CN102190839B - Gel polymer lithium ion battery, porous composite electrode and porous membrane composition - Google Patents
Gel polymer lithium ion battery, porous composite electrode and porous membrane composition Download PDFInfo
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- CN102190839B CN102190839B CN201010119052.2A CN201010119052A CN102190839B CN 102190839 B CN102190839 B CN 102190839B CN 201010119052 A CN201010119052 A CN 201010119052A CN 102190839 B CN102190839 B CN 102190839B
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- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 111
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 79
- 229920000642 polymer Polymers 0.000 title claims abstract description 73
- 239000002131 composite material Substances 0.000 title claims abstract description 26
- 239000000203 mixture Substances 0.000 title claims abstract description 21
- 239000012528 membrane Substances 0.000 title abstract description 4
- 239000000843 powder Substances 0.000 claims abstract description 73
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims abstract description 38
- 238000000034 method Methods 0.000 claims abstract description 33
- 239000002904 solvent Substances 0.000 claims abstract description 29
- 239000003960 organic solvent Substances 0.000 claims abstract description 10
- 239000000243 solution Substances 0.000 claims description 41
- 239000011259 mixed solution Substances 0.000 claims description 34
- 230000032683 aging Effects 0.000 claims description 32
- 239000011244 liquid electrolyte Substances 0.000 claims description 29
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 28
- 239000003292 glue Substances 0.000 claims description 25
- 235000015110 jellies Nutrition 0.000 claims description 25
- 239000008274 jelly Substances 0.000 claims description 25
- 238000011049 filling Methods 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 17
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 15
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 14
- 238000000576 coating method Methods 0.000 claims description 14
- 239000000499 gel Substances 0.000 claims description 14
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 14
- 238000002360 preparation method Methods 0.000 claims description 13
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 11
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 7
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 7
- 239000008151 electrolyte solution Substances 0.000 claims description 7
- 238000005096 rolling process Methods 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 238000007766 curtain coating Methods 0.000 claims description 6
- VUPKGFBOKBGHFZ-UHFFFAOYSA-N dipropyl carbonate Chemical compound CCCOC(=O)OCCC VUPKGFBOKBGHFZ-UHFFFAOYSA-N 0.000 claims description 6
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 5
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- CXHHBNMLPJOKQD-UHFFFAOYSA-M methyl carbonate Chemical compound COC([O-])=O CXHHBNMLPJOKQD-UHFFFAOYSA-M 0.000 claims description 4
- 238000005507 spraying Methods 0.000 claims description 4
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 3
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 3
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 3
- 239000013543 active substance Substances 0.000 claims description 3
- 239000011248 coating agent Substances 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 125000002573 ethenylidene group Chemical group [*]=C=C([H])[H] 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 15
- 239000007788 liquid Substances 0.000 abstract description 5
- 229920000098 polyolefin Polymers 0.000 abstract description 3
- 229920005569 poly(vinylidene fluoride-co-hexafluoropropylene) Polymers 0.000 abstract 3
- 239000002033 PVDF binder Substances 0.000 abstract 1
- 238000010521 absorption reaction Methods 0.000 abstract 1
- 230000002349 favourable effect Effects 0.000 abstract 1
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical group FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 abstract 1
- 230000004888 barrier function Effects 0.000 description 30
- 230000014759 maintenance of location Effects 0.000 description 30
- 150000001875 compounds Chemical class 0.000 description 20
- 239000006185 dispersion Substances 0.000 description 15
- 238000004090 dissolution Methods 0.000 description 15
- 238000005516 engineering process Methods 0.000 description 7
- 238000002156 mixing Methods 0.000 description 5
- 239000004902 Softening Agent Substances 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 229910003002 lithium salt Inorganic materials 0.000 description 3
- 159000000002 lithium salts Chemical class 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical class CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 239000011245 gel electrolyte Substances 0.000 description 2
- 239000012982 microporous membrane Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 230000006798 recombination Effects 0.000 description 2
- 238000005215 recombination Methods 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000000274 adsorptive effect Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 210000000988 bone and bone Anatomy 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 229920006037 cross link polymer Polymers 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000005486 organic electrolyte Substances 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 239000005518 polymer electrolyte Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
Classifications
-
- 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)
Abstract
The invention discloses a composition for preparing a porous membrane of a lithium ion battery electrode. The composition comprises 1-20% of polyvinylidene fluoride-hexafluoropropylene, 0.1-20% of inorganic ultrafine powder, and 0.1-20% of non-solvent and organic solvent of the polyvinylidene fluoride-hexafluoropropylene, wherein the mass ratio of hexafluoropropylene to polyvinylidene fluoride in the polyvinylidene fluoride-hexafluoropropylene is (6-20):100. The invention also discloses a lithium ion battery porous composite electrode and gel polymer lithium ion battery prepared from the composition. The technical process for preparing the gel polymer battery is simple, and does not need to add a polyolefin porous membrane in the assembly process, so that the production cost of the battery is greatly lowered and the production technique has wide application range; the composite porous electrode has the advantages of high liquid absorption rate and high porosity; and the battery has the advantages of favorable cycle performance and high conductivity.
Description
Technical field
The invention belongs to battery manufacture field, specifically relate to composition, lithium ion battery porous composite pole piece and gel polymer lithium ion battery for the preparation of electrodes of lithium-ion batteries porous-film.
Background technology
In existing lithium ion battery making processes, mostly adopt liquid electrolyte, liquid electrolyte is dissolved in carbonates organic solvent and is formed by lithium salts.For liquid electrolyte, in charge and discharge process, easily decompose and produce gas, form excessive vapour pressure at inside battery, easily there is bulging distortion in battery, even can be due to the excessive vapour pressure safety problem such as blast.Secondly, the easy corrosion cell shell of liquid electrolyte, causes leakage etc.Liquid state organic electrolyte is imflammable solvent in addition, and the danger such as blast on fire easily occur.
Polymer Li-ion battery is the new green environment protection chemical energy source occurring the nineties in 20th century.It has the advantages such as voltage is high, specific energy large, discharging voltage balance, good cycle, high-temperature behavior is good, safety performance is good and grow storage time.
Existing jelly glue polymer battery mainly contains two kinds of preparation methods: one is Bellcore technology, and another is on-site polymerization.
Bellcore technology is mainly announced in 1994 by bell communication research institute of the U.S. (Bellcore).They have delivered the patented technology of " a kind of polymer dielectric preparation method " (U.S. Patent number: US5296318) by name.According to the production technique of Bel's technology, need first polyvinylidene difluoride (PVDF)-R 1216 P (VDF-HFP) to be dissolved, added a large amount of plasticizer phthalic acid dibutylesters (DBP), silica dioxide granule, be coated on and on substrate, make P (VDF-HFP) film, then use a large amount of low boiling point solvents (as methyl alcohol) that softening agent is extracted, obtain microporous membrane, finally by compound to microporous membrane and electrode layer roll-in, make porous composite pole piece, in drying room, inject liquid electrolyte and make it activation and obtain polymer Li-ion battery.The shortcoming of this technology maximum is that technique is too complicated, and cost is high, and the extraction process of softening agent is complicated and be difficult to control, and hot recombination process easily produces micro-short circuit, causes battery decrease in yield.
And on-site polymerization is mainly that polymer monomer, initiator, electrolyte lithium salt are added in the battery assembling, makes polymer monomer generation polymerization by on-the-spot light or thermal initiation, thereby prepare jelly glue polymer battery.The greatest drawback of the method is, very harsh to oxygen and moisture requirement when polymerization, once the inadequate words of gel polymerisation can cause the performance of battery sharply to worsen.
Summary of the invention
The object of the invention is the too complexity of production technique in order to make up lithium ion battery porous composite pole piece in prior art, cost is high, the extraction process of softening agent is complicated and be difficult to control, hot recombination process easily produces micro-short circuit, cause the defect of battery decrease in yield, for providing one, people can simplify the technological process of production, the composition for the preparation of electrodes of lithium-ion batteries porous-film saving production cost.
Another object of the present invention is to provide a kind of lithium ion battery porous composite pole piece that adopts above-mentioned composition to prepare.
A further object of the present invention is to provide a kind of gel polymer lithium ion battery that contains above-mentioned porous composite pole piece and preparation method thereof.
The object of the invention is to realize by following technical proposals.
The invention discloses a kind of composition for the preparation of electrodes of lithium-ion batteries porous-film, described composition comprises:
Polyvinylidene difluoride (PVDF)-R 1216, wherein the mass ratio of R 1216 and vinylidene is 6～20: 100;
Inorganic superfine powder body;
Organic solvent;
The non-solvent of polyvinylidene difluoride (PVDF)-R 1216;
In described composition, the mass concentration of polyvinylidene difluoride (PVDF)-R 1216 is 1%～20%, and the mass concentration of inorganic superfine powder body is 0.1%～20%, and the mass concentration of non-solvent is 0.1%～20%.
Described organic solvent is preferably a kind of or several combination arbitrarily in dimethyl formamide, N,N-DIMETHYLACETAMIDE, dimethyl sulfoxide (DMSO), acetone, N-Methyl pyrrolidone or tetrahydrofuran (THF).
Described inorganic superfine powder body is preferably SiO
2, Al
2o
3, TiO
2, MgO or ZrO
2in a kind of or arbitrarily several combination.
Described non-solvent is preferably a kind of or several combination arbitrarily in ethanol, deionized water, Virahol, hexanaphthene, propyl carbinol, NSC 11801, propylene carbonate, methylcarbonate, diethyl carbonate or dipropyl carbonate.
In the concrete embodiment of the present invention, the preparation process of described composition comprises:
Polyvinylidene difluoride (PVDF)-R 1216 is dissolved in organic solvent, be configured to polyvinylidene difluoride (PVDF)-R 1216 solution, in polyvinylidene difluoride (PVDF)-R 1216 solution, add inorganic superfine powder body and mix, then inject the non-solvent of polyvinylidene difluoride (PVDF)-R 1216, ageing after stirring, makes the mixed solution of polyvinylidene difluoride (PVDF)-R 1216-superfine powder.
The present invention further discloses a kind of lithium ion battery porous composite pole piece, described pole piece is the active substance top layer that above-mentioned composition is coated to electrodes of lithium-ion batteries, can make solvent evaporates through heated baking, on pole piece, form composite porous film, thus the lithium ion battery porous composite pole piece obtaining.
The method of described coating can be curtain coating coating method, scraper for coating method, spraying method, rolling method or woodburytype.
The invention also discloses a kind of gel polymer lithium ion battery, described battery contains above-mentioned porous composite pole piece.
The invention also discloses a kind of preparation method of gel polymer lithium ion battery, described method comprises:
The active substance top layer that above-mentioned composition is coated to electrodes of lithium-ion batteries, can make solvent evaporates through heated baking, forms composite porous film on pole piece, obtains lithium ion battery porous composite pole piece;
Gained positive and negative plate assembles, and to assembling after battery in inject liquid electrolyte, battery is carried out after preliminary filling, again battery is carried out to heating and pressurizing baking, make composite porous film and electrolytic solution form gel, then carry out partial volume technique, make jelly glue polymer battery.
Described heating and pressurizing baking, Heating temperature scope is 60～100 DEG C, and pressure range is 0.2～1.0mPa, and be 0.5h～7h total heat-up time.
The technological process that present method is made jelly glue polymer battery is simple, need in the time of assembling, not add polyolefins porous diaphragm, greatly reduces the production cost of battery, and production technique is applied widely; The composite porous electrode pick up of manufacturing is high, porosity is high, Stability Analysis of Structures, cycle performance of battery, conducts electricity very well.Because inside battery ionogen exists with gel state, greatly improve the high-temperature behavior of battery, and avoided liquid cell problem, the problem includes: problems such as bulging leakages.Because battery is after gelation, there is not liquid electrolyte in inside, therefore greatly improved the safety performance of lithium ion battery.
Brief description of the drawings
Fig. 1 is the making schema of jelly glue polymer battery of the present invention;
Fig. 2 is the jelly glue polymer battery cycle life figure of the embodiment of the present invention 1;
Fig. 3 is the jelly glue polymer battery multiplying power discharging graphic representation of the embodiment of the present invention 1.
Embodiment:
The invention discloses a kind of novel method of utilizing combined electrode to prepare gel polymer lithium ion battery, the copolymer p of biasfluoroethylene-hexafluoropropylene (VDF-HFP) is dissolved in organic solvent, and add inorganic superfine powder body and a small amount of P (VDF-HFP) non-solvent, make the mixing solutions of P (VDF-HFP), again mixing solutions is coated on battery positive/negative plate, make solvent evaporates, on positive/negative plate, form composite porous film, then the positive/negative plate that comprises composite porous film is assembled into battery, and to assembling after battery in inject liquid electrolyte, battery is carried out to heating and pressurizing baking, make composite porous film and electrolytic solution form gel electrolyte, thereby make jelly glue polymer battery.
The present invention adopts the surface film of P (VDF-HFP) multipolymer as gel electrolyte, because PVDF has good resistance to anodic oxidation ability and physical strength, it also has larger specific inductivity in addition, be conducive to the dissociation of lithium salts, thereby improve the concentration of current carrier in polymer dielectric.In PVDF, introduce the degree of crystallinity that HFP can reduce PVDF, improve the ability of its adsorbing electrolyte solution.
The present invention adopts solvent pairs separation boring technique to prepare lithium ion battery porous composite pole piece, and the mixed solution of coating liquid comprises solvent and the non-solvent of P (VDF-HFP).After mixing solutions is coated on positive/negative plate, utilize the boiling-point difference of solvent and non-solvent, along with the volatilization of upper layer low boiling point solvent, organic solution starts phase-splitting, produces the mutually rich and stingy of organic polymer.Richness mutually in solvent few, polymkeric substance just precipitates into membrane bone frame, and is now distributed in stingy still more containing non-solvent in skeleton, after this part solvent slowly volatilizees, in stingy solution, a small amount of polymkeric substance shrinks with regard to crystallization and invests on skeleton, thereby produces micropore.And owing to having added inorganic superfine powder body in mixed solution, further strengthened the microvoid structure in combined electrode, more contribute to strengthen the adsorptive power of positive/negative plate to electrolytic solution.After solvent evaporates, P (VDF-HFP) forms uniform film, and the physical strength of this layer film is poor, plays a supporting role and positive/negative plate can be used as dirt settling.We utilize solvent pairs to separate boring technique, have save the step of utilizing low boiling point solvent extract softening agent in Bel's technology, have greatly simplified the technological process of production of battery, have saved production cost.
After composite porous film forms on pole piece, inject liquid electrolyte, the microvoid structure on compound porous pole piece absorbs a large amount of liquid electrolytes, and electrolytic solution is retained in micropore.Conventional lithium ion battery liquid electrolyte used is all applicable to the present invention.By heating, the organic solvent of liquid electrolyte is partly dissolved or swelling in P (VDF-HFP) micropore bracket.After cooling, solvent is gel with the swellable polymer system that the cross-linked polymer solid that can not be dissolved in wherein forms.In addition, heating and pressurization can make the P (VDF-HFP) of microporous polymer electrolyte film and the binding agent on pole piece produce the crosslinked of physics or chemistry, thereby make battery core internal structure tightr, be conducive to the smooth transmission conduction of lithium ion between inside battery positive and negative electrode.
To assemble by the prepared lithium ion battery positive and negative plate of the present invention, and to assembling after battery in inject liquid electrolyte, battery is carried out after preliminary filling, again battery is carried out to heating and pressurizing baking, Heating temperature scope is 60～100 DEG C, pressure range is 0.2～1.0mPa, and be 0.5h～7h total heat-up time.Make composite porous film and electrolytic solution form gel, then carry out partial volume technique, make jelly glue polymer battery, basically identical with existing liquid lithium ionic cell production technique, can additionally not increase battery preparation cost.And the prepared battery of the present invention, without adding polyolefins porous diaphragm, greatly reduces the manufacturing cost of battery, has simplified the process flow for assembling of lithium ion battery.
The invention is further illustrated by the following examples, and the present invention is not limited only to described embodiment.
Embodiment mono-
By 50.00g HFP: P (VDF-HFP) powder dissolution that VDF mass ratio is 15: 100, in 4.92kg tetrahydrofuran (THF), is mixed with P (VDF-HFP) solution.Again by 5.00g TiO
2dispersion of ultrafine powder, in above-mentioned P (VDF-HFP) solution, mixes, and then slowly injects 25.00g propyl carbinol, and P (VDF-HFP)-superfine powder mixed solution is made in ageing after stirring.
By above-mentioned gained P (VDF-HFP)-superfine powder mixed solution, adopt curtain coating coating method to be coated to lithium ion battery positive and negative plate top layer, after overbaking is dry, make the compound positive and negative plate of lithium ion battery porous.
The compound positive and negative plate of above-mentioned lithium ion battery porous is assembled into battery, injects liquid electrolyte.Battery is carried out to preliminary filling, then use the pressure of 0.5MPa, at 70 DEG C, battery is toasted to 4.0h, then after normal aging partial volume, make jelly glue polymer battery.
The cycle life figure of this routine gained gel polymer lithium ion battery and multiplying power discharging graphic representation are respectively as shown in Figures 2 and 3, result shows, its 300 times and 500 capability retentions adopt the polymer Li-ion battery of barrier film basic identical with tradition, and capability retention when 0.2C, 0.5C, 1C electric discharge adopts the polymer Li-ion battery of barrier film basic identical with tradition.
Embodiment bis-
By 250.00g HFP: P (VDF-HFP) powder dissolution that VDF mass ratio is 10: 100, in 4.40kg dimethyl formamide, is mixed with P (VDF-HFP) solution.Again by 50.00g MgO dispersion of ultrafine powder in above-mentioned P (VDF-HFP) solution, mix, then slowly inject 300.00g dipropyl carbonate, ageing after stirring, makes P (VDF-HFP)-superfine powder mixed solution.
By above-mentioned gained P (VDF-HFP)-superfine powder mixed solution, adopt curtain coating coating method to be coated to lithium ion battery positive and negative plate top layer, after overbaking is dry, make the compound positive and negative plate of lithium ion battery porous.
The compound positive and negative plate of above-mentioned lithium ion battery porous is assembled into battery, injects liquid electrolyte, battery is carried out to preliminary filling, then use the pressure of 0.4MPa, at 90 DEG C, battery is toasted to 5.0h, then after normal aging partial volume, make jelly glue polymer battery.
After tested, the battery that this example is made, its 300 times and 500 capability retentions adopt the polymer Li-ion battery of barrier film basic identical with tradition, and capability retention when 0.2C, 0.5C, 1C electric discharge adopts the polymer Li-ion battery of barrier film basic identical with tradition.
Embodiment tri-
By 500.00g HFP: P (VDF-HFP) powder dissolution that VDF mass ratio is 12: 100, in 3.60kg dimethyl sulfoxide (DMSO), is mixed with P (VDF-HFP) solution.Again by 300.00g Al
2o
3dispersion of ultrafine powder, in above-mentioned P (VDF-HFP) solution, mixes.Then slowly inject 600.00g propylene carbonate, ageing after stirring, makes P (VDF-HFP)-superfine powder mixed solution.
By above-mentioned gained P (VDF-HFP)-superfine powder mixed solution, adopt rolling method to be coated to lithium ion battery positive and negative plate top layer, after overbaking is dry, make the compound positive and negative plate of lithium ion battery porous.
The compound positive and negative plate of above-mentioned lithium ion battery porous is assembled into battery, injects liquid electrolyte, battery is carried out to preliminary filling, then use the pressure of 0.6MPa, at 80 DEG C, battery is toasted to 3.0h, then after normal aging partial volume, make jelly glue polymer battery.
After tested, the battery that this example is made, its 300 times and 500 capability retentions adopt the polymer Li-ion battery of barrier film basic identical with tradition, and capability retention when 0.2C, 0.5C, 1C electric discharge adopts the polymer Li-ion battery of barrier film basic identical with tradition.
Embodiment tetra-
By 750.00g HFP: P (VDF-HFP) powder dissolution that VDF mass ratio is 10: 100, in 2.35kg N,N-DIMETHYLACETAMIDE, is mixed with P (VDF-HFP) solution.Again by 1000.00g ZrO
2dispersion of ultrafine powder, in above-mentioned P (VDF-HFP) solution, mixes.Then slowly inject 900.00g propylene carbonate, ageing after stirring, makes P (VDF-HFP)-superfine powder mixed solution.
By above-mentioned gained P (VDF-HFP)-superfine powder mixed solution, adopt scraper for coating method to be coated to lithium ion battery positive and negative plate top layer, after overbaking is dry, make the compound positive and negative plate of lithium ion battery porous.
Above-mentioned lithium ion battery positive and negative plate is assembled into battery, injects liquid electrolyte, battery is carried out to preliminary filling, then use the pressure of 0.3MPa, at 100 DEG C, battery is toasted to 1.0h, then after normal aging partial volume, make jelly glue polymer battery.
After tested, the battery that this example is made, its 300 times and 500 capability retentions adopt the polymer Li-ion battery of barrier film basic identical with tradition, and capability retention when 0.2C, 0.5C, 1C electric discharge adopts the polymer Li-ion battery of barrier film basic identical with tradition.
Embodiment five
By 500.00g HFP: P (VDF-HFP) powder dissolution that VDF mass ratio is 6: 100, in 3.60kg N-Methyl pyrrolidone, is mixed with P (VDF-HFP) solution.Again by 600.00g TiO
2dispersion of ultrafine powder, in above-mentioned P (VDF-HFP) solution, mixes.Then slowly inject 300.00g NSC 11801, ageing after stirring, makes P (VDF-HFP)-superfine powder mixed solution.
By above-mentioned gained P (VDF-HFP)-superfine powder mixed solution, adopt rolling method to be coated to lithium ion battery positive and negative plate top layer, after overbaking is dry, make the compound positive and negative plate of lithium ion battery porous.Above-mentioned lithium ion battery positive and negative plate is assembled into battery, injects liquid electrolyte, battery is carried out to preliminary filling, then use the pressure of 0.3MPa, at 95 DEG C, battery is toasted to 2.0h, then after normal aging partial volume, make jelly glue polymer battery.
After tested, the battery that this example is made, its 300 times and 500 capability retentions adopt the polymer Li-ion battery of barrier film basic identical with tradition, and capability retention when 0.2C, 0.5C, 1C electric discharge adopts the polymer Li-ion battery of barrier film basic identical with tradition.
Embodiment six
By 1000.00g HFP: P (VDF-HFP) powder dissolution that VDF mass ratio is 20: 100, in 2.25kg dimethyl formamide, is mixed with P (VDF-HFP) solution.Again by 750.00g SiO
2dispersion of ultrafine powder, in above-mentioned P (VDF-HFP) solution, mixes.Then slowly inject 1000.00g dipropyl carbonate, ageing after stirring, makes P (VDF-HFP)-superfine powder mixed solution.
By above-mentioned gained P (VDF-HFP)-superfine powder mixed solution, adopt scraper for coating method to be coated to lithium ion battery positive and negative plate top layer, after overbaking is dry, make the compound positive and negative plate of lithium ion battery porous.Above-mentioned lithium ion battery positive and negative plate is assembled into battery, injects liquid electrolyte, battery is carried out to preliminary filling, then use the pressure of 0.4MPa, at 80 DEG C, battery is toasted to 6.0h, then after normal aging partial volume, make jelly glue polymer battery.
After tested, the battery that this example is made, its 300 times and 500 capability retentions adopt the polymer Li-ion battery of barrier film basic identical with tradition, and capability retention when 0.2C, 0.5C, 1C electric discharge adopts the polymer Li-ion battery of barrier film basic identical with tradition.
Embodiment seven
By 250.00g HFP: P (VDF-HFP) powder dissolution that VDF mass ratio is 10: 100, in 4.43kg acetone, is mixed with P (VDF-HFP) solution.Again by 20.00g SiO
2dispersion of ultrafine powder, in above-mentioned P (VDF-HFP) solution, mixes.Then slowly inject 300.00g methylcarbonate, ageing after stirring, makes P (VDF-HFP)-superfine powder mixed solution.
By above-mentioned gained P (VDF-HFP)-superfine powder mixed solution, adopt rolling method to be coated to lithium ion battery positive and negative plate top layer, after overbaking is dry, make the compound positive and negative plate of lithium ion battery porous.Above-mentioned lithium ion battery positive and negative plate is assembled into battery, injects liquid electrolyte, battery is carried out to preliminary filling, then use the pressure of 0.4MPa, at 85 DEG C, battery is toasted to 5.0h, then after normal aging partial volume, make jelly glue polymer battery.
After tested, the battery that this example is made, its 300 times and 500 capability retentions adopt the polymer Li-ion battery of barrier film basic identical with tradition, and capability retention when 0.2C, 0.5C, 1C electric discharge adopts the polymer Li-ion battery of barrier film basic identical with tradition.
Embodiment eight
By 250.00g HFP: P (VDF-HFP) powder dissolution that VDF mass ratio is 12: 100, in 4.55kg acetone, is mixed with P (VDF-HFP) solution.Again by 50.00gAl
2o
3dispersion of ultrafine powder, in above-mentioned P (VDF-HFP) solution, mixes.Then slowly inject 150.00g deionized water, ageing after stirring, makes P (VDF-HFP)-superfine powder mixed solution.
By above-mentioned gained P (VDF-HFP)-superfine powder mixed solution, adopt spraying method to be coated to lithium ion battery positive and negative plate top layer, after overbaking is dry, make the compound positive and negative plate of lithium ion battery porous.Above-mentioned lithium ion battery positive and negative plate is assembled into battery, injects liquid electrolyte, battery is carried out to preliminary filling, then use the pressure of 0.5MPa, at 80 DEG C, battery is toasted to 6.0h, then after normal aging partial volume, make jelly glue polymer battery.
After tested, the battery that this example is made, its 300 times and 500 capability retentions adopt the polymer Li-ion battery of barrier film basic identical with tradition, and capability retention when 0.2C, 0.5C, 1C electric discharge adopts the polymer Li-ion battery of barrier film basic identical with tradition.
Embodiment nine
By 50.00g HFP: P (VDF-HFP) powder dissolution that VDF mass ratio is 6: 100, in 4.92kg acetone, is mixed with P (VDF-HFP) solution.Again by 25.00g SiO
2dispersion of ultrafine powder, in above-mentioned P (VDF-HFP) solution, mixes.Then slowly inject 5.00g ethanol, ageing after stirring, makes P (VDF-HFP)-superfine powder mixed solution.
By above-mentioned gained P (VDF-HFP)-superfine powder mixed solution, adopt rolling method to be coated to lithium ion battery positive and negative plate top layer, after overbaking is dry, make the compound positive and negative plate of lithium ion battery porous.Above-mentioned lithium ion battery positive and negative plate is assembled into battery, injects liquid electrolyte, battery is carried out to preliminary filling, then use the pressure of 0.2MPa, at 85 DEG C, battery is toasted to 0.5h, then after normal aging partial volume, make jelly glue polymer battery.
After tested, the battery that this example is made, its 300 times and 500 capability retentions adopt the polymer Li-ion battery of barrier film basic identical with tradition, and capability retention when 0.2C, 0.5C, 1C electric discharge adopts the polymer Li-ion battery of barrier film basic identical with tradition.
Embodiment ten
By 250.00g HFP: P (VDF-HFP) powder dissolution that VDF mass ratio is 20: 100, in 4.55kg tetrahydrofuran (THF), is mixed with P (VDF-HFP) solution.Again by 50.00g TiO
2dispersion of ultrafine powder, in above-mentioned P (VDF-HFP) solution, mixes.Then slowly inject 150.00g hexanaphthene, ageing after stirring, makes P (VDF-HFP)-superfine powder mixed solution.
By above-mentioned gained P (VDF-HFP)-superfine powder mixed solution, adopt curtain coating coating method to be coated to lithium ion battery positive and negative plate top layer, after overbaking is dry, make the compound positive and negative plate of lithium ion battery porous.Above-mentioned lithium ion battery positive and negative plate is assembled into battery, injects liquid electrolyte, battery is carried out to preliminary filling, then use the pressure of 0.5MPa, at 75 DEG C, battery is toasted to 7.0h, then after normal aging partial volume, make jelly glue polymer battery.
After tested, the battery that this example is made, its 300 times and 500 capability retentions adopt the polymer Li-ion battery of barrier film basic identical with tradition, and capability retention when 0.2C, 0.5C, 1C electric discharge adopts the polymer Li-ion battery of barrier film basic identical with tradition.
Embodiment 11
By 500.00g HFP: P (VDF-HFP) powder dissolution that VDF mass ratio is 15: 100, in 3.90kg tetrahydrofuran (THF), is mixed with P (VDF-HFP) solution.Again by 200.00g SiO
2and 100.00gZrO
2dispersion of ultrafine powder, in above-mentioned P (VDF-HFP) solution, mixes.Then slowly inject 300.00g Virahol, ageing after stirring, makes P (VDF-HFP)-superfine powder mixed solution.
By above-mentioned gained P (VDF-HFP)-superfine powder mixed solution, adopt rolling method to be coated to lithium ion battery positive and negative plate top layer, after overbaking is dry, make the compound positive and negative plate of lithium ion battery porous.Above-mentioned lithium ion battery positive and negative plate is assembled into battery, injects liquid electrolyte, battery is carried out to preliminary filling, then use the pressure of 0.3MPa, at 80 DEG C, battery is toasted to 6.0h, then after normal aging partial volume, make jelly glue polymer battery.
After tested, the battery that this example is made, its 300 times and 500 capability retentions adopt the polymer Li-ion battery of barrier film basic identical with tradition, and capability retention when 0.2C, 0.5C, 1C electric discharge adopts the polymer Li-ion battery of barrier film basic identical with tradition.
Embodiment 12
By 50.00g HFP: P (VDF-HFP) powder dissolution that VDF mass ratio is 15: 100, in 4.85kg acetone, is mixed with P (VDF-HFP) solution.Again by 25.00g TiO
2with 25.00g Al
2o
3dispersion of ultrafine powder, in above-mentioned P (VDF-HFP) solution, mixes.Then slowly inject 5.00g methylcarbonate, ageing after stirring, makes P (VDF-HFP)-superfine powder mixed solution.
By above-mentioned gained P (VDF-HFP)-superfine powder mixed solution, adopt spraying method to be coated to lithium ion battery positive and negative plate top layer, after overbaking is dry, make the compound positive and negative plate of lithium ion battery porous.Above-mentioned lithium ion battery positive and negative plate is assembled into battery, injects liquid electrolyte, battery is carried out to preliminary filling, then use the pressure of 0.5MPa, at 80 DEG C, battery is toasted to 6.0h, then after normal aging partial volume, make jelly glue polymer battery.
After tested, the battery that this example is made, its 300 times and 500 capability retentions adopt the polymer Li-ion battery of barrier film basic identical with tradition, and capability retention when 0.2C, 0.5C, 1C electric discharge adopts the polymer Li-ion battery of barrier film basic identical with tradition.
Embodiment 13
By 1000.00g HFP: P (VDF-HFP) powder dissolution that VDF mass ratio is 10: 100, in 1.40kg tetrahydrofuran (THF) and 1.40kg acetone mixing solutions, is mixed with P (VDF-HFP) solution.Again by 250.00g MgO and 50.00g TiO
2dispersion of ultrafine powder, in above-mentioned P (VDF-HFP) solution, mixes.Then slowly inject 900.00g diethyl carbonate, ageing after stirring, makes P (VDF-HFP)-superfine powder mixed solution.
By above-mentioned gained P (VDF-HFP)-superfine powder mixed solution, adopt scraper for coating method to be coated to lithium ion battery positive and negative plate top layer, after overbaking is dry, make the compound positive and negative plate of lithium ion battery porous.Above-mentioned lithium ion battery positive and negative plate is assembled into battery, injects liquid electrolyte, battery is carried out to preliminary filling, then use the pressure of 0.5MPa, at 75 DEG C, battery is toasted to 5.0h, then after normal aging partial volume, make jelly glue polymer battery.
After tested, the battery that this example is made, its 300 times and 500 capability retentions adopt the polymer Li-ion battery of barrier film basic identical with tradition, and capability retention when 0.2C, 0.5C, 1C electric discharge adopts the polymer Li-ion battery of barrier film basic identical with tradition.
Embodiment 14
By 750.00g HFP: P (VDF-HFP) powder dissolution that VDF mass ratio is 6: 100, in 2.79kg dimethyl formamide and 0.56kg N,N-DIMETHYLACETAMIDE mixing solutions, is mixed with P (VDF-HFP) solution.Again by 600.00g SiO
2dispersion of ultrafine powder, in above-mentioned P (VDF-HFP) solution, mixes.Then slowly inject 225.00g dipropyl carbonate and 75.00g propylene carbonate, ageing after stirring, makes P (VDF-HFP)-superfine powder mixed solution.
By above-mentioned gained P (VDF-HFP)-superfine powder mixed solution, adopt curtain coating coating method to be coated to lithium ion battery positive and negative plate top layer, after overbaking is dry, make the compound positive and negative plate of lithium ion battery porous.Above-mentioned lithium ion battery positive and negative plate is assembled into battery, injects liquid electrolyte, battery is carried out to preliminary filling, then use the pressure of 0.5MPa, at 70 DEG C, battery is toasted to 4.0h, then after normal aging partial volume, make jelly glue polymer battery.
After tested, the battery that this example is made, its 300 times and 500 capability retentions adopt the polymer Li-ion battery of barrier film basic identical with tradition, and capability retention when 0.2C, 0.5C, 1C electric discharge adopts the polymer Li-ion battery of barrier film basic identical with tradition.
Embodiment 15
By 500.00g HFP: P (VDF-HFP) powder dissolution that VDF mass ratio is 12: 100, in 4.20kg tetrahydrofuran (THF), is mixed with P (VDF-HFP) solution.Again by 295.00g ZrO
2dispersion of ultrafine powder, in above-mentioned P (VDF-HFP) solution, mixes.Then slowly inject 3.00g propyl carbinol and 2.00g dipropyl carbonate, ageing after stirring, makes P (VDF-HFP)-superfine powder mixed solution.
By above-mentioned gained P (VDF-HFP)-superfine powder mixed solution, adopt woodburytype to be coated to lithium ion battery positive and negative plate top layer, after overbaking is dry, make the compound positive and negative plate of lithium ion battery porous.Above-mentioned lithium ion battery positive and negative plate is assembled into battery, injects liquid electrolyte, battery is carried out to preliminary filling, then use the pressure of 0.4MPa, at 60 DEG C, battery is toasted to 6.0h, then after normal aging partial volume, make jelly glue polymer battery.
After tested, the battery that this example is made, its 300 times and 500 capability retentions adopt the polymer Li-ion battery of barrier film basic identical with tradition, and capability retention when 0.2C, 0.5C, 1C electric discharge adopts the polymer Li-ion battery of barrier film basic identical with tradition.
Above content is in conjunction with concrete embodiment further description made for the present invention, can not assert that specific embodiment of the invention is confined to these explanations.For general technical staff of the technical field of the invention, without departing from the inventive concept of the premise, can also make some simple deduction or replace, all should be considered as belonging to protection scope of the present invention.
Claims (1)
1. a preparation method for gel polymer lithium ion battery, described method comprises:
By be coated to the active substance top layer of electrodes of lithium-ion batteries for the preparation of the composition of electrodes of lithium-ion batteries porous-film, make solvent evaporates, on pole piece, form composite porous film, obtain lithium ion battery porous composite pole piece; The method of described coating is curtain coating coating method, scraper for coating method, spraying method, rolling method or woodburytype;
The described composition for the preparation of electrodes of lithium-ion batteries porous-film comprises:
Polyvinylidene difluoride (PVDF)-R 1216, wherein the mass ratio of R 1216 and vinylidene is 6～20:100;
Inorganic superfine powder body;
Organic solvent;
The non-solvent of polyvinylidene difluoride (PVDF)-R 1216;
In described composition, the mass concentration of polyvinylidene difluoride (PVDF)-R 1216 is 1%～20%, and the mass concentration of inorganic superfine powder body is 0.1%～20%, and the mass concentration of non-solvent is 0.1%～20%;
Described organic solvent is a kind of or several combination arbitrarily in dimethyl formamide, N,N-DIMETHYLACETAMIDE, dimethyl sulfoxide (DMSO), acetone, N-Methyl pyrrolidone or tetrahydrofuran (THF);
Described inorganic superfine powder body is SiO
2, Al
2o
3, TiO
2, MgO or ZrO
2in a kind of or arbitrarily several combination;
Described non-solvent is a kind of or several combination arbitrarily in ethanol, deionized water, Virahol, hexanaphthene, propyl carbinol, NSC 11801, propylene carbonate, methylcarbonate, diethyl carbonate or dipropyl carbonate;
The preparation process of described composition comprises: polyvinylidene difluoride (PVDF)-R 1216 is dissolved in organic solvent, be configured to polyvinylidene difluoride (PVDF)-R 1216 solution, in polyvinylidene difluoride (PVDF)-R 1216 solution, add inorganic superfine powder body and mix, then inject the non-solvent of polyvinylidene difluoride (PVDF)-R 1216, ageing after stirring, makes the mixed solution of polyvinylidene difluoride (PVDF)-R 1216-superfine powder;
Gained positive and negative plate assembles, and injects liquid electrolyte in the battery after assembling, battery is carried out after preliminary filling, then battery is carried out to heating and pressurizing baking, makes composite porous film and electrolytic solution formation gel, makes jelly glue polymer battery;
Described heating and pressurizing baking, Heating temperature scope is 60～100 DEG C, and pressure range is 0.2～1.0mPa, and be 0.5h～7h total heat-up time.
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| CN201010119052.2A CN102190839B (en) | 2010-03-05 | 2010-03-05 | Gel polymer lithium ion battery, porous composite electrode and porous membrane composition |
| HK12101963.7A HK1161284A1 (en) | 2010-03-05 | 2012-02-27 | A gelatin polymer li-ion battery, porous complex electrode sheet and porous film composition |
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| CN103897207A (en) * | 2012-12-28 | 2014-07-02 | 海洋王照明科技股份有限公司 | Electrochemical power source diaphragm and preparation method thereof, and electrochemical cell or capacitor |
| CN110600662A (en) * | 2019-09-19 | 2019-12-20 | 湘潭大学 | Polyvinylidene fluoride-hexafluoropropylene/titanium dioxide composite membrane and preparation method and application thereof |
| CN110760225A (en) * | 2019-10-31 | 2020-02-07 | 深圳中科瑞能实业有限公司 | Production method of gel polymer electrolyte porous membrane |
| CN111342002B (en) * | 2020-05-15 | 2020-09-15 | 北京小米移动软件有限公司 | Lithium ion battery pole piece, preparation method thereof and lithium ion battery |
| CN112852079B (en) * | 2021-01-18 | 2022-09-06 | 陕西科技大学 | Super-hydrophobic self-cleaning radiation self-cooling material and preparation method thereof |
| CN113394447B (en) * | 2021-05-26 | 2022-09-23 | 浙江南都电源动力股份有限公司 | Electrolyte for preventing micro short circuit of solid-state battery, solid-state battery and preparation method |
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| CN101150182A (en) * | 2006-09-18 | 2008-03-26 | 深圳市比克电池有限公司 | Lithium ion battery electrode slice, electric core and its making method |
| CN101153084A (en) * | 2006-09-28 | 2008-04-02 | 万向电动汽车有限公司 | Polyalcohol microporous barrier for high ratio polyalcohol lithium ion power cell |
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| CN101150182A (en) * | 2006-09-18 | 2008-03-26 | 深圳市比克电池有限公司 | Lithium ion battery electrode slice, electric core and its making method |
| CN101153084A (en) * | 2006-09-28 | 2008-04-02 | 万向电动汽车有限公司 | Polyalcohol microporous barrier for high ratio polyalcohol lithium ion power cell |
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