Lithium-ion batteries(LIBs)suffer from float charge failure in the grid-scale storage market.However,the lack of a unified descriptor for the diverse reasons behind float charge failure poses a challenge.Here,a quanti...Lithium-ion batteries(LIBs)suffer from float charge failure in the grid-scale storage market.However,the lack of a unified descriptor for the diverse reasons behind float charge failure poses a challenge.Here,a quantitative analysis of active lithium loss is conducted across multiple temperatures into float charge of Li(Ni_(0.5)Co_(0.2)Mn_(0.3))O_(2)–graphite batteries.It is proposed that the active lithium loss can be used as a descriptor to describe the reasons for float charge quantitatively.Approximately 6.88%and 0.96%of active lithium are lost due to solid electrolyte interphase thickening and lithium deposition,which are primary and secondary failure reasons,respectively.These findings are confirmed by X-ray photoelectron spectroscopy depth profiling,scanning electron microscope,and accelerating rate calorimeter.Titration-gas chromatography and nuclear magnetic resonance are utilized to quantitatively analyze active lithium loss.Additionally,electrolyte decomposition at high temperatures also contributes to active lithium loss,as determined by Auger electron spectrum and nondestructive ultrasound measurements.Notably,no failure is detected in the cathode due to the relatively low working voltage of the float charge.These findings suggest that inhibiting active lithium loss can be an efficient way of delaying failure during high-temperature float charge processes in LIBs.展开更多
Anode-free Li metal batteries(AFLMBs)impose stringent demands on active Li utilization due to the absence of exogenous Li.Moreover,the poor cycling reversibility of Li metal and significant active Li loss have hindere...Anode-free Li metal batteries(AFLMBs)impose stringent demands on active Li utilization due to the absence of exogenous Li.Moreover,the poor cycling reversibility of Li metal and significant active Li loss have hindered the development of AFLMBs.Herein,for the first time,we establish the correlation between the electrochemical structural connectivity of Li deposits and the loss pathways of active Li.Li nucleation behavior is optimized via the self-driven formation of hydroxyl-modified lithiophilic Cu nanoparticles from CuOHF.Dense columnar Li stacks with stable bulk-phase electronic pathways and interfacial kinetic structures are achieved through a high-density spatial multidimensional nucleation mechanism,which restricts the quasi-linear accumulation of irreversible Li to only 0.003 mg per cycle.Meanwhile,the regulated Li growth process exhibits homogeneous and rapid interfacial mass transfer with extremely low concentration polarization.The anode-free LiFePO_(4) pouch cell retains 61.4%of its initial reversible capacity after 100 cycles.Insights into active Li utilization derived from this work will accelerate the development of high-performance AFLMBs.展开更多
Anode‐free lithium metal batteries(AFLMBs),also known as lithium metal batteries(LMBs)with zero excess lithium,have garnered significant attention due to their substantially higher energy density compared to conventi...Anode‐free lithium metal batteries(AFLMBs),also known as lithium metal batteries(LMBs)with zero excess lithium,have garnered significant attention due to their substantially higher energy density compared to conventional lithium metal anodes,improved safety characteristics,and lower production costs.However,the current cycling stability of AFLMBs faces formidable challenges primarily caused by significant lithium loss associated with the deposition of lithium metal.Therefore,this review focuses on the crucial aspects of lithium metal nucleation and growth on the anode side.Respectively,aiming to provide an in‐depth understanding of the deposition mechanisms,comprehensively summarize the corresponding scientific influencing factors,and analyze specific strategies for addressing these issues through the integration of relevant exemplary cases.Importantly,this review endeavors to offer a profound explication of the scientific essence and intricate mechanisms that underlie the diverse modification strategies.This review possesses the inherent capacity to greatly facilitate the progress and enlightenment of research in this field,offering a valuable resource for the researchers.展开更多
Lithium–sulfur batteries suffer from rapid capacity decay due to polysulfide dissolution and lithium anode instability.Sulfurized poly(acrylonitrile)(SPAN),which chemically anchors sulfur within its polymer matrix,ca...Lithium–sulfur batteries suffer from rapid capacity decay due to polysulfide dissolution and lithium anode instability.Sulfurized poly(acrylonitrile)(SPAN),which chemically anchors sulfur within its polymer matrix,can effectively suppress polysulfide dissolution.Pairing SPAN with the graphite(Gr)anode can circumvent challenges associated with lithium metal and achieve prolonged cycle life.For developing such long-life sulfur-based batteries,it is of great significance to understand their cycling decay mechanism and establish a reasonable acceleration test model,since it is beneficial for quickly evaluating the cycle properties and optimizing battery designs.This study systematically investigates the electrochemical dynamics and capacity decay mechanism of SPAN||Gr pouch cells cycled at 25–55℃.Multiscale analyses reveal that capacity fade arises from active lithium loss and increased resistance,both of which would be accelerated by higher temperatures.Leveraging the consistent decay mechanism across temperatures,an accelerated aging model based on the Arrhenius equation is developed.This model could predict cycling parameters at specific temperatures and reduce testing time by 50%.These insights and the accelerated aging model may provide critical guidance for developing long-life sulfur-based batteries for practical applications.展开更多
The flourishing expansion of the lithium-ion batteries(LIBs) market has led to a surge in the demand for lithium resources. Developing efficient recycling technologies for imminent large-scale retired LIBs can signifi...The flourishing expansion of the lithium-ion batteries(LIBs) market has led to a surge in the demand for lithium resources. Developing efficient recycling technologies for imminent large-scale retired LIBs can significantly facilitate the sustainable utilization of lithium resources. Here, we successfully extract active lithium from spent LIBs through a simple, efficient, and low-energy-consumption chemical leaching process at room temperature, using a solution comprised of polycyclic aromatic hydrocarbons and ether solvents. The mechanism of lithium extraction is elucidated by clarifying the relationship between the redox potential and extraction efficiency. More importantly, the reclaimed active lithium is directly employed to fabricate LiFePO_(4) cathode with performance comparable to commercial materials. When implemented in 56 Ah prismatic cells, the cells deliver stable cycling properties with a capacity retention of ~90% after 1200 cycles. Compared with the other strategies, this technical approach shows superior economic benefits and practical promise. It is anticipated that this method may redefine the recycling paradigm for retired LIBs and drive the sustainable development of industries.展开更多
基金supported by the National Key Research and Development(R&D)Program of China(2022YFB4101600)Key Research and Development(R&D)Projects of Shanxi Province(202102040201003,202202040201007)+1 种基金the Fundamental Research Program of Shanxi Province(20210302123008)the ICC CAS,SCJC-XCL-2023-13,CAS Project for Young Scientists in Basic Research(Grant No.YSBR-102).
文摘Lithium-ion batteries(LIBs)suffer from float charge failure in the grid-scale storage market.However,the lack of a unified descriptor for the diverse reasons behind float charge failure poses a challenge.Here,a quantitative analysis of active lithium loss is conducted across multiple temperatures into float charge of Li(Ni_(0.5)Co_(0.2)Mn_(0.3))O_(2)–graphite batteries.It is proposed that the active lithium loss can be used as a descriptor to describe the reasons for float charge quantitatively.Approximately 6.88%and 0.96%of active lithium are lost due to solid electrolyte interphase thickening and lithium deposition,which are primary and secondary failure reasons,respectively.These findings are confirmed by X-ray photoelectron spectroscopy depth profiling,scanning electron microscope,and accelerating rate calorimeter.Titration-gas chromatography and nuclear magnetic resonance are utilized to quantitatively analyze active lithium loss.Additionally,electrolyte decomposition at high temperatures also contributes to active lithium loss,as determined by Auger electron spectrum and nondestructive ultrasound measurements.Notably,no failure is detected in the cathode due to the relatively low working voltage of the float charge.These findings suggest that inhibiting active lithium loss can be an efficient way of delaying failure during high-temperature float charge processes in LIBs.
基金supported by the National Natural Science Foundation of China(Grant No.52372281)the Fundamental Research Funds for the Central Universities(Grant No.2232024G-07)+1 种基金the Key Laboratory of Advanced Fiber Materials(Grant No.KF2517)the Program for Professor of Special Appointment(Eastern Scholar)at Shanghai Institutions of Higher Learning.
文摘Anode-free Li metal batteries(AFLMBs)impose stringent demands on active Li utilization due to the absence of exogenous Li.Moreover,the poor cycling reversibility of Li metal and significant active Li loss have hindered the development of AFLMBs.Herein,for the first time,we establish the correlation between the electrochemical structural connectivity of Li deposits and the loss pathways of active Li.Li nucleation behavior is optimized via the self-driven formation of hydroxyl-modified lithiophilic Cu nanoparticles from CuOHF.Dense columnar Li stacks with stable bulk-phase electronic pathways and interfacial kinetic structures are achieved through a high-density spatial multidimensional nucleation mechanism,which restricts the quasi-linear accumulation of irreversible Li to only 0.003 mg per cycle.Meanwhile,the regulated Li growth process exhibits homogeneous and rapid interfacial mass transfer with extremely low concentration polarization.The anode-free LiFePO_(4) pouch cell retains 61.4%of its initial reversible capacity after 100 cycles.Insights into active Li utilization derived from this work will accelerate the development of high-performance AFLMBs.
基金supported by the Finance Science and Technology Project of the National Key R&D Program of China(No.2022YFB3803400)National Natural Science Foundation of China(22179135)+4 种基金Postdoctoral Fellowship Program of CPSF(GZC20232806)Shandong Provincial Natural Science Foundation(ZR2024QB297,ZR2023JQ003,ZR2022ZD11),Qingdao Postdoctoral Funding Program(QDBSH20240102103)Taishan Scholars of Shandong Province(No.ts201511063)Taishan Scholars Program for Young Expert of Shandong Province(tsqn202103145)Qingdao New Energy Shandong Laboratory(QIBEBT/SEI/QNESLS202304).
文摘Anode‐free lithium metal batteries(AFLMBs),also known as lithium metal batteries(LMBs)with zero excess lithium,have garnered significant attention due to their substantially higher energy density compared to conventional lithium metal anodes,improved safety characteristics,and lower production costs.However,the current cycling stability of AFLMBs faces formidable challenges primarily caused by significant lithium loss associated with the deposition of lithium metal.Therefore,this review focuses on the crucial aspects of lithium metal nucleation and growth on the anode side.Respectively,aiming to provide an in‐depth understanding of the deposition mechanisms,comprehensively summarize the corresponding scientific influencing factors,and analyze specific strategies for addressing these issues through the integration of relevant exemplary cases.Importantly,this review endeavors to offer a profound explication of the scientific essence and intricate mechanisms that underlie the diverse modification strategies.This review possesses the inherent capacity to greatly facilitate the progress and enlightenment of research in this field,offering a valuable resource for the researchers.
基金supported by the National Key R&D Program of China(2021YFB2400300)the National Natural Science Foundation of China(92472114)+1 种基金the Hubei Provincial Natural Science Foundation of China(2024AFA012)the Key R&D Program of Hubei Province(2024BAB092)。
文摘Lithium–sulfur batteries suffer from rapid capacity decay due to polysulfide dissolution and lithium anode instability.Sulfurized poly(acrylonitrile)(SPAN),which chemically anchors sulfur within its polymer matrix,can effectively suppress polysulfide dissolution.Pairing SPAN with the graphite(Gr)anode can circumvent challenges associated with lithium metal and achieve prolonged cycle life.For developing such long-life sulfur-based batteries,it is of great significance to understand their cycling decay mechanism and establish a reasonable acceleration test model,since it is beneficial for quickly evaluating the cycle properties and optimizing battery designs.This study systematically investigates the electrochemical dynamics and capacity decay mechanism of SPAN||Gr pouch cells cycled at 25–55℃.Multiscale analyses reveal that capacity fade arises from active lithium loss and increased resistance,both of which would be accelerated by higher temperatures.Leveraging the consistent decay mechanism across temperatures,an accelerated aging model based on the Arrhenius equation is developed.This model could predict cycling parameters at specific temperatures and reduce testing time by 50%.These insights and the accelerated aging model may provide critical guidance for developing long-life sulfur-based batteries for practical applications.
基金supported by the National Key Research and Development Program of China (2022YFB2404800)the National Natural Science Foundation of China (U1966214 and 22008082)。
文摘The flourishing expansion of the lithium-ion batteries(LIBs) market has led to a surge in the demand for lithium resources. Developing efficient recycling technologies for imminent large-scale retired LIBs can significantly facilitate the sustainable utilization of lithium resources. Here, we successfully extract active lithium from spent LIBs through a simple, efficient, and low-energy-consumption chemical leaching process at room temperature, using a solution comprised of polycyclic aromatic hydrocarbons and ether solvents. The mechanism of lithium extraction is elucidated by clarifying the relationship between the redox potential and extraction efficiency. More importantly, the reclaimed active lithium is directly employed to fabricate LiFePO_(4) cathode with performance comparable to commercial materials. When implemented in 56 Ah prismatic cells, the cells deliver stable cycling properties with a capacity retention of ~90% after 1200 cycles. Compared with the other strategies, this technical approach shows superior economic benefits and practical promise. It is anticipated that this method may redefine the recycling paradigm for retired LIBs and drive the sustainable development of industries.
