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Lithium-rich, cobalt-free oxides are promising potential positive electrode materials for lithium-ion batteries because of their high energy density, lower cost, and reduced environmental and ethical concerns. However, their commercial breakthrough is hindered because of their subpar electrochemical stability. This work studies the effect of aluminum doping on Li1.26Ni0.15Mn0.61O2 as a lithium-rich, cobalt-free layered oxide. Al doping suppresses voltage fade and improves the capacity retention from 46% for Li1.26Ni0.15Mn0.61O2 to 67% for Li1.26Ni0.15Mn0.56Al0.05O2 after 250 cycles at 0.2 C. The undoped material has a monoclinic Li2MnO3-type structure with spinel on the particle edges. In contrast, Al-doped materials (Li1.26Ni0.15Mn0.61-xAlxO2) consist of a more stable rhombohedral phase at the particle edges, with a monoclinic phase core. For this core-shell structure, the formation of Mn3+ is suppressed along with the material's decomposition to a disordered spinel, and the amount of the rhombohedral phase content increases during galvanostatic cycling. Whereas previous studies generally provided qualitative insight into the degradation mechanisms during electrochemical cycling, this work provides quantitative information on the stabilizing effect of the rhombohedral shell in the doped sample. As such, this study provides fundamental insight into the mechanisms through which Al doping increases the electrochemical stability of lithium-rich cobalt-free layered oxides.

A new cathode material, FeS2-decorated carbon nanofiber (CNF), is proposed for Li-S batteries. The structure and physicochemical properties of the material have been engineered to enhance the poor cycling stability typically displayed by sulfur composites. The composite material shows a complex architecture with a matrix of CNF hosting the sulfur and core-shell FeS2 nanoparticles acting as a catalyst for a solid phase conversion-type reaction. This cathode delivers high discharge capacities of 864, 798, 689, 595 and 455 mAhg−1 at C/10, C/5, C/2, 1C and 2C, respectively, with a stable capacity retention of 87% at 2C after 300 cycles. FeS2-decorated CNF has been characterised using several techniques, including in-situ battery measurements at the ALBA synchrotron facility and high-throughput microscopy, giving valuable insights into its charge/discharge reaction mechanism. The excellent performance obtained is combined with the use of just low-cost and abundant elements such as iron, sulfur and carbon, which makes this battery highly promising for the next generation of electrochemical energy storage devices.

Lithium–sulfur batteries (LSBs) with high energy density have the potential to replace current commercial lithium-ion batteries. However, the shuttle effect and the low conversion kinetics of lithium polysulfide (LiPS) remain the main challenges in the development of LSBs. In this study, a metal-free and simple-to-prepare carbon nitride with a high surface area and tubular morphology (CN-nt) is used as the sulfur host for LSBs. Due to its unique nanostructure and rich active sites, it not only effectively disperses the active sulfur material and anchors soluble polysulfide species, but it also promotes the nucleation process of Li2S, thus achieving fast and sustainable Li-S redox reactions. Experimental results show that the obtained S@CN-nt electrodes exhibit a high sulfur utilization of 1296.2 mAh g−1 at 0.1 C and a significant rate capability of 689.4 mAh g−1 at the high current rate of 3C. More importantly, the capacity retention reaches 87.7% after 500 cycles. This simple strategy of engineering unique carbon-based nanostructured hosts can inspire new ideas for developing cost-effective and metal-free host materials for sulfur-based batteries.

The electrochemical performance of room-temperature sodium-sulfur batteries (SSBs) is limited by slow reaction kinetics and sulfur loss in the form of sodium polysulfides (SPSs). Here, it is demonstrated that through electron spin polarization, at no additional energy cost, an external magnetic field (M on) generated by a permanent magnet can significantly improve the SPSs adsorption capacity and reaction dynamics of a ferrimagnetic sulfur host. More specifically, the preparation of a carbon nanofiber/CoFe2O4/S (CNF/CoFe2O4/S) cathode with unprecedented performance and stability at ambient temperature is detailed when M on. It is experimentally and theoretically demonstrated that the magnetic field polarizes the electrons of Co ions, enhancing the adsorption of SPSs and their catalytic conversion. CNF/CoFe2O4/S cathodes with spin polarization provide unprecedented decay rates down to 0.0039% per cycle at 1.0 C for 2700 cycles. The performance of SSBs is further tested, which has 248 mAh g−1 under 1.0 C after 100 cycles when M on. Furthermore, it is evidenced that even when removing the external magnetic field, the magnetic polarization effect persists, opening the door for practical applications. This study not only demonstrates an effective strategy to improve electrochemical performance in SSBs, but also contributes to the enrichments of spin effects in the fields of electrocatalysis.

An AB2X4 spinel structure, with tetrahedral A and octahedral B sites, is a paradigmatic class of catalysts with several possible geometric configurations and numerous applications, including polysulfide conversion in metal-sulfur batteries. Nonetheless, the influence of the geometric configuration and composition on the mechanisms of catalysis and the precise manner in which spinel catalysts facilitate the conversion of polysulfides remain unknown. To enable controlled exposure of single active configurations, herein, Cotd2+ and Cooh3+ in Co3O4 catalysts for sodium polysulfide conversion are in large part replaced by Fetd2+ and Feoh3+, respectively, generating FeCo2O4 and CoFe2O4. Through an examination of electrochemical activation energies, the characterization of symmetric cells, and theoretical calculations, we determine that Cooh3+ serves as the active site for the breaking of S-S bonds, while Cotd2+ functions as the active site for the formation of S-Na bonds. The current study underlines the subtle relationship between activity and geometric configurations of spinel catalysts, providing unique insights for the rational development of improved catalysts by optimizing their atomic geometric configuration.

Co-free Li-rich layered oxides are gaining interest as feasible positive electrode materials in lithium-ion batteries (LIBs) in terms of energy density, cost reduction, and alleviating safety concerns. Unfortunately, their commercialization is hindered by severe structural degradation that occurs during electrochemical operation. The study at hand demonstrates advanced structural engineering of a Li-rich Co-free oxide with composition Li1.1Ni0.35Mn0.55O2 by spray pyrolysis and subsequent calcination of an aqueous precursor, creating a segregated structure of two distinct layered phases with space groups R3̅m (rhombohedral) and C2/m (monoclinic). This particular structure was investigated with powder neutron diffraction, high-resolution analytical transmission electron microscopy imaging, and electron energy loss spectroscopic characterization. This complex structure contributes to the high electrochemical stability and good rate capability observed for this compound (160 mAh/g at C/3 and 100 mAh/g at 1C). These results provide new insights into the feasibility of developing and commercializing cobalt-free positive electrode materials for LIBs.

The shuttling of soluble lithium polysulfides (LiPS) and the sluggish Li–S conversion kinetics are two main barriers toward the practical application of lithium–sulfur batteries (LSBs). Herein, we propose the addition of copper selenide nanoparticles at the cathode to trap LiPS and accelerate the Li–S reaction kinetics. Using both computational and experimental results, we demonstrate the crystal phase and concentration of copper vacancies to control the electronic structure of the copper selenide, its affinity toward LiPS chemisorption, and its electrical conductivity. The adjustment of the defect density also allows for tuning the electrochemically active sites for the catalytic conversion of polysulfide. The optimized S/Cu1.8Se cathode efficiently promotes and stabilizes the sulfur electrochemistry, thus improving significantly the LSB performance, including an outstanding cyclability over 1000 cycles at 3 C with a capacity fading rate of just 0.029% per cycle, a superb rate capability up to 5 C, and a high areal capacity of 6.07 mAh cm–2 under high sulfur loading. Overall, the present work proposes a crystal phase and defect engineering strategy toward fast and durable sulfur electrochemistry, demonstrating great potential in developing practical LSBs., Peer Reviewed, Postprint (author's final draft)

Lithium-Sulfur is a promising technology for the next generation of batteries and research efforts for early-stage prototype implementation increased in recent years. For the development of a suitable Battery Management System, a state estimator is required; however, lithium-sulfur behavior presents a large non-observable region that may difficult the convergence of the state estimation algorithm leading to large errors or even instability. A dual Extended Kalman Filter is proposed to circumvent the non-observability region. This objective is achieved by combining a parameter estimation algorithm with a cell model that includes non-linear behavior such as self-discharge and cell degradation. The resulting dual Kalman filter is applied to lithium–sulfur batteries to estimate their State-of-Charge incorporating the effects of degradation, temperature, and self-discharge deviations., Peer Reviewed, Objectius de Desenvolupament Sostenible::7 - Energia Assequible i No Contaminant::7.b - Per a 2030, ampliar la infraestructura i millorar la tecnologia per tal d’oferir serveis d’energia moderns i sos­tenibles per a tots els països en desenvolupament, en particular els països menys avançats, els petits estats insulars en desenvolupament i els països en desenvolupament sense litoral, d’acord amb els programes de suport respectius, Objectius de Desenvolupament Sostenible::7 - Energia Assequible i No Contaminant, Postprint (published version)

The shuttling of soluble lithium polysulfides (LiPS) and the sluggish Li-S conversion kinetics are two main barriers toward the practical application of lithium-sulfur batteries (LSBs). Herein, we propose the addition of copper selenide nanoparticles at the cathode to trap LiPS and accelerate the Li-S reaction kinetics. Using both computational and experimental results, we demonstrate the crystal phase and concentration of copper vacancies to control the electronic structure of the copper selenide, its affinity toward LiPS chemisorption, and its electrical conductivity. The adjustment of the defect density also allows for tuning the electrochemically active sites for the catalytic conversion of polysulfide. The optimized S/Cu1.8Se cathode efficiently promotes and stabilizes the sulfur electrochemistry, thus improving significantly the LSB performance, including an outstanding cyclability over 1000 cycles at 3 C with a capacity fading rate of just 0.029% per cycle, a superb rate capability up to 5 C, and a high areal capacity of 6.07 mAh cm-2 under high sulfur loading. Overall, the present work proposes a crystal phase and defect engineering strategy toward fast and durable sulfur electrochemistry, demonstrating great potential in developing practical LSBs.

The shuttling behavior and sluggish conversion kinetics of intermediate lithium polysulfides (LiPS) represent the main obstacles to the practical application of lithium–sulfur batteries (LSBs). Herein, an innovative sulfur host is proposed, based on an iodine-doped bismuth selenide (I-Bi2Se3), able to solve these limitations by immobilizing the LiPS and catalytically activating the redox conversion at the cathode. The synthesis of I-Bi2Se3 nanosheets is detailed here and their morphology, crystal structure, and composition are thoroughly. Density-functional theory and experimental tools are used to demonstrate that I-Bi2Se3 nanosheets are characterized by a proper composition and micro- and nano-structure to facilitate Li+ diffusion and fast electron transportation, and to provide numerous surface sites with strong LiPS adsorbability and extraordinary catalytic activity. Overall, I-Bi2Se3/S electrodes exhibit outstanding initial capacities up to 1500 mAh g−1 at 0.1 C and cycling stability over 1000 cycles, with an average capacity decay rate of only 0.012% per cycle at 1 C. Besides, at a sulfur loading of 5.2 mg cm−2, a high areal capacity of 5.70 mAh cm−2 at 0.1 C is obtained with an electrolyte/sulfur ratio of 12 µL mg−1. This work demonstrated that doping is an effective way to optimize the metal selenide catalysts in LSBs.

We report a triple hybrid electrode (MXene/activated carbon (AC)/polyoxometalates (POMs)) combining the merits of three materials: MXene (high volumetric capacitance), AC (high gravimetric capacitance) and Phosphotungstate (fast redox). Phosphotungstic acid (HPW12) and tetraethylammonium phosphotungstate (TEAPW12) were the two POMs used to prepare MXene/AC/POMs triple hybrids. MXene/AC/TEAPW12 outperformed MXene/AC/HPW12 in 1 M tetraethylammonium tetrafluoroborate (TEABF4)/acetonitrile. Nano-dispersion of POMs facilitates charge storage through surface capacitive processes (91% at 2 mV s). MXene/AC/TEAPW12 delivered significantly higher gravimetric capacitance (87F g at 1 mV s) than MXene (40F g at 1 mV s) in the same organic electrolyte, without sacrificing much volumetric capacitance (less than 10%). The gravimetric capacitance of the triple hybrid was similar to that of MXene/AC, whereas its volumetric capacitance was 1.5 times higher. Replacing TEA cations with 1-ethyl-3-methylimidazolium cations (EMIM), the capacitance improved by 21%. Coupled with AC positive electrodes in an asymmetric cell, MXene/AC/TEAPW12 delivered 4.6 times higher gravimetric energy density and 3.5 times higher volumetric energy density than a similar MXene asymmetric cell at relatively high-power densities. This study proves that MXene/AC/TEAPW12 combines the merits and compensates for the demerits of each component and is a promising electrode material for organic-electrolyte supercapacitors.

The shuttling behavior and sluggish conversion kinetics of the intermediate lithium polysulfides (LiPS) represent the main obstructions to the practical application of lithium–sulfur batteries (LSBs). Herein, a 1D p–d conjugated metal–organic framework (MOF), Ni-MOF-1D, is presented as an efficient sulfur host to overcome these limitations. Experimental results and density functional theory calculations demonstrate that Ni-MOF-1D is characterized by a remarkable binding strength for trapping soluble LiPS species. Ni-MOF-1D also acts as an effective catalyst for S reduction during the discharge process and Li2S oxidation during the charging process. In addition, the delocalization of electrons in the p–d system of Ni-MOF-1D provides a superior electrical conductivity to improve electron transfer. Thus, cathodes based on Ni-MOF-1D enable LSBs with excellent performance, for example, impressive cycling stability with over 82% capacity retention over 1000 cycles at 3 C, superior rate performance of 575 mAh g-1 at 8 C, and a high areal capacity of 6.63 mAh cm-2 under raised sulfur loading of 6.7 mg cm-2. The strategies and advantages here demonstrated can be extended to a broader range of p–d conjugated MOFs materials, which the authors believe have a high potential as sulfur hosts in LSBs., Peer Reviewed, Postprint (author's final draft)

The shuttle effect and sluggish conversion kinetics of lithium polysulfides (LiPS) hamper the practical application of lithium–sulfur batteries (LSBs). Toward overcoming these limitations, herein an in situ grown C2N@NbSe2 heterostructure is presented with remarkable specific surface area, as a Li–S catalyst and LiPS absorber. Density functional theory (DFT) calculations and experimental results comprehensively demonstrate that C2N@NbSe2 is characterized by a suitable electronic structure and charge rearrangement that strongly accelerates the LiPS electrocatalytic conversion. In addition, heterostructured C2N@NbSe2 strongly interacts with LiPS species, confining them at the cathode. As a result, LSBs cathodes based on C2N@NbSe2/S exhibit a high initial capacity of 1545 mAh g-1 at 0.1 C. Even more excitingly, C2N@NbSe2/S cathodes are characterized by impressive cycling stability with only 0.012% capacity decay per cycle after 2000 cycles at 3 C. Even at a sulfur loading of 5.6 mg cm-2, a high areal capacity of 5.65 mAh cm-2 is delivered. These results demonstrate that C2N@NbSe2 heterostructures can act as multifunctional polysulfide mediators to chemically adsorb LiPS, accelerate Li-ion diffusion, chemically catalyze LiPS conversion, and lower the energy barrier for Li2S precipitation/decomposition, realizing the “adsorption-diffusion-conversion” of polysulfides., Award-winning, Postprint (author's final draft)

The shuttle effect and the sluggish reaction kinetics of lithium polysulfide (LiPS) seriously compromise the performance of lithium–sulfur batteries (LSBs). To overcome these limitations and enable the fabrication of robust LSBs, here the use of a Mott–Schottky catalyst based on bimetallic phos- phide CoFeP nanocrystals supported on carbon nitride tubular nanostruc- tures as sulfur hosts is proposed. Theoretical calculations and experimental data confirm that CoFeP@CN composites are characterized by a suitable electronic structure and charge rearrangement that allows them to act as a Mott–Schottky catalyst to accelerate LiPS conversion. In addition, the tubular geometry of CoFeP@CN composites facilitates the diffusion of Li ions, accommodates volume change during the reaction, and offers abundant lithi- ophilic/sulfiphilic sites to effectively trap soluble LiPS. Therefore, S@CoFeP@ CN electrodes deliver a superior rate performance of 630 mAh g-1 at 5 C, and remarkable cycling stability with 90.44% capacity retention over 700 cycles. Coin cells with high sulfur loading, 4.1 mg cm-2, and pouch cells with 0.1 Ah capacities are further produced to validate their superior cycling stability. In addition, it is demonstrated here that CoFeP@CN hosts greatly alleviate the often overlooked issues of low energy efficiency and serious self-discharging in LSBs., Peer Reviewed, Postprint (author's final draft)

Lithium–sulfur batteries (LSBs) are considered to be one of the most promising next generation energy storage systems due to their high energy density and low material cost. However, there are still some challenges for the commercialization of LSBs, such as the sluggish redox reaction kinetics and the shuttle effect of lithium polysulfides (LiPS). Here a 2D layered organic material, C2N, loaded with atomically dispersed iron as an effective sulfur host in LSBs is reported. X-ray absorption fine spectroscopy and density functional theory calculations prove the structure of the atomically dispersed Fe/C2N catalyst. As a result, Fe/C2N-based cathodes demonstrate significantly improved rate performance and long-term cycling stability. Fe/C2N-based cathodes display initial capacities up to 1540 mAh g-1 at 0.1 C and 678.7 mAh g-1 at 5 C, while retaining 496.5 mAh g-1 after 2600 cycles at 3 C with a decay rate as low as 0.013% per cycle. Even at a high sulfur loading of 3 mg cm-2, they deliver remarkable specific capacity retention of 587 mAh g-1 after 500 cycles at 1 C. This work provides a rational structural design strategy for the development of high-performance cathodes based on atomically dispersed catalysts for LSBs., Peer Reviewed, Postprint (author's final draft)

Lithium–sulfur batteries (LSBs) are considered to be one of the most promising next generation energy storage systems due to their high energy density and low material cost. However, there are still some challenges for the commercialization of LSBs, such as the sluggish redox reaction kinetics and the shuttle effect of lithium polysulfides (LiPS). Here a 2D layered organic material, C2N, loaded with atomically dispersed iron as an effective sulfur host in LSBs is reported. X‐ray absorption fine spectroscopy and density functional theory calculations prove the structure of the atomically dispersed Fe/C2N catalyst. As a result, Fe/C2N‐based cathodes demonstrate significantly improved rate performance and long‐term cycling stability. Fe/C2N‐based cathodes display initial capacities up to 1540 mAh g−1 at 0.1 C and 678.7 mAh g−1 at 5 C, while retaining 496.5 mAh g−1 after 2600 cycles at 3 C with a decay rate as low as 0.013% per cycle. Even at a high sulfur loading of 3 mg cm−2, they deliver remarkable specific capacity retention of 587 mAh g−1 after 500 cycles at 1 C. This work provides a rational structural design strategy for the development of high‐performance cathodes based on atomically dispersed catalysts for LSBs.

To commercially realize the enormous potential of lithium–sulfur batteries (LSBs) several challenges remain to be overcome. At the cathode, the lithium polysulfide (LiPS) shuttle effect must be inhibited and the redox reaction kinetics need to be substantially promoted. In this direction, this work proposes a cathode material based on a transition-metal selenide (TMSe) as both adsorber and catalyst and a hollow nanoreactor architecture: ZnSe/N-doped hollow carbon (ZnSe/NHC). It is here demonstrated both experimentally and by means of density functional theory that this composite provides three key benefits to the LSBs cathode: (i) A highly effective trapping of LiPS due to the combination of sulfiphilic sites of ZnSe, lithiophilic sites of NHC, and the confinement effect of the cage-based structure; (ii) a redox kinetic improvement in part associated with the multiple adsorption sites that facilitate the Li+ diffusion; and (iii) an easier accommodation of the volume expansion preventing the cathode damage due to the hollow design. As a result, LSB cathodes based on S@ZnSe/NHC are characterized by high initial capacities, superior rate capability, and an excellent stability. Overall, this work not only demonstrates the large potential of TMSe as cathode materials in LSBs but also probes the nanoreactor design to be a highly suitable architecture to enhance cycle stability.

Hollow MnxFe3-xO4 nanoparticles (NPs) with an average size of 15¿nm are produced from the solid state reaction of Fe3O4–Mn3O4 heterostructures. These heterostructures are synthesized through the seeded-growth of Mn3O4 crystal domains on the surface of hollow Fe3O4 NPs obtained by the nanoscale Kirkendall effect. Fe3O4–Mn3O4 heterostructures are subsequently annealed at 500¿°C, enough temperature to promote the interfusion of Fe and Mn ions, but without compromising the hollow geometry. MnxFe3-xO4 nanostructures are tested as anode in lithium-ion batteries (LIBs), delivering large lithium storage capacities and high-rate capabilities of 1054 mAh g-1 at 0.1¿A¿g-1 and 369 mAh g-1 at 5¿A¿g-1. Additionally, hollow MnxFe3-xO4 NPs display long cycling stability, with a capacity up to 887 mAh g-1 at 0.3¿A¿g-1 after 450 cycles. The excellent performance of hollow MnxFe3-xO4 NPs as anode for LIBs is associated with their crystal structure, composition, and the presence of carbonized ligands, which further promote electrical conductivity and buffer the volume changes during cycling. Additionally, the small particle size and hollow morphology improves the lithium kinetics, structural stability and cycling performance., Peer Reviewed, Postprint (author's final draft)

To realize fast-growing field of electric vehicles, rechargeable lithium-sulfur batteries (LSBs) have recently emerged as one of the most exciting alternatives to lithium-ion batteries (LIBs) owing to their higher theoretical energy density, 6 times higher than LIBs and lower cost. However, a poor utilization of the active material involved by the electrical insulating character of sulfur and lithium sulfides and a rapid degradation during charge/discharge processes still limit their practical application. Therefore, in this work, an urchin-shaped NiCo2Se4 (u-NCSe) nanostructures as efficient sulfur hosts were synthesized to overcome the limitations of lithium-sulfur batteries (LSBs) using selenization of Ni0.33Co0.67(CO3)0.5OH precursor. The u-NCSe showed a hollow structure with different distribution of Ni, Co and Se, which was proved by electron energy loss spectroscopy (EELS). Meanwhile, the high-resolution transmission electron microscopy (HRTEM) images indicated that the NiCo2Se4 nanostructures had a good crystallinity, in agreement with the cubic phase of NiCo2Se4 (space group: C12/m1). Owing to the hollow structure that can relieve volumetric expansion, a superior electrical conductivity to improve electron transfer, a high polarity to promote absorption of lithium polysulfides (LiPS), and outstanding electrocatalytic activity to accelerate LiPS conversion kinetics, S@u-NCSe delivers outstanding initial capacities up to 1403 mAh/g at 0.1 C and retains 626 mAh/g at 5 C with exceptional rate performance. More significantly, a very low capacity decay rate of only 0.016% per cycle is obtained after 2000 cycles at 3 C. Even at high sulfur loading (3.2 mg/cm2), a reversible capacity of 557 mAh/g is delivered after 600 cycles at 1 C. Density functional theory calculations further confirm the strong interaction between NCSe and LiPS, and cytotoxicity measure-ments prove the biocompatibility of NCSe. This work not only demonstrates that transition metal selenides can

This paper presents a large wound cell for in operando neutron diffraction (ND) from which high quality diffraction patterns are collected every 15 min while maintaining conventional electrochemical performance. Under in operando data collection conditions the oxygen atomic displacement parameters (ADPs) and cell parameters were extracted for Li0.18Sr0.66Ti0.5Nb0.5O3. Analysis of diffraction data collected under in situ conditions revealed that the lithium is located on the (0.5 0.5 0) site, corresponding to the 3c Wyckoff position in the cubic perovskite unit cell, after the cell is discharged to I V. When the cell is discharged under potentiostatic conditions the quantity of lithium on this site increases, indicating a potential position where lithium becomes pinned in the thermodynamically stable phase. During this potentiostatic step the oxygen ADPs reduce significantly. On discharge, however, the oxygen ADPs were observed to increase gradually as more lithium is inserted into the structure. Finally, the rate of unit cell expansion changed by similar to 44% once the lithium content approached similar to 0.17 Li per formula unit. A link between lithium content and degree of mobility, disorder of the oxygen positions and changing rate of unit cell expansion at various stages during lithium insertion and extraction is thus presented.