Enhanced rate performance and specific capacity in Ti-substituted P2-type layered oxide enabled by crystal structure and particle morphology modifications

Vasavan, Hari Narayanan; Badole, Manish; Dwivedi, Sushmita; Kumar, Deepu; Kumar, Pradeep; Kumar, Sunil

doi:10.1016/j.cej.2022.137662

Cited by 16 publications

(9 citation statements)

References 49 publications

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“…The figures in two descriptions indicate that in a crystal cell, the numbers of TM layers along the stacking direction are 3 and 2, respectively. Generally, a high Na content ( x > 0.8) enables the formation of a O3-type structure, while the P2-type structure has a low Na content ( x < 0.7) . In general, the P2-type layered oxides are likely to be affected by Na + /vacancy ordering and structure transition during the charge and discharge process, which can be relieved by adjusting the compositions of Na sites and TM sites. , Compared with P2-type layered oxides, O3-type layered oxides have sufficient Na content and high initial capacity, which benefit the application of SIBs with high energy density.…”

Section: Introductionmentioning

confidence: 99%

Slight Multielement Doping-Induced Structural Order–Disorder Transition for High-Performance Layered Na-Ion Oxide Cathodes

Guo

Zhao

Gao

et al. 2023

ACS Appl. Mater. Interfaces

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To realize concurrently the high-energy density and excellent cycling stability, maximum utilization of redox couple, minimization of detrimental phase transition, and structural degradation of O3-type layered oxide cathodes are critical for developing Na-ion batteries. Ni2+/Ni4+ redox couple showing multielectron reaction and higher redox potential is favorable to increase the energy density. However, the Jahn-Teller distortion of Ni3+ generated upon (dis)charging results in a strong anisotropy in the local crystal structure that causes irreversible interlayer bending and chemo-mechanical cracks of the cathode particles, compromising the electrochemical properties eventually. In this work, we show a slight multielement doping strategy that enlarges the amount of active redox components while minimizing the inactive contents. The results show that the uniform distribution of multiple components can help increase the disorder degree of atom arrangement and alleviate the structural changes and detrimental anisotropy cracks. As a proof of concept, a multielement-doped O3-type Na0.9Ni0.25Cu0.05Mg0.05Zn0.05Fe0.05Al0.05Mn0.40Ti0.05Sn0.05O2 oxide is rationally prepared that presents better chemo-mechanical stability and delayed O3-P3 phase transition behavior. Compared to the high Ni-content Na0.9Ni0.35Fe0.2Mn0.45O2 cathode, this as-prepared multielement material delivers a reversible capacity of about 120 mAh/g in the voltage range of 2–4.0 V, superior cycling stability with 90% of capacity retention after 500 cycles, and excellent rate capability (more than 70% of initial capacity at 5.0 C). This work indicates that the multielement doping method is highly suitable for the development of advanced Na-ion layered oxide cathodes.

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Section: Introductionmentioning

confidence: 99%

Slight Multielement Doping-Induced Structural Order–Disorder Transition for High-Performance Layered Na-Ion Oxide Cathodes

Guo

Zhao

Gao

et al. 2023

ACS Appl. Mater. Interfaces

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“…Compared to NNCT, NNCM and NNCMT LOs showed lower cell volumes and unit cell parameters. 55,56 This is expected as Ti 4+ ions (0.605 Å in 6 coordination) have a higher ionic radius compared to Mn 4+ ions (0.530 Å in 6 coordination), which would expand the unit cell, increasing its volume, as reported in the literature. 58−60 The Vesta software package 61 was used to generate the 3D image visualization of the NNCT unit cell using the refined parameters and is displayed in Figure 2.…”

Section: Xrd Figure 1a Displays the Xrd Patterns Of Nnct At Different...mentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

“…Several distortions to the crystal structure and particle morphology of the parent compound caused by introducing inactive substituents enable such property enhancements. For instance, in the case of Ti 4+ , we had reported that the presence of a larger ion (such as Ti ions) in place of Mn 4+ ions in Na 0.7 Ni 0.2 Cu 0.15 Mn 0.65 O 2 (NNCM) , led to the expansion of the unit cell and an increase in the area of the Na-ion conduction bottlenecks. Consequently, the Na 0.7 Ni 0.2 Cu 0.15 Mn 0.575 Ti 0.075 O 2 (NNCMT) cathode also showed improvements in its particle morphology (such as the increased size of the lateral surface through a majority of the ionic conduction occurs) and electrical properties which led to a remarkable improvement of 27% in the observed specific capacity of the parent compound at 0.1C-rate which subsequently increased to about 50% at 1C.…”

Section: Introductionmentioning

confidence: 99%

“…5 7 5 Ti 0 . 0 7 5 O 2 (NNCMT) 56 cathode also showed improvements in its particle morphology (such as the increased size of the lateral surface through a majority of the ionic conduction occurs) and electrical properties which led to a remarkable improvement of 27% in the observed specific capacity of the parent compound at 0.1C-rate which subsequently increased to about 50% at 1C.…”

Section: Introductionmentioning

confidence: 99%

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Excellent Structural Stability-Driven Cyclability in P2-Type Ti-Based Cathode for Na-Ion Batteries

Vasavan

Badole

Saxena

et al. 2023

ACS Appl. Energy Mater.

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In the current study, we have synthesized Ti-based P2-type Na0.7Ni0.2Cu0.1Ti0.65O2 (NNCT) through the sol–gel route and characterized it for its structural, electrical, and electrochemical properties. The analysis of X-ray diffraction (XRD) data confirmed the existence of a single P2 phase for the sample calcined at 950 °C with suppressed Na-ion vacancy ordering. Impedance studies and chronoamperometric data revealed that NNCT exhibited a poor conductivity of ∼1.37 × 10–7 S cm–1 at room temperature, with the electronic conductivity contribution to the total electrical conduction being only 0.4%. The sample exhibited specific capacities of 83, 54, and 42 mA h g–1 at discharge rates of 0.1C, 0.5C, and 1C, respectively, with remarkable cyclic stability of 96% capacity retention after 700 cycles at 0.5C which makes NNCT an attractive cathode for Na-ion batteries in stationary storage applications. The ex situ XRD analysis confirmed that NNCT maintains a single P2 phase during cycling between 2.0 and 4.2 V. NNCT also exhibited moisture stability, thus enabling the use of a cost-effective water-based slurry for cathode layer fabrication.

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Deciphering the role of optimal P2/O3 phase fraction in enhanced cyclability and specific capacity of layered oxide cathodes

Saxena,

Badole,

Vasavan

et al. 2024

Chemical Engineering Journal

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Enhanced rate performance and specific capacity in Ti-substituted P2-type layered oxide enabled by crystal structure and particle morphology modifications

Cited by 16 publications

References 49 publications

Slight Multielement Doping-Induced Structural Order–Disorder Transition for High-Performance Layered Na-Ion Oxide Cathodes

Slight Multielement Doping-Induced Structural Order–Disorder Transition for High-Performance Layered Na-Ion Oxide Cathodes

Excellent Structural Stability-Driven Cyclability in P2-Type Ti-Based Cathode for Na-Ion Batteries

Deciphering the role of optimal P2/O3 phase fraction in enhanced cyclability and specific capacity of layered oxide cathodes

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