Electrolyte design holds the greatest opportunity for the development of batteries that are capable of sub-zero temperature operation.To get the most energy storage out of the battery at low temperatures,improvements ...Electrolyte design holds the greatest opportunity for the development of batteries that are capable of sub-zero temperature operation.To get the most energy storage out of the battery at low temperatures,improvements in electrolyte chemistry need to be coupled with optimized electrode materials and tailored electrolyte/electrode interphases.Herein,this review critically outlines electrolytes’limiting factors,including reduced ionic conductivity,large de-solvation energy,sluggish charge transfer,and slow Li-ion transportation across the electrolyte/electrode interphases,which affect the low-temperature performance of Li-metal batteries.Detailed theoretical derivations that explain the explicit influence of temperature on battery performance are presented to deepen understanding.Emerging improvement strategies from the aspects of electrolyte design and electrolyte/electrode interphase engineering are summarized and rigorously compared.Perspectives on future research are proposed to guide the ongoing exploration for better low-temperature Li-metal batteries.展开更多
Rechargeable aqueous zinc(Zn) batteries hold great promise for large-scale energy storage,but their implementation is plagued by poor Zn reversibility and unsatisfactory low-temperature performance.Herein,we design a ...Rechargeable aqueous zinc(Zn) batteries hold great promise for large-scale energy storage,but their implementation is plagued by poor Zn reversibility and unsatisfactory low-temperature performance.Herein,we design a cell-nucleus structured electrolyte by introducing low-polarity 1,2-dimethoxyethane(DME) into dilute 1 M zinc trifluoromethanesulfonate(Zn(OTf)_(2)) aqueous solution,which features an OTf--rich Zn2^(+)-primary solvation sheath(PSS,inner nucleus) and the DMEmodulated Zn^(2+)-outer solvation sheath(outer layer).We find that DME additives with a low dosage do not participate in the Zn2+-PSS but reinforce the Zn-OTf-coordination,which guarantees good reaction kinetics under ultralow temperatures.Moreover,DME breaks the original H-bonding network of H2O,depressing the freezing point of electrolyte to-52.4℃.Such a cell-nucleus-solvation structure suppresses the H_(2)O-induced side reactions and forms an anion-derived solid electrolyte interphase on Zn and can be readily extended to 1,2-diethoxyethane.The as-designed electrolyte enables the Zn electrode deep cycling stability over 3500 h with a high depth-of-discharge of 51.3% and endows the Zn‖V_(2)O_(5)full battery with stable cycling over 1000 cycles at 40℃.This work would inspire the solvation structure design for low-temperature aqueous batteries.展开更多
The electrolyte integrated with lithium metal anodes is subjected to the issues of interfacial compatibility and stability,which strongly influence the performances of high-energy lithium metal batteries.Here,we repor...The electrolyte integrated with lithium metal anodes is subjected to the issues of interfacial compatibility and stability,which strongly influence the performances of high-energy lithium metal batteries.Here,we report a new electrolyte recipe viz.a moderately concentrated electrolyte comprising of 2.4 M lithium bis(fluorosulfonyl)imide(LiFSI)in a cosolvent mixture of fluorinated ethylene carbonate(FEC)and dimethyl carbonate(DMC)with relatively high ion conductivity.Owing to the preferential decomposition of LiFSI and FEC,an inorganic-rich interphase with abundant Li_(2)O and LiF nanocrystals is formed on lithium metal with improved robustness and ion transfer kinetics,enabling lithium plating/stripping with an extremely low overpotential of~8 mV and the average CE of 97%.When tested in Li||LiFePO_(4) cell,this electrolyte provides long-term cycling with a capacity retention of 98.3%after 1000 cycles at 1 C and an excellent rate performance of 20 C,as well as an areal capacity of 1.35 mA h cm^(-2)at the cathode areal loading of 9 mg cm^(-2).Moreover,the Li||LiFePO_(4) cell exhibits excellent wide-temperature performances(-40~60℃),including long-term cycling stability over 2600 cycles without visible capacity fading at 0℃,as well as extremely high average CEs of 99.6%and 99.8% over 400 cycles under-20℃ and 45℃.展开更多
The low-temperature performance of Li-ion batteries(LIBs) has important impacts on their commercial applications. Besides the metallic lithium deposition, which is regarded as one of the main failure mechanisms of the...The low-temperature performance of Li-ion batteries(LIBs) has important impacts on their commercial applications. Besides the metallic lithium deposition, which is regarded as one of the main failure mechanisms of the LIBs at low temperatures, the synergistic effects originating from the cathode, anode, electrolyte, and separators to the batteries are still not clear. Here, the 21700-type cylindrical batteries were evaluated at a wide range of temperatures to investigate the failure mechanism of batteries. Voltage relaxation, and the post-mortem analysis combined with the electrochemical tests, unravel that the capacity degradation of batteries at low temperature is related to the lithium plating at graphite anodes,the formation of unsatisfied solid deposited/decomposed electrolyte mixture phase on the anode, the precipitation of solvent in the electrolytes and the block of separator pores, and the uneven dissolved transition metal-ions from the cathode. We hope this finding may open up a new avenue to alleviate the capacity degradation of advanced LIBs at low temperatures and shed light on the development of outstanding low-temperature LIBs via simultaneous optimization of all the components including electrodes, electrolytes and separators.展开更多
Sulfide electrolyte-based all-solid-state batteries(ASSBs)are potential next generation energy storage technology due to the high ionic conductivity of sulfide electrolytes and potentially improved energy density and ...Sulfide electrolyte-based all-solid-state batteries(ASSBs)are potential next generation energy storage technology due to the high ionic conductivity of sulfide electrolytes and potentially improved energy density and safety.However,the performance of ASSBs at/below subzero temperatures has not been explored systematically.Herein,low temperature(LT)performance of LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2)(NCM811)|Li_(9.54)Si_(1.74)P_(1.44)S11.7Cl_(0.3)(LiSPSCl)|Li_(4)Ti_(5)O_(12)(LTO)ASSBs was investigated.By charging the ASSB to 6 V at−40℃,a capacity of 100.7 mAh∙g^(−1)at 20 mA∙g^(−1)was achieved,which is much higher than that charged to 4.3 V(4.6 mAh∙g^(−1))at−40℃.Moreover,atomic resolution microscopy revealed that the NCM811 remained almost intact even after being charged to 6 V.In contrast,NCM811 was entirely destructed when charged to 6 V at room temperature.The sharp difference arises from the large internal charge transfer resistance at LT which requires high voltage to overcome.Nevertheless,such high voltage is not harmful to the active material but beneficial to extracting most energy out of the ASSBs at LT.We also demonstrated that thinner electrolyte is favorable for LT operation of ASSBs due to the reduced ion transfer distance.This work provides new strategies to boost the capacity and energy density of sulfide-based ASSBs at LT for dedicated LT applications.展开更多
Graphite offers several advantages as an anode material,including its low cost,high theoretical capacity,extended lifespan,and low Li+-intercalation potential.However,the performance of graphite-based lithium-ion batt...Graphite offers several advantages as an anode material,including its low cost,high theoretical capacity,extended lifespan,and low Li+-intercalation potential.However,the performance of graphite-based lithium-ion batteries(LIBs)is limited at low temperatures due to several critical challenges,such as the decreased ionic conductivity of liquid electrolyte,sluggish Li+desolvation process,poor Li+diffusivity across the interphase layer and bulk graphite materials.Various approaches have therefore been explored to address these challenges.On the basis of graphite anode and corresponding LIBs,this review herein offers a comprehensive analysis of the latest advances in electrolyte engineering and electrode modification.First,electrolyte engineering is discussed in detail,highlighting the design of new electrolyte formula with broad liquid temperature range,optimized solvation structure,and well-performed inorganic-rich solid electrolyte interface.The advances in material modification have been then depicted with the view of improving the solid bulk diffusion rate to show general strategies with excellent performance at low temperatures.Finally,the corresponding challenges and opportunities have also been outlined to shed light on viable strategies for developing efficient and reliable graphite anode and graphite-based LIBs under low-temperature scenarios.展开更多
Alongside the pursuit of high energy density and long service life,the urgent demand for low-temperature performance remains a long-standing challenge for a wide range of Li-ion battery applications,such as electric v...Alongside the pursuit of high energy density and long service life,the urgent demand for low-temperature performance remains a long-standing challenge for a wide range of Li-ion battery applications,such as electric vehicles,portable electronics,large-scale grid systems,and special space/seabed/military purposes.Current Li-ion batteries suffer a major loss of capacity and power and fail to operate normally when the temperature decreases to-20℃.This deterioration is mainly attributed to poor Li-ion transport in a bulk carbonated ester electrolyte and its derived solid–electrolyte interphase(SEI).In this mini-review discussing the limiting factors in the Li-ion diffusion process,we propose three basic requirements when formulating electrolytes for low-temperature Liion batteries:low melting point,poor Liþaffinity,and a favorable SEI.Then,we briefly review emerging progress,including liquefied gas electrolytes,weakly solvating electrolytes,and localized high-concentration electrolytes.The proposed novel electrolytes effectively improve the reaction kinetics via accelerating Li-ion diffusion in the bulk electrolyte and interphase.The final part of the paper addresses future challenges and offers perspectives on electrolyte designs for low-temperature Li-ion batteries.展开更多
基金The work described in this paper was fully supported by a Grant from the City University of Hong Kong(Project No.9610641).
文摘Electrolyte design holds the greatest opportunity for the development of batteries that are capable of sub-zero temperature operation.To get the most energy storage out of the battery at low temperatures,improvements in electrolyte chemistry need to be coupled with optimized electrode materials and tailored electrolyte/electrode interphases.Herein,this review critically outlines electrolytes’limiting factors,including reduced ionic conductivity,large de-solvation energy,sluggish charge transfer,and slow Li-ion transportation across the electrolyte/electrode interphases,which affect the low-temperature performance of Li-metal batteries.Detailed theoretical derivations that explain the explicit influence of temperature on battery performance are presented to deepen understanding.Emerging improvement strategies from the aspects of electrolyte design and electrolyte/electrode interphase engineering are summarized and rigorously compared.Perspectives on future research are proposed to guide the ongoing exploration for better low-temperature Li-metal batteries.
基金supported by the National Natural Science Foundation of China (21925503, 21871149, 21835004, and 22075067)the Ministry of Education of China (B12015)+2 种基金Haihe Laboratory of Sustainable Chemical Transformations (CYZC202110)Hebei Natural Science Foundation (B2020201001)the Fundamental Research Funds for the Central Universities,Nankai University(020-63201046)。
文摘Rechargeable aqueous zinc(Zn) batteries hold great promise for large-scale energy storage,but their implementation is plagued by poor Zn reversibility and unsatisfactory low-temperature performance.Herein,we design a cell-nucleus structured electrolyte by introducing low-polarity 1,2-dimethoxyethane(DME) into dilute 1 M zinc trifluoromethanesulfonate(Zn(OTf)_(2)) aqueous solution,which features an OTf--rich Zn2^(+)-primary solvation sheath(PSS,inner nucleus) and the DMEmodulated Zn^(2+)-outer solvation sheath(outer layer).We find that DME additives with a low dosage do not participate in the Zn2+-PSS but reinforce the Zn-OTf-coordination,which guarantees good reaction kinetics under ultralow temperatures.Moreover,DME breaks the original H-bonding network of H2O,depressing the freezing point of electrolyte to-52.4℃.Such a cell-nucleus-solvation structure suppresses the H_(2)O-induced side reactions and forms an anion-derived solid electrolyte interphase on Zn and can be readily extended to 1,2-diethoxyethane.The as-designed electrolyte enables the Zn electrode deep cycling stability over 3500 h with a high depth-of-discharge of 51.3% and endows the Zn‖V_(2)O_(5)full battery with stable cycling over 1000 cycles at 40℃.This work would inspire the solvation structure design for low-temperature aqueous batteries.
基金the Innovation-Driven Project of Central South University(2019CX033)the National Natural Science Foundation of China(51904344 and 52172264)the Natural Science Foundation of Hunan Province of China(2021JJ10060 and 2022GK2033)。
文摘The electrolyte integrated with lithium metal anodes is subjected to the issues of interfacial compatibility and stability,which strongly influence the performances of high-energy lithium metal batteries.Here,we report a new electrolyte recipe viz.a moderately concentrated electrolyte comprising of 2.4 M lithium bis(fluorosulfonyl)imide(LiFSI)in a cosolvent mixture of fluorinated ethylene carbonate(FEC)and dimethyl carbonate(DMC)with relatively high ion conductivity.Owing to the preferential decomposition of LiFSI and FEC,an inorganic-rich interphase with abundant Li_(2)O and LiF nanocrystals is formed on lithium metal with improved robustness and ion transfer kinetics,enabling lithium plating/stripping with an extremely low overpotential of~8 mV and the average CE of 97%.When tested in Li||LiFePO_(4) cell,this electrolyte provides long-term cycling with a capacity retention of 98.3%after 1000 cycles at 1 C and an excellent rate performance of 20 C,as well as an areal capacity of 1.35 mA h cm^(-2)at the cathode areal loading of 9 mg cm^(-2).Moreover,the Li||LiFePO_(4) cell exhibits excellent wide-temperature performances(-40~60℃),including long-term cycling stability over 2600 cycles without visible capacity fading at 0℃,as well as extremely high average CEs of 99.6%and 99.8% over 400 cycles under-20℃ and 45℃.
基金supported by the National Natural Science Foundation of China (U1664255, 21875022, 51802020, U1564206)the National Key R&D Program of China (2016YFB0100301)+2 种基金the Science and Technology Innovation Foundation of Beijing Institute of Technology Chongqing Innovation Center (2020CX5100006)the Young Elite Scientists Sponsorship Program by CAST (2018QNRC001)support from Beijing Institute of Technology Research Fund Program for Young Scholars。
文摘The low-temperature performance of Li-ion batteries(LIBs) has important impacts on their commercial applications. Besides the metallic lithium deposition, which is regarded as one of the main failure mechanisms of the LIBs at low temperatures, the synergistic effects originating from the cathode, anode, electrolyte, and separators to the batteries are still not clear. Here, the 21700-type cylindrical batteries were evaluated at a wide range of temperatures to investigate the failure mechanism of batteries. Voltage relaxation, and the post-mortem analysis combined with the electrochemical tests, unravel that the capacity degradation of batteries at low temperature is related to the lithium plating at graphite anodes,the formation of unsatisfied solid deposited/decomposed electrolyte mixture phase on the anode, the precipitation of solvent in the electrolytes and the block of separator pores, and the uneven dissolved transition metal-ions from the cathode. We hope this finding may open up a new avenue to alleviate the capacity degradation of advanced LIBs at low temperatures and shed light on the development of outstanding low-temperature LIBs via simultaneous optimization of all the components including electrodes, electrolytes and separators.
基金This work was financially supported by the National Natural Science Foundation of China(Nos.22279112,51772262,5197010923,11575154,51971245,52022088,U20A20336,and 52002346)the Fok Ying-Tong Education Foundation of China(No.171064)+5 种基金the Natural Science Foundation of Hebei Province(Nos.B2022203018,B2018203297,B2020203037,and F2021203097)the Hebei One Hundred Talent Program(No.4570028)the High-Level Talents Research Program of the Yanshan University(Nos.00500021502 and 005000201)the Hebei Key Laboratory of Applied Chemistry after Operation Performance(No.22567616H)the Science and Technology Innovation Program of Hunan Province(No.2021RC3109)the Postgraduate Scientific Research Innovation Project of Xiangtan University(No.XDCX2022Y076).
文摘Sulfide electrolyte-based all-solid-state batteries(ASSBs)are potential next generation energy storage technology due to the high ionic conductivity of sulfide electrolytes and potentially improved energy density and safety.However,the performance of ASSBs at/below subzero temperatures has not been explored systematically.Herein,low temperature(LT)performance of LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2)(NCM811)|Li_(9.54)Si_(1.74)P_(1.44)S11.7Cl_(0.3)(LiSPSCl)|Li_(4)Ti_(5)O_(12)(LTO)ASSBs was investigated.By charging the ASSB to 6 V at−40℃,a capacity of 100.7 mAh∙g^(−1)at 20 mA∙g^(−1)was achieved,which is much higher than that charged to 4.3 V(4.6 mAh∙g^(−1))at−40℃.Moreover,atomic resolution microscopy revealed that the NCM811 remained almost intact even after being charged to 6 V.In contrast,NCM811 was entirely destructed when charged to 6 V at room temperature.The sharp difference arises from the large internal charge transfer resistance at LT which requires high voltage to overcome.Nevertheless,such high voltage is not harmful to the active material but beneficial to extracting most energy out of the ASSBs at LT.We also demonstrated that thinner electrolyte is favorable for LT operation of ASSBs due to the reduced ion transfer distance.This work provides new strategies to boost the capacity and energy density of sulfide-based ASSBs at LT for dedicated LT applications.
基金supported by the National Key Research and Development Program of China(2022YFB3803400)National Natural Science Foundation of China(22109028)+1 种基金Natural Science Foundation of Shanghai(22ZR1404400)Chenguang Program sponsored by Shanghai Education Development Foundation and Shanghai Municipal Education Commission(19CG01).
文摘Graphite offers several advantages as an anode material,including its low cost,high theoretical capacity,extended lifespan,and low Li+-intercalation potential.However,the performance of graphite-based lithium-ion batteries(LIBs)is limited at low temperatures due to several critical challenges,such as the decreased ionic conductivity of liquid electrolyte,sluggish Li+desolvation process,poor Li+diffusivity across the interphase layer and bulk graphite materials.Various approaches have therefore been explored to address these challenges.On the basis of graphite anode and corresponding LIBs,this review herein offers a comprehensive analysis of the latest advances in electrolyte engineering and electrode modification.First,electrolyte engineering is discussed in detail,highlighting the design of new electrolyte formula with broad liquid temperature range,optimized solvation structure,and well-performed inorganic-rich solid electrolyte interface.The advances in material modification have been then depicted with the view of improving the solid bulk diffusion rate to show general strategies with excellent performance at low temperatures.Finally,the corresponding challenges and opportunities have also been outlined to shed light on viable strategies for developing efficient and reliable graphite anode and graphite-based LIBs under low-temperature scenarios.
文摘Alongside the pursuit of high energy density and long service life,the urgent demand for low-temperature performance remains a long-standing challenge for a wide range of Li-ion battery applications,such as electric vehicles,portable electronics,large-scale grid systems,and special space/seabed/military purposes.Current Li-ion batteries suffer a major loss of capacity and power and fail to operate normally when the temperature decreases to-20℃.This deterioration is mainly attributed to poor Li-ion transport in a bulk carbonated ester electrolyte and its derived solid–electrolyte interphase(SEI).In this mini-review discussing the limiting factors in the Li-ion diffusion process,we propose three basic requirements when formulating electrolytes for low-temperature Liion batteries:low melting point,poor Liþaffinity,and a favorable SEI.Then,we briefly review emerging progress,including liquefied gas electrolytes,weakly solvating electrolytes,and localized high-concentration electrolytes.The proposed novel electrolytes effectively improve the reaction kinetics via accelerating Li-ion diffusion in the bulk electrolyte and interphase.The final part of the paper addresses future challenges and offers perspectives on electrolyte designs for low-temperature Li-ion batteries.
