Analysis of Black Mass Using ICPE-9800 for Enhancing Accuracy of EDX-7200 Results

Significance of the Topic

Precise elemental analysis of black mass from spent lithium-ion batteries is crucial for efficient recovery of critical metals such as nickel, cobalt and manganese. Reliable input data enable battery recyclers to optimize extraction processes, while black mass producers need consistent quality control to meet downstream process requirements.

Objectives and Study Overview

This application evaluates how inductively coupled plasma optical emission spectroscopy (ICP-OES) using Shimadzu’s ICPE-9800 Series can provide accurate reference values for energy-dispersive X-ray fluorescence (ED-XRF) performed with the EDX-7200. The aim is to establish calibration standards, assess analytical performance and demonstrate complementary strengths of both techniques.

Methodology and Instrumentation

Samples of black mass from eight European suppliers were ashed at 800 °C, digested in HCl/HNO₃ via microwave digestion and diluted prior to analysis. Calibration standards were prepared from single-element solutions with yttrium as an internal standard.

• ICP-OES instrument: ICPE-9820 with 1.2 kW RF power, axial/radial observation, cyclone spray chamber and peristaltic pump for sample introduction.
• ED-XRF instrument: EDX-7200 used for fast solid sample screening with minimal preparation.

Main Results and Discussion

Calibration curves for Al, Co, Cu, Li, Mn, Ni, P, S and Zn exhibited excellent linearity (R² > 0.9995). Detection limits (LOD) ranged from 0.001 mg/L for Co and Zn to 0.02 mg/L for Li and Ni. Continuous calibration verification over 3.5 hours showed internal standard stability within ±10 % and CCV recoveries within ±5 %.

Matrix effects were ruled out by dilution-recovery tests at 1×, 2× and 3× dilutions, all showing recoveries within 100 % ±10 %. Spectral interference assessment compared multiple emission lines: P was best measured at 178.287 nm, avoiding overlap with Cu/Fe, and Zn at 206.200 nm free from Ni/Cu interference.

Triplicate analyses of eight samples yielded element concentrations with average relative standard deviations (RSD) typically below 5 %, indicating good reproducibility and sample homogeneity.

Benefits and Practical Applications

• ICP-OES provides accurate reference data for calibrating ED-XRF, enabling rapid on-site screening with the EDX-7200.
• Liquid sample analysis allows straightforward dilution and spike-recovery tests to detect biases.
• Two-step preparation (ashing plus digestion) facilitates carbon determination by loss on ignition and simplifies vessel cleaning.

Future Trends and Opportunities

Advances may include automated sample preparation workflows integrating ashing and digestion steps, hybrid instruments combining XRF and ICP capabilities, and AI-driven spectral deconvolution for real-time interference correction. Expansion into continuous process monitoring and in-line analytics will further streamline battery recycling operations.

Conclusion

Shimadzu’s ICPE-9800 Series ICP-OES delivers highly reliable elemental data for black mass analysis, serving as an ideal calibration reference for the rapid ED-XRF screening by EDX-7200. The complementary use of both techniques balances speed and accuracy, supporting robust quality control in lithium-ion battery recycling.

References

1. Fast and accurate analysis of Black Mass using EDX-7200 facilitated by using ICPE-9820, Nellessen, Shimadzu Europa GmbH, Application News 05-SCA-125-031-EN.
2. Mousa et al. Characterization and Thermal Treatment of the Black Mass from Spent Lithium-Ion Batteries. Sustainability 2023, 15, 15.
3. Determination of Essential Metals and Trace Elements in Black Mass using ICPE-9820. Zhen Hao, Qi An, Shimadzu (Asia Pacific) Pte Ltd, Application News 04-AD-0298-EN.