CN107326722B - Preparation method of lithium battery diaphragm paper - Google Patents
Preparation method of lithium battery diaphragm paper Download PDFInfo
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- CN107326722B CN107326722B CN201710314004.0A CN201710314004A CN107326722B CN 107326722 B CN107326722 B CN 107326722B CN 201710314004 A CN201710314004 A CN 201710314004A CN 107326722 B CN107326722 B CN 107326722B
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H13/00—Pulp or paper, comprising synthetic cellulose or non-cellulose fibres or web-forming material
- D21H13/10—Organic non-cellulose fibres
- D21H13/12—Organic non-cellulose fibres from macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D21H13/14—Polyalkenes, e.g. polystyrene polyethylene
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H13/00—Pulp or paper, comprising synthetic cellulose or non-cellulose fibres or web-forming material
- D21H13/10—Organic non-cellulose fibres
- D21H13/12—Organic non-cellulose fibres from macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D21H13/18—Polymers of unsaturated acids or derivatives thereof, e.g. polyacrylonitriles
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H13/00—Pulp or paper, comprising synthetic cellulose or non-cellulose fibres or web-forming material
- D21H13/10—Organic non-cellulose fibres
- D21H13/20—Organic non-cellulose fibres from macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D21H13/24—Polyesters
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/20—Macromolecular organic compounds
- D21H17/21—Macromolecular organic compounds of natural origin; Derivatives thereof
- D21H17/24—Polysaccharides
- D21H17/25—Cellulose
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/63—Inorganic compounds
- D21H17/67—Water-insoluble compounds, e.g. fillers, pigments
- D21H17/68—Water-insoluble compounds, e.g. fillers, pigments siliceous, e.g. clays
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H19/00—Coated paper; Coating material
- D21H19/10—Coatings without pigments
- D21H19/14—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12
-
- 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
-
- 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
-
- 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
- H01M50/44—Fibrous material
-
- 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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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Dispersion Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Cell Separators (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a preparation method of lithium battery diaphragm paper. The method comprises the following steps: firstly, polypropylene fiber, polyacrylonitrile fiber and polyester fiber are defibered and dispersed to prepare mixed fiber slurry; adding ceramic waste particles as a filler, and obtaining lithium battery diaphragm paper after net surfing, press dehydration, drying and hot pressing; and (2) dispersing a proper amount of boron nitride in polyvinyl alcohol to obtain a coating liquid, coating the coating liquid on the lithium battery diaphragm paper, and performing calendaring treatment on a calendar to obtain the lithium battery diaphragm paper containing the insulating coating. The lithium battery diaphragm paper prepared by mixing the three fibers has excellent electrolyte absorption performance and higher thermal stability, so that the safety performance of a lithium battery is greatly improved. In addition, the ceramic waste is used as the filler, so that the waste is changed into valuable, and the cost of raw materials is greatly reduced.
Description
Technical Field
The invention relates to the field of pulping and papermaking, and particularly relates to a preparation method of lithium battery diaphragm paper.
Background
The battery diaphragm paper is used as a diaphragm material for separating a positive electrode from a negative electrode in a battery, mainly has the functions of preventing the positive electrode and the negative electrode in the battery from being in direct contact and short circuit, enabling ions in an electrolyte to freely pass between the positive electrode and the negative electrode and preventing electrons from freely passing through, and plays a role in lifting weight in each part forming the battery, and the advantages and disadvantages of the diaphragm material directly influence the key characteristics of the battery, such as the discharge capacity, the cycle service life, the charge-discharge current density and the like.
At present, the lithium battery diaphragm on the market mainly takes Polyethylene (PE) and polypropylene (PP) as representative polyolefin microporous stretched films, but the stretched film made of polyolefin has low porosity, liquid absorption amount and specific surface energy, poor affinity performance to electrolyte, extremely strong thermal shrinkage at a temperature of more than 100 ℃, poor dimensional stability, easy contact of positive and negative pole pieces of the battery, short circuit, instant generation of a large amount of heat, ignition and explosion of the battery, and influence on the safety of the power battery. Therefore, how to provide a lithium battery separator having both excellent electrolyte absorption performance and high thermal stability is an urgent problem to be solved in the art.
The patent (201610138294.3) discloses a method for producing lithium battery separator paper, which comprises the steps of uniformly mixing softwood bleached wood pulp, dissolving pulp and nanocellulose fiber according to the mass ratio of 1:1:3, adding polyoxyethylene, papermaking on a paper machine, drying, and calendering to obtain the nanocellulose lithium battery separator paper. The diaphragm has the characteristics of good isolation performance and good storage stability, and has the defects of complex preparation process, poor alkali resistance and easy corrosion by electrolyte.
Disclosure of Invention
The invention aims to overcome the defects and shortcomings, adopts the polypropylene fiber, the polyacrylonitrile fiber and the polyester fiber as the preparation raw materials of the diaphragm paper, can improve the physical strength performance of the diaphragm paper and ensure better alkali absorption performance, and simultaneously effectively prevents the diaphragm paper from losing the ion isolation effect due to the rupture because of the improvement of the strength of the diaphragm paper, thereby having better engineering practical value. In addition, the ceramic waste is used as the filler, so that the waste is changed into valuable, the raw material cost is greatly reduced, and conditions are created for large-scale production.
The invention is realized by the following technical scheme:
a lithium battery separator paper comprising the steps of:
(1) putting 40-55 parts by weight of polypropylene fiber into a dispersing barrel with a stirrer, adding water for defibering for 20-30 min until the polypropylene fiber is uniformly dispersed in a water phase to form polypropylene fiber slurry;
(2) putting 25-35 parts by weight of polyacrylonitrile fibers into a beating machine, adding water to discongest for 20-30 min, beating with a light knife for 40-60 min, and stopping beating until the fibers are completely dispersed and have no pulp point to form polyacrylonitrile fiber slurry;
(3) putting 20-30 parts by weight of polyester fibers into a beating machine, adding water to discompose for 20-30 min, beating with a light knife for 40-60 min, and stopping beating until the fibers are completely dispersed and have no pulp point to form polyester fiber pulp;
(4) putting all the three slurries into a slurry mixing tank, adding water until the concentration is 0.2-0.5%, adding 1-2mL of a dispersing agent, adding 35-53 parts of ceramic waste particles as a filler, and uniformly stirring to obtain a mixed slurry; and (3) dehydrating and forming, squeezing, drying and hot-press forming the diluted mixed slurry at a net part, and then carrying out subsequent paper rolling and cutting to obtain the lithium battery diaphragm paper.
(5) And (2) dispersing 1.0-1.2 parts of boron nitride in polyvinyl alcohol to obtain a coating liquid, coating the coating liquid on the lithium battery diaphragm paper, and performing calendaring treatment on a calendar to obtain the lithium battery diaphragm paper containing the insulating coating.
In the method, the length of the polypropylene fiber is 1mm-8mm, and the titer of the polypropylene fiber is 0.2-0.6 detx; the polyacrylonitrile fiber has the fiber length of 1mm-8mm and the fineness of 0.2-0.6 detx; the fiber length of the polyester fiber is 2mm-6mm, and the titer is 0.1-0.3 detx.
In the method, the dispersant is carboxymethyl cellulose or polyacrylamide, and the mass concentration of the dispersant is 0.1-1%.
In the method, the thermal-press molding temperature of the lithium battery diaphragm paper is 270-350 ℃, and the time is 3-6 min.
In the method, the lithium battery separator paper is characterized in that the quantitative amount of the lithium battery separator paper is 40-50g/m2。
In the above method, the lithium battery separator paper has a weight per unit area of 25g/m2-30g/m2。
In the method, the particle size of the ceramic waste particles is 0.02-1 μm.
Compared with the prior art, the invention has the advantages that:
(1) the invention takes the polypropylene fiber, the polyacrylonitrile fiber and the polyester fiber as the preparation raw materials of the diaphragm paper, not only can improve the physical strength performance of the diaphragm paper and ensure better alkali absorption performance, but also effectively prevents the diaphragm paper from losing the ion isolation effect due to the rupture because of the improvement of the strength of the diaphragm paper.
(2) The invention takes the ceramic waste as the filler, is beneficial to solving the problem of waste disposal, changes waste into valuable, and in addition, the ceramic waste has low price, thereby greatly reducing the manufacturing cost of the diaphragm paper and being beneficial to engineering popularization and application.
Detailed Description
The present invention will be described in further detail with reference to examples, but the embodiments of the present invention are not limited thereto.
Example 1
A preparation method of lithium battery separator paper comprises the following steps:
the fiber is screened according to the following standard, the fiber length of the polypropylene fiber is 2mm, and the titer is 0.2 detx; the polyacrylonitrile fiber has the fiber length of 1mm and the fineness of 0.2 detx; the polyester fiber has a fiber length of 2mm and a fineness of 0.1detx
Step 1: putting 40 parts by weight of polypropylene fiber into a dispersing barrel with a stirrer, adding water for defibering for 20min until the polypropylene fiber is uniformly dispersed in a water phase to form polypropylene fiber slurry;
step 2: putting 25 parts by weight of polyacrylonitrile fibers into a beating machine, adding water to discongest for 20min, beating with a light knife for 40min, and stopping beating until the fibers are completely dispersed and have no pulp point to form polyacrylonitrile fiber pulp;
and step 3: putting 20 parts by weight of polyester fiber into a beating machine, adding water to discompose for 20min, beating with a light knife for 40min, and stopping beating until the fiber is completely dispersed and has no pulp point to form polyester fiber pulp;
and 4, step 4: putting all the three slurries into a slurry mixing tank, adding water until the mass percentage concentration is 0.2%, adding 1mL of carboxymethyl cellulose with the mass concentration of 0.1%, adding 35 parts of ceramic waste particles with the particle size of 0.02 mu m as a filler, and uniformly stirring to obtain a mixed slurry; and (3) dehydrating and forming, squeezing, drying and hot-press forming the diluted mixed slurry at a net part, and then carrying out subsequent paper rolling and cutting to obtain the lithium battery diaphragm paper.
And 5: and dispersing 1.0 part of boron nitride in polyvinyl alcohol to obtain a coating liquid, coating the coating liquid on lithium battery separator paper, and performing calendaring treatment on a calendar to obtain the lithium battery separator paper containing the insulating coating.
Example 2
A preparation method of lithium battery separator paper comprises the following steps:
the fiber is screened according to the following standard, the fiber length of the polypropylene fiber is 6mm, and the titer is 0.4 detx; the polyacrylonitrile fiber has the fiber length of 5mm and the fineness of 0.4 detx; the polyester fiber has a fiber length of 4mm and a fineness of 0.2detx
Step 1: 50 parts by weight of polypropylene fiber is taken and put into a dispersing barrel with a stirrer, and water is added for defibering for 25min until the polypropylene fiber is uniformly dispersed in a water phase to form polypropylene fiber slurry;
step 2: putting 30 parts by weight of polyacrylonitrile fibers into a beating machine, adding water to defiber for 25min, beating for 50min by a light knife, and stopping beating until the fibers are completely dispersed and have no pulp point to form polyacrylonitrile fiber pulp;
and step 3: putting 25 parts by weight of polyester fiber into a beating machine, adding water to discongest for 25min, beating with a light knife for 50min, and stopping beating until the fiber is completely dispersed and has no pulp point to form polyester fiber pulp;
and 4, step 4: putting all the three slurries into a slurry mixing tank, adding water until the mass percentage concentration is 0.3%, adding 1.5mL of carboxymethyl cellulose with the mass concentration of 0.5%, adding 40 parts of ceramic waste particles with the particle size of 0.5 mu m as a filler, and uniformly stirring to obtain a mixed slurry; and (3) dehydrating and forming, squeezing, drying and hot-press forming the diluted mixed slurry at a net part, and then carrying out subsequent paper rolling and cutting to obtain the lithium battery diaphragm paper.
And 5: and dispersing 1.1 parts of boron nitride in polyvinyl alcohol to obtain a coating liquid, coating the coating liquid on lithium battery separator paper, and performing calendaring treatment on a calendar to obtain the lithium battery separator paper containing the insulating coating.
Example 3
A preparation method of lithium battery separator paper comprises the following steps:
the fiber is screened according to the following standard, the fiber length of the polypropylene fiber is 8mm, and the titer is 0.6 detx; the polyacrylonitrile fiber has the fiber length of 8mm and the fineness of 0.6 detx; the polyester fiber has a fiber length of 6mm and a fineness of 0.3detx
Step 1: putting 55 parts by weight of polypropylene fiber into a dispersing barrel with a stirrer, adding water for defibering for 30min until the polypropylene fiber is uniformly dispersed in a water phase to form polypropylene fiber slurry;
step 2: putting 35 parts by weight of polyacrylonitrile fibers into a beating machine, adding water to defiber for 30min, beating with a light knife for 60min, and stopping beating until the fibers are completely dispersed and have no pulp point to form polyacrylonitrile fiber pulp;
and step 3: putting 30 parts by weight of polyester fiber into a beating machine, adding water to defiber for 30min, beating with a light knife for 60min, and stopping beating until the fiber is completely dispersed and has no pulp point to form polyester fiber pulp;
and 4, step 4: putting all the three slurries into a slurry mixing tank, adding water until the mass percentage concentration is 0.5%, adding 2mL of polyacrylamide with the mass concentration of 1%, adding 53 parts of ceramic waste particles with the particle size of 1 mu m as a filler, and uniformly stirring to obtain a mixed slurry; and (3) dehydrating and forming, squeezing, drying and hot-press forming the diluted mixed slurry at a net part, and then carrying out subsequent paper rolling and cutting to obtain the lithium battery diaphragm paper.
And 5: and dispersing 1.2 parts of boron nitride in polyvinyl alcohol to obtain a coating liquid, coating the coating liquid on lithium battery separator paper, and performing calendaring treatment on a calendar to obtain the lithium battery separator paper containing the insulating coating.
The following tests were carried out on the lithium battery separator paper obtained in examples 1 to 3 and the lithium battery cell obtained using the separator:
(1) electrochemical resistance values of the different separators are shown in the following table:
as can be seen from the above table, at normal temperature, the electrochemical impedance of the lithium battery separator paper is not much different from that of the PP film. At normal temperature, the electrochemical impedance value of the lithium battery diaphragm paper does not change greatly; when the temperature rises, micropores in the lithium battery diaphragm paper are blocked, the electrochemical impedance value is increased, and the realization of the thermal shutdown effect is ensured.
(2) The charge and discharge performance of lithium ion batteries using different separators is shown in the following table:
in practical tests, it was found that the battery prepared from the composite separator obtained in examples 1 to 3 had a sharp increase in voltage to a set upper limit after 140 ℃/5min, and the current failed to charge normally, indicating that there was no normal channel for ion transport, and the separator achieved a thermal shutdown effect on the battery. Compared with the prior art, the PP film still charges and discharges normally under the condition of 140 ℃/5min, and the shutdown effect can not be realized, so that the safety use of the lithium battery is not facilitated.
(3) The cycle performance of lithium ion batteries using different separators is shown in the following table:
it can be seen that the capacity retention rate of the lithium ion batteries prepared in examples 1 to 3 is more than 88% after 600 cycles, while the capacity retention rate of the lithium ion batteries with the common PP film is only 82.2%, which shows that the lithium ion batteries prepared in examples 1 to 3 have good wettability between the diaphragm and the electrolyte, so that the batteries have excellent cycle performance
This is exhaustive in all embodiments. Any modification, equivalent replacement, and improvement made within the spirit and principle of the present invention should be included in the protection scope of the claims of the present invention.
Claims (1)
1. The preparation method of the lithium battery separator paper is characterized by comprising the following steps:
(1) putting 40-55 parts by weight of polypropylene fiber into a dispersing barrel with a stirrer, adding water for defibering for 20 ~ 30min, and uniformly dispersing in a water phase to obtain polypropylene fiber slurry;
(2) putting 25-35 parts by weight of polyacrylonitrile fibers into a beating machine, adding water to discongest for 20 ~ 30min, beating with a light knife for 40 ~ 60min, and stopping beating until the fibers are completely dispersed and have no pulp point to obtain polyacrylonitrile fiber slurry;
(3) putting 20-30 parts by weight of polyester fiber into a pulping machine, adding water to defiber for 20 ~ 30min, pulping for 40 ~ 60min by a light knife, and stopping pulping when the fiber is completely dispersed and has no pulp point to obtain polyester fiber pulp;
(4) putting polypropylene fiber slurry, polyacrylonitrile fiber slurry and polyester fiber slurry into a slurry mixing tank, adding water until the mass percentage concentration is 0.2-0.5%, adding 1-2mL of dispersant, adding 35-53 parts of ceramic waste particles as filler, and uniformly stirring to obtain mixed slurry; dewatering and forming, squeezing, drying and hot-press forming the diluted mixed slurry at a net part, and then carrying out subsequent paper rolling and cutting to obtain lithium battery diaphragm paper;
(5) dispersing 1.0-1.2 parts of boron nitride in polyvinyl alcohol to obtain a coating liquid, coating the coating liquid on lithium battery diaphragm paper, and performing calendaring treatment on a calendar to obtain the lithium battery diaphragm paper containing an insulating coating;
the length of the polypropylene fiber is 1mm-8mm, and the fineness is 0.2-0.6 detx; the polyacrylonitrile fiber has the fiber length of 1mm-8mm and the fineness of 0.2-0.6 detx; the length of the polyester fiber is 2mm-6mm, and the fineness is 0.1-0.3 detx;
the dispersant is carboxymethyl cellulose or polyacrylamide, and the mass concentration is 0.1-1%;
in the step (4), the hot-press molding temperature is 270-350 ℃, and the time is 3-6 min;
the quantitative amount of the lithium battery diaphragm paper is 40-50g/m2；
The particle size of the ceramic waste particles is 0.02-1 μm.
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| CN107724140A (en) * | 2017-11-14 | 2018-02-23 | 宁波日新恒力科技有限公司 | A kind of polyarylate fiber base battery barrier film and its preparation method and application |
| CN112271406B (en) * | 2020-10-30 | 2022-08-19 | 湖北第二师范学院 | Boron nitride fiber coated diaphragm for lithium ion battery and preparation method thereof |
| CN116556110A (en) * | 2023-06-06 | 2023-08-08 | 浙江鹏辰造纸研究所有限公司 | High-temperature-resistant heat insulation paper for thermal battery and preparation method thereof |
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| US4007059A (en) * | 1975-08-20 | 1977-02-08 | General Motors Corporation | Electrochemical cell electrode separator and method of making it and fuel cell containing same |
| JP5215008B2 (en) * | 2007-03-29 | 2013-06-19 | 日本板硝子株式会社 | Sealed lead-acid battery separator and sealed lead-acid battery |
| CN102522517A (en) * | 2011-12-22 | 2012-06-27 | 中国科学院青岛生物能源与过程研究所 | Cellulose/inorganic particle composite diaphragm for lithium secondary battery and preparation method thereof |
| CN105449143A (en) * | 2014-10-13 | 2016-03-30 | 万向A一二三***有限公司 | Lithium ion battery coating diaphragm and preparation method therefor |
| CN106229448B (en) * | 2016-08-13 | 2019-05-14 | 华南理工大学 | A kind of lithium battery diaphragm paper and preparation method thereof |
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