A hybrid solid/liquid electrolyte with superior security facilitates the implementation of high‐energy‐density storage devices, but it suffers from inferior chemical compatibility with cathodes. ...Herein, an optimal lithium difluoro(oxalato)borate salt was introduced to build in situ an amorphous cathode electrolyte interphase (CEI) between Ni‐rich cathodes and hybrid electrolyte. The CEI preserves the surface structure with high compatibility, leading to enhanced interfacial stability. Meanwhile, the space‐charge layer can be prominently mitigated at the solid/solid interface via harmonized chemical potentials, acquiring promoted interfacial dynamics as revealed by COMSOL simulation. Consequently, the amorphous CEI integrates the bifunctionality to provide an excellent cycling stability, high Coulombic efficiency, and favorable rate capability in high‐voltage Li‐metal batteries, innovating the design philosophy of functional CEI strategy for future high‐energy‐density batteries.
The CEI's advantage: An amorphous cathode electrolyte interphase (CEI) with superior chemical compatibility and plasticity was formed via in situ LiDFOB conversion. It endows high‐voltage hybrid solid/liquid batteries with significantly enhanced interfacial stability, durability, and dynamics.
Rechargeable magnesium batteries have attracted recent research attention because of abundant raw materials and their relatively low‐price and high‐safety characteristics. However, the sluggish ...kinetics of the intercalated Mg2+ ions in the electrode materials originates from the high polarizing ability of the Mg2+ ion and hinders its electrochemical properties. Here we report a facile approach to improve the electrochemical energy storage capability of the Li4Ti5O12 electrode in a Mg battery system by the synergy between Mg2+ and Li+ ions. By tuning the hybrid electrolyte of Mg2+ and Li+ ions, both the reversible capacity and the kinetic properties of large Li4Ti5O12 nanoparticles attain remarkable improvement.
Synergy between Mg2+ and Li+ ions: By controlling the collaborative electrochemistry of magnesium and lithium cations, Li4Ti5O12 electrodes (LTO; see picture) close to sub‐micron size gain extraordinary electrochemical energy storage capability. The electrodes show improved kinetics in rechargeable magnesium batteries.
Rechargeable lithium–metal batteries with a cell‐level specific energy of >400 Wh kg−1 are highly desired for next‐generation storage applications, yet the research has been retarded by poor ...electrolyte–electrode compatibility and rigorous safety concerns. We demonstrate that by simply formulating the composition of conventional electrolytes, a hybrid electrolyte was constructed to ensure high (electro)chemical and thermal stability with both the Li‐metal anode and the nickel‐rich layered oxide cathodes. By employing the new electrolyte, Li∥LiNi0.6Co0.2Mn0.2O2 cells show favorable cycling and rate performance, and a 10 Ah Li∥LiNi0.8Co0.1Mn0.1O2 pouch cell demonstrates a practical specific energy of >450 Wh kg−1. Our findings shed light on reasonable design principles for electrolyte and electrode/electrolyte interfaces toward practical realization of high‐energy rechargeable batteries.
Formulation of conventional electrolyte composition yields a hybrid solid/liquid electrolyte that is electrochemically compatible with the Li‐metal anode and the nickel‐rich layered oxide cathodes, which promises stable operation of a practical 10‐Ah‐grade pouch cell with a specific energy of >450 Wh kg−1.
As one of the most promising cathode candidates for room‐temperature sodium‐ion batteries (SIBs), P2‐type layered oxides face the challenge of simultaneously realizing high‐rate performance while ...achieving long cycle life. Here, a stable Na2/3Ni1/6Mn2/3Cu1/9Mg1/18O2 cathode material is proposed that consists of multiple‐layer oriented stacking nanoflakes, in which the nickel sites are partially substituted by copper and magnesium, a characteristic of the material that is confirmed by multiscale scanning transmission electron microscopy and electron energy loss spectroscopy techniques. Owing to the optimal morphology structure modulation and chemical element substitution strategy, the electrode displays remarkable rate performance (73% capacity retention at 30C compared to 0.5C) and outstanding cycling stability in Na half‐cell system couple with unprecedented full battery performance. The underlying thermal stability, phase stability, and Na+ storage mechanisms are clearly elucidated through the systematical characterizations of electrochemical behaviors, in situ X‐ray diffraction at different temperatures, and operando X‐ray diffraction upon Na+ deintercalation/intercalation. Surprisingly, a quasi‐solid‐solution reaction is switched to an absolute solid‐solution reaction and a capacitive Na+ storage mechanism is demonstrated via quantitative electrochemical kinetics calculation during charge/discharge process. Such a simple and effective strategy might reveal a new avenue into the rational design of excellent rate capability and long cycle stability cathode materials for practical SIBs.
A stable copper and magnesium cosubstituted Na2/3Ni1/6Mn2/3Cu1/9Mg1/18O2 cathode material consisting of multiple‐layer oriented stacking nanoflakes is reported. An optimal structure design and a chemical element substitution strategy are demonstrated to greatly improve Na+ transport kinetics and structural stability of P2‐type cathode material, resulting in high‐rate and long cycle life for a sodium‐ion battery.
Solid polymer electrolytes (SPEs) are promising candidates for developing high‐energy‐density Li metal batteries due to their flexible processability. However, the low mechanical strength as well as ...the inferior interfacial regulation of ions between SPEs and Li metal anode limit the suppress ion of Li dendrites and destabilize the Li anode. To meet these challenges, interfacial engineering aiming to homogenize the distribution of Li+/electron accompanied with enhanced mechanical strength by Mg3N2 layer decorating polyethylene oxide is demonstrated. The intermediary Mg3N2 in situ transforms to a mixed ion/electron conducting interlayer consisting of a fast ionic conductor Li3N and a benign electronic conductor Mg metal, which can buffer the Li+ concentration gradient and level the nonuniform electric current distribution during cycling, as demonstrated by a COMSOL Multiphysics simulation. These characteristics endow the solid full cell with a dendrite‐free Li anode and enhanced cycling stability and kinetics. The innovative interface design will accelerate the commercial application of high‐energy‐density solid batteries.
An in situ formed mixed ion/electron conducting interlayer formed from an intermediary Mg3N2 layer decorated on polyethylene oxide is designed. The as‐synthesized electrolyte manipulates ion and electron distributions on the surface of the Li anode, endowing the solid full cell with a dendrite‐free Li anode and enhanced cycling stability and kinetics.
Layered oxide cathodes usually exhibit high compositional diversity, thus providing controllable electrochemical performance for Na‐ion batteries. These abundant components lead to complicated ...structural chemistry, closely affecting the stacking preference, phase transition and Na+ kinetics. With this perspective, we explore the thermodynamically stable phase diagram of various P2/O3 composites based on a rational biphasic tailoring strategy. Then a specific P2/O3 composite is investigated and compared with its monophasic counterparts. A highly reversible structural evolution of P2/O3–P2/O3/P3–P2/P3–P2/Z/O3′–Z/O3′ based on the Ni2+/Ni3.5+, Fe3+/Fe4+ and Mn3.8+/Mn4+ redox couples upon sequential Na extraction/insertion is revealed. The reduced structural strain at the phase boundary alleviates the phase transition and decreases the lattice mismatch during cycling, endowing the biphasic electrode a large reversible capacity of 144 mAh g−1 with the energy density approaching 514 Wh kg−1.
A rational biphasic tailoring strategy to prepare layered composite cathodes with the desired phase ratio is proposed. Benefiting from the reversible phase transition within transition metal slabs and the decreased structure strain at the phase boundary of the intergrowth structure during Na extraction and insertion, the Com‐NaNMFT composite material demonstrates excellent electrochemical performance.
Layered O3‐type sodium oxides (NaMO2, M=transition metal) commonly exhibit an O3–P3 phase transition, which occurs at a low redox voltage of about 3 V (vs. Na+/Na) during sodium extraction and ...insertion, with the result that almost 50 % of their total capacity lies at this low voltage region, and they possess insufficient energy density as cathode materials for sodium‐ion batteries (NIBs). Therefore, development of high‐voltage O3‐type cathodes remains challenging because it is difficult to raise the phase‐transition voltage by reasonable structure modulation. A new example of O3‐type sodium insertion materials is presented for use in NIBs. The designed O3‐type Na0.7Ni0.35Sn0.65O2 material displays a highest redox potential of 3.7 V (vs. Na+/Na) among the reported O3‐type materials based on the Ni2+/Ni3+ couple, by virtue of its increased Ni−O bond ionicity through reduced orbital overlap between transition metals and oxygen within the MO2 slabs. This study provides an orbital‐level understanding of the operating potentials of the nominal redox couples for O3‐NaMO2 cathodes. The strategy described could be used to tailor electrodes for improved performance.
Batteries included: An O3‐type sodium insertion material, Na0.7Ni0.35Sn0.65O2, displays a high redox potential of 3.7 V versus Na+/Na (based on the Ni2+/Ni3+ couple). Reduced orbital hybridization between the oxygen 2p and nickel 3d orbitals within the metallic layers increases the Ni−O bond ionicity. Good structural reversibility is obtained because the O3‐type phase transforms reversibly into a P3‐type phase.
Chemical modification of electrode materials by heteroatom dopants is crucial for improving storage performance in rechargeable batteries. Electron configurations of different dopants significantly ...influence the chemical interactions inbetween and the chemical bonding with the host material, yet the underlying mechanism remains unclear. We revealed competitive doping chemistry of Group IIIA elements (boron and aluminum) taking nickel‐rich cathode materials as a model. A notable difference between the atomic radii of B and Al accounts for different spatial configurations of the hybridized orbital in bonding with lattice oxygen. Density functional theory calculations reveal, Al is preferentially bonded to oxygen and vice versa, and shows a much lower diffusion barrier than BIII. In the case of Al‐preoccupation, the bulk diffusion of BIII is hindered. In this way, a B‐rich surface and Al‐rich bulk is formed, which helps to synergistically stabilize the structural evolution and surface chemistry of the cathode.
A model study has been performed on Group IIIA element (boron and aluminum) co‐doped high‐nickel layered oxide cathode materials to understand competitive doping chemistry. A notable difference between the atomic radii of B and Al accounts for different spatial configurations of the hybridized orbital in bonding with lattice oxygen, resulting in the formation of a B‐rich surface and an Al‐rich bulk.
Herein, a composite polymer electrolyte with a viscoelastic and nonflammable interface is designed to handle the contact issue and preclude Li dendrite formation. The composite polymer electrolyte ...(cellulose acetate/polyethylene glycol/Li1.4Al0.4Ti1.6P3O12) exhibits a wide electrochemical window of 5 V (vs Li+/Li), a high Li+ transference number of 0.61, and an excellent ionic conductivity of above 10−4 S cm−1 at 60 °C. In particular, the intimate contact, low interfacial impedance, and fast ion‐transport process between the electrodes and solid electrolytes can be simultaneously achieved by the viscoelastic and nonflammable layer. Benefiting from this novel design, solid lithium metal batteries with either LiFePO4 or LiCoO2 as cathode exhibit superior cyclability and rate capability, such as a discharge capacity of 157 mA h g−1 after 100 cycles at C/2 and 97 mA h g−1 at 5C for LiFePO4 cathode. Moreover, the smooth and uniform Li surface after long‐term cycling confirms the successful suppression of dendrite formation. The viscoelastic and nonflammable interface modification of solid electrolytes provides a promising and general strategy to handle the interfacial issues and improves the operative safety of solid lithium metal batteries.
A strategy to stabilize and improve the electrode–electrolytes interface, via a viscoelastic interface design, is developed. The viscoelastic and nonflammable ionic liquids interface can construct an effective Li+ transport pathway in the cathode and maintain the interface stability at both anode and cathode. This finding provides a practical and promising strategy for optimizing the solid electrolytes‐electrode interface.
Solid‐state Li secondary batteries may become high energy density storage devices for the next generation of electric vehicles, depending on the compatibility of electrode materials and suitable ...solid electrolytes. Specifically, it is a great challenge to obtain a stable interface between these solid electrolytes and cathodes. Herein, this issue can be effectively addressed by constructing a poly(acrylonitrile‐co‐butadiene) coated layer onto the surface of LiNi0.6Mn0.2Co0.2O2 cathode materials. The polymer layer plays a vital role in working as a protective shell to retard side reaction and ameliorate the contact of the solid–solid interface during the cycling process. In the resultant solid‐state batteries, both rate capacity (99 mA h g−1 at 3 C) and cycling stability (75% capacity retention after 400 cycles) are improved after coating. This impressive performance highlights the great importance of layer modification in the cathode and inspires the development of solid‐state batteries toward practical applications.
To mitigate the interfacial problems between cathode and solid electrolyte, a soft poly(acrylonitrile‐co‐butadiene) nanolayer is coated onto the cathode materials. The soft layer can not only sustain an admirable physical contact during cycling but also retard uncontrolled side reactions of the interface by shielding the particles from direct contact with the solid electrolyte.
