CN113611828A - Zinc oxide composite material, preparation method thereof, negative electrode zinc paste and zinc-nickel storage battery - Google Patents
Zinc oxide composite material, preparation method thereof, negative electrode zinc paste and zinc-nickel storage battery Download PDFInfo
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- CN113611828A CN113611828A CN202110809557.XA CN202110809557A CN113611828A CN 113611828 A CN113611828 A CN 113611828A CN 202110809557 A CN202110809557 A CN 202110809557A CN 113611828 A CN113611828 A CN 113611828A
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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 307
- 239000002131 composite material Substances 0.000 title claims abstract description 129
- QELJHCBNGDEXLD-UHFFFAOYSA-N nickel zinc Chemical compound [Ni].[Zn] QELJHCBNGDEXLD-UHFFFAOYSA-N 0.000 title claims abstract description 36
- RNWHGQJWIACOKP-UHFFFAOYSA-N zinc;oxygen(2-) Chemical compound [O-2].[Zn+2] RNWHGQJWIACOKP-UHFFFAOYSA-N 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title abstract description 23
- 238000003860 storage Methods 0.000 title abstract description 22
- 239000000956 alloy Substances 0.000 claims abstract description 138
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 138
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 96
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 78
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 67
- 239000011701 zinc Substances 0.000 claims abstract description 65
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 63
- 238000000498 ball milling Methods 0.000 claims abstract description 53
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 41
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- 239000000463 material Substances 0.000 claims abstract description 11
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- 239000002184 metal Substances 0.000 claims description 35
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- 239000012752 auxiliary agent Substances 0.000 claims description 19
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- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 14
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- 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
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- 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
- 239000002245 particle Substances 0.000 claims description 12
- 238000005266 casting Methods 0.000 claims description 9
- 239000011258 core-shell material Substances 0.000 claims description 3
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims 2
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- 239000011573 trace mineral Substances 0.000 abstract description 10
- 235000013619 trace mineral Nutrition 0.000 abstract description 10
- 210000001787 dendrite Anatomy 0.000 abstract description 6
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- 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
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- 238000010309 melting process Methods 0.000 description 8
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 5
- XOLBLPGZBRYERU-UHFFFAOYSA-N SnO2 Inorganic materials O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 5
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(iii) oxide Chemical compound O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 description 5
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 5
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- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
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- 239000013543 active substance Substances 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 229940105847 calamine Drugs 0.000 description 3
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- 239000012535 impurity Substances 0.000 description 3
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- -1 nickel metal hydride Chemical class 0.000 description 3
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- CPYIZQLXMGRKSW-UHFFFAOYSA-N zinc;iron(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Fe+3].[Fe+3].[Zn+2] CPYIZQLXMGRKSW-UHFFFAOYSA-N 0.000 description 3
- 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
- 239000005751 Copper oxide Substances 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
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- 229910052786 argon Inorganic materials 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229910000416 bismuth oxide Inorganic materials 0.000 description 2
- OJIJEKBXJYRIBZ-UHFFFAOYSA-N cadmium nickel Chemical compound [Ni].[Cd] OJIJEKBXJYRIBZ-UHFFFAOYSA-N 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 2
- 229910000420 cerium oxide Inorganic materials 0.000 description 2
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 2
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- 239000006071 cream Substances 0.000 description 2
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000002003 electrode paste Substances 0.000 description 2
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- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 2
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 description 2
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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
- H01M4/36—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, 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 further zinc dendrite short circuit occurs and the like. 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 a zinc oxide alloy cast ball or a zinc oxide alloy block; and 2, carrying out continuous ball milling oxidation on the zinc oxide alloy cast balls or the zinc oxide alloy blocks at the temperature of below 200 ℃, sucking out the zinc oxide composite material from the ball mill through a negative pressure fan after ball milling oxidation, and collecting to obtain the zinc oxide composite material. The zinc oxide composite material has uniform dispersion of the trace elements, and in addition, the preparation method is simple and effective, and the trace elements are uniformly dispersed and well combined with the 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 of the zinc oxide composite material, negative electrode zinc paste and a zinc-nickel storage battery.
Background
The secondary chemical power products commercialized to date have only: lead-acid batteries, cadmium-nickel batteries, nickel metal hydride (abbreviated as nickel-hydrogen) batteries, and lithium ion batteries. Among them, cadmium-nickel batteries have been completely banned from use in the domestic market due to pollution problems. Lead acid batteries are also increasingly limited by pollution problems. The lithium ion battery has high specific energy, is a mainstream product in the secondary battery market at present, but contains toxic electrolyte, and once leakage occurs, the lithium ion battery has high harm (influence) to the environment, and the safety of the lithium ion battery has problems. The nickel-hydrogen battery has higher environmental friendliness, and the market share is not high all the time because of the factors of higher cost, shorter service life, no superiority of specific energy compared with the lithium ion battery and the like. Therefore, a new chemical power source having excellent environmental friendliness, safety, and life span is needed.
The zinc-nickel battery is green and environment-friendly, and has no toxic substances such as lead, cadmium, organic solvent and PF 5; the battery adopts a water system electrolyte system, works at low internal pressure and has the characteristic of high safety; and has the advantages of high specific power (more than 200W/kg), high specific energy (more than 80Wh/kg), wide working temperature range (-40 ℃ -60 ℃), large-current charge and discharge and the like, and the raw materials are rich in sources.
Therefore, the zinc-nickel battery has wide application fields, and particularly in the application fields with high requirements on safety and reliability and high requirements on environmental adaptation, such as high-speed trains, airplanes, battlefield environments and the like, the zinc-nickel battery is one of the best power supply candidates. However, the zinc-nickel battery has five problems: dendrites, zinc electrode deformation, hydrogen evolution, zinc electrode corrosion and zinc electrode passivation. The prior art has adopted zinc electrode modification to ameliorate the above problems.
The existing zinc electrode modification methods are various and comprise a mixing dispersion method, a coprecipitation method, a ball milling dispersion method, a carbon coating technology and the like. However, the above modification methods all have problems such as uneven doping. The doping method which is simple, effective, uniform in dispersion, good in combination, clean and environment-friendly is found, and the method is very urgent for manufacturing zinc electrode materials and batteries.
Disclosure of Invention
In view of the above analysis, the present invention aims to provide a zinc oxide composite material, a preparation method thereof, a 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 be uniformly dispersed in the zinc paste, and further, the quality problems such as zinc dendrite short circuit occur.
The purpose of the invention is mainly realized by the following technical scheme:
on one hand, the invention provides a zinc oxide composite material which 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 a 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 assistant oxides corresponding to the metal assistant are respectively PbO, CuO and Bi2O3、In2O3、Y2O3、CeO2、SnO2And Al2O3；
In the zinc oxide alloy, the weight content of the graphene is 0.01-2%, and the weight content of the metal additive is 0.01-10%.
In another aspect, the present invention provides a method for preparing a zinc oxide composite material, for preparing the above zinc oxide composite material, comprising the following steps:
step 1, melting zinc oxide alloy at low temperature, and injecting the obtained zinc liquid into a mold to cast a ball to obtain a zinc oxide alloy cast ball;
and 2, carrying out continuous ball milling oxidation on the zinc oxide alloy cast ball at the temperature of below 200 ℃, sucking out the zinc oxide composite material from the ball mill through a negative pressure fan after ball milling oxidation, and collecting to obtain the zinc oxide composite material.
Further, in step 1, the low-temperature melting temperature is 420-700 ℃;
the grain diameter of the prepared zinc oxide alloy casting ball is 20-60 mm.
Further, in the step 2, the temperature of ball milling oxidation is 140-;
after ball milling and oxidation, the granularity of the prepared zinc oxide composite material is 0.1-5 mu m.
Further, or, the zinc oxide alloy is processed by a cutting procedure to obtain a zinc oxide alloy block;
in the step 2, continuously ball-milling and oxidizing the zinc oxide alloy block at the temperature of below 200 ℃, sucking out the zinc oxide composite material from the ball mill by a negative pressure fan after ball-milling and oxidizing, and collecting to obtain the zinc oxide composite material;
the thickness of the zinc oxide alloy block is 10-50 mm.
Further, in the step 2, the rotating speed of a roller of the ball mill is 20-60rpm, and ball milling oxidation is carried out in an air environment;
the particle size of the zinc oxide composite material is 1-5 mu m.
Furthermore, 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 a 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 can realize at least one of the following beneficial effects:
(1) according to the invention, microelements are added into the zinc oxide alloy as a metal auxiliary agent, the metal auxiliary agent and zinc form an alloy, and the alloy is uniformly distributed in the zinc matrix in the form of atoms or compounds, so that the preparation process is simple, and uniform distribution of the microelements can be realized.
(2) According to the invention, the zinc oxide composite material is prepared by using the zinc oxide alloy, in the ball milling oxidation process, the zinc oxide alloy cast balls and the zinc oxide alloy blocks can collide with each other, the surface is continuously oxidized and crushed, after the ball milling oxidation is finished, the unoxidized zinc oxide alloy is arranged at the core part of the zinc oxide composite material, and as the graphene has higher tensile strength and extremely high toughness, the graphene can connect the zinc oxide alloy at the core part with the peripheral metal oxide to form a good conductive network.
(3) The zinc oxide composite material prepared by the invention keeps stable distribution of trace elements (metal additives) and graphene and other materials in the zinc paste preparation process and the subsequent battery production processes, and the phenomenon of uneven distribution of the trace elements of the additives caused by stirring equipment and process problems in the zinc paste preparation process is avoided.
(4) The invention can overcome the quality problems of the zinc electrode by the trace elements in the metal auxiliary agent in the zinc oxide alloy, such as: the invention has the advantages of solving the problems of uneven conductivity, easy hydrogen gas precipitation of the zinc electrode, zinc dendrite growth and the like, namely the invention can prepare the reliable zinc electrode and further manufacture the high-performance zinc system battery.
In the invention, the technical schemes can be combined with each other 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 will be realized and attained by the structure 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, wherein like reference numerals are used to designate like parts throughout.
FIG. 1 is a schematic diagram of a process for preparing a zinc oxide composite;
FIG. 2 is a schematic of a route to zinc oxide alloy preparation by carbon cladding techniques;
FIG. 3 is a micro-topography of the zinc oxide composite C-1 prepared in example 1.
Detailed Description
The preferred embodiments of the present invention will now be described in detail with reference to the accompanying drawings, which form a part hereof, and which together with the embodiments of the invention serve to explain the principles of the invention and not to limit its scope.
On one hand, the invention provides a zinc oxide composite material which 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 a 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 used 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 assistant oxides corresponding to the metal assistant are PbO, CuO and Bi respectively2O3、In2O3、Y2O3、CeO2、SnO2And Al2O3。
In the zinc oxide alloy, the weight content of the graphene is 0.01-2%, and the weight content of the metal additive is 0.01-10%.
Specifically, the invention provides a zinc oxide composite material, wherein an inner core of the composite material is a zinc oxide alloy (the zinc oxide alloy comprises zinc, graphene and a metal auxiliary agent), and an outer shell of the composite material is graphene/metal oxide (the metal oxide comprises ZnO and a metal auxiliary agent oxide), namely the zinc oxide composite material comprises the zinc oxide alloy at the inner part and the graphene/metal oxide which is positioned at the outer part of 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, the graphene is doped in the metal oxide to form a composite, and the composite is expressed in the form of graphene/metal oxide, for example, the composite formed by graphene and ZnO is expressed as graphene/ZnO, and graphene and Bi are expressed as2O3The formed composite is expressed as graphene/Bi2O3。
It is emphasized that, because the content of the graphene is relatively small and it is difficult to accurately measure the content of the graphene, the graphene part is doped in the metal oxide and forms a composite, and in order to embody the combination manner of the graphene and the metal oxide, the content of the composite of the graphene and the metal oxide is calculated by the content of the metal oxide; the testing method of the metal oxide is that the metal oxide in the compound is dissolved out by using a corresponding solvent, and the metal content in the solution is measured by using an ICP emission spectrometer.
Illustratively, in the above zinc oxide composite material: 50-95% of ZnO, 0.01-2% of graphene (e.g., 0.05% -2%), and 5-50% of zinc oxide alloy (e.g., 15-30%); the metal promoter oxide is present in an amount of 0 to 10% by weight (e.g., 0.001 to 5%).
In a third aspect, the present invention further provides a preparation method of a zinc oxide composite material, as shown in fig. 1, specifically including the following steps:
step 1, melting zinc oxide alloy at low temperature, wherein the melting temperature is 420-700 ℃; after the zinc oxide alloy is melted, injecting the obtained zinc liquid into a mould to cast balls, wherein the grain diameter of the prepared zinc oxide alloy cast balls is 20-60 mm;
and 2, casting the zinc oxide alloy balls, and then carrying out continuous ball milling oxidation in a ball mill, wherein the ball milling oxidation temperature is below 200 ℃, the rotating speed of a roller of the ball mill is 20-60rpm, the ball milling oxidation is carried out in an air environment, and after the ball milling oxidation, 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 to prepare the zinc oxide composite material.
In the step 1, the zinc oxide alloy is melted at low temperature of 420-700 ℃, which is beneficial to reducing the waste of 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 again. The thickness of the zinc oxide alloy block prepared by the cutting procedure is 10-50 mm; and carrying out continuous ball milling oxidation on the obtained zinc oxide alloy block at the temperature of below 200 ℃, sucking out the zinc oxide composite material from the ball mill by a negative pressure fan after ball milling oxidation, and collecting to obtain the zinc oxide composite material.
Compared with the prior art, the ball milling oxidation method is that the zinc oxide alloy is subjected to ball milling oxidation after being subjected to melting ball casting or cutting, graphene is uniformly distributed in a matrix, the ball milling oxidation temperature is controlled below 200 ℃ (for example, 140-.
In the step 1, the zinc oxide alloy is melted at low temperature, the graphene and the metal auxiliary agent can be well dispersed, and the two methods of melting, ball casting or ball milling and oxidation after dicing can avoid the agglomeration of the graphene and keep the uniform dispersion of the graphene.
Illustratively, in the zinc oxide alloy in the 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 additive is 0.1-10%.
Illustratively, in the zinc oxide alloy in step 1 above, the weight content of graphene is 0-2%, 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 the zinc oxide alloy in the step 1, the weight content of the graphene is 0.001 to 2%, and the weight content of the metal additive is 0.1 to 10%. The metal auxiliary agent is used as a doping agent of the 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 temperature of ball milling oxidation is 140-.
In the step 2, after ball milling oxidation, the particle size of the prepared zinc oxide composite material is 1-5 μm.
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 the apparent density of the zinc oxide composite material can be adjusted by positive pressure air volume and negative pressure air volume.
In the step 2, in the ball milling oxidation process, the zinc oxide alloy cast balls and the zinc oxide alloy cast balls collide with each other, the surfaces are continuously oxidized and crushed, metal components (zinc and metal auxiliaries) in the zinc oxide alloy cast balls can be converted into corresponding metal oxides, and graphene is not basically oxidized; 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 non-oxidized zinc oxide alloy is arranged at the core part of the zinc oxide composite material, and the graphene can connect the zinc oxide alloy at the core part and 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 invention further provides a method for preparing a zinc oxide alloy containing graphene by using a molten salt method, which specifically comprises the following steps:
step 1, melting salt of alkali metal halide and carbon-containing additive (such as TiC and B)4C. 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 percent of the carbon by weight of the carbon, and the salt mixture is obtained by uniformly mixing;
step 2, firstly putting 30-70% of salt mixture at the bottom of an alumina crucible, then putting zinc or zinc oxide alloy into the partial salt mixture, then putting the rest salt mixture at the top of the zinc or zinc oxide alloy, putting the zinc or zinc oxide alloy into a vertical heating furnace, heating to the temperature of 520-900 ℃ to melt the salt mixture and the zinc or zinc oxide alloy, decomposing the carbon-containing additive into carbon atoms, dispersing the carbon atoms into the molten 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 without 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 graphene-containing zinc oxide alloy by using a redox method, comprising the following steps:
step 1, preparing a graphene alloy;
dispersing natural graphite in water, and carrying out an oxidation reaction (exemplarily, the oxidation reaction is carried out for 20h-28h at 65-85 ℃) by taking sulfuric acid as an oxidant under a certain condition 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 performing a reduction reaction under certain conditions (illustratively, oxidation reaction at 55-70 ℃ for 15-25 h); after reduction, washing and drying the obtained reduction reaction system, placing the obtained reduction product in a closed container for heating, taking argon as protective gas, heating for a certain time, and cooling (exemplarily, heating at 750-850 ℃ for 5-15min) to obtain the graphene alloy.
And 2, adding the graphene alloy serving as a mother alloy into the molten zinc liquid to obtain the zinc oxide alloy containing graphene.
Illustratively, the zinc oxide composite material contains 0.1-3 wt% of Bi2O3The conductive capability of the 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 wt% of SnO2The conductivity can be improved, and the hydrogen evolution amount can be reduced.
Illustratively, the zinc oxide composite material contains 0.01-1% by weight of graphene.
Illustratively, the zinc oxide composite material contains 0.1-0.5% by weight of In2O3The 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 of a zinc-nickel secondary battery. Therefore, the invention also provides a negative electrode zinc paste, which is used for a zinc-nickel storage battery and comprises the zinc oxide composite material.
The zinc oxide composite material is used as a negative active material, and the weight content of the zinc oxide composite material is 70-99.8% by dry weight of the negative calamine cream after charging and discharging.
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 (e.g., optional carbon materials, PTFE, CMC, etc.) included in or used to prepare the negative electrode calamine of the present invention are well known in the art and will not be described in detail herein.
It is worth noting that the testing method of the metal oxide in the zinc oxide composite material of the invention is as follows: 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, calculating the content of the metal oxide, and taking the balance of the 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, for example, the zinc-nickel storage battery is prepared by homogenizing, pulling slurry, drying a polar plate, assembling, adding liquid and forming in sequence. The specific operating conditions are well known in the art and will not be described further herein.
The open-circuit voltage of the zinc-nickel storage battery is tested by a voltmeter; discharging and detecting the storage battery by using a charging and discharging machine to measure the discharged energy Q, weighing the mass m of the storage battery by using an electronic scale, wherein 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 amplification 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 and can be used as a negative active substance, and the prepared zinc-nickel storage battery has higher battery capacity, battery power and battery life (see tables 2 and 4), and has wide application prospects.
Example 1
The invention provides a preparation method of a zinc oxide composite material, which specifically comprises the following steps:
step 1, preparing a zinc oxide alloy (the zinc oxide alloy containing graphene is prepared by using a redox method provided by the fifth aspect), specifically as follows:
dispersing natural graphite in water, and carrying out oxidation reaction for 24 hours at 75 ℃ by using sulfuric acid as an oxidant; obtaining graphene oxide, dispersing and washing the graphene oxide by using ultrasonic waves, then 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 the temperature of 60 ℃; and after reduction, washing and drying the obtained reduction reaction system, placing the obtained reduction product in a closed container for heating, taking argon as protective gas, controlling the pressure of the protective gas to be 5 standard atmospheric pressures, heating at the temperature of 800 ℃, heating for 10min, and then cooling to obtain the graphene alloy.
Adding a graphene alloy serving as a master alloy into molten zinc liquid to obtain a zinc oxide alloy, wherein the zinc oxide alloy comprises the following components in percentage by 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 the zinc oxide composite material by using the zinc oxide alloy prepared in the step 1, wherein the preparation method comprises a low-temperature melting process, a ball-milling oxidation process and a winnowing collection process; the method comprises the following specific steps:
and (3) low-temperature melting process: adding zinc oxide alloy into a zinc melting furnace, heating to 550 ℃, and melting to obtain zinc liquid;
casting a zinc ball: and injecting the zinc liquid into a mold for molding, and then cooling to obtain zinc oxide spheres (with the particle size of 30 mm).
Ball milling and oxidizing: and (2) feeding the zinc oxide balls into an Shimadzu ball mill, controlling the rotating speed of a roller of the ball mill to be 50rpm, enabling the zinc oxide balls to collide and generate heat in the roller at 170 ℃, and oxidizing the zinc oxide balls in an air environment to form a powdery composite material, namely the zinc oxide composite material.
Air separation and collection: sucking out the zinc oxide composite material with the particle size of 2-5 microns in the ball mill by using a negative pressure fan, and collecting and reserving the zinc oxide composite material as C-1;
the mass composition of C-1 is as follows: graphene/ZnO 75%; 24% of zinc oxide alloy, wherein the zinc oxide alloy comprises: 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 micro-topography 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
The zinc oxide alloy was prepared according to the method of example 1, except that the zinc oxide alloy contained only zinc and graphene in the composition, the weight content of graphene was 0.2%, the remaining elements were metallic zinc and trace impurities, and the trace impurities were negligible.
Step 2, preparing the 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 specific steps:
and (3) low-temperature melting process: adding zinc oxide alloy into a zinc melting furnace, heating to 550 ℃, and melting to obtain zinc liquid;
casting a zinc ball: and injecting the zinc liquid into a mold for molding, and then cooling to obtain zinc oxide spheres (with the particle size of 30 mm).
Ball milling and oxidizing: and (2) feeding the zinc oxide balls into an Shimadzu ball mill, controlling the rotating speed of a roller of the ball mill to be 50rpm, enabling the zinc oxide balls to collide and generate heat in the roller at 170 ℃, and oxidizing the zinc oxide balls in an air environment to form a powdery composite material, namely the zinc oxide composite material.
Air separation and collection: sucking out the zinc oxide composite material with the particle size of 2-5 microns 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 percentage by mass: 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 preparation method of the zinc oxide composite material in the embodiment 2 in that: in the step 2, the zinc oxide alloy is cut into blocks to replace the zinc oxide alloy, and the zinc oxide alloy is melted and cast into balls; the method specifically comprises the following steps:
step 1, preparing zinc oxide alloy
The specific procedure was the same as in example 2.
Step 2, preparing a zinc oxide composite material by using the zinc oxide alloy prepared in the step 1;
sequentially carrying out zinc ingot feeding, zinc block punching, zinc block conveying and zinc block receiving on zinc oxide alloy to obtain cut blocks with the thickness of 30mm, and then carrying out ball milling oxidation process and air separation collection process; the method comprises the following specific steps:
ball milling and oxidizing: and (2) feeding the zinc oxide balls into an Shimadzu ball mill, controlling the rotating speed of a roller of the ball mill to be 50rpm, enabling the zinc oxide balls to collide and generate heat in the roller at 170 ℃, and oxidizing the zinc oxide balls in an air environment to form a powdery composite material, namely the zinc oxide composite material.
Air separation and collection: sucking out the zinc oxide composite material with the particle size of 2-5 microns in the ball mill by using a negative pressure fan, collecting and reserving for later use, recording the prepared zinc oxide composite material as C-3, wherein the mass composition of the zinc oxide composite material 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, homogenizing a negative electrode
Adding the zinc oxide composite material (C-1) prepared in the example 1, a carbon material, a dispersing agent and the like into a stirring kettle, after dry mixing for 8min, quickly adding deionized water within 4min, after stirring for 8min, stopping the machine for cleaning for 1min, then carrying out wet stirring for 3min, then slowly adding an HEC aqueous solution, PTFE and the like within 15min, and stirring for 10min to obtain a negative electrode zinc slurry, wherein the raw material formula is shown in Table 1;
table 1 raw material formulation of negative electrode zinc slurry
Step 2, slurry drawing
Performing slurry drawing operation on the cathode zinc slurry according to the specified gram weight;
step 3, drying
And (5) feeding the slurry drawing pole plate into a drying kiln for drying operation.
Step 4, assembling
And assembling the positive plate, the negative plate and the separator into a semi-finished battery according to the process requirements.
Step 5, liquid adding formation
Injecting electrolyte into the semi-finished battery by using a vacuum liquid injection machine, and then performing formation to perform electrochemical conversion on active substances in positive and negative electrode plates in the battery; the obtained zinc-nickel accumulator has the same performance as traditional zinc oxide and its formula (the traditional zinc oxide formula adopts additive method, and the additive is identical to the element content in the zinc oxide composite material), and its serial numbers are 1#, 2#, 3# (1#, 2#, 3# are parallel samples, and have no difference), and the traditional zinc oxide formula battery serial numbers are 4#, 5#, 6 #. The properties are shown in Table 2.
TABLE 2 comparison of the Performance of the Zn-Ni accumulators with the Performance of the conventional Zinc oxide and the formulated batteries
Example 5
In contrast to example 4, in which a zinc-nickel storage battery was manufactured using the zinc oxide alloy prepared in example 2 and referring to the method of application example 4, the negative electrode paste of this example was a zinc oxide composite material prepared by the method of example 2, the raw material formulation of the negative electrode paste is shown in table 3:
TABLE 3 raw material formulation of negative electrode calamine cream
In table 3, HEC means hydroxyethyl cellulose, and PTFE means polytetrafluoroethylene.
The properties of the obtained zinc-nickel secondary battery are shown in Table 4.
TABLE 4 Zinc-Nickel Battery Performance
It can be seen from the results in tables 2 and 4 that the use of the zinc oxide composite material of the present invention as the negative active material of a zinc-nickel secondary battery can improve the battery capacity, the battery power and the service life of the battery.
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 graphene alloy was prepared in the same manner as in example 1.
Adding a graphene alloy serving as a master alloy into molten zinc liquid to obtain a zinc oxide alloy, wherein the zinc oxide alloy comprises the following components in percentage by 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 the zinc oxide composite material by using the zinc oxide alloy prepared in the step 1, wherein the preparation method comprises a low-temperature melting process, a ball-milling oxidation process and a winnowing collection process; the method comprises the following specific steps:
and (3) low-temperature melting process: adding zinc oxide alloy into a zinc melting furnace, heating to 450 ℃, and melting to obtain zinc liquid;
casting a zinc ball: and injecting the zinc liquid into a mold for molding, and then cooling to obtain zinc oxide spheres (with the particle size of 40 mm).
Ball milling and oxidizing: and (2) feeding the zinc oxide balls into an Shimadzu ball mill, controlling the rotating speed of a roller of the ball mill to be 25rpm, enabling the zinc oxide balls to collide and generate heat in the roller at 190 ℃, and oxidizing the zinc oxide balls in an air environment to form a powdery composite material, namely the zinc oxide composite material.
Air separation and collection: sucking out the zinc oxide composite material with the grain diameter 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 percentage by mass: graphene/ZnO 73%; 26% of zinc oxide alloy, wherein the zinc oxide alloy comprises: 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 graphene alloy was prepared in the same manner as in example 1.
Adding a graphene alloy serving as a master alloy into molten zinc liquid to obtain a zinc oxide alloy, wherein the zinc oxide alloy comprises the following components in percentage by 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 the zinc oxide composite material by using the zinc oxide alloy prepared in the step 1, wherein the preparation method comprises a low-temperature melting process, a ball-milling oxidation process and a winnowing collection process; the method comprises the following specific steps:
and (3) low-temperature melting process: adding zinc oxide alloy into a zinc melting furnace, heating to 450 ℃, and melting to obtain zinc liquid;
casting a zinc ball: and injecting the zinc liquid into a mold for molding, and then cooling to obtain zinc oxide spheres (with the particle size of 40 mm).
Ball milling and oxidizing: and (2) feeding the zinc oxide balls into an Shimadzu ball mill, controlling the rotating speed of a roller of the ball mill to be 25rpm, enabling the zinc oxide balls to collide and generate heat in the roller at 190 ℃, and oxidizing the zinc oxide balls in an air environment to form a powdery composite material, namely the zinc oxide composite material.
Air separation and collection: sucking out the zinc oxide composite material with the grain diameter 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 percentage 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 examples 6 and 7 were used as negative electrode active materials of zinc-nickel secondary batteries, and zinc-nickel secondary batteries were prepared according to the method of example 4, and the battery performance of the zinc-nickel secondary batteries was comparable to the battery capacity, battery power and service life of the zinc-nickel secondary batteries prepared in example 4.
The existing zinc electrode modification methods comprise the following methods, and specifically refer to comparative examples 1 to 5:
comparative example 1
The comparison example provides a mixed dispersion method for modifying zinc oxide, and the specific process comprises the following steps: when the electrode is manufactured, the doping elements are mixed with zinc oxide and zinc powder to manufacture the electrode, and the doping elements and the zinc are doped together during the formation, so that the electrode performance can be improved. However, because the content of the additive elements is generally low, it is difficult to mix these trace elements uniformly by the additive mixing method, resulting in poor effect of the doping elements.
Comparative example 2
The comparative example provides a coprecipitation method for modifying zinc oxide, which specifically comprises the following steps: the method adopts soluble salt of doping elements and zinc oxide to carry out liquid phase deposition reaction in solution, and comprises the following steps:
step 1, weighing quantitative pure water, adding the pure water into a container with stirring and heating functions, turning on a stirrer, turning on a heater, and heating to a temperature T1;
step 2, adding a certain amount of polyethylene glycol, keeping the temperature T1, and uniformly stirring;
step 3, weighing quantitative ZnO powder, adding the ZnO powder into the solution, keeping the temperature T1, and uniformly stirring;
step 4, adding a certain amount of mixed solution containing Bi0.1M and HNO31M, controlling the dropping for about 30min, wherein the dropping speed is controlled by marking upper limit and lower limit scales on a dropping bottle and continuously stirring for about 30min after the dropping is finished;
and 5, measuring a certain amount of 1M NaOH solution, quickly adding the solution into the solution, and stirring for about 1 hour. The temperature was kept at T1. So that the pH should be close to 7;
step 6, stopping stirring to precipitate the solution, sucking out the clear liquid of the solution (putting the solution into a liquid storage tank for centralized treatment) after about 1 hour, adding quantitative pure water, stirring and cleaning, and sucking off the surface clear liquid after the solid is precipitated;
step 7, carrying out suction filtration treatment, adding acetone when the liquid level is right 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; in the same manner, coprecipitation of other elements can be carried out to obtain a coprecipitate of the other elements and zinc oxide.
The method can obtain the coprecipitate with uniform dispersion and better structure, but the process is complex, a large amount of chemical raw materials and water are consumed, the pollution risk is brought, and the process is not environment-friendly and not clean.
Comparative example 3
This comparison example provides a ball mill dispersion method modification zinc oxide, and specific process includes: mixing the zinc oxide with elements to be added, adding the mixture into a ball mill (or other dispersing equipment) for dispersing. The trace elements are fully contacted and rubbed with the zinc oxide in the ball mill to obtain a more uniform mixture. However, this method requires an additional step of ball milling dispersion, requires energy, and the resulting mixture may change in particle size, often resulting in physical dispersion of the mixture, poor binding of trace elements to zinc oxide, and poor doping effects.
Comparative example 4
The comparison example provides a carbon coating technology modified zinc oxide, which comprises the following specific processes: pre-polymerizing a carbon source and an assistant to obtain a small molecular polymer dissolved in water, mixing a metal coordination polymer solution and a zinc oxide ball mill to form a zinc oxide suspension, spray drying or freeze drying to obtain a precursor, and calcining to obtain the carbon-coated zinc oxide. The proportion of the carbon source, the auxiliary material, the modifier and the zinc oxide and the calcining process are changed, the modifier is the salt of the thiophilic element, and the proportion of the doping element in the carbon layer and the thickness of the obtained carbon coating layer are adjusted. The influence of the components, the morphology, the structure and the thickness of the carbon coating layer on the discharge capacity, the high-rate performance, the charge-discharge efficiency and the hydrogen escape potential of the cathode material is analyzed by a series of material analysis and characterization such as X-ray diffraction, a scanning electron microscope, a transmission electron microscope, an energy dispersion X-ray spectrum and an X-ray photoelectron spectrum, and electrochemical analysis means such as cyclic voltammetry, electrochemical impedance spectroscopy and constant current charge-discharge, and the like, so that the zinc cathode material meeting the technical indexes is obtained by condition optimization. The basic synthetic route is shown in FIG. 2.
The method can obtain carbon-coated zinc oxide, increase the conductivity of the zinc oxide material, form a zinc oxide protective shell, and prevent the formation of zinc dendrite and the dissolution and displacement of zinc oxide. However, this method, which can obtain a mixture (or compound) of zinc oxide and doping elements due to various doping and mixing methods, has poor dispersion uniformity, poor bonding, single doping material, excessive material consumption, and serious contamination.
Compared with the conventional method, the zinc-nickel battery assembled by the zinc oxide composite material prepared by the invention and the zinc-nickel battery prepared by the zinc oxide composite material prepared by the embodiment 4 and the embodiment 5 have no failure caused by short circuit of dendrite in a test, the cycle life of the battery is prolonged by about 1 time, and the stability of a zinc electrode is obviously reduced by about 38 percent due to the improvement of hydrogen evolution potential of the zinc oxide prepared by the conventional method.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are included in the scope of the present invention.
Claims (10)
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 a 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.
2. The zinc oxide composite of claim 1, wherein the zinc oxide alloy further comprises 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;
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%.
3. A method for preparing a zinc oxide composite material, for preparing the zinc oxide composite material of claim 1 or 2, comprising the steps of:
step 1, melting zinc oxide alloy at low temperature, and injecting the obtained zinc liquid into a mold to cast a ball to obtain a zinc oxide alloy cast ball;
and 2, carrying out continuous ball milling oxidation on the zinc oxide alloy cast ball at the temperature of below 200 ℃, sucking out the zinc oxide composite material from the ball mill through a negative pressure fan after ball milling oxidation, and collecting to obtain the zinc oxide composite material.
4. The method for preparing the zinc oxide composite material as claimed in claim 3, wherein in the step 1, the low-temperature melting temperature is 420-700 ℃;
the grain diameter of the prepared zinc oxide alloy casting ball is 20-60 mm.
5. The method for preparing the zinc oxide composite material as claimed in claim 3, wherein in the step 2, the temperature of the ball milling oxidation is 140-190 ℃;
after ball milling and oxidation, the granularity of the prepared zinc oxide composite material is 0.1-5 mu m.
6. The method of producing a zinc oxide composite material according to claim 3, wherein in the step 1, or after the zinc oxide alloy is processed by a dicing step, a zinc oxide alloy ingot is obtained;
in the step 2, the zinc oxide alloy block is subjected to continuous ball milling oxidation at a temperature below 200 ℃, and after ball milling oxidation, the zinc oxide composite material is sucked out of the ball mill by a negative pressure fan and collected to obtain the zinc oxide composite material;
the thickness of the zinc oxide alloy block is 10-50 mm.
7. The method for preparing a zinc oxide composite material according to claims 5 and 6, wherein in the step 2, the rotation speed of the ball mill roller is 20-60rpm, and the ball milling oxidation is performed in an air environment;
the particle size of the zinc oxide composite material is 1-5 mu m.
8. The method according to claim 3, wherein the zinc oxide alloy comprises 0.001 to 2% by weight of graphene, 0.001 to 2% by weight of lead, 0.001 to 2% by weight of copper, 0.001 to 1% by weight of bismuth, 0.001 to 0.5% by weight of indium, 0.001 to 0.5% by weight of yttrium, 0.001 to 15% by weight of cerium, 0.001 to 2% by weight of tin, and 0.001 to 0.5% by weight of aluminum.
9. A negative electrode zinc paste, which is characterized by being obtained by using the zinc oxide composite material according to claim 1 or 2;
alternatively, it is prepared by using the zinc oxide composite material prepared by claims 3 to 8.
10. A zinc-nickel secondary battery comprising the negative electrode zinc paste of claim 9.
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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 |
| 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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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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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 |
| 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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