Free-standing silicon anodes with high proportion of active materials have aroused great attention;however,the mechanical stability and electrochemical performance are severely suppressed.Herein,to resolve the appeal ...Free-standing silicon anodes with high proportion of active materials have aroused great attention;however,the mechanical stability and electrochemical performance are severely suppressed.Herein,to resolve the appeal issues,a free-standing anode with a"corrugated paper"shape on micro-scale and a topological crosslinking network on the submicron and nano-scale is designed.Essentially,an integrated three-dimensional electrode structure is constructed based on robust carbon nanotubes network with firmly anchored SiNPs via forming interlocking junctions.In which,the hierarchical interlocking structure is achieved by directional induction of the binder,which ensures well integration during cycling so that significantly enhances mechanical stability as well as electronic and ionic conductivity of electrodes.Benefiting from it,this anode exhibits outsta nding performance under harsh service conditions including high Si loading,ultrahigh areal capacity(33.2 mA h cm^(-2)),and high/low temperatures(-15-60℃),which significantly extends its practical prospect.Furthermore,the optimization mechanism of this electrode is explored to verify the crack-healing and structure-integration maintaining along cycling via a unique self-stabilization process.Thus,from both the fundamental and engineering views,this strategy offers a promising path to produce high-performance free-standing electrodes for flexible device applications especially facing volume effect challenges.展开更多
Silicon(Si)has emerged as a potent anode material for lithium-ion batteries(LIBs),but faces challenges like low electrical conductivity and significant volume changes during lithiation/delithiation,leading to material...Silicon(Si)has emerged as a potent anode material for lithium-ion batteries(LIBs),but faces challenges like low electrical conductivity and significant volume changes during lithiation/delithiation,leading to material pulverization and capacity degradation.Recent research on nanostructured Si aims to mitigate volume expansion and enhance electrochemical performance,yet still grapples with issues like pulverization,unstable solid electrolyte interface(SEI)growth,and interparticle resistance.This review delves into innovative strategies for optimizing Si anodes’electrochemical performance via structural engineering,focusing on the synthesis of Si/C composites,engineering multidimensional nanostructures,and applying non-carbonaceous coatings.Forming a stable SEI is vital to prevent electrolyte decomposition and enhance Li^(+)transport,thereby stabilizing the Si anode interface and boosting cycling Coulombic efficiency.We also examine groundbreaking advancements such as self-healing polymers and advanced prelithiation methods to improve initial Coulombic efficiency and combat capacity loss.Our review uniquely provides a detailed examination of these strategies in real-world applications,moving beyond theoretical discussions.It offers a critical analysis of these approaches in terms of performance enhancement,scalability,and commercial feasibility.In conclusion,this review presents a comprehensive view and a forward-looking perspective on designing robust,high-performance Si-based anodes the next generation of LIBs.展开更多
Binders could play crucial or even decisive roles in the fabrication of low-cost, stable and high-capacity electrodes. This is especially the case for the silicon (Si) anodes and sulfur (S) cathodes that undergo large...Binders could play crucial or even decisive roles in the fabrication of low-cost, stable and high-capacity electrodes. This is especially the case for the silicon (Si) anodes and sulfur (S) cathodes that undergo large volume change and active material loss in lithium-ion batteries during prolonged cycles. Herein, a hydrophilic polymer poly(methyl vinyl ether-alt-maleic acid) (PMVEMA) was explored as a dual-functional aqueous binder for the preparation of high-performance silicon anode and sulfur cathode. Benefiting from the dual functions of PMVEMA, i.e., the excellent dispersion ability and strong binding forces, the as-prepared electrodes exhibit improved capacity, rate capability and long-term cycling performance. In particular, the as-prepared Si electrode delivers a high initial discharge capacity of 1346.5 mAh g^(−1) at a high rate of 8.4 A/g and maintains 834.5 mAh g^(−1) after 300 cycles at 4.2 A/g, while the as-prepared S cathode exhibits enhanced cycling performance with high remaining discharge capacities of 663.4 mAh g^(−1) after 100 cycles at 0.2 C and 487.07 mAh g^(−1) after 300 cycles at 1 C, respectively. These encouraging results suggest that PMVEMA could be a universal binder to facilitate the green manufacture of both anode and cathode for high-capacity energy storage systems.展开更多
Silicon-based(Si)materials are promising anodes for lithium-ion batteries(LIBs)because of their ultrahigh theoretical capacity of 4200 mA h g^(−1).However,commercial applications of Si anodes have been hindered by the...Silicon-based(Si)materials are promising anodes for lithium-ion batteries(LIBs)because of their ultrahigh theoretical capacity of 4200 mA h g^(−1).However,commercial applications of Si anodes have been hindered by their drastic volume variation(∼300%)and low electrical conductivity.Here,to tackle the drawbacks,a hierarchical Si anode with double-layer coatings of a SiOx inner layer and a nitrogen(N),boron(B)co-doped carbon(C-NB)outer layer is elaborately designed by copyrolysis of Si-OH structures and a H3BO_(3)-doped polyaniline polymer on the Si surface.Compared with the pristine Si anodes(7mA h g^(−1) at 0.5 A g^(−1) after 340 cycles and 340 mA h g^(−1) at 5 A g^(−1)),the modified Si-based materials(Si@SiOx@C-NB nanospheres)present su perior cycling stability(reversible 1301 mA h g^(−1) at 0.5 A g^(−1) after 340 cycles)as well as excellent rate capability(690mA h g^(−1) at 5 A g^(−1))when used as anodes in LIBs.The unique double-layer coating structure,in which the inner amorphous SiOx layer acts as a buffer matrix and the outer defect-rich carbon enhances the electron diffusion of the whole anode,makes it possible to de liver excellent electrochemical properties.These results indicate that our double-layer coating strategy is a promising approach not only for the devel opment of sustainable Si anodes but also for the design of multielement-doped carbon nanomaterials.展开更多
We report the synthesis of a high‐performance graphitic carbon‐coated silicon(Si@GC)composite material for lithium‐ion batteries via a scalable production route.Porous Si is produced from the magnesiothermic reduct...We report the synthesis of a high‐performance graphitic carbon‐coated silicon(Si@GC)composite material for lithium‐ion batteries via a scalable production route.Porous Si is produced from the magnesiothermic reduction of commercial silica(SiO2)precursor followed by low‐temperature graphitic carbon coating using glucose as the precursor.The obtained Si@GC composite achieves an excellent reversible specific capacity of 1195 mAh g−1 and outstanding cycle stability.The thick Si@GC anode(3.4 mg cm^−2)in full cells with commercial lithium iron phosphate cathode delivers a remarkable performance of 800 mAh g^−1 specific capacity and 2.7 mAh cm^−2 areal capacity as well as 93.6%capacity retention after 200 cycles.展开更多
Silicon(Si)has been investigated as a promising anode material because of its high theoretical capacity(4200 m Ah g^(-1)).However,silicon anode suffers from huge volume changes during repeated charge–discharge cycles...Silicon(Si)has been investigated as a promising anode material because of its high theoretical capacity(4200 m Ah g^(-1)).However,silicon anode suffers from huge volume changes during repeated charge–discharge cycles.In this work,inspired by a remarkable success of the glutinous rice mortar in the Great Wall with ca.2000-year history,amylopectin(AP),the key ingredient responsible for the strong bonding force,is extracted from glutinous rice and utilized as a flexible,aqueous,and resilient binder to address the most challenging drastic volume-expansion and pulverization issues of silicon anode.Additionally,the removal of toxic N-methyl-2-pyrrolidone(NMP)organic solvent makes the electrode fabrication process environmentally friendly and healthy.The as-prepared Si-AP electrode with 60 wt%of Si can uphold a high discharge capacity of 1517.9 m Ah g^(-1)at a rate of 0.1 C after 100 cycles.The cycling stability of the Si-AP has been remarkably improved in comparison with both traditional polyvinylidene fluoride(PVDF)and aqueous carboxymethylcellulose(CMC)binders.Moreover,when the content of silicon in the Si-AP electrode increases to 70 wt%,a high discharge capacity of 1463.1 m Ah g^(-1)can still be obtained after 50 cycles at 0.1°C.These preliminary results suggest that the sustainably available and environmentally benign amylopectin binders could be a promising choice for the construction of highly stable silicon anodes.展开更多
Silicon has ultrahigh capacity,dendrite-free alloy lithiation mechanism and low cost and has been regarded as a promising anode candidate for solid-state battery.Owing to the low infiltration of solid-state electrolyt...Silicon has ultrahigh capacity,dendrite-free alloy lithiation mechanism and low cost and has been regarded as a promising anode candidate for solid-state battery.Owing to the low infiltration of solid-state electrolyte(SSE),not the unstable solid-electrolyte interphase(SEI),but the huge stress during lithiation-and delithiation-induced particle fracture and conductivity lost tend to be the main issues.In this study,starting with micron-Si,a novel monothetic carbon conductive framework and a MgO coating layer are designed,which serve as electron pathway across the whole electrode and stress releasing layer,respectively.In addition,the in situ reaction between Si and SSE helps to form a LiF-rich and mechanically stable SEI layer.As a result,the mechanical stability and charge transfer kinetics of the uniquely designed Si anode are significantly improved.Consequently,high initial Coulombic efficiency,high capacity and durable cycling stability can be achieved by applying the Si@MgO@C anode in SSB.For example,high specific capacity of 3224.6 mAh·g^(-1)and long cycling durability of 200 cycles are achieved.This work provides a new concept for designing alloy-type anode that combines surface coating on particle and electrode structure design.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-NH2 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
Si is a promising anode material for Li ion batteries because of its high specific capacity,abundant reserve,and low cost.However,its rate performance and cycling stability are poor due to the severe particle pulveriz...Si is a promising anode material for Li ion batteries because of its high specific capacity,abundant reserve,and low cost.However,its rate performance and cycling stability are poor due to the severe particle pulverization during the lithiation/delithiation process.The high stress induced by the Li concentration gradient and anisotropic deformation is the main reason for the fracture of Si particles.Here we present a new stress mitigation strategy by uniformly distributing small amounts of Sn and Sb in Si micron-sized particles,which reduces the Li concentration gradient and realizes an isotropic lithiation/delithiation process.The Si8.5Sn0.5Sb microparticles(mean particle size:8.22μm)show over 6000-fold and tenfold improvements in electronic conductivity and Li diffusivity than Si particles,respectively.The discharge capacities of the Si_(8.5)Sn_(0.5)Sb microparticle anode after 100 cycles at 1.0 and 3.0 A g^(-1)are 1.62 and 1.19 Ah g^(-1),respectively,corresponding to a retention rate of 94.2%and 99.6%,respectively,relative to the capacity of the first cycle after activation.Multicomponent microparticle anodes containing Si,Sn,Sb,Ge and Ag prepared using the same method yields an ultra-low capacity decay rate of 0.02%per cycle for 1000 cycles at 1 A g^(-1),corroborating the proposed mechanism.The stress regulation mechanism enabled by the industry-compatible fabrication methods opens up enormous opportunities for low-cost and high-energy-density Li-ion batteries.展开更多
Nowadays,silicon has become a promising anode active material for lithium-ion batteries due to its high specific capacity.However,traditional binder materials cannot effectively restrain the volume expansion of silico...Nowadays,silicon has become a promising anode active material for lithium-ion batteries due to its high specific capacity.However,traditional binder materials cannot effectively restrain the volume expansion of silicon during lithiation/delithiation.Inspired by the growth process of climbing plants,we sequentially crosslink sodium alginate with calcium ions and hyperbranched polyethyleneimine to construct a dual crosslinked network binder.During the sequentially crosslinking,sodium alginate preferentially crosslinks with Ca^(2+)to form the"trellis"network,which restricts the free movement of hyperbranched polyethyleneimine and guides it,like"vine",to gradually anchor on the surrounding"trellis"through hydrogen and ionic bonding.In this dual crosslinked network,the ionic ally crosslinked sodium alginate maintains the anode structural integrity;the anchored hyperbranched polyethyleneimine forms strong multidimensional hydrogen bonds with silicon nanoparticles through its amino-rich branch chains;and the network utilizes the bonding reversibility of hydrogen and ionic bonds to repeatedly eliminate the mechanical stress and self-heal the structure damages caused by the volume change of silicon.Benefited from the multifunction of the dual crosslinked network,the silicon anode has achieved an excellent electrochemical performance with a specific capacity of 2403 mAh·g^(-1)at the current density of500 mA·g^(-1)after 100 cycles.展开更多
Sulfide solid electrolyte(SE)is one of the most promising technologies for all-solid-state batteries(ASSBs)because of its high ionic conductivity and ductile mechanical properties.In order to further improve the energ...Sulfide solid electrolyte(SE)is one of the most promising technologies for all-solid-state batteries(ASSBs)because of its high ionic conductivity and ductile mechanical properties.In order to further improve the energy density of sulfide-based ASSBs and promote practical applications,silicon anodes with ultrahigh theoretical capacity(4,200 mAh·g^(−1))and rich resource abundance have broad commercial prospects.However,significant challenges including bulk instability of sulfide SEs and poor utilization of silicon materials have severely impeded the ASSBs from becoming viable.In this review,we first introduce the critical bulk properties of sulfide SEs and the most recent improving strategies covering the ionic conductivity,air stability,electrochemical window,mechanical stability,thermostability and solvent stability.Next,we introduce the main factors affecting the compatibility of silicon and sulfide SE,including the carbon’s effect,particle size of silicon,external pressure,silicon composite matrix and the depth of silicon’s lithiation.Finally,we discuss possible research directions in the future.We hope that this review can provide a comprehensive picture of the role of nanoscale approaches in recent advances in ASSBs with sulfide and silicon,as well as a source of inspiration for future research.展开更多
Silicon-based anodes with high theoretical capacity have intriguing potential applications for high energy density lithium-ion batteries(LIBs),while suffer from immense volumetric change and brittle solidstate electro...Silicon-based anodes with high theoretical capacity have intriguing potential applications for high energy density lithium-ion batteries(LIBs),while suffer from immense volumetric change and brittle solidstate electrolyte interface that causes collapse of electrodes.Here,a stress-dissipated conductive polymer binder(polyaniline with citric acid,PC)is developed to enhance the mechanical electrochemical performance between Si nanoparticles(SiNPs)and binders.Benefiting from the stable triangle network node of citric acid and a considerable distributed of hydroxyl groups,the PC binder can effectively dissipate the stress from SiNPs,thus providing an excellent cyclic stability of Si anodes.Both experimental results and theoretical calculation demonstrate the enhanced adhesion between binders and SiNPs could bond the particles tightly to form a robust electrode.The as-fabricated Si anode exhibits outstanding structural stability upon long-term cycles that exhibit a highly reversible capability of 1021 mA·h·g^(-1)over 500 cycles at a current density of 0.5 C(1 C¼4200mA·g^(-1)).Evidently,this stressdissipated binder design will provide a promising route to achieve long-life Si-based LIBs.展开更多
Silicon(Si)is a potential high-capacity anode material for the next-generation lithium-ion battery with high energy density.However,Si anodes suff er from severe interfacial chemistry issues,such as side reactions at ...Silicon(Si)is a potential high-capacity anode material for the next-generation lithium-ion battery with high energy density.However,Si anodes suff er from severe interfacial chemistry issues,such as side reactions at the electrode/electrolyte interface,leading to poor electrochemical cycling stability.Herein,we demonstrate the fabrication of a conformal fl uorine-containing carbon(FC)layer on Si particles(Si-FC)and its in situ electrochemical conversion into a LiF-rich carbon layer above 1.5 V(vs.Li^(+)/Li).The as-formed LiF-rich carbon layer not only isolates the active Si and electrolytes,leading to the suppression of side reactions,but also induces the formation of a robust solid-electrolyte interface(SEI),leading to the stable interfacial chemistry of as-designed Si-FC particles.The Si-FC electrode has a high initial Coulombic effi ciency(CE)of 84.8%and a high reversible capacity of 1450 mAh/g at 0.4 C(1000 mA/g)for 300 cycles.In addition,a hybrid electrode consisting of 85 wt%graphite and 15 wt%Si-FC,and mass 2.3 mg/cm^(2) loading delivers a high areal capacity of 2.0 mAh/cm^(2) and a high-capacity retention of 93.2%after 100 cycles,showing the prospects for practical use.展开更多
Despite advancements in silicon-based anodes for high-capacity lithium-ion batteries,their widespread commercial adoption is still hindered by significant volume expansion during cycling,especially at high active mass...Despite advancements in silicon-based anodes for high-capacity lithium-ion batteries,their widespread commercial adoption is still hindered by significant volume expansion during cycling,especially at high active mass loadings crucial for practical use.The root of these challenges lies in the mechanical instability of the material,which subsequently leads to the structural failure of the electrode.Here,we present a novel synthesis of a composite combining expanded graphite and silicon nanoparticles.This composite features a unique interlayer-bonded graphite structure,achieved through the application of a modified spark plasma sintering method.Notably,this innovative structure not only facilitates efficient ion and electron transport but also provides exceptional mechanical strength(Vickers hardness:up to658 MPa,Young's modulus:11.6 GPa).This strength effectively accommodates silicon expansion,resulting in an impressive areal capacity of 2.9 mA h cm^(-2)(736 mA h g^(-1)) and a steady cycle life(93% after 100cycles).Such outsta nding performance is paired with features appropriate for large-scale industrial production of silicon batteries,such as active mass loading of at least 3.9 mg cm^(-2),a high-tap density electrode material of 1.68 g cm^(-3)(secondary clusters:1.12 g cm^(-3)),and a production yield of up to 1 kg per day.展开更多
Silicon(Si)is widely used as a lithium‐ion‐battery anode owing to its high capacity and abundant crustal reserves.However,large volume change upon cycling and poor conductivity of Si cause rapid capacity decay and p...Silicon(Si)is widely used as a lithium‐ion‐battery anode owing to its high capacity and abundant crustal reserves.However,large volume change upon cycling and poor conductivity of Si cause rapid capacity decay and poor fast‐charging capability limiting its commercial applications.Here,we propose a multilevel carbon architecture with vertical graphene sheets(VGSs)grown on surfaces of subnanoscopically and homogeneously dispersed Si–C composite nanospheres,which are subsequently embedded into a carbon matrix(C/VGSs@Si–C).Subnanoscopic C in the Si–C nanospheres,VGSs,and carbon matrix form a three‐dimensional conductive and robust network,which significantly improves the conductivity and suppresses the volume expansion of Si,thereby boosting charge transport and improving electrode stability.The VGSs with vast exposed edges considerably increase the contact area with the carbon matrix and supply directional transport channels through the entire material,which boosts charge transport.The carbon matrix encapsulates VGSs@Si–C to decrease the specific surface area and increase tap density,thus yielding high first Coulombic efficiency and electrode compaction density.Consequently,C/VGSs@Si–C delivers excellent Li‐ion storage performances under industrial electrode conditions.In particular,the full cells show high energy densities of 603.5 Wh kg^(−1)and 1685.5 Wh L^(−1)at 0.1 C and maintain 80.7%of the energy density at 3 C.展开更多
Silicon(Si)has been studied as a promising alloying type anode for lithium-ion batteries due to its high specific capacity,low operating potential and abundant resources.Nevertheless,huge volume expansion during alloy...Silicon(Si)has been studied as a promising alloying type anode for lithium-ion batteries due to its high specific capacity,low operating potential and abundant resources.Nevertheless,huge volume expansion during alloying/dealloying processes and low electronic conductivity of Si anodes restrict their electrochemical performance.Thus,carbon(C)materials with special physical and chemical properties are applied in Si anodes to effectively solve these problems.This review focuses on current status in the exploration of Si/C anodes,including the lithiation mechanism and solid electrolyte interface formation,various carbon sources in Si/C anodes,such as traditional carbon sources(graphite,pitch,biomass),and novel carbon sources(MXene,graphene,MOFs-derived carbon,graphdiyne,etc.),as well as interfacial bonding modes of Si and C in the Si/C anodes.Finally,we summarize and prospect the selection of carbonaceous materials,structural design and interface control of Si/C anodes,and application of Si/C anodes in all-solid-state lithium-ion batteries and sodium-ion batteries et al.This review will help researchers in the design of novel Si/C anodes for rechargeable batteries.展开更多
Silicon anodes have drawn ever-increasing attention in lithium-ion batteries(LIBs) owing to their extremely high theoretical capacity and abundance in the earth. Despite promising advantages, the wide use of silicon a...Silicon anodes have drawn ever-increasing attention in lithium-ion batteries(LIBs) owing to their extremely high theoretical capacity and abundance in the earth. Despite promising advantages, the wide use of silicon anodes in LIBs is highly hindered by their fast capacity fading and low Coulombic efficiency arising from their substantial volumetric variation(>300%). Herein, we report a novel aqueous hybrid gel binder for silicon anodes via crosslinking sodium carboxymethyl cellulose(NaCMC) by an inorganic crosslinker-sodium borate. Not only this gel polymer binder can chemically bond to silicon nanoparticle, but also the deformable framework of this crosslinked binder is capable of maintaining electrode integrity, thus buffering dramatic volume change of silicon. Consequently, the silicon anode with this gel binder exhibits good cycle life(1211.5 mAh/g after 600 cycles) and high initial Coulombic efficiency(88.95%).展开更多
Silicon (Si) is a promising anode material for next-generation high-energy lithium-ion batteries (LIBs) due to its high capacity.However,the large volumetric expansion,poor ion conductivity and unstable solid electrol...Silicon (Si) is a promising anode material for next-generation high-energy lithium-ion batteries (LIBs) due to its high capacity.However,the large volumetric expansion,poor ion conductivity and unstable solid electrolyte interface (SEI) lead to rapid capacity fading and low rate performance.Herein,we report Si nitride (SiN) comprising stoichiometric Si_(3)N_(4) and Li-active anazotic SiN_(x) coated porous Si (p-Si@SiN)for high-performance anodes in LIBs.The ant-nest-like porous Si consisting of 3D interconnected Si nanoligaments and bicontinuous nanopores prevents pulverization and accommodates volume expansion during cycling.The Si_(3)N_(4) offers mechanically protective coating to endow highly structural integrity and inhibit superfluous formation of SEI.The fast ion conducting Li_(3)N generated in situ from lithiation of active SiN_(x) facilitates Li ion transport.Consequently,the p-Si@SiN anode has appealing electrochemical properties such as a high capacity of 2180 mAh g^(-1)at 0.5 A g^(-1) with 84%capacity retention after 200cycles and excellent rate capacity with discharge capacity of 721 mAh g^(-1) after 500 cycles at 5.0 A g^(-1).This work provides insights into the rational design of active/inactive nanocoating on Si-based anode materials for fast-charging and highly stable LIBs.展开更多
Lithium-ion battery anode used as silicon particles were obtained from different major suppliers,and they were characterized by different spectroscopic techniques and evaluated by electrochemical experiments.Correlati...Lithium-ion battery anode used as silicon particles were obtained from different major suppliers,and they were characterized by different spectroscopic techniques and evaluated by electrochemical experiments.Correlations between the key physical parameters and electrochemical properties of the silicon particles were investigated.Silicon particle size,surface oxygen content,-OH content and physical appearance are found to strongly influence the electrochemical properties of the Si anode.The particle size of 100 nm has great promise for the practical application of Si nanoparticles in the lithium-ion battery industry.An inverse correlation between the oxygen content and the reversible capacity or first coulombic efficiency was obtained.The-OH content by surface treatment contributes to enhanced cycling stability by the improved affinity between the Si particle and the water-soluble binder.Spherical Si particles perform better compared to irregular particles,and agglomeration dramatically decreases the cycling stability of the Si anode.Among the investigated Si particles,the sample that exhibited a reversible capacity of more than 2500 mAh g^(-1),a first coulombic efficiency of 89.26%and an excellent cycling stability,has great potential for use in the battery industry.展开更多
In this paper, two types of silicon(Si) particles ball-milled from n-type Si wafers, respectively, with resistivity values of 1 Ω·cm and 0.001 Ω·cm are deposited with silver(Ag). The Ag-deposited n-typ...In this paper, two types of silicon(Si) particles ball-milled from n-type Si wafers, respectively, with resistivity values of 1 Ω·cm and 0.001 Ω·cm are deposited with silver(Ag). The Ag-deposited n-type 1-Ω·cm Si particles(nl-Ag) and Ag-deposited n-type 0.001-Ω·cm Si particles(n0.001-Ag) are separately used as an anode material to assemble coin cells,of which the electrochemical performances are investigated. For the matching of work function between n-type 1-Ω·cm Si(nl) and Ag, nl-Ag shows discharge specific capacity of up to 683 mAh·g^-1 at a current density of 8.4 A·g^-1, which is40% higher than that of n0.001-Ag. Furthermore, the resistivity of nl-Ag is lower than half that of n0.001-Ag. Due to the mismatch of work function between n-type 0.001-Ω·cm Si(n0.001) and Ag, the discharge specific capacity of n0.001-Ag is 250.2 mAh·g^-1 lower than that of nl-Ag after 100 cycles.展开更多
基金sponsored by the National Natural Science Foundation of China(21905221,21805221)the Suzhou Technological innovation of key industries-research and development of key technologies(SGC2021118)。
文摘Free-standing silicon anodes with high proportion of active materials have aroused great attention;however,the mechanical stability and electrochemical performance are severely suppressed.Herein,to resolve the appeal issues,a free-standing anode with a"corrugated paper"shape on micro-scale and a topological crosslinking network on the submicron and nano-scale is designed.Essentially,an integrated three-dimensional electrode structure is constructed based on robust carbon nanotubes network with firmly anchored SiNPs via forming interlocking junctions.In which,the hierarchical interlocking structure is achieved by directional induction of the binder,which ensures well integration during cycling so that significantly enhances mechanical stability as well as electronic and ionic conductivity of electrodes.Benefiting from it,this anode exhibits outsta nding performance under harsh service conditions including high Si loading,ultrahigh areal capacity(33.2 mA h cm^(-2)),and high/low temperatures(-15-60℃),which significantly extends its practical prospect.Furthermore,the optimization mechanism of this electrode is explored to verify the crack-healing and structure-integration maintaining along cycling via a unique self-stabilization process.Thus,from both the fundamental and engineering views,this strategy offers a promising path to produce high-performance free-standing electrodes for flexible device applications especially facing volume effect challenges.
基金financially supported by the Jiangsu Distinguished Professors Project(No.1711510024)the funding for Scientific Research Startup of Jiangsu University(Nos.4111510015,19JDG044)+3 种基金the Jiangsu Provincial Program for High-Level Innovative and Entrepreneurial Talents Introductionthe National Natural Science Foundation of China(No.22008091)Natural Science Foundation of Guangdong Province(2023A1515010894)the Open Project of Luzhou Key Laboratory of Fine Chemical Application Technology(HYJH-2302-A).
文摘Silicon(Si)has emerged as a potent anode material for lithium-ion batteries(LIBs),but faces challenges like low electrical conductivity and significant volume changes during lithiation/delithiation,leading to material pulverization and capacity degradation.Recent research on nanostructured Si aims to mitigate volume expansion and enhance electrochemical performance,yet still grapples with issues like pulverization,unstable solid electrolyte interface(SEI)growth,and interparticle resistance.This review delves into innovative strategies for optimizing Si anodes’electrochemical performance via structural engineering,focusing on the synthesis of Si/C composites,engineering multidimensional nanostructures,and applying non-carbonaceous coatings.Forming a stable SEI is vital to prevent electrolyte decomposition and enhance Li^(+)transport,thereby stabilizing the Si anode interface and boosting cycling Coulombic efficiency.We also examine groundbreaking advancements such as self-healing polymers and advanced prelithiation methods to improve initial Coulombic efficiency and combat capacity loss.Our review uniquely provides a detailed examination of these strategies in real-world applications,moving beyond theoretical discussions.It offers a critical analysis of these approaches in terms of performance enhancement,scalability,and commercial feasibility.In conclusion,this review presents a comprehensive view and a forward-looking perspective on designing robust,high-performance Si-based anodes the next generation of LIBs.
基金This work was financially supported by the Australian Research Council(ARC)Discovery Projects(DP210103266 and DPI 701048343)the Griffith University Ph.D.Scholarships.
文摘Binders could play crucial or even decisive roles in the fabrication of low-cost, stable and high-capacity electrodes. This is especially the case for the silicon (Si) anodes and sulfur (S) cathodes that undergo large volume change and active material loss in lithium-ion batteries during prolonged cycles. Herein, a hydrophilic polymer poly(methyl vinyl ether-alt-maleic acid) (PMVEMA) was explored as a dual-functional aqueous binder for the preparation of high-performance silicon anode and sulfur cathode. Benefiting from the dual functions of PMVEMA, i.e., the excellent dispersion ability and strong binding forces, the as-prepared electrodes exhibit improved capacity, rate capability and long-term cycling performance. In particular, the as-prepared Si electrode delivers a high initial discharge capacity of 1346.5 mAh g^(−1) at a high rate of 8.4 A/g and maintains 834.5 mAh g^(−1) after 300 cycles at 4.2 A/g, while the as-prepared S cathode exhibits enhanced cycling performance with high remaining discharge capacities of 663.4 mAh g^(−1) after 100 cycles at 0.2 C and 487.07 mAh g^(−1) after 300 cycles at 1 C, respectively. These encouraging results suggest that PMVEMA could be a universal binder to facilitate the green manufacture of both anode and cathode for high-capacity energy storage systems.
基金supported by Joint Funds of the National Natural Science Foundation of China(U20A20280)the National Natural Science Foundation of China(21805083,52074119)+3 种基金the Academy of Sciences large apparatus United Fund of China(U1832187)the Scientific Research Fund of Hunan Provincial Education Department(19K058)the Science and Technology Planning Project of Hunan Province(2018TP1017)the High-Tech Leading Plan of Hunan Province(2020GK2072).
文摘Silicon-based(Si)materials are promising anodes for lithium-ion batteries(LIBs)because of their ultrahigh theoretical capacity of 4200 mA h g^(−1).However,commercial applications of Si anodes have been hindered by their drastic volume variation(∼300%)and low electrical conductivity.Here,to tackle the drawbacks,a hierarchical Si anode with double-layer coatings of a SiOx inner layer and a nitrogen(N),boron(B)co-doped carbon(C-NB)outer layer is elaborately designed by copyrolysis of Si-OH structures and a H3BO_(3)-doped polyaniline polymer on the Si surface.Compared with the pristine Si anodes(7mA h g^(−1) at 0.5 A g^(−1) after 340 cycles and 340 mA h g^(−1) at 5 A g^(−1)),the modified Si-based materials(Si@SiOx@C-NB nanospheres)present su perior cycling stability(reversible 1301 mA h g^(−1) at 0.5 A g^(−1) after 340 cycles)as well as excellent rate capability(690mA h g^(−1) at 5 A g^(−1))when used as anodes in LIBs.The unique double-layer coating structure,in which the inner amorphous SiOx layer acts as a buffer matrix and the outer defect-rich carbon enhances the electron diffusion of the whole anode,makes it possible to de liver excellent electrochemical properties.These results indicate that our double-layer coating strategy is a promising approach not only for the devel opment of sustainable Si anodes but also for the design of multielement-doped carbon nanomaterials.
文摘We report the synthesis of a high‐performance graphitic carbon‐coated silicon(Si@GC)composite material for lithium‐ion batteries via a scalable production route.Porous Si is produced from the magnesiothermic reduction of commercial silica(SiO2)precursor followed by low‐temperature graphitic carbon coating using glucose as the precursor.The obtained Si@GC composite achieves an excellent reversible specific capacity of 1195 mAh g−1 and outstanding cycle stability.The thick Si@GC anode(3.4 mg cm^−2)in full cells with commercial lithium iron phosphate cathode delivers a remarkable performance of 800 mAh g^−1 specific capacity and 2.7 mAh cm^−2 areal capacity as well as 93.6%capacity retention after 200 cycles.
基金financial support from the Australia Research Council Discovery Projects(DP160102627 and DP1701048343)of Australiathe 111 Project(D20015)of China Three Gorges University
文摘Silicon(Si)has been investigated as a promising anode material because of its high theoretical capacity(4200 m Ah g^(-1)).However,silicon anode suffers from huge volume changes during repeated charge–discharge cycles.In this work,inspired by a remarkable success of the glutinous rice mortar in the Great Wall with ca.2000-year history,amylopectin(AP),the key ingredient responsible for the strong bonding force,is extracted from glutinous rice and utilized as a flexible,aqueous,and resilient binder to address the most challenging drastic volume-expansion and pulverization issues of silicon anode.Additionally,the removal of toxic N-methyl-2-pyrrolidone(NMP)organic solvent makes the electrode fabrication process environmentally friendly and healthy.The as-prepared Si-AP electrode with 60 wt%of Si can uphold a high discharge capacity of 1517.9 m Ah g^(-1)at a rate of 0.1 C after 100 cycles.The cycling stability of the Si-AP has been remarkably improved in comparison with both traditional polyvinylidene fluoride(PVDF)and aqueous carboxymethylcellulose(CMC)binders.Moreover,when the content of silicon in the Si-AP electrode increases to 70 wt%,a high discharge capacity of 1463.1 m Ah g^(-1)can still be obtained after 50 cycles at 0.1°C.These preliminary results suggest that the sustainably available and environmentally benign amylopectin binders could be a promising choice for the construction of highly stable silicon anodes.
基金financially supported by the National Natural Science Foundation of China(No.22209075)the Natural Science Foundation of Jiangsu Province(BK20200800)。
文摘Silicon has ultrahigh capacity,dendrite-free alloy lithiation mechanism and low cost and has been regarded as a promising anode candidate for solid-state battery.Owing to the low infiltration of solid-state electrolyte(SSE),not the unstable solid-electrolyte interphase(SEI),but the huge stress during lithiation-and delithiation-induced particle fracture and conductivity lost tend to be the main issues.In this study,starting with micron-Si,a novel monothetic carbon conductive framework and a MgO coating layer are designed,which serve as electron pathway across the whole electrode and stress releasing layer,respectively.In addition,the in situ reaction between Si and SSE helps to form a LiF-rich and mechanically stable SEI layer.As a result,the mechanical stability and charge transfer kinetics of the uniquely designed Si anode are significantly improved.Consequently,high initial Coulombic efficiency,high capacity and durable cycling stability can be achieved by applying the Si@MgO@C anode in SSB.For example,high specific capacity of 3224.6 mAh·g^(-1)and long cycling durability of 200 cycles are achieved.This work provides a new concept for designing alloy-type anode that combines surface coating on particle and electrode structure design.
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-NH2 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This work was supported by the General Research Fund scheme of the Hong Kong Research Grants Council(Project No.15227121)the Hong Kong Polytechnic University(ZVGH).
文摘Si is a promising anode material for Li ion batteries because of its high specific capacity,abundant reserve,and low cost.However,its rate performance and cycling stability are poor due to the severe particle pulverization during the lithiation/delithiation process.The high stress induced by the Li concentration gradient and anisotropic deformation is the main reason for the fracture of Si particles.Here we present a new stress mitigation strategy by uniformly distributing small amounts of Sn and Sb in Si micron-sized particles,which reduces the Li concentration gradient and realizes an isotropic lithiation/delithiation process.The Si8.5Sn0.5Sb microparticles(mean particle size:8.22μm)show over 6000-fold and tenfold improvements in electronic conductivity and Li diffusivity than Si particles,respectively.The discharge capacities of the Si_(8.5)Sn_(0.5)Sb microparticle anode after 100 cycles at 1.0 and 3.0 A g^(-1)are 1.62 and 1.19 Ah g^(-1),respectively,corresponding to a retention rate of 94.2%and 99.6%,respectively,relative to the capacity of the first cycle after activation.Multicomponent microparticle anodes containing Si,Sn,Sb,Ge and Ag prepared using the same method yields an ultra-low capacity decay rate of 0.02%per cycle for 1000 cycles at 1 A g^(-1),corroborating the proposed mechanism.The stress regulation mechanism enabled by the industry-compatible fabrication methods opens up enormous opportunities for low-cost and high-energy-density Li-ion batteries.
基金financially supported by the National Natural Science Foundation of China(Nos.52002151 and 51905526)Jiaxing Science and Technology Project(No.2020AY10018)the Key Laboratory of Yam Materials Forming and Composite Processing Technology,Zhejiang Province(open project program,No.MTC2021-10)。
文摘Nowadays,silicon has become a promising anode active material for lithium-ion batteries due to its high specific capacity.However,traditional binder materials cannot effectively restrain the volume expansion of silicon during lithiation/delithiation.Inspired by the growth process of climbing plants,we sequentially crosslink sodium alginate with calcium ions and hyperbranched polyethyleneimine to construct a dual crosslinked network binder.During the sequentially crosslinking,sodium alginate preferentially crosslinks with Ca^(2+)to form the"trellis"network,which restricts the free movement of hyperbranched polyethyleneimine and guides it,like"vine",to gradually anchor on the surrounding"trellis"through hydrogen and ionic bonding.In this dual crosslinked network,the ionic ally crosslinked sodium alginate maintains the anode structural integrity;the anchored hyperbranched polyethyleneimine forms strong multidimensional hydrogen bonds with silicon nanoparticles through its amino-rich branch chains;and the network utilizes the bonding reversibility of hydrogen and ionic bonds to repeatedly eliminate the mechanical stress and self-heal the structure damages caused by the volume change of silicon.Benefited from the multifunction of the dual crosslinked network,the silicon anode has achieved an excellent electrochemical performance with a specific capacity of 2403 mAh·g^(-1)at the current density of500 mA·g^(-1)after 100 cycles.
基金supported by the National Key R&D Program of China(No.2018YFA0209600)the National Natural Science Foundation of China(Nos.22022813 and 21878268)the Leading Innovative and Entrepreneur Team Introduction Program of Zhejiang(No.2019R01006).
文摘Sulfide solid electrolyte(SE)is one of the most promising technologies for all-solid-state batteries(ASSBs)because of its high ionic conductivity and ductile mechanical properties.In order to further improve the energy density of sulfide-based ASSBs and promote practical applications,silicon anodes with ultrahigh theoretical capacity(4,200 mAh·g^(−1))and rich resource abundance have broad commercial prospects.However,significant challenges including bulk instability of sulfide SEs and poor utilization of silicon materials have severely impeded the ASSBs from becoming viable.In this review,we first introduce the critical bulk properties of sulfide SEs and the most recent improving strategies covering the ionic conductivity,air stability,electrochemical window,mechanical stability,thermostability and solvent stability.Next,we introduce the main factors affecting the compatibility of silicon and sulfide SE,including the carbon’s effect,particle size of silicon,external pressure,silicon composite matrix and the depth of silicon’s lithiation.Finally,we discuss possible research directions in the future.We hope that this review can provide a comprehensive picture of the role of nanoscale approaches in recent advances in ASSBs with sulfide and silicon,as well as a source of inspiration for future research.
基金supported by the National Natural Science Foundation of China(No.51977185,51972277)Southwest Jiaotong University Science and Technology Rising Star Program(No.2682021CG021).
文摘Silicon-based anodes with high theoretical capacity have intriguing potential applications for high energy density lithium-ion batteries(LIBs),while suffer from immense volumetric change and brittle solidstate electrolyte interface that causes collapse of electrodes.Here,a stress-dissipated conductive polymer binder(polyaniline with citric acid,PC)is developed to enhance the mechanical electrochemical performance between Si nanoparticles(SiNPs)and binders.Benefiting from the stable triangle network node of citric acid and a considerable distributed of hydroxyl groups,the PC binder can effectively dissipate the stress from SiNPs,thus providing an excellent cyclic stability of Si anodes.Both experimental results and theoretical calculation demonstrate the enhanced adhesion between binders and SiNPs could bond the particles tightly to form a robust electrode.The as-fabricated Si anode exhibits outstanding structural stability upon long-term cycles that exhibit a highly reversible capability of 1021 mA·h·g^(-1)over 500 cycles at a current density of 0.5 C(1 C¼4200mA·g^(-1)).Evidently,this stressdissipated binder design will provide a promising route to achieve long-life Si-based LIBs.
基金supported by the Innovation Fund of Wuhan National Laboratory for Optoelectronics of Huazhong University of Science and Technology.
文摘Silicon(Si)is a potential high-capacity anode material for the next-generation lithium-ion battery with high energy density.However,Si anodes suff er from severe interfacial chemistry issues,such as side reactions at the electrode/electrolyte interface,leading to poor electrochemical cycling stability.Herein,we demonstrate the fabrication of a conformal fl uorine-containing carbon(FC)layer on Si particles(Si-FC)and its in situ electrochemical conversion into a LiF-rich carbon layer above 1.5 V(vs.Li^(+)/Li).The as-formed LiF-rich carbon layer not only isolates the active Si and electrolytes,leading to the suppression of side reactions,but also induces the formation of a robust solid-electrolyte interface(SEI),leading to the stable interfacial chemistry of as-designed Si-FC particles.The Si-FC electrode has a high initial Coulombic effi ciency(CE)of 84.8%and a high reversible capacity of 1450 mAh/g at 0.4 C(1000 mA/g)for 300 cycles.In addition,a hybrid electrode consisting of 85 wt%graphite and 15 wt%Si-FC,and mass 2.3 mg/cm^(2) loading delivers a high areal capacity of 2.0 mAh/cm^(2) and a high-capacity retention of 93.2%after 100 cycles,showing the prospects for practical use.
基金supported by the National Research Foundation, Prime Minister’s Office, Singapore, under its Competitive Research Programme (CRP award number NRF-CRP22-2019-008)Medium-Sized Centre Programme (CA2DM)+1 种基金the Ministry of Education of Singapore, under its Research Centre of Excellence award to the Institute for Functional Intelligent Materials (I-FIM, Project No. EDUNC-33-18-279-V12)by the EDB Singapore, under its Space Technology Development Programme (S2219013-STDP)。
文摘Despite advancements in silicon-based anodes for high-capacity lithium-ion batteries,their widespread commercial adoption is still hindered by significant volume expansion during cycling,especially at high active mass loadings crucial for practical use.The root of these challenges lies in the mechanical instability of the material,which subsequently leads to the structural failure of the electrode.Here,we present a novel synthesis of a composite combining expanded graphite and silicon nanoparticles.This composite features a unique interlayer-bonded graphite structure,achieved through the application of a modified spark plasma sintering method.Notably,this innovative structure not only facilitates efficient ion and electron transport but also provides exceptional mechanical strength(Vickers hardness:up to658 MPa,Young's modulus:11.6 GPa).This strength effectively accommodates silicon expansion,resulting in an impressive areal capacity of 2.9 mA h cm^(-2)(736 mA h g^(-1)) and a steady cycle life(93% after 100cycles).Such outsta nding performance is paired with features appropriate for large-scale industrial production of silicon batteries,such as active mass loading of at least 3.9 mg cm^(-2),a high-tap density electrode material of 1.68 g cm^(-3)(secondary clusters:1.12 g cm^(-3)),and a production yield of up to 1 kg per day.
基金Guangdong Basic and Applied Basic Research Foundation,Grant/Award Number:2020A1515110762Research Grants Council of the Hong Kong Special Administrative Region,China,Grant/Award Number:R6005‐20Shenzhen Key Laboratory of Advanced Energy Storage,Grant/Award Number:ZDSYS20220401141000001。
文摘Silicon(Si)is widely used as a lithium‐ion‐battery anode owing to its high capacity and abundant crustal reserves.However,large volume change upon cycling and poor conductivity of Si cause rapid capacity decay and poor fast‐charging capability limiting its commercial applications.Here,we propose a multilevel carbon architecture with vertical graphene sheets(VGSs)grown on surfaces of subnanoscopically and homogeneously dispersed Si–C composite nanospheres,which are subsequently embedded into a carbon matrix(C/VGSs@Si–C).Subnanoscopic C in the Si–C nanospheres,VGSs,and carbon matrix form a three‐dimensional conductive and robust network,which significantly improves the conductivity and suppresses the volume expansion of Si,thereby boosting charge transport and improving electrode stability.The VGSs with vast exposed edges considerably increase the contact area with the carbon matrix and supply directional transport channels through the entire material,which boosts charge transport.The carbon matrix encapsulates VGSs@Si–C to decrease the specific surface area and increase tap density,thus yielding high first Coulombic efficiency and electrode compaction density.Consequently,C/VGSs@Si–C delivers excellent Li‐ion storage performances under industrial electrode conditions.In particular,the full cells show high energy densities of 603.5 Wh kg^(−1)and 1685.5 Wh L^(−1)at 0.1 C and maintain 80.7%of the energy density at 3 C.
基金supported by the National Natural Science Foundation of China(5197219862133007)the Taishan Scholars Program of Shandong Province(tsqn201812002,ts20190908)+1 种基金the Shenzhen Fundamental Research Program(JCYJ20190807093405503)The Natural Science Foundation of Shandong Province(No.ZR2020JQ19)。
文摘Silicon(Si)has been studied as a promising alloying type anode for lithium-ion batteries due to its high specific capacity,low operating potential and abundant resources.Nevertheless,huge volume expansion during alloying/dealloying processes and low electronic conductivity of Si anodes restrict their electrochemical performance.Thus,carbon(C)materials with special physical and chemical properties are applied in Si anodes to effectively solve these problems.This review focuses on current status in the exploration of Si/C anodes,including the lithiation mechanism and solid electrolyte interface formation,various carbon sources in Si/C anodes,such as traditional carbon sources(graphite,pitch,biomass),and novel carbon sources(MXene,graphene,MOFs-derived carbon,graphdiyne,etc.),as well as interfacial bonding modes of Si and C in the Si/C anodes.Finally,we summarize and prospect the selection of carbonaceous materials,structural design and interface control of Si/C anodes,and application of Si/C anodes in all-solid-state lithium-ion batteries and sodium-ion batteries et al.This review will help researchers in the design of novel Si/C anodes for rechargeable batteries.
基金supported by the National Natural Science Foundation of China(No.51602250)Thousand Youth Talents Plan Project of China
文摘Silicon anodes have drawn ever-increasing attention in lithium-ion batteries(LIBs) owing to their extremely high theoretical capacity and abundance in the earth. Despite promising advantages, the wide use of silicon anodes in LIBs is highly hindered by their fast capacity fading and low Coulombic efficiency arising from their substantial volumetric variation(>300%). Herein, we report a novel aqueous hybrid gel binder for silicon anodes via crosslinking sodium carboxymethyl cellulose(NaCMC) by an inorganic crosslinker-sodium borate. Not only this gel polymer binder can chemically bond to silicon nanoparticle, but also the deformable framework of this crosslinked binder is capable of maintaining electrode integrity, thus buffering dramatic volume change of silicon. Consequently, the silicon anode with this gel binder exhibits good cycle life(1211.5 mAh/g after 600 cycles) and high initial Coulombic efficiency(88.95%).
基金financially supported by the National Natural Science Foundation of China (U2004210, 51974208, U2003130, 21875080, 52002297)the Outstanding Youth Foundation of Natural Science Foundation of Hubei Province (2020CFA099)+2 种基金the Special Project of Central Government for Local Science and Technology Development of Hubei Province (2019ZYYD024)the Innovation group of Natural Science Foundation of Hubei Province (2019CFA020)the City University of Hong Kong Strategic Research Grants (7005505)。
文摘Silicon (Si) is a promising anode material for next-generation high-energy lithium-ion batteries (LIBs) due to its high capacity.However,the large volumetric expansion,poor ion conductivity and unstable solid electrolyte interface (SEI) lead to rapid capacity fading and low rate performance.Herein,we report Si nitride (SiN) comprising stoichiometric Si_(3)N_(4) and Li-active anazotic SiN_(x) coated porous Si (p-Si@SiN)for high-performance anodes in LIBs.The ant-nest-like porous Si consisting of 3D interconnected Si nanoligaments and bicontinuous nanopores prevents pulverization and accommodates volume expansion during cycling.The Si_(3)N_(4) offers mechanically protective coating to endow highly structural integrity and inhibit superfluous formation of SEI.The fast ion conducting Li_(3)N generated in situ from lithiation of active SiN_(x) facilitates Li ion transport.Consequently,the p-Si@SiN anode has appealing electrochemical properties such as a high capacity of 2180 mAh g^(-1)at 0.5 A g^(-1) with 84%capacity retention after 200cycles and excellent rate capacity with discharge capacity of 721 mAh g^(-1) after 500 cycles at 5.0 A g^(-1).This work provides insights into the rational design of active/inactive nanocoating on Si-based anode materials for fast-charging and highly stable LIBs.
基金The authors are very grateful to the National Natural Science Foundation of China(NSFC no.21875154 and 21473120)for funding.
文摘Lithium-ion battery anode used as silicon particles were obtained from different major suppliers,and they were characterized by different spectroscopic techniques and evaluated by electrochemical experiments.Correlations between the key physical parameters and electrochemical properties of the silicon particles were investigated.Silicon particle size,surface oxygen content,-OH content and physical appearance are found to strongly influence the electrochemical properties of the Si anode.The particle size of 100 nm has great promise for the practical application of Si nanoparticles in the lithium-ion battery industry.An inverse correlation between the oxygen content and the reversible capacity or first coulombic efficiency was obtained.The-OH content by surface treatment contributes to enhanced cycling stability by the improved affinity between the Si particle and the water-soluble binder.Spherical Si particles perform better compared to irregular particles,and agglomeration dramatically decreases the cycling stability of the Si anode.Among the investigated Si particles,the sample that exhibited a reversible capacity of more than 2500 mAh g^(-1),a first coulombic efficiency of 89.26%and an excellent cycling stability,has great potential for use in the battery industry.
基金Project supported by the China Postdoctoral Science Foundation(Grant No.2016M592115)the Jiangxi Postdoctoral Foundation,China(Grant No.2015KY12)+1 种基金the Fund from the Jiangxi Provincial Education Department,China(Grant No.150184)the Fund from Nanchang University,China(Grant No.CX2017006)
文摘In this paper, two types of silicon(Si) particles ball-milled from n-type Si wafers, respectively, with resistivity values of 1 Ω·cm and 0.001 Ω·cm are deposited with silver(Ag). The Ag-deposited n-type 1-Ω·cm Si particles(nl-Ag) and Ag-deposited n-type 0.001-Ω·cm Si particles(n0.001-Ag) are separately used as an anode material to assemble coin cells,of which the electrochemical performances are investigated. For the matching of work function between n-type 1-Ω·cm Si(nl) and Ag, nl-Ag shows discharge specific capacity of up to 683 mAh·g^-1 at a current density of 8.4 A·g^-1, which is40% higher than that of n0.001-Ag. Furthermore, the resistivity of nl-Ag is lower than half that of n0.001-Ag. Due to the mismatch of work function between n-type 0.001-Ω·cm Si(n0.001) and Ag, the discharge specific capacity of n0.001-Ag is 250.2 mAh·g^-1 lower than that of nl-Ag after 100 cycles.