CN112563479B - Hydrogel-shaped zinc anode material, preparation method thereof, anode and battery - Google Patents
Hydrogel-shaped zinc anode material, preparation method thereof, anode and battery Download PDFInfo
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- CN112563479B CN112563479B CN202011434658.5A CN202011434658A CN112563479B CN 112563479 B CN112563479 B CN 112563479B CN 202011434658 A CN202011434658 A CN 202011434658A CN 112563479 B CN112563479 B CN 112563479B
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- 229910052725 zinc Inorganic materials 0.000 title claims abstract description 120
- 239000011701 zinc Substances 0.000 title claims abstract description 120
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title claims abstract description 118
- 239000010405 anode material Substances 0.000 title claims abstract description 62
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 229910052751 metal Inorganic materials 0.000 claims abstract description 78
- 239000002184 metal Substances 0.000 claims abstract description 78
- 239000007788 liquid Substances 0.000 claims abstract description 68
- 239000002131 composite material Substances 0.000 claims abstract description 31
- 229910052738 indium Inorganic materials 0.000 claims abstract description 17
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229920000642 polymer Polymers 0.000 claims abstract description 15
- 239000007864 aqueous solution Substances 0.000 claims abstract description 14
- 239000000017 hydrogel Substances 0.000 claims abstract description 13
- 230000008018 melting Effects 0.000 claims abstract description 13
- 238000002844 melting Methods 0.000 claims abstract description 13
- 238000002156 mixing Methods 0.000 claims abstract description 12
- 229910052718 tin Inorganic materials 0.000 claims abstract description 12
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 10
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000010438 heat treatment Methods 0.000 claims abstract description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 6
- 239000010936 titanium Substances 0.000 claims abstract description 6
- 229910052797 bismuth Inorganic materials 0.000 claims abstract description 4
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims abstract description 4
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 3
- 239000011572 manganese Substances 0.000 claims abstract description 3
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 3
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 3
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims abstract description 3
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 22
- 229910052733 gallium Inorganic materials 0.000 claims description 22
- 239000000243 solution Substances 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 7
- 239000007773 negative electrode material Substances 0.000 claims description 7
- -1 polyethylene Polymers 0.000 claims description 7
- 239000000679 carrageenan Substances 0.000 claims description 4
- 235000010418 carrageenan Nutrition 0.000 claims description 4
- 229920001525 carrageenan Polymers 0.000 claims description 4
- 229940113118 carrageenan Drugs 0.000 claims description 4
- 229920001223 polyethylene glycol Polymers 0.000 claims description 4
- UHVMMEOXYDMDKI-JKYCWFKZSA-L zinc;1-(5-cyanopyridin-2-yl)-3-[(1s,2s)-2-(6-fluoro-2-hydroxy-3-propanoylphenyl)cyclopropyl]urea;diacetate Chemical compound [Zn+2].CC([O-])=O.CC([O-])=O.CCC(=O)C1=CC=C(F)C([C@H]2[C@H](C2)NC(=O)NC=2N=CC(=CC=2)C#N)=C1O UHVMMEOXYDMDKI-JKYCWFKZSA-L 0.000 claims description 4
- 239000004698 Polyethylene Substances 0.000 claims description 3
- 150000004985 diamines Chemical class 0.000 claims description 3
- 229920000573 polyethylene Polymers 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 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 2
- 229920001817 Agar Polymers 0.000 claims description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 2
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 2
- 229920002125 Sokalan® Polymers 0.000 claims description 2
- 239000008272 agar Substances 0.000 claims description 2
- 229940023476 agar Drugs 0.000 claims description 2
- 235000010419 agar Nutrition 0.000 claims description 2
- 239000000783 alginic acid Substances 0.000 claims description 2
- 235000010443 alginic acid Nutrition 0.000 claims description 2
- 229920000615 alginic acid Polymers 0.000 claims description 2
- 229960001126 alginic acid Drugs 0.000 claims description 2
- 150000004781 alginic acids Chemical class 0.000 claims description 2
- 229920002674 hyaluronan Polymers 0.000 claims description 2
- 229960003160 hyaluronic acid Drugs 0.000 claims description 2
- 229920002401 polyacrylamide Polymers 0.000 claims description 2
- 239000004584 polyacrylic acid Substances 0.000 claims description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 230000007547 defect Effects 0.000 abstract description 3
- 239000011521 glass Substances 0.000 description 12
- 230000008021 deposition Effects 0.000 description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 9
- 229910001297 Zn alloy Inorganic materials 0.000 description 8
- 229910052799 carbon Inorganic materials 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 210000001787 dendrite Anatomy 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 239000003792 electrolyte Substances 0.000 description 7
- 239000000758 substrate Substances 0.000 description 6
- 238000011056 performance test Methods 0.000 description 5
- 239000000499 gel Substances 0.000 description 4
- 239000011261 inert gas Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000010008 shearing Methods 0.000 description 4
- 239000010935 stainless steel Substances 0.000 description 4
- 229910001220 stainless steel Inorganic materials 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 3
- 239000010406 cathode material Substances 0.000 description 3
- 238000004146 energy storage Methods 0.000 description 3
- 239000006260 foam Substances 0.000 description 3
- 239000003365 glass fiber Substances 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- WJZHMLNIAZSFDO-UHFFFAOYSA-N manganese zinc Chemical compound [Mn].[Zn] WJZHMLNIAZSFDO-UHFFFAOYSA-N 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 2
- 210000004027 cell Anatomy 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000007493 shaping process Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000003828 vacuum filtration Methods 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 230000010802 Oxidation-Reduction Activity Effects 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000005489 elastic deformation Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- BSWGGJHLVUUXTL-UHFFFAOYSA-N silver zinc Chemical compound [Zn].[Ag] BSWGGJHLVUUXTL-UHFFFAOYSA-N 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 238000012546 transfer 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
- H01M4/36—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
- 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
- H01M4/04—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
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The application belongs to the technical field of batteries, and particularly relates to a hydrogel-shaped zinc anode material, a preparation method thereof, an anode and a battery. The application discloses a preparation method of a hydrogel-shaped zinc anode material, which comprises the following steps: step 1, heating a first metal to a molten state to prepare a first metal liquid; step 2, mixing a second metal with the first metal liquid to prepare a composite metal liquid; step 3, mixing the composite metal liquid and the polymer aqueous solution to prepare a hydrogel shaped zinc anode material; wherein the melting point of the first metal is lower than the melting point of the second metal; the second metal is selected from one or more of zinc, indium, tin, bismuth, titanium, nickel, vanadium and manganese. The zinc anode material, the preparation method thereof, the anode and the battery can effectively solve the technical defects of low safety and poor electrochemical performance of the traditional zinc anode material.
Description
Technical Field
The application belongs to the technical field of batteries, and particularly relates to a hydrogel-shaped zinc anode material, a preparation method thereof, an anode and a battery.
Background
The metal zinc cathode is an ideal cathode material of a secondary battery due to the fact that the theoretical capacity of the metal zinc cathode is high (820 mAh.g -1), the oxidation-reduction potential is relatively low (0.76V relative to a standard hydrogen electrode), the cost is low, the safety is high, and the metal zinc cathode has good electrochemical stability in water, and is particularly suitable for the fields of large-scale energy storage, wearable equipment and the like. However, the conventional metallic zinc anode material may cause dendrite formation due to non-uniform zinc deposition, and the continuous zinc dendrite growth may pierce the separator and cause internal short circuit of the battery, seriously affecting the service life and the safety of the battery.
In view of this problem, the scientific community has proposed different solutions including zinc negative electrode surface treatment and the use of composite electrodes and the like. However, in the known method, there are few solutions capable of improving both the safety and the electrochemical performance of the zinc anode material.
Disclosure of Invention
In view of the above, the application aims to provide a hydrogel-shaped zinc anode material, a preparation method thereof, an anode and a battery, and the technical defects of low safety and poor electrochemical performance of the existing zinc anode material can be effectively overcome.
The application discloses a preparation method of a hydrogel-shaped zinc anode material, which comprises the following steps:
Step 1, heating a first metal to a molten state to prepare a first metal liquid;
Step 2, mixing a second metal with the first metal liquid to prepare a composite metal liquid;
Step 3, mixing the composite metal liquid and the polymer aqueous solution to prepare a hydrogel shaped zinc anode material; wherein the melting point of the first metal is lower than the melting point of the second metal; the second metal is selected from one or more of zinc, indium, tin, bismuth, titanium, nickel, vanadium and manganese.
Wherein the first metal liquid in the step 1 is prepared by melting in an inert atmosphere; and 2, melting the composite metal liquid in the step 2 under an inert atmosphere to obtain the composite metal liquid.
In another embodiment, the first metal is selected from one or more of gallium, indium, and tin.
In another embodiment, the first metal is gallium; the second metal is zinc, indium, tin and bismuth.
In another embodiment, the composite metal liquid comprises, in mass percent: 76% gallium, 12% indium and 12% zinc.
In another embodiment, the composite metal liquid comprises, in mass percent: 71% gallium, 20% indium, 8% zinc and 1% tin.
The melting point of the first metal is lower than the melting point of the second metal, and the melting point of each metal of the first metal is lower than the melting point of each metal of the second metal.
In another embodiment, the composite metal liquid accounts for 70-99% of the zinc anode material according to the mass percentage; the polymer aqueous solution accounts for 1% -30% of the zinc anode material.
In another embodiment, the composite metal liquid accounts for 85-90% of the zinc anode material according to the mass percentage; the polymer aqueous solution accounts for 10% -15% of the zinc anode material.
In another embodiment, the zinc comprises 3 to 30% of the composite metal liquid.
In another embodiment, the zinc comprises 8-12% of the composite metal liquid.
In another embodiment, the solute of the aqueous polymer solution is selected from one or more of polyethylene oxide, polyethylene glycol, polyvinyl alcohol, polyacrylamide, polyacrylic acid, alginic acid, carrageenan, agar, hyaluronic acid and polyethylene diamine.
In another embodiment, the aqueous polymer solution has a water content of 10% to 80%.
In another embodiment, the mixing of the composite metal liquid and the aqueous polymer solution comprises: and (5) shearing and dispersing.
The application discloses a hydrogel-shaped zinc anode material, which comprises the hydrogel-shaped zinc anode material prepared by the preparation method.
In another embodiment, the hydrogel-formed zinc anode material has controllable forming property and fluidity in a temperature range of-30-100 ℃; the viscosity of the hydrogel-formed zinc anode material is 1000-100000cP.
The third aspect of the application discloses a negative electrode, which comprises a hydrogel-shaped zinc negative electrode material prepared by the preparation method or the hydrogel-shaped zinc negative electrode material.
Specifically, the negative electrode comprises a hydrogel-shaped zinc negative electrode material prepared by the preparation method or the hydrogel-shaped zinc negative electrode material, and at least one current collector.
The zinc anode material shaped by the hydrogel is in a liquid state when in operation, and preferably, the current collector is at least one of carbon paper, graphene foam, carbon tube paper, stainless steel foil, stainless steel net, foam copper, copper foil, titanium foil, foam titanium, titanium net, carbon-coated stainless steel net, conductive plastic-coated stainless steel net and cutting titanium net; the hydrogel-shaped zinc anode material can be directly coated on a current collector or soaked in the porous conductive substrate by a vacuum filtration method.
A fourth aspect of the application discloses a battery comprising the negative electrode.
Specifically, the battery is a secondary battery; the secondary battery comprises a zinc ion battery, a zinc-manganese battery, a zinc-silver battery, a zinc solid-state battery and a zinc-air battery.
The composite metal liquid is one kind of liquid zinc alloy, and the liquid zinc alloy has excellent flowability, high elastic deformation capacity, low heat expansion coefficient and other special performance, and the liquid zinc alloy is hydrogel shaped to solve the dendrite problem of zinc negative electrode and increase its oxidation-reduction activity.
The application has the beneficial effects that:
In one aspect, the application discloses a hydrogel-shaped zinc anode material and a preparation method thereof, wherein the zinc anode material is prepared by adopting a melting method, and a composite metal liquid and a polymer aqueous solution are mixed, so that the hydrogel-shaped zinc anode material can be in a liquid state and has fluidity within the temperature range of-30-100 ℃. On the other hand, the application discloses application of the hydrogel-shaped zinc anode material in a secondary battery, and the zinc dendrite problem is radically eliminated by utilizing the fluidity and deformability of the hydrogel-shaped zinc anode material, so that the cycle stability and the service life of the zinc secondary battery anode are improved. In addition, compared with the traditional solid-liquid interface, the liquid-liquid interface between the hydrogel shaped zinc anode material and the electrolyte has better ion dynamic transmission characteristics, and the interface charge transmission resistance and the mass transfer resistance are obviously reduced, so that the application of the zinc secondary battery in energy type of large-scale energy storage and power type of rapid energy storage and release is realized.
In conclusion, the hydrogel-forming zinc anode material provided by the application is in a liquid state in the charge and discharge process of a battery, and has fluidity and deformability. When in use, on one hand, zinc dendrite is avoided, and the service life and the use safety of the zinc secondary battery are greatly improved; on the other hand, a liquid-liquid interface is formed between the liquid hydrogel shaped zinc anode material and the electrolyte, so that the interface ion transmission energy barrier can be effectively reduced, and the rate capability of the zinc secondary battery is improved.
Drawings
In order to more clearly illustrate the embodiments of the present application or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below.
FIG. 1 is a graph of zinc deposition/stripping test voltage versus time for a first negative electrode made of a first hydrogel-forming zinc negative electrode material provided in example 1 of the present application;
FIG. 2 is a photograph of a second hydrogel-forming zinc anode material according to example 2 of the present application;
FIG. 3 is a 500-cycle plot of a second cell made of a second hydrogel-forming zinc anode material provided in example 2 of the present application;
FIG. 4 is a graph of zinc deposition/stripping test voltage versus time for a metallic zinc anode provided in comparative example 1 of the present application;
Fig. 5 is a graph of zinc deposition/stripping test voltage versus time for a liquid zinc alloy negative electrode prepared without mixing with an aqueous polymer solution provided in comparative example 2 of the present application.
Detailed Description
The application provides a hydrogel-shaped zinc anode material, a preparation method thereof, an anode and a battery, which are used for solving the technical defects of low safety and poor electrochemical performance of the zinc anode material in the prior art.
The following description of the technical solutions in the embodiments of the present application will be clear and complete, and it is obvious that the described embodiments are only some embodiments of the present application, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the application without making any inventive effort, are intended to be within the scope of the application.
Wherein, the raw materials or reagents of the following examples are all commercial or homemade, the purity of gallium used in the following examples is >99%, the purity of indium is >99%, the purity of zinc is >99%, and the purity of tin is >99%.
Example 1
The embodiment of the application provides a zinc anode material formed by hydrogel, an anode and a battery, and the specific preparation method comprises the following steps:
1. And measuring 76% by mass of gallium, 12% by mass of indium and 12% by mass of zinc. Then, the raw gallium is heated to 29 ℃ under the protection of inert gas, so that the raw gallium is melted, and the raw gallium is poured into a glass container after heating is stopped, so as to prepare the first metal liquid. And pouring the indium and zinc metals in the determined proportion into the glass container, and mechanically stirring the glass container and the first metal liquid at room temperature to uniformly mix the components to prepare the composite metal liquid. Mixing the composite metal liquid with a carrageenan aqueous solution (the concentration of the carrageenan is 20%) according to a mass ratio of 9:1, shearing and dispersing to obtain the uniform and stable liquid first hydrogel shaped zinc anode material.
2. And coating the first hydrogel-formed zinc anode material on the surface of a titanium foil current collector to prepare a first anode, and taking the first anode as an electrode material to perform zinc deposition/stripping test. A first cell was prepared using a glass fiber film as the separator and a 2M aqueous solution of ZnSO 4 as the electrolyte.
3. The results of the zinc deposition/stripping test of the first hydrogel-forming zinc anode material at a current of 0.1mA/cm 2 are shown in fig. 1. The liquid hydrogel shaped zinc cathode material has lower zinc deposition/stripping voltage, and is proved to have smaller overpotential, higher ion diffusion rate and better dynamic performance.
Example 2
The embodiment of the application provides a second hydrogel-shaped zinc anode material, an anode and a battery, and the specific preparation method comprises the following steps:
1. 71% by mass of gallium, 20% by mass of indium, 8% by mass of zinc and 1% by mass of tin are measured. Then, the raw gallium is heated to 29 ℃ under the protection of inert gas, so that the raw gallium is melted, and the raw gallium is poured into a glass container after heating is stopped, so as to prepare the first metal liquid. And pouring the indium, zinc and tin metals in the determined proportion into the glass container, and mechanically stirring the glass container and the first metal liquid at room temperature to uniformly mix the components to prepare the composite metal liquid. The solidifying point of the composite metal liquid is about 5 ℃ through measurement; the density at 18℃is 6.52g/cm 3 and the conductivity is about 3.5X10 6 S/m. The obtained composite metal liquid and PEG aqueous solution (the concentration of PEG is 20%) are mixed according to the mass ratio of 8.5: and 1.5, shearing and dispersing after mixing to obtain the uniform and stable liquid second hydrogel-shaped zinc anode material.
2. And (3) vacuum-filtering a liquid second hydrogel-shaped zinc anode material in a porous carbon paper substrate to serve as a second anode (as shown in fig. 2, fig. 2 is a physical photograph of the second zinc anode material provided in embodiment 2 of the application), taking MnO 2 as a cathode material, taking 2M ZnSO 4 aqueous solution as electrolyte, assembling a second battery, and carrying out related electrochemical performance test on the second battery.
The first 500 cycles of the second battery of this example were performed at a charge/discharge rate of 10C as shown in fig. 3. The embodiment shows that the liquid zinc alloy gel cathode can work well in an actual zinc ion battery, and has good cycle stability and rate capability.
Example 3
The embodiment of the application provides a zinc anode material formed by a third hydrogel, an anode and a battery, and the specific preparation method comprises the following steps:
1. 71 parts of gallium with purity of 99 percent, 20 parts of indium with purity of 99 percent, 8 parts of zinc with purity of 99 percent and 1 part of tin with purity of 99 percent are measured according to mass percent. Then, the raw gallium is heated to 29 ℃ under the protection of inert gas, so that the raw gallium is melted, and the raw gallium is poured into a glass container after heating is stopped, so as to prepare the first metal liquid. And pouring the indium, zinc and tin metals in the determined proportion into the glass container, and mechanically stirring the glass container and the first metal liquid at room temperature to uniformly mix the components to prepare the composite metal liquid. The alloy has a solidification point of about 5 ℃ as determined; the density at 18℃is 6.52g/cm 3 and the conductivity is about 3.5X10 6 S/m. Mixing the obtained composite metal liquid with polyethylene diamine according to a mass ratio of 8:2, shearing and dispersing after mixing to obtain the uniform and stable liquid zinc anode material shaped by the third hydrogel.
2. And vacuum-filtering a liquid third hydrogel-formed zinc anode material in a porous carbon paper substrate to serve as a third anode, taking MnO 2 as a positive electrode material and taking KOH aqueous solution as electrolyte, assembling an alkaline zinc-manganese battery and carrying out related electrochemical performance test.
The liquid zinc alloy gel negative electrode after the circulation of the alkaline zinc-manganese battery does not find dendrite generation, which shows that the liquid zinc alloy gel negative electrode can effectively avoid zinc dendrite generation in the battery.
Comparative example 1
The application provides an electrochemical performance test with a solid metal zinc sheet as a negative electrode, which comprises the following specific steps:
Solid metallic zinc sheets were used as a comparison and a zinc deposition/stripping test was performed. The metallic zinc sheet was polished to smooth and then directly used as a negative electrode, a glass fiber film was used as a separator, and a 2M aqueous ZnSO 4 solution was used as an electrolyte, and the results of the zinc deposition/stripping test of the metallic zinc electrode of this comparative example were shown in FIG. 4 at a current of 0.1mA/cm 2. The deposition stripping voltage of the hydrogel-shaped zinc anode material is far greater than that of the zinc anode materials of the embodiment 1 and the embodiment 2, which shows that the hydrogel-shaped zinc anode material has smaller interface impedance and can effectively improve the multiplying power performance of a zinc secondary battery.
Comparative example 2
The application provides an electrochemical performance test of a composite metal liquid which is filtered in vacuum and used as a negative electrode in a porous carbon paper substrate, and the electrochemical performance test comprises the following specific steps:
the preparation method of the negative electrode of the comparative example includes:
1. And measuring 76% by mass of gallium, 12% by mass of indium and 12% by mass of zinc. Then, the raw gallium is heated to 29 ℃ under the protection of inert gas, so that the raw gallium is melted, and the raw gallium is poured into a glass container after heating is stopped, so as to prepare the first metal liquid. Pouring the indium and zinc metals in a certain proportion into the glass container, and mechanically stirring the glass container and the first metal liquid at room temperature to uniformly mix the components to prepare composite metal liquid;
2. The composite metal liquid is arranged in the porous carbon paper substrate in a vacuum filtration mode to prepare a negative electrode, a glass fiber film is used as a diaphragm, a 2M ZnSO 4 aqueous solution is used as electrolyte, and the zinc deposition/stripping test result of the negative electrode of the comparative example is shown in figure 5 under the current of 0.1mA/cm 2.
Fig. 5 illustrates that the composite metal liquid not compounded with the polymer gel of this comparative example is strong in fluidity and weak in adhesion to the porous carbon paper substrate, and the liquid zinc alloy flows in the battery, which quickly causes short-circuit failure of the battery. Under high external forces, liquid leakage can also occur.
From the data, the hydrogel shaped zinc anode material contains a polymer aqueous solution, so that the adhesion with a current collector can be increased, the short circuit and liquid leakage of a battery can be prevented, and the zinc anode material is subjected to shaping post-treatment, so that the zinc anode material has shaping property and fluidity, the problem of zinc dendrite is fundamentally solved, and the cycle stability and the service life of a zinc secondary battery anode are improved.
The foregoing is merely a preferred embodiment of the present application and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present application, which are intended to be comprehended within the scope of the present application.
Claims (9)
1. The preparation method of the hydrogel-shaped zinc anode material is characterized by comprising the following steps of:
Step 1, heating a first metal to a molten state to prepare a first metal liquid;
Step 2, mixing a second metal with the first metal liquid to prepare a composite metal liquid;
Step 3, mixing the composite metal liquid and the polymer aqueous solution to prepare a hydrogel shaped zinc anode material; wherein the melting point of the first metal is lower than the melting point of the second metal; the second metal is selected from one or more of zinc, indium, tin, bismuth, titanium, nickel, vanadium and manganese;
the first metal is selected from one or more of gallium, indium, and tin.
2. The preparation method of claim 1, wherein the composite metal liquid accounts for 70-99% of the zinc anode material according to mass percent; the polymer aqueous solution accounts for 1% -30% of the zinc anode material.
3. The method of claim 1, wherein the zinc comprises 3-30% of the composite metal liquid.
4. The method according to claim 1, wherein the solute of the aqueous polymer solution is one or more selected from polyethylene oxide, polyethylene glycol, polyvinyl alcohol, polyacrylamide, polyacrylic acid, alginic acid, carrageenan, agar, hyaluronic acid and polyethylene diamine.
5. The method of claim 1, wherein the aqueous polymer solution has a water content of 10% to 80%.
6. A hydrogel-forming zinc anode material, comprising the hydrogel-forming zinc anode material prepared by the preparation method of any one of claims 1 to 5.
7. The zinc anode material of claim 6, wherein the hydrogel-forming zinc anode material has controlled formability and flowability over a temperature range of-30 to 100 ℃; the viscosity of the hydrogel-formed zinc anode material is 1000-100000cP.
8. A negative electrode comprising the hydrogel-forming zinc negative electrode material produced by the production method according to any one of claims 1 to 5 or the hydrogel-forming zinc negative electrode material according to claim 6 or 7.
9. A battery comprising the anode of claim 8.
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