CO_(2)hydrogenation is an attractive way to store and utilize carbon dioxide generated by industrial processes,as well as to produce valuable chemicals from renewable and abundant resources.Iron catalysts are commonly...CO_(2)hydrogenation is an attractive way to store and utilize carbon dioxide generated by industrial processes,as well as to produce valuable chemicals from renewable and abundant resources.Iron catalysts are commonly used for the hydrogenation of carbon oxides to hydrocarbons.Iron-molybdenum catalysts have found numerous applications in catalysis,but have been never evaluated in the CO_(2)hydrogenation.In this work,the structural properties of iron-molybdenum catalysts without and with a promoting alkali metal(Li,Na,K,Rb,or Cs)were characterized using X-ray diffraction,hydrogen temperatureprogrammed reduction,CO_(2)temperature-programmed desorption,in-situ^(57)Fe Mossbauer spectroscopy and operando X-ray adsorption spectroscopy.Their catalytic performance was evaluated in the CO_(2)hydrogenation.During the reaction conditions,the catalysts undergo the formation of an iron(Ⅱ)molybdate structure,accompanied by a partial reduction of molybdenum and carbidization of iron.The rate of CO_(2)conversion and product selectivity strongly depend on the promoting alkali metals,and electronegativity was identified as an important factor affecting the catalytic performance.Higher CO_(2)conversion rates were observed with the promoters having higher electronegativity,while low electronegativity of alkali metals favors higher light olefin selectivity.展开更多
Alkali metals(Li,Na,and K)are promising candidates for high-performance rechargeable alkali metal battery anodes due to their high theoretical specific capacity and low electrochemical potential.However,the actual app...Alkali metals(Li,Na,and K)are promising candidates for high-performance rechargeable alkali metal battery anodes due to their high theoretical specific capacity and low electrochemical potential.However,the actual application of alkali metal anodes is impeded by the challenges of alkali metals,including their high chemical reactivity,uncontrolled dendrite growth,unstable solid electrolyte interphase,and infinite volume expansion during cycling processes.Introducing carbon nanotube-based nanomaterials in alkali metal anodesis an effective solution to these issues.These nanomaterials have attracted widespread attention owing to their unique properties,such as their high specific surface area,superior electronic conductivity,and excellent mechanical stability.Considering the rapidly growing research enthusiasm for this topic in the last several years,we review recent progress on the application of carbon nanotube-based nanomaterials in stable and dendrite-free alkali metal anodes.The merits and issues of alkali metal anodes,as well as their stabilizing strategies are summarized.Furthermore,the relationships among methods of synthesis,nano-or microstructures,and electrochemical properties of carbon nanotube-based alkali metal anodes are systematically discussed.In addition,advanced characterization technologies on the reaction mechanism of carbon nanotube-based nanomaterials in alkali metal anodes are also reviewed.Finally,the challenges and prospects for future study and applications of carbon nanotube-based AMAs in high-performance alkali metal batteries are discussed.展开更多
The ever-growing pursuit of high energy density batteries has triggered extensive efforts toward developing alkali metal(Li,Na,and K)battery(AMB)technologies owing to high theoretical capacities and low redox potentia...The ever-growing pursuit of high energy density batteries has triggered extensive efforts toward developing alkali metal(Li,Na,and K)battery(AMB)technologies owing to high theoretical capacities and low redox potentials of metallic anodes.Typically,for new battery systems,the electrolyte design is critical for realizing the battery electrochemistry of AMBs.Conventional electrolytes in alkali ion batteries are generally unsuitable for sustaining the stability owing to the hyper-reactivity and dendritic growth of alkali metals.In this review,we begin with the fundamentals of AMB electrolytes.Recent advancements in concentrated and fluorinated electrolytes,as well as functional electrolyte additives for boosting the stability of Li metal batteries,are summarized and discussed with a special focus on structure-composition-performance relationships.We then delve into the electrolyte formulations for Na-and K metal batteries,including those in which Na/K do not adhere to the Li-inherited paradigms.Finally,the challenges and the future research needs in advanced electrolytes for AMB are highlighted.This comprehensive review sheds light on the principles for the rational design of promising electrolytes and offers new inspirations for developing stable AMBs with high performance.展开更多
Alkali metal-carbon dioxide(Li/Na/K-CO_(2))batteries are emerging electrochemical energy storage technologies in the context of the energy crisis and the urgent demand for carbon neutrality.Alkali metal-CO_(2) batteri...Alkali metal-carbon dioxide(Li/Na/K-CO_(2))batteries are emerging electrochemical energy storage technologies in the context of the energy crisis and the urgent demand for carbon neutrality.Alkali metal-CO_(2) batteries offer a new strategy for CO_(2) fixation and utilization,and thus has been receiving considerable attention in recent years.Considerable progress has been achieved since alkali metal-CO_(2) batteries were invented,especially in terms of development of new electrode materials,and yet,research is lacking on the underlying mechanisms of the systems.This is the first typical review focusing on the electrochemical mechanisms of metal-CO_(2) batteries that summarizes the current understanding of and provides insights into the thermodynamic reaction pathways,the kinetic characteristics,and the crucial factors determining the reaction mechanisms in alkali metal-CO_(2) batteries.The review starts with the fundamental concepts of alkali metal-CO_(2) batteries,followed by a comprehensive discussion of the working mechanisms on cathodes and anodes.Moreover,the operation mechanisms of state-of-the-art electrolytes,including liquid and(quasi-)solid-state electrolytes,are also described.Finally,we identify the unsolved problems in current alkali metal-CO_(2) batteries and propose potential topics for future research.展开更多
Alkali metal hydroxide and hydride composite systems contain both protic (H bonded with O) and hydridic hydrogen. The interaction of these two types of hydrides produces hydrogen. The enthalpy of dehydrogenation inc...Alkali metal hydroxide and hydride composite systems contain both protic (H bonded with O) and hydridic hydrogen. The interaction of these two types of hydrides produces hydrogen. The enthalpy of dehydrogenation increased with the increase of atomic number of alkali metals, i.e., -23 kJ/molnz for LiOH-LiH, 55.34 kJ/moln: for NaOH-NaH and 222 kJ/molH2 for KOH-KH. These thermodynamic calculation results were consistent with our experimental results. H2 was released from LiOH-LiH system during ball milling. The dehydrogenation temperature of NaOH-NaH system was about 150 ℃; whereas KOH and KH did not interact with each other during the heating process. Instead, KH decomposed by itself. In these three systems, NaOH-NaH was the only reversible hydrogen storage system, the enthalpy of dehydrogenation was about 55.65 kJ/molHz, and the corresponding entropy was ca. 101.23 J/(molHz .K), so the temperature for releasing 1.0 bar H2 was as high as 518 ℃, showing unfavorable thermodynamic properties. The activation energy for hydrogen desorption of NaOH-NaH was found to be 57.87 kJ/mol, showing good kinetic properties.展开更多
Rechargeable alkali metal-air batteries are considered as the most promising candidate for the power source of electric vehicles(EVs) due to their high energy density. However, the practical application of metal-air b...Rechargeable alkali metal-air batteries are considered as the most promising candidate for the power source of electric vehicles(EVs) due to their high energy density. However, the practical application of metal-air batteries is still challenging. In the past decade, many strategies have been purposed and explored, which promoted the development of metal-air batteries. The reaction mechanisms have been gradually clarified and catalysts have been rationally designed for air cathodes. In this review, we summarize the recent development of alkali metal-air batteries from four parts: metal anodes, electrolytes, air cathodes and reactant gases, wherein we highlight the important achievement in this filed. Finally problems and prospective are discussed towards the future development of alkali metal-air batteries.展开更多
Metal-organic frameworks (MOFs) have attracted much attention as adsorbents for the separation of CO2 from flue gas or natural gas. Here, a typical metal-organic framework HKUST-I(also named Cu-BTC or MOF-199) was...Metal-organic frameworks (MOFs) have attracted much attention as adsorbents for the separation of CO2 from flue gas or natural gas. Here, a typical metal-organic framework HKUST-I(also named Cu-BTC or MOF-199) was chemically reduced by doping it with alkali metals (Li, Na and K) and they were further used to investigate their CO2 adsorption capacities. The structural information, surface chemistry and thermal behavior of the prepared adsorbent samples were characterized by X-ray powder diffraction (XRD), thermo-gravimetric analysis (TGA) and nitrogen adsorption-desorption isotherm analysis. The results showed that the CO2 storage capacity of HKUST-1 doped with moderate quantities of Li+, Na+ and K+, individually, was greater than that of unmodified HKUST-1. The highest CO2 adsorption uptake of 8.64 mmol/g was obtained with 1K-HKUST-1, and it was ca. 11% increase in adsorption capacity at 298 K and 18 bar as compared with HKUST- 1. Moreover, adsorption tests showed that HKUST-1 and 1K-HKUST-1 displayed much higher adsorption capacities of CO2 than those of N2. Finally, the adsorption/desorption cycle experiment revealed that the adsorption performance of 1K-HKUST-1 was fairly stable, without obvious deterioration in the adsorption capacity of CO2 after 10 cycles.展开更多
Surface properties (viz. surface area, basicity/base strength distribution, and crystal phases) of alkali metal doped CaO (alkali metal/Ca= 0.1 and 0.4) catalysts and their catalytic activity/selectivity in oxidat...Surface properties (viz. surface area, basicity/base strength distribution, and crystal phases) of alkali metal doped CaO (alkali metal/Ca= 0.1 and 0.4) catalysts and their catalytic activity/selectivity in oxidative coupling of methane (OCM) to higher hydrocarbons at different reaction conditions (viz. temperature, 700 and 750 ℃; CH4/O2 ratio, 4.0 and 8.0 and space velocity, 5140-20550 cm^3 ·g^-1·h^-1) have been investigated. The influence of catalyst calcination temperature on the activity/selectivity has also been investigated. The surface properties (viz. surface area, basicity/base strength distribution) and catalytic activity/selectivity of the alkali metal doped CaO catalysts are strongly influenced by the alkali metal promoter and its concentration in the alkali metal doped CaO catalysts. An addition of alkali metal promoter to CaO results in a large decrease in the surface area but a large increase in the surface basicity (strong basic sites) and the C2+ selectivity and yield of the catalysts in the OCM process. The activity and selectivity are strongly influenced by the catalyst calcination temperature. No direct relationship between surface basicity and catalytic activity/selectivity has been observed. Among the alkali metal doped CaO catalysts, Na-CaO (Na/Ca = 0.1, before calcination) catalyst (calcined at 750 ℃), showed best performance (C2+ selectivity of 68.8% with 24.7% methane conversion), whereas the poorest performance was shown by the Rb-CaO catalyst in the OCM process.展开更多
EAB zeolite was successfully prepared and applied to selective adsorption of Li^(+),Na^(+)and K^(+)ions.The physical and chemical properties of the adsorbent were characterized by X-ray diffraction(XRD),X-ray fluoresc...EAB zeolite was successfully prepared and applied to selective adsorption of Li^(+),Na^(+)and K^(+)ions.The physical and chemical properties of the adsorbent were characterized by X-ray diffraction(XRD),X-ray fluorescence(XRF),scanning electron microscope(SEM)and thermogravimetry(TG)methods.The ion exchange behaviours for Li^(+),Na^(+)and K^(+)ions in monomcomponent and multicomponent solutions were studied.In independent ion exchange,the ion exchange capacities ratiosα(/Na/Li)andα(K/Li)were 3.8 and 6.2,respectively.In competitive ion exchange,the selectivitiesβ(Na/Li)andβ(K/Li)increased with the initial concentrations and reached 409 and 992 when the initial concentrations was 100 mmol/L.The thermodynamic study results showed that Gibbs free energy change(ΔGΘ)of ion exchange reaction between Li-EAB and K^(+)was-34.96 kJ/mol,indicating that ion exchange of K^(+)ions was more energetically favourable than Li^(+)ions.The calculation results showed that the energy barriers of ion exchange increased in the order K^(+)Na^(+)<Li^(+).The study shows that EAB zeolite is potential to be used in the separation of alkali ions.展开更多
The electronic structures and field emission properties of capped CNT55 systems with or without alkali metal atom adsorption were systematically investigated by density functional theory calculation.The results indica...The electronic structures and field emission properties of capped CNT55 systems with or without alkali metal atom adsorption were systematically investigated by density functional theory calculation.The results indicate that the adsorption of alkali metal on the center site of a CNT tip is energetically favorable.In addition,the adsorption energies increase with the introduction of the electric field.The excessive negative charges on CNT tips make electron emittance much easier and result in a decrease in work function.Furthermore,the inducing effect by positively charged alkali metal atoms can be reasonably considered as the dominant reason for the improvement in field emission properties.展开更多
A series of mesoporous smectite like materials incorporated with alkali metals such as Li, Na, K and Cs has been synthesized with the hydrothermal method. The crystalline and the pore structures of the materials synt...A series of mesoporous smectite like materials incorporated with alkali metals such as Li, Na, K and Cs has been synthesized with the hydrothermal method. The crystalline and the pore structures of the materials synthesized significantly change with the introduction of alkali metals. The addition of Li gives highly ordered layer phases, while the incorporation of Cs yields much less crystalline structures. Although Na or K has little effect on the crystalline structure, they modify the pore structure.展开更多
A semi-empirical atomic structure model method is developed in the framework of a relativistic case. This method starts from Dirac-Fock calculations using B-spline basis set. The core-valence electron correction is th...A semi-empirical atomic structure model method is developed in the framework of a relativistic case. This method starts from Dirac-Fock calculations using B-spline basis set. The core-valence electron correction is then treated in a semiempirical core polarization potential. As an application, the polarization properties of alkali metal atoms, including the static polarizabilities and long-range two-body dispersion coefficients, have been calculated. Our results are in good agreement with the results obtained from ab initio relativistic many-body perturbation method and the available experimental measurements.展开更多
A microwave plasma torch (MPT) simultaneous spectrometer was used to study the spectral character and the matrix effect on alkali metal ions in solution. The main parameters were optimized. The microwave forward pow...A microwave plasma torch (MPT) simultaneous spectrometer was used to study the spectral character and the matrix effect on alkali metal ions in solution. The main parameters were optimized. The microwave forward power was 100 W. The argon flow rate that was used to sustain the Ar-MPT included the flow rate of carrier gas and the flow rate of support gas, which were 0. 8 and 1.0 L/min, respectively. The HC1 concentration in the solution was 0.02 mol/L. The observation height was 9. 0 ram. The detection limits of Li, Na, K, Rb, and Cs were 0. 0003, 0. 0004, 0. 009, 0.07 and 2.4 mg/L, respectively, and the resuhs obtained by the Ar-MPT were compared with those obtained by argon inductively coupled plasma(Ar-ICP) and argon microwave induced plasma(Ar-MIP). The interference effects of several matrix elements were also studied.展开更多
The temporal characteristics of GaAs NEA and alkali metal photocathodes are studied using Monte Carlo simulation method. The electron transit time and its distribution functions in the photocathodes are calculated. Ba...The temporal characteristics of GaAs NEA and alkali metal photocathodes are studied using Monte Carlo simulation method. The electron transit time and its distribution functions in the photocathodes are calculated. Based on the results, the time modulation transfer functions and temporal resolutions of the photocathodes are obtained. The results show that the response time and temporal resolution of alkali metal photocathode is in femitosecond order and those of GaAs NEA photocathode are in picosecond order.展开更多
Alkali metal ion batteries(AMIBs)are playing an irreplaceable part in the energy revolution,due to their intrinsic advantages of large capacity/power density and abundance of alkali metal ions in the earth’s crust.De...Alkali metal ion batteries(AMIBs)are playing an irreplaceable part in the energy revolution,due to their intrinsic advantages of large capacity/power density and abundance of alkali metal ions in the earth’s crust.Despite their great promise,the inborn deficiencies of commercial graphite and other anodes being researched so far call for the quest of better alternatives that exhibit all-round performance with the balance of energy/power density and cycling stability.Gallium-based materials,with impressive capacity utilization and self-healing ability,provide an anticipated solution to this conundrum.In this review,an overview on the recent progress of gallium-based anodes and their storage mechanism is presented.The current strategies used as engineering solutions to meet the scientific challenges ahead are discussed,in addition to the insightful outlook for possible future study.展开更多
In this paper, the interaction parameters in the subregular solution model, λ1 and λ2, are regarded as a linear function of temperature, T. Therefore, the molar excess Gibbs energy of A-B binary system may be reexpr...In this paper, the interaction parameters in the subregular solution model, λ1 and λ2, are regarded as a linear function of temperature, T. Therefore, the molar excess Gibbs energy of A-B binary system may be reexpressed as follows:Gm^E=xAxB[(λ11+λ12T)+(λ21+λ22T)xB]The calculation of the model parameters, λ11, λ12, λ21and λ22, was carried out numerically from the phase diagrams for 11 alkali metal-alkali halide or alkali earth metal-halide systems. In addition, artificial neural network trained by known data has been used to predict the values of these model parameters. The predicted results are in good agreement with the .calculated ones. The applicability of the subregular solution model to the alkali metal-alkali halide or alkali earth metal-halide systems were tested by comparing the available experimental composition along the boundary of miscibility gap with the calculated ones which were obtained by using genetic algorithm. The good agreement between the calculated and experimental results across the entire liquidus is valid evidence in support of the model.展开更多
A series of red emitting ZnTiO3 phosphors co-doped with Eu3+) and alkali metal ions(Li+, Na+ and K+) was prepared by sol-gel method. The crystal structure of the phosphors was investigated by using X-ray diffra...A series of red emitting ZnTiO3 phosphors co-doped with Eu3+) and alkali metal ions(Li+, Na+ and K+) was prepared by sol-gel method. The crystal structure of the phosphors was investigated by using X-ray diffraction(XRD) and transmission electron microscopy(TEM) after annealing at 700 ℃. The results show that the crystal structure belongs to the hexagonal phase of ZnTiO3 with space group R-3:R. The influence of site occupancy of different alkali metal ions on the emission of ZnTiO3:Eu3+) phosphors was investigated in detail. The emission intensity was significantly enhanced by introducing alkali metal ions. In contrast to Eu3+) singly doped ZnTiO3, the red emission intensities of ZnTiO3:Eu3+) with 4 mol% alkali metal ions(Li+, Na+, K+) were enhanced by about 2.1, 1.7 and 1.4 times, respectively. In addition, the Commission Internationale Ed I'eclairage(CIE) chromaticity coordinates of ZnTiO3:Eu3+), Li+(0.672, 0.328) are quite similar to the National Television Standard Committee(NTSC) standard values for the red(0.670, 0.380).展开更多
A plane wave density functional theory method was used to investigate the adsorption properties of isolated alkali metal atoms, including Li, Na, K, Rb and Cs on-top of the F 0 s defective center of MgO(001) surface...A plane wave density functional theory method was used to investigate the adsorption properties of isolated alkali metal atoms, including Li, Na, K, Rb and Cs on-top of the F 0 s defective center of MgO(001) surface. Among all the alkali metals, the lithium atom binds most strongly with the highest adsorption energy of 0.67 eV and the shortest distance of about 0.257 nm between metal and the surface, the binding energy for the sodium atom comes second, and just half of this value for the other alkali metal atoms. The relatively strong interaction of Li with the F 0 s center can be explained by a more covalent bonding involved, evidenced by results of both the projected density of states and the projected charge density. The bonding mechanism is discussed in detail.展开更多
The catalytic effects of alkali metal ions(Na^(+)and K^(+))on NO_(x)precursor formation during coal pyrolysis were investigated using the N-containing compound pyridine as a model compound.Density functional theory ca...The catalytic effects of alkali metal ions(Na^(+)and K^(+))on NO_(x)precursor formation during coal pyrolysis were investigated using the N-containing compound pyridine as a model compound.Density functional theory calculations at the B3LYP/6-31G(d,p)level of theory were conducted to elucidate the mechanism of pyridine pyrolysis and the pathways for HCN formation.The calculation results indicate that Na^(+)and K^(+)have distinct influences on different pyrolysis reactions;these alkali metal ions facilitate the initial hydrogen transfer from C_(1)to N and C_(2),whereas they hinder the other hydrogen migration reactions.Both Na^(+)and K^(+)significantly reduce the activation energies for C–C bond breakage and triple-bond formation,whereas they increase the activation energies for the isomerization reactions.The different effects essentially result from the distinct charge distributions induced by the two ions.Due to the distinct influences on the different reactions,the rate-determining steps are modulated,affecting the competitiveness of the different possible pathways of HCN formation.The formation of HCN from pyridine is promoted in the presence of Na^(+)and K^(+)because all the overall activation energies are decreased for different pathways.The calculation results agree well with previous experimental studies.Thus,the findings offer a new and promising approach to reveal the formation mechanism of NO_(x)and facilitate the control of NO_(x)for coal utilization.展开更多
基金financial support from European Union(Interreg FWVL V project PSYCHE)from the French National Research Agency(Multiprobe project,ANR-20-CE42-0007)。
文摘CO_(2)hydrogenation is an attractive way to store and utilize carbon dioxide generated by industrial processes,as well as to produce valuable chemicals from renewable and abundant resources.Iron catalysts are commonly used for the hydrogenation of carbon oxides to hydrocarbons.Iron-molybdenum catalysts have found numerous applications in catalysis,but have been never evaluated in the CO_(2)hydrogenation.In this work,the structural properties of iron-molybdenum catalysts without and with a promoting alkali metal(Li,Na,K,Rb,or Cs)were characterized using X-ray diffraction,hydrogen temperatureprogrammed reduction,CO_(2)temperature-programmed desorption,in-situ^(57)Fe Mossbauer spectroscopy and operando X-ray adsorption spectroscopy.Their catalytic performance was evaluated in the CO_(2)hydrogenation.During the reaction conditions,the catalysts undergo the formation of an iron(Ⅱ)molybdate structure,accompanied by a partial reduction of molybdenum and carbidization of iron.The rate of CO_(2)conversion and product selectivity strongly depend on the promoting alkali metals,and electronegativity was identified as an important factor affecting the catalytic performance.Higher CO_(2)conversion rates were observed with the promoters having higher electronegativity,while low electronegativity of alkali metals favors higher light olefin selectivity.
基金supported by the National Key Research and Development Program of China(2020YFB1713500)the Chinese 02 Special Fund(2017ZX02408003)+1 种基金Open Fund of State Key Laboratory of Advanced Refractories(SKLAR202210)the Foundation of Department of Science and Technology of Henan Province(212102210219).
文摘Alkali metals(Li,Na,and K)are promising candidates for high-performance rechargeable alkali metal battery anodes due to their high theoretical specific capacity and low electrochemical potential.However,the actual application of alkali metal anodes is impeded by the challenges of alkali metals,including their high chemical reactivity,uncontrolled dendrite growth,unstable solid electrolyte interphase,and infinite volume expansion during cycling processes.Introducing carbon nanotube-based nanomaterials in alkali metal anodesis an effective solution to these issues.These nanomaterials have attracted widespread attention owing to their unique properties,such as their high specific surface area,superior electronic conductivity,and excellent mechanical stability.Considering the rapidly growing research enthusiasm for this topic in the last several years,we review recent progress on the application of carbon nanotube-based nanomaterials in stable and dendrite-free alkali metal anodes.The merits and issues of alkali metal anodes,as well as their stabilizing strategies are summarized.Furthermore,the relationships among methods of synthesis,nano-or microstructures,and electrochemical properties of carbon nanotube-based alkali metal anodes are systematically discussed.In addition,advanced characterization technologies on the reaction mechanism of carbon nanotube-based nanomaterials in alkali metal anodes are also reviewed.Finally,the challenges and prospects for future study and applications of carbon nanotube-based AMAs in high-performance alkali metal batteries are discussed.
基金financial support from Natural Science Foundation of Inner Mongolia(No.2019MS05068)Inner Mongolia scientific and technological achievements transformation project(CGZH2018132)+3 种基金Inner Mongolia major science and technology project(2020ZD0024)the research project of Inner Mongolia Electric Power(Group)Co.,Ltd for post-doctoral studies,the Hong Kong Polytechnic University start-up funding,National Nature Science Foundation of China(No.51872157)Shenzhen Key Laboratory on Power Battery Safety Research(No.ZDSYS201707271615073)financial support from the Australian Research Council(DE190100445).
文摘The ever-growing pursuit of high energy density batteries has triggered extensive efforts toward developing alkali metal(Li,Na,and K)battery(AMB)technologies owing to high theoretical capacities and low redox potentials of metallic anodes.Typically,for new battery systems,the electrolyte design is critical for realizing the battery electrochemistry of AMBs.Conventional electrolytes in alkali ion batteries are generally unsuitable for sustaining the stability owing to the hyper-reactivity and dendritic growth of alkali metals.In this review,we begin with the fundamentals of AMB electrolytes.Recent advancements in concentrated and fluorinated electrolytes,as well as functional electrolyte additives for boosting the stability of Li metal batteries,are summarized and discussed with a special focus on structure-composition-performance relationships.We then delve into the electrolyte formulations for Na-and K metal batteries,including those in which Na/K do not adhere to the Li-inherited paradigms.Finally,the challenges and the future research needs in advanced electrolytes for AMB are highlighted.This comprehensive review sheds light on the principles for the rational design of promising electrolytes and offers new inspirations for developing stable AMBs with high performance.
基金support from the National Natural Science Foundation of China (52072257)the National Key Research and Development Program of China (2019YFE0118800).
文摘Alkali metal-carbon dioxide(Li/Na/K-CO_(2))batteries are emerging electrochemical energy storage technologies in the context of the energy crisis and the urgent demand for carbon neutrality.Alkali metal-CO_(2) batteries offer a new strategy for CO_(2) fixation and utilization,and thus has been receiving considerable attention in recent years.Considerable progress has been achieved since alkali metal-CO_(2) batteries were invented,especially in terms of development of new electrode materials,and yet,research is lacking on the underlying mechanisms of the systems.This is the first typical review focusing on the electrochemical mechanisms of metal-CO_(2) batteries that summarizes the current understanding of and provides insights into the thermodynamic reaction pathways,the kinetic characteristics,and the crucial factors determining the reaction mechanisms in alkali metal-CO_(2) batteries.The review starts with the fundamental concepts of alkali metal-CO_(2) batteries,followed by a comprehensive discussion of the working mechanisms on cathodes and anodes.Moreover,the operation mechanisms of state-of-the-art electrolytes,including liquid and(quasi-)solid-state electrolytes,are also described.Finally,we identify the unsolved problems in current alkali metal-CO_(2) batteries and propose potential topics for future research.
基金supported by the National Natural Science Foundation of China(51301161)973 Project(2010CB631304)the Project of National Natural Science Funds for Distinguished Young Scholar(51225206)
文摘Alkali metal hydroxide and hydride composite systems contain both protic (H bonded with O) and hydridic hydrogen. The interaction of these two types of hydrides produces hydrogen. The enthalpy of dehydrogenation increased with the increase of atomic number of alkali metals, i.e., -23 kJ/molnz for LiOH-LiH, 55.34 kJ/moln: for NaOH-NaH and 222 kJ/molH2 for KOH-KH. These thermodynamic calculation results were consistent with our experimental results. H2 was released from LiOH-LiH system during ball milling. The dehydrogenation temperature of NaOH-NaH system was about 150 ℃; whereas KOH and KH did not interact with each other during the heating process. Instead, KH decomposed by itself. In these three systems, NaOH-NaH was the only reversible hydrogen storage system, the enthalpy of dehydrogenation was about 55.65 kJ/molHz, and the corresponding entropy was ca. 101.23 J/(molHz .K), so the temperature for releasing 1.0 bar H2 was as high as 518 ℃, showing unfavorable thermodynamic properties. The activation energy for hydrogen desorption of NaOH-NaH was found to be 57.87 kJ/mol, showing good kinetic properties.
基金supported by NSFC(21473094 and21421001)MOE Innovation Team(IRT13022) in China
文摘Rechargeable alkali metal-air batteries are considered as the most promising candidate for the power source of electric vehicles(EVs) due to their high energy density. However, the practical application of metal-air batteries is still challenging. In the past decade, many strategies have been purposed and explored, which promoted the development of metal-air batteries. The reaction mechanisms have been gradually clarified and catalysts have been rationally designed for air cathodes. In this review, we summarize the recent development of alkali metal-air batteries from four parts: metal anodes, electrolytes, air cathodes and reactant gases, wherein we highlight the important achievement in this filed. Finally problems and prospective are discussed towards the future development of alkali metal-air batteries.
文摘Metal-organic frameworks (MOFs) have attracted much attention as adsorbents for the separation of CO2 from flue gas or natural gas. Here, a typical metal-organic framework HKUST-I(also named Cu-BTC or MOF-199) was chemically reduced by doping it with alkali metals (Li, Na and K) and they were further used to investigate their CO2 adsorption capacities. The structural information, surface chemistry and thermal behavior of the prepared adsorbent samples were characterized by X-ray powder diffraction (XRD), thermo-gravimetric analysis (TGA) and nitrogen adsorption-desorption isotherm analysis. The results showed that the CO2 storage capacity of HKUST-1 doped with moderate quantities of Li+, Na+ and K+, individually, was greater than that of unmodified HKUST-1. The highest CO2 adsorption uptake of 8.64 mmol/g was obtained with 1K-HKUST-1, and it was ca. 11% increase in adsorption capacity at 298 K and 18 bar as compared with HKUST- 1. Moreover, adsorption tests showed that HKUST-1 and 1K-HKUST-1 displayed much higher adsorption capacities of CO2 than those of N2. Finally, the adsorption/desorption cycle experiment revealed that the adsorption performance of 1K-HKUST-1 was fairly stable, without obvious deterioration in the adsorption capacity of CO2 after 10 cycles.
文摘Surface properties (viz. surface area, basicity/base strength distribution, and crystal phases) of alkali metal doped CaO (alkali metal/Ca= 0.1 and 0.4) catalysts and their catalytic activity/selectivity in oxidative coupling of methane (OCM) to higher hydrocarbons at different reaction conditions (viz. temperature, 700 and 750 ℃; CH4/O2 ratio, 4.0 and 8.0 and space velocity, 5140-20550 cm^3 ·g^-1·h^-1) have been investigated. The influence of catalyst calcination temperature on the activity/selectivity has also been investigated. The surface properties (viz. surface area, basicity/base strength distribution) and catalytic activity/selectivity of the alkali metal doped CaO catalysts are strongly influenced by the alkali metal promoter and its concentration in the alkali metal doped CaO catalysts. An addition of alkali metal promoter to CaO results in a large decrease in the surface area but a large increase in the surface basicity (strong basic sites) and the C2+ selectivity and yield of the catalysts in the OCM process. The activity and selectivity are strongly influenced by the catalyst calcination temperature. No direct relationship between surface basicity and catalytic activity/selectivity has been observed. Among the alkali metal doped CaO catalysts, Na-CaO (Na/Ca = 0.1, before calcination) catalyst (calcined at 750 ℃), showed best performance (C2+ selectivity of 68.8% with 24.7% methane conversion), whereas the poorest performance was shown by the Rb-CaO catalyst in the OCM process.
文摘EAB zeolite was successfully prepared and applied to selective adsorption of Li^(+),Na^(+)and K^(+)ions.The physical and chemical properties of the adsorbent were characterized by X-ray diffraction(XRD),X-ray fluorescence(XRF),scanning electron microscope(SEM)and thermogravimetry(TG)methods.The ion exchange behaviours for Li^(+),Na^(+)and K^(+)ions in monomcomponent and multicomponent solutions were studied.In independent ion exchange,the ion exchange capacities ratiosα(/Na/Li)andα(K/Li)were 3.8 and 6.2,respectively.In competitive ion exchange,the selectivitiesβ(Na/Li)andβ(K/Li)increased with the initial concentrations and reached 409 and 992 when the initial concentrations was 100 mmol/L.The thermodynamic study results showed that Gibbs free energy change(ΔGΘ)of ion exchange reaction between Li-EAB and K^(+)was-34.96 kJ/mol,indicating that ion exchange of K^(+)ions was more energetically favourable than Li^(+)ions.The calculation results showed that the energy barriers of ion exchange increased in the order K^(+)Na^(+)<Li^(+).The study shows that EAB zeolite is potential to be used in the separation of alkali ions.
基金Project supported by the Key Program of the National Natural Science Foundation of China(Grant Nos.21031001 and U1034003)the National Natural Science Foundation of China(Grant Nos.20971040 and 21173072)the Cultivation Fund of the Key Scientific and Technical Innovation Project,Ministry of Education of China(Grant No.708029)
文摘The electronic structures and field emission properties of capped CNT55 systems with or without alkali metal atom adsorption were systematically investigated by density functional theory calculation.The results indicate that the adsorption of alkali metal on the center site of a CNT tip is energetically favorable.In addition,the adsorption energies increase with the introduction of the electric field.The excessive negative charges on CNT tips make electron emittance much easier and result in a decrease in work function.Furthermore,the inducing effect by positively charged alkali metal atoms can be reasonably considered as the dominant reason for the improvement in field emission properties.
文摘A series of mesoporous smectite like materials incorporated with alkali metals such as Li, Na, K and Cs has been synthesized with the hydrothermal method. The crystalline and the pore structures of the materials synthesized significantly change with the introduction of alkali metals. The addition of Li gives highly ordered layer phases, while the incorporation of Cs yields much less crystalline structures. Although Na or K has little effect on the crystalline structure, they modify the pore structure.
基金supported by the National Basic Research Program of China(Grant No.2012CB821305)the National Natural Science Foundation of China(Grant Nos.11034009 and 11274246)
文摘A semi-empirical atomic structure model method is developed in the framework of a relativistic case. This method starts from Dirac-Fock calculations using B-spline basis set. The core-valence electron correction is then treated in a semiempirical core polarization potential. As an application, the polarization properties of alkali metal atoms, including the static polarizabilities and long-range two-body dispersion coefficients, have been calculated. Our results are in good agreement with the results obtained from ab initio relativistic many-body perturbation method and the available experimental measurements.
文摘A microwave plasma torch (MPT) simultaneous spectrometer was used to study the spectral character and the matrix effect on alkali metal ions in solution. The main parameters were optimized. The microwave forward power was 100 W. The argon flow rate that was used to sustain the Ar-MPT included the flow rate of carrier gas and the flow rate of support gas, which were 0. 8 and 1.0 L/min, respectively. The HC1 concentration in the solution was 0.02 mol/L. The observation height was 9. 0 ram. The detection limits of Li, Na, K, Rb, and Cs were 0. 0003, 0. 0004, 0. 009, 0.07 and 2.4 mg/L, respectively, and the resuhs obtained by the Ar-MPT were compared with those obtained by argon inductively coupled plasma(Ar-ICP) and argon microwave induced plasma(Ar-MIP). The interference effects of several matrix elements were also studied.
文摘The temporal characteristics of GaAs NEA and alkali metal photocathodes are studied using Monte Carlo simulation method. The electron transit time and its distribution functions in the photocathodes are calculated. Based on the results, the time modulation transfer functions and temporal resolutions of the photocathodes are obtained. The results show that the response time and temporal resolution of alkali metal photocathode is in femitosecond order and those of GaAs NEA photocathode are in picosecond order.
基金the National Key R&D Research Program of China(Grant No.2018YFB0905400)the National Natural Science Foundation of China(Grant Nos.51872277,21606003,51902062,51972067,51802044,51925207 and U1910210)+2 种基金the Fundamental Research Funds for the Central Universities(WK2060140026)the DNL cooperation Fund,CAS(DNL180310)the Guangdong Natural Science Funds for Distinguished Young Scholar(Grant No.2019B151502039)。
文摘Alkali metal ion batteries(AMIBs)are playing an irreplaceable part in the energy revolution,due to their intrinsic advantages of large capacity/power density and abundance of alkali metal ions in the earth’s crust.Despite their great promise,the inborn deficiencies of commercial graphite and other anodes being researched so far call for the quest of better alternatives that exhibit all-round performance with the balance of energy/power density and cycling stability.Gallium-based materials,with impressive capacity utilization and self-healing ability,provide an anticipated solution to this conundrum.In this review,an overview on the recent progress of gallium-based anodes and their storage mechanism is presented.The current strategies used as engineering solutions to meet the scientific challenges ahead are discussed,in addition to the insightful outlook for possible future study.
文摘In this paper, the interaction parameters in the subregular solution model, λ1 and λ2, are regarded as a linear function of temperature, T. Therefore, the molar excess Gibbs energy of A-B binary system may be reexpressed as follows:Gm^E=xAxB[(λ11+λ12T)+(λ21+λ22T)xB]The calculation of the model parameters, λ11, λ12, λ21and λ22, was carried out numerically from the phase diagrams for 11 alkali metal-alkali halide or alkali earth metal-halide systems. In addition, artificial neural network trained by known data has been used to predict the values of these model parameters. The predicted results are in good agreement with the .calculated ones. The applicability of the subregular solution model to the alkali metal-alkali halide or alkali earth metal-halide systems were tested by comparing the available experimental composition along the boundary of miscibility gap with the calculated ones which were obtained by using genetic algorithm. The good agreement between the calculated and experimental results across the entire liquidus is valid evidence in support of the model.
基金Supported by Department of Social Development Project of Jiangsu Province(BE2015659)Science and Technology Project of Anhui Province(1604a0802122)Collaborative Innovation Center Project in Jiangsu Province(GX2015302)
文摘A series of red emitting ZnTiO3 phosphors co-doped with Eu3+) and alkali metal ions(Li+, Na+ and K+) was prepared by sol-gel method. The crystal structure of the phosphors was investigated by using X-ray diffraction(XRD) and transmission electron microscopy(TEM) after annealing at 700 ℃. The results show that the crystal structure belongs to the hexagonal phase of ZnTiO3 with space group R-3:R. The influence of site occupancy of different alkali metal ions on the emission of ZnTiO3:Eu3+) phosphors was investigated in detail. The emission intensity was significantly enhanced by introducing alkali metal ions. In contrast to Eu3+) singly doped ZnTiO3, the red emission intensities of ZnTiO3:Eu3+) with 4 mol% alkali metal ions(Li+, Na+, K+) were enhanced by about 2.1, 1.7 and 1.4 times, respectively. In addition, the Commission Internationale Ed I'eclairage(CIE) chromaticity coordinates of ZnTiO3:Eu3+), Li+(0.672, 0.328) are quite similar to the National Television Standard Committee(NTSC) standard values for the red(0.670, 0.380).
基金supported by the National Natural Science Foundation of China (Grant No.60877017)the Innovation Program of Shanghai Municipal Education Commission (Grant No.08YZ04)
文摘A plane wave density functional theory method was used to investigate the adsorption properties of isolated alkali metal atoms, including Li, Na, K, Rb and Cs on-top of the F 0 s defective center of MgO(001) surface. Among all the alkali metals, the lithium atom binds most strongly with the highest adsorption energy of 0.67 eV and the shortest distance of about 0.257 nm between metal and the surface, the binding energy for the sodium atom comes second, and just half of this value for the other alkali metal atoms. The relatively strong interaction of Li with the F 0 s center can be explained by a more covalent bonding involved, evidenced by results of both the projected density of states and the projected charge density. The bonding mechanism is discussed in detail.
基金This work was supported by the National Key Research Development Program of China(2017YFB0601900)National Nature Science Foundation of China(51806220,51922040),China Postdoctoral Science Foundation(2019TQ0091)+1 种基金Grants from Fok Ying Tung Education Foundation(161051)Fundamental Research Funds for the Central Universities(2020MS020,2020DF01).
文摘The catalytic effects of alkali metal ions(Na^(+)and K^(+))on NO_(x)precursor formation during coal pyrolysis were investigated using the N-containing compound pyridine as a model compound.Density functional theory calculations at the B3LYP/6-31G(d,p)level of theory were conducted to elucidate the mechanism of pyridine pyrolysis and the pathways for HCN formation.The calculation results indicate that Na^(+)and K^(+)have distinct influences on different pyrolysis reactions;these alkali metal ions facilitate the initial hydrogen transfer from C_(1)to N and C_(2),whereas they hinder the other hydrogen migration reactions.Both Na^(+)and K^(+)significantly reduce the activation energies for C–C bond breakage and triple-bond formation,whereas they increase the activation energies for the isomerization reactions.The different effects essentially result from the distinct charge distributions induced by the two ions.Due to the distinct influences on the different reactions,the rate-determining steps are modulated,affecting the competitiveness of the different possible pathways of HCN formation.The formation of HCN from pyridine is promoted in the presence of Na^(+)and K^(+)because all the overall activation energies are decreased for different pathways.The calculation results agree well with previous experimental studies.Thus,the findings offer a new and promising approach to reveal the formation mechanism of NO_(x)and facilitate the control of NO_(x)for coal utilization.