One dimensional carbon-based composites as cathodes for lithium-sulfur battery

doi:10.1016/j.jmst.2021.12.048

Abstract

Abstract:

Lithium-sulfur batteries (LSBs), owing to their much higher energy density compared to the traditional lithium-ion battery, are deemed as one of the most promising candidates for the energy storage system. However, several issues including shuttle effect, lithium dendrites, and volumetric expansion seriously impede the commercial applications of LSBs. One-dimensional carbon materials (1DCMs) have been widely used as the matrix material for LSBs due to their high surface area, superior conductivity, good flexibility, excellent mechanical stability, and functional modifiability. In this review, the recent progress in 1D carbon-based composites as cathode including metal compounds/1DCMs, MOFs/1DCMs, MXenes/1DCMs, and polymers/1DCMs were discussed. Different strategies for polysulfide confinement and analysis of the functions of various components in the composites were summarized detailly. In the end, the current challenges of LSBs were systematically summarized, and the future outlooks were proposed, aiming at providing a comprehensive insight into the design of new host materials for next-generation LSBs.

Key words: One-dimensional carbon materials, Composites, Lithium-sulfur batteries, Cathode, Suttle effect

Jin Luo, Keke Guan, Wen Lei, Shaowei Zhang, Quanli Jia, Haijun Zhang. One dimensional carbon-based composites as cathodes for lithium-sulfur battery[J]. J. Mater. Sci. Technol., 2022, 122: 101-120.

Figures/Tables 15

Fig. 1. (a) Schematic representation of LSBs and drawbacks of the sulfur cathode; (b) charge/discharge voltage profile of LSBs and corresponding intermediate sulfur species.

Fig. 2. Schematic illustrations of 1DCM-based nanocomposites.

Table 1. Structural designs, host materials, and synthesis methods for 1DCM-based composites.

Structural design	Host materials	Synthesis method	Refs.
1DCM-coated nanostructure	MnO₂@HCF	Template-assisted method	[35]
	Fe₃O₄-NC	Polymerization-assisted synthesis	[36]
	SnS@CNTs	Solvothermal method	[37]
	CNT/CoS-NSs	Solvothermal method	[38]
1DCM-wrapped nanostructure	Peapod-like MnO/C	Polymerization-assisted synthesis	[39]
	Co@NHCRs	Template-directed thermal treatment method	[40]
	Sn/SnO₂@C	Electrospinning	[41]
	Fe/Fe₃C@N-CNT	CVD	[42]
1DCM-supported nanostructure	CNF@Co₃S₄	Hydrothermal method	[43]
	C@WS₂	Hydrothermal method	[44]
	Mo₂C/CNT	Heat treatment	[45]
	S@PCNFs-Cu	Electrospinning	[46]
	ZIF-8@CNTs	Electrospinning	[47]
	CNF/S/PANI	Polymerization-assisted synthesis	[48]

Fig. 3. (a) Illustration of Co-CNF synthesis and redox reaction of LiPSs. Potentiostatic discharge curves of a Li2S8 at 2.115 V on (b) CNF electrode and (c) Co-CNF electrode [55]. (Reproduced with permission. Copyright 2019, Elsevier.) (d) Schematic illustration for the fabrication of Co@NHCRs (Co-CH: cobalt carbonate hydroxide). (e) Electrostatic potential maps of C, N-C, and Co@N-C, and DFT calculations showing the interaction between Li-S and various carbon substrates [40]. (Reproduced with permission. Copyright 2016, Elsevier.).

Fig. 4. (a) Fabrication of the MnO2@HCF/S composite, and comparation between MnO2@HCF/S composite and HCF/S. (b) TEM images of MnO2@SiO2@C, MnO2@HCF, and MnO2@HCF/S. (Reproduced with permission. Copyright 2015, Wiley-VCH.) (c) Prolonged cycling performance of MnO2@HCF/S at 0.5 C and the corresponding Coulombic efficiency [35]. (d) Schematic illustration of the S@Fe3O4-NC@ACC synthesis. (e) Comparison of LiPS adsorption of ACC, NC@ACC, and Fe3O4-NC@ACC [36]. (Reproduced with permission. Copyright 2018, Wiley-VCH.) (f) Schematic of the LiPS adsorption and diffusion on the surface of various non-conductive metal oxides [86]. (Reproduced with permission. Copyright 2016, Springer Nature.).

Table 2. Performance of metal oxides/1DCM composites.

Host material	Carbon/Carbon source	Synthesis method	Sulfur loading (content)	Electrochemical performance	Refs.
MnO₂@HCF	Tetraethyl orthosilicate	Template-assisted method and thermal treatment	3.5 mg cm^-2 (71%)	1216 mAh g^-1 at 0.2 C	[35]
MnO₂/GO/CNTs	CNTs	One-pot chemical method and thermal treatment	2.8 mg cm^-2 (64%)	1500 mAh g^-1 at 0.05 C	[88]
CNF@S/MnO₂	PAN/PS	Electrospinning and thermal treatment	1.0-1.2 mg cm^-2 (79.5%)	728 mAh g^-1 at 3.0 C	[89]
MnO@PNC	PPy	Thermal treatment	3.0 mg cm^-2 (75%)	802 mAh g^-1 at 5.0 C	[76]
CNTs/MnO	CNTs	Pyrolysis method	1.0 mg cm^-2 (N/A)	716 mAh g^-1 at 5.0 C	[90]
CNF-MnO	PAN	Electrospinning and thermal treatment	1.0-1.4 mg cm^-2 (60%)	683.2 mAh g^-1 at 1.0 C	[91]
Mn₃O₄@CNF	PAN	Electrospinning and thermal treatment	11 mg cm^-2 (50%)	1055 mAh g^-1 at 0.1 C	[92]
TiO₂-ACF	ACF cloth	Electrospinning and thermal treatment	3.0 mg cm^-2 (N/A)	915 mAh g^-1 at 0.2 C	[81]
TiO₂-HCFs	PVP	Electrospinning and thermal treatment	67-80% (Li₂S)	400 mAh g^-1(Li₂S) at 5 C.	[82]
S-HMT@CNT^a	MWCNT s	Hydrothermal treatment	2.7 mg cm^-2 (56%)	848 mAh g^-1at 5.0 C.	[33]
TiO₂-B/CNT	CNTs	Hydrothermal treatment	3.2 mg cm^-2 (N/A)	580 mAh g^-1 after 300 cycles at 1.0 C	[93]
Fe₃O₄-NC@ACC	Carbon fiber cloth and PPy	Thermal treatment	4.7 mg cm^-2 (N/A)	1316 mAh g^-1 at 0.1 C	[36]
Fe₃O₄@CNTs	PVP	Thermal treatment	5.5 mg cm^-2 (75%)	538.5 mAh g^-1 after 1800 cycles at 1.0 C	[84]
NiFe₂O₄-CNTs	Carboxylated CNTs	Thermal treatment	5.0 mg cm^-2 (80%)	∼550 mAh g^-1 at 5.0 C	[94]
CNTs/CoO	PMMA and CNTs	Spray drying	2.2 mg cm^-2 (73%)	1340 mAh g^-1 at 0.2 C	[95]
CoO/Co@PCF	Carbon cloth	Thermal treatment	∼3.0 mg cm^-2 (61.2%)	1214.2 mAh g^-1 at 0.1 C	[96]
Co₃O₄/NCNT/LCNT^b	CNTs	Sol-gel method and heat treatment	12 mg cm^-2 (N/A)	1104 mAh g^-1 at 0.5 C	[97]
TiO₂/Co₃O₄-CNTs	C₂H₂	CVD	N/A	1270 mAh g^-1 at 0.2 C	[98]
SnO₂@rGO/CNTs	CNTs	CVD	N/A (65.5%)	1205.4 mAh g^-1 at 0.1 C	[99]
CeO₂/CNTP^c	CNTP	Spray drying	4.6 mg cm^-2 (60%)	1217 mAh g^-1 at 0.5 C	[100]
CeO₂@CNF	PAN	Electrospinning and thermal treatment	8.6 mg cm^-2 (70.2%)	789 mAh g^-1 after 300 cycles at 0.1 C	[101]
CeO₂@CNT	MWNTs	Solvothermal reaction	1.3-1.6 mg cm^-2 (59.8%)	1359 mAh g^-1 at 0.1 C	[102]

Table 2. Performance of metal oxides/1DCM composites.

Host material	Carbon/Carbon source	Synthesis method	Sulfur loading (content)	Electrochemical performance	Refs.
MnO₂@HCF	Tetraethyl orthosilicate	Template-assisted method and thermal treatment	3.5 mg cm^-2 (71%)	1216 mAh g^-1 at 0.2 C	[35]
MnO₂/GO/CNTs	CNTs	One-pot chemical method and thermal treatment	2.8 mg cm^-2 (64%)	1500 mAh g^-1 at 0.05 C	[88]
CNF@S/MnO₂	PAN/PS	Electrospinning and thermal treatment	1.0-1.2 mg cm^-2 (79.5%)	728 mAh g^-1 at 3.0 C	[89]
MnO@PNC	PPy	Thermal treatment	3.0 mg cm^-2 (75%)	802 mAh g^-1 at 5.0 C	[76]
CNTs/MnO	CNTs	Pyrolysis method	1.0 mg cm^-2 (N/A)	716 mAh g^-1 at 5.0 C	[90]
CNF-MnO	PAN	Electrospinning and thermal treatment	1.0-1.4 mg cm^-2 (60%)	683.2 mAh g^-1 at 1.0 C	[91]
Mn₃O₄@CNF	PAN	Electrospinning and thermal treatment	11 mg cm^-2 (50%)	1055 mAh g^-1 at 0.1 C	[92]
TiO₂-ACF	ACF cloth	Electrospinning and thermal treatment	3.0 mg cm^-2 (N/A)	915 mAh g^-1 at 0.2 C	[81]
TiO₂-HCFs	PVP	Electrospinning and thermal treatment	67-80% (Li₂S)	400 mAh g^-1(Li₂S) at 5 C.	[82]
S-HMT@CNT^a	MWCNT s	Hydrothermal treatment	2.7 mg cm^-2 (56%)	848 mAh g^-1at 5.0 C.	[33]
TiO₂-B/CNT	CNTs	Hydrothermal treatment	3.2 mg cm^-2 (N/A)	580 mAh g^-1 after 300 cycles at 1.0 C	[93]
Fe₃O₄-NC@ACC	Carbon fiber cloth and PPy	Thermal treatment	4.7 mg cm^-2 (N/A)	1316 mAh g^-1 at 0.1 C	[36]
Fe₃O₄@CNTs	PVP	Thermal treatment	5.5 mg cm^-2 (75%)	538.5 mAh g^-1 after 1800 cycles at 1.0 C	[84]
NiFe₂O₄-CNTs	Carboxylated CNTs	Thermal treatment	5.0 mg cm^-2 (80%)	∼550 mAh g^-1 at 5.0 C	[94]
CNTs/CoO	PMMA and CNTs	Spray drying	2.2 mg cm^-2 (73%)	1340 mAh g^-1 at 0.2 C	[95]
CoO/Co@PCF	Carbon cloth	Thermal treatment	∼3.0 mg cm^-2 (61.2%)	1214.2 mAh g^-1 at 0.1 C	[96]
Co₃O₄/NCNT/LCNT^b	CNTs	Sol-gel method and heat treatment	12 mg cm^-2 (N/A)	1104 mAh g^-1 at 0.5 C	[97]
TiO₂/Co₃O₄-CNTs	C₂H₂	CVD	N/A	1270 mAh g^-1 at 0.2 C	[98]
SnO₂@rGO/CNTs	CNTs	CVD	N/A (65.5%)	1205.4 mAh g^-1 at 0.1 C	[99]
CeO₂/CNTP^c	CNTP	Spray drying	4.6 mg cm^-2 (60%)	1217 mAh g^-1 at 0.5 C	[100]
CeO₂@CNF	PAN	Electrospinning and thermal treatment	8.6 mg cm^-2 (70.2%)	789 mAh g^-1 after 300 cycles at 0.1 C	[101]
CeO₂@CNT	MWNTs	Solvothermal reaction	1.3-1.6 mg cm^-2 (59.8%)	1359 mAh g^-1 at 0.1 C	[102]

Fig. 5. (a) Schematic illustration and (b) SEM and TEM images of the structural advantages of the double-shelled hollow Co9S8@CNTs nanospheres. (c) Optimized adsorption configurations with key bond lengths (bond orders) of Li2S6 on Co9S8, and the corresponding front-view and side-view electron density difference images of Li2S6 on Co9S8 surfaces [107]. (Reproduced with permission. Copyright 2019, Royal Society of Chemistry.) (d) Schematic illustration of the process of synthesizing S/CNF@Co3S4 and the interaction between Li2S6 and Co3S4 nanosheets. (e) Image of the Li2S6 adsorption test and UV-vis spectra for Blank Li2S6, CNF, and CNF@Co3S4 [43]. (f) Schematic illustration for the preparation of WS2 vertically aligned on the CNFs. (g) Long-term cycling stability test over 1500 cycles at 2 C [44]. (Reproduced with permission. Copyright 2016, Wiley-VCH.).

Fig. 6. (a) Li2S6 adsorption by carbon and metal sulfides. (b) Corresponding simulation of Li2S6 adsorbed on the surface of metal sulfides [128]. (Reproduced with permission. Copyright 2017, HighWire.) (c) Schematic diagrams of LiPSs anchored on the polar host surface through S-binding in metal sulfide cathodes [103]. (Reproduced with permission. Copyright 2017, American Chemical Society.).

Table 3. Different metal sulfides integrated with 1DCMs.

Host material	Carbon/Carbon source	Synthesis method	Sulfur loading (content)	Electrochemical performance	Refs.
MWCNT/Co₉S₈	MWCNTs	Hydrothermal	1.0 mg cm^-2 (60%)	1124 mAh g^-1 at 0.1 C	[106]
Co₉S₈/MWCNTs	MWCNTs	Solvothermal	1.5 mg cm^-2 (76.08%)	1154 mAh g^-1 at 0.1 C	[129]
Co₉S₈@CNTs	C₂H₂	CVD	5.5 mg cm^-2 (68.67%)	676.7 mAh g^-1 at 10 C	[107]
CNF@Co₃S₄	PAN	Electrospinning and thermal treatment	6.8 mg cm^-2 (N/A)	4.1 mA h cm^-2 at 0.1 C	[43]
CNTs/Co₃S₄-NBs^a	MWCNTs	Self-templated	3.5 mg cm^-2 (∼70%)	954 mAh g^-1 at 1 C	[130]
CoS/C/CNT	CNTs	Spray drying	3.0 mg cm^-2 (59.2%)	1031 mAh g^-1 at 500 mA g^-1	[109]
CNTs/CoS-NSs	CNT and PAN	Electrospinning and thermal treatment	1.0-1.5 mg cm^-2 (76.5%)	1425 mAh g^-1 at 0.2 C	[38]
FSC/MoS₂/CNTs^b	Fish scales and CNTs	Thermal treatment and hydrothermal	1.8-2.0 mg cm^-2 (70.47%)	671.6 mAh g^-1 at 2.0 C	[113]
MoS₂/CNTs	CNTs	Hydrothermal	2.6 mg cm^-2 (88%)	1473 mAh g^-1 at 0.2 C	[114]
NSCNTs/MoS₂^c	CNTs	Hydrothermal	2.2 mg cm^-2 (88.3%)	814 mAh g^-1 at 1 C	[115]
TiS₂@NSC	Cotton	Thermal treatment	7.7 mg cm^-2 (N/A)	5.9 mAh cm^-2 after 100 cycles at 0.1 C	[119]
SnS₂@CNT	CNTs	Hydrothermal	4.8 mg cm^-2 (78%)	1375 mAh g^-1 at 0.1 C	[122]
C@WS₂	CNFs	Hydrothermal	1.2 mg cm^-2 (N/A)	∼1051 mAh g^-1 at 0.1 C	[44]
NiCo₂S₄@CNTs	Carboxylated CNTs	Hydrothermal	0.8 mg cm^-2 (66%)	758 mAh g^-1 at 2.0 C	[126]

Fig. 7. (a) Schematic illustration of the fabrication procedure of multi-yolk/shell structured composite. (b) Schematic illustration of the Li2S nucleation and growth on the composite surface (left) and on the carbon surface (right). (Reproduced with permission. Copyright 2020, Elsevier.) (c) Long-term cycling performance of cathode at a rate of 1 C. (d) Schematic illustration of the synthesis process of Fe/Fe3C@N-CNT/S. (e) Ultralight Fe/Fe3C@N-CNT [42]. (Reproduced with permission. Copyright 2019, Royal Society of Chemistry.) (f) Schematic illustration of the synthesis process of S-Mo2C/CNT. (g) Cycling performance of S-Mo2C/CNT at 1 C over 100 cycles with a sulfur loading of 2.5 mg cm-2 and (h) charge/discharge profiles of S-Mo2C/CNT at different current rates [45]. (Reproduced with permission. Copyright 2018, IOP Publishing.).

Fig. 8. (a) LiPS absorptivity evaluated by UV/vis absorption spectroscopy. (b) Discharge/charge capacity cycled at various current densities from 0.2 to 4 C [152]. (Reproduced with permission. Copyright 2018, Royal Society of Chemistry.) (c) Schematic illustration of the functions of the CNT-MoP component. (d) Rate capability and (e) long-term cycling stability of CNT-MoP/GO-S in comparison with that of CNT/GO-S [158]. (Reproduced with permission. Copyright 2017, Springer Nature.) (f) Schematic of the preparation of the dual-functional graphene/PP/Al2O3 separator. (g) Rate performances at various current densities [164]. (Reproduced with permission. Copyright 2017, Wiley-VCH.).

Fig. 9. (a) Photos of a ZIF-8@CNT hybrid that is flexible and compressible. SEM images of (b) S-ZIF-8@CNTs and (c) L-ZIF-8@CNTs [47]. (Reproduced with permission. Copyright 2018, Wiley-VCH.) (d) Schematic illustration for the synthesis of nanohybrids fabric. (e) SEM and TEM images of the cathode [174]. (Reproduced with permission. Copyright 2018, Royal Society of Chemistry.) (f) Fabrication of the hierarchical S@CNTs/Co3S4@NC electrode. (g) TEM images of CNTs/Co3S4@NC showing highly dispersed Co3S4 nanoparticles within the nanocubes [175]. (Reproduced with permission. Copyright 2019, American Chemical Society.).

Fig. 10. (a) Schematic illustration of the preparation process of N-MXene@CNT microspheres. SEM images of (b) multilayered Ti3C2 MXene and (c) N-Ti3C2@CNT microspheres [189]. (Reproduced with permission. Copyright 2019, Springer Nature.) (d) Schematic display of the growth routine of Mo2C-CNT composites and the formation process of Mo2C. (e) XPS survey scan of Mo2C-CNT/S. (f) Schematic illustration of the interaction between hydroxyl-decorated Mo2C and LiPSs. (g) Cycling performances of the Mo2C-CNT/S and Mo2C/S at 0.1 C [190]. (Reproduced with permission. Copyright 2018, Wiley-VCH.).

Fig. 11. (a) Schematic diagram of the action of the S-CNT-PPy composite towards improving cathode performance [200]. (Copyright 2013, Wiley-VCH.) (b) Schematic illustration and (c) SEM and TEM images of CNF/S/PANI [48]. (Reproduced with permission. Copyright 2018, Wiley-VCH.) (d) Schematic illustration for the synthesis of P@E-CNTs/S [203]. (Reproduced with permission. Copyright 2018, Wiley-VCH.) (e) Schematic illustration and (f) photographs of the flexible SPAN-CNT. (g) Electrochemical performance of SPAN-CNT composites [212]. (Reproduced with permission. Copyright 2019, Elsevier.) (h) Schematic illustration for the nucleation-growth/decomposition of Li2S nanoflakes of the SPAN/CNT nanofibers. (i) Cyclic performance of SPAN/CNT for longer-term operation at 800 mA g-1 [213]. (Reproduced with permission. Copyright 2019, Wiley-VCH.).

Table 4. Electrochemical performance of various polymer/1DCM composite.

Cathode	Precursor	Initial capacity (mAh g^-1)	Current density	Capacity retention	Refs.
PPy-MWCNT	PPy	852	0.1 C	∼56%/100 cycles/0.1 C	[218]
CNF-S-PANI	PANI	1278	0.2 C	76%/300 cycles/0.2 C	[48]
P@E-CNTs/S	PANI	1215	0.2 C	80%/200 cycles/0.2 C	[203]
SPAN/CNT	PAN	1610	0.2 C	NG/500 cycles/1.0 C	[212]
SPAN/CNT	PAN	1180	800 mA g^-1	No fading	[213]
CoS₂-SPAN-PAN	PAN	1322	0.2 C	NG/400 cycles/1.0 C	[217]

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