CN116759522A - Preparation method of modified zinc cathode and application of modified zinc cathode in water-based zinc ion battery - Google Patents
Preparation method of modified zinc cathode and application of modified zinc cathode in water-based zinc ion battery Download PDFInfo
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- CN116759522A CN116759522A CN202310591448.4A CN202310591448A CN116759522A CN 116759522 A CN116759522 A CN 116759522A CN 202310591448 A CN202310591448 A CN 202310591448A CN 116759522 A CN116759522 A CN 116759522A
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- 150000003751 zinc Chemical class 0.000 title claims abstract description 46
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 44
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 68
- 239000011701 zinc Substances 0.000 claims abstract description 65
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 63
- 229920002674 hyaluronan Polymers 0.000 claims abstract description 18
- 229960003160 hyaluronic acid Drugs 0.000 claims abstract description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 28
- 244000137852 Petrea volubilis Species 0.000 claims description 23
- 238000001035 drying Methods 0.000 claims description 21
- KIUKXJAPPMFGSW-DNGZLQJQSA-N (2S,3S,4S,5R,6R)-6-[(2S,3R,4R,5S,6R)-3-Acetamido-2-[(2S,3S,4R,5R,6R)-6-[(2R,3R,4R,5S,6R)-3-acetamido-2,5-dihydroxy-6-(hydroxymethyl)oxan-4-yl]oxy-2-carboxy-4,5-dihydroxyoxan-3-yl]oxy-5-hydroxy-6-(hydroxymethyl)oxan-4-yl]oxy-3,4,5-trihydroxyoxane-2-carboxylic acid Chemical compound CC(=O)N[C@H]1[C@H](O)O[C@H](CO)[C@@H](O)[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@H](O[C@H]2[C@@H]([C@@H](O[C@H]3[C@@H]([C@@H](O)[C@H](O)[C@H](O3)C(O)=O)O)[C@H](O)[C@@H](CO)O2)NC(C)=O)[C@@H](C(O)=O)O1 KIUKXJAPPMFGSW-DNGZLQJQSA-N 0.000 claims description 16
- 239000007864 aqueous solution Substances 0.000 claims description 12
- 238000004140 cleaning Methods 0.000 claims description 12
- 239000003792 electrolyte Substances 0.000 claims description 10
- 235000019441 ethanol Nutrition 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- 238000005498 polishing Methods 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 230000004048 modification Effects 0.000 claims description 5
- 238000012986 modification Methods 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 239000002002 slurry Substances 0.000 claims description 4
- 238000001291 vacuum drying Methods 0.000 claims description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical group [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- 239000011230 binding agent Substances 0.000 claims description 3
- 239000011248 coating agent Substances 0.000 claims description 3
- 238000000576 coating method Methods 0.000 claims description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 2
- 239000006183 anode active material Substances 0.000 claims description 2
- DCYOBGZUOMKFPA-UHFFFAOYSA-N iron(2+);iron(3+);octadecacyanide Chemical compound [Fe+2].[Fe+2].[Fe+2].[Fe+3].[Fe+3].[Fe+3].[Fe+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] DCYOBGZUOMKFPA-UHFFFAOYSA-N 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 239000011572 manganese Substances 0.000 claims description 2
- 239000007774 positive electrode material Substances 0.000 claims description 2
- 229960003351 prussian blue Drugs 0.000 claims description 2
- 239000013225 prussian blue Substances 0.000 claims description 2
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 2
- 239000012498 ultrapure water Substances 0.000 claims description 2
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 2
- 229910052720 vanadium Inorganic materials 0.000 claims description 2
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 4
- 239000012528 membrane Substances 0.000 claims 1
- 210000001787 dendrite Anatomy 0.000 abstract description 6
- 239000011241 protective layer Substances 0.000 abstract description 6
- 230000008021 deposition Effects 0.000 abstract description 5
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 5
- 239000001257 hydrogen Substances 0.000 abstract description 5
- 229910052751 metal Inorganic materials 0.000 abstract description 5
- 239000002184 metal Substances 0.000 abstract description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 4
- 238000005260 corrosion Methods 0.000 abstract description 4
- 230000007797 corrosion Effects 0.000 abstract description 4
- 238000009792 diffusion process Methods 0.000 abstract description 2
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 2
- 230000001681 protective effect Effects 0.000 abstract 2
- 150000001875 compounds Chemical class 0.000 abstract 1
- 150000002431 hydrogen Chemical class 0.000 abstract 1
- 230000001939 inductive effect Effects 0.000 abstract 1
- 238000001556 precipitation Methods 0.000 abstract 1
- 210000004027 cell Anatomy 0.000 description 10
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 3
- 229960001763 zinc sulfate Drugs 0.000 description 3
- 229910000368 zinc sulfate Inorganic materials 0.000 description 3
- 239000002131 composite material Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 2
- 239000008151 electrolyte solution Substances 0.000 description 2
- 229940021013 electrolyte solution Drugs 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 1
- 239000006245 Carbon black Super-P Substances 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000002791 soaking 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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/04—Processes of manufacture in general
- H01M4/0402—Methods of deposition of the material
- H01M4/0404—Methods of deposition of the material by coating on electrode collectors
-
- 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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/42—Alloys based on zinc
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Primary Cells (AREA)
Abstract
The invention belongs to the technical field of water-based zinc ion batteries, and discloses a preparation method of a modified zinc negative electrode, wherein a zinc-hyaluronic acid compound protective film is loaded on the surface of zinc foil to form the modified zinc negative electrode. Compared with the prior art, the zinc-philic group contained in the compound protective film on the surface of the modified zinc anode can limit the two-dimensional diffusion of zinc ions, thereby inducing the uniform deposition of the zinc ions and reducing the growth of dendrites. The protective layer can occupy hydrogen evolution active sites, inhibit the precipitation of hydrogen, isolate active water molecules from directly contacting zinc metal, and reduce the corrosion of water molecules to a zinc anode. The preparation process of the modified zinc cathode adopted by the invention has the advantages of simple operation, low cost and easy realization of large-scale production.
Description
Technical Field
The invention belongs to the technical field of water-based zinc ion batteries, and relates to a preparation method of a modified zinc anode and application of the modified zinc anode in the water-based zinc ion battery.
Background
Because of the disadvantages of limited lithium metal reserves, high price, poor safety, etc., the development of new batteries has become a necessary trend. The zinc metal battery has the advantages of high theoretical capacity, proper oxidation-reduction potential, abundant natural reserves of zinc metal, environmental protection, relatively low price of zinc metal and the like, and has wide prospect in the energy storage field. However, commercial applications of zinc ion batteries still face many challenges such as dendrite growth, hydrogen evolution reactions, corrosion, passivation, etc. at zinc cathodes. Therefore, it is important to develop a simple and effective modified zinc cathode so as to solve a series of problems existing in zinc ion batteries.
Disclosure of Invention
The invention aims to provide a preparation method of a modified zinc cathode, which has low cost and simple operation, can inhibit a series of side reactions existing in a zinc ion battery and improve the electrochemical performance of the zinc ion battery.
The invention is realized by the following technical scheme.
A preparation method of a modified zinc anode comprises the following steps:
step 1: preparing aqueous solution of hyaluronic acid, and uniformly stirring for later use;
step 2: polishing the zinc sheet to remove the surface oxide layer, then cleaning with absolute ethyl alcohol and water, and drying to obtain a pretreated zinc sheet;
step 3: immersing the zinc sheet pretreated in the step 2 in aqueous solution of hyaluronic acid for surface modification;
step 4: and (3) cleaning the zinc sheet soaked in the step (3) with water and ethanol, and drying to obtain the modified zinc cathode.
In the step 1, the concentration of the aqueous solution of the hyaluronic acid is 0.1-20g/L, and the water used is one of deionized water and ultrapure water.
In the step 2 of the process, the process is carried out,
the polishing method comprises the following steps: the zinc sheets are respectively polished by abrasive paper of 500# sand paper, 1500# sand paper, 2000# sand paper and 2500# sand paper;
the cleaning mode is as follows: sequentially carrying out ultrasonic cleaning on the surface of the zinc sheet for 3-50 minutes by using absolute ethyl alcohol and water, wherein the ultrasonic power is 30-45W;
the drying is normal pressure drying or vacuum drying, and the time is 2-24 hours.
In the step 3, soaking is carried out at room temperature and normal pressure for 1-48 hours.
In the step 4, washing with water and ethanol for 1-5 times; the drying is normal pressure drying or vacuum drying, and the time is 2-24 hours.
The modified zinc cathode prepared by the method is applied to a water-based zinc ion battery, wherein the water-based zinc ion battery is a water-based zinc ion symmetrical button battery or a water-based zinc ion button full battery.
Further, when the modified zinc cathode is used for preparing the water-based zinc ion symmetrical button cell, the steps are as follows: the modified zinc sheet is used as a positive electrode and a negative electrode, and is assembled with a diaphragm and electrolyte to form the water-based zinc ion symmetrical button cell, and the water-based zinc ion symmetrical button cell is kept stand for 2-24 hours.
Further, when the modified zinc cathode is used for preparing the water-based zinc ion button full battery, the steps are as follows: the method comprises the steps of selecting a slurry prepared by mixing an anode active material with conductive carbon black, a binder and a solvent, coating the slurry on a current collector, and drying to obtain an anode; and assembling the anode, the diaphragm, the modified zinc cathode and the electrolyte into the water-based zinc ion button full battery.
Wherein the solutes of the electrolyte are ZnSO 4 、ZnCl 2 、Zn(CF 3 SO 3 ) 2 At least one of the electrolyte solutions has the concentration of 1-3mol/L, and the electrolyte solution is dripped on the diaphragm with the dosage of 20-200 microliters.
Wherein the positive electrode active material is one of manganese-based, vanadium-based and Prussian blue; the current collector is a titanium foil of 20-200 microns.
The beneficial effects of the invention are as follows:
compared with the prior art, the zinc-hyaluronic acid composite protective layer is creatively introduced on the surface of the zinc cathode. The zinc-philic group contained in the composite protective layer can limit the two-dimensional diffusion of zinc ions, so that the uniform deposition of the zinc ions is induced, and the growth of dendrites is reduced. On one hand, the protective layer can occupy hydrogen evolution active sites to inhibit hydrogen from being evolved. On the other hand, the protective layer can isolate water from directly contacting zinc metal, so that corrosion of water molecules to the zinc cathode is reduced. The preparation process of the modified zinc cathode adopted by the invention has the advantages of simple operation, low cost and easy realization of large-scale production. In a word, the invention adjusts the deposition state of zinc ions through the hyaluronic acid protective layer, thereby obtaining the zinc cathode with water corrosion resistance, no dendrite and long service life.
Drawings
FIG. 1 is an SEM image of the surface of a polished and cleaned zinc foil in example 1;
FIG. 2 is an SEM image of a modified zinc foil after immersing in hyaluronic acid in example 1;
FIG. 3 is an SEM image of the surface of a zinc sheet after 50 cycles of a zinc// zinc symmetric cell composed of zinc foil without hyaluronic acid immersed in example 1 (current density of 5mA cm) -2 )；
FIG. 4 is an SEM image of the surface of a zinc sheet after 50 cycles of a zinc// zinc symmetric cell composed of zinc foil impregnated with hyaluronic acid in example 1 (current density of 5mA cm) -2 )；
FIG. 5 is a graph showing time-voltage curves (current density: 5mA cm) of a symmetric battery using non-immersed zinc flakes as positive and negative electrodes and modified zinc flakes as positive and negative electrodes, respectively, in example 1 -2 )；
FIG. 6 is a graph showing time-voltage curves (current density: 10mA cm) of a symmetric battery using non-immersed zinc flakes as positive and negative electrodes and modified zinc flakes as positive and negative electrodes, respectively, in example 2 -2 )；
FIG. 7 is a test of the cycle stability of a zinc// vanadium pentoxide full cell using unmodified zinc sheets and modified zinc sheets as negative electrodes, respectively, in example 3.
Detailed description of the preferred embodiments
The essential features and significant developments of the invention are further illustrated below by way of specific examples, but the invention is by no means limited to the examples described.
Example 1
Step 1: preparing hyaluronic acid aqueous solution with the concentration of 3.875g/L, and uniformly stirring for later use;
step 2: polishing zinc sheets by using 500# sand paper, 1000# sand paper, 1500# sand paper, 2000# sand paper and 2500# sand paper, cleaning the zinc sheets by using deionized water and absolute ethyl alcohol for 3 times respectively, and drying the zinc sheets after cleaning to obtain pretreated zinc sheets; as shown in fig. 1, the zinc sheet surface is relatively flat;
step 3: immersing the pretreated zinc sheet in aqueous solution of hyaluronic acid for 1 hour to carry out surface modification;
step 4: washing the zinc sheet soaked in the step 4 by using water and ethanol, and drying to obtain a modified zinc sheet cathode; as shown in fig. 2, there was little difference from the surface condition of the pretreated zinc sheet.
Step 5: the pretreated zinc sheets are respectively selected as positive electrodes and negative electrodes or the modified zinc sheets are selected as positive electrodes and negative electrodes, and the water-based zinc ion symmetrical battery is assembled by the zinc sheets, a diaphragm and 100 microliters of 2mol/L zinc sulfate electrolyte, and is stood for 4 hours.
Selecting a current density of 5mA cm -2 And a volume density of 5mA h cm -2 And performing constant current charge and discharge test. As shown in fig. 5, the symmetrical cell composed of the pretreated zinc sheet was short-circuited only for 80 hours. The symmetrical battery composed of the modified zinc sheets can be stably circulated for more than 3600 hours, and the cycle life is obviously prolonged.
After 50 times of charge-discharge cycles are operated, sampling and detection are respectively carried out, as shown in figure 3, uneven zinc deposition occurs on the surface of the pretreated zinc sheet after 50 times of charge-discharge cycles are operated, and zinc dendrites appear; as shown in fig. 4, the modified zinc sheet was subjected to 50 charge-discharge cycles with uniform zinc deposition on the surface without zinc dendrites.
Example 2
Step 1: preparing aqueous solution of hyaluronic acid with concentration of 7.75g/L, and uniformly stirring for later use;
step 2: polishing zinc sheets by using 500# sand paper, 1000# sand paper, 1500# sand paper, 2000# sand paper and 2500# sand paper, cleaning the zinc sheets by using deionized water and absolute ethyl alcohol for 3 times respectively, and drying the zinc sheets after cleaning to obtain pretreated zinc sheets;
step 3: immersing the pretreated zinc sheet in aqueous solution of hyaluronic acid for 1 hour to carry out surface modification;
step 4: washing the zinc sheet soaked in the step 4 by using water and ethanol, and drying to obtain a modified zinc sheet cathode;
step 5: the pretreated zinc sheets are respectively selected as positive electrodes and negative electrodes or the modified zinc sheets are selected as positive electrodes and negative electrodes, and the water-based zinc ion symmetrical battery is assembled by the zinc sheets, a diaphragm and 100 microliters of 2mol/L zinc sulfate electrolyte, and is stood for 4 hours.
The current density was selected to be 10mA cm -2 And a volume density of 10mA h cm -2 And performing constant current charge and discharge test. As shown in fig. 6, the symmetrical cell composed of the pretreated zinc sheet was short-circuited only by 42 hours. The symmetrical battery composed of the modified zinc sheets can stably circulate for more than 900 hours, and the cycle life is obviously prolonged.
Example 3
Step 1: preparing hyaluronic acid aqueous solution with the concentration of 3.875g/L, and uniformly stirring for later use;
step 2: polishing zinc sheets by using 500# sand paper, 1000# sand paper, 1500# sand paper, 2000# sand paper and 2500# sand paper, cleaning the zinc sheets by using deionized water and absolute ethyl alcohol for 3 times respectively, and drying the zinc sheets after cleaning to obtain pretreated zinc sheets;
step 3: immersing the pretreated zinc sheet in aqueous solution of hyaluronic acid for 1 hour to carry out surface modification;
step 4: washing the zinc sheet soaked in the step 4 by using water and ethanol, and drying to obtain a modified zinc sheet cathode;
step 5: active substance V 2 O 5 Mixing the anode with a binder PVDF and conductive carbon black Super P in an NMP solvent, coating the mixture on a titanium foil current collector, and drying the mixture to obtain an anode;
step 5: the pretreated zinc sheet and the modified zinc sheet are respectively selected as negative electrodes, and are assembled into a water-based zinc ion full battery together with a diaphragm and 100 microliters of 2mol/L zinc sulfate electrolyte, and the water-based zinc ion full battery is kept stand for 4 hours. And selecting the current density of 10A/g for long-time constant-current charge and discharge test.
As shown in FIG. 7, after 1000 charge/discharge cycles, the specific discharge capacity of the full cell using the modified zinc anode reached 131mAh g -1 Specific discharge capacity of 102 mAh.g compared with full cell using unmodified zinc anode -1 Has obvious improvement.
Claims (10)
1. The preparation method of the modified zinc anode is characterized by comprising the following steps:
step 1: preparing aqueous solution of hyaluronic acid, and uniformly stirring for later use;
step 2: polishing the zinc sheet to remove the surface oxide layer, then cleaning with absolute ethyl alcohol and water, and drying to obtain a pretreated zinc sheet;
step 3: immersing the zinc sheet pretreated in the step 2 in aqueous solution of hyaluronic acid for surface modification;
step 4: and (3) cleaning the zinc sheet soaked in the step (3) with water and ethanol, and drying to obtain the modified zinc cathode.
2. The method for producing a modified zinc anode according to claim 1, wherein in step 1, the concentration of the aqueous solution of hyaluronic acid is 0.1 to 20g/L, and the water used is one of deionized water and ultrapure water.
3. The method for producing a modified zinc anode according to claim 1, wherein in step 2,
the polishing method comprises the following steps: the zinc sheets are respectively polished by abrasive paper of 500# sand paper, 1500# sand paper, 2000# sand paper and 2500# sand paper;
the cleaning mode is as follows: sequentially carrying out ultrasonic cleaning on the surface of the zinc sheet for 3-50 minutes by using absolute ethyl alcohol and water, wherein the ultrasonic power is 30-45W;
the drying is normal pressure drying or vacuum drying, and the time is 2-24 hours.
4. The method for producing a modified zinc anode according to claim 1, wherein in step 3, the immersing is performed at room temperature and normal pressure for 1 to 48 hours.
5. The method for producing a modified zinc anode according to claim 1, wherein in step 4, the number of washing with water and ethanol is 1 to 5 times; the drying is normal pressure drying or vacuum drying, and the time is 2-24 hours.
6. The use of the modified zinc cathode prepared by the preparation method according to any one of claims 1 to 5 in an aqueous zinc ion battery, wherein the aqueous zinc ion battery is an aqueous zinc ion symmetrical button battery or an aqueous zinc ion button full battery.
7. The use according to claim 6, wherein the modified zinc cathode for the preparation of an aqueous zinc ion symmetric button cell comprises the steps of: the modified zinc sheet is used as a positive electrode and a negative electrode, and is assembled with a diaphragm and electrolyte to form the water-based zinc ion symmetrical button cell, and the water-based zinc ion symmetrical button cell is kept stand for 2-24 hours.
8. The use according to claim 6, wherein the modified zinc cathode is used for preparing a full cell of an aqueous zinc ion button, comprising the steps of: the method comprises the steps of selecting a slurry prepared by mixing an anode active material with conductive carbon black, a binder and a solvent, coating the slurry on a current collector, and drying to obtain an anode; and assembling the anode, the diaphragm, the modified zinc cathode and the electrolyte into the water-based zinc ion button full battery.
9. The use according to claim 7 or 8, wherein the solute of the electrolyte is ZnSO 4 、ZnCl 2 、Zn(CF 3 SO 3 ) 2 At least one of the above electrolytes has a concentration of 1-3mol/L and is added dropwise to the membrane in an amount of 20-200. Mu.L.
10. The use according to claim 8, wherein the positive electrode active material is one of manganese-based, vanadium-based, prussian blue; the current collector is a titanium foil of 20-200 microns.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310591448.4A CN116759522A (en) | 2023-05-24 | 2023-05-24 | Preparation method of modified zinc cathode and application of modified zinc cathode in water-based zinc ion battery |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310591448.4A CN116759522A (en) | 2023-05-24 | 2023-05-24 | Preparation method of modified zinc cathode and application of modified zinc cathode in water-based zinc ion battery |
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| CN116759522A true CN116759522A (en) | 2023-09-15 |
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| CN202310591448.4A Pending CN116759522A (en) | 2023-05-24 | 2023-05-24 | Preparation method of modified zinc cathode and application of modified zinc cathode in water-based zinc ion battery |
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| Country | Link |
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