WO2022156770A1 - Zinc-manganese battery containing modified nano zinc powder, and preparation method therefor - Google Patents
Zinc-manganese battery containing modified nano zinc powder, and preparation method therefor Download PDFInfo
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- WO2022156770A1 WO2022156770A1 PCT/CN2022/073196 CN2022073196W WO2022156770A1 WO 2022156770 A1 WO2022156770 A1 WO 2022156770A1 CN 2022073196 W CN2022073196 W CN 2022073196W WO 2022156770 A1 WO2022156770 A1 WO 2022156770A1
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- WIPO (PCT)
- Prior art keywords
- zinc
- zinc powder
- modified nano
- nano
- manganese battery
- Prior art date
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- WJZHMLNIAZSFDO-UHFFFAOYSA-N manganese zinc Chemical compound [Mn].[Zn] WJZHMLNIAZSFDO-UHFFFAOYSA-N 0.000 title claims abstract description 62
- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title abstract description 37
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 83
- RNWHGQJWIACOKP-UHFFFAOYSA-N zinc;oxygen(2-) Chemical compound [O-2].[Zn+2] RNWHGQJWIACOKP-UHFFFAOYSA-N 0.000 claims abstract description 54
- 239000002994 raw material Substances 0.000 claims abstract description 46
- 239000003792 electrolyte Substances 0.000 claims abstract description 42
- 239000011230 binding agent Substances 0.000 claims abstract description 41
- 239000000654 additive Substances 0.000 claims abstract description 38
- 230000000996 additive effect Effects 0.000 claims abstract description 37
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 41
- 239000007864 aqueous solution Substances 0.000 claims description 32
- 239000008151 electrolyte solution Substances 0.000 claims description 26
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 25
- 229920002125 Sokalan® Polymers 0.000 claims description 25
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 25
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 25
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 25
- 239000004584 polyacrylic acid Substances 0.000 claims description 25
- 239000000203 mixture Substances 0.000 claims description 24
- 239000004115 Sodium Silicate Substances 0.000 claims description 23
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 23
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 23
- 239000002245 particle Substances 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 9
- 229910052783 alkali metal Inorganic materials 0.000 claims description 3
- 150000001340 alkali metals Chemical class 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 239000002113 nanodiamond Substances 0.000 claims description 3
- 229920000193 polymethacrylate Polymers 0.000 claims description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 13
- 239000011248 coating agent Substances 0.000 abstract description 12
- 238000000576 coating method Methods 0.000 abstract description 12
- 238000004873 anchoring Methods 0.000 abstract description 3
- 238000005516 engineering process Methods 0.000 abstract description 3
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052753 mercury Inorganic materials 0.000 abstract description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 60
- 239000006185 dispersion Substances 0.000 description 40
- 229910021389 graphene Inorganic materials 0.000 description 36
- 239000002096 quantum dot Substances 0.000 description 36
- 239000007788 liquid Substances 0.000 description 30
- 238000002156 mixing Methods 0.000 description 12
- 229910052751 metal Inorganic materials 0.000 description 11
- 239000002184 metal Substances 0.000 description 11
- 239000000843 powder Substances 0.000 description 10
- 229920000642 polymer Polymers 0.000 description 9
- 238000003756 stirring Methods 0.000 description 8
- 230000008859 change Effects 0.000 description 7
- 239000000178 monomer Substances 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- 238000010008 shearing Methods 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 230000000379 polymerizing effect Effects 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- SUHOOTKUPISOBE-UHFFFAOYSA-N O-phosphoethanolamine Chemical compound NCCOP(O)(O)=O SUHOOTKUPISOBE-UHFFFAOYSA-N 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 238000004880 explosion Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229920001897 terpolymer Polymers 0.000 description 2
- KZEVSDGEBAJOTK-UHFFFAOYSA-N 1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-2-[5-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]-1,3,4-oxadiazol-2-yl]ethanone Chemical compound N1N=NC=2CN(CCC=21)C(CC=1OC(=NN=1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)=O KZEVSDGEBAJOTK-UHFFFAOYSA-N 0.000 description 1
- ZRPAUEVGEGEPFQ-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]pyrazol-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C=1C=NN(C=1)CC(=O)N1CC2=C(CC1)NN=N2 ZRPAUEVGEGEPFQ-UHFFFAOYSA-N 0.000 description 1
- CONKBQPVFMXDOV-QHCPKHFHSA-N 6-[(5S)-5-[[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]methyl]-2-oxo-1,3-oxazolidin-3-yl]-3H-1,3-benzoxazol-2-one Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C[C@H]1CN(C(O1)=O)C1=CC2=C(NC(O2)=O)C=C1 CONKBQPVFMXDOV-QHCPKHFHSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- OJIJEKBXJYRIBZ-UHFFFAOYSA-N cadmium nickel Chemical compound [Ni].[Cd] OJIJEKBXJYRIBZ-UHFFFAOYSA-N 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 230000009920 chelation Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000007717 exclusion Effects 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000002608 ionic liquid Substances 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- XLOMVQKBTHCTTD-UHFFFAOYSA-N zinc oxide Inorganic materials [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/42—Alloys based on zinc
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M6/00—Primary cells; Manufacture thereof
- H01M6/04—Cells with aqueous electrolyte
-
- 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
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
-
- 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
Definitions
- the invention relates to the technical field of zinc-manganese batteries, in particular to a zinc-manganese battery containing modified nano-zinc powder and a preparation method thereof.
- Battery refers to a part of the space of a cup, tank or other container or composite container that contains an electrolyte solution and metal electrodes to generate current, and can convert chemical energy into electrical energy. With positive and negative points. With the advancement of technology, batteries generally refer to small devices that can generate electricity. The ideal battery device needs to have the characteristics of large capacity, strong reversibility, fast charging and fast discharging, low cost, and environmental friendliness. Traditional alkaline manganese batteries, lithium-ion batteries, lead-acid batteries, cadmium-nickel batteries and various capacitors have been widely studied and applied in daily life. As an energy storage system, lead-acid batteries have been widely used in starting power supply, backup power supply, power supply, energy storage power supply and other fields due to their stable voltage and convenient use.
- Zinc-manganese batteries have environmental problems that cannot be ignored.
- the manufacturing and recycling process of acid batteries are prone to environmental pollution.
- Zinc-manganese batteries have received more and more attention in the battery field due to their simple structure, safety and environmental protection, and low cost.
- Zn/MnO2 batteries have lower requirements for the assembly environment and easy device assembly, and are also used in flexible and wearable fields. Unique advantages, these characteristics make zinc-manganese batteries have broad application prospects.
- Nano-zinc powder is modified by cage-type silsesquioxane nano-zinc powder, supplemented by ionic liquid to modify cage-type zinc powder.
- the synergistic effect of sesquisiloxane, ethanolamine phosphate and ethanolamine phosphate derivatives not only disperses the nano-zinc powder, but also has a good coordination chelation effect with the nano-zinc powder, which improves the overall performance of the battery uniformity, thereby extending the discharge performance and service life of the battery.
- the present invention solves the defects of limited actual capacity and poor temperature resistance of zinc-ion batteries in the prior art, and can obtain long cycle life and high energy density by adopting a simple process.
- Zinc-manganese battery with wide temperature resistance is provided.
- a first aspect of the present invention provides a zinc-manganese battery containing modified nano-zinc powder, comprising an outer shell, a positive electrode ring, a negative electrode zinc paste, a separator and an electrolyte solution; the raw materials of the negative electrode zinc paste include, in terms of weight ratio, 46-65% modified nano zinc powder, 3-7% binder, 27-46% electrolyte 2 and 1-4% additive.
- the modified nano-zinc powder is carbon quantum dot-coated nano-zinc powder.
- the carbon quantum dots include at least one of nanodiamond, graphene quantum dots, and fluorescent carbon particles.
- the carbon quantum dots are graphene quantum dots.
- the particle size of the nano-zinc powder in the carbon quantum dot-coated nano-zinc powder is 200-600 mesh.
- the binder includes at least one of carboxymethyl cellulose, sodium silicate, polyacrylic acid, and polymethacrylate.
- the additive is a cage-type silsesquioxane.
- the cage-type silsesquioxane includes at least one of vinyl-POSS, amino-POSS, epoxy-POSS, and hydroxyl-POSS.
- the second electrolyte is an alkali metal aqueous solution with a mass concentration of 32-40%.
- the second aspect of the present invention provides a zinc-manganese battery containing modified nano-zinc powder, and the preparation steps of the zinc-manganese battery containing modified nano-zinc powder include:
- the zinc-manganese battery containing the modified nano-zinc powder prepared by the invention adopts the technology of anchoring and coating the nano-zinc powder with carbon quantum dots, and has the following advantages:
- the battery cycle life is more than 1000 times, and the service life is long;
- the battery has a wide temperature resistance and can work normally under the conditions of -30°C-100°C;
- the battery does not add any lead-containing and mercury-containing materials, which is safe and environmentally friendly.
- compositions, step, method, article or device comprising the listed elements is not necessarily limited to those elements, but may include other elements not expressly listed or inherent to such composition, step, method, article or device elements.
- Polymer means a polymeric compound prepared by polymerizing monomers of the same or different types.
- the generic term “polymer” includes the terms “homopolymer”, “copolymer”, “terpolymer” and “interpolymer”.
- Interpolymer means a polymer prepared by polymerizing at least two different monomers.
- the generic term “interpolymer” includes the term “copolymer” (which is generally used to refer to a polymer prepared from two different monomers) and the term “terpolymer” (which is generally used to refer to three different monomers) polymer). It also includes polymers made by polymerizing more monomers.
- Blend means a polymer formed by co-mixing two or more polymers by physical or chemical means.
- the first aspect of the present invention provides a zinc-manganese battery containing modified nano-zinc powder, including an outer shell, a positive electrode ring, a negative electrode zinc paste, a separator and an electrolyte solution; the raw materials of the negative electrode zinc paste include, According to the weight ratio, 46-65% of modified nano zinc powder, 3-7% of binder, 27-46% of electrolyte 2 and 1-4% of additives.
- the modified nano-zinc powder is carbon quantum dot-coated nano-zinc powder.
- the carbon quantum dots include at least one of nanodiamond, graphene quantum dots, and fluorescent carbon particles.
- the carbon quantum dots are graphene quantum dots.
- Graphene quantum dots are commercially available, for example, Xi'an Qiyue Biotechnology Co., Ltd.
- the particle size of the nano-zinc powder in the carbon quantum dot-coated nano-zinc powder is 200-600 mesh.
- Nano-zinc powder with a particle size of 200-600 mesh can be commercially available, such as Hunan Xinweiling Metal New Material Technology Co., Ltd.
- the specific steps of coating the nano-zinc powder with the carbon quantum dots include:
- the volume fraction of ethanol in the aqueous ethanol solution is 1-5%.
- the mixing ratio of the nano-zinc powder raw material and the carbon quantum dot dispersion liquid is as follows: 10-35 mL of the carbon quantum dot dispersion liquid is mixed with each 1 g of the nano-zinc powder raw material.
- carbon quantum dots are rich in active groups, they have strong specific adsorption capacity for negative metal ions. On the one hand, they can play an anchoring and wrapping role, protect the active components of the electrode, and make the current density more uniform; on the other hand, it can significantly inhibit the negative electrode. Dendrite and corrosion phenomena, improve battery cycle life.
- the binder includes at least one of carboxymethyl cellulose, sodium silicate, polyacrylic acid, and polymethacrylate.
- the binder is carboxymethyl cellulose, sodium silicate and polyacrylic acid.
- the weight ratio of carboxymethyl cellulose, sodium silicate and polyacrylic acid is (1.5-4):(0.8-2.6):1.
- the additive is a cage silsesquioxane.
- the cage silsesquioxane includes at least one of vinyl-POSS, amino-POSS, epoxy-POSS, and hydroxyl-POSS.
- the cage-type silsesquioxane includes amino-POSS and/or hydroxyl-POSS.
- the second electrolyte is an alkali metal aqueous solution with a mass concentration of 32-40%.
- the second aspect of the present invention provides a zinc-manganese battery containing modified nano-zinc powder, and the preparation steps of the zinc-manganese battery containing modified nano-zinc powder include:
- a first aspect of this embodiment provides a zinc-manganese battery containing modified nano-zinc powder, including an outer shell, a positive electrode ring, a negative electrode zinc paste, a separator and an electrolyte solution 1; the raw materials of the negative electrode zinc paste include, according to the weight ratio , 53.5% modified nano zinc powder, 5% binder, 39% electrolyte two and 2.5% additive.
- the modified nano-zinc powder is carbon quantum dot-coated nano-zinc powder.
- the carbon quantum dots are graphene quantum dots.
- the particle size of the nano-zinc powder is 400 mesh, and it was purchased from Hunan Xinweiling Metal New Material Technology Co., Ltd.
- the specific steps of the graphene quantum dots coating nano zinc powder include:
- the volume fraction of ethanol in the ethanol aqueous solution is 2.8%.
- the mixing ratio of the nano-zinc powder raw material and the carbon quantum dot dispersion liquid is as follows: every 1 g of the nano-zinc powder raw material is mixed with 20 mL of the carbon quantum dot dispersion liquid.
- the binder is carboxymethyl cellulose, sodium silicate and polyacrylic acid; the weight ratio of carboxymethyl cellulose, sodium silicate and polyacrylic acid is 3:1.5:1.
- the additive was octahydroxycage silsesquioxane, which was purchased from Xi'an Qiyue Biotechnology Co., Ltd.
- the second electrolyte is a KOH aqueous solution with a mass concentration of 36%.
- the preparation steps of the zinc-manganese battery containing the modified nano-zinc powder include:
- a first aspect of this embodiment provides a zinc-manganese battery containing modified nano-zinc powder, including an outer shell, a positive electrode ring, a negative electrode zinc paste, a separator and an electrolyte solution 1; the raw materials of the negative electrode zinc paste include, according to the weight ratio , 50% modified nano zinc powder, 4% binder, 43% electrolyte two and 3% additive.
- the modified nano-zinc powder is carbon quantum dot-coated nano-zinc powder.
- the carbon quantum dots are graphene quantum dots.
- the particle size of the nano-zinc powder is 400 mesh, and it was purchased from Hunan Xinweiling Metal New Material Technology Co., Ltd.
- the specific steps of the graphene quantum dots coating nano zinc powder include:
- graphene quantum dot powder was added to 100mL ethanol aqueous solution, ultrasonically dispersed for 30min, stirred for 20min; ultrasonically oscillated, and sheared with a mechanical shearing machine for 4h to obtain a graphene quantum dot dispersion; the nano-zinc powder raw material and graphite
- the graphene quantum dot dispersion liquid is mixed, ball milled and dried to obtain the graphene quantum dot coated nano zinc powder.
- the volume fraction of ethanol in the ethanol aqueous solution is 2.8%.
- the mixing ratio of the nano-zinc powder raw material and the carbon quantum dot dispersion liquid is as follows: every 1 g of the nano-zinc powder raw material is mixed with 20 mL of the carbon quantum dot dispersion liquid.
- the binder is carboxymethyl cellulose, sodium silicate and polyacrylic acid; the weight ratio of carboxymethyl cellulose, sodium silicate and polyacrylic acid is 3:1.5:1.
- the additive was octahydroxycage silsesquioxane, which was purchased from Xi'an Qiyue Biotechnology Co., Ltd.
- the second electrolyte is a KOH aqueous solution with a mass concentration of 36%.
- the preparation steps of the zinc-manganese battery containing the modified nano-zinc powder include:
- a first aspect of this embodiment provides a zinc-manganese battery containing modified nano-zinc powder, including an outer shell, a positive electrode ring, a negative electrode zinc paste, a separator and an electrolyte solution 1; the raw materials of the negative electrode zinc paste include, according to the weight ratio , 63% modified nano zinc powder, 3% binder, 32% electrolyte two and 2% additive.
- the modified nano-zinc powder is carbon quantum dot-coated nano-zinc powder.
- the carbon quantum dots are graphene quantum dots.
- the particle size of the nano-zinc powder is 400 mesh, and it was purchased from Hunan Xinweiling Metal New Material Technology Co., Ltd.
- the specific steps of the graphene quantum dots coating nano zinc powder include:
- graphene quantum dot powder was added to 100mL ethanol aqueous solution, ultrasonically dispersed for 30min, stirred for 20min; ultrasonically oscillated, sheared with a mechanical shearing machine for 4h to obtain a graphene quantum dot dispersion; the nano-zinc powder raw material and graphite
- the graphene quantum dot dispersion liquid is mixed, ball milled and dried to obtain the graphene quantum dot coated nano zinc powder.
- the volume fraction of ethanol in the ethanol aqueous solution is 2.8%.
- the mixing ratio of the nano-zinc powder raw material and the carbon quantum dot dispersion liquid is as follows: every 1 g of the nano-zinc powder raw material is mixed with 20 mL of the carbon quantum dot dispersion liquid.
- the binder is carboxymethyl cellulose, sodium silicate and polyacrylic acid; the weight ratio of carboxymethyl cellulose, sodium silicate and polyacrylic acid is 3:1.5:1.
- the additive was octahydroxycage silsesquioxane, which was purchased from Xi'an Qiyue Biotechnology Co., Ltd.
- the second electrolyte is a KOH aqueous solution with a mass concentration of 36%.
- the preparation steps of the zinc-manganese battery containing the modified nano-zinc powder include:
- a first aspect of this embodiment provides a zinc-manganese battery containing modified nano-zinc powder, including an outer shell, a positive electrode ring, a negative electrode zinc paste, a separator and an electrolyte solution 1; the raw materials of the negative electrode zinc paste include, according to the weight ratio , 53.5% nano-zinc powder, 5% binder, 39% electrolyte two and 2.5% additive.
- the particle size of the nano-zinc powder is 400 mesh, and it was purchased from Hunan Xinweiling Metal New Material Technology Co., Ltd.
- the binder is carboxymethyl cellulose, sodium silicate and polyacrylic acid; the weight ratio of carboxymethyl cellulose, sodium silicate and polyacrylic acid is 3:1.5:1.
- the additive was octahydroxycage silsesquioxane, which was purchased from Xi'an Qiyue Biotechnology Co., Ltd.
- the second electrolyte is a KOH aqueous solution with a mass concentration of 36%.
- the preparation steps of the zinc-manganese battery containing the modified nano-zinc powder include:
- a first aspect of this embodiment provides a zinc-manganese battery containing modified nano-zinc powder, including a shell, a positive electrode ring, a negative electrode zinc paste, a separator and an electrolyte solution 1; the raw materials of the negative electrode zinc paste include, according to the weight ratio , 53.5% modified nano zinc powder, 5% binder, 39% electrolyte two and 2.5% additive.
- the modified nano-zinc powder is carbon quantum dot-coated nano-zinc powder.
- the carbon quantum dots are graphene quantum dots.
- the particle size of the nano-zinc powder is 400 mesh, and it was purchased from Hunan Xinweiling Metal New Material Technology Co., Ltd.
- the specific steps of the graphene quantum dots coating nano zinc powder include:
- the volume fraction of ethanol in the ethanol aqueous solution is 2.8%.
- the mixing ratio of the nano-zinc powder raw material and the carbon quantum dot dispersion liquid is as follows: every 1 g of the nano-zinc powder raw material is mixed with 5 mL of the carbon quantum dot dispersion liquid.
- the binder is carboxymethyl cellulose, sodium silicate and polyacrylic acid; the weight ratio of carboxymethyl cellulose, sodium silicate and polyacrylic acid is 3:1.5:1.
- the additive was octahydroxycage silsesquioxane, which was purchased from Xi'an Qiyue Biotechnology Co., Ltd.
- the second electrolyte is a KOH aqueous solution with a mass concentration of 36%.
- the preparation steps of the zinc-manganese battery containing the modified nano-zinc powder include:
- a first aspect of this embodiment provides a zinc-manganese battery containing modified nano-zinc powder, including an outer shell, a positive electrode ring, a negative electrode zinc paste, a separator and an electrolyte solution 1; the raw materials of the negative electrode zinc paste include, according to the weight ratio , 53.5% modified nano zinc powder, 5% binder, 39% electrolyte two and 2.5% additive.
- the modified nano-zinc powder is carbon quantum dot-coated nano-zinc powder.
- the carbon quantum dots are graphene quantum dots.
- the particle size of the nano-zinc powder is 60 meshes, purchased from Qingyuan County Tongxing Zinc Oxide Co., Ltd.
- the specific steps of the graphene quantum dots coating nano zinc powder include:
- the volume fraction of ethanol in the ethanol aqueous solution is 2.8%.
- the mixing ratio of the nano-zinc powder raw material and the carbon quantum dot dispersion liquid is as follows: every 1 g of the nano-zinc powder raw material is mixed with 20 mL of the carbon quantum dot dispersion liquid.
- the binder is carboxymethyl cellulose, sodium silicate and polyacrylic acid; the weight ratio of carboxymethyl cellulose, sodium silicate and polyacrylic acid is 3:1.5:1.
- the additive was octahydroxycage silsesquioxane, which was purchased from Xi'an Qiyue Biotechnology Co., Ltd.
- the second electrolyte is a KOH aqueous solution with a mass concentration of 36%.
- the preparation steps of the zinc-manganese battery containing the modified nano-zinc powder include:
- a first aspect of this embodiment provides a zinc-manganese battery containing modified nano-zinc powder, including an outer shell, a positive electrode ring, a negative electrode zinc paste, a separator and an electrolyte solution 1; the raw materials of the negative electrode zinc paste include, according to the weight ratio , 56% modified nano zinc powder, 5% binder, 39% electrolyte two.
- the modified nano-zinc powder is carbon quantum dot-coated nano-zinc powder.
- the carbon quantum dots are graphene quantum dots.
- the particle size of the nano-zinc powder is 400 mesh, and it was purchased from Hunan Xinweiling Metal New Material Technology Co., Ltd.
- the specific steps of the graphene quantum dots coating nano zinc powder include:
- the volume fraction of ethanol in the ethanol aqueous solution is 2.8%.
- the mixing ratio of the nano-zinc powder raw material and the carbon quantum dot dispersion liquid is as follows: every 1 g of the nano-zinc powder raw material is mixed with 20 mL of the carbon quantum dot dispersion liquid.
- the binder is carboxymethyl cellulose, sodium silicate and polyacrylic acid; the weight ratio of carboxymethyl cellulose, sodium silicate and polyacrylic acid is 3:1.5:1.
- the additive was octahydroxycage silsesquioxane, which was purchased from Xi'an Qiyue Biotechnology Co., Ltd.
- the second electrolyte is a KOH aqueous solution with a mass concentration of 36%.
- the preparation steps of the zinc-manganese battery containing the modified nano-zinc powder include:
- a first aspect of this embodiment provides a zinc-manganese battery containing modified nano-zinc powder, including an outer shell, a positive electrode ring, a negative electrode zinc paste, a separator and an electrolyte solution 1; the raw materials of the negative electrode zinc paste include, according to the weight ratio , 53.5% modified nano zinc powder, 5% binder, 39% electrolyte two and 2.5% additive.
- the modified nano-zinc powder is carbon quantum dot-coated nano-zinc powder.
- the carbon quantum dots are graphene quantum dots.
- the particle size of the nano-zinc powder is 400 mesh, and it was purchased from Hunan Xinweiling Metal New Material Technology Co., Ltd.
- the specific steps of the graphene quantum dots coating nano zinc powder include:
- the volume fraction of ethanol in the ethanol aqueous solution is 2.8%.
- the mixing ratio of the nano-zinc powder raw material and the carbon quantum dot dispersion liquid is as follows: every 1 g of the nano-zinc powder raw material is mixed with 20 mL of the carbon quantum dot dispersion liquid.
- the binder is carboxymethyl cellulose, sodium silicate and polyacrylic acid; the weight ratio of carboxymethyl cellulose, sodium silicate and polyacrylic acid is 1:1:2.
- the additive was octahydroxycage silsesquioxane, which was purchased from Xi'an Qiyue Biotechnology Co., Ltd.
- the second electrolyte is a KOH aqueous solution with a mass concentration of 36%.
- the preparation steps of the zinc-manganese battery containing the modified nano-zinc powder include:
- a first aspect of this embodiment provides a zinc-manganese battery containing modified nano-zinc powder, including an outer shell, a positive electrode ring, a negative electrode zinc paste, a separator and an electrolyte solution 1; the raw materials of the negative electrode zinc paste include, according to the weight ratio , 53.5% modified nano zinc powder, 5% binder, 39% electrolyte two and 2.5% additive.
- the modified nano-zinc powder is carbon quantum dot-coated nano-zinc powder.
- the carbon quantum dots are graphene quantum dots.
- the particle size of the nano-zinc powder is 400 mesh, and it was purchased from Hunan Xinweiling Metal New Material Technology Co., Ltd.
- the specific steps of the graphene quantum dots coating nano zinc powder include:
- the volume fraction of ethanol in the ethanol aqueous solution is 2.8%.
- the mixing ratio of the nano-zinc powder raw material and the carbon quantum dot dispersion liquid is as follows: every 1 g of the nano-zinc powder raw material is mixed with 20 mL of the carbon quantum dot dispersion liquid.
- the binder is carboxymethyl cellulose and polyacrylic acid; the weight ratio of carboxymethyl cellulose and polyacrylic acid is 3:1.
- the additive was octahydroxycage silsesquioxane, which was purchased from Xi'an Qiyue Biotechnology Co., Ltd.
- the second electrolyte is a KOH aqueous solution with a mass concentration of 36%.
- the preparation steps of the zinc-manganese battery containing the modified nano-zinc powder include:
- a first aspect of this embodiment provides a zinc-manganese battery containing modified nano-zinc powder, including an outer shell, a positive electrode ring, a negative electrode zinc paste, a separator and an electrolyte solution 1; the raw materials of the negative electrode zinc paste include, according to the weight ratio , 53.5% modified nano zinc powder, 5% binder, 39% electrolyte two and 2.5% additive.
- the modified nano-zinc powder is carbon quantum dot-coated nano-zinc powder.
- the carbon quantum dots are graphene quantum dots.
- the particle size of the nano-zinc powder is 400 mesh, and it was purchased from Hunan Xinweiling Metal New Material Technology Co., Ltd.
- the specific steps of the graphene quantum dots coating nano zinc powder include:
- the volume fraction of ethanol in the ethanol aqueous solution is 2.8%.
- the mixing ratio of the nano-zinc powder raw material and the carbon quantum dot dispersion liquid is as follows: every 1 g of the nano-zinc powder raw material is mixed with 20 mL of the carbon quantum dot dispersion liquid.
- the binder is carboxymethyl cellulose, sodium silicate and polyacrylic acid; the weight ratio of carboxymethyl cellulose, sodium silicate and polyacrylic acid is 3:1.5:1.
- the additive was octahydroxycage silsesquioxane, which was purchased from Xi'an Qiyue Biotechnology Co., Ltd.
- the second electrolyte is a KOH aqueous solution with a mass concentration of 36%.
- the preparation steps of the zinc-manganese battery containing the modified nano-zinc powder include:
- the batteries prepared in Examples 1-10 were placed at 100°C for 7 days to observe whether the batteries had bulging or liquid leakage; the evaluation grades were as follows:
- Level 0 no change, i.e. no perceptible change
- Level 1 very slight, i.e. just perceptible change
- Grade 2 Slight, that is, there is a noticeable change
- Level 3 Moderate, that is, there is a very noticeable change
- Level 4 large, that is, there is a large change
- the discharge capacity of the batteries prepared in Examples 1-10 was measured with reference to the national standard GB/T 31467.2-2015.
Abstract
The present invention relates to the technical field of zinc-manganese batteries, and in particular to a zinc-manganese battery containing modified nano zinc powder, and a preparation method therefor, comprising a shell, a positive electrode ring, negative electrode zinc paste, a separator, and a first electrolyte. The negative electrode zinc paste comprises the following raw materials in percentage by weight: 46-65% of modified nano zinc powder, 3-7% of a binder, 27-46% of a second electrolyte, and 1-4% of an additive. The zinc-manganese battery containing the modified nano zinc powder prepared in the present invention employs the technology of anchoring and coating nano zinc powder using carbon quantum dots, and has the following advantages: (1) the actual capacity and coulombic efficiency of the battery are high, and the practicability is strong; (2) the cycle life of the battery is more than 1000 times, and the service life is long; (3) the battery has a wide temperature resistance range and can normally work under the condition of -30℃-100℃; and (4) no lead-containing and mercury-containing material is added into the battery, and the battery is safe and environment-friendly.
Description
本发明涉及锌锰电池技术领域领域，尤其涉及一种含有改性纳米锌粉的锌锰电池及其制备方法。The invention relates to the technical field of zinc-manganese batteries, in particular to a zinc-manganese battery containing modified nano-zinc powder and a preparation method thereof.
电池(Battery)指盛有电解质溶液和金属电极以产生电流的杯、槽或其他容器或复合容器的部分空间，能将化学能转化成电能的装置。具有正极、负极之分。随着科技的进步，电池泛指能产生电能的小型装置。理想的电池器件需具备大容量、可逆性强、快充快放、成本低廉、环境友好等特点。传统的碱锰电池、锂离子电池、铅酸电池、镉镍电池以及各种电容器被广泛研究并在生活中得以应用。铅酸电池作为能量储存***，因电压稳定、使用方便，曾被广泛应用于启动电源、备用电源、动力电源、储能电源等领域，但是铅酸电池存在着无法被忽视的环保问题，在铅酸电池的制造和回收过程中，都容易产生环境污染。锌锰电池由于结构简单、安全环保、成本低廉等特点，在电池领域受到越来越多的关注；而且Zn/MnO2电池对于组装环境的要求较低、器件组装简易，在柔性及可穿戴领域也有独特的优势，这些特点使得锌锰电池的应用前景广阔。Battery refers to a part of the space of a cup, tank or other container or composite container that contains an electrolyte solution and metal electrodes to generate current, and can convert chemical energy into electrical energy. With positive and negative points. With the advancement of technology, batteries generally refer to small devices that can generate electricity. The ideal battery device needs to have the characteristics of large capacity, strong reversibility, fast charging and fast discharging, low cost, and environmental friendliness. Traditional alkaline manganese batteries, lithium-ion batteries, lead-acid batteries, cadmium-nickel batteries and various capacitors have been widely studied and applied in daily life. As an energy storage system, lead-acid batteries have been widely used in starting power supply, backup power supply, power supply, energy storage power supply and other fields due to their stable voltage and convenient use. However, lead-acid batteries have environmental problems that cannot be ignored. The manufacturing and recycling process of acid batteries are prone to environmental pollution. Zinc-manganese batteries have received more and more attention in the battery field due to their simple structure, safety and environmental protection, and low cost. Moreover, Zn/MnO2 batteries have lower requirements for the assembly environment and easy device assembly, and are also used in flexible and wearable fields. Unique advantages, these characteristics make zinc-manganese batteries have broad application prospects.
中国专利CN201910905455.0提供了一种含有改性纳米锌粉的碱性锌锰电池，采用笼型倍半硅氧烷纳米锌粉对纳米锌粉进行改性，辅以离子液体改性笼型倍半硅氧烷、乙醇胺磷酸酯和乙醇胺磷酸酯衍生物的协同作用，在对纳米锌粉起到分散作用的同时，使其与纳米锌粉具备良好的配位螯合作用，提高了电池整体性能的均一性，从而延长了电池的放电性能和使用寿命。但是该发明的配方复杂，工艺繁琐，成本较高，大量的掺杂更加考验原料的储存稳定性，局限了其实际应用环境。基于此，制备一种含有改性纳米锌粉的锌锰电池成为本领域亟待解决的问题。Chinese patent CN201910905455.0 provides an alkaline zinc-manganese battery containing modified nano-zinc powder. Nano-zinc powder is modified by cage-type silsesquioxane nano-zinc powder, supplemented by ionic liquid to modify cage-type zinc powder. The synergistic effect of sesquisiloxane, ethanolamine phosphate and ethanolamine phosphate derivatives not only disperses the nano-zinc powder, but also has a good coordination chelation effect with the nano-zinc powder, which improves the overall performance of the battery uniformity, thereby extending the discharge performance and service life of the battery. However, the formulation of the invention is complicated, the process is cumbersome, and the cost is high, and the large amount of doping further tests the storage stability of the raw materials, which limits its practical application environment. Based on this, the preparation of a zinc-manganese battery containing modified nano-zinc powder has become an urgent problem to be solved in the art.
发明内容SUMMARY OF THE INVENTION
本发明通过提供一种含有改性纳米锌粉的锌锰电池，解决了现有技术中锌离子电池实际容量有限，耐温性差的缺陷，采用简单工艺即可获得循环寿命长，能量密度高，耐温宽的锌锰电池。By providing a zinc-manganese battery containing modified nano-zinc powder, the present invention solves the defects of limited actual capacity and poor temperature resistance of zinc-ion batteries in the prior art, and can obtain long cycle life and high energy density by adopting a simple process. Zinc-manganese battery with wide temperature resistance.
本发明第一方面提供了一种含有改性纳米锌粉的锌锰电池，包括外壳，正极环，负极锌膏，隔膜和电解液一；所述负极锌膏的原料包括，按照重量比计，46～65％改性纳米锌粉，3～7％粘结剂，27～46％电解液二和1～4％添加剂。A first aspect of the present invention provides a zinc-manganese battery containing modified nano-zinc powder, comprising an outer shell, a positive electrode ring, a negative electrode zinc paste, a separator and an electrolyte solution; the raw materials of the negative electrode zinc paste include, in terms of weight ratio, 46-65% modified nano zinc powder, 3-7% binder, 27-46% electrolyte 2 and 1-4% additive.
在一种优选的实施方式中，所述改性纳米锌粉为碳量子点包覆纳米锌粉。In a preferred embodiment, the modified nano-zinc powder is carbon quantum dot-coated nano-zinc powder.
在一种优选的实施方式中，所述碳量子点包括纳米金刚石，石墨烯量子点，荧光碳颗粒中的至少一种。In a preferred embodiment, the carbon quantum dots include at least one of nanodiamond, graphene quantum dots, and fluorescent carbon particles.
在一种优选的实施方式中，所述碳量子点为石墨烯量子点。In a preferred embodiment, the carbon quantum dots are graphene quantum dots.
在一种优选的实施方式中，所述碳量子点包覆纳米锌粉中纳米锌粉的粒径为200-600目。In a preferred embodiment, the particle size of the nano-zinc powder in the carbon quantum dot-coated nano-zinc powder is 200-600 mesh.
在一种优选的实施方式中，所述粘结剂包括羧甲基纤维素，硅酸钠，聚丙烯酸，聚甲基丙烯酸酯中的至少一种。In a preferred embodiment, the binder includes at least one of carboxymethyl cellulose, sodium silicate, polyacrylic acid, and polymethacrylate.
在一种优选的实施方式中，所述添加剂为笼型倍半硅氧烷。In a preferred embodiment, the additive is a cage-type silsesquioxane.
在一种优选的实施方式中，所述笼型倍半硅氧烷包括乙烯基-POSS，氨基-POSS，环氧基-POSS，羟基-POSS中的至少一种。In a preferred embodiment, the cage-type silsesquioxane includes at least one of vinyl-POSS, amino-POSS, epoxy-POSS, and hydroxyl-POSS.
在一种优选的实施方式中，所述电解液二为质量浓度为32-40％的碱金属水溶液。In a preferred embodiment, the second electrolyte is an alkali metal aqueous solution with a mass concentration of 32-40%.
本发明第二方面提供了一种含有改性纳米锌粉的锌锰电池，所述含有改性纳米锌粉的锌锰电池的制备步骤包括：The second aspect of the present invention provides a zinc-manganese battery containing modified nano-zinc powder, and the preparation steps of the zinc-manganese battery containing modified nano-zinc powder include:
S1.制备改性纳米锌粉；S1. Preparation of modified nano-zinc powder;
S2.将改性纳米锌粉，粘结剂，电解液一和添加剂混合均匀，得到负极锌膏；S2. Mix the modified nano-zinc powder, the binder, the electrolyte solution one and the additive evenly to obtain a negative electrode zinc paste;
S3.将正极环放入外壳，并注入电解液二，加入隔膜，静置至隔膜完全润湿，加入负极锌膏，组装得到锌锰电池成品。S3. Put the positive electrode ring into the casing, inject the electrolyte 2, add the diaphragm, let it stand until the diaphragm is completely wet, add the negative electrode zinc paste, and assemble the finished zinc-manganese battery.
本发明制备得到的含有改性纳米锌粉的锌锰电池采用碳量子点锚固和包覆纳米锌粉技术，具有以下优点：The zinc-manganese battery containing the modified nano-zinc powder prepared by the invention adopts the technology of anchoring and coating the nano-zinc powder with carbon quantum dots, and has the following advantages:
(1)电池实际容量、库伦效率高，实用性强；(1) The actual capacity of the battery, the Coulomb efficiency are high, and the practicability is strong;
(2)电池循环寿命大于1000次，使用寿命长；(2) The battery cycle life is more than 1000 times, and the service life is long;
(3)电池耐温宽，能够在-30℃-100℃条件下正常工作；(3) The battery has a wide temperature resistance and can work normally under the conditions of -30℃-100℃;
(4)电池不添加任何含铅含汞材料，安全环保。(4) The battery does not add any lead-containing and mercury-containing materials, which is safe and environmentally friendly.
参选以下本发明的优选实施方法的详述以及包括的实施例可更容易地理解本发明的内容。除非另有限定，本文使用的所有技术以及科学术语具有与本发明所属领域普通技术人员通常理解的相同的含义。当存在矛盾时，以本说明书中的定义为准。The content of the present invention may be more readily understood by reference to the following detailed description of the preferred embodiments of the invention and the included examples. Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In case of conflict, the definitions in this specification will control.
如本文所用术语“由…制备”与“包含”同义。本文中所用的术语“包含”、“包括”、“具有”、“含有”或其任何其它变形，意在覆盖非排它性的包括。例如，包含所列要素的组合物、步骤、方法、制品或装置不必仅限于那些要素，而是可以包括未明确列出的其它要素或此种组合物、步骤、方法、制品或装置所固有的要素。As used herein, the term "prepared from" is synonymous with "comprising". As used herein, the terms "comprising," "including," "having," "containing," or any other variation thereof, are intended to cover non-exclusive inclusion. For example, a composition, step, method, article or device comprising the listed elements is not necessarily limited to those elements, but may include other elements not expressly listed or inherent to such composition, step, method, article or device elements.
连接词“由…组成”排除任何未指出的要素、步骤或组分。如果用于权利要求中，此短语将使权利要求为封闭式，使其不包含除那些描述的材料以外的材料，但与其相关的常规杂质除外。当短语“由…组成”出现在权利要求主体的子句中而不是紧接在主题之后时，其仅限定在该子句中描述的要素；其它要素并不被排除在作为整体的所述权利要求之外。The conjunction "consisting of" excludes any unspecified element, step or component. If used in a claim, this phrase would make the claim closed to the exclusion of materials other than those described, but with the exception of conventional impurities associated therewith. When the phrase "consisting of" appears in a clause in the body of a claim rather than immediately following the subject matter, it is limited only to the elements described in that clause; other elements are not excluded from the claim as a whole beyond the requirements.
当量、浓度、或者其它值或参数以范围、优选范围、或一系列上限优选值和下限优选值限定的范围表示时，这应当被理解为具体公开了由任何范围上限或优选值与任何范围下限或优选值的任一配对所形成的所有范围，而不论该范围是否单独公开了。例如，当公开了范围“1至5”时，所描述的范围应被解释为包括范围“1至4”、“1至3”、“1至2”、“1至2和4至5”、“1至3和5”等。当数值范围在本文中被描述时，除非另外说明，否则该范围意图包括其端值和在该范围内的所有整数和分数。When an amount, concentration, or other value or parameter is expressed as a range, preferred range, or a range bounded by a series of upper preferred values and lower preferred values, this should be understood as specifically disclosing any upper range limit or preferred value and any lower range limit or all ranges formed by any pairing of preferred values, whether or not the ranges are individually disclosed. For example, when a range of "1 to 5" is disclosed, the described range should be construed to include the ranges "1 to 4," "1 to 3," "1 to 2," "1 to 2, and 4 to 5." , "1 to 3 and 5", etc. When numerical ranges are described herein, unless stated otherwise, the ranges are intended to include the endpoints and all integers and fractions within the range.
单数形式包括复数讨论对象，除非上下文中另外清楚地指明。“任选的”或者“任意 一种”是指其后描述的事项或事件可以发生或不发生，而且该描述包括事件发生的情形和事件不发生的情形。The singular form includes the plural object of discussion unless the context clearly dictates otherwise. "Optional" or "either" means that the subsequently described item or event may or may not occur, and that the description includes instances where the event occurs and instances where it does not.
说明书和权利要求书中的近似用语用来修饰数量，表示本发明并不限定于该具体数量，还包括与该数量接近的可接受的而不会导致相关基本功能的改变的修正的部分。相应的，用“大约”、“约”等修饰一个数值，意为本发明不限于该精确数值。在某些例子中，近似用语可能对应于测量数值的仪器的精度。在本申请说明书和权利要求书中，范围限定可以组合和/或互换，如果没有另外说明这些范围包括其间所含有的所有子范围。Approximate terms in the specification and claims are used to modify a quantity, indicating that the invention is not limited to the specific quantity, but also includes acceptable amendments close to the quantity without causing a change in the relevant basic function. Accordingly, modification of a numerical value with "about", "about", etc. means that the invention is not limited to the precise numerical value. In some instances, the term of approximation may correspond to the precision of the instrument measuring the value. In the present specification and claims, range definitions may be combined and/or interchanged, and unless otherwise stated, these ranges include all subranges subsumed therebetween.
此外，本发明要素或组分前的不定冠词“一种”和“一个”对要素或组分的数量要求(即出现次数)无限制性。因此“一个”或“一种”应被解读为包括一个或至少一个，并且单数形式的要素或组分也包括复数形式，除非所述数量明显旨指单数形式。Furthermore, the indefinite articles "a" and "an" preceding an element or component of the invention are not limiting on the quantitative requirement (ie, the number of occurrences) of the element or component. Thus "a" or "an" should be read to include one or at least one, and elements or components in the singular also include the plural unless the number is clearly intended to be in the singular.
“聚合物”意指通过聚合相同或不同类型的单体所制备的聚合化合物。通用术语“聚合物”包含术语“均聚物”、“共聚物”、“三元共聚物”与“共聚体”。“共聚体”意指通过聚合至少两种不同单体制备的聚合物。通用术语“共聚体”包括术语“共聚物”(其一般用以指由两种不同单体制备的聚合物)与术语“三元共聚物”(其一般用以指由三种不同单体制备的聚合物)。其亦包含通过聚合更多种单体而制造的聚合物。“共混物”意指两种或两种以上聚合物通过物理的或化学的方法共同混合而形成的聚合物。"Polymer" means a polymeric compound prepared by polymerizing monomers of the same or different types. The generic term "polymer" includes the terms "homopolymer", "copolymer", "terpolymer" and "interpolymer". "Interpolymer" means a polymer prepared by polymerizing at least two different monomers. The generic term "interpolymer" includes the term "copolymer" (which is generally used to refer to a polymer prepared from two different monomers) and the term "terpolymer" (which is generally used to refer to three different monomers) polymer). It also includes polymers made by polymerizing more monomers. "Blend" means a polymer formed by co-mixing two or more polymers by physical or chemical means.
为了解决上述问题，本发明第一方面提供了一种含有改性纳米锌粉的锌锰电池，包括外壳，正极环，负极锌膏，隔膜和电解液一；所述负极锌膏的原料包括，按照重量比计，46～65％改性纳米锌粉，3～7％粘结剂，27～46％电解液二和1～4％添加剂。In order to solve the above problems, the first aspect of the present invention provides a zinc-manganese battery containing modified nano-zinc powder, including an outer shell, a positive electrode ring, a negative electrode zinc paste, a separator and an electrolyte solution; the raw materials of the negative electrode zinc paste include, According to the weight ratio, 46-65% of modified nano zinc powder, 3-7% of binder, 27-46% of electrolyte 2 and 1-4% of additives.
在一些优选的实施方式中，所述改性纳米锌粉为碳量子点包覆纳米锌粉。In some preferred embodiments, the modified nano-zinc powder is carbon quantum dot-coated nano-zinc powder.
在一些优选的实施方式中，所述碳量子点包括纳米金刚石，石墨烯量子点，荧光碳颗粒中的至少一种。In some preferred embodiments, the carbon quantum dots include at least one of nanodiamond, graphene quantum dots, and fluorescent carbon particles.
进一步优选，所述碳量子点为石墨烯量子点。石墨烯量子点可为市售，例如西安齐岳生物科技有限公司。Further preferably, the carbon quantum dots are graphene quantum dots. Graphene quantum dots are commercially available, for example, Xi'an Qiyue Biotechnology Co., Ltd.
在一些优选的实施方式中，所述碳量子点包覆纳米锌粉中纳米锌粉的粒径为200-600目。粒径为200-600目的纳米锌粉可为市售，例如湖南新威凌金属新材料科技股份有限公司。In some preferred embodiments, the particle size of the nano-zinc powder in the carbon quantum dot-coated nano-zinc powder is 200-600 mesh. Nano-zinc powder with a particle size of 200-600 mesh can be commercially available, such as Hunan Xinweiling Metal New Material Technology Co., Ltd.
在一些优选的实施方式中，所述碳量子点包覆纳米锌粉的具体步骤包括：In some preferred embodiments, the specific steps of coating the nano-zinc powder with the carbon quantum dots include:
将0.1-5g碳量子点粉体加入到100mL乙醇水溶液中，超声分散20-40min，搅拌15-30min；超声振荡，用机械剪切机剪切3-5h，得到碳量子点分散液；将纳米锌粉原料与碳量子点分散液混合，球磨干燥，得到碳量子点包覆纳米锌粉。Add 0.1-5 g of carbon quantum dot powder to 100 mL of ethanol aqueous solution, ultrasonically disperse for 20-40 min, and stir for 15-30 min; ultrasonically vibrate and shear with a mechanical shearing machine for 3-5 h to obtain a carbon quantum dot dispersion; The zinc powder raw material is mixed with the carbon quantum dot dispersion liquid, ball milled and dried to obtain the carbon quantum dot coated nano zinc powder.
在一些优选的实施方式中，所述乙醇水溶液中乙醇的体积分数为1-5％。In some preferred embodiments, the volume fraction of ethanol in the aqueous ethanol solution is 1-5%.
在一些优选的实施方式中，所述纳米锌粉原料和碳量子点分散液的混合比例为：每1g纳米锌粉原料混入10-35mL碳量子点分散液。In some preferred embodiments, the mixing ratio of the nano-zinc powder raw material and the carbon quantum dot dispersion liquid is as follows: 10-35 mL of the carbon quantum dot dispersion liquid is mixed with each 1 g of the nano-zinc powder raw material.
由于碳量子点富含活性基团，对负极金属离子有强特异性吸附能力，一方面能够起到锚固和包裹作用，保护电极活性成分，使电流密度更加均匀；另一方面能够显著抑制负极的枝晶和腐蚀现象，提升电池循环寿命。Because carbon quantum dots are rich in active groups, they have strong specific adsorption capacity for negative metal ions. On the one hand, they can play an anchoring and wrapping role, protect the active components of the electrode, and make the current density more uniform; on the other hand, it can significantly inhibit the negative electrode. Dendrite and corrosion phenomena, improve battery cycle life.
在一些优选的实施方式中，所述粘结剂包括羧甲基纤维素，硅酸钠，聚丙烯酸，聚甲基丙烯酸酯中的至少一种。In some preferred embodiments, the binder includes at least one of carboxymethyl cellulose, sodium silicate, polyacrylic acid, and polymethacrylate.
进一步优选，所述粘结剂为羧甲基纤维素，硅酸钠和聚丙烯酸。Further preferably, the binder is carboxymethyl cellulose, sodium silicate and polyacrylic acid.
更进一步优选，羧甲基纤维素，硅酸钠和聚丙烯酸的重量比为(1.5-4)∶(0.8-2.6)∶1。More preferably, the weight ratio of carboxymethyl cellulose, sodium silicate and polyacrylic acid is (1.5-4):(0.8-2.6):1.
在一些优选的实施方式中，所述添加剂为笼型倍半硅氧烷。In some preferred embodiments, the additive is a cage silsesquioxane.
在一些优选的实施方式中，所述笼型倍半硅氧烷包括乙烯基-POSS，氨基-POSS，环氧基-POSS，羟基-POSS中的至少一种。In some preferred embodiments, the cage silsesquioxane includes at least one of vinyl-POSS, amino-POSS, epoxy-POSS, and hydroxyl-POSS.
进一步优选，所述笼型倍半硅氧烷包括氨基-POSS和/或羟基-POSS。Further preferably, the cage-type silsesquioxane includes amino-POSS and/or hydroxyl-POSS.
在一些优选的实施方式中，所述电解液二为质量浓度为32-40％的碱金属水溶液。In some preferred embodiments, the second electrolyte is an alkali metal aqueous solution with a mass concentration of 32-40%.
本发明第二方面提供了一种含有改性纳米锌粉的锌锰电池，所述含有改性纳米锌粉的锌锰电池的制备步骤包括：The second aspect of the present invention provides a zinc-manganese battery containing modified nano-zinc powder, and the preparation steps of the zinc-manganese battery containing modified nano-zinc powder include:
S1.制备改性纳米锌粉；S1. Preparation of modified nano-zinc powder;
S2.将改性纳米锌粉，粘结剂，电解液一和添加剂混合均匀，得到负极锌膏；S2. Mix the modified nano-zinc powder, the binder, the electrolyte solution one and the additive evenly to obtain a negative electrode zinc paste;
S3.将正极环放入外壳，并注入电解液二，加入隔膜，静置至隔膜完全润湿，加入负极锌膏，组装得到锌锰电池成品。S3. Put the positive electrode ring into the casing, inject the electrolyte 2, add the diaphragm, let it stand until the diaphragm is completely wet, add the negative electrode zinc paste, and assemble the finished zinc-manganese battery.
实施例Example
为了更好的理解上述技术方案，下面将结合具体的实施方式对上述技术方案进行详细的说明。有必要在此指出的是，以下实施例只用于对本发明作进一步说明，不能理解为对本发明保护范围的限制，该领域的专业技术人员根据上述本发明的内容做出的一些非本质的改进和调整，仍属于本发明的保护范围。另外，如果没有其它说明，所用原料都是市售的，所述提取物的提取方法均为常规的提取方法。In order to better understand the above technical solutions, the above technical solutions will be described in detail below with reference to specific embodiments. It is necessary to point out that the following examples are only used to further illustrate the present invention, and should not be construed as limiting the scope of protection of the present invention, and some non-essential improvements made by those skilled in the art according to the above-mentioned content of the present invention and adjustment, still belong to the protection scope of the present invention. In addition, unless otherwise stated, the raw materials used are all commercially available, and the extraction methods of the extracts are all conventional extraction methods.
实施例1.Example 1.
本实施例第一方面提供了一种含有改性纳米锌粉的锌锰电池，包括外壳，正极环，负极锌膏，隔膜和电解液一；所述负极锌膏的原料包括，按照重量比计，53.5％改性纳米锌粉，5％粘结剂，39％电解液二和2.5％添加剂。A first aspect of this embodiment provides a zinc-manganese battery containing modified nano-zinc powder, including an outer shell, a positive electrode ring, a negative electrode zinc paste, a separator and an electrolyte solution 1; the raw materials of the negative electrode zinc paste include, according to the weight ratio , 53.5% modified nano zinc powder, 5% binder, 39% electrolyte two and 2.5% additive.
所述改性纳米锌粉为碳量子点包覆纳米锌粉。The modified nano-zinc powder is carbon quantum dot-coated nano-zinc powder.
所述碳量子点为石墨烯量子点。The carbon quantum dots are graphene quantum dots.
所述纳米锌粉的粒径为400目，购买自湖南新威凌金属新材料科技股份有限公司。The particle size of the nano-zinc powder is 400 mesh, and it was purchased from Hunan Xinweiling Metal New Material Technology Co., Ltd.
所述石墨烯量子点包覆纳米锌粉的具体步骤包括：The specific steps of the graphene quantum dots coating nano zinc powder include:
将3g石墨烯量子点粉体加入到100mL乙醇水溶液中，超声分散30min，搅拌20min；超声振荡，用机械剪切机剪切4h，得到石墨烯量子点分散液；将纳米锌粉原料与石墨烯量子点分散液混合，球磨干燥，得到石墨烯量子点包覆纳米锌粉。Add 3g graphene quantum dot powder to 100mL ethanol aqueous solution, ultrasonically disperse for 30min, stir for 20min; ultrasonically vibrate, shear with mechanical shearing machine for 4h to obtain graphene quantum dot dispersion; mix nano zinc powder raw material with graphene The quantum dot dispersion liquid is mixed, ball-milled and dried to obtain graphene quantum dot-coated nano-zinc powder.
所述乙醇水溶液中乙醇的体积分数为2.8％。The volume fraction of ethanol in the ethanol aqueous solution is 2.8%.
所述纳米锌粉原料和碳量子点分散液的混合比例为：每1g纳米锌粉原料混入20mL碳量子点分散液。The mixing ratio of the nano-zinc powder raw material and the carbon quantum dot dispersion liquid is as follows: every 1 g of the nano-zinc powder raw material is mixed with 20 mL of the carbon quantum dot dispersion liquid.
所述粘结剂为羧甲基纤维素，硅酸钠和聚丙烯酸；羧甲基纤维素，硅酸钠和聚丙烯酸的重量比为3∶1.5∶1。The binder is carboxymethyl cellulose, sodium silicate and polyacrylic acid; the weight ratio of carboxymethyl cellulose, sodium silicate and polyacrylic acid is 3:1.5:1.
所述添加剂为八羟基笼型倍半硅氧烷，购买自西安齐岳生物科技有限公司。The additive was octahydroxycage silsesquioxane, which was purchased from Xi'an Qiyue Biotechnology Co., Ltd.
所述电解液二为质量浓度为36％的KOH水溶液。The second electrolyte is a KOH aqueous solution with a mass concentration of 36%.
所述含有改性纳米锌粉的锌锰电池的制备步骤包括：The preparation steps of the zinc-manganese battery containing the modified nano-zinc powder include:
S1.制备改性纳米锌粉；S1. Preparation of modified nano-zinc powder;
S2.将改性纳米锌粉，粘结剂，电解液一和添加剂混合均匀，得到负极锌膏；S2. Mix the modified nano-zinc powder, the binder, the electrolyte solution one and the additive evenly to obtain a negative electrode zinc paste;
S3.将正极环放入外壳，并注入电解液二，加入隔膜，静置至隔膜完全润湿，加入负极锌膏，组装得到锌锰电池成品。S3. Put the positive electrode ring into the casing, inject the electrolyte 2, add the diaphragm, let it stand until the diaphragm is completely wet, add the negative electrode zinc paste, and assemble the finished zinc-manganese battery.
实施例2.Example 2.
本实施例第一方面提供了一种含有改性纳米锌粉的锌锰电池，包括外壳，正极环，负极锌膏，隔膜和电解液一；所述负极锌膏的原料包括，按照重量比计，50％改性纳米锌粉，4％粘结剂，43％电解液二和3％添加剂。A first aspect of this embodiment provides a zinc-manganese battery containing modified nano-zinc powder, including an outer shell, a positive electrode ring, a negative electrode zinc paste, a separator and an electrolyte solution 1; the raw materials of the negative electrode zinc paste include, according to the weight ratio , 50% modified nano zinc powder, 4% binder, 43% electrolyte two and 3% additive.
所述改性纳米锌粉为碳量子点包覆纳米锌粉。The modified nano-zinc powder is carbon quantum dot-coated nano-zinc powder.
所述碳量子点为石墨烯量子点。The carbon quantum dots are graphene quantum dots.
所述纳米锌粉的粒径为400目，购买自湖南新威凌金属新材料科技股份有限公司。The particle size of the nano-zinc powder is 400 mesh, and it was purchased from Hunan Xinweiling Metal New Material Technology Co., Ltd.
所述石墨烯量子点包覆纳米锌粉的具体步骤包括：The specific steps of the graphene quantum dots coating nano zinc powder include:
将3g石墨烯量子点粉体加入到100mL乙醇水溶液中，超声分散30mi n，搅拌20min；超声振荡，用机械剪切机剪切4h，得到石墨烯量子点分散液；将纳米锌粉原料与石墨烯量子点分散液混合，球磨干燥，得到石墨烯量子点包覆纳米锌粉。3g graphene quantum dot powder was added to 100mL ethanol aqueous solution, ultrasonically dispersed for 30min, stirred for 20min; ultrasonically oscillated, and sheared with a mechanical shearing machine for 4h to obtain a graphene quantum dot dispersion; the nano-zinc powder raw material and graphite The graphene quantum dot dispersion liquid is mixed, ball milled and dried to obtain the graphene quantum dot coated nano zinc powder.
所述乙醇水溶液中乙醇的体积分数为2.8％。The volume fraction of ethanol in the ethanol aqueous solution is 2.8%.
所述纳米锌粉原料和碳量子点分散液的混合比例为：每1g纳米锌粉原料混入20mL碳量子点分散液。The mixing ratio of the nano-zinc powder raw material and the carbon quantum dot dispersion liquid is as follows: every 1 g of the nano-zinc powder raw material is mixed with 20 mL of the carbon quantum dot dispersion liquid.
所述粘结剂为羧甲基纤维素，硅酸钠和聚丙烯酸；羧甲基纤维素，硅酸钠和聚丙烯酸的重量比为3∶1.5∶1。The binder is carboxymethyl cellulose, sodium silicate and polyacrylic acid; the weight ratio of carboxymethyl cellulose, sodium silicate and polyacrylic acid is 3:1.5:1.
所述添加剂为八羟基笼型倍半硅氧烷，购买自西安齐岳生物科技有限公司。The additive was octahydroxycage silsesquioxane, which was purchased from Xi'an Qiyue Biotechnology Co., Ltd.
所述电解液二为质量浓度为36％的KOH水溶液。The second electrolyte is a KOH aqueous solution with a mass concentration of 36%.
所述含有改性纳米锌粉的锌锰电池的制备步骤包括：The preparation steps of the zinc-manganese battery containing the modified nano-zinc powder include:
S1.制备改性纳米锌粉；S1. Preparation of modified nano-zinc powder;
S2.将改性纳米锌粉，粘结剂，电解液一和添加剂混合均匀，得到负极锌膏；S2. Mix the modified nano-zinc powder, the binder, the electrolyte solution one and the additive evenly to obtain a negative electrode zinc paste;
S3.将正极环放入外壳，并注入电解液二，加入隔膜，静置至隔膜完全润湿，加入负极锌膏，组装得到锌锰电池成品。S3. Put the positive electrode ring into the casing, inject the electrolyte 2, add the diaphragm, let it stand until the diaphragm is completely wet, add the negative electrode zinc paste, and assemble the finished zinc-manganese battery.
实施例3.Example 3.
本实施例第一方面提供了一种含有改性纳米锌粉的锌锰电池，包括外壳，正极环，负极锌膏，隔膜和电解液一；所述负极锌膏的原料包括，按照重量比计，63％改性纳米锌粉，3％粘结剂，32％电解液二和2％添加剂。A first aspect of this embodiment provides a zinc-manganese battery containing modified nano-zinc powder, including an outer shell, a positive electrode ring, a negative electrode zinc paste, a separator and an electrolyte solution 1; the raw materials of the negative electrode zinc paste include, according to the weight ratio , 63% modified nano zinc powder, 3% binder, 32% electrolyte two and 2% additive.
所述改性纳米锌粉为碳量子点包覆纳米锌粉。The modified nano-zinc powder is carbon quantum dot-coated nano-zinc powder.
所述碳量子点为石墨烯量子点。The carbon quantum dots are graphene quantum dots.
所述纳米锌粉的粒径为400目，购买自湖南新威凌金属新材料科技股份有限公司。The particle size of the nano-zinc powder is 400 mesh, and it was purchased from Hunan Xinweiling Metal New Material Technology Co., Ltd.
所述石墨烯量子点包覆纳米锌粉的具体步骤包括：The specific steps of the graphene quantum dots coating nano zinc powder include:
将3g石墨烯量子点粉体加入到100mL乙醇水溶液中，超声分散30mi n，搅拌20min；超声振荡，用机械剪切机剪切4h，得到石墨烯量子点分散液；将纳米锌粉原料与石墨烯量子点分散液混合，球磨干燥，得到石墨烯量子点包覆纳米锌粉。3g graphene quantum dot powder was added to 100mL ethanol aqueous solution, ultrasonically dispersed for 30min, stirred for 20min; ultrasonically oscillated, sheared with a mechanical shearing machine for 4h to obtain a graphene quantum dot dispersion; the nano-zinc powder raw material and graphite The graphene quantum dot dispersion liquid is mixed, ball milled and dried to obtain the graphene quantum dot coated nano zinc powder.
所述乙醇水溶液中乙醇的体积分数为2.8％。The volume fraction of ethanol in the ethanol aqueous solution is 2.8%.
所述纳米锌粉原料和碳量子点分散液的混合比例为：每1g纳米锌粉原料混入20mL碳量子点分散液。The mixing ratio of the nano-zinc powder raw material and the carbon quantum dot dispersion liquid is as follows: every 1 g of the nano-zinc powder raw material is mixed with 20 mL of the carbon quantum dot dispersion liquid.
所述粘结剂为羧甲基纤维素，硅酸钠和聚丙烯酸；羧甲基纤维素，硅酸钠和聚丙烯酸的重量比为3∶1.5∶1。The binder is carboxymethyl cellulose, sodium silicate and polyacrylic acid; the weight ratio of carboxymethyl cellulose, sodium silicate and polyacrylic acid is 3:1.5:1.
所述添加剂为八羟基笼型倍半硅氧烷，购买自西安齐岳生物科技有限公司。The additive was octahydroxycage silsesquioxane, which was purchased from Xi'an Qiyue Biotechnology Co., Ltd.
所述电解液二为质量浓度为36％的KOH水溶液。The second electrolyte is a KOH aqueous solution with a mass concentration of 36%.
所述含有改性纳米锌粉的锌锰电池的制备步骤包括：The preparation steps of the zinc-manganese battery containing the modified nano-zinc powder include:
S1.制备改性纳米锌粉；S1. Preparation of modified nano-zinc powder;
S2.将改性纳米锌粉，粘结剂，电解液一和添加剂混合均匀，得到负极锌膏；S2. Mix the modified nano-zinc powder, the binder, the electrolyte solution one and the additive evenly to obtain a negative electrode zinc paste;
S3.将正极环放入外壳，并注入电解液二，加入隔膜，静置至隔膜完全润湿，加入负极锌膏，组装得到锌锰电池成品。S3. Put the positive electrode ring into the casing, inject the electrolyte 2, add the diaphragm, let it stand until the diaphragm is completely wet, add the negative electrode zinc paste, and assemble the finished zinc-manganese battery.
实施例4.Example 4.
本实施例第一方面提供了一种含有改性纳米锌粉的锌锰电池，包括外壳，正极环，负极锌膏，隔膜和电解液一；所述负极锌膏的原料包括，按照重量比计，53.5％纳米锌粉，5％粘结剂，39％电解液二和2.5％添加剂。A first aspect of this embodiment provides a zinc-manganese battery containing modified nano-zinc powder, including an outer shell, a positive electrode ring, a negative electrode zinc paste, a separator and an electrolyte solution 1; the raw materials of the negative electrode zinc paste include, according to the weight ratio , 53.5% nano-zinc powder, 5% binder, 39% electrolyte two and 2.5% additive.
所述纳米锌粉的粒径为400目，购买自湖南新威凌金属新材料科技股份有限公司。The particle size of the nano-zinc powder is 400 mesh, and it was purchased from Hunan Xinweiling Metal New Material Technology Co., Ltd.
所述粘结剂为羧甲基纤维素，硅酸钠和聚丙烯酸；羧甲基纤维素，硅酸钠和聚丙烯酸的重量比为3∶1.5∶1。The binder is carboxymethyl cellulose, sodium silicate and polyacrylic acid; the weight ratio of carboxymethyl cellulose, sodium silicate and polyacrylic acid is 3:1.5:1.
所述添加剂为八羟基笼型倍半硅氧烷，购买自西安齐岳生物科技有限公司。The additive was octahydroxycage silsesquioxane, which was purchased from Xi'an Qiyue Biotechnology Co., Ltd.
所述电解液二为质量浓度为36％的KOH水溶液。The second electrolyte is a KOH aqueous solution with a mass concentration of 36%.
所述含有改性纳米锌粉的锌锰电池的制备步骤包括：The preparation steps of the zinc-manganese battery containing the modified nano-zinc powder include:
S1.制备改性纳米锌粉；S1. Preparation of modified nano-zinc powder;
S2.将改性纳米锌粉，粘结剂，电解液一和添加剂混合均匀，得到负极锌膏；S2. Mix the modified nano-zinc powder, the binder, the electrolyte solution one and the additive evenly to obtain a negative electrode zinc paste;
S3.将正极环放入外壳，并注入电解液二，加入隔膜，静置至隔膜完全润湿，加入负极锌膏，组装得到锌锰电池成品。S3. Put the positive electrode ring into the casing, inject the electrolyte 2, add the diaphragm, let it stand until the diaphragm is completely wet, add the negative electrode zinc paste, and assemble the finished zinc-manganese battery.
实施例5.Example 5.
本实施例第一方面提供了一种含有改性纳米锌粉的锌锰电池，包括外壳，正极环，负极锌膏，隔膜和电解液一；所述负极锌膏的原料包括，按照重量比计，53.5％改性纳米锌粉，5％粘结剂，39％电解液二和2.5％添加剂。A first aspect of this embodiment provides a zinc-manganese battery containing modified nano-zinc powder, including a shell, a positive electrode ring, a negative electrode zinc paste, a separator and an electrolyte solution 1; the raw materials of the negative electrode zinc paste include, according to the weight ratio , 53.5% modified nano zinc powder, 5% binder, 39% electrolyte two and 2.5% additive.
所述改性纳米锌粉为碳量子点包覆纳米锌粉。The modified nano-zinc powder is carbon quantum dot-coated nano-zinc powder.
所述碳量子点为石墨烯量子点。The carbon quantum dots are graphene quantum dots.
所述纳米锌粉的粒径为400目，购买自湖南新威凌金属新材料科技股份有限公司。The particle size of the nano-zinc powder is 400 mesh, and it was purchased from Hunan Xinweiling Metal New Material Technology Co., Ltd.
所述石墨烯量子点包覆纳米锌粉的具体步骤包括：The specific steps of the graphene quantum dots coating nano zinc powder include:
将3g石墨烯量子点粉体加入到100mL乙醇水溶液中，超声分散30min，搅拌20min；超声振荡，用机械剪切机剪切4h，得到石墨烯量子点分散液；将纳米锌粉原料与石墨烯量子点分散液混合，球磨干燥，得到石墨烯量子点包覆纳米锌粉。Add 3g graphene quantum dot powder to 100mL ethanol aqueous solution, ultrasonically disperse for 30min, stir for 20min; ultrasonically oscillate and shear with a mechanical shear for 4h to obtain a graphene quantum dot dispersion; mix the nano zinc powder raw material with graphene The quantum dot dispersion liquid is mixed, ball-milled and dried to obtain graphene quantum dot-coated nano-zinc powder.
所述乙醇水溶液中乙醇的体积分数为2.8％。The volume fraction of ethanol in the ethanol aqueous solution is 2.8%.
所述纳米锌粉原料和碳量子点分散液的混合比例为：每1g纳米锌粉原料混入5mL碳量子点分散液。The mixing ratio of the nano-zinc powder raw material and the carbon quantum dot dispersion liquid is as follows: every 1 g of the nano-zinc powder raw material is mixed with 5 mL of the carbon quantum dot dispersion liquid.
所述粘结剂为羧甲基纤维素，硅酸钠和聚丙烯酸；羧甲基纤维素，硅酸钠和聚丙烯酸的重量比为3∶1.5∶1。The binder is carboxymethyl cellulose, sodium silicate and polyacrylic acid; the weight ratio of carboxymethyl cellulose, sodium silicate and polyacrylic acid is 3:1.5:1.
所述添加剂为八羟基笼型倍半硅氧烷，购买自西安齐岳生物科技有限公司。The additive was octahydroxycage silsesquioxane, which was purchased from Xi'an Qiyue Biotechnology Co., Ltd.
所述电解液二为质量浓度为36％的KOH水溶液。The second electrolyte is a KOH aqueous solution with a mass concentration of 36%.
所述含有改性纳米锌粉的锌锰电池的制备步骤包括：The preparation steps of the zinc-manganese battery containing the modified nano-zinc powder include:
S1.制备改性纳米锌粉；S1. Preparation of modified nano-zinc powder;
S2.将改性纳米锌粉，粘结剂，电解液一和添加剂混合均匀，得到负极锌膏；S2. Mix the modified nano-zinc powder, the binder, the electrolyte solution one and the additive evenly to obtain a negative electrode zinc paste;
S3.将正极环放入外壳，并注入电解液二，加入隔膜，静置至隔膜完全润湿，加入负极锌膏，组装得到锌锰电池成品。S3. Put the positive electrode ring into the casing, inject the electrolyte 2, add the diaphragm, let it stand until the diaphragm is completely wet, add the negative electrode zinc paste, and assemble the finished zinc-manganese battery.
实施例6.Example 6.
本实施例第一方面提供了一种含有改性纳米锌粉的锌锰电池，包括外壳，正极环，负极锌膏，隔膜和电解液一；所述负极锌膏的原料包括，按照重量比计，53.5％改性纳米锌粉，5％粘结剂，39％电解液二和2.5％添加剂。A first aspect of this embodiment provides a zinc-manganese battery containing modified nano-zinc powder, including an outer shell, a positive electrode ring, a negative electrode zinc paste, a separator and an electrolyte solution 1; the raw materials of the negative electrode zinc paste include, according to the weight ratio , 53.5% modified nano zinc powder, 5% binder, 39% electrolyte two and 2.5% additive.
所述改性纳米锌粉为碳量子点包覆纳米锌粉。The modified nano-zinc powder is carbon quantum dot-coated nano-zinc powder.
所述碳量子点为石墨烯量子点。The carbon quantum dots are graphene quantum dots.
所述纳米锌粉的粒径为60目，购买自清苑县同兴氧化锌有限公司。The particle size of the nano-zinc powder is 60 meshes, purchased from Qingyuan County Tongxing Zinc Oxide Co., Ltd.
所述石墨烯量子点包覆纳米锌粉的具体步骤包括：The specific steps of the graphene quantum dots coating nano zinc powder include:
将3g石墨烯量子点粉体加入到100mL乙醇水溶液中，超声分散30min，搅拌20min；超声振荡，用机械剪切机剪切4h，得到石墨烯量子点分散液；将纳米锌粉原料与石墨烯量子点分散液混合，球磨干燥，得到石墨烯量子点包覆纳米锌粉。Add 3g graphene quantum dot powder to 100mL ethanol aqueous solution, ultrasonically disperse for 30min, stir for 20min; ultrasonically oscillate and shear with a mechanical shear for 4h to obtain a graphene quantum dot dispersion; mix the nano zinc powder raw material with graphene The quantum dot dispersion liquid is mixed, ball-milled and dried to obtain graphene quantum dot-coated nano-zinc powder.
所述乙醇水溶液中乙醇的体积分数为2.8％。The volume fraction of ethanol in the ethanol aqueous solution is 2.8%.
所述纳米锌粉原料和碳量子点分散液的混合比例为：每1g纳米锌粉原料混入20mL碳量子点分散液。The mixing ratio of the nano-zinc powder raw material and the carbon quantum dot dispersion liquid is as follows: every 1 g of the nano-zinc powder raw material is mixed with 20 mL of the carbon quantum dot dispersion liquid.
所述粘结剂为羧甲基纤维素，硅酸钠和聚丙烯酸；羧甲基纤维素，硅酸钠和聚丙烯酸的重量比为3∶1.5∶1。The binder is carboxymethyl cellulose, sodium silicate and polyacrylic acid; the weight ratio of carboxymethyl cellulose, sodium silicate and polyacrylic acid is 3:1.5:1.
所述添加剂为八羟基笼型倍半硅氧烷，购买自西安齐岳生物科技有限公司。The additive was octahydroxycage silsesquioxane, which was purchased from Xi'an Qiyue Biotechnology Co., Ltd.
所述电解液二为质量浓度为36％的KOH水溶液。The second electrolyte is a KOH aqueous solution with a mass concentration of 36%.
所述含有改性纳米锌粉的锌锰电池的制备步骤包括：The preparation steps of the zinc-manganese battery containing the modified nano-zinc powder include:
S1.制备改性纳米锌粉；S1. Preparation of modified nano-zinc powder;
S2.将改性纳米锌粉，粘结剂，电解液一和添加剂混合均匀，得到负极锌膏；S2. Mix the modified nano-zinc powder, the binder, the electrolyte solution one and the additive evenly to obtain a negative electrode zinc paste;
S3.将正极环放入外壳，并注入电解液二，加入隔膜，静置至隔膜完全润湿，加入负极锌膏，组装得到锌锰电池成品。S3. Put the positive electrode ring into the casing, inject the electrolyte 2, add the diaphragm, let it stand until the diaphragm is completely wet, add the negative electrode zinc paste, and assemble the finished zinc-manganese battery.
实施例7.Example 7.
本实施例第一方面提供了一种含有改性纳米锌粉的锌锰电池，包括外壳，正极环，负极锌膏，隔膜和电解液一；所述负极锌膏的原料包括，按照重量比计，56％改性纳米锌粉，5％粘结剂，39％电解液二。A first aspect of this embodiment provides a zinc-manganese battery containing modified nano-zinc powder, including an outer shell, a positive electrode ring, a negative electrode zinc paste, a separator and an electrolyte solution 1; the raw materials of the negative electrode zinc paste include, according to the weight ratio , 56% modified nano zinc powder, 5% binder, 39% electrolyte two.
所述改性纳米锌粉为碳量子点包覆纳米锌粉。The modified nano-zinc powder is carbon quantum dot-coated nano-zinc powder.
所述碳量子点为石墨烯量子点。The carbon quantum dots are graphene quantum dots.
所述纳米锌粉的粒径为400目，购买自湖南新威凌金属新材料科技股份有限公司。The particle size of the nano-zinc powder is 400 mesh, and it was purchased from Hunan Xinweiling Metal New Material Technology Co., Ltd.
所述石墨烯量子点包覆纳米锌粉的具体步骤包括：The specific steps of the graphene quantum dots coating nano zinc powder include:
将3g石墨烯量子点粉体加入到100mL乙醇水溶液中，超声分散30min，搅拌20min；超声振荡，用机械剪切机剪切4h，得到石墨烯量子点分散液；将纳米锌粉原料与石墨烯量子点分散液混合，球磨干燥，得到石墨烯量子点包覆纳米锌粉。Add 3g graphene quantum dot powder to 100mL ethanol aqueous solution, ultrasonically disperse for 30min, stir for 20min; ultrasonically oscillate and shear with a mechanical shear for 4h to obtain a graphene quantum dot dispersion; mix the nano zinc powder raw material with graphene The quantum dot dispersion liquid is mixed, ball-milled and dried to obtain graphene quantum dot-coated nano-zinc powder.
所述乙醇水溶液中乙醇的体积分数为2.8％。The volume fraction of ethanol in the ethanol aqueous solution is 2.8%.
所述纳米锌粉原料和碳量子点分散液的混合比例为：每1g纳米锌粉原料混入20mL碳量子点分散液。The mixing ratio of the nano-zinc powder raw material and the carbon quantum dot dispersion liquid is as follows: every 1 g of the nano-zinc powder raw material is mixed with 20 mL of the carbon quantum dot dispersion liquid.
所述粘结剂为羧甲基纤维素，硅酸钠和聚丙烯酸；羧甲基纤维素，硅酸钠和聚丙烯酸的重量比为3∶1.5∶1。The binder is carboxymethyl cellulose, sodium silicate and polyacrylic acid; the weight ratio of carboxymethyl cellulose, sodium silicate and polyacrylic acid is 3:1.5:1.
所述添加剂为八羟基笼型倍半硅氧烷，购买自西安齐岳生物科技有限公司。The additive was octahydroxycage silsesquioxane, which was purchased from Xi'an Qiyue Biotechnology Co., Ltd.
所述电解液二为质量浓度为36％的KOH水溶液。The second electrolyte is a KOH aqueous solution with a mass concentration of 36%.
所述含有改性纳米锌粉的锌锰电池的制备步骤包括：The preparation steps of the zinc-manganese battery containing the modified nano-zinc powder include:
S1.制备改性纳米锌粉；S1. Preparation of modified nano-zinc powder;
S2.将改性纳米锌粉，粘结剂，电解液一和添加剂混合均匀，得到负极锌膏；S2. Mix the modified nano-zinc powder, the binder, the electrolyte solution one and the additive evenly to obtain a negative electrode zinc paste;
S3.将正极环放入外壳，并注入电解液二，加入隔膜，静置至隔膜完全润湿，加入负极锌膏，组装得到锌锰电池成品。S3. Put the positive electrode ring into the casing, inject the electrolyte 2, add the diaphragm, let it stand until the diaphragm is completely wet, add the negative electrode zinc paste, and assemble the finished zinc-manganese battery.
实施例8.Example 8.
本实施例第一方面提供了一种含有改性纳米锌粉的锌锰电池，包括外壳，正极环，负极锌膏，隔膜和电解液一；所述负极锌膏的原料包括，按照重量比计，53.5％改性纳米锌粉，5％粘结剂，39％电解液二和2.5％添加剂。A first aspect of this embodiment provides a zinc-manganese battery containing modified nano-zinc powder, including an outer shell, a positive electrode ring, a negative electrode zinc paste, a separator and an electrolyte solution 1; the raw materials of the negative electrode zinc paste include, according to the weight ratio , 53.5% modified nano zinc powder, 5% binder, 39% electrolyte two and 2.5% additive.
所述改性纳米锌粉为碳量子点包覆纳米锌粉。The modified nano-zinc powder is carbon quantum dot-coated nano-zinc powder.
所述碳量子点为石墨烯量子点。The carbon quantum dots are graphene quantum dots.
所述纳米锌粉的粒径为400目，购买自湖南新威凌金属新材料科技股份有限公司。The particle size of the nano-zinc powder is 400 mesh, and it was purchased from Hunan Xinweiling Metal New Material Technology Co., Ltd.
所述石墨烯量子点包覆纳米锌粉的具体步骤包括：The specific steps of the graphene quantum dots coating nano zinc powder include:
将3g石墨烯量子点粉体加入到100mL乙醇水溶液中，超声分散30min，搅拌20min；超声振荡，用机械剪切机剪切4h，得到石墨烯量子点分散液；将纳米锌粉原料与石墨烯量子点分散液混合，球磨干燥，得到石墨烯量子点包覆纳米锌粉。Add 3g graphene quantum dot powder to 100mL ethanol aqueous solution, ultrasonically disperse for 30min, stir for 20min; ultrasonically oscillate and shear with a mechanical shear for 4h to obtain a graphene quantum dot dispersion; mix the nano zinc powder raw material with graphene The quantum dot dispersion liquid is mixed, ball-milled and dried to obtain graphene quantum dot-coated nano-zinc powder.
所述乙醇水溶液中乙醇的体积分数为2.8％。The volume fraction of ethanol in the ethanol aqueous solution is 2.8%.
所述纳米锌粉原料和碳量子点分散液的混合比例为：每1g纳米锌粉原料混入20mL碳量子点分散液。The mixing ratio of the nano-zinc powder raw material and the carbon quantum dot dispersion liquid is as follows: every 1 g of the nano-zinc powder raw material is mixed with 20 mL of the carbon quantum dot dispersion liquid.
所述粘结剂为羧甲基纤维素，硅酸钠和聚丙烯酸；羧甲基纤维素，硅酸钠和聚丙烯酸的重量比为1∶1∶2。The binder is carboxymethyl cellulose, sodium silicate and polyacrylic acid; the weight ratio of carboxymethyl cellulose, sodium silicate and polyacrylic acid is 1:1:2.
所述添加剂为八羟基笼型倍半硅氧烷，购买自西安齐岳生物科技有限公司。The additive was octahydroxycage silsesquioxane, which was purchased from Xi'an Qiyue Biotechnology Co., Ltd.
所述电解液二为质量浓度为36％的KOH水溶液。The second electrolyte is a KOH aqueous solution with a mass concentration of 36%.
所述含有改性纳米锌粉的锌锰电池的制备步骤包括：The preparation steps of the zinc-manganese battery containing the modified nano-zinc powder include:
S1.制备改性纳米锌粉；S1. Preparation of modified nano-zinc powder;
S2.将改性纳米锌粉，粘结剂，电解液一混合均匀，得到负极锌膏；S2. Mix the modified nano-zinc powder, the binder and the electrolyte evenly to obtain a negative electrode zinc paste;
S3.将正极环放入外壳，并注入电解液二，加入隔膜，静置至隔膜完全润湿，加入负极锌膏，组装得到锌锰电池成品。S3. Put the positive electrode ring into the casing, inject the electrolyte 2, add the diaphragm, let it stand until the diaphragm is completely wet, add the negative electrode zinc paste, and assemble the finished zinc-manganese battery.
实施例9.Example 9.
本实施例第一方面提供了一种含有改性纳米锌粉的锌锰电池，包括外壳，正极环，负极锌膏，隔膜和电解液一；所述负极锌膏的原料包括，按照重量比计，53.5％改性纳米锌粉，5％粘结剂，39％电解液二和2.5％添加剂。A first aspect of this embodiment provides a zinc-manganese battery containing modified nano-zinc powder, including an outer shell, a positive electrode ring, a negative electrode zinc paste, a separator and an electrolyte solution 1; the raw materials of the negative electrode zinc paste include, according to the weight ratio , 53.5% modified nano zinc powder, 5% binder, 39% electrolyte two and 2.5% additive.
所述改性纳米锌粉为碳量子点包覆纳米锌粉。The modified nano-zinc powder is carbon quantum dot-coated nano-zinc powder.
所述碳量子点为石墨烯量子点。The carbon quantum dots are graphene quantum dots.
所述纳米锌粉的粒径为400目，购买自湖南新威凌金属新材料科技股份有限公司。The particle size of the nano-zinc powder is 400 mesh, and it was purchased from Hunan Xinweiling Metal New Material Technology Co., Ltd.
所述石墨烯量子点包覆纳米锌粉的具体步骤包括：The specific steps of the graphene quantum dots coating nano zinc powder include:
将3g石墨烯量子点粉体加入到100mL乙醇水溶液中，超声分散30min，搅拌20min；超声振荡，用机械剪切机剪切4h，得到石墨烯量子点分散液；将纳米锌粉原料与石墨烯量子点分散液混合，球磨干燥，得到石墨烯量子点包覆纳米锌粉。Add 3g graphene quantum dot powder to 100mL ethanol aqueous solution, ultrasonically disperse for 30min, stir for 20min; ultrasonically oscillate and shear with a mechanical shear for 4h to obtain a graphene quantum dot dispersion; mix the nano zinc powder raw material with graphene The quantum dot dispersion liquid is mixed, ball-milled and dried to obtain graphene quantum dot-coated nano-zinc powder.
所述乙醇水溶液中乙醇的体积分数为2.8％。The volume fraction of ethanol in the ethanol aqueous solution is 2.8%.
所述纳米锌粉原料和碳量子点分散液的混合比例为：每1g纳米锌粉原料混入20mL碳量子点分散液。The mixing ratio of the nano-zinc powder raw material and the carbon quantum dot dispersion liquid is as follows: every 1 g of the nano-zinc powder raw material is mixed with 20 mL of the carbon quantum dot dispersion liquid.
所述粘结剂为羧甲基纤维素和聚丙烯酸；羧甲基纤维素和聚丙烯酸的重量比为3：1。The binder is carboxymethyl cellulose and polyacrylic acid; the weight ratio of carboxymethyl cellulose and polyacrylic acid is 3:1.
所述添加剂为八羟基笼型倍半硅氧烷，购买自西安齐岳生物科技有限公司。The additive was octahydroxycage silsesquioxane, which was purchased from Xi'an Qiyue Biotechnology Co., Ltd.
所述电解液二为质量浓度为36％的KOH水溶液。The second electrolyte is a KOH aqueous solution with a mass concentration of 36%.
所述含有改性纳米锌粉的锌锰电池的制备步骤包括：The preparation steps of the zinc-manganese battery containing the modified nano-zinc powder include:
S1.制备改性纳米锌粉；S1. Preparation of modified nano-zinc powder;
S2.将改性纳米锌粉，粘结剂，电解液一和添加剂混合均匀，得到负极锌膏；S2. Mix the modified nano-zinc powder, the binder, the electrolyte solution one and the additive evenly to obtain a negative electrode zinc paste;
S3.将正极环放入外壳，并注入电解液二，加入隔膜，静置至隔膜完全润湿，加入负极锌膏，组装得到锌锰电池成品。S3. Put the positive electrode ring into the casing, inject the electrolyte 2, add the diaphragm, let it stand until the diaphragm is completely wet, add the negative electrode zinc paste, and assemble the finished zinc-manganese battery.
实施例10.Example 10.
本实施例第一方面提供了一种含有改性纳米锌粉的锌锰电池，包括外壳，正极环，负极锌膏，隔膜和电解液一；所述负极锌膏的原料包括，按照重量比计，53.5％改性纳米锌粉，5％粘结剂，39％电解液二和2.5％添加剂。A first aspect of this embodiment provides a zinc-manganese battery containing modified nano-zinc powder, including an outer shell, a positive electrode ring, a negative electrode zinc paste, a separator and an electrolyte solution 1; the raw materials of the negative electrode zinc paste include, according to the weight ratio , 53.5% modified nano zinc powder, 5% binder, 39% electrolyte two and 2.5% additive.
所述改性纳米锌粉为碳量子点包覆纳米锌粉。The modified nano-zinc powder is carbon quantum dot-coated nano-zinc powder.
所述碳量子点为石墨烯量子点。The carbon quantum dots are graphene quantum dots.
所述纳米锌粉的粒径为400目，购买自湖南新威凌金属新材料科技股份有限公司。The particle size of the nano-zinc powder is 400 mesh, and it was purchased from Hunan Xinweiling Metal New Material Technology Co., Ltd.
所述石墨烯量子点包覆纳米锌粉的具体步骤包括：The specific steps of the graphene quantum dots coating nano zinc powder include:
将3g石墨烯量子点粉体加入到100mL乙醇水溶液中，搅拌20min；超声振荡，用机械剪切机剪切4h，得到石墨烯量子点分散液；将纳米锌粉原料与石墨烯量子点分散液混合，球磨干燥，得到石墨烯量子点包覆纳米锌粉。Add 3g graphene quantum dot powder into 100mL ethanol aqueous solution, stir for 20min; ultrasonically oscillate, shear with mechanical shear for 4h to obtain graphene quantum dot dispersion; mix nano zinc powder raw material and graphene quantum dot dispersion Mixing, ball milling and drying to obtain graphene quantum dot-coated nano-zinc powder.
所述乙醇水溶液中乙醇的体积分数为2.8％。The volume fraction of ethanol in the ethanol aqueous solution is 2.8%.
所述纳米锌粉原料和碳量子点分散液的混合比例为：每1g纳米锌粉原料混入20mL碳量子点分散液。The mixing ratio of the nano-zinc powder raw material and the carbon quantum dot dispersion liquid is as follows: every 1 g of the nano-zinc powder raw material is mixed with 20 mL of the carbon quantum dot dispersion liquid.
所述粘结剂为羧甲基纤维素，硅酸钠和聚丙烯酸；羧甲基纤维素，硅酸钠和聚丙烯酸的重量比为3∶1.5∶1。The binder is carboxymethyl cellulose, sodium silicate and polyacrylic acid; the weight ratio of carboxymethyl cellulose, sodium silicate and polyacrylic acid is 3:1.5:1.
所述添加剂为八羟基笼型倍半硅氧烷，购买自西安齐岳生物科技有限公司。The additive was octahydroxycage silsesquioxane, which was purchased from Xi'an Qiyue Biotechnology Co., Ltd.
所述电解液二为质量浓度为36％的KOH水溶液。The second electrolyte is a KOH aqueous solution with a mass concentration of 36%.
所述含有改性纳米锌粉的锌锰电池的制备步骤包括：The preparation steps of the zinc-manganese battery containing the modified nano-zinc powder include:
S1.制备改性纳米锌粉；S1. Preparation of modified nano-zinc powder;
S2.将改性纳米锌粉，粘结剂，电解液一和添加剂混合均匀，得到负极锌膏；S2. Mix the modified nano-zinc powder, the binder, the electrolyte solution one and the additive evenly to obtain a negative electrode zinc paste;
S3.将正极环放入外壳，并注入电解液二，加入隔膜，静置至隔膜完全润湿，加入负极锌膏，组装得到锌锰电池成品。S3. Put the positive electrode ring into the casing, inject the electrolyte 2, add the diaphragm, let it stand until the diaphragm is completely wet, add the negative electrode zinc paste, and assemble the finished zinc-manganese battery.
性能测试方法performance test method
高温稳定性：High temperature stability:
将实施例1-10制得的电池置于100℃条件下7天，观察电池有无鼓包、漏液现象；评价等级具体为：The batteries prepared in Examples 1-10 were placed at 100°C for 7 days to observe whether the batteries had bulging or liquid leakage; the evaluation grades were as follows:
0级：无变化，即无可觉察的变化；Level 0: no change, i.e. no perceptible change;
1级：很轻微，即刚可觉察的变化；Level 1: very slight, i.e. just perceptible change;
2级：轻微，即有明显觉察的变化；Grade 2: Slight, that is, there is a noticeable change;
3级：中等，即有很明显觉察的变化；Level 3: Moderate, that is, there is a very noticeable change;
4级：较大，即有较大的变化；Level 4: large, that is, there is a large change;
5级：严重，即有强烈的变化；Grade 5: Severe, that is, there are strong changes;
电池容量：battery capacity:
参照国标GB/T 31467.2-2015测定实施例1-10制得的电池的放电容量。The discharge capacity of the batteries prepared in Examples 1-10 was measured with reference to the national standard GB/T 31467.2-2015.
安全性：safety:
参照国标GB/T 31467.2-2015测定实施例1-10制得的电池的安全性能；设置挤压力为300kN，保持30min，观察1h，看电池有无着火或***现象。无着火或***现象为安全性优，有着火或***现象为安全性差。Refer to the national standard GB/T 31467.2-2015 to measure the safety performance of the batteries prepared in Examples 1-10; set the extrusion force to 300kN, keep it for 30min, observe for 1h, and see if the battery catches fire or explodes. No fire or explosion phenomenon is regarded as excellent safety, and fire or explosion phenomenon is regarded as poor safety.
性能测试数据performance test data
表1.实施例1-10的性能测试结果Table 1. Performance Test Results of Examples 1-10
| 高温稳定性High temperature stability | 电池容量mAh/gBattery capacitymAh/g | 安全性safety | |
| 实施例1Example 1 | 00 | 312312 | 优excellent |
| 实施例2Example 2 | 00 | 304304 | 优excellent |
| 实施例3Example 3 | 00 | 309309 | 优excellent |
| 实施例4Example 4 | 44 | 157157 | 差Difference |
| 实施例5Example 5 | 11 | 276276 | 优excellent |
| 实施例6Example 6 | 22 | 245245 | 优excellent |
| 实施例7Example 7 | 22 | 251251 | 差Difference |
| 实施例8Example 8 | 11 | 269269 | 优excellent |
| 实施例9Example 9 | 22 | 240240 | 差Difference |
| 实施例10Example 10 | 33 | 213213 | 差Difference |
最后指出，前述的实例仅是说明性的，用于解释本发明所述方法的一些特征。所附的权利要求旨在要求可以设想的尽可能广的范围，且本文所呈现的实施例仅是根据所有可能的实施例的组合的选择的实施方式的说明。因此，申请人的用意是所附的权利要求不被 说明本发明的特征的示例的选择限制。在权利要求中所用的一些数值范围也包括了在其之内的子范围，这些范围中的变化也应在可能的情况下解释为被所附的权利要求覆盖。Finally, it is pointed out that the foregoing examples are illustrative only and serve to explain some of the features of the method of the present invention. The appended claims are intended to claim the broadest conceivable scope and the embodiments presented herein are merely illustrative of selected implementations according to a combination of all possible embodiments. Accordingly, it is the applicant's intention that the appended claims not be limited by the selection of examples that characterize the invention. Some of the numerical ranges used in the claims also include sub-ranges within them, and variations within these ranges should also be construed, where possible, to be covered by the appended claims.
Claims (10)
- 一种含有改性纳米锌粉的锌锰电池，包括外壳，正极环，负极锌膏，隔膜和电解液一；其特征在于，所述负极锌膏的原料包括，按照重量比计，46～65％改性纳米锌粉，3～7％粘结剂，27～46％电解液二和1～4％添加剂。A zinc-manganese battery containing modified nano-zinc powder, comprising an outer shell, a positive electrode ring, a negative electrode zinc paste, a diaphragm and an electrolyte solution 1; it is characterized in that the raw materials of the negative electrode zinc paste include, in terms of weight ratio, 46-65 % modified nano-zinc powder, 3-7% binder, 27-46% electrolyte 2 and 1-4% additive.
- 根据权利要求1所述的一种含有改性纳米锌粉的锌锰电池，其特征在于，所述改性纳米锌粉为碳量子点包覆纳米锌粉。The zinc-manganese battery containing modified nano-zinc powder according to claim 1, wherein the modified nano-zinc powder is carbon quantum dot-coated nano-zinc powder.
- 根据权利要求2所述的一种含有改性纳米锌粉的锌锰电池，其特征在于，所述碳量子点包括纳米金刚石，石墨烯量子点，荧光碳颗粒中的至少一种。A zinc-manganese battery containing modified nano-zinc powder according to claim 2, wherein the carbon quantum dots comprise at least one of nanodiamond, graphene quantum dots, and fluorescent carbon particles.
- 根据权利要求2所述的一种含有改性纳米锌粉的锌锰电池，其特征在于，所述碳量子点为石墨烯量子点。A zinc-manganese battery containing modified nano-zinc powder according to claim 2, wherein the carbon quantum dots are graphene quantum dots.
- 根据权利要求2所述的一种含有改性纳米锌粉的锌锰电池，其特征在于，所述碳量子点包覆纳米锌粉中纳米锌粉的粒径为200-600目。A zinc-manganese battery containing modified nano-zinc powder according to claim 2, wherein the particle size of the nano-zinc powder in the carbon quantum dot-coated nano-zinc powder is 200-600 mesh.
- 根据权利要求1所述的一种含有改性纳米锌粉的锌锰电池，其特征在于，所述粘结剂包括羧甲基纤维素，硅酸钠，聚丙烯酸，聚甲基丙烯酸酯中的至少一种。A zinc-manganese battery containing modified nano-zinc powder according to claim 1, wherein the binder comprises carboxymethyl cellulose, sodium silicate, polyacrylic acid, polymethacrylate at least one.
- 根据权利要求1所述的一种含有改性纳米锌粉的锌锰电池，其特征在于，所述添加剂为笼型倍半硅氧烷。The zinc-manganese battery containing modified nano-zinc powder according to claim 1, wherein the additive is cage-type silsesquioxane.
- 根据权利要求7所述的一种含有改性纳米锌粉的锌锰电池，其特征在于，所述笼型倍半硅氧烷包括乙烯基-POSS，氨基-POSS，环氧基-POSS，羟基-POSS中的至少一种。The zinc-manganese battery containing modified nano-zinc powder according to claim 7, wherein the cage-type silsesquioxane comprises vinyl-POSS, amino-POSS, epoxy-POSS, hydroxyl - At least one of POSS.
- 根据权利要求8所述的一种含有改性纳米锌粉的锌锰电池，其特征在于，所述电解液二为质量浓度为32-40％的碱金属水溶液。The zinc-manganese battery containing modified nano-zinc powder according to claim 8, wherein the second electrolyte is an alkali metal aqueous solution with a mass concentration of 32-40%.
- 一种根据权利要求1-9任一项所述的含有改性纳米锌粉的锌锰电池的制备方法，其特征在于，制备步骤包括：A method for preparing a zinc-manganese battery containing modified nano-zinc powder according to any one of claims 1-9, wherein the preparation step comprises:S1.制备改性纳米锌粉；S1. Preparation of modified nano-zinc powder;S2.将改性纳米锌粉，粘结剂，电解液一和添加剂混合均匀，得到负极锌膏；S2. Mix the modified nano-zinc powder, the binder, the electrolyte solution one and the additive evenly to obtain a negative electrode zinc paste;S3.将正极环放入外壳，并注入电解液二，加入隔膜，静置至隔膜完全润湿，加入负极锌膏，组装得到锌锰电池成品。S3. Put the positive electrode ring into the casing, inject the electrolyte 2, add the diaphragm, let it stand until the diaphragm is completely wet, add the negative electrode zinc paste, and assemble the finished zinc-manganese battery.
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| CN104201357B (en) * | 2014-09-18 | 2016-10-19 | 温州大学 | A kind of graphene quantum dot-graphene composite material and preparation method thereof and purposes |
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| CN106784828A (en) * | 2016-12-30 | 2017-05-31 | 尹宗杰 | A kind of layer type casting moulding Graphene metallic composite and preparation method |
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