Mg-doped,carbon-coated,and prelithiated SiO_(x) as anode materials with improved initial Coulombic efficiency for lithium-ion batteries

Silicon suboxide(SiO_(x),x≈1)is promising in serving as an anode material for lithium-ion batteries with high capacity,but it has a low initial Coulombic efficiency(ICE)due to the irreversible formation of lithium silicates during the first cycle.In this work,we modify SiO_(x) by solid-phase Mg doping reaction using low-cost Mg powder as a reducing agent.We show that Mg reduces SiO_(2) in SiO_(x) to Si and forms MgSiO_(3) or Mg_(2)SiO_(4).The MgSiO_(3) or Mg_(2)SiO_(4) are mainly distributed on the surface of SiO_(x),which suppresses the irreversible lithium-ion loss and enhances the ICE of SiO_(x).However,the formation of MgSiO_(3) or Mg_(2)SiO_(4) also sacrifices the capacity of SiO_(x).Therefore,by controlling the reaction process between Mg and SiO_(x),we can tune the phase composition,proportion,and morphology of the Mg-doped SiO_(x) and manipulate the performance.We obtain samples with a capacity of 1226 mAh g^(–1) and an ICE of 84.12%,which show significant improvement over carbon-coated SiO_(x) without Mg doping.By the synergistical modification of both Mg doping and prelithiation,the capacity of SiO_(x) is further increased to 1477 mAh g^(–1) with a minimal compromise in the ICE(83.77%).

Recent advances in hard carbon anodes with high initial Coulombic efficiency for sodium-ion batteries

Initial Coulombic efficiency(ICE)has been widely adopted in battery research as a quantifiable indicator for the lifespan,energy density and rate performance of batteries.Hard carbon materials have been accepted as a promising anode family for sodium-ion batteries(SIBs)owing to their outstanding performance.However,the booming application of hard carbon anodes has been significantly slowed by the low ICE,leading to a reduced energy density at the cell level.This offers a challenge to develop high ICE hard carbon anodes to meet the applications of high-performance SIBs.Here,we discuss the definition and factors of ICE and describe several typical strategies to improve the ICE of hard carbon anodes.The strategies for boosting the ICE of such anodes are also systematically categorized into several aspects including structure design,surface engineering,electrolyte optimization and pre-sodiation.The key challenges and perspectives in the development of high ICE hard carbon anodes are also outlined.

Boosting high initial coulombic efficiency of hard carbon by in-situ electrochemical presodiation

Hard carbon(HC)is a promising anode material for sodium ion batteries(SIBs),whereas inferior initial coulombic efficiency(ICE)severely limits its practical application.In the present work,we propose an in situ electrochemical presodiation approach to improve ICE by mixing sodium biphenyl(Na-Bp)dimethoxyethane(DME)solution with DME-based ether electrolyte.A solid electrolyte interface(SEI)could be formed beforehand on the HC electrode and Na^(+)was absorbed to nanopores and graphene stacks,compensating for the sodium loss and preventing electrolyte decomposition during the initial charge and discharge cycle.By this way,the ICE of half-cells was increased to nearly 100%and that of full-cells from 45%to 96%with energy density from 132.9 to 230.5 W h kg^(-1).Our work provides an efficient and facile method for improving ICE,which can potentially promote the practical application of HCbased materials.

Enhancing Li cycling coulombic efficiency while mitigating “shuttle effect” of Li-S battery through sustained release of LiNO_(3)

In practical lithium-sulfur batteries(LSBs),the shuttle effect and Li cycling coulombic efficiency(CE) are strongly affected by the physicochemical properties of solid electrolyte interphase(SEI).LiNO_(3) is widely used as an additive in electrolytes to build a high-quality SEI,but its self-sacrificial nature limits the ability to mitigate the shuttle effect and stabilize Li anode during long-term cycling.To counteract LiNO_(3) consumption during long-term cycling without using a high initial concentration,inspired by sustainedrelease drugs,we encapsulated LiNO_(3) in lithiated Nafion polymer and added an electrolyte co-solvent(1,1,2,2-tetrafluoroethylene 2,2,2-trifluoromethyl ether) with poor LiNO_(3) solubility to construct highquality and durable F-and N-rich SEI.Theoretical calculations,experiments,multiphysics simulations,and in-situ observations confirmed that the F-and N-rich SEI can modulate lithium deposition behavior and allow persistent repair of SEI during prolonged cycling.Hence,the F-and N-rich SEI improves the Li anode cycling CE to 99.63% and alleviates the shuttle effect during long-term cycling.The lithium anode with sustainable F-and N-rich SEI shows a stable Li plating/stripping over 2000 h at 1 mA cm^(-2).As expected,Li‖S full cells with this SEI achieved a long lifespan of 250 cycles,far exceeding cells with a routine SEI.The Li‖S pouch cell based on F-and N-rich SEI also can achieve a high energy density of about300 Wh kg^(-1) at initial cycles.This strategy provides a novel design for high-quality and durable SEls in LSBs and may also be extendable to other alkali metal batteries.

Engineering Mesoporous Structure in Amorphous Carbon Boosts Potassium Storage with High Initial Coulombic Efficiency

Amorphous carbon shows great potential as an anode material for high-performance potassium-ion batteries;however,its abundant defects or micropores generally capture K ions,thus resulting in high irreversible capacity with low initial Coulombic efficiency(ICE)and limited practical application.Herein,pore engineering via a facile self-etching strategy is applied to achieve mesoporous carbon(meso-C)nanowires with interconnected framework.Abundant and evenly distributed mesopores could provide short K^+ pathways for its rapid diffusion.Compared to microporous carbon with highly disordered structure,the meso-C with Zn-catalyzed short-range ordered structure enables more K^+to reversibly intercalate into the graphitic layers.Consequently,the mesoC shows an increased capacity by ~100 mAh g^-1 at 0.1 A g^-1,and the capacity retention is 70.7% after 1000 cycles at 1 A g^-1.Multiple in/ex situ characterizations reveal the reversible structural changes during the charging/discharging process.Particularly,benefiting from the mesoporous structure with reduced specific surface area by 31.5 times and less defects,the meso-C generates less irreversible capacity with high ICE up to 76.7%,one of the best reported values so far.This work provides a new perspective that mesopores engineering can effectively accelerate K^+ diffusion and enhance K^+ adsorption/intercalation storage.

Natural Stibnite for Lithium‑/Sodium‑Ion Batteries:Carbon Dots Evoked High Initial Coulombic Efficiency

The application of Sb_(2)S_(3)with marvelous theoretical capacity for alkali metal-ion batteries is seriously limited by its poor electrical conductivity and low initial coulombic efficiency(ICE).In this work,natural stibnite modified by carbon dots(Sb_(2)S_(3)@xCDs)is elaborately designed with high ICE.Greatly,chemical processes of local oxidation–partial reduction–deep coupling for stibnite reduction of CDs are clearly demonstrated,confirmed with in situ high-temperature X-ray diffraction.More impressively,the ICE for lithium-ion batteries(LIBs)is enhanced to 85%,through the effect of oxygen-rich carbon matrix on C–S bonds which inhibit the conversion of sulfur to sulfite,well supported by X-ray photoelectron spectroscopy characterization of solid electrolyte interphase layers helped with density functional theory calculations.Not than less,it is found that Sb–O–C bonds existed in the interface effectively promote the electronic conductivity and expedite ion transmission by reducing the bandgap and restraining the slip of the dislocation.As a result,the optimal sample delivers a tremendous reversible capacity of 660 mAh g^(−1)in LIBs at a high current rate of 5 A g^(−1).This work provides a new methodology for enhancing the electrochemical energy storage performance of metal sulfides,especially for improving the ICE.

An almost full reversible lithium-rich cathode: Revealing the mechanism of high initial coulombic efficiency

Low initial Coulombic efficiency (ICE) is an important impediment to practical application of Li-rich layered oxides (LLOs), which is due to the irreversible oxygen release. It is generally considered that surface oxygen vacancies are conducive to the improvement of ICE of LLOs. To reveal the relation of oxygen vacancies and ICE, sample PLO (Li-Mn-Cr-O) and its treated product (TLO) are comprehensive investigated in this work. During the treated process, part of oxygen atoms return to original constructed vacancies. It makes oxygen vacancies in sample TLO much poorer than those in sample PLO, and induces the formation of Li-poor spinel-layered integrated structure. Electrochemical measurement indicates the ICE of sample PLO is only 80.8%, while sample TLO is almost full reversible with the ICE of ~97.1%. In term of high-energy X-ray diffraction, scanning transmission electron microscopy, X-ray photoelectron spectroscopy and synchrotron hard/soft X-ray absorption spectroscopy, we discover that the ICE is difficult to be improved significantly just by building oxygen vacancies. LLOs with high ICE not only have to construct suitable oxygen vacancies, but also require other components with Li-poor structure to stabilize oxygen. This work provides deep insight into the mechanism of high ICE, and will contribute to the design and development of LLOs for next-generation high-energy lithium-ion batteries.

Sn Alloy and Graphite Addition to Enhance Initial Coulombic Efficiency and Cycling Stability of SiO Anodes for Li-Ion Batteries

Silicon monoxide(SiO)has aroused increased attention as one of the most promising anodes for high-energy density Li-ion batteries.To enhance the initial Coulombic efficiencies(ICE)and cycle stability of SiO-based anodes,a new facile composition and electrode design strategy have been adapted to fabricate a SiO-Sn-Co/graphite(G)anode.It achieves a unique structure where tiny milled SiO-Sn-Co particles are dispersed among two graphite layers.In this hybrid electrode,Sn-Co alloys promoted Li;extraction kinetics,and the holistic reversibility of SiO and graphite enhanced the electrical conductivity.The SiO-Sn-Co/G electrode delivered an average ICE of 77.6%and a reversible capacity of 640 mAh g^(-1)at 800 mA g^(-1),and the capacity retention was above 98%after 100 cycles,which was much higher than that of the SiO with an ICE of 55.3%and a capacity retention of 50%.These results indicated that this was reliable method to improve the reversibility and cycle ability of the SiO anode.Furthermore,based on its easy and feasible fabrication process,it may provide a suitable choice to combine other alloy anodes with the graphite anode.

Cautious interpretation of coulombic efficiency(CE) in lithium metal batteries

The soaring demand for electrical energy storage technologies stimulated by advanced portable devices, prospering electric vehicles, and large-scale grid storage applications have triggered explosive research on Li metal battery (LMB), which has been widely acknowledged as the most promising energy storage technology of the future that can break the energy-density bottleneck of the state-of-art lithium-ion battery (LIB) technology [1,2].

Low-temperature-pyrolysis preparation of nanostructured graphite towards rapid potassium storage with high initial Coulombic efficiency

Industrially prepared artificial graphite(AG)is attractive for potassium-ion batteries(PIBs),but its rate performance is poor and the production process is energy intensive,so developing an efficient strategy to produce novel graphite with low energy consumption and high performance is economically important.Herein,a nanostructured graphite composed of multi-walled carbon nanotubes(MWCNTs)and graphite shells was prepared by one-pot method through low-temperature pyrolysis of iron-based metal-organic framework(MOF)and carbon source.The high graphitization degree of nanostructured graphite makes the initial Coulombic efficiency(ICE)exceed 80%,and the three-dimensional(3D)conductive network ensures a specific capacity of 234 mAh·g^(−1)after 1000 cycles at a high current density of 500 mA·g^(−1).In addition,the typical graphite potassium storage mechanism is also demonstrated by in situ X-ray diffraction(XRD)and in situ Raman spectroscopy,and its practicality is also proved by the voltage of the full cells.This work provides a feasible way to optimize the practical production process of AG and expand its application in energy storage.

Access to advanced sodium-ion batteries by presodiation:Principles and applications

Sodium-ion batteries(SIBs)are expected to offer affordability and high energy density for large-scale energy storage system.However,the commercial application of SIBs is hurdled by low initial coulombic efficiency(ICE),continuous Na loss during long-term operation,and low sodium-content of cathode materials.In this scenario,presodiation strategy by introducing an external sodium reservoir has been rationally proposed,which could supplement additional sodium ions into the system and thereby markedly improve both the cycling performance and energy density of SIBs.In this review,the significance of presodiation is initially introduced,followed by comprehensive interpretation on technological properties,underlying principles,and associated approaches,as well as our perspectives on present inferiorities and future research directions.Overall,this contribution outlines a distinct pathway towards the presodiation methodology,of significance but still in its nascent phase,which may inspire the targeted guidelines to explore new chemistry in this field.

Prelithiation strategies for silicon-based anode in high energy density lithium-ion battery

Green energy storage devices play vital roles in reducing fossil fuel emissions and achieving carbon neutrality by 2050.Growing markets for portable electronics and electric vehicles create tremendous demand for advanced lithium-ion batteries(LIBs)with high power and energy density,and novel electrode material with high capacity and energy density is one of the keys to next-generation LIBs.Silicon-based materials,with high specific capacity,abundant natural resources,high-level safety and environmental friendliness,are quite promising alternative anode materials.However,significant volume expansion and redundant side reactions with electrolytes lead to active lithium loss and decreased coulombic efficiency(CE)of silicon-based material,which hinders the commercial application of silicon-based anode.Prelithiation,preembedding extra lithium ions in the electrodes,is a promising approach to replenish the lithium loss during cycling.Recent progress on prelithiation strategies for silicon-based anode,including electrochemical method,chemical method,direct contact method,and active material method,and their practical potentials are reviewed and prospected here.The development of advanced Si-based material and prelithiation technologies is expected to provide promising approaches for the large-scale application of silicon-based materials.

Fabricating multi-porous carbon anode with remarkable initial coulombic efficiency and enhanced rate capability for sodium-ion batteries

Due to the abundant sodium reserves and high safety,sodium ion batteries(SIBs)are foreseen a promising future.While,hard carbon materials are very suitable for the anode of SIBs owing to their structure and cost advantages.However,the unsatisfactory initial coulombic efficiency(ICE)is one of the crucial blemishes of hard carbon materials and the slow sodium storage kinetics also hinders their wide application.Herein,with spherical nano SiO_(2)as pore-forming agent,gelatin and polytetrafluoroethylene as carbon sources,a multi-porous carbon(MPC)material can be easily obtained via a co-pyrolysis method,by which carbonization and template removal can be achieved synchronously without the assistance of strong acids or strong bases.As a result,the MPC anode exhibited remarkable ICE of 83%and a high rate capability(208 m Ah/g at 5 A/g)when used in sodium-ion half cells.Additionally,coupling with Na3V2(PO4)3as the cathode to assemble full cells,the as-fabricated MPC//NVP full cell delivered a good rate capability(146 m Ah/g at 5 A/g)as well,implying a good application prospect the MPC anode has.

Trimming the Degrees of Freedom via a K^(+) Flux Rectifier for Safe and Long‑Life Potassium‑Ion Batteries

High degrees of freedom(DOF)for K^(+)movement in the electrolytes is desirable,because the resulting high ionic conductivity helps improve potassium-ion batteries,yet requiring support from highly free and flammable organic solvent molecules,seriously affecting battery safety.Here,we develop a K^(+)flux rectifier to trim K ion’s DOF to 1 and improve electrochemical properties.Although the ionic conductivity is compromised in the K^(+)flux rectifier,the overall electrochemical performance of PIBs was improved.An oxidation stability improvement from 4.0 to 5.9 V was realized,and the formation of dendrites and the dissolution of organic cathodes were inhibited.Consequently,the K||K cells continuously cycled over 3,700 h;K||Cu cells operated stably over 800 cycles with the Coulombic efficiency exceeding 99%;and K||graphite cells exhibited high-capacity retention over 74.7%after 1,500 cycles.Moreover,the 3,4,9,10-perylenetetracarboxylic diimide organic cathodes operated for more than 2,100 cycles and reached year-scale-cycling time.We fabricated a 2.18 Ah pouch cell with no significant capacity fading observed after 100 cycles.

A comprehensive review of pre-lithiation/sodiation additives for Li-ion and Na-ion batteries

Lithium/Sodium-ion batteries(LIB/SIB)have attracted enormous attention as a promising electrochemical energy storage system due to their high energy density and long cycle life.One of the major hurdles is the initial irreversible capacity loss during the first few cycles owing to forming the solid electrolyte interphase layer(SEI).This process consumes a profusion of lithium/sodium,which reduces the overall energy density and cycle life.Thus,a suitable approach to compensate for the irreversible capacity loss must be developed to improve the energy density and cycle life.Pre-lithiation/sodiation is a widely accepted process to compensate for the irreversible capacity loss during the initial cycles.Various strategies such as physical,chemical,and electrochemical pre-lithiation/sodiation have been explored;however,these approaches add an extra step to the current manufacturing process.Alternative to these strategies,pre-lithiation/sodiation additives have attracted enormous attention due to their easy adaptability and compatibility with the current battery manufacturing process.In this review,we consolidate recent developments and emphasize the importance of using pre-lithiation/sodiation additives(anode and cathode)to overcome the irreversible capacity loss during the initial cycles in lithium/sodium-ion batteries.This review also addresses the technical and scientific challenges of using pre-lithiation/sodiation additives and offers the insights to boost the energy density and cycle life with their possible commercial exploration.The most important prerequisites for designing effective pre-lithiation/sodiation additives have been explored and the future directions have been discussed.

Spontaneous local redox reaction to passivate CNTs as lightweight current collector for high energy density lithium ion batteries

Extensive usage of highly conductive carbon materials with large specific surface area(e.g.,carbon nanotubes,CNTs)in lithium ion batteries(LIBs),especially as current collector of anodes,suffers from low initial coulombic efficiency(ICE),large interfacial resistance,and severe embrittlement,as the large specific surface area often results in severe interfacial decomposition of the electrolyte and the formation of thick and fluffy solid electrolyte interphase(SEI)during cycling of LIBs.Herein,we demonstrate that when the CNT-based current collector and Na foil(which are being stacked intimately upon each other)are being placed in Na+-based organic electrolyte,local redox reaction between the Na foil and the electrolyte would occur spontaneously,generating a thin and homogeneous NaF-based passivating layer on the CNTs.More importantly,we found that owing to the weak solvation behaviors of Na+in the organic electrolyte,the resulting passivation layer,which is rich in NaF,is thin and dense;when used as the anode current collector in LIBs,the pre-existing passivating layer can function effectively in isolating the anode from the solvated Li+,thus suppressing the formation of bulky SEI and the destructive intercalation of solvated Li+.The relevant half-cell(graphite as anode)exhibits a high ICE of 92.1%;the relevant pouch cell with thus passivated CNT film as current collectors for both electrodes(LiCoO_(2)as cathode,graphite as anode)displays a high energy density of 255 Wh kg^(-1),spelling an increase of 50%compared with that using the conventional metal current collectors.

A lean-zinc anode battery based on metal-organic framework-derived carbon

Improving zinc metal(Zn^(0))reversibility and minimizing the N/P ratio are critical to boosting the energy density of Zn^(0) batteries.However,in reality,an excess Zn source is usually adopted to offset the irreversible zinc loss and guarantee sufficient zinc cycling,which sacrifices the energy density and leads to poor practicability of Zn^(0) batteries.To address the above conundrum,here,we report a lean-Zn and hierarchical anode based on metal-organic framework(MOF)-derived carbon,where trace Zn^(0) is pre-reserved within the anode structure to make up for any irreversible zinc source loss.This allows us to construct low N/P ratio Zn^(0) full cells when coupling the lean-Zn anode with Zn-containing cathodes.Impressively,high Zn^(0) reversibility(average Coulombic efficiency of 99.4% for 3000 cycles)and long full-cell lifetime(92% capacity retention after 900 cycles)were realized even under the harsh lean-Zn condition(N/P ratio:1.34).The excellent Zn reversibility is attributed to the hierarchy structure that homogenizes zinc ion flux and electric field distribution,as confirmed by theoretical simulations,which therefore stabilizes Zn^(0) evolution.The lean-Zn anode design strategy will provide new insights into construction of high-energy Zn^(0) batteries for practical applications.

Improving the Initial Coulombic Efficiency of Carbonaceous Materials for Li/Na‑Ion Batteries:Origins,Solutions,and Perspectives

Carbonaceous materials for lithium(Li)/sodium(Na)-ion batteries have attracted significant attention because of their widespread availability,renewable nature,and low cost.During the past decades,although great efforts have been devoted to developing high-performance carbonaceous materials with high capacity,long life span,and excellent rate capability,the low initial Coulombic efficiency(ICE)of high-capacity carbonaceous materials seriously limits their practical applications.Various methods have been successfully exploited,and a revolutionary impact has been achieved through the utilization of different techniques.Different carbonaceous materials possess different ion storage mechanisms,which means that the initial capacity loss may vary.However,there has rarely been a special review about the origins of and progress in the ICE for carbonaceous materials from the angle of the crystal structure.Hence,in this review,the structural differences between and ion storage mechanisms of various carbonaceous materials are first introduced.Then,we deduce the correlative factors of low ICE and thereafter summarize the proposed strategies to address these issues.Finally,some challenges,perspectives,and future directions on the ICE of carbonaceous materials are given.This review will provide deep insights into the challenges of improving the ICE of carbonaceous anodes for high-energy Li/Na-ion batteries,which will greatly contribute to their commercialization process.

Layer stacked SiO_(x) microparticle with disconnected interstices enables stable interphase and particle integrity for lithium-ion batteries

Severe mechanical fractu re and unstable interphase,associated with the large volumetric expansion/contraction,significantly hinder the application of high-capacity SiO_(x)materials in lithium-ion batteries.Herein,we report the design and facile synthesis of a layer stacked SiO_(x)microparticle(LS-SiO_(x))material,which presents a stacking structure of SiO_(x)layers with abundant disconnected interstices.This LS-SiO_(x)microparticle can effectively accommodate the volume expansion,while ensuring negligible particle expansion.More importantly,the interstices within SiO_(x)microparticle are disconnected from each other,which efficiently prevent the electrolyte from infiltration into the interior,achieving stable electrode/-electrolyte interface.Accordingly,the LS-SiO_(x)material without any coating delivers ultrahigh average Coulombic efficiency,outstanding cycling stability,and full-cell applicability.Only 6 cycles can attain>99.92%Coulombic efficiency and the capacity retention at 0.05 A g^(-1)for 100 cycles exceeds99%.After 800 cycles at 1 A g^(-1),the thickness swelling of LS-SiO_(x)electrode is as low as 0.87%.Moreover,the full cell with pure LS-SiO_(x)anode exhibits capacity retention of 91.2%after 300 cycles at 0.2 C.This work provides a novel concept and effective approach to rationally design silicon-based and other electrode materials with huge volume variation for electrochemical energy storage applications.

Rational design of stretchable and conductive hydrogel binder for highly reversible SiP2 anode

The emerging SiP2with large capacity and suitable plateau is proposed to be the alternative anode for Li-ion batteries.However,typical SiP2still suffers from serious volume expansion and structural destruction,resulting in much Li-consumption and capacity fading.Herein,a novel stretchable and conductive Li-PAA@PEDOT:PSS binder is rationally designed to improve the cyclability and reversibility of SiP2.Interestingly,such Li-PAA@PEDOT:PSS hydrogel enables a better accommodation of volume expansion than PVDF binder(e.g.5.94% vs.68.73% of expansivity).More specially,the SiP2electrode with LiPAA@PEDOT:PSS binder is surprisingly found to enable unexpected structural recombination and selfhealing Li-storage processes,endowing itself with a high initial Coulombic efficiency(ICE) up to 93.8%,much higher than PVDF binder(ICE=70.7%) as well.Such unusual phenomena are investigated in detail for Li-PAA@PEDOT:PSS,and the possible mechanism shows that its Li-PAA component enables to prevent the pulverization of SiP2nanoparticles while the PEDOT:PSS greatly bridges fast electronic connection for the whole electrode.Consequently,after being further composited with carbon matrix,the SiP2/C with LiPAA@PEDOT:PSS hydrogel exhibits high reversibility(ICE> 93%),superior cyclability(>450 cycles),and rate capability(1520 mAh/g at 2000 mA/g) for LIBs.This highly stretchable and conductive binder design can be easily extended to other alloying materials toward advanced energy storage.