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.

Integrated Surface Modulation of Ultrahigh Ni Cathode Materials for Improved Battery Performance.

Ni-rich layered cathodes with ultrahigh nickel content (≥90%), for example LiNi0.9 Co0.1 O2 (NC0.9), are promising for next-generation high-energy Li-ion batteries (LIBs), but face stability issues related to structural degradation and side reactions during the electrochemical process. Here, surface modulation is demonstrated by integrating a Li+ -conductive nanocoating and gradient lattice doping to stabilize the active cathode efficiently for extended cycles. Briefly, a wet-chemistry process is developed to deposit uniform ZrO(OH)2 nanoshells around Ni0.905 Co0.095 (OH)2 (NC0.9-OH) hydroxide precursors, followed by high temperature lithiation to create reinforced products featuring Zr doping in the crust lattice decorated with Li2 ZrO3 nanoparticles on the surface. It is identified that the Zr4+ infiltration reconstructed the surface lattice into favorable characters such as Li+ deficiency and Ni3+ reduction, which are effective to combat side reactions and suppress phase degradation and crack formation. This surface control is able to achieve an optimized balance between surface stabilization and charge transfer, resulting in an extraordinary capacity retention of 96.6% after 100 cycles at 1 C and an excellent rate capability of 148.8 mA h g-1 at 10 C. This study highlights the critical importance of integrated surface modulation for high stability of cathode materials in next-generation LIBs.

Surface Lattice Modulation through Chemical Delithiation toward a Stable Nickel-Rich Layered Oxide Cathode.

Nickel-rich layered oxides (NLOs) are considered as one of the most promising cathode materials for next-generation high-energy lithium-ion batteries (LIBs), yet their practical applications are currently challenged by the unsatisfactory cyclability and reliability owing to their inherent interfacial and structural instability. Herein, we demonstrate an approach to reverse the unstable nature of NLOs through surface solid reaction, by which the reconstructed surface lattice turns stable and robust against both side reactions and chemophysical breakdown, resulting in improved cycling performance. Specifically, conformal La(OH)3 nanoshells are built with their thicknesses controlled at nanometer accuracy, which act as a Li+ capturer and induce controlled reaction with the NLO surface lattices, thereby transforming the particle crust into an epitaxial layer with localized Ni/Li disordering, where lithium deficiency and nickel stabilization are both achieved by transforming oxidative Ni3+ into stable Ni2+. An optimized balance between surface stabilization and charge transfer is demonstrated by a representative NLO material, namely, LiNi0.83Co0.07Mn0.1O2, whose surface engineering leads to a highly improved capacity retention and excellent rate capability with a strong capability to inhibit the crack of NLO particles. Our study highlights the importance of surface chemistry in determining chemical and structural behaviors and paves a research avenue in controlling the surface lattice for the stabilization of NLOs toward reliable high-energy LIBs.

A template-free assembly of Cu,N-codoped hollow carbon nanospheres as low-cost and highly efficient peroxidase nanozymes.

Developing carbon-based materials with high catalytic performance and sensitivity has significance in low-cost and highly efficient nanozymes. Herein, for the first time, Cu,N-codoped hollow carbon nanospheres (CuNHCNs) with highly active Cu-Nx sites were successfully assembled through a template-free strategy, in which Cu2+-poly(m-phenylenediamine) (Cu-PmPD) nanospheres were utilized as the source of Cu, N and C. Benefiting from the synergistic effect of the hollow spherical structure and optimized composition, the CuNHCN exhibits high affinity for 3,3',5,5'-tetramethylbenzidine and H2O2 with 0.0655 mM and 0.918 mM, respectively, which are superior to those of HRP and most metal-based nanozymes. Moreover, by employing glucose and ascorbic acid (AA) as biomolecule models, a CuNHCN-based colorimetric detection platform is developed. The CuNHCN exhibits superior peroxidase mimicking activity and sensitivity in detecting glucose and AA with a detection limit of 0.187 µM and 68.9 nM (S/N = 3), respectively. Also, the colorimetric detection based on the CuNHCN towards glucose and AA in human serum presents superior practicability and accuracy. The assay provides a new avenue for designing and fabricating low-cost peroxidase nanozymes with high performance in bioassays.

Synergistic effect of Mn doping and hollow structure boosting Mn-CoP/Co2P nanotubes as efficient bifunctional electrocatalyst for overall water splitting.

The sluggish kinetic of hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) severely hampers the commercial application of electrochemical water splitting, promoting the urgent exploration of high-efficient bifunctional electrocatalysts. Heteroatom doping and structure engineering have been identified as the most effective strategies to boost the catalytic activity of electrocatalysts. Herein, Mn doping and hollow structure were integrated in the design of Co-based transition metal phosphide catalyst to prepare Mn-CoP/Co2P nanotubes (denoted as Mn-CP NTs) by a facile template-free method. Confirmed by characterization analysis, the introduced Mn species were in high dispersion in the regular CoP/Co2P hollow tubular framework. Such a favorable design in composition and structure effectively boosted the catalytic activity of Mn-CP NTs toward electrochemical water splitting. The Mn-CP NTs showed superior HER and OER activity demonstrated by the low overpotentials of 82 mV (vs HER) and 309 mV (vs OER) at the current density of 10 mA cm-2, as well as the satisfactory durability. When used as both cathode and anode in electrolyzer for overall water splitting, only a low cell voltage of 1.67 V was required for the Mn-CP NTs to drive 10 mA cm-2, accompanied with excellent stability confirmed by over 50 h test.

Facile Construction of Nanofilms from a Dip-Coating Process to Enable High-Performance Solid-State Batteries.

The use of solid-state electrolytes (SSEs) instead of those liquid ones has found promising potential to achieve both high energy density and high safety for their applications in the next-generation energy storage devices. Unfortunately, SSEs also bring forth challenges related to solid-to-solid contact, making the stability of the electrode/electrolyte interface a formidable concern. Herein, using a garnet-type Li6.5La3Zr1.5Ta0.5O12 (LLZT) electrolyte as an example, we demonstrated a facile treatment based on the dip-coating technique, which is highly efficient in modifying the LLZT/Li interface by forming a MgO interlayer. Using polyvinyl pyrrolidone (PVP) as a coordination polymer, uniform and crack-free nanofilms are fabricated on the LLZT pellet with good control of the morphological parameters. We found that the MgO interlayer was highly effective to reduce the interfacial resistance to 6 Ω cm2 as compared to 1652 Ω cm2 of the unmodified interface. The assembled Li symmetrical cell was able to achieve a high critical current density of 1.2 mA cm-2 at room temperature, and it has a long cycling capability for over 4000 h. Using the commercialized materials of LiFePO4 and LiNi0.83Co0.07Mn0.1O2 as the cathode materials, the full cells based on the LLZT@MgO electrolyte showed excellent cyclability and high rate performance at 25 °C. Our study shows the feasibility of precise and controllable surface modification based on a simple liquid phase method and highlights the essential importance of interface control for the future application of high-performance solid-state batteries.

Advancing to 4.6 V Review and Prospect in Developing High-Energy-Density LiCoO2 Cathode for Lithium-Ion Batteries.

Layered LiCoO2 (LCO) is one of the most important cathodes for portable electronic products at present and in the foreseeable future. It becomes a continuous push to increase the cutoff voltage of LCO so that a higher capacity can be achieved, for example, a capacity of 220 mAh g-1 at 4.6 V compared to 175 mAh g-1 at 4.45 V, which is unfortunately accompanied by severe capacity degradation due to the much-aggravated side reactions and irreversible phase transitions. Accordingly, strict control on the LCO becomes essential to combat the inherent instability related to the high voltage challenge for their future applications. This review begins with a discussion on the relationship between the crystal structures and electrochemical properties of LCO as well as the failure mechanisms at 4.6 V. Then, recent advances in control strategies for 4.6 V LCO are summarized with focus on both bulk structure and surface properties. One closes this review by presenting the outlook for future efforts on LCO-based lithium ion batteries (LIBs). It is hoped that this work can draw a clear map on the research status of 4.6 V LCO, and also shed light on the future directions of materials design for high energy LIBs.

Anion Doping for Layered Oxides with a Solid-Solution Reaction for Potassium-Ion Battery Cathodes.

The development of potassium-ion batteries (PIBs) is challenged by the shortage of stable cathode materials capable of reversibly hosting the large-sized K+ (1.38 Å), which is prone to cause severe structural degradation and complex phase evolution during the potassiation/depotassiation process. Here, we identified that anionic doping of the layered oxides for PIBs is effective to combat their capacity fading at high voltage (>4.0 V). Taking P2-type K2/3Mn7/9Ni1/9Ti1/9O17/9F1/9 (KMNTOF) as an example, we showed that the partial substitution of O2- by F- enlarged the interlayer distance of the K2/3Mn7/9Ni1/9Ti1/9O2 (KMNTO), which becomes more favorable for fast K+ transition without violent structural destruction. Meanwhile, based on the experimental data and theoretical results, we identified that the introduction of F- anions effectively increased the redox-active Mn cationic concentration by lowering the average valence of the Mn element, accordingly providing more reversible capacity derived from the Mn3+/4+ redox couple, rather than oxygen redox. This anionic doping strategy enables the KMNTOF cathode to deliver a high reversible capacity of 132.5 mAh g-1 with 0.53 K+ reversible (de)intercalation in the structure. We expect that the discovery provides new insights into structural engineering for pursuing stable cathodes to facilitate the future applications of high-performance PIBs.

Accurately Localizing Multiple Nanoparticles in a Multishelled Matrix Through Shell-to-Core Evolution for Maximizing Energy-Storage Capability.

Robust and fast lithium energy storage with a high energy density is highly desired to accelerate the market adoption of electric vehicles. To realize such a goal requires the development of electrode materials with a high capacity, however, such electrode materials suffer from huge volume expansion and induced short cycling life. Here, using tin (Sn) as an example, an ideal structure is designed to effectively solve these problems by separately localizing multiple Sn nanoparticles in a nitrogen-doped carbon hollow multishelled structure with duplicated layers for carbon shell (Sn NPs@Nx C HoMS-DL). The fabricated composite can promote ion and electron diffusion owing to the conductive network formed by connected multiple shells and cores, effectively buffer the volume expansion, and maintain a stable electrode-electrolyte interface. Despite the challenging fabrication, such a structure is realized through an innovative and facile synthesis strategy of "in situ evolution of shell to core", which is applicable for diverse low-melting-point materials. As expected, such a structure enables the high-capacity electrode material to realize nearly its theoretical lithium-storage capability: the developed Sn NPs@Nx C HoMS-DL electrode maintains 96% of its theoretical capacity after 2000 cycles at 2C.

Construction of Li3PO4 nanoshells for the improved electrochemical performance of a Ni-rich cathode material.

A Li3PO4 nanocoating around a nickel-rich cathode material was successfully constructed via controlling the reaction between the electrode material and a preformed phosphorus-containing polymeric nanoshell; this not only effectively tackles the alkali residue challenge, but it also contributes to much-improved electrochemical performance being shown by a high-energy cathode.

Precise surface control of cathode materials for stable lithium-ion batteries.

The increasing demand for high-energy Li-ion batteries (LIBs) continues to push the development of electrode materials, particularly cathode materials, towards their capacity limits. Despite the enormous success, the stability and reliability of LIBs are becoming a serious concern due to the much-aggravated side reactions between electrode materials and organic electrolytes. How to stabilize the cathode/electrolyte interface is therefore an imperative and urgent task drawing considerable attention from both academia and industry. An active treatment on the surface of cathode materials, usually by introducing an inert protection layer, to diminish their side reaction with electrolytes turns out to be a reasonable and effective strategy. This Feature Article firstly outlines our synthesis efforts for the construction of a uniform surface nanocoating on various cathode materials. Different wet chemical routes have been designed to facilitate the control of growth kinetics of targeted coating species so that a precise surface coating could be achieved with nanometer accuracy. Furthermore, we showed the possibility to transform the outer coating layer into a surface doping effect through surface solid reaction at high temperature. A detailed discussion on the structure-performance relationship of these surface-controlled cathode materials is introduced to probe the stabilization mechanism. Finally, perspectives on the development tendency of high-energy cathodes for stable LIBs are provided.

Coordination-Assisted Precise Construction of Metal Oxide Nanofilms for High-Performance Solid-State Batteries.

The application of solid-state batteries (SSBs) is challenged by the inherently poor interfacial contact between the solid-state electrolyte (SSE) and the electrodes, typically a metallic lithium anode. Building artificial intermediate nanofilms is effective in tackling this roadblock, but their implementation largely relies on vapor-based techniques such as atomic layer deposition, which are expensive, energy-intensive, and time-consuming due to the monolayer deposited per cycle. Herein, an easy and low-cost wet-chemistry fabrication process is used to engineer the anode/solid electrolyte interface in SSBs with nanoscale precision. This coordination-assisted deposition is initiated with polyacrylate acid as a functional polymer to control the surface reaction, which modulates the distribution and decomposition of metal precursors to reliably form a uniform crack-free and flexible nanofilm of a large variety of metal oxides. For demonstration, artificial Al2O3 interfacial nanofilms were deposited on a ceramic SSE, typically garnet-structured Li6.5La3Zr1.5Ta0.5O12 (LLZT), that led to a significant decrease in the Li/LLZT interfacial resistance (from 2079.5 to 8.4 Ω cm2) as well as extraordinarily long cycle life of the assembled SSBs. This strategy enables the use of a nickel-rich LiNi0.83Co0.07Mn0.1O2 cathode to deliver a reversible capacity of 201.5 mAh g-1 at a considerable loading of 4.8 mg cm-2, featuring performance metrics for an SSB that is competitive with those of traditional Li-ion systems. Our study demonstrates the potential of solution-based routes as an affordable and scalable manufacturing alternative to vapor-based deposition techniques that can accelerate the development of SSBs for practical applications.

A General Synthesis Strategy for Hollow Metal Oxide Microspheres Enabled by Gel-Assisted Precipitation.

Hollow metal oxide microspheres (HMMs) have drawn enormous attention in different research fields. Reliable and scalable synthetic protocols applicable for a large variety of metal oxides are in emergent demand. Here we demonstrated that polymer hydrogel, such as the resorcinol formaldehyde (RF) one, existed as an efficient synthetic platform to build HMMs. Specifically, the RF gel forms stacked RF microspheres enlaced with its aqueous phase, where the following evaporation of the highly dispersed water leads to a gel-assisted precipitation (GAP) of the dissolved metal precursor onto the embedded polymeric solids suited for the creation of HMMs. By taking advantage of the structural features of hydrogel, this synthesis design avoids the delicate control on the usually necessitated coating process and provides a simple and effective synthetic process versatile for functional HMMs, particularly Nb2 O5 as a high-performance electrode material in Li-ion intercalation pseudocapacitor.

High-Performance Cathode Materials for Potassium-Ion Batteries: Structural Design and Electrochemical Properties.

Due to the obvious advantage in potassium reserves, potassium-ion batteries (PIBs) are now receiving increasing research attention as an alternative energy storage system for lithium-ion batteries (LIBs). Unfortunately, the large size of K+ makes it a challenging task to identify suitable electrode materials, particularly cathode ones that determine the energy density of PIBs, capable of tolerating the serious structural deformation during the continuous intercalation/deintercalation of K+ . It is therefore of paramount importance that proper design principles of cathode materials be followed to ensure stable electrochemical performance if a practical application of PIBs is expected. Herein, the current knowledge on the structural engineering of cathode materials acquired during the battle against its performance degradation is summarized. The K+ storage behavior of different types of cathodes is discussed in detail and the structure-performance relationship of materials sensitive to their different lattice frameworks is highlighted. The key issues facing the future development of different categories of cathode materials are also highlighted and perspectives for potential approaches and strategies to promote the further development of PIBs are provided.

Manipulating Particle Chemistry for Hollow Carbon-based Nanospheres: Synthesis Strategies, Mechanistic Insights, and Electrochemical Applications.

Hollow carbon-based nanospheres (HCNs) have been demonstrated to show promising potential in a large variety of research fields, particularly electrochemical devices for energy conversion/storage. The current synthetic protocols for HCNs largely rely on template-based routes (TBRs), which are conceptually straightforward in creating hollow structures but challenged by the time-consuming operations with a low yield in product as well as serious environmental concerns caused by hazardous etching agents. Meanwhile, they showed inadequate ability to build complex carbon-related architectures. Innovative strategies for HCNs free from extra templates thus are highly desirable and are expected to not only ensure precise control of the key structural parameters of hollow architectures with designated functionalities, but also be environmentally benign and scalable approaches suited for their practical applications.In this Account, we outline our recent research progress on the development of template-free protocols for the creation of HCNs with a focus on the acquired mechanical insight into the hollowing mechanism when no extra templates were involved. We demonstrated that carbon-based particles themselves could act as versatile platforms to create hollow architectures through an effective modulation of their inner chemistry. By means of reaction control, the precursor particles were synthesized into solid ones with a well-designed inhomogeneity inside in the form of different chemical parameters such as molecular weight, crystallization degree, and chemical reactivity, by which we not only can create hollow structures inside particles but also have the ability to tune the key features including compositions, porosity, and dimensional architectures. Accordingly, the functionalities of the prepared HCNs could be systematically altered or optimized for their applications. Importantly, the discussed synthesis approaches are facile and environmentally benign processes with potential for scale-up production.The nanoengineering of HNCs is found to be of special importance for their application in a large variety of electrochemical energy storage and conversion systems where the charge transfer and structural stability become a serious concern. Particular attention in this Account is therefore directed to the potential of HCNs in battery systems such as sodium ion batteries (NIBs) and potassium ion batteries (KIBs), whose electrochemical performances are plagued by the destructive volumetric deformation and sluggish charge diffusion during the intercalation/deintercalation of large-size Na+ or K+. We demonstrated that precise control of the multidimensional factors of the HCNs is critical to offer an optimized design of sufficient reactive sites, excellent charge and mass transport kinetics, and resilient electrode structure and also provide a model system suitable for the study of complicated metal-ion storage mechanisms, such as Na+ storage in a hard carbon anode. We expect that this Account will spark new endeavors in the development of HCNs for various applications including energy conversion and storage, catalysis, biomedicine, and adsorption.

Spherical Mesoporous Metal Oxides with Tunable Orientation Enabled by Growth Kinetics Control.

Recent advances in spherical mesoporous metal oxides (SMMOs) have demonstrated their enormous potential in a large variety of research fields. However, a direct creation of these materials with precise control on their key shape features, particularly pore architectures, remains a major challenge as compared to the widely explored counterpart of silica. Here, using Al2O3 as an example, we identified that deposition kinetics in solution played an essential role in the construction of different SMMOs. Specifically, a controlled Al3+ precipitation is critical to maintaining the electrostatic interaction between the inorganic precursors and the molecular templates, thereby achieving a designable assembly of these two components toward uniform mesoporous Al2O3-based nanospheres. We demonstrated that such a synthesis strategy is not only able to precisely control the channel orientations from concentric to radial and dendritic, a synthesis capability impeded so far for SMMOs, but is readily applicable to other metal oxides. Our study showed that the growth-kinetics control is a simple but powerful synthesis protocol and opened up a multifunctional platform to achieve systematic design of SMMOs for their future applications.

Dielectric Polarization in Inverse Spinel-Structured Mg2 TiO4 Coating to Suppress Oxygen Evolution of Li-Rich Cathode Materials.

High-energy Li-rich layered cathode materials (≈900 Wh kg-1 ) suffer from severe capacity and voltage decay during cycling, which is associated with layered-to-spinel phase transition and oxygen redox reaction. Current efforts mainly focus on surface modification to suppress this unwanted structural transformation. However, the true challenge probably originates from the continuous oxygen release upon charging. Here, the usage of dielectric polarization in surface coating to suppress the oxygen evolution of Li-rich material is reported, using Mg2 TiO4 as a proof-of-concept material. The creation of a reverse electric field in surface layers effectively restrains the outward migration of bulk oxygen anions. Meanwhile, high oxygen-affinity elements of Mg and Ti well stabilize the surface oxygen of Li-rich material via enhancing the energy barrier for oxygen release reaction, verified by density functional theory simulation. Benefited from these, the modified Li-rich electrode exhibits an impressive cyclability with a high capacity retention of ≈81% even after 700 cycles at 2 C (≈0.5 A g-1 ), far superior to ≈44% of the unmodified counterpart. In addition, Mg2 TiO4 coating greatly mitigates the voltage decay of Li-rich material with the degradation rate reduced by ≈65%. This work proposes new insights into manipulating surface chemistry of electrode materials to control oxygen activity for high-energy-density rechargeable batteries.

Solid-Solution-Based Metal Alloy Phase for Highly Reversible Lithium Metal Anode.

Lithium metal batteries are vital devices for high-energy-density energy storage, but the Li metal anode is highly reactive with electrolyte and forms uncontrolled dendrite that can cause undesirable parasitic reactions and, thus, poor cycling stability and raise safety concerns. Despite remarkable progress to partially solve these issues, the Li metal still plates at the electrode/electrolyte interface where the parasitic reactions and dendrite formation invariably occur. Here, we demonstrate the inward-growth plating of Li atoms into a metal foil of thickness of tens of micrometers while avoiding surface deposition, which is driven by the reversible solid-solution-based alloy phase change. Lithiation of the solid-solution alloy phase allows the freshly generated Li atoms at the surface to sink into the metal foil, while the reversible alloy phase change is companied by the dealloying reaction during delithiation, which extracts Li atoms from inside of the metal foil. The yielded dendrite free Li anode produces an enhanced Coulombic efficiency of 99.5 ± 0.2% with a reversible capacity of 1660 mA h g-1 (3.3 mA h cm-2).

Light-Driven Crawling of Molecular Crystals by Phase-Dependent Transient Elastic Lattice Deformation.

The light-driven crawling of a molecular crystal that can form three phases, (α, ß, and γ) is presented. Laser irradiation of the molecular crystal can generate phase-dependent transient elastic lattice deformation. The resulting elastic lattice deformation that follows scanning irradiation of a laser can actuate the different phases of molecular crystal to move with different velocity and direction. Because the γ phase has a large Young's modulus (ca. 26 GPa), a force of 0.1 µN can be generated under one laser spot. The generated force is sufficient to actuate the γ-formed molecular crystals in a wide dimensional range to move longitudinally at a velocity of about 60 µm min-1 , which is two orders of magnitude faster than the α and ß phases.