CN101740745B - Novel electron beam radiation grafting preparation process of polyolefin non-woven fabric alkaline battery diaphragm - Google Patents
Novel electron beam radiation grafting preparation process of polyolefin non-woven fabric alkaline battery diaphragm Download PDFInfo
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- Y02E60/10—Energy storage using batteries
Abstract
The invention belongs to the technical field of preparation of alkaline battery diaphragms, and discloses a novel electron beam radiation grafting preparation process of a polyolefin non-woven fabric alkaline battery diaphragm, which comprises the following steps: the polyolefin nonwoven fabric is used as a base material, and the polyolefin nonwoven fabric absorbed with the vinyl monomer aqueous solution moves in a spread state and is subjected to electron beam radiation by an electron beam radiation device. The preparation process has simple and continuous operation flow, can realize industrial production, and has the advantages of less homopolymer obtained, high utilization rate of the grafting monomer, uniform performance of the prepared battery diaphragm and lower cost, thereby having extremely wide industrial application prospect.
Description
Technical Field
The invention belongs to the technical field of preparation of alkaline battery diaphragms, and particularly relates to a novel electron beam radiation grafting preparation process of a polyolefin non-woven fabric alkaline battery diaphragm.
Background
The alkaline battery is a generic term for batteries using an aqueous solution of potassium hydroxide as an electrolyte, and includes alkaline zinc-manganese batteries, nickel-cadmium batteries, nickel-hydrogen batteries, nickel-zinc batteries, zinc-silver batteries, zinc-air batteries, and the like. The performance requirements of the battery on the battery diaphragm are similar, such as good chemical stability, hydrophilicity, mechanical strength, proper air permeability, structural characteristics of low pore diameter and high porosity and the like, but are not completely consistent to the required degree. Based on the above requirements, vinylon, nylon or polyolefin ultrafine short fibers are generally used to prepare alkaline battery separators. In contrast, vinylon and nylon have better hydrophilicity, but have poor chemical stability; polyolefins have good chemical stability, but they are not hydrophilic. Therefore, attempts have been made to introduce hydrophilic functional groups on the surface of polyolefin fibers by radiation grafting to impart hydrophilicity to the polyolefin fibers, thereby producing alkaline battery separators.
Conventional radiation grafting processes include co-radiation grafting and pre-radiation grafting. In the co-radiation grafting, a base material grafted by radiation is immersed in a grafting monomer solution and is placed in a radiation field for irradiation; the pre-radiation grafting is to place the base material in a radiation field for pre-radiation, then immerse the pre-radiated base material in a grafting monomer solution, and initiate graft copolymerization by using the residual trapped free radicals and peroxide groups on the base material under a certain temperature and inert atmosphere. The preparation of battery diaphragm by radiation grafting method began in the 70's of 20 th century, and the American RAI company firstly invented polyethylene radiation-grafted acrylic diaphragm and realized mass production. The Shanghai applied physical research institute of Chinese academy of sciences and the Japanese atomic force research institute successfully developed the preparation technology of the radiation grafted polyethylene diaphragm in the last 70 th century and were applied to the development of button cell diaphragms. After the 20 th century and the 80 th era, the radiation grafting modified battery diaphragm is successively used for a cadmium-nickel battery, a zinc-nickel battery, a hydrogen-nickel battery and the like. During the 80's of the 20 th century, diaphragm products from the Shanghai institute of applied physics of the Chinese academy of sciences, which have a high price to performance advantage, have gradually entered the international market, replacing the RAI corporation of America. The battery diaphragm prepared by the radiation grafting method has good lyophilic performance, and therefore the battery diaphragm always occupies a relatively important position in the application field of the battery diaphragm. The research and patent reports about the radiation grafting process at home and abroad are also more.
Non-patent document 2, tan Shaozao, etc., polymer science and engineering, 2000 (16) 3, 142-144, by grafting 4-vinylpyridine onto PP nonwoven fabric by pre-irradiation grafting method, various factors affecting the grafting reaction were studied, and preliminary studies were made on the kinetic problem. It was found that the grafting yield increased with increasing irradiation dose, grafting reaction time and reaction temperature.
Patent document 2, chinese patent, 2008, publication No. CN 101115546a, provides a method for producing a membrane to be assembled in a membrane electrode assembly. It pre-irradiates an FEP polymer base film with electron beams at a dose of 25kGy in an air atmosphere to form reaction centers (i.e., radicals) within the base film; then placing the pre-irradiated FEP film in a trap-type reaction tube filled with liquid monomer reaction mixture (such as alpha-methyl styrene, methacrylonitrile and the like) for purging so as to realize the formation of the graft copolymer; then the tube is sealed and moved to a water bath at 60 ℃; after reacting for 22 hours, removing the solution, and washing with acetone for three times; and removing the product, drying the product in a vacuum furnace at 50 ℃ for 3 hours, and then performing subsequent sulfonation treatment to obtain the product which can be used as a fuel cell diaphragm. It can be seen from the above that, the pre-irradiation grafting process requires a large amount of absorbed dose, causes a large damage to the substrate, requires a long time for the subsequent grafting reaction, requires a high grafting temperature, and the like, which brings great difficulties to the implementation of the industrial users of the pre-irradiation grafting process.
In conclusion, the conventional radiation grafting process is difficult to realize industrialization when the polyolefin non-woven fabric is subjected to radiation grafting of acrylic acid to produce the battery diaphragm.
Disclosure of Invention
The invention aims to provide a novel process for preparing a polyolefin non-woven fabric alkaline battery diaphragm by electron beam radiation grafting, and the battery diaphragm prepared by the process has uniform performance and can realize industrial production.
The invention adopts the following technical scheme:
the electron beam radiation grafting process for preparing alkali battery diaphragm of non-woven polyolefin fabric includes the following steps: the polyolefin non-woven fabric is used as a base material, the polyolefin non-woven fabric absorbed with the alkene monomer aqueous solution moves in an unfolded state and is subjected to electron beam radiation through an electron beam radiation device, and the moving speed is 3-50m/min.
The polyolefin non-woven fabric absorbed with the alkene monomer aqueous solution is subjected to electron beam radiation, then washed with water, dried and finally wound, wherein the washing temperature is 60-100 ℃, and the drying temperature is 60-140 ℃.
The movement speed is 5-40m/min, the washing temperature is 80-98 ℃, and the drying temperature is 80-110 ℃; the alkene monomer aqueous solution is adsorbed in the polyolefin non-woven fabric through a coating or padding process.
The polyolefin non-woven fabric is polypropylene fiber and/or ES fiber, and the surface density is 40-180 g.m -2 The thickness is 0.08-0.65 mm.
The fineness of the polypropylene fiber is 0.6-1.5 denier, the fineness of the ES fiber is 0.6-1.5 denier, and the polypropylene fiber is prepared by a hot air non-woven fabric process, a hot rolling non-woven fabric process or a wet papermaking non-woven fabric process.
The dosage of the alkene monomer aqueous solution is 100-400% of the weight of the polyolefin non-woven fabric; the vinyl monomer aqueous solution comprises the following components in percentage by mass: 5 to 40 percent of vinyl monomer, 0 to 5 percent of tackifier, 0.1 to 2 percent of wetting agent and the balance of water.
The dosage of the alkene monomer aqueous solution is 150-300% of the weight of the polyolefin non-woven fabric; the mass percentage of the vinyl monomer in the vinyl monomer aqueous solution is 10-30%.
The vinyl monomer is methacrylic acid, acrylic acid, maleic anhydride, itaconic acid, allyl sulfonic acid, allyl sulfonate, styrene sulfonic acid, styrene sulfonate, propylene sulfonic acid, sodium propylene sulfonate, methyl propylene sulfonic acid, sodium methyl propylene sulfonate, vinyl pyrrolidone, vinyl pyridine or diallyl dimethyl ammonium chloride; the tackifier is one or more of polyacrylamide, polyoxyethylene, polyvinyl alcohol, polyvinylpyrrolidone and sodium carboxymethylcellulose; the wetting agent is one or more of alkyl sodium sulfate, sodium alkyl benzene sulfonate, alkyl alcohol polyoxyethylene ether and alkylphenol polyoxyethylene ether.
The absorbed dose of the electron beam radiation is 10-100 kGy.
The absorbed dose of the electron beam radiation is 20-60 kGy.
The invention is different from the traditional intermittent irradiation grafting process, the invention takes the polyolefin non-woven fabric as the base material, and the polyolefin non-woven fabric absorbs the alkene monomer aqueous solution and then continuously passes through the electron beam radiation device in a spreading state movement mode to carry out electron beam radiation so as to lead the electron beam radiation to carry out graft copolymerization.
The grafting rate of radiation grafting, the conversion rate of vinyl monomers and the crosslinking efficiency among polymer molecules generated in the electron beam radiation process all depend on the absorbed dose, generally speaking, the higher the absorbed dose, the higher the grafting rate, the conversion rate of vinyl monomers and the crosslinking efficiency, but the polyolefin non-woven fabric can be damaged after being radiated, therefore, in the electron beam radiation process, the required absorbed dose simultaneously satisfies the requirements of improving the conversion rate of vinyl monomers as much as possible and reducing the radiation degradation of the polyolefin non-woven fabric substrate as much as possible, and the range of the absorbed dose of the electron beam is selected to be between 10 and 100kGy, and is preferably between 20 and 60kGy.
The coating or padding process is adopted to ensure that a certain amount of hydrophilic alkene monomer aqueous solution is uniformly adsorbed in the polyolefin non-woven fabric base material, so as to provide a precondition for uniform and sufficient subsequent graft copolymerization, the grafting rate of a grafted product can be controlled by adjusting the feeding amount and the mass fraction of the water-soluble alkene monomer, and the hydrophilic capacity and the air permeability of the hydrophilic polyolefin non-woven fabric alkaline battery diaphragm are further adjusted so as to adapt to different types of alkaline batteries.
After the grafting reaction, homopolymer and unreacted monomer are finally removed by washing, and finally, the product is obtained by drying and removing water. The alkene monomer used in the invention is of a molecular structure which is stable in alkali and contains unsaturated ethylenic bond and hydrophilic group; the function of the tackifier is to increase the solution viscosity to make it suitable for the coating process; the wetting agent is a compound which can increase the wettability of the water-soluble alkene monomer aqueous solution to the non-woven fabric base material and enables alkene monomers to quickly and uniformly permeate in the non-woven fabric base material.
The preparation process has simple and continuous operation flow, can realize industrial production, and has the advantages of less homopolymer, high utilization rate of the grafted monomer, uniform performance of the prepared battery diaphragm and lower cost, thereby having extremely wide industrial application prospect.
Drawings
FIG. 1 is a discharge life curve of a 1500mAh nickel-metal hydride battery made from the battery separator of example 1;
fig. 2 is a 1300mAh nickel-hydrogen battery discharge life curve made from the battery separator of example 5.
Detailed Description
Example 1
Preparing water-soluble alkene monomer aqueous solution with the mass percentage of 15 percent of acrylic acid, 0.1 percent of alkyl alcohol polyoxyethylene ether and 84.9 percent of water as grafting solution; the aqueous solution of the water-soluble vinyl monomer is uniformly adsorbed to the surface of the substrate with an areal density of 78 g.m by a coating process -2 In the polyolefin non-woven fabric base material with the thickness of 0.18mm, the dosage of the alkene monomer aqueous solution is 100 percent of the weight of the polyolefin non-woven fabric, and the polyolefin non-woven fabric base material is prepared by adopting polypropylene fiber with the fineness of 1.5 denier through a hot air non-woven fabric process;
then, the polyolefin non-woven fabric absorbed with the vinyl monomer aqueous solution continuously passes through an electron beam radiation device with the absorbed dose of 10kGy to carry out electron beam radiation in an unfolded state at the speed of 5m/min so as to carry out graft copolymerization on the polyolefin non-woven fabric; then washing at 80 ℃ to remove homopolymer and unreacted monomer, and finally drying at 80 ℃ to remove water, thus obtaining the hydrophilic polyolefin non-woven fabric alkaline battery diaphragm with the grafting rate of 9.7%.
Example 2
Preparing water-soluble alkene monomer aqueous solution with the mass percentage of 0.2 percent of polyacrylamide, 0.5 percent of polyvinyl alcohol, 8 percent of itaconic acid, 0.8 percent of alkyl sodium sulfate and 90.5 percent of water as grafting solution; the water-soluble alkene monomer aqueous solution is uniformly adsorbed on the surface with the density of 120 g.m by the padding process -2 In the polyolefin non-woven fabric base material with the thickness of 0.45mm, the dosage of the alkene monomer aqueous solution is 200 percent of the weight of the polyolefin non-woven fabric, the polyolefin non-woven fabric base material adopts polypropylene fiber with the fineness of 1.0 denier and ES fiber with the fineness of 1.0 denier, and the polyolefin non-woven fabric base material is prepared by a wet papermaking non-woven fabric process;
then, the polyolefin non-woven fabric absorbed with the vinyl monomer aqueous solution continuously passes through an electron beam radiation device with the absorbed dose of 20kGy to carry out electron beam radiation in an unfolded state at the speed of 10m/min so as to carry out graft copolymerization on the polyolefin non-woven fabric; then removing homopolymer and unreacted monomer by a 60 ℃ water washing procedure, and finally drying and removing water at 60 ℃ to prepare the hydrophilic polyolefin non-woven fabric alkaline battery diaphragm with the grafting rate of 22.8%.
Example 3
Preparing water-soluble alkene monomer aqueous solution with the mass percentage of 1.8 percent of polyvinyl alcohol, 14 percent of vinyl pyrrolidone, 0.5 percent of alkyl sodium sulfate, 0.5 percent of sodium alkyl benzene sulfonate and 83.2 percent of water as grafting solution; the aqueous solution of the water-soluble vinyl monomer is uniformly adsorbed on the surface of the substrate by a coating process to give an aqueous solution having an areal density of 90 g.m -2 In the polyolefin non-woven fabric base material with the thickness of 0.20mm, the dosage of the alkene monomer aqueous solution is 150 percent of the weight of the polyolefin non-woven fabric, and the polyolefin non-woven fabric base material is prepared by adopting ES fibers with the fineness of 0.6 denier through a hot air non-woven fabric process;
then continuously passing the polyolefin non-woven fabric adsorbed with the vinyl monomer aqueous solution through an electron beam radiation device with the absorbed dose of 60kGy to carry out electron beam irradiation in an unfolded state at the speed of 40m/min so as to carry out graft copolymerization on the polyolefin non-woven fabric; and then washing at 100 ℃ to remove homopolymer and unreacted monomer, and finally drying at 130 ℃ to remove water, thus obtaining the hydrophilic polyolefin non-woven fabric alkaline battery diaphragm with the grafting rate of 12%.
Example 4
Preparing water-soluble alkene monomer aqueous solution with the mass percent of 5 percent of polyoxyethylene, 32 percent of methacrylic acid, 2 percent of alkylphenol polyoxyethylene and 61 percent of water as grafting solution; the water-soluble alkene monomer aqueous solution is uniformly adsorbed on the surface with the density of 65 g.m by the padding process -2 In the polyolefin non-woven fabric base material with the thickness of 0.10mm, the using amount of the alkene monomer aqueous solution is 300 percent of the weight of the polyolefin non-woven fabric, and the polyolefin non-woven fabric base material is prepared by adopting polypropylene fiber with the fineness of 0.6 denier and ES fiber with the fineness of 1.0 denier through a wet papermaking non-woven fabric process;
then, the polyolefin non-woven fabric absorbed with the vinyl monomer aqueous solution continuously passes through an electron beam radiation device with the absorbed dose of 30kGy to carry out electron beam radiation in an unfolded state at the speed of 30m/min so as to carry out graft copolymerization on the polyolefin non-woven fabric; then washing with water at 70 ℃ to remove homopolymer and unreacted monomer, and finally drying at 110 ℃ to remove water, thus obtaining the hydrophilic polyolefin non-woven fabric alkaline battery diaphragm with the grafting rate of 50.2%.
Example 5
Preparing water-soluble alkene monomer aqueous solution with the mass percent of 0.4 percent of polyvinyl alcohol, 0.2 percent of polyoxyethylene, 0.1 percent of sodium alkyl benzene sulfonate, 8 percent of sodium propylene sulfonate, 12 percent of sodium styrene sulfonate and 79.3 percent of water as grafting solution; the aqueous solution of the water-soluble vinyl monomer is uniformly adsorbed to an area density of 40 g.m by a coating process -2 In the polyolefin non-woven fabric base material with the thickness of 0.08mm, the using amount of the alkene monomer aqueous solution is 400 percent of the weight of the polyolefin non-woven fabric, and the polyolefin non-woven fabric base material is prepared by a hot rolling non-woven fabric process by adopting polypropylene fiber with the fineness of 1.2 denier;
then, the polyolefin non-woven fabric absorbed with the vinyl monomer aqueous solution continuously passes through an electron beam radiation device with the absorbed dose of 100kGy to carry out electron beam radiation in an unfolded state at the speed of 50m/min so as to carry out graft copolymerization on the polyolefin non-woven fabric; and then removing homopolymer and unreacted monomer by washing at 65 ℃, and finally drying and removing water at 100 ℃ to obtain the hydrophilic polyolefin non-woven fabric alkaline battery diaphragm with the grafting rate of 15.3%.
And (3) performance test:
using the battery separator obtained in example 1, a plurality of nickel-metal hydride batteries having a battery capacity of 1500mAh were respectively manufactured according to a normal process, using the battery separator obtained in example 5, a plurality of nickel-metal hydride batteries having a battery capacity of 1300mAh were respectively manufactured according to a normal process, the charge performance thereof was examined using 4 samples, the cycle life was examined using 1 sample, the charge performance results are shown in tables 1 and 2 below, and the cycle life is shown in fig. 1 and 2:
table 1 example 1 battery separator preparation 1500mAh nickel-metal hydride battery high temperature charge retention
| EXAMPLE 1 |
1# | 2# | 3# | 4# | Mean value of |
| High temperature charge retention% | 82.07 | 83.94 | 84.53 | 84.15 | 83.67 |
Table 2 example 5 preparation of battery separator high temperature charge retention of 1300mAh nickel-hydrogen battery
| EXAMPLE 5 |
1# | 2# | 3# | 4# | Mean value of |
| High temperature charge retention% | 83.51 | 80.48 | 81.65 | 82.38 | 82.005 |
The data in tables 1 and 2 show that the batteries prepared by the battery diaphragms of the embodiments 1 and 5 of the invention have higher high-temperature charge retention rate and excellent performance, and meanwhile, the uniformity of the battery diaphragms produced by the process of the invention is good.
And (3) comparison test:
the qualified pole pieces (the weight range is controlled within 0.05 g/pcs) are selected, the separator prepared in example 5 and a NiH battery of 1300mAh manufactured by the Bao Eling company FV0613 separator in a normal process are selected for a comparative test, and the results are as follows.
TABLE 3 Capacity distribution
Table 3 the data illustrates: in terms of volume distribution, both the example 5 membrane and the FV0613 membrane were very concentrated; in terms of gram capacity performance, the membrane of example 5 of the present invention is superior to the FV0613 membrane.
TABLE 4 internal resistance distribution
| Categories | EXAMPLE 5 product | FV0613 |
| Maximum value (m omega) | 21.4 | 21.5 |
| Minimum value (m omega) | 18.4 | 18.3 |
| Mean value (m omega) | 19.3 | 19.3 |
The data in Table 4 show that there is no difference in the internal resistance distribution.
Charge and discharge conditions
TABLE 50.1C/0.2C Charge and discharge
TABLE 61C/1C Charge/discharge behavior
The data in tables 5 and 6 show that in the aspect of charge and discharge performance, the charging voltage of the diaphragm is slightly lower than FV-0613, and the discharging platform is slightly lower than FV-0613, so that the difference is small.
Relevant conditions for the above experiments:
the formation system of the nickel-metal hydride battery is as follows: charging for 420 minutes at a constant current of 0.2C, and discharging at a constant current of 0.5C until the voltage is 1.0V. The mixture is placed in an oven at 50 ℃ for 24 hours, and is subjected to 1C constant current charging for 90 minutes, 1C constant current discharging until the voltage is 1.0V, and 1C constant current charging for 72 minutes. The initial capacity is recorded.
Charge performance test conditions: and (4) storing the formed battery in a 50 ℃ oven for 7 days, and taking out. The remaining capacity was recorded by constant current discharge at 0.5C to a voltage of 1.0V. The percentage of the ratio of the residual capacity to the initial capacity is the high-temperature charge retention.
Cycle life test conditions: after formation, the battery was charged at 1C for 72min (Δ V =10 mV), stopped at 30min, and discharged at 1.0V at 1c; stopping for 60min, and repeatedly circulating; the 0.2C charging is carried out for 7.5h every 50 times, the 30min is stopped, and the 0.2C discharging is carried out to 1.0V.
Claims (10)
1. The electron beam radiation grafting preparation process of the polyolefin non-woven fabric alkaline battery diaphragm is characterized by comprising the following steps of: the polyolefin non-woven fabric is used as a base material, the polyolefin non-woven fabric absorbed with the alkene monomer aqueous solution moves in an unfolded state and is subjected to electron beam radiation through an electron beam radiation device, the moving speed is 3-50m/min, and the alkene monomer aqueous solution comprises the following components in percentage by mass: 5 to 40 percent of vinyl monomer, 0 to 5 percent of tackifier, 0.1 to 2 percent of wetting agent and the balance of water.
2. The process of claim 1, wherein the step of preparing the polyolefin non-woven fabric alkaline battery separator by electron beam radiation grafting comprises the following steps: the polyolefin non-woven fabric absorbed with the alkene monomer aqueous solution is subjected to electron beam radiation, then washed with water, dried and finally wound, wherein the washing temperature is 60-100 ℃, and the drying temperature is 60-140 ℃.
3. The process of claim 2, wherein the polyolefin nonwoven alkaline battery separator is prepared by electron beam radiation grafting, and the process comprises the following steps: the movement speed is 5-40m/min, the washing temperature is 80-98 ℃, and the drying temperature is 80-110 ℃; the alkene monomer aqueous solution is adsorbed in the polyolefin non-woven fabric through a coating or padding process.
4. The electron beam radiation grafting preparation process of the polyolefin non-woven fabric alkaline battery separator as claimed in any one of claims 1 to 3, characterized in that: the polyolefin non-woven fabric is polypropylene fiber and/or ES fiber, and the surface density is 40-180 g.m -2 The thickness is 0.08-0.65 mm.
5. The electron beam radiation grafting preparation process of the polyolefin non-woven fabric alkaline battery separator as claimed in claim 4, characterized in that: the fineness of the polypropylene fiber is 0.6-1.5 denier, the fineness of the ES fiber is 0.6-1.5 denier, and the polypropylene fiber is prepared by a hot air non-woven fabric process, a hot rolling non-woven fabric process or a wet papermaking non-woven fabric process.
6. The process for preparing polyolefin non-woven fabric alkaline battery separator according to any of claims 1 to 3 by electron beam radiation grafting, characterized in that: the dosage of the alkene monomer aqueous solution is 100-400% of the weight of the polyolefin non-woven fabric.
7. The electron beam radiation grafting preparation process of the polyolefin non-woven fabric alkaline battery separator as claimed in claim 6, characterized in that: the dosage of the alkene monomer aqueous solution is 150-300% of the weight of the polyolefin non-woven fabric; the mass percentage of the vinyl monomer in the vinyl monomer aqueous solution is 10-30%.
8. The process of claim 7, wherein the step of preparing the polyolefin non-woven fabric alkaline battery separator by electron beam radiation grafting comprises: the vinyl monomer is methacrylic acid, acrylic acid, maleic anhydride, itaconic acid, allyl sulfonic acid, allyl sulfonate, styrene sulfonic acid, styrene sulfonate, propylene sulfonic acid, sodium propylene sulfonate, methyl propylene sulfonic acid, sodium methyl propylene sulfonate, vinyl pyrrolidone, vinyl pyridine or diallyl dimethyl ammonium chloride; the tackifier is one or more of polyacrylamide, polyoxyethylene, polyvinyl alcohol, polyvinylpyrrolidone and sodium carboxymethylcellulose; the wetting agent is one or more of alkyl sodium sulfate, sodium alkyl benzene sulfonate, alkyl alcohol polyoxyethylene ether and alkylphenol polyoxyethylene ether.
9. The electron beam radiation grafting preparation process of the polyolefin non-woven fabric alkaline battery separator as claimed in any one of claims 1 to 3, characterized in that: the absorbed dose of the electron beam radiation is 10-100 kGy.
10. The process of claim 9, wherein the step of preparing the polyolefin non-woven fabric alkaline battery separator by electron beam radiation grafting comprises: the absorbed dose of the electron beam radiation is 20-60 kGy.
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