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EP0497675B1 - Verfahren zur Herstellung eines feinen dendritischen Pulvers und nach diesem Verfahren erzeugtes Pulver - Google Patents

Verfahren zur Herstellung eines feinen dendritischen Pulvers und nach diesem Verfahren erzeugtes Pulver Download PDF

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Publication number
EP0497675B1
EP0497675B1 EP92400200A EP92400200A EP0497675B1 EP 0497675 B1 EP0497675 B1 EP 0497675B1 EP 92400200 A EP92400200 A EP 92400200A EP 92400200 A EP92400200 A EP 92400200A EP 0497675 B1 EP0497675 B1 EP 0497675B1
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Prior art keywords
cadmium
powder
order
sponge
approximately
Prior art date
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Expired - Lifetime
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EP92400200A
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English (en)
French (fr)
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EP0497675A1 (de
Inventor
Luc Albert
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Metaleurop SA
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Metaleurop SA
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C5/00—Electrolytic production, recovery or refining of metal powders or porous metal masses
    • C25C5/02—Electrolytic production, recovery or refining of metal powders or porous metal masses from solutions

Definitions

  • the present invention relates to a process for preparing a dendritic cadmium powder, as well as a powder obtained by the process.
  • the electrode structures are particularly studied in order to be able to contain a charge of active material as high as possible (Number of amperes.hourest hour) and as available as possible (maximum intensity).
  • the negative electrode structure usually made of sintered nickel
  • PBT structure in which a mixture of cadmium oxide and metallic powder is coated on a strip.
  • the role of the conductive powder is to distribute the current of electrons homogeneously in the volume of the active mass of cadmium hydroxide.
  • Japanese patent application published under No. 55-76569 on 9.6.80 teaches the preparation of such a powder and its incorporation into the electrode in such proportions.
  • the present invention is based on the observation that, with a powder urn which deviates from the spherical shape (in other words with a form factor which is much greater than 1), and in particular with a dendritic powder, the electrical performance is greatly improved, and in particular the volume energy is increased.
  • a dendritic powder is added to the paste of the electrode in a quantity substantially lower than a spherical powder, resulting in a gain of weight.
  • Document FR-A-2 194 792 teaches a process for the preparation of a porous electrode from a cadmium powder of acicular or dendritic nature. This powder, obtained by deposition on an electrode then dry scraping, is then compressed to form the electrode, and is not intended to be used as a current distribution agent as mentioned above. More specifically, the operating conditions described in this document are such that the powder does not have the required fineness. In addition, the principle of electrolysis described in this patent oblique to work with small amounts of electricity, with extremely frequent scraping.
  • the present invention thus aims to propose an electrolytic process for obtaining a dendritic cadmium powder, which makes it possible to obtain, by appropriate control of simple parameters, a powder of quality and of particularly suitable characteristics, in particular in terms of fineness, incorporation into a negative nickel / cadmium accumulator electrode. It also proposes a process that can be implemented with large amounts of electricity, to obtain before powder reduction an electrode thickness of up to several centimeters without suffering from homogeneity defects.
  • the invention also relates to a dendritic cadmium powder as defined in claim 8.
  • An advantage of the method according to the invention resides in that it offers the possibility of constituting a metallic matrix whose physical characteristics can be chosen without having to undergo the strong constraint of the particle size distribution.
  • the inventors were able to determine the conditions for obtaining, by electrolytic deposition, a dendritic structure or else a sponge structure.
  • the transition from one form of structure to another follows from the mode of crystallization.
  • the dendritic structure evolves towards the sponge when the section of the crystals oriented in the field decreases and the two-dimensional germination continues on the pre-existing dendrites.
  • the constitution of the sponge by deposition on the cathode does not pose any particular starting difficulty.
  • Substrates can be used, for example stainless steel or titanium. It does not matter whether the surface is virgin or whether there remains a cadmium residue from the previous operation.
  • the separation of the sponge from its substrate is carried out by light mechanical means of conventional type.
  • the separated sponge is then washed in order to recover the electrolyte which still permeates it.
  • the particular structure of the sponge allows very effective washing with a very small amount of water.
  • the sponge proves to be perfectly chemically stable, either with respect to dissolution by acid attack or by air oxidation.
  • the second operation of the process consists in performing a shredding of the sponge. It is carried out in tank disintegration devices provided with specific stirring mobiles, operating continuously or discontinuously. In order to promote a complete release of particles of the sponge, it is preferable here to work with a pulp rate that does not exceed 200 g of dry matter per liter. As will be seen below, the peripheral speed of the stirring mobile is an important factor in obtaining an appropriate particle size.
  • a sieving operation intended to remove coarse particles, and preferably particles larger than 125 ⁇ m, is advantageously provided, but optionally.
  • the disintegration stage releases particles whose size and solidity are determined essentially by the operating conditions of the electrolytic stage of constitution of the sponge, and are only very weakly influenced by a too long residence time of the material in the disintegration apparatus and by the choice of the geometry of the stirring mobiles.
  • shredding mobiles have been tested, with or without counter-blades, without significantly modifying the morphology and the particle size of the powder. In addition, no overgrinding of the powder was observed.
  • the good mechanical strength of the particles constituting the pulp allows storage in the decanted state without modifying the particle size distribution.
  • the pulp obtained at the end of the disintegration can be pumped, for example by a centrifugal vortex pump, without undergoing any particle size alteration.
  • the morphology of the powder obtained is characteristic of the process according to the invention.
  • the particles have the form of ferns made up of a central column from which leave, with an angle of the order of 60 °, secondary ferns.
  • the overall shape is generally acicular, a shape well suited to the intended application.
  • the electrolysis cell can be supplied either with a pure cadmium solution or with metallic cadmium of appropriate purity.
  • a concentrated solution is preferably chosen.
  • the associated anion is advantageously sulfate.
  • the acidity of the solution can vary for example between 5 and 80 g / l of sulfuric acid.
  • the total content of metallic impurities in the solution, expressed relative to the cadmium must be less than 100 g / t.
  • the electrolysis cell is powered by cadmium metal
  • it can take any suitable form, preferably with a purity of 99.99% or better.
  • the electrolyte is composed of cadmium sulfate and sulfuric acid.
  • the acid content is conditioned by the search for a good ionic conductivity of the electrolyte. This content is advantageously between 5 and 100 g / l, a value close to 50 g / l being particularly advantageous because it gives a very good conductivity while limiting the acid corrosion of the sponge.
  • the cadmium concentration is preferably between 4 and 15 g / l, more preferably between 7 and 11 g / l.
  • the operating temperature is preferably maintained in a range between 20 and 35 ° C, more preferably between 25 and 30 ° C.
  • the cathode substrate is preferably stainless steel or titanium. It was found that good adhesion of the sponge was obtained with a surface roughness corresponding to the raw rolling state.
  • the circulation of the electrolyte is ensured either naturally when the oxygen is released, for a cell with insoluble anodes, or in a provoked way.
  • the choice of circulation type has practically no influence on the morphology of the sponge.
  • the duration of electrolysis between two debates is preferably between 4 and 8 hours. Under the optimized current density and cadmium concentration conditions as mentioned above, a duration of the order of 6 hours is particularly suitable.
  • the concrete design of the electrolysis cells is of the conventional type, and will not be described in detail. It is possible, for example, to use cells of the type used in the zinc or copper industry.
  • the composition of the electrolyte does not remain stable. Indeed, the reaction at the cathode, where the protons are reduced and hydrogen is generated, constitutes a parasitic reaction which causes a decrease in the acidity of the medium, with which is associated an increase in the cadmium concentration.
  • the electrolysis process with soluble anodes with an electrolysis process with insoluble anodes, working on the same electrolyte.
  • this surface constitutes a determined percentage of the total cathodic surface, a percentage equal to the cathodic faradic yield of hydrogen release, the excess of aforementioned anodic dissolution.
  • the acidity consumed by the above-mentioned parasitic reaction is also generated on the insoluble anodes.
  • the system is therefore globally balanced and can operate under stable conditions practically without the need for addition or purging, which guarantees constant quality for the sponge formed, and therefore for the powder.
  • the sponge After electrolysis then deburring and washing of the sponge as indicated above, the sponge is subjected to the disintegration operation.
  • the shredding action is carried out by an agitating mobile having no significant pumping or shearing function. We are mainly looking for a shock effect on the peripheral parts of the mobile which have a small active surface.
  • the essential parameter is the peripheral speed of the mobile. It is preferably situated between 20 and 50 m / s for diameters of stirring mobiles varying between 83 and 380 mm. For speeds lower than this range, a rapid increase in the rate of particles refused to sieving is observed. Concretely, it was found that, for a mobile with a diameter of 380 mm, a peripheral speed of 30 m / s was sufficient to reach a rejection rate at sieving at 125 ⁇ m of less than 0.5%.
  • the residence time of the sponges in the disintegration apparatus is for example between 3 and 5 minutes. However, it has been found that an excess of residence time of 100 to 200% over these durations has no consequence on the particle size distribution.
  • the pulp rate is fixed at a value compatible both with the productivity requirements of the process and with the requirement of conservation of the particle size distribution. Concretely, an amount of dry matter per liter of pulping solution between 50 and 200 g / l is suitable. Beyond the upper limit, the particle size distribution becomes coarser.
  • the pulp is sieved, as indicated above, for example using a vibrating sieve, to remove particles of a size greater than a determined size limit, preferably about 125 ⁇ m.
  • the pulp is then decanted and conditioned. An oxidation rate of less than 1% per month has been observed under wet storage conditions.
  • the process of the invention guarantees a very high titer in metallic cadmium compared to the total cadmium.
  • the final product is very little oxidized.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Powder Metallurgy (AREA)
  • Electrolytic Production Of Metals (AREA)

Claims (12)

  1. Verfahren zur Herstellung eines feinen dendritischen Cadmiumpulvers, dadurch gekennzeichnet, daß es die folgenden Stufen umfaßt:
    (a) elektrolytische Bildung von metallischem Cadmium auf einer Elektrode bei einer Stromdichte zwischen 700 und 1500 A/m2 und einer Cadmium-Konzentration in dem Elektrolyten, bestimmt durch die Gleichung: 100 A.m/kg ≤ J/(CD) ≤ 200 A.m/kg
    Figure imgb0006
     worin J für die Stromdichte, ausgedrückt in A/m2, und (CD) für die Cadmium-Konzentration, ausgedrückt in kg/m3, stehen,
    und mit einer Elektrolytlösung, die besteht aus Cadmiumsulfat und Schwefelsäure, deren Schwefelsäuregehalt zwischen 5 und 100 g/l liegt, unter Bildung eines Schwammes, der aus fein verwachsenen (eingesprengten) polymorphen Dendriten besteht,
    (b) Abtrennen (Ablösen) und Waschen des Schwammes,
    (c) Zerkleinern des Schwammes in einem Pulpen-Medium, um die Dendrite freizusetzen und um ein Dendrit-Pulver mit einer Teilchengröße, die im wesentlichen unterhalb eines vorgegebenen Grenzwertes liegt, zu erhalten.
  2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß die Stufe (a) bei einer Temperatur zwischen 20 und 35°C, vorzugsweise zwischen 25 und 30°C, durchgeführt wird.
  3. Verfahren nach einem der Ansprüche 1 und 2, dadurch gekennzeichnet, daß die Stufe (c) in einem Zerkleinerungs-Behälter mit einem Pulpen-Gehalt zwischen 50 und 200 g Cadmium pro Liter Lösung der eingesetzten Pulpe und mit einem beweglichen Rührkörper, dessen gegenüber der Pulpe aktive Oberfläche klein ist und dessen Umfangsgeschwindigkeit zwischen 20 und 50 m/s liegt, durchgeführt wird.
  4. Verfahren nach Anspruch 3, dadurch gekennzeichnet, daß die Stufe (c) für eine Zeitdauer von mehr als 3 min durchgeführt wird.
  5. Verfahren nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, daß die Stufe (a) durchgeführt wird durch Einführen von metallischem Cadmium in eine Elektrolyse-Vorrichtung und daß die Vorrichtung umfaßt mindestens eine Zelle, die mit löslichen Anoden arbeitet, und mindestens eine Zelle, die mit unlöslichen Anoden arbeitet, wobei die Kathodenoberfläche der mit unlöslichen Anoden arbeitenden Zelle(n) so ausgewählt wird, daß sie einen Prozentsatz der Kathodengesamtoberfläche darstellt, der gleich der kathodischen Faraday-Ausbeute an freigesetztem Wasserstoff ist.
  6. Verfahren nach einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, daß auf die Stufe (c) eine Stufe (d) folgt, in der die Pulpe gesiebt wird, um die Feststoffteilchen mit einer Größe oberhalb eines vorgegebenen Grenzwertes zu eliminieren.
  7. Verfahren nach Anspruch 6, dadurch gekennzeichnet, daß in der Stufe (d) die Teilchen mit einer Teilchengröße oberhalb etwa 125 µm eliminiert werden.
  8. Dendritisches Cadmiumpulver zur Herstellung einer Cadmium/Nickel-Akkumulator-Elektrode, dadurch gekennzeichnet, daß seine Teilchen die Form von Farnen haben, die umfassen eine zentrale Seele, von der Sekundärdendrite schräg abzweigen, wobei der Querschnitt der zentralen Seele zwischen etwa 4 und etwa 20 µm2 liegt und diese eine spezifische Oberflächengröße, bestimmt nach dem BET-Verfahren, zwischen etwa 1 und etwa 3 m2/g hat.
  9. Pulver nach Anspruch 8, dadurch gekennzeichnet, daß es eine Teilchengröße unterhalb 125 µm aufweist.
  10. Pulver nach Anspruch 9, dadurch gekennzeichnet, daß es einen d90 in der Größenordnung von 35 µm und einen d10 in der Größenordnung von 7 µm aufweist.
  11. Pulver nach einem der Ansprüche 8 bis 10, dadurch gekennzeichnet, daß es mindestens 95 % metallisches Cadmium enthält.
  12. Pulver nach einem der Ansprüche 8 bis 11, dadurch gekennzeichnet, daß der mittlere Winkel der Sekundärdendrite, bezogen auf die zentrale Seele, in der Größenordnung von 60° liegt.
EP92400200A 1991-01-28 1992-01-27 Verfahren zur Herstellung eines feinen dendritischen Pulvers und nach diesem Verfahren erzeugtes Pulver Expired - Lifetime EP0497675B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR9100922A FR2672061B1 (fr) 1991-01-28 1991-01-28 Procede d'obtention d'une poudre fine de cadmium dendritique et poudre obtenue par le procede.
FR9100922 1991-01-28

Publications (2)

Publication Number Publication Date
EP0497675A1 EP0497675A1 (de) 1992-08-05
EP0497675B1 true EP0497675B1 (de) 1996-09-04

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EP92400200A Expired - Lifetime EP0497675B1 (de) 1991-01-28 1992-01-27 Verfahren zur Herstellung eines feinen dendritischen Pulvers und nach diesem Verfahren erzeugtes Pulver

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US (1) US5496462A (de)
EP (1) EP0497675B1 (de)
JP (1) JPH06280073A (de)
AU (1) AU651425B2 (de)
DE (1) DE69213268T2 (de)
ES (1) ES2092065T3 (de)
FI (1) FI101086B (de)
FR (1) FR2672061B1 (de)
MX (1) MX9200330A (de)
NO (1) NO920347L (de)
TW (1) TW221463B (de)

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JP2002539595A (ja) * 1999-03-15 2002-11-19 ケース ウェスタン リザーブ ユニバーシティ 迅速な表面化学反応用の金属スポンジ
US7378010B2 (en) * 2004-07-22 2008-05-27 Phelps Dodge Corporation System and method for producing copper powder by electrowinning in a flow-through electrowinning cell
WO2024117191A1 (ja) * 2022-11-30 2024-06-06 パナソニックＩｐマネジメント株式会社 金属回収方法

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US3326721A (en) * 1963-06-10 1967-06-20 Ian H S Henderson Nickel cadmium batteries
US3400056A (en) * 1964-08-26 1968-09-03 Electric Storage Batteery Comp Electrolytic process for preparing electrochemically active cadmium
US3847784A (en) * 1972-07-28 1974-11-12 Mallory Battery Canada Porous cadmium anode and a method of forming it, and a primary cell using the anode
JPS5576560A (en) * 1978-12-01 1980-06-09 Hitachi Ltd Observation field moving device for electron microscope
US4414303A (en) * 1980-08-28 1983-11-08 Motorola, Inc. Cadmium negative electrode
JPH03153892A (ja) * 1989-11-11 1991-07-01 Dowa Mining Co Ltd 微細なカドミウム粉末の製造方法

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FI920374L (fi) 1992-07-29
TW221463B (de) 1994-03-01
US5496462A (en) 1996-03-05
AU1049792A (en) 1992-07-30
FI920374A0 (fi) 1992-01-28
DE69213268T2 (de) 1997-03-13
NO920347D0 (no) 1992-01-27
JPH06280073A (ja) 1994-10-04
ES2092065T3 (es) 1996-11-16
FR2672061A1 (fr) 1992-07-31
MX9200330A (es) 1992-09-01
NO920347L (no) 1992-07-29
DE69213268D1 (de) 1996-10-10
AU651425B2 (en) 1994-07-21
FR2672061B1 (fr) 1993-10-15
EP0497675A1 (de) 1992-08-05
FI101086B (fi) 1998-04-15

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