CHEM-C1240 General Chemistry Laboratory Course

Determination of Lithium and Manganese in Lithium Manganese

Oxide (LMO) by Atomic Absorption Spectrometry (AAS) and
Spectrophotometry

Tu Nhi Luong, 101770844

Minh Nguyen, 101725721

Report submitted 13.12.23

Table of Contents

1. Introduction..................................................................................................................2

2. Experimental.................................................................................................................3

2.1 Sample preparation................................................................................................................3

2.2 Spectrophotometry................................................................................................................3

2.3 Atomic Absorption Spectrometry (AAS)...............................................................................5

3. Results............................................................................................................................6

4. Error consideration......................................................................................................9

5. Discussions and conclusions.........................................................................................9

6. References....................................................................................................................10

1
 1. Introduction

Lithium Manganese Oxide (LMO) has been gaining attention as a cathode material for lithium-
ion batteries for its potential sustainability, cost-effectiveness and favorable technical
characteristics, including thermal stability, high-density power, and safety. Manganese is also
an abundant element. Therefore, LMO battery technology is applied in a wide variety of fields:
electric vehicles, medical devices, and consumer electronics. Among several LMO cathode
materials, the LiMn2O4 spinel cathode, thanks to its three-dimensional structure, has
demonstrated higher rate-capability compared to materials with two-dimensional structures,
allowing for rapid charging and discharging of the battery. However, LMO has certain
limitations. For example, it has relatively low electronic conductivity and exhibits capacity
fading over repeated charge-discharge cycles.

In this experiment, we determined the content of lithium and manganese in LMO by applying
AAS and spectrophotometry. AAS is based on the interaction between optical radiation and
atoms in the gas phase. During the measurement, the analyte is converted into gaseous atoms,
which can absorb the specific wavelength of light emitted by a light source called the hollow
cathode lamp. The reduction of the radiation intensity is then measured and used to calculate
the concentration of the analyte over Beer-Lambert Law. Similarly, spectrophotometry also
takes advantage of the light-absorbing property of matter. In this analysis method, the analyte
is put into a cuvette, which afterward a light beam of a specific wavelength will go through. The
intensity of the light passing through the cuvette is then detected and used to calculate the
concentration of the analyte over Beer-Lambert Law.

Based on our calculations of dividing the molar mass of both elements by the molar mass of
LiMn2O4, we expect the percentage of Li in LiMn 2O4 to be about 3.8674% and the percentage of
Mn to be about 60.7735%.

2
 2. Experimental

2.1 Sample preparation

We began preparing a dissolution of lithium manganese oxide by weighing 0.2006 g of lithium
manganese oxide powder using a weighing boat and the analytical weight for high precision.
The powder was then poured into a 250-ml beaker. Distilled water (DIW) was used in small
amounts to transfer all the powder on the weighing boat into the beaker. Next, we measured
40 mL of 1M HNO3 with a 100-mL graduated cylinder and transferred it to the 250-mL beaker
earlier, which was then placed onto the hot plate of around 100 oC and heated up but not
boiled. We measured 5 mL of 1% H2O2 and added it to the beaker one drop at a time using a
Pasteur pipette. At the same time, we stirred the solution constantly with a glass rod. In this
step, we had to reduce the heat as we observed bubbles in the solution. We also had to use
about 2.5 mL of additional 1% H2O2 solution for the sample to turn fully transparent. The
chemical reaction that happened in this step was:

2LiMn2O4 + 2H2O2 + 10H+  2Li+ + 4Mn2+ + 8H2O + 3O2

After turning fully transparent without any observable solid particles, the sample was taken off
the hotplate and left to cool to room temperature. When the sample was cooled, it was
transferred from the beaker into a 100-mL volumetric flask using a funnel. The glass rod and
beaker were rinsed using DIW into the same volumetric flask to minimize sample loss. The flask
was filled to the 100-mL mark with DIW and mixed thoroughly by inverting the flask 20 times.

2.2 Spectrophotometry
We prepared standards for Mn analysis by spectrophotometry by pipetting calculated amounts
of 0.010 mol/L KMnO4 solution into 100-mL volumetric flasks. The six standard solutions have
the KMnO4 concentration of 0.05, 0.1, 0.2, 0.3, 0.4, and 0.5 mmol/L, which meant the amount
3
of 0.010 mol/L KMnO4 solution pipetted into the flasks are 0.5, 1.0, 2.0, 3.0, 4.0, 5.0 mL,
respectively. A blank standard with no KMnO 4 was also prepared. All flasks were marked with
numbers carefully to avoid confusion. 1 mL of 1 mol/L HNO3 was then added to the seven
flasks. Afterwards, all of the flasks were fill to the 100-mL mark and mixed thoroughly by
turning upside down and back 20 times.

To prepare the sample solution, we pipetted 1 mL of the dissolved lithium manganese oxide
sample in Part 2.1 to a 250-mL beaker. 50 mL of 1 mol/L HNO 3 was then added, followed by
0.6003 g of KIO4. The content of the beaker was mixed with a glass rod. Next, we rinsed the
glass rod with small amounts of DIW to minimize loss and put the beaker onto a hotplate with
temperature set to 180 oC. A watch glass was used as a lid. The solution boiled and changed to
dark purple about 15 minutes later, indicating Mn2+ fully oxidizing to MnO4-.

The chemical reaction happened was:

2Mn2+ + 5IO4- + 3H2O  2MnO4- + 5IO3- + 6H+

The beaker was then taken off heat with a tissue in hand for protection and left to cool down to
room temperature. Once the solution was completely cooled, it was transferred completely to
a 100-mL volumetric flask using a funnel. The beaker was rinsed with small amounts of DIW to
ensure all the sample was delivered to the volumetric flask. Next, we filled the flask to the 100-
mL mark with DIW and mixed thoroughly.

For the spectrophotometric measurement, we first filled two measurement cuvettes with DIW
for measuring baseline and the reference. We then filled a measurement cuvette with each of
the seven standard solutions and placed the filled cuvettes next to their corresponding bottle to
avoid confusion. Similarly, we filled three measurement cuvettes with the sample solution
above. The cuvettes containing DIW of the reference and the measuring baseline were put first
into the spectrophotometer, and then in order, the measuring baseline cuvette was replaced by
the standard cuvettes and three sample cuvettes. The wavelength used for spectrophotometry
was 525 nm.

4
2.3 Atomic Absorption Spectrometry (AAS)
We first prepared a solution of 40 mg/L of Li pipetting 4 mL of 1000 mg/L lithium standard for
AAS solution into a 100-mL volumetric flask and filling the flask with 1 mol/L HNO3. We then
prepared standards for Li analysis by AAS by pipetting calculated amounts of 40 mg/L Li
solution into 100-mL volumetric flasks. The five standard solutions should have the Li
concentration of 0.4, 0.8, 1.2, 1.6, and 2.0 mmol/L, meaning the amount of 40 mg/L Li solution
pipetted into the flasks are 1, 2, 3, 4, 5 mL, respectively. A blank standard with no Li was also
prepared. All flasks were marked with numbers carefully to avoid confusion. 5 mL of 1 mol/L
HNO3 was then added to the six flasks. Afterwards, all of the flasks were fill to the 100-mL mark
and mixed thoroughly by turning upside down and back 20 times.

To prepare the parallel sample, we first filtrated around 30 mL of the dissolved lithium
manganese oxide sample in Part 2.1 to a beaker with a syringe and a microfilter. From the
filtrated sample solution, 1.3 mL was pipetted into a 100-mL volumetric flask. 5 mL of 1 mol/L
HNO3 was added, and the flask was then filled to the mark, followed by thorough mixing. These
steps were repeated two more times to make a total of three paralle samples.

In order, the standards and samples were put through the spectrometer. The wavelength used
for AAS was 670.8 nm.

5
 3. Results

Table 1. Results of Li analysis by AAS.

Li concentration Mass of Li in Li mass

in measured powder sample percentage in
sample [mg/L] [mg] powder sample
[%]

Sample 1 1.0440 8.0304 4.0152

Sample 2 0.9572 7.3634 3.6817

Sample 3 1.004 7.7197 3.8599

Result 1.0016 ± 0.1078 7.7045 ± 0.3707 3.8522± 0.1752

error

Table 2. Results of Mn analysis by spectrophotometry.

Mn Mass of Mn in Mn mass
concentration in powder sample percentage in
measured sample [mg] powder sample
[mg/L] [%]

JSample 1 5.4166 54.1657 9.0231

Sample 2 5.3938 53.9383 8.9852

Sample 3 5.3938 53.9383 8.9852

Result ± 5.4014 ± 0.0326 54.0141 ± 1.1416 8.9978 ± 0.1902

error

6
Figure 1. Absorbances of the standards as a function of Li concentration (mg/L) in AAS.

Calibration line equation: y = 0.0842x + 0.0114

Correlation coefficient: r = 0.9996

7
Figure 2. Absorbances of the standards as a function of Mn concentration (mmol/L) in
spectrophotometry.

Calibration line equation: y = 2.4156x – 0.0012

Correlation coefficient: r = 0.99999

8
 4. Error consideration

We conducted the analysis using the AAS method three times. In the first experiment, the
standards with concentration of 0.8, 1.2, and 1.6 mmol/L produced results deviating
considerably from values predicted by the trendline. In the second experiment, only the
standard with concentration of 0.8 mmol/L produced result deviating considerably from the
value predicted by the trendline. It is suspected that those errors are attributable to one of two
causes: errors being made while preparing the solutions or the solutions not being mixed
thoroughly enought before putting in the spectrometer. In the third experiment, all standards
produced results similar to or only marginally deviate from values predicted by the trendline.

The analysis using the spectrophotometry method was conducted once, and all standards
produced results similar to or only marginally deviate from values predicted by the trendline.

5. Discussions and conclusions

From the results measured above, we can confirm that the results for Li and Mn, with the
statistical error range, match with the mass percentages of the expected values for Li and Mn in
LiMn2O4.

Overall, the process and results are smoothly executed. However, more professional and
thorough actions, such as pipetting and mixing, can be done to improve the reliability of the
analysis.

Despite potential errors from the procedure, these methods are the suitable ways to carry out
this experiment, since they use AAS and spectrophotometry for measuring the elements, which
increases the accuracy. Therefore, they make the results more reliable than other basic
methods, such as titration or gravimetry, which involve more error-potential steps.

9
 6. References

Tong, L., Lankinen, T., Kuldeep, K., Silva, C., Leszczyńska N., Miikkulainen, V. Determination of Li
and Mn in lithium manganese oxide by using flame AAS and spectrophotometry, Laboratory
Instruction, Department of Chemistry and Materials Science, School of Chemical Engineering,
Aalto University, Espoo 2023.

Voitsekhovski, A. (2023, January 23). Lithium-ion manganese oxide (LMO) batteries. Aalto
University Wiki. https://wiki.aalto.fi/display/SSC/Lithium-ion+manganese+oxide+%28LMO
%29+batteries

Johnson, C. S. (2007). Development and utility of manganese oxides as cathodes in lithium

batteries. Journal of Power Sources, 165(2), 559–565.
https://doi.org/10.1016/j.jpowsour.2006.10.040

Lanz, M., Kormann, C., Steininger, H., Heil, G., Haas, O., & Novák, P. (2000). Large-agglomerate-
size lithium manganese oxide spinel with high rate capability for lithium-ion batteries. Journal
of The Electrochemical Society, 147(11), 3997. https://doi.org/10.1149/1.1394009

Butcher, D. J. (2005). Atomic absorption spectrometry | interferences and background

correction. Encyclopedia of Analytical Science, 157–163. https://doi.org/10.1016/b0-12-369397-
7/00025-x

Belford, R. (2021, December 26). 4.8: Spectrophotometry. Chemistry LibreTexts.

https://chem.libretexts.org/Courses/University_of_Arkansas_Little_Rock/
Chem_1402%3A_General_Chemistry_1_(Belford)/Text/4%3A_Stoichiometry
%3A_Quantitative_Information_about_Chemical_Reactions/4.8%3A_Spectrophotometry

Yi, T.-F., Zhu, Y.-R., Zhu, X.-D., Shu, J., Yue, C.-B., & Zhou, A.-N. (2009). A review of recent
developments in the surface modification of LIMN2O4 as cathode material of power lithium-ion
battery. Ionics, 15(6), 779–784. https://doi.org/10.1007/s11581-009-0373-x

10
Cai, C., & Koenig, G. M. (2022). Investigating dopants to improve sintered LiMn2O4 spinel
electrode electrochemical cycling limitations. Electrochimica Acta, 401, 139484.
https://doi.org/10.1016/j.electacta.2021.139484

Shao, X., Zhang, D., Li, H., & Cai, X. (2017). Selective method for the determination of
manganese in end-fitting of spoolable reinforced plastic line pipe for Petroleum Industries. IOP
Conference Series: Materials Science and Engineering, 250, 012001.
https://doi.org/10.1088/1757-899x/250/1/012001

11