Effect of Ferroelastic Zr0.92Y0.08O2 on the Charge-Discharge Cycling Performances of the Layered LiMnO2 Cathode Materials

doi:10.6023/A25030072

Abstract

Layered LiMnO₂ (LMO) with an orthorhombic structure is an abundant and inexpensive manganese-based cathode material for lithium-ion batteries, but it suffers from challenges such as poor charge-discharge cycle stability. To address this issue, nanoscale Y-stabilized ZrO₂ (Zr_0.92Y_0.08O₂, YSZ) is coated on LiMnO₂ crystallites by a wet-chemical method to improve its charge-discharge cycle performance in this paper. X-ray diffraction (XRD) and transmission electron microscope (TEM) analyses show that YSZ in the synthesized material has a tetragonal structure with a size distribution of 3~15 nm, coating LMO particles as thin layers or particles to form LMO@YSZ nanocomposites. High resolution transmission electron microscope (HRTEM) analysis reveals the presence of 90° ferroelastic domains in the tetragonal phase within the nanoscale YSZ surrounding LMO particles. Charge-discharge tests demonstrate that the maximum discharge capacity is 192 mAh•g⁻¹ at a current density of 20 mA•g⁻¹. After 300 cycles at 200 mA•g⁻¹, the capacity of the LMO@YSZ composite remains at 59% of its maximum capacity, significantly suppressing the decay of charge-discharge specific capacity compared to 36% for pure LiMnO₂. Scanning electron microscope (SEM) observations reveal that after 300 charge-discharge cycles, the uncoated LMO electrode contains cracks approximately 700 nm wide and over 40 μm long, which interweave to form isolated "island-like" regions in the electrode. In contrast, cracks are hardly observable in the YSZ-coated electrode, with particles in close contact. The number of cracks in the LMO@YSZ composite electrode are significantly suppressed. Considering ferroelastic domains in YSZ of the composite, it is inferred that the improved charge-discharge cycle performance of the LMO@YSZ composite is attributed to reduced or inhibited cracking from the experimental results. This may originate from the electrochemical-ferroelastic coupling effect between the LMO cathode material and YSZ ferroelastic material during charge-discharge processes, delivering stress energy in LMO to YSZ. As a result, the ferroelastic behavior of YSZ dissipate the stress energy in the cathode material, effectively suppressing crack generation in the electrode without hindering electron and lithium-ion diﬀusion, thereby improving the charge-discharge cycle performance of the LiMnO₂ electrode.

Key words: LiMnO₂, Y-stabilized ZrO₂, cathode materials, ferroelastic materials, lithium-ion battery

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Jicheng Lu, Lei Gou, Xiaojiu Liu, Xiaoyong Fan, Donglin Li. Effect of Ferroelastic Zr_0.92Y_0.08O₂ on the Charge-Discharge Cycling Performances of the Layered LiMnO₂ Cathode Materials[J]. Acta Chimica Sinica, 2025, 83(8): 844-852.

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Fig. & Tab. 9

Figure 1. (a) X-ray diffraction patterns of LMO samples; (b) XRD pattern of Zr0.92Y0.08O2 powder synthesized at 600 ℃ for 3 h under argon atmosphere

Figure 2. TEM images of as-synthesized LMO@1YSZ composite. (a) TEM showing YSZ coating layer on LMO particle; (b) HR-TEM showing ferroelastic domains and lattice strips corresponding to YSZ and LMO crystallites

Figure 3. SEM images of (a), (b) pure LMO and (c), (d) LMO@1YSZ samples at different magnifications

Figure 4. (a) The initial charge and discharge curves of pure LMO, LMO@1YSZ and LMO@3YSZ; (b) Charge and discharge curves for the 5th cycle of pure LMO, LMO@1YSZ, and LMO@3YSZ; (c) Charge and discharge curves of pure LMO, LMO@1YSZ, and LMO@3YSZ at maximum discharge capacity

电极名称	初始充电比容量/ (mAh•g⁻¹)	初始放电比容量/ (mAh•g⁻¹)	库伦效率
LMO	350.60	138.17	39.40%
LMO@1YSZ	323.28	157.60	48.75%
LMO@3YSZ	321.62	113.13	35.17%

Table 1. Initial charge-discharge capacity and Coulomb efficiency of pure LMO, LMO@1YSZ and LMO@3YSZ electrode

Figure 5. (a) CV curves of LMO and (b) LMO@1YSZ

Figure 6. Electrochemical properties of synthesized LMO, LMO@1YSZ, and LMO@3YSZ materials. (a), (b) Cycle performances at 0.1C and 1C; (c)~(e) charge-discharge curves at different cycles at 200 mA•g−1; (f) charge-discharge curves at 30th and 300th

Figure 7. Charge-discharge curves of the cycle with the maximum discharge capacity of (a) LMO@1YSZ and (b) LMO at different current densities

Figure 8. SEM images of (a), (c), (e) LMO and (b), (d), (f) LMO@1YSZ electrode pieces after cycling for 300th at a current density of 200 mA•g−1

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铁弹Zr_0.92Y_0.08O₂对层状LiMnO₂正极材料充放电循环行为的影响

Effect of Ferroelastic Zr_0.92Y_0.08O₂ on the Charge-Discharge Cycling Performances of the Layered LiMnO₂ Cathode Materials

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铁弹Zr0.92Y0.08O2对层状LiMnO2正极材料充放电循环行为的影响