CN114447311A - Zinc ion battery negative electrode material and preparation method and application thereof - Google Patents
Zinc ion battery negative electrode material and preparation method and application thereof Download PDFInfo
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- CN114447311A CN114447311A CN202210023126.5A CN202210023126A CN114447311A CN 114447311 A CN114447311 A CN 114447311A CN 202210023126 A CN202210023126 A CN 202210023126A CN 114447311 A CN114447311 A CN 114447311A
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- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 239000007773 negative electrode material Substances 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000011701 zinc Substances 0.000 claims abstract description 170
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 148
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 147
- 229910001297 Zn alloy Inorganic materials 0.000 claims abstract description 74
- 239000000463 material Substances 0.000 claims abstract description 70
- QELJHCBNGDEXLD-UHFFFAOYSA-N nickel zinc Chemical compound [Ni].[Zn] QELJHCBNGDEXLD-UHFFFAOYSA-N 0.000 claims abstract description 70
- 238000004070 electrodeposition Methods 0.000 claims abstract description 38
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 34
- 238000000034 method Methods 0.000 claims abstract description 23
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 14
- 238000000137 annealing Methods 0.000 claims abstract description 13
- 229910052751 metal Inorganic materials 0.000 claims abstract description 8
- 239000002184 metal Substances 0.000 claims abstract description 8
- 239000010406 cathode material Substances 0.000 claims abstract description 6
- 238000013329 compounding Methods 0.000 claims abstract description 3
- 238000010438 heat treatment Methods 0.000 claims description 37
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 32
- 239000002131 composite material Substances 0.000 claims description 22
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 18
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 18
- 235000019270 ammonium chloride Nutrition 0.000 claims description 16
- 239000002243 precursor Substances 0.000 claims description 16
- 238000001816 cooling Methods 0.000 claims description 15
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 14
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 14
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 14
- 238000004140 cleaning Methods 0.000 claims description 11
- 239000008367 deionised water Substances 0.000 claims description 11
- 229910021641 deionized water Inorganic materials 0.000 claims description 11
- 238000000151 deposition Methods 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 230000008569 process Effects 0.000 claims description 10
- 230000008021 deposition Effects 0.000 claims description 8
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 claims description 8
- 229910052697 platinum Inorganic materials 0.000 claims description 7
- 238000005498 polishing Methods 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- 238000009210 therapy by ultrasound Methods 0.000 claims description 7
- 239000003792 electrolyte Substances 0.000 claims description 5
- 244000137852 Petrea volubilis Species 0.000 claims description 3
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 2
- 238000000576 coating method Methods 0.000 abstract description 20
- 238000005260 corrosion Methods 0.000 abstract description 19
- 239000011248 coating agent Substances 0.000 abstract description 18
- 230000002035 prolonged effect Effects 0.000 abstract description 4
- 239000013078 crystal Substances 0.000 abstract description 3
- 210000004027 cell Anatomy 0.000 description 18
- 239000010410 layer Substances 0.000 description 18
- 239000000956 alloy Substances 0.000 description 14
- 230000007797 corrosion Effects 0.000 description 14
- 239000000758 substrate Substances 0.000 description 14
- 229910018605 Ni—Zn Inorganic materials 0.000 description 12
- 229910045601 alloy Inorganic materials 0.000 description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 238000002441 X-ray diffraction Methods 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 239000006227 byproduct Substances 0.000 description 6
- 238000010586 diagram Methods 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 210000001787 dendrite Anatomy 0.000 description 3
- QNDQILQPPKQROV-UHFFFAOYSA-N dizinc Chemical compound [Zn]=[Zn] QNDQILQPPKQROV-UHFFFAOYSA-N 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 238000011065 in-situ storage Methods 0.000 description 3
- 230000010287 polarization Effects 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000006911 nucleation Effects 0.000 description 2
- 238000010899 nucleation Methods 0.000 description 2
- 238000000399 optical microscopy Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000007774 positive electrode material Substances 0.000 description 2
- 239000011241 protective layer Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- VCPQWWKLNIMKND-UHFFFAOYSA-L zinc hydroxy sulfate Chemical compound [Zn++].OOS([O-])(=O)=O.OOS([O-])(=O)=O VCPQWWKLNIMKND-UHFFFAOYSA-L 0.000 description 2
- 229910000368 zinc sulfate Inorganic materials 0.000 description 2
- 239000011686 zinc sulphate Substances 0.000 description 2
- 239000013543 active substance Substances 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000012993 chemical processing Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000000879 optical micrograph Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Images
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/36—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
- 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
-
- 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
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The invention relates to a zinc ion battery cathode material and a preparation method and application thereof, wherein the zinc ion battery cathode material is obtained by sequentially compounding a nickel-zinc alloy and a metal nickel layer on the surface of a zinc sheet, and the nickel-zinc alloy comprises Ni2Zn11. The invention coats the nickel-zinc alloy layer on the zinc base by constant voltage electrodeposition and two-step annealing method, the nickel-zinc alloy layer and the zinc base are tightly jointed to form the nickel-zinc alloy coated zinc base material, the nickel-zinc alloy coated zinc base material used as the zinc ion battery negative electrode material has the characteristics of excellent electrochemical performance, high cycle stability and long cycle life, can solve the problems of dendritic crystal growth, self-corrosion, short cycle life and the like of the zinc ion battery negative electrode material, and can realize the self-corrosion of the zinc ion battery negative electrode material at 0.5mA cm‑2Under the current density of the nickel-zinc alloy coating zinc base material, the nickel-zinc alloy coating zinc base material can stably run for more than 1900 hours, and the cycle life is obviously prolonged.
Description
Technical Field
The invention belongs to the technical field of selection of materials used as electrode active substances, and particularly relates to a zinc ion battery negative electrode material and a preparation method and application thereof.
Background
Among the rechargeable batteries, the aqueous zinc ion battery is very much noticed because of its simple operation, and can use aqueous electrolyte, and the zinc metal negative electrode is easy to use. Zinc cathodes have many excellent characteristics including low cost, environmental protection, high theoretical capacity (up to 5854mAh L)-1) High zinc resource abundance, low electrochemical potential (-0.76V, relative to standard hydrogen electrodes), etc. However, the cycle life of the zinc cathode is low because the battery is easy to form dendrite, zinc oxide, zinc hydroxysulfate and other byproducts in the charge-discharge cycle process, so that the improvement of the zinc cathode is particularly important for prolonging the service life of the zinc ion battery. Generally, modification is performed from two aspects, namely, design of a negative electrode structure is performed, for example, a three-dimensional porous structure is constructed; and secondly, the zinc cathode is protected by a protective layer, such as a metal coating or a polymer coating.
Generally, the method for structurally designing the negative electrode is complex and difficult to operate, and the method for protecting the negative electrode through the protective layer has strong operability. Considering that the polymer coating generally has poor binding property with the zinc cathode, the metal coating is a very efficient strategy for protecting the zinc cathode. The nickel-zinc alloy is an excellent corrosion-resistant coating, has the characteristics of low hydrogen brittleness, high corrosion resistance, high stability, machinability and the like, and has greater advantages than bare zinc and other zinc alloy coatings. At present, the technology for combining the nickel-zinc alloy with the zinc cathode is not perfect enough, the binding property of the coating and the zinc cathode is poor, and the coating is easy to fall off in the process of charging and discharging the battery, so a new preparation method for combining the nickel-zinc alloy with the zinc substrate to improve the performance of the zinc ion battery cathode material is urgently needed to be found.
Disclosure of Invention
The invention aims to solve the technical problems in the prior art and provides a zinc ion battery negative electrode material, a preparation method and application thereof.
In order to solve the technical problems, the technical scheme provided by the invention is as follows:
the invention aims to provide a zinc ion battery cathode material, which is obtained by sequentially compounding a nickel-zinc alloy and a metal nickel layer on the surface of a zinc sheet, wherein the nickel-zinc alloy is Ni2Zn11。
According to the scheme, the total thickness of the nickel-zinc alloy layer and the metal nickel layer is 10-14 mu m.
The second purpose of the invention is to provide a preparation method of the zinc ion battery negative electrode material, which comprises the following specific steps:
1) polishing a zinc sheet by using sand paper, then carrying out ultrasonic treatment in acetone, and finally cleaning by using isopropanol to obtain the treated zinc sheet;
2) adding ammonium chloride and anhydrous nickel chloride into deionized water, and stirring until the ammonium chloride and the anhydrous nickel chloride are completely dissolved to obtain an electrochemical deposition precursor solution;
3) placing the zinc sheet treated in the step 1) as a working electrode, a platinum electrode as a counter electrode and a saturated calomel electrode as a reference electrode in the electrochemical deposition precursor solution obtained in the step 2), performing electrochemical deposition by adopting a three-electrode method, and depositing a nickel layer on the surface of the zinc sheet to obtain a Ni @ Zn composite material;
4) and (3) placing the Ni @ Zn composite material obtained in the step 3) into a tubular furnace for annealing treatment to obtain the nickel-zinc alloy coated zinc base material.
According to the scheme, the concentration of nickel chloride in the electrochemical deposition precursor solution in the step 2) is 0.01-0.2 mol/L, and the molar ratio of ammonium chloride to anhydrous nickel chloride is 10: 0.5 to 1.5.
According to the scheme, the electrochemical deposition process conditions in the step 3) are as follows: the working mode is a constant-voltage electrochemical deposition mode, the deposition voltage is-1 to-1.3V, and the deposition time is 300 to 3600 s.
According to the scheme, the annealing treatment process conditions in the step 4) are as follows: in the nitrogen atmosphere, firstly heating to 130-200 ℃ at a heating rate of 0.5-5 ℃/min, preserving heat for 0.5-3 h, then heating to 220-350 ℃ at a heating rate of 0.5-5 ℃/min, preserving heat for 0.5-3 h, and finally cooling to room temperature at a cooling rate of 0.5-5 ℃/min.
The third purpose of the invention is to provide the application of the zinc ion battery negative electrode material as a zinc ion battery negative electrode material.
The fourth purpose of the invention is to provide a zinc ion battery, which comprises a positive electrode, an electrolyte, a diaphragm and a negative electrode, wherein the negative electrode comprises the zinc ion battery negative electrode material.
Ni-Zn alloy material Ni2Zn11The zinc-based alloy coating has the characteristics of low hydrogen brittleness, high corrosion resistance, high stability, machinability and the like, and has greater advantages than untreated bare zinc and other zinc alloy coatings. The nickel-zinc alloy is combined with the zinc substrate to be used as a negative electrode material of a zinc ion battery, so that the self-corrosion of a zinc negative electrode and the generation of byproducts can be effectively slowed down, and the nickel-zinc alloy layer is prevented from being continuously consumed in the circulating process.
The invention has the beneficial effects that: 1. according to the invention, the nickel-zinc alloy layer is coated on the zinc base through constant-voltage electrodeposition and two-step annealing methods, the nickel-zinc alloy layer and the zinc base are tightly attached to form the nickel-zinc alloy coated zinc base material, the nickel-zinc alloy coated zinc base material used as the zinc ion battery negative electrode material has the characteristics of excellent electrochemical performance, high cycle stability and long cycle life, the problems of dendritic crystal growth, self-corrosion, short cycle life and the like of the zinc ion battery negative electrode material can be solved, and the zinc ion battery negative electrode material has the characteristics of 0.5mA cm and cm-2Under the current density of the nickel-zinc alloy coating zinc base material, the nickel-zinc alloy coating zinc base material can stably run for more than 1900 hours, and the cycle life is obviously prolonged. 2. The preparation method provided by the invention is simple to operate, short in process and low in energy consumption, so that the high-corrosion-resistance nickel-zinc alloy coated zinc base material can be rapidly produced in batches.
Drawings
FIG. 1 is XRD patterns of a zinc sheet treated in step 1), a Ni @ Zn composite material obtained in step 5) and a nickel-zinc alloy coated zinc base material obtained in step 6) in example 1 of the present invention;
FIG. 2 is SEM images of the zinc sheet treated in the step 1), the Ni @ Zn composite material obtained in the step 5) and the Ni-Zn alloy coated zinc base material obtained in the step 6) in the example 1;
FIG. 3 is a sectional view SEM photograph and a cross-sectional element distribution diagram of a nickel-zinc alloy clad zinc base material obtained in example 1;
FIG. 4 is an in-situ optical microscope image of the zinc base material coated with Ni-Zn alloy obtained in step 6) of example 1 and the charging test process of the zinc sheet processed in step 1);
FIG. 5 is a linear corrosion curve of the zinc base material coated with Ni-Zn alloy obtained in step 6) of example 1 and the zinc sheet treated in step 1) tested in a chemical workstation;
FIG. 6 is a voltage-time diagram of a test after assembling a symmetric cell by using the zinc base material coated with the nickel-zinc alloy obtained in step 6) of example 1 and the zinc sheet treated in step 1), respectively;
FIG. 7 shows the concentration of 0.5mA cm in a symmetrical cell assembled by using the Ni-Zn alloy clad Zn base material obtained in step 6) of example 1 and the Zn plate treated in step 1) respectively-1、0.5mAh cm-2XRD patterns of both materials after 50 cycles of the next cycle;
FIG. 8 shows a symmetrical cell assembled at 0.5mA cm using the Ni-Zn alloy clad Zn base material obtained in step 6) of example 1 and the Zn sheet treated in step 1) respectively-1、0.5mAh cm-2SEM images of both materials after 50 cycles of the lower cycle;
fig. 9 is a long cycle test chart of a full battery assembled by using the zinc base material coated with the nickel-zinc alloy obtained in step 6) of the present embodiment or the zinc sheet treated in step 1) as a negative electrode material and manganese dioxide as a positive electrode material.
Detailed Description
The principles and features of this invention are described below in conjunction with specific embodiments, which are set forth merely to illustrate the invention and are not intended to limit the scope of the invention. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
The invention provides a zinc ion battery cathode material, and a preparation method thereof comprises the following steps:
1) polishing a zinc sheet by using sand paper, then carrying out ultrasonic treatment in acetone, and finally cleaning by using isopropanol to obtain the treated zinc sheet;
2) adding ammonium chloride and anhydrous nickel chloride into deionized water, and stirring until the ammonium chloride and the anhydrous nickel chloride are completely dissolved to obtain an electrochemical deposition precursor solution;
3) placing the zinc sheet treated in the step 1) as a working electrode, a platinum electrode as a counter electrode and a saturated calomel electrode as a reference electrode in the electrochemical deposition precursor solution obtained in the step 2), performing electrochemical deposition by adopting a three-electrode method, and depositing a nickel layer on the surface of the zinc sheet to obtain a Ni @ Zn composite material;
4) and (3) placing the Ni @ Zn composite material obtained in the step 3) into a tubular furnace for annealing treatment to obtain the nickel-zinc alloy coated zinc base material.
In the embodiment, the zinc-zinc alloy is coated on the zinc substrate by constant-voltage electrodeposition and a two-step annealing method, and the nickel-zinc alloy layer and the zinc substrate are tightly attached to form the zinc-zinc alloy coated zinc substrate material, so that the zinc-zinc alloy coated zinc substrate material used as the zinc ion battery negative electrode material has the characteristics of excellent electrochemical performance, high cycle stability and long cycle life, can solve the problems of dendritic crystal growth, self-corrosion, short cycle life and the like of the zinc ion battery negative electrode material, and can realize the conditions that the zinc ion battery negative electrode material is short in cycle life and the like at 0.5mA cm-2Under the current density of the nickel-zinc alloy coating zinc base material, the nickel-zinc alloy coating zinc base material can stably run for more than 1900 hours, and the cycle life is obviously prolonged.
In the constant-voltage electrochemical deposition process, the voltage of the electrochemical deposition is in a range of-1V to-1.3V, preferably-1.2V, and the first time period is in a range of 300s to 3600s, preferably 600 s.
Further, the step of putting the Ni @ Zn composite material into a tube furnace for two-step heating annealing treatment to obtain the nickel-zinc alloy coated zinc base material comprises the following steps: and putting the Ni @ Zn composite material into a tubular furnace, heating for a first time period by heating, then heating for a second time period by heating, and cooling to obtain the nickel-zinc alloy coated zinc substrate material.
Specifically, the heating temperature of the first time period is in the range of 130 ℃ to 200 ℃, preferably 140 ℃, the heating rate is in the range of 0.5 ℃/min to 5 ℃/min, preferably 1 ℃/min, and the heating time is in the range of 0.5h to 3h, preferably 1 h; the heating temperature of the second time is in the range of 220 ℃ to 350 ℃, preferably 240 ℃, and the heating rate is inThe heating time is within the range of 0.5 ℃/min to 5 ℃/min, preferably 1 ℃/min, and the heating time is within the range of 0.5h to 3h, preferably 1 h; n at atmospheric pressure (760Torr) throughout the annealing process2(50sccm) in a gas flow, and the cooling rate at the final cooling is in the range of 0.5 to 5 ℃/min, preferably 1 ℃/min.
On the basis of the above embodiments, the present invention provides the following specific examples of the zinc ion battery negative electrode material and the preparation method thereof.
Example 1
A preparation method of a zinc ion battery negative electrode material comprises the following steps:
1) taking a zinc sheet (the thickness is 0.2mm) with the area of 1cm multiplied by 2cm, polishing the zinc sheet by using 2000-mesh abrasive paper, then carrying out ultrasonic treatment on the zinc sheet in acetone for 30min, and finally cleaning the zinc sheet with isopropanol for three times to remove surface pollution to obtain a treated zinc sheet;
2) weighing 2.675g of ammonium chloride and 0.648g of anhydrous nickel chloride, adding into 50mL of deionized water, and stirring for 3 hours at room temperature until the ammonium chloride and the anhydrous nickel chloride are completely dissolved to obtain an electrochemical deposition precursor solution;
3) an electrochemical deposition platform is built by adopting a three-electrode method, the zinc sheet treated in the step 1) is used as a working electrode, a platinum electrode is used as a counter electrode, a saturated calomel electrode is used as a reference electrode, and the three electrodes are immersed into the electrochemical deposition precursor solution obtained in the step 2) to the same depth;
4) opening the electrochemical workstation, setting the working mode to be a constant-voltage electrochemical deposition mode, setting the voltage to be-1.2V and the deposition time to be 600s, starting the electrochemical workstation, taking out the working electrode after the electrochemical workstation stops working, and respectively cleaning the working electrode with deionized water and ethanol for three times;
5) wrapping the cleaned working electrode with filter paper, and naturally drying the wrapped working electrode in a ventilated place to obtain the Ni @ Zn composite material;
6) putting the Ni @ Zn composite material into a tube furnace, and introducing N2Setting a program to carry out annealing treatment, heating to 140 ℃ at a heating rate of 1 ℃/min, preserving heat for 1h, heating to 240 ℃ at a heating rate of 1 ℃/min, preserving heat for 1h, cooling at a cooling rate of 1 ℃/min, and taking the mixture after the temperature is reduced to room temperatureAnd obtaining a sample, namely the nickel-zinc alloy coated zinc substrate material.
In this embodiment, X-ray diffraction (XRD) patterns of the zinc sheet (B-Zn) treated in step 1), the Ni @ Zn composite material (Ni @ Zn) obtained in step 5) and the nickel-zinc alloy clad zinc base material (Ni-Zn alloy) obtained in step 6) are shown in fig. 1, and the XRD patterns indicate that a nickel peak can be detected by the Ni @ Zn composite material, and correspond to PDF # 87-0712; the peak of the nickel-zinc alloy can be detected by the nickel-zinc alloy coating zinc base material, which corresponds to PDF #03-065-2Zn11After the constant-pressure electrochemical deposition, a nickel layer is successfully plated on the zinc substrate, and after the two-step annealing treatment, part of the nickel layer and the zinc substrate are combined to generate the nickel-zinc alloy. Zn, Ni and Ni can be observed from the XRD curve of the zinc base material coated by the nickel-zinc alloy2Zn11Three different peaks, indicating that the final sample contains Zn, Ni2Zn11And Ni, namely the Ni-Zn alloy is a Zn layer and Ni2Zn11Sandwich structure of layers and Ni layers.
In this embodiment, the surface appearances of the zinc sheet (bare zinc) treated in step 1), the Ni @ Zn composite material obtained in step 5), and the nickel-zinc alloy coated zinc base material obtained in step 6) are shown in fig. 2, and compared with the smooth surface of bare zinc, the surface of the Ni @ Zn composite material obtained by constant-pressure electrochemical deposition is locally and uniformly distributed, but has fine stripe ravines, and prismatic particles on the surface of the nickel-zinc alloy coated zinc base material formed after further two-step heating and annealing treatment are finer and more uniformly distributed. From the cross section (figure 3 left) of the nickel-zinc alloy coated zinc substrate material, it can be clearly observed that the thickness of the whole coating is about 12 μm, and the coating is tightly connected with the zinc substrate, which shows that the binding property of the coating and the zinc substrate is very excellent. However, since the interface is not sufficiently sharp because the nickel-zinc alloy layer is closely connected to the zinc layer and the nickel layer, only the thickness of the overall plating layer can be observed by SEM. The element distribution diagrams of the cross-sectional views of the zinc base material coated with the nickel-zinc alloy in the middle and right of fig. 3 are respectively, and the thickness of the coating layer is about 12 μm.
The nickel-zinc alloy coated zinc substrate material prepared by the invention can be used for a zinc ion battery negative electrode material and is symmetrically chargedTesting the performance of the cell, selecting 2M ZnSO4The solution is used as electrolyte, GF/A glass fiber is used as a diaphragm, and a CR2016 type battery shell is assembled into a button cell.
Assembling the zinc base material coated with the nickel-zinc alloy obtained in the step 6) or the zinc sheet treated in the step 1) through an in-situ mold, and then performing chemical processing at a working station at a speed of 10mA cm-2The current density of (a) was tested for charging for 20min and observed in real time by optical microscopy, with in situ optical microscopy of the two materials at different time periods as shown in figure 4. The corrosion of the bare zinc can be observed in 4min, and the corrosion phenomenon of the bare zinc cathode is obviously aggravated after the reaction is carried out for 20 min. In contrast, no corrosion phenomenon is observed even after 20min, which shows that the zinc base material coated by the nickel-zinc alloy can control the generation of by-products, reduce the corrosion phenomenon and has high corrosion resistance. It can also be seen after 20min that the zinc dendrites of the nickel zinc alloy clad zinc base material grow more uniformly than bare zinc.
Also under the chemical workstation, three electrodes are used at 2M ZnSO4The linear corrosion test is performed in the electrolyte, the nickel-zinc alloy coated zinc-based base material obtained in step 6) of this embodiment or the zinc sheet processed in step 1) is used as a working electrode, the foil is used as a counter electrode, and the saturated calomel electrode is used as a reference electrode, and the obtained linear corrosion curve is shown in fig. 5, which indicates that the nickel-zinc alloy coated zinc-based base material can significantly reduce the corrosion current, thereby slowing down the corrosion rate. The test result shows that the nickel-zinc alloy coated zinc base material can slow down the corrosion of the zinc cathode.
The symmetric cell is assembled by using the nickel-zinc alloy coated zinc base material obtained in the step 6) of the embodiment or the zinc sheet treated in the step 1), the long-term cycling stability of the two materials is tested by observing the electroplating/stripping behavior of zinc in the symmetric cell, and a 2016 type button cell is selected for assembly. The voltage-time diagram of two symmetrical cells is shown in FIG. 6, and the test results show that the cells are at 0.5mA cm-2Current density of 0.5mAh cm-2Although the difference of initial polarization between the nickel-zinc alloy clad zinc base material and the bare zinc is not clearObviously, the voltage is about 38mV, but a symmetrical battery prepared by the zinc base material coated by the nickel-zinc alloy shows excellent cycle stability, can stably run for more than 1900h, and has obviously prolonged cycle life. Even more surprising is that the polarization voltage of a symmetrical cell made with a zinc base material coated with a nickel zinc alloy dropped to 24mV after 1900 hours. The inset shows a detailed voltage curve, indicating that the polarization tends to decrease with increasing number of cycles.
FIG. 7 shows the current cell density at 0.5mA cm for a symmetrical cell assembled by using the Ni-Zn alloy clad Zn base material obtained in step 6) or the Zn plate treated in step 1) of the present example-1、0.5mAh cm-2The XRD patterns of the two materials after 50 cycles of lower circulation show that the peaks of zinc hydroxyl sulfate by-products can be obviously observed in the XRD patterns of the bare zinc after 50 cycles of circulation, and the peaks of the zinc base material coated by the nickel-zinc alloy about the by-products are not obvious, which shows that the zinc cathode can be well protected by the zinc base material coated by the nickel-zinc alloy, and the generation of the by-products is reduced.
FIG. 8 shows the current cell density at 0.5mA cm for a symmetrical cell assembled by using the Ni-Zn alloy clad Zn base material obtained in step 6) or the Zn plate treated in step 1) of the present example-1、0.5mAh cm-2And SEM images of the two materials after 50 cycles of lower circulation show that the nucleation size of zinc on the surface of the bare zinc is obviously larger than that of the zinc base material coated with the nickel-zinc alloy under the same magnification, which shows that the zinc base material coated with the nickel-zinc alloy can well control the nucleation growth of zinc and slow down the generation of zinc dendrites.
FIG. 9 is a long cycle test chart of a full cell assembled by using the Ni-Zn alloy coated Zn base material obtained in step 6) or the Zn plate treated in step 1) as a negative electrode material and manganese dioxide as a positive electrode material, wherein the full cell of the Ni-Zn alloy coated Zn base material is shown in 1A g-1Can stably operate and circulate 1000 times under the current density, and the discharge capacity is from the initial 101mAh g-1Increased to 154mAh g at turn 20-1Finally, 123mAh g was maintained in the 1000 th cycle-1The capacity retention rate was 79.8%. While the capacity of the bare zinc full cell is 140mAh g from the first-1After 1000 cycles, the concentration is reduced to 76mAh g-1Capacity retention of only54.2％。
Example 2
A preparation method of a zinc ion battery negative electrode material comprises the following steps:
1) taking a zinc sheet with the area of 1cm multiplied by 2cm, polishing the zinc sheet by using 2000-mesh abrasive paper, then carrying out ultrasonic treatment in acetone for 0.5h, and finally cleaning the zinc sheet for three times by using isopropanol to remove surface pollution to obtain a treated zinc sheet;
2) weighing 2.675g of ammonium chloride and 0.648g of anhydrous nickel chloride, adding into 50mL of deionized water, and stirring at room temperature for 3h until the ammonium chloride and the anhydrous nickel chloride are completely dissolved to obtain an electrochemical deposition precursor solution;
3) an electrochemical deposition platform is built by adopting a three-electrode method, the zinc sheet treated in the step 1) is used as a working electrode, a platinum electrode is used as a counter electrode, a saturated calomel electrode is used as a reference electrode, and the three electrodes are immersed into the electrochemical deposition precursor solution obtained in the step 2) to the same depth;
4) opening the electrochemical workstation, setting the working mode to be a constant-voltage electrochemical deposition mode, setting the voltage to be-1.2V and the deposition time to be 1800s, then starting the electrochemical workstation, taking out the working electrode after the electrochemical workstation stops working, and respectively cleaning the working electrode with deionized water and ethanol for three times;
5) wrapping the cleaned working electrode with filter paper, and naturally drying in a ventilated place to obtain the Ni @ Zn composite material;
6) putting the Ni @ Zn composite material into a tube furnace, and introducing N2Setting a program, firstly heating to 150 ℃ at a heating rate of 1 ℃/min, preserving heat for 1h, then heating to 270 ℃ at a heating rate of 2 ℃/min, preserving heat for 1h, finally cooling at a cooling rate of 1 ℃/min, and taking out after the temperature is reduced to room temperature, wherein the obtained sample is the nickel-zinc alloy coated zinc-based base material.
The positive electrode and the negative electrode materials are all assembled into a symmetrical battery by adopting the zinc base material coated by the nickel-zinc alloy obtained in the embodiment, and the concentration of the zinc base material is 0.5mA cm-1Under the current density, the circulation can stably run for more than 1200 h.
Example 3
A preparation method of a zinc ion battery negative electrode material comprises the following steps:
1) taking a zinc sheet with the area of 1cm multiplied by 2cm, polishing the zinc sheet by using 2000-mesh abrasive paper, then carrying out ultrasonic treatment in acetone for 0.5h, and finally cleaning the zinc sheet by using isopropanol for three times to remove surface pollution to obtain the treated zinc sheet;
2) weighing 2.675g of ammonium chloride and 0.648g of anhydrous nickel chloride, adding into 50mL of deionized water, and stirring for 3 hours at room temperature until the ammonium chloride and the anhydrous nickel chloride are completely dissolved to obtain an electrochemical deposition precursor solution;
3) an electrochemical deposition platform is built by adopting a three-electrode method, the zinc sheet treated in the step 1) is used as a working electrode, a platinum electrode is used as a counter electrode, a saturated calomel electrode is used as a reference electrode, and the three electrodes are immersed into the electrochemical deposition precursor solution obtained in the step 2) to the same depth;
4) opening the electrochemical workstation, setting the working mode to be a constant-voltage electrochemical deposition mode, setting the voltage to be-1.1V and the deposition time to be 3600s, then starting the electrochemical workstation, taking out the working electrode after the electrochemical workstation stops working, and respectively cleaning the working electrode with deionized water and ethanol for three times;
5) wrapping the cleaned working electrode with filter paper, and naturally drying the wrapped working electrode in a ventilated place to obtain the Ni @ Zn composite material;
6) putting the Ni @ Zn composite material into a tube furnace, and introducing N2Setting a program, firstly heating to 130 ℃ at a heating rate of 2 ℃/min, preserving heat for 1h, then heating to 300 ℃ at a heating rate of 1 ℃/min, preserving heat for 1h, finally cooling at a cooling rate of 2 ℃/min, and taking out after the temperature is reduced to room temperature, wherein the obtained sample is the nickel-zinc alloy coated zinc base material.
The positive electrode and the negative electrode materials are all assembled into a symmetrical battery by adopting the zinc base material coated by the nickel-zinc alloy obtained in the embodiment, and the concentration of the zinc base material is 0.5mA cm-1Under the current density, the circulation can stably run for more than 800 h.
Example 4
A preparation method of a zinc ion battery negative electrode material comprises the following steps:
1) taking a zinc sheet with the area of 1cm multiplied by 2cm, polishing the zinc sheet by using 2000-mesh abrasive paper, then carrying out ultrasonic treatment in acetone for 0.5h, and finally cleaning the zinc sheet for three times by using isopropanol to remove surface pollution to obtain the treated zinc sheet;
2) weighing 2.675g of ammonium chloride and 0.648g of anhydrous nickel chloride, adding into 50mL of deionized water, and stirring at room temperature for 3h until the ammonium chloride and the anhydrous nickel chloride are completely dissolved to obtain an electrochemical deposition precursor solution;
3) an electrochemical deposition platform is built by adopting a three-electrode method, the zinc sheet treated in the step 1) is used as a working electrode, a platinum electrode is used as a counter electrode, a saturated calomel electrode is used as a reference electrode, and the three electrodes are immersed into the electrochemical deposition precursor solution obtained in the step 2) to the same depth;
4) opening the electrochemical workstation, setting the working mode to be a constant-voltage electrochemical deposition mode, setting the voltage to be-1.3V and the deposition time to be 600s, then starting the electrochemical workstation, taking out the working electrode after the electrochemical workstation stops working, and respectively cleaning the working electrode with deionized water and ethanol for three times;
5) wrapping the cleaned working electrode with filter paper, and naturally drying the wrapped working electrode in a ventilated place to obtain the Ni @ Zn composite material;
6) putting the Ni @ Zn composite material into a tube furnace, and introducing N2Setting a program, firstly heating to 140 ℃ at a heating rate of 2 ℃/min, preserving heat for 1h, then heating to 250 ℃ at a heating rate of 2 ℃/min, preserving heat for 1h, finally cooling at a cooling rate of 1 ℃/min, and taking out after the temperature is reduced to room temperature, wherein the obtained sample is the nickel-zinc alloy coated zinc-based base material.
The positive electrode and the negative electrode materials are all assembled into a symmetrical battery by adopting the zinc base material coated by the nickel-zinc alloy obtained in the embodiment, and the concentration of the zinc base material is 0.5mA cm-1Under the current density, the circulation can stably run for nearly 900 h.
Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention, and that variations, modifications, substitutions and alterations can be made to the above embodiments by those of ordinary skill in the art within the scope of the present invention.
Claims (8)
1. The zinc ion battery negative electrode material is characterized in that zinc ions are used for electrolysisThe cell cathode material is obtained by sequentially compounding a nickel-zinc alloy and a metal nickel layer on the surface of a zinc sheet, wherein the nickel-zinc alloy comprises the component Ni2Zn11。
2. The negative electrode material of the zinc-ion battery as claimed in claim 1, wherein the total thickness of the nickel-zinc alloy layer and the metal nickel layer is 10-14 μm.
3. The preparation method of the zinc ion battery negative electrode material as claimed in claim 1 or 2, which is characterized by comprising the following specific steps:
1) polishing a zinc sheet by using sand paper, then carrying out ultrasonic treatment in acetone, and finally cleaning by using isopropanol to obtain the treated zinc sheet;
2) adding ammonium chloride and anhydrous nickel chloride into deionized water, and stirring until the ammonium chloride and the anhydrous nickel chloride are completely dissolved to obtain an electrochemical deposition precursor solution;
3) placing the zinc sheet treated in the step 1) as a working electrode, a platinum electrode as a counter electrode and a saturated calomel electrode as a reference electrode in the electrochemical deposition precursor solution obtained in the step 2), performing electrochemical deposition by adopting a three-electrode method, and depositing a nickel layer on the surface of the zinc sheet to obtain a Ni @ Zn composite material;
4) and (3) placing the Ni @ Zn composite material obtained in the step 3) into a tubular furnace for annealing treatment to obtain the nickel-zinc alloy coated zinc base material.
4. The preparation method of the negative electrode material of the zinc-ion battery according to claim 3, wherein the concentration of nickel chloride in the electrochemical deposition precursor solution in the step 2) is 0.01-0.2 mol/L, and the molar ratio of ammonium chloride to anhydrous nickel chloride is 10: 0.5 to 1.5.
5. The preparation method of the negative electrode material of the zinc-ion battery as claimed in claim 3, wherein the electrochemical deposition process conditions in step 3) are as follows: the working mode is a constant-voltage electrochemical deposition mode, the deposition voltage is-1 to-1.3V, and the deposition time is 300 to 3600 s.
6. The preparation method of the negative electrode material of the zinc-ion battery according to claim 3, wherein the annealing treatment process conditions in the step 4) are as follows: in the nitrogen atmosphere, firstly heating to 130-200 ℃ at a heating rate of 0.5-5 ℃/min, preserving heat for 0.5-3 h, then heating to 220-350 ℃ at a heating rate of 0.5-5 ℃/min, preserving heat for 0.5-3 h, and finally cooling to room temperature at a cooling rate of 0.5-5 ℃/min.
7. Use of the zinc ion battery negative electrode material of claim 1 or 2 as a zinc ion battery negative electrode material.
8. A zinc ion battery comprising a positive electrode, an electrolyte, a separator and a negative electrode, wherein the negative electrode comprises the zinc ion battery negative electrode material according to claim 1 or 2.
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| TW385566B (en) * | 1998-04-28 | 2000-03-21 | Energy Consortium Holding Llc | A rechargeable battery having a plated Zinc/Zinc oxide electrode and a method for manufacturing the same |
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