Pre-lithiation methods address the challenges of low initial coulombic efficiency(ICE)and reduced energy density in lithium-ion batteries(LIBs)by adding additional lithium sources to compensate for initial irreversibl...Pre-lithiation methods address the challenges of low initial coulombic efficiency(ICE)and reduced energy density in lithium-ion batteries(LIBs)by adding additional lithium sources to compensate for initial irreversible Li+losses.The direct contact pre-lithiation(DC-Pr)method has garnered extensive attention due to its simplicity,convenience as well as significant effects on the improved cycling durability.Considering the most important factors,i.e.,effectiveness and uniformity,this review focuses on the anode DC-Pr method for LIBs with the lithium sources from Li foil,stabilized lithium metal powder(SLMP),lithium-rich alloys,and physical vapor deposition of lithium metal.After summarizations and discussions,the review overviews the challenges and prospects for DC-Pr methods,aiming to provide guidance for the construction and developments of practical LIBs.展开更多
Considering the growing pre-lithiation demand for high-performance Si-based anodes and consequent additional costs caused by the strict pre-lithiation environment,developing effective and environmentally stable pre-li...Considering the growing pre-lithiation demand for high-performance Si-based anodes and consequent additional costs caused by the strict pre-lithiation environment,developing effective and environmentally stable pre-lithiation additives is a challenging research hotspot.Herein,interfacial engineered multifunctional Li_(13)Si_(4)@perfluoropolyether(PFPE)/LiF micro/nanoparticles are proposed as anode pre-lithiation additives,successfully constructed with the hybrid interface on the surface of Li_(13)Si_(4)through PFPE-induced nucleophilic substitution.The synthesized multifunctional Li_(13)Si_(4)@PFPE/LiF realizes the integration of active Li compensation,long-term chemical structural stability in air,and solid electrolyte interface(SEI)optimization.In particular,the Li_(13)Si_(4)@PFPE/LiF with a high pre-lithiation capacity(1102.4 mAh g^(-1))is employed in the pre-lithiation Si-based anode,which exhibits a superior initial Coulombic efficiency of 102.6%.Additionally,in situ X-ray diffraction/Raman,density functional theory calculation,and finite element analysis jointly illustrate that PFPE-predominant hybrid interface with modulated abundant highly electronegative F atoms distribution reduces the water adsorption energy and oxidation kinetics of Li_(13)Si_(4)@PFPE/LiF,which delivers a high pre-lithiation capacity retention of 84.39%after exposure to extremely moist air(60%relative humidity).Intriguingly,a LiF-rich mechanically stable bilayer SEI is constructed on anodes through a pre-lithiation-driven regulation for the behavior of electrolyte decomposition.Benefitting from pre-lithiation via multifunctional Li_(13)Si_(4)@PFPE/LiF,the full cell and pouch cell assembled with pre-lithiated anodes operate with long-time stability of 86.5%capacity retention over 200 cycles and superior energy density of 549.9 Wh kg^(-1),respectively.The universal multifunctional pre-lithiation additives provide enlightenment on promoting large-scale applications of pre-lithiation on commercial high-energy-density and long-cycle-life lithium-ion batteries.展开更多
Developing single-crystalline Ni-rich cathodes is an effective strategy to improve the safety and cycle life of Li-ion batteries(LIBs).However,the easy-to-loss of Li and O in high-temperature lithiation results in uns...Developing single-crystalline Ni-rich cathodes is an effective strategy to improve the safety and cycle life of Li-ion batteries(LIBs).However,the easy-to-loss of Li and O in high-temperature lithiation results in unsatisfactory ordered layered structure and stoichiometry.Herein,we demonstrate the synthesis of highly-ordered and fully-stoichiometric single-crystalline LiNi_(0.83)Co_(0.12)Mn_(0.05)O_(2)(SC-NCM83)cathodes by the regulation of pre-lithiation kinetics.The well-balanced pre-lithiation kinetics have been proved to greatly improve the proportion of layered phase in the intermediate by inhibiting the formation of metastable spinel phase,which promoted the rapid transformation of the intermediate into highly-ordered layered SC-NCM83 in the subsequent lithiation process.After coating a layer of Li_(2)O–B_(2)O_(3),the resultant cathodes deliver superior cycling stability with 90.9%capacity retention at 1C after 300 cycles in pouch-type full batteries.The enhancement mechanism has also been clarified.These findings exhibit fundamental insights into the pre-lithiation kinetics process for guiding the synthesis of high-quality singlecrystalline Ni-rich cathodes.展开更多
A commentary on pressure-induced pre-lithiation towards Si anodes in allsolid-state Li-ion batteries(ASSLIBs)using sulfide electrolytes(SEs)is presented.First,feasible pre-lithiation technologies for Si anodes in SE-b...A commentary on pressure-induced pre-lithiation towards Si anodes in allsolid-state Li-ion batteries(ASSLIBs)using sulfide electrolytes(SEs)is presented.First,feasible pre-lithiation technologies for Si anodes in SE-based ASSLIBs especially the significant pressure-induced pre-lithiation strategies are briefly reviewed.Then,a recent achievement by Meng et al.in this field is elaborated in detail.Finally,the significance of Meng’s work is discussed.展开更多
Aluminum(Al)exhibits excellent electrical conductivity,mechanical ductility,and good chemical compatibility with high-ionic-conductivity electrolytes.This makes it more suitable as an anode material for all-solid-stat...Aluminum(Al)exhibits excellent electrical conductivity,mechanical ductility,and good chemical compatibility with high-ionic-conductivity electrolytes.This makes it more suitable as an anode material for all-solid-state lithium batteries(ASSLBs)compared to the overly reactive metallic lithium anode and the mechanically weak silicon anode.This study finds that the pre-lithiated Al anode demonstrates outstanding interfacial stability with the Li_6PS_5Cl(LPSCl)electrolyte,maintaining stable cycling for over 1200 h under conditions of deep charge-discharge.This paper combines the pre-lithiated Al anode with a high-nickel cathode,LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2),paired with the highly ionic conductive LPSCl electrolyte,to design an ASSLB with high energy density and stability.Using anode pre-lithiation techniques,along with dual-reinforcement technology between the electrolyte and the cathode active material,the ASSLB achieves stable cycling for 1000 cycles at a 0.2C rate,with a capacity retention rate of up to 82.2%.At a critical negative-to-positive ratio of 1.1,the battery's specific energy reaches up to 375 Wh kg^(-1),and it maintains over 85.9%of its capacity after 100 charge-discharge cycles.This work provides a new approach and an excellent solution for developing low-cost,high-stability all-solid-state batteries.展开更多
Silicon is considered one of the most promising candidates for incorporation into carbon-based anodes in lithium-ion batteries(LIBs)due to its high specific capacity.However,the significant volume changes during charg...Silicon is considered one of the most promising candidates for incorporation into carbon-based anodes in lithium-ion batteries(LIBs)due to its high specific capacity.However,the significant volume changes during charge and discharge cycles lead to repeated reconstruction of the solid electrolyte interface(SEI)film and continuous loss of active lithium.Pre-lithiation method is regarded as a highly attractive approach for effectively compensating for active lithium loss during the charge and discharge cycles of LIBs.Constructing a stable SEI film is particularly crucial in the pre-lithiation process.In this study,we developed a direct contact pre-lithiation(DC-Pr)method to create a temperature-tailored robust SEI film interface on silicon-carbon(Si@C)electrodes.By investigating the morphology,structure,and composition of the SEI formed on Si@C electrodes at different pre-lithiation temperatures(50,25,0,and-25℃),we demonstrated that controlling the lithiation temperature to regulate the migration rate of lithium ions within the Si@C electrode yields a lithiated Si@C anode(25-Pr-Si@C)at 25℃ with a continuous,uniform SEI film(~3.65 nm)enriched with Li_(2)O-LiF,which exhibits synergistic effects.Importantly,the initial Coulombic efficiency(ICE)of 25-Pr-Si@C significantly improved from 85.4% in the unlithiated Si@C electrode(Blank-Si@C)to 106.1%.Additionally,the full cell configuration using a high areal loading of lithiated Si@C(~5.5 mA h cm^(-2))as the anode and NCM811 as the cathode(NCM811||25-Pr-Si@C)demonstrated superior cycling performance,maintaining 69.4% of capacity retention and achieving a Coulombic efficiency of over 99.7% after 150 cycles(0.5 C).Therefore,this simple and efficient experimental design provides a high-performance,controllable,and scalable pre-lithiation method for LIBs,paving the way for the commercialization of LIBs utilizing pre-lithiation techniques.展开更多
Li_(2)NiO_(2)has emerged as a promising cathode pre-lithiation additive capable of substantially enhancing the energy density and cycling durability of next-generation lithium-ion batteries.However,its practical deplo...Li_(2)NiO_(2)has emerged as a promising cathode pre-lithiation additive capable of substantially enhancing the energy density and cycling durability of next-generation lithium-ion batteries.However,its practical deployment is hindered by intrinsic surface structural instability under ambient conditions.Although prior studies have reported residual alkali formation on Li_(2)NiO_(2)surfaces and proposed coating strategies,critical knowledge gaps persist regarding the temporal evolution of alkali byproducts and industrially viable modification approaches.Through multiscale in situ characterizations combining X-ray diffraction(XRD),Raman spectroscopy,and X-ray photoelectron spectroscopy(XPS),we reveal a stratified residual alkali architecture:the inner layer predominantly comprises Li_(2)CO_(3)while the outer layer is dominated by LiOH,despite minimal bulk structural alterations.Leveraging these insights,we developed a facile carbon-coating strategy enabling scalable synthesis of hundred-gram batches.The conformal carbon layer effectively mitigates structural degradation and suppresses alkali formation,facilitating the integration of high-content pre-lithiation additives.LiFePO_(4)||graphite pouch cells incorporating 2.5% modified Li_(2)NiO_(2)demonstrate enhanced specific capacity with exceptional stability—exhibiting negligible energy decay(99.58%retention)over 500 cycles at 0.5P and maintaining 81.15% energy retention under aggressive 4P/4P cycling conditions over 1000 cycles.Remarkably,pouch cells with 8% additive loading achieve zero energy density decay after 1000 cycles at 4P/4P.This work provides a practical and scalable solution for advancing high-energy-density lithium-ion battery technologies.展开更多
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 ...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.展开更多
Similar to lithium-ion batteries(LIBs),during the first charge/discharge process of lithium-ion capacitors(LICs),lithium-intercalated anodes(e.g.,silicon,graphite,and hard carbon)also exhibit irreversible lithium inte...Similar to lithium-ion batteries(LIBs),during the first charge/discharge process of lithium-ion capacitors(LICs),lithium-intercalated anodes(e.g.,silicon,graphite,and hard carbon)also exhibit irreversible lithium intercalation behaviors,such as the formation of a solid electrolyte interface(SEI),which will consume Li^(+)in the electrolyte and significantly reduce the electrochemical performance of the system.Therefore,pre-lithiation is an indispensable procedure for LICs.At present,commercial LICs mostly use lithium metal as the lithium source to compensate for the irreversible capacity loss,which has the demerits of operational complexity and danger.However,the pre-lithiation strategy based on cathode sacrificial lithium salts(CSLSs)has been proposed,which has the advantages of low cost,simple operation,environmental protection,and safety.Therefore,there is an urgent need for a timely and comprehensive summary of the application of CSLSs to LICs.In this review,the important roles of pre-lithiation in LICs are detailed,and different pre-lithiation methods are reviewed and compared systematically and comprehensively.After that,we systematically discuss the pre-lithiation strategies based on CSLSs and mainly introduce the lithium extraction mechanism of CSLSs and the influence of intrinsic characteristics and doping amount of CSLSs on LICs performance.In addition,a summary and outlook are conducted,aiming to provide the essential basic knowledge and guidance for developing a new pre-lithiation technology.展开更多
The development of high-energy-density Li-ion batteries is hindered by the irreversible capacity loss during the initial charge-discharge process.Therefore,pre-lithiation technology has emerged in the past few decades...The development of high-energy-density Li-ion batteries is hindered by the irreversible capacity loss during the initial charge-discharge process.Therefore,pre-lithiation technology has emerged in the past few decades as a powerful method to supplement the undesired lithium loss,thereby maximizing the energy utilization of LIBs and extending their cycle life.Lithium oxalate(Li_(2)C_(2)O_(4)),with a high lithium content and excellent air stability,has been considered one of the most promising materials for lithium compensation.However,the sluggish electrochemical decomposition kinetics of the material severely hinders its further commercial application.Here,we introduce a recrystallization strategy combined with atomic Ni catalysts to modulate the mass transport and decomposition reaction kinetics.The decomposition potential of Li_(2)C_(2)O_(4)is significantly decreased from~4.90V to~4.30V with a high compatibility with the current battery systems.In compared to the bare NCM//Li cell,the Ni/N-rGO and Li_(2)C_(2)O_(4)composite(Ni-LCO)modified cell releases an extra capacity of~11.7%.Moreover,this ratio can be magnified in the NCM//SiOx full cell,resulting in a 30.4%higher reversible capacity.Overall,this work brings the catalytic paradigm into the pre-lithiation technology,which opens another window for the development of high-energy-density battery systems.展开更多
Li_(3)VO_(4)has been a promising insertion anode material for Li-ion batteries,which has high theoretical capacity(up to~600 m Ah g^(-1))and safe Li insertion voltage(0.5–1 V vs.Li/Li^(+)).However,the low initial Cou...Li_(3)VO_(4)has been a promising insertion anode material for Li-ion batteries,which has high theoretical capacity(up to~600 m Ah g^(-1))and safe Li insertion voltage(0.5–1 V vs.Li/Li^(+)).However,the low initial Coulombic efficiency(ICE)has always been the bottleneck limiting its commercialisation.Here,we propose a facile pre-lithiation method to controllably elevate the ICE by the post-treatment of the prepared Li_(3)VO_(4)composite electrode based on an immersion reaction.In this process,the whole electrode was immersed in the liquid Li source,via which the ICE of the Li_(3)VO_(4)electrode can be controllably elevated from 80%to over 100%within 5 min of pre-lithiation.Rather than the traditional powder treatment for pre-lithiation,this process we proposed minimizes the impact of pre-lithiation on the battery assembly process.Moreover,we further investigated the effect of this pre-lithiation process on the functional components in the electrode.For the first time the ICE of Li_(3)VO_(4)electrode was elevated to 100%.As a result,the initial reversible capacity of LiFePO_(4)||Li_(3)VO_(4)full cell was improved from 44.0 to146.3 m Ah g-1,demonstrating the feasibility and great potential of the process.展开更多
Mesoporous carbon（MC） material with high specific surface area（1432 m^2/g）, large pore volume（2.894 cm^3/g） and appropriate mesopore structure（about 6.5 nm） has been prepared. We use the magnesium citrate as t...Mesoporous carbon（MC） material with high specific surface area（1432 m^2/g）, large pore volume（2.894 cm^3/g） and appropriate mesopore structure（about 6.5 nm） has been prepared. We use the magnesium citrate as the precursor of the carbon material and the nano-sized magnesium oxide（MgO）particles as template provided by magnesium citrate. The structure characterization and the electrochemical performance of MC are investigated. Compared with commercial activated carbon（AC） cathode, the utilization of MC cathode can obviously improve the energy density of LIC device. When the MC cathode is coupled with pre-lithiated hard carbon（HC） anode, the LIC device shows the optimal electrochemical performance, high energy density up to 95.4 Wh/kg and power density as high as 7.4 kW/kg（based on active material mass of two electrodes）, excellent capacity retention of 97.3% after 2000 cycles. The present work indicates the combination of MC electrode with HC electrodes as promising candidates for the realization of LIC with high energy density, high power density and long cycle life.展开更多
The poor rate capability and low capacity are huge barriers to realize the commercial applications of battery-type transition metal compounds(TMCs) cathode.Herein,numerous Se vacancy defects are introduced into the Ni...The poor rate capability and low capacity are huge barriers to realize the commercial applications of battery-type transition metal compounds(TMCs) cathode.Herein,numerous Se vacancy defects are introduced into the Ni_(3)Se_(2)lamellas by pre-lithiation technique,which can be acted as a novel class of battery-type cathode for hybrid supercapacitors.Appropriately modulating the contents of the preembedded lithium(Li) ions can induce a controllable vacancy content in the series of as-prepared products,effectively endowing a fast reaction kinetic and high activity for the cathode.Benefiting from the distinct design,the optimized cathode(Li2-Ni_(3)Se_(2)) presents a high specific capacity of 236 mA h g^(-1)at1 A g^(-1),importantly,it can still possess 117 mA h g^(-1)when the current density is increased up to 100A g^(-1),exhibiting relatively high rate capability.It is much superior to other battery-type TMC cathodes reported in previous studies.Moreover,the cathode also shows the excellent cycling stability with 92%capacity retention after 3,000 cycles.In addition,a hybrid supercapacitor(HSC) is assembled with the obtained Li2-Ni_(3)Se_(2)as the cathode and active carbon(AC) as the anode,which delivers a high energy density of 77 W h kg^(-1)at 4 kW kg^(-1)and long-term durability(90% capacitance retention after 10,000 cycles).Therefore,the strategy not only provides an effective way to realize the controllable vacancy content in TMCs for achieving high-perfo rmance cathodes for HSC,but also further promotes their large-scale applications in the energy storage fields.展开更多
Silicon anodes are considered to be the most promising alternatives owing to their theoretical specific capacity,which is almost 10 times higher than that of graphite anodes.However,huge volume changes during charging...Silicon anodes are considered to be the most promising alternatives owing to their theoretical specific capacity,which is almost 10 times higher than that of graphite anodes.However,huge volume changes during charging and discharging affect their interface stability,which strongly limits their application in commercial batteries.Herein,a popcorn-structured silicon-carbon composite(SiNPs@graphene@C),composed of silicon nanoparticles(SiNPs),graphene spheres and pitch-based carbon,is prepared by spraydrying followed by a wet process.The resulting SiNPs@graphene@C composite has good flexibility and elastic-strain capacity due to the graphene substrate,and it possesses macrostructural integrity and mechanical stability during cycling due to the rigid carbon–carbon chemical bonds.As a result,it shows a discharge-specific capacity of 481.3 mAh g^(-1)and a capacity retention of 82.9%after 500 cycles at 1 A g^(-1).Besides,the initial coulomb efficiency is increased from 65.7%to 86.5%by pre-lithiation,which improves the feasibility of commercialising the SiNPs@graphene@C composite.展开更多
Li_(2)C_(2)O_(4),with a high theoretical capacity of 525 mAh·g^(−1)and good air stability,is regarded as a more attractive cathode prelithiation additive in contrast to the reported typical inorganic pre-lithiati...Li_(2)C_(2)O_(4),with a high theoretical capacity of 525 mAh·g^(−1)and good air stability,is regarded as a more attractive cathode prelithiation additive in contrast to the reported typical inorganic pre-lithiation compounds which are quite air sensitive.However,its obtained capacity is much lower than the theoretical value and its delithiation potential(>4.7 V)is too high to match with the most commercial cathode materials,which greatly impedes its practical application.Herein,we greatly improve the pre-lithiation performance of Li_(2)C_(2)O_(4)as cathode additive with fulfilled capacity at a much-reduced delithiation voltage,enabling its wide applicability for typical commercial cathodes.We increase the capacity of Li_(2)C_(2)O_(4)from 436 to 525 mAh·g^(−1)by reducing its particle size.Through optimizing the types of conductive additives,introducing nano-morphological NiO,MnO2,etc.as catalysts,and innovatively designing a bilayer electrode,the delithiation potential of Li_(2)C_(2)O_(4)is successfully reduced from 4.778 to 4.288 V.We systematically study different particle size,conductive additives,and catalysts on the delithiation behavior of Li_(2)C_(2)O_(4).Finally,it is applied to pre-lithiate the hard carbon anode,and it is found that Li_(2)C_(2)O_(4)could effectively increase the capacity of the full cell from 79.0 to 140.0 mAh·g^(−1)in the first cycle.In conclusion,our study proves that improving the reactivity is an effective strategy to boost the pre-lithiation of Li_(2)C_(2)O_(4).展开更多
Li3N is an excellent zero-residue positive electrode pre-lithiation additive to offset the initial lithium loss in lithium-ion capacitors. However, Li3N has an intrinsic problem of poor compatibility with commonly use...Li3N is an excellent zero-residue positive electrode pre-lithiation additive to offset the initial lithium loss in lithium-ion capacitors. However, Li3N has an intrinsic problem of poor compatibility with commonly used aprotic polar solvents in electrode manufacture procedure due to its high reactivity with commonly used solvents like N-methy-2-pyrrolidone(NMP) and etc. It is the Valley of Death between research and large-scale commercialization of Li-ion capacitors using Li3N as prelithiation agent. In this work, Li3N containing electrode is prepared by a commercially adoptable route for the first time, using N,Ndimethylformamide(DMF) to homogenate the electrode slurry. The DMF molecular stabilizing mechanism is confirmed via experiment analysis and DFT simulation, indicating that the dehydrogenation energy for DMF is obviously larger than other commonly used solvents such as NMP and etc. The soft package lithium-ion capacitors(LIC250) with only 12 wt% Li3N addition in AC positive electrode exhibits excellent rate capability, cyclic stability and ultrahigh specific energy. Its specific energy is 2.3 times higher than the Li3N-free devices, with energy retention as high as 90% after 10,000 cycles.展开更多
Due to the high reactivity between the lithium metal and traditional organic liquid electrolyte,the reaction of lithium metal electrode is usually uneven and there are also unexpected side reactions.Therefore,construc...Due to the high reactivity between the lithium metal and traditional organic liquid electrolyte,the reaction of lithium metal electrode is usually uneven and there are also unexpected side reactions.Therefore,construction of a stable solid electrolyte interface(SEI)is highly essential to improve the performance of lithium metal anode.Herein,a sandwich-like gel polymer electrolyte(GPE)is accurately prepared by in-situ polymerization of Polyacrylonitrile(PAN)nanofiber membrane with trihydroxymethylpropyl trimethylacrylate(TMPTMA)and 1,6-hexanediol diacrylate(HDDA).The resulting GPE with a tightly cross-linked gel skeleton exhibits high ionic conductivity and electrochemical window of 5.6 V versus Li/Li^(+).In particular,the pretreatment of Li metal anode can improve the interfacial wettability,and the synergy of the chemically pretreated Li metal anode surface and the GPE can electrochemically in situ generate SEI with compositionally stable and fluorine-rich inorganic components.Owing to these unique advantages,the interfacial compatibility between the GPE and lithium metal is greatly improved.Meanwhile,the formed SEI can inhibit the formation of lithium dendrites,and decomposition of GPE would be alleviated.The assembled Li-FEC|GPE|LiFePO_(4) full cell shows a high initial discharge capacity of 157.1 mA h g^(-1),and maintains a capacity retention of 92.3%after 100 cycles at 0.2C.展开更多
基金sponsored by the financial support from Shanghai Oriental Talent ProgramOn-campus Scene Verification Project of Tongji University(kh0170020242359)+4 种基金Shanghai Research Institute of China Shenhua Coal-to-Liquids Chemical Co.,LtdNational Natural Science Foundation of China(52307249)the National Science Foundation of Shanghai Province(23ZR1465900)the Fundamental Research Funds for the Central Universities at Tongji University(PA2022000668,22120220426)the Nanchang Automotive Institute of Intelligence&New Energy of Tongji University(TPD-TC202211-02,20212CCH_(4)5004)。
文摘Pre-lithiation methods address the challenges of low initial coulombic efficiency(ICE)and reduced energy density in lithium-ion batteries(LIBs)by adding additional lithium sources to compensate for initial irreversible Li+losses.The direct contact pre-lithiation(DC-Pr)method has garnered extensive attention due to its simplicity,convenience as well as significant effects on the improved cycling durability.Considering the most important factors,i.e.,effectiveness and uniformity,this review focuses on the anode DC-Pr method for LIBs with the lithium sources from Li foil,stabilized lithium metal powder(SLMP),lithium-rich alloys,and physical vapor deposition of lithium metal.After summarizations and discussions,the review overviews the challenges and prospects for DC-Pr methods,aiming to provide guidance for the construction and developments of practical LIBs.
基金Huaiyu Shao acknowledges the Shenzhen-Hong Kong-Macao Science and Technology Plan Project(Category C)(Grant No.SGDX20220530111004028)the Macao Science and Technology Development Fund(FDCT)for funding(FDCT No.0013/2024/RIB1,FDCT-MOST joint project No.0026/2022/AMJ and No.006/2022/ALC of the Macao Centre for Research and Development in Advanced Materials[2022–2024])+2 种基金the Multi-Year Research Grant(MYRG)from University of Macao(project No.MYRG-GRG2023-00140-IAPME-UMDF and No.MYRG-GRG2024-00206-IAPME)Natural Science Foundation of Guangdong Province(Grant No.2023A1515010765)Science and Technology Program of Guangdong Province of China(Grant No.2023A0505030001)。
文摘Considering the growing pre-lithiation demand for high-performance Si-based anodes and consequent additional costs caused by the strict pre-lithiation environment,developing effective and environmentally stable pre-lithiation additives is a challenging research hotspot.Herein,interfacial engineered multifunctional Li_(13)Si_(4)@perfluoropolyether(PFPE)/LiF micro/nanoparticles are proposed as anode pre-lithiation additives,successfully constructed with the hybrid interface on the surface of Li_(13)Si_(4)through PFPE-induced nucleophilic substitution.The synthesized multifunctional Li_(13)Si_(4)@PFPE/LiF realizes the integration of active Li compensation,long-term chemical structural stability in air,and solid electrolyte interface(SEI)optimization.In particular,the Li_(13)Si_(4)@PFPE/LiF with a high pre-lithiation capacity(1102.4 mAh g^(-1))is employed in the pre-lithiation Si-based anode,which exhibits a superior initial Coulombic efficiency of 102.6%.Additionally,in situ X-ray diffraction/Raman,density functional theory calculation,and finite element analysis jointly illustrate that PFPE-predominant hybrid interface with modulated abundant highly electronegative F atoms distribution reduces the water adsorption energy and oxidation kinetics of Li_(13)Si_(4)@PFPE/LiF,which delivers a high pre-lithiation capacity retention of 84.39%after exposure to extremely moist air(60%relative humidity).Intriguingly,a LiF-rich mechanically stable bilayer SEI is constructed on anodes through a pre-lithiation-driven regulation for the behavior of electrolyte decomposition.Benefitting from pre-lithiation via multifunctional Li_(13)Si_(4)@PFPE/LiF,the full cell and pouch cell assembled with pre-lithiated anodes operate with long-time stability of 86.5%capacity retention over 200 cycles and superior energy density of 549.9 Wh kg^(-1),respectively.The universal multifunctional pre-lithiation additives provide enlightenment on promoting large-scale applications of pre-lithiation on commercial high-energy-density and long-cycle-life lithium-ion batteries.
基金supported by the National Natural Science Foundation of China(21975074,91834301)the Innovation Program of Shanghai Municipal Education Commissionthe Fundamental Research Funds for the Central Universities.
文摘Developing single-crystalline Ni-rich cathodes is an effective strategy to improve the safety and cycle life of Li-ion batteries(LIBs).However,the easy-to-loss of Li and O in high-temperature lithiation results in unsatisfactory ordered layered structure and stoichiometry.Herein,we demonstrate the synthesis of highly-ordered and fully-stoichiometric single-crystalline LiNi_(0.83)Co_(0.12)Mn_(0.05)O_(2)(SC-NCM83)cathodes by the regulation of pre-lithiation kinetics.The well-balanced pre-lithiation kinetics have been proved to greatly improve the proportion of layered phase in the intermediate by inhibiting the formation of metastable spinel phase,which promoted the rapid transformation of the intermediate into highly-ordered layered SC-NCM83 in the subsequent lithiation process.After coating a layer of Li_(2)O–B_(2)O_(3),the resultant cathodes deliver superior cycling stability with 90.9%capacity retention at 1C after 300 cycles in pouch-type full batteries.The enhancement mechanism has also been clarified.These findings exhibit fundamental insights into the pre-lithiation kinetics process for guiding the synthesis of high-quality singlecrystalline Ni-rich cathodes.
基金supported by grants from the National Natural Science Foundation of China(Grant Nos.52072136,52272201,52172229,51972257)Yanchang Petroleum-WHUT Joint Program(yc-whlg-2022ky-05)Fundamental Research Funds for the Central Universities(104972024RSCrc0006)for financial support.
文摘A commentary on pressure-induced pre-lithiation towards Si anodes in allsolid-state Li-ion batteries(ASSLIBs)using sulfide electrolytes(SEs)is presented.First,feasible pre-lithiation technologies for Si anodes in SE-based ASSLIBs especially the significant pressure-induced pre-lithiation strategies are briefly reviewed.Then,a recent achievement by Meng et al.in this field is elaborated in detail.Finally,the significance of Meng’s work is discussed.
基金the technical support for Nano-X from Suzhou Institute of Nano-Tech and NanoBionics,Chinese Academy of Sciences(SINANO)supported by the National Key R&D Program of China(2021YFB3800300)+2 种基金the National Natural Science Foundation of China(22179059,22239002,92372201)the science and technology innovation fund for emission peak and carbon neutrality of Jiangsu province(BK20231512,BK20220034)the Key R&D project funded by department of science and technology of Jiangsu Province(BE2020003)。
文摘Aluminum(Al)exhibits excellent electrical conductivity,mechanical ductility,and good chemical compatibility with high-ionic-conductivity electrolytes.This makes it more suitable as an anode material for all-solid-state lithium batteries(ASSLBs)compared to the overly reactive metallic lithium anode and the mechanically weak silicon anode.This study finds that the pre-lithiated Al anode demonstrates outstanding interfacial stability with the Li_6PS_5Cl(LPSCl)electrolyte,maintaining stable cycling for over 1200 h under conditions of deep charge-discharge.This paper combines the pre-lithiated Al anode with a high-nickel cathode,LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2),paired with the highly ionic conductive LPSCl electrolyte,to design an ASSLB with high energy density and stability.Using anode pre-lithiation techniques,along with dual-reinforcement technology between the electrolyte and the cathode active material,the ASSLB achieves stable cycling for 1000 cycles at a 0.2C rate,with a capacity retention rate of up to 82.2%.At a critical negative-to-positive ratio of 1.1,the battery's specific energy reaches up to 375 Wh kg^(-1),and it maintains over 85.9%of its capacity after 100 charge-discharge cycles.This work provides a new approach and an excellent solution for developing low-cost,high-stability all-solid-state batteries.
基金the financial support from the Shanghai Oriental Talent Program(QNDS2024007)On-Campus Scene Verification Project of Tongji University(kh0170020242359)+4 种基金Shanghai Research Institute of China Shenhua Coal-to-Liquids Chemical Co.,Ltd.the National Natural Science Foundation of China(52307249)National Science Foundation of Shanghai Province(23ZR1465900)Fundamental Research Funds for the Central Universities at Tongji University(PA2022000668,22120220426)Nanchang Automotive Institute of Intelligence&New Energy of Tongji University(TPDTC202211-02)。
文摘Silicon is considered one of the most promising candidates for incorporation into carbon-based anodes in lithium-ion batteries(LIBs)due to its high specific capacity.However,the significant volume changes during charge and discharge cycles lead to repeated reconstruction of the solid electrolyte interface(SEI)film and continuous loss of active lithium.Pre-lithiation method is regarded as a highly attractive approach for effectively compensating for active lithium loss during the charge and discharge cycles of LIBs.Constructing a stable SEI film is particularly crucial in the pre-lithiation process.In this study,we developed a direct contact pre-lithiation(DC-Pr)method to create a temperature-tailored robust SEI film interface on silicon-carbon(Si@C)electrodes.By investigating the morphology,structure,and composition of the SEI formed on Si@C electrodes at different pre-lithiation temperatures(50,25,0,and-25℃),we demonstrated that controlling the lithiation temperature to regulate the migration rate of lithium ions within the Si@C electrode yields a lithiated Si@C anode(25-Pr-Si@C)at 25℃ with a continuous,uniform SEI film(~3.65 nm)enriched with Li_(2)O-LiF,which exhibits synergistic effects.Importantly,the initial Coulombic efficiency(ICE)of 25-Pr-Si@C significantly improved from 85.4% in the unlithiated Si@C electrode(Blank-Si@C)to 106.1%.Additionally,the full cell configuration using a high areal loading of lithiated Si@C(~5.5 mA h cm^(-2))as the anode and NCM811 as the cathode(NCM811||25-Pr-Si@C)demonstrated superior cycling performance,maintaining 69.4% of capacity retention and achieving a Coulombic efficiency of over 99.7% after 150 cycles(0.5 C).Therefore,this simple and efficient experimental design provides a high-performance,controllable,and scalable pre-lithiation method for LIBs,paving the way for the commercialization of LIBs utilizing pre-lithiation techniques.
基金financial support from the Science and Technology Projects of State Grid Corporation of China(5100-202499473A-3-6-RW)。
文摘Li_(2)NiO_(2)has emerged as a promising cathode pre-lithiation additive capable of substantially enhancing the energy density and cycling durability of next-generation lithium-ion batteries.However,its practical deployment is hindered by intrinsic surface structural instability under ambient conditions.Although prior studies have reported residual alkali formation on Li_(2)NiO_(2)surfaces and proposed coating strategies,critical knowledge gaps persist regarding the temporal evolution of alkali byproducts and industrially viable modification approaches.Through multiscale in situ characterizations combining X-ray diffraction(XRD),Raman spectroscopy,and X-ray photoelectron spectroscopy(XPS),we reveal a stratified residual alkali architecture:the inner layer predominantly comprises Li_(2)CO_(3)while the outer layer is dominated by LiOH,despite minimal bulk structural alterations.Leveraging these insights,we developed a facile carbon-coating strategy enabling scalable synthesis of hundred-gram batches.The conformal carbon layer effectively mitigates structural degradation and suppresses alkali formation,facilitating the integration of high-content pre-lithiation additives.LiFePO_(4)||graphite pouch cells incorporating 2.5% modified Li_(2)NiO_(2)demonstrate enhanced specific capacity with exceptional stability—exhibiting negligible energy decay(99.58%retention)over 500 cycles at 0.5P and maintaining 81.15% energy retention under aggressive 4P/4P cycling conditions over 1000 cycles.Remarkably,pouch cells with 8% additive loading achieve zero energy density decay after 1000 cycles at 4P/4P.This work provides a practical and scalable solution for advancing high-energy-density lithium-ion battery technologies.
基金the support of the Deputyship for Research and Innovation-Ministry of Education,Kingdom of Saudi Arabia,for this research through a grant(NU/IFC/INT/01/002)under the Institutional Funding Committee at Najran University,Kingdom of Saudi Arabiathe support from the National Research Foundation of Korea(NRF)funded by the Brain Pool program(2021H1D3A2A02039346)。
文摘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.
基金supported by the National Natural Science Foundation of China[grant number 22005318,22075303]the Western Young Scholars Foundations of Chinese Academy of Sciences,the Science Fund of Shandong Laboratory of Yantai Advanced Materials and Green Manufacturing(AMGM2022A02)the Provincial Youth Science and Technology Fund Program of Gansu Province[Project No.21JR7RA092].
文摘Similar to lithium-ion batteries(LIBs),during the first charge/discharge process of lithium-ion capacitors(LICs),lithium-intercalated anodes(e.g.,silicon,graphite,and hard carbon)also exhibit irreversible lithium intercalation behaviors,such as the formation of a solid electrolyte interface(SEI),which will consume Li^(+)in the electrolyte and significantly reduce the electrochemical performance of the system.Therefore,pre-lithiation is an indispensable procedure for LICs.At present,commercial LICs mostly use lithium metal as the lithium source to compensate for the irreversible capacity loss,which has the demerits of operational complexity and danger.However,the pre-lithiation strategy based on cathode sacrificial lithium salts(CSLSs)has been proposed,which has the advantages of low cost,simple operation,environmental protection,and safety.Therefore,there is an urgent need for a timely and comprehensive summary of the application of CSLSs to LICs.In this review,the important roles of pre-lithiation in LICs are detailed,and different pre-lithiation methods are reviewed and compared systematically and comprehensively.After that,we systematically discuss the pre-lithiation strategies based on CSLSs and mainly introduce the lithium extraction mechanism of CSLSs and the influence of intrinsic characteristics and doping amount of CSLSs on LICs performance.In addition,a summary and outlook are conducted,aiming to provide the essential basic knowledge and guidance for developing a new pre-lithiation technology.
基金supported by National Natural Science Foundation of China(Grant No.52002094)Guangdong Basic and Applied Basic Research Foundation(Grant No.2019A1515110756)+2 种基金Shenzhen Science and Technology Program(Grant No.JCYJ20210324121411031,JSGG202108021253804014,RCBS20210706092218040)the Shenzhen Steady Support Plan(GXWD20221030205923001,GXWD20201230155427003-20200824103000001)School Research Startup Expenses of Harbin Institute of Technology(Shenzhen)(Grant No.DD29100027,DD45001022).
文摘The development of high-energy-density Li-ion batteries is hindered by the irreversible capacity loss during the initial charge-discharge process.Therefore,pre-lithiation technology has emerged in the past few decades as a powerful method to supplement the undesired lithium loss,thereby maximizing the energy utilization of LIBs and extending their cycle life.Lithium oxalate(Li_(2)C_(2)O_(4)),with a high lithium content and excellent air stability,has been considered one of the most promising materials for lithium compensation.However,the sluggish electrochemical decomposition kinetics of the material severely hinders its further commercial application.Here,we introduce a recrystallization strategy combined with atomic Ni catalysts to modulate the mass transport and decomposition reaction kinetics.The decomposition potential of Li_(2)C_(2)O_(4)is significantly decreased from~4.90V to~4.30V with a high compatibility with the current battery systems.In compared to the bare NCM//Li cell,the Ni/N-rGO and Li_(2)C_(2)O_(4)composite(Ni-LCO)modified cell releases an extra capacity of~11.7%.Moreover,this ratio can be magnified in the NCM//SiOx full cell,resulting in a 30.4%higher reversible capacity.Overall,this work brings the catalytic paradigm into the pre-lithiation technology,which opens another window for the development of high-energy-density battery systems.
基金supported by the National Natural Science Foundation of China(52072138)the Shenzhen Science and TechnologyProgram(JCYJ2022530160816038and JCYJ20220818100418040)+1 种基金the Postdoctoral Fellowship Program of China Postdoctoral Science Foundation(GZC20230879)the China Postdoctoral Science Foundation(2023M74247)。
文摘Li_(3)VO_(4)has been a promising insertion anode material for Li-ion batteries,which has high theoretical capacity(up to~600 m Ah g^(-1))and safe Li insertion voltage(0.5–1 V vs.Li/Li^(+)).However,the low initial Coulombic efficiency(ICE)has always been the bottleneck limiting its commercialisation.Here,we propose a facile pre-lithiation method to controllably elevate the ICE by the post-treatment of the prepared Li_(3)VO_(4)composite electrode based on an immersion reaction.In this process,the whole electrode was immersed in the liquid Li source,via which the ICE of the Li_(3)VO_(4)electrode can be controllably elevated from 80%to over 100%within 5 min of pre-lithiation.Rather than the traditional powder treatment for pre-lithiation,this process we proposed minimizes the impact of pre-lithiation on the battery assembly process.Moreover,we further investigated the effect of this pre-lithiation process on the functional components in the electrode.For the first time the ICE of Li_(3)VO_(4)electrode was elevated to 100%.As a result,the initial reversible capacity of LiFePO_(4)||Li_(3)VO_(4)full cell was improved from 44.0 to146.3 m Ah g-1,demonstrating the feasibility and great potential of the process.
基金financially supported by the National Natural Science Foundation of China(No.51603147)Tianjin Application Foundation and Advanced Technology Research Plan Project(Nos.15ZCZDGX00270,14RCHZGX00859)China Postdoctoral Science Foundation(No.2017M621079)
文摘Mesoporous carbon（MC） material with high specific surface area（1432 m^2/g）, large pore volume（2.894 cm^3/g） and appropriate mesopore structure（about 6.5 nm） has been prepared. We use the magnesium citrate as the precursor of the carbon material and the nano-sized magnesium oxide（MgO）particles as template provided by magnesium citrate. The structure characterization and the electrochemical performance of MC are investigated. Compared with commercial activated carbon（AC） cathode, the utilization of MC cathode can obviously improve the energy density of LIC device. When the MC cathode is coupled with pre-lithiated hard carbon（HC） anode, the LIC device shows the optimal electrochemical performance, high energy density up to 95.4 Wh/kg and power density as high as 7.4 kW/kg（based on active material mass of two electrodes）, excellent capacity retention of 97.3% after 2000 cycles. The present work indicates the combination of MC electrode with HC electrodes as promising candidates for the realization of LIC with high energy density, high power density and long cycle life.
基金supported by the National Natural Science Foundation of China(Grant No.51672144,51572137,51702181,52072196,52002199,52002200)the Major Basic Research Program of Natural Science Foundation of Shandong Province(Grant No.ZR2020ZD09)+6 种基金the Shandong Provincial Key Research and Development Program(SPKR&DP)(Grant No.2019GGX102055)the Natural Science Foundation of Shandong Province(Grant No.ZR2019BEM042,ZR2020QE063)the Innovation and Technology Program of Shandong Province(Grant No.2020KJA004)the Guangdong Basic and Applied Basic Research Foundation(Grant No.2019A1515110933)the China Postdoctoral Science Foundation(Grant No.2020M683450)the Taishan Scholars Program of Shandong Province(No.ts201511034)the Postdoctoral Innovation Project of Shandong Province(Grant no.202101020)。
文摘The poor rate capability and low capacity are huge barriers to realize the commercial applications of battery-type transition metal compounds(TMCs) cathode.Herein,numerous Se vacancy defects are introduced into the Ni_(3)Se_(2)lamellas by pre-lithiation technique,which can be acted as a novel class of battery-type cathode for hybrid supercapacitors.Appropriately modulating the contents of the preembedded lithium(Li) ions can induce a controllable vacancy content in the series of as-prepared products,effectively endowing a fast reaction kinetic and high activity for the cathode.Benefiting from the distinct design,the optimized cathode(Li2-Ni_(3)Se_(2)) presents a high specific capacity of 236 mA h g^(-1)at1 A g^(-1),importantly,it can still possess 117 mA h g^(-1)when the current density is increased up to 100A g^(-1),exhibiting relatively high rate capability.It is much superior to other battery-type TMC cathodes reported in previous studies.Moreover,the cathode also shows the excellent cycling stability with 92%capacity retention after 3,000 cycles.In addition,a hybrid supercapacitor(HSC) is assembled with the obtained Li2-Ni_(3)Se_(2)as the cathode and active carbon(AC) as the anode,which delivers a high energy density of 77 W h kg^(-1)at 4 kW kg^(-1)and long-term durability(90% capacitance retention after 10,000 cycles).Therefore,the strategy not only provides an effective way to realize the controllable vacancy content in TMCs for achieving high-perfo rmance cathodes for HSC,but also further promotes their large-scale applications in the energy storage fields.
基金supported by the Gansu Provincial Department of Education:Industrial Support Program Project(2021CYZC-18)the Major Science and Technology Projects of Gansu Province(21ZD4GA031)+2 种基金the Key R&D plan of Gansu Province(21YF5GA079)the Lanzhou University of Technology Hongliu First-class Discipline Construction ProgramEducation Department of Gansu Province:Excellent Graduate Student Innovation Star Project(2021CXZX-456)。
文摘Silicon anodes are considered to be the most promising alternatives owing to their theoretical specific capacity,which is almost 10 times higher than that of graphite anodes.However,huge volume changes during charging and discharging affect their interface stability,which strongly limits their application in commercial batteries.Herein,a popcorn-structured silicon-carbon composite(SiNPs@graphene@C),composed of silicon nanoparticles(SiNPs),graphene spheres and pitch-based carbon,is prepared by spraydrying followed by a wet process.The resulting SiNPs@graphene@C composite has good flexibility and elastic-strain capacity due to the graphene substrate,and it possesses macrostructural integrity and mechanical stability during cycling due to the rigid carbon–carbon chemical bonds.As a result,it shows a discharge-specific capacity of 481.3 mAh g^(-1)and a capacity retention of 82.9%after 500 cycles at 1 A g^(-1).Besides,the initial coulomb efficiency is increased from 65.7%to 86.5%by pre-lithiation,which improves the feasibility of commercialising the SiNPs@graphene@C composite.
基金the financial support provided by the National Natural Science Foundation of China(No.52072138)the National Key Research and Development Program of China(No.2018YFE0206900)+1 种基金the Shenzhen Science and Technology Program(No.JCYJ20220530160816038)the Australian Research Council(ARC)through the Discovery Project(No.DP180102297).
文摘Li_(2)C_(2)O_(4),with a high theoretical capacity of 525 mAh·g^(−1)and good air stability,is regarded as a more attractive cathode prelithiation additive in contrast to the reported typical inorganic pre-lithiation compounds which are quite air sensitive.However,its obtained capacity is much lower than the theoretical value and its delithiation potential(>4.7 V)is too high to match with the most commercial cathode materials,which greatly impedes its practical application.Herein,we greatly improve the pre-lithiation performance of Li_(2)C_(2)O_(4)as cathode additive with fulfilled capacity at a much-reduced delithiation voltage,enabling its wide applicability for typical commercial cathodes.We increase the capacity of Li_(2)C_(2)O_(4)from 436 to 525 mAh·g^(−1)by reducing its particle size.Through optimizing the types of conductive additives,introducing nano-morphological NiO,MnO2,etc.as catalysts,and innovatively designing a bilayer electrode,the delithiation potential of Li_(2)C_(2)O_(4)is successfully reduced from 4.778 to 4.288 V.We systematically study different particle size,conductive additives,and catalysts on the delithiation behavior of Li_(2)C_(2)O_(4).Finally,it is applied to pre-lithiate the hard carbon anode,and it is found that Li_(2)C_(2)O_(4)could effectively increase the capacity of the full cell from 79.0 to 140.0 mAh·g^(−1)in the first cycle.In conclusion,our study proves that improving the reactivity is an effective strategy to boost the pre-lithiation of Li_(2)C_(2)O_(4).
基金the National Natural Science Foundation of China(51673199 and 51677176)Youth Inn ovation Promotion Association of Chinese Academy of Sciences(2015148)+4 种基金Dalian National Laboratory for Clean Energy(DNL180307)Innovation Foundation of Dalian Institute of Chemical PhysicsChinese Academy of Sciences(ZZBS201615 and ZZBS201708)Dalian Science and Technology Star Program(2016RQ026)The authors also thank Lei Shi for the helpful discussion on Li3N related reaction.
文摘Li3N is an excellent zero-residue positive electrode pre-lithiation additive to offset the initial lithium loss in lithium-ion capacitors. However, Li3N has an intrinsic problem of poor compatibility with commonly used aprotic polar solvents in electrode manufacture procedure due to its high reactivity with commonly used solvents like N-methy-2-pyrrolidone(NMP) and etc. It is the Valley of Death between research and large-scale commercialization of Li-ion capacitors using Li3N as prelithiation agent. In this work, Li3N containing electrode is prepared by a commercially adoptable route for the first time, using N,Ndimethylformamide(DMF) to homogenate the electrode slurry. The DMF molecular stabilizing mechanism is confirmed via experiment analysis and DFT simulation, indicating that the dehydrogenation energy for DMF is obviously larger than other commonly used solvents such as NMP and etc. The soft package lithium-ion capacitors(LIC250) with only 12 wt% Li3N addition in AC positive electrode exhibits excellent rate capability, cyclic stability and ultrahigh specific energy. Its specific energy is 2.3 times higher than the Li3N-free devices, with energy retention as high as 90% after 10,000 cycles.
基金This work was supported by the National Natural Science Foundation of China(22008053,52002111)Key Research and Development Program of Hebei Province(20310601D,205A4401D)+2 种基金the Natural Science Foundation of Hebei Province(B2021208061)the High Level Talents Funding of Hebei Province(A202005006)the Science Foundation of University of Hebei Province(BJ2020026,BJ2021001).
文摘Due to the high reactivity between the lithium metal and traditional organic liquid electrolyte,the reaction of lithium metal electrode is usually uneven and there are also unexpected side reactions.Therefore,construction of a stable solid electrolyte interface(SEI)is highly essential to improve the performance of lithium metal anode.Herein,a sandwich-like gel polymer electrolyte(GPE)is accurately prepared by in-situ polymerization of Polyacrylonitrile(PAN)nanofiber membrane with trihydroxymethylpropyl trimethylacrylate(TMPTMA)and 1,6-hexanediol diacrylate(HDDA).The resulting GPE with a tightly cross-linked gel skeleton exhibits high ionic conductivity and electrochemical window of 5.6 V versus Li/Li^(+).In particular,the pretreatment of Li metal anode can improve the interfacial wettability,and the synergy of the chemically pretreated Li metal anode surface and the GPE can electrochemically in situ generate SEI with compositionally stable and fluorine-rich inorganic components.Owing to these unique advantages,the interfacial compatibility between the GPE and lithium metal is greatly improved.Meanwhile,the formed SEI can inhibit the formation of lithium dendrites,and decomposition of GPE would be alleviated.The assembled Li-FEC|GPE|LiFePO_(4) full cell shows a high initial discharge capacity of 157.1 mA h g^(-1),and maintains a capacity retention of 92.3%after 100 cycles at 0.2C.
