Carbon Nanofiber Network Research Articles

Carbonization-Temperature-Dependent Electrical Properties of Carbon Nanofibers-From Nanoscale to Macroscale.

An exact understanding of the conductivity of individual fibers and their networks is crucial to tailor the overall macroscopic properties of polyacrylonitrile (PAN)-based carbon nanofibers (CNFs). Therefore, microelectrical properties of CNF networks and nanoelectrical properties of individual CNFs, carbonized at temperatures from 600 to 1000 °C, are studied by means of conductive atomic force microscopy (C-AFM). At the microscale, the CNF networks show good electrical interconnections enabling a homogeneously distributed current flow. The network's homogeneity is underlined by the strong correlation of macroscopic conductivities, determined by the four-point-method, and microscopic results. Both, microscopic and macroscopic electrical properties, solely depend on the carbonization temperature and the exact resulting fiber structure. Strikingly, nanoscale high-resolution current maps of individual CNFs reveal a large highly resistive surface fraction, representing a clear limitation. Highly resistive surface domains are either attributed to disordered highly resistive carbon structures at the surface or the absence of electron percolation paths in the bulk volume. With increased carbonization temperature, the conductive surface domains grow in size resulting in a higher conductivity. This work contributes to existing microstructural models of CNFs by extending them by electrical properties, especially electron percolation paths.

Ordered porous metal oxide embedded dense carbon network design as high-performance interlayer for stable lithium-sulfur batteries

The design of multifunctional interlayer is important for the suppression of lithium polysulfides (LiPSs) shuttle effect in lithium-sulfur (Li-S) batteries. Herein, a multifunctional interlayer fabrication strategy is developed by depositing ordered porous metal oxide embedded with nitrogen-doped carbon nanotubes (NCNT) on the carbon nanofibers (CNFs) skeleton. In this design strategy, three-dimensional ordered macroporous N, Co-doped titanium oxides (N,Co-TiOx) is uniformly deposited on CNFs network, then in-situ growth of NCNT is implemented within the ordered porous oxides framework and CNFs, forming dense-structured adsorption/catalytic multifunctional interlayer (N,Co-TiOx/NCNT@CNFs). The ordered porous N,Co-TiOx together with the implemented NCNT not only provides an effective physical barrier for polysulfides diffusion, but also offers strong chemical interaction with LiPSs adsorption and promoted catalytic conversion kinetics. With these merits, the Li-S battery with N,Co-TiOx/NCNT@CNFs interlayer delivers an impressive rate capability of 638 mAh g-1 at a current density of 5 C. The cell also shows excellent cycling performance with a capacity decay of 0.033 % per cycle after 500 cycles at 1 C. More importantly, the Li-S pouch cells with N,Co-TiOx/NCNT@CNFs interlayer achieve a capacity of 806 mA h g−1 at sulfur loading of 4.0 mg cm−2 after 50 cycles at 0.1 C. This ordered porous metal oxide embedded dense carbon network design provides alternative strategy for the development of high-performance Li-S batteries interlayer.

Graphene sheets assembled into three-dimensional networks of carbon nanofibers: A nano-engineering approach for binder-free supercapacitor electrodes

The design and synthesis of flexible and free-standing carbon nanofibers membrane with good electrochemical properties have recently attracted much attention in energy storage applications. Herein, we fabricated graphene sheets-incorporated three-dimensional carbon nanofibers membrane (3D-GCNFs) as effective electrode materials for supercapacitors. The electrospun two-dimensional (2D) graphene oxide sheets-incorporated polyacrylonitrile nanofibers (GO/PAN NFs) were transformed into 3D membrane by a gas-forming technique using sodium borohydride. Subsequent thermal treatment converted the 2D-assembled GO/PAN NFs membrane into the low-density 3D-GCNFs membrane. The morphology and electrochemical performances of the as-prepared 3D membrane were systematically investigated using state-of-the-art techniques. It was found that the electrochemical performance of the as-obtained 3D-GCNFs membrane was greatly improved compared to the 2D counterparts. As a binder-free electrode, the materials exhibited a high areal capacitance of 318 mF/cm2 at a current density of 1 mA/cm2 and good cyclic stability of up to 98.5% after 5000 cycles. In addition, a symmetrical supercapacitor was constructed using the 3D-GCNFs membrane as both negative and positive electrodes. The device exhibited areal capacitance of 240 mF/cm2 at a current density of 1 mA/cm2, an energy density of 33.33 mWh/cm2, a power density of 1000 mW/cm2, and capacitance retention of 103% after 5000 cycles. The improved performance of the 3D-GCNFs membrane was attributed to its high electrical conductivity due to the absence of binders, high porosity, and conductive networks that form efficient channels for electrolyte penetration and effectively shorten the transmission distance. We believe that this study not only provides a reference for the introduction of 3D CNFs-based composite membranes, but also demonstrates their great potential for energy storage applications.

Hydrogen-bond-mediated micelle aggregating self-assembly towards carbon nanofiber networks for high-energy and long-life zinc ion capacitors

Designing well-orchestrated carbon nanostructure is critical for Zn-ion capacitors with superb capacitive activity and durability. Herein, a hydrogen-bond-mediated micelle aggregating self-assembly strategy is developed to design interweaved carbon nanofiber networks (TB-DA-80) for propelling Zn-ion storage capability. In the strategy, the intermolecular hydrogen bonds between solvent molecules and hydrophilic segments of block copolymer (F127) is regulated by controlling temperature in polymerization, which could induce aggregating self-assembly of micelles. It has been revealed that hydrogen bonding is reduced by increasing temperature due to the enhancement of thermal motion of solvent molecular. The self-assembled micelles could guide the interweavement of carbon nanofiber networks, which maximize the accessibility of surface-active sites and stimulate ion migration throughout 3D architecture. Then, the assembled carbon nanofiber networks-based Zn-ion capacitor delivers an ultrahigh energy density of 163 Wh kg−1 and a super-stable cycle lifespan with a 90.5% capacity retention after 400, 000 cycles at 20 A/g. Systematic studies untangle that the excellent electrochemical metrics root in the synergy of physical Zn2+ and H+ dual-ion co-uptake and robust chemical redox of Zn2+ with carbonyl/pyridine motifs to form O − Zn − N bonds. This study provides a platform for the elaborate fabrication of nanoarchitectured carbon cathodes towards advanced energy storage.

Incorporation of FexOy nanoparticles into 3D interlinked porous carbon nanofiber networks to synergistically enhance the electrical insulation, electromagnetic wave absorbing/shielding performance and thermal conductivity

The property incompatibility among heat conduction, electromagnetic wave (EMW) absorption/shielding, and electrical insulation has restricted the synchronous enhancement and application of polymer-based composites. Herein, we first synthesized porous 3D interlinked C nanofiber/FexOy (CNF/FexOy) wafers for significantly enhanced properties by a simple sol–gel and annealing route. The texture, composition, defects and the resulting properties can conveniently be manipulated via altering Fe3+ concentration and annealing temperature. The CNF/FexOy wafers exhibit a high heat conductivity (3.22 W/mK) at a low loading (30 wt%) thanks to the shorter continuous thermal transfer paths and the increased phonon mean free path and thermal capacity of phonons per volume. Moreover, CNF/FexOy wafers possess a wide absorption band (9.36 GHz), prominent EMI shielding effectiveness (SET ≥ 20 dB over C, X, and Ku bands), excellent electrical insulation (σ = 0.00991 S/m), and enhanced mechanical/hydrophobicity properties, surpassing most reported fillers. These enhancements could be explained by the fact that the cooperative action of porous structures, defects, and magnetic/dielectric FexOy hinder electron migration and improve the impedance matching and multiple-scattering of materials. The silicone composites supported by 3D interlinked CNF/FexOy wafers have great potential as a filler with high-performance EMI shielding/absorption and thermal control in next-generation flexible electronics.

Temperature-dependent synthesis of SnO2 or Sn embedded in hollow porous carbon nanofibers toward customized lithium-ion batteries

Lithium-ion batteries (LIBs) have been widely used as grid-level energy storage systems to power electric vehicles, hybrid electric vehicles, and portable electronic devices. However, it is a big challenge to develop high-capacity electrode materials with large energy storage and ultrafast charging capability simultaneously due to the sluggish charge carrier transport in bulk materials and fragments of active materials. To address this issue, composite electrodes of SnO2 nanodots and Sn nanoclusters embedded in hollow porous carbon nanofibers (denoted as SnO2@HPCNFs and Sn@HPCNFs) were respectively constructed programmatically for customized LIBs. Highly interconnected carbon nanofiber networks served as fast electron transport pathways. Additionally, the hierarchical hollow and porous structure facilitated rapid Li-ion diffusion and alleviated the volume expansion of Sn and SnO2. SnO2@HPCNFs delivered a remarkably high capacity of 899.3 mA h g−1 at 0.1 A g−1 due to enhanced Li adsorption and high ionic diffusivity. Meanwhile, Sn@HPCNFs displayed fast charging capability and superior high rate performance of 238.8 mA h g−1 at 5 A g−1 (∼10 C) due to the synergetic effect of enhanced Li-ion storage in the bulk pores of Sn and improved electronic conductivity. The investigation of the electrochemical behaviors of SnO2 and Sn by tailoring the carbonization temperature provides new insight into constructing high-capacity anode materials for high-performance energy storage devices.

Co-Co9S8-NC particles anchored on 3D hyperfine carbon nanofiber networks with a hierarchical structure as a catalyst promoting polysulfide conversion for lithium–sulfur batteries

The shuttle effect of lithium polysulfides has been an important factor limiting the practical application of lithium–sulfur batteries. CNF/Co-Co9S8-NC composites with a 3D hierarchical structure were prepared as the polysulfide electrocatalyst.

In-situ encapsulating ultrafine CoFe2O4 nanoparticle into porous N-doped carbon nanofiber membrane as self-standing anode for enhanced lithium storage performance

The ultrasmall CoFe2O4 nanoparticles in situ encapsulated in porous N-doped carbon nanofibers membranes (CFO@PNCFM) with different pore structures have been prepared by electrospinning and subsequent carbonization. When immediately used as self-standing anodes for lithium-ion batteries (LIBs), the optimized CFO@PNCFM exhibits superior lithium storage properties with high rate capability (476.5 mAh g−1 at 2 A g−1) and long stable cycle life (755.8 mAh g−1 at 100 mA g−1 after 200 cycles). The outstanding electrochemical performance may be mainly ascribed to the synergistic effect of special 3D conductive porous carbon nanofibers (PCNFs) network and ultrafine CoFe2O4 nanoparticles in energy storage, which can significantly enhance the utilization efficiency of electroactive materials and improve the charge-transport kinetics. Moreover, the CoFe2O4 nanoparticles bonded closely to PCNFs through strong metal-oxygen bridges, which promote the electron capture and transfer from PCNFs to CoFe2O4, and thus achieving fast electrochemical reaction kinetics. Meanwhile, the porous structure can not only alleviate the volume change during charge/discharge cycles, but also supply numerous active sites for lithium storage, resulting in a high reversible capacity as well as good cycle stability and rate performance.

Three-dimensional MOF-derived host with surface-preferred and spatial-selective effect for dendrite-free lithium metal battery

The large-scale applications of lithium metal batteries (LMBs) are still impeded by the unsatisfactory electrochemical performance of Li metal anode associated with the infinite volumetric change and the uncontrollable Li dendrite growth. Herein, free-standing and robust nitrogen-doped 3D porous carbon nanofibers networks embedded with Zn-carbon hybrid nanocages are obtained as stable hosts for guiding uniform Li nucleation and accommodating volume expansion. Benefiting from the reduced local current density and abundant lithiophilic sites with low nucleation barriers, the as-prepared NCNFs-Zn-CCs electrode can achieve a low overpotential of 20 mV at 3 mA cm−2 and a stable Li plating/stripping process for 3200 h were achieved in symmetric cells. This work opens a new avenue to explore and broaden the applications of lithiophilic carbon materials in next-generation lithium metal batteries with excellent cycling stability and rate performance.

Three-dimensional carbon nanofiber networks encapsulated in cobalt–molybdenum metal clusters on nitrogen-doped carbon as ultra-efficient electrocatalysts for hydrogen evolution reactions

Efficient and cost-effective catalysts have been developed for the production of hydrogen via water electrolysis. In this study, we develop a strategy for the fabrication of carbon nanofiber catalysts loaded with CoMo clusters covered by a nitrogen-doped carbon network (CoMo/CN@CNFs/MEL). The surface of two-dimensional carbon fibers was coated with a nitrogen-doped carbon network via melamine pyrolysis, thereby forming three-dimensional (3D) networks. These 3D network catalysts exhibited excellent catalytic performance in the hydrogen evolution reaction with 1 M KOH, requiring an overpotential of only 148 mV to reach a current density of 10 mA cm−2 owing to synergistic effects resulting from their structure and composition. The catalytic performance of the CoMo/CN@CNFs/MEL catalysts was comparable to that of commercial Pt/C at high current densities owing to their unique structural features, including restricted Co–Mo clusters, porous nitrogen-doped carbon frameworks, continuous conducting carbon nanofibers, and carbon nitride networks. This work provides a promising approach to transition metal-based catalysts with improved stability and atom utilization efficiency.

Carbonized Bacterial Cellulose Decorated with ZIF-8 Derived Iron Single-Atom Catalyst Nanocages As a Cathode Host for Lithium-Sulfur Batteries

Li-S chemistry is regarded as promising next-generation battery technology. However, its complex redox process and long-chain lithium polysulfides shuttling are hindering the development of practical Li-S battery technology. Various electrocatalysts are being investigated to address the problem by expediting reaction kinetics. Here we report Fe single metal atom catalyst (Fe-SAC) used in the sulfur cathode of Li-S batteries.Fe-SAC is synthesized using a modified metal-organic framework (MOF)-based approach, in which the low vapor pressure Fe element substitutes Zn during pyrolysis of ZIF-8 to attain Fe-N4 moieties by being coordinated with four substitutional nitrogen atoms in the graphene lattice. A freestanding 3D structure with Fe-SAC-functionalized carbon nanocages linked by a carbon nanofiber network is applied as the sulfur cathode scaffold. Here the nanocages are derived from Fe-doped ZIF with Fe-N4 SAC moieties embedded on the inside and outside surfaces. The carbon nanofiber network is derived from the carbonization of bacterial cellulose.We report several methods for assessing Fe-SAC catalytic function on sulfide redox reactions for the prepared electrode in cells with lithium polysulfides electrolytes. Electrochemical studies compare the performance of the nanostructured electrodes with or without Fe-SAC to confirm the catalytic effects in improving the Li-S battery performance. Accordingly, the prepared composite cathode delivers a high initial capacity of 1338 mAh/g at 0.1C and excellent rate capability at 2C with a reversible capacity of 840 mAh/g.

Efficient dual conductive network based on layered double hydroxide nanospheres and nanosheets anchored in N-carbon nanofibers for asymmetric supercapacitors

A green electrode material with dual conductive networks via electrospinning with carbonization and co-precipitation method is constructed. Nitrogen-based carbon nanofiber network (CCP-N) is used as the inner-conductive, electrochemical-active substrate and flexible skeleton. The Co Ni layered double hydroxide (Co Ni LDH) nanosheets and flower-like nanospheres, which randomly and closely covering the surface of CCP-N, respectively, just as the fungus grow on trunks in nature, is regarded as outer-conductive and active substance collector in order to provide abundant active centers, sufficient reaction interface to advance fast electrolyte ions diffusion and electrons transport. Furthermore, the growth process of Co Ni LDH on CCP-N is observed by controlling growth time and the Co/Ni ratio of the precursor solution. It is found that the optimal Co/Ni ratio was 2:1, while that optimal growth time is 12 h. The specific capacitance of Co Ni LDH@CCP-N electrode reaches 1319.4 F g-1 at 1 A g-1. The assembled asymmetric supercapacitor device (CCP-N @ Co Ni LDH//CCP-N) possesses a high energy density of 48.1 W h kg-1 at power density of 576.8 W kg-1, excellent cycling stability of 82.2% retention after 10,000 cycles. The results clearly indicate the Co Ni LDH@CCP-N materials have enormously potential in energy storage. This work puts forward a novel strategy for the design and fabrication of green and advanced supercapacitors materials with high power density and energy density.

3D electronic channels wrapped Large-Sized SnSe as flexible electrode for Sodium-Ion batteries

Transition metal selenides are regarded as the promising anode materials for sodium-ion batteries (SIBs) due to their high theoretical capacitie. However, they still suffer from some fatal flaws including short lifetime and sluggish cycling kinetics. Herein, a free-standing, binder-free electrode was developed by electrospinning and subsequent thermal treatment process, in which three-dimensional (3D) N-doped carbon nanofibers and tin selenide are cross-linked with each other (SnSe/NCF). The synergistic effect of SnSe microsheets and carbon fibers shortens the ion transport channel and increases more active sites. N-doped carbon network not only improves electrical conductivity but also prevents pulverization of the material. The as-prepared SnSe/NCF electrodes exhibit good electrical conductivity and flexibility owing to the highly carbonized carbon nanofiber network. The SnSe/NCF electrode exhibits superior specific capacity with (576.7 mAh g−1 at 0.2 A g−1), ultra-long lifetime (286.4 mAh g−1 after 2100 cycles at 2.0 A g−1) and excellent rate performance (576.7 mAh g−1 at 5 A g−1) as a stand-alone anode for SIBs. This work provides a promising approach for developing flexible energy storage devices.

Electrochemical Properties of LiFePO4 Cathodes: The Effect of Carbon Additives

The influence of different conductive additives (carbon nanofibers (CNFs), carbon nanoplatelets, and pyrolytic carbon from sucrose (Sucr) or polyvinylidene fluoride) on the morphology, electron conductivity, and electrochemical performance of LiFePO4-based cathodes was investigated to develop the most efficient strategy for the fabrication of high-rate cathodes. Pyrolytic carbon effectively prevents the growth of LiFePO4 grains and provides contact between them, CNFs provide fast long-range conductive pathways, while carbon nanoplatelets can be embedded in carbon coatings as high-conductive “points” which enhance the rate capability and decrease the capacity fading of LFP. The LiFePO4/CSucr/CNF showed better performance than the other cathodes due to the synergy of the high-conductive CNF network (the electronic conductivity was 1.3 × 10−2 S/cm) and the shorter Li+ ion path (the lithium-ion diffusion coefficient was 2.1 × 10−11 cm2/s). It is shown that the formation of composites based on LFP and carbon nanomaterials via mortar grinding is a more promising strategy for electrode material manufacturing than ball milling.

Petal-like NiCoP sheets on 3D nitrogen-doped carbon nanofiber network as a robust bifunctional electrocatalyst for water splitting

Searching high-active, stable and abundant bifunctional catalysts to replace noble metals for hydrogen and oxygen evolution reactions (HER and OER) is desired. Herein, petal-like NiCoP sheets were synthesized on carbon paper covered with a 3D nitrogen-doped carbon nanofiber network (NiCoP/CNNCP) by a simple hydrothermal process followed by phosphorization. The HER overpotential in 0.5 M H2SO4 and OER overpotential in 1 M KOH of the NiCoP/CNNCP electrode only required 55 mV and 260 mV to drive a current density of 10 mA cm−2, respectively, which was comparable or even better than most nickel-and cobalt-based phosphide catalysts. The overall water-splitting electrolyzer with an asymmetric electrolyte system assembled using NiCoP/CNNCP as bifunctional electrodes required an extremely low cell voltage of 1.04 V to achieve a current density of 10 mA cm−2, which was much lower than almost all alkaline electrolysis systems.

NiCoO2 and polypyrrole decorated three-dimensional carbon nanofiber network with coaxial cable-like structure for high-performance supercapacitors

Designing optimized nano-sized architecture is a promising approach to prepare high-performance electrode materials for supercapacitors. In this work, a hierarchical multi-shelled structure has been successfully synthesized, which consists of a 3D carbon nanofiber network as a supporting scaffold prepared by carbonization of aramid nanofiber aerogel, an intermediate polypyrrole (PPy) bonding layer and a NiCoO2 outer shell, just like a coaxial cable in the structure. The intermediate PPy layer facilitates the uniform deposition of NiCoO2 by providing more anchor sites, and enhances the electrical contact between carbon nanofiber network and NiCoO2 shell due to its high conductivity and good compatibility with two different substances. The synergistic effect of the hierarchical configuration endows the electrode material with a high specific capacitance of 1037 F g−1at 1 A g−1and excellent cycling stability (∼89% of initial capacitance after 7000 cycles). Moreover, an asymmetric supercapacitor based on the composite and activated carbon achieves a high energy density of 37.7 Wh kg−1 at a power density of 465 W kg−1 in 1.65 V. This work may provide a feasible strategy to design high-performance hybrid electrodes for energy storage devices.

High sensitivity and broad linearity range pressure sensor based on hierarchical in-situ filling porous structure

Flexible piezoresistive pressure sensor with high sensitivity over a broad linearity range have been attracting tremendous attention for its applications in health monitoring, artificial intelligence, and human-machine interfaces. Herein, we report a hierarchical in-situ filling porous piezoresistive sensor (HPPS) by direct ink writing (DIW) printing and curing of carbon nanofibers (CNFs)/polydimethylsiloxane (PDMS) emulsion. Hierarchical geometry significantly increases the contact area, distributes stress to multilayered lattice and internal porous structure, resulting in a broad sensing range. Moreover, unlike conventional hollow porous structure, the CNFs networks in-situ filling porous structure generates more contact sites and conductive pathways during compression, thereby achieving high sensitivity and linearity over entire sensing range. Therefore, the optimized HPPS achieves high sensitivity (4.7 kPa−1) and linearity (coefficient of determination, R2 = 0.998) over a broad range (0.03–1000 kPa), together with remarkable response time and repeatability. Furthermore, the applications in diverse pressure scenarios and healthcare monitoring are demonstrated.

A High Conductive Composite Bipolar Plate with Conductive Network Constructed by Chemical Vapor Deposition

In this study, a highly conductive composite bipolar plate with an embedded conductive carbon nanofiber network was prepared by chemical vapor deposition, and a conductive network was constructed inside the composite bipolar plate. The latter network was then compared with a conductive network formed by directly adding carbon nanotubes more evenly distributed. The optimum preparation methods of vapor-grown carbon fibers and the fiber content were analyzed, and the specific surface area and porosity of the bipolar plates were measured and analyzed using a BET test. The results show that the carbon nanofibers prepared under the conditions of 700 °C and a content of 2% exhibited the best effect on improving the performance of the bipolar plates. The conductivity of the prepared bipolar plates could reach 255.2 S/cm, which is 22.1% higher than treatment with multi-walled carbon nanotubes. The bending strength of the prepared bipolar plates was 47.92 MPa, and the interface contact resistance was 6.24 mΩ·cm2. In conclusion, the bipolar plates modified with vapor-grown carbon fibers were a promising kind of material for proton exchange membrane fuel cells.

Silicon nanocrystals-embedded carbon nanofibers from hybrid polyacrylonitrile – TEOS precursor as high-performance lithium-ion battery anodes

The high capacity of silicon (Si) for lithium incorporation makes it a promising anode material for lithium-ion batteries; however, pulverization of Si due to huge volume changes during lithiation/delithiation leads to significant capacity loss during cycling. To address challenges in low cyclability, nanostructured Si in carbon nanocomposites offers an attractive solution. In this study, we report an efficient method for the synthesis of a nanocomposite containing Si nanoparticles homogeneously embedded in an electrically conductive carbon nanofiber (CNF) network. Electrospinning of polyacrylonitrile (PAN) solution containing hydrolyzed tetraethyoxysilane (TEOS), as a Si precursor, and subsequent carbonization of hybrid nanofibers yielded a composite of SiO2 ultrafine nano-domains in the carbon network (C-SiO2). Low temperature molten salt-assisted aluminothermic reduction of C-SiO2 nanofibers allowed us to produce a C-Si/SiOx nanocomposite without forming detrimental SiC, which is thermodynamically favorable at high temperatures in a system with a high interfacial surface area between the carbon and SiO2 phases. The nanocomposite C-Si/SiOx anodes showed a reversible capacity of 860 mAh g−1 at a current rate of 200 mA g−1, retaining a capacity of 680 mAh g−1 after 100 cycles. In addition, the nanocomposite anodes delivered a reversible capacity of 569 mAh g−1 at a current rate of 400 mA g−1 while maintaining 95% of maximum capacity after subsequent 100 cycles. This study demonstrates the capability of designing nanocomposite anodes from reaction precursors combined with low-temperature aluminothermic reduction to produce a capacity-retaining anode composite of Si nanocrystals uniformly dispersed in the carbon matrix.

Self-supported hierarchically porous 3D carbon nanofiber network comprising Ni/Co/NiCo2O4 nanocrystals and hollow N-doped C nanocages as sulfur host for highly reversible Li–S batteries

Hierarchically porous nitrogen-doped carbon nanofibers (P-N-CNF) comprise well-embedded metallic-Ni/Co and spinel-type NiCo2O4 nanocrystals (Ni-Co/NiCo2O4) along with metal-organic framework-derived hollow nitrogen-doped carbon nanocages (HNC), denoted as P-N-CNF@NCO/HNC, are rationally designed as cathode substrates for advanced lithium-sulfur batteries with feasible parameters. The highly conductive and porous N-CNF matrix provides numerous conductive channels for rapid ionic and electronic transfer. HNC guarantees efficient impregnation of a large volume of active material along with high loading, channelizing the volume variation stress, and ensuring efficient electrolyte percolation, which is crucial for uniform dispersion and high active sulfur utilization, especially at low electrolyte/sulfur (E/S) ratios. The metallic-Ni/Co and polar spinel-type NiCo2O4 nanoparticles offer sufficient chemisorption sites to prevent polysulfide migration towards the anode. Li-S cells assembled using P-N-CNF@NCO/HNC as an advanced host and lithium polysulfide catholyte as the starting material displayed stable electrochemical performance even with strident battery parameters, including high sulfur content (79.8 wt%), high sulfur loading (7.7 mg cm−2), and low E/S ratio (8.0 µL mg−1). The cell displays a maximum areal capacity of 5.4 mA h cm−2 that stabilizes to 2.8 mA h cm−2 after 160 cycles at 0.1 C and is comparable to the theoretical threshold of presently available commercial systems.