3140 Chem. Mater.

1999, 11, 3140-3146

Synthesis of Nickel Hydroxide by Homogeneous

Alkalinization. Precipitation Mechanism
Galo J. de A. A. Soler-Illia,† Matı́as Jobbágy,† Alberto E. Regazzoni,*,‡ and
Miguel A. Blesa‡
INQUIMAE, Facultad de Ciencias Exactas y Naturales, Universidad de Buenos Aires,
Pabellón II, Ciudad Universitaria, 1428-Buenos Aires, Argentina, and
Unidad de Actividad Quı́mica, Comisión Nacional de Energı́a Atómica,
Av. del Libertador 8250, 1429-Buenos Aires, Argentina
Received April 19, 1999. Revised Manuscript Received July 21, 1999

Uniform microcrystalline nickel(II) hydroxide particles have been prepared via the
homogeneous alkalinization of nickel(II) nitrate solutions by urea hydrolysis. The nature of
the precipitated solids depends on the temperature of synthesis. At ca. 423 K, i.e., under
the hydrothermal conditions attained by microwave heating, â-Ni(OH)2 forms upon the fast
ripening of R-Ni(OH)2. In the range 363-343 K, R-Ni(OH)2 is always the final product. The
evolution of the systems during the precipitation of R-Ni(OH)2 is analyzed in terms of the
kinetic factors that control nucleation and growth. A precipitation mechanism, based on
the principle of minimal structural change, is proposed; it is suggested that the edge-on
condensation of Ni4(OH)44+ tetramers is a key step in the sequence of events that conduct
from hexaaquo Ni2+ to R-Ni(OH)2.

Introduction depends on the microstructural, as well as the textural,

characteristics of the active material,11 a simple and
Nickel (hydr)oxides are the active material of the reliable synthesis procedure becomes a matter of im-
cathodes of rechargeable alkaline batteries. As such, portance.
their electrochemical and crystallochemical properties The most commonly used precipitation procedures are
have been thoroughly studied.1-5 Different solid phases indeed simple; basically, they involve the mixing of
have been described: R- and â-Ni(OH)2, with Ni in the nickel salt solutions and bases. However, due to the very
+2 oxidation state, and â- and γ-NiOOH, with Ni in the large supersaturations that are attained, reproducibility
+3 state, all of them involved in the charge-discharge is seldom warranted, especially when R-Ni(OH)2 is the
cycles.6 Among the hydroxides,7 R-Ni(OH)2 is the most desired product. For instance, this procedure leads to
active material because of its larger conductivity, which mixtures of R and â hydroxides if the precipitation
is ionic in nature.2,3 With the aim of improving the reaction is not quenched rapidly.12 The difficulties
cycling durability of Ni cathodes, attempts have been intrinsic to this procedure are further illustrated by the
made to block the R-Ni(OH)2 f â-Ni(OH)2 ripening by fact that solids described as âbc (badly crystallized â-Ni-
enhancing the stability of the hydrotalcite-like R- (OH)2)13 and as “neither R nor â”14 have been prepared
phase.8-10 Since the overall performance of Ni cathodes at essentially the same synthesis conditions. To obtain
single-phase R-Ni(OH)2 samples, addition of surface-
† Universidad de Buenos Aires. active solutes was found to be necessary.15
‡ Unidad de Actividad Quı́mica.
* To whom correspondence should be addressed. Homogeneous precipitation procedures, in which the
(1) Delahaye-Vidal, A.; Beaudoin, B.; Sac-Epée, N.; Tekaia-Ehlsis- degree of supersaturation is gradually increased, are
sen, K.; Audemer, A.; Figlarz, M. Solid State Ionics 1996, 84, 239. more easy to control and should not face the liabilities
(2) Barnard, R.; Randell, C. F.; Tye, F. L. J. Appl. Electrochem.
1980, 10, 109. of the aforementioned ones. Among these procedures,
(3) Barnard, R.; Randell, C. F.; Tye, F. L. J. Appl. Electrochem.
1980, 10, 127.
(4) Portemer, F.; Delahaye-Vidal, A.; Figlarz, M. J. Electrochem. (8) Delahaye-Vidal, A.; Figlarz, M. J. Appl. Electrochem. 1987, 17,
Soc. 1992, 139, 671. 589.
(5) Oliva, P.; Leonardi, J.; Laurent, F.; Delmas, C.; Braconnier, J. (9) Faure, C.; Delmas, C.; Willmann, P. J. Power Sources 1991, 35,
J.; Figlarz, M.; Fievet, F.; de Guibert, A. J. Power Sources 1982, 8, 263.
229. (10) Tekaia-Ehisissen, K.; Delahaye-Vidal, A.; Genin, P.; Figlarz,
(6) Bode, H.; Dehmelt, K.; Witte, J. Electrochim. Acta 1966, 11, M.; Willmann, P. J. Mater. Chem. 1993, 3, 883.
1079. (11) Figlarz, M.; Gérand, B.; Delahaye-Vidal, A.; Dumont, B.; Harb,
(7) Whereas the notation â-Ni(OH)2 identifies a hydroxide that is F.; Coucou, A. Solid State Ionics 1990, 43, 143.
an isomorph of brucite, the notation R-Ni(OH)2 has been frequently (12) Le Bihan, S.; Guenot, J.; Figlarz, M. C. R. Acad. Sci. Paris
used to describe a set of compounds with chemical compositions that 1970, C270, 2131.
are more proper of basic salts rather than of a hydroxide. The latter (13) Fouassier, M.; Faure, C.; Delmas, C. J. Power Sources 1991,
notation, however, denotes the typical turbostratic nature of these 35, 279.
compounds, i.e., the random orientation of the defective brucite-like (14) Rajamathi, M.; Subbanna, G. N.; Kamath, P. V. J. Mater.
Ni(OH)2 layers that are spaced along the c-axis by intercalated water Chem. 1997, 7, 2293.
molecules. In what follows, R-Ni(OH)2 identifies these hydrotalcite- (15) Kamath, P. V.; Ismail, J.; Ahmed, M. F.; Subbanna, G. N.;
like compounds without implying any specific stoichiometry. Gopalakrishnan, J. J. Mater. Chem. 1993, 3, 1285.

10.1021/cm9902220 CCC: $18.00 © 1999 American Chemical Society

Published on Web 10/15/1999
Synthesis of Nickel Hydroxide Chem. Mater., Vol. 11, No. 11, 1999 3141

homogeneous alkalinization by urea hydrolysis is per-

haps one of the most suitable.16 In fact, the urea method
has already been used to prepared single-phase R-Ni-
(OH)2 powders.17-20 The further advantages of this
procedure have been nicely illustrated by Avena et al.19
In some cases, however, R + âbc mixtures have been
obtained. This seems to be a consequence of the rather
restricted range of experimental conditions that has
been explored.
Clearly, the optimization of any synthesis procedure
requires not only a systematic experimental study but
also sound knowledge of the involved processes. Sur-
prisingly, none of the previous works address the
nucleation and growth mechanism. In this paper, we
investigate the precipitation of nickel(II) hydroxide from
urea-containing solutions under a wide range of experi-
mental conditions, including hydrothermal conditions
attained by microwave heating, and analyze the pro-
cesses that lead to the formation of the solid particles.
Figure 1. Time dependence of pH (upper) and Ni(II) concen-
Experimental Section tration (lower) during the aging of the [Ni(II)]0 ) 5.4 × 10-3
mol dm-3 system at 363 K.
Materials. Nickel nitrate stock solutions (0.025 mol dm-3)
were prepared by dissolving Ni2(OH)2CO3 in dilute HNO3 (final The precipitated solids were then collected by filtration
pH ∼ 3), filtered through 0.22 µm pore-size cellulose nitrate through 0.22 µm pore size cellulose nitrate membranes,
membranes, and stored in plastic bottles. washed three times with cold deionized water, and dried in
All solutions were made up using analytical grade reagents vacuo at room temperature. Supernatant solutions were stored
and deionized water (18 MΩ cm) obtained from a Milli-Q for chemical analyses; pH was measured ((0.02 units) using
apparatus. All glassware was washed using diluted HNO3 (1:1 a combined glass-electrode, and Ni(II) was determined, within
volume ratio) and rinsed thoroughly with water and steam. 1%, by atomic absorption spectrometry (AAS).
Synthesis Procedures. Nickel hydroxide particles were Sample Characterization. The synthesized solids were
prepared by aging solutions containing nickel nitrate (1 × 10-3 characterized by powder X-ray diffraction (PXRD) in a Siemens
mol dm-3 e [Ni(NO3)2] e 5 × 10-3 mol dm-3) and urea (0.5 D-5000 instrument, using the graphite-filtered Cu KR radia-
mol dm-3) at prefixed temperatures for different periods. Two tion (λ ) 1.5406 Å); peak analyses were performed with a
series of experiments were performed. In one of them, the profile fitting software.23 All fwhm (full width at half-
temperature was kept constant at 363 K and the initial nickel maximum), from which crystallite sizes were determined, were
concentration, [Ni(II)]0, varied. In the other, [Ni(II)]0 was fixed corrected for instrumental broadening using a highly crystal-
at 5.4 × 10-3 mol dm-3 and the temperature varied between line quartz specimen as reference.
343 and ca. 423 K. In all cases, the initial pH was fixed at 5.0 Scanning electron microscopy images were obtained with a
( 0.1 by the addition of NH3. Philips SEM 515 equipment. Fourier transform infrared
Experiments were performed as follows. Fresh starting (FTIR) spectra were recorded in a Nicolet 510 P spectrometer
solutions were prepared by mixing the necessary amounts of using KBr pellets. Elemental analyses (C, H, and N) were
the Ni(II) stock solution, solid urea, and water to yield the carried out in a Carlo Erba CHON-S analyzer. Ni contents
desired reactant concentrations. Filtered aliquots (10 cm3) were were assessed by AAS of dissolved solids; oxygen contents were
poured into 20 cm3 screw-capped borosilicate test tubes, which calculated by difference. TG and DSC measurements were
were then placed in a thermostatic water bath preheated at performed at 5.0 K min-1, under a nitrogen flow to prevent
the working temperature ((0.5 K). After prefixed time inter- Ni(II) oxidation.
vals, the tubes were removed from the water bath and
immersed in an ice-water mixture to quench the reaction; the Results
temperature drop during the first minute of cooling was ca.
60%. The Evolution of the Systems. To determine the
At temperatures above 373 K, the experiments were carried best synthesis conditions, the changes in the composi-
out in a commercial CEM MDS 2000 microwave digestor using tion of the solutions were recorded as a function of the
a 20 cm3 heavy duty Teflon vessel. The working temperature,
which should be reached in less than 3 min,21 was estimated aging time. The evolution of pH and of dissolved Ni(II)
from the set maximum pressure using the coexistence curve concentration during the aging of the [Ni(II)]0 ) 5.4 ×
of pure water.22 10-3 mol dm-3 system at 363 K are shown in Figure 1.
Precipitation starts once a certain critical pH value is
(16) Soler-Illia, G. J. de A. A.; Jobbágy, M.; Candal, R. J.; Regazzoni,
exceeded. Soon after the precipitation onset, the pH
A. E.; Blesa, M. A. J. Dispersion Sci. Technol. 1998, 19, 207. drops as a consequence of the inversion of the unbalance
(17) Maruthiprasad, B. S.; Sastri, M. N.; Rajagopal, S.; Seshan, K.; of the rates of urea hydrolysis and base consumption
Krishnamurthy, K. R.; Rao, T. S. R. Proc. Indian Acad. Sci. 1988, 100,
459. that is prompted by the burst of nuclei.16,24 Later, the
(18) Durand-Keklikian, L.; Haq, I.; Matijevic, E. Colloids Surf. A rate of urea hydrolysis offsets that of base consumption,
1994, 92, 267.
(19) Avena, M. J.; Vázquez, M. V.; Carbonio, R. E.; de Pauli, C. P.;
Macagno, V. A. J. Appl. Electrochem. 1994, 24, 256. (22) Harvey, A. H.; Peskin, A. P.; Klein, S. A. NIST Standard
(20) Dixit, M.; Subbanna, G. N.; Kamath, P. V. J. Mater. Chem. Reference Database 10; NIST/ASME Steam Properties, Ver. 2.11;
1996, 6, 1429. USSC: Washington, DC, 1996.
(21) Kingston, H. M.; Jassie, L. B. Introduction to Microwave (23) Diffrac-AT 3.0, Siemens, 1993.
Sample Preparation; ACS Professional Publications: Washington, DC, (24) Candal, R. J.; Regazzoni, A. E.; Blesa, M. A. Colloids Surf. A
1988. 1993, 79, 191.
3142 Chem. Mater., Vol. 11, No. 11, 1999 Soler-Illia et al.

Table 1. Precipitation Onsets of r-Ni(OH)2

[Ni(II)]0,
exp no. 103/mol dm-3 T/K t*/min pH* log Ω*
K902 1.50 363 15 8.08 0.53
K903 2.85 363 18 7.93 0.52
K905 4.25 363 20 7.88 0.59
S590 5.40 363 22 7.81 0.56
S580 5.40 353 45 7.68 0.30
S570 5.40 343 160 7.83 0.59
S5M 5.40 ca. 423 <5

Figure 3. Evolution of the crystallite size during the precipi-

tation of R-Ni(OH)2 from the [Ni(II)]0 ) 5.4 × 10-3 mol dm-3
system at 363 K; the arrow indicates the onset of precipitation.
Inset: crystallite height plotted as a function of the precipitated
fraction.

presented as a function of the reduced time, τ ) t/t*,

where t*, also listed in Table 1, is the time required to
reach the precipitation onset. The curves overlap each
other. The master curves presented in Figure 2 indicate
that, once the temperature dependence of t* has been
established, the aging time required to reach a certain
precipitation extent can be estimated from just a refer-
ence experiment. Further, they convey the idea that the
same overall precipitation mechanism operates under
the different synthesis conditions.
PXRD patterns of the solids precipitated during the
aging of the [Ni(II)]0 ) 5.4 × 10-3 mol dm-3 system at
363 K show peaks, which gain in definition as the aging
Figure 2. Evolution of dissolved Ni(II) concentration (A) and progresses, at 7.25, 3.614, 2.657, and 1.552 Å; they
pH (B) during the aging of the [Ni(II)]0 ) 5.4 × 10-3 mol dm-3 correspond to the [003], [006], [012], and [110] reflec-
system at 343 (O), 353 (0), and 363 K (b). (A) presents the pH tions of R-Ni(OH)2, respectively.26 Figure 3 depicts the
dependence of [Ni(II)]. In (B), pH is plotted as a function of evolution of the size of the crystallites along the [003]
the reduced time (τ ) t/t*). and [110] directions. It shows that the growth is highly
anisotropic; note the almost instantaneous development
and a well-defined pH plateau accompanies massive of the basal planes, which is followed by a much slower
precipitation. growth along the c-direction. The height of the crystal-
Table 1 shows that the pH values at the precipitation lites, L003, levels off once most of the Ni(II) has been
onsets, pH*, although fairly independent of tempera- removed from solution; the inset in Figure 3 shows that
ture, depend on the initial Ni(II) concentration. Instead, L003 increases almost linearly with the fraction of
Ω*, the derived supersaturations (calculated as IAP*/ precipitated Ni(II). Figure 3 further indicates that a
Kps, where IAP* is the ion activity product at the crystalline, albeit turbostratic, solid forms as soon as
precipitation onset and Kps is the solubility product of the precipitation is triggered.
nickel hydroxide, which was taken from ref 25), are Crystallite sizes presented in Figure 3 were calculated
constant and independent of the synthesis conditions using the Warren modification of the Scherrer equation,
(Table 1); the only exception is experiment S580. Thus,
Ω* ) 100.56(0.05 can be identified as the critical super- Kλ
saturation. Bhkl(2θ) ) (1)
Lhkl cos θ
Figure 2a shows the changes of the dissolved Ni(II)
concentration at three different temperatures, plotted
where Bhkl is the fwhm of a given [hkl] peak, Lhkl is the
as a function of the measured pH. At a fixed [Ni(II)]0,
crystallite size along the [hkl] direction, and K is the
the extent of precipitation is solely determined by the
structure factor, which takes into account the strong
evolution of pH, irrespective of the synthesis tempera-
asymmetry of the [hk0] reflections that is produced by
ture. The observed right-leaned hump reflects again the
the turbostraticity of R-Ni(OH)2; for the [hk0] reflections,
faster rate of base consumption (compared to that of
K ) 1.84, and for the [00l] ones, K ) 0.94.27
urea hydrolysis) caused by the burst of nuclei. The
Synthesis of r-Ni(OH)2. PXRD patterns of samples
observed overlap further suggests that the overall shape
synthesized under different experimental conditions are
of the pH evolution is also independent of temperature,
presented in Figure 4. At 363 K and below, R-Ni(OH)2
although in different time scales. Figure 2b shows the
course followed by pH at the different temperatures,
(26) Braconnier, J. J.; Delmas, C.; Fouassier, M.; Figlarz, M.;
Beaudouin, B.; Hagenmueller, P. Rev. Chim. Miner. 1984, 21, 496.
(25) Novak-Adamic, D.; Kosovic, B. J. Inorg. Nucl. Chem. 1973, 35, (27) Klug, H. P.; Alexander, L. E. X-Ray Diffraction Procedures, 2nd
2371. ed.; Wiley: New York, 1974.
Synthesis of Nickel Hydroxide Chem. Mater., Vol. 11, No. 11, 1999 3143

those at 1600 and 1430 cm-1 are assigned to the νCdO

doublet of bidentate and monodentate carbonate ions
in Cs symmetry.29 The band at 680 cm-1 corresponds to
the δO-H wagging vibration.5
The bands of cyanate (2250 cm-1) and carbonate (1600
and 1430 cm-1) denote the incorporation of the byprod-
ucts of urea hydrolysis within the solid particles.
Incorporation of carbonate is a characteristic of most of
the solids synthesized via the urea method; actually, in
many cases, the final product is a basic carbonate.16,30,31
Incorporation of cyanate, however, is rare and has been
reported only in the case of nickel hydroxide.17,18,20 The
reason for this distinct behavior may be traced back to
the comparatively high pH at which nickel hydroxide
precipitates (cf. ref 32) and to the rather inert nature
of the d8 Ni2+ ions; as pH rises, the hydrolysis of urea
slows down and the steady-state concentration of cyan-
ate increases considerably,16 thus favoring the likely
Figure 4. PXRD patterns of powders obtained upon the aging incorporation of robust NiOCN+ complexes into the
of the [Ni(II)]0 ) 5.4 × 10-3 mol dm-3 system at different
conditions: (a) 180 min at 343 K; (b) 5 min at ca. 423 K; (c) 30
growing Ni(OH)2 sheets. Elemental analyses of typical
min at ca. 423 K. samples are in the order 4.7% N, 5.8% C, 2.0% H, and
51.0% Ni and yield the formula Ni(OH)1.27(CO3)0.17-
(OCN)0.39‚0.46H2O, which is in good agreement with
earlier results.17
Undoubtedly, OCN- and CO32- replace lattice OH-
ions or, in the words of Delahaye-Vidal et al.,1 take up
OH vacancies. These anions cannot be electrostatically
intercalated within the interlamellar space of R-Ni-
(OH)2, for such an intercalation is only akin to LDHs
(layered double hydroxides), the “positive” counterpart
of clays.33,34 It has been suggested,35 however, that the
protonation of basal OH groups may provide the re-
quired excess of positive charge. This possibility is
indeed unlikely, because among the different types of
surface OH groups, tricoordinated OH2 is the most
acidic one.36
Figure 5. FTIR spectra of powders obtained upon the aging Nickel hydroxide particles prepared by other common
of the [Ni(II)]0 ) 5.4 × 10-3 mol dm-3 system at different procedures, say, dropwise addition of ammonia to Ni-
conditions: (a) 180 min at 343 K; (b) 5 min at ca. 423 K; (c) 30 (II) nitrate solutions, present a somewhat lower degree
min at ca. 423 K. of OH substitution and yield, typically, Ni(OH)1.43-
(CO3)0.19(NO3)0.19‚1.8H2O.1 They also present larger
is always the final product; at ca. 423 K, instead, the water contents, which are reflected in their larger d003
initially formed R-Ni(OH)2 (pattern b) evolves to â-Ni- spacings that may be up to 8.5 Å. Such spacings
(OH)2 (pattern c) in a rather short period (30 min). The correspond to the thickness of a poorly packed water
lattice parameters of the synthesized R-Ni(OH)2 par- layer separating the octahedral Ni(OH)2 sheets.5 The
ticles are a ) 3.103 Å and c ) 21.75 Å. The latter, lower interbasal distances characterizing the R-Ni(OH)2
derived from the measured interbasal distance (d003 ) particles prepared by the urea method, on the other
7.25 Å), is in good agreement with those reported earlier hand, are consistent with interlamellar heights that
for R-Ni(OH)2 particles precipitated from urea-contain- correspond to a loose water monolayer.37 The origin of
ing solutions18,20 but is somewhat lower than those
reported for R-Ni(OH)2 particles prepared using other (29) Nakamoto, K. Infrared and Raman Spectra of Inorganic and
precipitation procedures.1,5 The final sizes of the R-Ni- Coordination Compounds, 4th ed.; Wiley: New York, 1986; p 220.
(OH)2 crystallites range from 150 to 200 Å. (30) Candal, R. J.; Regazzoni, A. E.; Blesa, M. A. J. Mater. Chem.
1992, 2, 657.
Figure 5 presents the FTIR spectra of the different (31) Soler-Illia, G. J. de A. A.; Candal, R. J.; Regazzoni, A. E.; Blesa,
samples. Spectra a and b are typical of R-Ni(OH)2 M. A. Chem. Mater. 1997, 9, 184.
(32) (a) Baes, C. F.; Mesmer, P. E. The Hydrolysis of Cations; John
particles prepared by the urea method.18,20 The narrow Wiley: New York, 1976. (b) Smith, R. M.; Martell, A. E. Critical
band at 3650 cm-1 corresponds to the νO-H stretching Stability Constants; Plenum: New York, 1989; Vol. 6.
of the geminal OH groups of the brucite-like structure. (33) Brindley, G. W.; Kikkawa, S. Am. Mineral. 1979, 64, 836.
(34) LDHs have the formula M(II)1-xM(III)x(OH)2Xx/n.yH2O, where
The broad band centered at 3400 cm-1 is due to the νO-H n is the charge number of the exchangeable anion X. See, e.g.:
vibration of H-bonded water molecules located in the Constantino, V.; Pinnavaia, T. J. Inorg. Chem. 1995, 34, 883.
interlamellar space of the turbostratic structure of R-Ni- (35) Kamath, P. V.; Annal-Therese, G. H.; Gopalakrishnan, J. J.
Solid State Chem. 1997, 128, 38.
(OH)2. The very strong absorption band at 2250 cm-1 (36) (a) Hiemstra, T.; van Riemsdijk, W. H.; Bolt, G. H. J. Colloid
is assigned to the νCtN vibration of OCN- anions,28 and Interface Sci. 1989, 133, 91. (b) Hiemstra, T.; de Wit, J. C. M.; van
Riemsdijk, W. H. J. Colloid Interface Sci. 1989, 133, 105. (c) Hiemstra,
T.; van Riemsdijk, W. H. Colloids Surf. 1991, 59, 7.
(28) Forster, D.; Goodgame, D. M. L. J. Chem. Soc. 1965, 262. (37) Le Bihan, S.; Figlarz, M. Thermochim. Acta 1973, 6, 319.
3144 Chem. Mater., Vol. 11, No. 11, 1999 Soler-Illia et al.

Figure 6. TG (a) and DSC (b) of R-Ni(OH)2 obtained by aging

the [Ni(II)]0 ) 5.4 × 10-3 mol dm-3 system at 343 K for 180
min. Temperature ramp, 5 K min-1; N2 flow, 50 cm3 min-1; Figure 7. SEM micrograph of R-Ni(OH)2 particles synthesized
the sample was vacuum-dried before TG analysis. by aging the [Ni(II)]0 ) 5.4 × 10-3 mol dm-3 system at 343 K
for 180 min.
this singular disparity is unclear and cannot be at- Synthesis of â-Ni(OH)2. As shown in Figure 4
tributed to any possible effect due to the presence of (pattern c), the urea method is also suitable for the
cyanate. Perhaps, this disparity would reflect a subtle synthesis of â-Ni(OH)2. In this case, however, hydro-
difference in the growth mechanisms operating under thermal conditions are required; in fact, at 363 K, no
the different synthesis conditions. â-Ni(OH)2 could be detected, even when the systems
were aged for up to 96 h. The lattice parameters of the
The different water contents of the R-Ni(OH)2 samples
formed â-Ni(OH)2 particles are a ) 3.119 Å and c )
prepared by the different procedures are further re-
4.560 Å, and as judged from the FTIR results (see
flected in their overall thermal behaviors. Figure 6
spectrum c in Figure 5), they are cyanate-free and
indicates that the thermal decomposition of R-Ni-
contain only a modest amount of carbonate. Morpho-
(OH)1.27(CO3)0.17(OCN)0.39‚0.46H2O to NiO (bunsenite)
logically, the particles resemble those of R-Ni(OH)2 (cf.
takes place in a single endothermic step centered at 593
Figure 7).
K (DSC), in which interlamellar and condensation water
Although the characteristics of the synthesized â-Ni-
molecules, as well as carbonate and cyanate decomposi-
(OH)2 particles are roughly the same of those prepared
tion products, are released simultaneously (TGA); the
by prolonged boiling of highly alkaline R-Ni(OH)2 sus-
shallow band centered at ca. 373 K (DSC) corresponds
pensions,1,5 the hydrothermal aging of nickel nitrate
to the loss of physisorbed water. In the case of samples
solutions containing urea has clear advantages: the
with larger water contents, instead, formation of NiO
synthesis is rapid and involves a single operation.
is preceded by the partial loss of interlamellar water
Indeed, at ca. 423 K, an aging period of just 30 min
molecules that takes place within 393-433 K;37 this
suffices to produce pure â-Ni(OH)2 powders.
partial dehydration leads to water contents of about 0.6
molecules per nickel and is followed by a reduction of
Discussion
the interbasal distance to ca. 7.0 Å. These different
thermal behaviors should indicate the larger interaction This work shows that once the adequate experimental
between the interlamellar water molecules and the conditions have been set, the urea method is a very
octahedral Ni(OH)2 sheets in the monolayer configura- suitable procedure for the synthesis of single-phase
tion. Interestingly, the presence of cyanate in the R-Ni- R-Ni(OH)2 and â-Ni(OH)2 powders. Although the rela-
(OH)2 particles synthesized by the urea method does not tively high contents of cyanate of the R-Ni(OH)2 powders
affect the temperature at which NiO forms.18-20,37,38 prepared by this method may constitute an important
The SEM micrograph presented in Figure 7 shows the liability of the material, our results demonstrate that
typical morphology of the synthesized R-Ni(OH)2 par- the presence of cyanate does not affect its crystal-
ticles. Although they exhibit the expected crystalline lochemical properties (Figure 4) or its thermal ones
habit, their petal-like shape denotes a certain degree (Figure 6); furthermore, the electrochemical response
of unordered crystallite aggregation; note that the of R + âbc samples seems not to be affected by the
average particle size is much larger than the nominal presence of cyanate.19
size of the crystallites. While the common R-Ni(OH)2 The precipitation of nickel hydroxide from urea-
preparation procedures seem to provide conditions containing solutions can be rationalized interpreting the
under which aggregation is minimized (small hexagonal Ostwald step rule39 in terms of the principle of minimal
platelets usually form), the mild conditions of the urea structural change;40,41 this implies that the coordinative
method favor the formation of crystalline aggregates.16 environment of the aqueous species that promote nucle-
In fact, spherical aggregates of R-Ni(OH)2 have been
prepared via the urea method, albeit under different (39) Ostwald, W. Z. Phys. Chem. 1897, 22, 289.
(40) Hückel, W. Theoretische Grundlagen der Organischen Chemie;
experimental conditions.18 Akademische Verlagsgellschaft: Leipzig, 1934.
(41) Boldyreva, E. In Implications of Molecular and Material
Structure for New Technologies; Howard, J. A. K., Allen, F. H., Shields,
(38) Gabr, R. M.; El-Naimi, A. N.; Al-Thani, M. G. Thermochim. G. P., Eds.; NATO-ASI Series E; Kluwer Academic Press: Dordretch,
Acta 1992, 197, 307. 1999; p 151.
Synthesis of Nickel Hydroxide Chem. Mater., Vol. 11, No. 11, 1999 3145

Figure 8. Schematic representation of the sequence of events that lead to the nucleation of R-Ni(OH)2.

ation should closely resemble those of the ions in the which are assumed to be stages of a smooth sequence
solid state. As urea hydrolyzes, that conducts to the solid and not dead-end entities.
Condensation along the Ni3 plane of the tetramers leads
k1
OC(NH2)2 {\ } OCN- + NH4+ (2) to
k -1

k2
OCN- + H+ + 2H2O 98 HCO3- + NH4+ (3)

different nickel hydroxo species form along with cyanate bonds (the prime denotes ions of a different tetramer),
and bicarbonate complexes. At the precipitation onset where the bridging OH- ions lose their coordination to
(say, pH 7.81), the hexaaquo Ni2+ ion predominates, the out-of-plane Ni(4); formation of Ni(1)-OH-Ni(1′)
NiOH+, NiOCN+, Ni(OCN)20, and NiHCO3+ accounting and Ni(2)-OH-Ni(2′) bonds and release of two H3O+
for about 1, 10, 1, and 3%, respectively;42 Ni2(OH)22+ take place simultaneously. Aggregation of additional
and Ni4(OH)44+ are negligible. Yet, the constancy of Ω* tetramers defines the close-packed arrangement of OH-
(Table 1) indicates that only OH- ions participate in ions and reduces the number of bonds linking the out-
nuclei formation. Since nucleation of metal (hydrous)- of-plane Ni(4) ions, which, at a certain point, are ejected
oxides is often preceded by the formation of oligomeric from the growing polyion. Once the size of the polyion
hydroxo moieties,43,44 the role of the polynuclear species surpasses a critical value, subsequent growth proceeds
should be central, especially that of Ni4(OH)44+, in which by incorporation of hydroxylated and complexed mono-
OH- ions are already tricoordinated.45,46 Thus, we mers.
propose that the nucleation of R-Ni(OH)2 is driven by This bidimensional condensation model, in line with
the edge-on condensation of tetrameric units (see the the periodic bond chain (PBC) approach,48 leads to single
scheme presented in Figure 8); a similar nucleation Ni(OH)2 layers, which must serve as templates for the
mechanism has already been postulated for monoclinic condensation of further tetramers that triggers the
ZrO2.47 This process is the continuation of the olation nucleation and growth of the next layers in a turbo-
reactions that lead to the dimer and to the tetramer, stratic fashion. Accordingly, the crystallites identified
at almost the precipitation onset (Figure 3) are com-
(42) The distribution of aqueous Ni(II) species was calculated posed of seven Ni(OH)2 layers with a basal dimension
solving eqs 2 and 3 under the assumption that all hydrolytic and
complexation reactions involving Ni(II) are equilibrated; kinetic data of ca. 19 nm, i.e., about 35 × 35 unit cells. Although
and equilibrium constants were taken from refs 16 and 32, respectively. other nucleation pathways can be envisaged, all of them
For further details, see: Soler-Illia, G. J. de A. A. Ph.D. Thesis, invoke aqueous Ni(II) species that have not been
Universidad de Buenos Aires, Argentina, 1998.
(43) Matijević, E. Pure Appl. Chem. 1980, 52, 1179. described in the literature.
(44) Livage, J.; Henry, M.; Sanchez, C. Prog. Solid State Chem. As the aging proceeds, further growth in the c-
1988, 18, 259. direction takes place (Figure 3). The linear relationship
(45) Kolski, G. B.; Kjeldahl, N. K.; Margerum, D. W. Inorg. Chem.
1969, 8, 1211. between L003 and the fraction of precipitated nickel (see
(46) It should be recalled that in the brucite-like Ni(OH)2 layers inset in Figure 3) suggests that the number of crystal-
each OH- ion is tricoordinated to Ni2+ ions that occupy one-half of the
octahedral holes of the hexagonal close packing of hydroxide ions.
(47) Bleier, A.; Cannon, R. M. Mater. Res. Soc. Symp. Proc. 1986, (48) Hartman, P. In Crystal Growth: an Introduction; Hartman,
73, 71. P., Ed.; North-Holland: Amsterdam, 1973.
3146 Chem. Mater., Vol. 11, No. 11, 1999 Soler-Illia et al.

lites remains constant after the burst of nuclei; viz., (Figure 4). This result is another example of the well-
nucleation and particle growth occur separately. This known Ostwald step rule. According to Le Bihan and
is a consequence of the fast relief of the supersaturation Figlarz52 and Delahaye-Vidal et al.,1 this transformation
that occurs soon after the precipitation onset (see Figure proceeds through a dissolution-recrystallization mech-
2). The growth of the xy-planes, on the other hand, is anism, despite the similarities of the crystal structures.
rapidly arrested; L110 remains constant during the Although the factual evidence is scarce, the absence of
entire aging (Figure 3). This is probably due to a cyanate in the final solids (Figure 5, spectrum c)
blocking action by CO32- or, more likely, OCN-; the supports this contention. Crystallization of â-Ni(OH)2
poisoning of growth sites by anions is well-known.49 The should follow essentially the same precipitation se-
size of the final polycrystalline petal-like particles quence outlined above.
(Figure 7) is, however, determined by the extent of the
ordered aggregation of crystallites (primary particles)
Acknowledgment. This work was partially sup-
along the basal direction, in line, again, with the PBC
ported by grants from UBA (EX036) and CONICET (PIP
approach; ordered aggregation of primary particles is
4196). G.J. de A.A.S.-I. thanks the Fellowship awarded
well documented.50,51 This process may be assisted by
by UBA. A.E.R. and M.A.B. are members of CONICET.
carbonate anions, which can not only reduce the charge
Thanks are due to Grupo Análisis de Trazas, IN-
of the edges of the “flat” crystallites but also bridge them
tightly. QUIMAE, for sharing their microwave digestor. The
Under hydrothermal conditions (423 K), the initially authors are grateful to Gabbo’s, where rendezvous were
precipitated R-Ni(OH)2 readily ripens into â-Ni(OH)2 sparkling, indeed.
CM9902220
(49) Sunagawa, I. Estudios Geolog. 1982, 38, 127.
(50) Hsu, W. P.; Ronnquist, L.; Matijević, E. Langmuir 1988, 4, 31.
(51) Ocaña, M.; Matijević, E. J. Mater. Res. 1990, 5, 1083. (52) Le Bihan, S.; Figlarz, M. J. Cryst. Growth 1972, 13/14, 458.