Lithium-Gold Electrochemical Alloying: Clarifying Reaction Pathways and Products Using Operando XRD

Gold electrodes are used in lithium-ion battery research despite their high cost and unclear reactivity with lithium. Many equilibrium phases of gold-lithium (Au-Li) exist—solid solutions alpha, beta, and delta, and intermetallic phases AuLi 3 and Au 4 Li 15 . During the first alloying reaction, the equilibrium alpha and beta phases are seemingly bypassed; a phase, presumably delta, forms at a potential of 0.25 V (all potentials vs Li/Li + ), followed by the formation of AuLi 3 at 0.15 V at all conditions tested and Au 4 Li 15 at 0.05 V in select conditions. Alloying reactions are reversible to (delta), followed by the formation of another phase near 0.3 V and a low Li content phase at potentials above 0.4 V during de-alloying. Observed diffraction peaks only partially align with previous reports for all phases other than Au 4 Li 15 . The second alloying/de-alloying cycle is reversible between a low Li content phase (not pure gold) and the terminal phase. Some reaction hysteresis is present at low Li content. While the (delta)/AuLi 3 reaction had a consistent potential during alloying and de-alloying, the potential otherwise varied strongly with temperature, rate, and composition, implying that gold quasi-reference electrodes may not be suitable for lithium-ion battery research.