Suppress oxygen evolution of lithium-rich manganese-based cathode materials via an integrated strategy

Improving the reversibility of anionic redox and inhibiting irreversible oxygen evolution are the main challenges in the application of high reversible capacity Li-rich Mn-based cathode materials.A facile synchronous lithiation strategy combining the advantages of yttrium doping and LiYO_(2) surface coating is proposed.Yttrium doping effectively suppresses the oxygen evolution during the delithiation process by increasing the energy barrier of oxygen evolution reaction through strong Y–O bond energy.LiYO_(2) nanocoating has the function of structural constraint and protection,that protecting the lattice oxygen exposed to the surface,thus avoiding irreversible oxidation.As an Li^(+) conductor,LiYO_(2) nano-coating can provide a fast Li^(+) transfer channel,which enables the sample to have excellent rate performance.The synergistic effect of Y doping and nano-LiYO_(2) coating integration suppresses the oxygen release from the surface,accelerates the diffusion of Li^(+)from electrolyte to electrode and decreases the interfacial side reactions,enabling the lithium ion batteries to obtain good electrochemical performance.The lithium-ion full cell employing the Y-1 sample(cathode)and commercial graphite(anode)exhibit an excellent specific energy density of 442.9 Wh kg^(-1) at a current density of 0.1C,with very stable safety performance,which can be used in a wide temperature range(60 to-15℃)stable operation.This result illustrates a new integration strategy for advanced cathode materials to achieve high specific energy density.

Smart materials for safe lithium-ion batteries against thermal runaway

In recent years,the new energy storage system,such as lithium ion batteries(LIBs),has attracted much attention.In order to meet the demand of industrial progress for longer cycle life,higher energy density and cost efficiency,a quantity of research has been conducted on the commercial application of LIBs.However,it is difficult to achieve satisfying safety and cycling performance simultaneously.There may be thermal runaway(TR),external impact,overcharge and overdischarge in the process of battery abuse,which makes the safety problem of LIBs more prominent.In this review,we summarize recent progress in the smart safety materials design towards the goal of preventing TR of LIBs reversibly from different abuse conditions.Benefiting from smart responsive materials and novel structural design,the safety of LIBs can be improved a lot.We expect to provide a comprehensive reference for the development of smart and safe lithium-based battery materials.

Design of multifunctional polymeric binders in silicon anodes for lithium‐ion batteries

Silicon(Si)is a promising anode material for lithium‐ion batteries(LIBs)owing to its tremendously high theoretical storage capacity(4200 mAh g−1),which has the potential to elevate the energy of LIBs.However,Si anodes exhibit severe volume change during lithiation/delithiation processes,resulting in anode pulverization and delamination with detrimental growth of solid electrolyte interface layers.As a result,the cycling stability of Si anodes is insufficient for commercialization in LIBs.Polymeric binders can play critical roles in Si anodes by affecting their cycling stability,although they occupy a small portion of the electrodes.This review introduces crucial factors influencing polymeric binders'properties and the electrochemical performance of Si anodes.In particular,we emphasize the structure–property relationships of binders in the context of molecular design strategy,functional groups,types of interactions,and functionalities of binders.Furthermore,binders with additional functionalities,such as electrical conductivity and self‐healability,are extensively discussed,with an emphasis on the binder design principle.

Multilevel carbon architecture of subnanoscopic silicon for fast‐charging high‐energy‐density lithium‐ion batteries

Silicon(Si)is widely used as a lithium‐ion‐battery anode owing to its high capacity and abundant crustal reserves.However,large volume change upon cycling and poor conductivity of Si cause rapid capacity decay and poor fast‐charging capability limiting its commercial applications.Here,we propose a multilevel carbon architecture with vertical graphene sheets(VGSs)grown on surfaces of subnanoscopically and homogeneously dispersed Si–C composite nanospheres,which are subsequently embedded into a carbon matrix(C/VGSs@Si–C).Subnanoscopic C in the Si–C nanospheres,VGSs,and carbon matrix form a three‐dimensional conductive and robust network,which significantly improves the conductivity and suppresses the volume expansion of Si,thereby boosting charge transport and improving electrode stability.The VGSs with vast exposed edges considerably increase the contact area with the carbon matrix and supply directional transport channels through the entire material,which boosts charge transport.The carbon matrix encapsulates VGSs@Si–C to decrease the specific surface area and increase tap density,thus yielding high first Coulombic efficiency and electrode compaction density.Consequently,C/VGSs@Si–C delivers excellent Li‐ion storage performances under industrial electrode conditions.In particular,the full cells show high energy densities of 603.5 Wh kg^(−1)and 1685.5 Wh L^(−1)at 0.1 C and maintain 80.7%of the energy density at 3 C.

Insights on advanced g‐C_(3)N_(4)in energy storage:Applications,challenges,and future

Graphitic carbon nitride(g‐C_(3)N_(4))is a highly recognized two‐dimensional semiconductor material known for its exceptional chemical and physical stability,environmental friendliness,and pollution‐free advantages.These remarkable properties have sparked extensive research in the field of energy storage.This review paper presents the latest advances in the utilization of g‐C_(3)N_(4)in various energy storage technologies,including lithium‐ion batteries,lithium‐sulfur batteries,sodium‐ion batteries,potassium‐ion batteries,and supercapacitors.One of the key strengths of g‐C_(3)N_(4)lies in its simple preparation process along with the ease of optimizing its material structure.It possesses abundant amino and Lewis basic groups,as well as a high density of nitrogen,enabling efficient charge transfer and electrolyte solution penetration.Moreover,the graphite‐like layered structure and the presence of largeπbonds in g‐C_(3)N_(4)contribute to its versatility in preparing multifunctional materials with different dimensions,element and group doping,and conjugated systems.These characteristics open up possibilities for expanding its application in energy storage devices.This article comprehensively reviews the research progress on g‐C_(3)N_(4)in energy storage and highlights its potential for future applications in this field.By exploring the advantages and unique features of g‐C_(3)N_(4),this paper provides valuable insights into harnessing the full potential of this material for energy storage applications.

Effects of Al,F dual substitutions on the structure and electrochemical properties of lithium manganese oxide

Spinel LiMn2O4 and F, Al-doped spinel LiAl0.05Mn1.95O3.58F0.02 have been synthesized by a soft chemistry method using adipic acid as the chelating agent. The synthesized spine/materials were characterized by differential thermal analysis （DTA） and thermogravimetery （TG）, X-ray diffraction （XRD）, scanning electron microscopy （SEM）, cyclic voltammetry （CV）, and chargedischarge testing. The results indicate that all the samples have high phase purity, and fluorine is important in controlling the morphology; the doped aluminum enhances the stability of spinel LiMn2O4. The charge-discharge tests indicate that LiAl0.05Mn1.95O4 has high capacity retention, which is 92.60% of the initial after 50 cycles. It is found that the novel compound LiAl0.05Mn1.95O3.98F0.02 with smaller particles can offer much higher capacity, whose initial discharge capacity is 126.5 mAh·g^-1. The cyclic voltammetric experiments disclose the enhanced reversibility of the F, Al^3＋-modified spinel as compared with the undoped spinel.

Phase Equilibria of the Aqueous Systems Containing Lithium and Carbonate Ions

1 Introduction Alkaline lakes are widely distributed in the area of the Qinghai-Tibet Plateau.Most of the salt lakes are famous for their high concentration of lithium,potassium,magnesium,boron(Ma,2000).In recent years,as a new energy material,lithium and its compounds are widely used in the new area,such as aerospace industry,nuclear

Investigation on step overcharge to self-heating behavior and mechanism analysis of lithium ion batteries

To obtain intrinsic overcharge boundary and investigate overcharge mechanism,here we propose an innovative method,the step overcharge test,to reduce the thermal crossover and distinguish the overcharge thermal behavior,including 5%state of charge(SOC)with small current overcharge and resting until the temperature equilibrium under adiabatic conditions.The intrinsic thermal response and the self-excitation behaviour are analysed through temperature and voltage changes during the step overcharge period.Experimental results show that the deintercalated state of the cathode is highly correlated to self-heating parasitic reactions.Before reaching the upper limit of Negative/Positive(N/P)ratio,the temperature changes little,the heat generation is significantly induced by the reversible heat(endothermic)and ohmic heat,which could balance each other.Following that the lithium metal is gradually deposited on the surface of the anode and reacts with electrolyte upon overcharge,inducing selfheating side reaction.However,this spontaneous thermal reaction could be“self-extinguished”.When the lithium in cathode is completely deintercalated,the boundary point of overcharge is about 4.7 V(~148%SOC,>40℃),and from this point,the self-heating behaviour could be continuously triggered until thermal runaway(TR)without additional overcharge.The whole static and spontaneous process lasts for 115 h and the side reaction heat is beyond 320,000 J.The continuous self-excitation behavior inside the battery is attributed to the interaction between the highly oxidized cathode and the solvent,which leads to the dissolution of metal ions.The dissolved metal ions destroy the SEI(solid electrolyte interphase)film on the surface of the deposited Li of anode,which induces the thermal reaction between lithium metal and the solvent.The interaction between cathode,the deposited Li of anode,and solvent promotes the temperature of the battery to rise slowly.When the temperature of the battery reaches more than 60℃,the reaction between lithium metal and solvent is accelerated.After the temperature rises rapidly to the melting point of the separator,it triggers the thermal runaway of the battery due to the short circuit of the battery.

Conductivity and applications of Li-biphenyl-1,2-dimethoxyethane solution for lithium ion batteries

The total conductivity of Li-biphenyl-1,2-dimethoxyethane solution（Li_xBp（DME）_（9.65）, Bp = biphenyl, DME = 1,2-dimethoxyethane, x = 0.25, 0.50, 1.00, 1.50, 2.00） is measured by impedance spectroscopy at a temperature range from 0℃ to 40℃. The Li_（1.50）Bp（DME）_（9.65） has the highest total conductivity 10.7 m S/cm. The conductivity obeys Arrhenius law with the activation energy（E_（a（x=0.50））= 0.014 eV, E_（a（x=1.00））= 0.046 eV）. The ionic conductivity and electronic conductivity of Li_xBp（DME）_（9.65） solutions are investigated at 20℃ using the isothermal transient ionic current（ITIC） technique with an ion-blocking stainless steal electrode. The ionic conductivity and electronic conductivity of Li_（1.00）Bp（DME）_（9.65） are measured as 4.5 mS/cm and 6.6 mS/cm, respectively. The Li_（1.00）Bp（DME）_（9.65） solution is tested as an anode material of half liquid lithium ion battery due to the coexistence of electronic conductivity and ionic conductivity. The lithium iron phosphate（LFP） and Li_（1.5）Al_（0.5）Ti_（1.5）（PO_4）_3（LATP） are chosen to be the counter electrode and electrolyte, respectively. The assembled cell is cycled in the voltage range of 2.2 V-3.75 V at a current density of 50 mA/g. The potential of Li_（1.00）Bp（DME）_（9.65） solution is about 0.3 V vs. Li~＋/Li, which indicates the solution has a strong reducibility. The Li_（1.00）Bp（DME）_（9.65） solution is also used to prelithiate the anode material with low first efficiency, such as hard carbon, soft carbon and silicon.

Vanadium Nitride Nanoparticles as Anode Material for Lithium Ion Hybrid Capacitor Applications

A high production efficiency synthesis method was used to produce a stacked vanadium nitride nanoparticle structure with an inexpensive raw material as an anode material and high surface area polystyrene was used the cathode material for lithium ion hybrid capacitors. The Li-HCs cell displayed an excellent specific capacitance of 64.2 F·g^-1 at a current density of 0.25 A·g^-1 and a wide potential window of 0.01 to 3.5 V. Furthermore, the device exhibited a high energy density of 109.3 W·h·kg^-1 at a power density of 512.3 W·kg^-1 and retained an energy density of 69.2 W·h·kg^-1 at a high power density of 3 498.9 W· kg^-1 at 2 A·g^-1. Due to the short synthesis time and simple raw materials, this method is suitable for industrial production.

PNb_(9)O_(25) nanofiber as a high-voltage anode material for advanced lithium ions batteries

If the operating voltage of anode materials is below 1.0 V versus Lit/Li,the side reaction between electrolyte and anode materials will occur extensively.Thus,high-voltage anode materials have aroused interest recently.In this work,we report the preparation of PNb9O25 nanofiber via a facile electrospinning method.The PNb9O25 nanofiber shows the high rate performance and excellent cycling performance when it is used as anode in lithium ions batteries.For instance,the PNb9O25 nanofiber can deliver a capacity of 233,212.1,193.8,and 181.4 mA h g^(-1) at 0.2,1,3,and 6C,respectively.After 1000 cycles,it can reach at 134.3 mA h g^(-1) with capacity retention of 70.9%.Meanwhile,the ex situ X-ray photoelectron spectroscopy technique has been adopted to investigate the evolution in valence state of each element for PNb9O25 nanofiber.In addition,the PNb9O25 nanofiber is chosen as the anode material in lithium ion full cell in this work,demonstrating the potential for practical application.

Solid–liquid Phase Equilibria in the Aqueous Ternary System Containing Lithium,Potassium,and Sulfate ions at 288.15 K

1 Introduction Salt lakes are widely distributed in the western of China,especially in the area of Qinghai-Xizang(Tibet)Plateau.A series of salt lakes in the Qaidam Basin,located in Qinghai Province,China,is famous for their abundance of lithium,potassium and boron resources(Zheng et al,1988;Deng et al,2012).It is well known that the

A surfactant-modified composite separator for high safe lithium ion battery

Separators have been gaining increasing attention to improve the performance of lithium ion batteries(LIBs),especially for high safe and long cycle life.However,commercial polyolefin separators still face the problems of rapid capacity decay and safety issues due to the poor wettability with electrolytes and low thermal stability.Herein,a novel composite separator is proposed by introducing a surfactant of sodium dodecyl thiosulfate(SDS)into the polytetrafluoroethylene(PTFE)substrate with the binder of polyacrylic acid(PAA)through the suction filtration method.The introduction of PAA/SDS enhances the adsorption energy between PTFE substrate and electrolyte through density functional theory calculations,which improves wettability and electrolyte uptake of the separator significantly.The asachieved composite separator enables the LIBs to own high Li^(+)conductivity(0.64×10^(-3)S cm^(-1))and Li^(+)transference number(0.63),further leading to a high capacity retention of 93.50%after 500 cycles at 1 C.In addition,the uniform and smooth surface morphology of Li metal employed the composite separator after cycling indicates that the lithium dendrites can be successfully inhibited.This work indicates a promising route for the preparation of a novel composite separator for high safe LIBs.

Improving Cyclic Stability and Rate Performance of Lithium Ion Batteries Using La^(3+)Modified LiNi_(0.6)Co_(0.2)Mn_(0.2)O_(2)Cathode Materials

La_(4)NiLiO_(8)-coated NCM622 samples were prepared through a sol-gel method,and the electrochemical performance as cathode materials was investigated.It is revealed that part of the introduced La^(3+)ions produce a coating layer on the surface of NCM622 particles,while the rest occupy the 3b position of the lattice.The optimized sample exhibits a capacity retention of 96.54%after 100 cycles under 1C rate with a discharge specific capacity of 117.54 mAh·g^(-1)under 5C rate,much higher than those of the unmodified sample.The results show that the addition of La^(3+)ion can greatly improve the cyclic stability and the rate performance of NCM622.

Interfacial nitrogen engineering of robust silicon/MXene anode toward high energy solid-state lithium-ion batteries

Replacing the conventional carbonate electrolyte by solid-state electrolyte (SSE) will offer improved safety for lithium-ion batteries.To further improve the energy density,Silicon (Si) is attractive for next generation solid-state battery (SSB) because of its high specific capacity and low cost.High energy density and safe Si-based SSB,however,is plagued by large volume change that leads to poor mechanical stability and slow lithium ions transportation at the multiple interfaces between Si and SSE.Herein,we designed a self-integrated and monolithic Si/two dimensional layered T_(3)C_(2)T_(x)(MXene,T_(x) stands for terminal functional groups) electrode architecture with interfacial nitrogen engineering.During a heat treatment process,the polyacrylonitrile not only converts into amorphous carbon (a-C) that shells Si but also forms robust interfacial nitrogen chemical bonds that anchors Si and MXene.During repeated lithiation and delithiation processes,the robust interfacial engineered Si/MXene configuration enhances the mechanical adhesion between Si and MXene that improves the structure stability but also contributes to form stable solid-electrolyte interphase (SEI).In addition,the N-MXene provides fast lithium ions transportation pathways.Consequently,the Si/MXene with interfacial nitrogen engineering (denoted as Si-N-MXene) deliveres high-rate performance with a specific capacity of 1498 m Ah g^(-1) at a high current of 6.4 A g^(-1).A Si-N-MXene/NMC full cell exhibited a capacity retention of 80.5%after 200 cycles.The Si-N-MXene electrode is also applied to SSB and shows a relative stable cycling over 100 cycles,demonstrating the versatility of this concept.

Dual modification of LiNi_(0.83)Co_(0.11)Mn_(0.06)O_(2) cathode materials by K^(+) doping and Li_(3)PO_(4) coating for lithium ions batteries

Li_(3)PO_(4)@Li_(0.99)K_(0.01)Ni_(0.83)Co_(0.11)Mn_(O.06)O_(2)(NCM-KP) cathode powders are synthesized via K^(+)doping in calcination processes and H_3PO_4 coating in sol-gel processes.K^(+) precisely enters into the lattice to widen the(003) plane to 0.4746 nm with a lower cationic disordered degree of 1.87%.Moreover,the surface residual lithium salts are treated by H_3PO_4 to generate a uniform Li_(3)PO_(4) coating layer of approximately 11.41 nm,which completely covers on the surface of secondary spherical particles to improve the interfacial stability.At 25℃,the NCM-KP electrode delivers a discharge specific capacity of 148.9 mAh·g^(-1) with a remarkable capacity retention ratio of 84.1% after 200 cycles at 1.0C and retains a high reversible specific capacity of 154.4 mAh·g^(-1) at 5.0C.Even at 1.0C and 60℃,it can maintain a reversible discharge specific capacity of 114.6 mAh·g^(-1) with 0.21% of capacity decay per cycle after 200 cycles,which is significantly lower than 0.40% for the pristine NCM powders.Importantly,the charge transfer resistance of 238.89 Ω for the NCM-KP electrode is significantly lower than 947.41 Ω for the pristine NCM one by restricting the interfacial side reactions.Therefore,combining K+doping and Li_(3)PO_(4) coating is an effective strategy to enable the significant improvement of the electrochemical property of high-nickel cathode materials,which may be mainly attributed to the widened diffusion pathway and the formed Li_(3)PO_(4) protective layer,thus promoting Li~+diffusion rate and preventing the erosion of HF.

Preparation and electrochemical properties of Y-doped Li_3V_2(PO_4)_3 cathode materials for lithium batteries

Y-doped Li3V2（PO4）3 cathode materials were prepared by a carbothermal reduction（CTR） process.The properties of the Y-doped Li3V2（PO4）3 were investigated by X-ray diffraction（XRD） and electrochemical measurements.XRD studies showed that the Y-doped Li3V2（PO4）3 had the same monoclinic structure as the undoped Li3V2（PO4）3.The Y-doped Li3V2（PO4）3 samples were investigated on the Li extraction/insertion performances through charge/discharge, cyclic voltammogram（CV）, and electrochemical impedance spectra（EIS）.The optimal doping content of Y was x=0.03 in Li3V2-xYx（PO4）3 system.The Y-doped Li3V2（PO4）3 samples showed a better cyclic ability.The electrode reaction reversibility was enhanced, and the charge transfer resistance was decreased through the Y-doping.The improved electrochemical perormances of the Y-doped Li3V2（PO4）3 cathode materials were attributed to the addition of Y3＋ ion by stabilizing the monoclinic structure.

The efficiency and toxicity of dodecafluoro-2-methylpentan-3-one in suppressing lithium-ion battery fire

Currently,the effective and clean suppression of lithium-ion battery(LIB)fires remains a challenge.The present work investigates the use of various inhibitor doses(Xin)of dodecafluoro-2-methylpentan-3-one(C_(6) F_(12)O)in 300 Ah LIBs,and systematically examines the thermal and toxic hazards of the extinguished batteries via real scale combustion and gas analysis.The inhibitor is shown to be completely effective.The inhibition mechanism involves a combination of chemical inhibition and physical cooling.While the chemical inhibition effect tends to saturate with increasing Xin,the physical cooling remains effective at higher inhibitor doses.However,extinguishing the battery fire with a high Xin of C_(6)F_(12)O is found to incur serious toxicity problems.These results are expected to provide a guideline for the design of inhibitor doses for the suppression of LIB fires.

Insights into Enhanced Capacitive Behavior of Carbon Cathode for Lithium Ion Capacitors: The Coupling of Pore Size and Graphitization Engineering

The lack of methods to modulate intrinsic textures of carbon cathode has seriously hindered the revelation of in-depth relationship between inherent natures and capacitive behaviors,limiting the advancement of lithium ion capacitors(LICs).Here,an orientateddesigned pore size distribution(range from 0.5 to 200 nm)and graphitization engineering strategy of carbon materials through regulating molar ratios of Zn/Co ions has been proposed,which provides an effective platform to deeply evaluate the capacitive behaviors of carbon cathode.Significantly,after the systematical analysis cooperating with experimental result and density functional theory calculation,it is uncovered that the size of solvated PF6-ion is about 1.5 nm.Moreover,the capacitive behaviors of carbon cathode could be enhanced attributed to the controlled pore size of 1.5-3 nm.Triggered with synergistic effect of graphitization and appropriate pore size distribution,optimized carbon cathode(Zn90Co10-APC)displays excellent capacitive performances with a reversible specific capacity of^50 mAh g-1at a current density of 5 A g-1.Furthermore,the assembly pre-lithiated graphite(PLG)//Zn90Co10-APC LIC could deliver a large energy density of 108 Wh kg-1 and a high power density of 150,000 W kg-1 as well as excellent long-term ability with 10,000 cycles.This elaborate work might shed light on the intensive understanding of the improved capacitive behavior in LiPF<sub>6 electrolyte and provide a feasible principle for elaborate fabrication of carbon cathodes for LIC systems.

Synthesis and applications of MOF-derived porous nanostructures

Metal organic frameworks(MOFs) represent a class of porous material which is formed by strong bonds between metal ions and organic linkers. By careful selection of constituents, MOFs can exhibit very high surface area, large pore volume, and excellent chemical stability.Research on synthesis, structures and properties of various MOFs has shown that they are promising materials for many applications, such as energy storage, gas storage, heterogeneous catalysis and sensing. Apart from direct use, MOFs have also been used as support substrates for nanomaterials or as sacrificial templates/precursors for preparation of various functional nanostructures. In this review, we aim to present the most recent development of MOFs as precursors for the preparation of various nanostructures and their potential applications in energy-related devices and processes. Specifically, this present survey intends to push the boundaries and covers the literatures from the year 2013 to early 2017,on supercapacitors, lithium ion batteries, electrocatalysts, photocatalyst, gas sensing, water treatment, solar cells, and carbon dioxide capture.Finally, an outlook in terms of future challenges and potential prospects towards industrial applications are also discussed.