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Solid-state lithium metal batteries require accommodation of electrochemically generated mechanical stress inside the lithium: this stress can be1,2 up to 1 gigapascal for an overpotential of 135 millivolts. Maintaining the mechanical and electrochemical stability of the solid structure despite physical contact with moving corrosive lithium metal is a demanding requirement. Using in situ transmission electron microscopy, we investigated the deposition and stripping of metallic lithium or sodium held within a large number of parallel hollow tubules made of a mixed ionic-electronic conductor (MIEC). Here we show that these alkali metals-as single crystals-can grow out of and retract inside the tubules via mainly diffusional Coble creep along the MIEC/metal phase boundary. Unlike solid electrolytes, many MIECs are electrochemically stable in contact with lithium (that is, there is a direct tie-line to metallic lithium on the equilibrium phase diagram), so this Coble creep mechanism can effectively relieve stress, maintain electronic and ionic contacts, eliminate solid-electrolyte interphase debris, and allow the reversible deposition/stripping of lithium across a distance of 10 micrometres for 100 cycles. A centimetre-wide full cell-consisting of approximately 1010 MIEC cylinders/solid electrolyte/LiFePO4-shows a high capacity of about 164 milliampere hours per gram of LiFePO4, and almost no degradation for over 50 cycles, starting with a 1× excess of Li. Modelling shows that the design is insensitive to MIEC material choice with channels about 100 nanometres wide and 10-100 micrometres deep. The behaviour of lithium metal within the MIEC channels suggests that the chemical and mechanical stability issues with the metal-electrolyte interface in solid-state lithium metal batteries can be overcome using this architecture.
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Employing high voltage cobalt-free spinel LiNi0.5 Mn1.5 O4 (LNMO) as a cathode is promising for high energy density and cost-effectiveness, but it has challenges in all-solid-state batteries (ASSBs). Here, it is revealed that the limitation of lithium argyrodite sulfide solid electrolyte (Li6 PS5 Cl) with the LNMO cathode is due to the intrinsic chemical incompatibility and poor oxidative stability. Through a careful analysis of the interphase of LNMO, it is elucidated that even the halide solid electrolyte (Li3 InCl6 ) with high oxidative stability can be decomposed to form resistive interphase layers with LNMO in ASSBs. Interestingly, with Fe-doping and a Li3 PO4 protective layer coating, LNMO with Li3 InCl6 displays stable cycle performance with a stabilized interphase at a high voltage (≈4.7 V) in ASSBs. The enhanced interfacial stability with the extended electrochemical stability window through doping and coating enables high electrochemical stability with LNMO in ASSBs. This work provides guidance for employing high-voltage cathodes in ASSBs and highlights the importance of stable interphases to enable stable cycling in ASSBs.
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A new perovskite KOsO_{3} has been stabilized under high-pressure and high-temperature conditions. It is cubic at 500 K (Pm-3m) and undergoes subsequent phase transitions to tetragonal at 320 K (P4/mmm) and rhombohedral (R-3m) at 230 K as shown from refining synchrotron x-ray powder diffraction (SXRD) data. The larger orbital overlap integral and the extended wave function of 5d electrons in the perovskite KOsO_{3} allow to explore physics from the regime where Mott and Hund's rule couplings dominate to the state where the multiple interactions are on equal footing. We demonstrate an exotic magnetic ordering phase found by neutron powder diffraction along with physical properties via a suite of measurements including magnetic and transport properties, differential scanning calorimetry, and specific heat, which provide comprehensive information for a system at the crossover from localized to itinerant electronic behavior.
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All-solid-state lithium-metal batteries offer higher energy density and safety than lithium-ion batteries, but their practical applications have been pushed back by the sluggish Li+ transport, unstable electrolyte/electrode interface, and/or difficult processing of their solid-state electrolytes. Li+ -conducting composite polymer electrolytes (CPEs) consisting of sub-micron particles of an oxide solid-state electrolyte (OSSE) dispersed in a solid, flexible polymer electrolyte (SPE) have shown promises to alleviate the low Li+ conductivity of SPE, and the high rigidity and large interfacial impedance of OSSEs. Solution casting has been by far the most widely used procedure for the preparation of CPEs in research laboratories; however, this method imposes several drawbacks including particle aggregation and settlement during a long-term solvent evaporation step, excessive use of organic solvents, slow production time, and mechanical issues associated with handling of ultra-thin films of CPEs (<50 µm). To address these challenges, an electrophoretic deposition (EPD) method is developed to in situ deposit ultra-thin CPEs on lithium-iron-phosphate (LFP) cathodes within just a few minutes. EPD-prepared CPEs have shown better electrochemical performance in the lithium-metal battery than those CPEs prepared by solution casting due to a better dispersion of OSSE within the SPE matrix and improved CPE contact with LFP cathodes.
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Flexible and low-cost poly(ethylene oxide) (PEO)-based electrolytes are promising for all-solid-state Li-metal batteries because of their compatibility with a metallic lithium anode. However, the low room-temperature Li-ion conductivity of PEO solid electrolytes and severe lithium-dendrite growth limit their application in high-energy Li-metal batteries. Here we prepared a PEO/perovskite Li3/8Sr7/16Ta3/4Zr1/4O3 composite electrolyte with a Li-ion conductivity of 5.4 × 10-5 and 3.5 × 10-4 S cm-1 at 25 and 45 °C, respectively; the strong interaction between the F- of TFSI- (bis-trifluoromethanesulfonimide) and the surface Ta5+ of the perovskite improves the Li-ion transport at the PEO/perovskite interface. A symmetric Li/composite electrolyte/Li cell shows an excellent cyclability at a high current density up to 0.6 mA cm-2 A solid electrolyte interphase layer formed in situ between the metallic lithium anode and the composite electrolyte suppresses lithium-dendrite formation and growth. All-solid-state Li|LiFePO4 and high-voltage Li|LiNi0.8Mn0.1Co0.1O2 batteries with the composite electrolyte have an impressive performance with high Coulombic efficiencies, small overpotentials, and good cycling stability.
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The layered oxide Na0.67CoO2 with Na+ occupying trigonal prismatic sites between CoO2 layers exhibits a remarkably high room temperature oxygen evolution reaction (OER) activity in alkaline solution. The high activity is attributed to an unusually short O-O separation that favors formation of peroxide ions by O--O- interactions followed by O2 evolution in preference to the conventional route through surface O-OH- species. The dependence of the onset potential on the pH of the alkaline solution was found to be consistent with the loss of H+ ions from the surface oxygen to provide surface O- that may either be attacked by solution OH- or react with another O-; a short O-O separation favors the latter route. The role of a strong hybridization of the O-2p and low-spin CoIII/CoIV π-bonding d states is also important; the OER on other CoIII/CoIV oxides is compared with that on Na0.67CoO2 as well as that on IrO2.
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Great progress has been achieved in the research field of topological states of matter during the past decade. Recently, a quasi-1-dimensional bismuth bromide, Bi4Br4, has been predicted to be a rotational symmetry-protected topological crystalline insulator; it would also exhibit more exotic topological properties under pressure. Here, we report a thorough study of phase transitions and superconductivity in a quasihydrostatically pressurized α-Bi4Br4 crystal by performing detailed measurements of electrical resistance, alternating current magnetic susceptibility, and in situ high-pressure single-crystal X-ray diffraction together with first principles calculations. We find a pressure-induced insulator-metal transition between â¼3.0 and 3.8 GPa where valence and conduction bands cross the Fermi level to form a set of small pockets of holes and electrons. With further increase of pressure, 2 superconductive transitions emerge. One shows a sharp resistance drop to 0 near 6.8 K at 3.8 GPa; the transition temperature gradually lowers with increasing pressure and completely vanishes above 12.0 GPa. Another transition sets in around 9.0 K at 5.5 GPa and persists up to the highest pressure of 45.0 GPa studied in this work. Intriguingly, we find that the first superconducting phase might coexist with a nontrivial rotational symmetry-protected topology in the pressure range of â¼3.8 to 4.3 GPa; the second one is associated with a structural phase transition from monoclinic C2/m to triclinic P-1 symmetry.
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It remains a great challenge to explore desirable cathodes for sodium-ion batteries to satisfy the ever-increasing demand for large-scale energy storage systems. In this Letter, we report a NASICON-structured Na4MnCr(PO4)3 cathode with high specific capacity and operation potential. The reversible access of the Mn2+/Mn3+ (3.75/3.4 V), Mn3+/Mn4+ (4.25/4.1 V), and Cr3+/Cr4+ (4.4/4.3 V vs Na/Na+) redox couples in a Na4MnCr(PO4)3 cathode endows a distinct three-electron redox reaction during the insertion/extraction process. The highly stable NASICON structure with a small volume variation upon cycling ensures long-time cycling stability (73.3% capacity retention after 500 cycles within the potential region of 2.5-4.6 V). The impedance analysis and interface characterization indicate that the evolution of a cathode electrolyte interphase at high potential is correlated with the capacity fading, while the robustness of the NASICON framework is redemonstrated.
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The application of flexible, robust, and low-cost solid polymer electrolytes in next-generation all-solid-state lithium metal batteries has been hindered by the low room-temperature ionic conductivity of these electrolytes and the small critical current density of the batteries. Both issues stem from the low mobility of Li+ ions in the polymer and the fast lithium dendrite growth at the Li metal/electrolyte interface. Herein, Mg(ClO4)2 is demonstrated to be an effective additive in the poly(ethylene oxide) (PEO)-based composite electrolyte to regulate Li+ ion transport and manipulate the Li metal/electrolyte interfacial performance. By combining experimental and computational studies, we show that Mg2+ ions are immobile in a PEO host due to coordination with ether oxygen and anions of lithium salts, which enhances the mobility of Li+ ions; more importantly, an in-situ formed Li+-conducting Li2MgCl4/LiF interfacial layer homogenizes the Li+ flux during plating and increases the critical current density up to a record 2 mA cm-2. Each of these factors contributes to the assembly of competitive all-solid-state Li/Li, LiFePO4/Li, and LiNi0.8Mn0.1Co0.1O2/Li cells, demonstrating the importance of surface chemistry and interfacial engineering in the design of all-solid-state Li metal batteries for high-current-density applications.
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We report a thorough study of the transport properties of the normal and superconducting states of black phosphorus (BP) under magnetic field and high pressure with a large-volume apparatus that provides hydrostatic pressure to induce transitions from the layered A17 phase to the layered A7 phase and to the cubic phase of BP. Quantum oscillations can be observed at P ≥ 1 GPa in both resistivity and Hall voltage, and their evolutions with pressure in the A17 phase imply a continuous enlargement of Fermi surface. A significantly large magnetoresistance (MR) at low temperatures is observed in the A7 phase that becomes superconducting below a superconducting transition temperature Tc â¼ 6-13 K. Tc increases continuously with pressure on crossing the A7 to the cubic phase boundary. The strong MR effect can be fit by a modified Kohler's rule. A correlation between Tc and fitting parameters suggests that phonon-mediated interactions play dominant roles in driving the Cooper pairing, which is further supported by our density functional theory (DFT) calculations. The change of effective carrier mobility in the A17 phase under pressure derived from the MR effect is consistent with that obtained from the temperature dependence of the quantum oscillations. In situ single-crystal diffraction under high pressure indicates a total structural reconstruction instead of simple stretching of the A17 phase layers in the A17-to-A7-phase transition. This finding helps us to interpret transport properties on crossing the phase transition under high pressure.
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We present the first results of in situ scanning electron microscopy (SEM) of an all-solid Li battery with a nickel-manganese-cobalt-oxide (NMC-622) cathode at 50 °C and an operating voltage of 2.7-4.3 V. Experiments were conducted under a constant current at several C rates (nC rate: cycling in 1/n h): C/12, C/6, and C/3. The microstructure evolution during cycling was monitored by continuous secondary electron imaging. We found that the chemical degradation of the solid polymer electrolyte (SPE) was the main mechanism for battery failure. This degradation was observed in the form of a gradual thinning of the SPE as a function of cycling time, resulting in gas generation from the cell. We also present various dynamic electrochemical and mechanical phenomena, as observed by SEM images, and compare the performance of this battery with that of an all-solid Li battery with a LiFePO4 cathode.
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The integration of Li2 S6 within a poly(ethylene oxide) (PEO)-based polymer electrolyte is demonstrated to improve the polymer electrolyte's ionic conductivity because the strong interplay between O2- (PEO) and Li+ from Li2 S6 reduces the crystalline volume within the PEO. The Li/electrolyte interface is stabilized by the in situ formation of an ultra-thin Li2 S/Li2 S2 layer via the reaction between Li2 S6 and lithium metal, which increases the ionic transport at the interface and suppresses lithium dendrite growth. A symmetric Li/Li cell with the Li2 S6 -integrated composite electrolyte has excellent cyclability and a high critical current density of 0.9â mA cm-2 at 40 °C. Impressive electrochemical performance is demonstrated with all-solid-state Li/LiFePO4 and high-voltage Li/LiNi0.8 Mn0.1 Co0.1 O2 cells at 40 °C.
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The unclear Li+ local environment and Li+ conduction mechanism in solid polymer electrolytes, especially in a ceramic/polymer composite electrolyte, hinder the design and development of a new composite electrolyte. Moreover, both the low room-temperature Li+ conductivity and large interfacial resistance with a metallic lithium anode of a polymer membrane limit its application below a relatively high temperature. Here we have identified the Li+ distribution and Li+ transport mechanism in a composite polymer electrolyte by investigating a new solid poly(ethylene oxide) (PEO)-based NASICON-LiZr2(PO4)3 composite with 7Li relaxation time and 6Li â 7Li trace-exchange NMR measurements. The Li+ population of the two local environments in the composite electrolytes depends on the Li-salt concentration and the amount of ceramic filler. A composite electrolyte with a [EO]/[Li+] ratio n = 10 and 25 wt % LZP filler has a high Li+ conductivity of 1.2 × 10-4 S cm-1 at 30 °C and a low activation energy owing to the additional Li+ in the mobile A2 environment. Moreover, an in situ formed solid electrolyte interphase layer from the reaction between LiZr2(PO4)3 and a metallic lithium anode stabilized the Li/composite-electrolyte interface and reduced the interfacial resistance, which provided a symmetric Li/Li cell and all-solid-state Li/LiFePO4 and Li/LiNi0.8Co0.1Mn0.1O2 cells a good cycling performance at 40 °C.
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Perovskite oxides have attracted much attention for enabling the oxygen-evolution reaction (OER) over the past decades. Nevertheless, their poor conductivity is still a barrier hindering their use. Herein, we report a catalyst prototype of Co-based antiperovskite nitrides CuNCo3-xVx (0 ≤ x ≤ 1) to be a highly effective OER electrocatalyst. The synthesized CuNCo3-xVx exhibits greatly enhanced activity and stability toward the OER in alkaline medium. The CuNCo2.4V0.6 shows a mere 235 mV of overpotential to reach 10 mA cm-2, which is comparable to that of Ir/C (232 mV). More importantly, the CuNCo2.4V0.6 is more durable than the conventional Ir/C catalyst. The CuNCo2.4V0.6 catalyst enabled a Zn-air battery to exhibit a cycle life of 143 h with a much higher cell efficiency. The V-substituted CuNCo2.4V0.6 provides a higher content of the desirable Co3+ species in the post-OER catalyst, which ensures a high activity over a long-term operation. With these enhanced effects enabled by the compositional flexibility of CuNCo3-xVx antiperovskite nitride, a feasible strategy for optimizing an electrocatalyst with tunable properties is provided.
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A group of newly reported antiperovskite nitrides Cux In1-x NNi3 (0≤x≤1) with tunable composition are employed as electrocatalysts for the hydrogen evolution reaction (HER). Cu0.4 In0.6 NNi3 shows the highest intrinsic performance among all developed catalysts with an overpotential of merely 42â mV at 10â mA cmgeo -2 . Stability tests at a high current density of 100â mA cmgeo -2 show its super-stable performance with only 7â mV increase in overpotential after more than 60 hours of measurement, surpassing commercial Pt/C (increase of 170â mV). By partial substitution, the derived antiperovskite nitride achieves a smaller kinetic barrier of water dissociation compared to the unsubstituted InNNi3 and CuNNi3 , revealed by first-principle calculations. It is found that the partially substituted Cux In1-x NNi3 possesses a thermal neutral and desirable Gibbs free energy of hydrogen for HER, ascribed to the tailoring of the energy of d-band center arose by the A-site (A=Cu or In) substitution and a resulting optimization of adsorbate interactions.
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Galvanic replacement reactions have been studied as a versatile route to synthesize nanostructured alloys. However, the galvanic replacement chemistry of alkali metals has rarely been explored. A protective interphase layer will be formed outside templates when the redox potential exceeds the potential windows of nonaqueous solutions, and the complex interfacial chemistry remains elusive. Here, we demonstrate the formation of room-temperature liquid metal alloys of Na and K via galvanic replacement reaction. The fundamentals of the reaction at such low potentials are investigated via a combined experimental and computational method, which uncovers the critical role of solid-electrolyte interphase in regulating the migration of Na ions and thus the alloying reaction kinetics. With in situ formed NaK liquid alloys as an anode, the dendritic growth of alkali metals can be eliminated thanks to the deformable and self-healing features of liquid metals. The proof-of-concept battery delivers reasonable electrochemical performance, confirming the generality of this in situ approach and design principle for next-generation dendrite-free batteries.
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Controllable synthesis of atomically ordered intermetallic nanoparticles (NPs) is crucial to obtain superior electrocatalytic performance for fuel cell reactions, but still remains arduous. Herein, we demonstrate a novel and general hydrogel-freeze drying strategy for the synthesis of reduced graphene oxide (rGO) supported Pt3 M (M=Mn, Cr, Fe, Co, etc.) intermetallic NPs (Pt3 M/rGO-HF) with ultrasmall particle size (about 3â nm) and dramatic monodispersity. The formation of hydrogel prevents the aggregation of graphene oxide and significantly promotes their excellent dispersion, while a freeze-drying can retain the hydrogel derived three-dimensionally (3D) porous structure and immobilize the metal precursors with defined atomic ratio on GO support during solvent sublimation, which is not afforded by traditional oven drying. The subsequent annealing process produces rGO supported ultrasmall ordered Pt3 M intermetallic NPs (≈3â nm) due to confinement effect of 3D porous structure. Such Pt3 M intermetallic NPs exhibit the smallest particle size among the reported ordered Pt-based intermetallic catalysts. A detailed study of the synthesis of ordered intermetallic Pt3 Mn/rGO catalyst is provided as an example of a generally applicable method. This study provides an economical and scalable route for the controlled synthesis of Pt-based intermetallic catalysts, which can pave a way for the commercialization of fuel cell technologies.
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Li+ -conducting oxides are considered better ceramic fillers than Li+ -insulating oxides for improving Li+ conductivity in composite polymer electrolytes owing to their ability to conduct Li+ through the ceramic oxide as well as across the oxide/polymer interface. Here we use two Li+ -insulating oxides (fluorite Gd0.1 Ce0.9 O1.95 and perovskite La0.8 Sr0.2 Ga0.8 Mg0.2 O2.55 ) with a high concentration of oxygen vacancies to demonstrate two oxide/poly(ethylene oxide) (PEO)-based polymer composite electrolytes, each with a Li+ conductivity above 10-4 â S cm-1 at 30 °C. Li solid-state NMR results show an increase in Li+ ions (>10 %) occupying the more mobile A2 environment in the composite electrolytes. This increase in A2-site occupancy originates from the strong interaction between the O2- of Li-salt anion and the surface oxygen vacancies of each oxide and contributes to the more facile Li+ transport. All-solid-state Li-metal cells with these composite electrolytes demonstrate a small interfacial resistance with good cycling performance at 35 °C.
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Potassium manganese hexacyanoferrate (KMHCF) is a low-cost Prussian blue analogue (PBA) having a rigid and open framework that can accommodate large alkali ions. Herein, the synthesis of KMHCF and its application as a high-performance cathode in sodium-ion batteries (NIBs) is reported. High-quality KMHCF with low amounts of crystal water and defects and with homogeneous microstructure is obtained by controlling the nucleation and grain growth by using a high-concentration citrate solution as a precipitation medium. The obtained KMHCF exhibits superior cycling and rate performance as a NIB cathode, showing 80% capacity retention after 1000 cycles at 1 C and a high capacity of 95 mA h g-1 at 20 C. Unlike conventional single-cation batteries, the hybrid NIB with KMHCF as cathode and Na as anode in Na-ion electrolyte displays three reversible plateaus that involve stepwise insertion/extraction of both K+ and Na+ in the PBA framework. In later cycling, the K+ -Na+ cointercalated phase is partially converted into a cubic sodium manganese hexacyanoferrate (NaMHCF) phase due to the increasing replacement of Na+ for K+ .
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A solid electrolyte with a high Li-ion conductivity and a small interfacial resistance against a Li metal anode is a key component in all-solid-state Li metal batteries, but there is no ceramic oxide electrolyte available for this application except the thin-film Li-P oxynitride electrolyte; ceramic electrolytes are either easily reduced by Li metal or penetrated by Li dendrites in a short time. Here, we introduce a solid electrolyte LiZr2(PO4)3 with rhombohedral structure at room temperature that has a bulk Li-ion conductivity σLi = 2 × 10-4 Sâ cm-1 at 25 °C, a high electrochemical stability up to 5.5 V versus Li+/Li, and a small interfacial resistance for Li+ transfer. It reacts with a metallic lithium anode to form a Li+-conducting passivation layer (solid-electrolyte interphase) containing Li3P and Li8ZrO6 that is wet by the lithium anode and also wets the LiZr2(PO4)3 electrolyte. An all-solid-state Li/LiFePO4 cell with a polymer catholyte shows good cyclability and a long cycle life.