CN102108635B - Method for preparing battery diaphragm material by irradiation grafting of acrylic acid - Google Patents
Method for preparing battery diaphragm material by irradiation grafting of acrylic acid Download PDFInfo
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract
The method for preparing the battery diaphragm material by radiation grafting of acrylic acid, which is disclosed by the invention, uses PP non-woven fabric as a raw material to graft acrylic acid, and comprises the following steps: washing PP non-woven fabric with acetone; then B, washing with distilled water, and airing; C. pre-irradiating the dried non-woven fabric; D. preparing an acrylic acid aqueous solution; E. soaking the non-woven fabric subjected to pre-irradiation in an acrylic acid aqueous solution, and adding ferrous sulfate and concentrated sulfuric acid to perform grafting reaction; F. and cleaning the surface of the grafted non-woven fabric with acetone, airing and packaging. The method of the invention improves the material performance, the resistance of the battery diaphragm material can reach 17.46 ohm, the voltage can reach 1.357v, the high temperature performance and the anti-oxidation performance are excellent, and the invention is suitable for being applied to the large-current high-power battery.
Description
Technical Field
The invention relates to a battery diaphragm material, in particular to a method for preparing the battery diaphragm material by radiation grafting of acrylic acid.
Background
With the rapid development of electronic technology, the pace of updating in the mobile communication and computer industries is greatly accelerated. The electric appliance element is required to be smaller in size, more complete in function and longer in standby time. For this reason, batteries in the electric storage elements are one of the important elements in which improvement is required. The battery diaphragm is known as the third pole of the battery, is one of the important components of cadmium-nickel and hydrogen-nickel batteries, and plays the roles of isolating the cathode and the anode, preventing the battery from short circuit, absorbing electrolyte, enabling conductive particles to pass through smoothly, enabling gas to permeate the diaphragm and the like. The quality of the material directly affects the charge and discharge performance, high and low temperature performance, charge storage and service life of the battery, and therefore, the battery diaphragm material is required to have excellent acid and alkali resistance and low resistance. Multiple selection of synthetic fibers through battery separators such as: polyamide fiber, polyethanol fiber, polypropylene fiber, polyester fiber, polyolefin fiber, etc. the preferred material is polyolefin fiber with excellent wear resistance, elasticity, acid and alkali resistance, oxidation resistance, high temperature resistance and light weight. However, the molecular structure of the polyolefin fiber has no hydrophilic gene, the crystallinity is very high, the cross section of the fiber is circular, and the fiber has strong hydrophobicity, and the requirement of the battery diaphragm can be met only by modifying the fiber. The cadmium-nickel and hydrogen-nickel battery diaphragm material is basically imported, because the cadmium-nickel and hydrogen-nickel battery diaphragm material is used for batteries such as mobile phones in the United states and Japan and is still under research in the aspect of the battery.
Polyolefin films are generally non-polar and poorly hydrophilic and cannot be used directly as battery separators. The surface of the film or the polyolefin macromolecular chain is grafted with groups capable of carrying out ion exchange through radiation grafting, so that the hydrophilicity of the polyolefin film can be improved, the ion exchange function can be endowed, and the requirements of the battery diaphragm are met.
In the 60 s of the 20 th century, the united states RAI company used benzene as a solvent to graft acrylic acid and methacrylic acid on the surfaces of polyethylene, polypropylene and polytetrafluoroethylene films by radiation technology, successfully prepared alkaline battery separators, and put into mass production in the middle of the 70 s. Radiation grafting technology in aqueous systems was developed in the early 80 s. In China, the polyethylene-g-acrylic acid film is successfully prepared by applying an aqueous solution system adopted by a physical research institute in Shanghai of Chinese academy of sciences as early as 20 th century in 70 s through a co-radiation grafting technology and is successfully applied to button cells.
At present, diaphragm materials prepared by radiation grafting modification are widely applied to button silver-zinc, zinc-manganese, zinc-air and other batteries, secondary silver-zinc, cadmium-nickel, zinc-nickel, cylindrical hydrogen-nickel batteries and the like. The radiation grafting modified polyolefin battery diaphragm has many advantages of lyophilic property, strong liquid retention capacity, high capacity of assembled batteries, long cycle life and the like, and is often used as a diaphragm of a large-capacity and high-power-density battery.
The alkaline high-energy battery (including nickel-hydrogen battery, cadmium-nickel battery and alkaline manganese battery) has the characteristics of large current and high power, and the service life of the alkaline high-energy battery is 7 to 8 times longer than that of a common battery. The alkaline battery diaphragm belongs to a cation exchange membrane, mainly comprises a carboxylic acid type weak acid cation exchange membrane and a sulfonic acid type strong acid cation exchange membrane, and the two membranes can be prepared by adopting a radiation grafting method. Weakly acidic cation membranes are usually prepared by radiation grafting of monomers such as acrylic acid or methacrylic acid on polymer membranes such as polyethylene, polypropylene and PTFE, while for strongly acidic cation exchange membranes, there are two radiation grafting methods, and one method which is researched and reported is to graft styrene on a polymer (mainly fluorine-containing polymer) membrane by radiation and then sulfonate benzene rings; the second method is to graft a vinyl sulfonate monomer directly onto the polymer film by irradiation.
However, the polyethylene film is reacted with acrylic acid to carry out graft copolymerization, and usually the polyethylene film is irradiated with poly and then grafted by chemical reaction, which has the technical defects that the required irradiation dose is too large, and reaches 200 to 900Kgy, and the chemical reaction needs to add an initiator and the like.
The PP non-woven fabric can be used as the alkaline battery diaphragm after being subjected to surface modification treatment by low-temperature plasma treatment. By plasma treatment, polar genes such as carboxyl, hydroxyl and the like are introduced to the surface of the non-woven fabric, so that the infiltration performance of the PP non-woven fabric alkaline electrolyte is improved, the alkali absorption rate and the alkali absorption rate are increased, and the use requirement of the battery diaphragm is further met. In the plasma modification method of the PP non-woven fabric for the alkaline battery diaphragm, generally, firstly, the PP non-woven fabric needs to be washed, and a sample is placed in an acetone solvent and cleaned by ultrasonic oscillation so as to remove oil stains and other impurities on the surface. Then washing with distilled water, and drying at 50-60 ℃. And taking out the dried PP non-woven fabric for plasma surface treatment. During treatment, the non-woven fabric is suspended in a plasma treatment chamber, a vacuum extraction valve is opened, and after a certain background vacuum degree is reached, working gas is introduced to reach the required working air pressure. And turning on a radio frequency power supply, adjusting to the required power, and taking out the sample after processing for a certain time. The battery separator performance depends on the process parameters during plasma processing.
However, the plasma and substrate surface interactions are mainly radical activation, cross-linking and surface etching, which compete with each other. Therefore, the plasma grafting of acrylic acid has the disadvantage of low grafting ratio and limited use effect.
Disclosure of Invention
The invention aims to provide a novel method for preparing a battery diaphragm material by irradiating and grafting acrylic acid.
The method for preparing the battery diaphragm material by radiation grafting of acrylic acid, which is disclosed by the invention, uses PP non-woven fabric as a raw material to graft acrylic acid, and comprises the following steps:
washing PP non-woven fabric with acetone; then the
B. Cleaning with distilled water, and air drying;
C. pre-irradiating the dried PP non-woven fabric;
D. preparing an acrylic acid aqueous solution;
E. soaking the PP non-woven fabric subjected to pre-irradiation in an acrylic acid aqueous solution, and adding ferrous sulfate and concentrated sulfuric acid to perform grafting reaction;
F. and cleaning the surface of the grafted PP non-woven fabric with acetone, airing and packaging.
The irradiation dose of the pre-irradiation in the step C is 4-20kgy, and preferably 8-15kgy.
In the step D, the acrylic acid aqueous solution prepared by adding water to the industrial acrylic acid has the volume concentration of 5-40%, preferably 20-30%.
When the PP non-woven fabric is soaked in an acrylic acid aqueous solution, the ratio of the mass of the PP non-woven fabric to the volume of the acrylic acid aqueous solution is 1; the ratio of the ferrous sulfate mass to the PP non-woven fabric mass is 1:100 to 5, preferably 2:100 to 4, wherein the ratio of the volume of concentrated sulfuric acid to the mass of the PP non-woven fabric is 1; the initial temperature of the grafting reaction is 40 to 60 ℃, and the grafting reaction time is 4 to 8 hours.
The non-woven fabric battery diaphragm is a mainstream product of the battery diaphragm and mainly comprises a nylon fiber battery diaphragm, a polypropylene fiber battery diaphragm and a vinylon battery diaphragm. Among them, polypropylene fibers are most chemically stable, but it is necessary to increase the alkali absorption rate and the alkali absorption speed. The non-woven polypropylene (PP) fabric is used as a base material, and acrylic acid is grafted by radiation to prepare the mercury-free alkaline zinc-manganese dioxide battery diaphragm. In the traditional alkaline zinc-manganese battery, mercury or mercury compounds are added to improve the thermodynamic stability of the powdery zinc anode and inhibit the hydrogen evolution phenomenon of zinc. However, the mercury volatilization in the production process and the battery waste can cause environmental pollution, so that the realization of the mercury-free alkaline zinc-manganese battery is a good development direction. In mercury-free alkaline zinc-manganese batteries, the phenomenon of acicular dendrites of zinc oxide growing from the anode, which cause the penetration of the separator to cause short-circuiting of the battery, requires an increase in the wet strength of the separator and a reduction in the pore size of the separator.
The method of the invention optimizes the main influencing factors of the pre-irradiation grafting of acrylic acid on the PP non-woven fabric, such as: pre-radiation dose and dose rate, grafting reaction time and temperature, acrylic acid concentration in a monomer system, a catalyst and the like. During the grafting reaction, a certain amount of ferrous sulfate and concentrated sulfuric acid are added to prevent homopolymerization of acrylic acid monomers, so that the problem of self-polymerization of acrylic acid in a high-dose environment is solved, and the grafting rate is improved. And finally, the acetone can be used for thoroughly washing off acid liquor and homopolymer on the surface, so that the product quality is ensured.
The method of the invention improves the material performance, the resistance of the battery diaphragm material can reach 17.46 ohm, the voltage can reach 1.357v, the high temperature performance and the anti-oxidation performance are excellent, and the battery diaphragm material is suitable for being applied to a large-current high-power battery.
Detailed Description
Example 1
A. Soaking 10kg of PP non-woven fabric in acetone for 2 hours, and removing greasy substances on the surface layer.
B. Washing PP non-woven fabric with distilled water, and drying.
C. And placing the dried PP non-woven fabric into a container, and irradiating with the irradiation dose of 4kgy.
D. Preparing an acrylic acid aqueous solution: the volume concentration of the acrylic acid aqueous solution prepared by adding water into industrial acrylic acid is 5 percent.
E. The PP non-woven fabric which is well pre-irradiated is soaked in 300l of acrylic acid water solution, 0.1kg of ferrous sulfate and 9l of concentrated sulfuric acid are added, the initial temperature of grafting reaction is 40 ℃, and the grafting reaction time is 4 hours.
F. And cleaning the surface of the grafted non-woven fabric with acetone, airing and packaging.
Example 2
A. Soaking 10kg of PP non-woven fabric in acetone for 12h, and removing greasy substances on the surface layer.
B. Washing PP non-woven fabric with distilled water, and drying.
C. And placing the dried PP non-woven fabric into a container, and irradiating with the irradiation dose of 10kgy.
D. Preparing an acrylic acid aqueous solution: the volume concentration of the acrylic acid aqueous solution prepared by adding water into industrial acrylic acid is 20 percent.
E. The PP non-woven fabric which is well pre-irradiated is soaked in 250l of acrylic acid water solution, 0.3kg of ferrous sulfate and 20l of concentrated sulfuric acid are added, the initial temperature of the grafting reaction is 50 ℃, and the grafting reaction time is 6 hours.
F. And cleaning the surface of the grafted non-woven fabric with acetone, airing and packaging.
Example 3
A. Soaking 10kg of PP non-woven fabric in acetone for 24 hours, and removing greasy substances on the surface layer.
B. Washing PP non-woven fabric with distilled water, and drying.
C. And placing the dried PP non-woven fabric into a container, and irradiating with the irradiation dose of 20kgy.
D. Preparing an acrylic acid aqueous solution: the volume concentration of the acrylic acid aqueous solution prepared by adding water into industrial acrylic acid is 40 percent.
E. The PP non-woven fabric which is well pre-irradiated is soaked in 150l of acrylic acid water solution, 0.5kg of ferrous sulfate and 50l of concentrated sulfuric acid are added, the initial temperature of the grafting reaction is 60 ℃, and the grafting reaction time is 8 hours.
F. And cleaning the surface of the grafted non-woven fabric with acetone, airing and packaging.
Example 4
A. Soaking 10kg of PP non-woven fabric in acetone for 12h, and removing greasy substances on the surface layer.
B. Washing PP non-woven fabric with distilled water, and drying.
C. And placing the dried PP non-woven fabric into a container, and irradiating with the irradiation dose of 12kgy.
D. Preparing an acrylic acid aqueous solution: the volume concentration of the acrylic acid aqueous solution prepared by adding water into industrial acrylic acid is 25 percent.
E. The PP non-woven fabric which is well pre-irradiated is soaked in 220l of acrylic acid water solution, 0.3kg of ferrous sulfate and 15l of concentrated sulfuric acid are added, the initial temperature of the grafting reaction is 50 ℃, and the grafting reaction time is 6 hours.
F. And cleaning the surface of the grafted non-woven fabric with acetone, airing and packaging.
Claims (7)
1. The method for preparing the battery diaphragm material by radiation grafting of acrylic acid uses PP non-woven fabric as a raw material to graft the acrylic acid, and is characterized in that: the method comprises the following steps:
washing PP non-woven fabric with acetone; then the
B. Cleaning with distilled water, and air drying;
C. pre-irradiating the dried PP non-woven fabric with the irradiation dose of 4-20kgy;
D. preparing an acrylic acid aqueous solution;
E. soaking the PP non-woven fabric subjected to pre-irradiation in an acrylic acid aqueous solution, and adding ferrous sulfate and concentrated sulfuric acid to perform a grafting reaction;
F. and cleaning the surface of the grafted PP non-woven fabric with acetone, airing and packaging.
2. The method for preparing the battery separator material by radiation grafting of acrylic acid according to claim 1, wherein: in the step A, soaking PP non-woven fabric in acetone for 2 to 24h.
3. The method for preparing the battery separator material by radiation grafting of acrylic acid according to claim 1, wherein: and C, pre-irradiating the glass substrate in the step C, wherein the irradiation dose of the pre-irradiation is 8 to 15kgy.
4. The method for preparing the battery separator material by radiation grafting of acrylic acid according to claim 1, wherein: in the step D, industrial acrylic acid is added with water to prepare an acrylic acid aqueous solution with the volume concentration of 5-40%.
5. The method for preparing a battery separator material by radiation grafting acrylic acid according to claim 1 or 4, wherein: in the step D, industrial acrylic acid is added with water to prepare an acrylic acid aqueous solution with the volume concentration of 20-30%.
6. The method for preparing the battery separator material by radiation grafting of acrylic acid according to claim 1, wherein: in the step E, when the PP non-woven fabric is soaked in the acrylic acid aqueous solution, the ratio of the mass of the PP non-woven fabric to the volume of the acrylic acid aqueous solution is 1; the ratio of the ferrous sulfate mass to the PP non-woven fabric mass is 1:100 to 5, wherein the ratio of the volume of concentrated sulfuric acid to the mass of the PP non-woven fabric is 1.2 to 1; the initial temperature of the grafting reaction is 40 to 60 ℃, and the grafting reaction time is 4 to 8 hours.
7. The method for preparing battery separator material by radiation grafting acrylic acid according to claim 1 or 6, characterized in that: in the step E, when the PP non-woven fabric is soaked in the acrylic acid aqueous solution, the ratio of the mass of the PP non-woven fabric to the volume of the acrylic acid aqueous solution is 1 to 20-1; the ratio of the ferrous sulfate mass to the PP non-woven fabric mass is 2:100 to 4, wherein the ratio of the volume of concentrated sulfuric acid to the mass of the PP non-woven fabric is 1; the initial temperature of the grafting reaction is 40 to 60 ℃, and the grafting reaction time is 4 to 8 hours.
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| CN2011100266463A CN102108635B (en) | 2011-01-25 | 2011-01-25 | Method for preparing battery diaphragm material by irradiation grafting of acrylic acid |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107799698A (en) * | 2016-08-31 | 2018-03-13 | 住友化学株式会社 | The manufacture method of nonaqueous electrolytic solution secondary battery distance piece |
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|---|---|---|---|---|
| CN105860124A (en) * | 2015-01-22 | 2016-08-17 | 中国科学院上海应用物理研究所 | Pre-irradiation method for grafting of polymer material with hydrophilic monomer |
| CN107447514A (en) * | 2017-08-29 | 2017-12-08 | 苏州市苏真床垫有限公司 | A kind of cationic monomer graft polypropylene non-woven fabrics and preparation method thereof |
| CN112133871A (en) * | 2020-09-24 | 2020-12-25 | 湖南省凯纳方科技有限公司 | Surface grafting method of mh-ni battery diaphragm |
| CN112126113A (en) * | 2020-09-24 | 2020-12-25 | 湖南省凯纳方科技有限公司 | Surface grafting modifier for mh-ni battery diaphragm |
| CN112226166A (en) * | 2020-10-14 | 2021-01-15 | 湖北迈可瑞橡塑有限公司 | Method for bonding PTFE (polytetrafluoroethylene) plate and metal |
| CN114221091A (en) * | 2021-12-17 | 2022-03-22 | 深圳市量能科技有限公司 | Irradiation modification method for lithium ion battery diaphragm |
| CN117024828A (en) * | 2023-08-26 | 2023-11-10 | 桂林理工大学 | Method for preparing triboelectric material by dynamic co-irradiation technology |
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| JPS55105962A (en) * | 1979-01-18 | 1980-08-14 | Matsushita Electric Ind Co Ltd | Separator for cell |
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| US5922417A (en) * | 1991-07-09 | 1999-07-13 | Scimat Limited | Polymeric sheet |
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