Journal of Crystal Growth 373 (2013) 111117

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Journal of Crystal Growth

journal homepage: www.elsevier.com/locate/jcrysgro

Polyelectrolyte effects on the crystallization phenomena of the

lithium carbonate
Hiroto Watamura n, Hironobu Marukawa, Izumi Hirasawa
Department of Applied Chemistry, School of Advanced Science and Engineering, Waseda University, 3-4-1 Okubo, Shinjuku-ku, Tokyo 169-8555, Japan

a r t i c l e i n f o

abstract

Available online 16 November 2012

Anionic polyelectrolyte effects on the lithium carbonate crystallization phenomena were investigated.
Li2CO3 crystals were obtained by reactive crystallization with seed crystals. Polyelectrolytes were
dissolved into the reactive eld before the reaction. Obtained crystals were observed with scanning
electron microscopy (SEM) and crystal size and agglomeration degree were measured by the SEM
images. The results show that Li2CO3 crystallized different shape and size from absence of polyelectrolyte in those reactive elds. Especially polyacrylic acid (PAA) improved on the agglomeration of the
crystals and shaped them high aspect needles. Thus other experimental conditions including PAA
molecular weight and concentration, reaction time, supersaturation by Li concentration were investigated in addition. As a result, obtained crystals were not different in each PAA molecular weight
reactive elds. Meanwhile PAA concentration has optimum range. Li2CO3 formed less agglomeration
and higher aspect around 1 g/l. In the concentration, Li2CO3 did not agglomerate regardless of aging
time and Li concentration. Moreover crystals became rectangle shape in higher Li concentration.(020)
face intensity of the rectangle shape crystals increased according to XRD pattern. PAA affected the
facial growth. These results may provide a method of morphological change and clearly crystallization
of Li2CO3.
& 2012 Elsevier B.V. All rights reserved.

Keywords:
A1. Crystal structure
A1. X-ray diffraction
A2. Growth from high temperature solutions
A2. Seed crystals
B1.Lithium compounds

1. Introduction
Lithium resources are utilized in the industry as the form of
lithium carbonate, because of their stability and simple form. A
large variety of applications are attempted, such as battery
electrode [1], add-in material to ceramic or glass [2], lubricity
agent and pharmaceutical agent [3]. These applications require
customized quality, especially size, morphology and monodispersion in the functional materials. However studies on controlling quality of lithium carbonate are not investigated well, as
Li2CO3 crystals tend to form agglomerate stronger than other
carbonates and encrustation easily. Additionally, Li2CO3 has
higher solubility than other sparingly soluble carbonates and
particular precipitation behavior. Studies on supersolubility [4,5]
or kinetics [6] were investigated on lithium carbonate. However,
few studies on controlling crystal size or morphology were
reported on crystallization concept.
Various methods of producing carbonate have been investigated, asprecipitation [710], gasliquid reaction of carbon dioxide [1113], bio-mineralization [1417] and so on. Reactive
crystallization is one of the simple methods to obtain carbonates,

Corresponding author. Tel.: 81 352863215; fax: 81 332086896.

E-mail address: watamu-hiro@fuji.waseda.jp (H. Watamura).

0022-0248/$ - see front matter & 2012 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.jcrysgro.2012.10.060

such as CaCO3[1821], BaCO3[22], which suggests that temperature, pH, concentration, uidized state and aging time have a
great inuence on crystal size and/or shape. Recently, soluble
polyelectrolyte additive in the reactive eld has been focused by
researchers. This is an effective method to control morphology. In
the reactive crystallization of sulfates or metal nano-sized particles, Polyethylenimine(PEI) which has amine groups, inhibited
growth, continuously nucleation and agglomeration. Monodispersed ne crystals were obtained [2328]. In carbonates,
especially CaCO3, polyelectrolyte or organic impurity effects were
actively investigated from bio-mineral synthesis [2932]. Some
researchers suggested that polyelectrolyte which has carboxylic
groups is effective for CaCO3 [33,34]. The carboxylic groups bind
the cations by strong interaction, lead morphological change and/
or less agglomeration.
These effects have some prospects to improve lithium
carbonate crystals. So in this research, we studied the reactive
crystallization of lithium carbonate in the polyelectrolyte reactive
eld. Two type polyelectrolyte, Polyacrylamide (PAM) which has
amine groups and Polyacrylic acid (PAA) which has carboxylic
groups were investigated. And effects of experimental
conditions including polyelectrolyte molecular weight and concentration, reaction time, supersaturation in the PAA reactive eld
which was especially effective one were investigated and
discussed.

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H. Watamura et al. / Journal of Crystal Growth 373 (2013) 111117

Nomenclature

a
n

agglomeration ratio, #/#

crystal number, #

2. Experimental
2.1. Materials
All chemicals are commercially available and are of analytical
grade. Lithium chloride and sodium carbonate were purchased
from Wako Pure Chemical Industries, Ltd. Polyacrylic acid (PAA;
Mw 5000 and 25,000: Wako Pure Chemical Industries, Ltd.) and
polyacrylamide (PAM: Poly sciences, Inc.) were used.
The solutions were prepared with deionized water which ltrated
through 1 mm membrane lter to eliminate the solid impurities.
2.2. Experimental procedure
The reactive crystallization of Li2CO3 was performed in
the solution of Polyelectrolyte using a single-jet crystallizer.

C
na
Ksp
S

Experimental set up is shown in Fig. 1. A 500 mL glass crystallizer

with water jacket was regulated at 65 1C by a thermostat.150 mL
Na2CO3 solution prepared in crystallizer and 1.0 g/L PAA or PAM
dissolved in the solution. 150 mL of LiCl solution was fed into the
crystallizer with 2.5 mL/min feeding rate. The sodium carbonate
solution and lithium chloride solution were prepared with
1.0 mol/Land 0.8 mol/L. Agitation rate was set at 400 rounds per
minute. Seed crystals were added at 30 min later in the feeding
time. The solution was kept for 1 h as aging time since completed
feeding. Obtained crystals were ltered by membrane lter which
have 0.45 mm pore sizes in suction ltration, and dried under
reduced pressure. Dried crystals were observed with a KEYENCE
VE-8800scanning electron microscope and measured the crystal
composition with Rigaku Rint-1100 powder X-ray diffraction.
Specic faces were not dened because of the agglomeration
behavior. Actually crystal shape which has three dimensions
should be regarded, but crystal size can dened only two dimension for at-screen image analysis on SEM photographs. So the
mean crystal size were dened the average length on longer
direction as long axis and shorter direction as short axis
for instance. About crystal numbers, crystals which concluded
ill-dened shapes were counted each single crystal by eyes.
The number of crystals analyzed from a single sample was
approximately 1000. The agglomeration ratio was dened by
Eq. (1).

Fig. 1. Experimental set up. 1-feed tank; 2-rotary pump; 3-agitatior; 4-water
jacket; 5-thermometer and 6-heater.

concentration, mol/L
agglomeration crystal number, #
solubility product constant
relative supersaturation

na
n

where n is the number of all crystals and na is number of

agglomerated crystals. The relative supersaturation was calculated by Eq. (2). Lithium carbonate is sparingly soluble compared
with other lithium compounds. Lithium has strong ionization
tendency and carbonates have enough concentration and high pH

Fig. 2. Obtained lithium carbonate crystals in the polyelectrolyte solution. (a) Additive-free (b) PAA and (c) PAM.

H. Watamura et al. / Journal of Crystal Growth 373 (2013) 111117

to ionize as carbonate ions, so supersaturation ratio is calculated

by Eq. (2) for instance,
11=3
0
2 
C Li
C CO23
A
S@
2
K sp

113

concentration was varied from 0.8 and 1.0, respectively. As

reference experiments, the Li2CO3 crystallized in the absence of
polyelectrolyte, and all the other conditions kept the same.

We investigated more detail in on the PAA effect, because

crystals became clear and less agglomerated in the PAA reactive
eld. In the experiment, the molecular weight of PAA was varied
from 5000 and 25,000; concentration of PAA was varied from 0 to
3 g/L; aging time was varied from 1 to 4 h; supersaturation by Li

Fig. 3. Effect of polyelectrolytes on crystal size.

Fig. 5. Effect of PAA amount. (a) Mean crystal size and (b) aspect ratio.

Fig. 4. Effect of Polyelectrolytes on CSD. (a) Long axis and (b) short axis.

Fig. 6. Effect of PAA concentrations. (a) Aspect ratio and (b) agglomeration ratio.

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H. Watamura et al. / Journal of Crystal Growth 373 (2013) 111117

3. Results and discussion

3.1. Effects of polyelectrolyte in the reactive eld
Typical effects of polyelectrolytes were shown in Fig. 2. Crystal
sizes were widely dispersed and strongly agglomerated in the

absence of polyelectrolyte. Crystals showed wide columnar shape

with agglomeration. In the PAA reactive eld, Li2CO3 crystals
became needle shaped; high aspect ratio and agglomeration was
improved. In the PAM reactive eld, crystals became plate-like
and some crystals grew radial shape. PAA and PAM signicantly
changed the shapes of Li2CO3 crystals.

Fig. 7. Li2CO3 crystals depended PAA concentration.PAA concentration (a) 0 g/L, (b) 0.1 g/L, (c) 1.0 g/L and (d) 3.0 g/L.

Fig. 8. Parameters depended on aging time. (a) Mean crystal size on long axis, (b) mean crystal size on short axis, (c) aspect ratio and (d) agglomeration ratio.

H. Watamura et al. / Journal of Crystal Growth 373 (2013) 111117

Figs. 3 and 4 showed the mean crystal size and crystal size
distributions on various reactive elds. PAA and PAM dominantly
inuenced on long axis to have larger size. Meanwhile signicant
differences appeared on the short axis direction. In the PAA
condition, crystal growth of long axis was increased and the short
axis decreased. It was suggested the effect appeared by PAA and Li
ion interaction. In the PAM condition, crystal growth of long and
short axis were increased. But crystal growth of the at face as
shown in Fig. 2(c) was inhibited, and some crystals became platelike. The functional group of PAM is different from PAA. So it was
assumed that different effects were observed. The detailed
mechanisms of effects were not clear, but polyelectrolytes had a
great inuence on the crystallization of Li2CO3. Especially PAA is
an effective polyelectrolyte which controlled shape and agglomeration clearly in the Li2CO3 crytals. It was suggested that the PAA
not only control crystal growth but also nucleation phase with
less agglomeration. Therefore we examined about PAA effects in
following sections.
3.2. Effect of PAA on reactive crystallization eld
3.2.1. Effects of molecular weight on crystal shape
The effect of molecular weight on PAA was investigated.
Obtained crystalline properties were shown in Fig. 5. The effect
with and without PAA was apparent. But difference between Mw
5000 and 25,000 was not recognized. Li2CO3of similar morphology crystallized at Mw 5000 and Mw 25,000, and high aspect
needle crystals were obtained. Both PAA of Mw 5000 and 25,000
improved agglomeration. So it was suggested that lithium carbonate crystallized in same mechanism.

agglomeration. Considering the crystal size, clash has not

occurred well in the absence of PAA eld as crystals formed
agglomeration strongly. The inhibition effect of the growth rate
on the short axis was found approximating 3.1. Therefore aspect
ratio decreased moderately in the PAA reactive eld, and retained
a similar value in the absence of PAA eld.

3.2.4. Effect of supersaturation

PAA effects were shown in different supersaturation. It was
performed on Li ion concentration 1.0 mol/l (S 1.24) and results
were shown in Fig. 9. In the additive-free state, agglomeration of
Li2CO3 were formed just approximating 0.8 mol/l (S 1.07) and
unstructured shape. When the PAA dissolved in the reactive eld,
crystals became structured shape and dispersed. In addition,
crystals grew larger than S 1.07 and changed into the rectangle
plate shape because the number of Li ions captured by PAA when
excess Li ions were concluded in the reactive eld. And PAA was
adsorbed on specic crystal face, agglomeration was inhibited.
In order to obtain crystal qualitative analysis, X-ray diffraction
patterns of obtained crystals were measured. The results were
shown in Fig. 10. All peaks of Li2CO3 appeared and obtained
crystals were dened to Li2CO3. The intensity of some faces
increased. Especially on the (020) face intensity was signicantly
different between S1.07 and 1.24. Morphometric differences of
these results were conrmed by Fig. 2(b) and Fig. 9(b). Different

3.2.2. Effect of PAA concentration

The effect of PAA concentration was investigated, when
enough amounts were presented in the reactive elds. The
experimental results were shown in Fig. 6. Mean crystal size
obtained with each PAA concentration were widely scattered. And
the effect of PAA addition on crystal was not found. But shapes
and agglomeration were affected by PAA. In a small amount of
PAA, crystals became high aspect needles and the effects were
almost kept same with increasing PAA concentration. Meanwhile
different tendency was found on the agglomeration ratio. The
optimum amount to improve agglomeration was existed near
1.0 g/l. Agglomeration was inhibited with increasing PAA concentration and PAA inhibited rapidly nucleation, each crystal separated till 1 g/l. But over 1 g/l PAA concentration, agglomeration
ratio was increased. Fig. 7 showed these aspects. Li2CO3 crystallized as needle shapes in a small amount of PAA. The effect was
kept same regardless of increasing PAA concentration. However
Li2CO3 crystals agglomerated with maintaining needle shapes
over 1.0 g/L. According to Fig. 7(d), needle crystals were adhered
together. In the small amount of PAA, PAA has an inuence on
crystal shape. But when an excess amount was added, PAA
accelerated agglomeration by interaction among PAA and crystals.
So crystals attached each other and formed agglomeration.
3.2.3. Effect of aging time
The results of aging time dependence were shown in Fig. 8. In
the absence of PAA eld, crystals grew larger size both on long
axis and short axis with progressing aging time. Meanwhile in the
PAA reactive eld, crystal growth on long axis was decreased
compared with absence of PAA, and crystal size became different
between absence and presence of PAA over 2 or 4 h. It is
considered that crystal breakage caused crystal size as needle
crystals contacted with each other or surface of vessel or stirrer
more frequently in the PAA reactive eld because of the less

115

Fig. 9. Obtained Li2CO3 on S 1.24. (a) Additive-free and (b) PAA 5000.

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H. Watamura et al. / Journal of Crystal Growth 373 (2013) 111117

Fig. 10. X-ray pattern of Li2CO3. (a) Commercial, (b) PAA; Mw 5000 S 1.07 and
(c) PAA; Mw 5000 S 1.24.

crystal shapes and XRD peaks were resulted from facial growth
alteration. The relation between captured Li ions by PAA and free
Li ions were changed with increasing of fed Li ion concentration,
particular facial growth rate was developed.

4. Conclusions
Polyelectrolytes had a signicant inuence on reactive crystallization of Li2CO3. In the PAM reactive eld, Li2CO3 crystals grew
to have the plated shape. The agglomeration rate was not
improved. In the PAA reactive eld, crystal growth was increased
on long axis and decreased on short axis. Thus crystals had high
aspect needle shape. In addition, agglomeration ratio was
decreased. These effects were not inuenced on the PAA molecular
weight. But aging time or PAA concentration were inuenced. PAA
has suitable range of addition, and improved agglomeration. This
effect was recognized in case of increasing Li concentration.
However crystal shape changed from needles to rectangle plates
because of the interaction between PAA and Li ions.

References
[1] Jeffrey W. Fergus, Resent developments in cathode materials for lithium ion
batteries, Journal of Power Sources 195 (2010) 939954.

[2] C.J. Leo, A.K. Thakur, G.V. SubbaRao, B.V.R. Chowdari, Effect of glass-ceramic
ller on properties of polyethylene oxideLiCF3SO3 complex, Journal of Power
Sources 115 (2003) 295304.
[3] John H. Lazarus, Alan M. McGregor, Marion Ludgate, Chris Darke, Fionula
M. Creagh, Chris J. Kingswood, Effect of lithium carbonate therapy on thyroid
immune status in manic depressive patients: a prospective study, Journal of
Affective Disorders 11 (1986) 155160.
[4] Yuzhu Sun, Xingfu Song, Jin Wang, Yan Luo, Jianguo Yu, Unseeded
supersolubility of lithium carbonate: experimental measurement and simulation with mathematical models, Journal of Crystal Growth 311 (2009)
47144719.
[5] Yuzhu Sun, Xingfu Song, Jin Wang, Yan Luo, Jianguo Yu, Determination of
seeded supersolubility of lithium carbonate using FBRM, Journal of Crystal
Growth 312 (2010) 294300.
[6] Wen-tao Yi, Chun-yan Yan, Pei-hua Ma, Crystallization kinetics of
Li2CO3 from LiHCO3 solutions, Journal of Crystal Growth 312 (2010)
23452350.
[7] O.S. Pokrovsky, Precipitation of calcium and magnesium carbonates from
homogeneous supersaturated solutions, Journal of Crystal Growth 186 (1998)
233239.
[8] Damir Kralj, Neda Vdovic, The inuence of some naturally occurring minerals
on the precipitation of calcium carbonate polymorphs, Water Research 34
(2000) 179184.
[9] Song Liu, Rongjun Ma, Rongying Jiang, Fangcheng Luo, Precipitation and
characterization of cerous carbonate, Journal of Crystal Growth 206 (1999)
8892.
[10] Karl-Johan Westin, Ake C. Rasmuson, Precipitation of calcium carbonate in
the presence of citrate and EDTA, Desalination 159 (2003) 107118.
[11] Diego Gomez-Diaz, Jose M. Navaza, Begona Sanjurjo, Analysis of mass
transfer in the precipitation process of calcium carbonate using a gas/liquid
reaction, Chemical Engineering Journal 116 (2006) 203209.
[12] Wang Mo Jung, Sung Hoon Kang, Woo-Sik Kim, Chang Kyun Choi, Particle
morphology of calcium carbonate precipitated by gas-liquid reaction
in a CouetteTaylor reactor, Chemical Engineering Science 55 (2000)
733747.
[13] Sung Hoon Kang, Sang Goo Lee, Wang Mo Jung, Min Chan Kim, Woo-Sik Kim,
Chang Kyun Choi, Robert S. Feigelson, Effect of Taylor vortices on calcium
carbonate crystallization by gasliquid reaction, Journal of Crystal Growth
254 (2003) 196205.
[14] ImGyu Kim, Byung Hoon Jo, Dong Gyun Kang, Chang Sup Kim, Yoo
Seong Choi, Hyung Joon Cha, Biomineralization-based conversion of carbon
dioxide to calcium carbonate using recombinant carbonic anhydrase, Chemosphere 87 (2012) 10911096.
[15] Yunfeng Jiao, Qingling Feng, Xiaoming Li, The co-effect of collagen and
magnesium ions on calcium carbonate biomineralization, Material Science
and Engineering C 26 (2006) 648652.
[16] M.A. Rivadeneyra, G. Delgado, A. Ramos-Cormenzana, R. Delgado, Biomineralization of carbonates by Halomonaseurihalinain solid and liquid media
with different salinities: crystal formation sequence, Research in Microbiology 149 (1998) 277287.
[17] H. Eldereld, C.J. Bertram, J. Erez, A biomineralization model for the
incorporation of trace elements into foraminiferal calcium carbonate, Earth
and Planetary Science Letters 142 (1996) 409423.
[18] Yasushi Kotaki, Hideki Tsuge, Reactive crystallization of calcium carbonate in
a batch crystallizer, Journal of Crystal Growth 99 (1990) 10921097.
[19] Kazuya Tamura, Hideki Tsuge, Characteristics of multistage column crystallizer for gasliquid reactive crystallization of calcium carbonate, Chemical
Engineering Science 61 (2006) 58185826.
[20] Mitsutaka Kitamura, Haruo Konno, Atsunari Yasui, Hirokatsu Masuoka, Controlling factors and mechanism of reactive crystallization of calcium carbonate polymorphs from calcium hydroxide suspensions, Journal of Crystal
Growth 236 (2002) 323332.
[21] Masakazu Matsumoto, Tomohiro Fukunaga, Kaoru Onoe, Polymorph control
of calcium carbonate by reactive crystallization using microbubble technique, Chemical Research and Design 88 (2010) 16241630.
[22] Pao-Chi Chen, K.L. Kou, H.K. Tai, S.L. Jin, C.L. Lye, C.Y. Lin, Removal of carbon
dioxide by reactive crystallization in ascrubber-kinetics of barium carbonate
crystals, Journal of Crystal Growth 237239 (2002) 21662171.
[23] Takashi Mikami, Takahiro Sakuma, Izumi Hirasawa, CSD-controlled reactive
crystallization of SrSO4 in the presence of polyethylenimine, Chemical
Engineering Research and Design 88 (2010) 12001205.
[24] Takashi Mikami, Yuta Takayasu, Izumi Hirasawa, PEI-assisted preparation of
Au nanoparticles via reductive crystallization process, Chemical Engineering
Research and Design 88 (2010) 12481251.
[25] Izumi Hirasawa, Takashi Mikami, Akio Katayama, Takahiro Sakuma, Strategy
to obtain nm size crystals through precipitation in the presence of polyelectrolyte, Chemical Engineering and Technology 29 (2006) 212214.
[26] Takashi Mikami, Izumi Hirasawa, Polyelectrolyte-assisted reactive crystallization of SrSO4 to obtain monodispersed nano/micro-particles, Chemical
Engineering and Technology 33 (2010) 797803.
[27] Takashi Mikami, Izumi Hirasawa, Quality-controlled reactive crystallization
of SrSO4 to produce high-valued chemicals, Chemical Engineering and
Technology 33 (2010) 775779.
[28] Takashi Mikami, Yuta Takayasu, Junpei Watanabe, Izumi Hirasawa, Inuence
of polyethyleneimine addition on crystal size distribution of Au nanocrystals,
Chemical Engineering and Technology 34 (2011) 583586.

H. Watamura et al. / Journal of Crystal Growth 373 (2013) 111117

[29] F. Manoli, E. Dalas, Calcium carbonate crystallization in the presence of

glutamic acid, Journal of Crystal Growth 222 (2001) 293297.
[30] F. Manoli, J. Kanakis, P. Malkaj, E. Dalas, The effect of aminoacids on the
crystal growth of calcium carbonate, Journal of Crystal Growth 236 (2002)
363370.
[31] Qiu Yu, Huang-Dong Ou, Rui-Qi Song, An-Wu Xu, The effect of polyacrylamide on the crystallization of calcium carbonate: synthesis of aragonite
single-crystal nano-rods andhollow vatarite hexagons, Journal of Crystal
Growth 286 (2006) 178183.

117

[32] F. Manoli, S. Koutsopoulos, E. Dalas, Crystallization of calcite on chitin,

Journal of Crystal Growth 182 (1997) 116124.
[33] M. Euvrard, A. Martinod, A. Neville, Effects of carboxylic polyelectrolytes on
the growth of calcium carbonate, Journal of Crystal Growth 317 (2011)
7078.
[34] Jiaguo Yu, Ming Lei, Bei Cheng, Xiujian Zhao, Effects of PAA additive and
temperature on morphology of calcium carbonate particles, Journal of Solid
State Chemistry 177 (2004) 681689.