Oxide-Based Solid-State Batteries: A Perspective on Composite Cathode Architecture

The garnet-type phase Li₇La₃Zr₂O₁₂ (LLZO) attracts significant attention as an oxide solid electrolyte to enable safe and robust solid-state batteries (SSBs) with potentially high energy density. However, while significant progress has been made in demonstrating compatibility with Li metal, integrating LLZO into composite cathodes remains a challenge. The current perspective focuses on the critical issues that need to be addressed to achieve the ultimate goal of an all-solid-state LLZO-based battery that delivers safety, durability, and pack-level performance characteristics that are unobtainable with state-of-the-art Li-ion batteries. This perspective complements existing reviews of solid/solid interfaces with more emphasis on understanding numerous homo- and heteroionic interfaces in a pure oxide-based SSB and the various phenomena that accompany the evolution of the chemical, electrochemical, structural, morphological, and mechanical properties of those interfaces during processing and operation. Finally, the insights gained from a comprehensive literature survey of LLZO–cathode interfaces are used to guide efforts for the development of LLZO-based SSBs.     

KxVPO4F (x∼0): A New High-Voltage and Low-Stain Cathode Material for Ultrastable Calcium Rechargeable Batteries

The utilization of high-voltage intercalation cathodes in calcium-ion batteries (CIBs) is impeded by the substantial size and divalent character of Ca²⁺ ions, which result in pronounced volume alterations and sluggish ion mobility, consequently causing inferior reversibility and low energy/power densities. To tackle these issues, polyanionic K-vacant K_xVPO₄F (x∼0, designated as K₀VPF) is proposed as high-voltage and ultra-stable cathode material in CIBs. The K₀VPF demonstrates a decent calcium storage capacity of 75 mAh g⁻¹ at 10 mA g⁻¹ and remarkable capacity retention of 84.2% over 1000 cycles. The average working voltage of the K₀VPF is 3.85 V versus Ca²⁺/Ca, representing the highest value reported for CIB cathodes to date. The combined experimental and theoretical investigations revealed that the low volume changes and hopping diffusion barriers contribute to the extraordinary stability and high-power capabilities, respectively, of K₀VPF. The distribution of Ca ions into polyanionic frameworks with pronounced spatial separation effectively attenuates the Ca²⁺–Ca²⁺ repulsive force and thus augmenting the Ca migration kinetics. The high voltage of K₀VPF is attributed to the inductive effect from the largely electronegative fluorine. In conjunction with a calcium metal anode and a compatible electrolyte, Ca metal full cells featured a record-high energy density of ≈300 Wh kg⁻¹.     

Boundary-Free Metal–Organic Framework Glasses Enable Highly Stable All-Solid-State Lithium–Oxygen Battery

Rechargeable lithium–oxygen batteries (LOBs) are considered to be one of the most promising energy storage systems. However, the use of reactive lithium (Li) metal and the formation of Li dendrites during battery operation would lead to serious safety concerns, especially when flammable liquid electrolytes are utilized. Herein, superior metal–organic framework (MOF) glass-based solid-state electrolytes (SSEs) is developed for stable all-solid-state LOBs (SSLOBs). These non-flammable and boundary-free MOF glass SSEs are capable of suppressing the dendrite growth and exhibiting long-term Li stripping/plating stability, contributing to superior Li⁺ conductivity (5 × 10⁻⁴ S cm⁻¹ at 20 °C), high Li⁺ transference number (0.86), and good electrochemical stability. It is discovered that discharge product deposition behavior in the solid-solid interface can be well regulated by the ion/electron mixed conducted cathode fabricated with MOF glass SSEs and electronic conductive polymers. As a result, the SSLOBs can be stably recharged for 400 cycles with a low polarization gap and deliver a high capacity of 13552 mAh g⁻¹. The development of this proposed MOF glass displays great application potential in energy storage systems with good safety and high energy density.     

New Insight into Ni‐Rich Layered Structure for Next‐Generation Li Rechargeable Batteries

An increase in the amount of nickel in LiMO₂ (M = Ni, Co, Mn) layered system is actively pursued in lithium‐ion batteries to achieve higher capacity. Nevertheless, fundamental effects of Ni element in the three‐component layered system are not systematically studied. Therefore, to unravel the role of Ni as a major contributor to the structural and electrochemical properties of Ni‐rich materials, Co‐fixed LiNi_0.5+xCo_0.2Mn_0.3–xO₂ (x = 0, 0.1, and 0.2) layered materials are investigated. The results, on the basis of synchrotron‐based characterization techniques, present a decreasing trend of Ni²⁺ content in Li layer with increasing total Ni contents. Moreover, it is discovered that the c_hex.‐lattice parameter of layered system is not in close connection with the interslab thickness related to actual Li ion pathway. The interslab thickness increases with increasing Ni concentration even though the c_hex.‐lattice parameter decreases. Furthermore, the lithium ion pathway is preserved in spite of the fact that the c‐axis is collapsed at highly deintercalated states. Also, a higher Ni content material shows better structural properties such as larger interslab thickness, lower cation disorder, and smoother phase transition, resulting in better electrochemical properties including higher Li diffusivity and lower overpotential when comparing materials with lower Ni content.     

Hollow CuS Nanoboxes as Li‐Free Cathode for High‐Rate and Long‐Life Lithium Metal Batteries

Transition metal sulfides hold promising potentials as Li‐free conversion‐type cathode materials for high energy density lithium metal batteries. However, the practical deployment of these materials is hampered by their poor rate capability and short cycling life. In this work, the authors take the advantage of hollow structure of CuS nanoboxes to accommodate the volume expansion and facilitate the ion diffusion during discharge–charge processes. As a result, the hollow CuS nanoboxes achieve excellent rate performance (≈371 mAh g^?1 at 20 C) and ultra‐long cycle life (>1000 cycles). The structure and valence evolution of the CuS nanobox cathode are identified by scanning electron microscopy, transmission electron microscopy, and X‐ray photoelectron spectroscopy. Furthermore, the lithium storage mechanism is revealed by galvanostatic intermittent titration technique and operando Raman spectroscopy for the initial charge–discharge process and the following reversible processes. These results suggest that the hollow CuS nanobox material is a promising candidate as a low‐cost Li‐free cathode material for high‐rate and long‐life lithium metal batteries.     

The First Report on Excellent Cycling Stability and Superior Rate Capability of Na3V2(PO4)3 for Sodium Ion Batteries

Sodium ion batteries are attractive for the rapidly emerging large‐scale energy storage market for intermittent renewable resources. Currently a viable cathode material does not exist for practical non‐aqueous sodium ion battery applications. Here we disclose a high performance, durable electrode material based on the 3D NASICON framework. Porous Na₃V₂(PO₄)₃/C was synthesized using a novel solution‐based approach. This material, as a cathode, is capable of delivering an energy storage capacity of ～400 mWh/g vs. sodium metal. Furthermore, at high current rates (10, 20 and 40 C), it displayed remarkable capacity retention. Equally impressive is the long term cycle life. Nearly 50% of the initial capacity was retained after 30,000 charge/discharge cycles at 40 C (4.7 A/g). Notably, coulombic efficiency was 99.68% (average) over the course of cycling. To the best of our knowledge, the combination of high energy density, high power density and ultra long cycle life demonstrated here has never been reported before for sodium ion batteries. We believe our findings will have profound implications for developing large‐scale energy storage systems for renewable energy sources.     

An In Situ Interface Reinforcement Strategy Achieving Long Cycle Performance of Dual‐Ion Batteries

Dual‐ion batteries (DIBs) with high operation voltage offer promising candidates for low‐cost clean energy chemistries. However, there still exist tough issues, including structural collapse of the graphite cathode due to solvent co‐intercalation and electrolyte decomposition on the electrode/electrolyte interface, which results in unsatisfactory cyclability and fast battery failure. Herein, Li₄Ti₅O₁₂ (LTO) modified mesocarbon microbeads (MCMBs) are proposed as a cathode material. The LTO layer functions as a skeleton and offers electrocatalytic active sites for in situ generation of a favorable and compatible cathode electrolyte interface (CEI) layer. The synergetic LTO‐CEI network can change the thermodynamic behavior of the PF₆^? intercalation process and maintain the structural integrity of the graphite cathode, as a “Great Wall” to protect the cathode from structural collapse and electrolyte decomposition. Such LTO‐CEI reinforced cathode exhibits a prolonged cyclability with 85.1% capacity retention after 2000 cycles even at cut‐off potential of 5.4 V versus Li⁺/Li. Moreover, the LTO‐modified MCMB (+)//prelithiated MCMB (?) full cell exhibits a high energy density of ≈200 Wh kg^?1, remarkably enhanced cyclability with 93.5% capacity retention after 1000 cycles. Undoubtedly, this work offers in‐depth insight into interface chemistry, which can arouse new originality to boost the development of DIBs.     

A New High Power LiNi0.81Co0.1Al0.09O2 Cathode Material for Lithium‐Ion Batteries

Among the various Ni‐based layered oxide systems in the form of LiNi_1‐y‐zCo_yAl_zO₂ (NCA), the compostions between y = 0.1–0.15, z = 0.05 are the most successful and commercialized cathodes used in electric vehicles (EVs) and hybrid electric vehicles (HEVs). However, tremendous research effort has been dedicted to searching for better composition in NCA systems to overcome the limitations of these cathodes, particularly those that arise when they are used use at high discharge/charge rates (>5C) and in high temperature (60 °C) environments. In addition, improving the thermal stability at 4.5 V is also very important in terms of the total amount of heat generated and the onset temperature. Here, a new NCA composition in the form of LiNi_0.81Co_0.1Al_0.09O₂ (y = 0.1, z = 0.09) is reported for the first time. Compared to the LiNi_0.85Co_0.1Al_0.05O₂ cathode, LiNi_0.81Co_0.1Al_0.09O₂ exhibits an excellent rate capability of 155 mAh g^?1 at 10 C with a cut‐off voltage range between 3 and 4.5 V, corresponding to 562 Wh kg^?1 at 24 °C. It additionally provides significantly improved thermal stability and electrochemical performance at the high temperature of 60 °C, with a discharge capacity of 122 mAh g^?1 after 200 cycles with capacity retention of 59%.