CN105304850A - Mixed paint for composite membrane of lithium ion battery, composite membrane and preparation method thereof, and lithium ion battery - Google Patents
Mixed paint for composite membrane of lithium ion battery, composite membrane and preparation method thereof, and lithium ion battery Download PDFInfo
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- CN105304850A CN105304850A CN201510593686.4A CN201510593686A CN105304850A CN 105304850 A CN105304850 A CN 105304850A CN 201510593686 A CN201510593686 A CN 201510593686A CN 105304850 A CN105304850 A CN 105304850A
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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
- H01M50/446—Composite material consisting of a mixture of organic and inorganic materials
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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
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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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
- H01M50/403—Manufacturing processes of separators, membranes or diaphragms
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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
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
The invention relates to mixed paint for a composite membrane of a lithium ion battery, and also relates to the composite membrane using the mixed paint and a preparation method thereof, and the lithium ion battery, and belongs to the technical field of the lithium ion batteries. The mixed paint for the composite membrane of the lithium ion battery is prepared from the following components in parts by weight: 45 to 63 parts of organic macromolecule microspheres, 35 to 53 parts of inorganic ceramic particles and 2 to 10 parts of an additive, wherein a melting point temperature or a softening point temperature of the organic macromolecule microspheres is lower than a hot smelting temperature of a base membrane used for the membrane of the lithium ion battery. According to the composite membrane of the lithium ion battery, which utilizes the mixed paint, a micro-pore blocking effect of the organic macromolecule microspheres is more sufficient, a lithium ion transmission channel is completely cut off and the safety of the lithium ion battery is greatly improved.
Description
Technical field
The present invention relates to a kind of lithium ion battery composite separation membrane compo, also relate to composite diaphragm using this compo and preparation method thereof and lithium ion battery simultaneously, belong to technical field of lithium ion.
Background technology
Lithium ion battery is with advantages such as its high energy ratio, memory-less effect, long-lives, be widely used at the numerous areas comprising portable type electronic product, but lithium ion battery is under the application conditions of various complexity, there is the potential hazard of blasting and burning.Along with the development of ev industry, the defect in this security performance of lithium ion battery becomes more obvious, seriously constrains the application of lithium ion battery in fields such as electrokinetic cells.
From current research report, overcharge, inside and outside short circuit, extruding, vibration, collision and the factor such as overheated all may bring out lithium ion battery generation unsafe factor.On the one hand, lithium ion battery adopts organic solution electrolyte, when battery be in overcharge state time organic solvent easily produce irreversible oxidation Decomposition at positive electrode surface, in the generation of a large amount of imflammable gas of simultaneous of releasing amount of heat, cause internal temperature of battery and pressure sharply to rise, thus bring the danger of blast, burning to battery.On the other hand, there is a series of potential exothermic reaction in inside lithium ion cell self, when battery in use causes internal temperature rise larger because of the short circuit of a variety of causes inside and outside, side reaction is just easily induced, as rise when internal temperature of battery more than 120 DEG C time, carbon anode surface passivating film will decompose, the embedding Li-C Electrode of exposed high activity in the electrolytic solution reacts with organic solvent generation very exothermic thereupon, temperature is caused to rise further, and progressively cause the decomposition of electrolytic salt and cathode material, and the very exothermic reaction etc. between embedding Li-C Electrode and adhesive, thus cause battery thermal runaway, blast.Because now widely used electrolyte solvent system is low-flash organic carbonate class, when battery explosion, also can cause violent burning, increase the weight of the extent of injury of safety hazards.
In order to improve the fail safe of lithium ion battery, needing the cell reaction fail safe control technology by novelty, eliminating the Solicitation mechanism that various sensitiveness side reaction occurs, solving the safety issue of lithium ion battery.At the surface-coated inorganic material coating of traditional lithium-ion polyolefin membrane, polyalkene diaphragm shrinkage degree at high temperature can be reduced, thus when avoiding internal temperature of battery to raise, the both positive and negative polarity short circuit that polyolefin shrink causes, thus the fail safe improving battery.But the closed pore temperature of this composite diaphragm is higher, general more than 150 DEG C, when the temperature that battery causes due to external short circuit raises, the micropore of barrier film is closed not in time, ion transfer channels is still unimpeded, short circuit current still can pass through, and then causes heat to assemble rapidly, causes serious consequence.
Application number is the Chinese invention patent of 201310673490.7, discloses a kind of lithium ion battery composite separation membrane, in the side of microporous polyolefin film coating organic high polymer microsphere coating, at another side coating inorganic ceramic coating.This invention does not change the hot melting temperature of microporous polyolefin film self, but after the compound of organic high polymer microsphere coating, reduces the hot closed pore temperature of composite diaphragm.In the selection of organic high polymer microsphere material, by the hot melting temperature range limit of organic high polymer microsphere, be set as the temperature range lower limit that battery may worsen.Like this, when battery temperature reaches the initial temperature that side reaction may occur, organic high polymer microsphere base coating generation melting, the macromolecule of melting enters the micropore of microporous polyolefin film, blocking duct, cut off ion transfer channels, prevented the continuation of battery side reaction from occurring, serve the effect reducing composite diaphragm closed pore temperature.
But, find in actual production and application process, adopt aforesaid way to obtain composite diaphragm and still there are some problems.This composite diaphragm adopts mode organic high polymer microsphere layer and inorganic, ceramic layer being coated in respectively microporous polyolefin film both sides, organic high polymer microsphere is separated with inorganic ceramic particle, when battery temperature raises, organic high polymer microsphere layer generation melting, enter the duct of microporous barrier, and now in battery temperature be still in higher temperature, generally be higher than the melt temperature of organic high polymer microsphere, organic high polymer microsphere is caused to be in this labile state of melting, cannot be fixed in the duct of microporous barrier, insufficient to the blocking in polyolefin micropore duct, not thorough to the cut-out of lithium ion transmission channels.
In addition, find in actual production process, above-mentioned composite diaphragm is adding man-hour, owing to needing to apply different coatings respectively in microporous polyolefin film both sides, need more exchange device after apply a kind of material, then carry out the coating of another kind of material, changing in device procedures, easily cause being coated with the change on the coating material recurring structure that is covered with, reduce the quality of the composite diaphragm that end value obtains.And this mode complex process, adds equipment and production cost.
Summary of the invention
The object of the present invention is to provide a kind of lithium ion battery composite separation membrane compo, to improve the blocking effect of organic high polymer microsphere to the basement membrane micropore that lithium ion battery composite separation membrane uses.Second object of the present invention is to provide a kind of lithium ion battery composite separation membrane using above-mentioned compo.3rd object of the present invention is the preparation method providing the above-mentioned lithium ion battery composite separation membrane in a kind of mountain.4th object of the present invention is to provide a kind of lithium ion battery using above-mentioned lithium ion battery composite separation membrane.
In order to realize above object, the technical scheme of lithium ion battery composite separation membrane compo of the present invention is as follows:
A kind of lithium ion battery composite separation membrane compo, it is characterized in that: the component comprising following parts by weight: the binding agent of the organic high polymer microsphere of 45-63 part, the inorganic ceramic particle of 5-53 part, 2-10 part, the hot melting temperature of the basement membrane that the fusing point of described organic high polymer microsphere or softening point temperature use lower than described lithium ion battery separator.
Lithium ion battery composite separation membrane compo of the present invention employs organic high polymer microsphere and inorganic ceramic particle, the mixing of this coating is coated in after in membrane surface, the composite diaphragm obtained is coated with the compo layer of organic high polymer microsphere and ceramic particle, when battery normally uses, organic high polymer microsphere can ensure the unobstructed of polyolefin micropore membrane aperture, do not hinder effective transmission of lithium ion, when internal temperature of battery raises and reaches the melt temperature of organic high polymer microsphere, organic high polymer microsphere melting also enters the micropore of microporous polyolefin film, block its micropore canals, cut off lithium ion transmission channels, even if temperature continues to raise in battery, because ceramic particle is blended in the middle of macromolecule, certain restriction is played to organic high polymer microsphere, make the blocking microporous effect of organic high polymer microsphere more abundant, the thorough passage having cut off lithium ion and transmitted, increase substantially the fail safe of lithium ion battery.In addition, the present invention adopts organic high polymer microsphere and inorganic ceramic particle mixing coating, weakens the composite diaphragm crimp even avoiding independent coated ceramic particle and cause.
The fusing point of described organic high polymer microsphere or softening temperature are 90-140 DEG C.Because battery is when temperature reaches about 140 DEG C, electrolyte starts to decompose, may side reaction be there is in battery, simultaneously, in cell fabrication processes, the bake out temperature of battery-active pole piece mostly at about 85 DEG C, so, the hot melting temperature of organic high polymer microsphere is set as 90-140 DEG C not only can stop battery generation side reaction but also battery pole piece can be avoided to dry impact on organic high polymer microsphere.Further, this temperature is preferably 100 ~ 130 DEG C.
The technical scheme of composite diaphragm of the present invention is as follows:
A kind of composite diaphragm, comprise basement membrane and be coated in the compo layer on surface, described basement membrane one or both sides, described compo layer is above-mentioned lithium ion battery composite separation membrane compo.
Described basement membrane is microporous polyolefin film.
Composite diaphragm of the present invention uses above-mentioned compo, and the organic high polymer microsphere in this compo is any one homopolymers or wherein several arbitrarily copolymer in ethene, propylene, styrene, vinyl chloride, vinylidene, acrylonitrile, acrylate, vinylacetate.Organic high polymer microsphere has certain imbibition and protects fluidity, improve the pick up of lithium ion battery composite separation membrane, and there is certain chemical-resistance, ensure that long-time infiltration is not dissolved in normal temperature electrolyte, not swelling, in addition, the present invention's preferred organic high polymer microsphere construction unit is simple, avoid the group that strong polar group, conjugated double bond are large, there is good processing characteristics, can the micropore of fast blocking microporous polyolefin film, realize the Thermal shutdown of barrier film.In order to improve the Thermal shutdown performance of lithium ion battery composite separation membrane further, the one of described organic high polymer microsphere more preferably in polyethylene, polypropylene, polystyrene, polyvinyl chloride, polyacrylonitrile, polyacrylate, polyvinyl acetate, styrene divinyl copolymer, AN-AE, ethylene-vinyl acetate copolymer.
Inorganic ceramic particle can for conventional ceramic particle, such as, be Al
2o
3, TiO
2, SiO
2, MgO, ZnO, ZrO
2, SnO
2in any one or a few.
The particle of organic high polymer microsphere is close with the aperture of microporous polyolefin film, general, and the particle diameter of described organic high polymer microsphere is 0.01-2.0 μm, more preferably 0.07-1.5 μm.The particle diameter of inorganic ceramic particle and the particle diameter of organic high polymer microsphere also keep close, to avoid inorganic ceramic particle, obstruction is caused to the micropore that organic polymer enters microporous polyolefin film, therefore, the particle diameter of described inorganic ceramic particle is 0.01-2.0 μm, more preferably 0.05-1.5 μm.
The thickness of compo layer is crossed conference and is caused organic high polymer microsphere can not enter rapidly in the micropore of microporous polyolefin film after melting, and thickness is excessive that the impedance of composite diaphragm also can be caused to increase, reduce the electrical efficiency of composite diaphragm, if the thickness of compo layer is too small, the amount of organic high polymer microsphere can be caused again less, can not block the micropore of microporous polyolefin film completely, therefore, the thickness of described compo layer is 2 ~ 6 μm.
Microporous polyolefin film is the lithium ion battery separator that this area is commonly used, as polyethene microporous membrane PE or microporous polypropylene membrane PP or PP-PE-PP trilamellar membrane.The thickness of microporous polyolefin film crosses the impedance that conference increases composite diaphragm, and composite diaphragm of the present invention comprises compo layer, increase the intensity of composite diaphragm, the microporous polyolefin film of less thickness is selected to meet the demands, general, the thickness of microporous polyolefin film is 8-60 μm, more preferably 20-32 μm.
The porosity of described microporous polyolefin film is 30-50%.
In order to make organic high polymer microsphere and inorganic ceramic particle and binding agent disperse more even, binding agent of the present invention comprises the first binding agent for mixing with organic high polymer microsphere and is used for the second binding agent of mixing with ceramic particle.
Described binding agent is one or more in Kynoar and copolymer, acrylate and copolymer thereof, acrylic acid and copolymer thereof, polyvinyl alcohol, carboxymethyl cellulose, polyurethane.
The technical scheme of the preparation method of composite diaphragm of the present invention is as follows:
The preparation method of above-mentioned composite diaphragm, comprises the following steps:
1) inorganic ceramic particle, the first binding agent are mixed with water, obtain inorganic ceramic slurry;
Organic high polymer microsphere, the second binding agent are mixed with water, obtains organic high polymer microsphere slurry;
2) by step 1) the inorganic ceramic slurry that obtains and organic high polymer microsphere slurry mix, and obtains composite mortar;
3) by step 2) composite mortar that obtains is coated in the surface of described basement membrane, and dry, obtain lithium ion battery composite separation membrane.
The preparation method of composite diaphragm of the present invention applies after organic high polymer microsphere slurry and the mixing of ceramic particle slurry in microporous polyolefin film again, and coating procedure is continuous, does not need more exchange device, and technique is simple, reduces production cost.
In drying course, be subject to high temperature in order to avoid organic high polymer microsphere and cause structural change, ensureing drying efficiency again simultaneously, the temperature of drying in described step (3) is 60-85 DEG C.
The solid content of described organic high polymer microsphere slurry is 15-30%, and the solid content of described ceramic size is 30-40%.
In described step (1), the mass ratio of ceramic particle and the first additive is 11.5 ~ 19:1, and the mass ratio of organic high polymer microsphere and Second addition is 9 ~ 13.3:1.
Coating in described step (3) adopt in transfer coating, intaglio plate coating continuously, spraying, blade coating any one.
The technical scheme of lithium ion battery of the present invention is as follows:
A kind of lithium ion battery, uses above-mentioned composite diaphragm.
Lithium ion battery prepared by the present invention uses above-mentioned composite diaphragm, this composite diaphragm has good permeability and lower heat-shrinkable, be elevated to the hot melting temperature of basement membrane in temperature before, can well by the blockage of the micro orifice of basement membrane, realize Thermal shutdown, use the lithium ion battery of composite diaphragm of the present invention to have good cycle performance, in circulation after 500 weeks, capability retention reaches more than 90%, and substantially increases the fail safe of lithium battery.
Embodiment
Below in conjunction with embodiment, the present invention is further detailed.
Embodiment 1
Lithium ion battery composite separation membrane compo in the present embodiment, comprises the component of following parts by weight: the particle diameter of 90 parts is styrene-divinylbenzene copolymer (PS yl) microballoon of 0.7 μm, and the particle diameter of 95 parts is the Al of 0.5 μm
2o
3particle, the binding agent of 15 parts, binding agent comprises the first binding agent and the second binding agent, first binding agent is the PVA of 10 parts, second binding agent is the CMC of 5 parts, the hot melting temperature of the basement membrane that the fusing point of styrene-divinylbenzene copolymer microballoon or softening point temperature use lower than described lithium ion battery separator.
Lithium ion battery composite separation membrane in the present embodiment, comprise basement membrane and be coated in the compo layer of described basement membrane one side surface, described compo layer comprises the component of following parts by weight: the particle diameter of 95 parts is styrene-divinylbenzene copolymer (PS yl) microballoon of 0.7 μm, and the particle diameter of 90 parts is the Al of 0.5 μm
2o
3particle, the binding agent of 15 parts, binding agent comprises the first binding agent and the second binding agent, first binding agent is the CMC of 5 parts, second binding agent is the PVA of 10 parts, the hot melting temperature of the basement membrane that the fusing point of styrene-divinylbenzene copolymer microballoon or softening point temperature use lower than described lithium ion battery separator.In the present embodiment, basement membrane is microporous polypropylene membrane (PP), and the thickness of described poly-third hydrocarbon microporous barrier is 20 μm, and porosity is 40%, and the thickness of compo layer is 4 μm, and the thickness of lithium ion battery composite separation membrane is 24 μm.
In the present embodiment, the preparation method of lithium ion battery composite separation membrane comprises the following steps:
(1) particle diameter adding 95 parts in deionized water is the Al of 0.5 μm
2o
3particle, high speed dispersor stirs 1h, adds the binding agent CMC of 5 parts, and high speed dispersor stirs 1h, obtains the inorganic ceramic slurry that solid content is 40%;
In deionized water, add the styrene-divinylbenzene copolymer microballoon that 90 parts of particle diameters are 0.7 μm, high speed dispersor stirs 1h, adds the binding agent PVA of 10 parts, and high speed dispersor stirs 1h, obtains the organic high polymer microsphere slurry that solid content is 15%;
(2) inorganic ceramic slurry step (1) obtained and organic high polymer microsphere slurry mix and blend 0.5h in high speed dispersor, obtain composite mortar;
(3) adopt continuous gravure coating process to be coated in the composite mortar that step (2) obtains thickness is 20 μm, porosity be the side of the microporous polypropylene membrane of 40% on the surface, 60 DEG C of oven dry, thickness of coating layer 4 μm, obtains the lithium ion battery composite separation membrane that thickness is 24 μm.
The lithium ion battery of the present embodiment uses above-mentioned lithium ion battery composite separation membrane as barrier film.
The lithium ion battery of the present embodiment is prepared as follows:
(1) preparation of positive plate: add 93 parts of positive electrode active materials LiNi in solvent NMP
1/3co
1/3mn
1/3o
2, the conductive agent carbon black of 4 parts and the binding agent PVDF of 3 parts, mix and blend, obtains the anode sizing agent that solid content is 50%, and obtained anode sizing agent being coated in thickness is on the plus plate current-collecting body aluminium foil of 20 μm, and dry, roll-in obtains positive plate;
(2) preparation of negative plate: add 95 parts of negative electrode active material graphite powders, 2 parts of conductive agent carbon blacks, 1 part of thickener CMC and 2 part of binding agent SBR in solvent deionized water, mix and blend obtains the cathode size that solid content is 30%, obtained cathode size being coated in thickness is on the negative current collector Copper Foil of 10 μm, and dry, roll-in obtains negative plate;
(3) preparation of battery core: positive plate, composite diaphragm, negative plate lamination are made battery core;
(4) assembling of lithium ion battery: battery core is entered shell, inject electrolyte, in described electrolyte, electrolytic salt is the lithium hexafluoro phosphate LiPF of 1mol/L
6, electrolyte solvent is dimethyl carbonate DMC+ ethylene carbonate EC+ methyl ethyl carbonate EMC, encapsulate after fluid injection, obtain lithium ion battery.
Embodiment 2
Lithium ion battery composite separation membrane compo in the present embodiment, comprises the component of following parts by weight: the particle diameter of 93 parts is the AN-AE microballoon of 0.7 μm, and the particle diameter of 92 parts is the SiO of 0.9 μm
2particle, the binding agent of 15 parts, binding agent comprises the first binding agent and the second binding agent, first binding agent is the LA132 of 7 parts, second binding agent is the PVDF of 8 parts, the hot melting temperature of the basement membrane that the fusing point of AN-AE microballoon or softening point temperature use lower than described lithium ion battery separator.
Lithium ion battery composite separation membrane in the present embodiment, comprise basement membrane and be coated in the compo layer of described basement membrane both side surface, described compo layer comprises the component of following parts by weight: the particle diameter of 93 parts is the AN-AE microballoon of 0.7 μm, and the particle diameter of 92 parts is the SiO of 0.9 μm
2particle, the binding agent of 15 parts, binding agent comprises the first binding agent and the second binding agent, first binding agent is the LA132 of 7 parts, second binding agent is the PVDF of 8 parts, the hot melting temperature of the basement membrane that the fusing point of AN-AE microballoon or softening point temperature use lower than described lithium ion battery separator.In the present embodiment, basement membrane is microporous polypropylene membrane (PP), and the thickness of described poly-third hydrocarbon microporous barrier is 20 μm, and porosity is 40%, and the thickness of compo layer is 3 μm, and the thickness of lithium ion battery composite separation membrane is 26 μm.
In the present embodiment, the preparation method of lithium ion battery composite separation membrane comprises the following steps:
(1) particle diameter adding 92 parts in deionized water is the SiO of 0.9 μm
2particle, high speed dispersor stirs 1h, adds the binding agent PVDF of 8 parts, and high speed dispersor stirs 1h, obtains the inorganic ceramic slurry that solid content is 35%;
In deionized water, add the AN-AE microballoon that 93 parts of particle diameters are 0.7 μm, high speed dispersor stirs 1h, adds the binding agent LA132 of 7 parts, and high speed dispersor stirs 1h, obtains the organic high polymer microsphere slurry that solid content is 20%;
(2) inorganic ceramic slurry step (1) obtained and organic high polymer microsphere slurry mix and blend 0.5h in high speed dispersor, obtain composite mortar;
(3) adopt continuous gravure coating process to be coated in the composite mortar that step (2) obtains thickness is 20 μm, porosity be the side of the microporous polypropylene membrane of 40% on the surface, repeat this opposite side operating in microporous polypropylene membrane to apply on the surface, 85 DEG C of oven dry, equal 3 μm of thickness of coating layer in microporous polypropylene membrane both side surface, obtains the lithium ion battery composite separation membrane that thickness is 26 μm.
The lithium ion battery of the present embodiment uses above-mentioned lithium ion battery composite separation membrane as barrier film.
In the present embodiment, the preparation method of lithium ion battery is with embodiment 1.
Embodiment 3
Lithium ion battery composite separation membrane compo in the present embodiment, comprises the component of following parts by weight: the particle diameter of 90 parts is ethylene-vinyl acetate copolymer (EVA) microballoon of 0.7 μm, and the particle diameter of 93 parts is the TiO of 1.0 μm
2particle, the binding agent of 15 parts, binding agent comprises the first binding agent and the second binding agent, first binding agent is the LA132 of 10 parts, second binding agent is the PVDF of 7 parts, the hot melting temperature of the basement membrane that the fusing point of ethylene-vinyl acetate copolymer microballoon or softening point temperature use lower than described lithium ion battery separator.
Lithium ion battery composite separation membrane in the present embodiment, comprise basement membrane and be coated in the compo layer of described basement membrane both side surface, described compo layer comprises the component of following parts by weight: the particle diameter of 90 parts is ethylene-vinyl acetate copolymer (EVA) microballoon of 0.7 μm, and the particle diameter of 93 parts is the TiO of 1.0 μm
2particle, the binding agent of 15 parts, binding agent comprises the first binding agent and the second binding agent, first binding agent is the LA132 of 10 parts, second binding agent is the PVDF of 7 parts, the hot melting temperature of the basement membrane that the fusing point of ethylene-vinyl acetate copolymer microballoon or softening point temperature use lower than described lithium ion battery separator.In the present embodiment, basement membrane is microporous polypropylene membrane (PP), and the thickness of described poly-third hydrocarbon microporous barrier is 32 μm, and porosity is 40%, and the thickness of compo layer is 3 μm, and the thickness of lithium ion battery composite separation membrane is 38 μm.
In the present embodiment, the preparation method of lithium ion battery composite separation membrane comprises the following steps:
(1) particle diameter adding 93 parts in deionized water is the TiO of 1.0 μm
2particle, high speed dispersor stirs 1h, adds the binding agent PVDF of 7 parts, and high speed dispersor stirs 1h, obtains the inorganic ceramic slurry that solid content is 30%;
In deionized water, add the ethylene-vinyl acetate copolymer microballoon that 90 parts of particle diameters are 0.7 μm, high speed dispersor stirs 1h, adds the binding agent LA132 of 10 parts, and high speed dispersor stirs 1h, obtains the organic high polymer microsphere slurry that solid content is 30%;
(2) inorganic ceramic slurry step (1) obtained and organic high polymer microsphere slurry mix and blend 0.5h in high speed dispersor, obtain composite mortar;
(3) adopt continuous gravure coating process to be coated in the composite mortar that step (2) obtains thickness is 32 μm, porosity be the side of the microporous polypropylene membrane of 40% on the surface, repeat this opposite side operating in microporous polypropylene membrane to apply on the surface, 70 DEG C of oven dry, equal 3 μm of thickness of coating layer in microporous polypropylene membrane both side surface, obtains the lithium ion battery composite separation membrane that thickness is 38 μm.
The lithium ion battery of the present embodiment uses above-mentioned lithium ion battery composite separation membrane as barrier film.
In the present embodiment, the preparation method of lithium ion battery is with embodiment 1.
Test example
Following test has been carried out to the lithium ion battery composite separation membrane obtained in embodiment 1-3 and the lithium ion battery that utilizes composite diaphragm obtained:
(1) permeability under different temperatures
The microporous polypropylene membrane of the lithium ion battery composite separation membrane that Example 1-3 obtains and uncoated composite coating, being placed in temperature is that the vacuum drying oven of 80 DEG C, 120 DEG C, 125 DEG C, 140 DEG C heats 30min, according to TAPPIT460 standard test barrier film ventilative value at different temperatures, the results are shown in Table 1.
The permeability of composite diaphragm under table 1 different temperatures
As can be seen from Table 1, lithium ion battery composite separation membrane plug-hole completely at 125 DEG C of preparing of embodiment 1 ~ 3.Illustrate that organic high polymer microsphere melts 120 ~ 125 DEG C of temperature ranges and infiltrates the micropore of microporous polyolefin film, blocking diaphragm micro-hole duct, reaches closed pore effect.And common PP film ventilative value after 140 DEG C of process doubles relative to former film, it is that barrier film base material softens as seen, closed pore does not occur.Therefore, the softening point temperature of organic high polymer microsphere of the present invention is lower than the closed pore temperature of microporous polyolefin film, can by the blockage of the micro orifice of film before temperature suffered by microporous polyolefin film rises to its closed pore temperature, thus early cut-off lithium ion transmission channels, prevent internal short-circuit of battery, improve the fail safe of battery.
(2) heat-shrinkable under different temperatures
The microporous polypropylene membrane of the lithium ion battery composite separation membrane that Example 1-3 obtains and uncoated composite coating, being placed in temperature is that the baking oven of 80 DEG C, 100 DEG C, 120 DEG C, 140 DEG C, 160 DEG C heats 2h, measure barrier film percent thermal shrinkage at different temperatures, the results are shown in Table 2.
The heat-shrinkable of composite diaphragm under table 2 different temperatures
As can be seen from Table 2, the lithium ion battery composite separation membrane of embodiment 1 ~ 3 preparation heat-shrinkable is at each temperature all much smaller than common PP film.When the temperature increases, because the thermal endurance of inorganic ceramic particle in composite coating is comparatively strong, composite diaphragm shrinkage phenomenon is less; When temperature reaches 160 DEG C, the percent thermal shrinkage of composite diaphragm is still less than 1.0%, and common PP film melts completely.
(3) absorbent
The microporous polypropylene membrane of the lithium ion battery composite separation membrane that Example 1-3 obtains and uncoated composite coating, is placed in electrolyte respectively and soaks 30min, and weigh the weight of barrier film before and after soaking, the liquid absorption of unit of account area barrier film, the results are shown in Table 3.
The absorbent of the different barrier film of table 3
As can be seen from Table 3, the absorbent of the lithium ion battery composite separation membrane of embodiment 1 ~ 3 preparation is obviously better than common PP film.Because the coating be coated on composite diaphragm has space, the porosity of composite diaphragm can be significantly improved, make up microporous polyolefin film and the low defect of pole piece porosity, improve the interface, top layer of barrier film, improve the liquid-keeping property of composite diaphragm, thus improve the cycle performance of lithium ion battery.
(4) electrochemical impedance
For checking the Thermal shutdown effect of lithium ion battery composite separation membrane, the microporous polypropylene membrane of the lithium ion battery composite separation membrane that Example 1-3 obtains and uncoated composite coating, trial-production button cell, and carry out the electrochemical impedance test under different temperatures.The results are shown in Table 4.
The electrochemical impedance value of the different barrier film of table 4
As can be seen from Table 4, at normal temperatures, the electrochemical impedance of the electrochemical impedance of composite diaphragm and the microporous polypropylene membrane of uncoated composite coating is unanimous on the whole, and namely composite coating can not affect the electrochemical impedance value of barrier film at normal temperatures; When the temperature increases, the organic high polymer microsphere fusing in composite coating, enters in diaphragm micro-hole, blocks its duct, ensure the realization of Thermal shutdown effect.
(5) charge-discharge performance of the lithium ion battery of different barrier film is applied
For checking the Thermal shutdown effect of composite diaphragm, the microporous polypropylene membrane of lithium ion battery composite separation membrane prepared by Example 1-3 and uncoated composite coating, trial-production button cell, tests the charge-discharge performance that it carries out under different temperatures.The results are shown in Table 5.
The charge status of the different barrier film of table 5
As can be seen from the charge status of table 5 kind of different barrier film, lithium ion battery composite separation membrane prepared by embodiment 1-3 can cut off the discharge and recharge path of battery 140 DEG C time, serves Thermal shutdown effect.Find when actual tests, during charging, melt under high temperature due to the organic high polymer microsphere in coating, battery voltage after 140 DEG C/5min prepared by the composite diaphragm that embodiment 1-3 obtains sharply increases to capping, electric current cannot charge normal, show the normal channel not having ion transfer, this barrier film achieves the Thermal shutdown effect to battery.
(6) cycle performance of the lithium ion battery of different barrier film is applied
Lithium ion battery prepared by Example 1-3 and adopt the lithium ion battery of common PP film preparation, measure lithium ion battery under the multiplying power condition of 1C/1C, the capability retention of different cycle period, the results are shown in Table 6.
The cycle performance of the lithium ion battery of different barrier film applied by table 6
As can be seen from Table 6, the life-span of lithium ion battery prepared by embodiment 1-3, in circulation after 500 weeks, capability retention reached more than 90%, and the capability retention of common PP film lithium ion battery only 79.4%.Illustrate that the wettability of lithium ion battery composite separation membrane prepared by embodiment 1-3 and electrolyte is better, thus make battery have superior cycle performance.
(7) security performance of the lithium ion battery of different barrier film is applied
Lithium ion battery prepared by Example 1-3 and adopt the lithium ion battery of common PP film preparation, measures its security performance respectively, the results are shown in Table 7.
The security performance of the lithium ion battery of different barrier film applied by table 7
As can be seen from Table 7, the lithium ion battery that prepared by embodiment 1-3 has superior security performance.
Claims (9)
1. a lithium ion battery composite separation membrane compo, it is characterized in that: the component comprising following parts by weight: the binding agent of the organic high polymer microsphere of 45-63 part, the inorganic ceramic particle of 35-53 part, 2-10 part, the hot melting temperature of the basement membrane that the fusing point of described organic high polymer microsphere or softening point temperature use lower than described lithium ion battery separator.
2. lithium ion battery composite separation membrane compo as claimed in claim 1, is characterized in that: the fusing point of described organic high polymer microsphere or softening temperature are 90-140 DEG C.
3. a composite diaphragm, is characterized in that: comprise basement membrane and be coated in the compo layer on surface, described basement membrane one or both sides, and described compo layer is the compo in claim 1-2 described in any one.
4. composite diaphragm as claimed in claim 3, it is characterized in that, described organic high polymer microsphere is the one in polyethylene, polypropylene, polystyrene, polyvinyl chloride, polyacrylonitrile, polyacrylate, polyvinyl acetate, styrene divinyl copolymer, AN-AE, ethylene-vinyl acetate copolymer.
5. composite diaphragm as claimed in claim 3, it is characterized in that, described inorganic ceramic particle is Al
2o
3, TiO
2, SiO
2, MgO, ZnO, ZrO
2, SnO
2in any one or a few.
6. composite diaphragm as claimed in claim 3, it is characterized in that, the particle diameter of described organic high polymer microsphere is 0.01-2.0 μm, and the particle diameter of described inorganic ceramic particle is 0.01-2.0 μm.
7. composite diaphragm as claimed in claim 3, it is characterized in that, described binding agent comprises the first binding agent and the second binding agent.
8. a preparation method for composite diaphragm as claimed in claim 7, is characterized in that: comprise the following steps:
1) inorganic ceramic particle, the first binding agent are mixed with water, obtain inorganic ceramic slurry;
Organic high polymer microsphere, the second binding agent are mixed with water, obtains organic high polymer microsphere slurry;
2) by step 1) the inorganic ceramic slurry that obtains and organic high polymer microsphere slurry mix, and obtains composite mortar;
3) by step 2) composite mortar that obtains is coated in the surface of described basement membrane, and dry, obtain lithium ion battery composite separation membrane.
9. a lithium ion battery, is characterized in that, uses composite diaphragm as claimed in claim 3.
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Application publication date: 20160203 |