monomer can use any known to making the polymer monomer of full solid state polymer electrolyte film, be preferably methyl methacrylate (MMA), vinyl cyanide (AN), maleic anhydride (MAh), two or more arbitrary combination in the monomers such as vinyl-acetic ester (VAc), more preferably, described monomer is methyl methacrylate (MMA), the combination of vinyl cyanide (AN) and maleic anhydride (MAh), and MMA: AN: MAh (mass ratio)=(0.5-3): (9-6): (0.5-1), or described monomer is selected from methyl methacrylate (MMA), the combination of vinyl cyanide (AN) and vinyl-acetic ester (VAc), and MMA: AN: VAc=(0.5-3): (9-6): (0.5-1).
The preferred hexafluoro lithium aluminate of described nanoparticle (Li
3alF
6), hexafluoro sodium aluminate (Na
3alF
6), potassium hexafluoroaluminate (K
3alF
6), one or more in aluminium nitride (AlN), five kinds of nanoparticles of boron nitride (BN), more preferably, described nanoparticle is hexafluoro lithium aluminate (Li
3alF
6), hexafluoro sodium aluminate (Na
3alF
6), potassium hexafluoroaluminate (K
3alF
6) in one or more.Take the monomer of 100 weight parts as benchmark, the addition of described nanoparticle is 1-25 weight part, and preferably, the addition of nanoparticle is 5-20 weight part.
Described the first solvent is one or more the arbitrary combination in acetonitrile, acetone, N-N dimethyl formamide, tetrahydrofuran (THF); Take the monomer of 100 weight parts as benchmark, the addition of described the first solvent is 300-1900 weight part; Described the first solvent mainly plays the effect of dissolved monomer and dispersing nanometer particle.
Described initiator can use the initiator that can cause above-mentioned monomer polymerization known in those skilled in the art, preferably at least one in Diisopropyl azodicarboxylate (AIBN), benzoyl peroxide (BPO), take the monomer of 100 weight parts as benchmark, the addition of described initiator is 0.05-5 weight part, and preferably the addition of initiator is 0.07-2 weight part.
In order to make monomer and the nanoparticle dispersion effect in solution better, adopt mechanical stirring or magnetic agitation, the equipment of described mechanical stirring or magnetic agitation is conventionally known to one of skill in the art, for example: described mechanical stirring can adopt conventional chemical reaction mechanical stirrer to carry out; Preferably use magnetic stirring apparatus, when use, open after magnetic stirring apparatus, because instrument base is magnetic, in mixing solutions, put into magneton, thereby can under magneticaction, the rotation by magneton stir the mixing solutions that obtains mixing to mixing solutions.
In this step, described initiated polymerization belongs to thermal-initiated polymerization, it should be noted that, if adopt a step intensification polymerization, heat up and can cause too soon polymerization incomplete, point two step intensification polymerization meetings make polymerization effect better, thereby, in this step, the condition of initiated polymerization is that mixing solutions is first warming up to 30-60 ℃ of prepolymerization 4-8h gradually, then continues to be warming up to 60-80 ℃ and make mixed solution thermopolymerization 1-3h; The intermediate processing of the solution of polyreaction gained is to adopt liquid straight-chain paraffin to precipitate, for example: adopt normal hexane, octane to precipitate.
In this step, described the second solvent can be same with the first solvent phase, also can be not identical; The second solvent mainly plays the effect of dissolving or dispersed polymeres particle, and, during due to masking, need polymers soln to there is certain curtain coating, after film makes, require again this solvent to volatilize, thereby require the second solvent to there is preferably volatile performance and ductility, the solvent that possesses above-mentioned performance in prior art all can be used as the second solvent in the present invention, preferably, the second solvent is one or more the arbitrary combination in acetonitrile, acetone, N-N dimethyl formamide, tetrahydrofuran (THF).
In described polymers soln, described nanometer particle-modified polymer beads adds as the case may be, the polymers soln that is suitable for making polymer dielectric film to make is as the criterion, in general, take the second solvent of 100 weight parts as benchmark, the content of described nanometer particle-modified polymer beads is 0.1-4 weight part.
The kind of described lithium salts and consumption have been conventionally known to one of skill in the art, can use any knownly to making the lithium salts of full solid state polymer electrolyte film, and in the present invention, described lithium salts is preferably LiPF
6, LiClO
4, LiBF
4, LiCF
3sO
3in one or more; And the mol ratio of described lithium salts and described monomer is 1: (8-24).
In this step, the effect of stirring at the temperature of the 50-80 ℃ temperature that is to raise can make nanometer particle-modified polymer beads softening, and can improve nanometer particle-modified polymer beads and the lithium salts solubleness in solvent, the pourable film making solution that forms thickness, is conducive to follow-up masking.In step, in the time that nanometer particle-modified polymer beads is dissolved in the second solvent, due to the bonding force of polymer beads inside and the quantum size effect of nanoparticle and surface effects, the nanoparticle that makes to be doped in polymer beads still can keep satisfactory stability and dispersed uniformly in the second solvent, there will not be and reunites and disperse inhomogeneous phenomenon.
This step is conventional steps, the method that adopts polymers soln to make polymer dielectric film has been conventionally known to one of skill in the art, for example: can be by resulting polymers solution casting on the similar smooth templates such as tetrafluoroethylene template, aluminum foil plate or sheet glass, and the thickness of fixing film is 60-110 μ m, after solvent volatilizees completely, obtaining thickness is the gel polymer electrolyte film of 60-110 μ m.
Make full solid state polymer electrolyte film by above-mentioned steps 1-3, described full solid state polymer electrolyte film comprises polymeric matrix, in described polymeric matrix doped with nanoparticle; The preferred hexafluoro lithium aluminate of described nanoparticle (Li
3alF
6), hexafluoro sodium aluminate (Na
3alF
6), potassium hexafluoroaluminate (K
3alF
6), one or more in aluminium nitride (AlN), five kinds of nanoparticles of boron nitride (BN), more preferably, described nanoparticle is hexafluoro lithium aluminate (Li
3alF
6), hexafluoro sodium aluminate (Na
3alF
6), potassium hexafluoroaluminate (K
3alF
6) in one or more.The median size of described nanoparticle is 1-200nm, the nanoparticle that preferably median size is 1-25nm.Take the monomer of 100 weight parts as benchmark, the addition of described nanoparticle is 1-25 weight part, and preferably, the addition of nanoparticle is 5-20 weight part.
The gel polymer electrolyte film and the full solid state polymer electrolyte film that are prepared by aforesaid method may be used in polymer Li-ion battery.Described polymer Li-ion battery comprises: positive pole, negative pole and the polymer dielectric film between described positive pole and negative pole, in the time that described full solid state polymer electrolyte film is applied to polymer Li-ion battery, do not draw electrolytical imbibition process.And in the time that described gel polymer electrolyte film is applied to polymer Li-ion battery, need to have imbibition technique, the electrolytic solution of described imbibition process using is by LiPF
6, NSC 11801 (EC), methylcarbonate (DMC) and Methyl ethyl carbonate (EMC) composition, the mass ratio of wherein EC: DMC: EMC is 1: 1: 1, LiPF
6volumetric molar concentration get 1mol/L.
Below in conjunction with specific embodiment, the present invention is described in further detail, but embodiments of the present invention are not limited to this.
(1) polymerization is used monomers methyl methacrylate (MMA), vinyl cyanide (AN) and maleic anhydride (MAh) are analytical pure, before polymerization, first remove the stopper in monomer by distillation.
Under nitrogen atmosphere, by the nanometer Li of the monomer M MA of 100 weight parts, AN and MAh (mass ratio of MMA, AN and MAh is 1: 8: 1) and 10 weight parts
3alF
6be dissolved in appropriate acetonitrile, add again the AIBN of 0.1 weight part, after mixing, obtain mixing solutions under magnetic agitation, by described mixing solutions initiated polymerization, first be warmed up to 45 ℃ of prepolymerization 6h, then continue to be warming up to 70 ℃ of thermopolymerization 2.5h, then will react normal hexane precipitation for gained solution, be dried, obtain nanometer particle-modified polymer beads A1.
(2) the described nanometer particle-modified polymer beads A1 of 1 weight part is dissolved in the acetonitrile of 100 weight parts, at 60 ℃, stirs, obtain polymers soln B1.
(3) resulting polymers solution B 1 is poured in tetrafluoroethylene template, and the thickness of fixing film is 70 μ m, after solvent volatilizees completely, obtains doped with Li
3alF
6the gel polymer electrolyte film C1 of nanoparticle.
(1) mass ratio of MMA, AN and MAh is 2: 7: 1, adds the nanometer AlN of 10 weight parts, then adds the BPO of 1 weight part, and all the other make nanometer particle-modified polymer beads A2 all with embodiment 1.
(2) the nanometer particle-modified polymer beads A2 of 2 weight parts is dissolved in the acetone of 100 weight parts, at 70 ℃, stirs, obtain polymers soln B2.
(3) thickness of fixing film is 85 μ m, and all the other obtain the gel polymer electrolyte film C2 doped with AlN nanoparticle all with embodiment 1.
(1) mass ratio of MMA, AN and MAh is 3: 6: 1, adds the nanometer K of 8 weight parts
3alF
6nanometer Na with 7 weight parts
3alF
6, then add the BPO of 0.25 weight part and the AIBN of 0.25 weight part, all the other all with embodiment 1, make nanometer particle-modified polymer beads A3.
(2) the nanometer particle-modified polymer beads A3 of 3 weight parts is dissolved in the acetonitrile of 100 weight parts, at 65 ℃, stirs, obtain polymers soln B3.
(3) thickness of fixing film is 100 μ m, and all the other, must be doped with K all with embodiment 1
3alF
6nanoparticle and Na
3alF
6the gel polymer electrolyte film C3 of nanoparticle.
Monomer M MA, the AN of (1) 100 weight part and VAc (mass ratio of MMA, AN and VAc is 3: 6: 1), add the nanometer AlN of 7 weight parts and the nanometer BN of 8 weight parts, add again the BPO of 0.5 weight part and the AIBN of 0.5 weight part, all the other make nanometer particle-modified polymer beads A4 all with embodiment 1.
(2) the nanometer particle-modified polymer beads A4 of 4 weight parts is dissolved in the acetonitrile of 100 weight parts, at 75 ℃, stirs, obtain polymers soln B4.
(3) thickness of fixing film is 110 μ m, and all the other obtain the gel polymer electrolyte film C4 doped with AlN nanoparticle and BN nanoparticle all with embodiment 1.
Embodiment 5
Except step (2), all the other steps and processing condition are all with identical with embodiment 1, step (2) in embodiment 5 is: the nanometer particle-modified polymer beads A1 of weight part is dissolved in the acetonitrile of 100 weight parts, then adds LiPF
6, wherein the mol ratio of Li and monomer (MMA, AN and MAh) is 16, after dissolving, at 60 ℃, stirs, and obtains polymers soln B1 ', then makes doped with Li according to the step (3) of embodiment 1
3alF
6the full solid state polymer electrolyte film C5 of nanoparticle.
Embodiment 6
Except step (2), all the other steps and processing condition are all with identical with embodiment 2, step (2) in embodiment 6 is: the nanometer particle-modified polymer beads A2 of 2 weight parts is dissolved in the acetone of 100 weight parts, then adds LiClO
4, wherein the mol ratio of Li and monomer is 20, after dissolving, at 70 ℃, stirs, and obtains polymers soln B2 ', then makes the full solid state polymer electrolyte film C6 doped with AlN nanoparticle according to the step (3) of embodiment 2.
comparative example 1
Except not adding nanoparticle, all the other steps and processing condition, all with embodiment 1, obtain gel polymer electrolyte film D1.
comparative example 2
Except changing the step that adds of nanoparticle into step (2), nanoparticle changes SiO into
2outward, all the other steps and processing condition are all identical with embodiment 1, obtain gel polymer electrolyte film D2.
comparative example 3
Except not adding nanoparticle, all the other steps and processing condition, all with embodiment 5, obtain full solid state polymer electrolyte film D3.
comparative example 4
Except changing the step that adds of nanoparticle into step (2), nanoparticle changes SiO into
2outward, all the other steps and processing condition are all identical with embodiment 5, obtain gel polymer electrolyte film D4.
performance test
1, pick up test
Fig. 1 is the pick up of embodiment 1-4 and comparative example 1-2 gained gel polymer electrolyte membrane sample.The pick up of polymeric film is that gel polymer electrolyte film was immersed in to electrolytic solution after 2 hours, calculates according to following formula 1:
(formula 1)
In formula, W1 and W2 represent respectively the dry film soaking before electrolytic solution and the weight of soaking the wet film after electrolytic solution.
As can be seen from Figure 1: adopt preparation method of the present invention to add the pick up of the gel polymer electrolyte film that nanoparticle makes all very high, reach as high as 312%, far away higher than the gel polymer electrolyte film that does not add nanoparticle, and also higher than adopting direct batch mixing method to add nanometer SiO
2the pick up of the polymer dielectric film making.Absolutely prove: adopt the prepared gel polymer electrolyte film doped with nanoparticle of preparation method of the present invention to there is splendid absorbent.
2, mechanical strength test
The physical strength of gel polymer electrolyte membrane sample embodiment 1-4 and comparative example 1-2 being obtained with XLS-05 type strength tester is tested.Calculate with formula Δ F=P/ (bd), wherein Δ F (kg/cm
2) be the physical strength of film, P is maximal destruction load (kg), and b is sample width (cm), and d is thickness of sample (cm), and test result is in table 1.
Test result shows: adopt the prepared polymer dielectric film doped with nanoparticle of preparation method of the present invention to have splendid mechanical property.
3, ac impedance measurement
The gel-state polymer electrolyte of lithium-ion battery (through imbibition technique) that embodiment 1-6 and comparative example 1-4 are obtained and full solid state polymer electrolyte film are (without imbibition, can directly test) sample be placed between two stainless steels (SS) electrode, carry out alternating-current impedance experiment, intersection point linear and real axis is the resistance of polymer dielectric, (wherein L represents the thickness of polymer dielectric can to obtain thus the ionic conductivity of polymer dielectric: σ=L/AR, A is the contact area of stainless steel plate and film, R is the resistance of polymer dielectric).The ionic conductivity that calculates gel polymer electrolyte and all solid state electrolyte film is listed in table 1.
Test result shows: adopt preparation method of the present invention to add gel polymer electrolyte that nanoparticle makes and the ionic conductivity of full solid state polymer electrolyte film, apparently higher than not adding nanoparticle or adding nanometer SiO by common batch mixing method
2the ionic conductivity of the gel polymer electrolyte obtaining and full solid state polymer electrolyte film.
4, the test of lithium ion transference number
First in glove box respectively by the gel polymer electrolyte of preparing in embodiment 1-6 and comparative example 1-4 (through imbibition technique) and full solid state polymer electrolyte film (without imbibition, can directly test) sample is sandwiched between two parallel lithium sheets, thereby be assembled into the button cell model of " lithium electrode | polymer dielectric film | lithium electrode ", then utilize timing amperometric measurement method, adopt the CHI660C type electrochemical workstation of Shanghai Chen Hua instrument company, above 10 battery models are clipped in the fixture of electrochemical workstation successively, and apply the constant voltage of 3 volts at two ends, to be designated as initial current I at the electric current of executing alive moment generation
i, reduce gradually and be tending towards a stationary value with after-current, this stable electrical flow valuve is designated as to I
∞.
Adopt the above result of measuring according to the transference number of ions t of following formula calculated for gel state polymer dielectric and full solid state polymer electrolyte film
+(being lithium ion transference number):
t
+＝I
∞/I
i
The results are shown in Table 1 for it.
As shown in Table 1: adopt preparation method of the present invention to add gel polymer electrolyte that nanoparticle obtains and the lithium ion transference number of full solid state polymer electrolyte film, apparently higher than not adding nanoparticle or adding nanometer SiO by common batch mixing method
2the gel polymer electrolyte film obtaining and the lithium ion transference number of full solid state polymer electrolyte film.
5, electrochemical stability window test:
The gel polymer electrolyte (through imbibition technique) that embodiment 1-4 is obtained with comparative example 1-2 is assembled into button cell together with metal lithium sheet, its structure is: stainless steel plate/gel polymer electrolyte/Li, carries out electrochemical stability window test.It is to adopt linear sweep voltammetry to determine the electrochemical window of gel polymer electrolyte, and wherein stainless steel plate is working electrode, and metal lithium sheet is to electrode and reference electrode.Gained decomposition voltage is listed in table 1.Consult Fig. 2, be the decomposition voltage graphic representation of embodiment 1 simultaneously, and the decomposition voltage recording after the gel polymer electrolyte film imbibition of illustrated embodiment 1 is 5.7, and decomposition voltage is higher.
Test result shows: adopt preparation method of the present invention, the decomposition voltage of the gel polymer electrolyte that interpolation nanoparticle obtains is high, can be compatible with high voltage electrode material, because can better apply to polymer Li-ion battery.
6, button cell specific storage, first charge-discharge efficiency test:
Specific storage and first charge-discharge efficiency are all in the upper test of BK-6016AR cabinet (Guangzhou Lanqi Electronic Industrial Co., Ltd.'s production).
Styrene-butadiene rubber(SBR) (SBR) and carboxymethyl cellulose (CMC) are dissolved in after distilled water, and with at room temperature high-speed stirring 3.5h of synthetic graphite, conductive agent, its mass ratio is: 2.5: 1.5: 90: 6.The material being stirred is applied on Copper Foil, vacuum-drying 24h under room temperature after drying, compacting in flakes, the gel polymer electrolyte obtaining through imbibition technique with lithium sheet and embodiment 1-4 and comparative example 1-2 gained gel polymer electrolyte film is assembled into CR2016 simulated battery; Be assembled in (content of water and oxygen is less than 3ppm) in the glove box that is filled with argon gas of battery operates.
Electric current with 0.1C is discharged to 2.5V by above-mentioned simulated battery first from 0.005V, records loading capacity, the quality of specific storage=loading capacity/synthetic graphite.
With the continuous current of 0.5 milliampere, above-mentioned simulated battery is charged to 0.005 volt, then with the continuous current of 0.2 milliampere by battery discharge to 2.5 volt, record loading capacity and initial charge capacity first, first charge-discharge efficiency=loading capacity/initial charge capacity × 100% first.Test result is listed in table 1.
From test result: adopt the polymer dielectric doped with nanoparticle that preparation method of the present invention makes can effectively improve specific storage and the first charge-discharge efficiency of button cell.
Table 1
1), comparative example 1-4 and comparative example 1-2 can know test result:: the gel polymer electrolyte film making by preparation method of the present invention, and does not have doped with nanometer particle or add nanometer SiO by common batch mixing method
2the gel polymer electrolyte obtaining is compared, there are preferably absorbent and physical strength, the ionic conductivity of the gel polymer electrolyte obtaining after imbibition is high, transference number of ions is high, electrochemical stability is good, and it is as the dielectric film of polymer Li-ion battery, be assembled into after CR2016 button cell, specific storage and first charge-discharge efficiency significantly improve.
2), comparative example 5-6 and comparative example 3-4 can know: the full solid state polymer electrolyte film making by preparation method of the present invention, and does not have doped with nanometer particle or add nanometer SiO by common batch mixing method
2the full solid state polymer electrolyte obtaining is compared, and ionic conductivity and lithium ion transference number are significantly improved.
3), comparative example 1 can know with embodiment 4 with embodiment 2, embodiment 3: add sodium aluminum fluoride (Li
3alF
6, Na
3alF
6, K
3alF
6in one or more) over-all properties of the gel polymer electrolyte film that obtains of nanoparticle (absorbent, physical strength, ionic conductivity, transference number of ions, and the performance such as electrochemical stability) is better than adding the over-all properties of the gel state electrolyte film that BN, AlN nanoparticle obtain.
4), comparative example 5 can know with embodiment 6: add sodium aluminum fluoride nanoparticle (Li
3alF
6, Na
3alF
6, K
3alF
6in one or more) over-all properties (ionic conductivity, lithium ion transference number) of the full solid state polymer electrolyte film that obtains is better than adding the over-all properties of all solid state electrolyte film that BN, AlN nanoparticle obtain.
Claims (10)
1. a preparation method for polymer dielectric film, is characterized in that, comprises the steps:
Modification: under inert gas atmosphere, monomer is dissolved in the first solvent, add nanoparticle, add again initiator to mix and obtain mixing solutions, by described mixing solutions initiated polymerization, again the solution of polyreaction gained precipitated, be dried, obtain nanometer particle-modified polymer beads; Described nanoparticle is Li
3alF
6, Na
3alF
6, K
3alF
6in one or more;
Masking: described nanometer particle-modified polymer beads is dissolved in the second solvent, obtains polymers soln, then adopt polymers soln to make described polymer dielectric film.
2. the preparation method of polymer dielectric film according to claim 1, is characterized in that, described monomer is selected from least two kinds in methacrylic ester, vinyl cyanide, maleic anhydride, vinyl-acetic ester;
Described the first solvent is selected from one or more in acetonitrile, acetone, N-N dimethyl formamide, tetrahydrofuran (THF);
Described initiator is selected from least one in Diisopropyl azodicarboxylate, benzoyl peroxide;
Take the monomer of 100 weight parts as benchmark, the addition of described nanoparticle is 1-25 weight part, and the addition of described the first solvent is 300-1900 weight part, and the addition of described initiator is 0.05-5 weight part.
3. the preparation method of polymer dielectric film according to claim 1, is characterized in that, in modification procedure, described initiated polymerization is that mixing solutions is first warming up to 30-60 ℃ of prepolymerization 4-8h gradually, then continues to be warming up to 60-80 ℃ of thermopolymerization 1-3h; The intermediate processing of polyreaction gained solution is to adopt liquid straight-chain paraffin to precipitate.
4. the preparation method of polymer dielectric film according to claim 1, is characterized in that, in masking step, described the second solvent is selected from one or more in acetonitrile, acetone, N-N dimethyl formamide, tetrahydrofuran (THF); Take the second solvent of 100 weight parts as benchmark, the addition of described nanometer particle-modified polymer beads is 0.1-4 weight part.
5. the preparation method of polymer dielectric film according to claim 1, is characterized in that, in masking step, polymers soln is poured in template, after solvent evaporates, obtain polymer dielectric film, the thickness of resulting polymers dielectric film is 60-110 μ m.
6. according to the preparation method of the polymer dielectric film described in claim 1-5 any one, it is characterized in that, in masking step, in described polymers soln, also add and be dissolved with lithium salts.
7. the preparation method of polymer dielectric film according to claim 6, is characterized in that, described lithium salts is LiPF
6, LiClO
4, LiBF
4, LiCF
3sO
3in one or more, the mol ratio of described lithium salts and described monomer is 1:(8-24).
8. a polymer dielectric film, is characterized in that, the method as described in claim 1-7 any one of employing makes, and described polymer dielectric film comprises polymeric matrix, in described polymeric matrix doped with nanoparticle; Described nanoparticle is selected from Li
3alF
6, Na
3alF
6, K
3alF
6in one or more.
9. polymer dielectric film according to claim 8, wherein, the median size of described nanoparticle is 1-200 nm; Take the weight of the polymeric matrix of 100 weight parts as benchmark, the content of described nanoparticle is 1-25 weight part.
10. a polymer Li-ion battery, comprise: positive pole, negative pole and the polymer dielectric film between described positive pole and negative pole, it is characterized in that, described polymer dielectric film is the polymer dielectric film described in any one in claim 8,9.
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| CN103441301B (en) * | 2013-09-11 | 2017-09-12 | 东莞新能源科技有限公司 | Lithium ion battery gel electrolyte and preparation method thereof |
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