Electrode Materials For Batteries Research Articles

An innovative synthesis of carbon-coated TiO2 nanoparticles as a host for Na+ intercalation in sodium-ion batteries.

In this work, an innovative route to synthesize an anatase TiO2@C composite is presented. The synthesis was conducted using a soft chemistry microwave-assisted method using titanium(IV) butoxide as a titanium precursor. The residual (un)converted titanium precursor remaining after TiO2 synthesis was used as a carbon precursor and thermally treated under H2 to obtain nanoparticles of the TiO2@C composite. A superior reversible specific capacity was obtained with TiO2@C (120 mA h g-1 at a C/20 rate, 3rd cycle) compared to that with pristine TiO2 (66.5 mA h g-1 at a C/20 rate, 3rd cycle), in agreement with the importance of carbon coating addition to TiO2 nanoparticles as negative electrode materials for sodium-ion batteries.

Organic Electrode Materials for Energy Storage and Conversion: Mechanism, Characteristics, and Applications.

ConspectusLithium ion batteries (LIBs) with inorganic intercalation compounds as electrode active materials have become an indispensable part of human life. However, the rapid increase in their annual production raises concerns about limited mineral reserves and related environmental issues. Therefore, organic electrode materials (OEMs) for rechargeable batteries have once again come into the focus of researchers because of their design flexibility, sustainability, and environmental compatibility. Compared with conventional inorganic cathode materials for Li ion batteries, OEMs possess some unique characteristics including flexible molecular structure, weak intermolecular interaction, being highly soluble in electrolytes, and moderate electrochemical potentials. These unique characteristics make OEMs suitable for applications in multivalent ion batteries, low-temperature batteries, redox flow batteries, and decoupled water electrolysis. Specifically, the flexible molecular structure and weak intermolecular interaction of OEMs make multivalent ions easily accessible to the redox sites of OEMs and facilitate the desolvation process on the redox site, thus improving the low-temperature performance, while the highly soluble nature enables OEMs as redox couples for aqueous redox flow batteries. Finally, the moderate electrochemical potential and reversible proton storage and release of OEMs make them suitable as redox mediators for water electrolysis. Over the past ten years, although various new OEMs have been developed for Li-organic batteries, Na-organic batteries, Zn-organic batteries, and other battery systems, batteries with OEMs still face many challenges, such as poor cycle stability, inferior energy density, and limited rate capability. Therefore, previous reviews of OEMs mainly focused on organic molecular design for organic batteries or strategies to improve the electrochemical performance of OEMs. A comprehensive review to explore the characteristics of OEMs and establish the correlation between these characteristics and their specific application in energy storage and conversion is still lacking.In this Account, we initially provide an overview of the sustainability and environmental friendliness of OEMs for energy storage and conversion. Subsequently, we summarize the charge storage mechanisms of the different types of OEMs. Thereafter, we explore the characteristics of OEMs in comparison with conventional inorganic intercalation compounds including their structural flexibility, high solubility in the electrolyte, and appropriate electrochemical potential in order to establish the correlations between their characteristics and potential applications. Unlike previous reviews that mainly introduce the electrochemical performance progress of different organic batteries, this Account specifically focuses on some exceptional applications of OEMs corresponding to the characteristics of organic electrode materials in energy storage and conversion, as previously published by our groups. These applications include monovalent ion batteries, multivalent ion batteries, low-temperature batteries, redox flow batteries with soluble OEMs, and decoupled water electrolysis employing organic electrodes as redox mediators. We hope that this Account will make an invaluable contribution to the development of organic electrode materials for next-generation batteries and help to unlock a world of potential energy storage applications.

Carbothermal reduction between MOF-derived carbon and spent battery powder for metal recovery: Thermogravimetric behavior and kinetic analysis

The combined hydrometallurgical and pyrometallurgical process is an innovative method for recycling spent batteries. This process includes a carbothermic reduction step that reduces the valence of valuable metals in the batteries, facilitating subsequent leaching, which is a crucial stage in the recycling process. Additionally, the use of new carbon materials in electrode materials for ternary lithium batteries, referred to as LIBs, is increasing. These materials typically have high porosity and a large specific surface area. In this study, two types of nanoporous carbon (NC) commonly used in electrodes, namely Al-PCP-800 and ZIF-8–800, were prepared to investigate their effects on the carbothermic reduction stage of recycling spent batteries. The carbothermal reduction reactions of spent LIBs powder mixed with activated carbon and the two types of NC were examined using a thermogravimetric balance (TG/DTG). Kinetic characteristics were calculated in the interval of maximum weight loss rate using five kinetic models: VM, RPM, URCM, KAS, and FWO. The kinetic analysis revealed that the KAS and FWO models, which exhibited higher correlation coefficients, more accurately described the carbothermic reduction reactions. TG analysis showed that the sample mixed with 25 % ZIF-8–800 achieved the lowest temperature at the weight loss peak for the maximum weight loss rate, 769°C at a heating rate of 20 °C/min. Additionally, the reaction activity of NC with the positive material in the spent LIBs powder was stronger than that of activated carbon. Among the models, the sample mixed with 25 % ZIF-8–800 exhibited the lowest activation energies, recorded at 171.83, 28.48, 122.22, 199.49, and 143.45 kJ/mol, respectively. XRD and XPS characterizations of the roasted products from the spent LIBs powder mixed with the three carbon materials at various roasting end temperatures demonstrated that the cathode materials initially decomposed into Mn3O4, NiO, CoO, Li2O, and Li2CO3. At higher temperatures, Mn3O4, NiO, and CoO were further reduced to MnO, pure metallic Co, and pure metallic Ni, respectively. The sample mixed with ZIF-8–800 showed the most substantial reduction of metallic elements, with the relative contents of pure metallic Ni, pure metallic Co, and low-valent Mn elements reaching 5.50 %, 4.41 %, and 71.29 %, respectively, at a final roasting temperature of 800 °C. Therefore, NC demonstrated greater reactivity in the reduction reactions with the cathode material in the spent LIBs powder, ranking in the order of ZIF-8–800 > Al-PCP-800 > activated carbon.

High Capacity and Fast Kinetics Enabled by Metal-Doping in Prussian Blue Analogue Cathodes for Sodium-Ion Batteries.

Prussian blue analogues (PBAs) have gained tremendous attention as promising low-cost electrochemically-tunable electrode materials, which can accommodate large Na+ ions with attractive specific capacity and charge-discharge kinetics. However, poor cycling stability caused by lattice strain and volume change remains to be improved. Herein, metal-doping strategy has been demonstrated in FeNiHCF, Na1.40Fe0.90Ni0.10[Fe(CN)6]0.85·1.3H2O, delivering a capacity as high as 148 mAh g‒1 at 10 mA g‒1. At an exceptionally high rate of 25.6 A g‒1, a reversible capacity of ~55 mAh g‒1 still can be obtained with a very small capacity decay rate of 0.02% per cycle for 1000 cycles, considered one of the best among all metal-doped PBAs. This exhibits the stabilizing effect of Ni doping which enhances structural stability and long-term cyclability. In situ synchrotron X-ray diffraction reveals an extremely small (~1%) change in unit cell parameters. The Ni substitution is found to increase the electronic conductivity and redox activity, especially at the low-spin (LS) Fe center due to inductive effect. This larger capacity contribution from LS Fe2+C6/Fe3+C6 redox couple is responsible for stable high-rate capability of FeNiHCF. The insight gained in this work may pave the way for the design of other high-performance electrode materials for sustainable sodium-ion batteries.

Investigation of fracture patterns and effect on capacity in all-solid-state batteries based on peridynamic electro-chemo-mechanical model

The evolution of complex fracture patterns of composite electrodes in all-solid-state batteries (ASSBs) during electrochemical cycles is one of the main phenomena driving capacity degradation. Such fracture patterns in active materials usually involve cracks with various orientations. While conventional wisdom usually treats fracture as ultimate failure of materials in many scenarios, the effect of crack in batteries is worth further investigation. Here, a concurrently coupled electro-chemo-mechanical model based on peridynamics has been developed to study fracture patterns and electrochemical performances of composite anodes during processes of charge and discharge. The framework consists of a classic bond-based peridynamic mechanical model, an electrochemical model, and a coupling technique to reflect the interaction between them in a bidirectional manner. The bond-based peridynamic mechanical model considers the active material’s elastic–plastic deformation and the solid electrolyte’s elastic deformation. The fracture energies of the active material, the solid electrolyte, and the interface are also incorporated into this model. The electrochemical model considers the volume expansion of the active material caused by the intercalation of lithium ions and the Butler-Volmer relation of charge transfer on the interface. Various parametric analyses are performed using this modeling framework to investigate the effects of external pressure, fracture energies of active material and solid electrolyte, and Young’s modulus on fracture patterns and electrochemical performances. It is found that different material parameters result in distinct fracture patterns in the active material with radial cracks or circumferential cracks, thus profoundly affecting the rates of charge and discharge. This work demonstrates the importance of considering the complex fracture patterns in electrode materials of batteries and provides insights for selecting more suitable electrode materials to mitigate capacity degradation.

Constructing in-situ polymerized electrolyte for room-temperature solid-state chloride ion battery with enhanced electrochemical performance

Considering large volume variation and dissolution issues of some promising electrode materials for chloride ion batteries (CIB), the construction of solid polymer electrolytes (SPE) for efficient chloride ion transport is intriguing. However, this is hindered by low ionic conductivity of chloride SPEs and poor cycling performance of CIBs. Herein, an in-situ polymerized and cross-linked poly(ethylene glycol) diacrylate-based chloride SPE with a low plasticizer content of succinonitrile is designed, yielding a room-temperature ionic conductivity of 7.6 × 10−5 S cm−1, which is higher than that of previously reported SPEs for CIBs. Moreover, the use of the as-prepared SPE achieves an integrated organic cathode with significantly enhanced rate performance and capacity retention of 96.1% after 100 cycles at room temperature, which is much higher than 49.9% (80 cycles) of the cathode in the CIB with a sandwiched structure. These improved performance is also superior to that of other reported cathodes coupled with different chloride SPEs. The chloride ion transfer mechanism of the cathode is revealed by X-ray photoelectron spectroscopy and energy dispersive spectroscopy.

Improved cycle stability and high-rate capability of LiNbO3-coated Li3VO4 as anode material for lithium-ion battery

Lithium vanadate (Li3VO4) has garnered considerable attention as an alternative negative electrode material for non-aqueous lithium-ion batteries due to its high capacity, energy efficiency, and stable discharge voltage. Nonetheless, the Li3VO4 material displays a low rate capability, attributed mainly to its poor intrinsic electronic conductivity. Here, we report the synthesis of lithium niobate LiNbO3-coated Li3VO4 (LVO@LNO) using a one-pot sol-gel method. The resulting LVO@LNO demonstrates a high reversible capacity of approximately 530 mAh/g, which is more than double that of free Li3VO4. To explore the effect of the LNO coating process on the morphological and structural properties, Raman, XRD, operando XRD, XPS, SEM and HTEM analyses were conducted. To explain the enhancement of electronic conductivity in our modified material after a LiNbO3 coating, we conducted an Ex-Situ electrochemical impedance (EIS) and Density Functional Theory (DFT) computational study. Additionally, we designed a full cell utilizing a 1 wt% LNO-coated LVO anode and NMC-811 cathode. The cell yielded an output voltage of approximately 2.8 V with a high initial specific capacity of 350 mAh/g versus to the anode, at 1C with a capacity retention of 85 % after 100 cycles.

Heavily vanadium-doped LiFePO4 olivine as electrode material for Li-ion aqueous rechargeable batteries

Since LiFePO4 batteries play a major role in the transition to safe, more affordable and sustainable energy production, numerous strategies have been applied to modify LFP cathode, with the aim of improving its electrochemistry. In this contribution, a highly vanadium-doped LiFe0.9V0.1PO4/C composite (LFP/C-10V) is synthesized using the glycine combustion method and characterized by x-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), Thermogravimetry Differential Thermal Analysis (TGDTA) and Cyclic Voltammetry (CV). It is shown that 10wt.% of vanadium can substitute Fe positions, thus decreasing unit cell volume, which is followed by generation of Li3V2PO4 traces, as detected by CV. High vanadium doping does not change the carbon content in the composite (≈13 wt%) but improves its electronic conductivity and electrochemical performance in both aqueous and organic electrolytes. The reversibility and current response are increasing following the trend: LFP/C, LFP/C -3mol%V, LFP/C - 5 mol % and LFP/C-10 mol %. The best specific capacity is obtained for the most highly doped olivine, which exhibits a reversible process at 1 mV s−1 in an aqueous electrolyte, thus showing a peak-to-peak distance of 56 mV. The high capacity of LFPC-10V is measured in both LiNO3 and NaNO3 electrolytes amounting to around 100 mAh g−1 at 20 mV s−1. Still, the material is only stable in LiNO3 electrolyte, making it more suitable for Li than Na-ion aqueous rechargeable batteries.

Uncovering the potential of two-dimensional AlB2 monolayer as a negative electrode material for alkali metal ion batteries: A DFT study

The electrode's material properties have an important role in the efficient performance of metal ion batteries. The possibility of using the two-dimensional AlB2 monolayer as the negative electrode material of lithium, sodium, and potassium ions was explored by the first-principles calculation in this study. It turns out that the storage capacity of AlB2 for Li, Na, and K ions is superior to that of many reported negative electrodes, which are about 1102, 1102, and 413 mA h g−1, respectively. The migration barriers for Li, Na, and K ions in the monolayer of AlB2 are 0.428, 0.162, and 0.019 eV, respectively, indicating that the AlB2 monolayer can be charged and discharged rapidly. Therefore, AlB2 is promising as a potential anode material for alkali metal ion batteries.

Layer‑by‑layer assembled binder-free hydrated vanadium oxide-acetylene black electrode for flexible aqueous zinc ion battery

Vanadium oxides are potential positive electrode materials for aqueous zinc ion batteries (ZIBs) owing to their advantages of high theoretical capacity, low cost, and so on. Developments of methods for preparing binder-free vanadium oxide electrodes on a large scale and further investigation of their Zn2+ storage mechanisms are essential for expanding their uses in large-scale energy storage systems and wearable electronics. In this work, binder-free electrodes with hydrated vanadium oxide (V2O5·nH2O, denoted as VOH)-acetylene black (AB) on carbon cloth (VOH-AB/CC) are fabricated by a simple and scalable method which combined low-temperature hydrothermal treatment with layer-by-layer drop/spray-coating process. The AB can greatly improve the electrical conductivity of VOH, thereby enhancing the electrochemical performance. The as-prepared electrode with 20 wt% of AB (VOH-AB2/CC) delivers a high capacity of 280 mA h g−1 at 1 A/g and a good rate capability of 205 mA h g−1 at 4 A/g, which is better than many of the reported binder-free vanadium base electrodes. Besides, excellent cycling performance with 89 % retention rate after 3000 cycles at 4 A/g is achieved on the VOH-AB2/CC electrode. Furthermore, a storage mechanism of Zn2+/H+/H2O insertion accompanied by the formation of basic zinc salt precipitate during the discharging process is proposed by the aid of ex-situ XRD and XPS techniques. Additionally, the flexible Quasi-Solid-State ZIB constructed using VOH-AB/CC as positive electrode can work well at different bending states and two ZIBs connected in series can lighten a light-emitting diode even under bending state. This work provides a low-cost, time-saving, environmental-friendly and scalable method to fabricate binder-free hydrated vanadium oxide electrodes for flexible aqueous ZIBs.

AB-type dual-phase high-entropy alloys as negative electrode of Ni-MH batteries: Impact of interphases on electrochemical performance

High-entropy alloys (HEAs) and their corresponding high-entropy hydrides are new potential candidates for negative electrode materials of nickel-metal hydride (Ni-MH) batteries. This study investigates the cyclic electrochemical hydrogen storage performance of two AB-type HEAs (A: hydride-forming elements, B: non-hydride-forming elements) in Ni-MH batteries. TiV2ZrCrMnFeNi with a dual-phase structure shows a fast activation and a low charge transfer impedance with a discharge capacity of 150 mAhg−1, while TiV1.5Zr1.5CrMnFeNi with a single phase shows a slow activation and a capacity of only 60 mAhg−1. The better electrochemical performance of TiV2ZrCrMnFeNi was attributed to its higher vanadium/zirconium ratio and abundant interphase boundaries, which act as hydrogen paths and heterogeneous hydride nucleation sites. These results suggest the high potential of dual-phase HEAs as new active electrode materials for Ni-MH batteries.

Pompon Mum-like SiO2/C Nanospheres with High Performance as Anodes for Lithium-Ion Batteries

SiO2 has a much higher theoretical specific capacity (1965 mAh g−1) than graphite, making it a promising anode material for lithium-ion batteries, but its low conductivity and volume expansion problems need to be improved urgently. In this work, pompon mum-like SiO2/C nanospheres with the sandwich and porous nanostructure were obtained by using dendritic fibrous nano silica (DFNS) and glucose as matrix and carbon source, respectively, through hydrothermal, carbonization and etching operations. The influence of SiO2 content and porous structure on its electrochemical performance was discussed in detail. The final results showed that the C/DFNS-6 with a SiO2 content of 6 wt% exhibits the best electrochemical performance as a negative electrode material for lithium-ion batteries due to its optimal specific surface area, porosity, and appropriate SiO2 content. C/DFNS-6 displays a high specific reversible capacity of 986 mAh g−1 at 0.2 A g−1 after 200 cycles, and 529 mAh g−1 at a high current density (1.0 A g−1) after 300 cycles. It also has excellent rate capability, with a reversible capacity that rises from 599 mAh g−1 to 1066 mAh g−1 when the current density drops from 4.0 A g−1 to 0.2 A g−1. These SiO2/C specific pompon mum-like nanospheres with excellent electrochemical performance have great research significance in the field of lithium-ion batteries.

DFT combined to Boltzmann transport theory for optoelectronic and thermoelectric properties investigations for Se (4 & 8 (at.%)) doped Li2SnS3

Cubic Li2SnS3 emerges as a noteworthy ionic conductor and a viable electrode material for lithium secondary batteries. Its application extends to solar cell technologies, owing to its commendable optoelectronic properties and high-power conversion efficiency. In this study, we present density functional theory (DFT)-based first principles calculations for Li2SnS3-xSex (x = 0, 4, and 8% (atomic percent (at.%)) utilizing the modified Becke Johnson (mBJ) approximations, proposing a compelling alternative. Our investigation reveals significant optical absorption in the ultraviolet region for Li2SnS3-xSex (x = 0, 4, and 8%), accompanied by modest effective mass and indirect band gaps of 2.18 eV for the pristine material. Conversely, doped materials exhibit direct band gaps, with values of 2.113 eV for 4% and 2.026 eV for 8%. Furthermore, the calculated thermoelectric power factor underscores the potential and efficacy of Li2SnS3-xSex in thermoelectric energy devices. The findings not only highlight the material’s promise for solar applications but also underscore its candidacy as a novel solid-state electrolyte for lithium-ion batteries. This stems from its robust thermal stability and notable lithium-ion conductivity, positioning Li2SnS3 as a compelling candidate for advanced energy storage technologies.

Ti─O─C Bonding at 2D Heterointerfaces of 3D Composites for Fast Sodium Ion Storage at High Mass Loading Level.

3D composite electrodes have shown extraordinary promise as high mass loading electrode materials for sodium ion batteries (SIBs). However, they usually show poor rate performance due to the sluggish Na+ kinetics at the heterointerfaces of the composites. Here, a 3D MXene-reduced holey graphene oxide (MXene-RHGO) composite electrode with Ti─O─C bonding at 2D heterointerfaces of MXene and RHGO is developed. Density functional theory (DFT) calculations reveal the built-in electric fields (BIEFs) are enhanced by the formation of bridged interfacial Ti─O─C bonding, that lead to not only faster diffusion of Na+ at the heterointerfaces but also faster adsorption and migration of Na+ on the MXene surfaces. As a result, the 3D composite electrodes show impressive properties for fast Na+ storage. Under high current density of 10mAcm-2, the 3D MXene-RHGO composite electrodes with high mass loading of 10mgcm-2 achieve a strikingly high and stable areal capacity of 3mAhcm-2, which is same as commercial LIBs and greatly exceeds that of most reported SIBs electrode materials. The work shows that rationally designed bonding at the heterointerfaces represents an effective strategy for promoting high mass loading 3D composites electrode materials forward toward practical SIBs applications.

Improved photoelectrochemical performance of tungsten-catalyzed graphene nanoplatelet electrodes prepared by hot-wire chemical vapor deposition at low substrate temperatures

The current increase in demand for graphene in various energy applications such as electrode materials for supercapacitors, batteries, thermoelectric, and hydrogen production via water-splitting, the production of high-quality graphene, considering its fascinating physical and electrical properties, high-yield, and large-area has becoming more challenging at the research and development level. Therefore, in this work, graphene nanoplatelets (GNPs) were directly grown on tungsten nanoparticle (W NP)-coated p-type crystalline silicon and quartz substrates using hot-wire chemical vapor deposition at low substrate temperatures (<500 °C). Prior to the GNP deposition, a plasma process was employed to induce the formation of W NPs, which act as a metal catalyst for facilitating the growth of large-area and multi-layer GNPs. The W NPs were formed at substrate temperatures ranging from 250 to 550 °C, with the largest graphene sheet was grown at 450 °C. Higher substrate temperatures promote the growth of high-quality graphene layers with high intensities of G (IG) and 2D bands (I2D), and high I2D/IG ratio values. The GNP photoelectrode prepared at 450 °C demonstrated better photoelectrochemical responses with the highest photocurrent density of 1.65 mA/cm2 at 1.5 VAg/AgCl, the lowest charge transfer resistance (14.0 kΩ), and the highest donor density (2.57 × 10 28 cm−3) compared to the tungsten carbide thin film and W NP electrodes prepared at the same temperature. The effects of substrate temperature on the optical, structural, and photoelectrochemical properties of the as-grown GNPs are discussed.

Disentangling the ligand and electronic structure in KVPO4F1-xOx positive electrode materials by valence-to-core X-ray emission spectroscopy

Understanding the intricate crystal structure of polyanionic positive electrode materials is essential for elucidating the mechanisms involved during cycling and predicting the working potential of the electrode. To achieve this goal, a clear comprehension of how the coordination environment of the transition metal ion influences the ionicity/covalency of the metal-ligand bonds is necessary. Yet, discriminating these ligands poses challenges due to the limited sensitivity to light elements of common characterization techniques such as X-ray diffraction (XRD) and extended X-ray absorption fine structure (EXAFS) analysis. To address this issue, we employed valence-to-core Kβ X-ray emission spectroscopy combined with ab initio modelling and conducted a systematic investigation using potassium vanadium oxyfluoride phosphate compounds with the general formula KVPO4F1-xOx (x = 0, 0.25, 0.5, 0.75, 1). Our approach allows distinguishing the contributions of VF, VO, and VO bonds at the Kβ" region, with intensities highly correlated to the F− and O2− anion composition. Additionally, the evolution of the features at the Kβ2,5 region is highly correlated to the presence of short VO bonds, strongly influencing the electrode potential of the material. Density of state (DOS) analysis based on ab initio modelling of the end member compounds KVPO4F and KVOPO4 further supports the existence of VF and VO bonding through the mixing of F/O p-DOS with V d-DOS. Overall, we present a detailed and reliable approach for understanding the occupied electronic states of the bulk material, proving valuable for a thorough comprehension of the structure of positive electrode materials in batteries.

Fluorinated carbon as high-performance cathode for aqueous zinc primary batteries.

Fluorinated carbon (CFx) has been extensively served as promising positive electrode material for lithium primary batteries due to its high energy density. However, there are comparatively far less reports about the use of CFx on other battery systems, let alone on the research of aqueous batteries. Herein in this study, we employed CFx as the cathode active for aqueous zinc batteries for the first time and systematically investigated its electrochemical behavior under a series of aqueous zinc-ion electrolytes. As is discovered that the F/C ratio (the x value in CFx) of CFx have significant effects on the electrochemical performance of aqueous Zn/CFx batteries. Specifically, CF0.85 exhibits excellent electrochemical property with delivering a remarkable discharge capacity of 503 mA h g-1 and energy density of 388 W h kg-1 (at a current rate of 30 mA g-1 under temperature of 25 °C), much better than several other CFx electrode with F/C ratio of 0.70, 0.95, and 1.10, respectively. Besides, it also exhibits decent temperature performance with discharge capacities of 550 mA h g-1 at 50 °C and 460 mA h g-1 at 0 °C under current density of 30 mA g-1. Furthermore, the electrochemical discharge mechanism based on conversion reaction was further uncovered by applying XPS, XRD, SEM and EDS elemental analysis characterization techniques. In conclusion, these results demonstrate the potential application value of CFx in aqueous zinc primary batteries.

Hierarchical Ni3V2O8@N-Doped Carbon Hollow Double-Shell Microspheres for High-Performance Lithium-Ion Storage.

Transition metal oxides (TMOs) are highly dense in energy and considered as promising anode materials for a new generation of alkaline ion batteries. However, their electrode structure is disrupted due to significant volume changes during charging and discharging, resulting in the short cycle life of batteries. In this paper, the hierarchical Ni3V2O8@N-doped carbon (Ni3V2O8@NC) hollow double-shell microspheres were prepared and used as electrode materials for lithium-ion batteries (LIBs). The utilization efficiency and ion transfer rate of Ni3V2O8 were improved by the hollow microsphere structure formed through nanoparticle self-assembly. Furthermore, the uniform N-doped carbon layer not only enhanced the structural stability of Ni3V2O8, but also improved the overall electrical conductivity of the composite. The Ni3V2O8@NC electrode has an initial discharge capacity of up to 1167.3 mAh g-1 at a current density of 0.3 A g-1, a reversible capacity of up to 726.5 mAh g-1 after 200 cycles, and still has a capacity of 567.6 mAh g-1 after 500 cycles at a current density of 1 A g-1, indicating that the material has good cycle stability and high-rate capability. This work presents new findings on the design and fabrication of complex porous double-shell nanostructures.

Lithium-ion battery electrode properties of hydrogen boride.

Recently, hydrogen boride (HB) with a pseudo-two-dimensional sheet structure was successfully synthesized, and it is theoretically predicted to have high potential as a negative electrode material for alkali metal ion batteries, making it a promising new candidate. This study represents the first experimental examination of the negative electrode properties of HB. HB was synthesized via cation exchange from MgB2. The confirmation of HB synthesis was achieved through various spectroscopic experiments, including synchrotron radiation X-ray diffraction and X-ray photoelectron spectroscopy, in addition to direct observation using transmission electron microscopy. The HB electrode was prepared by mixing the HB powder sample with conductive additive carbon black and a polymer binder. A test cell was assembled with the HB electrode as the working electrode, and lithium metal as the counter and reference electrodes, and its battery electrode properties were evaluated. Although reversible charge-discharge curves with good reversibility were observed, the reversible capacity was 100 ± 20 mA h g-1 which is significantly smaller than the theoretical predictions. Nitrogen gas adsorption experiments were performed on the HB powder sample to determine the specific surface area indicating that the HB sheets were stacked together. It is plausible to consider that this stacking structure led to a reduced lithium-ion storage capacity compared to the theoretical predictions.

Triazacoronene‐Based 2D Conductive Metal–Organic Framework for High‐Capacity Lithium Storage

Abstract2D conductive metal–organic frameworks (2D c‐MOFs) have attracted increasing attention as promising electrode materials for rechargeable batteries due to their designable periodic motifs, large specific surface areas, and prominent electrical conductivity. However, the development of 2D c‐MOF electrode materials with functionality remains a significant challenge because of the limited electroactive ligand motifs available. Herein, a hexahydroxy‐substituted triazacoronene ligand (6OH‐TAC) is deliberately designed and synthesized, which coordinates with Cu2+ ions to form an unprecedented 2D c‐MOF (Cu‐TAC) with functionality sites of efficient lithium storage. The synergistic effect of TAC and CuO4 enables Cu‐TAC as an anode for lithium‐ion batteries with a superior reversible capacity of 772.4 mAh g−1 at 300 mA g−1, remarkable rate performance, and outstanding long‐term cyclability (83% capacity retention at 300 mA g−1 for 600 cycles). These metrics outperform almost all 2D c‐MOF‐based electrodes, shedding light on new opportunities for energy storage devices.