CN109950515A - A kind of Silicon Based Anode Materials for Lithium-Ion Batteries and preparation method thereof - Google Patents
A kind of Silicon Based Anode Materials for Lithium-Ion Batteries and preparation method thereof Download PDFInfo
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Abstract
The present invention provides a kind of Silicon Based Anode Materials for Lithium-Ion Batteries and preparation method thereof, which is made of at least one layer of protective layer of silicon particle and the package silicon particle, wherein the substance for being 1.5~4.5eV comprising forbidden bandwidth in the protective layer.Scheme provided by the invention can effectively inhibit the side reaction of silicon and electrolyte, to improve the cyclical stability of silicon based anode material.
Description
Technical field
The present invention relates to technical field of lithium batteries, in particular to a kind of Silicon Based Anode Materials for Lithium-Ion Batteries and its preparation side
Method.
Background technique
Negative electrode material due to silicon as lithium ion battery has theoretical specific capacity high (4200mAh/g), volume energy close
Spend big (9786mAh/cm3) the characteristics of, and the averagely de- lithium platform rather moderate (0.4V) of silicium cathode, in addition, due to silicon source
Extensively, at low cost, silicon is considered to have one of lithium ion battery negative material of potentiality.
Currently, the development bottleneck problem of silicium cathode material is poor cyclical stability.For this problem, propose
Negative electrode material is used as by silicon and carbon are compound, this method can improve the stability of silicium cathode to a certain extent, but still without
Method solve silicon in electrolyte anion or the generation such as anionic group such as hexafluoro-phosphate radical, fluoro ethyl carbonate base it is irreversible
Side reaction.Moreover, the study found that the presence of carbon can be catalyzed the side reaction of silicon and electrolyte.
Summary of the invention
The embodiment of the invention provides a kind of Silicon Based Anode Materials for Lithium-Ion Batteries and preparation method thereof, can effectively press down
The side reaction of silicon and electrolyte processed.
A kind of Silicon Based Anode Materials for Lithium-Ion Batteries, by least one layer of protective layer group of silicon particle and the package silicon particle
At, wherein the substance for being 1.5~4.5eV comprising forbidden bandwidth in the protective layer.
Preferably,
The apparent density of each layer protective layer is 1.2-4g/cm3。
Preferably,
The protective layer includes: one of metal fluoride, carbide, metal nitride, metal oxide or more
Kind.
Preferably,
The partial size of the silicon particle is 0.02~50 μm；
The protective layer be one layer when, the protective layer with a thickness of 0.002~20 μm；
When the protective layer is two layers, any one intermediate protective layer with a thickness of 0.002~20 μm, outer protective layer
With a thickness of 0.002~10 μm.
Preferably,
The partial size of the silicon particle is 50nm~300nm.
Preferably,
In the Silicon Based Anode Materials for Lithium-Ion Batteries of every mass parts, the mass fraction of the silicon particle is 10%~
95%, the total mass fraction of the protective layer is 5%~90%.
Preferably,
In the Silicon Based Anode Materials for Lithium-Ion Batteries of every mass parts, the mass fraction of the silicon particle is 60%~
85%, the total mass fraction of the protective layer is 15%~40%.
The preparation method of any of the above-described Silicon Based Anode Materials for Lithium-Ion Batteries, comprising:
The step of wrapping up at least one layer of protective layer by way of chemical deposition for the silicon particle, wherein the protection
The forbidden bandwidth of layer is 1.5~4.5eV.
Preferably, it is described be the silicon particle packing protective layer the step of, comprising:
The step of generating metal nitride protective layer, in ethanol by a certain amount of stock dispersion, ultrasonic treatment 0.5~
2h stirs 0.5~2h, forms mixed liquor, a certain amount of organic ester solution comprising metal group is added dropwise in Xiang Suoshu mixed liquor,
After addition finishes, at 60~150 DEG C, 2-3h is heated, the solid material that filtering/centrifugation obtains is placed in by filtering/centrifugation
In fixed bed reactors, it is passed through inert gas in Xiang Suoshu fixed bed reactors, and is heated to 850 DEG C, by the inert gas
Switch to ammonia, continuous heating 5h is cooled to room temperature and obtains target product, wherein the raw material include: silicon particle or comprising
The intermediate objective object of silicon particle；
Alternatively,
The step of generating metal nitride protective layer, a certain amount of raw material is layered on sponge, applies the pressure of 5~10MPa
The raw material is rolled into the thin slice that thickness is not more than 1mm by power, and the thin slice by the thickness no more than 1mm is put into magnetron sputtering
In device, the thin slice splash-proofing sputtering metal protective layer of 1mm is not more than for the thickness, sputters 0.5~2h of duration, obtains intermediate product,
The intermediate product is placed in tube furnace, inert gas is passed through, and is heated to 700~850 DEG C, the inert gas is cut
Change ammonia into, 2~8h of continuous heating is cooled to room temperature and obtains target product, wherein the raw material includes: silicon particle or packet
The intermediate objective object of silicon-containing particles；
Alternatively,
The step of generating metal fluoride protective layer, by a certain amount of stock dispersion in 1:1 ethanol/water solution, ultrasound
0.5~2h is handled, 0.5~2h is stirred, NH is added4F and metal chloride aqueous solution, continue 1~3h of stirring, pass through evaporation mode
Be evaporated liquid, remaining solid will be evaporated and be put into tube furnace, in Xiang Suoshu tube furnace, be passed through inert gas be heated to 700~
900 DEG C, 1~5h of heating is maintained, room temperature is cooled to and obtains target product, wherein the raw material includes: silicon particle or comprising silicon
The intermediate objective object of particle；
Alternatively,
The step of generating metal oxide protective layer, a certain amount of raw material is layered on sponge, applies the pressure of 5~10MPa
The raw material is rolled into the thin slice that thickness is not more than 2mm by power, and the thin slice by the thickness no more than 2mm is put into magnetron sputtering
In device, the thin slice splash-proofing sputtering metal protective layer of 2mm is not more than for the thickness, sputters 0.5~2h of duration, obtains intermediate product,
Then 1~5h is maintained with 400~800 DEG C of temperature in Muffle furnace, is cooled to room temperature and obtains target product.The raw material packet
It includes: silicon particle or the intermediate objective object comprising silicon particle.
Alternatively,
The step of generating metal carbides, a certain amount of silicon particle is placed in tube furnace, with certain gas velocity to institute
It states and is passed through inert gas in tube furnace, the tubular type in-furnace temperature is increased to 1300-1400 DEG C, the inert gas is switched
At carbon source, continues 15min, the carbon-source gas is switched to inert gas, is continually fed into the inert gas to the tubular type
Furnace is cooled to room temperature, and obtains the silicon particle with silicon carbide layer.The raw material includes: silicon particle or the centre comprising silicon particle
Object.
Preferably,
The intermediate objective object comprising silicon particle, comprising: the silicon particle is protected by the generation metal nitride
The step of the step of the step of layer/generation metal fluoride protective layer/generation metal oxide protective layer, is prepared into
To the target product with a protective layer.
Preferably,
The intermediate objective object comprising silicon particle, comprising: the silicon particle with carbon-coating.
The embodiment of the invention provides a kind of Silicon Based Anode Materials for Lithium-Ion Batteries and preparation method thereof, the lithium ion batteries
The substance for being 1.5~4.5eV comprising forbidden bandwidth in protective layer in silicon based anode material, can prevent silicon particle and electrolyte
In anion or anionic group such as hexafluoro-phosphate radical, fluoro ethyl carbonate base etc. react, but silicon can't be inhibited
Grain is reacted with lithium ion, and therefore, silicon based anode material provided in an embodiment of the present invention is by preventing in silicon particle and electrolyte
Anion or anionic group such as hexafluoro-phosphate radical, fluoro ethyl carbonate base etc. react, and effectively improve silicon substrate
The cyclical stability of negative electrode material.
Detailed description of the invention
In order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, to embodiment or will show below
There is attached drawing needed in technical description to be briefly described, it should be apparent that, the accompanying drawings in the following description is the present invention
Some embodiments for those of ordinary skill in the art without creative efforts, can also basis
These attached drawings obtain other attached drawings.
Fig. 1 is the 3 d structure model figure of Silicon Based Anode Materials for Lithium-Ion Batteries provided by one embodiment of the present invention；
Fig. 2 is the XRD diagram that side reaction occurs for characterization silicon and electrolyte provided by one embodiment of the present invention；
Fig. 3 is that side reaction TEM and EDS figure occur for characterization silicon provided by one embodiment of the present invention and electrolyte；
Fig. 4 is the TEM figure of cladding TiN protective layer in the surface Si provided by one embodiment of the present invention；
Fig. 5 is that there is characterization provided by one embodiment of the present invention the silicon based anode material of protective layer to inhibit side reaction
XRD diagram；
Fig. 6 is that there is characterization provided by one embodiment of the present invention the silicon based anode material of protective layer to inhibit side reaction
EELS Mapping figure；
Fig. 7 is the silicon based anode material cycle performance figure that characterization provided by one embodiment of the present invention has protective layer.
Specific embodiment
In order to make the object, technical scheme and advantages of the embodiment of the invention clearer, below in conjunction with the embodiment of the present invention
In attached drawing, technical scheme in the embodiment of the invention is clearly and completely described, it is clear that described embodiment is
A part of the embodiment of the present invention, instead of all the embodiments, based on the embodiments of the present invention, those of ordinary skill in the art
Every other embodiment obtained without making creative work, shall fall within the protection scope of the present invention.
The embodiment of the present invention provides a kind of Silicon Based Anode Materials for Lithium-Ion Batteries, the Silicon Based Anode Materials for Lithium-Ion Batteries
(following abbreviation silicon based anode materials) is made of at least one layer of protective layer of silicon particle and package silicon particle, wherein in protective layer
The substance for being 1.5~4.5eV comprising forbidden bandwidth.Wherein, the 3 d structure model figure of silicon based anode material can as shown in Figure 1,
It is the silicon based anode material comprising two layers of protective layer in Fig. 1, most the inside is silicon particle, and outer coversheet is protective layer.
The XRD result provided from Fig. 2 can be seen that when not having protective layer, negative electrode material of the silicon as lithium ion battery
When, after silicon reacts at a certain temperature with electrolyte, there is cenotype Li2SiF6, it is secondary anti-to illustrate that silicon and electrolyte have occurred
It answers.In addition, from silicon particle that Fig. 3-A is provided and electrolyte react after TEM figure and the silicon particle that provides of Fig. 3-B and electrolysis
The EDS of carbon after the silicon particle and electrolyte that EDSMapping figure, Fig. 3-C of silicon particle are provided after liquid reacts react
The result for the EDS Mapping figure that Mapping figure and Fig. 3-D provide the fluorine after silicon particle reacts with electrolyte can be bright
Aobvious finds out, the reunion of large area, while the aggregation of F element has occurred in silicon particle, further demonstrates between silicon and electrolyte
The generation of side reaction.
Due to the substance for being 1.5~4.5eV comprising forbidden bandwidth in protective layer, can prevent in silicon particle and electrolyte
Anion or anionic group such as hexafluoro-phosphate radical, fluoro ethyl carbonate base etc. react, but can't inhibit silicon particle with
The reaction of lithium ion, therefore, silicon lithium cell cathode material provided in an embodiment of the present invention is by preventing in silicon particle and electrolyte
Anion or anionic group such as hexafluoro-phosphate radical, fluoro ethyl carbonate base etc. react, and effectively improve silicon substrate
The cyclical stability of negative electrode material.
The anion or anion prevented in electrolyte in order to enable the protective layer in silicon based anode material to play
The apparent density of the purpose that group is contacted with silicon particle, every protective layer need to meet 1.2-4g/cm3。
In addition, above-mentioned at least one layer protective layer include metal fluoride, carbide, metal nitride, in metal oxide
One or more.
In an alternative embodiment of the invention, in order to guarantee the fully wrapped around silicon particle of protective layer, meanwhile, guarantee to be formed
Protective layer be enough to prevent silicon particle in electrolyte anion or anionic group react, the silicon particle in silicon based anode material
Partial size is 0.02~50 μm；Protective layer be one layer when, protective layer with a thickness of 0.002~20 μm；Protective layer is at least two layers
When, any one intermediate protective layer with a thickness of 0.002~20 μm, outer protective layer with a thickness of 0.002~10 μm.It is worth saying
Bright, when protective layer is at least two layers, intermediate protective layer refers to any one between silicon particle and outermost layer protective layer
Layer, for example, one layer between silicon particle and outermost layer protective layer is intermediate protective layer when protective layer is two layers；Protection
When layer is three layers, two layers between silicon particle and outermost layer protective layer is intermediate protective layer.
It is worth noting that there is no bright between protective layer and protective layer when having at least two layers of protective layer outside silicon particle
Aobvious boundary, the protective layer that the embodiment of the present invention limits refer to silicon particle or are once protected to protective layer silicon particle
Sheath generation step, then it is assumed that be that silicon particle forms a protective layer or increases one layer of guarantor for the silicon particle with protective layer
Sheath.Such as to silicon particle carry out generate metal nitride protective layer the step of operation, then the embodiment of the present invention i.e. be considered for
Wrap up the protective layer of one layer of metal nitride in silicon particle surface；Silicon particle with protective layer is carried out to generate metal nitride guarantor
The step of sheath, then the embodiment of the present invention is considered to increase outside the protective layer having had for the silicon particle with protective layer
The protective layer of one layer of metal nitride is added.
In an alternative embodiment of the invention, it is preferable that the partial size of silicon particle is 50nm~300nm, the silicon particle partial size position
The integrality of protective layer formation can be preferably controlled in 50nm~300nm range, while silicon-based anode can be effectively improved
The yield of material, the yield of the silicon based anode material refer to that the amount of the silicon particle with protective layer accounts for the ratio of raw material.
In an alternative embodiment of the invention, in order to guarantee the performance of silicon based anode material, need to guarantee the silicon of every mass parts
In sill, the mass fraction of silicon particle is 10%~95%, and the total mass fraction of protective layer is 5%~90%.Preferably, often
In the silicon based anode material of mass parts, the mass fraction of silicon particle is 60%~80%, and the total mass fraction of protective layer is 20%
~40%.
The preparation method of above-mentioned silicon based anode material, comprising: wrap up at least one by way of chemical deposition for silicon particle
The step of layer protective layer, wherein the forbidden bandwidth of protective layer is 1.5~4.5eV.
Specifically, the step of being silicon particle packing protective layer, can be with are as follows: the step of generating metal nitride protective layer.The life
The step of at metal nitride protective layer are as follows: in ethanol by a certain amount of stock dispersion, be ultrasonically treated 0.5~2h, ultrasound at
Continue 0.5~2h of stirring after the completion of reason, form mixed liquor, is added into mixed liquor a certain amount of organic molten comprising metal group
Liquid after addition finishes, at 60~150 DEG C, heats 2-3h, the solid material that filtering/centrifugation obtains is put in filtering/centrifugation
It is placed in fixed bed reactors, inert gas is passed through into fixed bed reactors, and be heated to 850 DEG C, inert gas is switched
At ammonia, continuous heating 5h is cooled to room temperature and obtains target product, wherein raw material includes: silicon particle or comprising silicon particle
Intermediate objective object.
In addition, the step of generating metal nitride protective layer can also be that a certain amount of raw material is layered on sponge, apply
Raw material is rolled into the thin slice that thickness is not more than 1mm by the pressure of 5~10MPa, and the thin slice by thickness no more than 1mm is put into magnetic control
In sputtering equipment, the thin slice splash-proofing sputtering metal protective layer of 1mm is not more than for thickness, sputters 0.5~2h of duration, obtains intermediate product,
Intermediate product is placed in tube furnace, inert gas is passed through, and is heated to 700~850 DEG C, inert gas is switched into ammonification
Gas, 2~8h of continuous heating are cooled to room temperature and obtain target product, wherein raw material includes: silicon particle or comprising silicon particle
Intermediate objective object.
In addition, the step of being silicon particle packing protective layer, can also be, the step of generating metal fluoride protective layer.The life
The step of at metal fluoride protective layer are as follows: by a certain amount of stock dispersion in 1:1 ethanol/water solution, ultrasonic treatment 0.5~
2h stirs 0.5~2h, and NH is added4F and metal chloride aqueous solution, continue 1~3h of stirring, are evaporated liquid by evaporation mode,
Remaining solid will be evaporated to be put into tube furnace, into tube furnace, inert gas is passed through and is heated to 700~900 DEG C, maintain heating
1~5h is cooled to room temperature and obtains target product, wherein raw material includes: silicon particle or the intermediate objective object comprising silicon particle.
In addition, the step of being silicon particle packing protective layer, can also be, the step of generating metal oxide protective layer.The life
The step of at metal oxide protective layer can include: a certain amount of raw material is layered on sponge, the pressure of 5~10MPa is applied, it will
Raw material is rolled into the thin slice that thickness is not more than 2mm, and the thin slice by thickness no more than 2mm is put into magnetic control sputtering device, is thickness
Thin slice splash-proofing sputtering metal protective layer no more than 2mm, sputter 0.5~2h of duration, obtain intermediate product, then in Muffle furnace with
400~800 DEG C of temperature maintains 1~5h, is cooled to room temperature and obtains target product.Raw material includes: silicon particle or comprising silicon
The intermediate objective object of grain.
In addition, the step of being silicon particle packing protective layer, can also be, the step of generating carbide protective layer.The carbide
The step of protective layer are as follows: a certain amount of raw material is placed in fluidized-bed reactor, with the gas velocity of 0.05~0.24m/s to fluidisation
It is passed through inert gas in bed reactor, fluidized-bed reactor cavity temperature is increased to 1000~1400 DEG C, inert gas is cut
It changes carbon-source gas into, maintains 30~80min, carbon-source gas is switched to inert gas, is continually fed into inert gas to fluidized bed
It is cooled to room temperature in reactor cavity, obtains the product with silicon carbide layer.Raw material includes: silicon particle or comprising in silicon particle
Between object.
The above-mentioned intermediate objective object comprising silicon particle can be the silicon particle with carbon-coating, or silicon particle is by life
The silicon particle with metal nitride protective layer formed at the step of metal nitride protective layer can also pass through for silicon particle
The silicon particle with metal fluoride protective layer or silicon particle that the step of generating metal fluoride protective layer is formed are by giving birth to
The silicon particle with metal oxide protective layer formed at the step of metal oxide protective layer can also be the silicon comprising silicon
Carbon complex, the siliceous alloys such as sial, silicon zinc.
The preparation method of the above-mentioned silicon particle with carbon-coating includes: that a certain amount of silicon particle is placed in fluidized-bed reactor
It is interior, inert gas is passed through into fluidized-bed reactor with the gas velocity of 0.004~0.05m/s, by fluidized-bed reactor cavity temperature
700~900 DEG C are increased to, inert gas is switched into carbon-source gas, 20~60min is maintained, carbon-source gas is switched to inertia
Gas is continually fed into inert gas and is cooled to room temperature to fluidized-bed reactor is intracavitary, obtains the silicon particle with carbon-coating.
In addition, the above-mentioned generation metal nitride protective layer the step of/generation metal fluoride protective layer the step of/generation
After the step of metal oxide protective layer, the target product that can also generate these steps is placed in reactor, with 0.005
~0.05m/s gas velocity is passed through inert gas, controls the cavity temperature of reactor to 700~900 DEG C, inert gas is switched to gas
The carbon-source gas of 0.005~0.12m/s of speed maintains 10~80min, carbon-source gas is switched to inert gas, is cooled to room temperature,
Obtain the product at least two layers protective layer, wherein carbon-source gas includes methane, one of ethane and ethylene or more
Kind.
By above-mentioned preparation method it is found that the silicon lithium cell cathode material with carbon-coating, needs to guarantee directly to wrap in carbon-coating
When wrapping up in silicon particle, need to continue to wrap up at least one layer of metal fluoride layer or metal nitride layer or metal oxide outside carbon-coating
Layer or carbide lamella.And silicon directly is being wrapped up at least one layer of metal fluoride layer or metal nitride layer or metal oxide layer
After particle, can also outside at least one layer of metal fluoride layer or metal nitride layer or metal oxide layer or carbide lamella after
One layer of carbon-coating of continuous package.
In addition, it is worth noting that, the protective layer being wrapped in outside silicon particle is usually no more than three layers.
Below with the detailed description of several specific embodiments.
Embodiment 1:
80nm silicon face coat one layer of carbon, carbon-coating with a thickness of 10nm or so, outside coats one layer of titanium nitride again, nitridation
The thickness of titanium layer is in 10nm or so.The mass fraction of silicon is 82.4%, and the mass fraction of intermediate carbon-coating is 6.3%, outermost layer nitrogen
The mass fraction for changing titanium is 11.3%, and the apparent density of material is in 1.2-2.0g/cm3。
Embodiment is as follows:
Nano silica fume made from mist projection granulating is placed in fluidized-bed reactor.Inertia is passed through with the gas velocity of 0.01m/s
Gas is fluidized and is heated to 900 DEG C, and gas source is then switched to ethylene gas, then control a length of 30min when reacting leads to
Enter inert gas to be cooled to room temperature, obtains the Si@C-material of carbon coating silicon particle；
In ethanol by the dispersion of Si C-material, it is ultrasonically treated 1h, stirring 1 hour, keeps material uniform after the completion of ultrasonic treatment
In ethanol, the solution containing titanium source such as butyl titanate/isopropyl titanate is then added dropwise, wherein every 10g Si C in dispersion
After material need to add solution of the 50mL containing titanium source, addition to finish, 95 DEG C are heated to, reacts 3h, then is coated on Si C-material surface
One layer of TiO2。
Next obtained solid material is placed in fixed bed reactors, is passed through inert gas and is heated to 850 DEG C, so
After switch to ammonia, for continuous heating 5h to get final product Si@C@TiN is arrived, i.e. one layer of carbon-coating, carbon-coating are wrapped up in silicon particle surface
Wrap up one layer of titanium nitride layer in surface.
Embodiment 2
50nm silicon face coat one layer of titanium nitride, titanium nitride with a thickness of 50nm, outside coats one layer of carbon-coating, carbon-coating again
Thickness in 10nm or so.The mass fraction of silicon is 82.4%, the mass fraction of middle nitride titanium 14.3%, outermost layer carbon
Mass fraction is 3.3%., the apparent density of material is in 2.5-3.0g/cm3。
Embodiment is as described below:
Take the silicon powder dispersion that diameter is 50nm in ethanol, stirring 1 hour after the completion of being ultrasonically treated 1 hour, being ultrasonically treated,
Keep material evenly dispersed in ethanol, 50mL solution containing titanium source is then added dropwise and is heated to 75 DEG C, instead after addition finishes
2h is answered, coats one layer of TiO on the surface of the material2, solid material is obtained by filtering/centrifugation；
Obtained solid material is placed in fixed bed reactors, inert gas is passed through and is heated to 850 DEG C, switch ammonification
Gas reacts 5h, switches to inert atmosphere and be cooled to room temperature, obtain the silicon particle Si@TiN for being enclosed with titanium nitride；
Si@TiN is placed in reactor, inert gas is passed through with the gas velocity of 0.05m/s and is heated, it is warm to 800 DEG C,
Then gas source is switched into ethane carbon source, reaction time 15min then passes to inert gas and is cooled to room temperature, obtains product
Si@TiN@C-material.
Embodiment 3
100nm silicon face coat one layer of silicon carbide, silicon carbide with a thickness of 40nm or so.The mass fraction of silicon is
86.2%, the mass fraction of silicon carbide layer is 13.8%., the apparent density of material is in 1.0-2.0g/cm3。
Embodiment is as described below:
It takes a certain amount of silicon powder, places in tube furnace, inert gas is passed through with 0.24m/s gas velocity and is fluidized and is heated to
1400 DEG C, gas source is then switched into methane carbon source, reaction time 60min then passes to inert gas and is cooled to room temperature, obtains
To product Si@SiC material.
Embodiment 4
100nm silicon face coat one layer of silicon carbide, silicon carbide with a thickness of 40nm or so, outside coats one layer of nitridation again
Titanium layer, the thickness of titanium nitride layer is in 50nm or so.The mass fraction of silicon is 75.5%, and the mass fraction of intermediate silicon carbide layer exists
10.8%, the mass fraction of titanium nitride layer is 14.7%., the apparent density of material is in 1.5-2.5g/cm3。
Embodiment is as described below:
The product Si@SiC material that embodiment 3 obtains is dispersed in 1L ethyl alcohol, 1h is ultrasonically treated, 1h is stirred, makes material
It is evenly dispersed that solution of tetrabutyl titanate is then added dropwise in ethanol, after addition finishes, 60 DEG C are heated to, reacts 3h,
Material surface coats one layer of TiO2, filtering/centrifugation obtains solid material；
Next obtained solid material is placed in fixed bed reactors, is passed through inert gas and is heated to 850 DEG C, it will
Inert gas switches to ammonia, reacts 5h, is cooled to room temperature and obtains final product Si@SiC@TiN.
Embodiment 5
Coat one layer of titanium nitride in 1 μm of silicon face, titanium nitride with a thickness of 200nm.The mass fraction of silicon is 58.5%, in
Between titanium nitride mass fraction 41.5%, the apparent density of material is in 2.8-3.5g/cm3。
Embodiment is as follows:
It takes the Si powder dispersion that diameter is 1 μm in ethanol, is ultrasonically treated 1h, stirs 1h, material is made to be dispersed in ethyl alcohol
In, solution of tetrabutyl titanate is then added dropwise, after addition finishes, is heated to 75 DEG C, reacts 3h, coat one on the surface of the material
Layer TiO2, filtering/centrifugation obtains solid material；
Obtained solid material is placed in fixed bed reactors, inert gas is passed through and is heated to 850 DEG C, then switch
At ammonia, 6h is reacted, room temperature is cooled to and obtains product Si TiN.The TEM of the product schemes as shown in figure 4, can be obvious from Fig. 4
Find out, outermost interplanar distance matches with TiN, it can be seen that outermost layer cladding be TiN layer.
Embodiment 6
Coat one layer of titanium nitride in 1 μm of silicon face, the titanium nitride with a thickness of 200nm, outside coats one layer of titanium nitride again,
The thickness of the titanium nitride layer of outer layer is in 100nm or so.The mass fraction of silicon is 50.3%, and the mass fraction of middle nitride titanium exists
33.3%, the mass fraction of outermost layer titanium nitride layer is 16.4%, and the apparent density of material is in 2.5-3.5g/cm3。
Embodiment is as follows:
The Si@TiN material that embodiment 5 obtains is layered on sponge, applies the pressure of 5~10MPa, it is little to be rolled into thickness
In the thin slice of 1mm, the thin slice by thickness no more than 1mm is put into magnetic control sputtering device, and the thin slice for thickness no more than 1mm sputters
Coat of metal sputters duration 2h, obtains intermediate product, intermediate product is placed in tube furnace, is passed through inert gas, and add
Heat switches to ammonia to 850 DEG C, by inert gas, and continuous heating 2h is cooled to room temperature and obtains product Si@TiN@TiN.
Embodiment 7
Coat one layer of aluminium nitride in 5 μm of silicon faces, aluminium nitride with a thickness of 200nm, the mass fraction of silicon is 85.3%, outside
The mass fraction of layer protective layer is 14.7%.The apparent density of material is in 2.0-2.5g/cm3。
Embodiment is as follows:
The silicon powder that diameter is 5 μm is equably layered on sponge, the pressure of 5MPa is then applied, silicon powder and sponge are rolled
Together into an entirety.Then the silicon wafer being rolled into is put into magnetic control sputtering device, is sputtered by magnetic control sputtering device
1h obtains intermediate product Si@Al in one layer of Al of uniformly sputtering of silicon powder；
Intermediate product Si@Al is placed in tube furnace, inert gas is passed through and is heated to 700 DEG C, then switch to ammonia,
6h is reacted, inert gas is then passed through and is cooled to room temperature and obtain product Si@AlN.
Embodiment 8
90nm silicon face coat one layer of aluminium nitride, aluminium nitride with a thickness of 500nm, outermost coats one layer of nitridation again
Titanium, the thickness of titanium nitride is at 1 μm or so, and the mass fraction of silicon is 10.3%, and the mass fraction of outer protective layer is 40.4%, most
The mass fraction of outer layer carbon is 50.3%.The apparent density of material is in 3.5-4.0g/cm3。
Embodiment is as follows:
Diameter is that the silicon powder of 90nm is equably layered on sponge, then applies 8MPa pressure, silicon powder and sponge are rolled into
Become an entirety together；The silicon wafer being rolled into is put into magnetic control sputtering device, 1.5h is sputtered by magnetic control sputtering device,
One layer of Al of uniformly sputtering of silicon powder, obtains Si@Al intermediate product.
Next obtained material is placed in tube furnace, is passed through inert gas and is heated to 850 DEG C, then switches ammonification
Gas reacts 8h, obtains product Si@AlN；
In ethanol by product Si AlN dispersion, it is ultrasonically treated 2h, stirs 2h, formed mixed liquor, be added dropwise into mixed liquor
A certain amount of organic ester solution comprising metal group, after addition finishes, at 95 DEG C, heating 3h, filtering/centrifugation, incited somebody to action
The solid material that filter/centrifugation obtains is placed in fixed bed reactors, inert gas is passed through into fixed bed reactors, and heat
To 850 DEG C, inert gas is switched into ammonia, continuous heating 5h is cooled to room temperature and obtains product Si@AlN@TiN.
Embodiment 9
One layer of aluminum fluoride is coated in 20 μm of silicon faces, in 500nm or so, the mass fraction of silicon is the thickness of aluminum fluoride
90.2%, the mass fraction of outer protective layer is 9.8%.The apparent density of material is in 3.0-4.0g/cm3。
Embodiment is as follows:
Si powder being dispersed in the solution of ethanol/water 1:1, is ultrasonically treated 1h, stirring 1h makes silicon powder be uniformly dispersed,
Then NH is added4F and Al (NO3)3〃9H2O aqueous solution, sufficiently reacts 1h after addition, steamed liquid by the method for evaporation
It is dry, it is passed through inert gas in tube furnace and is heated to 700 DEG C, and maintains 2h, obtains product Si@AlF3。
Embodiment 10
Coat one layer of carbon in 20 μm of silicon faces, carbon with a thickness of 500nm or so, outermost coats one layer of aluminum fluoride, fluorine again
Change the thickness of aluminium at 1 μm or so, the mass fraction of silicon is 88.2%, and the mass fraction of carbon-coating is 4.2%, aluminum fluoride protective layer
Mass fraction is 7.6%.The apparent density of material is in 3.3-4.3g/cm3。
Embodiment is as follows:
Silicon powder is placed in fluidized-bed reactor.Inert gas is passed through with the gas velocity of 0.025m/s to be fluidized and heated
To 800 DEG C, gas source is then switched into the carbon source that methane and ethane mix, reaction time 30min then passes to inert gas
It is cooled to room temperature, obtains carbon-coated material Si@C；
Si@C is dispersed in the solution of ethanol/water 1:1,1h is ultrasonically treated, stirring 1h makes silicon powder be uniformly dispersed,
Then NH is added4F and Al (NO3)3〃9H2O aqueous solution, sufficiently reacts 2h after addition, steamed liquid by the method for evaporation
It is dry, it is passed through inert gas in tube furnace and is heated to 800 DEG C, and maintains 3h, obtains product Si@C@AlF3。
Embodiment 11
30nm silicon face coat one layer of carbon, carbon with a thickness of 5nm, outermost coats one layer of aluminum fluoride again, aluminum fluoride
Thickness is 78.5% in 5nm or so, the mass fraction of silicon, and the mass fraction of outer protective layer is 9.6%, outermost layer AlF3Matter
Measuring score is 11.9%.The apparent density of material is in 1.1-1.8g/cm3。
Experimental program is as follows:
The nano silica fume for taking 100g mist projection granulating is placed in the fluidized-bed reactor that diameter is 1000mm.With 0.01m/s
Gas velocity be passed through inert gas and fluidized and be heated to 900 DEG C, gas source is then switched into carbon source, can be methane, ethane,
One or more of carbon-source gas such as ethylene, reaction time 30min then pass to inert gas and are cooled to room temperature, obtain
To carbon-coated Si@C-material.
1g Si@C-material is taken, is dispersed in the solution of ethanol/water 1:1, ultrasound, stirring each hour makes silicon
Powder is uniformly dispersed, and is then being slowly added into NH4F and Al (NO3)3〃9H2O aqueous solution sufficiently reacts 1h, then after addition
Liquid is evaporated by the method for evaporation, inert gas is then passed through in tube furnace and is heated to 700 DEG C, and maintains 2h, is obtained
Si@C@AlF3Product.
Embodiment 12
Diameter is that 40 μm of silicon powder is equably layered on sponge, then applies 8MPa pressure, silicon powder and sponge are rolled into
Become an entirety together；The silicon wafer being rolled into is put into magnetic control sputtering device, 5h is sputtered by magnetic control sputtering device, in silicon
One layer of Al of uniformly sputtering of powder, obtains Si@Al intermediate product.Then by product in Muffle furnace 800-900 DEG C of temperature
3h is forged under degree, obtains Si@Al2O3Target product.Wherein Al2O3Thickness at 10-13 μm, mass fraction is 32% or so.
Embodiment 13
300nm silicon face coat one layer of silicon carbide, silicon carbide with a thickness of 80nm or so, outside coats one layer of carbon again
Layer, the thickness of carbon-coating is in 50nm or so.The mass fraction of silicon is 79.5%, the mass fraction of intermediate silicon carbide layer 15.8%,
The mass fraction of titanium nitride layer is 4.7%.
Embodiment is as described below:
It takes a certain amount of silicon powder, places in tube furnace, inert gas is passed through with 0.5m/s gas velocity and is fluidized and is heated to
1400 DEG C, gas source is then switched into methane carbon source, reaction time 120min then passes to inert gas and is cooled to room temperature,
Obtain product Si@SiC material.
Si@SiC material is placed in fluidized-bed reactor.Inert gas is passed through with the gas velocity of 0.01m/s to be fluidized
And 900 DEG C are heated to, gas source is then switched into ethylene gas, it is cold to then pass to inert gas by control a length of 30min when reacting
But to room temperature, Si@SiC@C-material is obtained.The Si@SiC@C-material that the embodiment is obtained respectively is as negative electrode material and Si@C
After material is reacted as negative electrode material with electrolyte, XRD is tested, obtains the comparing result of XRD as shown in figure 5, can be with from Fig. 5
Find out, the material with protective layer such as SiC can effectively inhibit Li2SiF6Generation, can effectively inhibit silicon and electricity
Solve the side reaction of liquid.In addition, the Si@SiC@C-material that embodiment is obtained is as negative electrode material and electrolyte contacts by multiple
After charge and discharge cycles, EELS Mapping is carried out to the Si@SiC@C negative electrode material after circulation, obtains silicon member as shown in FIG. 6
Element, F element and Li distribution diagram of element, can significantly find out from Fig. 6, and F element is mainly distributed on the surface of particle, and Li
Element inside and outside material it can be seen that, illustrate that@SiC protective layer can prevent F-Infiltration, inhibit the generation of side reaction, together
When Li can be connected again+Effect.
In addition, the Si@C@TiN by providing embodiment 1 measures its cycle performance, obtained survey as negative electrode material
Test result is as shown in Figure 7.As can be known from Fig. 7, which stablizes 120 circle of circulation under the current density of 1A/g, holds
Amount remains within 1000mAh/g or more.
It can be improved negative electrode material cycle performance in order to more accurately show protective layer, to further illustrate protection
Layer can inhibit side reaction, as shown in the table, the cycle performance of the negative electrode material with different protective layers.With the cathode with carbon-coating
Material is compared, and the cycle performance of the negative electrode material with protective layer is more preferably.
Above-mentioned 1 μm of Si@C refers to, silicon particle surface have carbon-coating, carbon-coating with a thickness of 1 μm；Si@C80nm refers to, silicon
Grain surface have carbon-coating, carbon-coating with a thickness of 80nm.
Above-mentioned each embodiment can at least reach it is following the utility model has the advantages that
1. the substance for being in embodiments of the present invention, 1.5~4.5eV comprising forbidden bandwidth in protective layer, can prevent silicon
Particle in electrolyte anion or anionic group such as hexafluoro-phosphate radical, fluoro ethyl carbonate base etc. react, but simultaneously
It will not inhibit reacting for silicon particle and lithium ion, therefore, silicon lithium cell cathode material provided in an embodiment of the present invention passes through prevention
Silicon particle in electrolyte anion or anionic group such as hexafluoro-phosphate radical, fluoro ethyl carbonate base etc. react, and
Effectively improve the cyclical stability of silicon based anode material.
2. in embodiments of the present invention, the apparent density of every protective layer meets 1.2-4g/cm3, silicon lithium can be made electric
Protective layer in the negative electrode material of pond can play the anion or the mesh that contacts with silicon particle of anionic group prevented in electrolyte
, and silicon particle partial size is located at 50nm~300nm range can preferably control the integrality of protective layer formation, while can have
Improve the yield of silicon based anode material in effect ground.
3. being in embodiments of the present invention, 0.02~50 μm by the silicon particle partial size in control silicon based anode material；?
Protective layer be one layer when, protective layer with a thickness of 0.002~20 μm；When protective layer is at least two layers, any one intermediate protection
Layer with a thickness of 0.002~20 μm, outer protective layer with a thickness of 0.002~10 μm, can guarantee the fully wrapped around silicon of protective layer
Particle, meanwhile, guarantee the protective layer to be formed be enough to prevent silicon particle in electrolyte anion or anionic group react.
It should be noted that, in this document, such as first and second etc relational terms are used merely to an entity
Or operation is distinguished with another entity or operation, is existed without necessarily requiring or implying between these entities or operation
Any actual relationship or order.Moreover, the terms "include", "comprise" or its any other variant be intended to it is non-
It is exclusive to include, so that the process, method, article or equipment for including a series of elements not only includes those elements,
It but also including other elements that are not explicitly listed, or further include solid by this process, method, article or equipment
Some elements.In the absence of more restrictions, the element limited by sentence " including one ", is not arranged
Except there is also other identical factors in the process, method, article or apparatus that includes the element.
Finally, it should be noted that the foregoing is merely presently preferred embodiments of the present invention, it is merely to illustrate skill of the invention
Art scheme, is not intended to limit the scope of the present invention.Any modification for being made all within the spirits and principles of the present invention,
Equivalent replacement, improvement etc., are included within the scope of protection of the present invention.
Claims (10)
1. a kind of Silicon Based Anode Materials for Lithium-Ion Batteries, which is characterized in that by silicon particle and at least the one of the package silicon particle
Layer protective layer composition, wherein the substance for being 1.5~4.5eV comprising forbidden bandwidth in the protective layer.
2. Silicon Based Anode Materials for Lithium-Ion Batteries according to claim 1, which is characterized in that
The apparent density of each layer protective layer is 1.2-4g/cm3。
3. Silicon Based Anode Materials for Lithium-Ion Batteries according to claim 1, which is characterized in that
The protective layer includes: one or more of metal fluoride, carbide, metal nitride, metal oxide.
4. Silicon Based Anode Materials for Lithium-Ion Batteries according to claim 1, which is characterized in that
The partial size of the silicon particle is 0.02~50 μm；
The protective layer be one layer when, the protective layer with a thickness of 0.002~20 μm；
When the protective layer is two layers, any one intermediate protective layer with a thickness of 0.002~20 μm, the thickness of outer protective layer
Degree is 0.002~10 μm.
5. Silicon Based Anode Materials for Lithium-Ion Batteries according to claim 4, which is characterized in that
The partial size of the silicon particle is 50nm~300nm.
6. Silicon Based Anode Materials for Lithium-Ion Batteries according to claim 1, which is characterized in that
In the Silicon Based Anode Materials for Lithium-Ion Batteries of every mass parts, the mass fraction of the silicon particle is 10%~95%,
The total mass fraction of the protective layer is 5%~90%.
7. Silicon Based Anode Materials for Lithium-Ion Batteries according to claim 6, which is characterized in that
In the Silicon Based Anode Materials for Lithium-Ion Batteries of every mass parts, the mass fraction of the silicon particle is 60%~85%,
The total mass fraction of the protective layer is 15%~40%.
8. the preparation method of any Silicon Based Anode Materials for Lithium-Ion Batteries of claim 1 to 7 characterized by comprising
The step of wrapping up at least one layer of protective layer by way of chemical deposition for the silicon particle, wherein the protective layer
Forbidden bandwidth is 1.5~4.5eV.
9. preparation method according to claim 8, which is characterized in that the step for the silicon particle packing protective layer
Suddenly, comprising:
The step of generating metal nitride protective layer in ethanol by a certain amount of stock dispersion is ultrasonically treated 0.5~2h, stirs
0.5~2h is mixed, mixed liquor is formed, a certain amount of organic ester solution comprising metal group is added dropwise in Xiang Suoshu mixed liquor, be added
After finishing, at 60~150 DEG C, 2-3h is heated, the solid material that filtering/centrifugation obtains is placed in fixation by filtering/centrifugation
In bed reactor, it is passed through inert gas in Xiang Suoshu fixed bed reactors, and be heated to 850 DEG C, the inert gas is switched
At ammonia, continuous heating 5h is cooled to room temperature and obtains target product, wherein the raw material includes: silicon particle or comprising silicon
The intermediate objective object of grain；
Alternatively,
The step of generating metal nitride protective layer, a certain amount of raw material is layered on sponge, applies the pressure of 5~10MPa, will
The raw material is rolled into the thin slice that thickness is not more than 1mm, and the thin slice by the thickness no more than 1mm is put into magnetic control sputtering device
It is interior, the thin slice splash-proofing sputtering metal protective layer of 1mm is not more than for the thickness, sputters 0.5~2h of duration, intermediate product is obtained, by institute
It states intermediate product to be placed in tube furnace, is passed through inert gas, and be heated to 700~850 DEG C, the inert gas is switched to
Ammonia, 2~8h of continuous heating are cooled to room temperature and obtain target product, wherein the raw material includes: silicon particle or comprising silicon
The intermediate objective object of particle；
Alternatively,
The step of generating metal fluoride protective layer, by a certain amount of stock dispersion in 1:1 ethanol/water solution, ultrasonic treatment
0.5~2h stirs 0.5~2h, and NH is added4F and metal chloride aqueous solution, continue 1~3h of stirring, are evaporated by evaporation mode
Liquid will be evaporated remaining solid and be put into tube furnace, in Xiang Suoshu tube furnace, be passed through inert gas and be heated to 700~900
DEG C, 1~5h of heating is maintained, room temperature is cooled to and obtains target product, wherein the raw material includes: silicon particle or comprising silicon
The intermediate objective object of grain；
Alternatively,
The step of generating metal oxide protective layer, a certain amount of raw material is layered on sponge, applies the pressure of 5~10MPa, will
The raw material is rolled into the thin slice that thickness is not more than 2mm, and the thin slice by the thickness no more than 2mm is put into magnetic control sputtering device
It is interior, the thin slice splash-proofing sputtering metal protective layer of 2mm is not more than for the thickness, sputters 0.5~2h of duration, obtains intermediate product, then
1~5h is maintained with 400~800 DEG C of temperature in Muffle furnace, room temperature is cooled to and obtains target product, the raw material includes: silicon
Particle or intermediate objective object comprising silicon particle；
Alternatively,
The step of generating metal carbides, a certain amount of silicon particle is placed in tube furnace, with certain gas velocity to the pipe
It is passed through inert gas in formula furnace, the tubular type in-furnace temperature is increased to 1300-1400 DEG C, the inert gas is switched into carbon
Source continues 15min, the carbon-source gas is switched to inert gas, it is cold to the tube furnace to be continually fed into the inert gas
But to room temperature, the silicon particle with silicon carbide layer is obtained, the raw material includes: silicon particle or the intermediate objective comprising silicon particle
Object.
10. preparation method according to claim 9, which is characterized in that
The intermediate objective object comprising silicon particle, comprising: the silicon particle is by the generation metal nitride protective layer
Tool is prepared in the step of the step of step/generation metal fluoride protective layer/generation metal oxide protective layer
There is the target product of a protective layer；
Alternatively,
The intermediate objective object comprising silicon particle, comprising: the silicon particle with carbon-coating.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110571426A (en) * | 2019-09-10 | 2019-12-13 | 石家庄尚太科技有限公司 | Nitrogen-doped silicon-carbon composite negative electrode material and preparation method thereof |
| CN110993931A (en) * | 2019-12-23 | 2020-04-10 | 上海纳米技术及应用国家工程研究中心有限公司 | Modification method of silicon negative electrode material for lithium ion battery |
| CN112164780A (en) * | 2020-09-29 | 2021-01-01 | Oppo广东移动通信有限公司 | Silicon-based negative electrode material, preparation method thereof and related product |
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| CN112670474A (en) * | 2020-12-23 | 2021-04-16 | 清华大学 | Pre-lithiation material and preparation thereof, precursor material, lithium battery negative electrode slurry and lithium battery |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103545497A (en) * | 2013-10-18 | 2014-01-29 | 中国第一汽车股份有限公司 | Lithium ion battery cathode material with two-shell layer structure and preparation method thereof |
| CN105742583A (en) * | 2014-12-31 | 2016-07-06 | 三星电子株式会社 | Composite anode active material, anode including the composite anode active material, and lithium secondary battery including the anode |
| CN108390049A (en) * | 2018-04-16 | 2018-08-10 | 清华大学 | A kind of silicon@silicon carbide@carbon composite material of core-shell structure and preparation method thereof |
| CN108539150A (en) * | 2018-03-26 | 2018-09-14 | 合肥国轩高科动力能源有限公司 | A kind of comprehensive silicon negative material and preparation method thereof |
-
2019
- 2019-04-23 CN CN201910329186.8A patent/CN109950515A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103545497A (en) * | 2013-10-18 | 2014-01-29 | 中国第一汽车股份有限公司 | Lithium ion battery cathode material with two-shell layer structure and preparation method thereof |
| CN105742583A (en) * | 2014-12-31 | 2016-07-06 | 三星电子株式会社 | Composite anode active material, anode including the composite anode active material, and lithium secondary battery including the anode |
| CN108539150A (en) * | 2018-03-26 | 2018-09-14 | 合肥国轩高科动力能源有限公司 | A kind of comprehensive silicon negative material and preparation method thereof |
| CN108390049A (en) * | 2018-04-16 | 2018-08-10 | 清华大学 | A kind of silicon@silicon carbide@carbon composite material of core-shell structure and preparation method thereof |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112242504A (en) * | 2019-07-18 | 2021-01-19 | 北京清创硅谷科技有限公司 | Silicon carbide coated hollow silicon material, preparation method thereof, and electrode and electrochemical device using same |
| CN110571426A (en) * | 2019-09-10 | 2019-12-13 | 石家庄尚太科技有限公司 | Nitrogen-doped silicon-carbon composite negative electrode material and preparation method thereof |
| CN110993931A (en) * | 2019-12-23 | 2020-04-10 | 上海纳米技术及应用国家工程研究中心有限公司 | Modification method of silicon negative electrode material for lithium ion battery |
| CN112164780A (en) * | 2020-09-29 | 2021-01-01 | Oppo广东移动通信有限公司 | Silicon-based negative electrode material, preparation method thereof and related product |
| CN112670474A (en) * | 2020-12-23 | 2021-04-16 | 清华大学 | Pre-lithiation material and preparation thereof, precursor material, lithium battery negative electrode slurry and lithium battery |
| CN112670474B (en) * | 2020-12-23 | 2022-12-02 | 清华大学 | Pre-lithiation material and preparation thereof, precursor material, lithium battery negative electrode slurry and lithium battery |
| CN114229807A (en) * | 2021-12-06 | 2022-03-25 | 成都佰思格科技有限公司 | Si @ SiOx-TiN/C composite negative electrode material, preparation method and lithium ion battery |
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