Photo-assisted Rechargeable Metal Batteries for Energy Conversion and Storage

Solar cells hold a function of photovoltaic conversion,while rechargeable metal batteries have an advantage of high energy storage.The conventional charge mode of batteries is made based on complete utilization of electric energy.The combination of solar cells and rechargeable metal batteries brings a new opportunity for the development of photo-assisted rechargeable batteries,in which the solar energy can be utilized to partially achieve photo-charging with or without external electrical bias.This review highlights the working mechanism and structure design of photo-assisted rechargeable metal batteries according to the characteristics of rechargeable metal batteries and advantage of the photovoltaic technology.In particular,the recent advances are introduced for photo-assisted rechargeable batteries based on light-weight metal anodes,including metal lithium,metal sodium,and metal zinc.The working features of the integrated devices are also discussed for energy saving under photo-assisted charging mode.Finally,a future outlook is provided for further improving the performance of photoassisted rechargeable metal batteries.

Recent progress in thermodynamic and kinetics modification of magnesium hydride hydrogen storage materials

Hydrogen energy has emerged as a pivotal solution to address the global energy crisis and pave the way for a cleaner,low-carbon,secure,and efficient modern energy system.A key imperative in the utilization of hydrogen energy lies in the development of high-performance hydrogen storage materials.Magnesium-based hydrogen storage materials exhibit remarkable advantages,including high hydrogen storage density,cost-effectiveness,and abundant magnesium resources,making them highly promising for the hydrogen energy sector.Nonetheless,practical applications of magnesium hydride for hydrogen storage face significant challenges,primarily due to their slow kinetics and stable thermodynamic properties.Herein,we briefly summarize the thermodynamic and kinetic properties of MgH2,encompassing strategies such as alloying,nanoscaling,catalyst doping,and composite system construction to enhance its hydrogen storage performance.Notably,nanoscaling and catalyst doping have emerged as more effective modification strategies.The discussion focuses on the thermodynamic changes induced by nanoscaling and the kinetic enhancements resulting from catalyst doping.Particular emphasis lies in the synergistic improvement strategy of incorporating nanocatalysts with confinement materials,and we revisit typical works on the multi-strategy optimization of MgH2.In conclusion,we conduct an analysis of outstanding challenges and issues,followed by presenting future research and development prospects for MgH2 as hydrogen storage materials.

Self‑Assembly of Binderless MXene Aerogel for Multiple‑Scenario and Responsive Phase Change Composites with Ultrahigh Thermal Energy Storage Density and Exceptional Electromagnetic Interference Shielding

The severe dependence of traditional phase change materials(PCMs)on the temperature-response and lattice deficiencies in versatility cannot satisfy demand for using such materials in complex application scenarios.Here,we introduced metal ions to induce the self-assembly of MXene nanosheets and achieve their ordered arrangement by combining suction filtration and rapid freezing.Subsequently,a series of MXene/K^(+)/paraffin wax(PW)phase change composites(PCCs)were obtained via vacuum impregnation in molten PW.The prepared MXene-based PCCs showed versatile applications from macroscale technologies,successfully transforming solar,electric,and magnetic energy into thermal energy stored as latent heat in the PCCs.Moreover,due to the absence of binder in the MXene-based aerogel,MK3@PW exhibits a prime solar-thermal conversion efficiency(98.4%).Notably,MK3@PW can further convert the collected heat energy into electric energy through thermoelectric equipment and realize favorable solar-thermal-electric conversion(producing 206 mV of voltage with light radiation intensity of 200 mw cm^(−2)).An excellent Joule heat performance(reaching 105℃with an input voltage of 2.5 V)and responsive magnetic-thermal conversion behavior(a charging time of 11.8 s can achieve a thermal insulation effect of 285 s)for contactless thermotherapy were also demonstrated by the MK3@PW.Specifically,as a result of the ordered arrangement of MXene nanosheet self-assembly induced by potassium ions,MK3@PW PCC exhibits a higher electromagnetic shielding efficiency value(57.7 dB)than pure MXene aerogel/PW PCC(29.8 dB)with the same MXene mass.This work presents an opportunity for the multi-scene response and practical application of PCMs that satisfy demand of next-generation multifunctional PCCs.

Recent progress of W_(18)O_(49)nanowires for energy conversion and storage

W_(18)O_(49)nanowires(W_(18)O_(49)NWs)with unique one-dimension structures and excellent electron/ions transport properties have attracted increasing attention in academia and industry because of their potential applications in many energy-related devices.In the past decades,many research articles related to W_(18)O_(49)have been published,but there are insufficient review articles focusing on W_(18)O_(49)NWs.In this review,we present the crystal structure of W_(18)O_(49)and briefly introduce the synthesis methods and growth mechanism of W_(18)O_(49)NWs.Moreover,their applications in energy conversion and storage devices are summarized.Finally,the current challenges and opportunities for applying W_(18)O_(49)NWs are provided.We hope this review can promote the development of W_(18)O_(49)NWs in energy conversion,storage,and other promising applications.

Review on porous nanomaterials for adsorption and photocatalytic conversion of CO_2

Photocatalytic conversion of“greenhouse gas”CO2is considered to be one of the most effective ways to alleviate current energy and environmental problems without additional energy consumption and pollutant emission.The performance of many traditional semiconductor photocatalysts is not efficient enough to satisfy the requirements of practical applications because of their limited specific surface area and low CO2adsorption capacity.Therefore,the exploration of photocatalysts with high CO2uptake is significant in the field of CO2conversion.Recently the porous materials appeared to be a kind of superior candidate for enriching the CO2molecules on the surface of photocatalysts for catalytic conversion.This paper first summarizes the advances in the development of nanoporous adsorbents for CO2capture.Three main classes of porous materials are considered:inorganic porous materials,metal organic frameworks,and microporous organic polymers.Based on systematic research on CO2uptake,we then highlight the recent progress in these porous‐material‐based photocatalysts for CO2conversion.Benefiting from the improved CO2uptake capacity,the porous‐material‐based photocatalysts exhibited remarkably enhanced efficiency in the reduction of CO2to chemical fuels,such as CO,CH4,and CH3OH.Based on reported recent achievements,we predict a trend of development in multifunctional materials with both high adsorption capability and photocatalytic performance for CO2utilization.

Lithium storage performance of {010}-faceted and [111]-faceted anatase TiO2 nanocrystals

As a popular anode material for lithium-ion batteries,anatase TiO2 nanoparticles with exposed{001}facets usually exhibit exceptional lithium storage performance owing to more accessible sites and fast migration of lithium ions along the good crystalline channels.However,there are few researches on the lithium storage capability of TiO2 nanocrystals with other high-energy facets owing to lack of effective synthesis method for controlling crystal facets.Herein,anatase TiO2 nanocrystals with exposed{010}-and[111]-facets are successfully prepared by using the delaminated tetratitanate nanoribbons as precursors.The electrochemical properties of these TiO2 nanocrystals with high-energy surfaces and the comparison with commercial TiO2 nanoparticles(P25)are studied.It is found that the cycle and rate performance of TiO2 nanocrystals is highly improved by reducing the particle size of nanocrystals.Moreover,TiO2 nanocrystals with exposed{010}-and[111]-facets exhibit better lithium storage capacities in comparison with P25 without a specific facet though P25 has smaller particle size than these TiO2 nanocrystals,indicating that the exposed facets of TiO2 nanocrystals have an important impact on their lithium storage capacity.Therefore,the synthesis design of high-performance TiO2 materials applied in the next-generation secondary batteries should both consider the particle size and the exposed facets of nanocrystals.

Integration of cobalt selenide nanocrystals with interlayer expanded 3D Se/N Co-doped carbon networks for superior sodium-ion storage

Rational electrode structure design is of great significance for realizing superior Na^(+)storage performance.Herein,a metal salt-induced polymer blowing-bubble approach followed by selenization procedure is developed to in-situ generate abundant sub-10 nm CoSe_(2) nanocrystals on 3D Se/N co-doped carbon networks(CoSe_(2)@3DSNC).The phase transition from Co to CoSe_(2) and the incorporation of Se into the carbon layer are realized simultaneously to establish above configuration,in which the CoSe_(2) nanocrystals are anchored on interlayer expanded carbon networks.Such unique configuration endows electrode with lower Na+diffusion energy barrier,higher Na+storage capability and better structural durability.Reflected in SIBs,the optimized CoSe_(2)@3 DSNC delivers superior rate capability(310 m Ah g^(-1) at 10 A g^(-1))and excellent longterm cycling stability(409 m Ah g^(-1) after 1200 cycles at 5 A g^(-1)).Moreover,this configuration can also be obtained in other metal selenides-carbon composite through a similar approach.

Compositional and Hollow Engineering of Silicon Carbide/Carbon Microspheres as High-Performance Microwave Absorbing Materials with Good Environmental Tolerance

Microwave absorbing materials(MAMs)characterized by high absorption efficiency and good environmental tolerance are highly desirable in practical applications.Both silicon carbide and carbon are considered as stable MAMs under some rigorous conditions,while their composites still fail to produce satisfactory microwave absorption performance regardless of the improvements as compared with the individuals.Herein,we have successfully implemented compositional and structural engineering to fabricate hollow Si C/C microspheres with controllable composition.The simultaneous modulation on dielectric properties and impedance matching can be easily achieved as the change in the composition of these composites.The formation of hollow structure not only favors lightweight feature,but also generates considerable contribution to microwave attenuation capacity.With the synergistic effect of composition and structure,the optimized SiC/C composite exhibits excellent performance,whose the strongest reflection loss intensity and broadest effective absorption reach-60.8 dB and 5.1 GHz,respectively,and its microwave absorption properties are actually superior to those of most SiC/C composites in previous studies.In addition,the stability tests of microwave absorption capacity after exposure to harsh conditions and Radar Cross Section simulation data demonstrate that hollow SiC/C microspheres from compositional and structural optimization have a bright prospect in practical applications.

Composition Engineering Opens an Avenue Toward Efficient and Sustainable Nitrogen Fixation

In this work,we open an avenue toward rational design of potential efficient catalysts for sustainable ammonia synthesis through composition engineering strategy by exploiting the synergistic effects among the active sites as exemplified by diatomic metals anchored graphdiyne via the combination of hierarchical high-throughput screening,first-principles calculations,and molecular dynamics simulations.Totally 43 highly efficient catalysts feature ultralow onset potentials(|U_(onset)|≤0.40 V)with Rh-Hf and Rh-Ta showing negligible onset potentials of 0 and-0.04 V,respectively.Extremely high catalytic activities of Rh-Hf and Rh-Ta can be ascribed to the synergistic effects.When forming heteronuclears,the combinations of relatively weak(such as Rh)and relatively strong(such as Hf or Ta)components usually lead to the optimal strengths of adsorption Gibbs free energies of reaction intermediates.The origin can be ascribed to the mediate d-band centers of Rh-Hf and Rh-Ta,which lead to the optimal adsorption strengths of intermediates,thereby bringing the high catalytic activities.Our work provides a new and general strategy toward the architecture of highly efficient catalysts not only for electrocatalytic nitrogen reduction reaction(eNRR)but also for other important reactions.We expect that our work will boost both experimental and theoretical efforts in this direction.

Revealing the key role of non-solvating diluents for fast-charging and low temperature Li-ion batteries

Fast-charging and low temperature operation are of vital importance for the further development of lithium-ion batteries(LIBs),which is hindered by the utilization of conventional carbonate-based electrolytes due to their slow kinetics,narrow operating temperature and voltage range.Herein,an acetonitrile(AN)-based localized high-concentration electrolyte(LHCE)is proposed to retain liquid state and high ionic conductivity at ultra-low temperatures while possessing high oxidation stability.We originally reveal the excellent thermal shielding effect of non-solvating diluent to prevent the aggregation of Li^(+) solvates as temperature drops,maintaining the merits of fast Li transport and facile desolvation as at room temperature,which bestows the graphite electrode with remarkable low temperature performance(264 mA h g^(-1) at-20 C).Remarkably,an extremely high capacity retention of 97%is achieved for high-voltage high-energy graphite||NCM batteries after 250 cycles at-20 C,and a high capacity of 110 mA h g^(-1)(71%of its room-temperature capacity)is retained at-30°C.The study unveils the key role of the non-solvating diluents and provides instructive guidance in designing electrolytes towards fast-charging and low temperature LIBs.

Molecular and atomic manipulation of metal-organic framework-derived LiCoMnO_(4):An oxygen-deficient strategy for advanced lithium storage

As a novel class of high-voltage cathode materials,spinel lithium transition metal oxides have been faced with demerits including pronounced structural instability caused by Jahn-Teller distortion(especially at the lower voltage region)and severe capacity degradation despite their intriguing electrochemical properties.To extend their functionalities as broad-voltage cathodes,the sacrificial template method has been regarded as a promising way to realize structural and compositional control for desirable electrochemical behaviors.Herein,we report a synthetic protocol to directionally prepare Li Co Mn O_(4)(LCMO)using carboxyl-based metal-organic frameworks(MOFs)as self-sacrificing templates.Impressively,LCMO derived from Co Mn-BDC(H_(2)BDC=1,4-benzenedicarboxylate)displays superior electrochemical performances with a specific capacity of 151.6 m Ah g^(-1)at 1 C(150 m A g^(-1))after 120 cycles and excellent rate capacity of 91.9 m Ah g^(-1)at 10 C due to the morphology control,microstructural modulation,and atomic manipulation of the MOF precursor.Bestowed by the optimized atomic and electronic structure,abundant oxygen vacancies,and the nanostructure retained from MOF precursors,LCMO materials display extraordinary electrochemical properties,which have been extensively verified by both experimental and theoretical studies.This work not only provides guidelines for the directional design of spinel materials at molecular and atomic levels but also sheds light on the practical use of LIBs with broad range voltage.

Advances of Synergistic Electrocatalysis Between Single Atoms and Nanoparticles/Clusters

Combining single atoms with clusters or nanoparticles is an emerging tactic to design efficient electrocatalysts.Both synergy effect and high atomic utilization of active sites in the composite catalysts result in enhanced electrocatalytic performance,simultaneously provide a radical analysis of the interrelationship between structure and activity.In this review,the recent advances of single-atomic site catalysts coupled with clusters or nanoparticles are emphasized.Firstly,the synthetic strategies,characterization,dynamics and types of single atoms coupled with clusters/nanoparticles are introduced,and then the key factors controlling the structure of the composite catalysts are discussed.Next,several clean energy catalytic reactions performed over the synergistic composite catalysts are illustrated.Eventually,the encountering challenges and recommendations for the future advancement of synergistic structure in energy-transformation electrocatalysis are outlined.

Side chain modulated ferrocene derivative as the interstitial conductive medium for high-performance and stable perovskite solar cells

The interfacial nonradiative recombination loss caused by the deep traps and mismatched band alignment restrained the commercial viability of perovskite solar cells(PSCs). Herein, we have constructed ferrocene carboxylic acid(FcA) and octafluoropentyl-ferrocenyl-carboxylate(OFFcA) interstitial conductive mediums to modulate the integral heterointerface properties and the photovoltaic performances of PSCs.By comparing the passivation strengths of the two molecules, we found that the synergistic effects among Fc/Fc^(+)redox shuttle, C=O group, and F substituents realize the optimal elimination of interfacial trap sources. Electron-withdrawing F groups reinforce the capacity of the Fc/Fc^(+)redox shuttle for the healing of metallic Pb defects and provide extensive anchoring sites to stabilize the organic components.Additionally, the homogeneity of the OFFcA layer as well as the humidity stability of perovskite film are facilitated through the introduction of F substituents, which reduce the contact resistance and improve the interfacial charge transfer. The champion OFFcA-modified device delivers an exceptional PCE of 23.62%, exceeding those of the control(PCE=22.32%) and FcA-modified(PCE=23.06%) devices.Moreover, the unencapsulated OFFcA-modified device retains 82.7% of the primary efficiency at 60%RH for more than 50 d and only loses less than 10% of the primary efficiency when stored in a glove box for more than 2000 h.

A-site assisted perovskite crystallization via ion-exchange MOFs for high efficient and stable perovskite solar cells

Here,a novel strategy is proposed targeting the volatility of A-site cations and the disordered arrangement of perovskite grains through employing Cs~+contained metal-organic frameworks In-aip(Cs)obtained by ion-exchange and crystalline transform.Interatomic forces between Cs-O atoms split the pore channels of the pristine In-aip,endowing In-aip(Cs)with multidimensional charge transport channels,In addition,the partially freed Cs~+in the interlayer compensates for the vacancy of A-site cations during the perovskite preparation process.The In-aip(Cs)modified perovskite films have a flat morphology,large grains and excellent optoelectronic properties.Benefiting from the high-quality perovskite films and faster charge extraction,the In-aip(Cs)-modified PSCs achieved a champion PCE of 23.03%,superior to the In-aip-modified(22.29%)and control device(21.13%),More importantly,the unencapsulated PSCs modified with In-aip(Cs)exhibited outstanding humidity and thermal stability.Over a period of almost 1000 h,the unencapsulated In-aip(Cs)-modified device retained 85%of its initial PCE after storing in a glove box at 85℃,and retained 87%of the primary PCE upon storage in ambient condition at 25℃under a humidity of 40%.

Synergism of solar-driven interfacial evaporation and photo-Fenton Cr(Ⅵ) reduction by sustainable Bi-MOF-based evaporator from waste polyester

The integration of interfacial solar steam generation and photocatalytic degradation technology has pro-vided a promising platform to simultaneously produce freshwater and degrade pollutants.However,con-structing low-cost,multi-functional evaporators for treating Cr(Ⅵ)-polluted water remains challenging,and the synergistic mechanism on Cr(Ⅵ)reduction is fuzzy.Herein,we propose the combined strategy of ball milling and solution mixing for the sustainable production of Bi-MOF microrod from waste poly(ethylene terephthalate),and construct Bi-MOF-based solar evaporators for simultaneous photo-Fenton Cr(Ⅵ)reduction and freshwater production.Firstly,the evaporator comprised of Bi-MOF microrod and graphene nanosheet possesses high light absorption,efficient photothermal conversion,and good hydro-philic property.Attributing to the advantages,the hybrid evaporator exhibits the evaporation rate of 2.16 kg m^(-2) h^(-1) and evaporation efficiency of 87.5%under 1 kW m^(-2) of irradiation.When integrating with photo-Fenton reaction,the Cr(Ⅵ)reduction efficiency is 91.3%,along with the reaction kinetics of 0.0548 min^(-1),surpassing many advanced catalysts.In the outdoor freshwater production and Cr(Ⅵ)reduction,the daily accumulative water yield is 5.17 kg m^(-2) h^(-1),and the Cr(Ⅵ)reduction efficiency is 99.9%.Furthermore,we prove that the localization effect derived from the interfacial solar-driven evap-oration enhances H_(2)O_(2) activation for the photo-Fenton reduction of Cr(Ⅵ).Based on the result of density functional theory,Bi-MOF microrod provides rich active centers for H_(2)O_(2) activation to produce active sites such as e-or-O_(2).This study not only proposes a new strategy to construct multi-functional solar evaporators for freshwater production and catalytic reduction of pollutants,but also advances the chem-ical upcycling of waste polyesters.

Mild polarization electric field in ultra-thin BN-Fe-graphene sandwich structure for efficient nitrogen reduction

The electrocatalytic N_(2)reduction reaction(NRR)is expected to supersede the traditional Haber-Bosch technology for NH3 production under ambient conditions.The activity and selectivity of electrochemical NRR are restricted to a strong polarized electric field induced by the catalyst,correct electron transfer direction,and electron tunneling distance between bare electrode and active sites.By coupling the chemical vapor deposition method with the poly(methyl methacylate)-transfer method,an ultrathin sandwich catalyst,i.e.,Fe atoms(polarized electric field layer)sandwiched between ultrathin(within electron tunneling distance)BN(catalyst layer)and graphene film(conducting layer),is fabricated for electrocatalytic NRR.The sandwich catalyst not only controls the transfer of electrons to the BN surface in the correct direction under applied voltage but also suppresses hydrogen evolution reaction by constructing a neutral polarization electric field without metal exposure.The sandwich electrocatalyst NRR system achieve NH3 yield of 8.9μg h^(−1)cm^(−2)and Faradaic Efficiency of 21.7%.The N_(2)adsorption,activation,and polarization electric field changes of three sandwich catalysts(BN-Fe-G,BN-Fe-BN,and G-Fe-G)during the electrocatalytic NRR are investigated by experiments and density functional theory simulations.Driven by applied voltage,the neutral polarized electric field induced by BN-Fe-G leads to the high activity of electrocatalytic NRR.

Time-Resolved Oxidation State Changes Are Key to Elucidating the Bifunctionality of Perovskite Catalysts for Oxygen Evolution and Reduction

In a unified regenerative fuel cell(URFC)or reversible fuel cell,the oxygen bifunctional catalyst must switch reversibly between the oxygen reduction reaction(ORR),fuel cell mode,and the oxygen evolution reaction(OER),electrolyzer mode.However,it is often unclear what effect alternating between ORR and OER has on the electrochemical behavior and physiochemical properties of the catalyst.Herein,operando X-ray absorption spectroscopy(XAS)is utilized to monitor the continuous and dynamic evolution of the Co,Mn,and Fe oxidation states of perovskite catalysts Ba_(0.5)Sr_(0.5)Co_(0.8)Fe_(0.2)O_(3-δ)(BSCF)and La_(0.4)Sr_(0.6)MnO_(3-δ)(LSM),while the potential is oscillated between reducing and oxidizing potentials with cyclic voltammetry.The results reveal the importance of investigating bifunctional catalysts by alternating between fuel cell and electrolyzer operation and highlight the limitations and challenges of bifunctional catalysts.It is shown that the requirements for ORR and OER performance are divergent and that the oxidative potentials of OER are detrimental to ORR activity.These findings are used to give guidelines for future bifunctional catalyst design.Additionally,it is demonstrated how sunlight can be used to reactivate the ORR activity of LSM after rigorous cycling.

High donor-number and low content electrolyte additive for stabilizing zinc metal anode

The aqueous zinc ion batteries(AZIBs)are thought as promising competitors for electrochemical energy storage,though their wide application is curbed by the uncontrollable dendrite growth and gas evolution side reactions.Herein,to stabilize both zinc anodes and water molecules,we developed a modified electrolyte by adding a trace amount of N,N-diethylformanmide(DEF)into the ZnSO_(4)electrolyte for the first time in zinc ion batteries.The effectiveness of DEF is predicted by the comparison of donor number and its preferential adsorption behavior on the zinc anode is further demonstrated by several spectroscopy characterizations,electrochemical methods,and molecular dynamics simulation.The modified electrolyte with 5%v.t.DEF content can ensure a stable cycling life longer than 3400 h of Zn‖Zn symmetric cells and an ultra-reversible Zn stripping/plating process with a high coulombic efficiency of 99.7%.The Zn‖VO_(2)full cell maintains a capacity retention of 83.5%and a 104 mA h g^(-1)mass capacity after 1000cycles.This work provides insights into the role of interfacial adsorption behavior and the donor number of additive molecules in designing low-content and effective aqueous electrolytes.

Electro‑copolymerized film of ruthenium catalyst and redox mediator for electrocatalytic water oxidation

Electro-copolymerized film containing ruthenium complexes as electron-transfer(or redox)mediators and water-oxidation catalysts by an oxidative copolymerization method is presented.The addition of the redox mediator significantly improved the electrocatalytic water-oxidation activity and reduced the overpotential to 220 mV.The prepared electrode showed a water-oxidation catalytic rate constant kobs of 31.7 s^(-1)and an initial turnover frequency of 1.01 s^(-1)in 1000 s by potential electrolysis at 1.7 V applied bias vs NHE(normal hydrogen electrode).The kinetic isotope effect study suggests that the catalytic water oxidation reaction on the electrode surface occurs via a bimolecular coupling mechanism.

Intramolecular Hydrogen Bond Improved Durability and Kinetics for Zinc‑Organic Batteries

Organic compounds have the advantages of green sustainability and high designability,but their high solubility leads to poor durability of zinc-organic batteries.Herein,a high-performance quinone-based polymer(H-PNADBQ)material is designed by introducing an intramolecular hydrogen bonding(HB)strategy.The intramolecular HB(C=O⋯N-H)is formed in the reaction of 1,4-benzoquinone and 1,5-naphthalene diamine,which efficiently reduces the H-PNADBQ solubility and enhances its charge transfer in theory.In situ ultraviolet-visible analysis further reveals the insolubility of H-PNADBQ during the electrochemical cycles,enabling high durability at different current densities.Specifically,the H-PNADBQ electrode with high loading(10 mg cm^(-2))performs a long cycling life at 125 mA g^(-1)(>290 cycles).The H-PNADBQ also shows high rate capability(137.1 mAh g^(−1)at 25 A g^(−1))due to significantly improved kinetics inducted by intramolecular HB.This work provides an efficient approach toward insoluble organic electrode materials.