CN116646617A - Preparation method and application of composite gel electrolyte for zinc ion battery - Google Patents
Preparation method and application of composite gel electrolyte for zinc ion battery Download PDFInfo
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- CN116646617A CN116646617A CN202310462418.3A CN202310462418A CN116646617A CN 116646617 A CN116646617 A CN 116646617A CN 202310462418 A CN202310462418 A CN 202310462418A CN 116646617 A CN116646617 A CN 116646617A
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- ion battery
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- 239000011245 gel electrolyte Substances 0.000 title claims abstract description 84
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 239000002131 composite material Substances 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 54
- 238000005303 weighing Methods 0.000 claims abstract description 23
- 239000008151 electrolyte solution Substances 0.000 claims abstract description 9
- 239000000243 solution Substances 0.000 claims description 89
- 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 78
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 78
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims description 78
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims description 78
- 229920002907 Guar gum Polymers 0.000 claims description 66
- 239000000665 guar gum Substances 0.000 claims description 66
- 235000010417 guar gum Nutrition 0.000 claims description 66
- 229960002154 guar gum Drugs 0.000 claims description 66
- 239000000499 gel Substances 0.000 claims description 41
- 238000000034 method Methods 0.000 claims description 31
- 239000008367 deionised water Substances 0.000 claims description 23
- 229910021641 deionized water Inorganic materials 0.000 claims description 23
- 238000004090 dissolution Methods 0.000 claims description 19
- 229910052751 metal Inorganic materials 0.000 claims description 19
- 239000002184 metal Substances 0.000 claims description 19
- 239000003792 electrolyte Substances 0.000 claims description 14
- 229920006318 anionic polymer Polymers 0.000 claims description 10
- 239000003795 chemical substances by application Substances 0.000 claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 9
- 150000003839 salts Chemical class 0.000 claims description 8
- 150000003751 zinc Chemical class 0.000 claims description 8
- 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 7
- 108010010803 Gelatin Proteins 0.000 claims description 7
- 229920002472 Starch Polymers 0.000 claims description 7
- 239000008273 gelatin Substances 0.000 claims description 7
- 229920000159 gelatin Polymers 0.000 claims description 7
- 235000019322 gelatine Nutrition 0.000 claims description 7
- 235000011852 gelatine desserts Nutrition 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 claims description 7
- 229920000642 polymer Polymers 0.000 claims description 7
- 235000010413 sodium alginate Nutrition 0.000 claims description 7
- 239000000661 sodium alginate Substances 0.000 claims description 7
- 229940005550 sodium alginate Drugs 0.000 claims description 7
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 claims description 7
- 239000008107 starch Substances 0.000 claims description 7
- 235000019698 starch Nutrition 0.000 claims description 7
- 239000000230 xanthan gum Substances 0.000 claims description 7
- 235000010493 xanthan gum Nutrition 0.000 claims description 7
- 229920001285 xanthan gum Polymers 0.000 claims description 7
- 229940082509 xanthan gum Drugs 0.000 claims description 7
- 229920000161 Locust bean gum Polymers 0.000 claims description 6
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 6
- 235000010420 locust bean gum Nutrition 0.000 claims description 6
- 239000000711 locust bean gum Substances 0.000 claims description 6
- 150000002696 manganese Chemical class 0.000 claims description 6
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 6
- 239000002243 precursor Substances 0.000 claims description 6
- 239000012266 salt solution Substances 0.000 claims description 6
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 6
- 150000004676 glycans Chemical class 0.000 claims description 5
- 229920001282 polysaccharide Polymers 0.000 claims description 5
- 239000005017 polysaccharide Substances 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 4
- 229910052748 manganese Inorganic materials 0.000 claims description 4
- 239000011572 manganese Substances 0.000 claims description 4
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 4
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 3
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 3
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 3
- 125000000129 anionic group Chemical group 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 239000011565 manganese chloride Substances 0.000 claims description 3
- 235000002867 manganese chloride Nutrition 0.000 claims description 3
- 229940099607 manganese chloride Drugs 0.000 claims description 3
- 229940099596 manganese sulfate Drugs 0.000 claims description 3
- 239000011702 manganese sulphate Substances 0.000 claims description 3
- 235000007079 manganese sulphate Nutrition 0.000 claims description 3
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 3
- 239000004246 zinc acetate Substances 0.000 claims description 3
- 239000011592 zinc chloride Substances 0.000 claims description 3
- 235000005074 zinc chloride Nutrition 0.000 claims description 3
- 229960001763 zinc sulfate Drugs 0.000 claims description 3
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 3
- -1 manganese salt Chemical class 0.000 claims description 2
- 235000019422 polyvinyl alcohol Nutrition 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 230000008719 thickening Effects 0.000 claims description 2
- 229960000314 zinc acetate Drugs 0.000 claims description 2
- 235000013904 zinc acetate Nutrition 0.000 claims description 2
- 229960001939 zinc chloride Drugs 0.000 claims description 2
- 239000002562 thickening agent Substances 0.000 claims 2
- 238000002156 mixing Methods 0.000 abstract description 48
- 239000011701 zinc Substances 0.000 abstract description 44
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 abstract description 37
- 229910052725 zinc Inorganic materials 0.000 abstract description 37
- 239000011259 mixed solution Substances 0.000 abstract description 36
- 238000007086 side reaction Methods 0.000 abstract description 5
- 230000007797 corrosion Effects 0.000 abstract description 4
- 238000005260 corrosion Methods 0.000 abstract description 4
- 238000011161 development Methods 0.000 abstract description 3
- 239000010405 anode material Substances 0.000 abstract description 2
- 239000000843 powder Substances 0.000 description 74
- 210000004027 cell Anatomy 0.000 description 24
- 238000003760 magnetic stirring Methods 0.000 description 21
- 238000004132 cross linking Methods 0.000 description 20
- 239000011521 glass Substances 0.000 description 20
- 238000010438 heat treatment Methods 0.000 description 20
- 239000012456 homogeneous solution Substances 0.000 description 20
- 210000001787 dendrite Anatomy 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 229940021013 electrolyte solution Drugs 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- 239000000017 hydrogel Substances 0.000 description 3
- ISPYRSDWRDQNSW-UHFFFAOYSA-L manganese(II) sulfate monohydrate Chemical compound O.[Mn+2].[O-]S([O-])(=O)=O ISPYRSDWRDQNSW-UHFFFAOYSA-L 0.000 description 3
- RZLVQBNCHSJZPX-UHFFFAOYSA-L zinc sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Zn+2].[O-]S([O-])(=O)=O RZLVQBNCHSJZPX-UHFFFAOYSA-L 0.000 description 3
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 240000008886 Ceratonia siliqua Species 0.000 description 1
- 235000013912 Ceratonia siliqua Nutrition 0.000 description 1
- 239000002000 Electrolyte additive Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 229920000591 gum Polymers 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000007614 solvation Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000012360 testing method Methods 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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
-
- 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
- H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
- H01M10/38—Construction or manufacture
-
- 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
- H01M2300/0085—Immobilising or gelification of electrolyte
-
- 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
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Primary Cells (AREA)
Abstract
The application provides a preparation method and application of a composite gel electrolyte for a water-based zinc ion battery, wherein the preparation method comprises the following steps: preparing electrolyte solution, weighing film forming components, preparing mixed solution, preparing gel electrolyte and cutting. The gel electrolyte is prepared by a simple blending mode, the operation is simple, the preparation is easy, and the cost is low; the application reduces the free water content through abundant polar groups in the composite gel electrolyte, reduces side reaction and corrosion of the anode material; the cycle performance of the zinc cathode is greatly improved, the development of a zinc battery is facilitated, and the zinc cathode is suitable for popularization and application.
Description
Technical Field
The application belongs to the technical field of water-based zinc ion batteries, and particularly relates to a preparation method and application of a composite gel electrolyte for a zinc ion battery.
Background
The water-based zinc ion battery has the advantages of high theoretical specific capacity, high coulombic efficiency, high energy density, safety, environmental protection and the like, and is considered as one of the next generation candidate batteries with the most commercial application prospect at present. However, the practical application of the zinc ion battery is severely restricted by defects such as zinc dendrite growth, electrode/electrolyte interface side reaction and the like in the charge-discharge cycle process, and the rate performance and the cycle performance of the zinc ion battery are greatly influenced. At the same time, dendrites may penetrate the separator, thereby causing internal shorting of the cell, further impeding the commercialization of aqueous zinc ion cells. Accordingly, many studies have been conducted in recent years in an effort to suppress zinc dendrite growth, mainly including negative electrode material structural design and surface modification (such as construction of a coating layer having a nanopore structure, polymer layer coating modification, etc.), electrolyte composition optimization, development of electrolyte additives, and the like. Although these methods can inhibit zinc dendrite formation and growth to some extent, they have limited effect on alleviating side reactions of metallic zinc in aqueous environments due to inherent activity. Another key problem of the aqueous zinc ion battery is that after serious physical damage, electrolyte leakage problem may occur, resulting in deterioration of energy storage function, deterioration of reliability and maintainability of the battery, and even serious safety accident may be caused.
Compared with the water-based electrolyte, the polymer gel electrolyte has a unique pore channel structure, so that the polymer gel electrolyte has water retention property, the risk of electrolyte leakage can be effectively avoided, and the safety performance of the battery can be effectively improved; in addition, the gel electrolyte with multifunctional charged groups can effectively solve zinc dendrites, while Zn 2+ The solvation structure may be controlled by charged groups to further eliminate side reactions of high rate performance zinc cells.
Disclosure of Invention
This section is intended to outline some aspects of embodiments of the application and to briefly introduce some preferred embodiments. Some simplifications or omissions may be made in this section as well as in the description of the application and in the title of the application, which may not be used to limit the scope of the application.
The present application has been made in view of the above and/or problems occurring in the prior art.
Therefore, the application aims to overcome the defects in the prior art and provide a preparation method of the composite gel electrolyte for the water-based zinc ion battery.
In order to solve the technical problems, the application provides the following technical scheme: a method for preparing a composite gel electrolyte for an aqueous zinc ion battery, comprising the following steps:
preparing a salt solution: adding metal salt into deionized water for dissolution to prepare a metal salt solution with a certain molar concentration;
preparing a precursor liquid: sequentially adding an anionic high molecular polymer and a natural high molecular polymer with film forming property into the salt solution, and uniformly stirring to prepare a precursor solution; preparing a composite gel electrolyte: pouring the prepared precursor liquid into a mould, standing and cooling at a certain temperature until gel is formed, and obtaining the gel electrolyte.
As a preferable embodiment of the method for preparing a composite gel electrolyte for an aqueous zinc ion battery according to the present application, wherein: and preparing an electrolyte solution, wherein the metal salt comprises one or two of zinc salt and manganese salt.
As a preferable embodiment of the method for preparing a composite gel electrolyte for an aqueous zinc ion battery according to the present application, wherein: and preparing an electrolyte solution, wherein the metal salt comprises one or more of zinc sulfate, zinc chloride, zinc acetate, manganese sulfate and manganese chloride.
As a preferable embodiment of the method for preparing a composite gel electrolyte for an aqueous zinc ion battery according to the present application, wherein: the metal salt is metal zinc salt and metal manganese salt, and the metal zinc salt is as follows: metal manganese salt=10 to 30:1.
As a preferable embodiment of the method for preparing a composite gel electrolyte for an aqueous zinc ion battery according to the present application, wherein: and weighing the film forming component, wherein the film forming agent is thickening polysaccharide.
As a preferable embodiment of the method for preparing a composite gel electrolyte for an aqueous zinc ion battery according to the present application, wherein: the film forming agent comprises one or more of guar gum, locust bean gum, xanthan gum, starch, gelatin and polyvinyl alcohol, and the anionic polymer compound comprises one or more of sodium carboxymethyl cellulose, sodium alginate and sodium polyacrylate.
As a preferable embodiment of the method for preparing a composite gel electrolyte for an aqueous zinc ion battery according to the present application, wherein: the film forming agent comprises the following components in mass: anionic polymer compound=1 to 6:1.
As a preferable embodiment of the method for preparing a composite gel electrolyte for an aqueous zinc ion battery according to the present application, wherein: the film forming agent is guar gum, and the anionic polymer compound is sodium carboxymethyl cellulose.
It is another object of the present application to provide the use of a composite gel electrolyte for an aqueous zinc ion battery.
In order to solve the technical problems, the application provides the following technical scheme: an application of a composite gel electrolyte for an aqueous zinc ion battery, comprising: the gel electrolyte is used as a separator and electrolyte of a zinc ion battery.
The application has the beneficial effects that:
(1) The gel electrolyte is prepared by a simple blending mode, the operation is simple, the preparation is easy, and the cost is low;
(2) The application reduces free water content through abundant polar groups in the composite gel electrolyte, reduces side reaction and corrosion of anode materials, and utilizes anionic groups in the composite gel electrolyte to induce zinc ions to be uniformly deposited so as to reduce zinc dendrite;
(3) The gel electrolyte provided by the application can be applied to a water-based zinc ion battery, the cycle performance of a zinc cathode is greatly improved, the development of the zinc battery is facilitated, and the gel electrolyte is suitable for popularization and application.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings that are needed in the description of the embodiments will be briefly described below, it being obvious that the drawings in the following description are only some embodiments of the present application, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art. Wherein:
FIG. 1 is a graph showing the cycle performance of example 11 of the present application using a composite gel electrolyte in combination with a common manganese-based material;
FIG. 2 is a graph showing the cycle performance of a zinc electrode using a composite gel electrolyte in example 11 of the present application;
FIG. 3 is a stress-strain curve of the gel electrolyte prepared in example 11 of the present application.
Detailed Description
In order that the above-recited objects, features and advantages of the present application will become more apparent, a more particular description of the application will be rendered by reference to specific embodiments thereof which are illustrated in the appended drawings.
In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present application, but the present application may be practiced in other ways other than those described herein, and persons skilled in the art will readily appreciate that the present application is not limited to the specific embodiments disclosed below.
Further, reference herein to "one embodiment" or "an embodiment" means that a particular feature, structure, or characteristic can be included in at least one implementation of the application. The appearances of the phrase "in one embodiment" in various places in the specification are not necessarily all referring to the same embodiment, nor are separate or alternative embodiments mutually exclusive of other embodiments.
Example 1
In this example, a gel electrolyte for zinc cell and a method for preparing the same, which forms gel by simple blending and physical crosslinking, comprises the steps of:
(1) ZnSO is added to 4 ·7H 2 O and MnSO 4 ·H 2 O is dissolved in deionized water, and is dissolved to be clear and transparent under magnetic stirring (400 rmp), and then the solution is transferred into a volumetric flask for constant volume to obtain the solution with the molar concentration of 1mol L -1 ZnSO of (2) 4 And a molar concentration of 0.1mol L –1 MnSO of (2) 4 Mixing the solutions;
(2) 10mL of the prepared ZnSO is measured 4 And MnSO 4 The mass concentration of the guar gum after dissolution is 60g L -1 And sodium carboxymethylcellulose at a mass concentration of 5g L -1 Weighing guar gum and sodium carboxymethyl cellulose;
(3) Adding weighed guar gum powder and sodium carboxymethyl cellulose powder to the formulated ZnSO 4 And MnSO 4 Fully dissolving guar gum powder and sodium carboxymethyl cellulose powder in ZnSO in the mixed solution under the water bath heating of 70 DEG C 4 And MnSO 4 Forming a uniform mixed solution in the mixed solution;
(4) The obtained homogeneous solution was cast in a glass mold, and left to stand and cool at a temperature of 25 ℃ for 24 hours until gel was formed, to obtain a gel electrolyte.
Example 2
In this example, a gel electrolyte for zinc cell and a method for preparing the same, which forms gel by simple blending and physical crosslinking, comprises the steps of:
(1) ZnSO is added to 4 ·7H 2 O and MnSO 4 ·H 2 O is dissolved in deionized water, and is dissolved to be clear and transparent under magnetic stirring (400 rmp), and then the solution is transferred into a volumetric flask for constant volume to obtain the solution with the molar concentration of 1.5mol L -1 ZnSO of (2) 4 And a molar concentration of 0.1mol L –1 MnSO of (2) 4 Mixing the solutions;
(2) 10mL of the prepared ZnSO is measured 4 And MnSO 4 Mixing the solution according to the mass of the guar gum after dissolutionThe concentration is 60g L -1 And sodium carboxymethylcellulose at a mass concentration of 5g L -1 Weighing guar gum and sodium carboxymethyl cellulose;
(3) Adding weighed guar gum powder and sodium carboxymethyl cellulose powder to the formulated ZnSO 4 And MnSO 4 Fully dissolving guar gum powder and sodium carboxymethyl cellulose powder in ZnSO in the mixed solution under the water bath heating of 70 DEG C 4 And MnSO 4 Forming a uniform mixed solution in the mixed solution;
(4) The obtained homogeneous solution was cast in a glass mold, and left to stand and cool at a temperature of 25 ℃ for 24 hours until gel was formed, to obtain a gel electrolyte.
Example 3
In this example, a gel electrolyte for zinc cell and a method for preparing the same, which forms gel by simple blending and physical crosslinking, comprises the steps of:
(1) ZnSO is added to 4 ·7H 2 O and MnSO 4 ·H 2 O is dissolved in deionized water, and is dissolved to be clear and transparent under magnetic stirring (400 rmp), and then the solution is transferred into a volumetric flask for constant volume to obtain the solution with the molar concentration of 2mol L -1 ZnSO of (2) 4 And a molar concentration of 0.1mol L –1 MnSO of (2) 4 Mixing the solutions;
(2) 10mL of the prepared ZnSO is measured 4 And MnSO 4 The mass concentration of the guar gum after dissolution is 60g L -1 And sodium carboxymethylcellulose at a mass concentration of 5g L -1 Weighing guar gum and sodium carboxymethyl cellulose;
(3) Adding weighed guar gum powder and sodium carboxymethyl cellulose powder to the formulated ZnSO 4 And MnSO 4 Fully dissolving guar gum powder and sodium carboxymethyl cellulose powder in ZnSO in the mixed solution under the water bath heating of 70 DEG C 4 And MnSO 4 Forming a uniform mixed solution in the mixed solution;
(4) The obtained homogeneous solution was cast in a glass mold, and left to stand and cool at a temperature of 25 ℃ for 24 hours until gel was formed, to obtain a gel electrolyte.
Example 4
In this example, a gel electrolyte for zinc cell and a method for preparing the same, which forms gel by simple blending and physical crosslinking, comprises the steps of:
(1) ZnSO is added to 4 ·7H 2 O and MnSO 4 ·H 2 O is dissolved in deionized water, and is dissolved to be clear and transparent under magnetic stirring (400 rmp), and then the solution is transferred into a volumetric flask for constant volume to obtain the solution with the molar concentration of 2.5mol L -1 ZnSO of (2) 4 And a molar concentration of 0.1mol L –1 MnSO of (2) 4 Mixing the solutions;
(2) 10mL of the prepared ZnSO is measured 4 And MnSO 4 The mass concentration of the guar gum after dissolution is 60g L -1 And sodium carboxymethylcellulose at a mass concentration of 5g L -1 Weighing guar gum and sodium carboxymethyl cellulose;
(3) Adding weighed guar gum powder and sodium carboxymethyl cellulose powder to the formulated ZnSO 4 And MnSO 4 Fully dissolving guar gum powder and sodium carboxymethyl cellulose powder in ZnSO in the mixed solution under the water bath heating of 70 DEG C 4 And MnSO 4 Forming a uniform mixed solution in the mixed solution;
(4) The obtained homogeneous solution was cast in a glass mold, and left to stand and cool at a temperature of 25 ℃ for 24 hours until gel was formed, to obtain a gel electrolyte.
Example 5
In this example, a gel electrolyte for zinc cell and a method for preparing the same, which forms gel by simple blending and physical crosslinking, comprises the steps of:
(1) ZnSO is added to 4 ·7H 2 O and MnSO 4 ·H 2 O is dissolved in deionized water, and is dissolved to be clear and transparent under magnetic stirring (400 rmp), and then the solution is transferred into a volumetric flask for constant volume to obtain the solution with the molar concentration of 3mol L -1 ZnSO of (2) 4 And a molar concentration of 0.1mol L –1 MnSO of (2) 4 Mixing the solutions;
(2) 10mL of the prepared ZnSO is measured 4 And MnSO 4 The mass concentration of the guar gum after dissolution is 60g L -1 And sodium carboxymethylcellulose at a mass concentration of 5g L -1 Weighing guar gum and sodium carboxymethyl cellulose;
(3) Adding weighed guar gum powder and sodium carboxymethyl cellulose powder to the formulated ZnSO 4 And MnSO 4 Fully dissolving guar gum powder and sodium carboxymethyl cellulose powder in ZnSO in the mixed solution under the water bath heating of 70 DEG C 4 And MnSO 4 Forming a uniform mixed solution in the mixed solution;
(4) The obtained homogeneous solution was cast in a glass mold, and left to stand and cool at a temperature of 25 ℃ for 24 hours until gel was formed, to obtain a gel electrolyte.
Example 6
In this example, a gel electrolyte for zinc cell and a method for preparing the same, which forms gel by simple blending and physical crosslinking, comprises the steps of:
(1) ZnCl 2 And MnSO 4 ·H 2 O is dissolved in deionized water, and is dissolved to be clear and transparent under magnetic stirring (400 rmp), and then the solution is transferred into a volumetric flask for constant volume to obtain the solution with the molar concentration of 2mol L -1 ZnCl of (C) 2 And a molar concentration of 0.1mol L –1 MnSO of (2) 4 Mixing the solutions;
(2) 10mL of prepared ZnCl is measured 2 And MnSO 4 The mass concentration of the guar gum after dissolution is 60g L -1 And sodium carboxymethylcellulose at a mass concentration of 5g L -1 Weighing guar gum and sodium carboxymethyl cellulose;
(3) Adding weighed guar gum powder and sodium carboxymethyl cellulose powder to the prepared ZnCl 2 And MnSO 4 Fully dissolving sodium carboxymethyl cellulose powder and guar gum powder in the mixed solution under the water bath heating at 70 ℃ to form a uniform solution;
(4) The obtained homogeneous solution was cast in a glass mold, and left to stand and cool at a temperature of 25 ℃ for 24 hours until gel was formed, to obtain a gel electrolyte.
Example 7
In this example, a gel electrolyte for zinc cell and a method for preparing the same, which forms gel by simple blending and physical crosslinking, comprises the steps of:
(1) Zn (CH) 3 COOH) 2 ·2H 2 O and MnSO 4 ·H 2 O is dissolved in deionized water, and is dissolved to be clear and transparent under magnetic stirring (400 rmp), and then the solution is transferred into a volumetric flask for constant volume to obtain the solution with the molar concentration of 2mol L -1 Zn (CH) 3 COOH) 2 ·2H 2 O and molar concentration of 0.1mol L –1 MnSO of (2) 4 Mixing the solutions;
(2) 10mL of the prepared Zn (CH) 3 COOH) 2 And MnSO 4 The mass concentration of the guar gum after dissolution is 60g L -1 And sodium carboxymethylcellulose at a mass concentration of 5g L -1 Weighing guar gum and sodium carboxymethyl cellulose;
(3) The weighed guar gum powder and sodium carboxymethyl cellulose powder are added to the prepared Zn (CH) 3 COOH) 2 And MnSO 4 Fully dissolving sodium carboxymethyl cellulose powder and guar gum powder in the mixed solution under the water bath heating at 70 ℃ to form a uniform solution;
(4) The obtained homogeneous solution was cast in a glass mold, and left to stand and cool at a temperature of 25 ℃ for 24 hours until gel was formed, to obtain a gel electrolyte.
Example 8
In this example, a gel electrolyte for zinc cell and a method for preparing the same, which forms gel by simple blending and physical crosslinking, comprises the steps of:
(1) ZnCl 2 And MnSO 4 ·H 2 O is dissolved in deionized water, and is dissolved to be clear and transparent under magnetic stirring (400 rmp), and then the solution is transferred into a volumetric flask for constant volume to obtain the solution with the molar concentration of 2mol L -1 ZnCl of (C) 2 And a molar concentration of 0.1mol L –1 MnCl of (C) 2 Mixing the solutions;
(2) 10mL of prepared ZnCl is measured 2 And MnCl 2 The mass concentration of the guar gum after dissolution is 60g L -1 And sodium carboxymethylcellulose at a mass concentration of 5g L -1 Weighing guar gum and sodium carboxymethyl cellulose;
(3) Adding weighed guar gum powder and sodium carboxymethyl cellulose powder to the prepared ZnCl 2 And MnCl 2 Fully dissolving sodium carboxymethyl cellulose powder and guar gum powder in the mixed solution under the water bath heating at 70 ℃ to form a uniform solution;
(4) The obtained homogeneous solution was cast in a glass mold, and left to stand and cool at a temperature of 25 ℃ for 24 hours until gel was formed, to obtain a gel electrolyte.
Example 9
In this example, a gel electrolyte for zinc cell and a method for preparing the same, which forms gel by simple blending and physical crosslinking, comprises the steps of:
(1) ZnSO is added to 4 ·7H 2 O and MnSO 4 ·H 2 O is dissolved in deionized water, and is dissolved to be clear and transparent under magnetic stirring (400 rmp), and then the solution is transferred into a volumetric flask for constant volume to obtain the solution with the molar concentration of 2mol L -1 ZnSO of (2) 4 And a molar concentration of 0.1mol L –1 MnSO of (2) 4 Mixing the solutions;
(2) 10mL of the prepared ZnSO is measured 4 And MnSO 4 The mass concentration of the guar gum after dissolution is 60g L -1 And sodium carboxymethylcellulose at a mass concentration of 10g L -1 Weighing guar gum and sodium carboxymethyl cellulose;
(3) Adding weighed guar gum powder and sodium carboxymethyl cellulose powder to the formulated ZnSO 4 And MnSO 4 Fully dissolving sodium carboxymethyl cellulose powder and guar gum powder in the mixed solution under the water bath heating at 70 ℃ to form a uniform solution;
(4) The obtained homogeneous solution was cast in a glass mold, and left to stand and cool at a temperature of 25 ℃ for 24 hours until gel was formed, to obtain a gel electrolyte.
Example 10
In this example, a gel electrolyte for zinc cell and a method for preparing the same, which forms gel by simple blending and physical crosslinking, comprises the steps of:
(1) ZnSO is added to 4 ·7H 2 O and MnSO 4 ·H 2 O is dissolved in deionized water, and is dissolved to be clear and transparent under magnetic stirring (400 rmp), and then the solution is transferred into a volumetric flask for constant volume to obtain the solution with the molar concentration of 2mol L -1 ZnSO of (2) 4 And a molar concentration of 0.1mol L –1 MnSO of (2) 4 Mixing the solutions;
(2) 10mL of the prepared ZnSO is measured 4 And MnSO 4 The mass concentration of the guar gum after dissolution is 60g L -1 And sodium carboxymethylcellulose at a mass concentration of 20g L -1 Weighing guar gum and sodium carboxymethyl cellulose;
(3) Adding weighed guar gum powder and sodium carboxymethyl cellulose powder to the formulated ZnSO 4 And MnSO 4 Fully dissolving guar gum powder and sodium carboxymethyl cellulose powder in the mixed solution under the water bath heating at 70 ℃ to form a uniform solution;
(4) The obtained homogeneous solution was cast in a glass mold, and left to stand and cool at a temperature of 25 ℃ for 24 hours until gel was formed, to obtain a gel electrolyte.
Example 11
In this example, a gel electrolyte for zinc cell and a method for preparing the same, which forms gel by simple blending and physical crosslinking, comprises the steps of:
(1) ZnSO is added to 4 ·7H 2 O and MnSO 4 ·H 2 O is dissolved in deionized water, and is dissolved to be clear and transparent under magnetic stirring (400 rmp), and then the solution is transferred into a volumetric flask for constant volume to obtain the solution with the molar concentration of 2mol L -1 ZnSO of (2) 4 And a molar concentration of 0.1mol L –1 MnSO of (2) 4 Mixing the solutions;
(2) 10mL of the prepared ZnSO is measured 4 And MnSO 4 The mass concentration of the guar gum after dissolution is 60g L -1 And sodium carboxymethylcellulose at a mass concentration of 30g L -1 Weighing guar gum and sodium carboxymethyl cellulose;
(3) Adding weighed guar gum powder and sodium carboxymethyl cellulose powder to the formulated ZnSO 4 And MnSO 4 Fully dissolving guar gum powder and sodium carboxymethyl cellulose powder in the mixed solution under the water bath heating at 70 ℃ to form a uniform solution;
(4) The obtained homogeneous solution was cast in a glass mold, and left to stand and cool at a temperature of 25 ℃ for 24 hours until gel was formed, to obtain a gel electrolyte.
Example 12
In this example, a gel electrolyte for zinc cell and a method for preparing the same, which forms gel by simple blending and physical crosslinking, comprises the steps of:
(1) ZnSO is added to 4 ·7H 2 O and MnSO 4 ·H 2 O is dissolved in deionized water, and is dissolved to be clear and transparent under magnetic stirring (400 rmp), and then the solution is transferred into a volumetric flask for constant volume to obtain the solution with the molar concentration of 2mol L -1 ZnSO of (2) 4 And a molar concentration of 0.1mol L –1 MnSO of (2) 4 Mixing the solutions;
(2) 10mL of the prepared ZnSO is measured 4 And MnSO 4 The mass concentration of the guar gum after dissolution is 60g L -1 And sodium carboxymethylcellulose at a mass concentration of 50g L -1 Weighing guar gum and sodium carboxymethyl cellulose;
(3) Adding weighed guar gum powder and sodium carboxymethyl cellulose powder to the formulated ZnSO 4 And MnSO 4 Fully dissolving guar gum powder and sodium carboxymethyl cellulose powder in the mixed solution under the water bath heating at 70 ℃ to form a uniform solution;
(4) The obtained homogeneous solution was cast in a glass mold, and left to stand and cool at a temperature of 25 ℃ for 24 hours until gel was formed, to obtain a gel electrolyte.
Example 13
In this example, a gel electrolyte for zinc cell and a method for preparing the same, which forms gel by simple blending and physical crosslinking, comprises the steps of:
(1) ZnSO is added to 4 ·7H 2 O and MnSO 4 ·H 2 O is dissolved in deionized water, and is dissolved to be clear and transparent under magnetic stirring (400 rmp), and then the solution is transferred into a volumetric flask for constant volume to obtain the solution with the molar concentration of 2mol L -1 ZnSO of (2) 4 And a molar concentration of 0.1mol L –1 MnSO of (2) 4 Mixing the solutions;
(2) 10mL of the prepared ZnSO is measured 4 And MnSO 4 The mass concentration of the guar gum after dissolution is 60g L -1 And sodium carboxymethylcellulose at a mass concentration of 60g L -1 Weighing guar gum and sodium carboxymethyl cellulose;
(3) Adding weighed guar gum powder and sodium carboxymethyl cellulose powder to the formulated ZnSO 4 And MnSO 4 Fully dissolving guar gum powder and sodium carboxymethyl cellulose powder in the mixed solution under the water bath heating at 70 ℃ to form a uniform solution;
(4) The obtained homogeneous solution was cast in a glass mold, and left to stand and cool at a temperature of 25 ℃ for 24 hours until gel was formed, to obtain a gel electrolyte.
Example 14
In this example, a gel electrolyte for zinc cell and a method for preparing the same, which forms gel by simple blending and physical crosslinking, comprises the steps of:
(1) ZnSO is added to 4 ·7H 2 O and MnSO 4 ·H 2 O is dissolved in deionized water, and is dissolved to be clear and transparent under magnetic stirring (400 rmp), and then the solution is transferred into a volumetric flask for constant volume to obtain the solution with the molar concentration of 2mol L -1 ZnSO of (2) 4 And a molar concentration of 0.1mol L –1 MnSO of (2) 4 Mixing the solutions;
(2) 10mL of the prepared ZnSO is measured 4 And MnSO 4 Mixing the solution according to the gum mass concentration of locust bean after dissolution of 50g L -1 And sodium carboxymethylcellulose at a mass concentration of 25g L -1 Weighing locust bean gum and sodium carboxymethyl cellulose;
(3) Adding weighed locust bean gum powder and sodium carboxymethylcellulose powder into the prepared ZnSO 4 And MnSO 4 Fully dissolving locust bean gum powder and sodium carboxymethyl cellulose powder in the mixed solution under the water bath heating at 70 ℃ to form a uniform solution;
(4) The obtained homogeneous solution was cast in a glass mold, and left to stand and cool at a temperature of 25 ℃ for 24 hours until gel was formed, to obtain a gel electrolyte.
Example 15
In this example, a gel electrolyte for zinc cell and a method for preparing the same, which forms gel by simple blending and physical crosslinking, comprises the steps of:
(1) ZnSO is added to 4 ·7H 2 O and MnSO 4 ·H 2 O is dissolved in deionized water, and is dissolved to be clear and transparent under magnetic stirring (400 rmp), and then the solution is transferred into a volumetric flask for constant volume to obtain the solution with the molar concentration of 2mol L -1 ZnSO of (2) 4 And a molar concentration of 0.1mol L –1 MnSO of (2) 4 Mixing the solutions;
(2) 10mL of the prepared ZnSO is measured 4 And MnSO 4 The mass concentration of the mixed solution is 100g L according to the dissolved xanthan gum -1 And sodium carboxymethylcellulose at a mass concentration of 50g L -1 Weighing xanthan gum and sodium carboxymethyl cellulose;
(3) Adding weighed xanthan gum powder and sodium carboxymethylcellulose powder to the formulated ZnSO 4 And MnSO 4 Fully dissolving xanthan gum powder and sodium carboxymethylcellulose powder in the mixed solution under the water bath heating at 70 ℃ to form uniform solution;
(4) The obtained homogeneous solution was cast in a glass mold, and left to stand and cool at a temperature of 25 ℃ for 24 hours until gel was formed, to obtain a gel electrolyte.
Example 16
In this example, a gel electrolyte for zinc cell and a method for preparing the same, which forms gel by simple blending and physical crosslinking, comprises the steps of:
(1) ZnSO is added to 4 ·7H 2 O and MnSO 4 ·H 2 O is dissolved in deionized water, and is dissolved to be clear and transparent under magnetic stirring (400 rmp), and then the solution is transferred into a volumetric flask for constant volume to obtain the solution with the molar concentration of 2mol L -1 ZnSO of (2) 4 And a molar concentration of 0.1mol L –1 MnSO of (2) 4 Mixing the solutions;
(2) 10mL of the prepared ZnSO is measured 4 And MnSO 4 Mixing the solution according to the mass concentration of 40g L of the gelatin after dissolution -1 And sodium carboxymethylcellulose at a mass concentration of 20g L -1 Weighing gelatin and sodium carboxymethyl cellulose;
(3) Adding weighed gelatin and sodium carboxymethyl cellulose powder to the formulated ZnSO 4 And MnSO 4 Fully dissolving gelatin and sodium carboxymethyl cellulose powder in the mixed solution under the water bath heating at 70 ℃ to form a uniform solution;
(4) The obtained homogeneous solution was cast in a glass mold, and left to stand and cool at a temperature of 25 ℃ for 24 hours until gel was formed, to obtain a gel electrolyte.
Example 17
In this example, a gel electrolyte for zinc cell and a method for preparing the same, which forms gel by simple blending and physical crosslinking, comprises the steps of:
(1) ZnSO is added to 4 ·7H 2 O and MnSO 4 ·H 2 O is dissolved in deionized water, and is dissolved to be clear and transparent under magnetic stirring (400 rmp), and then the solution is transferred into a volumetric flask for constant volume to obtain the solution with the molar concentration of 2mol L -1 ZnSO of (2) 4 And mole ofAt a concentration of 0.1mol L –1 MnSO of (2) 4 Mixing the solutions;
(2) 10mL of the prepared ZnSO is measured 4 And MnSO 4 Mixing the solution according to the mass concentration of the starch after dissolution of 40 to 40g L -1 And sodium carboxymethylcellulose at a mass concentration of 20g L -1 Weighing starch and sodium carboxymethyl cellulose;
(3) Adding weighed starch and sodium carboxymethyl cellulose powder to the formulated ZnSO 4 And MnSO 4 In the mixed solution, under the water bath heating at 70 ℃, starch and sodium carboxymethyl cellulose powder are fully dissolved in the mixed solution to form a uniform solution;
(4) The obtained homogeneous solution was cast in a glass mold, and after standing and cooling at 25 ℃, it was impossible to form a film, and it was impossible to use it as an electrolyte alone.
Example 18
In this example, a gel electrolyte for zinc cell and a method for preparing the same, which forms gel by simple blending and physical crosslinking, comprises the steps of:
(1) ZnSO is added to 4 ·7H 2 O and MnSO 4 ·H 2 O is dissolved in deionized water, and is dissolved to be clear and transparent under magnetic stirring (400 rmp), and then the solution is transferred into a volumetric flask for constant volume to obtain the solution with the molar concentration of 2mol L -1 ZnSO of (2) 4 And a molar concentration of 0.1mol L –1 MnSO of (2) 4 Mixing the solutions;
(2) 10mL of the prepared ZnSO is measured 4 And MnSO 4 Mixed solution with mass concentration of 40g L of guar gum after dissolution -1 And sodium alginate with mass concentration of 20g L -1 Weighing guar gum and sodium alginate;
(3) Adding weighed guar gum powder and sodium alginate powder into prepared ZnSO 4 And MnSO 4 Fully dissolving guar gum powder and sodium alginate powder in the mixed solution under the water bath heating at 70 ℃ to form a uniform solution;
(4) The obtained homogeneous solution was cast in a glass mold, and left to stand and cool at a temperature of 25 ℃ for 24 hours until gel was formed, to obtain a gel electrolyte.
Example 19
In this example, a gel electrolyte for zinc cell and a method for preparing the same, which forms gel by simple blending and physical crosslinking, comprises the steps of:
(1) ZnSO is added to 4 ·7H 2 O and MnSO 4 ·H 2 O is dissolved in deionized water, and is dissolved to be clear and transparent under magnetic stirring (400 rmp), and then the solution is transferred into a volumetric flask for constant volume to obtain the solution with the molar concentration of 2mol L -1 ZnSO of (2) 4 And a molar concentration of 0.1mol L –1 MnSO of (2) 4 Mixing the solutions;
(2) 10mL of the prepared ZnSO is measured 4 And MnSO 4 The mass concentration of the guar gum after dissolution is 60g L -1 And sodium polyacrylate with mass concentration of 30g L -1 Weighing guar gum and sodium polyacrylate;
(3) Adding weighed guar gum powder and sodium polyacrylate powder to the formulated ZnSO 4 And MnSO 4 Fully dissolving guar gum powder and sodium polyacrylate powder in the mixed solution under the water bath heating at 70 ℃ to form a uniform solution;
(4) The obtained homogeneous solution was cast in a glass mold, and left to stand and cool at a temperature of 25 ℃ for 24 hours until gel was formed, to obtain a gel electrolyte.
Example 20
In this example, a gel electrolyte for zinc cell and a method for preparing the same, which forms gel by simple blending and physical crosslinking, comprises the steps of:
(1) ZnSO is added to 4 ·7H 2 O and MnSO 4 ·H 2 O is dissolved in deionized water, and is dissolved to be clear and transparent under magnetic stirring (400 rmp), and then the solution is transferred into a volumetric flask for constant volume to obtain the solution with the molar concentration of 2mol L -1 ZnSO of (2) 4 And a molar concentration of 0.1mol L –1 MnSO of (2) 4 Mixing the solutions;
(2) 10mL of the prepared ZnSO is measured 4 And MnSO 4 The mass concentration of the mixed solution is 30g L according to the dissolved polyvinyl alcohol -1 And sodium carboxymethylcellulose at a mass concentration of 15g L -1 Weighing polyvinyl alcohol and sodium carboxymethyl cellulose;
(3) Adding weighed polyvinyl alcohol and sodium carboxymethyl cellulose powder to the prepared ZnSO 4 And MnSO 4 In the mixed solution, polyvinyl alcohol and sodium carboxymethyl cellulose powder are fully dissolved in the mixed solution under the water bath heating at 70 ℃ to form a uniform solution;
(4) The obtained homogeneous solution was cast in a glass mold, and left to stand and cool at a temperature of 25 ℃ for 24 hours until gel was formed, to obtain a gel electrolyte.
Comparative example 1
ZnSO is added to 4 ·7H 2 O and MnSO 4 ·H 2 O is dissolved in deionized water, and is dissolved to be clear and transparent under magnetic stirring, and then the solution is transferred into a volumetric flask for constant volume to obtain the solution with the molar concentration of 2mol L -1 ZnSO of (2) 4 And a molar concentration of 0.1mol L –1 MnSO of (2) 4 The solution is mixed, glass fiber is used as a separator, and the solution is used as an electrolyte for a zinc ion battery.
Example 21
Electrochemical performance test:
uniformly mixing a manganese-based positive electrode material, acetylene black and polyvinylidene fluoride according to a mass ratio of 70:20:10, coating the mixture on a titanium foil, drying the titanium foil for 8 hours in a blast oven at 80 ℃, and pressing the dried titanium foil into a wafer with a diameter of 14mm to obtain a positive electrode plate; the metal zinc is used as a counter electrode, and the composite gel electrolyte prepared by the application is used as a diaphragm and an electrolyte to assemble the button cell.
Electrochemical performance test is carried out by adopting Shenzhen Xinwei BST-5V type battery tester, and the charge-discharge voltage range is 0.9V-1.9V (vs. Zn) 2+ Zn) at a test temperature of 25 ℃.
Table 1 shows electrochemical properties of zinc ion batteries prepared in examples 1 to 20 and comparative example 1
As can be seen from table 1, the composite hydrogel electrolyte prepared in example 11 has the best combination of electrochemical performance and conductivity properties when applied to a zinc ion battery.
The properties of the finished products obtained from examples 1 to 5 were available, and in the production of electrolyte solutions, for the use of zinc sulfate and manganese sulfate, the preparation of finished products was possible with the mass ratio of the substances based on zinc sulfate heptahydrate and manganese sulfate monohydrate in the range of 10:1 to 30:1, and the corresponding data in table 1 indicate that it has good effects, with 20:1 being the preferred ratio of zinc sulfate heptahydrate and manganese sulfate monohydrate based on the data in terms of the circularity and capacity retention rate.
The properties of the finished products prepared in examples 3, 6, 7 and 8 are available, and the raw materials for preparing the electrolyte, which can be used in the application, comprise zinc chloride and zinc acetate besides zinc sulfate heptahydrate, and manganese chloride besides manganese sulfate monohydrate, namely the electrolyte solution can be prepared by depending on corresponding zinc salts and manganese salts, so that the application has great universality for the raw material types.
The properties of the finished products prepared in examples 1 to 5 and 9 to 13 were obtainable, and the mass ratio of the film former to the anionic polymer compound used in the present application was 1 to 6:1.
the properties of the finished products obtained in examples 1 to 5 and 14 to 20 were available, the types of film forming agents used in the present application include guar gum, locust bean gum, xanthan gum, starch, gelatin, and polysaccharides having viscosity such as polyacrylate, while the types of anionic polymer compounds may include sodium carboxymethyl cellulose, sodium alginate, and sodium polyacrylate, all of which may be used as raw materials of the anionic polymer compounds used in my application, and in various examples, the amounts used were changed in accordance with the types of raw materials, but the types of film forming agents are preferably guar gum, and the types of anionic surfactant are preferably sodium carboxymethyl cellulose, based on the effects that can be achieved by the types of raw materials. In example 17, the film was not produced, that is, not all polysaccharides were used as the raw material for producing the film.
It is also possible to obtain that the electrolyte solution and the film-forming component provided in my application have synergistic effects, and that even a change in the kind or amount of the viscous polysaccharide or the anionic polymer compound in the zinc salt, manganese salt or film-forming component used in the electrolyte solution may cause a decrease in the effect or conductivity after the final battery cycle, compared to example 11, which is the best in achieving the effects.
As can be seen from Table 1, when the composite hydrogel electrolyte prepared by the application is applied to a zinc ion battery, the composite hydrogel electrolyte has better mechanical property and electrochemical property, because the guar gum is used as a substrate for preparing the zinc ion battery gel electrolyte, the content of free water is reduced from the root, the problems of hydrogen evolution, corrosion and the like caused by solvent water are inhibited, the reversibility of a zinc cathode is improved, and the good electrochemical property can be maintained after multiple cycles. And secondly, the anionic polymer sodium carboxymethyl cellulose is introduced in a simple blending mode to guide zinc ions to be uniformly deposited, so that dendrite and corrosion problems of the zinc electrode are effectively relieved, and the cycle performance of the zinc electrode is greatly improved.
It should be noted that the above embodiments are only for illustrating the technical solution of the present application and not for limiting the same, and although the present application has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that the technical solution of the present application may be modified or substituted without departing from the spirit and scope of the technical solution of the present application, which is intended to be covered in the scope of the claims of the present application.
Claims (8)
1. A preparation method of a composite gel electrolyte for a water-based zinc ion battery is characterized by comprising the following steps: the method comprises the following steps:
preparing a salt solution: adding metal salt into deionized water for dissolution to prepare a metal salt solution with a certain molar concentration;
preparing a precursor liquid: sequentially adding an anionic high molecular polymer and a natural high molecular polymer with film forming property into the salt solution, and uniformly stirring to prepare a precursor solution; preparing a composite gel electrolyte: pouring the prepared precursor liquid into a mould, standing and cooling at a certain temperature until gel is formed, and obtaining the gel electrolyte.
2. The method for producing a composite gel electrolyte for an aqueous zinc-ion battery according to claim 1, characterized in that: in the preparation of the electrolyte solution, the metal salt comprises one or two of zinc salt and manganese salt.
3. The method for producing a composite gel electrolyte for an aqueous zinc-ion battery according to claim 1 or 2, characterized in that: in the preparation of the electrolyte solution, the metal salt comprises one or more of zinc sulfate, zinc chloride, zinc acetate, manganese sulfate and manganese chloride.
4. The method for producing a composite gel electrolyte for an aqueous zinc-ion battery according to claim 1 or 2, characterized in that: the metal salt is metal zinc salt and metal manganese salt, and the metal zinc salt is as follows: metal manganese salt=10 to 30:1.
5. The method for producing a composite gel electrolyte for an aqueous zinc-ion battery according to claim 1, characterized in that: in the weighing film-forming component, the film-forming agent is a thickening agent, and the thickening agent is thickening polysaccharide.
6. The method for producing a composite gel electrolyte for an aqueous zinc-ion battery according to claim 1 or 5, characterized in that: the film forming agent comprises one or more of guar gum, locust bean gum, xanthan gum, starch, gelatin and polyvinyl alcohol, and the anionic polymer compound comprises one or more of sodium carboxymethyl cellulose, sodium alginate and sodium polyacrylate.
7. The method for producing a composite gel electrolyte for an aqueous zinc-ion battery according to claim 1 or 5, characterized in that: the film forming agent comprises the following components in mass: anionic polymer compound=1 to 6:1.
8. An application of a composite gel electrolyte for an aqueous zinc ion battery, which is characterized in that: the gel electrolyte is used as a separator and electrolyte of a zinc ion battery.
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| CN117164899B (en) * | 2023-11-01 | 2024-02-02 | 中科南京绿色制造产业创新研究院 | Gel electrolyte, preparation method thereof and zinc ion battery containing gel electrolyte |
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