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.

Effects of Different Concentrations of Sulfate Ions on Carbonate Crude Oil Desorption:Experimental Analysis and Molecular Simulation

Low salinity water containing sulfate ions can significantly alter the surface wettability of carbonate rocks.Nevertheless,the impact of sulfate concentration on the desorption of oil film on the surface of carbonate rock is still unknown.This study examines the variations in the wettability of the surface of carbonate rocks in solutions containing varying amounts of sodium sulfate and pure water.The problem is addressed in the framework of molecular dynamics simulation(Material Studio software)and experiments.The experiment’s findings demonstrate that sodium sulfate can increase the rate at which oil moisture is turned into water moisture.The final contact angle is smaller than that of pure water.The results of the simulations show that many water molecules travel down the water channel under the influence of several powerful forces,including the electrostatic force,the van der Waals force and hydrogen bond,crowding out the oil molecules on the calcite’s surface and causing the oil film to separate.The relative concentration curve of water and oil molecules indicates that the separation rate of the oil film on the surface of calcite increases with the number of sulfate ions.

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.

Experimental Study on the Chloride Ion Concentration of Cement Pastes Prepared with Limestone Powder

To investigate the impact of limestone powder on the chloride ion concentration coefficient of cement pastes,various techniques such as scanning electron microscopy(SEM),X-ray diffraction(XRD),thermogravimetric analysis(TGA),and mercury-porosimetry(MIP)were employed in this paper.The findings demonstrate that the creation of Friedel's salt is inversely associated with the addition of limestone powder,that is,Friedel's salt production is lessened by adding more limestone powder,however,the coefficient of chloride ion concentration initially decreased and then increased again,as does the porosity,and most likely the pore size as well.The specific surface area of limestone powder has increased,and the content of Friedel’s salt increased first and then decreased.However,the shifting trend of Friedel's salt and chloride ion concentration coefficient is in direct opposition,and the pore structure was therefore significantly enhanced.The results of this study offer robust theoretical backing for the inclusion of limestone powder in concrete and provide a positive assessment of its potential applications.

Enhanced axonal regeneration and functional recovery of the injured sciatic nerve in a rat model by lithium-loaded electrospun nanofibrous scaffolds

Increasing evidence indicates that engineered nerve grafts have great potential for the regeneration of peripheral nerve injuries(PNIs).While most studies have focused only on the topographical features of the grafts,we have considered both the biophysical and biochemical manipulations in our applied nanoscaffold.To achieve this,we fabricated an electrospun nanofibrous scaffold(ENS)containing polylactide nanofibers loaded with lithium(Li)ions,a Wnt/β-catenin signaling activator.In addition,we seeded human adipose-derived mesenchymal stem cells(hADMSCs)onto this engineered scaffold to examine if their differentiation toward Schwann-like cells was induced.We further examined the efficacy of the scaffolds for nerve regeneration in vivo via grafting in a PNI rat model.Our results showed that Li-loaded ENSs gradually released Li within 11 d,at concentrations ranging from 0.02 to(3.64±0.10)mmol/L,and upregulated the expression of Wnt/β-catenin target genes(cyclinD1 and c-Myc)as well as those of Schwann cell markers(growth-associated protein 43(GAP43),S100 calcium binding protein B(S100B),glial fibrillary acidic protein(GFAP),and SRY-box transcription factor 10(SOX10))in differentiated hADMSCs.In the PNI rat model,implantation of Li-loaded ENSs with/without cells improved behavioral features such as sensory and motor functions as well as the electrophysiological characteristics of the injured nerve.This improved function was further validated by histological analysis of sciatic nerves grafted with Li-loaded ENSs,which showed no fibrous connective tissue but enhanced organized myelinated axons.The potential of Li-loaded ENSs in promoting Schwann cell differentiation of hADMSCs and axonal regeneration of injured sciatic nerves suggests their potential for application in peripheral nerve tissue engineering.

A layered multifunctional framework based on polyacrylonitrile and MOF derivatives for stable lithium metal anode

Composite Li metal anodes based on three-dimensional(3D) porous frameworks have been considered as an effective material for achieving stable Li metal batteries with high energy density.However,uneven Li deposition behavior still occurs at the top of 3D frameworks owing to the local accumulation of Li ions.To promote uniform Li deposition without top dendrite growth,herein,a layered multifunctional framework based on oxidation-treated polyacrylonitrile(OPAN) and metal-organic framework(MOF) derivatives was proposed for rationally regulating the distribution of Li ions flux,nucleation sites,and electrical conductivity.Profiting from these merits,the OPAN/carbon nano fiber-MOF(CMOF) composite framework demonstrated a reversible Li plating/stripping behavior for 500 cycles with a stable Coulombic efficiency of around 99.0% at the current density of 2 mA/cm~2.Besides,such a Li composite anode exhibited a superior cycle lifespan of over 1300 h under a low polarized voltage of 18 mV in symmetrical cells.When the Li composite anode was paired with LiFePO_(4)(LFP) cathode,the obtained full cell exhibited a stable cycling over 500 cycles.Moreover,the COMSOL Multiphysics simulation was conducted to reveal the effects on homogeneous Li ions distribution derived from the above-mentioned OPAN/CMOF framework and electrical insulation/conduction design.These electrochemical and simulated results shed light on the difficulties of designing stable and safe Li metal anode via optimizing the 3D frameworks.

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.

Empowering the Future: Exploring the Construction and Characteristics of Lithium-Ion Batteries

Lithium element has attracted remarkable attraction for energy storage devices, over the past 30 years. Lithium is a light element and exhibits the low atomic number 3, just after hydrogen and helium in the periodic table. The lithium atom has a strong tendency to release one electron and constitute a positive charge, as Li . Initially, lithium metal was employed as a negative electrode, which released electrons. However, it was observed that its structure changed after the repetition of charge-discharge cycles. To remedy this, the cathode mainly consisted of layer metal oxide and olive, e.g., cobalt oxide, LiFePO4, etc., along with some contents of lithium, while the anode was assembled by graphite and silicon, etc. Moreover, the electrolyte was prepared using the lithium salt in a suitable solvent to attain a greater concentration of lithium ions. Owing to the lithium ions’ role, the battery’s name was mentioned as a lithium-ion battery. Herein, the presented work describes the working and operational mechanism of the lithium-ion battery. Further, the lithium-ion batteries’ general view and future prospects have also been elaborated.

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.

Engineering Multi‑field‑coupled Synergistic Ion Transport System Based on the Heterogeneous Nanofluidic Membrane for High‑Efficient Lithium Extraction

The global carbon neutrality strategy brings a wave of rechargeable lithium‐ion batteries technique development and induces an ever-growing consumption and demand for lithium(Li).Among all the Li exploitation,extracting Li from spent LIBs would be a strategic and perspective approach,especially with the low energy consumption and eco-friendly membrane separation method.However,current membrane separation systems mainly focus on monotonous membrane design and structure optimization,and rarely further consider the coordination of inherent structure and applied external field,resulting in limited ion transport.Here,we propose a heterogeneous nanofluidic membrane as a platform for coupling multi-external fields(i.e.,lightinduced heat,electrical,and concentration gradient fields)to construct the multi-field-coupled synergistic ion transport system(MSITS)for Li-ion extraction from spent LIBs.The Li flux of the MSITS reaches 367.4 mmol m^(−2)h^(−1),even higher than the sum flux of those applied individual fields,reflecting synergistic enhancement for ion transport of the multi-field-coupled effect.Benefiting from the adaptation of membrane structure and multi-external fields,the proposed system exhibits ultrahigh selectivity with a Li^(+)/Co^(2+)factor of 216,412,outperforming previous reports.MSITS based on nanofluidic membrane proves to be a promising ion transport strategy,as it could accelerate ion transmembrane transport and alleviate the ion concentration polarization effect.This work demonstrated a collaborative system equipped with an optimized membrane for high-efficient Li extraction,providing an expanded strategy to investigate the other membrane-based applications of their common similarities in core concepts.

Equilibrium concentration of lithium ion in sodium aluminate solution

Excess lithium in alumina is significantly bad for aluminum reduction.In this study,the concentration variation of lithium ion in sodium aluminate solution with addition of synthetic lithium aluminate was investigated.Elevating temperature,increasing caustic soda concentration,reducing alumina concentration or raising molar ratioαk improved equilibrium concentration of lithium ion in sodium aluminate solution.Agitation speed had a minimal effect on lithium ion concentration.Over 0.65 g/L lithium ion equilibrium concentration was observed in digestion process,whereas 35 mg/L lithium ion concentration remained in solution after precipitation time of 9 h.Moreover,equilibrium concentration decreased sharply from digestion of boehmite or diaspore to seed precipitation,about 95%lithium was precipitated into red mud(bauxite residue)and aluminum hydroxide.This study provides a valuable perspective in removal or extraction of lithium from sodium aluminate solution in alumina refineries.

Full-chain enhanced ion transport toward stable lithium metal anodes

The dendrite growth that results from the slow electrode process kinetics prevents the lithium(Li) metal anode from being used in practical applications. Here, full-chain enhanced ion transport for stabilizing Li metal anodes is proposed. Experimental and theoretical studies confirm that full-chain enhanced ion transport(electrocrystallization, mass transport in the electrolyte and diffusion in solid electrolyte interphase) under magnetoelectrochemistry contributes to a homogeneous, dense, and dendrite-free morphology. Specifically, the enhanced electrocrystallization behavior promotes the Li nucleation;the enhanced mass transport in the electrolyte alleviates the ion concentration gradient at the electrode surface, which helps to inhibit dendrite growth;and the enhanced diffusion in the solid electrolyte interphase further homogenizes the Li deposition behavior, obtaining regular and uniform Li particles.Consequently, the Li metal anode has exceptional cycling stability in both symmetric and full cells,and the pouch cell performs long cycles(170 cycles) in practice evaluation. This work advances fundamental knowledge of the magneto-dendrite effect and offers a new perspective on stabilizing metal anodes.

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.

High Ion-Selectivity of Garnet Solid Electrolyte Enabling Separation of Metallic Lithium

Ionic selectivity is of significant importance in both fundamental science and practical applications.For instance,an ion-selective material allows the passage of a particular kind of ions while blocking the others,which could be used for purification of materials.Herein,the Li-ion-selectivity of a garnet-type solid electrolyte is discussed by comparing the difference of activation energy between different ions migrating in solids.The high ion-selectivity is confirmed by harvesting high-purity metallic lithium(99.98 wt%)from low-lithium-purity sources(80 wt%)at a moderate temperature(190℃).This gives it huge potential in separating lithium with impurities especially alkali and alkali-earth elements.The cost of metallic lithium production is only 25%of the international lithium price.The proposed electrochemical metallic lithium separating method is advantageous compared with the traditional process in terms of efficiency,safety,and cost.

Bottom-up lithium growth guided by Ag concentration gradient in 3D PVDF framework towards stable lithium metal anode

Three-dimensional(3 D)frameworks have received much attention as an effective modification strategy for next-generation high-energy-density lithium metal batteries.However,the top-growth mode of lithium(Li)on the 3 D framework remains a tough challenge.To achieve a uniform bottom-up Li growth,a scheme involving Ag concentration gradient in 3 D PVDF framework(C-Ag/PVDF)is proposed.Ag nanoparticles with a concentration gradient induce an interface activity gradient in the 3 D framework,and this gradient feature is still maintained during the cycle.As a result,the C-Ag/PVDF framework delivers a long lifespan over 1800 h at a current density of 1 mA cm^(-2) with a capacity of 1 mAh cm^(-2),and shows an ultra-long life(>1300 h)even at a high current density of 4 mA cm^(-2) with a capacity of 4 mAh cm^(-2).The advantage of concentration gradient provides further insights into the optimal design of the 3 D framework for stable Li metal anode.

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.

Facile construction of a multilayered interface for a durable lithium‐rich cathode

Layered lithium-rich manganese-based oxide(LRMO)has the limitation of inevitable evolution of lattice oxygen release and layered structure transformation.Herein,a multilayer reconstruction strategy is applied to LRMO via facile pyrolysis of potassium Prussian blue.The multilayer interface is visually observed using an atomic-resolution scanning transmission electron microscope and a high-resolution transmission electron microscope.Combined with the electrochemical characterization,the redox of lattice oxygen is suppressed during the initial charging.In situ X-ray diffraction and the high-resolution transmission electron microscope demonstrate that the suppressed evolution of lattice oxygen eliminates the variation in the unit cell parameters during initial(de)lithiation,which further prevents lattice distortion during long cycling.As a result,the initial Coulombic efficiency of the modified LRMO is up to 87.31%,and the rate capacity and long-term cycle stability also improved considerably.In this work,a facile surface reconstruction strategy is used to suppress vigorous anionic redox,which is expected to stimulate material design in high-performance lithium ion batteries.

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.

The tri-band high spectral resolution spectrometer with gratings in tandem for the charge-exchange recombination spectroscopy diagnostic system on HL-2A tokamak

Charge-exchange(CX) recombination spectroscopy is a powerful tool monitoring ion temperature and plasma rotation with good temporal and spatial resolutions. A compact, new design for a high-throughput, tri-band high spectral resolution spectrometer has been developed for the charge-exchange recombination spectroscopy measurement on the HL-2A tokamak. The simultaneous measurements of He II(468.57 nm), C VI(529.1 nm), and Dα(656.1 nm accompanied by beam emission spectra) with an acquisition frequency up to 400 Hz are achieved by vertically binning the spectrum from each fiber in experiments. Initial results indicate that the system can provide radial profiles of not only ion temperature and rotation velocity,but also concentration of carbon. For the case of helium, the measurements for the ion temperature and rotation velocity are straightforward but the apparent concentration associated with the observed CX intensity is obviously too high. Modeling of the active He II CX feature including plume contributions needs to be carried out to extract the true helium concentration.The spectrometer could become a prototype for the ITER charge-exchange recombination spectroscopy diagnostic and the pilot experiments, as presented here, demonstrate the possibility of impurity concentrations measurements based on the combined measurement of local beam emission and charge-exchange recombination spectroscopy spectra.