Suppressing metal corrosion through identification of optimal crystallographic plane for Zn batteries.

Direct use of metals as battery anodes could significantly boost the energy density, but suffers from limited cycling. To make the batteries more sustainable, one strategy is mitigating the propensity for metals to form random morphology during plating through orientation regulation, e.g., hexagonal Zn platelets locked horizontally by epitaxial electrodeposition or vertically aligned through Zn/electrolyte interface modulation. Current strategies center around obtaining (002) faceted deposition due to its minimum surface energy. Here, benefiting from the capability of preparing a library of faceted monocrystalline Zn anodes and controlling the orientation of Zn platelet deposits, we challenge this conventional belief. We show that while monocrystalline (002) faceted Zn electrode with horizontal epitaxy indeed promises the highest critical current density, the (100) faceted electrode with vertically aligned deposits is the most important one in suppressing Zn metal corrosion and promising the best reversibility. Such uniqueness results from the lowest electrochemical surface area of (100) faceted electrode, which intrinsically builds upon the surface atom diffusion barrier and the orientation of the pallets. These new findings based on monocrystalline anodes advance the fundamental understanding of electrodeposition process for sustainable metal batteries and provide a paradigm to explore the processing-structure-property relationships of metal electrodes.

Reconstructable Carbon Monolayer-MoS2 Intercalated Heterostructure Enabled by Atomic Layers-Confined Topotactic Transformation for Ultrafast Lithium Storage.

The intercalation structure of two-dimensional materials with expanded interlayer distance can facilitate mass transport, which is promising in fast-charging lithium-ion batteries (LIBs). However, the designed intercalation structures will be pulverized and destroyed under tough working conditions, causing overall performance deterioration of the batteries. Here, we present that an intercalated heterostructure made of the typical layered material of MoS2 intercalated by N-doped graphene-like carbon monolayer (MoS2/g-CM) through a polymer intercalation strategy exhibits a unique behavior of reversible reconstructability as an LIB anode during cycling. A mechanism of "carbon monolayers-confined topotactic transformation" is proposed, which is evidenced by substantial in/ex situ characterizations. The intercalated heterostructure of MoS2/g-CM featuring a reconstructable property and efficient interlayer electron/ion transport exhibits an unprecedented rate capability up to 50 A g-1 and outstanding long cyclability. Moreover, the proposed strategy based on g-CM intercalation has been extended to the MoSe2 system, also realizing reconstructability of the intercalated heterostructure and improved LIB performance, demonstrating its versatility and great potential in applications.

Boosted Mg-CO2 Batteries by Amine-Mediated CO2 Capture Chemistry and Mg2+ -Conducting Solid-electrolyte Interphases.

Mg-CO2 battery has been considered as an ideal system for energy conversion and CO2 fixation. However, its practical application is significantly limited by the poor reversibility and sluggish kinetics of CO2 cathode and Mg anode. Here, a new amine mediated chemistry strategy is proposed to realize a highly reversible and high-rate Mg-CO2 battery in conventional electrolyte. Judiciously combined experimental characterization and theoretical computation unveiled that the introduced amine could simultaneously modify the reactant state of CO2 and Mg2+ to accelerate CO2 cathodic reactions on the thermodynamic-kinetic levels and facilitate the formation of Mg2+ -conductive solid-electrolyte interphase (SEI) to enable highly reversible Mg anode. As a result, the Mg-CO2 battery exhibits boosted stable cyclability (70 cycles, more than 400 h at 200 mA g-1 ) and high-rate capability (from 100 to 2000 mA g-1 with 1.5 V overpotential) even at -15 °C. This work opens a newly promising avenue for advanced metal-CO2 batteries.

Space-Confined Atomic Clusters Catalyze Superassembly of Silicon Nanodots within Carbon Frameworks for Use in Lithium-Ion Batteries.

Incorporating nanoscale Si into a carbon matrix with high dispersity is desirable for the preparation of lithium-ion batteries (LIBs) but remains challenging. A space-confined catalytic strategy is proposed for direct superassembly of Si nanodots within a carbon (Si NDs⊂C) framework by copyrolysis of triphenyltin hydride (TPT) and diphenylsilane (DPS), where Sn atomic clusters created from TPT pyrolysis serve as the catalyst for DPS pyrolysis and Si catalytic growth. The use of Sn atomic cluster catalysts alters the reaction pathway to avoid SiC generation and enable formation of Si NDs with reduced dimensions. A typical Si NDs⊂C framework demonstrates a remarkable comprehensive performance comparable to other Si-based high-performance half LIBs, and higher energy densities compared to commercial full LIBs, as a consequence of the high dispersity of Si NDs with low lithiation stress. Supported by mechanic simulations, this study paves the way for construction of Si/C composites suitable for applications in future energy technologies.

In Situ Observation and Electrochemical Study of Encapsulated Sulfur Nanoparticles by MoS2 Flakes.

Sulfur is an attractive cathode material for next-generation lithium batteries due to its high theoretical capacity and low cost. However, dissolution of its lithiated product (lithium polysulfides) into the electrolyte limits the practical application of lithium sulfur batteries. Here we demonstrate that sulfur particles can be hermetically encapsulated by leveraging on the unique properties of two-dimensional materials such as molybdenum disulfide (MoS2). The high flexibility and strong van der Waals force in MoS2 nanoflakes allows effective encapsulation of the sulfur particles and prevent its sublimation during in situ TEM studies. We observe that the lithium diffusivities in the encapsulated sulfur particles are in the order of 10-17 m2 s-1. Composite electrodes made from the MoS2-encapsulated sulfur spheres show outstanding electrochemical performance, with an initial capacity of 1660 mAh g-1 and long cycle life of more than 1000 cycles.

Direct Superassemblies of Freestanding Metal-Carbon Frameworks Featuring Reversible Crystalline-Phase Transformation for Electrochemical Sodium Storage.

High-power sodium-ion batteries (SIBs) with long-term cycling attract increasing attention for large-scale energy storage. However, traditional SIBs toward practical applications still suffer from low rate capability and poor cycle induced by pulverization and amorphorization of anodes at high rate (over 5 C) during the fast ion insertion/extraction process. The present work demonstrates a robust strategy for a variety of (Sb-C, Bi-C, Sn-C, Ge-C, Sb-Bi-C) freestanding metal-carbon framework thin films via a space-confined superassembly (SCSA) strategy. The sodium-ion battery employing the Sb-C framework exhibits an unprecedented performance with a high specific capacity of 246 mAh g-1, long life cycle (5000 cycles), and superb capacity retention (almost 100%) at a high rate of 7.5 C (3.51A g-1). Further investigation indicates that the unique framework structure enables unusual reversible crystalline-phase transformation, guaranteeing the fast and long-cyclability sodium storage. This study may open an avenue to developing long-cycle-life and high-power SIBs for practical energy applications.

Probing lithium germanide phase evolution and structural change in a germanium-in-carbon nanotube energy storage system.

Lithium alloys of group IV elements such as silicon and germanium are attractive candidates for use as anodes in high-energy-density lithium-ion batteries. However, the poor capacity retention arising from volume swing during lithium cycling restricts their widespread application. Herein, we report high reversible capacity and superior rate capability from core-shell structure consisting of germanium nanorods embedded in multiwall carbon nanotubes. To understand how the core-shell structure helps to mitigate volume swings and buffer against mechanical instability, transmission electron microscopy, X-ray diffraction, and in situ (7)Li nuclear magnetic resonance were used to probe the structural rearrangements and phase evolution of various Li-Ge alloy phases during (de)alloying reactions with lithium. The results provide insights into amorphous-to-crystalline transition and lithium germanide alloy phase transformation, which are important reactions controlling performance in this system.

Effect of NiO Addition on the Sintering and Electrochemical Properties of BaCe0.55Zr0.35Y0.1O3-δ Proton-Conducting Ceramic Electrolyte.

Proton ceramic fuel cells offer numerous advantages compared with conventional fuel cells. However, the practical implementation of these cells is hindered by the poor sintering activity of the electrolyte. Despite extensive research efforts to improve the sintering activity of BCZY, the systematic exploration of the utilization of NiO as a sintering additive remains insufficient. In this study, we developed a novel BaCe0.55Zr0.35Y0.1O3-δ (BCZY) electrolyte and systematically investigated the impact of adding different amounts of NiO on the sintering activity and electrochemical performance of BCZY. XRD results demonstrate that pure-phase BCZY can be obtained by sintering the material synthesized via solid-state reaction at 1400 °C for 10 h. SEM analysis revealed that the addition of NiO has positive effects on the densification and grain growth of BCZY, while significantly reducing the sintering temperature required for densification. Nearly fully densified BCZY ceramics can be obtained by adding 0.5 wt.% NiO and annealing at 1350 °C for 5 h. The addition of NiO exhibits positive effects on the densification and grain growth of BCZY, significantly reducing the sintering temperature required for densification. An anode-supported full cell using BCZY with 0.5 wt.% NiO as the electrolyte reveals a maximum power density of 690 mW cm-2 and an ohmic resistance of 0.189 Ω cm2 at 650 °C. Within 100 h of long-term testing, the recorded current density remained relatively stable, demonstrating excellent electrochemical performance.

A Redox-Active Covalent Organic Framework with Highly Accessible Aniline-Fused Quinonoid Units Affords Efficient Proton Charge Storage.

Owing to their intrinsic safety and sustainability, aqueous proton batteries have emerged as promising energy devices. Nevertheless, the corrosion or dissolution of electrode materials in acidic electrolytes must be addressed before practical applications. In this study, a cathode material based on a redox-active 2D covalent organic framework (TPAD-COF) with aniline-fused quinonoid units featuring inherently regular open porous channels and excellent stability is developed. The TPAD-COF cathode delivers a high capacity of 126 mAh g-1 at 0.2 A g-1 , paired with long-term cycling stability with capacity retention of 84% after 5000 cycles at 2 A g-1 . Comprehensive ex situ spectroscopy studies correlated with density functional theory (DFT) calculations reveal that both the -NH- and C=O groups of the aniline-fused quinonoid units exhibit prominent redox activity of six electrons during the charge/discharge processes. Furthermore, the assembled punch battery consisting of a TPAD-COF//anthraquinone (AQ) all-organic system delivers a discharge capacity of 115 mAh g-1 at 0.5 A g-1 after 130 cycles, implying the potential application of the TPAD-COF cathode in aqueous proton batteries. This study provides a new perspective on the design of electrode materials for aqueous proton batteries with long-term cycling performance and high capacity.

Temperature-dependent interphase formation and Li+ transport in lithium metal batteries.

High-performance Li-ion/metal batteries working at a low temperature (i.e., <-20 °C) are desired but hindered by the sluggish kinetics associated with Li+ transport and charge transfer. Herein, the temperature-dependent Li+ behavior during Li plating is profiled by various characterization techniques, suggesting that Li+ diffusion through the solid electrolyte interface (SEI) layer is the key rate-determining step. Lowering the temperature not only slows down Li+ transport, but also alters the thermodynamic reaction of electrolyte decomposition, resulting in different reaction pathways and forming an SEI layer consisting of intermediate products rich in organic species. Such an SEI layer is metastable and unsuitable for efficient Li+ transport. By tuning the solvation structure of the electrolyte with a lower lowest unoccupied molecular orbital (LUMO) energy level and polar groups, such as fluorinated electrolytes like 1 mol L-1 lithium bis(fluorosulfonyl)imide (LiFSI) in methyl trifluoroacetate (MTFA): fluoroethylene carbonate (FEC) (8:2, weight ratio), an inorganic-rich SEI layer more readily forms, which exhibits enhanced tolerance to a change of working temperature (thermodynamics) and improved Li+ transport (kinetics). Our findings uncover the kinetic bottleneck for Li+ transport at low temperature and provide directions to enhance the reaction kinetics/thermodynamics and low-temperature performance by constructing inorganic-rich interphases.

Actualizing a High-Energy Bipolar-Stacked Solid-State Battery with Low-Cost Mechanically Robust Nylon Mesh-Reinforced Composite Polymer Electrolyte Membranes.

To meet the rapidly growing and diversified demand for energy storage, advanced rechargeable batteries with high-performance materials and efficient battery configuration are widely being exploited and developed. Bipolar-stacked electrode coupling with solid-state electrolytes enables achieving batteries with high output voltage, high energy density, and simple components. Here, a polymer electrolyte membrane is designed with polyethylene oxide containing bis(trifluoromethanesulfonyl)-imide as the electrolyte, succinonitrile as the plasticizer, and nylon mesh as a reinforcement for the bipolar-stacked battery. The as-prepared nylon mesh-reinforced polymer electrolyte membrane shows advantageous features, that is, excellent ionic conductivity (3.38 × 10-4 S cm-1) at room temperature, low interface impedance, and good tolerance against the expansion caused by the plating/stripping of the Li anode and the electrode upon cycling. When used as a polymer electrolyte membrane in the bipolar-stacked battery, the LiFePO4(LFP)-Li4Ti5O12(LTO) cell with three cells connected in series delivers a higher discharge voltage (5.4 V) and a volumetric energy density (0.328 mW h cm-3), nearly 3 times as much as that of the LFP-LTO battery. In addition, LiFePO4-Li pouch cells using the polymer electrolyte membrane can sustain the abuse tests including bending, cutting, and nail penetration well. These results pave a new avenue to develop high-performance polymer electrolyte membranes and allow for the design of high-voltage and volumetric energy density bipolar-stacked batteries.

Lithiated Sulfur-Incorporated, Polymeric Cathode for Durable Lithium-Sulfur Batteries with Promoted Redox Kinetics.

Even though lithium-sulfur (Li-S) batteries have made much progress in terms of the delivered specific capacity and cycling stability by the encapsulation of sulfur within conductive carbon matrixes or polar materials, challenges such as low active sulfur utilization and unacceptable Coulombic efficiency are still hindering their commercial use. Herein, a lithium-rich conjugated sulfur-incorporated, polymeric material based on poly(Li2S6-r-1,3-diisopropenylbenzene) (DIB) is developed as a cathode material for high rate and stable Li-S batteries. Motivated by extra Li+ ions affording fast Li+ redox kinetics across the conjugated aromatic backbones, the Li-rich sulfur-based copolymer exhibits high delivery capacities (934 mAh g-1 at 120 cycles), impressive rate capabilities (727 mAh g-1 even under a current of 2 A g-1), and long electrochemical cycling performance over 500 cycles. Moreover, by use of the elastic nature and thermoplastic properties of the sulfur-incorporated, polymeric material, a prototype of a flexible Li-S pouch cell is constructed by using a poly(Li2S6-r-DIB) copolymer cathode and paired with the flexible carbon cloth/Si/Li anode, which exhibits stable electrochemical performance (658 mAh g-1 after 100 cycles) and operational capability even under folding at various angle (30°, 60°, 90°, 120°, 150°, 180°). This work extends the molecular-design approach to obtaining a high-performance organosulfur cathode material by introducing extra Li+ ions to promote redox kinetics, which provides valuable guidance for the development of high-performance Li-S batteries for practical applications.

A Bifunctional-Modulated Conformal Li/Mn-Rich Layered Cathode for Fast-Charging, High Volumetric Density and Durable Li-Ion Full Cells.

Lithium- and manganese-rich (LMR) layered cathode materials hold the great promise in designing the next-generation high energy density lithium ion batteries. However, due to the severe surface phase transformation and structure collapse, stabilizing LMR to suppress capacity fade has been a critical challenge. Here, a bifunctional strategy that integrates the advantages of surface modification and structural design is proposed to address the above issues. A model compound Li1.2Mn0.54Ni0.13Co0.13O2 (MNC) with semi-hollow microsphere structure is synthesized, of which the surface is modified by surface-treated layer and graphene/carbon nanotube dual layers. The unique structure design enabled high tap density (2.1 g cm-3) and bidirectional ion diffusion pathways. The dual surface coatings covalent bonded with MNC via C-O-M linkage greatly improves charge transfer efficiency and mitigates electrode degradation. Owing to the synergistic effect, the obtained MNC cathode is highly conformal with durable structure integrity, exhibiting high volumetric energy density (2234 Wh L-1) and predominant capacitive behavior. The assembled full cell, with nanographite as the anode, reveals an energy density of 526.5 Wh kg-1, good rate performance (70.3% retention at 20 C) and long cycle life (1000 cycles). The strategy presented in this work may shed light on designing other high-performance energy devices.

Horizontally arranged zinc platelet electrodeposits modulated by fluorinated covalent organic framework film for high-rate and durable aqueous zinc ion batteries.

Rechargeable aqueous zinc-ion batteries (RZIBs) provide a promising complementarity to the existing lithium-ion batteries due to their low cost, non-toxicity and intrinsic safety. However, Zn anodes suffer from zinc dendrite growth and electrolyte corrosion, resulting in poor reversibility. Here, we develop an ultrathin, fluorinated two-dimensional porous covalent organic framework (FCOF) film as a protective layer on the Zn surface. The strong interaction between fluorine (F) in FCOF and Zn reduces the surface energy of the Zn (002) crystal plane, enabling the preferred growth of (002) planes during the electrodeposition process. As a result, Zn deposits show horizontally arranged platelet morphology with (002) orientations preferred. Furthermore, F-containing nanochannels facilitate ion transport and prevent electrolyte penetration for improving corrosion resistance. The FCOF@Zn symmetric cells achieve stability for over 750 h at an ultrahigh current density of 40 mA cm-2. The high-areal-capacity full cells demonstrate hundreds of cycles under high Zn utilization conditions.

Initiating a Reversible Aqueous Zn/Sulfur Battery through a "Liquid Film".

Sulfur cathodes have been under intensive study in various systems, such as Li/S, Na/S, Mg/S, and Al/S batteries. However, to date, Zn/S chemistry has never been reported. The first reliable aqueous Zn/polysulfide system activated by a "liquid film" comprising 4-(3-butyl-1-imidazolio)-1-butanesulfoni ionic liquid (IL) encapsulated within PEDOT:PSS. CF3 SO3 - anions in the IL operating as Zn2+ -transfer channels is reported. Moreover, the PEDOT:PSS network retains the IL, which renders Zn2+ -transfer channels and a polysulfide cathode with enhanced structural stability. The Zn/polysulfide system delivers extraordinary capacity of 1148 mAh g-1 and overwhelming energy density of 724.7 Wh kg-1 cathode at 0.3 Ag-1 . During the discharging phase, S6 2- is dominantly reduced by Zn to S2- (S6   →  S2- ). During the charging phase, these short chains are oxidized to form long-chain Znx Liy S3-6 . A further optimized high-concentrated salt electrolyte is used to improve the reversibility of the battery, demonstrating an extended lifetime over 1600 cycles at 1 Ag-1 with a capacity retention of 204 mAh g-1 . This facile approach and the superior performance of the developed aqueous Zn/S chemistry provide a new platform for sulfur-based battery and potentially solve the problems of other metal/sulfur batteries.

3D Lithiophilic "Hairy" Si Nanowire Arrays @ Carbon Scaffold Favor a Flexible and Stable Lithium Composite Anode.

Lithium metal anode is considered to be a promising candidate for high-energy-density lithium-based batteries. However, the safety issue induced by uncontrollable dendrite growth hinders the commercialization of a Li anode. Herein, self-supported three-dimensional flexible carbon cloth covered with a lithiophilic silicon nanowire array is constructed as the host for loading of molten Li to achieve the C/SiNW/Li composite anode. The electrode component of the carbon cloth provides the flexible and conductive substrate to accommodate the volume change during the stripping/plating of Li and facilitate more efficient electron transport, while silicon nanowires improve the wettability of the carbon host to liquefied Li and render uniform Li deposition on the surface of the composite electrode. The as-prepared C/SiNW/Li composite anode exhibits enhanced cycling stability with a low hysteresis of 40 mV for more than 200 h and a better rate tolerance even at a current density of up to 5 mA cm-2. When coupling with the LiNi0.5Mn1.5O4 cathode, the full cells using the C/SiNW/Li composite anode demonstrate a remarkable electrochemical performance with an exceptional rate performance of up to 10 C and stable long-term cycling (the capacity retention of 62% at a 5 C rate over 2000 cycles), which is much higher than the cells with pure Li anode. This work provides a universal strategy to fabricate the flexible and stable carbon-based Li metal anode toward high-energy-density batteries.

A polymer-direct-intercalation strategy for MoS2/carbon-derived heteroaerogels with ultrahigh pseudocapacitance.

The intercalation strategy has become crucial for 2D layered materials to achieve desirable properties, however, the intercalated guests are often limited to metal ions or small molecules. Here, we develop a simple, mild and efficient polymer-direct-intercalation strategy that different polymers (polyethyleneimine and polyethylene glycol) can directly intercalate into the MoS2 interlayers, forming MoS2-polymer composites and interlayer-expanded MoS2/carbon heteroaerogels after carbonization. The polymer-direct-intercalation behavior has been investigated by substantial characterizations and molecular dynamic calculations. The resulting composite heteroaerogels possess 3D conductive MoS2/C frameworks, expanded MoS2 interlayers (0.98 nm), high MoS2 contents (up to 74%) and high Mo valence (+6), beneficial to fast and stable charge transport and enhanced pseudocapacitive energy storage. Consequently, the typical MoS2/N-doped carbon heteroaerogels exhibit outstanding supercapacitor performance, such as ultrahigh capacitance, remarkable rate capability and excellent cycling stability. This study offers a new intercalation strategy which may be generally applicable to 2D materials for promising energy applications.

Hybrid Anatase/Rutile Nanodots-Embedded Covalent Organic Frameworks with Complementary Polysulfide Adsorption for High-Performance Lithium-Sulfur Batteries.

The shuttling effect of polysulfides species seriously deteriorates the performance of Li-S batteries, representing the major obstacle for their practical use. However, the exploration of ideal cathodes that can suppress the shuttling of all polysulfides species is challenging. Herein, we propose an ingenious and effective strategy for constructing hybrid-crystal-phase TiO2/covalent organic framework (HCPT@COF) composites where hybrid anatase/rutile TiO2 nanodots (10 nm) are uniformly embedded in the interlayers of porous COFs. The synthesis was realized via a multiple-step reaction relay accompanying by a pseudo-topotactic transformation of three-dimensional layered structures from 1,4-dicyanobenzene monomer-embedded Ti-intermediate networks to HCPT nanodots-embedded COF frameworks. The HCPT@COF/S cathodes show superior comprehensive performance such as high specific capacity, long cycling stability, and remarkable rate capability for Li-S batteries, owing to the complementary anchoring effect of hybrid anatase/rutile TiO2 in the HCPT@COF composite, which is evidenced by substantial characterizations including X-ray photoelectron spectroscopy and density functional theory calculations.

Antipulverization Electrode Based on Low-Carbon Triple-Shelled Superstructures for Lithium-Ion Batteries.

The realization of antipulverization electrode structures, especially using low-carbon-content anode materials, is crucial for developing high-energy and long-life lithium-ion batteries (LIBs); however, this technology remains challenging. This study shows that SnO2 triple-shelled hollow superstructures (TSHSs) with a low carbon content (4.83%) constructed by layer-by-layer assembly of various nanostructure units can withstand a huge volume expansion of ≈231.8% and deliver a high reversible capacity of 1099 mAh g-1 even after 1450 cycles. These values represent the best comprehensive performance in SnO2 -based anodes to date. Mechanics simulations and in situ transmission electron microscopy suggest that the TSHSs enable a self-synergistic structure-preservation behavior upon lithiation/delithiation, protecting the superstructures from collapse and guaranteeing the electrode structural integrity during long-term cycling. Specifically, the outer shells during lithiation processes are fully lithiated, preventing the overlithiation and the collapse of the inner shells; in turn, in delithiation processes, the underlithiated inner shells work as robust cores to support the huge volume contraction of the outer shells; meanwhile, the middle shells with abundant pores offer sufficient space to accommodate the volume change from the outer shell during both lithiation and delithiation. This study opens a new avenue in the development of high-performance LIBs for practical energy applications.