Sn-based Intermetallic Compounds for Li-ion Batteries: Structures, Lithiation Mechanism, and Electrochemical Performances

On account of the lower theoretical capacity of the traditional graphite,the development of reliable anode materials with high capacity and energy density for application in lithium-ion batteries(LIBs)is zealously pursued to meet the ever-increasing power demands for portable mobile devices or(hybrid)electronic vehicles.

A simple model for diffusion-induced dislocations during the lithiation of crystalline materials

Assuming that the lithiation reaction occurs randomly in individual small particles in the vicinity of the reaction front, a simple model of diffusion- induced dislocations was developed. The diffusion-induced dislocations are con- trolled by the misfit strain created by the diffusion of solute atoms or the phase transformation in the vicinity of the reaction front. The dislocation density is proportional to the total surface area of the ＂lithiated particle＂ and inversely pro- portional to the particle volume. The diffusion-induced dislocations relieve the diffusion-induced stresses.

In situ tracking of the lithiation and sodiation process of disodium terephthalate as anodes for rechargeable batteries by Raman spectroscopy

Organic compounds represent an appealing group of electrode materials for rechargeable batteries due to their merits of biomass,sustainability,environmental friendliness,and processability.Disodium terephthalate(Na_(2)C_(8)H_(4)O_(4),Na_(2)TP),an organic salt with a theoretical capacity of 255 mAh·g^(-1),is electroactive towards both lithium and sodium.However,its electrochemical energy storage(EES)process has not been directly observed via in situ characterization techniques and the underlying mechanisms are still under debate.Herein,in situ Raman spectroscopy was employed to track the de/lithiation and de/sodiation processes of Na2TP.The appearance and then disappearance of the–COOLi Raman band at 1625 cm^(-1) during the de/lithiation,and the increase and then decrease of the–COONa Raman band at 1615 cm^(-1) during the de/sodiation processes of Na2TP elucidate the one-step with the 2Li+or 2Na+transfer mechanism.We also found that the inferior cycling stability of Na2TP as an anode for sodium-ion batteries(SIBs)than lithium-ion batteries(LIBs)could be due to the larger ion radium of Na+than Li+,which results in larger steric resistance and polarization during EES.The Na2TP,therefore,shows greater changes in spectra during de/sodiation than de/lithiation.We expect that our findings could provide a reference for the rational design of organic compounds for EES.

Tailoring V_(2)CT_(x) to form a derivative hybrid by partial oxidation for enhanced lithiation behavior

Utilizing MXene to form the multifunctional derivative is a route to construct high-performance electrode materials.To address this issue,V_(2)CT_(x) MXene was employed to realize a derivative of VOx/V_(2)CT_(x) MXene via a partial oxidation process.Relying on the annealing in the air atmosphere,the controlled oxidation behavior transformed V_(2)CT_(x) MXene partially to V_(2)O_(5) and formed a derivative hybrid of V_(2)O_(5)/V_(2)CT_(x) MXene.As a result,a package of capacity,rate performance,and cyclability can be enhanced.This work explores the derived behavior of MXenes and provides a route for constructing the hybrid with less interface contact.Furthermore,these findings can be extended to other MXene materials.

A chemo-mechanical model for fully-coupled lithiation reaction and stress generation in viscoplastic lithiated silicon

Development of stresses in silicon(Si) anodes of lithium-ion batteries is strongly affected by its mechanical properties. Recent experiments reveal that the mechanical behavior of lithiated silicon is viscoplastic, thereby indicating that lithiation-induced mechanical stresses are dependent on the lithiation reaction rate. Experimental evidence also accumulates that the rate of lithiation reaction is conversely affected by the magnitude of mechanical stresses. These experimental observations demonstrate that lithiation reaction and stress generation in silicon anodes are fully coupled. In this work, we formulate a chemo-mechanical model considering the two-way coupling between lithiation reaction and viscoplastic deformation in silicon nanoparticle anodes.Based on the model, the position of the lithiation interface, the interface velocity, and the lithiation-induced stresses can be solved simultaneously via numerical methods. The predicted interface velocity is in line with experimental measurements reported in the literature. We demonstrate that the lithiation-induced stress field depends on the lithiation reaction through two parameters:the migration velocity and the position of the lithiation interface. We identify a stress-mitigation mechanism in viscoplastic silicon anodes: the stress-regulated lithiation reaction at the interface serves as a "brake" to reduce the interface velocity and mitigate the lithiation-induced stresses, protecting the Si nanoparticle anode from being subjected to excessive mechanical stresses.

Unshackling the reversible capacity of SiO_(x)/graphite-based full cells via selective LiF-induced lithiation

Composite Si@SiO_(x)/C anodes with high specific capacity are considered the most promising alternatives to graphite in industrial lithium-ion batteries.However,their cycling stability remains a limiting factor,which originates from the severe volume deformation of silicon-derived species.In this work,the cyclabilities of composite anodes are improved by unshackling the highly reversible lithium storage capabilities from the redundancy capacity of the anode materials.A selective LiF-induced lithiation strategy is proposed based on exploiting interface separation energy differences between LiF and the active materials.An interesting preferential redeposition of LiF is observed at the Si@SiO_(x) particles,which differentiates the otherwise similar lithiation potentials of LiC_(x) and Li_(15)Si_(4),thereby enabling lithium storage in graphite that was previously underused.The resulting full cell exhibits better rate and cycling performances without sacrificing specific capacity.In an ultra-high area capacity full cell(4.9 mA h cm^(-2)),the capacity retention increases markedly from 66.1% to 94.2% after 300 cycles.The selective lithiation strategy developed herein is feasible for practical industrial applications,and importantly,it requires no changes to the existing mature lithium-ion battery manufacturing process.This study offers a new approach for the development of silicon/graphite composite anodes with long cycling lifetimes.

Surplus energy utilization of spent lithium-ion batteries for high-profit organolithiums

It is challenging to efficiently and economically recycle many lithium-ion batteries(LIBs)because of the low valuation of commodity metals and materials,such as LiFePO_(4).There are millions of tons of spent LIBs where the barrier to recycling is economical,and to make recycling more feasible,it is required that the value of the processed recycled material exceeds the value of raw commodity materials.The presented research illustrates improved profitability and economics for recycling spent LIBs by utilizing the surplus energy in lithiated graphite to drive the preparation of organolithiums to add value to the recycled lithium materials.This study methodology demonstrates that the surplus energy of lithiated graphite obtained from spent LIBs can be utilized to prepare high-value organolithiums,thereby significantly improving the economic profitability of LIB recycling.Organolithiums(R-O-Li and R-Li)were prepared using alkyl alcohol(R-OH)and alkyl bromide(R-Br)as substrates,where R includes varying hindered alkyl hydrocarbons.The organolithiums extracted from per kilogram of recycled LIBs can increase the economic value between$29.5 and$226.5 kg^(−1) cell.The value of the organolithiums is at least 5.4 times the total theoretical value of spent materials,improving the profitability of recycling LIBs over traditional pyrometallurgical($0.86 kg^(−1) cell),hydrometallurgical($1.00 kg^(−1) cell),and physical direct recycling methods($5.40 kg^(−1) cell).

Localized-domains staging structure and evolution in lithiated graphite

Intercalation provides to the host materials a means for controlled variation of many physical/chemical properties and dominates the reactions in metal‐ion batteries.Of particular interest is the graphite intercalation compounds with intriguing staging structures,which however are still unclear,especially in their nanostructure and dynamic transition mechanism.Herein,the nature of the staging structure and evolution of the lithium(Li)‐intercalated graphite was revealed by cryogenic‐transmission electron microscopy and other methods at the nanoscale.The intercalated Li‐ions distribute unevenly,generating local stress and dislocations in the graphitic structure.Each staging compound is found macroscopically ordered but microscopically inhomogeneous,exhibiting a localized‐domains structural model.Our findings uncover the correlation between the long‐range ordered structure and short‐range domains,refresh the insights on the staging structure and transition of Li‐intercalated/deintercalated graphite,and provide effective ways to enhance the reaction kinetic in rechargeable batteries by defect engineering.

Effects of Cr content on electrochemical properties of melt-spun Al_(75-x)Si_(25)Cr_x alloy anodes for lithium-ion batteries

Melt-spun Al75-xSi25Crx （x=2, 4, 7, 10, mole fraction, %） alloys were investigated as anode materials for lithium-ion batteries. The as-quenched ribbons consist of nano-grains and metallic glass. The electrochemical measurements reveal that an activation behavior is exhibited in the anodes. The specific capacity of the A173Si25Cr2 anodes can reach a maximum of 1119 mA.h/g and maintain at 586 mA·hg after 30 cycles. A more stable cycle performance is shown and a capacity loss is only 24% over 30 cycles for Al71Si25Cr4. The intermetallic compounds with Li cannot be detected in the lithiated anodes. After the ribbons were annealed, the specific capacities become much lower due to the formation of inert Al13SiaCr4, and an A1Li phase can be tested in the lithiated anodes. The Cr dissolved in the non-equilibrium alloys causes low lithiation activity and strong structure stability, which could be the main reason of the activation and a restriction of structure evolution.

Strong dependency of lithium diffusion on mechanical constraints in high-capacity Li-ion battery electrodes

The effect of external constraints on Li diffusion in high-capacity Li-ion battery electrodes is investigated using a coupled finite deformation theory. It is found that thinfilm electrodes on rigid substrates experience much slower diffusion rates compared with free-standing films with the same material properties and geometric dimensions. More importantly, the study reveals that mechanical driving forces tend to retard diffusion in highly-constrained thin films when lithiation-induced softening is considered, in contrast to the fact that mechanical driving forces always enhance diffusion when deformation is fully elastic. The results provide further proof that nano-particles are a better design option for nextgeneration alloy-based electrodes compared with thin films.

First-principles insight into Li and Na ion storage in graphene oxide

The structural, electronic, and adsorption properties of Li/Na ions on graphene decorated by epoxy groups are investigated by first-principles calculations based on density functional theory.Our results show that the concentration of epoxy groups remarkably affects the structural and electronic properties of graphene.The bandgaps change monotonically from0.16 eV to 3.35 eV when the O coverage increases from 12.5% to 50%(O/C ratio).Furthermore, the highest lithiation potential of 2.714 V is obtained for the case of graphene oxide(GO) with 37.5 % O coverage, while the highest sodiation potential is 1.503 V for GO with 12.5% O coverage.This clearly demonstrates that the concentration of epoxy groups has different effects on Li and Na storage in GO.Our results provide a new insight into enhancing the Li and Na storage by tuning the concentration of epoxy groups on GO.

A lithiated gel polymer electrolyte with superior interfacial performance for safe and long-life lithium metal battery

Rechargeable lithium metal batteries(LMBs)have gained much attention recently.However,the short lifespan and safety issues restrict their commercial applications.Here we report a novel gel polymer electrolyte(GPE)based on lithiated poly(vinyl chloride-r-acrylic acid)(PVCAALi)to realize dendritesuppressing and long-term stable lithium metal cycling.PVC chains ensure the quick gelation process and high electrolyte uptake,and lithiated PAA segments enable the increase of mechanical strength,acceleration of lithium-ion transmission and improvement of interfacial compatibility.PVCAALi GPE showed much higher mechanical strength compared with other free-standing GPEs in previous works.It displays a superior ionic conductivity of 1.50 m S cm^(-1) and a high lithium-ion transference number of 0.59 at room temperature.Besides,the lithiated GPE exhibits excellent interfacial compatibility with lithium metal anodes.Lithium symmetrical cells with PVCAALi GPE yield low hysteresis of 50 m V over1000 h at 1.0 m A cm^(-2).And the possible mechanism of the lithiated GPE with improved lithium-ion transfer and interfacial property was discussed.Accordingly,both the Li4Ti5O12/Li and lithium-sulfur(Li-S)cells assembled with PVCAALi GPE show outstanding electrochemical performance,retaining high discharge capacities of 133.8 m Ah g^(-1) and 603.8 m Ah g^(-1) over 200 cycles,respectively.This work proves excellent application potential of the highly effective and low-cost PVCAALi GPE in safe and long-life LMBs.

Ab initio Calculations of the Formation Energies of Lithium Intercalations in SnSb

SnSb has attracted a great attention in recent investigations as an anode material for Li ion batteries. The formation energies and electronic properties of the Li intercalations in SnSb have been calculated within the framework of local density functional theory and the first-principles pseudopotential technique. The changes of volumes, band structures, charge density analysis and the electronic density of states for the Li intercalations are presented. The results show that the average Li intercalation formation energy per Li atom is around 2.7 eV.

Electrochemical Intercalation of Lithium into Raw and Mild Oxide-treated Carbon Nanotubes Prepared by CVD

The raw carbon nanotubes (CNTs) prepared by chemical vapor deposition (CVD) were used in electrochemical lithiation. To remove the impurity the mild oxidation was done on the samples. The electrochemical characteristics of the two samples are investigated by the galvanostatic charge-discharge measurements and cyclic voltammetry. The structural and interfacial changes of the CNTs electrode were analyzed by XRD and FT-IR. The samples show a reversibility of lithium intercalation and de-intercalation. The reversible capacities of the first five cycles are larger than 300 mAh/g and the irreversible capacity of the first cycle was much larger than that mentioned in literatures. There is no identical change in the structure during the charge and discharge. The reactions at the interface between electrode and the electrolyte are similar to those of other carbonaceous materials.

Lithiated Nafion-garnet ceramic composite electrolyte membrane for solid-state lithium metal battery

Single-ion conducting solid polymer electrolytes are expected to play a vital role in the realization of solid-state Li metal batteries.In this work,a lithiated Nafion(Li-Nafion)-garnet ceramic Li6.25La3 Zr2 Al0.25O12(LLZAO)composite solid electrolyte(CSE)membrane with 30μm thickness was prepared for the first time.By employing X-ray photoelectron spectroscopy and transmission electron microscope,the interaction between LLZAO and Li-Nafion was investigated.It is found that the LLZAO interacts with the Li-Nafion to form a space charge layer at the interface between LLZAO and Li-Nafion.The space charge layer reduces the migration barrier of Li-ions and improves the ionic conductivity of the CSE membrane.The CSE membrane containing 10 wt%LLZAO exhibits the highest ionic conductivity of2.26×10-4 S cm-1 at 30℃among the pristine Li-Nafion membrane,the membrane containing 5 wt%,20 wt%,and 30 wt%LLZAO,respectively.It also exhibits a high Li-ion transference number of 0.92,and a broader electrochemical window of 0-+4.8 V vs.Li+/Li than that of 0-+4.0 V vs.Li+/Li for the pristine Li-Nafion membrane.It is observed that the CSE membrane not only inhibits the growth of Li dendrites but also keeps excellent electrochemical stability with the Li electrode.Benefitting from the above merits,the solid-state LiFePO4/Li cell fabricated with the CSE membrane was practically charged and discharged at 30℃.The cell exhibits an initial reversible discharge specific capacity of 160 mAh g-1 with 97%capacity retention after 100 cycles at 0.2 C,and maintains discharge specific capacity of 126 mAh g-1 after500 cycles at 1 C.The CSE membrane prepared with Li-Nafion and LLZAO is proved to be a promising solid electrolyte for advanced solid-state Li metal batteries.

Enhanced Electrochemical Performance of Poly(ethylene oxide)Composite Polymer Electrolyte via Incorporating Lithiated Covalent Organic Framework

The lithiated covalent organic framework(named TpPa-SO_(3) Li),which was prepared by a mild chemical lithiation strategy,was introduced in poly(ethylene oxide)(PEO)to produce the composite polymer electrolytes(CPEs).Li-ion can transfer along the PEO chain or across the layer of TpPa-SO_(3) Li within the nanochannels,resulting in a high Li-ion conductivity of3.01×10^(-4)S/cm at 60℃.When the CPE with 0.75 wt.%TpPa-SO_(3) Li was used in the LiFePO_(4)‖Li solid-state battery,the cell delivered a stable capacity of 125 mA·h/g after 250 cycles at 0.5 C,60℃.In comparison,the cell using the CPE without TpPa-SO_(3) Li exhibited a capacity of only 118 mA·h/g.

A long-life and safe lithiated graphite-selenium cell with competitive gravimetric and volumetric energy densities

Lithium-selenium(Li-Se) battery is a promising system with high theoretical gravimetric and volumetric energy densities, while its long-term cyclability is hard to realize, especially when a practical Se cathode with high Se content, high Se loading, and high density is employed. The main obstacles are the sluggish conversion kinetics of the dense Se cathodes and the continuous deterioration of the Li-metal anodes.Here, by introducing an acetonitrile(AN)-based electrolyte and replacing the Li electrode with a lithiated graphite, we successfully build a hybrid conversion-intercalation system using a high-content(80 wt%),decent-loading(3.0 mg cm^(-2)), and low-porosity(44%) Se cathode. The as-designed lithiated graphite||Se(LG||Se) cell demonstrated a high Se utilization(97.4%), a long cycle life(3000 cycles), and an ultrahigh average Coulombic efficiency(99.98%). The cell also works well under lean-electrolyte(2 l L mg^(-1)) condition and shows outstanding safety performance in the nail-penetrating test. The combination affords the competitive comprehensive performances, including high volumetric and gravimetric energy densities, long cycling life, and superb safety of the LG||Se cell. In addition, with a newly-designed threeelectrode pouch cell, the lithiation of the graphite anodes could be done with an in-situ lithiation process,indicating the high potential of the as-proposed LG||Se cell for the practical applications.

Gas electrodes with nickel based current collectors for molten carbonate electrolyte thermo-electrochemical cells

Thermo-electrochemical cells with inexpensive molten carbonate electrolyte and(CO2|O2) gas electrodes allow the possible conversion of high temperature waste heat from industrial processes into electricity.The cell containing eutectic(Li,Na)2CO3 electrolyte with solid Mg O dispersion delivers a large Seebeck coefficient of-1.7 m V/K. At present, the(CO2|O2) gas electrodes use metallic gold as current collectors in order to avoid the formation of interfering oxide layers during operation. For further reduction in energy generation cost, the gold current collectors should be replaced with an inexpensive and stable alternative.In this study, the suitability of the(molten carbonate fuel cell) MCFC’s nickel-based cathodes to operate the molten-carbonate thermo-electrochemical cell, was investigated. Ni current collectors were examined in two different states, as Ni O and as lithiated Ni O(LixNi1-xO). The Ni O phase shows higher stability than the LixNi1-xO while the Seebeck coefficient remains above-1.2 m V/K.

Revealing proton-coupled exchange mechanism in aqueous ion-exchange synthesis of nickel-rich layered cathodes for lithium-ion batteries

Ion exchange is a promising synthetic method for alleviating severe cation mixing in traditional layered oxide materials for lithium-ion batteries,leading to enhanced structural stability.However,the underlying mechanisms of ion exchange are still not fully understood.Such a fundamental study of the ion-exchange mechanism is needed for achieving the controllable synthesis of layered oxides with a stable structure.Herein,we thoroughly unearth the underlying mechanism that triggers the ion exchange of Ni-rich materials in aqueous solutions by examining time-resolved structural evolution combined with theoretical calculations.Our results reveal that the reaction pathway of ion exchange can be divided into two steps:protonation and lithiation.The proton is the key to achieving charge balance in the ion exchange process,as revealed by X-ray adsorption spectroscopy and inductive coupled plasma analysis.In addition,the intermediate product shows high lattice distortion during ion exchange,but it ends up with a most stable product with high lattice energy.Such apparent discrepancies in lattice energy between materials before and after ion exchange emphasize the importance of synthetic design in structural stability.This work provides new insights into the ion-exchange synthesis of Ni-rich oxide materials,which advances the development of cathode materials for high-performance lithium-ion batteries.

Lithiated Graphdiyne Quantum Dots for Stable Lithium Metal Anodes

Here,a facile strategy is proposed for the preparation of lithiated graphdiyne quantum dots(GDY-Li QDs)with conjugated sp-and sp2-hybridized carbons by the self-assembly technique ofπ–πstacking of lithiated hexaethynylbezene under mild conditions.The as-prepared GDY-Li QDs,containing stacked multialkynyl aromatic backbone and abundant lithium(Li),show an average diameter of about 2.6 nm and good dispersion in the solvents.These distinctive structures endow GDY-Li QDs with superior properties that cannot be matched by traditional QDs,such as strong ion adsorption,Li-ion self-concentration,high Li-ion conductivity,the nanoconfinement effect,and ion solvation regulation.Benefiting from these features,GDY-Li QDs can stabilize Limetal anodes to effectively suppress Li-dendrite growth and significantly improve its Li plating/stripping coulombic efficiency(99.3%in the carbonate electrolyte).The full cells with GDY-Li QDs protected Li-metal anodes,and LiNi_(0.8)Co_(0.1)Mn^(0.1)O_(2)cathodes delivered high capacity and excellent cycling stability at high rates,which demonstrates the great potential of GDY-Li QDs for application in fast-charging Li-metal batteries.