CN108002389B - The method and silicon powder of zinc bismuth alloy coated Si magnesium granules preparation foam-like silicon powder - Google Patents
The method and silicon powder of zinc bismuth alloy coated Si magnesium granules preparation foam-like silicon powder Download PDFInfo
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- CN108002389B CN108002389B CN201711271948.0A CN201711271948A CN108002389B CN 108002389 B CN108002389 B CN 108002389B CN 201711271948 A CN201711271948 A CN 201711271948A CN 108002389 B CN108002389 B CN 108002389B
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- C01B33/00—Silicon; Compounds thereof
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Abstract
The invention discloses a kind of methods of zinc bismuth alloy coated Si magnesium granules preparation foam-like silicon powder, comprising: 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 respectively in conjunction 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 removal zinc, bismuth and magnesium.It is lower than the zinc bismuth alloy coated Si magnesium alloy particles of magnesium burning point by using not oxidizable, fusing point, in conjunction under certain temperature solid-state diffusion processing and hypoxemia oxidation processing technique be the present invention obtain have microcellular structure foam silicon powder, improve preparation efficiency and foam silicon powder primary particle degree it is smaller.
Description
Technical field
The present invention relates to the preparation method of foam-like silicon powder more particularly to a kind of zinc bismuth alloy coated Si magnesium granules preparation bubbles
The method of foam shape silicon powder further relates to a kind of using foam-like silicon powder prepared by this method.
Background technique
Since silicon has the theoretical specific capacity (4200mAh/g) than high ten times of graphite cathode or more, replaced using silicon present
Common graphite cathode has become the target of high-energy density power battery research.Silicon has volume expansion as cathode in use
Greatly, silicon particle rupture, dusting, the disadvantage that first charge-discharge coulombic efficiency is low and impedance is high；It is a series of for disadvantages mentioned above
Improved method has been found effectively, the rupture of bulk silicon can be such as reduced using nanoscale silicon particle, using porous structure silicon
Grain can be relieved the volume 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 constituted has become the research hotspot of battery material.
The method for preparing nano silica fume has high-energy ball milling method, plasma heating vaporization condensation process, chemical method etc., wherein high
Energy ball grinding method is 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
The device is complicated for thermal evaporation condensation method, though the nano-silicon primary particle sphericity such as a kind of prior art preparation is high, this spherical shape
Nano-silicon is difficult to combine the after polymerization silicon particle for being formed with 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 large specific surface area of manufacture, but nano silica fume is manufactured using silane, 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, and the hydrofluoric acid used has highly corrosive, and not easy to operate, problem of environmental pollution is also difficult to solve.
The method of preparation porous silicon powder also has been reported that, such as a kind of silicon that three-dimensional dendritic crackle is prepared with using liquid nitrogen chilling
Micro mist manufacturing method, but the silicon powder of this method preparation has the shortcomings that silicon particle uniformity is poor；Such as a kind of utilization silicon, magnesium powder
The silicon magnesium compound method that pyrolytic obtains porous silicon again is synthesized, but the stereoscan photograph of patent disclosure confirms this side
The primary particle of the porous silicon of method preparation is larger, and using this porous silicon powder is in mass ratio silicon/carbon Compound Negative of 1: 1 preparation
Pole haves the shortcomings that similarly coulombic efficiency (59%) is low for the first time with metal silicium cathode, low coulombic efficiency for the first time and silicon powder it is primary
Grain graininess is related, the porous silicon powder of therefore this method preparation not can solve application problem of the crystalline silicon as cathode.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
It being kept the temperature in the bath of pure bismuth liquation, part magnesium is promoted to be dissolved in bismuth liquation, the powder of taking-up passes through nitric acid acidwashing again to remove bismuth and magnesium,
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 strict environmental Kuznets Curves means to reduce the risk of explosion of magnesium dust；And it is taken off in further bismuth liquation bath
Magnesium processing, needs the temperature of bismuth liquation at 450 DEG C or more, i.e. burning point (300 DEG C) about 150 DEG C of the temperature higher than magnesium, such temperature
Under magnesium easily ignition aoxidize, cause the high temperature spontaneous combustion burning of powder processed, thus bring silicon particle rapidly grow up and
The oxidation of silicon, therefore industrialized production porous nano silicon powder technique controlling difficulty is very big in this way, is especially difficult to control
The granularity of nano silica fume；A kind of utilization metal chloride fused-salt medium long-time heat preservation (10h~15h) point is also disclosed in the prior art
Si-Mg alloy powder, then the method that porous silicon is obtained by chlorohydric acid pickling are solved, this process eliminates the kindlings of magnesium in industrialized production
Burning risk, but technique requires long-time heat preservation, there is a problem of that powder preparation efficiency is low.
Summary of the invention
In view of this, the purpose of the present invention is to provide a kind of zinc bismuth alloy coated Si magnesium granules preparation foam-like silicon powders
Method and foam-like silicon powder, to solve above-described at least partly technical problem.
According to an aspect of the present invention, a kind of method of zinc bismuth alloy coated Si magnesium granules preparation foam-like silicon powder is provided,
Include:
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
With bismuth metal respectively in conjunction with magnesium pasc reaction；
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 removal zinc, bismuth and magnesium.
Further, in the zinc bismuth alloy, the mass percent of zinc is 0.1%-7.5%.
Further, after pickling removal zinc, bismuth and magnesium further include: ball milling and calcining in the medium of carbonaceous organic material
Forming surface has the foam silicon powder 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 following one:
Si-Mg alloy powder is mixed with metal zinc, the mixed-powder of bismuth meal or with zinc bismuth alloy powder, and using mechanical
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, passes through mechanical stirring 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 in the heat-treatment furnace of agitating device, pass through machinery
It stirs and heats 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 carry out pickling removal zinc, bismuth and magnesium include: by
Si-Mg alloy powder after oxidation processes carries out pickling, and pickling solution 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 silicon powder is made.
Further, ball milling and calcining specifically include in the medium of carbonaceous organic material: original foam shape silicon powder 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 tetrahydro furan
It mutters solution, polyvinyl alcohol water solution and polyimides/nmp solution.
According to another aspect of the present invention, a kind of foam-like silicon powder is provided comprising 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 silicon powder is less than 70nm and/or the specific surface of the foam-like silicon powder
Product is 26m2/ g~38m2/ g and/or the pore size are 5nm~100nm.
In accordance with a further aspect of the present invention, a kind of lithium ion battery, including negative electrode material are provided, the negative electrode material include with
Upper any foam-like silicon powder.
Through the above scheme, it is known that the beneficial effect of preparation method of the invention, foam silicon powder and lithium ion battery exists
In:
(1) it in preparation method of the present invention, on Si-Mg alloy powder surface, forms relatively stable, fusing point in air and is fired lower 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 powder processed certainly
Powder burning problem, can greatly improve production efficiency at the same time caused by firing；
(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 aforementioned magnesium in the prior art
Vigorous combustion problem is aoxidized, and as caused by magnesium combustion heating the shortcomings that silicon particle abnormal growth.
(4) there is the foam silicon powder 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 lower than 5%), better than the porous silicon powder of existing other technology preparations.
(5) in this preparation method it, using conventional intermediate frequency vacuum smelting method, overcomes and aforementioned uses magnesium in the prior art
The security risk of the kindling of magnesium powder dust in workshop existing for powder, explosion is suitable for industrialized mass production using 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 silicon powder is obtained in preparation method of the invention.
Detailed description of the invention
Fig. 1 is the method flow diagram of zinc bismuth alloy coated Si magnesium granules of embodiment of the present invention preparation foam-like silicon powder.
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 silicon powder prepared by the embodiment of the present invention one.
Fig. 4 is the X-ray diffracting spectrum of foam silicon powder prepared by the embodiment of the present invention one.
Specific embodiment
In this application, " primary particle granularity " refers to: single silicon crystal grain partial size.
It is emphasized that word "comprising" or " comprising " do not exclude the presence of element or step not listed in the claims
Suddenly.In addition, unless specifically described or the step of must sequentially occur, there is no restriction for the sequences of above-mentioned steps in listed above, and
It can change or rearrange according to required design.And above-described embodiment can be mixed each other based on the considerations of design and reliability
It closes collocation to use using or with other embodiments mix and match, i.e., the technical characteristic in different embodiments can freely form
More embodiments.
It unless there are known entitled phase otherwise anticipates, the numerical parameter in this specification and appended claims is approximation, energy
Enough bases pass through the resulting required characteristic changing of content of this disclosure.Specifically, all be used in specification and claim
The middle content for indicating composition, the number of reaction condition etc., it is thus understood that repaired by the term of " about " in all situations
Decorations.Under normal circumstances, the meaning expressed refers to include by specific quantity ± 10% variation in some embodiments, some
± 5% variation in embodiment, ± 1% variation in some embodiments, in some embodiments ± 0.5% variation.
It is an object of the invention to overcome the shortcoming of the preparation method of existing porous silicon powder and nano silica fume, one is proposed
Zinc bismuth alloy of the kind using fusing point lower than magnesium burning point forms clad in Si-Mg alloy powder particle surface, then passes through solid-state diffusion
Alloying realizes that the controllable control aoxidized at a slow speed with silicon nanocrystal of magnesium is grown up, finally by pickling in conjunction with hypoxemia oxidation technology
With medium ball milling and heat treatment process, preparing surface has carbonaceous conductive layer and possesses the method for the foam silicon powder of microcellular structure.Mainly
It is to use the zinc bismuth alloy coated Si magnesium alloy particles that not oxidizable, fusing point is lower than magnesium burning point, in conjunction under certain temperature
Solid-state diffusion processing and hypoxemia oxidation processing technique are that the present invention obtains the foam silicon powder with microcellular structure.
Fig. 1 is the method flow diagram of zinc bismuth alloy coated Si magnesium granules of embodiment of the present invention preparation foam-like silicon powder.Fig. 1 institute
Show, this method specifically includes that
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 respectively in conjunction with magnesium pasc reaction；
S104: the Si-Mg alloy powder after solid-state diffusion is heat-treated carries out oxidation processes；And
S105: the Si-Mg alloy powder after oxidation processes is subjected to pickling removal 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 some 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 at 1100 DEG C or more, be poured Si-Mg alloy ingot.Then it can will obtain
Si-Mg alloy ingot nitrogen atmosphere protection under be crushed, cross sieve classification.Using conventional intermediate frequency vacuum smelting method, before overcoming
It states in the prior art using the security risk of the kindling of workshop magnesium powder dust existing for magnesium powder, explosion.
In some embodiments, small intermediate frequency vacuum smelting furnace can be selected, according to melting graphite crucible capacity ingredient, 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 ingredient
It is melted with a small amount of blocky magnesium, melt temperature is controlled in fusion process while 1100-1200 DEG C, is added step by step remaining
Metal MAG block, after finally keeping the temperature 2-5 minutes, the cast iron mold being poured into after 250-300 DEG C of preheating obtains Si-Mg alloy ingot；
Then Si-Mg alloy ingot after cooling takes out, and under dry air atmosphere, is less than using the rough and torn granularity that is broken to of jaw crusher
After 5mm, sieve classification is crossed after vibratory milling in the case where there is nitrogen atmosphere protection.
For step S102: in some 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 lower 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 lower than magnesium burning point, will subtract 897098 and lack silicon
The surface oxidation fire risk of magnesium alloy powder.
In some embodiments, powder mixer tool alloying and/or at a certain temperature can be selected in method for coating
Melt stirs cladding process.
For method for coating, can selected from it is following any one: one, 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；Two, 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
The mixing of bismuth alloy powder, 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, passes through mechanical stirring and heat mixed powder.
In some embodiments, for step S103, by the zinc bismuth alloy cladding Si-Mg alloy powder of acquisition in vacuum or lazy
Property gas such as nitrogen, argon atmosphere under, temperature be higher than clad zinc bismuth alloy eutectic point temperature (254.5 DEG C), be 300-
550 DEG C, keep the temperature progress solid-state diffusion processing in 0.25-1.0 hours.Solid-state diffusion heat treatment process will can promote zinc bismuth alloy packet
The diffusion reaction of coating and magnesium forms bismuth magnesium, zinc-magnesium metallic compound, eliminates the quilt caused by magnesium kindling in this heat treatment process
Powder burning problem caused by powder spontaneous combustion is handled, production efficiency can be greatly improved at the same time.
In some embodiments, can select granularity is the Si-Mg alloy powder of 20-300 mesh, and preferred size is 80-200 mesh
Si-Mg alloy powder it is appropriate, by the weight of 1: 3-5 ratio-dependent cladding metal powder, and coating metal powder is by Zn content
For the zinc bismuth alloy powder of 0.1%-7.5% (mass percent)；Above-mentioned Si-Mg alloy powder and cladding metal powder are packed into not
It becomes rusty in cylinder of steel, supplying 2-4 times of mixed-powder weight, diameter are the sintered carbide ball of 6-12mm, and are filled with nitrogen or argon gas guarantor
Shield sealing, using common rotary mill mixing and ball milling 12-48 hours.Then can also make under the conditions ofs 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.
For the degree of perfection for further improving 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, control in-furnace temperature is zinc bismuth eutectic point or more, i.e., temperature is
265-355 DEG C, powder is heated by mechanical stirring and promotes cladding, to form fine and close clad 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
Into in clad zinc and bismuth metal respectively in conjunction with magnesium pasc reaction.Solid-state diffusion heat treatment process will can promote zinc bismuth alloy
The diffusion reaction of clad and magnesium forms bismuth magnesium, zinc-magnesium metallic compound, eliminates in this heat treatment process caused by magnesium kindling
Powder burning problem, can greatly improve production efficiency at the same time caused by powder spontaneous combustion processed.
In some embodiments, the coated composite powder that step S102 can be obtained is packed into tubular type vacuum drying oven, maintains vacuum degree
In 200Pa hereinafter, 300-550 DEG C of heat preservation 0.25-1.0h of selection temperature carries 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: the 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, will overcome the problems, such as the quick oxidation vigorous combustion of aforementioned magnesium in the prior art, and as caused by magnesium combustion heating
The shortcomings that silicon particle abnormal growth.
In some embodiments, above-mentioned oxidation processes are in the oxygen-nitrogen mixture body that oxygen content volume accounting is 5-20%
It carries out, the temperature of oxidation processes is 300-650 DEG C.
In some embodiments, the powder after the solid-state diffusion of acquisition being heat-treated, is packed into tubular type vacuum drying oven, leads to
Entering the oxygen-nitrogen mixture body that oxygen content is 5-20% (volume ratio) and maintaining furnace pressure is 0.05-0.1MPa, in in-furnace temperature
It is that 0.25-2 hours completion hypoxemia oxidation processes are kept the temperature at 300-650 DEG C.
For step S105, the Si-Mg alloy powder after oxidation processes is subjected to pickling removal zinc, bismuth and magnesium.The pickling
Step removes oxide (such as magnesia, bismuth oxide and zinc oxide) and the not residual metal (magnesium, bismuth and zinc) of complete oxidation,
After washing several times, acquisition original foam silicon powder after drying, being sieved.
In some embodiments, can by the Si-Mg alloy powder after oxidation processes carry out pickling, pickling solution be hydrochloric acid and/
Or nitric acid, to remove oxide and metal impurities, then it is washed to neutral after drying original foam shape silicon powder is made.
It in some embodiments, can be by the powder after oxidation processes, in the excess for being 1: 1 with the volume ratio of deionized water
Immersion treatment 1-5h in hydrochloric acid and/or nitric acid solution, to remove oxide and not the residual metal impurity of complete oxidation, through more
Original foam silicon powder is obtained after secondary washing, drying, sieving.
It in some embodiments, can also include step S106 after step S105: in the medium of carbonaceous organic material
Ball milling and calcining form the foam silicon powder that there is the microcellular structure of carbonaceous conductive layer on surface.
The medium of carbonaceous organic material is chosen, 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 some embodiments, above-mentioned and ball milling and calcining can be with are as follows: by original foam shape silicon powder 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.
It in some embodiments, can be by the original foam silicon powder that step S105 is obtained, in suitable zirconia ball and ball
For material than lower progress medium ball mill crushing, ball-milling medium uses mass percent for the polyvinyl alcohol water solution of 5-10%, adjusts silicon
The volume content of powder and ball is not more than the 80% of liquor capacity, and Ball-milling Time can adjust as needed, be usually no more than 2 hours；
In order to obtain stable carbonaceous conductive layer in final spongy silicon powder surface, such as pitch acetone soln, pitch tetrahydro 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 lower than 100 DEG C
After drying, in nitrogen atmosphere after 500~650 DEG C of calcined crushed processing, bubble as shown in Figure 3 with microcellular structure is obtained
Foam silicon powder.
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 well known to personnel is to obtain certain carbonaceous conductive layer on Si powder surface.
According to another aspect of an embodiment of the present invention, a kind of foam-like silicon powder is also provided comprising 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, and easier combination is formed with the after polymerization silicon particle in a large amount of gaps, is conducive to subsequent work
Skill processing.Above-mentioned foam-like silicon powder, micro cellular voids are uniform, and the crystallinity of silicon particle is high, and powder entirety oxygen content is low.
In some 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 some embodiments, the primary particle granularity of the foam-like silicon powder is less than 70nm and/or the foam-like silicon powder
Specific surface area is 26m2/ g~38m2/g。
According to another aspect of an embodiment of the present invention, a kind of lithium ion battery, including negative electrode material are also provided, the cathode material
Material includes the foam-like silicon powder of any description above.
To make the objectives, technical solutions, and advantages of the present invention clearer, below in conjunction with specific embodiment, and reference
Attached drawing, the present invention is described in further detail.Following embodiment narration is used to describe this technology, rather than carries out to the present invention
Limitation.Cognition is arrived various equivalent variations described below by the technical field of the invention personnel.
Embodiment one:
(1) small intermediate frequency vacuum smelting furnace is selected, according to melting graphite crucible capacity, by every furnace ingredient 1kg, siliceous 30-
The ratio of 35% (mass percent) prepares silico briquette and MAG block, under an argon atmosphere first by the silicon and a small amount of blocky magnesium in ingredient
Fusing controls melt temperature while 1100-1200 DEG C in fusion process, adds remaining metal MAG block step by step, finally
After heat preservation 2-5 minutes, the cast iron mold being poured into after 250-300 DEG C of preheating obtains Si-Mg alloy ingot；
(2) Si-Mg alloy ingot after cooling is taken out, under dry air atmosphere, is broken to using jaw crusher is rough and torn
After granularity is less than 5mm, the vibratory milling in the case where there is nitrogen atmosphere protection, after sieve classification；
(3) selecting granularity is the Si-Mg alloy powder of 20-300 mesh, and preferred size is the Si-Mg alloy powder 200 of 40-100 mesh
Gram, 1000 grams of cladding metal powders are equipped in 1: 5 ratio, cladding metal powder is preferably 30 grams of metal zinc of -100 mesh by granularity
It is mixed with 970 grams of metal bismuth meal, above-mentioned Si-Mg alloy powder and cladding metal powder is packed into the stainless cylinder of steel that diameter is 185mm
In, it is incorporated 2-4 times of sintered carbide ball of above-mentioned mixed-powder weight, 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 hours；
(4) further, the coated composite powder after above-mentioned ball milling mixing is 1200 grams total, it is incorporated with the heat of agitating device
In treatment furnace, under nitrogen atmosphere protection, control in-furnace temperature is 265-355 DEG C, 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) it by the coated composite powder of acquisition, is packed into tubular type vacuum drying oven, maintains vacuum degree in 200Pa hereinafter, selection temperature 300-
550 DEG C, preferably furnace temperature is 350-450 DEG C, and heat preservation is diffused heat treatment for 0.5 hour, and scanning electron microscopic observation (see Fig. 2) is shown
Form diffused alloy layer.
(6) it by powder after the diffusion heat treatments of acquisition, is packed into tubular type vacuum drying oven, being passed through oxygen content is 5-20% (volume
Than), preferably oxygen content is 10% oxygen-nitrogen mixture body, and maintaining furnace inner gas pressure is about 0.05MPa, in-furnace temperature 300-
650 DEG C, preferably furnace temperature is 400-450 DEG C, keeps the temperature 0.5 hour low oxygen content oxidation processes for completing coated composite powder；
(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 after washing several times, is dried, mistake with removing oxide and not the residual metal impurity of complete oxidation
Sieve obtains original foam silicon powder；
(8) original foam silicon powder is subjected to medium ball mill crushing, ball-milling medium under suitable zirconia ball and ratio of grinding media to material
It uses mass percent for 10% polyvinyl alcohol water solution, adjusts the volume content of silicon powder and ball no more than liquor capacity
80%, ball milling 1 hour；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 silicon powder of microcellular structure 1.:
Show that foam silicon powder gap is uniform through scanning electron microscopic observation (see Fig. 3), the granularity of the primary particle of foam silicon powder is small
In 50nm, and x-ray analysis (see Fig. 4) shows that a silicon particle of foam silicon powder has good crystallinity, and X-ray map does not have
Occur amorphous phase (mainly silica)
| Primary particle granularity (nanometer) | Foam silicon powder specific surface area (m2/g) | ||
| Embodiment one | Foam silicon powder is 1. | < 50nm | 38m2/g |
| Embodiment two | Foam silicon powder is 2. | < 70nm | 33m2/g |
| Embodiment three | Foam silicon powder is 3. | < 100nm | 30m2/g |
| Example IV | Foam silicon powder is 4. | < 60nm | 35m2/g |
| Embodiment five | Foam silicon powder is 5. | < 100nm | 28m2/g |
| Embodiment six | Foam silicon powder 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 silicon powder 1. is about 38m2/ g (is shown in Table 1).
Table 1
Embodiment two:
(1) (2) are the same as example 1；
(3) preferred size is 200 grams of Si-Mg alloy powder of 100-200 mesh, is equipped with 1000 grams of cladding metals in 1: 5 ratio
Powder, cladding metal powder are preferably mixed by granularity for 50 grams and 950 grams of metal bismuth meal of metal zinc less than 100 mesh, will be upper
It states Si-Mg alloy powder and coats metal powder and be fitted into the stainless cylinder of steel that diameter is 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
Rotary mill mixing and ball milling 36 hours；
(4) it is the same as example 1；
(5) it is the same as example 1；
(6) it by powder after the diffusion heat treatments of acquisition, is packed into tubular type vacuum drying oven, being passed through oxygen content is 5-25% (volume
Than), preferably oxygen content is 10% oxygen-nitrogen mixture body, and maintaining furnace inner gas pressure is about 0.05MPa, in-furnace temperature 350-
650 DEG C, preferably furnace temperature is 500-550 DEG C, keeps the temperature 0.5 hour low oxygen content oxidation processes for completing coated composite powder；
(7) it is the same as example 1；
(8) it is the same as example 1；
The foam silicon powder that embodiment two obtains is 2. 2. similar to the foam silicon powder of embodiment one, and gap is uniform, and crystallinity is good
It is good, occur without apparent silica amorphous phase；The primary particle granularity of foam silicon powder is less than 70nm, and nitrogen adsorption assay is real
Applying the specific surface area of the foam silicon powder of example two 2. is about 33m2/ g (is shown in Table 1).
Embodiment three:
(1) (2) are the same as example 1；
(3) preferred size is 200 grams of Si-Mg alloy powder of 200-300 mesh, is equipped with 1000 grams of cladding metals in 1: 5 ratio
Powder, cladding metal powder are preferably mixed by granularity for 75 grams and 925 grams of metal bismuth meal of metal zinc less than 100 mesh, will be upper
It states Si-Mg alloy powder and coats metal powder and be fitted into the stainless cylinder of steel that diameter is 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
Rotary mill mixing and ball milling 36 hours；
(4) coated composite powder after above-mentioned ball milling mixing is 1000 grams total, it is incorporated in the heat-treatment furnace of agitating device,
Under nitrogen atmosphere protection, control in-furnace temperature is 265-355 DEG C, 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 fine and close clad on Si-Mg alloy powder surface.
(5) it is the same as example 1；
(6) it by powder after the diffusion heat treatments of acquisition, is packed into tubular type vacuum drying oven, being passed through oxygen content is 5-20% (volume
Than), preferably oxygen content is 5% oxygen-nitrogen mixture body, and maintaining furnace inner gas pressure is about 0.1MPa, in-furnace temperature 350-
650 DEG C, preferably furnace temperature is 550-600 DEG C, keeps the temperature 1 hour low oxygen content oxidation processes for completing coated composite powder；
(7) it is the same as example 1；
(8) it is the same as example 1；
The foam silicon powder that embodiment three obtains is 3. similar to the foam silicon powder of above-described embodiment, and gap is uniform, and crystallinity is good
It is good, occur without apparent silica amorphous phase；The primary particle granularity of foam silicon powder is less than 100nm, nitrogen adsorption assay
The specific surface area of the foam silicon powder of embodiment two 2. is about 30m2/ g (is shown in Table 1).
Example IV:
(1) (2) are the same as example 1；
(3) preferred size is 200 grams of Si-Mg alloy powder of 40-100 mesh, is equipped with 800 grams of cladding metals in 1: 4 ratio
Powder, cladding metal powder are preferably mixed by granularity for 25 grams and 775 grams of metal bismuth meal of metal zinc less than 100 mesh, will be upper
It states Si-Mg alloy powder and coats metal powder and be fitted into the stainless cylinder of steel that diameter is 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
Rotary mill mixing and ball milling 36 hours；
(4) it is the same as example 1；
(5) it is the same as example 1；
(6) it by powder after the diffusion heat treatments of acquisition, is packed into tubular type vacuum drying oven, being passed through oxygen content is 5-20% (volume
Than), preferably oxygen content is 10% oxygen-nitrogen mixture body, and maintaining furnace inner gas pressure is about 0.1MPa, in-furnace temperature 350-
650 DEG C, preferably furnace temperature is 350-400 DEG C, keeps the temperature 0.5 hour low oxygen content oxidation processes for completing coated composite powder；
(7) it is the same as example 1；
(8) it is the same as example 1；
The foam silicon powder that example IV obtains is 4. similar to the foam silicon powder of above-described embodiment, and gap is uniform, and crystallinity is good
It is good, occur without apparent silica amorphous phase；The primary particle granularity of foam silicon powder is less than 60nm, and nitrogen adsorption assay is real
Applying the specific surface area of the foam silicon powder of example two 2. is about 35m2/ g (is shown in Table 1).
Embodiment five:
(1) (2) are the same as example 1；
(3) preferred size is 200 grams of Si-Mg alloy powder of 100-200 mesh, is equipped with 800 grams of cladding metals in 1: 4 ratio
Powder, cladding metal powder are preferably mixed by granularity for 40 grams and 760 grams of metal bismuth meal of metal zinc less than 100 mesh, will be upper
It states Si-Mg alloy powder and coats metal powder and be fitted into the stainless cylinder of steel that diameter is 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
Rotary mill mixing and ball milling 36 hours；
(4) coated composite powder after above-mentioned ball milling mixing is 1000 grams total, it is incorporated in the heat-treatment furnace of agitating device,
Under nitrogen atmosphere protection, control in-furnace temperature is 265-355 DEG C, 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 fine and close clad on Si-Mg alloy powder surface.
(5) it is the same as example 1；
(6) it by powder after the diffusion heat treatments of acquisition, is packed into tubular type vacuum drying oven, being passed through oxygen content is 5-25% (volume
Than), preferably oxygen content is 15% oxygen-nitrogen mixture body, and maintaining furnace inner gas pressure is about 0.05MPa, in-furnace temperature 350-
650 DEG C, preferably furnace temperature is 450-500 DEG C, keeps the temperature 1 hour low oxygen content oxidation processes for completing coated composite powder；
(7) it is the same as example 1；
(8) it is the same as example 1；
The foam silicon powder that embodiment five obtains is 5. similar to the foam silicon powder of above-described embodiment, and gap is uniform, and crystallinity is good
It is good, occur without apparent silica amorphous phase；The primary particle granularity of foam silicon powder is less than 100nm, nitrogen adsorption assay
The specific surface area of the foam silicon powder of embodiment two 5. is about 28m2/ g (is shown in Table 1).
Embodiment six:
(1) (2) are the same as example 1；
(3) preferred size is 200 grams of Si-Mg alloy powder of 40-100 mesh, is equipped with 600 grams of cladding metals in 1: 3 ratio
Powder, cladding metal powder are preferably mixed by granularity for 30 grams and 570 grams of metal bismuth meal of metal zinc less than 100 mesh, will be upper
It states Si-Mg alloy powder and coats metal powder and be fitted into the stainless cylinder of steel that diameter is 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
Rotary mill mixing and ball milling 48 hours；
(4) coated composite powder after above-mentioned ball milling mixing is 800 grams total, it is incorporated in the heat-treatment furnace of agitating device,
Under nitrogen atmosphere protection, control in-furnace temperature is 265-355 DEG C, 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 fine and close clad on Si-Mg alloy powder surface.
(5) it is the same as example 1；
(6) it by powder after the diffusion heat treatments of acquisition, is packed into tubular type vacuum drying oven, being passed through oxygen content is 5-25% (volume
Than), preferably oxygen content is 10% oxygen-nitrogen mixture body, and maintaining furnace inner gas pressure is about 0.1MPa, in-furnace temperature 350-
650 DEG C, preferably furnace temperature is 400-450 DEG C, keeps the temperature 1 hour low oxygen content oxidation processes for completing coated composite powder；
(7) it is the same as example 1；
(8) it is the same as example 1；
The foam silicon powder that embodiment six obtains is 6. similar to the foam silicon powder of above-described embodiment, and gap is uniform, and crystallinity is good
It is good, occur without apparent silica amorphous phase；The primary particle granularity of foam silicon powder is less than 120nm, nitrogen adsorption assay
The specific surface area of the foam silicon powder of embodiment two 5. is about 26m2/ g (is shown in Table 1).
Comparative example:
As the comparison 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.), it presses
Following step is prepared for as the porous silicon powder compared.
(1) silicon, magnesium powder mixed powder are heated to 1000-1100 DEG C and keep the temperature 3-4 hours under helium protection, with synthesis
Mg-si master alloy powder；
(2) the mg-si master alloy powder that granularity is 100-200 mesh 500-550 DEG C of excessive pure bismuth is immersed under protection of argon gas to melt
In liquid bath, and 0.5 hour is kept the temperature to promote part magnesium to be dissolved in bismuth liquation；
(3) powder that takes out that treated from 500-550 DEG C of pure bismuth liquation bath, pour into no argon gas protection, it is open
In stainless steel boat, there is that a small amount of oxide yellow object is formed, powder starts spontaneous combustion and extends to whole powder therewith first；
(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 washing several times, dries, after sieving, obtain the porous silicon powder of comparative example.
The porous silicon powder crystallinity that comparative example obtains is good, occurs without apparent 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 further in detail the purpose of the present invention, technical scheme and beneficial effects
Describe in detail bright, it should be understood that the above is only a specific embodiment of the present invention, is not intended to restrict 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 protection of the invention
Within the scope of.
Claims (9)
1. a kind of method of zinc bismuth alloy coated Si magnesium granules preparation foam-like silicon powder, comprising:
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 respectively in conjunction with magnesium pasc reaction；
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 removal zinc, bismuth and magnesium.
2. the method according to claim 1, wherein
In the zinc bismuth alloy, the mass percent of zinc is 0.1%-7.5%.
3. the method according to claim 1, wherein after pickling removal zinc, bismuth and magnesium further include: have carbon containing
Ball milling and calcining form the foam silicon powder that there is the microcellular structure of carbonaceous conductive layer on surface in the medium of machine object.
4. the method according to claim 1, wherein the surface in Si-Mg alloy powder coats zinc bismuth alloy
The mode of layer is selected from following one:
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, passes through mechanical stirring 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 mill, and
And the mixed powder after mechanical ball mill is incorporated in the heat-treatment furnace of agitating device, mechanical stirring is passed through and heats mixed powder progress
Cladding.
5. the method according to claim 1, wherein the temperature of solid-state diffusion heat treatment is 300-550 DEG C.
6. the method according to claim 1, wherein it is 5- that the oxidation processes, which are in oxygen content volume accounting,
It is carried out in 20% oxygen-nitrogen mixture body, the temperature of oxidation processes is 300-650 DEG C.
7. according to the method described in claim 3, it is characterized in that, the Si-Mg alloy powder by after oxidation processes carries out
Pickling removal zinc, bismuth and magnesium include:
Si-Mg alloy powder after oxidation processes is subjected to pickling, pickling solution 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 silicon powder is made.
8. according to the method described in claim 7, it is characterized in that in the medium of carbonaceous organic material ball milling and calcining it is specific
Include:
Original foam shape silicon powder is subjected to ball milling in the medium of carbonaceous organic material, obtains slurry；And
500~650 DEG C of calcinings in nitrogen atmosphere, obtain carbon coating layer after slurry is dried.
9. according to the method described in claim 8, it is characterized in that, the medium of the carbonaceous organic material is selected from following at least one
Kind:
Pitch acetone soln, pitch tetrahydrofuran solution, polyvinyl alcohol water solution and PI/NMP solution.
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| JP4936357B2 (en) * | 2006-03-30 | 2012-05-23 | 住友軽金属工業株式会社 | Aluminum alloy plate for battery case lid with excellent laser weldability |
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