关键词: 离子色谱, 阴离子, 碳酸锂, 在线基体去除, 双抑制

Abstract:

A method was developed for the determination of trace anions in battery-grade lithium carbonate. In this method, lithium carbonate was dissolved in ultrapure water with ultrasound assistance, and its matrix was removed using an on-line matrix-removal method. In the matrix-removal process, the sample was first passed through an ADRS600(4 mm) suppressor (suppressor current, 150 mA; external water flow rate, 2 mL/min). Hydrogen and lithium ions were then completely exchanged via the ion-exchange membrane in the suppressor, converting the lithium carbonate into carbonic acid. The carbonic acid entered the waste-liquid channel in the form of carbon dioxide through a CRD 200(4 mm) carbonate removal device to remove the lithium carbonate matrix. Finally, the target anions were automatically enriched on an IonPac UTAC-LP2 concentration column (35 mm×3 mm) and automatically transferred to a chromatographic system using valve-switching technology. The chromatographic system featured an IonPac AG18 column (50 mm×2 mm) as the protection column and an IonPac AS18 column (250 mm×2 mm) as the analytical column. The column temperature was 30 ℃, gradient elution was performed using KOH solution as the eluent, and the pump flow rate was 0.30 mL/min. An ADRS600(2 mm) suppressor, suppressor current of 25 mA, injection volume of 250 μL, and conductance detector were also used. The results showed good linear relationships (r≥ 0.999) for F^-, Cl^-, ${\mathrm{N}\mathrm{O}}_2^{-}$, Br^-, ${\mathrm{N}\mathrm{O}}_3{}^{-}$, and ${\mathrm{S}\mathrm{O}}_4{}^{2-}$ in their respective concentration ranges. The limits of detection (LODs) and quantification (LOQs) were 0.05-0.88 and 0.15-2.92 μg/L, respectively. Lithium carbonate samples were tested six consecutive times, and the relative standard deviations (RSDs) of the peak areas of each ion were less than 0.73%. The same lithium carbonate samples were injected after 0, 2, 4, 8, 12, 18, and 24 h, and the RSD of the peak areas of each ion was less than 0.96%. The average recoveries ranged from 93.3% to 99.3%, and the RSDs (n=6) of samples spiked at three levels were in the range of 0.97%-3.45%. The proposed method has a low method limit of quantification of only 0.5 mg/kg for each ion analyzed and is capable of the simultaneous analysis of multiple ions. Thus, it is suitable for the detection of trace anions in battery-grade lithium carbonate.

Key words: ion chromatography (IC), anions, lithium carbonate, on-line matrix-removal, double-inhibition