CN108428876A - A kind of high performance silicon/carbon nano composite anode material and preparation method thereof - Google Patents
A kind of high performance silicon/carbon nano composite anode material and preparation method thereof Download PDFInfo
- Publication number
- CN108428876A CN108428876A CN201810261003.9A CN201810261003A CN108428876A CN 108428876 A CN108428876 A CN 108428876A CN 201810261003 A CN201810261003 A CN 201810261003A CN 108428876 A CN108428876 A CN 108428876A
- Authority
- CN
- China
- Prior art keywords
- silicon
- carbon
- particle
- high performance
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- H—ELECTRICITY
- 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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/364—Composites as mixtures
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- H—ELECTRICITY
- 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
- 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
-
- H—ELECTRICITY
- 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
- 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
-
- Y—GENERAL 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The present invention provides a kind of high performance silicon/carbon nano composite anode materials and preparation method thereof.The high performance silicon/carbon nano composite anode material, which is characterized in that comprising the Nano carbon balls shape particle with mesopore orbit, simple substance silicon particle is filled with inside spherical particle and/or in mesopore orbit.The features such as there is silicon/carbon compound cathode materials prepared by the present invention porous structure, simple substance silicon particle to be dispersed in inside carbon skeleton and mesopore orbit, and lithium ion charge and discharge process Volumetric expansion is low, electrochemistry stable cycle performance.
Description
Technical field
The invention belongs to field of lithium ion battery material, and in particular to a kind of preparation side of high performance silicon carbon negative pole material
Method.
Background technology
In order to meet energy demand of new generation, exploitation new type lithium ion battery electrode material be meet the following electric vehicle with
And portable electronic device development is necessary.Since rich reserves (26.4%, second), environment are friendly in the earth's crust for element silicon
It is good, and with lithium alloying can occur at normal temperatures for silicon, have the specific capacity for decupling commercialization graphite-like electrode material, because
This silicon-based anode is the most potential next-generation negative material for replacing graphite cathode.But silicium cathode material is in de-, embedding lithium
During to will appear volume change excessive (300%), repeatedly embrittlement occurs for material after cycle, specific capacity reduces, electric conductivity
Difference, a series of problems, such as generating unstable solid-state electrolytic solution interface (SEI).In order to overcome the problems, such as these, scientific research personnel carries out
A large amount of trials introduce buffer layer using Composite technology and are expanded come compensating material.
Carbonaceous negative material volume change in charge and discharge process is smaller, has preferable cyclical stability, and graphite
The carbon of change is good electronic conductor.In addition, silicon is close with carbon geochemistry property, it is commonly used for the preferred matrix compound with silicon.
In silicon/carbon complex system, silicon particle provides lithium storage content as active material, and carbon can improve siliceous material
Electric conductivity, and elemental silicon can be disperseed, avoid the reunion of silicon particle.Therefore, silicon/carbon composite combines the advantages of the two,
Height ratio capacity and longer cycle life are shown, the hot spot of Recent study is become, is expected to substitute graphite as lithium of new generation
Ion battery cathode material.
In recent years, the patent report about silicon/carbon compound cathode materials is increasing, number of patent application
201611218746.5 silicon-carbon cathode material and preparation method, a kind of 201710524085.7 high-performance silicon-carbon of number of patent application is negative
By nanometer in 210710074206.2 silicon-carbon cathode material of preparation method and number of patent application of pole material and preparation method thereof
In Si powder and graphite dispersion to organic precursor, then it is distributed in pitch is further coated after drying, finally sintering,
It crushes, screening obtains negative material.The first circle capacity of silicon-carbon cathode material made from this method is in 600-1200mAh/g, silicon
Mass fraction be usually no more than 20%.This method is limited by silica flour size and dispersing technology, and silicon and the compound of carbon are only
Physical bond, the uniform mixing being difficult to realize on molecular scale.201710270902.0 silicon-carbon cathode material of number of patent application and
First simple substance silicon face is handled in preparation method, organo-functional group in grafting, then by itself and modified quasiflake graphite
Alkene mixes, and introduces another organic matter later and polymerisation occurs for the organo-functional group on elementary silicon surface, enhance silicon and stone
Chemical bonding between black alkene should although negative material obtained by this method has higher first circle specific capacity 1764mAh/g
Preparation method is cumbersome, and materials conductive performance can be deteriorated after graphene is carried out oxidation modification, and the introducing of gas chromatography
Ion transmission can be influenced, the dynamic performance of material is caused to be decayed.
The studies above shows that these silicon-carbon cathode materials are all to mix silicon nanoparticle and various carbon base bodies at present
It closes, is physical bond between silicon and carbon, since volume change is big during removal lithium embedded for silicon, with the progress of cycle, silicon-carbon
Between combination become to eventually lead to the separation of silicon and carbon material worse and worse, to lose point contact.And simple substance used
Silicon particle size is in 100nm or more, repeatedly after cycle, due to SEI films caused by volume expansion thicken it is more, to make long week
Phase cyclical stability declines.
Invention content
The purpose of the present invention is to provide a kind of silicon-carbon composite cathode material for negative electrode of lithium ion battery, material tools
There is the characteristics of Volumetric expansion is low, stable cycle performance.
In order to achieve the above object, the present invention provides a kind of high performance silicon/carbon nano composite anode material, feature exists
In including the Nano carbon balls shape particle with mesopore orbit, elemental silicon is filled with inside spherical particle and/or in mesopore orbit
Grain.
Preferably, the size of the silicon particle is less than 10nm.
Preferably, the mesopore orbit is orderly distributed on Nano carbon balls shape particle.
Preferably, the aperture of the mesopore orbit is 2-10nm.
Preferably, a diameter of 100-200nm of the Nano carbon balls shape particle.
The present invention also provides the preparation methods of above-mentioned high performance silicon/carbon nano composite anode material, which is characterized in that
Including：Mesoporous organosilicon nano particle is prepared, mesoporous organosilicon particle is carbonized, carbonizing production is with mesopore orbit
Carbon skeleton is scattered with silicon oxygen bond inside carbon skeleton in carbon-carbon bond network, and the carbonizing production of gained is carried out aluminothermic reduction, carbon skeleton
Internal silicon oxygen bond fracture, forms simple substance silicon particle, is dispersed in mesopore orbit.
Preferably, the silicon oxygen bond is dispersed in inside carbon skeleton in carbon-carbon bond network.
Preferably, the preparation method of the mesoporous organosilicon nano particle includes：It is mixed with deionized water in ethyl alcohol
In alkaline solution system, surfactant is added, organosilane precursor is added after stirring, continues to obtain after being stirred overnight uniformly
The suspension of dispersion centrifuges, and drying obtains mesoporous organosilicon powder.
Preferably, the organosilane precursor is the organosilicon containing alkyl or aromatic group.
It is highly preferred that the organosilane precursor is the organosilicon containing double triethoxysilicane alkyl.It is highly preferred that institute
The organosilicon containing double triethoxysilicane alkyl stated is bis- (triethoxysilicane alkyl) ethane of 1,2- or the bis- (triethoxies of Isosorbide-5-Nitrae-
Silylation) benzene.
It is highly preferred that the pattern of the mesoporous organosilicon is spherical, orderly mesopore orbit, aperture are dispersed on sphere
Range is connected by four kinds of silicon, oxygen, carbon, hydrogen elements in the form of chemical bond in 2-5nm, ball wall.
Preferably, the charing carries out in an inert atmosphere.It is highly preferred that the inert atmosphere refers to argon gas or nitrogen
Gas.
Preferably, described to be reduced to aluminothermic reduction.
It is highly preferred that the aluminothermic reduction refers to aluminothermy fused salt reduction method, reducing agent used is aluminium chloride and aluminium powder
Mixture.
Preferably, the carbonizing production is spherical, orderly mesopore orbit is dispersed on sphere, ball wall is by silicon, oxygen, carbon
Three kinds of elements are connected in the form of chemical bond.
Preferably, the preparation method of the high performance silicon/carbon nano composite anode material includes：By cetyl front three
Base ammonium bromide is added in deionized water, ethyl alcohol and the ammonia spirit of mixing, stirs 1-3h；Organosilane precursor solution is added to stir
It mixes overnight；Wherein, for mechanical agitation rotating speed at 300-500 revs/min, temperature selects 25-60 degree；Gained suspension is centrifuged
Separation, centrifuge speed selects 6000-15000 revs/min, then is washed successively with ethyl alcohol and deionized water, dries in an oven；
Gained white powder is placed in tube furnace, is carbonized under inert gas shielding.Carbonization temperature is 400-800 degree, and carbonization time is
8-12h, heating rate are 1-5 degrees/min；Later, carbonizing production is mixed with aluminium powder and chlorination aluminium powder, 200-300 degree into
Row aluminothermic reduction；Reduction gained crude product is washed with water, dilute hydrochloric acid, ethyl alcohol respectively, and silicon-carbon cathode material is prepared after dry.
Silicon-carbon cathode material in the present invention is obtained by order mesoporous organic silicon granule after charing, reduction.
Organosilane precursor in the present invention contains silylation and organic group such as alkyl or virtue with silylation bridging
Perfume base group, carbon source of the above-mentioned organic group as silicon-carbon cathode material, the preferred phenyl ring of the organic group.
Preferably, the volume ratio of ethyl alcohol and deionized water in the alkaline solution system that the ethyl alcohol is mixed with deionized water
It is 1: 3~1: 2, basic solvent selects ammonium hydroxide, and the volume ratio of ammonium hydroxide and deionized water is 1: 100~1: 50；Surfactant selects
Select cetyl trimethylammonium bromide, the molar ratio of surfactant and deionized water is 1: 10000~1: 1000, organic silicon source
The molar ratio of presoma and deionized water is 1: 1000~1: 500.
Preferably, the carbonization temperature is 400~800 degree, and inert atmosphere is nitrogen or argon gas.
Preferably, fused salt used in the aluminothermic reduction is aluminium chloride and aluminium powder, carbonizing production and aluminium powder and chlorination aluminium powder
Mass ratio is 1: 0.5~1.2: 5~15.
Preferably, the aluminothermic reduction temperature is 200-300 degree.
The invention belongs to novel energy resource material technology field, more particularly to a kind of high performance lithium ion battery silicon/carbon nanometer
The controllable method for preparing of composite negative pole material, specific preparation process are as follows：Using various organosilicons as raw material, pass through sol-gel
Method prepares porous organic nano material, by the fused salts reduction process such as high temperature carbonization and the hot aluminothermy of magnesium, can finally obtain
Silicon/carbon nano composite anode material.
Compared with prior art, the beneficial effects of the invention are as follows：
1. the organic group type of mesoporous organosilicon material is various, different types of organic group can be selected according to demand
Group, it is hereby achieved that the Si-C composite material with different silicon carbon ratios.
It is that lithium ion transport and silicon particle volume are swollen 2. mesoporous organosilicon particle surface is uniform-distribution with the duct of 2-10nm
It is swollen to provide channel and space.
3. the silicon particle size in gained Si-C composite material nano particle is less than 10nm, and is evenly distributed on carbon skeleton
In, it ensure that the stability of long period cycle.
4. the aromatic carbon source of selection can obtain the higher carbon skeleton of degree of graphitization after charing, be conducive to electronics
Transmission.
5. there is silicon/carbon compound cathode materials prepared by the present invention porous structure, simple substance silicon particle to be dispersed in carbon skeleton
Inside mesopore orbit, the features such as lithium ion charge and discharge process Volumetric expansion is low, electrochemistry stable cycle performance.
Description of the drawings
Fig. 1 is the structural schematic diagram of silicon/carbon compound cathode materials of the present invention.
Fig. 2 is the transmission electron microscope picture of the silicon/carbon compound cathode materials of one embodiment of the invention 1.
Fig. 3 is the x-ray diffraction pattern of the silicon/carbon compound cathode materials of one embodiment of the invention 1.
Fig. 4 is the first charge-discharge curve graph of the silicon/carbon compound cathode materials of one embodiment of the invention 2.
Specific implementation mode
Present invention will be further explained below with reference to specific examples.It should be understood that these embodiments are merely to illustrate the present invention
Rather than it limits the scope of the invention.In addition, it should also be understood that, after reading the content taught by the present invention, people in the art
Member can make various changes or modifications the present invention, and such equivalent forms equally fall within the application the appended claims and limited
Range.
Temperature in the present invention is unless otherwise specified degree Celsius.
Embodiment 1
A kind of high performance silicon/carbon nano composite anode material, as shown in Figure 1, comprising being the mesoporous of 2-10nm with aperture
The nanometer spherical particle of a diameter of 100-200nm in duct is filled with elemental silicon inside spherical particle and/or in mesopore orbit
Grain.The size of the silicon particle is less than 10nm.
The preparation method of the high performance silicon/carbon nano composite anode material is：
Mesoporous organosilicon nano particle is prepared, the preparation method of the mesoporous organosilicon nano particle is：By 280mL go from
Sub- water, 120mL ethyl alcohol are added 600mgCTAB after the mixing of 2mL concentrated ammonia liquors, stir 1-3h, wherein mechanical agitation rotating speed is 400
Rev/min, temperature selects 25 degree, 0.5mL1 is then added, bis- (triethoxysilicane alkyl) benzene (BTEB) of 4- are stirred overnight, obtain
It to evenly dispersed suspension, centrifuges, centrifuge speed selects 8000 revs/min, then uses ethyl alcohol and deionized water successively
Wash each three times, place baking oven dry to obtain particle size range 100-200nm order mesoporous organosilicon powder.
Gained white mesoporous organosilicon powder is placed in tube furnace and is carbonized, with 3 degree mins under nitrogen atmosphere protection
The heating rate of clock rises to 600 degree, natural cooling after being kept for 6 hours.Gained carbonizing production is black powder, for mesoporous hole
The carbon skeleton in road, evenly dispersed silicon oxygen bond in carbon-carbon bond network inside carbon skeleton.
Black powder and aluminium powder, the aluminum chloride powder of certain mass are weighed with mass ratio as 1：1：10 ratio mixing, puts
It sets in stainless steel sealing container, 250 DEG C of progress aluminothermic reductions is warming up to, and keep 8h, by the carbonizing production carbon skeleton of gained
Internal silicon oxygen bond fracture, forms simple substance silicon particle, is dispersed in mesopore orbit.
Products therefrom is cleaned and centrifuged with deionized water, then is washed several times with the dilute hydrochloric acid of 0.1M, ethyl alcohol is finally used
It is centrifuged after washing three times and dry, the product after drying is our negative material.
Gained negative material prepares negative plate by the following method：Using product obtained as nano-silicone wire/carbon negative electrode active material
Matter, Super-P carbon blacks are conductive agent, and CMC is binder, and in mass ratio 6: 2: 2 after mixing, is solvent tune with deionized water
Slurry is made slurry in planetary deaeration agitating device, then is coated slurry on copper foil with automatic smearing machine, and coating thickness is 7.5 μ
Then electrode is placed on 80 DEG C of vacuum drying ovens and dries 12h, then negative plate is cut into the size of needs with electrode preparing device by m.
It is prepared by battery：The button-shaped half-cells of LIR2032 using lithium piece be used as to electrode, in glove box according to negative electrode casing,
The sequence assembling button cell of electrode slice, diaphragm, lithium piece, stainless steel gasket, spring leaf, anode cover.Electrolyte be adopted as dissolved with
Ethylene carbonate (ethylene carbonate, EC)/dimethyl carbonate (dimethylcarbonate, DMC)/5wt% fluoro
Diethyl carbonate (the diethyl of ethylene carbonate (fluoroethylene carbonate, FEC) additive modification
Carbonate, DEC) (volume ratio 3: 4: 3) solution 1M LiPF6。
Battery testing：Using new prestige battery test system
Embodiment 2
A kind of high performance silicon/carbon nano composite anode material, including the diameter with the mesopore orbit that aperture is 2-10nm
For the nanometer spherical particle of 100-200nm, simple substance silicon particle is filled with inside spherical particle and/or in mesopore orbit.Described
The size of silicon particle is less than 10nm.
The preparation method of the high performance silicon/carbon nano composite anode material is：
Mesoporous organosilicon nano particle is prepared, the preparation method of the mesoporous organosilicon nano particle is：By 280mL go from
Sub- water, 120mL ethyl alcohol are added 800mgCTAB after the mixing of 2mL concentrated ammonia liquors, stir 1-3h, wherein mechanical agitation rotating speed is 400
Rev/min, temperature selects 25 degree, 1mL1 is then added, bis- (triethoxysilicane alkyl) ethane (BTEE) of 2- are stirred overnight, obtain
It to evenly dispersed suspension, centrifuges, centrifuge speed selects 9000 revs/min, then uses ethyl alcohol and deionized water successively
Wash each three times, place baking oven dry to obtain particle size range 100-200nm order mesoporous organosilicon powder.
Gained white mesoporous organosilicon powder is placed in tube furnace and is carbonized, with 3 degree mins under nitrogen atmosphere protection
The heating rate of clock rises to 500 degree, natural cooling after being kept for 6 hours.Gained carbonizing production is black powder, for mesoporous hole
The carbon skeleton in road, evenly dispersed silicon oxygen bond in carbon-carbon bond network inside carbon skeleton.
It weighs black powder and aluminium powder, the aluminum chloride powder of certain mass to mix with the ratio that mass ratio is 1: 1: 10, put
It sets in stainless steel sealing container, 220 DEG C of progress aluminothermic reductions is warming up to, and keep 8h, by the carbonizing production carbon skeleton of gained
Internal silicon oxygen bond fracture, forms simple substance silicon particle, is dispersed in mesopore orbit.
Products therefrom is cleaned and centrifuged with deionized water, then is washed several times with the dilute hydrochloric acid of 0.1M, ethyl alcohol is finally used
It is centrifuged after washing three times and dry, the product after drying is our negative material.
Prepared by electrode and battery assembling uses method same as Example 1, is not repeating.
Embodiment 3
A kind of high performance silicon/carbon nano composite anode material, including the diameter with the mesopore orbit that aperture is 2-10nm
For the nanometer spherical particle of 100-200nm, simple substance silicon particle is filled with inside spherical particle and/or in mesopore orbit.Described
The size of silicon particle is less than 10nm.
The preparation method of the high performance silicon/carbon nano composite anode material is：
Mesoporous organosilicon nano particle is prepared, the preparation method of the mesoporous organosilicon nano particle is：By 280mL go from
Sub- water, 150mL ethyl alcohol are added 800mgCTAB after the mixing of 2mL concentrated ammonia liquors, stir 1-3h, wherein mechanical agitation rotating speed is 400
Rev/min, temperature selects 25 degree, and 0.5mL1, bis- (triethoxysilicane alkyl) benzene (BTEB) of 4- and the positive silicic acid of 0.5mL is then added
Ethyl ester is stirred overnight, and obtains evenly dispersed suspension, is centrifuged, and centrifuge speed selects 10000 revs/min, then successively
It is washed each three times with ethyl alcohol and deionized water, places baking oven and dry to obtain particle size range in the order mesoporous organic of 100-200nm
Si powder.
Gained white mesoporous organosilicon powder is placed in tube furnace and is carbonized, with 2 degree mins under nitrogen atmosphere protection
The heating rate of clock rises to 800 degree, natural cooling after being kept for 6 hours.Gained carbonizing production is black powder, for mesoporous hole
The carbon skeleton in road, evenly dispersed silicon oxygen bond in carbon-carbon bond network inside carbon skeleton.
Black powder and aluminium powder, the aluminum chloride powder of certain mass are weighed with mass ratio as 1：0.8：8 ratio mixing,
It is placed in stainless steel sealing container, 230 DEG C of progress aluminothermic reductions is warming up to, and keep 8h, by the carbonizing production carbon bone of gained
Silicon oxygen bond fracture inside frame, forms simple substance silicon particle, is dispersed in mesopore orbit.
Products therefrom is cleaned and centrifuged with deionized water, then is washed several times with the dilute hydrochloric acid of 0.2M, ethyl alcohol is finally used
It is centrifuged after washing three times and dry, the product after drying is our negative material.
Prepared by electrode and battery assembling uses method same as Example 1, is not repeating.
Comparative example 1
According to the method for embodiment 3, bis- (triethoxysilicane alkyl) benzene of Isosorbide-5-Nitrae-are not added, remaining is same as Example 3, no
It repeats again.
Attached drawing 2 is the transmission electron microscope picture for the silicon-carbon composite cathode material that embodiment 1 obtains, from the figure, it can be seen that simple substance
Silicon particle is uniformly mixed in the three-dimensional framework of mesoporous carbon.And the XRD diagram of attached drawing 3 demonstrates the presence of elemental silicon, in addition from
The collection of illustrative plates of attached drawing 3 can also be seen that near 25 degree, there are one very high peaks, which represents degree of graphitization, from the strong of peak
From the point of view of degree, the degree of graphitization of carbon is very high in prepared negative material.Fig. 4 is preceding the two of the negative material that embodiment 2 obtains
Secondary cyclic voltammetry curve, it can be seen from the figure that the charging platform of first lap, near 0.2V, exactly the feature of silicium cathode charges
Platform.Therefore, with this method, silicon/anode composite is successfully prepared.
Table 1, the chemical property of the battery of silicon-carbon cathode material assembling prepared by more different embodiment and comparative examples.
It can be obtained by table 1, the silicon-carbon cathode material of function admirable can be prepared in the present invention, be with the silicon-carbon cathode material
The battery core that negative electrode active material assembles has excellent chemical property.Specifically, although comparative example 1 is with highest embedding
Lithium capacity, but due to the generation of surface SEI films, leading to it, reversible capacity is minimum for the first time, and coulombic efficiency only has 30% for the first time.And
The reversible capacity for the first time of embodiment 1 is 69% in 1000mAh/g or more, for the first time coulombic efficiency, and individual pen capacity declines after 500 circle cycles
Lapse rate is 0.08%, good cycling stability.Embodiment 2 and the obtained silicon-carbon cathode material of embodiment 3 also have lower
Capacity attenuation rate, for the first time reversible capacity reach twice or more of Carbon anode theoretical capacity.
The announcement said according to the above description, those skilled in the art in the invention can also carry out the above embodiment
Change and modification.It is replaced than step 2 as will be described and step 3, can equally obtain silicon/carbon negative pole material.For another example use
The method of magnesiothermic reduction is restored.Therefore, the invention is not limited in above-mentioned specific implementation mode, every art technologies
Any conspicuously improved, replacement or modification that personnel are made on the basis of the present invention belongs to the protection model of the present invention
It encloses.In addition, although having used some specific terms in this specification, these terms are merely for convenience of description, not right
The present invention constitutes any restrictions.
Claims (10)
1. a kind of high performance silicon/carbon nano composite anode material, which is characterized in that include the Nano carbon balls shape with mesopore orbit
Particle is filled with simple substance silicon particle inside spherical particle and/or in mesopore orbit.
2. high performance silicon/carbon nano composite anode material as described in claim 1, which is characterized in that the silicon particle
Size is less than 10nm；The aperture of the mesopore orbit is 2-10nm；A diameter of 100- of the Nano carbon balls shape particle
200nm。
3. the preparation method of high performance silicon as claimed in claim 1 or 2/carbon nano composite anode material, which is characterized in that packet
It includes：Mesoporous organosilicon nano particle is prepared, mesoporous organosilicon particle is carbonized, carbonizing production is the carbon with mesopore orbit
Skeleton is scattered with silicon oxygen bond inside carbon skeleton in carbon-carbon bond network, the carbonizing production of gained is carried out aluminothermic reduction, in carbon skeleton
The silicon oxygen bond in portion is broken, and is formed simple substance silicon particle, is dispersed in mesopore orbit.
4. the preparation method of high performance silicon as claimed in claim 3/carbon nano composite anode material, which is characterized in that described
The preparation method of mesoporous organosilicon nano particle include：In the alkaline solution system that ethyl alcohol is mixed with deionized water, addition
Surfactant adds organosilane precursor after stirring, continues to obtain evenly dispersed suspension after being stirred overnight, centrifugation point
From drying obtains mesoporous organosilicon powder.
5. the preparation method of high performance silicon as claimed in claim 4/carbon nano composite anode material, which is characterized in that described
Organosilane precursor be the organosilicon containing double triethoxysilicane alkyl.
6. the preparation method of high performance silicon as claimed in claim 3/carbon nano composite anode material, which is characterized in that described
Charing carry out in an inert atmosphere.
7. the preparation method of high performance silicon as claimed in claim 3/carbon nano composite anode material, which is characterized in that described
Be reduced to aluminothermic reduction；Fused salt used in the aluminothermic reduction is aluminium chloride and aluminium powder, carbonizing production and aluminium powder and chlorination aluminium powder
Mass ratio be 1: 0.5~1.2: 5~15；The aluminothermic reduction temperature is 200-300 degree.
8. the preparation method of high performance silicon as claimed in claim 3/carbon nano composite anode material, which is characterized in that described
The alkaline solution system that is mixed with deionized water of ethyl alcohol in the volume ratio of ethyl alcohol and deionized water be 1: 3~1: 2, basic solvent
The volume ratio of selection ammonium hydroxide, ammonium hydroxide and deionized water is 1: 100~1: 50；Surfactant selects cetyl trimethyl bromination
The molar ratio of ammonium, surfactant and deionized water is 1: 10000~1: 1000, and organic silicon source presoma and deionized water are rubbed
You are than being 1: 1000~1: 500.
9. the preparation method of high performance silicon as claimed in claim 3/carbon nano composite anode material, which is characterized in that described
Carbonization temperature is 400~800 degree.
10. the preparation method of high performance silicon as claimed in claim 1 or 2/carbon nano composite anode material, which is characterized in that packet
It includes：Cetyl trimethylammonium bromide is added in deionized water, ethyl alcohol and the ammonia spirit of mixing, 1-3h is stirred；It is added
Organosilane precursor solution is stirred overnight；Wherein, for tool speed of agitator at 300-500 revs/min, temperature selects 25-60 degree；By institute
It obtains suspension to be centrifuged, centrifuge speed selects 6000-15000 revs/min, then ethyl alcohol and deionization is used to wash successively
It washs, dries in an oven；Gained white powder is placed in tube furnace, is carbonized under inert gas shielding.Carbonization temperature is 400-
800 degree, carbonization time 8-12h, heating rate is 1-5 degrees/min；Later, carbonizing production and aluminium powder and chlorination aluminium powder are mixed
It closes, aluminothermic reduction is carried out in 200-300 degree；Reduction gained crude product is washed with water, dilute hydrochloric acid, ethyl alcohol respectively, is prepared after dry
Obtain silicon-carbon cathode material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810261003.9A CN108428876B (en) | 2018-03-27 | 2018-03-27 | High-performance silicon/carbon nano composite negative electrode material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810261003.9A CN108428876B (en) | 2018-03-27 | 2018-03-27 | High-performance silicon/carbon nano composite negative electrode material and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108428876A true CN108428876A (en) | 2018-08-21 |
| CN108428876B CN108428876B (en) | 2020-08-11 |
Family
ID=63159234
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810261003.9A Active CN108428876B (en) | 2018-03-27 | 2018-03-27 | High-performance silicon/carbon nano composite negative electrode material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108428876B (en) |
Cited By (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109786706A (en) * | 2019-01-17 | 2019-05-21 | 新奥石墨烯技术有限公司 | Negative electrode material and preparation method thereof, cathode and battery |
| CN109817925A (en) * | 2019-01-24 | 2019-05-28 | 广东凯金新能源科技股份有限公司 | Lithium ion secondary battery Si oxide composite negative pole material and preparation method |
| CN110071272A (en) * | 2019-04-12 | 2019-07-30 | 东华大学 | A kind of boron doping silicon substrate composite negative pole material and its preparation method and application |
| US10424786B1 (en) | 2018-12-19 | 2019-09-24 | Nexeon Limited | Electroactive materials for metal-ion batteries |
| US10508335B1 (en) | 2019-02-13 | 2019-12-17 | Nexeon Limited | Process for preparing electroactive materials for metal-ion batteries |
| GB2578797A (en) * | 2018-11-08 | 2020-05-27 | Nexeon Ltd | Electroactive materials for metal-Ion batteries |
| GB2578796A (en) * | 2018-11-08 | 2020-05-27 | Nexeon Ltd | Electroactive materials for metal-ion batteries |
| CN111435734A (en) * | 2019-12-27 | 2020-07-21 | 蜂巢能源科技有限公司 | Porous silicon-carbon composite negative electrode material and preparation method thereof |
| CN112234181A (en) * | 2020-10-27 | 2021-01-15 | 合肥工业大学 | Two-dimensional silicon oxide/carbon composite lithium ion battery cathode material and preparation method thereof |
| CN112479177A (en) * | 2020-11-26 | 2021-03-12 | 天能帅福得能源股份有限公司 | Preparation method of ordered mesoporous silicon-carbon composite material |
| US10964940B1 (en) | 2020-09-17 | 2021-03-30 | Nexeon Limited | Electroactive materials for metal-ion batteries |
| GB2587328A (en) * | 2019-09-10 | 2021-03-31 | Nexeon Ltd | Silicon-carbon composite materials and methods |
| CN113461016A (en) * | 2021-06-30 | 2021-10-01 | 松山湖材料实验室 | Silicon-carbon negative electrode material and preparation method and application thereof |
| CN113770374A (en) * | 2021-09-13 | 2021-12-10 | 西南科技大学 | Hollow carbon nanosphere/Al/Fe2O3Direct writing preparation method of base nano thermite |
| CN114122370A (en) * | 2021-10-29 | 2022-03-01 | 西安交通大学 | Negative electrode material for inducing silane deposition through porous carbon double bond modification and preparation method and application thereof |
| CN114520313A (en) * | 2020-11-20 | 2022-05-20 | 华为技术有限公司 | Silicon-carbon composite material and preparation method and application thereof |
| WO2023093893A1 (en) * | 2021-11-27 | 2023-06-01 | 兰溪致德新能源材料有限公司 | Nano-silicon-oxygen-carbon structure composite material and preparation method therefor, negative electrode and electrochemical device |
| CN116287829A (en) * | 2023-03-24 | 2023-06-23 | 承德天大钒业有限责任公司 | Aluminum-molybdenum-carbon alloy and preparation method thereof |
| US11905593B2 (en) | 2018-12-21 | 2024-02-20 | Nexeon Limited | Process for preparing electroactive materials for metal-ion batteries |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103305965A (en) * | 2013-06-04 | 2013-09-18 | 清华大学深圳研究生院 | Silicon-carbon composite material with nano micropores and preparation method as well as application thereof |
| CN103427073A (en) * | 2013-08-05 | 2013-12-04 | 同济大学 | Preparation method of mesoporous Si/C composite microsphere as lithium battery negative electrode material |
| CN103840140A (en) * | 2012-11-21 | 2014-06-04 | 清华大学 | Porous carbon silicon composite material and preparation method thereof |
| JP2015230850A (en) * | 2014-06-05 | 2015-12-21 | 株式会社リコー | Lithium sulfur secondary battery |
| CN107123790A (en) * | 2016-02-24 | 2017-09-01 | 宁波富理电池材料科技有限公司 | A kind of porous silicon-base composite negative pole material, preparation method and lithium ion battery |
-
2018
- 2018-03-27 CN CN201810261003.9A patent/CN108428876B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103840140A (en) * | 2012-11-21 | 2014-06-04 | 清华大学 | Porous carbon silicon composite material and preparation method thereof |
| CN103305965A (en) * | 2013-06-04 | 2013-09-18 | 清华大学深圳研究生院 | Silicon-carbon composite material with nano micropores and preparation method as well as application thereof |
| CN103427073A (en) * | 2013-08-05 | 2013-12-04 | 同济大学 | Preparation method of mesoporous Si/C composite microsphere as lithium battery negative electrode material |
| JP2015230850A (en) * | 2014-06-05 | 2015-12-21 | 株式会社リコー | Lithium sulfur secondary battery |
| CN107123790A (en) * | 2016-02-24 | 2017-09-01 | 宁波富理电池材料科技有限公司 | A kind of porous silicon-base composite negative pole material, preparation method and lithium ion battery |
Cited By (33)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2578797B (en) * | 2018-11-08 | 2020-11-11 | Nexeon Ltd | Electroactive materials for metal-Ion batteries |
| US11688849B2 (en) | 2018-11-08 | 2023-06-27 | Nexeon Limited | Electroactive materials for metal-ion batteries |
| US11165054B2 (en) | 2018-11-08 | 2021-11-02 | Nexeon Limited | Electroactive materials for metal-ion batteries |
| US11695110B2 (en) | 2018-11-08 | 2023-07-04 | Nexeon Limited | Electroactive materials for metal-ion batteries |
| US11011748B2 (en) | 2018-11-08 | 2021-05-18 | Nexeon Limited | Electroactive materials for metal-ion batteries |
| GB2578796B (en) * | 2018-11-08 | 2020-12-16 | Nexeon Ltd | Electroactive materials for metal-ion batteries |
| GB2578797A (en) * | 2018-11-08 | 2020-05-27 | Nexeon Ltd | Electroactive materials for metal-Ion batteries |
| GB2578796A (en) * | 2018-11-08 | 2020-05-27 | Nexeon Ltd | Electroactive materials for metal-ion batteries |
| US10658659B1 (en) | 2018-12-19 | 2020-05-19 | Nexeon Limited | Electroactive materials for metal-ion batteries |
| GB2580033B (en) * | 2018-12-19 | 2021-03-10 | Nexeon Ltd | Electroactive materials for metal-Ion batteries |
| GB2580033A (en) * | 2018-12-19 | 2020-07-15 | Nexeon Ltd | Electroactive materials for metal-Ion batteries |
| US10424786B1 (en) | 2018-12-19 | 2019-09-24 | Nexeon Limited | Electroactive materials for metal-ion batteries |
| US11715824B2 (en) | 2018-12-19 | 2023-08-01 | Nexeon Limited | Electroactive materials for metal-ion batteries |
| US10938027B2 (en) | 2018-12-19 | 2021-03-02 | Nexeon Limited | Electroactive materials for metal-ion batteries |
| US11905593B2 (en) | 2018-12-21 | 2024-02-20 | Nexeon Limited | Process for preparing electroactive materials for metal-ion batteries |
| CN109786706A (en) * | 2019-01-17 | 2019-05-21 | 新奥石墨烯技术有限公司 | Negative electrode material and preparation method thereof, cathode and battery |
| CN109817925A (en) * | 2019-01-24 | 2019-05-28 | 广东凯金新能源科技股份有限公司 | Lithium ion secondary battery Si oxide composite negative pole material and preparation method |
| US10508335B1 (en) | 2019-02-13 | 2019-12-17 | Nexeon Limited | Process for preparing electroactive materials for metal-ion batteries |
| CN110071272A (en) * | 2019-04-12 | 2019-07-30 | 东华大学 | A kind of boron doping silicon substrate composite negative pole material and its preparation method and application |
| GB2587328A (en) * | 2019-09-10 | 2021-03-31 | Nexeon Ltd | Silicon-carbon composite materials and methods |
| GB2587328B (en) * | 2019-09-10 | 2021-12-22 | Nexeon Ltd | Composite materials and methods |
| CN111435734A (en) * | 2019-12-27 | 2020-07-21 | 蜂巢能源科技有限公司 | Porous silicon-carbon composite negative electrode material and preparation method thereof |
| US10964940B1 (en) | 2020-09-17 | 2021-03-30 | Nexeon Limited | Electroactive materials for metal-ion batteries |
| CN112234181A (en) * | 2020-10-27 | 2021-01-15 | 合肥工业大学 | Two-dimensional silicon oxide/carbon composite lithium ion battery cathode material and preparation method thereof |
| CN114520313A (en) * | 2020-11-20 | 2022-05-20 | 华为技术有限公司 | Silicon-carbon composite material and preparation method and application thereof |
| WO2022105279A1 (en) * | 2020-11-20 | 2022-05-27 | 华为技术有限公司 | Silicon-carbon composite material and preparation method therefor and application thereof |
| CN112479177A (en) * | 2020-11-26 | 2021-03-12 | 天能帅福得能源股份有限公司 | Preparation method of ordered mesoporous silicon-carbon composite material |
| CN113461016A (en) * | 2021-06-30 | 2021-10-01 | 松山湖材料实验室 | Silicon-carbon negative electrode material and preparation method and application thereof |
| CN113770374A (en) * | 2021-09-13 | 2021-12-10 | 西南科技大学 | Hollow carbon nanosphere/Al/Fe2O3Direct writing preparation method of base nano thermite |
| CN114122370A (en) * | 2021-10-29 | 2022-03-01 | 西安交通大学 | Negative electrode material for inducing silane deposition through porous carbon double bond modification and preparation method and application thereof |
| CN114122370B (en) * | 2021-10-29 | 2023-12-19 | 西安交通大学 | Porous carbon double bond modified silane deposition-induced negative electrode material and preparation method and application thereof |
| WO2023093893A1 (en) * | 2021-11-27 | 2023-06-01 | 兰溪致德新能源材料有限公司 | Nano-silicon-oxygen-carbon structure composite material and preparation method therefor, negative electrode and electrochemical device |
| CN116287829A (en) * | 2023-03-24 | 2023-06-23 | 承德天大钒业有限责任公司 | Aluminum-molybdenum-carbon alloy and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108428876B (en) | 2020-08-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108428876A (en) | A kind of high performance silicon/carbon nano composite anode material and preparation method thereof | |
| CN107579239B (en) | A kind of graphene/solid electrolyte compound coating silicon composite cathode and preparation method thereof | |
| CN105895886B (en) | A kind of sodium-ion battery transition metal phosphide/porous anode composite and preparation method thereof | |
| CN101510602B (en) | Method for preparing silicon composite cathode material of lithium ion battery | |
| CN102916167B (en) | Mesoporous silicon compound as lithium ion battery negative material and preparation method thereof | |
| CN106025221B (en) | A kind of preparation method of silicon/carbon graphite composite negative pole material | |
| CN106099113A (en) | A kind of nucleocapsid structure Si-C composite material and preparation method thereof | |
| CN109461921B (en) | Preparation method of modified silicon-based alloy composite negative electrode material of lithium ion battery | |
| CN106935861B (en) | A kind of sodium-ion battery carbon negative pole material and preparation method thereof | |
| CN102983317A (en) | Silicon-based composite material and preparation method thereof, silicon-carbon composite material and lithium ion battery | |
| CN109449421B (en) | Silicon-based alloy composite negative electrode material of lithium ion battery and preparation method thereof | |
| CN112234181B (en) | Two-dimensional silicon oxide/carbon composite lithium ion battery cathode material and preparation method thereof | |
| CN104393272A (en) | Lithium titanate cathode composite material and preparation method | |
| CN108666560A (en) | Lithium ion battery, nano silicon material and preparation method thereof | |
| CN104103821A (en) | Preparation method for silicon-carbon anode material | |
| Zhao et al. | Nitrogen/oxygen codoped hierarchical porous Carbons/Selenium cathode with excellent lithium and sodium storage behavior | |
| CN104282894B (en) | A kind of preparation method of porous Si/C complex microsphere | |
| Zhang et al. | Carbon coated SiO nanoparticles embedded in hierarchical porous N-doped carbon nanosheets for enhanced lithium storage | |
| Wang et al. | Facile synthesis of boron-doped porous carbon as anode for lithium–ion batteries with excellent electrochemical performance | |
| CN108899499A (en) | Based on phosphatic negative electrode material of Sb/Sn and preparation method thereof and the application in sodium-ion battery | |
| CN110071272A (en) | A kind of boron doping silicon substrate composite negative pole material and its preparation method and application | |
| CN105552308A (en) | Negative electrode of lithium ion battery, lithium ion battery and application of lithium ion battery | |
| CN115207344B (en) | Preparation of FexSey@CN composite material and electrochemical energy storage application thereof | |
| CN108649191A (en) | The preparation method and its resulting materials of a kind of antimony/nitrogen-doped graphene compound and application | |
| CN104362320A (en) | Positive electrode material of lithium-sulfur battery and preparation method of positive electrode material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |