Poly(anthraquinonyl sulfide) cathode for potassium-ion batteries

Potassium-ion batteries (KIBs) are a promising sustainable energy storage technology due to the high abundance and low cost of potassium. Carbon anode materials for KIBs have seen great successes, but the development of cathode materials is yet to catch up. In this study, poly(anthraquinonyl sulfide) (PAQS) is evaluated as a cathode material for KIBs. It exhibits a high reversible capacity of 200 mAh/g, which is the highest value for a potassium storage cathode material. The cell shows two slopes averaged at 2.1 and 1.6 V vs. K⁺/K. It shows a good cycling performance with the capacity retention of 75% after 50 cycles at a rate of C/10. These preliminary results indicate that PAQS is a promising cathode material for KIBs.     

Cotton-derived oxygen/sulfur co-doped hard carbon as advanced anode material for potassium-ion batteries

Hard carbon is regarded as promising anode materials for potassium-ion batteries(KIBs)owing to their low price and easy availability.However,the limited rate capability still needs to be improved.Herein,we demonstrate the fabrication of oxygen/sulfur co-doped hard carbon through a facile hydrolyzationsulfuration process of skimmed cotton.The simultaneous dopants significantly improve potassium ion diffusion rate.When served as the anode for KIBs,this hydrolyzed hard carbon delivered a high reversible capacity(409 mAh/g at 0.1 A/g),superior rate capability(135 mAh/g at 2 A/g)and excellent cyclability(about 120 mAh/g overt 500 cycles at 2 A/g).This work provides a facile strategy to prepare low-cost doped-hard carbon with superior potassium storage property.     

Ca_2Nb_2O_7 as a Novel Open-framework Anode Material for Potassium-ion Batteries

Potassium-ion batteries(KIBs)are a promising alternative to Lithium-based energy storage systems owning to the low cost and rich abundance of potassium resources,but are facing challenges in designing low-cost hosts that can reversibly accommodate large-size K⁺with fast diffusion kinetics.Herein,we report a novel 3D inorganic open framework of Ca₂Nb₂O₇(CNO)as an anode for KIBs.The open framework structure affords interstitial vacancies available for storing K⁺and allows a facile diffusion of K⁺,thus resulting in excellent structural stability and fast reaction kinetics.The CNO electrode delivers a reversible specific capacity of 65.3 and 52.2 mAh/g at 5 and 10 mA/g,respectively.Moreover,CNO exhibits excellent long-term cyclability with 92.53%capacity retention over 700 cycles at 10 mA/g.This will trigger more investigations into open-framework-based materials for stable and fast KIBs.     

Electrolyte Chemistry Enables Simultaneous Stabilization of Potassium Metal and Alloying Anode for Potassium‐Ion Batteries

Alloying anodes are promising high‐capacity electrode materials for K‐ion batteries (KIBs). However, KIBs based on alloying anodes suffer from rapid capacity decay due to the instability of K metal and large volume expansion of alloying anodes. Herein, the effects of salts and solvents on the cycling stability of KIBs based on a typical alloying anode such as amorphous red phosphorus (RP) are investigated, and the potassium bis(fluorosulfonyl)imide (KFSI) salt‐based carbonate electrolyte is versatile to achieve simultaneous stabilization of K metal and RP electrodes for highly stable KIBs. This salt‐solvent complex with a moderate solvation energy can alleviate side reactions between K metal and the electrolyte and facilitate K⁺ ion diffusion/desolvation. Moreover, robust SEI layers that form on K metal and RP electrodes can suppress K dendrite growth and resist RP volume change. This strategy of electrolyte regulation can be applicable to other alloying anodes for high‐performance KIBs.     

High reversible capacity and rate capability of ZnCo2O4/graphene nanocomposite anode for high performance lithium ion batteries

A facile and straightforward method was adopted to synthesize ZnCo₂O₄/graphene nanocomposite anode. In the first step, pure ZnCo₂O₄ nanoparticles were synthesized using urea-assisted auto-combustion synthesis followed by annealing at a low temperature of 400 °C. In the second step, in order to synthesize ZnCo₂O₄/graphene nanocomposite, the obtained pure ZnCo₂O₄ nanoparticles were milled with 10 wt% reduced graphene nanosheets using high energy spex mill for 30 s. The ZnCo₂O₄ nanoparticles, with particle sizes of 25–50 nm, were uniformly dispersed and anchored on the reduced graphene nanosheets. Compared with pure ZnCo₂O₄ nanoparticles anode, significant improvements in the electrochemical performance of the nanocomposite anode were obtained. The resulting nanocomposite delivered a reversible capacity of 1124.8 mAh g⁻¹ at 0.1 C after 90 cycles with 98% Coulombic efficiency and high rate capability of 515.9 mAh g⁻¹ at 4.5 C, thus exhibiting one of the best lithium storage properties among the reported ZnCo₂O₄ anodes. The significant enhancement of the electrochemical performance of the nanocomposite anode could be credited to the strong synergy between ZnCo₂O₄ and graphene nanosheets, which maintain excellent electronic contact and accommodate the large volume changes during the lithiation/delithiation process.     

Facile simultaneous polymerization enabled in-situ confinement of size-tailored GeO2 nanocrystals in continuous S-Doped carbons for lithium storage

GeO₂ is a promising anode material for lithium ion batteries due to its high theoretical capacity (1126 mAh g^?1 for reversibly storing 4.4 Li⁺), and moderately low operating voltage (<1.5 V). Nevertheless, the fabrication of truly durable GeO₂ anode with satisfactory rate capability and cycling stability remains a big challenge because of its inherent low conductivity, and the large volume expansion upon charge-discharge that causes severe capacity fading. In this study, an innovative nanostructure with size-adjustable GeO₂ nanoparticles (16–26 nm) embedded in continuous S-doped carbon (GeO₂/S-doped carbon, GSC) has been successfully fabricated via a facile in-situ simultaneous polymerization method followed by heat treatment. The electrochemical results indicate that the as-prepared GSC composites show high reversible capacity (672.9 mAh g^?1 at 50 mA g^?1), superior rate capability (332.9 mAh g^?1 at 1000 mA g^?1), and long-term cycle life (179 mAh g^?1 after 500 cycles at 1000 mA g^?1) as anode materials for lithium ion batteries. The excellent electrochemical performance of GSC nanocomposites could be ascribed to the homogeneous and continuous S-doped carbon matrix, which provides shortened ion diffusion pathway, increased electrical conductivity, enhanced structural stability, and introduced surface/interface property.     

State-of-the-art anodes of potassium-ion batteries: synthesis,chemistry, and applications

The growing demand for green energy has fueled the exploration of sustainable and eco-friendly energy storage systems. To date, the primary focus has been solely on the enhancement of lithium-ion battery (LIB) technologies. Recently, the increasing demand and uneven distribution of lithium resources have prompted extensive attention toward the development of other advanced battery systems. As a promising alternative to LIBs, potassium-ion batteries (KIBs) have attracted considerable interest over the past years owing to their resource abundance, low cost, and high working voltage. Capitalizing on the significant research and technological advancements of LIBs, KIBs have undergone rapid development, especially the anode component, and diverse synthesis techniques, potassiation chemistry, and energy storage applications have been systematically investigated and proposed. In this review, the necessity of exploring superior anode materials is highlighted, and representative KIB anodes as well as various structural construction approaches are summarized. Furthermore, critical issues, challenges, and perspectives of KIB anodes are meticulously organized and presented. With a strengthened understanding of the associated potassiation chemistry, the composition and microstructural modification of KIB anodes could be significantly improved.

State-of-the-art tendency, present critical issues and future opportunities of anode active materials in potassium ion batteries are systematically summarized.     

Co2P/Sn4P3 particle encapsulated in N,P codoped carbon nanocubes for efficient sodium storage

Phosphorus-based materials as the anode for sodium-ion batteries have drawn extensive attention because of their high theoretical capacity and low insertion potential. Nevertheless, the severe volume variation and low electric conductivity hindered their further practical applications. Herein, a novel Co₂P/Sn₄P₃ hybrid encapsulated in carbon nanocubes was fabricated by a coprecipitation method followed by phosphating progress. Accompanying with the N, P codoping and abundant grain boundaries, which facilitates electric transport and provides rich active sites, the as-synthesized Co₂P/Sn₄P₃@C anode delivered a high charge specific capacity of 185.6 mA h g^?1 after 400 cycles at the current density of 1000 mA g^?1 and outstanding cycling stability with a high capacity retention of 86.9%. Kinetics exploration indicated that the capacity was governed by the surface pseudo-capacitive controlled process due to the abundant defects originated from heteroatom doping and grain boundaries.     

Binder-free carbon-coated nanocotton transition metal oxides integrated anodes by laser surface ablation for lithium-ion batteries

In this paper, an efficient laser surface ablation strategy for producing binder-free carbon-coated nanocotton CoO-Co integrated anode is reported. The fabrication process introduces in-situ growing nanocotton-like CoO on the surface of Co foil via ablating with a nanosecond laser. After that, coated with dopamine as carbon source, the CoO-Co composite foil is heated in Argon atmosphere to form a CoO@C-Co foil as an anode of LIB. The laser surface ablation exhibits high fabrication speed (~10 minutes) and significantly reduces the processing time. The obtained binder-free CoO@C-Co integrated anode shows a unique cotton-like villous structure with large specific surface area and an active material/current collector integrated architecture, which provides a stabilized rapid electronic conduction path. When tested as an anode for LIBs, the CoO@C-Co integrated anode possesses superior performance: First discharge capacity of 1301.5 mAh g⁻¹ is achieved at a current density of 0.1 A g⁻¹. Also at a high current density of 1.5 A g⁻¹, the second discharge capacity of 791.7 mAh g⁻¹ is achieved. After 800 cycles, reversible capacities of 799.8 mAh g⁻¹ can still be achieved with an average coulombic efficiency of nearly 100%. In addition, this strategy is suitable for the production of other carbon coated transition metal oxides integrated anodes, such as NiO@C-Ni, Fe₂O₃/Fe₃O₄@C-Fe, and CuO/Cu₂O@C-Cu integrated anodes.     

Interconnected MnCO3 nanostructures anchored on carbon fibers with enhanced potassium storage performance

Potassium-ion batteries (PIBs) have gained considerable attention in the past decade because of the rich potassium reserves in our planet. However, the development of anode materials is still a major challenge because of the hard reaction kinetics and poor cycling stability in the insertion/extraction process. Herein, we report interconnected MnCO₃ nanostructures anchored on carbon fibers (MnCO₃/CF) composites as anode for PIBs. The MnCO₃/CF can be directly used as anode on PIBs, avoiding the addition of polyvinylidene fluoride (PVDF) binders and the complicated slurry coating onto copper process. The nanosized MnCO₃ nanostructures are interconnected with each other, which can provide short ions diffusion length during the charge/discharge process. The MnCO₃ nanostructures are firmly anchored on the surface of CF through C–Mn bonds, ensuring cycling stability. Also, the CF with good electronic conductivity guarantees fast electrons transportation in MnCO₃/CF system. Benefiting from the advantageous features mentioned earlier, the MnCO₃/CF anode behaves enhanced potassium storage performance compared with that of pure MnCO₃ anode. The MnCO₃/CF anode delivers a high capacity of 462 mAh/g at 50 mA/g after 100 cycles, whereas the capacity of pure MnCO₃ anode is only 134 mAh/g at 50 mA/g after 80 cycles. This work demonstrates the prospect of metal carbonate as anode materials for PIBs and provides a useful strategy to design advanced anode materials for PIBs.     

Energy-saving seawater electrolysis for hydrogen production

The change in the polarization potentials of anode and cathode due to pH change on electrode surfaces during galvanostatic polarization was examined in 0.5 M NaCl solutions of different pH. On the basis of these results, feeding of the anolyte after oxygen evolution to the cathode compartment for hydrogen production was examined for energy-saving seawater electrolysis. This was assumed to prevent the occurrence of a large pH difference on cathode and anode in electrolysis of neutral solution if sufficient H⁺ is permeated through the membrane. The cell performance was examined using Nafion 115 or Selemion HSF membranes for separation of anode and cathode compartments. The permeation fraction of H⁺ with Nafion 115 was 45–65% in 0.5 M NaCl and was about 90% in 0.25 M Na₂SO₄. These values were smaller than 97% necessary for prevention of the occurrence of pH difference on cathode and anode. The permeation fraction of H⁺ with Selemion HSF became more than 97% during electrolysis of 0.025 M Na₂SO₄, and the cell voltage was kept at low values. These results indicate the effectiveness of our seawater feeding system if the 97% H⁺ permeation fraction through the membrane is attained. Contribution to the Fall Meeting of the European Materials Research Society, Symposium D: 9th International Symposium on Electrochemical/Chemical Reactivity of Metastable, Warsaw, 17th-21st September, 2007.     

Impact of reforming catalyst on the anodic polarisation resistance in single-chamber SOFC fed by methane

This paper emphasises the electrochemical and catalytic properties of a Ni–10% GDC (10% gadolinium-doped ceria) cermet anode of a single-chamber solid oxide fuel cell (SC-SOFC). Innovative coupling of electrochemical impedance spectroscopy with gas chromatography measurements was carried out to characterise the anode material using an operando approach. The experiments were conducted in a symmetric anode/electrolyte/anode cell prepared by slurry coating resulting in 100 μm-thick anode layers. The electrochemical performance was assessed using a two-electrode arrangement between 400 °C and 650 °C, in a methane-rich atmosphere containing CH₄, O₂ and H₂O in a 14:2:6 volumetric ratio. The insertion of a Pt–CeO₂ based catalyst with high specific surface area inside the cermet layer was found to promote hydrogen production from the Water Gas Shift reaction and consequently to improve the electrochemical performances. Indeed, a promising polarisation resistance value of 12 Ω cm² was achieved at 600 °C with a catalytic loading of only 15 wt.%.     

High capacity SnxSbyCuz composite anodes for lithium ion batteries

To increase the volumetric discharge capacity of negative electrode for rechargeable lithium batteries, a composite anode Sn_xSb_yCu_z has been synthesized by using high energy mechanical ball milling method. The synthesized composite anode materials have been characterized by X-ray diffraction and SEM analysis. The charge/discharge characteristics of the fabricated coin cells have been evaluated galvanostatically in the potential range 0.01–2 V using 1 M LiPF₆ in 1:1 EC/DEC as electrolyte. Results indicate that the composition with 90 wt% Sn, 8 wt% Sb and 2 wt% Cu delivers an average discharge capacity of 740 mAh g⁻¹ over the investigated 50 cycles which is a potential candidate for use as an anode material for lithium rechargeable cells.     

Sr2NiMoO6−δ as anode material for LaGaO3-based solid oxide fuel cell

The double-perovskite Sr₂NiMoO_6−δ (SNMO) was investigated as an anode material of a solid oxide fuel cell (SOFC). With a 300 μm thick La_0.9Sr_0.1Ga_0.8Mg_0.2O_3−σ (LSGM) disk as electrolyte and Ba_0.5Sr_0.5Co_0.8Fe_0.2O_3−δ as the cathode, the SNMO anode showed power densities of 819 mW cm⁻² in hydrogen at 1123 K. Moreover, there was no buffer layer between anode and electrolyte, which would reduce design techniques and save design cost. After test no chemical reaction was discovered between anode and electrolyte. The anode exhibited good conductivity and the value was around 60 S cm⁻¹ in H₂. Also it had almost linear thermal expansion from room temperature to 1253 K and the average thermal expansion coefficient was about 12.14 × 10⁻⁶ K⁻¹, which was quite close to that of La_0.9Sr_0.lGa_0.8Mg_0.2O₃ (12.17 × 10⁻⁶ K⁻¹) electrolyte.     

Power-generating property of direct CH4 fueled SOFC using LaGaO3 electrolyte

A composite anode of NiFe–MgO (2.5 wt.%)–La_0.9Sr_0.1Ga_0.8Mg_0.2O₃ (LSGM) (10 wt.%) for solid oxide fuel cells using directly CH₄ as fuel was studied. Compared with previously reported NiFe–LSGM (10 wt.%) cermet anode, the NiFe–MgO–LSGM anode exhibited superior power generation performance, stability under CH₄ atmosphere at 973 K, and high tolerance against the carbon deposition. These improvements by the additives are explained by the increase in basic property of anode material. The anode activity of NiFe–MgO–LSGM cermet for CH₄ fuel is still lower than that for H₂ one. However, comparing with that of NiFe–LSGM cermet, anodic overpotential slightly decreased by the addition of MgO, suggesting the improved surface activity.     

Improvement in performance of a direct ethanol fuel cell: Effect of sulfuric acid and Ni-mesh

A direct ethanol fuel cell (DEFC) is developed with low catalyst loading at anode and cathode compared to that reported in the literature. Pt/Ru (40%:20% by wt.)/C and Pt-black were used as anode and cathode catalyst with loadings in the range of 0.5–1.2 mg/cm². The temperatures of anode and cathode were varied from 34 °C to 110 °C, and the pressure was maintained at 1 bar. Although low catalyst loading was used, the cell performance is enhanced by 40–50% with the use of low concentration of sulfuric acid in ethanol and Ni-mesh as current collector at the anode. The power density 15 mW/cm² at 32 mA/cm² of current density is obtained from the single cell with 0.5 mg/cm² loading of Pt–Ru/C at anode (90 °C) and Pt-black at cathode (110 °C). The performance of DEFC increases with the increase in ethanol and sulfuric acid concentrations, electrocatalyst loadings up to 1 mg cm⁻² at anode and cathode. However, the performance of DEFC decreases with further increase in electrocatalyst loading.     

Kinetics for the Oxygen Evolution Reaction and Application of the Ti/SnO<Subscript>2</Subscript> + RuO<Subscript>2</Subscript> + MnO<Subscript>2</Subscript> Electrode

A Ti/SnO₂ + RuO₂ + MnO₂ electrode was prepared by thermal decomposition of their salts. Results from SEM and XPS analyses, respectively, indicate that the coating layer exhibits a compact structure and the oxidation state of Mn in the coating layer is +IV. The experimental activation energy for the oxygen evolution reaction, which increased linearly with increasing overpotential, is about 8 kJ⋅mol⁻¹ at the equilibrium potential (η=0). The electrocatalytic characteristics of the anode are discussed in terms of ligand substitution reaction mechanisms (Sn1 and Sn2). It was found that the transition state for oxygen evolution at the anode in acidic solution follows a dissociative mechanism (Sn1 reaction). The Ti/SnO₂ + RuO₂ + MnO₂ anode in conjunction with UV illumination was used to degrade phenol solutions, where the concentration of phenol remaining was determined by high-performance liquid chromatography (HPLC). The results indicate that the degradation efficiency of phenol on the anode can reach 96.3% after photoelectrocatalytic oxidation for 3 h.     

A novel single phase cathode material for a proton-conducting SOFC

A novel single phase BaCe_0.5Bi_0.5O_3 ? δ (BCB) was employed as a cathode material for a proton-conducting solid oxide fuel cell (SOFC). The single cell, consisting of a BaZr_0.1Ce_0.7Y_0.2O_3 ? δ (BZCY7)-NiO anode substrate, a BZCY7 anode functional layer, a BZCY7 electrolyte membrane and a BCB cathode layer, was assembled and tested from 600 to 700 °C with humidified hydrogen (～3% H₂O) as the fuel and the static air as the oxidant. An open-circuit potential of 0.96 V and a maximum power density of 321 mW cm^?2 were obtained for the single cell. A relatively low interfacial polarization resistance of 0.28Ω cm² at 700 °C indicated that the BCB was a promising cathode material for proton-conducting SOFCs.     

Fabrication by Co-extrusion and electrochemical characterization of micro-tubular hollow fibre solid oxide fuel cells

A phase inversion process was used to co-extrude cerium–gadolinium oxide (Ce_0.9Gd_0.1O_1.95)/NiO–CGO dual-layer hollow fibres (HF), which were then sintered to form, respectively, the electrolyte and high porosity anode precursor of a solid oxide fuel cell (SOFC) with anode inner diameter of 0.8 mm. Graded CGO–lanthanum strontium cobalt ferrite (La_0.6Sr_0.4Fe_0.8Co_0.2O₃) cathode layers were then painted onto the CGO electrolyte to form a micro-tubular HF-SOFC. With a carefully designed anode current collector, this produced maximum power densities of 1186–5864 W m^? 2 at 450–570 °C. High magnification imaging analysis revealed large three-phase boundary regions within the anode, a dense electrolyte layer and clearly highlighted the multiple CGO–LSCF cermet and pure LSCF cathode layers. The performance of the HF-SOFC with a twenty millimetre active length showed no degradation after four thermal cycles between 300 °C and 570 °C.     

Activation of a single-chamber solid oxide fuel cell by a simple catalyst-assisted in-situ process

Initialization is a critical processing step that has thus far limited the application of the single-chamber solid oxide fuel cell (SC-SOFC). In-situ initialization of a SC-SOFC with a nickel-based anode by methane–air mixtures was investigated. Porous Ru–CeO₂ was used as a catalyst layer over a Ni-ScSZ cermet anode. Catalytic testing demonstrated Ru–CeO₂ had high activity for methane oxidation. The Ru in the catalyst layer catalyzed the formation of syngas, which successfully reduced the nickel oxide to metallic nickel in the anode. Single cells with a La_0.8Sr_0.2MnO₃ (LSM) cathode, initialized by this in-situ reduction method, delivered peak power densities of 205 and 327 mW cm⁻² at 800 °C and 850 °C, respectively. Such performances were better than those of the cell without the Ru–CeO₂ catalyst layer that was initialized by an ex-situ reduction method were.