Structural characterization and electrochemical hydrogen storage properties of Ti2−xZrxNi (x = 0, 0.1, 0.2) alloys prepared by mechanical alloying

•Amorphous Ti2Ni was synthesized by mechanical alloying.•We studied the influence of milling time and Zr substitution.•Ti2−xZrxNi exhibit cycling stability in the electrochemical performance tests.•Zr substitution brings about oxidation problem to the Ti–Ni system.

Nominal Ti2Ni was synthesized under argon atmosphere at room temperature using a planetary high-energy ball mill. The effect of milling time and Zr substitution for Ti on the microstructure was characterized by XRD, SEM and TEM, and the discharge capacities of Ti2−xZrxNi (x = 0, 0.1, 0.2) were examined by electrochemical measurements at galvanostatic conditions. XRD analysis shows that amorphous phase of Ti2Ni can be elaborated by 60 h of milling, whereas Zr substitution hinders amorphization process of the system. The products of ball milling nominal Ti2−xZrxNi (x = 0.1, 0.2) were austenitic (Ti, Zr)Ni and partly TiO, despite the fact that the operation was carried out under argon atmosphere. By comparing the SEM micrographs, it is found that the amorphous phase of Ti2Ni was formed in the stage of cold-welding during milling, while with Zr substitution particles were flaky and finer, inhomogeneous in size distribution with massive agglomeration. TEM analysis was carried out and confirmed the observations via XRD. In the electrochemical tests, amorphous Ti2Ni shows the best discharge capacity at 102 mAh/g at a current density of 40 mA/g. Without need of activation, it exhibits extraordinary cycling stability under room temperature. On the other hand, the effect of Zr substitution on the electrochemical property of Ti2Ni is tricky, as superficially the discharge capacity drops drastically with Zr substitution, but with increase of Zr content (from x = 0.1 to x = 0.2), the discharge capacity increases generally, which credits to larger unit-cell-volume provided by ZrNi compared to TiNi. It is also found that the Ti–Ni system becomes significantly susceptible to oxidation when Zr is introduced to the initial powders as mechanical alloying is deployed as a synthesis method.