Structure and Electrochemical properties of coconut shell-based hard carbon as anode materials for potassium ion batteries

HUANG Tao^1
,,
PENG Da-chun¹,
CHEN Zui¹,
XIA Xiao-hong^{1, 2},
CHEN Yu-xi^{1, 2},
LIU Hong-bo^{1, 2
, ,}

1.
College of Material Science and Engineering, Hunan University, Changsha 410082, China
2.
Hunan Province Key Laboratory for Advanced Carbon Materials Applied Technology, Hunan University, Changsha 410082, China

Funds: National Natural Science Foundation of China (51772083, 51402101); Science and Technology Planning Project of Hunan Province (2018GK1030)

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Author Bio:
HUANG Tao, Master Student. E-mail: 494579391@qq.com

Corresponding author: LIU Hong-bo, Professor.E-mail: hndxlhb@163.com

摘要

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Abstract: Biomorphic hard carbon recently attracted widely interest as anode materials for potassium ion batteries (PIBs) owing to their high reversible capacity, but high preparation cost and poor cycle stability significantly hinder its practical application. In this study, coconut shell-derived hard carbon (CSHC) was prepared from waste biomass coconut shell using a one-step carbonization method, which was further used as anode materials for potassium ion batteries. The effects of carbonization temperature on the microstructure and electrochemical properties of the CSHC materials were investigated by X-ray diffraction, nitrogen adsorption-desorption isotherms, Raman spectroscopy, scanning electron microscope, transmission electron microscope, and cyclic voltammetry, etc. The results suggested that the coconut shell hard carbon carbonized at 1 000 °C (CSHC-10) possessed suitable graphite microcrystallines size, pore structure and surface defect content, which exhibited the best electrochemical performance. Specifically, CSHC-10 presented a high reversible specific capacity of 254 mAh·g⁻¹ at 30 mA·g⁻¹ with an initial Coulombic efficiency of 75.0%, and the capacity retention was 87.5% after 100 cycles and 75.9% after 400 cycles at 100 mA·g⁻¹. The CSHC with high capacity and good cycling stability demonstrates to be an excellent potassium storage material.
- Potassium ion battery /
- Coconut shell-based hard carbon /
- Carbonization temperature /
- Microstructure /
- Electrochemical performance

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Figure 1. Schematic illustration for the synthesis of coconut shell-derived hard carbon (CSHC).

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Figure 2. SEM images of (a) CSHC-8, (b) CSHC-10, and (c) CSHC-12. HRTEM images of (d) CSHC-8, (e) CSHC-10, and (f) CSHC-12.

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Figure 3. (a) N₂ adsorption-desorption isotherms and (b) BJH pore size distribution of the CSHC materials prepared from different carbonization temperatures.

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Figure 4. (a) XRD patterns, (b) Raman spectra, (d) XPS spectra, and (e) high-resolution C1s spectrum of the CSHC materials prepared from different carbonization temperatures; (c) the deconvoluted Raman spectra, and (f) high-resolution O1s spectrum of CSHC-10.

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Figure 5. (a) The first charge/discharge profiles, and (b) Capacity proportion contributed by different voltage regions during the first discharge process of the CSHC materials prepared from different carbonization temperatures; CV curves of (c) CSHC-8, (d) CSHC-10, (e) CSHC-12.

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Figure 6. (a) Rate capability (b) Capacity retention at various current densities, and (c) Cyclic performance of the CSHC materials prepared from different carbonization temperatures; (d) Long-term cyclic performance of CSHC-10 at 100 mA·g^-1.

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Figure 7. The EIS curves and corresponding equivalent circuit model of the CSHC materials prepared from different carbonization temperatures.

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Table 1. The structural parameters and XPS element analysis of the CSHC materials prepared from different carbonization temperatures

Samples	S_BET m²·g⁻¹	V_pore cm³·g⁻¹	d₀₀₂ nm	L_c nm	L_a nm	I_D/I_G	XPS analysis /%
Samples	S_BET m²·g⁻¹	V_pore cm³·g⁻¹	d₀₀₂ nm	L_c nm	L_a nm	I_D/I_G	C	O	N	C―C	C―OH	C＝O
CSHC-8	217.5	0.149	0.389	1.04	5.89	3.26	88.79	10.24	0.97	59.12	29.83	11.04
CSHC-10	78.5	0.061	0.386	1.15	6.52	2.95	89.52	9.54	0.94	59.63	29.71	10.65
CSHC-12	9.3	0.011	0.377	1.24	7.40	2.60	91.19	7.85	0.95	61.33	27.05	11.62

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Table 2. The fitting values of the resistance components in the equivalent circuit.

Smples	R_S/Ω	R_F/Ω	R_ct/Ω
CSHC-8	1.3	186.4	95.9
CSHC-10	5.2	56.2	535.5
CSHC-12	4.6	11.7	772.9

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