CN109461890A - Silicon-carbon cathode material, preparation method and lithium ion battery - Google Patents
Silicon-carbon cathode material, preparation method and lithium ion battery Download PDFInfo
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- CN109461890A CN109461890A CN201710795274.8A CN201710795274A CN109461890A CN 109461890 A CN109461890 A CN 109461890A CN 201710795274 A CN201710795274 A CN 201710795274A CN 109461890 A CN109461890 A CN 109461890A
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- H01M4/02—Electrodes composed of, or comprising, active material
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- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- 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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- 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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- H—ELECTRICITY
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Abstract
The present invention provides a kind of silicon-carbon cathode material, preparation method and lithium ion battery.The raw material of the silicon-carbon cathode material includes silicon materials, graphitic carbon material, binder and additive, the silicon-carbon cathode material includes: silicon-carbon compound and the carbon layer that is coated on outside the silicon-carbon compound, wherein, the silicon-carbon compound is combined by the silicon materials and the graphitic carbon material, and the carbon layer is amorphous carbon coating layer.It is calculated according to the gross mass of the silicon-carbon cathode material, the mass ratio of the silicon materials is 10-60%, and the mass ratio of the graphitic carbon material is 30-80%, and the mass ratio of the carbon layer is 3-20%.Silicon-carbon cathode material according to the present invention overcomes and solves current silicium cathode material under the conditions of high capacity, the disadvantage that cyclical stability is poor, conductivity is low, low efficiency is inferior.
Description
Technical field
The present invention relates to a kind of silicon-carbon cathode material, preparation method and lithium ion batteries, more particularly, to a kind of use
In the silicon-carbon cathode material with high-energy density of lithium ion battery, preparation method and in high-energy density power battery
The middle application as cathode.
Background technique
It since lithium ion battery has the important advantage of high voltage, high capacity, and has extended cycle life, have a safety feature, make
It is many-sided with wide in portable electronic device, electric car, energy storage, space technology, biomedical engineering, national defense industry etc.
Wealthy application prospect becomes last decade and research and New Energy Industry heat that following a very long time is widely paid close attention to
Point.
Silicon can generate Li with lithium alloyage at normal temperature15Si4Phase, theoretical specific capacity are up to 3572mAh/g, are much higher than quotient
Industry graphite theoretical specific capacity (372mAh/g), and rich reserves (26.4%, occupy the 2nd) in crustal elements, while at
This is cheap, environmental-friendly, therefore silicium cathode material is paid close attention to and developed by scientific research and industrial circle personnel always, is most latent at present
Power and most good next-generation lithium ion battery negative material.
However, elemental silicon in charge and discharge process there are huge volume expansion, reach as high as 300%.Huge volume
The disadvantages of effect and lower conductivity, limits the commercialization large-scale application of silicium cathode technology.
Summary of the invention
In view of the above problem in the prior art, for solve above-mentioned these problems whole or at least one, propose this
Invention.
An aspect of of the present present invention provides a kind of silicon-carbon cathode material, overcomes and solves current silicium cathode material in Gao Rong
Under the conditions of amount, cyclical stability is poor, conductivity is low, low efficiency is inferior disadvantage.The raw material of the silicon-carbon cathode material includes silicon material
Material, graphitic carbon material, binder and additive, the silicon-carbon cathode material include: silicon-carbon compound and are coated on the silicon-carbon
Carbon layer outside compound, wherein the silicon-carbon compound is passed through described viscous by the silicon materials and the graphitic carbon material
Knot agent and additive are combined, and the carbon layer is amorphous carbon coating layer, and wherein, according to the silicon-carbon cathode material
Gross mass calculate, wherein the mass ratio of the silicon materials is 10-60%, the mass ratio of the graphitic carbon material is 30-80%,
The mass ratio of the carbon layer is 3-20%.
According to an aspect of the present invention, the carbon layer with a thickness of 0.1mm-0.5mm.
According to an aspect of the present invention, the silicon materials include nano silica fume, and the graphitic carbon material includes modified graphite,
The binder and additive include sucrose, glucose, phenolic resin, starch, gelatin, pitch, carbon nanotube, graphene, different
At least one of propyl alcohol, polyaniline, polyvinylpyrrolidone and Ketjen black, wherein the granularity D50 of the nano silica fume is
1nm-100nm, and wherein, the modified graphite include in crystalline flake graphite, amorphous graphite, spherical graphite and artificial graphite extremely
Few one kind.
According to an aspect of the present invention, the modified graphite is crystalline flake graphite, and granularity D50 is 1 μm -30 μm, and for not
The crystalline flake graphite of one-size combines.
Another aspect provides one kind can industrial mass preparation, simple production process, cyclical stability
The preparation method of good silicon-carbon cathode material, the preparation method includes: preparation step, prepares silicon materials, graphitic carbon material, glues
Agent and additive are tied as raw material；The graphitic carbon material and the silicon materials are being dissolved in the viscous of organic solvent by mixing step
It is mixed and stirred for, is dried at a predetermined temperature until organic solvent volatilizees completely in knot agent and additive solution, it is raw
It is combined silicon-carbon compound at by the silicon materials and the graphitic carbon material；And carbonization, it is multiple to resulting silicon-carbon
It closes object and carries out charing sintering to form the carbon layer as amorphous carbon coating layer, the silicon-carbon cathode material is made, wherein press
It is calculated according to the gross mass of the silicon-carbon cathode material, wherein the mass ratio of the silicon materials is 10-60%, the graphitic carbon material
Mass ratio be 30-80%, the mass ratio of the carbon layer is 3-20%.
According to another aspect of the present invention, the sintering temperature of the carbonization is 600-1200 DEG C, heating rate 1-
10 DEG C/min, sintering time is 5-20 hours.
It is yet another aspect of the present invention to provide a kind of lithium ion batteries comprising silicon-carbon cathode material as described above.
Another aspect of the present invention, the capacity of the silicon-carbon cathode material are recycling 100 times in 480-550mAh/g
Afterwards, capacity remains at 92% or more.
Silicon-carbon cathode material according to an exemplary embodiment of the present invention overcomes and solves current silicium cathode material in Gao Rong
Under the conditions of amount, cyclical stability is poor, conductivity is low, low efficiency is inferior disadvantage.It can industry in addition, the present invention also provides one kind
Change be prepared on a large scale, the preparation method of the silicon-carbon cathode material of simple production process, good cycling stability.System through the invention
Preparation Method is prepared for capacity in the silicon-carbon cathode material of 480-550mAh/g, and after circulation 100 times, capacity is remained at
92% or more.
According to the description of exemplary embodiment, other feature of the invention be will be apparent with reference to the accompanying drawings.
Detailed description of the invention
In order to more clearly explain the technical solutions in the embodiments of the present application, make required in being described below to embodiment
Attached drawing is briefly described, it should be apparent that, the accompanying drawings in the following description is only some implementations as described in this application
Example, for those of ordinary skill in the art, without creative efforts, can also obtain according to these attached drawings
Obtain other attached drawings.
Fig. 1 is SEM (scanning electron microscope) figure of silicon-carbon cathode material prepared by according to embodiments of the present invention 1.
Fig. 2 is according to embodiments of the present invention 1 volume change figure of silicon-carbon cathode material under the conditions of charge and discharge.
Fig. 3 is the preparation flow figure of silicon-carbon cathode material according to the present invention.
Fig. 4 is the flow chart according to the present invention for preparing graphitic carbon material.
Specific embodiment
Hereinafter describe the embodiment of the present invention in detail with reference to the accompanying drawings.It should be appreciated that following embodiments and unawareness
The figure limitation present invention, also, about the means according to the present invention solved the problems, such as, it is not absolutely required to be retouched according to following embodiments
The whole combinations for the various aspects stated.For simplicity, to identical structure division or step, identical label or mark have been used
Number, and the description thereof will be omitted.
Compared to volume expansion of the elemental silicon in silicium cathode material in charge and discharge process, huge bulk effect and compared with
The disadvantages of low conductivity, silicon-carbon cathode material volume change in charge and discharge process is smaller, has preferable cyclical stability
Energy and excellent electric conductivity, and carbon negative pole material itself is the mixed conductor of ion and electronics.
In addition, silicon is close with carbon geochemistry property, the two can combine closely, therefore carbon is commonly used for the preferred base compound with silicon
Matter.In Si/C compound system, Si particle provides lithium storage content as active material；It is negative that C can buffer silicon in charge and discharge process
The volume change of pole, and the electric conductivity of Si material can be improved, moreover it is possible to avoid Si particle from reuniting in charge and discharge cycles.Cause
This Si/C composite material of the invention combines the advantages of the two, shows height ratio capacity and compared with long circulation life, is very suitable to
Lithium ion battery applied to a new generation.The knot of the silicon-carbon cathode material of embodiment according to the present invention is described referring now to attached drawing
Structure, preparation method and application etc..
The raw material of silicon-carbon cathode material of the invention includes silicon materials, graphitic carbon material, binder and additive.It is right below
Each raw material is described in detail.
[graphitic carbon material]
Graphitic carbon material in the present invention includes modified graphite.Modified graphite can be crystalline flake graphite, amorphous graphite, spherical shape
One or more of graphite, artificial graphite.In other words, modified graphite includes crystalline flake graphite, amorphous graphite, spherical graphite, people
Make at least one of graphite.Preferably, modified graphite is crystalline flake graphite, and granularity D50 is 1 μm -30 μm, and is varigrained
Crystalline flake graphite combination.According to the present invention, crystalline flake graphite (such as natural flake graphite) is crushed under certain conditions, is whole
Shape and classification make granularity in above-mentioned suitable range, to prepare graphitic carbon material according to an embodiment of the present invention.Specifically,
Breaking method can use any of method in the prior art, as long as the required granularity of the present invention can be obtained.
[silicon materials]
Silicon materials in the present invention include nano silica fume, and wherein the granularity D50 of silicon powder is 1nm-100nm.According to the present invention,
Silicon powder is crushed under certain protective condition, makes the granularity of silicon materials in above-mentioned suitable range, to prepare basis
The silicon materials of the embodiment of the present invention.Specifically, breaking method can be using known method in the prior art, for example, protecting
It protects under the atmosphere of gas and is crushed and the physical crushings methods such as impact comminution using extruding.However, the invention is not limited thereto, can adopt
With known any breaking method, as long as the required granularity of the present invention can be obtained.
[binder and additive]
Binder and additive in the present invention are at least one of following substances: sucrose, glucose, phenolic resin,
Starch, gelatin, pitch, carbon nanotube, graphene, isopropanol, polyaniline, polyvinylpyrrolidone, Ketjen black.Binder and add
Agent is added to play the role of bonding and dispersion.However, can be used can be realized the present invention is not limited to above-mentioned binder and additive
The organic matter of bonding and peptizaiton.
[silicon-carbon cathode material]
Silicon-carbon cathode material of the invention includes silicon-carbon compound and the carbon layer that is coated on outside silicon-carbon compound.Silicon-carbon
Compound is combined by silicon materials and graphitic carbon material, and carbon layer is amorphous carbon coating layer.According to silicon-carbon cathode material
Gross mass calculates, and the mass ratio of silicon materials is 10-60%, and the mass ratio of graphitic carbon material is 30-80%, the mass ratio of carbon layer
For 3-20%.In general, to carbon layer without thickness requirement, preferably with a thickness of 0.1mm-0.5mm.The thickness of carbon layer is can
Control, it can be controlled according to the operating condition (for example, carbonization time etc.) of carbonization process.
Specifically, silicon-carbon cathode is to be prepared by nano silica fume, modified graphite, binder and additive for raw material.
Wherein silicon powder partial size D50 is 1nm-100nm.Modified graphite is crystalline flake graphite, in amorphous graphite, spherical graphite, artificial graphite
One or more, preferably crystalline flake graphite, granularity D50 are 1 μm -30 μm, are combined for varigrained crystalline flake graphite.Binder and
Additive is at least one of following substances: sucrose, glucose, phenolic resin, starch, gelatin, pitch, carbon nanotube, stone
Black alkene, isopropanol, polyaniline, polyvinylpyrrolidone, Ketjen black.
[preparation method of silicon-carbon cathode material]
Fig. 3 is the preparation flow figure of silicon-carbon cathode material according to the present invention.Fig. 4 is according to the present invention to prepare graphitic carbon
The flow chart of material.The preparation method of silicon-carbon cathode material according to the present invention is described in detail below with reference to Fig. 3 and Fig. 4.
Graphitic carbon material is prepared in the step s 100 referring to Fig. 3, wherein the preparation process of graphitic carbon material is referring in Fig. 4
Step S101-S104 shown in.
In step s101, exemplary embodiment of the present invention prepares conduct using varigrained natural flake graphite
The modified graphite of graphitic carbon material, but the invention is not restricted to this, can using amorphous graphite as described above, spherical graphite,
Modified graphite of the preparations such as artificial graphite as graphitic carbon material.
In step S102 and S103, set pulverization conditions to be crushed to natural flake graphite, shaping and classification.Tool
Body, pulverization conditions can be set to natural scale stone according to crushing temperature well known in the prior art, protection atmosphere etc.
Ink crushed, shaping and classification, to prepare the modified graphite as graphitic carbon material.
In step S104, determine whether the granularity D50 of gained modified graphite meets predetermined condition.In example of the invention
Property embodiment in, D50 be 1 μm -30 μm.If being unsatisfactory for predetermined condition (being "No" in S104), step returns to S103.If
Meet predetermined condition (being "Yes" in S104), then graphitic carbon material preparation is completed.
Referring back to Fig. 3, in step s 200, silicon materials are prepared, wherein the preparation process and graphitic carbon material of silicon materials
Preparation process it is similar, its detailed description will be omitted.Silicon materials in the present invention include nano silica fume, and breaking method can use
Known method in the prior art, as long as it is 1nm-100nm that granularity D50, which is prepared,.
To sum up, the step of silicon materials, graphitic carbon material are as raw material completion is prepared.Next, in step S110 and S210
In, prepared nano-silicon and graphite are respectively put into ethanol solution ultrasonic disperse certain time.Then, in step S300,
The above-mentioned solution by decentralized processing is poured into the binder and additive solution for being dissolved in organic solution (for example, toluene) in proportion
In (for example, cold primer-oil).Then, in step S400, mechanical stirring until solution at thick, then at a certain temperature
Sample is dried in a vacuum until solvent volatilizees completely.Then, in step S500, charing burning is carried out to dry solid
Knot, wherein sintering temperature is 600-1200 DEG C, and heating rate is 1-10 DEG C/min, and sintering time is 5-20 hours.Finally, it makes
Obtain the silicon-carbon cathode material in clad structure.It is calculated according to the gross mass of silicon-carbon cathode material according to the present invention, wherein silicon material
The mass ratio of material is 10-60%, and the mass ratio of graphitic carbon material is 30-80%, and the mass ratio of carbon layer is 3-20%.
Embodiment 1
Embodiment according to the present invention 1 carries out the nano silica fume crushed Zhi get as silicon materials to silicon powder particle, so that its
Granularity D50 is 30nm.Natural flake graphite is crushed, shaping and grading system must as the modified graphite of graphitic carbon material,
So that the granularity D50 of modified graphite is 30 μm.It is certain that obtained nano-silicon and graphite are respectively put into ethanol solution ultrasonic disperse
It after time, is subsequently poured into the cold primer-oil for being dissolved in toluene, three's (nano-silicon: graphite: pitch) mass ratio is 1: 8: 1.It is mechanical
Stirring is until at thick, then 12h is dried in a vacuum until solvent volatilizees completely at a certain temperature in sample by solution.It is right
Dry solid carries out charing sintering, and sintering temperature is 650 DEG C, and heating rate is 2 DEG C/min, and sintering time is 6 hours.According to
Silicon-carbon cathode material prepared by the embodiment of the present invention 1, calculates according to gross mass, and the mass ratio of silicon materials is 10%, graphite
The mass ratio of carbon material is 80%, and the mass ratio of carbon layer is 10%.
Embodiment 2
Embodiment according to the present invention 2 carries out the nano silica fume crushed Zhi get as silicon materials to silicon powder particle, so that its
Granularity D50 is 80nm.Amorphous graphite is crushed, shaping and grading system must as the modified graphite of graphitic carbon material so that
The granularity D50 of modified graphite is 20 μm.Obtained nano-silicon and graphite are respectively put into ethanol solution ultrasonic disperse certain time
Afterwards, it is subsequently poured into the phenol resin solution for being dissolved in toluene, three's (nano-silicon: graphite: phenolic resin) mass ratio is 2: 7: 1.
Mechanical stirring is until at thick, then 10h is dried in a vacuum until solvent is waved completely at a certain temperature in sample by solution
Hair.Charing sintering is carried out to dry solid, sintering temperature is 850 DEG C, and heating rate is 5 DEG C/min, and sintering time is 10 small
When.Silicon-carbon cathode material prepared by embodiment according to the present invention 2, calculates according to gross mass, and the mass ratio of silicon materials is
20%, the mass ratio of graphitic carbon material is 65%, and the mass ratio of carbon layer is 15%.
For the sake of simplicity, the description to embodiment 3-5 is omitted and lists silicon prepared by embodiment 1-5 in table 1
Capacity retention ratio after each component content of carbon negative pole material and 100 circulations.
[chemical property of silicon-carbon cathode material]
Fig. 1 is the SEM figure of silicon-carbon cathode material prepared by according to embodiments of the present invention 1.Fig. 2 is to implement according to the present invention
Volume change figure of the silicon-carbon cathode material of example 1 under the conditions of charge and discharge.Table 1 instantiates the electrochemistry of silicon-carbon cathode material
Energy.
As shown in Figure 1, silicon-carbon cathode material prepared by according to embodiments of the present invention 1 is in uniform coated core-shell structure.
Can be seen that silicon-carbon cathode material according to an embodiment of the present invention from Fig. 2 and table 1,0.1C fills at ambient temperature
Under discharging condition, 100 circulation volumes remain at 92% or more.
The chemical property of 1 silicon-carbon cathode material of table
In other words, silicon-carbon cathode material according to an exemplary embodiment of the present invention overcomes and solves current silicium cathode material
Under the conditions of high capacity, cyclical stability is poor, conductivity is low, low efficiency is inferior disadvantage.
In addition, the present invention also provides it is a kind of can industrial mass preparation, simple production process, good cycling stability
The preparation method of silicon-carbon cathode material.It is negative in the silicon-carbon of 480-550mAh/g to be prepared for capacity for preparation method through the invention
Pole material, and after circulation 100 times, capacity remains at 92% or more.
Moreover, it relates to which a kind of includes high-energy density silicon-carbon cathode material according to an exemplary embodiment of the present invention
The lithium ion battery of material.However the invention is not limited thereto, silicon-carbon cathode material of the invention can not only be applied to lithium-ion electric
Chi Zhong can also be applied in other high-energy density power batteries as cathode.
Although exemplary embodiments describe the present invention for reference above, above-described embodiment is only to illustrate this hair
Bright technical concepts and features, it is not intended to limit the scope of the present invention.What all Spirit Essences according to the present invention were done
Any equivalent variations or modification, should be covered by the protection scope of the present invention.
Claims (10)
1. a kind of silicon-carbon cathode material, raw material includes silicon materials, graphitic carbon material, binder and additive, and the silicon-carbon is negative
Pole material includes silicon-carbon compound and the carbon layer that is coated on outside the silicon-carbon compound,
Wherein, the silicon-carbon compound is compound by the binder and additive by the silicon materials and the graphitic carbon material
It forming, the carbon layer is amorphous carbon coating layer, and
Wherein, it is calculated according to the gross mass of the silicon-carbon cathode material, the mass ratio of the silicon materials is 10-60%, the stone
The mass ratio of black carbon material is 30-80%, and the mass ratio of the carbon layer is 3-20%.
2. silicon-carbon cathode material according to claim 1, wherein the carbon layer with a thickness of 0.1mm-0.5mm.
3. silicon-carbon cathode material according to claim 1, wherein
The silicon materials include nano silica fume, and the graphitic carbon material includes modified graphite, and the binder and additive include
Sucrose, glucose, phenolic resin, starch, gelatin, pitch, carbon nanotube, graphene, isopropanol, polyaniline, polyvinyl pyrrole
At least one of alkanone and Ketjen black,
Wherein, the granularity D50 of the nano silica fume is 1nm-100nm, and
Wherein, the modified graphite includes at least one of crystalline flake graphite, amorphous graphite, spherical graphite, artificial graphite.
4. silicon-carbon cathode material according to claim 3, wherein the modified graphite is crystalline flake graphite, and granularity D50 is 1 μ
M-30 μm, and be the combination of varigrained crystalline flake graphite.
5. a kind of preparation method of silicon-carbon cathode material, the preparation method include:
Preparation step prepares silicon materials, graphitic carbon material, binder and additive as raw material；
Mixing step, by the graphitic carbon material and the silicon materials in the binder and additive solution for being dissolved in organic solvent
It is mixed and stirred for, is dried at a predetermined temperature until organic solvent volatilizees completely, generation is by the silicon materials and institute
State the silicon-carbon compound that graphitic carbon material is combined；And
Carbonization carries out charing to resulting silicon-carbon compound and is sintered to form the carbon layer as amorphous carbon coating layer,
The silicon-carbon cathode material is made,
Wherein, it is calculated according to the gross mass of the silicon-carbon cathode material, the mass ratio of the silicon materials is 10-60%, the stone
The mass ratio of black carbon material is 30-80%, and the mass ratio of the carbon layer is 3-20%.
6. preparation method according to claim 5, wherein the carbon layer with a thickness of 0.1mm-0.5mm.
7. preparation method according to claim 5, wherein
The silicon materials include nano silica fume, and the graphitic carbon material includes modified graphite, and the binder and additive include
Sucrose, glucose, phenolic resin, starch, gelatin, pitch, carbon nanotube, graphene, isopropanol, polyaniline, polyvinyl pyrrole
At least one of alkanone and Ketjen black,
Wherein, the granularity D50 of the nano silica fume is 1nm-100nm, and
Wherein, the modified graphite includes at least one of crystalline flake graphite, amorphous graphite, spherical graphite and artificial graphite.
8. preparation method according to claim 7, wherein the modified graphite is crystalline flake graphite, and granularity D50 is 1 μm -30
μm, and be the combination of varigrained crystalline flake graphite.
9. a kind of lithium ion battery comprising silicon-carbon cathode material as claimed in any of claims 1 to 4.
10. lithium ion battery according to claim 9, wherein the capacity of the silicon-carbon cathode material is in 480-550mAh/
Mg, and after circulation 100 times, capacity remains at 92% or more.
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| CN110021749A (en) * | 2019-04-26 | 2019-07-16 | 蜂巢能源科技有限公司 | Silicon-carbon cathode material and preparation method thereof, battery |
| CN110350161A (en) * | 2019-06-18 | 2019-10-18 | 长沙矿冶研究院有限责任公司 | A kind of preparation method of silicon-carbon cathode presoma |
| CN111244421A (en) * | 2020-01-19 | 2020-06-05 | 浙江开化元通硅业有限公司 | Preparation method of silicon-graphite cathode composite material, product and application of silicon-graphite cathode composite material |
| CN111509215A (en) * | 2020-04-26 | 2020-08-07 | 盐城工学院 | Preparation method of high-first-efficiency long-cycle lithium battery negative electrode silicon-carbon material |
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| CN111755677A (en) * | 2020-07-06 | 2020-10-09 | 马鞍山科达普锐能源科技有限公司 | Core-shell structure porous silicon negative electrode material for lithium ion battery and preparation method thereof |
| WO2022151648A1 (en) * | 2021-01-14 | 2022-07-21 | 广东凯金新能源科技股份有限公司 | High-capacity highly stable silicon-carbon negative electrode material and preparation method therefor |
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