CN103236552A - high-capacity alkaline zinc-manganese battery - Google Patents
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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 dioxide batteries, which have 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), which have uniform diameter and height dimensions, must be supplemented with more active material, such as positive manganese dioxide and negative zinc powder, to increase the cell's capacity. But also can fully improve the utilization rate of the active material and output more electric energy by selecting reasonable electrochemical reaction conditions. 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 proper amount of adhesive and KOH electrolyte, mixing uniformly, tabletting, granulating and looping to obtain ring-structured positive electrode mixtureA compound (I) is provided. 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 discharges, the negative active material zinc powder and the OH from the positive electrode - 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 accelerated, 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, especially in the medium-and-small current discharge mode of the battery, because the utilization rate of the negative zinc powder is greatly improved, the final product-ZnO of the negative zinc powder in the electrochemical reaction is greatly increased and accumulated on the surface of the active zinc powder, the density of ZnO is small, the volume is large, the migration of KOH electrolyte is blocked, the polarization of the electrolyte solvent increases the internal resistance of the battery, and the zinc powder and OH are inhibited - The electrochemical reaction of the ions causes a significant drop in the cell voltage.
Improving the low-current discharge of the alkaline zinc-manganese battery and increasing the service time of the battery, the method needs 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 dioxide battery, which comprises a shell, a positive ring, calamine cream, a diaphragm sleeve, a sealing ring, a negative bottom, a copper needle and a small bowl, wherein an insulating ring is embedded on the negative 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 capacity of the existing alkaline zinc-manganese battery is smaller and the service life 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 the discharge capacity of the battery is greatly improved.
The technical scheme adopted by the invention for solving the technical problem 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 glycol
The 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 water solution, and has the functions of wettability and metal corrosion inhibition, and has better stability and oxidation resistance in strong alkali. The organic matter is properly added into the cathode calamine cream of the alkaline zinc-manganese dioxide battery, has certain influence on the gas suppression of the battery, has the function of corrosion resistance 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 solution 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. Moreover, the phenomenon can only be reflected by adding the cathode calamine cream 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 battery 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 the OH of KOH electrolyte - And transferring ions to maintain 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 calamine cream. Below this lower limit, the discharge time of the battery is not significantly prolonged, and above this upper limit, the internal resistance of the battery increases and the discharge time of the battery 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 zinc paste. 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 ester has the general formula:
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 potassium hydroxide aqueous solution 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 influenced when the heating temperature is too high, and the dissolution time is too long when the heating temperature is too low.
The beneficial effects of the invention are:
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 an alkaline zinc-manganese battery according to 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:
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 using specific embodiments and with reference to 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 electrode ring 2, a zinc paste 3, a diaphragm paper 4, a sealing ring 5, a copper nail 6 and a negative electrode 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:
The specific embodiment of the invention is as follows:
(1) Manufacture of positive electrode ring
500g of electrolytic manganese dioxide (produced by Guangxi Eh Man Camilao chemical Co., ltd.) with purity of more than or equal to 90% and specific surface area of 30-35M is taken 2 The alkaline potential is more than or equal to 270mV, 40g of expanded graphite (baotou crystal element) and 2.5g of low molecular weight polyethylene adhesive powder (Huangshan Bernoulli 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, flaked, 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 Body chemical Co., ltd.) was added to the aqueous solution of 10g38% KOH, the mixture was heated to 60 to 65 ℃ and stirred for 30 minutes, and then 25mg of an alkyl alcohol polyoxy-alcohol was addedVinyl ether phosphate OEP-98 (produced by Huangma chemical group in Zhejiang province) is fully stirred and dispersed, and is 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 stirred evenly, the mixture is placed at room temperature for 12 hours, and then vacuum degassing is carried out to prepare zinc paste which is used 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 at 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 drying, filling 6.3g of the zinc paste prepared in the step (2) into the diaphragm paper cylinders, curling and coating a sealant on a machine, 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 negative electrode cover cap into the negative electrode zinc paste, and finally sealing and forming the battery.
After the new cell is placed at room temperature of 20 ℃ for 48 hours, constant-temperature discharge detection comparison is carried out on the new cell and an alkaline zinc-manganese battery (a control cell) without adding 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. Discharge is compared with a detection instrument for 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(s) of
TABLE 1
(2) A discharge mode: 10ohm,24h/day continuous playback; as shown in Table 2: unit: minute(s) of
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 is added to the negative zinc paste, the cell impedance is significantly increased, which proves that there are attachments on the surface of the negative zinc powder. 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 (8)
1. A high-capacity alkaline zinc-manganese dioxide battery comprises a steel shell, a positive ring, zinc paste, diaphragm paper, a sealing ring, a copper nail and a negative cover, and is characterized in that: and adding alkyl alcohol polyoxyethylene ether phosphate and an aluminum compound into the zinc paste for modification to obtain the high-capacity alkaline zinc-manganese battery.
2. The high capacity alkaline zinc-manganese dioxide cell of claim 1, characterized by: the dosage of the alkyl alcohol polyoxyethylene ether phosphate is 0.004-0.05% of the weight of the zinc paste.
3. The high capacity alkaline zinc-manganese dioxide battery of claim 1, characterized by: the aluminum compound is used in an amount of 0.003-0.02 wt% of the zinc paste, calculated on aluminum basis.
4. The large capacity alkaline zinc-manganese dioxide cell according to claim 1, 2 or 3, characterized in that: the general formula of the alkyl alcohol polyoxyethylene ether phosphate is as follows:
wherein R represents a linear or branched saturated alkyl group having 2 to 1 carbon atoms0 and n is an integer of 4 to 10.
5. The large capacity alkaline zinc-manganese dioxide cell according to claim 1, 2 or 3, characterized in that: the aluminum compound is selected from one or more of aluminum hydroxide, aluminum sulfate, aluminum nitrate and aluminum silicate.
6. The high capacity alkaline zinc-manganese dioxide battery as claimed in claim 1, 2 or 3, wherein: the alkyl alcohol polyoxyethylene ether phosphate and the aluminum compound are dissolved in the potassium hydroxide water 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.
7. The high capacity alkaline zinc-manganese dioxide battery of claim 6, characterized by: the mass concentration of the potassium hydroxide aqueous solution is 5-38%.
8. The high capacity alkaline zinc-manganese dioxide battery of claim 6, 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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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104269560A (en) * | 2014-09-10 | 2015-01-07 | 南昌大学 | High-energy zinc-manganese 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 |
| CN111740177A (en) * | 2019-07-26 | 2020-10-02 | 瑞新材料科技(香港)有限公司 | Positive electrode material, positive electrode, battery, and battery pack |
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| JPS63285868A (en) * | 1987-05-19 | 1988-11-22 | Fuji Elelctrochem Co Ltd | Alkaline battery |
| JP2001325957A (en) * | 2000-05-16 | 2001-11-22 | Toshiba Battery Co Ltd | Alkaline secondary cell |
| CN101366135A (en) * | 2006-06-28 | 2009-02-11 | 松下电器产业株式会社 | Alkaline dry battery |
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2013
- 2013-03-14 CN CN201310081502.7A patent/CN103236552B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63285868A (en) * | 1987-05-19 | 1988-11-22 | Fuji Elelctrochem Co Ltd | Alkaline battery |
| JP2001325957A (en) * | 2000-05-16 | 2001-11-22 | Toshiba Battery Co Ltd | Alkaline secondary cell |
| CN101366135A (en) * | 2006-06-28 | 2009-02-11 | 松下电器产业株式会社 | Alkaline dry battery |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104269560A (en) * | 2014-09-10 | 2015-01-07 | 南昌大学 | High-energy zinc-manganese 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 |
| CN111740177A (en) * | 2019-07-26 | 2020-10-02 | 瑞新材料科技(香港)有限公司 | Positive electrode material, positive electrode, battery, and battery pack |
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