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Contents lists available at ScienceDirect

Particuology
journal homepage: www.elsevier.com/locate/partic

Effects of temperature on conversion of Li2 CO3 to LiOH in Ca(OH)2

suspension
Bo Yuan a,b , Jing Wang b , Wei Cai a,b , Yurong Yang a,b , Meigui Yi a,∗ , Lan Xiang b,∗
a
College of Chemical Engineering, Sichuan University, Chengdu 610065, China
b
Department of Chemical Engineering, Tsinghua University, Beijing 100084, China

a r t i c l e i n f o a b s t r a c t

Article history: The effects of temperature on the conversion of Li2 CO3 to LiOH in a Ca(OH)2 suspension were investigated.
Received 2 December 2016 Li2 CO3 microplates were used as the Li source. The results showed that Li2 CO3 was converted to LiOH via
Received in revised form 16 January 2017 in situ ion-exchange and dissolution–precipitation routes. The formation of mixed Cax Li2−2x CO3 inter-
Accepted 22 January 2017
mediate species confirmed that at 25 ◦ C needle-like CaCO3 was formed heterogeneously on the Li2 CO3
Available online xxx
surface via in situ ion-exchange. At 60–100 ◦ C, isolated CaCO3 agglomerates were formed homogeneously
via dissolution–precipitation. Temperature increases accelerated the dissolution and conversion of Li2 CO3
Keywords:
to LiOH, producing solutions with high [CO3 2− ]/[Ca2+ ] ratios; this favored homogeneous precipitation of
Lithium carbonate (Li2 CO3 )
Causticization
isolated CaCO3 agglomerates.
In situ ion-exchange © 2017 Chinese Society of Particuology and Institute of Process Engineering, Chinese Academy of
Dissolution–precipitation Sciences. Published by Elsevier B.V. All rights reserved.

Introduction
High-purity Li2 CO3 is widely used to fabricate Li-containing pos-
itive electrode materials (e.g., LiCoO2 , LiNiO2 , LiMnO2 , LiMn2 O4 ,
LiFePO4 , Li4 Ti5 O12 , LiNi1/3 Co1/3 Mn0.3 O2 , LiNi0.4 Co0.2 Mn0.4 O2 ,
LiNi0.5 Co0.2 Mn0.3 O2 , LiNi0.4 Co0.4 Mn0.2 O2 , and LiNi0.8 Co0.1 Mn0.1 O2 )
(Jiang & Abraham, 1996; Liu et al., 2014; Zou, Ding, & Chen,
2014;) and Li-containing electrolytes (e.g., LiPF6 , LiBF4 , LiAsF6 ,
and LiB(C2 O4 )2 ) (Heider, Oesten, & Jungnitz, 1999; Mu, Zeng, &
Yu, 2014; Yang et al., 2010). The rapid development of Li-based
batteries in recent years has stimulated research on high-purity
Li2 CO3 (Huang, Yan, Wan, & Jiang, 2000; Li & Lucht, 2007).
Various methods have been developed for the synthesis of high-
purity Li2 CO3 , e.g., recrystallization, causticization–carbonization,
carbonation–decomposition, electrodialysis, and ion exchange
(Jiang, Wang, Wang, Feng, & Xu, 2014; Sun, Song, Wang, & Yu,
2011, 2012; Tsuge & Kuze, 2006; Yi, Yan, & Ma, 2010, 2011). How-
ever, most of these methods have low efficiencies; for example,
the efficiency of recrystallization is limited by the low solubil-
ity of Li2 CO3 (1.33 g per 100 mL at 20 ◦ C and 0.72 g per l00 mL
at 100 ◦ C) and only impurities with positive temperature coeffi-
cients, such as sulfate and zinc, can be removed effectively (Yi, Yan,
Dai, Li, & Ma, 2005). The efficiency of carbonation–decomposition
(Li2 CO3 + CO2 + H2 O → 2LiHCO3 ; 2LiHCO3 → Li2 CO3 + CO2 + H2 O) is
also low because of the poor solubility of LiHCO3 (7.4 g per l00 mL
at 20 ◦ C) (Amouzegar, Amant, & Harrison, 2000; Brown & Boryta,
1993; Boryta, Kullberg, & Thurston, 2007; Harrison & Blanchet,
2015). Causticization–carbonization is more widely used than
other methods to fabricate pure Li2 CO3 because it is simple and
cheap (Brown & Falletta, 1980). Crude Li2 CO3 is converted to soluble
LiOH by causticization with a Ca(OH)2 suspension and impurities
such as K+ , Na+ , Ca2+ , Mg2+ , Fe3+ , Cl− , CO3 2− , SO4 2− , and SiO2 in
the crude Li2 CO3 are either dissolved (e.g., K+ , Na+ , and Cl− ) or
precipitated out (e.g., Ca2+ , Mg2+ , CO3 2− , SO4 2− , and SiO2 ). The
LiOH solution containing soluble impurities is then converted to
a purified Li2 CO3 precipitate by carbonation with CO2 ; the solu-
ble impurities remain in the solution. However, the efficiency of
causticization (Li2 CO3 + Ca(OH)2 → 2LiOH + CaCO3 ) is low because
of the long reaction time and low conversion ratio; the reasons for
this are still unclear. In the present work, we therefore investigated
the effects of temperature on precipitation and ion dissolution to
determine the primary causticization mechanism at various tem-
peratures.
Experimental
Experimental procedure

Commercially available analytical-grade chemicals (Modern

∗ Corresponding authors. Oriental (Beijing) Technology Development CD., LTD, Beijing,
E-mail addresses: meiguiyi@scu.edu.cn (M. Yi), xianglan@mail.tsinghua.edu.cn China) were used. Ca(OH)2 was mixed with deionized water under
(L. Xiang). stirring (300 rpm), heated (5 ◦ C/min) to 25–100 ◦ C, and the tem-

http://dx.doi.org/10.1016/j.partic.2017.01.005
1674-2001/© 2017 Chinese Society of Particuology and Institute of Process Engineering, Chinese Academy of Sciences. Published by Elsevier B.V. All rights reserved.

Please cite this article in press as: Yuan, B., et al. Effects of temperature on conversion of Li2 CO3 to LiOH in Ca(OH)2 suspension.
Particuology (2017), http://dx.doi.org/10.1016/j.partic.2017.01.005
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Fig. 1. Morphology (a), and XRD (b), and EDS (c) patterns of Li2 CO3 raw material.

perature was maintained for 0.5 h to give a suspension containing
8.0 wt% Ca(OH)2 . The Ca(OH)2 suspension was mixed with an
equimolar amount of Li2 CO3 , stirred (300 rpm), and kept under
isothermal conditions at 25–100 ◦ C for 0–10.0 h. The precipitate
was separated using a microfiltration membrane of average pore
size 0.1 ␮m, washed three times with deionized water, and dried
at 95 ◦ C for 6.0 h. The solutions were collected for chemical analyses.
rates were 5◦ /min for normal XRD analysis and 0.0053◦ /min for
precise XRD analysis. The surface electric potentials of the sam-
ples were measured using a zeta potential analyzer (ZetaPALS,
Brookhaven Instrument Corporation, USA). Dissolved Ca2+ and Li+
were detected using an ion chromatography system (CIC-300,
Shenghan Chromatography Technology Co., Ltd, Qingdao, China)
equipped with an SH-CC-3 column. Dissolved OH− was determined
by HCl titration.

Characterization

The sample morphologies were examined using field-emission
scanning electron microscopy (SEM; JSM 7401F, JEOL, Japan)
equipped with energy-dispersive X-ray spectroscopy. The compo-
sitions and structures of the samples were identified by powder
X-ray diffraction (XRD; D8 advanced, Bruker, Germany) using
Cu K␣ radiation ( = 1.54178 Å), with Al2 O3 with a certified cell
parameter of 0.25527 nm as the internal standard. The scanning
Results and discussion
Fig. 1 shows the morphology, and the XRD and energy-
dispersive X-ray spectroscopy (EDS) patterns of the Li2 CO3 raw
material. Fig. 1(a) shows that it consisted of rectangular microplates
of length 15–35 ␮m, width 5–15 ␮m, and thickness 1–5 ␮m. The
XRD pattern (Fig. 1(b)) is consistent with that of monoclinic Li2 CO3

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Fig. 2. Li2 CO3 to LiOH conversion ratios (a) and XRD patterns (b) of causticization products formed at 10.0 h:  Li2 CO3 , * CaCO3 , and 䊉 Ca(OH)2 .

Fig. 3. SEM images of causticization products formed at (a) 25 ◦ C, 3 min; (b) 25 ◦ C, 60 min; (c) 25 ◦ C, 10 h; (d) 60 ◦ C, 3 min; (e) 60 ◦ C, 60 min; (f) 60 ◦ C, 10 h; (g) 100 ◦ C, 3 min;
(h) 100 ◦ C, 60 min; and (i) 100 ◦ C, 10 h.

(JCPDS 87-0729). EDS (Fig. 1(c)) shows the presence of C and O, but
Li was not detected because of the limitations of EDS detection.
Fig. 2 shows the conversion ratios of Li2 CO3 to LiOH and the XRD
patterns of the causticization products formed at 25–100 ◦ C. The
Li2 CO3 conversion ratio increased rapidly during the first 20 min
and then increased gradually (Fig. 2(a)). Increasing the temperature
promoted causticization (e.g., the conversion ratios at 1.0 h were
52.5%, 59.0%, and 59.5% at 25, 60, and 100 ◦ C, respectively) but only
64%–68% of Li2 CO3 was converted to LiOH even after 10.0 h. The
XRD patterns in Fig. 2(b) show the coexistence of CaCO3 , Li2 CO3 , and
Ca(OH)2 in the causticization products formed at 10.0 h, confirming
partial conversion of Li2 CO3 to LiOH.

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Fig. 4. EDS patterns of CaCO3 formed during causticization.
The time-resolved morphology evolutions of the causticiza-
tion products formed at 25–100 ◦ C are shown in Fig. 3. At 25 ◦ C,
worm-like CaCO3 particles were formed heterogeneously on the
Li2 CO3 surface after reaction for 3 min (Fig. 3(a)). The particle den-
sity increased and the shape gradually changed from worm-like
to needle-like with increasing reaction time (Fig. 3(b)). The shape
and dimensions of the formed CaCO3 -wrapped Li2 CO3 microcrys-
tals were almost the same as those of the Li2 CO3 microplates in the
mother liquor; a few isolated CaCO3 particles, i.e., not on Li2 CO3
(Fig. 3(c)), were formed, suggesting that in situ ion-exchange is
the dominant mechanism in the conversion of Li2 CO3 to LiOH at
25 ◦ C. In this mechanism, two Li+ ions on the Li2 CO3 surface are
replaced in situ by one Ca2+ ion and then CaCO3 particles are formed
directly on the Li2 CO3 surface (Li2 CO3 (s) + Ca2+ → CaCO3 (s) + 2Li+ ).
At 60–100 ◦ C, only a few CaCO3 rods were formed on the Li2 CO3
surface and most of them were present as isolated agglomerates
(Fig. 3(d)–(i)). The significant decrease in the Li2 CO3 particle size
Fig. 5. Effects of temperature on XRD patterns of CaCO3 formed during causticization.
Please cite this article in press as: Yuan, B., et al. Effects of temperature on conversion of Li2 CO3 to LiOH in Ca(OH)2 suspension.
Particuology (2017), http://dx.doi.org/10.1016/j.partic.2017.01.005
(the length, width, and thickness decreased to ca. 8, 3, and 0.8 ␮m,
respectively, after reaction for 1 h) and the presence of many holes
in the Li2 CO3 crystals (Fig. 3(f) and (i)) indicate formation of CaCO3
mainly via a dissolution–precipitation route at 60–100 ◦ C, i.e.,
Li2 CO3 dissolution (Li2 CO3 (s) → 2Li+ + CO3 2− ) followed by CaCO3
precipitation from solution (Ca2+ + CO3 2− → CaCO3 (s)).
Fig. 4 shows the EDS patterns for CaCO3 formed at 25–100 ◦ C
after causticization for 10.0 h. The Ca:C:O atomic ratios for CaCO3
formed at 25, 60, and 100 ◦ C were 1:1.10:3.68, 1:1.04:3.27, and
1:1.01:3.35, respectively, i.e., a little lower than that (1:1:3) for
pure CaCO3 , suggesting the formation of Cax Li2−2x CO3 intermediate
species.
Fig. 5 shows the effects of temperature on the XRD patterns of
CaCO3 formed at 25–100 ◦ C after causticization for 10 h. Table 1
summarizes the peak deviations and corresponding lattice spac-
ings of the CaCO3 samples. The shifts to the right of the diffraction
peaks for the (104), (113), and (116) planes and the decreases in
the corresponding lattice spacings compared with those of pure
CaCO3 (JCPDS 83-0578) could be caused by superimposition of
CaCO3 and Li2 CO3 peaks or the substitution of some Ca2+ by Li+ in
the structure, because the radius of Li+ (0.68 Å) is smaller than that
of Ca2+ (1.00 Å) (Hou, Wang, Wang, Chen, & Xiang, 2014; Madejová,
Pálková, & Komadel, 2006). The diffraction peak shifts for the (024)
and (018) planes, where there is no Li2 CO3 peak (see Supporting
Information, Fig. S1), suggests the formation of a Cax Li2−2x CO3 solid
solution. A solid solution could be formed by imperfect in situ ion-
exchange (Li2 CO3 (s) + xCa2+ → Cax Li2−2x CO3 + 2xLi+ ) because ion
exchange at the solid–liquid interface can be kinetically controlled
by a diffusion-limited process. The peak deviations and shrinkage
of the lattice spacings were most significant at 25 ◦ C, showing that
at room temperature CaCO3 was mainly formed via in situ ion-
exchange.
The effects of temperature on the relationship between the
two competing mechanisms could be related to the concen-
trations of soluble ions, including [CO3 2− ] and [Ca2+ ], and the
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Table 1
Peak deviations and lattice spacings of CaCO3.

CaCO3 (104) (113) (116)

Deviation (o ) Spacing (Å) Deviation (o ) Spacing (Å) Deviation (o ) Spacing (Å)

Standard – 3.0345 – 2.2841 – 1.8748

25 ◦ C 0.1821 3.0187 0.1693 2.2765 0.1599 1.8704
60 ◦ C 0.1013 3.0268 0.0946 2.2807 0.0762 1.8735
100 ◦ C 0.0998 3.0269 0.0916 2.2808 0.0726 1.8736

Fig. 6. Effects of temperature on [CO3 2− ] (a), [Ca2+ ] (b), and [CO3 2− ]/[Ca2+ ] (c).

[CO3 2− ]/[Ca2+ ] ratio. [CO3 2+ ] or [Ca2+ ] depends on the dynamic
balance between dissolution of Li2 CO3 or Ca(OH)2 and precipi-
tation of CaCO3 . Fig. 6(a) shows that [CO3 2− ] initially increased
with reaction time, indicating that Li2 CO3 dissolution was faster
than CaCO3 precipitation. The subsequent decrease in [CO3 2− ] is
attributed to CaCO3 precipitation being faster than Li2 CO3 dissolu-
tion. An increase in the temperature from 25 to 100 ◦ C and less
wrapping by CaCO3 accelerated Li2 CO3 dissolution, leading to a
rapid increase in [CO3 2− ] at high temperatures.
The initial [Ca2+ ] decreased with increasing temperature
because of the low solubility of Ca(OH)2 at high temperatures. A
higher temperature thermodynamically (lower solubility of CaCO3
at high temperatures than that at room temperature) and kinet-
ically favors precipitation of CaCO3 , leading to decreasing [Ca2+ ]
with increasing temperature (Fig. 6(b)). The data in Fig. 6(c) show
that the [CO3 2− ]/[Ca2+ ] ratio at 25 ◦ C was much lower than those
at 60–100 ◦ C. The lower [CO3 2− ]/[Ca2+ ] ratio (ca. 0.1–2) at 25 ◦ C
indicates the presence of abundant Ca2+ ions in solution. This
favors in situ ion-exchange because the positively charged Ca2+ is
adsorbed on the negatively charged Li2 CO3 surface and replaces
Li+ in Li2 CO3 (the zeta potential of Li2 CO3 declined from −3.8 to
−16.8 mV with increasing causticization time from 0 to 1.0 h). The
high [CO3 2− ]/[Ca2+ ] ratios at high temperatures show the presence
of abundant CO3 2− ions in solution. This inhibits the adsorption of
Ca2+ or CO3 2− on the negatively charged Li2 CO3 surface, promoting
the homogeneous precipitation of CaCO3 from solution.
The effects of temperature on the conversion of Li2 CO3 to LiOH
are summarized schematically in Fig. 7. Li2 CO3 is converted to
LiOH more quickly at high temperatures than at room tempera-
ture because accelerated dissolution of Li2 CO3 produces solutions
with high [CO3 2− ]/[Ca2+ ] ratios, and this favors the homogeneous
precipitation of CaCO3 agglomerates. At room temperature, the
low [CO3 2− ]/[Ca2+ ] ratio favors Ca2+ adsorption on the negatively
charged Li2 CO3 surface and promotes in situ ion-exchange.
Conclusions
The effects of temperature on the conversion of Li2 CO3 to LiOH in
a Ca(OH)2 suspension were investigated. CaCO3 was mainly formed
via in situ ion-exchange at 25 ◦ C, and via dissolution–precipitation
at 60–100 ◦ C. Increasing the temperature from 25 to 100 ◦ C
accelerated the dissolution and conversion of Li2 CO3 to LiOH, pro-
ducing solutions with high [CO3 2− ]/[Ca2+ ] ratios. This favored the
homogeneous precipitation of isolated CaCO3 agglomerates via
dissolution–precipitation.

Please cite this article in press as: Yuan, B., et al. Effects of temperature on conversion of Li2 CO3 to LiOH in Ca(OH)2 suspension.
Particuology (2017), http://dx.doi.org/10.1016/j.partic.2017.01.005
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Fig. 7. Schematic diagram of conversion of Li2 CO3 to LiOH at different temperatures.
Acknowledgment
This work was supported by the National Science Foundation of
China (Nos. 51234003 and 51374138).
Appendix A. Supplementary data
Supplementary data associated with this article can be found,
in the online version, at http://dx.doi.org/10.1016/j.partic.2017.01.
005.
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