The study about the low-temperature performance of lithium-ion batteries (LIB) is of great significance at extreme temperatures, such as polar scientific research, space exploration, deep-sea exploration, military fields, and so on. In this study, normal devices and symmetrical devices were fabricated by ternary Li(Ni0.5Mn0.3Co0.2)O2 as cathode and graphite as anode at 25 and −20 °C. The results show that the specific discharge capacity of normal device is up to 120 mAh g−1 at 1 C and 25 °C. The specific capacity and energy density at 0.2 C and −20 °C are 106.05 mAh g−1 and 376.53 mWh g−1, respectively, which can reach 92.82% of that at 1 C and 25 °C. The value of activation energy Ea of the interface reaction of the LIB is calculated to be 63.72 kJ/mol by the Arrhenius equation. When the temperature dropped from 25 to −20 °C, the lattice spacing of Li1−x(Ni0.5Mn0.3Co0.2)O2 hardly changed, while the lattice spacing (002) of graphite reduces 0.00248 Å. In addition, some cracks were observed on the charged cathode at −20 °C. We carried out quasi-in situ electrochemical impedance spectroscopy (EIS) when the voltages of normal device discharged to 3.8, 3.6, 3.4, 3.2, and 3.0 V. Unlike the relationship of voltage–resistance at 25 °C, the values of the series resistance (Rs), charge transfer resistance (Rct), and ion transfer resistance (Rit) gradually decrease as the voltage decreases at −20 °C. Compared with the resistance of the symmetrical device based on the anode at 25 °C, the values of Rs and Rit at −20 °C both obviously increase. The main reason of performance degradation for normal device at −20 °C is large ion transfer resistance and the decrease of lattice spacing of the graphite (002).