Lithium nickel oxide(Li_(2)NiO_(2)),as a sacrificial cathode prelithiation additive,has been used to compensate for the lithium loss for improving the lifespan of lithium-ion batteries(LIBs).However,high-cost Li_(2)Ni...Lithium nickel oxide(Li_(2)NiO_(2)),as a sacrificial cathode prelithiation additive,has been used to compensate for the lithium loss for improving the lifespan of lithium-ion batteries(LIBs).However,high-cost Li_(2)NiO_(2)suffers from inferior delithiation kinetics during the first cycle.Herein,we investigated the effects of the cost-effective copper substituted Li_(2)Ni_(1-x)Cu_(x)O_(2)(x=0,0.2,0.3,0.5,0.7)synthesized by a high-temperature solid-phase method on the structure,morphology,electrochemical performance of graphite‖LiFePO_(4)battery.The X-ray diffraction(XRD)refinement result demonstrated that Cu substitution strategy could be favorable for eliminating the NiO_(x)impurity phase and weakening Li-O bond.Analysis on density of states(DOS)indicates that Cu substitution is good for enhancing the electronic conductivity,as well as reducing the delithi-ation voltage polarization confirmed by electrochemical characterizations.Therefore,the optimal Li_(2)Ni_(0.7)Cu_(0.3)O_(2)delivered a high delithiation capacity of 437 mAh·g^(-1),around 8%above that of the pristine Li_(2)NiO_(2).Furthermore,a graphite‖LiFePO_(4)pouch cell with a nominal capacity of 3000 mAh demonstrated a notably improved reversible capacity,energy density and cycle life through introducing 2 wt%Li_(2)Ni_(0.7)Cu_(0.3)O_(2)additive,delivering a 6.2 mAh·g^(-1)higher initial discharge capacity and achieving around 5%improvement in capacity retentnion at 0.5P over 1000 cycles.Additionally,the post-mortem analyses testified that the Li_(2)Ni_(0.7)Cu_(0.3)O_(2)additive could suppress solid electrolyte interphase(SEI)decomposition and homogenize the Li distribution,which benefits to stabilizing interface between graphite and electrolyte,and alleviating dendritic Li plating.In conclusion,the Li_(2)Ni_(0.7)Cu_(0.3)O_(2)additive may offer advantages such as lower cost,lower delithiation voltage and higher prelithiation capacity compared with Li_(2)NiO_(2),making it a promising candidate of cathode prelithiation additive for next-generation LIBs.展开更多
The demand for high safety and high reliability lithium-ion batteries(LIBs)is strongly considered for practical applications.However,due to their inherent self-discharge properties or abuse,LIBs face the threat of ove...The demand for high safety and high reliability lithium-ion batteries(LIBs)is strongly considered for practical applications.However,due to their inherent self-discharge properties or abuse,LIBs face the threat of over-discharge,which induces premature end of life and increased risk of thermal runaway.In addition,a strong demand for batteries with zero-volt storage is strongly considered for aerospace and implantable medical devices.In this review,we firstly introduce the necessity and the importance of over-discharge and zero-volt protection for LIBs.The mechanism of damage to the Cu current collectors and SEI induced by potential changes during over-discharge is presented.The current over-discharge protection strategies based on whether the zero-crossing potential of the electrodes is summarized.Finally,the fresh insights into the material design of cathode prelithiation additives are presented from the perspective of over-discharge protection.展开更多
The ever-increasing environmental/energy crisis as well as the rapid upgrading of mobile devices had stimulated intensive research attention on promising alternative energy storage and conversion devices.Among these d...The ever-increasing environmental/energy crisis as well as the rapid upgrading of mobile devices had stimulated intensive research attention on promising alternative energy storage and conversion devices.Among these devices,alkali metal ion batteries,such as lithium-ion batteries(LIBs) had attracted increasing research attention due to its several advantages including,environmental friendliness,high power density,long cycle life and excellent reversibility.It had been widely used in consumer electronics,electric vehicles,and large power grids et ac.Silicon-based(silicon and their oxides,carbides) anodes had been widely studied.Its several advantages including low cost,high theoretical capacity,natural abundance,and environmental friendliness,which shows great potential as anodes of LIBs.In this review,we summarized the recently progress in the synthetic method of silicon matrix composites.The empirical method for prelithiation of silicon-based materials were also provided.Further,we also reviewed some novel characterization methods.Finally,the new design,preparation methods and properties of these nano materials were reviewed and compared.We hoped that this review can provide a general overview of recent progress and we briefly highlighted the current challenges and prospects,and will clarify the future trend of silicon anode LIBs research.展开更多
The solvation structure of Li^(+) in chemical prelithiation reagent plays a key role in improving the low initial Coulombic efficiency(ICE) and poor cycle performance of silicon-based materials. Never theless, the che...The solvation structure of Li^(+) in chemical prelithiation reagent plays a key role in improving the low initial Coulombic efficiency(ICE) and poor cycle performance of silicon-based materials. Never theless, the chemical prelithiation agent is difficult to dope active Li^(+) in silicon-based anodes because of their low working voltage and sluggish Li^(+) diffusion rate. By selecting the lithium–arene complex reagent with 4-methylbiphenyl as an anion ligand and 2-methyltetrahydrofuran as a solvent, the as-prepared micro-sized Si O/C anode can achieve an ICE of nearly 100%. Interestingly, the best prelithium efficiency does not correspond to the lowest redox half-potential(E_(1/2)), and the prelithiation efficiency is determined by the specific influencing factors(E_(1/2), Li^(+) concentration, desolvation energy, and ion diffusion path). In addition, molecular dynamics simulations demonstrate that the ideal prelithiation efficiency can be achieved by choosing appropriate anion ligand and solvent to regulate the solvation structure of Li^(+). Furthermore, the positive effect of prelithiation on cycle performance has been verified by using an in-situ electrochemical dilatometry and solid electrolyte interphase film characterizations.展开更多
Prelithiation technology is widely considered a feasible route to raise the energy density and elongate the cycle life of lithium-ion batteries.The principle of prelithiation is to introduce extra active Li ions in th...Prelithiation technology is widely considered a feasible route to raise the energy density and elongate the cycle life of lithium-ion batteries.The principle of prelithiation is to introduce extra active Li ions in the battery so that the lithium loss during the first charge and long-term cycling can be compensated.Such an effect does not need to change the major electrode material or battery structure and is compatible with the majority of current lithium-ion battery production lines.At this stage,various prelithiation methods have been reported,some of which are already in the pilot-scale production stage.But there is still no definitive development roadmap for prelithiation.In this review,we first introduce the influence of prelithiation on electrochemical performance from a theoretical point of view and then compare the pros and cons of different prelithiation methods in different battery manufacturing stages.Finally,we discuss the challenges and future development trends of prelithiation.We aim to build up a bridge between academic research and industrial application.Some engineering problems in the promotion of prelithiation technique are extensively discussed,including not only the implementation of prelithiation but also some collateral issues on battery designing and management.展开更多
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 advan...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.展开更多
Lithium-ion capacitors(LICs),consisting of a capacitor-type material and a battery-type material together with organic electrolytes,are the state-of-the-art electrochemical energy storage devices compared with superca...Lithium-ion capacitors(LICs),consisting of a capacitor-type material and a battery-type material together with organic electrolytes,are the state-of-the-art electrochemical energy storage devices compared with supercapacitors and batteries.Owing to their unique characteristics,LICs received a lot of attentions,and great progresses have been achieved,especially in the exploration of cathode and anode materials.Prelithiation techniques are regarded as indispensable procedures for LICs systems,which can compensate for the initial irreversible capacity loss,increase the Li^(+)concentration in the electrolyte,raise the working voltage and resolve the safety and cycle stability issues;however,its research progress is slow,and there is not enough attention until now.In this overview,we look into the ongoing processes on the recent development of prelithiation technologies,especially in organic electrolyte consumption-type LICs.In particular,some prelithiation strategies for LICs are summarized and discussed in detail,including the ex situ electrochemical method,in situ electrochemical method,and cathode prelithiation additives method.Moreover,we propose some unresolved challenges and prospects for prelithiation technologies from the basic research ideas and future key research directions.This work aims to bring up new insights to reassess the significance of premetallation strategies for advanced hybrid-ion capacitors based on the currently proposed prelithiation strategies.展开更多
Lithium ion capacitors(LICs)have been widely used as energy storage devices due to their high energy density and high power density.For LICs,pre-lithiation of negative electrode is necessary.In this work,we employ a b...Lithium ion capacitors(LICs)have been widely used as energy storage devices due to their high energy density and high power density.For LICs,pre-lithiation of negative electrode is necessary.In this work,we employ a bifunctional Li6CoO4(LCO)as cathodic pre-lithiation reagent to improve the electrochemical performance of LICs.The synthesized LCO exhibited high first charge specific capacity of 721 mAh g-1and extremely low initial coulombic efficiency of 3.19%,providing sufficient Li+ for the pre-lithiation of negative electrode in the first charge.Simultaneously,Li6–xCoOy is generated from LCO during the first charge process,which exhibits pseudocapacitive property and contributes to capacity in form of surface capacitance during subsequent cycles,increasing the capacity of capacitive positive electrode.With the appropriate amounts of addition to the positive side in LICs,this bifunctional prelithiation reagent LCO shows significantly improved the electrochemical performance with the energy density of 78.5 Wh kg-1after 300 cycles between 2.0 and 4.2 V at 250 mA g-1.展开更多
With the increasing market demand for high-performance lithium-ion batteries with high-capacity electrode materials,reducing the irreversible capacity loss in the initial cycle and compensating for the active lithium ...With the increasing market demand for high-performance lithium-ion batteries with high-capacity electrode materials,reducing the irreversible capacity loss in the initial cycle and compensating for the active lithium loss during the cycling process are critical challenges.In recent years,various prelithiation strategies have been developed to overcome these issues.Since these approaches are carried out under a wide range of conditions,it is essential to evaluate their suitability for large-scale commercial applications.In this review,these strategies are categorized based on different battery assembling stages that they are implemented in,including active material synthesis,the slurry mixing process,electrode pretreatment,and battery fabrication.Furthermore,their advantages and disadvantages in commercial production are discussed from the perspective of thermodynamics and kinetics.This review aims to provide guidance for the future development of prelithiation strategies toward commercialization,which will potentially promote the practical application of next-generation high-energy-density lithium-ion batteries.展开更多
During the last decade,the rapid development of lithium-ion battery(LIB)energy storage systems has provided significant support for the efficient operation of renewable energy stations.In the coming years,the service ...During the last decade,the rapid development of lithium-ion battery(LIB)energy storage systems has provided significant support for the efficient operation of renewable energy stations.In the coming years,the service life demand of energy storage systems will be further increased to 30 years from the current 20 years on the basis of the equivalent service life of renewable energy stations.However,the life of the present LIB is far from meeting such high demand.Therefore,research on the next-generation LIB with ultra-long service life is imminent.Prelithiation technology has been widely studied as an important means to compensate for the initial coulombic efficiency loss and improve the service life of LIBs.This review systematically summarized the different prelithiation methods from anode and cathode electrodes.Moreover,the large-scale industrialization challenge and the possibility of the existing prelithiation technology are analyzed,based on three key parameters:industry compatibility,prelithiation efficiency,and energy density.Finally,the future trends of improvement in LIB performance by other overlithiated cathode materials are presented,which gives a reference for subsequent research.展开更多
Silicon monoxide(SiO)is regarded as a potential candidate for anode materials of lithium-ion batteries(LIBs).Unfortunately,the application of SiO is limited by poor initial Coulombic efficiency(ICE)and unsteady solid ...Silicon monoxide(SiO)is regarded as a potential candidate for anode materials of lithium-ion batteries(LIBs).Unfortunately,the application of SiO is limited by poor initial Coulombic efficiency(ICE)and unsteady solid electrolyte interface(SEI),which induce low energy,short cycling life,and poor rate properties.To address these drawbacks of SiO,we achieve in-situ construction of robust and fast-ion conducting F,N-rich SEI layer on prelithiated micro-sized SiO(P-μSiO)via the simple and continuous treatment ofμSiO in mild lithium 4,4′-dimethylbiphenyl solution and nonflammable hexafluorocyclotriphosphazene solution.Chemical prelithiation eliminates irreversible capacity through pre-forming inactive lithium silicates.Meanwhile,the symbiotic F,N-rich SEI with good mechanical stability and fast Li^(+)permeability is conductive to relieve volume expansion ofμSiO and boost the Li+diffusion kinetics.Consequently,the P-μSiO realizes an impressive electrochemical performance with an elevated ICE of 99.57%and a capacity retention of 90.67%after 350 cycles.Additionally,the full cell with P-μSiO anode and commercial LiFePO_(4) cathode displays an ICE of 92.03%and a high reversible capacity of 144.97 mA h g^(-1).This work offers a general construction strategy of robust and ionically conductive SEI for advanced LIBs.展开更多
The commercialization of silicon-based anodes is affected by their low initial Coulombic efficiency(ICE)and capacity decay,which are attributed to the formation of an unstable solid electrolyte interface(SEI)layer.Her...The commercialization of silicon-based anodes is affected by their low initial Coulombic efficiency(ICE)and capacity decay,which are attributed to the formation of an unstable solid electrolyte interface(SEI)layer.Herein,a feasible and cost-effective prelithiation method under a localized highconcentration electrolyte system(LHCE)for the silicon-silica/graphite(Si-SiO_(2)/C@G)anode is designed for stabilizing the SEI layer and enhancing the ICE.The thin SiO_(2)/C layers with-NH_(2) groups covered on nano-Si surfaces are demonstrated to be beneficial to the prelithiation process by density functional theory calculations and electrochemical performance.The SEI formed under LHCE is proven to be rich in ionic conductivity,inorganic substances,and flexible organic products.Thus,faster Li+transportation across the SEI further enhances the prelithiation effect and the rate performance of Si-SiO_(2)/C@G anodes.LHCE also leads to uniform decomposition and high stability of the SEI with abundant organic components.As a result,the prepared anode shows a high reversible specific capacity of 937.5 mAh g^(-1)after 400 cycles at a current density of 1 C.NCM 811‖Li-SSGLHCE full cell achieves a high-capacity retention of 126.15 mAh g^(-1)at 1 C over 750 cycles with 84.82%ICE,indicating the great value of this strategy for Si-based anodes in large-scale applications.展开更多
Prelithiation has been intensively investigated in high-capacity lithiumion batteries(LIBs).However,the optimization of prelithiation degrees for long service life of LIBs still remains a challenge.The positive effect...Prelithiation has been intensively investigated in high-capacity lithiumion batteries(LIBs).However,the optimization of prelithiation degrees for long service life of LIBs still remains a challenge.The positive effect of prelithiation on suppressing degradation of LIBs,besides directly pursuing the high first Coulomb efficiency which has been widely reported in the literature,is revealed and discussed based on an analytical model focusing on the interfacial delamination in electrodes.For full charge-discharge cycling,well-designed prelithiation can effectively suppress the delamination and reduce the debonding size by approximately 25%,compared with the case without prelithiation.For the strategy combining partial charge-discharge cycling and prelithiation,the largest reversible capacity without debonding can be significantly improved by approximately100%with well-designed prelithiation.This work is expected to provide a prelithiation design principle and further improve the mechanical stability of LIB electrodes.展开更多
Silicon oxide(SiO_(x))anodes have emerged as a promising substitute for graphite anodes owing to their high specific capacity and cost-effectiveness.However,they face challenges including significant volume expansion-...Silicon oxide(SiO_(x))anodes have emerged as a promising substitute for graphite anodes owing to their high specific capacity and cost-effectiveness.However,they face challenges including significant volume expansion-induced electrode cracking and unsatisfactory initial Coulombic efficiency.Herein,we use a prelithiation strategy to address these challenges for quasi-solid-state batteries using a garnet-type solid electrolyte.Using a contact-based prelithiation configuration,full prelithiation of SiO_(x) anodes were achieved through spontaneous lithium-ion intercalation assisted by molten salts.The garnet-type solid electrolyte based full cells are assembled with fully prelithiated SiO_(x) anodes and LiFePO_(4) cathode using molten salts as interface layer.The quasi-solid-state full cells with high initial coulombic efficiency maintain exceptional cycling stability with over 80%capacity retention after 300 cycles.The molten salt modulates the solid electrolyte interphase composition for SiO_(x) anodes and effectively suppressing SiO_(x) particle fracture during cycling.This work offers a practical route toward highenergy-density lithium batteries for next-generation energy storage.展开更多
Silicon possesses a high theoretical capacity,making it a potential contender for lithium-ion battery(LIB)anodes.Nonetheless,its practical usage is challenged by low electrical conductivity and significant volume expa...Silicon possesses a high theoretical capacity,making it a potential contender for lithium-ion battery(LIB)anodes.Nonetheless,its practical usage is challenged by low electrical conductivity and significant volume expansion during cycling.Here,we synthesized a novel silicon/carbon(Si/C)anode doped with ZnO via a template-derived method and high-temperature carbonization.The carbon structure,originated from metal-organic frameworks(MOFs)and ZnO doping,substantially enhanced the electrochemical properties of the composite material.It exhibited an initial capacity of 2100.3 mA h g^(-1)at a current density of 0.2 A g^(-1)and demonstrated excellent capacity retention over successive cycles.Moreover,the composite material displayed superior rate performance at higher current densities of 2 A g^(-1)and 3 A g^(-1).To address the low initial Coulombic efficiency(ICE)of siliconbased materials,we adopted a direct contact prelithiation approach and optimized the lithiation process by controlling the prelithiation time.After 30 min of prelithiation,the ICE reached 97.9%,thereby reducing the initial irreversible capacity loss(ICL)and realizing stable discharge-charge in subsequent cycles.This rational design provides valuable insights for achieving high-performance silicon anode.展开更多
Lithium-ion batteries are widely used in portable electronics and electric vehicles due to their high energy density,stable cycle life,and low self-discharge.However,irreversible lithium loss during the formation of t...Lithium-ion batteries are widely used in portable electronics and electric vehicles due to their high energy density,stable cycle life,and low self-discharge.However,irreversible lithium loss during the formation of the solid electrolyte interface greatly impairs energy density and cyclability.To compensate for the lithium loss,introducing an external lithium source,that is,a prelithiation agent,is an effective strategy to solve the above problems.Compared with other prelithiation strategies,cathode prelithiation is more cost-effective with simpler operation.Among various cathode prelithiation agents,we first systematically summarize the recent progress of Li_(2)S-based prelithiation agents,and then propose some novel strategies to tackle the current challenges.This review provides a comprehensive understanding of Li_(2)S-based prelithiation agents and new research directions in the future.展开更多
The low initial Coulombic efficiency(ICE)of SiOx anode caused by the irreversible generation of LiySiOz and Li20 during lithiation process limits its application for high energy-density lithium-ion batteries.Herein,we...The low initial Coulombic efficiency(ICE)of SiOx anode caused by the irreversible generation of LiySiOz and Li20 during lithiation process limits its application for high energy-density lithium-ion batteries.Herein,we report a molten-salt-induced thermochemical.prelithiation strategy for regulating the electrochemically active Si/O ratio of SiOx and thus enhancing ICE through thermal treatment of pre-synthesized LiNH2-coated SiOx in molten LiCl at 700℃.Bulk SiOx micro-particle was transformed into pomegranatelike prelithiated micro-cluster composite(M-Li-SiOx)with SiOx core and outer nano-sized agglomerates consisting of Li2Si20s,SiO2,and Si.Through the analysis of the reaction intermediates,molten-UC!could initiate reactions and promote mass transfer by the continuous extraction of oxygen component from SiOx particle inner in the form of inert Li2Si20s and SiO2 nanotubes to realize the.prelithiation.The degree of prelithiation can be regulated by adjusting the coating amount of LiNH2 layer,and the resulted M-Li-SiOx displays a prominent improvement of ICE from 58.73%to 88.2%.The graphite/M-Li-SiOx(8:2)composite electrode delivers a.discharge capacity of 497.29 mAh·g^(-1) with an ICE of 91.79%.By pairing graphite/M-Li-SiOx anode and LiFeP04 cathode in a full-cell an enhancement of energy density of 37.25%is realized compared with the full-cell containing graphite/SiOx anode.Furthermore,,ex-situ X-ray photoelectron spectroscopy(XPS)/Raman/X-ray diffraction(XRD)and related electrochemical measurements reveal the SiOx core and Si of M-Li-SiOx participate in the lithiation,and pre-generated Li2Si20s with u+diffusivity and pomegranate-like.structure reduces the reaction resistance and interface impedance of the solid electrolyte interphase(SEI)film.展开更多
Chemical prelithiation is regarded as a crucial method for improving the initial Coulombic efficiency(ICE)of Li-storage anodes.Herein,a substituent-engineered Li-cyanonaphthalene chemical prelithiation system is desig...Chemical prelithiation is regarded as a crucial method for improving the initial Coulombic efficiency(ICE)of Li-storage anodes.Herein,a substituent-engineered Li-cyanonaphthalene chemical prelithiation system is designed to simultaneously enhance the ICE and construct a multifunctional interfacial film for SiO electrodes.X-ray photoelectron spectroscopy(XPS),electron energy-loss spectroscopy(EELS),nuclear magnetic resonance(NMR)spectroscopy and atomic force microscopy(AFM)prove that the Licyanonaphthalene prelithiation reagent facilitates the formation of a rectified solid electrolyte interface(SEI)film in two ways:(1)generation of a gradient SEI film with an organic outer layer(dense Ncontaining organics,ROCO_(2)Li)and an inorganic LiF-enriched inner layer;(2)homogenization of the horizontal distribution of the composition,mechanical properties and surface potential.As a result,the prelithiated SiO electrode exhibits an ICE above 100%,enhanced CEs during cycling,better cycle stability and inhibition of lithium dendrite formation in the overcharged state.Notably,the prelithiated hard carbon/SiO(9:1)‖LHCoO_(2) cell displays an enhancement in the energy density of 62.3%.展开更多
In order to address the issues of low initial Coulombic efficiency of SiO_(x)-C composite anode due to the formation of solid electrolyte interphase,irreversible conversion reaction,and large volume change,the prelith...In order to address the issues of low initial Coulombic efficiency of SiO_(x)-C composite anode due to the formation of solid electrolyte interphase,irreversible conversion reaction,and large volume change,the prelithiation method using metal lithium has been employed as one of effective solutions.However,violent side reactions with liquid electrolyte for prelithiation lead to low prelithiation efficiency and induce poor interface between the SiO_(x)-C electrode and liquid electrolyte.Here,a new prelithiation method with so called solid-state corrosion of lithium is developed.By replacing liquid electrolyte with solid-state electrolyte of carbon-incorporated lithium phosphorus oxynitride(LiCPON),not only various side reactions associated with metal lithium are avoided,but also the perfect interface is achieved from the decomposition products of LiCPON.The successful implementation of solid-state corrosion prelithiation can be confirmed by changes in optical image,scanning electron microscopy,and X-ray diffraction.Compared with pristine electrode,the initial Coulombic efficiency of the prelithiated electrode using solid electrolyte can be increased by about 10%,reaching 98.6%in half cell and 88.9%in full cell.Compared with prelithiated electrode using liquid electrolyte,the prelithiation efficiency of the prelithiated anode with solid-state corrosion can be increased from 25.7%to 82.8%.Solid-state corrosion of lithium is expected to become a useful method for prelithiation of SiO_(x)-C composite electrode with high initial Coulombic efficiency and large prelithiation efficiency.展开更多
Chemical prelithiation is widely proven to be an effective strategy to address the low initial coulombic efficiency(ICE)of promising SiO_(x) anode.Though the reagent composition has been widely explored,the Li^(+) sol...Chemical prelithiation is widely proven to be an effective strategy to address the low initial coulombic efficiency(ICE)of promising SiO_(x) anode.Though the reagent composition has been widely explored,the Li^(+) solvation structure,which practically plays the cornerstone role in the prelithiation ability,rate,uniformility,has rarely been explored.A novel environmentally-friendly reagent with weak solvent cyclopentyl methyl ether(CPME)is proposed that enables both improved ICE and spatial homogeneous solid electrolyte interphase(SEl).And the prelithiation behavior and mechanism were explored focused on the Li^(+) solvation structure.Both theoretical investigation and spectroscopic results suggest that weak solvent feature of CPME reduces the solvent coordination number and decreases the Li^(+) desolvation energy.展开更多
基金supported by the Significant Science and Technology Project in Xiamen(Future Industry Field)(Grant No.3502Z20231057).
文摘Lithium nickel oxide(Li_(2)NiO_(2)),as a sacrificial cathode prelithiation additive,has been used to compensate for the lithium loss for improving the lifespan of lithium-ion batteries(LIBs).However,high-cost Li_(2)NiO_(2)suffers from inferior delithiation kinetics during the first cycle.Herein,we investigated the effects of the cost-effective copper substituted Li_(2)Ni_(1-x)Cu_(x)O_(2)(x=0,0.2,0.3,0.5,0.7)synthesized by a high-temperature solid-phase method on the structure,morphology,electrochemical performance of graphite‖LiFePO_(4)battery.The X-ray diffraction(XRD)refinement result demonstrated that Cu substitution strategy could be favorable for eliminating the NiO_(x)impurity phase and weakening Li-O bond.Analysis on density of states(DOS)indicates that Cu substitution is good for enhancing the electronic conductivity,as well as reducing the delithi-ation voltage polarization confirmed by electrochemical characterizations.Therefore,the optimal Li_(2)Ni_(0.7)Cu_(0.3)O_(2)delivered a high delithiation capacity of 437 mAh·g^(-1),around 8%above that of the pristine Li_(2)NiO_(2).Furthermore,a graphite‖LiFePO_(4)pouch cell with a nominal capacity of 3000 mAh demonstrated a notably improved reversible capacity,energy density and cycle life through introducing 2 wt%Li_(2)Ni_(0.7)Cu_(0.3)O_(2)additive,delivering a 6.2 mAh·g^(-1)higher initial discharge capacity and achieving around 5%improvement in capacity retentnion at 0.5P over 1000 cycles.Additionally,the post-mortem analyses testified that the Li_(2)Ni_(0.7)Cu_(0.3)O_(2)additive could suppress solid electrolyte interphase(SEI)decomposition and homogenize the Li distribution,which benefits to stabilizing interface between graphite and electrolyte,and alleviating dendritic Li plating.In conclusion,the Li_(2)Ni_(0.7)Cu_(0.3)O_(2)additive may offer advantages such as lower cost,lower delithiation voltage and higher prelithiation capacity compared with Li_(2)NiO_(2),making it a promising candidate of cathode prelithiation additive for next-generation LIBs.
基金supported by the Beijing Natural Science Foundation(L233004)National Natural Science Foundation of China(62071274 and 22393900)+2 种基金National Key Research and Development Program of China(2021YFB2400300)Shuimu Tsinghua Scholar ProgramTsinghua University Initiative Scientific Research Program.
文摘The demand for high safety and high reliability lithium-ion batteries(LIBs)is strongly considered for practical applications.However,due to their inherent self-discharge properties or abuse,LIBs face the threat of over-discharge,which induces premature end of life and increased risk of thermal runaway.In addition,a strong demand for batteries with zero-volt storage is strongly considered for aerospace and implantable medical devices.In this review,we firstly introduce the necessity and the importance of over-discharge and zero-volt protection for LIBs.The mechanism of damage to the Cu current collectors and SEI induced by potential changes during over-discharge is presented.The current over-discharge protection strategies based on whether the zero-crossing potential of the electrodes is summarized.Finally,the fresh insights into the material design of cathode prelithiation additives are presented from the perspective of over-discharge protection.
基金financially supported by the International Science & Technology Cooperation Program of China under 2019YFE0100200the NSAF (Grant No. U1930113)+2 种基金the Beijing Natural Science Foundation (Grant No. L182022)the 13th Five-Year Plan of Advance Research and Sharing Techniques by the Equipment Department (41421040202)the SAST (2018-114).
文摘The ever-increasing environmental/energy crisis as well as the rapid upgrading of mobile devices had stimulated intensive research attention on promising alternative energy storage and conversion devices.Among these devices,alkali metal ion batteries,such as lithium-ion batteries(LIBs) had attracted increasing research attention due to its several advantages including,environmental friendliness,high power density,long cycle life and excellent reversibility.It had been widely used in consumer electronics,electric vehicles,and large power grids et ac.Silicon-based(silicon and their oxides,carbides) anodes had been widely studied.Its several advantages including low cost,high theoretical capacity,natural abundance,and environmental friendliness,which shows great potential as anodes of LIBs.In this review,we summarized the recently progress in the synthetic method of silicon matrix composites.The empirical method for prelithiation of silicon-based materials were also provided.Further,we also reviewed some novel characterization methods.Finally,the new design,preparation methods and properties of these nano materials were reviewed and compared.We hoped that this review can provide a general overview of recent progress and we briefly highlighted the current challenges and prospects,and will clarify the future trend of silicon anode LIBs research.
基金supported by the National Natural Science Foundation of China (21875107, U1802256, and 22209204)Leading Edge Technology of Jiangsu Province (BK20220009), the Natural Science Foundation of Jiangsu Province (BK20221140)+2 种基金the China Postdoctoral Science Foundation (2022M713364)Jiangsu Specially Appointed Professors ProgramPriority Academic Program Development of Jiangsu Higher Education Institutions (PAPD)。
文摘The solvation structure of Li^(+) in chemical prelithiation reagent plays a key role in improving the low initial Coulombic efficiency(ICE) and poor cycle performance of silicon-based materials. Never theless, the chemical prelithiation agent is difficult to dope active Li^(+) in silicon-based anodes because of their low working voltage and sluggish Li^(+) diffusion rate. By selecting the lithium–arene complex reagent with 4-methylbiphenyl as an anion ligand and 2-methyltetrahydrofuran as a solvent, the as-prepared micro-sized Si O/C anode can achieve an ICE of nearly 100%. Interestingly, the best prelithium efficiency does not correspond to the lowest redox half-potential(E_(1/2)), and the prelithiation efficiency is determined by the specific influencing factors(E_(1/2), Li^(+) concentration, desolvation energy, and ion diffusion path). In addition, molecular dynamics simulations demonstrate that the ideal prelithiation efficiency can be achieved by choosing appropriate anion ligand and solvent to regulate the solvation structure of Li^(+). Furthermore, the positive effect of prelithiation on cycle performance has been verified by using an in-situ electrochemical dilatometry and solid electrolyte interphase film characterizations.
基金National Natural Science Foundation of China,Grant/Award Numbers:22179045,5202780089。
文摘Prelithiation technology is widely considered a feasible route to raise the energy density and elongate the cycle life of lithium-ion batteries.The principle of prelithiation is to introduce extra active Li ions in the battery so that the lithium loss during the first charge and long-term cycling can be compensated.Such an effect does not need to change the major electrode material or battery structure and is compatible with the majority of current lithium-ion battery production lines.At this stage,various prelithiation methods have been reported,some of which are already in the pilot-scale production stage.But there is still no definitive development roadmap for prelithiation.In this review,we first introduce the influence of prelithiation on electrochemical performance from a theoretical point of view and then compare the pros and cons of different prelithiation methods in different battery manufacturing stages.Finally,we discuss the challenges and future development trends of prelithiation.We aim to build up a bridge between academic research and industrial application.Some engineering problems in the promotion of prelithiation technique are extensively discussed,including not only the implementation of prelithiation but also some collateral issues on battery designing and management.
基金This work was supported by Guangdong Basic and Applied Basic Research Foundation(2019A1515110530,2022A1515010486)Shenzhen Science and Technology Program(JCYJ20210324140804013)Tsinghua Shenzhen International Graduate School(QD2021005N,JC2021007).
文摘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.
基金financially supported by the National Natural Science Foundation of China(Nos.U1802256,21975283,21773118 and 21875107)the Key Research and Development Program in Jiangsu Province(No.BE2018122)+1 种基金the general research Project of Jiangsu Key Laboratory of Coal-based Greenhouse Gas Control and Utilization(No.2022KF03)the Fundamental Research Funds for the Central Universities(No.2022QN1088)。
文摘Lithium-ion capacitors(LICs),consisting of a capacitor-type material and a battery-type material together with organic electrolytes,are the state-of-the-art electrochemical energy storage devices compared with supercapacitors and batteries.Owing to their unique characteristics,LICs received a lot of attentions,and great progresses have been achieved,especially in the exploration of cathode and anode materials.Prelithiation techniques are regarded as indispensable procedures for LICs systems,which can compensate for the initial irreversible capacity loss,increase the Li^(+)concentration in the electrolyte,raise the working voltage and resolve the safety and cycle stability issues;however,its research progress is slow,and there is not enough attention until now.In this overview,we look into the ongoing processes on the recent development of prelithiation technologies,especially in organic electrolyte consumption-type LICs.In particular,some prelithiation strategies for LICs are summarized and discussed in detail,including the ex situ electrochemical method,in situ electrochemical method,and cathode prelithiation additives method.Moreover,we propose some unresolved challenges and prospects for prelithiation technologies from the basic research ideas and future key research directions.This work aims to bring up new insights to reassess the significance of premetallation strategies for advanced hybrid-ion capacitors based on the currently proposed prelithiation strategies.
基金supported by the National Natural Science Foundation of China (51974370)the Program of Huxiang Young Talents (2019RS2002)the Innovation and Entrepreneurship Project of Hunan Province, China (Grant No.2018GK5026)。
文摘Lithium ion capacitors(LICs)have been widely used as energy storage devices due to their high energy density and high power density.For LICs,pre-lithiation of negative electrode is necessary.In this work,we employ a bifunctional Li6CoO4(LCO)as cathodic pre-lithiation reagent to improve the electrochemical performance of LICs.The synthesized LCO exhibited high first charge specific capacity of 721 mAh g-1and extremely low initial coulombic efficiency of 3.19%,providing sufficient Li+ for the pre-lithiation of negative electrode in the first charge.Simultaneously,Li6–xCoOy is generated from LCO during the first charge process,which exhibits pseudocapacitive property and contributes to capacity in form of surface capacitance during subsequent cycles,increasing the capacity of capacitive positive electrode.With the appropriate amounts of addition to the positive side in LICs,this bifunctional prelithiation reagent LCO shows significantly improved the electrochemical performance with the energy density of 78.5 Wh kg-1after 300 cycles between 2.0 and 4.2 V at 250 mA g-1.
基金Soft Science Research Project of Guangdong Province,Grant/Award Number:2017B030301013Shenzhen Science and Technology Research Grant,Grant/Award Number:JCYJ20200109140416788。
文摘With the increasing market demand for high-performance lithium-ion batteries with high-capacity electrode materials,reducing the irreversible capacity loss in the initial cycle and compensating for the active lithium loss during the cycling process are critical challenges.In recent years,various prelithiation strategies have been developed to overcome these issues.Since these approaches are carried out under a wide range of conditions,it is essential to evaluate their suitability for large-scale commercial applications.In this review,these strategies are categorized based on different battery assembling stages that they are implemented in,including active material synthesis,the slurry mixing process,electrode pretreatment,and battery fabrication.Furthermore,their advantages and disadvantages in commercial production are discussed from the perspective of thermodynamics and kinetics.This review aims to provide guidance for the future development of prelithiation strategies toward commercialization,which will potentially promote the practical application of next-generation high-energy-density lithium-ion batteries.
基金funded by the National Natural Science Foundation of China(No.U21A20170(X.He))the Ministry of Science and Technology of China(No.2019YFE0100200(X.He)and 2019YFA0705703(L.Wang))the Tsinghua University Initiative Scientific Research Program(No.2019Z02UTY06(X.He)and 2019THFS0132(L.Wang)).The authors also thank Joint Work Plan for Research Projects under the Clean Vehicles Consortium at U.S.and China-Clean Energy Research Center(CERC-CVC2.0,2016-2020)
文摘During the last decade,the rapid development of lithium-ion battery(LIB)energy storage systems has provided significant support for the efficient operation of renewable energy stations.In the coming years,the service life demand of energy storage systems will be further increased to 30 years from the current 20 years on the basis of the equivalent service life of renewable energy stations.However,the life of the present LIB is far from meeting such high demand.Therefore,research on the next-generation LIB with ultra-long service life is imminent.Prelithiation technology has been widely studied as an important means to compensate for the initial coulombic efficiency loss and improve the service life of LIBs.This review systematically summarized the different prelithiation methods from anode and cathode electrodes.Moreover,the large-scale industrialization challenge and the possibility of the existing prelithiation technology are analyzed,based on three key parameters:industry compatibility,prelithiation efficiency,and energy density.Finally,the future trends of improvement in LIB performance by other overlithiated cathode materials are presented,which gives a reference for subsequent research.
基金financially supported by the National Natural Science Foundation of China(Nos.51972198 and 62133007)the Natural Science Foundation of Shandong Province(ZR2020JQ19)the Taishan Scholars Program of Shandong Province(Nos.tsqn201812002 and ts20190908)。
文摘Silicon monoxide(SiO)is regarded as a potential candidate for anode materials of lithium-ion batteries(LIBs).Unfortunately,the application of SiO is limited by poor initial Coulombic efficiency(ICE)and unsteady solid electrolyte interface(SEI),which induce low energy,short cycling life,and poor rate properties.To address these drawbacks of SiO,we achieve in-situ construction of robust and fast-ion conducting F,N-rich SEI layer on prelithiated micro-sized SiO(P-μSiO)via the simple and continuous treatment ofμSiO in mild lithium 4,4′-dimethylbiphenyl solution and nonflammable hexafluorocyclotriphosphazene solution.Chemical prelithiation eliminates irreversible capacity through pre-forming inactive lithium silicates.Meanwhile,the symbiotic F,N-rich SEI with good mechanical stability and fast Li^(+)permeability is conductive to relieve volume expansion ofμSiO and boost the Li+diffusion kinetics.Consequently,the P-μSiO realizes an impressive electrochemical performance with an elevated ICE of 99.57%and a capacity retention of 90.67%after 350 cycles.Additionally,the full cell with P-μSiO anode and commercial LiFePO_(4) cathode displays an ICE of 92.03%and a high reversible capacity of 144.97 mA h g^(-1).This work offers a general construction strategy of robust and ionically conductive SEI for advanced LIBs.
基金National Natural Science Foundation of China,Grant/Award Number:22179006Natural Science Foundation of Zhejiang Province,Grant/Award Number:LQ23E020002+4 种基金National Natural Science Foundation of China,Grant/Award Numbers:52202284,52072036Cooperation between Industry and Education Project of Ministry of Education,Grant/Award Number:220601318235513WenZhou Natural Science Foundation,Grant/Award Numbers:G20220019,G20220021State Key Laboratory of Electrical Insulation and Power Equipment,Xi'an Jiaotong University,Grant/Award Number:EIPE22208Key Research and Development Program of Henan province,China,Grant/Award Number:231111242500。
文摘The commercialization of silicon-based anodes is affected by their low initial Coulombic efficiency(ICE)and capacity decay,which are attributed to the formation of an unstable solid electrolyte interface(SEI)layer.Herein,a feasible and cost-effective prelithiation method under a localized highconcentration electrolyte system(LHCE)for the silicon-silica/graphite(Si-SiO_(2)/C@G)anode is designed for stabilizing the SEI layer and enhancing the ICE.The thin SiO_(2)/C layers with-NH_(2) groups covered on nano-Si surfaces are demonstrated to be beneficial to the prelithiation process by density functional theory calculations and electrochemical performance.The SEI formed under LHCE is proven to be rich in ionic conductivity,inorganic substances,and flexible organic products.Thus,faster Li+transportation across the SEI further enhances the prelithiation effect and the rate performance of Si-SiO_(2)/C@G anodes.LHCE also leads to uniform decomposition and high stability of the SEI with abundant organic components.As a result,the prepared anode shows a high reversible specific capacity of 937.5 mAh g^(-1)after 400 cycles at a current density of 1 C.NCM 811‖Li-SSGLHCE full cell achieves a high-capacity retention of 126.15 mAh g^(-1)at 1 C over 750 cycles with 84.82%ICE,indicating the great value of this strategy for Si-based anodes in large-scale applications.
基金the National Natural Science Foundation of China(Nos.12072183,11872236 and 12172205)。
文摘Prelithiation has been intensively investigated in high-capacity lithiumion batteries(LIBs).However,the optimization of prelithiation degrees for long service life of LIBs still remains a challenge.The positive effect of prelithiation on suppressing degradation of LIBs,besides directly pursuing the high first Coulomb efficiency which has been widely reported in the literature,is revealed and discussed based on an analytical model focusing on the interfacial delamination in electrodes.For full charge-discharge cycling,well-designed prelithiation can effectively suppress the delamination and reduce the debonding size by approximately 25%,compared with the case without prelithiation.For the strategy combining partial charge-discharge cycling and prelithiation,the largest reversible capacity without debonding can be significantly improved by approximately100%with well-designed prelithiation.This work is expected to provide a prelithiation design principle and further improve the mechanical stability of LIB electrodes.
基金support from the National Natural Science Foundation of China(Nos.92472119,52222311,and 22279070)the Natural Science Foundation of Shanghai(No.24ZR1451200)Development Fund for Schools of ShanghaiTech University.The microscopy experiments were supported by the Center for High-resolution Electron Microscopy(CћEM)at ShanghaiTech University.
文摘Silicon oxide(SiO_(x))anodes have emerged as a promising substitute for graphite anodes owing to their high specific capacity and cost-effectiveness.However,they face challenges including significant volume expansion-induced electrode cracking and unsatisfactory initial Coulombic efficiency.Herein,we use a prelithiation strategy to address these challenges for quasi-solid-state batteries using a garnet-type solid electrolyte.Using a contact-based prelithiation configuration,full prelithiation of SiO_(x) anodes were achieved through spontaneous lithium-ion intercalation assisted by molten salts.The garnet-type solid electrolyte based full cells are assembled with fully prelithiated SiO_(x) anodes and LiFePO_(4) cathode using molten salts as interface layer.The quasi-solid-state full cells with high initial coulombic efficiency maintain exceptional cycling stability with over 80%capacity retention after 300 cycles.The molten salt modulates the solid electrolyte interphase composition for SiO_(x) anodes and effectively suppressing SiO_(x) particle fracture during cycling.This work offers a practical route toward highenergy-density lithium batteries for next-generation energy storage.
基金supported by the National Key R&D Program of China(No.2022YFA1504100)the Anhui Provincial Major Science and Technology Project(No.202203a05020017)+4 种基金the National Natural Science Foundation of China(Nos.52222210,51925207,U1910210,52161145101,51972067,51902062,and 52002083)the“Transformational Technologies for Clean Energy and Demonstration”Strategic Priority Research Program of Chinese Academy of Sciences(No.XDA21000000)the National Synchrotron Radiation Laboratory(No.KY2060000173)the Joint Fund of the Yulin University and the Dalian National Laboratory for Clean Energy(No.YLU-DNL Fund 2021002)the Fundamental Research Funds for the Central Universities(No.WK2060140026)。
文摘Silicon possesses a high theoretical capacity,making it a potential contender for lithium-ion battery(LIB)anodes.Nonetheless,its practical usage is challenged by low electrical conductivity and significant volume expansion during cycling.Here,we synthesized a novel silicon/carbon(Si/C)anode doped with ZnO via a template-derived method and high-temperature carbonization.The carbon structure,originated from metal-organic frameworks(MOFs)and ZnO doping,substantially enhanced the electrochemical properties of the composite material.It exhibited an initial capacity of 2100.3 mA h g^(-1)at a current density of 0.2 A g^(-1)and demonstrated excellent capacity retention over successive cycles.Moreover,the composite material displayed superior rate performance at higher current densities of 2 A g^(-1)and 3 A g^(-1).To address the low initial Coulombic efficiency(ICE)of siliconbased materials,we adopted a direct contact prelithiation approach and optimized the lithiation process by controlling the prelithiation time.After 30 min of prelithiation,the ICE reached 97.9%,thereby reducing the initial irreversible capacity loss(ICL)and realizing stable discharge-charge in subsequent cycles.This rational design provides valuable insights for achieving high-performance silicon anode.
基金National Natural Science Foundation of China,Grant/Award Number:22002045Guangdong Basic and Applied Basic Research Foundation,Grant/Award Number:2023A1515030164+1 种基金Special Topics in Key Areas for Universities in Guangdong Province,Grant/Award Number:2023ZDZX3001Hong Kong Scholars Program 2022,Grant/Award Numbers:G-YZ5Y,XJ2022026。
文摘Lithium-ion batteries are widely used in portable electronics and electric vehicles due to their high energy density,stable cycle life,and low self-discharge.However,irreversible lithium loss during the formation of the solid electrolyte interface greatly impairs energy density and cyclability.To compensate for the lithium loss,introducing an external lithium source,that is,a prelithiation agent,is an effective strategy to solve the above problems.Compared with other prelithiation strategies,cathode prelithiation is more cost-effective with simpler operation.Among various cathode prelithiation agents,we first systematically summarize the recent progress of Li_(2)S-based prelithiation agents,and then propose some novel strategies to tackle the current challenges.This review provides a comprehensive understanding of Li_(2)S-based prelithiation agents and new research directions in the future.
基金support by the National Natural Science Foundation of China(Nos.21701163,21831006,21975244,21521001,and 22075268)the Natural Science Foundation of Anhui Provincial(No.1808085QB25)。
文摘The low initial Coulombic efficiency(ICE)of SiOx anode caused by the irreversible generation of LiySiOz and Li20 during lithiation process limits its application for high energy-density lithium-ion batteries.Herein,we report a molten-salt-induced thermochemical.prelithiation strategy for regulating the electrochemically active Si/O ratio of SiOx and thus enhancing ICE through thermal treatment of pre-synthesized LiNH2-coated SiOx in molten LiCl at 700℃.Bulk SiOx micro-particle was transformed into pomegranatelike prelithiated micro-cluster composite(M-Li-SiOx)with SiOx core and outer nano-sized agglomerates consisting of Li2Si20s,SiO2,and Si.Through the analysis of the reaction intermediates,molten-UC!could initiate reactions and promote mass transfer by the continuous extraction of oxygen component from SiOx particle inner in the form of inert Li2Si20s and SiO2 nanotubes to realize the.prelithiation.The degree of prelithiation can be regulated by adjusting the coating amount of LiNH2 layer,and the resulted M-Li-SiOx displays a prominent improvement of ICE from 58.73%to 88.2%.The graphite/M-Li-SiOx(8:2)composite electrode delivers a.discharge capacity of 497.29 mAh·g^(-1) with an ICE of 91.79%.By pairing graphite/M-Li-SiOx anode and LiFeP04 cathode in a full-cell an enhancement of energy density of 37.25%is realized compared with the full-cell containing graphite/SiOx anode.Furthermore,,ex-situ X-ray photoelectron spectroscopy(XPS)/Raman/X-ray diffraction(XRD)and related electrochemical measurements reveal the SiOx core and Si of M-Li-SiOx participate in the lithiation,and pre-generated Li2Si20s with u+diffusivity and pomegranate-like.structure reduces the reaction resistance and interface impedance of the solid electrolyte interphase(SEI)film.
基金supported by the National Key Research and Development Program of China(2017YFA0206703)the National Natural Science Foundation of China(21701163,21671181,21831006,22075268)Ningbo Veken Battery Co.,Ltd.(2018B10043)。
文摘Chemical prelithiation is regarded as a crucial method for improving the initial Coulombic efficiency(ICE)of Li-storage anodes.Herein,a substituent-engineered Li-cyanonaphthalene chemical prelithiation system is designed to simultaneously enhance the ICE and construct a multifunctional interfacial film for SiO electrodes.X-ray photoelectron spectroscopy(XPS),electron energy-loss spectroscopy(EELS),nuclear magnetic resonance(NMR)spectroscopy and atomic force microscopy(AFM)prove that the Licyanonaphthalene prelithiation reagent facilitates the formation of a rectified solid electrolyte interface(SEI)film in two ways:(1)generation of a gradient SEI film with an organic outer layer(dense Ncontaining organics,ROCO_(2)Li)and an inorganic LiF-enriched inner layer;(2)homogenization of the horizontal distribution of the composition,mechanical properties and surface potential.As a result,the prelithiated SiO electrode exhibits an ICE above 100%,enhanced CEs during cycling,better cycle stability and inhibition of lithium dendrite formation in the overcharged state.Notably,the prelithiated hard carbon/SiO(9:1)‖LHCoO_(2) cell displays an enhancement in the energy density of 62.3%.
基金supported by the National Natural Science Foundation of China(No.22279022)the Joint Funds of the National Natural Science Foundation of China(No.U20A20336)the Tianmu Lake Institute of Advanced Energy Storage Technologies Scientist Studio Program(No.TIESSS0002).
文摘In order to address the issues of low initial Coulombic efficiency of SiO_(x)-C composite anode due to the formation of solid electrolyte interphase,irreversible conversion reaction,and large volume change,the prelithiation method using metal lithium has been employed as one of effective solutions.However,violent side reactions with liquid electrolyte for prelithiation lead to low prelithiation efficiency and induce poor interface between the SiO_(x)-C electrode and liquid electrolyte.Here,a new prelithiation method with so called solid-state corrosion of lithium is developed.By replacing liquid electrolyte with solid-state electrolyte of carbon-incorporated lithium phosphorus oxynitride(LiCPON),not only various side reactions associated with metal lithium are avoided,but also the perfect interface is achieved from the decomposition products of LiCPON.The successful implementation of solid-state corrosion prelithiation can be confirmed by changes in optical image,scanning electron microscopy,and X-ray diffraction.Compared with pristine electrode,the initial Coulombic efficiency of the prelithiated electrode using solid electrolyte can be increased by about 10%,reaching 98.6%in half cell and 88.9%in full cell.Compared with prelithiated electrode using liquid electrolyte,the prelithiation efficiency of the prelithiated anode with solid-state corrosion can be increased from 25.7%to 82.8%.Solid-state corrosion of lithium is expected to become a useful method for prelithiation of SiO_(x)-C composite electrode with high initial Coulombic efficiency and large prelithiation efficiency.
基金supported by projects from the National Natural Science Foundation of China(No.U20A20145)State Key Laboratory of Polymer Materials Engineering(No.sklpme2020-3-02)+6 种基金Sichuan Provincial Department of Science and Technology(No.2020YFG0022,No.2022YFG0124)Dazhou Department of Science and Technology(No.21ZDYF0001)Guangyuan Department of Science and Technology(No.22ZDYF0047)Sichuan Province Science and Technology Achievement Transfer and Transformation Project(No.21ZHSF0111)2020 Strategic Cooperation Project between Sichuan University and Suining Municipal People's Government Government(No.20221500008704170)the Open Project of State Key Laboratory of Environment-friendly Energy.Materials(No.20KFHG07)Start-up funding of Chemistry and Chemical Engineering Guangdong Laboratory(No.2122010).
文摘Chemical prelithiation is widely proven to be an effective strategy to address the low initial coulombic efficiency(ICE)of promising SiO_(x) anode.Though the reagent composition has been widely explored,the Li^(+) solvation structure,which practically plays the cornerstone role in the prelithiation ability,rate,uniformility,has rarely been explored.A novel environmentally-friendly reagent with weak solvent cyclopentyl methyl ether(CPME)is proposed that enables both improved ICE and spatial homogeneous solid electrolyte interphase(SEl).And the prelithiation behavior and mechanism were explored focused on the Li^(+) solvation structure.Both theoretical investigation and spectroscopic results suggest that weak solvent feature of CPME reduces the solvent coordination number and decreases the Li^(+) desolvation energy.
