CN105161661A - Composite diaphragm for lithium ion battery, preparation method of composite diaphragm, and lithium ion battery - Google Patents
Composite diaphragm for lithium ion battery, preparation method of composite diaphragm, and lithium ion battery Download PDFInfo
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- CN105161661A CN105161661A CN201510660432.XA CN201510660432A CN105161661A CN 105161661 A CN105161661 A CN 105161661A CN 201510660432 A CN201510660432 A CN 201510660432A CN 105161661 A CN105161661 A CN 105161661A
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- lithium ion
- ion battery
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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
-
- 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
-
- 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
-
- 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
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
-
- 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
- H01M50/411—Organic material
- H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
- H01M50/417—Polyolefins
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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
- H01M50/411—Organic material
- H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
- H01M50/423—Polyamide resins
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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
- H01M50/443—Particulate material
-
- 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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- 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
Abstract
The invention provides a composite diaphragm for a lithium ion battery. The composite diaphragm comprises a diaphragm matrix and a functional coating composited onto the surface of the diaphragm matrix; the functional coating is prepared from one or more functional substances and one or more adhesives; the functional substances comprise a phosphorous-containing compound, a nitrogen-containing compound and an inorganic silicon compound. The composite lithium ion battery diaphragm has the advantages that the surface of the diaphragm matrix is coated with a layer of the functional coating, the functional coating can quickly absorb redundant heat of the lithium ion battery when the temperature of the lithium ion battery is increased, the absorbed heat serves as reaction entropy and spontaneously responds to a chemical reaction, and a protective layer is formed on the surface of the composite diaphragm; on one hand, the temperature of the lithium ion battery can be effectively prevented from continuing increasing, and thermal contraction of the composite diaphragm can be reduced; on the other hand, active layers on the cathode and anode of the lithium ion battery can be passivated, potential safety hazards of the lithium ion battery can be controlled radically, and the safety of the lithium ion battery can be guaranteed.
Description
Technical field
The invention belongs to technical field of lithium ion, be specifically related to a kind of lithium ion battery composite separation membrane and preparation method thereof and a kind of lithium ion battery.
Background technology
Battery diaphragm refers to the porous material that one deck is thin between anode and negative pole, is part very crucial in battery, has a direct impact the fail safe of battery and cost.It has the mechanical strength that macroion permeability is become reconciled, and in electrolyte to system such as battery, chemical substance used and solvent have long-time stability.Typical organic barrier film is microporous polyolefin film, as polyethene microporous membrane or microporous polypropylene membrane.Due to structure of chemical composition and the moulding process of polyolefin self, determine its process based prediction model, cause it and there are some defects in lithium-ion power battery dissepiment application aspect.
Microporous polyolefin film is used for the main Problems existing of battery diaphragm to be had: (1) polyolefin is as non-polar material, and poor with the electrolyte compatibility of strong polarity, the liquid-keeping property causing it is poor; (2) microporous polyolefin film many employings mechanical stretching pore, or organic solvent extraction pore after mechanical stretching, then obtained by thermal finalization.Finally cause this film to have shape memory effect, when temperature is higher, barrier film trends towards the shape recovering stretching cephacoria, causes larger thermal contraction.Although polyolefinic fusion temperature is lower, base material easily produces fusing in temperature more than more than 165 DEG C, and micropore is disappeared, and blocks ionic conduction and so-called fuse protection effect.But due to microporous polyolefin film there is fusing time, also along with volume contraction, membrane area reduces, and makes barrier film lose iris action between both positive and negative polarity, thus causes inside battery both positive and negative polarity to be short-circuited, cause cells burst even to explode, produce potential safety hazard.
The fail safe how improving lithium ion battery is the important topic of the industry, is also an extremely urgent key problem in technology difficult problem.The main cause of lithium ion battery generation potential safety hazard is caused to be that battery occurs caused by the thermal runaway of irreversible electrochemistry side reaction generation.Therefore, the thermal stability improving barrier film is the important leverage of lithium ion battery security.
Be used for the approach of the thermal stability improving barrier film mainly by the physical property of high temperature resistant material in industry, at the resistant to elevated temperatures inorganic matter of polyolefinic surface-coated if alundum (Al2O3) and high temperature resistant organic substance are as aramid fiber etc., or develop resistant to elevated temperatures diaphragm matrix as polyimide diaphragm etc.But the further rising of battery temperature can not be stoped, the fail safe of battery cannot be ensured efficiently.
Summary of the invention
In view of this, the technical problem to be solved in the present invention is to provide a kind of lithium ion battery composite separation membrane and preparation method thereof and a kind of lithium ion battery, adopt lithium ion battery composite separation membrane provided by the invention that battery temperature can be suppressed to raise, ensure the fail safe of battery.
The invention provides a kind of lithium ion battery composite separation membrane, comprise diaphragm matrix and be compound in the functional coat on described diaphragm matrix surface, described functional coat is prepared from by functional materials and adhesive, described functional materials be selected from phosphorus-containing compound, nitrogen-containing compound and inorganic silicon compounds one or more.
Preferably, described functional materials is selected from one or more in pentaerythrite melamine phosphate and its esters, APP, poly-phosphoramide types compound, organophosphazene poly mer, polysiloxanes compounds and thiourea.
Preferably, described functional materials is selected from one or more in melamine cyanurate, pentaerythrite melamine phosphate, ammonium polyphosphate, dimethyl silicone polymer and melamine pyrophosphate.
Preferably, the mass ratio of described functional materials and adhesive is (90 ~ 99): (1 ~ 10).
Preferably, the one side thickness of described functional coat is 3 ~ 6 μm.
Preferably, described diaphragm matrix is selected from microporous polyolefin film or polyolefin-based ceramic membrane.
Preferably, described binding agent is one or more in Kynoar and copolymer, acrylic acid and copolymer thereof, acrylate and copolymer, polyvinyl alcohol, carboxymethyl cellulose and polyurethane.
Present invention also offers a kind of preparation method of lithium ion battery composite separation membrane, comprise the following steps:
A) be scattered in solvent by functional materials and adhesive, obtain mixed slurry, described functional materials is selected from phosphorus-containing compound, containing one or more in nitrogen compound and inorganic silicon compounds;
B) described mixed slurry is coated on diaphragm matrix surface, dries, obtain lithium ion battery composite separation membrane.
Preferably, the mode of described coating is selected from transfer coating, dip-coating, blade coating, rotogravure application, spraying or silk screen printing.
Present invention also offers a kind of lithium ion battery, comprise positive pole, negative pole, barrier film and electrolyte, described barrier film is above-mentioned lithium ion battery composite separation membrane.
Preferably, the active material of described positive pole is selected from LiFePO
4, LiMn
2o
4, LiCoO
2, LiV
2o
5, LiNiO
2, LiNi
(1-x-y)co
xal
yo
2, LiNi
(1-m-n)co
mmn
no
2and LiCo
zni
(1-z)o
2one or more in material, wherein, 0≤x≤1,0≤y≤1, x+y=1; 0≤m≤1,0≤n≤1, m+n=1; 0≤z≤1.
Compared with prior art, the invention provides a kind of lithium ion battery composite separation membrane, comprise diaphragm matrix and be compound in the functional coat on described diaphragm matrix surface, described functional coat is prepared from by functional materials and adhesive, and described functional materials is selected from phosphorus-containing compound, containing one or more in nitrogen compound and inorganic silicon compounds.Lithium ion battery composite separation membrane provided by the invention is one deck functional coat in diaphragm matrix surface-coated; this functional coat is when lithium ion battery temperature raises; the waste heat of battery can be absorbed fast; as reaction entropy; spontaneously respond chemical reaction; protective layer is generated at membrane surface; the continuation of the temperature of battery can be effectively suppressed to raise on the one hand; reduce the thermal contraction of barrier film; on the other hand can the active layer of passivation cell anode and cathode; control the potential safety hazard of battery from root, ensure the fail safe of battery.In addition, because functional coating hardness of the present invention is less, the process loss in cell fabrication processes can be reduced, thus reduce the production cost of battery.
Result shows, lithium ion battery composite separation membrane provided by the invention all shows less thermal contraction at different temperature, has good thermal stability; The liquid absorption of described lithium ion battery composite separation membrane in 30 minutes is 61 ~ 89g/m
2; Described composite diaphragm is prepared into lithium ion battery, its capability retention > 90% in 1500 cycle periods, and when carrying out cell safety test, there is superior security performance.
Embodiment
The invention provides a kind of lithium ion battery composite separation membrane, comprise diaphragm matrix and be compound in the functional coat on described diaphragm matrix surface, described functional coat is prepared from by functional materials and adhesive, and described functional materials is selected from phosphorus-containing compound, containing one or more in nitrogen compound and inorganic silicon compounds.
Lithium ion battery separator provided by the invention comprises diaphragm matrix.The diaphragm matrix of the present invention to described lithium ion battery does not have particular restriction, well known to a person skilled in the art the diaphragm matrix that can be used for lithium ion battery.In the present invention, described diaphragm matrix is preferably microporous polyolefin film or polyolefin-based ceramic membrane.Microporous polyolefin film of the present invention can be microporous polypropylene membrane, also can be polyethene microporous membrane, also can be the laminated film of different types of microporous polyolefin film.Described in polyolefin-based ceramic membrane of the present invention, ceramic material is preferably aluminium oxide or boehmite.In embodiments more of the present invention, described diaphragm matrix is microporous polypropylene membrane; In other embodiments of the present invention, described diaphragm matrix is polyethene microporous membrane.In other embodiments of the present invention, described diaphragm matrix is polyvinyl ceramic diaphragm; In other embodiments of the present invention, described diaphragm matrix is polypropylene-base ceramic diaphragm.In the present invention, the thickness of described diaphragm matrix is preferably 10 ~ 60 μm, is preferably 10 ~ 55 μm, is more preferably 15 ~ 50 μm, most preferably is 12 ~ 25 μm.
Lithium ion battery separator provided by the invention also comprises the functional coat being compound in described diaphragm matrix surface, and described functional coat is prepared from by functional materials and adhesive.
Functional coat provided by the invention comprises functional materials; the described functional materials for the preparation of lithium ion battery separator surface-functional coating, when battery temperature raises, can absorb the heat of battery, as reaction entropy; spontaneously respond chemical reaction, generate protective layer at membrane surface.In the present invention, described functional materials is selected from one or more in phosphorus-containing compound, nitrogen-containing compound and inorganic silicon compounds.
Preferably, described functional materials is selected from one or more in pentaerythrite melamine phosphate and its esters, APP, poly-phosphoramide types compound, organophosphazene poly mer, polysiloxanes compounds and thiourea.
Preferred, described functional materials be selected from melamine cyanurate and derivative, pentaerythrite melamine phosphate and derivative, ammonium polyphosphate and derivative thereof, dimethyl silicone polymer and derivative thereof and melamine pyrophosphate and derivative thereof one or more.
Most preferred, described functional materials be selected from melamine cyanurate, pentaerythrite melamine phosphate, ammonium polyphosphate, dimethyl silicone polymer and melamine pyrophosphate one or more.
In embodiments more of the present invention, described functional materials is selected from melamine cyanurate (MCA); In other embodiments of the present invention, described functional materials is selected from pentaerythrite melamine phosphate (PPMS); In other embodiments of the present invention, described functional materials is selected from Melamine pyrophosphate (MPP); In other embodiments of the present invention, described functional materials is selected from melamine phosphate (MPOP); In other embodiments of the present invention, described functional materials is selected from ammonium polyphosphate (APP); In other embodiments of the present invention, described functional materials is selected from the mixture of Melamine pyrophosphate (MPP) and melamine cyanurate (MCA); In other embodiments of the present invention, described functional materials is selected from coated ammonium polyphosphate (APP) particle of dimethyl silicone polymer (PDMS), wherein, the mass ratio of described dimethyl silicone polymer and ammonium polyphosphate is preferably 80:15.The present invention does not have particular restriction to above-mentioned coated method, preferably carries out coated by the following method:
By polydimethylsiloxane and ammonium polyphosphate on high speed dispersor with the linear velocity rapid stirring 15 ~ 60min of 10 ~ 80m/s, obtain the ammonium polyphosphate particle (PDMS-APP) that dimethyl silicone polymer is coated.
Functional coat provided by the invention also comprises binding agent, described binding agent be selected from Kynoar and copolymer, acrylic acid and copolymer thereof, acrylate and copolymer, polyvinyl alcohol, carboxymethyl cellulose and polyurethane one or more, be preferably in PVDF membrane (PVDF), butadiene-styrene rubber (SBR) and LA132 aqueous binder one or more.The present invention's binding agent used can with diaphragm matrix close adhesion, thus this binding agent just ensure that the tight bond of functional coat and diaphragm matrix.Two-layer bonding is tight, avoids in vibration, bends or in folding process, occur shedding phenomenon, ensure the uniformity of electric current in battery charge and discharge process.
In the present invention, the mass ratio of described functional materials and adhesive is (80 ~ 99): (1 ~ 20), is preferably (90 ~ 99): (1 ~ 10).In some embodiments in the present invention, the mass ratio of described functional materials and adhesive is 96:4; In other embodiments of the present invention, the mass ratio of described functional materials and adhesive is 97:3; In other embodiments of the present invention, the mass ratio of described functional materials and adhesive is 98:2, in other embodiments of the present invention, the mass ratio of described functional materials and adhesive is 95:5, in other embodiments of the present invention, the mass ratio of described functional materials and adhesive is 95.5:4.5.
In the present invention, described functional coat can be compound in the one side of described diaphragm matrix, also can be compound in the two-sided of described diaphragm matrix.
The one side thickness of functional coat of the present invention is 2 ~ 15 μm, is preferably 3 ~ 6 μm.In embodiments more of the present invention, the thickness of described coating is 3 μm; In other embodiments of the present invention, the thickness of described coating is 4 μm; In other embodiments of the present invention, the thickness of described coating is 5 μm.
In the present invention, the thickness of described lithium ion battery composite separation membrane is 12 ~ 75 μm, is preferably 15 ~ 70 μm, is more preferably 15 ~ 37 μm.
Present invention also offers the preparation method of above-mentioned lithium ion battery composite separation membrane, comprise the following steps:
A) be scattered in solvent by functional materials and adhesive, obtain mixed slurry, described functional materials comprises phosphorus-containing compound, containing one or more in nitrogen compound and inorganic silicon compounds;
B) described mixed slurry is coated on diaphragm matrix surface, dries, obtain lithium ion battery composite separation membrane.
First functional materials and adhesive are scattered in solvent by the present invention, obtain mixed slurry.The method of the present invention to described dispersion does not have particular restriction, well known to a person skilled in the art process for dispersing.In the present invention, preferably disperse as follows:
In high speed dispersor, functional materials and adhesive are scattered in after in solvent respectively and mix again, obtain mixed slurry.
The linear velocity of described high speed dispersor is preferably with 10 ~ 80m/s, and jitter time is preferably 10min ~ 90min.Described solvent include but not limited in deionized water, ethanol, benzene, toluene, NMP and acetone one or more.In embodiments more of the present invention, described solvent is preferably deionized water or NMP.After the mixed slurry prepared, adopt the solid content in solvent adjustment mixed slurry, solid content in final control mixed slurry is 30wt% ~ 60wt%, be preferably 35wt% ~ 50wt%, in the adjustment mixed slurry that the present invention is used, the solvent of solid content includes but not limited to one or more in deionized water, ethanol, benzene, toluene, NMP and acetone.
After obtaining mixed slurry, described mixed slurry is coated on diaphragm matrix surface, dries, obtain lithium ion battery composite separation membrane.
The present invention does not have particular restriction to the method that described mixed slurry is coated on diaphragm matrix surface, well known to a person skilled in the art painting method.In the present invention, transfer coating, dip-coating, blade coating, rotogravure application, spraying or silk screen printing is preferably adopted.
After described mixed slurry is coated on diaphragm matrix surface, dries, obtain lithium ion battery composite separation membrane.The mode of the present invention to described oven dry does not have particular restriction, well known to a person skilled in the art furnace drying method.In the present invention, the temperature of described oven dry is preferably 40 ~ 90 DEG C.
Present invention also offers a kind of lithium ion battery, comprise positive pole, negative pole, barrier film and electrolyte, described barrier film is selected from above-mentioned lithium ion battery composite separation membrane.The kind of the present invention to described positive pole, negative pole and electrolyte does not have particular restriction, well known to a person skilled in the art the kind of lithium ion cell positive, negative pole and electrolyte.
In the present invention, the active material of described positive pole includes but not limited to LiFePO
4, LiMn
2o
4, LiCoO
2, LiV
2o
5, LiNiO
2, LiNi
(1-x-y)co
xal
yo
2, LiNi
(1-m-n)co
mmn
no
2and LiCo
zni
(1-z)o
2one or more in material, wherein, 0≤x≤1,0≤y≤1, x+y=1; 0≤m≤1,0≤n≤1, m+n=1; 0≤z≤1.
Described negative electrode active material include but not limited in graphite, hard carbon, lithium titanate and soft carbon one or more.
Lithium ion battery composite separation membrane provided by the invention, by the resistant to elevated temperatures physical property of its functional coating, can increase the thermal stability of barrier film, reduces the thermal contraction of barrier film.When battery temperature raises, the preliminary fail safe ensureing battery, makes battery rapidly the potential safety hazards such as internal short-circuit can not occur.
Lithium ion battery composite separation membrane provided by the invention, by the chemical property that its functional coating is excellent, after battery temperature raises, functional coating can absorb the waste heat of battery fast, as reaction entropy, spontaneously responds chemical reaction, generates protective layer.On the one hand, effectively suppress the continuation of the temperature of battery to raise, on the other hand, the active layer of passivation cell anode and cathode, controls the potential safety hazard of battery from root, ensures the fail safe of battery.
In addition, because functional coating hardness of the present invention is less, the process loss in cell fabrication processes can be reduced, thus reduce the production cost of battery.
Result shows, lithium ion battery composite separation membrane provided by the invention all shows less thermal contraction at different temperature, has good thermal stability; The liquid absorption of described lithium ion battery composite separation membrane in 30 minutes is 61 ~ 89g/m
2; Described composite diaphragm is prepared into lithium ion battery, its capability retention > 90% in 1500 cycle periods, and when carrying out cell safety test, there is superior security performance.
In order to understand the present invention further, be described lithium ion battery composite separation membrane provided by the invention and preparation method thereof and lithium ion battery below in conjunction with embodiment, protection scope of the present invention is not limited by the following examples.
Embodiment 1
A. the preparation of mixed slurry
According to the mass ratio of 96:4, accurately take melamine cyanurate (MCA), PVDF membrane (PVDF).MCA and PVDF is dispersed in solvent N-methyl pyrilidone (NMP) by high speed dispersor respectively, obtain MCA slurry and PVDF slurry, again that two kinds of slurry agitation are even, and be 50wt% by the solid content that solvent NMP controls in slurry, obtain mixed slurry.
B. the preparation of composite diaphragm
Mixed slurry is coated in the polypropylene one side of the Biaxially oriented polypropylene barrier film ceramic diaphragm of 25 μm, dry at 80 DEG C, the thickness obtaining coating is 4 μm, obtains the composite diaphragm of functional coat/bidirectional stretching polypropylene film/ceramic layer.Wherein, ceramic layer to be purity be 99.999% nano aluminium oxide.
C. battery makes
1) preparation of positive pole: add the active material LiNi that mass fraction is respectively 93wt% in solvent NMP
1/3co
1/3mn
1/3o
2, the conductive agent carbon black of 4wt% and the binding agent PVDF of 3wt%, mix obtained tertiary cathode slurry, anode sizing agent being evenly coated in thickness is that on the plus plate current-collecting body Al paper tinsel of 20 μm, drying obtains positive pole, and roll-in is for subsequent use;
2) preparation of negative pole: add the negative electrode active material graphite powder that mass fraction is respectively 95wt% in solvent deionized water, the binding agent SBR (butadiene-styrene rubber) of the conductive agent carbon black of 2wt%, the thickener CMC (sodium carboxymethylcellulose) of 1wt% and 2wt%, mix and obtain cathode size, cathode size being evenly coated in thickness is on the negative current collector Cu paper tinsel of 10 μm, drying obtains negative pole, and roll-in is for subsequent use;
3) assembling of lithium ion battery: function barrier film, positive pole and negative pole lamination are formed assembly, and wherein functional coating presses close to the positive pole of battery.
4) injection of electrolyte: inject electrolyte to lithium-ion battery module, obtain lithium rechargeable battery.Described electrolyte is LiPF
6in the system of EC, EMC and DMC composition, described LiPF
6concentration be 1mol/L, EC, the volume ratio of EMC and DMC is 1: 1: 1.
Embodiment 2
A. the preparation of mixed slurry
According to the mass ratio of 98:2, accurately take pentaerythrite melamine phosphate (PPMS) and PVDF membrane (PVDF).PPMS and PVDF is dispersed in solvent NMP by high speed dispersor respectively, obtains PPMS slurry and PVDF slurry, more above-mentioned two kinds of slurries are uniformly dispersed, and regulate solid content in slurry to be 39wt% by solvent NMP, obtain mixed slurry.
B. the preparation of composite diaphragm
Mixed slurry is coated in the polyethylene one side of the polyvinyl ceramic diaphragm of 25 μm, dry at 65 DEG C, controlling coating thickness is 3 μm, obtains the composite diaphragm of functional coat/polyethylene film/ceramic layer.Wherein, ceramic layer to be purity be 99.999% nano aluminium oxide.
C. battery makes
The process that battery makes, with embodiment 1, is only the composite diaphragm in embodiment 1 is replaced with the composite diaphragm that the present embodiment prepares.
Embodiment 3
A. the preparation of mixed slurry
Ammonium polyphosphate (APP), dimethyl silicone polymer (PDMS) and butadiene-styrene rubber (SBR) is accurately taken according to the mass ratio of active ingredient 80:15:5, by polydimethylsiloxane and ammonium polyphosphate on high speed dispersor with the linear velocity rapid stirring 30min of 50m/s, obtain the APP particle (PDMS-APP) that PDMS is coated.PDMS-APP is dispersed in deionized water by high speed dispersor, then SBR is added in above-mentioned mixed liquor, be uniformly dispersed, being 60wt% by controlling solid content in interpolation deionized water slurry, obtaining mixed slurry.
B. the preparation of composite diaphragm
Mixed slurry is coated in the polypropylene one side of the Biaxially oriented polypropylene base ceramic diaphragm of 20 μm, dry at 70 DEG C, the thickness obtaining applying is 5 μm, obtains the composite diaphragm of functional coat/bidirectional stretching polypropylene film/ceramic layer.Wherein, ceramic layer to be purity be 99.999% nano aluminium oxide.
C. battery makes
The process that battery makes, with embodiment 1, is only the composite diaphragm in embodiment 1 is replaced with the composite diaphragm that the present embodiment prepares.
Embodiment 4
A. the preparation of mixed slurry
Melamine pyrophosphate (MPP) and LA132 is accurately taken according to the mass fraction of active ingredient 95.5:4.5, MPP and LA132 will be dispersed in deionized water by high speed dispersor respectively, obtain MPP slurry and LA132 slurry, again above-mentioned two kinds of slurries are uniformly dispersed, and be 45wt% by deionized water control solid content, obtain mixed slurry.
B. the preparation of composite diaphragm
Mixed slurry is coated in the two-sided of the polyethylene diagrams of 20 μm, dries at 80 DEG C, controlling one side coating thickness is 3 μm.
C. battery makes
The process that battery makes, with embodiment 1, is only the composite diaphragm in embodiment 1 is replaced with the composite diaphragm that the present embodiment prepares.
Embodiment 5
A. the preparation of mixed slurry
Melamine phosphate (MPOP) and SBR is accurately taken according to the mass fraction of active ingredient 97:3, MPOP will be dispersed in deionized water by high speed dispersor respectively, SBR is added above-mentioned slurry to be uniformly dispersed, and be 40wt% by deionized water control solid content, obtain mixed slurry.
B. the preparation of composite diaphragm
Mixed slurry is coated in the two-sided of the Biaxially oriented polypropylene barrier film of 16 μm, dries at 80 DEG C, controlling one side coating thickness is 4 μm.
C. battery makes
The process that battery makes, with embodiment 1, is only the composite diaphragm in embodiment 1 is replaced with the composite diaphragm that the present embodiment prepares.
Embodiment 6
A. the preparation of mixed slurry
Ammonium polyphosphate (APP) and PVDF membrane (PVDF) is accurately taken according to the mass fraction of active ingredient 98:2, APP and PVDF will be dispersed in NMP by high speed dispersor respectively, obtain APP slurry and PVDF slurry, again above-mentioned two kinds of slurries are uniformly dispersed, and be 30wt% by NMP control solid content, obtain mixed slurry.
B. the preparation of composite diaphragm
Mixed slurry is coated in the one side of the polyethylene diagrams of 16 μm, dries at 65 DEG C, controlling one side coating thickness is 4 μm.
C. battery makes
The process that battery makes, with embodiment 1, is only the composite diaphragm in embodiment 1 is replaced with the composite diaphragm that the present embodiment prepares.
Embodiment 7
A. the preparation of mixed slurry
Melamine pyrophosphate (MPP), melamine cyanurate (MCA) and SBR is accurately taken according to the mass fraction of active ingredient 50:45:5, on high speed dispersor, just MPP and MCA is dispersed in deionized water, again SBR is added above-mentioned slurry to be uniformly dispersed, and be 55wt% by deionized water control solid content, obtain mixed slurry.
B. the preparation of composite diaphragm
Mixed slurry is coated in the one side of the Biaxially oriented polypropylene barrier film of 12 μm, dries at 70 DEG C, controlling one side coating thickness is 5 μm.
C. battery makes
The process that battery makes, with embodiment 1, is only the composite diaphragm in embodiment 1 is replaced with the composite diaphragm that the present embodiment prepares.
Embodiment 8
A. the preparation of mixed slurry
Ammonium polyphosphate (APP), melamine cyanurate (MCA) and PVDF is accurately taken according to the mass fraction of active ingredient 50:47:3, MPP and MCA is dispersed in NMP by high speed dispersor, again PVDF is added above-mentioned slurry to be uniformly dispersed, and be 35wt% by NMP control solid content, obtain mixed slurry.
B. the preparation of composite diaphragm
Mixed slurry is coated in the two-sided of the polyethylene diagrams of 12 μm, dries at 80 DEG C, controlling one side coating thickness is 3 μm.
C. battery makes
The process that battery makes, with embodiment 1, is only the composite diaphragm in embodiment 1 is replaced with the composite diaphragm that the present embodiment prepares.
Comparative example 1
Select 25 μm of Biaxially oriented polypropylene barrier films to make batteries, cell manufacturing process, with embodiment 1, is only the composite diaphragm in embodiment 1 is replaced with the barrier film that this comparative example provides.
Comparative example 2
Select 25 μm of polyethylene diagrams to make batteries, cell manufacturing process, with embodiment 1, is only the composite diaphragm in embodiment 1 is replaced with the barrier film that this comparative example provides.
Embodiment
1, the film shrink that embodiment 1 ~ 8 and comparative example 1 ~ 2 provide is measured
Lithium ion battery composite separation membrane prepared by Example 1 ~ 8 and the film that ratio 1 ~ 2 provides are placed in the baking oven 2h that temperature is 80 DEG C, 100 DEG C, 120 DEG C, 140 DEG C, 160 DEG C respectively, the percent thermal shrinkage of composite diaphragm under mensuration different temperatures, the results detailed in following table 1, table 1 is the percent thermal shrinkage of different temperatures lower diaphragm plate.
The percent thermal shrinkage of table 1 different temperatures lower diaphragm plate
As can be seen from Table 1, composite diaphragm prepared by embodiment 1 ~ 8 all shows less thermal contraction at different temperature, has good thermal stability.
2, the absorbency of the film that embodiment 1 ~ 8 and comparative example 1 ~ 2 provide is measured
Lithium ion battery composite separation membrane prepared by Example 1 ~ 8 and the film that ratio 1 ~ 2 provides are placed in electrolyte respectively and soak 30min, the weight of barrier film before and after soaking is weighed in confined space, the liquid absorption of unit of account area barrier film, the results detailed in Table 2, table 2 is the absorbent of different barrier film.
The absorbent of the different barrier film of table 2
As can be seen from Table 2, the absorbent of lithium ion battery composite separation membrane that prepared by embodiment is obviously better than comparative example.Because the coating being coated in composite diaphragm two sides all 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 liquid-keeping property of composite diaphragm, thus increase the cycle performance of lithium ion battery.
3, the cycle performance of battery is measured
Measure embodiment 1 ~ 8 and the capability retention of the lithium ion battery that comparative example 1 ~ 2 provides at the different cycle period of 1C/1C, the results detailed in following table 3, table 3 is the cycle performance of the lithium ion battery applying different barrier film.
The cycle performance of the lithium ion battery of different barrier film applied by table 3
As shown in Table 3, the wettability of lithium ion battery function barrier film prepared by embodiment 1 ~ 8 and electrolyte is better, thus makes battery have superior cycle performance.
4, the multiplying power discharging property of battery is measured
The capability retention that the lithium ion battery that mensuration embodiment 1 ~ 8 and comparative example 1 ~ 2 provide discharges under 3C multiplying power, the results detailed in following table 4, table 4 is the multiplying power discharging property of the lithium ion battery applying different barrier film.
The high rate performance of the lithium ion battery of different barrier film applied by table 4
5, the security performance of test battery
Adopt the method (power accumulator safety requirements used for electric vehicle and test method) of GB/T31485-2015 to carry out security performance test to battery prepared by embodiment 1 ~ 8 and comparative example 1 ~ 2, the results are shown in Table 5, table 5 is cell safety test result.
Table 5 cell safety test result
As can be seen from Table 5, the lithium ion battery that prepared by embodiment 1 ~ 8 has superior security performance.
The above is only the preferred embodiment of the present invention; it should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention; can also make some improvements and modifications, these improvements and modifications also should be considered as protection scope of the present invention.
Claims (11)
1. a lithium ion battery composite separation membrane, it is characterized in that, comprise diaphragm matrix and be compound in the functional coat on described diaphragm matrix surface, described functional coat is prepared from by functional materials and adhesive, described functional materials be selected from phosphorus-containing compound, nitrogen-containing compound and inorganic silicon compounds one or more.
2. composite diaphragm according to claim 1, it is characterized in that, described functional materials be selected from pentaerythrite melamine phosphate and its esters, APP, poly-phosphoramide types compound, organophosphazene poly mer, polysiloxanes compounds and thiourea one or more.
3. composite diaphragm according to claim 2, it is characterized in that, described functional materials be selected from melamine cyanurate, pentaerythrite melamine phosphate, ammonium polyphosphate, dimethyl silicone polymer and melamine pyrophosphate one or more.
4. composite diaphragm according to claim 1, is characterized in that, the mass ratio of described functional materials and adhesive is (90 ~ 99): (1 ~ 10).
5. composite diaphragm according to claim 1, is characterized in that, the one side thickness of described functional coat is 3 ~ 6 μm.
6. composite diaphragm according to claim 1, is characterized in that, described diaphragm matrix is selected from microporous polyolefin film or polyolefin-based ceramic diaphragm.
7. composite diaphragm according to claim 1, is characterized in that, described binding agent is one or more in Kynoar and copolymer, acrylic acid and copolymer thereof, acrylate and copolymer, polyvinyl alcohol, carboxymethyl cellulose and polyurethane.
8. a preparation method for lithium ion battery composite separation membrane, is characterized in that, comprises the following steps:
A) be scattered in solvent by functional materials and adhesive, obtain mixed slurry, described functional materials is selected from phosphorus-containing compound, containing one or more in nitrogen compound and inorganic silicon compounds;
B) described mixed slurry is coated on diaphragm matrix surface, dries, obtain lithium ion battery composite separation membrane.
9. preparation method according to claim 8, is characterized in that, the mode of described coating is selected from transfer coating, dip-coating, blade coating, rotogravure application, spraying or silk screen printing.
10. a lithium ion battery, it is characterized in that, comprise positive pole, negative pole, barrier film and electrolyte, the lithium ion battery composite separation membrane that described barrier film prepares for the lithium ion battery composite separation membrane described in claim 1 ~ 7 or the preparation method described in claim 8 ~ 9.
11. lithium ion batteries according to claim 10, is characterized in that, the active material of described positive pole is selected from LiFePO
4, LiMn
2o
4, LiCoO
2, LiV
2o
5, LiNiO
2, LiNi
(1-x-y)co
xal
yo
2, LiNi
(1-m-n)co
mmn
no
2and LiCo
zni
(1-z)o
2one or more in material, wherein, 0≤x≤1,0≤y≤1, x+y=1; 0≤m≤1,0≤n≤1, m+n=1; 0≤z≤1.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201510660432.XA CN105161661A (en) | 2015-10-14 | 2015-10-14 | Composite diaphragm for lithium ion battery, preparation method of composite diaphragm, and lithium ion battery |
| PCT/CN2015/092663 WO2017063218A1 (en) | 2015-10-14 | 2015-10-23 | Composite separator for lithium ion battery and preparation method therefor, and lithium ion battery |
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| CN201510660432.XA CN105161661A (en) | 2015-10-14 | 2015-10-14 | Composite diaphragm for lithium ion battery, preparation method of composite diaphragm, and lithium ion battery |
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| WO (1) | WO2017063218A1 (en) |
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