CN118292277A - Water-based zinc ion battery diaphragm based on electrostatic spinning and preparation method thereof - Google Patents
Water-based zinc ion battery diaphragm based on electrostatic spinning and preparation method thereof Download PDFInfo
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- CN118292277A CN118292277A CN202410287254.XA CN202410287254A CN118292277A CN 118292277 A CN118292277 A CN 118292277A CN 202410287254 A CN202410287254 A CN 202410287254A CN 118292277 A CN118292277 A CN 118292277A
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- polyvinyl alcohol
- nanofiber membrane
- solution
- separator
- water
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 34
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 238000010041 electrostatic spinning Methods 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title abstract description 13
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 77
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 77
- 239000012528 membrane Substances 0.000 claims abstract description 67
- 239000002121 nanofiber Substances 0.000 claims abstract description 53
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims abstract description 50
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims abstract description 42
- 238000009987 spinning Methods 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 24
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims abstract description 21
- 230000008021 deposition Effects 0.000 claims abstract description 16
- 238000001035 drying Methods 0.000 claims abstract description 15
- 229920000767 polyaniline Polymers 0.000 claims abstract description 14
- 238000004132 cross linking Methods 0.000 claims abstract description 12
- 238000011065 in-situ storage Methods 0.000 claims abstract description 6
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 6
- 238000010438 heat treatment Methods 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 50
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 40
- 239000003792 electrolyte Substances 0.000 claims description 16
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 230000008569 process Effects 0.000 claims description 7
- 238000002347 injection Methods 0.000 claims description 6
- 239000007924 injection Substances 0.000 claims description 6
- 238000001523 electrospinning Methods 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 2
- 239000011701 zinc Substances 0.000 abstract description 37
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 abstract description 33
- 229910052725 zinc Inorganic materials 0.000 abstract description 33
- 210000001787 dendrite Anatomy 0.000 abstract description 12
- 230000012010 growth Effects 0.000 abstract description 10
- 230000005684 electric field Effects 0.000 abstract description 7
- 229920000642 polymer Polymers 0.000 abstract 1
- 239000003365 glass fiber Substances 0.000 description 22
- 230000000052 comparative effect Effects 0.000 description 18
- 239000008367 deionised water Substances 0.000 description 11
- 229910021641 deionized water Inorganic materials 0.000 description 11
- 239000002033 PVDF binder Substances 0.000 description 9
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 210000004027 cell Anatomy 0.000 description 7
- 230000004048 modification Effects 0.000 description 7
- 238000012986 modification Methods 0.000 description 7
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 6
- 239000000835 fiber Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- -1 zinc trifluoromethane iodate Chemical group 0.000 description 6
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 5
- 230000014759 maintenance of location Effects 0.000 description 5
- 229910001220 stainless steel Inorganic materials 0.000 description 5
- 239000010935 stainless steel Substances 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- 230000009286 beneficial effect Effects 0.000 description 4
- 238000011049 filling Methods 0.000 description 4
- 239000007774 positive electrode material Substances 0.000 description 4
- CMZUMMUJMWNLFH-UHFFFAOYSA-N sodium metavanadate Chemical group [Na+].[O-][V](=O)=O CMZUMMUJMWNLFH-UHFFFAOYSA-N 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 229910000166 zirconium phosphate Inorganic materials 0.000 description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 3
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 3
- 235000011130 ammonium sulphate Nutrition 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000005457 ice water Substances 0.000 description 3
- 230000001788 irregular Effects 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 125000004433 nitrogen atom Chemical group N* 0.000 description 3
- 230000002035 prolonged effect Effects 0.000 description 3
- 229910021642 ultra pure water Inorganic materials 0.000 description 3
- 239000012498 ultrapure water Substances 0.000 description 3
- 238000009736 wetting Methods 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 230000008595 infiltration Effects 0.000 description 2
- 238000001764 infiltration Methods 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 239000002952 polymeric resin Substances 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 229920003002 synthetic resin Polymers 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 102000004310 Ion Channels Human genes 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 229910007565 Zn—Cu Inorganic materials 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 239000006183 anode active material Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- TVZPLCNGKSPOJA-UHFFFAOYSA-N copper zinc Chemical compound [Cu].[Zn] TVZPLCNGKSPOJA-UHFFFAOYSA-N 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000012983 electrochemical energy storage Methods 0.000 description 1
- 238000003411 electrode reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 238000000265 homogenisation Methods 0.000 description 1
- 230000010220 ion permeability Effects 0.000 description 1
- JQJCSZOEVBFDKO-UHFFFAOYSA-N lead zinc Chemical compound [Zn].[Pb] JQJCSZOEVBFDKO-UHFFFAOYSA-N 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000004222 uncontrolled growth Effects 0.000 description 1
- 235000012431 wafers Nutrition 0.000 description 1
Classifications
-
- 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
Landscapes
- Cell Separators (AREA)
Abstract
The invention belongs to the technical field of batteries, and particularly discloses a water-based zinc ion battery diaphragm based on electrostatic spinning and a preparation method thereof. The preparation method of the diaphragm comprises the following steps: firstly, taking a polyvinyl alcohol solution as a spinning solution, carrying out electrostatic spinning and drying to obtain a polyvinyl alcohol nanofiber membrane; then heating the polyvinyl alcohol nanofiber membrane, and performing thermal crosslinking treatment to obtain a polyvinyl alcohol porous nanofiber membrane; finally, immersing the polyvinyl alcohol porous nanofiber membrane in an aniline solution, dropwise adding an ammonium persulfate solution, standing, carrying out in-situ polymerization reaction, and forming a polyaniline deposition layer on the surface of the polyvinyl alcohol porous nanofiber membrane to obtain the polymer. The diaphragm prepared by the method has good reversibility of zinc stripping deposition, can inhibit dendrite growth, homogenize an interface electric field of a negative electrode, stabilize the zinc negative electrode, realize long cycle life of a water-based zinc ion battery, reduce the use cost of the battery and improve the volume energy density of the battery.
Description
Technical Field
The invention belongs to the technical field of batteries, and particularly relates to a water-based zinc ion battery diaphragm based on electrostatic spinning and a preparation method thereof.
Background
Electrochemical energy storage technologies (e.g., lithium, sodium, zinc ion batteries) have evolved over the years to produce heat. Among various energy storage devices, the aqueous zinc ion battery has great application potential in the field of large-scale energy storage due to the advantages of excellent high safety, low cost, high theoretical capacity, low oxidation-reduction potential and the like. However, the problems of dendrite growth of the negative electrode and side reactions (hydrogen evolution reaction and corrosion reaction) on the electrode surface are restricted in practical application, and the coulomb efficiency and the cycle stability of the battery are seriously affected. On the surface of the electrode, the uneven distribution of the electric field on the surface of the zinc sheet and the uneven distribution of the electric field and the irregular dendritic growth are brought about by the uncontrolled growth of dendrites at the protruding parts due to the 'tip effect' existing in the zinc deposition process and the zinc metal corrosion and hydrogen evolution reaction. In order to solve the problems, various strategies are proposed from different angles to cope with the problems, such as surface modification of a zinc negative electrode, structural design of the negative electrode, electrolyte optimization and the like, and certain progress is made in the aspects of novel negative electrodes and electrolyte. The diaphragm is used as an inactive component in the battery, so that direct contact of the anode and the cathode can be avoided, and the diaphragm can be used as an ion channel to have a remarkable influence on the performance of the battery.
Currently, typical separators for aqueous zinc ion batteries include glass fiber, polyolefin separators and filter paper separators, wherein: glass fibers are widely used in aqueous zinc ion batteries due to their porosity, high ionic conductivity and excellent electrolyte wettability, but glass fibers have a strong affinity for zinc, which can guide zinc ions to grow in the direction of the separator during zinc deposition, and can easily puncture the separator to cause short circuits. Polyolefin separators have poor wettability to aqueous electrolytes due to their strong chemical properties, resulting in large interfacial contact resistance that is not suitable for use in aqueous zinc ion batteries. The filter paper membrane has the advantages of good hydrophilicity and low cost, but the irregular pore structure and poor mechanical property of the filter paper membrane can aggravate the uneven deposition of zinc.
Therefore, the design and development of the novel diaphragm material have important significance for realizing long-circulating water-based zinc ion batteries.
Disclosure of Invention
The present invention aims to solve at least one of the technical problems in the prior art described above. Therefore, the invention provides the water-based zinc ion battery diaphragm based on electrostatic spinning and the preparation method thereof, and the diaphragm has good reversibility of zinc stripping deposition, can inhibit dendrite growth, homogenize an interface electric field of a negative electrode, stabilize the zinc negative electrode, realize long cycle life of the water-based zinc ion battery, reduce the use cost of the battery and improve the volume energy density of the battery.
To solve the above technical problems, a first aspect of the present invention provides a method for preparing a separator, including the following steps:
(1) Taking a polyvinyl alcohol solution as a spinning solution, carrying out electrostatic spinning and drying to obtain a polyvinyl alcohol nanofiber membrane;
(2) Heating the polyvinyl alcohol nanofiber membrane, and performing thermal crosslinking treatment to obtain a polyvinyl alcohol porous nanofiber membrane;
(3) Immersing the polyvinyl alcohol porous nanofiber membrane in an aniline solution, dropwise adding an ammonium persulfate solution, standing, performing in-situ polymerization reaction, and forming a polyaniline deposition layer on the surface of the polyvinyl alcohol porous nanofiber membrane to obtain the diaphragm.
Specifically, the invention firstly takes a specific polymer resin material polyvinyl alcohol solution as spinning solution, and prepares a polyvinyl alcohol nanofiber membrane by adopting an electrostatic spinning mode; then carrying out thermal crosslinking treatment on the polyvinyl alcohol nanofiber membrane to obtain a polyvinyl alcohol porous nanofiber membrane, wherein the fiber membrane has good reversibility of zinc stripping deposition, is beneficial to prolonging the long cycle life of a battery, and the porous structure ensures free shuttling of zinc ions; meanwhile, the carbonyl functional groups rich in the surface of the film layer and the strong home position action of carbonyl and zinc lead the electric field on the surface of the zinc cathode to be evenly distributed, thereby being beneficial to 002 crystal face deposition of zinc, inhibiting growth of zinc dendrites and being beneficial to improving the initial capacity and capacity retention rate of the battery. Finally, polyaniline modification is carried out on the polyvinyl alcohol porous nanofiber membrane, so that abundant N atoms are added on the surface of the membrane layer, the homogenization of the interface electric field of the negative electrode is facilitated, the zinc negative electrode is stabilized, and the cycle life of the battery is further prolonged.
Preferably, in step (1), the solvent of the polyvinyl alcohol solution is water. The preparation process comprises the following steps: adding polyvinyl alcohol (PVA) into water, and magnetically stirring at 80-90 deg.c for 30-50min to obtain homogeneous aqueous solution of polyvinyl alcohol.
Preferably, in the step (1), the mass concentration of the polyvinyl alcohol solution is 8-12%.
Preferably, in the step (1), the process parameters of the electrospinning are as follows: the injection speed of the spinning solution is 0.8-1.2mL/h, the spinning voltage is 18-20kV, the rotating speed of the receiving roller is 1000-1200r/min, the receiving distance is 9-13cm, and the spinning temperature is 25-30 ℃.
Preferably, in the step (1), the electrospinning is performed using a 22# stainless steel needle, and a tin foil is used as a receiving substrate.
Preferably, in step (1), the drying is performed under vacuum at 50-60 ℃ for 6-12 hours.
Preferably, in the step (2), the temperature of the thermal crosslinking treatment is 120-150 ℃.
Preferably, in the step (2), the time of the thermal crosslinking treatment is 30-40min.
Preferably, in the step (3), the aniline solution is prepared from hydrochloric acid, aniline and water; the volume ratio of the hydrochloric acid to the aniline to the water is 1: (0.3-0.5): (10-30). The aniline solution is formed by dispersing hydrochloric acid and aniline in water, and the concentration of the hydrochloric acid is 10-15mol/L.
Preferably, in the step (3), the ammonium persulfate solution is prepared from hydrochloric acid, ammonium persulfate and water; in the ammonium persulfate solution, the concentration of ammonium persulfate is 0.1-0.2mol/L, and the concentration of hydrochloric acid is 0.4-0.8mol/L. The preparation method of the ammonium persulfate solution comprises the following steps: ammonium persulfate is firstly dissolved in water, and then hydrochloric acid with the concentration of 10-15mol/L is added dropwise.
Preferably, in the step (3), the volume ratio of the aniline solution and the ammonium persulfate solution is 1: (0.8-1.2).
Preferably, in the step (3), the standing time is 20-40min.
Preferably, in step (3), after the standing, the method further comprises the steps of cleaning and drying the membrane.
Preferably, in the step (3), the washing is performed by adopting deionized water and ethanol in sequence, so as to remove the redundant aniline solution and ammonium persulfate solution.
Preferably, in step (3), the drying is performed under vacuum at 50-60 ℃ for 10-15 hours.
In a second aspect of the present invention, there is provided a separator manufactured by the above manufacturing method, comprising a polyvinyl alcohol porous nanofiber membrane and a polyaniline deposition layer formed on an outer surface of the polyvinyl alcohol porous nanofiber membrane.
A third aspect of the present invention provides an aqueous zinc-ion battery comprising a positive electrode, a negative electrode, an electrolyte and the separator described above.
Preferably, the active material of the positive electrode is sodium vanadate.
Preferably, the negative electrode is a zinc sheet.
Preferably, the electrolyte is zinc trifluoromethane iodate.
Specifically, the water-based zinc ion battery provided by the invention uses sodium vanadate as an anode active material, a zinc sheet as a cathode, and zinc trifluoromethane iodate as an electrolyte, and the diaphragm is adopted, so that the free shuttle of zinc ions is ensured by utilizing good porosity of the diaphragm; the surface of the diaphragm is rich in carbonyl functional groups, and the strong coordination of carbonyl and zinc can inhibit the growth of zinc dendrites; meanwhile, the modification of polyaniline adds rich N atoms to the surface of the diaphragm, so that the cycle life of the battery can be further prolonged. Therefore, the aqueous zinc ion battery of the invention not only has high initial capacity and good capacity retention rate, but also has excellent battery cycle life.
Compared with the prior art, the technical scheme of the invention has at least the following technical effects or advantages:
(1) According to the invention, a specific polymer resin material polyvinyl alcohol is firstly prepared into a porous nanofiber membrane in an electrostatic spinning mode, and then polyaniline is used for carrying out surface modification on the porous nanofiber membrane to prepare the polyvinyl alcohol porous nanofiber membrane with the polyaniline deposited on the surface, and the membrane has good porosity, rich surface components and controllable electrospinning parameters, so that the application of the membrane in a water-based zinc ion battery is assisted.
(2) The membrane prepared by the method has good reversibility of zinc stripping deposition, is beneficial to prolonging the long cycle life of the battery, and the porous structure ensures free shuttling of zinc ions. Meanwhile, the carbonyl functional groups rich in the surface of the film layer and the strong home position action of carbonyl and zinc enable the electric field on the surface of the zinc cathode to be uniformly distributed, so that the growth of zinc dendrites can be effectively inhibited, and the initial capacity and the good capacity retention rate of the battery are ensured. In addition, the polyaniline is modified to add rich N atoms on the surface of the diaphragm, so that the zinc cathode can be stabilized, and the cycle life of the battery is further prolonged.
Drawings
FIG. 1 is a graphical representation of the physical comparison of the fibrous membranes prepared in steps (1) - (3) of example 1;
FIG. 2 is a surface scanning electron microscope image of the separator prepared in example 1;
FIG. 3 is a physical view of the glass fiber of comparative example 1;
FIG. 4 is a surface scanning electron micrograph of a zinc anode after 40 cycles of a symmetrical battery assembled from the separator prepared in example 1 and the glass fiber of comparative example 1;
FIG. 5 is a graph comparing coulombic efficiencies of an asymmetric cell assembled from a separator prepared in example 1 and glass fibers of comparative example 1;
FIG. 6 is a long cycle chart of a symmetrical battery assembled from the separator prepared in example 1 and the glass fiber of comparative example 1;
FIG. 7 is a graph comparing specific discharge capacity and coulombic efficiency of an aqueous zinc ion battery assembled from a separator prepared in example 1 and glass fibers of comparative example 1;
FIG. 8 is a long cycle chart of a symmetrical cell assembled from the fibrous membranes prepared in steps (1) - (3) of example 1;
FIG. 9 is a graph showing the result of impregnating the electrolyte with the separator prepared in the step (2) of example 1 and comparative example 2.
Detailed Description
The present invention is described in detail below with reference to examples to facilitate understanding of the present invention by those skilled in the art. It is specifically pointed out that the examples are given solely for the purpose of illustration of the invention and are not to be construed as limiting the scope of the invention, since numerous insubstantial modifications and variations of the invention will be within the scope of the invention, as described above, will become apparent to those skilled in the art. Meanwhile, the raw materials mentioned below are not specified, and are all commercial products; the process steps or preparation methods not mentioned in detail are those known to the person skilled in the art.
Example 1
A method of preparing a separator, comprising the steps of:
(1) 1.0g of polyvinyl alcohol (molecular weight 1799) is added into 4mL of ultrapure water and magnetically stirred for 30min at 90 ℃ to obtain uniform spinning solution with the mass concentration of 10%; then filling the spinning solution into a 5mL injector, placing the injector into electrostatic spinning equipment, and performing electrostatic spinning by using a 22# stainless steel needle; then the prepared nanofiber membrane is placed in a vacuum oven at 50 ℃ for drying for 12 hours; the polyvinyl alcohol nanofiber membrane is obtained, and the appearance of the polyvinyl alcohol nanofiber membrane is shown in figure 1A.
Wherein: the electrostatic spinning process parameters are as follows: the injection speed was 0.8mL/h, the spinning voltage was 20kV, tin foil was used as the receiving substrate, the receiving drum rotation speed was 1000r/min, the receiving distance was 10cm, and the spinning temperature was set at 25 ℃.
(2) And (3) placing the polyvinyl alcohol nanofiber membrane prepared in the step (1) in a baking oven at 140 ℃ for heat crosslinking treatment for 40min to obtain the polyvinyl alcohol porous nanofiber membrane, wherein the appearance of the polyvinyl alcohol porous nanofiber membrane is shown in a figure 1B, the membrane after heat crosslinking is light yellow, and the surface of the membrane is regular.
(3) Dissolving 3.2mmol of ammonium persulfate (NH 4)2S2O8) in 20mL of deionized water, dropwise adding 1mL of hydrochloric acid (HCl, 12 mol/L) to prepare an ammonium persulfate solution, dispersing 1mL of hydrochloric acid (HCl, 12 mol/L) and 400 mu L of aniline (C 6H7 N) in 20mL of deionized water to prepare an aniline solution, completely wetting the polyvinyl alcohol porous nanofiber membrane (with the area of about 10cm 2) prepared in the step (2) in the aniline solution of an ice water bath, dropwise adding the ammonium sulfate solution into the aniline solution, standing for 30min, performing in-situ polymerization reaction, forming a polyaniline deposition layer on the surface of the polyvinyl alcohol porous nanofiber membrane, finally washing with deionized water and ethanol, and drying in a vacuum oven at 60 ℃ for 12 hours to obtain the diaphragm of the embodiment, wherein the appearance of the diaphragm is shown in FIG. 1C, and the outer surface of the membrane is uniformly deposited with a black polyaniline deposition layer.
Fig. 2 is a surface scanning electron microscope image of the separator prepared in example 1, and it can be seen from fig. 2 that the separator has high surface porosity and long-range order of fibers, and can provide a good channel for zinc ion transmission.
Example 2
A method of preparing a separator, comprising the steps of:
(1) 0.8g of polyvinyl alcohol (molecular weight 1799) is added into 9.2mL of ultrapure water, and the mixture is magnetically stirred for 30min at 90 ℃ to obtain a uniform spinning solution with the mass concentration of 8%; then filling the spinning solution into a 5mL injector, placing the injector into electrostatic spinning equipment, and performing electrostatic spinning by using a 22# stainless steel needle; then the prepared nanofiber membrane is placed in a vacuum oven at 50 ℃ for drying for 12 hours; and obtaining the polyvinyl alcohol nanofiber membrane.
Wherein: the electrostatic spinning process parameters are as follows: the injection speed was 0.8mL/h, the spinning voltage was 18kV, tin foil was used as the receiving substrate, the receiving drum rotation speed was 1200r/min, the receiving distance was 15cm, and the spinning temperature was set at 25 ℃.
(2) And (3) placing the polyvinyl alcohol nanofiber membrane prepared in the step (1) in a baking oven at 140 ℃ for heat crosslinking treatment for 40min to obtain the polyvinyl alcohol porous nanofiber membrane.
(3) Dissolving 3.2mmol of ammonium persulfate (NH 4)2S2O8) in 20mL of deionized water, dropwise adding 1mL of hydrochloric acid (HCl, 12 mol/L) to prepare an ammonium persulfate solution, dispersing 1mL of hydrochloric acid (HCl, 12 mol/L) and 400 mu L of aniline (C 6H7 N) in 20mL of deionized water to prepare an aniline solution, completely wetting the polyvinyl alcohol porous nanofiber membrane (with the area of about 10cm 2) prepared in the step (2) in the aniline solution of an ice water bath, dropwise adding the ammonium sulfate solution into the aniline solution, standing for 30min, performing in-situ polymerization reaction, forming a polyaniline deposition layer on the surface of the polyvinyl alcohol porous nanofiber membrane, finally washing with deionized water and ethanol, and drying in a vacuum oven at 60 ℃ for 12 hours to obtain the diaphragm of the embodiment.
Example 3
(1) 0.9G of polyvinyl alcohol (molecular weight 1799) is added into 9.1mL of ultrapure water, and the mixture is magnetically stirred for 30min at 90 ℃ to obtain uniform spinning solution with the mass concentration of 9%; then filling the spinning solution into a 5mL injector, placing the injector into electrostatic spinning equipment, and performing electrostatic spinning by using a 22# stainless steel needle; then the prepared nanofiber membrane is placed in a vacuum oven at 50 ℃ for drying for 12 hours; and obtaining the polyvinyl alcohol nanofiber membrane.
Wherein: the electrostatic spinning process parameters are as follows: the injection speed was 1.2mL/h, the spinning voltage was 19kV, tin foil was used as the receiving substrate, the receiving drum rotation speed was 1100r/min, the receiving distance was 15cm, and the spinning temperature was set at 25 ℃.
(2) And (3) placing the polyvinyl alcohol nanofiber membrane prepared in the step (1) in a baking oven at 140 ℃ for heat crosslinking treatment for 40min to obtain the polyvinyl alcohol porous nanofiber membrane.
(3) Dissolving 3.2mmol of ammonium persulfate (NH 4)2S2O8) in 20mL of deionized water, dropwise adding 1mL of hydrochloric acid (HCl, 12 mol/L) to prepare an ammonium persulfate solution, dispersing 1mL of hydrochloric acid (HCl, 12 mol/L) and 400 mu L of aniline (C 6H7 N) in 20mL of deionized water to prepare an aniline solution, completely wetting the polyvinyl alcohol porous nanofiber membrane (with the area of about 10cm 2) prepared in the step (2) in the aniline solution of an ice water bath, dropwise adding the ammonium sulfate solution into the aniline solution, standing for 30min, performing in-situ polymerization reaction, forming a polyaniline deposition layer on the surface of the polyvinyl alcohol porous nanofiber membrane, finally washing with deionized water and ethanol, and drying in a vacuum oven at 60 ℃ for 12 hours to obtain the diaphragm of the embodiment.
Comparative example 1
The commercial Whatman glass fiber/F has a pore size of 0.6-0.8 μm, and the appearance of the fiber film is shown in FIG. 3, and the surface of the fiber film is rough and irregular.
Comparative example 2
A method of preparing a separator, comprising the steps of:
1.2g of polyvinylidene fluoride (PVDF, molecular weight 180000) is added into 4.8g of N, N-dimethylformamide, and the mixture is magnetically stirred for 90min to obtain a uniform spinning solution with the mass concentration of 20%; then filling the spinning solution into a 10mL injector, placing the injector into electrostatic spinning equipment, and performing electrostatic spinning by using a 22# stainless steel needle; then the prepared nanofiber membrane is placed in a vacuum oven at 70 ℃ for drying for 8 hours; the polyvinylidene fluoride nanofiber membrane of this comparative example was obtained. Wherein: the electrostatic spinning process parameters are as follows: the injection speed was 1.0mL/h, the spinning voltage was 15kV, tin foil was used as the receiving substrate, the receiving drum rotation speed was 1100r/min, the receiving distance was 10cm, and the spinning temperature was set at 25 ℃.
Application example
A method of making a battery comprising the steps of:
(1) Preparation of a positive electrode material: 0.3g of vanadium pentoxide was dissolved in 10mL of sodium chloride aqueous solution, continuously stirred for 72 hours, and then washed with deionized water for 6 times to form orange-red gel, and then dried in a vacuum oven at 60 ℃ for 12 hours to obtain a positive electrode material sodium vanadate (NVO).
(2) Preparing a positive electrode plate: the positive electrode material NVO, conductive carbon black (Super P Li) and polyvinylidene fluoride (PVDF) prepared in the step (1) are mixed according to the mass ratio of 7:2:1, uniformly dispersing N-methyl pyrrolidone (NMP) solvent, blending to a proper viscosity, coating on carbon cloth, drying in a vacuum oven at 60 ℃ for 12 hours, and cutting into pole piece wafers with the diameter of 10 mm;
(3) Preparation of Zn-Zn symmetric cell: a 2025 button cell was produced by using a high-purity zinc sheet as a positive electrode and a negative electrode, 1mol/L zinc trifluoromethane iodate as an electrolyte, and the separator prepared in example 1 and the glass fiber of comparative example 1 as separator materials, respectively;
(4) Preparation of Zn-Cu asymmetric cell: 2025 button cell was produced using copper sheets and zinc sheets as positive and negative electrodes, 1mol/L zinc trifluoromethane iodate as electrolyte, and the separator prepared in example 1 and the glass fiber of comparative example 1 as separator materials, respectively;
(5) Preparation of a water-based zinc ion battery: and (3) taking a high-purity zinc sheet as a negative electrode, taking 1mol/L zinc trifluoromethane iodate as an electrolyte, respectively taking the diaphragm prepared in the example 1 and the glass fiber prepared in the comparative example 1 as diaphragm materials, and taking the NVO pole sheet prepared in the step (2) as a positive electrode to prepare the 2025 button cell.
Performance testing
1. Inhibiting dendrite growth
According to the method of the application example of the invention, a Zn-Zn symmetric battery is assembled by using the diaphragm (modified polyvinyl alcohol) prepared in the example 1 and the glass fiber of the comparative example 1, and a scanning electron microscope diagram of the surface of a zinc cathode after the symmetric battery circulates for 40 circles under the current density of 1mA cm -2 is shown in figure 4. As can be seen from fig. 4, on the surface of the negative electrode of the battery using glass fiber, dendrites grow seriously and develop <101> crystal planes, and some residual fiber of glass fiber appears on the surface of the zinc sheet, because the affinity of the glass fiber and the zinc sheet is strong, zinc dendrites are guided to grow toward the direction of the separator, and the structure of the glass fiber is proved to be difficult to maintain structural integrity; the modified polyvinyl alcohol diaphragm used on the surface of the battery cathode has no obvious dendrite growth and no residual fiber on the surface, which proves that the modified polyvinyl alcohol diaphragm prepared by the invention can effectively inhibit dendrite growth.
2. Electrochemical Properties
The separator (modified polyvinyl alcohol) prepared in example 1 and the glass fiber of comparative example 1 were assembled into a zn—cu asymmetric battery according to the method of the application example of the present invention, and the coulombic efficiency of the asymmetric battery was measured at a current density of 1mA cm -2, and the result is shown in fig. 5. As can be seen from fig. 5, the battery using the modified polyvinyl alcohol separator maintained good coulombic efficiency after 1000 cycles, about 99%.
The separator (modified polyvinyl alcohol) prepared in example 1 and the glass fiber of comparative example 1 were assembled into a Zn-Zn symmetrical battery according to the method of application example of the present invention, and the long cycle performance of the symmetrical battery was tested at a current density of 2mA cm -2, and the results are shown in fig. 6. As can be seen from fig. 6, the battery using the modified polyvinyl alcohol separator can be stably circulated for more than 1400 hours.
The separator (modified polyvinyl alcohol) prepared in example 1 and the glass fiber of comparative example 1 were assembled into an aqueous zinc ion battery according to the method of the application example of the present invention, and the specific discharge capacity and coulombic efficiency of the aqueous zinc ion battery were measured at a current density of 1A g -1, and the results are shown in fig. 7. As can be seen from fig. 7, the aqueous zinc ion battery using the modified polyvinyl alcohol separator, which uses the sodium vanadate positive electrode material as well, has a higher initial capacity than the aqueous zinc ion battery using the glass fiber, and also has a slightly higher coulombic efficiency; under the current density of 1Ag -1, the capacity of the aqueous zinc ion battery using the modified polyvinyl alcohol diaphragm after 240 circles is 229.4mAh g -1, and the capacity retention rate is 81.4%; the capacity of the aqueous zinc ion battery using glass fiber was only 121.6mAh g -1, and the capacity retention rate was 60.6%, indicating that the modified polyvinyl alcohol separator showed excellent cycle life.
According to the method of application example of the present invention, the polyvinyl alcohol nanofiber membrane (polyvinyl alcohol), the polyvinyl alcohol porous nanofiber membrane (crosslinked polyvinyl alcohol) and the modified polyvinyl alcohol membrane prepared in the steps (1) - (3) in the example 1 were assembled into a Zn-Zn symmetric battery, and the long cycle performance of the symmetric battery was tested at a current density of 1mA cm -2, and the results are shown in FIG. 8. As can be seen from fig. 8, the modified polyvinyl alcohol separator has stronger ion permeability, ensuring a long cycle life of the battery.
3. Wettability by water
100 Mu L of zinc trifluoromethane iodate serving as an electrolyte of 1mol/L is respectively dripped on the surfaces of the polyvinyl alcohol porous nanofiber membrane (crosslinked polyvinyl alcohol) prepared in the step (2) in the example 1 and the polyvinylidene fluoride nanofiber membrane (polyvinylidene fluoride) prepared in the comparative example 2, and the infiltration performance of the two diaphragms to the electrolyte is observed, and the result is shown in FIG. 9. As can be seen from fig. 9, the polyvinylidene fluoride separator has a low degree of wettability to the electrolyte, whereas the crosslinked polyvinyl alcohol separator completely wets the electrolyte. Therefore, the modified polyvinyl alcohol diaphragm prepared by the invention has good infiltration performance and meets the use requirement of a battery diaphragm; however, the polyvinylidene fluoride nanofiber membrane prepared in comparative example 2 is not suitable for the application of battery separator due to poor wettability.
It will be apparent to those skilled in the art that several simple deductions or substitutions may be made without departing from the inventive concept. Accordingly, it is intended that all such modifications as would be within the scope of this invention be included within the scope of this invention. The above embodiments are preferred embodiments of the present invention, and all similar processes and equivalent modifications are intended to fall within the scope of the present invention.
Claims (10)
1. A method of making a separator comprising the steps of:
(1) Taking a polyvinyl alcohol solution as a spinning solution, carrying out electrostatic spinning and drying to obtain a polyvinyl alcohol nanofiber membrane;
(2) Heating the polyvinyl alcohol nanofiber membrane, and performing thermal crosslinking treatment to obtain a polyvinyl alcohol porous nanofiber membrane;
(3) Immersing the polyvinyl alcohol porous nanofiber membrane in an aniline solution, dropwise adding an ammonium persulfate solution, standing, performing in-situ polymerization reaction, and forming a polyaniline deposition layer on the surface of the polyvinyl alcohol porous nanofiber membrane to obtain the diaphragm.
2. The method for producing a separator according to claim 1, wherein in the step (1), the solvent of the polyvinyl alcohol solution is water; and/or, the mass concentration of the polyvinyl alcohol solution is 8-12%.
3. The method for preparing a separator according to claim 1, wherein in the step (1), the process parameters of the electrospinning are: the injection speed of the spinning solution is 0.8-1.2mL/h, the spinning voltage is 18-20kV, the rotating speed of the receiving roller is 1000-1200r/min, the receiving distance is 9-13cm, and the spinning temperature is 25-30 ℃.
4. The method of producing a separator according to claim 1, wherein in the step (1), the drying is performed under vacuum at 50 to 60 ℃ for 6 to 12 hours.
5. The method for producing a separator according to claim 1, wherein in the step (2), the temperature of the thermal crosslinking treatment is 120 to 150 ℃; and/or the time of the thermal crosslinking treatment is 30-40min.
6. The method of preparing a separator according to any one of claims 1 to 5, wherein in step (3), the aniline solution is prepared from hydrochloric acid, aniline and water; the volume ratio of the hydrochloric acid to the aniline to the water is 1: (0.3-0.5): (10-30).
7. The method for producing a separator according to any one of claims 1 to 5, wherein in the step (3), the ammonium persulfate is formulated of hydrochloric acid, ammonium persulfate and water; in the ammonium persulfate solution, the concentration of ammonium persulfate is 0.1-0.2mol/L, and the concentration of hydrochloric acid is 0.4-0.8mol/L.
8. The method of producing a separator according to any one of claims 1 to 5, wherein in the step (3), the time of standing is 20 to 40 minutes.
9. A separator manufactured by the method of manufacturing a separator according to any one of claims 1 to 8, the separator comprising a polyvinyl alcohol porous nanofiber membrane and a polyaniline deposition layer formed on an outer surface of the polyvinyl alcohol porous nanofiber membrane.
10. An aqueous zinc ion battery comprising a positive electrode, a negative electrode, an electrolyte and the separator of claim 9.
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