CN113223867B - Cellulose diaphragm for hybrid capacitor and preparation method thereof - Google Patents
Cellulose diaphragm for hybrid capacitor and preparation method thereof Download PDFInfo
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- 239000003990 capacitor Substances 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000002002 slurry Substances 0.000 claims abstract description 41
- 239000000835 fiber Substances 0.000 claims abstract description 39
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- 229920001410 Microfiber Polymers 0.000 claims abstract description 32
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/52—Separators
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
-
- 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
- Y02E60/13—Energy storage using capacitors
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- Microelectronics & Electronic Packaging (AREA)
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- Cell Separators (AREA)
Abstract
The invention belongs to the technical field of preparation of cellulose diaphragms for hybrid capacitors, and relates to a cellulose diaphragm for a hybrid capacitor and a preparation method thereof. The invention provides a preparation method of cellulose diaphragm paper with a gradient pore structure for a mixed capacitor by uniformly blending micro fibers and skeleton fibers and regulating and controlling the proportion of the micro fibers to the skeleton fibers in slurry. The slurry suspension formed by using the micro fibers as the main raw materials has the advantages of high drainage resistance, low porosity, low wet paper web strength and easy breaking, the problems can be effectively solved by adding the framework fibers, and the preparation of the cellulose diaphragm paper with the porosity of 40-60% in the middle section of the gradient distribution of the pores and the porosity of 62-80% in the first half section and the second half section is realized by regulating and controlling the proportion of the micro fibers to the framework fibers in the raw materials, so that the balance problem between the power characteristics of the mixed capacitor and the electric leakage is solved.
Description
Technical Field
The invention belongs to the technical field of preparation of cellulose diaphragms for hybrid capacitors, and relates to a cellulose diaphragm for a hybrid capacitor and a preparation method thereof.
Background
In recent years, the energy storage technology of the super capacitor has been greatly improved, but the double-layer capacitor is subject to a physical ion adsorption/desorption energy storage mechanism, and the energy density of the super capacitor is greatly improved in a short period of time, which is a worldwide technical problem (< 10 Wh/kg). The introduction of chemical energy storage and the construction of a hybrid capacitor with a physical and chemical synergistic energy storage effect are feasible technical approaches. Hybrid capacitors have received increasing academic and industrial attention, combining the principles of operation of both lithium ion batteries and electric double layer capacitors.
The diaphragm is one of the key materials of the hybrid capacitor, and is mainly used for preventing electron conduction, preventing internal short circuit caused by contact between two electrodes and ensuring that ions in electrolyte can smoothly pass through. The separator plays an important role in the electrochemical performance and the safety performance of the hybrid capacitor. The common polyolefin diaphragm of the lithium ion battery has low porosity, is not beneficial to the rapid migration of ions, and directly affects the multiplying power characteristic of the hybrid capacitor; secondly, polyolefin diaphragms have poor wettability and liquid retention and are difficult to meet the long-cycle requirement of the hybrid capacitor; again, polyolefin-based separators are poor in thermal stability and difficult to meet the safety requirements of hybrid capacitors at high power charge and discharge. In summary, a separator for a polyolefin-based lithium ion battery is not suitable for a hybrid capacitor.
The cellulose membrane has high porosity, excellent thermal stability and good wettability, and is widely applied to super capacitors. In contrast, cellulose membranes meet the requirements of hybrid capacitance for power characteristics, cycle characteristics and thermal stability, and are proven for use in hybrid capacitors. The comprehensive application results show that the common commercial cellulose diaphragm has high porosity, so that the leakage current of the hybrid capacitor is overlarge, and the storage, grouping and balancing of the hybrid capacitor are provided with great challenges. Researchers reduce the porosity of the diaphragm by adopting nano cellulose as a raw material, but the diameter of the nano cellulose is too small, and the drainage resistance is too large in the paper making process of diaphragm preparation, so that engineering is difficult; and secondly, the lower porosity of the nanocellulose diaphragm causes excessive internal resistance of the device, and the rate performance is influenced. In the practical application process, the balance relation between the leakage and the power characteristic of the hybrid capacitor is solved.
Disclosure of Invention
The invention aims at solving the problems in the prior art, and provides a cellulose diaphragm with gradient porosity distribution for a hybrid capacitor and a preparation method thereof, which solve the problem of unbalance between the power characteristic and electric leakage of the hybrid capacitor.
The aim of the invention can be achieved by the following technical scheme:
a cellulose diaphragm for a hybrid capacitor, wherein the porosity of the diaphragm is distributed in a gradient manner, the porosity of a middle section is 40-60%, and the porosities of a first half section and a second half section are 62-80%.
In the above-mentioned cellulose separator for a hybrid capacitor, the thickness of the cellulose separator is 10 to 50. Mu.m.
In order to ensure the requirement of the hybrid capacitor on leakage current, the high proportion of microfibers is adopted in raw materials to reduce the porosity of the diaphragm paper, the thickness of the diaphragm is controlled to ensure the power characteristic of the device, and the mechanical strength of the thin diaphragm with high microfiber content is poor; on the contrary, the mechanical strength of the diaphragm is moderate, and the porosity is relatively large. The leakage current performance of the device is generally improved by improving the thickness of the diaphragm, the energy density of the device is reduced due to the thick diaphragm, the problem is solved by the diaphragm with gradient distribution of porosity, the middle low-porosity diaphragm layer is used for reducing the leakage current of the device, the front half section and the rear half section of the high-porosity diaphragm layer are thin to play a supporting role, the migration rate of ions is not influenced on the premise of improving the strength of the diaphragm, and the diaphragm has high ion migration and high pressure maintaining capacity.
In the above-mentioned cellulose separator for a hybrid capacitor, the porosity of the first half and the second half is 62 to 80%.
In the above-mentioned cellulose separator for a hybrid capacitor, the raw materials in the intermediate stage are in mass ratio of 1: the mixture of the skeletal fiber cake and the fine fiber cake of (2-9).
In the cellulose separator for the hybrid capacitor, the raw materials of the first half and the second half are in mass ratio of 1: the fine fiber-pulp cake and the skeletal fiber-pulp cake of (1-4).
The morphology and the interlacing structure of the fibrous raw material have a decisive influence on the properties of the cellulosic separator. According to the invention, the microfibers and the skeleton fibers are uniformly blended, wherein the skeleton fibers play a role of a skeleton, so that the mechanical strength of the diaphragm is improved; the microfiber plays roles of filling and blocking pores, improves the pore structure of the diaphragm, and modulates the porosity of the diaphragm.
In the above-mentioned cellulose separator for a hybrid capacitor, the microfiber in the microfiber slurry has a diameter of 10 to 300nm and a length of 1 to 50. Mu.m. Preferably, the microfibers are selected from one or more of natural plant fiber wood, cotton, soybean hulls, hemp, sisal, liu Ke, banana hulls, pea hulls.
In the cellulose membrane for the hybrid capacitor, the diameter of the skeleton fiber in the skeleton fiber paste is 0.5-5 mu m, and the length is 100-500 mu m.
The smaller the diameter and the shorter the length of the micro fibers, the smaller the porosity of the separator paper formed by interweaving the micro fibers after papermaking, the fine fibers can play a role in pore filling and pore blocking, and the short fibers cause the strength of the crosslinked separator to be poor. The skeleton fiber is coarse and long fiber, plays the roles of skeleton and meridian in the diaphragm, has long length, can improve the mechanical property of the diaphragm, and has large pore and large pore diameter after interweaving due to the coarse diameter of the skeleton fiber.
The invention also provides a preparation method of the cellulose membrane for the hybrid capacitor, which comprises the following steps:
s1, firstly, mixing the micro fiber paste with the skeleton fiber paste according to the mass ratio of (0.25-1): 1, uniformly mixing to obtain a mixture A;
s2, mixing the micro fiber paste with the skeleton fiber paste according to the mass ratio of (2-9): 1, uniformly mixing to obtain a mixture B;
s3, respectively stirring the mixture A and the mixture B at a rotating speed of 1500-2000rpm to obtain slurry suspension A and slurry suspension B;
s4, sequentially injecting samples in a paper machine according to the sequence of the slurry suspension A, the slurry suspension B and the slurry suspension A to prepare a wet cellulose membrane;
and S5, sequentially carrying out suction filtration, primary drying, hot pressing, secondary drying and rolling on the wet cellulose membrane to obtain the cellulose membrane with gradient porosity distribution comprising a middle section, a first half section and a second half section.
The invention provides a preparation method of cellulose diaphragm paper with a gradient pore structure for a mixed capacitor by uniformly blending micro fibers and skeleton fibers and regulating and controlling the proportion of the micro fibers to the skeleton fibers in slurry. The slurry suspension formed by using the microfibers as the main raw materials has the advantages of high drainage resistance, low porosity, low wet paper web strength and easy breaking, the problems can be effectively solved by adding the skeleton fibers, and the preparation of the cellulose diaphragm paper with gradient distribution of pores is realized by regulating and controlling the proportion of the microfibers to the skeleton fibers in the raw materials, so that the balance problem between the power characteristics of the mixed capacitor and the electric leakage is solved.
In the preparation method of the cellulose membrane for the hybrid capacitor, the mass ratio of the slurry suspension A and the slurry suspension B which are sequentially sampled in S4 is (1-3): (4-8). Wherein the mass ratio of the slurry suspension A of the two injections is 1:1.
According to the invention, the preparation of cellulose diaphragm paper with gradient distribution of porosity is realized by changing the sample injection sequence of micro-fiber and skeleton fiber slurry suspensions with different proportions in the papermaking process. The proportion of skeleton fibers in the slurry suspension A is higher, and the porosity of the separator paper prepared after papermaking is higher; the proportion of micro fibers in the slurry suspension B is higher, and the porosity of the prepared diaphragm paper is smaller.
Specifically, the invention comprises two cellulose pulp dispensers A and B, the order of pulp suspension A- & gt B- & gt A is implemented in a paper machine by the regulation and control of a sample injection valve A and a sample injection valve B, then suction filtration, drying in a multi-stage drying hot-pressing device and hot-pressing are sequentially carried out, and finally a cellulose diaphragm is obtained by rolling in a rolling device. If the sampling sequence is changed once, the porosity distribution of the cellulose membrane is changed, so that the cellulose membrane becomes large in middle porosity and small in two sides, and the internal resistance of the membrane is increased.
In the preparation method of the cellulose membrane for the hybrid capacitor, the primary drying temperature of S5 is 80-100 ℃ and the time is 2-3 hours; the secondary drying temperature is 100-130 ℃ and the secondary drying time is 10-12.
In the preparation method of the cellulose membrane for the hybrid capacitor, the S5 hot pressing is carried out at 110-125 ℃ and 10-30Mpa.
Compared with the prior art, the invention has the following beneficial effects:
1. the cellulose diaphragm prepared by the invention has the characteristic of gradient distribution of porosity, the porosity in the middle of the diaphragm is low, the porosity in the front half section and the back half section is high, and compared with the diaphragm with uniform porosity, the diaphragm with gradient distribution of porosity can solve the imbalance between the ion diffusion rate and the leakage current.
2. The invention utilizes the middle low-porosity diaphragm thin layer to reduce leakage current of the device, and the first half section and the second half section of the high-porosity diaphragm thin layer play a supporting role, so that the migration rate of ions is not influenced on the premise of improving the strength of the diaphragm, and the diaphragm has high ion migration and high pressure maintaining capacity.
3. The invention has the advantages of simple and easily obtained raw materials, environment-friendly and pollution-free preparation process and suitability for large-scale industrial production.
Drawings
FIG. 1 is a scanning electron micrograph of a cellulose membrane prepared in example 1 of the present invention;
FIG. 2 is a schematic diagram of the equipment required in the membrane manufacturing process of example 1 of the present invention:
1. cellulose dispersers a and B;
2. a paper machine;
3. multistage drying hot-pressing equipment;
4. winding device
5. A sample injection valve A;
6. and a sample injection valve B.
Detailed Description
The following are specific examples of the present invention, and the technical solutions of the present invention are further described, but the present invention is not limited to these examples.
As shown in fig. 2, the separator manufacturing process of the present invention comprises, from left to right, a cellulose disperser a, a cellulose disperser B1, a sample valve A5, a sample valve B6, a paper machine 2, a multi-stage drying and hot-pressing device 3, and a winding device 4.
Example 1:
s1, preparing a microfiber raw material with an average diameter of 200nm and an average length of 50 mu m; backbone fibers having an average diameter of 3 μm and an average length of 200 μm;
s2, firstly, mixing the micro fiber paste with the skeleton fiber paste according to the mass ratio of 1:2.3, uniformly mixing to obtain a mixture A;
s3, mixing the micro fiber paste with the skeleton fiber paste according to a mass ratio of 2.3:1, uniformly mixing to obtain a mixture B;
s4, respectively feeding the mixture A and the mixture B into a cellulose disperser A and a cellulose disperser B in the equipment shown in the figure 2, and stirring for 30min at a rotating speed of 1500rpm to obtain slurry A suspension and slurry B suspension;
s5, sequentially injecting samples in a paper machine in the sequence of the slurry A suspension, the slurry B suspension and the slurry A suspension through the regulation and control of the sample injection valve A and the sample injection valve B to prepare a wet cellulose membrane; the corresponding mass ratio of slurry suspension sample injection is 3:4:3.
S6, carrying out suction filtration on the wet cellulose membrane, then placing the wet cellulose membrane in a multi-stage drying hot-pressing device, drying at 95 ℃, hot-pressing at 20Mpa and 120 ℃, dewatering and drying for 12 hours under the vacuum drying condition at 120 ℃, and finally rolling the wet cellulose membrane by a rolling device to obtain the cellulose membrane with the thickness of 25 mu m, the porosity of the middle section of 50% and the porosity of the first half section and the second half section of 70%.
Example 2:
s1, preparing a microfiber raw material with an average diameter of 10nm and an average length of 1 mu m; a backbone fiber having an average diameter of 0.5 μm and an average length of 100 μm;
s2, firstly, mixing the micro fiber paste with the skeleton fiber paste according to the mass ratio of 1:2.3, uniformly mixing to obtain a mixture A;
s3, mixing the micro fiber paste with the skeleton fiber paste according to a mass ratio of 2.3:1, uniformly mixing to obtain a mixture B;
s4, respectively feeding the mixture A and the mixture B into a cellulose disperser A and a cellulose disperser B in the equipment shown in the figure 2, and stirring for 30min at a rotating speed of 1500rpm to obtain slurry A suspension and slurry B suspension;
s5, sequentially injecting samples in a paper machine in the sequence of the slurry A suspension, the slurry B suspension and the slurry A suspension through the regulation and control of the sample injection valve A and the sample injection valve B to prepare a wet cellulose membrane; the corresponding mass ratio of slurry suspension sample injection is 1:4:1.
S6, carrying out suction filtration on the wet cellulose membrane, then placing the wet cellulose membrane in a multi-stage drying hot-pressing device, drying at 95 ℃, then carrying out hot pressing at 20Mpa and 120 ℃, carrying out dewatering and drying for 12 hours under the vacuum drying condition at 120 ℃, and finally rolling to obtain the cellulose membrane with the thickness of 25 mu m, the porosity of the middle section of 45% and the porosities of the first half section and the second half section of 65%.
Example 3:
the difference from example 1 was only that the cellulose membrane had a thickness of 100 μm, and finally a cellulose membrane having a porosity of 50% in the middle section and a porosity of 70% in the first and second half sections was obtained.
Example 4:
the difference from example 1 is only that the mass ratio of the injected slurry suspension A, slurry suspension B and slurry suspension A is 3:1:3, and finally the cellulose membrane with the porosity of the middle section of 50% and the porosity of the first half section and the second half section of 70% is obtained.
Comparative example 1:
the difference from example 1 was only that the sample was introduced into the paper machine in the order of the slurry B, slurry A and slurry B, and finally wound up to obtain a cellulose membrane having a thickness of 25. Mu.m, a porosity of 70% in the middle and a porosity of 50% in the first and second half.
Comparative example 2:
the difference from example 1 is that only the pulp suspension of the fine fiber paste and the skeleton fiber paste with the mass ratio of 3:2 is injected in a paper machine, and finally the cellulose membrane with the thickness of 25 μm and the porosity of 64% is obtained by rolling.
The test standards for the porosities of examples 1-4 and comparative examples 1-2 were GB/T10799-2008.
Table 1: results of testing the properties of the cellulose separators prepared in examples 1 to 4 and comparative examples 1 to 2
In summary, the internal resistance index corresponds to the ion diffusion rate (the smaller the internal resistance, the faster the ion diffusion); leakage current corresponds to pressure maintaining capability, and both ion diffusion rate and pressure maintaining capability are contradictory. The cellulose membrane prepared by the invention has the characteristic of gradient distribution of porosity, the porosity in the middle of the membrane is low, the porosity at two sides of the membrane is high, compared with the membrane with uniform porosity, the membrane with gradient distribution of the porosity can solve the imbalance of ion diffusion rate and pressure maintaining capacity, and the overall cellulose membrane has small internal resistance and strong pressure maintaining capacity.
The point values in the technical scope of the present invention are not exhaustive, and the new technical solutions formed by equivalent substitution of single or multiple technical features in the technical solutions of the embodiments are also within the scope of the present invention; meanwhile, in all the listed or unrecited embodiments of the present invention, each parameter in the same embodiment represents only one example of the technical scheme (i.e. a feasibility scheme), and no strict coordination and limitation relation exists between each parameter, wherein each parameter can be replaced with each other without violating axiom and the requirement of the present invention, except what is specifically stated.
The technical means disclosed by the scheme of the invention is not limited to the technical means disclosed by the technical means, and also comprises the technical scheme formed by any combination of the technical features. While the foregoing is directed to embodiments of the present invention, it will be appreciated by those skilled in the art that changes and modifications may be made without departing from the principles of the invention, and such changes and modifications are intended to be included within the scope of the invention.
The specific embodiments described herein are offered by way of example only to illustrate the spirit of the invention. Those skilled in the art may make various modifications or additions to the described embodiments or substitutions thereof without departing from the spirit of the invention or exceeding the scope of the invention as defined in the accompanying claims.
Claims (5)
1. The cellulose diaphragm for the hybrid capacitor is characterized in that the porosity of the diaphragm is in gradient distribution, the porosity of the middle section is 40-60%, and the porosities of the first half section and the second half section are 62-80%;
the thickness of the cellulose diaphragm is 10-50 mu m;
the raw materials of the middle section are in mass ratio of 1: the skeletal fiber cake and micro fiber cake mixture of (2-9);
the raw materials of the first half section and the second half section are in mass ratio of 1: the mixture of the fine fiber paste and the skeletal fiber paste of (1-4);
the diameter of the microfiber in the microfiber paste is 10-300nm, and the length is 1-50 mu m;
the diameter of the skeleton fiber in the skeleton fiber paste is 0.5-5 mu m, and the length is 100-500 mu m.
2. A method for producing a cellulose separator for a hybrid capacitor according to claim 1, comprising the steps of:
s1, firstly, mixing the micro fiber paste with the skeleton fiber paste according to the mass ratio of (0.25-1): 1, uniformly mixing to obtain a mixture A;
s2, mixing the micro fiber paste with the skeleton fiber paste according to the mass ratio of (2-9): 1, uniformly mixing to obtain a mixture B;
s3, respectively stirring the mixture A and the mixture B at a rotating speed of 1500-2000rpm to obtain slurry suspension A and slurry suspension B;
s4, sequentially injecting samples in a paper machine according to the sequence of the slurry suspension A, the slurry suspension B and the slurry suspension A to prepare a wet cellulose membrane;
and S5, sequentially carrying out suction filtration, primary drying, hot pressing, secondary drying and rolling on the wet cellulose membrane to obtain the cellulose membrane with gradient porosity distribution comprising a middle section, a first half section and a second half section.
3. The preparation method of the cellulose membrane for the hybrid capacitor according to claim 2, wherein the mass ratio of the slurry suspension A and the slurry suspension B which are sequentially sampled in S4 is (1-3): (4-8).
4. The method for preparing a cellulose membrane for a hybrid capacitor according to claim 2, wherein the primary drying temperature of S5 is 80-100 ℃ for 2-3 hours; the secondary drying temperature is 100-130 ℃ and the secondary drying time is 10-12h.
5. The method for producing a cellulose membrane for a hybrid capacitor according to claim 2, wherein the S5 hot press is 110-125℃and 10-30MPa.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103199300A (en) * | 2013-04-22 | 2013-07-10 | 上海双奥能源技术有限公司 | Coated lithium ion battery diaphragm |
| CN104350631A (en) * | 2012-04-10 | 2015-02-11 | 加州理工学院 | Novel separators for electrochemical systems |
| CN105103364A (en) * | 2013-03-26 | 2015-11-25 | 日产自动车株式会社 | Nonaqueous-electrolyte secondary battery |
| CN106654119A (en) * | 2016-11-14 | 2017-05-10 | 宁波中车新能源科技有限公司 | Mixed coating diaphragm and preparation method and application thereof |
| CN110656529A (en) * | 2019-09-12 | 2020-01-07 | 中国制浆造纸研究院有限公司 | Fine fiber, preparation method and application thereof, and preparation method of diaphragm for electrical equipment |
| CN110911614A (en) * | 2019-11-14 | 2020-03-24 | 深圳中兴新材技术股份有限公司 | Stretching device and method for preparing multilayer polymer diaphragm and diaphragm prepared by stretching device |
-
2021
- 2021-03-23 CN CN202110307048.7A patent/CN113223867B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104350631A (en) * | 2012-04-10 | 2015-02-11 | 加州理工学院 | Novel separators for electrochemical systems |
| CN105103364A (en) * | 2013-03-26 | 2015-11-25 | 日产自动车株式会社 | Nonaqueous-electrolyte secondary battery |
| CN103199300A (en) * | 2013-04-22 | 2013-07-10 | 上海双奥能源技术有限公司 | Coated lithium ion battery diaphragm |
| CN106654119A (en) * | 2016-11-14 | 2017-05-10 | 宁波中车新能源科技有限公司 | Mixed coating diaphragm and preparation method and application thereof |
| CN110656529A (en) * | 2019-09-12 | 2020-01-07 | 中国制浆造纸研究院有限公司 | Fine fiber, preparation method and application thereof, and preparation method of diaphragm for electrical equipment |
| CN110911614A (en) * | 2019-11-14 | 2020-03-24 | 深圳中兴新材技术股份有限公司 | Stretching device and method for preparing multilayer polymer diaphragm and diaphragm prepared by stretching device |
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