CN111900312A - High-performance lithium battery diaphragm and preparation method thereof - Google Patents
High-performance lithium battery diaphragm and preparation method thereof Download PDFInfo
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D10/00—Physical treatment of artificial filaments or the like during manufacture, i.e. during a continuous production process before the filaments have been collected
- D01D10/06—Washing or drying
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/0007—Electro-spinning
- D01D5/0015—Electro-spinning characterised by the initial state of the material
- D01D5/003—Electro-spinning characterised by the initial state of the material the material being a polymer solution or dispersion
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/0007—Electro-spinning
- D01D5/0061—Electro-spinning characterised by the electro-spinning apparatus
- D01D5/0092—Electro-spinning characterised by the electro-spinning apparatus characterised by the electrical field, e.g. combined with a magnetic fields, using biased or alternating fields
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
- D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
- D01F8/10—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one other macromolecular compound obtained by reactions only involving carbon-to-carbon unsaturated bonds as constituent
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
- D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
- D01F8/16—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one other macromolecular compound obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds as constituent
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- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
- D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
- D04H1/4382—Stretched reticular film fibres; Composite fibres; Mixed fibres; Ultrafine fibres; Fibres for artificial leather
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- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/70—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres
- D04H1/72—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged
- D04H1/728—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged by electro-spinning
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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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- Manufacturing & Machinery (AREA)
- Dispersion Chemistry (AREA)
- Cell Separators (AREA)
Abstract
The invention discloses a lithium battery diaphragm which comprises high-performance resin Polybenzimidazole (PBI), polyethylene-lithium vinyl alcohol (EVOH-Li) and cellulose acetate @ boehmite. The invention provides a preparation method of a lithium battery diaphragm, which comprises the steps of preparing EVOH-Li/cellulose acetate @ boehmite and high-heat-resistant PBI/cellulose acetate @ boehmite spinning solutions, injecting the spinning solutions on a receiving device through an injector and the like by using a high-voltage electrostatic spinning device, and drying to obtain the lithium battery diaphragm. The high-voltage electrostatic spinning technology is adopted, and the obtained diaphragm has high porosity, excellent smoothness and cycle performance, high temperature resistance and other excellent performances.
Description
Technical Field
The invention relates to the technical field of lithium ion battery diaphragm materials, in particular to a lithium battery diaphragm and a preparation method thereof.
Background
With the development of new energy industry, the demand of battery diaphragm will be larger and larger in the future, and the requirements on the preparation technology and material selection of the diaphragm are also improved; the excellent performance of the lithium battery diaphragm, which is one of four major components of the lithium ion battery, directly affects the capacity, safety, cyclicity and other properties of the battery, such as the interface structure, internal resistance and the like of the battery. At present, most lithium battery diaphragms are still PP/PE and modified diaphragms thereof, and the problems of poor heat resistance of the diaphragms, low battery power and cycle rate and safety caused by low conductivity and mobility of the lithium ion battery diaphragms exist; therefore, the development of high-performance lithium battery separators has become a research focus and a hot spot in the lithium battery industry.
The materials and structures used by the lithium ion battery separator directly influence the performance of the lithium ion battery, and high-voltage electrostatic spinning in the current technology for preparing the separator attracts much attention of researchers, among which, the electrospun fiber membrane is particularly favored by the researchers, and the research shows that the electrospun fiber membrane still needs to be improved in the aspects of porosity, liquid absorption rate and ion mobility, and the improvement of the heat resistance and flame retardance of the separator is a problem which needs to be solved urgently from the aspect of safety.
Disclosure of Invention
In order to overcome the defects, the invention aims to provide a lithium battery diaphragm which is high-temperature resistant, good in dimensional stability, high-efficiency and flame-retardant and has high cycle rate and a preparation method thereof.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows, and the preparation method of the lithium battery diaphragm comprises the following steps:
(1) preparation of lithium polyethylene-vinylalcohol (EVOH-Li);
(2) preparing an EVOH-Li and Polybenzimidazole (PBI) spinning solution;
(3) preparing cellulose acetate @ boehmite nanoparticles;
(4) preparing a composite spinning solution;
(5) carrying out high-voltage electrostatic spinning to obtain a fiber membrane;
(6) and (3) drying, namely placing the fiber membrane obtained in the previous step in an oven for drying to obtain the composite electrostatic spinning fiber membrane.
Preferably, the synthesizing EVOH-Li in the step (1) comprises: firstly, respectively dissolving EVOH and lithium tert-butoxide in DMAc, then uniformly mixing the EVOH and the lithium tert-butoxide, adding a certain amount of 1, 3-propane sultone after the EVOH and the lithium tert-butoxide fully react, pouring the reaction product into water, repeatedly washing and drying to obtain EVOH-Li.
Preferably, the synthesizing EVOH-Li in the step (1) comprises: respectively adding 5-10 parts by mass of EVOH resin and 4-8 parts by mass of lithium tert-butoxide into 50 parts by mass of DMAc, stirring and dispersing to dissolve the EVOH resin and the lithium tert-butoxide, mixing the EVOH resin and the DMAc after dissolution, stirring and dispersing uniformly, adding 2-8 parts by mass of 1, 3-propane sultone into the mixture, stirring, pouring reactants into 100 parts of water after the reactants are fully dissolved, fully washing until solids are separated out, collecting and drying to obtain EVOH-Li solids.
Preferably, the preparation of the EVOH-Li and PBI spinning solution in the step (2) comprises the steps of taking 10-15 parts by mass of EVOH-Li solid, adding 15-30 parts by mass of DMAc, uniformly stirring to prepare the EVOH-Li spinning solution, taking 1-5 parts by mass of soluble PBI solid, adding 10-20 parts by mass of DMAc, and uniformly stirring to prepare the PBI spinning solution.
Preferably, said step (3) of preparing cellulose acetate @ boehmite nanoparticles comprises: taking 3-9 parts of cellulose acetate solution and 0.2-0.8 part of boehmite particles by mass fraction, adding 0.01-0.05 part of surfactant, and uniformly stirring to prepare the cellulose acetate @ boehmite particles.
Preferably, the surfactant in step (3) is one or more selected from sodium stearyl sulfate, sodium stearate and nonionic surfactants.
Preferably, the step (4) of preparing the composite spinning solution comprises: respectively taking 10-15 parts of EVOH-Li spinning solution and PBI spinning solution by mass fraction, adding 3-6 parts of cellulose acetate @ boehmite particles, and uniformly mixing to obtain the EVOH-Li/cellulose acetate @ boehmite spinning solution and the high-heat-resistant PBI/cellulose acetate @ boehmite spinning solution.
Further, the electrostatic spinning device comprises a direct-current voltage power supply, an injection pump, an injection needle and a receiving device, the spinning solution is contained in the injector, the injection needle is installed on the injection pump, the needle is connected with the positive electrode of the high-voltage power supply, the receiving device is connected with the negative electrode of the high-voltage generator for electrospinning, the fiber membrane obtained through electrostatic spinning is received on an aluminum foil receiving table and solidified, and the electrostatic spinning fiber membrane is obtained.
Preferably, in the step (5), the distance between the needle of the syringe and the upper surface of the receiving platform is 10-25 cm, and the applied voltage is 8-25 KV.
Preferably, in the step (5), the advancing speed of the syringe is 0.2-0.5 ml/h.
Preferably, in the step (5), the spinning temperature interval is 25-30 ℃, and the humidity is 25-35%.
Preferably, in the step (6), the drying temperature is 60-75 ℃, and the drying time is 2-6 h.
The lithium battery diaphragm and the preparation method thereof have the beneficial effects that: the ionic polymer is used as a diaphragm raw material to improve the ion density; spinning by using high-performance resin and performing post-crosslinking treatment on the spun fiber; high-temperature-resistant nanoparticles are added into the spinning matrix liquid to improve the dimensional stability of the fiber membrane; the novel porous fiber membrane preparation method-high-voltage electrostatic spinning is adopted as a support technology to jointly prepare the high-performance battery diaphragm. The diaphragm prepared by the method is flat, adjustable in thickness and high in porosity, can contain more electrolyte and provides more channels for transmission of ions in the diaphragm.
Detailed Description
The following detailed description of specific embodiments of the present invention is provided to illustrate and explain the present invention and to be understood not to limit the present invention.
The preparation method of the lithium battery diaphragm comprises the following steps:
(1) preparing EVOH-Li and PBI spinning solution: firstly, weighing 5g of EVOH and 4g of lithium tert-butoxide, respectively putting the EVOH and the lithium tert-butoxide into a three-neck flask, adding 50g of DMAc into an electric heating constant-temperature water bath kettle at 65 ℃ to dissolve the DMAc completely, pouring the lithium tert-butoxide solution into the three-neck flask filled with the EVOH solution, continuously stirring for four hours, adding 2g of 1, 3-propane sulfonic acid lactone after the lithium tert-butoxide fully reacts, and continuously stirring for 4 hours; and preparing the EVOH-Li and PBI spinning solution, namely taking 10g of EVOH-Li solid, adding 25g of DMAc into the EVOH-Li solid, uniformly stirring to prepare the EVOH-Li spinning solution, taking 3g of soluble PBI solid, adding 15g of DMAc into the soluble PBI solid, and uniformly stirring to prepare the PBI spinning solution.
(2) Preparation of cellulose acetate @ boehmite nanoparticles: preparing cellulose acetate @ boehmite nanoparticles comprises: taking 3g of cellulose acetate solution and 0.4g of boehmite particles, adding 0.01g of sodium octadecyl sulfate, and uniformly stirring in an electric heating constant-temperature water bath kettle at 50 ℃ to prepare the cellulose acetate @ boehmite particles.
(3) Preparing a composite spinning solution: respectively taking 10g of EVOH-Li spinning solution and PBI spinning solution, adding 3g of cellulose acetate @ boehmite particles, and uniformly stirring in an electric heating constant-temperature water bath kettle at 65 ℃ to prepare EVOH-Li/cellulose acetate @ boehmite spinning solution and high-heat-resistant PBI/cellulose acetate @ boehmite spinning solution.
(4) Carrying out high-voltage electrostatic spinning to obtain a fiber membrane: and a layer of aluminum foil is wrapped on the receiving roller, the aluminum foil and the spinning solutions are respectively contained in the injectors of the two electrostatic spinning devices, the distance between the needle head of the injector and the receiving platform is 15 cm, the needle head is connected with the anode of a high-voltage power supply, and the metal cylinder paved with the aluminum foil is connected with the cathode. Setting spinning parameters: the temperature was 30 ℃, the humidity was 30% and the spinning rate was 0.4 ml/h. Starting the device, adjusting the voltage value to make the front end of the needle cylinder present a stable Taylor cone, spinning for 6h, and collecting a fiber membrane with the thickness of about 20 μm on a roller.
(5) And (5) curing, namely placing the fiber membrane obtained in the step (4) in a 65 ℃ oven for curing for 4 h to obtain the composite electrostatic spinning fiber membrane.
Through the steps (1) - (5), the battery diaphragm with high temperature resistance, good dimensional stability, excellent flame retardant property and excellent cycle performance can be obtained, the dimensional stability and the heat-resistant flame retardant property of the fiber membrane can be effectively improved by adding the cellulose acetate @ boehmite particles, and the heat resistance and the mechanical property of the fiber membrane are improved by compounding the EVOH-Li and the soluble PBI.
The embodiments of the present invention are only for illustrating the technical solutions of the present invention, and not for limiting the same. Therefore, any omissions, modifications, and the like that may be made within the principles of the invention are intended to be included within the scope of the invention.
Claims (11)
1. A lithium battery separator characterized by: the thickness of the diaphragm is 5-50 μm, and the porosity is 50-95%.
2. A preparation method of a lithium battery diaphragm is characterized by comprising the following steps:
(1) preparation of lithium polyethylene-vinylalcohol (EVOH-Li);
(2) preparing polyethylene-lithium vinyl alcohol (EVOH-Li) and Polybenzimidazole (PBI) spinning solution;
(3) preparing cellulose acetate @ boehmite nanoparticles;
(4) preparing a composite spinning solution;
(5) carrying out high-voltage electrostatic spinning on the spinning solution to prepare a fiber membrane;
(6) and (5) drying, namely placing the fiber membrane obtained in the step (5) in an oven for drying to obtain the composite electrostatic spinning fiber membrane.
3. The method for preparing a lithium battery separator according to claim 2, wherein in the step (1), the polyethylene-lithium vinyl alcohol (EVOH-Li) is prepared by respectively dissolving EVOH and lithium tert-butoxide in N, N-dimethylacetamide (DMAc), uniformly mixing the EVOH and the lithium tert-butoxide, adding a certain amount of 1, 3-propane sulfonic acid lactone after the mixture is fully reacted, pouring the reaction product into water, repeatedly washing and drying to obtain the EVOH-Li.
4. The method for preparing a lithium battery separator according to claim 2, wherein the step (2) of preparing the EVOH-Li and PBI spinning solution comprises: EVOH-Li solid and soluble Polybenzimidazole (PBI) resin are respectively and uniformly mixed with DMAc to prepare spinning solution.
5. The method of preparing a lithium battery separator as claimed in claim 2, wherein the step (3) of preparing cellulose acetate @ boehmite nanoparticles comprises: the cellulose acetate solution and the boehmite particles are added with a surfactant and stirred uniformly to prepare the cellulose acetate @ boehmite particles.
6. The method for preparing a lithium battery separator according to claim 2, wherein in the step (3), the surfactant is one or more selected from the group consisting of sodium stearyl sulfate, sodium stearate, and a nonionic surfactant.
7. The method for preparing a lithium battery separator according to claim 2, wherein the step (4) of preparing the composite spinning solution comprises: and (2) respectively taking the EVOH-Li spinning solution and the PBI spinning solution prepared in the step (1), adding the cellulose acetate @ boehmite particles prepared in the step (2), and uniformly mixing to prepare the EVOH-Li/cellulose acetate @ boehmite spinning solution and the high-heat-resistance PBI/cellulose acetate @ boehmite spinning solution.
8. The method for preparing a lithium battery separator as claimed in claim 2, wherein in the step (5), the distance between the needle of the syringe and the upper surface of the receiving table is 10 to 25 cm, and the applied voltage is 8 to 25 KV.
9. The method for preparing a lithium battery separator as claimed in claim 2, wherein the advancing speed of the syringe in the step (5) is 0.2 to 0.5 ml/h.
10. The method for preparing a lithium battery separator as claimed in claim 2, wherein in the step (5), the spinning temperature is 25 to 30 ℃ and the humidity is 25 to 35%.
11. The method for preparing a lithium battery separator according to claim 2, wherein the drying temperature is 60 to 75 ℃ and the drying time is 2 to 6 hours in the step (6).
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| Application Number | Priority Date | Filing Date | Title |
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| CN202010629637.2A CN111900312A (en) | 2020-07-03 | 2020-07-03 | High-performance lithium battery diaphragm and preparation method thereof |
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| CN202010629637.2A CN111900312A (en) | 2020-07-03 | 2020-07-03 | High-performance lithium battery diaphragm and preparation method thereof |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113690539A (en) * | 2021-07-28 | 2021-11-23 | 南京林业大学 | Preparation method of high-performance cellulose-based lithium ion battery diaphragm |
| CN115241599A (en) * | 2022-07-27 | 2022-10-25 | 云南中宣液态金属科技有限公司 | Preparation device and preparation method of battery diaphragm and battery diaphragm |
| CN116162192A (en) * | 2022-09-07 | 2023-05-26 | 安徽普力通新材料科技有限公司 | Resin for cracking-resistant heat-vulcanized adhesive and composition thereof |
| CN115241599B (en) * | 2022-07-27 | 2024-06-07 | 云南中宣液态金属科技有限公司 | Preparation device and preparation method of battery diaphragm and battery diaphragm |
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| CN104752658A (en) * | 2013-12-27 | 2015-07-01 | 中国科学院青岛生物能源与过程研究所 | Flame-retardant cellulose diaphragm of lithium battery prepared through electrostatic spinning |
| CN107437630A (en) * | 2016-05-26 | 2017-12-05 | 上海恩捷新材料科技股份有限公司 | A kind of lithium battery isolation membrane and its production and use |
| CN109273643A (en) * | 2018-09-25 | 2019-01-25 | 合肥先杰新能源科技有限公司 | The preparation method of lithium battery fire-retardant cellulose diaphragm |
| CN110233222A (en) * | 2019-07-12 | 2019-09-13 | 哈尔滨理工大学 | A method of preparing strong mechanical performance battery diaphragm |
| CN110323390A (en) * | 2019-07-10 | 2019-10-11 | 哈尔滨理工大学 | A kind of new method preparing high heat resistance high intensity battery diaphragm |
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2020
- 2020-07-03 CN CN202010629637.2A patent/CN111900312A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104752658A (en) * | 2013-12-27 | 2015-07-01 | 中国科学院青岛生物能源与过程研究所 | Flame-retardant cellulose diaphragm of lithium battery prepared through electrostatic spinning |
| CN107437630A (en) * | 2016-05-26 | 2017-12-05 | 上海恩捷新材料科技股份有限公司 | A kind of lithium battery isolation membrane and its production and use |
| CN109273643A (en) * | 2018-09-25 | 2019-01-25 | 合肥先杰新能源科技有限公司 | The preparation method of lithium battery fire-retardant cellulose diaphragm |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113690539A (en) * | 2021-07-28 | 2021-11-23 | 南京林业大学 | Preparation method of high-performance cellulose-based lithium ion battery diaphragm |
| CN113690539B (en) * | 2021-07-28 | 2023-04-07 | 南京林业大学 | Preparation method of high-performance cellulose-based lithium ion battery diaphragm |
| CN115241599A (en) * | 2022-07-27 | 2022-10-25 | 云南中宣液态金属科技有限公司 | Preparation device and preparation method of battery diaphragm and battery diaphragm |
| CN115241599B (en) * | 2022-07-27 | 2024-06-07 | 云南中宣液态金属科技有限公司 | Preparation device and preparation method of battery diaphragm and battery diaphragm |
| CN116162192A (en) * | 2022-09-07 | 2023-05-26 | 安徽普力通新材料科技有限公司 | Resin for cracking-resistant heat-vulcanized adhesive and composition thereof |
| CN116162192B (en) * | 2022-09-07 | 2024-05-14 | 安徽普力通新材料科技有限公司 | Resin for cracking-resistant heat-vulcanized adhesive and composition thereof |
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Application publication date: 20201106 |