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CN105826533A - Silicon-carbon composite for lithium ion battery and preparation method of silicon-carbon composite - Google Patents

Silicon-carbon composite for lithium ion battery and preparation method of silicon-carbon composite Download PDF

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Publication number
CN105826533A
CN105826533A CN201610181025.5A CN201610181025A CN105826533A CN 105826533 A CN105826533 A CN 105826533A CN 201610181025 A CN201610181025 A CN 201610181025A CN 105826533 A CN105826533 A CN 105826533A
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silicon
carbon composite
ion battery
lithium ion
composite material
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黄钊文
肖文平
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Shunde Vocational and Technical College
Shunde Polytechnic
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Shunde Vocational and Technical College
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Priority to CN201610181025.5A priority Critical patent/CN105826533A/en
Publication of CN105826533A publication Critical patent/CN105826533A/en
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/362Composites
    • H01M4/366Composites as layered products
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B82NANOTECHNOLOGY
    • B82YSPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00Nanotechnology for materials or surface science, e.g. nanocomposites
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/05Accumulators with non-aqueous electrolyte
    • H01M10/052Li-accumulators
    • H01M10/0525Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/38Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/386Silicon or alloys based on silicon
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/58Selection 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
    • H01M4/583Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H01M4/587Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/62Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/628Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage using batteries

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • General Chemical & Material Sciences (AREA)
  • Electrochemistry (AREA)
  • Composite Materials (AREA)
  • Materials Engineering (AREA)
  • Nanotechnology (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Inorganic Chemistry (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

The invention relates to a silicon-carbon composite for a lithium ion battery and a preparation method of the silicon-carbon composite.The silicon-carbon composite is characterized in that the silicon-carbon composite is of a core-shell structure which comprises a core and a shell layer wrapping the core; the core is prepared from, 86.8% to 95.8% of graphite, 4.2% to 11% of nanocrystallized Si, 0% to 2.2% of transition metal element M and 0% to 2.2% of lithium salt, graphite serves as the inner layer of the core, and nanocrystallized Si and the transition metal element M or lithium salt are dispersed on the surface of the inner layer; the shell layer is formed by organic matter cracked carbon, the organic matter can be one of acid organic matter, sugar organic matter, resin organic matter and asphalt.The mass ratio of organic matter cracked carbon to the core is 11% to 42%, and the percent is mass percent.The advantages that high circulating stability and capacity are achieved, and the bottleneck problems of the volume effect of a silicon-carbon negative-electrode material and low primary coulombic efficiency can be solved are achieved.

Description

Silicon-carbon composite material for lithium ion battery and preparation method thereof
Technical field
The present invention relates to a kind of Silicon-carbon composite material for lithium ion battery and preparation method thereof.
Background technology
At present, negative material is mainly graphite-like carbon negative pole material, has basically reached its theoretical specific capacity, limit lithium from The further development of sub-battery.Silicon, owing to having the theoretical specific capacity of up to 3000mAh/g, is considered the replacement of carbon negative pole material Property product, but in charge and discharge process, there is bigger bulk effect, cause material efflorescence actual effect, show poor circulation steady Qualitative.
The nanorize of silicon is generally considered to reduce the impact of its bulk effect, it addition, the volumetric expansion for silicon is left a blank in advance Between be also considered as solve bulk effect important channel.
Summary of the invention
It is an object of the invention to overcome the deficiencies in the prior art and provide a kind of Silicon-carbon composite material for lithium ion battery and Its preparation method, has the feature of high cyclical stability, high power capacity, can solve silicon-carbon cathode material bulk effect and coulomb first Inefficient bottleneck problem.
In order to achieve the above object, the Silicon-carbon composite material for lithium ion battery of the present invention is achieved in that its feature The structure being Si-C composite material is nucleocapsid structure, and nucleocapsid structure includes kernel and the shell being coated on outside kernel;In described Core includes transition metal M's and 0%-2.2% of nanorize Si, 0%-2.2% of the graphite of 86.8%-95.8%, 4.2%-11% Lithium salts, described graphite is the internal layer of kernel, and the Si of described nanorize and transition metal M or lithium salts are dispersed in the table of internal layer Face;Described shell is made up of organic cracking carbon, and described Organic substance can be that acids Organic substance, saccharide Organic substance, resinae are organic Thing, the one of Colophonium, organic cracking carbon is 11%-42% with the mass ratio of kernel, and above-mentioned percentage ratio is mass percent.
In the technical program, allow between described graphite surface and shell to exist with carbon nano-fiber and CNT group The cushion become.
In the technical program, described lithium salts is lithium titanate or lithium carbonate;Described transition metal M be ferrum, cobalt, nickel, Copper or aluminum.
In the technical program, described acids Organic substance is citric acid.
In the technical program, described saccharide Organic substance is glucose or sucrose.
In the technical program, described resinae Organic substance is epoxy resin or phenolic resin.
In the technical program, described Colophonium is the Colophonium of various phosphorus content.
In order to achieve the above object, the preparation method of the Silicon-carbon composite material for lithium ion battery of the present invention is realized in , it is characterised in that preparation process is as follows:
Step one
By the graphite of 86.8%-95.8%, transition metal M and 0%-2.2% of nanorize Si, 0%-2.2% of 4.2%-11% The mixture that lithium salts is formed puts into ball milling mixing in planetary ball mill, obtains mixture A, and ratio of grinding media to material is 5:1-20:1, at ball Adding dehydrated alcohol to solid content during mill is 10%-50%, and ball is the zirconia ball that diameter is less than 5mm, and Ball-milling Time is 3- 30 hours, obtain mixture B;
Step 2
It is the one that 11%-42% weighs acids, saccharide, resinae and Colophonium by the mass ratio of organic cracking carbon Yu mixture A Organic substance, by Organic substance after fully dissolving, adds in mixture B, continues ball milling 3-30 hour;
Step 3
After ball milling terminates, through fully putting into high-temperature heating in tube furnace or batch-type furnace after drying, period leads to inert gas shielding, Heating rate is 2-4 DEG C/min, and thermostat temperature and basis of time organic cracking rule are carried out, such as saccharide organic insulating temperature Degree is 300-500 DEG C, constant temperature time is 4-6 hour, and acids organic insulating temperature is 450-600 DEG C, constant temperature time is 4-6 Hour, resinae organic insulating temperature is 400-600 DEG C, constant temperature time is 4-6 hour, and asphalt thermal insulation temperature is 850- 1000 DEG C, constant temperature time be 4-6 hour;
Step 4
Naturally take out after being down to room temperature, cross 200 mesh sieves, obtain Silicon-carbon composite material for lithium ion battery;
When if desired preparing multilayer package, repeat step 2 and step 3.
In the technical program, described noble gas is nitrogen or argon.
In the technical program, being dried as vacuum drying or being spray-dried after ball milling terminates in step 3.
Present invention advantage compared with prior art is: has the feature of high cyclical stability, high power capacity, can solve silicon-carbon The bottleneck problem that negative material bulk effect and first coulombic efficiency are low.
Accompanying drawing explanation
Fig. 1 be the present invention use spherical graphite as the sample topography figure of kernel,
Fig. 2 be the present invention be use flaky graphite as the sample topography figure of kernel,
Fig. 3 be the present invention use spherical graphite as the section shape appearance figure of the sample of kernel,
Fig. 4 be the present invention use flaky graphite as the section shape appearance figure of the sample of kernel,
Fig. 5 embodiment one prepares the shape appearance figure of gained sample,
Fig. 6 embodiment two prepares the shape appearance figure of gained sample,
Fig. 7 embodiment three prepares the shape appearance figure of gained sample,
Fig. 8 embodiment four prepares the shape appearance figure of gained sample,
Fig. 9 embodiment five prepares the shape appearance figure of gained sample,
Figure 10 embodiment six prepares the shape appearance figure of gained sample,
Figure 11 embodiment seven prepares the shape appearance figure of gained sample.
Detailed description of the invention
Below in conjunction with the accompanying drawings the detailed description of the invention of the present invention is described further.At this it should be noted that for The explanation of these embodiments is adapted to assist in and understands the present invention, but is not intended that limitation of the invention.Additionally, it is disclosed below As long as each embodiment of the present invention in involved technical characteristic do not constitute conflict each other and just can be combined with each other.
Embodiment one
It is a kind of Silicon-carbon composite material for lithium ion battery, and its structure is nucleocapsid structure, and nucleocapsid structure includes kernel and cladding Shell outside kernel;Described kernel includes the spherical graphite of 91.3%, the cobalt of the Si of the nanorize of 7.6% and 1.1%, described stone Ink is the internal layer of kernel, and as shown in Figures 1 and 3, the Si of described nanorize and cobalt are dispersed in the surface of internal layer;Described shell is by having Machine thing cracking carbon is constituted, and organic cracking carbon is glucose or sucrose, and organic cracking carbon is 26% with the mass ratio of kernel, on Stating percentage ratio is mass percent.
Its preparation process is as follows:
Step one
The mixture that spherical graphite by 91.3%, the cobalt of the Si of the nanorize of 7.6% and 1.1% are formed puts into planetary ball mill Middle ball milling mixes, and obtains mixture A, and ratio of grinding media to material is 12:1, and adding dehydrated alcohol to solid content in mechanical milling process is 30%, ball Being the diameter zirconia ball that is less than 5mm, Ball-milling Time is 16 hours, obtains mixture B;
Step 2
It is 26% to weigh glucose or sucrose by the mass ratio of organic cracking carbon Yu mixture A, by glucose or sucrose through organic After solution fully dissolves, add in mixture B, continue ball milling 16 hours;
Step 3
After ball milling terminates, putting into high-temperature heating in batch-type furnace after being sufficiently spray-dried, period leads to argon shield, heating rate Being 3 DEG C/min, thermostat temperature and basis of time organic cracking rule are carried out, and glucose or sucrose holding temperature are 450 DEG C, permanent The temperature time is 5 hours;
Step 4
Naturally take out after being down to room temperature, cross 200 mesh sieves, obtain Silicon-carbon composite material for lithium ion battery,
As shown in Figure 5;When if desired preparing multilayer package, repeat step 2 and step 3.
Embodiment two
It is a kind of Silicon-carbon composite material for lithium ion battery, and its structure is nucleocapsid structure, and nucleocapsid structure includes kernel and cladding Shell outside kernel;Described kernel includes flake graphite, the nanorize Si of 11%, the ferrum of 1.1% and the metatitanic acid of 1.1% of 86.8% Lithium, described graphite is the internal layer of kernel, and as shown in Figures 2 and 4, described nanorize Si, ferrum and lithium titanate are dispersed in the table of internal layer Face;Described shell is made up of organic cracking carbon, and described Organic substance is citric acid, and organic cracking carbon with the mass ratio of kernel is 42%, above-mentioned percentage ratio is mass percent.
Its preparation process is as follows:
Step one
The mixture that the lithium titanate of flake graphite, the nanorize Si of 11%, the ferrum of 1.1% and 1.1% by 86.8% is formed puts into row In planetary ball mill, ball milling mixing, obtains mixture A, and ratio of grinding media to material is 5:1, adds dehydrated alcohol to solid content in mechanical milling process Being 10%, ball is the zirconia ball that diameter is less than 5mm, and Ball-milling Time is 3 hours, obtains mixture B;
Step 2
It is 42% to weigh citric acid by the mass ratio of organic cracking carbon Yu mixture A, citric acid is fully dissolved through organic solution After, add in mixture B, continue ball milling 3 hours;
Step 3
After ball milling terminates, putting into high-temperature heating in tube furnace after fully vacuum drying, period leads to nitrogen protection, and heating rate is 2 DEG C/min, thermostat temperature and basis of time organic cracking rule are carried out, and citric acid holding temperature is 450 DEG C, constant temperature time is 6 hours;
Step 4
Naturally take out after being down to room temperature, cross 200 mesh sieves, obtain Silicon-carbon composite material for lithium ion battery,
As shown in Figure 6;When if desired preparing multilayer package, repeat step 2 and step 3.
Embodiment three
It is a kind of Silicon-carbon composite material for lithium ion battery, and its structure is nucleocapsid structure, and nucleocapsid structure includes kernel and cladding Shell outside kernel;Described kernel includes the spherical graphite of 95.8%, the Si of the nanorize of 4.2%, and described graphite is kernel Internal layer, as shown in Figures 1 and 3, the Si of described nanorize is dispersed in the surface of internal layer;Described shell is by organic cracking carbon structure Becoming, described Organic substance is epoxy resin or phenolic resin, and organic cracking carbon is 11% with the mass ratio of kernel, above-mentioned percentage ratio For mass percent.
Its preparation process is as follows:
Step one
Spherical graphite by 95.8%, the mixture of the Si of the nanorize of 4.2% put into ball milling mixing in planetary ball mill, obtain Mixture A, ratio of grinding media to material is 20:1, and adding dehydrated alcohol to solid content in mechanical milling process is 50%, and ball is that diameter is less than 5mm Zirconia ball, Ball-milling Time is 30 hours, obtains mixture B;
Step 2
It is 11% to weigh epoxy resin or phenolic resin, by epoxy resin or phenol by the mass ratio of organic cracking carbon Yu mixture A Urea formaldehyde, after organic solution is fully dissolved, adds in mixture B, continues ball milling 3-30 hour;
Step 3
After ball milling terminates, putting into high-temperature heating in tube furnace after sufficiently vacuum drying, period leads to nitrogen protection, heating rate Being 4 DEG C/min, thermostat temperature and basis of time organic cracking rule are carried out, and epoxy resin or phenolic resin holding temperature are 600 DEG C, constant temperature time be 4 hours;
Step 4
Naturally take out after being down to room temperature, cross 200 mesh sieves, obtain Silicon-carbon composite material for lithium ion battery,
As shown in Figure 7;When if desired preparing multilayer package, repeat step 2 and step 3.
Embodiment four
It is a kind of Silicon-carbon composite material for lithium ion battery, and its structure is nucleocapsid structure, and nucleocapsid structure includes kernel and cladding Shell outside kernel;Described kernel includes the flake graphite of 90%, the nickel of the nanorize Si and 1% of 9%, and described graphite is kernel Internal layer, as shown in Figures 2 and 4, described nanorize Si and nickel are dispersed in the surface of internal layer;Described shell is by organic cracking carbon Constituting, described Organic substance is the Colophonium of phosphorus content 70%, and organic cracking carbon is 30% with the mass ratio of kernel, and above-mentioned percentage ratio is Mass percent.
In the present embodiment, allow to exist with carbon nano-fiber and CNT group between described graphite surface and shell The cushion become.
Its preparation process is as follows:
Step one
The mixture that flake graphite by 90%, the nickel of the nanorize Si and 1% of 9% are formed is put into ball milling in planetary ball mill and is mixed Closing, obtain mixture A, ratio of grinding media to material is 10:1, and adding dehydrated alcohol to solid content in mechanical milling process is 20%, and ball is that diameter is little In the zirconia ball of 5mm, Ball-milling Time is 10 hours, obtains mixture B;
Step 2
It is 21% Colophonium weighing phosphorus content by the mass ratio of cracking carbon with mixture A, the Colophonium of phosphorus content is filled through organic solution Divide after dissolving, add in mixture B, continue ball milling 10 hours;
Step 3
After ball milling terminates, putting into high-temperature heating in batch-type furnace after being sufficiently spray-dried, period leads to inert gas shielding, heats up Speed is 3 DEG C/min, and thermostat temperature and basis of time organic cracking rule are carried out, the asphalt thermal insulation temperature containing charcoal is 900 DEG C, Constant temperature time is 6 hours;
Step 4
Naturally take out after being down to room temperature, cross 200 mesh sieves, obtain Silicon-carbon composite material for lithium ion battery,
As shown in Figure 8;When if desired preparing multilayer package, repeat step 2 and step 3.
Embodiment five
It is a kind of Silicon-carbon composite material for lithium ion battery, and its structure is nucleocapsid structure, and nucleocapsid structure includes kernel and cladding Shell outside kernel;Described kernel includes the spherical graphite of 92.8%, the copper of the nanorize Si and 2.2% of 5%, and described graphite is The internal layer of kernel, as shown in Figures 1 and 3, the Si of described nanorize and copper are dispersed in the surface of internal layer;Described shell is by Organic substance Cracking carbon is constituted, and described Organic substance is citric acid, and organic cracking carbon is 32% with the mass ratio of kernel, and above-mentioned percentage ratio is matter Amount percentage ratio.
Its preparation process is as follows:
Step one
The mixture that spherical graphite by 92.8%, the copper of the nanorize Si and 2.2% of 5% are formed puts into ball in planetary ball mill Mill mixing, obtains mixture A, and ratio of grinding media to material is 9:1, and adding dehydrated alcohol to solid content in mechanical milling process is 40%, and ball is diameter Less than the zirconia ball of 5mm, Ball-milling Time is 15 hours, obtains mixture B;
Step 2
It is 32% to weigh citric acid by the mass ratio of organic cracking carbon Yu mixture A, citric acid is fully dissolved through organic solution After, add in mixture B, continue ball milling 10 hours;
Step 3
After ball milling terminates, putting into high-temperature heating in tube furnace after sufficiently vacuum drying, period leads to nitrogen protection, heating rate Being 4 DEG C/min, thermostat temperature and basis of time organic cracking rule are carried out, and citric acid holding temperature is 500 DEG C, constant temperature time It it is 5 hours;
Step 4
Naturally take out after being down to room temperature, cross 200 mesh sieves, obtain Silicon-carbon composite material for lithium ion battery,
As shown in Figure 9;When if desired preparing multilayer package, repeat step 2 and step 3.
Embodiment six
It is a kind of Silicon-carbon composite material for lithium ion battery, and its structure is nucleocapsid structure, and nucleocapsid structure includes kernel and cladding Shell outside kernel;Described kernel includes the flake graphite of 88.8%, the lithium carbonate of the nanorize Si and 2.2% of 9%, described stone Ink is the internal layer of kernel, and as shown in Figures 2 and 4, the Si of described nanorize and lithium carbonate are dispersed in the surface of internal layer;Described shell Being made up of organic cracking carbon, described Organic substance is glucose or sucrose, and organic cracking carbon is 20% with the mass ratio of kernel, Above-mentioned percentage ratio is mass percent.
In the present embodiment, allow to exist with carbon nano-fiber and CNT group between described graphite surface and shell The cushion become.
Its preparation process is as follows:
Step one
The mixture that flake graphite by 88.8%, the lithium carbonate of the nanorize Si and 2.2% of 9% are formed puts into planetary ball mill Middle ball milling mixes, and obtains mixture A, and ratio of grinding media to material is 15:1, and adding dehydrated alcohol to solid content in mechanical milling process is 45%, ball Being the diameter zirconia ball that is less than 5mm, Ball-milling Time is 20 hours, obtains mixture B;
Step 2
It is 20% to weigh glucose or sucrose by the mass ratio of organic cracking carbon Yu mixture A, by glucose or sucrose through organic After solution fully dissolves, add in mixture B, continue ball milling 20 hours;
Step 3
After ball milling terminates, putting into high-temperature heating in tube furnace after sufficiently vacuum drying, period leads to nitrogen protection, heating rate Being 4 DEG C/min, thermostat temperature and basis of time organic cracking rule are carried out, and glucose or sucrose holding temperature are 300 DEG C, perseverance The temperature time is 6 hours;
Step 4
Naturally take out after being down to room temperature, cross 200 mesh sieves, obtain Silicon-carbon composite material for lithium ion battery,
As shown in Figure 10;When if desired preparing multilayer package, repeat step 2 and step 3.
Embodiment seven
It is a kind of Silicon-carbon composite material for lithium ion battery, and its structure is nucleocapsid structure, and nucleocapsid structure includes kernel and cladding Shell outside kernel;Described kernel includes the spherical graphite of 90% and the nanorize Si of 10%, and described graphite is the internal layer of kernel, As shown in Figures 1 and 2, the Si of described nanorize is dispersed in the surface of internal layer;Described shell is made up of organic cracking carbon, described Organic substance is epoxy resin or phenolic resin, and organic cracking carbon is 18% with the mass ratio of kernel, and above-mentioned percentage ratio is quality hundred Proportion by subtraction.
Its preparation process is as follows:
Step one
Spherical graphite and the mixture of the nanorize Si formation of 10% by 90% put into ball milling mixing in planetary ball mill, obtain Mixture A, ratio of grinding media to material is 18:1, and adding dehydrated alcohol to solid content in mechanical milling process is 25%, and ball is that diameter is less than 5mm Zirconia ball, Ball-milling Time is 25 hours, obtains mixture B;
Step 2
It is 18% title epoxy resin or phenolic resin by the mass ratio of organic cracking carbon Yu mixture A, by epoxy resin or phenolic aldehyde Resin, after organic solution is fully dissolved, adds in mixture B, continues ball milling 18 hours;
Step 3
After ball milling terminates, putting into high-temperature heating in tube furnace or batch-type furnace after sufficiently vacuum drying, period leads to argon guarantor Protecting, heating rate is 2 DEG C/min, and thermostat temperature and basis of time organic cracking rule are carried out, epoxy resin or phenolic resin Holding temperature is 400 DEG C, constant temperature time is 6 hours;
Step 4
Naturally take out after being down to room temperature, cross 200 mesh sieves, obtain Silicon-carbon composite material for lithium ion battery,
As shown in figure 11;When if desired preparing multilayer package, repeat step 2 and step 3.
In the embodiment above, saccharide organic insulating temperature can select in the range of 300-500 DEG C, its constant temperature time Can select in the range of 4-6 hour;Acids organic insulating temperature can select in the range of 450-600 DEG C, and constant temperature time can be Select in the range of 4-6 hour;Resinae organic insulating temperature can select in the range of 400-600 DEG C, and constant temperature time can be at 4-6 Select in the range of hour;Asphalt thermal insulation temperature can select in the range of 850-1000 DEG C, and constant temperature time can be 4-6 hour scope Interior selection.
Above in association with accompanying drawing, embodiments of the present invention are explained in detail, but the present invention is not limited to described reality Execute mode.For the ordinary skill in the art, to these in the case of without departing from the principle of the present invention and objective Embodiment carries out multiple change, revises, replaces and deform and still fall within the scope of the present invention.

Claims (10)

1. a Silicon-carbon composite material for lithium ion battery, it is characterised in that the structure of Si-C composite material is nucleocapsid structure, core Shell structure includes kernel and the shell being coated on outside kernel;Described kernel includes the graphite of 86.8%-95.8%, the receiving of 4.2%-11% The lithium salts of transition metal M and 0%-2.2% of riceization Si, 0%-2.2%, described graphite is the internal layer of kernel, described nanorize Si and transition metal M or lithium salts be dispersed in the surface of internal layer;Described shell is made up of organic cracking carbon, described organic Thing can be acids Organic substance, saccharide Organic substance, resinae Organic substance, the one of Colophonium, organic cracking carbon and the quality of kernel Ratio is 11%-42%, and above-mentioned percentage ratio is mass percent.
Silicon-carbon composite material for lithium ion battery the most according to claim 1, it is characterised in that at described graphite surface and shell Allow between Ceng to exist with the cushion of carbon nano-fiber with CNT composition.
Silicon-carbon composite material for lithium ion battery the most according to claim 1, it is characterised in that described lithium salts is lithium titanate Or lithium carbonate;Described transition metal M is ferrum, cobalt, nickel, copper or aluminum.
Silicon-carbon composite material for lithium ion battery the most according to claim 1, it is characterised in that described acids Organic substance is Citric acid.
Silicon-carbon composite material for lithium ion battery the most according to claim 1, it is characterised in that described saccharide Organic substance is Glucose or sucrose.
Silicon-carbon composite material for lithium ion battery the most according to claim 1, it is characterised in that described resinae Organic substance It is epoxy resin or phenolic resin.
Silicon-carbon composite material for lithium ion battery the most according to claim 1, it is characterised in that described Colophonium is various containing The Colophonium of carbon amounts.
8. the preparation method of a Silicon-carbon composite material for lithium ion battery, it is characterised in that preparation process is as follows:
Step one
By the graphite of 86.8%-95.8%, transition metal M and 0%-2.2% of nanorize Si, 0%-2.2% of 4.2%-11% The mixture that lithium salts is formed puts into ball milling mixing in planetary ball mill, obtains mixture A, and ratio of grinding media to material is 5:1-20:1, at ball Adding dehydrated alcohol to solid content during mill is 10%-50%, and ball is the zirconia ball that diameter is less than 5mm, and Ball-milling Time is 3- 30 hours, obtain mixture B;
Step 2
It is the one that 11%-42% weighs acids, saccharide, resinae and Colophonium by the mass ratio of organic cracking carbon Yu mixture A Organic substance, by Organic substance after fully dissolving, adds in mixture B, continues ball milling 3-30 hour;
Step 3
After ball milling terminates, through fully putting into high-temperature heating in tube furnace or batch-type furnace after drying, period leads to inert gas shielding, Heating rate is 2-4 DEG C/min, and thermostat temperature and basis of time organic cracking rule are carried out, such as saccharide organic insulating temperature Degree is 300-500 DEG C, constant temperature time is 4-6 hour, and acids organic insulating temperature is 450-600 DEG C, constant temperature time is 4-6 Hour, resinae organic insulating temperature is 400-600 DEG C, constant temperature time is 4-6 hour, and asphalt thermal insulation temperature is 850- 1000 DEG C, constant temperature time be 4-6 hour;
Step 4
Naturally take out after being down to room temperature, cross 200 mesh sieves, obtain Silicon-carbon composite material for lithium ion battery;
When if desired preparing multilayer package, repeat step 2 and step 3.
The preparation method of Silicon-carbon composite material for lithium ion battery the most according to claim 8, its. it is characterised by described lazy Property gas is nitrogen or argon.
The preparation method of Silicon-carbon composite material for lithium ion battery the most according to claim 8, it is characterised in that step 3 Middle ball milling terminate after be dried for vacuum drying or be spray-dried.
CN201610181025.5A 2016-03-28 2016-03-28 Silicon-carbon composite for lithium ion battery and preparation method of silicon-carbon composite Pending CN105826533A (en)

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CN107170965A (en) * 2017-05-04 2017-09-15 中南大学 Si-C composite material and its preparation method and application
CN107170965B (en) * 2017-05-04 2019-12-24 中南大学 Silicon-carbon composite material and preparation method and application thereof
CN108448103A (en) * 2018-04-25 2018-08-24 华南理工大学 A kind of high performance silicon carbon composite with nucleocapsid and preparation method thereof and the application in lithium ion battery
CN108878776A (en) * 2018-07-17 2018-11-23 四川聚能仁和新材料有限公司 A kind of battery cathode sheet and preparation method thereof and a kind of battery
CN108963226A (en) * 2018-07-17 2018-12-07 四川聚能仁和新材料有限公司 C silicon/activity silicon/charcoal core-shell structure composite negative pole material and preparation method thereof
CN108878776B (en) * 2018-07-17 2021-03-09 四川聚能仁和新材料有限公司 Battery negative plate and preparation method thereof, and battery
CN108987707B (en) * 2018-07-18 2021-10-26 顺德职业技术学院 Phosphorus-copper negative electrode material for lithium ion battery and preparation method thereof
CN108987707A (en) * 2018-07-18 2018-12-11 顺德职业技术学院 A kind of lithium ion battery phosphor-copper negative electrode material and preparation method thereof
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CN109103438A (en) * 2018-08-30 2018-12-28 马鞍山科达普锐能源科技有限公司 A kind of lithium ion battery core-shell structure negative electrode material and preparation method thereof
CN109728288A (en) * 2018-09-06 2019-05-07 长兴材料工业股份有限公司 Si-C composite material and preparation method thereof, cathode of lithium battery and lithium battery
CN109411717A (en) * 2018-09-28 2019-03-01 华南理工大学 A kind of negative electrode material and preparation method thereof through prelithiation with high reversible capacity
US11063253B2 (en) 2018-11-30 2021-07-13 National Cheng Kung University Composite particle for electrode
CN109671942A (en) * 2018-12-24 2019-04-23 成都硅宝科技股份有限公司 A kind of lithium-ion battery silicon-carbon anode material and preparation method thereof
CN112713262A (en) * 2019-12-16 2021-04-27 宁波杉杉新材料科技有限公司 Silicon monoxide composite material, electrode, lithium ion battery and preparation method and application thereof
CN112670489A (en) * 2019-12-16 2021-04-16 宁波杉杉新材料科技有限公司 Silicon-carbon composite material, electrode, lithium ion battery and preparation method and application thereof

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