Electrochemical synthesis of materials has contributed to significant breakthroughs in materials processing by replacing high temperature, cost and energy intensive pyrometallurgical processes. Although electrodeposition as a technology for reduction of elements and alloys has been practiced since at least the 1940s, a current key and exciting question is to identify and develop electrodeposition strategies for the growth of secondary battery cathodes. Specifically, we focus on anodic electrolytic deposition methods to grow alkali-ion intercalated, layered/spinel transition metal oxide intercalation cathode systems. State-of-the-art synthesis for layered oxide cathodes for Li and Na-ion battery involves prolonged high temperature (>700°C) processing for long reaction times (~24 hours) under high oxygen pressure, followed by slurry casting after mixing with binders and additives. Here, we demonstrate an intermediate temperature (250-350°C) electrodeposition process to grow alkali ion (Li+, Na+) intercalated transition metal oxides across multiple transition metal chemistries of the Li system (orthorhombic LiMnO2, Li2MnO3, LiNixMn1-xO4, LiMn2O4, LiCoO2) and Na system (O3 and P2 NaxCoO2, O’3 NaxMnO2) in thick film form factors. Even though our cathodes are electrochemically grown at the lowest reported synthesis temperature and reaction times, they retain the key structural and electrochemical performance of the high temperature bulk synthesized analogues. The key features of this alternate high throughput cathode manufacturing technique include formation of binder-and-additive-free, tens of microns thick, >75% dense electrodeposits exhibiting near theoretical gravimetric capacity, low tortuosity, and chemical diffusion coefficient of Li+/Na+ ions. Our findings highlight the influence of the unique molten hydroxide-based solution chemistry platform and electrochemical processing parameters, on regulating the phase assemblage, designing the microstructure, and controlling crystallographic orientation during electrocrystallization.
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