Corrosion and wetting behaviour of metals and steels with molten alkali carbonates

The corrosion and wetting behaviour of metals and steels with molten alkali carbonates is of particular interest for the design of molten carbonate fuel cells. Such cells, operating at 650 °C with a lithium and potassium carbonate electrolyte, offer a very corrosive medium for fuel cell components.Static corrosion tests under simulated anode conditions have shown that rhodium, ruthenium, platinum, palladium, silver, gold, Nickel 200 and Monel 400 exhibit no measurable corrosion over a 100 h period. Copper, Kanthal and Fecralloy exhibit good resistance with thin protective oxide layers. Stainless steels show less resistance to attack with thicker more permeable oxide coatings being formed.In addition, contact angle measurements indicate that copper, gold, silver and ruthenium demonstrate appreciable non-wetting under a H₂-CO₂ atmosphere. Steels are substantially wetted.     

Electrochemical properties of Li<Subscript>4</Subscript>Ti<Subscript>5</Subscript>O<Subscript>12</Subscript>/C and Li<Subscript>4</Subscript>Ti<Subscript>5</Subscript>O<Subscript>12</Subscript>/C/Ag nanomaterials

We have prepared and characterized lithium titanate-based anode materials, Li₄Ti₅O₁₂/C and Li₄Ti₅O₁₂/C/Ag, using polyvinylidene fluoride as a carbon source. The formation of such materials has been shown to be accompanied by fluorination of the lithium titanate surface and the formation of a highly conductive carbon coating. The highest electrochemical capacity (175 mAh/g at a current density of 20 mA/g) is offered by the Li₄Ti₅O₁₂-based anode materials prepared using 5% polyvinylidene fluoride. The addition of silver nanoparticles ensures a further increase in electrical conductivity and better cycling stability of the materials at high current densities.     

Lithium iron oxide as alternative anode for li-ion batteries

Lithium–iron oxide Li–Fe–O was synthesized by solid state reaction between Li₂CO₃ and Fe₂O₃. The sample was characterized by X-ray powder diffraction. The XRD patterns showed well defined reflections corresponding to α-LiFeO₂ and the spinel LiFe₅O₈ in a molar ratio of 9:1. The material was tested as alternative anode for lithium-ion batteries. It exhibited good cyclability delivering about 120 mAh/g after 500 deep charge/discharge cycles. Unlikely, the use of the material as intercalation anode in practical cells is hindered by the irreversible uptake of lithium that takes place during the first lithium insertion. X-ray diffraction pattern showed that during this step a reduction of the lithium iron oxide occurs leading to the formation of lithium oxide and iron metal.     

High Performance Lithium‐Ion Batteries Using Layered 2H‐MoTe2 as Anode

The major challenges faced by candidate electrode materials in lithium‐ion batteries (LIBs) include their low electronic and ionic conductivities. 2D van der Waals materials with good electronic conductivity and weak interlayer interaction have been intensively studied in the electrochemical processes involving ion migrations. In particular, molybdenum ditelluride (MoTe₂) has emerged as a new material for energy storage applications. Though 2H‐MoTe₂ with hexagonal semiconducting phase is expected to facilitate more efficient ion insertion/deinsertion than the monoclinic semi‐metallic phase, its application as an anode in LIB has been elusive. Here, 2H‐MoTe₂, prepared by a solid‐state synthesis route, has been employed as an efficient anode with remarkable Li⁺ storage capacity. The as‐prepared 2H‐MoTe₂ electrodes exhibit an initial specific capacity of 432 mAh g^?1 and retain a high reversible specific capacity of 291 mAh g^?1 after 260 cycles at 1.0 A g^?1. Further, a full‐cell prototype is demonstrated by using 2H‐MoTe₂ anode with lithium cobalt oxide cathode, showing a high energy density of 454 Wh kg^?1 (based on the MoTe₂ mass) and capacity retention of 80% over 100 cycles. Synchrotron‐based in situ X‐ray absorption near‐edge structures have revealed the unique lithium reaction pathway and storage mechanism, which is supported by density functional theory based calculations.     

Thermally stimulated polarization and depolarization current (TSPC/TSDC) techniques for studying ion motion in glass

The feasibility of studying ionic motion in glass using thermally stimulated polarization (TSPC)/depolarization current (TSDC) techniques was investigated with 4Na₂O-96SiO₂ and 30PbO-70SiO₂ (mol %) glasses. The TSPC peaks in these glasses were dependent on glass composition and attributed to bulk polarization. The high temperature background TSPC is shown to be due to the d.c. conductivity, whereas the TSPC/TSDC peaks in the 4Na₂O glass are attributed to shorter range Na⁺ motion.     

In Situ Designing a Gradient Li+ Capture and Quasi-Spontaneous Diffusion Anode Protection Layer toward Long-Life Li−O2 Batteries

Lithium metal is the only anode material that can enable the Li−O₂ battery to realize its high theoretical energy density (≈3500 Wh kg⁻¹). However, the inherent uncontrolled dendrite growth and serious corrosion limitations of lithium metal anodes make it experience fast degradation and impede the practical application of Li−O₂ batteries. Herein, a multifunctional complementary LiF/F-doped carbon gradient protection layer on a lithium metal anode by one-step in situ reaction of molten Li with poly(tetrafluoroethylene) (PTFE) is developed. The abundant strong polar C-F bonds in the upper carbon can not only act as Li⁺ capture site to pre-uniform Li⁺ flux but also regulate the electron configuration of LiF to make Li⁺ quasi-spontaneously diffuse from carbon to LiF surface, avoiding the strong Li⁺-adhesion-induced Li aggregation. For LiF, it can behave as fast Li⁺ conductor and homogenize the nucleation sites on lithium, as well as ensure firm connection with lithium. As a result, this well-designed protection layer endows the Li metal anode with dendrite-free plating/stripping and anticorrosion behavior both in ether-based and carbonate ester-based electrolytes. Even applied protected Li anodes in Li−O₂ batteries, its superiority can still be maintained, making the cell achieve stable cycling performance (180 cycles).     

In situ synthesis of SnO2/graphene nanocomposite and their application as anode material for lithium ion battery

SnO₂/graphene nanocomposite was prepared via an in situ chemical synthesis method. The nanocomposite was characterized by X-ray diffraction, filed emission scanning electron microscope and transmission electron microscope, which revealed that tiny SnO₂ nanoparticles could be homogeneously distributed on the graphene matrix. The electrochemical performance of the SnO₂/graphene nanocomposite as anode material was measured by galvanostatic charge/discharge cycling. The SnO₂/graphene nanocomposite showed a reversible capacity of 665 mAh/g after 50 cycles and an excellent cycling performance for lithium ion battery, which was ascribed to the three-dimensional architecture of SnO₂/graphene nanocomposite. These results suggest that SnO₂/graphene nanocomposite would be a promising anode material for lithium ion battery.     

Electroless deposition of superconducting MgB2 films on various substrates

The superconducting properties of magnesium diboride (MgB₂) films prepared by electroless deposition on various substrates including silver, gold and silicon are reported. In this study, MgB₂ films were fabricated on silver, gold, and silicon using an electroless plating technique, while controlling the redox potential to improve the deposition quality. The structure, morphology, and superconducting properties of the samples were investigated using X-ray diffraction, magnetometry, scanning electron microscopy, and Raman spectroscopy. X-ray diffraction and Raman spectroscopy confirmed that the films are polycrystalline MgB₂ but also contain some impurity phases. All the MgB₂ films show superconducting transitions near 39 K, the value for bulk MgB₂, with the superconducting volume fraction ranging from approximately 1 to 2%. We find a strong dependence of film quality with the oxidation potential of the bath.     

Early Lithium Plating Behavior in Confined Nanospace of 3D Lithiophilic Carbon Matrix for Stable Solid‐State Lithium Metal Batteries

Considerable efforts are devoted to relieve the critical lithium dendritic and volume change problems in the lithium metal anode. Constructing uniform Li⁺ distribution and lithium “host” are shown to be the most promising strategies to drive practical lithium metal anode development. Herein, a uniform Li nucleation/growth behavior in a confined nanospace is verified by constructing vertical graphene on a 3D commercial copper mesh. The difference of solid‐electrolyte interphase (SEI) composition and lithium growth behavior in the confined nanospace is further demonstrated by in‐depth X‐ray photoelectron spectrometer (XPS) and line‐scan energy dispersive X‐ray spectroscopic (EDS) methods. As a result, a high Columbic efficiency of 97% beyond 250 cycles at a current density of 2 mA cm^?2 and a prolonged lifespan of symmetrical cell (500 cycles at 5 mA cm^?2) can be easily achieved. More meaningfully, the solid‐state lithium metal cell paired with the composite lithium anode and LiNi_0.5Co_0.2Mn_0.3O₂ (NCM) as the cathode also demonstrate reduced polarization and extended cycle. The present confined nanospace–derived hybrid anode can further promote the development of future all solid‐state lithium metal batteries.     

Horizontal Growth of Lithium on Parallelly Aligned MXene Layers towards Dendrite‐Free Metallic Lithium Anodes

Although metallic lithium is an extremely promising anode for lithium‐based batteries due to its high theoretical capacity, the uncontrollable growth of lithium dendrites, in particular under deep stripping and plating, have stagnated its application. It is demonstrated that parallelly aligned MXene (Ti₃C₂T_x ) layers enable the efficient guiding of lithium nucleation and growth on the surface of 2D MXene nanosheets, giving rise to horizontal‐growth lithium anodes. Moreover, the inherent fluorine terminations in MXene afford a uniform and durable solid electrolyte interface with lithium fluoride at the anode/electrolyte interface, efficiently regulating electromigration of lithium ions. Thus, a dendrite‐free lithium anode with a long cycle life up to 900 h and excellent deep stripping–plating capabilities up to 35 mAh cm^?2 is achieved, which can further serve as an anode for a lithium metal battery, exhibiting high cycle stability up to 1000 cycles.     

Fluorinated co-solvent promises Li-S batteries under lean-electrolyte conditions

Practical lithium-sulfur batteries stipulate the use of a lean-electrolyte and a high Coulombic efficiency of the lithium metal anode. Herein, we employ 1,1,2,2-tetrafluoroethyl 2,2,2-trifluoroethyl ether as a co-solvent in the electrolyte of Li-S batteries to meet the demands. The co-solvent fosters the formation of a LiF-rich solid electrolyte interphase on lithium metal anode, as revealed by Ab initio molecular dynamics and Femtosecond Stimulated Raman spectroscopy. The co-solvent results in an average Coulombic efficiency of 99.4% for lithium plating/stripping cycles. Full cells with a capacity ratio of 2 between lithium anode and the S@PAN cathode (3 mg_s cm⁻²) exhibited a stable cycle life over 100 cycles at an electrolyte/sulfur ratio of 2 µL mg⁻¹, validating the high Coulombic efficiency of the lithium anode and demonstrating the compatibility of the electrolyte with both electrodes. To enhance the energy density, we prepared a hybrid cathode composed of 45 wt.% VS₂ mixed with ZnS-coated Li₂S@graphene as the cathode. Based on the mass of both electrodes and the electrolyte, the full cell delivers an energy density of 483 Wh kg⁻¹, which demonstrates viable Li-S batteries with the lean-electrolyte.     

In Situ Construction of Stable Tissue‐Directed/Reinforced Bifunctional Separator/Protection Film on Lithium Anode for Lithium–Oxygen Batteries

To achieve a high reversibility and long cycle life for Li–O₂ battery system, the stable tissue‐directed/reinforced bifunctional separator/protection film (TBF) is in situ fabricated on the surface of metallic lithium anode. It is shown that a Li–O₂ cell composed of the TBF‐modified lithium anodes exhibits an excellent anodic reversibility (300 cycles) and effectively improved cathodic long lifetime (106 cycles). The improvement is attributed to the ability of the TBF, which has chemical, electrochemical, and mechanical stability, to effectively prevent direct contact between the surface of the lithium anode and the highly reactive reduced oxygen species (Li₂O₂ or its intermediate LiO₂) in cell. It is believed that the protection strategy describes here can be easily extended to other next‐generation high energy density batteries using metal as anode including Li–S and Na–O₂ batteries.     

Lithium Silicide Surface Enrichment: A Solution to Lithium Metal Battery

The propensity of lithium dendrite formation during the charging process of lithium metal batteries is linked to inhomogeneity on the lithium surface layer. The high reactivity of lithium and the complex surface structure of the native layer create “hot spots” for fast dendritic growth. Here, it is demonstrated that a fundamental restructuring of the lithium surface in the form of lithium silicide (Li_xSi) can effectively eliminate the surface inhomogeneity on the lithium surface. In situ optical microscopic study is carried out to monitor the electrochemical deposition of lithium on the Li_xSi‐modified lithium electrodes and the bare lithium electrode. It is observed that a much more uniform lithium dissolution/deposition on the Li_xSi‐modified lithium anode can be achieved as compared to the bare lithium electrode. Full cells paring the modified lithium anode with sulfur and LiFePO₄ cathodes show excellent electrochemical performances in terms of rate capability and cycle stability. Compatibility of the anode enrichment method with mass production process also offers a practical way for enabling lithium metal anode for next‐generation lithium batteries.     

In situ synthesis of SnO2 nanosheet/graphene composite as anode materials for lithium-ion batteries

A novel SnO₂/graphene composite has been synthesized via an in situ chemical synthesis method, in which single crystal SnO₂ nanosheets are uniformly grown on graphene support. The as-prepared products were characterized by X-ray diffraction, field emission scanning electron microscope, transmission electron microscope, Thermogravimetric analyses and Nitrogen adsorption/desorption. When used as an anode material for lithium ion batteries, the SnO₂/graphene composite exhibits an enhanced reversible lithium storage capacity and good cyclic performance. The first discharge and charge capacities are 1,366 and 975 mAh g^?1, respectively. After 100 cycles, the reversible discharge capacity is still maintained at 451 mAh g^?1 at the current densities of 100 mA g^?1, indicating that it’s a promising anode material for high performance lithium ion batteries.     

High‐Coulombic‐Efficiency Carbon/Li Clusters Composite Anode without Precycling or Prelithiation

Lithium metal has attracted much research interest as a possible anode material for high‐energy‐density lithium‐ion batteries in recent years. However, its practical use is severely limited by uncontrollable deposition, volume expansion, and dendrite formation. Here, a metastable state of Li, Li cluster, that forms between LiC₆ and Li dendrites when over‐lithiating carbon cloth (CC) is discovered. The Li clusters with sizes in the micrometer and submicrometer scale own outstanding electrochemical reversibility between Li⁺ and Li, allowing the CC/Li clusters composite anode to demonstrate a high first‐cycle coulombic efficiency (CE) of 94.5% ± 1.0% and a stable CE of 99.9% for 160 cycles, which is exceptional for a carbon/lithium composite anode. The CC/Li clusters composite anode shows a high capacity of 3 mAh cm^?2 contributed by both Li⁺ intercalation and Li‐cluster formation, and excellent cycling stability with a signature sloping voltage profile. Furthermore, the CC/Li clusters composite anode can be assembled into full cells without precycling or prelithiation. The full cells containing bare CC as the anode and excessive LiCoO₂ as the cathode exhibit high specific capacity and good cyclic stability in 200 cycles, stressing the advantage of controlled formation of Li clusters.     

Dual‐Layered Film Protected Lithium Metal Anode to Enable Dendrite‐Free Lithium Deposition

Lithium metal batteries (such as lithium–sulfur, lithium–air, solid state batteries with lithium metal anode) are highly considered as promising candidates for next‐generation energy storage systems. However, the unstable interfaces between lithium anode and electrolyte definitely induce the undesired and uncontrollable growth of lithium dendrites, which results in the short‐circuit and thermal runaway of the rechargeable batteries. Herein, a dual‐layered film is built on a Li metal anode by the immersion of lithium plates into the fluoroethylene carbonate solvent. The ionic conductive film exhibits a compact dual‐layered feature with organic components (ROCO₂Li and ROLi) on the top and abundant inorganic components (Li₂CO₃ and LiF) in the bottom. The dual‐layered interface can protect the Li metal anode from the corrosion of electrolytes and regulate the uniform deposition of Li to achieve a dendrite‐free Li metal anode. This work demonstrates the concept of rational construction of dual‐layered structured interfaces for safe rechargeable batteries through facile surface modification of Li metal anodes. This not only is critically helpful to comprehensively understand the functional mechanism of fluoroethylene carbonate but also affords a facile and efficient method to protect Li metal anodes.     

Nanoarray Architecture of Ultra-Lithiophilic Metal Nitrides for Stable Lithium Metal Anodes

Lithium metal anode (LMA) is puzzled by the serious issues corresponding to infinite volume change and notorious lithium dendrite during long-term stripping/plating process. Herein, the transition metal nitrides array with outstanding lithiophilicity, including CoN, VN, and Ni₃N, are decorated onto carbon framework as “nests” to uniform Li nucleation and guide Li metal deposition. These transition metal nitrides with excellent conductivity can guarantee the fast electron transport, therefore maintain a stable interface for Li reduction. In addition, the designed multi-dimensional structure of metal nitride array decorated carbon framework can effectively regulate the growth of Li metal during the stripping/plating process. Of note, attributing to the lattice-matching between CoN and Li metal, the composite Li/CoN@CF anode exhibits ultra-stable cycling performance in symmetrical cells (over 4000 h@1 mA cm⁻² with 1 mAh cm⁻² and 1000h@20 mA cm⁻² with 20 mAh cm⁻²). The assembled full cells based on Li/CoN@CF composite anode, LiFePO₄ or S as cathodes, deliver excellent cycling stability and rate capability. This strategy provides an effective approach to develop a stable lithium metal anode for lithium metal batteries.     

Dendrite‐Free Lithium Anodes with Ultra‐Deep Stripping and Plating Properties Based on Vertically Oriented Lithium–Copper–Lithium Arrays

Although lithium metal is the best anode for lithium‐based batteries, the uncontrollable lithium dendrites especially under deep stripping and plating states hamper its practical applications. Here, a dendrite‐free lithium anode is developed based on vertically oriented lithium–copper–lithium arrays, which can be facilely produced via traditional rolling or repeated stacking approaches. Such vertically oriented arrays not only enable both the lithium‐ion flux and the electric field to be regulated, but also can act as a “dam” to guide the regular plating of lithium, thus efficiently buffering the volume change of the lithium anode upon cycling. As a consequence, the vertically oriented anode exhibits an excellent deep stripping and plating capability upto 50 mAh cm^?2, high rate capabilities (20 mA cm^?2), and long cycle life (2000 h). Based on this anode, a full lithium battery with a LiCoO₂ cathode delivers a good cycle life, holding great potential for practical lithium‐metal batteries with high energy densities.     

Additive‐Assisted Novel Dual‐Salt Electrolyte Addresses Wide Temperature Operation of Lithium–Metal Batteries

In this study, self‐synthesized lithium trifluoro(perfluoro‐tert‐butyloxyl)borate (LiTFPFB) is combined with lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) to formulate a novel 1 m dual‐salt electrolyte, which contains lithium difluorophosphate (LiPO₂F₂) additive and dominant carbonate solvents with low melting point and high boiling point. The addition of LiPO₂F₂ into this novel dual‐salt electrolyte dramatically improves cycleability and rate capability of a LiNi_0.5Mn_0.3Co_0.2O₂/Li (NMC/Li) battery, ranging from ?40 to 90 °C. The NMC/Li batteries adopt a Li–metal anode with low thickness of 100 µm (even 50 µm) and a moderately high cathode mass loading level of 10 mg cm^?2. For the first time, this paper provides valuable perspectives for developing practical lithium–metal batteries over a wide temperature range.     

Field-Induced Transitions in RECo0.50Mn0.50O3 (RE = Dy, Eu)

We have studied the magnetization at high magnetic field for bulk ceramic samples of EuCo_0.50Mn_0.50O₃ and DyCo_0.50Mn_0.50O₃ at low temperature. For the Dy sample we can see two field transitions (near 2 T and 5 T) and the magnetization measured at 20 T (6.7 μ_B) is near the expected value (M _S =6.76 μ_B) if we consider a ferrimagnetic model of two sublattices fully aligned, one in opposition to the other. For the Eu sample we have five step transitions on the hysteresis curves (near 1; 3; 4; 5 and 6 T) and the measured magnetization at 20 T (2.6 μ_B) is lower than the expected value (M _S =3.87 μ_B), suggesting this is a case of Van Vleck magnetism. Nickel-containing samples of similar composition have been measured but no field-induced anomaly has been found.