Given the environmental pollution and thermal risks of lithium-ion batteries, it is necessary to recycle and evaluate the safety of spent lithium-ion batteries. Here, lithium tin alloys (LixSny) were prepared via mechanical alloying to simulate the tin anode materials at different lithium-embedded states. Among them, the Li22Sn5 alloy showed the optimum hydrolysis performance, releasing 351 mL g−1 hydrogen in 10 s at 293 K. The safety evaluation was carried out based on hydrolysis performance, maximum adiabatic temperature rise, and other parameters. The Li22Sn5 alloy required 738.8 mL of water to cool down to 303 K. Moreover, the reaction rates can be precisely controlled by tailoring the solution components, which effectively promoted the security and controllability for practical application. In addition, the hydrogen production of Li22Sn5 sample after hydrogenation increased to 624 mL g−1, even at a subzero temperature of 243 K, 510 mL g−1 hydrogen can be generated within 30 s. This study provides a new idea for the safety evaluation and recycling of tin anode materials in spent lithium-ion batteries. •The hydrogen production performance of lithium tin alloys was investigated.•The safety of lithium tin alloy phases of tin anode was evaluated.•The reaction rate can be precisely controlled by adjusting solution composition.•Li22Sn5 hydride generated 510 mL g−1 within 30 s at 243 K.