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CN111446402A - Process method for preparing lithium battery diaphragm by using 3D printing technology - Google Patents

Process method for preparing lithium battery diaphragm by using 3D printing technology Download PDF

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Publication number
CN111446402A
CN111446402A CN202010316823.0A CN202010316823A CN111446402A CN 111446402 A CN111446402 A CN 111446402A CN 202010316823 A CN202010316823 A CN 202010316823A CN 111446402 A CN111446402 A CN 111446402A
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China
Prior art keywords
diaphragm
film
substrate
lithium battery
ceramic powder
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Pending
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CN202010316823.0A
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Chinese (zh)
Inventor
柴春芳
陈卫
揭垚
戴鹏
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Zhejiang Jidun New Material Technology Co ltd
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Zhejiang Jidun New Material Technology Co ltd
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Priority to CN202010316823.0A priority Critical patent/CN111446402A/en
Publication of CN111446402A publication Critical patent/CN111446402A/en
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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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B7/00—Mixing; Kneading
    • B29B7/02—Mixing; Kneading non-continuous, with mechanical mixing or kneading devices, i.e. batch type
    • B29B7/22—Component parts, details or accessories; Auxiliary operations
    • B29B7/28—Component parts, details or accessories; Auxiliary operations for measuring, controlling or regulating, e.g. viscosity control
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B7/00—Mixing; Kneading
    • B29B7/80—Component parts, details or accessories; Auxiliary operations
    • B29B7/82—Heating or cooling
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C64/00—Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
    • B29C64/10—Processes of additive manufacturing
    • B29C64/106—Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material
    • B29C64/112—Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material using individual droplets, e.g. from jetting heads
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C64/00—Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
    • B29C64/20—Apparatus for additive manufacturing; Details thereof or accessories therefor
    • B29C64/205—Means for applying layers
    • B29C64/209—Heads; Nozzles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y10/00—Processes of additive manufacturing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y30/00—Apparatus for additive manufacturing; Details thereof or accessories therefor
    • 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
    • H01M50/446—Composite material consisting of a mixture of organic and inorganic materials
    • 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
    • H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
    • 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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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Mechanical Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Electrochemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Composite Materials (AREA)
  • Inorganic Chemistry (AREA)
  • Cell Separators (AREA)

Abstract

A process method for preparing a lithium battery diaphragm by using a 3D printing technology comprises the following steps of A), uniformly mixing a diaphragm substrate, superfine ceramic powder and one of PVDF and PMMA in a mixer according to a required proportion, transferring the mixture to a grinding machine, and grinding to obtain a mixed material with a required granularity; B) transferring the obtained mixed material to a heater with stirring, heating to melt the material, adding an organic solvent to adjust the viscosity of the material, and stirring for 2-5 h; C) and transferring the melted material to a material injector of a 3D printer, pushing a piston of the injector to enable the material to be sprayed on the substrate in a certain shape and thickness through a 3D printer nozzle, completely cooling, solidifying and molding, peeling off the substrate, and rolling to obtain the multifunctional composite diaphragm embedded with the superfine nano ceramic powder. The invention has the following beneficial effects: and (3) obtaining the thickness-controllable multifunctional composite diaphragm embedded with the superfine nano ceramic powder by applying a 3D printing technology.

Description

Process method for preparing lithium battery diaphragm by using 3D printing technology
Technical Field
The invention belongs to the field of lithium ion batteries, and particularly relates to a process method for preparing a lithium battery diaphragm by using a 3D printing technology.
Background
With the increasing proliferation of consumer electronics, electric vehicles, energy storage systems, and other fields, the development of these fields is greatly restricted by factors such as performance and cost of lithium ion batteries. The diaphragm is one of four main materials of the lithium ion battery, is always concerned by people, research work on performance development and cost reduction of the lithium ion battery is not stopped, and particularly, a functional ceramic diaphragm, an organic material coating diaphragm and a composite diaphragm of the two materials are the mainstream of the current market.
However, due to the limitation of the process and the material, the existing various diaphragms have some problems to be solved: 1) the pore forming of the base film is not uniform, and local defects are inevitable; 2) the inorganic material ceramic diaphragm and the PVDF or PMMA coating film have uneven coating thickness, the coating process is complex, and the coating is easy to fall off; 3) the thin-layer diaphragm has larger thermal shrinkage; 4) inorganic waste residues and organic solvents are easy to be generated in the coating process, and the like; 5) the thickness of the diaphragm is difficult to control; 6) the process is complex and the processing cost is high.
Based on the needs of the current market, people are continuously improving the process and performance of the existing diaphragm, such as reducing the thickness of PP and PE diaphragms, improving the consistency, using novel coating materials, reducing the thickness of the coating, and the like; meanwhile, people also devote themselves to the development of membranes made of various new materials, such as non-woven fabrics, polyimide, PVDF and the like; and new technologies such as gravure coating, spray coating, electrostatic spinning, etc. have been developed in the processing method. But the problems of uniformity, no defect, no falling off of a coating, controllable thickness shrinkage, perfect compounding of various materials, economic and environment-friendly process and the like are not thoroughly solved.
Patent CN110277527A mixes polypropylene and nucleating agent, then extrudes and casts the mixture in turn to obtain a cast sheet, and carries out bidirectional synchronous stretching on the cast sheet to obtain a polypropylene microporous membrane, patent CN110600655A carries out blending of aliphatic polyketone and nucleating agent, and is melted and extruded to obtain a cast prefabricated membrane with high β crystal content, and the cast prefabricated membrane is subjected to heat treatment, bidirectional stretching and heat setting in turn to obtain a bidirectional stretched aliphatic polyketone microporous membrane, patent CN110112352A adds a heat-decomposable polymer into a polar protic solvent, then adds aromatic diamine, then adds aromatic dianhydride, and is stirred to carry out polymerization reaction to obtain a polyamic acid solution, the polyamic acid solution is subjected to vacuum defoamation and is prepared into a polyimide diaphragm membrane by a casting method, patent CN110277530A is formed by interweaving and winding of composite fiber structures of ultrahigh molecular weight polyethylene, ultrahigh molecular weight polypropylene and bacterial cellulose, the diameter is 600nm-2.5 μm, the thickness of the diaphragm is 16-45 μm, patent CN110808351A carries out coupling reaction by a bischloromonomer containing imide ring structure to form polyimide resin powder containing thioether structures, then polyimide resin powder is combined with PVDF resin to form PI/PI resin, PVDF/PVDF resin, the composite membrane material, and the high-organic matter composite membrane material has no more defects in the environment, and is not influenced by the three-based composite membrane process.
The patent CN110504402A obtains the ceramic diaphragm by coating the modified alumina on the surface of the diaphragm by a traditional coating mode. In patent CN110391383A, a high-temperature resistant adhesive is mixed with aramid fiber and a pore-forming agent to form a mixed suspension emulsion; and spraying the obtained mixed suspension emulsion on the surface of a conventional polyolefin diaphragm in a spraying manner, and performing stress relief treatment in a low-temperature environment with nitrogen protection to obtain the aramid fiber coated lithium battery diaphragm. In patent CN110591134A, the modified PMMA is prepared by reacting active groups in guanidine salt with polar groups in a PMMA copolymer precursor through an initiator AIBNAnd the raw materials are crosslinked under the bonding action. The modified PMMA and polysiloxane are compounded, mixed and coated on a diaphragm to obtain the high-specific-capacity flame-retardant lithium battery separator. In patent CN110838567A, high-adhesion emulsion, PVDF, dispersant, thickener, binder and deionized water are used as raw materials to obtain modified PVDF slurry of the diaphragm, and the modified PVDF slurry is coated to obtain the diaphragm with strong adhesion with a negative plate. In patent CN209461548U, Al is coated on the upper surface and the lower surface of a non-woven fabric basal membrane respectively and sequentially2O3Coating and SiO2/Al2O3Coating to obtain the non-woven fabric ceramic diaphragm of the composite material. Patent CN110660949A mixes PVDF, polyvinyl alcohol solution, deionized water and CMC water solution, adds dispersant, CMC water solution, deionized water and alumina powder; adding coagulant and wetting agent, stirring to obtain composite slurry; and coating the composite slurry on a PE diaphragm to obtain the inorganic and organic composite coating diaphragm. Patent CN110429224A comprises a base film layer and a composite coating layer, wherein one side or two sides of the base film layer are coated with the composite coating layer, and the composite coating layer is a water-based coating layer formed by polyvinylidene fluoride PVDF and hollow alumina particles or a mixture of alumina and magnesia. In the above method, whether the coating material is inorganic alumina, silica, magnesia, or organic PVDF, PMMA, aramid, whether the base film is mature PP, PE film, or non-woven fabric, polyimide, etc., the process requires the coating material to be made into slurry and coated on the surface of the base material by various means. The defects are as follows: 1) the process is complex, a base film is required to be prepared firstly, then the slurry is prepared, and then the modified coating material is coated on the base film by a one-time or multi-time coating method; 2) the coating material is easy to fall off, and the coating has local defects; 3) the thickness of the coating is not easy to control; 4) the loss of the base film is large, and the production cost is high; 5) the thin-layer diaphragm is difficult to prepare and has large high-temperature thermal shrinkage.
Patent CN106229446A, adding a main nanofiber material into an organic solvent, heating and stirring to uniformly dissolve the main nanofiber material in the organic solvent to obtain a saturated solution of the main nanofiber material and the organic solvent; adding inorganic nano powder particles into an organic solvent, and stirring to obtain inorganic nano powder particle-organic solvent slurry; adding the inorganic nano powder particles-organic solvent slurry into the nanofiber main material-organic solvent saturated solution, and uniformly mixing and stirring to obtain electrostatic spinning slurry; and spinning the electrostatic spinning slurry on multi-head electrostatic spinning equipment to obtain the composite fiber membrane consisting of the composite nano fibers. The process can generate multifunctional composite diaphragm at one time, but the thickness of the composite diaphragm is difficult to control, the width of the composite diaphragm is narrow, the local thickness is not uniform, the pore channel is not uniform, and local defects are easy to exist.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a process method for preparing a lithium battery diaphragm by using a 3D printing technology, which comprises the steps of taking a diaphragm substrate, superfine ceramic powder and PVDF or PMMA as main materials, uniformly mixing the main materials, grinding the main materials to a certain granularity, heating and melting the main materials, adding an organic solvent to adjust the viscosity, printing a diaphragm structure embedded with the superfine nano ceramic powder and formed by the diaphragm substrate and the PVDF or PMMA on a substrate by using a 3D printer, controlling the thickness by rolling, cooling and solidifying the diaphragm structure, and rolling the diaphragm structure to obtain the multifunctional composite diaphragm with a uniform structure.
The invention is realized by the following technical scheme.
Uniformly mixing the diaphragm base material, the superfine ceramic powder, the PVDF or diaphragm base material, the superfine ceramic powder and the PMMA in a mixer according to a required proportion, transferring the mixture into a drum-type dry grinding machine, and grinding to obtain a mixed material with a required granularity.
Transferring the obtained mixed material to a heater with stirring, heating to melt the material, adding an organic solvent to adjust the viscosity of the material so that the material has certain fluidity, and fully stirring for 2-5 h.
Transferring the melted material to a material injector of a 3D printer, pushing a piston of the injector to enable the material to be sprayed on a substrate in a certain shape and thickness through a 3D printer nozzle according to a preset program, removing residual solvent through an oven, cooling to enable a primary film to be properly solidified, pressing to the required thickness through a roller, completely cooling, solidifying, molding, peeling from the substrate, and rolling to obtain the multifunctional composite diaphragm embedded with the superfine nano ceramic powder, wherein the multifunctional composite diaphragm is composed of a diaphragm base material and PVDF or PMMA.
Preferably, the separator base material is one of PP, PE, and nonwoven fabric.
Preferably, the ultrafine ceramic powder is one or more of alumina, zirconia, boehmite, magnesium hydroxide, barium sulfate, silica and aluminum nitride.
Preferably, the particle size of the superfine ceramic powder is between 30 and 200 nm.
Preferably, the granularity of the diaphragm base material, the superfine ceramic powder and the PVDF or PMMA mixed material after being ground in a drum-type dry grinding machine is 10-100 mu m.
Preferably, the mass ratio of the superfine ceramic powder is 10-30% of that of the base film material; the mass ratio of PVDF or PMMA is 1-10% of the base film material.
Preferably, the organic solvent is one of NMP, DMAC, DMF, TEP and DMS in an amount adjusted to a desired viscosity of the material.
Preferably, the viscosity of the material for 3D printing is 70000-100000 mPa.s.
Preferably, the arrangement width of the spray heads of the 3D printer is 0.1-2m, and the number of the spray heads is not limited.
Preferably, the nozzle is capable of ejecting the film threads, a plurality of the film threads constitute the separator, and the thickness of the prepared separator is 1 to 20 μm.
Preferably, the prepared diaphragm is internally provided with a plurality of regularly arranged and regularly shaped film holes, the film holes are square, circular or regular polygon, and the aperture of the film holes is 30-100 nm.
Preferably, the width of the multifunctional composite diaphragm embedded with the superfine nano ceramic powder is between 0.1 and 2 m.
Preferably, the diameter of the film wire is 50-300 nm.
Preferably, a grafting cross-linking agent, preferably triethoxyvinylsilane, is added into the diaphragm base material, the superfine ceramic powder and the PVDF or PMMA mixed material for properly grafting and cross-linking the PP or PE material.
The process method for preparing the multifunctional lithium battery composite diaphragm by the 3D printing technology provided by the embodiment of the invention comprises the steps of taking a diaphragm substrate, superfine ceramic powder and PVDF or PMMA as main materials, uniformly mixing the main materials, grinding the main materials to a required granularity, heating and melting the main materials, adding an organic solvent to adjust viscosity, printing a diaphragm structure which is formed by the diaphragm substrate and the PVDF or PMMA and is embedded with the superfine nano ceramic powder on a substrate by using a 3D printer, controlling the thickness by rolling, cooling and solidifying the diaphragm structure, and rolling the diaphragm structure to obtain the multifunctional composite diaphragm with a uniform structure. Compared with the prior art: and (3) obtaining the thickness-controllable multifunctional composite diaphragm embedded with the superfine nano ceramic powder by applying a 3D printing technology.
Drawings
FIG. 1 is a flow chart of the present invention.
Fig. 2 is one of the schematic views of the separator of the present invention.
Fig. 3 is a second schematic view of the separator of the present invention.
Fig. 4 is a schematic structural view of a film line of the present invention.
Detailed Description
The invention is further described with reference to the following drawings and detailed description.
And step A), uniformly mixing the diaphragm substrate, the superfine ceramic powder and the PVDF or PMMA in a mixer according to a required proportion, transferring the uniformly mixed materials into a drum-type dry grinding machine, and grinding to obtain mixed material powder with a required granularity.
Wherein the diaphragm base material is one of PP, PE and non-woven fabrics. The superfine ceramic powder is one or more of alumina, zirconia, boehmite, magnesium hydroxide, barium sulfate, silicon oxide and aluminum nitride, and the granularity of the superfine ceramic powder is 30-200 nm. The mass ratio of the superfine ceramic powder is 10-30% of that of the base film material; the mass ratio of PVDF or PMMA is 1-10% of the base film material. The granularity of the diaphragm base material, the superfine ceramic powder and the PVDF or PMMA mixed material after being ground in a drum-type dry grinding machine is 10-100 mu m.
And B), transferring the obtained powder into a heater with a stirrer, heating to melt the material, adding an organic solvent to adjust the viscosity of the material so that the material has certain fluidity, and fully stirring for 2-5 hours.
Wherein the organic solvent is one of NMP, DMAC, DMF, TEP and DMS, and the dosage is adjusted to the viscosity required by the material. The material viscosity is 70000-100000 mPa.s.
And step C), transferring the melted material to a material injector of a 3D printer, pushing a piston of the injector to enable the material to be sprayed on the substrate in a certain shape and thickness through a 3D printer nozzle according to a preset program, removing residual solvent through an oven, cooling to enable the primary film to be primarily solidified, pressing to the required thickness through a roller, completely cooling, solidifying, molding, peeling off the substrate, and rolling to obtain the multifunctional composite diaphragm embedded with the superfine nano ceramic powder and composed of the diaphragm substrate and PVDF or PMMA.
The arrangement width of the spray heads of the 3D printer is 0.1-2m, the spray heads can spray film lines 3, a plurality of film lines 3 form a diaphragm, the thickness of the prepared diaphragm is 1-20 mu m, a plurality of regularly arranged and regularly shaped film holes 1 are formed in the prepared diaphragm, the film holes 1 are square, circular or regular polygon, the aperture of the film holes is 30-100nm, the width 2 of the diaphragm of the multifunctional composite diaphragm embedded with the superfine nano ceramic powder is 0.1-2m, and the diameter of the film lines is 50-300 nm.
The embodiment of the invention provides a multifunctional composite diaphragm which is prepared by taking a diaphragm substrate, superfine ceramic powder and PVDF or PMMA as main materials, uniformly mixing the materials, heating and melting the materials, adding an organic solvent to adjust viscosity, printing a diaphragm structure embedded with the superfine nano ceramic powder and formed by the diaphragm substrate and the PVDF or PMMA on a substrate by using a 3D printer, controlling the thickness by rolling, cooling and curing the diaphragm structure, and rolling the diaphragm structure to obtain the multifunctional composite diaphragm with a uniform structure.
In order to better understand the technical scheme provided by the present invention, the following examples respectively illustrate the specific processes for preparing the multifunctional lithium battery composite separator by using the methods provided by the above examples of the present invention.
Example 1
Step 1, uniformly mixing the PP diaphragm substrate, the superfine alumina powder and the PVDF in a mixer according to the ratio of 7:2:1, transferring the uniformly mixed materials to a drum-type dry grinding machine, and grinding the materials to obtain mixed material powder with the granularity of 30 mu m.
And 2, transferring the mixed material powder obtained in the step 1 to a heater with stirring, heating to 180 ℃ to melt the material, adding NMP to adjust the viscosity of the material to 80000mPa.s so that the material has certain fluidity, and fully stirring for 3 hours. And obtaining the material to be printed.
And 3, transferring the melted material to be printed into a material injector of the 3D printer, wherein the arrangement width of the spray heads of the 3D printer is 1.5 m.
The thickness, pore shape and diameter, film line diameter, printing speed, etc. of the diaphragm are set by a printer computer. After the printing is started, the injector piston is pushed to enable the material to be sprayed on the substrate through a 3D printer nozzle in a circular pore channel with the thickness of 20 microns according to a preset program, and the film forming speed is 2 m/min. After printing and film forming, the film passes through a vacuum oven with the temperature of 135 ℃, residual solvent is removed, the primary film is cooled to be properly solidified, the primary film is pressed to 10 mu m by a rolling shaft, the primary film is peeled from a substrate after being completely cooled, solidified and formed, and the PP/PVDF/alumina multifunctional composite diaphragm with the embedded superfine alumina film and the circular pore canal, wherein the diameter of the embedded superfine alumina film is 100nm, is obtained by rolling.
Example 2
Step 1, uniformly mixing the PE diaphragm substrate, the superfine alumina powder and the PVDF in a mixer according to the ratio of 7:2:1, transferring the uniformly mixed materials into a drum-type dry grinding machine, and grinding the materials into mixed material powder with the granularity of 30 mu m.
And 2, transferring the mixed material powder obtained in the step 1 to a heater with stirring, heating to 175 ℃ to melt the material, adding NMP to adjust the viscosity of the material to 80000mPa.s so that the material has certain fluidity, and fully stirring for 3 hours. And obtaining the material to be printed.
And 3, transferring the melted material to be printed into a material injector of the 3D printer, wherein the arrangement width of the spray heads of the 3D printer is 1.5 m.
The thickness, pore shape and diameter, film line diameter, printing speed, etc. of the diaphragm are set by a printer computer. After the printing is started, the injector piston is pushed to enable the material to be sprayed on the substrate through a 3D printer nozzle in a circular pore channel with the thickness of 20 microns according to a preset program, and the film forming speed is 2 m/min. After printing and film forming, the film passes through a vacuum oven with the temperature of 135 ℃, residual solvent is removed, the film is cooled to enable the primary film to be properly solidified, the primary film is pressed to 10 mu m through a rolling shaft, the primary film is peeled from a substrate after being completely cooled, solidified and formed, and the PE/PVDF/alumina multifunctional composite diaphragm with the embedded superfine alumina film and the circular pore passage with the linear diameter of 100nm, which is composed of PE and PVDF, is obtained by rolling.
Example 3
Step 1, uniformly mixing the polypropylene non-woven fabric diaphragm base material, the superfine alumina powder and the PVDF in a mixer according to the ratio of 7:2:1, transferring the uniformly mixed material to a drum-type dry grinding machine, and grinding the material to obtain mixed material powder with the granularity of 30 mu m.
And 2, transferring the mixed material powder obtained in the step 1 to a heater with stirring, heating to 175 ℃ to melt the material, adding NMP to adjust the viscosity of the material to 80000mPa.s so that the material has certain fluidity, and fully stirring for 3 hours. And obtaining the material to be printed.
And 3, transferring the melted material to be printed into a material injector of the 3D printer, wherein the arrangement width of the spray heads of the 3D printer is 1.5 m.
The thickness, pore shape and diameter, film line diameter, printing speed, etc. of the diaphragm are set by a printer computer. After the printing is started, the injector piston is pushed to enable the material to be sprayed on the substrate through a 3D printer nozzle in a circular pore channel with the thickness of 20 microns according to a preset program, and the film forming speed is 2 m/min. After printing and film forming, the film passes through a vacuum oven with the temperature of 135 ℃, residual solvent is removed, the film is cooled to enable the primary film to be properly solidified, the primary film is pressed to 10 mu m through a rolling shaft, the primary film is peeled from a substrate after being completely cooled, solidified and formed, and the circular pore channel non-woven fabric/PVDF/alumina multifunctional composite diaphragm which is composed of non-woven fabric and PVDF and is embedded with a superfine alumina film and has the linear diameter of 100nm is obtained by rolling.
Example 4
Step 1, uniformly mixing the PE diaphragm substrate, the superfine alumina powder and the PMMA in a mixer according to the ratio of 7:2:1, transferring the uniformly mixed materials into a drum-type dry grinding machine, and grinding the materials into mixed material powder with the granularity of 30 mu m.
And 2, transferring the mixed material powder obtained in the step 1 to a heater with stirring, heating to 200 ℃ to melt the material, adding NMP to adjust the viscosity of the material to 80000mPa.s so that the material has certain fluidity, and fully stirring for 3 hours. And obtaining the material to be printed.
And 3, transferring the melted material to be printed into a material injector of the 3D printer, wherein the arrangement width of the spray heads of the 3D printer is 1.5 m.
The thickness, pore shape and diameter, film line diameter, printing speed, etc. of the diaphragm are set by a printer computer. After the printing is started, the injector piston is pushed to enable the material to be sprayed on the substrate through a 3D printer nozzle in a circular pore channel with the thickness of 20 microns according to a preset program, and the film forming speed is 2 m/min. After printing and film forming, the film passes through a vacuum oven with the temperature of 135 ℃, residual solvent is removed, the film is cooled to enable the primary film to be properly solidified, the primary film is pressed to 10 mu m through a rolling shaft, the primary film is peeled from a substrate after being completely cooled, solidified and formed, and the PE/PMMA/alumina multifunctional composite diaphragm with the embedded superfine alumina film and the circular pore passage with the linear diameter of 100nm, which is formed by PE and PMMA, is obtained by rolling.
Example 5
Step 1, uniformly mixing the PP diaphragm substrate, the ultrafine boehmite powder and the PVDF in a mixer according to the ratio of 7:2:1, transferring the uniformly mixed materials to a drum-type dry grinding machine, and grinding the materials to obtain mixed material powder with the granularity of 30 mu m.
And 2, transferring the mixed material powder obtained in the step 1 to a heater with stirring, heating to 175 ℃ to melt the material, adding NMP to adjust the viscosity of the material to 80000mPa.s so that the material has certain fluidity, and fully stirring for 3 hours. And obtaining the material to be printed.
And 3, transferring the melted material to be printed into a material injector of the 3D printer, wherein the arrangement width of the spray heads of the 3D printer is 1.5 m.
The thickness, pore shape and diameter, film line diameter, printing speed, etc. of the diaphragm are set by a printer computer. After the printing is started, the injector piston is pushed to enable the material to be sprayed on the substrate through a 3D printer nozzle in a circular pore channel with the thickness of 20 microns according to a preset program, and the film forming speed is 2 m/min. After printing and film forming, the film is put into a vacuum oven with the temperature of 135 ℃, residual solvent is removed, the film is cooled to enable the primary film to be properly solidified, the film is pressed to 10 mu m through a rolling shaft, the film is stripped from a substrate after being completely cooled, solidified and formed, and the round pore PP/PVDF/boehmite multifunctional composite diaphragm with the embedded superfine oxygen boehmite film line diameter of 100nm and composed of PP and PVDF is obtained by rolling.
Example 6
Step 1, uniformly mixing the PP diaphragm substrate, the superfine alumina powder and the PVDF in a mixer according to the ratio of 7:2:1, transferring the uniformly mixed materials to a drum-type dry grinding machine, and grinding the materials to obtain mixed material powder with the granularity of 30 mu m.
And 2, transferring the mixed material powder obtained in the step 1 to a heater with stirring, heating to 175 ℃ to melt the material, adding NMP to adjust the viscosity of the material to 80000mPa.s so that the material has certain fluidity, and fully stirring for 3 hours. And obtaining the material to be printed.
And 3, transferring the melted material to be printed into a material injector of the 3D printer, wherein the arrangement width of the spray heads of the 3D printer is 1.5 m.
The thickness, pore shape and diameter, film line diameter, printing speed, etc. of the diaphragm are set by a printer computer. After the printing is started, the injector piston is pushed to enable the material to be sprayed on the substrate through a 3D printer nozzle in a circular pore channel with the thickness of 20 microns according to a preset program, and the film forming speed is 2 m/min. After printing and film forming, the film passes through a vacuum oven with the temperature of 135 ℃, residual solvent is removed, the primary film is cooled to be properly solidified, the primary film is pressed to 10 mu m by a rolling shaft, the primary film is peeled from a substrate after being completely cooled, solidified and formed, and the PP/PVDF/alumina multifunctional composite diaphragm with the embedded superfine alumina film and the regular hexagonal pore canal with the linear diameter of 100nm, which is composed of PP and PVDF, is obtained by rolling.
Example 7
Step 1, uniformly mixing the PE diaphragm substrate, the superfine alumina powder and the PVDF in a mixer according to the ratio of 7:2:1, transferring the uniformly mixed materials into a drum-type dry grinding machine, and grinding the materials into mixed material powder with the granularity of 30 mu m.
And 2, transferring the mixed material powder obtained in the step 1 to a heater with a stirrer, heating to 175 ℃ to melt the material, adding DMAC (dimethylacetamide) to adjust the viscosity of the material to 80000mPa.s, enabling the material to have certain fluidity, and fully stirring for 3 hours. And obtaining the material to be printed.
And 3, transferring the melted material to be printed into a material injector of the 3D printer, wherein the arrangement width of the spray heads of the 3D printer is 1.5 m.
The thickness, pore shape and diameter, film line diameter, printing speed, etc. of the diaphragm are set by a printer computer. After the printing is started, the injector piston is pushed to enable the material to be sprayed on the substrate through a 3D printer nozzle in a circular pore channel with the thickness of 20 microns according to a preset program, and the film forming speed is 2 m/min. After printing and film forming, the film passes through a vacuum oven with the temperature of 135 ℃, residual solvent is removed, the film is cooled to enable the primary film to be properly solidified, the primary film is pressed to 10 mu m through a rolling shaft, the primary film is peeled from a substrate after being completely cooled, solidified and formed, and the PE/PVDF/alumina multifunctional composite diaphragm with the embedded superfine alumina film and the regular hexagonal pore passage with the linear diameter of 100nm is obtained by rolling.
Example 8
Step 1, uniformly mixing the PE diaphragm substrate, the superfine alumina powder and the PVDF in a mixer according to the ratio of 7:2:1, transferring the uniformly mixed materials into a drum-type dry grinding machine, and grinding the materials into mixed material powder with the granularity of 30 mu m.
Step 2, transferring the mixed material powder obtained in the step 1 to a heater with a stirrer, and heating to 175 ℃ to melt the material, wherein the mixing time is 20 min;
step 3, adding DMAC to adjust the viscosity of the material to 80000mPa.s, and sampling and detecting to obtain a material to be printed with the PE gel content of 5%;
and 4, transferring the melted material to be printed into a material injector of the 3D printer, wherein the arrangement width of the spray heads of the 3D printer is 1.5 m.
The thickness, pore shape and diameter, film line diameter, printing speed, etc. of the diaphragm are set by a printer computer. After the printing is started, the injector piston is pushed to enable the material to be sprayed on the substrate through a 3D printer nozzle in a circular pore channel with the thickness of 20 microns according to a preset program, and the film forming speed is 2 m/min. After printing and film forming, the film is put into a vacuum oven with the temperature of 135 ℃, residual solvent is removed, the film is cooled to enable the primary film to be properly solidified, the film is pressed to 10 mu m by a rolling shaft, the film is peeled from a substrate after being completely cooled, solidified and formed, and the PE/PVDF/alumina multifunctional composite diaphragm with the embedded superfine alumina film and the regular hexagonal pore passage with the linear diameter of 100nm, which is composed of PE and PVDF, is obtained by rolling, and the gel degree of the PE is 15%.
The scope of the present invention includes, but is not limited to, the above embodiments, and the present invention is defined by the appended claims, and any alterations, modifications, and improvements that may occur to those skilled in the art are all within the scope of the present invention.

Claims (10)

1. A process method for preparing a lithium battery diaphragm by using a 3D printing technology is characterized in that in the step A), a diaphragm substrate, superfine ceramic powder and one of PVDF and PMMA are uniformly mixed in a mixer according to a required proportion and then transferred to a grinder to be ground to obtain a mixed material with a required granularity; B) transferring the obtained mixed material to a heater with stirring, heating to melt the material, adding an organic solvent to adjust the viscosity of the material, and stirring for 2-5 h; C) transferring the melted material to a material injector of a 3D printer, pushing a piston of the injector to enable the material to be sprayed on a substrate in a certain shape and thickness through a 3D printer nozzle, taking the substrate, removing residual solvent through an oven, cooling to enable primary film making to be preliminarily solidified, pressing to the required thickness through a roller, completely cooling, solidifying, stripping from the substrate, and rolling to obtain the multifunctional composite diaphragm embedded with the superfine nano ceramic powder.
2. The process for preparing a lithium battery separator according to claim 1, wherein in the step a), the ultrafine ceramic powder is one or more of alumina, zirconia, boehmite, magnesium hydroxide, barium sulfate, silica and aluminum nitride, and the particle size of the ultrafine ceramic powder is 30-200 nm.
3. The process method for preparing a lithium battery separator by using a 3D printing technology as claimed in claim 1, wherein in the step A), the separator substrate is one of PP, PE and non-woven fabrics.
4. The process method for preparing the lithium battery diaphragm by using the 3D printing technology as claimed in claim 1, wherein in the step A), the mass ratio of the superfine ceramic powder is 10-30% of that of the base film material, and the mass ratio of the PVDF or PMMA is 1-10% of that of the base film material, taking the base film material as the center.
5. The process for preparing a lithium battery separator by using a 3D printing technology as claimed in claim 1, wherein in the step A), the particle size of the mixed material after grinding is 10-100 μm.
6. The process of claim 1, wherein in step B), the organic solvent is one of NMP, DMAC, DMF, TEP and DMS, and the amount is adjusted to the required viscosity of the material, and the required viscosity of the material is 70000-100000 mPa.s.
7. The process method for preparing the lithium battery diaphragm by using the 3D printing technology as claimed in claim 1, wherein in the step C), the arrangement width of the spray head of the 3D printer is 0.1-2m, the spray head can spray the film lines (3), the diaphragm is formed by a plurality of film lines (3), and the thickness of the prepared diaphragm is 1-20 μm.
8. The process method for preparing the lithium battery diaphragm by using the 3D printing technology as claimed in claim 1, wherein in the step C), the prepared diaphragm is internally provided with a plurality of regularly arranged and regularly shaped diaphragm holes (1), the diaphragm holes (1) are square, circular or regular polygon, and the aperture of the diaphragm holes is 30-100 nm.
9. The process method for preparing the lithium battery separator by using the 3D printing technology as claimed in claim 1, wherein in the step C), the width (2) of the multifunctional composite separator embedded with the ultrafine nano ceramic powder is between 0.1 and 2 m.
10. The process for preparing a lithium battery separator according to claim 7, wherein in step C), the diameter of the film wire is 50-300 nm.
CN202010316823.0A 2020-04-21 2020-04-21 Process method for preparing lithium battery diaphragm by using 3D printing technology Pending CN111446402A (en)

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