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On the recovery of spent nickel-cadmium batteries

Article · January 1999

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 Panayotova M., Panayotov V., On the recovery of spent Nickel-Cadmium batteries, Proc. of XII Balkan
Mineral Processing Congress, 10-14 June 2007, Delphi, Greece, NTUA, G. N Anastassakis, (ed)., 559-564,
2007

ON THE RECOVERY OF SPENT NICKEL-CADMIUM BATTERIES

ABSTRACT
Spent nickel-cadmium (NiCd) batteries represent harmful waste, which at proper handling, processing and
recycling could be turned in useful raw material. Work, described in the paper, is devoted to finding optimal
conditions for Cd and Ni recovery from spent batteries. Influence of temperature, solid to liquid ratio and
sulfuric acid concentration on the leaching was studied. Linear sweep voltammetry (LSV) was used in an
attempt to determine the conditions at which metals can be electrowinned at high grade from the mixed
leachate. Influence of heavy metal ions concentration in the mixed solution, electrode material, leachate pH
and agitation on the deposition of the metals of interest was investigated. Possibility to use LSV tests for
fast determination of the potential at which heavy metals can be electrowinned with satisfactory grade is
checked by correlating the data on optimal potential determined by LSV and on the grade of electrowinned
metal at that potential.

INTRODUCTION
Rechargeable NiCd batteries are found in the market as large industrial and small, sealed-type batteries for
cordless power tools, telecommunications, emergency lighting and security, and portable household
applications including hearing aids, heart monitors, tooth brushes, shavers, laptop computers, pagers,
electronic toys, and MP3-players. The sealed batteries account for about 80 % of the cadmium
consumption in the battery market. They are sold for consumer uses in a number of different sizes as
individual battery cells or as incorporated in appliances. The remaining 20 % of cadmium is consumed in
large industrial NiCd batteries ("open" type batteries) which are generally sold to and used by a small group
of professional users - for railroad, aerospace, electric vehicles and standby power, etc. The worldwide
market of NiCd batteries continues to grow, nevertheless that for some areas (Western Europe), other
battery types are gaining market share. Nickel-cadmium batteries are popular because of their good
performance (can be recharged up to 1000 times and are less sensitive to abuse due to overcharging) and
because they are the least expensive of the secondary batteries. The trends in the usage of portable
consumer NiCd batteries shows that cordless power tools take up an increasing part of the consumption
whereas the use for cellular telephones has ceased on the world market.
Nickel-cadmium batteries pose little hazard in use, but are a danger in landfills. Metal emissions from
batteries to water originate (96-98 %) from landfilling and incineration. Two per cent of the Cd and Ni
emission to water occur during battery manufacturing (Rydh, 2001). It has been found by degradation tests
(Oda, 1989) that Cd from whole batteries would not be released for two to four decades in a landfill
subjected to normal rainfall. The main concern is that over time landfills will be abandoned, may be
exposed to construction works, erosion by flooding, etc. and this renders them in a long-term source of
releases of cadmium and other hazardous substances to the environment. The emission of Cd to air takes
place mainly (99 %) in the incineration and landfilling activities. By use of best available techniques, the
emission of Cd to air from modern incineration plants is usually around 1 % of the Cd in the waste (Rydh,
2001). Uncontrolled burning and dumping of waste is known to take place in many countries worldwide. For
nickel, 82 % of the emissions occur during incineration and landfilling, while 15 % originates from raw
materials extraction. From an environmental perspective, the optimum recycling rate for NiCd batteries
tends to be close to 100%.
Nowadays metals’ recycling is likely to be seen as an environmental activity, but it has existed for many
centuries as an economic activity. Batteries manufactured with recycled Ni and Cd instead of virgin metals
posses 16 % lower primary energy use. The costs of Ni extraction from primary sources are higher
compared to those for recycled metal.
Many countries have implemented systems for separate collection of NiCd batteries in order to minimize
the contamination of the general waste stream with cadmium. These countries have found it difficult to
achieve satisfactory collection rates (over 50 %) for small batteries. The remaining part of batteries ends up
in municipal solid waste. It turned out that separate collection and treatment implies significant extra costs
to society. Some countries have therefore worked goal-oriented towards minimizing NiCd battery
consumption, e.g. by introducing import fee systems which also have the role of covering society's costs for
separate collection and treatment of waste batteries. Sweden and Denmark have specific taxes on NiCd
batteries, including power tool batteries. Large industrial batteries are easy to collect and they are recycled
at a rate of about 80 percent.
At legislation level Directive 2006/66/EC, entered in force 26 September 2006, deals with batteries
recycling. The main provisions of this Directive can be summarized as follows: a) Member States must
establish a national collection system to allow consumers to return spent batteries free of charge; b) The
recycling target is 90 %; c) Additional target of 80 % of all portable NiCd batteries generated annually; d)
Member States must monitor the quantities of NiCd batteries in the municipal solid waste stream; e) Nickel-
cadmium batteries recycling should recover 100 % of the Cd and 75 % of the average weight of the
batteries; f) The battery producers should finance the collection and treatment requirements.
Cadmium from spent NiCd batteries can be recovered using pyrometallurgical or hydro-metallurgical
processes. Generally, the recycling plants employ pyrometallurgical processes. In this process, Cd is
volatilized and the resultant fume and dust are collected as flue dust in bag-houses or electrostatic
precipitators. The dust is recycled to upgrade the Cd content (Llewellyn, 1992). The feedstock is sorted to
avoid an introduction of Hg or Pb to the distillation. Electrolyte is emptied from large batteries and they are
dismantled mechanically. The separators are then removed together with the plastic casings, and then the
cadmium is recovered by distillation. It is the processing of battery scrap prior to distillation that is so
expensive. For large, vented cells, from which the Ni plates are removed prior to distillation, there are no
major problems. The purity of recycled Cd is high. For domestic, sealed cells, however, separating the
compacted nickel hydroxide from the cadmium plates and fibrous support material is very tedious and
costly (Holt, 1990). That is why the small proportion of domestic, sealed batteries that is recycled is usually
fed into the furnace as whole cells. The plastic casings and separators of the small sealed batteries are
burned off at a lower temperature prior to a higher temperature treatment required for volatilization and
condensation of cadmium content. Nickel metal is formed that alloys with the cadmium and reduces yields.
Recycling technology is required for small, domestic, sealed cells that allow separation of Ni and Cd.
A technique for spent NiCd batteries recycling, which makes separation of Cd and Ni possible, has been
developed at laboratory-scale. NH3-H2CO3 aqueous solution was used as leaching means (Xianghua,
2000). If the NH3 concentration is sufficiently high and the ratio of H2CO3 to NH3 is properly adjusted, both
Ni(OH)2 and Cd(OH)2 quickly dissolve into leaching solution. Then Ni(OH)2 can be converted into insoluble
NiO by calcination at 500 oC, and CdO from Cd(OH)2 by calcination maintains good solubility in NH3-H2CO3
aqueous solution. The yields of 99.8 % for Ni and 97.6 % for Cd are obtained, and the purities of recovered
Ni and Cd are 99.9% and 98.6 %, respectively.
A technique for domestic, sealed NiCd batteries recycling has been proposed (Cox, 1999). It is based on
chlorination of the battery. The resulting cadmium chloride may be sold directly to appropriate consumers
or electrolyzed to recover the cadmium metal. Chlorine and hydrogen chloride were found to be suitable
chlorinating agents. The latter was produced by the controlled combustion of polyvinyl chloride scrap. The
chlorination technique relies on the thermodynamic instability of cadmium oxide with respect to its chloride
and on the relative stability of iron and nickel oxides with respect to their chlorides in the presence of a
dilute chlorinating agent.
Cadmium recycling from chemical bath deposition of CdS thin layers by dissolution and electrowinning has
been described (Malinowska, 2002). Cadmium-bearing cake is dissolved in sulfuric acid solution 0.2-
0.5 mol/l mixed with hydrogen peroxide (about 1 mol/l) at molar ratio H2O2/Cd 5). Then the H2O2 is
completely removed from the solution and Cd is recycled by electrowinning.
The present paper describes and attempt to find optimal conditions for Cd and Ni recovery from small,
domestic, sealed spent batteries by avoiding pyrometallurgical processes, which turned out not very
suitable for small cells.

METHODS AND MATERIALS

Fully discharged, domestic, sealed NiCd batteries were prepared for dissolution by removing the plastic
labels and shredding. Then the material was subjected to leaching with solutions of H2SO4 with different
concentrations: 1, 2, 4 and 6 M. Experiments were carried out at ambient temperature, 50 and 95 oC and
ratios solid/liquid of 1/5, 1/10 and 1/20. Most suitable leaching conditions were determined on the basis of
amounts of leached metals and the cost of leaching. Concentration of dissolved metals was determined by
ICP-AES. Linear sweep voltammetry (LSV) was used in order to determine the conditions at which metals
could be electrowinned from the mixed leachate. Gill AC potentiostat-galvanostat (ACM Instruments) with
the corresponding software was used. Influence of heavy metal ions concentration in single and mixed
solution, leachate pH and agitation on the deposition potential of the metals of interest was investigated by
registration of polarization curves at rate of 1 mV/min. Electrowinning was carried at predetermined (from
the polarization curves) fixed potential and the grade of electrowinned metal was determined by ICP-AES
(after proper dissolution).

RESULTS AND DISCUSSION

The optimum leaching conditions found were: H2SO4 - 4 M, temperature 95 oC and ratio solid/liquid = 1/10.
Leachate contained Ni - 50 g/L, Cd - 25 g/L and Co approximately 1 g/L. Polarization curves of single ions
solutions at concentrations found in the leachate are presented in Figure II.6.1. Influence of initial ions
concentration on the polarization behavior is presented in Figures II.6.2 – II.6.4. Changes in polarization
behavior due to mixing are presented in Figures II.6.5 – II.6.7. The influence of solution pH value is
presented in Figures II.6.8 – II.6.10.
-140 -30
-120
-25
I/area, mA.cm-2
I/area, mA.cm-2

-100
-20
-80
-60 -15

-40 -10

-20 -5
0 0
-600 -700 -800 -900 -1000 -1100 -500 -700 -900 -1100
E vs. AgCl, mV E vs. AgCl, mV

Figure II.6.1. Polarization curves of single Figure II.6.2. Polarization curves of Ni ions
ions solutions:  1 M Ni, - - - -0.2 M Cd, at concentrations:  1 M Ni, - - - -0.4 M Ni,
 …….0.02 M Co …….0.1 M Ni

-140 -30
-120
-25
I/area, mA.cm-2

-100

I/area, mA.cm-2
-20
-80
-15
-60
-40 -10
-20 -5
0 0
-500 -700 -900 -1100 -500 -700 -900 -1100
E vs. AgCl, mV E vs.AgCl, mV

Figure II.6.3: Polarization curves of Cd ions at Figure II.6.4: Polarization curves of Co ions
at concentrations:  0.4 M Cd, - - - -0.2 M Cd, concen-trations:  0.2 M Co, - - - -0.1 M
Co,
…….0.02 M Cd ….0.005 M Co

A pronounced deposition of Ni and Co started at potentials much more negative than theoretically
calculated by using the Nernst equation. Deposition of Cd started at potentials near to calculated (Fig.
II.6.1) and significantly different from potentials of Ni and Co deposition. This finding points at the eventual
possibility for Cd electrowinning even from mixed solutions. As with their standard electrode potentials,
values at which Ni and Co deposition started are very near (the statement holds true both for initial
practically negligible and for the well pronounced deposition). This poses question about the Ni and Co
separation.
Decrease in ions concentration in solution due to their electrowinning decreases their deposition current (as
expected) and changes (to some extent) the deposition potential. The potential shift was close to
theoretically calculated for Cd and deviated from calculated for Co and especially for Ni (Figs. II.6.2 –
II.6.4). A certain synergism in metals deposition was observed for mixed Ni – Co solutions and significant
deposition practically started at close potentials for mixed solutions and single ion solutions (Fig. II.6.5).
From mixed Ni – Cd solutions cadmium deposition prevailed, even from solutions with the ratio Ni
concentration / Cd concentration = 20, while from solutions with very low Cd concentration (0.01M) a
mixture of Ni and Cd most probably would be deposited (Fig. II.6.6).

-30 -90
-80
-25
-70
I/area, mA.cm-2

I/area, Ma.cm-2

-20 -60
-50
-15
-40
-10 -30
-5 -20
-10
0 0
-500 -600 -700 -800 -900 -1000 -500 -600 -700 -800 -900 -1000
E vs. AgCl, mV E vs. AgCl, mV
 Figure II.6.5. Polarization curves in mixed Figure II.6.6. Polarization curves in mixed
solutions:  1M Ni + 0.02 M Co, …… 1 M Ni solutions:  1M Ni + 0.2 M Cd, - - - - 1 M Ni
+ 0.01 M Co, - - - - 1M Ni, -.-.-.- 0.02 M Co + 0.05 M Cd, -. -. -. - 1M Ni + 0.01 M Cd, ....... 1M Ni,
-..-..-..- 0.2 M Cd
Figure II.6.7. Polarization curves in mixed Figure II.6.8. Influence of solution pH:
-90 -80
-80
-70
-70
I/area, mA.cm-2

-60
-60

I/area, mA.cm-2
-50 -50
-40 -40
-30 -30
-20 -20
-10 -10
0
0
-600 -700 -800 -900 -1000
-600 -800 -1000
E vs. AgCl, mV E vs. AgCl, mV

solutions:  1M Ni + 0.2 M Cd + 0.02M Co,  0.4 M Ni at pH 1, ….. 0.1 M Ni at pH 1,

......... 1 M Ni + 0.02 M Cd + 0.02 M Co, - - - 0.4 M Ni and pH 2, -.-.-.-0.1 M Ni and pH 2,
-. -. -. - 1M Ni + 0.01 M Cd + 0.02 M Co,  0.4 M Ni and pH 3, -..-..- 0.1 M Ni and pH 3
- - - - 1M Ni, -..-..-..- 0.2 M Cd

Predominately Cd deposition could be expected from the mixed solution containing heavy metals in
concentrations equal to the concentrations obtained in battery leachate. Probably mixed deposition of Ni
and Co would predominate at Cd concentrations ≤ 0.01M (Fig. II.6.7).
A decrease in solution pH value increased the cathodic current in Ni solutions, but decreased yield in Ni
deposition. (The statement was supported by observation of H2 bubbles during the polarization process and
semiquantitative analysis of the deposited material.) It seems that pH around 3 is the optimum for Ni
deposition – Fig. II.6.8. Solution pH value has not influenced significantly the potential at which appreciable
Cd deposition started; the cathodic current increased with acidification and significant decrease in the
deposition yield was not obtained – Fig. II.6.9. It is clear from Figure II.6.10 that the best pH value (from the
studied range) for Co deposition is pH 3. (Non-smoothed polarization curves are indicative for H2 deposition
and bubbles blowing.)

-200 -40

-150 -30
-2

I/area, mA.cm-2
I/area, mA.cm

-100 -20

-10
-50

0
0
-800 -900 -1000 -1100 -1200
-600 -700 -800 -900 -1000
E vs. AgCl, mV E vs. AgCl, mV

Figure II.6.9. Influence of solution pH:  0.4 M Cd Figure II.6.10. Influence of solution pH:
at pH 1, ….. 0.1 M Cd at pH 1, - - - 0.4 M Cd …… 0.4 M Co at pH 1, - - - - 0.1 M Co at pH 1,
 and pH 2, -.-.-.-0.1 M Cd and pH 2,  0.4 M Cd -.-. - 0.4 M Co and pH 2, -0.1 M Co and pH 2,
and pH 3, -..-..- 0.1 M Cd and pH 3. -..-..-0.4 M Co and pH 3,  0.1 M Co and pH
3.

Influence of stirring on the deposition was studied at pH 3. It has been found that the potential at which Cd
deposition started practically was not influenced by the stirring. However, current density was increased
3÷4 times due to the formation of dendrites (with typical appearance). Potential at which Ni deposition
commenced was moved by 30÷50 mV to the negative direction in non-stirred solutions, this way becoming
more close to the values at which Co deposition started. No significant changes in current density were
observed (compared to the corresponding stirred solutions). Deposit was rich in pits. Potential at which Co
deposition started practically was not influenced by the stirring. Current density was increased 1.2÷1.5
times due to the formation of some dendrites. Some pits were observed on the electrode surface when
dendrites were removed.
Change in electrode material from steel to cadmium did not influence practically the potential at which the
deposition process started from Cd solutions. In mixed solutions, at enough high Cd concentration (≥0.01
M) the potential at which deposition started was not influenced and deposition current was increased when
steel electrode was replaced by Cd electrode. Potential at which Ni deposition started was moved to more
negative values when the process was led on Cd electrode. Usage of cobalt electrode did not improve the
situation with respect to separate deposition of Ni and Co. Results obtained suggest the idea that
practically, from mixed (Ni, Cd≥0.01 M, Co) solutions, after an initial deposition of Cd on steel electrode,
the process continues as exhaustive Cd deposition on Cd electrode, and when the amount of Cd is too
small Ni and later traces of Co are deposited.
Electrolysis, carried out for 5 hours in solutions containing 1M Ni + 0.2 M Cd + 0.02 M Co, at fixed
potentials of -705 mV, -720 mV, - 740 mV, -760 mV and -780 mV (all vs. Ag,AgCl reference electrode with
potential = 0.222 mV vs. SHE), showed that predominately Cd is deposited. Material deposited at potentials
of -705 mV, -720 mV, and - 740 mV contained about 97-98 % Cd. Deposit obtained at -760 mV contained
1-2 % Ni, while the deposit received at -780 mV contained about 94-95 % Cd, 2-3 % Ni and traces of Co.

CONCLUSIONS
Heavy metals from spent NiCd batteries can be successfully leached with 4 M H2SO4 at temperature 95 oC
and ratio solid/liquid = 1/10. Electrochemical methods (Linear sweep voltammentry and electrolysis at fixed
potential) may be used to study different factors that influence metals electrowinning from the leachate. If
the electrowinning process is carried in the optimum range of potentials (-740 ÷-760 mV vs. Ag,AgCl
electrode), acceptable recoveries of Cd (97÷98 %) could be achieved.

REFERENCES
Cox, A. & Fray, D. (1999) Recycling of cadmium from domestic, sealed NiCd battery waste by use of
chlorination Trans. Instn Min. Metall. (Sect. C: Mineral Process. Extr. Metall.), 108: pp. C153-C158.
Holt, G. & Horn, G. (1990) Recycling of nickel–cadmium batteries by physical processing: experimental
studies on both large and small batteries. In Recycling of metalliferous materials, London: IMM, pp. 93–
102.
Llewellyn, T. (1992) Cadmium. Minerals yearbook 1992 (Bureau of Mines) 1: pp. 271-280.
Malinowska, B. & Rakib, M. & Durand, G. (2002) Cadmium recovery and recycling from chemical bath
deposition of CdS thin layers. Progress in Photovoltaics: Research and Applications 10: pp. 215 – 228.
Oda, S. (1989) The disposal of NiCd batteries in landfills and the affect of cadmium on the human system,
Proceedings, 1st Int. Seminar on Battery Waste Management, Deerfield beach, FL., June 8-10, pp.173-
180.
 Rydh, C. & Karlström, M. (2001) Life cycle assessment of recycling portable nickel-cadmium batteries.
Resources, Conservation and Recycling 38: pp. 64-76.
Xianghua, K. & Pingnan, W. (2000) Recycling of spent nickel-cadmium batteries Journal of University of
Science and Technology (Beijing) 7: pp. 126-131.

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