Thioacetamide Additive Homogenizing Zn Deposition Revealed by In Situ Digital Holography for Advanced Zn Ion Batteries

Zinc ion batteries are considered as potential energy storage devices due to their advantages of low-cost,high-safety,and high theoretical capacity.However,dendrite growth and chemical corrosion occurring on Zn anode limit their commercialization.These problems can be tackled through the optimization of the electrolyte.However,the screening of electrolyte additives using normal electrochemical methods is time-consuming and labor-intensive.Herein,a fast and simple method based on the digital holography is developed.It can realize the in situ monitoring of electrode/electrolyte interface and provide direct information concerning ion concentration evolution of the diffusion layer.It is effective and time-saving in estimating the homogeneity of the deposition layer and predicting the tendency of dendrite growth,thus able to value the applicability of electrolyte additives.The feasibility of this method is further validated by the forecast and evaluation of thioacetamide additive.Based on systematic characterization,it is proved that the introduction of thioacetamide can not only regulate the interficial ion flux to induce dendrite-free Zn deposition,but also construct adsorption molecule layers to inhibit side reactions of Zn anode.Being easy to operate,capable of in situ observation,and able to endure harsh conditions,digital holography method will be a promising approach for the interfacial investigation of other battery systems.

"Win-Win"Scenario of High Energy Density and Long Cycling Life in a Novel Na_(3.9)MnCr_(0.9)Zr_(0.1)(PO_(4))_(3)Cathode

The development of high-energy and long-lifespan NASICON-type cathode materials for sodium-ion batteries has always been a research hotspot but a daunting challenge.Although Na_(4)MnCr(PO_(4))_(3)has emerged as one of the most promising high-energy-density cathode materials owing to its three-electron reactions,it still suffers from serious structural distortion upon repetitive charge/discharge processes caused by the Jahn-Teller active Mn^(3+).Herein,the selective substitution of Cr by Zr in Na_(4)MnCr(PO_(4))_(3)was explored to enhance the structural stability,due to the pinning effect of Zr ions and the≈2.9-electron reactions,as-prepared Na_(3.9)MnCr_(0.9)Zr_(0.1)(PO_(4))_(3)/C delivers a high capacity retention of 85.94%over 500 cycles at 5 C and an ultrahigh capacity of 156.4 mAh g^(-1)at 0.1 C,enabling the stable energy output as high as 555.2 Wh kg^(-1).Moreover,during the whole charge/discharge process,a small volume change of only 6.7%was verified by in situ X-ray diffraction,and the reversible reactions of Cr^(3+)/Cr^(4+),Mn^(3+)/Mn^(4+),and Mn^(2+)/Mn^(3+)redox couples were identified via ex situ X-ray photoelectron spectroscopy analyses.Galvanostatic intermittent titration technique tests and density functional theory calculations further demonstrated the fast reaction kinetics of the Na_(3.9)MnCr_(0.9)Zr_(0.1)(PO_(4))_(3)/C electrode.This work offers new opportunities for designing high-energy and high-stability NASICON cathodes by ion doping.

碳包覆纳米SnSb合金作为高性能钠离子电池负极材料

采用喷雾热解法合成了碳包覆的SnSb/C合金复合材料,利用X射线粉末衍射仪(XRD)、场发射扫描电子显微镜(FESEM)、透射电子显微镜(TEM)等方法对产物的物相和形貌进行了表征,其中SnSb/C颗粒为10 nm左右的复合材料(10-SnSb/C)作为钠离子电池负极时,表现出优异的循环和倍率性能。首圈放电达到722.1 mAh·g^−1,首圈库仑效率86.3%,在100、1000、3000 mA·g^−1下比容量分别为607.7、645.4、452.2 mAh·g^−1,在1000 mA·g^−1电流下循环200周后可逆容量达到623 mAh·g^−1,容量保持率为95%。SnSb/C复合材料出色的储钠性能源于其完全被碳包裹的纳米结构,该结构可以有效提高活性物质的利用率,促进电子、离子的传导,并且抑制纳米粒子在长循环过程中的粉化和团聚。

Recent advances in electrospun electrode materials for sodium-ion batteries

Sodium-ion batteries(SIBs)have been considered as an ideal choice for the next generation large-scale energy storage applications owing to the rich sodium resources and the analogous working principle to that of lithium-ion batteries(LIBs).Nevertheless,the larger size and heavier mass of Na^(+)ion than those of Li^(+)ion often lead to sluggish reaction kinetics and inferior cycling life in SIBs compared to the LIB counterparts.The pursuit of promising electrode materials that can accommodate the rapid and stable Na-ion insertion/extraction is the key to promoting the development of SIBs toward a commercial prosperity.One-dimensional(1 D)nanomaterials demonstrate great prospects in boosting the rate and cycling performances because of their large active surface areas,high endurance for deformation stress,short ions diffusion channels,and oriented electrons transfer paths.Electrospinning,as a versatile synthetic technology,features the advantages of controllable preparation,easy operation,and mass production,has been widely applied to fabricate the 1 D nanostructured electrode materials for SIBs.In this review,we comprehensively summarize the recent advances in the sodium-storage cathode and anode materials prepared by electrospinning,discuss the effects of modulating the spinning parameters on the materials’micro/nano-structures,and elucidate the structure-performance correlations of the tailored electrodes.Finally,the future directions to harvest more breakthroughs in electrospun Na-storage materials are pointed out.

Graphene oxide assisted facile hydrothermal synthesis of LiMn_(0.6)Fe_(0.4)PO_4 nanoparticles as cathode material for lithium ion battery

Assisted by graphene oxide（GO）,nano-sized LiMn0.6Fe0.4PO4 with excellent electrochemical performance was prepared by a facile hydrothermal method as cathode material for lithium ion battery.SEM and TEM images indicate that the particle size of LiMn0.6Fe0.4PO4（S2）was about 80 nm in diameter.The discharge capacity of LiMn0.6Fe0.4PO4 nanoparticles was 140.3 mAh-g^1 in the first cycle.It showed that graphene oxide was able to restrict the growth of LiMn0.6Fe0.4PO4 and it in situ reduction of GO could improve the electrical conductivity of LiMn0.6Fe0.4PO4 material.

Development Strategies in Transition Metal Borides for Electrochemical Water Splitting

Electrochemical water splitting is a feasible method for producing environmental benignity energy of hydrogen,while high price and low availability on the earth of noble electrocatalysts constrain their global-scale application.Transition metal borides(TMBs)have displayed unique metalloid characteristic and outstanding performance for oxygen evolution reaction(OER)and hydrogen evolution reaction(HER)in the last few decades.Herein,recent developments of the TMBs for HER and OER are summarized.Initially,the impact factors and relevant evaluation of electrocatalytic performance are described,that is,overpotential,Tafel slope and exchange current density,stability,faradaic efficiency,turnover frequency,mass and specific activities.Moreover,the optimization strategies of borides are emphasized,which principally include coupling with effective substrates,elemental doping,phase modification,interfacial engineering,and morphology control.Finally,in order to reach the goal of application,the remaining challenges and perspectives are given to point out a direction for enhancing the performance of borides.

Intercalation engineering of layered vanadyl phosphates for high performance zinc-ion batteries

Aqueous zinc-ion batteries(ZIBs) have attracted great attention as the candidates for large-scale energy storage system,recently,because of their low cost,environment-friendly,high safety,and high theoretical energy densities.Among the numerous cathode materials,layered structure vanadium based polyanionic compounds,such as VOPO_(4),exhibit high specific capacity for Zn ion storage.However,the low Zn ion diffusion coefficient and limited interlayer spacing make the cathodes low reversible capacity and inferior cycling stability.Herein,K ions were pre-intercalated into the VOPO_(4) layers via ions exchange adopting VOPO_(4)·2 H_(2) O as the precursor.When evaluated as the cathode for ZIBs,an excellent cycle stability of 400 cycles under a current density of 500 mA g^(-1) was achieved by the obtained KVOPO_(4) electrode,verifying the positive effect of intercalation engineering.Furtherly,a solid-solution reaction Zn ion storage mechanism was confirmed.This study provides a new insight to explore high performance cathode materials for ZIBs.

Coupled cobalt-doped molybdenum carbide@N-doped carbon nanosheets/nanotubes supported on nickel foam as a binder-free electrode for overall water splitting

In an attempt to develop low-cost,non-noble-metal bifunctional electrocatalysts for water electrolysis in alkaline media,cobalt-doped molybdenum carbide@N-doped carbon nanosheets/nanotubes were fabricated by using C3N4 as the carbon source on a 3D porous nickel foam substrate.Benefiting from the optimized electronic structure and enhanced mass and charge transport,as well as the 3D conducting pathway,MoxCoy@N-CNSs/CNTs shows superior performance towards both the hydrogen evolution reaction(HER)and oxygen evolution reaction(OER)in an alkaline medium.The optimal electrocatalyst is Mo2Co1@N-CNSs/CNTs,which reveals a current density of 10 mA cm^-2 at the low overpotentials of 99 mV and 300 mV for the HER and OER,respectively,and a relatively low cell voltage(1.63 V)for the overall water electrolysis.The method of optimizing the composition and nanostructure of a material provides a new avenue for the development and utilization of high-performance electrocatalysts.

Influence of interlayer water molecules in Ni-based catalysts for oxygen evolution reaction

Nickel-iron layered double hydroxides(NiFe LDHs) have been identified as one of the best promising electrocatalysts-candidates for oxygen evolution reaction(OER). However, the catalytic activity effected by interlayer water molecules is ignored and rarely reported. Herein, Ni(OH)_2, NiFe LDHs vertically aligned Ni foam are designed for OER. As a contrast, the corresponding electrocatalysts with the removal of the interlayer water molecules(Ni(OH)_2-AT, NiFe LDHs-AT) are developed to probe into the influence of the interlayer water molecules towards OER. As expected, NiFe LDH nanoplates exhibit excellent catalytic performance and durability for water electrolysis in alkaline conditions with lower overpotential and smaller Tafel slope compared to those of NiFe LDHs-AT, which are influenced mainly by stability of crystal structure due to the existence of interlayer water molecules. The discovery opens up a similar pathway by controlling the amount of water molecules to boost catalytic performance for studying other electrocatalysts with heteroatom dopant.

Electron modulation of cobalt carbonate hydroxide by Mo doping for urea-assisted hydrogen production

Combining urea oxidation reaction(UOR) with hydrogen evolution reaction(HER) is an effective method for energy saving and highly efficient electrocatalytic hydrogen production. Herein, molybdenumincorporated cobalt carbonate hydroxide nanoarrays(CoxMoyCH) are designed and synthesized as a bifunctional catalyst towards UOR and HER. Benefiting from the Mo doping, the dispersed nanoarray structure and redistributed electron density, the CoxMoyCH catalyst display outstanding catalytic performance and durability for both HER and UOR, affording the overpotential of 82 m V for HER and delivering a low potential of the 1.33 V for UOR(vs. reversible hydrogen electrode, RHE) to attain a current density of 10 m A cm^(-2), respectively. Remarkably, when CoxMoyCH was applied as bifunctional catalyst in a twoelectrode electrolyzer, a working voltage of 1.40 V is needed in urea-assisted water electrolysis at10 m A cm^(-2) and without apparent decline for 40 h, outperforming the working voltage of 1.51 V in conventional water electrolysis.

In/ex-situ Raman spectra combined with EIS for observing interface reactions between Ni-rich layered oxide cathode and sulfide electrolyte

The interfacial instability between Ni-rich layered oxide cathodes and sulfide electrolytes is a serious problem,leading to poor electrochemical properties of all-solid-state lithium batteries(ASSLB).The chemical/electrochemical side reactions are considered to be the origin of the interfacial deterioration.However,the influence of chemical and electrochemical side reactions on the interfacial deterioration is rarely studied specifically.In this work,the deterioration mechanism of the interface between LiNi0.85-xCo0.15AlxO2 and Li10GeP2S12 is investigated in detail by combining in/ex-situ Raman spectra and Electrochemical Impedance Spectroscopy(EIS).It can be determined that chemical side reaction between LiNi0.8Co0.15Al0.05O2 and Li10GeP2S12 will occur immediately once contacted,and the interfacial deterioration becomes more serious after charge-discharge process under the dual effects of chemical and electrochemical side reactions.Moreover,our research reveals that the interfacial stability and the cycle performance of ASSLB can be greatly enhanced by increasing Al-substitution for Ni in LiNi0.85-xCo0.15AlxO2.In particular,the capacity retention of LiNi0.6Co0.15Al0.25O2 cathode after 200 cycles can reach 81.9%,much higher than that of LiNi0.8Co0.15Al0.05O2 cathode(12.5%@200 cycles).This work gives an insight to study the interfacial issues between Ni-rich layered oxide cathode and sulfide electrolyte for ASSLBs.

Novel application of LiCoO_2 as a high-performance candidate material for supercapacitor

Electrochemical performances of LiCoO_2 as a candidate material for supercapacitor are systematically investigated. LiCoO_2 nanomaterials are synthesized via hydrothermal reaction with consequent calcination process. And the particle size increases as the calcination temperature rises. LCO-650 sample with the largest particle size displays the maximum capacitances of 817.5 F·g^-1 with the most outstanding capacity retention rate of 96.8% after 2000 cycles. It is shown that large particle size is beneficial to the electrochemical and structural stability of LiCoO_2 materials. We speculate that the micron-sized waste LiCoO_2 materials have great potential for supercapacitor application. It may provide a novel recovered approach for spent LIBs and effectively relieve the burdens on the resource waste and environment pollution.

Synergetic effects of NaAlH_4-TiF_3 co-additive on dehydriding reaction of Mg(AlH_4)_2

The effects of NaA1H4, TiF3 and NaA1H4-TiF3 co-additive on dehydriding reaction of Mg（A1H4）2 are systematically investigated. The on- set dehydrogenation temperature of the co-doped Mg（A1H4）2 composites decreased to 74 ℃, which is about 59 ℃ lower than that of pure Mg（A1H4）2. The dehydrogenation kinetics of NaA1H4-TiF3 co-doped Mg（A1H4）2 sample was also improved, which released about 94% hydrogen within 48 min, but no visible hydrogen was released from pure Mg（A1H4）2 under the same conditions. The activation energy of co-doped Mg（A1H4）2 was 85.6 kJ.mol-t, which was significantly lower than that of additive-free Mg（A1H4）2 sample. The synergetic effects of NaA1H4 and TiF3 on the dehydrogenation performance of Mg（A1H4）2 were confirmed. In addition, a possible catalytic mechanism is discussed, regarding the different roles of NaA1H4 and TiF3 on Mg（A1H4）2.

Crystalline-amorphous interfaces of NiO-CrO_(x)electrocatalysts for boosting the urea oxidation reaction

The overall energy efficiency of electrochemical systems is severely hindered by the traditional anodic oxygen evolution reaction(OER).Utilizing urea oxidation reaction(UOR)with lower thermodynamic potential to replace OER provides a promising strategy to enhance the energy efficiency.Amorphous and heterojunctions electrocatalysts have been aroused extensive studies owing to their unique physicochemical properties and outperformed activity.Herein,we report a simple method to construct a novel crystalline-amorphous NiO-CrO_(x)heterojunction grown on Ni foam for UOR electrocatalyst.The NiO-CrO_(x)electrocatalyst displays excellent UOR performance with an ultralow working potential of 1.32 V at 10 mA·cm^(−2)and ultra-long stability about 5 days even at 100 mA·cm^(−2).In-situ Raman analysis and temperature-programmed desorption(TPD)measurement verify that the presence of the amorphous CrO_(x)phase can boost the reconstruction from NiO to active NiOOH species and enhance adsorption ability of urea molecule.Besides,the unique crystalline-amorphous interfaces are also benefit to improving the UOR performance.

Conversion reaction lithium metal batteries

Contemporary social problems,such as energy shortage and environmental pollution,require developing green energy storage technologies in the context of sustainable development.With the application of secondary battery technology becoming widespread,the development of traditional lithium(Li)-ion batteries,which are based on insertion/deinsertion reactions,has hit a bottleneck;instead,conversion-type lithium metal batteries(LMBs)have attracted considerable attention owing to the high theoretical capacity of Li metal anodes.In this review,Li-S,Li-O_(2),and Li-SOCl_(2)batteries are used as examples to summarize LMBs based on their conversion reactions from the perspectives of cathode material,anode material,electrolyte,separator,and current collector.Key challenges exist regarding the conversion reactions of various batteries.To achieve the optimum performance and improve the application effect,several improvement strategies have been proposed in relation to reasonable designs of next-generation high-performance rechargeable batteries.

Ni_(2)P/NiMoP heterostructure as a bifunctional electrocatalyst for energy-saving hydrogen production

Electrochemical water splitting is a sustainable and feasible strategy for hydrogen production but is hampered by the sluggish anodic oxygen evolution reaction(OER).Herein,an effective approach is introduced to significantly decrease the cell voltage by replacing the anodic OER with a urea oxidation reaction(UOR).A Ni_(2)P/NiMoP nanosheet catalyst with a hierarchical architecture is uniformly grown on a nickel foam(NF)substrate through a simple hydrothermal and phosphorization method.The Ni_(2)P/NiMoP achieves impressive HER activity,with a low overpotential of only 22 mV at 10 mA cm^(-2)and a low Tafel slope of 34.5 mV dec^(−1).In addition,the oxidation voltage is significantly reduced from 1.49 V to 1.33 V after the introduction of 0.33 M urea.Notably,a two-electrode electrolyzer employing Ni_(2)P/NiMoP as a bifunctional catalyst exhibits a current density of 10 mA cm^(-2)at a cell voltage of 1.35 V and excellent long-term durability after 80 h.

Transition-Metal(Fe,Co,and Ni)-Based Nanofiber Electrocatalysts for Water Splitting

Electrochemical water splitting is a fascinating technology for sustainable hydrogen production,and electrocatalysts are essential to accelerate the sluggish hydrogen and oxygen evolution reactions(HER and OER).Transition-metal-based electrocatalysts have attracted enormous interests due to the abundant resources,low cost,and comparable catalytic performance to noble metals.Among these studies,fibrous materials possess distinct advantages,such as unique structure,high active surface area,and fast electron transport.Herein,the most recent progress of nanofiber electrocatalysts on synthesis and application in HER and OER is summarized,with emphasis on iron-,cobalt-,and nickel-based materials.Moreover,the challenge and prospects of fibrous-structured electrocatalysts on water splitting is provided.

PEM water electrolysis for hydrogen production:fundamentals,advances,and prospects

Hydrogen,as a clean energy carrier,is of great potential to be an alternative fuel in the future.Proton exchange membrane(PEM)water electrolysis is hailed as the most desired technology for high purity hydrogen production and self-consistent with volatility of renewable energies,has ignited much attention in the past decades based on the high current density,greater energy efficiency,small mass-volume characteristic,easy handling and maintenance.To date,substantial efforts have been devoted to the development of advanced electrocatalysts to improve electrolytic efficiency and reduce the cost of PEM electrolyser.In this review,we firstly compare the alkaline water electrolysis(AWE),solid oxide electrolysis(SOE),and PEM water electrolysis and highlight the advantages of PEM water electrolysis.Furthermore,we summarize the recent progress in PEM water electrolysis including hydrogen evolution reaction(HER)and oxygen evolution reaction(OER)electrocatalysts in the acidic electrolyte.We also introduce other PEM cell components(including membrane electrode assembly,current collector,and bipolar plate).Finally,the current challenges and an outlook for the future development of PEM water electrolysis technology for application in future hydrogen production are provided.

N-doped ZrO_(2) nanoparticles embedded in a N-doped carbon matrix as a highly active and durable electrocatalyst for oxygen reduction

Fabricating highly efficient and robust oxygen reduction reaction(ORR)electrocatalysts is challenging but desirable for practical Zn-air batteries.As an early transition-metal oxide,zirconium dioxide(ZrO_(2))has emerged as an interesting catalyst owing to its unique characteristics of high stability,anti-toxicity,good catalytic activity,and small oxygen adsorption enthalpies.However,its intrinsically poor electrical conductivity makes it difficult to serve as an ORR electrocatalyst.Herein,we report ultrafine N-doped ZrO_(2) nanoparticles embedded in an N-doped porous carbon matrix as an ORR electrocatalyst(N-ZrO_(2)/NC).The N-ZrO_(2)/NC catalyst displays four-electron reduction of oxygen in O.1 M KOH,Upon employment in a Zn-air battery,N-ZrO,/NC presented an exellent activity and long-term durability with a half-wave potential(E,v2)of 0.84 V and a selectivity for the intriguing powerdensity of 185.9 mwcm^(-2).anda high secific capacity of 797.9 mA h gzni,exceeding those of commercial Pt/C(122.1 mw cm^(-2) and 782.5 mA h gzn),This excellent performance is mainly ttributed to the ultrafine ZrO_(2) nanoparticles the conductive carbon substrate,and the modifed electronic band structure of ZrO_(2) after N-doping.Density functional theory calculations demonstrated that N-doping can reduce the band-gap of ZrO_(2) from 3.96 eV to 3.33 eV through the hybridization of the p state of the N atom with the 2p state of the oxygen atom;this provides enhanced electrical conductivity and results in faster electron-transfer kinetics.This work provides a new approach for the design of other enhanced semiconductor and insulator materials.

Hierarchical Engineering for High-Energy-Oriented Sodium-Ion Batteries

CONSPECTUS:Sodium-ion batteries(SIBs)have obtained extensive attention as desirable candidates for smart grids and large-scale energy storage systems(ESSs)because they have the conspicuous advantages of resource abundance and competitive price.However,the biggish radius and heavier molar mass of Na^(+) and the lower negative redox potential of Na^(+)/Na give rise to low volumetric/gravimetric energy densities,sluggish reaction dynamics,and an inferior life-span.It is therefore crucial to concentrate on the development of tailored electrode materials with robust architectures and expedited Na+diffusion kinetics so as to take SIB energy systems one step closer to practical applications.