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CN113067097A - A kind of lithium ion battery separator paper and preparation method thereof - Google Patents

A kind of lithium ion battery separator paper and preparation method thereof Download PDF

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Publication number
CN113067097A
CN113067097A CN202110212114.2A CN202110212114A CN113067097A CN 113067097 A CN113067097 A CN 113067097A CN 202110212114 A CN202110212114 A CN 202110212114A CN 113067097 A CN113067097 A CN 113067097A
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lithium ion
ion battery
slurry
battery separator
separator paper
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刘泽华
王慧
欧章明
薛奎
王高升
窦文芳
池凯
石爽
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Shanghai Yike New Material Technology Co ltd
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Tianjin University of Science and Technology
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • 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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  • General Chemical & Material Sciences (AREA)
  • Cell Separators (AREA)

Abstract

本发明公开了一种锂离子电池隔膜纸，其主要成分包括酚醛纤维、芳纶沉析纤维和植物纤维。同时，本发明还公开了所述锂离子电池隔膜纸的制备方法。本发明锂离子电池隔膜纸具有优异的阻燃、耐高温性能，克服了现有聚烯烃类电池隔膜纸不耐高温、孔隙率低等缺点，同时可以通过调整纤维配比和工艺条件来满足不同的隔膜要求。The invention discloses a lithium ion battery separator paper, the main components of which include phenolic fiber, aramid fiber and plant fiber. Meanwhile, the invention also discloses a preparation method of the lithium ion battery separator paper. The lithium ion battery separator paper of the invention has excellent flame retardancy and high temperature resistance, overcomes the shortcomings of the existing polyolefin battery separator paper, such as high temperature resistance and low porosity, and can meet different requirements by adjusting the fiber ratio and process conditions. diaphragm requirements.

Description

Lithium ion battery diaphragm paper and preparation method thereof
The technical field is as follows:
the invention relates to the technical field of battery diaphragm paper, in particular to lithium ion battery diaphragm paper and a preparation method thereof.
Background art:
the lithium ion battery consists of a positive electrode cover, a negative electrode cover, a positive electrode, a negative electrode, an electrolyte and a diaphragm. The diaphragm is the most important component in the battery and is used for separating the positive electrode and the negative electrode of the battery and preventing the positive electrode and the negative electrode from contacting to generate short circuit; in addition, when electrochemical reaction occurs, a channel is provided for ion transmission, and current is formed. The superiority and inferiority of the battery separator directly affect the capacity, cycle performance and safety performance of the battery, and thus the separator must have insulation properties, good mechanical strength, high porosity, and excellent electrolyte wettability and thermal stability.
The lithium ion battery diaphragm which is commercially available at present is mainly a polyolefin diaphragm, and the diaphragm has good chemical stability and mechanical strength and a mature manufacturing process. However, the diaphragm has low porosity and poor electrolyte wettability, so that the ion transmission performance is poor, the battery is slowly charged and discharged, and the cycle service life is shortened. In addition, the thermal shrinkage rate of the polyolefin diaphragm is high at high temperature, when the battery is discharged at high power, overcharged or violently impacted, the local heat of the battery reaches the melting point of the diaphragm, the diaphragm is melted to enable the positive electrode and the negative electrode to be in direct contact, the battery can catch fire or explode, and great potential safety hazards exist. Therefore, it is very important to find raw materials and process conditions with strong thermal stability and good electrolyte wettability to prepare the battery separator.
The invention content is as follows:
in view of the above, the invention provides the lithium ion battery separator paper and the preparation method thereof, and the separator paper prepared by the method has more excellent comprehensive performance, and has the characteristics of excellent high temperature resistance and flame retardant property, high porosity and good electrolyte wettability.
The technical scheme of the invention is as follows:
the lithium ion battery diaphragm paper is prepared by mixing and papermaking the following sizing agent, polyoxyethylene and tributyl phosphate in parts by weight:
Figure BDA0002951812810000021
wherein the slurry A is prepared by cutting and defibering phenolic fibers; the slurry B is prepared by defibering and pulping aramid fibrid, the beating degree is 15-40 DEG SR, and the fiber length is not more than 1.8 mm; the slurry C is prepared by defibering and pulping plant fibers, and the beating degree of the slurry C is 40-90 DEG SR.
Further, the quantitative ratio of the lithium ion battery separator paper is 25g/m2～60g/m2The thickness is 40-100 μm, the porosity is 40-80%, and the average pore diameter is 0.5-6 μm.
Preferably, the plant fiber is bleached softwood fiber or unbleached softwood fiber produced by a chemical, semi-chemical or chemimechanical process.
On the basis, the invention further provides a preparation method of the lithium ion battery separator paper, which comprises the following steps:
1) mixing, namely mixing the slurry A, the slurry B and the slurry C to obtain mixed slurry, and fluffing and dispersing the mixed slurry uniformly; wherein the slurry A is prepared by cutting and defibering phenolic fibers; the slurry B is prepared by defibering and pulping aramid fibrid, the beating degree is 15-40 DEG SR, and the fiber length is not more than 1.8 mm; the pulp C is prepared by defibering and pulping plant fibers, and the beating degree of the pulp C is 40-90 DEG SR;
2) and (3) papermaking, namely papermaking the uniformly dispersed mixed slurry to obtain paper sheets, thus obtaining the lithium ion battery diaphragm paper.
Further, the preparation method of the lithium ion battery separator paper provided by the invention further comprises the following steps after the paper making treatment in the step 2): and 3) dipping, namely dipping the lithium ion battery diaphragm paper obtained by papermaking in a phenolic resin solution, and then drying.
Further, the preparation method of the lithium ion battery separator paper provided by the invention further comprises the following steps after the dipping treatment in the step 3): step 4), hot pressing, namely, carrying out hot pressing treatment on the lithium ion battery diaphragm paper treated in the step 3) in a flat vulcanizing machine: the hot pressing temperature is 130-180 ℃, the hot pressing pressure is 3-5 MPa, and the hot pressing time is 2-5 min.
Preferably, in the slurry mixing process of the step 1), adding a proper amount of polyethylene oxide into the mixed slurry; in the papermaking process of the step 2), a proper amount of tributyl phosphate is added into the mixed slurry.
Preferably, the phenolic resin solution used for the impregnation treatment in step 3) is alcohol-soluble phenolic resin, the solvent is methanol, and the mass percentage concentration of the solution is 5-10%.
Preferably, the paper making process of the mixed slurry in the step 2) comprises: wet papermaking and vacuum drying treatment after papermaking are adopted, wherein the temperature of the vacuum drying treatment after papermaking is 80-105 ℃, and the drying time is 6-10 min; the dipping time in the step 3) is 20-60 s, the drying mode after dipping is oven drying, and the drying time is 5-10 min.
Preferably, the plant fiber is bleached softwood fiber or unbleached softwood fiber produced by a chemical, semi-chemical or chemimechanical process.
The lithium ion battery diaphragm paper has excellent flame retardant and high temperature resistance, overcomes the defects of poor electrolyte wettability, low porosity and the like of the existing polyolefin battery diaphragm paper, and can meet different diaphragm requirements by adjusting the fiber ratio and process conditions.
Description of the drawings:
FIG. 1 is a 500 scanning electron micrograph of a portion of a product according to an embodiment of the present invention; a, B, C, D corresponds to the lithium ion battery separator paper products prepared in example 6, example 3, example 2 and example 1 respectively.
Fig. 2 is a result of a flame retardant performance test of products according to various embodiments of the present invention, wherein 6 products correspond to the products prepared in embodiments 1, 2, 3, 4, 5, and 6 in sequence from left to right in the figure.
Fig. 3 is a thermal shrinkage test result of products of each example of the invention and a conventional lithium ion battery separator on the market, wherein 7 products correspond to the lithium ion battery separators of examples 1, 2, 3, 4, 5 and 6 of the invention from left to right in sequence.
The specific implementation mode is as follows:
the technical solution and effects of the present invention will be further described with reference to the following embodiments and drawings.
Example 1
In the embodiment, the lithium ion battery separator paper is prepared by mixing and papermaking the following slurry, polyethylene oxide and tributyl phosphate in parts by weight:
Figure BDA0002951812810000041
wherein, the slurry A is prepared by cutting phenolic fiber and then defibering the cut phenolic fiber by a standard defibering device; the sizing agent B is prepared by defibering aramid fibrid by a standard defibering device and further pulping by a groove type pulping machine or a PFI pulping machine, wherein the beating degree is 35 DEG SR and the fiber length is less than 1.8 mm; the pulp C is prepared by defibering bleached softwood fibers by a standard defibering device and further fibrillating the bleached softwood fibers by a trough type beater or a PFI beater, wherein the beating concentration is controlled to be 10 percent, so that the beating degree of the finally obtained pulp C is 80 DEG SR.
The lithium ion battery separator paper in the embodiment is prepared by the following steps:
1) mixing, namely mixing the slurry A, the slurry B and the slurry C to obtain mixed slurry, adding polyoxyethylene into the mixed slurry, and then untwining and uniformly dispersing the mixed slurry.
2) And (3) papermaking, namely performing papermaking treatment on the mixed slurry: adopting a wet papermaking method, and adding tributyl phosphate into the mixed slurry in the papermaking process; and (3) carrying out vacuum drying treatment after papermaking, wherein the temperature of the vacuum drying treatment is 80 ℃, and the drying time is 10 min.
In the above-described step 1) and step 2), the addition amounts of the slurry A, the slurry B, the slurry C, the polyethylene oxide and the tributyl phosphate were determined with reference to the parts by weight given in the first paragraph of this example.
3) And (3) dipping the lithium ion battery diaphragm paper manufactured by the paper making in the step 2) in 7% (mass percent) of phenolic resin solution for 20s, and then drying in an oven for 5 min. The phenolic resin solution used in the step adopts alcohol-soluble phenolic resin, and the solvent is methanol.
4) Hot pressing, namely, carrying out hot pressing treatment on the lithium ion battery diaphragm paper subjected to the dipping treatment in the step 3) in a flat vulcanizing machine: the hot pressing temperature is 180 ℃, the hot pressing pressure is 3MPa, and the hot pressing time is 3 min. And preparing the lithium ion battery diaphragm paper.
Example 2
In the embodiment, the lithium ion battery separator paper is prepared by mixing and papermaking the following slurry, polyethylene oxide and tributyl phosphate in parts by weight:
Figure BDA0002951812810000051
Figure BDA0002951812810000061
wherein, the slurry A is prepared by cutting phenolic fiber and then defibering the cut phenolic fiber by a standard defibering device; the sizing agent B is prepared by defibering aramid fibrid by a standard defibering device and further pulping by a groove type pulping machine or a PFI pulping machine, wherein the beating degree is 33 DEG SR and the fiber length is less than 1.8 mm; the pulp C is prepared by defibering bleached softwood fibers by a standard defibering device and further fibrillating the bleached softwood fibers by a trough type beater or a PFI beater, wherein the beating concentration is controlled to be 10 percent, so that the beating degree of the finally obtained pulp C is 75 DEG SR.
The lithium ion battery separator paper in the embodiment is prepared by the following steps:
1) mixing, namely mixing the slurry A, the slurry B and the slurry C to obtain mixed slurry, adding polyoxyethylene into the mixed slurry, and then untwining and uniformly dispersing the mixed slurry.
2) And (3) papermaking, namely performing papermaking treatment on the mixed slurry: adopting a wet papermaking method, and adding tributyl phosphate into the mixed slurry in the papermaking process; and (3) carrying out vacuum drying treatment after papermaking, wherein the temperature of the vacuum drying treatment is 100 ℃, and the drying time is 10 min.
In the above-described step 1) and step 2), the addition amounts of the slurry A, the slurry B, the slurry C, the polyethylene oxide and the tributyl phosphate were determined with reference to the parts by weight given in the first paragraph of this example.
3) Dipping, dipping the lithium ion battery diaphragm paper manufactured by the paper making in the step 2) in 10% (mass percent) of phenolic resin solution for 40s, and then drying in an oven for 10 min. The phenolic resin solution used in the step adopts alcohol-soluble phenolic resin, and the solvent is methanol.
4) Hot pressing, namely, carrying out hot pressing treatment on the lithium ion battery diaphragm paper subjected to the dipping treatment in the step 3) in a flat vulcanizing machine: hot pressing temperature 150 deg.C, hot pressing pressure 5MPa, and hot pressing time 5 min. And preparing the lithium ion battery diaphragm paper.
Example 3
In the embodiment, the lithium ion battery separator paper is prepared by mixing and papermaking the following slurry, polyethylene oxide and tributyl phosphate in parts by weight:
Figure BDA0002951812810000071
wherein, the slurry A is prepared by cutting phenolic fiber and then defibering the cut phenolic fiber by a standard defibering device; the sizing agent B is prepared by defibering aramid fibrid by a standard defibering device and further pulping by a groove type pulping machine or a PFI pulping machine, wherein the beating degree is 36 DEG SR and the fiber length is less than 1.8 mm; the pulp C is prepared by defibering bleached softwood fibers by a standard defibering device and further fibrillating the bleached softwood fibers by a groove type beater or a PFI beater, wherein the beating concentration is controlled to be 10 percent, so that the beating degree of the finally obtained pulp C is 81 DEG SR.
The lithium ion battery separator paper in the embodiment is prepared by the following steps:
1) mixing, namely mixing the slurry A, the slurry B and the slurry C to obtain mixed slurry, adding polyoxyethylene into the mixed slurry, and then untwining and uniformly dispersing the mixed slurry.
2) And (3) papermaking, namely performing papermaking treatment on the mixed slurry: adopting a wet papermaking method, and adding tributyl phosphate into the mixed slurry in the papermaking process; and (3) carrying out vacuum drying treatment after papermaking, wherein the temperature of the vacuum drying treatment is 105 ℃, and the drying time is 6 min.
In the above-described step 1) and step 2), the addition amounts of the slurry A, the slurry B, the slurry C, the polyethylene oxide and the tributyl phosphate were determined with reference to the parts by weight given in the first paragraph of this example.
3) Dipping, dipping the lithium ion battery diaphragm paper manufactured by the paper making in the step 2) in 5% (mass percent) of phenolic resin solution for 60s, and then drying in an oven for 10 min. The phenolic resin solution used in the step adopts alcohol-soluble phenolic resin, and the solvent is methanol.
4) Hot pressing, namely, carrying out hot pressing treatment on the lithium ion battery diaphragm paper subjected to the dipping treatment in the step 3) in a flat vulcanizing machine: the hot pressing temperature is 160 ℃, the hot pressing pressure is 3MPa, and the hot pressing time is 4 min. And preparing the lithium ion battery diaphragm paper.
Example 4
In the embodiment, the lithium ion battery separator paper is prepared by mixing and papermaking the following slurry, polyethylene oxide and tributyl phosphate in parts by weight:
Figure BDA0002951812810000081
wherein, the slurry A is prepared by cutting phenolic fiber and then defibering the cut phenolic fiber by a standard defibering device; the sizing agent B is prepared by defibering aramid fibrid by a standard defibering device and further pulping by a groove type pulping machine or a PFI pulping machine, wherein the beating degree is 35 DEG SR and the fiber length is less than 1.8 mm; the pulp C is prepared by defibering bleached softwood fibers by a standard defibering device and further fibrillating the bleached softwood fibers by a trough type beater or a PFI beater, wherein the beating concentration is controlled to be 10 percent, so that the beating degree of the finally obtained pulp C is 80 DEG SR.
The lithium ion battery separator paper in the embodiment is prepared by the following steps:
1) and mixing, namely mixing the slurry A, the slurry B and the slurry C to obtain mixed slurry, and then fluffing and dispersing the mixed slurry uniformly.
2) And (3) papermaking, namely performing papermaking treatment on the mixed slurry: adopting a wet method for manufacturing paper; and (3) carrying out vacuum drying treatment after papermaking, wherein the temperature of the vacuum drying treatment is 90 ℃, and the drying time is 10 min.
In the above steps 1) and 2), the amounts of slurry a, slurry B and slurry C to be added were determined with reference to the parts by weight given in the first paragraph of this example.
3) And (3) dipping the lithium ion battery diaphragm paper manufactured by the paper making in the step 2) in 7% (mass percent) of phenolic resin solution for 30s, and then drying in an oven for 8 min. The phenolic resin solution used in the step adopts alcohol-soluble phenolic resin, and the solvent is methanol.
4) Hot pressing, namely, carrying out hot pressing treatment on the lithium ion battery diaphragm paper subjected to the dipping treatment in the step 3) in a flat vulcanizing machine: the hot pressing temperature is 180 ℃, the hot pressing pressure is 3MPa, and the hot pressing time is 2 min. And preparing the lithium ion battery diaphragm paper.
Example 5
In the embodiment, the lithium ion battery separator paper is prepared by mixing and papermaking the following slurry, polyethylene oxide and tributyl phosphate in parts by weight:
Figure BDA0002951812810000091
wherein, the slurry A is prepared by cutting phenolic fiber and then defibering the cut phenolic fiber by a standard defibering device; the sizing agent B is prepared by defibering aramid fibrid by a standard defibering device and further pulping by a groove type pulping machine or a PFI pulping machine, wherein the beating degree is 35 DEG SR and the fiber length is less than 1.8 mm; the pulp C is prepared by defibering bleached softwood fibers by a standard defibering device and further fibrillating the bleached softwood fibers by a trough type beater or a PFI beater, wherein the beating concentration is controlled to be 10 percent, so that the beating degree of the finally obtained pulp C is 85 DEG SR.
The lithium ion battery separator paper in the embodiment is prepared by the following steps:
1) mixing, namely mixing the slurry A, the slurry B and the slurry C to obtain mixed slurry, adding polyoxyethylene into the mixed slurry, and then untwining and uniformly dispersing the mixed slurry.
2) And (3) papermaking, namely performing papermaking treatment on the mixed slurry: adopting a wet method for manufacturing paper; and (3) carrying out vacuum drying treatment after papermaking, wherein the temperature of the vacuum drying treatment is 90 ℃, and the drying time is 10 min.
In the above-mentioned step 1) and step 2), the addition amounts of the slurry A, the slurry B, the slurry C and the polyethylene oxide were determined with reference to the parts by weight given in the first stage of this example.
3) And (3) dipping the lithium ion battery diaphragm paper manufactured by the paper making in the step 2) in 7% (mass percent) of phenolic resin solution for 30s, and then drying in an oven for 8 min. The phenolic resin solution used in the step adopts alcohol-soluble phenolic resin, and the solvent is methanol.
4) Hot pressing, namely, carrying out hot pressing treatment on the lithium ion battery diaphragm paper subjected to the dipping treatment in the step 3) in a flat vulcanizing machine: the hot pressing temperature is 180 ℃, the hot pressing pressure is 3MPa, and the hot pressing time is 3 min. And preparing the lithium ion battery diaphragm paper.
Example 6
In the embodiment, the lithium ion battery separator paper is prepared by mixing and papermaking the following slurry, polyethylene oxide and tributyl phosphate in parts by weight:
Figure BDA0002951812810000101
wherein, the slurry A is prepared by cutting phenolic fiber and then defibering the cut phenolic fiber by a standard defibering device; the sizing agent B is prepared by defibering aramid fibrid by a standard defibering device and further pulping by a groove type pulping machine or a PFI pulping machine, wherein the beating degree is 35 DEG SR and the fiber length is less than 1.8 mm; the pulp C is prepared by defibering bleached softwood fibers by a standard defibering device and further fibrillating the bleached softwood fibers by a trough type beater or a PFI beater, wherein the beating concentration is controlled to be 10 percent, so that the beating degree of the finally obtained pulp C is 80 DEG SR.
The lithium ion battery separator paper in the embodiment is prepared by the following steps:
1) and mixing, namely mixing the slurry A, the slurry B and the slurry C to obtain mixed slurry, and then fluffing and dispersing the mixed slurry uniformly.
2) And (3) papermaking, namely performing papermaking treatment on the mixed slurry: adopting a wet papermaking method, and adding tributyl phosphate into the mixed slurry in the papermaking process; and (3) carrying out vacuum drying treatment after papermaking, wherein the temperature of the vacuum drying treatment is 90 ℃, and the drying time is 10 min.
In the above-mentioned step 1) and step 2), the amounts of slurry a, slurry B, slurry C and tributyl phosphate added were determined with reference to the parts by weight given in the first paragraph of this example.
3) Dipping, dipping the lithium ion battery diaphragm paper manufactured by the paper making in the step 2) in 10% (mass percent) of phenolic resin solution for 60s, and then drying in an oven for 10 min. The phenolic resin solution used in the step adopts alcohol-soluble phenolic resin, and the solvent is methanol.
4) Hot pressing, namely, carrying out hot pressing treatment on the lithium ion battery diaphragm paper subjected to the dipping treatment in the step 3) in a flat vulcanizing machine: the hot pressing temperature is 180 ℃, the hot pressing pressure is 3MPa, and the hot pressing time is 3 min. And preparing the lithium ion battery diaphragm paper.
Example 7
The physical properties of the lithium ion battery separator paper obtained in the above 6 examples were measured, and the results are shown in table 1. Compared with the commercially available conventional lithium ion battery diaphragm material (the porosity is about 40 percent and the thermal shrinkage at 160 ℃ is about 28 percent), the lithium ion battery diaphragm paper obtained by 6 embodiments has the characteristics of stable thermal performance, high porosity, high liquid absorption rate and good electrolyte wettability, so that the lithium ion battery diaphragm paper has higher safety performance.
Table 1 physical property test results of products of examples of the present invention
Figure BDA0002951812810000121
FIG. 1 is a 500 scanning electron micrograph of a portion of a product according to an embodiment of the present invention. As can be seen from figure 1, the lithium ion battery diaphragm paper prepared by the method has the advantages of compact and uniform surface, high porosity, certain physical strength and good liquid retention capacity.
Fig. 2 is a result of a flame retardant performance test of products of various embodiments of the invention, and the determination method refers to GB/T14656-2009 "flame retardant paper and paperboard burning performance test method". As can be seen from the measurement results shown in FIG. 2, the average char length of each example was 115mm or less, and both the afterflame time and the ignition time in the course of the experiment were 0 s. The lithium ion battery diaphragm paper prepared by the invention has excellent flame retardant property.
FIG. 3 shows the results of the thermal shrinkage test of the products of the examples of the present invention and the conventional lithium ion battery separator on the market, wherein the test condition is that the separator is continuously heated for 1h at 160 ℃. The result shows that the conventional lithium ion battery diaphragm sold in the market is obviously deformed and shrunk after being heated, and 6 lithium ion battery diaphragm paper products prepared by the invention basically keep unchanged and show excellent high-temperature resistance.

Claims (10)

1.一种锂离子电池隔膜纸，其特征在于：由如下重量份的浆料、聚氧化乙烯以及磷酸三丁酯经混合、抄造制得：1. a lithium ion battery separator paper, is characterized in that: by the slurry of following weight portion, polyoxyethylene and tributyl phosphate, make through mixing, copying:
Figure FDA0002951812800000011
Figure FDA0002951812800000011
 其中，所述浆料A由酚醛纤维经切短、疏解后制得；所述浆料B由芳纶沉析纤维经疏解、打浆后制得，其叩解度为15～40°SR且纤维长度不超过1.8mm；所述浆料C由植物纤维经疏解、打浆后制得，其叩解度为40～90°SR。Wherein, the slurry A is prepared from phenolic fibers after being chopped and dredged; the slurry B is prepared from aramid precipitation fibers after decoupling and beating, and the beating degree is 15-40°SR and the fiber length is No more than 1.8mm; the pulp C is prepared by dissolving and beating plant fibers, and its beating degree is 40-90°SR. 2.根据权利要求1所述的锂离子电池隔膜纸，其特征在于：所述锂离子电池隔膜纸的定量为25g/m2～60g/m2，厚度为40～100μm，孔隙率为40％～80％，平均孔径为0.5μm～6μm。2 . The lithium ion battery separator paper according to claim 1 , wherein the lithium ion battery separator paper has a quantitative weight of 25g/m 2 to 60g/m 2 , a thickness of 40 to 100 μm, and a porosity of 40%. 3 . ~80%, the average pore size is 0.5μm ~ 6μm. 3.根据权利要求1或2所述的锂离子电池隔膜纸，其特征在于：所述植物纤维为化学法、半化学法或化学机械法制得的漂白针叶木纤维或未漂针叶木纤维。3. The lithium ion battery separator paper according to claim 1 or 2, wherein the plant fiber is a bleached softwood fiber or an unbleached softwood fiber obtained by a chemical method, a semi-chemical method or a chemical-mechanical method. 4.一种锂离子电池隔膜纸的制备方法，其特征在于包括如下步骤：4. a preparation method of lithium ion battery separator paper, is characterized in that comprising the steps: 1)混合，将浆料A、浆料B和浆料C进行混合得到混合浆料，将所述混合浆料疏解分散均匀；其中，所述浆料A由酚醛纤维经切短、疏解后制得；所述浆料B由芳纶沉析纤维经疏解、打浆后制得，其叩解度为15～40°SR且纤维长度不超过1.8mm；所述浆料C由植物纤维经疏解、打浆后制得，其叩解度为40～90°SR；1) Mixing, mixing slurry A, slurry B and slurry C to obtain a mixed slurry, and dispersing the mixed slurry uniformly; wherein, the slurry A is made of phenolic fibers after cutting and dispersing. Obtained; the slurry B is prepared from aramid fibrids after dispersing and beating, and its beating degree is 15-40°SR and the fiber length does not exceed 1.8 mm; the slurry C is prepared by dissolving and beating plant fibers After preparation, its beating degree is 40～90°SR; 2)抄造，将疏解分散均匀的所述混合浆料抄造成纸页，即得到锂离子电池隔膜纸。2) Papermaking, the dissolving and uniformly dispersed mixed slurry is formed into paper sheets, that is, lithium ion battery separator paper is obtained. 5.根据权利要求4所述的锂离子电池隔膜纸的制备方法，其特征在于：在所述步骤2)的抄造处理后还包括：步骤3)浸渍，将抄造得到的所述锂离子电池隔膜纸于酚醛树脂溶液中浸渍，之后进行干燥。5. The preparation method of lithium ion battery separator paper according to claim 4, characterized in that: after the papermaking process of the step 2), it further comprises: step 3) dipping, and the lithium ion battery separator obtained by the papermaking process The paper is dipped in a phenolic resin solution and then dried. 6.根据权利要求5所述的锂离子电池隔膜纸的制备方法，其特征在于：在所述步骤3)的浸渍处理后还包括：步骤4)热压，将经过所述步骤3)处理后的锂离子电池隔膜纸于平板硫化机中进行热压处理：热压温度130℃～180℃、热压压力3MPa～5Mpa、热压时间2min～5min。6. The preparation method of lithium ion battery separator paper according to claim 5, characterized in that: after the dipping treatment in the step 3), the method further comprises: step 4) hot pressing, after the treatment in the step 3) The lithium ion battery separator paper is hot-pressed in a flat vulcanizer: hot-pressing temperature 130℃～180℃, hot-pressing pressure 3MPa-5Mpa, hot-pressing time 2min-5min. 7.根据权利要求5或6所述的锂离子电池隔膜纸的制备方法，其特征在于：所述步骤1)的浆料混合过程中，还包括向所述混合浆料中加入适量聚氧化乙烯；所述步骤2)的抄造过程中，还包括向所述混合浆料中加入适量磷酸三丁酯。7. The preparation method of lithium ion battery separator paper according to claim 5 or 6, characterized in that: in the slurry mixing process of the step 1), it also comprises adding an appropriate amount of polyethylene oxide to the mixed slurry ; In the papermaking process of the step 2), it also includes adding an appropriate amount of tributyl phosphate to the mixed slurry. 8.根据权利要求7所述的锂离子电池隔膜纸的制备方法，其特征在于：所述步骤3)中用于浸渍处理的酚醛树脂溶液采用醇溶性酚醛树脂，溶剂为甲醇，溶液的质量百分比浓度为5％～10％。8. The preparation method of lithium ion battery separator paper according to claim 7, wherein the phenolic resin solution used for the impregnation treatment in the step 3) adopts alcohol-soluble phenolic resin, the solvent is methanol, and the mass percentage of the solution is The concentration is 5% to 10%. 9.根据权利要求8所述的锂离子电池隔膜纸的制备方法，其特征在于：所述步骤2)中对混合浆料的抄造处理包括：采用湿法抄造以及抄造后的真空干燥处理，其中抄造后真空干燥处理的温度为80℃～105℃，干燥时间为6min～10min；所述步骤3)中的浸渍时间为20s～60s，浸渍后的干燥方式为烘箱干燥，干燥时间为5min～10min。9 . The preparation method of lithium ion battery separator paper according to claim 8 , wherein the papermaking treatment of the mixed slurry in the step 2) comprises: adopting wet papermaking and vacuum drying after the papermaking, wherein The temperature of vacuum drying treatment after papermaking is 80°C～105°C, and the drying time is 6min～10min; the dipping time in the step 3) is 20s～60s, the drying method after dipping is oven drying, and the drying time is 5min～10min . 10.根据权利要求4、5、6、8、9中任意一项所述的锂离子电池隔膜纸的制备方法，其特征在于：所述植物纤维为化学法、半化学法或化学机械法制得的漂白针叶木纤维或未漂针叶木纤维。10. The preparation method of lithium ion battery separator paper according to any one of claims 4, 5, 6, 8, and 9, characterized in that: the plant fiber is obtained by chemical method, semi-chemical method or chemical mechanical method bleached softwood fibers or unbleached softwood fibers.
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CN114709560A (en) * 2022-04-15 2022-07-05 江南大学 A kind of lithium ion battery separator paper and preparation method thereof

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