AN-S-403
2025-04
Anions in lithium-ion battery solvents
Determination of anions in N-methylpyrrolidone (NMP) by ion chromatography (IC)
Summary
N-Methylpyrrolidone (also known as N-methyl-2-pyrrolidone or NMP) is an organic solvent used to make slurry in battery manufacturing and is a key raw material for the lithium-ion battery (LIB) industry. It serves as an effective solvent for electrode binders, such as polyvinylidene fluoride, which are essential for maintaining electrode stability [1,2]. NMP is completely removed during the manufacturing process and can be recycled efficiently [3]. Global demand for NMP is high and it accounts for a substantial percentage of lithium-ion battery manufacturing costs [4].
NMP impurity analysis is crucial to assess the quality of both newly fabricated and recycled NMP. Ion chromatography (IC) with matrix elimination is a robust and reliable technique to quantify impurities in NMP in the µg/L range. Using this method, battery manufacturers can ensure the proper composition and electrochemical behavior of the electrolyte and evaluate Li-ion battery stability and safety.
Metrohm's intelligent Preconcentration Technique with Matrix Elimination (MiPCT-ME) quantifies anions in N-methyl pyrrolidone down to the µg/L range without sample treatment or dilution steps
Sample and sample preparation
A volume of 500 µL NMP was directly injected into the preconcentration column (PCC) of the IC without any treatment using an 800 Dosino (807 Dosing Unit 5 mL). The PCC, which is installed in place of a sample loop, captures the target ions and enables matrix removal. This allows trace analysis of anions even in complex matrices.
Experimental
The application was carried out using a 930 Compact IC Flex with MiPCT-ME and a fixed injection volume of 500 µL (preconcentration volume). A volume of 1.5 mL ultrapure water (UPW) was used for rinsing the PCC to remove the matrix. For further experimental details, see Table 1.
The IC system setup is schematically shown in Figure 1. Calibration ranged from 5 to 100 µg/L, prepared as mixed standards containing fluoride, chloride, nitrite, bromide, nitrate, phosphate, and sulfate. To guarantee comparability, standards were injected via the PCC as well.
Parameter | Setting |
---|---|
Detection | Conductivity |
Column | Metrosep A Supp 7 - 250/4.0 |
Preconcentration column | Metrosep A PCC 2 HC/4.0 |
Injection volume | 500 µL |
Temperature | 45 °C |
Eluent | 3.2 mmol/L Na2CO3 + 1.0 mmol/L NaHCO3 |
Suppression | Sequential suppression |
Regenerant | 100 mmol/L H2SO4 |
Flow | 0.7 mL/min |
Results
Anions were separated and eluted from the Metrosep A Supp 7 column in less than 34 minutes under isocratic conditions. Concentrations ranged from 11−76 µg/L.
The undiluted NMP sample was measured both unspiked and spiked with 30 µg/L standard ions, reaching a recovery of 90−120 % even for the very low concentrated ions (Table 2).
Figure 2 shows the separation of anions in NMP. Baseline separation is achieved for the indicated anions. The chromatogram shows two early eluting peaks which were not identified. Most likely these peaks account for acetate and formate showing the enormous potential for further development and thereby allowing quantification of other relevant anions.
Analyte | NMP unspiked (µg/L) |
Spike (µg/L) | NMP spiked (µg/L) |
Recovery (%) |
---|---|---|---|---|
Fluoride | 48.94 | 30 | 80.23 | 104.3 |
Chloride | 74.5 | 30 | 102.83 | 94.3 |
Nitrite | 76.31 | 30 | 103.35 | 90.1 |
Bromide | <1 | 30 | 27.89 | 93.0 |
Nitrate | 28.99 | 30 | 58.87 | 99.6 |
Phosphate | 11.21 | 30 | 47.04 | 119.4 |
Sulfate | 15.55 | 30 | 43.65 | 93.7 |
Conclusion
The concentrations of the measured anions in NMP range from 11 to 76 µg/L. Such low analyte concentrations in combination with an interfering matrix can be challenging for chromatography. Metrohm MiPCT-ME is capable of measuring trace anions in a widely used solvent of the lithium battery manufacturing process. This analytical technique can make a major contribution to guarantee the quality, lifetime, and safety of lithium batteries.
The method can easily be transferred to other relevant solvents like methanol, ethanol, acetone, and 2‑propanol.
References
- Yue, M.; Azam, S.; Zhang, N.; et al. Residual NMP and Its Impacts on Performance of Lithium-Ion Cells. J. Electrochem. Soc. 2024, 171 (5), 050515. DOI:10.1149/1945-7111/ad4396
- The role of NMP in the production process of lithium batteries - Shenyang East Chemical Science-Tech Co., Ltd.(ES CHEM Co.,Ltd). https://www.eschemy.com/news/the-role-of-nmp-in-the-production-process-of-lithium-batteries (accessed 2024-08-16).
- Darcel, C. What is NMP Solvent?. https://www.maratek.com/blog/what-is-nmp-solvent (accessed 2024-08-16).
- The Advanced Rechargeable & Lithium Batteries Association. Recommendation about N-Methyl-Pyrrolidone (NMP; CAS No. 872-50-4) Proposal for Inclusion in Annex XIV for Authorization, 2017.