CN116200961A - High-temperature-resistant aramid battery diaphragm paper and preparation method and application thereof - Google Patents

High-temperature-resistant aramid battery diaphragm paper and preparation method and application thereof Download PDF

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Publication number
CN116200961A
CN116200961A CN202310340968.8A CN202310340968A CN116200961A CN 116200961 A CN116200961 A CN 116200961A CN 202310340968 A CN202310340968 A CN 202310340968A CN 116200961 A CN116200961 A CN 116200961A
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China
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aramid
fiber
temperature
diaphragm paper
basalt
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杨斌
庞瑞雪
张美云
宋顺喜
谭蕉君
聂景怡
张静茹
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Shaanxi University of Science and Technology
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Shaanxi University of Science and Technology
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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
    • D21H13/02—Synthetic cellulose fibres
    • 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
    • D21H27/00—Special paper not otherwise provided for, e.g. made by multi-step processes
    • 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
    • H01M50/44—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)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Paper (AREA)

Abstract

The invention discloses high temperature resistant aramid fiber battery diaphragm paper, a preparation method and application thereof, wherein aramid fiber and basalt fiber are mixed, the aramid fiber diaphragm paper is prepared by a wet papermaking process, the diaphragm paper is treated by a hot pressing process, the production process is simple and feasible, the problems of loose paper structure, poor interface binding force, low mechanical strength and compressive strength and the like caused by the difference of the components of the aramid fiber diaphragm paper are avoided, the prepared diaphragm paper has high temperature resistance and flame retardance, the safety and stability of the battery can be effectively improved, a lighter, thinner and smaller high-capacity battery can be manufactured, and a great development opportunity is provided in the fields of new energy and high-end consumer products so as to realize the development of higher quality of the aramid fiber industry.

Description

High-temperature-resistant aramid battery diaphragm paper and preparation method and application thereof
Technical Field
The invention belongs to the technical field of polymer fibers and lithium ion batteries, and particularly relates to high-temperature-resistant aramid battery diaphragm paper and a preparation method and application thereof.
Background
At present, a Lithium Ion Battery (LIB) diaphragm still has a certain gap from a battery requirement standard in the aspects of cost, safety, energy density and the like, and particularly, the Lithium Ion Battery (LIB) diaphragm still faces challenges in the aspects of safety performance and the like, and limits the application of high-performance batteries. The separator materials used in the lithium ion battery are mainly microporous polyolefin films such as Polyethylene (PE), polypropylene (PP) and single-layer or multi-layer composite films, and although the separator materials have the advantages of excellent chemical stability, simple preparation process, low production cost, good mechanical properties, proper pore diameter structure and the like, the separator has extremely poor heat resistance, and the separator is easy to shrink and melt after the battery is heated during operation. In recent years, safety accidents such as fire and explosion caused by overheating of a diaphragm of a lithium ion battery frequently happen, so that the safety of the lithium ion battery is an urgent problem, which greatly influences the future development and application of the lithium ion battery, and therefore, further improvement of the safety and the thermal stability of the diaphragm is an important point for the research and development of diaphragm materials, and the development of novel diaphragm materials with excellent thermal stability and high mechanical strength is urgent.
The Aramid Fiber (AF) is a high-performance fiber produced by a high-molecular liquid crystal spinning technology for the first time, and the dosage in the high-performance composite material is inferior to that of the carbon fiber, so that the high-performance composite material has the excellent performances of high strength, high modulus, good stability, high temperature resistance, corrosion resistance, low density and the like. The aramid fiber plays important roles in interface reinforcement and material toughening due to the unique characteristics of structure, high temperature resistance and high mechanical strength, and has become a reinforcing construction material with great potential for constructing high-performance composite materials. The most outstanding characteristics of the aramid fiber are that the aramid fiber has excellent high temperature resistance, can be stably used at a high temperature of 220 ℃ and has no aging phenomenon, the heat shrinkage rate is only 1% at a temperature of about 250 ℃, the phenomena of shrinkage, embrittlement, softening or melting can not be sent when the aramid fiber is exposed at a high temperature of 300 ℃ in a certain time, the decomposition temperature is above 370 ℃, the carbonization temperature is 400 ℃, and certain treated and modified aramid fibers can not be decomposed or melted even at a temperature of 560 ℃. The aramid fiber also has excellent flame retardant effect, the limiting oxygen index is 28 percent, which is higher than the oxygen content of 21 percent in the air, is not easy to burn and not combustion-supporting in the air, can be rapidly extinguished after burning, and has extremely strong self-extinguishing property. Therefore, the high-temperature-resistant and flame-retardant characteristics also expand the application of the aramid fiber in high-temperature special environments and industries, and the aramid fiber is widely applied to the fields of fire-fighting rescue fireproof suits, high-temperature operation departments heat-resistant fireproof clothes, aircraft cabin flame-retardant materials and the like.
Basalt fiber is an inorganic fiber with a diameter of 9-17 μm and a length of 25-3 mm. The basalt mainly comprises the components of working temperature which can reach 200 ℃ at the lowest and 1000 ℃ at the highest, can be stably used for a long time at the temperature above 760 ℃ and can be suitable for high-temperature and corrosive working environments. At present, a great deal of researchers are researching the application of basalt fiber, but the application is mainly focused on the aspects of building, spinning, heat insulation, friction and the like, and the research and report that basalt fiber is used as a novel material for improving the temperature resistance of a battery diaphragm are rare.
At present, researchers have studied a preparation method of a lithium ion battery diaphragm by using aramid fiber, and a Chinese patent application with publication number CN112751135A published in 5 month 4 of 2021 discloses a method of preparing the aramid fiber diaphragm by mixing inorganic and organic polymers and then coating, which can ensure that the diaphragm keeps good high temperature resistance and thermal stability at high temperature, but the porosity of the diaphragm is reduced due to the fact that a coated material fills a diaphragm gap, so that the ion conductivity of the diaphragm is affected. In both the chinese patent application publication No. CN111668425A published in 9/15 in 2020 and the chinese patent application publication No. CN113285171a published in 8/20 in 2021, meta-aramid pulp prepared from meta-phenylenediamine, isophthaloyl chloride, calcium hydroxide and dimethylacetamide is proposed, and after solution viscosity is adjusted, a diaphragm is prepared by stretching.
At present, the problem that a common battery diaphragm is easy to shrink when heated needs to be solved.
Disclosure of Invention
The invention aims to solve the problem that a common battery diaphragm is easy to shrink when heated, and provides high-temperature resistant aramid battery diaphragm paper, a preparation method and application thereof.
In order to achieve the above purpose, the invention adopts the following technical scheme:
a preparation method of high-temperature-resistant aramid battery diaphragm paper comprises the following steps:
step one: dispersing aramid fiber and basalt fiber in water, and adding a dispersing agent to fully untangling and dispersing to obtain an aramid fiber/basalt fiber aqueous dispersion, namely an aramid fiber/basalt fiber mixed slurry;
step two: carrying out wet papermaking forming on the aramid fiber/basalt fiber mixed slurry obtained in the first step to obtain aramid fiber/basalt fiber, and squeezing and drying the aramid fiber/basalt fiber to obtain aramid fiber/basalt composite diaphragm paper, namely aramid paper-based diaphragm paper;
step three: and (3) carrying out hot pressing on the aramid fiber paper-based diaphragm paper obtained in the step (II) to obtain the high-temperature-resistant aramid fiber battery diaphragm paper.
Further, the basalt fiber in the first step adopts modified basalt fiber, and the preparation method of the modified basalt fiber is that the basalt fiber is subjected to calcination and then modified and activated by using sodium hydroxide or a silane coupling agent to obtain the modified basalt fiber.
Further, the mass concentration of the aramid fiber/basalt fiber aqueous dispersion liquid in the first step is 0.5-1.5%; in the first step, the aramid fiber adopts meta-aramid chopped fiber and meta-aramid fibrid.
Further, the adding sequence of the intermediate aramid chopped fiber, the basalt fiber and the meta-aramid fibrid in the step one is as follows: firstly adding meta-aramid chopped fibers and basalt fibers, after untwining and dispersing at 10000-15000 r, adding meta-aramid fibrids, and continuing untwining and dispersing at 10000-15000 r.
5. The preparation method of the high-temperature-resistant aramid battery diaphragm paper according to claim 4, wherein the mass ratio of the intermediate aramid chopped fiber to the basalt fiber is (10-50): (50-10), after meta-aramid fibrid is added, the mass ratio of the aramid fiber to the modified basalt fiber is (50-90): (50-10).
Further, the pressing pressure in the second step is 0.4MPa, and the pressing time is 3-5 min.
Further, in the second step, the vacuum pressure is-0.1 MPa, the drying temperature is 85-110 ℃, and the drying time is 5-8 min.
Further, in the third step, the hot pressing temperature is 180-200 ℃, the hot pressing pressure is 8-12 MPa, the hot pressing time is 1-3 min, and the hot pressing times are 1-3 times.
The high-temperature-resistant aramid battery separator paper is prepared by the preparation method.
An application of high-temperature resistant aramid battery diaphragm paper in preparing lithium ion batteries.
Compared with the prior art, the invention has the following beneficial technical effects:
according to the invention, the wet-process forming papermaking method is used for preparing the diaphragm, and then the hot-press process is used for carrying out post-treatment to improve the interface bonding strength of the aramid fiber-based material, and meanwhile, the strength and toughness of the aramid fiber battery diaphragm paper are obviously improved, so that the problem that the common battery diaphragm is easy to shrink when heated is solved; compared with the traditional diaphragm forming method, the diaphragm preparation method adopted by the invention has the advantages of simpler and more efficient preparation process, environmental protection, and capabilities of providing new thought and theoretical guidance for preparing high-performance battery diaphragm paper and enriching the preparation technology and theory of the existing basalt fiber reinforced composite material.
The invention utilizes the excellent spinnability, fire resistance and corrosion resistance of the aramid fiber and combines the excellent dimensional stability, fire resistance and corrosion resistance of the basalt fiber, and the obtained aramid fiber battery diaphragm paper has excellent comprehensive performance. The diaphragm paper has the advantages of thinner thickness, chemical corrosion resistance, stable size, no shrinkage at the temperature of more than 200 ℃, and capability of stably working in a high-temperature environment. The aramid fiber battery diaphragm paper has good self-extinguishing property and high safety, the limiting oxygen index of the diaphragm paper can reach 35, the ignition is not easy to occur, the combustion is not continuous, the combustion can be rapidly controlled when the battery is subjected to thermal runaway in the use process, and the safety and the durability of the power battery are improved.
The preparation method of the aramid battery diaphragm paper by using the wet forming mode is simple in preparation process and simple in operation, and is doped with meta-aramid precipitation and other differentiated aramid fibers as a binding material, so that the binding force between the fibers is enhanced, an ideal pore structure can be effectively built, the overall performance of the aramid battery diaphragm is improved, and the ionic conductivity of the diaphragm is improved. The aramid fiber and basalt fiber have higher thermal stability and dimensional stability, the aramid paper and basalt composite paper prepared by the wet forming technology have more pores, and the aramid fiber and basalt composite paper is expected to meet the performance requirements of lithium ion battery diaphragms on ion resistance, chemical and thermal stability, mechanical strength and the like, and the preparation of the aramid paper-based battery diaphragm by a low-cost papermaking process has great potential to become a new generation of LIB battery diaphragm material.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the invention.
Fig. 1 is an SEM image of the high temperature resistant aramid battery separator paper prepared in example 4 of the present invention.
Fig. 2 is a schematic combustion diagram of the high temperature resistant aramid battery separator paper prepared in example 4 of the present invention.
Detailed Description
The present invention is described in further detail below:
a high temperature resistant aramid battery diaphragm paper is formed by utilizing an aramid fiber and basalt fiber dispersion liquid wet method, wherein the mass ratio of the aramid fiber to the basalt fiber is (50-90): (50-10). The raw materials are subjected to the steps of fiber sizing, wet forming, hot pressing film forming and the like to obtain the high-temperature-resistant aramid fiber battery diaphragm paper, wherein the ration is 20g/m 2 . The aramid fiber adopts meta-aramid chopped fiber and meta-aramid fibrid.
A preparation method of high-temperature-resistant aramid battery diaphragm paper comprises the following steps:
(1) Preparing fiber slurry: taking a certain mass of meta-aramid chopped fiber, basalt fiber and PEO dispersing agent in water, wherein the mass of the meta-aramid chopped fiber is 10-50 parts, the mass of the basalt fiber is 50-10 parts, and the mass fraction of PEO is 0.5%; stirring and dispersing 10000-15000 r, adding 40-50 parts of meta-aramid fibrid, and continuously dispersing 10000-15000 r to obtain the aramid fiber/basalt fiber mixed slurry with the mass concentration of 0.5-1.5%. The length of the meta-aramid chopped fiber is 0.3-1.2 mm, the diameter of the meta-aramid chopped fiber is 7-12 mu m, the basalt fiber adopts modified basalt fiber, and the basalt fiber is calcined and then modified and activated by sodium hydroxide or a silane coupling agent to obtain modified basalt fiber, wherein the calcining temperature is 350 ℃ and the calcining time is 2 hours. The length of the modified basalt fiber is 7mm, and the diameter of the modified basalt fiber is 9-12 mu m. The mass ratio of the meta-aramid chopped fiber to the basalt fiber is (10-50): (50-10), after meta-aramid fibrid is added, the mass ratio of the aramid fiber to the basalt fiber is (50-90): (50-10).
(2) Wet forming: pouring the slurry stirred and dispersed in the first step into a molding barrel of a sheet making machine, filtering water, molding on a 200-mesh net, putting into a squeezer, squeezing for 3-5 min by using the pressure of 0.4MPa, putting into a vacuum dryer, drying at the vacuum pressure of-0.1 MPa and the temperature of 85-110 ℃ for 5-8 min, and obtaining the aramid fiber/basalt composite diaphragm paper.
(3) Hot pressing to form a film: and (3) placing the aramid fiber/basalt fiber composite diaphragm paper obtained in the step two into a flat vulcanizing machine for hot pressing treatment, wherein the temperature is set at 180-200 ℃, the pressure is 8-12 MPa, the time is 1-3 min, the times are 1-3 times, and taking out and standing for 5min after hot pressing is finished for cooling, so that the hot-pressed high-temperature-resistant aramid fiber battery diaphragm paper is obtained.
An application of high-temperature resistant aramid battery diaphragm paper in preparing lithium ion batteries.
The invention is described in further detail below with reference to examples:
example 1
The high-temperature-resistant aramid battery diaphragm paper is formed by utilizing an aramid fiber and basalt fiber dispersion liquid wet method, wherein the mass ratio of the aramid fiber to the basalt fiber is 50:50. the raw materials are subjected to the steps of fiber sizing, wet forming, hot pressing film forming and the like to obtain the high-temperature-resistant aramid fiber battery diaphragm paper, wherein the ration is 20g/m 2 。
A preparation method of high-temperature-resistant aramid battery diaphragm paper comprises the following steps:
(1) Preparing fiber slurry: taking a certain mass of meta-aramid chopped fiber, basalt fiber and PEO dispersing agent in water, wherein the mass of the meta-aramid chopped fiber is 10 parts, the mass of the basalt fiber is 50 parts, and the mass fraction of PEO is 0.5%; stirring and dispersing 10000r, then adding 40 parts by mass of meta-aramid fibrid, and continuing dispersing 15000r to obtain the aramid fiber/basalt fiber mixed slurry with the mass concentration of 0.5%.
(2) Wet forming: pouring the slurry stirred and dispersed in the first step into a molding barrel of a sheet making machine, filtering water, molding on a 200-mesh net, putting into a squeezer, squeezing for 3min by using the pressure of 0.4MPa, putting into a vacuum dryer, drying at the vacuum pressure of-0.1 MPa and the temperature of 85 ℃ for 5min, and obtaining the aramid fiber/basalt composite diaphragm paper.
(3) Hot pressing to form a film: and (3) placing the aramid fiber/basalt fiber composite diaphragm paper obtained in the step (II) into a flat vulcanizing machine for hot pressing treatment, wherein the temperature is set at 180 ℃, the pressure is 8MPa, the time is 1min, the times are 2 times, and taking out and standing for 5min after hot pressing is finished for cooling, so that the hot-pressed high-temperature-resistant aramid fiber battery diaphragm paper is obtained.
And preparing the lithium ion battery by using the high-temperature resistant aramid battery diaphragm paper.
Example 2
The high-temperature-resistant aramid battery diaphragm paper is formed by utilizing an aramid fiber and basalt fiber dispersion liquid wet method, wherein the mass ratio of the aramid fiber to the basalt fiber is 75:25. the raw materials are subjected to the steps of fiber sizing, wet forming, hot pressing film forming and the like to obtain the high-temperature-resistant aramid fiber battery diaphragm paper, wherein the ration is 20g/m 2 。
A preparation method of high-temperature-resistant aramid battery diaphragm paper comprises the following steps:
(1) Preparing fiber slurry: taking a certain mass of meta-aramid chopped fiber, basalt fiber and PEO dispersing agent in water, wherein the mass of the meta-aramid chopped fiber is 25 parts, the mass of the basalt fiber is 25 parts, and the mass fraction of PEO is 0.5%; after stirring and dispersing for 11000r, adding 50 parts by mass of meta-aramid fibrid, and continuously dispersing for 14000r to obtain the aramid fiber/basalt fiber mixed slurry with the mass concentration of 0.8%.
(2) Wet forming: pouring the slurry stirred and dispersed in the first step into a molding barrel of a sheet making machine, filtering water, molding on a 200-mesh net, putting into a squeezer, squeezing for 4min by using the pressure of 0.4MPa, putting into a vacuum dryer, drying at the vacuum pressure of-0.1 MPa and the temperature of 90 ℃ for 6min, and obtaining the aramid fiber/basalt composite diaphragm paper.
(3) Hot pressing to form a film: and (3) placing the aramid fiber/basalt fiber composite diaphragm paper obtained in the step (II) into a flat vulcanizing machine for hot pressing treatment, wherein the temperature is set to 190 ℃, the pressure is 9MPa, the time is 2min, the times are 2 times, and after the hot pressing is finished, the aramid fiber/basalt fiber composite diaphragm paper is taken out and kept stand for 5min for cooling, so that the hot-pressed high-temperature-resistant aramid fiber battery diaphragm paper is obtained.
Example 3
A high temperature resistant aramid battery diaphragm paper is formed by a aramid fiber and basalt fiber dispersion liquid wet method, wherein the aramid fiber and basalt fiber are mixed with one another to form a paperThe mass ratio of (2) is 70:30. the raw materials are subjected to the steps of fiber sizing, wet forming, hot pressing film forming and the like to obtain the high-temperature-resistant aramid fiber battery diaphragm paper, wherein the ration is 20g/m 2 。
A preparation method of high-temperature-resistant aramid battery diaphragm paper comprises the following steps:
(1) Preparing fiber slurry: taking a certain mass of meta-aramid chopped fiber, basalt fiber and PEO dispersing agent in water, wherein the mass of the meta-aramid chopped fiber is 25 parts, the mass of the basalt fiber is 30 parts, and the mass fraction of PEO is 0.5%; and adding 45 parts by mass of meta-aramid fibrid after stirring and dispersing 12000r, and continuously dispersing 12000r to obtain the aramid fiber/basalt fiber mixed slurry with the mass concentration of 1%.
(2) Wet forming: pouring the slurry stirred and dispersed in the first step into a molding barrel of a sheet making machine, filtering water, molding on a 200-mesh net, putting into a squeezer, squeezing for 5min by using the pressure of 0.4MPa, putting into a vacuum dryer, drying at the vacuum pressure of-0.1 MPa and the temperature of 100 ℃ for 6min, and obtaining the aramid fiber/basalt composite diaphragm paper.
(3) Hot pressing to form a film: and (3) placing the aramid fiber/basalt fiber composite diaphragm paper obtained in the step (II) into a flat vulcanizing machine for hot pressing treatment, wherein the temperature is set to be 200 ℃, the pressure is 10MPa, the time is 1min, the times are 3 times, and taking out and standing for 5min after the hot pressing is finished, and cooling the aramid fiber/basalt fiber composite diaphragm paper to obtain the hot-pressed high-temperature-resistant aramid fiber battery diaphragm paper.
Example 4
The high-temperature-resistant aramid battery diaphragm paper is formed by utilizing an aramid fiber and basalt fiber dispersion liquid wet method, wherein the mass ratio of the aramid fiber to the basalt fiber is 40:60. the raw materials are subjected to the steps of fiber sizing, wet forming, hot pressing film forming and the like to obtain the high-temperature-resistant aramid fiber battery diaphragm paper, wherein the ration is 20g/m 2 。
A preparation method of high-temperature-resistant aramid battery diaphragm paper comprises the following steps:
(1) Preparing fiber slurry: taking a certain mass of meta-aramid chopped fiber, basalt fiber and PEO dispersing agent in water, wherein the mass of the meta-aramid chopped fiber is 35 parts, the mass of the basalt fiber is 15 parts, and the mass fraction of PEO is 0.5%; after 13000r stirring and dispersing, 50 parts of meta-aramid fibrid is added for continuing to disperse 11000r, and the aramid fiber/basalt fiber mixed slurry with the mass concentration of 1.2% is obtained.
(2) Wet forming: pouring the slurry stirred and dispersed in the first step into a molding barrel of a sheet making machine, filtering water, molding on a 200-mesh net, putting into a squeezer, squeezing for 4min by using the pressure of 0.4MPa, putting into a vacuum dryer, drying at the vacuum pressure of-0.1 MPa and the temperature of 105 ℃ for 7min, and obtaining the aramid fiber/basalt composite diaphragm paper.
(3) Hot pressing to form a film: and (3) placing the aramid fiber/basalt fiber composite diaphragm paper obtained in the step (II) into a flat vulcanizing machine for hot pressing treatment, wherein the temperature is set to 190 ℃, the pressure is 11MPa, the time is 2min, the times are 1, and after hot pressing is finished, the aramid fiber/basalt fiber composite diaphragm paper is taken out and kept stand for 5min for cooling, so that the hot-pressed high-temperature-resistant aramid fiber battery diaphragm paper is obtained.
An SEM image of the high temperature resistant aramid battery separator paper prepared in example 4 is shown in fig. 1. The combustion schematic diagram of the high-temperature resistant aramid battery separator paper prepared in example 4 is shown in fig. 2.
The high temperature resistant aramid fiber battery diaphragm paper prepared in the embodiment 4 is detected and characterized, the combustion is shown in a figure 2, and the partial indexes are respectively 1, and the thickness of the diaphragm paper is 35 mu m; 2. quantification: 20g/m 2 The method comprises the steps of carrying out a first treatment on the surface of the 3. Tensile strength: 30MPa; 4. the diaphragm paper is not broken after burning, and the burning does not continue to have a self-extinguishing function.
Example 5
The high-temperature-resistant aramid battery diaphragm paper is formed by utilizing an aramid fiber and basalt fiber dispersion liquid wet method, wherein the mass ratio of the aramid fiber to the basalt fiber is 90:10. the raw materials are subjected to the steps of fiber sizing, wet forming, hot pressing film forming and the like to obtain the high-temperature-resistant aramid fiber battery diaphragm paper, wherein the ration is 20g/m 2 。
A preparation method of high-temperature-resistant aramid battery diaphragm paper comprises the following steps:
(1) Preparing fiber slurry: taking a certain mass of meta-aramid chopped fiber, basalt fiber and PEO dispersing agent in water, wherein the mass of the meta-aramid chopped fiber is 50 parts, the mass of the basalt fiber is 10 parts, and the mass fraction of PEO is 0.5%; stirring and dispersing 15000r, adding 40 parts by mass of meta-aramid fibrid, and continuously dispersing 10000r to obtain the aramid fiber/basalt fiber mixed slurry with the mass concentration of 1.5%.
(2) Wet forming: pouring the slurry stirred and dispersed in the first step into a molding barrel of a sheet making machine, filtering water, molding on a 200-mesh net, putting into a squeezer, squeezing for 3min by using the pressure of 0.4MPa, putting into a vacuum dryer, drying at the vacuum pressure of-0.1 MPa and the temperature of 110 ℃ for 8min, and obtaining the aramid fiber/basalt composite diaphragm paper.
(3) Hot pressing to form a film: and (3) placing the aramid fiber/basalt fiber composite diaphragm paper obtained in the step (II) into a flat vulcanizing machine for hot pressing treatment, wherein the temperature is set to be 200 ℃, the pressure is set to be 12MPa, the time is set to be 3min, the times are set to be 2 times, and the aramid fiber/basalt fiber composite diaphragm paper is taken out and kept stand for 5min after hot pressing is finished for cooling, so that the hot-pressed high-temperature-resistant aramid fiber battery diaphragm paper is obtained.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention and not for limiting the scope of protection thereof, and although the present invention has been described in detail with reference to the above embodiments, it should be understood by those of ordinary skill in the art that: various changes, modifications, or equivalents may be made to the particular embodiments of the invention by those skilled in the art after reading the present disclosure, but such changes, modifications, or equivalents are within the scope of the invention as defined in the appended claims.

Claims (10)

1. The preparation method of the high-temperature-resistant aramid battery diaphragm paper is characterized by comprising the following steps of:
step one: dispersing aramid fiber and basalt fiber in water, and adding a dispersing agent to fully untangling and dispersing to obtain an aramid fiber/basalt fiber aqueous dispersion, namely an aramid fiber/basalt fiber mixed slurry;
step two: carrying out wet papermaking forming on the aramid fiber/basalt fiber mixed slurry obtained in the first step to obtain aramid fiber/basalt fiber, and squeezing and drying the aramid fiber/basalt fiber to obtain aramid fiber/basalt composite diaphragm paper, namely aramid paper-based diaphragm paper;
step three: and (3) carrying out hot pressing on the aramid fiber paper-based diaphragm paper obtained in the step (II) to obtain the high-temperature-resistant aramid fiber battery diaphragm paper.
2. The preparation method of the high-temperature-resistant aramid battery diaphragm paper is characterized in that the basalt fiber in the first step adopts modified basalt fiber, and the preparation method of the modified basalt fiber is that the basalt fiber is subjected to calcination and then modified activation by using sodium hydroxide or a silane coupling agent to obtain the modified basalt fiber.
3. The method for preparing high temperature resistant aramid battery diaphragm paper according to claim 1, wherein the mass concentration of the aramid fiber/basalt fiber aqueous dispersion in the first step is 0.5% -1.5%; in the first step, the aramid fiber adopts meta-aramid chopped fiber and meta-aramid fibrid.
4. The method for preparing high temperature resistant aramid battery separator paper according to claim 3, wherein the adding sequence of the intermediate aramid chopped fiber, basalt fiber and meta-aramid fibrid is as follows: firstly adding meta-aramid chopped fibers and basalt fibers, after untwining and dispersing at 10000-15000 r, adding meta-aramid fibrids, and continuing untwining and dispersing at 10000-15000 r.
5. The preparation method of the high-temperature-resistant aramid battery diaphragm paper according to claim 4, wherein the mass ratio of the intermediate aramid chopped fiber to the basalt fiber is (10-50): (50-10), after meta-aramid fibrid is added, the mass ratio of the aramid fiber to the modified basalt fiber is (50-90): (50-10).
6. The method for preparing the high-temperature-resistant aramid battery diaphragm paper according to claim 1, wherein the pressing pressure in the second step is 0.4MPa, and the pressing time is 3-5 min.
7. The method for preparing the high-temperature-resistant aramid battery diaphragm paper according to claim 1, wherein the vacuum pressure in the drying process in the second step is-0.1 MPa, the drying temperature is 85-110 ℃, and the drying time is 5-8 min.
8. The method for preparing the high-temperature-resistant aramid battery diaphragm paper according to claim 1, wherein the hot pressing temperature in the third step is 180-200 ℃, the hot pressing pressure is 8-12 MPa, the hot pressing time is 1-3 min, and the hot pressing times are 1-3 times.
9. A high temperature resistant aramid battery separator paper, characterized in that it is produced by the production method as claimed in any one of claims 1 to 8.
10. Use of the high temperature resistant aramid battery separator paper of claim 9 in the preparation of lithium ion batteries.
CN202310340968.8A 2023-03-31 2023-03-31 High-temperature-resistant aramid battery diaphragm paper and preparation method and application thereof Pending CN116200961A (en)

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105538808A (en) * 2015-12-25 2016-05-04 耀奇鑫科技（深圳）有限公司 Hybrid fiber enhanced composite material and preparation process of hybrid fiber enhanced composite material
CN108232089A (en) * 2018-01-05 2018-06-29 吉林大学 A kind of lithium ion battery diatomite diaphragm and preparation method thereof
CN110528314A (en) * 2019-06-19 2019-12-03 武汉纺织大学 A kind of composite sheet and its preparation method and application of the polyphenylene sulfide superfine fiber containing melt-blown
CN113725556A (en) * 2021-09-02 2021-11-30 深圳市星源材质科技股份有限公司 Nonwoven fabric and battery separator
CN115207559A (en) * 2022-06-28 2022-10-18 陈克复 High-performance aramid fiber diaphragm and preparation method and application thereof
CN115663399A (en) * 2022-12-28 2023-01-31 江苏卓高新材料科技有限公司 Composite diaphragm and preparation method and application thereof

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105538808A (en) * 2015-12-25 2016-05-04 耀奇鑫科技（深圳）有限公司 Hybrid fiber enhanced composite material and preparation process of hybrid fiber enhanced composite material
CN108232089A (en) * 2018-01-05 2018-06-29 吉林大学 A kind of lithium ion battery diatomite diaphragm and preparation method thereof
CN110528314A (en) * 2019-06-19 2019-12-03 武汉纺织大学 A kind of composite sheet and its preparation method and application of the polyphenylene sulfide superfine fiber containing melt-blown
CN113725556A (en) * 2021-09-02 2021-11-30 深圳市星源材质科技股份有限公司 Nonwoven fabric and battery separator
CN115207559A (en) * 2022-06-28 2022-10-18 陈克复 High-performance aramid fiber diaphragm and preparation method and application thereof
CN115663399A (en) * 2022-12-28 2023-01-31 江苏卓高新材料科技有限公司 Composite diaphragm and preparation method and application thereof

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