Poor Li plating reversibility and high thermal runaway risks are key challenges for fast charging lithiumion batteries with graphite anodes.Herein,a dielectric and fire-resistant separator based on hybrid nanofibers o...Poor Li plating reversibility and high thermal runaway risks are key challenges for fast charging lithiumion batteries with graphite anodes.Herein,a dielectric and fire-resistant separator based on hybrid nanofibers of barium sulfate(BS)and bacterial cellulose(BC)is developed to synchronously enhance the battery's fast charging and thermal-safety performances.The regulation mechanism of the dielectric BS/BC separator in enhancing the Li^(+)ion transport and Li plating reversibility is revealed.(1)The Max-Wagner polarization electric field of the dielectric BS/BC separator can accelerate the desolvation of solvated Li^(+)ions,enhancing their transport kinetics.(2)Moreover,due to the charge balancing effect,the dielectric BS/BC separator homogenizes the electric field/Li^(+)ion flux at the graphite anode-separator interface,facilitating uniform Li plating and suppressing Li dendrite growth.Consequently,the fast-charge graphite anode with the BS/BC separator shows higher Coulombic efficiency(99.0%vs.96.9%)and longer cycling lifespan(100 cycles vs.59 cycles)than that with the polypropylene(PP)separator in the constantlithiation cycling test at 2 mA cm^(-2).The high-loading LiFePO4(15.5 mg cm^(-2))//graphite(7.5 mg cm^(-2))full cell with the BS/BC separator exhibits excellent fast charging performance,retaining 70%of its capacity after 500 cycles at a high rate of 2C,which is significantly better than that of the cell with the PP separator(retaining only 27%of its capacity after 500 cycles).More importantly,the thermally stable BS/BC separator effectively elevates the critical temperature and reduces the heat release rate during thermal runaway,thereby significantly enhancing the battery's safety.展开更多
Fast-charging lithium-ion batteries are highly required,especially in reducing the mileage anxiety of the widespread electric vehicles.One of the biggest bottlenecks lies in the sluggish kinetics of the Li^(+)intercal...Fast-charging lithium-ion batteries are highly required,especially in reducing the mileage anxiety of the widespread electric vehicles.One of the biggest bottlenecks lies in the sluggish kinetics of the Li^(+)intercalation into the graphite anode;slow intercalation will lead to lithium metal plating,severe side reactions,and safety concerns.The premise to solve these problems is to fully understand the reaction pathways and rate-determining steps of graphite during fast Li^(+)intercalation.Herein,we compare the Li^(+)diffusion through the graphite particle,interface,and electrode,uncover the structure of the lithiated graphite at high current densities,and correlate them with the reaction kinetics and electrochemical performances.It is found that the rate-determining steps are highly dependent on the particle size,interphase property,and electrode configuration.Insufficient Li^(+)diffusion leads to high polarization,incomplete intercalation,and the coexistence of several staging structures.Interfacial Li^(+)diffusion and electrode transportation are the main rate-determining steps if the particle size is less than 10μm.The former is highly dependent on the electrolyte chemistry and can be enhanced by constructing a fluorinated interphase.Our findings enrich the understanding of the graphite structural evolution during rapid Li^(+)intercalation,decipher the bottleneck for the sluggish reaction kinetics,and provide strategic guidelines to boost the fast-charging performance of graphite anode.展开更多
With the increased demand from the storage of renewable energy sources,some safe and inexpensive energy storage technologies instead of Li-ion batteries become urgently needed.Therefore,K-ion batteries(KIBs)have attra...With the increased demand from the storage of renewable energy sources,some safe and inexpensive energy storage technologies instead of Li-ion batteries become urgently needed.Therefore,K-ion batteries(KIBs)have attracted much attention and evolved significant development because of the low price,safety,and similar property compared with Li-ion batteries.Due to the high reversibility,stability,and low potential plateau,graphite becomes a current research focus and is regarded as one of the most promising KIB’s anode materials.In this review,we mainly discuss the electrochemical reaction mechanism of graphite during potassiation-depotassiation process and analyze the effects of electrode/electrolyte interface on graphite for Kion storage.Besides,we summarize several kinds of methods to improve the performance of graphite for KIBs,including the design of graphite structure,selection of appropriate binder,solvent chemistry,and salt chemistry.Meanwhile,a concept of“relative energy density”is raised,which can be more accurate to evaluate the genuine electrochemical performance of graphite anode involving the specific capacity and potential.In addition,we also summarize the considerable challenges to current graphite anode in KIBs and we believe our work will offer alterative solutions to further explore high-performance graphite anode of K-ion storage.展开更多
"Dissolution,migration,and deposition"of transition metal ions (TMIs) result in capacity degradation of lithium-ion batteries (LIBs).Understanding such detrimental mechanism of TMIs is critical to the develo..."Dissolution,migration,and deposition"of transition metal ions (TMIs) result in capacity degradation of lithium-ion batteries (LIBs).Understanding such detrimental mechanism of TMIs is critical to the development of LIBs with long cycle life.In most previous works,TMIs were directly introduced into the electrolyte to investigate such a detrimental mechanism.In these cases,the TMIs are deposited directly on the fresh anode surface.However,in the practical battery system,the TMIs are deposited on the anode covered with solid electrolyte interphase (SEI) film.Whether the pre-presence of SEI film on anode surface influences the deposition and detriment of TMIs is unclear.In this work,the deposition of Co element on graphite anode with and without SEI film were systematically studied.The results clearly show that,in comparison with that of fresh graphite (SEI-free),the presence of SEI film aggravates the deposition of Co ions due to the Li^(+)–Co^(2+) ion exchange between the SEI and Co^(2+)-containing electrolyte without the driving of the electric field,leading to faster capacity fading of graphite anode.Therefore,how to regulate electrolytes and film-forming additives to design the components of SEI and prevent its exchange with TMIs,is a crucial way to inhibit the deposition and detriment of TMIs on graphite anode.展开更多
{3-[2-(2-methoxyethoxy) ethoxy]-propyl} triethoxysilane (TESM2) was synthesized and used as an electrolyte additive to improve the performances of lithium-ion batteries (LIBs). The electrochemical properties of the el...{3-[2-(2-methoxyethoxy) ethoxy]-propyl} triethoxysilane (TESM2) was synthesized and used as an electrolyte additive to improve the performances of lithium-ion batteries (LIBs). The electrochemical properties of the electrolyte (1 mol/L lithium hexafluorophosphate (LiPF 6 )/ethylene carbonate (EC):diethylene carbonate (DEC):dimethyl carbonate (DMC), 1:1:1) with different contents of TESM2 were characterized by ionic conductivity measurement, galvanostatic charge/discharge test of graphite/Li half cells, and electrochemical impedance spectroscopy. Both the cycling performances and C-rate capabilities of graphite/Li half cells were significantly improved with an optimized content of 15% TESM2 in the electrolyte. The graphite/Li half cell delivered a very high specific capacity of 370 mAh/g at 0.2C rate without any capacity loss for 60 cycles, and retained a capacity of 292 mAh/g at 2C rate. The solid electrolyte interphase (SEI) film on the surface of the graphite anode was investigated by scanning electron microscopy (SEM) and energy dispersive spectroscopy (EDS), indicating that TESM2 was effectively involved in the formation of SEI film on the surface of graphite.展开更多
Weakly-solvated electrolytes(WSEs)utilizing solvents with weak coordination ability offer advantages for low-potential graphite anode owing to their facile desolvation process and anions-derived inorganic-rich solid e...Weakly-solvated electrolytes(WSEs)utilizing solvents with weak coordination ability offer advantages for low-potential graphite anode owing to their facile desolvation process and anions-derived inorganic-rich solid electrolyte interphase(SEI)film.However,these electrolytes face challenges in achieving a balance between the weak solvation affinity and high ionic conductivity,as well as between rigid inorganic-rich SEI and flexible SEI for long-term stability.Herein,we introduce 1,3-dioxolane(DOL)and lithium bis(trifluoromethanesulfonyl)-imide(LiTFSI)as functional additives into a WSE based on nonpolar cyclic ether(1,4-dioxane).The well-formulated WSE not only preserves the weakly solvated features and anion-dominated solvation sheath,but also utilizes DOL to contribute organic species for stabilizing the SEI layer.Benefitting from these merits,the optimized electrolyte enables graphite anode with excellent fast-charging performance(210 mAh/g at 5 C)and outstanding cycling stability(600 cycles with a capacity retention of 82.0%at room temperature and 400 cycles with a capacity retention of 80.4%at high temper-ature).Furthermore,the fabricated LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2)||graphite full cells demonstrate stable operation for 140 cycles with high capacity retention of 80.3%.This work highlights the potential of tailoring solvation sheath and interphase properties in WSEs for advanced electrolyte design in graphite-based lithium-ion batteries.展开更多
In this paper, the formation mechanism of the passive SEI film at the natural graphite anodes was investigated with tilt: electrochemical impedance spectroscopy (EIS). A characteristic semicircle was observed in the l...In this paper, the formation mechanism of the passive SEI film at the natural graphite anodes was investigated with tilt: electrochemical impedance spectroscopy (EIS). A characteristic semicircle was observed in the lower frequency range of the EIS spectrum for the irreversible charge process (lithium intercalation) at ca. 0.75V, 0.40V and 0.20V.展开更多
Recycling graphite anode from spent lithium-ion batteries(SLIBs)is regarded as a crucial approach to promoting sustainable energy storage industry.However,the recycled graphite(RG)generally presents degraded structure...Recycling graphite anode from spent lithium-ion batteries(SLIBs)is regarded as a crucial approach to promoting sustainable energy storage industry.However,the recycled graphite(RG)generally presents degraded structure and performance.Herein,the residual fluoride self-activated effect is proposed for the upgraded utilization of RG.Simple and low-energy water immersion treatment not only widens the interlayer spacing,but also retains appropriate fluoride on the surface of RG.Theoretical analysis and experiments demonstrate that the residual fluoride can optimize Li~+migration and deposition kinetics,resulting in better Li~+intercalation/deintercalation in the interlayer and more stable Li metal plating/stripping on the surface of RG,As a result,the designed LFP||RG full cells achieve ultrahigh reversibility(~100%Coulombic efficiency),high capacity retention(67%after 200 cycles,0.85 N/P ratio),and commendable adaptability(stable cycling without short-circuiting,0.15 N/P ratio).The energy density is improved from 334 Wh kg^(-1)of 1.1 N/P ratio to 367 Wh kg^(-1)of 0.85 N/P ratio(total mass based on cathode and anode).The exploration of RG by residual fluoride self-activated effect achieves upgraded utilization beyond fresh commercial graphite and highlights a new strategy for efficient reuse of SLIBs.展开更多
Graphite interfaces are an important part of the anode in lithium-ion batteries(LIBs),significantly influencing Li intercalation kinetics.Graphite anodes adopt different stacking sequences depending on the concentrati...Graphite interfaces are an important part of the anode in lithium-ion batteries(LIBs),significantly influencing Li intercalation kinetics.Graphite anodes adopt different stacking sequences depending on the concentration of the intercalated Li ions.In this work,we performed first-principles calculations to comprehensively address the energetics and dynamics of Li intercalation and Li vacancy diffusion near the no n-basal edges of graphite,namely the armchair and zigzag-edges,at high Li concentration.We find that surface effects persist in stage-Ⅱ that bind Li strongly at the edge sites.However,the pronounced effect previously identified at the zigzag edge of pristine graphite is reduced in LiC_(12),penetrating only to the subsurface site,and eventually disappearing in LiC_(6).Consequently,the distinctive surface state at the zigzag edge significantly impacts and restrains the charging rate at the initial lithiation of graphite anodes,whilst diminishes with an increasing degree of lithiation.Longer diffusion time for Li hopping to the bulk site from either the zigzag edge or the armchair edge in LiC_(6) was observed during high state of charge due to charge repulsion.Effectively controlling Li occupation and diffusion kinetics at this stage is also crucial for enhancing the charge rate.展开更多
To improve the rate capability and cyclability of natural graphite anode for Li-ion batteries,a novel modification approach was developed.The modification approach included two steps:(a)high-energy ball milling in a r...To improve the rate capability and cyclability of natural graphite anode for Li-ion batteries,a novel modification approach was developed.The modification approach included two steps:(a)high-energy ball milling in a rotary autoclave containing alumina balls,H_3PO_4 and ethanol;(b)coating with pyrolytic carbon from phenlic resin.The treated graphite shows obvious improvement compared with the original natural graphite in electrochemical properties such as cyclability and rate capability,especially at high current density.The primary reasons leading to the improvement in rate capability and cyclability are that the diffusion impedance of Li^+ in graphite is reduced due to the fact that P filtered into graphite layers can mildly increase interlayer distances,and the fact that the structural stability of graphite surface is enhanced since the coated pyrolytic carbon can depress the co-intercalation of solvated lithium ion.展开更多
Cycling and rate performance of natural graphite is still limited by the sluggish kinetics of lithium ions,which can be improved by surface modifications in previous research.Among these methods,amorphous carbon coati...Cycling and rate performance of natural graphite is still limited by the sluggish kinetics of lithium ions,which can be improved by surface modifications in previous research.Among these methods,amorphous carbon coating has been proved to be mature and efficient.However,the significance of coating uniformity in relation to solid electrolyte interphase(SEI)has been largely overlooked.In this study,the uniformity of amorphous carbon coating is adjusted by the particle size of pitch.When discharged-charged at 1 C,graphite half-cells with such uniform coating show 90.3%of the capacity at 0.1 C,while that is 82.1%for non-uniform coating.Additionally,improved initial coulombic efficiency and cycling stability are demonstrated.These can be attributed to graphite anodes featuring a uniform carbon coating that promotes effective and homogeneous LiF formation within the inorganic matrix.This leads to the establishment of a stabilized SEI,confirmed by time-of-flight secondary ion mass spectrometry(TOF-SIMS).This work provides valuable reference into the rational control of graphite interfaces for high electrochemical performance.展开更多
Graphite is a dominant anode material for lithium-ion batteries(LIBs)due to its outstanding electrochemical performance.However,slow lithium ion(Li+)kinetics of graphite anode restricts its further application.Herein,...Graphite is a dominant anode material for lithium-ion batteries(LIBs)due to its outstanding electrochemical performance.However,slow lithium ion(Li+)kinetics of graphite anode restricts its further application.Herein,we report that high-temperature shock(HTS)can drive spent graphite(SG)into defect-rich recycled graphite(DRG)which is ideal for high-rate anode.The DRG exhibits the charging specific capacity of 323 mAh/g at a high current density of 2 C,which outperforms commercial graphite(CG,120 mAh/g).The eminent electrochemical performance of DRG can be attributed to the recovery of layered structure and partial remaining defects of SG during ultrafast heating and cooling process,which can effectively reduce total strain energy,accelerate the phase transition in thermodynamics and improve the Li+diffusion.This study provides a facile strategy to guide the re-graphitization of SG and design high performance battery electrode materials by defect engineering from the atomic level.展开更多
Lithium plating on graphite anode is triggered by harsh conditions of fast charge and low temperature,which sig-nificantly accelerates SOH(state of health)degradation and may cause safety issues of lithium ion batteri...Lithium plating on graphite anode is triggered by harsh conditions of fast charge and low temperature,which sig-nificantly accelerates SOH(state of health)degradation and may cause safety issues of lithium ion batteries(LIBs).This paper has reviewed recent research progress of lithium plating on graphite anode.Firstly,we summarize the forming mechanisms of Li plating with(corresponding influence factors,the detect-ing methods and hazard of Li plating.Then,approaches to suppress Li plating are discussed,including anode surface modification,electrolyte composition optimization and development of optimal charge.strategies.Finally,we con-clude and propose the remaining challenges and prospects in terms of mechanism research,detecting approaches,and suppressing methods of Li plating.This review highlights the development of Li plating research and plays a guiding rule of further study on Li plating in LIBs.展开更多
Although graphite anodes operated with representative de/intercalation patterns at low potentials are considered highly desirable for K-ion batteries,the severe capacity fading caused by consecutive reduction reaction...Although graphite anodes operated with representative de/intercalation patterns at low potentials are considered highly desirable for K-ion batteries,the severe capacity fading caused by consecutive reduction reactions on the aggressively reactive surface is inevitable given the scarcity of effective protecting layers.Herein,by introducing a flame-retardant localized high-concentration electrolyte with retentive solvation configuration and relatively weakened anion-coordination and non-solvating fluorinated ether,the rational solid electrolyte interphase characterized by well-balanced inorganic/organic components is tailored in situ.This effectively prevented solvents from excessively decomposing and simultaneously improved the resistance against K-ion transport.Consequently,the graphite anode retained a prolonged cycling capability of up to 1400 cycles(245 mA h g,remaining above 12 mon)with an excellent capacity retention of as high as 92.4%.This is superior to those of conventional and high-concentration electrolytes.Thus,the optimized electrolyte with moderate salt concentration is perfectly compatible with graphite,providing a potential application prospect for K-storage evolution.展开更多
Due to the presence of graphite flake cascades, the real graphite anode of Li-ion battery shows non-iso- tropic characteristic. The present work developed an ellipsoid-based simulated annealing method and numeri- call...Due to the presence of graphite flake cascades, the real graphite anode of Li-ion battery shows non-iso- tropic characteristic. The present work developed an ellipsoid-based simulated annealing method and numeri- cally reconstructed the three-dimensional microstructure of a graphite anode. The reconstructed anode is a composite of three clearly distinguished phases： pore （or electrolyte）, graphite, and solid additives, well representing the non- isotropic heterogeneous characteristic of real graphite anode. Characterization analysis of the reconstructed electrode gives information such as the connectivity of individual phase, the specific interracial area between solid and pore phase, and the pore size distribution. The effects of the ellipsoid size on the structural characteristics of graphite anode were particularly studied. As the size of the ellipsoidal particle slightly increases, the average pore diameter increases and as a result the specific interfacial area between the solid and pore phase in the reconstructed area decreases; compared with the equatorial radius, the polar radius of ellipsoidal graphite particles has more sig- nificant influence on the characteristics of electrode microstructure.展开更多
1 Results Propylene carbonate (PC) is well known having a series of excellent properties including low melting point,wide liquid-phase range and wide electrochemical window.In addition,PC is well compatible with diffe...1 Results Propylene carbonate (PC) is well known having a series of excellent properties including low melting point,wide liquid-phase range and wide electrochemical window.In addition,PC is well compatible with different cathode materials.However,the poor compatibility of PC with graphite anode limits the utilization of PC solvent into lithium ion batteries.It is generally accepted that PC molecules co-intercalate into graphite interlayer with solvated Li ions and cause exfoliation of graphite structur...展开更多
As lithium(Li)-ion batteries expand their applications,operating over a wide temperature range becomes increasingly important.However,the lowtemperature performance of conventional graphite anodes is severely hampered...As lithium(Li)-ion batteries expand their applications,operating over a wide temperature range becomes increasingly important.However,the lowtemperature performance of conventional graphite anodes is severely hampered by the poor diffusion kinetics of Li ions(Li^(+)).Here,zinc oxide(ZnO) nanoparticles are incorporated into the expanded graphite to improve Li^(+)diffusion kinetics,resulting in a significant improvement in lowtemperature performance.The ZnO-embedded expanded graphite anodes are investigated with different amounts of ZnO to establish the structurecharge storage mechanism-performance relationship with a focus on lowtemperature applications.Electrochemical analysis reveals that the ZnOembedded expanded graphite anode with nano-sized ZnO maintains a large portion of the diffusion-controlled charge storage mechanism at an ultra-low temperature of-50℃ Due to this significantly enhanced Li^(+)diffusion rate,a full cell with the ZnO-embedded expanded graphite anode and a LiNi_(0.88)Co_(0.09)Al_(0.03)O_(2)cathode delivers high capacities of 176 mAh g^(-1)at20℃ and 86 mAh g^(-1)at-50℃ at a high rate of 1 C.The outstanding low-temperature performance of the composite anode by improving the Li^(+)diffusion kinetics provides important scientific insights into the fundamental design principles of anodes for low-temperature Li-ion battery operation.展开更多
Lithium-ion battery has greatly changed our lifestyle and the solid electrolyte interphase(SEI)covered on the graphite anode determines the service life of a battery.The formation method and the formation temperature ...Lithium-ion battery has greatly changed our lifestyle and the solid electrolyte interphase(SEI)covered on the graphite anode determines the service life of a battery.The formation method and the formation temperature at initial cycle of a battery determine the feature of the SEI.Herein,we investigate the gap of formation behavior in both a half cell(graphite matches with lithium anode)and a full cell(graphite matches with NCM,short for LiNixCoyMn1-x-yO2)at different temperatures.We conclude that high temperature causes severe side reactions and low temperature will result in low ionic conductive SEI layer,the interface formed at room temperature owns the best ionic conductivity and stability.展开更多
A capacity increase is often observed in the early stage of Li-ion battery cycling.This study explores the phenomena involved in the capacity increase from the full cell,electrodes,and materials perspective through a ...A capacity increase is often observed in the early stage of Li-ion battery cycling.This study explores the phenomena involved in the capacity increase from the full cell,electrodes,and materials perspective through a combination of non-destructive diagnostic methods in a full cell and post-mortem analysis in a coin cell.The results show an increase of 1%initial capacity for the battery aged at 100%depth of discharge(DOD)and 45℃.Furthermore,large DODs or high temperatures accelerate the capacity increase.From the incremental capacity and differential voltage(IC-DV)analysis,we concluded that the increased capacity in a full cell originates from the graphite anode.Furthermore,graphite/Li coin cells show an increased capacity for larger DODs and a decreased capacity for lower DODs,thus in agreement with the full cell results.Post-mortem analysis results show that a larger DOD enlarges the graphite dspace and separates the graphite layer structure,facilitating the Li+diffusion,hence increasing the battery capacity.展开更多
The co-utilization of silicon(Si) and graphite(G) has been considered as the preferred strategy to achieve high energy density anode materials,but the effective synergistic integration of Si and graphite is still a ch...The co-utilization of silicon(Si) and graphite(G) has been considered as the preferred strategy to achieve high energy density anode materials,but the effective synergistic integration of Si and graphite is still a challenge and it is necessary to find a scheme to accommodate the large-scale production of Si/graphite anodes.In this work,silicon cutting waste from the photovoltaic industry was used as raw material,mixed with graphite,pitch,and polyvinylpyrrolidone,and subjected to high-energy ball milling.The mixture was then heated in an Ar atmosphere for the carbon coating,and the resulting Si/graphite/carbon(Si/G/C) composite was etched to remove the thicker SiOx layer formed on the Si surface to allow the pores between the Si and the carbon matrix to obtain Si@voids/G@C.Benefiting from the integrated structural design and the significantly enhanced electronic conductivity,the Si/G@voids@C composite exhibited the first dischargespecific capacity of 2530 mAh·g^(-1) with an initial coulombic efficiency(ICE) of 86.7%,and the remaining capacity exceeded 1000 mAh·g^(-1) after 550 cycles at 1.5A·g^(-1).Notably,full lithium-ion batteries with a Si/G@voids@C anode and LiFePO_4 cathode delivered a stable capacity of 140 mAh·g^(-1).The synthesis method is facile and cost-effective,providing an integration strategy for Si and G with a potential scheme for large-scale commercial applications.展开更多
基金financially supported by the National Natural Science Foundation of China(Grant No.52202328,52372099)the Shanghai Sailing Program(22YF1455500).
文摘Poor Li plating reversibility and high thermal runaway risks are key challenges for fast charging lithiumion batteries with graphite anodes.Herein,a dielectric and fire-resistant separator based on hybrid nanofibers of barium sulfate(BS)and bacterial cellulose(BC)is developed to synchronously enhance the battery's fast charging and thermal-safety performances.The regulation mechanism of the dielectric BS/BC separator in enhancing the Li^(+)ion transport and Li plating reversibility is revealed.(1)The Max-Wagner polarization electric field of the dielectric BS/BC separator can accelerate the desolvation of solvated Li^(+)ions,enhancing their transport kinetics.(2)Moreover,due to the charge balancing effect,the dielectric BS/BC separator homogenizes the electric field/Li^(+)ion flux at the graphite anode-separator interface,facilitating uniform Li plating and suppressing Li dendrite growth.Consequently,the fast-charge graphite anode with the BS/BC separator shows higher Coulombic efficiency(99.0%vs.96.9%)and longer cycling lifespan(100 cycles vs.59 cycles)than that with the polypropylene(PP)separator in the constantlithiation cycling test at 2 mA cm^(-2).The high-loading LiFePO4(15.5 mg cm^(-2))//graphite(7.5 mg cm^(-2))full cell with the BS/BC separator exhibits excellent fast charging performance,retaining 70%of its capacity after 500 cycles at a high rate of 2C,which is significantly better than that of the cell with the PP separator(retaining only 27%of its capacity after 500 cycles).More importantly,the thermally stable BS/BC separator effectively elevates the critical temperature and reduces the heat release rate during thermal runaway,thereby significantly enhancing the battery's safety.
基金supported by the National Natural Science Foundation of China(NSFC No.52172257 and 22005334)the Natural Science Foundation of Beijing(Grant No.Z200013)the National Key Research and Development Program of China(Grant No.2022YFB2502200).
文摘Fast-charging lithium-ion batteries are highly required,especially in reducing the mileage anxiety of the widespread electric vehicles.One of the biggest bottlenecks lies in the sluggish kinetics of the Li^(+)intercalation into the graphite anode;slow intercalation will lead to lithium metal plating,severe side reactions,and safety concerns.The premise to solve these problems is to fully understand the reaction pathways and rate-determining steps of graphite during fast Li^(+)intercalation.Herein,we compare the Li^(+)diffusion through the graphite particle,interface,and electrode,uncover the structure of the lithiated graphite at high current densities,and correlate them with the reaction kinetics and electrochemical performances.It is found that the rate-determining steps are highly dependent on the particle size,interphase property,and electrode configuration.Insufficient Li^(+)diffusion leads to high polarization,incomplete intercalation,and the coexistence of several staging structures.Interfacial Li^(+)diffusion and electrode transportation are the main rate-determining steps if the particle size is less than 10μm.The former is highly dependent on the electrolyte chemistry and can be enhanced by constructing a fluorinated interphase.Our findings enrich the understanding of the graphite structural evolution during rapid Li^(+)intercalation,decipher the bottleneck for the sluggish reaction kinetics,and provide strategic guidelines to boost the fast-charging performance of graphite anode.
基金supports from the National Natural Science Foundation of China(51772135,52002115)the Fundamental Research Funds for the Central Universities(21617330)Science and Technology Development Project of Henan Province(212102210487)。
文摘With the increased demand from the storage of renewable energy sources,some safe and inexpensive energy storage technologies instead of Li-ion batteries become urgently needed.Therefore,K-ion batteries(KIBs)have attracted much attention and evolved significant development because of the low price,safety,and similar property compared with Li-ion batteries.Due to the high reversibility,stability,and low potential plateau,graphite becomes a current research focus and is regarded as one of the most promising KIB’s anode materials.In this review,we mainly discuss the electrochemical reaction mechanism of graphite during potassiation-depotassiation process and analyze the effects of electrode/electrolyte interface on graphite for Kion storage.Besides,we summarize several kinds of methods to improve the performance of graphite for KIBs,including the design of graphite structure,selection of appropriate binder,solvent chemistry,and salt chemistry.Meanwhile,a concept of“relative energy density”is raised,which can be more accurate to evaluate the genuine electrochemical performance of graphite anode involving the specific capacity and potential.In addition,we also summarize the considerable challenges to current graphite anode in KIBs and we believe our work will offer alterative solutions to further explore high-performance graphite anode of K-ion storage.
基金supported by the National Natural Science Foundation of China (21972049, 21573080)the Guangdong Program for Distinguished Young Scholar (2017B030306013)the Special Funds for the Cultivation of Guangdong College Students’ Scientific and Technological Innovation ("Climbing Program" pdjh2021b0140)。
文摘"Dissolution,migration,and deposition"of transition metal ions (TMIs) result in capacity degradation of lithium-ion batteries (LIBs).Understanding such detrimental mechanism of TMIs is critical to the development of LIBs with long cycle life.In most previous works,TMIs were directly introduced into the electrolyte to investigate such a detrimental mechanism.In these cases,the TMIs are deposited directly on the fresh anode surface.However,in the practical battery system,the TMIs are deposited on the anode covered with solid electrolyte interphase (SEI) film.Whether the pre-presence of SEI film on anode surface influences the deposition and detriment of TMIs is unclear.In this work,the deposition of Co element on graphite anode with and without SEI film were systematically studied.The results clearly show that,in comparison with that of fresh graphite (SEI-free),the presence of SEI film aggravates the deposition of Co ions due to the Li^(+)–Co^(2+) ion exchange between the SEI and Co^(2+)-containing electrolyte without the driving of the electric field,leading to faster capacity fading of graphite anode.Therefore,how to regulate electrolytes and film-forming additives to design the components of SEI and prevent its exchange with TMIs,is a crucial way to inhibit the deposition and detriment of TMIs on graphite anode.
基金supported by the National Natural Science Foundation of China (No. 50973112)the Hundred Talents Program of the Chinese Academy of Sciences (CAS), the CAS-Guangdong Collaboration Program (No. 20108)+1 种基金the Science & Technology Project of Guangzhou (No. 11A44061500)the Amperex Technology Ltd. (China)
文摘{3-[2-(2-methoxyethoxy) ethoxy]-propyl} triethoxysilane (TESM2) was synthesized and used as an electrolyte additive to improve the performances of lithium-ion batteries (LIBs). The electrochemical properties of the electrolyte (1 mol/L lithium hexafluorophosphate (LiPF 6 )/ethylene carbonate (EC):diethylene carbonate (DEC):dimethyl carbonate (DMC), 1:1:1) with different contents of TESM2 were characterized by ionic conductivity measurement, galvanostatic charge/discharge test of graphite/Li half cells, and electrochemical impedance spectroscopy. Both the cycling performances and C-rate capabilities of graphite/Li half cells were significantly improved with an optimized content of 15% TESM2 in the electrolyte. The graphite/Li half cell delivered a very high specific capacity of 370 mAh/g at 0.2C rate without any capacity loss for 60 cycles, and retained a capacity of 292 mAh/g at 2C rate. The solid electrolyte interphase (SEI) film on the surface of the graphite anode was investigated by scanning electron microscopy (SEM) and energy dispersive spectroscopy (EDS), indicating that TESM2 was effectively involved in the formation of SEI film on the surface of graphite.
基金support from the National Key Research and Development Program of China(No.2022YFB2402200)National Natural Science Foundation of China(No.22109028)+1 种基金Natural Science Foundation of Shanghai(No.22ZR1404400)Chenguang Program sponsored by Shanghai Education Development Foundation and Shanghai Municipal Education Commission(No.19CG01).
文摘Weakly-solvated electrolytes(WSEs)utilizing solvents with weak coordination ability offer advantages for low-potential graphite anode owing to their facile desolvation process and anions-derived inorganic-rich solid electrolyte interphase(SEI)film.However,these electrolytes face challenges in achieving a balance between the weak solvation affinity and high ionic conductivity,as well as between rigid inorganic-rich SEI and flexible SEI for long-term stability.Herein,we introduce 1,3-dioxolane(DOL)and lithium bis(trifluoromethanesulfonyl)-imide(LiTFSI)as functional additives into a WSE based on nonpolar cyclic ether(1,4-dioxane).The well-formulated WSE not only preserves the weakly solvated features and anion-dominated solvation sheath,but also utilizes DOL to contribute organic species for stabilizing the SEI layer.Benefitting from these merits,the optimized electrolyte enables graphite anode with excellent fast-charging performance(210 mAh/g at 5 C)and outstanding cycling stability(600 cycles with a capacity retention of 82.0%at room temperature and 400 cycles with a capacity retention of 80.4%at high temper-ature).Furthermore,the fabricated LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2)||graphite full cells demonstrate stable operation for 140 cycles with high capacity retention of 80.3%.This work highlights the potential of tailoring solvation sheath and interphase properties in WSEs for advanced electrolyte design in graphite-based lithium-ion batteries.
文摘In this paper, the formation mechanism of the passive SEI film at the natural graphite anodes was investigated with tilt: electrochemical impedance spectroscopy (EIS). A characteristic semicircle was observed in the lower frequency range of the EIS spectrum for the irreversible charge process (lithium intercalation) at ca. 0.75V, 0.40V and 0.20V.
基金the National Natural Science Foundation of China(21975212)the Industry Leading Key Projects of Fujian Province(2022H0057)the High-level talent start-up Foundation of Xiamen Institute of Technology for financial support。
文摘Recycling graphite anode from spent lithium-ion batteries(SLIBs)is regarded as a crucial approach to promoting sustainable energy storage industry.However,the recycled graphite(RG)generally presents degraded structure and performance.Herein,the residual fluoride self-activated effect is proposed for the upgraded utilization of RG.Simple and low-energy water immersion treatment not only widens the interlayer spacing,but also retains appropriate fluoride on the surface of RG.Theoretical analysis and experiments demonstrate that the residual fluoride can optimize Li~+migration and deposition kinetics,resulting in better Li~+intercalation/deintercalation in the interlayer and more stable Li metal plating/stripping on the surface of RG,As a result,the designed LFP||RG full cells achieve ultrahigh reversibility(~100%Coulombic efficiency),high capacity retention(67%after 200 cycles,0.85 N/P ratio),and commendable adaptability(stable cycling without short-circuiting,0.15 N/P ratio).The energy density is improved from 334 Wh kg^(-1)of 1.1 N/P ratio to 367 Wh kg^(-1)of 0.85 N/P ratio(total mass based on cathode and anode).The exploration of RG by residual fluoride self-activated effect achieves upgraded utilization beyond fresh commercial graphite and highlights a new strategy for efficient reuse of SLIBs.
基金financial support from the National Natural Science Foundation of China(52203303)the International Partnership Program of the Chinese Academy of Sciences(321GJHZ2023189FN)+2 种基金the Natural Science Foundation of Guangdong Province(2022A1515010076)the Shenzhen Science and Technology Program(SGDX20211123151002003)the Shenzhen International Cooperation Program(GJHZ20220913142812025)。
文摘Graphite interfaces are an important part of the anode in lithium-ion batteries(LIBs),significantly influencing Li intercalation kinetics.Graphite anodes adopt different stacking sequences depending on the concentration of the intercalated Li ions.In this work,we performed first-principles calculations to comprehensively address the energetics and dynamics of Li intercalation and Li vacancy diffusion near the no n-basal edges of graphite,namely the armchair and zigzag-edges,at high Li concentration.We find that surface effects persist in stage-Ⅱ that bind Li strongly at the edge sites.However,the pronounced effect previously identified at the zigzag edge of pristine graphite is reduced in LiC_(12),penetrating only to the subsurface site,and eventually disappearing in LiC_(6).Consequently,the distinctive surface state at the zigzag edge significantly impacts and restrains the charging rate at the initial lithiation of graphite anodes,whilst diminishes with an increasing degree of lithiation.Longer diffusion time for Li hopping to the bulk site from either the zigzag edge or the armchair edge in LiC_(6) was observed during high state of charge due to charge repulsion.Effectively controlling Li occupation and diffusion kinetics at this stage is also crucial for enhancing the charge rate.
文摘To improve the rate capability and cyclability of natural graphite anode for Li-ion batteries,a novel modification approach was developed.The modification approach included two steps:(a)high-energy ball milling in a rotary autoclave containing alumina balls,H_3PO_4 and ethanol;(b)coating with pyrolytic carbon from phenlic resin.The treated graphite shows obvious improvement compared with the original natural graphite in electrochemical properties such as cyclability and rate capability,especially at high current density.The primary reasons leading to the improvement in rate capability and cyclability are that the diffusion impedance of Li^+ in graphite is reduced due to the fact that P filtered into graphite layers can mildly increase interlayer distances,and the fact that the structural stability of graphite surface is enhanced since the coated pyrolytic carbon can depress the co-intercalation of solvated lithium ion.
基金Project(52377220)supported by the National Natural Science Foundation of ChinaProject(kq2208265)supported by the Natural Science Foundation of Changsha,Hunan Province,ChinaProject supported by State Key Laboratory of Powder Metallurgy(Central South University,Changsha,China)。
文摘Cycling and rate performance of natural graphite is still limited by the sluggish kinetics of lithium ions,which can be improved by surface modifications in previous research.Among these methods,amorphous carbon coating has been proved to be mature and efficient.However,the significance of coating uniformity in relation to solid electrolyte interphase(SEI)has been largely overlooked.In this study,the uniformity of amorphous carbon coating is adjusted by the particle size of pitch.When discharged-charged at 1 C,graphite half-cells with such uniform coating show 90.3%of the capacity at 0.1 C,while that is 82.1%for non-uniform coating.Additionally,improved initial coulombic efficiency and cycling stability are demonstrated.These can be attributed to graphite anodes featuring a uniform carbon coating that promotes effective and homogeneous LiF formation within the inorganic matrix.This leads to the establishment of a stabilized SEI,confirmed by time-of-flight secondary ion mass spectrometry(TOF-SIMS).This work provides valuable reference into the rational control of graphite interfaces for high electrochemical performance.
基金the financial support from the National Natural Science Foundation of China(Nos.52171219 and 91963113).
文摘Graphite is a dominant anode material for lithium-ion batteries(LIBs)due to its outstanding electrochemical performance.However,slow lithium ion(Li+)kinetics of graphite anode restricts its further application.Herein,we report that high-temperature shock(HTS)can drive spent graphite(SG)into defect-rich recycled graphite(DRG)which is ideal for high-rate anode.The DRG exhibits the charging specific capacity of 323 mAh/g at a high current density of 2 C,which outperforms commercial graphite(CG,120 mAh/g).The eminent electrochemical performance of DRG can be attributed to the recovery of layered structure and partial remaining defects of SG during ultrafast heating and cooling process,which can effectively reduce total strain energy,accelerate the phase transition in thermodynamics and improve the Li+diffusion.This study provides a facile strategy to guide the re-graphitization of SG and design high performance battery electrode materials by defect engineering from the atomic level.
基金This work was supported by National Key R&D Program of China(2016YFB0100301)National Natural Science Foundation of China(21875022,51802020)+2 种基金Science and Technology Innovation Foundation of Beijing Institute of Technology Chongqing Innova tion Center(2020CX5100006)Young Elite Scientists Sponsor ship Program by CAST(2018QNRC001)L.Chen and N.Li acknowledge the support from Beijing Institute of Technology Research Fund Program for Young Scholars.
文摘Lithium plating on graphite anode is triggered by harsh conditions of fast charge and low temperature,which sig-nificantly accelerates SOH(state of health)degradation and may cause safety issues of lithium ion batteries(LIBs).This paper has reviewed recent research progress of lithium plating on graphite anode.Firstly,we summarize the forming mechanisms of Li plating with(corresponding influence factors,the detect-ing methods and hazard of Li plating.Then,approaches to suppress Li plating are discussed,including anode surface modification,electrolyte composition optimization and development of optimal charge.strategies.Finally,we con-clude and propose the remaining challenges and prospects in terms of mechanism research,detecting approaches,and suppressing methods of Li plating.This review highlights the development of Li plating research and plays a guiding rule of further study on Li plating in LIBs.
基金supported by the National Natural Science Foundation of China(91963118 and 52173246)Science Technology Program of Jilin Province(20200201066JC)the 111 Project(B13013)。
文摘Although graphite anodes operated with representative de/intercalation patterns at low potentials are considered highly desirable for K-ion batteries,the severe capacity fading caused by consecutive reduction reactions on the aggressively reactive surface is inevitable given the scarcity of effective protecting layers.Herein,by introducing a flame-retardant localized high-concentration electrolyte with retentive solvation configuration and relatively weakened anion-coordination and non-solvating fluorinated ether,the rational solid electrolyte interphase characterized by well-balanced inorganic/organic components is tailored in situ.This effectively prevented solvents from excessively decomposing and simultaneously improved the resistance against K-ion transport.Consequently,the graphite anode retained a prolonged cycling capability of up to 1400 cycles(245 mA h g,remaining above 12 mon)with an excellent capacity retention of as high as 92.4%.This is superior to those of conventional and high-concentration electrolytes.Thus,the optimized electrolyte with moderate salt concentration is perfectly compatible with graphite,providing a potential application prospect for K-storage evolution.
基金supported by the Key Scientific Development Project of Guangdong Province(2015A030308019)the Guangzhou Scientific and Technological Development Plan(2014J4100217)the Hundred Talents Program of Chinese Academy of Sciences
文摘Due to the presence of graphite flake cascades, the real graphite anode of Li-ion battery shows non-iso- tropic characteristic. The present work developed an ellipsoid-based simulated annealing method and numeri- cally reconstructed the three-dimensional microstructure of a graphite anode. The reconstructed anode is a composite of three clearly distinguished phases： pore （or electrolyte）, graphite, and solid additives, well representing the non- isotropic heterogeneous characteristic of real graphite anode. Characterization analysis of the reconstructed electrode gives information such as the connectivity of individual phase, the specific interracial area between solid and pore phase, and the pore size distribution. The effects of the ellipsoid size on the structural characteristics of graphite anode were particularly studied. As the size of the ellipsoidal particle slightly increases, the average pore diameter increases and as a result the specific interfacial area between the solid and pore phase in the reconstructed area decreases; compared with the equatorial radius, the polar radius of ellipsoidal graphite particles has more sig- nificant influence on the characteristics of electrode microstructure.
文摘1 Results Propylene carbonate (PC) is well known having a series of excellent properties including low melting point,wide liquid-phase range and wide electrochemical window.In addition,PC is well compatible with different cathode materials.However,the poor compatibility of PC with graphite anode limits the utilization of PC solvent into lithium ion batteries.It is generally accepted that PC molecules co-intercalate into graphite interlayer with solvated Li ions and cause exfoliation of graphite structur...
基金supported by an Early Career Faculty Grant from NASA’s Space Technology Research Grants Program (80NSSC18K1509)supported by the Institute for Electronics and Nanotechnology Seed Grant and performed in part at the Georgia Tech Institute for Electronics and Nanotechnology, a member of the National Nanotechnology Coordinated Infrastructure (NNCI), which was supported by the National Science Foundation (ECCS-2025462)
文摘As lithium(Li)-ion batteries expand their applications,operating over a wide temperature range becomes increasingly important.However,the lowtemperature performance of conventional graphite anodes is severely hampered by the poor diffusion kinetics of Li ions(Li^(+)).Here,zinc oxide(ZnO) nanoparticles are incorporated into the expanded graphite to improve Li^(+)diffusion kinetics,resulting in a significant improvement in lowtemperature performance.The ZnO-embedded expanded graphite anodes are investigated with different amounts of ZnO to establish the structurecharge storage mechanism-performance relationship with a focus on lowtemperature applications.Electrochemical analysis reveals that the ZnOembedded expanded graphite anode with nano-sized ZnO maintains a large portion of the diffusion-controlled charge storage mechanism at an ultra-low temperature of-50℃ Due to this significantly enhanced Li^(+)diffusion rate,a full cell with the ZnO-embedded expanded graphite anode and a LiNi_(0.88)Co_(0.09)Al_(0.03)O_(2)cathode delivers high capacities of 176 mAh g^(-1)at20℃ and 86 mAh g^(-1)at-50℃ at a high rate of 1 C.The outstanding low-temperature performance of the composite anode by improving the Li^(+)diffusion kinetics provides important scientific insights into the fundamental design principles of anodes for low-temperature Li-ion battery operation.
基金supported by National Key Research and Development Program(2016YFA0202500)the National Natural Science Foundation of China(21776019)Beijing Natural Science Foundation(L182021)。
文摘Lithium-ion battery has greatly changed our lifestyle and the solid electrolyte interphase(SEI)covered on the graphite anode determines the service life of a battery.The formation method and the formation temperature at initial cycle of a battery determine the feature of the SEI.Herein,we investigate the gap of formation behavior in both a half cell(graphite matches with lithium anode)and a full cell(graphite matches with NCM,short for LiNixCoyMn1-x-yO2)at different temperatures.We conclude that high temperature causes severe side reactions and low temperature will result in low ionic conductive SEI layer,the interface formed at room temperature owns the best ionic conductivity and stability.
基金supported by a grant from the China Scholarship Council(202006370035 and 202006220024)supported by the National Natural Science Foundation of China(52107229)。
文摘A capacity increase is often observed in the early stage of Li-ion battery cycling.This study explores the phenomena involved in the capacity increase from the full cell,electrodes,and materials perspective through a combination of non-destructive diagnostic methods in a full cell and post-mortem analysis in a coin cell.The results show an increase of 1%initial capacity for the battery aged at 100%depth of discharge(DOD)and 45℃.Furthermore,large DODs or high temperatures accelerate the capacity increase.From the incremental capacity and differential voltage(IC-DV)analysis,we concluded that the increased capacity in a full cell originates from the graphite anode.Furthermore,graphite/Li coin cells show an increased capacity for larger DODs and a decreased capacity for lower DODs,thus in agreement with the full cell results.Post-mortem analysis results show that a larger DOD enlarges the graphite dspace and separates the graphite layer structure,facilitating the Li+diffusion,hence increasing the battery capacity.
基金financially supported by the National Natural Science Foundation of China (Nos.51974143,52274408,5220041313,52164050 and 51904134)Major Science and Technology Projects in Yunnan Province (Nos.202102AB080016,202103AA080004 and 202202AB080010)+3 种基金Yunnan Fundamental Research Projects (No.202201AW070014)Yunnan Ten Thousand Talents Project (No.YNWR-QNBJ-2018-111)Yunnan High-level Talent Project (No.YNQR-GCC-2019-010)the Program for Innovative Research Team in University of Ministry of Education of China (No.IRT_17R48)。
文摘The co-utilization of silicon(Si) and graphite(G) has been considered as the preferred strategy to achieve high energy density anode materials,but the effective synergistic integration of Si and graphite is still a challenge and it is necessary to find a scheme to accommodate the large-scale production of Si/graphite anodes.In this work,silicon cutting waste from the photovoltaic industry was used as raw material,mixed with graphite,pitch,and polyvinylpyrrolidone,and subjected to high-energy ball milling.The mixture was then heated in an Ar atmosphere for the carbon coating,and the resulting Si/graphite/carbon(Si/G/C) composite was etched to remove the thicker SiOx layer formed on the Si surface to allow the pores between the Si and the carbon matrix to obtain Si@voids/G@C.Benefiting from the integrated structural design and the significantly enhanced electronic conductivity,the Si/G@voids@C composite exhibited the first dischargespecific capacity of 2530 mAh·g^(-1) with an initial coulombic efficiency(ICE) of 86.7%,and the remaining capacity exceeded 1000 mAh·g^(-1) after 550 cycles at 1.5A·g^(-1).Notably,full lithium-ion batteries with a Si/G@voids@C anode and LiFePO_4 cathode delivered a stable capacity of 140 mAh·g^(-1).The synthesis method is facile and cost-effective,providing an integration strategy for Si and G with a potential scheme for large-scale commercial applications.
