10th INTERNATIONAL CONFERENCE ON LITHIUM, INDUSTRIAL MINERALS AND ENERGY

October 23-25, Antofagasta, Chile

Modeling and Simulation of the Co-precipitation

Synthesis Process of the Precursor Material for the
LNMO Type Lithium-Ion Battery Cathode in a
Semibatch
1 1
Reactor 1,2 M.Arratia , L. Rojas , M. Grágeda
1Center for Advanced Research in Lithium and Industrial Minerals, University of Antofagasta, Avenue Universidad de Antofagasta 02800, Antofagasta, Chile.
2Chemical Engineering Department, University of Antofagasta, Avenue Universidad de Antofagasta 02800, Antofagasta, Chile

E-mail: [email protected]

1 INTRODUCTION (a)
(b)

The material LiNi0.5Mn1.5O4 (LNMO) is a promising cathode material due to

its high voltage (4.7 V) and theoretical capacity (147 mAh/g), surpassing the
NH4 OH
cathode material LiNixCoyMnzO2. The absence of cobalt in these materials
reduces costs and is more environmentally friendly, and the spinel structure Na2 CO3

of LNMO enhances structural stability compared to LMO. The synthesis of

layered cathode particles is achieved through precursor co-precipitation,
followed by a calcination step to form the lithiated structure. The structure MnSO4
V0 𝜌
and morphology of the final cathode particles, obtained after calcination,
often resemble the precursors generated in the co-precipitation process. This NiSO4

study proposes to model and simulate the co-precipitation synthesis process

of LNMO-type cathode precursor materials in a semi-batch reactor using
MATLAB. The objective is to establish a precise control strategy to adjust
the process conditions according to desired parameters: process pH, 2+
morphology, distribution, and particle size. The semi-batch reactor for the 1Τ4 Ni2+ (𝑎𝑞) + 3Τ4 Mn2+ (𝑎𝑞) + nNH4 OH(𝑎𝑞) ⟶ Ni1Τ4 Mn3Τ4 NH3 n (𝑎𝑞)
+ nH2 O(𝑙) (1)
experimental tests and its corresponding diagram are shown in Figure 1. 2+ 2−
Ni1Τ4 Mn3Τ4 NH3 n (𝑎𝑞)
+ CO3 (𝑎𝑞) + nH2 O(𝑙) ⟶ Ni1Τ4 Mn3Τ4 CO3 𝑠
+ nNH4 OH 𝑎𝑞 (2)

2 RESULTS AND DISCUSSION Figure 1.. a) Semi-batch reactor for the experimental tests b) Semi-batch co-precipitation reactor diagram.

The kinetic modeling and equilibrium analysis of chemical reactions (1) and
(2) were carried out by applying mass balances and the principle of
electroneutrality to determine the pH of the solution in the reactor, as shown
Ni1/4 Mn3/4 CO3
in equations (3-11). TMCO3 TM OH 2
dV σni=1 ρi0 𝑣i0 σni=1 ρi0 𝑣i0
= 𝟑 V = V0 + t (𝟒)
dt ρ ρ
σni=1 ρi0 vi0 σni=1 ρi0 vi0
d c i ci0 vi0 − ci ρ dci ci
ρ (a) (b) (c)
= + ri 5 = ri − 6
dt σni=1 ρi0 vi0 dt σni=1 ρi0 vi0
V0 + t V0 + t
ρ ρ
cMn2+ T = Mn2+ σ4i=1 βMn,i NH3 i 7 cNi2+ T = Ni2+ σ6i=1 βNi,i NH3 i
8

cNH3 = NH3 + NH4+ + Mn2+ σ4i=1 i ∙ βMn,i NH3 i + Ni2+ σ6i=1 i ∙ βNi,i NH3 i 9
T

𝑐𝐶𝑂3 = CO2−
3 + HCO−
3 + H2 CO3 10 Na+ + H + = 2 CO2−
3 + HCO−
3 + OH
− 11
T
Carbonate Complex Hydroxide Carbonate Complex Hydroxide

The parameters and equilibrium constants of the ionic reactions Carbonate Complex Hydroxide

occurring in the process are collectively presented in Table 1. Figure 3. Variation of pH with time inside the reactor
Table 1. Process parameters and equilibrium constants at 60°C. (d) (e) (f)

Figure 2. (a-c) Variation of free Mn2+ and Ni2+ concentrations with pH at 0.15M, 1M, and 2M, respectively. (d-f) Distribution
diagram of Mn2+ and Ni2+ complexes at different pH and concentrations of 0.15M, 1M, and 2M, respectively.

In lower pH ranges, specifically between 7.5 and 8, the formation of metal complexes commences.
Under acidic pH conditions, below 7.5, precipitates of individual transition metal carbonates are
generated. Lastly, at pH levels exceeding 10, precipitates of Mn and Ni hydroxides are formed.
(Figures 2a-c) depict the concentrations of transition metals at different pH levels and various NH3
concentrations, confirming the formation of carbonates, mixed carbonates, and hydroxides
precipitates.

3 CONCLUSIONS
In conclusion, at 60°C, the co-precipitation process has been shown to result in the formation of
complexes and, hence, the precipitation of the precursor in the pH range of 8 to 10. An NH3
As a preliminary result, this work focuses on a study of the complexation concentration of 1 M has been identified as optimal for the formation of complexes of both Mn and
equilibrium of transition metals Mn2+ and Ni2+ under various conditions of Ni. In the future, it is expected to conduct a kinetic study of particle size evolution and validate the
total NH3 concentration and different pH values. To achieve this, the simulation through a comparison with experimental results. Likewise, it is anticipated that the
material balance equations (equations 7-11) were solved in MATLAB, behavior of the operational variables can be predicted, enabling the development of a valuable tool
leading to the construction of a species distribution diagram (Figure 2 d-f) for process analysis and optimization.
for NH3 concentrations of 0.15 M, 1 M, and 2 M. The results reveal that as
the NH3 concentration increases, the molar percentage of metal complexes
4 ACKNOWLEDGEMENTS
also rises. Furthermore, it is observed that the precipitation of the Authors thank to “Plataforma Baterías de Litio” Project SQM-CELIMIN UA, ANID/FONDAP
Ni1/4Mn3/4CO3 precursor occurs within a pH range between 8 and 10. N°15110019 and PUENTE N° 1522A0006 projects for the financial support.

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