Silicon(Si)and carbon(C)composites hold the promise for replacing the commercial graphite anode,thus increasing the energy density of lithium-ion batteries(LIBs).To mitigate the formation of SiC,this paper reports a m...Silicon(Si)and carbon(C)composites hold the promise for replacing the commercial graphite anode,thus increasing the energy density of lithium-ion batteries(LIBs).To mitigate the formation of SiC,this paper reports a molten salt electrolysis approach to prepare C-Si composite by the electrolysis of C-SiO2 composites.Unlike the conventional way of making a C coating on Si,C-SiO2 composites were prepared by pyrolyzing the low-cost sucrose and silica.The electrochemical deoxidation of the C-SiO2 composites not only produces nanostructured Si inside the C matrix but also introduces voids between the C and Si owing to the volume shrinkage from converting SiO2 to Si.More importantly,the use of Mg ion-containing molten salts precludes the generation of SiC,and the electrolytic Si@C composite anode delivers a capacity of about 1500 mAh g-1 after 100 cycles at a current density of 500 mA g-1.Further,the Si@C‖LiNi0.6Co0.2Mn0.2O2 full cell delivers a high energy density of 608 Wh kg-1.Overall,the molten salt approach provides a one-step electrochemical way to convert oxides@C to metals@C functional materials.展开更多
Electrical conductivity of molten binary and ternary mixtures based on the system NaF-AlF3-SiO2 was investigated by means of a tube–cell （made of pyrolytic boron nitride） with stationary electrodes. Viscosity of th...Electrical conductivity of molten binary and ternary mixtures based on the system NaF-AlF3-SiO2 was investigated by means of a tube–cell （made of pyrolytic boron nitride） with stationary electrodes. Viscosity of the binary system Na3AlF6-SiO2 was measured by computerized torsion pendulum method. It was found that conductivity and viscosity varied linearly with temperature in all investigated mixtures. Obtained content dependence of electrical conductivity （isotherms） was divided into two parts. First, one represented the content region up to 10%（mole fraction） of SiO2;second, the region was with a higher content of SiO2 （from 10%up to 40%）. While the conductivity considerably decreased with content of SiO2 in the second part; it surprisingly rose in the low content range. A small addition of SiO2 to the molten cryolite （up to 10%） could slightly increase viscosity, but had no influence on the slope of this dependence since it is responsible for a glassy-networks formation in the melt. Further addition of SiO2 to the molten cryolite had a huge effect on the viscosity.展开更多
Silicon has a large impact on the energy supply and economy in the modern world. In industry, high purity silicon is firstly prepared by carbothermic reduction of silica with the produced raw silicon being further ref...Silicon has a large impact on the energy supply and economy in the modern world. In industry, high purity silicon is firstly prepared by carbothermic reduction of silica with the produced raw silicon being further refined by a modified Siemens method. This process suffers from the disadvantages of high cost and contaminant release and emission. As an alternative, the molten salt electrolysis approach, particularly the FFC Cambridge Process(FFC: Fray-Farthing-Chen), could realize high purity silicon products with morphology-controllable nanostructures at low or mild temperatures(generally 650–900 ℃). In this article, we review the development, reaction mechanisms, and electrolysis conditions of silicon production by the FFC Cambridge Process. Applications of the silicon products from electrolysis in molten salts are also discussed in terms of energy applications, including using them as the photovoltaic element in solar cells and as the charge storage phase in the negative electrode(negatrode) of lithium ion batteries.展开更多
Using FFC-Cambridge Process to prepare Si from SiO2 is a promising method to prepare nanostructured and highly pure silicon for solar cells.However,the method still has many problems unsolved and the controlling effec...Using FFC-Cambridge Process to prepare Si from SiO2 is a promising method to prepare nanostructured and highly pure silicon for solar cells.However,the method still has many problems unsolved and the controlling effect of the cell voltage on silicon product is not clear.Here we report in this article that nano cluster-like silicon product with purity of 99.95%has been prepared by complete conversion of raw material SiO2,quartz glass plate,using constant cell voltage electrolysis FFC-Cambridge Process.By analysis of XRD,EDS,TEM,HRTEM and ICP-AES as well as the discussion from the thermodynamics calculation,the morphology and components of the product based on the change of cell voltage are clarified.It is clear that pure silicon could be prepared at the cell voltage of 1.7 2.1 V in this reaction system.The silicon material have cluster-like structure which are made of silicon nanoparticles in 20 100 nm size.Interestingly,the cluster-like nano structure of the silicon can be tuned by the used cell voltage.The purity,yield and the energy cost of silicon product prepared at the optimized cell voltage are discussed.The purity of the silicon product could be further improved,hence this method is promising for the preparation of solar grade silicon in future.展开更多
Aluminum silicon titanium master alloys were prepared in the laboratory by electrolysis of silica and titania dissolved in cryolite alumina melts. Alloys containing up to 12 mass% Si and 2.6 mass% Ti were formed af...Aluminum silicon titanium master alloys were prepared in the laboratory by electrolysis of silica and titania dissolved in cryolite alumina melts. Alloys containing up to 12 mass% Si and 2.6 mass% Ti were formed after about 90 min of electrolysis at 950℃. The current efficiency for the preparation of the Al Si Ti alloys varied with time, temperature and cathodic current density. It is concluded that this electrolytic method may be an interesting alternative to the direct metal mixing process for formation of Al Si Ti master alloys.展开更多
The electrochemical behavior of lanthanide elements deposited on liquid zinc cathodes was studied using cyclic voltammetry(CV)and open circuit chronopotentiometry(OCP).We observed a"bimodal effect"in the equ...The electrochemical behavior of lanthanide elements deposited on liquid zinc cathodes was studied using cyclic voltammetry(CV)and open circuit chronopotentiometry(OCP).We observed a"bimodal effect"in the equilibrium deposition potentials of zinc with lanthanides.A mathematic equation is derived to illustrate the relationship between the equilibrium potential of the intermetallic compounds formed by lanthanide elements and zinc and their atomic radius.This equation is not only applicable to lanthanide elements but also hold for other elements such as alkali metal lithium,alkaline earth metal magnesium,calcium and transition metal niobium,which have crucial theoretical significance for the electrolysis of intermetallic compounds,the separation,and extraction of metals.展开更多
基金the financial support from the National Training Program of Innovation and Entrepreneurship for Undergraduates(201810145075)Fundamental Research Funds for the Central Universities(N172505002)+2 种基金NSFC(51704060)National Thousand Youth Talent Program of Chinathe 111 Project(B16009)
文摘Silicon(Si)and carbon(C)composites hold the promise for replacing the commercial graphite anode,thus increasing the energy density of lithium-ion batteries(LIBs).To mitigate the formation of SiC,this paper reports a molten salt electrolysis approach to prepare C-Si composite by the electrolysis of C-SiO2 composites.Unlike the conventional way of making a C coating on Si,C-SiO2 composites were prepared by pyrolyzing the low-cost sucrose and silica.The electrochemical deoxidation of the C-SiO2 composites not only produces nanostructured Si inside the C matrix but also introduces voids between the C and Si owing to the volume shrinkage from converting SiO2 to Si.More importantly,the use of Mg ion-containing molten salts precludes the generation of SiC,and the electrolytic Si@C composite anode delivers a capacity of about 1500 mAh g-1 after 100 cycles at a current density of 500 mA g-1.Further,the Si@C‖LiNi0.6Co0.2Mn0.2O2 full cell delivers a high energy density of 608 Wh kg-1.Overall,the molten salt approach provides a one-step electrochemical way to convert oxides@C to metals@C functional materials.
基金supported by the Science and Technology Assistance Agency (APVV-0460-10 and SK-CN-0029-12)Slovak Grant Agency (VEGA 2/0116/14 and VEGA 2/0095/12)+2 种基金the National Natural Science Foundation of China (51322406)the Program for New Century Excellent Talents (NCET-13-0107)Ministry of Education of China
文摘Electrical conductivity of molten binary and ternary mixtures based on the system NaF-AlF3-SiO2 was investigated by means of a tube–cell （made of pyrolytic boron nitride） with stationary electrodes. Viscosity of the binary system Na3AlF6-SiO2 was measured by computerized torsion pendulum method. It was found that conductivity and viscosity varied linearly with temperature in all investigated mixtures. Obtained content dependence of electrical conductivity （isotherms） was divided into two parts. First, one represented the content region up to 10%（mole fraction） of SiO2;second, the region was with a higher content of SiO2 （from 10%up to 40%）. While the conductivity considerably decreased with content of SiO2 in the second part; it surprisingly rose in the low content range. A small addition of SiO2 to the molten cryolite （up to 10%） could slightly increase viscosity, but had no influence on the slope of this dependence since it is responsible for a glassy-networks formation in the melt. Further addition of SiO2 to the molten cryolite had a huge effect on the viscosity.
基金supported by the National Natural Science Foundation of China (No.51602234)Ningbo Municipal Government (3315 Plan and 2014A35001-1)UK Engineering and Physical Science Research Council (EP/J000582/1, GR/R68078)。
文摘Silicon has a large impact on the energy supply and economy in the modern world. In industry, high purity silicon is firstly prepared by carbothermic reduction of silica with the produced raw silicon being further refined by a modified Siemens method. This process suffers from the disadvantages of high cost and contaminant release and emission. As an alternative, the molten salt electrolysis approach, particularly the FFC Cambridge Process(FFC: Fray-Farthing-Chen), could realize high purity silicon products with morphology-controllable nanostructures at low or mild temperatures(generally 650–900 ℃). In this article, we review the development, reaction mechanisms, and electrolysis conditions of silicon production by the FFC Cambridge Process. Applications of the silicon products from electrolysis in molten salts are also discussed in terms of energy applications, including using them as the photovoltaic element in solar cells and as the charge storage phase in the negative electrode(negatrode) of lithium ion batteries.
基金supported by the Solar Energy Initiative of the Knowledge Innovation Program of the Chinese Academy of Sciences(Grant No.KGCX2-YW-395)
文摘Using FFC-Cambridge Process to prepare Si from SiO2 is a promising method to prepare nanostructured and highly pure silicon for solar cells.However,the method still has many problems unsolved and the controlling effect of the cell voltage on silicon product is not clear.Here we report in this article that nano cluster-like silicon product with purity of 99.95%has been prepared by complete conversion of raw material SiO2,quartz glass plate,using constant cell voltage electrolysis FFC-Cambridge Process.By analysis of XRD,EDS,TEM,HRTEM and ICP-AES as well as the discussion from the thermodynamics calculation,the morphology and components of the product based on the change of cell voltage are clarified.It is clear that pure silicon could be prepared at the cell voltage of 1.7 2.1 V in this reaction system.The silicon material have cluster-like structure which are made of silicon nanoparticles in 20 100 nm size.Interestingly,the cluster-like nano structure of the silicon can be tuned by the used cell voltage.The purity,yield and the energy cost of silicon product prepared at the optimized cell voltage are discussed.The purity of the silicon product could be further improved,hence this method is promising for the preparation of solar grade silicon in future.
文摘Aluminum silicon titanium master alloys were prepared in the laboratory by electrolysis of silica and titania dissolved in cryolite alumina melts. Alloys containing up to 12 mass% Si and 2.6 mass% Ti were formed after about 90 min of electrolysis at 950℃. The current efficiency for the preparation of the Al Si Ti alloys varied with time, temperature and cathodic current density. It is concluded that this electrolytic method may be an interesting alternative to the direct metal mixing process for formation of Al Si Ti master alloys.
文摘The electrochemical behavior of lanthanide elements deposited on liquid zinc cathodes was studied using cyclic voltammetry(CV)and open circuit chronopotentiometry(OCP).We observed a"bimodal effect"in the equilibrium deposition potentials of zinc with lanthanides.A mathematic equation is derived to illustrate the relationship between the equilibrium potential of the intermetallic compounds formed by lanthanide elements and zinc and their atomic radius.This equation is not only applicable to lanthanide elements but also hold for other elements such as alkali metal lithium,alkaline earth metal magnesium,calcium and transition metal niobium,which have crucial theoretical significance for the electrolysis of intermetallic compounds,the separation,and extraction of metals.
