CN110676416A - Alkaline battery diaphragm and preparation method thereof - Google Patents
Alkaline battery diaphragm and preparation method thereof Download PDFInfo
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- CN110676416A CN110676416A CN201911085132.8A CN201911085132A CN110676416A CN 110676416 A CN110676416 A CN 110676416A CN 201911085132 A CN201911085132 A CN 201911085132A CN 110676416 A CN110676416 A CN 110676416A
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- microporous membrane
- polyolefin microporous
- alkaline battery
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- 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
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- 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
- H01M50/411—Organic material
- H01M50/429—Natural polymers
- H01M50/4295—Natural cotton, cellulose or wood
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- 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
-
- 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
- H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
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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
- 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
Abstract
The invention provides a preparation method of an alkaline battery diaphragm, which comprises the steps of soaking a polyolefin microporous membrane in surface active liquid for hydrophilic treatment, then carrying out first drying treatment to obtain a hydrophilic polyolefin microporous membrane, and respectively laminating and bonding at least one layer of hydrophilic polyolefin microporous membrane and at least one layer of auxiliary liquid absorption diaphragm on the surfaces of two sides of a main diaphragm by adopting an adhesive. The preparation method provided by the invention is simple and feasible in process, and avoids the problem of possible environmental pollution caused by the radiation grafting process. The hydrophilic polyolefin microporous membrane is laminated and adhered to one side surface of the main diaphragm, so that the main diaphragm can be effectively protected, the alkali resistance and the oxidation resistance of the alkaline battery diaphragm are improved, the liquid absorption and retention performances of the alkaline battery diaphragm are further improved in cooperation with the auxiliary liquid absorption diaphragm, and the internal resistance of the alkaline battery diaphragm is effectively reduced. The invention also provides the alkaline battery diaphragm prepared by the preparation method.
Description
Technical Field
The invention relates to the technical field of battery diaphragms, in particular to an alkaline battery diaphragm and a preparation method thereof.
Background
The alkaline battery is a high-capacity dry battery, has better characteristics than a carbon battery, has large electric capacity, and is suitable for occasions requiring large discharge capacity and long-term use. The lower the internal resistance of the diaphragm in the alkaline battery suitable for high-rate discharge, the more the requirement of high-current discharge can be met, and certain isolation performance and mechanical strength are required to ensure that the active substances of the electrodes at two ends cannot be in direct contact, thereby ensuring the storage and service life of the battery.
The diaphragm of the alkaline battery commonly used in the prior art is formed by compounding cellophane and non-woven fabrics, can meet the requirement of heavy current discharge, but the cellophane has poor alkali resistance and oxidation resistance, so that the service life of the alkaline battery can not meet the requirement.
The preparation method of the composite diaphragm for the secondary alkaline zinc-manganese dioxide battery disclosed in the Chinese patent application with the publication number of CN105098127A adopts gamma rays or electron beams to irradiate a diaphragm substrate, and hydrophilic substances are grafted on the surface of the diaphragm substrate, so that the alkali resistance of the diaphragm substrate is improved, and the application requirement of a high-rate discharge battery is met. However, radiation grafting requires high radiation safety due to complex process and is prone to environmental pollution, which limits the batch production and application of such membranes.
Therefore, there is a need to develop a new method for preparing a separator for alkaline batteries to solve the above problems in the prior art.
Disclosure of Invention
The invention aims to provide a preparation method of an alkaline battery diaphragm with simple process and environmental friendliness and the alkaline battery diaphragm obtained by the preparation method, so as to effectively reduce the internal resistance of the alkaline battery diaphragm and improve the alkaline resistance and oxidation resistance of the alkaline battery diaphragm.
In order to achieve the above object, the method for preparing the alkaline battery separator of the present invention comprises:
s1: providing a main diaphragm, a polyolefin microporous membrane and an auxiliary liquid absorption diaphragm;
s2: soaking the polyolefin microporous membrane in a surface active liquid for hydrophilic treatment, taking out the polyolefin microporous membrane to obtain a wet hydrophilic polyolefin microporous membrane, and then performing first drying treatment on the wet hydrophilic polyolefin microporous membrane to obtain a hydrophilic polyolefin microporous membrane;
s3: and respectively laminating and bonding at least one layer of hydrophilic polyolefin microporous membrane and at least one layer of auxiliary liquid absorption membrane on the surfaces of two sides of the main membrane by adopting an adhesive to obtain an alkaline battery membrane to be treated, and then carrying out second drying treatment on the alkaline battery membrane to be treated to obtain the alkaline battery membrane.
The preparation method has the beneficial effects that: the polyolefin microporous membrane is soaked in the surface active liquid for hydrophilic treatment, the process is simple and feasible, and the problem of environmental pollution possibly caused by the radiation grafting process is avoided. The hydrophilic polyolefin microporous membrane and the auxiliary liquid absorption diaphragm which are obtained after the hydrophilic treatment and the first drying treatment are respectively bonded on the surfaces of two sides of the main diaphragm, the hydrophilic polyolefin microporous membrane can effectively protect the main diaphragm, the alkali resistance and the oxidation resistance of the alkaline battery diaphragm are improved, the liquid absorption performance of the alkaline battery diaphragm is further improved by the hydrophilic polyolefin microporous membrane and the auxiliary liquid absorption diaphragm, and the internal resistance of the alkaline battery diaphragm is effectively reduced.
Preferably, in the step S2, the surface active liquid includes any one or more of a phosphate group hydrophilic functional group and a sulfonate group hydrophilic functional group to support any one or more of the phosphate group hydrophilic functional group and the sulfonate group hydrophilic functional group on the inner surface and the outer surface of the polyolefin microporous membrane by the activation treatment. The beneficial effects are that: endowing the polyolefin microporous membrane with good hydrophilic performance so as to be beneficial to improving the alkali resistance and oxidation resistance of the alkaline battery diaphragm and further reducing the internal resistance of the alkaline battery diaphragm.
Further preferably, the surface active liquid is composed of an anionic surfactant, a polyalcohol substance and water, the anionic surfactant is any one or more of alkyl phosphate compounds and alkyl sulfonate compounds, the mass percentage of the anionic surfactant in the surface active liquid is 0.1-20%, and the mass percentage of the polyalcohol substance in the surface active liquid is 0.1-10%.
More preferably, the polyalcohol substances are one or more of polyethylene glycol, polyglycerol and polypropylene glycol, the number average molecular weight of the polyethylene glycol is 100-2000, the number average molecular weight of the polyglycerol is 100-800, and the number average molecular weight of the polypropylene glycol is 200-2000.
Further preferably, in the step S2, the temperature of the hydrophilic treatment is between room temperature and 40 ℃, the time is between 10 seconds and 20 minutes, and the weight of the hydrophilic polyolefin microporous membrane is increased by 5 to 15 percent of the mass of the polyolefin microporous membrane compared with that of the polyolefin microporous membrane.
Preferably, the main component material of the polyolefin microporous membrane is polypropylene, the thickness is 5-40 microns, and the porosity is 20-55%. The beneficial effects are that: the alkaline battery separator is endowed with good mechanical strength and alkali resistance.
Preferably, the main component material of the main diaphragm is cellophane, the thickness is 15-45 microns, and the areal density is 20-60 grams per square meter. The beneficial effects are that: so as to effectively prevent the penetration and migration of the positive and negative electrode active materials.
Preferably, the auxiliary liquid absorption diaphragm is non-woven fabric, the main component material of the non-woven fabric is vinylon, the thickness of the non-woven fabric is 0.05-0.15 mm, and the surface density of the non-woven fabric is 15-50 g/square meter. The beneficial effects are that: the alkaline battery separator is endowed with good liquid absorption and retention performance.
Preferably, the thickness of an adhesive layer formed by the adhesive between adjacent layers is 0.1-1 micron, the adhesive is composed of water and any one or more of polyalcohols, polyacrylic acids and carboxymethyl celluloses, and the mass percent of any one or more of polyalcohols, polyacrylic acids and carboxymethyl celluloses accounts for 1-30% of the adhesive. The beneficial effects are that: the liquid absorption performance of the alkaline battery separator is not influenced while good bonding performance is provided.
The alkaline battery diaphragm comprises the main diaphragm, the auxiliary liquid absorption diaphragm and the hydrophilic polyolefin microporous diaphragm, wherein at least one layer of the hydrophilic polyolefin microporous diaphragm and at least one layer of the auxiliary liquid absorption diaphragm are respectively laminated and bonded on the surfaces of two sides of the main diaphragm through the adhesive.
The alkaline battery diaphragm has the beneficial effects that: the hydrophilic polyolefin microporous membrane obtained after the hydrophilic treatment and the first drying treatment and the hydrophilic polyolefin microporous membrane are respectively bonded on the surfaces of two sides of the main diaphragm, the hydrophilic polyolefin microporous membrane can effectively protect the main diaphragm, the alkali resistance and the oxidation resistance of the alkaline battery diaphragm are improved, the liquid absorption and retention performances of the alkaline battery diaphragm are further improved by the aid of the auxiliary liquid absorption diaphragm, and the internal resistance of the alkaline battery diaphragm is effectively reduced.
Drawings
Fig. 1 is a flow chart of a method of making an alkaline battery separator of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are a part of the embodiments of the present invention, but not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without inventive step based on the embodiments of the present invention, are within the scope of protection of the present invention. Unless defined otherwise, technical or scientific terms used herein shall have the ordinary meaning as understood by one of ordinary skill in the art to which this invention belongs.
In view of the problems in the prior art, an embodiment of the present invention provides a method for preparing an alkaline battery separator, and with reference to fig. 1, the method includes:
s1: providing a main diaphragm, a polyolefin microporous membrane and an auxiliary liquid absorption diaphragm;
s2: soaking the polyolefin microporous membrane in a surface active liquid for hydrophilic treatment, taking out the polyolefin microporous membrane to obtain a wet hydrophilic polyolefin microporous membrane, and then performing first drying treatment on the wet hydrophilic polyolefin microporous membrane to obtain a hydrophilic polyolefin microporous membrane;
s3: and respectively laminating and bonding at least one layer of hydrophilic polyolefin microporous membrane and at least one layer of auxiliary liquid absorption membrane on the surfaces of two sides of the main membrane by adopting an adhesive to obtain an alkaline battery membrane to be treated, and then carrying out secondary drying treatment on the alkaline battery membrane to be treated to obtain the alkaline battery membrane.
In some embodiments of the present invention, the surface active liquid includes any one or more of a hydrophilic functional group containing a phosphoric acid group and a hydrophilic functional group containing a sulfonic acid group.
In some embodiments of the present invention, the surfactant solution is composed of an anionic surfactant, a polyalcohol substance and a solvent, wherein the anionic surfactant is any one or more of alkyl phosphate compounds and alkyl sulfonate compounds. Specifically, the solvent is water.
In some embodiments of the present invention, the alkyl phosphate compound is any one of a monoalkyl ether phosphate potassium salt and an isooctyl alcohol polyoxyethylene ether phosphate sodium salt. The alkyl sulfonate compound is any one of sodium dodecyl sulfonate and sodium dibutyl naphthalene sulfonate.
In some embodiments of the present invention, the main component material of the polyolefin microporous membrane is polypropylene. The auxiliary liquid absorption diaphragm is made of non-woven fabric, and the main component material of the non-woven fabric is vinylon. The main component material of the main diaphragm is cellophane.
In some embodiments of the present invention, the adhesive is composed of water and any one or more of polyalcohols, polyacrylics and carboxymethylcelluloses. The polyvinyl alcohol substance is polyvinyl alcohol, the polyacrylic acid substance is sodium polyacrylate, and the carboxymethyl cellulose substance is sodium carboxymethyl cellulose.
Polypropylene microporous membranes according to embodiments of the present invention are available from sierward (Celgard) corporation, usa. The glassine paper is from Shandong Henggang New materials GmbH, and the vinylon non-woven fabric is from Zhejiang Pengten paper-making research institute GmbH.
The technical solution of the present invention is described in detail by specific examples below.
Example 1
The present example provides a first method of making and a first alkaline battery separator obtained by the first method of making.
The first preparation method specifically comprises the following steps:
s11: a polypropylene microporous membrane having a mass of 0.511 g, a porosity of 41%, and a thickness of 25 μm was provided as the polyolefin microporous membrane. Cellophane having an areal density of 40 grams per square centimeter and a thickness of 28 micrometers was provided as the primary membrane. Vinylon nonwoven fabric having an areal density of 20 g/m and a thickness of 0.07 mm was provided as the auxiliary liquid-absorbent separator.
The lengths and the widths of the polypropylene microporous membrane, the cellophane and the vinylon non-woven fabric are all 200 millimeters.
S12: 0.5 g of sodium dibutylnaphthalenesulfonate, 6 g of potassium monoalkyl ether phosphate and 4 g of polyethylene glycol having a number average molecular weight of 400 were dissolved in 100ml of water and mixed uniformly to form the surfactant solution.
And (5) immersing the polypropylene microporous membrane in the step (S11) in the surface active liquid for 5 minutes to finish the hydrophilic treatment.
And then taking out the polypropylene microporous membrane obtained after the hydrophilic treatment and hanging the polypropylene microporous membrane until no obvious liquid dripping is observed so as to obtain the wet hydrophilic polypropylene microporous membrane.
And carrying out the first drying treatment on the wet hydrophilic polyolefin microporous membrane for 2 minutes at the temperature of 60 ℃ and under normal pressure to obtain a hydrophilic polypropylene microporous membrane with the mass of 0.558 g, wherein the weight increase of the hydrophilic polypropylene microporous membrane compared with the polypropylene microporous membrane accounts for 9.2% of the mass of the polypropylene microporous membrane.
S13: 8 g of polyvinyl alcohol having a number average molecular weight of 17 ten thousand was dissolved in 100ml of water and mixed uniformly to serve as the adhesive.
And laminating and bonding the hydrophilic polypropylene microporous membrane on one side surface of the cellophane through the adhesive, and laminating and bonding the vinylon non-woven fabric on the other side surface of the cellophane to form a first alkaline battery diaphragm to be treated. The thickness of the adhesive layer formed by the adhesive between the adjacent film layers is 0.1-1 micron.
And carrying out second drying treatment on the first alkaline battery diaphragm to be treated at the temperature of 60 ℃ and under normal pressure for 5 minutes to obtain the first alkaline battery diaphragm.
Example 2
This example provides a second method of preparation and a second alkaline battery separator obtained by the second method of preparation.
The second preparation method differs from the first preparation method of example 1 in that:
in the step S11, cellophane with an area density of 50 g/cm and a thickness of 35 μm is provided as the main separator.
Example 3
This example provides a third method of manufacture and a third alkaline battery separator obtained by the third method of manufacture.
The third preparation method specifically comprises the following steps:
s31: and providing a polypropylene microporous membrane with the mass of 0.409 g, the porosity of 35% and the thickness of 20 microns as the polyolefin microporous membrane. Cellophane having an areal density of 30 grams per square centimeter and a thickness of 22 microns was provided as the primary membrane. Vinylon nonwoven fabric having an areal density of 30 g/m and a thickness of 0.10 mm was provided as the auxiliary liquid-absorbent separator.
The lengths and the widths of the polypropylene microporous membrane, the cellophane and the vinylon non-woven fabric are all 200 millimeters.
S32: 15 g of sodium dodecyl sulfonate and 9 g of polyglycerol having a number average molecular weight of 200 were dissolved in 100ml of water and mixed uniformly to form the surfactant solution.
Immersing the polypropylene microporous membrane in the step S31 in the surface active liquid for 50 seconds to complete the hydrophilic treatment.
And then taking out the polypropylene microporous membrane obtained after the hydrophilic treatment and hanging the polypropylene microporous membrane until no obvious liquid dripping is observed so as to obtain the wet hydrophilic polypropylene microporous membrane.
And (3) carrying out the first drying treatment on the wet hydrophilic polyolefin microporous membrane for 2 minutes at the temperature of 60 ℃ and under normal pressure to obtain a hydrophilic polypropylene microporous membrane with the mass of 0.438 g, wherein the weight increase of the hydrophilic polypropylene microporous membrane in comparison with the polypropylene microporous membrane in the step S31 is 7.1% of the mass percentage of the hydrophilic polypropylene microporous membrane.
S33: 5 g of sodium polyacrylate having a number average molecular weight of 200 ten thousand and 2 g of polyvinyl alcohol having a number average molecular weight of 17 ten thousand were dissolved in 100ml of water and mixed uniformly to serve as the adhesive.
And laminating and bonding the hydrophilic polypropylene microporous membrane on one side surface of the cellophane through the adhesive, and laminating and bonding the vinylon non-woven fabric on the other side surface of the cellophane to form a first to-be-treated alkaline battery diaphragm. The thickness of the adhesive layer formed by the adhesive between the adjacent film layers is 0.1-1 micron.
And carrying out second drying treatment on the first alkaline battery diaphragm to be treated at the temperature of 60 ℃ and under normal pressure for 5 minutes to obtain a third alkaline battery diaphragm.
Example 4
This example provides a fourth method of making and a fourth alkaline battery separator obtained by the fourth method of making.
The fourth production method differs from the third production method of example 3 in that:
in the step S31, a cellophane having an areal density of 40 g/cm and a thickness of 28 μm is provided as the main separator.
Example 5
This example provides a fifth method of manufacture and a fifth alkaline battery separator obtained by the fifth method of manufacture.
The fifth preparation method specifically comprises the following steps:
s51: and providing a polypropylene microporous membrane with the mass of 0.385 g, the porosity of 55% and the thickness of 25 micrometers as the polyolefin microporous membrane. Cellophane having an areal density of 30 grams per square centimeter and a thickness of 22 microns was provided as the primary membrane. Vinylon nonwoven fabric having an areal density of 40 g/m and a thickness of 0.12 mm was provided as the auxiliary liquid-absorbent separator.
The lengths and the widths of the polypropylene microporous membrane, the cellophane and the vinylon non-woven fabric are all 200 millimeters.
S52: 0.8 g of isooctanol polyoxyethylene ether sodium phosphate, 0.3 g of polypropylene glycol having a number average molecular weight of 1000 and 0.2 g of polyethylene glycol having a number average molecular weight of 1200 were dissolved in 100ml of water and mixed uniformly to form the surface active liquid.
Immersing the polypropylene microporous membrane in the step S51 in the surface active liquid for 10 minutes to complete the hydrophilic treatment.
And then taking out the polypropylene microporous membrane obtained after the hydrophilic treatment and hanging the polypropylene microporous membrane until no obvious liquid dripping is observed so as to obtain the wet hydrophilic polypropylene microporous membrane.
And (2) carrying out the first drying treatment on the wet hydrophilic polyolefin microporous membrane for 5 minutes at the temperature of 60 ℃ and under normal pressure to obtain a hydrophilic polypropylene microporous membrane with the mass of 0.433 g, wherein the weight gain of the hydrophilic polypropylene microporous membrane compared with the polypropylene microporous membrane in the step S51 is 12.5% of the mass percentage of the polypropylene microporous membrane.
S53: 12 g of sodium carboxymethylcellulose having a number average molecular weight of 6400 was dissolved in 100ml of water and mixed uniformly to serve as the adhesive.
And laminating and bonding the hydrophilic polypropylene microporous membrane on one side surface of the cellophane through the adhesive, and laminating and bonding the vinylon non-woven fabric on the other side surface of the cellophane to form a first alkaline battery diaphragm to be treated. The thickness of the adhesive layer formed by the adhesive between the adjacent film layers is 0.1-1 micron.
And carrying out second drying treatment on the first alkaline battery diaphragm to be treated for 5 minutes at the temperature of 60 ℃ and under normal pressure to obtain a fifth alkaline battery diaphragm.
Example 6
This example provides a sixth manufacturing method and a sixth alkaline battery separator obtained by the sixth manufacturing method.
The sixth production method is different from the fifth production method of example 5 in that:
in the step S51, cellophane with an area density of 50 g/cm and a thickness of 35 μm is provided as the main separator.
In the examples of the present invention, the swelling rate, the alkali absorption rate and the resistance of the 6 alkaline battery separators in examples 1 to 6 were examined, and the test results are shown in table 1.
The method for testing the swelling rate and the alkali absorption rate specifically comprises the following steps: soaking an alkaline battery diaphragm to be tested with a certain mass and size in a potassium hydroxide aqueous solution with the mass concentration of 30% for 2 hours, taking out the alkaline battery diaphragm, and scraping the potassium hydroxide aqueous solution remained on the surface of the alkaline battery diaphragm to be tested to obtain a wet alkaline battery diaphragm to be tested. And weighing the wet alkaline battery diaphragm to be tested, measuring the length and the width, and calculating the longitudinal expansion rate, the transverse expansion rate and the alkali absorption rate.
The longitudinal expansion rate is the percentage of the difference between the width of the wet alkaline battery separator to be tested and the width of the alkaline battery separator to be tested in the width of the alkaline battery separator to be tested.
The transverse expansion rate is the percentage of the difference between the length of the wet-state to-be-tested alkaline battery diaphragm and the length of the to-be-tested alkaline battery diaphragm in the length of the to-be-tested alkaline battery diaphragm.
The alkali absorption rate is the percentage of the difference between the quality of the wet alkaline battery diaphragm to be tested and the quality of the wet alkaline battery diaphragm to be tested in the quality of the alkaline battery diaphragm to be tested.
The resistance testing method specifically comprises the following steps: the method comprises the steps of soaking an alkaline battery diaphragm to be tested in a potassium hydroxide aqueous solution with the mass concentration of 30% for 2 hours, transferring the alkaline battery diaphragm to an electrolytic cell, taking the potassium hydroxide aqueous solution with the mass concentration of 30% as an electrolyte, and measuring resistance by adopting an electrochemical analyzer which is produced by Shanghai Chen Hua apparatus Co., ltd and is in the model of CHI 604.
TABLE 1
As can be seen from table 1, the alkaline battery separators of examples 1 to 6 of the present invention have a longitudinal expansion rate of not more than 2.5% and a transverse expansion rate of not more than 7%, have good alkali resistance and dimensional stability, and can effectively avoid the problem of deformation and short circuit in the alkaline electrolyte.
In addition, the alkaline absorption rate of the alkaline battery diaphragm of the embodiment 1-6 of the invention after 2 hours is as high as 647% -765%, the electrolyte is rapidly absorbed, the conductivity of ions is facilitated when the battery is continuously discharged, and the problem of short circuit caused by electron conduction generated by direct contact of a positive electrode and a negative electrode is avoided.
Electricity of alkaline Battery separators according to examples 1-6 of the inventionResistance of not more than 0.15 omega cm 2 The electrolyte has very low internal resistance, can be effectively penetrated by ions of the electrolyte, and is beneficial to the migration process of the alkali liquor between the pole pieces.
Inventive example the longitudinal tensile strength and the transverse tensile strength of 6 kinds of alkaline battery separators of examples 1 to 6 were respectively examined at a tensile rate of 300 mm/min in accordance with JIS L1096, wherein the number of each alkaline battery separator subjected to the test was 10, and the average value was taken as the test result. Tests show that the 6 alkaline battery separators do not deform or break visually when the transverse tensile strength in the length direction is up to 500N/cm, and do not deform or break visually when the longitudinal tensile strength in the width direction is up to 1000N/cm. It can be seen that the alkaline battery separator of the embodiment of the invention has good mechanical strength.
Although the embodiments of the present invention have been described in detail hereinabove, it is apparent to those skilled in the art that various modifications and variations can be made to these embodiments. However, it is to be understood that such modifications and variations fall within the scope and spirit of the present invention as set forth in the following claims. Moreover, the invention as described herein is capable of other embodiments and of being practiced or of being carried out in various ways.
Claims (10)
1. A method of making an alkaline battery separator, comprising:
s1: providing a main diaphragm, a polyolefin microporous membrane and an auxiliary liquid absorption diaphragm;
s2: soaking the polyolefin microporous membrane in a surface active liquid for hydrophilic treatment, taking out the polyolefin microporous membrane to obtain a wet hydrophilic polyolefin microporous membrane, and then performing first drying treatment on the wet hydrophilic polyolefin microporous membrane to obtain a hydrophilic polyolefin microporous membrane;
s3: and respectively laminating and bonding at least one layer of hydrophilic polyolefin microporous membrane and at least one layer of auxiliary liquid absorption membrane on the surfaces of two sides of the main membrane by adopting an adhesive to obtain an alkaline battery membrane to be treated, and then carrying out second drying treatment on the alkaline battery membrane to be treated to obtain the alkaline battery membrane.
2. The production method according to claim 1, characterized in that in the step S2, the surface active liquid contains any one or more of a phosphoric acid group hydrophilic functional group and a sulfonic acid group hydrophilic functional group to support any one or more of the phosphoric acid group hydrophilic functional group and the sulfonic acid group hydrophilic functional group on the inner surface and the outer surface of the polyolefin microporous membrane by the activation treatment.
3. The preparation method of claim 2, wherein the surface active liquid comprises an anionic surfactant, a polyalcohol substance and water, the anionic surfactant is one or more of alkyl phosphate compounds and alkyl sulfonate compounds, the mass percent of the anionic surfactant in the surface active liquid is 0.1-20%, and the mass percent of the polyalcohol substance in the surface active liquid is 0.1-10%.
4. The method according to claim 3, wherein the polyalcohol is one or more of polyethylene glycol, polyglycerol and polypropylene glycol, the polyethylene glycol has a number average molecular weight of 100 to 2000, the polyglycerol has a number average molecular weight of 100 to 800, and the polypropylene glycol has a number average molecular weight of 200 to 2000.
5. The preparation method according to claim 3, wherein in the step S2, the temperature of the hydrophilic treatment is room temperature to 40 ℃, the time is 10 seconds to 20 minutes, and the weight of the hydrophilic polyolefin microporous membrane is increased by 5 to 15 percent of the mass of the polyolefin microporous membrane compared with the weight of the polyolefin microporous membrane.
6. The method of claim 1, wherein the polyolefin microporous membrane is mainly composed of polypropylene, has a thickness of 5 to 40 μm, and has a porosity of 20 to 55%.
7. The method of claim 1 wherein the primary component material of the primary membrane is cellophane having a thickness of 15-45 microns and an areal density of 20-60 grams per square meter.
8. The method of claim 1, wherein the auxiliary liquid-absorbing separator is a nonwoven fabric, the nonwoven fabric is composed mainly of vinylon, and has a thickness of 0.05 to 0.15 mm and an areal density of 15 to 50 g/m.
9. The method according to claim 1, wherein an adhesive layer formed by the adhesive between adjacent layers has a thickness of 0.1 to 1 μm, the adhesive is composed of water and any one or more of polyalcohols, polyacrylics and carboxymethylcellulose, and the mass percentage of any one or more of polyalcohols, polyacrylics and carboxymethylcellulose is 1 to 30%.
10. An alkaline battery separator produced by the production method according to any one of claims 1 to 9, comprising the main separator, the auxiliary liquid-absorbent separator, and the hydrophilic polyolefin microporous membrane, wherein at least one of the hydrophilic polyolefin microporous membrane and at least one of the auxiliary liquid-absorbent separator is laminated and bonded to the surfaces of both sides of the main separator via the adhesive, respectively.
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| CN111769244A (en) * | 2020-07-16 | 2020-10-13 | 广州鹏辉能源科技股份有限公司 | Composite membrane structure for mercury-free zinc air battery |
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