Organic electrode materials for fast-rate,high-power battery applications

The development of new battery materials with fast charging/discharging capabilities is necessary to meet the growing demands of modern technologies.While counter ion transport in inorganic materials(generally by de/intercalation)currently limits charge/discharge rates in lithium-ion batteries,the weak intermolecular forces in organic materials result in flexible,spacious structures that offer improved ion transport capabilities.Herein,we present the principles which enable fast rate capabilities in organic electrode materials,accompanied by specific literature examples illustrating exceptional rate performances.We discuss approaches to material design which support electron and/or ion transport and the limitations associated with each approach.This review aims to highlight the unique characteristics of organic materials as high-power density electrodes and inspire continued work in the field.

An in-situ self-etching enabled high-power electrode for aqueous zinc-ion batteries

Sluggish storage kinetics is considered as the main bottleneck of cathode materials for fast-charging aqueous zinc-ion batteries(AZIBs).In this report,we propose a novel in-situ self-etching strategy to unlock the Palm tree-like vanadium oxide/carbon nanofiber membrane(P-VO/C)as a robust freestanding electrode.Comprehensive investigations including the finite element simulation,in-situ X-ray diffraction,and in-situ electrochemical impedance spectroscopy disclosed it an electrochemically induced phase transformation mechanism from VO to layered Zn_(x)V_(2)O_5·nH_(2)O,as well as superior storage kinetics with ultrahigh pseudocapacitive contribution.As demonstrated,such electrode can remain a specific capacity of 285 mA h g^(-1)after 100 cycles at 1 A g^(-1),144.4 mA h g^(-1)after 1500 cycles at 30 A g^(-1),and even 97 mA h g^(-1)after 3000 cycles at 60 A g^(-1),respectively.Unexpectedly,an impressive power density of 78.9 kW kg^(-1)at the super-high current density of 100 A g^(-1)also can be achieved.Such design concept of in-situ self-etching free-standing electrode can provide a brand-new insight into extending the pseudocapacitive storage limit,so as to promote the development of high-power energy storage devices including but not limited to AZIBs.

Supercritical-hydrothermal accelerated solid state reaction route for synthesis of LiMn_2O_4 cathode material for high-power Li-ion batteries

Synthesis of the spinel structure lithium manganese oxide （LiMn2O4） by supercritical hydrothermal （SH） accelerated solid state reaction （SSR） route was studied. The impacts of the reaction pressure, reaction temperature and reaction time of SH route, and the calcination temperature of SSR route on the purity, particle morphology and electrochemical properties of the prepared LiMn2O4 materials were studied. The experimental results show that after 15 min reaction in SH route at 400 ℃ and 30 MPa, the reaction time of SSR could be significantly decreased, e.g. down to 3 h with the formation temperature of 800 ℃, compared with the conventional solid state reaction method. The prepared LiMn2O4 material exhibits good crystallinity, uniform size distribution and good electrochemical performance, and has an initial specific capacity of 120 mA.h/g at a rate of 0.1C （1C=148 mA/g） and a good rate capability at high rates, even up to 50C.

Surface-Engineered Li4Ti5O12 Nanostructures for High-Power Li-Ion Batteries

Materials with high-power charge–discharge capabilities are of interest to overcome the power limitations of conventional Li-ion batteries.In this study,a unique solvothermal synthesis of Li4Ti5O12 nanoparticles is proposed by using an off-stoichiometric precursor ratio.A Li-deficient off-stoichiometry leads to the coexistence of phaseseparated crystalline nanoparticles of Li4Ti5O12 and TiO2 exhibiting reasonable high-rate performances.However,after the solvothermal process,an extended aging of the hydrolyzed solution leads to the formation of a Li4Ti5O12 nanoplate-like structure with a self-assembled disordered surface layer without crystalline TiO2.The Li4Ti5O12 nanoplates with the disordered surface layer deliver ultrahighrate performances for both charging and discharging in the range of 50–300C and reversible capacities of 156 and 113 mAh g−1 at these two rates,respectively.Furthermore,the electrode exhibits an ultrahigh-charging-rate capability up to 1200C(60 mAh g−1;discharge limited to 100C).Unlike previously reported high-rate half cells,we demonstrate a high-power Li-ion battery by coupling Li4Ti5O12 with a high-rate LiMn2O4 cathode.The full cell exhibits ultrafast charging/discharging for 140 and 12 s while retaining 97 and 66% of the anode theoretical capacity,respectively.Room-(25℃),low-(−10℃),and high-(55℃)temperature cycling data show the wide temperature operation range of the cell at a high rate of 100C.

Numerical Investigation on Thermal Performance of Two-Phase Immersion Cooling Method for High-Power Electronics

The power density of electronic components grows continuously,and the subsequent heat accumulation and temperature increase inevitably affect electronic equipment’s stability,reliability and service life.Therefore,achieving efficient cooling in limited space has become a key problem in updating electronic devices with high performance and high integration.Two-phase immersion is a novel cooling method.The computational fluid dynamics(CFD)method is used to investigate the cooling performance of two-phase immersion cooling on high-power electronics.The two-dimensional CFD model is utilized by the volume of fluid(VOF)method and Reynolds StressModel.Lee’s model was employed to calculate the phase change rate.The heat transfer coefficient along the heatedwalls and the shear-lift force on bubbles are calculated.The simulation data are verified with the literature results.The cooling performance of different coolants has been studied.The results indicate that the boiling heat transfer coefficient can be enhanced by using a low boiling point coolant.The methanol is used as the cooling medium for further research.In addition,the mass flow rate and inlet temperature are investigated to assess the thermal performance of twophase immersion cooling.The average temperature of the high-power electronics is 80℃,and the temperature difference can be constrained to 8℃.Meanwhile,the convective heat transfer coefficient reaches 2740 W/(m2・℃)when the inlet temperature is 50℃,and the mass flow rate is 0.3 kg/s.In conclusion,the results demonstrated that two-phase immersion cooling has provided an effective method for the thermal management of high-power electronics.

Nitrogen-doped carbon stabilized Li Fe0.5Mn0.5PO4/rGO cathode materials for high-power Li-ion batteries

Exploring high ion/electron conductive olivine-type transition metal phosphates is of vital significance to broaden their applicability in rapid-charging devices.Herein,we report an interface engineered Li Fe0.5Mn0.5PO4/rGO@C cathode material by the synergistic effects of r GO and polydopamine-derived N-doped carbon.The well-distributed Li Fe0.5Mn0.5PO4nanoparticles are tightly anchored on r GO nanosheet benefited by the coating of N-doped carbon layer.The design of such an architecture can effectively suppress the agglomeration of nanoparticles with a shortened Li+transfer path.Meantime,the high-speed conducting network has been constructed by r GO and N-doped carbon,which exhibits the face-to-face contact with Li Fe0.5Mn0.5PO4nanoparticles,guaranteeing the rapid electron transfer.These profits endow the Li Fe0.5Mn0.5PO4/rGO@C hybrids with a fast charge-discharge ability,e.g.a high reversible capacity of 105 m Ah·g^-1at 10 C,much higher than that of the Li Fe0.5Mn0.5PO4@C nanoparticles(46 mA·h·g^-1).Furthermore,a 90.8%capacity retention can be obtained even after cycling 500 times at 2 C.This work gives a new avenue to fabricate transition metal phosphate with superior electrochemical performance for high-power Li-ion batteries.

Strategies for Rational Design of High-Power Lithium-ion Batteries

Lithium-ion batteries(LIBs)have shown considerable promise as an energy storage system due to their high conversion efficiency,size options(from coin cell to grid storage),and free of gaseous exhaust.For LIBs,power density and energy density are two of the most important parameters for their practical use,and the power density is the key factor for applications such as fast-charging electric vehicles,high-power portable tools,and power grid stabilization.A high rate of performance is also required for devices that store electrical energy from seasonal or irregular energy sources,such as wind energy and wave energy.Significant efforts have been made over the last several years to improve the power density of LIBs through anodes,cathodes,and electrolytes,and much progress has been made.To provide a comprehensive picture of these recent achievements,this review discusses the progress made in high-power LIBs from 2013 to the present,including general and fundamental principles of high-power LIBs,challenges facing LIB development today,and an outlook for future LIB development.

Vanadium-based polyanionic compounds as cathode materials for sodium-ion batteries:Toward high-energy and high-power applications

Sodium ion batteries(SIBs)have been regarded as one of the alternatives to lithium ion batteries owing to their wide availability and significantly low cost of sodium sources.However,they face serious challenges of low energy&power density and short cycling lifespan owing to the heavy mass and large radius of Na^(+).Vanadium-based polyanionic compounds have advantageous characteristic of high operating voltage,high ionic conductivity and robust structural framework,which is conducive to their high energy&power density and long lifespan for SIBs.In this review,we will overview the latest V-based polyanionic compounds,along with the respective characteristic from the intrinsic crystal structure to performance presentation and improvement for SIBs.One of the most important aspect is to discover the essential problems existed in the present V-based polyanionic compounds for high-energy&power applications,and point out most suitable solutions from the crystal structure modulation,interface tailoring and electrode configuration design.Moreover,some scientific issues of V-based polyanionic compounds shall be also proposed and related future direction shall be provided.We believe that this review can serve as a motivation for further development of novel V-based polyanionic compounds and drive them toward high energy&power applications in the near future.

ZIF-derived holey electrode with enhanced mass transfer and N-rich catalytic sites for high-power and long-life vanadium flow batteries

Electrode materials with good redox kinetics,excellent mass transfer characteristics and ultra-high stability play a crucial role in reducing the life-cycle cost and prolonging the maintenance-free time of the vanadium flow batteries(VFB).Herein,a nitrogen-doped porous graphite felt electrode(N-PGF)is proposed by growing ZIF-67 nanoparticles on carbon fibers and then calcinating and acid etching.The multi-scale structure of“carbon fiber gap(electrolyte flow),micro/nano pore(active species diffusion)and Nitrogen active center(reaction site)”in N-PGF electrode effectively increases the catalytic sites and promotes mass transfer characteristics.Reasonable electrode design makes the battery show excellent rate performance and ultra-high cycling stability.The peak power density of the battery reaches 1006 mW cm^(-2).During 1000 cycles at 150 mA cm^(-2),the average discharge capacity and average discharge energy of N-PGF increase substantially by 11.6%and 23.4%compared with the benchmark thermal activated graphite felt,respectively.More excitingly,after ultra-long term(5000 cycles)operation at an ultra-high current density(300 mA cm^(-2)),N-PGF exhibits an unprecedented energy efficiency retention(99.79%)and electrochemical performance stability.

Prussian Blue Analogue‑Templated Nanocomposites for Alkali‑Ion Batteries:Progress and Perspective

Lithium-ion batteries(LIBs)have dominated the portable electronic and electrochemical energy markets since their commercialisation,whose high cost and lithium scarcity have prompted the development of other alkali-ion batteries(AIBs)including sodium-ion batteries(SIBs)and potassium-ion batteries(PIBs).Owing to larger ion sizes of Na^(+)and K^(+)compared with Li^(+),nanocomposites with excellent crystallinity orientation and well-developed porosity show unprecedented potential for advanced lithium/sodium/potassium storage.With enticing open rigid framework structures,Prussian blue analogues(PBAs)remain promising self-sacrificial templates for the preparation of various nanocomposites,whose appeal originates from the well-retained porous structures and exceptional electrochemical activities after thermal decomposition.This review focuses on the recent progress of PBA-derived nanocomposites from their fabrication,lithium/sodium/potassium storage mechanism,and applications in AIBs(LIBs,SIBs,and PIBs).To distinguish various PBA derivatives,the working mechanism and applications of PBA-templated metal oxides,metal chalcogenides,metal phosphides,and other nanocomposites are systematically evaluated,facilitating the establishment of a structure–activity correlation for these materials.Based on the fruitful achievements of PBA-derived nanocomposites,perspectives for their future development are envisioned,aiming to narrow down the gap between laboratory study and industrial reality.

A hollow tubular NiCo layacknered double hydroxide@Ag nanowire structure for high-power-density flexible aqueous Ni//Zn battery

Flexible aqueous Ni//Zn batteries have attracted much attention as promising candidates for energy storage in the field of flexible electronics.However,the Ni-based cathodes still face the challenges of poor conductivity,confined charge/mass transfer,and non-flexibility.In this work,we designed a hollow tubular structure consisting of a conductive silver nanowire (Ag NW) wrapped by active Ni Co layered double hydroxide (LDH),for enhancing the electrical conductivity,improving the charge/mass transfer kinetics,and facilitating the ion penetration.By optimizing the contents of Ni,Co and Ag NW,the Ni_(4)Co LDH@Ag_(1.5)NW composite shows a maximum specific capacity of 115.83 m Ah g^(-1)at 0.1 A g^(-1)measured in a two-electrode system.Highlightingly,the flexible aqueous Ni//Zn battery assembled by Ni_(4)Co LDH@Ag_(1.5)NW interwoven with multi-walled carbon nanotube cathode and Zn foil anode realizes a high power density of 160μW cm^(-2)at the energy density of 23.14μWh cm^(-2),which is superior compared with those of oxide/hydroxide based devices and even higher than those of many carbon-based supercapacitors,showing its promising potentials for flexible energy storage applications.

Catalyst–Support Interaction in Polyaniline‑Supported Ni_(3)Fe Oxide to Boost Oxygen Evolution Activities for Rechargeable Zn‑Air Batteries

Catalyst–support interaction plays a crucial role in improving the catalytic activity of oxygen evolution reaction(OER).Here we modulate the catalyst–support interaction in polyaniline-supported Ni_(3)Fe oxide(Ni_(3)Fe oxide/PANI)with a robust hetero-interface,which significantly improves oxygen evolution activities with an overpotential of 270 mV at 10 mA cm^(-2)and specific activity of 2.08 mA cm_(ECSA)^(-2)at overpotential of 300 mV,3.84-fold that of Ni_(3)Fe oxide.It is revealed that the catalyst–support interaction between Ni_(3)Fe oxide and PANI support enhances the Ni–O covalency via the interfacial Ni–N bond,thus promoting the charge and mass transfer on Ni_(3)Fe oxide.Considering the excellent activity and stability,rechargeable Zn-air batteries with optimum Ni_(3)Fe oxide/PANI are assembled,delivering a low charge voltage of 1.95 V to cycle for 400 h at 10 mA cm^(-2).The regulation of the effect of catalyst–support interaction on catalytic activity provides new possibilities for the future design of highly efficient OER catalysts.

Model based SOC estimation for high-power Li-ion battery packs used on FCHVs

A model based method which recruited the extended Kalman filter （EKF） to estimate the full state of charge （SOC） of Li-ion battery was proposed. The underlying dynamic behavior of the cell pack was described based on an equivalent circuit comprising of two capacitors and three resistors. Measurements in two tests were applied to compare the SOC estimated by model based EKF estimation with the SOC calculated by coulomb counting. Results have shown that the proposed method is able to perform a good estimation of the SOC of battery packs. Moreover, a corresponding battery management systems （BMS） including software and hardware based on this method was designed.

Electrochemical properties of high-power lithium ion batteries made from modified spinel LiMn_2O_4

A prismatic 204056-type high power lithium-ion battery was developed.Modified LiMn2O4 and carbonaceous mesophase sphere(CMS)were adopted as the cathode and anode,respectively.The effects of proportion of conductive carbon black in cathode and the rest time after discharge on the electrochemical properties of batteries were investigated.The electrochemical tests show that the proportion of conductive carbon black in cathodes affects the high rate capability and discharge voltage plateau distinctly.The battery with 3.0%of conductive carbon black in cathode shows excellent electrochemical performances when being charged/discharged within 2.5-4.2 V at room temperature.The discharge capacity at 20C rate is 94.4%of that at 1C rate,and the capacity retention ratio charged at 1C and discharged at 5C is 86.6%after 390 cycles at room temperature.The test result of impulse discharge at 50C for 5 s shows that the battery has outstanding high rate discharge performance when the battery is in the depth of charge of 90%,75%,60%,45%,30%and 15%.The battery also shows good charge performance.When the battery is charged at 0.5C,1C,2C and 4C,the ratios of capacity for constant current charge are 98.4%,96.4%,91.0%and 72.9%of the whole charge capacity,respectively.In addition,the rest time after discharge affects the cycle performance distinctly when the battery is discharged at high rate.

Defect Engineering:Can it Mitigate Strong Coulomb Effect of Mg^(2+)in Cathode Materials for Rechargeable Magnesium Batteries?

Rechargeable magnesium batteries(RMBs)have been considered a promising“post lithium-ion battery”system to meet the rapidly increasing demand of the emerging electric vehicle and grid energy storage market.However,the sluggish diffusion kinetics of bivalent Mg^(2+)in the host material,related to the strong Coulomb effect between Mg^(2+)and host anion lattices,hinders their further development toward practical applications.Defect engineering,regarded as an effective strategy to break through the slow migration puzzle,has been validated in various cathode materials for RMBs.In this review,we first thoroughly understand the intrinsic mechanism of Mg^(2+)diffusion in cathode materials,from which the key factors affecting ion diffusion are further presented.Then,the positive effects of purposely introduced defects,including vacancy and doping,and the corresponding strategies for introducing various defects are discussed.The applications of defect engineering in cathode materials for RMBs with advanced electrochemical properties are also summarized.Finally,the existing challenges and future perspectives of defect engineering in cathode materials for the overall high-performance RMBs are described.

Photo‑Energized MoS_(2)/CNT Cathode for High‑Performance Li–CO_(2)Batteries in a Wide‑Temperature Range

Li–CO_(2) batteries are considered promising energy storage systems in extreme environments such as Mars;however,severe performance degradation will occur at a subzero temperature owning to the sluggish reaction kinetics.Herein,a photo-energized strategy adopting sustainable solar energy in wide working temperature range Li–CO_(2) battery was achieved with a binder-free MoS_(2)/carbon nanotube(CNT)photo-electrode as cathode.The unique layered structure and excellent photoelectric properties of MoS_(2) facilitate the abundant generation and rapid transfer of photo-excited carriers,which accelerate the CO_(2) reduction and Li_(2)CO_(3) decomposition upon illumination.The illuminated battery at room temperature exhibited high discharge voltage of 2.95 V and mitigated charge voltage of 3.27 V,attaining superior energy efficiency of 90.2%and excellent cycling stability of over 120 cycles.Even at an extremely low temperature of−30℃,the battery with same electrolyte can still deliver a small polarization of 0.45 V by the photoelectric and photothermal synergistic mechanism of MoS_(2)/CNT cathode.This work demonstrates the promising potential of the photo-energized wide working temperature range Li–CO_(2) battery in addressing the obstacle of charge overpotential and energy efficiency.

Constructing Donor–Acceptor‑Linked COFs Electrolytes to Regulate Electron Density and Accelerate the Li^(+)Migration in Quasi‑Solid‑State Battery

Regulation the electronic density of solid-state electrolyte by donor–acceptor(D–A)system can achieve highly-selective Li^(+)transportation and conduction in solid-state Li metal batteries.This study reports a high-performance solid-state electrolyte thorough D–A-linked covalent organic frameworks(COFs)based on intramolecular charge transfer interactions.Unlike other reported COFbased solid-state electrolyte,the developed concept with D–A-linked COFs not only achieves electronic modulation to promote highly-selective Li^(+)migration and inhibit Li dendrite,but also offers a crucial opportunity to understand the role of electronic density in solid-state Li metal batteries.The introduced strong electronegativity F-based ligand in COF electrolyte results in highlyselective Li^(+)(transference number 0.83),high ionic conductivity(6.7×10^(-4)S cm^(−1)),excellent cyclic ability(1000 h)in Li metal symmetric cell and high-capacity retention in Li/LiFePO_(4)cell(90.8%for 300 cycles at 5C)than substituted C-and N-based ligands.This is ascribed to outstanding D–A interaction between donor porphyrin and acceptor F atoms,which effectively expedites electron transferring from porphyrin to F-based ligand and enhances Li^(+)kinetics.Consequently,we anticipate that this work creates insight into the strategy for accelerating Li^(+)conduction in high-performance solid-state Li metal batteries through D–A system.

Molecule‑Level Multiscale Design of Nonflammable Gel Polymer Electrolyte to Build Stable SEI/CEI for Lithium Metal Battery

The risk of flammability is an unavoidable issue for gel polymer electrolytes(GPEs).Usually,flameretardant solvents are necessary to be used,but most of them would react with anode/cathode easily and cause serious interfacial instability,which is a big challenge for design and application of nonflammable GPEs.Here,a nonflammable GPE(SGPE)is developed by in situ polymerizing trifluoroethyl methacrylate(TFMA)monomers with flame-retardant triethyl phosphate(TEP)solvents and LiTFSI–LiDFOB dual lithium salts.TEP is strongly anchored to PTFMA matrix via polarity interaction between-P=O and-CH_(2)CF_(3).It reduces free TEP molecules,which obviously mitigates interfacial reactions,and enhances flame-retardant performance of TEP surprisingly.Anchored TEP molecules are also inhibited in solvation of Li^(+),leading to anion-dominated solvation sheath,which creates inorganic-rich solid electrolyte interface/cathode electrolyte interface layers.Such coordination structure changes Li^(+)transport from sluggish vehicular to fast structural transport,raising ionic conductivity to 1.03 mS cm^(-1) and transfer number to 0.41 at 30℃.The Li|SGPE|Li cell presents highly reversible Li stripping/plating performance for over 1000 h at 0.1 mA cm^(−2),and 4.2 V LiCoO_(2)|SGPE|Li battery delivers high average specific capacity>120 mAh g^(−1) over 200 cycles.This study paves a new way to make nonflammable GPE that is compatible with Li metal anode.

Octylamine-Supporting Interlayer Expanded Molybdenum Diselenide as a High-Power Cathode for Rechargeable Mg Batteries

Rechargeable Mg batteries(RMBs)are a promising large-scale energy-storage technology with low cost and high safety,but the performance is limited by the inferior kinetics of Mg-intercalation cathodes.In the present study,an octylamine-supporting interlayer expanded molybdenum diselenide(e-MoSe_(2))is synthesized and used as cathode for RMBs,in comparison with ordinary crystalline MoSe_(2).The octylamine molecules introduced show a strong interaction with the MoSe_(2)layers and increase the layer spacing significantly from 6.46 to 11.5Å.e-MoSe_(2)shows a high Mg-storage capacity of 238 mAh g^(-1)at 50 mA g^(-1)and a superior rate performance of 39 mAh g^(-1)at 10 A g1,far advantageous over crystalline MoSe_(2).e-MoSe_(2)also shows a considerably high structure stability during repeated magnesiation/demagnesiation,providing an outstanding cycling stability for 1000 cycles.Further electrochemical tests demonstrate the high Mg^(2+)diffusion coefficients in e-MoSe_(2).Theoretical computation indicates the interlayer expansion changes the Mg^(2+)diffusion paths from"hollow site→hollow site"to"hollow site→Se atom site→hollow site",largely decreasing the energy barrier and improving the Mg^(2+)diffusion kinetics.The present work highlights an efficient strategy for the improvement of Mg-storage performance for RMB cathodes.

Analysis of high-power disk laser welding stability based on classification of plume and spatter characteristics

Classification of plume and spatter images was studied to evaluate the welding stability. A high-speed camera was used to capture the instantaneous images of plume and spatters during high power disk laser welding. Characteristic parameters such as the area and number of spatters, the average grayscale of a spatter image, the entropy of a spatter grayscale image, the coordinate ratio of the plume centroid and the welding point, the polar coordinates of the plume centroid were defined and extracted. Karhunen-Loeve transform method was used to change the seven characteristics into three primary characteristics to reduce the dimensions. Also, K-nearest neighbor method was used to classify the plume and spatter images into two categories such as good and poor welding quality. The results show that plume and spatter have a close relationship with the welding stability, and two categories could be recognized effectively using K-nearest neighbor method based on Karhunen-Loeve transform.