Ternary Anode Research Articles

Olivine-Type Fe2GeX4 (X = S, Se, and Te): A Novel Class of Anode Materials for Exceptional Sodium Storage Performance.

The introduction of abundant metals to form ternary germanium-based chalcogenides can dilute the high price and effectively buffer the volume variation of germanium. Herein, olivine-structured Fe2GeX4 (X = S, Se, and Te) are synthesized by a chemical vapor transport method to compare their sodium storage properties. A series of in situ and ex situ measurements validate a combined intercalation-conversion-alloying reaction mechanism of Fe2GeX4. Fe2GeS4 exhibits a high capacity of 477.9mA h g-1 after 2660 cycles at 8 A g-1, and excellent rate capability. Furthermore, the Na3V2(PO4)3//Fe2GeS4 full cell delivers a capacity of 375.5mA h g-1 at 0.5 A g-1, which is more than three times that of commercial hard carbon, with a high initial Coulombic efficiency of 93.23%. Capacity-contribution and kinetic analyses reveal that the alloying reaction significantly contributes to the overall capacity and serves as the rate-determining step within the reaction for both Fe2GeS4 and Fe2GeSe4. Upon reaching a specific cycle threshold, the assessment of the kinetic properties of Fe2GeX4 primarily relies on the ion diffusion process that occurs during charging. This work demonstrates that Fe2GeX4 possesses promising practical potential to outperform hard carbon, offering valuable insights and impetus for the advancement of ternary germanium-based anodes.

Influence of Polypyrrole on Phosphorus- and TiO2-Based Anode Nanomaterials for Li-Ion Batteries.

Phosphorus (P) and TiO2 have been extensively studied as anode materials for lithium-ion batteries (LIBs) due to their high specific capacities. However, P is limited by low electrical conductivity and significant volume changes during charge and discharge cycles, while TiO2 is hindered by low electrical conductivity and slow Li-ion diffusion. To address these issues, we synthesized organic-inorganic hybrid anode materials of P-polypyrrole (PPy) and TiO2-PPy, through in situ polymerization of pyrrole monomer in the presence of the nanoscale inorganic materials. These hybrid anode materials showed higher cycling stability and capacity compared to pure P and TiO2. The enhancements are attributed to the electrical conductivity and flexibility of PPy polymers, which improve the conductivity of the anode materials and effectively buffer volume changes to sustain structural integrity during the charge and discharge processes. Additionally, PPy can undergo polymerization to form multi-component composites for anode materials. In this study, we successfully synthesized a ternary composite anode material, P-TiO2-PPy, achieving a capacity of up to 1763 mAh/g over 1000 cycles.

3D Ternary Alloy Artificial Interphase Toward Ultra‐Stable and Dendrite‐Free Aqueous Zinc Batteries

AbstractRechargeable aqueous zinc‐ion batteries (AZIBs) are one of the most promising post‐lithium battery technologies due to their low cost, high safety, and environmental friendliness. However, their practical development is hindered by the issues of Zn metal anodes, including dendrite growth, passivation, hydrogen evolution and other side reactions. Herein, to circumvent these issues, a facile and universal alloy electrodeposition strategy is proposed to construct a 3D structured ternary Zn alloy artificial interphase layer on Zn foil as an anode for high‐performance AZIBs. The density functional theory (DFT) theoretical calculations, in situ optical visualization and spectroscopic results validate that the zincophilic Zn─Sn─Bi@Zn ternary alloy anode with lower migration energy barrier and weak hydrogen adsorption sites can promote the uniform Zn deposition and suppress hydrogen evolution reactions. The Zn─Sn─Bi@Zn//NH4V4O10 full cell demonstrates a high specific capacity 110.4 mAh g−1 even after 10 000 cycles at 5.0 A g−1. Notably, the full cell with a high NH4V4O10 cathode loading mass of ≈20.0 mg cm−2 maintains cyclic stability for 400 cycles. This work proposes an innovative Zn‐based ternary alloy anode methodology as a design strategy for advanced AZIBs and beyond.

Effective Cu-Fe oxide/ multidimensional nanocarbon-coupled ternary composite-based anode: Mechanistic insight into interface tuning for swift Li-ion diffusion

This work focused on engineering the hybrid nanocomposite-based anode comprising CuFe2O4 (CFO), reduced graphene oxide (RG), and functionalized carbon nanotubes (FC) to investigate its Li-ion storage kinetics. The ternary nanocomposites CFO/RG/FC (CFO-C) demonstrated a specific capacity (SC) of 760 mAh/g at a Cdensity of 200 mA/g after 100 electrochemical charge-discharge cycles and an SC of 450 mAh/g at a high Cdensity of 500 mA/g after 300 electrochemical cycles. Results revealed that the addition of RG and FC aided in enhancing the electrical transport at the interface, in turn, it assisted in augmenting the Li-ion storage capability from ∼240 to ∼760 mAh/g at the end of 100 charge-discharge cycles with a Cdensity of 200 mA/g. RG and FC acted as anchoring sites for CFO and spacer, respectively, which resulted in improved electrical transport to accelerate Li-ion diffusion transport by fivefold. Such composite anode is a probable candidate as the high-performance anode in designing high-energy density Li-ion battery applications.

3D Printed Sodium‐Ion Batteries via Ternary Anode Design Affording Hybrid Ion Storage Mechanism

AbstractSodium‐ion batteries (SIB), as one of the most appealing grid‐scale energy storage devices, have to deal with the trade‐off between the capacity output and rate performance. Utilizing 3D‐printed (3DP) anode materials with hybrid sodium storage mechanism and elevated mass loading is promising yet poorly explored. Herein, the design of a prototype ternary composite is reported, MoS2@Bi/N‐doped carbon, as a sodium storage candidate to achieve high reversible capacity (604 mAh g−1 at 0.1 A g−1 with an initial output of 709 mAh g−1) and outstanding rate capability (169.6 mAh g−1 at 15 A g−1), outperforming the state‐of‐the‐art reports. This is realized by delicate structural and interfacial engineering of the composite anode, markedly synergizing the conversion‐typed MoS2, alloy‐typed Bi, and adsorption‐typed N‐doped carbon. Theoretical simulations and operando instrumental analysis elaborate the reasons of the boosted electrochemical performance. Encouragingly, a fully 3DP SIB affording an areal mass loading of up to 11.7 mg cm−2 is demonstrated, retaining a capacity of 114 mAh g−1 at 1.0 A g−1. This work would facilitate the design of 3DP SIB devices with the employment of advanced electrodes harnessing hybrid ion storage features.

Preparation and electrochemical performances for silicon-carbon ternary anode materials with artificial graphite as conductive skeleton

Preparation and electrochemical performances for silicon-carbon ternary anode materials with artificial graphite as conductive skeleton

Boosting Solid-State Reconversion Reactivity to Mitigate Lithium Trapping for High Initial Coulombic Efficiency.

An initial Coulombic efficiency (ICE) higher than 90% is crucial for industrial lithium-ion batteries, but numerous electrode materials are not standards compliant. Lithium trapping, due to i) incomplete solid-state reaction of Li+ generation and ii) sluggish Li+ diffusion, undermines ICE in high-capacity electrodes (e.g., conversion-type electrodes). Current approaches mitigating lithium trapping emphasize ii) nanoscaling (<50nm) to minimize Li+ diffusion distance, followed by severe solid electrolyte interphase formation and inferior volumetric energy density. Herein,this work accentuates i) instead, to demonstrate that the lithium trapping can be mitigated by boosting the solid-state reaction reactivity. As a proof-of-concept, ternary LiFeO2 anodes, whose discharged products contain highly reactive vacancy-rich Fe nanoparticles, can alleviate lithium trapping and enable a remarkable average ICE of ≈92.77%, much higher than binary Fe2 O3 anodes (≈75.19%). Synchrotron-based techniques and theoretical simulations reveal that the solid-state reconversion reaction for Li+ generation between Fe and Li2 O can be effectively promoted by the Fe-vacancy-rich local chemical environment. The superior ICE is further demonstrated by assembled pouch cells. This work proposes a novel paradigm of regulating intrinsic solid-state chemistry to ameliorate electrochemical performance and facilitate industrial applications of various advanced electrode materials.

Unraveling the atomic-level manipulation mechanism of tin-based ternary anodes via hetero-anion engineering for stable sodium ion storage

The gradual retardation of heterogeneous interface reactions during extended cycling results in significant capacity loss, particularly in the initial few cycles. This is due to the inhomogeneous distribution and structural degradation of heterointerfaces. Currently, a range of atomic-level tuning strategies are employed to enhance the intrinsic transfer characteristics for sodium-ion batteries (SIBs). Herein, the defect-rich single-phase ternary tin sulfide selenide (SnSe1.33S0.67) anode is constructed via favorable heteroatom(S) introducing. Such a defective open structure employed as anodes for SIBs, delivers a superior rate performance of 452.3 mAh g−1 at 5.0 A g−1, and excellent cycling stability, with a capacity retention of 535.8 mAh g−1 after 500 cycles at 1.0 A g−1. The exceptional performance is attributed to the rapid diffusion of ions/electrons through lattice defects and heteroatom coexistence, as well as the high tolerance for volume changes resulting from optimized phase transition modes and enhanced structural rigidity, as demonstrated by experimental results and density functional theory (DFT) calculations. Through the heteroatoms injection strategy, this work offers deeper insights into the correlation between precise regulation of internal defects and superior storage performance in SIBs.

Highly lithiophilic and structurally stable Cu–Zn alloy skeleton for high-performance Li-rich ternary anodes

Lithium (Li)-rich ternary alloy, comprising a multi-alloy phase as the built-in three-dimensional (3D) framework and a Li metal phase as a reversible Li reservoir, is a promising high-energy–density anode for rechargeable Li metal batteries. The introduction of metal/metalloid components to the alloy can effectively regulate Li deposition and maintain the dimensional integrity of the Li anode. Herein, the lithium–copper–zinc (Li–Cu–Zn) ternary alloy, as a new type of alloy anode, is synthesized via a facile thermal melting method. The fully delithiated 3D scaffold comprised two Cu–Zn alloy phases named CuZn and CuZn5. These alloy phases exhibit higher lithiophilicity and structural stability than Li–Zn and Li–Cu alloys. Moreover, the CuZn phase is electrochemically inert, ensuring the geometric stability of the anode, while the CuZn5 phase can readily undergo alloying reaction with Li to form the LiZn phase, thereby facilitating uniform Li nucleation and deposition. The hybridized multiphase alloy structure and specific energy storage mechanism of the Cu–Zn based alloy scaffold in the ternary alloy anode facilitate dendrite-free Li deposition and prolonged cycle lifetime. The Li metal full battery based on lithium iron phosphate (LiFePO4) cathode exhibits high cycling stability with high-capacity retention of 95.4% after 1000 cycles at 1C.

Enhanced membraneless fuel cells by electrooxidation of ethylene glycol with a nanostructured cobalt metal catalyst

The advancement of effective and long-lasting electrocatalysts for energy storage devices is crucial to reduce the impact of the energy crisis. In this study, a two-stage reduction process was used to synthesize carbon-supported cobalt alloy nanocatalysts with varying atomic ratios of cobalt, nickel and iron. The formed alloy nanocatalysts were investigated using energy-dispersive X-ray spectroscopy, X-ray diffraction, and transmission electron microscopy to determine their physicochemical characterization. According to XRD results, Cobalt-based alloy nanocatalysts form a face-centered cubic solid solution pattern, illustrating thoroughly mixed ternary metal solid solutions. Transmission electron micrographs also demonstrated that samples of carbon-based cobalt alloys displayed homogeneous dispersion at particle sizes ranging from 18 to 37 nm. Measurements of cyclic voltammetry, linear sweep voltammetry, and chronoamperometry revealed that iron alloy samples exhibited much greater electrochemical activity than non-iron alloy samples. The alloy nanocatalysts were evaluated as anodes for the electrooxidation of ethylene glycol in a single membraneless fuel cell to assess their robustness and efficiency at ambient temperature. Remarkably, in line with the results of cyclic voltammetry and chronoamperometry, the single-cell test showed that the ternary anode works better than its counterparts. The significantly higher electrochemical activity was observed for alloy nanocatalysts containing iron than for non-iron alloy catalysts. Iron stimulates nickel sites to oxidize cobalt to cobalt oxyhydroxides at lower over-potentials, which contributes to the improved performance of ternary alloy catalysts containing iron.

Amorphous MnO2-Modified FeOOH Ternary Composite with High Pseudocapacitance As Anode for Lithium-Ion Batteries

The development of high-capacity anodes that are stable at high rates is of immediate interest as a potential alternative to the commercial graphite anode in lithium-ion batteries (LIBs). Conversion-based transition metal oxides, known for their high theoretical capacities, have been extensively studied in this regard. In this work, a ternary FeOOH-rGO-MnO2 composite has been suitably designed to address the limitations of the bare FeOOH anode arising from poor conductivity and volume expansion. A simple low-temperature synthesis method was employed to obtain a uniform distribution of FeOOH nanorods over the rGO matrix, which was further modified with a buffer layer of amorphous MnO2 nanosheets. While cycling at high rates, the modified composite anode delivered capacities of 956, 842, and 688 mAh g–1 at 1, 2, and 5 A g–1, respectively, for 200 cycles along with a cycling stability of 900 mAh g–1 at 1 A g–1 for 100 cycles. Various electrochemical techniques were used to analyze the superior performance of the ternary composite anode. The carbon matrix effectively provides favorable pathways for electron conduction and aids in the stable SEI formation, while the amorphous MnO2 sustains the structural integrity of the electrode by controlling volume expansion. Further, the exceptional stability of the anode at high rates was attributed to the marked increase in capacitive contribution in the FeOOH-rGO-MnO2 ternary composite anode, paving the way for faster electrode kinetics.

AlSixP: A new family of ternary Si-based anodes for Li-ion batteries with superior Li-storage properties

Silicon, as the highest capacity lithium-ion battery (LIB) anode material, has been commercialized due to its mature industrial foundation, abundant reserves, and environmental benign. However, its relatively slow Li-ionic and electronic conductivity impede its large-scale application when fast charging and discharging are required. To significantly improve the reaction kinetics, we propose to co-introduce aluminum and phosphorus into silicon at the same time, forming a novel family AlSi x P (x = 1, 3, 6) solid solutions. As anodes for LIBs, the equimolar compound of AlSiP presents longer cycling stability and much higher rate performance than Si counterparts due to the faster electronic and Li-ionic conductivity and the rich underlithiated electrochemical intermediates of which reduce the volume variation. The AlSi 3 P and AlSi 6 P are also prepared and present similar Li-storage superiority, suggesting the AlSi x P series materials are promising to be utilized in the real world.

Modifying SiO as a ternary composite anode material((SiOx/G/SnO2)@C) for Lithium battery with high Li-ion diffusion and lower volume expansion

The silicon suboxide (SiO) anode material is considered to be a promising anode material of Lithium-ion batteries (LIBs), because of its high theoretical capacity. However, there are severe problems for SiO, including the huge volume change (200%), the low electrical conductivity and the low first Coulombic efficiency. In order to solve those problems, a ternary composite ((SiOx/G/SnO2)@C) (G denotes graphite) with carbon coating layer is prepared by ball milling, spray drying and sintering. In the composite, graphite as one part of the active materials, can improve the Coulombic efficiency and control volume change of SiOx. To further restrain the high-volume change of SiOx, the carbon coating layer is designed. In particular, owing to the presence of SnO2, a better electrochemical performance for (SiOx/G/SnO2)@C is obtained. The results show that the first charging capacity of (SiOx/G/SnO2)@C can reach 382.6 mAh g−1 at current density of 100 mA g−1 and the Coulombic efficiency is improved from 62.2% to 74.9%. After 110 cycles, the charging capacity is 424.6 mAh g−1 and the capacity retention rate is 103.9%. In addition, after 90 cycles of rate performance test, (SiOx/G/SnO2)@C exhibited the highest capacity retention of 104.7%.

Enhanced reaction kinetics enabled by a bi-element co-doping strategy for high-performance ternary Si-based anodes of Li-ion batteries

The slow electron and Li-ion transport as well as poor ability to resist against volume variation restrict severely the Si anodes commercialization. Herein, we, for the first time propose a three-in-one approach by co-introducing Al and P into Si to form the complete solid solutions of AlSixP (x = 2/3, 2, 6) by a facile and low-cost mechanical ball milling method. As LIBs anodes, first-principles calculations and experimental measurements demonstrate that the AlSi6P sample has the fastest Li-ionic and electronic conductivities among materials of AlSi2/3P, AlSi2P, AlSi6P and Si8, thus offering the best Li-storage performances of large reversible capacity, high energy efficiency, long cycling life and fast rate capability. The crystallographic, spectrographic and electrochemical characterizations demonstrate that the AlSi6P sample stores Li-ions by a reversible process of Li-intercalation reaction and then conversion reaction where a Li-ionic conductor of LiSi2P3, and electronic conductors of Li12Al3Si4 and Li15Si4 were produced simultaneously, thus delivering excellent Li-storage performances. The AlSi6P@graphite composite achieves 1,496 mA h g−1 after 100 cycles at 500 mA g−1, 1,058 mA h g−1 after 500 cycles, and 1,159 mA h g−1 at 10,000 mA g−1, thus holding the promise to be applied in the near future. This co-doping strategy provides guidance and a new direction for the design of new energy materials.

Ternary chalcogenide anodes for high-performance potassium-ion batteries and hybrid capacitors via composition-mediated bond softening and intermediate phase

• Composition-tunable ternary chalcogenides is designed to achieve highly-reversible potassium ion storage. • Bi/Sb composition-induced chemical bond softening shows outstanding structure stability. • Intermediate quaternary phase K 3 (Bi,Sb)Se 3 promotes a reversible conversion/alloying reaction based on 12-electron transfer. • The K-ion full cell devices demonstrate 76.9 W h kg −1 /1964.2 W kg −1 for batteries and 54.3 W h kg −1 /3685.7 W kg −1 for hybrid capacitors, respectively. Despite the high potassium-ion storage of chalcogenide anodes relative to intercalation-based graphite, inhibition of their large volume change during the potassiation/depotassiation process, and stabilization of reversible electrochemical reactions to ensure efficient electron/ion transfer remain challenging. Here we report composition-tunable ternary chalcogenides that achieve highly reversible potassium-ion storage through synergistic interactions between elements. A series of Bi 2−x Sb x Se 3 ternary chalcogenide (x = 0, 0.25, 1, 1.75, 2) solid solutions with a full composition range are designed using a facile high energy mechanical milling method. Sb 2 Se 3 substituted by Bi gives rise to a chemical bond softening effect that accompanies structural transition and maintains excellent structural stability. Meanwhile, the intermediate quaternary-phase K 3 (Bi,Sb)Se 3 enables a highly reversible 12-electron transfer conversion/alloying reaction during the potassiation/depotassiation process. Various electrochemical analyses show that Bi 2−x Sb x Se 3 inherits the advantages of binary Sb 2 Se 3 (high capacity) and Bi 2 Se 3 (stability) while balancing their respective disadvantages, confirming the synergistic effect of ternary chalcogenide systems. By engineering Bi 2−x Sb x Se 3 implemented into potassium-ion based full cells, we demonstrate a high energy/power density of 76.9 W h kg −1 /1964.2 W kg −1 for batteries and 54.3 W h kg −1 /3685.7 W kg −1 for hybrid capacitors. This work illustrates how to exploit the underlying multilateral science and the relevant electrochemistry of ternary chalcogenides to achieve excellent electrochemical performance, suggesting a new avenue of anode design for potassium-ion storage. .

The fabrication of hierarchical porous nano-SnO2@carbon@humic acid ternary composite for enhanced capacity and stability as anode material for lithium ion battery

High performance of SnO2 @C@HA ternary anode material was fabricated by microwave-assisted hydrothermal and subsequent calcination process in the presence of humic acid (HA) and super P. In the calcination process, tin hydroxide is converted to tin oxide and then be crystallized. For comparison purpose, two other composites including SnO2 @C and SnO2 @HA are also prepared, and the structures, morphology and electrochemical performances of these composites are investigated in detail. The results showed that the addition of HA improved the dispersibility of the SnO2 nanoparticles and the specific surface area of the composite. Electrochemical measurement showed that the SnO2 @C@HA anode exhibited high retention capacity during charge-discharge cycling as compared to that of the binary systems, which was attributed to the porous hierarchical structure and high conductivity of SnO2 @C@HA. The reversible specific capacity of SnO2 @C@HA anode can be maintained at 612.0 mA h g−1 after 500 cycles at a current density of 500 mA g−1.

Composition dependent electrochemical properties of earth-abundant ternary nitride anodes

Growing energy storage demands on lithium-ion batteries necessitate exploration of new electrochemical materials as next-generation battery electrode materials. In this work, we investigate the previously unexplored electrochemical properties of earth-abundant and tunable Zn1−xSn1+xN2 (x = −0.4 to x = 0.4) thin films, which show high electrical conductivity and high gravimetric capacity for Li insertion. Enhanced cycling performance is achieved compared to previously published end-members Zn3N2 and Sn3N4, showing decreased irreversible loss and increased total capacity and cycle stability. The average reversible capacity observed is &amp;gt;1050 mAh/g for all compositions and 1220 mAh/g for Zn-poor (x = 0.2) films. Extremely Zn-rich films (x = −0.4) show improved adhesion; however, Zn-rich films undergo a phase transformation on the first cycle. Zn-poor and stoichiometric films do not exhibit significant phase transformations which often plague nitride materials and show no required overpotential at the 0.5 V plateau. Cation composition x is explored as a mechanism for tuning relevant mechanical and electrochemical properties, such as capacity, overpotential, phase transformation, electrical conductivity, and adhesion. The lithiation/delithiation experiments confirm the reversible electrochemical reactions. Without any binding additives, the as-deposited electrodes delaminate resulting in fast capacity degradation. We demonstrate the mechanical nature of this degradation through decreased electrode thinning, resulting in cells with improved cycling stability due to increased mechanical stability. Combining composition and electrochemical analysis, this work demonstrates for the first time composition dependent electrochemical properties for the ternary Zn1−xSn1+xN2 and proposes earth-abundant ternary nitride anodes for increased reversible capacity and cycling stability.

Stable and fast Si−M−C ternary anodes enabled by interfacial engineering

For lithium storage, the co-hybridization of silicon with metal and carbon matrices is a promising strategy to mitigate the intrinsic challenges of silicon anodes. However, current Si–M–C ternary materials often suffer from nonuniform distribution of triple components, and Si is physically combined to M/C dual matrices with weak interactions. Herein, we propose an interpenetrating hydrogel-enabled methodology for the formation of chemical-bonded and uniform-distributed Si−M−C ternary materials. As a proof-of-concept illustration, commercial Si particles have been in situ immobilized within Sn nanorod-filled graphene gel framework, and are covalently bonded with Sn/G dual matrices via interfacial Si–O–Sn and Si–O–C bondings. Thanks to the rationally designed composition and structure, the Si–Sn@G gel framework anode manifests long cycling life (983 mA h g−1 in the 100th cycle at 0.5 A g−1) and good rate capability (717 and 514 mA h g−1 at 5 and 10 A g−1, respectively).

A lithiophilic/lithiophobic ternary alloy anode with Ag concentration gradients guides uniform Li deposition.

A Li92.5Cu5Ag2.5 ternary alloy anode was designed with controlled lithiophilic/lithiophobic gradients to induce bottom-up Li deposition. The inert metal Cu served as a rigid framework that maintains structural stability, while the lithiophilic metal Ag provided abundant Li deposition sites. Such an ultrathin Li-rich composite anode (Li content as low as 10 mA h cm-2) affords stable cycling over 1200 h.

AMORPHOUS CUSEP2/GRAPHENE COMPOSITES AS ANODE MATERIAL FOR ADVANCED POTASSIUM-ION BATTERY

The ternary amorphous CuSeP2 was designed and prepared as the anode material of potassium ion battery for the first time, and its electrochemical performance was also investigated. After ball-milling with commercial graphene powder, it is used as the anode material for potassium ion battery with reversible specific capacity up to 300 mAh g-1, and the corresponding initial coulombic efficiency is close to 60%. What’s more, the specific capacity remains above 150 mAh g-1 after 100 cycles at 200 mA g-1. When increasing the current density to 1000 mA g-1, the CuSeP2/graphene composites still has a potassium storage specific capacity of 100 mAh g-1. Our results show that the potassium storage mechanism of the ternary CuSeP2 anode material is a typical conversion reaction and the introduction of Cu can not only buffer the volume expansion during the subsequent electrochemical reaction, but also effectively enhance the electrochemical reversibility of potassium ion.