The optimization of electrolytes and the material removal mechanisms for Cu electrochemical mechanical planarization(ECMP)at different pH values including 5-methyl-1H-benzotriazole(TTA),hydroxyethylidenediphosphoric a...The optimization of electrolytes and the material removal mechanisms for Cu electrochemical mechanical planarization(ECMP)at different pH values including 5-methyl-1H-benzotriazole(TTA),hydroxyethylidenediphosphoric acid(HEDP),and tribasic ammonium citrate(TAC)were investigated by electrochemical techniques,X-ray photoelectron spectrometer(XPS)analysis,nano-scratch tests,AFM measurements,and polishing of Cu-coated blanket wafers.The experimental results show that the planarization efficiency and the surface quality after ECMP obtained in alkali-based solutions are superior to that in acidic-based solutions,especially at pH=8.The optimal electrolyte compositions(mass fraction)are 6% HEDP,0.3% TTA and 3% TAC at pH=8.The main factor affecting the thickness of the oxide layer formed during ECMP process is the applied potential.The soft layer formation is a major mechanism for electrochemical enhanced mechanical abrasion.The surface topography evolution before and after electrochemical polishing(ECP)illustrates the mechanism of mechanical abrasion accelerating electrochemical dissolution,that is,the residual stress caused by the mechanical wear enhances the electrochemical dissolution rate.This understanding is beneficial for optimization of ECMP processes.展开更多
Electrochemical mechanical polishing(ECMP)is a new and highly promising technology.A specific challenge for integrating Ru as barrier in Cu interconnect structures is the galvanic corrosion of Cu that occurs during EC...Electrochemical mechanical polishing(ECMP)is a new and highly promising technology.A specific challenge for integrating Ru as barrier in Cu interconnect structures is the galvanic corrosion of Cu that occurs during ECMP.To mitigate the problem,the benzotriazole(BTA)and ascorbic acid(AA)were chosen as selective anodic and cathodic inhibitors for Cu and Ru,respectively.The optimization of electrolytes at different pHs including BTA,hydroxyethylidenediphosphoric acid(HEDP),and AA were investigated using electrochemical methods.The Ru/Cu removal rate and the planarization efficiency during Ru/Cu ECMP can be approximated using electrochemical measurements of the removal rate,with and without surface abrasion.Chemical systems that exhibit a 1:1 selectivity between the barrier layer and copper would be ideal for the barrier removal step of ECMP.Optimized slurry consists of 20.0 wt%HEDP,0.5 wt%BTA,and 0.3 wt%AA at pH 2.2.Using the optimized slurry,the selectivity of Ru to Cu is near 1.Electrochemical measurements of open circuit potentials,potentiodynamic polarization,and impedance spectroscopy were performed to investigate the galvanic corrosion between ruthenium and copper.展开更多
Sweat is a hypotonic fluid excreted by sweat glands to cool the body. There are conflicting reports on whether or not body composition has an effect on thermoregulatory responses especially during exercise. This study...Sweat is a hypotonic fluid excreted by sweat glands to cool the body. There are conflicting reports on whether or not body composition has an effect on thermoregulatory responses especially during exercise. This study was aimed at determining and comparing sweat rate and electrolyte composition in underweight (BMI BMI 30 kg/m<sup>2</sup>) during moderate exercise. Forty women (19 - 25 years) were used during this study after assessing their health status. They were stratified for BMI with each group having a total of ten women. It was ensured that all the women used in the study were euhydrated before commencing the research. Before sweat collection, the treadmill was calibrated according to the Bruce Treadmill Protocol. Sweat samples were obtained with a sweat suction apparatus from a 120 cm<sup>2</sup> circular area marked on the skin of the face and neck, after a 15 minute fast walk on a treadmill at an inclination of 15° and at a speed of 4.2 km/h at 27°C room temperature. The time at which sweating commenced in the subjects was recorded. Sweat rate (L/hour) was calculated using the formula: sweat rate (L/hr) = (pre-exercise body weight - Post-exercise body weight)/exercise duration. Each sweat sample was collected and analysed immediately. The results showed that obese women had a significantly (P < 0.05) higher sweat rate and underweight women had a significantly (P < 0.05) lower sweat rate than all the other groups. Furthermore, subjects with a high body surface area showed significantly higher sweat rates compared to subjects with lower body surface area. Sweat electrolyte composition did not change in all BMI groups. In conclusion, obese subjects are more likely to develop fluid imbalances than underweight and normal weight subjects during moderate exercise. Also, underweight women might be at a thermoregulatory disadvantage because of their reduced body fat and body surface area.展开更多
A carbonate-based electrolyte containing a self-synthesized trimethylsilyl-benzenesulfonate(TMSBS)multifunctional additive is developed to enhance the all-climate performance of pouch NaNi_(0.33)Fe_(0.33)Mn_(0.33)O_(2...A carbonate-based electrolyte containing a self-synthesized trimethylsilyl-benzenesulfonate(TMSBS)multifunctional additive is developed to enhance the all-climate performance of pouch NaNi_(0.33)Fe_(0.33)Mn_(0.33)O_(2)(NFM)/hard carbon(HC)sodium-ion batteries(SIBs)over a wide range from−30 to 60℃.The pouch cells exhibit an 18.1%increase in capacity retention after 250 cycles at room temperature and an 11.3%increase after 240 cycles at 45℃.The low-temperature discharging of different rates at−30℃and the cycling at−10℃demonstrate the adaptability of TMSBS-containing electrolytes at low temperatures.Compared to traditional commercial electrolytes,this electrolyte can prevent excessive dissolution of interfacial films of two electrodes,purify undesirable substances of electrolyte composition,and optimize electrode interfaces and solvation structure.In addition,based on the gas analysis in the cyclic process at 45℃and the storage at 60℃by employing both in-situ and non-in-situ techniques,it reveals that TMSBS can suppress the side reactions of gas evolution,thereby ensuring the safety of SIBs.This work presents a practical strategy for upgrading commercial SIBs and highlights the importance of rational electrolyte design for practical applications.展开更多
To address the limitations of contemporary lithium-ion batteries,particularly their low energy density and safety concerns,all-solid-state lithium batteries equipped with solid-state electrolytes have been identified ...To address the limitations of contemporary lithium-ion batteries,particularly their low energy density and safety concerns,all-solid-state lithium batteries equipped with solid-state electrolytes have been identified as an up-and-coming alternative.Among the various SEs,organic–inorganic composite solid electrolytes(OICSEs)that combine the advantages of both polymer and inorganic materials demonstrate promising potential for large-scale applications.However,OICSEs still face many challenges in practical applications,such as low ionic conductivity and poor interfacial stability,which severely limit their applications.This review provides a comprehensive overview of recent research advancements in OICSEs.Specifically,the influence of inorganic fillers on the main functional parameters of OICSEs,including ionic conductivity,Li+transfer number,mechanical strength,electrochemical stability,electronic conductivity,and thermal stability are systematically discussed.The lithium-ion conduction mechanism of OICSE is thoroughly analyzed and concluded from the microscopic perspective.Besides,the classic inorganic filler types,including both inert and active fillers,are categorized with special emphasis on the relationship between inorganic filler structure design and the electrochemical performance of OICSEs.Finally,the advanced characterization techniques relevant to OICSEs are summarized,and the challenges and perspectives on the future development of OICSEs are also highlighted for constructing superior ASSLBs.展开更多
High-energy-density lithium(Li)–air cells have been considered a promising energy-storage system,but the liquid electrolyte-related safety and side-reaction problems seriously hinder their development.To address thes...High-energy-density lithium(Li)–air cells have been considered a promising energy-storage system,but the liquid electrolyte-related safety and side-reaction problems seriously hinder their development.To address these above issues,solid-state Li–air batteries have been widely developed.However,many commonly-used solid electrolytes generally face huge interface impedance inLi–air cells and also showpoor stability towards ambient air/Li electrodes.Herein,we fabricate a differentiating surface-regulated ceramic-based composite electrolyte(DSCCE)by constructing disparately LiI-containing polymethyl methacrylate(PMMA)coating and Poly(vinylidene fluoride-co-hexafluoropropylene)(PVDF-HFP)layer on both sides of Li_(1.5)Al_(0.5)Ge_(1.5)(PO_(4))_(3)(LAGP).The cathode-friendly LiI/PMMA layer displays excellent stability towards superoxide intermediates and also greatly reduces the decomposition voltage of discharge products in Li–air system.Additionally,the anode-friendly PVDF-HFP coating shows low-resistance properties towards anodes.Moreover,Li dendrite/passivation derived from liquid electrolyte-induced side reactions and air/I-attacking can be obviously suppressed by the uniformand compact composite framework.As a result,the DSCCE-based Li–air batteries possess high capacity/low voltage polarization(11,836mAh g^(-1)/1.45Vunder 500mAg^(-1)),good rate performance(capacity ratio under 1000mAg^(-1)/250mAg^(-1) is 68.2%)and longterm stable cell operation(~300 cycles at 750 mA g^(-1) with 750 mAh g^(-1))in ambient air.展开更多
High-performance lithium metal batteries benefit from the construction of composite polymer electrolytes(CPEs)which are synthesized by incorporating inorganic fillers into polymer matrices[1].However,the random distri...High-performance lithium metal batteries benefit from the construction of composite polymer electrolytes(CPEs)which are synthesized by incorporating inorganic fillers into polymer matrices[1].However,the random distribution of added fillers within the polymer matrix can lead to tortuous ion pathways and longer transmission distances(Fig.1).As a result,the ion transport capability of CPEs may decrease,while interface contact may deteriorate.Therefore,the organized arrangement of fillers emerges as a crucial consideration in constructing electrolyte membranes.One highly effective approach is the adoption of a vertically aligned filler configuration,where ceramic fillers are constructed to be perpendicular to the electrolyte membrane.If so,the filler/electrolyte interface impedance can be significantly reduced,while continuous ion transport channels along the specified direction are formed,thus significantly enhancing the ion conduction(Fig.1(a))[1].展开更多
Determining the optimal ceramic content of the ceramics-in-polymer composite electrolytes and the appropriate stack pressure can effectively improve the interfacial contact of solid-state batteries(SSBs).Based on the ...Determining the optimal ceramic content of the ceramics-in-polymer composite electrolytes and the appropriate stack pressure can effectively improve the interfacial contact of solid-state batteries(SSBs).Based on the contact mechanics model and constructed by the conjugate gradient method,continuous convolution,and fast Fourier transform,this paper analyzes and compares the interfacial contact responses involving the polymers commonly used in SSBs,which provides the original training data for machine learning.A support vector regression model is established to predict the relationship between the content of ceramics and the interfacial resistance.The Bayesian optimization and K-fold cross-validation are introduced to find the optimal combination of hyperparameters,which accelerates the training process and improves the model’s accuracy.We found the relationship between the content of ceramics,the stack pressure,and the interfacial resistance.The results can be taken as a reference for the design of the low-resistance composite electrolytes for solid-state batteries.展开更多
Ionic covalent organic framework(COF)lamellar membranes are the alternative materials as promising Li^(+)conductors for all-solid-state lithium batteries.However,COF lamellar membrane suffers from poor structural stab...Ionic covalent organic framework(COF)lamellar membranes are the alternative materials as promising Li^(+)conductors for all-solid-state lithium batteries.However,COF lamellar membrane suffers from poor structural stability and inevitable cross-layer transfer resistance due to the weak interaction at interface of adjacent nanosheets.Herein,a lamellar polymer-threaded ionic COF(PEI@TpPa-SO_(3)Li)composite electrolyte with single Li^(+)conduction was prepared by assembling lithium sulfonated COF(TpPa-SO_(3)Li)nanosheets and then threading them with polyethyleneimine(PEI)chains.It reveals that the threaded PEI chains induce the oriented permutation of pore channel of PEI@TpPa-SO_(3)Li electrolyte through electrostatic interaction between-NH_(2)/-NH-and-SO_(3)Li groups.This enables the construction of continuous and aligned-SO_(3)^(-)...Li^(+)...-NH_(2)/-NH-pairs along pore channels,which act as efficient Li^(+)conducting sites and afford high Li^(+)hopping conduction(1.4×10^(-4)S cm^(-1)at 30℃)with a high Young's modulus of 408.7 MP and wide electrochemical stability window of 0~4.7 V.The assembled LiFePO_(4)‖Li and LiNi_(0.8)Mn_(0.1)Co_(0.1)O_(2)‖Li half-cells achieve high discharge capacities of 155.0 mAh g^(-1)and 167.2 mAh g^(-1)at 30℃under0.2 C,respectively,with high capacity retention of 98%after 300 cycles.This study provides an alternative route to highly ion-conductive lamellar porous electrolytes for high-performance energy devices.展开更多
Sulfide solid electrolytes with an ultrahigh ionic conductivity are considered to be extremely promising alternatives to liquid electrolytes for next-generation lithium batteries.However,it is difficult to obtain a th...Sulfide solid electrolytes with an ultrahigh ionic conductivity are considered to be extremely promising alternatives to liquid electrolytes for next-generation lithium batteries.However,it is difficult to obtain a thin solid electrolyte layer with good mechanical properties due to the weak binding ability between their powder particles,which seriously limits the actual energy density of sulfide all-solid-state lithium batteries(ASSLBs).Fortunately,the preparation of sulfide-polymer composite solid electrolyte(SPCSE)membranes by introducing polymer effectively reduces the thickness of solid electrolytes and guarantees high mechanical properties.In this review,recent progress of SPCSE membranes for ASSLBs is summarized.The classification of components in SPCSE membranes is first introduced briefly.Then,the preparation methods of SPCSE membranes are categorized according to process characteristics,in which the challenges of different methods and their corresponding solutions are carefully reviewed.The energy densities of the full battery composed of SPCSE membranes are further given whenever available to help understanding the device-level performance.Finally,we discuss the potential challenges and research opportunities for SPCSE membranes to guide the future development of high-performance sulfide ASSLBs.展开更多
Solid-state sodium batteries offer new opportunities for emerging applications with sensitivity to safety and cost.However,the prevailing composite electrolyte structure,as a core component,is still poorly conductive ...Solid-state sodium batteries offer new opportunities for emerging applications with sensitivity to safety and cost.However,the prevailing composite electrolyte structure,as a core component,is still poorly conductive to Na ions.Herein,a 3D architecture design of Na^(+)conductive Na_(3)Zr_(2)Si_(2)PO_(12)framework is introduced to in situ compound with polymer electrolyte,subtly inducing an anion-enriched interface that acts as rapid ion immigration channel.Multiple continuous and fast Na^(+)transport pathways are built via the amorphization of polymer matrix,the consecutive skeleton,and the induced anion-adsorbed interface,resulting in a high ionic conductivity of4.43×10^(-4)S.cm^(-1).Notably,the design of 3D skeleton not only enables the content of inorganic part exceeds 60wt%without any sign of agglomeration,but also endows the composite electrolyte reach a high transference number of 0.61 by immobilizing the anions.The assembled quasisolid-state cells exhibit high practical safety and can stably work for over 1500 cycles with 83.1%capacity retention.This tactic affords new insights in designing Na^(+)conductive composite electrolytes suffering from slow ion immigration for quasi-solid-state sodium batteries.展开更多
This study demonstrates the successful fabrication of solid-state bilayers using LiFePO_(4)(LFP)cathodes and Li_(1.3)Al_(0.3)Ti_(1.7)(PO_(4))_(3)(LATP)-based Composite Solid Electrolytes(CSEs)via Cold Sintering Proces...This study demonstrates the successful fabrication of solid-state bilayers using LiFePO_(4)(LFP)cathodes and Li_(1.3)Al_(0.3)Ti_(1.7)(PO_(4))_(3)(LATP)-based Composite Solid Electrolytes(CSEs)via Cold Sintering Process(CSP).By optimizing the sintering pressure,it is achieved an intimate contact between the cathode and the solid electrolyte,leading to an enhanced electrochemical performance.Bilayers cold sintered at 300 MPa and a low-sintering temperature of 150℃exhibit high ionic conductivities(0.5 mS cm^(-1))and stable specific capacities at room temperature(160.1 mAh g^(-1)LFP at C/10 and 75.8 mAh g^(-1)_(LFP)at 1 C).Moreover,an operando electrochemical impedance spectroscopy(EIS)technique is employed to identify limiting factors of the bilayer kinetics and to anticipate the overall electrochemical behavior.Results suggest that capacity fading can occur in samples prepared with high sintering pressures due to a volume reduction in the LFP crystalline cell.This work demonstrates the potential of CSP to produce straightforward high-performance bilayers and introduces a valuable non-destructive instrument for understanding and avoiding degradation in solid-state lithium-based batteries.展开更多
Solid-state batteries(SSBs)with thermal stable solid-state electrolytes(SSEs)show intrinsic capacity and great potential in energy density improvement.SSEs play critical role,however,their low ionic conductivity at ro...Solid-state batteries(SSBs)with thermal stable solid-state electrolytes(SSEs)show intrinsic capacity and great potential in energy density improvement.SSEs play critical role,however,their low ionic conductivity at room temperature and high brittleness hinder their further development.In this paper,polypropylene(PP)-polyvinylidene fluoride(PVDF)-Li_(1.3)Al_(0.3)Ti_(1.7)(PO_(4))_(3)(LATP)-Lithium bis(trifluoromethane sulphonyl)imide(LiTFSI)multi-layered composite solid electrolyte(CSE)is prepared by a simple separator coating strategy.The incorporation of LATP nanoparticle fillers and high concentration LiTFSI not only reduces the crystallinity of PVDF,but also forms a solvation structure,which contributes to high ionic conductivity in a wide temperature.In addition,using a PP separator as the supporting film,the mechanical strength of the electrolyte was improved and the growth of lithium dendrites are effectively inhibited.The results show that the CSE prepared in this paper has a high ionic conductivity of 6.38×10^(-4)S/cm at room temperature and significantly improves the mechanical properties,the tensile strength reaches 11.02 MPa.The cycle time of Li/Li symmetric cell assembled by CSE at room temperature can exceed 800 h.The Li/LFP full cell can cycle over 800 cycles and the specific capacity of Li/LFP full cell can still reach 120 m Ah/g after 800 cycles at 2 C.This CSE has good cycle stability and excellent mechanical strength at room temperature,which provides an effective method to improve the performance of solid electrolytes under moderate condition.展开更多
Recently,high-entropy materials are attracting enormous attention in battery applications,encompassing both electrode materials and solid electrolytes,due to the pliability and diversification in material composition ...Recently,high-entropy materials are attracting enormous attention in battery applications,encompassing both electrode materials and solid electrolytes,due to the pliability and diversification in material composition and electronic structure.Theoretically,the rapid ion transport and the abundance of surface defects in high-entropy materials suggest a potential for enhancing the performance of composite solid-state electrolytes(CPEs).Herein,using a high-entropy oxide(HEO)filler to assess its potential contributions to CPEs is proposed.The distinctive structural distortions in HEO significantly improve the ionic conductivity(5×10^(−4) S·cm^(−1) at 60℃)and Li-ion transference number(0.57)of CPEs.Furthermore,the enhanced Li-ion transport capability extends the critical current density from 0.6 to 1.5 mA·cm^(−2) in Li/Li symmetric cells.In addition,all-solid-state batteries incorporating the HEO-modified CPEs exhibit superior rate performance and cycling stability.The work will enrich the application of HEOs in CPEs and provide fundamental understanding.展开更多
Composite solid electrolytes(CSEs)are promising for solid-state Li metal batteries but suffer from inferior room-temperature ionic conductivity due to sluggish ion transport and high cost due to expensive active ceram...Composite solid electrolytes(CSEs)are promising for solid-state Li metal batteries but suffer from inferior room-temperature ionic conductivity due to sluggish ion transport and high cost due to expensive active ceramic fillers.Here,a host–vip inversion engineering strategy is proposed to develop superionic CSEs using cost-effective SiO_(2) nanoparticles as passive ceramic hosts and poly(vinylidene fluoride-hexafluoropropylene)(PVH)microspheres as polymer vips,forming an unprecedented“polymer vip-in-ceramic host”(i.e.,PVH-in-SiO_(2))architecture differing from the traditional“ceramic vip-in-polymer host”.The PVH-in-SiO_(2) exhibits excellent Li-salt dissociation,achieving high-concentration free Li+.Owing to the low diffusion energy barriers and high diffusion coefficient,the free Li+is thermodynamically and kinetically favorable to migrate to and transport at the SiO_(2)/PVH interfaces.Consequently,the PVH-in-SiO_(2) delivers an exceptional ionic conductivity of 1.32.10−3 S cm−1 at 25℃(vs.typically 10−5–10−4 S cm−1 using high-cost active ceramics),achieved under an ultralow residual solvent content of 2.9 wt%(vs.8–15 wt%in other CSEs).Additionally,PVH-in-SiO_(2) is electrochemically stable with Li anode and various cathodes.Therefore,the PVH-in-SiO_(2) demonstrates excellent high-rate cyclability in LiFePO4|Li full cells(92.9%capacity-retention at 3C after 300 cycles under 25℃)and outstanding stability with high-mass-loading LiFePO4(9.2 mg cm−1)and high-voltage NCM622(147.1 mAh g−1).Furthermore,we verify the versatility of the host–vip inversion engineering strategy by fabricating Na-ion and K-ion-based PVH-in-SiO_(2) CSEs with similarly excellent promotions in ionic conductivity.Our strategy offers a simple,low-cost approach to fabricating superionic CSEs for large-scale application of solid-state Li metal batteries and beyond.展开更多
Li_(6)PS_(5)Cl is a highly wanted sulfide-solid-electrolyte(SSE)for developing all-solid-state lithium batteries,due to its high ionic conductivity,good processability and abundant compositional elements.However,its c...Li_(6)PS_(5)Cl is a highly wanted sulfide-solid-electrolyte(SSE)for developing all-solid-state lithium batteries,due to its high ionic conductivity,good processability and abundant compositional elements.However,its cyclability is poor because of harmful side reactions at the Li_(6)PS_(5)Cl/Li interface and growth of lithium dendrites inside Li_(6)PS_(5)Cl phase.Herein,we report a simple interface-engineering remedy to boost the electrochemical performance of Li_(6)PS_(5)Cl,by coating its surface with a Li-compatible electrolyte Li3OCl having low electronic conductivity.The obtainedLi_(6)PS_(5)Cl@Li_(3)OCl core@shell structure exhibits a synergistic effect.Consequently,compared with the bare Li_(6)PS_(5)Cl,this composite electrolyte exhibits great performance improvements:1)In Li|electrolyte|Li symmetric cells,the critical current density at 30℃gets increased from 0.6 mA cm^(-2)to 1.6 mA cm^(-2),and the lifetime gets prolonged from 320 h to 1400 h at the cycling current of 0.2 mA cm^(-2)or from 10 h to 900 h at the cycling current of 0.5 mA cm^(-2);2)In Li|electrolyte|NCM721 full cells running at 30℃,the cycling capacity at 0.2 C(or 0.5 C)gets enhanced by 20%(or from unfeasible to be feasible)for 100 cycles and the rate capability reaches up to 2 C from 0.2 C;and in full cells running at 60℃,the cycling capacity is increased by 7%at 0.2 C and the rate capability is enhanced to 3.0 C from 0.5 C.The experimental studies and theoretical computations show that the performance enhancements are due to the confined electron penetration and suppressed lithium dendrites growth at theLi_(6)PS_(5)Cl@Li_(3)OCl interface.展开更多
Polymer solid-state lithium batteries(SSLB)are regarded as a promising energy storage technology to meet growing demand due to their high energy density and safety.Ion conductivity,interface stability and battery asse...Polymer solid-state lithium batteries(SSLB)are regarded as a promising energy storage technology to meet growing demand due to their high energy density and safety.Ion conductivity,interface stability and battery assembly process are still the main challenges to hurdle the commercialization of SSLB.As the main component of SSLB,poly(1,3-dioxolane)(PDOL)-based solid polymer electrolytes polymerized in-situ are becoming a promising candidate solid elec-trolyte,for their high ion conductivity at room temperature,good battery elec-trochemical performances,and simple assembly process.This review analyzes opportunities and challenges of PDOL electrolytes toward practical application for polymer SSLB.The focuses include exploring the polymerization mechanism of DOL,the performance of PDOL composite electrolytes,and the application of PDOL.Furthermore,we provide a perspective on future research directions that need to be emphasized for commercialization of PDOL-based electrolytes in SSLB.The exploration of these schemes facilitates a comprehensive and profound understanding of PDOL-based polymer electrolyte and provides new research ideas to boost them toward practical application in solid-state batteries.展开更多
otentiometric oxygen sensors have been widely used in internal combustion engines,industrial boilers,and metallurgical heat treatment furnaces.However,traditional oxygen sensors based on yttria-stabilized zirconia(YSZ...otentiometric oxygen sensors have been widely used in internal combustion engines,industrial boilers,and metallurgical heat treatment furnaces.However,traditional oxygen sensors based on yttria-stabilized zirconia(YSZ)electrolyte can only be operated at elevated temperatures(>750℃)due to their rela-tively low ionic conductivity.In this study,we present a highly efficient micro-oxygen sensor that can be operated at a temperature as low as 300℃.This micro-oxygen sensor incorporates a composite solid electrolyte,i.e.,well-aligned gadolinium-doped cerium oxide(CGO)nanofibers embedded within a YSZ matrix(YSZ/CGO_(f)).The arrays of CGO nanofibers in the YSZ matrix are parallel to the conduction direc-tion,providing rapid conducting channels for oxygen ions.Benefitting from this design,the composite electrolyte leads to a conductivity of four times higher than that of traditional YSZ solid electrolytes at low temperatures.This enhancement in conductivity is attributed to the presence of a defective interfacial region between CGO_(f)and YSZ,which promotes the mobility of oxygen ions.The strategy of constructing fast ionic conduction in the composite electrolyte by using well-aligned nanofibers may be considered for the design and optimization of other micro/nano-devices including sensors,batteries,and fuel cells.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
The research of poly(ethylene oxide)(PEO)-based solid composite electrolyte with high ionic conductivity and excellent interfacial stability is the key to the development of all-solid-state lithium-ion batteries(ASSLI...The research of poly(ethylene oxide)(PEO)-based solid composite electrolyte with high ionic conductivity and excellent interfacial stability is the key to the development of all-solid-state lithium-ion batteries(ASSLIBs). Herein, uniform nanorod structured CeO_(2) fillers were controllably synthesized by electrospinning, which were subsequently filled into PEO polymer to prepare CeO_(2)/PEO solid composite electrolyte. The addition of CeO_(2) nanorods can reduce both the glass transition temperature and the melting point of PEO polymer, and also interact with PEO and lithium bis(trifluoromethanesulphonyl)imide(LITFSI) by Lewis acid—base reaction. Therefore, the solid composite electrolyte exhibits a high ionic conductivity of 4.52 × 10^(-4)S/cm, a wide electrochemical stability window of about 4.8 V, and a good interfacial stability with Li at 55℃. Moreover, the LiFePO_4/Li ASSLIB divulges the discharging specific capacity of 165, 162, 156 and 146 mA,h/g at 0.2, 0.5, 1 and 2 C, respectively, and achieves the capacity retention of 90.3% after 150 cycles at 0.5 C. Consequently, one dimensional CeO_(2) nanorods can be considered as an alternative filler for polymeric solid electrolyte.展开更多
基金Project(50975058)supported by the National Science Foundation of China
文摘The optimization of electrolytes and the material removal mechanisms for Cu electrochemical mechanical planarization(ECMP)at different pH values including 5-methyl-1H-benzotriazole(TTA),hydroxyethylidenediphosphoric acid(HEDP),and tribasic ammonium citrate(TAC)were investigated by electrochemical techniques,X-ray photoelectron spectrometer(XPS)analysis,nano-scratch tests,AFM measurements,and polishing of Cu-coated blanket wafers.The experimental results show that the planarization efficiency and the surface quality after ECMP obtained in alkali-based solutions are superior to that in acidic-based solutions,especially at pH=8.The optimal electrolyte compositions(mass fraction)are 6% HEDP,0.3% TTA and 3% TAC at pH=8.The main factor affecting the thickness of the oxide layer formed during ECMP process is the applied potential.The soft layer formation is a major mechanism for electrochemical enhanced mechanical abrasion.The surface topography evolution before and after electrochemical polishing(ECP)illustrates the mechanism of mechanical abrasion accelerating electrochemical dissolution,that is,the residual stress caused by the mechanical wear enhances the electrochemical dissolution rate.This understanding is beneficial for optimization of ECMP processes.
基金the National Natural Science Foundation of China(No.50975058)。
文摘Electrochemical mechanical polishing(ECMP)is a new and highly promising technology.A specific challenge for integrating Ru as barrier in Cu interconnect structures is the galvanic corrosion of Cu that occurs during ECMP.To mitigate the problem,the benzotriazole(BTA)and ascorbic acid(AA)were chosen as selective anodic and cathodic inhibitors for Cu and Ru,respectively.The optimization of electrolytes at different pHs including BTA,hydroxyethylidenediphosphoric acid(HEDP),and AA were investigated using electrochemical methods.The Ru/Cu removal rate and the planarization efficiency during Ru/Cu ECMP can be approximated using electrochemical measurements of the removal rate,with and without surface abrasion.Chemical systems that exhibit a 1:1 selectivity between the barrier layer and copper would be ideal for the barrier removal step of ECMP.Optimized slurry consists of 20.0 wt%HEDP,0.5 wt%BTA,and 0.3 wt%AA at pH 2.2.Using the optimized slurry,the selectivity of Ru to Cu is near 1.Electrochemical measurements of open circuit potentials,potentiodynamic polarization,and impedance spectroscopy were performed to investigate the galvanic corrosion between ruthenium and copper.
文摘Sweat is a hypotonic fluid excreted by sweat glands to cool the body. There are conflicting reports on whether or not body composition has an effect on thermoregulatory responses especially during exercise. This study was aimed at determining and comparing sweat rate and electrolyte composition in underweight (BMI BMI 30 kg/m<sup>2</sup>) during moderate exercise. Forty women (19 - 25 years) were used during this study after assessing their health status. They were stratified for BMI with each group having a total of ten women. It was ensured that all the women used in the study were euhydrated before commencing the research. Before sweat collection, the treadmill was calibrated according to the Bruce Treadmill Protocol. Sweat samples were obtained with a sweat suction apparatus from a 120 cm<sup>2</sup> circular area marked on the skin of the face and neck, after a 15 minute fast walk on a treadmill at an inclination of 15° and at a speed of 4.2 km/h at 27°C room temperature. The time at which sweating commenced in the subjects was recorded. Sweat rate (L/hour) was calculated using the formula: sweat rate (L/hr) = (pre-exercise body weight - Post-exercise body weight)/exercise duration. Each sweat sample was collected and analysed immediately. The results showed that obese women had a significantly (P < 0.05) higher sweat rate and underweight women had a significantly (P < 0.05) lower sweat rate than all the other groups. Furthermore, subjects with a high body surface area showed significantly higher sweat rates compared to subjects with lower body surface area. Sweat electrolyte composition did not change in all BMI groups. In conclusion, obese subjects are more likely to develop fluid imbalances than underweight and normal weight subjects during moderate exercise. Also, underweight women might be at a thermoregulatory disadvantage because of their reduced body fat and body surface area.
基金supported by the Scientific Research Innovation Project of Graduate School of South China Normal University。
文摘A carbonate-based electrolyte containing a self-synthesized trimethylsilyl-benzenesulfonate(TMSBS)multifunctional additive is developed to enhance the all-climate performance of pouch NaNi_(0.33)Fe_(0.33)Mn_(0.33)O_(2)(NFM)/hard carbon(HC)sodium-ion batteries(SIBs)over a wide range from−30 to 60℃.The pouch cells exhibit an 18.1%increase in capacity retention after 250 cycles at room temperature and an 11.3%increase after 240 cycles at 45℃.The low-temperature discharging of different rates at−30℃and the cycling at−10℃demonstrate the adaptability of TMSBS-containing electrolytes at low temperatures.Compared to traditional commercial electrolytes,this electrolyte can prevent excessive dissolution of interfacial films of two electrodes,purify undesirable substances of electrolyte composition,and optimize electrode interfaces and solvation structure.In addition,based on the gas analysis in the cyclic process at 45℃and the storage at 60℃by employing both in-situ and non-in-situ techniques,it reveals that TMSBS can suppress the side reactions of gas evolution,thereby ensuring the safety of SIBs.This work presents a practical strategy for upgrading commercial SIBs and highlights the importance of rational electrolyte design for practical applications.
基金supported by the National Natural Science Foundation of China(Grant No.22075064,52302234,52272241)Zhejiang Provincial Natural Science Foundation of China under Grant No.LR24E020001+2 种基金Natural Science of Heilongjiang Province(No.LH2023B009)China Postdoctoral Science Foundation(2022M710950)Heilongjiang Postdoctoral Fund(LBH-Z21131),National Key Laboratory Projects(No.SYSKT20230056).
文摘To address the limitations of contemporary lithium-ion batteries,particularly their low energy density and safety concerns,all-solid-state lithium batteries equipped with solid-state electrolytes have been identified as an up-and-coming alternative.Among the various SEs,organic–inorganic composite solid electrolytes(OICSEs)that combine the advantages of both polymer and inorganic materials demonstrate promising potential for large-scale applications.However,OICSEs still face many challenges in practical applications,such as low ionic conductivity and poor interfacial stability,which severely limit their applications.This review provides a comprehensive overview of recent research advancements in OICSEs.Specifically,the influence of inorganic fillers on the main functional parameters of OICSEs,including ionic conductivity,Li+transfer number,mechanical strength,electrochemical stability,electronic conductivity,and thermal stability are systematically discussed.The lithium-ion conduction mechanism of OICSE is thoroughly analyzed and concluded from the microscopic perspective.Besides,the classic inorganic filler types,including both inert and active fillers,are categorized with special emphasis on the relationship between inorganic filler structure design and the electrochemical performance of OICSEs.Finally,the advanced characterization techniques relevant to OICSEs are summarized,and the challenges and perspectives on the future development of OICSEs are also highlighted for constructing superior ASSLBs.
基金supported by the National Natural Science Foundation of China(22379074)Young Science and Technology Talent Program of Inner Mongolia Province(NJYT24001)+4 种基金Natural Sciences and Engineering Research Council of Canada(NSERC)GLABAT Solid-State Battery Inc.,China Automotive Battery Research Institute Co.Ltd,Canada Research Chair Program(CRC)Canada Foundation for Innovation(CFI)Ontario Research Fundsupported by the Chinese Scholarship Council.
文摘High-energy-density lithium(Li)–air cells have been considered a promising energy-storage system,but the liquid electrolyte-related safety and side-reaction problems seriously hinder their development.To address these above issues,solid-state Li–air batteries have been widely developed.However,many commonly-used solid electrolytes generally face huge interface impedance inLi–air cells and also showpoor stability towards ambient air/Li electrodes.Herein,we fabricate a differentiating surface-regulated ceramic-based composite electrolyte(DSCCE)by constructing disparately LiI-containing polymethyl methacrylate(PMMA)coating and Poly(vinylidene fluoride-co-hexafluoropropylene)(PVDF-HFP)layer on both sides of Li_(1.5)Al_(0.5)Ge_(1.5)(PO_(4))_(3)(LAGP).The cathode-friendly LiI/PMMA layer displays excellent stability towards superoxide intermediates and also greatly reduces the decomposition voltage of discharge products in Li–air system.Additionally,the anode-friendly PVDF-HFP coating shows low-resistance properties towards anodes.Moreover,Li dendrite/passivation derived from liquid electrolyte-induced side reactions and air/I-attacking can be obviously suppressed by the uniformand compact composite framework.As a result,the DSCCE-based Li–air batteries possess high capacity/low voltage polarization(11,836mAh g^(-1)/1.45Vunder 500mAg^(-1)),good rate performance(capacity ratio under 1000mAg^(-1)/250mAg^(-1) is 68.2%)and longterm stable cell operation(~300 cycles at 750 mA g^(-1) with 750 mAh g^(-1))in ambient air.
基金supported by the National Natural Science Foundation of China(No.51972293)Hangzhou Key Research Program Project(2023SZD0099)LingYan Project(2024C01090).
文摘High-performance lithium metal batteries benefit from the construction of composite polymer electrolytes(CPEs)which are synthesized by incorporating inorganic fillers into polymer matrices[1].However,the random distribution of added fillers within the polymer matrix can lead to tortuous ion pathways and longer transmission distances(Fig.1).As a result,the ion transport capability of CPEs may decrease,while interface contact may deteriorate.Therefore,the organized arrangement of fillers emerges as a crucial consideration in constructing electrolyte membranes.One highly effective approach is the adoption of a vertically aligned filler configuration,where ceramic fillers are constructed to be perpendicular to the electrolyte membrane.If so,the filler/electrolyte interface impedance can be significantly reduced,while continuous ion transport channels along the specified direction are formed,thus significantly enhancing the ion conduction(Fig.1(a))[1].
基金the National Natural Science Foundation of China(12102085)the Postdoctoral Science Foundation of China(2023M730504)the Sichuan Province Regional Innovation and Cooperation Project(2024YFHZ0210).
文摘Determining the optimal ceramic content of the ceramics-in-polymer composite electrolytes and the appropriate stack pressure can effectively improve the interfacial contact of solid-state batteries(SSBs).Based on the contact mechanics model and constructed by the conjugate gradient method,continuous convolution,and fast Fourier transform,this paper analyzes and compares the interfacial contact responses involving the polymers commonly used in SSBs,which provides the original training data for machine learning.A support vector regression model is established to predict the relationship between the content of ceramics and the interfacial resistance.The Bayesian optimization and K-fold cross-validation are introduced to find the optimal combination of hyperparameters,which accelerates the training process and improves the model’s accuracy.We found the relationship between the content of ceramics,the stack pressure,and the interfacial resistance.The results can be taken as a reference for the design of the low-resistance composite electrolytes for solid-state batteries.
基金supported by the financial support from the National Key Research and Development Program(2022YFB3805204,2022YFB3805201)National Natural Science Foundation of China(22478362)+2 种基金Joint Foundation for Science and Technology Research&Development Plan of Henan Province(222301420003 and 232301420038)Key Scientific and Technological Project of Henan Province(242102321032)Foundation of Henan Educational Committee(22A530003)。
文摘Ionic covalent organic framework(COF)lamellar membranes are the alternative materials as promising Li^(+)conductors for all-solid-state lithium batteries.However,COF lamellar membrane suffers from poor structural stability and inevitable cross-layer transfer resistance due to the weak interaction at interface of adjacent nanosheets.Herein,a lamellar polymer-threaded ionic COF(PEI@TpPa-SO_(3)Li)composite electrolyte with single Li^(+)conduction was prepared by assembling lithium sulfonated COF(TpPa-SO_(3)Li)nanosheets and then threading them with polyethyleneimine(PEI)chains.It reveals that the threaded PEI chains induce the oriented permutation of pore channel of PEI@TpPa-SO_(3)Li electrolyte through electrostatic interaction between-NH_(2)/-NH-and-SO_(3)Li groups.This enables the construction of continuous and aligned-SO_(3)^(-)...Li^(+)...-NH_(2)/-NH-pairs along pore channels,which act as efficient Li^(+)conducting sites and afford high Li^(+)hopping conduction(1.4×10^(-4)S cm^(-1)at 30℃)with a high Young's modulus of 408.7 MP and wide electrochemical stability window of 0~4.7 V.The assembled LiFePO_(4)‖Li and LiNi_(0.8)Mn_(0.1)Co_(0.1)O_(2)‖Li half-cells achieve high discharge capacities of 155.0 mAh g^(-1)and 167.2 mAh g^(-1)at 30℃under0.2 C,respectively,with high capacity retention of 98%after 300 cycles.This study provides an alternative route to highly ion-conductive lamellar porous electrolytes for high-performance energy devices.
基金supported by grants from the National Natural Science Foundation of China(Nos.52072136,52172229,52272201,52302303,51972257)Yanchang Petroleum-WHUT Joint Program(No.yc-whlg-2022ky-05)Fundamental Research Funds for the Central Universities(Nos.104972024RSCrc0006,2023IVA106)for financial support。
文摘Sulfide solid electrolytes with an ultrahigh ionic conductivity are considered to be extremely promising alternatives to liquid electrolytes for next-generation lithium batteries.However,it is difficult to obtain a thin solid electrolyte layer with good mechanical properties due to the weak binding ability between their powder particles,which seriously limits the actual energy density of sulfide all-solid-state lithium batteries(ASSLBs).Fortunately,the preparation of sulfide-polymer composite solid electrolyte(SPCSE)membranes by introducing polymer effectively reduces the thickness of solid electrolytes and guarantees high mechanical properties.In this review,recent progress of SPCSE membranes for ASSLBs is summarized.The classification of components in SPCSE membranes is first introduced briefly.Then,the preparation methods of SPCSE membranes are categorized according to process characteristics,in which the challenges of different methods and their corresponding solutions are carefully reviewed.The energy densities of the full battery composed of SPCSE membranes are further given whenever available to help understanding the device-level performance.Finally,we discuss the potential challenges and research opportunities for SPCSE membranes to guide the future development of high-performance sulfide ASSLBs.
基金financially supported by Guangdong Basic and Applied Basic Research Foundation(Nos.2023A1515011055 and 2022A1515011438)the Key Project of Shenzhen Basic Research(No.JCYJ2022081800003006)the Basic Research Project of the Science and Technology Innovation Commission of Shenzhen(No.JCYJ20220531101013028)。
文摘Solid-state sodium batteries offer new opportunities for emerging applications with sensitivity to safety and cost.However,the prevailing composite electrolyte structure,as a core component,is still poorly conductive to Na ions.Herein,a 3D architecture design of Na^(+)conductive Na_(3)Zr_(2)Si_(2)PO_(12)framework is introduced to in situ compound with polymer electrolyte,subtly inducing an anion-enriched interface that acts as rapid ion immigration channel.Multiple continuous and fast Na^(+)transport pathways are built via the amorphization of polymer matrix,the consecutive skeleton,and the induced anion-adsorbed interface,resulting in a high ionic conductivity of4.43×10^(-4)S.cm^(-1).Notably,the design of 3D skeleton not only enables the content of inorganic part exceeds 60wt%without any sign of agglomeration,but also endows the composite electrolyte reach a high transference number of 0.61 by immobilizing the anions.The assembled quasisolid-state cells exhibit high practical safety and can stably work for over 1500 cycles with 83.1%capacity retention.This tactic affords new insights in designing Na^(+)conductive composite electrolytes suffering from slow ion immigration for quasi-solid-state sodium batteries.
基金support from Generalitat Valenciana under Pla Complementari“Programa de Materials Avanc¸ats”,2022(grant number MFA/2022/030)Ministerio de Ciencia,Innovaci´on y Universidades(Spain)(grant number MCIN/AEI/10.13039/501100011033)+1 种基金support from UJI(UJI-2023-16 and GACUJIMC/2023/08)Generalitat Valenciana through FPI Fellowship Program(grant numbers ACIF/2020/294 and CIACIF/2021/050).
文摘This study demonstrates the successful fabrication of solid-state bilayers using LiFePO_(4)(LFP)cathodes and Li_(1.3)Al_(0.3)Ti_(1.7)(PO_(4))_(3)(LATP)-based Composite Solid Electrolytes(CSEs)via Cold Sintering Process(CSP).By optimizing the sintering pressure,it is achieved an intimate contact between the cathode and the solid electrolyte,leading to an enhanced electrochemical performance.Bilayers cold sintered at 300 MPa and a low-sintering temperature of 150℃exhibit high ionic conductivities(0.5 mS cm^(-1))and stable specific capacities at room temperature(160.1 mAh g^(-1)LFP at C/10 and 75.8 mAh g^(-1)_(LFP)at 1 C).Moreover,an operando electrochemical impedance spectroscopy(EIS)technique is employed to identify limiting factors of the bilayer kinetics and to anticipate the overall electrochemical behavior.Results suggest that capacity fading can occur in samples prepared with high sintering pressures due to a volume reduction in the LFP crystalline cell.This work demonstrates the potential of CSP to produce straightforward high-performance bilayers and introduces a valuable non-destructive instrument for understanding and avoiding degradation in solid-state lithium-based batteries.
基金supported by National Natural Science Foundation of China(No.22209075)。
文摘Solid-state batteries(SSBs)with thermal stable solid-state electrolytes(SSEs)show intrinsic capacity and great potential in energy density improvement.SSEs play critical role,however,their low ionic conductivity at room temperature and high brittleness hinder their further development.In this paper,polypropylene(PP)-polyvinylidene fluoride(PVDF)-Li_(1.3)Al_(0.3)Ti_(1.7)(PO_(4))_(3)(LATP)-Lithium bis(trifluoromethane sulphonyl)imide(LiTFSI)multi-layered composite solid electrolyte(CSE)is prepared by a simple separator coating strategy.The incorporation of LATP nanoparticle fillers and high concentration LiTFSI not only reduces the crystallinity of PVDF,but also forms a solvation structure,which contributes to high ionic conductivity in a wide temperature.In addition,using a PP separator as the supporting film,the mechanical strength of the electrolyte was improved and the growth of lithium dendrites are effectively inhibited.The results show that the CSE prepared in this paper has a high ionic conductivity of 6.38×10^(-4)S/cm at room temperature and significantly improves the mechanical properties,the tensile strength reaches 11.02 MPa.The cycle time of Li/Li symmetric cell assembled by CSE at room temperature can exceed 800 h.The Li/LFP full cell can cycle over 800 cycles and the specific capacity of Li/LFP full cell can still reach 120 m Ah/g after 800 cycles at 2 C.This CSE has good cycle stability and excellent mechanical strength at room temperature,which provides an effective method to improve the performance of solid electrolytes under moderate condition.
基金supported by the National Natural Science Foundation of China(No.52002094)Shenzhen Science and Technology Program(Nos.JCYJ20210324121411031,JSGG202108021253804014 and RCBS20210706092218040)Shenzhen Steady Support Plan(Nos.GXWD20221030205923001 and GXWD20201230155427003-20200824103000001).
文摘Recently,high-entropy materials are attracting enormous attention in battery applications,encompassing both electrode materials and solid electrolytes,due to the pliability and diversification in material composition and electronic structure.Theoretically,the rapid ion transport and the abundance of surface defects in high-entropy materials suggest a potential for enhancing the performance of composite solid-state electrolytes(CPEs).Herein,using a high-entropy oxide(HEO)filler to assess its potential contributions to CPEs is proposed.The distinctive structural distortions in HEO significantly improve the ionic conductivity(5×10^(−4) S·cm^(−1) at 60℃)and Li-ion transference number(0.57)of CPEs.Furthermore,the enhanced Li-ion transport capability extends the critical current density from 0.6 to 1.5 mA·cm^(−2) in Li/Li symmetric cells.In addition,all-solid-state batteries incorporating the HEO-modified CPEs exhibit superior rate performance and cycling stability.The work will enrich the application of HEOs in CPEs and provide fundamental understanding.
基金financial support from the National Natural Science Foundation of China(Nos.52250010 and 52201242)the 261 Project of MIIT,Natural Science Foundation of Jiangsu Province(No.BK20240179)the Young Elite Scientists Sponsorship Program by CAST(No.2021QNRC001).
文摘Composite solid electrolytes(CSEs)are promising for solid-state Li metal batteries but suffer from inferior room-temperature ionic conductivity due to sluggish ion transport and high cost due to expensive active ceramic fillers.Here,a host–vip inversion engineering strategy is proposed to develop superionic CSEs using cost-effective SiO_(2) nanoparticles as passive ceramic hosts and poly(vinylidene fluoride-hexafluoropropylene)(PVH)microspheres as polymer vips,forming an unprecedented“polymer vip-in-ceramic host”(i.e.,PVH-in-SiO_(2))architecture differing from the traditional“ceramic vip-in-polymer host”.The PVH-in-SiO_(2) exhibits excellent Li-salt dissociation,achieving high-concentration free Li+.Owing to the low diffusion energy barriers and high diffusion coefficient,the free Li+is thermodynamically and kinetically favorable to migrate to and transport at the SiO_(2)/PVH interfaces.Consequently,the PVH-in-SiO_(2) delivers an exceptional ionic conductivity of 1.32.10−3 S cm−1 at 25℃(vs.typically 10−5–10−4 S cm−1 using high-cost active ceramics),achieved under an ultralow residual solvent content of 2.9 wt%(vs.8–15 wt%in other CSEs).Additionally,PVH-in-SiO_(2) is electrochemically stable with Li anode and various cathodes.Therefore,the PVH-in-SiO_(2) demonstrates excellent high-rate cyclability in LiFePO4|Li full cells(92.9%capacity-retention at 3C after 300 cycles under 25℃)and outstanding stability with high-mass-loading LiFePO4(9.2 mg cm−1)and high-voltage NCM622(147.1 mAh g−1).Furthermore,we verify the versatility of the host–vip inversion engineering strategy by fabricating Na-ion and K-ion-based PVH-in-SiO_(2) CSEs with similarly excellent promotions in ionic conductivity.Our strategy offers a simple,low-cost approach to fabricating superionic CSEs for large-scale application of solid-state Li metal batteries and beyond.
基金supported by the National Key Research and Development Program of China (2018YFE0111600)Haihe Laboratory of Sustainable Chemical Transformations for financial supportpartially supported by the Graduate Top-notch Innovation Award Plan in Liberal Arts and Science of Tianjin University for the Year of 2023 (B2-2023-012)
文摘Li_(6)PS_(5)Cl is a highly wanted sulfide-solid-electrolyte(SSE)for developing all-solid-state lithium batteries,due to its high ionic conductivity,good processability and abundant compositional elements.However,its cyclability is poor because of harmful side reactions at the Li_(6)PS_(5)Cl/Li interface and growth of lithium dendrites inside Li_(6)PS_(5)Cl phase.Herein,we report a simple interface-engineering remedy to boost the electrochemical performance of Li_(6)PS_(5)Cl,by coating its surface with a Li-compatible electrolyte Li3OCl having low electronic conductivity.The obtainedLi_(6)PS_(5)Cl@Li_(3)OCl core@shell structure exhibits a synergistic effect.Consequently,compared with the bare Li_(6)PS_(5)Cl,this composite electrolyte exhibits great performance improvements:1)In Li|electrolyte|Li symmetric cells,the critical current density at 30℃gets increased from 0.6 mA cm^(-2)to 1.6 mA cm^(-2),and the lifetime gets prolonged from 320 h to 1400 h at the cycling current of 0.2 mA cm^(-2)or from 10 h to 900 h at the cycling current of 0.5 mA cm^(-2);2)In Li|electrolyte|NCM721 full cells running at 30℃,the cycling capacity at 0.2 C(or 0.5 C)gets enhanced by 20%(or from unfeasible to be feasible)for 100 cycles and the rate capability reaches up to 2 C from 0.2 C;and in full cells running at 60℃,the cycling capacity is increased by 7%at 0.2 C and the rate capability is enhanced to 3.0 C from 0.5 C.The experimental studies and theoretical computations show that the performance enhancements are due to the confined electron penetration and suppressed lithium dendrites growth at theLi_(6)PS_(5)Cl@Li_(3)OCl interface.
基金We express our sincere appreciation to the National Natural Science Foundation of China(No.51474113(M.Jing),22279070[L.Wang]and U21A20170[X.He])the Ministry of Science and Technology of China(No.2019YFA0705703[L.Wang]).And we would like to thank the“Explorer 100”cluster system of Tsinghua National Laboratory for Information Science and Technology for facility support.
文摘Polymer solid-state lithium batteries(SSLB)are regarded as a promising energy storage technology to meet growing demand due to their high energy density and safety.Ion conductivity,interface stability and battery assembly process are still the main challenges to hurdle the commercialization of SSLB.As the main component of SSLB,poly(1,3-dioxolane)(PDOL)-based solid polymer electrolytes polymerized in-situ are becoming a promising candidate solid elec-trolyte,for their high ion conductivity at room temperature,good battery elec-trochemical performances,and simple assembly process.This review analyzes opportunities and challenges of PDOL electrolytes toward practical application for polymer SSLB.The focuses include exploring the polymerization mechanism of DOL,the performance of PDOL composite electrolytes,and the application of PDOL.Furthermore,we provide a perspective on future research directions that need to be emphasized for commercialization of PDOL-based electrolytes in SSLB.The exploration of these schemes facilitates a comprehensive and profound understanding of PDOL-based polymer electrolyte and provides new research ideas to boost them toward practical application in solid-state batteries.
基金supported by the Fundamental Research Funds for the Central Universities(Nos.2023MS093,JB2023106)the National Natural Science Foundation of China(Nos.52073156,52202234,91960104).
文摘otentiometric oxygen sensors have been widely used in internal combustion engines,industrial boilers,and metallurgical heat treatment furnaces.However,traditional oxygen sensors based on yttria-stabilized zirconia(YSZ)electrolyte can only be operated at elevated temperatures(>750℃)due to their rela-tively low ionic conductivity.In this study,we present a highly efficient micro-oxygen sensor that can be operated at a temperature as low as 300℃.This micro-oxygen sensor incorporates a composite solid electrolyte,i.e.,well-aligned gadolinium-doped cerium oxide(CGO)nanofibers embedded within a YSZ matrix(YSZ/CGO_(f)).The arrays of CGO nanofibers in the YSZ matrix are parallel to the conduction direc-tion,providing rapid conducting channels for oxygen ions.Benefitting from this design,the composite electrolyte leads to a conductivity of four times higher than that of traditional YSZ solid electrolytes at low temperatures.This enhancement in conductivity is attributed to the presence of a defective interfacial region between CGO_(f)and YSZ,which promotes the mobility of oxygen ions.The strategy of constructing fast ionic conduction in the composite electrolyte by using well-aligned nanofibers may be considered for the design and optimization of other micro/nano-devices including sensors,batteries,and fuel cells.
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Project supported by the Education Department of Henan Province(22A170017)the Science and Technology Department of Henan Province(232102240011)+1 种基金Henan Institute of Science and Technology(2016034)National College Students'Innovation and Entrepreneurship Training Program(202211071012)。
文摘The research of poly(ethylene oxide)(PEO)-based solid composite electrolyte with high ionic conductivity and excellent interfacial stability is the key to the development of all-solid-state lithium-ion batteries(ASSLIBs). Herein, uniform nanorod structured CeO_(2) fillers were controllably synthesized by electrospinning, which were subsequently filled into PEO polymer to prepare CeO_(2)/PEO solid composite electrolyte. The addition of CeO_(2) nanorods can reduce both the glass transition temperature and the melting point of PEO polymer, and also interact with PEO and lithium bis(trifluoromethanesulphonyl)imide(LITFSI) by Lewis acid—base reaction. Therefore, the solid composite electrolyte exhibits a high ionic conductivity of 4.52 × 10^(-4)S/cm, a wide electrochemical stability window of about 4.8 V, and a good interfacial stability with Li at 55℃. Moreover, the LiFePO_4/Li ASSLIB divulges the discharging specific capacity of 165, 162, 156 and 146 mA,h/g at 0.2, 0.5, 1 and 2 C, respectively, and achieves the capacity retention of 90.3% after 150 cycles at 0.5 C. Consequently, one dimensional CeO_(2) nanorods can be considered as an alternative filler for polymeric solid electrolyte.
