Continuous Hydrothermal Synthesis of Metal Germanates (M2GeO4; M = Co, Mn, Zn) for High‐Capacity Negative Electrodes in Li‐Ion Batteries

Nanosized metal germanates ( M 2 GeO 4 ; M = Co, Mn, Zn) are synthesized using a continuous hydrothermal flow synthesis process for the first time. The electrochemical properties of all samples as active materials for negative electrodes in Li‐ion half cells are explored. The galvanostatic and potentiodynamic testing is conducted in the potential range of 3.00–0.05 V versus Li/Li + . The results suggest that both alloying and conversion reactions associated with Ge contribute to the stored charge capacity; Zn 2 GeO 4 shows a high specific capacity of 600 mAh g −1 (ten cycles at 0.1 A g −1 ) due to alloying and conversion reactions for both Ge and Zn. Mn 2 GeO 4 is studied for the first time as a potential negative electrode material in a Li‐ion half cell; an excellent specific charge capacity of 510 mAh g −1 (10 cycles per 0.1 A g −1 ) is obtained with a significant contribution to charge arising from the conversion reaction of Mn to MnO upon delithiation. In contrast, Co 2 GeO 4 only shows a specific capacity of 240 mAh g −1 , after ten cycles at the same current rate, which suggests that cobalt has little or no benefit for enhancing stored charge in germanate.