CN1060697C - Composition and method for chemical copper plating of rare-earth containing nickle-based hydrogen storage alloy - Google Patents
Composition and method for chemical copper plating of rare-earth containing nickle-based hydrogen storage alloy Download PDFInfo
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- CN1060697C CN1060697C CN95101640A CN95101640A CN1060697C CN 1060697 C CN1060697 C CN 1060697C CN 95101640 A CN95101640 A CN 95101640A CN 95101640 A CN95101640 A CN 95101640A CN 1060697 C CN1060697 C CN 1060697C
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Abstract
The present invention relates to a formula and a process which are used for chemical copper plating of a hydrogen storage alloy powder. The formula of the present invention comprises the components of water as a solvent, 0.5 to 50 g/cubic liter of copper salt, 0.1 to 28 ml/ cubic liter of acid, 2 to 20 g/cubic liter of organic hydroxycarboxylic acid and 0.5 to 10 g/cubic liter of lanthanum-rich rare earth; in the method of the present invention, the hydrogen storage alloy powder is poured in a chemical copper plating liquid by stirring at a room temperature, and the chemical copper plating liquid and the hydrogen storage alloy powder are continuously stirred for 15 to 80 minutes, and filtered and dried after being stirred. The formula of the present invention reduces the loss of rare earth in the hydrogen storage alloy powder, enhances the capacity of the hydrogen storage alloy powder, and has the advantages of no toxic reagent, no environmental pollution, simple method, easy operation, and uniform thickness of the copper plating.
Description
The present invention relates to a kind of electroplate liquid formulation of no current electroless plating of rare-earth Ni-base hydrogen bearing alloy powder and the technology of electroless plating, more precisely is the prescription of chemical bronze plating liquid of rare-earth Ni-base hydrogen bearing alloy powder and the technology of electroless copper.
Rare-earth Ni-base hydrogen bearing alloy is the excellent material that is widely used in nickel-hydrogen battery negative pole at present.But it has two shortcomings: the first is put in the hydrogen process inhaling repeatedly, and lattice parameter changes, and its volume is increased when inhaling hydrogen, shrinks when putting hydrogen, thereby causes the efflorescence of alloy.For example: the LaNi of 80 μ m (200 order) granularity
5After 10 circulations, 99.5% alloy powder has become 40 μ m (400 order).It two is that the alloy powder surface is very easily oxidized, forms the passive state oxide film and loses activity.
Electroless copper is the effective means that solution hydrogen-storage alloy powder oxidation and efflorescence are inscribed together.The advantage of electroless copper method is that copper facing powder good conductivity activates fast.This method is fit to hydrogen-storage alloy powder particulate irregularity, all copper facing effectively on the particle of any pattern again.
The Japanese documentation spy opens flat 3-247735 proposition is easy to see through hydrogen on rare-earth Ni-base hydrogen bearing alloy powder sub-surface coats with the method for no current electroless plating palladium, copper, wherein a kind of metallic membrane of nickel.
The prescription that the spy opens clear 62-22370 proposition chemical bronze plating liquid is copper sulfate 15 gram/liters, and sodium bicarbonate is 10 gram/liters, Seignette salt 30 gram/liters, sodium hydroxide 20 gram/liters, (37%) 100 milliliter/liter of formaldehyde, 24 ℃ of temperature.
(novel hydrogen storage material and application scientific seminar paper compilation thereof such as Qin Guangrong; " 863 " hydrogen storage material special topic group, December nineteen ninety, hydrogen-storage alloy particulate chemistry copper-plating technique performance study P193); the chemical bronze plating liquid that proposes is EDTA (disodium ethylene diamine tetraacetate, C
10H
14N
2O
3Na
2 2H
2O) 3.5 grams/100 ml waters, copper sulfate 3.5 gram/100 ml waters mix EDTA solution and the copper-bath volume ratio by 1: 1 again.Its copper-plating technique is: at first the rare-earth Ni-base hydrogen bearing alloy powder is carried out sensitization with tindichloride solution (3.0 gram tindichloride are dissolved in the 100ml water) and handle, use PdCl again
2(0.1 gram PdCl
2Be dissolved in 100 ml waters) carry out activation treatment.Hydrogen-storage alloy powder particles adding concentration after the activation is 30% formaldehyde, and is stand-by.The solution that the EDTA liquid for preparing and copper sulfate solution were mixed in 1: 1 by volume, slowly be heated to 47-48 ℃, adjust PH=10～12 of above-mentioned mixing solutions with the sodium hydroxide solution of 1N, pour into then in the good hydrogen-storage alloy powder to be plated of activation, under 47-48 ℃ temperature, continue to stir, up on all particulates, all plating copper film, use the deionized water wash clean, in vacuum drying oven, powder is dried.
The investigator who has (nickle/metal hydrides battery, Ministry of Machine-building and Electronics Industry's power supply staff intelligence net, on July 15th, 1991, P38-42, the nickle/metal hydrides store battery of employing micro-capsule formula alloy) proposes hydrogen-storage alloy powder (LaNi
2.5Co
2.4Al
0.3) in the aqueous hydrochloric acid of tindichloride, activate, the hydrogen-storage alloy powder after will activating then in 30 ℃ of dippings, stirring, carries out electroless copper in containing cupric tartrate (II), formaldehyde and sodium hydroxide chemical bronze plating liquid.
(Journal of Alloys and Compounds 182,1992,321-330), the prescription of used chemical plating copper liquid is to contain 1.5 gram copper sulfate, 0.8 milliliter of sulfuric acid in 100 milliliters chemical bronze plating liquid to Choong-Ngeon Park.Its technology is with 2.5 gram rare-earth Ni-base hydrogen bearing alloy powder (its particulate size for less than 100 μ m), is immersed in 100 milliliters of above-mentioned chemical bronze plating liquids 1-5 and divides kind under room temperature.
The technical recipe that has in above-mentioned reference document need carry out pretreatment process such as sensitization, activation, has increased cost, and technical process is long, complexity, and strengthened the solution loss of rare-earth Ni-base hydrogen bearing alloy powder middle-weight rare earths again; And the Recipe that has has used for example formaldehyde of deleterious chemical reagent, has polluted environment, influences operator's health.The prescription and the technology thereof of the chemical bronze plating liquid that Choong-Ngeon Park is proposed, though this prescription and technology thereof do not need pretreatment process such as sensitization, activation, also without deleterious chemical reagent such as formaldehyde, but the shortcoming that the time that still exists electroless copper is restive, because reaction is very fierce, many platings one minute, the rare-earth Ni-base hydrogen bearing alloy powder after the plating spontaneous combustion of will generating heat; Plated less 1 minute, the quality of the copper film that coats does not just reach requirement, and exist the rare-earth Ni-base hydrogen bearing alloy powder in the electroless copper process, the shortcoming that the rare earth solution loss is big, the rare earth solution loss is greatly the shortcoming that substitution method itself is brought, come on the copper clad, a part of rare earth in the rare-earth Ni-base hydrogen bearing alloy powder just dissolves, and has destroyed CaCu
5Structure descends the hydrogen storage performance of rare-earth Ni-base hydrogen bearing alloy powder to some extent.
Purpose of the present invention just is to study the prescription of the chemical bronze plating liquid of preparing a kind of new rare-earth Ni-base hydrogen bearing alloy powder, makes the skin of rare-earth Ni-base hydrogen bearing alloy powder plate layer of copper, makes it be difficult for oxidation and efflorescence; In prescription, do not use deleterious chemical reagent, free from environmental pollution, do not influence health of operators; And reduce solution loss again widely at electroless copper process middle-weight rare earths, improve the capacity of copper-clad rare-earth Ni-base hydrogen bearing alloy powder.
Another object of the present invention is to work out a kind of new rare-earth Ni-base hydrogen bearing alloy efflorescence copper coating, make its technology simple, flow process shortens, reduce the fierce degree of reaction greatly, make reaction process be easy to control, make the rare-earth Ni-base hydrogen bearing alloy powder after copper facing not have heating, the phenomenon of no spontaneous combustion.
The prescription of the chemical bronze plating liquid of a kind of rare-earth Ni-base hydrogen bearing alloy powder of the present invention, with water is solvent, a kind of mantoquita that in chemical bronze plating liquid, contains 0.5～50 gram/liter, 0.1 a kind of acid of～28 milliliters/liter, a kind of organic hydroxy-acid of 2-20 gram/liter, the lanthanum rich rare earth of 0.5-10 gram/liter (total amount of rare earth ∑ RE＞99.0%).
Said a kind of mantoquita is wherein a kind of of copper sulfate, cupric chloride, cupric nitrate, neutralized verdigris, is good with copper sulfate, cupric chloride a kind of mantoquita wherein again; Said a kind of acid is a kind of acid wherein of sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid, acetic acid, again with a kind of acid wherein of sulfuric acid, hydrochloric acid for well; Said a kind of organic hydroxy-acid is wherein a kind of of citric acid, tartrate, lactic acid, oxysuccinic acid, is good with citric acid, tartrate a kind of organic hydroxy-acid wherein again.Used lanthanum rich rare earth (total amount of rare earth ∑ RE＞99%) contains lanthanum 20-90% (weight percentage) and is advisable.Used aqueous solvent is distilled water, ion exchanged water a kind of water wherein.
At cupric ion (Cu
2+) during with the directed replacement(metathesis)reaction of hydrogen-storage alloy element, add the stablizer of a certain amount of organic hydroxy-acid as reaction, when especially adding a kind of acid wherein of citric acid, tartrate, can reduce the fierce degree of reaction, reaction is quantitatively gently carried out as reaction stabilizer.And organic hydroxy-acid, especially citric acid, tartrate is put the hydrogen activity to the suction of hydrogen-storage alloy powder in the plating process that certain restraining effect is also arranged, and makes plating process safety, effectively, and the hydrogen-storage alloy powder after the plating can not generate heat, spontaneous combustion.
In chemical plating fluid, add an amount of lanthanum rich rare earth [∑ RE＞99.0% contains lanthanum 20-90% (weight percentage)], can reduce loss, can improve the weight ratio capacity of copper-clad hydrogen-storage alloy powder again at plating process middle-weight rare earths.
With the JSM-840 scanning electronic microscope hydrogen-storage alloy powder of copper-clad has been carried out morphology analysis; (see figure 1) can see that copper-clad hydrogen-storage alloy powder surface is the round shaped grain of projection from the photo; distribution is uniform; the copper layer border of the spherical microcapsule of this layer is adjacent with circle; produce many micro-pores, help inhaling and put the hydrogen process, make the copper layer both protect alloy as a string bag; make it be difficult for oxidation and efflorescence, do not influence its hydrogen storage capacity again.
In order further to confirm the homogeneity of copper plate, carried out the high pressure breakthrough experiment at copper facing particle surface pit and groove place with the TN-5500 energy spectrometer, under 16KV voltage, all have only the copper peak to occur, and all substrates element and copper occur simultaneously under 17KV voltage, its result and plane, high spot are consistent, copper-clad layer thickness unanimity on the hydrogen-storage alloy powder is described, has plated copper equally equably at particulate pit, groove place.
The method of the electroless copper of a kind of rare-earth Ni-base hydrogen bearing alloy powder of the present invention, with water is solvent, prescription by above-mentioned chemical bronze plating liquid, make a kind of mantoquita that contains 0.5～50 gram/liter in its chemical bronze plating liquid, 0.1 a kind of acid of～28 milliliters/liter, a kind of organic hydroxy-acid of 2-20 gram/liter, the lanthanum rich rare earth of 0.5-10 gram/liter (total amount of rare earth ∑ RE＞99.0%); The mean particle size for the treatment of copper-plated rare-earth Ni-base hydrogen bearing alloy powder is at 40～150 μ m, and the weight (gram) for the treatment of copper-plated rare-earth Ni-base hydrogen bearing alloy powder and the volume (liter) of chemical bronze plating liquid are than being 1～80 to restrain: 1 liter; To treat while stirring that at room temperature copper-plated rare-earth Ni-base hydrogen bearing alloy powder pours in the chemical bronze plating liquid, and continue to stir 15-80 minute, and stop to stir, filter, washing, oven dry.
In the process of electroless copper, the mean particle size for the treatment of copper-plated rare-earth Ni-base hydrogen bearing alloy powder is at 40～150 μ m, and the weight (gram) for the treatment of copper-plated rare-earth Ni-base hydrogen bearing alloy powder and the volume (liter) of chemical bronze plating liquid are than being 1～80 to restrain: 1 liter; Feed intake time that the back continue to stir that finishes is 15-80 minute, is advisable with 20～60 minutes again, can not influence the quality of plating back hydrogen-storage alloy powder between at this moment in scope inherence ± 10 minute.The speed that stirs makes hydrogen-storage alloy powder be evenly distributed in chemical bronze plating liquid and is advisable, but its stirring velocity with 50-120 rev/min for better.Filter with the method that the one of ordinary skill in the art all knows, for example filter with B, wash 2～10 times with water after, again with after the alcohol washing, in 30-60 ℃ of oven dry.Be lower than 30 ℃ of oven dry, the speed of oven dry is too slow.
If in chemical bronze plating liquid, do not add lanthanum rich rare earth (∑ RE＞99.0%), in substitution method electroless copper process, the rare earth loss amount of its rare-earth Ni-base hydrogen bearing alloy powder self is directly proportional with the copper facing amount, be that the copper facing amount is in 1～50% (weight percentage, down together) in the scope, the loss amount of rare earth is between 0.33～18% (weight percentage, down together), wherein except that the displacement loss, also comprise solution loss.But, in chemical bronze plating liquid, behind the lanthanum rich rare earth of adding sufficient quantity, then can significantly reduce the loss of rare earth nickel hydrogen-storage alloy powder middle-weight rare earths, the minimizing amplitude is 10-50%, can improve the capacity 10-30mAh/g of copper-clad rare-earth Ni-base hydrogen bearing alloy powder again.
In addition, when in the chemical bronze plating liquid of acid such as mantoquita such as organic hydroxy-acid's such as adding citric acid, tartrate not copper sulfate and sulfuric acid, coating copper, the plating time is short, and variable range is narrow, generally to control time＜5 minute of plating, the spontaneous combustion of will generating heat of rare earth nickel hydrogen-storage alloy powder after the bull point clock plating, the copper amount error of few one minute its plating will＞10%.
The simulated battery method is adopted in the cubic content measurement of rare-earth Ni-base hydrogen bearing alloy powder.The making of battery is that the nickel bar point that will shear is welded on the nickel foam sheet, tested hydrogen-storage alloy powder, mixes well with alcohol in the ratio and the nickel powder of 1: 1 (weight ratio), and the nickel foam that is coated in 20mm * 20mm is online, dries.With 4 tons/square centimeter pressure compactings in flakes, do anodal with excessive sintered nickel electrode, with the nylon nonwoven fabrics is barrier film, puts into tetrafluoroethylene simulation opening Experimental cell tube, and adding the 6N potassium hydroxide aqueous solution is electrolytic solution, based on Ni/MH cell reaction principle, adopt constant current discharge, charging current is 0.2c, 5 hours duration of charging, discharging current 0.2c is put till the 1.0V.Under 25 ℃ temperature 10 times repeatedly.
The advantage of the electroless copper liquid formula of rare-earth Ni-base hydrogen bearing alloy powder of the present invention is:
1. in prescription of the present invention, reduced loss amount at electroless copper process middle-weight rare earths Ni-base hydrogen bearing alloy powder middle-weight rare earths, improved the capacity 10-30mAh/g of the hydrogen-storage alloy powder behind the copper-clad again owing to added lanthanum rich rare earth.
2. owing to added organic hydroxy-acids such as citric acid, tartrate in the prescription of the present invention, make that the hydrogen-storage alloy powder after the copper facing does not have heating, no dieseling.
3. in prescription of the present invention, do not use deleterious chemical reagent, free from environmental pollution, do not influence health of operators.
The advantage of the method for the electroless copper of a kind of rare-earth Ni-base hydrogen bearing alloy powder of the present invention is:
1. electroless copper plating method of the present invention has saved sensitization, the activation treatment process, and technology is simple, has shortened flow process; Owing to added organic hydroxy-acids such as citric acid, tartrate, make reaction process be easy to control, make that the rare-earth Ni-base hydrogen bearing alloy powder after copper facing does not have heating, the phenomenon of no spontaneous combustion.
2. make that with electroless copper plating method of the present invention copper-plated thickness is even; copper-clad layer on the rare-earth Ni-base hydrogen bearing alloy powder behind the resulting copper-clad has formed the protective layer of string bag shape at hydrogen-storage alloy particle skin; both reduced contacting of hydrogen-storage alloy powder and water, oxygen, alkaline matter; make it be difficult for oxidation, reached anti-atomizing purpose again.
The morphology analysis of the rare-earth Ni-base hydrogen bearing alloy powder behind Fig. 1 copper-clad
Used instrument is JSM～840 scanning electronic microscope, condition: voltage 20KV, amplify 3000 times.
More specifically describe the present invention with following non-limiting examples is more detailed, will help the understanding to the present invention and advantage thereof, protection scope of the present invention is not subjected to the qualification of these embodiment, and protection scope of the present invention is decided by claim.
Embodiment 1
The prescription of chemical bronze plating liquid in the present embodiment contains the CuSO of 7.85 gram/liters for being solvent with distilled water in chemical bronze plating liquid
45H
2O, the sulfuric acid of 3 milliliters/liter, the citric acid of 10 gram/liters, the lanthanum rich rare earth of 0.8 gram/liter (total amount of rare earth ∑ RE＞99.3%).
Be the MmNi of 60 μ m with 40 gram mean particle sizes while stirring at room temperature
3.6(MnCoAl)
1.4Hydrogen-storage alloy powder pour in the above-mentioned chemical plating fluid of 1 liter, continue to stir 20 minutes, plating is finished, and filters with B immediately, with distilled water wash 3 times, again with after the raw spirit washing 2 times, in 50 ℃ of oven dry, preserves.
There is not copper-plated MmNi
3.6(MnCoAl)
1.4The weight ratio capacity of naked powder be 310mAh/g (sparking voltage 1.18～1.21V), the copper content of this hydrogen-storage alloy powder after the copper facing is 5% (weight percentage), copper thickness 4000A °, chemical bronze plating liquid middle-weight rare earths content after the plating is 1.20 gram/liters, the rare earth loss only is 0.4 gram, and the theoretical value that rare earth should lose is 0.66 gram, reduce rare earth loss amount 24%, volume test is the result prove, the weight ratio capacity of this hydrogen-storage alloy powder behind the copper-clad is 304mAh/g (sparking voltage 1.20-1.23V).Morphology analysis is the result prove, coating is even, and hole is arranged, and is string bag shape.
Comparative Example A An
With reference document Journal of Alloys and Compounds 182,1992, the prescription of 321-330 carries out electroless copper, and its prescription is a solvent with distilled water, contains 7.85 gram/liter CuSO in this chemical bronze plating liquid
45H
2O, 8 milliliters/liter sulfuric acid.
At room temperature while stirring with 40 grams, mean particle size is the MmNi of 60 μ m
3.6(MnCoAl)
1.4Hydrogen-storage alloy powder is poured in 1 liter the above-mentioned chemical bronze plating liquid, constantly stirs, and strict control hydrogen-storage alloy powder and plating bath duration of contact are 4 minutes.Plating is finished, and filters with B immediately, uses distilled water wash 3 times, again with after the raw spirit washing 2 times, in 50 ℃ of oven dry, preserves.
It is 5% that the result obtains the copper-clad amount, and copper thickness 4000A °, capacity is the hydrogen-storage alloy powder behind the copper-clad of 290mAh/g (sparking voltage 1.20-1.23V).Rare earth loss amount on this hydrogen-storage alloy powder is 1.08 grams.There is not copper-plated MmNi
3.6(MnCoAl)
1.4The weight ratio capacity of naked powder be 310mAh/g.
Embodiment 2
Its working method and condition are substantially with embodiment 1, and that only different is the CuSO that contains 15.8 gram/liters in chemical bronze plating liquid
45H
2O, the sulfuric acid of 4 milliliters/liter, the citric acid of 12 gram/liters, the lanthanum rich rare earth of 1.5 gram/liters (total amount of rare earth ∑ RE＞99.3%, containing the lanthanum amount is 58%).
At room temperature, be the MmNi of 60 μ m with 40 gram mean particle sizes while stirring
3.6(MnCoAl)
1.4Hydrogen-storage alloy powder pour in the chemical bronze plating liquid of 1 liter, continue to stir 20 minutes, the volume (liter) of the weight of hydrogen-storage alloy powder (gram) and chemical bronze plating liquid is than being 40 to restrain: 1 liter, the speed of stirring are 80 rev/mins, 45 ℃ of oven dry.
The result obtains the hydrogen-storage alloy powder of copper-clad amount 10%; Copper thickness 5500A °.Plating back liquid middle-weight rare earths content is 2.3 gram/liters, the rare earth substantial loss is 0.8 gram, and the theoretical value of loss is 1.32 grams, has reduced rare earth loss amount 39%, the capacity of the hydrogen-storage alloy powder behind the copper-clad is 300mAh/g (sparking voltage 1.20-1.23V), and the morphology analysis result is with embodiment 1.
Comparative Examples B
Its working method and condition are basic with comparing embodiment A, and that only different is the CuSO that contains 15.80 gram/liters in this chemical bronze plating liquid
45H
2O, 8 milliliters/liter sulfuric acid.Stirring velocity is 80 rev/mins, and 45 ℃ of oven dry are preserved.
The result obtains copper-clad amount 10%, and copper thickness 6000A °, capacity is the hydrogen-storage alloy powder behind the copper-clad of 280mAh/g (sparking voltage 1.20-1.23V), and the rare earth loss amount is 1.62 grams.
Embodiment 3
Its working method and condition are substantially with embodiment 1, and that only different is the CuSO that contains 31.5 gram/liters in chemical bronze plating liquid
45H
2O, the sulfuric acid of 6 milliliters/liter, 15 gram/liter citric acids, the lanthanum rich rare earth of 2.0 gram/liters (total amount of rare earth ∑ RE＞99.3%, containing the lanthanum amount is 58%).
At room temperature, be the MmNi of 60 μ m with 40 gram mean particle sizes while stirring
3.6(MnCoAl)
1.4Hydrogen-storage alloy powder pour in the chemical bronze plating liquid of 1 liter, continue to stir 35 minutes, the volume (liter) of the weight of hydrogen-storage alloy powder (gram) and chemical bronze plating liquid is than being 40 to restrain: 1 liter, stirring velocity are 90 rev/mins, 55 ℃ of oven dry, preservation.
The result obtains copper-clad amount 20%, copper thickness 8000A ° hydrogen-storage alloy powder, plating back liquid middle-weight rare earths content is 3.8 gram/liters, the rare earth substantial loss is 1.8 grams, and the theoretical value of loss is 2.64 grams, reduced loss amount 32%, the capacity of the hydrogen-storage alloy powder behind the copper-clad is 280mAh/g (sparking voltage 1.20-1.23V), and the morphology analysis result is with embodiment 1.
Comparing embodiment C
Its working method and condition are basic with comparing embodiment A, and that only different is the CuSO that contains 31.50 gram/liters in this chemical bronze plating liquid
45H
2O, the sulfuric acid of 8 milliliters/liter, stirring velocity is 90 rev/mins, 55 ℃ of oven dry, preserves.
The result obtains copper-clad amount 20%, and copper thickness 8000A °, capacity is the hydrogen-storage alloy powder behind the copper-clad of 250mAh/g (sparking voltage 1.20-1.23V), and the rare earth loss amount is 3.50 grams.
Embodiment 4
Its working method and condition be with embodiment 2, and only different is replaces citric acid with tartrate or lactic acid or oxysuccinic acid, result and embodiment 2 with.
Embodiment 5
Its working method and condition are substantially with embodiment 1, and only different is to contain 21.48 gram/liter CuCl in chemical bronze plating liquid
25H
2O, 5 milliliters/liter hydrochloric acid, the citric acid of 20 gram/liters, the lanthanum rich rare earth of 2.0 gram/liters (total amount of rare earth ∑ RE＞99.3%, containing the lanthanum amount is 58%).
At room temperature, be the MmNi of 60 μ m with 40 gram mean particle sizes while stirring
3.6(MnCoAl)
1.4Hydrogen-storage alloy powder pour in the chemical bronze plating liquid of 1 liter, continue to stir 40 minutes, the volume (liter) of the weight of hydrogen-storage alloy powder (gram) and chemical bronze plating liquid is than being 40 to restrain: 1 liter, stirring velocity are 85 rev/mins, 52 ℃ of oven dry, preservation.
The result obtains copper-clad amount 19.3%5, copper thickness 7500A ° hydrogen-storage alloy powder, plating back liquid middle-weight rare earths content is 4.0 gram/liters, the rare earth substantial loss is 2.0 grams, and the theoretical value of loss is 2.55 grams, the amount of reducing the loss 22%, the capacity of the hydrogen-storage alloy powder behind the copper-clad are 275mAh/g (sparking voltage 1.20-1.23V), and the morphology analysis result is with embodiment 1.
Claims (8)
1. the prescription of the chemical bronze plating liquid of a rare-earth Ni-base hydrogen bearing alloy powder, with water is solvent, a kind of mantoquita that contains 0.5-50 gram/liter, 0.1-28 a kind of acid of milliliter/liter, it is characterized in that, a kind of organic hydroxy-acid of also containing 2-20 gram/liter, the lanthanum rich rare earth of 0.5-10 gram/liter, total amount of rare earth ∑ RE＞99.0%.
2. according to the prescription of the chemical bronze plating liquid of claim 1, it is characterized in that said mantoquita is wherein a kind of of copper sulfate, cupric chloride, cupric nitrate, neutralized verdigris.
3. according to the prescription of the chemical bronze plating liquid of claim 1, it is characterized in that said acid is wherein a kind of of sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid, acetic acid.
4. according to the prescription of the chemical bronze plating liquid of claim 1, it is characterized in that said organic hydroxy-acid is wherein a kind of of citric acid, tartrate, lactic acid, oxysuccinic acid.
5. according to the prescription of the chemical bronze plating liquid of claim 1, it is characterized in that, contain lanthanum 20-90% weight percentage in the said lanthanum rich rare earth.
6. the method for the electroless copper of a rare-earth Ni-base hydrogen bearing alloy powder is characterized in that,
(1). with water is solvent, a kind of mantoquita that contains 0.5-50 gram/liter in the chemical bronze plating liquid, a kind of acid of 0.1-28 milliliter/liter, a kind of organic hydroxy-acid of 2-20 gram/liter, 0.5-10 the lanthanum rich rare earth of gram/liter, total amount of rare earth ∑ RE＞99.0%.
(2). the mean particle size for the treatment of copper-plated rare-earth Ni-base hydrogen bearing alloy powder is 40-150 μ m,
(3). the weight (gram) for the treatment of copper-plated rare-earth Ni-base hydrogen bearing alloy powder and the volume (liter) of chemical bronze plating liquid are than being 1～80 to restrain: 1 liter,
(4). will treat while stirring that at room temperature copper-plated rare-earth Ni-base hydrogen bearing alloy powder pours in the chemical bronze plating liquid, and continue to stir 15-80 minute, and stop to stir, filter oven dry.
8. according to the method for the electroless copper of claim 6, it is characterized in that, continue to stir 20-60 minute.
9. according to the method for the electroless copper of claim 6, it is characterized in that stirring velocity is 50-120 rev/min.
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| CN1094807C (en) * | 1998-04-21 | 2002-11-27 | 冶金工业部钢铁研究总院 | Method for surface chemical nickel plating of nickel-base alloy powder |
| CN103422078B (en) * | 2012-05-22 | 2016-04-27 | 比亚迪股份有限公司 | A kind of chemical bronze plating liquid and preparation method thereof |
| CN103203452A (en) * | 2013-03-28 | 2013-07-17 | 桂林理工大学 | Method of surface copper plating modification for AB3 type hydrogen storage alloy |
| CN103611932B (en) * | 2013-12-18 | 2016-04-13 | 江苏科技大学 | The sonochemistry preparation method of the coated phosphorus nickel alloy layer of a kind of Copper Powder Surface |
| CN103811725B (en) * | 2014-01-28 | 2016-02-10 | 东南大学 | The surface treatment method of hydrogen bearing alloy |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6222370A (en) * | 1985-07-22 | 1987-01-30 | Matsushita Electric Ind Co Ltd | Nickel-hydrogen alkaline storage battery |
| JPH03247735A (en) * | 1990-02-23 | 1991-11-05 | Nippon Yakin Kogyo Co Ltd | Rare earth metal-nickel series hydrogen storage alloy and material for occluding hydrogen |
| CN1058235A (en) * | 1990-07-18 | 1992-01-29 | 北京有色金属研究总院 | The manufacture method that contains the Wimet of rare earth |
-
1995
- 1995-02-24 CN CN95101640A patent/CN1060697C/en not_active Expired - Lifetime
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6222370A (en) * | 1985-07-22 | 1987-01-30 | Matsushita Electric Ind Co Ltd | Nickel-hydrogen alkaline storage battery |
| JPH03247735A (en) * | 1990-02-23 | 1991-11-05 | Nippon Yakin Kogyo Co Ltd | Rare earth metal-nickel series hydrogen storage alloy and material for occluding hydrogen |
| CN1058235A (en) * | 1990-07-18 | 1992-01-29 | 北京有色金属研究总院 | The manufacture method that contains the Wimet of rare earth |
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| CN1129620A (en) | 1996-08-28 |
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