CN114628708B - Mercury-free lead-free cadmium-free zinc-manganese battery and manufacturing method thereof - Google Patents

Mercury-free lead-free cadmium-free zinc-manganese battery and manufacturing method thereof Download PDF

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CN114628708B
CN114628708B CN202210322577.9A CN202210322577A CN114628708B CN 114628708 B CN114628708 B CN 114628708B CN 202210322577 A CN202210322577 A CN 202210322577A CN 114628708 B CN114628708 B CN 114628708B
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free
mercury
zinc
paper
layer paper
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CN114628708A (en
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徐增富
李树波
程方军
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Hangzhou Eternal Battery Co ltd
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Hangzhou Eternal Battery Co ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M6/00—Primary cells; Manufacture thereof
    • H01M6/04—Cells with aqueous electrolyte
    • H01M6/045—Cells with aqueous electrolyte characterised by 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
    • 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
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/44—Fibrous material
    • 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
    • H01M6/06—Dry cells, i.e. cells wherein the electrolyte is rendered non-fluid
    • H01M6/08—Dry cells, i.e. cells wherein the electrolyte is rendered non-fluid with cup-shaped electrodes
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0002—Aqueous electrolytes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0085—Immobilising or gelification of electrolyte
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0088—Composites
    • H01M2300/0091—Composites in the form of mixtures
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

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  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Primary Cells (AREA)

Abstract

The invention discloses a mercury-free lead-free cadmium-free zinc-manganese battery, which comprises mercury-free slurry layer paper, a bottom bowl, a re-pressing ring, a carbon rod, an iron bottom, a combined cap, a zinc cylinder, an outer cladding insulating layer and a battery cell, wherein the mercury-free slurry layer paper is in a cylindrical shape, and the bottom bowl is arranged at the lower end of an inner cavity of the mercury-free slurry layer paper; the metal elements such as magnesium, titanium, tin, indium and bismuth are used for replacing most of lead, mercury and cadmium on the traditional battery zinc cylinder, and the metals such as magnesium, titanium, tin, indium and bismuth are added into the negative electrode zinc material to replace toxic heavy metals such as lead and cadmium in the common battery negative electrode, so that the defects of the negative electrode zinc in the aspects of ductility and corrosion inhibition performance after the negative electrode is removed are overcome, and in addition, the corrosion inhibition performance of the mercury-free slurry layer paper is enhanced by improving the formula of the mercury-free slurry layer paper pulp. Through the synergistic effect of the two aspects, the hydrogen evolution overpotential of zinc in the battery is improved, the self-discharge of the battery is reduced, and the gas evolution of the battery is reduced.

Description

Mercury-free lead-free cadmium-free zinc-manganese battery and manufacturing method thereof
Technical Field
The invention relates to the technical field of zinc-manganese batteries, in particular to a mercury-free lead-free cadmium-free zinc-manganese battery and a manufacturing method thereof.
Background
The mercury-free lead-free cadmium-free battery is a development trend of future batteries, but the zinc-manganese dry batteries on the market at present are mercury-free low-lead low-cadmium batteries (lead is less than or equal to 0.1000 percent and cadmium is less than or equal to 0.01 percent), but lead and cadmium are heavy metals limited to use by the International environmental protection organization, and lead and cadmium are forbidden to be used for the zinc-manganese dry batteries before the end of 11 months of 2025 in China, and lead is required to be less than or equal to 0.004 percent and cadmium is required to be less than or equal to 0.002 percent. Because in zinc of the negative electrode of the zinc-manganese dry battery, lead and cadmium play a role in improving ductility and corrosion inhibition performance, after lead and cadmium removal, difficulty is brought to the punching of a negative electrode zinc cylinder, corrosion inhibition performance is also greatly reduced, natural manganese is partially used in the positive electrode powder of the common zinc-manganese dry battery, the impurity content is higher, the corrosion inhibition effect of the mercury corrosion inhibitor is not ideal, the self discharge of the battery is serious during the storage period, and the quality problems of air inflation, liquid leakage, electrical property reduction and the like are easily caused, so that the storage performance and the safety performance of the battery are influenced.
Disclosure of Invention
The invention aims to provide a mercury-free, lead-free, cadmium-free zinc-manganese battery and a manufacturing method thereof, so as to solve the problems in the background technology.
In order to achieve the above purpose, the present invention provides the following technical solutions: a mercury-free lead-free cadmium-free zinc-manganese battery and a manufacturing method thereof, the mercury-free lead-free cadmium-free zinc-manganese battery comprises:
the mercury-free pulp layer paper is arranged in a cylinder shape;
the bottom bowl is arranged at the lower end of the inner cavity of the mercury-free pulp layer paper;
the re-pressing ring is arranged at the upper end of the inner cavity of the mercury-free pulp layer paper, and a through hole is formed in the center of the re-pressing ring;
the lower end of the carbon rod is arranged in the inner cavity of the mercury-free slurry layer paper, and the upper end of the carbon rod is positioned through a through hole at the center of the re-pressing ring;
the combined cap is arranged at the uppermost end of the mercury-free slurry layer paper, and the upper end of the carbon rod is coated by the combined cap;
the zinc cylinder is coated on the outer side surface of the mercury-free pulp layer paper, and is of a cylindrical structure with a sealed bottom surface;
the iron bottom is attached to the bottom surface of the zinc cylinder;
the outer cladding insulating layer is arranged on the outer side surface of the zinc cylinder in a cladding mode;
the battery cell is arranged in the inner cavity of the mercury-free slurry layer paper, and the lower end of the carbon rod is coated by the battery cell.
Preferably, the bottom bowl is a scanning body with a cross section in a transverse L shape, and the side edge of the bottom bowl is fixedly bonded with the inner side wall of the mercury-free slurry layer paper.
Preferably, the re-pressing ring is of a scanning body structure with a concave section, and the inner side wall and the outer side wall of the re-pressing ring are respectively fixedly bonded with the outer side wall of the carbon rod and the inner side wall of the mercury-free slurry layer paper.
Preferably, the combined cap is formed by combining a first cap body and a second cap body, a clamping groove is formed in the first cap body, a bayonet is formed in the second cap body, the bayonet corresponds to the clamping groove, and the upper side end of the zinc cylinder is clamped between the clamping groove and the bayonet.
Preferably, the zinc cylinder comprises the following materials in percentage by mass: 0.001-0.01% of magnesium, 0.02-0.05% of titanium, 0.001-0.005% of tin, 0.005-0.01% of indium, 0.005-0.015% of bismuth, 0.002-0.004% of lead, 0.001-0.002% of cadmium and the balance of zinc.
The method for manufacturing the mercury-free lead-free cadmium-free zinc-manganese battery comprises the following steps of:
step one: proportioning and melting the raw materials;
step two: pouring and forming a zinc plate;
step three: punching, cake washing and extrusion of the zinc plate;
step four: preparing mercury-free pulp layer paper;
step five: and (3) assembling the battery body.
Preferably, in the proportioning and melting process of the raw materials, zinc and titanium are mixed, heated and melted to prepare titanium-zinc alloy, and then mixed with magnesium, tin, indium, bismuth and zinc according to a proportion, and heated to 430-440 ℃ to obtain a melt.
Preferably, the mercury-free paper is used as an isolation layer, and the mercury-free paper is prepared by coating the double sides of the K8 cable paper with mercury-free electric paste and drying at 100-105 ℃.
Preferably, the raw material components of the mercury-free electropaste comprise (in mass percent): 9-11% of zinc chloride, 16-19% of ammonium chloride, 5-7% of flour, 3-5% of glutinous rice flour, 10-12% of etherified starch, 0.08-0.15% of polyvinyl alcohol, 0.02-0.04% of polyacrylamide, 0.005-0.015% of boric acid, 0.04-0.15% of alkylphenol ethoxylate, 0.03-0.05% of bismuth trichloride, 0.001-0.003% of indium chloride and the balance of water.
Compared with the prior art, the invention has the beneficial effects that:
1. the mercury-free and lead-free zinc-manganese battery is composed of mercury-free slurry layer paper, a bottom bowl, a re-pressing ring, a carbon rod, an iron bottom, a combined cap, a zinc cylinder, an outer cladding insulating layer and a battery core, and most of lead, mercury and cadmium on the traditional battery zinc cylinder are replaced by metal elements such as magnesium, titanium, tin, indium and bismuth. Through the synergistic effect of the two aspects, the hydrogen evolution overpotential of zinc in the battery is improved, the self-discharge of the battery is reduced, and the gas evolution of the battery is reduced;
2. the mercury-free paste formula coated by the mercury-free slurry layer paper is optimized, and the specific proportion and the process enable the mercury-free lead-free cadmium-free battery to achieve a good corrosion inhibition effect, so that the self-discharge of the battery is remarkably reduced, and the possibility of liquid leakage and gas expansion in the discharging process and the storage process of the battery is greatly reduced.
Drawings
FIG. 1 is a schematic diagram of the structure of the present invention;
FIG. 2 is an enlarged schematic view of the structure A in FIG. 1;
fig. 3 is an enlarged schematic view of the structure at B in fig. 1.
In the figure: the device comprises mercury-free slurry layer paper 1, a bottom bowl 2, a double-pressing ring 3, a carbon rod 4, an iron bottom 5, a zinc cylinder 6, an outer cladding insulating layer 7, a battery cell 8, a first cap 9 and a second cap 10.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Referring to fig. 1-3, the present invention provides a technical solution: the mercury-free lead-free cadmium-free zinc-manganese battery comprises mercury-free pulp paper 1, a bottom bowl 2, a double-pressing ring 3, a carbon rod 4, an iron bottom 5, a combined cap, a zinc cylinder 6, an outer cladding insulating layer 7 and a battery core 8, wherein the mercury-free pulp paper 1 is in a cylindrical shape, the bottom bowl 2 is arranged at the lower end of an inner cavity of the mercury-free pulp paper 1, the double-pressing ring 3 is arranged at the upper end of the inner cavity of the mercury-free pulp paper 1, a through hole is formed in the center position of the double-pressing ring 3, the lower end of the carbon rod 4 is arranged in the inner cavity of the mercury-free pulp paper 1, the upper end of the carbon rod 4 is positioned through the through hole in the center position of the double-pressing ring 3, the combined cap is arranged at the uppermost end of the mercury-free pulp paper 1, the upper end of the carbon rod 4 is clad through the combined cap, the zinc cylinder 6 is clad on the outer side surface of the mercury-free pulp paper 1, the zinc cylinder 6 is in a cylindrical structure with a bottom surface seal, the iron bottom 5 is in a joint with the bottom surface of the zinc cylinder 6, the lower end of the zinc cylinder 6 is in a cylindrical structure, the inner cavity of the zinc cylinder 6 is clad on the outer side of the inner cavity of the mercury-free pulp paper 1, and the upper end of the electric core is clad on the outer side of the carbon rod 4.
The bottom bowl 2 is a scanning body with a transverse L-shaped section, and the side edge of the bottom bowl 2 is fixedly bonded with the inner side wall of the mercury-free pulp layer paper 1.
The re-pressing ring 3 is a scanning body structure with a concave section, and the inner and outer side walls of the re-pressing ring 3 are respectively fixedly bonded with the outer side wall of the carbon rod 4 and the inner side wall of the mercury-free slurry layer paper 1.
The combined cap is formed by combining a first cap body 9 and a second cap body 10, a clamping groove is formed in the first cap body 9, a bayonet is formed in the second cap body 10, the bayonet corresponds to the clamping groove, and the upper side end of the zinc cylinder 6 is clamped between the clamping groove and the bayonet.
Example 1
The zinc cylinder 6 is made of the following materials in percentage by mass: 0.005% magnesium, 0.03% titanium, 0.003% tin, 0.008% indium, 0.01% bismuth, 0.003% lead, 0.001% cadmium and the balance zinc.
The manufacturing method of the mercury-free lead-free cadmium-free zinc-manganese battery comprises the following steps:
step one: proportioning and melting the raw materials;
step two: pouring and forming a zinc plate;
step three: punching, cake washing and extrusion of the zinc plate;
step four: preparing mercury-free pulp layer paper;
step five: and (3) assembling the battery body.
In the proportioning and melting process of the raw materials, zinc and titanium are firstly mixed, heated and melted to prepare titanium-zinc alloy, and then mixed with magnesium, tin, indium, bismuth and zinc according to a proportion, and heated to 430 ℃ to obtain a melt.
The raw material components of the mercury-free electropaste comprise (by mass percent): 10% of zinc chloride, 17% of ammonium chloride, 6% of flour, 4% of glutinous rice flour, 10% of etherified starch, 0.1% of polyvinyl alcohol, 0.03% of polyacrylamide, 0.01% of boric acid, 0.11% of alkylphenol ethoxylates, 0.04% of bismuth trichloride, 0.002% of indium chloride and the balance of water.
Mixing zinc chloride, ammonium chloride and water according to the mass ratio, and purifying by a zinc hanging plate, wherein the iron content is less than or equal to 0.0001%, and the corrosion test is qualified;
mixing zinc chloride, ammonium chloride and water according to the mass ratio, and purifying by hanging zinc slag, wherein the iron content is less than or equal to 0.0001%, and the corrosion test is qualified to obtain high-concentration electrolyte; adding polyacrylamide accounting for 0.15% of the mass of the high-concentration electrolyte into the high-concentration electrolyte, soaking, and fully stirring until the polyacrylamide is completely dissolved to obtain the high-concentration electrolyte;
adding low-concentration electrohydraulic liquid, polyvinyl alcohol solution, glutinous rice flour, etherified starch, alkylphenol ethoxylate and polyacrylamide solution into a ceramic jar according to a proportion, fully stirring until uniform, then slowly adding indium chloride aqueous solution (10wt%) and bismuth trichloride aqueous solution (10wt%) in sequence, stirring while adding, and uniformly mixing to obtain the composite material;
and then coating a layer of mercury-free electric paste on one side of the K8 cable paper by a coating machine, stirring the paper continuously before the coating of the mercury-free electric paste to uniformly distribute the components, drying the paper by a 100 ℃ oven, coating the other side of the paper, and finally rolling and cutting the paper to obtain the mercury-free slurry layer paper.
The preparation steps of the battery are as follows:
cutting the mercury-free pulp layer paper 1, setting the paper closely to the inner wall of the zinc cylinder 6, arranging the cutting bottom bowl 2 at the bottom of the zinc cylinder 6 and setting the paper closely to the bottom wall of the zinc cylinder 6; after the cell powder is pressed and molded to obtain a cell 8, the cell 8 is placed in a zinc cylinder 6, the molded cell 8 is separated from the zinc cylinder 6 by utilizing mercury-free slurry layer paper 1, a re-pressing ring 3 is arranged above the molded cell 8 for re-pressing, a carbon rod 4 is inserted in the cell 8, glue is coated on the upper edge of the inner wall of the zinc cylinder 6 and the upper part of the carbon rod 4, a combined cap is covered on the top of the zinc cylinder, and then a trademark is sleeved, and heat shrinkage is performed after the iron bottom 5 is covered.
Example two
The zinc cylinder 6 is made of the following materials in percentage by mass: 0.001% of magnesium, 0.03% of titanium, 0.003% of tin, 0.008% of indium, 0.01% of bismuth, 0.003% of lead, 0.001% of cadmium and the balance of zinc.
The manufacturing method of the mercury-free lead-free cadmium-free zinc-manganese battery comprises the following steps:
step one: proportioning and melting the raw materials;
step two: pouring and forming a zinc plate;
step three: punching, cake washing and extrusion of the zinc plate;
step four: preparing mercury-free pulp layer paper;
step five: and (3) assembling the battery body.
In the proportioning and melting process of the raw materials, zinc and titanium are firstly mixed, heated and melted to prepare titanium-zinc alloy, and then mixed with magnesium, tin, indium, bismuth and zinc according to a proportion, and heated to 430 ℃ to obtain a melt.
The raw material components of the mercury-free electropaste comprise (by mass percent): 10% of zinc chloride, 17% of ammonium chloride, 6% of flour, 4% of glutinous rice flour, 10% of etherified starch, 0.1% of polyvinyl alcohol, 0.03% of polyacrylamide, 0.01% of boric acid, 0.11% of alkylphenol ethoxylates, 0.04% of bismuth trichloride, 0.002% of indium chloride and the balance of water.
Mixing polyvinyl alcohol, boric acid and water according to the mass ratio, heating in water bath to boil, and stirring while heating to obtain the final product;
mixing zinc chloride, ammonium chloride and water according to the mass ratio, and purifying by hanging zinc slag, wherein the iron content is less than or equal to 0.0001%, and the corrosion test is qualified to obtain high-concentration electrolyte; adding polyacrylamide accounting for 0.15% of the mass of the high-concentration electrolyte into the high-concentration electrolyte, soaking, and fully stirring until the polyacrylamide is completely dissolved to obtain the high-concentration electrolyte;
adding low-concentration electrohydraulic liquid, polyvinyl alcohol solution, glutinous rice flour, etherified starch, alkylphenol ethoxylate and polyacrylamide solution into a ceramic jar according to a proportion, fully stirring until uniform, then slowly adding indium chloride aqueous solution (10wt%) and bismuth trichloride aqueous solution (10wt%) in sequence, stirring while adding, and uniformly mixing to obtain the composite material;
and then coating a layer of mercury-free electric paste on one side of the K8 cable paper by a coating machine, stirring the paper continuously before the coating of the mercury-free electric paste to uniformly distribute the components, drying the paper by a 100 ℃ oven, coating the other side of the paper, and finally rolling and cutting the paper to obtain the mercury-free slurry layer paper.
The preparation steps of the battery are as follows:
cutting the mercury-free pulp layer paper 1, setting the paper closely to the inner wall of the zinc cylinder 6, arranging the cutting bottom bowl 2 at the bottom of the zinc cylinder 6 and setting the paper closely to the bottom wall of the zinc cylinder 6; after the cell powder is pressed and molded to obtain a cell 8, the cell 8 is placed in a zinc cylinder 6, the molded cell 8 is separated from the zinc cylinder 6 by utilizing mercury-free slurry layer paper 1, a re-pressing ring 3 is arranged above the molded cell 8 for re-pressing, a carbon rod 4 is inserted in the cell 8, glue is coated on the upper edge of the inner wall of the zinc cylinder 6 and the upper part of the carbon rod 4, a combined cap is covered on the top of the zinc cylinder, and then a trademark is sleeved, and heat shrinkage is performed after the iron bottom 5 is covered.
Example III
The zinc cylinder 6 is made of the following materials in percentage by mass: 0.01% of magnesium, 0.03% of titanium, 0.003% of tin, 0.008% of indium, 0.01% of bismuth, 0.003% of lead, 0.001% of cadmium and the balance of zinc.
The manufacturing method of the mercury-free lead-free cadmium-free zinc-manganese battery comprises the following steps:
step one: proportioning and melting the raw materials;
step two: pouring and forming a zinc plate;
step three: punching, cake washing and extrusion of the zinc plate;
step four: preparing mercury-free pulp layer paper;
step five: and (3) assembling the battery body.
In the proportioning and melting process of the raw materials, zinc and titanium are firstly mixed, heated and melted to prepare titanium-zinc alloy, and then mixed with magnesium, tin, indium, bismuth and zinc according to a proportion, and heated to 430 ℃ to obtain a melt.
The raw material components of the mercury-free electropaste comprise (by mass percent): 10% of zinc chloride, 17% of ammonium chloride, 6% of flour, 4% of glutinous rice flour, 10% of etherified starch, 0.1% of polyvinyl alcohol, 0.03% of polyacrylamide, 0.01% of boric acid, 0.11% of alkylphenol ethoxylates, 0.04% of bismuth trichloride, 0.002% of indium chloride and the balance of water.
Mixing polyvinyl alcohol, boric acid and water according to the mass ratio, heating in water bath to boil, and stirring while heating to obtain the final product;
mixing zinc chloride, ammonium chloride and water according to the mass ratio, and purifying by hanging zinc slag, wherein the iron content is less than or equal to 0.0001%, and the corrosion test is qualified to obtain high-concentration electrolyte; adding polyacrylamide accounting for 0.15% of the mass of the high-concentration electrolyte into the high-concentration electrolyte, soaking, and fully stirring until the polyacrylamide is completely dissolved to obtain the high-concentration electrolyte;
adding low-concentration electrohydraulic liquid, polyvinyl alcohol solution, glutinous rice flour, etherified starch, alkylphenol ethoxylate and polyacrylamide solution into a ceramic jar according to a proportion, fully stirring until uniform, then slowly adding indium chloride aqueous solution (10wt%) and bismuth trichloride aqueous solution (10wt%) in sequence, stirring while adding, and uniformly mixing to obtain the composite material;
and then coating a layer of mercury-free electric paste on one side of the K8 cable paper by a coating machine, stirring the paper continuously before the coating of the mercury-free electric paste to uniformly distribute the components, drying the paper by a 100 ℃ oven, coating the other side of the paper, and finally rolling and cutting the paper to obtain the mercury-free slurry layer paper.
The preparation steps of the battery are as follows:
cutting the mercury-free pulp layer paper 1, setting the paper closely to the inner wall of the zinc cylinder 6, arranging the cutting bottom bowl 2 at the bottom of the zinc cylinder 6 and setting the paper closely to the bottom wall of the zinc cylinder 6; after the cell powder is pressed and molded to obtain a cell 8, the cell 8 is placed in a zinc cylinder 6, the molded cell 8 is separated from the zinc cylinder 6 by utilizing mercury-free slurry layer paper 1, a re-pressing ring 3 is arranged above the molded cell 8 for re-pressing, a carbon rod 4 is inserted in the cell 8, glue is coated on the upper edge of the inner wall of the zinc cylinder 6 and the upper part of the carbon rod 4, a combined cap is covered on the top of the zinc cylinder, and then a trademark is sleeved, and heat shrinkage is performed after the iron bottom 5 is covered.
Example IV
The zinc cylinder 6 is made of the following materials in percentage by mass: 0.005% magnesium, 0.02% titanium, 0.003% tin, 0.008% indium, 0.01% bismuth, 0.003% lead, 0.001% cadmium and the balance zinc.
The manufacturing method of the mercury-free lead-free cadmium-free zinc-manganese battery comprises the following steps:
step one: proportioning and melting the raw materials;
step two: pouring and forming a zinc plate;
step three: punching, cake washing and extrusion of the zinc plate;
step four: preparing mercury-free pulp layer paper;
step five: and (3) assembling the battery body.
In the proportioning and melting process of the raw materials, zinc and titanium are firstly mixed, heated and melted to prepare titanium-zinc alloy, and then mixed with magnesium, tin, indium, bismuth and zinc according to a proportion, and heated to 430 ℃ to obtain a melt.
The raw material components of the mercury-free electropaste comprise (by mass percent): 10% of zinc chloride, 17% of ammonium chloride, 6% of flour, 4% of glutinous rice flour, 10% of etherified starch, 0.1% of polyvinyl alcohol, 0.03% of polyacrylamide, 0.01% of boric acid, 0.11% of alkylphenol ethoxylates, 0.04% of bismuth trichloride, 0.002% of indium chloride and the balance of water.
Mixing polyvinyl alcohol, boric acid and water according to the mass ratio, heating in water bath to boil, and stirring while heating to obtain the final product;
mixing zinc chloride, ammonium chloride and water according to the mass ratio, and purifying by hanging zinc slag, wherein the iron content is less than or equal to 0.0001%, and the corrosion test is qualified to obtain high-concentration electrolyte; adding polyacrylamide accounting for 0.15% of the mass of the high-concentration electrolyte into the high-concentration electrolyte, soaking, and fully stirring until the polyacrylamide is completely dissolved to obtain the high-concentration electrolyte;
adding low-concentration electrohydraulic liquid, polyvinyl alcohol solution, glutinous rice flour, etherified starch, alkylphenol ethoxylate and polyacrylamide solution into a ceramic jar according to a proportion, fully stirring until uniform, then slowly adding indium chloride aqueous solution (10wt%) and bismuth trichloride aqueous solution (10wt%) in sequence, stirring while adding, and uniformly mixing to obtain the composite material;
and then coating a layer of mercury-free electric paste on one side of the K8 cable paper by a coating machine, stirring the paper continuously before the coating of the mercury-free electric paste to uniformly distribute the components, drying the paper by a 100 ℃ oven, coating the other side of the paper, and finally rolling and cutting the paper to obtain the mercury-free slurry layer paper.
The preparation steps of the battery are as follows:
cutting the mercury-free pulp layer paper 1, setting the paper closely to the inner wall of the zinc cylinder 6, arranging the cutting bottom bowl 2 at the bottom of the zinc cylinder 6 and setting the paper closely to the bottom wall of the zinc cylinder 6; after the cell powder is pressed and molded to obtain a cell 8, the cell 8 is placed in a zinc cylinder 6, the molded cell 8 is separated from the zinc cylinder 6 by utilizing mercury-free slurry layer paper 1, a re-pressing ring 3 is arranged above the molded cell 8 for re-pressing, a carbon rod 4 is inserted in the cell 8, glue is coated on the upper edge of the inner wall of the zinc cylinder 6 and the upper part of the carbon rod 4, a combined cap is covered on the top of the zinc cylinder, and then a trademark is sleeved, and heat shrinkage is performed after the iron bottom 5 is covered.
Example five
The zinc cylinder 6 is made of the following materials in percentage by mass: 0.005% magnesium, 0.05% titanium, 0.003% tin, 0.008% indium, 0.01% bismuth, 0.003% lead, 0.001% cadmium and the balance zinc.
The manufacturing method of the mercury-free lead-free cadmium-free zinc-manganese battery comprises the following steps:
step one: proportioning and melting the raw materials;
step two: pouring and forming a zinc plate;
step three: punching, cake washing and extrusion of the zinc plate;
step four: preparing mercury-free pulp layer paper;
step five: and (3) assembling the battery body.
In the proportioning and melting process of the raw materials, zinc and titanium are firstly mixed, heated and melted to prepare titanium-zinc alloy, and then mixed with magnesium, tin, indium, bismuth and zinc according to a proportion, and heated to 430 ℃ to obtain a melt.
The raw material components of the mercury-free electropaste comprise (by mass percent): 10% of zinc chloride, 17% of ammonium chloride, 6% of flour, 4% of glutinous rice flour, 10% of etherified starch, 0.1% of polyvinyl alcohol, 0.03% of polyacrylamide, 0.01% of boric acid, 0.11% of alkylphenol ethoxylates, 0.04% of bismuth trichloride, 0.002% of indium chloride and the balance of water.
Mixing polyvinyl alcohol, boric acid and water according to the mass ratio, heating in water bath to boil, and stirring while heating to obtain the final product;
mixing zinc chloride, ammonium chloride and water according to the mass ratio, and purifying by hanging zinc slag, wherein the iron content is less than or equal to 0.0001%, and the corrosion test is qualified to obtain high-concentration electrolyte; adding polyacrylamide accounting for 0.15% of the mass of the high-concentration electrolyte into the high-concentration electrolyte, soaking, and fully stirring until the polyacrylamide is completely dissolved to obtain the high-concentration electrolyte;
adding low-concentration electrohydraulic liquid, polyvinyl alcohol solution, glutinous rice flour, etherified starch, alkylphenol ethoxylate and polyacrylamide solution into a ceramic jar according to a proportion, fully stirring until uniform, then slowly adding indium chloride aqueous solution (10wt%) and bismuth trichloride aqueous solution (10wt%) in sequence, stirring while adding, and uniformly mixing to obtain the composite material;
and then coating a layer of mercury-free electric paste on one side of the K8 cable paper by a coating machine, stirring the paper continuously before the coating of the mercury-free electric paste to uniformly distribute the components, drying the paper by a 100 ℃ oven, coating the other side of the paper, and finally rolling and cutting the paper to obtain the mercury-free slurry layer paper.
The preparation steps of the battery are as follows:
cutting the mercury-free pulp layer paper 1, setting the paper closely to the inner wall of the zinc cylinder 6, arranging the cutting bottom bowl 2 at the bottom of the zinc cylinder 6 and setting the paper closely to the bottom wall of the zinc cylinder 6; after the cell powder is pressed and molded to obtain a cell 8, the cell 8 is placed in a zinc cylinder 6, the molded cell 8 is separated from the zinc cylinder 6 by utilizing mercury-free slurry layer paper 1, a re-pressing ring 3 is arranged above the molded cell 8 for re-pressing, a carbon rod 4 is inserted in the cell 8, glue is coated on the upper edge of the inner wall of the zinc cylinder 6 and the upper part of the carbon rod 4, a combined cap is covered on the top of the zinc cylinder, and then a trademark is sleeved, and heat shrinkage is performed after the iron bottom 5 is covered.
Example six
The zinc cylinder 6 is made of the following materials in percentage by mass: 0.005% magnesium, 0.03% titanium, 0.001% tin, 0.008% indium, 0.01% bismuth, 0.003% lead, 0.001% cadmium and the balance zinc.
The manufacturing method of the mercury-free lead-free cadmium-free zinc-manganese battery comprises the following steps:
step one: proportioning and melting the raw materials;
step two: pouring and forming a zinc plate;
step three: punching, cake washing and extrusion of the zinc plate;
step four: preparing mercury-free pulp layer paper;
step five: and (3) assembling the battery body.
In the proportioning and melting process of the raw materials, zinc and titanium are firstly mixed, heated and melted to prepare titanium-zinc alloy, and then mixed with magnesium, tin, indium, bismuth and zinc according to a proportion, and heated to 430 ℃ to obtain a melt.
The raw material components of the mercury-free electropaste comprise (by mass percent): 10% of zinc chloride, 17% of ammonium chloride, 6% of flour, 4% of glutinous rice flour, 10% of etherified starch, 0.1% of polyvinyl alcohol, 0.03% of polyacrylamide, 0.01% of boric acid, 0.11% of alkylphenol ethoxylates, 0.04% of bismuth trichloride, 0.002% of indium chloride and the balance of water.
Mixing polyvinyl alcohol, boric acid and water according to the mass ratio, heating in water bath to boil, and stirring while heating to obtain the final product;
mixing zinc chloride, ammonium chloride and water according to the mass ratio, and purifying by hanging zinc slag, wherein the iron content is less than or equal to 0.0001%, and the corrosion test is qualified to obtain high-concentration electrolyte; adding polyacrylamide accounting for 0.15% of the mass of the high-concentration electrolyte into the high-concentration electrolyte, soaking, and fully stirring until the polyacrylamide is completely dissolved to obtain the high-concentration electrolyte;
adding low-concentration electrohydraulic liquid, polyvinyl alcohol solution, glutinous rice flour, etherified starch, alkylphenol ethoxylate and polyacrylamide solution into a ceramic jar according to a proportion, fully stirring until uniform, then slowly adding indium chloride aqueous solution (10wt%) and bismuth trichloride aqueous solution (10wt%) in sequence, stirring while adding, and uniformly mixing to obtain the composite material;
and then coating a layer of mercury-free electric paste on one side of the K8 cable paper by a coating machine, stirring the paper continuously before the coating of the mercury-free electric paste to uniformly distribute the components, drying the paper by a 100 ℃ oven, coating the other side of the paper, and finally rolling and cutting the paper to obtain the mercury-free slurry layer paper.
The preparation steps of the battery are as follows:
cutting the mercury-free pulp layer paper 1, setting the paper closely to the inner wall of the zinc cylinder 6, arranging the cutting bottom bowl 2 at the bottom of the zinc cylinder 6 and setting the paper closely to the bottom wall of the zinc cylinder 6; after the cell powder is pressed and molded to obtain a cell 8, the cell 8 is placed in a zinc cylinder 6, the molded cell 8 is separated from the zinc cylinder 6 by utilizing mercury-free slurry layer paper 1, a re-pressing ring 3 is arranged above the molded cell 8 for re-pressing, a carbon rod 4 is inserted in the cell 8, glue is coated on the upper edge of the inner wall of the zinc cylinder 6 and the upper part of the carbon rod 4, a combined cap is covered on the top of the zinc cylinder, and then a trademark is sleeved, and heat shrinkage is performed after the iron bottom 5 is covered.
Form one
Magnesium (Mg) Titanium Tin (Sn) Indium (indium) Bismuth Iron content
Example 1 0.005％ 0.03％ 0.003％ 0.008％ 0.01％ 0.00005％
Example two 0.001％ 0.03％ 0.003％ 0.008％ 0.01％ 0.00006％
Example III 0.01％ 0.03％ 0.003％ 0.008％ 0.01％ 0.00004％
Example IV 0.005％ 0.02％ 0.003％ 0.008％ 0.01％ 0.00003％
Example five 0.005％ 0.05％ 0.003％ 0.008％ 0.01％ 0.00006％
Example six 0.005％ 0.03％ 0.001％ 0.008％ 0.01％ 0.00009％
Compared with the prior art, the invention has the beneficial effects that.
Working principle: by comparing the experimental results in the first to sixth embodiments, it can be found that in the fourth embodiment, after zinc chloride, ammonium chloride and water are mixed according to the mass ratio, and by hanging zinc slag for purification treatment, the iron content is 0.00003%, and the content is the lowest, so that the scheme in the fourth embodiment is optimal, and therefore, metal elements such as magnesium, titanium, tin, indium and bismuth can be obtained to replace lead and cadmium toxic heavy metals in the traditional battery zinc cylinder.
Although embodiments of the present invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made therein without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.

Claims (3)

1. A mercury-free lead-free cadmium-free zinc-manganese battery is characterized in that: the mercury-free lead-free cadmium-free zinc-manganese battery comprises:
a mercury-free pulp layer paper (1), wherein the mercury-free pulp layer paper (1) is arranged in a cylinder shape;
the bottom bowl (2) is arranged at the lower end of the inner cavity of the mercury-free pulp layer paper (1);
the re-pressing ring (3) is arranged at the upper end of the inner cavity of the mercury-free pulp layer paper (1), and a through hole is formed in the center of the re-pressing ring (3);
the lower end of the carbon rod (4) is arranged in the inner cavity of the mercury-free pulp layer paper (1), and the upper end of the carbon rod (4) is positioned through a through hole at the central position of the re-pressing ring (3);
the combined cap is arranged at the uppermost end of the mercury-free slurry layer paper (1), and the upper end of the carbon rod (4) is coated by the combined cap;
the zinc cylinder (6) is coated on the outer side surface of the mercury-free pulp layer paper (1), and the zinc cylinder (6) is of a cylindrical structure with a sealed bottom surface;
the iron bottom (5) is attached to the bottom surface of the zinc cylinder (6);
the outer coating insulating layer (7) is coated on the outer side surface of the zinc cylinder (6);
the battery cell (8) is arranged in the inner cavity of the mercury-free paper (1), and the battery cell (8) covers the lower end of the carbon rod (4);
the bottom bowl (2) is a scanning body with a transverse L-shaped section, and the side edge of the bottom bowl (2) is fixedly bonded with the inner side wall of the mercury-free slurry layer paper (1);
the re-pressing ring (3) is of a scanning body structure with a concave section, and the inner side wall and the outer side wall of the re-pressing ring (3) are respectively fixedly bonded with the outer side wall of the carbon rod (4) and the inner side wall of the mercury-free slurry layer paper (1);
the combined cap is formed by combining a first cap body (9) and a second cap body (10), a clamping groove is formed in the first cap body (9), a bayonet is formed in the second cap body (10), the bayonet corresponds to the clamping groove, and the upper side end of the zinc cylinder (6) is clamped between the clamping groove and the bayonet;
the manufacturing method of the mercury-free lead-free cadmium-free zinc-manganese battery comprises the following steps:
step one: proportioning and melting the raw materials;
step two: pouring and forming a zinc plate;
step three: punching, cake washing and extrusion of the zinc plate;
step four: preparing mercury-free pulp layer paper;
step five: assembling the battery body;
the mercury-free paper in the preparation process of the mercury-free paper in the fourth step is prepared by coating the double sides of the K8 cable paper with mercury-free electric paste and drying at 100-105 ℃;
the mercury-free electric paste comprises the following raw material components in percentage by mass: 10% of zinc chloride, 17% of ammonium chloride, 6% of flour, 4% of glutinous rice flour, 10% of etherified starch, 0.1% of polyvinyl alcohol, 0.03% of polyacrylamide, 0.01% of boric acid, 0.11% of alkylphenol ethoxylates, 0.04% of bismuth trichloride, 0.002% of indium chloride and the balance of water;
the zinc cylinder (6) is made of the following materials in percentage by mass: 0.001-0.01% of magnesium, 0.02-0.05% of titanium, 0.001-0.005% of tin, 0.005-0.01% of indium, 0.005-0.015% of bismuth, 0.002-0.004% of lead, 0.001-0.002% of cadmium and the balance of zinc.
2. A mercury-free, lead-free, cadmium-free zinc-manganese battery according to claim 1, wherein: in the proportioning and melting process of the raw materials, zinc and titanium are firstly mixed, heated and melted to prepare titanium-zinc alloy, and then mixed with magnesium, tin, indium, bismuth and zinc according to a proportion, and heated to 430-440 ℃ to obtain a melt.
3. A mercury-free, lead-free, cadmium-free zinc-manganese battery according to claim 1, wherein: the mercury-free pulp layer paper is used as an isolation layer.
CN202210322577.9A 2022-03-29 2022-03-29 Mercury-free lead-free cadmium-free zinc-manganese battery and manufacturing method thereof Active CN114628708B (en)

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