CN105098127A - Composite diaphragm for secondary alkaline zinc-manganese battery and preparation method thereof - Google Patents
Composite diaphragm for secondary alkaline zinc-manganese battery and preparation method thereof Download PDFInfo
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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
- H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
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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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- 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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Abstract
A composite diaphragm for secondary alkaline zinc-manganese battery and its preparation method, in the field of battery diaphragm technology, the composite diaphragm is a two-layer composite structure composed of polypropylene microporous membrane and wet non-woven fabric containing superfine polyolefin fiber and vinylon fiber, and the thickness of the composite diaphragm is 0.08mm to 0.12mm. The composite diaphragm of the invention has the following performances: (1) The existence of the microporous membrane enables the microporous membrane to have good zinc dendrite resistance; (2) The composite diaphragm can be easily processed into a diaphragm tube by an automatic winding machine; (3) The composite membrane is grafted with acrylic acid and/or sodium styrene sulfonate through radiation to endow the inner surface and the outer surface of the composite membrane with carboxyl and/or sulfonic hydrophilic functional groups, so that the composite membrane has permanent hydrophilicity; and (4) the composite diaphragm has good chemical stability.
Description
Technical Field
The invention belongs to the technical field of battery diaphragms, and particularly relates to a composite diaphragm for a secondary alkaline zinc-manganese battery and a preparation method thereof.
Background
Conventional alkaline zinc-manganese batteries are disposable high specific energy batteries and attempts have been made to make rechargeable secondary batteries without changing their basic structure. Even if the cycle number is only dozens of times, the use value of the alkaline zinc-manganese battery is greatly improved. In order to achieve this, many research and development have been carried out on electrode materials, and the chargeability of the electrode materials has been substantially solved. However, zinc oxide dendrite problems at the zinc electrode still hinder the development of secondary alkaline zinc-manganese batteries. Secondary alkaline zinc-manganese batteries have not been well developed to date.
In order to solve the problem of zinc oxide dendrite of the secondary alkaline zinc-manganese dioxide battery, one of the main methods adopted by people is to improve the dendrite resistance of the diaphragm, wherein an effective method commonly adopted is to adopt a hydrated cellulose membrane and a conventional non-woven fabric diaphragm to be compounded together to be used as the diaphragm of the secondary alkaline zinc-manganese dioxide battery. However, the method has some disadvantages, one is that the cellulose hydrate membrane is easy to be degraded by alkali in high-concentration potassium hydroxide electrolyte, which affects the service life of the battery; and secondly, in the process of using the diaphragm of the alkaline zinc-manganese battery, the diaphragm needs to be processed into a diaphragm tube in the shape of a test tube, and the bottom of the diaphragm tube is formed by hot melt adhesion. And the processing is completed on an automatic pipe coiling machine. The presence of a hydrated cellulose film makes this process difficult because the hydrated cellulose film is not heat fusible. People can only complete the processing process by carefully and manually coiling the pipe, and the production efficiency is very low.
Disclosure of Invention
The invention aims to provide a composite diaphragm for a secondary alkaline zinc-manganese dioxide battery and a preparation method thereof.
Based on the purpose, the invention adopts the following technical scheme:
a composite diaphragm for secondary alkaline Zn-Mn battery is composed of a polypropylene microporous membrane and a wet non-woven fabric containing superfine polyolefine fibres and vinylon fibres, and features that its thickness is 0.08-0.12 mm.
The surface of the composite membrane contains carboxyl and/or sulfonic functional groups obtained by radiation grafting.
The preparation method of the composite diaphragm for the secondary alkaline zinc-manganese dioxide battery comprises the following steps:
(1) Thermally compounding a polypropylene microporous membrane and wet non-woven fabric containing superfine polyolefin fibers and vinylon fibers together to prepare a diaphragm base material, wherein the thermal compounding temperature is 135-150 ℃;
(2) Carrying out gamma-ray or electron beam radiation on the diaphragm base material prepared in the step (1), wherein the absorbed dose is 15 to 40kGy; loading the irradiated diaphragm base material into a grafting reactor, adding a grafting solution, heating to a reaction temperature for grafting reaction, and after the reaction is finished, washing with water and drying to obtain a grafting modified diaphragm base material, wherein the grafting rate is 5-15%;
(3) And (3) hot-rolling and shaping the diaphragm base material obtained in the step (2) into a diaphragm with uniform thickness.
In the step (2), the mass ratio of the grafting liquid to the diaphragm base material is (3~6): 1, the reaction temperature is 50-90 ℃, and the reaction time is 3~8 hours.
The hot rolling temperature in the step (3) is 90-130 ℃.
The grafting liquid consists of deionized water, a wetting agent and acrylic acid and/or sodium styrene sulfonate, wherein the mass fraction of the water is 88 to 94.5 percent, the mass fraction of the wetting agent is 0.5 to 2.0 percent, and the mass fraction of the acrylic acid and/or sodium styrene sulfonate is 5.0 to 10.0 percent.
Preferably, the thickness of the polypropylene microporous membrane is 10 to 25 μm (the surface density of the polypropylene microporous membrane in the thickness range is generally 5 to 12.5g/m 2 The porosity is 40% -60%).
In the step (1): the areal density of the wet-process non-woven fabric containing the superfine polyolefin fibers and the vinylon fibers is 30 to 60g/m 2 (the diameter of the fiber contained in the wet-process non-woven fabric containing the superfine polyolefin fiber and the vinylon fiber in the area density range is 10 to 30 mu m, and the length of the contained fiber is 3 to 12mm) is a composite fiber with a skin-core structure, wherein the core layer is polypropylene, and the skin layer is polyethylene; the mass fraction of the superfine polyolefin fiber in the wet non-woven fabric is 20 to 50 percent; the adopted vinylon fiber comprises the following components in percentage by mass50% to 80%.
The wetting agent in the invention belongs to a surfactant, and can be one or a mixture of more than two of the following compounds: sodium dodecyl sulfate, sodium alkyl benzene sulfonate, alkyl alcohol polyoxyethylene ether, alkylphenol polyoxyethylene ether, dodecenyl sulfonate and the like.
The thermal compounding process in the invention is that a mesh belt type thermal compounding machine is used for bonding a polypropylene microporous membrane and a wet-process non-woven fabric containing superfine polyolefin fibers and vinylon fibers together, and the adopted mesh belt type thermal compounding machine comprises an unreeling system, a hot cylinder, a closed circulating covering belt on the hot cylinder and a reeling system. The compounding process includes setting the microporous polypropylene film and the wet non-woven fabric containing superfine polyolefin fiber and vinylon fiber in the unwinding station of a hot compounding machine to make the microporous polypropylene film below, superposing the two film layers, compounding in a hot compounding machine to form the base diaphragm material, and winding in a winding system at 135-150 deg.c.
The radiation grafting process comprises the following steps: firstly, irradiating the composite diaphragm substrate by gamma-rays or electron beams, wherein the absorbed dose is 15 to 40kGy; then, the irradiated membrane substrate is rolled into a grafting reactor, sealed and vacuumized, then grafting liquid is sucked into the grafting reactor from the bottom of the grafting reactor in vacuum, the liquid inlet speed is controlled, the grafting liquid is fully permeated into the membrane substrate, and then the membrane substrate is heated to the reaction temperature for grafting reaction; and finally, cleaning the diaphragm substrate after the grafting reaction process by using an open-width washing machine to remove unreacted substances, homopolymers and auxiliaries in the grafting solution, wherein the open-width washing machine comprises an unreeling system, a washing system, a drying system and a reeling system.
The hot rolling process is completed by a hot rolling mill, and the hot rolling mill comprises an unreeling machine, a hot rolling roller, a reeling machine, a heating system and an electric control system.
The composite diaphragm of the invention has the following performances: (1) The existence of the microporous membrane enables the microporous membrane to have good zinc dendrite resistance; (2) The composite diaphragm can be easily processed into a diaphragm tube by an automatic winding machine; (3) The composite membrane is grafted with acrylic acid and/or sodium styrene sulfonate through radiation to endow the inner surface and the outer surface of the composite membrane with carboxyl and/or sulfonic hydrophilic functional groups, so that the composite membrane has permanent hydrophilicity; and (4) the composite diaphragm has good chemical stability.
Detailed Description
The technical solution of the present invention is further described in detail with reference to the following specific examples, but the scope of the present invention is not limited thereto.
The wet-laid nonwoven fabric comprising ultrafine polyolefin fibers and vinylon fibers used in the following examples had an areal density of 30 to 60g/m 2 The diameter of the contained fiber is 10 to 30 mu m, and the length is 3 to 12mm; the adopted superfine polyolefin fiber is a composite fiber with a skin-core structure, the core layer is polypropylene, the skin layer is polyethylene, and the fiber fineness is not more than 1.5 denier at most; the mass fraction of the superfine polyolefin fiber in the wet non-woven fabric is 20 to 50 percent; the vinylon fiber is used in 50-80 wt%.
Example 1
A preparation method of a composite diaphragm for a secondary alkaline zinc-manganese dioxide battery comprises the following steps: (1) Mixing 10 μm thick polypropylene microporous membrane with 25g/m 2 Thermally compounding wet-process non-woven fabrics containing superfine polyolefin fibers and vinylon fibers with surface density together by a heat-sealing machine at the temperature of 135 ℃ to form a diaphragm base material;
(2) Placing the diaphragm substrate in a cobalt 60 gamma-ray radiation source, controlling the position and time of the diaphragm substrate in a radiation chamber to ensure that the absorption dose received by the diaphragm substrate is 40kGy, stopping radiation when the radiation time is over half, turning the diaphragm substrate up and down and back and continuing to perform radiation in the next half to ensure that the diaphragm substrate receives radiation uniformly;
(3) And (2) loading the irradiated membrane substrate into a grafting reactor, sealing, vacuumizing, then sucking grafting liquid into the grafting reactor from the bottom of the grafting reactor in vacuum, controlling the liquid inlet speed to fully soak the grafting liquid into the membrane substrate, and then heating to the reaction temperature for grafting reaction. Cleaning the membrane substrate after the grafting reaction process by a water washing machine to remove unreacted substances and homopolymers, and then drying by a dryer at 100 ℃ to obtain the membrane substrate with the grafting rate of 7.6%; the grafting reaction conditions were: the mass ratio of the grafting solution to the diaphragm base material is 3.5, the reaction temperature is 85 ℃, and the reaction time is 3 hours; the grafting solution has the chemical composition as follows: the mass percent of water is 94.5%, the mass percent of octyl alcohol polyoxyethylene ether is 0.5%, and the mass percent of acrylic acid is 5.0%;
(3) The grafted diaphragm base material is hot rolled by a hot rolling mill to form a diaphragm with the thickness of 0.08 +/-0.02 mm, and the hot rolling temperature is 90 ℃.
The obtained diaphragm is detected: the sheet resistance was 33 m.OMEGA.cm for a 40wt% aqueous potassium hydroxide solution 2 The liquid absorption amount is 431 percent, the liquid absorption rate is 55s/2.5cm, and the requirement of the secondary alkaline zinc-manganese dioxide battery on the diaphragm is met. The material is applied to an LR03 type secondary alkaline zinc-manganese dioxide battery, and the initial discharge capacity is 839mAh through tests. 0.2ItA charging, 1.0ItA discharging, the discharge capacity is 621mAh after 100 cycles.
Example 2
A preparation method of a composite diaphragm for a secondary alkaline zinc-manganese dioxide battery comprises the following steps:
(1) Mixing a polypropylene microporous membrane with the thickness of 16 mu m and the mixture of 30g/m 2 Thermally compounding the wet non-woven fabric containing superfine polyolefin fiber and vinylon fiber in surface density at 140 ℃ by a heat sealing machine to form a diaphragm base material;
(2) Continuously passing the diaphragm substrate through an electron accelerator in an unfolded state for radiation, and controlling the beam flow of the electron accelerator and the conveying speed of the diaphragm substrate to make the absorbed dose received by the diaphragm substrate be 25kGy;
(3) Loading the irradiated membrane substrate into a grafting reactor, sealing, vacuumizing, then sucking grafting liquid into the grafting reactor from the bottom of the grafting reactor in vacuum, controlling the liquid inlet speed to enable the grafting liquid to fully permeate into the membrane substrate, and then heating to the reaction temperature for grafting reaction; cleaning the membrane substrate after the grafting reaction process by a water washing machine to remove unreacted substances and homopolymers, and then drying by a dryer at 110 ℃ to obtain the membrane substrate with the grafting rate of 6.7%; the grafting reaction conditions were: the mass ratio of the grafting solution to the diaphragm base material is 4.5; the grafting solution has the chemical composition as follows: the mass percent of water is 94.0%, the mass percent of nonylphenol polyoxyethylene ether is 1.0%, the mass percent of acrylic acid is 3.0%, and the mass percent of sodium styrene sulfonate is 2.0%;
(4) And (3) hot rolling the grafted diaphragm base material by a hot rolling mill to form a diaphragm with the thickness of 0.1 +/-0.02 mm, wherein the hot rolling temperature is 100 ℃.
The obtained diaphragm is detected: the sheet resistance was 38 m.OMEGA.. Cm for a 40wt% aqueous potassium hydroxide solution 2 The liquid absorption amount is 487 percent, the liquid absorption rate is 47s/2.5cm, and the requirement of the secondary alkaline zinc-manganese dioxide battery on the diaphragm is met. The material is applied to an LR6 type secondary alkaline zinc-manganese battery, and the initial discharge capacity is 1752mAh through tests. 0.2ItA charging, 1.0ItA discharging, after 100 cycles, the discharge capacity is 1326mAh.
Example 3
A preparation method of a composite diaphragm for a secondary alkaline zinc-manganese dioxide battery comprises the following steps:
(1) Mixing a polypropylene microporous membrane with a thickness of 20 μm and a polypropylene microporous membrane with a thickness of 30g/m 2 Thermally compounding wet-process non-woven fabrics containing superfine polyolefin fibers and vinylon fibers with surface density together by a heat-sealing machine at the temperature of 150 ℃ to form a diaphragm base material;
(2) Continuously passing the diaphragm substrate through an electron accelerator in an unfolded state for radiation, and controlling the beam flow of the electron accelerator and the conveying speed of the diaphragm substrate to make the absorbed dose received by the diaphragm substrate be 15kGy;
(3) Loading the irradiated diaphragm substrate into a grafting reactor, sealing, vacuumizing, then sucking a grafting solution into the grafting reactor from the bottom of the grafting reactor in vacuum, controlling the liquid inlet speed to enable the grafting solution to fully permeate the diaphragm substrate, heating to the reaction temperature to carry out grafting reaction, cleaning the diaphragm substrate subjected to the grafting reaction process by a water washer to remove unreacted substances and homopolymers, and drying by a dryer at 120 ℃ to obtain the diaphragm substrate with the grafting rate of 9.3%; the grafting reaction conditions were: the mass ratio of the grafting solution to the diaphragm base material is 5.6, the reaction temperature is 50 ℃, and the reaction time is 8 hours; the grafting solution has the chemical composition as follows: the mass percent of the water is 88.5%, the mass percent of the sodium dodecyl sulfate is 1.5%, the mass percent of the acrylic acid is 6.0%, and the mass percent of the sodium styrene sulfonate is 4.0%;
(4) And (3) hot rolling the grafted diaphragm base material by a hot rolling mill to form a diaphragm with the thickness of 0.12 +/-0.02 mm, wherein the hot rolling temperature is 130 ℃.
The obtained diaphragm is detected: the sheet resistance of the aqueous solution of 40% potassium hydroxide was 43 m.OMEGA.. Cm 2 The liquid absorption amount is 521%, the liquid absorption rate is 67s/2.5cm, and the requirement of the secondary alkaline zinc-manganese dioxide battery on the diaphragm is met. The lithium-manganese dioxide battery is applied to an LR6 type secondary alkaline zinc-manganese battery, and the initial discharge capacity is 1682mAh through tests. 0.2ItA charging, 1.0ItA discharging, the discharge capacity after 100 cycles is 1278mAh.
Claims (8)
1. The composite diaphragm for the secondary alkaline zinc-manganese dioxide battery is characterized by being of a two-layer composite structure consisting of a polypropylene microporous membrane and a wet-process non-woven fabric containing superfine polyolefin fibers and vinylon fibers, and the thickness of the composite diaphragm is 0.08mm to 0.12mm.
2. The composite separator for a secondary alkaline zinc-manganese dioxide battery according to claim 1, characterized in that the surface of the composite separator contains carboxyl and/or sulfonic functional groups obtained by radiation grafting.
3. The composite separator for the secondary alkaline zinc-manganese dioxide battery as claimed in claim 1, wherein the polypropylene microporous membrane has a thickness of 10 to 25 μm.
4. The composite diaphragm for the secondary alkaline zinc-manganese dioxide battery as claimed in claim 1, wherein the wet-process non-woven fabric containing the ultrafine polyolefin fibers and the vinylon fibers has an areal density of 30 to 60g/m 2 (ii) a The superfine polyolefin fiber is a composite fiber with a skin-core structure, wherein the core layer is polypropylene, and the skin layer is polyethylene; the mass fraction of the superfine polyolefin fiber in the wet non-woven fabric is 20 to 50 percent; the vinylon fiber is used in 50-80 wt%.
5. A method for preparing the composite separator for the secondary alkaline zinc-manganese dioxide battery of any one of claims 1 to 4, characterized by comprising the following steps:
(1) Thermally compounding a polypropylene microporous membrane and wet non-woven fabric containing superfine polyolefin fibers and vinylon fibers together to prepare a diaphragm base material, wherein the thermal compounding temperature is 135-150 ℃;
(2) Carrying out gamma-ray or electron beam radiation on the diaphragm substrate prepared in the step (1), wherein the absorbed dose is 15 to 40kGy; loading the irradiated diaphragm base material into a grafting reactor, adding a grafting solution, heating to a reaction temperature for grafting reaction, and after the reaction is finished, washing with water and drying to obtain a grafting modified diaphragm base material, wherein the grafting rate is 5-15%;
(3) And (3) hot-rolling and shaping the diaphragm base material obtained in the step (2) into a diaphragm with uniform thickness.
6. The preparation method of the composite diaphragm for the secondary alkaline zinc-manganese dioxide battery according to claim 5, wherein the mass ratio of the grafting solution to the diaphragm base material in the step (2) is (3~6: 1), the reaction temperature is 50-90 ℃, and the reaction time is 3~8 hours.
7. The preparation method of the composite diaphragm for the secondary alkaline zinc-manganese dioxide battery according to claim 5, wherein the hot rolling temperature in the step (3) is 90-130 ℃.
8. The preparation method of the composite diaphragm for the secondary alkaline zinc-manganese dioxide battery as claimed in claim 5, wherein the grafting solution consists of deionized water, a wetting agent, acrylic acid and/or sodium styrene sulfonate, and the mass fraction of water is 88 to 94.5%, the mass fraction of the wetting agent is 0.5 to 2.0%, and the mass fraction of the acrylic acid and/or sodium styrene sulfonate is 5.0 to 10.0%, in percentage by mass.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109326762A (en) * | 2018-10-26 | 2019-02-12 | 中原工学院 | A kind of wet forming battery diaphragm and preparation method thereof that aperture is controllable |
| CN110707371A (en) * | 2019-10-14 | 2020-01-17 | 吉凯阳科技(杭州)有限公司 | Alkaline zinc-manganese rechargeable battery |
| WO2021037173A1 (en) * | 2019-08-28 | 2021-03-04 | 宁德时代新能源科技股份有限公司 | Solid-state electrolyte membrane and solid-state lithium-metal battery including same, battery module, battery pack, and device |
Families Citing this family (1)
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| CN107677582A (en) * | 2017-09-19 | 2018-02-09 | 合肥国轩高科动力能源有限公司 | A kind of method of testing and its device of lithium ion battery separator transparent liquid rate |
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