BACKGROUND: Previous studies have demonstrated that scorpion venom in the scorpion can inhibit epilepsy and apoptosis. However, it remains unclear whether ethanol extracts of scorpion (EES) exhibit similar effects....BACKGROUND: Previous studies have demonstrated that scorpion venom in the scorpion can inhibit epilepsy and apoptosis. However, it remains unclear whether ethanol extracts of scorpion (EES) exhibit similar effects. OBJECTIVE: To investigate the effects of EES on hippocampal apoptosis and caspase-3 expression, and to compare the effects on sodium valproate (positive control drug) in a rat model of status epilepticus induced by lithium chloride-pilocarpine. DESIGN, TIME AND SETTING: This randomized, controlled study was conducted at the Drug Research and Development Center, Kanghong Pharmaceuticals Group, and the Department of Pathology, Sichuan Academy of Medical Sciences & Sichuan Provincial People's Hospital, China from May 2007 to April 2008. MATERIALS: EES were prepared by Huashen Pharmaceutical, China. Sodium valproate (Hunan Xiangzhong Pharmaceutical, China) and lithium chloride-pilocarpine (Sigma, USA) were also used in the present study. METHODS: From a total of 156 rats, six served as normal controls. The remaining rats were intraperitoneally injected with lithium chloride-pilocarpine to establish status epileptlcus models, and then assigned to five groups (n = 30, respectively). Animals in each group were administered drugs at 15 minutes after epileptic seizure by gavage, i.e. in the normal control and model groups, rats were treated with 1 mL/0.1 kg saline. The sodium valproate group was administered 120 mg/kg/d sodium valproate. The low-, moderate-, and high-dose EES groups received treatments of 290, 580 and 1 160 mg/kg/d EES. The dispensed concentration was 1 mL/0.1 kg. Rat seizure behavior was observed. If status epilepticus did not terminated after 1 hour, the rats were intraperitoneally administered atropine (1 mg/kg) and diazepam (10 mg/kg) to terminate seizure. These rats were continuously observed for 6 hours to ensure seizure termination. Then rats were treated with the above-mentioned drugs at 8:00 am each day until sacrifice, which took place 4 hours after drug administration. MAIN OUTCOME MEASURES: Terminal dUTP nick end labeling (TUNEL)-positive cells and caspase-3 expression were, respectively, determined by TUNEL and immunohistochemistry at 6, 24 48, and 72 hours, as well as 7 days, after status epilepticus. Behavioral changes were also measured. RESULTS: A few caspase-3-positive cells were observed. TUNEL- and caspase-3-positive ceils were mainly visible in the hippocampal CA1 and CA3 regions 6 hours following status epilepticus in the model and drug intervention groups. The number of TUNEL-positive cells reached a peak at 48 hours following status epilepticus in the sodium valproate group, as well as the moderate- and high-dose EES groups, and number of TUNEL-positive cells reached a peak at 72 hours in the model and low-dose EES groups. The number of caspase-3-positive cells reached a peak at 48 hours in each group. Following treatment of sodium valproate and EES, the number of TUNEL- and caspase-3-positive cells significantly decreased compared with the model group at various time points (P 〈 0.05). The number of TUNEL- and caspase-3-positive cells was greatest in the low-dose EES group, followed by the moderate- and high-dose EES groups. The number of TUNEL- and caspase-3-positive cells was similar between the sodium valproate and high-dose EES groups. Epileptic seizure was significantly improved in the sodium valproate group, as well as the moderate- and high-dose EES groups, compared with the model group (P〈 0.05 or P〈 0.01). Treatment with sodium valproate and high-dose EES resulted in the best outcome, although the results were similar (P 〉 0.05). CONCLUSION: A dose of 1 160 mg/kg/d EES significantly inhibited status epilepticus. This outcome corresponded to a decreased number of apoptotlc cells and caspase-3-positive cells, which was similar to sodium valproate. These results suggest that it is not necessary to extract a component from the scorpion for the treatment of epilepsy. The high dose of EES significantly inhibited epilepsy, which correlated with decreased hippocampal caspase-3 expression.展开更多
The present study analyzed the effects of ethanol extracts of scorpion on epilepsy prevention and hippocampal expression of glial fibrillary acidic protein in a lithium chloride-pilocarpine epileptic rat model. Result...The present study analyzed the effects of ethanol extracts of scorpion on epilepsy prevention and hippocampal expression of glial fibrillary acidic protein in a lithium chloride-pilocarpine epileptic rat model. Results were subsequently compared with valproic acid. Results showed gradually- increased hippocampal glial fibrillary acidic protein expression following model establishment; glial fibrillary acidic protein mRNA expression was significantly increased at 3 days, reached a peak at 7 days, and then gradually decreased thereafter. Ethanol extracts of scorpion doses of 580 and 1 160 mg/kg, as well as 120 mg/kg valproic acid, led to a decreased number of glial fibrillary acidic protein-positive cells and glial fibrillary acidic protein mRNA expression, as well as decreased seizure grades and frequency of spontaneously recurrent seizures. The effects of 1 160 mg/kg ethanol extracts of scorpion were equal to those of 120 mg/kg valproic acid. These results suggested that the anti-epileptic effect of ethanol extracts of scorpion were associated with decreased hippocampal glial fibrillary acidic protein expression in a rat model of lithium chlofide-pilocarpine induced epilepsy.展开更多
Safe batteries are the basis for next-generation application scenarios such as portable energy storage devices and electric vehicles,which are crucial to achieving carbon neutralization.Electrolytes,separators,and ele...Safe batteries are the basis for next-generation application scenarios such as portable energy storage devices and electric vehicles,which are crucial to achieving carbon neutralization.Electrolytes,separators,and electrodes as main components of lithium batteries strongly affect the occurrence of safety accidents.Responsive materials,which can respond to external stimuli or environmental change,have triggered extensive attentions recently,holding great promise in facilitating safe and smart batteries.This review thoroughly discusses recent advances regarding the construction of high-safety lithium batteries based on internal thermal-responsive strategies,together with the corresponding changes in electrochemical performance under external stimulus.Furthermore,the existing challenges and outlook for the design of safe batteries are presented,creating valuable insights and proposing directions for the practical implementation of safe lithium batteries.展开更多
Lithium–sulfur(Li–S)batteries are supposed to be one of the most potential next-generation batteries owing to their high theoretical capacity and low cost.Nevertheless,the shuttle effect of firm multi-step two-elect...Lithium–sulfur(Li–S)batteries are supposed to be one of the most potential next-generation batteries owing to their high theoretical capacity and low cost.Nevertheless,the shuttle effect of firm multi-step two-electron reaction between sulfur and lithium in liquid electrolyte makes the capacity much smaller than the theoretical value.Many methods were proposed for inhibiting the shuttle effect of polysulfide,improving corresponding redox kinetics and enhancing the integral performance of Li–S batteries.Here,we will comprehensively and systematically summarize the strategies for inhibiting the shuttle effect from all components of Li–S batteries.First,the electrochemical principles/mechanism and origin of the shuttle effect are described in detail.Moreover,the efficient strategies,including boosting the sulfur conversion rate of sulfur,confining sulfur or lithium polysulfides(LPS)within cathode host,confining LPS in the shield layer,and preventing LPS from contacting the anode,will be discussed to suppress the shuttle effect.Then,recent advances in inhibition of shuttle effect in cathode,electrolyte,separator,and anode with the aforementioned strategies have been summarized to direct the further design of efficient materials for Li–S batteries.Finally,we present prospects for inhibition of the LPS shuttle and potential development directions in Li–S batteries.展开更多
The widespread adoption of lithium-ion batteries has been driven by the proliferation of portable electronic devices and electric vehicles,which have increasingly stringent energy density requirements.Lithium metal ba...The widespread adoption of lithium-ion batteries has been driven by the proliferation of portable electronic devices and electric vehicles,which have increasingly stringent energy density requirements.Lithium metal batteries(LMBs),with their ultralow reduction potential and high theoretical capacity,are widely regarded as the most promising technical pathway for achieving high energy density batteries.In this review,we provide a comprehensive overview of fundamental issues related to high reactivity and migrated interfaces in LMBs.Furthermore,we propose improved strategies involving interface engineering,3D current collector design,electrolyte optimization,separator modification,application of alloyed anodes,and external field regulation to address these challenges.The utilization of solid-state electrolytes can significantly enhance the safety of LMBs and represents the only viable approach for advancing them.This review also encompasses the variation in fundamental issues and design strategies for the transition from liquid to solid electrolytes.Particularly noteworthy is that the introduction of SSEs will exacerbate differences in electrochemical and mechanical properties at the interface,leading to increased interface inhomogeneity—a critical factor contributing to failure in all-solidstate lithium metal batteries.Based on recent research works,this perspective highlights the current status of research on developing high-performance LMBs.展开更多
An anion-rich electric double layer(EDL)region is favorable for fabricating an inorganic-rich solid-electrolyte interphase(SEI)towards stable lithium metal anode in ester electrolyte.Herein,cetyltrimethylammonium brom...An anion-rich electric double layer(EDL)region is favorable for fabricating an inorganic-rich solid-electrolyte interphase(SEI)towards stable lithium metal anode in ester electrolyte.Herein,cetyltrimethylammonium bromide(CTAB),a cationic surfactant,is adopted to draw more anions into EDL by ionic interactions that shield the repelling force on anions during lithium plating.In situ electrochemical surface-enhanced Raman spectroscopy results combined with molecular dynamics simulations validate the enrichment of NO_(3)^(−)/FSI−anions in the EDL region due to the positively charged CTA^(+).In-depth analysis of SEI structure by X-ray photoelectron spectroscopy and time-of-flight secondary ion mass spectrometry results confirmed the formation of the inorganic-rich SEI,which helps improve the kinetics of Li^(+)transfer,lower the charge transfer activation energy,and homogenize Li deposition.As a result,the Li||Li symmetric cell in the designed electrolyte displays a prolongated cycling time from 500 to 1300 h compared to that in the blank electrolyte at 0.5 mA cm^(-2) with a capacity of 1 mAh cm^(-2).Moreover,Li||LiFePO_(4) and Li||LiCoO_(2) with a high cathode mass loading of>10 mg cm^(-2) can be stably cycled over 180 cycles.展开更多
Improving the long-term cycling stability and energy density of all-solid-state lithium(Li)-metal batteries(ASSLMBs)at room temperature is a severe challenge because of the notorious solid–solid interfacial contact l...Improving the long-term cycling stability and energy density of all-solid-state lithium(Li)-metal batteries(ASSLMBs)at room temperature is a severe challenge because of the notorious solid–solid interfacial contact loss and sluggish ion transport.Solid electrolytes are generally studied as two-dimensional(2D)structures with planar interfaces,showing limited interfacial contact and further resulting in unstable Li/electrolyte and cathode/electrolyte interfaces.Herein,three-dimensional(3D)architecturally designed composite solid electrolytes are developed with independently controlled structural factors using 3D printing processing and post-curing treatment.Multiple-type electrolyte films with vertical-aligned micro-pillar(p-3DSE)and spiral(s-3DSE)structures are rationally designed and developed,which can be employed for both Li metal anode and cathode in terms of accelerating the Li+transport within electrodes and reinforcing the interfacial adhesion.The printed p-3DSE delivers robust long-term cycle life of up to 2600 cycles and a high critical current density of 1.92 mA cm^(−2).The optimized electrolyte structure could lead to ASSLMBs with a superior full-cell areal capacity of 2.75 mAh cm^(−2)(LFP)and 3.92 mAh cm^(−2)(NCM811).This unique design provides enhancements for both anode and cathode electrodes,thereby alleviating interfacial degradation induced by dendrite growth and contact loss.The approach in this study opens a new design strategy for advanced composite solid polymer electrolytes in ASSLMBs operating under high rates/capacities and room temperature.展开更多
All-solid-state lithium metal batteries(ASSLMBs)with solid electrolytes(SEs)have emerged as a promising alternative to liquid electrolyte-based Li-ion batteries due to their higher energy density and safety.However,si...All-solid-state lithium metal batteries(ASSLMBs)with solid electrolytes(SEs)have emerged as a promising alternative to liquid electrolyte-based Li-ion batteries due to their higher energy density and safety.However,since ASSLMBs lack the wetting properties of liquid electrolytes,they require stacking pressure to prevent contact loss between electrodes and SEs.Though previous studies showed that stacking pressure could impact certain performance aspects,a comprehensive investigation into the effects of stacking pressure has not been conducted.To address this gap,we utilized the Li_(6)PS_(5)Cl solid electrolyte as a reference and investigated the effects of stacking pressures on the performance of SEs and ASSLMBs.We also developed models to explain the underlying origin of these effects and predict battery performance,such as ionic conductivity and critical current density.Our results demonstrated that an appropriate stacking pressure is necessary to achieve optimal performance,and each step of applying pressure requires a specific pressure value.These findings can help explain discrepancies in the literature and provide guidance to establish standardized testing conditions and reporting benchmarks for ASSLMBs.Overall,this study contributes to the understanding of the impact of stacking pressure on the performance of ASSLMBs and highlights the importance of careful pressure optimization for optimal battery performance.展开更多
Solid-state lithium metal batteries(SSLMBs)show great promise in terms of high-energy-density and high-safety performance.However,there is an urgent need to address the compatibility of electrolytes with high-voltage ...Solid-state lithium metal batteries(SSLMBs)show great promise in terms of high-energy-density and high-safety performance.However,there is an urgent need to address the compatibility of electrolytes with high-voltage cathodes/Li anodes,and to minimize the electrolyte thickness to achieve highenergy-density of SSLMBs.Herein,we develop an ultrathin(12.6μm)asymmetric composite solid-state electrolyte with ultralight areal density(1.69 mg cm^(−2))for SSLMBs.The electrolyte combining a garnet(LLZO)layer and a metal organic framework(MOF)layer,which are fabricated on both sides of the polyethylene(PE)separator separately by tape casting.The PE separator endows the electrolyte with flexibility and excellent mechanical properties.The LLZO layer on the cathode side ensures high chemical stability at high voltage.The MOF layer on the anode side achieves a stable electric field and uniform Li flux,thus promoting uniform Li^(+)deposition.Thanks to the well-designed structure,the Li symmetric battery exhibits an ultralong cycle life(5000 h),and high-voltage SSLMBs achieve stable cycle performance.The assembled pouch cells provided a gravimetric/volume energy density of 344.0 Wh kg^(−1)/773.1 Wh L^(−1).This simple operation allows for large-scale preparation,and the design concept of ultrathin asymmetric structure also reveals the future development direction of SSLMBs.展开更多
Silicon(Si)is a promising anode material for lithium‐ion batteries(LIBs)owing to its tremendously high theoretical storage capacity(4200 mAh g−1),which has the potential to elevate the energy of LIBs.However,Si anode...Silicon(Si)is a promising anode material for lithium‐ion batteries(LIBs)owing to its tremendously high theoretical storage capacity(4200 mAh g−1),which has the potential to elevate the energy of LIBs.However,Si anodes exhibit severe volume change during lithiation/delithiation processes,resulting in anode pulverization and delamination with detrimental growth of solid electrolyte interface layers.As a result,the cycling stability of Si anodes is insufficient for commercialization in LIBs.Polymeric binders can play critical roles in Si anodes by affecting their cycling stability,although they occupy a small portion of the electrodes.This review introduces crucial factors influencing polymeric binders'properties and the electrochemical performance of Si anodes.In particular,we emphasize the structure–property relationships of binders in the context of molecular design strategy,functional groups,types of interactions,and functionalities of binders.Furthermore,binders with additional functionalities,such as electrical conductivity and self‐healability,are extensively discussed,with an emphasis on the binder design principle.展开更多
Clay-type Li deposits are poised to play a pivotal role in addressing the surging global demand for Li.The McDermitt clay-type Li deposit,located in Nevada,is the largest Li deposit in the United States,with Li hosted...Clay-type Li deposits are poised to play a pivotal role in addressing the surging global demand for Li.The McDermitt clay-type Li deposit,located in Nevada,is the largest Li deposit in the United States,with Li hosted by a clay-rich sequence of smectite-dominated intervals and illite-dominated intervals,respectively.However,the occurrence of Li and the genesis of Li-bearing minerals within smectite-dominated intervals have not been thoroughly investigated in previous research.Here,we studied the mineralogy,the in-situ Li distribution,and the bonding environments of Li within the smectite intervals using a combination of instru-mental techniques including scanning electron microscope,transmission electron microscope,time-of-flight secondary ion mass spectrometry,and nuclear magnetic resonance.Our results indicate that the smectite exhibits low crystallinity characteristics of lacustrine clay authigenesis and is com-monly found tofill the interstices among volcanic minerals or envelop them;Li is mainly hosted by Mg-smectite rather than the volcanic minerals.Within the tuffaceous sediment samples,the volcanic glass has undergone a transformation,resulting in its complete disappearance and alteration into clay minerals.Owing to the octahedral sites of Mg-smectite bounded in Li,it is referred to be hectorite.We interpret that the hectorite’s precipitation occurs in a high saline-alkaline water environment,a result of McDermitt tuffdissolution.This conclusion can be supported by the coexistence of spherulitic calcite and hectorite.Overall,this study confirms hectorite as the main Li-bearing mineral and increases the understanding of the genetic model of hectorite formation in intracontinental caldera basins.展开更多
Li metal batteries using high-voltage layered oxides cathodes are of particular interest due to their high energy density.However,they suffer from short lifespan and extreme safety concerns,which are attributed to the...Li metal batteries using high-voltage layered oxides cathodes are of particular interest due to their high energy density.However,they suffer from short lifespan and extreme safety concerns,which are attributed to the degradation of layered oxides and the decomposition of electrolyte at high voltage,as well as the high reactivity of metallic Li.The key is the development of stable electrolytes against both highvoltage cathodes and Li with the formation of robust interphase films on the surfaces.Herein,we report a highly fluorinated ether,1,1,1-trifluoro-2-[(2,2,2-trifluoroethoxy)methoxy]ethane(TTME),as a cosolvent,which not only functions as a diluent forming a localized high concentration electrolyte(LHCE),but also participates in the construction of the inner solvation structure.The TTME-based electrolyte is stable itself at high voltage and induces the formation of a unique double-layer solid electrolyte interphase(SEI)film,which is embodied as one layer rich in crystalline structural components for enhanced mechanical strength and another amorphous layer with a higher concentration of organic components for enhanced flexibility.The Li||Cu cells display a noticeably high Coulombic efficiency of 99.28%after 300 cycles and Li symmetric cells maintain stable cycling more than 3200 h at 0.5 mA/cm^(2) and 1.0m Ah/cm^(2).In addition,lithium metal cells using LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2) and Li CoO_(2) cathodes(both loadings~3.0 m Ah/cm^(2))realize capacity retentions of>85%over 240 cycles with a charge cut-off voltage of 4.4 V and 90%for 170 cycles with a charge cut-off voltage of 4.5 V,respectively.This study offers a bifunctional ether-based electrolyte solvent beneficial for high-voltage Li metal batteries.展开更多
Exploration of advanced gel polymer electrolytes(GPEs)represents a viable strategy for mitigating dendritic lithium(Li)growth,which is crucial in ensuring the safe operation of high energy density Li metal batteries(L...Exploration of advanced gel polymer electrolytes(GPEs)represents a viable strategy for mitigating dendritic lithium(Li)growth,which is crucial in ensuring the safe operation of high energy density Li metal batteries(LMBs).Despite this,the application of GPEs is still hindered by inadequate ionic conductivity,low Li^(+)transference number,and subpar physicochemical properties.Herein,Ti O_(2-x)nanofibers(NF)with oxygen vacancy defects were synthesized by a one-step process as inorganic fillers to enhance the thermal/mechanical/ionic-transportation performances of composite GPEs.Various characterizations and theoretical calculations reveal that the oxygen vacancies on the surface of Ti O_(2-x)NF accelerate the dissociation of Li PF_6,promote the rapid transfer of free Li^(+),and influence the formation of Li F-enriched solid electrolyte interphase.Consequently,the composite GPEs demonstrate enhanced ionic conductivity(1.90m S cm^(-1)at room temperature),higher lithium-ion transference number(0.70),wider electrochemical stability window(5.50 V),superior mechanical strength,excellent thermal stability(210℃),and improved compatibility with lithium,resulting in superior cycling stability and rate performance in both Li||Li,Li||Li Fe PO_(4),and Li||Li Ni_(0.8)Co_(0.1)Mn_(0.1)O_(2)cells.Overall,the synergistic influence of nanofiber morphology and enriched oxygen vacancy structure of fillers on electrochemical properties of composite GPEs is comprehensively investigated,thus,it is anticipated to shed new light on designing high-performance GPEs LMBs.展开更多
The function of solid electrolytes and the composition of solid electrolyte interphase(SEI)are highly significant for inhibiting the growth of Li dendrites.Herein,we report an in-situ interfacial passivation combined ...The function of solid electrolytes and the composition of solid electrolyte interphase(SEI)are highly significant for inhibiting the growth of Li dendrites.Herein,we report an in-situ interfacial passivation combined with self-adaptability strategy to reinforce Li_(0.33)La_(0.557)TiO_(3)(LLTO)-based solid-state batteries.Specifically,a functional SEI enriched with LiF/Li_(3)PO_(4) is formed by in-situ electrochemical conversion,which is greatly beneficial to improving interface compatibility and enhancing ion transport.While the polarized dielectric BaTiO_(3)-polyamic acid(BTO-PAA,BP)film greatly improves the Li-ion transport kinetics and homogenizes the Li deposition.As expected,the resulting electrolyte offers considerable ionic conductivity at room temperature(4.3 x 10~(-4)S cm^(-1))and appreciable electrochemical decomposition voltage(5.23 V)after electrochemical passivation.For Li-LiFePO_(4) batteries,it shows a high specific capacity of 153 mA h g^(-1)at 0.2C after 100 cycles and a long-term durability of 115 mA h g^(-1)at 1.0 C after 800 cycles.Additionally,a stable Li plating/stripping can be achieved for more than 900 h at 0.5 mA cm^(-2).The stabilization mechanisms are elucidated by ex-situ XRD,ex-situ XPS,and ex-situ FTIR techniques,and the corresponding results reveal that the interfacial passivation combined with polarization effect is an effective strategy for improving the electrochemical performance.The present study provides a deeper insight into the dynamic adjustment of electrode-electrolyte interfacial for solid-state lithium batteries.展开更多
Inhomogeneous lithium-ion(Li^(+))deposition is one of the most crucial problems,which severely deteriorates the performance of solid-state lithium metal batteries(LMBs).Herein,we discovered that covalent organic frame...Inhomogeneous lithium-ion(Li^(+))deposition is one of the most crucial problems,which severely deteriorates the performance of solid-state lithium metal batteries(LMBs).Herein,we discovered that covalent organic framework(COF-1)with periodically arranged boron-oxygen dipole lithiophilic sites could directionally guide Li^(+)even deposition in asymmetric solid polymer electrolytes.This in situ prepared 3D cross-linked network Poly(ACMO-MBA)hybrid electrolyte simultaneously delivers outstanding ionic conductivity(1.02×10^(-3)S cm^(-1)at 30°C)and excellent mechanical property(3.5 MPa).The defined nanosized channel in COF-1 selectively conducts Li^(+)increasing Li^(+)transference number to 0.67.Besides,The COF-1 layer and Poly(ACMO-MBA)also participate in forming a boron-rich and nitrogen-rich solid electrolyte interface to further improve the interfacial stability.The Li‖Li symmetric cell exhibits remarkable cyclic stability over 1000 h.The Li‖NCM523 full cell also delivers an outstanding lifespan over 400 cycles.Moreover,the Li‖LiFePO_(4)full cell stably cycles with a capacity retention of 85%after 500 cycles.the Li‖LiFePO_(4)pouch full exhibits excellent safety performance under pierced and cut conditions.This work thereby further broadens and complements the application of COF materials in polymer electrolyte for dendrite-free and high-energy-density solid-state LMBs.展开更多
The safety valve is an important component to ensure the safe operation of lithium-ion batteries(LIBs).However,the effect of safety valve type on the thermal runaway(TR)and gas venting behavior of LIBs,as well as the ...The safety valve is an important component to ensure the safe operation of lithium-ion batteries(LIBs).However,the effect of safety valve type on the thermal runaway(TR)and gas venting behavior of LIBs,as well as the TR hazard severity of LIBs,are not known.In this paper,the TR and gas venting behavior of three 100 A h lithium iron phosphate(LFP)batteries with different safety valves are investigated under overheating.Compared to previous studies,the main contribution of this work is in studying and evaluating the effect of gas venting behavior and TR hazard severity of LFP batteries with three safety valve types.Two significant results are obtained:(Ⅰ)the safety valve type dominates over gas venting pressure of battery during safety venting,the maximum gas venting pressure of LFP batteries with a round safety valve is 3320 Pa,which is one order of magnitude higher than other batteries with oval or cavity safety valve;(Ⅱ)the LFP battery with oval safety valve has the lowest TR hazard as shown by the TR hazard assessment model based on gray-fuzzy analytic hierarchy process.This study reveals the effect of safety valve type on TR and gas venting,providing a clear direction for the safety valve design.展开更多
Solid polymer electrolyte(SPE) shows great potential for all-solid-state batteries because of the inherent safety and flexibility;however, the unfavourable Li+deposition and large thickness hamper its development and ...Solid polymer electrolyte(SPE) shows great potential for all-solid-state batteries because of the inherent safety and flexibility;however, the unfavourable Li+deposition and large thickness hamper its development and application. Herein, a laminar MXene functional layer-thin SPE layer-cathode integration(MXene-PEO-LFP) is designed and fabricated. The MXene functional layer formed by stacking rigid MXene nanosheets imparts higher compressive strength relative to PEO electrolyte layer. And the abundant negatively-charged groups on MXene functional layer effectively repel anions and attract cations to adjust the charge distribution behavior at electrolyte–anode interface. Furthermore,the functional layer with rich lithiophilic groups and outstanding electronic conductivity results in low Li nucleation overpotential and nucleation energy barrier. In consequence, the cell assembled with MXene-PEO-LFP, where the PEO electrolyte layer is only 12 μm, much thinner than most solid electrolytes, exhibits uniform, dendrite-free Li+deposition and excellent cycling stability. High capacity(142.8 mAh g-1), stable operation of 140 cycles(capacity decay per cycle, 0.065%), and low polarization potential(0.5 C) are obtained in this Li|MXene-PEO-LFP cell,which is superior to most PEO-based electrolytes under identical condition. This integrated design may provide a strategy for the large-scale application of thin polymer electrolytes in all-solid-state battery.展开更多
Silicon(Si)is widely used as a lithium‐ion‐battery anode owing to its high capacity and abundant crustal reserves.However,large volume change upon cycling and poor conductivity of Si cause rapid capacity decay and p...Silicon(Si)is widely used as a lithium‐ion‐battery anode owing to its high capacity and abundant crustal reserves.However,large volume change upon cycling and poor conductivity of Si cause rapid capacity decay and poor fast‐charging capability limiting its commercial applications.Here,we propose a multilevel carbon architecture with vertical graphene sheets(VGSs)grown on surfaces of subnanoscopically and homogeneously dispersed Si–C composite nanospheres,which are subsequently embedded into a carbon matrix(C/VGSs@Si–C).Subnanoscopic C in the Si–C nanospheres,VGSs,and carbon matrix form a three‐dimensional conductive and robust network,which significantly improves the conductivity and suppresses the volume expansion of Si,thereby boosting charge transport and improving electrode stability.The VGSs with vast exposed edges considerably increase the contact area with the carbon matrix and supply directional transport channels through the entire material,which boosts charge transport.The carbon matrix encapsulates VGSs@Si–C to decrease the specific surface area and increase tap density,thus yielding high first Coulombic efficiency and electrode compaction density.Consequently,C/VGSs@Si–C delivers excellent Li‐ion storage performances under industrial electrode conditions.In particular,the full cells show high energy densities of 603.5 Wh kg^(−1)and 1685.5 Wh L^(−1)at 0.1 C and maintain 80.7%of the energy density at 3 C.展开更多
Lithium recovery from spent lithium-ion batteries(LIBs)have attracted extensive attention due to the skyrocketing price of lithium.The medium-temperature carbon reduction roasting was proposed to preferential selectiv...Lithium recovery from spent lithium-ion batteries(LIBs)have attracted extensive attention due to the skyrocketing price of lithium.The medium-temperature carbon reduction roasting was proposed to preferential selective extraction of lithium from spent Li-CoO_(2)(LCO)cathodes to overcome the incomplete recovery and loss of lithium during the recycling process.The LCO layered structure was destroyed and lithium was completely converted into water-soluble Li2CO_(3)under a suitable temperature to control the reduced state of the cobalt oxide.The Co metal agglomerates generated during medium-temperature carbon reduction roasting were broken by wet grinding and ultrasonic crushing to release the entrained lithium.The results showed that 99.10%of the whole lithium could be recovered as Li2CO_(3)with a purity of 99.55%.This work provided a new perspective on the preferentially selective extraction of lithium from spent lithium batteries.展开更多
Lithium recovery from end-of-life Li-ion batteries(LIBs)through pyro-and hydrometallurgical recycling processes involves several refining stages,with high consumption of reagents and energy.A competitive technological...Lithium recovery from end-of-life Li-ion batteries(LIBs)through pyro-and hydrometallurgical recycling processes involves several refining stages,with high consumption of reagents and energy.A competitive technological alternative is the electrochemical oxidation of the cathode materials,whereby lithium can be deintercalated and transferred to an electrolyte solution without the aid of chemical extracting compounds.This article investigates the potential to selectively recover Li from LIB cathode materials by direct electrochemical extraction in aqueous solutions.The process allowed to recovering up to 98%of Li from high-purity commercial cathode materials(LiMn_(2)O_(4),LiCoO_(2),and Li Ni_(1/3)Mn_(1/3)Co_(1/3)O_(2))with a faradaic efficiency of 98%and negligible co-extraction of Co,Ni,and Mn.The process was then applied to recover Li from the real waste LIBs black mass obtained by the physical treatment of electric vehicle battery packs.This black mass contained graphite,conductive carbon,and metal impurities from current collectors and steel cases,which significantly influenced the evolution and performances of Li electrochemical extraction.Particularly,due to concomitant oxidation of impurities,lithium extraction yields and faradaic efficiencies were lower than those obtained with high-purity cathode materials.Copper oxidation was found to occur within the voltage range investigated,but it could not quantitatively explain the reduced Li extraction performances.In fact,a detailed investigation revealed that above 1.3 V vs.Ag/Ag Cl,conductive carbon can be oxidized,contributing to the decreased Li extraction.Based on the reported experimental results,guidelines were provided that quantitatively enable the extraction of Li from the black mass,while preventing the simultaneous oxidation of impurities and,consequently,reducing the energy consumption of the proposed Li recovery method.展开更多
基金the National Natural Science Foundation of China,No.30740035the Tackle Key Program of Sichuan Province,No.05SG1672
文摘BACKGROUND: Previous studies have demonstrated that scorpion venom in the scorpion can inhibit epilepsy and apoptosis. However, it remains unclear whether ethanol extracts of scorpion (EES) exhibit similar effects. OBJECTIVE: To investigate the effects of EES on hippocampal apoptosis and caspase-3 expression, and to compare the effects on sodium valproate (positive control drug) in a rat model of status epilepticus induced by lithium chloride-pilocarpine. DESIGN, TIME AND SETTING: This randomized, controlled study was conducted at the Drug Research and Development Center, Kanghong Pharmaceuticals Group, and the Department of Pathology, Sichuan Academy of Medical Sciences & Sichuan Provincial People's Hospital, China from May 2007 to April 2008. MATERIALS: EES were prepared by Huashen Pharmaceutical, China. Sodium valproate (Hunan Xiangzhong Pharmaceutical, China) and lithium chloride-pilocarpine (Sigma, USA) were also used in the present study. METHODS: From a total of 156 rats, six served as normal controls. The remaining rats were intraperitoneally injected with lithium chloride-pilocarpine to establish status epileptlcus models, and then assigned to five groups (n = 30, respectively). Animals in each group were administered drugs at 15 minutes after epileptic seizure by gavage, i.e. in the normal control and model groups, rats were treated with 1 mL/0.1 kg saline. The sodium valproate group was administered 120 mg/kg/d sodium valproate. The low-, moderate-, and high-dose EES groups received treatments of 290, 580 and 1 160 mg/kg/d EES. The dispensed concentration was 1 mL/0.1 kg. Rat seizure behavior was observed. If status epilepticus did not terminated after 1 hour, the rats were intraperitoneally administered atropine (1 mg/kg) and diazepam (10 mg/kg) to terminate seizure. These rats were continuously observed for 6 hours to ensure seizure termination. Then rats were treated with the above-mentioned drugs at 8:00 am each day until sacrifice, which took place 4 hours after drug administration. MAIN OUTCOME MEASURES: Terminal dUTP nick end labeling (TUNEL)-positive cells and caspase-3 expression were, respectively, determined by TUNEL and immunohistochemistry at 6, 24 48, and 72 hours, as well as 7 days, after status epilepticus. Behavioral changes were also measured. RESULTS: A few caspase-3-positive cells were observed. TUNEL- and caspase-3-positive ceils were mainly visible in the hippocampal CA1 and CA3 regions 6 hours following status epilepticus in the model and drug intervention groups. The number of TUNEL-positive cells reached a peak at 48 hours following status epilepticus in the sodium valproate group, as well as the moderate- and high-dose EES groups, and number of TUNEL-positive cells reached a peak at 72 hours in the model and low-dose EES groups. The number of caspase-3-positive cells reached a peak at 48 hours in each group. Following treatment of sodium valproate and EES, the number of TUNEL- and caspase-3-positive cells significantly decreased compared with the model group at various time points (P 〈 0.05). The number of TUNEL- and caspase-3-positive cells was greatest in the low-dose EES group, followed by the moderate- and high-dose EES groups. The number of TUNEL- and caspase-3-positive cells was similar between the sodium valproate and high-dose EES groups. Epileptic seizure was significantly improved in the sodium valproate group, as well as the moderate- and high-dose EES groups, compared with the model group (P〈 0.05 or P〈 0.01). Treatment with sodium valproate and high-dose EES resulted in the best outcome, although the results were similar (P 〉 0.05). CONCLUSION: A dose of 1 160 mg/kg/d EES significantly inhibited status epilepticus. This outcome corresponded to a decreased number of apoptotlc cells and caspase-3-positive cells, which was similar to sodium valproate. These results suggest that it is not necessary to extract a component from the scorpion for the treatment of epilepsy. The high dose of EES significantly inhibited epilepsy, which correlated with decreased hippocampal caspase-3 expression.
基金sponsored by the National Natural Science Foundation of China, No. 30740035Key Scientific and Technological Project of Sichuan Province, No. 05SG1672
文摘The present study analyzed the effects of ethanol extracts of scorpion on epilepsy prevention and hippocampal expression of glial fibrillary acidic protein in a lithium chloride-pilocarpine epileptic rat model. Results were subsequently compared with valproic acid. Results showed gradually- increased hippocampal glial fibrillary acidic protein expression following model establishment; glial fibrillary acidic protein mRNA expression was significantly increased at 3 days, reached a peak at 7 days, and then gradually decreased thereafter. Ethanol extracts of scorpion doses of 580 and 1 160 mg/kg, as well as 120 mg/kg valproic acid, led to a decreased number of glial fibrillary acidic protein-positive cells and glial fibrillary acidic protein mRNA expression, as well as decreased seizure grades and frequency of spontaneously recurrent seizures. The effects of 1 160 mg/kg ethanol extracts of scorpion were equal to those of 120 mg/kg valproic acid. These results suggested that the anti-epileptic effect of ethanol extracts of scorpion were associated with decreased hippocampal glial fibrillary acidic protein expression in a rat model of lithium chlofide-pilocarpine induced epilepsy.
基金supported by the National Natural Science Foundation of China(22179070,U1932220)the Natural Science Foundation of Jiangsu Province(BK20220073)the Fundamental Research Funds for the Central Universities(RF1028623157)。
文摘Safe batteries are the basis for next-generation application scenarios such as portable energy storage devices and electric vehicles,which are crucial to achieving carbon neutralization.Electrolytes,separators,and electrodes as main components of lithium batteries strongly affect the occurrence of safety accidents.Responsive materials,which can respond to external stimuli or environmental change,have triggered extensive attentions recently,holding great promise in facilitating safe and smart batteries.This review thoroughly discusses recent advances regarding the construction of high-safety lithium batteries based on internal thermal-responsive strategies,together with the corresponding changes in electrochemical performance under external stimulus.Furthermore,the existing challenges and outlook for the design of safe batteries are presented,creating valuable insights and proposing directions for the practical implementation of safe lithium batteries.
基金support from the “Joint International Laboratory on Environmental and Energy Frontier Materials”“Innovation Research Team of High-Level Local Universities in Shanghai”support from the National Natural Science Foundation of China (22209103)
文摘Lithium–sulfur(Li–S)batteries are supposed to be one of the most potential next-generation batteries owing to their high theoretical capacity and low cost.Nevertheless,the shuttle effect of firm multi-step two-electron reaction between sulfur and lithium in liquid electrolyte makes the capacity much smaller than the theoretical value.Many methods were proposed for inhibiting the shuttle effect of polysulfide,improving corresponding redox kinetics and enhancing the integral performance of Li–S batteries.Here,we will comprehensively and systematically summarize the strategies for inhibiting the shuttle effect from all components of Li–S batteries.First,the electrochemical principles/mechanism and origin of the shuttle effect are described in detail.Moreover,the efficient strategies,including boosting the sulfur conversion rate of sulfur,confining sulfur or lithium polysulfides(LPS)within cathode host,confining LPS in the shield layer,and preventing LPS from contacting the anode,will be discussed to suppress the shuttle effect.Then,recent advances in inhibition of shuttle effect in cathode,electrolyte,separator,and anode with the aforementioned strategies have been summarized to direct the further design of efficient materials for Li–S batteries.Finally,we present prospects for inhibition of the LPS shuttle and potential development directions in Li–S batteries.
基金This work is supported by the Technologies R&D Program of Huzhou City(No.2022JB01)the Key Research and Development Program of Zhejiang Province(No.2023C01127)the Highstar Corporation HSD20210118.
文摘The widespread adoption of lithium-ion batteries has been driven by the proliferation of portable electronic devices and electric vehicles,which have increasingly stringent energy density requirements.Lithium metal batteries(LMBs),with their ultralow reduction potential and high theoretical capacity,are widely regarded as the most promising technical pathway for achieving high energy density batteries.In this review,we provide a comprehensive overview of fundamental issues related to high reactivity and migrated interfaces in LMBs.Furthermore,we propose improved strategies involving interface engineering,3D current collector design,electrolyte optimization,separator modification,application of alloyed anodes,and external field regulation to address these challenges.The utilization of solid-state electrolytes can significantly enhance the safety of LMBs and represents the only viable approach for advancing them.This review also encompasses the variation in fundamental issues and design strategies for the transition from liquid to solid electrolytes.Particularly noteworthy is that the introduction of SSEs will exacerbate differences in electrochemical and mechanical properties at the interface,leading to increased interface inhomogeneity—a critical factor contributing to failure in all-solidstate lithium metal batteries.Based on recent research works,this perspective highlights the current status of research on developing high-performance LMBs.
基金financial support from Singapore Ministry of Education under its AcRF Tier 2 Grant No MOE-T2EP10123-0001Singapore National Research Foundation Investigatorship under Grant No NRF-NRFI08-2022-0009Academic Excellence Foundation of BUAA for PhD Students(applicant:Hongfei Xu).
文摘An anion-rich electric double layer(EDL)region is favorable for fabricating an inorganic-rich solid-electrolyte interphase(SEI)towards stable lithium metal anode in ester electrolyte.Herein,cetyltrimethylammonium bromide(CTAB),a cationic surfactant,is adopted to draw more anions into EDL by ionic interactions that shield the repelling force on anions during lithium plating.In situ electrochemical surface-enhanced Raman spectroscopy results combined with molecular dynamics simulations validate the enrichment of NO_(3)^(−)/FSI−anions in the EDL region due to the positively charged CTA^(+).In-depth analysis of SEI structure by X-ray photoelectron spectroscopy and time-of-flight secondary ion mass spectrometry results confirmed the formation of the inorganic-rich SEI,which helps improve the kinetics of Li^(+)transfer,lower the charge transfer activation energy,and homogenize Li deposition.As a result,the Li||Li symmetric cell in the designed electrolyte displays a prolongated cycling time from 500 to 1300 h compared to that in the blank electrolyte at 0.5 mA cm^(-2) with a capacity of 1 mAh cm^(-2).Moreover,Li||LiFePO_(4) and Li||LiCoO_(2) with a high cathode mass loading of>10 mg cm^(-2) can be stably cycled over 180 cycles.
基金This work was financially supported by Stable Support Plan Program for Higher Education Institutions(20220815094504001)Shenzhen Key Laboratory of Advanced Energy Storage(ZDSYS20220401141000001)+1 种基金This work was also financially supported by the Shenzhen Science and Technology Innovation Commission(GJHZ20200731095606021,20200925155544005)the Project of Hetao Shenzhen-Hong Kong Science and Technology Innovation Cooperation Zone(HZQB-KCZYB-2020083)。
文摘Improving the long-term cycling stability and energy density of all-solid-state lithium(Li)-metal batteries(ASSLMBs)at room temperature is a severe challenge because of the notorious solid–solid interfacial contact loss and sluggish ion transport.Solid electrolytes are generally studied as two-dimensional(2D)structures with planar interfaces,showing limited interfacial contact and further resulting in unstable Li/electrolyte and cathode/electrolyte interfaces.Herein,three-dimensional(3D)architecturally designed composite solid electrolytes are developed with independently controlled structural factors using 3D printing processing and post-curing treatment.Multiple-type electrolyte films with vertical-aligned micro-pillar(p-3DSE)and spiral(s-3DSE)structures are rationally designed and developed,which can be employed for both Li metal anode and cathode in terms of accelerating the Li+transport within electrodes and reinforcing the interfacial adhesion.The printed p-3DSE delivers robust long-term cycle life of up to 2600 cycles and a high critical current density of 1.92 mA cm^(−2).The optimized electrolyte structure could lead to ASSLMBs with a superior full-cell areal capacity of 2.75 mAh cm^(−2)(LFP)and 3.92 mAh cm^(−2)(NCM811).This unique design provides enhancements for both anode and cathode electrodes,thereby alleviating interfacial degradation induced by dendrite growth and contact loss.The approach in this study opens a new design strategy for advanced composite solid polymer electrolytes in ASSLMBs operating under high rates/capacities and room temperature.
基金supported by National Key Research and Development Program of China(No.2021YFF0500600)Key R&D Projects in Henan Province(221111240100)China Postdoctoral Science Foundation(2022TQ0291 and 2022M712869)
文摘All-solid-state lithium metal batteries(ASSLMBs)with solid electrolytes(SEs)have emerged as a promising alternative to liquid electrolyte-based Li-ion batteries due to their higher energy density and safety.However,since ASSLMBs lack the wetting properties of liquid electrolytes,they require stacking pressure to prevent contact loss between electrodes and SEs.Though previous studies showed that stacking pressure could impact certain performance aspects,a comprehensive investigation into the effects of stacking pressure has not been conducted.To address this gap,we utilized the Li_(6)PS_(5)Cl solid electrolyte as a reference and investigated the effects of stacking pressures on the performance of SEs and ASSLMBs.We also developed models to explain the underlying origin of these effects and predict battery performance,such as ionic conductivity and critical current density.Our results demonstrated that an appropriate stacking pressure is necessary to achieve optimal performance,and each step of applying pressure requires a specific pressure value.These findings can help explain discrepancies in the literature and provide guidance to establish standardized testing conditions and reporting benchmarks for ASSLMBs.Overall,this study contributes to the understanding of the impact of stacking pressure on the performance of ASSLMBs and highlights the importance of careful pressure optimization for optimal battery performance.
基金the National Natural Science Foundation of China(22178120)the China Postdoctoral Science Foundation(2022TQ0173,2023M731922,2022M720076,BX20220182,2023M731921,2023M731919,2023M741919).
文摘Solid-state lithium metal batteries(SSLMBs)show great promise in terms of high-energy-density and high-safety performance.However,there is an urgent need to address the compatibility of electrolytes with high-voltage cathodes/Li anodes,and to minimize the electrolyte thickness to achieve highenergy-density of SSLMBs.Herein,we develop an ultrathin(12.6μm)asymmetric composite solid-state electrolyte with ultralight areal density(1.69 mg cm^(−2))for SSLMBs.The electrolyte combining a garnet(LLZO)layer and a metal organic framework(MOF)layer,which are fabricated on both sides of the polyethylene(PE)separator separately by tape casting.The PE separator endows the electrolyte with flexibility and excellent mechanical properties.The LLZO layer on the cathode side ensures high chemical stability at high voltage.The MOF layer on the anode side achieves a stable electric field and uniform Li flux,thus promoting uniform Li^(+)deposition.Thanks to the well-designed structure,the Li symmetric battery exhibits an ultralong cycle life(5000 h),and high-voltage SSLMBs achieve stable cycle performance.The assembled pouch cells provided a gravimetric/volume energy density of 344.0 Wh kg^(−1)/773.1 Wh L^(−1).This simple operation allows for large-scale preparation,and the design concept of ultrathin asymmetric structure also reveals the future development direction of SSLMBs.
基金National Research Foundation,Grant/Award Number:2022R1A2C1092273。
文摘Silicon(Si)is a promising anode material for lithium‐ion batteries(LIBs)owing to its tremendously high theoretical storage capacity(4200 mAh g−1),which has the potential to elevate the energy of LIBs.However,Si anodes exhibit severe volume change during lithiation/delithiation processes,resulting in anode pulverization and delamination with detrimental growth of solid electrolyte interface layers.As a result,the cycling stability of Si anodes is insufficient for commercialization in LIBs.Polymeric binders can play critical roles in Si anodes by affecting their cycling stability,although they occupy a small portion of the electrodes.This review introduces crucial factors influencing polymeric binders'properties and the electrochemical performance of Si anodes.In particular,we emphasize the structure–property relationships of binders in the context of molecular design strategy,functional groups,types of interactions,and functionalities of binders.Furthermore,binders with additional functionalities,such as electrical conductivity and self‐healability,are extensively discussed,with an emphasis on the binder design principle.
基金This work was financially supported by the National Natural Science Foundation of China(Grant Nos.92162214,41773015,and U1812402)the Key Research and Development Program of Yunnan Province(202103AQ100003).
文摘Clay-type Li deposits are poised to play a pivotal role in addressing the surging global demand for Li.The McDermitt clay-type Li deposit,located in Nevada,is the largest Li deposit in the United States,with Li hosted by a clay-rich sequence of smectite-dominated intervals and illite-dominated intervals,respectively.However,the occurrence of Li and the genesis of Li-bearing minerals within smectite-dominated intervals have not been thoroughly investigated in previous research.Here,we studied the mineralogy,the in-situ Li distribution,and the bonding environments of Li within the smectite intervals using a combination of instru-mental techniques including scanning electron microscope,transmission electron microscope,time-of-flight secondary ion mass spectrometry,and nuclear magnetic resonance.Our results indicate that the smectite exhibits low crystallinity characteristics of lacustrine clay authigenesis and is com-monly found tofill the interstices among volcanic minerals or envelop them;Li is mainly hosted by Mg-smectite rather than the volcanic minerals.Within the tuffaceous sediment samples,the volcanic glass has undergone a transformation,resulting in its complete disappearance and alteration into clay minerals.Owing to the octahedral sites of Mg-smectite bounded in Li,it is referred to be hectorite.We interpret that the hectorite’s precipitation occurs in a high saline-alkaline water environment,a result of McDermitt tuffdissolution.This conclusion can be supported by the coexistence of spherulitic calcite and hectorite.Overall,this study confirms hectorite as the main Li-bearing mineral and increases the understanding of the genetic model of hectorite formation in intracontinental caldera basins.
基金the financial supports from the KeyArea Research and Development Program of Guangdong Province (2020B090919001)the National Natural Science Foundation of China (22078144)the Guangdong Natural Science Foundation for Basic and Applied Basic Research (2021A1515010138 and 2023A1515010686)。
文摘Li metal batteries using high-voltage layered oxides cathodes are of particular interest due to their high energy density.However,they suffer from short lifespan and extreme safety concerns,which are attributed to the degradation of layered oxides and the decomposition of electrolyte at high voltage,as well as the high reactivity of metallic Li.The key is the development of stable electrolytes against both highvoltage cathodes and Li with the formation of robust interphase films on the surfaces.Herein,we report a highly fluorinated ether,1,1,1-trifluoro-2-[(2,2,2-trifluoroethoxy)methoxy]ethane(TTME),as a cosolvent,which not only functions as a diluent forming a localized high concentration electrolyte(LHCE),but also participates in the construction of the inner solvation structure.The TTME-based electrolyte is stable itself at high voltage and induces the formation of a unique double-layer solid electrolyte interphase(SEI)film,which is embodied as one layer rich in crystalline structural components for enhanced mechanical strength and another amorphous layer with a higher concentration of organic components for enhanced flexibility.The Li||Cu cells display a noticeably high Coulombic efficiency of 99.28%after 300 cycles and Li symmetric cells maintain stable cycling more than 3200 h at 0.5 mA/cm^(2) and 1.0m Ah/cm^(2).In addition,lithium metal cells using LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2) and Li CoO_(2) cathodes(both loadings~3.0 m Ah/cm^(2))realize capacity retentions of>85%over 240 cycles with a charge cut-off voltage of 4.4 V and 90%for 170 cycles with a charge cut-off voltage of 4.5 V,respectively.This study offers a bifunctional ether-based electrolyte solvent beneficial for high-voltage Li metal batteries.
基金supported by the National Natural Science Foundation of China(52122702,52277215)the Natural Science Foundation of Heilongjiang Province of China(JQ2021E005)。
文摘Exploration of advanced gel polymer electrolytes(GPEs)represents a viable strategy for mitigating dendritic lithium(Li)growth,which is crucial in ensuring the safe operation of high energy density Li metal batteries(LMBs).Despite this,the application of GPEs is still hindered by inadequate ionic conductivity,low Li^(+)transference number,and subpar physicochemical properties.Herein,Ti O_(2-x)nanofibers(NF)with oxygen vacancy defects were synthesized by a one-step process as inorganic fillers to enhance the thermal/mechanical/ionic-transportation performances of composite GPEs.Various characterizations and theoretical calculations reveal that the oxygen vacancies on the surface of Ti O_(2-x)NF accelerate the dissociation of Li PF_6,promote the rapid transfer of free Li^(+),and influence the formation of Li F-enriched solid electrolyte interphase.Consequently,the composite GPEs demonstrate enhanced ionic conductivity(1.90m S cm^(-1)at room temperature),higher lithium-ion transference number(0.70),wider electrochemical stability window(5.50 V),superior mechanical strength,excellent thermal stability(210℃),and improved compatibility with lithium,resulting in superior cycling stability and rate performance in both Li||Li,Li||Li Fe PO_(4),and Li||Li Ni_(0.8)Co_(0.1)Mn_(0.1)O_(2)cells.Overall,the synergistic influence of nanofiber morphology and enriched oxygen vacancy structure of fillers on electrochemical properties of composite GPEs is comprehensively investigated,thus,it is anticipated to shed new light on designing high-performance GPEs LMBs.
基金financially supported by the National Natural Science Foundation of China (51971080)the Shenzhen Bureau of Science,Technology and Innovation Commission (GXWD20201230155427003-20200730151200003 and JSGG20200914113601003)。
文摘The function of solid electrolytes and the composition of solid electrolyte interphase(SEI)are highly significant for inhibiting the growth of Li dendrites.Herein,we report an in-situ interfacial passivation combined with self-adaptability strategy to reinforce Li_(0.33)La_(0.557)TiO_(3)(LLTO)-based solid-state batteries.Specifically,a functional SEI enriched with LiF/Li_(3)PO_(4) is formed by in-situ electrochemical conversion,which is greatly beneficial to improving interface compatibility and enhancing ion transport.While the polarized dielectric BaTiO_(3)-polyamic acid(BTO-PAA,BP)film greatly improves the Li-ion transport kinetics and homogenizes the Li deposition.As expected,the resulting electrolyte offers considerable ionic conductivity at room temperature(4.3 x 10~(-4)S cm^(-1))and appreciable electrochemical decomposition voltage(5.23 V)after electrochemical passivation.For Li-LiFePO_(4) batteries,it shows a high specific capacity of 153 mA h g^(-1)at 0.2C after 100 cycles and a long-term durability of 115 mA h g^(-1)at 1.0 C after 800 cycles.Additionally,a stable Li plating/stripping can be achieved for more than 900 h at 0.5 mA cm^(-2).The stabilization mechanisms are elucidated by ex-situ XRD,ex-situ XPS,and ex-situ FTIR techniques,and the corresponding results reveal that the interfacial passivation combined with polarization effect is an effective strategy for improving the electrochemical performance.The present study provides a deeper insight into the dynamic adjustment of electrode-electrolyte interfacial for solid-state lithium batteries.
基金financially supported by the National Natural Science Foundation of China(No.52273081,No.22278329)Young Talent Support Plan of Xi’an Jiaotong University+2 种基金Natural Science Basic Research Program of Shaanxi(No.2022TD-27,No.2020-JC-09)the financial support from Swedish Research Council Grant(2021-05839)the“Young Talent Support Plan”of Xi’an Jiaotong University
文摘Inhomogeneous lithium-ion(Li^(+))deposition is one of the most crucial problems,which severely deteriorates the performance of solid-state lithium metal batteries(LMBs).Herein,we discovered that covalent organic framework(COF-1)with periodically arranged boron-oxygen dipole lithiophilic sites could directionally guide Li^(+)even deposition in asymmetric solid polymer electrolytes.This in situ prepared 3D cross-linked network Poly(ACMO-MBA)hybrid electrolyte simultaneously delivers outstanding ionic conductivity(1.02×10^(-3)S cm^(-1)at 30°C)and excellent mechanical property(3.5 MPa).The defined nanosized channel in COF-1 selectively conducts Li^(+)increasing Li^(+)transference number to 0.67.Besides,The COF-1 layer and Poly(ACMO-MBA)also participate in forming a boron-rich and nitrogen-rich solid electrolyte interface to further improve the interfacial stability.The Li‖Li symmetric cell exhibits remarkable cyclic stability over 1000 h.The Li‖NCM523 full cell also delivers an outstanding lifespan over 400 cycles.Moreover,the Li‖LiFePO_(4)full cell stably cycles with a capacity retention of 85%after 500 cycles.the Li‖LiFePO_(4)pouch full exhibits excellent safety performance under pierced and cut conditions.This work thereby further broadens and complements the application of COF materials in polymer electrolyte for dendrite-free and high-energy-density solid-state LMBs.
基金supported by the National Key R&D Program of China(No.2021YFB2402001)the Postgraduate Innovation and Entrepreneurship Practice Project of Anhui Province(No.2022cxcysj013)+2 种基金the China Postdoctoral Science Foundation(No.2022T150615)the Fundamental Research Funds for the Central Universities(No.WK5290000002)supported by Youth Innovation Promotion Association CAS(No.Y201768)。
文摘The safety valve is an important component to ensure the safe operation of lithium-ion batteries(LIBs).However,the effect of safety valve type on the thermal runaway(TR)and gas venting behavior of LIBs,as well as the TR hazard severity of LIBs,are not known.In this paper,the TR and gas venting behavior of three 100 A h lithium iron phosphate(LFP)batteries with different safety valves are investigated under overheating.Compared to previous studies,the main contribution of this work is in studying and evaluating the effect of gas venting behavior and TR hazard severity of LFP batteries with three safety valve types.Two significant results are obtained:(Ⅰ)the safety valve type dominates over gas venting pressure of battery during safety venting,the maximum gas venting pressure of LFP batteries with a round safety valve is 3320 Pa,which is one order of magnitude higher than other batteries with oval or cavity safety valve;(Ⅱ)the LFP battery with oval safety valve has the lowest TR hazard as shown by the TR hazard assessment model based on gray-fuzzy analytic hierarchy process.This study reveals the effect of safety valve type on TR and gas venting,providing a clear direction for the safety valve design.
基金This work is supported by National Natural Science Founda-tion of China(U2004199)National Key Research and Devel-opment Program of China(2018YFD0200606)+1 种基金China Postdoctoral Science Foundation(2021T140615),Natural Sci-enceFoundationofHenanProvince(212300410285)Young Talent Support Project of Henan Province(2021HYTP028).
文摘Solid polymer electrolyte(SPE) shows great potential for all-solid-state batteries because of the inherent safety and flexibility;however, the unfavourable Li+deposition and large thickness hamper its development and application. Herein, a laminar MXene functional layer-thin SPE layer-cathode integration(MXene-PEO-LFP) is designed and fabricated. The MXene functional layer formed by stacking rigid MXene nanosheets imparts higher compressive strength relative to PEO electrolyte layer. And the abundant negatively-charged groups on MXene functional layer effectively repel anions and attract cations to adjust the charge distribution behavior at electrolyte–anode interface. Furthermore,the functional layer with rich lithiophilic groups and outstanding electronic conductivity results in low Li nucleation overpotential and nucleation energy barrier. In consequence, the cell assembled with MXene-PEO-LFP, where the PEO electrolyte layer is only 12 μm, much thinner than most solid electrolytes, exhibits uniform, dendrite-free Li+deposition and excellent cycling stability. High capacity(142.8 mAh g-1), stable operation of 140 cycles(capacity decay per cycle, 0.065%), and low polarization potential(0.5 C) are obtained in this Li|MXene-PEO-LFP cell,which is superior to most PEO-based electrolytes under identical condition. This integrated design may provide a strategy for the large-scale application of thin polymer electrolytes in all-solid-state battery.
基金Guangdong Basic and Applied Basic Research Foundation,Grant/Award Number:2020A1515110762Research Grants Council of the Hong Kong Special Administrative Region,China,Grant/Award Number:R6005‐20Shenzhen Key Laboratory of Advanced Energy Storage,Grant/Award Number:ZDSYS20220401141000001。
文摘Silicon(Si)is widely used as a lithium‐ion‐battery anode owing to its high capacity and abundant crustal reserves.However,large volume change upon cycling and poor conductivity of Si cause rapid capacity decay and poor fast‐charging capability limiting its commercial applications.Here,we propose a multilevel carbon architecture with vertical graphene sheets(VGSs)grown on surfaces of subnanoscopically and homogeneously dispersed Si–C composite nanospheres,which are subsequently embedded into a carbon matrix(C/VGSs@Si–C).Subnanoscopic C in the Si–C nanospheres,VGSs,and carbon matrix form a three‐dimensional conductive and robust network,which significantly improves the conductivity and suppresses the volume expansion of Si,thereby boosting charge transport and improving electrode stability.The VGSs with vast exposed edges considerably increase the contact area with the carbon matrix and supply directional transport channels through the entire material,which boosts charge transport.The carbon matrix encapsulates VGSs@Si–C to decrease the specific surface area and increase tap density,thus yielding high first Coulombic efficiency and electrode compaction density.Consequently,C/VGSs@Si–C delivers excellent Li‐ion storage performances under industrial electrode conditions.In particular,the full cells show high energy densities of 603.5 Wh kg^(−1)and 1685.5 Wh L^(−1)at 0.1 C and maintain 80.7%of the energy density at 3 C.
基金the Science and Technology Key Project of Anhui Province,China(No.2022e03020004).
文摘Lithium recovery from spent lithium-ion batteries(LIBs)have attracted extensive attention due to the skyrocketing price of lithium.The medium-temperature carbon reduction roasting was proposed to preferential selective extraction of lithium from spent Li-CoO_(2)(LCO)cathodes to overcome the incomplete recovery and loss of lithium during the recycling process.The LCO layered structure was destroyed and lithium was completely converted into water-soluble Li2CO_(3)under a suitable temperature to control the reduced state of the cobalt oxide.The Co metal agglomerates generated during medium-temperature carbon reduction roasting were broken by wet grinding and ultrasonic crushing to release the entrained lithium.The results showed that 99.10%of the whole lithium could be recovered as Li2CO_(3)with a purity of 99.55%.This work provided a new perspective on the preferentially selective extraction of lithium from spent lithium batteries.
基金the Horizon Europe Project“Batteries reuse and direct production of high performances cathodic and anodic materials and other raw materials from batteries recycling using low cost and environmentally friendly technologies” (RHINOCEROS project,grant no.101069685)。
文摘Lithium recovery from end-of-life Li-ion batteries(LIBs)through pyro-and hydrometallurgical recycling processes involves several refining stages,with high consumption of reagents and energy.A competitive technological alternative is the electrochemical oxidation of the cathode materials,whereby lithium can be deintercalated and transferred to an electrolyte solution without the aid of chemical extracting compounds.This article investigates the potential to selectively recover Li from LIB cathode materials by direct electrochemical extraction in aqueous solutions.The process allowed to recovering up to 98%of Li from high-purity commercial cathode materials(LiMn_(2)O_(4),LiCoO_(2),and Li Ni_(1/3)Mn_(1/3)Co_(1/3)O_(2))with a faradaic efficiency of 98%and negligible co-extraction of Co,Ni,and Mn.The process was then applied to recover Li from the real waste LIBs black mass obtained by the physical treatment of electric vehicle battery packs.This black mass contained graphite,conductive carbon,and metal impurities from current collectors and steel cases,which significantly influenced the evolution and performances of Li electrochemical extraction.Particularly,due to concomitant oxidation of impurities,lithium extraction yields and faradaic efficiencies were lower than those obtained with high-purity cathode materials.Copper oxidation was found to occur within the voltage range investigated,but it could not quantitatively explain the reduced Li extraction performances.In fact,a detailed investigation revealed that above 1.3 V vs.Ag/Ag Cl,conductive carbon can be oxidized,contributing to the decreased Li extraction.Based on the reported experimental results,guidelines were provided that quantitatively enable the extraction of Li from the black mass,while preventing the simultaneous oxidation of impurities and,consequently,reducing the energy consumption of the proposed Li recovery method.