CN105958023A - Preparation method of aluminum oxide coated silicon cathode material - Google Patents
Preparation method of aluminum oxide coated silicon cathode material Download PDFInfo
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- CN105958023A CN105958023A CN201610399056.8A CN201610399056A CN105958023A CN 105958023 A CN105958023 A CN 105958023A CN 201610399056 A CN201610399056 A CN 201610399056A CN 105958023 A CN105958023 A CN 105958023A
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Abstract
The invention provides a preparation method of an aluminum oxide coated silicon cathode material. The preparation method comprises the following steps: (A) in an oxygen-containing atmosphere, carrying out heat treatment of 500-1000 DEG C on nanometer silicon powder to obtain preoxidized nanometer silicon; (B) mixing the preoxidized nanometer silicon with aluminum powder and tin powder, and carrying out heat treatment of 400-900 DEG C to obtain an intermediate; and (C) treating the intermediate with acid or an oxidant to obtain the aluminum oxide coated silicon cathode material. In the preparation method, the thickness of an aluminum oxide coating layer can be controlled by adjusting the technological conditions of nanometer silicon preoxidization; the reaction raw materials are simple, flammable and combustible organic reactants and complex vacuum systems do not need to be used in the preparation process, the operation process is simple and practicable, the practicability degree is high, and the cost is low. The silicon substrate cathode material prepared and obtained by the preparation method has more stable surface structure in the lithium deembedding and embedding process, and is high in capacity retention ratio, high in cycling stability and high in performance.
Description
Technical field
The present invention relates to lithium ion battery material technical field, particularly relate to a kind of alumina-coated silicium cathode
The preparation method of material.
Background technology
Lithium ion battery have have extended cycle life, energy density is high, running voltage high, self-discharge rate is low,
The advantages such as volume is little and lightweight, be widely used in various portable electric appts, back-up source,
Energy-storage battery and electric automobile etc..At present, the commercial lithium-ion batteries negative material of main flow is carbon back
Material negative material, the most most widely used is graphite, and its theoretical specific capacity is 372mAh/g, but real
Capacity in the battery of border the most closely its power-carrying.Along with people are to lithium ion battery energy density
Requirement more and more higher, exploitation has the Novel cathode material for lithium ion battery of more high power capacity becomes research
One of focus.
The theoretical specific capacity of silicon is more than 10 times of graphite, reaches 4200mAh/g it is considered to be most send out
The cathode material for high capacity lithium ion battery of future generation of exhibition potentiality.But, silicon is during de-, embedding lithium
There are huge change in volume and surface can not form stable solid electrolyte film, cause capacity with circulation
Decay rapidly, the problem that coulombic efficiency is the highest, seriously hinder the application of its large-scale commercial.Because
This, research worker proposes nanorize, Surface coating and prepares the methods such as composite, to improving
The performance of silicon based anode material.
At present, Surface coating is the important means improving surface and interface stability.About silicium cathode material surface
The research of cladding is a lot, and wherein effectiveness comparison is apparent that Al2O3Cladding.Al2O3Clad is permissible
The suppression electrolyte decomposition on silicon based anode material surface, forms more stable solid electrolyte film.Pass through
Technique for atomic layer deposition (ALD) cladding Al2O3, the uniform cladding of atomic level can be reached.But
ALD need to use inflammable and explosive organo-aluminum compound and complicated vacuum-control(led) system, and cost is high, efficiency
Low and relatively difficult to the cladding of dusty material.Therefore, the most controlled a kind of Al is sought2O3Coated Si
Method be necessary.
Summary of the invention
In view of this, the application provides the preparation method of a kind of alumina-coated silicium cathode material, the present invention
The preparation method provided is simple, easy and simple to handle, low cost.
The present invention provides the preparation method of a kind of alumina-coated silicium cathode material, comprises the following steps:
A) under an oxygen-containing atmosphere, by nano silica fume through the heat treatment of 500～1000 DEG C, pre-oxidized
Nano-silicon；
B) nano-silicon of described pre-oxidation is mixed with aluminium powder and glass putty, through the heat treatment of 400～900 DEG C,
Obtain intermediate；
C) by the acid of described intermediate or oxidizer treatment, alumina-coated silicium cathode material is obtained.
Preferably, described step A) in, the time of described heat treatment is 10min～3h.
Preferably, described step A) in, described oxygen-containing atmosphere is selected from air or oxygen atmosphere.
Preferably, described step B) in, described heat treatment is carried out under an inert atmosphere.
Preferably, described step B) in, the time of described heat treatment is 1min～20h.
Preferably, described step B) in, described aluminium powder and glass putty gross mass and the mass ratio of nano silica fume
More than 1:2；
The quality of described glass putty accounts for the aluminium powder percent with glass putty gross mass more than 0 and less than or equal to 80%.
Preferably, described step B) in, the particle diameter of described aluminium powder and glass putty is independently selected from 100nm～50
μm。
Preferably, described step B) in, in the nano-silicon of described pre-oxidation, the thickness of oxide layer is
1nm～20nm.
Preferably, described step C) in, described acid is selected from hydrochloric acid, hydrobromic acid, sulphuric acid, nitric acid and acetic acid
In one or more；
Or, one or more in ferric chloride, copper chloride and bromine of described oxidant.
Preferably, described step C) particularly as follows: by the acid of described intermediate or oxidizer treatment, then
Through washing and solid-liquid separation, obtain alumina-coated silicium cathode material.
Compared with prior art, the present invention by nano silica fume under an oxygen-containing atmosphere through 500～1000 DEG C of heat treatments,
Make nano-silicon surface form oxide layer, obtain the nano-silicon of pre-oxidation；By nano-silicon and the metal of pre-oxidation
Aluminium powder and metallic tin powder mixing, through the heat treatment of 400～900 DEG C, then by acid or oxidizer treatment,
To alumina-coated silicium cathode material.The present invention utilizes metallic tin and metallic aluminium mixed-powder, at relatively low temperature
The oxide layer of the lower reduced nano silicon face of degree, and then coated aluminum oxide.In the present invention, alumina-coated
The thickness of layer can be controlled by the process conditions of regulation nano-silicon pre-oxidation；Reaction raw materials is simple, preparation
Process need not use inflammable and explosive organic reactant and complicated vacuum system, and operating process is the easiest
OK, degree of being practical is high, low cost.The silicon based anode material that the present invention prepares is in de-, embedding lithium mistake
Having more stable surface texture in journey, capability retention is high, good cycling stability, function admirable.
Accompanying drawing explanation
Fig. 1 is the stereoscan photograph of embodiment 1 gained silicon based anode material；
Fig. 2 is the transmission electron microscope photo of embodiment 1 gained silicon based anode material.
Detailed description of the invention
Below the technical scheme in the embodiment of the present invention is clearly and completely described, it is clear that retouched
The embodiment stated is only a part of embodiment of the present invention rather than whole embodiments.Based on the present invention
In embodiment, the institute that those of ordinary skill in the art are obtained under not making creative work premise
There are other embodiments, broadly fall into the scope of protection of the invention.
The invention provides the preparation method of a kind of alumina-coated silicium cathode material, comprise the following steps:
A) under an oxygen-containing atmosphere, by nano silica fume through the heat treatment of 500～1000 DEG C, pre-oxidized
Nano-silicon；
B) nano-silicon of described pre-oxidation is mixed with aluminium powder and glass putty, through the heat treatment of 400～900 DEG C,
Obtain intermediate；
C) by the acid of described intermediate or oxidizer treatment, alumina-coated silicium cathode material is obtained.
The preparation process that the present invention provides is simple, easy and simple to handle, low cost；Prepared by the present invention
Silicon based anode material there is excellent combination property.
Nano silica fume is placed in reaction vessel by the embodiment of the present invention, carries out heat treatment in oxygen-containing atmosphere,
Make nano-silicon surface form oxide layer by this pre-oxidation process, obtain the nano-silicon of pre-oxidation.
In embodiments of the present invention, described nano silica fume is the particle diameter silica flour at 1nm～500nm, preferably adopts
With the silica flour that particle diameter is 10nm～100nm；Described reaction vessel can be Muffle furnace commonly used in the art or pipe
Formula stove.In some embodiments of the invention, the D50 particle diameter of silica flour used is 100nm.Described oxygen-containing
Atmosphere includes air, oxygen atmosphere and other oxygen-containing mixed atmospheres, preferably air or oxygen atmosphere, more
It is preferably oxygen atmosphere.In the present invention, the temperature of described heat treatment is 500 DEG C～1000 DEG C, is preferably
600 DEG C～900 DEG C.In some embodiments of the invention, the heating rate of described heat treatment can be 5～10 DEG C
/min。
In the present invention, above-mentioned heat treatment makes nano-silicon pre-oxidize, and forms certain thickness oxygen on its surface
Change layer, obtain the nano-silicon of pre-oxidation.During pre-oxidation, the time of described heat treatment is preferably 10min～3h,
More preferably 0.5h～2h.In some currently preferred embodiments of the present invention, nano-silicon Pre oxidation is
650 DEG C, the time is 2h；Or Pre oxidation is 750 DEG C, the time is 1h；Or Pre oxidation is
800 DEG C, the time is 0.5h.In an embodiment of the present invention, oxide layer in the nano-silicon of described pre-oxidation
Thickness can be 1nm～20nm.
After obtaining the nano-silicon of pre-oxidation, embodiment of the present invention cooling such as the mode of natural cooling, by itself and
Metallic aluminium powder and metallic tin powder uniformly mix, and carry out heat treatment under conditions of temperature is 400～900 DEG C,
To intermediate.
The present invention uses metallic tin powder and metallic aluminium powder, by the heat treatment reduced nano silicon table of lower temperature
The oxide layer in face, reduction effect is more preferable.In the present invention, described aluminium powder and glass putty gross mass and nano-silicon
The mass ratio of powder is preferably greater than 1:2, more preferably (1:1)～(50:1), most preferably (8:1)～
(30:1).The quality of described glass putty accounts for the percent of aluminium powder and glass putty gross mass and is preferably greater than 0 and is less than
In 80%, more preferably 20%～70%, most preferably 25%～40%.In an embodiment of the present invention,
The metal dust that described aluminium powder and glass putty are well known to those skilled in the art；Silica flour used by the embodiment of the present invention,
Aluminium powder and glass putty are analytical pure or higher purity.The particle diameter of described aluminium powder and glass putty can be independently selected from
100nm～50 μm, in some embodiments of the invention, described aluminium powder and glass putty granularity are 200 mesh.
During reduction reaction of the present invention, described heat treatment is carried out the most under an inert atmosphere, obtains
Intermediate；Described inert atmosphere such as nitrogen atmosphere, argon gas atmosphere etc., preferably argon gas atmosphere.Described heat
The temperature processed is 400～900 DEG C, preferably 500～800 DEG C, most preferably 520～600 DEG C.Described heat
The time processed is preferably 1min～20h, more preferably 0.5h～10h, most preferably 1h～5h.
After obtaining intermediate, the embodiment of the present invention is lowered the temperature, and finally processes with acid or oxidant,
Thus obtain being coated with the silicon based anode material of aluminium oxide.
The embodiment of the present invention uses acid or oxidant, preferably can be removed by unreacted metal with acid；Wherein,
Described acid preferably is selected from one or more in hydrochloric acid, hydrobromic acid, sulphuric acid, nitric acid and acetic acid, more preferably
Hydrochloric acid or nitric acid.Or, described oxidant preferably be selected from the one in ferric chloride, copper chloride and bromine or
Multiple.The source of described acid and oxidant is commercially available, as used commercially available concentrated hydrochloric acid.In the present invention
Some embodiments in, with concentrated hydrochloric acid, unreacted metal dust is dissolved after cooling, until no longer produce
Bubble, metal dust is completely dissolved.
The embodiment of the present invention is by after the acid of described intermediate or oxidizer treatment, through washing and solid-liquid separation,
Obtain alumina-coated silicium cathode material.In an embodiment of the present invention, the mode of described solid-liquid separation is
Filter or centrifugation.The embodiment of the present invention can with centrifuge by nano silica fume and reacted solution separating,
Again through water or ethanol purge several times, it is dried, i.e. obtains the nano-silicon of alumina-coated.Wherein, described
Water is preferably deionized water.Described being dried preferably is carried out in vacuum drying oven；Described dry temperature can be
80 DEG C, the time can be 24h.
After obtaining silicon based anode material, the present invention is scanned electronic microscope photos (SEM), transmission electricity to it
The detection such as (TEM) and charge-discharge performance analyzed by mirror.Result shows, it is silica-based negative that the present invention prepares
Pole material surface is coated with protective layer of alumina；It may be considered has nucleocapsid structure, at silicon grain
One layer of aluminium oxide of Surface coating, silicon is core, aluminium oxide is shell.Further, prepared by the present invention
Silicon based anode material has more stable surface texture, excellent performance in de-, process of intercalation.By this
The silicon based anode material of bright offer is used for lithium ion battery, and application is good.
In sum, nano-silicon is carried out heat treatment in oxygen-containing atmosphere by the embodiment of the present invention, forms surface
Oxide layer, mixes the nano-silicon of pre-oxidation with metallic aluminium powder and metallic tin powder subsequently, and carries out heat treatment,
Remove unreacted metal again, thus obtain the silicon based anode material of alumina-coated.Gained silicon-based anode
The surface stability of material is good, and the surface side reaction occurred in de-, process of intercalation is few, capability retention
Height, good cycling stability.The present invention uses pre-oxidation and mock silver reduction to prepare this material, aluminium oxide
Cladding process is raw materials used simply, and the thickness of alumina-coated layer is easy to control, and whole method need not use
Inflammable and explosive organo-aluminum compound and complicated vacuum-control(led) system, process is simple, properties of product
Good, degree of being practical is high.
In order to be further appreciated by the application, alumina-coated silicon the application provided below in conjunction with embodiment
The preparation method of negative material is specifically described.
In following example, silica flour used, aluminium powder and glass putty are the granularity of analytical pure, aluminium powder and glass putty
It is 200 mesh.
Embodiment 1
The nano silica fume of 0.2 gram of 100nm (D50) is placed in tube furnace, in 650 DEG C in oxygen atmosphere
Process 2h, obtain the nano silica fume of pre-oxidation.After cooling, by silica flour and 2 grams of metallic aluminium powders of pre-oxidation
Uniformly mix with 1 gram of metallic tin powder, then process 2h in 560 DEG C in argon gas atmosphere, obtain intermediate.
Wherein, the heating rate of heat treatment is 5 DEG C/min；Cooling method is natural cooling.
After cooling, process intermediate with concentrated hydrochloric acid (mass percent is 37%), by unreacted metal
Powder dissolves, until no longer producing bubble, metal dust is completely dissolved；With centrifuge by nano silica fume
With reacted solution separating, then clean (cleaning process have certain loss) several times through deionized water；
Nano-silicon product after cleaning is placed in the vacuum drying oven of 80 DEG C and is dried 24h, obtains 0.18 gram of aluminium oxide
The nano-silicon of cladding, is the silicon based anode material of alumina-coated.
After obtaining silicon based anode material, the present invention is scanned electronic microscope photos (SEM) and transmission electricity to it
Mirror analyzes (TEM).It is embodiment 1 gained silicon based anode material that result sees Fig. 1 and Fig. 2, Fig. 1
Stereoscan photograph；Fig. 2 is the transmission electron microscope photo of embodiment 1 gained silicon based anode material.The present invention
The silicon based anode material Surface coating prepared has protective layer of alumina, the thickness ginseng of alumina-coated layer
Being shown in Table 1, table 1 is the relation of nano-silicon Pre oxidation, time and alumina-coated layer thickness.
The present invention carries out the chemical property detections such as discharge and recharge, and concrete grammar includes: gained nano-silicon negative pole
Material forms silicon-carbon complex through carbon cladding, and carbon content is 40wt%.Use CR2016 button cell,
With lithium metal for electrode, electrode plates by above-mentioned silicon-carbon complex, bonding agent (Kynoar),
And conductive black composition, three's mass ratio is 8:1:1；Electrolyte is the LiPF of 1mol/L6(ethylene
Carbonic ester) EC:(dimethyl carbonate) DMC (the two ratio is 1:1, v/v) solution, electric current density
For 100mA/g, voltage range 0.01V～1.5V, the active substance i.e. load capacity of silicon-carbon complex is
2mg/cm2.The capacity of battery is according to the Mass Calculation of silicon-carbon complex, and testing result sees table 2, table 2
Chemical property for embodiment 1～3 gained silicon based anode material.
Embodiment 2
The nano silica fume of 0.2 gram of 100nm (D50) is placed in tube furnace, in 750 DEG C in oxygen atmosphere
Process 1h, obtain the nano silica fume of pre-oxidation.After cooling, by silica flour and 2 grams of metallic aluminium powders of pre-oxidation
Uniformly mix with 1 gram of metallic tin powder, then process 2h in 560 DEG C in argon gas atmosphere, obtain intermediate.
Wherein, the heating rate of heat treatment is 5 DEG C/min；Cooling method is natural cooling.
After cooling, process intermediate with the concentrated hydrochloric acid of same embodiment 1, unreacted metal dust dissolved,
Until no longer producing bubble, metal dust is completely dissolved；With centrifuge by nano silica fume and reacted
Solution separating, then clean several times through deionized water；Nano-silicon product after cleaning is placed in 80 DEG C true
Empty baking oven is dried 24h, obtains the nano-silicon of 0.18 gram of alumina-coated.
The silicon based anode material Surface coating that the present invention prepares has protective layer of alumina, alumina-coated
The thickness of layer sees table 1.Carrying out chemical property detection according to the method in embodiment 1, result sees table
2。
Embodiment 3
The nano silica fume of 0.2 gram of 100nm (D50) is placed in tube furnace, in 800 DEG C in oxygen atmosphere
Process 30min, obtain the nano silica fume of pre-oxidation.After cooling, by silica flour and 2 grams of metallic aluminiums of pre-oxidation
Powder and 1 gram of metallic tin powder uniformly mix, then process 2h in 560 DEG C in argon gas atmosphere, obtain intermediate.
Wherein, the heating rate of heat treatment is 5 DEG C/min；Cooling method is natural cooling.
After cooling, process intermediate with the concentrated hydrochloric acid of same embodiment 1, unreacted metal dust dissolved,
Until no longer producing bubble, metal dust is completely dissolved；With centrifuge by nano silica fume and reacted
Solution separating, then clean several times through deionized water.Nano-silicon product after cleaning is placed in 80 DEG C true
Empty baking oven is dried 24h, obtains the nano-silicon of 0.18 gram of alumina-coated.
The silicon based anode material Surface coating that the present invention prepares has protective layer of alumina, alumina-coated
The thickness of layer sees table 1.Carrying out chemical property detection according to the method in embodiment 1, result sees table
2。
Embodiment 4～7
Prepare the nano-silicon of alumina-coated according to the method for embodiment 1, difference is pre-oxidation
Temperature, time difference；The thickness of alumina-coated layer sees table 1.
The relation of table 1 nano-silicon Pre oxidation, time and alumina-coated layer thickness
In the present invention, the thickness of alumina-coated layer can by regulation nano-silicon pre-oxidation temperature and
Time controls.Above example is preferred version of the present invention, by suitably changing pre-oxidation atmosphere and time,
The conditions such as the temperature and time of metal reduction, equally obtain the nano-silicon of alumina-coated.
The chemical property of table 2 embodiment 1～3 gained silicon based anode material
As shown in Table 2, the silicon based anode material that prepared by the present invention has more stable in de-, process of intercalation
Surface texture, capability retention is high, good cycling stability；Wherein alumina-coated layer thickness is 1～3nm
Time, best results.
Embodiment 8
The nano silica fume of 0.3 gram of 100nm (D50) is placed in tube furnace, in 650 DEG C in oxygen atmosphere
Process 2h, obtain the nano silica fume of pre-oxidation.After cooling, by silica flour and 3 grams of metallic aluminium powders of pre-oxidation
Uniformly mix with 1 gram of metallic tin powder, then process 2h in 560 DEG C in argon gas atmosphere, obtain intermediate.
Wherein, the heating rate of heat treatment is 5 DEG C/min；Cooling method is natural cooling.
After cooling, process intermediate with concentrated hydrochloric acid (mass percent is 37%), by unreacted metal
Powder dissolves, until no longer producing bubble, metal dust is completely dissolved；With centrifuge by nano silica fume
With reacted solution separating, then through deionized water clean several times；Nano-silicon product after cleaning is put
In the vacuum drying oven of 80 DEG C, it is dried 24h, obtains the nano-silicon of 0.25 gram of alumina-coated, be oxidation
The silicon based anode material of aluminum cladding.
Embodiment 9
The nano silica fume of 0.2 gram of 100nm (D50) is placed in tube furnace, in 650 DEG C in oxygen atmosphere
Process 2h, obtain the nano silica fume of pre-oxidation.After cooling, by silica flour and 3 grams of metallic aluminium powders of pre-oxidation
Uniformly mix with 1 gram of metallic tin powder, then process 3h in 520 DEG C in argon gas atmosphere, obtain intermediate.
Wherein, the heating rate of heat treatment is 5 DEG C/min；Cooling method is natural cooling.
After cooling, process intermediate with concentrated hydrochloric acid (mass percent is 37%), by unreacted metal
Powder dissolves, until no longer producing bubble, metal dust is completely dissolved；With centrifuge by nano silica fume
With reacted solution separating, then through deionized water clean several times；Nano-silicon product after cleaning is put
In the vacuum drying oven of 80 DEG C, it is dried 24h, obtains the nano-silicon of 0.18 gram of alumina-coated, be oxidation
The silicon based anode material of aluminum cladding.
Embodiment 10
The nano silica fume of 0.2 gram of 100nm (D50) is placed in tube furnace, in 650 DEG C in oxygen atmosphere
Process 2h, obtain the nano silica fume of pre-oxidation.After cooling, by silica flour and 2 grams of metallic aluminium powders of pre-oxidation
Uniformly mix with 1 gram of metallic tin powder, then process 2h in 560 DEG C in argon gas atmosphere, obtain intermediate.
Wherein, the heating rate of heat treatment is 5 DEG C/min；Cooling method is natural cooling.
After cooling, process intermediate with nitric acid (mass percent is 10%), by unreacted metal powder
End is dissolved, until no longer producing bubble, metal dust is completely dissolved；With centrifuge by nano silica fume and
Reacted solution separating, then clean several times through deionized water；Nano-silicon product after cleaning is placed in
The vacuum drying oven of 80 DEG C is dried 24h, obtains the nano-silicon of 0.18 gram of alumina-coated, be aluminium oxide
The silicon based anode material of cladding.
Comparative example 1
The nano silica fume of 0.2 gram of 100nm (D50) is placed in tube furnace, in 650 DEG C in oxygen atmosphere
Process 2h, obtain the nano silica fume of pre-oxidation.After cooling, by silica flour and 2 grams of metallic aluminium powders of pre-oxidation
Uniformly mix with 1 gram of metallic tin powder, then process 5min in 950 DEG C in argon gas atmosphere, obtain intermediate.
Wherein, the heating rate of heat treatment is 5 DEG C/min；Cooling method is natural cooling.
After cooling, process intermediate with hydrochloric acid (mass percent is 37%), by unreacted metal powder
End is dissolved, until no longer producing bubble, metal dust is completely dissolved；With centrifuge by nano silica fume and
Reacted solution separating, then clean several times through deionized water；Nano-silicon product after cleaning is placed in
The vacuum drying oven of 80 DEG C is dried 24h, obtains 0.18 gram of product.
This product comprises the silicon grain of a large amount of micron-scale, the surface alumina oxide of this kind of large scale silicon grain
Layer is few, and the nano-silicon content of alumina-coated is little.
Comparative example 2
The nano silica fume of 0.2 gram of 100nm (D50) is placed in tube furnace, in 650 DEG C in oxygen atmosphere
Process 2h, obtain the nano silica fume of pre-oxidation.After cooling, by silica flour and 2 grams of metallic aluminium powders of pre-oxidation
Uniformly mix with 1 gram of metal magnesium powder, then process 2h in 600 DEG C in argon gas atmosphere, obtain intermediate.
Wherein, the heating rate of heat treatment is 5 DEG C/min；Cooling method is natural cooling.
After cooling, processing intermediate with hydrochloric acid (mass percent is 10%), intermediate is completely dissolved,
Do not obtain the nano-silicon of alumina-coated.
As seen from the above embodiment, the present invention utilizes metallic tin and metallic aluminium mixed-powder, at lower temperature
The oxide layer of lower reduced nano silicon face, and then coated aluminum oxide.In the present invention, alumina-coated layer
Thickness can by regulation nano-silicon pre-oxidation process conditions control；Reaction raw materials is simple, prepares
Journey need not use inflammable and explosive organic reactant and complicated vacuum system, and operating process is simple,
Degree of being practical is high, low cost.The silicon based anode material that the present invention prepares is in de-, process of intercalation
Having more stable surface texture, capability retention is high, good cycling stability, function admirable.
The above is only the preferred embodiment of the present invention, it is noted that for making the art
Professional and technical personnel, on the premise of without departing from the technology of the present invention principle, is that by implementing these
The multiple amendment of example, and these amendments also should be regarded as the scope that the present invention should protect.
Claims (10)
1. a preparation method for alumina-coated silicium cathode material, comprises the following steps:
A) under an oxygen-containing atmosphere, by nano silica fume through the heat treatment of 500～1000 DEG C, pre-oxidized
Nano-silicon；
B) nano-silicon of described pre-oxidation is mixed with aluminium powder and glass putty, through the heat treatment of 400～900 DEG C,
Obtain intermediate；
C) by the acid of described intermediate or oxidizer treatment, alumina-coated silicium cathode material is obtained.
Preparation method the most according to claim 1, it is characterised in that described step A) in, institute
The time stating heat treatment is 10min～3h.
Preparation method the most according to claim 1, it is characterised in that described step A) in, institute
State oxygen-containing atmosphere selected from air or oxygen atmosphere.
Preparation method the most according to claim 1, it is characterised in that described step B) in, institute
State heat treatment to carry out under an inert atmosphere.
Preparation method the most according to claim 1, it is characterised in that described step B) in, institute
The time stating heat treatment is 1min～20h.
Preparation method the most according to claim 1, it is characterised in that described step B) in, institute
State aluminium powder and the glass putty gross mass mass ratio with nano silica fume more than 1:2；
The quality of described glass putty accounts for the aluminium powder percent with glass putty gross mass more than 0 and less than or equal to 80%.
Preparation method the most according to claim 6, it is characterised in that described step B) in, institute
State the particle diameter of aluminium powder and glass putty independently selected from 100nm～50 μm.
Preparation method the most according to claim 7, it is characterised in that described step B) in, institute
Stating the thickness of oxide layer in the nano-silicon of pre-oxidation is 1nm～20nm.
9. according to the preparation method described in any one in claim 1～8, it is characterised in that described step
Rapid C) in, one or more in hydrochloric acid, hydrobromic acid, sulphuric acid, nitric acid and acetic acid of described acid；
Or, one or more in ferric chloride, copper chloride and bromine of described oxidant.
Preparation method the most according to claim 9, it is characterised in that described step C) particularly as follows:
By the acid of described intermediate or oxidizer treatment, it is then passed through washing and solid-liquid separation, obtains aluminium oxide bag
Cover silicium cathode material.
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| CN114883551B (en) * | 2022-07-11 | 2022-09-27 | 深圳索理德新材料科技有限公司 | Alumina-coated nano silicon and continuous preparation method and system thereof |
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