Porous core–shell CoMn_2O_4 microspheres as anode of lithium ion battery with excellent performances and their conversion reaction mechanism investigated by XAFS

Porous core-shell CoMn204 microspheres of ca. 3-5μm in diameter were synthesized and served as an-ode of lithium ion battery. Results demonstrate that the as-synthesized CoMn204 materials exhibit excel-lent electrochemical properties. The CoMn204 anode can deliver a large capacity of 1070 mAh g-1 in thefirst discharge, a reversible capacity of 500 mAh g^-1 after 100 cycles with a coulombic efficiency of 98.5% at a charge-discharge current density of 200 mA g^-l, and a specific capacity of 385 mAh g^-1 at a muchhigher charge-discharge current density of 1600mA g^-1. Synchrotron X-ray absorption fine structure（XAFS） techniques were applied to investigate the conversion reaction mechanism of the CoMn204 anode.The X-ray absorption near edge structure （XANES） spectra revealed that, in the first discharge-charge cy-cle, Co and Mn in CoMn204 were reduced to metallic Co and Mn when the electrode was discharged to0.01 V, while they were oxidized respectively to CoO and MnO when the electrode was charged to 3.0V.Experiments of both XANE5 and extended X-ray absorption fine structure （EXAFS） revealed that neithervalence evolution nor phase transition of the porous core-shell CoMn204 microspheres could happen inthe discharge plateau from 0.8 to 0.6V, which demonstrates the formation of solid electrolyte interface（SEI） on the anode.

Chloride ion battery:A new emerged electrochemical system for next-generation energy storage

In the scope of developing new electrochemical concepts to build batteries with high energy density,chloride ion batteries(CIBs)have emerged as a candidate for the next generation of novel electrochemical energy storage technologies,which show the potential in matching or even surpassing the current lithium metal batteries in terms of energy density,dendrite-free safety,and elimination of the dependence on the strained lithium and cobalt resources.However,the development of CIBs is still at the initial stage with unsatisfactory performance and several challenges have hindered them from reaching commercialization.In this review,we examine the current advances of CIBs by considering the electrode material design to the electrolyte,thus outlining the new opportunities of aqueous CIBs especially combined with desalination,chloride redox battery,etc.With respect to the developing road of lithium ion and fluoride ion batteries,the possibility of using solid-state chloride ion conductors to replace liquid electrolytes is tentatively discussed.Going beyond,perspectives and clear suggestions are concluded by highlighting the major obstacles and by prescribing specific research topics to inspire more efforts for CIBs in large-scale energy storage applications.

Lithium-ion and solvent co-intercalation enhancing the energy density of fluorinated graphene cathode

Fluorinated carbons CF_xhold the highest theoretical energy density(e.g.,2180 W h kg^(-1)when x=1)among all cathode materials of lithium primary batteries.However,the low conductivity and severe polarization limit it to achieve its theory.In this study,we design a new electrolyte,namely 1 M LiBF_(4)DMSO:DOL(1:9 vol.),achieving a high energy density in Li/CF_xprimary cells.The DMSO with a small molecular size and high donor number successfully solvates Li^(+)into a defined Li^(+)-solvation structure.Such solvated Li^(+)can intercalate into the large-spacing carbon layers and achieve an improved capacity.Consequently,when discharged to 1.0 V,the CF_(1.12)cathode demonstrates a specific capacity of 1944 m A h g^(-1)with a specific energy density of 3793 W h kg^(-1).This strategy demonstrates that designing the electrolyte is powerful in improving the electrochemical performance of CF_(x) cathode.

Ni0.85 Se hexagonal nanosheets as an advanced conversion cathode for Mg secondary batteries

Mg secondary batteries are promising scalable secondary batteries for next-generation energy storage.However,Mg-storage cathode materials are greatly demanded to construct high-performance Mg batteries.Electrochemical conversion reaction provides plenty of cathode options,and strategy for cathode selection and performance optimization is of special significance.In this work,Ni0.85Se with nanostructures of dispersive hexagonal nanosheets(D-Ni0.85Se)and flower-like assembled nanosheets(F-Ni0.85Se)is synthesized and investigated as Mg-storage cathodes.Compared with F-Ni0.85Se,D-Ni0.85Se delivers a higher specific capacity of 168 mAh g^-1 at 50 mA g^-1 as well as better rate performance,owing to its faster Mg^2+-diffusion and lower resistance.D-Ni0.85Se also exhibits a superior cycling stability over 500cycles.An investigation on mechanism indicates an evolution of Ni0.85Se towards NiSe with cycling,and the Mg-storage reaction occurs between NiSe and metallic Ni^0.The present work demonstrates that advanced conversion-type Mg battery cathode materials could be constructed by soft selenide anions,and the electrochemical properties could be manipulated by rational material morphology optimization.

Electrochemical activation of oxygen atom of SnO2 to expedite efficient conversion reaction for alkaline-ion(Li+/Na+/K+)storages

SnO2-based anode materials have attracted much attention due to high capacity and relatively mild voltage platforms.However,limited by low initial Coulombic efficiency(ICE)and poor stability,its practical application is still challenging.Recently,it has been found that compositing carbon or metal particles with SnO2 is an effective strategy to achieve high alkaline-ion storages.Although this strategy may improve the kinetics and ICE of the electrochemical reaction,the specific mechanism has not been clearly elucidated.In this work,we found that the invalidation SnO2 may go through two steps:1)the conversion process from SnO2 to Sn and Li2O;2)the collapse of the electrode material resulted from huge volume changes during the alloyed Sn with alkaline ions.To address these issues,a unique robust Co-NC shell derived from ZIF-67 is introduced,in which the transited metallic Co nanoparticles could accelerate the decomposition of Sn-O and Li-O bonds,thus expedite the kinetics of conversion reaction.As a result,the SnO2@Co-NC electrode achieves a more complete and efficient transfer between SnO2 and Sn phases,possessing a potential to achieve high alkaline-ion(Li+/Na+/K+)storages.

Reducing voltage hysteresis of metal oxide anodes to achieve high energy efficiency for Li-ion batteries

In the past two decades,a lot of high-capacity conversion-type metal oxides have been intensively studied as alternative anode materials for Li-ion batteries with higher energy density.Unfortunately,their large voltage hysteresis(0.8-1.2 V) within reversed conversion reactions results in huge round-trip inefficiencies and thus lower energy efficiency(50%-75%) in full cells than those with graphite anodes.This remains a long-term open question and has been the most serious drawback toward application of metal oxide anodes.Here we clarify the origins of voltage hysteresis in the typical SnO2anode and propose a universal strategy to minimize it.With the established in situ phosphating to generate metal phosphates during reversed conversion reactions in synergy with boosted reaction kinetics by the added P and Mo,the huge voltage hysteresis of 0.9 V in SnO_(2),SnO_(2)-Mo,and 0.6 V in SnO2-P anodes is minimized to 0.3 V in a ternary SnO_(2)-Mo-P(SOMP) composite,along with stable high capacity of 936 mA h g^(-1)after 800 cycles.The small voltage hysteresis can remain stable even the SOMP anode operated at high current rate of10 A g^(-1)and wide-range temperatures from 60 to 30℃,resulting in a high energy efficiency of88.5% in full cells.This effective strategy to minimize voltage hysteresis has also been demonstrated in Fe2O3,Co3O4-basded conversion-type anodes.This work provides important guidance to advance the high-capacity metal oxide anodes from laboratory to industrialization.

Fluorinated soft carbon as an ultra-high energy density potassium-ion battery cathode enabled by a ternary phase K_(x)FC

Fluorinated carbons(CFx)have been widely applied as lithium primary batteries due to their ultra-high energy density.It will be a great promise if CFx can be rechargeable.In this study,we rationally tune the C-F bond strength for the alkaline intercalated CFx via importing an electronegative weaker element K instead of Li.It forms a ternary phase K_(x)FC instead of two phases(LiF+C)in lithium-ion batteries.Meanwhile,we choose a large layer distance and more defects CFx,namely fluorinated soft carbon,to accommodate K.Thus,we enable CFx rechargeable as a potassium-ion battery cathode.In detail fluorinated soft carbon CF_(1.01) presents a reversible specific capacity of 339 mA h g^(-1)(797 Wh kg^(-1))in the 2nd cycle and maintains 330 mA h g^(-1)(726 Wh kg^(-1))in the 15th cycle.This study reveals the importance of tuning chemical bond stability using different alkaline ions to endow batteries with rechargeability.This work provides good references for focusing on developing reversible electrode materials from popular primary cell configurations.

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.

Neutral color and self-healable electrochromic system based on CuI/Cu and I_(3)^(-)/I^(-)conversions

The electrochromic(EC)mechanisms of inorganic materials are usually based on reversible cation insertion/extraction or metal deposition/dissolution,which are plagued by ion trapping and dendrite growth,respectively.In this paper,a novel conversion-type electrochromic mechanism is proposed,by making good use of the CuI/Cu redox couple.This CuI-based electrochromic system shows a neutral color switching from transparent and dim grey.By simply increasing the bleaching voltage,I_(3)^(-)/I^(-)redox couple can be further activated.The generated I_(3)^(-)will readily react with Cu,effectively improving the conversion reversibility and thereby rejuvenating the degraded electrochromic performance.Thanks to the well-designed electrode and the self-healing ability,this conversion electrochromic system achieves rapid response times(tcoloring:23 s,tbleaching:6 s),decant optical modulation amplitude(26.4%),high coloration efficiency(86.15 cm^(2)·C^(-1)),admirable cyclic durability(without performance degradation after 480 cycles)and excellent optical memory ability(transmittance variation<1%after 10 h open-circuit storage).The establishment of this conversion-type electrochromism may inspire the exploration of novel electrochromic materials and devices.

长焰煤热解半焦气化反应动力学研究

为获得升温速率对长焰煤热解半焦气化反应的影响,利用热重分析仪对半焦在不同升温速率(5、10、20、30、40 ℃/min)条件下的气化反应进行了研究,并采用Flunm-Wall-Ozawa(FWO)和Friedman等转化率法进行半焦气化动力学参数的分析计算。结果表明,升温速率的增大不利于半焦的气化,升温速率越快、气化反应温度越高,且气化后期气化速率峰会出现重叠;2种等转化率法求得的半焦气活化能分别为145.91±32 kJ/mol和149.21±7 kJ/mol;采用等转化率方法研究半焦气化动力学可行。

High Initial Reversible Capacity and Long Life of Ternary SnO_(2)-Co-carbon Nanocomposite Anodes for Lithium-Ion Batteries

The two major limitations in the application of SnO_2 for lithium?ion battery(LIB) anodes are the large volume variations of SnO_2 during repeated lithiation/delithiation processes and a large irreversible capacity loss during the first cycle, which can lead to a rapid capacity fade and unsatisfactory initial Coulombic e ciency(ICE). To overcome these limitations, we developed composites of ultrafine SnO_2 nanoparticles and in situ formed Co(CoSn) nanocrystals embedded in an N?doped carbon matrix using a Co?based metal–organic framework(ZIF?67). The formed Co additives and structural advantages of the carbon?confined SnO_2/Co nanocomposite e ectively inhibited Sn coarsening in the lithiated SnO_2 and mitigated its structural degradation while facilitating fast electronic transport and facile ionic di usion. As a result, the electrodes demonstrated high ICE (82.2%), outstanding rate capability(～ 800 mAh g^(-1) at a high current density of 5 A g^(-1)), and long?term cycling stability(～ 760 mAh g^(-1) after 400 cycles at a current density of 0.5 A g^(-1)). This study will be helpful in developing high?performance Si(Sn)?based oxide, Sn/Sb?based sulfide, or selenide electrodes for LIBs. In addition, some metal organic frameworks similar to ZIF?67 can also be used as composite templates.

Carbon Encapsulated Nickel Nanocomposites for the Cathode in Advanced Lithium Sulfur Batteries

Lithium sulfur(Li-S)batteries are poised to be the next generation of high-density energy storage devices.In recent years,the concept of“electrocatalysis”has been introduced into the field of Li-S batteries,and some transition metals have been proved to catalyze the electrochemical conversion reaction of sulfur species.In this study,carbon encapsulated nickel nanoparticles(Ni@C)with a specific surface area of 146 m^(2)/g are shown to play a definitive electrocatalytic role for the sulfur cathode.With Ni@C incorporated,the Ni@C/G-S electrode achieved a better electrochemical performance than the G-S electrode.Moreover,the reversible capacity and cycle stability were further improved through chemical modifications of the carbon shell.The influence of doping with different elements on the Li-S battery performance was also investigated in detail.Higher specific capacities of 1229 mA·h/g,927 mA·h/g,and 830 mA·h/g were achieved at 0.2 C,0.5 C,and 1.0 C for the N-Ni@C-G/S electrode.Besides,the B-Ni@C-G/S electrode possessed a best cycle stability.

Metallic phase W_(0.9)Mo_(0.1)S_(2)for high-performance anode of sodium ion batteries through suppressing the dissolution of polysulfides

WS_(2)with layered graphite-like structure as anode for sodium ion batteries has high specific capacity.However,the poor cycling performance and rate capability of WS_(2)caused by the low electronic conductivity and structure changes during cycles inhibit its practical application.Herein,metallic phase(1T)W_(x)Mo_(1−x)S2(x=1,0.9,0.8 and 0.6)with high electronic conductivity and expanded interlayer spacing of 0.95 nm was directly prepared via a simple hydrothermal method.Specially,1T W_(0.9)Mo_(0.1)S_(2)as anode for sodium ion batteries displays high capacities of 411 mAh g^(-1)at 0.1 A g^(-1)after 180 cycles and 262 mAh g^(-1)at 1 A g^(-1)after 280 cycles and excellent rate capability(245 mAh g^(-1)at 5 A g^(-1)).The full cell based on Na_(3)V_(2)(PO_(4))_(2)O_(2)F/C cathode and 1T W_(0.9)Mo_(0.1)S_(2)anode also exhibits high capacity and good cycling performance.The irreversible electrochemical reaction of 1T W_(0.9)Mo_(0.1)S_(2)with Na ions during first few cycles results in the main products of W-Mo alloy and S.The strong adsorption of W-Mo alloy with polysulfides can effectively suppress the dissolution and shuttle effect of polysulfides,which ensures the excellent cycling performance of 1T W_(0.9)Mo_(0.1)S_(2).

Reversible potassium storage in ultrafine CF_(x): A superior cathode material for potassium batteries and its mechanism

Current studies of cathodes for potassium batteries(PBs) mainly focus on the intercalation-type materials.The conversion-type materials that possess much higher theoretical capacities are rarely discussed in previous literatures.In this work,carbon fluoride(CF_x) is reported as a high capacity conversion-type cathode for PBs for the first time.The material delivers a remarkable discharge capacity of>250 mAh g^(-1) with mid-voltage of 2.6 V at 20 mA g^(-1).Moreover,a highly reversible capacity of around 95 mAh g^(-1) is achieved at 125 mA g^(-1) and maintained for 900 cycles,demonstrating its excellent cycling stability.The mechanism of this highly reversible conversion reaction is further investigated by nuclear magnetic resonance spectra,X-ray diffraction,and transmission electron microscopy studies.According to the analyses,the C-F bond in the cycled material is different from that in the pristine state,which presents relatively higher reversibility.This finding offers important insights for further improving the performance of the CF_x.This work not only demonstrates the CF_x as a high performance cathode for PBs,but also paves a new avenue of exploring conversion-type cathodes for high energy density PBs.

Exploration of cobalt selenite-carbon composite porous nanofibers as anode for sodium-ion batteries and unveiling their conversion reaction mechanism

Efforts have been made to develop a promising anode material with a novel composition for sodiumion batteries(SIBs).In this study,the sodium-ion storage mechanism of transition metal selenite that comprises transition metal cation coupled with two anions is studied.Amorphous cobalt selenite(CoSeO_(3))-carbon composite nanofibers containing numerous pores are synthesized via electrospinning process.Upon heat treatment of the electrospun nanofibers containing selenium,CoSe_(2)nanoclusters are formed.During the subsequent oxidation,CoSe_(2)transformed into amorphous CoSeO_(3)and some part of carbon was oxidized into CO_(2),leaving the pores inside the nanofiber.To unveil the electrochemical reaction mechanism,analytical methods including cyclic voltammetry,ex-situ X-ray photoelectron spectroscopy,ex-situ transmission electron microscopy,and in-situ electrochemical impedance spectroscopy techniques were adopted.Based on the analyses,the following conversion reaction from the second cycle onward is suggested:CoO+xSeO_(2)+(1-x)Se+4(x+1)Na^(+)+4(x+1)e~-?Co+(2x+1)Na_(2)O+Na_(2)Se.Furthermore,the electrochemical properties of porous CoSeO_(3)-carbon composite nanofibers are analyzed in detail.The anode material exhibited stable cycle stability up to 200 cycles at 0.5 A g^(-1)and high rate performance up to 5 A g^(-1).

Thermodynamic Properties of Non-Oxide Composite Refractories

For initiative application of non-oxides in refractories, it is essential to study thermodynamic properties of non-oxides. The stability and stable order of non-ox- ides under oxidized atmosphere are analyzed firstly and then a new process, “converse reaction sintering”, is proposed. The results of study on oxidation mechanism of silicon and aluminum nitrides indicate that the gaseous suboxides can be produced observably when the oxygen partial pressure is lower than “conversion oxygen partial pressure”. The suboxides can be deposited near the surface of composite to become a compact layer. This causes the material possessing a performance of “self-impedient oxidation”. Metal Si and Al are the better additives for increasing the density and width of compact layer and increasing the ability of anti-oxidation and anti-corrosion. The study on Si3 N4-Al2O3, Si3N4-MgO, Si3 N4-SiC systems is also enumerated as examples in the paper. The experimental results show that the converse reaction sintering is able to make high performance composites and metal Si and Al not only can promote the sintering but also increase the density and width of compact layer.

An in-situ generated Bi-based sodiophilic substrate with high structural stability for high-performance sodium metal batteries

Sodium(Na)metal anode exhibits a potential candidate in next-generation rechargeable batteries owing to its advantages of high earth abundance and low cost.Unfortunately,the practical development of sodium metal batteries is inherently plagued by challenges such as the side reactions and the growth of Na dendrites.Herein we report a highly stable Bi-based“sodiophilic”substrate to stabilize Na anode,which is created by in-situ electrochemical reactions of 3D hierarchical porous Bi_(2)MoO_(6)(BMO)microspheres.BMO is initially transformed into the Bi“nanoseeds”embedded in the Na-Mo-O matrix.Subsequently,the Bi nanoseeds working as preferential nucleation sites through the formation of BiNa alloy enable the non-dendritic Na deposition.The asymmetric cells based on such BMO-based substrate can deliver a long-term cycling for 600 cycles at a large capacity of 4 m Ah cm^(-2) and for 800 cycles at a high current density of 10 m A cm^(-2).Even at a high depth of discharge(66.67%),the Na-predeposited BMO(Na@BMO)electrodes can cycle for more than 1600 h.The limited Na@BMO anodes coupled with the Na_(3)V_(2)(PO_(4))_(3) cathodes(N/P ratio of 3)in full cells also show excellent electrochemical performance with a capacity retention of about 97.4%after 1100 cycles at 2 C.

煤低温氧化动力学参数测试方法对比研究

针对现有研究缺乏对不同煤低温氧化动力学参数测试方法的对比分析,采用Coats-Redfern法、q/m法及Starink等转化率法3种测试方法分别计算煤低温氧化动力学参数,并以煤氧化自热反应时间和自燃临界堆积厚度作为对比参量比较3种方法的准确性。通过绝热氧化装置和同步热分析仪进行了煤样在纯氧和贫氧条件下的绝热氧化实验、多升温速率实验和恒温实验。根据热分析实验结果,分别采用3种方法计算煤低温氧化动力学参数。依据获得的动力学参数计算煤氧化自热反应时间和自燃临界堆积厚度。将计算结果与实测的煤氧化自热反应时间和采空区实际遗煤厚度进行对比,评价3种方法的准确性。实验结果表明:①通过绝热氧化实验实测的煤氧化自热温度变化率随时间的推移均逐渐增大;采用Coats-Redfern法计算得到的温度在0~8 h(q/m法为0~10 h)内几乎不发生变化,超过这一时间段后温度迅速升高;采用Starink等转化率法获得的温度变化趋势与绝热氧化实验实测结果类似。②采空区实际遗煤厚度大于Coats-Redfern法计算得到的临界堆积厚度;采用q/m法获得的临界堆积厚度超过了该工作面所在煤层厚度,与实际明显不符;采用Starink等转化率法获得的计算结果与实际较为接近。③采用Starink等转化率法获得的预测结果与实测结果更为接近,表明Starink等转化率法得到的煤低温氧化动力学参数较其他2种测试方法更为准确。

Chalcogen cathode and its conversion electrochemistry in rechargeable Li/Na batteries

Chalcogen elements,such as sulfur(S),selenium(Se),tellurium(Te)and the interchalcogen compounds,have been studied extensively as cathode materials for the next-generation rechargeable lithium/sodium(Li/Na)batteries.The high energy output of the Li/Na-chalcogen battery originates from the two-electron conversion reaction between chalcogen cathode and alkali metal anode,through which both electrodes are able to deliver high theoretical capacities.The reaction also leads to parasitic reactions that deteriorate the chemical environment in the battery,and different cathode-anode combinations show their own features.In this article,we intend to discuss the fundamental conversion electrochemistry between chalcogen elements and alkali metals and its potential influence,either positive or negative,on the performance of batteries.The strategies to improve the conversion electrochemistry of chalcogen cathode are also reviewed to offer insights into the reasonable design of rechargeable Li/Nachalcogen batteries.

A semiclassical molecular dynamics of the photochromic ring-opening reaction of spiropyran

The photochromic ring-opening reaction of spiropyran（SP） has been investigated by a realistic semiclassical dynamics simulation,accompanied by SA3-CASSCF（12 10）/MS-CASPT2 potential energy curves（PECs） of S0–S2.The main simulation results show the dominate pathway corresponds to the ringopening process of trans-SP to form the most stable merocyanine（MC） product.These findings provide more important complementarity for interpreting experimental observations.