CN103236552B - high-capacity alkaline zinc-manganese battery - Google Patents
high-capacity alkaline zinc-manganese battery Download PDFInfo
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- CN103236552B CN103236552B CN201310081502.7A CN201310081502A CN103236552B CN 103236552 B CN103236552 B CN 103236552B CN 201310081502 A CN201310081502 A CN 201310081502A CN 103236552 B CN103236552 B CN 103236552B
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- WJZHMLNIAZSFDO-UHFFFAOYSA-N manganese zinc Chemical compound [Mn].[Zn] WJZHMLNIAZSFDO-UHFFFAOYSA-N 0.000 title claims abstract description 36
- RNWHGQJWIACOKP-UHFFFAOYSA-N zinc;oxygen(2-) Chemical compound [O-2].[Zn+2] RNWHGQJWIACOKP-UHFFFAOYSA-N 0.000 claims abstract description 31
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 30
- 125000005233 alkylalcohol group Chemical group 0.000 claims abstract description 28
- -1 aluminum compound Chemical class 0.000 claims abstract description 28
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 26
- 239000010452 phosphate Substances 0.000 claims abstract description 26
- 229940051841 polyoxyethylene ether Drugs 0.000 claims abstract description 26
- 229920000056 polyoxyethylene ether Polymers 0.000 claims abstract description 26
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 25
- 238000007789 sealing Methods 0.000 claims abstract description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052802 copper Inorganic materials 0.000 claims abstract description 7
- 239000010949 copper Substances 0.000 claims abstract description 7
- 230000004048 modification Effects 0.000 claims abstract description 6
- 238000012986 modification Methods 0.000 claims abstract description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 57
- 239000000203 mixture Substances 0.000 claims description 29
- 235000014692 zinc oxide Nutrition 0.000 claims description 13
- 239000011787 zinc oxide Substances 0.000 claims description 13
- 239000007864 aqueous solution Substances 0.000 claims description 12
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 6
- SZKTYYIADWRVSA-UHFFFAOYSA-N zinc manganese(2+) oxygen(2-) Chemical compound [O--].[O--].[Mn++].[Zn++] SZKTYYIADWRVSA-UHFFFAOYSA-N 0.000 claims description 6
- 239000006071 cream Substances 0.000 claims description 4
- CPYIZQLXMGRKSW-UHFFFAOYSA-N zinc;iron(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Fe+3].[Fe+3].[Zn+2] CPYIZQLXMGRKSW-UHFFFAOYSA-N 0.000 claims description 4
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 3
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 claims description 3
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 3
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 3
- 229940105847 calamine Drugs 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 229910052864 hemimorphite Inorganic materials 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 2
- 229910000831 Steel Inorganic materials 0.000 abstract description 6
- 239000010959 steel Substances 0.000 abstract description 6
- 238000003860 storage Methods 0.000 abstract description 4
- 208000028659 discharge Diseases 0.000 description 55
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 22
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 20
- 239000003792 electrolyte Substances 0.000 description 14
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 8
- 230000002035 prolonged effect Effects 0.000 description 8
- 238000003487 electrochemical reaction Methods 0.000 description 7
- 230000005012 migration Effects 0.000 description 6
- 238000013508 migration Methods 0.000 description 6
- 150000002500 ions Chemical class 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000011149 active material Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- 229920002125 Sokalan® Polymers 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 2
- 239000010405 anode material Substances 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000004134 energy conservation Methods 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Substances OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- 230000005764 inhibitory process Effects 0.000 description 2
- 239000007773 negative electrode material Substances 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 239000004584 polyacrylic acid Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 208000033978 Device electrical impedance issue Diseases 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 229910001297 Zn alloy Inorganic materials 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 150000001399 aluminium compounds Chemical class 0.000 description 1
- 229940077746 antacid containing aluminium compound Drugs 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 239000000565 sealant Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000009849 vacuum degassing Methods 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
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- Battery Electrode And Active Subsutance (AREA)
- Primary Cells (AREA)
Abstract
The invention discloses a high-capacity alkaline zinc-manganese battery, which aims to solve the problems that the capacity of the existing alkaline zinc-manganese battery is small, and the service life of the battery is short under the condition of medium and small current discharge. The invention comprises a steel shell, an anode ring, a zinc paste, diaphragm paper, a sealing ring, a copper nail and a cathode cover, wherein alkyl alcohol polyoxyethylene ether phosphate and an aluminum compound are added into the zinc paste for modification, so that the high-capacity alkaline zinc-manganese battery is obtained. The invention has longer discharge time, smaller self-discharge and better battery storage performance under the condition of medium and small current continuous discharge, and greatly improves the battery discharge capacity.
Description
Technical Field
The invention relates to the technical field of battery production, in particular to a high-capacity alkaline zinc-manganese battery.
Background
The alkaline zinc-manganese battery is convenient for large-scale production due to reasonable structural design, has excellent electrochemical performance and higher cost performance, and is welcomed by consumers. Since the mercury-free alkaline zinc-manganese battery is put into the market, the safe, environment-friendly and high-performance alkaline zinc-manganese battery is better appreciated by the market.
The alkaline zinc-manganese battery has 4-5 times higher capacitance than common carbon battery and low cost. The alkaline zinc-manganese battery in the current market can meet the requirements of high-power small electronic products such as digital cameras, flashlights, electric shavers, electric toys and the like. However, many consumers choose to use low-power electronic products such as flashlights, MP3 s, semiconductors, radios, etc., and seek high-capacity alkaline zinc-manganese batteries, namely, alkaline zinc-manganese batteries with long discharge time, small self-discharge and good battery storage performance.
Standard cylindrical cells, such as LR03 (7 # cell), LR6 (5 # cell), LR14 (2 # cell), whose diameter and height dimensions are uniformly specified, must be supplemented with more active material, such as alkaline zinc-manganese cell positive manganese dioxide and negative zinc powder, to increase the cell's capacity. And reasonable electrochemical reaction conditions are selected to fully improve the utilization rate of the active material and output more electric energy. This cell design with more active material added is limited and the electrochemical reaction to some extent to increase the cell's capacity is affected by the size of the cell's steel can interior volume.
The working principle of the alkaline zinc-manganese battery is as follows:
the electrochemical expression of the alkaline zinc-manganese battery is as follows:
and (3) battery reaction:
negative electrode:
and (3) positive electrode:
and (3) total reaction:
the positive electrode of the alkaline zinc-manganese battery is mainly manganese dioxide (MnO) 2 ) Graphite, adding a proper amount of adhesive and KOH electrolyte, uniformly mixing, tabletting, granulating and looping to prepare the ring-structured anode mixture. And the negative electrode is mainly a slurry-like negative electrode mixture made of zinc powder, a water-absorbent polymer and a KOH electrolyte.
When the alkaline zinc-manganese battery is discharged, the negative active material zinc powder and the positive electrode OH - Ions are supplied to the surface of the negative zinc powder through continuous migration of the electrolyte to perform electrochemical reaction to release electrons. As the discharge continues, the zincate concentration on the surface of the zinc powder gradually increases and tends to saturate, and ZnO or Zn (OH) begins to be generated on the surface of the electrode 2 The film is loosened, so that the real surface area of the zinc electrode is reduced, the current density is increased, the electrode polarization is intensified, the internal resistance of the battery is increased, the working voltage of the battery is obviously reduced, the discharge current is reduced, and finally the discharge is stopped.
Measures to prevent passivation of the zinc electrode are control of current density and improvement of OH - Under the condition of ion migration, particularly in a medium-and-small current discharge mode of the battery, because the utilization rate of negative zinc powder is greatly improved, znO which is a final product of the negative zinc powder in the electrochemical reaction is greatly increased and accumulated on the surface of active zinc powder, the density of ZnO is small, the volume is large, KOH electrolyte migration is hindered, the polarization of an electrolyte solvent increases the internal resistance of the battery, and the zinc powder and OH are inhibited - Electrochemistry of ionsThe reaction causes a significant drop in the cell voltage.
Improving the low current discharge in the alkaline zinc-manganese battery to increase the service time of the battery, and trying to reduce the migration resistance of the electrolyte and facilitate OH - Ion supplement, and the slow decline of battery operating voltage is maintained. The invention of CN101728546A discloses a novel alkaline zinc-manganese battery, which comprises a shell, an anode ring, zinc paste, a diaphragm sleeve, a sealing ring, a cathode bottom, a copper needle and a small bowl, wherein an insulating ring is embedded on the cathode bottom. The alkaline zinc-manganese battery has small capacity, and still cannot solve the problem of short service time of the battery under the condition of medium and small current discharge.
Disclosure of Invention
The invention aims to solve the problems that the existing alkaline zinc-manganese battery has smaller capacity and the service time of the battery is short under the condition of medium and small current discharge, and provides a high-capacity alkaline zinc-manganese battery which has longer discharge time, smaller self-discharge and better battery storage performance under the condition of medium and small current continuous discharge and greatly improves the discharge capacity of the battery.
The technical scheme adopted by the invention for solving the technical problems is as follows:
a high-capacity alkaline zinc-manganese battery comprises a steel shell, an anode ring, a zinc paste, diaphragm paper, a sealing ring, a copper nail and a cathode cover, wherein alkyl alcohol polyoxyethylene ether phosphate and an aluminum compound are added into the zinc paste for modification, so that the high-capacity alkaline zinc-manganese battery is obtained.
Alkyl alcohol polyoxyethylene ether phosphate (REP) is synthesized by condensation reaction of alkyl alcohol and ethylene glycolThe alkyl alcohol of the molecule has certain hydrophobicity in water. The chemical structure of polyoxyethylene has certain hydrophilicity. The chemical has certain dispersivity in strong alkali aqueous solution, and also has the functions of wettability and metal corrosion inhibition, and has better stability and oxidation resistance in strong alkali. The organic matter is added into the cathode zinc paste of alkaline zinc-manganese battery in proper amount, and it is chargedThe pool gas inhibition has certain influence, has corrosion resistance effect on zinc powder in KOH electrolyte, improves the self-discharge performance of the battery, reduces the defect of liquid leakage and gas expansion of the battery, and prolongs the storage period of the battery. However, the discharge performance of the battery cannot be improved, and the capacity of the battery cannot be increased. Repeated research tests show that when the organic matters and the aluminum compounds are heated, stirred and uniformly mixed, the mixture is added into alkaline KOH electrolyte, and then the alkaline KOH electrolyte, the water-absorbing polyacrylic acid, the active negative zinc powder and the like are prepared into the alkaline zinc-manganese battery produced by the calamine cream, the electrochemical performance of the alkaline zinc-manganese battery is obviously changed, particularly the battery has a medium and small current continuous discharge mode, the discharge time of the battery is prolonged, and more electric capacity is provided.
Formation of Al (OH) from aluminium compounds in alkaline solutions 4 (H 2 O 2 ) 2- And Al (OH) 6 (H 2 O) 3-
The hydrated ion, which forms a mixture with the alkyl alcohol polyoxyethylene ether phosphate, is denoted by REP-Al. The action mechanism of the REP-Al mixture on the cathode zinc paste of the alkaline zinc-manganese battery is not quite clear, but the comparison experiment of the low-current discharge in the battery shows that when the discharge working voltage of the battery reaches a low-voltage section, the discharge time of the battery is obviously prolonged, and the lower the voltage, the more obvious the discharge time of the low-voltage section is prolonged, but the intermittent discharge mode has little influence. And the phenomenon can only be reflected by adding the cathode zinc paste after the two compounds are pretreated according to a certain proportion, and the specific electrochemical performance can be displayed.
We think that when the battery is in the low-voltage section at the later stage of medium and small current discharge, a large amount of negative zinc powder discharge product ZnO is generated, and the ZnO is precipitated and covered on the surface of active zinc powder, so that OH is generated - The migration of ions in the electrolyte is inhibited, and the increase of ZnO film thickness on the surface of the zinc powder is inhibited, and the interior of active zinc powder particles is lack of OH - The electrochemical reaction of the cell is limited by the ions and the voltage drop discharge is terminated. When the REP-Al mixture is added into the cathode zinc paste, on one hand, the ordered and compact accumulation of the ZnO film is prevented, and a porous and loose ZnO film is formed, so that the migration of the electrolyte is kept in a certain channel. On the other hand, the polyoxyethylene block molecular chain of REP-Al has higher conductivity and accelerates KOHElectrolyte OH - And the transfer of the ions maintains the electrochemical reaction of the battery. Hydrated Al 3+ The molecular structure has certain property of adsorbing water molecules, and is continuously supplied to the electrochemical reaction on the surface of the zinc powder to generate current, so that large electric quantity is provided, and the service life of the battery is prolonged.
According to the invention, alkyl alcohol polyoxyethylene ether phosphate and an aluminum compound are added into the zinc paste for modification, so that the medium and small current discharge performance is greatly improved, the battery capacity is increased, the service life of the battery is prolonged, and the improvement on medium and small current continuous discharge is more prominent. The preparation process is simple, the production cost is low, and the discharge capacity of the battery is greatly improved.
Preferably, the dosage of the alkyl alcohol polyoxyethylene ether phosphate is 0.004-0.05% of the weight of the zinc paste. Below this lower limit the cell discharge time is not significantly prolonged, above this upper limit the cell internal resistance increases and the cell discharge time decreases inversely.
Preferably, the aluminum compound is used in an amount of 0.003% to 0.02% by weight of aluminum based on the weight of the calamine cream. When the dosage is less than the lower limit dosage, the discharge time of the battery is not obviously changed, and when the dosage is more than the upper limit dosage, needle-shaped zinc oxide particles are easily generated when the battery discharges, so that the diaphragm paper is damaged to form the micro short circuit of the battery. The invention can also adopt zinc alloy powder containing aluminum to replace aluminum compounds.
Preferably, the alkyl alcohol polyoxyethylene ether phosphate has the general formula:
wherein R represents a straight-chain or branched-chain saturated alkyl group, the number of carbon atoms of the alkyl group is an integer of 2-10, and n is an integer of 4-10.
Preferably, the aluminum compound is selected from one or more of aluminum hydroxide, aluminum sulfate, aluminum nitrate and aluminum silicate.
Preferably, the alkyl alcohol polyoxyethylene ether phosphate and the aluminum compound are dissolved in the potassium hydroxide aqueous solution to form a mixture of the alkyl alcohol polyoxyethylene ether phosphate and the aluminum compound, and then the mixture is added into the zinc paste.
Preferably, the mass concentration of the potassium hydroxide aqueous solution is 5-38%.
Preferably, the aluminum compound is added into the potassium hydroxide aqueous solution, heated to 40-90 ℃ for dissolution, then the alkyl alcohol polyoxyethylene ether phosphate is added, stirred and mixed evenly, and the mixture of the alkyl alcohol polyoxyethylene ether phosphate and the aluminum compound is formed after cooling. The amount of the aqueous solution of potassium hydroxide is the amount of the solvent in which the solute is dissolved. The aluminum compound is difficult to dissolve and needs to be heated for dissolution, the heating temperature cannot be too high or too low, the performance is easily affected by too high temperature, and the too low dissolution time is too long.
The invention has the beneficial effects that:
1. the zinc paste is modified by adding alkyl alcohol polyoxyethylene ether phosphate and an aluminum compound, so that the discharge performance of medium and small currents is greatly improved, the capacity of the battery is increased, the service life of the battery is prolonged, and the improvement on continuous discharge of the medium and small currents is particularly remarkable.
2. The preparation process is simple, the production cost is low, and the discharge capacity of the battery is greatly improved.
3. The utilization rate of resources is improved, the use cost of consumers is reduced, and the method has practical significance on social energy conservation and emission reduction.
Drawings
Fig. 1 is a schematic diagram of a structure of an alkaline zinc-manganese dioxide cell of the present invention.
FIG. 2 is a graph comparing the impedance of an alkaline zinc manganese cell of the invention with a control cell;
in the figure: a: the invention relates to an alkaline zinc-manganese battery; c: a control cell;
and (3) testing conditions are as follows:
high frequency: 10000Hz, low frequency: 0.01Hz, amplitude: the pressure of the mixture is 0.005V,
electrochemical workstation model: CH1600D (Shanghai Chen Hua apparatus Co.).
Fig. 3 is a graph comparing the discharge curves of the alkaline zinc-manganese cell of the invention and a control cell.
Figure 4 is a graph comparing the performance of the alkaline zinc manganese cell of the invention with a control cell.
In the figure: 1. the device comprises a steel shell, 2, a positive electrode ring, 3, zinc paste, 4, diaphragm paper, 5, a sealing ring, 6, a copper nail, 7 and a negative electrode cover.
Detailed Description
The technical solution of the present invention is further specifically described below by way of specific examples in conjunction with the accompanying drawings.
In the present invention, the raw materials and equipment used are commercially available or commonly used in the art, unless otherwise specified. The methods in the following examples are conventional in the art unless otherwise specified.
As shown in fig. 1, the high-capacity alkaline zinc-manganese dioxide battery comprises a steel shell 1, a positive ring 2, a zinc paste 3, a diaphragm paper 4, a sealing ring 5, a copper nail 6 and a negative cover 7, wherein alkyl alcohol polyoxyethylene ether phosphate and an aluminum compound are added into the zinc paste for modification to obtain the high-capacity alkaline zinc-manganese dioxide battery, and the specific operations are as follows: firstly, adding an aluminum compound into a potassium hydroxide aqueous solution, heating to 40-90 ℃ for dissolving, then adding alkyl alcohol polyoxyethylene ether phosphate, stirring and mixing uniformly, cooling to form a mixture of the alkyl alcohol polyoxyethylene ether phosphate and the aluminum compound, and then adding into the zinc paste. The dosage of the alkyl alcohol polyoxyethylene ether phosphate is 0.004-0.05 percent of the weight of the zinc paste, the dosage of the aluminum compound is calculated by aluminum, the dosage of the aluminum is 0.003-0.02 percent of the weight of the zinc paste, and the general formula of the alkyl alcohol polyoxyethylene ether phosphate is as follows:
wherein R represents a straight chain or branched chain saturated alkyl group, the number of carbon atoms of the alkyl group is an integer of 2-10, and n is an integer of 4-10. The aluminum compound is selected from one or more of aluminum hydroxide, aluminum sulfate, aluminum nitrate and aluminum silicate, and the mass concentration of the potassium hydroxide aqueous solution is 5-38%.
The specific embodiment of the invention is as follows:
(1) Manufacture of positive electrode ring
500g of electrolytic manganese dioxide (produced by Guangxi Eichman Kang Mi Lao chemical Co., ltd.) with purity of more than or equal to 90% and specific surface area of 30-35M 2 And/g, the alkaline potential is more than or equal to 270mV, 40g of expanded graphite (Baotou crystal), 2.5g of low molecular weight polyethylene adhesive powder (Huang Shanbei Noo chemical company) are added, the mixture is rapidly stirred and dispersed, 25g of 40wt% potassium hydroxide electrolyte is added, the mixture is stirred for 10 minutes, and then the mixture is rolled, sliced, crushed and granulated. The size of the granulated anode material is 20-80 meshes, the apparent specific gravity is 1.54g/ml, the height of 4 rings of the anode material of the LR6 battery after ring forming is 10.5mm, the outer diameter of the ring is 13.4mm, and the total weight of 4 anode rings of each battery is 10.6-10.7g.
(2) Preparation of modified calamine cream
First, 150mgAl (OH) was weighed 3 (manufactured by Tianjin Bodi chemical Co., ltd.) was added to a 10g38% KOH aqueous solution, heated to 60-65 ℃ and stirred for 30 minutes, then 25mg of alkyl alcohol polyoxyethylene ether phosphate OEP-98 (manufactured by Huangjiang Royal chemical Co., ltd.) was added thereto and sufficiently stirred and dispersed, and slowly cooled to obtain a REP-Al mixture.
Take 100g468 # The zinc powder alloy (Jinlingnan scientific and technological Limited in Shenzhen) has indium content of 0.028% (w/w), bismuth content of 0.022%, particle size of 300-75 μm of about 70%, and apparent density of 2.9g/cm 3 . 10g of REP-Al mixture, 40g38% KOH aqueous solution (containing 6% ZnO), 0.5g of polyacrylic acid (binder), 0.4g of sodium polyacrylate DK-500 (binder, manufactured by Sanyo chemical Co., ltd., japan), and 100g of 468 g of the mixture # After the zinc powder alloy is evenly stirred, the mixture is placed at room temperature for 12 hours, and vacuum degassing is carried out to prepare zinc paste as a negative electrode material of the battery.
(3) Battery assembly
Pressing four positive electrode rings with the total weight of 10.6-10.7g into an LR6 nickel plated steel shell coated with a graphite conductive film on the inner layer, transferring VLM2523-110 diaphragm paper cylinders (manufactured by NKK company of Japan) along the inner diameter of the positive electrode rings, injecting 1.4g of 36% potassium hydroxide electrolyte into each battery diaphragm paper cylinder, after absorbing, filling 6.3g of the zinc paste prepared in the step (2) into the diaphragm paper cylinders, performing on-machine edge rolling, coating a sealant, combining a sealing ring and a negative electrode cover to prepare a battery negative electrode cover cap, welding the battery negative electrode cover cap with a copper nail serving as a negative electrode current collector together, inserting the battery into the negative electrode zinc paste, and finally sealing and molding the battery.
After the new cell was left at 20 ℃ for 48 hours, a constant-temperature discharge test was performed with respect to an alkaline zinc-manganese cell (control cell) without the addition of the REP-Al mixture.
Comparison of Experimental data
The cells with the addition of the REP-Al mixture (invention) were compared with the cells without the addition of the REP-Al mixture (control cell), and the other formulation processes were the same as those of the experimental cells. The discharge is compared with a detection instrument in a detection environment (20 +/-2 ℃ RH 35-75%): an automatic discharge detection system for PM-2000 battery.
(1) Discharge mode: 3.9ohm,24h/day continuous discharge; as shown in table 1: unit: minute (min)
TABLE 1
。
(2) A discharge mode: 10ohm,24h/day continuous discharge; as shown in table 2: unit: minute (min)
TABLE 2
。
(3) Discharge mode: 360mA, 24h/day; as shown in table 3: unit: minute (min)
TABLE 3
。
(4) The following is a comparison of the presence or absence of the organic compounds with REP (addition of 0.05% (w/w of the total weight of the zinc paste) OEP-98 alkyl alcohol polyoxyethylene ether phosphate (without aluminum compound) compared to a control cell discharge experiment) with a discharge mode of 3.9ohm,1h/day intervals, see Table 4;
TABLE 4
。
As can be seen from FIG. 2, when the REP-Al mixture was added to the negative zinc paste, the cell impedance increased significantly, demonstrating that there was an attachment on the negative zinc powder surface. It can be seen from tables 1-4 and fig. 3 and 4 that the alkaline zn-mn cell has different voltage discharge time distributions in stages for significantly improving the service life of the cell in the medium and small current continuous discharge mode by adding the REP-Al mixture to the negative electrode zinc paste. The negative electrode zinc paste added with the REP-Al mixture is generally obviously improved in battery discharge under the working voltage of 1V, and compared with a comparison battery, the stage discharge time is prolonged under the condition of low-stage working voltage discharge of the battery, so that the obvious evidence that a plurality of ZnO discharge products accumulated on the surfaces of the negative electrode zinc powder particles at the later stage of discharge obstruct the diffusion of electrolyte, the internal resistance of the battery is increased, the voltage is obviously reduced, and the set working voltage time of the battery is stopped in advance is also clearly demonstrated. The control experiment is repeated, only one chemical substance (REP) is added into the cathode zinc paste, and the discharge of the battery is basically not changed greatly when the control battery is discharged. The chemical mixture is added in the industrial production of the battery, the process is simple, the cost is lower, and the discharge capacity of the battery is greatly improved. The utilization rate of resources is improved, the use cost of consumers is reduced, and the method has practical significance on social energy conservation and emission reduction.
The above-described embodiments are only preferred embodiments of the present invention, and are not intended to limit the present invention in any way, and other variations and modifications may be made without departing from the spirit of the invention as set forth in the claims.
Claims (4)
1. The utility model provides a high capacity basicity zinc-manganese cell, includes steel-shelled, anodal ring, calamine cream, diaphragm paper, sealing washer, copper nail and negative pole lid, its characterized in that: adding alkyl alcohol polyoxyethylene ether phosphate and an aluminum compound into the zinc paste for modification to obtain a high-capacity alkaline zinc-manganese battery; the dosage of the alkyl alcohol polyoxyethylene ether phosphate is 0.004 to 0.05 percent of the weight of the zinc paste; the amount of the aluminum compound is calculated by aluminum, and the amount of the aluminum is 0.003 to 0.02 percent of the weight of the zinc paste; the general formula of the alkyl alcohol polyoxyethylene ether phosphate ester is as follows:
wherein R represents a straight-chain or branched-chain saturated alkyl group, the number of carbon atoms of the alkyl group is an integer of 2-10, and n is an integer of 4-10; the aluminum compound is selected from one or more of aluminum hydroxide, aluminum sulfate, aluminum nitrate and aluminum silicate.
2. The high capacity alkaline zinc-manganese dioxide cell of claim 1, characterized by: the alkyl alcohol polyoxyethylene ether phosphate and the aluminum compound are dissolved in the potassium hydroxide aqueous solution to form a mixture of the alkyl alcohol polyoxyethylene ether phosphate and the aluminum compound, and then the mixture is added into the zinc paste.
3. The high capacity alkaline zinc-manganese dioxide cell of claim 2, characterized by: the mass concentration of the potassium hydroxide aqueous solution is 5-38%.
4. The high capacity alkaline zinc-manganese dioxide cell of claim 2, characterized by: firstly, adding an aluminum compound into a potassium hydroxide aqueous solution, heating to 40-90 ℃ for dissolving, then adding alkyl alcohol polyoxyethylene ether phosphate, stirring and mixing uniformly, and cooling to form a mixture of the alkyl alcohol polyoxyethylene ether phosphate and the aluminum compound.
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