A mathematical model of vibrissa motoneurons (vMN), which has been developed by Harish and Golomb, can show repetitive spiking in response to a transient external stimulation. The vMN model is described by a system of...A mathematical model of vibrissa motoneurons (vMN), which has been developed by Harish and Golomb, can show repetitive spiking in response to a transient external stimulation. The vMN model is described by a system of nonlinear ordinary differential equations based on the Hodgkin-Huxley scheme. The vMN model is regulated by various types of ionic conductances, such as persistent sodium, transient sodium, delayed-rectifier potassium, and slow ionic conductances (e.g., slowly activating potassium afterhyperpolarization (AHP) conductance and h conductance). In the present study, a numerical simulation analysis of the vMN model was performed to investigate the effect of variations in the transient sodium and the slow ionic conductance values on the response of the vMN model to a transient external stimulation. Numerical simulations revealed that when both the transient sodium and the AHP conductances are eliminated, the vMN model shows a bistable behavior (i.e., a stimulation-triggered transition between dynamic states). In contrast, none of the following induce the transition alone: 1) elimination of the transient sodium conductance;2) elimination of the AHP conductance;3) elimination of the h conductance;or 4) elimination of both the transient sodium and the h conductances.展开更多
A previous study proposed a mathematical model of A-type horizontal cells in the rabbit retina. This model, which was constructed based on the Hodgkin-Huxley model, was described by a system of nonlinear ordinary diff...A previous study proposed a mathematical model of A-type horizontal cells in the rabbit retina. This model, which was constructed based on the Hodgkin-Huxley model, was described by a system of nonlinear ordinary differential equations. The model contained five types of voltage-dependent ionic conductances: sodium, calcium, delayed rectifier potassium, transient outward potassium, and anomalous rectifier potassium conductances. The previous study indicated that when the delayed rectifier potassium conductance had a small value, depolarizing stimulation could change the dynamic state of the model from a hyperpolarized steady state to a depolarized steady state. However, how this change was affected by variations in the ionic conductance values was not clarified in detail in the previous study. To clarify this issue, in the present study, we performed numerical simulation analysis of the model and revealed the differences among the five types of ionic conductances.展开更多
A previous study has proposed a mathematical model of type-A medial vestibular nucleus neurons (mVNn). This model is described by a system of nonlinear ordinary differential equations, which is based on the Hodgkin-Hu...A previous study has proposed a mathematical model of type-A medial vestibular nucleus neurons (mVNn). This model is described by a system of nonlinear ordinary differential equations, which is based on the Hodgkin-Huxley formalism. The type-A mVNn model contains several ionic conductances, such as the sodium conductance, calcium conductance, delayed-rectifier potassium conductance, transient potassium conductance, and calcium-dependent potassium conductance. The previous study revealed that spontaneous repetitive spiking in the type-A mVNn model can be suppressed by hyperpolarizing stimulation. However, how this suppression is affected by the ionic conductances has not been clarified in the previous study. The present study performed numerical simulation analysis of the type-A mVNn model to clarify how variations in the different ionic conductance values affect the suppression of repetitive spiking. The present study revealed that the threshold for the transition from a repetitive spiking state to a quiescent state is differentially sensitive to variations in the ionic conductances among the different types of ionic conductance.展开更多
Bacterial cellulose(BC)was innovatively combined with zwitterionic copolymer acrylamide and sulfobetaine methacrylic acid ester[P(AM-co-SBMA)]to build a dual-network porous structure gel polymer electrolytes(GPEs)with...Bacterial cellulose(BC)was innovatively combined with zwitterionic copolymer acrylamide and sulfobetaine methacrylic acid ester[P(AM-co-SBMA)]to build a dual-network porous structure gel polymer electrolytes(GPEs)with high ionic conductivity.The dual network structure BC/P(AM-co-SBMA)gels were formed by a simple one-step polymerization method.The results show that ionic conductivity of BC/P(AM-co-SBMA)GPEs at the room temperature are 3.2×10^(-2) S/cm@1 M H_(2)SO_(4),4.5×10^(-2) S/cm@4 M KOH,and 3.6×10^(-2) S/cm@1 M NaCl,respectively.Using active carbon(AC)as the electrodes,BC/P(AM-co-SBMA)GPEs as both separator and electrolyte matrix,and 4 M KOH as the electrolyte,a symmetric solid supercapacitors(SSC)(AC-GPE-KOH)was assembled and testified.The specific capacitance of AC electrode is 173 F/g and remains 95.0%of the initial value after 5000 cycles and 86.2%after 10,000 cycles.展开更多
A composite solid electrolyte comprising a Cu-Al bimetallic metal-organic framework(CAB),lithium salt(LiTFSI)and polyethylene oxide(PEO)was fabricated through molecular grafting to enhance the ionic conductivity of th...A composite solid electrolyte comprising a Cu-Al bimetallic metal-organic framework(CAB),lithium salt(LiTFSI)and polyethylene oxide(PEO)was fabricated through molecular grafting to enhance the ionic conductivity of the PEO-based electrolytes.Experimental and molecular dynamics simulation results indicated that the electrolyte with 10 wt.%CAB(PL-CAB-10%)exhibits high ionic conductivity(8.42×10~(-4)S/cm at 60℃),high Li+transference number(0.46),wide electrochemical window(4.91 V),good thermal stability,and outstanding mechanical properties.Furthermore,PL-CAB-10%exhibits excellent cycle stability in both Li-Li symmetric battery and Li/PL-CAB-10%/LiFePO4 asymmetric battery setups.These enhanced performances are primarily attributable to the introduction of the versatile CAB.The abundant metal sites in CAB can react with TFSI~-and PEO through Lewis acid-base interactions,promoting LiTFSI dissociation and improving ionic conductivity.Additionally,regular pores in CAB provide uniformly distributed sites for cation plating during cycling.展开更多
Sulfide-based inorganic solid electrolytes are promising materials for high-performance safe solid-state batteries.The high ion conductivity,mechanical characteristics,and good processability of sulfide-based inorgani...Sulfide-based inorganic solid electrolytes are promising materials for high-performance safe solid-state batteries.The high ion conductivity,mechanical characteristics,and good processability of sulfide-based inorganic solid electrolytes are desirable properties for realizing high-performance safe solid-state batteries by replacing conventional liquid electrolytes.However,the low chemical and electrochemical stability of sulfide-based inorganic solid electrolytes hinder the commercialization of sulfide-based safe solid-state batteries.Particularly,the instability of sulfide-based inorganic solid electrolytes is intensified in the cathode,comprising various materials.In this study,carbonate-based ionic conductive polymers are introduced to the cathode to protect cathode materials and suppress the reactivity of sulfide electrolytes.Several instruments,including electrochemical spectroscopy,X-ray photoelectron spectroscopy,and scanning electron microscopy,confirm the chemical and electrochemical stability of the polymer electrolytes in contact with sulfide-based inorganic solid electrolytes.Sulfide-based solid-state cells show stable electrochemical performance over 100 cycles when the ionic conductive polymers were applied to the cathode.展开更多
Carbon was used as electronic conductive agent, and metasilicic acid lithium (Li<sub>2</sub>SiO<sub>3</sub>) as ionic conductive agent, the two factors were investigated cooperatively. We evalu...Carbon was used as electronic conductive agent, and metasilicic acid lithium (Li<sub>2</sub>SiO<sub>3</sub>) as ionic conductive agent, the two factors were investigated cooperatively. We evaluated their effect by using spherical spinel LiMn<sub>2</sub>O<sub>4</sub> which prepared ourselves as cathode material. Then Li<sub>2</sub>SiO<sub><sub></sub>3</sub>/carbon surface coating on LiMn<sub><sub></sub>2</sub>O<sub>4</sub> (LMO/C/LSO) which Li<sub><sub></sub>2</sub>SiO<sub><sub></sub>3</sub> inside and carbon/Li<sub><sub></sub>2</sub>SiO<sub><sub></sub>3</sub> coated LiMn<sub><sub></sub>2</sub>O<sub><sub></sub>4</sub> (LMO/LSO/C) were prepared, All of materials were characterized by X-ray diffraction (XRD) and electrochemical test;spherical LiMn<sub></sub>2O<sub></sub>4 was characterized by scanning electron microscopy (SEM);and coated materials were characterized by transmission electron microscopy (TEM). While uncoated spinel LiMn<sub><sub></sub>2</sub>O<sub><sub></sub>4</sub> maintained 72% of capacity in 60 cycles by the rate of 0.2C, and LMO/LSO/C showed the best electrochemical performance, 89% of the initial capacity remained after 75 cycles at 0.2C. Furthermore, the rate performance of LMO/LSO/C also improved obviously, about 30 mAh·g<sup>-1</sup> of capacity attained at the rate of 5C, higher than LMO/C/LSO and bare LiMn<sub><sub></sub>2</sub>O<sub><sub></sub>4</sub>.展开更多
Sodium-ion batteries are expected to be more affordable for stationary applications than lithium-ion batteries,while still offering sufficient energy density and operational capacity to power a significant segment of ...Sodium-ion batteries are expected to be more affordable for stationary applications than lithium-ion batteries,while still offering sufficient energy density and operational capacity to power a significant segment of the battery market.Despite this,thermal runaway explosions associated with organic electrolytes have led to concerns regarding the safety of sodium-ion batteries.Among electrolytes,ionic liquids are promising because they have negligible vapor pressure and show high thermal and electrochemical stability.This review discusses the safety contributions of these electrolyte properties for high-temperature applications.The ionic liquids provide thermal stability while at the same time promoting high-voltage window battery operations.Moreover,apart from cycle stability,there is an additional safety feature attributed to modified ultra-concentrated ionic liquid electrolytes.Concerning these contributions,the following have been discussed,heat sources and thermal runaway mechanisms,thermal stability,the electrochemical decomposition mechanism of stable cations,and the ionic transport mechanism of ultra-concentrated ionic liquid electrolytes.In addition,the contributions of hybrid electrolyte systems consisting of ionic liquids with either organic carbonate or polymers are also discussed.The thermal stability of ionic liquids is found to be the main contributor to cell safety and cycle stability.For high-temperature applications where electrolyte safety,capacity,and cycle stability are important,highly concentrated ionic liquid electrolyte systems are potential solutions for sodium-ion battery applications.展开更多
Ionic thermoelectrics(i-TE) possesses great potential in powering distributed electronics because it can generate thermopower up to tens of millivolts per Kelvin. However,as ions cannot enter external circuit, the uti...Ionic thermoelectrics(i-TE) possesses great potential in powering distributed electronics because it can generate thermopower up to tens of millivolts per Kelvin. However,as ions cannot enter external circuit, the utilization of i-TE is currently based on capacitive charge/discharge, which results in discontinuous working mode and low energy density. Here,we introduce an ion–electron thermoelectric synergistic(IETS)effect by utilizing an ion–electron conductor. Electrons/holes can drift under the electric field generated by thermodiffusion of ions, thus converting the ionic current into electrical current that can pass through the external circuit. Due to the IETS effect, i-TE is able to operate continuously for over 3000 min.Moreover, our i-TE exhibits a thermopower of 32.7 mV K^(-1) and an energy density of 553.9 J m^(-2), which is more than 6.9 times of the highest reported value. Consequently, direct powering of electronics is achieved with i-TE. This work provides a novel strategy for the design of high-performance i-TE materials.展开更多
Solid polymer electrolytes(SPEs)have emerged as one of the most promising candidates for building solid-state lithium batteries due to their excellent flexibility,scalability,and interfacial compatibility with electro...Solid polymer electrolytes(SPEs)have emerged as one of the most promising candidates for building solid-state lithium batteries due to their excellent flexibility,scalability,and interfacial compatibility with electrodes.However,the low ionic conductivity and poor cyclic stability of SPEs do not meet the requirements for practical applications of lithium batteries.Here,a novel polymer dispersed ionic liquid-based solid polymer electrolyte(PDIL-SPE)is fabricated using the in situ polymerization-induced phase separation(PIPS)method.The as-prepared PDIL-SPE possesses both outstanding ionic conductivity(0.74 mS cm^(-1) at 25℃)and a wide electrochemical window(up to 4.86 V),and the formed unique three-dimensional(3D)co-continuous structure of polymer matrix and ionic liquid in PDIL-SPE can promote the transport of lithium ions.Also,the 3D co-continuous structure of PDIL-SPE effectively accommodates the severe volume expansion for prolonged lithium plating and stripping processes over 1000 h at 0.5 mA cm^(-2) under 25℃.Moreover,the LiFePO_(4)//Li coin cell can work stably over 150 cycles at a 1 C rate under room temperature with a capacity retention of 90.6%from 111.1 to 100.7 mAh g^(-1).The PDIL-SPE composite is a promising material system for enabling the ultrastable operation of solid-state lithium-metal batteries.展开更多
The development and application of high-capacity energy storage has been crucial to the global transition from fossil fuels to green energy.In this context,metal-organic frameworks(MOFs),with their unique 3D porous st...The development and application of high-capacity energy storage has been crucial to the global transition from fossil fuels to green energy.In this context,metal-organic frameworks(MOFs),with their unique 3D porous structure and tunable chemical functionality,have shown enormous potential as energy storage materials for accommodating or transporting electrochemically active ions.In this perspective,we specifically focus on the current status and prospects of anionic MOF-based quasi-solid-state-electrolytes(anionic MOF-QSSEs)for lithium metal batteries(LMBs).An overview of the definition,design,and properties of anionic MOF-QSSEs is provided,including recent advances in the understanding of their ion transport mechanism.To illustrate the advantages of using anionic MOF-QSSEs as electrolytes for LMBs,a thorough comparison between anionic MOF-QSSEs and other well-studied electrolyte systems is made.With these in-depth understandings,viable techniques for tuning the chemical and topological properties of anionic MOF-QSSEs to increase Li+conductivity are discussed.Beyond modulation of the MOFs matrix,we envisage that solvent and solid-electrolyte interphase design as well as emerging fabrication techniques will aid in the design and practical application of anionic MOF-QSSEs.展开更多
Lithium metal batteries assembled with solid-state electrolyte can offer high safety and volumetric energy density compared to liquid electrolyte.The polymer solid-state electrolytes of poly(ethylene oxide)(PEO)are wi...Lithium metal batteries assembled with solid-state electrolyte can offer high safety and volumetric energy density compared to liquid electrolyte.The polymer solid-state electrolytes of poly(ethylene oxide)(PEO)are widely used in lithium metal solid-state batteries due to their unique properties.However,there are still some defects such as low ionic conductivity at room temperature and weak inhibition of lithium dendrite growth.Herein,the spiny inorganic nanofibers heterostructure with mullite whiskers grown on the surface of aluminum fluoride(AlF_(3))nanofibers are introduced into the PEOLi TFSI electrolytes for the first time to prepare composite solid-state electrolytes.The AlF_(3)as a strong Lewis acid can adsorb anions and promote the dissociation of Li salts.Besides,the specially threedimensional(3D)structure enlarges the effective contacting interface with the PEO polymer,which allows the lithium ions to be transported not only along the large aspect ratio of AlF3nanofibers,but also along the mullite phase in the transmembrane direction rapidly.Thereby,the transport channel of lithium ions at the spiny inorganic nanofibers-polymer interface is further improved.Benefiting from these advantages,the obtained composite solid-state electrolyte has a high ionic conductivity of 1.58×10^(-4)S cm^(-1)at 30℃and the lithium ions transfer number of 0.53.In addition,the AlF3has strong binding energy with anions,low electronic conductivity and wide electrochemical stability window,and reduced nucleation overpotential of lithium during cycling,which is positive for lithium dendrite suppression in solid-state electrolytes.Thus,the assembled symmetric Li/Li symmetric batteries exhibit stable cycling performance at different area capacities of 0.15,0.2,0.3 and 0.4 m A h cm^(-2).More importantly,the LiFePO_(4)(LFP)/Li battery still has 113.5 m A h g-1remaining after 400 cycles at 50℃and the Coulomb efficiency is nearly 100%during the long cycle.Overall,the interconnected structure of 3D spiny inorganic heterostructure nanofiber constitutes fast and uninterrupted lithium ions transport channels,maximizing the synergistic effect of interfacial transport of inorganic fillers and reducing PEO crystallinity,thus providing a novel approach to high performance solid-state electrolytes.展开更多
Glassy electrolytes could be a potential candidate for all-solid-state batteries that are considered new-generation energy storage devices. As glasses are one of the potential fast ion-conducting electrolytes, progres...Glassy electrolytes could be a potential candidate for all-solid-state batteries that are considered new-generation energy storage devices. As glasses are one of the potential fast ion-conducting electrolytes, progressive advances in glassy electrolytes have been undergoing to get commercial attention. However, the challenges offered by ionic conductivity at room temperature (10<sup>−5</sup> - 10<sup>−3</sup> S∙cm<sup>−1</sup>) in comparison to those of organic liquid electrolytes (10<sup>−2</sup> S∙cm<sup>−1</sup>) hindered the applicability of such electrolytes. To enhance the research development on ionic conductivity, the overall picture of the ionic conductivity of glassy electrolytes is reviewed in this article with a focus on alkali oxide and sulfide glasses. We portray here the techniques applied for alkali ion conductivity enhancement, such as methods of glass preparation, host optimization, doping, and salt addition for enhancing alkali ionic conductivity in the glasses.展开更多
All-solid-state batteries(ASSBs)are a class of safer and higher-energy-density materials compared to conventional devices,from which solid-state electrolytes(SSEs)are their essential components.To date,investigations ...All-solid-state batteries(ASSBs)are a class of safer and higher-energy-density materials compared to conventional devices,from which solid-state electrolytes(SSEs)are their essential components.To date,investigations to search for high ion-conducting solid-state electrolytes have attracted broad concern.However,obtaining SSEs with high ionic conductivity is challenging due to the complex structural information and the less-explored structure-performance relationship.To provide a solution to these challenges,developing a database containing typical SSEs from available experimental reports would be a new avenue to understand the structureperformance relationships and find out new design guidelines for reasonable SSEs.Herein,a dynamic experimental database containing>600 materials was developed in a wide range of temperatures(132.40–1261.60 K),including mono-and divalent cations(e.g.,Li^(+),Na^(+),K^(+),Ag^(+),Ca^(2+),Mg^(2+),and Zn^(2+))and various types of anions(e.g.,halide,hydride,sulfide,and oxide).Data-mining was conducted to explore the relationships among different variates(e.g.,transport ion,composition,activation energy,and conductivity).Overall,we expect that this database can provide essential guidelines for the design and development of high-performance SSEs in ASSB applications.This database is dynamically updated,which can be accessed via our open-source online system.展开更多
Extending the ionic conductivity is the pre-requisite of electrolytes in fuel cell technology for high-electrochemical performance.In this regard,the introduction of semiconductor-oxide materials and the approach of h...Extending the ionic conductivity is the pre-requisite of electrolytes in fuel cell technology for high-electrochemical performance.In this regard,the introduction of semiconductor-oxide materials and the approach of heterostructure formation by modulating energy bands to enhance ionic conduction acting as an electrolyte in fuel cell-device.Semiconductor(n-type;SnO_(2))plays a key role by introducing into p-type SrFe_(0.2)Ti_(0.8)O_(3-δ)(SFT)semiconductor perovskite materials to construct p-n heterojunction for high ionic conductivity.Therefore,two different composites of SFT and SnO_(2)are constructed by gluing p-and n-type SFT-SnO_(2),where the optimal composition of SFT-SnO_(2)(6∶4)heterostructure electrolyte-based fuel cell achieved excellent ionic conductivity 0.24 S cm^(-1)with power-output of 1004 mW cm^(-2)and high OCV 1.12 V at a low operational temperature of 500℃.The high power-output and significant ionic conductivity with durable operation of 54 h are accredited to SFT-SnO_(2)heterojunction formation including interfacial conduction assisted by a built-in electric field in fuel cell device.Moreover,the fuel conversion efficiency and considerable Faradaic efficiency reveal the compatibility of SFT-SnO_(2)heterostructure electrolyte and ruled-out short-circuiting issue.Further,the first principle calculation provides sufficient information on structure optimization and energy-band structure modulation of SFT-SnO_(2).This strategy will provide new insight into semiconductor-based fuel cell technology to design novel electrolytes.展开更多
Chloride solid electrolytes possess multiple advantages for the construction of safe,energy-dense allsolid-state sodium batteries,but presently the chlorides with sufficiently high cost-competitiveness for commerciali...Chloride solid electrolytes possess multiple advantages for the construction of safe,energy-dense allsolid-state sodium batteries,but presently the chlorides with sufficiently high cost-competitiveness for commercialization almost all exhibit low Na-ion conductivities of around 10^(-5)S cm^(-1)or lower.Here,we report a chloride solid electrolyte,Na_(2.7)ZFCl_(5.3)O_(0.7),which reaches a Na-ion conductivity of 2.29×10^(-4)S cm^(-1)at 25℃without involving overly expensive raw materials such as rare-earth chlorides or Na_(2)S.In addition to the efficient ion transport,Na_(2.7)ZrCl_(5.3)O_(0.7)also shows an excellent deformability surpassing that of the widely studied Na_(3)PS_(4),Na_(3)SbS_(4),and Na_(2)ZrCl_(6)solid electrolytes.The combination of these advantages allows the all-solid-state cell based on Na_(2.7)ZrCl_(5.3)O_(0.7)and NaCrO_(2)to realize stable room-temperature cycling at a much higher specific current than those based on other non-viscoelastic chloride solid electrolytes in literature(120 mA g^(-1)vs.12-55 mA g^(-1));after 100 cycles at such a high rate,the Na_(2.7)ZFCl_(5.3)O_(0.7)-based cell can still deliver a discharge capacity of 80 mAh g^(-1)at25℃.展开更多
Composite solid-state electrolytes represent a critical pathway that balances the interface compatibility and lithium-ion conductivity in all-solid-state batteries.The quest for stable and highly ion-conductive combin...Composite solid-state electrolytes represent a critical pathway that balances the interface compatibility and lithium-ion conductivity in all-solid-state batteries.The quest for stable and highly ion-conductive combinations between polymers and fillers is vital,but blind attempts are often made due to a lack of understanding of the mechanisms involved in the interaction between polymers and fillers.Herein,we employ in-situ polymerization to prepare a polymer based on an ether-nitrile copolymer with high cathode stability as the foundation and discuss the performance enhancement mechanisms of argyrodite and nano-alumina.With 1%content of sulfide interacting with the polymer at the two-phase interface,the local enhancement of lithium-ion migration capability can be achieved,avoiding the reduction in capacity due to the low ion conductivity of the passivation layer during cycling.The capacity retention after 50cycles at 0.5 C increases from 83.5%to 94.4%.Nano-alumina,through anchoring the anions and interface inhibition functions,eventually poses an initial discharge capacity of 136.8 m A h g^(-1)at 0.5 C and extends the cycling time to 1000 h without short-circuiting in lithium metal batteries.Through the combined action of dual fillers on the composite solid-state electrolyte,promising insights are provided for future material design.展开更多
Additives in the electrolytes of Li-S batteries aim to increase overall capacity,improve Li ion conductivity,enhance cyclability,and mitigate the shuttle effect,which is one of the major issues of this system.Here,the...Additives in the electrolytes of Li-S batteries aim to increase overall capacity,improve Li ion conductivity,enhance cyclability,and mitigate the shuttle effect,which is one of the major issues of this system.Here,the use of water as an additive in the commonly used electrolyte,1.0 M LiTFSI/1.0%(w/w) LiNO_(3) and a 1:1 mixture of 1,3-dioxolane(DOL) and 1,2-dimethoxyethane(DME) was investigated.We used Co_(2)Mn_(0.5)Al_(0.5)O_(4)(CMA) as an electrocatalyst anchored on an activated carbon(AC) electrode with added sulfur via a melt-diffusion process.The structural analysis of CMA via Rietveld refinement showed interatomic spaces that can promote ionic conductivity,facilitating Li^(+) ion migration.Electrochemical tests determined 1600 ppm as the optimal water concentration,significantly reducing the shuttle effect.Post-mortem XPS analysis focused on the lithium metal anode revealed the formation of Li_(2)O layers in dry samples and LiOH in wet samples.Better capacity was observed in wet samples,which can be attributed to the superior ionic conductivity of LiOH at the electrode/electrolyte interface,surpassing that of Li_(2)O by 12 times.Finally,Operando FTIR experiments provided real-time insights into electrolyte degradation and SEI formation,elucidating the activity mechanisms of water and Li_(2)CO_(3) over the cycles.This work presents results that could aid future advancements in Li-S battery technology,offering possibilities to mitigate its challenges with inexpensive and scalable additives.展开更多
The growing demand for substitutes of lithium chemistries in battery leads to a surge in budding novel anion-based electrochemical energy storage,where the chloride ion batteries(CIBs)take over the role.The applicatio...The growing demand for substitutes of lithium chemistries in battery leads to a surge in budding novel anion-based electrochemical energy storage,where the chloride ion batteries(CIBs)take over the role.The application of CIBs is limited by the dissolution and side reaction of chloride-based electrode materials in a liquid electrolyte.On the flipside,its solid-state electrolytes are scarcely reported due to the challenge in realizing fast Cl^(-)conductivity.The present study reports[Al(DMSO)_(6)]Cl_(3),a solid-state metal-organic material,allows chloride ion transfer.The strong Al-Cl bonds in AlCl_(3)are broken down after coordinating of Al^(3+)by ligand DMSO,and Cl^(-)in the resulting compound is weakly bound to complexions[Al(DMSO)_(6)]^(3+),which may facilitate Cl^(-)migration.By partial replacement of Cl^(-)with PF_(6)^(-),the room-temperature ionic conductivity of as-prepared electrolyte is increased by one order of magnitude from 2.172×10^(-5)S cm^(-1)to 2.012×10^(-4)S cm^(-1).When they are assembled with Ag(anode)/Ag-AgCl(cathode)electrode system,reversible electrochemical redox reactions occur on both sides,demonstrating its potential for solid-state chloride ion batteries.The strategy by weakening the bonding interaction using organic ligands between Cl^(-)and central metallic ions may provide new ideas for developing solid chloride-ion conductors.展开更多
Ga-doped Li_(7)La_(3)Zr_(2)O_(12)(Ga-LLZO)has long been considered as a promising garnet-type electrolyte candidate for all-solid-state lithium metal batteries(ASSLBs)due to its high room temperature ionic conductivit...Ga-doped Li_(7)La_(3)Zr_(2)O_(12)(Ga-LLZO)has long been considered as a promising garnet-type electrolyte candidate for all-solid-state lithium metal batteries(ASSLBs)due to its high room temperature ionic conductivity.However,the typical synthesis of Ga-LLZO is usually accompanied by the formation of undesired LiGaO_(2) impurity phase that causes severe instability of the electrolyte in contact with molten Li metal during half/full cell assembly.In this study,we show that by simply engineering the defect chemistry of Ga-LLZO,namely,the lithium deficiency level,LiGaO_(2) impurity phase is effectively inhibited in the final synthetic product.Consequently,defect chemistry engineered Ga-LLZO exhibits excellent electrochemical stability against lithium metal,while its high room temperature ionic conductivity(~1.9×10^(-3)S·cm^(-1))is well reserved.The assembled Li/Ga-LLZO/Li symmetric cell has a superior critical current density of 0.9 mA·cm^(-2),and cycles stably for 500 hours at a current density of 0.3 mA·cm^(-2).This research facilitates the potential commercial applications of high performance Ga-LLZO solid electrolytes in ASSLBs.展开更多
文摘A mathematical model of vibrissa motoneurons (vMN), which has been developed by Harish and Golomb, can show repetitive spiking in response to a transient external stimulation. The vMN model is described by a system of nonlinear ordinary differential equations based on the Hodgkin-Huxley scheme. The vMN model is regulated by various types of ionic conductances, such as persistent sodium, transient sodium, delayed-rectifier potassium, and slow ionic conductances (e.g., slowly activating potassium afterhyperpolarization (AHP) conductance and h conductance). In the present study, a numerical simulation analysis of the vMN model was performed to investigate the effect of variations in the transient sodium and the slow ionic conductance values on the response of the vMN model to a transient external stimulation. Numerical simulations revealed that when both the transient sodium and the AHP conductances are eliminated, the vMN model shows a bistable behavior (i.e., a stimulation-triggered transition between dynamic states). In contrast, none of the following induce the transition alone: 1) elimination of the transient sodium conductance;2) elimination of the AHP conductance;3) elimination of the h conductance;or 4) elimination of both the transient sodium and the h conductances.
文摘A previous study proposed a mathematical model of A-type horizontal cells in the rabbit retina. This model, which was constructed based on the Hodgkin-Huxley model, was described by a system of nonlinear ordinary differential equations. The model contained five types of voltage-dependent ionic conductances: sodium, calcium, delayed rectifier potassium, transient outward potassium, and anomalous rectifier potassium conductances. The previous study indicated that when the delayed rectifier potassium conductance had a small value, depolarizing stimulation could change the dynamic state of the model from a hyperpolarized steady state to a depolarized steady state. However, how this change was affected by variations in the ionic conductance values was not clarified in detail in the previous study. To clarify this issue, in the present study, we performed numerical simulation analysis of the model and revealed the differences among the five types of ionic conductances.
文摘A previous study has proposed a mathematical model of type-A medial vestibular nucleus neurons (mVNn). This model is described by a system of nonlinear ordinary differential equations, which is based on the Hodgkin-Huxley formalism. The type-A mVNn model contains several ionic conductances, such as the sodium conductance, calcium conductance, delayed-rectifier potassium conductance, transient potassium conductance, and calcium-dependent potassium conductance. The previous study revealed that spontaneous repetitive spiking in the type-A mVNn model can be suppressed by hyperpolarizing stimulation. However, how this suppression is affected by the ionic conductances has not been clarified in the previous study. The present study performed numerical simulation analysis of the type-A mVNn model to clarify how variations in the different ionic conductance values affect the suppression of repetitive spiking. The present study revealed that the threshold for the transition from a repetitive spiking state to a quiescent state is differentially sensitive to variations in the ionic conductances among the different types of ionic conductance.
基金Funded by National Natural Science Foundation of China(No.51472166)。
文摘Bacterial cellulose(BC)was innovatively combined with zwitterionic copolymer acrylamide and sulfobetaine methacrylic acid ester[P(AM-co-SBMA)]to build a dual-network porous structure gel polymer electrolytes(GPEs)with high ionic conductivity.The dual network structure BC/P(AM-co-SBMA)gels were formed by a simple one-step polymerization method.The results show that ionic conductivity of BC/P(AM-co-SBMA)GPEs at the room temperature are 3.2×10^(-2) S/cm@1 M H_(2)SO_(4),4.5×10^(-2) S/cm@4 M KOH,and 3.6×10^(-2) S/cm@1 M NaCl,respectively.Using active carbon(AC)as the electrodes,BC/P(AM-co-SBMA)GPEs as both separator and electrolyte matrix,and 4 M KOH as the electrolyte,a symmetric solid supercapacitors(SSC)(AC-GPE-KOH)was assembled and testified.The specific capacitance of AC electrode is 173 F/g and remains 95.0%of the initial value after 5000 cycles and 86.2%after 10,000 cycles.
基金supported by the National Natural Science Foundation of China(No.21501015)the Hunan Provincial Natural Science Foundation,China(No.2022JJ30604)Hunan Provincial Key Laboratory of Materials Protection for Electric Power and Transportation,China(No.2022CL01)。
文摘A composite solid electrolyte comprising a Cu-Al bimetallic metal-organic framework(CAB),lithium salt(LiTFSI)and polyethylene oxide(PEO)was fabricated through molecular grafting to enhance the ionic conductivity of the PEO-based electrolytes.Experimental and molecular dynamics simulation results indicated that the electrolyte with 10 wt.%CAB(PL-CAB-10%)exhibits high ionic conductivity(8.42×10~(-4)S/cm at 60℃),high Li+transference number(0.46),wide electrochemical window(4.91 V),good thermal stability,and outstanding mechanical properties.Furthermore,PL-CAB-10%exhibits excellent cycle stability in both Li-Li symmetric battery and Li/PL-CAB-10%/LiFePO4 asymmetric battery setups.These enhanced performances are primarily attributable to the introduction of the versatile CAB.The abundant metal sites in CAB can react with TFSI~-and PEO through Lewis acid-base interactions,promoting LiTFSI dissociation and improving ionic conductivity.Additionally,regular pores in CAB provide uniformly distributed sites for cation plating during cycling.
基金supported by the Enhancement of Performance and Production Technology of Lithium-based Next-generation Rechargeable Battery(project number 20012371)from the Ministry of Trade,Industry and Energy(MOTIE)of Koreasupported by project number KS2322-20(A Study on the Convergence Materials for Off-Grid Energy Conversion/Storage Integrated Devices)of the Korea Research Institute of Chemical Technology(KRICT).
文摘Sulfide-based inorganic solid electrolytes are promising materials for high-performance safe solid-state batteries.The high ion conductivity,mechanical characteristics,and good processability of sulfide-based inorganic solid electrolytes are desirable properties for realizing high-performance safe solid-state batteries by replacing conventional liquid electrolytes.However,the low chemical and electrochemical stability of sulfide-based inorganic solid electrolytes hinder the commercialization of sulfide-based safe solid-state batteries.Particularly,the instability of sulfide-based inorganic solid electrolytes is intensified in the cathode,comprising various materials.In this study,carbonate-based ionic conductive polymers are introduced to the cathode to protect cathode materials and suppress the reactivity of sulfide electrolytes.Several instruments,including electrochemical spectroscopy,X-ray photoelectron spectroscopy,and scanning electron microscopy,confirm the chemical and electrochemical stability of the polymer electrolytes in contact with sulfide-based inorganic solid electrolytes.Sulfide-based solid-state cells show stable electrochemical performance over 100 cycles when the ionic conductive polymers were applied to the cathode.
文摘Carbon was used as electronic conductive agent, and metasilicic acid lithium (Li<sub>2</sub>SiO<sub>3</sub>) as ionic conductive agent, the two factors were investigated cooperatively. We evaluated their effect by using spherical spinel LiMn<sub>2</sub>O<sub>4</sub> which prepared ourselves as cathode material. Then Li<sub>2</sub>SiO<sub><sub></sub>3</sub>/carbon surface coating on LiMn<sub><sub></sub>2</sub>O<sub>4</sub> (LMO/C/LSO) which Li<sub><sub></sub>2</sub>SiO<sub><sub></sub>3</sub> inside and carbon/Li<sub><sub></sub>2</sub>SiO<sub><sub></sub>3</sub> coated LiMn<sub><sub></sub>2</sub>O<sub><sub></sub>4</sub> (LMO/LSO/C) were prepared, All of materials were characterized by X-ray diffraction (XRD) and electrochemical test;spherical LiMn<sub></sub>2O<sub></sub>4 was characterized by scanning electron microscopy (SEM);and coated materials were characterized by transmission electron microscopy (TEM). While uncoated spinel LiMn<sub><sub></sub>2</sub>O<sub><sub></sub>4</sub> maintained 72% of capacity in 60 cycles by the rate of 0.2C, and LMO/LSO/C showed the best electrochemical performance, 89% of the initial capacity remained after 75 cycles at 0.2C. Furthermore, the rate performance of LMO/LSO/C also improved obviously, about 30 mAh·g<sup>-1</sup> of capacity attained at the rate of 5C, higher than LMO/C/LSO and bare LiMn<sub><sub></sub>2</sub>O<sub><sub></sub>4</sub>.
基金funded by CUA bursary,Ireland a project titled:Fabrication of solid-state electrolytes for batteries in smartphones and electric vehicles (EVs)。
文摘Sodium-ion batteries are expected to be more affordable for stationary applications than lithium-ion batteries,while still offering sufficient energy density and operational capacity to power a significant segment of the battery market.Despite this,thermal runaway explosions associated with organic electrolytes have led to concerns regarding the safety of sodium-ion batteries.Among electrolytes,ionic liquids are promising because they have negligible vapor pressure and show high thermal and electrochemical stability.This review discusses the safety contributions of these electrolyte properties for high-temperature applications.The ionic liquids provide thermal stability while at the same time promoting high-voltage window battery operations.Moreover,apart from cycle stability,there is an additional safety feature attributed to modified ultra-concentrated ionic liquid electrolytes.Concerning these contributions,the following have been discussed,heat sources and thermal runaway mechanisms,thermal stability,the electrochemical decomposition mechanism of stable cations,and the ionic transport mechanism of ultra-concentrated ionic liquid electrolytes.In addition,the contributions of hybrid electrolyte systems consisting of ionic liquids with either organic carbonate or polymers are also discussed.The thermal stability of ionic liquids is found to be the main contributor to cell safety and cycle stability.For high-temperature applications where electrolyte safety,capacity,and cycle stability are important,highly concentrated ionic liquid electrolyte systems are potential solutions for sodium-ion battery applications.
基金financially supported by research grants from the Natural Science Foundation of China [Grant No. 62074022 (K.S.), 12004057 (Y.J.Z.), 52173235 (M.L.)]the Natural Science Foundation of Chongqing [cstc2021jcyj-jqX0015 (K.S.)]+3 种基金Chongqing Talent Plan [cstc2021ycjh-bgzxm0334 (S.S.C.), CQYC2021059206 (K.S.)]Fundamental Research Funds for the Central Universities [No. 2020CDJQY-A055 (K.S.)]the Key Laboratory of Low-grade Energy Utilization Technologies and Systems [Grant No. LLEUTS-201901 (K.S.)]support from Chongqing Postgraduate Research and Innovation Project (CYS22032)。
文摘Ionic thermoelectrics(i-TE) possesses great potential in powering distributed electronics because it can generate thermopower up to tens of millivolts per Kelvin. However,as ions cannot enter external circuit, the utilization of i-TE is currently based on capacitive charge/discharge, which results in discontinuous working mode and low energy density. Here,we introduce an ion–electron thermoelectric synergistic(IETS)effect by utilizing an ion–electron conductor. Electrons/holes can drift under the electric field generated by thermodiffusion of ions, thus converting the ionic current into electrical current that can pass through the external circuit. Due to the IETS effect, i-TE is able to operate continuously for over 3000 min.Moreover, our i-TE exhibits a thermopower of 32.7 mV K^(-1) and an energy density of 553.9 J m^(-2), which is more than 6.9 times of the highest reported value. Consequently, direct powering of electronics is achieved with i-TE. This work provides a novel strategy for the design of high-performance i-TE materials.
基金supported by the National Key R&D Program of China (2020YFE0100200)the National Natural Science Foundation of China (Grant Nos.51921002,51927806).
文摘Solid polymer electrolytes(SPEs)have emerged as one of the most promising candidates for building solid-state lithium batteries due to their excellent flexibility,scalability,and interfacial compatibility with electrodes.However,the low ionic conductivity and poor cyclic stability of SPEs do not meet the requirements for practical applications of lithium batteries.Here,a novel polymer dispersed ionic liquid-based solid polymer electrolyte(PDIL-SPE)is fabricated using the in situ polymerization-induced phase separation(PIPS)method.The as-prepared PDIL-SPE possesses both outstanding ionic conductivity(0.74 mS cm^(-1) at 25℃)and a wide electrochemical window(up to 4.86 V),and the formed unique three-dimensional(3D)co-continuous structure of polymer matrix and ionic liquid in PDIL-SPE can promote the transport of lithium ions.Also,the 3D co-continuous structure of PDIL-SPE effectively accommodates the severe volume expansion for prolonged lithium plating and stripping processes over 1000 h at 0.5 mA cm^(-2) under 25℃.Moreover,the LiFePO_(4)//Li coin cell can work stably over 150 cycles at a 1 C rate under room temperature with a capacity retention of 90.6%from 111.1 to 100.7 mAh g^(-1).The PDIL-SPE composite is a promising material system for enabling the ultrastable operation of solid-state lithium-metal batteries.
基金financially supported by the Scientific Research Startup Funds from Tsinghua Shenzhen International Graduate School。
文摘The development and application of high-capacity energy storage has been crucial to the global transition from fossil fuels to green energy.In this context,metal-organic frameworks(MOFs),with their unique 3D porous structure and tunable chemical functionality,have shown enormous potential as energy storage materials for accommodating or transporting electrochemically active ions.In this perspective,we specifically focus on the current status and prospects of anionic MOF-based quasi-solid-state-electrolytes(anionic MOF-QSSEs)for lithium metal batteries(LMBs).An overview of the definition,design,and properties of anionic MOF-QSSEs is provided,including recent advances in the understanding of their ion transport mechanism.To illustrate the advantages of using anionic MOF-QSSEs as electrolytes for LMBs,a thorough comparison between anionic MOF-QSSEs and other well-studied electrolyte systems is made.With these in-depth understandings,viable techniques for tuning the chemical and topological properties of anionic MOF-QSSEs to increase Li+conductivity are discussed.Beyond modulation of the MOFs matrix,we envisage that solvent and solid-electrolyte interphase design as well as emerging fabrication techniques will aid in the design and practical application of anionic MOF-QSSEs.
基金supported by the National Natural Science Foundation of China(51973157,61904123,52103061,52203066)the Science&Technology Development Fund of Tianjin Education Commission for Higher Education(2018KJ196)+3 种基金the project funded by China Postdoctoral Science Foundation(2021T140419)Tianjin Municipal College Student’Innovation and Entrepreneurship Training Program(202110058052)the National Innovation and Entrepreneurship Training Program for College Students(202110058017)the State Key Laboratory of Membrane and Membrane Separation,Tiangong University。
文摘Lithium metal batteries assembled with solid-state electrolyte can offer high safety and volumetric energy density compared to liquid electrolyte.The polymer solid-state electrolytes of poly(ethylene oxide)(PEO)are widely used in lithium metal solid-state batteries due to their unique properties.However,there are still some defects such as low ionic conductivity at room temperature and weak inhibition of lithium dendrite growth.Herein,the spiny inorganic nanofibers heterostructure with mullite whiskers grown on the surface of aluminum fluoride(AlF_(3))nanofibers are introduced into the PEOLi TFSI electrolytes for the first time to prepare composite solid-state electrolytes.The AlF_(3)as a strong Lewis acid can adsorb anions and promote the dissociation of Li salts.Besides,the specially threedimensional(3D)structure enlarges the effective contacting interface with the PEO polymer,which allows the lithium ions to be transported not only along the large aspect ratio of AlF3nanofibers,but also along the mullite phase in the transmembrane direction rapidly.Thereby,the transport channel of lithium ions at the spiny inorganic nanofibers-polymer interface is further improved.Benefiting from these advantages,the obtained composite solid-state electrolyte has a high ionic conductivity of 1.58×10^(-4)S cm^(-1)at 30℃and the lithium ions transfer number of 0.53.In addition,the AlF3has strong binding energy with anions,low electronic conductivity and wide electrochemical stability window,and reduced nucleation overpotential of lithium during cycling,which is positive for lithium dendrite suppression in solid-state electrolytes.Thus,the assembled symmetric Li/Li symmetric batteries exhibit stable cycling performance at different area capacities of 0.15,0.2,0.3 and 0.4 m A h cm^(-2).More importantly,the LiFePO_(4)(LFP)/Li battery still has 113.5 m A h g-1remaining after 400 cycles at 50℃and the Coulomb efficiency is nearly 100%during the long cycle.Overall,the interconnected structure of 3D spiny inorganic heterostructure nanofiber constitutes fast and uninterrupted lithium ions transport channels,maximizing the synergistic effect of interfacial transport of inorganic fillers and reducing PEO crystallinity,thus providing a novel approach to high performance solid-state electrolytes.
文摘Glassy electrolytes could be a potential candidate for all-solid-state batteries that are considered new-generation energy storage devices. As glasses are one of the potential fast ion-conducting electrolytes, progressive advances in glassy electrolytes have been undergoing to get commercial attention. However, the challenges offered by ionic conductivity at room temperature (10<sup>−5</sup> - 10<sup>−3</sup> S∙cm<sup>−1</sup>) in comparison to those of organic liquid electrolytes (10<sup>−2</sup> S∙cm<sup>−1</sup>) hindered the applicability of such electrolytes. To enhance the research development on ionic conductivity, the overall picture of the ionic conductivity of glassy electrolytes is reviewed in this article with a focus on alkali oxide and sulfide glasses. We portray here the techniques applied for alkali ion conductivity enhancement, such as methods of glass preparation, host optimization, doping, and salt addition for enhancing alkali ionic conductivity in the glasses.
基金supported by the Ensemble Grant for Early Career Researchers 2022 and the 2023 Ensemble Continuation Grant of Tohoku University,the Hirose Foundation,the Iwatani Naoji Foundation,and the AIMR Fusion Research Grantsupported by JSPS KAKENHI Nos.JP23K13599,JP23K13703,JP22H01803,and JP18H05513+2 种基金the Center for Computational Materials Science,Institute for Materials Research,Tohoku University for the use of MASAMUNEIMR(Nos.202212-SCKXX0204 and 202208-SCKXX-0212)the Institute for Solid State Physics(ISSP)at the University of Tokyo for the use of their supercomputersthe China Scholarship Council(CSC)fund to pursue studies in Japan.
文摘All-solid-state batteries(ASSBs)are a class of safer and higher-energy-density materials compared to conventional devices,from which solid-state electrolytes(SSEs)are their essential components.To date,investigations to search for high ion-conducting solid-state electrolytes have attracted broad concern.However,obtaining SSEs with high ionic conductivity is challenging due to the complex structural information and the less-explored structure-performance relationship.To provide a solution to these challenges,developing a database containing typical SSEs from available experimental reports would be a new avenue to understand the structureperformance relationships and find out new design guidelines for reasonable SSEs.Herein,a dynamic experimental database containing>600 materials was developed in a wide range of temperatures(132.40–1261.60 K),including mono-and divalent cations(e.g.,Li^(+),Na^(+),K^(+),Ag^(+),Ca^(2+),Mg^(2+),and Zn^(2+))and various types of anions(e.g.,halide,hydride,sulfide,and oxide).Data-mining was conducted to explore the relationships among different variates(e.g.,transport ion,composition,activation energy,and conductivity).Overall,we expect that this database can provide essential guidelines for the design and development of high-performance SSEs in ASSB applications.This database is dynamically updated,which can be accessed via our open-source online system.
基金supported by the National Natural Science Foundation of China(Grant No.32250410309 and 52105582)Natural Science Foundation of Guangdong Province(Grant No.2022A1515010894 and 2022B0303040002)+1 种基金Fundamental Research Foundation of Shenzhen(JCYJ20210324095210030 and JCYJ20220818095810023)Shenzhen-Hong Kong-Macao S&T Program(Category C:SGDX20210823103200004)
文摘Extending the ionic conductivity is the pre-requisite of electrolytes in fuel cell technology for high-electrochemical performance.In this regard,the introduction of semiconductor-oxide materials and the approach of heterostructure formation by modulating energy bands to enhance ionic conduction acting as an electrolyte in fuel cell-device.Semiconductor(n-type;SnO_(2))plays a key role by introducing into p-type SrFe_(0.2)Ti_(0.8)O_(3-δ)(SFT)semiconductor perovskite materials to construct p-n heterojunction for high ionic conductivity.Therefore,two different composites of SFT and SnO_(2)are constructed by gluing p-and n-type SFT-SnO_(2),where the optimal composition of SFT-SnO_(2)(6∶4)heterostructure electrolyte-based fuel cell achieved excellent ionic conductivity 0.24 S cm^(-1)with power-output of 1004 mW cm^(-2)and high OCV 1.12 V at a low operational temperature of 500℃.The high power-output and significant ionic conductivity with durable operation of 54 h are accredited to SFT-SnO_(2)heterojunction formation including interfacial conduction assisted by a built-in electric field in fuel cell device.Moreover,the fuel conversion efficiency and considerable Faradaic efficiency reveal the compatibility of SFT-SnO_(2)heterostructure electrolyte and ruled-out short-circuiting issue.Further,the first principle calculation provides sufficient information on structure optimization and energy-band structure modulation of SFT-SnO_(2).This strategy will provide new insight into semiconductor-based fuel cell technology to design novel electrolytes.
基金the financial support from the Strategic Priority Research Program of the Chinese Academy of Sciences(XDB0450201)the National Key R&D Program of China(2018YFA0209600)+2 种基金USTC Research Funds of the Double FirstClass Initiative(YD2060002033)the Fundamental Research Funds for the Central Universities(WK2060000060)the National Synchrotron Radiation Laboratory(KY2060000199)。
文摘Chloride solid electrolytes possess multiple advantages for the construction of safe,energy-dense allsolid-state sodium batteries,but presently the chlorides with sufficiently high cost-competitiveness for commercialization almost all exhibit low Na-ion conductivities of around 10^(-5)S cm^(-1)or lower.Here,we report a chloride solid electrolyte,Na_(2.7)ZFCl_(5.3)O_(0.7),which reaches a Na-ion conductivity of 2.29×10^(-4)S cm^(-1)at 25℃without involving overly expensive raw materials such as rare-earth chlorides or Na_(2)S.In addition to the efficient ion transport,Na_(2.7)ZrCl_(5.3)O_(0.7)also shows an excellent deformability surpassing that of the widely studied Na_(3)PS_(4),Na_(3)SbS_(4),and Na_(2)ZrCl_(6)solid electrolytes.The combination of these advantages allows the all-solid-state cell based on Na_(2.7)ZrCl_(5.3)O_(0.7)and NaCrO_(2)to realize stable room-temperature cycling at a much higher specific current than those based on other non-viscoelastic chloride solid electrolytes in literature(120 mA g^(-1)vs.12-55 mA g^(-1));after 100 cycles at such a high rate,the Na_(2.7)ZFCl_(5.3)O_(0.7)-based cell can still deliver a discharge capacity of 80 mAh g^(-1)at25℃.
基金supported by the Science and Technology Commission of Shanghai Municipality(No.19DZ2270100),China。
文摘Composite solid-state electrolytes represent a critical pathway that balances the interface compatibility and lithium-ion conductivity in all-solid-state batteries.The quest for stable and highly ion-conductive combinations between polymers and fillers is vital,but blind attempts are often made due to a lack of understanding of the mechanisms involved in the interaction between polymers and fillers.Herein,we employ in-situ polymerization to prepare a polymer based on an ether-nitrile copolymer with high cathode stability as the foundation and discuss the performance enhancement mechanisms of argyrodite and nano-alumina.With 1%content of sulfide interacting with the polymer at the two-phase interface,the local enhancement of lithium-ion migration capability can be achieved,avoiding the reduction in capacity due to the low ion conductivity of the passivation layer during cycling.The capacity retention after 50cycles at 0.5 C increases from 83.5%to 94.4%.Nano-alumina,through anchoring the anions and interface inhibition functions,eventually poses an initial discharge capacity of 136.8 m A h g^(-1)at 0.5 C and extends the cycling time to 1000 h without short-circuiting in lithium metal batteries.Through the combined action of dual fillers on the composite solid-state electrolyte,promising insights are provided for future material design.
基金the financial support from the Brazilian funding agencies FAPESP. (2024/01031-1, 2022/022220, 2020/04281-8, 21/14442-1, 17/11986-5)support from FAPESP through the research project Pi (2022/02901-4)+2 种基金CAPES (1740195)CNPq through the research grant (313672/2021-0)support Shell and the strategic importance of the support given by ANP (Brazil’s National Oil, Natural Gas and Biofuels Agency) through the R & D levy regulation。
文摘Additives in the electrolytes of Li-S batteries aim to increase overall capacity,improve Li ion conductivity,enhance cyclability,and mitigate the shuttle effect,which is one of the major issues of this system.Here,the use of water as an additive in the commonly used electrolyte,1.0 M LiTFSI/1.0%(w/w) LiNO_(3) and a 1:1 mixture of 1,3-dioxolane(DOL) and 1,2-dimethoxyethane(DME) was investigated.We used Co_(2)Mn_(0.5)Al_(0.5)O_(4)(CMA) as an electrocatalyst anchored on an activated carbon(AC) electrode with added sulfur via a melt-diffusion process.The structural analysis of CMA via Rietveld refinement showed interatomic spaces that can promote ionic conductivity,facilitating Li^(+) ion migration.Electrochemical tests determined 1600 ppm as the optimal water concentration,significantly reducing the shuttle effect.Post-mortem XPS analysis focused on the lithium metal anode revealed the formation of Li_(2)O layers in dry samples and LiOH in wet samples.Better capacity was observed in wet samples,which can be attributed to the superior ionic conductivity of LiOH at the electrode/electrolyte interface,surpassing that of Li_(2)O by 12 times.Finally,Operando FTIR experiments provided real-time insights into electrolyte degradation and SEI formation,elucidating the activity mechanisms of water and Li_(2)CO_(3) over the cycles.This work presents results that could aid future advancements in Li-S battery technology,offering possibilities to mitigate its challenges with inexpensive and scalable additives.
基金supported by the Czech Science Foundation(GACR No.2016124J)supported by the grant of Specific university researchgrant No.A2_FCHT_2022_056
文摘The growing demand for substitutes of lithium chemistries in battery leads to a surge in budding novel anion-based electrochemical energy storage,where the chloride ion batteries(CIBs)take over the role.The application of CIBs is limited by the dissolution and side reaction of chloride-based electrode materials in a liquid electrolyte.On the flipside,its solid-state electrolytes are scarcely reported due to the challenge in realizing fast Cl^(-)conductivity.The present study reports[Al(DMSO)_(6)]Cl_(3),a solid-state metal-organic material,allows chloride ion transfer.The strong Al-Cl bonds in AlCl_(3)are broken down after coordinating of Al^(3+)by ligand DMSO,and Cl^(-)in the resulting compound is weakly bound to complexions[Al(DMSO)_(6)]^(3+),which may facilitate Cl^(-)migration.By partial replacement of Cl^(-)with PF_(6)^(-),the room-temperature ionic conductivity of as-prepared electrolyte is increased by one order of magnitude from 2.172×10^(-5)S cm^(-1)to 2.012×10^(-4)S cm^(-1).When they are assembled with Ag(anode)/Ag-AgCl(cathode)electrode system,reversible electrochemical redox reactions occur on both sides,demonstrating its potential for solid-state chloride ion batteries.The strategy by weakening the bonding interaction using organic ligands between Cl^(-)and central metallic ions may provide new ideas for developing solid chloride-ion conductors.
基金financially supported by the National Natural Science Foundation of China (Grant No.52171221)the National Key Research and Development Program of China (Grant No.2019YFA0704900)。
文摘Ga-doped Li_(7)La_(3)Zr_(2)O_(12)(Ga-LLZO)has long been considered as a promising garnet-type electrolyte candidate for all-solid-state lithium metal batteries(ASSLBs)due to its high room temperature ionic conductivity.However,the typical synthesis of Ga-LLZO is usually accompanied by the formation of undesired LiGaO_(2) impurity phase that causes severe instability of the electrolyte in contact with molten Li metal during half/full cell assembly.In this study,we show that by simply engineering the defect chemistry of Ga-LLZO,namely,the lithium deficiency level,LiGaO_(2) impurity phase is effectively inhibited in the final synthetic product.Consequently,defect chemistry engineered Ga-LLZO exhibits excellent electrochemical stability against lithium metal,while its high room temperature ionic conductivity(~1.9×10^(-3)S·cm^(-1))is well reserved.The assembled Li/Ga-LLZO/Li symmetric cell has a superior critical current density of 0.9 mA·cm^(-2),and cycles stably for 500 hours at a current density of 0.3 mA·cm^(-2).This research facilitates the potential commercial applications of high performance Ga-LLZO solid electrolytes in ASSLBs.