Influence of synthesis method on morphology and functional properties of li-rich layered oxides

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Abstract

The influence of the precursor synthesis method on the functional properties of cathode material based on lithium-rich oxides was studied. Precursors were obtained by co-precipitation method (hydroxide and carbonate precursors) and solvothermal method (hydroxide and oxalate precursors). Within the selected synthesis methods, the parameters were changed by varying the precipitant and pH of precipitation during the synthesis by co-precipitation method and the reaction medium/precipitant combinations during the solvothermal synthesis method. The solid-phase reaction of the investigated precursors with lithium source and subsequent high-temperature annealing resulted in lithium-rich layered oxides of the composition Li1.2Ni0.133Mn0.534Co0.133O2. The sample synthesized by solvothermal method exhibits high discharge capacity values of 233.2 mAh/g (0.1 C) and 175.3 mAh/g (0.5 C) with residual discharge capacity of 94 and 80.5%, respectively. The samples with comparable electrochemical performance are similar in morphology. These materials are agglomerated and characterized by a bimodal distribution with maxima in the 14–19 μm and 55–60 μm regions. An approach that takes into account the relationship between morphology and electrochemical properties will allow the preparation of higher performance electrode materials for lithium-ion battery.

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About the authors

A. A. Medvedeva

Kurnakov Institute of General and Inorganic Chemistry Russian Academy of Sciences

Author for correspondence.
Email: anna.ev.medvedeva@gmail.com
Russian Federation, Moscow, 119991

E. V. Makhonina

Kurnakov Institute of General and Inorganic Chemistry Russian Academy of Sciences

Email: anna.ev.medvedeva@gmail.com
Russian Federation, Moscow, 119991

M. M. Klimenko

Kurnakov Institute of General and Inorganic Chemistry Russian Academy of Sciences

Email: anna.ev.medvedeva@gmail.com
Russian Federation, Moscow, 119991

Y. A. Politov

Kurnakov Institute of General and Inorganic Chemistry Russian Academy of Sciences

Email: anna.ev.medvedeva@gmail.com
Russian Federation, Moscow, 119991

A. M. Rumyantsev

Ioffe Institute Russian Academy of Sciences

Email: anna.ev.medvedeva@gmail.com
Russian Federation, St Petersburg, 194021

Y. M. Koshtyal

Ioffe Institute Russian Academy of Sciences

Email: anna.ev.medvedeva@gmail.com
Russian Federation, St Petersburg, 194021

A. S. Goloveshkin

Nesmeyanov Institute of Organoelement Compounds of Russian Academy of Sciences

Email: anna.ev.medvedeva@gmail.com
Russian Federation, Moscow, 119334

A. A. Kurlykin

Kurnakov Institute of General and Inorganic Chemistry Russian Academy of Sciences

Email: anna.ev.medvedeva@gmail.com
Russian Federation, Moscow, 119991

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Supplementary files

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3. Fig. 1. Microphotographs of the precursors: carbonate-based PR-CC (a), oxalate-based PR-S3 (b), and hydroxide-based PR-SH (c), PR-S1 (d), and PR-S2 (e).

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4. Fig. 2. Microphotographs of the lithiated oxides LR-CC (a), LR-S3 (b), LR-SH (c), LR-S1 (d) and LR-S2 (e).

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5. Fig. 3. Differential agglomerate size distribution curves for samples based on hydroxide precursors LR-CC, LR-S1, LR-S2 (a), carbonate precursor LR-CC (b) and oxalate precursor LR-S3 (c).

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6. Fig. 4. Diffractograms of lithiated samples (a), enlarged area 20-25 2θ (b).

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7. Fig. 5. Dependence of discharge capacity on cycle number for synthesized samples at 0.1C (a) and 0.4C (b).

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8. Fig. 6. Charge-discharge curves of synthesized samples at 0.4C.

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9. Fig. 7. Dependences of stress on cycle number (a) and specific energy value (b) for the synthesized samples.

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10. Fig. 8. Curves of the first derivative of capacitance on voltage from voltage (dQ/dV) for 2 cycles (a) and 67 cycles (b).

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