Nickel aluminum layered double hydroxide (NiAl LDH) with nitrate in its interlayer is investigated as a negative electrode material for lithium-ion batteries (LIBs). The effect of the potential range (i.e., 0.01–3.0 V and 0.4–3.0 V vs. Li+/Li) and of the binder on the performance of the material is investigated in 1 M LiPF6 in EC/DMC vs. Li. The NiAl LDH electrode based on sodium alginate (SA) binder shows a high initial discharge specific capacity of 2586 mAh g−1 at 0.05 A g−1 and good stability in the potential range of 0.01–3.0 V vs. Li+/Li, which is better than what obtained with a polyvinylidene difluoride (PVDF)-based electrode. The NiAl LDH electrode with SA binder shows, after 400 cycles at 0.5 A g−1, a cycling retention of 42.2% with a capacity of 697 mAh g−1 and at a high current density of 1.0 A g−1 shows a retention of 27.6% with a capacity of 388 mAh g−1 over 1400 cycles. In the same conditions, the PVDF-based electrode retains only 15.6% with a capacity of 182 mAh g−1 and 8.5% with a capacity of 121 mAh g−1, respectively. Ex situ X-ray photoelectron spectroscopy (XPS) and ex situ X-ray absorption spectroscopy (XAS) reveal a conversion reaction mechanism during Li+ insertion into the NiAl LDH material. X-ray diffraction (XRD) and XPS have been combined with the electrochemical study to understand the effect of different cutoff potentials on the Li-ion storage mechanism.