Structural Engineering of Anode Materials for Low-Temperature Lithium-Ion Batteries:Mechanisms,Strategies,and Prospects

The severe degradation of electrochemical performance for lithium-ion batteries(LIBs)at low temperatures poses a significant challenge to their practical applications.Consequently,extensive efforts have been contributed to explore novel anode materials with high electronic conductivity and rapid Li^(+)diffusion kinetics for achieving favorable low-temperature performance of LIBs.Herein,we try to review the recent reports on the synthesis and characterizations of low-temperature anode materials.First,we summarize the underlying mechanisms responsible for the performance degradation of anode materials at subzero temperatures.Second,detailed discussions concerning the key pathways(boosting electronic conductivity,enhancing Li^(+)diffusion kinetics,and inhibiting lithium dendrite)for improving the low-temperature performance of anode materials are presented.Third,several commonly used low-temperature anode materials are briefly introduced.Fourth,recent progress in the engineering of these low-temperature anode materials is summarized in terms of structural design,morphology control,surface&interface modifications,and multiphase materials.Finally,the challenges that remain to be solved in the field of low-temperature anode materials are discussed.This review was organized to offer valuable insights and guidance for next-generation LIBs with excellent low-temperature electrochemical performance.

Surface engineering of P2-type cathode material targeting long-cycling and high-rate sodium-ion batteries

The widespread interest in layered P2-type Mn-based cathode materials for sodium-ion batteries(SIBs)stems from their cost-effectiveness and abundant resources.However,the inferior cycle stability and mediocre rate performance impede their further development in practical applications.Herein,we devised a wet chemical precipitation method to deposit an amorphous aluminum phosphate(AlPO_(4),denoted as AP)protective layer onto the surface of P2-type Na_(0.55)Ni_(0.1)Co_(0.7)Mn_(0.8)O_(2)(NCM@AP).The resulting NCM@5AP electrode,with a 5 wt%coating,exhibits extended cycle life(capacity retention of78.4%after 200 cycles at 100 mA g^(-1))and superior rate performance(98 mA h g^(-1)at 500 mA g^(-1))compared to pristine NCM.Moreover,our investigation provides comprehensive insights into the phase stability and active Na^(+)ion kinetics in the NCM@5AP composite electrode,shedding light on the underlying mechanisms responsible for the enhanced performance observed in the coated electrode.

Green synthesis of ZSM-5 using silica fume and catalytic co-cracking of lignin and plastics for production of monocyclic aromatics

ZSM-5 with hierarchical pore structure was synthesized by a simple two-step hydrothermal crystallization from silica fume without using any organic ammonium templates.The synthesized ZSM-5 were oval shaped particles with a particle size about 2.0 μm and weak acid-dominated with proper Brønsted(B)and Lewis(L)acid sites.The ZSM-5 was used for catalytic co-cracking of n-octane and guaiacol,lowdensity polyethylene(LDPE)and alkali lignin(AL)to enhance the production of benzene,toluene,ethylbenzene and xylene(BTEX).The most significant synergistic effect occurred at n-octane/guaiacol at 1:1 and LDPE/AL at 1:3,under the condition,the achieved BTEX selectivity were 24%and 33%(mass)higher than the calculated values(weighted average).The highest BTEX selectivity reached 88.5%,which was 3.7%and 54.2%higher than those from individual cracking LDPE and AL.The synthesized ZSM-5 exhibited superior catalytic performance compared to the commercial ZSM-5,indicating potential application prospect.

Electrochemical Carbon Dioxide Reduction to Ethylene:From Mechanistic Understanding to Catalyst Surface Engineering

Electrochemical carbon dioxide reduction reaction(CO_(2)RR)provides a promising way to convert CO_(2)to chemicals.The multicarbon(C_(2+))products,especially ethylene,are of great interest due to their versatile industrial applications.However,selectively reducing CO_(2)to ethylene is still challenging as the additional energy required for the C–C coupling step results in large overpotential and many competing products.Nonetheless,mechanistic understanding of the key steps and preferred reaction pathways/conditions,as well as rational design of novel catalysts for ethylene production have been regarded as promising approaches to achieving the highly efficient and selective CO_(2)RR.In this review,we first illustrate the key steps for CO_(2)RR to ethylene(e.g.,CO_(2)adsorption/activation,formation of~*CO intermediate,C–C coupling step),offering mechanistic understanding of CO_(2)RR conversion to ethylene.Then the alternative reaction pathways and conditions for the formation of ethylene and competitive products(C_1 and other C_(2+)products)are investigated,guiding the further design and development of preferred conditions for ethylene generation.Engineering strategies of Cu-based catalysts for CO_(2)RR-ethylene are further summarized,and the correlations of reaction mechanism/pathways,engineering strategies and selectivity are elaborated.Finally,major challenges and perspectives in the research area of CO_(2)RR are proposed for future development and practical applications.

Nano-Au-decorated hierarchical porous cobalt sulfide derived from ZIF-67 toward optimized oxygen evolution catalysis:Important roles of microstructures and electronic modulation

Enhancing both the number of active sites available and the intrinsic activity of Co-based electrocatalysts simultaneously is a desirable goal.Herein,a ZIF-67-derived hierarchical porous cobalt sulfide decorated by Au nanoparticles(NPs)(denoted as HP-Au@CoxSy@ZIF-67)hybrid is synthesized by low-temperature sulfuration treatment.The well-defined macroporous-mesoporous-microporous structure is obtained based on the combination of polystyrene spheres,as-formed CoxSy nanosheets,and ZIF-67 frameworks.This novel three-dimensional hierarchical structure significantly enlarges the three-phase interfaces,accelerating the mass transfer and exposing the active centers for oxygen evolution reaction.The electronic structure of Co is modulated by Au through charge transfer,and a series of experiments,together with theoretical analysis,is performed to ascertain the electronic modulation of Co by Au.Meanwhile,HP-Au@CoxSy@ZIF-67 catalysts with different amounts of Au were synthesized,wherein Au and NaBH4 reductant result in an interesting“competition effect”to regulate the relative ratio of Co^(2+)/Co^(3+),and moderate Au assists the electrochemical performance to reach the highest value.Consequently,the optimized HP-Au@CoxSy@ZIF-67 exhibits a low overpotential of 340 mV at 10 mA cm^(-2)and a Tafel slope of 42 mV dec-1 for OER in 0.1 M aqueous KOH,enabling efficient water splitting and Zn-air battery performance.The work here highlights the pivotal roles of both microstructural and electronic modulation in enhancing electrocatalytic activity and presents a feasible strategy for designing and optimizing advanced electrocatalysts.

Discrimination of polysorbate 20 by high-performance liquid chromatography-charged aerosol detection and characterization for components by expanding compound database and library

Analyzing polysorbate 20(PS20)composition and the impact of each component on stability and safety is crucial due to formulation variations and individual tolerance.The similar structures and polarities of PS20 components make accurate separation,identification,and quantification challenging.In this work,a high-resolution quantitative method was developed using single-dimensional high-performance liquid chromatography(HPLC)with charged aerosol detection(CAD)to separate 18 key components with multiple esters.The separated components were characterized by ultra-high-performance liquid chromatography-quadrupole time-of-flight mass spectrometry(UHPLC-Q-TOF-MS)with an identical gradient as the HPLC-CAD analysis.The polysorbate compound database and library were expanded over 7-time compared to the commercial database.The method investigated differences in PS20 samples from various origins and grades for different dosage forms to evaluate the composition-process relationship.UHPLC-Q-TOF-MS identified 1329 to 1511 compounds in 4 batches of PS20 from different sources.The method observed the impact of 4 degradation conditions on peak components,identifying stable components and their tendencies to change.HPLC-CAD and UHPLC-Q-TOF-MS results provided insights into fingerprint differences,distinguishing quasi products.

Recent progress and future prospects of high-entropy materials for battery applications

Due to the energy crisis caused by limited fossil fuel reserves,extensive use of the renewable energy sources such as wind or solar energy is deemed to replace the use of traditional fossil fuels in the future^([1−3]).However,most renewable energy sources face the same problem,which is the intermittency of energy.For example,solar energy cannot be utilized at night.That means the continuous energy demand required for large-scale power grids can’t be satisfied by a single solar panel model.

Metal–Organic Gel Leading to Customized Magnetic‑Coupling Engineering in Carbon Aerogels for Excellent Radar Stealth and Thermal Insulation Performances

Metal–organic gel(MOG)derived composites are promising multi-functional materials due to their alterable composition,identifiable chemical homogeneity,tunable shape,and porous structure.Herein,stable metal–organic hydrogels are prepared by regulating the complexation effect,solution polarity and curing speed.Meanwhile,collagen peptide is used to facilitate the fabrication of a porous aerogel with excellent physical properties as well as the homogeneous dispersion of magnetic particles during calcination.Subsequently,two kinds of heterometallic magnetic coupling systems are obtained through the application of Kirkendall effect.FeCo/nitrogen-doped carbon(NC)aerogel demonstrates an ultra-strong microwave absorption of−85 dB at an ultra-low loading of 5%.After reducing the time taken by atom shifting,a FeCo/Fe3O4/NC aerogel containing virus-shaped particles is obtained,which achieves an ultra-broad absorption of 7.44 GHz at an ultra-thin thickness of 1.59 mm due to the coupling effect offered by dual-soft-magnetic particles.Furthermore,both aerogels show excellent thermal insulation property,and their outstanding radar stealth performances in J-20 aircraft are confirmed by computer simulation technology.The formation mechanism of MOG is also discussed along with the thermal insulation and electromagnetic wave absorption mechanism of the aerogels,which will enable the development and application of novel and lightweight stealth coatings.

Research Progress on Distribution,Sources and Ecological Effects of Phthalate in Soil

Phthalate esters(PAEs)are widely used as main plasticizers in plastic products,agricultural regulators,toys,and other fields.This paper reviewed the research progress on the distribution,sources,and ecological effects of PAEs.The effects of PAEs on soil microorganisms,animals,plants and soil properties were explored in sequence,providing effective theoretical basis for future research on PAEs.

Screening of Polyphosphate Accumulating Organisms and Their Phosphorus Removal Performance

[Objectives]To study the phosphorus removal performance of phosphate accumulating organisms(PAOs).[Methods]Activated sludge from domestic sewage treatment plant was used as the strain source,and phosphate accumulating organisms were screened by plate streaking method and dilution coating plate method.Six kinds of excellent phosphate accumulating organisms were obtained by metachromatic granule staining experiment,total phosphorus experiment and simulated sewage phosphorus removal experiment to assist the observation of bac-terial morphology and experiment of phosphorus removal capacity.In addition,the influencing factors of phosphorus removal capacity(nitrogen source,trace metal ions)were analyzed.[Results]In the case of simulated sewage,the phosphorus removal rate of strain b was the highest,reaching 66.25%,while the phosphorus removal rate of strain e and f was about 10%lower than that of the phosphorus uptake experiment.[Conclusions]This study is expected to provide a theoretical reference for the gradual optimization of the screening method of phosphorus re-moval bacteria in domestic sewage treatment.

High valence metals engineering strategies of Fe/Co/Ni-based catalysts for boosted OER electrocatalysis

Electrocatalysis for the oxygen evolution reactions(OER)has attracted much attention due to its important role in water splitting and rechargeable metal-air batteries.Therefore,designing highly efficient and low-cost catalysts for OER process is essential as the conventional catalysts still rely on precious metals.Transition metal-based compounds have been widely investigated as active OER catalysts,and renewed interest in the high valence metals engineered compounds has been achieved for superior catalytic activity and stability.However,an in-depth understanding of the construction strategies and induced effects for the high valence metals engineered catalysts is still lacking and desired.In this review,we have summarized the construction strategies of high valence metals as dopants or formed heterostructures with the iron/cobalt/nickel(Fe/Co/Ni)-based catalysts.Then the induced effects on Fe/Co/Ni-based catalysts by incorporating high valence metals,e.g.,accelerating the surface reconstruction,forming amorphous structure,generating vacancies/defects,and acting as stabilizers,are highlighted.The impacts of high valence metals on OER performance are elucidated based on different elements,including molybdenum(Mo),tungsten(W),cerium(Ce),vanadium(V),chromium(Cr),manganese(Mn),niobium(Nb),zirconium(Zr).The correlations of construction strategies,induced effects,catalytic activity and OER reaction pathways are elaborated.Finally,the remaining challenges for further enhancements of OER performance induced by high valence metals are presented.

KOH-assisted aqueous synthesis of bimetallic metal-organic frameworks and their derived selenide composites for efficient lithium storage

To solve low efficiency,environmental pollution,and toxicity for synthesizing zeolitic imidazolate frameworks(ZIFs)in organic solvents,a KOH-assisted aqueous strategy is proposed to synthesize bimetallic ZIFs polyhedrons,which are used as precursors to prepare bimetallic selenide and N-doped carbon(NC)composites.Among them,Fe–Co–Se/NC retains the three-dimensional(3D)polyhedrons with mesoporous structure,and Fe–Co–Se nanoparticles are uniform in size and evenly distributed.When assessed as anode material for lithium-ion batteries,Fe–Co–Se/NC achieves an excellent initial specific capacity of 1165.9 m Ah·g^(-1)at 1.0 A·g^(-1),and the reversible capacity of Fe–Co–Se/NC anode is 1247.4 m Ah·g^(-1)after 550 cycles.It is attributed to that the uniform composite of bimetallic selenides and N-doped carbon can effectively tune redox active sites,the stable 3D structure of Fe–Co–Se/NCs guarantees the structural stability and wettability of the electrolyte,and the uniform distribution of Fe–Co–S nanoparticles in size esuppresses the volume expansion and accelerates the electrochemical reaction kinetics.

KOH-assisted aqueous synthesis of ZIF-67 with high-yield and its derived cobalt selenide/carbon composites for high-performance Li-ion batteries

To solve the environmental pollution and low yield during the sythesis of zeolitic imidazolate frameworks(ZIFs)and their derived materials,a KOH-assisted aqueous strategy is proposed to synthesize cobalt zeolitic imidazolate framework(ZIF-67)polyhedrons,which are used as precursors to prepare cobalt selenide/carbon composites with different crystal phases(Co_(0.85)Se,CoSe_2).When evaluated as anode material for lithium ion batteries,Co_(0.85)Se/C composites deliver a reversible capacity of 758.7 m A·h·g^(-1)with a capacity retention rate of 90.5%at 1.0 A·g^(-1)after 500 cycles,and the superior rate capability is 620 m A·h·g^(-1)at 2.0 A·g^(-1).The addition of KOH accelerates the production of ZIF-67 crystals by boosting deprotonation of dimethylimidazole,resulting in rapid growth and structures transition from two-dimensional to three-dimensional of ZIF-67 in aqueous solution,which greatly promotes the application of MOFs in the field of energy storage and conversion.

Recent progress and future prospect of novel multi-ion storage devices

Rechargeable batteries,especially lithium-ion batteries(LIBs),have made rapid development since the 21st century,greatly facilitating people's lives[1−6].Based on considerations of cost and existing problems(such as safety issues due to LIBs stacking strategy and unsatisfactory performance for various applications),researchers have explored alternative technologies to LIBs to meet the needs for wide application scenarios[5].Among them,multi-ion storage devices such as dual-ion batteries(DIBs)and metal-ion hybrid capacitors(MIHCs)are considered promising alternative energy storage devices of LIBs due to their unique multi-ion storage mechanism.In a multi-ion storage device,cations and anions carry charges back and forth between the electrolyte and the electrodes at the same time,unlike the rocking chair mechanism of LIBs[7].Generally,the anodes of DIBs and MIHCs work in a similar mechanism to LIBs,storing charge through redox reactions.The main difference among them is the mechanism of the cathodes during charging and discharging[8].In DIBs,the battery-type cathode stores anions through the Faraday reaction.

Rational construction of Ag@MIL-88B(V)-derived hierarchical porous Ag-V_(2)O_(5) heterostructures with enhanced diffusion kinetics and cycling stability for aqueous zinc-ion batteries

With the advantages of the multiple oxidation states and highly open crystal structures,vanadium-based composites have been considered as the promising cathode materials for aqueous zinc-ion batteries(ZIBs).However,the inherent inferior electrical conductivity,low specific surface area,and sluggish Zn^(2+)diffusion kinetics of the traditional vanadium-based oxides have greatly impeded their development.Herein,a novel hierarchical porous spindle-shaped Ag-V_(2)O_(5) with unique heterostructures was rationally designed via a simple MOF-assisted synthetic method and applied as stable cathode for aqueous ZIBs.The high specific surface area and hierarchically porous superstructures endowed Ag-V_(2)O_(5) with sufficient electrochemical active sites and shortened the diffusion pathways of Zn^(2+),which was beneficial to accelerate the reversible transport of Zn^(2+)and deliver a high specific capacity(426 mA h g^(-1) at 0.1 A g^(-1) and 96.5%capacity retention after 100 cycles).Meanwhile,the self-built-in electric fields at the heterointerface of Ag-V_(2)O_(5) electrode could strengthen the synergistic coupling interaction between Ag and V_(2)O_(5),which can effectively enhance the electric conductivity and maintain the structural integrity,resulting in superb rate capability(326.1 mA h g^(-1) at 5.0 A g^(-1))and remarkable cycling stability(89.7%capacity retention after 2000 cycles at 5.0 A g^(-1)).Moreover,the reversible Zn^(2+)storage mechanism was further investigated and elucidated by kinetics analysis and DFT calculations.

Design of ZnSe-CoSe heterostructure decorated in hollow N-doped carbon nanocage with generous adsorption and catalysis sites for the reversibly fast kinetics of polysulfide conversion

Although lithium-sulfur batteries(Li SBs)are regarded as one of the most promising candidates for the next-generation energy storage system,the actual industrial application is hindered by the sluggish solid–liquid phase conversion kinetics,severe shuttle effect,and low sulfur loadings.Herein,a zeolitic imidazolate framework(ZIF)derived heterogeneous ZnSe-CoSe nanoparticles encapsulated in hollow N-doped carbon nanocage(ZnSe-CoSe-HNC)was designed by etching with tannic acid as a multifunctional electrocatalyst to boost the polysulfide conversion kinetics in LiSBs.The hollow structure in ZIF ensures large inner voids for sulfur and buffering volume expansions.Abundant exposed ZnSe-CoSe heterogeneous interfaces serve as bifunctional adsorption-catalytic centers to accelerate the conversion kinetics and alleviate the shuttle effect.Together with the highly conductive framework,the ZnSe-CoSeHNC/S cathode exhibits a high initial reversible capacity of 1305.3 m A h g-1at 0.2 C,high-rate capability,and reliable cycling stability under high sulfur loading and lean electrolyte(maintaining at 745 m A h g-1after 200 cycles with a high sulfur loading of 6.4 mg cm-2and a low electrolyte/sulfur ratio of 6μL mg^(-1)).Theoretical calculations have demonstrated the heterostructures of ZnSe-CoSe offer higher binding energy to lithium polysulfides than that of ZnSe or CoSe,facilitating the electron transfer to lithium polysulfides.This work provides a novel heterostructure with superior catalytic ability and hollow conductive architecture,paving the way for the practical application of functional sulfur electrodes.

Combined “Gateway” and “Spillover” effects originated from a CeNi_(5) alloy catalyst for hydrogen storage of MgH_(2)

Efficient catalysts enable MgH2 with superior hydrogen storage performance.Herein,we successfully synthesized a catalyst composed of Ce and Ni (i.e.CeNi_(5) alloy) with splendid catalytic action for boosting the hydrogen storage property of magnesium hydride (MgH_(2))The MgH2–5wt%CeNi_(5) composite’s initial hydrogen release temperature was reduced to 174℃ and approximately 6.4wt%H_(2) was released at 275℃ within 10 min.Besides,the dehydrogenation enthalpy of MgH_(2) was slightly decreased by adding CeNi_(5).For hydrogenation,the fully dehydrogenated sample absorbed 4.8wt%H_(2) at a low temperature of 175℃.The hydrogenation apparent activation energy was decreased from(73.60±1.79) to (46.12±7.33) kJ/mol.Microstructure analysis revealed that Mg_(2)Ni/Mg_(2)NiH_(4) and CeH_(2.73) were formed during the process of hydrogen absorption and desorption,exerted combined“Gateway”and“Spillover”effects to reduce the operating temperature and improve the hydrogen storage kinetics of MgH_(2).Our work provides an example of merging“Gateway”and“Spillover”effects in one catalyst and may shed light on designing novel highly-effective catalysts for MgH_(2) in near future.

Electronic and thermal properties of Ag-doped single crystal zinc oxide via laser-induced technique

The doping of ZnO has attracted lots of attention because it is an important way to tune the properties of ZnO.Postdoping after growth is one of the efficient strategies.Here,we report a unique approach to successfully dope the single crystalline ZnO with Ag by the laser-induced method,which can effectively further post-treat grown samples.Magnetron sputtering was used to coat the Ag film with a thickness of about 50 nm on the single crystalline ZnO.Neodymium-doped yttrium aluminum garnet(Nd:YAG)laser was chosen to irradiate the Ag-capped ZnO samples,followed by annealing at700℃for two hours to form ZnO:Ag.The three-dimensional(3D)information of the elemental distribution of Ag in ZnO was obtained through time-of-flight secondary ion mass spectrometry(TOF-SIMS).TOF-SIMS and core-level x-ray photoelectron spectroscopy(XPS)demonstrated that the Ag impurities could be effectively doped into single crystalline ZnO samples as deep as several hundred nanometers.Obvious broadening of core level XPS profiles of Ag from the surface to depths of hundred nms was observed,indicating the variance of chemical state changes in laser-induced Ag-doped ZnO.Interesting features of electronic mixing states were detected in the valence band XPS of ZnO:Ag,suggesting the strong coupling or interaction of Ag and ZnO in the sample rather than their simple mixture.The Ag-doped ZnO also showed a narrower bandgap and a decrease in thermal diffusion coefficient compared to the pure ZnO,which would be beneficial to thermoelectric performance.

Engineering Strategies for Suppressing the Shuttle Effect in Lithium–Sulfur Batteries

Lithium–sulfur(Li–S)batteries are supposed to be one of the most potential next-generation batteries owing to their high theoretical capacity and low cost.Nevertheless,the shuttle effect of firm multi-step two-electron reaction between sulfur and lithium in liquid electrolyte makes the capacity much smaller than the theoretical value.Many methods were proposed for inhibiting the shuttle effect of polysulfide,improving corresponding redox kinetics and enhancing the integral performance of Li–S batteries.Here,we will comprehensively and systematically summarize the strategies for inhibiting the shuttle effect from all components of Li–S batteries.First,the electrochemical principles/mechanism and origin of the shuttle effect are described in detail.Moreover,the efficient strategies,including boosting the sulfur conversion rate of sulfur,confining sulfur or lithium polysulfides(LPS)within cathode host,confining LPS in the shield layer,and preventing LPS from contacting the anode,will be discussed to suppress the shuttle effect.Then,recent advances in inhibition of shuttle effect in cathode,electrolyte,separator,and anode with the aforementioned strategies have been summarized to direct the further design of efficient materials for Li–S batteries.Finally,we present prospects for inhibition of the LPS shuttle and potential development directions in Li–S batteries.

Study on Physical and Chemical Behaviors of Rare Earths in Preparing Ceramic Tube Supported Palladium Film by Electroless Plating

The rare earths of ytterbium, lanthanum, praseodymium, neodymium and their binary mixtures were respectively added into the traditional electroless plating solution to prepare thin palladium film on the inner surface of porous ceramic tube. The experimental results shows that the addition of rare earths increases palladium deposition rates and the binary mixtures are superior to the single rare earths and the mixture of ytterbium-lanthanum is the most efficient. Adding the mixture of ytterbium-lanthanum can also reduce the plating temperature by 10 ~ 20℃, shrink the metal crystal size and improve the film densification compared to those by traditional electroless plating. A thin palladium film with 5μm was prepared and the film made a highly pure hydrogen with a molar fraction of more than 99.97% from a H2-N2 gas mixture. More attentions were paid to analyze the physical and chemical behaviors of the rare earths in palladium film preparation.