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Applications Note

Rapid, Acid-Free Analysis of Cathode Powders

Automated & quantitative determination of major elemental components and impurities

Laser Ablation | ICP Analysis | LaserTRAX Robotic System

Accurate and Precise | Solid Sample Analysis

Figure 1. LaserTRAX system with Avio 500 Series ICP

LaserTRAX: Robotic solid sample handling with automated barcode-reading for LA-ICP

Brief
Battery cathode materials are pressed into pellets and analyzed by laser ablation ICPOES (LA-ICP).
Simplification of the sample preparation not only eliminates the need for the time-consuming,
hazardous acid digestion steps, but also decreases the time from sample receipt to result to <5
minutes.

The novel method provides quantification of major elements and trace impurities in NMC powders
with the benefits of:

1) Reduction in sample preparation time from 30-60 minutes to <3 minutes

2) Elimination of acid related to preparation and waste disposal
3) Major and trace elements determinations with a single automated method

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Introduction
Cathode materials, such as LiNixMnyCo1-x-yO2 (NMC), have been identified as one of the most promising
materials for improving the performance of batteries. The performance and qualities of these
materials can be greatly impacted by the ratio of Ni-Mn-Co and Li, as well as the impurities in the
materials. The analysis of these materials has been reliant on acid digestion and subsequent analysis,
Class 1 Laser
for example flame atomic absorption spectrometry (FAAS), complexometric titration, and solution-ICP.
Interlocked Enclosure These methods are time-consuming, taking 30-60 minutes to digest a sample, all while generating
- Customizable for sample volumes hazardous waste.
- Add/remove samples during operation
- Extraction available
LA-ICP completely eliminates all acid waste generated in the sample preparation process and in the
operation of the ICP. In addition, samples can be prepared and analyzed in under 4 minutes; all while
Robotic Sample Handling meeting requirements stated in Chinese Standard YS/T 798-2012. Battery materials, such as LFP, LCO,
- Reduced operator input NMC, or NCA, can also be directly analyzed as a solid, with major and trace determination being done
- Fully-automated sample handling simultaneously.
- 24/7 operation

Laser Module
Various laser modules are
available depending on the
LaserTRAX
Avio 500

application requirements

LaserTRAX is a next-generation, single-unit instrument that fully automates the process of sample
SelfSeal Sample Chamber handling, laser sampling, ICP detection, data reduction and report generation. LaserTRAX is capable
- 5 s gas purge per sample of high-throughput (>500 pressed cathode samples per day) solid sampling. The system provides
- Automated chamber cleaning seamless sample flow by combining four main components (Figure 2):
- High sample transport efficiency
- Enhanced signal response
- Rapid sample changeover 1) Sample delivery and ablation
a. Robotic arm for sample loading
High-Throughput b. Sample Changer (SC) carousel
- Up to 5X faster than conventional laser ablation c. SelfSealTM laser cell
2) ESL 266 laser (193nm also available)
Barcode Scanner 3) ICP detection system (ICPMS also available)
- Reads sample ID 4) ESL LaserTRAX software for seamless operation and LIMS compatible data reduction
- Two-way LIMS communication
Figure 2. LaserTRAX features diagram - Auto-builds real-time ICP run list

Operation is simplified through the LaserTRAX user interface. Once samples are loaded into the system,
the user simply defines the number of samples and the frequency of blanks, standards, and QCs. The
sequence is then generated and the user starts the analysis. Figure 3 shows the order of operation for
this method.

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LaserTRAX Analytical Cycle

Robotic Sample Handling ICP Data Acquisition

Start Start
Operator Sample associated
loads samples ICP is triggered
with barcode
in vials on by LaserTRAX
is made available to LIMS
autosampler deck
Laser
Ablation
Piston is lowered
and sample is removed ICP acquires
LaserTRAX
from carousel multi-element data
calculates data
Sample (<60 s)
Sample
Aerosol
to ICPMS
Laser fires (including
Robot picks up sample
pre-ablation)
and scans barcode
(~85 s)

Ni Mn Co

Piston pushes sample up

Sample is loaded
to SelfSeal chamber and
onto carousel
purges (~5 s)

Carousel rotates
to laser position

232.003 293.305 238.892

nm nm nm
Figure 3. LaserTRAX sample to sample time is defined by the analytical conditions. In this example, the system is purged (5 s), a pre-
ablation is done to remove any surface contamination (25 s), major components and trace impurities elements are measured (<60 s),
cell is cleaned with N2 purge and next sample is sealed (10 s) for a total analytical time of <2 minutes. During the analytical cycle, the
robot unloads a previously analyzed sample, picks up the next sample, scans barcode, and loads next sample onto carousel.
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Instrumentation
A PerkinElmer Avio 500 was implemented with the LaserTRAX for this application. A simultaneous Table 3. NMC Powders with different molar ratios analyzed Table 4. Mass fractions of NMC 111 and NMC 622 in the
instrument is required for this analysis because it acquires all analytes in one acquisition which mixtures
Molar Ratios of Major Components
produces more stable major component molar ratios. ICP parameters can be found in Table 1 and Cathode Li Ni Mn Co O Sample NMC 111 Mass NMC 622 Mass
analyte information can be found in Table 2. Materials Fraction (%) Fraction (%)

NMC 111 1 0.33 0.33 0.33 2 Mix 1 25 75

NMC 532 1 0.5 0.3 0.2 2 Mix 2 50 50

Sample and Standard Preparation NMC 622 1 0.6 0.2 0.2 2 Mix 3 75 25

Three ternary cathode materials of different compositions were utilized in these experiments (Table
3). Three mixtures of NMC 111 and NMC 622 were prepared according to the mass fractions shown
in Table 4. Sample preparation is fast and simple for LaserTRAX samples (Fig. 4). The sample is scooped (~0.2 g)
and then pressed in a 13 mm die in a hydraulic press at 10 T for 30 seconds. Samples are then loaded
into an ESI sample holder. For the analysis of ternary cathode materials, samples were prepared
such that the analytical surface of the pellet was a solid layer of NMC. This prevents any dilution of
Table 1. LaserTRAX and ICP Parameters Table 2. Wavelengths for major and trace
the sample, resulting in better detection limits and a more homogeneous sample. A sample can be
elements
Parameters weighed, pressed, and ready for analysis in under 2 minutes.
Major Elements
LaserTRAX Setting
Analyte Wavelength (nm)
Raster Pattern Size 1 mm x 1 mm
Co 238.892
Ablation Spot Size (µm) 180
Li 610.362 Sample is scooped and Pellet is ejected from Sample is loaded into
Repetition Rate (Hz) 5
pressed into pellet (~60 s) press (<15 s) sample holder and barcode
Mn 293.305
Scan Speed (µm/sec) 100 sticker is attached (~30 s)
Ni 232.003
Warm Up Time (s) 5
Trace Elements
Laser Cell Gas Flow Rate (L/min) 0.8
Analyte Wavelength (nm)
Pre-ablation Passes 1
Al 396.153
ICP
Ba 455.403
Quartz ZipTorch for laser only (T20Q-37)
Torch
Nitride ZipTorch for laser + solution (ZTN-D-37) Be 313.107
Injector Diameter (mm) 2 Ca 396.847
Plasma Gas Flow (L/min) 14 Cu 324.752
Auxiliary Gas Flow (L/min) 1 Fe 259.939
Torch Position -3 Mg 285.213
ICP RF Power (W) 1500 Na 589.592
Viewing Mode Axial Sr 407.771
Stabilization Delay (s) 15 Zr 343.823
Integration Time (s) 0.01

Read Time (s) 8

Figure 4. Sample preparation process is reduced from 30-60 minutes acid digestion to <2 minutes for pressed pellets.
Replicates 3

Laser Mixing Chamber (S011787)

Ar Addition Gas Flow (L/min) 0.13 (ICP nebulizer gas)

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Results and Discussion

LaserTRAX automatically processes ICP (can also be used for ICPMS) data and displays the calculated To prove the technique for a range of NMC materials, NMC samples with different metal molar ratios
values in real time. The number of standards, standard concentrations, blanks, QC concentrations, and were prepared and analyzed using NMC 111 as the reference standard. The analysis was repeated
sample ID information can all be imported with barcode IDs, eliminating user error associated with 5 times to demonstrate the robustness of the analytical method (Table 6). Precision for all sample
sample ordering or transcription. Together, these features ensure the correct answer is associated types was within ±0.24 mol % for Co, ±0.42 mol % for Mn, ±0.59 mol % for Ni, and ±0.03 mol % for Li/
with the corresponding sample every time. Metals for the 5 analytical measurements.

Xceleri, the ESL LaserTRAX software, automatically converts the major component data to the final
molar ratios. Equations 1 through 5 (Appendix A) show the calculations in detail.

Molar ratios are an important characteristic of the NMC materials with different ratios of metals Table 6. LaserTRAX determined mol % compared to reference value

providing different properties. The undiluted preparation of the NMC allows for more reproducibility Co Mn Ni Li/Metals
between samples, which provides confidence that the results obtained are correct for that material. Reference LA-ICPOES Reference LA-ICPOES Reference LA-ICPOES Reference LA-ICPOES
Sample
To show the stability of the LaserTRAX analysis, 8 replicate NMC 111 samples were prepared and Value (mol %) (mol %) Value (mol %) (mol %) Value (mol %) (mol %) Value (mol %) (mol %)
analyzed. Excellent precision, < 0.4% RSD, was displayed for the 8 samples analyzed representing a NMC 532 19.50 19.26 ± 0.17 32.77 32.19 ± 0.42 47.73 48.54 ± 0.59 1.05 1.07 ± 0.02
stable and reproducible method. The sample repeatability measurements are shown in Table 5. NMC 622 19.48 19.59 ± 0.19 22.50 22.96 ± 0.20 58.02 57.45 ± 0.36 1.06 1.04 ± 0.02

Mix 1 23.18 22.98 ± 0.08 25.15 25.59 ± 0.16 51.67 51.44 ± 0.21 1.06 1.04 ± 0.03

Mix 2 26.70 26.51 ± 0.08 27.77 28.05 ± 0.19 45.53 45.43 ± 0.25 1.08 1.07 ± 0.02
Table 5. Pressed pellet sample prep and analysis yields <0.4% RSD
Mix 3 30.70 30.19 ± 0.24 30.44 30.58 ± 0.39 38.86 39.23 ± 0.57 1.09 1.06 ± 0.02
Sample Number Co Mol % Mn Mol % Ni Mol % (Li Mol %)
*All samples were analyzed 5 times (n = 5)
(Co+Mn+Ni Mol %)

1 32.91 33.12 32.91 1.04

2 33.11 32.95 32.89 1.04

3 32.87 33.10 32.98 1.05

Comparing the results from LaserTRAX and the reference values, there was excellent agreement.
4 32.77 33.08 33.10 1.05 The determined molar ratios were within ±0.51 mol % for Co, ±0.58 mol % for Mn, ±0.81 mol % for Ni,
5 32.79 33.19 33.01 1.04 and ±0.03 mol % for Li /Metals for the NMC 532, NMC 622, and the 3 mixtures.
6 32.93 33.14 32.91 1.04

7 33.01 33.10 32.84 1.04

For the analysis of trace contaminants, Standard Addition (SA) calibration was utilized by spiking
a series of NMC 111 material. Examples of the SA calibration curves are shown in Figure 5 for Mg,
8 32.81 33.13 33.08 1.04
Cu, Ca, and Fe. The calibrations show good linearity (>0.95) and LODs are all below recommended
Average 32.90 ± 0.11 33.10 ± 0.06 32.97 ± 0.09 1.04 ± 0.003
manufacturing requirements for ternary cathode quality assurance (Table 7). Concentrations were
RSD (%) 0.33 0.19 0.26 0.30 determined for the common contaminants of interest in these types of cathode materials.

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MgMg Cu Cu Table 7. LaserTRAX determined mol % compared to reference value

Analyte Al Ba Be Ca Cu Fe Mg Na Sr Zr
500 500 700 700
R 2
0.993 1.000 0.994 0.996 0.990 0.996 0.999 0.955 0.995 0.993
600 600
400 400 Manufacturing

Intensity (cps)
Intensity (cps)
500 500 N/A N/A N/A <300 <300 <300 <300 <300 N/A N/A
Intensity (cps)
Intensity (cps)

Requirements (ppm)
300 300 400 400 LOD 9.6 0.58 7.5 0.19 4.1 9.6 3.0 6.2 0.10 0.70

200 200 300 300 NMC 111 93.4 1.13 14.3 43.0 <LOD <LOD 27.4 210 0.96 316
200 200 NMC 532 1846 4.12 <LOD 32.6 <LOD 19.8 25.0 159 21.0 10.1
100 100 y = 3.02x
y = 3.02x
+ 79.3
+ 79.3 y = 4.71x
y = 4.71x
+ 167.60
+ 167.60
100 100 R² = R²
0.99
= 0.99 NMC 622 1096 1.55 9.18 28.9 <LOD 11.5 21.4 261 12.9 4.21
R² = R²
0.999
= 0.999
0 0 0 0 Mix 1 982 1.27 11.1 29.8 <LOD <LOD 25.9 228 9.20 87.5
0 0 50 50 100 100 0 0 50 50 100 100 150 150
Concentration
Concentration
(ppm)
(ppm) Concentration
Concentration
(ppm)
(ppm)

Conclusion
Ca Ca Fe Fe
The analysis of NMC can be greatly simplified by analyzing pressed-pellets by LaserTRAX rather
80008000 100 100
than digesting the materials. Sample preparation time is reduced to under 3 minutes and analysis
70007000
80 80 in under 4 minutes. Acid digestion is completely eliminated from the sample preparation procedure.
60006000
Intensity (cps)
Intensity (cps)

Intensity (cps)
Intensity (cps)

User intervention is drastically reduced after samples have been delivered to the autosampler deck of
50005000 60 60 the robot. Stability of molar ratios is exceptional, with RSD < 0.4% for 8 replicate pellets of NMC 111.
40004000 LaserTRAX is able to differentiate between samples with small changes in molar ratio. Stability of
30003000 40 40
the analytical method from run to run is excellent, with an RSD less than 3% over 5 runs. LaserTRAX
20002000 y = 57.2x
y = 57.2x
+ 3,061
+ 3,061 y = 0.813x
y = 0.813x
+ 4.341
+ 4.341 correlated well with established reference values, with ± 2% difference for Co, Mn, and Ni, and within
20 20
10001000 R² = R²
0.996
= 0.996 R² = R²
0.996
= 0.996 ± 5% difference for Li. LaserTRAX is the ideal tool for the analysis of cathode materials to provide
0 0 0 0 accurate, precise, and rapid results using automation without the need for corrosive acids.
0 0 20 20 40 40 60 60 0 0 50 50 100 100 150 150
Concentration
Concentration
(ppm)
(ppm) Concentration
Concentration
(ppm)
(ppm)

Figure 5. Standard Addition calibration curves for Mg, Cu, Ca, and Fe

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 Appendix A
Equations
First, concentration is determined for each analyte by dividing by the slope of the calibration
curve created by the standard.

Equation 1.
Conc.(X)=Int(X)/m

Where X is the analyte and m is the slope determined by the calibration curve.

Next, concentration is converted to moles by dividing the concentration by the molar mass of the analyte.

Equation 2.
Moles(X)=Conc.(X)/M

Where M is the molar mass of the analyte.

The moles of total metals in NMC can obtained by summing the moles of Co, Mn, and Ni.

Equation 3.
Moles(Metals)= Moles(Co)+Moles(Mn)+Moles(Ni)

The molar ratio for each of the metals is then calculated by dividing the moles of the analyte by the
sum of the moles of the major metal analytes and multiplied by 100 to convert to a percentage.

Equation 4. Moles(X)
Molar Ratio(X)= Moles(Metals) *100

And the ratio of Li to total metals can be found by dividing the molar ratio of lithium by the molar
ratio of total metals.

Equation 5.
Li:Metals Ratio= Moles(Li)
Moles(Metals)

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