CN102263290B - Polymer battery and preparation method thereof - Google Patents
Polymer battery and preparation method thereof Download PDFInfo
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- CN102263290B CN102263290B CN201010190242.3A CN201010190242A CN102263290B CN 102263290 B CN102263290 B CN 102263290B CN 201010190242 A CN201010190242 A CN 201010190242A CN 102263290 B CN102263290 B CN 102263290B
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Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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- Secondary Cells (AREA)
- Cell Separators (AREA)
Abstract
The invention discloses a polymer battery. The polymer battery comprises a positive pole, a negative pole and a polymer electrolyte, wherein the polymer electrolyte is positioned between the positive pole and the negative pole; the polymer electrolyte comprises a porous diaphragm and an electrolyte, wherein the electrolyte is accommodated in the holes of the porous diaphragm in a gelatin/solution form, the porous diaphragm comprises a first porous membrane, a second porous membrane and a porous basilemma, and the porous basilemma is positioned between the first porous membrane and the second porous membrane; the porosity of the first porous membrane is 40%-70%, the porosity of the second porous membrane is 30%-40%, and the porosity of the porous basilemma is 25%-45%; the first porous membrane consists of polymers with 10%-25% of crystallinity, and the second porous membrane consists of polymers with 25%-40% crystallinity; the average particle size of the first porous membrane is 0.06-0.2 mu m, the average particle size of the second porous membrane is 0.06-0.2 mu m, and the average particle size of the porous basilemma is 0.02-0.08 mu m; and the first porous membrane in the polymer battery is contacted with the negative pole, and the second porous membrane is contacted with the positive pole.
Description
Technical field
The invention relates to a kind of polymer battery and preparation method thereof.
Background technology
It is high that polymer lithium cell electric pond has specific energy, have extended cycle life, and the advantages such as processing characteristics that security performance is good and good.Since within 1999, putting on market, caused people's extensive attention.Compare with traditional liquid lithium ionic cell, except having the advantages such as high voltage, high-energy-density, long circulation life, environmental protection and memory-less effect, because adopt non-current state electrolyte in poly-lithium battery, overcome well liquid lithium ion and existed in the dead of night, the potential safety hazards such as even blast on fire.Shell can also adopt aluminum-plastic composite membrane as packing simultaneously, replace aluminum hull and box hat that traditional li battery shell is used, more flexible in design, because it is light that aluminum-plastic composite membrane weight is wanted, polymer Li-ion battery has surpassed significantly the liquid lithium ion battery that adopts aluminum hull or firm shell on gravimetric specific energy.Therefore polymer Li-ion battery has in following E-consumer field the trend that progressively replaces liquid lithium ion battery.
The inside of poly-lithium battery does not adopt liquid electrolyte, but adopts non-current state polymer dielectric.The polymer dielectric that is used at present lithium battery field mainly contains two classes, comprises solid electrolyte and gel/solution state electrolyte.Solid electrolyte is all generally to adopt as prepared by the polyethers high polymer of polyethylene glycol oxide (PEO) class. utilizes lithium ion to realize ion in the coordination of PEO based polyalcohol Zhong Yang functional group and effect and move, yet under its room temperature, ionic conductivity also do not reach 10
-3the level of S/cm, although at high temperature can reach, has limited range of application.In order to improve the ionic conductivity under the normal temperature of polymer dielectric, produced gel/solution state electrolyte, because the electrolyte of colloidal state can, as solid electrolyte, avoid battery leakage, the high ionic conductivity that has kept again liquid electrolyte, application very extensively.Gel polymer electrolyte can be divided into chemical gel and physical gel type according to preparation method at present.Chemical gel technology also claims in-situ polymerization technique, this technique will be by containing polymerisable monomer, mix with liquid electrolyte with initator, together inject battery, by methods such as heating, trigger monomer polymerization, forms the electrolyte of gel state, and in the electrolyte of gel state, has the network-like skeleton being comprised of high polymer.If application number is that CN200410026814.9 discloses a kind of polymer electrolyte lithium-ion battery, it mainly consists of positive and negative electrode composite component, barrier film composite component and four kinds of composite components of external packing composite component between positive and negative electrode composite component; Wherein diaphragm element is to knit the barrier film of reticular fiber structure as the skeleton of composite component, adds the mixture that colloidal polymer electrolyte forms, and it is characterized in that: polymer dielectric is alternately present in the surface and micropore of described barrier film with continuous state; Described continuous state replaces after electrolytic polymer is grown two and three dimensions polymer network and produced chemical action with electrolyte by monomer and initator generation thermopolymer chemical reaction and forms; It has the effect of powerful bonding agent, positive and negative electrode composite component and barrier film are bonded together securely, form an integral body with self bulk strength and rigidity, but in cyclic process, the electrolyte at negative pole place constantly decomposes, its surperficial SEI film constantly thickens, because both positive and negative polarity place polymer dielectric is almost consistent, the electrolyte of negative pole face decomposes very fast, causes larger polarization, be easy to produce dendrite, cause the cycle performance of battery poor.
In prior art, the U.S. Bellcore technology initiative development physical gel/solution technique, their technical process is for adopting Kynoar-hexafluoropropylene copolymer (PVDF-HFP) as skeletal matrix material, by abstracting method, prepare porous membrane, by physical adsorption process, electrolyte enters in the hole of PVDF-HFP barrier film.In whole technical process, the production of polymer dielectric does not relate to the courses of reaction such as chemical polymerization.As disclosed a kind of colloidal polymer electrolyte lithium ion battery in application number CN200610053298.8, it mainly consists of positive and negative electrode composite component, barrier film composite component and four kinds of composite components of external packing composite component between positive and negative electrode composite component; Wherein, barrier film composite component is to knit the barrier film of reticular fiber structure as the skeleton of composite component, add the mixture that colloidal polymer electrolyte forms, it is characterized in that: in polymer, electrolyte is present in the surface of described barrier film and micropore with continuous state colloid; Described continuous state colloidal electrolyte polymer forms after being grown two and three dimensions polymer network and produced chemical action with electrolyte by monomer and initator generation thermopolymer chemical reaction; It has the effect of powerful bonding agent, and positive and negative electrode composite component and barrier film are bonded together, and forms the integral body of self bulk strength and rigidity, but has equally the poor defect of cycle performance by this polymer battery, also has potential safety hazard simultaneously.
Summary of the invention
Object of the present invention is intended to overcome and in prior art, has that cycle performance of battery is poor, the defect of poor stability, and a kind of good cycle, polymer battery that security performance is good and preparation method thereof are provided.
For this reason, the invention provides a kind of polymer battery, this polymer battery comprises positive pole, negative pole, polymer dielectric, described polymer dielectric is between positive pole and negative pole, this polymer dielectric comprises porous septum and electrolyte, wherein, electrolyte is contained in the hole of described porous septum with the form of gel/solution, porous septum comprises the first perforated membrane, the second perforated membrane and porous basement membrane, porous basement membrane is between the first perforated membrane and the second perforated membrane, wherein the porosity of the first perforated membrane is 40-70%, the porosity of the second perforated membrane is 30-40%, the porosity of porous basement membrane is 25-45%, the polymer that the first perforated membrane is 10-25% by degree of crystallinity forms, the polymer that the second perforated membrane is 25-40% by degree of crystallinity forms, the average pore size of described the first perforated membrane is 0.06-0.2 μ m, the average pore size of the second perforated membrane is 0.06-0.2 μ m, the average pore size of porous basement membrane is 0.02-0.08 μ m, and the first perforated membrane in polymer battery contacts with negative pole, the second perforated membrane contacts with anodal.
The preparation method of above-mentioned battery diaphragm is also provided simultaneously, and the method comprises:
A preparation method for polymer battery, the method comprises:
1) will contain the first polymer and the first solvent, the first pore creating material obtains the first coating liquid after mixing, and the first coating liquid is coated onto on a surface of porous matrix; Heat for the first time, remove solvent and the pore creating material of the first coating liquid; To contain the second polymer and the second solvent, the second pore creating material obtains the second coating liquid after mixing, and is coated onto on another surface of above-mentioned porous matrix; Heat for the second time, remove solvent and the pore creating material of the second coating liquid, obtain porous septum;
2) anodal, negative pole are pressurizeed mutually compound with the porous septum of step 1 preparation by heating, then complex is plugged in battery container, inject the electrolyte in battery container, electrolyte is contained in the space of porous septum with the form of gel/solution, then encapsulation, obtains polymer battery, wherein, the first perforated membrane contacts with negative pole, and the second perforated membrane contacts with anodal.
Asymmetric polymer electrolyte prepared in accordance with the present invention has good ionic conductivity, because the polymer dielectric of the side towards negative pole has higher ionic conductance, more pick up, be conducive to suppress the growth of the dendrite of lithium, thereby avoid the deterioration of battery short circuit and performance, improved the security performance of battery, the cycle performance of battery also significantly gets a promotion simultaneously.
Embodiment
Inventor finds by great many of experiments, in polymer lithium secondary battery, and because anode and negative electrode are all to embed the active material that goes out lithium ion with embedding, lithium ion reciprocating motion in organic electrolyte or the polymer dielectric between negative electrode and anode.Lithium ion has different embeddings and embedding to go out the difference of complexity in anode and negative electrode, especially on anode, prior art adopts the material with carbon elements such as graphite as negative pole, if the embedding of lithium ion is more difficult, easily cause Li dendrite, affect the fail safe of battery, simultaneously due in battery actual cycle process, continuous consumption along with electrolyte, the SEI film at negative pole place constantly thickens, and both positive and negative polarity is inconsistent for the wear rate of electrolyte, the consumption at negative pole place is faster than positive pole place, if diaphragm design is become to the equal barrier film of liquid absorption of both sides, will cause so negative pole surface polarization to increase, embedding lithium difficulty, easily produce dendrite, thereby cause the reduction of the cycle performance of battery, stability decreases.When serious, may cause safety problem.
And in existing technology, electrolyte between the both positive and negative polarity of polymer battery is the polymer dielectric of barrier film and anodal contact-making surface and barrier film and negative pole contact-making surface especially, no matter still almost consistent in nature from quality, and the difference going out in the lip-deep embedding embedding of both positive and negative polarity due to lithium ion, it is for the polymer dielectric near anodal and close negative pole, consumption along with electrolyte, negative pole embedding lithium is difficulty further, and because both positive and negative polarity is to electrolytical different depletion rate, electrolyte near negative pole face reduces gradually, in the time of even dry, easily impel the growth of Li dendrite, once Li dendrite, through polymer dielectric, make both positive and negative polarity conducting, will there is battery short circuit, when serious, battery can occur burns, even blast, therefore, the cycle performance of the security performance of raising polymer battery and raising battery becomes and improves a most important ring in battery performance.Meanwhile, both positive and negative polarity is different for electrolytical depletion rate, can cause the cycle performance of battery to decline.
For this reason, a kind of polymer battery, this polymer battery comprises positive pole, negative pole, polymer dielectric, described polymer dielectric is between positive pole and negative pole, this polymer dielectric comprises porous septum and electrolyte, wherein, electrolyte is contained in the hole of described porous septum with the form of gel/solution, hole barrier film comprises the first perforated membrane, the second perforated membrane and porous basement membrane, porous basement membrane is between the first perforated membrane and the second perforated membrane, wherein the porosity of the first perforated membrane is 40-70%, the porosity of the second perforated membrane is 30-40%, the porosity of porous basement membrane is 25-45%, the polymer that the first perforated membrane is 10-25% by degree of crystallinity forms, the polymer that the second perforated membrane is 25-45% by degree of crystallinity forms, the average grain diameter of described the first perforated membrane is 0.06-0.2 μ m, the average pore size of the second perforated membrane is 0.06-0.2 μ m, the average pore size of porous basement membrane is 0.02-0.08 μ m, and the first perforated membrane in polymer battery contacts with negative pole, the second perforated membrane contacts with anodal.
Wherein, the first perforated membrane and the second perforated membrane can be separately independently by Kynoar-hexafluoropropylene, Kynoar-chlorotrifluoroethylene, Kynoar, polymethyl methacrylate, polyethylene glycol oxide, PPOX, polyacrylonitrile, polyvinyl chloride, one or more compositions in polyvinyl acetate, porous basement membrane is by polyethylene, polypropylene, polyimides, polysulfones, polychlorostyrene carbamate, polyvinyl chloride, cellulose, polypropylene is fine, polyvinylidene fluoride, one or more compositions in polytetrafluoroethylene.
Here, why inventor will select to adopt the polymer that degree of crystallinity is different to form the first perforated membrane and the second perforated membrane, is because there is amorphous phase and crystalline phase in selected polymer.Amorphous area imbibition swelling in electrolyte, adopt lower degree of crystallinity to be conducive to the more electrolyte of absorption of polymer porous film, and in the present invention, during practical set battery, the less one side of degree of crystallinity in polymer porous film is contacted with negative pole, and this is because the electrolyte of close negative pole is easy to dry up.
Wherein porous matrix can be polyethylene, polypropylene, and polyimides, polysulfones, polychlorostyrene carbamate, polyvinyl chloride, cellulose, polypropylene is fine, polyvinylidene fluoride, one or more in polytetrafluoroethylene.
Wherein, in the present invention, can also add the inorganic filler of 1-5 % by weight in first, second coating liquid, it is distributed in polymer porous film.The introducing of inorganic nano-particle can further improve mechanical performance and the heat resistance of polymer porous film of the present invention; The present invention, for the not special restriction of kind of inorganic nano-particle, can be the conventional inorganic nano-particle in this area.Concrete, for example, inorganic micro-and nano-particles can be silicon dioxide, zirconium dioxide, aluminium oxide, titanium dioxide, cupric oxide and γ-LiAlO
2in one or more.Average grain diameter is 20-200nm.
The thickness of described the first perforated membrane is 2-15 μ m, and the thickness of porous basement membrane is 9-50 μ m, and the thickness of the second perforated membrane is 2-15 μ m.
A preparation method for battery diaphragm, the method comprises:
1) will contain the first polymer and the first solvent, the first pore creating material obtains the first coating liquid after mixing, and the first coating liquid is coated onto on a surface of porous basement membrane; Heating, removes solvent and pore creating material in the first coating liquid for the first time; To contain the second polymer and the second solvent, the second pore creating material obtains the second coating liquid after mixing, and is coated onto on another surface of above-mentioned porous matrix; Heat for the second time, remove solvent and the pore creating material of the second coating liquid, obtain porous septum;
2) anodal, negative pole are pressurizeed mutually compound with the porous septum of step 1 preparation by heating, then complex is plugged in battery container, inject the electrolyte in battery container, electrolyte is contained in the hole of porous septum with the form of gel/solution, then encapsulation, obtains polymer battery, wherein, the first perforated membrane contacts with negative pole, and the second perforated membrane contacts with anodal.
The first perforated membrane raw material of telling in described step 1 is selected from the first polymer and is selected from Kynoar-hexafluoropropylene, Kynoar-chlorotrifluoroethylene, Kynoar, polymethyl methacrylate, polyethylene glycol oxide, PPOX, polyacrylonitrile, polyvinyl chloride, one or more in polyvinyl acetate, described the first solvent and described the second solvent are acetone independently of one another, N, dinethylformamide, N, N-dimethylacetylamide, 1-METHYLPYRROLIDONE, acetonitrile, dimethyl sulfoxide (DMSO), one or more in butanone and oxolane, the first pore creating material is selected from water, toluene, ethanol, butanols, glycerol, isopropyl alcohol, butanediol, dimethyl carbonate, methyl ethyl carbonate, ethyl acetate, normal heptane, one or more in normal octane.
The total weight of the first coating liquid of take in described step 1 is benchmark, and the weight ratio of the first polymer, the first solvent and the first pore creating material is 2-30: 30-96: 2-40.
The mode various heating means known in those skilled in the art of the heating described in described step 1, the temperature of heating is 40-120 ℃, the time of heating is 1-60min.
The second perforated membrane raw material of telling in described step 1 is selected from the second polymer and is selected from Kynoar-hexafluoropropylene, Kynoar-chlorotrifluoroethylene, Kynoar, polymethyl methacrylate, polyethylene glycol oxide, PPOX, polyacrylonitrile, polyvinyl chloride, one or more in polyvinyl acetate, described the first solvent and described the second solvent are acetone independently of one another, N, dinethylformamide, N, N-dimethylacetylamide, 1-METHYLPYRROLIDONE, acetonitrile, dimethyl sulfoxide (DMSO), one or more in butanone and oxolane, the second pore creating material is selected from water, toluene, ethanol, butanols, glycerol, isopropyl alcohol, butanediol, dimethyl carbonate, methyl ethyl carbonate, ethyl acetate, normal heptane, one or more in normal octane.
The total weight of the second coating liquid of take in described step 3 is benchmark, and the weight ratio of the second polymer, the second solvent and the second pore creating material is 2-30: 30-96: 2-40.
Heating-up temperature in wherein said step 4 is 40-120 ℃, and the time of heating is 1-60min.
In above-mentioned step 1 coating process, for the thickness applying, can control the distance with porous matrix by controlling the gap of scraper, hang the method for too much amount.Or a pair of mayer rod (Mayer bar) standing facing each other by certain intervals is wiped too much coating fluid etc. off.In above-mentioned step 1, by by a series of baking box with uniform temperature of perforated membrane process, make solvent and pore creating material volatilization in the first coating liquid, the second coating liquid, the temperature of above-mentioned heating is 40-120 ℃.
Particularly, for obtaining first porous polymer with higher porosity, in the coating liquid of preparing in above-mentioned step, control and can obtain adding of pore creating material.Wherein the content of pore creating material is in certain scope, and the Content of Pore-forming Agents in the first polymer is greater than the content of the pore creating material in the second polymer.
The present invention provides a kind of asymmetric polymer electrolyte simultaneously, comprises polymer porous film and electrolyte, and electrolyte is contained in the hole of polymer porous film with the form of gel/solution, and wherein the first perforated membrane and the second perforated membrane have different pick ups.Electrolyte is the necessary component of battery.The present invention is not particularly limited for electrolyte, can be the conventional polymer battery electrolyte in this area, and polymer porous film of the present invention can absorb more electrolyte.In polymer dielectric of the present invention, the weight ratio of electrolyte and porous septum is 1-10: 1.
The present invention is not particularly limited for the preparation method of polymer lithium secondary battery and the composition of anodal and negative pole, and for example, positive pole can be for containing the aluminium foil of cobalt acid lithium, and negative pole can be for containing the Copper Foil of graphite.Below in conjunction with embodiment, the present invention is described in detail.
Embodiment 1
By Kynoar-hexafluoropropylene (degree of crystallinity 10%) and deionized water dissolving in acetone in, stir, obtain the first coating liquid, in this first coating liquid, the content of Kynoar-hexafluoropropylene is 6 % by weight, the content of deionized water is 10 % by weight, and the content of acetone is 84 % by weight.By polyethylene porous matrix, (porosity is 35%, average pore size is 0.08 μ m, thickness is 20 μ m) be fixed on glass plate, use the mayer rod of model #6, on a face of the polyethylene porous membrane that the first polymer solution is coated in, by the above-mentioned polyethylene porous matrix that is coated with the first coating liquid at 60 ℃ of dry 10min, obtain adhering to the porous basement membrane of the first perforated membrane, mayer rod is 3 μ m with the gap of polyethylene porous membrane herein, Kynoar-hexafluoropropylene (degree of crystallinity 30%) and toluene are dissolved in acetone, after mixing, obtain the second coating liquid, in the second coating liquid, the content of Kynoar-hexafluoropropylene is 6 % by weight, the content of toluene is 10 % by weight, the content of acetone is 84%, then the second coating liquid is coated on the another side of porous basement membrane with mayer rod, coating thickness is 3 μ m, the porous basement membrane that is attached with the second coating liquid is put into drying box, under the condition of 65 ℃, heating 30min, obtain porous septum sample A1, the average pore size tester that adopts precise and tiny Gao Bo, Beijing science and technology Co., Ltd to produce is tested sample, the average pore size that shows the first perforated membrane is 0.06 μ m, the average pore size of the second perforated membrane is 0.1 μ m.
The porous septum obtaining is inserted in battery container, and the ratio that is 2: 1 according to the weight ratio of electrolyte and porous septum in battery container, inject electrolytical solution, wherein, described electrolytical solution be in the mixed solvent that ethylene carbonate and dimethyl carbonate are 1: 1 according to volume ratio containing the lithium hexafluoro phosphate solution of 1M, after encapsulation, obtain polymer battery sample T1.
Embodiment 2
By Kynoar-hexafluoropropylene (degree of crystallinity 20%) and deionized water dissolving in acetone, stir, obtain the first polymer solution, in this first polymer solution, the content of Kynoar-hexafluoropropylene is 10 % by weight, the content of deionized water is 13 % by weight, and the content of acetone is 77 % by weight.Polypropylene porous matrix is fixed on glass plate, uses the mayer rod of model #6, the first coating liquid is coated on a face of polypropylene (porosity is 60%, and average pore size is 0.03 μ m, and thickness is 15 μ m).The above-mentioned polypropylene porous matrix that is coated with the first polymer solution is dried, obtains being attached to lip-deep first perforated membrane of porous basement membrane, mayer rod is 5 μ m with the gap of polypropylene porous film herein.
Kynoar-hexafluoropropylene (degree of crystallinity 40%) and isopropyl alcohol are dissolved in acetone, are stirred to and evenly obtain the second polymer solution.In this second polymer solution, the content of Kynoar-hexafluoropropylene is that the content of 12 % by weight, isopropyl alcohol is that the content of 78 % by weight, isopropyl alcohol is that 10 % by weight, the fixing rod of mayer are herein 5 μ m with the gap of polypropylene porous film.Again above-mentioned the second polymer solution is coated on the another side of polypropylene porous basement membrane.The above-mentioned polypropylene porous matrix that is coated with the second polymer solution is dried, obtains porous septum sample A2, the average pore size that shows the first perforated membrane is 0.08 μ m, and the average pore size of the second perforated membrane is 0.2 μ m.
The porous septum obtaining is inserted in battery container, and the ratio that is 10: 1 according to the weight ratio of electrolyte and porous septum in battery container, inject electrolyte, wherein, described electrolyte be in the mixed solvent that ethylene carbonate and dimethyl carbonate are 1: 1 according to volume ratio containing the lithium hexafluoro phosphate solution of 1M, after encapsulation, obtain polymer battery sample T2.
Embodiment 3
By Kynoar-chlorotrifluoroethylene (degree of crystallinity 25%) and deionized water dissolving in acetone, stir, obtain the first polymer solution, in this first polymer solution, the content of Kynoar-hexafluoropropylene is 10 % by weight, the content of deionized water is 12 % by weight, and the content of acetone is 77 % by weight.Polyethylene porous basement membrane (porosity is 60%, and average pore size is 0.03 μ m, and thickness is 15 μ m) is fixed on glass plate, uses the mayer rod of model #6, the first polymer solution is coated on a poly face.The above-mentioned polyethylene porous matrix that is coated with the first polymer solution is dried, obtains being attached to lip-deep first perforated membrane of porous basement membrane.Mayer rod is 4 μ m with the gap of polyethylene porous membrane herein.
Configure the second porous solution, wherein the content of Kynoar (degree of crystallinity 40%) is 10 % by weight, the content of deionized water is 12 % by weight, the content of acetone is 78 % by weight, the polyethylene porous matrix that above-mentioned preparation has been adhered to the first perforated membrane is fixed on glass plate, use the mayer rod of model #6, the second polymer solution is coated on the another one face of polyethylene porous basement membrane, after dry, porous septum sample A3, mayer rod is 5 μ m with the gap of polyethylene porous membrane herein, the average pore size that shows the first perforated membrane is 0.07 μ m, the average pore size of the second perforated membrane is 0.15 μ m.
The porous septum obtaining is inserted in battery container, and the ratio that is 10: 1 according to the weight ratio of electrolyte and porous septum in battery container, inject electrolyte, wherein, described electrolyte be in the mixed solvent that ethylene carbonate and dimethyl carbonate are 1: 1 according to volume ratio containing the lithium hexafluoro phosphate solution of 1M, after encapsulation, form polymer battery sample T3
Embodiment 4
The present embodiment is used for illustrating battery diaphragm provided by the present invention and preparation method thereof.
Polymethyl methacrylate (degree of crystallinity 12%) and Kynoar-chlorotrifluoroethylene (degree of crystallinity is 20%) and toluene are dissolved in acetone, stir, obtain the first polymer solution, in this first polymer solution, the content of Kynoar-hexafluoropropylene is 4 % by weight, and the content of Kynoar-chlorotrifluoroethylene is 3%, and the content of toluene is 12 % by weight, content 2 % by weight of titanium dioxide (average grain diameter 30nm), the content of acetone is 79 % by weight.Polyethylene porous basement membrane (porosity is 35%, and average pore size is 0.08 μ m, and thickness is 20 μ m) is fixed on glass plate, uses the mayer rod of model #6, the first polymer solution is coated on a poly face.The above-mentioned polyethylene porous matrix that is coated with the first polymer solution is dried, obtains being attached to lip-deep first perforated membrane of porous matrix.Mayer rod is 3 μ m with the gap of polyethylene porous membrane herein.
Kynoar-hexafluoropropylene (degree of crystallinity 37%) and toluene are dissolved in acetone, are stirred to and evenly obtain the second polymer solution.In this second polymer solution, the content of Kynoar-hexafluoropropylene is that the content of 12 % by weight, acetone is that the content of 78 % by weight, toluene is that 10 % by weight, the fixing rod of mayer are herein 4 μ m with the gap of polypropylene porous film.Again above-mentioned the second polymer solution is coated on the another side of polyethylene porous matrix, the above-mentioned polyethylene porous matrix that is coated with the second polymer solution is dried, obtain porous septum sample A4, the average pore size that shows the first perforated membrane is 0.09 μ m, and the average pore size of the second perforated membrane is 0.17 μ m.
The porous septum obtaining is inserted in battery container, and the ratio that is 4: 1 according to the weight ratio of electrolyte and porous septum in battery container, inject electrolyte, wherein, described electrolyte be in the mixed solvent that ethylene carbonate and dimethyl carbonate are 2: 1 according to volume ratio containing the bis trifluoromethyl sulfoamido lithium solution of 1M, after encapsulation, form polymer battery sample T4.
Embodiment 5
The present embodiment is used for illustrating battery diaphragm provided by the present invention and preparation method thereof.
Polymethyl methacrylate (degree of crystallinity 22%), Kynoar-chlorotrifluoroethylene (degree of crystallinity is 18%), Kynoar (degree of crystallinity 20%) and toluene are dissolved in acetone, stir, obtain the first polymer solution, in this first polymer solution, the content of Kynoar-hexafluoropropylene is 3 % by weight, the content of Kynoar-chlorotrifluoroethylene is 3%, the content of Kynoar is 2%, the content of ethanol is 15 % by weight, the content of zirconia (average grain diameter 60nm) is 3 % by weight, and the content of acetone is 74 % by weight.Polyethylene porous matrix is fixed on glass plate, uses the mayer rod of model #6, the first polymer solution is coated on a poly face.The above-mentioned polyethylene porous matrix that is coated with the first polymer solution is dried, obtains being attached to lip-deep first perforated membrane of porous matrix.Mayer rod is 4 μ m with the gap of polyethylene porous membrane herein, and the average pore size that shows the first perforated membrane is 0.1 μ m, and the average pore size of the second perforated membrane is 0.2 μ m.
Kynoar-hexafluoropropylene (degree of crystallinity 40%), Kynoar-chlorotrifluoroethylene (degree of crystallinity is 35%) and ethanol are dissolved in butanone, are stirred to and evenly obtain the second coating liquid.In this second polymer solution, the content of Kynoar-hexafluoropropylene is that the content of 4 % by weight, Kynoar-chlorotrifluoroethylene is that the content of 4 % by weight ethanol is that the content of 15 % by weight, zirconia (average grain diameter 60nm) is that the content of 1 % by weight, acetone is 76 % by weight.The fixing rod of mayer is herein 4 μ m with the gap of polypropylene porous film.Again above-mentioned the second polymer solution is coated on the another side of polyethylene porous matrix.The above-mentioned polyethylene porous matrix that is coated with the second polymer solution is dried, obtains being attached to another lip-deep second perforated membrane of porous matrix.
The polymer porous film obtaining is immersed to electrolyte solution.Wherein, described electrolyte is in propene carbonate/methyl ethyl carbonate/diethyl carbonate=2: the lithium hexafluoro phosphate lithium that contains 1M in the mixed solvent of 1: 1 (volume ratio).Flood after 60 minutes and take out and obtain according to polymer dielectric of the present invention.
Comparative example 1
Adopt the method identical with embodiment 1 to prepare polymer battery, the porosity of different is the first perforated membrane is 40%, the porosity of the second perforated membrane is 40%, the average pore size of the first perforated membrane is 0.07 μ m, the average pore size of the second perforated membrane is 0.07 μ m, the PPOX that the first perforated membrane is 40% by degree of crystallinity forms, the PPOX that the second perforated membrane is 40% by degree of crystallinity forms, in preparation first, during the second perforated membrane, the first coating liquid, polymer in the second coating liquid, the weight ratio of solvent and pore creating material is 3: 3: 4, the final polymer battery sample CT1 that obtains.
Embodiment 5-10
The present embodiment is used for the properties of the prepared sample of test implementation example 1-5, and described properties is as follows:
1, the mensuration of porosity: adopt mercury injection method to test the porosity of the porous septum of preparing in embodiment according to the regulation of GBT 21650.1-2008, test result is in Table 1.
2, loop test: adopt prepared perforated membrane, carry out the test of normal temperature 1C electric current charge-discharge performance.Record the surplus ratio of battery capacity after 400 times.The discharge capacity of battery before capability retention=(discharge capacity of battery before the discharge capacity-circulation of the battery after 400 times of circulating)/circulation wherein, test result is in Table 1.
Table 1
| Sample number into spectrum | The first perforated membrane porosity (%) | The second perforated membrane porosity (%) | Battery capacity surplus ratio (%) after 400 times circulates |
| T1 | 40 | 30 | 92 |
| T2 | 52 | 35 | 90 |
| T3 | 70 | 40 | 89 |
| T4 | 61 | 37 | 94 |
| T5 | 55 | 40 | 93 |
| CT1 | 40 | 40 | 75 |
From table 1, can find out that battery provided by the present invention has good cycle performance, and because polymer battery provided by the present invention structurally has asymmetric porous septum, thereby make Li dendrite be not easy to puncture barrier film, thereby polymer battery provided by the present invention has good cycle performance and good security performance simultaneously.
Claims (10)
1. a polymer battery, this polymer battery comprises positive pole, negative pole, polymer dielectric, described polymer dielectric is between positive pole and negative pole, this polymer dielectric comprises porous septum and electrolyte, wherein, electrolyte is contained in the hole of described porous septum with the form of gel/solution, porous septum comprises the first perforated membrane, the second perforated membrane and porous basement membrane, porous basement membrane is between the first perforated membrane and the second perforated membrane, wherein the porosity of the first perforated membrane is 40-70%, the porosity of the second perforated membrane is 30-40%, the porosity of porous basement membrane is 25-45%, the polymer that the first perforated membrane is 10-25% by degree of crystallinity forms, the polymer that the second perforated membrane is 25-40% by degree of crystallinity forms, the average pore size of described the first perforated membrane is 0.06-0.2 μ m, the average pore size of the second perforated membrane is 0.06-0.2 μ m, the average pore size of porous basement membrane is 0.02-0.08 μ m, and the first perforated membrane in polymer battery contacts with negative pole, the second perforated membrane contacts with anodal, wherein the first perforated membrane and the second perforated membrane have different pick ups.
2. polymer battery according to claim 1, the average pore size of described the first perforated membrane is 0.07-0.18 μ m, and the average pore size of the second perforated membrane is 0.07-0.18 μ m, and the average pore size of porous basement membrane is 0.03-0.08 μ m.
3. polymer battery according to claim 1, described the first perforated membrane and the second perforated membrane respectively independently one or more in Kynoar-hexafluoropropylene, Kynoar-chlorotrifluoroethylene, Kynoar, polymethyl methacrylate, polyethylene glycol oxide, PPOX, polyacrylonitrile, polyvinyl chloride, polyvinyl acetate form, porous basement membrane is fine by polyethylene, polypropylene, polyimides, polysulfones, polychlorostyrene carbamate, polyvinyl chloride, cellulose, polypropylene, one or more in polyvinylidene fluoride, polytetrafluoroethylene form.
4. polymer battery according to claim 1, the thickness of described the first perforated membrane is 2-15 μ m, and the thickness of porous basement membrane is 9-50 μ m, and the thickness of the second perforated membrane is 2-15 μ m, and the weight ratio of electrolyte and porous septum is 1-10:1.
5. a preparation method for polymer battery, the method comprises:
(1) will contain the first polymer and the first solvent, the first pore creating material obtains the first coating liquid after mixing, and the first coating liquid is coated onto on a surface of porous basement membrane; Heating, removes solvent and pore creating material in the first coating liquid for the first time, obtains the first perforated membrane; To contain the second polymer and the second solvent, the second pore creating material obtains the second coating liquid after mixing, and is coated onto on another surface of above-mentioned porous basement membrane; Heat for the second time, remove solvent and the pore creating material of the second coating liquid, obtain the second perforated membrane;
(2) anodal, negative pole are pressurizeed mutually compound with porous septum prepared by step (1) by heating, then complex is plugged in battery container, inject the electrolyte in battery container, electrolyte is contained in the hole of porous septum with the form of gel/solution, then encapsulation, obtains polymer battery, wherein, the first perforated membrane contacts with negative pole, and the second perforated membrane contacts with anodal;
The porosity of described the first perforated membrane is 40-70%, the porosity of the second perforated membrane is 30-40%, the porosity of porous basement membrane is 25-45%, the polymer that the first perforated membrane is 10-25% by degree of crystallinity forms, the polymer that the second perforated membrane is 25-40% by degree of crystallinity forms, the average pore size of described the first perforated membrane is 0.06-0.2 μ m, the average pore size of the second perforated membrane is 0.06-0.2 μ m, the average pore size of porous basement membrane is 0.02-0.08 μ m, the polymer that wherein forms the first perforated membrane is different from the degree of crystallinity of the polymer of composition the second perforated membrane, the first perforated membrane and the second perforated membrane have different pick ups.
6. the preparation method of polymer battery according to claim 5, the first polymer described in described step (1), the second polymer is independently selected from respectively Kynoar-hexafluoropropylene, Kynoar-chlorotrifluoroethylene, Kynoar, polymethyl methacrylate, polyethylene glycol oxide, PPOX, polyacrylonitrile, polyvinyl chloride, one or more in polyvinyl acetate, described the first solvent and described the second solvent are selected from acetone independently of one another, N, dinethylformamide, N, N-dimethylacetylamide, 1-METHYLPYRROLIDONE, acetonitrile, dimethyl sulfoxide (DMSO), one or more in butanone and oxolane.
7. the preparation method of polymer battery according to claim 5, the total weight of the first coating liquid of take in described step (1) is benchmark, the weight ratio of the first polymer, the first solvent and the first pore creating material is 2-30:30-96:2-40.
8. the preparation method of polymer battery according to claim 5, the temperature of heating for the first time described in described step (1) is 40-120 ℃, the time of heating is 1-60min.
9. the preparation method of polymer battery according to claim 5, the total weight of the second coating liquid of take in described step (1) is benchmark, the weight ratio of the second polymer, the second solvent and the second pore creating material is 2-30:30-96:2-40.
10. the preparation method of polymer battery according to claim 5, the heating-up temperature for the second time in wherein said step (1) is 40-120 ℃, the time of heating is 1-60min.
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| CN101662041A (en) * | 2008-08-29 | 2010-03-03 | 深圳市比克电池有限公司 | Method for preparing gel polymer lithium ion battery |
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| WO1998037589A1 (en) * | 1997-02-21 | 1998-08-27 | Motorola Inc. | Polymeric electrolyte and electrochemical cell using same |
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| US6187231B1 (en) * | 1996-10-01 | 2001-02-13 | Celanese Ventures Gmbh | Process for producing polymeric films for use as fuel cells |
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| CN101662041A (en) * | 2008-08-29 | 2010-03-03 | 深圳市比克电池有限公司 | Method for preparing gel polymer lithium ion battery |
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