Well-dispersed Pt/RuO2-decorated mesoporous N-doped carbon as a hybrid electrocatalyst for Li–O2 batteries

Despite their high energy density, the poor cycling performance of lithium–oxygen (Li–O₂) batteries limits their practical application. Therefore, to improve cycling performance, considerable attention has been paid to the development of an efficient electrocatalyst for the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER). Catalysts that can more effectively reduce the overpotential and improve the cycling performance for the OER during charging are of particular interest. In this study, porous carbon derived from protein-based tofu was investigated as a catalyst support for the oxygen electrode (O₂-electrode) of Li–O₂ batteries, wherein ORR and OER occur. The porous carbon was synthesized using carbonization and KOH activation, and RuO₂ and Pt electrocatalysts were introduced to improve the electrical conductivity and catalytic performance. The well-dispersed Pt/RuO₂ electrocatalysts on the porous N-doped carbon support (Pt/RuO₂@ACT) showed excellent ORR and OER catalytic activity. When incorporated into a Li–O₂ battery, the Pt/RuO₂@ACT O₂-electrode exhibited a high specific discharge capacity (5724.1 mA h g⁻¹ at 100 mA g⁻¹), a low discharge–charge voltage gap (0.64 V at 2000 mA h g⁻¹), and excellent cycling stability (43 cycles with a limit capacity of 1000 mA h g⁻¹). We believe that the excellent performance of the Pt/RuO₂@ACT electrocatalyst is promising for accelerating the commercialization of Li–O₂ batteries.

The excellent performance of the Pt/RuO₂@ACT electrocatalyst is promising for accelerating the commercialization of Li–O₂ batteries.     

Metal–organic framework derived hollow porous CuO–CuCo2O4 dodecahedrons as a cathode catalyst for Li–O2 batteries

Herein, hollow porous CuO–CuCo₂O₄ dodecahedrons are synthesized by using a simple self-sacrificial metal–organic framework (MOF) template, which resulted in dodecahedron morphology with hierarchically porous architecture. When evaluated as a cathodic electrocatalyst in lithium–oxygen batteries, the CuO–CuCo₂O₄ composite exhibits a significantly enhanced electrochemical performance, delivering an initial capacity of 6844 mA h g⁻¹ with a remarkably decreased discharge/charge overpotential to 1.15 V (vs. Li/Li⁺) at a current density of 100 mA g⁻¹ and showing excellent cyclic stability up to 111 charge/discharge cycles under a cut-off capacity of 1000 mA h g⁻¹ at 400 mA g⁻¹. The outstanding electrochemical performance of CuO–CuCo₂O₄ composite can be owing to the intrinsic catalytic activity, unique porous structure and the presence of substantial electrocatalytic sites. The ex situ XRD and SEM are also carried out to reveal the charge/discharge behavior and demonstrate the excellent reversibility of the CuO–CuCo₂O₄ based electrode.

Metal–organic framework derived porous CuO–CuCo₂O₄ dodecahedrons as a cathode catalyst for Li–O₂ batteries with significantly enhanced rate and cyclic performance.     

Excellent oxygen evolution reaction of NiO with a layered nanosphere structure as the cathode of lithium–oxygen batteries

A layered nanosphere structured NiO catalyst was successfully synthesized by a simple and efficient hydrothermal method as a cathode material for lithium–oxygen (Li–O₂) batteries. Cyclic voltammetry (CV), dual electrode voltammetry (DECV) and chronoamperometry (CA) by rotating ring-disk electrode (RRDE) were carried out to investigate the catalytic activity of this catalyst for the oxygen evolution reaction (OER). The results revealed that the layered nanosphere NiO exhibited excellent electrochemical performance, stability and a typical four-electron reaction as a cathode electrocatalyst for rechargeable nonaqueous Li–O₂ batteries. The overpotential of the NiO is only up to 0.61 V. X-ray photoelectron spectroscopy (XPS) characterization shows that the Li₂O₂ and Li₂CO₃ formed during the discharge process and decomposed after charging. Moreover, the cut-off voltage of discharging is about 2.0 V in the NiO-based Li–O₂ batteries, while the specific capacity is up to 3040 mA h g⁻¹. There is no obvious performance decline of the battery after 50 cycles at a current density of 0.1 mA cm⁻² with a superior limited specific capacity of 800 mA h g⁻¹. Herein, the layered nanosphere structured NiO catalyst is considered a promising cathode electrocatalyst for Li–O₂ batteries.

A layered nanosphere structured NiO catalyst was synthesized by a simple and efficient hydrothermal method as a cathode material for lithium–oxygen (Li–O₂) batteries.     

CeO2-modified P2–Na–Co–Mn–O cathode with enhanced sodium storage characteristics

To improve the cycling stability and dynamic properties of layered oxide cathodes for sodium-ion batteries, surface modified P2–Na_0.67Co_0.25Mn_0.75O₂ with different levels of CeO₂ was successfully synthesized by the solid-state method. X-ray photoelectron spectra, X-ray diffraction and Raman spectra show that the P2-structure and the oxidation state of cobalt and manganese of the pristine oxide are not affected by CeO₂ surface modification, and a small amount of Ce⁴⁺ ions have been reduced to Ce³⁺ ions, and a few Ce ions have entered the crystal lattice of the P2-oxide surface during modification with CeO₂. In a voltage range of 2.0–4.0 V at a current density of 20 mA g⁻¹, 2.00 wt% CeO₂-modified Na_0.67Co_0.25Mn_0.75O₂ delivers a maximum discharge capacity of 135.93 mA h g⁻¹, and the capacity retentions are 91.96% and 83.38% after 50 and 100 cycles, respectively. However, the pristine oxide presents a low discharge capacity of 116.14 mA h g⁻¹, and very low retentions of 39.83% and 25.96% after 50 and 100 cycles, respectively. It is suggested that the CeO₂ modification enhances not only the maximum discharge capacity, but also the electric conductivity and the sodium ion diffusivity, resulting in a significant enhancement of the cycling stability and the kinetic characteristics of the P2-type oxide cathode.

The CeO₂ modification significantly enhances the maximum discharge capacity and cycling stability of a P2–Na_0.67Co_0.25Mn_0.75O₂ cathode.     

Self-supporting V2O5 nanofiber-based electrodes for magnesium–lithium-ion hybrid batteries

The increasing demand for high energy, sustainable and safer rechargeable electrochemical storage systems for portable devices and electric vehicles can be satisfied by the use of hybrid batteries. Hybrid batteries, such as magnesium–lithium-ion batteries (MLIBs), using a dual-salt electrolyte take advantage of both the fast Li⁺ intercalation kinetics of lithium-ion batteries (LIBs) and the dendrite-free anode reactions. Here we report the utilization of a binder-free and self-supporting V₂O₅ nanofiber-based cathode for MLIBs. The V₂O₅ cathode has a high operating voltage of ∼1.5 V vs. Mg/Mg²⁺ and achieves storage capacities of up to 386 mA h g⁻¹, accompanied by an energy density of 280 W h kg⁻¹. Additionally, a good cycling stability at 200 mA g⁻¹ over 500 cycles is reached. The structural integrity of the V₂O₅ cathode is preserved upon cycling. This work demonstrates the suitability of the V₂O₅ cathode for MLIBs to overcome the limitations of LIBs and MIBs and to meet the future demands of advanced electrochemical storage systems.

This work shows the feasibility of a self-supporting V₂O₅ nanofiber-based cathode for magnesium–lithium-ion batteries reaching an energy density of 280 W h kg⁻¹.     

TiO2-decorated porous carbon nanofiber interlayer for Li–S batteries

Lithium–sulfur (Li–S) batteries are the most promising energy storage systems owing to their high energy density. However, shuttling of polysulfides detracts the electrochemical performance of Li–S batteries and thus prevents the commercialization of Li–S batteries. Here, TiO₂@porous carbon nanofibers (TiO₂@PCNFs) are fabricated via combining electrospinning and electrospraying techniques and the resultant TiO₂@PCNFs are evaluated for use as an interlayer in Li–S batteries. TiO₂ nanoparticles on PCNFs are observed from SEM and TEM images. A high initial discharge capacity of 1510 mA h g⁻¹ is achieved owing to the novel approach of electrospinning the carbon precursor and electrospraying TiO₂ nanoparticles simultaneously. In this approach TiO₂ nanoparticles capture polysulfides with strong interaction and the PCNFs with high conductivity recycle and re-use the adsorbed polysulfides, thus leading to high reversible capacity and stable cycling performance. A high reversible capacity of 967 mA h g⁻¹ is reached after 200 cycles at 0.2C. The cell with the TiO₂@PCNF interlayer also delivers a reversible capacity of around 1100 mA h g⁻¹ at 1C, while the cell without the interlayer exhibits a lower capacity of 400 mA h g⁻¹. Therefore, this work presents a novel approach for designing interlayer materials with exceptional electrochemical performance for high performance Li–S batteries.

Lithium–sulfur (Li–S) batteries are the most promising energy storage systems owing to their high energy density.     

Electrochemical studies of a high voltage Na4Co3(PO4)2P2O7–MWCNT composite through a selected stable electrolyte

Cathode materials that operate at high voltages are required to realize the commercialization of high-energy-density sodium-ion batteries. In this study, we prepared different composites of sodium cobalt mixed-phosphate with multiwalled carbon nanotubes (Na₄Co₃(PO₄)₂P₂O₇–MWCNTs) by the sol–gel synthesis technique. The crystal structure and microstructure were characterized by using PXRD, TGA, Raman spectroscopy, SEM and TEM. The electrochemical properties of the Na₄Co₃(PO₄)₂P₂O₇–20 wt% MWCNT composite were explored using two different electrolytes. The composite electrode exhibited excellent cyclability and rate capabilities with the electrolyte composed of 1 M sodium hexafluorophosphate in ethylene carbonate:dimethyl carbonate (EC:DMC). The composite electrode delivered stable discharge capacities of 80 mA h g⁻¹ and 78 mA h g⁻¹ at room and elevated (55 °C) temperatures, respectively. The average discharge voltage was around 4.45 V versus Na⁺/Na, which corresponded to the Co^2+/3+ redox couple. The feasibility of the Na₄Co₃(PO₄)₂P₂O₇ cathode for sodium-ion batteries has been confirmed in real time using a full cell configuration vs. NaTi₂(PO₄)₃–20 wt% MWCNT, and it delivers an initial discharge capacity of 78 mA h g⁻¹ at 0.2C rate.

Na₄Co₃(PO₄)₂P₂O₇–MWCNT composites in 1 M NaPF₆ in EC:DMC electrolytes deliver stable discharge capacities of 80 mA h g⁻¹ and 78 mA h g⁻¹ at normal and elevated temperatures, respectively. In a full cell configuration vs. NaTi₂(PO₄)₃–MWCNT, they deliver an initial discharge capacity of 78 mA h g⁻¹ at 0.2C rate.     

Effects of Al-dopant at Ni or Co sites in LiNi0.6Co0.3Ti0.1O2 on interlayer slabs (Li–O) and intralayer slabs (TM–O) and their influence on the electrochemical performance of cathode materials

In order to satisfy the energy demands of the electromobility market, further improvements in cathode materials are receiving much attention, especially high energy density cathode materials for Li-ion batteries (LIBs). In this work, the self-propagating combustion (SPC) method is use to synthesise undoped LiNi_0.6Co_0.3Ti_0.1O₂ (LNCT), novel nano-sized Al-doped LiNi_0.6Co_0.3−xAl_xTi_0.1O₂ (LCA) and LiNi_0.6−xCo_0.3Al_xTi_0.1O₂ (LNA) (x = 0.01) cathode materials. LNCT, LCA and LNA were annealed at 700 °C for 24 h. Following the synthesis, the phase, chemical structure and purity of the materials were analysed using X-ray diffraction (XRD). Based on the XRD results, all materials exhibit a single-phase structure with rhombohedral layered structure. Based on the HRTEM and EDX results, all samples exhibit polyhedral-like shapes, while the Al-doped samples display smaller crystallite sizes compared to the undoped sample. As for the electrochemical performances, the initially discharged capacity of LCA (238.6 mA h g⁻¹) is higher than that of LNA (214.7 mA h g⁻¹) and LNCT (150.5 mA h g⁻¹). However, LNA has a lower loss of capacity after the 50^th cycle compared to the LCA sample, which makes it a more excellent candidate for electrochemical applications. The main reason for the excellent electrochemical behaviour of LNA is due to lower cation mixing. Furthermore, Rietveld refinements reveal that the LNA sample has a longer atomic distance of Li–O and shorter TM–O in the cathode structure, which makes Li⁺ ion diffusion more efficient, leading to excellent electrochemical performance. These findings further proved the potential of the novel nano cathode material of LiNi_0.6−xCo_0.3Al_xTi_0.1O₂ (LNA) to replace the existing commercialized cathode materials for rechargeable Li-ion batteries.

Al substitute into Ni site increase Li–O and reduce M–O atomic distance lead to excellent cycleability with high energy density.     

Bagasse as a carbon structure with high sulfur content for lithium–sulfur batteries

A bagasse-based 3D carbon matrix (BC) with high specific surface area and high conductivity was obtained by carbonization and pore-forming processes with bagasse as the carbon precursor and K₂FeO₄ as the pore-former. The microporous structure and nitrogenous functional groups were determined in the prepared carbon matrix, which could allow high sulfur loading and improve the polysulfide absorption capacity during cycling. After sulfur infusion, the S/BC composite with 68.8% sulfur content was obtained. The lithium–sulfur (Li–S) battery with the S/BC cathode shows high specific capacity and good cycling performance. It delivers a specific capacity of 1360 mA h g⁻¹ at 0.2C and remains at 790 mA h g⁻¹ after 200 cycles. At 1C, the Li–S with this composite cathode exhibits 601 mA h g⁻¹ after 150 cycles. This work offers a new kind of green material and a new method for Li–S batteries.

Bagasse-based carbon matrix with microporous structure and nitrogenous functional groups could have high sulfur loading and excellent polysulfide absorption capacity.     

Nanostructured RuO2–Co3O4@RuCo-EO with low Ru loading as a high-efficiency electrochemical oxygen evolution catalyst

Electrochemical water splitting technology is considered to be the most reliable method for converting renewable energy such as wind and solar energy into hydrogen. Here, a nanostructured RuO₂/Co₃O₄–RuCo-EO electrode is designed via magnetron sputtering combined with electrochemical oxidation for the oxygen evolution reaction (OER) in an alkaline medium. The optimized RuO₂/Co₃O₄–RuCo-EO electrode with a Ru loading of 0.064 mg cm⁻² exhibits excellent electrocatalytic performance with a low overpotential of 220 mV at the current density of 10 mA cm⁻² and a low Tafel slope of 59.9 mV dec⁻¹ for the OER. Compared with RuO₂ prepared by thermal decomposition, its overpotential is reduced by 82 mV. Meanwhile, compared with RuO₂ prepared by magnetron sputtering, the overpotential is also reduced by 74 mV. Furthermore, compared with the RuO₂/Ru with core–shell structure (η = 244 mV), the overpotential is still decreased by 24 mV. Therefore, the RuO₂/Co₃O₄–RuCo-EO electrode has excellent OER activity. There are two reasons for the improvement of the OER activity. On the one hand, the core–shell structure is conducive to electron transport, and on the other hand, the addition of Co adjusts the electronic structure of Ru.

The optimized RuO₂/Co₃O₄–RuCo-EO electrode with Ru loading of 0.064 mg cm⁻² exhibits the excellent oxygen evolution activity with an overpotential of 220 mV at the current density of 10 mA cm⁻² and a Tafel slope of 59.9 mV dec⁻¹.     

Lychee-like TiO2@TiN dual-function composite material for lithium–sulfur batteries

Lithium–sulfur (Li–S) batteries are promising candidates for next generation rechargeable batteries because of their high energy density of 2600 W h kg⁻¹. However, the insulating nature of sulfur and Li₂S, the “shuttle effect” of lithium polysulfides (LiPSs), and the volumetric change of sulfur electrodes limit the practical application of Li–S batteries. Here, lychee-like TiO₂@TiN hollow spheres (LTTHS) have been developed that combine the advantages of high adsorption TiO₂ and high conductivity TiN to achieve smooth adsorption/spread/conversion of LiPSs and use them as a sulfur host material in Li–S batteries for the first time. The cathode exhibits an initial specific capacity of 1254 mA h g⁻¹ and a reversible capacity of 533 mA h g⁻¹ after 500 cycles at 0.2C, which corresponds to an average coulombic efficiency up to 99%. The cell with the LTTHS@S cathode achieved an extended lifespan of over 1000 cycles. Such good performance can be assigned to the good adsorption and catalysis of the dual-function TiO₂@TiN composite. This work proved that the TiO₂@TiN composite can be an attractive matrix for sulfur cathodes.

Lithium–sulfur (Li–S) batteries are promising candidates for next generation rechargeable batteries because of their high energy density of 2600 W h kg⁻¹.     

A mesoporous tungsten carbide nanostructure as a promising cathode catalyst decreases overpotential in Li–O2 batteries

Lithium–oxygen (Li–O₂) batteries as promising energy storage devices possess high gravimetric energy density and low emission. However, poor reversibility of electrochemical reactions at the cathode significantly affects the electrochemical properties of nonaqueous Li–O₂ batteries, and low charge–discharge efficiency also results in short cycle-life. In this work, functional air cathodes containing mesoporous tungsten carbide nanoparticles for improving the reversibility of positive reactions in Li–O₂ cells are designed. Mesoporous tungsten carbides are synthesized with mesoporous carbon nitride as the reactive template and carbon source. And mesoporous tungsten carbides in cathode materials display better electrochemical performance in Li–O₂ cells in comparison with mesoporous carbon nitride and hard carbon. Tungsten carbide-1 (WC-1) with larger specific surface area promotes reversible formation and decomposition of Li₂O₂ at the cathode and lower charge overpotential (about 0.93 V) at 100 mA g⁻¹, which allows the Li–O₂ cell to run up to 100 cycles. In addition, synergistic interaction between WC-1 and LiI could further decrease the charging overpotentials of Li–O₂ cells and improve the charge–discharge performances of the Li–O₂ cells. These results indicate that mesoporous electrocatalysts can be utilized as promising functional materials for Li–O₂ cells to decrease overpotentials.

Tungsten carbide with large specific surface area catalyzes reversible formation/decomposition of Li₂O₂ with low overpotential in a Li–O₂ cell.     

Polyvinylchloride-derived N,S co-doped carbon as an efficient sulfur host for high-performance Li–S batteries

The intrinsic polysulfide shuttle in lithium–sulfur (Li–S) batteries have significantly limited their practical applications. Conductive carbon materials with heteroatom doping and rich porosity is the most common strategy for the effective prevention of polysulfide shuttle, but are usually obtained with high costs and tedious procedures. Herein, we managed to obtain highly porous N, S-codoped carbon materials (NS-C) through treating waste plastic of polyvinylchloride (PVC) with KOH. The resulting NS-C was revealed to be highly efficient hosts for sulfur cathode, achieving large reversible capacities of 1205 mA h g⁻¹ and 836 mA h g⁻¹ at 0.1C and 1.0C, respectively, and remaining at 550 mA h g⁻¹ after 500 cycles at 1C rate, showing an outstanding cycling stability. The significantly enhanced cycling performance was mainly ascribed to both the hierarchically porous structure and heavy N, S co-dopants, which respectively provided physical blocks and chemical affinity for the efficient immobilization of intermediate lithium polysulfides. The results provide an effective paradigm in the surface chemistry and sulfur cathode materials design for high-performance Li–S batteries and a new application for recycled plastic waste.

The intrinsic polysulfide shuttle in lithium–sulfur (Li–S) batteries have significantly limited their practical applications.     

Ruthenium oxide modified hierarchically porous boron-doped graphene aerogels as oxygen electrodes for lithium–oxygen batteries

Suitable catalysts and reasonable structures for oxygen electrodes can effectively improve the electrochemical performance of lithium–oxygen batteries. In this work, ruthenium oxide modified boron-doped hierarchically porous reduced graphene aerogels (RuO₂-B-HRG) are prepared by a sol–gel and subsequent low temperature annealing method and used as oxygen electrodes. The RuO₂ nanoparticles (5–10 nm) are uniformly anchored in the three-dimensional B-HRG continuous electric network. The RuO₂-B-HRG aerogel possesses a large specific surface area (287.211 m² g⁻¹) and numerous mesopores and micropores. The pores facilitate electrolyte impregnation and oxygen diffusion, and they provide greatly increased accommodation space for the discharge products. Electrochemical tests show that the RuO₂-B-HRG/KB enables the electrode overpotential to decrease, and the rate capability and the cycling stability are enhanced compared with pure HRG. The enhanced performance is ascribed to the bifunctional catalytic activity of RuO₂-B-HRG and its unique three-dimensional porous architecture. The method is proved to be an effective strategy to combine porous carbon materials and nanoscale catalysts as electrodes for Li–O₂ batteries.

Hierarchically porous RuO₂-B-HRG is a great bifunctional catalyst and effectively improve the performance of non-aqueous Li–O₂ batteries.     

Suppressing self-discharge of Li–B/CoS2 thermal batteries by using a carbon-coated CoS2 cathode

Thermal batteries with molten salt electrolytes are used for many military applications, primarily as power sources for guided missiles. The Li–B/CoS₂ couple is designed for high-power, high-voltage thermal batteries. However, their capacity and safe properties are influenced by acute self-discharge that results from the dissolved lithium anode in molten salt electrolytes. To solve those problems, in this paper, carbon coated CoS₂ was prepared by pyrolysis reaction of sucrose at 400 °C. The carbon coating as a physical barrier can protect CoS₂ particles from damage by dissolved lithium and reduce the self-discharge reaction. Therefore, both the discharge efficiency and safety of Li–B/CoS₂ thermal batteries are increased remarkably. Discharge results show that the specific capacity of the first discharge plateau of carbon-coated CoS₂ is 243 mA h g⁻¹ which is 50 mA h g⁻¹ higher than that of pristine CoS₂ at a current density of 100 mA cm⁻². The specific capacity of the first discharge plateau at 500 mA cm⁻² for carbon-coated CoS₂ and pristine CoS₂ are 283 mA h g⁻¹ and 258 mA h g⁻¹ respectively. The characterizations by XRD and DSC indicate that the carbonization process has no noticeable influence on the intrinsic crystal structure and thermal stability of pristine CoS₂.

Suppressing self-discharge of Li–B/CoS₂ thermal batteries through modifying the CoS₂ cathode with a protective carbon coating layer.     

An investigation of Li2TiO3–coke composite anode material for Li-ion batteries

Anode material Li₂TiO₃–coke was prepared and tested for lithium-ion batteries. The as-prepared material exhibits excellent cycling stability and outstanding rate performance. Charge/discharge capacities of 266 mA h g⁻¹ at 0.100 A g⁻¹ and 200 mA h g⁻¹ at 1.000 A g⁻¹ are reached for Li₂TiO₃–coke. A cycling life-time test shows that Li₂TiO₃–coke gives a specific capacity of 264 mA h g⁻¹ at 0.300 A g⁻¹ and a capacity retention of 92% after 1000 cycles of charge/discharge.

Anode material Li₂TiO₃–coke was prepared and tested for lithium-ion batteries. The as-prepared material exhibits excellent cycling stability and outstanding rate performance.     

Nitrogen,sulfur-codoped micro–mesoporous carbon derived from boat-fruited sterculia seed for robust lithium–sulfur batteries

The diverse textures and tunable surface properties of abundant bioresources offer great opportunities to utilize biochar materials as sulfur hosts for naturally boosting the electrochemical performances of Li–S batteries. Herein, a N, S-codoped micro–mesoporous carbon was synthesized from boat-fruited sterculia seed, and used as a sulfur host matrix for Li–S batteries. After sulfur infiltration (≈62% sulfur) and cell assembly, the obtained S/NSBC cathode shows outstanding discharge–charge performance, good rate capability, and especially long cycling stability. A high initial discharge capacity of 1478 mA h g⁻¹ was achieved at 0.1C, and the reversible discharge capacity was still retained at 649 mA h g⁻¹ after 500 cycles at 0.5C with ultralow decay rate of 0.08% per cycle, and especially zero-capacity-decay after 300 cycles. Such superior electrochemical performance of S/NSBC cathode is attributed to the synergy of the unique 3D conductive micro–mesoporous frameworks and huge N, S-codoped polar surface within the carbon matrix, which can physically confine the dissolved polysulfides within the pore structures, and chemically anchor the polysulfides through chemical interaction between lithium polysulfides and N and S sites, thus enabling the favorable reaction kinetics, efficient utilization of sulfur, and effective mitigation of polysulfide diffusion and shuttling within the cathode. This work well manifests the great feasibility and superiority of utilizing bioresources for high performance Li–S batteries.

Physical confinement and chemical adsorption of polysulfides on boat-fruited sterculia seed derived nitrogen, sulfur-codoped micro–mesoporous carbon for robust lithium–sulfur batteries.     

Three-dimensional ordered macroporous ZIF-8 nanoparticle-derived nitrogen-doped hierarchical porous carbons for high-performance lithium–sulfur batteries

Lithium–sulfur (Li–S) batteries have attracted considerable attention due to their ultra-high specific capacity and energy density. However, there are still problems to be resolved such as poor conductivity of sulfur cathodes and dissolution of polysulfides in organic electrolytes. Herein, a novel ZIF-8-derived nitrogen-doped connected ordered macro–microporous carbon (COM-MPC) was developed by a dual solvent-assisted in situ crystallization method within a face-centered cubic stacking sphere template, which acts as an advanced sulfur host for enhanced Li–S battery performance. Compared with the conventional predominant microporous C-ZIF-8, the unique hierarchical macro–microporous structure with nitrogen doping not only renders polysulfide intermediates enhanced entrapment by confining the effect of micropores and chemisorption of doping N atoms, but also facilitates electrolyte accessibility and efficient ion transport owing to the ordered macroporous structure. Benefitting from this, the COM-MPC@S cathode delivers a high initial specific capacity of 1498.5 mA h g⁻¹ and a reversible specific capacity of 1118.9 mA h g⁻¹. Moreover, the COM-MPC@S cathode exhibits 82.3% of capacity retention within 10th to 50th cycle at 0.5C and a large capacity of 608.5 mA h g⁻¹ after 50 cycles at a higher rate of 1C, and this enhanced cycling stability and rate capability demonstrate great practical application potential in Li–S battery systems.

Lithium–sulfur (Li–S) batteries have attracted considerable attention due to their ultra-high specific capacity and energy density.     

Hydrothermal-template synthesis and electrochemical properties of Co3O4/nitrogen-doped hemisphere-porous graphene composites with 3D heterogeneous structure

Despite the high capacity of Co₃O₄ employed in lithium-ion battery anodes, the reduced conductivity and grievous volume change of Co₃O₄ during long cycling of insertion/extraction of lithium-ions remain a challenge. Herein, an optimized nanocomposite, Co₃O₄/nitrogen-doped hemisphere-porous graphene composite (Co₃O₄/N-HPGC), is synthesized by a facile hydrothermal-template approach with polystyrene (PS) microspheres as a template. The characterization results demonstrate that Co₃O₄ nanoparticles are densely anchored onto graphene layers, nitrogen elements are successfully introduced by carbamide and the nanocomposites maintain the hemispherical porous structure. As an anode material for lithium-ion batteries, the composite material not only maintains a relatively high lithium storage capacity (the first discharge specific capacity can reach 2696 mA h g⁻¹), but also shows significantly improved rate performance (1188 mA h g⁻¹ at 0.1 A g⁻¹, 344 mA h g⁻¹ at 5 A g⁻¹) and enhanced cycling stability (683 mA h g⁻¹ after 500 cycles at 1 A g⁻¹). The enhanced electrochemical properties of Co₃O₄/N-HPGC nanocomposites can be ascribed to the synergistic effects of Co₃O₄ nanoparticles, novel hierarchical structure with hemisphere-pores and nitrogen-containing functional groups of the nanomaterials. Therefore, the developed strategy can be extended as a universal and scalable approach for integrating various metal oxides into graphene-based materials for energy storage and conversion applications.

The Co₃O₄/N-HPGC nanocomposites synthesized by a hydrothermal-template approach with polystyrene microspheres as the template possess excellent electrochemical performance.     

Sulfur encapsulated in thermally reduced graphite oxide as a cathode for Li–S batteries

Rechargeable Li–S batteries are receiving ever-increasing attention due to their high theoretical energy density and inexpensive raw sulfur materials. However, their practical applications have been hindered by short cycle life and limited power density owing to the poor electronic conductivity of sulfur species, diffusion of soluble polysulfide intermediates (Li₂S_n, n = 4–8) and the large volume change of the S cathode during charge/discharge. Optimizing the carbon framework is considered as an effective approach for constructing high performance S/carbon cathodes because the microstructure of the carbon host plays an important role in stabilizing S and restricting the “shuttle reaction” of polysulfides in Li–S batteries. In this work, reduced graphite oxide (rGO) materials with different oxidation degree were investigated as the matrix to load the active material by an in situ thermally reducing graphite oxide (GO) and intercalation strategy under vacuum at 600 °C. It has been found that the loaded amount of S embedded in the rGO layer for the S/carbon cathode and its electrochemical performance strongly depended on the oxidation degree of GO. In particular, on undergoing CS₂ treatment, the rGO–S cathode exhibits extraordinary performances in Li–S batteries. For instance, at a current density of 0.2 A g⁻¹, the optimized rGO–S cathode shows a columbic efficiency close to 100% and retains a capacity of around 750 mA h g⁻¹ with progressive cycling up to over 250 cycles.

Reduced graphite oxide materials with different oxidation degree were investigated as the matrix to load sulfur by an in situ thermal-reduction and intercalation strategy. The C/S composite cathode exhibits a superior electrochemical properties.