Hierarchical porous nanowire-like MoS2/CoNiO2 nanohybrids were synthesized via the hydrothermal process. CoNiO2 nanowires were selected due to the edge site, high surface/volume ratio, and superior electrochemical characteristics as the porous backbone for decoration of layered MoS2 nanoflakes to construct innovative structure hierarchical three-dimensional (3D) porous NWs MoS2/CoNiO2 hybrids with excellent charge accumulation and efficient ion transport capabilities. Physicochemical analyses were conducted on the developed hybrid composite, revealing conclusive evidence that the CoNiO2 nanowires have been securely anchored onto the surface of the MoS2 nanoflake array. The electrochemical results strongly proved the benefit of the hierarchical 3D porous MoS2/CoNiO2 hybrid structure for the charge storage kinetics. The synergistic characteristics arising from the MoS2/CoNiO2 composite yielded a notably high specific capacitance of 1340 F/g at a current density of 0.5 A/g. Furthermore, the material exhibited sustained cycling stability, retaining 95.6% of its initial capacitance after 10â¯000 long cycles. The asymmetric device comprising porous MoS2/CoNiO2//activated carbon encompassed outstanding energy density (93.02 Wh/kg at 0.85 kW/kg) and cycling stability (94.1% capacitance retention after 10â¯000 cycles). Additionally, the successful illumination of light-emitting diodes underscores the significant potential of the synthesized MoS2/CoNiO2 (2D/1D) hybrid for practical high-energy storage applications.
Gels are attracting materials for energy storage technologies. The strategic development of hydrogels with enhanced physicochemical properties, such as superior mechanical strength, flexibility, and charge transport capabilities, introduces novel prospects for advancing next-generation batteries, fuel cells, and supercapacitors. Through a refined comprehension of gelation chemistry, researchers have achieved notable progress in fabricating hydrogels endowed with stimuli-responsive, self-healing, and highly stretchable characteristics. This mini-review delineates the integration of hydrogels into batteries, fuel cells, and supercapacitors, showcasing compelling instances that underscore the versatility of hydrogels, including tailorable architectures, conductive nanostructures, 3D frameworks, and multifunctionalities. The ongoing application of creative and combinatorial approaches in functional hydrogel design is poised to yield materials with immense potential within the domain of energy storage.
While formamidinium lead iodide (FAPbI3) halide perovskite (HP) exhibits improved thermal stability and a wide band gap, its practical applicability is chained due to its room temperature phase transition from pure black (α-phase) to a non-perovskite yellow (δ-phase) when exposed to humidity. This phase transition is due to the fragile ionic bonding between the cationic and anionic parts of HPs during their formation. Herein, we report the synthesis of water-stable, red-light-emitting α-phase FAPbI3 nanocrystals (NCs) using five different amines to overcome these intrinsic phase instabilities. The structural, morphological, and electronic characterization were obtained using X-ray diffraction (XRD), field emission scanning electron microscope (FESEM), and X-ray photoelectron spectroscopy (XPS), respectively. The photoluminescence (PL) emission and single-particle imaging bear the signature of dual emission in several amines, indicating a self-trapped excited state. Our simple strategy to stabilize the α-phase using various amine interfacial interactions could provide a better understanding and pave the way for a novel approach for the stabilization of perovskites for prolonged durations and their multifunctional applications.
A solid-solution cathode of LiCoPO4-LiNiPO4 was investigated as a potential candidate for use with the Li4Ti5O12 (LTO) anode in Li-ion batteries. A pre-synthesized nickel-cobalt hydroxide precursor is mixed with lithium and phosphate sources by wet ball milling, which results in the final product, LiNiyCo1-yPO4 (LNCP) by subsequent heat treatment. Crystal structure and morphology of the product were analyzed by X-ray powder diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and scanning electron microscopy (SEM). Its XRD patterns show that LNCP is primarily a single-phase compound and has olivine-type XRD patterns similar to its parent compounds, LiCoPO4 and LiNiPO4. Synchrotron X-ray absorption spectroscopy (XAS) analysis, however, indicates that Ni doping in LiCoPO4 is unfavorable because Ni2+ is not actively involved in the electrochemical reaction. Consequently, it reduces the charge storage capability of the LNCP cathode. Additionally, ex situ XRD analysis of cycled electrodes confirms the formation of the electrochemically inactive rock salt-type NiO phase. The discharge capacity of the LNCP cathode is entirely associated with the Co3+/Co2+ redox couple. The electrochemical evaluation demonstrated that the LNCP cathode paired with the LTO anode produced a 3.12 V battery with an energy density of 184 Wh kg-1 based on the cathode mass.
Lithium-ion batteries (LIBs) remain at the forefront of energy research due to their capability to deliver high energy density. Understanding their degradation mechanism has been essential due to their rapid engagement in modern electric vehicles (EVs), where battery failure may incur huge losses to human life and property. The literature on this intimidating issue is rapidly growing and often very complex. This review strives to succinctly present current knowledge contributing to a more comprehensible understanding of the degradation mechanism. First, this review explains the fundamentals of LIBs and various degradation mechanisms. Then, the degradation mechanism of novel Li-rich cathodes, advanced characterization techniques for identifying it, and various theoretical models are presented and discussed. We emphasize that the degradation process is not only tied to the charge-discharge cycles; synthesis-induced stress also plays a vital role in catalyzing the degradation. Finally, we propose further studies on advanced battery materials that can potentially replace the layered cathodes.
We examine the performance of a number of single-atom M-N/C electrocatalysts with a common structure in order to deconvolute the activity of the framework N/C support from the metal M-N4 sites in M-N/Cs. The formation of the N/C framework with coordinating nitrogen sites is performed using zinc as a templating agent. After the formation of the electrically conducting carbon-nitrogen metal-coordinating network, we (trans)metalate with different metals producing a range of different catalysts (Fe-N/C, Co-N/C, Ni-N/C, Sn-N/C, Sb-N/C, and Bi-N/C) without the formation of any metal particles. In these materials, the structure of the carbon/nitrogen framework remains unchanged-only the coordinated metal is substituted. We assess the performance of the subsequent catalysts in acid, near-neutral, and alkaline environments toward the oxygen reduction reaction (ORR) and ascribe and quantify the performance to a combination of metal site activity and activity of the carbon/nitrogen framework. The ORR activity of the carbon/nitrogen framework is about 1000-fold higher in alkaline than it is in acid, suggesting a change in mechanism. At 0.80 VRHE, only Fe and Co contribute ORR activity significantly beyond that provided by the carbon/nitrogen framework at all pH values studied. In acid and near-neutral pH values (pH 0.3 and 5.2, respectively), Fe shows a 30-fold improvement and Co shows a 5-fold improvement, whereas in alkaline pH (pH 13), both Fe and Co show a 7-fold improvement beyond the baseline framework activity. The site density of the single metal atom sites is estimated using the nitrite adsorption and stripping method. This method allows us to deconvolute the framework sites and metal-based active sites. The framework site density of catalysts is estimated as 7.8 × 1018 sites g-1. The metal M-N4 site densities in Fe-N/C and Co-N/C are 9.4 × 1018 sites-1 and 4.8 × 1018 sites g-1, respectively.
Designing highly conductive and (electro)chemical stable inorganic solid electrolytes using cost-effective materials is crucial for developing all-solid-state batteries. Here, we report halide nanocomposite solid electrolytes (HNSEs) ZrO2(-ACl)-A2ZrCl6 (A = Li or Na) that demonstrate improved ionic conductivities at 30 °C, from 0.40 to 1.3 mS cm-1 and from 0.011 to 0.11 mS cm-1 for Li+ and Na+, respectively, compared to A2ZrCl6, and improved compatibility with sulfide solid electrolytes. The mechanochemical method employing Li2O for the HNSEs synthesis enables the formation of nanostructured networks that promote interfacial superionic conduction. Via density functional theory calculations combined with synchrotron X-ray and 6Li nuclear magnetic resonance measurements and analyses, we demonstrate that interfacial oxygen-substituted compounds are responsible for the boosted interfacial conduction mechanism. Compared to state-of-the-art Li2ZrCl6, the fluorinated ZrO2-2Li2ZrCl5F HNSE shows improved high-voltage stability and interfacial compatibility with Li6PS5Cl and layered lithium transition metal oxide-based positive electrodes without detrimentally affecting Li+ conductivity. We also report the assembly and testing of a Li-In||LiNi0.88Co0.11Mn0.01O2 all-solid-state lab-scale cell operating at 30 °C and 70 MPa and capable of delivering a specific discharge of 115 mAh g-1 after almost 2000 cycles at 400 mA g-1.
Enhancing the participation of the lattice oxygen mechanism (LOM) in several perovskites to significantly boost the oxygen evolution reaction (OER) is daunting. With the rapid decline in fossil fuels, energy research is turning toward water splitting to produce usable hydrogen by significantly reducing overpotential for other half-cells' OER. Recent studies have shown that in addition to the conventional adsorbate evolution mechanism (AEM), participation of LOM can overcome their prevalent scaling relationship limitations. Here, we report the acid treatment strategy and bypass the cation/anion doping strategy to significantly enhance LOM participation. Our perovskite demonstrated a current density of 10 mA cm-2 at an overpotential of 380 mV and a low Tafel slope (65 mV dec-1) much lower than IrO2 (73 mV dec-1). We propose that the presence of nitric acid-induced defects regulates the electronic structure and thereby lowers oxygen binding energy, allowing enhanced LOM participation to boost OER significantly.
Two-dimensional layered transition metal dichalcogenides have emerged as promising materials for supercapacitors and hydrogen evolution reaction (HER) applications. Herein, the molybdenum sulfide (MoS2 )@vanadium sulfide (VS2 ) and tungsten sulfide (WS2 )@VS2 hybrid nano-architectures prepared via a facile one-step hydrothermal approach is reported. Hierarchical hybrids lead to rich exposed active edge sites, tuned porous nanopetals-decorated morphologies, and high intrinsic activity owing to the strong interfacial interaction between the two materials. Fabricated supercapacitors using MoS2 @VS2 and WS2 @VS2 electrodes exhibit high specific capacitances of 513 and 615 F g- 1 , respectively, at an applied current of 2.5 A g- 1 by the three-electrode configuration. The asymmetric device fabricated using WS2 @VS2 electrode exhibits a high specific capacitance of 222 F g- 1 at an applied current of 2.5 A g- 1 with the specific energy of 52 Wh kg- 1 at a specific power of 1 kW kg- 1 . For HER, the WS2 @VS2 catalyst shows noble characteristics with an overpotential of 56 mV to yield 10 mA cm- 2 , a Tafel slope of 39 mV dec-1 , and an exchange current density of 1.73 mA cm- 2 . In addition, density functional theory calculations are used to evaluate the durable heterostructure formation and adsorption of hydrogen atom on the various accessible sites of MoS2 @VS2 and WS2 @VS2 heterostructures.
Grid-scale energy storage applications can benefit from rechargeable sodium-ion batteries. As a potential material for making non-cobalt, nickel-free, cost-effective cathodes, earth-abundant Na2/3Fe1/2Mn1/2O2 is of particular interest. However, Mn3+ ions are particularly susceptible to the Jahn-Teller effect, which can lead to an unstable structure and continuous capacity degradation. Modifying the crystal structure by aliovalent doping is considered an effective strategy to alleviate the Jahn-Teller effect. Using a sol-gel synthesis route followed by heat treatment, we succeeded in preparing an Mg-doped Na2/3Fe1-yMnyO2 cathode. Its electrochemical properties and charge compensation mechanism were then studied using synchrotron-based X-ray absorption spectroscopy and in situ X-ray diffraction techniques. The results revealed that Mg doping reduced the number of Mn3+ Jahn-Teller centers and alleviated high voltage phase transition. However, Mg doping was unable to suppress the P2-P'2 phase transition at a low voltage discharge. An initial discharge capacity of about 196 mAh g-1 was obtained at a current density of 20 mAh g-1, and 60% of rate capability was maintained at a current density of 200 mAh g-1 in a voltage range of 1.5-4.3 V. This study will greatly contribute to the ongoing search for advanced and efficient cathodes from earth-abundant elements for rechargeable sodium-ion batteries operable at room temperature.
We explore a phase engineering strategy to improve the electrochemical performance of transition metal sulfides (TMSs) in anode materials for lithium-ion batteries (LIBs). A one-pot hydrothermal approach has been employed to synthesize MoS2 nanostructures. MoS2 and MoO3 phases can be readily controlled by straightforward calcination in the (200-300) °C temperature range. An optimized temperature of 250 °C yields a phase-engineered MoO3@MoS2 hybrid, while 200 and 300 °C produce single MoS2 and MoO3 phases. When tested in LIBs anode, the optimized MoO3@MoS2 hybrid outperforms the pristine MoS2 and MoO3 counterparts. With above 99% Coulombic efficiency (CE), the hybrid anode retains its capacity of 564 mAh g-1 after 100 cycles, and maintains a capacity of 278 mAh g-1 at 700 mA g-1 current density. These favorable characteristics are attributed to the formation of MoO3 passivation surface layer on MoS2 and reactive interfaces between the two phases, which facilitate the Li-ion insertion/extraction, successively improving MoO3@MoS2 anode performance.
Activation of oxygen redox during the first cycle has been reported as the main trigger of voltage hysteresis during further cycles in high-energy-density Li-rich 3d-transition-metal layered oxides. However, it remains unclear whether hysteresis only occurs due to oxygen redox. Here, it is identified that the voltage hysteresis can highly correlate to cationic reduction during discharge in the Li-rich layered oxide, Li1.2 Ni0.4 Mn0.4 O2 . In this material, the potential region of discharge accompanied by hysteresis is apparently separated from that of discharge unrelated to hysteresis. The quantitative analysis of soft/hard X-ray absorption spectroscopies discloses that hysteresis is associated with an incomplete cationic reduction of Ni during discharge. The galvanostatic intermittent titration technique shows that the inevitable energy consumption caused by hysteresis corresponds to an overpotential of 0.3 V. The results unveil that hysteresis can also be affected by cationic redox in Li-rich layered cathodes, implying that oxygen redox cannot be the only reason for the evolution of voltage hysteresis. Therefore, appropriate control of both cationic and anionic redox of Li-rich layered oxides will allow them to reach their maximum energy density and efficiency.
Sodium-ion batteries (SIBs) hold great potential for use in large-scale grid storage applications owing to their low energy cost compared to lithium analogs. The symmetrical SIBs employing Na3 V2 (PO4 )3 (NVP) as both the cathode and anode are considered very promising due to negligible volume changes and longer cycle life. However, the structural changes associated with the electrochemical reactions of symmetrical SIBs employing NVP have not been widely studied. Previous studies on symmetrical SIBs employing NVP are believed to undergo one mole of Na+ storage during the electrochemical reaction. However, in this study, it is shown that there are significant differences during the electrochemical reaction of the symmetrical NVP system. The symmetrical sodium-ion cell undergoes ≈2 moles of Na+ reaction (intercalation and deintercalation) instead of 1 mole of Na+ . A simultaneous formation of Na5 V2 (PO4 )3 phase in the anode and NaV2 (PO4 )3 phase in the cathode is revealed by synchrotron-based X-ray diffraction and X-ray absorption spectroscopy. A symmetrical NVP cell can deliver a stable capacity of ≈99 mAh g-1 , (based on the mass of the cathode) by simultaneously utilizing V3+ /V2+ redox in anode and V3+ /V4+ redox in cathode. The current study provides new insights for the development of high-energy symmetrical NIBs for future use.
Cation-disordered rocksalt (DRX) cathodes have been viewed as next-generation high-energy density materials surpassing conventional layered cathodes for lithium-ion battery (LIB) technology. Utilizing the opportunity of a better cation mixing facility in DRX, we synthesize Na-doped DRX as an efficient electrocatalyst toward oxygen evolution reaction (OER). This novel OER electrocatalyst generates a current density of 10 mA cm−2 at an overpotential (η) of 270 mV, Tafel slope of 67.5 mV dec−1, and long-term stability >5.5 days' superior to benchmark IrO2 (η = 330 mV with Tafel slope = 74.8 mV dec−1). This superior electrochemical behavior is well supported by experiment and sparse Gaussian process potential (SGPP) machine learning-based search for minimum energy structure. Moreover, as oxygen binding energy (OBE) on the surface closely relates to OER activity, our density functional theory (DFT) calculations reveal that Na-doping assists in facile O2 evolution (OBE = 5.45 eV) compared with pristine-DRX (6.51 eV).
2-D transition metal carbides (TMCs)-based anode materials offer competitive performance in lithium-ion batteries (LIBs) owing to its excellent conductivity; cheaper, flexible uses; and superior mechanical stability. However, the electrochemical energy storage of TMCs is still the major obstacle due to their modest capacity and the trends of restacking/aggregation. In this report, the Mo2C nanosheets were attached on conductive CNT network to form a hierarchical 2D hybrid structure, which not only alleviated the aggregation of the Mo2C nanoparticle and facilitated the rapid transference of ion/electron, but also adapted effectually to the hefty volume expansion of Mo2C nanosheets and prevented restacking/collapse of Mo2C structure. Benefitting from the layered Mo2@CNT hybrid structure, the charge/discharge profile produced a 200 mAh g-1 discharge-specific capacity (second cycle) and 132 mAh g-1 reversible-discharge discharge-specific capacity (after 100 cycles) at 50 mA g-1 current density, with high-speed competency and superior cycle stability. The improved storage kinetics for Mo2@CNT hybrid structure are credited to the creation of numerous active catalytic facets and association reaction between the CNT and Mo2C, promoting the efficient electron transfer and enhancing the cycling stability.
Herein, we formulated a new O3-type layered Na0.80[Fe0.40Co0.40Ti0.20]O2 (NFCTO) cathode material for sodium-ion batteries (SIBs) using a double-substitution concept of Co in the parent NaFe0.5Co0.5O2, having the general formula Na1-x[Fe0.5-x/2Co0.5-x/2M4+x]O2 (M4+ = tetravalent ions). The NFCTO electrode delivers a first discharge capacity of 108 mAhg-1 with 80% discharge capacity retention after 50 cycles. Notably, the first charge-discharge profile shows asymmetric yet reversible redox reactions. Such asymmetric redox reactions and electrochemical properties of the NFCTO electrode were correlated with the phase transition behavior and charge compensation reaction using synchrotron-based in situ XRD and ex situ X-ray absorption spectroscopy. This study provides an exciting opportunity to explore the interplay between the rich chemistry of Na1-x[Fe0.5-x/2Co0.5-x/2M4+x]O2 and sodium storage properties, which may lead to the development of new cathode materials for SIBs.
Nitrogen-doped porous carbons containing atomically dispersed iron are prime candidates for substituting platinum-based catalysts for oxygen reduction reaction (ORR) in fuel cells. These carbon catalysts are classically synthesizedviacomplicated routes involving multiple heat-treatment steps to form the desired Fe-Nx sites. We herein developed a highly active FeNC catalyst comprising of exclusive Fe-Nx sites by a simplified solid-state synthesis protocol involving only a single heat-treatment. Imidazole is pyrolyzed in the presence of an inorganic salt-melt resulting in highly porous carbon sheets decorated with abundant Fe-Nx centers, which yielded a high density of electrochemically accessible active sites (1.36 × 1019 sites g-1) as determined by the in situ nitrite stripping technique. The optimized catalyst delivered a remarkable ORR activity with a half-wave potential (E1/2) of 0.905 VRHE in alkaline electrolyte surpassing the benchmark Pt catalyst by 55 mV. In acidic electrolyte, an E1/2 of 0.760 VRHE is achieved at a low loading level (0.29 mg cm-2). In PEMFC tests, a current density of 2.3 mA cm-2 is achieved at 0.90 ViR-free under H2-O2 conditions, reflecting high kinetic activity of the optimized catalyst.
Owing to their high Li+ conductivities, mechanical sinterability, and solution processability, sulfide Li argyrodites have attracted much attention as enablers in the development of high-performance all-solid-state batteries with practicability. However, solution-processable Li argyrodites have been developed only for a composition of Li6PS5X (X = Cl, Br, I) with insufficiently high Li+ conductivities (â¼10-4 S cm-1). Herein, we report the highest Li+ conductivity of 0.54 mS cm-1 at 30 °C (Li6.5P0.5Ge0.5S5I) for solution-processable iodine-based Li argyrodites. A comparative investigation of three iodine-based argyrodites of unsubstituted and Ge- and Sn-substituted solution-processed Li6PS5I with varied heat-treatment temperature elucidates the effect of microstructural evolution on Li+ conductivity. Notably, local nanostructures consisting of argyrodite nanocrystallites in solution-processed Li6.5P0.5Ge0.5S5I have been directly captured by cryogenic transmission electron microscopy, which is a first for sulfide solid electrolyte materials. Specifically, the promising electrochemical performances of all-solid-state batteries at 30 °C employing LiCoO2 electrodes tailored by the infiltration of Li6.5P0.5Ge0.5S5I-ethanol solutions are successfully demonstrated.
For the realization of sodium-ion batteries (SIBs), high-performance anode materials are urgently required with the advantages of being low-cost and environment-friendly. In this work, layered-type NaVO3 is prepared by the simple solid-state route with a rod-like morphology and used as an anode material for SIBs. The NaVO3 electrode exhibits a high specific capacity of 196 mA h g-1 during the first cycle and retains a capacity of 125 mA h g-1 at the 80th cycle with a high Coulombic efficiency of >99%, demonstrating high reversibility. The sodium diffusion coefficient in NaVO3 is measured using electrochemical impedance spectroscopy (1.368 × 10-15 cm2 s-1), the galvanostatic intermittent titration technique (1.15715 × 10-13 cm2 s-1), and cyclic voltammetry (2.7935 × 10-16 cm2 s-1). Furthermore, the reaction mechanism during the sodiation/desodiation process is investigated using in situ X-ray diffraction and X-ray absorption near the edge structure analysis, which suggests the formation of an amorphous-like phase and reversible redox reaction of V4+ â V5+, respectively.
In order to improve the electrochemical kinetics of anatase titania (TiO2), Mn-doped TiO2 incorporated with functionalized multiwall carbon nanotubes (MWCNTs) has been prepared by a modified hydrothermal method and tested for both lithium (LIB) and sodium-ion battery (SIB) anodes. The size of the TiO2 particles is controlled to â¼35-40 nm, with almost even distribution on the MWCNTs surface. The nanostructuring and appropriate doping of cost-effective manganese into the TiO2 host improved the electrochemical performance in terms of high rate capability and specific capacity for both the rechargeable battery systems. For the LIBs, the charge capacity of the 5% Mn-TiO2/MWCNT anode is 226.3 mA h g-1 in the first cycle, and is retained at 176.4 mA h g-1 after 80 cycles as compared with the SIBs, in which the charge capacity is 152.1 mA h g-1 in the first cycle, and is retained at 121.4 mA h g-1 after 80 cycles. After testing the electrodes at a high current rate of 20C, the nanocomposite electrode can still demonstrate charge capacities of 131.2 and 117.2 mA h g-1 at a 0.1C rate for LIBs and SIBs, respectively. The incorporation of Mn-ions (2+, 4+) is found to play a crucial role in terms of defects and vacancy creation, increasing conduction band electrons and lattice expansion to facilitate alkali metal ion diffusion for superior electrochemical performance. The combination of heteroatom doping and use of a highly conductive additive in the form of MWCNTs has resulted in excellent electrode integrity, high ion accessibility, and fast electron transport. Its outstanding cycling stability and remarkable rate performance make the 5% Mn-TiO2/MWCNT a promising anode material for high-performance LIBs and SIBs.
