CN116565447A - Hydrophilic composite diaphragm for secondary zinc-manganese battery and preparation method thereof - Google Patents
Hydrophilic composite diaphragm for secondary zinc-manganese battery and preparation method thereof Download PDFInfo
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- CN116565447A CN116565447A CN202310752441.6A CN202310752441A CN116565447A CN 116565447 A CN116565447 A CN 116565447A CN 202310752441 A CN202310752441 A CN 202310752441A CN 116565447 A CN116565447 A CN 116565447A
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- 239000002131 composite material Substances 0.000 title claims abstract description 39
- WJZHMLNIAZSFDO-UHFFFAOYSA-N manganese zinc Chemical group [Mn].[Zn] WJZHMLNIAZSFDO-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000012528 membrane Substances 0.000 claims abstract description 50
- 239000002346 layers by function Substances 0.000 claims abstract description 34
- 238000000034 method Methods 0.000 claims abstract description 33
- 125000000524 functional group Chemical group 0.000 claims abstract description 24
- 239000006255 coating slurry Substances 0.000 claims abstract description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000011230 binding agent Substances 0.000 claims abstract description 16
- 150000001875 compounds Chemical class 0.000 claims abstract description 15
- 229920001477 hydrophilic polymer Polymers 0.000 claims abstract description 12
- 238000001035 drying Methods 0.000 claims abstract description 10
- 238000003756 stirring Methods 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 9
- 238000007790 scraping Methods 0.000 claims abstract description 9
- -1 polypropylene Polymers 0.000 claims description 9
- 239000003365 glass fiber Substances 0.000 claims description 8
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 7
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 7
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 7
- 125000003368 amide group Chemical group 0.000 claims description 6
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims description 5
- 229920002101 Chitin Polymers 0.000 claims description 5
- 239000004743 Polypropylene Substances 0.000 claims description 5
- 239000002174 Styrene-butadiene Substances 0.000 claims description 5
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 claims description 5
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 claims description 5
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 5
- 239000004816 latex Substances 0.000 claims description 5
- 229920000126 latex Polymers 0.000 claims description 5
- 229920001155 polypropylene Polymers 0.000 claims description 5
- 239000000661 sodium alginate Substances 0.000 claims description 5
- 235000010413 sodium alginate Nutrition 0.000 claims description 5
- 229940005550 sodium alginate Drugs 0.000 claims description 5
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims description 5
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims description 5
- 239000011115 styrene butadiene Substances 0.000 claims description 5
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 5
- 229920001661 Chitosan Polymers 0.000 claims description 4
- 239000002033 PVDF binder Substances 0.000 claims description 4
- 239000004698 Polyethylene Substances 0.000 claims description 4
- 229920002125 Sokalan® Polymers 0.000 claims description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 4
- 229920002401 polyacrylamide Polymers 0.000 claims description 4
- 239000004584 polyacrylic acid Substances 0.000 claims description 4
- 229920000573 polyethylene Polymers 0.000 claims description 4
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 4
- 239000004677 Nylon Substances 0.000 claims description 3
- 239000000853 adhesive Substances 0.000 claims description 3
- 230000001070 adhesive effect Effects 0.000 claims description 3
- 125000003277 amino group Chemical group 0.000 claims description 3
- 229920002678 cellulose Polymers 0.000 claims description 3
- 239000001913 cellulose Substances 0.000 claims description 3
- 239000004745 nonwoven fabric Substances 0.000 claims description 3
- 229920001778 nylon Polymers 0.000 claims description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 2
- 150000001299 aldehydes Chemical class 0.000 claims description 2
- 229920002635 polyurethane Polymers 0.000 claims description 2
- 239000004814 polyurethane Substances 0.000 claims description 2
- 239000011701 zinc Substances 0.000 abstract description 20
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 abstract description 16
- 229910052725 zinc Inorganic materials 0.000 abstract description 16
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 abstract description 12
- 230000008021 deposition Effects 0.000 abstract description 4
- 125000005842 heteroatom Chemical group 0.000 abstract description 3
- 229920000642 polymer Polymers 0.000 abstract description 3
- 230000009834 selective interaction Effects 0.000 abstract description 2
- 238000012360 testing method Methods 0.000 description 16
- QNDQILQPPKQROV-UHFFFAOYSA-N dizinc Chemical compound [Zn]=[Zn] QNDQILQPPKQROV-UHFFFAOYSA-N 0.000 description 10
- 239000003792 electrolyte Substances 0.000 description 10
- 239000011148 porous material Substances 0.000 description 8
- 238000010277 constant-current charging Methods 0.000 description 7
- 210000001787 dendrite Anatomy 0.000 description 7
- 238000007599 discharging Methods 0.000 description 7
- 239000011888 foil Substances 0.000 description 7
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 239000002002 slurry Substances 0.000 description 6
- 230000008961 swelling Effects 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 230000000149 penetrating effect Effects 0.000 description 4
- 239000012466 permeate Substances 0.000 description 4
- 238000000151 deposition Methods 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 230000005012 migration Effects 0.000 description 3
- 238000013508 migration Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 210000004027 cell Anatomy 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000002715 modification method Methods 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 208000032953 Device battery issue Diseases 0.000 description 1
- 125000003172 aldehyde group Chemical group 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000007600 charging Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000001755 magnetron sputter deposition Methods 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/403—Manufacturing processes of separators, membranes or diaphragms
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
-
- 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
- H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
- H01M50/417—Polyolefins
-
- 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
- H01M50/431—Inorganic 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Cell Separators (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a preparation method of a hydrophilic composite membrane for a secondary zinc-manganese battery, which is characterized by comprising the following steps of: adding water into a hydrophilic high molecular compound with O-rich functional groups or N-rich functional groups to swell, adding a binder, and uniformly mixing and stirring to prepare hydrophilic functional layer coating slurry; and (3) scraping the hydrophilic functional layer coating slurry on a base film, and drying to obtain the hydrophilic composite diaphragm. The method directly knife coats a hydrophilic polymer functional layer on a base film, and the method is used for preparing Zn through a large number of O or N hetero atoms on the polymer 2+ Selective interaction to promote zinc goldBelongs to uniform deposition and improves the cycle reversibility of the zinc ion battery.
Description
Technical Field
The invention belongs to the field of new materials, and particularly relates to a hydrophilic composite diaphragm for a secondary zinc-manganese battery and a preparation method thereof.
Background
The water system secondary zinc-manganese battery is widely paid attention to by people with the advantages of high capacity, high safety, low cost, green friendliness and the like, and is considered to be one of the power supply systems of large-scale energy storage and wearable electronic equipment with the most extensive development potential. However, serious side reactions such as metal dendrite growth, corrosion, hydrogen evolution and the like can occur on the surface of the zinc cathode in the aqueous solution, so that the coulomb efficiency of the battery is low, the capacity is rapidly attenuated, and the cycle life is greatly shortened. Therefore, the separator mainly used for large-scale application of the water-based secondary zinc-manganese battery is a glass fiber separator with high strength. However, when the metal dendrite is used as a diaphragm, the metal dendrite is not selective to migration of zinc ions, and is easy to cause self-discharge or uncontrolled and non-uniform deposition of zinc ions in the charging process, and finally the formed metal dendrite can penetrate through the whole diaphragm, so that short circuit and battery failure are caused, and even safety problems are caused.
Based on the method, researchers modify the surface of the diaphragm by changing the diaphragm base material or by a magnetron sputtering method and the like to improve the selectivity of zinc ion migration, regulate and control uniform deposition of zinc and inhibit or resist dendrite growth, thereby improving the circulation capacity of the zinc ion battery. For example, a functional supermolecule modified glass fiber diaphragm (GF@SM) is used as a diaphragm of the water-based zinc ion battery, so that the migration behavior of zinc ions in the electrolyte between the positive electrode and the negative electrode is regulated, the growth of negative dendrites is effectively reduced, and the electrochemical performance of the water-based zinc ion battery is greatly improved.
However, the currently adopted diaphragm modification methods of supermolecular materials and the like have complex process and high cost, often use toxic and harmful organic reagents, and are not suitable for large-scale preparation and production. Therefore, a membrane modification method which is simple in process, environment-friendly and safe and can greatly prolong the service life of the water-based zinc ion batteries such as the secondary zinc-manganese battery is needed.
Disclosure of Invention
In order to solve the technical problems, the invention provides a preparation method of a hydrophilic composite membrane for a secondary zinc-manganese battery, and also provides the hydrophilic composite membrane for the secondary zinc-manganese battery prepared by the method. The method directly knife coats a hydrophilic polymer functional layer on a base film, and the method is used for preparing Zn through a large number of O or N hetero atoms on the polymer 2+ The selective interaction promotes the uniform deposition of zinc metal and improves the cycle reversibility of the zinc ion battery.
To achieve the first object, the present invention is realized by the following technical solutions: the preparation method of the hydrophilic composite membrane for the secondary zinc-manganese battery is characterized by comprising the following steps of: adding water into a hydrophilic high molecular compound with O-rich functional groups or N-rich functional groups to swell, adding a binder, and uniformly mixing and stirring to prepare hydrophilic functional layer coating slurry; and (3) scraping the hydrophilic functional layer coating slurry on a base film, and drying to obtain the hydrophilic composite diaphragm.
The hydrophilic functional layer coating slurry partially permeates into the pore structure of the base film to form an interpenetrating structure, and partially does not permeate into the pore structure of the base film to form a layered structure.
In the scheme, the method comprises the following steps: the O-rich functional group is at least one of hydroxyl, carboxyl, aldehyde or sulfonic acid.
In the scheme, the method comprises the following steps: the N-rich functional group is at least one of an amide group or an amino group.
In the scheme, the method comprises the following steps: the O-rich functional group or the N-rich functional group is positioned on a side chain of the hydrophilic high molecular compound. Avoiding the hydrophobic carbon chain from breaking the continuous hydrophilic network formed by the O-rich functional group or the N-rich functional group.
In the scheme, the method comprises the following steps: the hydrophilic polymer compound is one of polyvinyl alcohol, polyacrylic acid, polyacrylamide, cellulose, chitin and chitosan. Avoiding the hydrophobic carbon chain from breaking the continuous hydrophilic network formed by the O-rich functional group or the N-rich functional group.
In the scheme, the method comprises the following steps: the concentration of the hydrophilic polymer compound which swells in water is 40-240 mg.ml -1 。
In the scheme, the method comprises the following steps: the binder is at least one of sodium carboxymethyl cellulose, sodium alginate, styrene-butadiene latex, aqueous polyurethane or polyvinyl alcohol aqueous adhesive; the mass ratio of the hydrophilic high molecular compound to the binder is 2:1-100:1.
In the scheme, the method comprises the following steps: the base membrane is one of a glass fiber membrane, a polypropylene membrane, a polyethylene membrane, a non-woven fabric membrane, a polyvinylidene fluoride filter membrane or a nylon filter membrane.
In the scheme, the method comprises the following steps: the average thickness of the hydrophilic functional layer in the prepared hydrophilic composite membrane is 10-150 mu m.
The hydrophilic composite membrane for the secondary zinc-manganese battery is prepared by the preparation method of the hydrophilic composite membrane for the secondary zinc-manganese battery.
The beneficial effects are that:
the invention uses a large amount of O or N hetero atoms in the functional layer to pair Zn 2+ Increases the nucleation overpotential of zinc and induces Zn 2+ Inhibiting the formation and growth of zinc dendrites; and the water molecules on the surface of the zinc cathode are competing for through the hydrogen bond, so that the activity of the water is reduced, and side reactions such as corrosion, hydrogen evolution and the like are reduced. According to the test, the assembled zinc-zinc symmetrical battery with the hydrophilic composite membrane prepared by the invention is 1mA cm -2 Can stably circulate 1390h in the constant current charge and discharge test. The preparation process of the composite diaphragm is simple, easy to repeat and low in cost, can obviously improve the cycle life of the zinc electrode in the aqueous electrolyte, and can be widely applied to aqueous zinc ion batteries such as secondary zinc-manganese batteries.
The hydrophilic composite membrane for the secondary zinc-manganese battery directly scrapes and coats the functional layer on the base membrane, is simple to operate, is economical and quick, and is convenient for repeated experiments and mass production. The preparation process of the composite diaphragm is simple, easy to repeat and low in cost, can obviously improve the cycle life of the zinc electrode in the aqueous electrolyte, and can be widely applied to aqueous zinc ion batteries such as secondary zinc-manganese batteries.
Drawings
FIG. 1 is a scanning electron microscope image of a hydrophilic composite membrane in example 5.
FIG. 2 is a graph of the zinc-zinc symmetrical cell of example 5 at 1mA cm -2 And the cycle life of constant current charge and discharge is 1h respectively under the current density.
FIG. 3 is a graph showing that the zinc-zinc symmetrical cell of comparative example 1 was at 1 mA.cm -2 And the cycle life of constant current charge and discharge is 1h respectively under the current density.
Detailed Description
The invention will be further described with reference to examples and figures
The preparation method of the hydrophilic composite membrane for the secondary zinc-manganese battery comprises the following steps: adding water into a hydrophilic high molecular compound with O-rich functional groups or N-rich functional groups to swell, adding a binder, and uniformly mixing and stirring to prepare hydrophilic functional layer coating slurry; and (3) scraping the hydrophilic functional layer coating slurry on a base film, and drying to obtain the hydrophilic composite diaphragm.
The O-rich functional group is at least one of a hydroxyl group, a carboxyl group, an aldehyde group or a sulfonic acid group. The N-rich functional group is at least one of an amide group or an amino group. The O-rich functional group or the N-rich functional group is located on the side chain of the hydrophilic polymer compound. Such as one of polyvinyl alcohol, polyacrylic acid, polyacrylamide, cellulose, chitin and chitosan. The concentration of the hydrophilic polymer compound which swells with water is 40-240 mg.ml -1 . The binder is at least one of sodium carboxymethyl cellulose, sodium alginate, styrene-butadiene latex ammonia, aqueous polyester or polyvinyl alcohol aqueous adhesive; the mass ratio of the hydrophilic high molecular compound to the binder is 2:1-100:1. The base membrane is one of a glass fiber membrane, a polypropylene membrane, a polyethylene membrane, a non-woven fabric membrane, a polyvinylidene fluoride filter membrane or a nylon filter membrane. The average thickness of the hydrophilic functional layer in the hydrophilic composite membrane is 10-150 mu m.
Example 1
18g of hydrophilic polymer polyvinyl alcohol with hydroxyl-containing side chains is added into 100mL of deionized water for swelling, and then 0.9g of sodium carboxymethyl cellulose binder is addedMixing and stirring uniformly to prepare hydrophilic functional layer coating slurry; and (3) scraping the hydrophilic functional layer coating slurry on the glass fiber membrane, penetrating the slurry into the pore structure of the base membrane to form an interpenetrating structure, and drying to obtain the hydrophilic composite membrane with the average thickness of the hydrophilic functional layer of 60 um. The diaphragm and two zinc foils are used as positive and negative electrodes and 2M ZnSO is used as a cathode 4 And (3) carrying out constant current charge and discharge test on the electrolyte and the assembled zinc-zinc symmetrical battery. At 1 mA.cm -2 Constant current charging for 1h and cross current discharging for 1h, and performing a cycle test. The results show that the cycle life of the symmetrical battery reaches 620h.
Example 2
15g of hydrophilic high polymer polyacrylic acid with carboxyl groups on side chains is added into 100mL of deionized water for swelling, and then 1.35g of sodium carboxymethyl cellulose binder is added for mixing and stirring uniformly, so as to prepare hydrophilic functional layer coating slurry; and (3) scraping the hydrophilic functional layer coating slurry on the polypropylene diaphragm, wherein the slurry does not permeate into the pore structure of the base film to form a layered structure, and drying to obtain the hydrophilic composite diaphragm with the average thickness of the hydrophilic functional layer of 10 um. The diaphragm and two zinc foils are used as positive and negative electrodes and 2M ZnSO is used as a cathode 4 And (3) carrying out constant current charge and discharge test on the electrolyte and the assembled zinc-zinc symmetrical battery. At 1 mA.cm -2 Constant current charging for 1h and cross current discharging for 1h, and performing a cycle test. The results show that the cycle life of the symmetrical battery reaches 430h.
Example 3
Adding 4g of hydrophilic polymer polyacrylamide with amide groups in side chains into 100mL of deionized water for swelling, then adding 1.8g of sodium alginate binder, and uniformly mixing and stirring to prepare hydrophilic functional layer coating slurry; and (3) scraping the hydrophilic functional layer coating slurry on the polyethylene membrane, wherein the slurry does not permeate into the pore structure of the base membrane to form a layered structure, and drying to obtain the hydrophilic composite membrane with the average thickness of the hydrophilic functional layer of 100 um. The diaphragm and two zinc foils are used as positive and negative electrodes and 2M ZnSO is used as a cathode 4 And (3) carrying out constant current charge and discharge test on the electrolyte and the assembled zinc-zinc symmetrical battery. At 1 mA.cm -2 Constant current charging for 1h,and discharging for 1h by cross flow, and performing a cycle test. The results show that the cycle life of the symmetrical battery reaches 770 hours.
Example 4
Adding 18g of hydrophilic polymer chitosan with side chains containing hydroxyl and amino into 100mL of deionized water for swelling, then adding 0.18g of styrene-butadiene latex ammonia binder, mixing and stirring uniformly to prepare hydrophilic functional layer coating slurry; and (3) scraping the hydrophilic functional layer coating slurry on the polyvinylidene fluoride filter membrane, penetrating the slurry into the pore structure of the base membrane to form an interpenetrating structure, and drying to obtain the hydrophilic composite membrane with the average thickness of the hydrophilic functional layer of 150 um. The diaphragm and two zinc foils are used as positive and negative electrodes and 2MZnSO 4 And (3) carrying out constant current charge and discharge test on the electrolyte and the assembled zinc-zinc symmetrical battery. At 1 mA.cm -2 Constant current charging for 1h and cross current discharging for 1h, and performing a cycle test. The result shows that the cycle life of the symmetrical battery reaches 940h.
Example 5
Adding 18g of hydrophilic macromolecule chitin with side chains containing hydroxyl and amide groups into 100mL of deionized water for swelling, then adding 0.9g of sodium alginate binder, mixing and stirring uniformly to prepare hydrophilic functional layer coating slurry; and (3) scraping the hydrophilic functional layer coating slurry on the glass fiber membrane, penetrating the slurry into the pore structure of the base membrane to form an interpenetrating structure, and drying to obtain the hydrophilic composite membrane with the average thickness of the hydrophilic functional layer of 60 um. The diaphragm and two zinc foils are used as positive and negative electrodes and 2M ZnSO is used as a cathode 4 And (3) carrying out constant current charge and discharge test on the electrolyte and the assembled zinc-zinc symmetrical battery. At 1 mA.cm -2 Constant current charging for 1h and cross current discharging for 1h, and performing a cycle test. The result shows that the cycle life of the symmetrical battery reaches 1390h.
Example 6
Adding 24g of hydrophilic polymer chitin with side chains containing hydroxyl groups and amide groups into 100mL of deionized water for swelling, then adding 0.72g of styrene-butadiene latex binder, mixing and stirring uniformly to prepare hydrophilic functional layer coating slurry; blade coating a hydrophilic functional layer coating slurry on a polypropylene separator, the slurry not penetrating into the base filmIn the pore structure, a layered structure is formed, and the hydrophilic composite membrane with the average thickness of the hydrophilic functional layer of 20um can be obtained after drying. The diaphragm and two zinc foils are used as positive and negative electrodes and 2M ZnSO is used as a cathode 4 And (3) carrying out constant current charge and discharge test on the electrolyte and the assembled zinc-zinc symmetrical battery. At 1 mA.cm -2 Constant current charging for 1h and cross current discharging for 1h, and performing a cycle test. The results show that the symmetrical battery cycle life reaches 920h.
Comparative example 1
Glass fiber is used as a diaphragm, two zinc foils are used as positive and negative electrodes, and 2M ZnSO is used as a cathode 4 And (3) electrolyte, namely assembling a zinc-zinc symmetrical battery, and performing constant current charge and discharge test. At 1 mA.cm -2 Constant current charging for 1h and cross current discharging for 1h, and performing a cycle test. The result shows that the cycle life of the symmetrical battery reaches 180h.
Although embodiments of the present invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made therein without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (10)
1. The preparation method of the hydrophilic composite membrane for the secondary zinc-manganese battery is characterized by comprising the following steps of: adding water into a hydrophilic high molecular compound with O-rich functional groups or N-rich functional groups to swell, adding a binder, and uniformly mixing and stirring to prepare hydrophilic functional layer coating slurry; and (3) scraping the hydrophilic functional layer coating slurry on a base film, and drying to obtain the hydrophilic composite diaphragm.
2. The method for preparing the hydrophilic composite separator for the secondary zinc-manganese battery according to claim 1, wherein the method comprises the following steps: the O-rich functional group is at least one of hydroxyl, carboxyl, aldehyde or sulfonic acid.
3. The method for preparing the hydrophilic composite separator for the secondary zinc-manganese battery according to claim 1, wherein the method comprises the following steps: the N-rich functional group is at least one of an amide group or an amino group.
4. The method for preparing the hydrophilic composite separator for the secondary zinc-manganese battery according to claim 1, wherein the method comprises the following steps: the O-rich functional group or the N-rich functional group is positioned on a side chain of the hydrophilic high molecular compound.
5. The method for preparing the hydrophilic composite separator for the secondary zinc-manganese battery, according to claim 4, wherein the method comprises the following steps: the hydrophilic polymer compound is one of polyvinyl alcohol, polyacrylic acid, polyacrylamide, cellulose, chitin and chitosan.
6. The method for preparing the hydrophilic composite separator for the secondary zinc-manganese battery according to any one of claims 1 to 4, which is characterized in that: the concentration of the hydrophilic polymer compound which swells in water is 40-240 mg.ml -1 。
7. The method for preparing the hydrophilic composite separator for the secondary zinc-manganese battery according to claim 6, wherein the method comprises the following steps: the binder is at least one of sodium carboxymethyl cellulose, sodium alginate, styrene-butadiene latex, aqueous polyurethane or polyvinyl alcohol aqueous adhesive; the mass ratio of the hydrophilic high molecular compound to the binder is 2:1-100:1.
8. The method for preparing the hydrophilic composite separator for the secondary zinc-manganese battery according to claim 7, wherein the method comprises the following steps: the base membrane is one of a glass fiber membrane, a polypropylene membrane, a polyethylene membrane, a non-woven fabric membrane, a polyvinylidene fluoride filter membrane or a nylon filter membrane.
9. The method for preparing the hydrophilic composite separator for the secondary zinc-manganese battery according to claim 8, wherein the method comprises the following steps: the average thickness of the hydrophilic functional layer in the prepared hydrophilic composite membrane is 10-150 mu m.
10. A hydrophilic composite separator for a secondary zinc-manganese battery, which is prepared by the preparation method of the hydrophilic composite separator for a secondary zinc-manganese battery according to any one of claims 1 to 9.
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