The use of UV/vis absorption to measure diffusion coefficients in LiPF6 electrolytic solutions

This work describes the measurement of the diffusion coefficient in lithium-battery electrolytic solutions. We have adapted the method of restricted diffusion to measure diffusion coefficients of LiPF6 in various solvents using ultraviolet/visible (UV/vis) absorption. The use of UV/vis absorption provides a simple alternative to more arduous experiments and reduces the potential for experimental error due to side reactions. The diffusion coefficient was seen to decrease with concentration according to the following: D = 3.018 X 10(-5) exp(-0.357c) for LiPF6 in acetonitrile and D = 2.582 X 10(-5) exp(- 2.856c) for LiPF6 in ethylene carbonate/diethyl carbonate (with D in cm(2)/s and c in mol/L). This technique may be useful for any liquid solution with a UV-active species of D greater than 10(-6) cm(2)/s. (c) 2007 The Electrochemical Society.