CN107437603A - Composite diaphragm for lithium ion battery and preparation method thereof and lithium ion battery - Google Patents
Composite diaphragm for lithium ion battery and preparation method thereof and lithium ion battery Download PDFInfo
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- CN107437603A CN107437603A CN201710540555.9A CN201710540555A CN107437603A CN 107437603 A CN107437603 A CN 107437603A CN 201710540555 A CN201710540555 A CN 201710540555A CN 107437603 A CN107437603 A CN 107437603A
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- ceramic
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- ion battery
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/403—Manufacturing processes of separators, membranes or diaphragms
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The present invention relates to technical field of lithium ion, disclose composite diaphragm for lithium ion battery and preparation method thereof and lithium ion battery, the composite diaphragm for lithium ion battery, ceramic membrane comprising polymeric matrix and coated in polymeric body surface, the ceramic membrane is made up of ceramic slurry, the ceramic slurry includes dispersant, binding agent and powder, and the powder includes following material：Ceramic particle, ceramic whisker and cellulose, the mechanical performance that the present invention adds laminated film by adding ceramic fibre in ceramic slurry, make it not come off from polymeric matrix, keep good cementitiousness, suppress ceramic diaphragm dry linting；The addition of cellulose improves barrier film and absorbs and keep electrolyte ability, moreover it is possible to effectively reduces the percent thermal shrinkage of barrier film at high temperature.
Description
Technical field
The present invention relates to technical field of lithium ion, and in particular to composite diaphragm for lithium ion battery and preparation method thereof
And lithium ion battery.
Background technology
In recent years, as the exhaustion of earth resource and the enhancing of social environment consciousness, green clean energy resource turn into storage
The important directions in field can be converted with energy.Electrochmical power source turns into production and life as basic energy reserve and reforming unit
An essential part in work.In today of portable electric appts high speed development, to the demand of chargeable electrochmical power source more
It is great urgency.For the secondary cells such as more traditional NI-G, plumbic acid, lithium ion battery has its high-energy-density, longevity
Life and the characteristic such as environmentally safe, have been widely used as the electrical source of power of portable electric appts at present.In recent years, China
Lithium ion battery industry achieves large development, and production capacity has leapt to the whole world the 3rd.With the arrival of low-carbon economy, lithium ion is moved
The demand of power battery will be increasing.And the biggest obstacle that electrokinetic cell faces is safety problem.
Lithium ion under conditions of high current, due to the limitation of electrode material performance itself, is easily caused lithium metal in negative pole table
Face deposits, and forms a large amount of dendrite.The presence of these dendrite easily pierces barrier film, causes inside battery micro-short circuit so as to trigger safety hidden
Suffer from, therefore, it is possible to say, battery diaphragm directly affects to battery security, is build security electrokinetic cell crucial group
One of part.For the high-capacity battery currently as research and development focus, because negative pole is using capacity is higher but ionic conductivity
Lower non-carbon or poor carbon system, the surface enrichment of lithium metal is more also easy to produce, thus for this kind of battery, the performance of barrier film
It is particularly important.Further, since the electrode material of high power capacity, also there is bulk effect, the continuous expansion of volume is with shrinking inherently
Surface easily to barrier film and interface therebetween produce harmful effect.It can be said that barrier film not only affects the resistance to heat energy of battery
Power, also contribute to the electrochemistry overall characteristic such as capacity, cycle performance of battery.
Commercial li-ion battery diaphragm mainly has polyethylene (PE), polypropylene single-layer septum (PP), and PP/PE/PP at present
Trilamellar membrane.Membrane for polymer is light, has good electronic isolation performance, and its deficiency is due to that the general fusing point of polymer is relatively low,
When heat abuse occurs for battery, because the heat localization of inside battery easily deforms and both positive and negative polarity is set directly to contact so as to draw
Hair short circuit.To improve barrier film security, occur in recent years it is many by inorganic filler coated in polyalkene diaphragm surface to improve
The heat endurance of barrier film, still, short circuit phenomenon can still occur after battery working time is longer, and ceramic-coated separator is simultaneously
Also reduce the wetting capacity of barrier film and electrolyte；In addition, not surface treated inorganic filler powder easily produces reunion, and
Come off from polyalkene diaphragm surface, influence the performance of separator product.
The content of the invention
For the deficiencies in the prior art, an object of the present invention be to provide a kind of lithium ion battery with it is compound every
Film, not only with good heat endurance, also with excellent moisture retention.
The second object of the present invention is to provide a kind of preparation method of lithium ion battery laminated film.
The third object of the present invention is to provide a kind of lithium ion battery.
To achieve these goals, the present invention provides a kind of composite diaphragm for lithium ion battery, comprising polymeric matrix and
Ceramic membrane coated in polymeric body surface, the ceramic membrane are made up of ceramic slurry, and the ceramic slurry, which includes, to be divided
Powder, binding agent and powder, the powder include following material：Ceramic particle, ceramic whisker and cellulose.
A kind of preparation method of lithium ion battery laminated film, the preparation method comprise the following steps：
A, swelling treatment is carried out to cellulose, obtains swollen cellulose；
B, ceramic particle and ceramic whisker are well mixed in dispersant, then add swollen cellulose, be well mixed
After add binding agent, obtain ceramic slurry after stirring；
Ceramic slurry is coated in the surface of polymeric matrix, obtain lithium ion battery laminated film C,.
Present invention also offers a kind of lithium ion battery, the lithium ion battery, positive pole, negative pole, barrier film and electrolysis are included
Liquid, the barrier film are above-mentioned composite diaphragm for lithium ion battery.
Pass through above-mentioned technical proposal, the machine that the present invention adds laminated film by adding ceramic fibre in ceramic slurry
Tool performance, it is not come off from polymeric matrix, keep good cementitiousness, suppress ceramic diaphragm dry linting；Cellulose
Addition improve barrier film absorb and keep electrolyte ability, moreover it is possible to effectively reduce the percent thermal shrinkage of barrier film at high temperature, carry
The high service life of battery.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Embodiment
The embodiment of the present invention is described in detail below.It is it should be appreciated that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to limit the invention.
The end points of disclosed scope and any value are not limited to the accurate scope or value herein, these scopes or
Value should be understood to comprising the value close to these scopes or value.For number range, between the endpoint value of each scope, respectively
It can be combined with each other between the endpoint value of individual scope and single point value, and individually between point value and obtain one or more
New number range, these number ranges should be considered as specific open herein.
A kind of composite diaphragm for lithium ion battery, the ceramic thin comprising polymeric matrix and coated in polymeric body surface
Film, the ceramic membrane are made up of ceramic slurry, and the ceramic slurry includes dispersant, binding agent and powder, the powder bag
Containing following material：Ceramic particle, ceramic whisker and cellulose.
According to the present invention, the ceramic particle can be alumina particle, yttria particles, metatitanic acid k particle, zirconium oxide
Particle, titanium dioxide granule, silica dioxide granule, barium sulfate particle, barium titanate particles, calcium carbonate granule, magnesium oxide particle, oxygen
Change at least one of zinc particle, silicon-carbide particle and boron nitride particle.
According to the present invention, the influence of the particle diameter of ceramic particle to ceramic coating is very big, (>=1 μ when ceramic particle is excessive
M), the adhesion between ceramic molecular and matrix is weaker, using one section when after, easily occur " dry linting phenomenon ", make ceramics
Particle drops from matrix, it is preferred that the micro- 10~100nm of particle diameter of ceramic particle in the present invention, it is further preferred that the pottery
Porcelain powder can be prepared by wet chemical method, such as hydrothermal synthesis method, coprecipitation etc..
According to the present invention, the main component of ceramic slurry is ceramic particle in the prior art, after slurry drying is molded, its
Mechanical strength is poor, such as tensile strength, rupture strength and high-temperature shrinkage performance, in order to strengthen the levelability of coating, in order to improve
The mechanical performance of laminated film, the present invention in laminated film in also contain ceramic whisker, it is preferred that the ceramic whisker is oxygen
It is brilliant to change al whisker, yittrium oxide whisker, zirconium oxide whisker, titanium dioxide crystal whisker, silica whisker, barium sulfate crystal whisker, barium titanate
At least one of palpus, calcium carbonate crystal whisker, magnesia crystal whisker, ZnOw, silicon carbide whisker and boron nitride crystal whisker, further
Preferably, 10~150nm of diameter of the ceramic whisker, length are 500nm~3 μm.
According to the present invention, the content of each material has large effect to the performance of barrier film in powder, such as works as ceramic particle
When content is larger, the mechanical performance of barrier film is poor, and when the content of ceramic fibre is larger, it is viscous between ceramic slurry and matrix
It is smaller to tie power, is easily come off from matrix, it is preferred that on the basis of the gross weight of powder, the powder includes following parts by weight
Material：Ceramic particle 75~96%, ceramic whisker 3~20% and cellulose 1~5%, more preferably ceramic particle 83%, pottery
Porcelain whisker 12% and cellulose 5%.
According to the present invention, cellulose has excellent moisture pick-up properties, water-retaining property and heat endurance, has with electrolyte good
Compatibility, it can absorb and retain more electrolyte, advantage is had more on cycle performance, be advantageous to improve the cyclicity of battery
Energy；In addition, cellulose also has good swelling behavior, when lithium ion battery negative or positive electrode under long-time high current work
When Volume Changes are produced when making, cellulose can resist Volume Changes, improve the stability and service life of battery.
According to the present invention, in order to further improve the mechanical performance of laminated film, also contain polymerization in the ceramic slurry
Thing spinning, it is preferred that the polymer spinning is Kynoar spinning, polytetrafluoroethylene (PTFE) spinning, pi spinning, poly- ammonia
Carbamate spinning, polyvinyl alcohol spinning, polypropylene spinning, polyhexafluoropropylene spinning, polyacrylonitrile spinning, poly terephthalic acid
At least one of the spinning of second diester and polymethyl methacrylate spinning；It is further preferred that the polymer spinning is straight
Footpath is 50nm~1 μm.
, according to the invention it is preferred to, the dispersant is n-butanol, cyclohexanol, ethanol, 1-METHYLPYRROLIDONE, three second
Base hexyl phosphoric acid, lauryl sodium sulfate, methyl anyl alcohol, cellulose derivative, polyacrylamide, guar gum, fatty acid polyglycol second
At least one of diol ester, castor oil, glyceryl monostearate, glyceryl tristearate and oleic acid acyl.
According to the present invention, also contain thickener in the ceramic slurry, it is preferred that the thickener be methylcellulose,
At least one of hydroxyethyl cellulose, sodium carboxymethylcellulose and hydroxypropyl methyl cellulose.
, according to the invention it is preferred to, the binding agent be butadiene-styrene rubber, cellulose and its derivates, Kynoar, partially
Viton copolymers, PAEK, polyacrylic acid, polyacrylate and its derivative, polyacrylonitrile, acrylic acid
At least one in ester-acrylonitrile copolymer, copolymer in cinnamic acrylic ester, APEO, polysulfones and polytetrafluoroethylene (PTFE)
Kind.
According to the present invention, surfactant is also contained in the ceramic slurry, the surfactant is stearate, oil
Hydrochlorate, lauryl sulfate, dodecyl benzene sulfonate, dioctyl succinate disulfonate acid, liver sodium taurocholate etc., monostearate are sweet
Grease, APEO, Pluronic F68, fatty acid sorbitol ester, polyoxyethylene sorbitan ester, polyoxy
At least one of ethene fatty acid ester and polyoxyethylene aliphatic alcohol ether.
According to the present invention, polymeric matrix be influence composite diaphragm performance an important factor for one of, it is preferred that the polymerization
Thing matrix is Kynoar, polytetrafluoroethylene (PTFE), polyvinyl alcohol, polypropylene, polyhexafluoropropylene, polyacrylonitrile, poly- terephthaldehyde
At least one of sour second diester and polymethyl methacrylate.
The present invention also provides a kind of preparation method of composite diaphragm for lithium ion battery, comprises the steps of：
A, swelling treatment is carried out to cellulose, obtains swollen cellulose；
B, ceramic particle and ceramic whisker are well mixed in dispersant, then add swollen cellulose, be well mixed
After add binding agent, obtain ceramic slurry after stirring；
Ceramic slurry is coated in the surface of polymeric matrix, after drying, obtain lithium ion battery laminated film C,.
According to the present invention, the ceramic slurry is coated in the surface of polymeric matrix, the speed of the coating by rubbing method
It is 30-80 DEG C to spend for 5-100m/min, drying temperature, and the thickness of obtained ceramic coating is 0.1- after ceramic slurry coating basement membrane
50μm。
According to the present invention, in step, the swelling treatment step of the cellulose is：By cellulose in aqueous solution
2~24h is soaked, washing, ultrasound, filtering, obtains swollen cellulose；
In order to improve the swelling efficiency of cellulose, the aqueous solution is deionized water or alkaline solution, is preferably alkalescence
Solution, such as copper ammon solution, cupri-ethylene diamine solution, sodium hydroxide/aqueous solution of urea, sodium hydroxide/urea/zinc oxide aqueous solution.
In order to further improve the swelling efficiency of cellulose, according to the present invention, the temperature of the aqueous solution is 25~90
℃。
A kind of lithium ion battery, comprising positive pole, negative pole, barrier film and electrolyte, the barrier film is used for above-mentioned lithium ion battery
Composite diaphragm.
According to the present invention, the positive pole includes positive active material, conductive agent and binding agent, and the positive active material can
Think material known in those skilled in the art, such as LixMO2Or LiyM2O4(in formula, M is transition metal, 0≤x≤1,0≤y
≤ 2) lithium-contained composite oxide, the oxide of spinelle shape, the metal chalcogenide of layer structure, the olivine structural represented
Deng being more specifically LiCoO2Deng lithium and cobalt oxides, LiMn2O4Deng lithium manganese oxide, LiNiO2Deng lithium nickel oxide, Li4/3Ti5/3O4Deng Li-Ti oxide, li-mn-ni compound oxide, lithium manganese nickel cobalt composite oxides；With LiMPO4(M=Fe, Mn,
The material of olivine-type crystalline texture etc. such as Ni)；The preparation method of the positive pole can use conventional preparation method.Example
Such as, positive electrode is mixed with solvent, coats and/or be filled on the conducting base, dried, rolled or do not roll, you can
Obtain the positive pole.
According to the present invention, the negative pole includes negative electrode active material, conductive agent and binding agent, and the negative electrode active material can
Think material known in those skilled in the art, can be that can be embedded in-deintercalation lithium metal, the compound of lithium.Such as aluminium,
Various materials such as the alloy or oxide of silicon, tin etc., carbon material etc. may be used as negative electrode active material.Oxide can enumerate two
Titanium oxide etc., carbon material can enumerate graphite, pyrolysis carbons, coke class, glassy carbons, organic high molecular compound and burn till
Body, mesophase-carbon micro-beads etc.；The preparation method of the negative pole can use conventional preparation method.For example, by negative material with
Solvent mixes, and coats and/or is filled on the conducting base, dries, and rolls or does not roll, you can obtains the negative pole.
Practical electrolyte is nonaqueous electrolytic solution in the present invention, and it is molten that the nonaqueous solvents includes carbonates, ethers, fluorine class
Agent etc., such as ethylene carbonate, propene carbonate, butylene, gamma-butyrolacton, diethyl carbonate, methyl ethyl carbonate, diformazan
Ether tetraethylene glycol (TEGDME), glycol dimethyl ether (DME), the nitrile such as chain phosphotriester, the 3- methoxypropionitriles such as trimethyl phosphate
At least one of class solvent, 2- trifluoromethyl hexafluoro propyl group ether, 2- trifluoromethyl hexafluoro propyl group propyl ether etc..
The present invention will be described in detail by way of examples below.
Embodiment 1
A kind of lithium ion battery, it is made up of positive pole, negative pole and barrier film, its preparation method is as follows：
(1) preparation of positive pole
By 100 parts by weight positive active material LiNi0.33Co0.33Mn0.34O2, 4 parts by weight of binder polyvinylidene fluoride
(PVDF), 4 parts by weight conductive agent acetylene blacks are added in 50 parts by weight 1-METHYLPYRROLIDONEs (NMP), are then being stirred under vacuum
Stirring forms uniform anode sizing agent in machine；The slurry is uniformly coated to wide 400mm, on thick 20 μm aluminium foil, then 120
DEG C drying, under 1.6MPa pressure after roll-in on cutting machine cutting obtain size for 385mm × 42mm × 135 μm just
Pole, the dressing density of obtained positive plate is 3.4g/cm3。
(2) preparation of negative pole
By 100 parts by weight negative electrode active material native graphites, 4 parts by weight of binder polytetrafluoroethylene (PTFE) (PTFE), 4 parts by weight
Conductive agent carbon black is added in 45 parts by weight dimethyl sulfoxides (DMSO), and then stirring formation is stable, homogeneous in de-airing mixer
Cathode size；The slurry is uniformly coated to wide 400mm, on thick 10 μm copper foil, existed after 120 DEG C of drying, rollings
Cutting obtains the negative pole that size is 43mm × 355mm × 135 μm on cutting machine, wherein containing 2.7g negative materials.
(3) preparation of barrier film
A, 1.3 part by weight of cellulose are soaked into 2h in 2M sodium hydroxide (40 DEG C) solution, are then filtered to remove filtrate,
Filter residue is washed with water to neutrality, then ultrasonic disperse 30min, is filtrated to get swollen cellulose；
B, by the parts by weight (average grain diameter 20nm) of metatitanic acid k particle 20, the parts by weight (average grain diameter of silica dioxide granule 16
For 40nm), the parts by weight (average diameter 50nm) of polytetrafluoroethylene (PTFE) spinning 2.2 and the parts by weight (average diameter of silica whisker 2
For 10nm, average length 800nm) it is well mixed in the parts by weight of n-butanol 45, swollen cellulose is then added, is well mixed
After add the parts by weight of acrylic ester-acrylonitrile copolymer 4.5, the parts by weight of hydroxyethyl cellulose 3 and neopelex
4.5 parts by weight, ceramic slurry is obtained after stirring；
Ceramic slurry is coated in the surface of 20cm × 6m polyvinyl alcohol matrix with 20m/min coating speed, so C,
Afterwards in 50 DEG C of dry 6h, the thickness for obtaining ceramic coating is 1 μm of lithium ion battery laminated film.
(4) assembling of battery
By LiPF6LiPF is configured to ethylene carbonate (EC) and diethyl carbonate (DEC)6Concentration is 1.0 mol/Ls
(wherein, EC and DEC volume ratio is 1 to solution：1) nonaqueous electrolytic solution, is obtained.By positive pole, composite diaphragm, negative pole successively with winding
Machine is laminated the electrode group for being wound into scroll, and obtained electrode group is put into the battery case of one end open, and with 3.8g/Ah's
Amount injects above-mentioned nonaqueous electrolytic solution, and lithium ion battery is made after sealing.
Embodiment 2
A kind of lithium ion battery, it is made up of positive pole, negative pole and barrier film, its preparation method is as follows：
(1) preparation method of positive pole is the same as embodiment 1；
(2) preparation method of negative pole is the same as embodiment 1；
(3) preparation of barrier film：
A, the parts by weight of cellulose 1.5 are soaked into 5h in sodium hydroxide/aqueous solution of urea (25 DEG C), is then filtered to remove filter
Liquid, filter residue is washed with water to neutrality, then ultrasonic disperse 30min, is filtrated to get swollen cellulose；
B, by the parts by weight (average grain diameter 10nm) of magnesium oxide particle 9, the parts by weight of titanium dioxide granule 20, (average grain diameter is
50nm), the parts by weight (average diameter 100nm) of polyurethanes spinning 0.72 and the parts by weight of yittrium oxide whisker 5.8 are (average straight
Footpath is 100nm, and average length is 2 μm) it is well mixed in the parts by weight of ethanol 40, swollen cellulose is then added, is well mixed
After add the parts by weight of glyceryl tristearate 15, the parts by weight of hydroxypropyl methyl cellulose 2, the parts by weight of polyacrylonitrile 2.9,12
The parts by weight of sodium alkyl sulfate 5.5, ceramic slurry is obtained after stirring；
Ceramic slurry is coated in the surface of 20cm × 6m polyhexafluoropropylene matrix with 50m/min coating speed C,
Then in 80 DEG C of dry 6h, the thickness for obtaining ceramic coating is 5 μm of lithium ion battery laminated film.
(4) assembly method of battery is the same as embodiment 1.
Embodiment 3
A kind of lithium ion battery, it is made up of positive pole, negative pole and barrier film, its preparation method is as follows：
(1) preparation method of positive pole is the same as embodiment 1；
(2) preparation method of negative pole is the same as embodiment 1；
(3) preparation of barrier film：
A, the parts by weight of cellulose 0.6 are soaked into 2h in 1M urea liquid (60 DEG C), is then filtered to remove filtrate, will filter
Slag is washed with water to neutrality, then ultrasonic disperse 30min, is filtrated to get swollen cellulose；
B, by the parts by weight (average grain diameter 50nm) of Zinc oxide particles 26.5, the parts by weight (average diameter of ZnOw 3.3
For 50nm, average length is 1.5 μm) and the parts by weight (average diameter 200nm) of Kynoar spinning 1.5 in fatty acid polyglycol second
It is well mixed in the parts by weight of diol ester 62, then adds swollen cellulose, vinylidene-hexafluoro third is added after well mixed
The parts by weight of alkene copolymer 4.6, the parts by weight of sodium carboxymethylcellulose 2, the parts by weight of polyoxyethylene fatty acid ester 1.54, after stirring
Obtain ceramic slurry；
Ceramic slurry is coated in the surface of 20cm × 6m polyhexafluoropropylene matrix with 30m/min coating speed C,
Then in 50 DEG C of dry 6h, the thickness for obtaining ceramic coating is 20 μm of lithium ion battery laminated film.
(4) assembly method of battery is the same as embodiment 1.
Embodiment 4
A kind of lithium ion battery, it is made up of positive pole, negative pole and barrier film, its preparation method is as follows：
(1) preparation method of positive pole is the same as embodiment 1；
(2) preparation method of negative pole is the same as embodiment 1；
(3) preparation of barrier film：
A, the parts by weight of cellulose 1.57 are soaked into 24h (90 DEG C) in water, then ultrasonic disperse 30min, be filtrated to get molten
Swollen cellulose；
B, by the parts by weight (average grain diameter 80nm) of alumina particle 24, the parts by weight of alumina whisker 6.3, (average diameter is
150nm, average length 500nm) and the parts by weight (average diameter 500nm) of polyvinyl alcohol spinning 0.3 in the weight of methyl anyl alcohol 57
Measure in part and be well mixed, then add swollen cellulose, the parts by weight of Kynoar 3.8, polyoxy second are added after well mixed
The parts by weight of alkene-poiyoxypropylene copolymer 7.9, ceramic slurry is obtained after stirring；
Ceramic slurry is coated in the surface of 20cm × 6m polyhexafluoropropylene matrix with 100m/min coating speed C,
Then in 30 DEG C of dry 6h, the thickness for obtaining ceramic coating is 0.1 μm of lithium ion battery laminated film.
(4) assembly method of battery is the same as embodiment 1.
Embodiment 5
A kind of lithium ion battery, it is made up of positive pole, negative pole and barrier film, its preparation method is as follows：
(1) preparation method of positive pole is the same as embodiment 1；
(2) preparation method of negative pole is the same as embodiment 1；
(3) preparation of barrier film：
A, the parts by weight of cellulose 0.3 are soaked into 5h in 2M sodium carbonate liquor (50 DEG C), is then filtered to remove filtrate, will
Filter residue is washed with water to neutrality, then ultrasonic disperse 30min, is filtrated to get swollen cellulose；
B, by the parts by weight (average grain diameter 100nm) of zirconia particles 29, the parts by weight (average diameter of boron nitride crystal whisker 0.9
For 100nm, average length is 3 μm) and the parts by weight of polyhexafluoropropylene spinning 0.9 (average diameter is 1 μm) in N- crassitudes
Be well mixed in the parts by weight of ketone 61, then add swollen cellulose, added after well mixed the parts by weight of polyacrylate 4.6,
The parts by weight of polyoxyethylene sorbitan ester 2.7, ceramic slurry is obtained after stirring；
Ceramic slurry is coated in the surface of 20cm × 6m polyhexafluoropropylene matrix with 5m/min coating speed, so C,
Afterwards in 60 DEG C of dry 6h, the thickness for obtaining ceramic coating is 50 μm of lithium ion battery laminated film.
(4) assembly method of battery is the same as embodiment 1.
Embodiment 6
A kind of lithium ion battery, it is made up of positive pole, negative pole and barrier film, its preparation method is as follows：
(1) preparation method of positive pole is the same as embodiment 1；
(2) preparation method of negative pole is the same as embodiment 1；
(3) preparation of barrier film:
According to the method similar to embodiment 1, polymer spinning is not contained in the different ceramic slurries, is embodied
Process is as follows：
A, 1.3 weight part by weight of cellulose are soaked into 2h in 2M sodium hydroxide (40 DEG C) solution, be then filtered to remove
Filtrate, filter residue is washed with water to neutrality, then ultrasonic disperse 30min, is filtrated to get swollen cellulose；
B, by the parts by weight (average grain diameter 20nm) of metatitanic acid k particle 20, the parts by weight (average grain diameter of silica dioxide granule 16
For 40nm) and the parts by weight of silica whisker 2 (average diameter 10nm, average length 800nm) in the parts by weight of n-butanol 45
In be well mixed, then add swollen cellulose, the weight of acrylic ester-acrylonitrile copolymer 4.5 added after well mixed
Part, the parts by weight of hydroxyethyl cellulose 3 and the parts by weight of neopelex 4.5, ceramic slurry is obtained after stirring；
Ceramic slurry is coated in the surface of 20cm × 6m polyvinyl alcohol matrix with 20m/min coating speed, so C,
Afterwards in 50 DEG C of dry 6h, the thickness for obtaining ceramic coating is 1 μm of lithium ion battery laminated film.
(4) assembly method of battery is the same as embodiment 1.
Comparative example 1
A kind of lithium ion battery, it is made up of positive pole, negative pole and barrier film, its preparation method is as follows：
(1) preparation method of positive pole is the same as embodiment 1；
(2) preparation method of negative pole is the same as embodiment 1；
(3) preparation of barrier film:
According to the method similar to embodiment 1, cellulose, specific implementation process are not contained in the different ceramic slurries
It is as follows：
A, by the parts by weight (average grain diameter 20nm) of metatitanic acid k particle 20, the parts by weight (average grain diameter of silica dioxide granule 16
For 40nm), the parts by weight (average diameter 50nm) of polytetrafluoroethylene (PTFE) spinning 2.2 and the parts by weight (average diameter of silica whisker 2
For 10nm, average length 800nm) it is well mixed in the parts by weight of n-butanol 45, swollen cellulose is then added, is well mixed
After add the parts by weight of acrylic ester-acrylonitrile copolymer 4.5, the parts by weight of hydroxyethyl cellulose 3 and neopelex
4.5 parts by weight, ceramic slurry is obtained after stirring；
Ceramic slurry is coated in the surface of 20cm × 6m polyvinyl alcohol matrix with 20m/min coating speed, so B,
Afterwards in 50 DEG C of dry 6h, the thickness for obtaining ceramic coating is 1 μm of lithium ion battery laminated film.
(4) assembly method of battery is the same as embodiment 1.
Comparative example 2
A kind of lithium ion battery, it is made up of positive pole, negative pole and barrier film, its preparation method is as follows：
(1) preparation method of positive pole is the same as embodiment 1；
(2) preparation method of negative pole is the same as embodiment 1；
(3) preparation of barrier film:
According to the method similar to embodiment 1, ceramic whisker is not contained in the different ceramic slurries, was embodied
Journey is as follows：
A, 1.3 part by weight of cellulose are soaked into 2h in 2M sodium hydroxide (40 DEG C) solution, are then filtered to remove filtrate,
Filter residue is washed with water to neutrality, then ultrasonic disperse 30min, is filtrated to get swollen cellulose；
B, by the parts by weight (average grain diameter 20nm) of metatitanic acid k particle 20, the parts by weight (average grain diameter of silica dioxide granule 16
For 40nm), the parts by weight (average diameter 50nm) of polytetrafluoroethylene (PTFE) spinning 2.2 in the parts by weight of n-butanol 45 be well mixed, so
After add swollen cellulose, add the parts by weight of acrylic ester-acrylonitrile copolymer 4.5, hydroxyethyl cellulose after well mixed
3 parts by weight and the parts by weight of neopelex 4.5, ceramic slurry is obtained after stirring；
Ceramic slurry is coated in the surface of 20cm × 6m polyvinyl alcohol matrix with 20m/min coating speed, so C,
Afterwards in 50 DEG C of dry 6h, the thickness for obtaining ceramic coating is 1 μm of lithium ion battery laminated film.
(4) assembly method of battery is the same as embodiment 1.
Performance test
The composite diaphragm that is obtained respectively to the obtained composite diaphragms of embodiment 1-6 and comparative example 1-2 carry out tensile strength,
Peel strength, 150 DEG C work 1h percent thermal shrinkage, pick up test and circulation 500 times after capacity reserved be measured,
Experimental result such as table 1.
Peel strength：Using the peel strength of CN201510999464.2 method testing film.
Barrier film percent thermal shrinkage method of testing：Every kind of barrier film cuts 3 100mm × 100mm samples, measurement MD directions length note
For L0, sample is put into assigned temperature convection oven, the length note L in measurement MD directions is taken out after the defined time, heat is received
The calculation formula of shrinkage is as follows：
Δ L=(L-L0)/L0× 100%
The method of testing of TD directions shrinkage factor is same as above.
Three sample percent thermal shrinkages are measured, are then averaged as the percent thermal shrinkage of such a barrier film.
According to the pick up of CN201310418684.2 method test compound barrier film, wherein electrolyte is methyl esters/carbonic acid
Diethylester (mass ratio 1: 1: 1).
Battery capacity method of testing：Charged with constant voltage charging method, limitation electric current is 0.1C (65mA), final voltage
For 4.4 volts；Discharged in a manner of constant-current discharge, discharge current is 1C (650mA), and the blanking voltage of electric discharge is 3.0 volts.
The performance table for the laminated film that the embodiment 1-6 of table 1, comparative example 1-2 are obtained
By above test result, can learn：The thickness of polymeric body surface ceramic coating is bigger, its tensile strength
Also it is bigger, contrasted by embodiment 1 and embodiment 6 it is known that the polymer spinning stretching that can not only increase composite diaphragm is strong
Degree, also increase the peel strength of composite diaphragm；Embodiment 1 can obtain with the contrast of comparative example 1, and the addition of cellulose significantly increases
The heat endurance of composite diaphragm is added；The contrast of embodiment 1 and comparative example 2 can obtain, ceramic whisker significantly increase it is compound every
The tensile strength of film.
The preferred embodiment of the present invention described in detail above, still, the present invention are not limited in above-mentioned embodiment
Detail, in the range of the technology design of the present invention, a variety of simple variants can be carried out to technical scheme, this
A little simple variants belong to protection scope of the present invention.
It is further to note that each particular technique feature described in above-mentioned embodiment, in not lance
In the case of shield, it can be combined by any suitable means.In order to avoid unnecessary repetition, the present invention to it is various can
The combination of energy no longer separately illustrates.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should equally be considered as content disclosed in this invention.
Claims (10)
1. a kind of composite diaphragm for lithium ion battery, the ceramic thin comprising polymeric matrix and coated in polymeric body surface
Film, the ceramic membrane are made up of ceramic slurry, and the ceramic slurry includes dispersant, binding agent and powder, it is characterised in that
The powder includes following material：Ceramic particle, ceramic whisker and cellulose.
2. composite diaphragm for lithium ion battery according to claim 1, wherein, it is described on the basis of the gross weight of powder
Powder includes the material of following parts by weight：Ceramic particle 75~96%, ceramic whisker 3~20% and cellulose 1~5%.
3. composite diaphragm for lithium ion battery according to claim 1 or 2, wherein, the ceramic particle is aluminium oxide granule
Grain, yttria particles, metatitanic acid k particle, zirconia particles, titanium dioxide granule, silica dioxide granule, barium sulfate particle, metatitanic acid
At least one of titanate particle, calcium carbonate granule, magnesium oxide particle, Zinc oxide particles, silicon-carbide particle and boron nitride particle, it is excellent
Choosing, the micro- 10~100nm of particle diameter of the ceramic particle；
And/or the ceramic whisker is alumina whisker, yittrium oxide whisker, zirconium oxide whisker, titanium dioxide crystal whisker, silica
Whisker, barium sulfate crystal whisker, barium titanate whisker, calcium carbonate crystal whisker, magnesia crystal whisker, ZnOw, silicon carbide whisker and nitridation
At least one of boron whisker, it is preferred that 10~150nm of diameter of the ceramic whisker, length are 500nm~3 μm.
4. composite diaphragm for lithium ion battery according to claim 1, wherein, also contain polymer in the ceramic slurry
Spinning.
5. composite diaphragm for lithium ion battery according to claim 4, wherein, the polymer spinning is Kynoar
It is spinning, polytetrafluoroethylene (PTFE) spinning, pi spinning, polyurethanes spinning, polyvinyl alcohol spinning, polypropylene spinning, poly-
In hexafluoropropene spinning, polyacrylonitrile spinning, PET spinning and polymethyl methacrylate spinning extremely
Few one kind；
Preferably, a diameter of 50nm~1 μm of the polymer spinning.
6. composite diaphragm for lithium ion battery according to claim 1, wherein, the polymeric matrix is polyvinylidene fluoride
Alkene, polytetrafluoroethylene (PTFE), polyvinyl alcohol, polypropylene, polyhexafluoropropylene, polyacrylonitrile, PET and poly- methyl
At least one of methyl acrylate.
7. a kind of preparation method of composite diaphragm for lithium ion battery according to claim 1~6 any one, its feature
It is, comprises the steps of：
A, swelling treatment is carried out to cellulose, obtains swollen cellulose；
B, ceramic particle and ceramic whisker are well mixed in dispersant, then add swollen cellulose, after being well mixed again
Binding agent is added, ceramic slurry is obtained after stirring；
Ceramic slurry is coated in the surface of polymeric matrix, obtain lithium ion battery laminated film C,.
8. the preparation method of composite diaphragm for lithium ion battery according to claim 7, wherein, in step, the fibre
Tieing up plain swelling treatment step is：Cellulose is soaked into 2~24h in aqueous solution, washing, ultrasound, filtering, it is fine to obtain swelling
Dimension element；
Preferably, the aqueous solution is deionized water or alkaline solution.
9. the preparation method of composite diaphragm for lithium ion battery according to claim 8, wherein, the temperature of the aqueous solution
Spend for 25~90 DEG C.
10. a kind of lithium ion battery, include positive pole, negative pole, barrier film and electrolyte, it is characterised in that the barrier film is according to power
Profit requires composite diaphragm for lithium ion battery described in 1~6 any one or according to claim 7~10 any one
The composite diaphragm for lithium ion battery that preparation method is prepared.
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Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010202987A (en) * | 2009-02-27 | 2010-09-16 | Asahi Kasei Corp | Composite sheet material and method for producing the same |
| CN105489819A (en) * | 2016-02-01 | 2016-04-13 | 华东理工大学 | Lithium ion battery ceramic diaphragm paste |
| CN105529425A (en) * | 2014-11-19 | 2016-04-27 | 比亚迪股份有限公司 | Ceramic diaphragm and preparation method and application thereof |
| CN106058126A (en) * | 2016-01-14 | 2016-10-26 | 万向A二三系统有限公司 | Functional coating diaphragm and battery containing same |
| CN106058124A (en) * | 2016-05-29 | 2016-10-26 | 合肥国轩高科动力能源有限公司 | Production method for lithium-ion battery separator |
| CN106450108A (en) * | 2016-10-29 | 2017-02-22 | 曲阜师范大学 | Preparation method of modified cellulose lithium battery diaphragm under sodium hydroxide/urea system |
| CN106654117A (en) * | 2016-10-29 | 2017-05-10 | 曲阜师范大学 | Preparation method for modified cellulose lithium battery diagraph in ionic liquid system |
| CN106784539A (en) * | 2017-01-24 | 2017-05-31 | 厦门大学 | A kind of non-woven fabrics ceramic diaphragm and its preparation method and application |
| CN206271796U (en) * | 2016-09-29 | 2017-06-20 | 天津中聚新能源科技有限公司 | A kind of lithium ion battery composite separation membrane |
-
2017
- 2017-07-05 CN CN201710540555.9A patent/CN107437603A/en active Pending
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010202987A (en) * | 2009-02-27 | 2010-09-16 | Asahi Kasei Corp | Composite sheet material and method for producing the same |
| CN105529425A (en) * | 2014-11-19 | 2016-04-27 | 比亚迪股份有限公司 | Ceramic diaphragm and preparation method and application thereof |
| CN106058126A (en) * | 2016-01-14 | 2016-10-26 | 万向A二三系统有限公司 | Functional coating diaphragm and battery containing same |
| CN105489819A (en) * | 2016-02-01 | 2016-04-13 | 华东理工大学 | Lithium ion battery ceramic diaphragm paste |
| CN106058124A (en) * | 2016-05-29 | 2016-10-26 | 合肥国轩高科动力能源有限公司 | Production method for lithium-ion battery separator |
| CN206271796U (en) * | 2016-09-29 | 2017-06-20 | 天津中聚新能源科技有限公司 | A kind of lithium ion battery composite separation membrane |
| CN106450108A (en) * | 2016-10-29 | 2017-02-22 | 曲阜师范大学 | Preparation method of modified cellulose lithium battery diaphragm under sodium hydroxide/urea system |
| CN106654117A (en) * | 2016-10-29 | 2017-05-10 | 曲阜师范大学 | Preparation method for modified cellulose lithium battery diagraph in ionic liquid system |
| CN106784539A (en) * | 2017-01-24 | 2017-05-31 | 厦门大学 | A kind of non-woven fabrics ceramic diaphragm and its preparation method and application |
Non-Patent Citations (1)
| Title |
|---|
| 娄春华等主编: "《聚合物结构与性能》", 31 May 2016, 哈尔滨：哈尔滨工程大学出版社 * |
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| CN109273644A (en) * | 2018-09-25 | 2019-01-25 | 合肥先杰新能源科技有限公司 | The preparation method of lithium ion fiber base battery diaphragm |
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| WO2021073441A1 (en) * | 2019-10-17 | 2021-04-22 | 华南理工大学 | Lithium ion battery composite diaphragm |
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