CN111029513A - Preparation method of new energy battery diaphragm material - Google Patents

Preparation method of new energy battery diaphragm material Download PDF

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Publication number
CN111029513A
CN111029513A CN201911285366.7A CN201911285366A CN111029513A CN 111029513 A CN111029513 A CN 111029513A CN 201911285366 A CN201911285366 A CN 201911285366A CN 111029513 A CN111029513 A CN 111029513A
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new energy
preparation
energy battery
heating
powder
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陈庆
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Anhui Mailutong Network Technology Co Ltd
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Anhui Mailutong Network Technology Co Ltd
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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
    • 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
    • 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
    • H01M50/411—Organic material
    • 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
    • H01M50/44—Fibrous material
    • 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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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Cell Separators (AREA)

Abstract

The invention provides a preparation method of a new energy battery diaphragm material, which relates to the field of new energy battery materials and comprises the following steps: preparing mullite powder; preparing a composite porous ceramic component; adding lithium chloride, a composite porous ceramic component and a suspension stabilizer into a PVA aqueous solution in sequence, stirring uniformly, transferring the mixture to an electrostatic spinning instrument, spinning under the conditions of electrostatic voltage of 15kV and plate spacing of 20cm, directly forming a film on a tin foil paper, drying the obtained film body in a drying box at 80-90 ℃ for 15-20h, then putting the dried film body in a muffle furnace, heating to 600 ℃ for 650 ℃, preserving heat for 3-5h, and naturally cooling to room temperature to obtain a finished product.

Description

Preparation method of new energy battery diaphragm material
Technical Field
The invention relates to the field of new energy battery materials, in particular to a preparation method of a new energy battery diaphragm material.
Background
With the gradual popularization of new energy automobiles, the demand for new energy battery materials will continuously increase in the future. The lithium ion battery has become the main type of new energy batteries because of the advantages of high working voltage, large energy density, long cycle life, no memory effect and the like, the lithium ion battery consists of a positive electrode, a negative electrode, an electrolyte and a polymer isolating membrane, the membrane is a high value-added material with the highest technical barrier in a lithium battery material, and the membrane has the main functions of isolating the positive electrode and the negative electrode to prevent the battery, preventing the positive electrode and the negative electrode of the lithium ion battery from short circuit, providing a channel for transporting ions and being communicated under the out-of-control conditionThe main material is porous polymer film including Polyethylene (PE) or polypropylene (PP), so called polyethylene film and PE film, because of the restriction of material melting point, the film breaking temperature of the diaphragm is lower, such as about 140 ℃ of PE film and about 160 ℃ of PP film, when the battery is not used, the diaphragm is easy to shrink or even melt, which causes the battery short circuit to cause serious accidents, and ceramic particles (such as Al particles)2O3、SiO2) The composite membrane has the advantages of high dielectric constant, good chemical stability, large specific surface area, good lyophilic property, high thermal stability and the like, is often combined with a polymer binder to be coated on the surface of a polyolefin membrane or a non-woven fabric membrane, or is mixed with other polymers to prepare the composite membrane, so that the thermal stability of the membrane is improved, the wettability of electrolyte is improved, and the safety performance of the lithium ion battery is further improved.
Chinese patent CN 107732106 a discloses a battery diaphragm slurry, a battery diaphragm, a lithium ion battery and their respective preparation methods, the preparation of the battery diaphragm slurry comprises the following steps: dissolving aramid fiber in an acid solution to perform carboxylation treatment on the aramid fiber; adding the carboxylated aramid fiber into a first solvent, and diluting and dissolving to obtain a first mixed solution; adding a filler into a second solvent to obtain a second mixed solution; and mixing the first mixed solution and the second mixed solution to obtain the battery diaphragm slurry dissolved with the aramid fiber. Through the technical scheme, the battery diaphragm slurry and the preparation method thereof can effectively dissolve aramid fiber, and solve the problem that the aramid fiber is difficult to dissolve in the prior art, so that conditions are provided for preparing the battery diaphragm; the aramid fiber is reasonably and effectively dissolved in the preparation process, so that the air permeability and the heat shrinkage are good.
Chinese patent CN 108682773 a discloses a lithium battery separator, comprising: lithium-based montmorillonite and polyolefin resin. The invention also provides a preparation method of the lithium battery diaphragm, which comprises the steps of pre-mixing the lithium-based montmorillonite subjected to dehydration pretreatment with a liquid material step by step, extruding the pre-mixed material with polyolefin resin, and carrying out sheet casting, stretching, extracting, drying and the like to obtain the lithium battery diaphragm. Firstly, adding a premix formed by lithium-based montmorillonite and a pore-forming agent into an extruder, and adding polyolefin resin at 1/4-1/3 of the extruder to improve the mixing effect of raw materials and finally obtain the lithium battery diaphragm with wider porosity control range and uniform pore diameter. The lithium battery diaphragm prepared by the invention has excellent rate charge and discharge performance and safety in the lithium battery prepared by the lithium battery diaphragm with high porosity and low porosity.
Disclosure of Invention
Technical problem to be solved
Aiming at the defects of the prior art, the invention provides a preparation method of a new energy battery diaphragm material.
(II) technical scheme
In order to achieve the purpose, the invention is realized by the following technical scheme:
a preparation method of a new energy battery diaphragm material comprises the following steps:
(1) mechanically stirring and uniformly mixing dry aluminum trichloride and ethyl orthosilicate, adding the mixture into ether, mechanically stirring for 30-40min at 500r/min for 300-;
(2) uniformly mixing mullite powder, cordierite powder, boron nitride powder and rho-alumina to obtain a mixture, and mixing the mullite powder, the cordierite powder, the boron nitride powder and the rho-alumina in a ball: mixing materials: the mass ratio of water is 4-8: 1.5-3: 1, ball-milling for 4-6h in a ball mill, mixing the obtained slurry with a sodium carboxymethylcellulose aqueous solution, mechanically stirring for 10-15min at 800r/min, adding a gel Isobam104, mechanically stirring for 20-40min at 1200r/min, adding triethanolamine dodecyl sulfate, mechanically stirring at a constant speed for 10-20min, removing air in the slurry under negative pressure, and injecting into a mold;
(3) placing the mold in a vacuum oven at 80-85 ℃ for drying so as to solidify the slurry into blocks, transferring the blocks into a carbon tube furnace, heating to 1700-1800 ℃ in the nitrogen atmosphere, sintering for 2-4h, cooling the furnace to room temperature, and crushing to obtain a composite porous ceramic component;
(4) adding lithium chloride, a composite porous ceramic component and a suspension stabilizer into a PVA aqueous solution in sequence, stirring uniformly, transferring the mixture to an electrostatic spinning instrument, spinning under the conditions of electrostatic voltage of 15kV and plate spacing of 20cm, directly forming a film on a tin foil paper, drying the obtained film body in a drying box at 80-90 ℃ for 15-20h, then placing the film body in a muffle furnace, heating to 600-plus-material 650 ℃, preserving heat for 3-5h, and naturally cooling to room temperature to obtain a finished product.
Further, in the step (1), the molar mass ratio of aluminum trichloride to ethyl orthosilicate to diethyl ether is 12: 5: 10-20.
Further, in the step (1), the primary heating speed is 2-5 ℃/min, and the secondary heating speed is 8-12 ℃/min.
Further, in the step (2), the mass ratio of the mullite powder to the cordierite powder to the boron nitride powder to the rho-alumina is 5-10: 3-6: 1-2: 1.
further, the mass concentration of the sodium carboxymethylcellulose aqueous solution in the step (2) is 1-3%.
Further, the temperature increase rate at the time of sintering in step (3) was 3 ℃/min.
Further, the mass concentration of the PVA aqueous solution in the step (4) is 8-15%.
Further, the suspension stabilizer in the step (4) is organic modified sodium bentonite.
Further, the organic modified sodium bentonite is any one of dodecyl dimethyl benzyl ammonium chloride modified sodium bentonite, tetradecyl dimethyl benzyl ammonium chloride modified sodium bentonite, hexadecyl trimethyl ammonium chloride modified sodium bentonite and octadecyl trimethyl ammonium chloride modified sodium bentonite.
Further, the temperature rise speed in the step (4) is 4-6 ℃/min.
(III) advantageous effects
The invention provides a preparation method of a new energy battery diaphragm material, which has the following beneficial effects:
the temperature and the temperature rise speed are controlled in the mullite preparation process, the prepared mullite has stable property and uniform properties, and experiments show that the mullite grains are not developed enough and not strong enough when the temperature is lower than the sintering temperature of the mullite preparation process, the calcining temperature is too high, the difference of the growth speeds of crystals along all directions is reduced, the mullite grains are coarsened, and the thickness of the diaphragm material is increased, so that the sintering at 1280-1300 ℃ is the most reasonable interval; the composite material is compounded with cordierite, a large pore can be formed in a cordierite structure, vibration can be carried out on the pore during heat collection, the thermal shrinkage rate of a diaphragm material is improved by adding the composite material, boron nitride is high temperature resistant and chemical corrosion resistant, the thermal stability and chemical stability of the diaphragm material can be improved after the composite material is added, functional groups on the surface of the boron nitride are few, and only a small amount of hydroxyl and amino exist, so that the wettability of a ceramic material is relatively reduced after the boron nitride is added, through continuous experiments, the inventor finds that the wettability of an electrolyte of the ceramic material is greatly improved after the triethanolamine dodecyl sulfate is added, analyzes the existence of possibly long alkyl chains, improves the wettability of the surface of the ceramic material, thereby improving the absorption capacity of the electrolyte, the diaphragm material is prepared by utilizing an electrostatic spinning method, the method is simple, the operation is easy, the film forming is uniform, and the prepared, the lithium ion battery has the advantages of small thermal shrinkage, high air permeability and oxygen index, good safety performance, higher liquid absorption, low internal resistance and high ionic conductivity, and is beneficial to the diffusion of lithium ions.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1:
a preparation method of a new energy battery diaphragm material comprises the following specific steps:
mechanically stirring and uniformly mixing dry aluminum trichloride and tetraethoxysilane, and then adding the mixture into diethyl ether, wherein the molar mass ratio of the aluminum trichloride to the tetraethoxysilane is 12: 5: 12, mechanically stirring for 40min at a speed of 400r/min, heating for reflux reaction for 22h, then carrying out reduced pressure evaporation to obtain a gel material, grinding and crushing, placing in a carbon tube furnace, heating to 610 ℃ for the first time, preserving heat for 3h, heating to 1285 ℃ for the second time, preserving heat for 6h to obtain mullite powder, wherein the first heating speed is 4 ℃/min, and the second heating speed is 10 ℃/min; according to the mass ratio of 10: 5: 1: 1, uniformly mixing mullite powder, cordierite powder, boron nitride powder and rho-alumina to obtain a mixture, wherein the weight ratio of the mullite powder to the cordierite powder is as follows: mixing materials: the mass ratio of water is 8: 2: 1, ball-milling the obtained slurry in a ball mill for 6 hours, mixing the obtained slurry with a sodium carboxymethylcellulose aqueous solution with the mass concentration of 1.5%, mechanically stirring for 12 minutes at the speed of 800r/min, adding a gelling agent Isobam104, mechanically stirring for 25 minutes at the speed of 1200r/min, adding lauryl triethanolamine sulfate, mechanically stirring at a constant speed for 18 minutes, removing air in the slurry at a negative pressure, and injecting the mixture into a mold; placing the mould in a vacuum oven at 82 ℃ for drying so as to solidify the slurry into blocks, then transferring the blocks into a carbon tube furnace, heating to 1800 ℃ at 3 ℃/min in the nitrogen atmosphere for sintering for 4h, cooling the furnace to room temperature, and crushing to obtain a composite porous ceramic component; sequentially adding lithium chloride, a composite porous ceramic component and organic modified sodium bentonite into a PVA (polyvinyl alcohol) aqueous solution with the mass concentration of 12%, uniformly stirring, transferring to an electrostatic spinning instrument, spinning under the conditions of electrostatic voltage of 15kV and plate spacing of 20cm, directly forming a film on a tin foil paper, drying the obtained film body in a drying box at 85 ℃ for 18h, then putting the film body in a muffle furnace, heating to 620 ℃ at 6 ℃/min, preserving heat for 4h, and naturally cooling to room temperature to obtain a finished product.
Example 2:
a preparation method of a new energy battery diaphragm material comprises the following specific steps:
mechanically stirring and uniformly mixing dry aluminum trichloride and tetraethoxysilane, and then adding the mixture into diethyl ether, wherein the molar mass ratio of the aluminum trichloride to the tetraethoxysilane is 12: 5: mechanically stirring for 40min at the speed of 20 r/min and 350r/min, heating, refluxing for 20h, evaporating to dryness under reduced pressure to obtain a gel material, grinding, crushing, placing in a carbon tube furnace, heating to 620 ℃ for the first time, preserving heat for 2h, heating to 1290 ℃ for the second time, preserving heat for 6h to obtain mullite powder, wherein the heating rate of the second time is 4 ℃/min, and the heating rate of the first time is 12 ℃/min; according to the mass ratio of 8: 4: 2: 1, uniformly mixing mullite powder, cordierite powder, boron nitride powder and rho-alumina to obtain a mixture, wherein the weight ratio of the mullite powder to the cordierite powder is as follows: mixing materials: the mass ratio of water is 6: 2: 1, ball-milling for 5 hours in a ball mill, mixing the obtained slurry with a sodium carboxymethylcellulose aqueous solution with the mass concentration of 2%, mechanically stirring for 12 minutes at 750r/min, adding a gelling agent Isobam104, mechanically stirring for 35 minutes at 1100r/min, adding lauryl triethanolamine sulfate, mechanically stirring at a constant speed for 20 minutes, removing air in the slurry at a negative pressure, and injecting into a mold; placing the mould in a vacuum oven at 82 ℃ for drying so as to solidify the slurry into blocks, transferring the blocks into a carbon tube furnace, heating to 1760 ℃ at 3 ℃/min in the nitrogen atmosphere for sintering for 4h, cooling the furnace to room temperature, and crushing to obtain a composite porous ceramic component; adding lithium chloride, a composite porous ceramic component and organic modified sodium bentonite into a PVA (polyvinyl alcohol) aqueous solution with the mass concentration of 12%, uniformly stirring, transferring to an electrostatic spinning instrument, spinning under the conditions of electrostatic voltage of 15kV and plate spacing of 20cm, directly forming a film on a tin foil paper, drying the obtained film body in a drying box at 85 ℃ for 18h, then putting the film body in a muffle furnace, heating to 620 ℃ at 6 ℃/min, preserving heat for 5h, and naturally cooling to room temperature to obtain a finished product.
Example 3:
a preparation method of a new energy battery diaphragm material comprises the following specific steps:
mechanically stirring and uniformly mixing dry aluminum trichloride and tetraethoxysilane, and then adding the mixture into diethyl ether, wherein the molar mass ratio of the aluminum trichloride to the tetraethoxysilane is 12: 5: mechanically stirring for 32min at a speed of 400r/min, heating for reflux reaction for 22h, then evaporating to dryness under reduced pressure to obtain a gel material, grinding and crushing, placing in a carbon tube furnace, heating to 610 ℃ for the first time, preserving heat for 3h, heating to 1300 ℃ for the second time, preserving heat for 5.5h to obtain mullite powder, wherein the first heating speed is 4 ℃/min, and the second heating speed is 12 ℃/min; according to the mass ratio of 10: 4: 1: 1, uniformly mixing mullite powder, cordierite powder, boron nitride powder and rho-alumina to obtain a mixture, wherein the weight ratio of the mullite powder to the cordierite powder is as follows: mixing materials: the mass ratio of water is 8: 2: 1, ball-milling for 5 hours in a ball mill, mixing the obtained slurry with a sodium carboxymethylcellulose aqueous solution with the mass concentration of 1%, mechanically stirring for 12 minutes at the speed of 800r/min, adding a gelling agent Isobam104, mechanically stirring for 40 minutes at the speed of 1150r/min, adding lauryl triethanolamine sulfate, mechanically stirring at a constant speed for 15 minutes, removing air in the slurry at a negative pressure, and injecting into a mold; placing the mold in a vacuum oven at 84 ℃ for drying so as to solidify the slurry into blocks, transferring the blocks into a carbon tube furnace, heating to 1780 ℃ at 3 ℃/min in the nitrogen atmosphere for sintering for 3h, cooling the furnace to room temperature, and crushing to obtain a composite porous ceramic component; sequentially adding lithium chloride, a composite porous ceramic component and organic modified sodium bentonite into a PVA (polyvinyl alcohol) aqueous solution with the mass concentration of 10%, uniformly stirring, transferring to an electrostatic spinning instrument, spinning under the conditions of electrostatic voltage of 15kV and plate spacing of 20cm, directly forming a film on a tin foil paper, drying the obtained film body in a drying box at 80 ℃ for 18h, then putting in a muffle furnace, heating to 630 ℃ at the speed of 5 ℃/min, preserving heat for 4h, and naturally cooling to room temperature to obtain a finished product.
Example 4:
a preparation method of a new energy battery diaphragm material comprises the following specific steps:
mechanically stirring and uniformly mixing dry aluminum trichloride and tetraethoxysilane, and then adding the mixture into diethyl ether, wherein the molar mass ratio of the aluminum trichloride to the tetraethoxysilane is 12: 5: mechanically stirring for 30min at the speed of 350r/min, heating for reflux reaction for 24h, then carrying out reduced pressure evaporation to obtain a gel material, grinding and crushing, placing in a carbon tube furnace, heating to 620 ℃ for the first time, preserving heat for 1h, heating to 1280 ℃ for the second time, preserving heat for 5h to obtain mullite powder, wherein the first heating speed is 4 ℃/min, and the second heating speed is 10 ℃/min; according to the mass ratio of 10: 4: 2: 1, uniformly mixing mullite powder, cordierite powder, boron nitride powder and rho-alumina to obtain a mixture, wherein the weight ratio of the mullite powder to the cordierite powder is as follows: mixing materials: the mass ratio of water is 8: 2: 1, ball-milling for 5 hours in a ball mill, mixing the obtained slurry with a sodium carboxymethylcellulose aqueous solution with the mass concentration of 2%, mechanically stirring for 12 minutes at the speed of 800r/min, adding a gelling agent Isobam104, mechanically stirring for 35 minutes at the speed of 1050r/min, adding lauryl triethanolamine sulfate, mechanically stirring at a constant speed for 20 minutes, removing air in the slurry at a negative pressure, and injecting into a mold; placing the mould in a vacuum oven at 82 ℃ for drying so as to solidify the slurry into blocks, transferring the blocks into a carbon tube furnace, heating to 1760 ℃ at 3 ℃/min in the nitrogen atmosphere for sintering for 3h, cooling the furnace to room temperature, and crushing to obtain a composite porous ceramic component; adding lithium chloride, a composite porous ceramic component and organic modified sodium bentonite into 10% PVA aqueous solution in sequence, stirring uniformly, transferring to an electrostatic spinning instrument, spinning under the conditions of electrostatic voltage of 15kV and plate spacing of 20cm, directly forming a film on the tin foil paper, drying the obtained film body in a drying box at 90 ℃ for 18h, then placing in a muffle furnace, heating to 640 ℃ at 4 ℃/min, preserving heat for 4.5h, and naturally cooling to room temperature to obtain a finished product.
Example 5:
a preparation method of a new energy battery diaphragm material comprises the following specific steps:
mechanically stirring and uniformly mixing dry aluminum trichloride and tetraethoxysilane, and then adding the mixture into diethyl ether, wherein the molar mass ratio of the aluminum trichloride to the tetraethoxysilane is 12: 5: mechanically stirring for 30min at the speed of 300r/min, heating for reflux reaction for 20h, then carrying out reduced pressure evaporation to obtain a gel material, grinding and crushing, placing in a carbon tube furnace, heating to 600 ℃ for the first time, preserving heat for 1h, heating to 1280 ℃ for the second time, preserving heat for 4h to obtain mullite powder, wherein the first heating speed is 2 ℃/min, and the second heating speed is 8 ℃/min; according to the mass ratio of 5: 3: 1: 1, uniformly mixing mullite powder, cordierite powder, boron nitride powder and rho-alumina to obtain a mixture, wherein the weight ratio of the mullite powder to the cordierite powder is as follows: mixing materials: the mass ratio of water is 4: 1.5: 1, ball-milling for 4 hours in a ball mill, mixing the obtained slurry with a sodium carboxymethylcellulose aqueous solution with the mass concentration of 1%, mechanically stirring for 10 minutes at 600r/min, adding a gelling agent Isobam104, mechanically stirring for 20 minutes at 1000r/min, adding lauryl triethanolamine sulfate, mechanically stirring at a constant speed for 10 minutes, removing air in the slurry under negative pressure, and injecting into a mold; placing the mold in a vacuum oven at 80 ℃ for drying so as to solidify the slurry into blocks, transferring the blocks into a carbon tube furnace, heating to 1700 ℃ at 3 ℃/min in the nitrogen atmosphere for sintering for 2h, cooling the furnace to room temperature, and crushing to obtain a composite porous ceramic component; sequentially adding lithium chloride, a composite porous ceramic component and organic modified sodium bentonite into a PVA (polyvinyl alcohol) aqueous solution with the mass concentration of 8%, uniformly stirring, transferring to an electrostatic spinning instrument, spinning under the conditions of electrostatic voltage of 15kV and plate spacing of 20cm, directly forming a film on a tin foil paper, drying the obtained film body in a drying box at 80 ℃ for 15h, then putting in a muffle furnace, heating to 600 ℃ at 4 ℃/min, preserving heat for 3h, and naturally cooling to room temperature to obtain a finished product.
Example 6:
a preparation method of a new energy battery diaphragm material comprises the following specific steps:
mechanically stirring and uniformly mixing dry aluminum trichloride and tetraethoxysilane, and then adding the mixture into diethyl ether, wherein the molar mass ratio of the aluminum trichloride to the tetraethoxysilane is 12: 5: mechanically stirring for 40min at a speed of 500r/min, heating for reflux reaction for 25h, evaporating to dryness under reduced pressure to obtain a gel material, grinding, crushing, placing in a carbon tube furnace, heating to 630 ℃ for the first time, preserving heat for 3h, heating to 1300 ℃ for the second time, preserving heat for 6h to obtain mullite powder, wherein the first heating speed is 5 ℃/min, and the second heating speed is 12 ℃/min; according to the mass ratio of 10: 6: 2: 1, uniformly mixing mullite powder, cordierite powder, boron nitride powder and rho-alumina to obtain a mixture, wherein the weight ratio of the mullite powder to the cordierite powder is as follows: mixing materials: the mass ratio of water is 8: 3: 1, ball-milling the obtained slurry in a ball mill for 6 hours, mixing the obtained slurry with a sodium carboxymethylcellulose aqueous solution with the mass concentration of 3%, mechanically stirring for 15 minutes at the speed of 800r/min, adding a gelling agent Isobam104, mechanically stirring for 40 minutes at the speed of 1200r/min, adding lauryl triethanolamine sulfate, mechanically stirring at a constant speed for 20 minutes, removing air in the slurry at a negative pressure, and injecting the mixture into a mold; placing the mould in a vacuum oven for drying at 85 ℃ to solidify the slurry into blocks, transferring the blocks into a carbon tube furnace, heating to 1800 ℃ at 3 ℃/min in the nitrogen atmosphere, sintering for 4h, cooling the furnace to room temperature, and crushing to obtain a composite porous ceramic component; adding lithium chloride, a composite porous ceramic component and organic modified sodium bentonite into a PVA (polyvinyl alcohol) aqueous solution with the mass concentration of 15% in sequence, stirring uniformly, transferring to an electrostatic spinning instrument, spinning under the conditions of electrostatic voltage of 15kV and plate spacing of 20cm, directly forming a film on a tin foil paper by the spun yarn, drying the obtained film body in a drying box at 90 ℃ for 20h, then putting the film body in a muffle furnace, heating to 650 ℃ at 6 ℃/min, preserving heat for 5h, and naturally cooling to room temperature to obtain a finished product.
Example 7:
a preparation method of a new energy battery diaphragm material comprises the following specific steps:
mechanically stirring and uniformly mixing dry aluminum trichloride and tetraethoxysilane, and then adding the mixture into diethyl ether, wherein the molar mass ratio of the aluminum trichloride to the tetraethoxysilane is 12: 5: mechanically stirring for 30min at a speed of 500r/min, heating for reflux reaction for 25h, then carrying out reduced pressure evaporation to obtain a gel material, grinding and crushing, placing in a carbon tube furnace, heating to 600 ℃ for the first time, preserving heat for 3h, heating to 1280 ℃ for the second time, preserving heat for 6h to obtain mullite powder, wherein the first heating speed is 2 ℃/min, and the second heating speed is 12 ℃/min; according to the mass ratio of 5: 6: 1: 1, uniformly mixing mullite powder, cordierite powder, boron nitride powder and rho-alumina to obtain a mixture, wherein the weight ratio of the mullite powder to the cordierite powder is as follows: mixing materials: the mass ratio of water is 8: 1.5: 1, ball-milling the obtained slurry in a ball mill for 6 hours, mixing the obtained slurry with a sodium carboxymethylcellulose aqueous solution with the mass concentration of 1%, mechanically stirring for 10 minutes at the speed of 800r/min, adding a gelling agent Isobam104, mechanically stirring for 20 minutes at the speed of 1200r/min, adding lauryl triethanolamine sulfate, mechanically stirring at a constant speed for 20 minutes, removing air in the slurry under negative pressure, and injecting the mixture into a mold; placing the mould in a vacuum oven to dry at 80 ℃ so as to solidify the slurry into blocks, then transferring the blocks into a carbon tube furnace, heating to 1800 ℃ at 3 ℃/min in the nitrogen atmosphere, sintering for 2h, cooling the furnace to room temperature, and crushing to obtain a composite porous ceramic component; adding lithium chloride, a composite porous ceramic component and organic modified sodium bentonite into a PVA (polyvinyl alcohol) aqueous solution with the mass concentration of 15% in sequence, stirring uniformly, transferring to an electrostatic spinning instrument, spinning under the conditions of electrostatic voltage of 15kV and plate spacing of 20cm, directly forming a film on a tin foil paper, drying the obtained film body in a drying box at 80 ℃ for 20h, then placing in a muffle furnace, heating to 650 ℃ at 4 ℃/min, preserving heat for 3h, and naturally cooling to room temperature to obtain a finished product.
Example 8:
a preparation method of a new energy battery diaphragm material comprises the following specific steps:
mechanically stirring and uniformly mixing dry aluminum trichloride and tetraethoxysilane, and then adding the mixture into diethyl ether, wherein the molar mass ratio of the aluminum trichloride to the tetraethoxysilane is 12: 5: mechanically stirring for 40min at the speed of 300r/min, heating, refluxing, reacting for 20h, evaporating to dryness under reduced pressure to obtain a gel material, grinding, crushing, placing in a carbon tube furnace, heating to 630 ℃ for the first time, keeping the temperature for 1h, heating to 1300 ℃ for the second time, keeping the temperature for 4h to obtain mullite powder, wherein the first heating speed is 5 ℃/min, and the second heating speed is 8 ℃/min; according to the mass ratio of 10: 3: 2: 1, uniformly mixing mullite powder, cordierite powder, boron nitride powder and rho-alumina to obtain a mixture, wherein the weight ratio of the mullite powder to the cordierite powder is as follows: mixing materials: the mass ratio of water is 4: 3: 1, ball-milling for 4 hours in a ball mill, mixing the obtained slurry with a sodium carboxymethylcellulose aqueous solution with the mass concentration of 3%, mechanically stirring for 15 minutes at 600r/min, adding a gelling agent Isobam104, mechanically stirring for 40 minutes at 1000r/min, adding lauryl triethanolamine sulfate, mechanically stirring at a constant speed for 10 minutes, removing air in the slurry under negative pressure, and injecting into a mold; placing the mold in a vacuum oven at 85 ℃ for drying so as to solidify the slurry into blocks, transferring the blocks into a carbon tube furnace, heating to 1700 ℃ at 3 ℃/min in the nitrogen atmosphere for sintering for 4h, cooling the furnace to room temperature, and crushing to obtain a composite porous ceramic component; sequentially adding lithium chloride, a composite porous ceramic component and organic modified sodium bentonite into a PVA (polyvinyl alcohol) aqueous solution with the mass concentration of 8%, uniformly stirring, transferring to an electrostatic spinning instrument, spinning under the conditions of electrostatic voltage of 15kV and plate spacing of 20cm, directly forming a film on a tin foil paper, drying the obtained film body in a drying box at 90 ℃ for 15h, then putting the film body into a muffle furnace, heating to 600 ℃ at 6 ℃/min, preserving heat for 5h, and naturally cooling to room temperature to obtain a finished product.
The following table 1 shows the performance test results of the new energy battery separator materials of examples 1 to 3 of the present invention:
table 1:
Figure BDA0002317821460000111
as can be seen from the above Table 1, the battery separator material of the present invention has the advantages of thin thickness, small thermal shrinkage, high air permeability and oxygen index, good safety performance, high liquid absorption, easy diffusion of lithium ions, low internal resistance and high ionic conductivity.
It is noted that, herein, relational terms such as first and second, and the like may be used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Also, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. Without further limitation, an element defined by the phrase "comprising an … …" does not exclude the presence of other identical elements in a process, method, article, or apparatus that comprises the element.
The above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.

Claims (10)

1. A preparation method of a new energy battery diaphragm material is characterized by comprising the following steps:
(1) mechanically stirring and uniformly mixing dry aluminum trichloride and ethyl orthosilicate, adding the mixture into ether, mechanically stirring for 30-40min at 500r/min for 300-;
(2) uniformly mixing mullite powder, cordierite powder, boron nitride powder and rho-alumina to obtain a mixture, and mixing the mullite powder, the cordierite powder, the boron nitride powder and the rho-alumina in a ball: mixing materials: the mass ratio of water is 4-8: 1.5-3: 1, ball-milling for 4-6h in a ball mill, mixing the obtained slurry with a sodium carboxymethylcellulose aqueous solution, mechanically stirring for 10-15min at 800r/min, adding a gel Isobam104, mechanically stirring for 20-40min at 1200r/min, adding triethanolamine dodecyl sulfate, mechanically stirring at a constant speed for 10-20min, removing air in the slurry under negative pressure, and injecting into a mold;
(3) placing the mold in a vacuum oven at 80-85 ℃ for drying so as to solidify the slurry into blocks, transferring the blocks into a carbon tube furnace, heating to 1700-1800 ℃ in the nitrogen atmosphere, sintering for 2-4h, cooling the furnace to room temperature, and crushing to obtain a composite porous ceramic component;
(4) adding lithium chloride, a composite porous ceramic component and a suspension stabilizer into a PVA aqueous solution in sequence, stirring uniformly, transferring the mixture to an electrostatic spinning instrument, spinning under the conditions of electrostatic voltage of 15kV and plate spacing of 20cm, directly forming a film on a tin foil paper, drying the obtained film body in a drying box at 80-90 ℃ for 15-20h, then placing the film body in a muffle furnace, heating to 600-plus-material 650 ℃, preserving heat for 3-5h, and naturally cooling to room temperature to obtain a finished product.
2. The preparation method of the new energy battery diaphragm material according to claim 1, wherein the molar mass ratio of the aluminum trichloride to the ethyl orthosilicate to the ethyl ether in the step (1) is 12: 5: 10-20.
3. The preparation method of the new energy battery separator material according to claim 1, wherein in the step (1), the primary temperature rise rate is 2-5 ℃/min, and the secondary temperature rise rate is 8-12 ℃/min.
4. The preparation method of the new energy battery separator material according to claim 1, wherein the mass ratio of the mullite powder, the cordierite powder, the boron nitride powder and the rho-alumina in the step (2) is 5-10: 3-6: 1-2: 1.
5. the preparation method of the new energy battery separator material according to claim 1, wherein the mass concentration of the sodium carboxymethyl cellulose aqueous solution in the step (2) is 1-3%.
6. The preparation method of the new energy battery separator material according to claim 1, wherein the temperature rise rate during the sintering in the step (3) is 3 ℃/min.
7. The preparation method of the new energy battery separator material according to claim 1, wherein the mass concentration of the PVA aqueous solution in the step (4) is 8-15%.
8. The preparation method of the new energy battery separator material according to claim 1, wherein the suspension stabilizer in the step (4) is organically modified sodium bentonite.
9. The preparation method of the new energy battery separator material of claim 8, wherein the organic modified sodium bentonite is any one of dodecyl dimethyl benzyl ammonium chloride modified sodium bentonite, tetradecyl dimethyl benzyl ammonium chloride modified sodium bentonite, hexadecyl trimethyl ammonium chloride modified sodium bentonite, and octadecyl trimethyl ammonium chloride modified sodium bentonite.
10. The preparation method of the new energy battery separator material according to claim 9, wherein the temperature rise rate in the step (4) is 4-6 ℃/min.
CN201911285366.7A 2019-12-13 2019-12-13 Preparation method of new energy battery diaphragm material Withdrawn CN111029513A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114335884A (en) * 2021-12-10 2022-04-12 国网江西省电力有限公司电力科学研究院 Method for preparing lithium ion battery diaphragm material by using biological membrane

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114335884A (en) * 2021-12-10 2022-04-12 国网江西省电力有限公司电力科学研究院 Method for preparing lithium ion battery diaphragm material by using biological membrane
CN114335884B (en) * 2021-12-10 2023-10-20 国网江西省电力有限公司电力科学研究院 Method for preparing lithium ion battery diaphragm material by using biological film

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