CN106591891A - Method for preparing nanometer porous material from compact material - Google Patents
Method for preparing nanometer porous material from compact material Download PDFInfo
- Publication number
- CN106591891A CN106591891A CN201611129196.XA CN201611129196A CN106591891A CN 106591891 A CN106591891 A CN 106591891A CN 201611129196 A CN201611129196 A CN 201611129196A CN 106591891 A CN106591891 A CN 106591891A
- Authority
- CN
- China
- Prior art keywords
- metal
- anode
- powder
- fused salt
- target substance
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C5/00—Electrolytic production, recovery or refining of metal powders or porous metal masses
- C25C5/04—Electrolytic production, recovery or refining of metal powders or porous metal masses from melts
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/33—Silicon
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Nanotechnology (AREA)
- Materials Engineering (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Physics & Mathematics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Composite Materials (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a method for preparing a nanometer porous material from a compact material. Fused salt containing alkali metal or alkaline-earth metal M halide serves as media, ions of metal M are reduced on the compact target material A through an electrochemical method, an alloy of the material A and the metal M is generated, and the compact target material A has volume expansion. The alloy serves as an anode, the metal M is dissolved out from the alloy, nanometer channels are reserved in the final product, and therefore the nanometer porous material A is obtained. The method is simple in process, environmentally friendly and low in cost, the nanometer porous material with the size of native metal particles being smaller than 20 nm can be obtained, and the prepared nanometer porous material has good circulation stability when serving as an ion battery cathode material.
Description
Technical field
The present invention relates to a kind of method that dense material is prepared into into nano-porous materials, i.e., using melten salt electriochemistry method
Compact metal or semiconductor are prepared into into nano porous metal or nano porous semiconductor material.
Background technology
Porous silicon all has weight in fields such as photoelectron, energy conversion, lithium ion battery, environmental monitoring, biology sensors
The using value wanted.But preparing for porous silicon, especially nano-structure porous silicon is particularly difficult.
Porous silicon mainly includes two kinds of porous surface silicon layer and body phase porous silicon.By carrying out in the electrolyte containing HF
Anodic corrodes, and can generate that one layer of porous silicon, Parameter adjustable and reproducible, but efficiency is low, yield in monocrystalline silicon surface
Low, hydrofluoric acid toxicity corrosivity and waste water are serious.Porous silicon surface layer also can be prepared by chemical attack, will silicon put
In containing HF and oxidant (such as HNO3、NaNO3Deng) solution in perform etching.The method production efficiency is slightly higher, but also needs long-time anti-
Should, low yield, product lack of homogeneity, it is difficult to repeat.Lithographic method is all difficult to prepare porous silica body phase material.
The preparation method of body phase porous silicon mainly has following three kinds:
The first is by first silicon and reactive magnesium will be prepared into Mg2Si, then be oxidized to Mg with chemical oxidization method
MgO, is then removed MgO by pickling, can obtain body phase porous silica material.But whole technical process flow process length, spent acid row
Put serious.And the consumption of magnesium reducing agent causes cost to dramatically increase.
Second is that porous silicon (Nano Energy, 2016,20,68-75) is prepared by magnesiothermic reduction silica.
The method is originated and MgO accessory substance problems except above-mentioned magnesium, also two main difficulties.What first product early stage was generated
MgO can hinder carrying out completely for subsequent reactions;Its two be product silicon be easy to further with magnesium vapor reaction generate Mg2The by-products such as Si
Thing.
The third is that electroreduction solid silica negative electrode is also expected to prepare porous silicon in the fused salts such as calcium chloride
(J.Mater.Chem.A, 2013,1,10243), but silica dielectric reacts in itself difficult, and silica is direct when being electrolysed
Oxonium ion is generated during electrochemical reduction, oxonium ion needs to move to anode discharge and be discharged, thus it is difficult to face anode.Its master
Reason is wanted to be that the anode that can be used at present is still confined to material with carbon element, the anode discharge of oxonium ion can cause anode consumption, discharge CO2
Gas, and the latter is easy to dissolving under electrolysate oxonium ion existence condition and into electrolyte and moves to cathodic discharge, leads
Cause current efficiency to reduce and floating carbon etc. is formed in molten-salt electrolysis liquid.
It can be seen that, above-mentioned lithographic method yield, efficiency are low, and environmental problem is serious;Active metal alloying or reducing process are high
Noble metal consumption is big, complex process, severe reaction conditions;Electrolysis face that kinetics of electrode process is difficult, anode is difficult and
It is difficult to prepare nano-structure porous silicon.Extensively apply front in terms of photoelectron, energy conversion, ion battery in view of nano-structure porous silicon
Scape, at present in the urgent need to developing the economy, environmental protection, the high nano-structure porous silicon new preparation technology of product quality.
The content of the invention
For the deficiencies in the prior art, the present invention provides a kind of low cost, pollute and few prepare dense material
Into the method for nano-porous materials.
The present invention provide technical scheme be:
A kind of method that dense material is prepared into into nano-porous materials, comprises the following steps:
(1) (i) using the target substance A of solid-state as negative electrode, using the fused salt containing metal M halide as medium,
Cathodic polarization is carried out under the conditions of 300-950 DEG C, makes metal M and target substance A that alloying reaction to occur, obtain M-A alloys;Or
(ii) reacted by the DIRECT ALLOYING of metal M and target substance A, obtain M-A alloys;
Described target substance A is one or more in ii IA-VIA race element;
Described negative electrode is the dense material of target substance A or the porous former of dense powder shape target substance A;
Described metal M is alkaline-earth metal or alkali metal, and described fused salt is alkaline-earth halide fused salt or alkali metal
Halide fused salt;
(2) using the M-A alloys obtained by step (1) as anode, using the fused salt containing metal M halide as medium,
Anode polarization is carried out under the conditions of 300-950 DEG C, the metal M dissolutions in M-A alloys are made;
(3) step (1) and step (2) are repeated in several times, target electrode is taken out, residual fused salt is removed, target is obtained
The nano-porous materials of substance A.
In step (1), by target substance A:A () is directly as electrode;(b) be fixed on net made by solid-state conductive metal or
As electrode in basket;Or (c) is compounded on solid-state conductive metal as electrode;
Anode in step (1) is the simple substance or alloy of metal M, and the voltage between negative electrode and anode is controlled during cathodic polarization
For -0.8-1.2V;Or the anode in step (1) is graphite, precipitation of the cathode potential relative to metal M is controlled during cathodic polarization
Potential is higher by 0.01-1.2V;
Negative electrode in step (2) for metal M simple substance or alloy, or for solid-state conductive metal, by the polarization of M-A alloy anodes
When, the voltage of 0.5-2.5V is applied between anode and negative electrode;
Described solid-state conductive metal is the alloy of one or more in nickel, iron, titanium, molybdenum, tungsten.
In step (1), the porous former of described dense powder shape target substance A is obtained by following preparation method:
Porous body is prepared into after dense powder shape target substance A directly or with additive is mixed, described additive is conducting metal
The solid constituent of powder, carbon material powder or the fused-salt medium;The dense material of described target substance A is sheet, bulk
Or bar-shaped target substance A.
In step (1), the porous former of described dense powder shape target substance A be silica flour, silicon boron compound powder,
Silicon phosphorus composite powder, aluminium-antimony alloy powder, antimony powder end, germanium tin alloy powder, CaCl2Porous body made by-silicon mixed-powder
In one kind, the dense material of described target substance A is silicon chip;Described additive is graphite powder, Graphene powder or oxidation
Graphene powder.
In step (1), described metal M is the one kind in Mg, Ca, Li.
In step (3), the mode for removing residual fused salt is:A () removes residual fused salt by washing or pickling;Or (b) is lazy
Property atmosphere or vacuum condition under be distilled off remain fused salt.
Described target substance A is one or more in Si, B, Ga, Al, Ge, Sn, Sb, Bi, Te.
In step (1) and step (2) high-temperature full sealed Ag/AgCl electrodes are adopted for reference electrode;During cathodic polarization, electricity
Gesture is 0.01-0.2V relative to the evolution or deposition potential of metal M;During anode polarization, potential is 0.5- relative to the evolution or deposition potential of metal M
2.5V。
Step (1) and step (2) adopt galvanostatic polarization mode;Polarization current 0.1-5A/g;Polarization electricity reaches conjunction
It is more than aurification theory desired volume.
The inventive principle of the present invention is as follows:
The present invention, as working electrode, makes the ion of metal M exist using fine and close target substance A using the method for electrochemistry
Reduce on target substance A, so as to generate the alloy of target substance A and metal M, the target substance A for making densification occurs volumetric expansion,
Then using alloy as anode, the dissolution from alloy by metal M leaves nano pore, so as to be received in final product
The target substance A of meter Duo Kong.When the present invention adopts fused-salt medium for electrolyte, the porous process phase of the target substance A of densification
When the process that target substance A is transferred to again in fused salt from target substance A is transferred to from fused salt in the ion of M.And, when adopting
During with metal M or its alloy as to electrode, then as the target substance A of the into/out densification of the ion of metal M, to electricity
Extremely go up and just happens is that the ion of metal M leaves/return to metal M or its alloy.Therefore using of the invention by fine and close mesh
Mark substance A becomes after the target substance A of nanoporous, fused-salt medium and electrode substantially can be restored completely, therefore is one
Plant production procedure short, pollution is few, process is simple, it is easy to quantity-produced low-cost technologies.
When the present invention carries out target substance A porous, the loss of target substance A is not resulted in, this and traditional hydrofluoric acid
Solution etches silicon is essentially different, and the latter is by consuming silicon come pore-creating thus discharge is serious;With traditional magnesium vapor technology phase
Than the technology of the present invention does not consume or consume on a small quantity active metal, and the subsequent treatment problem without magnesia substantially;With dioxy
SiClx electrolysis is compared, because there is no the kinetic difficulty of silica dielectric process in the technology of the present invention, thus can be more
Carry out under low temperature, the nano-structure porous silicon smaller so as to obtain primary partical.It can be seen that the present invention is compared to existing document report
Road technology is respectively provided with significant advantage.And, the present invention extend to other ii IA-VA race solid metallics it is either nonmetallic or
Its alloy.
The present invention can prepare the porous layer of controllable thickness by controlling electricity in fine and close silicon face, naturally it is also possible to will
Silicon chip, silico briquette and silica flour etc. are completely transformed into nano-structure porous silicon, therefore compare conventional method, and controllability is very good.Institute of the present invention
The nanoporous silica flour of preparation is highly uniform, can be used as high performance lithium ionic cell cathode material.It is suitable for will cause
Close B, Ga, Al, Ge, Sn, Sb, Bi, Te simple substance or its alloy is changed into nano-porous materials.
The present invention using alkali metal or alkaline-earth metal M or its alloy as to electrode, with the molten chloride of metal M or it is mixed
Conjunction fused salt is electrolyte, and metal M is transformed into into the nano-porous materials of target substance A through cathodic polarization/anode polarization circulation.
In cathodic polarization, because the alloying process of M and A is spontaneous, therefore, negative electrode M constitutes galvanic cell with anode A, now, control
Voltage between negative electrode processed and anode, such as 0-1.2V, can control alloying speed, and electricity now can be also externally provided in principle
Energy.Can apply the voltage of a negative sense, it is preferable that -0.8-0V sometimes for ohmmic drop, solid liquid phase diffusion resistance is overcome.
In subsequent process of anodic polarization, then have to provide external energy, it is preferable that in working electrode and to applying between electrode
The voltage of 0.5-2.5V.
The nanoporous of target substance A can also be carried out using three-electrode system, such as, and can be using such as patent CN
200420017446.7 disclosed high-temperature full sealed Ag/AgCl reference electrodes, the reference electrode can be in various chlorides
Steady operation in fused salt and its mixed salt, can for a long time, repeated multiple timesly be used.During cathodic polarization, it is preferable that by potential control
Working electrode is higher by 0.01-1.2V relative to the evolution or deposition potential of metal M;During anode polarization, it is preferable that control work potential is relative
0.5-2.5V is higher by the evolution or deposition potential of metal M.With this understanding, can be using graphite and other solid metallic anodes.
Nanoporous can also be carried out to target substance A in the form of constant current, it is preferred that step (1) negative electrode pole
Galvanic current density and step (2) Anodic polarization current density are 0.1A/g-5A/g.Constant current mode is particularly advantageous in nano surface
The preparation of porous layer, can be by control reaction time (polarize electricity) come the thickness of control surface porous layer.When preparation body phase
During nano-porous materials, electricity is set to reach more than alloying theory institute subfam. Spiraeoideae.
For nanoporous powder body material is prepared, the fine and close powder body material of target substance A is adopted for raw material, now, first will
Raw material is prepared into formed body and reserved certain porosity, the volumetric expansion that not only available buffer alloying process is brought, can be with
Promote solid liquid phase diffusion.Preferably, the volume of the powder compacts of target substance A is fine and close more than after target substance A and M alloyings
The volume of state.Target substance A and its but its density is calculated with the volume of the fine and close state of the alloy of M, therefore, A densification powders
The minimum porosity of formed body can calculate acquisition.The solid constituent of fused salt can be added in shaping reserving porosity, the latter
To melt in fused salt, so as to form ion channel in the electrodes.Sometimes some inert substance powders, such as metal powder can be added
End and carbon dust etc., to increase electrode conductivuty, or are conducive to target substance to disperse, and now can first deduct when porosity is calculated
The volume of this portions additive.
Also first target substance A and metal M can be prepared into the alloy of M-A by chemical reaction, then with M-A alloys as sun
Pole, with the simple substance or alloy of metal M, or solid-state conductive metallic nickel, iron, titanium, molybdenum, tungsten etc. are negative electrode, and energization makes the M in negative electrode
Dissolution obtains nanoporous A, makes negative electrode that the deposition of M to occur, and the latter can be re-used for preparing alloy with fine and close A, so as to realize following
Ring is utilized.
After the completion of nanoporous, working electrode takes out from fused salt, by the fused-salt medium containing a small amount of body in porous body,
Washing is removed in water, diluted acid after can cooling down, then conventional or vacuum drying;Also can be gone by organic solvent washing if necessary
Remove.Further, since alkali metal, alkaline-earth halide fused salt are easy to volatilization, therefore also can be in inert atmosphere or vacuum condition
Under, removed by heating evaporation, can also avoid the reaction of prepared nano-porous materials and water.
Description of the drawings
Fig. 1 is the TEM figures of densification silicon grain before reaction in the embodiment of the present invention 1.
Fig. 2 is the TEM figures that nanoporous silica flour is obtained in the embodiment of the present invention 1 after reaction.
Fig. 3 is the XRD of the nanoporous silica flour prepared in the embodiment of the present invention 2.
Fig. 4 is the SEM figures of the nanoporous silica flour prepared in the embodiment of the present invention 3.
Fig. 5 is the cycle performance figure that the nanoporous silica flour prepared in the embodiment of the present invention 3 is used as lithium cell negative pole material.
Fig. 6 is the cycle performance figure that the nano-silicone wire/carbon material prepared in the embodiment of the present invention 5 is used as lithium cell negative pole.
Fig. 7 is the cycle performance figure that the silicon power raw material of the embodiment of the present invention 3 is used as lithium cell negative pole material.
Specific embodiment
Below in conjunction with drawings and Examples, the present invention is described further.It is further right that these descriptions are intended merely to
The present invention is illustrated, rather than is limited the invention.Mainly using negative electrode and anode to reality in following embodiment descriptions
The process that border occurs carries out scientific description, it should be pointed out that for the target electrode of the present invention, silicon, antimony, germanium such as in embodiment
Tin alloy etc., working electrode as mentioned above, and the metal electrode such as matching Ca, Li is to electrode.
Embodiment 1
(1) the fine and close Si powder that 1g particle diameters are 3 μm or so is prepared into into the porous test piece that porosity is 70% or so, uses molybdenum
Net is compound to porous test piece on molybdenum bar collector as negative electrode.With fused salt (CaCl2+ NaCl) as medium, with calcium metal work
For anode, it is 0.2V that voltage between negative electrode and anode is controlled at 550 DEG C, maintains more than 350min, makes Si and Ca reactions, is formed
Calcium silicon.
(2) with calcium silicon as anode, calcium metal as negative electrode, 550 DEG C of fused salt (CaCl2+ NaCl) be medium, 550 DEG C
Apply the voltage of -2.2V between a cathode and an anode, react 120min, make the Ca dissolutions in calcium silicon.
(3) electrode is taken out from fused salt, room temperature is cooled to, is vacuum dried after washing, the elementary particle size for obtaining is 20nm
The nanometer body phase porous silicon powder of left and right.The TEM pictures of silicon as shown in Figure 1 and Figure 2, can substantially observe densification before and after reaction
Silicon grain becomes loose porous silicon grain after reaction.
Embodiment 2
(1) the fine and close Si powder that 1g particle diameters are 2 μm or so is prepared into the porous test piece of porosity 70% or so, molybdenum net is used
Porous test piece is compound on molybdenum bar collector as negative electrode.With fused salt (MgCl2+ NaCl+KCl) it is medium, be with magnesium metal
Anode, at 500 DEG C negative electrode and more than anode in short circuit 350min are made, and make Si and Mg reactions, form mg-si master alloy.
(2) with mg-si master alloy as anode, magnesium metal as negative electrode, 500 DEG C of fused salt (MgCl2+ NaCl+KCl) it is medium,
Apply voltage response 150min of -1.5V between negative electrode and anode, make the Mg dissolutions in mg-si master alloy.
(3) electrode is taken out from fused salt, room temperature is cooled to, is vacuum dried after washing, obtain nanoporous silica flour, its XRD
As shown in figure 3, obtaining the nanometer body phase porous silicon powder particle of elementary particle size 20nm or so.
Embodiment 3
(1) by fine and close Si powder that 1g particle diameters are 1 μm or so and 0.5g CaCl2It is well mixed, makes porous test piece, uses
Molybdenum net is compound to porous test piece on molybdenum bar collector as negative electrode, and negative electrode is immersed into fused salt (CaCl2+ NaCl) in 30min, make
CaCl in porous test piece2In dissolving in fused salt, with calcium metal (20g or so) as anode, make between negative electrode and anode at 600 DEG C
Apply the voltage of -0.2V, maintain 250min, make Si and Ca reactions, form calcium silicon.
(2) with calcium silicon as anode, calcium metal as negative electrode, 600 DEG C of fused salt (CaCl2+ NaCl) it is medium, in negative electrode
Apply the voltage of -1.8V and between anode, maintain 120min, make the Ca dissolutions in calcium silicon.
(3) electrode is taken out from fused salt, room temperature is cooled to, is vacuum dried after washing, it is receiving for 20min to obtain basic particle diameter
Meter Ti Xiang porous silicon powders, its SEM figure is as shown in Figure 4.
Nanometer body phase porous silicon powder prepared by the embodiment is used as lithium cell negative pole material, and its cycle performance is as shown in Figure 5.
The raw material silica flour of the present embodiment is tested as lithium cell negative pole material, as a result as shown in Figure 7, it is seen that substantially without cyclicity
Energy.
Embodiment 4
(1) silicon chip of long 1cm, width 1cm, thickness 2mm is fixed on tungsten bar collector as negative electrode.In fused salt (MgCl2+
NaCl+KCl in), with magnesium metal (5g) as anode, the voltage 10min for applying 0.1V between negative electrode and anode is made at 550 DEG C,
Make by cathodic polarization electricity 35C/cm2, the silicon layer for making the μ m-thick of silicon chip surface about 10 reacts, in silicon chip surface generation about 30
μ m-thick Si-Mg alloy.
(2) silicon chip using surface obtained in step (1) with Si-Mg alloy is used as anode, with magnesium metal as negative electrode, 550 DEG C
Fused salt (MgCl2+ NaCl+KCl) it is medium, -1.8V voltages are applied between a cathode and an anode, 10min is maintained, make silicon chip table
Mg dissolutions in the mg-si master alloy in face.
(3) electrode is taken out from fused salt, room temperature is cooled to, is vacuum dried after washing, in silicon chip surface the μ of thickness about 30 is obtained
The Nanosurface phase porous silicon layer of m.
Embodiment 5
(1) by fine and close silica flour that 1g particle diameters are 0.5 μm or so and 0.5g graphite powder ball milling mixings, it is prepared into porosity 50%
The test piece of the graphite powder coated Si of left and right, is compound to test piece on molybdenum bar collector as negative electrode with molybdenum net.In 550 DEG C of fused salt
(MgCl2+ NaCl+KCl) in, with magnesium metal (5g) as anode, the voltage of 0.2V is applied between negative electrode and anode, maintain
300min, makes Si and Mg reactions generate mg-si master alloy, so as to obtain the mixture of carbon and mg-si master alloy.
(2) with the mixture of carbon and mg-si master alloy as anode, magnesium metal as negative electrode, 550 DEG C of fused salt (MgCl2+NaCl+
KCl it is) medium, the voltage of -1.4V is applied between negative electrode and anode, maintain reaction 150min, makes the Mg in magnesium silicon-carbon alloy molten
Go out.
(3) electrode is taken out from fused salt, room temperature is cooled to, after washing be vacuum dried, obtain nanometer body phase porous silicon powder with
The elementary particle size of the compound of carbon, wherein silica flour is 20nm or so.
The compound of nanometer body phase porous silicon powder manufactured in the present embodiment and carbon is used as into lithium cell negative pole material, is shown good
Good cyclical stability, its cycle performance is as shown in Figure 6.
Embodiment 6
(1) the fine and close silica flour that 1g particle diameters are 1 μm or so is prepared into into the porous test piece that porosity is 70% or so, uses molybdenum net
Porous test piece is compound on molybdenum bar collector as negative electrode.With fused salt (CaF2+ KF) it is medium, with calcium metal (20 grams or so)
For anode, negative electrode and more than anode in short circuit 300min are made at 850 DEG C, make Si and Ca reactions, generate calcium silicon.
(2) with calcium silicon as anode, calcium metal as negative electrode, 850 DEG C of fused salt (CaF2+ KF) be medium, in negative electrode and
Apply the voltage of -1.7V between anode, maintain reaction 200min, make the Ca dissolutions in calcium silicon.
(3) electrode is taken out from fused salt, room temperature is cooled to, is vacuum dried after washing, obtain a nanometer body phase porous silicon powder.
Embodiment 7
(1) the fine and close Si powder that 1g particle diameters are 0.3 μm or so is prepared into the porous test piece of porosity 70% or so, molybdenum is used
Net is compound to porous test piece on molybdenum bar collector as negative electrode.With fused salt (MgF2+MgCl2) it is medium, with magnesium silver alloy (matter
Amount compares 1:2;30 grams or so) it is anode, apply the voltage of -0.7V between a cathode and an anode at 700 DEG C, 300min is maintained, make
Si and Mg react into mg-si master alloy.
(2) with mg-si master alloy as anode, magnesium silver alloy as negative electrode, 700 DEG C of fused salt (MgF2+MgCl2) it is medium, in the moon
Apply the voltage of -1.0V between pole and anode, maintain 200min, make the Mg dissolutions in mg-si master alloy.
(3) electrode is taken out from fused salt, room temperature is cooled to, is vacuum dried after washing, obtain elementary particle size for 30nm
The nanometer body phase porous silicon powder of left and right.
Embodiment 8
(1) 1g densification silicon boron compound powder is prepared into into the porous test piece that porosity is 75% or so, will be many with tungsten net
It is negative electrode that hole test piece is compound on tungsten bar collector.With fused salt (CaCl2+ NaCl) it is medium, with (20 grams or so) works of calcium metal
For anode, anode and cathode short circuit more than 400min is made at 700 DEG C, make silicon boron alloy react into calcium silicon boron alloy with Ca.
(2) with calcium silicon boron alloy as anode, calcium metal as negative electrode, 700 DEG C of fused salt (CaCl2+ NaCl) it is medium, in the moon
Apply the voltage of -1.7V between pole and anode, maintain 200min, make the Ca dissolutions in calcium silicon boron alloy.
(3) electrode is taken out from fused salt, room temperature is cooled to, is vacuum dried after washing, obtained nanometer body phase porous silicon boron and answer
Compound powder.
Embodiment 9
(1) the fine and close aluminium-antimony alloy powder that 3g particle diameters are 2 μm or so is prepared into into the porous examination that porosity is 75% or so
Piece, is compound to porous test piece on tungsten bar collector as negative electrode with tungsten net.With fused salt (CaCl2+ NaCl) it is medium, with calcium gold
(20 grams or so) of category is anode, and at 600 DEG C negative electrode and more than anode in short circuit 400min are made, and makes aluminium-antimony alloy react into the conjunction of calcium aluminium antimony
Gold.
(2) with calcium aluminium-antimony alloy as anode, calcium metal as negative electrode, 600 DEG C of fused salt (CaCl2+ NaCl) it is medium, in the moon
Apply the voltage of -1.7V between pole and anode, maintain 200min, make the Ca dissolutions in calcium aluminium-antimony alloy.
(3) electrode is taken out from fused salt, room temperature is cooled to, is vacuum dried after washing, obtained nanometer body phase porous aluminum antimony and close
Bronze.
Embodiment 10
The fine and close antimony powder end that 1g particle diameters are 1 μm or so is prepared into into the porous test piece that porosity is 60% or so, molybdenum net is used
Porous test piece is compound on molybdenum bar collector as negative electrode.With fused salt (LiBr+KBr) as electrolyte, with metal Li as anode,
Negative electrode and more than anode in short circuit 300min are made at 400 DEG C, lithium antimony alloy is generated;
(2) with lithium antimony alloy as anode, metal Li as negative electrode, 400 DEG C of fused salt (LiBr+KBr) as electrolyte, in negative electrode
Apply the voltage of -1.5V and anode between, maintain 200min, make the Li dissolutions in lithium antimony alloy.
(3) electrode is taken out from fused salt, room temperature is cooled to, is vacuum dried after washing, obtain a nanometer body phase porous antimony powder.
Embodiment 11
(1) the fine and close germanium tin alloy powder that 0.5g particle diameters are 2 μm or so is prepared into into the porous that porosity is 60% or so
Test piece, is compound to porous test piece on tungsten bar collector as negative electrode with tungsten net.With fused salt (MgCl2+ NaCl+KCl) it is electrolysis
Matter, with magnesium metal as anode, at 450 DEG C negative electrode and more than anode in short circuit 350min is made, and makes generation magnesium germanium tin alloy.
(2) with magnesium germanium tin alloy as anode, magnesium metal as negative electrode, 450 DEG C of fused salt (MgCl2+ NaCl+KCl) it is electrolysis
Matter, applies between a cathode and an anode the voltage of -1.5V, maintains 200min, makes the Mg dissolutions in magnesium germanium tin alloy.
(3) electrode is taken out from fused salt, room temperature is cooled to, is vacuum dried after washing, obtain elementary particle size for 40nm
The nanometer body phase porous germanium tin alloy powder of left and right.
Embodiment 12
(1) negative electrode is done with the molybdenum sheet of 2cm*2cm, graphite is anode, fused salt (MgCl2+ NaCl+KCl) it is electrolyte,
Make to apply -2.8V voltages between anode and cathode under the conditions of 600 DEG C, 10g magnesium metals are deposited on molybdenum sheet, be prepared into metal magnesium electrode;
The micron-sized fine and close Si powders of 1g are prepared into into the porous test piece that porosity is 70% or so, are compound to porous test piece with molybdenum net
As negative electrode on molybdenum bar collector, using above-mentioned metal magnesium electrode as anode, with 600 DEG C of fused salt (MgCl2+ NaCl+KCl) be
Electrolyte, applies the voltage of 0.1V between anode and cathode, maintains more than 300min, generates mg-si master alloy.
(2) with mg-si master alloy as anode, metal magnesium electrode as negative electrode, 600 DEG C of fused salt (MgCl2+ NaCl+KCl) it is electricity
Xie Zhi, applies between a cathode and an anode the voltage of -1.5V, maintains 200min, makes the Mg dissolutions in mg-si master alloy.
(3) electrode is taken out from fused salt, room temperature is cooled to, is vacuum dried after washing, obtain elementary particle size for 20nm
The nanometer body phase porous silicon powder of left and right.
Embodiment 13
(1) the micron-sized fine and close Si powders of 1g are prepared into into the porous test piece that porosity is 70% or so, will be many with molybdenum net
It is negative electrode that hole test piece is compound on molybdenum bar collector, with graphite as anode, with fused salt (MgCl2+ NaCl+KCl) make electrolyte,
The voltage for applying -2.45V between negative electrode and anode is made under the conditions of 600 DEG C, makes to generate Si-Mg alloy on negative electrode.
(2) with mg-si master alloy as anode, with metallic nickel plate electrode as negative electrode, with 600 DEG C of fused salt (MgCl2+NaCl+
KCl) electrolyte is made, -1.5V voltages are applied between anode and cathode carries out reaction 200min, makes the Mg dissolutions in mg-si master alloy.
(3) electrode is taken out from fused-salt medium, room temperature is cooled to, is vacuum dried after washing, obtaining elementary particle size is
The nanometer body phase porous silicon powder of 20nm or so.
Embodiment 14
(1) the fine and close Si powder that 1g particle diameters are 5 μm or so is prepared into the porous test piece of porosity 70% or so, molybdenum net is used
Porous test piece is compound on molybdenum bar collector as negative electrode.With fused salt (MgCl2+ NaCl+KCl) it is electrolyte, with magnesium metal
For anode, anode and cathode short circuit 200min is made at 500 DEG C, make pasc reaction into mg-si master alloy.
(2) with mg-si master alloy as anode, magnesium metal as negative electrode, 500 DEG C of fused salt (MgCl2+ NaCl+KCl) it is electrolyte,
Apply the voltage of -1.5V between a cathode and an anode, maintain 120min, make the Mg dissolutions in mg-si master alloy.
(3) step (1) and step (2) repeated three times successively, electrode is then taken out from fused salt, be cooled to room
Temperature, is vacuum dried after washing, obtains the nanometer body phase porous silicon powder that elementary particle size is 20nm or so.
Embodiment 15
(1) the fine and close Si powder that 1g particle diameters are 2 μm or so is prepared into into the porous test piece that porosity is 70% or so, uses molybdenum
Net is compound to porous test piece on molybdenum bar collector as negative electrode.With fused salt (MgCl2+ NaCl+KCl) it is medium, with magnesium metal
For anode, negative electrode and more than anode in short circuit 300min are made at 600 DEG C, make pasc reaction into mg-si master alloy.
(2) with mg-si master alloy as anode, magnesium metal as negative electrode, 600 DEG C of fused salt (MgCl2+ NaCl+KCl) it is medium,
Applying -1.5V voltages between anode and cathode carries out reaction 120min, makes the Mg dissolutions in mg-si master alloy.
(3) electrode is taken out from fused salt, then vacuum distillation removes the salinity remained in electrode under the conditions of 650 DEG C,
Obtain the nanometer body phase porous silicon powder that elementary particle size is about 30nm.
Embodiment 16
(1) by after fine and close silica flour that 1g particle diameters are 0.5 μm or so and 0.5g graphite powder ball milling mixings, then with 1.8g magnesium metals
Mixed pressuring plate, the reaction in 700 DEG C of inert atmospheres prepares the mixture for generating graphite and mg-si master alloy.
(2) mixture of above-mentioned graphite and mg-si master alloy is pressed into into test piece of the porosity less than 30%, it is compound with molybdenum net
It is negative electrode, 520 DEG C of fused salt (MgCl with metal molybdenum on molybdenum bar collector as anode2+ NaCl+KCl) it is medium, in the moon
Apply the voltage of -1.4V between pole and anode, maintain reaction 150min, make the Mg dissolutions in mg-si master alloy.
(3) electrode is taken out from fused salt, room temperature is cooled to, after washing be vacuum dried, obtain nanometer body phase porous silicon powder with
The elementary particle size of the compound of carbon, wherein silica flour is 20nm or so.
Embodiment 17
(1) in 0.5g graphene oxides being dispersed in into water and ethanol, in the silica flour stirring for adding 1g particle diameters to be 0.5 μm or so
After mixing, drying, the test piece of the graphite oxide coated Si of porosity 40% or so is prepared into, after being heat-treated 2 hours at 250 DEG C,
Test piece is compound on molybdenum bar collector as negative electrode with molybdenum net.In 550 DEG C of fused salt (MgCl2+ NaCl+KCl) in, with magnesium gold
Category (5g) is anode, and the voltage of 0.2V is applied between negative electrode and anode, maintains 300min, makes Si and Mg reactions, generates magnesium silicon and closes
Gold, obtains the mixture of carbon and mg-si master alloy.
(2) mixture of above-mentioned graphite and mg-si master alloy is pressed into into test piece of the porosity less than 30%, it is compound with molybdenum net
It is negative electrode, 520 DEG C of fused salt (MgCl with metal molybdenum on molybdenum bar collector as anode2+ NaCl+KCl) it is medium, in the moon
Apply the voltage of -1.4V between pole and anode, maintain reaction 150min, make the Mg dissolutions in mg-si master alloy.
(3) electrode is taken out from fused salt, room temperature is cooled to, after washing be vacuum dried, obtain nanometer body phase porous silicon powder with
The elementary particle size of the compound of carbon, wherein silica flour is 20nm or so.
Embodiment 18
(1) the micron-sized fine and close Si powders of 1g are prepared into into the porous test piece that porosity is 70% or so, will be many with molybdenum net
It is negative electrode that hole test piece is compound on molybdenum bar collector, with graphite as anode, with fused salt (MgCl2+ NaCl+KCl) make electrolyte, adopt
With the high-temperature full sealed Ag/AgCl reference electrodes as disclosed in patent CN 200420017446.7 be reference (potential relative to
Metal Mg evolution or deposition potentials are 1.5V), cathode potential is controlled under the conditions of 600 DEG C relative to Mg evolution or deposition potential 0.01-0.15V, make
Mg-si master alloy is generated on negative electrode.
(2) with mg-si master alloy as anode, with metallic nickel plate electrode as negative electrode, with 600 DEG C of fused salt (MgCl2+NaCl+
KCl) make electrolyte, adopt high-temperature full sealed Ag/AgCl reference electrodes as disclosed in patent CN 200420017446.7 for
Reference (potential is 1.5V relative to metal Mg evolution or deposition potentials), anode potential control is entered relative to Mg evolution or deposition potential 0.8-1.5V
Row reaction 200-400min, makes the Mg dissolutions in mg-si master alloy.
(3) electrode is taken out from fused-salt medium, room temperature is cooled to, is vacuum dried after washing, obtaining elementary particle size is
The nanometer body phase porous silicon powder of 20nm or so.
Embodiment 19
(1) the p-doped silicon chip of long 1cm, width 1cm, thickness 1mm is fixed on tungsten bar collector as negative electrode.In fused salt
(MgCl2+ NaCl+KCl) in, with magnesium metal (5g) as anode, at 550 DEG C with constant current 0.1A difference cathodic polarization 6min,
12min or 5h, can make silicon chip surface generate about 30 μm, 60 μ m-thick mg-si master alloy or by the silicon chip become completely magnesium silicon close
Gold.
(2) silicon chip using surface obtained in step (1) with mg-si master alloy is used as anode, with magnesium metal as negative electrode, 550 DEG C
Fused salt (MgCl2+ NaCl+KCl) it is medium, anode polarization 8min, 15min or 310min are distinguished with constant current 0.1A, make
Mg dissolutions in mg-si master alloy.
(3) electrode is taken out from fused salt, room temperature is cooled to, is vacuum dried after washing, obtain thickness in silicon chip surface respectively
About 30 μm, 60 μm of Nanosurface phase porous silicon layer, or obtain body phase nano-structure porous silicon.
Embodiment 20
(1) the fine and close Si powder that 3g particle diameters are 2 μm or so is prepared into into the porous test piece that porosity is 80% or so, uses tungsten
Net is compound to porous test piece on tungsten bar collector as negative electrode.With fused salt (CaCl2+ NaCl) it is medium, with (20 grams of calcium metal
Left and right) it is anode, cathodic polarization is carried out with constant current 3A/g at 600 DEG C, make by polarizing electricity to generate Ca2Needed for Si is theoretical
Capacity 110%, makes generation calcium silicon.
(2) with calcium silicon as anode, calcium metal as negative electrode, 600 DEG C of fused salt (CaCl2+ NaCl) it is medium, in negative electrode
Apply the voltage of -1.7V and anode between, maintain 200min, make the Ca dissolutions in calcium silicon.
(3) electrode is taken out from fused salt, room temperature is cooled to, is vacuum dried after washing, obtained nanometer body phase porous aluminum antimony and close
Bronze.
Claims (9)
1. a kind of method that dense material is prepared into into nano-porous materials, it is characterised in that comprise the following steps:
(1) (i) using the target substance A of solid-state as negative electrode, using the fused salt containing metal M halide as medium, in 300-950
Cathodic polarization is carried out under the conditions of DEG C, makes metal M and target substance A that alloying reaction to occur, obtain M-A alloys;Or (ii) is logical
The DIRECT ALLOYING for crossing metal M and target substance A is reacted, and obtains M-A alloys;
Described target substance A is one or more in ii IA-VIA race element;
Described negative electrode is the dense material of target substance A or the porous former of dense powder shape target substance A;
Described metal M is alkaline-earth metal or alkali metal, and described fused salt is alkaline-earth halide fused salt or alkali metal halogenation
Thing fused salt;
(2) using the M-A alloys obtained by step (1) as anode, using the fused salt containing metal M halide as medium, in 300-
Anode polarization is carried out under the conditions of 950 DEG C, the metal M dissolutions in M-A alloys are made;
(3) step (1) and step (2) are repeated in several times, target electrode is taken out, residual fused salt is removed, target substance A is obtained
Nano-porous materials.
2. the method that dense material is prepared into into nano-porous materials according to claim 1, it is characterised in that:
In step (1), by target substance A:A () is directly as electrode;B () is fixed in net made by solid-state conductive metal or basket
As electrode;Or (c) is compounded on solid-state conductive metal as electrode;
Anode in step (1) for metal M simple substance or alloy, control during cathodic polarization voltage between negative electrode and anode be-
0.8-1.2V;Or the anode in step (1) is graphite, precipitation electricity of the cathode potential relative to metal M is controlled during cathodic polarization
Gesture is higher by 0.01-1.2V;
Negative electrode in step (2) for metal M simple substance or alloy, or for solid-state conductive metal, when M-A alloy anodes are polarized,
Apply the voltage of 0.5-2.5V between anode and negative electrode;
Described solid-state conductive metal is the alloy of one or more in nickel, iron, titanium, molybdenum, tungsten.
3. the method that dense material is prepared into into nano-porous materials according to claim 1, it is characterised in that:Step
(1) in, the porous former of described dense powder shape target substance A is obtained by following preparation method:By dense powder shape
Target substance A directly or after mixing with additive is prepared into porous body, and described additive is conductive metal powder, carbon materials feed powder
The solid constituent of the last or fused-salt medium;The dense material of described target substance A is sheet, block or bar-shaped object
Matter A.
4. the method that dense material is prepared into into nano-porous materials according to claim 3, it is characterised in that:Step
(1) in, the porous former of described dense powder shape target substance A is silica flour, silicon boron compound powder, silicon phosphorus compound powder
End, aluminium-antimony alloy powder, antimony powder end, germanium tin alloy powder, CaCl2One kind in porous body made by-silicon mixed-powder, it is described
Target substance A dense material be silicon chip;Described additive is graphite powder, Graphene powder or graphene oxide powder.
5. according to the method that dense material is prepared into nano-porous materials described in claim 1, it is characterised in that:Step
(1) in, described metal M is the one kind in Mg, Ca, Li.
6. the method that dense material is prepared into into nano-porous materials according to claim 1, it is characterised in that:Step
(3) in, the mode for removing residual fused salt is:A () removes residual fused salt by washing or pickling;Or (b) inert atmosphere or vacuum
Under the conditions of be distilled off remain fused salt.
7. the method that dense material is prepared into into nano-porous materials according to claim 1, it is characterised in that:Described
Target substance A is one or more in Si, B, Ga, Al, Ge, Sn, Sb, Bi, Te.
8. the method that dense material is prepared into into nano-porous materials according to claim 1, it is characterised in that:Step
(1) and in step (2) high-temperature full sealed Ag/AgCl electrodes are adopted for reference electrode;During cathodic polarization, reference electrode potential phase
Evolution or deposition potential for metal M is 0.01-0.2V;During anode polarization, reference electrode potential is relative to the evolution or deposition potential of metal M
0.5-2.5V。
9. the method that dense material is prepared into into nano-porous materials according to claim 1, it is characterised in that:Step
(1) and step (2) adopt galvanostatic polarization mode;Polarization current 0.1-5A/g;It is theoretical required that polarization electricity reaches alloying
It is more than capacity.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201611129196.XA CN106591891B (en) | 2016-12-09 | 2016-12-09 | A method of dense material is prepared into nano-porous materials |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201611129196.XA CN106591891B (en) | 2016-12-09 | 2016-12-09 | A method of dense material is prepared into nano-porous materials |
Publications (2)
Publication Number | Publication Date |
---|---|
CN106591891A true CN106591891A (en) | 2017-04-26 |
CN106591891B CN106591891B (en) | 2018-10-09 |
Family
ID=58597966
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201611129196.XA Active CN106591891B (en) | 2016-12-09 | 2016-12-09 | A method of dense material is prepared into nano-porous materials |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN106591891B (en) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN109037011A (en) * | 2018-09-20 | 2018-12-18 | 长沙恒扬电子有限公司 | A kind of audio electronics pipe with composite anode |
CN109763134A (en) * | 2018-12-27 | 2019-05-17 | 国联汽车动力电池研究院有限责任公司 | The preparation method of porous silicon |
CN110459769A (en) * | 2019-07-17 | 2019-11-15 | 武汉大学 | A kind of silicon-carbon solid sols, preparation method and the application of high dispersive |
CN117230459A (en) * | 2023-11-13 | 2023-12-15 | 中国科学院广州地球化学研究所 | In-situ preparation method and device of silicon-based nano-micron material |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2006321688A (en) * | 2005-05-19 | 2006-11-30 | Kyoto Univ | Method for manufacturing silicon |
WO2012165017A1 (en) * | 2011-05-30 | 2012-12-06 | 国立大学法人京都大学 | Process for producing silicon |
CN105347347A (en) * | 2015-12-08 | 2016-02-24 | 华中科技大学 | Method for preparing three-dimensional porous nanometer silicon at low temperature through molten-salt growth method |
CN105399100A (en) * | 2015-12-14 | 2016-03-16 | 东南大学 | Preparation method for nanoporous silicon |
CN105603465A (en) * | 2016-01-13 | 2016-05-25 | 武汉大学 | Method for electrochemically preparing nano porous silver-based metal catalysts |
-
2016
- 2016-12-09 CN CN201611129196.XA patent/CN106591891B/en active Active
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2006321688A (en) * | 2005-05-19 | 2006-11-30 | Kyoto Univ | Method for manufacturing silicon |
WO2012165017A1 (en) * | 2011-05-30 | 2012-12-06 | 国立大学法人京都大学 | Process for producing silicon |
CN105347347A (en) * | 2015-12-08 | 2016-02-24 | 华中科技大学 | Method for preparing three-dimensional porous nanometer silicon at low temperature through molten-salt growth method |
CN105399100A (en) * | 2015-12-14 | 2016-03-16 | 东南大学 | Preparation method for nanoporous silicon |
CN105603465A (en) * | 2016-01-13 | 2016-05-25 | 武汉大学 | Method for electrochemically preparing nano porous silver-based metal catalysts |
Non-Patent Citations (9)
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN109037011A (en) * | 2018-09-20 | 2018-12-18 | 长沙恒扬电子有限公司 | A kind of audio electronics pipe with composite anode |
CN109763134A (en) * | 2018-12-27 | 2019-05-17 | 国联汽车动力电池研究院有限责任公司 | The preparation method of porous silicon |
CN110459769A (en) * | 2019-07-17 | 2019-11-15 | 武汉大学 | A kind of silicon-carbon solid sols, preparation method and the application of high dispersive |
WO2021008579A1 (en) * | 2019-07-17 | 2021-01-21 | 武汉大学 | Highly dispersed silicon-carbon composite material, preparation method therefor, and application thereof |
CN110459769B (en) * | 2019-07-17 | 2021-06-04 | 武汉大学 | High-dispersion silicon-carbon solid sol, preparation method and application thereof |
US11489164B2 (en) | 2019-07-17 | 2022-11-01 | Wuhan University | Highly dispersed silicon-carbon solid sol, preparation method and application thereof |
CN117230459A (en) * | 2023-11-13 | 2023-12-15 | 中国科学院广州地球化学研究所 | In-situ preparation method and device of silicon-based nano-micron material |
Also Published As
Publication number | Publication date |
---|---|
CN106591891B (en) | 2018-10-09 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
Zhao et al. | Review on the electrochemical extraction of lithium from seawater/brine | |
Yedluri et al. | Enhanced electrochemical performance of nanoplate nickel cobaltite (NiCo 2 O 4) supercapacitor applications | |
CN106591891B (en) | A method of dense material is prepared into nano-porous materials | |
Xiao et al. | Up-scalable and controllable electrolytic production of photo-responsive nanostructured silicon | |
Ding et al. | Mesoporous cobalt selenide/nitrogen-doped carbon hybrid as bifunctional electrocatalyst for hydrogen evolution and oxygen reduction reactions | |
CN105304958B (en) | A kind of production method of long-life lithium-sulphur cell positive electrode | |
CN110359068B (en) | Method for preparing carbon nanotube coated metal material based on molten salt electrochemical method | |
Chen et al. | Facile synthesis of Cu2O nanorod arrays on Cu foam as a self-supporting anode material for lithium ion batteries | |
CN105609749A (en) | Silicon nanowire and application thereof | |
CN101603182B (en) | Electrochemical method for removing oxygen from oxide M1O | |
Zhu et al. | Bimetallic Bi–Sn microspheres as high initial coulombic efficiency and long lifespan anodes for sodium-ion batteries | |
CN107910495A (en) | A kind of graphene-based lithium ion battery negative material and preparation method thereof | |
US11489164B2 (en) | Highly dispersed silicon-carbon solid sol, preparation method and application thereof | |
Zhou et al. | Construction of porous disc-like lithium manganate for rapid and selective electrochemical lithium extraction from brine | |
Wheatle et al. | Electrochemical generation of hexacyanoferrate and hexacyanoruthanate electroactive films at nickel electrode surfaces: A promising synthetic approach for new electrode materials in metal ion batteries and supercapacitors | |
Beknalkar et al. | Preparation of CuMn2O4/Ti3C2 MXene composite electrodes for supercapacitors with high energy density and study on their charge transfer kinetics | |
CN114318397A (en) | Molybdenum-based electrocatalyst, preparation method thereof, bifunctional electrolytic cell and application thereof | |
Yu et al. | Laser sintering of Al nanoparticles for Al-air batteries | |
Kim et al. | Electrochemical properties of micron-sized SnO anode using a glyme-based electrolyte for sodium-ion battery | |
RU2692759C1 (en) | Lead-carbon metal composite material for electrodes of lead-acid batteries and a method for synthesis thereof | |
Wu et al. | Recent progress on modification strategies of alloy-based anode materials for alkali-ion batteries | |
LI et al. | Electro-deposition behavior and proof-of-concept operation in methanesulfonic acid-based crude lead electro-refining | |
Chen et al. | Integrating preparation of borides and separation of alkaline-and rare-earth ions through an electrochemical alloying approach in molten salts | |
CN104831306A (en) | Ultrafine silicon-based alloy powder and electrochemical preparation method thereof | |
Xu et al. | Dealloying of modified Al-Si alloy to prepare porous silicon as Lithium-ion battery anode material |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant | ||
TR01 | Transfer of patent right | ||
TR01 | Transfer of patent right |
Effective date of registration: 20230731 Address after: Room 602, Building 1, Service Station 1, Jinyang Science and Technology Industrial Park, Changling Street, Guiyang National High tech Industrial Development Zone, Guiyang City, Guizhou Province, 550000 Patentee after: Guizhou Jiasi Energy Technology Co.,Ltd. Address before: 430072 Hubei Province, Wuhan city Wuchang District of Wuhan University Luojiashan Patentee before: WUHAN University |