CN107221687B - A kind of mercury-free zinc paste composition and the mercury-free zinc and air cell with the composition - Google Patents
A kind of mercury-free zinc paste composition and the mercury-free zinc and air cell with the composition Download PDFInfo
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- CN107221687B CN107221687B CN201710462072.1A CN201710462072A CN107221687B CN 107221687 B CN107221687 B CN 107221687B CN 201710462072 A CN201710462072 A CN 201710462072A CN 107221687 B CN107221687 B CN 107221687B
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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
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Abstract
A kind of mercury-free zinc paste composition of the present invention and the mercury-free zinc and air cell with the composition belong to field of batteries, its battery structure includes mercury-free zinc load slurry, positive and negative anodes shell, sealing rubber ring, diaphragm, positive plate, diffusion paper etc., and wherein mercury-free zinc slurry is made of components such as mercury less zinc powder, inorganic gel agent, organic gel agent, surfactant, conducting polymer, electrolyte.Wherein surfactant is that the one or several kinds of alkyl benzene sulphonate, alkyl benzene carboxylic acid or derivatives thereof and Polyoxyalkylene ethers analog derivative collectively constitute.In the case where not adding mercury, such surfactant can reinforce the interaction in zinc slurry between zinc powder, end remains to that the low internal resistance state inside zinc slurry is maintained to improve discharge capacity and the discharge time of zinc and air cell to considerably increase the utilization rate of zinc powder after discharge.
Description
Technical field
A kind of mercury-free zinc paste composition of the present invention and the mercury-free zinc and air cell with the composition belong to field of batteries.
Background technique
Growing energy demand has been full of among the every aspect of life, Miniature Portable Unit such as wrist-watch,
Hearing aid, bluetooth headset etc. need high capacity button cell to provide the energy for it.Due to the high capacity and low cost of zinc and air cell
Etc. characteristics, most hearing aids currently on the market rely primarily on button zinc sky one-shot battery and provide energy for it.
Zinc and air cell is that a kind of air oxidation zinc load by anode provides the metal-air battery of energy, and advantage exists
In higher capacity and lower cost.Understand in zinc and air cell manufacturing process and zinc powder is fabricated to pulp-like and as cathode
It uses, is generated to reduce hydrogen, enhancing battery conductive, the mercury of about 1wt% can be added among zinc powder in traditional technique
It uses.Due to being one-shot battery, hearing aid button zinc and air cell can be discarded into ambient enviroment after using, because
And mercury therein can flow into environment therewith, be easy to cause damages to environment.Therefore it is gradually complete just to assign regulation several years ago for European Union
Realize that zinc and air cell is mercuryless in face.But when no longer adding mercury when zinc powder, in generation and battery that more gases certainly will be caused
The raising of resistance, especially the zinc active material of section conduction can gradually be converted to nonconducting zinc oxide after discharge, and internal resistance increases
The chemical reaction of battery can be further influenced again, so that zinc powder utilization efficiency be caused to decline, discharge capacity greatly reduces.
Summary of the invention
It is an object of the invention to avoid the deficiencies in the prior art, to provide a kind of mercury-free zinc paste composition.The combination
Object is related to a kind of surfactant system, and the one or more combination of these surfactant systems can be in the feelings for not adding mercury
Enhance the interaction between zinc powder under condition, reduces the internal resistance of cell, especially the nonconducting zinc oxide of section increases situation after discharge
Under be still able to maintain the low internal resistance of battery so that wherein zinc powder reaction is more complete, thus improve zinc and air cell discharge capacity and
Discharge time.
In order to solve the technical problem, present invention employs following technical solutions: a kind of mercury-free zinc paste composition includes mercury-free
Zinc powder, inorganic gel agent, organic gel agent, surfactant, conducting polymer and electrolyte, wherein mercury less zinc powder does not refer to
For the zinc of single chemical component, it is also possible to including other microcomponents such as aluminium, bismuth, indium, iron, copper etc..The granular size of zinc powder point
Cloth is between 10-1000 μm, and preferably 50-500 μm, further preferably between 100-300 μm.
Gelling agent can make zinc powder and aqueous solution form gel like high viscosity liquid, when principle is that gelling agent is dispersed in water
Forming tridimensional network latching moisture and granular zinc powder, the zinc powder and electrolyte of shape evenly dispersed in this way could preferably send out
Raw electrochemical reaction.Gelling agent system in the present invention by inorganic gel agent and organic gel agent one or more of mixing groups
At.Wherein inorganic gel agent is mainly silicate systems and aluminosilicate system compound, including magnesium silicate, sodium metasilicate, aluminium silicon
Sour potassium, calcium aluminosilicate etc., preferably sodium magnesium silicate chemicals, additive amount are the 0.01%-3% of zinc powder quality, preferably
0.1%-1%, further preferably 0.3%-0.5%.Organic gel agent is mainly that pectin class, alginates, cellulose spread out
Biology, polyacrylic etc., preferably polyacrylic compounds, additive amount are the 0.01%-3% of zinc powder quality, preferably
0.1%-1%, further preferably 0.3%-0.5%.
Surfactant system can make the particle zinc powder in gel combine even closer, enhance the phase interaction between them
With section zinc powder remains to that battery is made to maintain lower internal resistance when being gradually transformed into nonconducting zinc oxide after discharge, to improve
The utilization rate of zinc powder improves discharge capacity and the discharge time of zinc and air cell.Surfactant system in the present invention includes changing
Close one of I alkyl benzene sulphonate of object, alkyl benzene carboxylic acid or derivatives thereof and compound ii Polyoxyalkylene ethers analog derivative or several
Kind.
Alkyl benzene sulphonate, alkyl benzene carboxylic acid in the present invention or derivatives thereof, compound structure is
Wherein R1, R2, R3 and R4 are hydrogen-based-H, or the straight-chain containing C1-C18, branched or cricoid alkyl, alkylene or its is halogenated
Alkyl and aromatic derivant group, C1-C18 are preferably the straight-chain alkyl containing C8-C14, and in addition A is carboxyl-COOH or sulphur
Acidic group-SO2OH, B are hydrogen-based-H or oxygroup benzene sulfonic acid-OC4H6SO2OH and its derivative, and quality accounts for zinc powder mass ratio and exists
Between 0.01%-3%, between preferably 0.05%-1%, between further preferably 0.1%-0.5%.
Polyoxyalkylene ethers analog derivative in the present invention is preferably that polyoxyethylene ether analog derivative or polyoxypropylene ethers are derivative
Object or any combination thereof.Polyoxyalkylene ethers analog derivative such as compound ii structure in the present invention isWherein R group can be derived as any in R5R6N-, R7-O-, R8COO-, R9-C4H6O-
One kind, R5, R6, R7, R8, R9 can be hydrogen-based or straight-chain, branched or cricoid alkyl containing C1-C18, alkylene or its
Halohydrocarbyl, C1-C18 are preferably the alkyl containing C8-C14, and in addition the sum of m+n is more than or equal to 4 and is less than or equal to 100, preferably
It is less than or equal to 50 more than or equal to 10, quality accounts for zinc powder mass ratio between 0.01%-3%, preferably 0.05%-1%
Between, X group is hydrogen-based-H, sulfonic group-SO2OH or phosphate-PO (OH) 2 and its salt, further preferably for 0.1%-0.5% it
Between.
Conducting polymer in the present invention can be polypyrrole PPY, polyaniline PANI, polythiophene PT, polyacetylene PAC one
Kind or several combinations, account for zinc powder mass ratio between 0.001%-0.3%, between preferably 0.005%-0.1%, into
One step is preferably between 0.01%-0.05%.In addition, compound indium hydroxide In (OH) 3 is also possible to along with conducting polymer
It is added in cathode zinc slurry, additive amount is 0.01%-3%, the preferably 0.05%-0.5% of zinc powder quality, further excellent
It is selected as 0.1%-0.3%.
Electrolyte is potassium hydroxide KOH or sodium hydroxide NaOH and the alkaline solution that deionized water is made into, preferably hydrogen-oxygen
Change potassium KOH alkaline solution, electrolyte quality is about between the 18%-36% of zinc powder quality, between preferably 22%-30%, hydrogen
Potassium oxide KOH mass is about between the 25%-40% of electrolyte quality, between preferably 30%-35%.In addition, in electrolyte
The zinc oxide ZnO, preferably 1%-3% for accounting for about zinc powder quality 1%-5% can be contained.
For this purpose, the present invention also provides a kind of mercury-free zinc and air cell with above-mentioned composition, one kind is starched containing mercury-free zinc
The mercury-free zinc and air cell of composition, including negative electrode casing, sealing rubber ring, anode cover, diaphragm, collector, catalyst layer, waterproof and breathable
Film, air spread paper, airport, and sealing rubber ring is for cell sealing and battery plus-negative plate is made to insulate, the inside patch of sealing rubber ring
It closes in the outside of negative electrode casing, the outside of sealing rubber ring has then been bonded the inside of anode cover, and diaphragm has separated cathode zinc slurry and anode
Layer, collector, catalyst layer, waterproof ventilated membrane are arranged between diaphragm and anode cover, the abducent tongue slot in anode cover bottom
There is airport at bottom, and air diffusion paper is disposed on tongue, and negative electrode casing internal cavity is filled with mercury-free zinc paste composition.
Cathode shell material uses outer layer nickel, middle layer steel, internal layer copper three-layer composite structure, and wherein outer layer can prevent external rings
Corrosion of the border to steel shell, middle layer steel provide main mechanical strength for battery cathode shell, and internal layer copper makes battery case keep highly conductive
Property.In addition, the coating made of the possible one or more combination there are also one layer of tin, zinc or indium in layers of copper surface, to improve it
Hydrogen overvoltage makes cathode zinc slurry remain to maintain hydrogen output in appropriate degree in the case where not adding mercury.
Anode layer is via Teflon, manganese dioxide, active carbon and conductive carbon through dry method mixed at high speed, granulation, sieving, roller
Pressure, then it is combined with 6 roll-in of collector net.Then the waterproof ventilated membrane made of Teflon again roll-in be combined to
In the opposite other one side of collector net, the zinc and air cell positive plate in the present invention is obtained.Diaphragm be placed in cathode zinc slurry with just
Between pole piece, diaphragm is to be combined by non-woven fiber shape polypropylene layer with the polypropylene diaphragm with hydrophilic coating, thick
Degree is between 20-200 μm, preferably between 50-150 μm.
Compared with existing invention, obvious beneficial effect of the invention is not add traditional mercury in cathode zinc slurry and be changed to make
With a kind of surfactant system, this surfactant or these surfactants can effectively enhance mutual between zinc powder
Effect, section zinc powder remains to that battery is made to maintain lower internal resistance when being gradually transformed into nonconducting zinc oxide after discharge, to mention
The utilization rate of high zinc powder improves discharge capacity and the discharge time of zinc and air cell.In addition, obtained zinc and air cell meets European Union
With Environmental Protection in China requirement, environment will not be caused seriously as having mercury cell discarding in environment even if after use
It destroys.
Detailed description of the invention
Fig. 1 is the constant-resistance discharge figure that mercury-free zinc and air cell of the present invention and tradition have mercury zinc and air cell.
Fig. 2 is the pulsed discharge figure that mercury-free zinc and air cell of the present invention and tradition have mercury zinc and air cell.
Fig. 3 is mercury-free zinc and air cell structural schematic diagram of the present invention.
Specific embodiment
The invention patent is further described with reference to the accompanying drawings and detailed description.Wherein, attached drawing is only used for
Exemplary illustration, the limitation for being only schematic diagram, should not be understood as to this patent of expression；Reality in order to better illustrate the present invention
Example is applied, the certain components of attached drawing have omission, zoom in or out, and do not represent the size of actual object；To those skilled in the art
For, the omitting of some known structures and their instructions in the attached drawings are understandable.
In figure: negative electrode casing 1, mercury-free zinc paste composition 2, sealing rubber ring 3, anode cover 4, diaphragm 5, collector 6, catalyst layer 7,
Waterproof ventilated membrane 8, air spread paper 9, airport 10.
The cathode zinc slurry of high capacity mercury-free zinc and air cell in the present invention includes that following component (is with the quality of mercury less zinc powder
Basis): 0.18% indium hydroxide, 0.3% inorganic gel agent sodium magnesium silicate, 0.25% pentaerythrite polyacrylate,
0.025% polyaniline, 0.11% disodium 4-dodecyl-2,4 '-oxydibenzenesulfonate and 0.19% coco amine polyoxyethylene ether, and
The potassium hydroxide electrolyte that 25% mass concentration is 35%.
In order to illustrate beneficial effects of the present invention, comparative example is the zinc powder for being added to 1% mercury, and zinc slurry composition is to account for zinc powder
Indium hydroxide, 0.25% pentaerythrite polyacrylate and 25% mass concentration that quality is 0.18% are 35% hydroxide
Potassium electrolyte.
Fig. 1 is the constant-resistance discharge figure of the present invention and comparative example zinc and air cell, and discharging condition is 620 Ω constant-resistance discharges, this hair
The discharge time of bright zinc and air cell up to 80 more than hour, significantly larger than comparative example battery.Equally, Fig. 2 is of the invention and right
The pulsed discharge figure of ratio zinc and air cell, discharging condition are 2mA continuous discharge (1h59min59s500ms), 10mA pulsed discharge
(500ms) recycles six times and shelves 3h standing again, and recycling is until electric discharge terminates.Zinc and air cell of the present invention as can be seen from Figure 2
Discharge time (not including time of repose) equally at 80 hours or more, is equally significantly larger than comparative example battery.
Referring to Fig. 3, a kind of mercury-free zinc and air cell of the paste composition of zinc containing mercury-free, including negative electrode casing 1, mercury-free zinc paste composition
2, sealing rubber ring 3, anode cover 4, diaphragm 5, collector 6, catalyst layer 7, waterproof ventilated membrane 8, air spread paper 9, airport 10, close
Sealing rubber ring 3 is for cell sealing and battery plus-negative plate is made to insulate, and the inside of sealing rubber ring 3 is fitted in the outside of negative electrode casing 1, sealing
The outside of cushion rubber 3 has then been bonded the inside of anode cover 4, and diaphragm 5 has separated mercury-free zinc paste composition 2 and positive catalyst layer 7, afflux
Body 6, catalyst layer 7, waterproof ventilated membrane 8 are arranged between diaphragm 5 and anode cover 4, the abducent tongue slot bottom in 4 bottom of anode cover
There is airport 10, air diffusion paper 9 is disposed on tongue, 1 internal cavity of negative electrode casing is filled with mercury-free zinc paste composition 2.
Claims (3)
1. a kind of mercury-free zinc paste composition includes mercury less zinc powder, inorganic gel agent, organic gel agent, surfactant, conduction
Macromolecule and electrolyte further comprise other micro- it is characterized in that: the mercury less zinc powder and referring not to the zinc that unification studies point
Component is measured, the microcomponent is one of aluminium, bismuth, indium, iron, copper or its compound or a variety of, and the particle of mercury less zinc powder is big
It is small to be distributed between 10-1000 μm；Inorganic gel agent is sodium magnesium silicate, and the quality of inorganic gel agent is mercury less zinc powder quality
0.3%；Organic gel agent is pentaerythrite polyacrylate, and the quality of organic gel agent is the 0.25% of mercury less zinc powder quality；
Surfactant contains chemical compounds I and compound ii, and the chemical compounds I is disodium 4-dodecyl-2,4 '-oxydibenzenesulfonate, chemical compounds I
Quality be mercury less zinc powder quality 0.11%；Compound ii is coco amine polyoxyethylene ether, and the quality of compound ii is mercury-free
The 0.19% of zinc powder quality；Conducting polymer is polyaniline PANI, and the quality of conducting polymer is mercury less zinc powder quality
0.025%；Electrolyte is potassium hydroxide and the alkaline solution that deionized water is made into, and electrolyte quality is mercury less zinc powder quality
25%.
2. mercury-free zinc paste composition according to claim 1, it is characterized in that: the electrolyte is that potassium hydroxide basic is molten
Liquid, concentration 25%-40%.
3. a kind of mercury-free zinc and air cell with any mercury-free zinc paste composition of claim 1-2, including negative electrode casing, sealing
Cushion rubber, anode cover, diaphragm, collector, catalyst layer, waterproof ventilated membrane, air spread paper, airport, and sealing rubber ring is used for battery
It seals and battery plus-negative plate is made to insulate, the outside of negative electrode casing is fitted on the inside of sealing rubber ring, the outside of sealing rubber ring is then bonded
The inside of anode cover, diaphragm has separated cathode zinc slurry and positive plate, collector, catalyst layer, waterproof ventilated membrane are arranged in diaphragm
Between anode cover, the abducent tongue slot bottom in anode cover bottom has airport, and air diffusion paper is disposed on tongue,
Be characterized in: negative electrode casing internal cavity is filled with mercury-free zinc paste composition.
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| CN201710462072.1A CN107221687B (en) | 2017-06-19 | 2017-06-19 | A kind of mercury-free zinc paste composition and the mercury-free zinc and air cell with the composition |
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| CN110729482B (en) * | 2018-07-17 | 2021-03-23 | 横店集团东磁股份有限公司 | Negative electrode additive of alkaline zinc-manganese dry battery, negative electrode zinc paste containing negative electrode additive and alkaline zinc-manganese dry battery |
| CN109309218A (en) * | 2018-08-21 | 2019-02-05 | 浙江长虹飞狮电器工业有限公司 | Alkaline dry battery |
| CN110323368B (en) * | 2019-07-05 | 2022-01-28 | 东莞胜力电池实业有限公司 | Zinc-air button cell and preparation method thereof |
| CN111554880B (en) * | 2020-05-07 | 2023-02-28 | 珠海冠宇电池股份有限公司 | Negative plate, negative electrode slurry, preparation method of negative electrode slurry and battery |
| CN113346082A (en) * | 2021-05-28 | 2021-09-03 | 浙江野马电池股份有限公司 | Alkaline manganese battery with sodium alginate and preparation method thereof |
| CN114171721B (en) * | 2021-11-10 | 2024-05-10 | 贵州梅岭电源有限公司 | Zinc electrode in high-power zinc-silver reserve battery and preparation method thereof |
| CN114284542B (en) * | 2021-12-28 | 2024-02-06 | 山西中科华孚电池研究总院有限公司 | Manufacturing method of battery and battery |
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| US6872489B2 (en) * | 2002-02-27 | 2005-03-29 | Rovcal, Inc. | Alkaline cell with gassing inhibitors |
| US7179310B2 (en) * | 2003-07-03 | 2007-02-20 | The Gillette Company | Zinc/air cell with improved anode |
| US20070122699A1 (en) * | 2005-11-30 | 2007-05-31 | Rovcal, Inc. | Electrochemical cells having improved gelling agents |
| US8586244B2 (en) * | 2007-04-02 | 2013-11-19 | Eveready Battery Co., Inc. | Alkaline electrochemical cell having a negative electrode with solid zinc oxide and a surfactant |
| CN101271973B (en) * | 2008-05-09 | 2010-10-13 | 华南师范大学 | Non-mercury alkaline zinc-manganese and zinc-silver button cell cathode and manufacturing method thereof |
| CN101964255B (en) * | 2009-07-24 | 2012-07-04 | 清华大学 | Micro-nano composite zinc oxide slurry and preparation method and application thereof |
| CN102299389A (en) * | 2011-07-19 | 2011-12-28 | 浙江理工大学 | High-performance rechargeable battery |
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