Atomic Insights into Aluminium-Ion Insertion in Defective Anatase for Batteries

Aluminium batteries constitute a safe and sustainable high-energy-density electrochemical energy-storage solution. Viable Al-ion batteries require suitable electrode materials that can readily intercalate high-charge Al³⁺ ions. Here, we investigate the Al³⁺ intercalation chemistry of anatase TiO₂ and how chemical modifications influence the accommodation of Al³⁺ ions. We use fluoride- and hydroxide-doping to generate high concentrations of titanium vacancies. The coexistence of these hetero-anions and titanium vacancies leads to a complex insertion mechanism, attributed to three distinct types of host sites: native interstitial sites, single vacancy sites, and paired vacancy sites. We demonstrate that Al³⁺ induces a strong local distortion within the modified TiO₂ structure, which affects the insertion properties of the neighbouring host sites. Overall, specific structural features induced by the intercalation of highly polarising Al³⁺ ions should be considered when designing new electrode materials for polyvalent batteries.     

Halide-Free Synthesis of New Difluoro(oxalato)borate [DFOB]−-Based Ionic Liquids and Organic Ionic Plastic Crystals

The implementation of next-generation batteries requires the development of safe, compatible electrolytes that are stable and do not cause safety problems. The difluoro(oxalato)borate ([DFOB]⁻) anion has been used as an electrolyte additive to aid with stability, but such an approach has most commonly been carried out using flammable solvent electrolytes. As an alternative approach, utilisation of the [DFOB]⁻ anion to make ionic liquids (ILs) or Organic Ionic Plastic Crystals (OIPCs) allows the advantageous properties of ILs or OIPCs, such as higher thermal stability and non-volatility, combined with the benefits of the [DFOB]⁻ anion. Here, we report the synthesis of new [DFOB]⁻-based ILs paired with triethylmethylphosphonium [P₁₂₂₂]⁺, and diethylisobutylmethylphosphonium [P_122i4]⁺. We also report the first OIPCs containing the [DFOB]⁻ anion, formed by combination with the 1-ethyl-1-methylpyrrolidinium [C₂mpyr]⁺ cation, and the triethylmethylammonium [N₁₂₂₂]⁺ cation. The traditional synthetic route using halide starting materials has been successfully replaced by a halide-free tosylate-based synthetic route that is advantageous for a purer, halide free product. The synthesised [DFOB]⁻-based salts exhibit good thermal stability, while the ILs display relatively high ionic conductivity. Thus, the new [DFOB]⁻-based electrolytes show promise for further investigation as battery electrolytes both in liquid and solid-state form.     

An Aqueous Dual‐Ion Battery Cathode of Mn3O4 via Reversible Insertion of Nitrate

We report reversible electrochemical insertion of NO₃^? into manganese(II, III) oxide (Mn₃O₄) as a cathode for aqueous dual‐ion batteries. Characterization by TGA, FTIR, EDX, XANES, EXAFS, and EQCM collectively provides unequivocal evidence that reversible oxidative NO₃^? insertion takes place inside Mn₃O₄. Ex situ HRTEM and corresponding EDX mapping results suggest that NO₃^? insertion de‐crystallizes the structure of Mn₃O₄. Kinetic studies reveal fast migration of NO₃^? in the Mn₃O₄ structure. This finding may open a new direction for novel low‐cost aqueous dual‐ion batteries.     

Single Crystalline Na0.7MnO2 Nanoplates as Cathode Materials for Sodium‐Ion Batteries with Enhanced Performance

Single crystalline rhombus‐shaped Na_0.7MnO₂ nanoplates have been synthesized by a hydrothermal method. TEM and HRTEM analyses revealed that the Na_0.7MnO₂ single crystals predominantly exposed their (100) crystal plane, which is active for Na⁺‐ion insertion and extraction. When applied as cathode materials for sodium‐ion batteries, Na_0.7MnO₂ nanoplates exhibited a high reversible capacity of 163 mA h g^?1, a satisfactory cyclability, and a high rate performance. The enhanced electrochemical performance could be ascribed to the predominantly exposed active (100) facet, which could facilitate fast Na⁺‐ion insertion/extraction during the discharge and charge process.     

Stabilizing RbPbBr3 Perovskite Nanocrystals through Cs+ Substitution

ABX₃-type halide perovskite nanocrystals (NCs) have been a hot topic recently due to their fascinating optoelectronic properties. It has been demonstrated that A-site ions have an impact on their photophysical and chemical properties, such as the optical band gap and chemical stability. The pursuit of halide perovskite materials with diverse A-site species would deepen the understanding of the structure–property relationship of the perovskite family. In this work we have attempted to synthesize rubidium-based perovskite NCs. We have discovered that the partial substitution of Rb⁺ by Cs⁺ help to stabilize the orthorhombic RbPbBr₃ NCs at low temperature, which otherwise can only be obtained at high temperature. The inclusion of Cs⁺ into the RbPbBr₃ lattice results in highly photoluminescent Rb_1−xCs_xPbBr₃ NCs. With increasing amounts of Cs⁺, the band gaps of the Rb_1−xCs_xPbBr₃ NCs decrease, leading to a redshift of the photoluminescence peak. Also, the Rb_1−xCs_xPbBr₃ NCs (x=0.4) show good stability under ambient conditions. This work demonstrates the high structural flexibility and tunability of halide perovskite materials through an A-site cation substitution strategy and sheds light on the optimization of perovskite materials for application in high-performance optoelectronic devices.     

Abnormal Ionic Conductivities in Halide NaBi3O4Cl2 Induced by Absorbing Water and a Derived Oxhydryl Group

In hunting for safe and cost‐effective materials for post‐Li‐ion energy storage, the design and synthesis of high‐performance solid electrolytes (SEs) for all‐solid‐state batteries are bottlenecks. Many issues associated with chemical stability during processing and storage and use of the SEs in ambient conditions need to be addressed. Now, the effect of water as well as oxyhdryl group (^.OH) on NaBi₃O₄Cl₂ are investigated by evaluating ionic conductivity. The presence of water and ^.OH results in an increase in ionic conductivity of NaBi₃O₄Cl₂ owing to diffusion of H₂O into NaBi₃O₄Cl₂, partially forming binding ^.OH through oxygen vacancy repairing. Ab initio calculations reveal that the electrons significantly accumulate around ^.OH and induce a more negative charge center, which can promote Na⁺ hopping. This finding is fundamental for understanding the essential role of H₂O in halide‐based SEs and provides possible roles in designing water‐insensitive SEs through control of defects.     

New Oxyhalide Solid Electrolytes with High Lithium Ionic Conductivity >10 mS cm−1 for All-Solid-State Batteries

All-solid-state batteries (ASSBs) with inorganic solid electrolytes (SEs) have attracted significant interest as next-generation energy storage. Halides such as Li₃YCl₆ are promising candidates for SE because they combine high oxidation stability and deformability. However, the ionic conductivities of halide SEs are not as high as those of other SEs, especially sulfides. Here, we discover new lithium-metal-oxy-halide materials, LiMOCl₄ (M=Nb, Ta). They exhibit extremely high ionic conductivities of 10.4 mS cm⁻¹ for M=Nb and 12.4 mS cm⁻¹ for M=Ta, respectively, even in cold-pressed powder forms at room temperature, which are comparable to or surpass those of organic liquid electrolytes used in lithium-ion batteries. Bulk-type ASSB cells using the oxyhalides as the cathode SE demonstrate an outstanding rate capability with a capacity retention of 80 % at 5 C/0.1 C. We believe that the proposed oxyhalides are promising SE candidates for the practical applications of ASSBs.     

Improving Na+ transport kinetics and Na+ storage of hierarchical rhenium-nickel sulfide (ReS2@NiS2) hollow architecture by assembling layered 2D-3D heterostructures

Mixed metal sulfides have been widely used as anode material of sodium-ion batteries (SIBs) because of their excellent conductivity and sodium ion storage performance. Herein, ReS₂@NiS₂ heterostructures have been triumphantly designed and prepared through anchoring ReS₂ nanosheet arrays on the surface of NiS₂ hollow nanosphere. Specifically, the carbon nanospheres was used as hard template to synthesize NiS₂ hollow spheres as the substrate and then the ultrathin two-dimensional ReS₂ nanosheet arrays were uniformly grown on the surface of NiS₂. The internal hollow property provides sufficient space to relieve the volume expansion, and the outer two-dimensional nanosheet realizes the rapid electron transport and insertion/extraction of Na⁺. Owing to the great improvement of the transport kinetics of Na⁺, NiS₂@ReS₂ heterostructure electrode can achieve a high specific capacity of 400 mAh/g at the high current density of 1 A/g and still maintain a stable cycle stability even after 220 cycles. This hard template method not only paves a new way for the design and construct binary metal sulfide heterostructure electrode materials with outstanding electrochemical performance for Na⁺ batteries but also open up the potential applications of anode materials of SIBs.     

Safe,Low‐Cost,Fast‐Kinetics and Low‐Strain Inorganic‐Open‐Framework Anode for Potassium‐Ion Batteries

A key challenge for potassium‐ion batteries is to explore low‐cost electrode materials that allow fast and reversible insertion of large‐ionic‐size K⁺. Here, we report an inorganic‐open‐framework anode (KTiOPO₄), which achieves a reversible capacity of up to 102 mAh g^?1 (307 mAh cm^?3), flat voltage plateaus at a safe average potential of 0.82 V (vs. K/K⁺), a long lifespan of over 200 cycles, and K⁺‐transport kinetics ≈10 times faster than those of Na‐superionic conductors. Combined experimental analysis and first‐principles calculations reveal a charge storage mechanism involving biphasic and solid solution reactions and a cell volume change (9.5 %) even smaller than that for Li⁺‐insertion into graphite (≈10 %). KTiOPO₄ exhibits quasi‐3D lattice expansion on K⁺ intercalation, enabling the disintegration of small lattice strain and thus high structural stability. The inorganic open‐frameworks may open a new avenue for exploring low‐cost, stable and fast‐kinetic battery chemistry.     

Safe,Low‐Cost,Fast‐Kinetics and Low‐Strain Inorganic‐Open‐Framework Anode for Potassium‐Ion Batteries

A key challenge for potassium‐ion batteries is to explore low‐cost electrode materials that allow fast and reversible insertion of large‐ionic‐size K⁺. Here, we report an inorganic‐open‐framework anode (KTiOPO₄), which achieves a reversible capacity of up to 102 mAh g^?1 (307 mAh cm^?3), flat voltage plateaus at a safe average potential of 0.82 V (vs. K/K⁺), a long lifespan of over 200 cycles, and K⁺‐transport kinetics ≈10 times faster than those of Na‐superionic conductors. Combined experimental analysis and first‐principles calculations reveal a charge storage mechanism involving biphasic and solid solution reactions and a cell volume change (9.5 %) even smaller than that for Li⁺‐insertion into graphite (≈10 %). KTiOPO₄ exhibits quasi‐3D lattice expansion on K⁺ intercalation, enabling the disintegration of small lattice strain and thus high structural stability. The inorganic open‐frameworks may open a new avenue for exploring low‐cost, stable and fast‐kinetic battery chemistry.     

Electrochemical Phase Evolution of Metal‐Based Pre‐Catalysts for High‐Rate Polysulfide Conversion

In situ evolution of electrocatalysts is of paramount importance in defining catalytic reactions. Catalysts for aprotic electrochemistry such as lithium–sulfur (Li‐S) batteries are the cornerstone to enhance intrinsically sluggish reaction kinetics but the true active phases are often controversial. Herein, we reveal the electrochemical phase evolution of metal‐based pre‐catalysts (Co₄N) in working Li‐S batteries that renders highly active electrocatalysts (CoS_x). Electrochemical cycling induces the transformation from single‐crystalline Co₄N to polycrystalline CoS_x that are rich in active sites. This transformation propels all‐phase polysulfide‐involving reactions. Consequently, Co₄N enables stable operation of high‐rate (10 C, 16.7 mA cm^?2) and electrolyte‐starved (4.7 μL mg_S^?1) Li‐S batteries. The general concept of electrochemically induced sulfurization is verified by thermodynamic energetics for most of low‐valence metal compounds.     

Vanadium oxide gels as electrode materials for lithium batteries

Electrochemical lithium insertion has been studied in a large number of vanadium oxides with three dimensional framework structure. Several of these oxides have shown high capacities for lithium insertion and good reversibility.Pure solutions of decavanadic acid have shown to undergo spontaneous polycondensation reaction forming sols or gels of highly polymerized vanadium oxides, M _w 10⁶. After dehydration a series of xerogels with varying amounts of water, V₂O₅ · nH₂O, can be obtained. The structure of these xerogels consists of ribbons of corner and edge sharing VO₆ octahedra stabilized by interlayer water molecules. Under ambient conditions the water content corresponds to n=1.8, but this value can be reversibly changed under mild drying conditions.This report deals with the electrochemical insertion of lithium in dried vanadium oxide xerogels, with special regard to the use of these materials as electrodes in rechargeable lithium batteries.     

Proton Insertion Chemistry of a Zinc–Organic Battery

Proton storage in rechargeable aqueous zinc‐ion batteries (ZIBs) is attracting extensive attention owing to the fast kinetics of H⁺ insertion/extraction. However, it has not been achieved in organic materials‐based ZIBs with a mild electrolyte. Now, aqueous ZIBs based on diquinoxalino [2,3‐a:2′,3′‐c] phenazine (HATN) in a mild electrolyte are developed. Electrochemical and structural analysis confirm for the first time that such Zn–HATN batteries experience a H⁺ uptake/removal behavior with highly reversible structural evolution of HATN. The H⁺ uptake/removal endows the Zn–HATN batteries with enhanced electrochemical performance. Proton insertion chemistry will broaden the horizons of aqueous Zn–organic batteries and open up new opportunities to construct high‐performance ZIBs.     

Dual-Templating Approaches to Soybeans Milk-Derived Hierarchically Porous Heteroatom-Doped Carbon Materials for Lithium-Ion Batteries

Biomass derived carbon materials are widely available, cheap and abundant resources. The application of these materials as electrodes for rechargeable batteries shows great promise. To further explore their applications in energy storage fields, the structural design of these materials has been investigated. Hierarchical porous heteroatom-doped carbon materials (HPHCs) with open three-dimensional (3D) nanostructure have been considered as highly efficient energy storage materials. In this work, biomass soybean milk is chosen as the precursor to construct N, O co-doped interconnected 3D porous carbon framework via two approaches by using soluble salts (NaCl/Na₂CO₃ and ZnCl₂/Mg₅(OH)₂(CO₃)₄, respectively) as hard templates. The electrochemical results reveal that these structures were able to provide a stable cycling performance (710 mAh ⋅ g⁻¹ at 0.1 A ⋅ g⁻¹ after 300 cycles for HPHC-a, and 610 mAh ⋅ g⁻¹ at 0.1 A ⋅ g⁻¹ after 200 cycles for HPHC-b) in Li-ion battery and Na-ion storage (210 mAh ⋅ g⁻¹ at 0.1 A ⋅ g⁻¹ after 900 cycles for HPHC-a) as anodes materials, respectively. Further comparative studies showed that these improvements in HPHC-a performance were mainly due to the honeycomb-like structure containing graphene-like nanosheets and high nitrogen content in the porous structures. This work provides new approaches for the preparation of hierarchically structured heteroatom-doped carbon materials by pyrolysis of other biomass precursors and promotes the applications of carbon materials in energy storage fields.     

Surface Lattice Modulation Enables Stable Cycling of High-Loading All-solid-state Batteries at High Voltages

Halide solid electrolytes, known for their high ionic conductivity at room temperature and good oxidative stability, face notable challenges in all–solid–state Li–ion batteries (ASSBs), especially with unstable cathode/solid electrolyte (SE) interface and increasing interfacial resistance during cycling. In this work, we have developed an Al³⁺–doped, cation–disordered epitaxial nanolayer on the LiCoO₂ surface by reacting it with an artificially constructed AlPO₄ nanoshell; this lithium–deficient layer featuring a rock–salt–like phase effectively suppresses oxidative decomposition of Li₃InCl₆ electrolyte and stabilizes the cathode/SE interface at 4.5 V. The ASSBs with the halide electrolyte Li₃InCl₆ and a high–loading LiCoO₂ cathode demonstrated high discharge capacity and long cycling life from 3 to 4.5 V. Our findings emphasize the importance of specialized cathode surface modification in preventing SE degradation and achieving stable cycling of halide–based ASSBs at high voltages.     

Rational Synthesis of “Grape-like” Ni2V2O7 Microspheres as High-capacity Anodes for Rechargeable Lithium Batteries

Vanadates have received booming attention recently as promising materials for extensive electrochemical devices such as batteries and electrocatalysis. However, the enormous difficulties of achieving pure-phase transition metal vanadates, especially for nickel-based, hinder their exploitations. Herein, for the first time, by controlling the amount of ethylene glycol (EG) and reaction time, grape-like Ni₂V₂O₇ (or V₂O₅/Ni₂V₂O₇) microspheres were rationally fabricated. It is demonstrated that the EG can chelate both Ni²⁺ and VO₃⁻ to form organometallic precursors. As anode in lithium-ion batteries (LIBs), it could deliver superior reversible capacity of 1050 mAh/g at 0.1 A/g and excellent rate capability of 600 mAh/g at 4 A/g. The facile hydrothermal synthesis broadens the material variety of nickel vanadates and offers new opportunities for their wider applications in electrochemistry.     

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.     

Proton/Mg2+ Co-Insertion Chemistry in Aqueous Mg-Ion Batteries: From the Interface to the Inner

Co-insertion of protons happens widely and enables divalent-ion aqueous batteries to achieve high performances. However, detailed investigations and comprehensive understandings of proton co-insertion are scarce. Herein, we demonstrate that proton co-insertion into tunnel materials is determined jointly by interface derivation and inner diffusion: at the interface, hdrated Mg²⁺ has poor insertion kinetics, and therefore accumulates and hydrolyzes to produce protons; in the tunnels, co-inserted/lattice H₂O molecules block the Mg²⁺ diffusion while facilitate the proton diffusion. When monoclinic vanadium dioxide (VO₂(B)) anode is tested in Mg(CH₃COO)₂ aqueous solution, the formation of Mg-rich solid electrolyte interphase on the VO₂(B) electrode and co-insertion of derived protons are probed; in the tunnels, the diffusion energy barrier of Mg²⁺+H₂O is 2.7 eV, while that of the protons is 0.37 eV. Thus, protons dominate the subsequent insertion and inner diffusion. As a consequence, the VO₂(B) achieves a high capacity of 257.0 mAh g⁻¹ at 1 A g⁻¹, a high rate retention of 59.1 % from 1 to 8 A g⁻¹, and stable cyclability of 3000 times with a capacity retention of 81.5 %. This work provides an in-depth understanding of the proton co-insertion and may promote the development of rechargeable aqueous batteries.     

Magnesium Deintercalation From the Spinel-Type MgMn2-yFeyO4 (0.4≤y≤2.0) by Acid-Treatment and Electrochemistry

Rechargeable magnesium batteries attract lots of attention because of their high safety and low cost compared to lithium batteries, and it is needed to develop more efficient electrode materials. Although MgMn₂O₄ is a promising material for the positive electrode in Mg rechargeable batteries, it usually exhibits poor cyclability. To improve the electrochemical behavior, we have prepared nanoparticles of MgMn_2-yFe_yO₄. The XRD results have confirmed that when Mn³⁺ (Jahn-Teller ion) ions are replaced by Fe³⁺ (non-Jahn-Teller ion), the resulting MgMn_2-yFe_yO₄ is a cubic phase. The structure and theoretical voltage are theoretically calculated by using the DFT method. The obtained samples have been chemically treated in acid solution for partial demagnesiation, and it is observed that the presence of iron inhibits the deinsertion of Mg through disproportionation and favors the exchange reaction. The electrochemical behavior in non-aqueous magnesium cells has been explored.     

Chemical Origin of the Stability Difference between Copper(I)‐ and Silver(I)‐Based Halide Double Perovskites

Recently, Cu^I‐ and Ag^I‐based halide double perovskites have been proposed as promising candidates for overcoming the toxicity and instability issues inherent within the emerging Pb‐based halide perovskite absorbers. However, up to date, only Ag^I‐based halide double perovskites have been experimentally synthesized; there are no reports on successful synthesis of Cu^I‐based analogues. Here we show that, owing to the much higher energy level for the Cu 3d¹⁰ orbitals than for the Ag 4d¹⁰ orbitals, Cu^I atoms energetically favor 4‐fold coordination, forming [CuX₄] tetrahedra (X=halogen), but not 6‐fold coordination as required for [CuX₆] octahedra. In contrast, Ag^I atoms can have both 6‐ and 4‐fold coordinations. Our density functional theory calculations reveal that the synthesis of Cu^I halide double perovskites may instead lead to non‐perovskites containing [CuX₄] tetrahedra, as confirmed by our material synthesis efforts.