CN107293682A - Lithium ion battery and its barrier film - Google Patents
Lithium ion battery and its barrier film Download PDFInfo
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- CN107293682A CN107293682A CN201610204456.9A CN201610204456A CN107293682A CN 107293682 A CN107293682 A CN 107293682A CN 201610204456 A CN201610204456 A CN 201610204456A CN 107293682 A CN107293682 A CN 107293682A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—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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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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Abstract
The invention discloses a kind of lithium ion battery barrier film, it includes the inorganic coating isolated film base material, be distributed in isolation film base material at least one side, and the organic coating at least one inorganic coating is distributed in, wherein, the coating density of organic coating is 0.1mg/1540.25mm2~10mg/1540.25mm2.Relative to prior art, lithium ion battery barrier film of the present invention can improve the deformation of lithium ion battery and improve the expansive force that lithium-ion electric core can be born, so as to improve the cycle life of lithium ion battery.In addition, the invention also discloses a kind of lithium ion battery using lithium ion battery barrier film of the present invention.
Description
Technical field
The invention belongs to field of lithium ion battery, it is more particularly related to which a kind of have Ideal Cycle
The lithium ion battery and its barrier film of performance.
Background technology
As the important component of lithium ion battery, barrier film has weight to the cycle life of lithium ion battery
Influence.Existing lithium ion battery barrier film generally includes isolation film base material, is coated on isolation film base material extremely
Inorganic coating in few one side, and the organic coating being coated in inorganic coating at least one side.
Lithium ion battery completes, during recycling, and certain expansion can occur for anode and cathode slice,
As pole piece constantly expands, the expansive force that battery core is integrally born is gradually stepped up, and can cause phase occur between pole piece
The risk mutually extruded, and then influence the cycle performance and security performance of lithium ion battery.Meanwhile, in barrier film
Preparation process in, because the distribution of coating granule is more lax, (coating machine and winding after coating and winding
Machine has some tension), coating granule can make barrier film produce microcreping, and the organic coating of island and/or strip can be fallen into
Enter in microcreping pit, equivalent to have compressed coating layer thickness, so as to influence barrier film substrate surface organic coating thick
The uniformity of degree, therefore have impact on the cycle performance of expansive force that lithium ion battery can bear and lithium ion battery
And security performance.
In view of this, it is a kind of with acceptable highly expanded power, Ideal Cycle performance and safety it is necessory to provide
The lithium ion battery and its barrier film of performance.
The content of the invention
Present inventor passes through research and experimental analysis is found, the acceptable expansive force of lithium ion battery,
Cycle performance and security performance and organic coating coating density, the thickness of organic coating, organic painting in barrier film
Organic high score in the content and species of organic polymer particle and/or organic polymer emulsion, organic coating in layer
The content of binding agent, the thickness of isolation film base material in sub- grain graininess, organic coating, and inorganic coating
Thickness is relevant.
Found based on more than, the present invention is intended to provide a kind of have acceptable highly expanded power, Ideal Cycle performance
With the lithium ion battery and its barrier film of security performance.
In order to realize foregoing invention purpose, the invention provides a kind of lithium ion battery barrier film, it include every
The organic coating isolated in film base material at least one side is distributed in from film base material and directly or indirectly, wherein, it is described
The coating density of organic coating is 0.1mg/1540.25mm2~10mg/1540.25mm2。
Improved as one kind of lithium ion battery barrier film of the present invention, the thickness of the isolation film base material is
5-40μm。
Improved as one kind of lithium ion battery barrier film of the present invention, the isolation film base material is PE, PP, nothing
Spin cloth, PET, PVDF, PU, PA, PI, organic-inorganic blend film or PP/PE/PP.
Improved as one kind of lithium ion battery barrier film of the present invention, the organic coating includes organic polymer
Particle and/or organic polymer emulsion and binding agent.
Improved as one kind of lithium ion battery barrier film of the present invention, the organic polymer particle and/or organic
The weight content of macromolecule emulsion is 5%-95%, and the weight content of the binding agent is 5%-95%.
Improved as one kind of lithium ion battery barrier film of the present invention, the organic polymer particle and/or organic
Macromolecule emulsion be Kynoar, biasfluoroethylene-hexafluoropropylene polymer, styrene-butadiene,
At least one of polyacrylic acid, polyacrylate；The binding agent is polyamide, polyacrylonitrile, poly- third
Olefin(e) acid ester, polyacrylate, hydroxymethyl cellulose sodium, polyethylene give a tongue-lashing the poly- second of pyrrolidone, ethyl acetate, benzene
Alkene ether, polyvinylether, ethylene carbonate, propanetriol-diglycidyl-ether, propene carbonate, acetone, pure third
At least one of emulsion.
Improved as one kind of lithium ion battery barrier film of the present invention, the isolation film base material at least one side distribution
There is inorganic coating, the organic coating is distributed at least one inorganic coating, the organic coating is to winding
Lithium-ion electric core after hot pressing makes Gap abilities for 1-150 μm.
As lithium ion battery barrier film of the present invention one kind improve, the organic coating isolation film base material or
Area coverage ratio on inorganic coating is 1%-95%.
Improved as one kind of lithium ion battery barrier film of the present invention, the inorganic coating includes particles of inorganic material
And binding agent, the weight content of the inorganic particle is 5-95%, and the weight content of the binding agent is 5-95%.
In order to realize foregoing invention purpose, present invention also offers a kind of lithium ion battery, including anode pole piece,
Cathode pole piece, the barrier film being interval between anode pole piece and cathode pole piece, and electrolyte, wherein, institute
Barrier film is stated for foregoing lithium ion battery barrier film.
Relative to prior art, in lithium ion battery of the present invention, barrier film makes Gap equivalent in porous isolation
One layer of organic coating is applied on film, is pole piece circulation expansion headspace in lithium ion battery, so as to improve
Lithium ion battery bears the ability of expansive force, and improve lithium-ion electric core makes Gap abilities, improves lithium-ion electric
The cycle life and security performance in pond.
Brief description of the drawings
Below in conjunction with drawings and examples, lithium ion battery of the present invention and its barrier film are further described,
Wherein：
Fig. 1 show the end view of battery core in lithium ion battery of the present invention；
Fig. 2 is a kind of interlayer structure schematic diagram of lithium ion battery barrier film of the present invention.
Embodiment
In order that goal of the invention, technical scheme and the technique effect of the present invention become apparent from, below in conjunction with implementation
The present invention is described in more detail with comparative example for example.It should be appreciated that the implementation provided in this specification
Example is intended merely to explain the present invention, is not intended to limit the present invention.
Performance test
Low temperature analysis lithium test：1) lithium ion battery is shelved into 2h at 10 DEG C；2) 5min is stood；3)0.35C
Constant-current charge is to 4.35V；4) 5min is stood；5) 0.5C constant-current discharges are to 3.0V；Repeat 2) to 5) step 10
It is secondary, disassemble lithium ion battery and check whether anode surface analysis lithium occurs.
Cycle life is tested：1) lithium ion battery is shelved into 2h at 60 DEG C；2) 5min is stood；3) 2C constant currents
4.2V, then constant pressure (4.2V) charging are charged to until charging current 0.05C；4) 10min is stood；5) 3C constant currents
Release to 2.8V；6) 2) -5 are repeated) step, until battery core capacity is less than 70%.
Battery core makes Gap aptitude tests：
Gap refers to the organic coating thickness on two layers of barrier film being contacted on one layer of pole piece, more specifically,
Refer to the organic coating thickness for winding the battery core end after hot pressing, Gap measurement can be calculated as follows
Obtain：
Gap=(the L1-L2)/number of plies, Gap may be defined as naked battery core end for expanding the flat of available every layer of barrier film
Equal coating layer thickness.
It refer to shown in Fig. 1, Wind lithium ion core is divided into circular arc area and plane area, wherein, L1 is circle
Arc area innermost layer is to outermost distance；L2 is to most with circular arc area Winding Layer identical plane area innermost layer
The distance of outer layer；The number of plies is the number of plies of circular arc area barrier film 10.
In various embodiments of the present invention, Gap measurement is using Shanghai quintessence detection Science and Technology Ltd. model
For：GE Phoenix v | tome | x S 240 CT device scans, after CT device scans terminate, using computer
Survey Software, which can be tested, obtains L1, L2, and draws Gap.
Referring to Fig. 2, lithium ion battery barrier film 10 of the present invention includes isolation film base material 12, is distributed in isolation
Inorganic coating 14 on the one or both sides of film base material 12, and be distributed at least one inorganic coating 14
Organic coating 16.In various embodiments, can also be without using inorganic coating 14, by organic coating 16
It is dispensed directly onto the one or both sides of isolation film base material 12.It should be noted that Fig. 2 be only lithium of the present invention from
The interlayer structure schematic diagram of sub- battery isolating film 10, does not represent the microscopic appearance of each layer.
Embodiment 1-1 to 1-4 and comparative example 1-1 to 1-2
Embodiment 1-1
The preparation of anode pole piece：By positive active material ternary material NCM (Ni：Co：Mn=4：3：3)、
Conductive agent conductive carbon, binding agent Kynoar (PVDF) in mass ratio 96：2：2 well mixed are made have
The lithium ion battery anode glue size of certain viscosity；Anode sizing agent is uniformly coated on plus plate current-collecting body aluminium foil,
It is cold-pressed after being dried at 85 DEG C, then carries out trimming, cut-parts, slitting；After slitting at vacuum condition and 85 DEG C
Drying 4 hours, welds positive pole ear, anode slice of lithium ion battery is made.
The preparation of cathode pole piece：Negative electrode active material graphite, conductive agent conductive carbon, thickener methylol is fine
The plain sodium (CMC) of dimension, binding agent butadiene-styrene rubber (SBR) in mass ratio 97：1：1：1, which is made lithium ion battery, bears
Pole slurry；Cathode size is uniformly coated on negative current collector copper foil, at 85 DEG C dry after carry out trimming,
Cut-parts, slitting；Dried 4 hours at vacuum condition and 110 DEG C after slitting, weld negative lug, make lithium
Ion battery cathode pole piece.
The preparation of barrier film：Porous isolating membrane base material is used as from the polyethylene micropore film of 16 μ m-thicks.
The preparation of inorganic coating slurry：Inorganic coating slurry contain 30 parts by weight inorganic alchlor powder,
The polyethylene of 10 parts by weight gives a tongue-lashing the acetone solvent of pyrrolidone and 60 parts by weight, and specific preparation process is：
The first step：It is 100L's that the polyethylene of said ratio is given a tongue-lashing into pyrrolidone and the common 70Kg addition volumes of acetone
In double planetary mixer, disperse 3 hours at 25 DEG C；
Second step：Above-mentioned alundum (Al2O3) powder 30Kg is added in the mixer of the first step, at 35 DEG C
Scattered scattered 3 hours at a high speed down, low speed is stirred 1.5 hours slowly again afterwards, obtains inorganic coating slurry.
The preparation of inorganic coating：Surface coating is carried out to porous isolating membrane base material using dip coating manner, list is painted
Topcoat constructions；Drying is using one section of drying, and baking oven length is 10m, and baking oven design temperature is 55 DEG C, is applied
Cloth speed is 25m/min, and coating density is 5mg/cm2, a face inorganic coating thickness is 4 μm, inorganic coating
It is 90% in the area coverage ratio of porous isolating membrane base material.
The preparation of organic coating slurry：Organic coating slurry contains the Kynoar powder of 5 parts by weight, 40
The ethyl acetate of the acetone solvent of parts by weight and 55 parts by weight, specific preparation process is：
The first step：The common 95Kg of the acetoneand ethyl acetate of said ratio is added into the double-planet that volume is 100L
In mixer, stirring at low speed is mixed 1.5 hours at 25 DEG C；
Second step：5Kg Kynoar powder is added, high speed dispersing and dissolving 3 hours, are obtained at 35 DEG C
Organic coating slurry.
The preparation of organic coating：Porous isolation using plate gravure coating method to being surface-treated by inorganic coating
Film base material carries out surface coating, is coated with as barrier film two sided coatings structure, the weight and thickness of two sides organic coating
Degree is consistent；Drying is using one section of drying, and baking oven length is 10m, and oven temperature is 55 DEG C；Coating speed is
25m/min, organic coating coating density is 0.1mg/1540.25mm2, the thickness of organic coating is 30 μm,
After drying, organic coating is in island and wire pattern, organic coating on inorganic coating and on isolation film base material
It is 50% in the area coverage ratio of porous isolating membrane base material.
The preparation of electrolyte：Lithium hexafluoro phosphate is dissolved in ethylene carbonate, dimethyl carbonate and methyl ethyl carbonate
(volume ratio of ethylene carbonate, dimethyl carbonate and methyl ethyl carbonate is 1 to the in the mixed solvent of ester：2：1),
Obtain required electrolyte.
The preparation of lithium ion battery：Above-mentioned anode pole piece, cathode pole piece and barrier film are wound into lithium-ion electric
Core simultaneously injects electrolyte, and the process such as encapsulated, shaping, chemical conversion is prepared into lithium ion battery.
Refer to shown in table 1, embodiment 1-2 to 1-4 and comparative example 1-1 to 1-2 preparation process refer to
Embodiment 1-1 preparation process, wherein, isolation film base material, base material thickness, inorganic coating thickness, organic painting
In thickness degree, organic polymer particle and/or macromolecule emulsion in the granularity D50 and embodiment 1-1 of particle
Isolate film base material, base material thickness, inorganic coating thickness, organic coating thickness, organic polymer particle and/or
The granularity D50 all sames of particle, the difference is that only the coating density of organic coating in macromolecule emulsion.
The organic coating of table 1 is coated with the influence of density
As it can be seen from table 1 same separation film base material, base material thickness, inorganic coating thickness, organic coating
It is different organic in thickness, organic polymer particle and/or macromolecule emulsion in the case of the granularity D50 of particle
The influence for the circulation ability that coating coating density makes Gap abilities and lithium ion battery to barrier film is as follows：
1. when organic coating coating density is excessive (more than 10.0mg/1540.25mm2) when, although it is corresponding organic
Coating to make Gap very capable, but organic coating distribution excessively densification can cause in battery charge and discharge process
Barrier film diversion declines, and blackspot and low temperature analysis lithium occurs in barrier film surface, and organic coating is to lithium ion battery
Cycle life contribution decline；
2. (it is less than 0.1mg/1540.25mm when organic coating coating density is too small2) when, organic coating was distributed
In lax, cause the influence of organic coating island and/or strip pattern coating to isolation film base material formation microwave wave
Very big, battery core is actual to make that Gap abilities are very weak, and lithium ion battery bears the poor ability of expansive force, to lithium from
The contribution of sub- battery cycle life declines；
3. when organic coating is coated with density in 0.1mg/1540.25mm2-10.0mg/1540.25mm2Between when,
Organic coating island and/or strip pattern coating can reach the expected ability for making Gap, increase organic painting
While layer bears expansive force, anode analyses lithium without low temperature, so as to improve the cycle life of lithium ion battery；
In addition, organic coating coating density has certain linear relationship with making Gap abilities, coating density is bigger,
Make Gap abilities stronger.
Embodiment 2-1 to 2-4 and comparative example 2-1 to 2-2
Embodiment 2-1
The preparation of anode pole piece：By positive active material nickel-cobalt-manganese ternary material NCM (Ni：Co：Mn=4：
3：3), conductive agent conductive carbon, binding agent Kynoar (PVDF) in mass ratio 96：2：2 are well mixed
The lithium ion battery anode glue size with certain viscosity is made；Anode sizing agent is uniformly coated on plus plate current-collecting body
On aluminium foil, it is cold-pressed after being dried at 85 DEG C, then carry out trimming, cut-parts, slitting；In vacuum condition after slitting
With 85 DEG C at dry 4 hours, weld positive pole ear, anode slice of lithium ion battery is made.
The preparation of cathode pole piece：Negative electrode active material graphite, conductive agent conductive carbon, thickener methylol is fine
The plain sodium (CMC) of dimension, binding agent butadiene-styrene rubber (SBR) in mass ratio 97：1：1：1, which is made lithium ion battery, bears
Pole slurry；Cathode size is uniformly coated on negative current collector copper foil, at 85 DEG C dry after carry out trimming,
Cut-parts, slitting；Dried 4 hours at vacuum condition and 110 DEG C after slitting, weld negative lug, make lithium
Ion battery cathode pole piece.
The preparation of barrier film：Porous isolating membrane base material is used as from the polyethylene micropore film of 16 μ m-thicks.
The preparation of inorganic coating slurry：Inorganic coating slurry contain 30 parts by weight inorganic alchlor powder,
The polyethylene of 10 parts by weight gives a tongue-lashing the acetone solvent of pyrrolidone and 60 parts by weight, and specific preparation process is：
The first step：It is 100L's that the polyethylene of said ratio is given a tongue-lashing into pyrrolidone and the common 70Kg addition volumes of acetone
In double planetary mixer, disperse 3 hours at 25 DEG C；
Second step：Above-mentioned alundum (Al2O3) powder 30Kg is added in the mixer of the first step, at 35 DEG C
Scattered scattered 3 hours at a high speed down, low speed is stirred 1.5 hours slowly again afterwards, obtains inorganic coating slurry.
The preparation of inorganic coating：Surface coating is carried out to porous isolating membrane base material using dip coating manner, list is painted
Topcoat constructions；Drying is using one section of drying, and baking oven length is 10m, and baking oven design temperature is 55 DEG C, is applied
Cloth speed is 25m/min, and coating density is 5mg/cm2, a face inorganic coating thickness is 4 μm, inorganic coating
It is 80% in the area coverage ratio of porous isolating membrane base material.
The preparation of organic coating slurry：Organic coating slurry contains the polyacrylic acid of 20 parts by weight, 40 parts by weight
Polyacrylate and 40 parts by weight pure-acrylic emulsion, specific preparation process is：
The first step：It is 100L's that the common 80Kg of the polyacrylate and pure-acrylic emulsion of said ratio is added into volume
In double planetary mixer, stirring at low speed is mixed 1.5 hours at 25 DEG C；
Second step：20Kg polyacrylic acid is added, high speed dispersing and dissolving 3 hours at 25 DEG C obtain organic
Coating paste.
The preparation of organic coating：Porous isolation using plate gravure coating method to being surface-treated by inorganic coating
Film base material carries out surface coating, is coated with as barrier film two sided coatings, the weight and thickness one of two sides organic coating
Cause；Drying is using one section of drying, and baking oven length is 10m, and oven temperature is 55 DEG C；Coating speed is 25m/min,
Organic coating coating density is 1mg/1540.25mm2, the thickness of organic coating is 1 μm, organic after drying
Coating is in island and wire pattern on inorganic coating and on isolation film base material, and organic coating is in porous isolating membrane
The area coverage ratio of base material is 70%.
The preparation of electrolyte：Lithium hexafluoro phosphate is dissolved in ethylene carbonate, dimethyl carbonate and methyl ethyl carbonate
(volume ratio of ethylene carbonate, dimethyl carbonate and methyl ethyl carbonate is 1 to the in the mixed solvent of ester：2：1),
Obtain required electrolyte.
The preparation of lithium ion battery：Above-mentioned anode pole piece, cathode pole piece and barrier film are wound into lithium-ion electric
Core simultaneously injects electrolyte, and the process such as encapsulated, shaping, chemical conversion is prepared into lithium ion battery.
Ginseng is shown in Table 2, and embodiment 2-2 to 2-4 and comparative example 2-1 to 2-2 preparation process refer to reality
The preparation process of a 2-1 is applied, wherein, isolation film base material, base material thickness, inorganic coating thickness, organic high score
In sub- particle and/or macromolecule emulsion in the granularity D50 of particle, organic coating coating density and embodiment 2-1
Isolation film base material, base material thickness, inorganic coating thickness, organic polymer particle and/or macromolecule emulsion in
The granularity D50 of particle, organic coating coating density all same, the difference is that only the thickness of organic coating.
The influence of the organic coating thickness of table 2
From Table 2, it can be seen that same separation film base material, base material thickness, inorganic coating thickness, You Jigao
In molecule particles and/or macromolecule emulsion in the case of the granularity D50 of particle, organic coating coating density, no
The influence for the circulation ability that Gap abilities and lithium ion battery are made to barrier film with the thickness of organic coating is as follows：
1. when the thickness of organic coating excessive (more than 200 μm), battery core is actual to make Gap hyperenergias, has
The thickness of organic coating is excessive, i.e., ion channel is elongated, can cause barrier film in lithium ion battery charge and discharge process
Ion energy decline is led, blackspot and low temperature analysis lithium occurs in barrier film surface, and organic coating is to improving lithium-ion electric
The cycle life contribution in pond declines；
2. when the thickness of organic coating too small (being less than 1 μm), the actual Gap abilities of making of battery core are almost 0 μm,
Organic coating hardly increases the ability that lithium ion battery bears expansive force, now organic coating to improve lithium from
The circulation ability of sub- battery is almost without contribution；
3. when the thickness of organic coating is when between 1-200 μm, organic coating island and/or strip pattern coating
The expected ability for making Gap can be reached, while increase organic coating bears expansive force, anode is without low temperature
Lithium is analysed, so as to improve the circulation ability of lithium ion battery.
Embodiment 3-1 to 3-4 and comparative example 3-1 to 3-2
Embodiment 3-1
The preparation of anode pole piece：By positive active material nickel-cobalt-manganese ternary material NCM (N：C：M=4：3：
3), conductive agent conductive carbon, binding agent Kynoar (PVDF) in mass ratio 96：2：2 well mixed are made
Lithium ion battery anode glue size with certain viscosity；Anode sizing agent is uniformly coated on plus plate current-collecting body aluminium foil
On, it is cold-pressed after being dried at 85 DEG C, then carry out trimming, cut-parts, slitting；In vacuum condition and 85 DEG C after slitting
Lower drying 4 hours, welds positive pole ear, anode slice of lithium ion battery is made.
The preparation of cathode pole piece：Negative electrode active material graphite, conductive agent conductive carbon, thickener methylol is fine
The plain sodium (CMC) of dimension, binding agent butadiene-styrene rubber (SBR) in mass ratio 97：1：1：1, which is made lithium ion battery, bears
Pole slurry；Cathode size is uniformly coated on negative current collector copper foil, at 85 DEG C dry after carry out trimming,
Cut-parts, slitting；Dried 4 hours at vacuum condition and 110 DEG C after slitting, weld negative lug, make lithium
Ion battery cathode pole piece.
The preparation of barrier film：Porous isolating membrane base material is used as from the polyethylene micropore film of 16 μ m-thicks.
The preparation of inorganic coating slurry：Inorganic coating slurry contain 30 parts by weight inorganic alchlor powder,
The polyethylene of 10 parts by weight gives a tongue-lashing the acetone solvent of pyrrolidone and 60 parts by weight, and specific preparation process is：
The first step：It is 100L's that the polyethylene of said ratio is given a tongue-lashing into pyrrolidone and the common 70Kg addition volumes of acetone
In double planetary mixer, disperse 3 hours at 25 DEG C；
Second step：Above-mentioned alundum (Al2O3) powder 30Kg is added in the mixer of the first step, at 35 DEG C
Scattered scattered 3 hours at a high speed down, low speed is stirred 1.5 hours slowly again afterwards, obtains inorganic coating slurry.
The preparation of inorganic coating：Surface coating is carried out to porous isolating membrane base material using dip coating manner, list is painted
Topcoat constructions；Drying is using one section of drying, and baking oven length is 10m, and baking oven design temperature is 55 DEG C, is applied
Cloth speed is 25m/min, and coating density is 2.5mg/cm2, a face inorganic coating thickness is 4 μm, inorganic to apply
Layer is 50% in the area coverage ratio of porous isolating membrane base material.
The preparation of organic coating slurry：Organic coating slurry contains the polyacrylate of 5 parts by weight, 40 weight
The polyamide of part and the polyacrylonitrile of 55 parts by weight gather, and specific preparation process is：
The first step：It is the double of 100L that the poly- common 95Kg of the polyamide and polyacrylonitrile of said ratio is added into volume
In planetary mixer, stirring at low speed is mixed 1.5 hours at 25 DEG C；
Second step：5Kg polyacrylate is added, high speed dispersing and dissolving 3 hours at 35 DEG C obtain organic
Coating paste.
The preparation of organic coating：Porous isolation using plate gravure coating method to being surface-treated by inorganic coating
Film base material carries out surface coating, is coated with as barrier film two sided coatings structure, the weight and thickness of two sides organic coating
Degree is consistent；Drying is using one section of drying, and baking oven length is 10m, and oven temperature is 55 DEG C；Coating speed is
25m/min, organic coating coating density is 1mg/1540.25mm2, the thickness of organic coating is 30 μm, is done
After dry, organic coating is in island and wire pattern on inorganic coating and on isolation film base material, and organic coating exists
The area coverage ratio of porous isolating membrane base material is 50%.
The preparation of electrolyte：Lithium hexafluoro phosphate is dissolved in ethylene carbonate, dimethyl carbonate and methyl ethyl carbonate
(volume ratio of ethylene carbonate, dimethyl carbonate and methyl ethyl carbonate is 1 to the in the mixed solvent of ester：2：1),
Obtain required electrolyte.
The preparation of lithium ion battery：Above-mentioned anode pole piece, cathode pole piece and barrier film are wound into lithium-ion electric
Core simultaneously injects electrolyte, and the process such as encapsulated, shaping, chemical conversion is prepared into lithium ion battery.
Ginseng is shown in Table 3, and embodiment 3-2 to 3-4 and comparative example 3-1 to 3-2 preparation process refer to reality
The preparation process of a 3-1 is applied, wherein, isolation film base material, base material thickness, inorganic coating thickness, organic coating
Thickness, organic coating coating density isolate film base material, base material thickness, inorganic coating thickness with embodiment 3-1
Degree, organic coating thickness, organic coating coating density all same, the difference is that only in organic coating has
The content of machine polymeric particles and/or organic polymer emulsion.
The influence of organic polymer particle and/or organic polymer emulsion content in the organic coating of table 3
From table 3 it is observed that same separation film base material, base material thickness, inorganic coating thickness, organic painting
In the case of thickness degree, organic coating coating density, organic polymer particle and/or organic high in organic coating
The influence that the different content of molecule emulsion makes the cycle performance of Gap abilities and lithium ion battery to barrier film is as follows：
1. the too high levels of organic polymer particle and/or organic polymer emulsion (exceed in organic coating
When 95wt%), under identical organic coating coating density, organic coating distribution can be excessively fine and close, causes lithium ion
Barrier film diversion declines in battery charge and discharge process, and blackspot and low temperature analysis lithium occurs in barrier film surface, organic
Coating declines to the contribution for improving lithium ion battery circulation ability；
2. the content of organic polymer particle and/or organic polymer emulsion is too low in organic coating (being less than 5wt%)
When, identical organic coating is coated with density, and organic coating distribution can be excessively lax, causes organic coating island
And/or influence of the strip pattern coating to base material formation microwave wave is very big, the actual Gap abilities of making of battery core are not met
Theoretical value, the poor ability of expansive force is born to improving lithium ion battery, the circulation to improving lithium ion battery
Life-span contribution declines；
3. in organic coating the content of organic polymer particle and/or organic polymer emulsion 5%-95wt% it
Between when, organic coating island and/or strip pattern coating can reach the expected ability for making Gap, in increase
While organic coating bears expansive force, anode analyses lithium without low temperature, so as to improve the circulation energy of lithium ion battery
Power.
Embodiment 4-1 to 4-4 and comparative example 4-1 to 4-2
Embodiment 4-1
The preparation of anode pole piece：By positive active material nickel-cobalt-manganese ternary material NCM (N：C：M=4：3：
3), conductive agent conductive carbon, binding agent Kynoar (PVDF) in mass ratio 96：2：2 well mixed are made
Lithium ion battery anode glue size with certain viscosity；Anode sizing agent is uniformly coated on plus plate current-collecting body aluminium foil
On, it is cold-pressed after being dried at 85 DEG C, then carry out trimming, cut-parts, slitting；In vacuum condition and 85 DEG C after slitting
Lower drying 4 hours, welds positive pole ear, anode slice of lithium ion battery is made.
The preparation of cathode pole piece：Negative electrode active material graphite, conductive agent conductive carbon, thickener methylol is fine
The plain sodium (CMC) of dimension, binding agent butadiene-styrene rubber (SBR) in mass ratio 97：1：1：1, which is made lithium ion battery, bears
Pole slurry；Cathode size is uniformly coated on negative current collector copper foil, at 85 DEG C dry after carry out trimming,
Cut-parts, slitting；Dried 4 hours at vacuum condition and 110 DEG C after slitting, weld negative lug, make lithium
Ion battery cathode pole piece.
The preparation of barrier film：Porous isolating membrane base material is used as from the polyethylene micropore film of 16 μ m-thicks.
The preparation of inorganic coating slurry：Inorganic coating slurry contain 30 parts by weight inorganic alchlor powder,
The polyethylene of 10 parts by weight gives a tongue-lashing the acetone solvent of pyrrolidone and 60 parts by weight, and specific preparation process is：
The first step：It is 100L's that the polyethylene of said ratio is given a tongue-lashing into pyrrolidone and the common 70Kg addition volumes of acetone
In double planetary mixer, disperse 3 hours at 25 DEG C；
Second step：Above-mentioned alundum (Al2O3) powder 30Kg is added in the mixer of the first step, at 35 DEG C
Scattered scattered 3 hours at a high speed down, low speed is stirred 1.5 hours slowly again afterwards, obtains inorganic coating slurry.
The preparation of inorganic coating：Surface coating is carried out to porous isolating membrane base material using dip coating manner, list is painted
Topcoat constructions；Drying is using one section of drying, and baking oven length is 10m, and baking oven design temperature is 55 DEG C, is applied
Cloth speed is 25m/min, and coating density is 2.5mg/cm2, the thickness of a face inorganic coating is 4 μm, inorganic
Coating is 50% in the area coverage ratio of porous isolating membrane base material.
The preparation of organic coating slurry：Organic coating slurry contains the polyvinylidene fluoride polymer of 45 parts by weight
(D50：5-10 μm), the polyacrylonitrile of the polyamide of 30 parts by weight and 25 parts by weight gather, specific preparation process
For：
The first step：It is the double of 100L that the poly- common 55Kg of the polyamide and polyacrylonitrile of said ratio is added into volume
In planetary mixer, stirring at low speed is mixed 1.5 hours at 25 DEG C；
Second step：Addition 45Kg polyvinylidene fluoride polymers, high speed dispersing and dissolving 3 hours at 35 DEG C,
Obtain organic coating slurry.
The preparation of organic coating：Porous isolation using plate gravure coating method to being surface-treated by inorganic coating
Film base material carries out surface coating, is coated with as barrier film two sided coatings structure, the weight and thickness of two sides organic coating
Degree is consistent；Drying is using one section of drying, and baking oven length is 10m, and oven temperature is 55 DEG C；Coating speed is
25m/min, organic coating coating density is 1mg/1540.25mm2, the thickness of organic coating is 30 μm, is done
After dry, organic coating is in island and wire pattern on inorganic coating and on isolation film base material, and organic coating exists
The area coverage ratio of porous isolating membrane base material is 75%.
The preparation of electrolyte：Lithium hexafluoro phosphate is dissolved in ethylene carbonate, dimethyl carbonate and methyl ethyl carbonate
(volume ratio of ethylene carbonate, dimethyl carbonate and methyl ethyl carbonate is 1 to the in the mixed solvent of ester：2：1),
Obtain required electrolyte.
The preparation of lithium ion battery：Above-mentioned anode pole piece, cathode pole piece and barrier film are wound into lithium-ion electric
Core simultaneously injects electrolyte, and the process such as encapsulated, shaping, chemical conversion is prepared into lithium ion battery.
Ginseng is shown in Table 4, and embodiment 4-2 to 4-4 and comparative example 4-1 to 4-2 preparation process refer to reality
The preparation process of a 4-1 is applied, wherein, isolation film base material, base material thickness, inorganic coating thickness, organic coating
Thickness, organic coating coating density isolate film base material, base material thickness, inorganic coating thickness with embodiment 4-1
Degree, organic coating thickness, organic coating coating density all same, the difference is that only organic polymer
The granularity D50 of particle in grain and/or macromolecule emulsion.
The influence of organic polymer grain graininess in the organic coating of table 4
As can be seen from Table 4, same separation film base material, base material thickness, inorganic coating thickness, organic painting
In the case of thickness degree, organic coating coating density, different organic polymer particles and/or macromolecule emulsion
The influence that the granularity D50 of middle particle makes the cycle performance of Gap abilities and lithium ion battery to barrier film is as follows：
1. it is identical organic in organic coating during the granularity of organic polymer particle too high (D50 is more than 150 μm)
Under coating coating density, organic coating is blocked up, causes lithium ion battery charge and discharge process intermediate ion to dissociate passage
Distance is increased, that is, leads ion energy decline, and blackspot and low temperature analysis lithium, lithium ion battery occurs in barrier film surface
Internal resistance increases, and has harmful effect to the performance of lithium ion battery, organic coating is followed to improving lithium ion battery
The contribution of ring ability declines；
2. in organic coating during the granularity of organic polymer particle too low (D50 is less than 1 μm), identical organic painting
Under layer coating density, the thickness of organic coating is unable to reach requirement, and the actual Gap abilities of making of battery core are not inconsistent rationally
By value, the poor ability of expansive force is born to improving lithium ion battery, the circulation longevity to improving lithium ion battery
Life contribution declines；
3. the granularity (D50) of organic polymer particle is when between 1 μm -150 μm in organic coating, organic painting
Layer island and/or strip pattern coating can reach the expected ability for making Gap, bear swollen in increase organic coating
While expansive force, anode analyses lithium without low temperature, so as to improve the circulation ability of lithium ion battery.
Embodiment 5-1 to 5-3 and comparative example 5-1 to 5-2
Embodiment 5-1
The preparation of anode pole piece：By positive active material nickel-cobalt-manganese ternary material NCM (N：C：M=4：3：
3), conductive agent conductive carbon, binding agent Kynoar (PVDF) in mass ratio 96：2：2 well mixed are made
Lithium ion battery anode glue size with certain viscosity；Anode sizing agent is uniformly coated on plus plate current-collecting body aluminium foil
On, it is cold-pressed after being dried at 85 DEG C, then carry out trimming, cut-parts, slitting；In vacuum condition and 85 DEG C after slitting
Lower drying 4 hours, welds positive pole ear, anode slice of lithium ion battery is made.
The preparation of cathode pole piece：Negative electrode active material graphite, conductive agent conductive carbon, thickener methylol is fine
The plain sodium (CMC) of dimension, binding agent butadiene-styrene rubber (SBR) in mass ratio 97：1：1：1, which is made lithium ion battery, bears
Pole slurry；Cathode size is uniformly coated on negative current collector copper foil, at 85 DEG C dry after carry out trimming,
Cut-parts, slitting；Dried 4 hours at vacuum condition and 110 DEG C after slitting, weld negative lug, make lithium
Ion battery cathode pole piece.
The preparation of barrier film：Porous isolating membrane base material is used as from the polyethylene micropore film of 16 μ m-thicks.
The preparation of inorganic coating slurry：Inorganic coating slurry contain 30 parts by weight inorganic alchlor powder,
The polyethylene of 10 parts by weight gives a tongue-lashing the acetone solvent of pyrrolidone and 60 parts by weight, and specific preparation process is：
The first step：It is 100L's that the polyethylene of said ratio is given a tongue-lashing into pyrrolidone and the common 70Kg addition volumes of acetone
In double planetary mixer, disperse 3 hours at 25 DEG C；
Second step：Above-mentioned alundum (Al2O3) powder 30Kg is added in the mixer of the first step, at 35 DEG C
Scattered scattered 3 hours at a high speed down, low speed is stirred 1.5 hours slowly again afterwards, obtains inorganic coating slurry.
The preparation of inorganic coating：Surface coating is carried out to porous isolating membrane base material using dip coating manner, list is painted
Topcoat constructions；Drying is using one section of drying, and baking oven length is 10m, and baking oven design temperature is 55 DEG C, is applied
Cloth speed is 25m/min, and coating density is 5mg/cm2, a face inorganic coating thickness is 4 μm, inorganic coating
It is 95% in the area coverage ratio of porous isolating membrane base material.
The preparation of organic coating slurry：Organic coating slurry contain 95 parts by weight styrene-butadiene,
The polyamide of 2 parts by weight and the polyacrylonitrile of 3 parts by weight are poly-, and specific preparation process is：
The first step：The poly- common 5Kg of the polyamide and polyacrylonitrile of said ratio is added into the duplicate rows that volume is 100L
In star mixer, stirring at low speed is mixed 1.5 hours at 25 DEG C；
Second step：Addition 95Kg styrene-butadienes, high speed dispersing and dissolving 3 hours at 25 DEG C,
Obtain organic coating slurry.
The preparation of organic coating：Porous isolation using plate gravure coating method to being surface-treated by inorganic coating
Film base material carries out surface coating, is coated with as barrier film two sided coatings structure, the weight and thickness of two sides organic coating
Degree is consistent；Drying is using one section of drying, and baking oven length is 10m, and oven temperature is 55 DEG C；Coating speed is
25m/min, organic coating coating density is 1mg/1540.25mm2, the thickness of organic coating is 30 μm, is done
After dry, organic coating is in island and wire pattern on inorganic coating and on isolation film base material, and inorganic coating exists
The area coverage ratio of porous isolating membrane base material is 50%.
The preparation of electrolyte：Lithium hexafluoro phosphate is dissolved in ethylene carbonate, dimethyl carbonate and methyl ethyl carbonate
(volume ratio of ethylene carbonate, dimethyl carbonate and methyl ethyl carbonate is 1 to the in the mixed solvent of ester：2：1),
Obtain required electrolyte.
The preparation of lithium ion battery：Above-mentioned anode pole piece, cathode pole piece and barrier film are wound into lithium-ion electric
Core simultaneously injects electrolyte, and the process such as encapsulated, shaping, chemical conversion is prepared into lithium ion battery.
Refer to shown in table 5, embodiment 5-2 to 5-3 and comparative example 5-1 to 5-2 preparation process refer to
Embodiment 5-1 preparation process, wherein, isolation film base material, base material thickness, inorganic coating thickness, organic painting
Thickness degree, organic coating coating density isolate film base material, base material thickness, inorganic coating with embodiment 5-1
Thickness, organic coating thickness, organic coating coating density all same, the difference is that only in organic coating
Binder content.
The influence of binder content in the organic coating of table 5
As can be seen from Table 5, same separation film base material, base material thickness, inorganic coating thickness, organic painting
In the case of thickness degree, organic coating coating density, binding agent different content is made to barrier film in organic coating
Gap abilities, the cycle performance that expansive force and lithium ion battery are born to battery core influence it is as follows：
1. during binder content too high (more than 95wt%), in coating process, binding agent can be in barrier film table
Face film forming, causes ion can not pass freely through porous isolating membrane, slight low temperature analysis lithium occurs in barrier film, organic
Coating, which is contributed the circulation ability of lithium ion battery, to be declined；
2. binder content is too low (being less than 5wt%), easily there is dry linting in the organic coating after coating, causes reality
Border makes Gap abilities and is difficult to assess, and organic coating, which is contributed the circulation ability of lithium ion battery, to be declined；
3. binder content is between 5wt%-95wt%, organic coating island and/or strip pattern coating can
To reach the expected ability for making Gap, while increase organic coating bears expansive force, anode is analysed without low temperature
Lithium, so as to improve the cycle performance of lithium ion battery.
Embodiment 6-1 to 6-3 and comparative example 6-1 to 6-2
Embodiment 6-1
The preparation of anode pole piece：By positive active material nickel-cobalt-manganese ternary material NCM (N：C：M=4：3：
3), conductive agent conductive carbon, binding agent Kynoar (PVDF) in mass ratio 96：2：2 well mixed are made
Lithium ion battery anode glue size with certain viscosity；Anode sizing agent is uniformly coated on plus plate current-collecting body aluminium foil
On, it is cold-pressed after being dried at 85 DEG C, then carry out trimming, cut-parts, slitting；In vacuum condition and 85 DEG C after slitting
Lower drying 4 hours, welds positive pole ear, anode slice of lithium ion battery is made.
The preparation of cathode pole piece：Negative electrode active material graphite, conductive agent conductive carbon, thickener methylol is fine
The plain sodium (CMC) of dimension, binding agent butadiene-styrene rubber (SBR) in mass ratio 97：1：1：1, which is made lithium ion battery, bears
Pole slurry；Cathode size is uniformly coated on negative current collector copper foil, at 85 DEG C dry after carry out trimming,
Cut-parts, slitting；Dried 4 hours at vacuum condition and 110 DEG C after slitting, weld negative lug, make lithium
Ion battery cathode pole piece.
The preparation of barrier film：Porous isolating membrane base material is used as from the polyethylene micropore film of 5 μ m-thicks.
The preparation of inorganic coating slurry：Inorganic coating slurry contain 30 parts by weight inorganic alchlor powder,
The polyethylene of 10 parts by weight gives a tongue-lashing the acetone solvent of pyrrolidone and 60 parts by weight, and specific preparation process is：
The first step：It is 100L's that the polyethylene of said ratio is given a tongue-lashing into pyrrolidone and the common 70Kg addition volumes of acetone
In double planetary mixer, disperse 3 hours at 25 DEG C；
Second step：Above-mentioned alundum (Al2O3) powder 30Kg is added in the mixer of the first step, at 35 DEG C
Scattered scattered 3 hours at a high speed down, low speed is stirred 1.5 hours slowly again afterwards, obtains inorganic coating slurry.
The preparation of inorganic coating：Surface coating is carried out to porous isolating membrane base material using dip coating manner, list is painted
Topcoat constructions；Drying is using one section of drying, and baking oven length is 10m, and baking oven design temperature is 55 DEG C, is applied
Cloth speed is 25m/min, and coating density is 5mg/cm2, a face inorganic coating thickness is 2 μm, inorganic coating
It is 60% in the area coverage ratio of porous isolating membrane base material.
The preparation of organic coating slurry：The biasfluoroethylene-hexafluoropropylene that organic coating slurry contains 5 parts by weight gathers
The polyacrylonitrile of compound, the polyamide of 40 parts by weight and 55 parts by weight gathers, and specific preparation process is：
The first step：It is the double of 100L that the poly- common 95Kg of the polyamide and polyacrylonitrile of said ratio is added into volume
In planetary mixer, stirring at low speed is mixed 1.5 hours at 25 DEG C；
Second step：5Kg polyacrylate is added, high speed dispersing and dissolving 3 hours at 35 DEG C obtain organic
Coating paste.
The preparation of organic coating：Porous isolation using plate gravure coating method to being surface-treated by inorganic coating
Film base material carries out surface coating, is coated with as barrier film two sided coatings structure, the weight and thickness of two sides organic coating
Degree is consistent；Drying is using one section of drying, and baking oven length is 10m, and oven temperature is 55 DEG C；Coating speed is
25m/min, organic coating coating density is 0.75mg/1540.25mm2, the thickness of organic coating is 10 μm,
After drying, organic coating is in island and wire pattern, organic coating on inorganic coating and on isolation film base material
It is 30% in the area coverage ratio of porous isolating membrane base material.
The preparation of electrolyte：Lithium hexafluoro phosphate is dissolved in ethylene carbonate, dimethyl carbonate and methyl ethyl carbonate
(volume ratio of ethylene carbonate, dimethyl carbonate and methyl ethyl carbonate is 1 to the in the mixed solvent of ester：2：1),
Obtain required electrolyte.
The preparation of lithium ion battery：Above-mentioned anode pole piece, cathode pole piece and barrier film are wound into lithium-ion electric
Core simultaneously injects electrolyte, and the process such as encapsulated, shaping, chemical conversion is prepared into lithium ion battery.
Refer to shown in table 5, embodiment 6-2 to 6-3 and comparative example 6-1 to 6-2 preparation process refer to
Embodiment 6-1 preparation process, wherein, isolation film base material, inorganic coating thickness, organic coating thickness, have
Organic coating be coated with density with embodiment 6-1 isolate film base material, inorganic coating thickness, organic coating thickness,
Organic coating is coated with density all same, the difference is that only the thickness of base material.
The influence of the base material thickness of table 6
As can be seen from Table 6, same separation film base material, inorganic coating thickness, organic coating thickness, have
In the case of organic coating is coated with density, different base material thickness are to making Gap abilities and to improving lithium ion battery
Circulation ability influence it is as follows：
1. isolating, film base material is thicker, and organic coating island and/or strip pattern coating are less susceptible to form base material
The influence of microwave wave, the then actual value for making Gap gets over convergence theoretical value；
2. when barrier film base material thickness excessive (more than 40 μm), although organic coating can increase lithium ion battery
The ability of expansive force is born, but because base material thickness is blocked up, adds the influence of organic coating thickness, can be caused
Lithium ion battery is in charge and discharge process, and the ion energy of leading of porous septum declines, and slight low temperature analysis lithium occurs
Or serious low temperature analysis lithium phenomenon, cause organic coating island and/or strip to be coated with and followed to improving lithium ion battery
The contribution of ring ability declines；
3. when barrier film base material thickness too small (being less than 5 μm), organic coating island and/or strip pattern coating
Influence to the unrestrained wrinkle of base material formation microwave is very big, and the actual Gap abilities of making of battery core are very weak, and organic coating can be held
The expansive force received is reduced, and is declined so as to contribute the circulation ability for improving lithium ion battery；
4. when the thickness of isolation film base material is when between 5-40 μm, organic coating island and/or strip pattern are applied
Influence of the layer to base material formation microwave wave is smaller, under certain organic coating coating density, can reach expection
Gap ability is made, while increase organic coating bears expansive force, anode analyses lithium without low temperature, so as to carry
The cycle performance of high-lithium ion battery.
Embodiment 7-1 to 7-3 and comparative example 7-1 to 7-2
Embodiment 7-1
The preparation of anode pole piece：By positive active material nickel-cobalt-manganese ternary material NCM (N：C：M=4：3：
3), conductive agent conductive carbon, binding agent Kynoar (PVDF) in mass ratio 96：2：2 well mixed are made
Lithium ion battery anode glue size with certain viscosity；Anode sizing agent is uniformly coated on plus plate current-collecting body aluminium foil
On, it is cold-pressed after being dried at 85 DEG C, then carry out trimming, cut-parts, slitting；In vacuum condition and 85 DEG C after slitting
Lower drying 4 hours, welds positive pole ear, anode slice of lithium ion battery is made.
The preparation of cathode pole piece：Negative electrode active material graphite, conductive agent conductive carbon, thickener methylol is fine
The plain sodium (CMC) of dimension, binding agent butadiene-styrene rubber (SBR) in mass ratio 97：1：1：1, which is made lithium ion battery, bears
Pole slurry；Cathode size is uniformly coated on negative current collector copper foil, at 85 DEG C dry after carry out trimming,
Cut-parts, slitting；Dried 4 hours at vacuum condition and 110 DEG C after slitting, weld negative lug, make lithium
Ion battery cathode pole piece.
The preparation of barrier film：Porous isolating membrane base material is used as from the polyethylene micropore film of 16 μ m-thicks.
The preparation of inorganic coating slurry：Inorganic coating slurry contain 30 parts by weight inorganic alchlor powder,
The polyethylene of 10 parts by weight gives a tongue-lashing the acetone solvent of pyrrolidone and 60 parts by weight, and specific preparation process is：
The first step：It is 100L's that the polyethylene of said ratio is given a tongue-lashing into pyrrolidone and the common 70Kg addition volumes of acetone
In double planetary mixer, disperse 3 hours at 25 DEG C；
Second step：Above-mentioned alundum (Al2O3) powder 30Kg is added in the mixer of the first step, at 35 DEG C
Scattered scattered 3 hours at a high speed down, low speed is stirred 1.5 hours slowly again afterwards, obtains inorganic coating slurry.
The preparation of inorganic coating：Surface coating is carried out to porous isolating membrane base material using dip coating manner, list is painted
Topcoat constructions；Drying is using one section of drying, and baking oven length is 10m, and baking oven design temperature is 55 DEG C, is applied
Cloth speed is 25m/min, and coating density is 5mg/cm2, a face inorganic coating thickness is 1 μm, inorganic coating
It is 60% in the area coverage ratio of porous isolating membrane base material.
The preparation of organic coating slurry：The biasfluoroethylene-hexafluoropropylene that organic coating slurry contains 20 parts by weight gathers
The polyacrylonitrile of compound, the polyamide of 40 parts by weight and 40 parts by weight gathers, and specific preparation process is：
The first step：It is the double of 100L that the poly- common 80Kg of the polyamide and polyacrylonitrile of said ratio is added into volume
In planetary mixer, stirring at low speed is mixed 1.5 hours at 25 DEG C；
Second step：20Kg polyacrylate is added, high speed dispersing and dissolving 3 hours, are had at 35 DEG C
Organic coating slurry.
The preparation of organic coating：Porous isolation using plate gravure coating method to being surface-treated by inorganic coating
Film base material carries out surface coating, is coated with as barrier film two sided coatings structure, the weight and thickness of two sides organic coating
Degree is consistent；Drying is using one section of drying, and baking oven length is 10m, and oven temperature is 55 DEG C；Coating speed is
25m/min, organic coating coating density is 1mg/1540.25mm2, the thickness of organic coating is 10 μm, is done
After dry, organic coating is in island and wire pattern on inorganic coating and on isolation film base material, and organic coating exists
The area coverage ratio of porous isolating membrane base material is 80%.
The preparation of electrolyte：Lithium hexafluoro phosphate is dissolved in ethylene carbonate, dimethyl carbonate and methyl ethyl carbonate
(volume ratio of ethylene carbonate, dimethyl carbonate and methyl ethyl carbonate is 1 to the in the mixed solvent of ester：2：1),
Obtain required electrolyte.
The preparation of lithium ion battery：Above-mentioned anode pole piece, cathode pole piece and barrier film are wound into lithium-ion electric
Core simultaneously injects electrolyte, and the process such as encapsulated, shaping, chemical conversion is prepared into lithium ion battery.
Refer to shown in table 7, embodiment 7-2 to 7-3 and comparative example 7-1 to 7-2 preparation process refer to
Embodiment 7-1 preparation process, wherein, isolation film base material, base material thickness, organic coating thickness, organic painting
Layer coating density isolates film base material, base material thickness, organic coating thickness, organic coating with embodiment 7-1
Density all same is coated with, the thickness of inorganic coating is the difference is that only.
The influence of the inorganic coating thickness of table 7
As can be seen from Table 7, same separation film base material, base material thickness, organic coating thickness, organic painting
In the case of layer coating density, the thickness of different inorganic coatings barrier film is made Gap abilities and to improve lithium from
The influence of the cycle performance of sub- battery is as follows：
1. when the thickness of inorganic coating excessive (more than 10 μm), actual battery core makes Gap abilities and meets theoretical value,
Although now organic coating can increase the ability that battery bears expansive force, because inorganic coating is blocked up, lithium from
The ionic conductance ability of sub- battery barrier film in charge and discharge process declines, the circulation to improving lithium ion battery
Ability contribution declines；
2. when inorganic coating thickness too small (be less than 1 μm), in coating process, organic coating island and/or
Influence of the strip pattern coating to base material formation microwave wave is very big, and the actual Gap abilities of making of battery core are very weak, organic
Coating circulates the expansion space reserved in expansion process to lithium ion battery and reduced, to improving lithium ion battery
Circulation ability contribution declines；
3. when inorganic coating thickness is when between 1-10 μm, in coating process, organic coating island and/or
Influence of the strip pattern coating to base material formation microwave wave is smaller, can reach the expected ability for making Gap,
While increase organic coating bears expansive force, anode analyses lithium without low temperature, so as to improve following for lithium ion battery
Ring ability.
It should be noted that the announcement and teaching of book according to the above description, technology people of the art
Member can also be changed and be changed to above-mentioned embodiment.Therefore, the invention is not limited in be disclosed above
With the embodiment of description, some equivalent modifications and change to the present invention should also be as falling into the present invention's
In scope of the claims.Although in addition, used some specific terms in this specification, this
A little terms merely for convenience of description, do not constitute any limitation to the present invention.
Claims (10)
1. a kind of lithium ion battery barrier film, it includes isolation film base material and is directly or indirectly distributed in barrier film
Organic coating in base material at least one side, it is characterised in that：The coating density of the organic coating is
0.1mg/1540.25mm2~10mg/1540.25mm2。
2. lithium ion battery barrier film according to claim 1, it is characterised in that：The barrier film base
The thickness of material is 5-40 μm.
3. lithium ion battery barrier film according to claim 1, it is characterised in that：The barrier film base
Material is PE, PP, non-woven fabrics, PET, PVDF, PU, PA, PI, organic-inorganic blend film or PP/PE/PP.
4. lithium ion battery barrier film according to claim 1, it is characterised in that：The organic coating
Including organic polymeric particles and/or organic polymer emulsion and binding agent.
5. lithium ion battery barrier film according to claim 4, it is characterised in that：Organic high score
The weight content of sub- particle and/or organic polymer emulsion is 5%-95%, and the weight content of the binding agent is
5%-95%.
6. lithium ion battery barrier film according to claim 4, it is characterised in that：Organic high score
Sub- particle and/or organic polymer emulsion are Kynoar, biasfluoroethylene-hexafluoropropylene polymer, styrene
At least one of-butadiene polymer, polyacrylic acid, polyacrylate；The binding agent be polyamide,
Polyacrylonitrile, polyacrylate, polyacrylate, hydroxymethyl cellulose sodium, polyethylene give a tongue-lashing pyrrolidone, second
Acetoacetic ester, benzene polyvinylether, polyvinylether, ethylene carbonate, propanetriol-diglycidyl-ether, propylene carbonate
At least one of ester, acetone, pure-acrylic emulsion.
7. lithium ion battery barrier film according to any one of claim 1 to 6, it is characterised in that：
Inorganic coating is distributed with the isolation film base material at least one side, and it is inorganic that the organic coating is distributed at least one
On coating, the organic coating makes Gap abilities for 1-150 μm to the lithium-ion electric core after winding hot pressing.
8. lithium ion battery barrier film according to claim 7, it is characterised in that：The organic coating
Area coverage ratio on isolation film base material or inorganic coating is 1%-95%.
9. lithium ion battery barrier film according to claim 7, it is characterised in that：The inorganic coating
Including particles of inorganic material and binding agent, the weight content of the inorganic particle is 5-95%, the weight of the binding agent
Amount content is 5-95%.
10. a kind of lithium ion battery, including anode pole piece, cathode pole piece, it is interval in anode pole piece and negative pole pole
Barrier film between piece, and electrolyte, it is characterised in that：The barrier film is in claim 1 to 9
Lithium ion battery barrier film described in any one.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1384555A (en) * | 2001-05-08 | 2002-12-11 | 思凯德公司 | Cell partition of polymer |
| CN104852008A (en) * | 2015-05-06 | 2015-08-19 | 东莞市魔方新能源科技有限公司 | Isolating membrane for lithium ion secondary battery |
| CN105374968A (en) * | 2014-08-13 | 2016-03-02 | 三星Sdi株式会社 | Separator for lithium secondary battery, lithium secondary battery, and method of manufacturing the lithium secondary battery |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1384555A (en) * | 2001-05-08 | 2002-12-11 | 思凯德公司 | Cell partition of polymer |
| CN105374968A (en) * | 2014-08-13 | 2016-03-02 | 三星Sdi株式会社 | Separator for lithium secondary battery, lithium secondary battery, and method of manufacturing the lithium secondary battery |
| CN104852008A (en) * | 2015-05-06 | 2015-08-19 | 东莞市魔方新能源科技有限公司 | Isolating membrane for lithium ion secondary battery |
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