CN108002389A - Zinc bismuth alloy coated Si magnesium granules prepare the method and silica flour of foam-like silica flour - Google Patents
Zinc bismuth alloy coated Si magnesium granules prepare the method and silica flour of foam-like silica flour Download PDFInfo
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Abstract
The invention discloses a kind of method that zinc bismuth alloy coated Si magnesium granules prepare foam-like silica flour, including：Prepared silicon magnesium alloy powder；Zinc bismuth alloy layer is coated on the surface of Si-Mg alloy powder；The Si-Mg alloy powder that zinc bismuth alloy layer will be coated with carries out solid-state diffusion heat treatment, to promote zinc in clad and bismuth 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 zinc, bismuth and magnesium.It is less than the zinc bismuth 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 zinc bismuth 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 burning of processed powder, thus bring silicon grain rapidly grow up and
The oxidation of silicon, therefore industrialized production porous nano silica flour technique controlling difficulty is very big in this way, it is particularly unmanageable
The granularity of nano silica fume；One kind is also disclosed using metal chloride fused-salt medium long-time heat preservation (10h~15h) point in the prior art
Si-Mg alloy powder is solved, then the method for porous silicon is obtained by chlorohydric acid pickling, this process eliminates catching fire for magnesium in industrialized production
Burn 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 zinc bismuth 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.
According to an aspect of the present invention, there is provided a kind of method that zinc bismuth alloy coated Si magnesium granules prepare foam-like silica flour,
Including：
Prepared silicon magnesium alloy powder；
Zinc bismuth alloy layer is coated on the surface of Si-Mg alloy powder；
The Si-Mg alloy powder for being coated with zinc bismuth alloy layer is subjected to solid-state diffusion heat treatment, to promote the zinc in clad
Combined respectively with magnesium pasc reaction with bismuth 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 zinc, bismuth and magnesium.
Further, in the zinc bismuth alloy, the mass percent of zinc is 0.1%-7.5%.
Further, pickling further includes after removing zinc, bismuth 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 zinc bismuth alloy layer is selected from one below：
Si-Mg alloy powder is mixed with metal zinc, the mixed-powder of bismuth meal or with zinc bismuth alloy powder, and using machinery
The mode of ball milling is coated；
Si-Mg alloy powder is mixed with metal zinc, the mixed powder of bismuth meal or with zinc bismuth 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 metal zinc, the mixed powder of bismuth meal or with zinc bismuth 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 300-550 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 300-650 DEG C.
Further, the Si-Mg alloy powder by after oxidation processes, which carries out pickling removal zinc, bismuth 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 polyimides/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, the primary particle granularity of the silicon powder particle is less than 120nm.
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 70nm, and/or the ratio surface of the foam-like silica flour
Product is 26m2/ g~38m2/ g, and/or the pore size are 5nm~100nm.
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 zinc bismuth 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 zinc bismuth alloy clad and magnesium
Diffusion reaction, forms bismuth magnesium, zinc-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 zinc bismuth metallic 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 zinc bismuth 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 zinc bismuth alloy coated Si of embodiment of the present invention magnesium granules prepare foam-like silica flour.
Fig. 2 is the fine and close clad schematic diagram of Si-Mg alloy powder particle surface of the embodiment of the present invention.
Fig. 3 is the stereoscan photograph of foam silica flour prepared by the embodiment of the present invention one.
Fig. 4 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 numeral of the middle content for representing composition, reaction condition etc., it is thus understood that be that the term for being subject to " about " is repaiied in all situations
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 zinc bismuth 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 zinc bismuth 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 zinc bismuth 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：Zinc bismuth alloy layer is coated on the surface of Si-Mg alloy powder；
S103：The Si-Mg alloy powder for being coated with zinc bismuth alloy layer is subjected to solid-state diffusion heat treatment, to promote clad
In zinc and bismuth 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 zinc, bismuth 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 zinc bismuth alloy layer of magnesium burning point.In the step, by silicon
Magnesium alloy powder surface, forms the zinc bismuth alloy clad that relatively stable, fusing point in air is less than magnesium burning point, will subtract 897098 and lack silicon
The surface oxidation fire risk of magnesium alloy 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 metal zinc, bismuth meal
Mixed-powder is mixed with zinc bismuth alloy powder, and is coated by the way of mechanical ball mill；2nd, by Si-Mg alloy powder and gold
Belong to zinc powder, bismuth meal mixed powder or mixed with zinc bismuth 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 metal zinc, the mixed powder or and zinc of bismuth meal
Bismuth 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 zinc bismuth 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 zinc bismuth alloy eutectic point temperature (254.5 DEG C), be 300-
550 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 zinc bismuth alloy bag
The diffusion reaction of coating and magnesium, forms bismuth magnesium, zinc-magnesium metallic compound, eliminates the magnesium in this heat treatment process and catches fire caused quilt
Powder burning problem caused by handling 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 Zn content to coat metal dust
For the zinc bismuth alloy powder of 0.1%-7.5% (mass percent)；Above-mentioned Si-Mg alloy powder and cladding metal dust are loaded not
Become rusty in cylinder of steel, 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 guarantor
Shield sealing, using common rotary mill mixing and ball milling 12-48 it is small when.Then can also make under the conditions of suitable ratio of grinding media to material etc.
With well-known high-energy ball milling method, Si-Mg alloy powder and zinc bismuth alloy powder are sufficiently mixed and reach cladding mesh
's.
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 zinc bismuth eutectic point, i.e., temperature is
265-355 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 zinc bismuth alloy layer is subjected to solid-state diffusion heat treatment, to promote
Combined respectively with magnesium pasc reaction into the zinc in clad and bismuth metal.Solid-state diffusion heat treatment process, can promote zinc bismuth alloy
The diffusion reaction of clad and magnesium, forms bismuth magnesium, zinc-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, 300-550 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
The metal of (volume ratio 5-20%) the slow oxide alloy clad such as zinc bismuth gold 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 300-650 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 300-650 DEG C 0.25-2 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 zinc, bismuth and magnesium.The pickling
Step removes oxide (such as magnesia, bismuth oxide and zinc oxide) and the residual metal (magnesium, bismuth and zinc) without complete oxidation,
Original foam silica flour is obtained after repeatedly washing, drying, sieving.
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 be not more than liquor capacity 80%, Ball-milling Time can adjust as needed, be usually no more than 2 it is small when；
In order to obtain stable carbonaceous conductive layer in final spongy silicon powder surface, such as pitch acetone soln, pitch tetrahydrochysene also can be used
The solution containing organic carbon source such as tetrahydrofuran solution and PI/NMP solution.Powder slurries after ball milling are in the baking oven less than 100 DEG C
After drying, in nitrogen atmosphere after 500~650 DEG C of calcined crushed processing, the bubble as shown in Figure 3 with microcellular structure is obtained
Foam silica flour.
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 5nm~100nm, and the primary particle granularity of the silicon powder particle is less than
120nm.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 70nm and/or the foam-like silica flour
Specific surface area is 26m2/ g~38m2/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 equipped with 1000 grams of cladding metal powders, metal zinc 30 gram of the cladding metal powder preferably by granularity for -100 mesh in 1: 5 ratio
Mixed for 970 grams with metal bismuth meal, above-mentioned Si-Mg alloy powder and cladding metal powder are loaded to the stainless cylinder of steel of a diameter of 185mm
In, 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 is filled with
Nitrogen or argon gas protection sealing, using common rotary mill mixing and ball milling 48 it is small when；
(4) further, the coated composite powder after above-mentioned ball milling mixing is added up to 1200 grams, is incorporated with the heat of agitating device
In treatment furnace, under nitrogen atmosphere protection, it is 265-355 DEG C to control in-furnace temperature, and preferably in-furnace temperature is 300-320 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 300-
550 DEG C, preferably furnace temperature is 350-450 DEG C, and insulation 0.5 is diffused heat treatment when small, and scanning electron microscopic observation (see Fig. 2) is shown
Form diffused alloy layer.
(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 300- to maintain furnace inner gas pressure
650 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 0.5 is small；
(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
Immersion treatment 5h in solution, to remove oxide and the residual metal impurity without complete oxidation, through repeatedly washing, drying, mistake
Sieve, obtains 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. 3) shows that foam silica flour gap is uniform, and the granularity of the primary particle of foam silica flour is small
In 50nm, and x-ray analysis (see Fig. 4) show that a silicon grain of foam silica flour has good crystallinity, and X-ray collection of illustrative plates does not have
Occur amorphous phase (mainly silica)
| Primary particle granularity (nanometer) | Foam silica flour specific surface area (m2/g) | ||
| Embodiment one | Foam silica flour is 1. | ＜ 50nm | 38m2/g |
| Embodiment two | Foam silica flour is 2. | ＜ 70nm | 33m2/g |
| Embodiment three | Foam silica flour is 3. | ＜ 100nm | 30m2/g |
| Example IV | Foam silica flour is 4. | ＜ 60nm | 35m2/g |
| Embodiment five | Foam silica flour is 5. | ＜ 100nm | 28m2/g |
| Embodiment six | Foam silica flour is 6. | ＜ 120nm | 26m2/g |
| Comparative example | Porous silicon powder | 50-300nm | 9m2/g |
Feature broad peak, the specific surface area of nitrogen adsorption assay foam silica flour 1. is about 38m2/ 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 are preferably mixed by granularity for 950 grams of 50 grams of metal zinc and metal bismuth meal less than 100 mesh, will be upper
State Si-Mg alloy powder and cladding metal powder is fitted into the stainless cylinder of steel of a diameter of 185mm, be incorporated the 2-4 of above-mentioned mixed-powder weight
Times sintered carbide ball, the diameter of sintered carbide ball selects 6-12mm, and is filled with nitrogen or argon gas protection sealing, use are common
When rotary mill mixing and ball milling 36 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 5-25% (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
650 DEG C, preferably furnace temperature is 500-550 DEG C, and the low oxygen content oxidation processes of coated composite powder are completed when insulation 0.5 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 70nm, and nitrogen adsorption assay is real
It is about 33m to apply the specific surface area of the foam silica flour of example two 2.2/ 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 1000 grams of cladding metals are equipped with 1: 5 ratio
Powder, cladding metal powder are preferably mixed by granularity for 925 grams of 75 grams of metal zinc and metal bismuth meal less than 100 mesh, will be upper
State Si-Mg alloy powder and cladding metal powder is fitted into the stainless cylinder of steel of a diameter of 185mm, be incorporated the 2-4 of above-mentioned mixed-powder weight
Times sintered carbide ball, the diameter of sintered carbide ball selects 6-12mm, and is filled with nitrogen or argon gas protection sealing, use are common
When rotary mill mixing and ball milling 36 is small；
(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 265-355 DEG C to control in-furnace temperature, and preferably in-furnace temperature is 320-350 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
650 DEG C, preferably furnace temperature is 550-600 DEG C, and the low oxygen content oxidation processes of coated composite powder are completed when insulation 1 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 100nm, nitrogen adsorption assay
The specific surface area of the foam silica flour of embodiment two 2. is about 30m2/ g (is shown in Table 1).
Example IV：
(1) (2) are identical with embodiment one；
(3) preferred size is 200 grams of the Si-Mg alloy powder of 40-100 mesh, and 800 grams of cladding metals are equipped with 1: 4 ratio
Powder, cladding metal powder are preferably mixed by granularity for 775 grams of 25 grams of metal zinc and metal bismuth meal less than 100 mesh, will be upper
State Si-Mg alloy powder and cladding metal powder is fitted into the stainless cylinder of steel of a diameter of 185mm, be incorporated the 2-4 of above-mentioned mixed-powder weight
Times sintered carbide ball, the diameter of sintered carbide ball selects 6-12mm, and is filled with nitrogen or argon gas protection sealing, use are common
When rotary mill mixing and ball milling 36 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 0.1MPa, in-furnace temperature 350- to maintain furnace inner gas pressure
650 DEG C, preferably furnace temperature is 350-400 DEG C, and the low oxygen content oxidation processes of coated composite powder are completed when insulation 0.5 is small；
(7) it is identical with embodiment one；
(8) it is identical with embodiment one；
The foam silica flour that example IV obtains is 4. 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 60nm, and nitrogen adsorption assay is real
It is about 35m to apply the specific surface area of the foam silica flour of example two 2.2/ g (is shown in Table 1).
Embodiment five：
(1) (2) are identical with embodiment one；
(3) preferred size is 200 grams of the Si-Mg alloy powder of 100-200 mesh, and 800 grams of cladding metals are equipped with 1: 4 ratio
Powder, cladding metal powder are preferably mixed by granularity for 760 grams of 40 grams of metal zinc and metal bismuth meal less than 100 mesh, will be upper
State Si-Mg alloy powder and cladding metal powder is fitted into the stainless cylinder of steel of a diameter of 185mm, be incorporated the 2-4 of above-mentioned mixed-powder weight
Times sintered carbide ball, the diameter of sintered carbide ball selects 6-12mm, and is filled with nitrogen or argon gas protection sealing, use are common
When rotary mill mixing and ball milling 36 is small；
(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 265-355 DEG C to control in-furnace temperature, and preferably in-furnace temperature is 320-350 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 5-25% (volumes to be passed through oxygen content
Than), preferably oxygen content is 15% oxygen-nitrogen mixture body, and it is about 0.05MPa, in-furnace temperature 350- to maintain furnace inner gas pressure
650 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 1 is small；
(7) it is identical with embodiment one；
(8) it is identical with embodiment one；
The foam silica flour that embodiment five obtains is 5. 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 100nm, nitrogen adsorption assay
The specific surface area of the foam silica flour of embodiment two 5. is about 28m2/ g (is shown in Table 1).
Embodiment six：
(1) (2) are identical with embodiment one；
(3) preferred size is 200 grams of the Si-Mg alloy powder of 40-100 mesh, and 600 grams of cladding metals are equipped with 1: 3 ratio
Powder, cladding metal powder are preferably mixed by granularity for 570 grams of 30 grams of metal zinc and metal bismuth meal less than 100 mesh, will be upper
State Si-Mg alloy powder and cladding metal powder is fitted into the stainless cylinder of steel of a diameter of 185mm, be incorporated the 2-4 of above-mentioned mixed-powder weight
Times sintered carbide ball, the diameter of sintered carbide ball selects 6-12mm, and is filled with nitrogen or argon gas protection sealing, use are common
When rotary mill mixing and ball milling 48 is small；
(4) coated composite powder after above-mentioned ball milling mixing is added up to 800 grams, be incorporated with the heat-treatment furnace of agitating device,
Under nitrogen atmosphere protection, it is 265-355 DEG C to control in-furnace temperature, and preferably in-furnace temperature is 320-350 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 5-25% (volumes to be passed through oxygen content
Than), preferably oxygen content is 10% oxygen-nitrogen mixture body, and it is about 0.1MPa, in-furnace temperature 350- to maintain furnace inner gas pressure
650 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 1 is small；
(7) it is identical with embodiment one；
(8) it is identical with embodiment one；
The foam silica flour that embodiment six obtains is 6. 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 120nm, nitrogen adsorption assay
The specific surface area of the foam silica flour of embodiment two 5. is about 26m2/ 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 zinc bismuth alloy coated Si magnesium granules prepare foam-like silica flour, including：
Prepared silicon magnesium alloy powder；
Zinc bismuth alloy layer is coated on the surface of Si-Mg alloy powder；
The Si-Mg alloy powder for being coated with zinc bismuth alloy layer is subjected to solid-state diffusion heat treatment, to promote the zinc and bismuth 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 zinc, bismuth and magnesium.
2. according to the method described in claim 1, it is characterized in that,
In the zinc bismuth alloy, the mass percent of zinc is 0.1%-7.5%.
3. according to the method described in claim 1, it is characterized in that, pickling further includes after removing zinc, bismuth 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 zinc bismuth 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 metal zinc, the mixed-powder of bismuth meal or with zinc bismuth alloy powder, and uses mechanical ball mill
Mode coated；
Si-Mg alloy powder is mixed with metal zinc, the mixed powder of bismuth meal or with zinc bismuth 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 metal zinc, the mixed powder of bismuth meal or with zinc bismuth 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 300-
550℃。
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 300-650 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 zinc, bismuth 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, the silica flour
The primary particle granularity of grain is less than 120nm.
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 is less than 60nm, and/or
The specific surface area of the foam-like silica flour is 26m2/ g~38m2/ g, and/or
The pore size is 5nm~100nm.
13. a kind of lithium ion battery, including negative material, which includes any foams of claim 10-12
Shape silica flour.
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