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Zirconium-doped precursor regulates surface-bulk structure of LiCoO2 for stable performance at 4.5 V
Yuanyun Dou1, Yongchao Liu2, Guoqing Shen3
1School of Materials Science and Engineering, Anhui Provincial Key Laboratory of Advanced Functional Materials and Devices, Hefei University of Technology, Hefei, Anhui 230009, P. R. China. hfxiang@hfut.edu.cn.
This study introduces a novel precursor modification method to stabilize lithium cobalt oxide (LiCoO2) for high-voltage applications. The new Zirconium-modified LiCoO2 (Zr-LCO) material demonstrates improved cycle stability and rate capability, paving the way for advanced battery technologies.
Area of Science:
- Materials Science
- Electrochemistry
- Solid-State Chemistry
Background:
- High-voltage operation of lithium cobalt oxide (LiCoO2) is essential for enhancing energy density in lithium-ion batteries.
- However, high voltages (≥4.5 V) lead to bulk degradation and interfacial side reactions, limiting LiCoO2's performance and lifespan.
- Existing stabilization strategies often involve complex post-synthesis treatments and fail to achieve simultaneous bulk and surface improvements.
Purpose of the Study:
- To develop a novel, integrated strategy for stabilizing LiCoO2 at high voltages.
- To achieve simultaneous bulk doping and surface modification within a single LiCoO2 material.
- To enhance the cycle stability and rate capability of LiCoO2 cathodes for improved battery performance.
Main Methods:
- A precursor-doped modification strategy was employed, introducing Zirconium (Zr) during the cobalt carbonate (CoCO3) precursor preparation via coprecipitation.
- Sequential synthesis of Zr-modified Co3O4 and LiCoO2 was performed.
- Gradient sintering was utilized to facilitate Zr incorporation into the LiCoO2 lattice and surface segregation, forming Zr-modified LiCoO2 (Zr-LCO).
Main Results:
- The Zr-LCO material exhibited a unique integrated structure with both bulk doping and surface modification.
- Zr-LCO demonstrated significantly enhanced cycle stability, retaining 85% capacity after 100 cycles at 0.5 C.
- Excellent rate capability was observed, with 89% capacity retention at 5 C compared to 0.1 C.
- A 3 Ah pouch battery utilizing Zr-LCO maintained 92.7% capacity after 520 cycles.
Conclusions:
- The precursor modification strategy successfully achieved simultaneous control over the bulk and surface structures of LiCoO2.
- Zr-LCO offers a promising solution for developing high-voltage, long-life LiCoO2 cathodes.
- This approach presents a new, industrially viable pathway for advanced cathode material development.
