CN113611828B - Zinc oxide composite material, preparation method, negative electrode zinc paste and zinc-nickel storage battery - Google Patents
Zinc oxide composite material, preparation method, negative electrode zinc paste and zinc-nickel storage battery Download PDFInfo
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- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 title claims abstract description 607
- 239000011787 zinc oxide Substances 0.000 title claims abstract description 304
- 239000002131 composite material Substances 0.000 title claims abstract description 125
- QELJHCBNGDEXLD-UHFFFAOYSA-N nickel zinc Chemical compound [Ni].[Zn] QELJHCBNGDEXLD-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 238000003860 storage Methods 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- RNWHGQJWIACOKP-UHFFFAOYSA-N zinc;oxygen(2-) Chemical compound [O-2].[Zn+2] RNWHGQJWIACOKP-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 239000000956 alloy Substances 0.000 claims abstract description 146
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 146
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 104
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 82
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 69
- 239000011701 zinc Substances 0.000 claims abstract description 67
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 65
- 238000000498 ball milling Methods 0.000 claims abstract description 53
- 230000001590 oxidative effect Effects 0.000 claims abstract description 24
- 239000000463 material Substances 0.000 claims abstract description 10
- 238000005266 casting Methods 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims description 70
- 229910052751 metal Inorganic materials 0.000 claims description 36
- 239000002184 metal Substances 0.000 claims description 36
- 238000007254 oxidation reaction Methods 0.000 claims description 32
- 230000003647 oxidation Effects 0.000 claims description 29
- 230000008569 process Effects 0.000 claims description 29
- 239000012752 auxiliary agent Substances 0.000 claims description 23
- 229910052799 carbon Inorganic materials 0.000 claims description 20
- 238000010438 heat treatment Methods 0.000 claims description 17
- 229910052797 bismuth Inorganic materials 0.000 claims description 14
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 14
- 229910052684 Cerium Inorganic materials 0.000 claims description 13
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 13
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 13
- 229910052782 aluminium Inorganic materials 0.000 claims description 13
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 13
- 229910052802 copper Inorganic materials 0.000 claims description 13
- 239000010949 copper Substances 0.000 claims description 13
- 229910052738 indium Inorganic materials 0.000 claims description 13
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 13
- 229910052718 tin Inorganic materials 0.000 claims description 13
- 229910052727 yttrium Inorganic materials 0.000 claims description 13
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims description 13
- 239000000654 additive Substances 0.000 claims description 12
- 239000002245 particle Substances 0.000 claims description 12
- 239000011833 salt mixture Substances 0.000 claims description 12
- 238000002844 melting Methods 0.000 claims description 10
- 230000008018 melting Effects 0.000 claims description 10
- 230000000996 additive effect Effects 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 6
- HTUMBQDCCIXGCV-UHFFFAOYSA-N lead oxide Chemical compound [O-2].[Pb+2] HTUMBQDCCIXGCV-UHFFFAOYSA-N 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 150000003839 salts Chemical class 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 4
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 3
- 239000005751 Copper oxide Substances 0.000 claims description 3
- 229910000416 bismuth oxide Inorganic materials 0.000 claims description 3
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 3
- 229910000431 copper oxide Inorganic materials 0.000 claims description 3
- 239000011258 core-shell material Substances 0.000 claims description 3
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 claims description 3
- 229910003437 indium oxide Inorganic materials 0.000 claims description 3
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 claims description 3
- 229910000464 lead oxide Inorganic materials 0.000 claims description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 3
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 3
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 claims description 3
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 3
- 229910001887 tin oxide Inorganic materials 0.000 claims description 3
- 229910001508 alkali metal halide Inorganic materials 0.000 claims description 2
- 150000008045 alkali metal halides Chemical class 0.000 claims description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 239000006229 carbon black Substances 0.000 claims description 2
- 239000002003 electrode paste Substances 0.000 claims description 2
- 229910002804 graphite Inorganic materials 0.000 claims description 2
- 239000010439 graphite Substances 0.000 claims description 2
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims 2
- 239000011573 trace mineral Substances 0.000 abstract description 8
- 235000013619 trace mineral Nutrition 0.000 abstract description 8
- 210000001787 dendrite Anatomy 0.000 abstract description 5
- 229910044991 metal oxide Inorganic materials 0.000 description 20
- 150000004706 metal oxides Chemical class 0.000 description 20
- 239000007788 liquid Substances 0.000 description 18
- 239000000243 solution Substances 0.000 description 12
- 238000003756 stirring Methods 0.000 description 12
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
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- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 239000002002 slurry Substances 0.000 description 6
- 239000007773 negative electrode material Substances 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
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- DIIIISSCIXVANO-UHFFFAOYSA-N 1,2-Dimethylhydrazine Chemical compound CNNC DIIIISSCIXVANO-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 2
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- 229910052786 argon Inorganic materials 0.000 description 2
- OJIJEKBXJYRIBZ-UHFFFAOYSA-N cadmium nickel Chemical compound [Ni].[Cd] OJIJEKBXJYRIBZ-UHFFFAOYSA-N 0.000 description 2
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Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- 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
- H01M10/24—Alkaline accumulators
- H01M10/30—Nickel accumulators
-
- 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
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
-
- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Composite Materials (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention relates to a zinc oxide composite material and a preparation method thereof, negative electrode zinc paste and a zinc-nickel storage battery, belongs to the technical field of zinc-nickel battery materials, and solves the quality problems that trace elements in the existing zinc oxide are difficult to uniformly disperse in the zinc paste, and zinc dendrite short circuit and the like occur. The inner core of the zinc oxide composite material is zinc oxide alloy; the shell is graphene/ZnO obtained by ball milling and oxidizing zinc oxide alloy; the preparation method comprises the following steps: step 1, preparing zinc oxide alloy casting balls or zinc oxide alloy blocks; and 2, continuously ball-milling and oxidizing the zinc oxide alloy cast balls or the zinc oxide alloy blocks at the temperature below 200 ℃, and sucking out and collecting the zinc oxide composite material from the ball mill through a negative pressure fan after ball-milling and oxidizing to obtain the zinc oxide composite material. The zinc oxide composite material has uniform trace element dispersibility, and the preparation method is simple and effective, and the trace element is uniformly dispersed and well combined with zinc oxide alloy.
Description
Technical Field
The invention relates to the technical field of zinc-nickel storage batteries, in particular to a zinc oxide composite material, a preparation method, negative electrode zinc paste and a zinc-nickel storage battery.
Background
The only secondary chemical power products commercialized to date are: lead-acid batteries, nickel-cadmium batteries, nickel-metal hydride (nickel-hydrogen for short) batteries, and lithium ion batteries. Among them, cadmium-nickel batteries have been totally prohibited from being used in the civilian market due to pollution problems. Lead acid batteries are also increasingly limited by pollution problems. Lithium ion batteries have high specific energy, are currently the main stream products in the secondary battery market, but contain toxic electrolyte, once leaked, have high harm (influence) on the environment, and the safety of the lithium ion batteries is still a problem. The nickel-hydrogen battery has higher environmental friendliness, and has low market share because of factors such as higher cost, shorter service life, no advantage of specific energy compared with a lithium ion battery, and the like. Therefore, a new chemical power source excellent in environmental friendliness, safety, life and the like is demanded.
The zinc-nickel battery is environment-friendly, and has no toxic substances such as lead, cadmium, organic solvent, PF5 and the like; the battery adopts a water-based electrolyte system, works at low internal pressure and has the characteristic of high safety; has the advantages of high specific power (which can exceed 200W/kg), high specific energy (which can exceed 80 Wh/kg), wide working temperature range (-40 ℃ to 60 ℃), capability of large-current charge and discharge and the like, and the sources of raw materials are rich.
Therefore, the zinc-nickel battery has wide application fields, particularly in the application fields with high requirements on safety and reliability and high environmental adaptation requirements, such as high-speed trains, airplanes, battlefield environments and the like, and the zinc-nickel battery is one of the best power supply candidates. However, zinc-nickel batteries suffer from five problems: dendrite, zinc electrode deformation, hydrogen evolution, zinc electrode corrosion, and zinc electrode passivation. The prior art uses zinc electrode modification to ameliorate the above problems.
There are various modification methods of the existing zinc electrode, including a mixed dispersion method, a coprecipitation method, a ball-milling dispersion method, a carbon coating technique, and the like. However, the modification methods described above have problems such as uneven doping. The method for doping is simple, effective, uniformly dispersed, well combined, clean and environment-friendly, and is urgent for manufacturing zinc electrode materials and batteries.
Disclosure of Invention
In view of the above analysis, the invention aims to provide a zinc oxide composite material, a preparation method thereof, negative electrode zinc paste and a zinc-nickel battery, which are used for solving the technical problems that trace elements in the existing zinc oxide are difficult to uniformly disperse in the zinc paste, and then quality problems such as zinc dendrite short circuit and the like occur.
The aim of the invention is mainly realized by the following technical scheme:
in one aspect, the invention provides a zinc oxide composite material, wherein the zinc oxide composite material is a core-shell structure material;
the inner core of the zinc oxide composite material is zinc oxide alloy; zinc oxide alloys include zinc and graphene;
the outer shell of the zinc oxide composite material is graphene/ZnO obtained by ball milling and oxidizing zinc oxide alloy;
the zinc oxide composite material comprises the following components in percentage by weight: 1-50% of zinc oxide alloy and 50-99% of graphene/ZnO.
In one possible design, the zinc oxide alloy further includes a metal promoter;
the shell of the zinc oxide composite material also comprises a metal auxiliary agent oxide obtained by ball milling and oxidizing the metal auxiliary agent;
the metal auxiliary agent comprises one or more than two of lead, copper, bismuth, indium, yttrium, cerium, tin and aluminum; the metal auxiliary oxides corresponding to the metal auxiliary are PbO, cuO, bi respectively 2 O 3 、In 2 O 3 、Y 2 O 3 、CeO 2 、SnO 2 And Al 2 O 3 ；
In the zinc oxide alloy, the weight content of the graphene is 0.01-2%, and the weight content of the metal auxiliary agent is 0.01-10%.
In another aspect, the present invention provides a method for preparing a zinc oxide composite material, for preparing the zinc oxide composite material, comprising the steps of:
step 1, melting zinc oxide alloy at low temperature, and injecting the molten zinc into a die to cast balls after the molten zinc is melted to obtain zinc oxide alloy cast balls;
and 2, continuously ball-milling and oxidizing the zinc oxide alloy cast ball at the temperature below 200 ℃, and sucking out and collecting the zinc oxide composite material from the ball mill through a negative pressure fan after ball-milling and oxidizing to obtain the zinc oxide composite material.
Further, in step 1, the low temperature melting temperature is 420-700 ℃;
the grain size of the prepared zinc oxide alloy casting ball is 20-60mm.
Further, in the step 2, the ball milling oxidation temperature is 140-190 ℃;
after ball milling oxidation, the granularity of the prepared zinc oxide composite material is 0.1-5 mu m.
Further, or after the zinc oxide alloy is processed by a dicing process, a zinc oxide alloy block is obtained;
in the step 2, continuously ball-milling and oxidizing the zinc oxide alloy blocks at the temperature below 200 ℃, and sucking out and collecting the zinc oxide composite material from the ball mill through a negative pressure fan after ball-milling and oxidizing to obtain the zinc oxide composite material;
the thickness of the zinc oxide alloy block is 10-50mm.
Further, in the step 2, the rotating speed of the ball mill roller is 20-60rpm, and ball milling oxidation is carried out in an air environment;
the granularity of the zinc oxide composite material is 1-5 mu m.
Further, in the zinc oxide alloy, the weight content of graphene is 0.001-2%, the weight content of lead is 0.001-2%, the weight content of copper is 0.001-2%, the weight content of bismuth is 0.001-1%, the weight content of indium is 0.001-0.5%, the weight content of yttrium is 0.001-0.5%, the weight content of cerium is 0.001-15%, the weight content of tin is 0.001-2%, and the weight content of aluminum is 0.001-0.5%.
In a third aspect, the invention also provides negative electrode zinc paste, which is obtained by adopting the zinc oxide composite material.
In a fourth aspect, the invention also provides a zinc-nickel storage battery, which comprises the negative electrode zinc paste.
Compared with the prior art, the invention has at least one of the following beneficial effects:
(1) The trace elements are added into the zinc oxide alloy as the metal auxiliary agent, the metal auxiliary agent and zinc form the alloy, and the alloy is uniformly distributed in a zinc matrix in the form of atoms or compounds, so that the preparation process is simple, and the trace elements can be uniformly distributed.
(2) According to the invention, zinc oxide alloy is utilized to prepare the zinc oxide composite material, in the ball milling oxidation process, the zinc oxide alloy cast balls and the zinc oxide alloy blocks collide with each other, the surfaces are continuously oxidized and crushed, after the ball milling oxidation is finished, the core part of the zinc oxide composite material is the zinc oxide alloy which is not oxidized, and as graphene has higher tensile strength and extremely high toughness, the graphene can connect the zinc oxide alloy of the core part with the peripheral metal oxide to form a good conductive network.
(3) The zinc oxide composite material prepared by the invention has basically stable distribution of microelements (metal auxiliary agent) and graphene and other materials in the zinc paste during the preparation of the zinc paste and during the processes of subsequent battery production, and the phenomenon of uneven distribution of the auxiliary agent microelements caused by stirring equipment and process problems in the preparation of the zinc paste can be avoided.
(4) The invention can overcome the quality problems of zinc electrodes by microelements in metal assistants in zinc oxide alloy, such as: the invention can prepare reliable zinc electrode, and further manufacture high-performance zinc system battery.
In the invention, the technical schemes can be mutually combined to realize more preferable combination schemes. Additional features and advantages of the invention will be set forth in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention. The objectives and other advantages of the invention may be realized and attained by the embodiments of the invention particularly pointed out in the written description and drawings.
Drawings
The drawings are only for purposes of illustrating particular embodiments and are not to be construed as limiting the invention, like reference numerals being used to refer to like parts throughout the several views.
FIG. 1 is a schematic illustration of a preparation flow of a zinc oxide composite;
FIG. 2 is a roadmap for the preparation of zinc oxide alloys by carbon cladding techniques;
FIG. 3 is a graph of the microscopic morphology of the zinc oxide composite C-1 prepared in example 1.
Detailed Description
The following detailed description of preferred embodiments of the invention is made in connection with the accompanying drawings, which form a part hereof, and together with the description of the embodiments of the invention, are used to explain the principles of the invention and are not intended to limit the scope of the invention.
In one aspect, the invention provides a zinc oxide composite material, wherein the zinc oxide composite material is a core-shell structure material; the inner core of the zinc oxide composite material is zinc oxide alloy; zinc oxide alloys include zinc and graphene; the outer shell of the zinc oxide composite material is graphene/ZnO obtained by ball milling and oxidizing zinc oxide alloy; the zinc oxide composite material comprises the following components in percentage by weight: 1-50% of zinc oxide alloy and 50-99% of graphene/ZnO.
On the other hand, the invention also provides a zinc oxide composite material, wherein the zinc oxide alloy serving as the inner core in the zinc oxide composite material also comprises a metal auxiliary agent; the shell of the zinc oxide composite material also comprises a metal auxiliary agent oxide obtained by ball milling and oxidizing the metal auxiliary agent; the metal auxiliary agent comprises one or more than two of lead, copper, bismuth, indium, yttrium, cerium, tin and aluminum; the metal auxiliary oxides corresponding to the metal auxiliary are PbO, cuO, bi respectively 2 O 3 、In 2 O 3 、Y 2 O 3 、CeO 2 、SnO 2 And Al 2 O 3 。
In the zinc oxide alloy, the weight content of graphene is 0.01-2%, and the weight content of metal auxiliary agent is 0.01-10%.
Specifically, the invention provides a zinc oxide composite material, wherein the inner core of the composite material is zinc oxide alloy (the zinc oxide alloy comprises zinc, graphene and metal auxiliary agent), the outer shell is graphene/metal oxide (the metal oxide comprises ZnO and metal auxiliary agent oxide), namely the zinc oxide composite material comprises zinc oxide alloy in the inner part and graphene/metal oxide which is positioned outside the zinc oxide alloy and wraps the zinc oxide alloy, and part of graphene is inserted between the zinc oxide alloy and the metal oxide.
In the present invention, graphene is doped into a metal oxide to form a composite, and the composite is expressed as graphene/metal oxide, for example, a composite formed by graphene and ZnO is expressed as graphene/ZnO, and graphene and Bi 2 O 3 The complex formed is expressed as graphene/Bi 2 O 3 。
It should be emphasized that, since the content of the graphene is relatively small, and it is difficult to accurately measure the content of the graphene, the graphene portion may be doped in the metal oxide and form a composite, so as to represent the combination mode of the graphene and the metal oxide, the content of the composite of the graphene and the metal oxide is calculated according to the content of the metal oxide; the metal oxide test method is to dissolve out the metal oxide in the compound by using a corresponding solvent, and then to measure the metal content in the solution by using an ICP emission spectrometer.
Illustratively, in the zinc oxide composite described above: the weight content of ZnO is 50-95%, the weight content of graphene is 0.01-2% (e.g. 0.05% -2%), and the weight content of zinc oxide alloy is 5-50% (e.g. 15-30%); the metal promoter oxide is present in an amount of 0-10% by weight (e.g., 0.001-5%).
In a third aspect, the present invention further provides a method for preparing a zinc oxide composite material, as shown in fig. 1, specifically including the following steps:
step 1, melting zinc oxide alloy at a low temperature of 420-700 ℃; after the zinc oxide alloy is melted, the obtained zinc liquid is injected into a die to cast balls, and the grain size of the prepared zinc oxide alloy cast balls is 20-60mm;
and 2, continuously ball milling and oxidizing the zinc oxide alloy cast balls in a ball mill, wherein the ball milling and oxidizing temperature is below 200 ℃, the rotating speed of a ball mill roller is 20-60rpm, the ball milling and oxidizing are carried out in an air environment, and after the ball milling and oxidizing, the zinc oxide composite material with the granularity of 0.1-15 mu m is sucked out of the ball mill by a negative pressure fan and collected, so that the zinc oxide composite material is prepared.
In the step 1, the zinc oxide alloy is subjected to low-temperature melting under the low-temperature condition of 420-700 ℃ so as to reduce the waste of the zinc oxide slag.
In the step 1, the zinc oxide alloy may be processed by a dicing process and then ball-milled. The dicing process includes: the specific operating conditions of zinc ingot feeding, zinc block punching, zinc block conveying and zinc block receiving are well known in the art and are not described herein. The thickness of the zinc oxide alloy block is 10-50mm; and (3) continuously ball-milling and oxidizing the obtained zinc oxide alloy blocks at the temperature below 200 ℃, sucking out the zinc oxide composite material from the ball mill through a negative pressure fan after ball-milling and oxidizing, and collecting the zinc oxide composite material to obtain the zinc oxide composite material.
Compared with the prior art, the ball milling oxidation method is to perform ball milling oxidation on zinc oxide alloy after ball casting or dicing to uniformly distribute graphene in a matrix, and the ball milling oxidation temperature is controlled below 200 ℃ (for example, 140-190 ℃) to avoid graphene oxidation, so that the core of the formed zinc oxide composite material is a zinc oxide alloy component, and graphene can connect the zinc oxide alloy with peripheral metal oxides to form a good conductive network.
In the step 1, the zinc oxide alloy is melted at a low temperature, graphene and a metal auxiliary agent can be well dispersed, and the graphene agglomeration can be avoided by the two methods of ball milling and oxidation after ball casting or dicing, so that the uniform dispersion of the graphene can be maintained.
Illustratively, in the zinc oxide alloy in the above step 1, the weight content of graphene is 0-2%, the weight content of lead is 0-2%, the weight content of copper is 0-2%, the weight content of bismuth is 0-1%, the weight content of indium is 0-0.5%, the weight content of yttrium is 0-0.5%, the weight content of cerium is 0-1.5%, the weight content of tin is 0-2%, and the weight content of aluminum is 0-0.5%; the total weight content of the metal auxiliary agent is 0.1-10%.
Illustratively, in the zinc oxide alloy in the above step 1, the weight content of graphene is 0 to 2%, the weight content of lead is 0.001 to 2%, the weight content of copper is 0.001 to 2%, the weight content of bismuth is 0.001 to 1%, the weight content of indium is 0.001 to 0.5%, the weight content of yttrium is 0.001 to 0.5%, the weight content of cerium is 0.001 to 15%, the weight content of tin is 0.001 to 2%, and the weight content of aluminum is 0.001 to 0.5%.
In the zinc oxide alloy in the step 1, the weight content of the graphene is 0.001-2%, and the weight content of the metal auxiliary agent is 0.1-10%. The metal auxiliary agent is used as the doping agent of zinc oxide alloy, the capacity and the service life of the zinc-nickel storage battery can be further improved, and the type and the dosage of the metal auxiliary agent can be selected according to actual needs.
In the step 2, the ball milling oxidation temperature is 140-190 ℃.
In the step 2, after ball milling oxidation, the granularity of the prepared zinc oxide composite material is 1-5 mu m.
In the step 2, the ball milling oxidation is set as a continuous ball milling process, so that the zinc oxide composite material with more uniform particle size distribution can be obtained. In addition, the oxidation degree and apparent density of the zinc oxide composite material can be adjusted through positive pressure air quantity and negative pressure air quantity.
In the step 2, during ball milling oxidation, zinc oxide alloy cast balls and zinc oxide collide with each other, the surfaces of the zinc oxide alloy cast balls are continuously oxidized and crushed, metal components (zinc and metal additives) in the zinc oxide alloy cast balls are converted into corresponding metal oxides, and graphene is not oxidized basically; therefore, the graphene is uniformly distributed in the matrix and can form a complex with the metal oxide. After ball milling oxidation is finished, the core part of the zinc oxide composite material is a zinc oxide alloy which is not oxidized, and the graphene can connect the zinc oxide alloy of the core with the peripheral metal oxide to form a good conductive network because the graphene has higher tensile strength and extremely high toughness.
In a fourth aspect, the present invention also provides a method for preparing a zinc oxide alloy containing graphene by molten salt growth, specifically comprising the following steps:
step 1, mixing molten salt of alkali metal halide with carbon-containing additive (such as TiC, B 4 C. At least one of active carbon, carbon black, graphite and the like, wherein the addition amount of the carbon-containing additive is 0.005% -0.03% based on carbon, and the salt mixture is obtained;
step 2, firstly placing 30% -70% of salt mixture into the bottom of an alumina crucible, then placing zinc or zinc oxide alloy into the partial salt mixture, then placing the rest salt mixture into the top of zinc or zinc oxide alloy, placing into a vertical heating furnace, heating to 520-900 ℃ to melt the salt mixture and zinc or zinc oxide alloy, decomposing carbon-containing additives into carbon atoms, dispersing into the melted zinc or zinc oxide alloy, and heating for 0.5-5h to obtain a mixture;
and 3, cooling the mixture, and washing to remove the salt mixture, thereby obtaining the zinc oxide alloy.
It should be noted that the zinc oxide alloy containing no graphene can be prepared by the existing zinc oxide alloy preparation method.
In a fifth aspect, the present invention also provides a method for preparing a zinc oxide alloy containing graphene by using a redox method, comprising the steps of:
step 1, preparing graphene alloy;
dispersing natural graphite in water, and carrying out oxidation reaction (illustratively, oxidation reaction at 65-85 ℃ for 20-28 h) under certain conditions by taking sulfuric acid as an oxidant to obtain graphene oxide; dispersing graphene oxide by ultrasonic waves, washing, adding lead oxide, copper oxide, bismuth oxide, indium oxide, yttrium oxide, cerium oxide, tin oxide and aluminum oxide, adding a reducing agent dimethylhydrazine, and carrying out reduction reaction (illustratively, oxidizing reaction at 55-70 ℃ for 15-25 h) under certain conditions; after reduction, washing and drying the obtained reduction reaction system, heating the obtained reduction product in a closed container, taking argon as protective gas, and cooling (heating at 750-850 ℃ for 5-15min for example) after heating for a certain time to obtain the graphene alloy.
And 2, adding the graphene alloy serving as a master alloy into the molten zinc liquid to obtain the zinc oxide alloy containing graphene.
Illustratively, the zinc oxide composite material contains Bi with the weight content of 0.1-3% 2 O 3 The conductivity of zinc oxide can be improved to a certain extent, and the discharge capacity and the utilization rate of active substances of the zinc oxide can be improved.
Illustratively, the zinc oxide composite material contains 0.1-3% SnO by weight 2 The conductivity can be improved, and the hydrogen evolution amount can be reduced.
Illustratively, the zinc oxide composite contains 0.01-1% by weight of graphene.
Illustratively, the zinc oxide composite material comprisesIn content of 0.1-0.5% by weight 2 O 3 The hydrogen evolution overpotential of the zinc-nickel storage battery can be further improved, the hydrogen evolution is reduced, and the service life of the zinc-nickel storage battery is prolonged.
In the sixth aspect, the zinc oxide composite material can be used as positive and negative electrode active materials for a zinc-nickel secondary battery. The invention also provides a negative electrode zinc paste which is used for the zinc-nickel storage battery and comprises the zinc oxide composite material.
The zinc oxide composite material is used as a negative electrode active material, and the weight content of the zinc oxide composite material is 70-99.8% based on the dry weight of the negative electrode zinc paste after charge and discharge formation.
The negative electrode zinc paste provided by the invention adopts the zinc oxide composite material as a negative electrode active material; in addition, the specific types and amounts of additives (such as optional carbon materials, PTFE, CMC, etc.) included in or used in preparing the negative electrode paste of the present invention are well known in the art, and the present invention is not repeated.
It is noted that the test method of the metal oxide in the zinc oxide composite material comprises the following steps: and (3) dissolving out the metal oxide in the composite material by using a corresponding solvent, measuring the content of metal ions in the solution by using an ICP emission spectrometer, and calculating the content of the metal oxide, wherein the balance is zinc oxide alloy.
In a seventh aspect, the invention also provides a zinc-nickel storage battery, which adopts the zinc oxide composite material.
The zinc-nickel storage battery is prepared by referring to the existing method, and is prepared by sequentially homogenizing, pulping, drying polar plates, assembling, adding liquid and forming. The specific operating conditions are well known in the art and will not be described in detail herein.
The open circuit voltage of the zinc-nickel storage battery is tested by a voltmeter; specific energy is detected by discharging the storage battery through a charging and discharging motor, the discharged energy Q is measured, the mass m of the storage battery is weighed through an electronic scale, and the specific energy of the storage battery is= (Q/m) multiplied by 100%; the 2h rate capacity, the-15 ℃ low-temperature capacity, the 21.6A high-current discharge time and the cycle life are all tested according to the GB/T22199-2008 standard.
The zinc oxide composite material provided by the invention is applied to a zinc-nickel storage battery, can be used as a negative active substance, and has higher battery capacity, higher battery power and longer battery life (see tables 2 and 4), and has a wide application prospect.
Example 1
The invention provides a preparation method of a zinc oxide composite material, which specifically comprises the following steps:
step 1, preparing zinc oxide alloy (the zinc oxide alloy containing graphene is prepared by adopting a redox method provided by the fifth aspect), specifically comprising the following steps:
dispersing natural graphite in water, and carrying out oxidation reaction for 24 hours at 75 ℃ by taking sulfuric acid as an oxidant; obtaining graphene oxide, dispersing and washing the graphene oxide by ultrasonic waves, adding lead oxide, copper oxide, bismuth oxide, indium oxide, yttrium oxide, cerium oxide, tin oxide and aluminum oxide, adding a reducing agent dimethylhydrazine, and carrying out reduction reaction for 20 hours at 60 ℃; after reduction, washing and drying the obtained reduction reaction system, heating the obtained reduction product in a closed container, taking argon as protective gas, wherein the pressure of the protective gas is 5 standard atmospheres, the heating temperature is 800 ℃, the heating time is 10min, and then cooling to obtain the graphene alloy.
Adding graphene alloy as master alloy into molten zinc liquid to obtain zinc oxide alloy, wherein the zinc oxide alloy comprises the following components in mass: 0.2% of graphene, 0.05% of lead, 0.08% of copper, 0.4% of bismuth, 0.001% of indium, 0.001% of yttrium, 0.03% of cerium, 0.3% of tin and 0.02% of aluminum.
Step 2, preparing a zinc oxide composite material by utilizing the zinc oxide alloy prepared in the step 1, wherein the zinc oxide composite material comprises a low-temperature melting process, a ball milling oxidation process and a winnowing collection process; the method comprises the following steps:
low temperature melting process: adding zinc oxide alloy into a zinc melting furnace, and heating to 550 ℃ to melt the zinc oxide alloy to obtain zinc liquid;
casting zinc balls: the zinc liquid was poured into a mold to be molded, and then cooled to obtain zinc oxide spheres (particle diameter: 30 mm).
Ball milling oxidation process: the zinc oxide balls are sent into an Shimadzu ball mill, the rotating speed of a roller of the ball mill is controlled to be 50rpm, the zinc oxide balls collide and heat in the roller at 170 ℃, and are oxidized in an air environment to form a powdery composite material, namely the zinc oxide composite material.
Winnowing and collecting: sucking out zinc oxide composite material with the particle size of 2-5 mu m in the ball mill by using a negative pressure fan, collecting and keeping for later use, and recording as C-1;
the mass composition of C-1 is as follows: graphene/ZnO 75%; 24% of zinc oxide alloy, which contains: 0.2% of graphene, 0.05% of lead, 0.08% of copper, 0.4% of bismuth, 0.001% of indium, 0.001% of yttrium, 0.03% of cerium, 0.3% of tin and 0.02% of aluminum. The balance being impurities. The microstructure of C-1 is shown in FIG. 3.
Example 2
The invention provides another preparation method of a zinc oxide composite material, which specifically comprises the following steps:
step 1, preparing zinc oxide alloy
Zinc oxide alloy was prepared according to the method of example 1, except that the zinc oxide alloy contained only zinc and graphene, the graphene content by weight was 0.2%, and the remaining elements were metallic zinc and trace impurities, which were negligible.
Step 2, preparing a zinc oxide composite material, wherein the preparation process comprises a low-temperature melting process, a ball milling oxidation process and a winnowing collection process; the method comprises the following steps:
low temperature melting process: adding zinc oxide alloy into a zinc melting furnace, and heating to 550 ℃ to melt the zinc oxide alloy to obtain zinc liquid;
casting zinc balls: the zinc liquid was poured into a mold to be molded, and then cooled to obtain zinc oxide spheres (particle diameter: 30 mm).
Ball milling oxidation process: the zinc oxide balls are sent into an Shimadzu ball mill, the rotating speed of a roller of the ball mill is controlled to be 50rpm, the zinc oxide balls collide and heat in the roller at 170 ℃, and are oxidized in an air environment to form a powdery composite material, namely the zinc oxide composite material.
Winnowing and collecting: sucking out zinc oxide composite material with the particle size of 2-5 mu m in the ball mill by using a negative pressure fan, and collecting for later use; the prepared zinc oxide composite material is marked as C-2 and comprises the following components in mass percent: 75% of graphene/ZnO and 25% of zinc oxide alloy (graphene/Zn).
Example 3
The invention provides a preparation method of a zinc oxide composite material, which is different from the embodiment 2 in that: in step 2, the zinc oxide alloy is melted and cast into balls instead of cutting the zinc oxide alloy into blocks; the method specifically comprises the following steps:
step 1, preparing zinc oxide alloy
The specific preparation process is the same as in example 2.
Step 2, preparing a zinc oxide composite material by utilizing the zinc oxide alloy prepared in the step 1;
sequentially feeding zinc oxide alloy into a zinc ingot, punching zinc blocks, conveying the zinc blocks, collecting the zinc blocks to obtain cut blocks with the thickness of 30mm, and then performing a ball milling oxidation process and a winnowing collection process; the method comprises the following steps:
ball milling oxidation process: the zinc oxide balls are sent into an Shimadzu ball mill, the rotating speed of a roller of the ball mill is controlled to be 50rpm, the zinc oxide balls collide and heat in the roller at 170 ℃, and are oxidized in an air environment to form a powdery composite material, namely the zinc oxide composite material.
Winnowing and collecting: sucking out zinc oxide composite material with the particle size of 2-5 mu m in the ball mill by utilizing a negative pressure fan, collecting and reserving, and marking the prepared zinc oxide composite material as C-3, wherein the mass composition is as follows: 72% of graphene/ZnO and 28% of graphene/Zn.
Example 4
The embodiment provides a method for preparing a 1.6V-10Ah zinc-nickel storage battery, which specifically comprises the following steps:
step 1, anode homogenate
Adding the zinc oxide composite material (C-1), the carbon material, the dispersing agent and the like prepared in the embodiment 1 into a stirring kettle, dry-mixing for 8min, quickly adding deionized water within 4min, stirring for 8min, stopping for cleaning for 1min, wetting and stirring for 3min, slowly adding HEC aqueous solution, PTFE and the like within 15min, and stirring for 10min to obtain negative electrode zinc slurry, wherein the raw material formula is shown in the table 1;
table 1 raw material formulation of negative electrode zinc slurry
Step 2, pulling the slurry
The negative electrode zinc slurry is subjected to slurry pulling operation according to a specified gram weight;
step 3, drying
And (5) feeding the slurry pulling polar plate into a drying kiln for drying operation.
Step 4, assembling
Assembling the positive plate, the negative plate and the separator into a semi-finished battery according to the technological requirements.
Step 5, adding liquid to form
Injecting electrolyte into the semi-finished battery by using a vacuum electrolyte injection machine, and then performing formation to enable active substances in positive and negative green plates inside the battery to perform electrochemical conversion; the performance of the obtained zinc-nickel storage battery is the same as that of a traditional zinc oxide and formula battery (the traditional zinc oxide formula adopts an additive method, and the content of elements contained in the traditional zinc oxide composite material is the same as that of the zinc oxide composite material), the numbers of the zinc-nickel storage battery are 1# and 2# respectively (1 # and 3# are parallel samples, no distinction is made), and the numbers of the traditional zinc oxide formula battery are 4# and 5# and 6# respectively. The properties are shown in Table 2.
TABLE 2 comparison of Zinc-Nickel accumulator Performance with traditional Zinc oxide and formula Battery Performance
Example 5
The zinc-nickel storage battery prepared by the method of application example 4 was referred to by the zinc oxide alloy prepared in example 2, and the negative electrode zinc paste of this example was prepared by the zinc oxide composite material prepared in example 2, and the raw material formulation of the negative electrode zinc paste is shown in table 3:
TABLE 3 raw materials formulation of negative electrode zinc paste
In table 3, HEC refers to hydroxyethyl cellulose, and PTFE refers to polytetrafluoroethylene.
The properties of the obtained zinc-nickel secondary battery are shown in table 4.
TABLE 4 Performance of Zinc-Nickel accumulator
As can be seen from the results of tables 2 and 4, the zinc oxide composite material of the present invention was used as a negative electrode active material for a zinc-nickel secondary battery, and the battery capacity, the battery power and the service life of the battery were improved.
Example 6
The invention provides a preparation method of a zinc oxide composite material, which specifically comprises the following steps:
step 1, preparing zinc oxide alloy
In step 1, the preparation process of the graphene alloy is the same as example 1.
Adding graphene alloy as master alloy into molten zinc liquid to obtain zinc oxide alloy, wherein the zinc oxide alloy comprises the following components in mass: 1.8% of graphene, 1.7% of lead, 1.7% of copper, 0.6% of bismuth, 0.2% of indium, 0.03% of yttrium, 1.0% of cerium, 1.6% of tin and 0.1% of aluminum.
Step 2, preparing a zinc oxide composite material by utilizing the zinc oxide alloy prepared in the step 1, wherein the zinc oxide composite material comprises a low-temperature melting process, a ball milling oxidation process and a winnowing collection process; the method comprises the following steps:
low temperature melting process: adding zinc oxide alloy into a zinc melting furnace, and heating to 450 ℃ to melt the zinc oxide alloy to obtain zinc liquid;
casting zinc balls: the zinc liquid was poured into a mold to be molded, and then cooled to obtain zinc oxide spheres (particle diameter: 40 mm).
Ball milling oxidation process: the zinc oxide balls are sent into an Shimadzu ball mill, the rotating speed of a roller of the ball mill is controlled to be 25rpm, the zinc oxide balls collide and heat in the roller at 190 ℃, and are oxidized in an air environment to form a powdery composite material, namely the zinc oxide composite material.
Winnowing and collecting: sucking out zinc oxide composite material with the particle size of 3-5 mu m in the ball mill by using a negative pressure fan, and collecting for later use; the zinc oxide composite material comprises the following components in parts by mass: graphene/ZnO 73%; 26% of zinc oxide alloy, which contains: 1.8% of graphene, 1.7% of lead, 1.7% of copper, 0.6% of bismuth, 0.2% of indium, 0.03% of yttrium, 1.0% of cerium, 1.6% of tin and 0.1% of aluminum.
Example 7
The invention provides a preparation method of a zinc oxide composite material, which specifically comprises the following steps:
step 1, preparing zinc oxide alloy
In step 1, the preparation process of the graphene alloy is the same as example 1.
Adding graphene alloy as master alloy into molten zinc liquid to obtain zinc oxide alloy, wherein the zinc oxide alloy comprises the following components in mass: 1.0% of graphene, 1.0% of lead, 1.0% of copper, 0.8% of bismuth, 0.4% of indium, 0.04% of yttrium, 1.2% of cerium, 1.0% of tin and 0.3% of aluminum.
Step 2, preparing a zinc oxide composite material by utilizing the zinc oxide alloy prepared in the step 1, wherein the zinc oxide composite material comprises a low-temperature melting process, a ball milling oxidation process and a winnowing collection process; the method comprises the following steps:
low temperature melting process: adding zinc oxide alloy into a zinc melting furnace, and heating to 450 ℃ to melt the zinc oxide alloy to obtain zinc liquid;
casting zinc balls: the zinc liquid was poured into a mold to be molded, and then cooled to obtain zinc oxide spheres (particle diameter: 40 mm).
Ball milling oxidation process: the zinc oxide balls are sent into an Shimadzu ball mill, the rotating speed of a roller of the ball mill is controlled to be 25rpm, the zinc oxide balls collide and heat in the roller at 190 ℃, and are oxidized in an air environment to form a powdery composite material, namely the zinc oxide composite material.
Winnowing and collecting: sucking out zinc oxide composite material with the particle size of 3-5 mu m in the ball mill by using a negative pressure fan, and collecting for later use; the zinc oxide composite material comprises the following components in parts by mass: graphene/ZnO 74%; 25% of zinc oxide alloy, wherein the zinc oxide alloy comprises: 1.0% of graphene, 1.0% of lead, 1.0% of copper, 0.8% of bismuth, 0.4% of indium, 0.04% of yttrium, 1.2% of cerium, 1.0% of tin and 0.3% of aluminum.
The zinc oxide composite materials prepared in example 6 and example 7 were used as the negative electrode active material of a zinc-nickel storage battery, and a zinc-nickel storage battery was prepared according to the method of example 4, and the battery performance was comparable to the battery capacity, battery power and service life of the zinc-nickel storage battery prepared in example 4.
The existing zinc electrode modification methods include the following, see specifically comparative examples 1 to 5:
comparative example 1
The comparative example provides a zinc oxide modified by a mixed dispersion method, which comprises the following specific processes: the doping elements are mixed with zinc oxide and zinc powder to prepare the electrode, and the doping elements are doped with zinc during formation, so that the electrode performance can be improved. However, since the content of the additive elements is generally low, it is difficult to uniformly mix the trace elements by an additive mixing method, resulting in poor effect of the doping elements.
Comparative example 2
The comparative example provides a coprecipitation method modified zinc oxide, which specifically comprises the following steps: adopting soluble salt of doping element and zinc oxide in solution to carry out liquid phase deposition reaction, comprising the following steps:
step 1, weighing quantitative pure water, adding the pure water into a container with stirring and heating, opening a stirrer, and opening a heater to heat to a temperature T1;
step 2, adding quantitative polyethylene glycol, maintaining the temperature T1, and uniformly stirring;
step 3, weighing quantitative ZnO powder, adding the quantitative ZnO powder into the solution, maintaining the temperature T1, and uniformly stirring;
step 4, adding a quantitative mixed solution containing Bi0.1M and HNO31M, dropwise adding the mixed solution for about 30min, wherein the dropwise adding speed control method is that the upper limit and the lower limit of a dropwise adding bottle are marked, and stirring is continued for about 30min after the dropwise adding is finished;
and 5, measuring and quantifying a 1MNaOH solution, rapidly adding the solution into the solution, and stirring for about 1h. The temperature is always kept at T1. So that the pH value should be close to 7;
step 6, stopping stirring to precipitate the solution for about 1h, sucking out the clear solution (putting the clear solution into a liquid storage tank for centralized treatment), adding quantitative pure water, stirring and cleaning, and pumping out the surface clear solution after the solid is precipitated;
step 7, carrying out suction filtration, namely adding acetone when the liquid level is just close to the material, and continuing the suction filtration until no liquid flows out of the suction filtration funnel;
step 8, drying the filter cake to obtain a required coprecipitate, and finishing zinc oxide coating bismuth; the same method can also be used for coprecipitation of other elements, and coprecipitation of other elements and zinc oxide is obtained.
The method can obtain coprecipitate with uniform dispersion and good structure, but has complex process, needs to consume a large amount of chemical raw materials and a large amount of water, brings pollution risk, and is not environment-friendly and not clean.
Comparative example 3
The comparative example provides a ball milling dispersion method modified zinc oxide, which comprises the following specific processes: zinc oxide is mixed with elements to be added and added into a ball mill (or other dispersing equipment) for dispersion. The microelements are fully contacted with zinc oxide in a ball mill, and friction is carried out to obtain a uniform mixture. However, this method increases the ball milling and dispersing process, consumes energy, and the particle size of the obtained mixture is also changed, and the mixture is mostly physically dispersed, and the trace elements and zinc oxide are poorly combined, so that the doping effect is poor.
Comparative example 4
The comparative example provides a carbon-coated technology modified zinc oxide, which comprises the following specific processes: the preparation method comprises the steps of carrying out prepolymerization on a carbon source and an auxiliary agent to obtain a small molecular polymer dissolved in water, carrying out ball milling and mixing on a metal coordination polymer solution and zinc oxide to form a zinc oxide suspension, obtaining a precursor through spray drying or freeze drying and other methods, and calcining to obtain the carbon-coated zinc oxide. The ratio of carbon source, auxiliary material, modifier and zinc oxide, and calcination process are changed, the modifier is sulfur-philic salt, and the ratio of doping elements in the carbon layer and the thickness of the obtained carbon coating layer are adjusted. The method is characterized in that the influences of the components, morphology, structure and thickness of the carbon coating layer on the discharge capacity, high rate performance, charge and discharge efficiency and hydrogen evolution potential of the cathode material are analyzed through a series of material analysis and characterization such as X-ray diffraction, scanning electron microscopy, transmission electron microscopy, energy dispersion X-ray spectrum, X-ray photoelectron spectroscopy and the like and electrochemical analysis means such as cyclic voltammetry, electrochemical impedance spectroscopy, constant current charge and discharge and the like, and the zinc cathode material meeting technical indexes is obtained through condition optimization. The basic synthetic route is shown in figure 2.
The method can obtain zinc oxide coated with carbon material, increase conductivity of zinc oxide material, form protective shell of zinc oxide, and prevent zinc dendrite formation and zinc oxide dissolution and displacement. However, this method is poor in uniformity of dispersion, poor in combination, single in doping substance, excessive in consumed material, and serious in pollution, due to many doping and mixing methods, to obtain a mixture (or compound) of zinc oxide and doping elements.
Compared with the traditional method, the batteries prepared in the examples 4 and 5 are assembled by the zinc oxide composite material, the zinc-nickel battery assembled by the zinc oxide composite material has no failure caused by short circuit of dendrites, the cycle life of the battery is prolonged by about 1 time, the stability of a zinc electrode is obviously improved due to the zinc oxide prepared by the traditional method, and the water loss rate is reduced by about 38 percent due to the improvement of hydrogen evolution potential.
The present invention is not limited to the above-mentioned embodiments, and any changes or substitutions that can be easily understood by those skilled in the art within the technical scope of the present invention are intended to be included in the scope of the present invention.
Claims (5)
1. The zinc oxide composite material is characterized in that the zinc oxide composite material is a core-shell structure material;
the inner core of the zinc oxide composite material is zinc oxide alloy; the zinc oxide alloy comprises zinc and graphene;
the shell of the zinc oxide composite material is graphene/ZnO obtained by ball milling and oxidizing zinc oxide alloy;
the zinc oxide composite material comprises the following components in percentage by weight: 1-24% of zinc oxide alloy and 75-99% of graphene/ZnO;
the zinc oxide alloy also comprises a metal auxiliary agent;
the shell of the zinc oxide composite material further comprises a metal auxiliary oxide obtained by ball milling and oxidizing the metal auxiliary;
the metal auxiliary agent consists of lead, copper, bismuth, indium, yttrium, cerium, tin and aluminum;
in the zinc oxide alloy, the weight content of the graphene is 0.2-2%, the weight content of the lead is 0.001-2%, the weight content of the copper is 0.001-2%, the weight content of the bismuth is 0.001-1%, the weight content of the indium is 0.001-0.5%, the weight content of the yttrium is 0.001-0.5%, the weight content of the cerium is 0.001-1%, the weight content of the tin is 0.001-2%, and the weight content of the aluminum is 0.001-0.5%;
the metal auxiliary oxide consists of lead oxide, copper oxide, bismuth oxide, indium oxide, yttrium oxide, cerium oxide, tin oxide and aluminum oxide;
the graphene is used for connecting zinc oxide alloy at the inner core and metal auxiliary oxide at the outer shell to form a conductive network;
the preparation method of the zinc oxide composite material comprises the following steps:
step 1, melting zinc oxide alloy at a low temperature of 420-700 ℃, and injecting the molten zinc into a die to cast balls after melting to obtain zinc oxide alloy cast balls;
in the step 1, the preparation method of the zinc oxide alloy containing graphene comprises the following steps:
step 11, uniformly mixing molten salt of alkali metal halide with a carbon-containing additive to obtain a salt mixture;
the carbon-containing additive comprises TiC, B 4 C. At least one of active carbon, carbon black and graphite, wherein the addition amount of the carbon-containing additive is 0.005% -0.03% in terms of carbon;
step 12, firstly placing 30% -70% of the salt mixture into the bottom of an alumina crucible, then placing zinc or zinc oxide alloy into the salt mixture, then placing the rest of the salt mixture into the top of zinc or zinc oxide alloy, placing into a vertical heating furnace, heating to 520-900 ℃ to melt the salt mixture and zinc or zinc oxide alloy, decomposing a carbon-containing additive into carbon atoms, dispersing into the melted zinc or zinc oxide alloy, and heating for 0.5-5h to obtain a mixture;
step 13, cooling the mixture, and washing to remove the salt mixture therein, thereby obtaining zinc oxide alloy;
step 2, continuously ball-milling and oxidizing the zinc oxide alloy casting balls at 140-190 ℃, sucking out and collecting the zinc oxide composite material from the ball mill through a negative pressure fan after ball-milling and oxidizing to obtain the zinc oxide composite material,
wherein the rotating speed of the ball mill roller is 20-60rpm, and ball milling oxidation is carried out in an air environment; the granularity of the zinc oxide composite material is 1-5 mu m.
2. The zinc oxide composite material according to claim 1, wherein in the step 1, the particle size of the zinc oxide alloy cast balls produced is 20 to 60mm.
3. The zinc oxide composite according to claim 1, wherein in the step 1, or after the zinc oxide alloy is processed through a dicing process, a zinc oxide alloy block is obtained;
in the step 2, the zinc oxide alloy blocks are subjected to continuous ball milling oxidation at 140-190 ℃, and after ball milling oxidation, the zinc oxide composite material is sucked out of the ball mill through a negative pressure fan and collected, so that the zinc oxide composite material is obtained;
the thickness of the zinc oxide alloy block is 10-50mm.
4. A negative electrode zinc paste, which is obtained by using the zinc oxide composite material according to claim 1.
5. A zinc-nickel storage battery comprising the negative electrode paste according to claim 4.
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| CN107579219A (en) * | 2017-08-23 | 2018-01-12 | 北京航空航天大学 | For graphene/zinc oxide negative material of secondary zinc base battery and its preparation |
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| CN109585798A (en) * | 2017-09-29 | 2019-04-05 | 超威电源有限公司 | Graphene lead composite material and its preparation method and application and anode diachylon, cathode lead plaster |
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| CN103252228A (en) * | 2013-06-08 | 2013-08-21 | 江苏悦达墨特瑞新材料科技有限公司 | Preparation method of composite nanomaterial of nano ZnO and graphene nanosheet |
| CN107579219A (en) * | 2017-08-23 | 2018-01-12 | 北京航空航天大学 | For graphene/zinc oxide negative material of secondary zinc base battery and its preparation |
| CN107634192A (en) * | 2017-08-23 | 2018-01-26 | 北京航空航天大学 | A kind of zinc-base negative electrode battery material and preparation method thereof |
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