Ultrathin 3 V Spinel Clothed Layered Lithium-Rich Oxides as Heterostructured Cathode for High-Energy and High-Power Li-ion Batteries

In an attempt to overcome the drawbacks of high-capacity layered lithium-rich cathodes xLi2MnO3·(1–x)LiMO2(0-1 and maintains 259.8 mAh g^-1 after 80 cycles at 0.1 C rate.Meanwhile,it delivers outstanding rate discharge capacities of 229.4 mAh g^-1 at 1 C,216.8 mAh g^-1 at 2 C and 184.4 mAh g^-1 at 5 C as well as alleviated voltage fade.It is believed the ultrathin clothing spinel layer plays a vital role in the modification of the materials kinetics,and structural and electrochemical stability of the heterostructured cathode.     

β-MnO2 with proton conversion mechanism in rechargeable zinc ion battery

Rechargeable aqueous zinc ion battery(RAZIB)is a promising energy storage system due to its high safety,and high capacity.Among them,manganese oxides with low cost and low toxicity have drawn much attention.However,the under-debate proton reaction mechanism and unsatisfactory electrochemical performance limit their applications.Nanorod b-MnO₂ synthesized by hydrothermal method is used to investigate the reaction mechanism.As cathode materials for RAZIB,the Zn//b-MnO₂ delivers 355 mA h g^-1(based on cathode mass)at0.1 A g^-1,and retain 110 mA h g^-1 after 1000 cycles at 0.2 A g^-1.Different from conventional zinc ion insertion/extraction mechanism,the proton conversion and Mn ion dissolution/deposition mechanism of b-MnO₂ is proposed by analyzing the evolution of phase,structure,morphology,and element of b-MnO₂ electrode,the pH change of electrolyte and the determination of intermediate phase MnO OH.Zinc ion,as a kind of Lewis acid,also provides protons through the formation of ZHS in the proton reaction process.This study of reaction mechanism provides a new perspective for the development of Zn//MnO₂ battery chemistry.     

High capacity lithium-manganese-nickel-oxide composite cathodes with low irreversible capacity loss and good cycle life for lithium ion batteries

We report a method to eliminate the irreversible capacity of 0.4Li_2MnO_3·0.6LiNi_(0.5)Mn_(0.5)O_2(Li_(1.17)Ni_(0.25)Mn_(0.583)O_2) by decreasing lithium content to yield integrated layered-spinel structures.XRD patterns,High-resolution TEM image and electrochemical cycling of the materials in lithium cells revealed features consistent with the presence of spinel phase within the materials.When discharged to about 2.8 V,the spinel phase of LiM_2O_4(M=Ni,Mn) can transform to rock-salt phase of Li_2M_2O_4(M=Ni,Mn) during which the tetravalent manganese ions are reduced to an oxidation state of 3.0.So the spinel phase can act as a host to insert back the extracted lithium ions(from the layered matrix) that could not embed back into the layered lattice to eliminate the irreversible capacity loss and increase the discharge capacity.Their electrochemical properties at room temperature showed a high capacity(about 275 mAh g~(-1) at 0.1 C) and exhibited good cycling performance.     

Interfacial chemistry ofγ-glutamic acid-derived block polymer binder directing the interfacial compatibility of high voltage LiNi0.5Mn1.5O4 electrode

LiNi0.5Mn1.5O4(LNMO)spinel is one of the most promising high voltage cathode candidates for lithium ion batteries(LIBs).However,owing to the instability for organic electrolytes at 5V high voltage,it exhibits continuous oxidation,leading to the formation of unstable interface and the notorious dissolution of transition metal,which prevents the successful commercialization of LNMO.Herein,on the basis of energy level simulation,we present a high voltage resistant binder shielding strategy to address the challenging interfacial issue of LiNi0.5Mn1.5O4cathode.Our strategy is to design a novel poly(γ-glutamic acid)-c-1H,1H,9H,9H-perfluoro-1,9-nonanediol(γ-PGFO)binder with superior transition metal chelating effect and well-matched energy level to guarantee fantastic interfacial compatibility.It is demonstrated that the dissolution of transition metal is significantly suppressed in the presence ofγ-PGFO binder,which excels in the literature.It is also noted that intramolecular hydrogen binding of the well-designed binder can generate powerful facial-contact binding,which is significant for a promising binder.By encapsulating this binder inside the cathode matrix,the Li Ni0.5Mn1.5O4electrode exhibits a capacity of 105.8 m Ah g^-1after 500cycles at 1 C with a capacity retention of 88.2%,which is significantly superior to that of polyvinylidene fluoride(PVDF)/Li Ni0.5Mn1.5O4electrode(a capacity of 82.9 m Ah g^-1and a capacity retention of 63.4%).The overall Coulombic efficiency ofγ-PGFO/Li Ni0.5Mn1.5O4electrode is prominently improved to be 99.1%,compared with 95.5%of PVDF counterpart.The presented results demonstrate a promising strategy of amino acid-based binder with strong transition metal chelating capability for boosting the rapid development of high voltage lithium ion battery.     

Synthesis and Electrochemical Investigation of O3-Type High-nickel NCM Cathodes for Sodium-ion Batteries

Sodium ion batteries(SIBs)are promising energy storage devices for smart grid applications due to their low cost and the high abundance of sodium,but few cathode materials of SIBs with high energy density are available for practical applications.Herein,a series of NaNCM ternary materials(NCM=nickel-cobalt-manganese)is obtained by solid-phase reaction with well-regulated temperature and other reaction conditions.XRD results show that impure NiO phase is more likely to occur under high nickel content.The cross-section SEM indicates that the primary particles in the electrode materials are radially distributed along the radial direction,and the internal porous structure is conducive to the infiltration of electrolyte.The initial specific capacities of Na[Ni0.68Co0.10Mn0.22]O2(NaNCM712),Na[Ni0.6Co0.2Mn0.2]O2(NaNCM622)and Na[Ni0.4Co0.3Mn0.3]O2(NaNCM433)at 0.2 C are 165.5,153.1 and 146.8 mA·h/g,and the corresponding capacity retention rates are 63.2%,78.5%and 71.7%after 100 cycles.NaNCM712 possesses the highest initial specific capacity,and NaNCM433 delivers the best rate capability.The rate capabilities of high-nickel and low-cobalt NaNCM cathodes need to be further improved.Moreover,ex-situ XRD pattern reveals the structure evolution(from O3 type to P2 type)during a long cycling charge and discharge process.     

Understanding of performance degradation of LiNi_(0.80)Co_(0.10)Mn_(0.10)O_2 cathode material operating at high potentials

Inferior cycling stability, poor safety, and gas generation are long lasting problems of Ni-rich Li Ni0.80 Co0.10 Mn0.10 O2(NCM811) cathode material. Although much effort has been made, mechanisms for the above problems are poorly understood. Studying the cycling and float-charging characteristics of Li/NCM811 cells in high voltage conditions(4.5 V and 4.7 V, respectively), in this work we find that nearly all known problems with NCM811 material can be attributed to the oxidation of lattice oxygen occurring in the capacity region corresponding to H2 → H3 phase transition. While contributing to overall capacity,the oxidation of lattice oxygen results in a loss of oxygen through oxygen evolution and relative reactions between active oxygen evolution intermediates and electrolyte solvents. It is the loss of oxygen that results in irreversible layered-spinel-rocksalt phase transition, secondary particle cracking, and performance degradation. The conclusions of this work suggest that the priority for further research on NCM811 material should give to the suppression of oxygen evolution, followed by the use of the anti-oxygen electrolyte being chemically stable against the active oxygen evolution intermediates.     

Study on structural characteristics and adsorption performance of ultrasonic treated Mn-containing sulfur transfer agent

To prepare manganese-containing spinel sulfur transfer agent with acid peptization, ultrasonic wave is used for the first time to modify the structure of sulfur transfer agent in this work. Mini fixed bed reactor was used to investigate the effect of ultrasonic power, time and temperature on the structure and oxidation adsorption performance of sulfur transfer agent and the adsorption kinetics and mechanism of SO2 were analyzed. SEM, TEM, XRD and N2 adsorption-desorption techniques were employed to characterize and analyse the function of sulfur transfer agent. The results indicated that manganese-containing spinel is a kind of promising sulfur transfer agent and exhibits higher sulfur capacity and desulfurization degree under the selected conditions of the ultrasonic wave power of 60%, and with the treatment period for 3 h at a temperature of 60 ℃.     

Reduced graphene oxide doping flower-like Fe7S8 nanosheets for high performance potassium ion storage

Finding easy-to-operate strategy to obtain anode material with well-designed structure and excellent electrochemical performance is necessary to promote the development of the future potassium-ion batteries(PIBs).In this work,we synthesized reduced graphene oxide doping flower-like Fe₇S₈ nanosheets electrode materials using one-step hydrothermal strategy.The rGO@Fe₇S₈ composite is composed of homogeneous Fe₇S₈ and reduced graphene oxide thin nanosheets.This unique structure not only promotes the penetration of electrolyte and increases the conductive of the pure Fe₇S₈ electrode materials,but also relieves the volume expansion of K⁺ during charge/discharge process.When applied this interesting anode electrode for PIBs,the rGO@Fe₇S₈ exhibits excellent electrochemical performance.It delivers a high reversible specific capacity of 445 mAh g^-1 at 50 mA g^-1,excellent rate performance(284 mAhg^-1at 500 mA g^-1 and 237 mAh g^-1 at 1000 mA g^-1),and a high cycling stability at 100 mA g^-1(maintained 355 mAh g^-1 after 300 cycles).     

Reversible potassium storage in ultrafine CFx: 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.     

Hexagonal FeNi2Se4@C Nanoflakes as High Performance Anode Materials for Sodium-ion Batteries

Metal selenides have drawn significant attention as promising anode materials for sodium-ion batteries(SIBs)owing to their high electronic conductivity and reversible capacity.Herein,hexagonal FeNi2Se4@C nanoflakes were synthesized via a facile one-step hydrothermal method.They deliver a reversible capacity of 480.7 mA·h/g at 500 mA/g and a high initial Coulombic efficiency of 87.8%.Furthermore,a discharge capacity of 444.8 mA·h/g can be achieved at 1000 mA/g after 180 cycles.The sodium storage mechanism of FeNi2Se4@C is uncovered.In the discharge process,Fe and Ni nanoparticles are generated and distributed in Na2Se matrix homogeneously.In the charge process,FeNi2Se4 phase is formed reversibly.The reversible phase conversion of FeNi2Se4@C during cycling is responsible for the excellent electrochemical performance and enables FeNi2Se4@C nanoflakes promising anode materials for SIBs.     

Raising the capacity of lithium vanadium phosphate via anion and cation co-substitution

The pursuit for batteries with high specific energy provokes the research of high-voltage/capacity cathode materials with superior stability and safety as the alternative for lithium iron phosphate.Herein,using the sol-gel method,a lithium vanadium phosphate with higher average discharge voltage(3.8 V,vs.Li+/Li) was obtained from a single source for Mg2+ and Cl-co-substitution and uniform carbon coating,and a nearly theoretical capacity(130.1 mA h g^-1) and outstanding rate performance(25 C) are acquired together with splendid capacity retention(80%) after 650 cycles.This work reveals that the well-sized anion and cation substitution and uniform carbon coating are of both importance to accelerate kinetic performance in the context of nearly undisturbed crystal structure for other analogue materials.It is anticipated that the electrochemistry comprehension will shed light on preparing cathode materials with high energy density in the future.     

Nb2CTx MXene: High capacity and ultra-long cycle capability for lithium-ion battery by regulation of functional groups

MXenes are well known for their potential application in supercapacitors due to their high-rate intercalation pseudocapacitance and long cyclability.However,the reported low capacity of pristine MXenes hinders their practical application in lithium-ion batteries.In this work,a robust strategy is developed to control the functional groups of Nb_2 CT_x MXene.The capacity of pristine Nb_2 CT_x MXene can be significantly increased by Li~+ intercalation and surface modification.The specific capacity of the treated Nb_2 CT_x is up to 448 mAh g^-1 at 0.05 A g^-1,and at a large current density of 2 A g^-1 remains a high reversible capacity retention rate of 75% after an ultra-long cycle of 2000 cycles.These values exceed most of the reported pristine MXenes(including the most studied Ti_3 C_2 T_x) and carbon-based materials.It demonstrates that this strategy has great help to improve the electrochemical performance of pristine MXene,and the results enhance the promise of MXenes in the application of lithium-ion batteries.     

Sample Duplication Method for Monte Carlo Simulation of Large Reaction-Diffusion System

The sample duplication method for the Monte Carlo simulation of large reaction-diffusion system is proposed in this paper. It is proved that the sample duplication method will effectively raise the efficiency and statistical precision of the simulation without changing the kinetic behaviour of the reaction-diffusion system and the critical condition for the bifurcation of the steady-states. The method has been applied to the simulation of spatial and time dissipative structure of Brusselator under the Dirichlet boundary condition. The results presented in this paper definitely show that the sample duplication method provides a very efficient way to sol-'e the master equation of large reaction-diffusion system. For the case of two-dimensional system, it is found that the computation time is reduced at least by a factor of two orders of magnitude compared to the algorithm reported in literature.     

Influences of Na-Mn Ratio on Electrochemical Performances and Intercalation-Deintercalation Processes of Sodium Ion in NaxMnO2北大核心CSCD

In this work, NaxMnO2was synthesized by a solid-state reaction. The influences of Na:Mn ratio on the structure, morphology and electrochemical performance, and sodium ion intercalation/deintercalation processes were characterized by X-ray diffraction, X-ray photoelectron spectroscopy, field emission scanning electron microscopy, cyclic voltammetry, electrochemical impedance spectroscopy and galvanostatic charge-discharge test. The prepared NaxMnO2was mainly composed of Na0.7MnO2and Na0.91MnO2, and the content of Na0.91MnO2increased with the increase of Na:Mn ratio. However, the activation energy values of surface membrane diffusion, interfacial electrochemical reaction and Na+ diffusion in the bulk material first decreased and then increased with the increase of Na:Mn ratio, while the discharge capability first increased and then decreased with the increase of Na:Mn ratio. The sample synthesized with the Na:Mn ratio of 0.80 delivered a discharge capacity of 152.8 mAh·g-1with a capacity retention of 80.6% after 50 cycles at 1C. Even being charged/discharged at 5C, this sample still provided a discharge capacity of 88.3 mAh·g-1, showing good cycle-stability and rate performance. The activation energy values of surface membrane diffusion, interfacial electrochemical reaction and solid-phase diffusion were found to be 68.23, 40.07 and 57.62 kJ·mol-1, respectively. © Journal of Electrochemistry 2018.     

Perovskite LaFeO3 supported bi-metal catalyst for syngas methanation

LaFeO3 perovskite supported Ni and Ni-Fe catalysts were prepared and applied to methanation reaction of syngas.Two preparation methods were employed.One was one-step citrate complexing method,and the other was a two step method using citrate complexing method to produce LaFeO3 and followed by loading nickel oxide on it with impregnation.The structure evolution of the sample as prepared was investigated by XRD,TPR and TEM techniques.For the former,the chemical composites of the calcined sample are NiO-Fe2O3/LaFe1-xNix O3.After reduction and reaction of CO methanation,its composites convert to Fe-Ni@Ni/LaFeO3-La2O2CO3,in which Fe-Ni@Ni is metal particles in nano-size composed of nickel core and Fe-Ni alloy shell.For the latter,the chemical composites of the calcined sample are NiO/LaFeO3; and after reduction and reaction of CO methanation,its chemical composites change to Ni/LaFeO3.Ni/LaFeO3 catalyst is a little more active, while Fe-Ni@Ni/LaFeO3-La2O2CO3 is much more stable and shows very good resistance to carbon deposition.In this work it is aimed to show that the structure and composites of the catalysts can be tailored using perovskite-type oxide as precursor prepared with different methods and conditions.Therefore,it is a promising route to prepare supported bi-metal catalysts in nano-size for a lot of metals with desired catalytic performances.     

Concurrent recycling chemistry for cathode/anode in spent graphite/LiFePO4 batteries:Designing a unique cation/anion-co-workable dual-ion battery

With the increasing popularity of new en ergy electric vehicles,the dema nd for lithium-ion batteries(LIBs)has been growing rapidly,which will produce a large number of spent LIBs.Therefore,recycling of spe nt LIBs has become an urge nt task to be solved,otherwise it will inevitably lead to serious environmental pollution.Herein,a unique recycling strategy is proposed to achieve the concurrent reuse of cathode and anode in the spent graphite/LiFePO₄ batteries.Along with such recycling process,a unique cathode composed of recycled LFP/graphite(RLFPG)with cation/anion-co-storage ability is designed for new-type dual-ion battery(DIB).As a result,the recycle-derived DIB of Li/RLFPG is established with good electrochemical performance,such as an initial discharge capacity of 117.4 mA h g^-1 at 25 mA g^-1 and 78% capacity retention after 1000 cycles at 100 mA g^-1.The working mechanism of Li/RLFPG DIB is also revealed via in situ X-ray diffraction and electrode kinetics studies.This work not only presents a farreaching significance for large-scale recycling of spent LIBs in the future,but also proposed a sustainable and econo mical method to design n ew-type sec on dary batteries as recycling of spe nt LIBs.     

Monodispersed SWNTs Assembled Coating Layer as an Alterna-tive to Graphene with Enhanced Alkali-ion Storage Performance

Graphene coating is commonly used to improve the performance of electrode materials,while its steric hindrance effect hampers fast ion transport with compromised rate capability.Herein,a unique single-walled carbon nanotubes(SWNTs)coating layer,as an alternative to graphene,has been developed to improve the battery behavior of iron-based anodes.Benefiting from the structure merits of mesoporous SWNTs layer for fast electron/ion transport and hollow Fe₃O₄ for volume accommodation,as-prepared Fe₃O₄@SWNTs exhibited excellent lithium storage performance.It delivers a high capacity,excellent rate capability,and long lifespan with capacities of 582 mA·h·g^-1 at 5 A·g^-1 and 408 mA·h·g^-1 at 8 A·g^-1 remained after 1000 cycles.Such performance is better than graphene-coated Fe₃O₄ and other SWNT-Fe₃O₄ architectures.Besides,SWNTs coating is also used to improve the sodium and potassium storage performance of FeSe₂.The kinetics analysis and ex-situ experiment further reveal the effect of SWNTs coating for fast electron/ion transfer kinetics and good structure stability,thus leading to the superior performance of SWNTs-coated composites.     

Prediction of vapor-liquid-liquid-hydrate phase equilibrium for multicomponent systems containing tetrahydrofuran

Numbers of hydrate-based new techniques require the algorithm to be able to perform multiphase flash calculation where one phase is a gas hydrate phase.Tetrahydrofuran(THF)is frequently used as a thermodynamic promoter in the development of hydrate-based technique,which can reduce the hydrate formation pressure,especially when methane or hydrogen exists.However,it is a hard work to describe accurately the phase behavior of THF-water system due to their polarities.It has been proved that the water-in-oil(W/O)emulsion can raise the hydrate formation rate and improve the single stage separation efficiency,and furthermore prevent the hydrate from agglomeration to plug the facilities.The goal of this work is to present an extension of our previous work to the prediction of the vapor-liquid-liquid-hydrate equilibrium of such complex systems.These include ternary and quaternary mixtures with W/O emulsion containing THF.The proposed algorithm of four phase equilibrium calculation is very simple due to avoiding the complexity of simultaneous solution of the sophisticated equation group.The calculation results were found to be in satisfactory agreement with the experimental data.     

Carbon spheres with rational designed surface and secondary particle-piled structures for fast and stable sodium storage

The electrochemical performance of hard carbon in sodium storage is still limited by its poor cycling stability and rate capability because of the sluggish kinetics process.In this study,we use a simple and effective method to accelerate the kinetics process by engineering the structure of the electrode to promote its surface and near-surface reactions.This goal is realized by the use of slightly aggregated ultra-small carbon spheres.The large specific surface area formed by the small spheres can provide abundant active sites for electrochemical reactions.The abundant mesopores and macropores derived from the secondary particle piled structure of the carbon spheres could facilitate the transport of electrolytes,shorten the diffusion distance of Na⁺and accommodate the volume expansion during cycling.Benefiting from these unique structure features,PG700-3(carbon spheres with the diameters of 40-60 nm carbonized at 700℃)exhibits high performance for sodium storage.A high reversible capacity of 163 mAh g^-1 could be delivered at a current density of 1.0 A g^-1 after 100 cycles.Interestingly,at a current density of 10.0 A g^-1,the specific capacity of PG700-3 gradually increases to 140 mAh g^-1 after 10000 cycles,corresponding to a capacity retention of 112%.Given the enhanced kinetics of SIBs reactions,PG700-3 exhibits an excellent rate capability,i.e.,230 and 138 mAh g^-1 at 0.1 and 5.0 A g^-1,respectively.This study provides a facile method to attain high performance anode materials for SIBs.The design strategy and improvement mechanism could be extended to other materials for high rate applications.     

Core-shell structured SnSe@C microrod for Na-ion battery anode

The Sn Se nanoparticles encapsulated in the carbon nanofibers(Sn Se@C)with microrod morphology and core-shell structure are prepared by electrospinning and annealing process,and investigated as anode materials for sodium ion batteries.Benefiting from this unique structure,the Sn Se@C can deliver a reversible capacity of 283.8 m Ah g^-1 after 500 cycles at a high current density of 1.0 A g^-1.The sodium ion storage mechanisms of Sn Se are further characterized by ex-situ X-ray diffraction,high-resolution transmission electron microscope and selected area electron diffraction measurements.Besides,the excellent electrochemical performance of the electrodes is investigated by pseudocapacitance and in situ electrochemical impedance spectroscopy measurements.This work may provide a new avenue for synthesis of metal selenides with core-shell structure and a good idea for studying the kinetics process.