CN104064709B - Ceramic diaphragm and its prepare the method and battery of lithium rechargeable battery - Google Patents
Ceramic diaphragm and its prepare the method and battery of lithium rechargeable battery Download PDFInfo
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- CN104064709B CN104064709B CN201410251949.9A CN201410251949A CN104064709B CN 104064709 B CN104064709 B CN 104064709B CN 201410251949 A CN201410251949 A CN 201410251949A CN 104064709 B CN104064709 B CN 104064709B
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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
-
- 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
- H01M10/058—Construction or manufacture
- H01M10/0587—Construction or manufacture of accumulators having only wound construction elements, i.e. wound positive electrodes, wound negative electrodes and wound separators
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/446—Composite material consisting of a mixture of organic and inorganic materials
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The invention discloses ceramic diaphragm, it is that dendriform graft copolymer is synthesized in the presence of initiator by the monomer and enol class monomer of esters of acrylic acid, inorganic ceramic particle is subsequently adding to be uniformly dispersed, then it is applied on the single surface of barrier film base material or two surfaces and is formed, wherein inorganic ceramic granular absorption is on the copolymer and adhered to one another each other, so as to form the ceramic coating of the space network of densification between inorganic ceramic particle and between the copolymer, ceramic coating is adsorbed by the copolymer and barrier film base material, so between inorganic ceramic particle, form the network structure of a solid between the copolymer together with barrier film base material.Also disclose the method and battery for preparing lithium rechargeable battery.The present invention has heat endurance good, and operation control is simple, it is easy to industrialized production, and the stability of assembling procedure but also the security performance of guarantee battery, the effect of environmental protection and energy saving had not only been kept during the use of lithium ion battery.
Description
Technical field
The present invention relates to a kind of ceramic diaphragm, specifically, it is ceramic diaphragm and its prepares the side of lithium rechargeable battery
The technology of method and battery.
Background technology
Lithium rechargeable battery is big due to energy density, and operating voltage is high, the features such as light weight, in consumption electronic product,
Such as mobile phone, notebook computer, panel computer, bluetooth earphone, MP3, digital camera field have been obtained for being widely applied.With
The increasingly serious of environmental pollution and problem of energy crisis, lithium rechargeable battery is in the field such as electrokinetic cell and stationary electric power plant
Using also increasingly popularizing, but the safety issue of lithium rechargeable battery is always focus of concern.
The barrier film of lithium rechargeable battery is clipped between both positive and negative polarity as the isolation of both positive and negative polarity, and Main Function is to prevent just
Negative pole directly contact is short-circuited.The current main porous media being made up of TPOs such as polyethylene, polypropylene of barrier film, polyene
Hydrocarbon barrier film has the fusing point below 180 degree, when lithium rechargeable battery because internal or external factor causes the heating that is short-circuited
And during temperature rising, barrier film easily occurs thermal contraction causes the bigger short circuit generation of both positive and negative polarity, the thermal runaway of battery is caused to cause
Fire accident.In order to solve the above problems, industry is molecular porous by inorganic ceramic grain in one layer of membrane surface coating
Insulating barrier, because inorganic particulate has excellent heat endurance, the porous dielectric layer can be in barrier film thermal contraction as support
Layer prevents both positive and negative polarity directly contact, so as to avoid problem on fire.It is viscous between inorganic ceramic particle and barrier film in order to improve
Knot property, it is to avoid dusting problems, industry avoids this problem by the crosslinking between binding agent.Hyundai Motor Corporation
Patent CN101989651A is by the way that first by ceramic particle and binding agent and curing agent and initiator mixing coating, the later stage passes through hot polymerization
Close or ultraviolet irradiation to be chemically crosslinked to obtain between ceramic particle and ceramic particle is good with barrier film base material caking property
Ceramic diaphragm, the complex and follow-up thermal polymerization of the operation of the method for the patent or ultraviolet light can be to barrier film bases
The pore structure of material has a certain impact.It is core that the patent CN103035866A of Xiamen University passes through to construct in advance with inorganic matter,
Acrylate based polyalcohol replaces existing inorganic ceramic particle so as to improve ceramic particle and barrier film base for the compound of shell
Bonding between material avoids dusting problems, the compound preparation section complicated difficult control of the core shell structure in the method for the patent
System, it is difficult to meet the requirement of industrialized production.
The content of the invention
Good the invention provides a kind of heat endurance, operation control is simple, it is easy to industrialized production, in lithium ion battery
Not only the stability that assembling procedure had been kept during use but also the security performance for ensureing battery, the ceramic diaphragm of environmental protection and energy saving.
Simple present invention also offers operation control, it is easy to industrialized production, environmental protection and energy saving prepare lithium ion secondary electricity
The method and battery in pond.
The present invention is achieved through the following technical solutions.
A kind of ceramic diaphragm, it is characterised in that：The ceramic diaphragm is by the monomer and enol class list of esters of acrylic acid
Body synthesizes dendriform graft copolymer in the presence of initiator, is subsequently adding inorganic ceramic particle and is uniformly dispersed, and is then coated with
Formed on to the single surface of barrier film base material or two surfaces, wherein inorganic ceramic granular absorption is common in dendriform grafting
On polymers and the dendriform graft copolymer is adhered to one another each other, so as between inorganic ceramic particle and described common
Formed between polymers densification space network ceramic coating, ceramic coating by the dendriform graft copolymer with every
Film base material is adsorbed, between such inorganic ceramic particle, between the copolymer and barrier film base material forms the netted of a solid together
Structure.
There is no oxidation or reduction reaction in the inorganic ceramic particle, in lithium rechargeable battery while having electronics exhausted
Edge.
The inorganic ceramic particle is calcium oxide, zinc oxide, magnesia, titanium dioxide, silica, zirconium dioxide, two
Any one or a few in tin oxide, ceria, alundum (Al2O3), calcium carbonate, barium titanate, the inorganic ceramic particle
Grain diameter be 0.01~10 μm, the particle diameter of averaged particles is 0.1~5 μm, and the grain diameter of preferably inorganic ceramic particle is
0.1~6 μm, the particle diameter of averaged particles is 0.3~3 μm, and the dendriform graft copolymer is acrylic polymer, main chain
Selected from methyl acrylate, ethyl acrylate, butyl acrylate, isobutyl acrylate, methyl methacrylate, methacrylic acid second
Ester, butyl methacrylate, Isobutyl methacrylate, hydroxyethyl methacrylate, Ethylene Glycol Methyl methyl acrylate, poly- second
One or more in diol dimethacrylate, 3- methoxy-methyl acrylates, GMA, grafting
Predominantly enol class, selected from one or more in vinyl alcohol, propenyl, butenol, the dendriform graft copolymer passes through third
The monomer of olefin(e) acid esters is polymerized under initiator effect with enol class, and the initiator is azodiisobutyronitrile, mistake
BP, ammonium persulfate, the different toluene of peroxidating two, wherein one or more in di-t-butyl peroxide, acrylate
Monomer is 1 with the mass ratio of enol class monomer:0.01~1, acrylate monomer is 1 with the mass ratio of initiator:0.001~
0.2, the inorganic ceramic particle is 1 with the mass ratio of dendriform graft copolymer:0.1~1, the barrier film base material is PE or PP
Material, inorganic ceramic particle is 0.5~10 μm with the thickness of ceramic coating of dendriform graft copolymer composition.
A kind of preparation method of lithium rechargeable battery, it is characterised in that including：
1）The preparation of positive plate：By cobalt acid lithium, conductive carbon, binding agent Kynoar in 1-METHYLPYRROLIDONE solvent
It is well mixed to be made anode sizing agent, be then coated on aluminium foil and colded pressing after drying, slitting, cutting edge, tab welding, be made
Positive plate；
2）The preparation of negative plate:Graphite, conductive carbon, thickener sodium carboxymethylcellulose, binding agent butadiene-styrene rubber are being gone
In ionized water be well mixed be made cathode size, be then coated on Copper Foil and colded pressing after drying, slitting, cutting edge, lug
Welding, is made negative plate；
3）Barrier film base material：Made with PE or PP microporous membranes；
4）The preparation of the ceramic diaphragm：The main chain material is added in a solvent, and stirring makes it be uniformly dispersed, then
The alkene alcohols material is added, is stirred for, then rise high-temperature, add the initiator, normal temperature is cooled to after stirring, obtained
To dendriform graft copolymer solution, it is subsequently adding the stirring of inorganic ceramic particle and is ground in ball mill, prepares slurry,
Then the above-mentioned slurry made is uniformly covered on a surface of the barrier film base material, then carries out slitting, cutting edge；
5）The preparation of battery:Above-mentioned positive plate, ceramic diaphragm, negative plate are wound into battery core, then the battery core is placed in
In aluminium plastic packaging bag, electrolyte is injected, encapsulated, chemical conversion, the operation of capacity are made battery.
A kind of lithium rechargeable battery, including positive pole, negative pole, barrier film base material and electrolyte, it is characterised in that wherein every
Ceramic coating is coated with least one surface of film base material, the ceramic coating is that one kind will by dendriform graft copolymer
The three-dimensional network structure formed between inorganic ceramic particle, the dendriform graft copolymer and barrier film base material.
The present invention has following technique effect compared with prior art：
1）Ceramic diaphragm of the present invention due to by inorganic ceramic granular absorption on dendritic graft copolymer, inorganic
The fine and close space network formed between ceramic particle and between the copolymer, the ceramic coating passes through the tree
Branch type graft copolymer is adsorbed with barrier film base material, is thus provided that superpower caking property, and excellent heat endurance.
2）The present invention is in the tree by inorganic ceramic granular absorption by the coating structure i.e. ceramic coating for being provided
On branch shape graft copolymer and the dendriform graft copolymer is adhered to one another each other, so as between inorganic ceramic particle
And the ceramic coating of the space network of densification is formed between the copolymer, ceramic coating is grafted by the dendriform
Copolymer and barrier film base material, between such inorganic ceramic particle, between the copolymer and barrier film base material to form one together three-dimensional
Network structure.The space network keeps superpower cohesive force with barrier film base material, while foring the ceramics painting of densification again
Layer, so that with foregoing excellent heat endurance, and process is simple is easy to control.Ceramic diaphragm of the present invention is in lithium-ion electric
Both the stability of assembling procedure had been maintained during the use in pond, the security performance of battery had been in turn ensure that.
3）The present invention prepares the method and battery of lithium rechargeable battery, and operation control is simple, it is easy to industrialized production, ring
Protect energy-conservation.
Brief description of the drawings
Fig. 1 is the structural representation of ceramic diaphragm of the present invention.
Specific embodiment
Make further details of elaboration, but embodiments of the present invention not limited to this to the present invention with reference to embodiment.
Such as Fig. 1, ceramic diaphragm of the present invention is the effect by the monomer and enol class monomer of esters of acrylic acid in initiator
Lower synthesis dendriform graft copolymer 2, is subsequently adding inorganic ceramic particle 3 and is uniformly dispersed, and is then applied to the list of barrier film base material 1
Formed on one surface or two surfaces, wherein inorganic ceramic granular absorption is on the dendriform graft copolymer and the tree
Branch shape graft copolymer is adhered to one another each other, is caused so as to be formed between inorganic ceramic particle and between the copolymer
The ceramic coating of close space network, ceramic coating is adsorbed by the dendriform graft copolymer and barrier film base material, this
Between sample inorganic ceramic particle, between the copolymer and barrier film base material forms the network structure of a solid together.It is wherein inorganic
There is no oxidation or reduction reaction in ceramic particle, in lithium rechargeable battery while having electronic isolation.
Inorganic ceramic particle of the present invention be preferably calcium oxide, zinc oxide, magnesia, titanium dioxide, silica,
Any one or a few in zirconium dioxide, tin ash, ceria, alundum (Al2O3), calcium carbonate, barium titanate.Inorganic grain
The averaged particles of the particle of son select 0.1~5 μm of particle, and preferably 0.3~3 μm, granulometric range changes at 0.01~10 μm,
It is preferred that 0.1~6 μm of scope.Dendriform graft copolymer is acrylic polymer, and main chain is selected from methyl acrylate, propylene
Acetoacetic ester, butyl acrylate, isobutyl acrylate, methyl methacrylate, EMA, butyl methacrylate,
Isobutyl methacrylate, hydroxyethyl methacrylate, Ethylene Glycol Methyl methyl acrylate, glycol dimethacrylates
One or more in ester, 3- methoxy-methyl acrylates, GMA, grafting is mainly enol class, choosing
One or more from vinyl alcohol, propenyl, butenol.The dendriform graft copolymer is existed by the monomer of esters of acrylic acid
Initiator effect is lower to be polymerized with enol class, and described initiator is azodiisobutyronitrile, benzoyl peroxide, over cure
Sour ammonium, the different toluene of peroxidating two, one or more in di-t-butyl peroxide.The matter of acrylate monomer and enol class monomer
Amount is than being 1:0.1~1, acrylate monomer is 1 with the mass ratio of initiator:0.001~0.2.
Inorganic ceramic particle is 1 with the mass ratio of dendriform graft copolymer:0.1~1, the barrier film base material is PE or PP
Material, the thickness of ceramic coating of inorganic ceramic particle and dendriform graft copolymer composition is 0.5~10 μm, preferably 1~6 μm,
The ceramic coating is coated at least one surface of barrier film base material.
In order to the mixture that inorganic particulate and binding agent are formed is coated in into barrier film base material surface, it is possible to use this area is
Through well known any method, usable method includes：Dip-coating, die head apply (Slot coating), roller coat, comma transfer apply,
Intaglio plate is applied or its combination.Inorganic coating selectively can be coated on the single surface of barrier film or two surfaces.It is inorganic
Coating is that thickness of ceramic coating is 0.5~10 μm, preferably 1~6 μm.
Lithium rechargeable battery of the present invention, including positive pole, negative pole, barrier film base material and electrolyte, wherein barrier film base material
Ceramic coating is coated with least one surface, the ceramic coating is a kind of dendriform graft copolymer that passes through by inorganic ceramic
The three-dimensional network structure formed between particle, the dendriform graft copolymer and barrier film base material.
The preparation method of lithium rechargeable battery of the present invention, including：
1）The preparation of positive plate：By cobalt acid lithium, conductive carbon, binding agent Kynoar in 1-METHYLPYRROLIDONE solvent
In be well mixed be made anode sizing agent, be then coated on aluminium foil and colded pressing after dry, slitting, cutting edge, tab welding, make
Into positive plate；
2）The preparation of negative plate:Graphite, conductive carbon, thickener sodium carboxymethylcellulose, binding agent butadiene-styrene rubber are being gone
In ionized water be well mixed be made cathode size, be then coated on Copper Foil and colded pressing after drying, slitting, cutting edge, lug
Welding, is made negative plate；
3）Barrier film base material：Made with PE or PP microporous membranes；
4）The preparation of the ceramic diaphragm：The main chain material is added in the mixed solvent of ethanol and deionized water,
Stirring makes it be uniformly dispersed, and is subsequently adding the alkene alcohols material, is stirred for, and then rises high-temperature, initiator is added, after stirring
Normal temperature is cooled to, dendriform graft copolymer solution is obtained, the inorganic ceramic particle is subsequently added into, stirred and in ball mill
Middle grinding, prepares slurry, and then the above-mentioned slurry made is uniformly covered on a surface of the barrier film base material, then
Carry out slitting, cutting edge；
5）The preparation of battery:Above-mentioned positive plate, ceramic diaphragm, negative plate are wound into battery core, then the battery core is placed in
In aluminium plastic packaging bag, electrolyte is injected, encapsulated, chemical conversion, the operation of capacity are made battery.
Here is specific embodiment.
Comparative example 1：That is comparative example 1.
The preparation of positive plate：By cobalt acid lithium, conductive carbon, binding agent Kynoar in mass ratio 96：2.2：1.8 in N- first
It is well mixed in base pyrrolidones (NMP) solvent and is made anode sizing agent, is then coated on aluminium foil and is dried at 110 DEG C laggard
Row cold pressing, slitting, cutting edge, tab welding, be made positive plate.
The preparation of negative plate:Graphite, conductive carbon, thickener sodium carboxymethylcellulose, binding agent butadiene-styrene rubber are pressed into quality
Than 95：1.5：1.5：2.0 in deionized water be well mixed be made cathode size, be then coated on Copper Foil and at 85 DEG C dry
Colded pressing after dry, slitting, cutting edge, tab welding, be made negative plate.
Barrier film：Polyethylene micropore film that thickness is 9 μm is taken as barrier film.
The preparation of battery:Above-mentioned positive plate, barrier film, negative plate are wound into battery core, the battery core is then placed in plastic-aluminum
In packaging bag, electrolyte (ethylene carbonate is injected:Dimethyl carbonate:Methyl ethyl carbonate=1:2:1, comprising 1M hexafluorophosphoric acids
Lithium), the operation such as encapsulated, chemical conversion, capacity is made battery.
Comparative example 2：Comparative example 2
The preparation of positive plate：By cobalt acid lithium, conductive carbon, binding agent Kynoar in mass ratio 96：2.2：1.8 in N- first
It is well mixed in base pyrrolidones (NMP) solvent and is made anode sizing agent, is then coated on aluminium foil and is dried at 110 DEG C laggard
Row cold pressing, slitting, cutting edge, tab welding, be made positive plate.
The preparation of negative plate:Graphite, conductive carbon, thickener sodium carboxymethylcellulose, binding agent butadiene-styrene rubber are pressed into quality
Than 95：1.5：1.5：2.0 in deionized water be well mixed be made cathode size, be then coated on Copper Foil and at 85 DEG C dry
Colded pressing after dry, slitting, cutting edge, tab welding, be made negative plate.
Barrier film：Polyethylene micropore film that thickness is 9 μm is taken as barrier film.
The preparation of ceramic diaphragm：Polyacrylate dispersion (the content in the aqueous solution of 15wt% is first added in deionized water
40%) to stir 1h, be subsequently adding 85wt% Al2O3 particles (average grain diameter is 0.3 μm, the distribution of particle for 0.08~
1.5 μm) stirring 2h after, 1h is ground in ball mill, prepare slurry, solid content is 30%.Then will be made using intaglio plate coating
Above-mentioned slurry be uniformly covered on a surface of 9 μm of polyethylene micropore film, coating layer thickness is 4 μm, Ran Houji
Piece carries out slitting, cutting edge.
The preparation of battery:Above-mentioned positive plate, barrier film, negative plate are wound into battery core, the battery core is then placed in plastic-aluminum
In packaging bag, electrolyte (ethylene carbonate is injected:Dimethyl carbonate:Methyl ethyl carbonate=1:2:1, comprising 1M hexafluorophosphoric acids
Lithium), the operation such as encapsulated, chemical conversion, capacity is made battery.
Embodiments of the invention：
Embodiment 1
The preparation of positive plate：By cobalt acid lithium, conductive carbon, binding agent Kynoar in mass ratio 96：2.2：1.8 in N- first
It is well mixed in base pyrrolidones (NMP) solvent and is made anode sizing agent, is then coated on aluminium foil and is dried at 110 DEG C laggard
Row cold pressing, slitting, cutting edge, tab welding, be made positive plate.
The preparation of negative plate:Graphite, conductive carbon, thickener sodium carboxymethylcellulose, binding agent butadiene-styrene rubber are pressed into quality
Than 95：1.5：1.5：2.0 in deionized water be well mixed be made cathode size, be then coated on Copper Foil and at 85 DEG C dry
Colded pressing after dry, slitting, cutting edge, tab welding, be made negative plate.
Barrier film：Polyethylene micropore film that thickness is 9 μm is taken as barrier film.
The preparation of ceramic diaphragm：(the deionized water in the mixed solvent of ethanol and deionized water:Ethanol=1:1) added in
Methyl methacrylate (MMA), stirs 1H, is uniformly dispersed, and is subsequently adding propenyl, wherein methyl methacrylate and propylene
The mass ratio of alcohol is 1:0.8, stirring 1H is uniformly dispersed, and then temperature is increased to 75 degree, adds azodiisobutyronitrile, methyl-prop
E pioic acid methyl ester is 1 with the mass ratio of azodiisobutyronitrile:0.08, normal temperature is cooled to after stirring 2H, obtain dendriform graft copolymerization
Thing solution, solid content is 30%.Be subsequently added into Al2O3 particles (average grain diameter is 0.5 μm, the distribution of particle for 0.08~
1.5 μm), wherein Al2O3 is 85 with the mass ratio of dendriform graft copolymer:15, after stirring 2h, 1h is ground in ball mill,
Slurry is prepared, the solid content of the slurry is 50%.Then the above-mentioned slurry made is uniformly covered on 9 μ using intaglio plate coating
On one surface of the polyethylene micropore film of m, coating layer thickness is 4 μm, and then pole piece carries out slitting, cutting edge.It is of the invention normal
Temperature refers to 20-28 degrees Celsius.
The preparation of battery:Above-mentioned positive plate, barrier film, negative plate are wound into battery core, the battery core is then placed in plastic-aluminum
In packaging bag, electrolyte (ethylene carbonate is injected:Dimethyl carbonate:Methyl ethyl carbonate=1:2:1, comprising 1M hexafluorophosphoric acids
Lithium), the operation such as encapsulated, chemical conversion, capacity is made battery.
Embodiment 2
The preparation of positive plate：By cobalt acid lithium, conductive carbon, binding agent Kynoar in mass ratio 96：2.2：1.8 in N- first
It is well mixed in base pyrrolidones (NMP) solvent and is made anode sizing agent, is then coated on aluminium foil and is dried at 110 DEG C laggard
Row cold pressing, slitting, cutting edge, tab welding, be made positive plate.
The preparation of negative plate:Graphite, conductive carbon, thickener sodium carboxymethylcellulose, binding agent butadiene-styrene rubber are pressed into quality
Than 95：1.5：1.5：2.0 in deionized water be well mixed be made cathode size, be then coated on Copper Foil and at 85 DEG C dry
Colded pressing after dry, slitting, cutting edge, tab welding, be made negative plate.
Barrier film：Polypropylene microporous film that thickness is 12 μm is taken as barrier film.
The preparation of ceramic diaphragm：(the deionized water in the mixed solvent of ethanol and deionized water:Ethanol=1:1) added in
Methyl methacrylate (MMA), stirs 1H, is uniformly dispersed, and is subsequently adding propenyl, wherein methyl methacrylate and propylene
The mass ratio of alcohol is 1:0.8, stirring 1H is uniformly dispersed, and then temperature is increased to 75 degree, adds azodiisobutyronitrile, methyl-prop
E pioic acid methyl ester is 1 with the mass ratio of azodiisobutyronitrile:0.08, normal temperature is cooled to after stirring 2H, obtain dendriform graft copolymerization
Thing solution, solid content is 30%.(average grain diameter is 0.2 μm, and the distribution of particle is 0.08~1.0 to be subsequently added into TiO2 particles
μm), wherein TiO2 is 85 with the mass ratio of dendriform graft copolymer:15, after stirring 2h, 1h is ground in ball mill, prepare
Slurry is obtained, the solid content of the slurry is 30%.Then the above-mentioned slurry made is uniformly covered on 9 μm using intaglio plate coating
On one surface of polyethylene micropore film, coating layer thickness is 4 μm, and then pole piece carries out slitting, cutting edge.
The preparation of battery:Above-mentioned positive plate, barrier film, negative plate are wound into battery core, the battery core is then placed in plastic-aluminum
In packaging bag, electrolyte (ethylene carbonate is injected:Dimethyl carbonate:Methyl ethyl carbonate=1:2:1, comprising 1M hexafluorophosphoric acids
Lithium), the operation such as encapsulated, chemical conversion, capacity is made battery.
Embodiment 3
The preparation of positive plate：By cobalt acid lithium, conductive carbon, binding agent Kynoar in mass ratio 96：2.2：1.8 in N- first
It is well mixed in base pyrrolidones (NMP) solvent and is made anode sizing agent, is then coated on aluminium foil and is dried at 110 DEG C laggard
Row cold pressing, slitting, cutting edge, tab welding, be made positive plate.
The preparation of negative plate:Graphite, conductive carbon, thickener sodium carboxymethylcellulose, binding agent butadiene-styrene rubber are pressed into quality
Than 95：1.5：1.5：2.0 in deionized water be well mixed be made cathode size, be then coated on Copper Foil and at 85 DEG C dry
Colded pressing after dry, slitting, cutting edge, tab welding, be made negative plate.
Barrier film：Polypropylene microporous film that thickness is 9 μm is taken as barrier film.
The preparation of ceramic diaphragm：(the deionized water in the mixed solvent of ethanol and deionized water:Ethanol=1:1) added in
Methyl methacrylate (MMA), stirs 1H, is uniformly dispersed, and is subsequently adding propenyl, wherein methyl methacrylate and propylene
The mass ratio of alcohol is 1:0.8, stirring 1H is uniformly dispersed, and then temperature is increased to 75 degree, adds azodiisobutyronitrile, methyl-prop
E pioic acid methyl ester is 1 with the mass ratio of azodiisobutyronitrile:0.08, normal temperature is cooled to after stirring 2H, obtain dendriform graft copolymerization
Thing solution, solid content is 30%.(average grain diameter is 0.2 μm, and the distribution of particle is 0.08~1.0 to be subsequently added into TiO2 particles
μm), wherein TiO2 is 85 with the mass ratio of dendriform graft copolymer:15, after stirring 2h, 1h is ground in ball mill, prepare
Slurry is obtained, the solid content of the slurry is 30%.Then the above-mentioned slurry made is uniformly covered on 9 μm using dip-coating method
On two surfaces of polyethylene micropore film, coating layer thickness is 6 μm, and then pole piece carries out slitting, cutting edge.
The preparation of battery:Above-mentioned positive plate, barrier film, negative plate are wound into battery core, the battery core is then placed in plastic-aluminum
In packaging bag, electrolyte (ethylene carbonate is injected:Dimethyl carbonate:Methyl ethyl carbonate=1:2:1, comprising 1M hexafluorophosphoric acids
Lithium), the operation such as encapsulated, chemical conversion, capacity is made battery.
Here is that the ceramic diaphragm in the barrier film and the embodiment of the present invention of comparative example carries out thermal contraction test.
Coating strip force is tested：Barrier film is punched into the square sample of 20X100mm, will be made pottery using the 3M double faced adhesive tapes of 15mm
Porcelain coating is fixed on one block of steel plate, and 180 degree coating stripping test is carried out by tensilon, compares comparative example and embodiment
Coating cohesive force.Acquired results are shown in Table 1：
The comparative example of table 1 and embodiment ceramic coating cohesive force
As known from Table 1, the ceramic diaphragm coating cohesive force in the present invention using dendriform graft copolymer binding agent is improved
Clearly.
Thermal contraction test:Barrier film is punched into the square sample of 100X100mm, MD and TD directions are indicated, measurement is initial
MD and TD length, 2H is toasted in the baking oven for putting it into 130 degree, after taking-up test baking after MD and TD directions length,
Calculate percent thermal shrinkage=[(size after size-baking before baking)/red size before examination] X100%.Acquired results are shown in Table 2：
The comparative example of table 2 and embodiment barrier film percent thermal shrinkage
As known from Table 2, ceramic diaphragm of the present invention is obviously improved to thermal contraction, uses dendriform graft copolymer binding agent
Barrier film thermal contraction improvement becomes apparent from.
Here is that the lithium ion battery of comparative example and embodiment is circulated test
Cycle performance is tested:Lithium ion battery is charged using the multiplying power of 0.5C at 25 degrees c, the multiplying power discharging of 0.5C,
Carry out 500 circulations successively, the battery capacity under each loop test 0.5C multiplying powers, and with circulation before capacity under 25 degree of battery
It is compared, calculates the capability retention after circulation, capability retention=(the preceding battery of capacity/circulation after circulation under 0.5C multiplying powers
Capacity under 25 degree) X100%.
The comparative example of table 3 and embodiment circulation volume conservation rate
As known from Table 3, ceramic diaphragm of the present invention does not interfere with battery performance.
Here be comparative example and embodiment lithium ion battery circulation before and circulation after battery carry out drift bolt safety test
Drift bolt is tested：First battery is completely filled, is then tested according to the standard of UL1642, nail diameter is
2.5mm, drift bolt speed is 100mm/s.Drift bolt is carried out to the battery after the battery before circulation and 500 circulations respectively to survey safely
Examination.
Table 4 circulates the drift bolt test result of front and rear battery
As known from Table 4, the battery using the ceramic diaphragm of dendriform graft copolymer is electric before circulation and after 500 circulations
Pond all maintains security performance very high.
The announcement and elaboration of book according to the above description, those skilled in the art in the invention can also be to above-mentioned embodiment party
Formula carries out appropriate change and modification.Therefore, the invention is not limited in specific embodiment disclosed and described above, to this
Some practical modifications and changes should also be as falling into claim of the invention and protection domain.Although additionally, this specification
In used some specific terms, but these terms are merely for convenience of description, do not constitute any limitation to the present invention.
Claims (6)
1. a kind of ceramic diaphragm, it is characterised in that：The ceramic diaphragm is by the monomer and enol class monomer of esters of acrylic acid
Synthesize dendriform graft copolymer in the presence of initiator, be subsequently adding inorganic ceramic particle and be uniformly dispersed, be then applied to
Formed on the single surface of barrier film base material or two surfaces, wherein inorganic ceramic granular absorption is in the dendriform graft copolymerization
On thing and the dendriform graft copolymer is adhered to one another each other, so as between inorganic ceramic particle and the copolymerization
The ceramic coating of the space network of densification is formed between thing, ceramic coating passes through the dendriform graft copolymer and barrier film
Base material is adsorbed, between such inorganic ceramic particle, between the copolymer and barrier film base material forms the netted knot of a solid together
Structure.
2. ceramic diaphragm according to claim 1, it is characterised in that：The inorganic ceramic particle is in lithium rechargeable battery
There is no oxidation or reduction reaction, while having electronic isolation.
3. ceramic diaphragm according to claim 1 or claim 2, it is characterised in that：The inorganic ceramic particle is calcium oxide, oxidation
Zinc, magnesia, titanium dioxide, silica, zirconium dioxide, tin ash, ceria, alundum (Al2O3), calcium carbonate, metatitanic acid
Any one or more in barium, the grain diameter of the inorganic ceramic particle is 0.01~10 μm, and the particle diameter of averaged particles is
0.1~5 μm, the dendriform graft copolymer is acrylic polymer, and main chain is selected from methyl acrylate, acrylic acid second
Ester, butyl acrylate, isobutyl acrylate, methyl methacrylate, EMA, butyl methacrylate, methyl
Isobutyl acrylate, hydroxyethyl methacrylate, Ethylene Glycol Methyl methyl acrylate, polyethylene glycol dimethacrylate, 3-
One or more in methoxy-methyl acrylate, GMA, it is enol class to be grafted, selected from vinyl alcohol,
One or more in propenyl, butenol, the dendriform graft copolymer is made by the monomer of esters of acrylic acid in initiator
It is polymerized with enol class with lower, the initiator is azodiisobutyronitrile, benzoyl peroxide, ammonium persulfate, peroxide
Change one or more in two different toluene, di-t-butyl peroxide, wherein the mass ratio of acrylate monomer and enol class monomer
It is 1:0.01~1, acrylate monomer is 1 with the mass ratio of initiator:0.001~0.2,
The inorganic ceramic particle is 1 with the mass ratio of dendriform graft copolymer:0.1~1, the barrier film base material is PE or PP materials
Matter, inorganic ceramic particle is 0.5~10 μm with the thickness of ceramic coating of dendriform graft copolymer composition.
4. ceramic diaphragm according to claim 3, it is characterised in that：The grain diameter of the inorganic ceramic particle is 0.1~6
μm, the particle diameter of averaged particles is 0.3~3 μm.
5. a kind of preparation method of lithium rechargeable battery, it is characterised in that including：
1) preparation of positive plate：Cobalt acid lithium, conductive carbon, binding agent Kynoar are mixed in 1-METHYLPYRROLIDONE solvent
Uniformly be made anode sizing agent, be then coated on aluminium foil and colded pressing after drying, slitting, cutting edge, tab welding, be made positive pole
Piece；
2) preparation of negative plate:By graphite, conductive carbon, thickener sodium carboxymethylcellulose, binding agent butadiene-styrene rubber in deionization
In water be well mixed be made cathode size, be then coated on Copper Foil and colded pressing after drying, slitting, cutting edge, tab welding,
It is made negative plate；
3) barrier film base material：Made with PE or PP microporous membranes；
4) preparation of ceramic diaphragm described in claim 3：The main chain material is added in mixed solvent, stirring makes its dispersion equal
It is even, the alkene alcohols material is subsequently adding, it is stirred for, initiator then is added at selected temperature, cooled to after stirring often
Temperature, obtains dendriform graft copolymer solution, is subsequently added into the inorganic ceramic particle, stirs and is ground in ball mill, system
It is standby to obtain slurry, then obtained above-mentioned slurry is uniformly covered at least one surface of the barrier film base material, then enter
Row slitting, cutting edge；
5) preparation of battery:Above-mentioned positive plate, ceramic diaphragm, negative plate are wound into battery core, the battery core is then placed in plastic-aluminum
In packaging bag, electrolyte is injected, encapsulated, chemical conversion, the operation of capacity are made battery.
6. the lithium rechargeable battery that a kind of use claim 5 methods described is prepared, including positive pole, negative pole, barrier film base
Material and electrolyte, it is characterised in that ceramic coating is wherein coated with least one surface of barrier film base material, the ceramics are applied
Layer is a kind of dendriform graft copolymer that passes through by between inorganic ceramic particle, the dendriform graft copolymer and barrier film base material
The three-dimensional network structure of formation.
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| CN104659313B (en) * | 2015-02-26 | 2017-12-08 | 广东烛光新能源科技有限公司 | A kind of composite porous isolating membrane, the battery and preparation method thereof of the isolation film preparation |
| US10439249B2 (en) | 2015-03-23 | 2019-10-08 | Envision Aesc Energy Devices Ltd. | Lithium ion secondary battery |
| CN104835985A (en) * | 2015-03-24 | 2015-08-12 | 江苏乐能电池股份有限公司 | A preparing method of a high-specific-energy lithium ion battery |
| CN106784531A (en) * | 2016-08-29 | 2017-05-31 | 东莞市卓高电子科技有限公司 | A kind of preparation method of PMMA and its copolymer mixing coating barrier film |
| CN106654128B (en) * | 2017-01-18 | 2021-01-26 | 宁德新能源科技有限公司 | Secondary battery |
| CN106654123B (en) * | 2017-01-20 | 2020-01-24 | 东莞市卓高电子科技有限公司 | Preparation method of PVDF (polyvinylidene fluoride) or PVDF (polyvinylidene fluoride) copolymer coating diaphragm |
| CN107394278A (en) * | 2017-07-26 | 2017-11-24 | 王昌国 | A kind of manufacture method of lithium ion battery of electric automobile |
| CN111656588B (en) * | 2018-02-19 | 2023-12-22 | 日本瑞翁株式会社 | Binder composition for nonaqueous secondary battery electrode, slurry composition, electrode, and secondary battery |
| CN108923077A (en) * | 2018-06-26 | 2018-11-30 | 苏州英诺达自动化科技有限公司 | A kind of lithium battery preparation method with long service life |
| CN108878960B (en) * | 2018-07-03 | 2020-06-09 | 宁德卓高新材料科技有限公司 | Solid electrolyte positive electrode and solid battery |
| KR20200072993A (en) * | 2018-12-13 | 2020-06-23 | 현대자동차주식회사 | Lithium secondary battery and manufacturing method thereof |
| CN111180638A (en) * | 2020-01-17 | 2020-05-19 | 江苏厚生新能源科技有限公司 | PVDF (polyvinylidene fluoride) modified diaphragm and preparation method thereof |
| CN113871797A (en) * | 2020-06-11 | 2021-12-31 | 恒大新能源技术(深圳)有限公司 | Ceramic diaphragm and preparation method and application thereof |
| CN112521702B (en) * | 2020-06-22 | 2022-01-11 | 四川大学 | Polymer composition, flexible self-supporting film, and preparation method and application thereof |
| CN112142995A (en) * | 2020-08-24 | 2020-12-29 | 深圳市德立新材料科技有限公司 | Organic-inorganic composite grape particle structure material, slurry, diaphragm and preparation method |
| WO2022110223A1 (en) * | 2020-11-30 | 2022-06-02 | 宁德时代新能源科技股份有限公司 | Separator film, secondary battery containing same, related battery module thereof, battery pack and device |
| CN113629357A (en) * | 2021-07-23 | 2021-11-09 | 恒大新能源技术(深圳)有限公司 | Battery diaphragm, preparation method thereof and secondary battery |
| CN114335904B (en) * | 2022-02-28 | 2022-07-12 | 湖南中锂新材料科技有限公司 | Lithium battery composite diaphragm and preparation method and application thereof |
| CN117397109A (en) * | 2022-03-25 | 2024-01-12 | 宁德时代新能源科技股份有限公司 | Separator, preparation method thereof, battery and power utilization device |
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| US20040086782A1 (en) * | 2002-11-01 | 2004-05-06 | Celgard Inc. | Explosion-proof separator for Li-ion secondary batteries |
| KR100754746B1 (en) * | 2007-03-07 | 2007-09-03 | 주식회사 엘지화학 | Organic/inorganic composite separator having porous active coating layer and electrochemical device containing the same |
| CN102983299A (en) * | 2012-12-17 | 2013-03-20 | 天津工业大学 | Preparation and product of battery membrane material with low electrolyte leakage |
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