CN1328803C - Environment-friendly zinc-manganese battery cathode can - Google Patents
Environment-friendly zinc-manganese battery cathode can Download PDFInfo
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Abstract
The invention discloses an environment-friendly zinc-manganese battery cathode can, which is composed of a multi-element zinc-based alloy, wherein the multi-element zinc-based alloy comprises: 0.002-0.006 wt% indium, 0.001-0.01 wt% rare earth element and/or 0.001-0.018 wt% magnesium, but contains no non-accidental harmful substance mercury, cadmium and lead, and the accidental impurity iron in the alloy is less than or equal to 0.006wt%, copper is less than or equal to 0.002wt%, and tin is less than or equal to 0.003wt%. In addition, the alloy can also contain 0 to 0.009wt% of other modified elements such as titanium, zirconium, aluminum, silicon, silver, bismuth, calcium and the like. The corrosion rate, mechanical strength and discharge performance of the battery made of the zinc-based alloy reach or even exceed those of the battery cathode tanks containing mercury, cadmium and lead, and satisfactory processability is obtained in the plastic deformation processes of casting, plate rolling, cake punching, back extrusion and the like.
Description
Technical Field
The invention relates to an environment-friendly zinc-manganese battery cathode can, in particular to an environment-friendly zinc-manganese battery cathode can which is formed by multi-element zinc-based alloy without non-accidental harmful substances such as mercury, cadmium and lead, can be processed smoothly and keeps high performance.
Background
Since 1868 France Lekelang was made, zinc-manganese batteries have been developed for over 100 years, and are characterized by being convenient and safe to use and low in price, so far, the zinc-manganese batteries are the batteries with the widest primary battery use and the largest output, however, the zinc-manganese battery materials contain recognized toxic and harmful substances such as mercury, cadmium and lead which have serious influence on the environment and are dangerous to human health, and the phenomena are more and more valued by environmental scientists.
Generally, zinc manganese cell improvements are focused only on high capacity and high power performance, such as: the electric paste type battery is developed to a paper plate battery, and the general battery is developed to a high capacity C-type battery and a high power P-type battery.
In the present day of increasing awareness of environmental protection, the battery industry has been forced to advance toward green industrialization. Firstly the use of mercury should be avoided, secondly cadmium, and secondly lead-free. At present, the national environmental standards of China HJBZ009-1999 and GB/T7112-1998 require that the mercury content in the battery is less than or equal to 0.0001 percent, the battery has no temporary requirement on cadmium and lead, the European Union requires low cadmium and low lead, and the 98/101/EEC requires that the mercury content is less than or equal to 0.005 percent, the cadmium content is 0.025 percent and the lead content is 0.4 percent. The green environmental protection battery requires less than or equal to 0.001 percent of cadmium, less than or equal to 0.0015 percent of lead and less than or equal to 0.0001 percent of mercury, namely the waste battery does not pollute the environment, the zinc cathode can accounts for about 1/6 to 1/3 of the total weight of the battery, the green environmental protection battery can contain 0.006 to 0.003 percent of cadmium and 0.009 to 0.005 percent of lead when being converted into the battery cathode can.
It can be seen that the long-term formation of lead-cadmium-containing cathode cans plays an important role. The research on the effect of cadmium and lead in the cathode can is beneficial to realizing the replacement of the cadmium and lead by non-toxic elements, and the effect still reaches the performances of various original batteries.
As is well known, the manufacturing process of a negative can for a zinc-manganese battery is completed by the following procedure.
(1) Adding proper amount of cadmium and lead metals into pure zinc to melt the pure zinc to form ternary zinc-based alloy.
(2) The zinc-based solution flows into a continuous casting machine to be cast and cooled at a certain speed, and a continuous cast zinc-based alloy belt is obtained.
(3) The continuous casting zinc strip is rolled in a hot state by a two-roller rolling mill, and certain speed and rolling reduction are controlled to obtain a zinc-based alloy plate coil or plate with preset thickness.
(4) And punching in hot or cold state in a cake punching machine to obtain round or hexagonal zinc cake.
(5) On a mechanical or hydraulic extruder, the integral zinc can is obtained by a concave-convex die reverse extrusion method or a partial forward extrusion method.
(6) Cutting off a part of the redundant terminal according to a preset height.
In the process of manufacturing the cathode can according to the procedures, the zinc-based alloy material is subjected to processes of heating, melting, cooling, crystallization, solid-state to liquid-state and solid-state physical change, namely, processability, hot-state or cold-state rolling deformation and extrusion deformation, and plastic processing, when the processability of the material is insufficient, fracture, crack during rolling, and shape, burr and dimension defects, such as severe abrasion of a tool and a die, are formed during extrusion, so that continuous processing is interrupted, the yield is reduced, or the cost is increased, namely, the basic elements of the processing process.
After the finished cathode can is packaged, stored and transported, the cathode can is conveyed into a battery assembly line to undergo mechanical procedures of assembling an anode bag, a diaphragm plate, filling electrolyte, sealing battery curling, pressing a wire and the like, so that the cathode can is required to have proper mechanical strength, however, the improvement of the mechanical strength can cause the reduction of plastic processing, namely, the maintenance of the hardness and the extrusion temperature of a zinc alloy cake is another important factor.
The zinc-based cathode can is not only an active substance for electrode reaction in the battery, but also a container of the battery, and rapidly provides electricity after contacting with an electrolyte, so that zinc is gradually consumed, the zinc can becomes thin, the zinc can is also subjected to self-corrosion during the storage of the battery, capacity reduction or electrical property deterioration is caused, and perforation is caused in severe cases, so that the corrosion of the zinc can is reduced, which is the most important factor.
As described above, the negative electrode can is required to have good plastic workability, suitable mechanical strength, and low corrosiveness and maintain high electrochemical properties in three important factors during and after the manufacturing process, which are mainly related to the composition of the zinc-based alloy, and secondarily to guarantee various temperatures, speeds, processing ratios, equipment accuracy, and the like of the manufacturing process, such as melting, casting, rolling, stamping, extrusion.
For a long time, in order to improve the above characteristics, such as processability, mechanical strength, corrosion resistance and the like, a negative electrode can of a zinc-manganese battery takes lead, cadmium and zinc as main elements, generally the lead content is 0.4-0.8%, and the cadmium content is 0.035-0.06%, wherein the lead can improve the ductility of the zinc, plays a role in lubricating the interior of the metal when metal solid-state flow is generated in extrusion, can reduce the precipitation of hydrogen gas of a zinc electrode and improve the corrosion resistance, the cadmium is added to improve the precipitation potential of the hydrogen in the zinc electrode and reduce the self-solubility of the zinc electrode, so that the crystal grains of the zinc are refined and uniform, the surface unevenness of the zinc is improved, and the tensile strength and the yield strength of the zinc are improved.
Disclosure of Invention
The invention aims to solve the technical problem that an environment-friendly zinc-manganese battery cathode can is manufactured by selecting non-toxic elements which do not cause damage to the environment, replacing the conventional common lead, cadmium and mercury, adding the elements into a zinc-based alloy to form a multi-element zinc-based alloy with good processing performance, and not only influencing the performance of the battery but also increasing the manufacturing cost.
The technical scheme adopted by the invention for solving the technical problems is as follows: the environment-friendly zinc-manganese battery cathode can is composed of a multi-element zinc-based alloy, wherein the multi-element zinc-based alloy comprises: 0.002-0.006 wt% indium, 0.001-0.01 wt% rare earth element and/or 0.001-0.018 wt% magnesium, but no non-accidental harmful substance mercury, cadmium and lead, and the alloy contains accidental impurity Fe not more than 0.006wt%, cu not more than 0.002wt% and Sn not more than 0.003wt%.
The zinc-based alloy can also contain at least one of elements of titanium, zirconium, aluminum, silicon, silver, bismuth and calcium, and the content is 0.001 to 0.009wt percent.
The incidental impurity cadmium in the pure zinc used as the raw material of the zinc-based alloy is less than or equal to 0.003 weight percent, and the incidental impurity lead is less than or equal to 0.005 weight percent.
The preferable content of indium in the zinc-based alloy is 0.0025 to 0.0045wt percent.
The preferable content of the rare earth element in the zinc-based alloy is 0.006-0.009 wt%.
The preferable content of magnesium in the zinc-based alloy is 0.003 to 0.012wt percent.
The rare earth element is preferably at least one selected from lanthanum or cerium.
The limitation on the contents of impurities of iron, copper and tin is due to the consideration that a battery manufacturer can easily remove mercury as a corrosion inhibitor to manufacture a mercury-free battery. In the process of manufacturing the battery, mercury is often added into zinc powder as a corrosion inhibitor, the mercury is a substance extremely harmful to the environment and human health, and the problem of corrosion resistance of the cathode tank after the mercury is removed is solved. Of course, the addition of organic corrosion inhibitors to the electrolyte is also an effective solution.
In the periodic table, it can be seen that the most adjacent element to cadmium is indium whose atomic radius is close to that of cadmium and specific gravity is 7.3g/cm 3 Specific gravity of 7.14g/cm with respect to zinc 3 The zinc and the magnesium can also slow or inhibit the self-dissolution of the anode of the battery in the long-term storage process, lighten the self-discharge effect of the zinc, increase the mechanical strength of the cathode tank, and in addition, the magnesium can also increase the activity of the anode and improve the discharge performance of the battery.
In recent years, better effect is achieved by adding rare earth in non-ferrous metal smelting, and analysis shows that the addition of lanthanum rare earth metals such as metal lanthanum and metal cerium in zinc-based alloy can refine the macro and micro structure of a zinc plate, so that the surface quality of a battery cathode can is improved, the corrosion rate of acid and alkali resistance is further improved, the ductility increase can be achieved, and the battery cathode can has good cold and hot processability and low work hardening coefficient. This is indeed demonstrated in the following experiments.
The zinc-based alloy is further added with one or a mixture of more of elements such as titanium, zirconium, aluminum, silicon, silver, bismuth, calcium and the like, so that the comprehensive improvement effect can be achieved, for example, the ductility and the processability of titanium can be improved, the hydrogen evolution potential of bismuth can be improved, the corrosion of zinc electrode is reduced, the alloy is refined by silicon, zirconium and calcium, and the conductivity and the processability of aluminum and silver can be improved.
Further, it has been found in the study that the addition of indium is the most effective element for reducing the corrosion rate in view of the influence on the corrosion rate, and the corrosion rate decreases as the addition amount thereof increases, but the above range is preferable in view of the comprehensive performance and cost; from the influence on the discharge performance, the addition of indium is beneficial to the discharge performance, the addition of magnesium improves the discharge performance, but the addition of indium and magnesium is too much, the discharge performance is reduced, and the addition of rare earth metal and other improved elements also has certain influence on the discharge performance; from the influence on the alloy processability, the addition of a small amount of indium does not influence the processability, but the addition amount is too much, the processability is deteriorated, the addition of rare earth elements can improve the processability, the addition amount is increased, the processability is better, and the addition of magnesium and other improved metals has little influence on the processability in a limited range; in view of the influence on the hardness of the alloy, addition of indium has a certain effect on the increase in hardness, while addition of magnesium increases the hardness, and an increase in the amount of magnesium may necessitate an appropriate increase in the working temperature during working, but in addition, there is no other adverse effect.
Based on the analysis and the practice of manufacturing the cathode can for a long time, the inventor comprehensively considers the factors of the discharge performance, the corrosion resistance rate, the mechanical strength, the processing performance and the manufacturing cost of the battery, and achieves the purpose of manufacturing the environment-friendly zinc-manganese battery cathode can which has the performance equivalent to or even better than that of the traditional lead-cadmium-containing cathode can without adding harmful substances such as lead, cadmium and mercury from the environmental point of view.
From the description of the present disclosure and the results of the experimental analysis and the specific examples of the factors to be described later: compared with the existing cathode can containing harmful substances such as lead, cadmium, mercury and the like, the cathode can does not contain harmful substances such as lead, cadmium, mercury and the like, meets the requirement of modern environmental protection, does not pollute the environment by using the used waste battery, has the corrosion rate and the mechanical strength reaching or even exceeding those of the existing common cathode can containing lead, cadmium and mercury, and obtains satisfactory processability in the plastic deformation processes such as casting, plate rolling, cake punching, back extrusion and the like; in addition, the discharge performance of the battery manufactured by the lead-free lithium ion battery also reaches or even exceeds that of the existing common battery containing lead, cadmium and mercury.
Detailed Description
The present invention is described in further detail below with reference to examples.
The manufacturing of the zinc-manganese battery cathode can is carried out according to the conventional process, namely:
(1) Adding proper amount of elements into pure zinc according to the formula of the multielement zinc-based alloy, and melting the elements to form the multielement zinc-based alloy.
(2) The zinc-based alloy solution flows into a continuous casting machine to be cast and cooled at a certain speed, and a continuous cast zinc-based alloy belt is obtained.
(3) And (3) carrying out hot rolling on the continuous casting zinc strip by a two-roll mill, and controlling certain speed and rolling reduction to obtain a zinc-based alloy plate coil or plate with a preset thickness.
(4) And punching the zinc cake in a hot state or a cold state on a cake punching machine to obtain the round or hexagonal zinc cake.
(5) On a mechanical or hydraulic extruder, the integral zinc can is obtained by a concave-convex die reverse extrusion method or a partial forward extrusion method.
(6) A portion of the excess ends are cut off at a predetermined height.
The battery required by the discharge performance detection is also prepared according to the conventional process, and the specification of the battery is R6P.
The following test means generally adopted by cadmium-lead-containing cathode tanks with better evaluation performance are used as the basis, a series of experimental results are used for comparison, and the results of the invention are evaluated from the following important indexes:
(a) Firstly, corrosion resistance evaluation indexes are specified, namely, a zinc cathode tank is soaked in an acid electrolyte for a period of time, then the weight loss after corrosion is weighed, the percentage difference between the weight loss and the weight before corrosion is obtained, and the corrosion resistance is generally required to be less than or equal to 1%. The corrosion test method is as follows: three samples are taken and cleaned by pure water, are placed in an oven for drying for 2 hours at the temperature of 105 ℃, are weighed after cooling, are placed in 150ml of dilute hydrochloric acid liquid, (15 ml of high-quality hydrochloric acid is diluted to 150ml by pure water), are taken out after one hour, are dried for 2 hours at the temperature of 105 ℃, are weighed after cooling, and have no more than 1 percent of weight reduction compared with the weight reduction before soaking.
(b) The discharge performance evaluation adopts R6P type national standard GB/T7112-94, according to 1.8 ohm pulse discharge frequency, 3.9 ohm interval and continuous discharge time, 10 ohm interval discharge accumulated time and one year storage capacitance, 100 points are used as ideal indexes, a group of score indexes are obtained by insufficient points, and the full score rate is generally required to be not less than 90%.
(c) The workability evaluation is carried out by a conventional manufacturing process, and when elements such as indium, magnesium and the like are added, parameters such as temperature, speed, working ratio and the like of each process such as melting, casting, plate rolling, cake punching, extrusion and the like can be properly adjusted, so that the workability is improved, and the workability is expressed by numbers 1, 2 and 3 (wherein the larger the number is, the better the workability is) by taking three or more as ideal indexes such as no fracture according to a continuous casting process, no crack in a continuous rolling process, good extrusion plasticity and the like and giving a certain shortage or interruption of working as the next order.
(d) The evaluation of mechanical strength is measured by Vickers hardness HV of negative can cut pieces or Brinell hardness HB of zinc cakes, and HB38-45 is generally required.
The invention is described in detail below by using an R6P type high-power zinc-manganese battery cathode can and adopting a factor-horizontal orthogonal experiment, and the advantages and the important major and minor components of indium, magnesium, rare earth elements and other improved components are analyzed in terms of square difference. To find the best formulation and process conditions, the examples are described for non-limiting example purposes only.
1. Factor-horizon (see table 1)
Table 1 units: ppm of
| Level phi | Factors of the fact | |||
| Indium A | Magnesium B | Rare earth C | Other D | |
| I | 0 | 0 | 0 | 0 |
| II | 30 | 40 | 40 | 50 |
| III | 60 | 180 | 80 | 90 |
2. Example summary of factor-level analysis (see Table 2)
Table 2 units: ppm of
| Test No. | Factors of the design | |||
| Indium A | Magnesium B | Rare earth C | Other D | |
| 1 | 0 | 0 | 0 | 0 |
| 2 | 0 | 40 | 40 | 50 |
| 3 | 0 | 180 | 80 | 90 |
| 4 | 30 | 0 | 40 | 90 |
| 5 | 30 | 40 | 80 | 0 |
| 6 | 30 | 180 | 0 | 50 |
| 7 | 60 | 0 | 80 | 50 |
| 8 | 60 | 40 | 0 | 90 |
| 9 | 60 | 180 | 40 | 0 |
3. Experimental integrated results table (see Table 3)
4. Factor analysis
(a) Corrosion rate U (see Table 4)
TABLE 3
| Test No. | Corrosion rate% U | Discharge behavior V | Processability W | Hardness HBQ |
| 1 | 2.6 | 60 | 0 | 38 |
| 2 | 3.5 | 70 | 1 | 39 |
| 3 | 4.53 | 75 | 1 | 37 |
| 4 | 0.80 | 95 | 2 | 39 |
| 5 | 0.60 | 100 | 3 | 40 |
| 6 | 0.72 | 95 | 2 | 40 |
| 7 | 0.43 | 85 | 1 | 41 |
| 8 | 0.26 | 90 | 0 | 42 |
| 9 | 2.03 | 87 | 1 | 44 |
TABLE 4
(b) Discharge Property V (see Table 5)
(C) Processability W (see Table 6)
(d) Hardness Q (see Table 7)
TABLE 5
TABLE 6
TABLE 7
Explanation of primary and secondary analysis and determination of superior level of the above factors:
calculated values are:
I (1、2、3) (1、4、7) (1、6、8) (1、5、9)
II (4、5、6) (2、5、8) (2、4、9) (2、6、7)
III (7、8、9) (3、6、9) (3、5、7) (3、4、8)
I′ (1、2、3)/3 (1、4、7)/3 (1、6、8)/3 (1、5、9)/3
II′ (4、5、6)/3 (2、5、8)/3 (2、4、9)/3 (2、6、7)/3
III′ (7、8、9)/3 (3、6、9)/3 (3、5、7)/3 (3、4、8)/3
r: maximum-minimum of (I ', II ', III ');
the factors are primary and secondary: the R value is from large to small;
the better level is as follows: (I ', II ', III ') the corrosion rate U is minimum: such as A II′ =0.71, namely (4, 5, 6)/3 of the experiment number, and A is obtained by looking up 4, 5 and 6 II The content of indium is 30ppm, and the rest is the same; the discharge performance V is the maximum value, the processing performance W is the maximum value, and the hardness value Q is the maximum value, so that a better horizontal value can be obtained by the same method.
Evaluation of corrosion rate U:
in table 4, the R values are a =2.83, B =1.14, C =0.92, and D =0.31 in this order, the importance of the additive elements are a (indium), B (magnesium), C (rare earth), and D (other elements) in this order, and the content of the additive elements is the minimum value a of the average corrosion rate II′ ＝0.71、B I′ ＝1.28、C I′ ＝1.19、D II′ =1.55, indium is the most effective element for reducing the corrosion rate, and the corrosion rate decreases as the amount added increases.
Evaluation of discharge performance V:
the R values in the table 5 are A =28.34, B =6.67, C =5 in sequence. D =4.34, the importance of the additive elements is A (indium), B (magnesium), C (rare earth) and D (other elements) in sequence, and the content of the additive elements is the maximum value A of the average score fraction II′ ＝96.67、B II′ ＝86.67、C III′ ＝86.67、D III′ If the addition of indium is not less than 86.67 percent, the discharge performance is improved by adding magnesium, but if the addition amounts of indium and magnesium are too large, the discharge performance is reduced, and the discharge performance is influenced by adding rare earth metals and other improving elements.
Evaluation of processability W:
from table 6, R values are a =1.66, b =0.33, c =1 in this order. D =0, the importance of the additive elements is A (indium), C (rare earth), B (magnesium) and D (other elements) in sequence, and the content of the additive elements is the maximum value A of the processing satisfaction II′ ＝2.33、B II′ B III′ ＝1.33、C III′ ＝1.67、D I′ D II′ D III′ =1.33, it can be seen that addition of small amounts of indium does not affect processability, but too much addition results in poor processability, addition of rare earth elements improves processability, and addition of large amounts of indium results in better processability, and addition of magnesium and other modifying metals does not affect processability within a limited rangeIs large.
Evaluation of hardness value Q:
from table 7, R values are a =4.33, b =1, c =1.34 in this order. D =1.34, the importance of the additive elements being, in order, a (indium), C (rare earth), D (other elements), B (magnesium), the content a of the additive elements being III′ ＝42.33、B II′ B III′ ＝40.33、C II′ ＝40.67、D I′ 40.67, the addition of indium has a certain effect on the increase in hardness, while the addition of magnesium increases the hardness, and the increase in the amount of magnesium may necessitate an appropriate increase in the working temperature during working, but no other substance is usedAdverse effects.
In summary, the analysis results are as follows:
comprehensive evaluation of U, V, W and Q:
U：A→B→C→D
V：A→B→C→D
W：A→C→B→D
Q：A→C→D→B
it can be seen that: a is the most important component, B and C are the next most important components, and D is the less important component.
Preferred levels of content ranges (see table 1):
U：A II B I C I D III
V：A II B II C III D III
W：A II B IIIII C III D IIIIII
Q：A III B IIIII C II D I
according to four set important indexes, the corrosion resistance, the discharge performance, the processing performance and the hardness value are sequentially, and a better sequence is obtained after comprehensive balance: a. The II →B II →C III →D III Namely: 30ppm of indium, 40ppm of magnesium, 80ppm of rare earth and 90ppm of others
Based on the above-mentioned preferred level, the preferred proportion is selected from the above-mentioned factor-level examples and implemented again as follows:
adding indium into pure zinc by 0.003Wt%, magnesium by 0.004Wt%, rare earth by 0.008Wt%, and one or more of titanium, zirconium, aluminum, silicon, silver, bismuth and calcium by 0.009Wt% (excluding impurities brought in the raw materials). The R6P type zinc-manganese battery is manufactured by obtaining satisfactory processability through melting, casting hot rolling, cake punching and extrusion forming according to a conventional process, and the corrosion rate, hardness value and battery performance of the R6P type zinc-manganese battery are shown in a table 8.
Comparative example:
the R6P type zinc-manganese battery is prepared by adding 0.45 Wt% of lead and 0.035Wt% of cadmium into pure zinc according to the conventional process, and the corrosion rate hardness value and the battery performance are shown in Table 8.
TABLE 8
| Item | Examples | Comparative example | ||
| New electricity | Stored for one year | New electricity | Stored for one year | |
| Number of 1.8 ohm pulse discharges | 88 | 55 | 82 | 54 |
| 3.9 ohm interval discharge time/min | 54 | 52 | 56 | 51 |
| 10 ohm interval discharge time/min | 282 | 246 | 288 | 240 |
| Leak test | Without leakage | Without leakage | Without leakage | Without leakage |
| Corrosion rate% | 0.76 | 0.82 | ||
| Hardness HB | 39 | 41 | ||
In the comparison table 8, the corrosion resistance of the battery cathode can of the present invention is superior to that of the cathode can containing lead and cadmium, so the storage performance is improved, the number of pulse discharge times is also significantly increased, and the discharge performance required by high power is improved.
On the basis of the above experimental analyses, the following examples (in the examples, indium A added to pure zinc is metallic indium, magnesium B is metallic magnesium, rare earth metal C is 80% metallic lanthanum, 20% metallic cerium, and other modified metals D are 70% titanium, 20% calcium, 10% bismuth.) and comparative examples (see Table 9) were carried out:
as described and compared, the cathode can of the zn-mn cell of the present invention can be manufactured to have the same or even better performance as the conventional cathode can by adding indium, magnesium, rare earth or further safe metal elements such as titanium, zirconium, aluminum, silicon, silver, bismuth, calcium to the zinc-based alloy composition without adding harmful substances such as mercury, cadmium, lead, etc. in the aforementioned ratio range and preferred formula.
In addition, if the zinc-manganese battery cathode can contains less than or equal to 0.003Wt% of cadmium and less than or equal to 0.005Wt% of lead in pure zinc, the zinc-manganese battery assembled by the cathode can meet the requirements of green environment-friendly batteries with less than or equal to 0.0001Wt% of mercury, less than or equal to 0.001Wt% of cadmium and less than or equal to 0.0015 Wt% of lead, and the used waste batteries do not pollute the environment; if the incidental impurity iron in the zinc-based alloy is controlled to be less than or equal to 0.006wt%, or the incidental impurity copper is further controlled to be less than or equal to 0.002wt% and tin is further controlled to be less than or equal to 0.003wt%, the mercury-free battery can be manufactured by a battery manufacturer.
From the experimental results described herein, it can be seen that the corrosion resistance is significantly improved by adding indium to pure zinc, the hardness is improved by adding magnesium, the workability is improved, the corrosion rate and the discharge performance are improved, the metallographic structure is improved by adding rare earth, the ductility is improved, the corrosion rate is slowed down, and the comprehensive performance is excellent by adding other elements.
TABLE 9
| Fruit of Chinese wolfberry Test (experiment) Number (C) | The zinc-based alloy is added with metal elements and the content Wt% | Rotten food Etching solution Rate of change ％ | Hard Degree of rotation HB | Discharge performance | |||||||||||
| Lead (II) | Cadmium (Cd) | Indium (in) | Magnesium alloy | Rare earth element | Others (C) | 1.8 omega pulse discharge (times) | 3.9 omega interval discharge (minute) | 10 omega continuous discharge (minute) | Leakage-proof device Test of | ||||||
| New electricity | 12 months old | New electricity | 12 months old | New electricity | 12 months old | ||||||||||
| 1 | 0 | 0 | 0.002 | 0.018 | 0 | 0 | 0.82 | 42 | 85 | 53 | 55 | 51 | 287 | 240 | Without leakage |
| 2 | 0 | 0 | 0.002 | 0 | 0.01 | 0 | 0.81 | 39 | 83 | 51 | 54 | 50 | 285 | 240 | Without leakage |
| 3 | 0 | 0 | 0.006 | 0.001 | 0 | 0 | 0.46 | 40 | 84 | 53 | 56 | 52 | 287 | 242 | Without leakage |
| 4 | 0 | 0 | 0.006 | 0 | 0.001 | 0 | 0.55 | 39 | 83 | 52 | 55 | 51 | 286 | 241 | Without leakage |
| 5 | 0 | 0 | 0.003 | 0.004 | 0 | 0.001 | 0.78 | 40 | 86 | 54 | 56 | 52 | 287 | 243 | Without leakage |
| 6 | 0 | 0 | 0.003 | 0 | 0.004 | 0.001 | 0.81 | 39 | 85 | 52 | 54 | 51 | 285 | 241 | Without leakage |
| 7 | 0 | 0 | 0.003 | 0.004 | 0.004 | 0 | 0.77 | 40 | 86 | 53 | 55 | 51 | 286 | 242 | Without leakage |
| 8 | 0 | 0 | 0.003 | 0.004 | 0.008 | 0.001 | 0.72 | 40 | 87 | 54 | 53 | 50 | 284 | 245 | Without leakage |
| 9 | 0 | 0 | 0.003 | 0.004 | 0.008 | 0.009 | 0.76 | 41 | 88 | 55 | 54 | 52 | 282 | 246 | Without leakage |
| 10 | 0.45 | 0.035 | 0 | 0 | 0 | 0 | 0.82 | 41 | 82 | 54 | 56 | 51 | 288 | 240 | Without leakage |
| 11 | 0.45 | 0 | 0 | 0 | 0 | 0 | 0.86 | 40 | 81 | 52 | 54 | 50 | 284 | 238 | Without leakage |
Claims (7)
1. An environment-friendly zinc-manganese battery cathode can is composed of a multi-element zinc-based alloy, wherein the multi-element zinc-based alloy comprises: 0.002-0.006 wt% indium, 0.001-0.01 wt% rare earth element and/or 0.001-0.018 wt% magnesium, but no non-accidental harmful substance mercury, cadmium and lead, and accidental impurity iron less than 0.006wt%, copper less than 0.002wt% and tin less than 0.003wt% in the alloy.
2. The environment-friendly cathode can for zinc-manganese batteries according to claim 1, characterized in that the zinc-based alloy further comprises at least one of the elements titanium, zirconium, aluminum, silicon, silver, bismuth and calcium in an amount of 0.001-0.009 wt%.
3. The environment-friendly zinc-manganese battery cathode can according to claim 1 or 2, characterized in that the incidental impurities cadmium in the raw material pure zinc used by the zinc-based alloy is less than or equal to 0.003wt%, and lead is less than or equal to 0.005wt%.
4. The anode can of claim 1 or 2, wherein the content of indium in the zinc-based alloy is 0.0025-0.0045 wt%.
5. The negative electrode can of an environment-friendly zinc-manganese battery according to claim 1 or 2, wherein the content of rare earth elements in the zinc-based alloy is 0.006-0.009 wt%.
6. The environment-friendly zinc-manganese battery cathode can according to claim 1 or 2, characterized in that the content of magnesium in the zinc-based alloy is 0.003-0.012 wt%.
7. The anode can of claim 1 or 2, wherein the rare earth element is at least one of lanthanum or cerium.
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| CNB2003101091512A CN1328803C (en) | 2003-12-05 | 2003-12-05 | Environment-friendly zinc-manganese battery cathode can |
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| CNB2003101091512A CN1328803C (en) | 2003-12-05 | 2003-12-05 | Environment-friendly zinc-manganese battery cathode can |
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| CN1328803C true CN1328803C (en) | 2007-07-25 |
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Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100452489C (en) * | 2004-11-05 | 2009-01-14 | 松栢电池厂有限公司 | Dry battery cathode and manufacturing method thereof, and zinc-manganese dry battery using same |
| CN100452494C (en) * | 2004-11-16 | 2009-01-14 | 松栢电池厂有限公司 | Zinc granule for zinc-manganese dry cell and method for manufacturing same |
| CN100490216C (en) * | 2005-04-26 | 2009-05-20 | 江庆华 | Cell zinc tank preparing method |
| WO2006133641A1 (en) * | 2005-06-13 | 2006-12-21 | Liangzhi Lin | A zinc-manganese dry cell and negative alloy material and manufacture method thereof |
| CN100414745C (en) * | 2005-06-13 | 2008-08-27 | 林良智 | Zinc material for environment-friendly battery and manufacturing method thereof |
| CN100414744C (en) * | 2005-08-16 | 2008-08-27 | 林良智 | Lead-free environment-friendly zinc-manganese dry battery |
| CN107447130A (en) * | 2017-08-10 | 2017-12-08 | 嘉兴市大纽电池配件有限公司 | environment-friendly zinc material for zinc-manganese battery and preparation method thereof |
| CN114628708B (en) * | 2022-03-29 | 2024-03-01 | 杭州长命电池有限公司 | Mercury-free lead-free cadmium-free zinc-manganese battery and manufacturing method thereof |
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| CN1004778B (en) * | 1984-02-20 | 1989-07-12 | 松下电器产业株式会社 | Zinc-alkaline battery |
| JPH06302323A (en) * | 1993-04-14 | 1994-10-28 | Toshiba Battery Co Ltd | Manganese dry battery |
| US5425913A (en) * | 1990-02-08 | 1995-06-20 | S.A.Acec-Union Miniere N.V. | Zinc alloy for electrochemical battery cans |
| CN1311537A (en) * | 2000-10-31 | 2001-09-05 | 周炳利 | High specific energy mercury-free alloy zinc powder for alkaline battery, preparation method and device thereof |
| CN1442918A (en) * | 2002-03-05 | 2003-09-17 | 三井金属矿业株式会社 | Zinc alloy powder, negative electrode used for alkaline manganese dioxide battery and said battery |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1004778B (en) * | 1984-02-20 | 1989-07-12 | 松下电器产业株式会社 | Zinc-alkaline battery |
| US5425913A (en) * | 1990-02-08 | 1995-06-20 | S.A.Acec-Union Miniere N.V. | Zinc alloy for electrochemical battery cans |
| JPH06302323A (en) * | 1993-04-14 | 1994-10-28 | Toshiba Battery Co Ltd | Manganese dry battery |
| CN1311537A (en) * | 2000-10-31 | 2001-09-05 | 周炳利 | High specific energy mercury-free alloy zinc powder for alkaline battery, preparation method and device thereof |
| CN1442918A (en) * | 2002-03-05 | 2003-09-17 | 三井金属矿业株式会社 | Zinc alloy powder, negative electrode used for alkaline manganese dioxide battery and said battery |
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| CN1547274A (en) | 2004-11-17 |
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