Ti4+ doping coupled with zirconium nitrate solution quenching for synergistic modification of lithium-rich layered oxide cathodes
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摘要: 富锂层状氧化物（LLOs）是最具潜力的下一代锂电正极材料，但其体相-表面双重劣化引发的性能衰退问题严重制约商业化应用。研究提出体相Ti4+掺杂耦合硝酸锆溶液淬火的协同改性策略，构建“体相强化-表面防护”双重稳定体系。体相Ti4+取代Mn位点，以强Ti-O键抑制晶格氧释放、过渡金属（TM）迁移与不可逆相变；溶液淬火通过快速离子交换与原位结构重构，在颗粒表面构建具有“Zr4+掺杂和无序岩盐结构壳层”的Zr基多功能改性层，兼具界面阻隔、稳定晶格氧与拓宽锂离子通道的作用。结果表明：TZ-LNMO的结构稳定性与电化学性能大幅提升。具体而言，它在0.1C下可逆比容量达271.8 mAh/g，首次库伦效率（ICE）高达85.21%；1C下300次循环后容量保持率高达90.8%，平均放电电压每圈衰减速率仅为0.56 mV。Abstract: Lithium-rich layered oxides (LLOs) are the most promising next-generation cathode materials for lithium-ion batteries. However, the performance degradation triggered by their bulk-surface dual deterioration severely hinders commercial application. Herein, a synergistic modification strategy of bulk Ti4+ doping and zirconium nitrate solution quenching is proposed to construct a dual stabilization system of “bulk strengthening-surface protection.” Ti4+ substitutes Mn sites in the bulk, significantly inhibiting lattice oxygen release, transition metal (TM) ion migration, and irreversible structural phase transition via strong Ti-O bonds; solution quenching enables rapid ion exchange and in-situ structural reconstruction, forming a Zr-based multifunctional layer with Zr4+ doping and a disordered rock-salt shell on the particle surface, which functions as interfacial isolation, lattice oxygen stabilization and Li+ diffusion channel expansion. The results demonstrate that the structural stability and electrochemical performance of TZ-LNMO are remarkably enhanced. Specifically, it delivers a reversible specific capacity of 271.8 mAh/g with an Initial Coulombic efficiency (ICE) of 85.21% at 0.1C. After 300 cycles at 1C, the capacity retention reaches up to 90.8% with a small voltage fading rate of 0.56 mV per cycle.
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图 1 LNMO、T-LNMO和TZ-LNMO样品的SEM图像及TZ-LNMO的SEM-EDS面扫图像
SEM图像: (a)(d) LNMO，(b)(e) T-LNMO， (c)(f) TZ-LNMO；(g) TZ-LNMO的SEM-EDS 面扫图像
Figure 1. SEM images of LNMO, T-LNMO, and TZ-LNMO samples, and the SEM-EDS mapping images of TZ-LNMO
图 2 LNMO、T-LNMO和TZ-LNMO样品的XRD图谱
(a) XRD图谱总谱；(b) 部分衍射峰的放大图
Figure 2. XRD patterns of LNMO, T-LNMO, and TZ-LNMO samples
图 3 T-LNMO和TZ-LNMO样品的HAADF-STEM图像及FFT图像
(a) T-LNMO的TEM图像; (b) 表面和(c) 体相区域的HAADF-STEM图像及FFT图像; (d) TZ-LNMO的TEM图像; (e) 表面和(f) 体相区域的HAADF-STEM图像及FFT图像
Figure 3. HAADF-STEM images with FFT patterns of T-LNMO and TZ-LNMO samples
图 4 各正极材料的首次充放电曲线、dQ/dV曲线和倍率性能
(a)(b) 0.1C下的首次充放电曲线及其dQ/dV曲线; (c) LNMO和TZ-LNMO对的倍率性能; (d) ΔV随倍率变化曲线; (e) LNMO和(f) TZ-LNMO在不同倍率下的充放电曲线
Figure 4. Initial charge/discharge curves, dQ/dV curves and rate performance of various as-prepared cathode materials
图 5 各正极材料的循环性能
在1C下循环的：(a) 容量衰减曲线, (b) 平均放电电压衰减曲线, (c) 能量密度和能量效率变化曲线; LNMO和TZ-LNMO不同循环次数的：(d)( f) 充放电曲线, (e)(g) dQ/dV曲线; (h) LNMO和TZ-LNMO在0.1C下的循环性能
Figure 5. Cycling performance of various cathode materials
图 6 各正极材料在1C下200次循环后的SEM图像和HRTEM图像
SEM图像: (a) LNMO, (b) T-LNMO, (c) TZ-LNMO; HRTEM图像: (d)LNMO, (e) TZ-LNMO
Figure 6. SEM and HRTEM images of various cathode materials after 200 cycles at 1C
图 7 各正极材料在1C下200次循环后的XRD图谱和隔膜上沉积的过渡金属含量
(a) LNMO和(b) TZ-LNMO在循环前后的XRD图谱; (c) (003)(101)和(104)衍射峰的放大图; (d) LNMO、T-LNMO和TZ-LNMO电池隔膜上沉积的过渡金属含量
Figure 7. XRD patterns and transition metal (TM) content deposited on the separator of various cathode materials after 200 cycles at 1C
表 1 所有正极材料的ICP-OES分析结果
Table 1. ICP-OES analysis results of all cathode materials
Sample n(Li)∶n(Ni)∶n(Mn)∶n(Ti)∶n(Zr) LNMO 1.197∶0.201∶0.602∶0.000∶0.000 T-LNMO 1.196∶0.202∶0.574∶0.018∶0.000 Z-LNMO 1.184∶0.207∶0.609∶0.000∶0.007 TZ-LNMO 1.186∶0.203∶0.576∶0.020∶0.006 
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表 2 LNMO、T-LNMO和TZ-LNMO的晶格参数
Table 2. Refined structural data for LNMO, T-LNMO, and TZ-LNMO samples
Sample Space group Lattice parameter a/nm b/nm c/nm V/nm3 LNMO $ \mathrm{R}\overline{3}\mathrm{m} $ 0.28595 0.28595 1.42544 0.100943 T-LNMO $ \mathrm{R}\overline{3}\mathrm{m} $ 0.28596 0.28596 1.42584 0.100971 TZ-LNMO $ \mathrm{R}\overline{3}\mathrm{m} $ 0.28609 0.28609 1.42720 0.101162
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表 3 所有正极材料在1C倍率下的循环性能
Table 3. Cycling performance of all cathode materials at 1C
Sample Capacity/
(mAh·g−1)Capacity
retention/%Voltage
decay rate/
(mV·cycle−1)Energy density
after 300 cycles/
(Wh·kg−1)1st 300th LNMO 193.3 103.6 53.6 1.38 320.6 T-LNMO 205.8 150.8 73.3 1.19 488.4 Z-LNMO 203.9 166.5 81.6 0.87 556.0 TZ-LNMO 200.9 187.0 90.8 0.56 637.9
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