CN105406009A - Gel black core lithium ion battery and manufacturing method thereof - Google Patents
Gel black core lithium ion battery and manufacturing method thereof Download PDFInfo
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- CN105406009A CN105406009A CN201510979653.3A CN201510979653A CN105406009A CN 105406009 A CN105406009 A CN 105406009A CN 201510979653 A CN201510979653 A CN 201510979653A CN 105406009 A CN105406009 A CN 105406009A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/058—Construction or manufacture
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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
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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
- 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
Abstract
The invention relates to the technical field of lithium ion batteries, in particular to a manufacturing method of a gel black core lithium ion battery. The method comprises the following steps: firstly, preparing materials to manufacture a positive plate, a negative plate and a composite diaphragm; secondly, winding and packaging the positive plate, the negative plate and the composite diaphragm to obtain a semi-finished battery cell; and lastly, filling an electrolyte into the semi-finished battery cell, and performing curing to obtain the gel black core lithium ion battery. The composite diaphragm is prepared by the following specific steps: preparing a polymer solution; immersing the diaphragm in the polymer solution; taking the diaphragm immersed with the polymer solution out, and immersing the diaphragm in deionized water; and lastly, taking the diaphragm out of the deionized water, and drying the diaphragm to obtain the composite diaphragm with high-molecular polymer layers being formed on both sides. The high-molecular polymer layers with high porosities are formed on the composite diaphragm, and connected with micro-pores of the diaphragm in a zigzag way, so that the ion transport capacity of the composite diaphragm is increased, and the gel black core lithium ion battery has a relatively wide use temperature range and a longer cycle life.
Description
Technical field
The present invention relates to technical field of lithium ion, particularly relate to black core lithium ion battery of a kind of gel and preparation method thereof.
Background technology
Lithium ion battery is generally divided into liquid lithium ionic cell (LIB) and solid lithium ion battery (also known as polymer Li-ion battery, PLIB), due to the liquid state organics containing flowing in liquid lithium ionic cell, thus there is the such as potential safety hazard such as internal short-circuit of battery, electrolyte leakage; Solid lithium ion battery polymer instead of liquid electrolyte, can avoid electrolytical leakage, but the ionic conductivity of polymer dielectric is lower than the electrolytical conductivity of liquid phase; And gel polymer lithium ion battery can address these problems well.Adopt the operation principle of polymer Li-ion battery and the identical of liquid lithium ionic cell of gel polymer electrolyte, electrolyte unlike polymer Li-ion battery is adsorbed on polymer substrate by liquid organic electrolyte, be easy to make battery that is ultrathin and arbitrary shape, and more flexible in the design of battery appearance, the capacity density of battery can be improved, increase the useful life of battery, expand range of application.
But the requirement of gel polymer lithium ion battery to barrier film is higher, barrier film requires to have good absorbent and higher porosity, ensures the migration of ion, reduces the resistance of Ion transfer; And the barrier film mechanical strength adopting existing method to make is not high, temperature coefficient is large, and at room temperature barrier film still can play the effect of electronic isolation, is separated by the both positive and negative polarity of battery core; When temperature raises or battery is subject to certain external pressure effect, the mechanical degradation of barrier film, so that former septate shape and thickness cannot be kept, the both positive and negative polarity at some position in battery core may be caused to form short circuit, cause safety issue.In addition, the micropore of such barrier film is mutually through, inevitably brings molecule into, easily cause micro-short circuit in battery assembling process, affects capacity hold facility and the useful life of lithium ion battery, also affects porosity and the air penetrability of barrier film.
In addition, gel polymer lithium ion battery needs to use organic compound inflammable in a large number to extract plasticizer in process of production, adds difficulty and the cost of manufacture of large-scale production, and extends the production cycle.Therefore, prior art needs to be improved.
Summary of the invention
For above-mentioned the deficiencies in the prior art, an object of the present invention there are provided the preparation method of the black core lithium ion battery of a kind of gel, and this preparation method's technique is simple, production cost is low, and with short production cycle;
Two of object of the present invention is to provide this kind of black core lithium ion battery of gel.
To achieve these goals, technical scheme of the present invention is as follows:
The preparation method of the black core lithium ion battery of a kind of gel, comprise the steps: first to prepare material, prepare positive plate, negative plate, composite diaphragm, then make battery core semi-finished product by after described positive plate, described negative plate and described composite diaphragm winding, encapsulation, electrolyte is poured in described battery core semi-finished product subsequently and be cured and get final product; Prepare described composite diaphragm specifically to comprise the steps:
(1) polymer solution is prepared: be dissolved in by high molecular polymer in solvent;
(2) diaphragm paper is soaked in polymer solution;
(3) be soaked in again in deionized water after subsequently the described diaphragm paper having soaked polymer solution being taken out;
(4) finally taken out from described deionized water by described diaphragm paper and dry and obtain the described composite diaphragm that two sides is formed with high polymer layer, described composite diaphragm is black or lead.
Compared to prior art, the present invention is when the black core lithium ion battery of making gel, particularly when making composite diaphragm, owing to successively diaphragm paper being soaked in polymer solution and deionized water, its manufacture method is unique, adopt polymer solution dipping barrier film, the molecule (being generally high molecular polymerization composition granule) in micropore on diaphragm paper all can be flooded out; And then adopt deionized water to soak diaphragm paper, the solvent that can dissolve each other with water in macromolecule polymer solution and high molecular polymer can be separated, chop the connection between high molecular polymer and solvent off, the high polymer layer of the densification that diaphragm paper arranges is made to form all multiple holes, form the high polymer layer of high porosity, be connected with the micropore complications of diaphragm paper itself, increase the ion transport capability of composite diaphragm, the final colloidal black core lithium ion battery made is made to have wider serviceability temperature scope, longer cycle life.In addition, above-mentioned manufacture method technological process is simple, and running cost is low, and process is easy to control, and cost rate advantages of higher.
Preferably, be also added with conductive nano pipe in described polymer solution, wherein said conductive nano pipe can be carbon nano-tube.
Preferably, described step (2) also comprises drying and processing, is specially and is soaked in by diaphragm paper in polymer solution after process, take out at 60 ~ 90 DEG C of baking 3 ~ 10s; Particularly, described barrier film dipping soak time is in a polymer solution 30 ~ 120 seconds by described step (2).
Preferably, described solidification is to having poured into electrolyte and the battery core heating of sealing, then naturally cool, described heating-up temperature is 80 ~ 120 DEG C, and heating time is 100 ~ 300 seconds, relative to prior art, the heating-up temperature of solidifying in the application is low, heating time is short, can avoid the side effect that long-time at elevated temperature causes to battery, improves the chemical property of the black core lithium ion battery of gel.
Particularly, described high molecular polymer be that polymethyl methacrylate, polypropylene are fine, one or more in Kynoar, Kynoar-hexafluoropropylene copolymer, poly(ethylene oxide), polyvinyl acetate.
Particularly, described solvent is one or more in propene carbonate, cyclohexanone, acetone, butanone, 1-METHYLPYRROLIDONE, DMF, DMA and dibutyl phthalate.
Particularly, the mass fraction of high molecular polymer described in described polymer solution is 0.5% ~ 9.5%.
Preferably, the thickness of described high polymer layer is 1 ~ 8 μm, and the porosity of high polymer layer is 70% ~ 85%; Relative to prior art, this high polymer layer is thinner, and porosity is larger, shortens the distance of lithium ion motion, reduces the interface internal resistance in lithium ion battery, thus improves the chemical property of lithium ion battery.
Preferably, in described step (3), the dip time that be impregnated in by described barrier film in deionized water is 60 ~ 120 seconds.
Preferably, in described step (4), the bake out temperature of described oven dry is 60 ~ 85 DEG C, adopt low temperature drying, barrier film clot can be prevented, during high temperature drying, water loss on barrier film is too fast, the structure of high polymer layer is for remaining stable, and its agglomerating force increases, and is easy to cause barrier film curling.
Preferably, described barrier film is polyolefine isolating film, is made up of polyethylene and/or polypropylene; The described barrier film number of plies is n >=1 (n is integer).
The black core lithium ion battery of a kind of gel adopting preparation method as above to make, it comprises the naked battery core of positive plate, negative plate and composite diaphragm winding and encapsulates envelope plastic film and the electrolyte of described naked battery core, wherein said electrolyte is gel polymer electrolytes, described gel polymer electrolyte is poured in described envelope plastic film, and can be cured with described naked battery core, this gel polymer electrolytes is one or more mixtures in ethylene carbonate, diethyl carbonate and dimethyl carbonate, wherein not containing plasticizer.
Preferably, conductive agent in described positive plate and described negative plate is conductive nano agent, general employing carbon nano-tube, mainly conductive nano agent is as less in particle diameters such as carbon blacks than traditional conductive agent, the surface of positive active material or negative active core-shell material can better be coated on, greatly can improve the conductive capability between molecule and molecule, promote lithium ion battery charge-discharge performance, meet the requirement of at present lithium ion battery being filled soon.
The black core lithium ion battery of gel of the present invention, the electrolyte no longer containing free state in its battery core, thus avoids the harm of electrolyte leakage, corrosion; Simultaneously owing to there occurs curing reaction between positive plate, negative plate and composite diaphragm and gel polymer electrolytes, the positive plate of battery core, between composite diaphragm and negative plate, tight bond is together, battery core is defined entirety that one has certain mechanical strength, adds the mechanical strength of lithium ion battery; And the electrolyte in the present invention and the high polymer layer on composite diaphragm can be compatible, it can promote the transmission of lithium ion in composite diaphragm, makes lithium ion battery have the superperformances such as high-energy-density, long circulation life and low internal drop in wider temperature range; And in the present invention, decrease the use of plasticizer, reduce production difficulty, improve production security; In addition, because composite diaphragm except playing the effect of isolation both positive and negative polarity as common batteries barrier film, it also has higher porosity, thus himself also has the characteristic promoting ion transfer, and common diaphragm and electrolyte almost inconsistent, ion transmits and has substantially come by diffusion in barrier film, and the lithium ion battery that therefore the present invention makes has high-energy-density, the superperformance such as long circulation life and low internal drop in wider temperature range; In addition, adopt the black core lithium ion battery of gel that technical solution of the present invention is produced, preparation technology is simple, running cost is low, and process is easy to control, rate of finished products is high, fail safe advantages of higher.
Accompanying drawing explanation
Fig. 1 is the cycle performance comparison diagram of the embodiment of the present invention 1 and comparative example 1;
Fig. 2 is the charging and discharging curve comparison diagram of the embodiment of the present invention 1 and comparative example 1;
Fig. 3 is the cycle performance figure of the embodiment of the present invention 2;
Fig. 4 is the charging and discharging curve figure of the embodiment of the present invention 2;
Fig. 5 is the cycle performance figure of the embodiment of the present invention 3;
Fig. 6 is the charging and discharging curve figure of the embodiment of the present invention 3;
Fig. 7 is the effect schematic diagram after the black core lithium ion battery of gel of the present invention blocks.
Embodiment
For further setting forth the technological means and effect thereof that the present invention takes, be described in detail below in conjunction with the preferred embodiments of the present invention.
Embodiment 1
This embodiment makes the black core lithium ion battery of gel on the basis of manufacture craft of continuing to use conventional aluminum plastic film flexible-packed battery, the parts such as this battery positive plate, negative plate, composite diaphragm, electrolyte and plastic-aluminum packaging film, when it makes, first to prepare positive plate, negative plate, composite diaphragm; Specific as follows.
(1) making of positive plate
Prepare anode sizing agent: be dissolved in 1-METHYLPYRROLIDONE (NMP) by the Kynoar (PVDF) of 1 ~ 5 weight portion, then the carbon nano-tube of 4 ~ 12 weight portions is added, it is made fully to mix, finally add the positive active material of 80 ~ 100 weight portions, this positive active material is chosen as cobalt acid lithium, LiMn2O4, LiFePO 4, one or more in high-nickel material and trielement composite material, the present embodiment adopts cobalt acid lithium, and cobalt acid lithium, carbon nano-tube, mass ratio between Kynoar three is 93:4:3, anode sizing agent is made after mixing and stirring,
Coating positive plate: the upper and lower surface ready anode sizing agent being coated on 16 μm of aluminium foils, and toast at 130 DEG C, except desolventizing NMP, obtain described positive plate;
(2) making of negative plate
Prepare cathode size: be dissolved in by the Kynoar of 1 ~ 8 weight portion in 1-METHYLPYRROLIDONE (NMP), then the carbon nano-tube of 3 ~ 8 weight portions is added, it is made fully to mix, finally add the graphite of 85 ~ 95 weight portions, wherein the mass ratio of graphite, carbon nano-tube and Kynoar three is 92:3:5, makes cathode size after mixing and stirring;
Coating negative plate: the upper and lower surface ready cathode size being coated on 12 μm of Copper Foils, and baking, except desolventizing NMP, obtains described negative plate at 130 DEG C;
(3) making of composite diaphragm
Prepare polymer solution: be dissolved in 1-METHYLPYRROLIDONE by high molecular polymer Kynoar-hexafluoropropylene copolymer and appropriate conductive nanotube (carbon nano-tube), wherein in this polymer solution, the mass fraction of Kynoar-hexafluoropropylene copolymer is 0.5% ~ 9.5%, in the present embodiment preferably 5%, obtain polymer solution;
Coating diaphragm paper: the individual layer polyolefin PP/PE diaphragm paper of 20 μm to be directly immersed in above-mentioned polymer solution after 60 seconds, take out and toast 10 seconds at 90 DEG C, and then this diaphragm paper to be dipped in deionized water 60 seconds, take out subsequently, toast 6 minutes at 85 DEG C, dried, obtained the described composite diaphragm that two sides is formed with high polymer layer; The thickness of wherein said high polymer layer is 1 ~ 8 μm, and the porosity of high polymer layer is 70% ~ 85%;
(4) making of electrolyte
The mixture of the ethylene carbonate of lithium hexafluoro phosphate and (volume ratio is 1:1:1), diethyl carbonate, dimethyl carbonate is mixed and made into the lithium hexafluorophosphate electrolyte solution of 1mol/L;
(5) battery core makes
The wherein above making about positive plate, negative plate, composite diaphragm, electrolyte order in no particular order, the positive plate completed above-mentioned, negative plate, composite diaphragm winding makes naked battery core, specification is 3.1mm × 32mm × 48mm, after toasting a period of time under vacuo, toast 10 hours under being specially 90 DEG C of conditions, load in the aluminum-plastic composite membrane packaging of rushing casing forming; By aluminum-plastic composite membrane hot-pressing, edge-sealing, and retain liquid injection port formation battery core semi-finished product; Finally, the electrolyte of 2-5g is poured in battery core semi-finished product by liquid injection port, by liquid injection port hot-pressing, edge-sealing, after leaving standstill 5-10h, carry out curing reaction; In the present embodiment, the injection rate of concrete electrolyte is 2.3g, heating-up temperature is 87 DEG C, and heating time is 200 seconds, and the positive plate in aluminum-plastic composite membrane, negative plate, barrier film and electrolyte react, after solidification, battery core is cooled naturally, the positive plate of battery core, negative plate and barrier film are bonded together; Wherein, curing temperature is higher, larger to the side effect of battery, and the curing temperature of existing gel lithium ion battery is generally higher, and adopts 87 DEG C in the present embodiment, can improve the chemical property of the black core battery of gel in the present invention further; Finally test the battery made, its capacity is 550mAh, and as shown in Figure 1, charge-discharge performance as shown in Figure 2 for capability retention.
Embodiment 2
The manufacture method of the gel black core lithium ion battery of the present embodiment is substantially identical with embodiment 1, and difference is the setting of Material selec-tion and design parameter, and existing concise and to the point its concrete steps of description are as follows:
(1) making of positive plate
Prepare anode sizing agent: be dissolved in 1-METHYLPYRROLIDONE (NMP) by the Kynoar (PVDF) of 4 weight portions, then the carbon nano-tube of 4 weight portions is added, it is made fully to mix, finally add the LiMn2O4 of 92 weight portions, mass ratio wherein between LiMn2O4, carbon nano-tube, Kynoar three is 92:4:4, makes anode sizing agent after mixing and stirring;
Coating positive plate: the upper and lower surface ready anode sizing agent being coated on 12 μm of aluminium foils, and toast at 120 DEG C, except desolventizing NMP, obtain described positive plate;
(2) making of negative plate
Prepare cathode size: be dissolved in by the Kynoar of 5 weight portions in 1-METHYLPYRROLIDONE (NMP), then the carbon nano-tube of 3 weight portions is added, it is made fully to mix, finally add the native graphite of 92 weight portions, wherein the mass ratio of graphite, carbon nano-tube and Kynoar three is 92:3:5, makes cathode size after mixing and stirring;
Coating negative plate: the upper and lower surface ready cathode size being coated on 12 μm of Copper Foils, and baking, except desolventizing NMP, obtains described negative plate at 130 DEG C;
(3) making of composite diaphragm
Prepare polymer solution: be that the Kynoar-hexafluoropropylene copolymer of 1:1 and polyvinyl acetate and conductive nanotube are dissolved in the acetone and 1-METHYLPYRROLIDONE that mass ratio is 3:1 by mass ratio, wherein in this polymer solution, the mass fraction of Kynoar-hexafluoropropylene copolymer and polyvinyl acetate is 9.5%, obtains polymer solution;
Coating diaphragm paper: two-layer 20 μm of thick polyolefin PP/PE diaphragm papers to be directly immersed in above-mentioned polymer solution 40 seconds, toast 6 seconds at 80 DEG C after taking-up, then pore-creating in deionized water is dipped into, take out oven dry subsequently, obtain the described composite diaphragm that two sides is formed with high polymer layer; The thickness of wherein said high polymer layer is 1 ~ 8 μm, and the porosity of high polymer layer is 70% ~ 85%;
(4) making of electrolyte
The mixture of the ethylene carbonate of lithium hexafluoro phosphate and (volume ratio is 1:1:1), diethyl carbonate, dimethyl carbonate is mixed and made into the lithium hexafluorophosphate electrolyte solution of 1mol/L;
(5) battery core makes
The wherein above making about positive plate, negative plate, composite diaphragm, electrolyte order in no particular order, the positive plate completed above-mentioned, negative plate, membrane winding make naked battery core, specification is 3.1mm × 32mm × 48mm, toast 10 hours under 90 DEG C of conditions under vacuo, load in the aluminum-plastic composite membrane packaging of rushing casing forming; By aluminum-plastic composite membrane hot-pressing, edge-sealing, and retain liquid injection port formation battery core semi-finished product; Finally, the electrolyte of 2.8gd is poured in battery core semi-finished product by liquid injection port, by liquid injection port hot-pressing, edge-sealing, after leaving standstill 7h, carry out curing reaction; During solidification, concrete heating-up temperature is 80 DEG C, and heating time is 150 seconds, and the positive plate in aluminum-plastic composite membrane, negative plate, barrier film and electrolyte react, and battery core naturally cooled, make the positive plate of battery core, negative plate and barrier film be bonded together and get final product after solidification.
Carry out battery testing subsequently, its capacity is 550mAh, and as shown in Figure 3, the pure manganese material cycle performance of this gel black core lithium ion battery is good, and 1C circulates 500 weeks capability retentions more than 87% for capability retention; Charge-discharge performance as shown in Figure 4.
Embodiment 3
The manufacture method of the gel black core lithium ion battery of the present embodiment is substantially identical with embodiment 1, and difference is the setting of Material selec-tion and design parameter, and existing concise and to the point its concrete steps of description are as follows:
(1) making of positive plate, negative plate
In the present embodiment, positive active material is the mixture of trielement composite material and LiFePO 4, negative active core-shell material is the mixture of graphite and native graphite, wherein, in positive plate, the mass ratio of positive active material, carbon nano-tube and binding agent Kynoar is 90:3:7; In negative plate, the mass ratio of negative electrode active material, carbon nano-tube and binding agent Kynoar is 90:3:7;
(2) making of composite diaphragm and electrolyte
The solute of polymer solution to be mass ratio the be polyvinyl acetate of 1:2 and the mixture of poly(ethylene oxide) and appropriate conductive nanotube, solvent is N, dinethylformamide, mass fraction is 4.5%, and barrier film is three layers 10 μm thick polyolefin PP barrier films, and diaphragm paper soaks 1 minute in a polymer solution, 3s is toasted at 60 DEG C, soak 2 minutes in deionized water again, finally toast 5 minutes at 80 DEG C, obtain the described composite diaphragm that two sides is formed with high polymer layer; The thickness of wherein said high polymer layer is 1 ~ 8 μm, and the porosity of high polymer layer is 70% ~ 85%; The production method of electrolyte is identical with embodiment 1;
(5) battery core makes
The positive plate completed above-mentioned, negative plate, composite diaphragm winding makes naked battery core, and making specification is 3.1mm × 32mm × 48mm, toasts 10 hours under vacuo under 90 DEG C of conditions, loads in the aluminum-plastic composite membrane packaging of rushing casing forming; By aluminum-plastic composite membrane hot-pressing, edge-sealing, and retain liquid injection port formation battery core semi-finished product; Finally, the electrolyte of 3.0g is poured in battery core semi-finished product by liquid injection port, by liquid injection port hot-pressing, edge-sealing, after leaving standstill 7h, carry out curing reaction; During solidification, concrete heating-up temperature is 80 DEG C, and heating time is 150 seconds, and the positive plate in aluminum-plastic composite membrane, negative plate, barrier film and electrolyte react, and battery core naturally cooled, make the positive plate of battery core, negative plate and barrier film be bonded together and get final product after solidification.
Carry out battery testing subsequently, its capacity is 550mAh, and as shown in Figure 5, the pure ternary material cycle performance of this gel black core lithium ion battery is good for capability retention, and 1C circulates 500 weeks capacity maintenance matter rates more than 89%.Charge-discharge performance as shown in Figure 6.
Comparative example 1
The manufacture method of this comparative example lithium ion battery and the difference of embodiment 1 are Material selec-tion and manufacture method, and existing concise and to the point its concrete steps of description are as follows:
(1) making of positive plate, negative plate
Conductive agent in positive plate and negative plate is conductive black;
(2) making of barrier film and electrolyte
Diaphragm paper is immersed in after in macromolecule polymer solution and directly dries, and obtain required barrier film, and dry without the need to continuing to be soaked in water again, the production method of electrolyte is identical with embodiment 1;
(5) battery core makes
The positive plate completed above-mentioned, negative plate, membrane winding make naked battery core, and making specification is 3.1mm × 32mm × 48mm, toast 10 hours under vacuo under 90 DEG C of conditions, load in the aluminum-plastic composite membrane packaging of rushing casing forming; By aluminum-plastic composite membrane hot-pressing, edge-sealing, and retain liquid injection port formation battery core semi-finished product; Finally, the electrolyte of 3.0g is poured in battery core semi-finished product by liquid injection port, by liquid injection port hot-pressing, edge-sealing, after leaving standstill 7h, carry out curing reaction; During solidification, concrete heating-up temperature is 80 DEG C, and heating time is 150 seconds, and the positive plate in aluminum-plastic composite membrane, negative plate, barrier film and electrolyte react, and battery core naturally cooled, make the positive plate of battery core, negative plate and barrier film be bonded together and get final product after solidification.
Carry out battery testing subsequently, its capacity is 500mAh, and as shown in Figure 1, charge-discharge performance as shown in Figure 2 for capability retention.
Known from Fig. 1 and Fig. 2, compared to comparative example 1, gel black core lithium ion battery pure cobalt material circulation smooth performance prepared by embodiment 1,1C circulates 500 weeks capacity maintenance matter rates more than 95%, and the battery capacity conservation rate prepared in comparative example 1 is only about 90%; And the gel prepared in the present embodiment black core lithium ion battery efficiency for charge-discharge is apparently higher than the lithium ion battery in comparative example 1.
Electrolyte no longer containing free state in black its battery core of core lithium ion battery of gel prepared by the present invention, thus avoids the harm of electrolyte leakage, corrosion; Simultaneously owing to there occurs curing reaction between positive plate, negative plate and composite diaphragm and gel polymer electrolytes, the positive plate of battery core, between composite diaphragm and negative plate, tight bond is together, battery core is defined entirety that one has certain mechanical strength, add the mechanical strength of lithium ion battery, make it have the security performance of superelevation, directly cut in two under full power state, as shown in Figure 7, this gel black core lithium ion battery also there will not be bulging, leakage, the problem such as on fire.
Above-described embodiment, just preferred embodiment of the present invention, is not used for limiting the scope of the present invention, therefore all equivalences done with the structure described in the claims in the present invention, feature and principle change or modify, and all should be included within the claims in the present invention scope.
Claims (10)
1. the preparation method of the black core lithium ion battery of gel, comprise the steps: first to prepare material, prepare positive plate, negative plate, composite diaphragm, then make battery core semi-finished product by after described positive plate, described negative plate and described composite diaphragm winding, encapsulation, electrolyte is poured in described battery core semi-finished product subsequently and be cured and get final product; It is characterized in that, prepare described composite diaphragm and specifically comprise the steps:
(1) high molecular polymer and conductive nano pipe are dissolved in solvent prepare polymer solution;
(2) diaphragm paper is soaked in polymer solution;
(3) subsequently the described diaphragm paper having soaked polymer solution is soaked in deionized water again;
(4) finally described diaphragm paper is taken out from described deionized water and dry and obtain the described composite diaphragm that two sides is formed with high polymer layer.
2. the preparation method of the black core lithium ion battery of gel according to claim 1, is characterized in that: described high molecular polymer is that polymethyl methacrylate, polypropylene are fine, one or more in Kynoar, Kynoar-hexafluoropropylene copolymer, poly(ethylene oxide), polyvinyl acetate; Described solvent is one or more in propene carbonate, cyclohexanone, acetone, butanone, 1-METHYLPYRROLIDONE, DMF, DMA and dibutyl phthalate.
3. the preparation method of the black core lithium ion battery of gel according to claim 1, is characterized in that: described conductive nano pipe is carbon nano-tube.
4. the preparation method of the black core lithium ion battery of gel according to claim 1, is characterized in that: the mass fraction of high molecular polymer described in described polymer solution is 0.5% ~ 9.5%.
5. the preparation method of the black core lithium ion battery of gel according to claim 1, it is characterized in that: the thickness of described high polymer layer is 1 ~ 8 μm, the porosity of described high polymer layer is 50% ~ 85%.
6. the preparation method of the black core lithium ion battery of gel according to claim 1, is characterized in that: described step (2), is 30 ~ 120 seconds by described diaphragm paper dipping soak time in a polymer solution.
7. the preparation method of the black core lithium ion battery of gel according to claim 1, it is characterized in that: in described step (3), the dip time that be impregnated in by described diaphragm paper in deionized water is 60 ~ 120 seconds.
8. the preparation method of the black core lithium ion battery of gel according to claim 1, it is characterized in that: described step 2) also comprise drying and processing, described drying and processing, for being soaked in by diaphragm paper in polymer solution after process, takes out at 60 ~ 90 DEG C of baking 3 ~ 10s.
9. the preparation method of the black core lithium ion battery of gel according to claim 1, it is characterized in that: in described step (4), the bake out temperature of described oven dry is 60 ~ 85 DEG C.
10. the black core lithium ion battery of gel adopting the preparation method as described in any one of claim 1 ~ 9 to make, it comprises the naked battery core of positive plate, negative plate and composite diaphragm winding and encapsulates envelope plastic film and the electrolyte of described naked battery core, it is characterized in that: described electrolyte is gel polymer electrolytes, described gel polymer electrolyte is poured in described envelope plastic film, and can be cured with described naked battery core.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107994250A (en) * | 2016-10-26 | 2018-05-04 | 丰田自动车株式会社 | Rechargeable nonaqueous electrolytic battery and its manufacture method |
| US20210066692A1 (en) * | 2018-09-21 | 2021-03-04 | Lg Chem, Ltd. | Separator and electrochemical device comprising same |
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| CN101393975A (en) * | 2008-10-10 | 2009-03-25 | 深圳市邦凯电子有限公司 | Colloidal state polymer battery and composite diaphragm manufacturing method therefor |
| CN103872282A (en) * | 2014-03-31 | 2014-06-18 | 河南理工大学 | Polymer lithium ion battery diaphragm and preparation method thereof |
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- 2015-12-23 CN CN201510979653.3A patent/CN105406009A/en active Pending
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101393975A (en) * | 2008-10-10 | 2009-03-25 | 深圳市邦凯电子有限公司 | Colloidal state polymer battery and composite diaphragm manufacturing method therefor |
| CN103872282A (en) * | 2014-03-31 | 2014-06-18 | 河南理工大学 | Polymer lithium ion battery diaphragm and preparation method thereof |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107994250A (en) * | 2016-10-26 | 2018-05-04 | 丰田自动车株式会社 | Rechargeable nonaqueous electrolytic battery and its manufacture method |
| US20210066692A1 (en) * | 2018-09-21 | 2021-03-04 | Lg Chem, Ltd. | Separator and electrochemical device comprising same |
| US11784377B2 (en) * | 2018-09-21 | 2023-10-10 | Lg Energy Solution, Ltd. | Separator including porous coating layer with amorphous adhesive binder polymer and fluorinated binder polymer and electrochemical device including the same |
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