Application and exploration of nanofibrous strategy in electrode design

doi:10.1016/j.jmst.2020.10.015

Abstract

Abstract:

The key to develop high specific energy rechargeable batteries is development of new electrode materials. The existing electrode materials still have many problems: the shuttle effect and poor conductivity of the sulfur cathode, the inevitable volume expansion of the silicon anode and the lithium dendrite of the lithium metal anode that cause short circuits, etc. Nanofibers, as active electrical materials, conductive additives and electrode bodies, can play multiple roles in electrode design. More interestingly, nanofibers can be functionalized to obtain better controllable properties (i.e., electrolyte affinity, pore size distribution and surface electronic structure), thereby further enhancing electrochemical performance. In this article, the latest research progress in electrode design based on nanofibers is reviewed, including processing methods, structure, morphology and electrochemical performance. The key problems affecting the electrochemical performance of the electrode are also discussed, such as the preparation process, atomic structure, electrical conductivity, surface area and pore distribution of nanofibers, to provide reference points for nanofibers in excellent electrode design.

Key words: Nanofibers, Battery, Electrode, Energy storage

Yongliang Li, Hua Yuan, Yanbing Chen, Xiaoyu Wei, Kunyan Sui, Yeqiang Tan. Application and exploration of nanofibrous strategy in electrode design[J]. J. Mater. Sci. Technol., 2021, 74: 189-202.

Figures/Tables 11

Fig. 1. Schematic illustration of the microstructure evolution of electrodes.

Fig. 2. (a) Schematic configuration of electrospinning equipment [30]. (b) TEM images of the porous nanofibers by heating the TEOS/PAN composite nanofibers at 1200 °C in Ar/H2 atmosphere followed removing the Silica (SiO2) nanoparticles by HF solution [33]. (c) TEM and SEM images of hollow nanofibers, which were obtained by pyrolysis in air to remove the heavy mineral oil core in the TiO2-PVP nanofiber sheath [34]. (d) SEM image of the core/shell nanofiber of carbon shell and nanowire core [35]. (e) SEM and (f) TEM images of multichannel nanofiber by carbonizing multicore polymer nanofibers: PAN and poly methyl methacrylate (PMMA) [36].

Fig. 3. (a) Schematic configuration of thermal CVD process. (b) Schematic illustration of a CVD using hydrogen and methane as carbon sources [39]. (c) TEM of lattice image in the external part of the as-grown fiber; and (d) lattice image in the external part of the graphitized fiber [37].

Table 1 Correlation between the metal catalyst particles and crystallinity of CNFs produced at spreading temperature in CVD [39].

Catalysts	Type of CNFs	Diameter of CNFs (nm)
Fe	Amorphous	~25
Co	Highly graphitic	30-200
Ni	Amorphous	25-140
Pt	Partially graphitic	~80
Ru	Highly graphitic	~7
Rh	Amorphous	~40

Fig. 4. (a) Schematic illustration of synthetic the hollow CNFs by confined template method [45]. (b) Preparation process of TiO2@N-C@MoS2. (c)TEM images of the hierarchical tubular nanostructure of TiO2@N-C@MoS2 [46].

Fig. 5. (a) Preparation process of S/HPCF. SiO2 was used as porogens to form the mesopores and the micropores were produced via KOH activation [22]. (b) TEM images of CNTs@CNFs. (c) HRTEM, TEM images and SAED pattern of Ni@CNTs@CNFs [71]. (d) Preparation process of Meso-HACNF [75].

Fig. 6. (a) The synthesis process and structure of P@N-PHCNF and P/N-HCNF. (b) Schematic diagram of the potassiation/depotassiation process. (c) P - C chemical bonds and N-doped with enhanced adsorption energy for red P facilitate K+ diffusion and charge transfer [105]. The HRTEM images and lattice distance of (d) CNFs and (e) S-CNFs [106]. (f) The chemical model of B-N-F triply doped PCNFs. (g, h) The SEM images of the fresh electrode and after 50 cycles [107].

Fig. 7. (a) Elemental mapping images of TiN@CNFs. (b) SEM images of bare CNFs. (c) SEM images of TiN@CNFs (inset: HRTEM images) [114]. (d) Schematic illustration of the Li deposition occurring on bare Li foil and Co@CNFs [77]. (e) The transportation path of electrons and Na+ in TiO2 nanofibers [117]. (f) The synthesis processes for Sb@CNFs. In-situ TEM images of single Sb@CNF during (g) first potassiation and (h) first depotassiation [122].

Fig. 8. (a) Schematic illustration of Ni-CNFs-CNTs manufacturing process [131]. (b) Schematic illustration of porous hollow CNTs@CNFs nanostructure [71].

Fig. 9. (a) Schematic synthesis of the free-standing nanofiber mat [138]. (b) The cross-sectional image of H-SPAN nanofiber. (c) SEM image of H-SPAN nanofiber [73]. (d) Schematics diagram Li deposition on bare Cu foil and polymer nanofibers [141].

Table 2 Nanofiber host materials for different electrodes.

Materials	Electrodes	Electrochemical performance
CNFs [142]	S cathode	760 mA·h g^-1 after 50 cycles at 0.15 mA cm^-2
PCNFs [143]	S cathode	809.1 mA h g^-1 after 300 cycles at 0.5 C
N-doped PCNFs [144]	S cathode	830 mA·h g^-1 after 300 cycles at 0.5 C
Freestanding CNFs [145]	S cathode	1000 mA h g^-1 after 50 cycles at 100 mA g^-1
SPAN-VGCF [146]	S cathode	903 mA h g^-1 after 150 cycles at 1 C
TiO₂/TiO_xN_y-CNFs [147]	S cathode	1107 mA h g^-1 after 100 cycles at 1 C
Oxidized PAN [141]	Li metal anode	1 mAh cm^-2 and CE of 97.4% after 120 cycles at 3 mA cm^-2
N-doped CNFs [65]	Li metal anode	2 mAh cm^-2 and CE of 97% after 120 cycles at 2 mA cm^-2
Ni@CNFs [113]	Li metal anode	1 mAh cm^-2 after 500 cycles at 0.5 mA cm^-2
CoNi@NPCNFs [115]	Li metal anodeS cathode	2 mAh cm^-2 after 250 cycles at 1 mA cm^-2828 mA·h g ^-1 after 1200 cycles at 5 C
CNFs [52]	LIBs anode	450 mA·h g^-1 at 30 mA g^-1
N-doped CNFs [53]	LIBs anode	529 mA·h g^-1 after 50 cycles at 30 mA g^-1
CNTs/RGO nanofiber [148]	LIBs anode	374 mA·h g^-1 after 800 cycles at 500 mA g^-1
Sn@C-HCNFs [149]	LIBs anode	737 mA h g^-1 after 200 cycles at 0.5 C
Si@C-HCNFs [150]	LIBs anode	1601 mA h g^-1 after 50 cycles at 50 mA g^-1
MnO/CNFs [151]	LIBs anode	844 mA·h g^-1 after 800 cycles at 1 A g^-1
CNFs [152]	SIBs anode	176 mA h g^-1 after 600 cycles at 200 mA g^-1
N-doped PCNFs [153]	SIBs anode	217 mA h g^-1 after 10,000 cycles at 2 A g^-1
Graphene/CNFs [154]	SIBs anode	432 mA·h g^-1 after 100 cycles at 100 mA g^-1
Red P@PCNFs [155]	SIBs anode	700 mA h g^-1 after 920 cycles at 2 A g^-1
MoS₂@PCNFs [156]	LIBs anodeSIBs anode	1222 mA·h g^-1 after 1000 cycles at 1 A g^-1477 mA h g ^-1 after 1000 cycles at 1 A g^-1
PCNFs [157]	PIBs anode	210 mA·h g^-1 after 1200 cycles at 200 mA g^-1
N-doped CNFs [158]	PIBs anode	170 mA·h g^-1 after 1900 cycles at 1 C
Sn₄P₃@NCNFs [159]	PIBs anode	403 mA h g^-1 after 200 cycles at 50 mA g^-1

Table 2 Nanofiber host materials for different electrodes.

Materials	Electrodes	Electrochemical performance
CNFs [142]	S cathode	760 mA·h g^-1 after 50 cycles at 0.15 mA cm^-2
PCNFs [143]	S cathode	809.1 mA h g^-1 after 300 cycles at 0.5 C
N-doped PCNFs [144]	S cathode	830 mA·h g^-1 after 300 cycles at 0.5 C
Freestanding CNFs [145]	S cathode	1000 mA h g^-1 after 50 cycles at 100 mA g^-1
SPAN-VGCF [146]	S cathode	903 mA h g^-1 after 150 cycles at 1 C
TiO₂/TiO_xN_y-CNFs [147]	S cathode	1107 mA h g^-1 after 100 cycles at 1 C
Oxidized PAN [141]	Li metal anode	1 mAh cm^-2 and CE of 97.4% after 120 cycles at 3 mA cm^-2
N-doped CNFs [65]	Li metal anode	2 mAh cm^-2 and CE of 97% after 120 cycles at 2 mA cm^-2
Ni@CNFs [113]	Li metal anode	1 mAh cm^-2 after 500 cycles at 0.5 mA cm^-2
CoNi@NPCNFs [115]	Li metal anodeS cathode	2 mAh cm^-2 after 250 cycles at 1 mA cm^-2828 mA·h g ^-1 after 1200 cycles at 5 C
CNFs [52]	LIBs anode	450 mA·h g^-1 at 30 mA g^-1
N-doped CNFs [53]	LIBs anode	529 mA·h g^-1 after 50 cycles at 30 mA g^-1
CNTs/RGO nanofiber [148]	LIBs anode	374 mA·h g^-1 after 800 cycles at 500 mA g^-1
Sn@C-HCNFs [149]	LIBs anode	737 mA h g^-1 after 200 cycles at 0.5 C
Si@C-HCNFs [150]	LIBs anode	1601 mA h g^-1 after 50 cycles at 50 mA g^-1
MnO/CNFs [151]	LIBs anode	844 mA·h g^-1 after 800 cycles at 1 A g^-1
CNFs [152]	SIBs anode	176 mA h g^-1 after 600 cycles at 200 mA g^-1
N-doped PCNFs [153]	SIBs anode	217 mA h g^-1 after 10,000 cycles at 2 A g^-1
Graphene/CNFs [154]	SIBs anode	432 mA·h g^-1 after 100 cycles at 100 mA g^-1
Red P@PCNFs [155]	SIBs anode	700 mA h g^-1 after 920 cycles at 2 A g^-1
MoS₂@PCNFs [156]	LIBs anodeSIBs anode	1222 mA·h g^-1 after 1000 cycles at 1 A g^-1477 mA h g ^-1 after 1000 cycles at 1 A g^-1
PCNFs [157]	PIBs anode	210 mA·h g^-1 after 1200 cycles at 200 mA g^-1
N-doped CNFs [158]	PIBs anode	170 mA·h g^-1 after 1900 cycles at 1 C
Sn₄P₃@NCNFs [159]	PIBs anode	403 mA h g^-1 after 200 cycles at 50 mA g^-1

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