CN1547274A - Environment-friendly zinc-manganese battery cathode can - Google Patents
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Abstract
The invention discloses an environment-friendly zinc-manganese battery cathode can, which is composed of multi-element zinc-based alloy containing 0.002-0.006 wt% of indium and 0.001-0.01 wt% of rare earth elements; or the zinc alloy consists of multi-element zinc base alloy containing 0.002 to 0.006 weight percent of indium and 0.001 to 0.018 weight percent of magnesium; the zinc-based alloy can also contain 0.001 to 0.018 weight percent of magnesium; the zinc-based alloy of the latter can also contain 0.001 to 0.01 weight percent of rare earth elements; the alloy does not contain non-accidental harmful substances such as mercury, cadmium and lead. 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 cathode can made of the zinc-based alloy reach or even exceed those of the battery cathode can made of the common alloy containing mercury, cadmium and lead, and the zinc-based alloy achieves satisfactory processability in plastic deformation processes such as 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 made of multi-element zinc-based alloy without non-accidental harmful substances such as mercury, cadmium and lead, can be smoothly processed and keeps high performance.
Background
Since 1868 France Lekelang Xie Zhicheng, zinc-manganese battery has been developed for over 100 years, it is characterized by convenient and safe use and low price, and still is a battery with the widest use and the largest output of primary battery till now, however, the harmful substances recognized as mercury, cadmium, lead and the like in the zinc-manganese battery material have serious influence on the environment and endanger the health of people, 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 Chinese environmental standard HJBZ009-1999 and the national battery standard GB/T7112-1998 require that the mercury of 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 is less than or equal to 0.005 percent, the cadmium is 0.025 percent and the lead 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 lead-cadmium-containing cathode can has an important role. The research on the function of cadmium and lead in the cathode can is beneficial to realizing that the cadmium and lead are replaced by non-toxic elements, and the effect still reaches the performances of the 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) 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 backward 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 is the most important factor for rapidly providing electricity after contacting with an electrolyte, gradually consuming zinc, thinning the zinc can, and causing self-corrosion of the zinc can during storage of the battery, capacity reduction or electrical performance deterioration, and perforation in severe cases, thereby reducing the corrosivity of the zinc can.
As described above, the three important factors of the negative electrode can during and after the manufacturing process require good plastic workability, suitable mechanical strength, and low corrosiveness, and maintain high electrochemical properties, which are mainly related to the composition of zinc-based alloy, and are secondarily guaranteed by manufacturing processes such as various temperatures, speeds, processing ratios, equipment precision, and the like of 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 does not influence the performance of the battery, but also does not increase 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 multielement zinc-based alloy containing 0.002-0.006 wt% of indium, 0.001-0.01 wt% of rare earth elements and no non-accidental harmful substances such as mercury, cadmium and lead. Or a multi-element zinc-based alloy containing 0.002-0.006 wt% of indium, 0.001-0.018 wt% of magnesium and no non-accidental harmful substances such as mercury, cadmium and lead. The zinc-based alloy can also contain 0.001 to 0.018 weight percent of magnesium. The zinc-based alloy of the latter can also contain 0.001 to 0.01 weight percent of rare earth elements.
The zinc-based alloy can also contain at least one of modified 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 lead is less than or equal to 0.005 weight percent.
The incidental impurity iron in the zinc-based alloy is less than or equal to 0.006wt%.
Incidental impurities in the zinc-based alloy, namely copper is less than or equal to 0.002wt% and tin is less than or equal to 0.003wt%.
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 and 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 the zinc-containing compound to zinc of 7.14g/cm 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 lanthanum metal, cerium metal and the like 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 excessive, 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, the addition of indium has a certain effect on the hardness increase, while the addition of magnesium increases the hardness, and if the amount of magnesium is increased, the working temperature may need to be increased appropriately during working, but 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 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 experimental analysis of the factors to be described later, and the results of the specific examples, it can be seen that: 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 will be described in further detail 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) 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 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 for detecting the discharge performance 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 dried for 2 hours at 105 ℃ in an oven, are cooled and weighed, and then are put into 150ml of dilute hydrochloric acid liquid, (15 ml of high-quality hydrochloric acid is diluted to 150ml by pure water), the samples are taken out after one hour, are dried for 2 hours at 105 ℃, are cooled and weighed, and the weight reduction of the samples before soaking is not more than 1 percent.
(b) The discharge performance evaluation adopts R6P type national standard GB/T7112-94, 100 points are used as ideal indexes 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, a group of score indexes are obtained by deficiency and subtraction, 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 electrode can cut pieces or Brinell hardness HB of zinc cake, 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 fact | |||
| 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 major and minor analysis and determination of superior levels of the above factors:
calculated values:
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:
from table 5, R values are a =28.34, b =6.67, c =5 in this order. 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:
the R values in table 6 were a =1.66, b =0.33, c =1 in 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 determined according to 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 adding a small amount of indium does not affect processability, but too much amount of indium, processability becomes poor, addition of rare earth element improves processability, and addition of magnesium and other improved 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 element), 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′ In of 40.67, addition of in has a certain effect on hardness improvement, while addition of mg can improve hardness, and if the amount of mg is increased, it may be necessary to increase the processing temperature appropriately during processing, but there is no other adverse effect.
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, C is the next most important component, 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 II III C III D I II III
Q：A III B II III 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 corrosion rate, hardness value and battery performance of the R6P type zinc-manganese battery are shown in 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 (which illustrate that 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 Examination of 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 | 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 (12)
1. An environment protection type Zn-Mn battery negative electrode can is composed of multi-element Zn-base alloy containing indium (0.002-0.006 wt.%), rare-earth elements (0.001-0.01 wt.%) and non-accidental harmful substances (mercury, cadmium and lead).
2. An environment protection type Zn-Mn battery negative electrode can is composed of multi-element Zn-base alloy containing in (0.002-0.006 wt.%), mg (0.001-0.018 wt.%) and non-accidental harmful substances (mercury, cadmium and lead).
3. The environment-friendly zinc-manganese battery cathode can according to claim 1, characterized in that the zinc-based alloy further contains 0.001-0.018 wt% of magnesium.
4. The negative can of claim 2, wherein the zinc-based alloy further contains 0.001-0.01 wt% of rare earth elements.
5. The negative electrode can of an environment-friendly Zn-Mn battery as claimed in any one of claims 1 to 4, wherein the Zn-based alloy further contains at least one of modified elements of Ti, zr, al, si, ag, bi and Ca in an amount of 0.001-0.009 wt%.
6. The negative electrode can of zinc-manganese battery as claimed in any one of claims 1 to 4, wherein the incidental impurities cadmium in the pure zinc as the raw material of zinc-based alloy is less than or equal to 0.003wt%, and lead is less than or equal to 0.005wt%.
7. The negative electrode can of zinc-manganese battery as claimed in any one of claims 1 to 4, wherein the incidental amount of impurity iron in said zinc-based alloy is less than or equal to 0.006wt%.
8. The negative electrode can of zinc-manganese battery as claimed in any one of claims 1 to 4, wherein the incidental impurities in said zinc-based alloy are Cu < 0.002wt% and Sn < 0.003wt%.
9. The anode can of any one of claims 1 to 4, wherein the preferable content of indium in said zinc-based alloy is 0.0025-0.0045 wt%.
10. The negative electrode can of claim 1, 3 or 4, wherein the rare earth element in the zinc-based alloy is preferably contained in an amount of 0.006 to 0.009wt%.
11. The anode can of claim 2, 3 or 4, wherein the zinc alloy Jin Zhongmei is preferably contained in an amount of 0.003-0.012 wt%.
12. The anode can for an environmentally friendly zinc-manganese battery according to claim 1, 3 or 4, wherein the rare earth element is preferably selected from at least one of lanthanum and cerium.
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| Application Number | Priority Date | Filing Date | Title |
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| CNB2003101091512A CN1328803C (en) | 2003-12-05 | 2003-12-05 | Environment-friendly zinc-manganese battery cathode can |
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| Application Number | Priority Date | Filing Date | Title |
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| CNB2003101091512A CN1328803C (en) | 2003-12-05 | 2003-12-05 | Environment-friendly zinc-manganese battery cathode can |
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| CN1547274A true CN1547274A (en) | 2004-11-17 |
| CN1328803C CN1328803C (en) | 2007-07-25 |
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Cited By (8)
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| WO2006125364A1 (en) * | 2005-04-26 | 2006-11-30 | Asia Royal Development Limited | Environmental protection zinc pot for battery, and manufacture methode of the same |
| WO2006133641A1 (en) * | 2005-06-13 | 2006-12-21 | Liangzhi Lin | A zinc-manganese dry cell and negative alloy material and manufacture method thereof |
| CN100414744C (en) * | 2005-08-16 | 2008-08-27 | 林良智 | Lead-free environment-friendly zinc-manganese dry battery |
| CN100414745C (en) * | 2005-06-13 | 2008-08-27 | 林良智 | Zinc material for environment-friendly battery and manufacturing method thereof |
| 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 |
| 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 |
| CN114628708A (en) * | 2022-03-29 | 2022-06-14 | 杭州长命电池有限公司 | Mercury-free, lead-free and cadmium-free zinc-manganese battery and manufacturing method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60175368A (en) * | 1984-02-20 | 1985-09-09 | Matsushita Electric Ind Co Ltd | Zinc-alkaline primary cell |
| BE1003681A6 (en) * | 1990-02-08 | 1992-05-19 | Acec Union Miniere | Zinc alloy for sleeves for electrochemical batteries. |
| JP3592345B2 (en) * | 1993-04-14 | 2004-11-24 | 東芝電池株式会社 | Manganese dry cell |
| CN1121729C (en) * | 2000-10-31 | 2003-09-17 | 周炳利 | High specific energy mercury-free alloy zinc powder for alkaline battery, preparation method and device thereof |
| CA2418555A1 (en) * | 2002-03-05 | 2003-09-05 | Mitsui Mining & Smelting Company, Ltd. | Zinc alloy powder for alkaline manganese dioxide cell, and negative electrode for alkaline manganese dioxide cell, and alkaline manganese dioxide cell using same |
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2003
- 2003-12-05 CN CNB2003101091512A patent/CN1328803C/en not_active Expired - Fee Related
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| 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 |
| WO2006125364A1 (en) * | 2005-04-26 | 2006-11-30 | Asia Royal Development Limited | Environmental protection zinc pot for battery, and manufacture methode of the same |
| 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 |
| CN114628708A (en) * | 2022-03-29 | 2022-06-14 | 杭州长命电池有限公司 | Mercury-free, lead-free and cadmium-free zinc-manganese battery and manufacturing 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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