CN111086181A - Preparation method of lithium battery diaphragm - Google Patents
Preparation method of lithium battery diaphragm Download PDFInfo
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- CN111086181A CN111086181A CN201911384424.1A CN201911384424A CN111086181A CN 111086181 A CN111086181 A CN 111086181A CN 201911384424 A CN201911384424 A CN 201911384424A CN 111086181 A CN111086181 A CN 111086181A
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- 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
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/001—Combinations of extrusion moulding with other shaping operations
- B29C48/0018—Combinations of extrusion moulding with other shaping operations combined with shaping by orienting, stretching or shrinking, e.g. film blowing
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- 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
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/07—Flat, e.g. panels
- B29C48/08—Flat, e.g. panels flexible, e.g. films
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- 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
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/09—Articles with cross-sections having partially or fully enclosed cavities, e.g. pipes or channels
- B29C48/11—Articles with cross-sections having partially or fully enclosed cavities, e.g. pipes or channels comprising two or more partially or fully enclosed cavities, e.g. honeycomb-shaped
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- 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
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/285—Feeding the extrusion material to the extruder
- B29C48/288—Feeding the extrusion material to the extruder in solid form, e.g. powder or granules
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- 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
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/285—Feeding the extrusion material to the extruder
- B29C48/297—Feeding the extrusion material to the extruder at several locations, e.g. using several hoppers or using a separate additive feeding
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- 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
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/92—Measuring, controlling or regulating
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- 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
- B29C71/00—After-treatment of articles without altering their shape; Apparatus therefor
- B29C71/02—Thermal after-treatment
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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
- H01M50/411—Organic material
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- 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
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/9258—Velocity
- B29C2948/9259—Angular velocity
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- 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
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/92704—Temperature
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- 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
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92819—Location or phase of control
- B29C2948/92857—Extrusion unit
- B29C2948/92876—Feeding, melting, plasticising or pumping zones, e.g. the melt itself
- B29C2948/92885—Screw or gear
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- 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
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92819—Location or phase of control
- B29C2948/92857—Extrusion unit
- B29C2948/92904—Die; Nozzle zone
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2023/00—Use of polyalkenes or derivatives thereof as moulding material
- B29K2023/10—Polymers of propylene
- B29K2023/12—PP, i.e. polypropylene
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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Abstract
The invention provides a preparation method of a lithium battery diaphragm, which is characterized by comprising the following steps of a, carrying out high-temperature blending extrusion on ultra-polypropylene, β crystal form nucleating agent, antioxidant and reinforcing agent by an extrusion device, further cooling and granulating the extruded product to obtain α crystal form ultra-polypropylene particles, b, carrying out high-temperature blending extrusion on α crystal form ultra-polypropylene particles, sequentially passing the extruded product through a die head and a casting unit to obtain a casting sheet, c, carrying out crystallization treatment on the casting sheet by a heat treatment unit, d, sequentially carrying out longitudinal stretching heat setting treatment and transverse stretching heat setting treatment on the casting sheet after the crystallization treatment by a bidirectional stretching device, and e, sequentially carrying out heat setting step and cold setting on the casting sheet after the transverse stretching heat setting treatment to obtain the bidirectional stretching lithium battery diaphragm.
Description
Technical Field
The invention relates to the technical field of lithium ion battery materials, in particular to a preparation method of a lithium battery diaphragm.
Background
Under the big background of the national strong advocation of low carbon and environmental protection in recent years, the new energy industry in China is developed vigorously, and lithium batteries are highly concerned as new pets in the new energy industry, so that China currently becomes the largest lithium battery production base in the world, the second largest lithium battery production country and export countries. Lithium battery products account for 30% -40% of the world, and as an important core component of lithium batteries, lithium battery separators are high-value-added materials with the highest technical barrier in lithium battery materials, and account for more than 30% of the cost of the lithium batteries.
The separator has the main function of separating the positive and negative electrodes to prevent the electrodes from contacting and shorting while allowing electrolyte ions to pass freely. As one of the indispensable important components in the lithium ion battery, the performance of the lithium ion battery determines important parameters such as the interface structure and the electrolyte wettability of the battery, directly influences the capacity, the charge-discharge cycle and the safety performance of the battery, and plays an important role in improving the comprehensive performance of the battery.
At present, a lithium battery diaphragm mainly adopts a polyolefin microporous membrane, and important performance parameters of the lithium battery diaphragm comprise pore size distribution, porosity, air permeability, puncture resistance, thickness uniformity and the like. The main processes for preparing the polyolefin lithium ion battery diaphragm include a dry process and a wet process, wherein the dry process comprises a unidirectional stretching process and a bidirectional stretching process. However, the minimum thickness of the lithium battery separator prepared by the dry biaxial stretching process in the market can only reach 16 μm, and the thickness generally used is more than 20 μm. Meanwhile, the lithium battery diaphragm prepared by the process has the problems of uneven pore size distribution, uneven thickness, transverse thermal shrinkage, large porosity change and the like of micropores, and the service performance of the lithium battery is influenced.
Disclosure of Invention
The invention aims to overcome the defects in the prior art, and provides a preparation method of a lithium battery diaphragm, which is used for preparing the lithium battery diaphragm and solves the problems of nonuniform pore size distribution, nonuniform thickness, transverse thermal shrinkage, large porosity change and the like of the lithium battery diaphragm in the prior art.
The invention provides a preparation method of a lithium battery diaphragm, which comprises the following steps:
a preparation method of a lithium battery diaphragm is characterized by comprising the following steps:
a. blending and extruding the ultra-polypropylene, the β crystal form nucleating agent, the antioxidant and the reinforcing agent at high temperature by an extruding device, and further cooling and dicing the extruded product to obtain α crystal form ultra-polypropylene particles;
b. blending and extruding the α crystal form polypropylene particles at high temperature, and sequentially passing the extruded product through a die head and a casting sheet unit to obtain a casting sheet;
c. crystallizing the cast sheet through a heat treatment unit;
d. sequentially carrying out longitudinal stretching heat setting treatment and transverse stretching heat setting treatment on the crystallized casting sheet by using biaxial stretching equipment;
e. and sequentially carrying out heat setting and cold setting on the cast sheet subjected to transverse stretching and heat setting treatment to obtain the biaxial stretching lithium battery microporous membrane.
Further, the molecular weight of the ultra-polypropylene is 30-120 ten thousand, the molecular weight distribution is more than 8, the melt index is 2.0-4.0 g/10min, and the isotacticity is more than 95%.
Further, the β crystal form nucleating agent is a carboxylate nucleating agent, and the antioxidant is DLTP.
Further, the mass ratio of the ultra-polypropylene to the β crystal form nucleating agent is 85-95: 1, the mass ratio of the ultra-polypropylene to the antioxidant is 75-95: 1, and the mass ratio of the ultra-polypropylene to the reinforcing agent is 80-95: 1.
Further, the temperature of each section of the screw is 170-190 ℃ in the first zone, 190-215 ℃ in the second zone, 215-235 ℃ in the third zone, 235-280 ℃ in the fourth zone, 235-280 ℃ in the fifth zone, 235-280 ℃ in the sixth zone, 235-280 ℃ in the seventh zone, 235-280 ℃ in the eighth zone, 235-280 ℃ in the ninth zone, 235-280 ℃ in the tenth zone, the head temperature is 235-280 ℃ and the extrusion speed of the extrusion device is 400-700 rpm/min.
Further, the temperature of each section of the screw is 175-215 ℃, 205-215 ℃, 215-225 ℃, 225-235 ℃, 235-265 ℃ and 235-265 ℃ in sequence during extrusion by the extrusion device, the temperature of the die head is 225-265 ℃, and the extrusion speed of the extrusion device is 20-45 rpm/min.
Further, the temperature of the heat setting step is 90-140 ℃, and the temperature of the cold setting step is 20-50 ℃.
The casting device is further characterized in that the temperature of the casting unit is 100-140 ℃, and the temperature of the heat treatment unit is 100-140 ℃.
Further, in the step d: the total ratio of longitudinal stretching is 3-11, the stretching temperature is 65-115 ℃, and the heat setting temperature is 90-120 ℃; the total rate of transverse stretching is 3-11, the stretching temperature is 110-135 ℃, and the setting temperature is 145-180 ℃.
Further, the extruding device comprises a main feeder and an auxiliary feeder, wherein the main feeder is added with the ultra-polypropylene, the auxiliary feeder is added with the β crystal form nucleating agent, the antioxidant and the reinforcing agent, the filler speed of the main feeder is 40-80 rpm/min, and the filler speed of the auxiliary feeder is 15-40 rpm/min.
The preparation method of the ultrathin dry-method biaxially oriented lithium battery diaphragm has the beneficial effects that:
1. the production process has the advantages of simple process, low equipment cost and low investment.
2. The thickness of the prepared lithium battery diaphragm can be as low as 8 mu m, which is lower than the market level, the production cost of unit area is reduced, and the quality of the lithium battery diaphragm can be comparable to that of a lithium battery diaphragm prepared by a wet process.
3. The prepared lithium battery diaphragm has transverse and longitudinal thermal shrinkage of 0, uniform pore size distribution of the diaphragm micropores, better air permeability and high product yield of more than 70 percent.
4. The thickness range of the lithium battery diaphragm prepared by the process is far larger than that of the lithium battery diaphragm prepared by the common biaxial stretching process, and the lithium battery diaphragm has wide application range, can be used for power batteries, and has good market application prospect.
5. The production process has no environmental pollution.
Other characteristic features and advantages of the invention will become apparent from the following description of exemplary embodiments, which is to be read in connection with the accompanying drawings.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of the specification, illustrate embodiments of the invention and together with the description, serve to explain the principles of the invention. In the drawings, like reference numerals are used to indicate like elements. The drawings in the following description are directed to some, but not all embodiments of the invention. For a person skilled in the art, other figures can be derived from these figures without inventive effort.
Fig. 1 exemplarily shows a flow chart of a method for preparing an ultra-thin dry biaxially oriented lithium battery separator according to the present invention;
fig. 2 exemplarily shows a scanning electron micrograph of the microporous separator for a lithium battery prepared in example 1 of the present invention.
DETAILED DESCRIPTION OF EMBODIMENT (S) OF INVENTION
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 drawings in the embodiments of the present invention, and it is obvious that the described embodiments are some, but not all, embodiments of the present invention. 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. It should be noted that the embodiments and features of the embodiments in the present application may be arbitrarily combined with each other without conflict.
The invention provides a preparation method of an ultrathin dry-method biaxial tension lithium battery diaphragm, which comprises the following steps:
a. blending and extruding the ultra-polypropylene, the β crystal form nucleating agent, the antioxidant and the reinforcing agent at high temperature by an extruding device, and further cooling and dicing the extruded product to obtain α crystal form ultra-polypropylene particles;
b. blending and extruding the α crystal form polypropylene particles at high temperature, and sequentially passing the extruded product through a die head and a casting sheet unit to obtain a casting sheet;
c. crystallizing the cast sheet through a heat treatment unit;
d. sequentially carrying out longitudinal stretching heat setting treatment and transverse stretching heat setting treatment on the crystallized casting sheet by using biaxial stretching equipment;
e. and sequentially carrying out heat setting and cold setting on the cast sheet subjected to transverse stretching and heat setting treatment to obtain the biaxial stretching lithium battery microporous membrane.
Wherein the molecular weight of the ultra-polypropylene can be 30-120 ten thousand, the molecular weight distribution is more than 8, the melt index is 2.0-4.0 g/10min, and the isotacticity is more than 95%.The preferred molecular weight can be 30 ten thousand, 50 ten thousand, 100 ten thousand and 120 ten thousand, the molecular weight distribution is more than 8, the best is The selected molecular weight is 10, the melt index is 2.0-4.0 g/10min, preferably 2.0g/10min, 2.5g/10min, 3.3g/10min, 4.0g/10min, and the isotacticity is more than 95 percent, and the preferred isotacticity isThe content was 99%. Its advantages are low fusion index, high viscosity and low cost The lithium battery diaphragm has the advantages of uniform micropore diameter distribution, uniform thickness, small transverse heat shrinkage, variable porosity and good stability.
The β crystal form nucleating agent can be carboxylate nucleating agent, and can be selected from aromatic carboxylate or one or more of aromatic carboxylate, such as lithium benzoate, sodium benzoate, potassium benzoate and the like, and also can be selected from rare earth β crystal form nucleating agent.
Wherein the antioxidant can be one or more of antioxidant DLTP, antioxidant 1010, antioxidant 1076, antioxidant 168 or antioxidant 264.
Wherein, the reinforcing agent can be organic modified nano montmorillonite or liquid paraffin.
In general, the weight ratio of the ultra-polypropylene to the β crystal form nucleating agent can be 85-95: 1, preferably 87-92: 1, the weight ratio of the ultra-polypropylene to the antioxidant is 75-95: 1, preferably 80-90: 1, the weight ratio of the ultra-polypropylene to the reinforcing agent is 80-95: 1, preferably 85-90: 1, and under the condition of the weight ratio, the ultra-polypropylene and each additive can completely react, so that the subsequent extrusion process is facilitated, and the thinner lithium battery diaphragm can be obtained.
According to the practical use condition, the temperature of each section of the equipment during extrusion can be 170-190 ℃ in the first zone, 190-215 ℃ in the second zone, 215-235 ℃ in the third zone, 235-280 ℃ in the fourth zone, 235-280 ℃ in the fifth zone, 235-280 ℃ in the sixth zone, 235-280 ℃ in the seventh zone, 235-280 ℃ in the eighth zone, 235-280 ℃ in the ninth zone, 235-280 ℃ in the tenth zone, 235-280 ℃ in the head temperature, and 400-700 rpm/min in the extrusion speed, so that the crystallization speed is increased and the conversion from the β crystal form to the α crystal form is promoted, the higher porosity is obtained, the pore size distribution is more uniform, the two-way extrusion is more facilitated, and the thinner lithium battery diaphragm is obtained.
When the method is applied specifically, a precise double-screw extruder can be adopted as the extruding device, the extruding device comprises a main feeder and an auxiliary feeder, the main feeder is added with the ultra-polypropylene, the auxiliary feeder is added with β crystal form nucleating agent, antioxidant and reinforcing agent, the filler speed of the main feeder is 40-80 rpm/min, the filler speed of the auxiliary feeder is 15-40 rpm/min, and the ultra-polypropylene and a mixing machine can be fully mixed by controlling different feeding speeds.
When the single-screw extruder is used in the concrete application, the temperature of each section of the screw can be 175-215 ℃, 205-215 ℃, 215-225 ℃, 225-235 ℃, 235-265 ℃ and 235-265 ℃ in sequence when the single-screw extruder extrudes, the temperature of the die head is 225-265 ℃, and the extrusion speed of the single-screw extruder is 20-45 rpm/min.
The temperature of the casting sheet unit can be 100-140 ℃, a vacuum auxiliary mode paster is adopted, the temperature of a preheating roller adopted in the preheating shaping step is 100-140 ℃, the preheating unit at least comprises 3 preheating units, the preheating units are arranged on two sides of the casting sheet in a staggered mode, the purpose of the preheating units is to enable one surface of the casting sheet which is not in contact with the casting sheet unit to be heated to form secondary crystallization, the preheating units are generally heated by heat conduction oil, the operation can enable the surface temperature of the preheating units to be uniform, the casting sheet speed is greatly improved, the prepared casting sheet is more uniform, and the performance is stable.
In step d: the total ratio of longitudinal stretching can be 3-11, the stretching temperature is 65-115 ℃, the setting temperature is 90-120 ℃, the total ratio of transverse stretching is 3-11, the stretching temperature is 110-135 ℃, and the setting temperature is 145-180 ℃. And selecting specific stretching parameters to realize the bidirectional asynchronous stretching of the cast sheet. When the cast sheet is longitudinally stretched, the spherulites are broken to generate microfibers and simultaneously generate micro defects, and the micro defects are enlarged when the cast sheet is transversely stretched. The method is beneficial to micropore expansion, improves the air permeability of the diaphragm, enables the pore size distribution to be more uniform, and obtains a thinner lithium battery diaphragm. Wherein, adopt the customization fan during horizontal stretching, make the voltage-sharing wind channel, guarantee that each district's section temperature, wind pressure are even stable
In the heat setting process, the heat setting temperature can be 120-170 ℃, the temperature can be preferably 140 ℃ or 150 ℃, and the setting time is 5-30 min, preferably 10min, 20min and 25 min.
During drawing, the temperature of the heat setting roller can be 90-140 ℃, in a preferred embodiment, the temperature of the heat setting roller can be 110 ℃, the temperature of the heat setting roller can be 20-50 ℃, in a preferred embodiment, the temperature of the heat setting roller can be 38 ℃, setting is carried out at the next degree, the temperature of the cast piece is gradually cooled, the longitudinal and transverse heat shrinkage rates can be obviously improved, and the obtained transverse and/or longitudinal heat shrinkage rates can be 0.
According to a full-automatic thickness gauge and a scanning electron microscope, the thickness of the membrane after biaxial stretching can reach 8-12 microns, the diameter of a micropore is 0.05-0.1 micron, the air permeability range is 150-300, the porosity is 35-45%, the transverse thermal shrinkage is 0, and the longitudinal thermal shrinkage is 0.
For further understanding of the present invention, the following examples are provided to illustrate the preparation method of the ultra-thin dry-process biaxially oriented lithium battery separator provided by the present invention, and the scope of the present invention is not limited by the following examples.
Example 1
The ultra-polypropylene, the nucleating agent lithium benzoate, the antioxidant DLTP and the reinforcing agent organic modified nano montmorillonite are blended and extruded by a double-screw extruder to prepare ultra-polypropylene particles with the content of β crystal form nucleating agent of 0.05 wt%, and the temperature of each section of the screw is 185 ℃ in a first zone, 195 ℃ in a second zone, 220 ℃ in a third zone, 235 ℃ in a fourth zone, 245 ℃ in a fifth zone, 245 ℃ in a sixth zone, 245 ℃ in a seventh zone, 245 ℃ in an eighth zone, 245 ℃ in a ninth zone, 245 ℃ in a tenth zone, 245 ℃ in a head, 560rpm/min in an extruder, 64rpm/min in the filler speed of a main feeder, and the master batch with the filler speed of a subsidiary feeder of 21rpm/min is granulated by the double-screw extruder.
Then the ultra-polypropylene particles are extruded and cast by a single screw extruder to prepare thick sheets. The temperatures from the feeding port to the die port of the casting single-screw extruder were 180 ℃, 210 ℃, 220 ℃, 225 ℃, 245 ℃ and 245 ℃. The melt is processed by a 118 ℃ casting unit to form a casting sheet, and then secondary crystallization is carried out by a preheating unit, wherein the temperature of the preheating unit is 140 ℃, and the thickness of the casting sheet is 0.5 mm.
The method comprises the steps of longitudinal stretching and transverse stretching. The longitudinal stretching ratio and the transverse stretching ratio are both 4 times, and are similar to the wet stretching ratio. The longitudinal stretching temperature is 93 ℃, and the setting temperature is 108 ℃. The transverse stretching temperature is 120 ℃, and the setting temperature is 180 ℃.
The heat-setting temperature was 153 ℃. Setting time is 20 min.
And then, drawing by a hot forming roller and a cold forming roller, wherein the hot roller temperature is 110 ℃, and the cold roller temperature is 35 ℃ to finally obtain the ultrathin biaxial tension lithium battery microporous membrane.
Example 2
The method comprises the steps of blending and extruding the ultra-polypropylene, the nucleating agent lithium benzoate, the antioxidant DLTP and the reinforcing agent organically modified nano montmorillonite through a double-screw extruder to obtain ultra-polypropylene particles with the content of β crystal form nucleating agent of 0.05 wt%, wherein the temperature of each section of the screw is 170 ℃ in a first zone, 215 ℃ in a second zone, 280 ℃ in a third zone, 280 ℃ in a fourth zone, 280 ℃ in a fifth zone, 280 ℃ in a sixth zone, 280 ℃ in a seventh zone, 280 ℃ in an eighth zone, 280 ℃ in a ninth zone, 280 ℃ in a tenth zone, 280 ℃ in a sixth zone, 700rpm/min of the extruder, 80rpm/min of the filler speed of a main feeder, and 40pm/min of the filler speed of an auxiliary feeder, granulating the master batch through.
Then the ultra-polypropylene particles are extruded and cast by a single screw extruder to prepare thick sheets. The temperatures from the feeding port to the die of the casting single-screw extruder were 215 ℃, 225 ℃, 235 ℃, 265 ℃ and 265 ℃. The melt is processed by a 118 ℃ casting unit to form a casting sheet, and then secondary crystallization is carried out by a preheating unit, wherein the temperature of the preheating unit is 116 ℃, and the thickness of the casting sheet is 0.5 mm.
The method comprises the steps of longitudinal stretching and transverse stretching. The longitudinal stretching ratio and the transverse stretching ratio are both 11 times, and are similar to the wet stretching ratio. The longitudinal stretching temperature is 115 ℃, and the setting temperature is 90 ℃. The transverse stretching temperature is 130 ℃, and the setting temperature is 153 ℃.
The heat-setting temperature was 170 ℃. Setting time is 30 min.
And then, carrying out traction by a hot setting roller and a cold setting roller, wherein the temperature of the hot roller is 140 ℃, and the temperature of the cold roller is 50 ℃, and finally obtaining the ultrathin biaxial tension lithium battery microporous membrane.
Example 3
The preparation method comprises the steps of blending and extruding the ultra-polypropylene, the nucleating agent lithium benzoate, the antioxidant DLTP and the reinforcing agent organic modified nano montmorillonite by a double-screw extruder to prepare ultra-polypropylene particles with the content of β crystal form nucleating agent of 0.05 wt%, wherein the temperature of each section of the screw is 190 ℃ in a first zone, 190 ℃ in a second zone, 215 ℃ in a third zone, 235 ℃ in a fourth zone, 235 ℃ in a fifth zone, 235 ℃ in a sixth zone, 235 ℃ in a seventh zone, 235 ℃ in an eighth zone, 235 ℃ in a ninth zone, 235 ℃ in a tenth zone, 235 ℃ in a machine head, the speed of the extruder is 400rpm/min, the speed of the filler of a main feeder is 40rpm/min, and the master batch with the speed of the filler of an auxiliary.
Then the ultra-polypropylene particles are extruded and cast by a single screw extruder to prepare thick sheets. The temperatures from the feed port to the die of the casting single-screw extruder were 175 ℃, 205 ℃, 215 ℃, 225 ℃, 235 ℃ and 235 ℃. The melt is processed by a 118 ℃ casting unit to form a casting sheet, and then secondary crystallization is carried out by a preheating unit, wherein the temperature of the preheating unit is 100 ℃, and the thickness of the casting sheet is 0.5 mm.
The method comprises the steps of longitudinal stretching and transverse stretching. The longitudinal stretching ratio and the transverse stretching ratio are both 10 times, and are similar to the wet stretching ratio. The longitudinal stretching temperature is 65 ℃, and the setting temperature is 100 ℃. The transverse stretching temperature is 110 ℃, and the setting temperature is 145 ℃.
The heat setting temperature is 90 ℃. Setting time is 5 min.
And then, drawing by a hot forming roller and a cold forming roller, wherein the temperature of the hot roller is 90 ℃, and the temperature of the cold roller is 20 ℃ to finally obtain the ultrathin biaxial tension lithium battery microporous membrane.
Example 4
The ultra-polypropylene, the nucleating agent lithium benzoate, the antioxidant DLTP and the reinforcing agent organic modified nano montmorillonite are blended and extruded by a double-screw extruder to prepare ultra-polypropylene particles with β crystal form nucleating agent content of 0.05 wt%, and the temperature of each section of the screw is 180 ℃ in a first zone, 195 ℃ in a second zone, 220 ℃ in a third zone, 235 ℃ in a fourth zone, 245 ℃ in a fifth zone, 245 ℃ in a sixth zone, 245 ℃ in a seventh zone, 245 ℃ in an eighth zone, 245 ℃ in a ninth zone, 245 ℃ in a tenth zone, 245 ℃ in a machine head, the speed of the extruder is 500rpm/min, the speed of the filler of a main feeder is 50rpm/min, and the master batch with the speed of the filler of an auxiliary feeder of 30rpm/min is granulated.
Then the ultra-polypropylene particles are extruded and cast by a single screw extruder to prepare thick sheets. The temperatures of the single screw extruder from the feed port to the die were 200 deg.C, 210 deg.C, 215 deg.C, 220 deg.C, 250 deg.C, and 250 deg.C, respectively. The melt is processed by a 118 ℃ casting unit to form a casting sheet, and then secondary crystallization is carried out by a preheating unit, wherein the temperature of the preheating unit is 130 ℃, and the thickness of the casting sheet is 0.5 mm.
The method comprises the steps of longitudinal stretching and transverse stretching. The longitudinal stretching ratio and the transverse stretching ratio are both 9 times, and are similar to the wet stretching ratio. The longitudinal stretching temperature is 80 ℃, and the setting temperature is 110 ℃. The transverse stretching temperature is 120 ℃, and the setting temperature is 165 ℃.
The heat-setting temperature is 110 ℃. Setting time is 10 min.
And then, drawing by a hot forming roller and a cold forming roller, wherein the temperature of the hot roller is 120 ℃, and the temperature of the cold roller is 40 ℃ to finally obtain the ultrathin biaxial tension lithium battery microporous membrane.
The thickness, porosity, air permeability and mechanical properties of the lithium battery diaphragm are tested, the results are shown in table 1, and table 1 shows the performance test results of the lithium battery microporous diaphragm.
Comparative example
The ultra-polypropylene, the nucleating agent lithium benzoate, the antioxidant DLTP and the reinforcing agent organic modified nano montmorillonite are blended and extruded by a double-screw extruder to prepare ultra-polypropylene particles with the content of β crystal form nucleating agent of 0.15 wt%, and the temperature of each section of the screw is 175 ℃ in a first zone, 185 ℃ in a second zone, 210 ℃ in a third zone, 230 ℃ in a fourth zone, 230 ℃ in a fifth zone, 230 ℃ in a sixth zone, 230 ℃ in a seventh zone, 230 ℃ in an eighth zone, 230 ℃ in a ninth zone, 230 ℃ in a tenth zone, 230 ℃ in a head, the speed of the extruder is 500rpm/min, the speed of the filler of a main feeder is 50rpm/min, and the master batch with the speed of the filler of an auxiliary feeder of 30rpm/min is.
Then the ultra-polypropylene particles are extruded and cast by a single screw extruder to prepare thick sheets. The temperatures from the feed port to the die of the casting single-screw extruder were 165 ℃, 200 ℃, 210 ℃, 220 ℃, 230 ℃ and 230 ℃, respectively. The melt is processed by a 118 ℃ casting unit to form a casting sheet, and then secondary crystallization is carried out by a preheating unit, wherein the temperature of the preheating unit is 140 ℃, and the thickness of the casting sheet is 0.5 mm.
The method comprises the steps of longitudinal stretching and transverse stretching. The longitudinal stretching ratio and the transverse stretching ratio are both 4 times, and are similar to the wet stretching ratio. The longitudinal stretching temperature is 108 ℃, and the setting temperature is 118 ℃. The transverse stretching temperature is 130 ℃, and the setting temperature is 145 ℃.
The heat setting temperature is 153 ℃, and the setting time is 20 min.
And then, drawing by a hot forming roller and a cold forming roller, wherein the hot roller temperature is 110 ℃, and the cold roller temperature is 35 ℃ to finally obtain the ultrathin biaxial tension lithium battery microporous membrane.
The thickness, porosity, air permeability and mechanical properties of the lithium battery diaphragm are tested, the results are shown in table 1, and table 1 shows the performance test results of the lithium battery microporous diaphragm.
TABLE 1 Performance test results for microporous membranes of lithium batteries
In the above embodiment: the percentage ratios used, not specifically noted, are mass (weight) percentage ratios (wt% is mass percentage); the proportions used, not specifically noted, are mass (weight) proportions; the parts by weight may all be kilograms or tons.
In the above embodiment: the technological parameters (temperature, time, concentration, etc.) and the dosage values of the components in each step are within the range, and any point can be applied
The above-described aspects may be implemented individually or in various combinations, and such variations are within the scope of the present invention.
In this document, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that an 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 article or apparatus. Without further limitation, an element defined by the phrase "comprising … …" does not exclude the presence of additional like elements in the article or device comprising the element.
The above embodiments are merely to illustrate the technical solutions of the present invention and not to limit the present invention, and the present invention has been described in detail with reference to the preferred embodiments. It will be understood by those skilled in the art that various modifications and equivalent arrangements may be made without departing from the spirit and scope of the present invention and it should be understood that the present invention is to be covered by the appended claims.
Claims (10)
1. A preparation method of a lithium battery diaphragm is characterized by comprising the following steps:
a. blending and extruding the ultra-polypropylene, the β crystal form nucleating agent, the antioxidant and the reinforcing agent at high temperature by an extruding device, and further cooling and dicing the extruded product to obtain α crystal form ultra-polypropylene particles;
b. blending and extruding the α crystal form polypropylene particles at high temperature, and sequentially passing the extruded product through a die head and a casting sheet unit to obtain a casting sheet;
c. crystallizing the cast sheet through a heat treatment unit;
d. sequentially carrying out longitudinal stretching heat setting treatment and transverse stretching heat setting treatment on the crystallized casting sheet by using biaxial stretching equipment;
e. and sequentially carrying out heat setting and cold setting on the cast sheet subjected to transverse stretching and heat setting treatment to obtain the biaxial stretching lithium battery microporous membrane.
2. The method for preparing a lithium battery separator as claimed in claim 1, wherein the molecular weight of the ultra-polypropylene is 30 to 120 ten thousand, the molecular weight distribution is more than 8, the melt index is 2.0 to 4.0g/10min, and the isotacticity is more than 95%.
3. The method for preparing a lithium battery diaphragm as claimed in claim 1, wherein the β crystal form nucleating agent is a carboxylate nucleating agent, and the antioxidant is DLTP.
4. As claimed in claim 1The above-mentionedThe preparation method of the lithium battery diaphragm is characterized in that the mass ratio of the ultra-polypropylene to the β crystal form nucleating agent is 85-95: 1, the mass ratio of the ultra-polypropylene to the antioxidant is 75-95: 1, and the mass ratio of the ultra-polypropylene to the reinforcing agent is 80-95: 1.
5. As claimed in claim 1The above-mentionedThe preparation method of the lithium battery diaphragm is characterized in that the temperature of each section of the screw is 170-190 ℃ in the first zone, 190-215 ℃ in the second zone, 215-235 ℃ in the third zone, 235-280 ℃ in the fourth zone, 235-280 ℃ in the fifth zone, 235-280 ℃ in the sixth zone, 235-280 ℃ in the seventh zone, 235-280 ℃ in the eighth zone, 235-280 ℃ in the ninth zone, 235-280 ℃ in the tenth zone, 235-280 ℃ in the head temperature, and the extrusion speed of the extrusion device is 400-700 rpm/min.
6. As claimed in claim 1The above-mentionedThe preparation method of the lithium battery diaphragm is characterized in that the temperature of each section of a screw rod is 175-215 ℃, 205-215 ℃, 215-225 ℃, 225-235 ℃, 235-265 ℃ and the temperature of a die head is 225-265 ℃ in sequence when the extrusion device extrudes, and the extrusion speed of the extrusion device is 20-45 rpm/min.
7. As claimed in claim 1The above-mentionedThe preparation method of the lithium battery diaphragm is characterized in that the temperature of the heat setting step is 90-140 ℃, and the temperature of the cold setting step is 20-50 ℃.
8. A kit as claimed in any one of claims 1 to 7The above-mentionedThe preparation method of the lithium battery diaphragm is characterized in that the temperature of the casting roller is 100-140 ℃, and the temperature of the heat treatment unit is 100-140 ℃.
9. As claimed in claim 8The above-mentionedPreparation of lithium battery diaphragmA method, characterized in that in step d: the total ratio of longitudinal stretching is 3-11, the stretching temperature is 65-115 ℃, and the heat setting temperature is 90-120 ℃; the total rate of transverse stretching is 3-11, the stretching temperature is 110-135 ℃, and the setting temperature is 145-180 ℃.
10. As claimed in claim 8The above-mentionedThe preparation method of the lithium battery diaphragm is characterized in that the extrusion device comprises a main feeder and an auxiliary feeder, the main feeder is added with the ultra-polypropylene, the auxiliary feeder is added with the β crystal form nucleating agent, the antioxidant and the reinforcing agent, the filling speed of the main feeder is 40-80 rpm/min, and the filling speed of the auxiliary feeder is 15-40 rpm/min.
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| CN112259904A (en) * | 2020-09-28 | 2021-01-22 | 河北金力新能源科技股份有限公司 | High-strength low-shrinkage lithium ion battery diaphragm and preparation method thereof |
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| CN113067101B (en) * | 2021-03-19 | 2022-07-05 | 江苏厚生新能源科技有限公司 | High-rigidity lithium ion battery diaphragm and preparation method thereof |
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| CN114393853B (en) * | 2021-12-24 | 2024-04-09 | 武汉中兴创新材料技术有限公司 | Preparation method of polypropylene microporous membrane, polypropylene microporous membrane and application of polypropylene microporous membrane |
| CN115340725A (en) * | 2022-08-18 | 2022-11-15 | 浙江南洋华诚科技有限公司 | High-tensile-strength polypropylene film for lithium battery current collector and preparation method thereof |
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