Metal-ion Battery Anodes Research Articles

An insight into the electro-chemical properties of halogen (F, Cl and Br) doped BP and BN nanocages as anodes in metal-ion batteries

Here, electro-chemical properties of BN and BP nanocages as anodes in metal-ion batteries are examined. The effect of halogens adoption of BN and BP-NCs on electro-chemical properties of M-IBs are investigated. Results showed that the BP nanocages as anode electrode in M-IBs has higher efficiency than BN nanocages and the K-IB has higher cell voltage than N-IBs. Results indicated that the halogens adoption of BN and BP-NCs are improved the cell voltage of M-IBs. Results proved that the F-doped M-IBs have higher cell voltage than M-IBs. Finally, F-B17P18 as anodes in K-IB is proposed as suitable electrodes.

Recent progress on FeS2 as anodes for metal-ion batteries

The ever-growing demand for advanced battery technologies with high energy and power density, high security, prolonged cycle life, and sustainably low cost requires the development of novel electrode materials for lithium-ion batteries (LIBs), as well as the alternative electrochemical energy storage technologies of sodium-ion batteries (SIBs) and potassium-ion batteries (PIBs) for their abundant alkali metal elements resources. Among various anode materials, such as graphite, organic compounds, metal oxides, and chalcogenides, iron sulfides have attracted substantial interests for their high theoretical capacity and low price. Specifically, as a common mineral that has been already applied as electrode for primary battery, ferrous disulfide (FeS2) has been regarded as one of the promising candidate anode materials and studied widely. Unfortunately, there are some inherent problems handicapping its practical application for alkali-ion batteries, including limited ionic/electrical conductivity, the formation of soluble polysulfides, and large volume change. In the last decade, massive efforts have been devoted to solving those problems. In this review, the various synthesis strategies, the effect of morphologies and particle sizes, the energy storage mechanisms, and the electrochemical performances of FeS2 as anode for alkali-ion batteries (LIBs, SIBs, and PIBs) are summarized. Furthermore, the existing challenges and prospects of the development of FeS2-based anode materials for alkali-ion batteries are presented at last. In this review, the various synthesis strategies, the effect of morphologies and particle sizes, the energy storage mechanisms, and the electrochemical performances of FeS2 as anode for alkali-ion batteries are summarized. Furthermore, the existing challenges and prospects of the development of FeS2-based anode materials are also presented.

Gallium-based anodes for alkali metal ion batteries

Self-healing and dual mechanisms of conversion and alloying reaction endow gallium-based hosts a huge potential for alkali metal ion battery anodes. This review makes a summary of their energy storage mechanisms, challenges, and modification strategies to enhance the electrochemical performance. Alkali metal ion batteries (AMIBs) are playing an irreplaceable part in the energy revolution, due to their intrinsic advantages of large capacity/power density and abundance of alkali metal ions in the earth’s crust. Despite their great promise, the inborn deficiencies of commercial graphite and other anodes being researched so far call for the quest of better alternatives that exhibit all-round performance with the balance of energy/power density and cycling stability. Gallium-based materials, with impressive capacity utilization and self-healing ability, provide an anticipated solution to this conundrum. In this review, an overview on the recent progress of gallium-based anodes and their storage mechanism is presented. The current strategies used as engineering solutions to meet the scientific challenges ahead are discussed, in addition to the insightful outlook for possible future study.

Design strategies for nonaqueous multivalent-ion and monovalent-ion battery anodes

The inability of current battery technologies to keep up with the performance requirements of industry is pushing forward developments in electrochemistry. Specifically, the battery’s negative electrode, the anode, presents many unique chemical, physical and engineering challenges. Lithium-based battery technologies have dominated the past decade, but concerns about the limited supply of lithium in the Earth’s crust have led researchers to look towards alternative metal-ion technologies. Various alkali metals (such as sodium and potassium) and alkali earth metals (such as magnesium and calcium) have attracted significant research interest. In this Review, we analyse these technologies in a coherent manner, addressing the problems of each type of anode, rather than those of specific types of metal-ion batteries. Covering direct metal plating and stripping, intercalation-based, alloy-based and conversion-reaction-based anode technologies, this analysis will offer the reader a comprehensive understanding of the behaviour of different metal-ion anodes and of what can be learned by transferring knowledge between these different systems. Increasing demand for energy-storage systems will inevitably stress the Earth’s lithium supply; thus, the research focus is shifting towards other alkali and alkali earth metals. This Review compares and connects strategies to enable different multivalent and monovalent metal-ion battery anodes, including metal anodes and intercalation-based, alloy-based and conversion-reaction-based anodes.

Bco-C24: A new 3D Dirac nodal line semi-metallic carbon honeycomb for high performance metal-ion battery anodes

Three-dimensional porous carbon materials play a significant role in gas separation and energy storage. However, their low performances in energy storage hamper their applications. Herein, we propose a new possible category of carbon honeycomb (CHC), i.e. CHCs with asymmetrical channels (denoted as asymmetrical CHCs), to increase their performance. As an example, by cross-linking graphene sheet with sp3–hybridized carbon chains, we prepare a new 3D porous asymmetrical CHC, i.e. bco-C24. It is dynamically, thermally, and mechanically stable. Our first-principles calculations and tight binding results demonstrate that it possesses a significant electronic band structure of Dirac nodal lines, which are ascribed to the px and py orbitals of α carbon atoms in the graphene ribbons that have both α and β carbon atoms. It provides high carrier mobility between 7.98 × 105 and 9.99 × 105 m/s. It has high theoretical capacities (743.8/495.9/991.8/743.8 mA h/g), low diffusion barriers (0.077/0.032/0.117/0.169 eV), low average voltages, and negligible volume changes for Na/K/Ca/Li-ion batteries. This study not only constructs a new concept of asymmetrical CHCs and provides a strategy of cross-linking graphene sheets to create its sample structures, but also suggests new carriers for ion storage in the superior next generation metal-ion battery anodes.

Possibility of NiO, ZrO2, ZnO and GrO2 Attached to Silicon and Carbon Nanostructures as Anode of Battery: Computational Examination

In current study, possibility of Si-nanocage (Si48) and C-nanocage (C60) as anodes in LIB, NIB and KIB are examined via computational methods. Adsorption of Zinc oxide (ZnO), Germanium dioxide (GeO2), Nickel oxide (NiO) and Zirconium dioxide (ZrO2) on Si48 and C60 are examined. The potential of GeO2-Si-nanocage, ZnO-Si-nanocage, ZrO2-C-nanocage and NiO-C-nanocage as anodes in LIB, NIB and KIB are compared with Si-nanocage (Si48) and C-nanocage (C60). The Vcell of Si-nanocage, GeO2-Si-nanocage, ZnO-Si-nanocage, C-nanocage, ZrO2-C-nanocage and NiO-C-nanocage as anodes in MIBs are examined. NiO, ZnO, ZrO2 and GeO2 are increased Vcell of Si-nanocages and C-nanocages, significantly. The Li-, Na- and K-ion batteries with ZrO2 and GeO2 have greater Vcell in comparison to NiO and ZnO. ZrO2-C-nanocage and GeO2-Si-nanocage are suggested as high performance anodes in metal-ion batteries.

Adsorbed CdO, TiO, RuO2, and IrO2 to silicon nanotube and carbon nanocage for anode of metal-ion battery: a computational study

Potential of carbon nanocage (C52) and silicon nanotube (SiNT) as anodes in Li- and Na-ion batteries is examined. Effects of cadmium oxide, titanium oxide, ruthenium dioxide (RuO2), and iridium dioxide (IrO2) on abilities of C52 and SiNT as anodes in Li- and Na-ion batteries are investigated. Results indicated that the metal oxides and metal dioxides can increase Gad of nanocages and nanotubes. Results demonstrated that Li-ion batteries have higher Vcell than Na-ion batteries. The metal oxides can improve the cell voltage of Li- and Na-ion batteries. The RuO2–SiNT and IrO2–C52 as high-efficiency anodes in metal-ion batteries are proposed.

RETRACTED: DFT examination of potential of adsorbed Gallium oxide and Tin dioxide to carbon nanocages as anodes in metal ion batteries

Abstract Here, the abilities of carbon nanocages (C60, C72 and C84) as anode electrodes in lithium-ion battery (LIB) and potassium-ion battery (KIB) were examined by theoretical method. The effects of adsorbed Gallium oxide (GaO) and Tin dioxide (SnO2) on performances of C60, C72 and C84 as anode electrodes in LIB and KIB were investigated. The cell voltage (Vcell), Gibbs free energy (Gad), band gap energy (EHLG) and charge transferred (q) of studied complexes were calculated. Results indicated that Gibbs free energies of adsorption of GaO on C60, C72 and C84 nanocages were higher than SnO2. The band gap energy of GaO-C84 was lower than GaO-C60 and GaO-C72. Results showed that adsorbed SnO2 and GaO can increase the |q|, |Gad| and Vcell values of C60, C72 and C84 nanocages, significantly. Finally, the C84-SnO2 as novel anode electrodes in LIB and KIB with the highest Vcell was proposed to use in electrical machines.

Mechanical deformation: A feasible route for reconfiguration of inner interfaces to modulate the high performance of three-dimensional porous carbon material anodes in stretchable lithium-Ion batteries

The rapid development of stretchable electronics, which have wide applications from clinical applications to stretchable smart phones, requires numerous advanced stretchable energy technologies, such as stretchable batteries. However, maintaining performance in such batteries during deformation and developing stretchable batteries with suitable mechanical robustness for industrial applications remain challenges. In this work, by using first-principles calculations, the performance of three-dimensional (3D) topological semimetal porous carbon material bct-C40 anodes in stretchable lithium-ion batteries (LIBs) is investigated. We find that the mechanical deformation is a feasible route for reconfiguration of inner surfaces of porous carbon material anodes to modulate their high performance in stretchable LIBs. The bct-C40 anode delivers a high theoretical capacity of 893 mA h/g, which is approximately 2.4 times larger than that of the commercial graphite anode (372 mA h/g). Adsorption-activation-adsorption mechanism and (de)activation-adsorption mechanism are proposed for the capacities of the anode under strain-free and strained states, respectively. Under the strain-free state, the adsorption of Li atoms changes the size of porous of bct-C40 at the atomic scale and readjusts the electron distribution on bct-C40 at the electronic scale, activating more adsorption sites. Large tensile strains expand its inner space and inner surface area, forming new adsorption sites and boosting its high capacities. Large compressive strains undermine its inner surface and deactivate some adsorption sites, reducing its capacities. Small compressive and tensile strains play a little role in the inner surface and do not affect adsorption sites, retaining its high capacities. More excitingly, diffusion barriers under strain-free and strained states, which are sensitive to the inner surface, are (ultra)low, demonstrating that the anode has (ultra)fast charge/discharge rates. This work provides new insights for the modulatable performance of 3D porous carbon material anodes, and offers an approach to innovate high performance stretchable metal-ion battery anodes with suitable mechanical robustness.

Two-Dimensional Carbon-Based Auxetic Materials for Broad-Spectrum Metal-Ion Battery Anodes.

Auxetic materials possess special applications due to their unique negative Poisson's ratios (NPRs). As a classic 2D carbon material, the NPR of graphene is still deliberated. Introducing the NPR in graphene would increase its extraordinary properties, and the NPR together with other properties would bring more significant applications for graphene. In this Letter, on the basis of first-principles calculations, we reconfigure the structure of graphene, and, as an example, we propose a new 2D planar carbon allotrope, xgraphene, which is constructed by 5-6-7 carbon rings. Our theoretical calculations indicate that xgraphene has an NPR and constitutes a broad spectrum of metal ion battery anodes with high performance. Its maximum storage capacities are 930/1302/744/1488 mAh/g for Li/Na/K/Ca-ion batteries. It has low metal-ion diffusion energy barriers (≤0.49 eV) and low average open-circuit voltages (≤0.53 V). Our density functional theory results also showed that it is intrinsically metallic and possesses dynamic, thermal, and mechanical stabilities. Its intrinsic NPR, which stems from the weakness of coupling of carbon-carbon bonds, is found upon loading the uniaxial strain along the armchair direction. This work not only opens up a new direction for the design of the next-generation broad-spectrum energy-storage materials with low cost and high performance but also offers a class application for auxetic materials.

Heterostructural modulation of in situ growth of iron oxide/holey graphene framework nanocomposites as excellent electrodes for advanced lithium-ion batteries

Chemically integrated hybrid nanostructures of Fe2O3/holey graphene frameworks (Fe2O3/HGF) nanocomposites have been successfully synthesized via a glycerol activated process. Defected graphene oxides were first etched by a certain volume of hydrogen peroxide. Subsequently, multi-dimensionally nanosized Fe2O3 particles were generated and anchored on the defected graphene layers. Based on this method, the ability in synthesizing the exquisitely tune Fe2O3 nanoparticles with highly controllable nanostructures and desirable properties is demonstrated, ranging from zero-dimensional quantum dots (~4.42 nm) to one-dimensional nanorods, and eventually to two-dimensional nanosheets. As anodes for lithium-ion batteries, these hybrid Fe2O3/holey graphene frameworks electrodes exhibit excellent cyclic stability at 1 A g−1 after 500 cycles (73.59 mAh g−1 for quantum dots Fe2O3/HGF electrodes, 695.4 mAh g−1 for nanosheets Fe2O3/HGF electrodes and 805.6 mAh g−1 for nanorods Fe2O3/HGF electrodes, respectively) and specific capacity retention at the current density of 4 A g−1 (427.6 mAh g−1 for quantum dots Fe2O3/HGF electrodes, 374.2 mAh g−1 for nanosheets Fe2O3/HGF electrodes and 473.5 mAh g−1 for nanorods Fe2O3/HGF electrodes, respectively). This work reveals a facile way to modify the oxygenic defect sites of carbon-based materials, providing more attaching sites for metal oxides, and hopefully accelerating the commercialization of carbon-based nanocomposites as anodes for metal-ion batteries.

Examination of properties of nanocages (B18N18 and B18P18) as anode electrodes in metal-ion batteries

Performance of B18N18 and B18P18 as anodes in metal-ion batteries (MIBs) were examined. Effects of halogen adoption of B18N18 and B18P18 as anodes in MIBs were examined. The B18P18 as anode in MIBs has larger potential than B18N18. The K-ion battery takes larger voltage of cell and performance than Na- and Li-ion batteries. The halogen adoption of B18N18 and B18P18 improves the cell voltage of MIBs. The storage capacities of B18N18 and B18P18 nanocages for Li-ion batteries are 893 and 795 mAh/g, respectively. The cell voltages of F-doped MIBs were larger than Br- and Cl-doped MIBs. The F-B17P18 as anode in K-ion battery proposed as novel MIBs with the highest performance.

Reconfiguring graphene for high-performance metal-ion battery anodes

Reconfiguring structures in materials is one of the most important building approaches in new material design. The atomically precise control of reconfiguration of two-dimensional (2D) carbon-based materials reshapes their properties for engineering applications. Herein, by employing density functional theory and tight-binding modeling, we reconfigured atomically precise structure in graphene and proposed a new 2D carbon allotrope Θ-graphene. The reconfiguring procedure adopted was realized in experiments using an electron beam. It exhibits semiconductor features with a bandgap of 0.58 eV, and is extendable to semimetal or metal. Mechanically-induced directional-dependent topological node line states are formed and their origin is the breaking of the geometrical symmetry. The reconfiguring procedure reshapes the adsorption and diffusion properties of Θ-graphene, promoting its storage capacities for metal ions (876.65/1275.12/956.34 mA h/g for Li/Na/K- ion batteries) and lowing its metal ion-diffusion energy barriers (≤ 0.48 eV) and lowing its average open circuit voltages (≤ 0.60 V). The transition from semiconductor to metal with metal ions introduced improves its high electronic conductivity, which could be beneficial to the fast charge/discharge rates. Our results show that the reconfigured structure in graphene reshapes its properties, bringing it numerous promising engineering applications such as in metal-ion batteries and in nanoelectronic devices and in energy storage. This work provides a new channel for materials design and innovation by combining the reconfiguring strategy and the structure-property-application relationship, and opens up a new strategy to extend the applications of low-dimensional materials such as graphene and to promote their application performance.

Realizing stable lithium and sodium storage with high areal capacity using novel nanosheet-assembled compact CaV4O9 microflowers

Realizing stable cycling performance with high areal capacity is a great challenge for metal-ion battery anodes. Achieveing high areal capacity generally requires the electrode in a high active loading with increased electrode thickness, which is not beneficial to the cycling stability. In this work, novel nanosheet-assembled compact CaV4O9 microflowers are firstly synthesized through a facile method, which exhibit both high areal capacity and stable cycling performance at high mass loadings. The compact microflower structure leads to an increased tap density of the electrode materials, benefiting to reduce the anode thickness at high mass loadings. Meanwhile, the assembled nanosheets maintain the nano-effects of the active materials for favorable electrochemical reactions. These merits together with the intrinsic superior electrochemical properties of CaV4O9, result in the outstanding electrochemical performance. When used as Li-ion battery anodes, a high areal capcity of ~2.5 mAh cm−2 at a high mass loading of 4.4 mg cm−2 is obtained, and a stable cycling over 400 cycles with the areal capacity over 1.5 mAh cm−2 is demonstrated. Besides, the superior electrochemical performance at high mass loadings is also observed for Na storage. These achievements may pave the way for constructing applicable high-capacity and stable anode materials in metal-ion batteries.

ChemInform Abstract: Surface Engineering of Nanomaterials for Improved Energy Storage ‐ A Review

AbstractReview: 208 refs.

Surface engineering of nanomaterials for improved energy storage – A review

Nanomaterials bring extreme promise for a future wave of energy storage materials with high storage capacity, fast recharging capability, and better durability than bulk material counterparts. However, this promise is often overshadowed by greater surface area and higher reactivity of nanostructured active materials - obstacles that must be overcome to be practical. Specifically for energy storage systems, many materials that exhibit promise in bulk form for high capacity or energy density exhibit surfaces that are unstable or reactive in electrochemical environments when downsized to nanometer length scales. As a result, surface engineering can be a powerful tool to decouple bulk material properties from surface characteristics that often bottleneck energy storage applications of nanomaterials. This review discusses advances made toward the surface engineering of nanostructures in the context of four mechanistic roles that surface engineering can play. This includes (i) chemical activation, where the surface layer plays the active role in facilitating a Faradaic chemical process, (ii) solid electrolyte interphase (SEI) control, where a surface layer can lead to a stable artificial interface for Faradaic processes to occur, (iii) chemical passivation, where near atomically thin surface protective layers can protect from corrosion or unwanted electrochemical reactions at interfaces, and (iv) mechanical stability, where a thin layer can provide mechanical support to inhibit fracturing or mechanical failure. This review elucidates surface engineering as a multi-faceted tool for engineering materials for energy storage that intersects the quest for new materials and the rediscovery of old materials to break new ground in energy storage applications. The discussion concludes by highlighting key current challenges in surface engineering for pure metal anodes in metal-ion batteries and polysulfide immobilization in lithium-sulfur batteries.

Bridging the Fields of Solar Cell and Battery Research to Develop High-Performance Anodes for Photoelectrochemical Cells and Metal Ion Batteries

Solar-to-electricity energy conversion and large scale electricity storage technologies are key to achieve a sustainable development of society. For energy conversion, photoelectrochemical solar cells were proposed as an economic alternative to the conventional Si-based technology. For energy storage, metal-ion batteries are a very promising technology. Titania (TiO2) based anodes are widely used in photoelectrochemical cells and have recently emerged as safe, high-rate anodes for metal-ion batteries. In both applications, titania interacts with electrolyte species: molecules and metal ions. Details of this interaction determine the performance of the electrode in both technologies, but no unified theoretical description exists, e.g., there is no systematic description of the effects of Li, Na insertion into TiO2 on solar cell performance (while it is widely studied in battery research) and no description of effects of surface adsorbents on the performance of battery anodes (while they are widely studied in solar cell research). In fact, there is no systematic description of interactions of electrolyte species with TiO2 of different phases and morphologies. We propose a computation-focused study that will bridge the two fields that have heretofore largely been developing in parallel and will identify improved anode materials for both photoelectrochemical solar cells and metal-ion batteries.