CN108539099A - A kind of corrosion-resisting lithium battery diaphragm and preparation method thereof - Google Patents
A kind of corrosion-resisting lithium battery diaphragm and preparation method thereof Download PDFInfo
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- CN108539099A CN108539099A CN201810413744.4A CN201810413744A CN108539099A CN 108539099 A CN108539099 A CN 108539099A CN 201810413744 A CN201810413744 A CN 201810413744A CN 108539099 A CN108539099 A CN 108539099A
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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
- 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
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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- Y02E60/10—Energy storage using batteries
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Abstract
The invention discloses a kind of corrosion-resisting lithium battery diaphragms and preparation method thereof.The corrosion-resisting lithium battery diaphragm, including following raw material：Polypropylene, Kynoar, polyether acrylate, urethane acrylate, polyvinyl resin, maleic anhydride, nano silicon dioxide, nanometer alchlor, nano-titanium dioxide, antimony oxide, corrosion-resistant reinforcement modifying agent, corrosion-resistant reinforced filling, surface modifier；The corrosion-resisting lithium battery diaphragm is the base-material being tentatively kneaded by preparing base-material, and nano-titanium dioxide, antimony oxide, corrosion-resistant reinforcement modifying agent, corrosion-resistant reinforced filling and surface modifier then is added in the base-material being tentatively kneaded, after heating in twin-screw in extruder, shear at high temperature, plasticizing, stirring is plasticized, and is blended, blend melt is obtained, is then delivered in die head, is cooled and solidified in rapidly chilling roller, obtain sheet material, biaxial tension, extraction, obtains after thermal finalization.The corrosion-resisting lithium battery diaphragm of the present invention has excellent corrosion resistance.
Description
Technical field
The invention belongs to the preparing technical fields of lithium ion battery material, and in particular to a kind of corrosion-resisting lithium battery diaphragm and
Preparation method.
Background technology
Lithium battery develops rapidly in recent years, but lithium battery safety and high-performance be always restrict its development key ask
Topic, diaphragm are the electrical insulating property films for having porous structure, main function be positive and negative electrode is isolated and prevent electronics in battery from
It passes through self, while electrolyte solution intermediate ion can be allowed to be passed freely through in positive and negative interpolar, performance determines the interface knot of battery
Structure, internal resistance etc. directly affect the characteristics such as capacity, the cycle performance of battery.
A kind of Chinese patent application document " preparation method of lithium battery diaphragm（Application publication number：CN106784528A）" public
A kind of preparation method of lithium battery diaphragm has been opened, including：Modified inorganic nano-particle is placed in pore former, is stirred, is surpassed
Sound disperses, and obtains pre-dispersed solvent：First vistanex, the second vistanex and the pre-dispersed solvent are added to double
In screw extruder, shear at high temperature, plasticizing, blending obtain blend melt；The blend melt is delivered in T-shaped mould head, it is cold
But cure, obtain sheet material, by the sheet material biaxial tension, extraction obtains lithium battery diaphragm, this method passes through addition after thermal finalization
Ultra-high molecular weight polyethylene, it is ensured that the mechanical strength of diaphragm is used as heterogeneous nucleation agent, to obtain by adding inorganic nano-particle
Higher voidage, smaller pore size are obtained, micropore distribution evenly forms good heat resistance, therefore, lithium electricity
Pond diaphragm has excellent permeability, higher mechanical strength, thermal stability, it is ensured that the high security of battery, but its
Antiseptic property cannot be satisfied demand in actual use.
Chinese patent application document " a kind of lithium battery diaphragm and preparation method thereof and the application in lithium battery（Application is public
Announcement number：CN106876641A）" disclose a kind of lithium battery diaphragm and preparation method thereof and the application in lithium battery, lithium electricity
Pond diaphragm is inorganic nano fiber film, and inorganic constituents can enhance the thermal dimensional stability of lithium battery diaphragm, make lithium battery diaphragm
With enhancing lithium battery diaphragm and electrolyte wellability, inorganic nano fiber film porosity is higher, can improve lithium battery every
The electrolyte absorptivity and ionic conductivity of film, are conducive to the cycle and high rate performance that improve lithium battery, and this method uses quiet
The lithium battery diaphragm that Electrospinning is prepared has the advantages that high temperature resistant, high porosity, and obtained lithium battery diaphragm can be with
The high-temperature process of long period is born, and will not occur significantly to be heat-shrinked phenomenon, the technique letter of the lithium battery film is answered, productivity
Height, the lithium battery diaphragm being prepared disclosure satisfy that high-capacity lithium ion cell security requirement, but its corrosion resistance without
The needs of method meets in actual use.
Invention content
The object of the present invention is to provide a kind of corrosion-resisting lithium battery diaphragms and preparation method thereof, to solve in Chinese patent Shen
It please a kind of document " preparation method of lithium battery diaphragm（Application publication number：CN106784528A）" and Patent Application Publication " one kind
Lithium battery diaphragm and preparation method thereof and the application in lithium battery（Apply for notification number：CN106876641A）" disclosed in lithium electricity
The problem of on the basis of the diaphragm of pond, how optimizing component, dosage, method etc., improving the lithium battery diaphragm corrosion resistance.
In order to solve the above technical problems, the present invention uses following technical scheme：
A kind of corrosion-resisting lithium battery diaphragm, including following raw material：Polypropylene, Kynoar, polyether acrylate, polyurethane third
Olefin(e) acid ester, polyvinyl resin, maleic anhydride, nano silicon dioxide, nanometer alchlor, nano-titanium dioxide, antimony oxide,
Corrosion-resistant reinforcement modifying agent, corrosion-resistant reinforced filling, surface modifier；
The corrosion-resistant reinforcement modifying agent, as unit of parts by weight, including following raw material：20-30 parts of phenolic resin, rare earth chloride
4-8 parts, 3-6 parts of barium sulfate, 2-5 parts of weathered coal, 1-4 parts of bentonite, 3-6 parts of zeolite powder, 4-8 parts of nano-titanium dioxide, alkyl
2-6 parts of phenol polyethenoxy ether, 1-5 parts of neopelex, 4-8 parts of Silane coupling reagent KH-570；
The corrosion-resistant reinforced filling, as unit of parts by weight, including following raw material：15-25 parts of butyl acrylate, nano-silica
Change 4-8 parts of glass putty body, 3-9 parts of silane resin acceptor kh-550,2-6 parts of chitosan, 1-5 parts of bamboo powder, 4-8 parts of diatomite, distilled water
12-24 parts, 4-8 parts of maleic anhydride, 3-6 parts of ammonium persulfate, 2-8 parts of silane coupling agent KH-560；
The polyether acrylate, polyvinyl resin, maleic anhydride, nano-titanium dioxide, antimony oxide, corrosion-resistant reinforcement change
The weight ratio of property agent, corrosion-resistant reinforced filling and surface modifier is（20-40）：（8-12）：（4-6）：（2-5）：（3-6）：
（10-20）：（15-25）：（1-3）.
Further, the weight ratio is 30：10：5：3.5：4.5：2：15：20.
Further, as unit of parts by weight, including following raw material：80-120 parts of polypropylene, Kynoar 30-40
Part, 20-40 parts of polyether acrylate, 15-35 parts of urethane acrylate, 8-12 parts of polyvinyl resin, maleic anhydride 4-6
Part, 4-8 parts of nano silicon dioxide, 3-6 parts of nanometer alchlor, 2-5 parts of nano-titanium dioxide, 3-6 parts of antimony oxide, corrosion-resistant benefit
Strong 10-20 parts of modifying agent, reinforced filling 15-25 parts corrosion-resistant, 1-3 parts of surface modifier.
Further, the corrosion-resistant reinforcement modifying agent is prepared by following technique：It is dilute that chlorination is added in phenolic resin
It is uniformly mixed in soil, is warming up to 60-80 DEG C, kept the temperature 10-30min, kept stirring during heat preservation, then proceed to be warming up to
80-90 DEG C, 10-15min is kept the temperature, is then refluxed for 3-4h, then vacuum dehydration, then heat to 140-160 DEG C, keeps the temperature 5-
Barium sulfate, weathered coal, bentonite, zeolite powder, nano-titanium dioxide, alkylphenol-polyethenoxy is added in 15min after being cooled to room temperature
Ether, neopelex and Silane coupling reagent KH-570 are uniformly mixed, ultrasound-mechanical agitation point in 45-55 DEG C of water-bath
2-4h is dissipated, stratification removes supernatant liquor, lower reaction product layer is filtered, and washs, 750-850 DEG C is dried under vacuum to
Constant weight, grinding cross 150-250 mesh sieve to get to corrosion-resistant reinforcement modifying agent.
Further, the corrosion-resistant reinforced filling is prepared by following technique：By butyl acrylate and nano-silica
Change glass putty body to be uniformly mixed, silane resin acceptor kh-550 is then added and is uniformly mixed, stirs 20-28h in 38-46 DEG C, be cooled to
Room temperature is subsequently placed in ice-water bath and is crushed, and is ultrasonically treated 10-14min and obtains material a；Under nitrogen protection, by chitosan, bamboo
Powder, diatomite, distilled water and maleic anhydride are uniformly mixed, and then heat to 80-90 DEG C, keep the temperature 10-30min, then admixture
Expect that a and ammonium persulfate are uniformly mixed, addition silane coupling agent KH-560 is uniformly mixed after stirring 5-15min, then in 850-
1250r/min rotating speeds stir 50-70min, then heat to 85-95 DEG C, extract 40-50h, then in vacuum drying oven, 65-75
It DEG C dries to constant weight, is cooled to room temperature to obtain corrosion-resistant reinforced filling.
Further, the surface modifier is azobisisoheptonitrile, tetraethylenepentamine, anilinomethyl triethoxysilicane
Alkane is by weight 1-3：4-6：3-5 is mixed.
The present invention also provides a kind of preparation methods of corrosion-resisting lithium battery diaphragm, include the following steps：
S1：It stirs, be subsequently added into nano silicon dioxide and receive after polypropylene, Kynoar and urethane acrylate are heated up
Rice alchlor is uniformly mixed, and is stirred after continuing heating, is cooled to room temperature to obtain base-material；
S2：Polyether acrylate, polyvinyl resin, maleic anhydride is added after the base-material that S1 is obtained is heated up to be uniformly mixed,
It is stirred after continuing heating, is cooled to room temperature the base-material being tentatively kneaded；
S3：It will be stirred after the base-material heating of being tentatively kneaded of obtaining of S2, nano-titanium dioxide, antimony oxide, corrosion-resistant be then added
Reinforcement modifying agent, corrosion-resistant reinforced filling and surface modifier are uniformly mixed, and are stirred after continuing heating, are then squeezed in twin-screw
Go out in machine, shear at high temperature, be plasticized, stir, be plasticized, be blended, obtain blend melt, then by melt conveying to die head, in urgency
It is cooled and solidified on quickly cooling roller, obtains sheet material, then carry out biaxial tension, extracted, corrosion-resisting lithium battery diaphragm is obtained after thermal finalization.
Further, in S1, S1：After polypropylene, Kynoar and urethane acrylate are warming up to 110-120 DEG C
20-30min is stirred in 650-850r/min rotating speeds, nano silicon dioxide is subsequently added into and nanometer alchlor is uniformly mixed, after
Continue and stir 1-2h in 1200-1400r/min rotating speeds after being warming up to 140-160 DEG C, is cooled to room temperature to obtain base-material.
Further, in S2, polyether acrylate, polyethylene tree are added after the base-material that S1 is obtained is warming up to 90-110 DEG C
Fat, maleic anhydride are uniformly mixed, and 1-2h is stirred in 850-1050r/min rotating speeds after being continuously heating to 120-140 DEG C, cooling
The base-material being tentatively kneaded to room temperature.
Further, in S3, in 650-850r/min after the base-material being tentatively kneaded that S2 is obtained is warming up to 120-140 DEG C
Rotating speed stirs 1-2h, and nano-titanium dioxide, antimony oxide, corrosion-resistant reinforcement modifying agent, corrosion-resistant reinforced filling and table is then added
Face modifying agent is uniformly mixed, and 1-2h is stirred in 1500-2500r/min rotating speeds after being continuously heating to 150-160 DEG C, then in double spiral shells
In bar in extruder, shear at high temperature is plasticized, and is stirred, and is plasticized, and is blended, is obtained blend melt, then part melt conveying to die head
In, it is cooled and solidified in rapidly chilling roller, obtains sheet material, then carry out biaxial tension, extracted, corrosion-resistant lithium electricity is obtained after thermal finalization
Pond diaphragm.
The invention has the advantages that：
（1）By embodiment 1-3 and the data of comparative example 10 and comparative example 11 as it can be seen that corrosion-resistant lithium electricity made from embodiment 1-3
The corrosion resistance of pond diaphragm is significantly higher than the corrosion resistance of lithium battery material made from comparative example 10 and comparative example 11；Simultaneously
By the data of embodiment 1-3 as it can be seen that embodiment 1 is optimum embodiment, by embodiment 1 and the data of comparative example 1-9 as it can be seen that polyethers
It is acrylate, polyvinyl resin, maleic anhydride, nano-titanium dioxide, antimony oxide, corrosion-resistant reinforcement modifying agent, corrosion-resistant
Reinforced filling and surface modifier play synergistic effect in preparing corrosion-resisting lithium battery diaphragm, and collaboration improves the lithium battery
The corrosion resistance of material.
（2）Polyether acrylate, polyvinyl resin, maleic anhydride, nano-titanium dioxide, antimony oxide, corrosion-resistant benefit
Strong modifying agent, corrosion-resistant reinforced filling and surface modifier are as reinforcement system, wherein polyether acrylate and polyvinyl resin
For major ingredient, assigning reinforcement system enhances corrosion resistance, and maleic anhydride acts on polyether acrylate as modified monomer
During the melt process of polyvinyl resin, the corrosion resistance of polyether acrylate and polyvinyl resin is improved, addition
Nano-titanium dioxide and the corrosion-resistant modified filler of antimony oxide, for addition surface modifier as graft modification agent, realization will be corrosion-resistant
Reinforcement modifying agent, corrosion-resistant reinforced filling corrosion-resistant reinforcing property apply in the base-material of the lithium battery material, realize resistance to
Corrosion reinforcement modifying agent and the hydroxyl on corrosion-resistant reinforced filling surface realize and base-material under the grafting effect of surface modifier
In conjunction with the corrosion resistance for effectively increasing lithium battery material of the present invention improves.
（3）Corrosion-resistant reinforcement modifying agent is uniformly mixed by the way that phenolic resin to be added in rare earth chloride, is heated up, and is kept the temperature, and is protected
It is kept stirring in the process of temperature, then proceedes to heat up, kept the temperature, be then refluxed for, then vacuum dehydration, then heat up, kept the temperature, it is cooling
Barium sulfate, weathered coal, bentonite, zeolite powder, nano-titanium dioxide, alkyl phenol polyoxyethylene ether, dodecane are added after to room temperature
Base benzene sulfonic acid sodium salt and Silane coupling reagent KH-570 are uniformly mixed, ultrasound-mechanical agitation dispersion in water-bath, stratification, in removal
Layer clear liquid, lower reaction product layer is filtered, and is washed, is dried under vacuum to constant weight, is ground, sieving obtains, with phenolic resin
As resin binder, using rare earth chloride as modified initiator, with barium sulfate, weathered coal, bentonite, zeolite powder and nanometer titanium dioxide
Titanium is corrosion-resistant reinforced filling, using alkyl phenol polyoxyethylene ether and neopelex as surfactant, with silane
Coupling agent kh-570 realizes as modified grafting agent and carries out hydroxyl modification, realization and phenolic aldehyde to corrosion-resistant reinforced filling surface
Resin surface combines, and applies in the lithium battery diaphragm preparation of the present invention, effectively increases the corrosion resistant of lithium battery diaphragm of the present invention
Corrosion energy.
（4）Then corrosion-resistant reinforced filling is added by the way that butyl acrylate and nano tin oxide powder to be uniformly mixed
Silane resin acceptor kh-550 is uniformly mixed, and stirring is cooled to room temperature, and is subsequently placed in ice-water bath and is crushed, and supersound process obtains object
Expect a；Under nitrogen protection, chitosan, bamboo powder, diatomite, distilled water and maleic anhydride are uniformly mixed, are then heated up, kept the temperature,
Then material a is added and ammonium persulfate is uniformly mixed, silane coupling agent KH-560 is added after stirring and is uniformly mixed, is followed by stirring for,
Then it heats up, extracts, then in vacuum drying oven, dry to constant weight, be cooled to room temperature to obtain, with butyl acrylate and maleic acid
Acid anhydride is grafted monomers, with chitosan, bamboo powder, diatomite, nano tin oxide powder for corrosion-resistant reinforced filling, with ammonium persulfate
It is modified grafting agent with silane coupling agent KH-560 for initiator, table is carried out to corrosion-resistant reinforced filling by modified grafting agent
Face hydroxyl modification, realization are combined with grafted monomers, are applied in the lithium battery diaphragm preparation of the present invention, are effectively increased this
The corrosion resistance of lithium battery diaphragm.
（5）By the data of comparative example 12-14 as it can be seen that polyether acrylate, polyvinyl resin, maleic anhydride, nanometer
Titanium dioxide, antimony oxide, corrosion-resistant reinforcement modifying agent, corrosion-resistant reinforced filling and surface modifier weight ratio do not exist（20-
40）：（8-12）：（4-6）：（2-5）：（3-6）：（10-20）：（15-25）：（1-3）When in range, lithium battery material obtained
The corresponding numerical value of corrosion resistance and the numerical value of embodiment 1-3 are very different, and the numerical value of embodiment 1-3 are much smaller than, with existing skill
Art（Comparative example 10 and comparative example 11）Numerical value it is suitable.Polyether acrylate of the present invention, polyvinyl resin, maleic anhydride,
Nano-titanium dioxide, antimony oxide, corrosion-resistant reinforcement modifying agent, corrosion-resistant reinforced filling and surface modifier as reinforcement system,
By adding polyether acrylate, polyvinyl resin, maleic acid when embodiment 1-3 controls prepare corrosion-resisting lithium battery diaphragm
Acid anhydride, nano-titanium dioxide, antimony oxide, corrosion-resistant reinforcement modifying agent, corrosion-resistant reinforced filling and surface modifier weight ratio be
（20-40）：（8-12）：（4-6）：（2-5）：（3-6）：（10-20）：（15-25）：（1-3）, realize in reinforcement system using poly-
Ether acrylate and the excellent corrosion resistance of polyvinyl resin are modified grafted monomers with maleic anhydride, with nanometer two
Under titanium oxide and antimony oxide are acted on as corrosion-resistant reinforced filling, using polyether acrylate and polyvinyl resin as reinforcement system
For major ingredient, realizes that less corrosion-resistant reinforced filling acts on polyether acrylate and polyvinyl resin, improve polyethers propylene
The corrosion resistance of acid esters and polyvinyl resin, and under the grafting of surface modifier effect, corrosion-resistant reinforcement is utilized and is modified
The corrosion resistance strengthening action of agent effectively increases the corrosion resistance of the lithium battery material, while matching with corrosion-resistant reinforced filling
It closes, is applied in base-material under the action of surface modifier, effectively increase the corrosion resistance of the lithium battery material, as a result,
It is polyether acrylate, polyvinyl resin, maleic anhydride, nano-titanium dioxide, antimony oxide, corrosion-resistant reinforcement modifying agent, resistance to
Corrosion reinforced filling and surface modifier are applied to as reinforcement system in the preparation of the lithium battery material, effectively increase the lithium
The corrosion resistance of battery material.
（6）Surface modifier is azobisisoheptonitrile, tetraethylenepentamine, anilinomethyl triethoxysilane by certain ratio
Example mixes, using azobisisoheptonitrile and tetraethylenepentamine as crosslinking accelerator, with anilinomethyl triethoxysilicane
Alkane is graft modification agent, applies in the lithium battery diaphragm preparation of the present invention, effectively increases the corrosion-resistant of the lithium battery diaphragm
Property.
（7）The present invention obtains base-material by using resin refining glue material, then by nano silicon dioxide, nanometer alchlor,
Nano-titanium dioxide, antimony oxide, corrosion-resistant reinforcement modifying agent and corrosion-resistant reinforced filling carry out surface modifying agent, realize
Nano silicon dioxide, nanometer alchlor, nano-titanium dioxide, antimony oxide, corrosion-resistant reinforcement modifying agent and corrosion-resistant reinforcement are filled out
Expect the modification of surface hydroxyl, realizes and combined with base-material grafting, and then realize the reinforcement to base-material corrosion resistance, finally pass through
In double screw extruder, by shear at high temperature, it is plasticized, stirs, be plasticized, be blended, obtain blend melt, then extremely by melt conveying
It in die head, is cooled and solidified in rapidly chilling roller, obtains sheet material, then carry out biaxial tension, extracted, lithium battery is obtained after thermal finalization
Diaphragm, this method is easy to operate, efficient, and the obtained lithium ion battery separator of preparation has excellent corrosion resistance.
Specific implementation mode
For ease of more fully understanding the present invention, it is illustrated by the following examples, these examples belong to the protection of the present invention
Range, but do not limit the scope of the invention.
In embodiment, the corrosion-resisting lithium battery diaphragm, as unit of parts by weight, including following raw material：Polypropylene 80-
120 parts, 30-40 parts of Kynoar, 20-40 parts of polyether acrylate, 15-35 parts of urethane acrylate, polyvinyl resin
8-12 parts, 4-6 parts of maleic anhydride, 4-8 parts of nano silicon dioxide, 3-6 parts of nanometer alchlor, nano-titanium dioxide 2-5
Part, 3-6 parts of antimony oxide, 10-20 parts of corrosion-resistant reinforcement modifying agent, reinforced filling 15-25 parts corrosion-resistant, 1-3 parts of surface modifier.
Corrosion-resistant reinforcement modifying agent is prepared by following technique：20-30 parts of phenolic resin are added 4-8 parts by weight
It is uniformly mixed in rare earth chloride, is warming up to 60-80 DEG C, kept the temperature 10-30min, kept stirring during heat preservation, then proceed to rise
Temperature keeps the temperature 10-15min, is then refluxed for 3-4h, then vacuum dehydration to 80-90 DEG C, then heats to 140-160 DEG C, keeps the temperature 5-
15min, after being cooled to room temperature be added 3-6 parts of barium sulfate, 2-5 parts of weathered coals, 1-4 parts of bentonites, 3-6 parts of zeolite powders, 4-8 parts receive
Rice titanium dioxide, 2-6 parts of alkyl phenol polyoxyethylene ether, 1-5 parts of neopelexes and 4-8 parts of Silane coupling reagent KH-570s
It is uniformly mixed, ultrasound-mechanical agitation disperses 2-4h in 45-55 DEG C of water-bath, and stratification removes supernatant liquor, and lower layer is anti-
It answers product to be filtered, washs, 750-850 DEG C is dried under vacuum to constant weight, grinding, crosses 150-250 mesh sieve to get to corrosion-resistant benefit
Strong modifying agent.
Corrosion-resistant reinforced filling is prepared by following technique：15-25 parts of butyl acrylates and 4-8 parts are received by weight
Rice tin dioxide powder is uniformly mixed, and 3-9 parts of silane resin acceptor kh-550s are then added and are uniformly mixed, and 20- is stirred in 38-46 DEG C
28h is cooled to room temperature, and is subsequently placed in ice-water bath and is crushed, and is ultrasonically treated 10-14min and is obtained material a；Under nitrogen protection, will
2-6 parts of chitosans, 1-5 parts of bamboo powders, 4-8 parts of diatomite, 12-24 parts of distilled water and 4-8 parts of maleic anhydrides are uniformly mixed, and are then risen
Temperature keeps the temperature 10-30min to 80-90 DEG C, and a and 3-6 parts of ammonium persulfates of material are then added and are uniformly mixed, and adds after stirring 5-15min
Enter 2-8 parts of silane coupling agent KH-560 to be uniformly mixed, then stirs 50-70min in 850-1250r/min rotating speeds, then heat up
To 85-95 DEG C, 40-50h is extracted, then in vacuum drying oven, 65-75 DEG C dries to constant weight, and is cooled to room temperature to obtain corrosion-resistant benefit
Strong filler.
The preparation method of the corrosion-resisting lithium battery diaphragm, includes the following steps：
S1：In 650-850r/min rotating speeds after polypropylene, Kynoar and urethane acrylate are warming up to 110-120 DEG C
20-30min is stirred, nano silicon dioxide is subsequently added into and nanometer alchlor is uniformly mixed, after being continuously heating to 140-160 DEG C
1-2h is stirred in 1200-1400r/min rotating speeds, is cooled to room temperature to obtain base-material；
S2：Polyether acrylate, polyvinyl resin, maleic anhydride are added after the base-material that S1 is obtained is warming up to 90-110 DEG C
It is uniformly mixed, 1-2h is stirred in 850-1050r/min rotating speeds after being continuously heating to 120-140 DEG C, be cooled to room temperature to obtain preliminary
The base-material of mixing；
S3：1-2h is stirred in 650-850r/min rotating speeds after the base-material being tentatively kneaded that S2 is obtained is warming up to 120-140 DEG C, so
It is equal that nano-titanium dioxide, antimony oxide, corrosion-resistant reinforcement modifying agent, corrosion-resistant reinforced filling and surface modifier mixing are added afterwards
It is even, 1-2h is stirred in 1500-2500r/min rotating speeds after being continuously heating to 150-160 DEG C, then in twin-screw in extruder,
Shear at high temperature is plasticized, and is stirred, and is plasticized, and is blended, blend melt is obtained, then in part melt conveying to die head, in rapidly chilling roller
Cooling and solidifying, obtains sheet material, then carries out biaxial tension, extracts, corrosion-resisting lithium battery diaphragm is obtained after thermal finalization.
Embodiment 1
A kind of corrosion-resisting lithium battery diaphragm, as unit of parts by weight, including following raw material：100 parts of polypropylene, Kynoar 35
Part, 30 parts of polyether acrylate, 25 parts of urethane acrylate, 10 parts of polyvinyl resin, 5 part, nanometer two of maleic anhydride
4.5 parts of 6 part, nanometer alchlor of silica, 3.5 parts of nano-titanium dioxide, 4.5 parts of antimony oxide, corrosion-resistant reinforcement modifying agent 15
Part, 20 parts of corrosion-resistant reinforced filling, 2 parts of surface modifier.
Corrosion-resistant reinforcement modifying agent is prepared by following technique：6 parts of chlorinations are added in 25 parts of phenolic resin by weight
It is uniformly mixed in rare earth, is warming up to 70 DEG C, kept the temperature 20min, kept stirring during heat preservation, then proceed to be warming up to 85 DEG C,
12.5min is kept the temperature, is then refluxed for 3.5h, then vacuum dehydration, then heats to 150 DEG C, 10min is kept the temperature, after being cooled to room temperature
4.5 parts of barium sulfate, 3.5 parts of weathered coals, 2.5 parts of bentonites, 4.5 parts of zeolite powders, 6 parts of nano-titanium dioxides, 4 parts of alkyl phenols are added
Polyoxyethylene ether, 3 parts of neopelexes and 6 parts of Silane coupling reagent KH-570s are uniformly mixed, the ultrasound-in 50 DEG C of water-baths
Mechanical agitation disperses 3h, and stratification removes supernatant liquor, lower reaction product layer is filtered, and washs, and 800 DEG C of vacuum are dry
It is dry to constant weight, grinding crosses 200 mesh sieve to get to corrosion-resistant reinforcement modifying agent.
Corrosion-resistant reinforced filling is prepared by following technique：By weight by 20 parts of butyl acrylates and 6 parts of nanometers two
Tin oxide powder is uniformly mixed, and 6 parts of silane resin acceptor kh-550s are then added and are uniformly mixed, and for 24 hours in 42 DEG C of stirrings, is cooled to room
Temperature is subsequently placed in ice-water bath and is crushed, and is ultrasonically treated 12min and obtains material a；Under nitrogen protection, by 4 parts of chitosans, 3 portions of bamboos
Powder, 6 parts of diatomite, 18 parts of distilled water and 6 parts of maleic anhydrides are uniformly mixed, and are then heated to 85 DEG C, are kept the temperature 20min, then add
Enter material a and 4.5 parts of ammonium persulfates are uniformly mixed, 5 parts of silane coupling agent KH-560 of addition are uniformly mixed after stirring 10min, are connect
It and stirs 60min in 1050r/min rotating speeds, then heat to 90 DEG C, extract 45h, then in vacuum drying oven, 70 DEG C are dried to perseverance
Weight, is cooled to room temperature to obtain corrosion-resistant reinforced filling.
The preparation method of the corrosion-resisting lithium battery diaphragm, includes the following steps：
S1：It is stirred in 750r/min rotating speeds after polypropylene, Kynoar and urethane acrylate are warming up to 115 DEG C
25min, is subsequently added into nano silicon dioxide and nanometer alchlor is uniformly mixed, and is continuously heating to after 150 DEG C in 1300r/min
Rotating speed stirs 1.5h, is cooled to room temperature to obtain base-material；
S2：Polyether acrylate, polyvinyl resin, maleic anhydride are added after the base-material that S1 is obtained is warming up to 100 DEG C to mix
It closes uniformly, stirs 1.5h in 950r/min rotating speeds after being continuously heating to 130 DEG C, be cooled to room temperature the base-material being tentatively kneaded；
S3：1.5h is stirred in 750r/min rotating speeds after the base-material being tentatively kneaded that S2 is obtained is warming up to 130 DEG C, is then added and receives
Rice titanium dioxide, antimony oxide, corrosion-resistant reinforcement modifying agent, corrosion-resistant reinforced filling and surface modifier are uniformly mixed, after of continuing rising
Temperature stirs 1.5h to after 155 DEG C in 2000r/min rotating speeds, and then in twin-screw in extruder, shear at high temperature is plasticized, stirring,
Plasticizing is blended, obtains blend melt, then in part melt conveying to die head, cooled and solidified in rapidly chilling roller, obtain sheet material,
Then biaxial tension is carried out, extracts, corrosion-resisting lithium battery diaphragm is obtained after thermal finalization.
Embodiment 2
A kind of corrosion-resisting lithium battery diaphragm, as unit of parts by weight, including following raw material：80 parts of polypropylene, Kynoar 40
Part, 20 parts of polyether acrylate, 35 parts of urethane acrylate, 8 parts of polyvinyl resin, 6 parts of maleic anhydride, nano-silica
It is 6 parts of 4 part, nanometer alchlor of SiClx, 2 parts of nano-titanium dioxide, 6 parts of antimony oxide, 10 parts of corrosion-resistant reinforcement modifying agent, corrosion-resistant
25 parts of reinforced filling, 1 part of surface modifier.
Corrosion-resistant reinforcement modifying agent is prepared by following technique：8 parts of chlorinations are added in 20 parts of phenolic resin by weight
It is uniformly mixed in rare earth, is warming up to 60 DEG C, kept the temperature 30min, kept stirring during heat preservation, then proceed to be warming up to 80 DEG C,
15min is kept the temperature, is then refluxed for 3h, then vacuum dehydration, then heats to 160 DEG C, 5min is kept the temperature, 6 is added after being cooled to room temperature
Part barium sulfate, 2 parts of weathered coals, 4 parts of bentonites, 3 parts of zeolite powders, 8 parts of nano-titanium dioxides, 2 parts of alkyl phenol polyoxyethylene ether, 5
Part neopelex and 4 parts of Silane coupling reagent KH-570s are uniformly mixed, ultrasound-mechanical agitation dispersion in 55 DEG C of water-baths
2h, stratification remove supernatant liquor, lower reaction product layer are filtered, and wash, 850 DEG C are dried under vacuum to constant weight, grind
Mill crosses 150 mesh sieve to get to corrosion-resistant reinforcement modifying agent.
Corrosion-resistant reinforced filling is prepared by following technique：By weight by 15 parts of butyl acrylates and 8 parts of nanometers two
Tin oxide powder is uniformly mixed, and 3 parts of silane resin acceptor kh-550s are then added and are uniformly mixed, and is stirred 20h in 46 DEG C, is cooled to room
Temperature is subsequently placed in ice-water bath and is crushed, and is ultrasonically treated 14min and obtains material a；Under nitrogen protection, by 2 parts of chitosans, 5 portions of bamboos
Powder, 4 parts of diatomite, 24 parts of distilled water and 4 parts of maleic anhydrides are uniformly mixed, and are then heated to 90 DEG C, are kept the temperature 10min, then add
Enter material a and 6 parts of ammonium persulfates be uniformly mixed, stir and 8 parts of silane coupling agent KH-560 are added after 5min are uniformly mixed, then in
850r/min rotating speeds stir 70min, then heat to 85 DEG C, extract 50h, then in vacuum drying oven, 65 DEG C dry to constant weight, cold
But corrosion-resistant reinforced filling is obtained to room temperature.
The preparation method of the corrosion-resisting lithium battery diaphragm, includes the following steps：
S1：It is stirred in 850r/min rotating speeds after polypropylene, Kynoar and urethane acrylate are warming up to 110 DEG C
20min, is subsequently added into nano silicon dioxide and nanometer alchlor is uniformly mixed, and is continuously heating to after 160 DEG C in 1200r/min
Rotating speed stirs 2h, is cooled to room temperature to obtain base-material；
S2：Polyether acrylate, polyvinyl resin, maleic anhydride mixing are added after the base-material that S1 is obtained is warming up to 90 DEG C
Uniformly, 2h is stirred in 850r/min rotating speeds after being continuously heating to 140 DEG C, is cooled to room temperature the base-material being tentatively kneaded；
S3：1h is stirred in 850r/min rotating speeds after the base-material being tentatively kneaded that S2 is obtained is warming up to 120 DEG C, nanometer is then added
Titanium dioxide, antimony oxide, corrosion-resistant reinforcement modifying agent, corrosion-resistant reinforced filling and surface modifier are uniformly mixed, and continue to heat up
2h is stirred in 1500r/min rotating speeds after to 160 DEG C, then in twin-screw in extruder, shear at high temperature is plasticized, and is stirred, modeling
Change, is blended, obtains blend melt, then in part melt conveying to die head, cooled and solidified in rapidly chilling roller, obtain sheet material, so
After carry out biaxial tension, extract, corrosion-resisting lithium battery diaphragm is obtained after thermal finalization.
Embodiment 3
A kind of corrosion-resisting lithium battery diaphragm, as unit of parts by weight, including following raw material：120 parts of polypropylene, Kynoar 30
Part, 40 parts of polyether acrylate, 15 parts of urethane acrylate, 12 parts of polyvinyl resin, 4 part, nanometer two of maleic anhydride
3 parts of 8 part, nanometer alchlor of silica, 5 parts of nano-titanium dioxide, 3 parts of antimony oxide, 20 parts of corrosion-resistant reinforcement modifying agent, corrosion resistant
Lose 15 parts of reinforced filling, 3 parts of surface modifier.
Corrosion-resistant reinforcement modifying agent is prepared by following technique：4 parts of chlorinations are added in 30 parts of phenolic resin by weight
It is uniformly mixed in rare earth, is warming up to 80 DEG C, kept the temperature 10min, kept stirring during heat preservation, then proceed to be warming up to 90 DEG C,
10min is kept the temperature, is then refluxed for 4h, then vacuum dehydration, then heats to 140 DEG C, 15min is kept the temperature, 3 is added after being cooled to room temperature
Part barium sulfate, 5 parts of weathered coals, 1 part of bentonite, 6 parts of zeolite powders, 4 parts of nano-titanium dioxides, 6 parts of alkyl phenol polyoxyethylene ether, 1
Part neopelex and 8 parts of Silane coupling reagent KH-570s are uniformly mixed, ultrasound-mechanical agitation dispersion in 45 DEG C of water-baths
4h, stratification remove supernatant liquor, lower reaction product layer are filtered, and wash, 750 DEG C are dried under vacuum to constant weight, grind
Mill crosses 250 mesh sieve to get to corrosion-resistant reinforcement modifying agent.
Corrosion-resistant reinforced filling is prepared by following technique：By weight by 25 parts of butyl acrylates and 4 parts of nanometers two
Tin oxide powder is uniformly mixed, and 9 parts of silane resin acceptor kh-550s are then added and are uniformly mixed, and is stirred 28h in 38 DEG C, is cooled to room
Temperature is subsequently placed in ice-water bath and is crushed, and is ultrasonically treated 10min and obtains material a；Under nitrogen protection, by 6 parts of chitosans, 1 portion of bamboo
Powder, 8 parts of diatomite, 12 parts of distilled water and 8 parts of maleic anhydrides are uniformly mixed, and are then heated to 80 DEG C, are kept the temperature 30min, then add
Enter material a and 3 parts of ammonium persulfates are uniformly mixed, 2 parts of silane coupling agent KH-560 of addition are uniformly mixed after stirring 15min, then
50min is stirred in 1250r/min rotating speeds, then heats to 95 DEG C, extracts 40h, then in vacuum drying oven, 75 DEG C are dried to perseverance
Weight, is cooled to room temperature to obtain corrosion-resistant reinforced filling.
The preparation method of the corrosion-resisting lithium battery diaphragm, includes the following steps：
S1：It is stirred in 650r/min rotating speeds after polypropylene, Kynoar and urethane acrylate are warming up to 120 DEG C
30min, is subsequently added into nano silicon dioxide and nanometer alchlor is uniformly mixed, and is continuously heating to after 140 DEG C in 1400r/min
Rotating speed stirs 1h, is cooled to room temperature to obtain base-material；
S2：Polyether acrylate, polyvinyl resin, maleic anhydride are added after the base-material that S1 is obtained is warming up to 110 DEG C to mix
It closes uniformly, stirs 1h in 1050r/min rotating speeds after being continuously heating to 120 DEG C, be cooled to room temperature the base-material being tentatively kneaded；
S3：2h is stirred in 650r/min rotating speeds after the base-material being tentatively kneaded that S2 is obtained is warming up to 140 DEG C, nanometer is then added
Titanium dioxide, antimony oxide, corrosion-resistant reinforcement modifying agent, corrosion-resistant reinforced filling and surface modifier are uniformly mixed, and continue to heat up
1h is stirred in 2500r/min rotating speeds after to 150 DEG C, then in twin-screw in extruder, shear at high temperature is plasticized, and is stirred, modeling
Change, is blended, obtains blend melt, then in part melt conveying to die head, cooled and solidified in rapidly chilling roller, obtain sheet material, so
After carry out biaxial tension, extract, corrosion-resisting lithium battery diaphragm is obtained after thermal finalization.
Comparative example 1
It is essentially identical with the preparation process of embodiment 1, have only unlike prepare and lack in the raw material of corrosion-resisting lithium battery diaphragm
It is polyether acrylate, polyvinyl resin, maleic anhydride, nano-titanium dioxide, antimony oxide, corrosion-resistant reinforcement modifying agent, resistance to
Corrode reinforced filling and surface modifier.
Comparative example 2
It is essentially identical with the preparation process of embodiment 1, have only unlike prepare and lack in the raw material of corrosion-resisting lithium battery diaphragm
Polyether acrylate.
Comparative example 3
It is essentially identical with the preparation process of embodiment 1, have only unlike prepare and lack in the raw material of corrosion-resisting lithium battery diaphragm
Polyvinyl resin.
Comparative example 4
It is essentially identical with the preparation process of embodiment 1, have only unlike prepare and lack in the raw material of corrosion-resisting lithium battery diaphragm
Maleic anhydride.
Comparative example 5
It is essentially identical with the preparation process of embodiment 1, have only unlike prepare and lack in the raw material of corrosion-resisting lithium battery diaphragm
Nano-titanium dioxide.
Comparative example 6
It is essentially identical with the preparation process of embodiment 1, have only unlike prepare and lack in the raw material of corrosion-resisting lithium battery diaphragm
Antimony oxide.
Comparative example 7
It is essentially identical with the preparation process of embodiment 1, have only unlike prepare and lack in the raw material of corrosion-resisting lithium battery diaphragm
Corrosion-resistant reinforcement modifying agent.
Comparative example 8
It is essentially identical with the preparation process of embodiment 1, have only unlike prepare and lack in the raw material of corrosion-resisting lithium battery diaphragm
Corrosion-resistant reinforced filling.
Comparative example 9
It is essentially identical with the preparation process of embodiment 1, have only unlike prepare and lack in the raw material of corrosion-resisting lithium battery diaphragm
Surface modifier.
Comparative example 10
Using a kind of Chinese patent application document " preparation method of lithium battery diaphragm（Application publication number：CN106784528A）" in
Method described in specific embodiment 1-5 prepares lithium battery material.
Comparative example 11
Using Chinese patent application document " a kind of lithium battery diaphragm and preparation method thereof and the application in lithium battery（Application is public
Announcement number：CN106876641A）" in method described in specific embodiment 1-6 prepare lithium battery material.
Comparative example 12
It is essentially identical with the preparation process of embodiment 1, have only unlike prepare polyethers in the raw material of corrosion-resisting lithium battery diaphragm
Acrylate is 19 parts, polyvinyl resin is 13 parts, maleic anhydride is 3 parts, nano-titanium dioxide is 6 parts, antimony oxide 2
Part, corrosion-resistant reinforcement modifying agent are 22 parts, corrosion-resistant reinforced filling is 14 parts, 4 parts of surface modifier.
Comparative example 13
It is essentially identical with the preparation process of embodiment 1, have only unlike prepare polyethers in the raw material of corrosion-resisting lithium battery diaphragm
Acrylate is 41 parts, polyvinyl resin is 7 parts, maleic anhydride is 7 parts, nano-titanium dioxide is 1 part, antimony oxide 7
Part, corrosion-resistant reinforcement modifying agent are 9 parts, corrosion-resistant reinforced filling is 26 parts, 0.8 part of surface modifier.
Comparative example 14
It is essentially identical with the preparation process of embodiment 1, have only unlike prepare polyethers in the raw material of corrosion-resisting lithium battery diaphragm
Acrylate is 41 parts, polyvinyl resin is 7 parts, maleic anhydride is 3 parts, nano-titanium dioxide is 6 parts, antimony oxide 2
Part, corrosion-resistant reinforcement modifying agent are 23 parts, corrosion-resistant reinforced filling is 14 parts, 5 parts of surface modifier.
Corrosion resistance test is carried out to product made from embodiment 1-3 and comparative example 1-14, the results are shown in table below.
As seen from the above table：（1）By embodiment 1-3 and the data of comparative example 10 and comparative example 11 as it can be seen that embodiment 1-3 systems
The corrosion resistance of the corrosion-resisting lithium battery diaphragm obtained is significantly higher than lithium battery material made from comparative example 10 and comparative example 11
Corrosion resistance；Simultaneously by the data of embodiment 1-3 as it can be seen that embodiment 1 is optimum embodiment.
（2）By embodiment 1 and the data of comparative example 1-9 as it can be seen that polyether acrylate, polyvinyl resin, maleic acid
Acid anhydride, nano-titanium dioxide, antimony oxide, corrosion-resistant reinforcement modifying agent, corrosion-resistant reinforced filling and surface modifier are preparing corrosion resistant
Synergistic effect is played in erosion lithium battery diaphragm, collaboration improves the corrosion resistance of the lithium battery material；This is：Polyoxyalkylene acrylate
Ester, polyvinyl resin, maleic anhydride, nano-titanium dioxide, antimony oxide, corrosion-resistant reinforcement modifying agent, corrosion-resistant reinforcement are filled out
As reinforcement system, wherein polyether acrylate and polyvinyl resin is major ingredient, assigns reinforcement system and increases for material and surface modifier
Strong corrosion resistant performance, maleic anhydride are acted on as modified monomer at the melting of polyether acrylate and polyvinyl resin
During reason, the corrosion resistance of polyether acrylate and polyvinyl resin, the nano-titanium dioxide and antimony oxide of addition are improved
Corrosion-resistant modified filler, addition surface modifier are realized as graft modification agent by corrosion-resistant reinforcement modifying agent, corrosion-resistant reinforcement
The corrosion-resistant reinforcing property of filler applies in the base-material of the lithium battery material, realizes corrosion-resistant reinforcement modifying agent and corrosion-resistant
The hydroxyl on reinforced filling surface is realized under the grafting effect of surface modifier and is combined with base-material, effectively increases lithium of the present invention
The corrosion resistance of battery material improves.Wherein, corrosion-resistant reinforcement modifying agent is mixed by the way that phenolic resin to be added in rare earth chloride
Uniformly, it heating up, heat preservation keeps stirring during heat preservation, then proceedes to heat up, and keeps the temperature, is then refluxed for, then vacuum dehydration,
Then it heats up, keeps the temperature, barium sulfate, weathered coal, bentonite, zeolite powder, nano-titanium dioxide, alkyl phenol are added after being cooled to room temperature
Polyoxyethylene ether, neopelex and Silane coupling reagent KH-570 are uniformly mixed, ultrasound-mechanical agitation point in water-bath
It dissipates, stratification, removes supernatant liquor, lower reaction product layer is filtered, wash, be dried under vacuum to constant weight, grind, sieving
Obtain, using phenolic resin as resin binder, using rare earth chloride as modified initiator, with barium sulfate, weathered coal, bentonite,
Zeolite powder and nano-titanium dioxide are corrosion-resistant reinforced filling, using alkyl phenol polyoxyethylene ether and neopelex as
Surfactant realizes using Silane coupling reagent KH-570 as modified grafting agent and carries out hydroxyl to corrosion-resistant reinforced filling surface
Base is modified, and realization is combined with phenolic surface, is applied in the lithium battery diaphragm preparation of the present invention, is effectively increased the present invention
The corrosion resistance of lithium battery diaphragm.Corrosion-resistant reinforced filling is equal by mixing butyl acrylate and nano tin oxide powder
It is even, silane resin acceptor kh-550 is then added and is uniformly mixed, stirring is cooled to room temperature, and is subsequently placed in ice-water bath and is crushed, ultrasound
Processing obtains material a；Under nitrogen protection, chitosan, bamboo powder, diatomite, distilled water and maleic anhydride are uniformly mixed, then
Heating, heat preservation, is then added material a and ammonium persulfate is uniformly mixed, and silane coupling agent KH-560 is added after stirring and is uniformly mixed,
It is followed by stirring for, then heats up, extract, then in vacuum drying oven, dry to constant weight, be cooled to room temperature to obtain, with acrylic acid fourth
Ester and maleic anhydride are grafted monomers, with chitosan, bamboo powder, diatomite, nano tin oxide powder for corrosion-resistant reinforced filling,
It is modified grafting agent with silane coupling agent KH-560, by modified grafting agent to corrosion-resistant reinforcement using ammonium persulfate as initiator
Filler carries out conducting modification of surface hydroxy group, and realization is combined with grafted monomers, applies in the lithium battery diaphragm preparation of the present invention, has
Effect improves the corrosion resistance of the lithium battery diaphragm.
（3）By the data of comparative example 12-14 as it can be seen that polyether acrylate, polyvinyl resin, maleic anhydride, nanometer
Titanium dioxide, antimony oxide, corrosion-resistant reinforcement modifying agent, corrosion-resistant reinforced filling and surface modifier weight ratio do not exist（20-
40）：（8-12）：（4-6）：（2-5）：（3-6）：（10-20）：（15-25）：（1-3）When in range, lithium battery material obtained
The corresponding numerical value of corrosion resistance and the numerical value of embodiment 1-3 are very different, and the numerical value of embodiment 1-3 are much smaller than, with existing skill
Art（Comparative example 10 and comparative example 11）Numerical value it is suitable.Polyether acrylate of the present invention, polyvinyl resin, maleic anhydride,
Nano-titanium dioxide, antimony oxide, corrosion-resistant reinforcement modifying agent, corrosion-resistant reinforced filling and surface modifier as reinforcement system,
By adding polyether acrylate, polyvinyl resin, maleic acid when embodiment 1-3 controls prepare corrosion-resisting lithium battery diaphragm
Acid anhydride, nano-titanium dioxide, antimony oxide, corrosion-resistant reinforcement modifying agent, corrosion-resistant reinforced filling and surface modifier weight ratio be
（20-40）：（8-12）：（4-6）：（2-5）：（3-6）：（10-20）：（15-25）：（1-3）, realize in reinforcement system using poly-
Ether acrylate and the excellent corrosion resistance of polyvinyl resin are modified grafted monomers with maleic anhydride, with nanometer two
Under titanium oxide and antimony oxide are acted on as corrosion-resistant reinforced filling, using polyether acrylate and polyvinyl resin as reinforcement system
For major ingredient, realizes that less corrosion-resistant reinforced filling acts on polyether acrylate and polyvinyl resin, improve polyethers propylene
The corrosion resistance of acid esters and polyvinyl resin, and under the grafting of surface modifier effect, corrosion-resistant reinforcement is utilized and is modified
The corrosion resistance strengthening action of agent effectively increases the corrosion resistance of the lithium battery material, while matching with corrosion-resistant reinforced filling
It closes, is applied in base-material under the action of surface modifier, effectively increase the corrosion resistance of the lithium battery material, as a result,
It is polyether acrylate, polyvinyl resin, maleic anhydride, nano-titanium dioxide, antimony oxide, corrosion-resistant reinforcement modifying agent, resistance to
Corrosion reinforced filling and surface modifier are applied to as reinforcement system in the preparation of the lithium battery material, effectively increase the lithium
The corrosion resistance of battery material.
The above content is it cannot be assumed that present invention specific implementation is confined to these explanations, for the technical field of the invention
Those of ordinary skill for, under the premise of not departing from present inventive concept, a number of simple deductions or replacements can also be made, all answers
When being considered as belonging to present invention scope of patent protection determined by the appended claims.
Claims (10)
1. a kind of corrosion-resisting lithium battery diaphragm, which is characterized in that including following raw material：Polypropylene, Kynoar, polyethers propylene
Acid esters, urethane acrylate, polyvinyl resin, maleic anhydride, nano silicon dioxide, nanometer alchlor, nanometer two
Titanium oxide, antimony oxide, corrosion-resistant reinforcement modifying agent, corrosion-resistant reinforced filling, surface modifier；
The corrosion-resistant reinforcement modifying agent, as unit of parts by weight, including following raw material：20-30 parts of phenolic resin, rare earth chloride
4-8 parts, 3-6 parts of barium sulfate, 2-5 parts of weathered coal, 1-4 parts of bentonite, 3-6 parts of zeolite powder, 4-8 parts of nano-titanium dioxide, alkyl
2-6 parts of phenol polyethenoxy ether, 1-5 parts of neopelex, 4-8 parts of Silane coupling reagent KH-570；
The corrosion-resistant reinforced filling, as unit of parts by weight, including following raw material：15-25 parts of butyl acrylate, nano-silica
Change 4-8 parts of glass putty body, 3-9 parts of silane resin acceptor kh-550,2-6 parts of chitosan, 1-5 parts of bamboo powder, 4-8 parts of diatomite, distilled water
12-24 parts, 4-8 parts of maleic anhydride, 3-6 parts of ammonium persulfate, 2-8 parts of silane coupling agent KH-560；
The polyether acrylate, polyvinyl resin, maleic anhydride, nano-titanium dioxide, antimony oxide, corrosion-resistant reinforcement change
The weight ratio of property agent, corrosion-resistant reinforced filling and surface modifier is（20-40）：（8-12）：（4-6）：（2-5）：（3-6）：
（10-20）：（15-25）：（1-3）.
2. corrosion-resisting lithium battery diaphragm according to claim 1, which is characterized in that the weight ratio is 30：10：5：
3.5：4.5：2：15：20.
3. corrosion-resisting lithium battery diaphragm according to claim 1, which is characterized in that as unit of parts by weight, including it is following
Raw material：80-120 parts of polypropylene, 30-40 parts of Kynoar, 20-40 parts of polyether acrylate, urethane acrylate 15-35
Part, 3-6 parts of nanometer alchlor, is received 8-12 parts of polyvinyl resin, 4-6 parts of maleic anhydride, 4-8 parts of nano silicon dioxide
2-5 parts of titanium dioxide of rice, 3-6 parts of antimony oxide, 10-20 parts of corrosion-resistant reinforcement modifying agent, reinforced filling 15-25 parts corrosion-resistant, table
Modifying agent 1-3 parts of face.
4. corrosion-resisting lithium battery diaphragm according to claim 1, which is characterized in that the corrosion-resistant reinforcement modifying agent is by such as
It is prepared by lower technique：Phenolic resin is added in rare earth chloride and is uniformly mixed, is warming up to 60-80 DEG C, keeps the temperature 10-30min, is protected
It is kept stirring in the process of temperature, then proceedes to be warming up to 80-90 DEG C, keep the temperature 10-15min, be then refluxed for 3-4h, then vacuum is de-
Water then heats to 140-160 DEG C, keeps the temperature 5-15min, and barium sulfate, weathered coal, bentonite, zeolite are added after being cooled to room temperature
Powder, nano-titanium dioxide, alkyl phenol polyoxyethylene ether, neopelex and Silane coupling reagent KH-570 are uniformly mixed,
Ultrasound-mechanical agitation disperses 2-4h in 45-55 DEG C of water-bath, and stratification removes supernatant liquor, lower reaction product layer is carried out
It filters, washing, 750-850 DEG C is dried under vacuum to constant weight, grinding, crosses 150-250 mesh sieve to get to corrosion-resistant reinforcement modifying agent.
5. corrosion-resisting lithium battery diaphragm according to claim 1, which is characterized in that the corrosion-resistant reinforced filling is by as follows
It is prepared by technique：Butyl acrylate and nano tin oxide powder are uniformly mixed, silane resin acceptor kh-550 is then added
It is uniformly mixed, stirs 20-28h in 38-46 DEG C, be cooled to room temperature, be subsequently placed in ice-water bath and be crushed, be ultrasonically treated 10-14min
Obtain material a；Under nitrogen protection, chitosan, bamboo powder, diatomite, distilled water and maleic anhydride are uniformly mixed, are then heated up
To 80-90 DEG C, 10-30min is kept the temperature, material a is then added and ammonium persulfate is uniformly mixed, silane is added after stirring 5-15min
Coupling agent KH-560 is uniformly mixed, and then stirs 50-70min in 850-1250r/min rotating speeds, then heats to 85-95 DEG C, is taken out
40-50h is carried, then in vacuum drying oven, 65-75 DEG C dries to constant weight, and is cooled to room temperature to obtain corrosion-resistant reinforced filling.
6. corrosion-resisting lithium battery diaphragm according to claim 1, which is characterized in that the surface modifier is that azo two is different
Heptonitrile, tetraethylenepentamine, anilinomethyl triethoxysilane are by weight 1-3：4-6：3-5 is mixed.
7. a kind of preparation method according to claim 1-6 any one of them corrosion-resisting lithium battery diaphragms, which is characterized in that packet
Include following steps：
S1：It stirs, be subsequently added into nano silicon dioxide and receive after polypropylene, Kynoar and urethane acrylate are heated up
Rice alchlor is uniformly mixed, and is stirred after continuing heating, is cooled to room temperature to obtain base-material；
S2：Polyether acrylate, polyvinyl resin, maleic anhydride is added after the base-material that S1 is obtained is heated up to be uniformly mixed,
It is stirred after continuing heating, is cooled to room temperature the base-material being tentatively kneaded；
S3：It will be stirred after the base-material heating of being tentatively kneaded of obtaining of S2, nano-titanium dioxide, antimony oxide, corrosion-resistant be then added
Reinforcement modifying agent, corrosion-resistant reinforced filling and surface modifier are uniformly mixed, and are stirred after continuing heating, are then squeezed in twin-screw
Go out in machine, shear at high temperature, be plasticized, stir, be plasticized, be blended, obtain blend melt, then by melt conveying to die head, in urgency
It is cooled and solidified on quickly cooling roller, obtains sheet material, then carry out biaxial tension, extracted, corrosion-resisting lithium battery diaphragm is obtained after thermal finalization.
8. the preparation method of corrosion-resisting lithium battery diaphragm according to claim 7, which is characterized in that in S1, S1：By poly- third
Alkene, Kynoar and urethane acrylate be warming up to 110-120 DEG C after in 650-850r/min rotating speeds stir 20-30min,
It is subsequently added into nano silicon dioxide and nanometer alchlor is uniformly mixed, in 1200-1400r/ after being continuously heating to 140-160 DEG C
Min rotating speeds stir 1-2h, are cooled to room temperature to obtain base-material.
9. the preparation method of corrosion-resisting lithium battery diaphragm according to claim 7, which is characterized in that in S2, S1 is obtained
Base-material be warming up to 90-110 DEG C after be added polyether acrylate, polyvinyl resin, maleic anhydride be uniformly mixed, after of continuing rising
Temperature stirs 1-2h to after 120-140 DEG C in 850-1050r/min rotating speeds, is cooled to room temperature the base-material being tentatively kneaded.
10. the preparation method of corrosion-resisting lithium battery diaphragm according to claim 7, which is characterized in that in S3, S2 is obtained
The base-material being tentatively kneaded be warming up to 120-140 DEG C after in 650-850r/min rotating speeds stir 1-2h, nano-silica is then added
Change titanium, antimony oxide, corrosion-resistant reinforcement modifying agent, corrosion-resistant reinforced filling and surface modifier to be uniformly mixed, be continuously heating to
1-2h is stirred in 1500-2500r/min rotating speeds after 150-160 DEG C, then in twin-screw in extruder, shear at high temperature, plasticizing,
Stirring is plasticized, and is blended, is obtained blend melt, then in part melt conveying to die head, cool and solidify, obtain in rapidly chilling roller
Then sheet material carries out biaxial tension, extraction obtains corrosion-resisting lithium battery diaphragm after thermal finalization.
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| CN109755447A (en) * | 2018-12-17 | 2019-05-14 | 湖南艾华集团股份有限公司 | A kind of lithium battery diaphragm and preparation method thereof |
| CN111180639A (en) * | 2020-02-25 | 2020-05-19 | 江苏厚生新能源科技有限公司 | Lithium ion battery diaphragm with long cycle life and preparation method thereof |
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| CN113193304A (en) * | 2020-09-28 | 2021-07-30 | 蜂巢能源科技有限公司 | Composite reinforced diaphragm, preparation method thereof and battery |
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| CN109755447A (en) * | 2018-12-17 | 2019-05-14 | 湖南艾华集团股份有限公司 | A kind of lithium battery diaphragm and preparation method thereof |
| CN109742297A (en) * | 2018-12-29 | 2019-05-10 | 江西省通瑞新能源科技发展有限公司 | A kind of method that modified alta-mud prepares lithium battery diaphragm |
| CN111180639A (en) * | 2020-02-25 | 2020-05-19 | 江苏厚生新能源科技有限公司 | Lithium ion battery diaphragm with long cycle life and preparation method thereof |
| CN111180639B (en) * | 2020-02-25 | 2022-03-11 | 江苏厚生新能源科技有限公司 | Lithium ion battery diaphragm with long cycle life and preparation method thereof |
| CN111916630A (en) * | 2020-07-24 | 2020-11-10 | 蜂巢能源科技有限公司 | Composite diaphragm, preparation method thereof and battery |
| CN111916630B (en) * | 2020-07-24 | 2022-04-12 | 蜂巢能源科技有限公司 | Composite diaphragm, preparation method thereof and battery |
| CN113193304A (en) * | 2020-09-28 | 2021-07-30 | 蜂巢能源科技有限公司 | Composite reinforced diaphragm, preparation method thereof and battery |
| CN113193304B (en) * | 2020-09-28 | 2022-05-03 | 蜂巢能源科技有限公司 | Composite reinforced diaphragm, preparation method thereof and battery |
| CN114784454A (en) * | 2022-06-17 | 2022-07-22 | 宁波长阳科技股份有限公司 | High-temperature-resistant polyolefin microporous membrane and preparation method thereof |
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