Manipulating Layered P2@P3 Integrated Spinel Structure Evolution for High-Performance Sodium-Ion Batteries

Structural evolution of the cathode during cycling plays a vital role in the electrochemical performance of sodium-ion batteries. A strategy based on engineering the crystal structure coupled with chemical substitution led to the design of the layered P2@P3 integrated spinel oxide cathode Na_0.5Ni_0.1Co_0.15Mn_0.65Mg_0.1O₂, which shows excellent sodium-ion half/full battery performance. Combined analyses involving scanning transmission electron microscopy with atomic resolution as well as in situ synchrotron-based X-ray absorption spectra and in situ synchrotron-based X-ray diffraction patterns led to visualization of the inherent layered P2@P3 integrated spinel structure, charge compensation mechanism, structural evolution, and phase transition. This study provides an in-depth understanding of the structure-performance relationship in this structure and opens up a novel field based on manipulating structural evolution for the design of high-performance battery cathodes.     

Deciphering an Abnormal Layered‐Tunnel Heterostructure Induced by Chemical Substitution for the Sodium Oxide Cathode

Demands for large‐scale energy storage systems have driven the development of layered transition‐metal oxide cathodes for room‐temperature rechargeable sodium ion batteries (SIBs). Now, an abnormal layered‐tunnel heterostructure Na_0.44Co_0.1Mn_0.9O₂ cathode material induced by chemical element substitution is reported. By virtue of beneficial synergistic effects, this layered‐tunnel electrode shows outstanding electrochemical performance in sodium half‐cell system and excellent compatibility with hard carbon anode in sodium full‐cell system. The underlying formation process, charge compensation mechanism, phase transition, and sodium‐ion storage electrochemistry are clearly articulated and confirmed through combined analyses of in situ high‐energy X‐ray diffraction and ex situ X‐ray absorption spectroscopy as well as operando X‐ray diffraction. This crystal structure engineering regulation strategy offers a future outlook into advanced cathode materials for SIBs.     

A Hydrostable Cathode Material Based on the Layered P2@P3 Composite that Shows Redox Behavior for Copper in High‐Rate and Long‐Cycling Sodium‐Ion Batteries

Low‐cost layered oxides free of Ni and Co are considered to be the most promising cathode materials for future sodium‐ion batteries. Biphasic Na_0.78Cu_0.27Zn_0.06Mn_0.67O₂ obtained via superficial atomic‐scale P3 intergrowth with P2 phase induced by Zn doping, consisting of inexpensive transition metals, is a promising cathode for sodium‐ion batteries. The P3 phase as a covering layer in this composite shows not only in excellent electrochemical performance but also its tolerance to moisture. The results indicate that partial Zn substitutes can effectively control biphase formation for improving the structural/electrochemical stability as well as the ionic diffusion coefficient. Based on in situ synchrotron X‐ray diffraction coupled with electron‐energy‐loss spectroscopy, a possible Cu^2+/3+ redox reaction mechanism has now been revealed.     

Development and Investigation of a NASICON‐Type High‐Voltage Cathode Material for High‐Power Sodium‐Ion Batteries

Herein, we introduce a 4.0 V class high‐voltage cathode material with a newly recognized sodium superionic conductor (NASICON)‐type structure with cubic symmetry (space group P2₁3), Na₃V(PO₃)₃N. We synthesize an N‐doped graphene oxide‐wrapped Na₃V(PO₃)₃N composite with a uniform carbon coating layer, which shows excellent rate performance and outstanding cycling stability. Its air/water stability and all‐climate performance were carefully investigated. A near‐zero volume change (ca. 0.40 %) was observed for the first time based on in situ synchrotron X‐ray diffraction, and the in situ X‐ray absorption spectra revealed the V^3.2+/V^4.2+ redox reaction with high reversibility. Its 3D sodium diffusion pathways were demonstrated with distinctive low energy barriers. Our results indicate that this high‐voltage NASICON‐type Na₃V(PO₃)₃N composite is a competitive cathode material for sodium‐ion batteries and will receive more attention and studies in the future.     

Lithium‐Rich Layered Oxide Li1.18Ni0.15Co0.15Mn0.52O2 as the Cathode Material for Hybrid Sodium‐Ion Batteries

Li‐rich layered oxide Li_1.18Ni_0.15Co_0.15Mn_0.52O₂ (LNCM) is, for the first time, examined as the positive electrode for hybrid sodium‐ion battery and its Na⁺ storage properties are comprehensively studied in terms of galvanostatic charge–discharge curves, cyclic voltammetry and rate capability. LNCM in the proposed sodium‐ion battery demonstrates good rate capability whose discharge capacity reaches about 90 mA h g^?1 at 10 C rate and excellent cycle stability with specific capacity of about 105 mA h g^?1 for 200 cycles at 5 C rate. Moreover, ex situ ICP‐OES suggests interesting mixed‐ions migration processes: In the initial two cycles, only Li⁺ can intercalate into the LNCM cathode, whereas both Li⁺ and Na⁺ work together as the electrochemical cycles increase. Also the structural evolution of LNCM is examined in terms of ex situ XRD pattern at the end of various charge–discharge scans. The strong insight obtained from this study could be beneficial to the design of new layered cathode materials for future rechargeable sodium‐ion batteries.     

Electrochemical and Structural Study of Layered P2‐Type Na2/3Ni1/3Mn2/3O2 as Cathode Material for Sodium‐Ion Battery

P2‐type Na_2/3Ni_1/3Mn_2/3O₂ was synthesized by a controlled co‐precipitation method followed by a high‐temperature solid‐state reaction and was used as a cathode material for a sodium‐ion battery (SIB). The electrochemical behavior of this layered material was studied and an initial discharge capacity of 151.8 mA h g^?1 was achieved in the voltage range of 1.5–3.75 V versus Na⁺/Na. The retained discharge capacity was found to be 123.5 mA h g^?1 after charging/discharging 50 cycles, approximately 81.4 % of the initial discharge capacity. In situ X‐ray diffraction analysis was used to investigate the sodium insertion and extraction mechanism and clearly revealed the reversible structural changes of the P2‐Na_2/3Ni_1/3Mn_2/3O₂ and no emergence of the O2‐Ni_1/3Mn_2/3O₂ phase during the cycling test, which is important for designing stable and high‐performance SIB cathode materials.     

Nitride Spinel: An Ultraincompressible High‐Pressure Form of BeP2N4

Owing to its outstanding elastic properties, the nitride spinel γ‐Si₃N₄ is of considered interest for materials scientists and chemists. DFT calculations suggest that Si₃N₄‐analog beryllium phosphorus nitride BeP₂N₄ adopts the spinel structure at elevated pressures as well and shows outstanding elastic properties. Herein, we investigate phenakite‐type BeP₂N₄ by single‐crystal synchrotron X‐ray diffraction and report the phase transition into the spinel‐type phase at 47 GPa and 1800 K in a laser‐heated diamond anvil cell. The structure of spinel‐type BeP₂N₄ was refined from pressure‐dependent in situ synchrotron powder X‐ray diffraction measurements down to ambient pressure, which proves spinel‐type BeP₂N₄ a quenchable and metastable phase at ambient conditions. Its isothermal bulk modulus was determined to 325(8) GPa from equation of state, which indicates that spinel‐type BeP₂N₄ is an ultraincompressible material.     

Size‐Mediated Recurring Spinel Sub‐nanodomains in Li‐ and Mn‐Rich Layered Cathode Materials

Li‐ and Mn‐rich layered oxides are among the most promising cathode materials for Li‐ion batteries with high theoretical energy density. Its practical application is, however, hampered by the capacity and voltage fade after long cycling. Herein, a finite difference method for near‐edge structure (FDMNES) code was combined with in situ X‐ray absorption spectroscopy (XAS) and transmission electron microscopy/electron energy loss spectroscopy (TEM/EELS) to investigate the evolution of transition metals (TMs) in fresh and heavily cycled electrodes. Theoretical modeling reveals a recurring partially reversible LiMn₂O₄‐like sub‐nanodomain formation/dissolution process during each charge/discharge, which accumulates gradually and accounts for the Mn phase transition. From the modeling of spectra and maps of the valence state over large regions of the cathodes, it was found that the phase change is size‐dependent. After prolonged cycling, the TMs displayed different levels of inactivity.     

A Cation and Anion Dual Doping Strategy for the Elevation of Titanium Redox Potential for High‐Power Sodium‐Ion Batteries

Titanium‐based polyanions have been intensively investigated for sodium‐ion batteries owing to their superior structural stability and thermal safety. However, their low working potential hindered further applications. Now, a cation and anion dual doping strategy is used to boost the redox potential of Ti‐based cathodes of Na₃Ti_0.5V_0.5(PO₃)₃N as a new cathode material for sodium ion batteries. Both the Ti³⁺/Ti⁴⁺ and V³⁺/V⁴⁺ redox couples are reversibly accessed, leading to two distinctive voltage platforms at ca. 3.3 V and ca. 3.8 V, respectively. The remarkably improved cycling stability (86.3 %, 3000 cycles) can be ascribed to the near‐zero volume strain in this unusual cubic symmetry, which has been demonstrated by in situ synchrotron‐based X‐ray diffraction. First‐principles calculations reveal its well‐interconnected 3D Na diffusion pathways with low energy barriers, and the two‐sodium‐extracted intermediate NaTi_0.5V_0.5(PO₃)₃N is also a stable phase according to formation energy calculations.     

Hierarchical Surface Atomic Structure of a Manganese‐Based Spinel Cathode for Lithium‐Ion Batteries

The increasing use of lithium‐ion batteries (LIBs) in high‐power applications requires improvement of their high‐temperature electrochemical performance, including their cyclability and rate capability. Spinel lithium manganese oxide (LiMn₂O₄) is a promising cathode material because of its high stability and abundance. However, it exhibits poor cycling performance at high temperatures owing to Mn dissolution. Herein we show that when stoichiometric lithium manganese oxide is coated with highly doped spinels, the resulting epitaxial coating has a hierarchical atomic structure consisting of cubic‐spinel, tetragonal‐spinel, and layered structures, and no interfacial phase is formed. In a practical application of the coating to doped spinel, the material retained 90 % of its capacity after 800 cycles at 60 °C. Thus, the formation of an epitaxial coating with a hierarchical atomic structure could enhance the electrochemical performance of LIB cathode materials while preventing large losses in capacity.     

In Situ Three‐Dimensional Synchrotron X‐Ray Nanotomography of the (De)lithiation Processes in Tin Anodes

The three‐dimensional quantitative analysis and nanometer‐scale visualization of the microstructural evolutions of a tin electrode in a lithium‐ion battery during cycling is described. Newly developed synchrotron X‐ray nanotomography provided an invaluable tool. Severe microstructural changes occur during the first delithiation and the subsequent second lithiation, after which the particles reach a structural equilibrium with no further significant morphological changes. This reveals that initial delithiation and subsequent lithiation play a dominant role in the structural instability that yields mechanical degradation. This in situ 3D quantitative analysis and visualization of the microstructural evolution on the nanometer scale by synchrotron X‐ray nanotomography should contribute to our understanding of energy materials and improve their synthetic processing.     

Graphite‐Nanoplate‐Coated Bi2S3 Composite with High‐Volume Energy Density and Excellent Cycle Life for Room‐Temperature Sodium–Sulfide Batteries

Graphite‐nanoplate‐coated Bi₂S₃ composite (Bi₂S₃@C) has been prepared by a simple, scalable, and energy‐efficient precipitation method combined with ball milling. The Bi₂S₃@C composite was used as the cathode material for sodium–sulfide batteries. It delivered an initial capacity of 550 mAh g^?1 and high stable specific energy in the range of 275–300 Wh kg^?1 at 0.1 C, with an enhanced capacity retention of 69 % over 100 cycles. The unique structure demonstrates superior cycling stability, with a capacity drop of 0.3 % per cycle over 100 cycles, compared with that of bare Bi₂S₃. The sodium storage mechanism of Bi₂S₃ was investigated based on ex situ X‐ray diffraction and scanning transmission electron microscopy.     

An Aqueous Symmetric Sodium‐Ion Battery with NASICON‐Structured Na3MnTi(PO4)3

A symmetric sodium‐ion battery with an aqueous electrolyte is demonstrated; it utilizes the NASICON‐structured Na₃MnTi(PO₄)₃ as both the anode and the cathode. The NASICON‐structured Na₃MnTi(PO₄)₃ possesses two electrochemically active transition metals with the redox couples of Ti⁴⁺/Ti³⁺ and Mn³⁺/Mn²⁺ working on the anode and cathode sides, respectively. The symmetric cell based on this bipolar electrode material exhibits a well‐defined voltage plateau centered at about 1.4 V in an aqueous electrolyte with a stable cycle performance and superior rate capability. The advent of aqueous symmetric sodium‐ion battery with high safety and low cost may provide a solution for large‐scale stationary energy storage.     

The Proportion of Fe‐NX,N Doping Species and Fe3C to Oxygen Catalytic Activity in Core‐Shell Fe‐N/C Electrocatalyst

A bifunctional oxygen electrocatalyst composed of iron carbide (Fe₃C) nanoparticles encapsulated by nitrogen doped carbon sheets is reported. X‐ray photoelectron spectroscopy and X‐ray absorption near edge structure revealed the presence of several kinds of active sites (Fe?N_x sites, N doping sites) and the modulated electron structure of nitrogen doped carbon sheets. Fe₃C@N‐CSs shows excellent oxygen evolution and oxygen reduction catalytic activity owing to the modulated electron structure by encapsulated Fe₃C core via biphasic interfaces electron interaction, which can lower the free energy of intermediate, strengthen the bonding strength and enhance conductivity. Meanwhile, the contribution of the Fe?N_x sites, N doping sites and the effect of Fe₃C core for the electrocatalytic oxygen reaction is originally revealed. The Fe₃C@N‐CSs air electrode‐based zinc‐air battery demonstrates a high open circuit potential of 1.47 V, superior charge‐discharge performance and long lifetime, which outperforms the noble metal‐based zinc‐air battery.     

Understanding High‐Rate K+‐Solvent Co‐Intercalation in Natural Graphite for Potassium‐Ion Batteries

Graphite shows great potential as an anode material for rechargeable metal‐ion batteries because of its high abundance and low cost. However, the electrochemical performance of graphite anode materials for rechargeable potassium‐ion batteries needs to be further improved. Reported herein is a natural graphite with superior rate performance and cycling stability obtained through a unique K⁺‐solvent co‐intercalation mechanism in a 1 m KCF₃SO₃ diethylene glycol dimethyl ether electrolyte. The co‐intercalation mechanism was demonstrated by ex situ Fourier transform infrared spectroscopy and in situ X‐ray diffraction. Moreover, the structure of the [K‐solvent]⁺ complexes intercalated with the graphite and the conditions for reversible K⁺‐solvent co‐intercalation into graphite are proposed based on the experimental results and first‐principles calculations. This work provides important insights into the design of natural graphite for high‐performance rechargeable potassium‐ion batteries.     

SPring‐8 BL36XU: Synchrotron Radiation X‐Ray‐Based Multi‐Analytical Beamline for Polymer Electrolyte Fuel Cells under Operating Conditions

We designed and constructed a beamline BL36XU at the 8 GeV synchrotron radiation facility SPring‐8 to provide information required for the development of next‐generation polymer electrolyte fuel cells (PEFCs) by clarifying the dynamic aspects of structures and electronic states of cathode catalysts under PEFC operating conditions and in the deterioration processes by accelerated durability test protcols. To investigate the mechanism and degradation process for the cathode electrocatalysis in practical PEFCs, we developed advanced time‐ and spatially‐resolved in‐situ/operando X‐ray absorption fine structure measurement systems and complementary analytical systems (X‐ray emission spectroscopy (XES), X‐ray diffraction (XRD), X‐ray computer tomography (CT) and hard X‐ray photoelectron spectroscopy (HAXPES)) and combined them to develop multi‐analytical systems at BL36XU. Multi‐analytical systems are very powerful for observing spatial‐temporal features of the transient processes occurring in complex systems such as PEFCs. This account describes the design, performance, and research results of the BL36XU and multi‐analytical in‐situ/operando systems.     

A Sodium Manganese Oxide Cathode by Facile Reduction for Sodium Batteries

A nonstoichiometric sodium manganese oxide (Na_xMnO_2+δ) cathode useful for sodium batteries was synthesized by an ambient‐temperature strategy that involved facile reduction of aqueous sodium permanganate in sodium iodide and subsequent heat treatment at 600 °C. Combined powder X‐ray diffraction and synchrotron X‐ray diffraction analyses confirmed the annealed sample to belong to a Na_xMnO₂ phase with a P2‐hexagonal structure. The ICP‐AES results confirmed the stoichiometry of the sample to be Na_0.53MnO_2+δ. Electron microscopy studies revealed the particle size of the electrode to be in the range of a few hundred nanometers. The Na_0.53MnO_2+δ cathode delivered an average discharge capacity of 170 mA h g^?1 with a stable plateau at 2.1 V for the initial 25 cycles versus sodium. Ex situ XANES studies confirmed the reversible intercalation of sodium into Na_0.53MnO_2+δ and suggested the accommodation of over‐stoichiometric Mn⁴⁺ ions to contribute towards the performance of the electrode.     

A Low‐Cost and Environmentally Friendly Mixed Polyanionic Cathode for Sodium‐Ion Storage

Sodium‐ion batteries (NIBs) are the most promising alternatives to lithium‐ion batteries in the development of renewable energy sources. The advancement of NIBs depends on the exploration of new electrode materials and fundamental understanding of working mechanisms. Herein, via experimental and simulation methods, we develop a mixed polyanionic compound, Na₂Fe(C₂O₄)SO₄?H₂O, as a cathode for NIBs. Thanks to its rigid three dimensional framework and the combined inductive effects from oxalate and sulfate, it delivered reversible Na insertion/desertion at average discharging voltages of 3.5 and 3.1 V for 500 cycles with Coulombic efficiencies of ca. 99 %. In situ synchrotron X‐ray measurements and DFT calculations demonstrate the Fe²⁺/Fe³⁺ redox reactions contribute to electron compensation during Na⁺ desertion/insertion. The study suggests mixed polyanionic frameworks may provide promising materials for Na ion storage with the merits of low cost and environmental friendliness.     

Three‐Dimensional Fe2N@C Microspheres Grown on Reduced Graphite Oxide for Lithium‐Ion Batteries and the Li Storage Mechanism

Nanostructured iron compounds as lithium‐ion‐battery anode material have attracted considerable attention with respect to improved electrochemical energy storage and excellent specific capacity, so lots of iron‐based composites have been developed. Herein, a novel composite composed of three‐dimensional Fe₂N@C microspheres grown on reduced graphite oxide (denoted as Fe₂N@C‐RGO) has been synthesized through a simple and effective technique assisted by a hydrothermal and subsequent heating treatment process. As the anode material for lithium‐ion batteries, the synthetic Fe₂N@C‐RGO displayed excellent Li⁺‐ion storage performance with a considerable initial capacity of 847 mAh g^?1, a superior cycle stability (a specific discharge capacity of 760 mAh g^?1 remained after the 100th cycle), and an improved rate‐capability performance compared with those of the pure Fe₂N and Fe₂N‐RGO nanostructures. The good performance should be attributed to the existence of RGO layers that can facilitate to enhance the conductivity and shorten the lithium‐ion diffusion path; in addition, the carbon layer on the surface of Fe₂N can avert the structure decay caused by the volume change during the lithiation/delithiation process. Moreover, in situ X‐ray absorption fine‐structure analysis demonstrated that the excellent performance can be attributed to the lack of any obvious change in the coordination geometry of Fe₂N@C‐RGO during the charge/discharge processes.     

In‐situ XAFS Studies of Mn12 Molecular‐Cluster Batteries: Super‐Reduced Mn12 Clusters in Solid‐State Electrochemistry

In situ X‐ray absorption fine structure (XAFS) analyses were performed on rechargeable molecular cluster batteries (MCBs), which were formed by a lithium anode and cathode‐active material, [Mn₁₂O₁₂(CH₃CH₂C(CH₃)₂COO)₁₆(H₂O)₄] with tert‐pentyl carboxylate ligand (abbreviated as Mn12tPe), and with eight Mn³⁺ and four Mn⁴⁺ centers. This mixed valence cluster compound is used in an effort to develop a reusable in situ battery cell that is suitable for such long‐term performance tests. The Mn12tPe MCBs exhibit a large capacity of approximately 210 Ah kg⁻¹ in the voltage range V=4.0–2.0 V. The X‐ray absorption near‐edge structure (XANES) spectra exhibit a systematic change during the charging/discharging with an isosbestic point at 6555 eV, which strongly suggests that only either the Mn³⁺ or Mn⁴⁺ ions in the Mn12 skeleton are involved in this battery reaction. The averaged manganese valence, determined from the absorption‐edge energy, decreased monotonically from 3.3 to 2.5 in the first half of the discharging (4.0>V>2.8 V), but changed little in the second half (2.8>V>2.0 V). The former valence change indicates a reduction of the initial [Mn12]⁰ state by approximately ten electrons, which corresponds well with the half value of the observed capacity. Therefore, the large capacity of the Mn12 MCBs can be understood as being due to a combination of the redox change of the manganese ions and presumably a capacitance effect. The extended X‐ray absorption fine structure (EXAFS) indicates a gradual increase of the Mn²⁺ sites in the first half of the discharging, which is consistent with the XANES spectra. It can be concluded that the Mn12tPe MCBs would include a solid‐state electrochemical reaction, mainly between the neutral state [Mn12]⁰ and the super‐reduced state [Mn12]⁸⁻ that is obtained by a local reduction of the eight Mn³⁺ ions in Mn12 toward Mn²⁺ ions.