Horseshoe-shaped Hollow Porous Carbon: Synthesis by Hydrothermal Carbonization with Dual-template and Electrochemical Property

doi:10.15541/jim20220711

Abstract

Abstract:

The microreactor was constructed by using the block copolymer (P123)/sodium dodecyl sulfate (SDS) hybrid emulsion. Horseshoe-shaped hollow porous carbon was prepared by hydrothermal carbonization of xylose. The results showed that hydrothermal reaction of xylose occurred at interface between microreactor and solution. Hydrophilicity of PEO (hydrophilic block in P123) decreased at hydrothermal temperature of 160 ℃. Hybrid emulsion was swelled and destroyed gradually because PEO ran into the interior of emulsion. Furthermore, the morphology of microreactor could be regulated by the mass ratio of P123/SDS and the opening angle, and cavity diameter could be controlled by the hydrothermal time. Owing to the open cavity, the capacity of charges and ions was magnified and transport distance was reduced. In addition, specific capacitance and energy density of porous carbons were improved and showed positive correlation with cavity diameter. The horseshoe-shaped hollow porous carbon with largest opening angle (63°), cavity diameter (80 nm) and optimal supercapacitor performance was obtained at a P123/SDS mass ratio of 1.25 : 1 by hydrothermal method for 12 h. In a three-electrode system, the product showed a high specific capacitance of 292 F·g^-1 at a current density of 1 A·g^-1. In a two-electrode system, the product showed an excellent energy density (6.44 Wh·kg^-1), specific capacitance of 185 F·g^-1 at a current density of 0.2 A·g^-1 and outstanding cycling stability (94.83%) after 5000 cycles at a current density of 5 A·g^-1.

Key words: horseshoe-shape, hollow porous carbon, xylose, hydrothermal carbonization, template, interface

CLC Number:

TQ174

XU Zhou, LIU Yuxuan, CHI Junlin, ZHANG Tingting, WANG Shuyue, LI Wei, MA Chunhui, LUO Sha, LIU Shouxin. Horseshoe-shaped Hollow Porous Carbon: Synthesis by Hydrothermal Carbonization with Dual-template and Electrochemical Property[J]. Journal of Inorganic Materials, 2023, 38(8): 954-962.

Figures/Tables 18

Fig. 1 (a-f) SEM and (g-l) TEM images of carbon precursors with different P123/SDS mass ratios (a, g) HNS-S-12; (b, h) HNS-0.625-12; (c, i) HNS-1.25-12; (d, j) HNS-2.5-12; (e, k) HNS-5-12; (f, l) HNS-P-12

Fig. 2 (a-e) SEM and (f-j) TEM images of carbon precursors after hydrothermal treatment for different periods (a, f) HNS-1.25-3; (b, g) HNS-1.25-8; (c, h) HNS-1.25-12; (d, i) HNS-1.25-18; (e, j) HNS-1.25-24

Table 1 Average diameters of particles, inner cavities, carbon walls, opening angles, and pH dependence of different samples

Sample	Average diameter of particle/nm	Average diameter of inner cavity/nm	Average diameter of carbon wall/nm	Opening angle/(°)	pH dependence
HN_S-1.25-0	-	-	-	-	7.27
HN_S-1.25-3	-	-	-	-	3.53
HN_S-1.25-8	110	60	25	48	3.35
HN_S-1.25-12	140	80	30	63	3.32
HN_S-1.25-18	230	40	95	39	3.25
HN_S-1.25-24	300	0	150	0	3.18

Fig. 3 Morphology regulation mechanism of the horseshoe- shaped hollow porous carbon precursors

Fig. 4 (a) N2 adsorption-desorption isotherms and (b) pore size distribution curves of different samples

Fig. 5 FT-IR spectra of D-xylose and different carbon precursors

Fig. 6 (a) XPS total survey and (b) wettability of HNCS-1.25-8, HNCS-1.25-12, HNCS-1.25-18, and HNCS-1.25-24

Fig. 7 (a) CV curves at 5-100 mV∙s-1 and (b) GCD curves at 1-20 A∙g-1 of HNCS-1.25-12; (c) Specific capacitances and Coulombic efficiencies (inset) at 1-20 A∙g-1, (d) relationship between specific capacitance with diameter of cavity at 1 A∙g-1 and (e) Nyquist plots with equivalent circuit (inset) of different samples; (f) Cycling stability of HNCS-1.25-12

Fig. S1 (a) SEM and (b-d) TEM images of HNS-1.25-12

Fig. S2 (a, e) TEM images and (b-d) C, (f-h) O element mappings of (a-d) HNS-1.25-12 and (e-h) HNCS-1.25-12

Fig. S3 (a) Size distribution and Zeta potential, and (b) surface tension of micelle/emulsion in H2O

Fig. S4 TG curves of SDS, P123 and different carbon precursors

Fig. S5 (a) XRD patterns, (b) Raman spectra of HNS-1.25-12, HNCS-1.25-8, HNCS-1.25-12, HNCS-1.25-18, and HNCS-1.25-24

Fig. S6 (a) C1s and (b) O1s high resolution XPS spectra of HNCS-1.25-8, HNCS-1.25-12, HNCS-1.25-18 and HNCS-1.25-24

Fig. S7 (a) CV curves at 5 mV∙s-1 and (b) GCD curves at 1 A∙g-1 of different samples

Fig. S8 Electrochemical performance of different materials in two-electrode system (a) CV curves at 10-100 mV∙s-1 and (b) GCD curves at 0.2-5 A∙g-1 of HNCS-1.25-12; (c) Specific capacitances and Coulombic efficiencies (inset) at 0.2-5 A∙g-1;, (d) Ragone plot with inset showing picture of lit-up LED and (e) relationship between energy density and diameter of cavity at power density of 2500 W∙kg-1 for different samples; (g) Cycling stability of HNCS-1.25-12

Table S1 Textural parameters of different samples

Sample	Specific surface area, S_BET/(m²·g^-1)	Micropore specific surface area, S_micro /(m²·g^-1)	Ratio of micropore, S_micro/S_BET	Total pore volume /(cm³·g^-1)	Pore volume of micropore/(cm³·g^-1)	Average pore size/nm
HN_S-1.25-12	9	-	-	0.03	-	11.90
HNC_S-1.25-8	619	590	95.32%	0.23	0.22	1.49
HNC_S-1.25-12	611	581	95.09%	0.23	0.22	1.52
HNC_S-1.25-18	617	550	89.14%	0.32	0.21	1.84
HNC_S-1.25-24	588	518	88.10%	0.32	0.20	1.87

Table S2 Capacitive properties of doped-carbon materials reported in literature

Samples	Capacitance/ (F·g^-1)	Current density/ (A·g^-1)	Electrolyte	Ref.
NMHCS_S	240	0.2	6 mol∙L^-1 KOH	[9]
HFC	238	0.5	6 mol∙L^-1 KOH	[10]
Fe₂O₃@Gr-CNT/NF	114	1	2 mol∙L^-1 KOH	[11]
BHPC	187	0.5	6 mol∙L^-1 KOH	[12]
ACS	218	0.2	6 mol∙L^-1 NaOH	[13]
N-MWCNTs	184	0.5	5 mol∙L^-1 KOH	[14]
SC-ZN	263	0.5	6 mol∙L^-1 KOH	[15]
PN-ECB	265	0.5	6 mol∙L^-1 NaOH	[16]
NHPC	225	0.25	3 mol∙L^-1 NaOH	[17]
BPC_S	217	1	6 mol∙L^-1 KOH	[1]
rGONS	200	0.5	6 mol∙L^-1 KOH	[18]
HNC_S-1.25-12	292	1	6 mol∙L^-1 KOH	This work

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