Toward High-Performance Dihydrophenazine-Based Conjugated Microporous Polymer Cathodes for Dual-Ion Batteries through Donor–Acceptor Structural Design

Recent studies have demonstrated that dihydrophenazine (Pz) with high redox-reversibility and high theoretical capacity is an attractive building block to construct p-type polymer cathodes for dual-ion batteries. However, most reported Pz-based polymer cathodes to date still suffer from low redox activity, slow kinetics, and short cycling life. Herein, a donor–acceptor (D–A) Pz-based conjugated microporous polymer (TzPz) cathode is constructed by integrating the electron-donating Pz unit and the electron-withdrawing 2,4,6-triphenyl-1,3,5-triazine (Tz) unit into a polymer chain. The D–A type structure enhances the polymer conjugation degree and decreases the band gap of TzPz, facilitating electron transportation along the polymer skeletons. Therefore the TzPz cathode for dual-ion battery shows a high reversible capacity of 192 mAh g⁻¹ at 0.2 A g⁻¹ with excellent rate performance (108 mAh g⁻¹ at 30 A g⁻¹), which is much higher than that of its counterpart polymer BzPz produced from 1,3,5-triphenylbenzene (Bz) and Pz (148 and 44 mAh g⁻¹ at 0.2 and 10 A g⁻¹, respectively). More importantly, the TzPz cathode also shows a long and stable cyclability of more than 10 000 cycles. These results demonstrate that the D–A structural design is an efficient strategy for developing high-performance polymer cathodes for dual-ion batteries.     

Nitrate Additives Coordinated with Crown Ether Stabilize Lithium Metal Anodes in Carbonate Electrolyte

Lithium metal anodes (LMAs) are promising for next-generation batteries but have poor compatibility with the widely used carbonate-based electrolytes, which is a major reason for their severe dendrite growth and low Coulombic efficiency (CE). A nitrate additive to the electrolyte is an effective solution, but its low solubility in carbonates is a problem that can be solved using a crown ether, as reported. A rubidium nitrate additive coordinated with 18-crown-6 crown ether stabilizes the LMA in a carbonate electrolyte. The coordination promotes the dissolution of NO₃⁻ ions and helps form a dense solid electrolyte interface that is Li₃N-rich which guides uniform Li deposition. In addition, the Rb (18-crown-6)⁺ complexes are adsorbed on the dendrite tips, shielding them from Li deposition on the dendrite tips. A high CE of 97.1% is achieved with a capacity of 1 mAh cm⁻² in a half cell, much higher than when using the additive-free electrolyte (92.2%). Such an additive is very compatible with a nickel-rich ternary cathode at a high voltage, and the assembled full battery with a cathode material loading up to 10 mg cm⁻² shows an average CE of 99.8% over 200 cycles, indicating a potential for practical use.     

Harvesting Air and Light Energy via “All-in-One” Polymer Cathodes for High-Capacity,Self-Chargeable,and Multimode-Switching Zinc Batteries

Aqueous rechargeable Zinc (Zn)–polymer batteries are promising alternatives to prevalent Li-ion cells in terms of cost, safety, and rate capability but they suffer from limited specific capacity in addition to poor environmental adaptability. Herein, air and light are successfully utilized from external environments in single near-neutral two-electrode Zn batteries to enable remarkably improved electrochemical performance, fast self-charging, and switchable multimode-operation from Zn–polymer to Zn–air cells. This system is enabled by a well-designed polyaniline-nanorod-array based “all-in-one” cathode combining reversible redox capability, oxygen reduction activity, and photothermal-responsiveness. The initiative design allows perfect integration of multiple energy harvesting from ambient “air” and light, energy conversion, and storage in one single cathode. Thus, it can act as an efficient light-assisted electrically-rechargeable Zn–polymer cell featuring the highest specific capacity of 430.0 mAh g⁻¹ among all existing polymer cathodes. Without external power sources, it can be self-charged to deliver a high discharging capacity of 363.1 mAh g⁻¹ by concurrently harvesting chemical energy from air and light energy for only 20 min. It can also switch to a light-responsive Zn–air battery mode to surmount the output capacity limit of Zn–polymer battery mode for continued electricity supply.     

Structural Aspects of P2-Type Na0.67Mn0.6Ni0.2Li0.2O2 (MNL) Stabilization by Lithium Defects as a Cathode Material for Sodium-Ion Batteries

A known strategy for improving the properties of layered oxide electrodes in sodium-ion batteries is the partial substitution of transition metals by Li. Herein, the role of Li as a defect and its impact on sodium storage in P2-Na_0.67Mn_0.6Ni_0.2Li_0.2O₂ is discussed. In tandem with electrochemical studies, the electronic and atomic structure are studied using solid-state NMR, operando XRD, and density functional theory (DFT). For the as-synthesized material, Li is located in comparable amounts within the sodium and the transition metal oxide (TMO) layers. Desodiation leads to a redistribution of Li ions within the crystal lattice. During charging, Li ions from the Na layer first migrate to the TMO layer before reversing their course at low Na contents. There is little change in the lattice parameters during charging/discharging, indicating stabilization of the P2 structure. This leads to a solid-solution type storage mechanism (sloping voltage profile) and hence excellent cycle life with a capacity of 110 mAh g^-1 after 100 cycles. In contrast, the Li-free compositions Na_0.67Mn_0.6Ni_0.4O₂ and Na_0.67Mn_0.8Ni_0.2O₂ show phase transitions and a stair-case voltage profile. The capacity is found to originate from mainly Ni³⁺/Ni⁴⁺ and O^2-/O^2-δ redox processes by DFT, although a small contribution from Mn⁴⁺/Mn⁵⁺ to the capacity cannot be excluded.     

Evolution of Local Structural Ordering and Chemical Distribution upon Delithiation of a Rock Salt–Structured Li1.3Ta0.3Mn0.4O2 Cathode

Lithium‐rich disordered rock‐salt oxides have attracted great interest owing to their promising performance as Li‐ion battery cathodes. While experimental and theoretical efforts are critical in advancing this class of materials, a fundamental understanding of key property changes upon Li extraction is largely missing. In the present study, single‐crystal synthesis of a new disordered rock‐salt cathode material, Li_1.3Ta_0.3Mn_0.4O₂ (LTMO), and its use as a model compound to investigate Li concentration–driven evolution of local cationic ordering, charge compensation, and chemical distribution are reported. Through the combined use of 2D and 3D X‐ray nanotomography, it is shown that Li removal accompanied by oxygen oxidation is correlated with the development of morphological defects such as particle cracking. Chemical heterogeneity, quantified by subparticle level distribution of Mn valence state, is minimal during Mn redox, which drastically increases upon the formation of cracks during oxygen redox. Density functional theory and bond valence sum mismatch calculations reveal the presence of local short‐range ordering in the pristine oxide, which gradually disappears along with the extraction of Li. The study suggests that with cycling the transformation into true cation–disordered state can be expected, which likely impacts the voltage profile and obtainable energy density of the oxide cathodes.     

Inkjet-printed Ag@SDC core-shell nanoparticles as a high-performance cathode for low-temperature solid oxide fuel cells

This work demonstrates the superior thermostability of silver-based nanoparticle cathodes under continuous solid oxide fuel cell operation by coating the samarium-doped ceria (SDC) thin shell over silver nanoparticles. The Ag-core/SDC-shell (Ag@SDC) nanoparticles prepared by solvothermal synthesis (Ag core diameter = 48 nm; average SDC shell thickness = 2–5 nm) is inkjet-printed on electrolyte substrates as a thin film cathode. The Ag@SDC film survives the 48-h thermal annealing and its most porosities remain visibly un-agglomerated. The results of fuel cell current stability test show that the cell using the Ag@SDC nanoparticle cathode have only 3% of current degradation after 25 h, which is remarkably lower than that of the cell using the bare Ag nanoparticle cathode (96.1%). In addition, the electrochemical performance of the bare silver cathode in oxygen reduction reaction has significantly improved because of the enhanced surface oxygen adsorption/dissociation process provided by the SDC thin shell.     

Mass-Producible,Quasi-Zero-Strain,Lattice-Water-Rich Inorganic Open-Frameworks for Ultrafast-Charging and Long-Cycling Zinc-Ion Batteries

Low-cost and high-safety aqueous Zn-ion batteries are an exceptionally compelling technology for grid-scale energy storage. However, their development has been plagued by the lack of stable cathode materials allowing fast Zn²⁺-ion insertion and scalable synthesis. Here, a lattice-water-rich, inorganic-open-framework (IOF) phosphovanadate cathode, which is mass-producible and delivers high capacity (228 mAh g⁻¹) and energy density (193.8 Wh kg⁻¹ or 513 Wh L⁻¹), is reported. The abundant lattice waters functioning as a “charge shield” enable a low Zn²⁺-migration energy barrier, (0.66 eV) even close to that of Li⁺ within LiFePO₄. This fast intrinsic ion-diffusion kinetics, together with nanostructure effect, allow the achievements of ultrafast charging (71% state of charge in 1.9 min) and an ultrahigh power density (7200 W kg⁻¹ at 107 Wh kg⁻¹). Equally important, the IOF exhibits a quasi-zero-strain feature (<1% lattice change upon (de)zincation), which ensures ultrahigh cycling durability (3000 cycles) and Coulombic efficiencies of 100%. The cell-level energy and power densities reach ≈90 Wh kg⁻¹ and ≈3320 W kg⁻¹, far surpassing commercial lead–acid, Ni–Cd, and Ni–MH batteries. Lattice-water-rich IOFs may open up new opportunities for exploring stable and fast-charging Zn-ion batteries.     

Enable high reversibility of Fe/Cu based fluoride conversion batteries via interfacial gas release and detergency of garnet electrolytes

Garnet-type Ta-doped Li₇La₃Zr₂O₁₂ (LLZTO) electrolyte suffers from unstable chemical passivation under air exposure, responsible for the poor interfacial wettability and conductivity with Li metal. Instead of conventional methods to remove surface contaminants by mechanical polishing, acid etching and high temperature reduction, herein we propose a simple strategy of interfacial gas release and detergency to smartly convert Li₂CO₃ passivation layer into ion-conductive Li₃PO₄ domains at mild temperature (∼200 ℃). The in-situ formation of PH₃ vapor and its phosphorization enables a dramatic decrease of Li/garnet interfacial resistance down to 2 Ω cm² at room temperature (RT). The improved interfacial wettability and conductivity endow the symmetric cells with ultra-stable galvanostatic cycling over 1500 h and high critical current density of 2.6 mA/cm². The high coulombic efficiency of Li plating enables a high reversibility of solid-state NCM811/Li cells even under a low N/P ratio (∼4) and high cut-off voltage of 4.5 V at RT. The prototype of fluoride-garnet solid-state batteries are successfully driven as rechargeable system (rather than widely known primary battery) with high conversion capacity (400 ∼ 500 mAh/g) and high-rate performance (251.2 mAh/g at 3 C). This interface infiltration-detergency approach provides a practical solution to the achievement of high-energy solid-state Li metal batteries.     

薄壁金属气囊抛撒性能流固耦合分析

为研究机载布撒器囊式抛撒系统中气囊的抛撒性能,以初始为扁平结构的薄壁金属(304不锈钢)气囊为研究对象,采用流固耦合的方法对其膨胀抛弹过程展开数值仿真分析,得到囊内的流场特性和囊壁的应力响应,计算结果与试验吻合较好.分析了入口边界条件及气囊结构对抛撒结果的影响,计算结果表明:气囊入口直径和入口边界条件是影响子弹分离速度和过载的关键因素,装药量、入口直径越大,子弹过载越大;一定装药量下,气囊入口直径不同时,子弹存在极限分离速度;气囊初始面积对子弹分离速度影响很小(仅4%),主要影响囊内的燃气压力,初始面积越大囊压越小,有利于降低囊壁的应力值.计算结果可为气囊结构的优化设计与工程实际应用提供重要参考.