Systematic engineering of BiVO_(4)photoanode for efficient photoelectrochemical water oxidation

BiVO_(4)is one of the most promising photoanode materials for photoelectrochemical(PEC)solar energy conversion,but it still suffers from poor photocurrent density due to insufficient light‐harvesting efficiency(LHE),weak photogenerated charge separation efficiency(Φ_(Sep)),and low water oxidation efficiency(Φ_(OX)).Herein,we tackle these challenges of the BiVO_(4)photoanodes using systematic engineering,including catalysis engineering,bandgap engineering,and morphology engineering.In particular,we deposit a NiCoO_(x)layer onto the BiVO_(4)photoanode as the oxygen evolution catalyst to enhance theΦ_(OX)of Fe‐g‐C_(3)N_(4)/BiVO_(4)for PEC water oxidation,and incorporate Fe‐doped graphite‐phase C_(3)N_(4)(Fe‐g‐C_(3)N_(4))into the BiVO_(4)photoanode to optimize the bandgap and surface areas to subsequently expand the light absorption range of the photoanode from 530 to 690 nm,increase the LHE andΦ_(Sep),and further improve the oxygen evolution reaction activity of the NiCoO_(x)catalytic layer.Consequently,the maximum photocurrent density of the as‐prepared NiCoO_(x)/Fe‐g‐C_(3)N_(4)/BiVO_(4)is remarkably boosted from 4.6 to 7.4 mA cm^(−2).This work suggests that the proposed systematic engineering strategy is exceptionally promising for improving LHE,Φ_(Sep),andΦ_(OX)of BiVO_(4)‐based photoanodes,which will substantially benefit the design,preparation,and large‐scale application of next‐generation high‐performance photoanodes.

Enhancing thermodynamic stability of single-crystal Ni-rich cathode material via a synergistic dual-substitution strategy

Nickel(Ni)-rich cathode materials have become promising candidates for the next-generation electrical vehicles due to their high specific capacity.However,the poor thermodynamic stability(including cyclic performance and safety performance or thermal stability)will restrain their wide commercial application.Herein,a single-crystal Ni-rich Li Ni_(0.83)Co_(0.12)Mn_(0.05)O_(2) cathode material is synthesized and modified by a dual-substitution strategy in which the high-valence doping element improves the structural stability by forming strong metal–oxygen binding forces,while the low-valence doping element eliminates high Li^(+)/Ni^(2+)mixing.As a result,this synergistic dual substitution can effectively suppress H2-H3 phase transition and generation of microcracks,thereby ultimately improving the thermodynamic stability of Ni-rich cathode material.Notably,the dual-doped Ni-rich cathode delivers an extremely high capacity retention of 81%after 250 cycles(vs.Li/Li+)in coin-type half cells and 87%after 1000 cycles(vs.graphite/Li^(+))in pouch-type full cells at a high temperature of 55℃.More impressively,the dual-doped sample exhibits excellent thermal stability,which demonstrates a higher thermal runaway temperature and a lower calorific value.The synergetic effects of this dual-substitution strategy pave a new pathway for addressing the critical challenges of Ni-rich cathode at high temperatures,which will significantly advance the high-energy-density and high-safety cathodes to the subsequent commercialization.

Green and scalable electrochemical routes for cost‐effective mass production of MXenes for supercapacitor electrodes

One of the most unique properties of two-dimensional carbides and nitrides of transition metals(MXenes)is their excellent water dispersibility and yet possessing superior electrical conductivity but their industrial-scale application is limited by their costly chemical synthesis methods.In this work,the niche feature of MXenes was capitalized in the packed-bed electrochemical reactor to produce MXenes at an unprecedented reaction rate and yield with minimal chemical waste.A simple NH4F solution was employed as the green electrolyte,which could be used repeatedly without any loss in its efficacy.Surprisingly,both fluoride and ammonium were found to play critical roles in the electrochemical etching,functionalization,and expansion of the layered parent materials(MAXs)through which the liberation of ammonia gas was observed.The electrochemically produced MXenes with excellent conductivity,applied as supercapacitor electrodes,could deliver an ultrahigh volumetric capacity(1408 F cm^(−3))and a volumetric energy density(75.8 Wh L^(−1)).This revolutionary green,energy-efficient,and scalable electrochemical route will not only pave the way for industrial-scale production of MXenes but also open up a myriad of versatile electrochemical modifications for improved functional MXenes.

Low-strain Co-free Li-rich layered cathode with excellent voltage and capacity stability

Owing to the inherent advantages of low cost and high capacity,cobalt(Co)-free lithium(Li)-rich layered oxides have become one of the most promising cathodes for next-generation high-energy lithium-ion batteries.However,these familial cathodes suffer from serious voltage decay due to many reasons,such as oxygen release and transition metal(TM)migration,which are closely related to nanoscale strain evolution.Here,by combining the synergistic effects of surface integration,bulk doping,and concentration gradient,we successfully construct a Co-free Li-rich layered cathode with a very small volumetric strain(1.05%)between 2.0 and 4.8 V,approaching the critical value of zero strain.Various characterizations indicate that the constructed zero-strain cathode can significantly suppress the TM migration,interfacial reactions,and structural degradation including cracks,lattice defects,phase evolution,and nanovoids,leading to improved voltage stability of Co-free Li-rich layered oxides during the prolonged cycles.This work provides a strategy to eliminate the lattice strain of Li-rich layered cathodes and facilitates the up-scaled application of the as-prepared cathode materials.

Strategies for Sustainable Production of Hydrogen Peroxide via Oxygen Reduction Reaction:From Catalyst Design to Device Setup

An environmentally benign,sustainable,and cost-effective supply of H_(2)O_(2)as a rapidly expanding consumption raw material is highly desired for chemical industries,medical treatment,and household disinfection.The electrocatalytic production route via electrochemical oxygen reduction reaction(ORR)offers a sustainable avenue for the onsite production of H_(2)O_(2)from O2 and H2O.The most crucial and innovative part of such technology lies in the availability of suitable electrocatalysts that promote two-electron(2e^(–))ORR.In recent years,tremendous progress has been achieved in designing efficient,robust,and cost-effective catalyst materials,including noble metals and their alloys,metalfree carbon-based materials,single-atom catalysts,and molecular catalysts.Meanwhile,innovative cell designs have significantly advanced electrochemical applications at the industrial level.This review summarizes fundamental basics and recent advances in H_(2)O_(2)production via 2e^(–)-ORR,including catalyst design,mechanistic explorations,theoretical computations,experimental evaluations,and electrochemical cell designs.Perspectives on addressing remaining challenges are also presented with an emphasis on the large-scale synthesis of H_(2)O_(2)via the electrochemical route.

二次电池研究进展

能源的存储和利用是当今科学和技术发展中的重大课题之一,尤其是作为高效的电能/化学能转化装置的二次电池相关技术一直是科学家研究的热点领域。在此背景下,本文较为系统地介绍目前二次电池的重要研究进展,将从二次电池的发展历史引入,再到其相关的基础理论知识的介绍。随后较为详细地讨论当前不同体系的二次电池及相关应的关键材料的研究进展,涉及到锂离子电池、钠离子电池、钾离子电池、镁离子电池、锌离子电池、钙离子电池、铝离子电池、氟离子电池、氯离子电池、双离子电池、锂-硫(硒)电池、钠-硫(硒)电池、钾-硫(硒)电池、多价金属-硫基电池、锂-氧电池、钠-氧电池、钾-氧电池、多价金属-氧气电池、锂-溴(碘)电池、水系金属离子电池、光辅助电池、柔性电池、有机电池、金属-二氧化碳电池等。此外,也介绍了电池研究中常见的电极反应过程表征技术,包括冷冻电镜、透射电镜、同步辐射、原位谱学表征、磁性表征等。本文将有助于研究人员对二次电池进行全面系统的了解与把握,并为之后二次电池的研究提供很好的指导作用。

A hydrophilic poly(methyl vinyl ether-alt-maleic acid) polymer as a green, universal, and dual-functional binder for high-performance silicon anode and sulfur cathode

Binders could play crucial or even decisive roles in the fabrication of low-cost, stable and high-capacity electrodes. This is especially the case for the silicon (Si) anodes and sulfur (S) cathodes that undergo large volume change and active material loss in lithium-ion batteries during prolonged cycles. Herein, a hydrophilic polymer poly(methyl vinyl ether-alt-maleic acid) (PMVEMA) was explored as a dual-functional aqueous binder for the preparation of high-performance silicon anode and sulfur cathode. Benefiting from the dual functions of PMVEMA, i.e., the excellent dispersion ability and strong binding forces, the as-prepared electrodes exhibit improved capacity, rate capability and long-term cycling performance. In particular, the as-prepared Si electrode delivers a high initial discharge capacity of 1346.5 mAh g^(−1) at a high rate of 8.4 A/g and maintains 834.5 mAh g^(−1) after 300 cycles at 4.2 A/g, while the as-prepared S cathode exhibits enhanced cycling performance with high remaining discharge capacities of 663.4 mAh g^(−1) after 100 cycles at 0.2 C and 487.07 mAh g^(−1) after 300 cycles at 1 C, respectively. These encouraging results suggest that PMVEMA could be a universal binder to facilitate the green manufacture of both anode and cathode for high-capacity energy storage systems.

Functional additives for solid polymer electrolytes in flexible and high-energy-density solid-state lithium-ion batteries

Solid polymer electrolytes(SPEs)have become increasingly attractive in solid-state lithium-ion batteries(SSLIBs)in recent years because of their inherent properties of flexibility,processability,and interfacial compatibility.However,the commercialization of SPEs remains challenging for flexible and high-energy-density LIBs.The incorporation of functional additives into SPEs could significantly improve the electrochemical and mechanical properties of SPEs and has created some historical milestones in boosting the development of SPEs.In this study,we review the roles of additives in SPEs,highlighting the working mechanisms and functionalities of the additives.The additives could afford significant advantages in boosting ionic conductivity,increasing ion transference number,improving high-voltage stability,enhancing mechanical strength,inhibiting lithium dendrite,and reducing flammability.Moreover,the application of functional additives in high-voltage cathodes,lithium-sulfur batteries,and flexible lithiumion batteries is summarized.Finally,future research perspectives are proposed to overcome the unresolved technical hurdles and critical issues in additives of SPEs,such as facile fabrication process,interfacial compatibility,investigation of the working mechanism,and special functionalities.

Interface Engineering of CoS/CoO@N‑Doped Graphene Nanocomposite for High‑Performance Rechargeable Zn–Air Batteries

Low cost and green fabrication of high-performance electrocatalysts with earth-abundant resources for oxygen reduction reaction(ORR)and oxygen evolution reaction(OER)are crucial for the large-scale application of rechargeable Zn-air batteries(ZABs).In this work,our density functional theory calculations on the electrocatalyst suggest that the rational construction of interfacial structure can induce local charge redistribution,improve the electronic conductivity and enhance the catalyst stability.In order to realize such a structure,we spatially immobilize heterogeneous CoS/CoO nanocrystals onto N-doped graphene to synthesize a bifunctional electrocatalyst(CoS/CoO@NGNs).The optimization of the composition,interfacial structure and conductivity of the electrocatalyst is conducted to achieve bifunctional catalytic activity and deliver outstanding efficiency and stability for both ORR and OER.The aqueous ZAB with the as-prepared CoS/CoO@NGNs cathode displays a high maximum power density of 137.8 mW cm^−2,a specific capacity of 723.9 mAh g^−1 and excellent cycling stability(continuous operating for 100 h)with a high round-trip efficiency.In addition,the assembled quasi-solid-state ZAB also exhibits outstanding mechanical flexibility besides high battery performances,showing great potential for applications in flexible and wearable electronic devices.

Housing Sulfur in Polymer Composite Frameworks for Li–S Batteries

Extensive efforts have been devoted to the design of micro-, nano-, and/or molecular structures of sulfur hosts to address the challenges of lithium–sulfur(Li–S) batteries, yet comparatively little research has been carried out on the binders in Li–S batteries. Herein, we systematically review the polymer composite frameworks that confine the sulfur within the sulfur electrode, taking the roles of sulfur hosts and functions of binders into consideration. In particular, we investigate the binding mechanism between the binder and sulfur host(such as mechanical interlocking and interfacial interactions), the chemical interactions between the polymer binder and sulfur(such as covalent bonding, electrostatic bonding, etc.), as well as the beneficial functions that polymer binders can impart on Li–S cathodes, such as conductive binders, electrolyte intake, adhesion strength etc. This work could provide a more comprehensive strategy in designing sulfur electrodes for long-life, large-capacity and high-rate Li–S battery.

Cyclohexanedodecol-Assisted Interfacial Engineering for Robust and High-Performance Zinc Metal Anode

Aqueous zinc-ion batteries(AZIBs)can be one of the most promising electrochemical energy storage devices for being non-flammable,low-cost,and sustainable.However,the challenges of AZIBs,including dendrite growth,hydrogen evolution,corrosion,and passivation of zinc anode during charging and discharging processes,must be overcome to achieve high cycling performance and stability in practical applications.In this work,we utilize a dual-func-tional organic additive cyclohexanedodecol(CHD)to firstly establish[Zn(H2O)5(CHD)]2+complex ion in an aqueous Zn electrolyte and secondly build a robust protection layer on the Zn surface to overcome these dilemmas.Systematic experiments and theoretical calculations are carried out to interpret the working mechanism of CHD.At a very low concentration of 0.1 mg mL^(−1) CHD,long-term reversible Zn plating/stripping could be achieved up to 2200 h at 2 mA cm^(−2),1000 h at 5 mA cm^(−2),and 650 h at 10 mA cm^(−2) at the fixed capacity of 1 mAh cm^(−2).When matched with V_(2)O_(5) cathode,the resultant AZIBs full cell with the CHD-modified electrolyte presents a high capacity of 175 mAh g^(−1) with the capacity retention of 92%after 2000 cycles under 2 A g^(−1).Such a performance could enable the commercialization of AZIBs for applications in grid energy storage and industrial energy storage.

DFT‑Guided Design and Fabrication of Carbon‑Nitride‑Based Materials for Energy Storage Devices:A Review

Carbon nitrides(including CN,C2N,C3N,C3N4,C4N,and C5N)are a unique family of nitrogen-rich carbon materials with multiple beneficial properties in crystalline structures,morphologies,and electronic configurations.In this review,we provide a comprehensive review on these materials properties,theoretical advantages,the synthesis and modification strategies of different carbon nitride-based materials(CNBMs)and their application in existing and emerging rechargeable battery systems,such as lithium-ion batteries,sodium and potassium-ion batteries,lithium sulfur batteries,lithium oxygen batteries,lithium metal batteries,zinc-ion batteries,and solid-state batteries.The central theme of this review is to apply the theoretical and computational design to guide the experimental synthesis of CNBMs for energy storage,i.e.,facilitate the application of first-principle studies and density functional theory for electrode material design,synthesis,and characterization of different CNBMs for the aforementioned rechargeable batteries.At last,we conclude with the challenges,and prospects of CNBMs,and propose future perspectives and strategies for further advancement of CNBMs for rechargeable batteries.

Suppressing Li Dendrites via Electrolyte Engineering by Crown Ethers for Lithium Metal Batteries

Electrolyte engineering is considered as an effective strategy to establish stable solid electrolyte interface(SEI),and thus to suppress the growth of lithium dendrites.In a recent study reported in Advanced Functional Materials by Ma group,discovered that strong coordination force could be founded between 15-Crown-5 ether(15-C-5) and Li+,which facilitates the crown ether(15-C-1) to participate in the solvation structure of Li+ in the electrolyte for the same purpose.Such a novel strategy might impact the design of highperformance and safe lithium metal batteries(LMB s).

Synergetic photocatalytic and thermocatalytic reforming of methanol for hydrogen production based on Pt@TiO_(2) catalyst

In order to efficiently produce H_(2),conventional methanol‐water thermocatalytic(TC)reforming requires a very high temperature due to high Gibbs free energy,while the energy conversion efficiency of methanol‐water photocatalytic(PC)reforming is far from satisfaction because of the kinetic limitation.To address these issues,herein,we incorporate PC and TC processes together in a specially designed reactor and realize simultaneous photocatalytic/thermocatalytic(PC‐TC)reforming of methanol in an aqueous phase.Such a design facilitates the synergetic effect of the PC and TC process for H_(2) production due to a lower energy barrier and faster reaction kinetics.The methanol‐water reforming based on the optimized 0.05%Pt@TiO_(2) catalyst delivers an outstanding H_(2) production rate in the PC‐TC process(5.66μmol H_(2)·g^(‒1) catalyst·s^(‒1)),which is about 3 and 7 times than those of the TC process(1.89μmol H_(2)·g^(‒1) catalyst·s^(‒1))and the PC process(0.80μmol H_(2)·g^(‒1) catalyst·s^(‒1)),respectively.Isotope tracer experiments,active intermediate trapping experiments,and theoretical calculations demonstrate that the photo‐generated holes and hydroxyl radicals could enhance the methanol dehydrogenation,water molecule splitting,and water‐gas shift reaction,while high temperature accelerates reaction kinetics.The proposed PC‐TC reforming of methanol for hydrogen production can be a promising technology to solve the energy and environmental issue in the closed‐loop hydrogen economy in the near future.

Nanoporous SiO_x coated amorphous silicon anode material with robust mechanical behavior for high-performance rechargeable Li-ion batteries

Silicon is a promising anode material for rechargeable Li-ion battery (LIB) due to its high energy density and relatively low operating voltage. However, silicon based electrodes suffer from rapid capacity degradation during electrochemical cycling. The capacity decay is predominantly caused by (i) cracking due to large volume variations during lithium insertion/extraction and (ii) surface degradation due to excessive solid electrolyte interface (SEI) formation. In this work, we demonstrate that coating of a-Si thin film with a Li-active, nanoporous SiOx layer can result in exceptional electrochemical performance in Li-ion battery. The SiOx layer provides improved cracking resistance to the thin film and prevent the active material loss due to excessive SEI formation, benefiting the electrode cycling stability. Half-cell experiments using this anode material show an initial reversible capacity of 2173 mAh g^-1 with an excellent coulombic efficiency of 90.9%. Furthermore, the electrode shows remarkable capacity retention of ~97% after 100 cycles at C/2 charging rate. The proposed anode architecture is free from Liinactive binders and conductive additives and provides mechanical stability during the charge/discharge process.

Cation-vacancy induced Li+ intercalation pseudocapacitance at atomically thin heterointerface for high capacity and high power lithium-ion batteries

It is challenging to create cation vacancies in electrode materials for enhancing the performance of rechargeable lithium ion batteries (LIBs). Herein, we utilized a strong alkaline etching method to successfully create Co vacancies at the interface of atomically thin Co_(3−x)O_(4)/graphene@CNT heterostructure for high-energy/power lithium storage. The creation of Co-vacancies in the sample was confirmed by high-resolution scanning transmission electron microscope (HRSTEM), X-ray photoelectron spectroscopy (XPS) and electron energy loss near-edge structures (ELNES). The obtained Co_(3−x)O_(4)/graphene@CNT delivers an ultra-high capacity of 1688.2 mAh g^(−1) at 0.2 C, excellent rate capability of 83.7% capacity retention at 1 C, and an ultralong life up to 1500 cycles with a reversible capacity of 1066.3 mAh g^(−1). Reaction kinetic study suggests a significant contribution from pseudocapacitive storage induced by the Co-vacancies at the Co_(3−x)O_(4)/graphene@CNT interface. Density functional theory confirms that the Co-vacancies could dramatically enhance the Li adsorption and provide an additional pathway with a lower energy barrier for Li diffusion, which results in an intercalation pseudocapacitive behavior and high-capacity/rate energy storage.

Honeycomb-like carbon materials derived from coffee extract via a “salty” thermal treatment for high-performance Li-I2 batteries

Sustainable,conductive,and porous carbon materials are ideal for energy storage materials.In this study,honeycomb-like carbon materials(HCM)are synthesized via a“salty”thermal treatment of abundant and sustainable coffee extract.Systematic materials characterization indicates that the as-prepared HCM consists of heteroatoms(N and O,etc.)doped ultra-thin carbon framework,possesses remarkable specific surface area,and excellent electrical conductivity.Such properties bestow HCM outstanding materials to be the blocking layer for Li-I2 battery,significantly eliminating the dissolution of I2 in the cathode region and stopping the I2 from shutting to anode compartment.Furthermore,our electrochemical investigation suggests that HCM could incur surface pseudo-capacitive iodine-ions charge storage and contribute additional energy storage capacity.As a result,the resultant Li-I2 battery achieves a robust and highly reversible capacity of 224.5 mAh·g−1 at the rate of 10 C.Even under a high rate of 50 C,the remarkable capacity of the as-prepared Li-I2 battery can still be maintained at 120.2 mAh·g−1 after 4000 cycles.

A focus review on 3D printing of wearable energy storage devices

Three-dimensional(3D)printing has gained popularity in a variety of applications,particularly in the manufacture of wearable devices.Aided by the large degree of freedom in customizable fabrication,3D printing can cater towards the practical requirements of wearable devices in terms of light weight and flexibility.In particular,this focus review aims to cover the important aspect of wearable energy storage devices(WESDs),which is an essential component of most wearable devices.Herein,the topics discussed are the fundamentals of 3D printing inks used,the optimizing strategies in improving the mechanical and electrochemical properties of wearable devices and the recent developments and challenges of wearable electrochemical systems such as batteries and supercapacitors.It can be expected that,with the development of 3D printing technology,realization of the full potential of WESDs and seamless integration into smart devices also needs further in-depth investigations.

Amylopectin from Glutinous Rice as a Sustainable Binder for High-Performance Silicon Anodes

Silicon(Si)has been investigated as a promising anode material because of its high theoretical capacity(4200 m Ah g^(-1)).However,silicon anode suffers from huge volume changes during repeated charge–discharge cycles.In this work,inspired by a remarkable success of the glutinous rice mortar in the Great Wall with ca.2000-year history,amylopectin(AP),the key ingredient responsible for the strong bonding force,is extracted from glutinous rice and utilized as a flexible,aqueous,and resilient binder to address the most challenging drastic volume-expansion and pulverization issues of silicon anode.Additionally,the removal of toxic N-methyl-2-pyrrolidone(NMP)organic solvent makes the electrode fabrication process environmentally friendly and healthy.The as-prepared Si-AP electrode with 60 wt%of Si can uphold a high discharge capacity of 1517.9 m Ah g^(-1)at a rate of 0.1 C after 100 cycles.The cycling stability of the Si-AP has been remarkably improved in comparison with both traditional polyvinylidene fluoride(PVDF)and aqueous carboxymethylcellulose(CMC)binders.Moreover,when the content of silicon in the Si-AP electrode increases to 70 wt%,a high discharge capacity of 1463.1 m Ah g^(-1)can still be obtained after 50 cycles at 0.1°C.These preliminary results suggest that the sustainably available and environmentally benign amylopectin binders could be a promising choice for the construction of highly stable silicon anodes.

Functional lithiophilic polymer modified separator for dendrite-free and pulverization-free lithium metal batteries

Severe performance drop and fire risk due to the uneven lithium(Li) dendrite formation and growth during charge/discharge process has been considered as the major obstacle to the practical application of Li metal batteries.So inhibiting dendrite growth and producing a stable and robust solid electrolyte interface(SEI) layer are essential to enable the use of Li metal anodes.In this work,a functional lithiophilic polymer composed of chitosan(CTS),polyethylene oxide(PEO),and poly(triethylene glycol dimethacrylate)(PTEGDMA),was homogeneously deposited on a commercial Celgard separator by combining electrospraying and polymer photopolymerization techniques.The lithiophilic environment offered by the CTS-PEO-PTEGDMA layer enables uniform Li deposition and facilitates the formation of a robust homogeneous SEI layer,thus prevent the formation and growth of Li dendrites.As a result,both Li/Li symmetric cells and LiFePO4/Li full cells deliver significantly enhanced electrochemical performance and cycle life.Even after 1000 cycles,the specific capacity of the modified full cell could be maintained at65.8 mAh g^(-1), twice which of the unmodified cell(32.8 mAh g^(-1)).The long-term cycling stability in Li/Li symmetric cells,dendrite-free anodes in SEM images and XPS analysis suggest that the pulverization of the Li anode was effectively suppressed by the lithiophilic polymer layer.