CN114927632B - Modified zinc metal sheet and preparation method and application thereof - Google Patents
Modified zinc metal sheet and preparation method and application thereof Download PDFInfo
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- CN114927632B CN114927632B CN202210529535.2A CN202210529535A CN114927632B CN 114927632 B CN114927632 B CN 114927632B CN 202210529535 A CN202210529535 A CN 202210529535A CN 114927632 B CN114927632 B CN 114927632B
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- 229910052751 metal Inorganic materials 0.000 title claims abstract description 50
- 239000002184 metal Substances 0.000 title claims abstract description 50
- 150000003751 zinc Chemical class 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 76
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 76
- 239000011701 zinc Substances 0.000 claims abstract description 76
- 238000000034 method Methods 0.000 claims abstract description 26
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 230000008569 process Effects 0.000 claims abstract description 10
- 150000002500 ions Chemical class 0.000 claims description 45
- 238000002347 injection Methods 0.000 claims description 38
- 239000007924 injection Substances 0.000 claims description 38
- 238000005468 ion implantation Methods 0.000 claims description 17
- 238000001816 cooling Methods 0.000 claims description 15
- 238000002513 implantation Methods 0.000 claims description 11
- 239000013077 target material Substances 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 244000137852 Petrea volubilis Species 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 238000005516 engineering process Methods 0.000 claims description 6
- 238000005498 polishing Methods 0.000 claims description 6
- 229910001297 Zn alloy Inorganic materials 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims 4
- 238000010438 heat treatment Methods 0.000 claims 2
- 210000001787 dendrite Anatomy 0.000 abstract description 9
- 239000003792 electrolyte Substances 0.000 abstract description 5
- 230000007797 corrosion Effects 0.000 abstract description 4
- 238000005260 corrosion Methods 0.000 abstract description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 3
- 238000003487 electrochemical reaction Methods 0.000 abstract description 3
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 3
- 239000001257 hydrogen Substances 0.000 abstract description 3
- 230000002829 reductive effect Effects 0.000 abstract description 2
- 238000007086 side reaction Methods 0.000 abstract description 2
- 239000000758 substrate Substances 0.000 description 15
- 229910045601 alloy Inorganic materials 0.000 description 9
- 239000000956 alloy Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 229910052802 copper Inorganic materials 0.000 description 5
- 238000002715 modification method Methods 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 238000011161 development Methods 0.000 description 4
- 238000007599 discharging Methods 0.000 description 4
- 230000000630 rising effect Effects 0.000 description 4
- 229910052709 silver Inorganic materials 0.000 description 4
- 238000009210 therapy by ultrasound Methods 0.000 description 4
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000002161 passivation Methods 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000006087 Silane Coupling Agent Substances 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 210000004027 cell Anatomy 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910000905 alloy phase Inorganic materials 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
- 238000010891 electric arc Methods 0.000 description 1
- 238000012983 electrochemical energy storage Methods 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000010884 ion-beam technique Methods 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000005486 organic electrolyte Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000010587 phase diagram Methods 0.000 description 1
- 230000005501 phase interface Effects 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 description 1
- 229910000165 zinc phosphate Inorganic materials 0.000 description 1
- -1 zinc phosphate-silane Chemical compound 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 229960001763 zinc sulfate Drugs 0.000 description 1
- 229910000368 zinc sulfate Inorganic materials 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
-
- 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
- H01M4/0421—Methods of deposition of the material involving vapour deposition
- H01M4/0423—Physical vapour deposition
-
- 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
Abstract
The invention discloses a modified zinc metal sheet and a preparation method and application thereof. The modified zinc metal sheet provided by the invention can form a stable and mild electrode/electrolyte interface on the surface of a zinc electrode, so that zinc ions are uniformly deposited in the electrochemical reaction process of the battery, the growth of zinc dendrites on the negative electrode side is greatly inhibited, and the occurrence of side reactions such as corrosion, hydrogen evolution and the like is reduced, thereby prolonging the charge-discharge cycle life of the water-based zinc ion battery.
Description
Technical Field
The invention belongs to the technical field of zinc ion batteries, and particularly relates to a modified zinc metal sheet and a preparation method and application thereof.
Background
With the development of human society, high-energy density lithium ion batteries have occupied the commercial rechargeable battery market, but the problems of limited lithium resources, high cost, unsafe large-scale organic electrolyte and the like limit the further development of the lithium ion batteries. Therefore, development of a new secondary battery that is safe, environmentally friendly and low in cost is a current trend.
The water-based zinc ion battery is considered to be a novel electrochemical energy storage device with the highest potential and application prospect due to the characteristics of low cost, high safety, simple operation, environmental friendliness and the like. However, when the metal zinc sheet is directly used as the cathode material of the novel water-based secondary zinc ion battery in neutral or weak acid electrolyte, the problems of hydrogen evolution, corrosion, passivation, dendrite growth and the like still exist, and the adverse effects on the capacity, coulomb efficiency and cycle performance of the battery are generated, so that the development and practical application of the zinc-based water-based battery are severely restricted.
In order to solve the existing problems, scientific researchers propose strategies for improving the stability of the traditional solid-liquid interface of the zinc cathode from different angles through analysis of an interface dendrite growth mechanism. For example, the method based on the modification of the zinc cathode electrode plate, the composition of electrolyte, the design of a diaphragm and the like are optimized to improve the reversibility in the zinc electroplating/stripping process and prolong the cycle life of the electrode. Surface modification of the negative electrode is also an effective strategy, attracting researchers' attention. For example, CN113690401a discloses a zinc metal negative electrode modified by an organic zinc phosphate-silane composite passivation film, and a preparation method and application thereof. By utilizing the characteristic that the silane coupling agent is hydrolyzed into silanol in water, after the silane coupling agent and the organic phosphoric acid chelating agent are uniformly mixed, metal zinc is added to carry out chemical reaction, and an organic zinc phosphate chelate-silane composite passivation film is generated on the surface of the zinc metal negative electrode in situ, so that the modified zinc metal negative electrode is obtained, and the uncontrollable dendrite growth of the zinc metal negative electrode can be obviously inhibited. However, the cost of the negative electrode for inhibiting dendrite growth prepared by the method is too high, and the applied organic compound method obviously cannot be produced in a large scale. In addition, CN113066990A discloses a preparation method and application of the zinc cathode modified three-dimensional current collector,the preparation method specifically comprises the following steps: firstly, depositing nano silver simple substance particles on the surface of a current collector by utilizing silver mirror reaction, and then applying certain current to the modified current collector by utilizing an electrochemical alloying method so as to enable part or even all of the nano silver particles on the surface to be converted into AgZn 3 The alloy phase interface layer can obtain the zinc negative electrode modified three-dimensional current collector, which can obviously inhibit the growth of zinc negative electrode dendrites and greatly prolong the cycle life of the zinc ion battery. However, the preparation method is limited by the constraint of a balance phase diagram, the chemical binding force, the solid solubility and the like, and the preparation process is complex.
It can be seen that there is still a need for more intensive research to construct a zinc metal anode with excellent properties and which is simpler and easier to implement.
Disclosure of Invention
Aiming at the defects or improvement demands of the prior art, the invention aims to provide a modified zinc metal sheet, a preparation method and application thereof, wherein a metal vapor vacuum ion source (MEVVA) ion implantation technology is adopted to dope metal ions into a pure zinc or zinc alloy sheet to obtain a modified zinc metal anode in a water system zinc ion battery.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
the invention relates to a preparation method of a modified zinc metal sheet, which is characterized in that doping ions are injected into the zinc metal sheet to obtain the modified zinc metal sheet, wherein the doping ions are at least one selected from Cu, al, sn, ag.
The inventors found that by using at least one of Cu, al, sn and Ag as a dopant ion source, the electrochemical properties of the finally obtained modified zinc sheet are optimal.
Preferably, the zinc metal in the zinc metal sheet is selected from pure zinc or zinc alloy, preferably pure zinc.
In a preferred scheme, the zinc metal sheet is pretreated firstly, and the pretreatment process is as follows: firstly, adopting metallographic sand paper and a polishing machine to sequentially polish and polish the zinc metal sheet, then using absolute ethyl alcohol to ultrasonically clean for more than 10 minutes, and drying by hot air. The surface natural oxide film and impurities are removed by pretreatment.
Preferably, the implantation of the doped ions adopts MEVVA source ion implantation technology.
Preferably, the doped ions are injected, the target material is selected from at least one of Cu, al, sn, ag targets, and the purity of the target material is more than 99.9%.
Preferably, the injection is performed by: the working vacuum degree is less than or equal to 4 multiplied by 10 -3 Pa, injection voltage of 40-50kV, and injection dosage of 1×10 15 -1×10 16 ions·cm -2 。
The inventor finds that under the process conditions, the implantation of doping ions is carried out, the implantation dosage is controlled within the range, and the electrochemical performance of the finally obtained modified zinc metal sheet is optimal.
Preferably, the temperature of the zinc metal sheet is controlled to be 25-50 ℃ during the injection.
Further preferably, the temperature of the zinc sheet is raised to 25-50 ℃ at a temperature rising rate of 30-35 ℃/h, then doping ions are implanted, and after the implantation is completed, the zinc sheet is cooled to room temperature at a temperature falling rate of 15-20 ℃/h.
The cooling speed is controlled within the range, so that residual stress in the sample can be avoided, and adverse effects of the residual stress on the stress corrosion resistance, the dimensional stability, the service life and the like of the sample are avoided.
In the actual operation process, after the injection is completed, the ion source and the vacuum device are closed, and the alloy is taken out after the furnace is cooled to room temperature.
The invention also provides the modified zinc metal sheet prepared by the preparation method.
The invention also provides application of the modified zinc metal sheet prepared by the preparation method, and the modified zinc metal sheet is assembled into a symmetrical battery or used as a negative electrode in a water-based zinc ion battery.
When the implantation of doped ions is used as a negative electrode in an aqueous zinc ion battery, CNT/MnO is used as a negative electrode 2 Or V 2 O 5 As the positive electrode.
The invention has the following beneficial effects:
(1) The invention relates to a surface modification method of a zinc metal negative electrode for a water system zinc ion battery, which adopts an ion implantation technology of an MEVVA ion source which is successfully developed by a metal vapor vacuum arc discharge technology principle. The ion beam implantation technology is characterized in that ions generated by an ion generating device are led out through tens of thousands of volts to form high-energy ions, the high-energy ions are implanted into the surface of a substrate and then collide with electric nuclei and electrons in the substrate, and when the energy of the ions is lost to energy exhaustion, the ions are used as doping atoms to stay in the substrate. The ion implantation method is a powerful implantation method, which is not affected by the solid solubility of the base material and can accurately dope any element. The ion implantation temperature can be changed at will, the implantation process is carried out under high vacuum, the surface of the substrate is not oxidized, the substrate is not deformed, and the surface roughness after implantation is not changed obviously. The doping depth can be controlled by changing the energy, and the repeatability is good. The implanted ions are directly combined with atoms or molecules near the surface of the material, have no clear interface with the substrate material, are mutually fused and firmly combined, and cannot generate stripping phenomenon.
(2) The zinc cathode after one or more ion implantation of Cu, al, sn and Ag generally has larger specific surface area, which increases zinc deposition sites in the electrochemical reaction process, inhibits the growth of zinc dendrites and other products and improves reaction kinetics. The invention can form stable and mild electrode/electrolyte interface on the surface of the zinc electrode, so that zinc ions are uniformly deposited in the electrochemical reaction process of the battery, the growth of zinc dendrites on the negative electrode side is greatly inhibited, and side reactions such as corrosion, hydrogen evolution and the like are reduced, thereby prolonging the charge-discharge cycle life of the water-based zinc ion battery.
(3) The preparation process is environment-friendly, the process parameters can be accurately controlled, the obtained modified layer has compact and uniform structure, strong binding force with a zinc substrate, no obvious interface and stable and reliable performance.
Drawings
Fig. 1 is a graph showing time-voltage comparison of a symmetric battery assembled by Cu ion implantation modified anode tabs obtained in example 1 with a symmetric battery assembled by pure zinc sheets.
Fig. 2 is a graph showing time-voltage comparison of a symmetric battery assembled by the Cu ion-implanted modified anode tabs obtained in example 2 with a symmetric battery assembled by pure zinc sheets.
Fig. 3 is a graph showing time-voltage comparison between a symmetrical battery assembled by Al ion implantation modified anode tabs obtained in example 3 and a symmetrical battery assembled by pure zinc sheets.
Fig. 4 is a time-voltage comparison graph of a symmetrical battery assembled by Al ion implantation modified anode tabs obtained in example 4 and a symmetrical battery assembled by pure zinc sheets.
Fig. 5 is a graph showing time-voltage comparison between a symmetrical battery assembled by the Sn ion-implanted modified negative electrode tabs obtained in example 5 and a symmetrical battery assembled by pure zinc sheets.
Fig. 6 is a time-voltage comparison graph of a symmetrical battery assembled by the Sn ion-implanted modified negative electrode tabs obtained in example 6 and a symmetrical battery assembled by pure zinc sheets.
Fig. 7 is a graph showing time-voltage comparison of a symmetrical battery assembled by Ag ion implantation modified anode tabs obtained in example 7 with a symmetrical battery assembled by pure zinc sheets.
Fig. 8 is a graph showing time-voltage comparison of a symmetrical battery assembled by Ag ion implantation modified anode tabs obtained in example 8 with a symmetrical battery assembled by pure zinc sheets.
Fig. 9 is a time-voltage comparison graph of a symmetrical battery assembled by the Sn ion-implanted modified anode tabs obtained in comparative example 1 and a symmetrical battery assembled by pure zinc sheets.
Fig. 10 is a time-voltage comparison graph of a symmetrical battery assembled by Ag ion injection modified anode tabs obtained in comparative example 2 and a symmetrical battery assembled by pure zinc sheets.
Detailed Description
The present invention will be described in further detail with reference to examples.
Example 1:
the embodiment provides a surface modification method of a zinc metal negative electrode for a water-based zinc ion battery, and the water-based zinc ion battery alloy negative electrode prepared by the method. The method comprises the following steps:
(1) Pretreatment: adopting metallographic sand paper and a polishing machine of different types to polish and polish the pure zinc sheet, placing the pure zinc sheet in an absolute ethanol solution for ultrasonic treatment for 10 minutes, and drying the pure zinc sheet by hot air;
(2) Performing Cu ion implantation on the pretreated pure zinc substrate, wherein the purity of a Cu target material is more than 99.9%, and the working vacuum degree is 4 multiplied by 10 -3 Pa, injection voltage of 40kV, and injection dose of 1×10 15 ions·cm -2 The substrate temperature was 25 ℃.
(3) And after the implantation is finished, the ion source and the vacuum device are closed, the ion source and the vacuum device are waited to be cooled to the room temperature, the cooling speed is controlled to be 20 ℃/h, and the alloy is taken out after the ion source and the vacuum device reach the room temperature, so that the Cu ion implantation modified anode is obtained.
Example 2:
the difference between this example and example 1 is that the injection voltage was 50kV and the injection dose was 1X 10 16 ions·cm -2 。
Example 3:
the embodiment provides a surface modification method of a zinc metal negative electrode for a water-based zinc ion battery, and the water-based zinc ion battery alloy negative electrode prepared by the method. The method comprises the following steps:
(1) Pretreatment: adopting metallographic sand paper and a polishing machine of different types to polish and polish the pure zinc sheet, placing the pure zinc sheet in an absolute ethanol solution for ultrasonic treatment for 10 minutes, and drying the pure zinc sheet by hot air;
(2) Carrying out Al ion implantation on the pretreated pure zinc substrate, wherein the purity of an Al target material is more than 99.9%, and the working vacuum degree is 4 multiplied by 10 -3 Pa, injection voltage of 40kV, and injection dose of 1×10 15 ions·cm -2 The substrate temperature is 30 ℃, and the temperature rising speed is 30 ℃/h.
(3) And after the injection is finished, the ion source and the vacuum device are closed, the cooling is waited to the room temperature, the cooling speed is controlled to be 20 ℃/h, and the alloy is taken out after the cooling reaches the room temperature, so that the Al ion injection modified cathode is obtained.
Example 4:
the difference between this example and example 3 is that the injection voltage was 50kV and the injection dose was 1X 10 16 ions·cm -2 。
Example 5:
the embodiment provides a surface modification method of a zinc metal negative electrode for a water-based zinc ion battery, and the water-based zinc ion battery alloy negative electrode prepared by the method. The method comprises the following steps:
(1) Pretreatment: adopting metallographic sand paper and a polishing machine of different types to polish and polish the pure zinc sheet, placing the pure zinc sheet in an absolute ethanol solution for ultrasonic treatment for 10 minutes, and drying the pure zinc sheet by hot air;
(2) Carrying out Sn ion implantation on the pretreated pure zinc substrate, wherein the purity of a Sn target material is more than 99.9%, and the working vacuum degree is 4 multiplied by 10 -3 Pa, injection voltage of 40kV, and injection dose of 1×10 15 ions·cm -2 The substrate temperature is 40 ℃, and the temperature rising speed is 35 ℃/h.
(3) And after the injection is finished, the ion source and the vacuum device are closed, the cooling is waited to the room temperature, the cooling speed is controlled to be 15 ℃/h, and the alloy is taken out after the cooling reaches the room temperature, so that the Sn ion injection modified anode is obtained.
Example 6:
the difference between this example and example 5 is that the injection voltage was 50kV and the injection dose was 1X 10 16 ions·cm -2 。
Example 7:
the embodiment provides a surface modification method of a zinc metal negative electrode for a water-based zinc ion battery, and the water-based zinc ion battery alloy negative electrode prepared by the method. The method comprises the following steps:
(1) Pretreatment: adopting metallographic sand paper and a polishing machine of different types to polish and polish the pure zinc sheet, placing the pure zinc sheet in an absolute ethanol solution for ultrasonic treatment for 10 minutes, and drying the pure zinc sheet by hot air;
(2) Carrying out Ag ion implantation on the pretreated pure zinc substrate, wherein the purity of an Ag target material is more than 99.9%, and the working vacuum degree is 4 multiplied by 10 -3 Pa, injection voltage of 40kV, and injection dosage of1×10 15 ions·cm -2 The substrate temperature is 50 ℃, and the temperature rising speed is 35 ℃/h.
(3) And after the injection is finished, the ion source and the vacuum device are closed, the cooling is waited to the room temperature, the cooling speed is controlled to be 15 ℃/h, and the alloy is taken out after the cooling reaches the room temperature, so that the Ag ion injection modified anode is obtained.
Example 8:
the difference between this example and example 7 is that the injection voltage was 50kV and the injection dose was 1X 10 16 ions·cm -2 。
Comparative example 1:
the comparative example differs from example 5 only in that the injection voltage was 50kV and the injection dose was 1X 10 17 ions·cm -2 And discharging air after injection is completed, discharging from the furnace, and air cooling to room temperature.
Comparative example 2:
the comparative example differs from example 7 only in that the injection voltage was 50kV and the injection dose was 1X 10 17 ions·cm -2 And discharging air after injection is completed, discharging from the furnace, and air cooling to room temperature.
The symmetrical button cell with CR2032 assembled by two zinc sheets prepared in each example and comparative example is compared with the symmetrical cell assembled by two cleaned pure zinc sheets, and the method uses a Wuhan blue CT 2001A system to make a current of 1mA cm -2 Current density, 1 mAh.cm -2 The electrochemical deposition/stripping cycle performance test was performed at the capacitance of (c). The electrolyte is 2M zinc sulfate, and the diaphragm is glass fiber filter paper.
As a result, as shown in fig. 1 to 10, the overpotential of the symmetrical battery assembled with the pure zinc sheets showed significant fluctuation with the increase of the number of cycles, indicating that the polarization of the battery was increasing as the charge and discharge cycles proceeded. The cycle life of the symmetrical battery assembled by the modified zinc metal negative electrode in comparative examples 1-2 is longer than that of the symmetrical battery assembled by the pure zinc sheet, but the voltage platform is not stable and short circuit occurs at about 200 hours. The symmetrical batteries assembled by the modified zinc metal cathodes in examples 1-8 are still very stable in voltage platform after repeated cycles, which shows that the cycle stability of the metal zinc cathodes with Cu, al, sn and Ag elements implanted on the surfaces is improved, zinc dendrites are obviously inhibited, and the service life of the water-based zinc ion battery is greatly prolonged.
Finally, it should be noted that: the embodiments described above are only for illustrating the technical solution of the present invention, and are not limiting; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced with equivalents; such modifications and substitutions do not depart from the spirit of the invention.
Claims (6)
1. A preparation method of a modified zinc metal sheet is characterized in that: implanting doping ions into the zinc metal sheet to obtain a modified zinc metal sheet, wherein the doping ions are Cu; the injection is as follows: degree of working vacuum4×10 -3 Pa, injection voltage of 40-50kV, injection dosage of 1 +.>10 15 -1/>10 16 ions/>cm -2 The method comprises the steps of carrying out a first treatment on the surface of the Heating the zinc metal sheet to 25-50 ℃ at a heating rate of 30-35 ℃/h, then injecting doping ions, and cooling to room temperature at a cooling rate of 15-20 ℃/h after the injection is completed;
the implantation of the doped ions adopts MEVVA source ion implantation technology.
2. The method for producing a modified zinc metal sheet according to claim 1, characterized in that: the zinc metal in the zinc metal sheet is selected from pure zinc or zinc alloy.
3. A method for producing a modified zinc metal sheet according to claim 1 or 2, characterized in that: the zinc metal sheet is pretreated firstly, and the pretreatment process is as follows: firstly, adopting metallographic sand paper and a polishing machine to sequentially polish and polish the zinc metal sheet, then using absolute ethyl alcohol to ultrasonically clean for more than 10 minutes, and drying by hot air.
4. A method for producing a modified zinc metal sheet according to claim 1 or 2, characterized in that: the doping ions are injected, the target material is selected from Cu, and the purity of the target material is more than 99.9%.
5. A modified zinc metal sheet produced by the production method according to any one of claims 1 to 4.
6. Use of the modified zinc sheet metal prepared by the preparation method according to any one of claims 1 to 4, characterized in that: the modified zinc metal sheet is assembled into a symmetrical battery or used as a negative electrode in a water-based zinc ion battery.
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Citations (15)
| Publication number | Priority date | Publication date | Assignee | Title |
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