CN108017057A - Tin-indium alloy coated Si magnesium granules prepare the method and silica flour of foam-like silica flour - Google Patents
Tin-indium alloy coated Si magnesium granules prepare the method and silica flour of foam-like silica flour Download PDFInfo
- Publication number
- CN108017057A CN108017057A CN201711272226.7A CN201711272226A CN108017057A CN 108017057 A CN108017057 A CN 108017057A CN 201711272226 A CN201711272226 A CN 201711272226A CN 108017057 A CN108017057 A CN 108017057A
- Authority
- CN
- China
- Prior art keywords
- powder
- tin
- indium
- silica flour
- alloy
- 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
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/02—Silicon
- C01B33/021—Preparation
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/16—Pore diameter
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Powder Metallurgy (AREA)
- Silicon Compounds (AREA)
Abstract
The invention discloses a kind of method that tin-indium alloy coated Si magnesium granules prepare foam-like silica flour, including：Prepared silicon magnesium alloy powder；Tin-indium alloy layer is coated on the surface of Si-Mg alloy powder；The Si-Mg alloy powder that tin-indium alloy layer will be coated with carries out solid-state diffusion heat treatment, to promote tin in clad and indium metal to be combined respectively with magnesium pasc reaction；Si-Mg alloy powder after solid-state diffusion is heat-treated carries out oxidation processes；And the Si-Mg alloy powder after oxidation processes is subjected to pickling and removes tin, indium and magnesium.It is less than the indium stannum alloy coated Si magnesium alloy particles of magnesium burning point by using not oxidizable, fusing point, it is that the present invention obtains the foam silica flour with microcellular structure with reference to the solid-state diffusion processing under certain temperature and hypoxemia oxidation processing technique, improves preparation efficiency and foam silica flour primary particle degree is smaller.
Description
Technical field
The present invention relates to the preparation method of foam-like silica flour, more particularly to a kind of tin-indium alloy coated Si magnesium granules to prepare bubble
The method of foam shape silica flour, further relates to a kind of foam-like silica flour using prepared by this method.
Background technology
Since silicon has theoretical specific capacity (4200mAh/g) of more than high ten times than graphite cathode, replaced using silicon present
Common graphite cathode has become the target of high-energy-density power battery research.Silicon has volumetric expansion in use as anode
Greatly, silicon grain rupture, dusting, first charge-discharge coulombic efficiency are low and the shortcomings that impedance is high；It is a series of for disadvantages mentioned above
Improved method has been found effective, the rupture of bulk silicon can be such as reduced using nanoscale silicon grain, using loose structure silicon
Grain can alleviate the volumetric expansion in charging process, and coated with carbon bed can then improve electric conductivity of silicon etc..In the studies above
As a result on the basis of, the preparation method for the porous silicon powder that nano silicon crystal is formed has become the research hotspot of battery material.
Preparing the method for nano silica fume has high-energy ball milling method, plasma heating vaporization condensation process, chemical method etc., wherein high
Can ball grinding method be applicable in generally, but it is time-consuming to prepare nano silica fume, and powder surface porosity is difficult to be formed；And plasma adds
Thermal evaporation condensation method equipment is complicated, though the nano-silicon primary particle sphericity as prepared by a kind of prior art is high, and it is this spherical
Nano-silicon is difficult to the after polymerization silicon grain for combining to form a large amount of gaps, is unfavorable for subsequent technique processing；Another existing skill
Pyrolysismethod in the silane plasma body of art, the nano silica fume specific surface area that it is manufactured is big, but using silane manufacture nano silica fume, it is former
Material cost is higher；On the other hand, a kind of chemical method prepares the technique of nano silica fume, and nano-silicon passes through hydrofluoric acid treatment titanium dioxide
Silicon is obtained with the mixture of silicon, its hydrofluoric acid used, there is highly corrosive, not easy to operate, and problem of environmental pollution is also difficult to solve.
The method for preparing porous silicon powder also has been reported that, such as a kind of silicon for having three-dimensional dendritic crackle using the preparation of liquid nitrogen chilling
Micro mist manufacture method, but silica flour prepared by this method has the shortcomings that silicon grain uniformity is poor；Such as one kind utilizes silicon, magnesium powder
The silicon magnesium compound method that pyrolytic obtains porous silicon again is synthesized, but stereoscan photograph disclosed in patent confirms this side
The primary particle of porous silicon prepared by method is larger, and it is in mass ratio 1: the 1 silicon/carbon Compound Negative prepared to utilize this porous silicon powder
There is the shortcomings that coulombic efficiency first (59%) same with metal silicium cathode is low in pole, low coulombic efficiency first and silica flour are once
The porous silicon powder that grain graininess is related therefore prepared by this method cannot solve application problem of the crystalline silicon as anode.And show
There is technology to disclose a kind of using silicon, magnesium powder synthesis Si-Mg alloy powder, Si-Mg alloy powder is immersed into a large amount of high temperature under helium protection
Kept the temperature in the bath of pure bismuth liquation, promote part magnesium to be dissolved in bismuth liquation, the powder of taking-up again by nitric acid acidwashing to remove bismuth and magnesium,
So as to obtain nano-structure porous silicon.The method is in the process of synthesis Si-Mg alloy powder, because using a large amount of magnesium powders, production process must
There must be such as helium protection of tight environmental Kuznets Curves means to reduce the risk of explosion of magnesium dust；And taken off in further bismuth liquation bath
Magnesium is handled, it is necessary to which the temperature of bismuth liquation is more than 450 DEG C, i.e., temperature is higher than about 150 DEG C of the burning point (300 DEG C) of magnesium, such temperature
Under magnesium easily ignition aoxidize, cause the high temperature spontaneous combustion of processed powder, so as to bring silicon grain rapidly to grow up and silicon
Oxidation, therefore industrialized production porous nano silica flour technique controlling difficulty is very big in this way, is particularly the grain of nano silica fume
Degree is unmanageable；The prior art is also disclosed one kind and decomposes silicon using metal chloride fused-salt medium long-time heat preservation (10h~15h)
Magnesium alloy powder, then the method by chlorohydric acid pickling acquisition porous silicon, this process eliminate the ignition of magnesium in industrialized production
Risk, but technological requirement long-time heat preservation, there are powder preparation efficiency it is low the problem of.
The content of the invention
In view of this, it is an object of the invention to provide a kind of tin-indium alloy coated Si magnesium granules to prepare foam-like silica flour
Method, and foam-like silica flour, to solve above-described at least part technical problem.
The first aspect of the present invention, there is provided a kind of method that tin-indium alloy coated Si magnesium granules prepare foam-like silica flour, bag
Include：
Prepared silicon magnesium alloy powder；
Tin-indium alloy layer is coated on the surface of Si-Mg alloy powder；
The Si-Mg alloy powder for being coated with tin-indium alloy layer is subjected to solid-state diffusion heat treatment, to promote the tin in clad
Combined respectively with magnesium pasc reaction with indium metal；
Si-Mg alloy powder after solid-state diffusion is heat-treated carries out oxidation processes；And
Si-Mg alloy powder after oxidation processes is subjected to pickling and removes tin, indium and magnesium.
Further, in the tin-indium alloy, the mass percent of tin is 10-60%.
Further, pickling further includes after removing tin, indium and magnesium：Ball milling and calcining in the medium of carbonaceous organic material
Forming surface has the foam silica flour of microcellular structure of carbonaceous conductive layer.
Further, the mode in the surface of Si-Mg alloy powder cladding tin-indium alloy layer is selected from one below：
Si-Mg alloy powder is mixed with metallic tin powder, the mixed-powder of indium powder or with tin-indium alloy powder, and using machinery
The mode of ball milling is coated；
Si-Mg alloy powder is mixed with metallic tin powder, the mixed powder of indium powder or with tin-indium alloy powder, is incorporated with after mixing
In the heat-treatment furnace of agitating device, by mechanical agitation and heat mixed powder and coated；And
Si-Mg alloy powder is mixed with metallic tin powder, the mixed powder of bismuth meal or with tin-indium alloy powder, and uses mechanical ball
The mode of mill realizes cladding；And the mixed powder after mechanical ball mill is incorporated with the heat-treatment furnace of agitating device, pass through machinery
Stir and heat mixed powder.
Further, the temperature of solid-state diffusion heat treatment is 200-500 DEG C.
Further, oxidation processes are carried out in the oxygen-nitrogen mixture body that oxygen content volume accounting is 5-20%, are aoxidized
The temperature of processing is 350-500 DEG C.
Further, the Si-Mg alloy powder by after oxidation processes, which carries out pickling removal tin, indium and magnesium, includes：Will
Si-Mg alloy powder after oxidation processes carries out pickling, and pickle is hydrochloric acid and/or nitric acid, miscellaneous to remove oxide and metal
Matter, then it is washed to neutral after drying original foam shape silica flour is made.
Further, ball milling and calcining specifically include in the medium of carbonaceous organic material：Original foam shape silica flour is existed
Ball milling is carried out in the medium of carbonaceous organic material, obtains slurry；And rear high-temperature calcination is dried in slurry, obtain carbon coating
Layer.
Further, the medium of the carbonaceous organic material is selected from following at least one：Pitch acetone soln, pitch tetrahydrochysene furan
Mutter solution, polyvinyl alcohol water solution and PI/NMP solution.
According to another aspect of the present invention, there is provided a kind of foam-like silica flour, it includes silicon powder particle, the silicon powder particle tool
There are multiple microcellular structures, pore size is 3nm~500nm, and the primary particle granularity of the silicon powder particle is less than 200nm.
Further, the surface of silicon powder particle also has carbonaceous conductive layer.
Further, the primary particle granularity of the foam-like silica flour is less than 150nm and/or the ratio surface of the foam-like silica flour
Product is 12m2/ g~18m2/g。
In accordance with a further aspect of the present invention, there is provided a kind of lithium ion battery, including negative material, the negative material include with
Upper any foam-like silica flour.
Through the above scheme, it is known that the beneficial effect of preparation method of the invention, foam silica flour and lithium ion battery exists
In：
(1) in preparation method of the present invention, on Si-Mg alloy powder surface, form relatively stable, fusing point in air and fired less than magnesium
The indium stannum alloy clad of point, will reduce the surface oxidation fire risk of Si-Mg alloy powder；
(2) the solid-state diffusion heat treatment process in preparation method of the present invention, will can promote tin-indium alloy clad and magnesium
Diffusion reaction, forms indium magnesium, tin magnesium metallic compound, eliminates the magnesium in this heat treatment process and catches fire caused processed powder certainly
Powder burning problem caused by combustion, at the same time can greatly improve production efficiency；
(3) (the volume ratio in low oxygen pressure, low oxygen content oxygen-nitrogen mixture body of the alloy-coated powder in preparation method of the present invention
5-20%) the metal such as indium tin compound of slow oxide alloy clad, will overcome the quick of foregoing magnesium in the prior art
Vigorous combustion problem is aoxidized, and as caused by magnesium combustion heating the shortcomings that silicon grain abnormal growth.
(4) there is the foam silica flour of the microcellular structure of carbonaceous conductive layer on the surface that this preparation method obtains, and micro cellular voids are uniform, silicon
The crystallinity of particle is high, and powder entirety oxygen content is low (being less than 5%), the porous silicon powder prepared better than existing other technologies.
(5) in this preparation method, using conventional intermediate frequency vacuum smelting method, overcome and foregoing use magnesium in the prior art
The security risk that workshop magnesium powder dust existing for powder catches fire, explodes, suitable industrialized mass production use is not oxidizable, fusing point is low
In the tin-indium alloy coated Si magnesium alloy particles of magnesium burning point, at the solid-state diffusion processing and hypoxemia oxidation under certain temperature
Reason is that the key point of microcellular structure foam silica flour is obtained in the preparation method of the present invention.
Brief description of the drawings
Fig. 1 is the method flow diagram that tin-indium alloy coated Si of embodiment of the present invention magnesium granules prepare foam-like silica flour.
Fig. 2 is the stereoscan photograph of foam silica flour prepared by the embodiment of the present invention one.
Fig. 3 is the X-ray diffracting spectrum of foam silica flour prepared by the embodiment of the present invention one.
Embodiment
In this application, " primary particle granularity " refers to：Single silicon crystal grain particle diameter.
It is emphasized that word "comprising" or " comprising " do not exclude the presence of element not listed in the claims or step
Suddenly.In addition, unless specifically described or the step of must sequentially occur, there is no restriction for the orders of above-mentioned steps in listed above, and
It can change or rearrange according to required design.And above-described embodiment can based on design and reliability consideration, mix each other
Close collocation to use using or with other embodiment mix and match, i.e., the technical characteristic in different embodiments can freely form
More embodiments.
Unless there are known entitled phase otherwise meaning, the numerical parameter in this specification and appended claims are approximations, energy
Enough required characteristic changings according to as obtained by content of this disclosure.Specifically, it is all to be used in specification and claim
The middle content for representing composition, the numeral of reaction condition etc., it is thus understood that be in all situations be subject to [about " term repaiied
Decorations.Under normal circumstances, the implication of its expression refers to include by specific quantity ± 10% change in certain embodiments, at some
± 5% change in embodiment, ± 1% change in certain embodiments, in certain embodiments ± 0.5% change.
Shortcoming it is an object of the invention to the preparation method for overcoming existing porous silicon powder and nano silica fume, proposes one
Kind forms clad using indium stannum alloy of the fusing point less than magnesium burning point in Si-Mg alloy powder particle surface, then passes through solid-state diffusion
Alloying, with reference to hypoxemia oxidation technology, realizes that the controllable oxidation at a slow speed and the control of silicon nanocrystal of magnesium are grown up, finally by pickling
With medium ball milling and heat treatment process, preparing surface has carbonaceous conductive layer and possesses the method for the foam silica flour of microcellular structure.Mainly
It is to employ the indium stannum alloy coated Si magnesium alloy particles that not oxidizable, fusing point is less than magnesium burning point, with reference under certain temperature
Solid-state diffusion processing and hypoxemia oxidation processing technique are that the present invention obtains the foam silica flour with microcellular structure.
Fig. 1 is the method flow diagram that tin-indium alloy coated Si of embodiment of the present invention magnesium granules prepare foam-like silica flour.Fig. 1 institutes
Show, this method mainly includes：
S101：Prepared silicon magnesium alloy powder；
S102：Tin-indium alloy layer is coated on the surface of Si-Mg alloy powder；
S103：The Si-Mg alloy powder for being coated with tin-indium alloy layer is subjected to solid-state diffusion heat treatment, to promote clad
In tin and indium metal combined respectively with magnesium pasc reaction；
S104：Si-Mg alloy powder after solid-state diffusion is heat-treated carries out oxidation processes；And
S105：Si-Mg alloy powder after oxidation processes is subjected to pickling and removes tin, indium and magnesium.
For step S101, prepared silicon magnesium alloy powder can be the powder that existing Si-Mg alloy is formed, or by
The alloy powder being prepared after silicon raw material and magnesium raw material mixing, for example, can be according to the siliceous 30-35% (quality of Si-Mg alloy
Percentage) ratio prepared silicon and MAG block.
In certain embodiments, for S101：Conventional intermediate frequency vacuum smelting method can be used, melting kettle uses graphite
Crucible, under an argon atmosphere first melts the silico briquette matched surely and MAG block, by ultimately forming siliceous 35% (mass percent)
Ratio substep addition metal MAG block, and control melt temperature more than 1100 DEG C, pour into a mould Si-Mg alloy ingot.Then will can obtain
Si-Mg alloy ingot nitrogen atmosphere protection under crush, cross sieve classification.Using conventional intermediate frequency vacuum smelting method, before overcoming
State the security risk caught fire, exploded using workshop magnesium powder dust existing for magnesium powder in the prior art.
In certain embodiments, small intermediate frequency vacuum smelting furnace can be selected, according to melting graphite crucible capacity dispensing, is pressed
The ratio prepared silicon and MAG block of the siliceous 30-35% of Si-Mg alloy (mass percent), under an argon atmosphere first by the silicon in dispensing
Melted with a small amount of block magnesium, control melt temperature to be added step by step remaining while 1100-1200 DEG C in fusion process
Metal MAG block, finally keep the temperature 2-5 minute after, be poured into through 250-300 DEG C preheating after cast iron mold, acquisition Si-Mg alloy ingot；
Then Si-Mg alloy ingot after cooling takes out, and under dry air atmosphere, is less than using jaw crusher coarse crushing to granularity
After 5mm, sieve classification is crossed after vibratory milling under having nitrogen atmosphere protection.
For step S102：In certain embodiments, by the Si-Mg alloy powder surface of the certain particle size prepared in S101,
One layer of cladding relatively stable, fusing point in the air of moisture content is less than the indium stannum alloy layer of magnesium burning point.In the step, by silicon
Magnesium alloy powder surface, forms the indium stannum alloy clad that relatively stable, fusing point in air is less than magnesium burning point, will reduce Si-Mg alloy
The surface oxidation fire risk of powder.
In certain embodiments, powder mixer tool alloying and/or at a certain temperature can be selected in method for coating
Liquation stirs cladding process.
For method for coating, can be selected from it is following any one：First, by Si-Mg alloy powder and metallic tin powder, indium powder
Mixed-powder is mixed with tin-indium alloy powder, and is coated by the way of mechanical ball mill；2nd, by Si-Mg alloy powder and gold
Belong to glass putty, indium powder mixed powder or mixed with tin-indium alloy powder, be incorporated with after mixing in the heat-treatment furnace of agitating device, pass through machine
Tool stirs and heats mixed powder and coated；And three, by Si-Mg alloy powder and metallic tin powder, the mixed powder or and tin of bismuth meal
Indium alloy powder mixes, and cladding is realized by the way of mechanical ball mill；And the mixed powder after mechanical ball mill is incorporated with stirring
In the heat-treatment furnace of device, by mechanical agitation and mixed powder is heated.
In certain embodiments, for step S103, the indium stannum alloy of acquisition is coated into Si-Mg alloy powder in vacuum or lazy
Property gas such as nitrogen, argon gas atmosphere under, temperature higher than clad indium stannum alloy eutectic point temperature (119 DEG C), be 350-500
DEG C, solid-state diffusion processing is carried out when insulation 0.25-1.0 is small.Solid-state diffusion heat treatment process, can promote tin-indium alloy clad
With the diffusion reaction of magnesium, form indium magnesium, tin magnesium metallic compound, eliminate the magnesium in this heat treatment process catch fire caused by it is processed
Powder burning problem caused by powder spontaneous combustion, at the same time can greatly improve production efficiency.
In certain embodiments, the Si-Mg alloy powder that granularity is 20-300 mesh can be selected, preferred size is 80-200 mesh
Si-Mg alloy powder it is appropriate, by the weight of 1: 3-5 ratio-dependent cladding metal dust, and it is by Theil indices to coat metal dust
For the tin-indium alloy powder of 10-60% (mass percent)；Above-mentioned Si-Mg alloy powder and cladding metal dust are loaded into stainless steel
In tank, be incorporated 2-4 times, the sintered carbide ball of a diameter of 6-12mm of mixed-powder weight, and be filled with nitrogen or argon gas protect it is close
Envelope, using common rotary mill mixing and ball milling 12-48 it is small when.Then crowd can also be used under the conditions of suitable ratio of grinding media to material etc.
Well known high-energy ball milling method, Si-Mg alloy powder and tin-indium alloy powder are sufficiently mixed and reach cladding purpose.
Further to improve the degree of perfection of clad, the mixed powder after above-mentioned ball milling mixing is selected, is incorporated with
In the heat-treatment furnace of agitating device, under nitrogen or argon, in-furnace temperature is controlled as more than tin indium eutectic point, i.e., temperature is
200-300 DEG C, powder is heated by mechanical agitation and promotes cladding, to form the clad of densification on Si-Mg alloy powder surface.
For step S103, the Si-Mg alloy powder for being coated with tin-indium alloy layer is subjected to solid-state diffusion heat treatment, to promote
Combined respectively with magnesium pasc reaction into the tin in clad and indium metal.Solid-state diffusion heat treatment process, can promote tin-indium alloy
The diffusion reaction of clad and magnesium, forms indium magnesium, tin magnesium metallic compound, eliminates caused by the magnesium in this heat treatment process catches fire
Powder burning problem caused by processed powder spontaneous combustion, at the same time can greatly improve production efficiency.
In certain embodiments, the coated composite powder that can be obtained step S102, loads in tubular type vacuum drying oven, maintains vacuum
In below 200Pa, 200-500 DEG C of insulation 0.25-1.0h of temperature is selected to carry out solid-state diffusion heat treatment；At the diffusion heat of this step
Reason can also fill in vacuum drying oven to be completed under inert gas such as nitrogen or argon gas protective atmosphere.
For step S104：Si-Mg alloy powder after solid-state diffusion is heat-treated carries out oxidation processes.Alloy-coated powder
Metal such as indium Sillim of (volume ratio 5-20%) slow oxide alloy clad in low oxygen pressure, low oxygen content oxygen-nitrogen mixture body
Belong to compound, the Quick Oxidation vigorous combustion problem of foregoing magnesium in the prior art will be overcome, and as caused by magnesium combustion heating
The shortcomings that silicon grain abnormal growth.
In certain embodiments, above-mentioned oxidation processes are in the oxygen-nitrogen mixture body that oxygen content volume accounting is 5-20%
Carry out, the temperature of oxidation processes is 350-500 DEG C.
In certain embodiments, the powder after the solid-state diffusion of acquisition can be heat-treated, loads in tubular type vacuum drying oven, leads to
It is 0.05-0.1MPa to enter the oxygen-nitrogen mixture body that oxygen content is 5-20% (volume ratio) and maintain furnace pressure, in in-furnace temperature
For keep the temperature at 350-500 DEG C 0.5-3 it is small when complete hypoxemia oxidation processes.
For step S105, the Si-Mg alloy powder after oxidation processes is subjected to pickling and removes tin, indium and magnesium.The pickling
Step removes oxide (such as magnesia, indium oxide and tin oxide) and the residual metal (magnesium, indium and tin) without complete oxidation,
Obtained after repeatedly washing, drying, sieving, obtain the original foam silica flour as shown in Figure 2 with microcellular structure..
In certain embodiments, can by after oxidation processes Si-Mg alloy powder carry out pickling, pickle for hydrochloric acid and/
Or nitric acid, to remove oxide and metal impurities, then it is washed to neutral after drying original foam shape silica flour is made.
In certain embodiments, can by the powder after oxidation processes, with excess that the volume ratio of deionized water is 1: 1
Immersion treatment 1-5h in hydrochloric acid and/or salpeter solution, to remove oxide and the residual metal impurity without complete oxidation, through more
Original foam silica flour is obtained after secondary washing, drying, sieving.
In certain embodiments, step S106 can also be included after step S105：In the medium of carbonaceous organic material
Ball milling and calcining form the foam silica flour that there is the microcellular structure of carbonaceous conductive layer on surface.
Chosen for the medium of carbonaceous organic material, can be various carbonaceous organic materials well known in the prior art, preferably
For following at least one：Pitch acetone soln, pitch tetrahydrofuran solution, polyvinyl alcohol water solution and PI/NMP solution.
In certain embodiments, above-mentioned and ball milling and calcining can be：By original foam shape silica flour in carbonaceous organic material
Ball milling is carried out in medium, obtains slurry；And rear high-temperature calcination is dried in slurry, obtain carbon coating layer.
In certain embodiments, can be by the original foam silica flour that step S105 is obtained, in suitable zirconia ball and ball
Material uses polyvinyl alcohol water solution of the mass percent for 5-10%, adjusts silicon than lower progress medium ball mill crushing, ball-milling medium
The volume content of powder and ball in the solution be not more than 80%, Ball-milling Time can adjust as needed, be usually no more than 2 it is small when；For
Stable carbonaceous conductive layer is obtained in final foam silicon powder surface, such as pitch acetone soln, pitch tetrahydrofuran also can be used
The solution containing organic carbon source such as solution and PI/NMP solution.Powder slurries after ball milling are dry in the baking oven less than 100 DEG C
Afterwards, in nitrogen atmosphere the carbon-coated foam silica flour with microcellular structure is obtained after 500~650 DEG C of calcined crushed processing.
Melting, mixing and ball milling described above, heat treatment, pickling are not limited in the preparation method of the embodiment of the present invention
Method, it is possible to use well known to a person skilled in the art method completion, the ball-milling medium in powder shattering process is also not necessarily limited to
Pitch acetone soln, pitch tetrahydrofuran solution, polyvinyl alcohol water solution and PI/NMP solution, can also add art technology
Organic high molecular compound known to personnel is with the certain carbonaceous conductive layer of Si powder surface acquisition.
Another aspect according to embodiments of the present invention, also provides a kind of foam-like silica flour, it includes silicon powder particle, the silicon
Powder particles have multiple microcellular structures, and pore size is 3nm~500nm, and the primary particle granularity of the silicon powder particle is less than
200nm.The primary particle granularity is smaller, the after polymerization silicon grain in a large amount of gaps is more easily combined to form, beneficial to follow-up work
Skill processing.Above-mentioned foam-like silica flour, micro cellular voids are uniform, and the crystallinity of silicon grain is high, and powder entirety oxygen content is low.
In certain embodiments, the surface of the silicon powder particle also has carbonaceous conductive layer.Specific generation type can be found in
Corresponding steps in above-mentioned preparation method, it will not be described here.
In certain embodiments, the primary particle granularity of the foam-like silica flour is less than 150nm and/or the foam-like silica flour
Specific surface area is 12m2/ g~18m2/g。
Another aspect according to embodiments of the present invention, also provides a kind of lithium ion battery, including negative material, the anode material
Material includes the foam-like silica flour described in any of the above.
For the object, technical solutions and advantages of the present invention are more clearly understood, below in conjunction with specific embodiment, and reference
Attached drawing, the present invention is described in further detail.Following embodiments narration is used for describing this technology, rather than the present invention is carried out
Limitation.The technical field of the invention personnel will recognize and arrive various equivalent variations described below.
Embodiment one：
(1) small intermediate frequency vacuum smelting furnace is selected, according to melting graphite crucible capacity, by every stove dispensing 1kg, siliceous 30-
The ratio of 35% (mass percent) prepares silico briquette and MAG block, under an argon atmosphere first by the silicon in dispensing and a small amount of block magnesium
Fusing, controls melt temperature to add remaining metal MAG block step by step, finally while 1100-1200 DEG C in fusion process
Insulation 2-5 minute after, be poured into through 250-300 DEG C preheating after cast iron mold, acquisition Si-Mg alloy ingot；
(2) by Si-Mg alloy ingot after cooling take out, under dry air atmosphere, using jaw crusher coarse crushing to
After granularity is less than 5mm, the vibratory milling in the case where there is nitrogen atmosphere protection, after sieve classification；
(3) the Si-Mg alloy powder that granularity is 20-300 mesh is selected, preferred size is the Si-Mg alloy powder 200 of 40-100 mesh
Gram, it is the cladding indium stannum alloy powder less than 100 mesh in 1: 4 800 grams of ratio outfit, granularity, cladding indium stannum alloy powder
Theil indices are 40% (mass percent), and above-mentioned Si-Mg alloy powder and clad alloy powder are loaded to the stainless steel of a diameter of 185mm
In tank, 2-4 times of sintered carbide ball of above-mentioned mixed-powder weight is incorporated, the diameter of sintered carbide ball selects 6-12mm, and fills
Enter nitrogen or argon gas protection sealing, using common rotary mill mixing and ball milling 12 it is small when；
(4) further, the coated composite powder after above-mentioned ball milling mixing is added up to 1000 grams, is incorporated with the heat of agitating device
In treatment furnace, under nitrogen atmosphere protection, it is 200-300 DEG C to control in-furnace temperature, and preferably in-furnace temperature is 240-280 DEG C,
Mixture of powders is stirred under about 100 revs/min of mixing speed, promotes cladding, to form densification on Si-Mg alloy powder surface
Clad.
(5) by the coated composite powder of acquisition, load in tubular type vacuum drying oven, maintain vacuum in below 200Pa, selection temperature 200-
500 DEG C, preferably furnace temperature is 350-400 DEG C, and insulation 0.5 is diffused heat treatment when small.
(6) by powder after the diffusion heat treatments of acquisition, load in tubular type vacuum drying oven, it is 5-20% (volumes to be passed through oxygen content
Than), preferably oxygen content is 10% oxygen-nitrogen mixture body, and it is about 0.05MPa, in-furnace temperature 350- to maintain furnace inner gas pressure
500 DEG C, preferably furnace temperature be 350-400 DEG C at insulation 1 it is small when complete coated composite powder low oxygen content oxidation processes；
(7) by the powder after low oxygen content oxidation processes, the excess nitric acid for being 1: 1 in the volume ratio of acid and deionized water
With in hydrochloric acid solution distinguish immersion treatment 5h, to remove oxide and the residual metal impurity without complete oxidation, through multiple water
Wash, dry, sieve, obtain original foam silica flour；
(8) original foam silica flour is subjected to medium ball mill crushing, ball-milling medium under suitable zirconia ball and ratio of grinding media to material
Mass percent is used to adjust the volume content of silica flour and ball no more than liquor capacity for 10% polyvinyl alcohol water solution
80%, when ball milling 1 is small；Powder slurries after ball milling after drying, in nitrogen atmosphere after about 650 DEG C of calcined crushed processing, obtain
There must be the foam silica flour of microcellular structure 1.；
Scanned electron microscopic observation (see Fig. 2) shows that foam silica flour gap is uniform, and the granularity of the primary particle of foam silica flour is small
In 180nm, and x-ray analysis (see Fig. 3) show that a silicon grain of foam silica flour has good crystallinity, X-ray collection of illustrative plates
There is not the feature broad peak of amorphous phase (mainly silica), the specific surface area of nitrogen adsorption assay foam silica flour 1. is about
15m2/ g (is shown in Table 1).
Table 1
Embodiment two：
(1) (2) are identical with embodiment one；
(3) preferred size is 200 grams of the Si-Mg alloy powder of 100-200 mesh, and 1000 grams of cladding metals are equipped with 1: 5 ratio
Powder, cladding metal powder preferably by the tin-indium alloy powder that granularity is stanniferous less than 100 purposes 25%, by above-mentioned Si-Mg alloy powder and
Cladding metal powder is fitted into the stainless cylinder of steel of a diameter of 185mm, is incorporated 2-4 times of hard alloy of above-mentioned mixed-powder weight
Ball, the diameter of sintered carbide ball select 6.12mm, and are filled with nitrogen or argon gas protection sealing, are mixed using common rotary mill
When conjunction ball milling 32 is small；
(4) it is identical with embodiment one；
(5) it is identical with embodiment one；
(6) by powder after the diffusion heat treatments of acquisition, load in tubular type vacuum drying oven, it is 5-20% (volumes to be passed through oxygen content
Than), preferably oxygen content is 10% oxygen-nitrogen mixture body, and it is about 0.05MPa, in-furnace temperature 350- to maintain furnace inner gas pressure
500 DEG C, preferably furnace temperature is 400-450 DEG C, and the low oxygen content oxidation processes of coated composite powder are completed when insulation 2 is small；
(7) it is identical with embodiment one；
(8) it is identical with embodiment one；
The foam silica flour that embodiment two obtains is 2. 2. similar to the foam silica flour of embodiment one, and gap is uniform, and crystallinity is good
It is good, occur without obvious silica amorphous phase；The primary particle granularity of foam silica flour is less than 150nm, nitrogen adsorption assay
The specific surface area of the foam silica flour of embodiment two 2. is about 18m2/ g (is shown in Table 1).
Embodiment three：
(1) (2) are identical with embodiment one；
(3) preferred size is 200 grams of the Si-Mg alloy powder of 200-300 mesh, and 600 grams of cladding metals are equipped with 1: 3 ratio
Powder, cladding metal powder are the cladding indium stannum alloy powder less than 100 mesh preferably by granularity, coat the Theil indices of indium stannum alloy powder
For 50% (mass percent), above-mentioned Si-Mg alloy powder and cladding metal powder are fitted into the stainless cylinder of steel of a diameter of 185mm, matched somebody with somebody
Enter 2-4 times of sintered carbide ball of above-mentioned mixed-powder weight, the diameter of sintered carbide ball selects 6-12mm, and be filled with nitrogen or
Argon gas protection sealing, using common rotary mill mixing and ball milling 28 it is small when；
(4) coated composite powder after above-mentioned ball milling mixing is added up to 1000 grams, be incorporated with the heat-treatment furnace of agitating device,
Under nitrogen atmosphere protection, it is 200-300 DEG C to control in-furnace temperature, and preferably in-furnace temperature is 230-260 DEG C, at about 100 revs/min
Mixture of powders is stirred under mixing speed, promotes cladding, to form the clad of densification on Si-Mg alloy powder surface.
(5) it is identical with embodiment one；
(6) by powder after the diffusion heat treatments of acquisition, load in tubular type vacuum drying oven, it is 5-20% (volumes to be passed through oxygen content
Than), preferably oxygen content is 5% oxygen-nitrogen mixture body, and it is about 0.1MPa, in-furnace temperature 350- to maintain furnace inner gas pressure
500 DEG C, preferably furnace temperature is 450.500 DEG C, and the low oxygen content oxidation processes of coated composite powder are completed when insulation 2 is small；
(7) it is identical with embodiment one；
(8) it is identical with embodiment one；
The foam silica flour that embodiment three obtains is 3. similar to the foam silica flour of above-described embodiment, and gap is uniform, and crystallinity is good
It is good, occur without obvious silica amorphous phase；The primary particle granularity of foam silica flour is less than 200nm, nitrogen adsorption assay
The specific surface area of the foam silica flour of embodiment two 2. is about 12m2/ g (is shown in Table 1).
Comparative example：
As the contrast with embodiment, reference literature the method (NANOLett.2014,14,4505-4510) (Bulk-
Nanoporous-Silicon Negative Electrode with Extremely HighCyclability for
Lithium-Ion Batteries Prepared Using a Top-DownProcess, Takeshi Wada, etc.), press
Following step, is prepared for as the porous silicon powder compared.
(1) by silicon, magnesium powder mixed powder under helium protection, be heated to 1000-1100 DEG C and keep the temperature 3-4 it is small when, with synthesis
Mg-si master alloy powder；
(2) the pure bismuth that granularity is immersed to 500-550 DEG C of excess under argon gas protection for the mg-si master alloy powder of 100-200 mesh melts
In bath of liquid, and keep the temperature 0.5 it is small when to promote part magnesium to be dissolved in bismuth liquation；
(3) powder from 500-550 DEG C of pure bismuth liquation bath after taking-up processing, is poured into no
In stainless steel boat, there is a small amount of oxide yellow thing formation first, powder starts spontaneous combustion and extends to whole powder therewith；
(4) yellow powder after above-mentioned spontaneous combustion is poured into immersion treatment 5h in excessive concentrated nitric acid solution, with remove oxide and
There is no the residual metal bismuth of complete oxidation, after repeatedly washing, drying, sieving, obtain the porous silicon powder of comparative example.
The porous silicon powder crystallinity that comparative example obtains is good, occurs without obvious silica amorphous phase；But porous silicon
The primary particle granularity of powder is 50-300nm, its specific surface area of nitrogen adsorption assay is about 9m2/ g (is shown in Table 1).
Particular embodiments described above, has carried out the purpose of the present invention, technical solution and beneficial effect further in detail
Describe in detail bright, it should be understood that the foregoing is merely the present invention specific embodiment, be not intended to limit the invention, it is all
Within the spirit and principles in the present invention, any modification, equivalent substitution, improvement and etc. done, should be included in the protection of the present invention
Within the scope of.
Claims (13)
1. a kind of method that tin-indium alloy coated Si magnesium granules prepare foam-like silica flour, including：
Prepared silicon magnesium alloy powder；
Tin-indium alloy layer is coated on the surface of Si-Mg alloy powder；
The Si-Mg alloy powder for being coated with tin-indium alloy layer is subjected to solid-state diffusion heat treatment, to promote the tin and indium in clad
Metal is combined with magnesium pasc reaction respectively；
Si-Mg alloy powder after solid-state diffusion is heat-treated carries out oxidation processes；And
Si-Mg alloy powder after oxidation processes is subjected to pickling and removes tin, indium and magnesium.
2. according to the method described in claim 1, it is characterized in that,
In the tin-indium alloy, the mass percent of tin is 10-60%.
3. according to the method described in claim 1, it is characterized in that, pickling further includes after removing tin, indium and magnesium：Have carbon containing
Ball milling and calcining form the foam silica flour that there is the microcellular structure of carbonaceous conductive layer on surface in the medium of machine thing.
4. preparation method according to claim 1, it is characterised in that described to coat tin indium on the surface of Si-Mg alloy powder
The mode of alloy-layer is selected from one below：
Si-Mg alloy powder is mixed with metallic tin powder, the mixed-powder of indium powder or with tin-indium alloy powder, and uses mechanical ball mill
Mode coated；
Si-Mg alloy powder is mixed with metallic tin powder, the mixed powder of indium powder or with tin-indium alloy powder, stirring is incorporated with after mixing
In the heat-treatment furnace of device, by mechanical agitation and heat mixed powder and coated；And
Si-Mg alloy powder is mixed with metallic tin powder, the mixed powder of bismuth meal or with tin-indium alloy powder, and using mechanical ball mill
Mode realizes cladding；And the mixed powder after mechanical ball mill is incorporated with the heat-treatment furnace of agitating device, pass through mechanical agitation
And heat mixed powder.
5. preparation method according to claim 1, it is characterised in that the temperature of the solid-state diffusion heat treatment is 200-
500℃。
6. preparation method according to claim 1, it is characterised in that the oxidation processes are to be in oxygen content volume accounting
Carried out in the oxygen-nitrogen mixture body of 5-20%, the temperature of oxidation processes is 350-500 DEG C.
7. preparation method according to claim 1, it is characterised in that the Si-Mg alloy powder by after oxidation processes
Carrying out pickling removal tin, indium and magnesium includes：
Si-Mg alloy powder after oxidation processes is subjected to pickling, pickle is hydrochloric acid and/or nitric acid, to remove oxide and gold
Belong to impurity, then it is washed to neutral after dry original foam shape silica flour is made.
8. preparation method according to claim 3, it is characterised in that ball milling and calcining in the medium of carbonaceous organic material
Specifically include：
Original foam shape silica flour is subjected to ball milling in the medium of carbonaceous organic material, obtains slurry；And
Rear high-temperature calcination is dried in slurry, obtains carbon coating layer.
9. preparation method according to claim 7, it is characterised in that the medium of the carbonaceous organic material be selected from it is following at least
It is a kind of：
Pitch acetone soln, pitch tetrahydrofuran solution, polyvinyl alcohol water solution and PI/NMP solution.
10. a kind of foam-like silica flour, it includes silicon powder particle, and the silicon powder particle has multiple microcellular structures, and pore size is
3nm~500nm, the primary particle granularity of the silicon powder particle are less than 200nm.
11. foam-like silica flour according to claim 10, it is characterised in that also led with carbon on the surface of the silicon powder particle
Electric layer.
12. foam-like silica flour according to claim 10, it is characterised in that
The primary particle granularity of the foam-like silica flour be less than 150nm and/or
The specific surface area of the foam-like silica flour is 12m2/ g~18m2/g。
13. a kind of lithium ion battery, including negative material, which includes any foams of claim 10-12
Shape silica flour.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711272226.7A CN108017057B (en) | 2017-12-05 | 2017-12-05 | The method and silicon powder of tin-indium alloy coated Si magnesium granules preparation foam-like silicon powder |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711272226.7A CN108017057B (en) | 2017-12-05 | 2017-12-05 | The method and silicon powder of tin-indium alloy coated Si magnesium granules preparation foam-like silicon powder |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108017057A true CN108017057A (en) | 2018-05-11 |
| CN108017057B CN108017057B (en) | 2019-09-06 |
Family
ID=62078591
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201711272226.7A Active CN108017057B (en) | 2017-12-05 | 2017-12-05 | The method and silicon powder of tin-indium alloy coated Si magnesium granules preparation foam-like silicon powder |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108017057B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117199378A (en) * | 2023-11-06 | 2023-12-08 | 浙江吉利控股集团有限公司 | Silicon-based negative electrode material and lithium ion battery |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102157731A (en) * | 2011-03-18 | 2011-08-17 | 上海交通大学 | Silicon and carbon compound anode material of lithium ion battery and preparation method of silicon and carbon compound anode material |
| CN105149574A (en) * | 2015-09-21 | 2015-12-16 | 中南大学 | Coating method iron-based magnetically soft alloy powder and preparation method of soft magnet composite material |
| CN105655555A (en) * | 2016-01-13 | 2016-06-08 | 浙江天能能源科技有限公司 | Silicon-carbon composite material, preparation method and application of silicon-carbon composite material |
-
2017
- 2017-12-05 CN CN201711272226.7A patent/CN108017057B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102157731A (en) * | 2011-03-18 | 2011-08-17 | 上海交通大学 | Silicon and carbon compound anode material of lithium ion battery and preparation method of silicon and carbon compound anode material |
| CN105149574A (en) * | 2015-09-21 | 2015-12-16 | 中南大学 | Coating method iron-based magnetically soft alloy powder and preparation method of soft magnet composite material |
| CN105655555A (en) * | 2016-01-13 | 2016-06-08 | 浙江天能能源科技有限公司 | Silicon-carbon composite material, preparation method and application of silicon-carbon composite material |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117199378A (en) * | 2023-11-06 | 2023-12-08 | 浙江吉利控股集团有限公司 | Silicon-based negative electrode material and lithium ion battery |
| CN117199378B (en) * | 2023-11-06 | 2024-03-12 | 浙江吉利控股集团有限公司 | Silicon-based negative electrode material and lithium ion battery |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108017057B (en) | 2019-09-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP2778130B1 (en) | Nano-silicon/carbon composite material and preparation method therefor | |
| TWI517478B (en) | A method of fabricating structured particles composed of silicon or a silicon-based material and their use in lithium rechargeable batteries | |
| CA2752844A1 (en) | Method for preparing a particulate of si or siox-based anode material, and material thus obtained | |
| CN103402921A (en) | Method for the production of an LMO product | |
| CN113948688B (en) | Modified pre-lithiated silica composite material and preparation method and application thereof | |
| EP3130023A1 (en) | Method and material for lithium ion battery anodes | |
| CN107074573A (en) | The preparation method and plate-like aluminum oxide powder of plate-like aluminum oxide powder | |
| CN111786014A (en) | Garnet type solid electrolyte powder with superfine particle size and preparation method thereof | |
| CN104744047A (en) | Method for preparing silicon nitride crucible through reactive sintering | |
| CN110408833A (en) | A kind of preparation method of NbTaTiZr high-entropy alloy and its powder | |
| CN112281014A (en) | Preparation method of rare earth alloyed magnesium-lithium alloy or aluminum-lithium alloy | |
| CN108546093A (en) | Short fine magnesium oxide-based crucible of enhancing of a kind of aluminium oxide and preparation method thereof | |
| CN103498060B (en) | Method for preparing metal vanadium | |
| CN108017057B (en) | The method and silicon powder of tin-indium alloy coated Si magnesium granules preparation foam-like silicon powder | |
| CN108002389B (en) | The method and silicon powder of zinc bismuth alloy coated Si magnesium granules preparation foam-like silicon powder | |
| CN113184870A (en) | Macro-particle-size-controllable LaB6Method for preparing powder | |
| CN114956085A (en) | Method for preparing antioxidant MXene through low-temperature molten salt system | |
| CN114956084A (en) | Preparation method of Al-doped MXene | |
| CN108039467A (en) | Its lithium ion battery of spongy silica flour and preparation method and application | |
| CN108039485B (en) | Foam-like silicon powder is with preparation method and using its lithium ion battery | |
| CN107999781B (en) | The method and ferrosilicon composite powder of zinc bismuth alloy cladding magnesium ferrosilicon particle preparation ferrosilicon powder | |
| CN114628661A (en) | Negative electrode material, preparation method thereof and lithium ion battery | |
| CN108011091A (en) | Indium bismuth alloy coats the method and ferrosilicon powder of magnesium ferrosilicon particle preparation ferrosilicon powder | |
| CN108039484B (en) | Spongy silicon powder, preparation method thereof and lithium ion battery | |
| CN111517800B (en) | Method for preparing high-purity superfine zirconium boride powder by grinding aid auxiliary sanding |
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 |