A nitroaromatic cathode with an ultrahigh energy density based on six-electron reaction per nitro group for lithium batteries.

Organic electrode materials have emerged as promising alternatives to conventional inorganic materials because of their structural diversity and environmental friendliness feature. However, their low energy densities, limited by the single-electron reaction per active group, have plagued the practical applications. Here, we report a nitroaromatic cathode that performs a six-electron reaction per nitro group, drastically improving the specific capacity and energy density compared with the organic electrodes based on single-electron reactions. Based on such a reaction mechanism, the organic cathode of 1,5-dinitronaphthalene demonstrates an ultrahigh specific capacity of 1,338 mAh⋅g-1 and energy density of 3,273 Wh⋅kg-1, which surpass all existing organic cathodes. The reaction path was verified as a conversion from nitro to amino groups. Our findings open up a pathway, in terms of battery chemistry, for ultrahigh-energy-density Li-organic batteries.

Zinc Powder Anodes for Rechargeable Aqueous Zinc-Based Batteries.

Aqueous rechargeable zinc-based batteries hold great promise for energy storage applications, with most research utilizing zinc foils as the anode. Conversely, the high tunability of zinc powder (Zn-P) makes it an ideal choice for zinc-based batteries, seamlessly integrating with current battery production technologies. However, challenges such as contact loss, dendrite formation, and a high tendency for corrosion significantly hamper the performance enhancement of Zn-P anodes. This review provides an overview of strategies adopted from various perspectives, including zinc powder optimization, electrode engineering, and electrolyte modification, to address these issues. Additionally, it explores the limitations of existing research and offers valuable insights into potential future directions for further advancements in Zn-P anodes.

A Comprehensive Evaluation of Battery Technologies for High-Energy Aqueous Batteries.

Aqueous batteries have garnered significant attention in recent years as a viable alternative to lithium-ion batteries for energy storage, owing to their inherent safety, cost-effectiveness, and environmental sustainability. This study offers a comprehensive review of recent advancements, persistent challenges, and the prospects of aqueous batteries, with a primary focus on energy density compensation of various battery engineering technologies. Additionally, cutting-edge high-energy aqueous battery designs are emphasized as a reference for future endeavors in the pursuit of high-energy storage solutions. Finally, a dual-compatibility battery configuration perspective aimed at concurrently optimizing cycle stability, redox potential, capacity utilization for both anode and cathode materials, as well as the selection of potential electrode candidates, is proposed with the ultimate goal of achieving cell-level energy densities exceeding 400 Wh kg-1.

Electrolyte Engineering Empowers Li||CFx Batteries to Achieve High Energy Density and Low Self-Discharge at Harsh Conditions.

Given its exceptional theoretical energy density (over 2000 Wh kg-1), lithium||carbon fluoride (Li||CFx) battery has garnered global attention. N-methylpyrrolidone (NMP)-based electrolyte is regarded as one promising candidate for tremendously enhancing the energy density of Li||CFx battery, provided self-discharge challenges can be resolved. This study successfully achieves a low self-discharge (LSD) and desirable electrochemical performance in Li||CFx batteries at high temperatures by utilizing NMP as the solvent and incorporating additional ingredients, including vinylene carbonate additive, as well as the dual-salt systems formed by LiBF4 with three different Li salts, namely lithium bis(oxalato)borate, lithium difluoro(oxalato)borate, and LiNO3. The experimental results unfold that the proposed methods not only minimize aluminum current collector corrosion, but also effectively passivate the Li metal anode. Among them, LiNO3 exhibits the most pronounced effect that achieves an energy density of ≈2400 Wh kg-1 at a current density of 10 mA g-1 at 30 °C, nearly 0% capacity-fade rate after 300 h of storage at 60 °C, and the capability to maintain a stable open-circuit voltage over 4000 h. This work provides a distinctive perspective on how to realize both high energy density and LSD rates at high temperature of Li||CFx battery.

Rational Design of High-Loading Electrodes with Superior Performances Toward Practical Application for Energy Storage Devices.

High-loading electrodes play a crucial role in designing practical high-energy batteries as they reduce the proportion of non-active materials, such as current separators, collectors, and battery packaging components. This design approach not only enhances battery performance but also facilitates faster processing and assembly, ultimately leading to reduced production costs. Despite the existing strategies to improve rechargeable battery performance, which mainly focus on novel electrode materials and high-performance electrolyte, most reported high electrochemical performances are achieved with low loading of active materials (<2 mg cm-2). Such low loading, however, fails to meet application requirements. Moreover, when attempting to scale up the loading of active materials, significant challenges are identified, including sluggish ion diffusion and electron conduction kinetics, volume expansion, high reaction barriers, and limitations associated with conventional electrode preparation processes. Unfortunately, these issues are often overlooked. In this review, the mechanisms responsible for the decay in the electrochemical performance of high-loading electrodes are thoroughly discussed. Additionally, efficient solutions, such as doping and structural design, are summarized to address these challenges. Drawing from the current achievements, this review proposes future directions for development and identifies technological challenges that must be tackled to facilitate the commercialization of high-energy-density rechargeable batteries.

Flexible Hybrid Supercapacitor Achieving 2.2 V with NiCo2S4/Polyaniline/MnO2 and N, S-Co-Doped Carbon Nanofibers for Ultra-High Energy Density.

Flexible all-solid-state asymmetric supercapacitors (FAASC) represent a highly promising power sources for wearable electronics. However, their energy density is relatively less as compared to the conventional batteries. Herein, a novel ultra-high energy density FAASC is developed using nickel-cobalt sulfide (NiCo2S4)/polyaniline (PANI)/manganese dioxide (MnO2) ternary composite on carbon fiber felt (CF) as positive and N, S-co-doped carbon nanofibers (CNF)/CF as negative electrode, respectively. Initially, porous δ-MnO2 nanoworm-like network is decorated on CF using potentiodynamic method. Subsequently, interconnected PANI nanostructures is grown on the MnO2 via a facile in situ chemical polymerization, followed by the electrodeposition of highly porous NiCo2S4 nanowalls. Benefiting from 3D porous structure of conductive CF and redox active properties of NiCo2S4, PANI and MnO2, FAASC achieved a superior energy storage capacity. Later, high-performance N, S-co-doped CNF/CF negative electrode is synthesized using electropolymerization of PANI nanofibers on CF, followed by the carbonization process. The assembled FAASC exhibits a wide voltage window of 2.2 V and remarkable specific capacitance of 143 F g-1 at a current density of 1 A g-1. The cell further delivers a superb energy density of 71.6 Wh kg-1 at a power density of 492.7 W kg-1, supreme cycle life and remarkable electrochemical stability under mechanical bending.

Recent Progress of Advanced Functional Separators in Lithium Metal Batteries.

As a representative in the post-lithium-ion batteries (LIBs) landscape, lithium metal batteries (LMBs) exhibit high-energy densities but suffer from low coulombic efficiencies and short cycling lifetimes due to dendrite formation and complex side reactions. Separator modification holds the most promise in overcoming these challenges because it utilizes the original elements of LMBs. In this review, separators designed to address critical issues in LMBs that are fatal to their destiny according to the target electrodes are focused on. On the lithium anode side, functional separators reduce dendrite propagation with a conductive lithiophilic layer and a uniform Li-ion channel or form a stable solid electrolyte interphase layer through the continuous release of active agents. The classification of functional separators solving the degradation stemming from the cathodes, which has often been overlooked, is summarized. Structural deterioration and the resulting leakage from cathode materials are suppressed by acidic impurity scavenging, transition metal ion capture, and polysulfide shuttle effect inhibition from functional separators. Furthermore, flame-retardant separators for preventing LMB safety issues and multifunctional separators are discussed. Further expansion of functional separators can be effectively utilized in other types of batteries, indicating that intensive and extensive research on functional separators is expected to continue in LIBs.

High-Energy-Density Solid-State Metal-Air Batteries: Progress, Challenges, and Perspectives.

Next-generation batteries have long been considered a transition to more sustainable storage technologies. Among them, metal-air batteries (MABs) with low cost, high safety, and environmental friendliness have shown great potential for future large-scale applications. Motivated by the desirable characteristics, significant progress is made in suppressing serious parasitic reactions, improving electrochemical performance, and increasing the energy density in MABs. Compared to the widely reported liquid electrolyte strategy, solid-state electrolytes (SSEs) can thoroughly solve the volatilization challenges of liquid electrolytes and protect the oxygen electrodes without the formation of diffusion-blocking oxide phases. Notably, SSEs for MABs are still in their infancy, and many thorny challenges still need to be solved. In this review, the main electrochemical mechanism, key challenges, and some important progress are sorted out for solid-state MABs, such as lithium-air, zinc-air, aluminum-air, and magnesium-air batteries. Besides their fundamental significance, these configurations are further compared in terms of energy density, cost, carbon footprint, energy consumption, rate performance, cycle performance, safety, and air stability of prevailing electrolytes.

High Safety Electrolyte Design for Enabling High Energy-Density System of LiNi0.8Co0.1Mn0.1O2//Phosphorus by Simultaneously Adjusting Dual Electrode/Electrolyte Interfaces.

The demand for state-of-the-art high-energy-density lithium-ion batteries is increasing. However, the low specific capacity of electrode materials in conventional full-cell systems cannot meet the requirements. Ni-rich layered oxide cathodes such as Li(Ni0.8Co0.1Mn0.1)O2 (NCM811) have a high theoretical specific capacity of 200 mAh g-1, but it is always accompanied by side reactions on the electrode/electrolyte interface. Phosphorus anode possesses a high theoretical specific capacity of 2596 mAh g-1, but it has a huge volume expansion (≈300%). Herein, a highly compatible and secure electrolyte is reported via introducing an additive with a narrow electrochemical window, Lithium difluoro(oxalato)borate (LiDFOB), into 1 m LiPF6 EC/DMC with tris (2,2,2-trifluoroethyl) phosphate (TFEP) as a cosolvent. LiDFOB participates in the formation of organic/inorganic hybrid electrode/electrolyte interface layers at both the cathode and anode sides. The side reactions on the surface of the NCM811 cathode and the volume expansion of the phosphorus anode are effectively alleviated. The NCM811//RP full cell in this electrolyte shows high capacity retention of 82% after 150 cycles at a 0.5C rate. Meanwhile, the electrolyte shows non-flammability. This work highlights the importance of manipulating the electrode/electrolyte interface layers for the design of lithium-ion batteries with high energy density.

Pseudocapacitive Storage in Molybdenum Oxynitride Nanostructures Reactively Sputtered on Stainless-Steel Mesh Towards an All-Solid-State Flexible Supercapacitor.

Exploiting pseudocapacitance in rationally engineered nanomaterials offers greater energy storage capacities at faster rates. The present research reports a high-performance Molybdenum Oxynitride (MoON) nanostructured material deposited directly over stainless-steel mesh (SSM) via reactive magnetron sputtering technique for flexible symmetric supercapacitor (FSSC) application. The MoON/SSM flexible electrode manifests remarkable Na+-ion pseudocapacitive kinetics, delivering exceptional ≈881.83 F g-1 capacitance, thanks to the synergistically coupled interfaces and junctions between nanostructures of Mo2N, MoO2, and MoO3 co-existing phases, resulting in enhanced specific surface area, increased electroactive sites, improved ionic and electronic conductivity. Employing 3D Bode plots, b-value, and Dunn's analysis, a comprehensive insight into the charge-storage mechanism has been presented, revealing the superiority of surface-controlled capacitive and pseudocapacitive kinetics. Utilizing PVA-Na2SO4 gel electrolyte, the assembled all-solid-state FSSC (MoON/SSM||MoON/SSM) exhibits impressive cell capacitance of 30.7 mF cm-2 (438.59 F g-1) at 0.125 mA cm-2. Moreover, the FSSC device outputs a superior energy density of 4.26 µWh cm-2 (60.92 Wh kg-1) and high power density of 2.5 mW cm-2 (35.71 kW kg-1). The device manifests remarkable flexibility and excellent electrochemical cyclability of ≈91.94% over 10,000 continuous charge-discharge cycles. These intriguing pseudocapacitive performances combined with lightweight, cost-effective, industry-feasible, and environmentally sustainable attributes make the present MoON-based FSSC a potential candidate for energy-storage applications in flexible electronics.

Extended Plateau Capacity of Hard Carbon Anode for High Energy Lithium-Ion Batteries.

Hard carbon materials have shown promising potential for sodium-ion storage due to accommodating larger sodium ions. However, as for lithium-ion storage, the challenge lies in tuning the high lithiation plateau capacities, which impacts the overall energy density. Here, hard carbon microspheres (HCM) are prepared by tailoring the cross-linked polysaccharide, establishing a comprehensive methodology to obtain high-performance lithium-ion batteries (LIBs) with long plateau capacities. The "adsorption-intercalation mechanism" for lithium storage is revealed combining in situ Raman characterization and ex situ nuclear magnetic resonance spectroscopy. The optimized HCM possesses reduced defect content, enriched graphitic microcrystalline, and low specific surface area, which is beneficial for fast lithium storage. Therefore, HCM demonstrates a high reversible capacity of 537 mAh g-1 with a significant low-voltage plateau capacity ratio of 55%, high initial Coulombic efficiency, and outstanding rate performance (152 mAh g-1 at 10 A g-1). Moreover, the full cell (HCM||LiCoO2) delivers outstanding fast-charging capability (4 min charge to 80% at 10 C) and impressive energy density of 393 Wh kg-1. Additionally, 80% reversible capacity can be delivered under -40 °C with competitive cycling stability. This work provides in-depth insights into the rational design of hard carbon structures with extended low-voltage plateau capacity for high energy LIBs.

Ultra-thin and Mechanically Stable LiCoO2-Electrolyte Interphase Enabled by Mg2+ Involved Electrolyte.

LiCoO2 (LCO) cathode materials have attracted significant attention for its potential to provide higher energy density in current Lithium-ion batteries (LIBs). However, the structure and performance degradation are exacerbated by increasing voltage due to the catastrophic reaction between the applied electrolyte and delithiated LCO. The present study focuses on the construction of physically and chemically robust Mg-integrated cathode-electrolyte interface (MCEI) to address this issue, by incorporating Magnesium bis(trifluoromethanesulfonyl)imide (Mg[TFSI]2) as an electrolyte additive. During formation cycles, the strong MCEI is formed and maintained its 2 nm thickness throughout long-term cycling. Notably, Mg is detected not only in the robust MCEI, but also imbedded in the surface of the LCO lattice. As a result, the parasitic interfacial side reactions, surface phase reconstruction, particle cracking, Co dissolution and shuttling are considerably suppressed, resulting in long-term cycling stability of LCO up to 4.5 V. Therefore, benefit from the double protection of the strong MCEI, the Li||LCO coin cell and the Ah-level Graphite||LCO pouch cell exhibit high capacity retention by using Mg-electrolyte, which are 88.13% after 200 cycles and 90.4% after 300 cycles, respectively. This work provides a novel approach for the rational design of traditional electrolyte additives.

In Situ Forming Gel Polymer Electrolyte for High Energy-Density Lithium Metal Batteries.

In situ forming gel polymer electrolyte (GPE) is one of the most feasible ways to improve the safety and cycle performances of lithium metal batteries with high energy density. However, most of the in situ formed GPEs are not compatible with high-voltage cathode materials. Here, this work provides a novel strategy to in situ form GPE based on the mechanism of Ritter reaction. The Ritter reaction in liquid electrolyte has the advantage of appropriate reaction temperature and no additional additives. The polymer chains are cross-linked by amide groups with the formation of GPE with superior electrochemical properties. The GPE has high ionic conductivity (1.84 mS cm-1 ), wide electrochemical stability window (>5.25 V) and high lithium ion transference number (≈0.78), compatible with high-voltage cathode materials. The Li|LiNi0.6 Co0.2 Mn0.2 O2 batteries with in situ formed GPE show excellent long-term cycle stability (93.4%, 300 cycles). The density functional theory calculation and X-ray photoelectron spectroscopy results verify that the amide and nitrile groups are beneficial for stabilizing cathode structure and promoting uniform Li deposition on Li anode. Furthermore, the in situ formed GPE exhibits excellent electrochemical performance in Graphite|LiMn2 O4 and Graphite|LiNi0.5 Co0.2 Mn0.3 O2 pouch batteries. This approach is adaptable to current battery technologies, which will be sure to promote the development of high energy-density lithium-ion batteries.

Architecting the Microenvironment Skeleton of Active Materials in High-Capacity Electrodes by Self-Assembled Nano-Building Blocks.

In analogy to the cell microenvironment in biology, understanding and controlling the active-material microenvironment (ME@AM) microstructures in battery electrodes is essential to the successes of energy storage devices. However, this is extremely difficult for especially high-capacity active materials (AMs) like sulfur, due to the poor controlling on the electrode microstructures. To conquer this challenge, here, a semi-dry strategy based on self-assembled nano-building blocks is reported to construct nest-like robust ME@AM skeleton in a solvent-and-stress-less way. To do that, poly(vinylidene difluoride) nanoparticle binder is coated onto carbon-nanofibers (NB@CNF) via the nanostorm technology developed in the lab, to form self-assembled nano-building blocks in the dry slurry. After compressed into an electrode prototype, the self-assembled dry-slurry is then bonded by in-situ nanobinder solvation. With this strategy, mechanically strong thick sulfur electrodes are successfully fabricated without cracking and exhibit high capacity and good C-rate performance even at a high AM loading (25.0 mg cm-2 by 90 wt% in the whole electrode). This study may not only bring a promising solution to dry manufacturing of batteries, but also uncover the ME@AM structuring mechanism with nano-binder for guiding the design and control on electrode microstructures.

Synthesis, Characterization and Energetic Properties of Hydroxymethyl-Bishomocubanone Derivatives.

The present work reports synthesis, characterization and theoretical insights on novel hydroxymethyl-bishomocubanone derivatives. Twelve new bishomocubanes (BHCs) were synthesized and fully characterized by various spectroscopic techniques and single crystal X-ray analysis. The densities of the title compounds were in the range of 1.30-1.59 g/cm3. Density-functional theory (DFT) based calculations at B3LYP/6-311++G(d,p) level of theory were performed on ten selected BHC based cage compounds. Propulsive and ballistic properties of newly synthesized hydroxymethyl-bishomocubanone derivatives in solid and liquid propulsion systems were calculated, and the results suggested that these compounds are superior to conventional fuel RP1 and binder HTPB. The detonation parameters revealed that these compounds are not explosive in nature and safe to use as solid propellants. Furthermore, kinetic and thermal stabilities of the title compounds were determined by HOMO-LUMO energy gap, ESP maps, impact sensitivity (h50) and bond dissociation energies (BDEs) followed by thermogravimetric analysis (TGA) and differential thermal analysis (DTA). Three compounds, a dinitroazide (Isp,vac=310.98 s), a dinitrate (Isp,vac=309.51 s), and a dinitronitrate (Isp,vac=309.20s) were found to be excellent candidates for volume limited applications.

Recent Theoretical and Experimental Advancements of Aluminum-Sulfur Batteries.

Aluminum-sulfur batteries (AlSBs) exhibit significant potential as energy storage systems due to their notable attributes, including a high energy density, cost-effectiveness, and abundant availability of aluminum and sulfur. In order to commercialize AlSBs, an understanding of their working principles is necessary. In this review, we examine the current advancements in cathodes, both in theory and practice, as well as the progress made in aqueous and nonaqueous electrolytes. We also explore the modifications made to separators and the theoretical understanding of problems associated with AlSBs. Furthermore, we discuss future research directions aimed at resolving these issues. Our aim is to summarize the current progress in AlSBs and, based on recent progress and understanding of the mechanism, help design a battery to overcome the challenges that such batteries have been facing.

Resolving Deactivation of Low-Spin Fe Sites by Redistributing Electron Density toward High-Energy Sodium Storage.

Prussian blue (PB) has been an emerging class of cathode material for sodium-ion batteries due to its low cost and high theoretical capacity. However, their working voltage and capacity are substantially restricted due to the deactivation of low-spin Fe sites. Herein, we demonstrate a universal strategy to activate the low-spin Fe sites of PB by hybridizing them with the π-π conjugated electronic conductors. The redistribution of electron density between π-π conjugated conductors and PB effectively promotes the participation of low-spin Fe sites in sodium storage. Consequently, the low-spin Fe-induced plateau is greatly aroused, resulting in a high specific capacity of 148.4 mAh g-1 and remarkable energy density of 444.2 Wh kg-1. In addition, the excellent structural stability enables superior cycling stability over 2500 cycles and outstanding rate performance. The work will provide fundamental insight into activating the low-spin Fe sites of PB for advanced battery technologies.

Polymethylenetetrazole: Synthesis, Characterization, and Energetic Properties.

The tetrazole moiety remains one of the most interesting scaffolds in the development of new high-energy density materials (HEDMs) because of its desired characteristics, such as high nitrogen content and heat of formation (HOF). The combination of several heterocycles with high HOF seems to be a promising strategy for obtaining energetic materials with superior properties. Herein, we report the synthesis and characterization of a tetrazole polymer, polymethylenetetrazole (PMT), as a potential HEDM. The compound was characterized using NMR, IR, and Raman spectroscopy. Its weight average molecular mass was obtained by static light scattering (SLS), and its physical properties by powder XRD analysis. The density, sensitivity to friction (FS), and impact (IS) of the compound were determined as well. The results of the thermal and energetic properties of PMT suggest that this polymer could be an insensitive explosive.

A High-Energy Aqueous All-Sulfur Battery.

Rechargeable aqueous batteries are promising energy storage devices because of their high safety and low cost. However, their energy densities are generally unsatisfactory due to the limited capacities of ion-inserted electrode materials, prohibiting their widespread applications. Herein, a high-energy aqueous all-sulfur battery was constructed via matching S/Cu2 S and S/CaSx redox couples. In such batteries, both cathodes and anodes undergo the conversion reaction between sulfur/metal sulfides redox couples, which display high specific capacities and rational electrode potential difference. Furthermore, during the charge/discharge process, the simultaneous redox of Cu2+ ion charge-carriers also takes place and contributes to a more two-electron transfer, which doubles the capacity of cathodes. As a result, the assembled aqueous all-sulfur batteries deliver a high discharge capacity of 447 mAh g-1 based on total mass of sulfur in cathode and anode at 0.1 A g-1 , contributing to an enhanced energy density of 393 Wh kg-1 . This work will widen the scope for the design of high-energy aqueous batteries.

High-Voltage Catholyte for High-Energy-Density Nonaqueous Redox Flow Battery.

Redox flow batteries (RFBs) with high energy densities are essential for efficient and sustainable long-term energy storage on a grid scale. To advance the development of nonaqueous RFBs with high energy densities, a new organic RFB system employing a molecularly engineered tetrathiafulvalene derivative ((PEG3/PerF)-TTF) as a high energy density catholyte was developed. When paired with a lithium metal anode, the two-electron-active (PEG3/PerF)-TTF catholyte produced a cell voltage of 3.56 V for the first reduction and 3.92 V for the second reduction process. In cyclic voltammetry and flow cell tests, the redox chemistry exhibited excellent cycling stability. The Li|(PEG3/PerF)-TTF batteries, with concentrations of 0.1 M and 0.5 M, demonstrated capacity retention rates of ~94% (99.87% per cycle, 97.52% per day) and 90% (99.93% per cycle, 99.16% per day), and the average Coulombic efficiencies of 99.38% and 98.35%, respectively. The flow cell achieved a high power density of 129 mW/cm2. Furthermore, owing to the high redox potential and solubility of (PEG3/PerF)-TTF, the flow cell attained a high operational energy density of 72 Wh/L (100 Wh/L theoretical). A 0.75 M flow cell exhibited an even higher operational energy density of 96 Wh/L (150 Wh/L theoretical).