CN106654119A - Mixed coating diaphragm and preparation method and application thereof - Google Patents
Mixed coating diaphragm and preparation method and application thereof Download PDFInfo
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- CN106654119A CN106654119A CN201610998791.0A CN201610998791A CN106654119A CN 106654119 A CN106654119 A CN 106654119A CN 201610998791 A CN201610998791 A CN 201610998791A CN 106654119 A CN106654119 A CN 106654119A
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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
- H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/52—Separators
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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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- 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
- Y02E60/13—Energy storage using capacitors
Abstract
The invention relates to a mixed coating diaphragm and a preparation method and an application thereof, and belongs to the technical field of an energy storage element. The mixed coating diaphragm comprises a base film, a ceramic granule coating layer and a polymer coating layer, wherein the ceramic granule coating layer is formed on one or two sides of the base film; and the polymer coating layer is formed on the base film and/or the ceramic granule coating layer. By forming the ceramic granule coating layer and the polymer coating layer on the base film concurrently, the mixed coating diaphragm provided by the invention obtains safety of a pure ceramic coating diaphragm as well as obtains advantages of a fluorine-containing polymer coating diaphragm, so that the wettability, ionic conductivity, high-temperature resistance, cycle life, rate capability and the like of the diaphragm can be improved; and when the mixed coating diaphragm is applied to a battery capacitor or a lithium ion battery, the discharge specific capacity, the cycle life and the safety of the battery capacitor or the lithium ion battery can be effectively improved.
Description
Technical field
The present invention relates to a kind of barrier film, more particularly to a kind of ceramic particle and the mixed coating barrier film of mixed with polymers coating
And its preparation method and application, belong to energy-storage travelling wave tube technical field.
Background technology
Battery capacitor is a kind of emerging energy-storage travelling wave tube, and it is by lithium ion battery active material and ultracapacitor active matter
Matter collectively as electrode material, therefore, it has the high power of the high-energy-density of lithium ion battery and ultracapacitor simultaneously
The characteristics of density, long circulation life, the development of hybrid-electric car can be met.
Battery capacitor as lithium ion battery, mainly by positive electrode, negative material, electrolyte, barrier film, encapsulating material
Five parts constitute, wherein, barrier film is typically using the TPO barrier film of lithium ion battery.And barrier film rises between positive and negative electrode
Electronic isolation, the effect for providing lithium ion mobility micro channel, are to ensure battery system safety, affect the crucial material of battery performance
Material.Although barrier film does not directly participate in electrode reaction, it affects cell dynamics process, decides discharge and recharge, the circulation of battery
The performances such as life-span, multiplying power.
By barrier film be used for power energy-storage travelling wave tube, its first concern is high security, next contribute to energy density and
The other performance that power density is played is required.Therefore, it requires that battery capacitor barrier film meets claimed below：1., with higher
Security, including by heat endurance, electrochemical stability, puncture resistant resistance to shorting performance；2., more preferable uniformity, including thickness,
Aperture and pore-size distribution etc.；3., preferable porosity and pore structure；4., higher imbibition ability and less resistance etc..
At present, it is commercialized lithium battery diaphragm and is mainly polyethylene (PE) film, polypropylene (PP) single or multiple lift composite membrane, its
In, PP barrier films and PP/PE/PP sandwich diaphragms are power lithium battery barrier films conventional at present.These polyolefin based materials have strong
Degree height, good corrosion resistance, chemically-resistant solvent, waterproof, it is nontoxic the advantages of, as barrier film base material, good mechanicalness can be provided
Energy and chemical stability, and with self-closing (shutdown) characteristic of high temperature, can to a certain extent ensure safety.But, this
A little polyolefin PP, PE barrier films are limited to by raw material physical property, and traditional organic solvent, such as：Ethylene carbonate (EC), carbon
Acid propylene ester (PC), diethyl carbonate (DEC) class electrolyte compatibility it is poor, and be easily deformed during close fusing point contraction etc. use
Limitation.Even the composite membrane of PP and PE, due to only about 30 DEG C of the fusion temperature difference of PP, PE, if heat release is excessive, temperature surpasses
When crossing fusion temperature (about 160 DEG C) of PP, it may occur that rupture of membranes or contraction, so as to cause internal short-circuit of battery, and then release a large amount of
Heat, and the generation of thermal runaway can cause very big hidden danger to the safety of battery.Therefore, using motive-power battery capacitance energy storage element
On, need to be modified barrier film.
At present, barrier film is modified and mainly have two methods, one kind is in polyalkene diaphragm surface coating inorganic ceramics
Powder, another kind is in polyalkene diaphragm surface coated polymer layer.Such as Chinese invention patent (publication number：CN105529425A)
Disclose a kind of ceramic diaphragm and its preparation method and application, make inorganic ceramic powder in the patent (particle diameter is 2-250nm)
For the main body filler of ceramic coating, while with the use of monodimension nanometer material (a diameter of 5-800nm, length is 500nm-50 μm)
As the reinforcer in ceramic coating, it is coated on an at least side surface of matrix and is dried, obtains ceramic diaphragm.The patent
Made by barrier film coating surface is smooth, gas permeability is high, while have preferable mechanical property and heat-shrinkable, but the patent
Made by barrier film there was only ceramic coating, without polymer coating, the performance such as pick up, heat resistance of barrier film is not enough, main application
In lithium battery.And for example Chinese invention patent (publication number：CN105932209A) disclose a kind of as lithium ion battery
Ceramic coating membrane and preparation method thereof, the patent adopts inorganic ceramic powder, fluorine-containing sulfimide lithium salts polymer P FSI-Li
With commercial binding agent (methacrylate (PMMA), butadiene-styrene rubber (SBR), sodium carboxymethylcellulose (CMC) and polyacrylic acid
(PAA) coating slurry) is prepared, slurry is coated in into basement membrane single or double with blade applicator and prepared ceramic diaphragm is dried.This is special
Profit reduces the electricity at film two ends by including in polymer P FSI-Li with more highly polar and ionic conductivity ionic group
Potential difference, it is achieved thereby that quickly discharge and recharge under big multiplying power.
The content of the invention
The purpose of the present invention is to be directed to the above-mentioned problems in the prior art, it is proposed that a kind of wettability is good, ion
Electrical conductivity is high, resistant to elevated temperatures mixed coating barrier film.
The purpose of the present invention can be realized by following technical proposal：A kind of mixed coating barrier film, the barrier film includes base
Film, ceramic particle coating and polymer coating, the ceramic particle coating is formed in basement membrane side or both sides, the polymer
Coating be formed on basement membrane and/or ceramic particle coating on.
Ceramic particle coating and polymer coating, polymer coating are formed with the basement membrane of the mixed coating barrier film of the present invention
Can be formed directly on basement membrane, or be formed in ceramic particle coating, but basement membrane and ceramic particle coating can not be formed at
Between.Because in the present invention, ceramic particle coating can construct resistance to as rigid backbone in membrane surface or internal void
Heat zone, can keep dimensional stability, increase the temperature difference of hot closed pore temperature and broken film temperature, prevent because of barrier film pyrocondensation, just,
Thermal runaway caused by cathode contact, improves the mechanical performance and resistance to elevated temperatures of barrier film, so as to improve barrier film security feature.And
Formed on basement membrane or ceramic particle coating and the preferable polymer coating of electrolyte blind date ability, it is possible to increase barrier film and electrolyte
Affinity, improve barrier film pick up and heat resistance, strengthen barrier film keep electrolyte ability, so as to improve mixed coating
The electrochemical properties of barrier film.Therefore, the present invention is made by being formed simultaneously with ceramic particle coating and polymer coating on basement membrane
The mixed coating barrier film of the present invention had both possessed the security of simple ceramic coating membrane, but also with each of polymer-coated barrier film
Item advantage, can improve the performances such as wettability, ionic conductivity, resistance to elevated temperatures, cycle life and the multiplying power of barrier film.
In a kind of above-mentioned mixed coating barrier film, the basement membrane is cellulose paper or MIcroporous polyolefin film, and thickness is 10-
30μm。
In a kind of above-mentioned mixed coating barrier film, the MIcroporous polyolefin film includes that PE films, PP films, PP/PE are double-deck multiple
In closing film, PP/PP double-layered compound films, PE/PE double-layered compound films, PP/PE/PP sandwich diaphragms, PE/PP/PE sandwich diaphragms
One or more.
In a kind of above-mentioned mixed coating barrier film, the ceramic particle coating by being made with major ingredient inorganic ceramic particle,
Thickness is 0.5-10 μm.
In a kind of above-mentioned mixed coating barrier film, the particle diameter of the inorganic ceramic particle is 0.01-1 μm, including three oxygen
Change two aluminium ceramic particles, SiO 2-ceramic particle, titanium dioxide ceramic particle, zirconia ceramic particle, tin ash pottery
One or more in porcelain particle, magnesia ceramics particle, calcium oxide ceramics particle.The inorganic ceramic particle of the present invention can be
Rigid backbone is formed in mixed coating barrier film, prevents barrier film from shrinking even melting under the high temperature conditions, to lift battery peace
Full performance.
In a kind of above-mentioned mixed coating barrier film, the polymer coating is made up of fluoropolymer, and thickness is 0.5-
10μm。
In a kind of above-mentioned mixed coating barrier film, the fluoropolymer is PVDF, P (VDF-HFP) and P (VDF-
TrFE one or more in).The fluorinated polymer material of the present invention has strong polarity and high dielectric constant, on barrier film
The fluoropolymer of the coating present invention can greatly promote the lyophily of barrier film, and contribute to the ionization of lithium salts.
Second purpose of the invention is the preparation method for providing above-mentioned mixed coating barrier film, and the preparation method includes：
Ceramic particle coating is formed at into side or both sides on basement membrane；With
By polymer coating be formed on basement membrane and/or ceramic particle coating on.
Specifically, the preparation method of mixed coating barrier film of the present invention is：Ceramic particle is scattered in into dividing for aqueous binders
Ceramic size is obtained in scattered glue, polymer is made into polymer glue；
Ceramic size is coated on again the one or both sides of basement membrane, is dried, obtain ceramic particle coated separator；
Then in the one or both sides coated polymer glue of ceramic particle coated separator, drying, obtain mixed coating every
Film.
Preferably, the aqueous binders include polyvinyl alcohol (PVA), gelatin (Gelatin), polyethylene glycol oxide
(PEO), sodium carboxymethylcellulose (CMC), butadiene-styrene rubber (SBR) and polyacrylate based terpolymers latex (LA132,
LA133 at least one in).
Preferably, the coating method includes the one kind in spraying, dip-coating, brushing, micro- rotogravure application or roller coat.
Second purpose of the invention is to provide the application of above-mentioned mixed coating barrier film, the mixed coating diaphragm application in
In battery capacitor or lithium ion battery.
Preferably, just extremely lithium ion battery electrode material LiMn2O4 and the electrode material for super capacitor of battery capacitor
The mixture of activated carbon.
Preferably, the negative pole of battery capacitor is lithium ion battery electrode material lithium titanate and electrode material for super capacitor
The mixture of activated carbon.
Preferably, electrolyte is lithium hexafluoro phosphate (LiPF6) it is dissolved in ethylene carbonate (EC), dimethyl carbonate
(DMC) mixed solution of composition.
Compared with prior art, the present invention has following advantage：
1. the present invention is on basement membrane by being formed simultaneously with ceramic particle coating and polymer coating, especially fluoropolymer
Thing coating, makes mixed coating barrier film of the invention both possess the security of simple ceramic coating membrane, but also with fluoropolymer
Thing coats every advantage of barrier film, can improve the wettability of barrier film, ionic conductivity, resistance to elevated temperatures, cycle life and
The performances such as multiplying power.
2. the preparation method of mixed coating barrier film of the present invention is simple, easily realizes industrialization.
3. the mixed coating diaphragm application of the present invention can be effectively improved into battery in battery capacitor or lithium ion battery
The specific discharge capacity of electric capacity or lithium ion battery, cycle life and security.
Description of the drawings
Fig. 1 is the structural representation of the mixed coating barrier film of embodiment 1；
Fig. 2 is the structural representation of the mixed coating barrier film of embodiment 2；
Fig. 3 is the structural representation of the mixed coating barrier film of embodiment 3；
Fig. 4 is the structural representation of the mixed coating barrier film of embodiment 4；
Fig. 5 is the structural representation of the mixed coating barrier film of embodiment 5.
In figure, 1, basement membrane；2nd, ceramic particle coating；3rd, polymer coating.
Specific embodiment
The specific embodiment of the present invention is the following is, and is described with reference to the drawings technical scheme is further retouched
State, but the present invention is not limited to these embodiments.
Embodiment 1：
2g CMC are weighed, with 100g deionized waters as decentralized medium, preparation dispersion glue are stirred under vacuum,
The alundum (Al2O3) for weighing 15g 50nm is placed in dispersion glue, and vacuum stirring obtains ceramic size.Ceramic size is passed through again
Micro- gravure coating process is coated on the two sides of 10 μm of PP/PE basement membranes, drying, obtains ceramic particle coated separator, ceramic particle
One side coating layer thickness control at 2 μm.
Weigh 6g PVDF and be stirred in 30g NMP, under vacuum and obtain PVDF glues.Then dip-coating is passed through
Method by PVDF glues be coated in it is above-mentioned made by ceramic particle coated separator two-sided, drying, the one side coating layer thickness of PVDF is 4
μm, mixed coating barrier film is made in finally cutting, and the structure of mixed coating barrier film is as shown in Figure 1.
Embodiment 2：
4g LA133 are weighed, with 100g deionized waters as decentralized medium, is stirred prepares dispersion agent under vacuum
Liquid, the silica for weighing 20g 100nm is placed in dispersion glue, and vacuum stirring obtains ceramic size.Ceramic size is led to again
The one side that spread coating is coated on 10 μm of PP basement membranes is crossed, is dried, obtain ceramic particle coated separator, the coating layer thickness of ceramic particle
Control is at 4 μm.
Weigh 3g P (VDF-HFP) and 2g PVDF and be stirred in 60g NMP, under vacuum and obtain PVDF and P
(VDF-HFP) mixed glue solution.Then by spraying process by mixed glue solution be coated in it is above-mentioned made by ceramic particle coated separator
Another side, drying, the thickness of the mixed coating of PVDF and P (VDF-HFP) is 4 μm, and mixed coating barrier film is made in finally cutting,
The structure of mixed coating barrier film is as shown in Figure 2.
Embodiment 3：
3g Gelatin are weighed, with 10g deionized waters as decentralized medium, is stirred prepares dispersion agent under vacuum
Liquid, the titanium dioxide of the silica and 10g 50nm that weigh 10g 80nm is placed in dispersion glue, and vacuum stirring is mixed
Ceramic size.Hybrid ceramic slurry is coated on again the one side of 20 μm of PP/PE/PP basement membranes by spread coating, is dried, made pottery
Porcelain grain coating barrier film, the coating layer thickness of ceramic particle is controlled at 2 μm.
Weigh 3g P (VDF-HFP) and 3g P (VDF-TrFE) are stirred in 80g NMP, under vacuum and obtain
The mixed glue solution of P (VDF-TrFE) and P (VDF-HFP).Then mixed glue solution is coated in by above-mentioned ceramic particle by spraying process
Two-sided, the drying of coated separator, the one side thickness of the mixed coating of P (VDF-TrFE) and P (VDF-HFP) is 2 μm, is finally cut
Mixed coating barrier film is made, the structure of mixed coating barrier film is as shown in Figure 3.
Embodiment 4：
3g PVA and 1g PEO are weighed, with 100g deionized waters as decentralized medium, preparation is stirred under vacuum
Dispersion glue, the titanium dioxide and 10g 100nm zirconium dioxides for weighing 10g 50nm is placed in dispersion glue, and vacuum stirring is obtained
Hybrid ceramic slurry.Hybrid ceramic slurry is coated on again two-sided, the drying of 20 μm of PP/PE/PP basement membranes by dip coating, is obtained
To ceramic particle coated separator, the one side coating layer thickness control of ceramic particle is at 6 μm.
Weigh 3g P (VDF-HFP) and 3g P (VDF-TrFE) are stirred in 80g NMP, under vacuum and obtain
The mixed glue solution of P (VDF-HFP) and P (VDF-TrFE).Then mixed glue solution is coated in by above-mentioned ceramic particle by spraying process
Any one side of coated separator, drying, the thickness of the mixed coating of P (VDF-TrFE) and P (VDF-HFP) is 3 μm, is finally cut
Mixed coating barrier film is made, the structure of mixed coating barrier film is as shown in Figure 4.
Embodiment 5：
4g LA132 are weighed, with 100g deionized waters as decentralized medium, is stirred prepares dispersion agent under vacuum
Liquid, the silica for weighing 20g 100nm is placed in dispersion glue, and vacuum stirring obtains ceramic size.Ceramic size is led to again
The one side that spread coating is coated on 10 μm of PE basement membranes is crossed, is dried, obtain ceramic particle coated separator, the coating layer thickness of ceramic particle
Control is at 4 μm.
Weigh 3g P (VDF-HFP) and 2g PVDF and be stirred in 60g NMP, under vacuum and obtain PVDF and P
(VDF-HFP) mixed glue solution.Then by spraying process by mixed glue solution be coated in it is above-mentioned made by ceramic particle coated separator
Ceramic particle coating on, drying, the thickness of the mixed coating of PVDF and P (VDF-HFP) is 4 μm, and mixing is made in finally cutting
Coated separator, the structure of mixed coating barrier film is as shown in Figure 5.
Comparative example 1：
Comparative example 1 is 10 μm of PP/PE barrier films, identical with the performance of PP/PE basement membranes of the present invention.
Comparative example 2：
Comparative example 2 is 10 μm of PP barrier films, identical with the performance of PP basement membranes of the present invention.
Comparative example 3：
Comparative example 3 is 10 μm of PP/PE/PP barrier films, identical with the performance of PP/PE/PP basement membranes of the present invention.
Comparative example 4：
Comparative example 4 is 10 μm of PE barrier films, identical with the performance of PE basement membranes of the present invention.
Barrier film in mixed coating barrier film made by above-described embodiment 1-5 and comparative example 1-4 is carried out into performance test comparison,
Detailed process and result are：
Difference 60 × 60mm of cutting2The above-mentioned barrier film of rule, area is designated as S0.Baking oven is then placed in 160 DEG C of holdings
20min, calculates the area of barrier film, is designated as S1.Recycle formula：η=(S0-S1)/S0× 100% shrinkage from mold dimensions, test result
It is shown in Table 1.
The each 0.5g of above-mentioned barrier film is weighed respectively, and weight is designated as M0.In being placed in identical electrolyte, take out after half an hour, claim
The weight of amount barrier film, weight is designated as M1.Recycle formula：β=(M0-M1)/M0× 100% calculates pick up, and test result is shown in Table
1。
Table 1：
By the diaphragm application of the mixed coating barrier film of the present invention and comparative example in battery capacitor and lithium ion battery, specifically
It is as follows：
Application Example 1-5：
The preparation of battery capacitor positive plate：100g LiMn2O4s and 20g activated carbons are weighed respectively, are carried out in ball mill at a high speed
Stirring 1h, is uniformly mixed to get composite A.PVDF and NMP is pressed into 1:10 mass ratioes carry out vacuum high-speed stirred 1.5h.Add
Conductive agent Super-P and composite A and appropriate NMP stirring 1.5h obtain anode sizing agent, A in slurry：Super-P：CNT：
PVDF=93:2:2:3.Slurry is coated on the corrosive aluminum foil two sides that thickness is 20 μm so that thickness of electrode is 190 μm.It is logical
Cross to be rolled after high-temperature baking and obtain positive plate.
The preparation of battery capacitor negative plate：Lithium titanate and activated carbon (mass ratio 100:20) the composite B being mixed to get,
Conductive agent is acetylene black, and binding agent is LA132, and dispersant is water.Composite B：Acetylene black：LA132=93：4：3, electrode is thick
Spend for 220 μm, preparation method is identical with positive plate.
It is prepared by battery core：Mixed coating barrier film made by positive and negative electrode pole piece and embodiment of the present invention 1-5 is passed sequentially through " Z "
Shape lamination makes battery core, and 170 DEG C of Jing vacuum is dried 18h.
The preparation of electrolyte：By LiPF6It is dissolved in (EC in the mixed solvent of EC and DMC：DMC=3:7by volume) make
Mixed solution.
Soft Roll sample preparation：Battery core is packaged in aluminum plastic film in glove box, after encapsulation, injection electrolyte, standing 12h
Forming and capacity dividing is fabricated to battery capacitor.
Comparison study example 1-4：
Comparison study example 1-4 differing only in using Application Example, the barrier film of Comparison study example 1-4 adopts comparative example
The barrier film of 1-4.
By battery capacitor made by Application Example 1-5 and made by Comparison study example 1-4, battery capacitor carries out performance
Test comparison.Battery capacitor Soft Roll sample is melted into respectively under 0.1C (1C=150mAh/g), is then tested under 2C
Cycle performance, writes down first discharge specific capacity.1000 calculating capability retentions of circulation, test result is shown in Table 2.
Table 2：
Application Example 6-10：
The preparation of positive plate：PVDF and NMP is pressed into 1:10 mass ratioes carry out vacuum high-speed stirred 1.5h, add 2g conductive agents
Super-P, carries out high-speed stirred 1h in ball mill, adds 96g LiMn2O4s and appropriate NMP stirring 1.5h obtain positive pole slurry
Material, LiMn2O4 in slurry：Super-P:PVDF=96:2:2.Slurry is coated on the corrosive aluminum foil two sides that thickness is 20 μm,
So that thickness of electrode is 190 μm.Rolled after high-temperature baking and obtain positive plate.
The preparation of negative plate：PVDF and NMP is pressed into 1:10 mass ratioes carry out vacuum high-speed stirred 1.5h, add conductive agent
2.5gSuper-P, carries out high-speed stirred 1h in ball mill, adds 95g lithium titanates and appropriate NMP stirring 1.5h obtain negative pole
Slurry, lithium titanate in slurry：Super-P:PVDF=95:2.5:2.5.Slurry is coated on into the corrosive aluminum foil two that thickness is 20 μm
On face so that thickness of electrode is 170 μm.Rolled after high-temperature baking and obtain negative plate.
It is prepared by battery core：Mixed coating barrier film made by positive and negative electrode pole piece and embodiment of the present invention 1-5 is passed sequentially through " Z "
Shape lamination makes battery core, and 170 DEG C of Jing vacuum is dried 18h.
Electrolyte：1mol/L LiPF6/EC+DMC+DEC。
Soft Roll sample preparation：Battery core is packaged in aluminum plastic film in glove box, after encapsulation, injection electrolyte, standing 12h
Forming and capacity dividing is fabricated to lithium ion battery.
Comparison study example 5-8：
Comparison study example 5-8 differing only in using Application Example, the barrier film of Comparison study example 5-8 adopts comparative example
The barrier film of 1-4.
By battery capacitor made by Application Example 6-10 and made by Comparison study example 5-8, battery capacitor carries out performance
Test comparison.Battery capacitor Soft Roll sample is melted into respectively under 0.1C (1C=150mAh/g), is then tested under 2C
Cycle performance, writes down first discharge specific capacity.1000 calculating capability retentions of circulation, test result is shown in Table 3.
Table 3：
It is of the invention after ceramic coated and fluoropolymer-coated knowable to table 1, table 2 and table 3, the high temperature resistant of barrier film
Property and pick up be all significantly larger than undressed polyalkene diaphragm, and effectively increase battery capacitor and lithium ion battery
Specific discharge capacity and cycle life.
In above-described embodiment and its alternative, basement membrane can also be cellulose paper, PP/PP double-layered compound films, PE/PE
Double-layered compound film, PE/PP/PE sandwich diaphragms.
In above-described embodiment and its alternative, the thickness of basement membrane also include 11 μm, 12 μm, 13 μm, 14 μm, 15 μm,
16 μm, 17 μm, 18 μm, 19 μm, 21 μm, 22 μm, 23 μm, 24 μm, 25 μm, 26 μm, 27 μm, 28 μm, 29 μm, 30 μm, and 10-
Any value between 30 μm.
In above-described embodiment and its alternative, the thickness of ceramic particle coating also include 0.5 μm, 1 μm, 3 μm, 5 μm,
7 μm, 8 μm, 9 μm, 10 μm, and any value between 0.5-10 μm.
In above-described embodiment and its alternative, the particle diameter of inorganic ceramic particle also includes 0.01 μm, 0.02 μm, 0.1 μ
m、0.15μm、0.2μm、0.25μm、0.3μm、0.35μm、0.4μm、0.45μm、0.5μm、0.55μm、0.6μm、0.65μm、0.7
μm, 0.75 μm, 0.8 μm, 0.85 μm, 0.9 μm, 0.95 μm, 1 μm, and any value between 0.01-1 μm.
In above-described embodiment and its alternative, inorganic ceramic particle also includes titanium dioxide ceramic particle, titanium dioxide
Zircon ceramic particle, stannic oxide ceramic particle, magnesia ceramics particle, calcium oxide ceramics particle, and aluminum oxide ceramic
Particle, SiO 2-ceramic particle, titanium dioxide ceramic particle, zirconia ceramic particle, stannic oxide ceramic particle, oxidation
Arbitrarily several mixing in magnesium ceramic particle, calcium oxide ceramics particle.
In above-described embodiment and its alternative, the thickness of polymer coating also includes 0.5 μm, 1 μm, 5 μm, 6 μm, 7 μ
M, 8 μm, 9 μm, 10 μm, and any value between 0.5-10 μm.
In above-described embodiment and its alternative, fluoropolymer can also be P (VDF-HFP), P (VDF-TrFE),
The mixing of PVDF and P (VDF-TrFE), PVDF and P (VDF-HFP), the mixing of P (VDF-TrFE) three.
In view of the present invention program embodiment is numerous, each embodiment experimental data is huge numerous, is not suitable for arranging one by one herein
Explanation is lifted, but the content of checking required for each embodiment and the final conclusion for obtaining are close to, the mixed coating barrier film for obtaining
Both possessed the security of simple ceramic coating membrane, but also with every advantage of fluoropolymer-coated barrier film, can improve
The performances such as the wettability of barrier film, ionic conductivity, resistance to elevated temperatures, cycle life and multiplying power.So herein not to each reality
The checking content for applying example and Application Example is illustrated one by one, only using embodiment 1-5 and Application Example 1-10 as generation
Table illustrates the excellent part of the present patent application.
Specific embodiment described herein is only explanation for example spiritual to the present invention.Technology neck belonging to of the invention
The technical staff in domain can be made various modifications to described specific embodiment or supplement or substituted using similar mode, but and
Do not deviate by the spirit of the present invention or surmount scope defined in appended claims.
It is skilled to this area although having made a detailed description and being cited some specific embodiments to the present invention
For technical staff, as long as it is obvious that can make various changes without departing from the spirit and scope of the present invention or correct.
Claims (9)
1. a kind of mixed coating barrier film, it is characterised in that the barrier film includes basement membrane, ceramic particle coating and polymer coating,
The ceramic particle coating is formed in basement membrane side or both sides, and the polymer coating is formed on basement membrane and/or ceramics
In grain coating.
2. a kind of mixed coating barrier film according to claim 1, it is characterised in that the basement membrane is cellulose paper or polyene
Hydrocarbon microporous barrier, thickness is 10-30 μm.
3. a kind of mixed coating barrier film according to claim 2, it is characterised in that the MIcroporous polyolefin film includes PE
Film, PP films, PP/PE double-layered compound films, PP/PP double-layered compound films, PE/PE double-layered compound films, PP/PE/PP sandwich diaphragms,
One or more in PE/PP/PE sandwich diaphragms.
4. a kind of mixed coating barrier film according to claim 1, it is characterised in that the ceramic particle coating is with major ingredient
Inorganic ceramic particle is made, and thickness is 0.5-10 μm.
5. a kind of mixed coating barrier film according to claim 4, it is characterised in that the particle diameter of the inorganic ceramic particle is
0.01-1 μm, including aluminum oxide ceramic particle, SiO 2-ceramic particle, titanium dioxide ceramic particle, zirconium dioxide pottery
One or more in porcelain particle, stannic oxide ceramic particle, magnesia ceramics particle, calcium oxide ceramics particle.
6. a kind of mixed coating barrier film according to claim 1, it is characterised in that the polymer coating is by fluoropolymer
Thing is made, and thickness is 0.5-10 μm.
7. a kind of mixed coating barrier film according to claim 6, it is characterised in that the fluoropolymer is PVDF, P
(VDF-HFP) one or more and in P (VDF-TrFE).
8. a kind of preparation method of the mixed coating barrier film as described in claim 1-7 is arbitrary, it is characterised in that the preparation side
Method includes：
Ceramic particle coating is formed at into side or both sides on basement membrane；With
By polymer coating be formed on basement membrane and/or ceramic particle coating on.
9. a kind of application of the mixed coating barrier film as described in claim 1-7 is arbitrary, it is characterised in that the mixed coating every
Film is applied in battery capacitor or lithium ion battery.
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