CN115084454A - Alkaline zinc-manganese battery cathode and preparation method thereof - Google Patents
Alkaline zinc-manganese battery cathode and preparation method thereof Download PDFInfo
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- CN115084454A CN115084454A CN202110941516.6A CN202110941516A CN115084454A CN 115084454 A CN115084454 A CN 115084454A CN 202110941516 A CN202110941516 A CN 202110941516A CN 115084454 A CN115084454 A CN 115084454A
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- zinc
- alkaline
- negative electrode
- manganese dioxide
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- WJZHMLNIAZSFDO-UHFFFAOYSA-N manganese zinc Chemical compound [Mn].[Zn] WJZHMLNIAZSFDO-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title description 7
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000000843 powder Substances 0.000 claims abstract description 26
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000011787 zinc oxide Substances 0.000 claims abstract description 21
- 239000007787 solid Substances 0.000 claims abstract description 20
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 18
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 18
- 239000002131 composite material Substances 0.000 claims abstract description 17
- 239000008367 deionised water Substances 0.000 claims abstract description 11
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 11
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000011230 binding agent Substances 0.000 claims abstract description 9
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 9
- 239000002994 raw material Substances 0.000 claims abstract description 9
- 235000014692 zinc oxide Nutrition 0.000 claims description 20
- 238000003756 stirring Methods 0.000 claims description 17
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 14
- SZKTYYIADWRVSA-UHFFFAOYSA-N zinc manganese(2+) oxygen(2-) Chemical compound [O--].[O--].[Mn++].[Zn++] SZKTYYIADWRVSA-UHFFFAOYSA-N 0.000 claims description 13
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 12
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 10
- 239000011259 mixed solution Substances 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 9
- 239000011347 resin Substances 0.000 claims description 8
- 229920005989 resin Polymers 0.000 claims description 8
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 claims description 6
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 239000007822 coupling agent Substances 0.000 claims description 6
- ZOIVSVWBENBHNT-UHFFFAOYSA-N dizinc;silicate Chemical group [Zn+2].[Zn+2].[O-][Si]([O-])([O-])[O-] ZOIVSVWBENBHNT-UHFFFAOYSA-N 0.000 claims description 6
- 150000002576 ketones Chemical class 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 239000004014 plasticizer Substances 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 239000006185 dispersion Substances 0.000 claims description 5
- 239000000243 solution Substances 0.000 claims description 5
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 4
- 239000002033 PVDF binder Substances 0.000 claims description 4
- 239000004110 Zinc silicate Substances 0.000 claims description 4
- 239000012752 auxiliary agent Substances 0.000 claims description 4
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 claims description 4
- 239000002482 conductive additive Substances 0.000 claims description 4
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 4
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 claims description 4
- 229920003063 hydroxymethyl cellulose Polymers 0.000 claims description 4
- 229940031574 hydroxymethyl cellulose Drugs 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 4
- GQIUQDDJKHLHTB-UHFFFAOYSA-N trichloro(ethenyl)silane Chemical compound Cl[Si](Cl)(Cl)C=C GQIUQDDJKHLHTB-UHFFFAOYSA-N 0.000 claims description 4
- 239000005050 vinyl trichlorosilane Substances 0.000 claims description 4
- 235000019352 zinc silicate Nutrition 0.000 claims description 4
- 229940105847 calamine Drugs 0.000 claims description 3
- 239000010406 cathode material Substances 0.000 claims description 3
- 239000006071 cream Substances 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 229910052864 hemimorphite Inorganic materials 0.000 claims description 3
- 238000009775 high-speed stirring Methods 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- -1 polyperoxyethylene Polymers 0.000 claims description 3
- 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 claims description 3
- 239000004115 Sodium Silicate Substances 0.000 claims description 2
- 229920002125 Sokalan® Polymers 0.000 claims description 2
- 239000012670 alkaline solution Substances 0.000 claims description 2
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 claims description 2
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 2
- 239000000347 magnesium hydroxide Substances 0.000 claims description 2
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 2
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 claims description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 2
- 239000004584 polyacrylic acid Substances 0.000 claims description 2
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 2
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 2
- 239000004800 polyvinyl chloride Substances 0.000 claims description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 7
- 238000011161 development Methods 0.000 abstract description 2
- 230000002035 prolonged effect Effects 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 11
- 239000011701 zinc Substances 0.000 description 10
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- 239000011572 manganese Substances 0.000 description 5
- 239000002048 multi walled nanotube Substances 0.000 description 5
- 229910021389 graphene Inorganic materials 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000002096 quantum dot Substances 0.000 description 4
- RNWHGQJWIACOKP-UHFFFAOYSA-N zinc;oxygen(2-) Chemical compound [O-2].[Zn+2] RNWHGQJWIACOKP-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 229910052797 bismuth Inorganic materials 0.000 description 3
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052738 indium Inorganic materials 0.000 description 3
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 3
- 238000004321 preservation Methods 0.000 description 3
- 230000002195 synergetic effect Effects 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical compound C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 238000007600 charging Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000001132 ultrasonic dispersion Methods 0.000 description 2
- 229910000497 Amalgam Inorganic materials 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 238000004873 anchoring Methods 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000010277 constant-current charging Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000036647 reaction Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 230000008093 supporting effect Effects 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/24—Electrodes for alkaline accumulators
- H01M4/244—Zinc electrodes
-
- 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
- H01M10/28—Construction or manufacture
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/24—Electrodes for alkaline accumulators
- H01M4/26—Processes of manufacture
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses an alkaline zinc-manganese battery cathode, which comprises the following raw materials in parts by weight: 30-80 parts of solid powder, 1-30 parts of alkaline agent, 1-10 parts of zinc oxide, 0.01-5 parts of silicate, 0.1-5 parts of binder and 10-60 parts of deionized water. The solid powder is carboxylated graphene quantum dots and a composite carbon nanotube material. After the cathode prepared in the invention is added into a zinc-manganese battery, the overall capacitance, conductivity and cycle performance of the battery are effectively improved, the service life of the zinc-manganese battery is effectively prolonged, and the cathode is suitable for popularization in the field of batteries and has wide development prospect.
Description
Technical Field
The invention relates to the field of IPC classified H01M10, in particular to an alkaline zinc-manganese battery cathode and a preparation method thereof.
Background
Since the advent of zinc ion batteries, it has been widely studied as a new type of battery. This is mainly because it has the following advantages: 1. the safety is high, and the material is non-combustible, non-explosive, and can be cooled or heated; 2. the battery has excellent battery performance, can realize quick charge and quick discharge, and has large specific energy and large specific capacity; 3. the cost is low, the cost per watt hour is not more than 0.6 yuan, the reserves are rich, the cost is low, the production is simple and convenient, and the continuity is high; 4. the service life is long, the full charging and discharging can be realized, and the recycling can be effectively carried out; 5. zero pollution, no toxicity, no harm, green and environmental protection. In recent years, zinc-manganese batteries have been widely used for civil use and industrial use, and are particularly suitable for use in equipment such as flash cameras, mini-recorders, video cameras, interphones, shavers, palm-type color television sets and game machines, toys, telemeters, alarms, calculators, hearing aids, flashlights, and electric clocks. With the increasing and increasing functions of instruments and equipment, the requirements on the high-power high-current discharge performance of the zinc-manganese battery are higher and higher.
The zinc paste is used as an important component material for preparing the zinc-manganese battery, and the performance of the zinc paste plays a key role in the discharge capacity and the service life of the zinc-manganese battery. In an alkaline zinc-manganese battery, the zinc cathode is easy to dissolve zinc in alkali liquor and generate hydrogen synchronously due to the thermodynamic instability of the zinc cathode, so that the air pressure in the battery is gradually increased, and the storage performance of the battery is reduced and the leakage of the battery is caused. The traditional solution is mainly to add mercury into zinc powder to form amalgam alloy, but the method is stopped at present because of the strong toxicity of mercury. At present, metals or metal oxides with high hydrogen evolution overpotential such as indium, bismuth and the like are added in the zinc powder smelting and zinc paste preparation process as the most extensive method. However, metals such as indium and bismuth are expensive, which causes a large cost burden, and the prepared zinc-manganese battery has defects in capacitance and cycle effect.
Therefore, the research on a novel zinc paste cathode which has a corrosion inhibition effect close to indium and bismuth and has good capacitance and circulation effects is very meaningful work.
Disclosure of Invention
In order to solve the problems, the invention provides a negative electrode of an alkaline zinc-manganese battery, which comprises the following raw materials in parts by weight: 30-80 parts of solid powder, 1-30 parts of an alkaline agent, 1-10 parts of zinc oxide, 0.01-5 parts of silicate, 0.1-5 parts of a binder and 10-60 parts of deionized water.
As a preferable scheme, the raw materials comprise the following components in parts by weight: 60-65 parts of solid powder, 10-15 parts of alkaline agent, 1-3 parts of zinc oxide, 0.01-0.5 part of silicate, 0.1-0.5 part of binder and 30-35 parts of deionized water.
In a preferred embodiment, the alkaline agent is at least one of potassium hydroxide, sodium hydroxide, lithium hydroxide and magnesium hydroxide.
In a preferred embodiment, the silicate is zinc silicate or di-zinc orthosilicate.
In a preferred embodiment, the binder is at least one of hydroxymethyl cellulose, sodium silicate, polyacrylic acid, and polymethyl methacrylate.
As a preferable scheme, the solid powder raw material comprises the following components in parts by weight: 40-50 parts of nano zinc powder, 1-10 parts of conductive additive, 15-20 parts of organic resin, 30-35 parts of ketone solvent, 1-5 parts of plasticizer and 1-3 parts of coupling agent.
As a preferable scheme, the particle size of the nano zinc powder is 300-600 nm; the organic resin is at least one of polyvinyl chloride, polyvinylidene fluoride and polyperoxyethylene resin; the ketone solvent is at least one of acetone, butanone and cyclohexanone; the plasticizer is at least one of dioctyl phthalate, n-octyl phthalate and dibutyl phthalate; the coupling agent is at least one of vinyl trichlorosilane, methyltrimethoxysilane and vinyl triethoxysilane.
As a preferable scheme, the conductive assistant is graphene quantum dots and composite carbon nanotubes.
As a preferable scheme, the graphene quantum dots are carboxylated graphene quantum dots.
As a preferable scheme, the composite carbon nanotube is a composite material of a carbon nanotube and zinc oxide.
The composite carbon nanotube is self-made, and the steps comprise the following steps (in parts by weight): (1) adding 0.5 part of multi-walled carbon nanotube into 150 parts of deionized water to form a mixed solution, and performing ultrasonic dispersion for 1-2 hours; (2) after complete dispersion, adding 20 parts of zinc nitrate hexahydrate and 4 parts of citric acid into the mixed solution, and stirring for reaction for 1-2 hours; (3) heating to 80-90 ℃, continuously stirring for reaction for 15-18 hours, then heating to 160-180 ℃, stopping stirring and carrying out heat preservation reaction for 20-40 minutes; (4) and taking out the solid powder, and placing the solid powder in a tube furnace at the temperature of 600 ℃ for heat preservation for 1-2 hours to obtain the composite material of the carbon nano tube and the zinc oxide.
As an optimal scheme, the weight ratio of the graphene quantum dots to the composite carbon nanotubes is 1-2: 3 to 5.
The second aspect of the invention provides a preparation method of the alkaline zinc-manganese dioxide battery cathode, which comprises the following steps: (1) weighing and mixing a conductive auxiliary agent, an organic resin, a ketone solvent, a plasticizer and a coupling agent, and then putting the mixture into a high-speed stirring dispersion reaction kettle to stir for 30-50 minutes at a high speed to obtain a mixed solution; (2) mixing and stirring the mixed solution obtained in the step (1) and nano zinc powder for 20-30 minutes, and then centrifuging, volatilizing and drying to obtain solid powder; (3) then putting the solid powder, the binder and the silicate into a mixer, and uniformly stirring to prepare dry powder; adding an alkaline agent and zinc oxide into deionized water to prepare a strong alkaline solution; (4) and (3) putting the dry powder and the strong base solution into a calamine cream machine, uniformly stirring, vacuumizing, and removing bubbles to obtain the cathode material.
The third aspect of the invention provides an application of the alkaline zinc-manganese battery cathode, including an application of the zinc-manganese battery cathode in an alkaline zinc-manganese battery.
As a preferable scheme, the positive electrode of the alkaline zinc-manganese dioxide battery is a cathode reaction, and the reaction formula of the cathode reaction is as follows:
MnO 2 +H 2 O+e→MnO(OH)+OH - ；
MnO(OH)+H 2 O+OH - →Mn(OH) 4 - ；
Mn(OH) 4 - +e→Mn(OH) 4 2- 。
as a preferable scheme, the negative electrode of the alkaline zinc-manganese dioxide battery is an anode reaction, and the reaction formula of the anode reaction is as follows:
Zn+2OH - →Zn(OH) 2 +2e；
Zn(OH) 2 +2OH - →Zn(OH) 4 2- 。
as a preferred scheme, the total cell reaction formula of the alkaline zinc-manganese dioxide cell is as follows:
Zn+MnO 2 +2H 2 O+4OH - →Mn(OH) 4 2- +Zn(OH) 4 2- 。
has the advantages that:
1. the zinc-manganese battery cathode prepared by the method can effectively reduce the precipitation amount of hydrogen in the working process of the battery, improve the storage performance of the zinc-manganese battery, improve the cycle performance of the battery and reduce the cost.
2. The cathode of the zinc-manganese battery prepared by the method effectively improves various performances of the zinc-manganese battery through the synergistic effect of the carboxylated graphene quantum dot material and the composite material of the carbon nano tube and the zinc oxide. The carboxylated graphene quantum dot material is rich in carboxyl, hydroxyl and other groups, has strong specific adsorption capacity on metal ions of the negative electrode, and can play a good role in anchoring and coating, so that the active ingredients of the motor are protected, the current density is more uniform, and the phenomena of dendritic crystals and corrosion of the negative electrode are effectively reduced under the synergistic effect of the carboxylated graphene quantum dot material and the composite carbon nanotube; the composite material of the carbon nano tube and the zinc oxide can obviously reduce the impedance of the cathode of the zinc-manganese battery, has a good supporting effect on an active substance of the cathode battery, effectively reduces the electrochemical risk of the zinc-manganese battery in the charging and discharging processes, and effectively improves the service quality and service life of the zinc-manganese battery by the synergistic effect of the carbon nano tube and the carboxyl graphene quantum dot material.
Detailed Description
Example 1
Embodiment 1 provides an alkaline zinc-manganese battery negative electrode, which comprises the following raw materials in parts by weight: 60 parts of solid powder, 12 parts of potassium hydroxide, 2 parts of zinc oxide, 0.2 part of zinc silicate, 0.3 part of hydroxymethyl cellulose and 35 parts of deionized water.
The solid powder comprises the following components in parts by weight: 40 parts of nano zinc powder (with the average particle size of 350nm), 8 parts of conductive additive, 15 parts of polyvinylidene fluoride, 30 parts of acetone, 2 parts of dioctyl phthalate and 1.5 parts of vinyl trichlorosilane.
Conductive assistant: a composite of carboxylated graphene quantum dots, carbon nanotubes and zinc oxide; the weight ratio of the two is 1: 3.
the composite material of carbon nanotubes and zinc oxide in this example was prepared by a process comprising the following steps (in parts by weight): (1) adding 0.5 part of multi-walled carbon nanotube into 150 parts of deionized water to form a mixed solution, and performing ultrasonic dispersion for 2 hours; (2) after complete dispersion, adding 20 parts of zinc nitrate hexahydrate and 4 parts of citric acid into the mixed solution, and stirring for reaction for 2 hours; (3) heating to 85 ℃, continuously stirring for reacting for 16 hours, then heating to 170 ℃, stopping stirring and preserving heat for reacting for 30 minutes; (4) and taking out the solid powder, and placing the solid powder in a tube furnace at the temperature of 600 ℃ for heat preservation for 2 hours to obtain the composite material of the carbon nano tube and the zinc oxide.
The embodiment also provides a preparation method of the alkaline zinc-manganese dioxide battery cathode, which comprises the following steps: (1) mixing 8 parts of conductive additive, 15 parts of polyvinylidene fluoride, 30 parts of acetone, 2 parts of dioctyl phthalate and 1.5 parts of vinyl trichlorosilane, and then putting the mixture into a high-speed stirring dispersion reaction kettle to stir at a high speed for 30-50 minutes to obtain a mixed solution; (2) mixing and stirring the mixed solution obtained in the step (1) with 40 parts of nano zinc powder (with the average particle size of 350nm) for 25 minutes, and then centrifuging, volatilizing and drying to obtain solid powder; (3) then 60 parts of solid powder, 0.3 part of hydroxymethyl cellulose and 0.2 part of zinc silicate are put into a mixer and stirred uniformly to prepare dry powder; adding 12 parts of potassium hydroxide and 2 parts of zinc oxide into 35 parts of deionized water to prepare a strong alkali solution; (4) and (3) putting the dry powder and the strong base solution into a calamine cream machine, uniformly stirring, vacuumizing, and removing bubbles to obtain the cathode material.
In the embodiment, the carboxylated graphene quantum dots are XF-090-1 products sold by Nanjing Xiancheng nano material science and technology Limited company.
In this embodiment, the multi-walled carbon nanotube is a multi-walled carbon nanotube product sold by Beijing Deke island gold technologies, Inc.
The negative electrode of the alkaline zinc-manganese battery obtained in this example was designated as T1.
Example 2
The embodiment of the present invention is different from embodiment 1 in that: the average grain diameter of the nano zinc powder is 600 nm.
The negative electrode of the alkaline zinc-manganese battery obtained in this example was designated as T2.
Example 3
The embodiment of the present invention is different from embodiment 1 in that: the weight ratio of the composite material of the graphene quantum dots, the carbon nano tubes and the zinc oxide is 2: 5.
the negative electrode of the alkaline zinc-manganese battery obtained in this example was designated as T3.
Comparative example 1
The embodiment of this comparative example is the same as example 1 except that: the weight ratio of the composite material of the graphene quantum dots, the carbon nano tubes and the zinc oxide is 5: 1.
the negative electrode of the alkaline zinc-manganese battery manufactured by the comparative example was recorded as D1.
Comparative example 2
The embodiment of this comparative example is the same as example 1 except that: the grain size of the nano zinc powder is 1000 nm.
The negative electrode of the alkaline zinc-manganese battery obtained in this comparative example was designated as D2.
Comparative example 3
The embodiment of this comparative example is the same as example 1 except that: the conductive auxiliary agent is a common multi-wall carbon nano tube.
The negative electrode of the alkaline zinc-manganese battery obtained in this comparative example was designated as D3.
Evaluation of Performance
Discharge capacity and cycle performance: a 2Ah LR6 model zinc-manganese battery was prepared using the negative electrodes prepared in the examples and comparative examples, and a secondary rechargeable cylindrical Zn/Mn battery was assembled using a stainless steel case, a positive electrode ring (containing an electrolyte), an electrolyte, and a negative electrode, the electrolyte in each cycle test of each battery being the same; the assembled battery was subjected to constant current charging and discharging at a current density of 0.1C in a voltage range of 0.8 to 2.2V to test the discharge capacity, 5 samples were tested in each comparative example of example, and the measured values were averaged over 100 cycles and reported in table 1.
TABLE 1
According to the alkaline zinc-manganese battery cathode and the preparation method thereof, the prepared cathode is added into a zinc-manganese battery, so that the overall capacitance, conductivity and cycle performance of the battery are effectively improved, the service life of the zinc-manganese battery is effectively prolonged, the alkaline zinc-manganese battery cathode is suitable for popularization in the field of batteries, and the alkaline zinc-manganese battery cathode has a wide development prospect. Wherein example 1 achieves the best performance index with the best weight ratio of the raw materials, etc.
Claims (10)
1. An alkaline zinc-manganese battery cathode, characterized in that: the raw materials comprise the following components in parts by weight: 30-80 parts of solid powder, 1-30 parts of alkaline agent, 1-10 parts of zinc oxide, 0.01-5 parts of silicate, 0.1-5 parts of binder and 10-60 parts of deionized water.
2. The alkaline zinc-manganese dioxide battery negative electrode of claim 1, characterized in that: the raw materials comprise the following components in parts by weight: 60-65 parts of solid powder, 10-15 parts of alkaline agent, 1-3 parts of zinc oxide, 0.01-0.5 part of silicate, 0.1-0.5 part of binder and 30-35 parts of deionized water.
3. The alkaline zinc-manganese dioxide battery negative electrode of claim 1, characterized in that: the alkaline agent is at least one of potassium hydroxide, sodium hydroxide, lithium hydroxide and magnesium hydroxide.
4. The alkaline zinc-manganese dioxide battery negative electrode of claim 1, characterized in that: the silicate is zinc silicate or di-zinc orthosilicate.
5. The alkaline zinc-manganese dioxide battery negative electrode of claim 1, characterized in that: the binder is at least one of hydroxymethyl cellulose, sodium silicate, polyacrylic acid and polymethyl methacrylate.
6. The alkaline zinc-manganese dioxide battery negative electrode of claim 1, characterized in that: the solid powder raw materials comprise the following components in parts by weight: 40-50 parts of nano zinc powder, 1-10 parts of conductive additive, 15-20 parts of organic resin, 30-35 parts of ketone solvent, 1-5 parts of plasticizer and 1-3 parts of coupling agent.
7. The alkaline zinc-manganese dioxide battery negative electrode of claim 6, characterized in that: the particle size of the nano zinc powder is 300-600 nm; the organic resin is at least one of polyvinyl chloride, polyvinylidene fluoride and polyperoxyethylene resin; the ketone solvent is at least one of acetone, butanone and cyclohexanone; the plasticizer is at least one of dioctyl phthalate, n-octyl phthalate and dibutyl phthalate; the coupling agent is at least one of vinyl trichlorosilane, methyltrimethoxysilane and vinyl triethoxysilane.
8. The alkaline zinc-manganese dioxide battery negative electrode of claim 6, characterized in that: the conductive auxiliary agent is graphene quantum dots and composite carbon nanotubes.
9. The alkaline zinc-manganese dioxide battery negative electrode of claim 8, characterized in that: the weight ratio of the graphene quantum dots to the composite carbon nanotubes is 1-2: 3 to 5.
10. The method for preparing the negative electrode of the alkaline zinc-manganese battery according to claim 6, characterized in that: the method comprises the following steps: (1) weighing and mixing a conductive auxiliary agent, an organic resin, a ketone solvent, a plasticizer and a coupling agent, and then putting the mixture into a high-speed stirring dispersion reaction kettle to stir for 30-50 minutes at a high speed to obtain a mixed solution; (2) mixing and stirring the mixed solution obtained in the step (1) and nano zinc powder for 20-30 minutes, and then centrifuging, volatilizing and drying to obtain solid powder; (3) then putting the solid powder, the binder and the silicate into a mixer, and uniformly stirring to prepare dry powder; adding an alkaline agent and zinc oxide into deionized water to prepare a strong alkaline solution; (4) and (3) putting the dry powder and the strong base solution into a calamine cream machine, uniformly stirring, vacuumizing, and removing bubbles to obtain the cathode material.
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