Nickel-rich ternary cathode materials (NRTCMs) have high energy density and a long cycle life, making them one of the cathode materials of LIB that are currently receiving much attention. However, it has shortcomings such as poor cycling performance (CP) and a high-capacity decay rate. Because of this, the study analyzed the modification effect of WO3 on NRTCM lithium batteries by preparing WO3-modified poly-crystal and single-crystal NCM622 materials under the existing conditions of better original cathode materials as reference samples. The results showed that in the morphology and structure testing, with the increase of WO3 addition, the c/a values of all NCM622-WO3 samples were greater than 4.95. In the analysis of cycling and rate performance (CRP), as W increased, the rate performance (RP) of the NCM622-W4.0 sample had a discharge specific capacity ratio of 86.2% at 10.0 C/1.0 C. In cyclic voltammetry testing, when the addition amount of WO3 was 1.0%, the polarization degree of SC-NCM622 sample was the weakest. In the AC impedance test, after six cycles, compared with the original sample, the Ret and R + Rct values of the NCM622-W sample modified with WO3 showed a significant downward trend. The above results prove that WO3 modification can lower the polarization of the material, effectively raising the CRP of the battery. It provides a reference path for the further progress of high capacity and stability ternary cathode materials.