CN109301228A - A kind of lithium ion battery silicon materials and preparation method thereof - Google Patents
A kind of lithium ion battery silicon materials and preparation method thereof Download PDFInfo
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- CN109301228A CN109301228A CN201811293432.0A CN201811293432A CN109301228A CN 109301228 A CN109301228 A CN 109301228A CN 201811293432 A CN201811293432 A CN 201811293432A CN 109301228 A CN109301228 A CN 109301228A
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- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
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- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/386—Silicon or alloys based on silicon
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- H—ELECTRICITY
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- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
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Abstract
The invention discloses a kind of lithium ion battery silicon materials, including containing silicon substrate, it include that main body and setting are equipped with porous structure at body surfaces and outwardly extending random protrusion, the surface of main body and at least one in inside containing silicon substrate, the average pore size of porous structure is 10-500nm；It containing silicon substrate is obtained by porous material is expanded.Lithium ion battery provided by the invention has unique structure with silicon materials, improves cycle performance of the silicon materials as negative electrode material when, while improving the compacted density of silicon materials.The present invention also provides a kind of preparation methods of lithium ion battery silicon materials, comprising: (1) material is carried out pitting or constructed, obtain porous material；(2) by porous material and be added into reaction kettle, under the pressure of 0.5-5.0Mpa and 200-400 DEG C at a temperature of react 0.5-2h, obtain lithium ion battery silicon materials.The preparation method is simple to operation.
Description
Technical field
The present invention relates to battery technology field, in particular to a kind of lithium ion battery silicon materials and preparation method thereof.
Background technique
Currently, various novel silicium cathode materials are concerned the (theory of silicon because of its capacity and multiplying power with superelevation
Capacity is 4200mAh/g), in addition, important element one of of the silicon as the earth, provides innate advantage for large scale preparation.So
And up to 300% or more volume expansion and contraction can occur in charge and discharge process for this material, cause the electricity on electrode living
Property substance powder of detached, the special capacity fade of material, or even can cause the puncture of diaphragm, battery is burst, and cells burst occurs very
To accidents such as explosions.Therefore, how to prepare with low thermal expansion, the silicium cathode material of high conductivity and stability has become section
Grind the important topic of boundary and industrial circle.
Summary of the invention
For the drawbacks described above for solving the prior art, the present invention provides a kind of lithium ion battery silicon materials and its preparation side
Method, production process are simple and efficient, and while realizing that lithium ion battery is inexpensively prepared with silicon materials, realize lithium ion battery
With the high conductivity and stability of silicon materials, and the relatively low bulk in charge and discharge process.
Specifically, in a first aspect, the present invention provides a kind of lithium ion battery silicon materials, including contain silicon substrate, it is described to contain
Silicon substrate includes main body and is arranged on the body surfaces and outwardly extending random protrusion, the surface and inside of the main body
In at least one at be equipped with porous structure, the average pore size of the porous structure is 10-500nm；The silicon substrate that contains is by more
The material in hole is expanded to be obtained.
Wherein, described to be primary particle containing silicon substrate or construct the second particle formed by multiple nano-scale particles.
Wherein, the pattern containing silicon substrate is that rice krispies is flower-shaped.
Wherein, the lithium ion battery silicon materials further include the carbon-coating for being coated on the siliceous matrix surface, the carbon
The surface topography of layer is consistent with the surface topography containing silicon substrate.
Wherein, the average-size of lithium ion battery silicon materials is 1-200 μm, specific surface area 5-60m2/ g, pressure
Real density is 1.6-2.0g/cm3。
Wherein, the protrusion is 10-500nm from the outwardly extending length of the main body, and the gap between the protrusion is big
Small is 10-500nm.
Second aspect, the present invention provide a kind of preparation method of lithium ion battery silicon materials, comprising the following steps:
(1) material is subjected to pitting or constructed, obtain porous material；
(2) the porous material in step (1) is added into reaction kettle, under the pressure of 0.5-5.0Mpa
0.5-2h is reacted at a temperature of with 200-400 DEG C, obtains lithium ion battery silicon materials.
Wherein, in step (1), the porous material is porous micron order primary particle or secondary porous
Grain, the preparation method of the porous material are specific as follows:
Micron order silicon-containing particles are subjected to pitting, obtain the porous micron order primary particle；Or
Multiple nanoscale silicon-containing particles are placed in water or lotion, after stirring, multiple nanoscale silicon-containing particles are reunited,
After drying, construct to obtain the porous second particle.
Wherein, in step (2), the porous material and carbon source are mixed according to mass ratio for 1:0.05-0.5
It closes, obtains mixture, the mixture is added and is reacted into reaction kettle, obtain the lithium ion battery silicon materials.
Wherein, the porous material that step (1) obtains expands after reacting in the reaction kettle, expansion
Rate is 5 times or more.
Using the above scheme, brought beneficial effect mainly has the following aspects to the present invention:
(1) lithium ion battery provided by the invention with silicon materials include contain silicon substrate, it is described containing silicon substrate include main body and
Setting is in the body surfaces and outwardly extending random protrusion, and such special construction is silicon materials in charge and discharge process
Sufficiently large expansion space has been reserved, the charge and discharge circulation life of silicon materials is extended；
(2) in the present invention, the surface containing silicon substrate is coated using carbon coating means, is remarkably improved compound
The electric conductivity and stability of material；
(3) preparation method of lithium ion battery silicon materials provided by the invention, preparation process are simple and efficient, cost compared with
It is low.
Detailed description of the invention
Fig. 1 is the structural schematic diagram of lithium ion battery silicon materials made from an embodiment of the present invention；
Fig. 2 is the preparation process schematic diagram of an embodiment of the present invention lithium ion battery silicon materials；
Fig. 3 is the preparation process schematic diagram of another embodiment lithium ion battery silicon materials of the present invention；
Fig. 4 is the preparation process schematic diagram of a further embodiment of this invention lithium ion battery silicon materials.
Specific embodiment
As described below is the preferred embodiment of the embodiment of the present invention, it is noted that for the common skill of the art
For art personnel, under the premise of not departing from implementation principle of the present invention, several improvements and modifications can also be made, these improve and
Retouching is also considered as the protection scope of the embodiment of the present invention.
Referring to Fig. 1, Fig. 1 is the structural schematic diagram of lithium ion battery silicon materials made from the embodiment of the present invention 1.This hair
Bright first aspect provides a kind of lithium ion battery silicon materials, including contains silicon substrate 10, and the silicon substrate that contains includes 1 He of main body
It is arranged at least one in 1 surface of main body and outwardly extending random raised 2, the surface and inside of the main body 1
Equipped with porous structure 3, the average pore size of the porous structure 3 is 10-500nm；The silicon substrate 1 that contains is by porous siliceous material
Expect expanded obtain.
In the present invention, described containing silicon substrate includes main body and setting in body surfaces and outwardly extending random convex
It rises, the main body is generally referred to as the middle section of silicon substrate, and the protrusion is configured around the main body.The main body
Size can be micron order or nanoscale.It is referred at the surface of the main body and at least one in inside equipped with porous structure:
The surface of the main body or the internal surface for being equipped with porous structure or the main body and inside are equipped with porous structure.
In the present invention, the silicon substrate that contains is obtained by porous material is expanded.The porous material
Surface and internal at least one at contain hole, after follow-up expansion, the aperture of some holes becomes larger, and some holes are even
Expansion is split, the silicon materials outwardly convex split, and ultimately form three-dimensional flower-shaped porous structure contains silicon substrate.Optionally, described
Porous material includes porous primary particle or porous second particle, and the second particle is by multiple nanoscales
Grain, which is constructed, to be formed.Still optionally further, the size of the primary particle is 1 μm -30 μm, is contained in the porous primary particle
There is nanoscale hole hole, the aperture of the nanoscale hole hole is 10-100nm, and the porosity of the primary particle is 60%-90%.
Still optionally further, the size of the second particle is 1 μm -20 μm.The size of the nano-scale particle is 10-100nm.It is described
Porous structure in second particle refers in second particle, the gap between nano-scale particle.The hole of porous second particle
Diameter is 10-100nm, and the porosity of the porous second particle is 50%-90%.
Preferably, the nano-scale particle can be solid or porous.When the nano-scale particle is porous knot
When structure, porous structure aperture is 1-5nm.
It is described to be primary particle containing silicon substrate or construct the second particle formed by multiple nano-scale particles in the present invention.
As porous primary particle expand described in containing silicon substrate be primary particle, construct formed two by multiple nano-scale particles
The silicon substrate that contains that secondary particle expansion obtains is second particle.When the second particle is expanded, multiple nanoscales
Gap between grain is split as hole expansion, to form silicon substrate." constructing " mentioned here refers to multiple nanoscales
Particle agglomeration or accumulation form second particle.Optionally, when it is described containing silicon substrate be primary particle when, the ruler containing silicon substrate
Very little is 30-150 μm.When it is described containing silicon substrate be construct the second particle formed by multiple nano-scale particles when, it is described contain silicon substrate
The size of body is 20-100 μm.
Optionally, the porous structure can be the expansion reserved space of silicon materials.The average pore size of the porous structure
For 10-500nm.Still optionally further, the average pore size of the porous structure is 10-50nm, 50-100nm or 100-500nm.
Optionally, the shape of the porous structure is unlimited, can be the shapes such as round, ellipse, polygon or irregular shape.
In the present invention, the surface containing silicon substrate is in random protrusion, described flower-shaped for rice krispies containing silicon substrate.It is described
Be containing silicon substrate obtained by porous material is expanded, wherein some holes even expand split, the silicon materials to split to
Outer lug forms protrusion, and convolution, distortion or overturning may further occur for these protrusions, to form rice krispies floral structure.It is optional
Ground, described containing silicon substrate includes main body and the protrusion that the body surfaces are arranged in.Still optionally further, the convex shape can
Think sheet, column, dendroid or linear.The length of the protrusion is 10-500nm, i.e., the described raised autonomous agent extends outwardly
Length be 10-500nm.Still optionally further, convolution, distortion or overturning can occur for the protrusion.Still optionally further, described
There can also be porous structure in protrusion, as shown in Figure 1.Still optionally further, existing gap size between the adjacent protrusion
For 10-500nm.These porous structures and gap further provide cushion space for silicon volume expansion.
In the present invention, the lithium ion battery silicon materials further include the carbon-coating for being coated on 10 surface containing silicon substrate
20, the surface topography of the carbon-coating 20 is consistent with the surface topography containing silicon substrate 10.Optionally, it is containing silicon substrate when described
Rice krispies is flower-shaped, and the carbon-coating for being coated on the flower-shaped siliceous matrix surface of the rice krispies can comply with the surface topography containing silicon substrate,
It is flower-shaped for rice krispies.Therefore, the surface topography of the carbon-coating and the surface topography containing silicon substrate are almost the same, finally obtained
Lithium ion battery silicon materials are whole also flower-shaped for rice krispies.Optionally, the carbon-coating can be porous structure, thus facilitate into
The volume expansion of one step inhibition silicon.Optionally, the porous aperture of the carbon-coating is 20-100nm.Optionally, the thickness of the carbon-coating
Degree is 10nm-2000nm.Still optionally further, the carbon-coating with a thickness of 10-200nm, 200nm-700nm or 700nm-
2000nm.In the present invention, the surface containing silicon substrate is coated using carbon coating means, is remarkably improved silicon materials
Electric conductivity and stability.
In the present invention, the material of the carbon-coating is selected from active carbon, graphite, graphene, carbon nanotube, carbon nano-fiber and charcoal
It is at least one of black.
In the present invention, the mass ratio containing silicon substrate and the carbon-coating is 1:0.03-0.3.
In the present invention, the average-size of lithium ion battery silicon materials is 1-200 μm.Optionally, average-size is
1-5 μm, 5-10 μm, 10-50 μm or 50-200 μm.
In the present invention, the specific surface area of lithium ion battery silicon materials is 5-60m2/g.Optionally, specific surface area is
50-60m2/g.The specific surface area for the lithium ion battery silicon materials that the present invention obtains is larger.
In the present invention, the compacted density of lithium ion battery silicon materials is 1.6-2.0g/cm3.Optionally, it is compacted close
Degree is 1.7-1.9g/cm3。
In the present invention, the material containing silicon substrate includes at least one of silicon and the sub- silicon of oxidation.
In the present invention, lithium metal is attached on the surface containing silicon substrate or in porous structure.Described it will contain silicon substrate
It is compound with lithium metal, lithium source can be supplemented for silicon materials, can effectively make up lithium ion battery and disappear in the process of initial charge
The lithium of consumption can allow lithium ion to deviate from from silicon materials, improve first charge-discharge efficiency in electric discharge.Optionally, the metal
Lithium and the molar ratio containing silicon substrate are 0.1-4:1.It is preferred that the lithium metal and the molar ratio containing silicon substrate are 0.5-
3:1.Further preferably, the lithium metal and the molar ratio containing silicon substrate are 1-2:1.
In the lithium ion battery silicon materials that first aspect present invention provides is three-dimensional flower-shaped porous structure containing silicon substrate,
Free space buffering is provided since its unique structure can expand for silicon in energy storage, without will cause lithium ion battery
Larger expansion occurs for volume in charge and discharge process when being applied to negative electrode material with silicon materials, so that negative electrode material is with excellent
Different cycle performance, in addition, silicon materials compacted density also with higher.
Second aspect of the present invention provides a kind of preparation method of lithium ion battery silicon materials, comprising the following steps:
(1) material is subjected to pitting or constructed, obtain porous material；
(2) the porous material in step (1) is added into reaction kettle, under the pressure of 0.5-5.0Mpa
0.5-2h is reacted at a temperature of with 200-400 DEG C, obtains lithium ion battery silicon materials.
In step of the present invention (1), the material is at least one of silicon and the sub- silicon of oxidation.Optionally, described
Material can be micron order silicon-containing particles, such as the micron order silicon-containing particles of specially 1-30 μm partial size, or nanometer
Grade silicon-containing particles, such as the nanoscale silicon-containing particles of specially 10-100nm partial size.Particular determination is not done to the shape of material,
It can be spherical or other shapes.
Referring to Fig. 2, the porous material is porous micro- in an embodiment of step of the present invention (1)
The preparation method of meter level primary particle, the porous micron order primary particle is specific as follows:
Micron order silicon-containing particles 31 described above are subjected to pitting, obtain the porous micron order primary particle 32.
The present invention uses the method for pitting to corrode to obtain porous structure material.Optionally, the hole of use
The method of erosion includes HF-HNO3Etch, Anodic etch or hydrothermal etching.Specifically, step (1) of the present invention is adopted
Hole etching method is HF-HNO3Etch, concrete technology include:
Material is added to HF-HNO3In system, and additive is added, under the conditions of 20-40 DEG C, reacts 1-4h,
Filtering, obtains porous silicon-containing material after washing.
In step of the present invention (1), the HF-HNO3In system, HF and HNO3Molar concentration rate be 1.5-5:1.
In step of the present invention (1), the additive is in oxalic acid, urea, sodium nitrite, acetic acid, methanol and ethyl alcohol
It is at least one.
In step of the present invention (1), the dosage of the additive is HNO3The 5-20% of quality.
In step of the present invention (1), many holes are contained on the surface and inside of the porous micron order primary particle 32
33.Optionally, these holes can be for through the hole of silicon materials or through the hole of silicon materials.Optionally, step (1) obtains
The porous micron order primary particle 32 aperture be 10-100nm.Optionally, the porous micron order primary particle
32 aperture is 20-80nm.
In the present invention, the porosity for the porous micron order primary particle 32 that step (1) obtains is 60%-
90%.
Referring to Fig. 3, the porous material is porous two in step of the present invention (1) another embodiment
The preparation method of secondary particle, the porous second particle is specific as follows:
Multiple nanoscale silicon-containing particles 41 are placed in water or lotion, after stirring, the multiple siliceous of the nanoscale
Grain 41 is reunited, and after drying, constructs to obtain the porous second particle 44.
In the present invention, the aperture of the porous second particle is 10-100nm.Here " porous " refers to nanoscale
After silicon-containing particles are reunited or are accumulated, the gap between nanoscale silicon-containing particles, as shown in 46 in Fig. 3.Optionally, described porous
Second particle size be micron order, such as the porous second particle size be 1-20 μm.Optionally, described porous
The porosity of second particle is 50%-90%.Preferably, the nano-scale particle can be solid or porous.Work as institute
State nano-scale particle be porous structure when, porous structure is having a size of 1-5nm.
Referring to Fig. 4, in step of the present invention (1) another embodiment, the preparation method of the porous second particle
It is specific as follows:
Nano-scale particle 41 is taken, pitting, the nanoscale are carried out to nano-scale particle 41 using the method for above-mentioned pitting
The surface and inside of grain go out multiple holes 43 by pitting, and during pitting, porous nano-scale particle is reunited, and washing is dried
After dry, construct to obtain porous second particle 42.
In step of the present invention (2), by the porous material and carbon source according to mass ratio be 1:0.05-0.5 into
Row mixing, obtains mixture, the mixture is added and is reacted into reaction kettle, obtain the lithium ion battery silicon material
Material.Optionally, the carbon source includes sucrose, lactose, glucose, starch, cellulose, high polymer cracking carbon, pitch cracking carbon, stone
At least one of black alkene and graphene oxide.Optionally, the porous silicon-containing material and the mass ratio of carbon source are 1:0.05-
0.1 or 1:0.1-0.5.In the present invention, the surface containing silicon substrate is coated using carbon coating means, is remarkably improved
The electric conductivity and stability of silicon materials.
In step of the present invention (2), reacted under the pressure of 0.5-1.5Mpa or under the pressure of 1.5-5.0Mpa.
In step of the present invention (2), the reaction time is 0.5-1h or 1-2h.
In step of the present invention (2), the porous silicon-containing material that step (1) obtains occurs swollen after reacting in a kettle
Swollen, expansion rate is 5 times or more.Specifically, expansion rate is 5-10 times." expansion rate " refers to the material body after expansion
The volume ratio of material before long-pending and unexpanded.
In step of the present invention (2), the Forming popcorn of the porous silicon-containing material that step (1) obtains in a kettle is greater than
Or it is equal to 95%." Forming popcorn " refers to that form the porous material of the flower-shaped composite material of rice krispies accounts for total porous contain
The weight ratio of silicon materials.
The porous material or mixture described above in step of the present invention (2), in the step (1)
Volume be the reaction kettle volume 5%-30%.Under the volume fraction, reaction is safe and efficient.
In step of the present invention (2), after reaction, reaction kettle is cooled to 100-150 DEG C, takes out lithium ion battery and use
Silicon materials.
In the present invention, many holes are contained in the porous material made from step (1).Optionally, this some holes
It hole can be for through the hole of silicon materials or through the hole of silicon materials.At high temperature under high pressure, the porous material
Will do it expansion, wherein the aperture for the hole having, which can expand, to become larger, some holes even expand split, the silicon materials to split to
Simultaneously convolution, distortion or overturning may occur for outer lug, and ultimately form three-dimensional flower-shaped porous structure contains silicon substrate.It is subsequent by carbon source
The carbon material of formation is coated on the surface containing silicon substrate, forms carbon-coating, obtains Si-C composite material.
In the present invention, lithium metal can also be added in step (2), by reaction, make lithium metal and the material
It is compound.
The preparation method for the lithium ion battery silicon materials that second aspect of the present invention provides, preparation process are simple and efficient, at
This is lower, and the lithium ion battery prepared silicon materials have special construction, and such special construction is silicon materials in charge and discharge
Sufficiently large expansion space has been reserved in the process, has extended the charge and discharge circulation life of silicon materials, improves its cycle performance, in addition,
Silicon materials compacted density also with higher.
Embodiment 1
A kind of preparation method of lithium ion battery silicon materials, comprising:
(1) preparation of porous silica material
10g micron silicon material is added to HF-HNO3Pitting is carried out in mixed solution, wherein HF and HNO3It is mole dense
Degree is added 4g oxalic acid, after isothermal reaction 4 hours, is filtered, washed to obtain porous silica material at 20 DEG C than being 1.5:1, porous to contain
The aperture of silicon materials is 10-50nm, porosity 60-80%.
(2) preparation of lithium ion battery silicon materials
Porous silica material obtained in step (1) is added into reaction kettle, the volume of reactant accounts for reaction kettle volume
20%, 300 DEG C are heated to, after reacting 1h, after being cooled to 100 DEG C, reaction kettle valve is quickly opened in safe material bin, is obtained
Lithium ion battery silicon materials.The Forming popcorn of porous silica material in a kettle is greater than 95%.
For lithium ion battery silicon materials made from embodiment 1 having a size of 1-10 μm, the aperture of porous structure is 50-100nm,
The length of protrusion is 100-200nm, specific surface area 50-60m2/ g, compacted density 1.7-2.0g/cm3。
Embodiment 2
A kind of preparation method of lithium ion battery silicon materials, comprising:
(1) preparation of porous silica material
10g micron order is aoxidized into sub- silicon materials and is added to HF-HNO3Pitting is carried out in mixed solution, wherein HF and HNO3's
Molar concentration rate is 5:1, and 2.5g urea is added, and at 80 DEG C after isothermal reaction 1 hour, is filtered, washed to obtain porous oxidation Asia
Silicon materials, the aperture of porous oxidation Asia silicon materials are 20-70nm, porosity 70-85%.
(2) preparation of lithium ion battery silicon materials
Porous oxidation Asia silicon materials obtained in step (1) are mixed according to mass ratio for 1:0.5, are mixed
Object is fed the mixture into reaction kettle, and the volume of reactant accounts for the 5% of reaction kettle volume, is heated to 200 DEG C, after reacting 2h,
After being cooled to 150 DEG C, reaction kettle valve is quickly opened in safe material bin, obtains lithium ion battery silicon materials.Porous oxygen
Change the Forming popcorn of sub- silicon materials in a kettle and is greater than 95%.
The size of the silicon materials of lithium ion battery made from embodiment 2 is 5-10 μm, and the aperture of porous structure is 100-
300nm, raised length are 300-400nm, specific surface area 50-60m2/ g, compacted density 1.7-2.0g/cm3。
Embodiment 3
A kind of preparation method of lithium ion battery silicon materials, comprising:
(1) preparation of porous silica material
10g micron silicon material is added to HF-HNO3Pitting is carried out in mixed solution, wherein HF and HNO3It is mole dense
Degree is added 7g sodium nitrite, after isothermal reaction 2 hours, is filtered, washed to obtain porous silica material at 40 DEG C than being 3:1.It is porous
The aperture of silicon materials is 70-100nm, porosity 80-90%.
(2) preparation of lithium ion battery silicon materials
Porous silica material obtained in step (1) is added into reaction kettle, the volume of reactant accounts for reaction kettle volume
30%, 400 DEG C are heated to, after reacting 0.5h, after being cooled to 120 DEG C, reaction kettle valve is quickly opened in safe material bin, is obtained
To lithium ion battery silicon materials.The Forming popcorn of porous silica material in a kettle is greater than 95%.
For lithium ion battery silicon materials made from embodiment 3 having a size of 10-30 μm, the aperture of porous structure is 300-
500nm, raised length are 400-500nm, specific surface area 50-60m2/ g, compacted density 1.7-2.0g/cm3。
Embodiment 4
A kind of preparation method of lithium ion battery silicon materials, comprising:
(1) preparation of porous silica material
10g nano silicone material is placed in water, after stirring, standing, multiple nanoscale silicon-containing particles are reunited, drying
Afterwards, it constructs to obtain porous silica material.The aperture of porous silica material is 10-20nm, porosity 50-70%.
(2) preparation of lithium ion battery silicon materials
Porous silica material obtained in step (1) is added into reaction kettle, the volume of reactant accounts for reaction kettle volume
30%, 400 DEG C are heated to, after reacting 0.5h, after being cooled to 120 DEG C, reaction kettle valve is quickly opened in safe material bin, is obtained
To lithium ion battery silicon materials.The Forming popcorn of porous silica material in a kettle is greater than 95%.
For lithium ion battery silicon materials made from embodiment 4 having a size of 1-20 μm, the aperture of porous structure is 100-
200nm, raised length are 100-200nm, specific surface area 50-60m2/ g, compacted density 1.7-2.0g/cm3。
Embodiment 5
A kind of preparation method of lithium ion battery silicon materials, comprising:
Porous silica material obtained in 1 step of embodiment (1) is mixed with sucrose according to mass ratio for 1:0.05, is obtained
It to mixture, feeds the mixture into reaction kettle, the volume of reactant accounts for the 20% of reaction kettle volume, is heated to 300 DEG C, instead
After answering 1h, after being cooled to 100 DEG C, reaction kettle valve is quickly opened in safe material bin, obtains lithium ion battery silicon materials.
The Forming popcorn of porous silica material in a kettle is greater than 95%.
Embodiment 6
A kind of preparation method of lithium ion battery silicon materials, comprising:
By porous oxidation Asia silicon materials obtained in (1) the step of embodiment 2 and glucose according to mass ratio be 1:0.5 into
Row mixing, obtains mixture, feeds the mixture into reaction kettle, the volume of reactant accounts for the 5% of reaction kettle volume, is heated to
200 DEG C, after reacting 2h, after being cooled to 150 DEG C, reaction kettle valve is quickly opened in safe material bin, obtains lithium ion battery
Use silicon materials.The Forming popcorn of porous oxidation Asia silicon materials in a kettle is greater than 95%.
Embodiment 7
A kind of preparation method of lithium ion battery silicon materials, comprising:
Porous silica material obtained in 3 step of embodiment (1) is mixed with pitch cracking carbon according to mass ratio for 1:0.1
It closes, obtains mixture, feed the mixture into reaction kettle, the volume of reactant accounts for the 30% of reaction kettle volume, is heated to 400
DEG C, after reacting 0.5h, after being cooled to 120 DEG C, reaction kettle valve is quickly opened in safe material bin, obtains lithium ion battery use
Silicon materials.The Forming popcorn of porous silica material in a kettle is greater than 95%.
Embodiment 8
A kind of preparation method of lithium ion battery silicon materials, comprising:
Porous silica material obtained in 4 step of embodiment (1) is mixed with pitch cracking carbon according to mass ratio for 1:0.1
It closes, obtains mixture, feed the mixture into reaction kettle, the volume of reactant accounts for the 30% of reaction kettle volume, is heated to 400
DEG C, after reacting 0.5h, after being cooled to 120 DEG C, reaction kettle valve is quickly opened in safe material bin, obtains lithium ion battery use
Silicon materials.The Forming popcorn of porous silica material in a kettle is greater than 95%.
Effect example
The present invention also provides comparative examples, to embody the effect of lithium ion battery silicon materials of the invention.
Comparative example 1
A kind of preparation method of Si-C composite material includes:
(1) preparation of porous silica material
10g micron silicon material is added to HF-HNO3Pitting is carried out in mixed solution, wherein HF and HNO3It is mole dense
Degree is added 4g oxalic acid, after isothermal reaction 4 hours, is filtered, washed to obtain porous silica material, obtain at 20 DEG C than being 1.5:1
The aperture of porous silicon-containing material is 10-50nm, porosity 60-80%.
(2) preparation of Si-C composite material
Porous silica material obtained in step (1) is mixed with sucrose according to mass ratio for 1:0.05, is mixed
Mixture is placed in tube furnace and is passed through under nitrogen at 700 DEG C the 6h that is carbonized, obtains carbon-coated porous silica material, i.e. silicon by object
Carbon composite.
Below by silicon-carbon composite wood made from lithium ion battery silicon materials made from above-described embodiment 5 and comparative example 1
Material, is assembled into button half-cell, further verifies its chemical property.Wherein, above-mentioned material is surveyed under conditions of 1C
Examination, the voltage ranges of charge and discharge are 0.01-2V, and test loop 100 and 300 enclose after capacity retention ratio.
The lithium ion battery of three-dimensional flower-shaped porous structure in embodiment 5 is discharged under conditions of 1C for the first time with silicon materials to be held
Amount is 2030mAh/g, and discharge capacity under conditions of 1C is 1950mAh/g to the Si-C composite material of comparative example 1 for the first time.In addition,
Lithium ion battery silicon materials in embodiment 5 are after the circle of circulation 300, and capacity retention ratio is 85% or more.And in comparative example 1
Si-C composite material after the circle of circulation 100, capacity retention ratio only has 80% or so, and after 300 circle of circulation, capacity is kept
Rate is 55% or so.From the foregoing, it can be seen that the embodiment of the present invention compares the lithium ion battery silicon it is found that embodiment with comparative example 1
The cycle performance of material is more preferable.In addition, the compacted density of comparative example 1 is only 1.6g/cm3Left and right, the lithium of the embodiment of the present invention 5 from
The compacted density of sub- battery silicon materials is higher.
One embodiment of the present invention above described embodiment only expresses, description is more in detail and specific, but simultaneously
Limitations on the scope of the patent of the present invention therefore cannot be interpreted as.It should be pointed out that for those of ordinary skill in the art
For, without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to guarantor of the invention
Protect range.Therefore, the scope of protection of the patent of the invention shall be subject to the appended claims.
Claims (10)
1. a kind of lithium ion battery silicon materials, which is characterized in that including containing silicon substrate, the silicon substrate that contains includes main body and sets
It sets at least one in the body surfaces and outwardly extending random protrusion, the surface and inside of the main body equipped with more
Pore structure, the average pore size of the porous structure are 10-500nm；The silicon substrate that contains is expanded by porous material
It obtains.
2. lithium ion battery silicon materials according to claim 1, which is characterized in that the silicon substrate that contains is primary particle
Or the second particle formed is constructed by multiple nano-scale particles.
3. lithium ion battery silicon materials according to claim 1, which is characterized in that the pattern containing silicon substrate is quick-fried
Popped rice shape.
4. lithium ion battery silicon materials according to claim 1, which is characterized in that the lithium ion battery silicon materials
It further include the carbon-coating for being coated on the siliceous matrix surface, the surface topography of the carbon-coating and the surface topography containing silicon substrate
Unanimously.
5. lithium ion battery silicon materials according to claim 1, which is characterized in that the lithium ion battery silicon materials
Average-size be 1-200 μm, specific surface area 5-60m2/ g, compacted density 1.6-2.0g/cm3。
6. lithium ion battery silicon materials according to claim 1, which is characterized in that the protrusion is outside from the main body
The length of extension is 10-500nm, and the gap size between the protrusion is 10-500nm.
7. a kind of preparation method of lithium ion battery silicon materials characterized by comprising
(1) material is subjected to pitting or constructed, obtain porous material；
(2) the porous material in step (1) is added into reaction kettle, under the pressure of 0.5-5.0Mpa and
0.5-2h is reacted at a temperature of 200-400 DEG C, obtains lithium ion battery silicon materials.
8. the preparation method of lithium ion battery silicon materials according to claim 7, which is characterized in that in step (1), institute
Stating porous material is porous micron order primary particle or porous second particle, the system of the porous material
Preparation Method is specific as follows:
Micron order silicon-containing particles are subjected to pitting, obtain the porous micron order primary particle；Or
Multiple nanoscale silicon-containing particles are placed in water or lotion, after stirring, multiple nanoscale silicon-containing particles are reunited, drying
Afterwards, it constructs to obtain the porous second particle.
9. the preparation method of lithium ion battery silicon materials according to claim 7, which is characterized in that, will in step (2)
The porous material is that 1:0.05-0.5 is mixed according to mass ratio with carbon source, mixture is obtained, by the mixing
Object is added to be reacted into reaction kettle, obtains the lithium ion battery silicon materials.
10. the preparation method of Si-C composite material according to claim 7, which is characterized in that step (1) obtains described
Porous material expands after reacting in the reaction kettle, and expansion rate is 5 times or more.
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