P3-Na0.45Ni0.2Mn0.8O2/Na2SeO4异质结构实现长寿命和高倍率钠离子电池,Advanced Energy Materials

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P3-Na0.45Ni0.2Mn0.8O2/Na2SeO4异质结构实现长寿命和高倍率钠离子电池
Advanced Energy Materials ( IF 24.4 ) Pub Date : 2023-09-24 , DOI: 10.1002/aenm.202302393
Tianyi Song ₁ , Chenchen Wang ₁ , Lei Kang ₂ , Wenjiao Yao ₃ , Heyi Wang ₄ , Huige Chen ₂ , Qi Liu ₅ , Yang Lu ₆ , Zhiqiang Guan ₁ , Anquan Zhu ₁ , Tianxing Kang ₁ , Yongbing Tang ₃ , Chun‐Sing LEE ₁

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钠基层状氧化物正极由于其高理论容量、低成本和简单的合成而成为商业钠离子电池的竞争候选者。具有大开放通道的P3型层状氧化物可实现快速Na ⁺传输，因此具有良好的倍率性能。然而，P3型氧化物较低的晶体对称性以及脱钠/钠化过程中Na层中Na ^{+含量的变化导致TMO}₂板（TM=过渡金属）之间静电排斥力发生较大变化，导致不可逆相变，并且快速发生相变。性能下降。在此，首次发现潜在的Na ⁺导体Na ₂ SeO ₄，它可以很容易地在P3-Na _0.45 Ni _0.2 Mn _0.8 O ₂上原位生长，形成新型异质结构P3-Na _0.45 Ni _0.2 Mn _0.8 O ₂ /Na ₂ SeO ₄。_{P3-Na 0.45} Ni _0.2 Mn _0.8 O ₂和 Na ₂ SeO ₄之间的协同作用可促进 Na ⁺扩散并抑制深钠化时的 P3-O3 相变，从而实现高倍率性能记录（容量保持率为 68.2%，保留在所有报道的P3型正极中，其在6400 mA g -1 时的容量为^83.9 mAh g ^{-1 ）和优异的循环稳定性（1000次循环后容量保持率为75%）。}因此，相信这种新颖的异质结构设计为促进层状氧化物阴极在钠离子电池中的实际应用开辟了一条新途径。

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P3-Na0.45Ni0.2Mn0.8O2/Na2SeO4 Heterostructure Enabling Long-Life and High-Rate Sodium-Ion Batteries

Sodium-based layered oxide cathodes are competitive candidates for commercial sodium-ion batteries owing to their high theoretical capacities, low costs, and simple synthesis. P3-type layered oxides with large open channels enable fast Na⁺ transport and hence good rate performance. However, the lower crystal symmetry of P3-type oxides and variation of Na⁺ contents in the Na layer during desodiation/sodiation lead to large electrostatic repulsion changes between TMO₂ slabs (TM=Transition Metal), resulting in irreversible phase transitions, and fast performance degradation. Herein, a potential Na⁺ conductor Na₂SeO₄ is first found that it can be easily in situ grown on P3-Na_0.45Ni_0.2Mn_0.8O₂ to form a novel heterostructure P3-Na_0.45Ni_0.2Mn_0.8O₂/Na₂SeO₄. The synergy between P3-Na_0.45Ni_0.2Mn_0.8O₂ and Na₂SeO₄ functions in promoting Na⁺ diffusion and suppressing P3-O3 phase transitions upon deep sodiation, which results in recorded high-rate capability (68.2% capacity retention with retained 83.9 mAh g⁻¹ capacity at 6400 mA g⁻¹) and superior cycling stability (capacity retention 75% after 1000 cycles) among all reported P3-type cathodes. Thus, it is believed that this novel heterostructure design opens a new pathway to promote practical applications for layered oxide cathodes in sodium-ion batteries.

更新日期：2023-09-24

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