CN107221652A - A kind of sulfur doping carbon material and preparation method thereof - Google Patents
A kind of sulfur doping carbon material and preparation method thereof Download PDFInfo
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- CN107221652A CN107221652A CN201710190759.4A CN201710190759A CN107221652A CN 107221652 A CN107221652 A CN 107221652A CN 201710190759 A CN201710190759 A CN 201710190759A CN 107221652 A CN107221652 A CN 107221652A
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- carbon material
- sulfur doping
- doping carbon
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- mixed liquor
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- 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
- H01M4/366—Composites as layered products
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- 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
- H01M4/58—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
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
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- 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
It is an object of the invention to provide a kind of sulfur doping carbon material with higher specific discharge capacity, the carbon layers having thicknesses of the sulfur doping carbon material are 20 300 nanometers, and sulfur content is 3 20wt%.Meanwhile, the invention also discloses the preparation method of above-mentioned sulfur doping carbon material.The sulfur doping carbon material that the present invention is provided has higher specific discharge capacity.
Description
Technical field
The invention belongs to technical field of lithium ion, and in particular to a kind of sulfur doping carbon material and preparation method thereof.
Background technology
Since 21 century, with the increasingly exhausted and increasingly serious environmental problem of the fossil energies such as coal, oil, to ensure
The sustainable development of society, seeks new clean energy resource as the common problem of the mankind.In the upsurge that new energy materialses are studied,
Emphasis of the advantages of lithium ion battery is because of its high-energy-density, overlength cycle life and high security as human research.
Lithium ion battery different reversible insertion and can deviate from the lithium intercalation compound of lithium ion as electricity using two kinds
Pond positive pole and negative pole, during charging, lithium ion is from positive pole deintercalation, by electrolyte and barrier film, in embedded negative pole, then phase during electric discharge
Instead, lithium ion is from negative pole deintercalation, embedded negative pole.At present, the compound containing lithium is used in lithium ion battery as positive pole material
Material, and carbon material turns into main flow commercial lithium because of its good chemical stability, electric conductivity, thermal conductivity, heat endurance, low cost etc.
The negative material of ion battery.But, with the popularization of electric automobile, electronic product is to portability, miniaturization and multifunction
Development, lithium ion battery can not gradually meet the demand of people, therefore, and we are in the urgent need to seeking the new height of high-energy
Can battery.
The content of the invention
It is an object of the invention to provide a kind of sulfur doping carbon material with higher specific discharge capacity.
The technical scheme that present invention solution above-mentioned technical problem is used is as follows：
A kind of sulfur doping carbon material is provided, wherein, the carbon layers having thicknesses of the sulfur doping carbon material are 20-300 nanometers, and sulphur contains
Measure as 3-20wt%.
Meanwhile, present invention also offers the preparation method of above-mentioned sulfur doping carbon material, including：By antimony acetate, thioacetyl
Amine and ethylene glycol mixing, are stirred vigorously, obtain mixed liquor；Then mixed liquor is placed in mortar, adds ethylenediamine tetra-acetic acid and enter
Row grinding, obtains predecessor；The predecessor is sintered again, the sulfur doping carbon material is obtained.
The technical scheme provided using the present invention, with following features：
The present invention is using thioacetamide as sulphur source, and using antimony acetate as plasticity medium, ethylene glycol is used as solvent, ethylenediamine
Tetraacethyl is as carbon source, in calcination process, thioacetamide and antimony acetate reaction generation antimonous sulfide, with calcination time
Extension, the antimony element volatilization in compound antimonous sulfide, and ethylenediamine tetra-acetic acid becomes carbon, calcining knot after high-temperature calcination
Shu Hou, that is, form a kind of unique structure -- the carbon-coating of sulphur Uniform Doped.When above-mentioned sulfur doping carbon material is used as lithium ion battery
Negative material is in use, it has excellent specific discharge capacity.
Brief description of the drawings
Fig. 1 is the SEM figures for the sulfur doping carbon material that the embodiment of the present invention 1 is prepared；
Fig. 2 is the battery discharge curve figure of sulfur doping carbon material prepared by invention the present embodiment 1；
Fig. 3 is the SEM figures for the sulfur doping carbon material that the embodiment of the present invention 2 is prepared；
Fig. 4 is the SEM figures for the sulfur doping carbon material that the embodiment of the present invention 3 is prepared.
Embodiment
In order that technical problem solved by the invention, technical scheme and beneficial effect are more clearly understood, below in conjunction with
Drawings and Examples, the present invention will be described in further detail.It should be appreciated that specific embodiment described herein is only used
To explain the present invention, it is not intended to limit the present invention.
In the sulfur doping carbon material that the present invention is provided, carbon layers having thicknesses are 20-300 nanometers, and sulfur content is 3-20wt%.
Under preferable case, carbon-coating length is 5-20 microns in above-mentioned sulfur doping carbon material.
In the case of further preferably, also contain nitrogen in the sulfur doping carbon material.Through electro-chemical test, work as sulfur doping
In carbon material during nitrogen also containing doping, its not only capacity it is high, and with more excellent beneficial electric conductivity, cyclical stability and times
Rate performance is also more preferable.
Meanwhile, the invention also discloses the preparation method of above-mentioned sulfur doping carbon material, specifically include：Including：By antimony acetate,
Thioacetamide and ethylene glycol mixing, are stirred vigorously, obtain mixed liquor；Then mixed liquor is placed in mortar, adds ethylenediamine
Tetraacethyl is ground, and obtains predecessor；The predecessor is sintered again, the sulfur doping carbon material is obtained.
According to the present invention, first, mixed liquor is prepared, the mixed liquor includes antimony acetate, thioacetamide and ethylene glycol.Specifically
, first antimony acetate and thioacetamide can be put into blender jar, add ethylene glycol and be stirred vigorously.
In mixed liquor, the relative amount of antimony acetate, thioacetamide and ethylene glycol can change interior in a big way, preferably feelings
Under condition, in above-mentioned mixed liquor, the content ratio of antimony acetate, thioacetamide and ethylene glycol is 1.0-6.0g：1.0-6.0g：4-
12ml.Inventor determines that the mass range of antimony acetate and thioacetamide in the present invention is within the above range through further investigation
Best effect can be obtained, can also obtain mixing sulphur carbon material higher than above range, but mixing sulphur excessively prevents it from forming perfection
Carbon-coating structure, cause chemical property to decline, can then make less than above range element sulphur in annealing process all or big portion
Divide volatilization, effect declines.
What those skilled in the art will be appreciated that, above-mentioned content is the proportionate relationship of three, does not represent the addition of three
Amount is only limitted in above range, i.e., the content of antimony acetate is not just for 1.0-6.0g.Three's addition need to only ensure in above-mentioned ratio
In the range of example.
According to the present invention, after antimony acetate, thioacetamide and ethylene glycol are mixed, under preferable case, it is stirred vigorously,
Antimony acetate, thioacetamide and ethylene glycol is set to be sufficiently mixed uniformly, the time of stirring is preferably 6-24h.It is above-mentioned antimony acetate, thio
Acetamide and ethylene glycol are material known to chemical field, can be obtained by conventional commercial.
Preparation is obtained after above-mentioned mixed liquor, and mixed liquor need to be placed in mortar, is added ethylenediamine tetra-acetic acid and is ground.Enter
During row grinding, the amount of the ethylenediamine tetra-acetic acid of addition can change interior in a big way, under preferable case, the ethylenediamine tetraacetic of addition
The mass ratio of antimony acetate is 0.2-4.0 in the amount and mixed liquor of acetic acid：1.0-6.0.It is used as the amount of the ethylenediamine tetra-acetic acid of carbon source
Unsuitable too little or too much, very few that final yield is reduced, crossing at most makes raw material mixing uneven, cannot uniformly mix sulphur
Carbon material.
The mortar material used during above-mentioned grinding operation is preferably agate.
After above-mentioned milled processed, that is, obtain predecessor.According to the present invention, also need the predecessor being sintered place
Reason, so as to obtain the sulfur doping carbon material.
In the present invention, under preferable case, the temperature of the sintering processes is 800-1100 DEG C, and the time is 2-6h, heating speed
Rate is 1-10 DEG C/min.
According to the present invention, above-mentioned sintering processes can be carried out under an inert atmosphere.Above-mentioned inert atmosphere can be using conventional argon
Gas, nitrogen etc..During sintering processes, gas flow rate is 10-40ml/min in preferably above-mentioned inert atmosphere.
In the present invention, under preferable case, above-mentioned sintering processes can be carried out in ammonia.When above-mentioned sintering processes are in ammonia
During progress, nitrogen, the carbon material of sulphur codope can obtain.When as lithium ion battery negative material in use, through electro-chemical test,
Its good conductivity, capacity is high, and cyclical stability and high rate performance are preferable.
The present invention is using thioacetamide as sulphur source, and using antimony acetate as plasticity medium, ethylene glycol is used as solvent, ethylenediamine
Tetraacethyl is as carbon source, in calcination process, thioacetamide and antimony acetate reaction generation antimonous sulfide, with calcination time
Extension, the antimony element volatilization in compound antimonous sulfide, and ethylenediamine tetra-acetic acid becomes carbon, calcining knot after high-temperature calcination
Shu Hou, that is, form a kind of unique structure -- the carbon-coating of sulphur Uniform Doped.When above-mentioned sulfur doping carbon material is used as lithium ion battery
Negative material is in use, it has excellent specific discharge capacity.
The present invention is further detailed by the following examples.
Embodiment 1
The present embodiment is used to illustrate sulfur doping carbon material disclosed by the invention and preparation method thereof.
4.5g antimony acetates and 4.5g thioacetamides are dissolved in 6ml ethylene glycol, and are stirred vigorously 12h at normal temperatures, is prepared
Uniform mixed liquor.Obtained mixed liquor is transferred in mortar, 1g ethylenediamine tetra-acetic acids are added, 2h, antimony acetate used is ground
Shanghai Aladdin biochemical technology limited company is purchased from thioacetamide, ethylene glycol is limited purchased from Chinese medicines group chemical reagent
Company, is that analysis is pure.
The predecessor that above-mentioned grinding is obtained is placed in tube furnace, and purity is passed through as 99.99% using 40mL/min flow velocity
Argon gas, be heated to 800 DEG C with 2 DEG C/min heating rate, then constant temperature 4h naturally cools to room temperature, the production of obtained black
Thing is sulfur doping carbon material, and tube furnace used is the open-type electron tubes type that Anhui Bei Yike equipment and technologies Co., Ltd produces
Stove.
Through constituent content analysis, sulfur content is 6wt% in the present embodiment 1.
Synthesized sulfur doping carbon material and conductive black, CMC are pressed into 80wt%：10wt%：10wt% ratio mixing
Uniformly, it is coated on copper foil.Its chemical property is tested using button cell.Electrolyte uses 1mol/L LiPF6/EC-
DEC-DMC(1：1：1, w/w) charged/discharged test, is carried out with 100mA/g.
Fig. 1 is the SEM figures of sulfur doping carbon material prepared by the present embodiment 1.
Fig. 2 is the battery discharge curve figure of sulfur doping carbon material prepared by the present embodiment 1.Can from Fig. 2 test results
Go out, the capacity of the battery of sulfur-bearing doping carbon material is high, and cyclical stability and high rate performance are preferable.
Embodiment 2
The present embodiment is used to illustrate sulfur doping carbon material disclosed by the invention and preparation method thereof.
3g antimony acetates and 3g thioacetamides are dissolved in 6ml ethylene glycol, and are stirred vigorously 12h at normal temperatures, prepares uniform
Mixed liquor, obtained mixed liquor is transferred in mortar, add 2g ethylenediamine tetra-acetic acids, grind 4h.
The predecessor that above-mentioned grinding is obtained is placed in tube furnace, and purity is passed through as 99.99% using 40mL/min flow velocity
Argon gas, be heated to 900 DEG C with 2 DEG C/min heating rate, then constant temperature 4h naturally cools to room temperature, the production of obtained black
Thing is sulfur doping carbon material.
Through constituent content analysis, sulfur content is 5wt% in the present embodiment 2.
Fig. 3 is the SEM figures of sulfur doping carbon material prepared by the present embodiment 2.
Embodiment 3
The present embodiment is used to illustrate sulfur doping carbon material disclosed by the invention and preparation method thereof.
4.5g antimony acetates and 3.0g thioacetamides are dissolved in 6ml ethylene glycol, and are stirred vigorously 12h at normal temperatures, is prepared
Uniform mixed liquor, obtained mixed liquor is transferred in mortar, adds 2g ethylenediamine tetra-acetic acids, grinds 4h.
The predecessor that above-mentioned grinding is obtained is placed in tube furnace, and purity is passed through as 99.9% using 40mL/min flow velocity
Ammonia, is heated to 1000 DEG C, then constant temperature 2h naturally cools to room temperature, obtained black product with 1 DEG C/min heating rate
As sulfur doping carbon material.
Through constituent content analysis, sulfur content is 8wt% in the present embodiment 3.
Fig. 4 is the SEM figures of sulfur doping carbon material prepared by the present embodiment 3.
The present invention is using thioacetamide as sulphur source, and using antimony acetate as plasticity medium, ethylene glycol is used as solvent, ethylenediamine
Tetraacethyl is as carbon source, in calcination process, thioacetamide and antimony acetate reaction generation antimonous sulfide, with calcination time
Extension, the antimony element volatilization in compound antimonous sulfide, and ethylenediamine tetra-acetic acid becomes carbon, calcining knot after high-temperature calcination
Shu Hou, that is, form a kind of unique structure -- the carbon-coating of sulphur Uniform Doped.When above-mentioned sulfur doping carbon material is used as lithium ion battery
Negative material is in use, it has excellent specific discharge capacity.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all essences in the present invention
Any modifications, equivalent substitutions and improvements made within refreshing and principle etc., should be included in the scope of the protection.
Claims (10)
1. a kind of sulfur doping carbon material, it is characterised in that the carbon layers having thicknesses of the sulfur doping carbon material are 20-300 nanometers, and sulphur contains
Measure as 3-20wt%.
2. sulfur doping carbon material according to claim 1, it is characterised in that carbon-coating length is 5-20 microns.
3. sulfur doping carbon material according to claim 1 or 2, it is characterised in that also contain in the sulfur doping carbon material
Nitrogen.
4. a kind of preparation method of sulfur doping carbon material, it is characterised in that including：By antimony acetate, thioacetamide and ethylene glycol
Mixing, is stirred vigorously, obtains mixed liquor；Then mixed liquor is placed in mortar, adds ethylenediamine tetra-acetic acid and be ground, obtain
Predecessor；The predecessor is sintered again, the sulfur doping carbon material is obtained.
5. preparation method according to claim 4, it is characterised in that in the mixed liquor, antimony acetate, thioacetamide and
The content ratio of ethylene glycol is 1.0-6.0g：1.0-6.0g：4-12ml.
6. preparation method according to claim 4, it is characterised in that antimony acetate, thioacetamide and ethylene glycol is violent
6-24h is stirred, the mixed liquor is obtained.
7. preparation method according to claim 4, it is characterised in that when being ground, the ethylenediamine tetra-acetic acid of addition
The mass ratio of amount and antimony acetate in mixed liquor is 0.2-4.0：1.0-6.0.
8. preparation method according to claim 4, it is characterised in that the temperature of the sintering processes is 800-1100 DEG C,
Time is 2-6h, and heating rate is 1-10 DEG C/min.
9. preparation method according to claim 4, it is characterised in that the sintering processes are carried out under an inert atmosphere, gas
Rate of flow of fluid is 10-40ml/min.
10. preparation method according to claim 4, it is characterised in that the sintering processes are carried out in ammonia, ammonia
Flow velocity is 10-40ml/min.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110247030A (en) * | 2019-05-23 | 2019-09-17 | 天津大学 | Method for preparing three-dimensional porous microspheres surrounded by nitrogen/sulfur co-doped carbon nanosheets embedded with metal/carbon yolk shell structures |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104108707A (en) * | 2014-07-25 | 2014-10-22 | 深圳新宙邦科技股份有限公司 | Sulfur-doped graphene and preparation method thereof |
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2017
- 2017-03-28 CN CN201710190759.4A patent/CN107221652A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104108707A (en) * | 2014-07-25 | 2014-10-22 | 深圳新宙邦科技股份有限公司 | Sulfur-doped graphene and preparation method thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110247030A (en) * | 2019-05-23 | 2019-09-17 | 天津大学 | Method for preparing three-dimensional porous microspheres surrounded by nitrogen/sulfur co-doped carbon nanosheets embedded with metal/carbon yolk shell structures |
| CN110247030B (en) * | 2019-05-23 | 2022-05-10 | 天津大学 | Method for preparing three-dimensional porous microspheres surrounded by nitrogen/sulfur co-doped carbon nanosheets embedded with metal/carbon yolk shell structures |
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Application publication date: 20170929 |