CN1529369A - Zinc powder for mercuryless alkali-manganese cell and preparing method thereof - Google Patents
Zinc powder for mercuryless alkali-manganese cell and preparing method thereof Download PDFInfo
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- CN1529369A CN1529369A CNA031511767A CN03151176A CN1529369A CN 1529369 A CN1529369 A CN 1529369A CN A031511767 A CNA031511767 A CN A031511767A CN 03151176 A CN03151176 A CN 03151176A CN 1529369 A CN1529369 A CN 1529369A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The zinc powder comprises 0.045-0.072 wt% indium, 0.012-0.055 wt% bismuth, 0.0015-0.0065 wt% aluminium and/or 0.050-0.0020 wt%calcium, rest as zinc. Plumbum is added if needed. The formula possesses ideal particle size distribution. The preparing method includes following steps in sequence: adding aluminium and/or calcium in advance, melting zinc ingot, adding indium and bismuth; then carrying out alloying, atomizing, sieving procedures. Advantages of the invented product are: zinc not containing mercury, low gassing quantity, preferable electrical property, large battery capacity, shock resistance and good stability in storage. Features of the preparing method are: high efficiency, high rate of finished products, low production cost, ideal particle size distribution and particle shape of zinc powder.
Description
Technical field
The invention belongs to the battery material field, relate to a kind of alkaline battery alloy zinc powder, especially a kind of mercury-free alkaline manganese dioxide battery zinc powder and preparation method thereof.
Background technology
As everyone knows, in the alkaline battery electrolyte of zinc as negative pole, the reduction potential of water is about-0.828V, and the oxidizing potential of zinc is about-1.211V, therefore, zinc and water can evolving hydrogen reaction take place and cause self-discharge of battery or " gas rises ", climb alkali even the phenomenon of blasting; In addition, after producing hydrogen, also can increase the interior resistance of battery.So traditional generally all can adopt the amalgamation zinc powder with zinc as the alkaline battery of negative electrode active material, wherein generally between 3～6wt%, the adding of mercury has improved overpotential of hydrogen evolution to mercury content, can reduce or avoid separating out of hydrogen.Yet mercury is that a kind of utmost point poisonous substance matter and chemical property are more stable, and long-term pollution and harm will be caused to environment for human survival and biological environment in the discarded back of mercurous battery.But, owing to contain mercury cell and have big capacity and good heavy-current discharge characteristic, made in the civilian battery consumption demand of its various countries since nearly ten years keep continuing always, growth fast, especially all the more so in developing country.But become today of knowing together in the whole world in sustainable development, developing environmental protection problem is more and more paid attention to by countries in the world.In order to protect environment, developed country set about developing low mercury cell and mercury-free battery already, and China's formal provision forbids producing the battery that mercury content is higher than battery quality 0.0001% from January 1st, 2005.Therefore, the development mercury-free alkaline manganese dioxide battery meets national industrial policies with zinc powder, and environmental protection is had far reaching significance.Simultaneously, along with mercury-free alkaline manganese dioxide battery production with 30～40% speed increases, the development mercury-free battery also have good social benefit and economic benefit with zinc powder.
The height of mercury content directly influences the gassing rate of battery in the alkaline cell zinc dust, and generally the gassing rate of zinc powder increases along with the reduction of mercury content, so, merely reducing the content of mercury in the battery zinc powder, the performance of battery just is difficult to meet the demands.Minority developed country has succeeded in developing alloy zinc powder without mercury in succession the beginning of the nineties, but from open content of coming out, and its important indicator gassing rate that can reflect the mercury less zinc powder quality is all greater than 0.08ml/5g3d, and is difficult to realize big electric current, the discharge of high specific energy.In addition, Chinese patent application 00132203.6 discloses " high specific energy alloy zinc powder without mercury for alkaline cell and its preparation method and equipment therefor thereof ", it has mixed rare earth element in battery zinc powder, the gassing rate of zinc powder under 45 ℃ of constant temperature is 0.03～0.04ml/5g3d, compares with the gassing rate that contains mercury zinc powder (about 0.01ml/5g3d) and still has certain gap.
Because the special role of mercury in alkaline Mn cell, in the process of development mercury-free alkaline manganese dioxide battery, battery circle scholars are seeking suitable for the mercury additive always.Present for the mercury additive be In, Bi, Pb, Al, Ca is several reaches common understanding substantially, but which specifically selects for use plant additive, their addition, and how between battery performance such as gassing rate and production cost, obtain rational balance etc. and then be still the problem that needs to continue research.In addition, because the fusing point of various additives is different, thereby its adding opportunity and addition sequence different in process of production, can directly influence the alloying process of zinc powder, and then influence microstructures such as the pattern of zinc powder and crystal orientation structure, finally cause the difference of battery electrical property.
Summary of the invention
Technical problem to be solved by this invention is the mercury-free alkaline manganese dioxide battery zinc powder that the low and superior electrical property of a kind of no mercury, gassing rate of compliance with environmental protection requirements is provided at above-mentioned prior art present situation.
Technical problem to be solved by this invention is that a kind of method for preparing above-mentioned mercury-free alkaline manganese dioxide battery with zinc powder is provided at above-mentioned prior art present situation.
The present invention solves the technical scheme that above-mentioned first technical problem adopts: this kind mercury-free alkaline manganese dioxide battery zinc powder, it is characterized in that, this zinc powder contains the indium (In) of 0.045～0.072wt%, the bismuth (Bi) of 0.012～0.055wt%, the aluminium (Al) of 0.0015～0.0065wt% and/or the calcium (Ca) of 0.0050～0.020wt%, and surplus is zinc (Zn).
This kind mercury-free alkaline manganese dioxide battery also contains the lead (Pb) of 0.050+0.005wt% with zinc powder.
The particle size distribution of this zinc powder is as follows:
The granularity weight percentage
＞850 μ m (+20 order) 0%
850 μ m～450 μ m (20～40 order) 0～15%
450 μ m～250 μ m (40～60 order) 15～35%
250 μ m～150 μ m (60～100 order) 30～55%
150 μ m～100 μ m (100～150 order) 10～30%
100 μ m～75 μ m (150～200 order) 5～25%
＜75 μ m (200 order) 0～15%
The particle of the existing needle-like of pattern of this zinc powder has spherical particle again, and wherein based on needle-like, the content of elongated piece is 50～65%.
Zinc is a kind of more active metal, it easily produces the electrochemistry unsteadiness under the effect of denier beavy metal impurity, the self-dissolving tendency is arranged in aqueous slkali, releasing hydrogen gas, both caused the leakage of battery inflatable, again easily owing to self-dissolving produces self discharge, the consumable anode active material, finally cause battery failure and scrap, therefore must add corrosion inhibiter, it is kept relative stability when battery storage, when battery operated, can show its electro-chemical activity again.
Al and Ca can reduce the overdischarge gassing rate, and Al can improve oxidative resistance simultaneously, can also form solid solution with zinc, and Ca can make the zinc powder spheroidization, and makes particle surface smooth full.But because Al fusing point height, the zinc powder that contains too high Al is difficult to make; And zinc powder is spheroidization too, the battery of making, and because of its contact resistance increases, vibration resistance is poor, so the content of Al and Ca should be controlled appropriately.
In can improve the separate out overpotential of hydrogen at the kirsite particle surface, be of great benefit to reducing gassing rate, but because In costs an arm and a leg, price per ton about about 1,000,000 yuans, therefore also should have a suitable scope greatly.
Bismuth can improve the separate out overpotential of hydrogen at zinc surface equally, but excessive gassing rate effect and not obvious is separated out in overdischarge.
Lead can make zinc surface hydrogen separate out the overpotential raising, and good anti-corrosion is arranged, but excessive, can bring harm to the contactee in the course of time.
Prescription is to the influence of distribution of particles:
Each trace element influences alloying process together in the prescription, because their difference, the pattern of zinc powder and the particle size distribution of particle also can be far from each other, and the particle size distribution of zinc particle and pattern have obvious influence to the performance of battery.
Find after deliberation, the particle of needle-like is more more favourable to the performance of battery than spheric granules, in addition, the particle size distribution of zinc powder, we find, desirable particle size distribution is preferably in 100 μ m～250 μ m, electrical properties such as its gassing rate and battery storage stability are all better, but the input and output rate of producing is lower, and production cost is higher, apparent density is low slightly and influence battery capacity, therefore, take all factors into consideration the each side actual conditions, we find that above-mentioned particle size distribution can guarantee that the performance of battery each side is all more satisfactory, and the production efficiency height, good product quality and stablizing.
Compared with prior art, the invention has the advantages that: 1, do not have mercury fully, thereby meet environmental protection requirement; 2, gassing rate has reached the level that contains mercury zinc powder below 0.01ml/5g3d, far below existing mercury less zinc powder; 3, superior electrical property, the battery capacity of making is big, shock resistance and battery storage stability are all better.
The present invention solves above-mentioned second technical scheme that technical problem adopted: this kind prepares the method for mercury-free alkaline manganese dioxide battery with zinc powder, it is characterized in that aluminium and/or the calcium that fusing point is high just places the Medium frequency induction furnace bottom when beginning to melt earlier, after melting fully Deng zinc ingot metal, in furnace temperature is to add indium and bismuth under 550 ℃～640 ℃ conditions, carry out alloying, stirred equably continuously 3～4 minutes, intermediate frequency furnace being threaded to 85KW heated up 8～14 minutes again, the control temperature is 650～720 ℃, stop heating then, pour into tundish while hot and carry out atomization process, sieve then and remove the particle of granularity, carry out the uniform particles processing at last and get product greater than 850 μ m.
Compared with prior art, the invention has the advantages that: the production efficiency height, the rate of finished products height, production cost is low, and the granule-morphology of product zinc powder and particle size distribution are good.
Embodiment
Below in conjunction with embodiment the present invention is described in further detail.
The preparation technology who is adopted among the embodiment is basic identical the difference to some extent except that adding metallic element, all be that aluminium and/or the calcium that fusing point is high just places the Medium frequency induction furnace bottom when beginning to melt earlier, after melting fully Deng zinc ingot metal, in furnace temperature is to add indium and bismuth under 550 ℃～640 ℃ conditions, and look prescription and need add lead, carry out alloying, stirred equably continuously 3～4 minutes, intermediate frequency furnace being threaded to 85KW heated up 8～14 minutes again, the control temperature is 650～720 ℃, stop heating then, pour into tundish while hot and carry out atomization process, sieve then and remove the particle of granularity greater than 850 μ m, the gained zinc powder is stirred gets product uniform particlesization at last.
Embodiment one
The present embodiment zinc powder is formed and particle size distribution sees Table 1.
The composition of zinc powder and particle size distribution among table 1 embodiment one
| Title | Test item | Detection method | Testing result |
| Chemical analysis | Indium (In) | Atomic absorption spectrophotometry | ????0.063％ |
| Bismuth (Bi) | ????0.028％ | ||
| Plumbous (Pb) | ????----- | ||
| Aluminium (Al) | ????0.0020％ | ||
| Calcium (Ca) | ????0.016％ | ||
| Mercury (Hg) | The cold atom absorption spectrophotometry | Do not detect | |
| Zinc oxide (ZnO) | The ammonium salt solution polarography | ????0.24％ | |
| Iron (Fe) | Atomic absorption spectrophotometry (enrichment of element) | ????0.0002％ | |
| Copper (Cu) | ????0.00001％ | ||
| Nickel (Ni) | ????0.00004％ | ||
| Cadmium (Cd) | Atomic absorption spectrophotometry | ????0.0002％ | |
| Arsenic (As) | AAS | ????＜0.00002％ | |
| Particle size distribution | ???＞850μm | The dry screen point-score | ????0 |
| ???850～450μm | ????3.2％ | ||
| ???450～250μm | ????20.0％ | ||
| ???250～150μm | ????49.2％ | ||
| ???150～100μm | ????16.0％ | ||
| ???100～75μm | ????8.5％ | ||
| ???＜75μm | ????2.9％ | ||
| Pattern | Spherical and elongated piece, elongated piece content is 60% | ||
The present embodiment zinc powder relatively sees Table 2 with the electrical property that contains mercury zinc powder.
By testing result and table 2 as can be seen, the present embodiment mercury less zinc powder is compared as follows with the performance that contains mercury zinc powder:
A, for gassing rate, the gassing rate of mercury less zinc powder is good slightly;
B, discharge time, mercury less zinc powder will be better than containing mercury zinc powder greatly;
C, open circuit voltage, about the same;
D, short circuit current and apparent gravity are because the relation of mercury contains mercury zinc powder and is better than mercury less zinc powder;
E, oxidizability aspect, mercury less zinc powder are better than and contain mercury zinc powder.
Zinc powder compares with the electrical property that contains mercury zinc powder among table 2 embodiment one
Embodiment two
The present embodiment zinc powder is formed and particle size distribution sees Table 3.
The present embodiment zinc powder relatively sees Table 4 with the electrical property that contains mercury zinc powder.
Zinc powder compares with the electrical property that contains mercury zinc powder among table 4 embodiment two
By testing result and table 4 as can be seen, the present embodiment mercury less zinc powder is compared as follows with the performance that contains mercury zinc powder:
A, for gassing rate, the two is about the same, mercury less zinc powder good slightly;
B, discharge time, mercury less zinc powder obviously is better than containing mercury zinc powder;
C, open circuit voltage, mercury less zinc powder are better than containing mercury zinc powder;
D, short circuit current are more or less the same, and contain the good slightly of mercury zinc powder;
E, oxidizability aspect, mercury less zinc powder is better than containing mercury zinc powder greatly;
F, apparent density because mercury is arranged, contain mercury zinc powder and are higher than mercury less zinc powder.
The composition of zinc powder and particle size distribution among table 3 embodiment two
| Title | Test item | Detection method | Testing result |
| Chemical analysis | Indium (In) | Atomic absorption spectrophotometry | ????0.056％ |
| Bismuth (Bi) | ????0.029％ | ||
| Plumbous (Pb) | ????0.048％ | ||
| Aluminium (Al) | ????0.0061％ | ||
| Calcium (Ca) | ????---- | ||
| Mercury (Hg) | The cold atom absorption spectrophotometry | ????9×10-6％ | |
| Zinc oxide (ZnO) | The ammonium salt solution polarography | ????0.14％ | |
| Iron (Fe) | Atomic absorption spectrophotometry (enrichment of element) | ????0.0002％ | |
| Copper (Cu) | ????＜0.0002％ | ||
| Nickel (Ni) | ????＜0.0002％ | ||
| Cadmium (Cd) | Atomic absorption spectrophotometry | ????＜0.0003％ | |
| Arsenic (As) | AAS | ||
| Particle size distribution | ????＞850μm | The dry screen point-score | ????0 |
| ????850～450μm | ????5.8％ | ||
| ????450～250μm | ????33％ | ||
| ????250～150μm | ????32％ | ||
| ????150～100μm | ????21.5％ | ||
| ????100～75μm | ????6.7％ | ||
| ????＜75μm | ????1.0％ | ||
| Pattern | Spherical and elongated piece, elongated piece content is 52% | ||
Embodiment three
The present embodiment zinc powder is formed and particle size distribution sees Table 5.
The present embodiment zinc powder relatively sees Table 6 with the electrical property that contains mercury zinc powder.
The composition of zinc powder and particle size distribution among table 5 embodiment three
| Title | Test item | Detection method | Testing result |
| Chemical analysis | Indium (In) | Atomic absorption spectrophotometry | ????0.049％ |
| Bismuth (Bi) | ????0.053％ | ||
| Plumbous (Pb) | ????---- | ||
| Aluminium (Al) | ????---- | ||
| Calcium (Ca) | ????0.020％ | ||
| Mercury (Hg) | The cold atom absorption spectrophotometry | Do not detect | |
| Zinc oxide (ZnO) | The ammonium salt solution polarography | ????0.21％ | |
| Iron (Fe) | Atomic absorption spectrophotometry (enrichment of element) | ????0.0002％ | |
| Copper (Cu) | ????0.00001％ | ||
| Nickel (Ni) | ????0.00003％ | ||
| Cadmium (Cd) | Atomic absorption spectrophotometry | ????0.00001％ | |
| Arsenic (As) | AAS | ????＜0.00002％ | |
| Particle size distribution | ????＞850μm | The dry screen point-score | ????0 |
| ????850～450μm | ????2.0％ | ||
| ????450～250μm | ????17.2％ | ||
| ????250～150μm | ????25.5％ | ||
| ????150～100μm | ????28.4％ | ||
| ????100～75μm | ????18.7％ | ||
| ????＜75μm | ????8.2％ | ||
| Pattern | Spherical and elongated piece, elongated piece content is 63% | ||
By testing result and table 6 as can be seen, the present embodiment mercury less zinc powder is compared as follows with the performance that contains mercury zinc powder:
A, for gassing rate, the two is about the same, mercury less zinc powder good slightly;
B, discharge time, mercury less zinc powder obviously is better than containing mercury zinc powder;
C, open circuit voltage, mercury less zinc powder are better than containing mercury zinc powder;
D, short circuit current are more or less the same, and contain the good slightly of mercury zinc powder;
E, oxidizability aspect, mercury less zinc powder is better than containing mercury zinc powder greatly;
F, apparent density because mercury is arranged, contain mercury zinc powder and are higher than mercury less zinc powder.
Zinc powder compares with the electrical property that contains mercury zinc powder among table 6 embodiment three
Embodiment four
The present embodiment zinc powder is formed and particle size distribution sees Table 7.
The present embodiment zinc powder relatively sees Table 8 with the electrical property that contains mercury zinc powder.
Zinc powder compares with the electrical property that contains mercury zinc powder among table 8 embodiment four
By testing result and table 8 as can be seen, the present embodiment mercury less zinc powder is compared as follows with the performance that contains mercury zinc powder:
A, for gassing rate, the two is about the same, mercury less zinc powder good slightly;
B, discharge time, mercury less zinc powder obviously is better than containing mercury zinc powder;
C, open circuit voltage, mercury less zinc powder are better than containing mercury zinc powder;
D, short circuit current are more or less the same, and contain the good slightly of mercury zinc powder;
E, oxidizability aspect, mercury less zinc powder is better than containing mercury zinc powder greatly;
F, apparent density because mercury is arranged, contain mercury zinc powder and are higher than mercury less zinc powder.
The composition of zinc powder and particle size distribution among table 7 embodiment four
| Title | Test item | Detection method | Testing result |
| Chemical analysis | Indium (In) | Atomic absorption spectrophotometry | ????0.069％ |
| Bismuth (Bi) | ????0.018％ | ||
| Plumbous (Pb) | ????---- | ||
| Aluminium (Al) | ????0.0025％ | ||
| Calcium (Ca) | ????0.0072％ | ||
| Mercury (Hg) | The cold atom absorption spectrophotometry | Do not detect | |
| Zinc oxide (ZnO) | The ammonium salt solution polarography | ????0.20％ | |
| Iron (Fe) | Atomic absorption spectrophotometry (enrichment of element) | ????0.0002％ | |
| Copper (Cu) | ????0.00001％ | ||
| Nickel (Ni) | ????0.00003％ | ||
| Cadmium (Cd) | Atomic absorption spectrophotometry | ????0.00001％ | |
| Arsenic (As) | AAS | ????＜0.00002％ | |
| Particle size distribution | ????＞850μm | The dry screen point-score | ????0 |
| ????850～450μm | ????2.0％ | ||
| ????450～250μm | ????21.2％ | ||
| ????250～150μm | ????45.5％ | ||
| ????150～100μm | ????18.5％ | ||
| ????100～75μm | ????10.4％ | ||
| ????＜75μm | ????2.4％ | ||
| Pattern | Spherical and elongated piece, elongated piece content is 64% | ||
Claims (5)
1, a kind of mercury-free alkaline manganese dioxide battery zinc powder, it is characterized in that, this zinc powder contains the indium (In) of 0.045～0.072wt%, the bismuth (Bi) of 0.012～0.055wt%, the aluminium (Al) of 0.0015～0.0065wt% and/or the calcium (Ca) of 0.0050～0.020wt%, and surplus is zinc (Zn).
2, mercury-free alkaline manganese dioxide battery zinc powder according to claim 1 is characterized in that also containing the lead (Pb) of 0.050 ± 0.005wt%.
3, mercury-free alkaline manganese dioxide battery zinc powder according to claim 1 and 2 is characterized in that the particle size distribution of this zinc powder is as follows:
The granularity weight percentage
＞850 μ m (+20 order) 0%
850 μ m～450 μ m (20～40 order) 0～15%
450 μ m～250 μ m (40～60 order) 15～35%
250 μ m～150 μ m (60～100 order) 30～55%
150 μ m～100 μ m (100～150 order) 10～30%
100 μ m～75 μ m (150～200 order) 5～25%
＜75 μ m (200 order) 0～15%
4, mercury-free alkaline manganese dioxide battery zinc powder according to claim 3 is characterized in that the particle of the existing needle-like of pattern of this zinc powder has spherical particle again, and wherein based on needle-like, the content of elongated piece is 50～65%.
5, a kind of method for preparing mercury-free alkaline manganese dioxide battery as claimed in claim 1 with zinc powder, it is characterized in that aluminium and/or the calcium that fusing point is high just places the Medium frequency induction furnace bottom when beginning to melt earlier, after melting fully Deng zinc ingot metal, in furnace temperature is to add indium and bismuth under 550 ℃～640 ℃ conditions, carry out alloying, stirred equably continuously 3～4 minutes, intermediate frequency furnace being threaded to 85KW heated up 8～14 minutes again, the control temperature is 650～720 ℃, stop heating then, pour into tundish while hot and carry out atomization process, sieve then and remove the particle of granularity, carry out the uniform particles processing at last and get product greater than 850 μ m.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA031511767A CN1529369A (en) | 2003-09-25 | 2003-09-25 | Zinc powder for mercuryless alkali-manganese cell and preparing method thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA031511767A CN1529369A (en) | 2003-09-25 | 2003-09-25 | Zinc powder for mercuryless alkali-manganese cell and preparing method thereof |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006133641A1 (en) * | 2005-06-13 | 2006-12-21 | Liangzhi Lin | A zinc-manganese dry cell and negative alloy material and manufacture method thereof |
| CN102011028A (en) * | 2010-11-04 | 2011-04-13 | 宁波双鹿能源科技有限公司 | Zinc powder used as electrode and preparation method thereof |
| CN104988353A (en) * | 2015-07-07 | 2015-10-21 | 江苏冶建锌业有限公司 | Cadmium-free lead-free super-fine zinc alloy powder and preparation method thereof |
-
2003
- 2003-09-25 CN CNA031511767A patent/CN1529369A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006133641A1 (en) * | 2005-06-13 | 2006-12-21 | Liangzhi Lin | A zinc-manganese dry cell and negative alloy material and manufacture method thereof |
| CN102011028A (en) * | 2010-11-04 | 2011-04-13 | 宁波双鹿能源科技有限公司 | Zinc powder used as electrode and preparation method thereof |
| CN102011028B (en) * | 2010-11-04 | 2014-11-26 | 宁波双鹿能源科技有限公司 | Zinc powder used as electrode and preparation method thereof |
| CN104988353A (en) * | 2015-07-07 | 2015-10-21 | 江苏冶建锌业有限公司 | Cadmium-free lead-free super-fine zinc alloy powder and preparation method thereof |
| CN104988353B (en) * | 2015-07-07 | 2017-01-11 | 江苏冶建锌业有限公司 | Cadmium-free lead-free super-fine zinc alloy powder and preparation method thereof |
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