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
The point-to-point contact mechanism in all-solid-state Li-S batteries(ASSLSBs)is not as efficient as a liquid electrolyte which has superior mobility in the electrode,resulting in a slower reaction kinetics and inade...The point-to-point contact mechanism in all-solid-state Li-S batteries(ASSLSBs)is not as efficient as a liquid electrolyte which has superior mobility in the electrode,resulting in a slower reaction kinetics and inadequate ionic/electronic conduction network between the S(or Li_(2)S),conductive carbon,and solid-state electrolytes(SSEs)for achieving a swift(dis)charge reaction.Herein,a series of hybrid ionic/electronic conduction triple-phase interfaces with transition metal and nitrogen co-doping were designed.The graphitic ordered mesoporous carbon frameworks(TM-N-OMCs;TM=Fe,Co,Ni,and Cu)serve as hosts for Li_(2)S and Li_(6)PS_(5)Cl(LPSC)and provide abundant reaction sites on the triple interface.Results from both experimental and computational research display that the combination of Cu-N co-dopants can promote the Li-ion diffusion for rapid transformation of Li_(2)S with adequate ionic(6.73×10^(−4)S·cm^(−1))/electronic conductivities(1.77×10^(−2)S·cm^(−1))at 25℃.The as-acquired Li_(2)S/Cu-N-OMC/LPSC electrode exhibits a high reversible capacity(1147.7 mAh·g^(−1))at 0.1 C,excellent capacity retention(99.5%)after 500 cycles at 0.5 C,and high areal capacity(7.08 mAh·cm^(−2)).展开更多
Lithium-sulfur(Li-S) batteries and lithium-selenium(Li-Se) batteries,as environmental protection energy storage systems with outstanding theoretical specific capacities and high energy densities,have become the hotspo...Lithium-sulfur(Li-S) batteries and lithium-selenium(Li-Se) batteries,as environmental protection energy storage systems with outstanding theoretical specific capacities and high energy densities,have become the hotspots of current researches.Besides,elemental S(Se) raw materials are widely sourced and their production costs are both low,which make them considered one of the new generations of high energy density electrochemical energy storage systems with the most potential for development.However,poor conductivity of elemental S/Se and the notorious "shuttle effect" of lithium polysulfides(polyselenides) severely hinder the commercialization of Li-S/Se batteries.Thanks to the excellent electrical conductivity and strong absorption of lithium polysulfide(polyselenide) about electronically conducting polymer,some of the above thorny problems have been effectively alleviated.The review presents the fundamental studies and current development trends of common electronically conducting polymers in various components of Li-S/Se batteries,which involves polyaniline(PANI) polypyrrole(PPy),and polythiophene(PTh) with its derivatives,e.g.polyethoxythiophene(PEDOT) and poly(3,4-ethylene dioxythiophene)-poly(styrenesulfonate)(PEDOT:PSS).Finally,the review not only summarizes the research directions and challenges facing the application of electronically conducting polymers,but also looks forward to the development prospects of them,which will provide a way for the practical use of electronically conducting polymers in Li-S/Se batteries with outstanding electrochemical properties in the short run.展开更多
A study on electronic conductivity of CaO-SiO2-Al2O3-FeOxslag system with Wagner polarization technique was carried out.The experimental data show that electronic conductivity is consisted of free electron conductivit...A study on electronic conductivity of CaO-SiO2-Al2O3-FeOxslag system with Wagner polarization technique was carried out.The experimental data show that electronic conductivity is consisted of free electron conductivity and electron hole conductivity and both are related to the content of Fe3+and Fe2+.Free electron conductivity is decreasing and electron hole conductivity is increasing while Fe3+changes to Fe2+.There is a maximum electronic conductivity at some ratio of ferric ions Fe3+to total ion content.Under the experimental conditions,the electronic conductivity is in the range of 10-4—10-2S/cm.展开更多
The ZrO2 (9mol% Y2O3) coating was prepared evenly on the surface of MgO partially stabilized zirconia (Mg-PSZ) tube (oxygen sensor probe) by dipping the green Mg-PSZ tube in a ZrO2 (9mol% Y2O3) slurry and then co-fir...The ZrO2 (9mol% Y2O3) coating was prepared evenly on the surface of MgO partially stabilized zirconia (Mg-PSZ) tube (oxygen sensor probe) by dipping the green Mg-PSZ tube in a ZrO2 (9mol% Y2O3) slurry and then co-firing at 1750°C for 8 h. The double-cell method was employed to measure the electronic conductivity parameter and exam the reproducibility of the coated Mg- PSZ tube. The experimental results indicate that the good thermal shock resistance of the Mg-PSZ tube can be retained when the coating thickness is not more than 3.4 μm. The ZrO2 (9mol% Y2O3) coating reduces the electronic conductivity parameter remarka- bly, probably due to the lower electronic conductivity of Y2O,-stabilized ZrO2 than that of MgO-stabilized ZrO2. Moreover, the ZrO2 (9mol% Y2O3) coating can improve the reproducibility and accuracy of the Mg-PSZ tube significantly in the low oxygen measure- ment. The smooth surface feature and lower electronic conductivity of the coated Mg-PSZ tube should be responsible for this im- provement.展开更多
We investigated the electronic heat capacity, thermal conductivity, and resistivity of UN using Quantum Espresso and EPW code. GGA, PBEsol functional was used. The calculated electronic heat coefficient was found to b...We investigated the electronic heat capacity, thermal conductivity, and resistivity of UN using Quantum Espresso and EPW code. GGA, PBEsol functional was used. The calculated electronic heat coefficient was found to be significantly reduced (0.0176 J<span style="white-space:nowrap;"><span style="white-space:nowrap;">⋅</span></span>mol<sup><span style="white-space:nowrap;">-</span>1</sup><span style="white-space:nowrap;"><span style="white-space:nowrap;">⋅</span></span>K<sup><span style="white-space:nowrap;">-</span>2</sup> versus 0.0006 J<span style="white-space:nowrap;"><span style="white-space:nowrap;">⋅</span></span>mol<sup><span style="white-space:nowrap;">-</span>1</sup><span style="white-space:nowrap;"><span style="white-space:nowrap;">⋅</span></span>K<sup><span style="white-space:nowrap;">-</span>2</sup>) when the non-local hybrid functional (B3LYP) was used. Furthermore, we calculated electrical resistivity using a very transparent Ziman’s formula for metals with the Eliashberg transport coupling function as implemented in EPW code for non-spin-polarized calculations. The number of mobile electrons in UN, as a function of temperature, was derived from the ratio of the calculated resistivity and available experimental data. The electronic thermal conductivity was evaluated from the calculated electronic resistivity via Wiedemann-Franz law with the number of mobility electrons (<em>n<sub>av</sub></em>) incorporated (averaged over the temperature range 300 K - 1000 K). Both the electronic thermal conductivity and resistivity, as calculated using newly evaluated <em>n<sub>av</sub></em>, compare well with experimental data at ~700 K, but to reproduce the observed trend as a function of temperature, the number of mobile electrons must decrease with the temperature as evaluated.展开更多
Silica-based anode is widely employed for high energy density Li-ion batteries owing to their high theoretical specific capacity(4200 m A h g-1).However,it is always accompanied by a huge volume expansion(300%)and shr...Silica-based anode is widely employed for high energy density Li-ion batteries owing to their high theoretical specific capacity(4200 m A h g-1).However,it is always accompanied by a huge volume expansion(300%)and shrinks during the lithiation/delithiation process,further leading to low cycle stability.Efforts to mitigate the adverse effects caused by volume expansion such as robust binder matrix,Coreshell structure,etc.,inevitably affect the electronic conductivity within the electrode.Herein,a high conductivity and elasticity Si anode(Ni-P-SBR(styrene-butadiene rubber)@Si)was designed and fabricated via the Ni-P-SBR composite-electroless-plating process.In this design,the Si particles are surrounded by SBR polymer and Ni particles,where the SBR can adapt to the volume change and Ni particles can provide the electrode with high electronic conductivity.Therefore,the Ni-P-SBR@Si delivers a high initial capacity of 3470 m A h g-1and presents capacity retention of 49.4%within 200 cycles at 600 m A g-1.Additionally,a high capacity of 1153 m A h g-1can be achieved at 2000 m A g-1and can be cycled stably under bending conditions.This strategy provides feasible ideas to solve the key issues that limit the practical application of Si anodes.展开更多
The structural transformations,oxygen releasing and side reactions with electrolytes on the surface are considered as the main causes of the performance degradation of Li-rich layered oxides(LROs)cathodes in Li-ion ba...The structural transformations,oxygen releasing and side reactions with electrolytes on the surface are considered as the main causes of the performance degradation of Li-rich layered oxides(LROs)cathodes in Li-ion batteries.Thus,stabilizing the surfaces of LROs is the key to realize their practical application in high energy density Li-ion batteries.Surface coating is regarded as one of the most effective strategies for high voltage cathodes.The ideal coating materials should prevent cathodes from electrolyte corrosion and possess both electronic and Li-ionic conductivities simultaneously.However,commonly reported coating materials are unable to balance these functions well.Herein,a new type of coating material,La_(2)CuO_(4)was introduced to mitigate the surface issues of LROs for the first time,due to its superb electronic conductivity(26-35 mS·cm^(-1))and lithium-ionic diffusion coefficient(10^(-12)-10^(-13)cm^(2)·s^(-1)).After coating with the La_(2)CuO_(4),the capacity retention of Li_(1.2)Ni_(0.54)Co_(0.13)Mn_(0.13)O_(2)cathode was increased to 85.9%(compared to 79.3%of uncoated cathode)after 150 cycles in the voltage range of 2.0-4.8 V.In addition,only negligible degradations on the deliverable capacity and rate capability were observed.展开更多
The high energy density and stability of solid-state lithium metal batteries(SSLMBs)have garnered great attention.Garnet-type oxides,especially Li_(6.4)La_(3)Zr_(1.4)Ta_(0.6)O_(12)(LLZTO),with high ionic conductivity,...The high energy density and stability of solid-state lithium metal batteries(SSLMBs)have garnered great attention.Garnet-type oxides,especially Li_(6.4)La_(3)Zr_(1.4)Ta_(0.6)O_(12)(LLZTO),with high ionic conductivity,wide electrochemical window,and stability to Li metal anode,are promising solid-state electrolyte(SSEs)materials for SSLMBs.However,Li/LLZTO interface issues including high interface resistance,inhomogeneous Li deposition,and Li dendrite growth have hindered the practical application of SSLMBs.Herein,a multi-functional Li–SnF_(2) composite anode with Li,LiF,and Li-Sn alloy was specifically designed and prepared.The composite anode improves the wettability to LLZTO,constructing an intimate contact interface between it and LLZTO.Meanwhile,ionic/electronic conductive paths in situ formed at the interface can effectively uniform Li deposition and suppress Li dendrite.The solid-state symmetric cell exhibits low interface resistance(11Ω·cm^(2)) and high critical current density(1.3 mA·cm^(−2))at 25℃.The full SSLMB based on LiFePO_(4) or LiNi_(0.5)Co_(0.2)Mn_(0.3)O_(2) cathode also shows stable cycling performance and high rate capability.This work provides a new composite anode strategy for achieving high-energy density and high-safety SSLMBs.展开更多
The main challenges in development of traditional liquid lithium-sulfur batteries are the shuttle effect at the cathode caused by the polysulfide and the safety concern at the Li metal anode arose from the dendrite fo...The main challenges in development of traditional liquid lithium-sulfur batteries are the shuttle effect at the cathode caused by the polysulfide and the safety concern at the Li metal anode arose from the dendrite formation.All-solid-state lithium-sulfur batteries have been proposed to solve the shuttle effect and prevent short circuits.However,solid-solid contacts between the electrodes and the electrolyte increase the interface resistance and stress/strain,which could result in the limited electrochemical performances.In this work,the cathode of all-solid-state lithium-sulfur batteries is prepared by depositing sulfur on the surface of the carbon nanotubes(CNTs@S)and further mixing with Li10GeP2S12 electrolyte and acetylene black agents.At 60℃,CNTs@S electrode exhibits superior electrochemical performance,delivering the reversible discharge capacities of 1193.3,959.5,813.1,569.6 and 395.5 mAhg^-1 at the rate of 0.1,0.5,1,2 and 5 C,respectively.Moreover,the CNTs@S is able to demonstrate superior high-rate capability of 660.3 mAhg^-1 and cycling stability of 400 cycles at a high rate of 1.0 C.Such uniform distribution of the CNTs,S and Li10GeP2S12 electrolyte increase the electronic and ionic conductivity between the cathode and the electrolyte hence improves the rate performance and capacity retention.展开更多
The electrochemical nature of reaction between melt and slag in a closed system was worked out. Experimental results demonstrated that both the rate and reaction extent increase when the electronic conductor or voltag...The electrochemical nature of reaction between melt and slag in a closed system was worked out. Experimental results demonstrated that both the rate and reaction extent increase when the electronic conductor or voltage was applied between melt and slag. The bigger the contact area of the conductor with melts is, the faster the reaction rate is. With the increase of applied voltage which is beneficial for electron's migration between metal and slags, the rate and extent of reaction increase.展开更多
Ce0.85Sm0.15O1.925 (SDC) and La0.9Sr0.1Ga0.5Mg0.2O2.85 (LSGM) were synthesized using Glycine-Nitrate Process (GNP), and the composite electrolytes were prepared by mixing SDC and LSGM. An X-ray diffraction patte...Ce0.85Sm0.15O1.925 (SDC) and La0.9Sr0.1Ga0.5Mg0.2O2.85 (LSGM) were synthesized using Glycine-Nitrate Process (GNP), and the composite electrolytes were prepared by mixing SDC and LSGM. An X-ray diffraction pattern indicated that the mixture of SDC and LSGM consisted of their original phases after heating at 1450 ℃ for 10 h. The electronic conductivity of SDC-LSGM composite electrolytes were measured by direct current polarization method using Hebb-Wagner ion blocking cell at 700-800 ℃ in the oxygen partial pressure range of 104-10-20 MPa and compared with the results of SDC. Typical polarization curves, which were theoretically predicted, were observed on all the samples. The slopes of lgσe-lgPo2 plot for all the composite electrolytes agreed with the theoretically predicted value of-1/4 at some intermediate oxygen partial pressures and -1/6 at low oxygen partial pressure. The electronic conductivity of SDC-LSGM composite electrolytes decreased with the increase in LSGM content, whereas the ionic transport number ti of all the samples increased with the increase in LSGM content.展开更多
The electrical conduction properties of dense BaCe0.9Mn0.1O3-d (BCM10) membrane were investigated in the temperature range of 600-900oC. High ionic and electronic conductivities at elevated temperatures make BCM10 a ...The electrical conduction properties of dense BaCe0.9Mn0.1O3-d (BCM10) membrane were investigated in the temperature range of 600-900oC. High ionic and electronic conductivities at elevated temperatures make BCM10 a potential ceramic material for hydrogen separation. Hydrogen permeation through BCM10 membranes was studied using a high- temperature permeation cell. Little hydrogen could be detected at the sweep side. However, appreciable hydrogen can permeate through BCM10 membrane coated with porous platinum black, which shows that the process of hydrogen permeation through BCM10 membranes was controlled by the catalytic decomposition and recomposition of hydrogen on the surfaces of BCM10 membranes.展开更多
The limited lithium resource in earth's crust has stimulated the pursuit of alternative energy storage technologies to lithium-ion battery.Potassium-ion batteries(KIBs)are regarded as a kind of promising candidate...The limited lithium resource in earth's crust has stimulated the pursuit of alternative energy storage technologies to lithium-ion battery.Potassium-ion batteries(KIBs)are regarded as a kind of promising candidate for large-scale energy storage owing to the high abundance and low cost of potassium resources.Nevertheless,further development and wide application of KIBs are still challenged by several obstacles,one of which is their fast capacity deterioration at high rates.A considerable amount of effort has recently been devoted to address this problem by developing advanced carbonaceous anode materials with diverse structures and morphologies.This review presents and highlights how the architecture engineering of carbonaceous anode materials gives rise to high-rate performances for KIBs,and also the beneficial conceptions are consciously extracted from the recent progress.Particularly,basic insights into the recent engineering strategies,structural innovation,and the related advances of carbonaceous anodes for high-rate KIBs are under specific concerns.Based on the achievements attained so far,a perspective on the foregoing,and proposed possible directions,and avenues for designing high-rate anodes,are presented finally.展开更多
By altering the electrochemical properties of slag, the decarburization reaction of Fe3+-based slag withFe-C droplet was studied. The results showed that a lot of free electrons and holes exist in the slag containing ...By altering the electrochemical properties of slag, the decarburization reaction of Fe3+-based slag withFe-C droplet was studied. The results showed that a lot of free electrons and holes exist in the slag containing transition metal oxides (such as TiO2 and Fe2O3). So electronic conduction in the slag increases. Finally, it led to the increment of the decarburization reaction rate between slag and Fe-C droplet, and mass fraction of carbon remaining indroplet decreases to a lower level.展开更多
Constructing layered-spinel composites is important to improve the rate performance of lithium-rich layered oxides.However,up to now,the effect of microstructure of composites on the rate performance has not been well...Constructing layered-spinel composites is important to improve the rate performance of lithium-rich layered oxides.However,up to now,the effect of microstructure of composites on the rate performance has not been well investigated.In this study,a series of samples were prepared by a simple protonation and de-protonation for the pristine layered material(LiMnNiCoO)obtained by sol-gel method.The characterizations of XRD,Raman and oxidation-reduction potentials of charge-discharge curves demonstrated that these samples after de-protonation are layered-spinel composites.When these composites were tested as a cathode of lithium-ion batteries,the sample treated with 0.1 M of nitric acid exhibited higher discharge capacities at each current density than that of other composites.The outstanding rate performance is attributed to the high concentration of conduction electron resulting from the low average valence state(44.2%of Ni)as confirmed by its high conductivity(1.124×10??mat39800Hz)and ambient temperature magnetic susceptibility(8.40×10emu/Oe?mol).This work has a guiding significance for the synthesis of high rate performance of lithium battery cathode materials.展开更多
The total conductivity of Li-biphenyl-1,2-dimethoxyethane solution(Li_xBp(DME)_(9.65), Bp = biphenyl, DME = 1,2-dimethoxyethane, x = 0.25, 0.50, 1.00, 1.50, 2.00) is measured by impedance spectroscopy at a tempe...The total conductivity of Li-biphenyl-1,2-dimethoxyethane solution(Li_xBp(DME)_(9.65), Bp = biphenyl, DME = 1,2-dimethoxyethane, x = 0.25, 0.50, 1.00, 1.50, 2.00) is measured by impedance spectroscopy at a temperature range from 0℃ to 40℃. The Li_(1.50)Bp(DME)_(9.65) has the highest total conductivity 10.7 m S/cm. The conductivity obeys Arrhenius law with the activation energy(E_(a(x=0.50))= 0.014 eV, E_(a(x=1.00))= 0.046 eV). The ionic conductivity and electronic conductivity of Li_xBp(DME)_(9.65) solutions are investigated at 20℃ using the isothermal transient ionic current(ITIC) technique with an ion-blocking stainless steal electrode. The ionic conductivity and electronic conductivity of Li_(1.00)Bp(DME)_(9.65) are measured as 4.5 mS/cm and 6.6 mS/cm, respectively. The Li_(1.00)Bp(DME)_(9.65) solution is tested as an anode material of half liquid lithium ion battery due to the coexistence of electronic conductivity and ionic conductivity. The lithium iron phosphate(LFP) and Li_(1.5)Al_(0.5)Ti_(1.5)(PO_4)_3(LATP) are chosen to be the counter electrode and electrolyte, respectively. The assembled cell is cycled in the voltage range of 2.2 V-3.75 V at a current density of 50 mA/g. The potential of Li_(1.00)Bp(DME)_(9.65) solution is about 0.3 V vs. Li~+/Li, which indicates the solution has a strong reducibility. The Li_(1.00)Bp(DME)_(9.65) solution is also used to prelithiate the anode material with low first efficiency, such as hard carbon, soft carbon and silicon.展开更多
Oxygen and nitrogen adsorption in single walled carbon nanotube (SWCNT) is studied by density function and discrete variational (DFT-DVM) method.The models of O 2 and N 2 adsorption in the SWCNT are optimized based...Oxygen and nitrogen adsorption in single walled carbon nanotube (SWCNT) is studied by density function and discrete variational (DFT-DVM) method.The models of O 2 and N 2 adsorption in the SWCNT are optimized based on the energy minimization.The calculated results of density of state,populations and energy gaps of the molecular orbitals show that oxygen adsorption in SWCNT increases the carbon nanotube`s electrical conductivity more notably than nitrogen adsorption,which is consistent with the experiment.展开更多
The change of conductivity, thickness and scanning electron microscopy (SEM) appearance of the anode film of CrWMn in 10% NaNO3 at different anode potential either with or without the magnetic field applied are inve...The change of conductivity, thickness and scanning electron microscopy (SEM) appearance of the anode film of CrWMn in 10% NaNO3 at different anode potential either with or without the magnetic field applied are investigated by testing film resistance, galvanostatic transient and using SEM to design magnetic circuit in magnetic assisted electrochemical machining (MAECM). The experiments show that the anode film has semi-conducting property. Compared with the situation without magnetic field applied, the resistance of the film formed at 1 .SV (anode potential) increased and decreased at 4.0V while B=0.4T and the magnetic north pole points toward anode. The SEM photo demonstrates that the magnetic field will densify the film in the passivation area and quicken dissolution of the anode metal in over-passivation area. Based on the influence of magnetic field on electrochemical machining(ECM) due to the changes of the anode film conductivity behavior, the magnetic north pole should be designed to point towards the workpiece surface that has been machined. Process experiments agree with the results of test analysis.展开更多
ESR studies have been undertaken for various chemical composition of electron beam evapo- rated a-Si_(1-x)Gd_x films with 0<x≤10at%.The experimental results show that the g value changes with (2.0043±0.0001)...ESR studies have been undertaken for various chemical composition of electron beam evapo- rated a-Si_(1-x)Gd_x films with 0<x≤10at%.The experimental results show that the g value changes with (2.0043±0.0001)≤g≤(2.0054±0.0001),the line shape factor l changes with(2.77±0.01)≤l≤(3.10± 0.01)and the linewidth △B_(pp)changes with 6.40×10^(-4)≤△B_(pp)≤7.00×10^(-4)T.The experimental results were analysed with Barnes S.E.dynamic theory of ESR spectrum based on the characteristics of the ESR parameters.It was shown that the changes of ESR parameters depend on the compensation of Gd atoms for the dangling bonds in a-Si film,and the exchange interaction between the conduction electrons and the spins in the host materials.展开更多
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supported by the National Natural Science Foundation of China(No.T2241003)the National Key Research and Development Program of China(No.2022YFB4003500)the Key R&D project of Hubei Province,China(No.2021AAA006).
文摘The point-to-point contact mechanism in all-solid-state Li-S batteries(ASSLSBs)is not as efficient as a liquid electrolyte which has superior mobility in the electrode,resulting in a slower reaction kinetics and inadequate ionic/electronic conduction network between the S(or Li_(2)S),conductive carbon,and solid-state electrolytes(SSEs)for achieving a swift(dis)charge reaction.Herein,a series of hybrid ionic/electronic conduction triple-phase interfaces with transition metal and nitrogen co-doping were designed.The graphitic ordered mesoporous carbon frameworks(TM-N-OMCs;TM=Fe,Co,Ni,and Cu)serve as hosts for Li_(2)S and Li_(6)PS_(5)Cl(LPSC)and provide abundant reaction sites on the triple interface.Results from both experimental and computational research display that the combination of Cu-N co-dopants can promote the Li-ion diffusion for rapid transformation of Li_(2)S with adequate ionic(6.73×10^(−4)S·cm^(−1))/electronic conductivities(1.77×10^(−2)S·cm^(−1))at 25℃.The as-acquired Li_(2)S/Cu-N-OMC/LPSC electrode exhibits a high reversible capacity(1147.7 mAh·g^(−1))at 0.1 C,excellent capacity retention(99.5%)after 500 cycles at 0.5 C,and high areal capacity(7.08 mAh·cm^(−2)).
基金the National Natural Science Foundation of China(51973157)the Special Grade of the Financial Support from the China Postdoctoral Science Foundation(2020T130469)+1 种基金the China Postdoctoral Science Foundation Grant(2019 M651047)the Science and Technology Plans of Tianjin(19PTSYJC00010)for their financial support。
文摘Lithium-sulfur(Li-S) batteries and lithium-selenium(Li-Se) batteries,as environmental protection energy storage systems with outstanding theoretical specific capacities and high energy densities,have become the hotspots of current researches.Besides,elemental S(Se) raw materials are widely sourced and their production costs are both low,which make them considered one of the new generations of high energy density electrochemical energy storage systems with the most potential for development.However,poor conductivity of elemental S/Se and the notorious "shuttle effect" of lithium polysulfides(polyselenides) severely hinder the commercialization of Li-S/Se batteries.Thanks to the excellent electrical conductivity and strong absorption of lithium polysulfide(polyselenide) about electronically conducting polymer,some of the above thorny problems have been effectively alleviated.The review presents the fundamental studies and current development trends of common electronically conducting polymers in various components of Li-S/Se batteries,which involves polyaniline(PANI) polypyrrole(PPy),and polythiophene(PTh) with its derivatives,e.g.polyethoxythiophene(PEDOT) and poly(3,4-ethylene dioxythiophene)-poly(styrenesulfonate)(PEDOT:PSS).Finally,the review not only summarizes the research directions and challenges facing the application of electronically conducting polymers,but also looks forward to the development prospects of them,which will provide a way for the practical use of electronically conducting polymers in Li-S/Se batteries with outstanding electrochemical properties in the short run.
基金Project Sponsored by National Natural Science Foundation(59874004)
文摘A study on electronic conductivity of CaO-SiO2-Al2O3-FeOxslag system with Wagner polarization technique was carried out.The experimental data show that electronic conductivity is consisted of free electron conductivity and electron hole conductivity and both are related to the content of Fe3+and Fe2+.Free electron conductivity is decreasing and electron hole conductivity is increasing while Fe3+changes to Fe2+.There is a maximum electronic conductivity at some ratio of ferric ions Fe3+to total ion content.Under the experimental conditions,the electronic conductivity is in the range of 10-4—10-2S/cm.
文摘The ZrO2 (9mol% Y2O3) coating was prepared evenly on the surface of MgO partially stabilized zirconia (Mg-PSZ) tube (oxygen sensor probe) by dipping the green Mg-PSZ tube in a ZrO2 (9mol% Y2O3) slurry and then co-firing at 1750°C for 8 h. The double-cell method was employed to measure the electronic conductivity parameter and exam the reproducibility of the coated Mg- PSZ tube. The experimental results indicate that the good thermal shock resistance of the Mg-PSZ tube can be retained when the coating thickness is not more than 3.4 μm. The ZrO2 (9mol% Y2O3) coating reduces the electronic conductivity parameter remarka- bly, probably due to the lower electronic conductivity of Y2O,-stabilized ZrO2 than that of MgO-stabilized ZrO2. Moreover, the ZrO2 (9mol% Y2O3) coating can improve the reproducibility and accuracy of the Mg-PSZ tube significantly in the low oxygen measure- ment. The smooth surface feature and lower electronic conductivity of the coated Mg-PSZ tube should be responsible for this im- provement.
文摘We investigated the electronic heat capacity, thermal conductivity, and resistivity of UN using Quantum Espresso and EPW code. GGA, PBEsol functional was used. The calculated electronic heat coefficient was found to be significantly reduced (0.0176 J<span style="white-space:nowrap;"><span style="white-space:nowrap;">⋅</span></span>mol<sup><span style="white-space:nowrap;">-</span>1</sup><span style="white-space:nowrap;"><span style="white-space:nowrap;">⋅</span></span>K<sup><span style="white-space:nowrap;">-</span>2</sup> versus 0.0006 J<span style="white-space:nowrap;"><span style="white-space:nowrap;">⋅</span></span>mol<sup><span style="white-space:nowrap;">-</span>1</sup><span style="white-space:nowrap;"><span style="white-space:nowrap;">⋅</span></span>K<sup><span style="white-space:nowrap;">-</span>2</sup>) when the non-local hybrid functional (B3LYP) was used. Furthermore, we calculated electrical resistivity using a very transparent Ziman’s formula for metals with the Eliashberg transport coupling function as implemented in EPW code for non-spin-polarized calculations. The number of mobile electrons in UN, as a function of temperature, was derived from the ratio of the calculated resistivity and available experimental data. The electronic thermal conductivity was evaluated from the calculated electronic resistivity via Wiedemann-Franz law with the number of mobility electrons (<em>n<sub>av</sub></em>) incorporated (averaged over the temperature range 300 K - 1000 K). Both the electronic thermal conductivity and resistivity, as calculated using newly evaluated <em>n<sub>av</sub></em>, compare well with experimental data at ~700 K, but to reproduce the observed trend as a function of temperature, the number of mobile electrons must decrease with the temperature as evaluated.
基金financial support from the National Natural Science Foundation of China(No.51673199,51972301)the Youth Innovation Promotion Association of CAS(2015148)+2 种基金the Youth Innovation Foundation of DICP(ZZBS201615,ZZBS201708)the Dalian Outstanding Young Scientific Talent(2018RJ03)the National Key Research and Development Project(2019YFA0705600)。
文摘Silica-based anode is widely employed for high energy density Li-ion batteries owing to their high theoretical specific capacity(4200 m A h g-1).However,it is always accompanied by a huge volume expansion(300%)and shrinks during the lithiation/delithiation process,further leading to low cycle stability.Efforts to mitigate the adverse effects caused by volume expansion such as robust binder matrix,Coreshell structure,etc.,inevitably affect the electronic conductivity within the electrode.Herein,a high conductivity and elasticity Si anode(Ni-P-SBR(styrene-butadiene rubber)@Si)was designed and fabricated via the Ni-P-SBR composite-electroless-plating process.In this design,the Si particles are surrounded by SBR polymer and Ni particles,where the SBR can adapt to the volume change and Ni particles can provide the electrode with high electronic conductivity.Therefore,the Ni-P-SBR@Si delivers a high initial capacity of 3470 m A h g-1and presents capacity retention of 49.4%within 200 cycles at 600 m A g-1.Additionally,a high capacity of 1153 m A h g-1can be achieved at 2000 m A g-1and can be cycled stably under bending conditions.This strategy provides feasible ideas to solve the key issues that limit the practical application of Si anodes.
基金Project supported by the National Key Research and Development Program of China(Grant No.2019YFE0100200)the National Natural Science Foundation of China(Grant No.U1964205)the Beijing Municipal Science and Technology Commission(Grant No.Z191100004719001)。
文摘The structural transformations,oxygen releasing and side reactions with electrolytes on the surface are considered as the main causes of the performance degradation of Li-rich layered oxides(LROs)cathodes in Li-ion batteries.Thus,stabilizing the surfaces of LROs is the key to realize their practical application in high energy density Li-ion batteries.Surface coating is regarded as one of the most effective strategies for high voltage cathodes.The ideal coating materials should prevent cathodes from electrolyte corrosion and possess both electronic and Li-ionic conductivities simultaneously.However,commonly reported coating materials are unable to balance these functions well.Herein,a new type of coating material,La_(2)CuO_(4)was introduced to mitigate the surface issues of LROs for the first time,due to its superb electronic conductivity(26-35 mS·cm^(-1))and lithium-ionic diffusion coefficient(10^(-12)-10^(-13)cm^(2)·s^(-1)).After coating with the La_(2)CuO_(4),the capacity retention of Li_(1.2)Ni_(0.54)Co_(0.13)Mn_(0.13)O_(2)cathode was increased to 85.9%(compared to 79.3%of uncoated cathode)after 150 cycles in the voltage range of 2.0-4.8 V.In addition,only negligible degradations on the deliverable capacity and rate capability were observed.
基金This study was financially supported by the National Natural Science Foundation of China(Nos.52177208,52171202,51971055 and 51871046)the National Safety Academic Fund(Nos.U1930208,U2030206 and U1730136).
文摘The high energy density and stability of solid-state lithium metal batteries(SSLMBs)have garnered great attention.Garnet-type oxides,especially Li_(6.4)La_(3)Zr_(1.4)Ta_(0.6)O_(12)(LLZTO),with high ionic conductivity,wide electrochemical window,and stability to Li metal anode,are promising solid-state electrolyte(SSEs)materials for SSLMBs.However,Li/LLZTO interface issues including high interface resistance,inhomogeneous Li deposition,and Li dendrite growth have hindered the practical application of SSLMBs.Herein,a multi-functional Li–SnF_(2) composite anode with Li,LiF,and Li-Sn alloy was specifically designed and prepared.The composite anode improves the wettability to LLZTO,constructing an intimate contact interface between it and LLZTO.Meanwhile,ionic/electronic conductive paths in situ formed at the interface can effectively uniform Li deposition and suppress Li dendrite.The solid-state symmetric cell exhibits low interface resistance(11Ω·cm^(2)) and high critical current density(1.3 mA·cm^(−2))at 25℃.The full SSLMB based on LiFePO_(4) or LiNi_(0.5)Co_(0.2)Mn_(0.3)O_(2) cathode also shows stable cycling performance and high rate capability.This work provides a new composite anode strategy for achieving high-energy density and high-safety SSLMBs.
基金supported by the National Key R&D Program of China (Grant no. 2016YFB0100105)the National Natural Science Foundation of China (Grant no. 51872303)+1 种基金Zhejiang Provincial Natural Science Foundation of China (Grant no. LD18E020004, LQ16E020003, LY18E020018, LY18E030011)Youth Innovation Promotion Association CAS (2017342)
文摘The main challenges in development of traditional liquid lithium-sulfur batteries are the shuttle effect at the cathode caused by the polysulfide and the safety concern at the Li metal anode arose from the dendrite formation.All-solid-state lithium-sulfur batteries have been proposed to solve the shuttle effect and prevent short circuits.However,solid-solid contacts between the electrodes and the electrolyte increase the interface resistance and stress/strain,which could result in the limited electrochemical performances.In this work,the cathode of all-solid-state lithium-sulfur batteries is prepared by depositing sulfur on the surface of the carbon nanotubes(CNTs@S)and further mixing with Li10GeP2S12 electrolyte and acetylene black agents.At 60℃,CNTs@S electrode exhibits superior electrochemical performance,delivering the reversible discharge capacities of 1193.3,959.5,813.1,569.6 and 395.5 mAhg^-1 at the rate of 0.1,0.5,1,2 and 5 C,respectively.Moreover,the CNTs@S is able to demonstrate superior high-rate capability of 660.3 mAhg^-1 and cycling stability of 400 cycles at a high rate of 1.0 C.Such uniform distribution of the CNTs,S and Li10GeP2S12 electrolyte increase the electronic and ionic conductivity between the cathode and the electrolyte hence improves the rate performance and capacity retention.
文摘The electrochemical nature of reaction between melt and slag in a closed system was worked out. Experimental results demonstrated that both the rate and reaction extent increase when the electronic conductor or voltage was applied between melt and slag. The bigger the contact area of the conductor with melts is, the faster the reaction rate is. With the increase of applied voltage which is beneficial for electron's migration between metal and slags, the rate and extent of reaction increase.
基金the National Natural Science Foundation of China (10674034)
文摘Ce0.85Sm0.15O1.925 (SDC) and La0.9Sr0.1Ga0.5Mg0.2O2.85 (LSGM) were synthesized using Glycine-Nitrate Process (GNP), and the composite electrolytes were prepared by mixing SDC and LSGM. An X-ray diffraction pattern indicated that the mixture of SDC and LSGM consisted of their original phases after heating at 1450 ℃ for 10 h. The electronic conductivity of SDC-LSGM composite electrolytes were measured by direct current polarization method using Hebb-Wagner ion blocking cell at 700-800 ℃ in the oxygen partial pressure range of 104-10-20 MPa and compared with the results of SDC. Typical polarization curves, which were theoretically predicted, were observed on all the samples. The slopes of lgσe-lgPo2 plot for all the composite electrolytes agreed with the theoretically predicted value of-1/4 at some intermediate oxygen partial pressures and -1/6 at low oxygen partial pressure. The electronic conductivity of SDC-LSGM composite electrolytes decreased with the increase in LSGM content, whereas the ionic transport number ti of all the samples increased with the increase in LSGM content.
基金The authors are grateful to Dr. Shane Roark (Eltron Research Inc.) and Mr. Jinwang Yan for beneficial discussion and suggestions. We would also like to acknowledge financial support from the Ministry of Science and Technology China (Grant No. G19990
文摘The electrical conduction properties of dense BaCe0.9Mn0.1O3-d (BCM10) membrane were investigated in the temperature range of 600-900oC. High ionic and electronic conductivities at elevated temperatures make BCM10 a potential ceramic material for hydrogen separation. Hydrogen permeation through BCM10 membranes was studied using a high- temperature permeation cell. Little hydrogen could be detected at the sweep side. However, appreciable hydrogen can permeate through BCM10 membrane coated with porous platinum black, which shows that the process of hydrogen permeation through BCM10 membranes was controlled by the catalytic decomposition and recomposition of hydrogen on the surfaces of BCM10 membranes.
基金National Natural Science Foundation of China,Grant/Award Numbers:51972121,51972270,51702262Tip-top Scientific and Technical Innovative Youth Talents of Guangdong Special Support Program,Grant/Award Number:2017TQ04C419Key Research and Development Program of Shaanxi Province,Grant/Award Number:2019TSLGY07-03。
文摘The limited lithium resource in earth's crust has stimulated the pursuit of alternative energy storage technologies to lithium-ion battery.Potassium-ion batteries(KIBs)are regarded as a kind of promising candidate for large-scale energy storage owing to the high abundance and low cost of potassium resources.Nevertheless,further development and wide application of KIBs are still challenged by several obstacles,one of which is their fast capacity deterioration at high rates.A considerable amount of effort has recently been devoted to address this problem by developing advanced carbonaceous anode materials with diverse structures and morphologies.This review presents and highlights how the architecture engineering of carbonaceous anode materials gives rise to high-rate performances for KIBs,and also the beneficial conceptions are consciously extracted from the recent progress.Particularly,basic insights into the recent engineering strategies,structural innovation,and the related advances of carbonaceous anodes for high-rate KIBs are under specific concerns.Based on the achievements attained so far,a perspective on the foregoing,and proposed possible directions,and avenues for designing high-rate anodes,are presented finally.
文摘By altering the electrochemical properties of slag, the decarburization reaction of Fe3+-based slag withFe-C droplet was studied. The results showed that a lot of free electrons and holes exist in the slag containing transition metal oxides (such as TiO2 and Fe2O3). So electronic conduction in the slag increases. Finally, it led to the increment of the decarburization reaction rate between slag and Fe-C droplet, and mass fraction of carbon remaining indroplet decreases to a lower level.
基金financially supported by NSFC(No.21571176,21611530688,21771171,21671077 and 21025104)
文摘Constructing layered-spinel composites is important to improve the rate performance of lithium-rich layered oxides.However,up to now,the effect of microstructure of composites on the rate performance has not been well investigated.In this study,a series of samples were prepared by a simple protonation and de-protonation for the pristine layered material(LiMnNiCoO)obtained by sol-gel method.The characterizations of XRD,Raman and oxidation-reduction potentials of charge-discharge curves demonstrated that these samples after de-protonation are layered-spinel composites.When these composites were tested as a cathode of lithium-ion batteries,the sample treated with 0.1 M of nitric acid exhibited higher discharge capacities at each current density than that of other composites.The outstanding rate performance is attributed to the high concentration of conduction electron resulting from the low average valence state(44.2%of Ni)as confirmed by its high conductivity(1.124×10??mat39800Hz)and ambient temperature magnetic susceptibility(8.40×10emu/Oe?mol).This work has a guiding significance for the synthesis of high rate performance of lithium battery cathode materials.
基金Project supported by the National Natural Science Foundation of China(Grant No.52315206)the Ministry of Science and Technology of China(Grant No.2016YFB0100100)the Beijing Municipal Science and Technology Commission,China(Grant No.D151100003115003)
文摘The total conductivity of Li-biphenyl-1,2-dimethoxyethane solution(Li_xBp(DME)_(9.65), Bp = biphenyl, DME = 1,2-dimethoxyethane, x = 0.25, 0.50, 1.00, 1.50, 2.00) is measured by impedance spectroscopy at a temperature range from 0℃ to 40℃. The Li_(1.50)Bp(DME)_(9.65) has the highest total conductivity 10.7 m S/cm. The conductivity obeys Arrhenius law with the activation energy(E_(a(x=0.50))= 0.014 eV, E_(a(x=1.00))= 0.046 eV). The ionic conductivity and electronic conductivity of Li_xBp(DME)_(9.65) solutions are investigated at 20℃ using the isothermal transient ionic current(ITIC) technique with an ion-blocking stainless steal electrode. The ionic conductivity and electronic conductivity of Li_(1.00)Bp(DME)_(9.65) are measured as 4.5 mS/cm and 6.6 mS/cm, respectively. The Li_(1.00)Bp(DME)_(9.65) solution is tested as an anode material of half liquid lithium ion battery due to the coexistence of electronic conductivity and ionic conductivity. The lithium iron phosphate(LFP) and Li_(1.5)Al_(0.5)Ti_(1.5)(PO_4)_3(LATP) are chosen to be the counter electrode and electrolyte, respectively. The assembled cell is cycled in the voltage range of 2.2 V-3.75 V at a current density of 50 mA/g. The potential of Li_(1.00)Bp(DME)_(9.65) solution is about 0.3 V vs. Li~+/Li, which indicates the solution has a strong reducibility. The Li_(1.00)Bp(DME)_(9.65) solution is also used to prelithiate the anode material with low first efficiency, such as hard carbon, soft carbon and silicon.
文摘Oxygen and nitrogen adsorption in single walled carbon nanotube (SWCNT) is studied by density function and discrete variational (DFT-DVM) method.The models of O 2 and N 2 adsorption in the SWCNT are optimized based on the energy minimization.The calculated results of density of state,populations and energy gaps of the molecular orbitals show that oxygen adsorption in SWCNT increases the carbon nanotube`s electrical conductivity more notably than nitrogen adsorption,which is consistent with the experiment.
基金National Defense Foundation of China (No.51318030401).
文摘The change of conductivity, thickness and scanning electron microscopy (SEM) appearance of the anode film of CrWMn in 10% NaNO3 at different anode potential either with or without the magnetic field applied are investigated by testing film resistance, galvanostatic transient and using SEM to design magnetic circuit in magnetic assisted electrochemical machining (MAECM). The experiments show that the anode film has semi-conducting property. Compared with the situation without magnetic field applied, the resistance of the film formed at 1 .SV (anode potential) increased and decreased at 4.0V while B=0.4T and the magnetic north pole points toward anode. The SEM photo demonstrates that the magnetic field will densify the film in the passivation area and quicken dissolution of the anode metal in over-passivation area. Based on the influence of magnetic field on electrochemical machining(ECM) due to the changes of the anode film conductivity behavior, the magnetic north pole should be designed to point towards the workpiece surface that has been machined. Process experiments agree with the results of test analysis.
文摘ESR studies have been undertaken for various chemical composition of electron beam evapo- rated a-Si_(1-x)Gd_x films with 0<x≤10at%.The experimental results show that the g value changes with (2.0043±0.0001)≤g≤(2.0054±0.0001),the line shape factor l changes with(2.77±0.01)≤l≤(3.10± 0.01)and the linewidth △B_(pp)changes with 6.40×10^(-4)≤△B_(pp)≤7.00×10^(-4)T.The experimental results were analysed with Barnes S.E.dynamic theory of ESR spectrum based on the characteristics of the ESR parameters.It was shown that the changes of ESR parameters depend on the compensation of Gd atoms for the dangling bonds in a-Si film,and the exchange interaction between the conduction electrons and the spins in the host materials.