CN105958041A - Method for preparing hollow microporous carbon sphere coated nanometer sulfur molecular material - Google Patents
Method for preparing hollow microporous carbon sphere coated nanometer sulfur molecular material Download PDFInfo
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- CN105958041A CN105958041A CN201610561608.0A CN201610561608A CN105958041A CN 105958041 A CN105958041 A CN 105958041A CN 201610561608 A CN201610561608 A CN 201610561608A CN 105958041 A CN105958041 A CN 105958041A
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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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- 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
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- 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
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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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- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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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
The invention discloses a method for preparing a hollow microporous carbon sphere coated nanometer sulfur molecular material, and belongs to the field of the chemical battery. The method comprises the steps of dissolving TPOS into a solution containing ethyl alcohol, water and ammonia water; then adding resorcinol and formaldehyde; carrying out centrifuging, washing, and calcining under argon after the reaction is finished; then mixing with an HF water solution to perform a corrosion reaction to obtain hollow microporous carbon spheres; and enabling the hollow microporous carbon spheres to be reacted with sublimed sulfur in a grinding and mixing manner to obtain the hollow microporous carbon sphere coated nanometer sulfur molecular material. The hollow microporous carbon sphere coated nanometer sulfur molecular material prepared by the invention is uniform in appearance, and relatively high in specific surface area and large-pore volume, so that the material can contain relatively high sulfur content; and therefore, electron transport can be facilitated, and an effect of improving the coulombic efficiency and the cycling stability of the battery can be achieved.
Description
Technical field
The invention belongs to chemical cell field, be specifically related to a kind of prepare the method that hollow microporous carbon bag covers nano-sulfur molecular material.
Background technology
The most serious environmental problem brought along with the day by day exhausted of Fossil fuel and burning thereof, in the urgent need to finding novel energy, portable set and the fast development of electric automobile such as mobile phone, notebook computer, digital camera simultaneously, can the secondary cell of repeatedly discharge and recharge be widely applied, wherein, coming across the lithium rechargeable battery of the nineties in 20th century is the electrochmical power source of new generation generally acknowledged the most in the world, viable commercial product developing rapidly in field of portable devices.But in fields such as electric automobile, Aero-Space and defence equipments, current commercialization lithium rechargeable battery is limited to energy density, far from the demand meeting technology development.Accordingly, it would be desirable to eager research and development have the mechanism of new electrochemical power sources of the features such as higher energy density, more long circulation life, low cost and environmental friendliness.
Wherein with lithium metal as negative pole, elemental sulfur is the lithium-sulfur rechargeable battery (abbreviation lithium-sulfur cell) of positive electrode, and its materials theory specific capacity and battery theory specific energy are higher, respectively reach 1672mAh g-1And 2600Wh/kg, the actual energy density of current lithium-sulfur cell has reached 390Wh/kg, far above other LiFeO4、LiCoO2Etc. business-like positive electrode.
Lithium-sulfur cell is in discharge process, and elemental sulfur is reduced to S-2During have multiple intermediate state generate, wherein Li2Sn (4≤n≤8) is soluble in organic electrolyte, spreads from positive to negative pole, along with the carrying out of electric discharge, finally generates Li at negative pole2S deposits, and Li2S does not dissolves in organic electrolyte, causes the problems such as lithium-sulfur cell cyclicity is poor, coulombic efficiency is low, self-discharge rate is high, has delayed the paces that it is practical.
Summary of the invention
It is an object of the invention to propose that a kind of preparation cost is cheap, preparation method is simple, cyclical stability is preferable, there is the lithium sulfur battery anode material hollow microporous carbon bag of hollow structure cover the preparation method of nano-sulfur molecular material.
The present invention comprises the following steps:
1) hollow microporous carbon ball is prepared: first tetrapropoxysilane (TPOS) be dissolved in the solution containing ethanol, water and ammonia, it is subsequently adding resorcinol and formaldehyde, it is stirred reaction, reaction is centrifugal after terminating, taking solid phase washing, then carry out corrosion reaction after solid phase being calcined under argon gas with HF aqueous solution, reaction is centrifugal after terminating, take solid phase with deionized water and washing with alcohol, be dried, obtain hollow microporous carbon ball；
In this step, tetrapropoxysilane hydrolyzes in the case of stirring, is condensed into silicon dioxide granule, and the oligomer co-agglomeration after then silicon dioxide granule is polymerized with resorcinol-formaldehyde is in silicon dioxide core particles；Under calcining, remove resorcinol-formaldehyde obtain silica-carbon (SiO2@C) composite；Then silica-carbon (the SiO2@C) composite obtained and HF aqueous solution are carried out corrosion reaction, to remove silicon dioxide therein, finally give hollow microporous carbon ball.
2) prepare hollow microporous carbon bag and cover nano-sulfur molecular material: hollow microporous carbon ball is reacted with Sublimed Sulfur ground and mixed, obtain hollow microporous carbon bag and cover nano-sulfur molecular material.
The advantage of present invention process is: can prepare under room temperature, method simple possible, and equipment requirements is simple, and raw material is easy to get, and cost is relatively low.The hollow microporous carbon bag prepared covers nano-sulfur molecular material, and pattern is homogeneous, has higher specific surface area and big pore volume, and material can be made to comprise higher sulfur content, it addition, the carbon-coating of outer layer can stop elemental sulfur to be reduced to S as protective layer-2During the solubility polysulfide that produces be dissolved in electrolyte, the carbon ball that high-temperature process is crossed simultaneously, its electric conductivity significantly improves, beneficially the transmission of electronics, can reach to improve the effect of coulombic efficiency and the cyclical stability of battery.
Further, in step 1) of the present invention, the mixing ratio of tetrapropoxysilane (TPOS) and resorcinol is 30mmol: 1g, under this amount, carbon source can be made to be fully used, it is to avoid waste of material.
In step 1), the speed of two times centrifugal is 5000r/min.There is a requirement that down, both can ensure that and washed away impurity, can ensure that again carbon ball will not cause because rotating speed is too high being destroyed.
In step 1), calcining heat is 700 DEG C under argon gas, can protect carbon ball, it is to avoid be oxidized to carbon dioxide, also improves the electric conductivity of material simultaneously.
In step 1), the mass concentration of hydrofluoric acid aqueous solution used is 10%, in order to fully remove silicon dioxide.
In step 1), described dry temperature conditions is 60 DEG C.Can well remove moisture removal at a temperature of this, be also possible to prevent temperature too high simultaneously, structure and crystal formation to material damage.
Step 2) in, described hollow microporous carbon ball is 1: 4 with the mixing quality ratio of Sublimed Sulfur.If sulfur consumption is too high, then can result in big sulfur fast, and then cause cell performance decay too fast, otherwise, then battery performance is poor, and under ratio, the chemical property of material is best.
Step 2) in, hollow microporous carbon ball is 155 DEG C with the reaction condition of Sublimed Sulfur, and the time is 15h, because with this understanding, the resistance of sulfur molecule is minimum, and after reaction terminates, elementary analysis result shows that sulfur content is 78.039%, and this explanation content is higher.
Accompanying drawing explanation
Fig. 1 is the scanning electron microscope (SEM) photograph that the hollow microporous carbon bag using the present invention to prepare covers nano-sulfur molecular material.
Fig. 2 is the transmission electron microscope picture of the hollow microporous carbon ball using the present invention to prepare.
Fig. 3 is the transmission electron microscope picture that the hollow microporous carbon bag using the present invention to prepare covers nano-sulfur molecular material.
Fig. 4 is the X-ray diffractogram that the hollow microporous carbon bag using the present invention to prepare covers nano-sulfur molecular material.
Fig. 5 is that the hollow microporous carbon bag using the present invention to prepare covers the nano-sulfur molecular material charging cycle performance map as lithium sulfur battery anode material.
Fig. 6 is that the hollow microporous carbon bag using the present invention to prepare covers the nano-sulfur molecular material discharge cycles performance map as lithium sulfur battery anode material.
Detailed description of the invention
One, preparation technology:
Embodiment 1:
1) prepare hollow microporous carbon ball: by 12mmol(3.46mL) tetrapropoxysilane (TPOS) be dissolved in the solution being made up of 70mL ethanol, 10mL water and 3mL ammonia, stir 15min.It is subsequently adding under the resorcinol of 0.4g and the formaldehyde of 1mL, stirring condition and carries out reacting 24 hours.
After reaction terminates, it is centrifuged 10min with 5000r/min, takes solid phase and carry out washing and collecting solid.
The solid 700 DEG C of calcinings under argon gas that will collect, then carry out corrosion reaction by 10%HF aqueous solution, remove silicon dioxide therein, finally it is centrifuged 10min with 5000r/min, takes solid phase and first wash 2 times, then ethanol washes 1 time, it is dried at 60 DEG C, collects solid, prepare hollow microporous carbon ball.
2) prepare hollow microporous carbon bag and cover nano-sulfur molecular material: by prepared hollow microporous carbon ball with Sublimed Sulfur in 1: 4 ratio ground and mixed, at 155 DEG C, then react 15h, both obtained hollow microporous carbon bag and covered nano-sulfur molecular material.
Embodiment 2
1) prepare hollow microporous carbon ball: by 60mmol(17.3ml) tetrapropoxysilane (TPOS) be dissolved in the solution containing 350mL ethanol, 50mL water and 15mL ammonia, stir 15min.It is subsequently adding under the resorcinol of 2.0g and 5mL formaldehyde, stirring condition and carries out reacting 24 hours.
After reaction terminates, it is centrifuged 10min with 5000r/min, takes solid phase and carry out washing and collecting solid.
The solid 700 DEG C of calcinings under argon gas that will collect, then carry out corrosion reaction by 10%HF aqueous solution, remove silicon dioxide therein, finally it is centrifuged 10min with 5000r/min, takes solid phase and first wash 2 times, then ethanol washes 1 time, it is dried at 60 DEG C, collects solid, prepare hollow microporous carbon ball.
2) prepare hollow microporous carbon bag and cover nano-sulfur molecular material: by prepared hollow microporous carbon ball with Sublimed Sulfur in 1: 4 ratio ground and mixed, at 155 DEG C, then react 15h, both obtained hollow microporous carbon bag and covered nano-sulfur molecular material.
Embodiment 3
1) prepare hollow microporous carbon ball: by 120mmol(34.6ml) tetrapropoxysilane (TPOS) be dissolved in the solution containing 700mL ethanol, 500mL water and 30mL ammonia, stir 15min.Be subsequently adding 4.0 resorcinol and 10mL formaldehyde, stirring condition under carry out reacting 24 hours.
After reaction terminates, it is centrifuged 10min with 5000r/min, takes solid phase and carry out washing and collecting solid.
The solid 700 DEG C of calcinings under argon gas that will collect, then carry out corrosion reaction by 10%HF aqueous solution, remove silicon dioxide therein, finally it is centrifuged 10min with 5000r/min, takes solid phase and first wash 2 times, then ethanol washes 1 time, it is dried at 60 DEG C, collects solid, prepare hollow microporous carbon ball.
2) prepare hollow microporous carbon bag and cover nano-sulfur molecular material: by prepared hollow microporous carbon ball with Sublimed Sulfur in 1: 4 ratio ground and mixed, at 155 DEG C, then react 15h, both obtained hollow microporous carbon bag and covered nano-sulfur molecular material.
Two, product checking:
Fig. 1 is the scanning electron microscope (SEM) photograph that the hollow microporous carbon bag using the present invention to prepare covers nano-sulfur molecular material.Visible, prepared sample topography is homogeneous.
Fig. 2 is the transmission electron microscope picture of the hollow microporous carbon ball using the present invention to prepare.Visible, prepared sample is hollow microporous structure.
Fig. 3 is the transmission electron microscope picture that the hollow microporous carbon bag using the present invention to prepare covers nano-sulfur molecular material.Visible, prepared sample structure is clear, and nano-sulfur molecule is well in hollow microporous carbon ball.
Fig. 4 is the X-ray diffractogram that the hollow microporous carbon bag using the present invention to prepare covers nano-sulfur molecular material.In the diagram, curve located above represents the X-ray diffractogram of hollow microporous carbon ball, shows that the hollow microporous carbon ball of synthesis is amorphous carbon material；The curve being located below represents hollow microporous carbon bag and covers X-ray diffractogram and the characteristic peak thereof of nano-sulfur molecular material.
What in Fig. 5, black square represented is under different multiplying powers, and the hollow microporous carbon bag using the present invention to prepare covers the nano-sulfur molecular material charge specific capacity as the battery of lithium sulfur battery anode material.
What in Fig. 6, black square represented is under different multiplying powers, and the hollow microporous carbon bag using the present invention to prepare covers the nano-sulfur molecular material specific discharge capacity as the battery of lithium sulfur battery anode material.
Claims (8)
1. prepare the method that hollow microporous carbon bag covers nano-sulfur molecular material for one kind, it is characterised in that comprise the following steps:
1) first tetrapropoxysilane is dissolved in the solution containing ethanol, water and ammonia, it is subsequently adding resorcinol and formaldehyde, it is stirred reaction, reaction is centrifugal after terminating, taking solid phase washing, then carry out corrosion reaction after solid phase being calcined under argon gas with HF aqueous solution, reaction is centrifugal after terminating, take solid phase with deionized water and washing with alcohol, be dried, obtain hollow microporous carbon ball；
2) hollow microporous carbon ball is reacted with Sublimed Sulfur ground and mixed, obtain hollow microporous carbon bag and cover nano-sulfur molecular material.
2., according to the preparation method described in claim 1, it is characterised in that in described step 1), tetrapropoxysilane is 30mmol: 1g with the mixing ratio of resorcinol.
3., according to the preparation method described in claim 1, it is characterised in that in described step 1), described centrifugal speed is 5000r/min.
4., according to the preparation method described in claim 1, it is characterised in that in described step 1), the temperature of described calcining is 700 DEG C.
5., according to the preparation method described in claim 1, it is characterised in that in described step 1), the mass concentration of described HF aqueous solution is 10%.
6., according to the preparation method described in claim 1, it is characterised in that in described step 1), described baking temperature is 60 DEG C.
7. according to the preparation method described in claim 1, it is characterised in that described step 2) in, described hollow microporous carbon ball is 1: 4 with the mixing quality ratio of Sublimed Sulfur.
8. according to the preparation method described in claim 1, it is characterised in that described step 2) in, described empty microporous carbon ball is 155 DEG C with the temperature conditions of the reaction of Sublimed Sulfur, and the response time is 15h.
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106328951A (en) * | 2016-09-28 | 2017-01-11 | 昆明理工大学 | Preparation method of porous carbon electrode material of lithium-sulfur battery |
| CN106935839A (en) * | 2017-05-16 | 2017-07-07 | 扬州大学 | A kind of micro- cube of preparation method of composite of carbon coating potassium phosphotungstate |
| CN106992291A (en) * | 2017-04-19 | 2017-07-28 | 扬州大学 | Manganese dioxide modification core shell structure-hollow microporous carbon ball coats the preparation method of nanometer sulfur molecule |
| CN107010605A (en) * | 2017-05-23 | 2017-08-04 | 兰州大学 | The preparation method of micro-nano sulfur granules |
| CN107760668A (en) * | 2017-12-06 | 2018-03-06 | 中国农业科学院油料作物研究所 | Hollow meso-porous nano carbon ball immobilised enzymes and preparation method thereof |
| CN108123127A (en) * | 2017-12-24 | 2018-06-05 | 林荣铨 | A kind of vanadic anhydride/graphene-hollow carbon sphere nanocomposite and preparation method thereof |
| CN109841805A (en) * | 2017-11-29 | 2019-06-04 | 中国科学院大连化学物理研究所 | The hollow carbon sulphur anode composite material of sheet manganese dioxide cladding and preparation and application |
| CN110828190A (en) * | 2018-08-10 | 2020-02-21 | 南京理工大学 | Hollow mesoporous carbon sphere @ nickel hydroxide nanocomposite and preparation method thereof |
| CN111244404A (en) * | 2018-11-29 | 2020-06-05 | 中国科学院大连化学物理研究所 | Flaky MoS2-xCoated hollow porous carbon sphere @ sulfur composite material and preparation and application thereof |
| CN112786830A (en) * | 2021-03-30 | 2021-05-11 | 齐鲁工业大学 | Co-HCS/S composite lithium-sulfur battery positive electrode material and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106328951A (en) * | 2016-09-28 | 2017-01-11 | 昆明理工大学 | Preparation method of porous carbon electrode material of lithium-sulfur battery |
| CN106992291A (en) * | 2017-04-19 | 2017-07-28 | 扬州大学 | Manganese dioxide modification core shell structure-hollow microporous carbon ball coats the preparation method of nanometer sulfur molecule |
| CN106935839A (en) * | 2017-05-16 | 2017-07-07 | 扬州大学 | A kind of micro- cube of preparation method of composite of carbon coating potassium phosphotungstate |
| CN106935839B (en) * | 2017-05-16 | 2019-06-14 | 扬州大学 | A kind of preparation method of micro- cube of composite material of carbon coating potassium phosphotungstate |
| CN107010605A (en) * | 2017-05-23 | 2017-08-04 | 兰州大学 | The preparation method of micro-nano sulfur granules |
| CN109841805A (en) * | 2017-11-29 | 2019-06-04 | 中国科学院大连化学物理研究所 | The hollow carbon sulphur anode composite material of sheet manganese dioxide cladding and preparation and application |
| CN107760668A (en) * | 2017-12-06 | 2018-03-06 | 中国农业科学院油料作物研究所 | Hollow meso-porous nano carbon ball immobilised enzymes and preparation method thereof |
| CN108123127A (en) * | 2017-12-24 | 2018-06-05 | 林荣铨 | A kind of vanadic anhydride/graphene-hollow carbon sphere nanocomposite and preparation method thereof |
| CN110828190A (en) * | 2018-08-10 | 2020-02-21 | 南京理工大学 | Hollow mesoporous carbon sphere @ nickel hydroxide nanocomposite and preparation method thereof |
| CN110828190B (en) * | 2018-08-10 | 2022-02-18 | 南京理工大学 | Hollow mesoporous carbon sphere @ nickel hydroxide nanocomposite and preparation method thereof |
| CN111244404A (en) * | 2018-11-29 | 2020-06-05 | 中国科学院大连化学物理研究所 | Flaky MoS2-xCoated hollow porous carbon sphere @ sulfur composite material and preparation and application thereof |
| CN111244404B (en) * | 2018-11-29 | 2021-05-04 | 中国科学院大连化学物理研究所 | Flaky MoS2-xCoated hollow porous carbon sphere @ sulfur composite material and preparation and application thereof |
| CN112786830A (en) * | 2021-03-30 | 2021-05-11 | 齐鲁工业大学 | Co-HCS/S composite lithium-sulfur battery positive electrode material and preparation method thereof |
| CN112786830B (en) * | 2021-03-30 | 2023-02-28 | 齐鲁工业大学 | Co-HCS/S composite lithium-sulfur battery positive electrode material and preparation method thereof |
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