Hybrid Anode Research Articles

Ag Nanoparticle-Decorated Mesocarbon Microbeads for Homogeneous Lithium Deposition toward Stable Hybrid Anodes

Ag Nanoparticle-Decorated Mesocarbon Microbeads for Homogeneous Lithium Deposition toward Stable Hybrid Anodes

A lithiophilic hyperbranched polymer-decorated three-dimensional carbon skeleton boosting highly reversible lithium metal anode

The short cycling lifespan and serious safety issues caused by the crazy growth of dendrites, have severely restricted the practical application of Li metal anodes (LMAs) in high energy density batteries. Here, a three-dimensional (3D) porous conductive framework enriched with lithiophilic functional groups is proposed for stabilizing Li metal anodes, which is fabricated by coating hyperbranched polyol (HP) on the carbon fiber cloth (CFC) through a simple esterification reaction. The abundant lithiophilic groups distributed on HP can disperse the Li ion flow and guide the uniform nucleation of Li. The 3D porous skeleton not only promotes ion diffusion and electron transport but also provides adequate space for Li storage. Symmetrical battery configurated with CFC@HP-Li hybrid anode demonstrates stable cycling over 800 h with low voltage hysteresis at a current density of 2 mA cm−2. With a commercial LiFePO4 (LFP) cathode, the CFC@HP-Li//LFP full battery can realize a high capacity retention rate of 88.9% and a stable Coulombic efficiency (CE) close to 100% after 500 cycles at 2 C. The CFC@HP-Li anode, which is constructed by a modification of LMAs using the targeted lithiophilic coating, provides a promising strategy for the exploration of high-performance Li metal batteries (LMBs).

Three‐Dimensional Hierarchical Ternary Nanostructures Bismuth/Polypyrrole/CNTs for High Performance Potassium‐Ion Battery Anodes

Comprehensive SummaryIn recent years, the anode materials of bismuth(Bi)‐based potassium ion batteries with high theoretical capacity and suitable potassium ion insertion potential have attracted extensive attention. However, due to the volume expansion of Bi, the performance of Bi‐based anode materials is not ideal during potassium ion (de)intercalation. In order to solve these problems, we report a three‐dimensional (3D) ternary bismuth nanoparticles/conductive polymers/carbon nanotubes (Bi/PPy/CNT) hybrid anode material for K‐ion batteries. At a current density of 100 mA·g–1, its reversible capacity reaches 302 mAh·g–1 after 200 cycles, while it reaches 195.7 mAh·g–1 after 600 cycles at 1 A·g–1. Its excellent performance is attributed to the hydrogel network which provides a range of electron transport networks and high porosity. Carbon nanotubes are used as electron enhancers to reduce the volume expansion of Bi particles during the reaction. This study provides a prerequisite for expanding the application of 3D ternary materials.

Hierarchical 1D/2D V3S4@N, S-Codoped rGO Hybrids as High-Performance Anode Materials for Fast and Stable Lithium-Ion Storage

Vanadium sulfides, possessing high theoretical specific capacity and diverse structures, are regarded as attractive and promising anode materials for Li storage. Unfortunately, their practical applications are restricted by intrinsic drawbacks, like inferior structure stability, large volume variation, and even polysulfide dissolutions. Herein, we display a hierarchical one-dimensional/two-dimensional (1D/2D) hybrid material with 1D V3S4 nanofibers supported on 2D N, S-codoped graphene nanosheets and further unveil its electrochemical mechanism for Li-storage and origin of enhanced performance. When applied in LIBs, the optimized 1D/2D hybrid anodes deliver a stable capacity of 717 mA h g–1 over 90 cycles at 100 mA g–1, prolonged cycling stability over 1000 cycles at 1 A g–1, and an excellent rate capability of 370 mA g–1 at 5 A g–1, which are superior to those of the pure V3S4 anode. Such structural design and engineering may provide inspiration for exploring other nanocomposites to achieve desired electrochemical performance.

Insights into the enhanced Lithium-Ion storage performance of CoSx/Carbon polyhedron hybrid anode

In this work, the 3D cobalt sulfide/carbon polyhedral (CoSx/CP) hybrids (x = 1, 2) have been fancily prepared by employing the ZIF-67 as template. The as-prepared CoSx/CP inherit the structure of ZIF-67, realizing the polyhedral structure where the CoSx nanoparticles are well embedded. The battery performance measurements demonstrate that the CoS2 has played a significant role contributing to the lithium ions batteries (LIBs) performance of CoSx/CP. As a result, the capacity of the optimized CoSx/CP is 562 mAh g−1 after 300 cycles at 0.5 A g−1. When cycled at 10 A g−1, it delivers a reversible specific capacity of 131 mAh g−1. The electrochemical analysis points out that the optimized CoSx/CP possesses diverse electrochemical reactions and the lowest charge transfer resistance. Moreover, the insertion mechanism and structural evolution process of CoSx/CP are examined by the in-situ XRD. Beyond that, the unique nanoarchitecture of CoSx/CP guarantees the high specific surface area which enables the large electrode–electrolyte contract area, fast ions diffusion/electron transfer and robust structural stability. Meanwhile, the carbon skeleton is deductive to confine the huge volume expansion of CoSx as well.

Engineering Sodium Metal Anode with Sodiophilic Bismuthide Penetration for Dendrite-Free and High-Rate Sodium-Ion Battery

Sodium (Na) metal batteries with a high volumetric energy density that can be operated at high rates are highly desirable. However, an uneven Na-ion migration in bulk Na anodes leads to localized deposition/dissolution of sodium during high-rate plating/stripping behaviors, followed by severe dendrite growth and loose stacking. Herein, we engineer the Na hybrid anode with sodiophilic Na3Bi-penetration to develop the abundant phase-boundary ionic transport channels. Compared to intrinsic Na, the reduced adsorption energy and ion-diffusion barrier on Na3Bi ensure even Na+ nucleation and rapid Na+ migration within the hybrid electrode, leading to uniform deposition and dissolution at high current densities. Furthermore, the bismuthide enables compact Na deposition within the sodiophilic framework during cycling, thus favoring a high volumetric capacity. Consequently, the obtained anode was endowed with a high current density (up to 5 mA∙cm−2), high areal capacity (up to 5 mA∙h∙cm−2), and long-term cycling stability (up to 2800 h at 2 mA∙cm−2).

High‐performance Sn‐based anode with robust lignin‐derived hard carbon support for sodium‐ion batteries

AbstractTin anode has great potential for sodium‐ion batteries owing to its high theoretical capacity, but its tremendous volume expansion during the sodium (de)alloying processes leads to the structural degradation and cycling instability. Herein, we report a new design strategy by using low‐cost enzymatic hydrolysis lignin‐derived hard carbon as an ideal support for Sn particles dispersion. Sn can be uniformly anchored on the robust carbon substrate, to efficiently relieve Sn volume expansion upon cycling. In addition, conductive hard carbon support can facilitate electrons to transfer and further enhance Na+ storage capacity and accelerate facile Na+ diffusion in the Sn/C hybrid anodes. The resultant Sn/C hybrids as anodes deliver high‐rate performance as well as distinguished cycling stability in view of high reversible capacity of 374 mAh g−1 at 20 mA g−1 and capacity retention of 91% at 1000 mA g−1 after 1000 cycles, benefiting from high electrical conductivity, highly dispersed Sn particles and suitable pore structure. This work is expected to provide fresh insight into cost‐effective Sn‐based anodes for sodium ion batteries.

Enhanced bioenergy and nutrients recovery from wastewater using hybrid anodes in microbial nutrient recovery system

BackgroundThe combined microbial fuel cell–microbial nutrient recovery system has lately been thoroughly explored from an engineering standpoint. The relevance of microbial communities in this process, on the other hand, has been widely underestimated.ResultsA lab-scale microbial nutrients recovery system was created in this work, and the microbial community structure was further defined, to give a thorough insight into the important microbial groups in the present system. We reported for the first-time different hybrid anodes of activated carbon and chitosan that were used in the microbial nutrient recovery system for bioenergy production, and, for the removal of COD and recovery of nutrients present in the wastewater. The hybrid anodic materials were studied to adapt electrochemically active bacteria for the recovery of nutrients and energy generation from wastewater without the need for an external source of electricity. The potential of the created hybrid anodes in terms of nutrients recovery, chemical oxygen demand elimination, and energy generation from municipal wastewater was thoroughly examined and compared with each other under similar operating conditions. When the COD loading was 718 mg/L, a total COD removal of ~ 79.2% was achieved with a hybrid activated carbon and chitosan anode having an equal ratio after 10 days of the operation cycle. The maximum power density estimated for hybrid anode (~ 870 mWm−2) was found.ConclusionOverall, this work reveals a schematic self-driven way for the collection and enrichment of nutrients (~ 72.9% phosphorus recovery and ~ 73% ammonium recovery) from municipal wastewater, as well as consistent voltage production throughout the operation.

Diglyme-based electrolytes boosting high-rate and stable sodium-ion storage for three-dimensional VS4/Reduced graphene oxide hybrid anodes

VS4, as a promising anode material for sodium ion batteries (SIBs), has attracted great attention due to its large interchain distance of 5.83 Å. However, the reported VS4 anodes always show a low capacity and unstable cycling performance. Herein, a three-dimensional (3D)-VS4/reduced graphene oxide (rGO) hybrid (denoted 3D-VS4/rGO) has been prepared, having a structure of VS4 nanorods (85.8 wt%) uniformly anchored to flexible graphene sheets to form a 3D hierarchical framework. It is interesting found that such anode shows superior electrochemical performance with excellent rate capability (700 mAh g−1 at 5 A g−1) and long cyclic stability (587 mAh g−1 over 400 cycles at 5 A g−1) in 1 M NaPF6 diglyme-based electrolyte, much better than the performance in 1 M NaCF3SO3 diglyme-based electrolyte. The simulation results reveal that the different coordination shell structure of Na+ of different sodium salts in the electrolyte is the main reason for the performance differences, and a smaller solvation shell of Na+-solvent in NaPF6 rather than that of Na + -anion-solvent in NaCF3SO3 led to the fast reaction kinetics in the sodiation/desodiation process, showing the importance of electrode and electrolyte matching in improving the electrochemical performance of SIBs.

In-situ continuous hydrothermal synthesis of TiO2 nanoparticles on conductive N-doped MXene nanosheets for binder-free Li-ion battery anodes

Anode materials are key to determining the energy density, cyclability and of life recyclability for Li-ion energy storage systems. High surface area materials, such as MXenes, can be manufactured with improved electrochemical properties that remove the need for polymeric binders or hazardous chemicals that pose a challenge to recycle Li-ion batteries. However, there remains a challenge to produce Li-ion anode materials that are binder free and poses energy storage characteristics that match the current carbon-based electrodes. Here we show the synthesis of N-doped MXene-TiO2 hybrid anode materials using an aqueous route. N-doped TiO2-MXene was modified using a single step continuous hydrothermal process. Capacity tests indicate an improvement from the initial specific energy capacity of 305 mAhg−1 to 369 mAhg−1 after 100 cycles at a charge rate of 0.1 C and a Coulombic efficiency of 99.7%. This compares to 252 mAhg−1 for the unmodified MXene which exhibited significant capacity fade to 140 mAhg−1. The ability to manufacture a Li-ion anode that does not require toxic chemicals for processing into an electrode and exhibits good energy storage characteristics in a binder free system is a significant step forward for energy storage applications.

SnO2/SnS2 heterostructure@ MXene framework as high performance anodes for hybrid lithium-ion capacitors

Among all kinds of energy storage devices, lithium-ion capacitors (LICs) emerged victorious because of their advantages of high energy densities and power densities. The main issue that limits the performance of LICs is the mismatch in reaction kinetics caused by the disparate energy storage mechanisms of the positive and negative materials. Herein, a Sn-based heterostructure@MXene anode material was synthesized to achieve excellent rate performance and to increase the lithium storage capacity, which enables a good match with the cathode. In the synthesized hybrid electrode, the heterostructure can regulate the charge transmission at interfaces and improve the kinetics of electron conduction and ion diffusion. Meanwhile, the highly conductive MXene can buffer the large volumetric change of SnS2/SnO2 nanoparticles, and synergically improve electrochemical properties of the hybrid electrode. The hybrid electrode exhibited remarkable rate performance and cycle stability, showing 619 mAh g−1 at 0.5 A g−1 after 200 cycles, which greatly reduced the kinetic gap with capacitor-type cathodes. The assembled LICs based on the SnS2/SnO2@MXene hybrid anode and nitrogen-doped activated carbon (N-AC) cathode offer a high power/energy density (maximum 11.25 kW kg−1 and 145.2 Wh kg−1) and a long cycling life (93.6% capacity retention after 2000 discharges/charges). This unique structure and the composition design provide a promising path for the fast kinetic LICs anode materials.

A dual lithiated alloy interphase layer for high-energy–density lithium metal batteries

Lithium metal batteries represent potential candidates for high-energy–density batteries. However, non-uniform Li deposition and dendrite growth limit the practical applications of Li anodes in solid-state and liquid-phase battery systems. This report investigates the conversion mechanism of an aluminum coordination compound (Al(MMP)3) at the interface of a lithium metal anode. Based on the proposed mechanism, a novel dual alloy comprising a LixAl-LixP hybrid interphase is designed to promote interfacial charge balance. Under the synergic effect of a fluoropolymer, the organic/inorganic protective layer containing the dual lithiated alloy exhibits short-term Li storage and rapid Li+ transport, thereby limiting the accumulation of inactive lithium and decreasing the Li+ migration barrier. Upon implementing the hybrid anode, the electrochemical life span of the Li metal battery exceeds 2000 h. Moreover, pairing with a Ni-rich cathode leads to excellent capacity retention and stable coulomb efficiency. The developed strategy can guide future advancements in lithium metal batteries with long cycle lives.

Large areal capacity all-in-one lithium-ion battery based on boron-doped silicon/carbon hybrid anode material and cellulose framework

Si, featuring ultra-large theoretical specific capacity, is a very promising alternative to graphite for Li-ion batteries (LIBs). However, Si suffers from intrinsic low electrical conductivity and structural instability upon lithiation, thereby severely deteriorating its electrochemical performance. To address these issues, B-doping into Si, N-doped carbon coating layer, and carbon nanotube conductive network are combined in this work. The obtained Si/C hybrid anode material can be “grown” onto the Cu foil without using any binder and delivers large specific capacity (2328 mAh g−1 at 0.2 A g−1), great rate capability (1296.8 mAh g−1 at 4 A g−1), and good cyclability (76.7% capacity retention over 500 cycles). Besides, a cellulose separator derived from cotton is found to be superior to traditional polypropylene separator. By using cellulose as both the separator host and the mechanical skeleton of two electrodes, a flexible all-in-one paper-like LIB is assembled via a facile layer-by-layer filtration method. In this all-in-one LIB, all the components are integrated together with robust interfaces. This LIB is able to offer commercial-level areal capacity of 3.47 mAh cm−2 (corresponding to 12.73 mWh cm−2 and 318.3 mWh cm−3) and good cycling stability even under bending. This study offers a new route for optimizing Si-based anode materials and constructing flexible energy storage devices with a large areal capacity.

Catkin-Derived Hybrid Anode for High-Performance Lithium Ion Batteries

Catkin-Derived Hybrid Anode for High-Performance Lithium Ion Batteries

Potassium-Enriched Graphite for Use as Stable Hybrid Anodes in High-Efficiency Potassium Batteries

Potassium-Enriched Graphite for Use as Stable Hybrid Anodes in High-Efficiency Potassium Batteries

In situ growth of CoO nanosheets on a carbon fiber derived from corn cellulose as an advanced hybrid anode for lithium-ion batteries

A facile method is proposed to prepare CoO/carbon fiber (CoO/CF) hybrids by employing corn cellulose as the biocarbon source for high-performance lithium ion batteries.

Hybrid Design of Bulk‐Na Metal Anode to Minimize Cycle‐Induced Interface Deterioration of Solid Na Metal Battery

AbstractThe pursuit for high‐energy and intrinsically safe energy storage is significantly driving the development of solid‐state alkali metal batteries. The interfacial contact between the metal anode and the solid electrolyte plays a key role in enabling stable cycling of solid batteries. However, the sluggish alkali atom replenishment rate during stripping unavoidably leads to the interface deterioration that destroys the initial physical contact by forming interfacial voids and triggering the dendrite growth. Herein, a hybrid bulk Na anode approach is proposed by incorporating an ion‐conducting phase into a metallic Na matrix, constructing an abundant interfacial electrochemical reaction area and enabling a balanced Na replenishment and consumption to minimize cycle‐induced interface deterioration. Specific attention is paid to the effects of the second phase on the wettability and creep ability of hybrid Na metal. A high critical current density (3.1 mA cm‐2) and long cycling life (6000 h in 0.5 mA cm‐2) are achieved for the symmetric cells. Full cells coupling the hybrid anode with the Na3V2(PO4)3/C cathode deliver excellent cyclability over 7300 cycles at a high rate of 5 C. The viewpoint of balancing the consumption and replenishment rate of metal atoms paves a new way for designing cycle‐stable anode/electrolyte interface in solid‐state batteries.

Enhancing the Catalytic Activity and Coking Tolerance of the Perovskite Anode for Solid Oxide Fuel Cells through In Situ Exsolution of Co-Fe Nanoparticles

The in situ exsolved nanoparticles from the perovskite matrix have achieved increasing attention and wide applications in solid oxide fuel cells (SOFCs) due to their excellent stability and high catalytic activity. Herein, an A-site-deficient (Ba0.9La0.1)0.95Co0.7Fe0.2Nb0.1O3 – δ (BL95CFN) perovskite oxide with in situ exsolved Co-Fe nanoparticles is developed and investigated as an anode for SOFCs. Compared with stoichiometric BLCFN, a tiny A-site deficiency (5%) promoted the exsolution of cobalt and iron from the perovskite matrix of BL95CFN. This hybrid anode catalyst showed excellent electrochemical performance. The polarization resistance is 0.11 Ω cm2 for the BL95CFN anode at 750 °C, about 42% lower than that of the BLCFN anode. The maximum peak density (MPD) reaches 513.2 mW cm–2 at 750 °C for an electrolyte-supported single cell with the BL95CFN anode. The high electrochemical performance could be attributed to the accelerated hydrogen surface exchange process provided by exsolved Co-Fe nanoparticles and oxygen ion transport in the A-site-deficient perovskite matrix. High-resolution transmission electron microscope (HRTEM) reveals that exsolved Co-Fe nanoparticles are embedded in the oxide matrix, forming a firm anchoring structure, which ensures excellent anode coking tolerance. At the current density of 200 mA cm–2, the output voltage of the single cell remained stable within 200 h in methane fuel. Overall, the high catalytic activity and coking tolerance of the hybrid electrocatalyst manifest a bright prospect of application in SOFCs and electrolytic cells.

Critical roles of reduced graphene oxide in the electrochemical performance of silicon/reduced graphene oxide hybrids for high rate capable lithium-ion battery anodes

Silicon/reduced graphene oxide (Si/rGO) composite electrodes have been investigated for the multiple benefits of rGO in providing mechanical integrity to buffer the silicon volume expansion, while maintaining electronic contact with Si to provide a Li-ion transport pathway and to form a uniform solid electrolyte interface (SEI) layer. In particular, we extensively studied the properties of rGO particles that were reduced from three different routes, namely by heat treatment (TrGO), by chemical treatment (CrGO), and by plasma treatment (PrGO), and co-related them to the electrochemical performance of Si/rGO hybrid anodes. Our results revealed that decreased structural and functional group defects in rGO led to a higher initial columbic efficiency (ICE) of 84%, whereas a higher sphericity of rGO particles resulted in a more stable cycle-life performance for Si/rGO electrodes with 93% capacity retention after 100 cycles at 1C/1C rates. We also observed the important role of the electrical conductivity of rGO in the electrochemical performance of Si/rGO at faster charging-discharging rates, resulting in a capacity of 1000 mAh/g at 2C/2C rates.

In situ growth of NaTiO2 nanotubes on Ti3C2Fx for enhanced sodium ion batteries

In this paper, we aim to prepare NaTiO2 nanotubes (NTO NTs) in situ on Ti3C2Fx as hybrid anode for enhanced sodium-ion batteries (SIBs). As expected, the NTO/Ti3C2Fx anode exhibits low charge transfer resistance of 88.38 Ω and delivers high specific capacity of 130.2 mAh·g−1 after 800 cycles at 100 mA·g−1 with Coulombic efficiency nearly to 100%. This is attributed to the fact that the NTO NTs perpendicularly grow on both sides of Ti3C2Fx, which not only increases the electrode-electrolytes interaction and expands the layer spacing of Ti3C2Fx, leading to high Na+ diffusion, but also promotes the storage of Na+.