CN113964289A - Surface organic phosphoric acid etched composite zinc-philic passive film modified zinc metal cathode and preparation method and application thereof - Google Patents
Surface organic phosphoric acid etched composite zinc-philic passive film modified zinc metal cathode and preparation method and application thereof Download PDFInfo
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- 229910052751 metal Inorganic materials 0.000 title claims abstract description 78
- 239000002184 metal Substances 0.000 title claims abstract description 77
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 title claims abstract description 64
- 150000003751 zinc Chemical class 0.000 title claims abstract description 48
- 229910000147 aluminium phosphate Inorganic materials 0.000 title claims abstract description 32
- 239000002131 composite material Substances 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 78
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 78
- 239000011701 zinc Substances 0.000 claims abstract description 78
- 238000002161 passivation Methods 0.000 claims abstract description 23
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 10
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 10
- 239000010452 phosphate Substances 0.000 claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 9
- 238000005530 etching Methods 0.000 claims abstract description 9
- 238000011065 in-situ storage Methods 0.000 claims abstract description 7
- 238000001035 drying Methods 0.000 claims description 13
- IMQLKJBTEOYOSI-GPIVLXJGSA-N Inositol-hexakisphosphate Chemical compound OP(O)(=O)O[C@H]1[C@H](OP(O)(O)=O)[C@@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@@H]1OP(O)(O)=O IMQLKJBTEOYOSI-GPIVLXJGSA-N 0.000 claims description 11
- 238000004140 cleaning Methods 0.000 claims description 9
- YDONNITUKPKTIG-UHFFFAOYSA-N [Nitrilotris(methylene)]trisphosphonic acid Chemical compound OP(O)(=O)CN(CP(O)(O)=O)CP(O)(O)=O YDONNITUKPKTIG-UHFFFAOYSA-N 0.000 claims description 8
- 238000002791 soaking Methods 0.000 claims description 8
- BAERPNBPLZWCES-UHFFFAOYSA-N (2-hydroxy-1-phosphonoethyl)phosphonic acid Chemical compound OCC(P(O)(O)=O)P(O)(O)=O BAERPNBPLZWCES-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- IMQLKJBTEOYOSI-UHFFFAOYSA-N Phytic acid Natural products OP(O)(=O)OC1C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C1OP(O)(O)=O IMQLKJBTEOYOSI-UHFFFAOYSA-N 0.000 claims description 6
- 239000000467 phytic acid Substances 0.000 claims description 6
- 229940068041 phytic acid Drugs 0.000 claims description 6
- 235000002949 phytic acid Nutrition 0.000 claims description 6
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Inorganic materials O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- 229940120146 EDTMP Drugs 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 229940090960 diethylenetriamine pentamethylene phosphonic acid Drugs 0.000 claims description 4
- DUYCTCQXNHFCSJ-UHFFFAOYSA-N dtpmp Chemical compound OP(=O)(O)CN(CP(O)(O)=O)CCN(CP(O)(=O)O)CCN(CP(O)(O)=O)CP(O)(O)=O DUYCTCQXNHFCSJ-UHFFFAOYSA-N 0.000 claims description 4
- NFDRPXJGHKJRLJ-UHFFFAOYSA-N edtmp Chemical compound OP(O)(=O)CN(CP(O)(O)=O)CCN(CP(O)(O)=O)CP(O)(O)=O NFDRPXJGHKJRLJ-UHFFFAOYSA-N 0.000 claims description 4
- 239000002105 nanoparticle Substances 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 3
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 3
- 239000012498 ultrapure water Substances 0.000 claims description 3
- 239000010865 sewage Substances 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims 1
- 239000002245 particle Substances 0.000 abstract description 8
- 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 abstract description 6
- 229910000165 zinc phosphate Inorganic materials 0.000 abstract description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 5
- 239000013522 chelant Substances 0.000 abstract description 5
- 230000007797 corrosion Effects 0.000 abstract description 5
- 238000005260 corrosion Methods 0.000 abstract description 5
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 5
- 239000001257 hydrogen Substances 0.000 abstract description 5
- 230000008021 deposition Effects 0.000 abstract description 3
- 239000007773 negative electrode material Substances 0.000 abstract 2
- 230000000052 comparative effect Effects 0.000 description 13
- 239000000243 solution Substances 0.000 description 9
- 235000012431 wafers Nutrition 0.000 description 8
- 238000009826 distribution Methods 0.000 description 7
- 238000013112 stability test Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 238000010586 diagram Methods 0.000 description 5
- 230000005684 electric field Effects 0.000 description 5
- 210000004027 cell Anatomy 0.000 description 4
- 230000001351 cycling effect Effects 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 238000011056 performance test Methods 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 238000007086 side reaction Methods 0.000 description 3
- 229920000388 Polyphosphate Polymers 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 230000005520 electrodynamics Effects 0.000 description 2
- 238000006056 electrooxidation reaction Methods 0.000 description 2
- 238000005421 electrostatic potential Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 239000001205 polyphosphate Substances 0.000 description 2
- 235000011176 polyphosphates Nutrition 0.000 description 2
- 238000004080 punching Methods 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 2
- 229960001763 zinc sulfate Drugs 0.000 description 2
- 229910000368 zinc sulfate Inorganic materials 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000004807 desolvation Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000005486 organic electrolyte Substances 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- HTPGOQRGCUSPGR-UHFFFAOYSA-N phosphoric acid silane Chemical compound [SiH4].OP(O)(O)=O HTPGOQRGCUSPGR-UHFFFAOYSA-N 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000005303 weighing 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
- 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
- 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
- H01M4/42—Alloys based on zinc
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
-
- 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
-
- 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
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- General Chemical & Material Sciences (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention relates to the technical field of water-based zinc ion batteries, in particular to a zinc metal cathode modified by a composite zinc-philic passivation film with organic phosphoric acid etched on the surface, and a preparation method and application thereof. The preparation method comprises the steps of carrying out chemical reaction on the organic phosphate solution and the zinc metal negative electrode, etching the surface of the zinc negative electrode, generating nano zinc particles on the surface to reconstruct the surface appearance of the negative electrode, and simultaneously generating an organic zinc phosphate nano zinc-philic chelate passivation film in situ on the surface of the zinc metal negative electrode to obtain the modified zinc metal negative electrode. The chemical reaction can realize the regulation and control of the surface structure of the obtained zinc metal negative electrode material and generate a stable chelate passivation film, and the modified zinc metal negative electrode material can obviously inhibit the dendritic growth of a zinc negative electrode, realize the uniform and compact deposition of zinc on the surface of the zinc negative electrode, inhibit the hydrogen evolution corrosion and greatly prolong the cycle life of the zinc ion battery when being applied to a water system zinc ion battery system.
Description
Technical Field
The invention relates to the technical field of water-based zinc ion batteries, in particular to a zinc metal cathode modified by a composite zinc-philic passivation film with organic phosphoric acid etched on the surface, and a preparation method and application thereof.
Background
Lithium Ion Batteries (LIBs) occupy the dominant position of current commercial batteries due to their high energy density and long cycle life, and have broad application prospects in mobile electronic devices, electric vehicles, and large-scale grid energy storage systems. However, lithium ion batteries also have significant disadvantages, such as a shortage of metallic lithium resources, high cost and harsh preparation conditions, toxic organic electrolytes, and potential safety problems, which have severely hampered their further applications, and have prompted researchers to turn their attention to other metal ion batteries, such as potassium, sodium, magnesium, and zinc. The zinc metal has the advantages of abundant reserves, low equilibrium potential, high hydrogen overpotential and high theoretical capacity (820 mA.h/g) in nature, zinc has the highest energy in stable metal elements in an aqueous solution, low oxidation-reduction potential (-0.76V), environmental friendliness and the like.
In the electrochemical reaction process of the zinc ion battery, zinc ions can carry more free charges, theoretically, the zinc ion battery has higher energy density than a lithium ion battery, and under the same discharge capacity, fewer ions are desorbed from a positive electrode material, so that the crystal structure of the material is not easy to damage, and the good stability of an electrode is ensured, therefore, the zinc ion secondary battery becomes a current research hotspot. However, the metal zinc cathode still faces some considerable problems, and in the battery cycle process, the metal zinc cathode faces the problems of dendritic crystal growth, slow corrosion and passivation on the surface, inevitable hydrogen evolution and the like, so that the battery capacity is attenuated, the coulombic efficiency and the cycle stability are reduced, the volume is expanded, even the dendritic crystal pierces a diaphragm to cause short circuit, the safety problem is caused, and the like, and the development and the application of the water-based zinc ion battery are seriously hindered.
Disclosure of Invention
In order to solve the technical problems, the invention utilizes the characteristics of organic phosphoric acid polyphosphate groups to carry out chemical reaction with commercial zinc sheets to etch the surface of the zinc metal and generate organic zinc phosphate in situ, and nano zinc particles generated by etching enable the surface of the zinc metal cathode to be three-dimensional and regulate and control the distribution of an electric field; the special phosphate group in the organic zinc phosphate has the advantages of high zinc ion adsorption energy and low electrostatic potential, so that the water system battery assembled by the zinc metal cathode modified by the composite zinc-philic passive film etched by organic phosphate on the surface is constructed, the electrochemical corrosion under the water system environment is inhibited, the high stability of the electrode structure is ensured, and the zinc ion battery with high energy density, long circulation and low cost is obtained.
In order to achieve the purpose, the embodiment of the invention provides a preparation method of a zinc metal negative electrode modified by a composite zinc-philic passivation film with organic phosphoric acid etched on the surface, which comprises the following steps:
s1, ultrasonically cleaning and drying the zinc sheet by using deionized water and an organic solvent to obtain a pretreated zinc sheet;
and S2, placing the pretreated zinc sheet into an organic phosphoric acid solution for soaking reaction, and then cleaning and drying to obtain the modified zinc metal cathode.
Further, the mass concentration of the organic phosphoric acid solution is 5-120 g/L; the organic phosphoric acid is any one of phytic acid, aminotrimethylene phosphonic Acid (ATMP), hydroxyethylidene diphosphonic acid (HEDP), ethylenediamine tetramethylene phosphonic acid (EDTMP), diethylenetriamine pentamethylene phosphonic acid (DTPMP) and aminotrimethylene phosphonic Acid (ATP).
Further, the soaking reaction time in the step S2 is 5-40 min.
Further, the organic solvent in the step S1 is one or two of ethanol and acetone in sewage; the drying conditions are as follows: vacuum at 20-40 deg.C.
Further, the step S2 of washing and drying specifically includes:
cleaning with deionized water or ultrapure water;
drying at 20-40 deg.C under vacuum.
Based on the same inventive concept, the embodiment of the invention also provides a surface organic phosphoric acid etched composite zinc-philic passive film modified zinc metal cathode, and the modified zinc metal cathode is obtained by the preparation method;
the surface of the modified zinc metal cathode is etched by organic phosphoric acid to generate a nano-scale particle surface, and a covering nano-scale zinc-philic passive film is generated in situ.
Further, the size of the nano-scale particles is 200-400nm, and the thickness of the zinc-philic passivation film is 150-1500 nm.
Based on the same invention concept, the embodiment of the invention also provides the application of the surface organic phosphoric acid etched composite zinc-philic passive film modified zinc metal cathode obtained by the preparation method, and the modified zinc metal cathode is assembled into a symmetrical battery;
or assembling the modified zinc metal negative electrode as a negative electrode and CNT/MnO2 as a positive electrode to obtain the water-based zinc ion battery.
Has the advantages that:
(1) according to the invention, an environment-friendly, green and harmless organic phosphate solution is selected, the characteristics of organic phosphate polyphosphate groups are utilized, the organic phosphate solution and commercial zinc sheets are subjected to chemical reaction to etch the surface of a zinc metal and generate organic zinc phosphate in situ, nano zinc particles generated by etching enable the surface of a zinc metal cathode to be three-dimensional, and the distribution of an electric field is regulated and controlled; the special phosphate group in the organic zinc phosphate has the advantages of high zinc ion adsorption energy and low electrostatic potential, and through the characteristics, the organic phosphoric acid is utilized to etch the zinc metal surface, so that primary zinc oxide is eliminated, the nano zinc particles are generated, the surface state is reconstructed, and meanwhile, a layer of nano zinc-philic hydrophobic passivation film is coated, so that the pole piece impedance is reduced, the affinity capacity for zinc is enhanced, the desolvation effect is realized to a certain degree, the surface electric field distribution of the zinc cathode is regulated, the generation of side reactions such as the growth of zinc dendrites and hydrogen evolution corrosion is inhibited based on uniform surface potential distribution, and the zinc metal cathode is protected to realize long-cycle stability.
(2) The modified zinc metal cathode prepared by the invention simultaneously utilizes the surface structure design and the artificial SEI film technology, and the nano zinc three-dimensional structure generated by in-situ etching regulates the distribution of an electric field to induce the subsequent uniform deposition of zinc ions; the zinc organic phosphate chelate generated in situ exerts the special advantages of phosphate groups, and realizes the long cycle stability of the zinc metal cathode. Modification by the inventionThe modified zinc metal cathode has higher current density and larger capacity (1 mAcm)-21mAh cm-2) The class stability cycle exceeds 1350 h.
(3) The invention is suitable for the storage and high cycling stability of the commercial zinc sheet, the nano zinc particles generated by surface etching reconstruct the surface three-dimensional state and obviously uniform electric field distribution, the zinc organophosphate passive film has stronger capacity of isolating air and water, is beneficial to the storage and use of the commercial zinc sheet, improves the electrochemical performance and cycling stability of the zinc cathode, and effectively improves the performance of the water system zinc ion battery.
Drawings
FIG. 1 is an SEM image of a surface organic phosphoric acid etched composite zinc-philic passivation film modified zinc metal cathode obtained in example 1 of the present invention;
FIG. 2 is an electrodynamic polarization curve of the modified zinc metal cathode with the surface organic phosphate-etched composite zinc-philic passivation film obtained in example 1 of the present invention and an unmodified commercial zinc sheet in a 2M zinc sulfate aqueous solution;
fig. 3 is a time-voltage comparison graph of cycle stability tests performed on a symmetric cell assembled from a modified zinc metal negative electrode and an unmodified zinc metal negative electrode obtained in example 1 of the present invention;
fig. 4 is a graph of the specific capacity and efficiency of the full battery cycle of the modified zinc metal negative electrode obtained in example 1 of the present invention;
FIG. 5 is a time-voltage diagram of a cycle stability test of a symmetrical battery assembled with a modified zinc metal negative electrode obtained in example 2 of the present invention;
FIG. 6 is a time-voltage diagram of a cycle stability test performed on a symmetrical battery assembled with a modified zinc metal negative electrode obtained in example 3 of the present invention;
FIG. 7 is a time-voltage diagram of a cycle stability test performed on a symmetrical battery assembled with a modified zinc metal negative electrode obtained in example 4 of the present invention;
fig. 8 is an SEM image of a modified zinc metal negative electrode obtained in comparative example 1 of the present invention;
FIG. 9 is a time-voltage diagram of a cycle stability test of a symmetrical cell assembled with a modified zinc metal negative electrode obtained in comparative example 2 of the present invention;
fig. 10 is a time-voltage diagram of a cycle stability test of a symmetrical battery assembled with a modified zinc metal negative electrode obtained in comparative example 3 of the present invention.
Detailed Description
In order to more clearly illustrate the technical content of the present invention, the detailed description is given herein with reference to specific examples and drawings, and it is obvious that the examples are only preferred embodiments of the technical solution, and other technical solutions that can be obviously derived by those skilled in the art from the technical content disclosed still belong to the protection scope of the present invention.
In the embodiment of the present invention, the chemical reagents used can be prepared by the methods of purchase or existing preparation methods, and the equipment used is the conventional equipment in the prior art.
Example 1
Firstly, preparing a zinc metal wafer to be modified: taking a commercial three-dimensional net-shaped zinc sheet with a certain area and thickness of 0.1mm, then punching the sheet into a circular sheet with the diameter of 16mm by using a sheet punching machine, then pressing the surface of the punched zinc sheet to be flat by using a weight, sequentially ultrasonically cleaning the pressed zinc sheet for 10 minutes by using ultrapure water and ethanol, and then drying the zinc sheet in a vacuum oven at 30 ℃ for later use.
Weighing 1.5g of phytic acid, adding the phytic acid into a beaker containing 25mL of distilled water, stirring to fully dissolve the phytic acid, then clamping 2 commercial zinc metal wafers prepared in advance, putting the commercial zinc metal wafers into the solution, soaking for 10min, wherein bubbles are gradually generated on the surfaces of the zinc wafers, the phytic acid solution is gradually lightened from yellow brown, taking the zinc wafers out of the solution after 10min, cleaning the zinc wafers by using the distilled water, drying the zinc wafers in a vacuum oven at 30 ℃ for 12h, and drying the surfaces of the zinc wafers to obtain the zinc metal cathode modified by the organic phosphoric acid etched composite zinc-philic passivation film on the surfaces.
Example 2
In the embodiment, a parallel test similar to that of the embodiment 1 is carried out, wherein the concentration of the phytic acid solution is 100g/L, and other preparation methods are completely the same as the embodiment 1, so that the zinc metal negative electrode modified by the composite zinc-philic passivation film etched by organic phosphate on the surface is obtained.
Example 3
In this embodiment, similar parallel tests are performed as in examples 1 and 2, wherein the time for soaking the cleaned and dried zinc sheet in the phytic acid solution is 30min, and other preparation methods are completely the same as those in example 1, so as to obtain the zinc metal negative electrode modified by the composite zinc-philic passivation film etched by organic phosphoric acid on the surface.
Example 4
In this example, similar parallel tests as those in examples 1 and 2 were performed, wherein the selected organophosphate was hydroxyethylidene diphosphonic acid (HEDP), and the other preparation methods were completely the same as those in example 1, to obtain a zinc metal negative electrode modified by a composite zinc-philic passivation film etched by surface organophosphate.
Comparative example 1
In the comparative example, the concentration of phytic acid was 2.5g/L, and the other preparation methods were exactly the same as in example 1 to obtain a modified zinc metal negative electrode.
Comparative example 2
In the comparative example, the soaking time in the phytic acid solution is 60min, and the other preparation methods are completely the same as the example 1 to obtain the modified zinc metal negative electrode.
Comparative example 3
The phosphoric acid used in this comparative example was not an organic phosphoric acid but an inorganic phosphoric acid, and other preparation methods were exactly the same as in example 1 to obtain a modified zinc metal negative electrode.
And (3) performance testing:
the microstructure representation of the modified zinc metal cathodes obtained in the example 1 and the comparative example 1 is carried out by adopting a scanning electron microscope, specifically, detailed SEM images shown in the figure 1 and the figure 8 are shown in the figure 1, the obtained zinc sheet has nano zinc particles generated by etching on the surface and is coated with a uniform zinc organic phosphate chelate passivation film, and the nano zinc particles are distributed under the chelate, so that the stable zinc deposition in the subsequent electrochemical alloying process and the inhibition of side reactions such as hydrogen evolution reaction and the like are facilitated; the modified zinc metal anode prepared under the conditions in fig. 9 has the surface with obvious nano zinc particles generated by phosphoric acid corrosion, but has no obvious dense passivation film structure, which may be caused by insufficient reaction requirements due to low concentration of phytic acid solution.
The zinc metal negative electrode modified by the organic phosphate-silane composite passivation film obtained in the example 1 and a commercial zinc sheet are subjected to electrodynamic polarization curve measurement in a 2M zinc sulfate aqueous solution, as shown in fig. 2, the surface organic phosphate etched composite zinc-philic passivation film modified zinc metal negative electrode obtained in the example has the advantages of obviously reduced corrosion current and excellent electrochemical corrosion resistance.
The modified zinc metal negative electrode obtained in the example 1 is assembled into a symmetrical battery to be subjected to electrochemical performance test, and commercial zinc sheets are used for comparison, the result is shown in figure 3, the modified zinc metal negative electrode obtained in the example 1 is continuously charged and discharged for 1h under the current density of 1mAcm-2, and the cycling stability is tested, so that the modified zinc metal negative electrode obtained in the example 1 shows excellent cycling performance, can be stably cycled for more than or equal to 1350h under the current density of 1mAcm-2, and shows excellent stability. The modified zinc metal negative electrode obtained in example 1 and a CNT/MnO2 positive electrode sheet are assembled into a full cell for electrochemical performance test, and a commercial zinc sheet is used for comparison, the result is shown in FIG. 4, a charge-discharge test is carried out under the current density of 1A/g, and the specific capacity is more than or equal to 230mAh/g when the cell is cycled for 200 circles.
The modified zinc metal anodes obtained in examples 2, 3 and 4 were assembled into symmetrical batteries and subjected to electrochemical performance tests, and the results are shown in fig. 5, 6 and 7, which show that the cycle time under the same test conditions was respectively close to 700h, 640h and 600h, and the results are similar to those in example 1, and the battery has excellent cycle performance.
The modified zinc metal cathodes obtained in the embodiment 1 and the comparative example 2 are respectively assembled into a symmetrical battery for electrochemical performance test, and the result is shown in fig. 9, the electrochemical performance of the symmetrical battery of the modified zinc metal cathode prepared in the comparative example 1 is only 244 hours after cycle time, the electrochemical performance table is obviously reduced, a thicker passivation film structure is generated due to overlong chemical reaction time during soaking, the conductivity of the zinc metal cathode is reduced, and the stable structure of the cathode is damaged due to over-severe etching on the surface of a zinc sheet. As shown in fig. 10, the electrochemical performance of the symmetrical battery with the modified zinc metal cathode prepared in comparative example 3 is limited by the loose and porous distribution of zinc phosphate generated by inorganic phosphoric acid, the serious surface etching, the occurrence of side reactions inhibited by the structure of the passivation film, and the obvious decline of the electrochemical performance.
The above-mentioned embodiments are only preferred embodiments of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered as the technical scope of the present invention, and equivalents and modifications of the technical solutions and concepts of the present invention should be covered by the scope of the present invention.
Claims (8)
1. A preparation method of a zinc metal cathode modified by a composite zinc-philic passive film etched by organic phosphoric acid on the surface is characterized by comprising the following steps:
s1, ultrasonically cleaning and drying the zinc sheet by using deionized water and an organic solvent to obtain a pretreated zinc sheet;
and S2, placing the pretreated zinc sheet into an organic phosphoric acid solution for soaking reaction, and then cleaning and drying to obtain the modified zinc metal cathode.
2. The preparation method of the surface organic phosphoric acid etched composite zinc-philic passive film modified zinc metal cathode as claimed in claim 1, wherein the mass concentration of the organic phosphoric acid solution is 5-120 g/L; the organic phosphoric acid is any one of phytic acid, aminotrimethylene phosphonic Acid (ATMP), hydroxyethylidene diphosphonic acid (HEDP), ethylenediamine tetramethylene phosphonic acid (EDTMP), diethylenetriamine pentamethylene phosphonic acid (DTPMP) and aminotrimethylene phosphonic Acid (ATP).
3. The preparation method of the zinc metal negative electrode with the modified zinc-philic passivation film etched on the surface by using the organic phosphoric acid as the raw material according to claim 1, wherein the soaking reaction time in the step S2 is 5-40 min.
4. The preparation method of the surface organic phosphoric acid etched composite zinc-philic passive film modified zinc metal cathode as claimed in claim 1, wherein the organic solvent of step S1 is one or two of sewage ethanol and acetone; the drying conditions are as follows: vacuum at 20-40 deg.C.
5. The preparation method of the surface organic phosphoric acid etched composite zinc-philic passive film modified zinc metal cathode as claimed in claim 1, wherein the step S2 of cleaning and drying specifically comprises the steps of:
cleaning with deionized water or ultrapure water;
drying at 20-40 deg.C under vacuum.
6. A surface organic phosphoric acid etching composite zinc-philic passive film modified zinc metal cathode is characterized in that the modified zinc metal cathode is obtained by the preparation method of any claim 1 to 5;
the surface of the modified zinc metal cathode is etched by organic phosphoric acid to generate a nano-scale particle surface, and a covering nano-scale zinc-philic passive film is generated in situ.
7. The surface organic phosphoric acid etched composite zinc-philic passivation film modified zinc metal cathode as claimed in claim 6, wherein the size of the nano-scale particles is 200-400nm, and the thickness of the zinc-philic passivation film is 150-1500 nm.
8. Use of a zinc metal negative electrode modified by a surface organic phosphate etched composite zinc-philic passive film obtained by the preparation method according to any of claims 1 to 5 or according to any of claims 6 to 7, wherein the modified zinc metal negative electrode is assembled into a symmetrical battery;
or using the modified zinc metal negative electrode as a negative electrode, CNT/MnO2And assembling the positive electrode to obtain the water-based zinc ion battery.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114824278A (en) * | 2022-05-24 | 2022-07-29 | 北京大学深圳研究生院 | SEI film reaction liquid, modification method of zinc negative electrode and modified zinc negative electrode |
| CN115911244A (en) * | 2022-11-18 | 2023-04-04 | 天津大学 | Zinc metal negative electrode with insoluble zinc salt anticorrosive coating and water-based zinc battery |
| CN116504911A (en) * | 2023-06-25 | 2023-07-28 | 吉林大学 | Amorphous zinc oxide coating modified zinc anode, preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20200099056A1 (en) * | 2017-03-24 | 2020-03-26 | Real Power Industrial Limited Company | Negative electrode of secondary cell, manufacturing method thereof, and secondary cell |
| CN113540395A (en) * | 2021-07-21 | 2021-10-22 | 重庆大学 | Film forming liquid for artificial SEI film on surface of negative electrode of rechargeable magnesium battery and preparation method |
-
2021
- 2021-10-26 CN CN202111248048.0A patent/CN113964289A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20200099056A1 (en) * | 2017-03-24 | 2020-03-26 | Real Power Industrial Limited Company | Negative electrode of secondary cell, manufacturing method thereof, and secondary cell |
| CN113540395A (en) * | 2021-07-21 | 2021-10-22 | 重庆大学 | Film forming liquid for artificial SEI film on surface of negative electrode of rechargeable magnesium battery and preparation method |
Non-Patent Citations (1)
| Title |
|---|
| XIA WANG等: ""Stable Zinc Metal Anodes with Textured Crystal Faces and Functional Zinc Compound Coatings"", 《ADV. FUNCT. MATER》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114824278A (en) * | 2022-05-24 | 2022-07-29 | 北京大学深圳研究生院 | SEI film reaction liquid, modification method of zinc negative electrode and modified zinc negative electrode |
| CN114824278B (en) * | 2022-05-24 | 2024-09-13 | 北京大学深圳研究生院 | SEI film reaction liquid, modification method of zinc anode and modified zinc anode |
| CN115911244A (en) * | 2022-11-18 | 2023-04-04 | 天津大学 | Zinc metal negative electrode with insoluble zinc salt anticorrosive coating and water-based zinc battery |
| CN116504911A (en) * | 2023-06-25 | 2023-07-28 | 吉林大学 | Amorphous zinc oxide coating modified zinc anode, preparation method and application thereof |
| CN116504911B (en) * | 2023-06-25 | 2023-09-05 | 吉林大学 | Amorphous zinc oxide coating modified zinc anode, preparation method and application thereof |
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