Effect of precursor drying temperature on the morphology and electrochemical performance of lithium-rich manganese-based cathode materials
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摘要: 以過渡金屬硫酸鹽、氫氧化鈉、氨水為原料，通過連續共沉淀–高溫固相法制備了富鋰錳基正極材料Li1.17Ni0.33Mn0.5O2。對其進行了包括微觀形貌、宏觀形貌、晶體結構、電化學性能等方面的表征，研究了前驅體烘干溫度對于粒度較小前驅體的宏觀形貌及鋰化后正極材料的微觀形貌和電化學性能的影響。結果表明，烘干溫度較高的前驅體在烘干后出現了明顯了宏觀燒結現象，鋰化并涂布后出現了明顯的顆粒；烘干溫度較低的前驅體在烘干后并未出現宏觀燒結現象，鋰化并涂布后未出現明顯的顆粒。在電化學性能方面，前驅體烘干溫度較高的正極材料在經歷50個循環后，可逆比容量只剩下85%，下降比較明顯；前驅體烘干溫度較低的正極材料在經歷了50個循環后，可逆比容量未出現明顯下降。Abstract: With the gradually increasing consumption of coal, oil, and natural gas and the increasing environmental pollution, recyclable secondary energy has become crucial to solving energy and environmental problems. Lithium-ion batteries have penetrated into all aspects of life. Its high energy density, high voltage platform, long life, and environment-friendly characteristics make it widely in-demand. Lithium-ion batteries are used in devices such as mobile phones, tablet computers, and electric vehicles, in which requirements of energy density, rate, and cycle performance are high. The high-capacity lithium-rich material can provide a reversible specific capacity higher than 250 mA·h·g–1 and an energy density of up to 600 W·h·kg–1, making it a positive electrode material. Being a scarce and strategic resource, the price of cobalt has considerably increased. The price fluctuation of cobalt directly affects the cost of the full battery. Drying conditions have a minor effect on most cathode materials and precursors and do not affect the size, morphology, and elemental distribution of their precursors. Thus, virtually no one has explored the effects of such drying conditions. Herein, we studied the drying conditions of cobalt-free lithium-rich cathode materials and explored the influence of drying condition on the morphology and electrochemical performance of cathode materials. Using sodium hydroxide, which is a transition metal sulfate, and ammonia as raw materials, a lithium-rich manganese-based cathode material (Li1.17Ni0.33Mn0.5O2) was prepared via coprecipitation followed by sintering at 900 ℃. The influence of the precursor drying temperature on the macro and micro morphology and electrochemical performance was studied. The results show that the precursor displays a clear macro sintering phenomenon, and particles appear after lithiation at a higher drying temperature. The precursor with the lower drying temperature did not display a macro sintering phenomenon, and no obvious particles appeared after lithiation. After 50 cycles, the remaining capacity of the high drying temperature was only 85%, which is a significant drop. The cathode material with the lower drying temperature did not decrease significantly in capacity after 50 cycles.
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Key words:
- cathode material /
- precursor /
- granularity /
- drying /
- electrochemical performance
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圖 1 LLO1和LLO2前驅體及正極材料涂布后宏觀形貌。（a）LLO1前驅體；（b）LLO2前軀體；（c）LLO1正極材料；（d）LLO2正極材料
Figure 1. Macro morphology of precursor and cathode materials: (a) precursor of LLO1; (b) precursor of LLO2; (c) cathode material of LLO1; (d) cathode material of LLO2
圖 2 存在大顆粒的樣品輥壓后宏觀形貌
Figure 2. Macroscopic morphology of samples with large particles after rolling
圖 3 LLO1（a）和LLO2（b）樣品的微觀形貌
Figure 3. Electron microprobe images of LLO1 sample (a) and LLO2 sample (b)
圖 4 LLO1（a）和LLO2（b）樣品XRD圖及精修后圖譜
Figure 4. XRD pattern and Rietveld refinement results of LLO1 sample (a) and LLO2 sample (b)
圖 5 LLO1和LLO2的倍率（a）及循環性能（b）
Figure 5. Rate capacity (a) and cycling capacity (b) of LLO1 and LLO2
表 1 不同樣品的Rietveld精修結果表
Table 1. Summary of Rietveld refinement results
Sample a/nm c/nm I(003)/I(104) NiLi Bragg R Rp Rwp χ2 LLO1 0.28669 1.42566 2.01 2.87% 0.77 1.96 2.79 1.748 LLO2 0.28642 1.42382 2.40 3.04% 1.02 2.15 2.98 1.795 
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