Electrical transport properties of bismuth vanadate (BiVO 4 ) are studied under high pressures with electrochemical impedance spectroscopy. A pressure-induced ionic-electronic transition is found in BiVO 4. Below 3.0 GPa, BiVO 4 has ionic conduction behavior. The ionic resistance decreases under high pressures due to the increasing migration rate of O 2− ions. Above 3.0 GPa the channels for ion migration are closed. Transport mechanism changes from the ionic to the electronic behavior. First-principles calculations show that bandgap width narrows under high pressures, causing the continuous decrease of electrical resistance of BiVO 4.
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