CN111525185A - Flexible zinc ion battery polymer electrolyte and preparation and application thereof - Google Patents
Flexible zinc ion battery polymer electrolyte and preparation and application thereof Download PDFInfo
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- CN111525185A CN111525185A CN202010236716.7A CN202010236716A CN111525185A CN 111525185 A CN111525185 A CN 111525185A CN 202010236716 A CN202010236716 A CN 202010236716A CN 111525185 A CN111525185 A CN 111525185A
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- 239000005518 polymer electrolyte Substances 0.000 title claims abstract description 61
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000003792 electrolyte Substances 0.000 claims abstract description 30
- 239000000230 xanthan gum Substances 0.000 claims abstract description 21
- 235000010493 xanthan gum Nutrition 0.000 claims abstract description 21
- 229920001285 xanthan gum Polymers 0.000 claims abstract description 21
- 229940082509 xanthan gum Drugs 0.000 claims abstract description 21
- 229920000742 Cotton Polymers 0.000 claims abstract description 17
- 239000011230 binding agent Substances 0.000 claims abstract description 14
- 229920002678 cellulose Polymers 0.000 claims abstract description 14
- 239000001913 cellulose Substances 0.000 claims abstract description 14
- 239000003999 initiator Substances 0.000 claims abstract description 14
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000007864 aqueous solution Substances 0.000 claims abstract description 12
- 239000000203 mixture Substances 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 9
- 238000002791 soaking Methods 0.000 claims abstract description 6
- 229920001046 Nanocellulose Polymers 0.000 claims description 19
- 229920000642 polymer Polymers 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 14
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical group [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 12
- 239000011259 mixed solution Substances 0.000 claims description 11
- 239000011521 glass Substances 0.000 claims description 10
- 229920006254 polymer film Polymers 0.000 claims description 9
- 229940099596 manganese sulfate Drugs 0.000 claims description 8
- 235000007079 manganese sulphate Nutrition 0.000 claims description 8
- 239000011702 manganese sulphate Substances 0.000 claims description 8
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 8
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 8
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 8
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 6
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical group C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 238000000227 grinding Methods 0.000 claims description 5
- 229960001763 zinc sulfate Drugs 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 4
- 239000011148 porous material Substances 0.000 claims description 3
- 238000007334 copolymerization reaction Methods 0.000 claims description 2
- 238000003760 magnetic stirring Methods 0.000 claims description 2
- 239000013078 crystal Substances 0.000 abstract description 4
- 230000000379 polymerizing effect Effects 0.000 abstract 1
- 239000000499 gel Substances 0.000 description 58
- 239000012528 membrane Substances 0.000 description 32
- 239000011701 zinc Substances 0.000 description 25
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 24
- 229910052725 zinc Inorganic materials 0.000 description 24
- 229920002401 polyacrylamide Polymers 0.000 description 16
- 239000011244 liquid electrolyte Substances 0.000 description 10
- 239000000843 powder Substances 0.000 description 10
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- 239000007784 solid electrolyte Substances 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 230000009286 beneficial effect Effects 0.000 description 6
- 239000011245 gel electrolyte Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 230000008021 deposition Effects 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 5
- 238000010998 test method Methods 0.000 description 5
- 238000004146 energy storage Methods 0.000 description 4
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 4
- 230000010287 polarization Effects 0.000 description 4
- 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 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 239000004744 fabric Substances 0.000 description 3
- 239000003365 glass fiber Substances 0.000 description 3
- 238000001000 micrograph Methods 0.000 description 3
- 235000010413 sodium alginate Nutrition 0.000 description 3
- 239000000661 sodium alginate Substances 0.000 description 3
- 229940005550 sodium alginate Drugs 0.000 description 3
- 150000003751 zinc Chemical class 0.000 description 3
- FHVDTGUDJYJELY-UHFFFAOYSA-N 6-{[2-carboxy-4,5-dihydroxy-6-(phosphanyloxy)oxan-3-yl]oxy}-4,5-dihydroxy-3-phosphanyloxane-2-carboxylic acid Chemical compound O1C(C(O)=O)C(P)C(O)C(O)C1OC1C(C(O)=O)OC(OP)C(O)C1O FHVDTGUDJYJELY-UHFFFAOYSA-N 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- 229940072056 alginate Drugs 0.000 description 2
- 235000010443 alginic acid Nutrition 0.000 description 2
- 229920000615 alginic acid Polymers 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000011267 electrode slurry Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 210000004027 cell Anatomy 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000005357 flat glass Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000000017 hydrogel Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Inorganic materials O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229920005615 natural polymer Polymers 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 239000005486 organic electrolyte Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 238000004154 testing of material Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0065—Solid electrolytes
- H01M2300/0082—Organic polymers
-
- 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 Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Dispersion Chemistry (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
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- Materials Engineering (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention relates to a flexible zinc ion battery polymer electrolyte, and preparation and application thereof, wherein the flexible zinc ion battery polymer electrolyte comprises: uniformly mixing acrylamide and xanthan gum, adding the mixture into a cotton nano-cellulose aqueous solution, polymerizing at constant temperature in the presence of an initiator and a binder, and soaking the mixture in an electrolyte to obtain the gel polymer electrolyte. The gel polymer electrolyte obtained by the invention has high ionic conductivity and mechanical property, can effectively reduce the interface resistance of the battery and inhibit the growth of dendritic crystals, and can improve the cycle stability of the flexible zinc ion battery. The invention has wide application prospect in the field of flexible zinc ion battery electrolyte.
Description
Technical Field
The invention belongs to the field of rechargeable aqueous zinc ion battery electrolytes, and particularly relates to a flexible zinc ion battery polymer electrolyte and preparation and application thereof.
Background
In recent years, great demands for integrated new electronic devices such as wearable electronic devices and flexible displays have led to the development of energy storage devices in electronic devices. In order to adapt to the characteristics of wearable and flexible devices, energy storage devices such as batteries and the like are required to realize the flexible function. Furthermore, the safety of the battery itself and the use of the battery is critical for wearable electronic devices. The traditional rechargeable batteries such as lithium ion batteries and the like are still the mainstream applications of energy storage devices, but active metal lithium and toxic and flammable organic electrolyte in the lithium ion batteries greatly limit the applications of the rechargeable batteries in the field of wearable electronic equipment.
The zinc ion battery becomes a novel energy storage device with great development potential due to high theoretical specific capacity (820mAh/g), and is considered as a substitute of the traditional battery. In addition, the metal zinc has the advantages of abundant resources, safety, no toxicity, stability in water and the like. However, to realize further commercial practical application of the flexible zinc ion battery, several key challenges still exist in the aspect of the electrolyte, including the problems of difficult liquid electrolyte leakage encapsulation, low ionic conductivity of the solid electrolyte, poor mechanical properties of the solid electrolyte, and the like, which seriously affect the cycle life, zinc negative electrode zinc ion stripping/deposition efficiency, and other key properties of the flexible zinc ion battery, thereby hindering the commercialization process thereof.
Based on the current key challenges of flexible zinc ion battery electrolytes, a high molecular polymer can be prepared to be combined with a zinc salt electrolyte as a solid electrolyte of a zinc ion battery aiming at the solid electrolyte so as to avoid the problem of liquid leakage of the liquid electrolyte (j.p.tafur and a.j.f.romero, j.membr.sci.,2014,469,499.), but the ionic conductivity of the solid electrolyte needs to be further improved so as to reduce the interface resistance inside the battery, thereby improving the capacity and the service life of the battery; the solid electrolyte mainly containing hydrogel polymer can be prepared, the ionic conductivity of the solid electrolyte is effectively improved (Huang Y, Zhong M, Shi F, et al, Angew. chem., int.Ed,2017,56, 9141), but the solid electrolyte has low mechanical strength and is unstable.
Patent CN110085925A prepares a zinc alginate based polymer composite gel electrolyte membrane, but the three-dimensional layered structure of the gel polymer adopted by the membrane is very easily affected by the concentration of zinc salt in the electrolyte and pH, resulting in poor stability of the gel polymer electrolyte, and thus the cycle stability of the membrane is poor when the membrane is applied to a zinc ion battery.
Disclosure of Invention
The invention aims to solve the technical problems of providing a flexible zinc ion battery polymer electrolyte, and preparation and application thereof, overcoming the defects of easy leakage, low ionic conductivity and poor mechanical property of a solid polymer electrolyte in the prior zinc ion battery liquid electrolyte package, and improving the key properties of the flexible zinc ion battery such as cycling stability, zinc negative electrode zinc ion uniform deposition and the like.
The gel polymer is obtained by copolymerization of components including acrylamide, xanthan gum, nanocellulose, an initiator and a binder according to parts by weight, wherein the mass ratio of the acrylamide to the xanthan gum to the nanocellulose to the initiator to the binder is 1: 0.01-0.05: 8-10: 0.01-0.02: 0.001 to 0.002.
The nano-cellulose is cotton nano-cellulose, the diameter of the cellulose is 4-10 nm, and the length of the cellulose is 1-3 mu m; the initiator is ammonium persulfate; the binder is N, N' -methylene bisacrylamide.
The preparation method of the gel polymer comprises the following steps:
(1) mixing and grinding acrylamide powder and xanthan gum powder uniformly, adding the mixture into a nano-cellulose aqueous solution, stirring uniformly, adding an initiator and a binder, continuing stirring uniformly, and performing vacuum defoaming treatment to obtain a uniformly viscous mixed solution; wherein the mass ratio of the acrylamide to the xanthan gum to the nano cellulose aqueous solution is 1: 0.01-0.05: 8-10; the mass ratio of the initiator to the binder is 1: 0.05 to 0.1;
(2) pouring the mixed solution obtained in the step (1) into a sealed glass mold, and curing at constant temperature to obtain the xanthan gum and cotton nanocellulose modified polyacrylamide gel polymer electrolyte membrane with a porous structure.
The preferred mode of the above preparation method is as follows:
the nano-cellulose in the step (1) is cotton nano-cellulose, the diameter of the cellulose is 4-10 nm, and the length of the cellulose is 1-3 mu m; the initiator is ammonium persulfate; the binder is N, N' -methylene bisacrylamide.
The stirring in the step (1) is room-temperature magnetic stirring; the stirring time is 0.5-12 h; the time of vacuum defoaming treatment is 0.5-2 h.
The thickness specification of the glass mold in the step (2) is 0.5-3 mm.
The constant-temperature curing in the step (2) comprises the following steps: and (3) placing the mixture in a blast oven for constant temperature curing, wherein the temperature of the blast oven is 60-80 ℃, and the curing time is 2-6 h.
The gel polymer electrolyte is obtained by soaking the gel polymer in an electrolyte.
The electrolyte is a mixed aqueous solution of zinc sulfate and manganese sulfate; wherein the mass ratio of zinc sulfate to manganese sulfate to water is 1: 0.01-0.04: 1.5 to 2.
The gel polymer electrolyte is of a porous structure, and the aperture is 30-100 microns.
The preparation method of the gel polymer electrolyte comprises the following steps: soaking the gel polymer film in electrolyte to obtain a gel polymer electrolyte; wherein the soaking time is 12-48 h.
The invention provides an application of the gel polymer electrolyte in a flexible zinc ion battery.
The invention discloses a method for testing the performance of a flexible zinc ion battery of a gel polymer electrolyte membrane, which comprises the following steps: the active material manganese oxide electrode slurry is coated on a carbon cloth to prepare an anode, the other carbon cloth is electrochemically deposited to prepare a zinc cathode, and the prepared gel polymer electrolyte membrane, the active material manganese oxide electrode slurry, the other carbon cloth and the zinc cathode are assembled into a flexible zinc ion battery according to a sandwich structure to carry out electrochemical test.
The ionic conductivity of the single polyacrylamide gel electrolyte is low, and the ionic conductivity needs to be further improved so as to reduce the interfacial resistance of the electrode and the electrolyte and reduce the polarization. Therefore, when the polyacrylamide is compounded with other natural polymers, a great amount of polar functional groups such as hydroxyl and carboxyl possessed by other polymers and a great amount of intermolecular hydrogen bonding force existing among the polymers can be utilized, and the fixing capacity of the polyacrylamide on electrolyte ions and the water absorption of the gel electrolyte are improved. Meanwhile, the composite gel electrolyte can enhance the mechanical property of single polyacrylamide and is beneficial to inhibiting the dendritic crystal growth of the zinc cathode.
According to the invention, xanthan gum and cotton nanocellulose are introduced into polyacrylamide to improve the mechanical property of the gel polymer electrolyte, and the gel polymer electrolyte is soaked in a high-concentration zinc sulfate and manganese sulfate mixed solution to improve the ionic conductivity.
Advantageous effects
(1) The gel polymer electrolyte membrane prepared by the invention can obviously improve the ionic conductivity and the mechanical property of a single polyacrylamide gel electrolyte, can play the dual roles of a battery electrolyte and a diaphragm, and is more effectively applied to a flexible zinc ion battery (as shown in figures 2 and 3, compared with single polyacrylamide, the gel polymer electrolyte membrane prepared by the invention has obvious improvement on the ionic conductivity and the mechanical property, and is very beneficial to the electrochemical property of a flexible water system battery).
(2) The gel polymer electrolyte membrane prepared by the invention has lower interface resistance and higher mechanical property, reduces the polarization of the battery, and is beneficial to the uniform deposition of zinc ions of a zinc cathode (as can be seen from figure 4, when the gel polymer electrolyte prepared by the invention is used as the battery electrolyte, the interface resistance value is lower than that of a single polyacrylamide electrolyte, and the polarization of the battery is beneficial to being reduced), and in addition, as can be seen from figure 6, when the gel polymer electrolyte prepared by the invention is applied to the zinc ion battery, the problem of dendritic crystals of the cathode is relieved, because the gel polymer electrolyte can ensure the uniform deposition of the zinc ions and inhibit the further growth of the dendritic crystals to a certain extent compared with a liquid electrolyte).
(3) The gel polymer electrolyte membrane prepared by the invention avoids the defects of liquid leakage and difficult packaging of the traditional liquid electrolyte, and can obtain excellent circulation stability when being applied to a flexible water system zinc ion battery.
(4) The gel polymer electrolyte membrane prepared by the invention has rich material sources, is safe and nontoxic and is environment-friendly; the preparation process is simple, easy to operate and low in cost, and has wide application prospect in the field of zinc ion battery electrolytes.
Drawings
FIG. 1(a) is a sealed glass mold disclosed in the present invention, wherein 1 represents a flat glass, and 2 represents a grooved glass; (b) is a scanning electron micrograph of the gel polymer electrolyte membrane prepared in example 1 of the present invention;
FIG. 2 is a stress-strain graph of a gel polymer electrolyte membrane prepared in example 1 of the present invention;
FIG. 3 is an ion conductivity impedance graph of a gel polymer electrolyte membrane prepared in example 2 of the present invention;
FIG. 4 is a graph showing the AC impedance of a flexible zinc ion battery having a gel polymer electrolyte membrane prepared in example 2 according to the present invention as an electrolyte;
FIG. 5 is a graph showing the cycle stability of a flexible zinc ion battery electrolyte using a gel polymer electrolyte membrane prepared in example 3 according to the present invention under 4C conditions;
FIG. 6 is a scanning electron microscope image of the surface of a metal zinc sheet before and after the test when the gel polymer electrolyte membrane prepared in example 3 of the present invention and the liquid electrolyte of comparative example 1 are applied to a zinc symmetric cell; wherein (a) is the smooth surface of the metal zinc sheet after polishing; (b) the surface of the metal zinc sheet is a glass fiber diaphragm and a liquid electrolyte contrast group; (c) the surface of the metal zinc sheet of the experimental group of the gel polymer electrolyte prepared by the invention.
Detailed Description
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.
The starting materials referred to in the examples include acrylamide powder: shanghai test, not less than 98%; xanthan gum powder: wacky, molecular weight 1000000; cotton nanocellulose: guilinqi Hongkie technologies, Inc., CNF-C, cellulose diameter 4-10 nm, length 1-3 μm.
The test method and the standard related to the embodiment comprise that the mechanical property test method in the attached figure 2 is to adopt a universal material testing machine Instron to carry out tensile test on the gel polymer electrolyte, and the standard is to ensure the tensile rate of the testing machine to be consistent and the specification of the tested material to be consistent; the test method of fig. 3 is that a gel polymer electrolyte membrane is clamped by double stainless steel sheets, and impedance is tested by an electrochemical workstation; the test method of fig. 4 is to apply gel polymer electrolyte to a flexible zinc ion battery and test the impedance through an electrochemical workstation; the test method shown in fig. 5 is to apply gel polymer electrolyte to the flexible zinc ion battery and test the cycle performance of the battery through a blue battery test system.
Example 1
(1) Mixing and grinding 2g of acrylamide powder and 100mg of xanthan gum powder uniformly, adding the mixture into 20g of cotton nanocellulose aqueous solution, magnetically stirring for 6 hours at room temperature, adding 30mg of ammonium persulfate initiator and 3mg of N, N' -methylene bisacrylamide binder, continuously stirring for 1 hour, and then carrying out vacuum defoaming treatment for 0.5 hour to obtain uniform and viscous mixed solution.
(2) Pouring the obtained uniform viscous mixed solution into a self-made sealed glass mold (shown in figure 1 a) with the thickness specification of 1mm, and placing the mixture in a forced air oven to be cured for 4 hours at the constant temperature of 70 ℃ to obtain a gel polymer film.
(3) The resulting gel polymer film was immersed in 20ml of 2mol L-1Zinc sulfate and 0.1mol L of-1And mixing the manganese sulfate with the electrolyte for 24 hours to obtain the xanthan gum and cotton nanocellulose modified polyacrylamide gel polymer electrolyte membrane with a porous structure.
The scanning electron microscope image of the gel polymer electrolyte membrane prepared in the embodiment is shown in fig. 1, and it can be seen that the microstructure of the gel polymer electrolyte membrane is porous, the pore size is about 30-100 μm, and the large pore size is beneficial to the rapid migration of electrolyte ions and improves the ionic conductivity.
The stress-strain curve of the gel polymer electrolyte membrane prepared in this example is shown in fig. 2, and it can be seen that the polyacrylamide gel polymer electrolyte modified by xanthan gum and cotton nanocellulose simultaneously has the maximum stress and strain values, which are 84kPa and 2070% respectively, which indicates that the xanthan gum and cotton nanocellulose can improve the mechanical strength and toughness of single polyacrylamide.
Example 2
(1) Mixing and grinding 2g of acrylamide powder and 80mg of xanthan gum powder uniformly, adding the mixture into 20g of cotton nanocellulose aqueous solution, magnetically stirring for 6 hours at room temperature, adding 30mg of ammonium persulfate initiator and 3mg of N, N' -methylene bisacrylamide binder, continuously stirring for 1 hour, and then carrying out vacuum defoaming treatment for 0.5 hour to obtain uniform and viscous mixed solution.
(2) And pouring the obtained uniform and viscous mixed solution into a self-made sealed glass mold with the thickness specification of 1mm, and placing the self-made sealed glass mold into a forced air oven to be cured for 4 hours at the constant temperature of 70 ℃ to obtain the gel polymer film.
(3) The resulting gel polymer film was immersed in 20ml of 2mol L-1Zinc sulfate and 0.1mol L of-1And mixing the manganese sulfate with the electrolyte for 24 hours to obtain the xanthan gum and cotton nanocellulose modified polyacrylamide gel polymer electrolyte membrane with a porous structure.
The ion conductivity impedance graph of the gel polymer electrolyte membrane prepared in this example is shown in fig. 3, and it can be seen that the impedance value of the polyacrylamide gel polymer electrolyte modified by xanthan gum and cotton nanocellulose at the same time is the smallest, and is 0.4 Ω, that is, the ion conductivity is the highest.
Fig. 4 shows an alternating current impedance diagram of the gel polymer electrolyte membrane applied to the flexible zinc ion battery, and it can be seen that the interface impedance value of the flexible zinc ion battery adopting the polyacrylamide gel polymer electrolyte modified by xanthan gum and cotton nanocellulose is minimum and 25 Ω, which reduces polarization of the battery and is beneficial to improving electrochemical performance of the battery.
Example 3
(1) Mixing and grinding 2g of acrylamide powder and 50mg of xanthan gum powder uniformly, adding the mixture into 20g of cotton nanocellulose aqueous solution, magnetically stirring for 6 hours at room temperature, adding 30mg of ammonium persulfate initiator and 3mg of N, N' -methylene bisacrylamide binder, continuously stirring for 1 hour, and then carrying out vacuum defoaming treatment for 0.5 hour to obtain uniform and viscous mixed solution.
(2) And pouring the obtained uniform and viscous mixed solution into a self-made sealed glass mold with the thickness specification of 1mm, and placing the self-made sealed glass mold into a forced air oven to be cured for 4 hours at the constant temperature of 70 ℃ to obtain the gel polymer film.
(3) The resulting gel polymer film was immersed in 20ml of 2mol L-1Zinc sulfate and 0.1mol L of-1And mixing the manganese sulfate with the electrolyte for 24 hours to obtain the xanthan gum and cotton nanocellulose modified polyacrylamide gel polymer electrolyte membrane with a porous structure.
The cycle performance chart of the gel polymer electrolyte membrane applied to the flexible zinc-ion battery is shown in fig. 5, and it can be seen that the capacity retention rate of the battery is 94.9% after 500 cycles under the charge-discharge cycle condition of 4C, which indicates that the electrolyte membrane can enable the zinc-ion battery to have excellent cycle stability.
Comparative example 1
The gel polymer electrolyte prepared in the embodiment 3 of the invention is applied to a zinc symmetrical battery, the positive electrode and the negative electrode of the zinc symmetrical battery are polished smooth metal zinc sheets, and a scanning electron microscope image of the surface of the metal zinc sheet under a constant current test condition is shot. Under the same conditions, the gel polymer electrolyte was replaced with a conventional glass fiber separator and a liquid electrolyte. As shown in fig. 6, 6(a) is the polished smooth surface of the metallic zinc sheet, 6(b) is the surface of the metallic zinc sheet of the comparative group of the glass fiber separator and the liquid electrolyte, and 6(c) is the surface of the metallic zinc sheet of the experimental group of the gel polymer electrolyte prepared according to the present invention. It can be seen that the gel polymer electrolyte can significantly improve the uniform deposition of zinc ions and inhibit the growth of zinc dendrites, compared with a liquid electrolyte.
Comparative example 2
Patent CN110085925A prepares a zinc alginate based polymer composite gel electrolyte membrane, which comprises the following steps: preparing sodium alginate aqueous solution with certain concentration, coating the sodium alginate aqueous solution on a zinc cathode, immersing the zinc cathode in zinc salt electrolyte for ion exchange reaction, and performing in-situ crosslinking to obtain the sodium alginate aqueous solutionGel electrolyte membrane for MnO2a/Zn zinc ion battery. The zinc ion battery prepared by the comparative example has a capacity retention rate of 78.2% after 100 cycles under the constant current charge/discharge condition of 1A/g (about 3C). Compared with example 3, the gel polymer electrolyte membrane prepared by the invention can improve the cycle stability of the zinc ion battery.
Claims (10)
1. A gel polymer, characterized in that the gel polymer comprises, in parts by weight: the components of acrylamide, xanthan gum, nano-cellulose, an initiator and a binder in a mass ratio of 1: 0.01-0.05: 8-10: 0.01-0.02: 0.001 to 0.002, obtained by copolymerization.
2. The gel polymer of claim 1, wherein the nanocellulose is cotton nanocellulose, the cellulose diameter is 4-10 nm, and the length is 1-3 μm; the initiator is ammonium persulfate; the binder is N, N' -methylene bisacrylamide.
3. A method of preparing a gel polymer comprising:
(1) mixing and grinding acrylamide and xanthan gum uniformly, adding the mixture into a nano-cellulose aqueous solution, stirring uniformly, adding an initiator and a binder, continuing stirring uniformly, and performing vacuum defoaming treatment to obtain a mixed solution; wherein the mass ratio of the acrylamide to the xanthan gum to the nano cellulose aqueous solution is 1: 0.01-0.05: 8-10; the mass ratio of the initiator to the binder is 1: 0.05 to 0.1;
(2) pouring the mixed solution obtained in the step (1) into a sealed glass mold, and curing at constant temperature to obtain the gel polymer film.
4. The preparation method according to claim 3, wherein the stirring in step (1) is room temperature magnetic stirring; the stirring time is 0.5-12 h; the time of vacuum defoaming treatment is 0.5-2 h.
5. The preparation method according to claim 3, wherein the constant temperature curing in the step (2) is as follows: and (3) placing the mixture in a blast oven for constant temperature curing, wherein the temperature of the blast oven is 60-80 ℃, and the curing time is 2-6 h.
6. A gel polymer electrolyte obtained by immersing the gel polymer of claim 1 in an electrolyte.
7. The electrolyte of claim 3, wherein the electrolyte is a mixed aqueous solution of zinc sulfate and manganese sulfate; wherein the mass ratio of zinc sulfate to manganese sulfate to water is 1: 0.01-0.04: 1.5 to 2.
8. The electrolyte of claim 3, wherein the gel polymer electrolyte is a porous structure with a pore size of 30-100 μm.
9. A method for preparing the gel polymer electrolyte of claim 6, comprising: soaking the gel polymer film in electrolyte to obtain a gel polymer electrolyte; wherein the soaking time is 12-48 h.
10. Use of the gel polymer electrolyte of claim 6 in a flexible zinc-ion battery.
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| CN112563627A (en) * | 2020-12-10 | 2021-03-26 | 中南大学 | Flexible zinc-air battery gel electrolyte and preparation method and application thereof |
| CN112898596A (en) * | 2021-01-21 | 2021-06-04 | 西南大学 | Hydrogel electrolyte and super capacitor thereof |
| CN113097574A (en) * | 2021-02-22 | 2021-07-09 | 江苏师范大学 | Preparation method of solid-liquid mixed electrolyte of zinc ion battery |
| CN113782827A (en) * | 2021-09-15 | 2021-12-10 | 山东省科学院新材料研究所 | Solid electrolyte film and preparation method and application thereof |
| CN114122534A (en) * | 2020-08-28 | 2022-03-01 | 中国科学院上海硅酸盐研究所 | Zinc dendrite-resistant solid zinc-based battery electrolyte and preparation method thereof |
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| CN114421027A (en) * | 2022-01-24 | 2022-04-29 | 吉林大学 | Environment-friendly degradable zinc double-ion battery gel electrolyte, preparation method and application thereof in zinc double-ion battery |
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