CN110451475A - A kind of preparation method of Pitch-based Carbon microballoon and its application as sodium ion battery electrode material - Google Patents
A kind of preparation method of Pitch-based Carbon microballoon and its application as sodium ion battery electrode material Download PDFInfo
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- CN110451475A CN110451475A CN201910605539.2A CN201910605539A CN110451475A CN 110451475 A CN110451475 A CN 110451475A CN 201910605539 A CN201910605539 A CN 201910605539A CN 110451475 A CN110451475 A CN 110451475A
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- based carbon
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
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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
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
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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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
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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
A kind of preparation method of Pitch-based Carbon microballoon and its application as sodium ion battery electrode material, are related to sodium ion battery electrode material field.It is added in high-temperature silicon oil after asphalt powder and surfactant are mixed, the heating and thermal insulation in air atmosphere, so that it is melted balling-up and surface oxidation while occurring, it obtains regular appearance, realized infusible pitch microballoon, then it is separated from emulsion system, drying is washed, most obtains final product through 800-1600 DEG C of charing process afterwards.The electrode material is in 50mA g‑1Current density under show 250-450mA h g‑1Specific discharge capacity, 1A g‑1Current density under circulation 100 circle still have 140-250mA h g‑1Capacity, have high specific discharge capacity and good cyclical stability.
Description
Technical field
The present invention relates to sodium ion battery electrode material field, in particular to the preparation method of a kind of Pitch-based Carbon microballoon and
Its application as sodium ion battery electrode material.
Background technique
The advantages that lithium ion battery is by its energy density height, good cycling stability, has in energy storage field and widely answers
With.However, limiting the further development of lithium ion battery since lithium resource reserves are not high and are unevenly distributed.Sodium element
Reserves are very rich, and are located at same main group with lithium, have similar chemical property, therefore the research to sodium-ion battery
There is boundless prospect with application.
Currently, people are existing to the research of sodium-ion battery positive material very much, however negative electrode material is often also to determine
The key factor of battery performance quality, thus the development and utilization of negative electrode material are also very important.Carbon Materials, especially stone
Black class material, is widely used in field of lithium ion battery at present.However sodium ion has biggish radius, nothing
Image of Buddha lithium ion is effectively inserted into graphite flake layer like that forms intercalation compound, thus graphite type material is not appropriate for applying
In sodium electricity cathode.
Unformed charcoal has biggish graphite flake layer spacing, mixed and disorderly microstructure and defective bit abundant, these are special
Point both contributes to the storage of sodium ion, to make material specific capacity with higher.It is spherical compared with the irregular material of pattern
Material has higher bulk density, so as to provide higher volume and capacity ratio.Therefore, try to prepare a kind of spherical shape
The Carbon Materials of non crystalline structure can show higher specific capacity when being used for anode material of lithium-ion battery.
Pitch is that the cheap industrial products of one kind can prepare a variety of Carbon Materials using it as presoma.Currently, people
To the research of the microballoon class material of asphaltic base be concentrated mainly on mesocarbon microspheres (Mesocarbon microbeads,
MCMB on).MCMB after graphitization processing can be widely used in lithium ion secondary battery, but height graphite
The structure of change is unfavorable for its application in sodium-ion battery.Lijun Song et al. is by carrying out low-temperature carbonization processing to MCMB
(700 DEG C), obtained product have certain disordering degree, when being used as anode material of lithium-ion battery, in 25mA g-1Electricity
There is 232mA h g under current density-1Reversible capacity [Song L-J, Liu S-S, Yu B-J, Wang C-Y, Li M-
W.Anode performance of mesocarbon microbeads for sodium-ion
batteries.Carbon.2015；95:972-7.].A kind of patent CN108529585A " the modified interphase of sodium-ion battery
Preparation method of the carbon microspheres as negative electrode material " etches mesocarbon microspheres by using sodium hydroxide, in carbon microspheres surface system
It makes mesoporous, alleviates the bulk effect that generates in charge and discharge process, to improve it when as anode material of lithium-ion battery
Cyclical stability.However, these results are compared with application of the MCMB in lithium electrical domain, either reversible capacity, or circulation are steady
Qualitative and high rate performance all has very big gap.Other than mesocarbon microspheres, also there is researcher directly with pitch for original
Material prepares common asphaltic base microballoon.Zhang Yonggang et al. has prepared milli by the way that pitch is mixed with naphthalene, using suspension method
The pitch microballoon of the pitch microballoon of meter level, this larger size is suitable for active carbon adsorption material, and it is negative not to be suitable for battery
Pole material [Zhang Yonggang, Wang Chengyang suspension method prepare research [J] the charcoal element of bitumen ball, 2002 (3): 7-10.].
Using cheap pitch as raw material, a kind of higher Pitch-based Carbon microballoon of disordering degree is prepared, when its conduct
When anode material of lithium-ion battery, higher reversible capacity and high rate performance are shown, is had broad application prospects.
Summary of the invention
In view of the above problems in the prior art, the object of the present invention is to provide a kind of preparations of novel Pitch-based Carbon microballoon
Method is made as follows:
Step 1: material asphalt substance is crushed, sieving, take it is a certain amount of be added in high temperature resistant silicone oil, be added simultaneously
Surfactant；
Step 2: under certain stirring rate, system is heated to 200~300 DEG C, keeps the temperature 1~10h, the mistake
Cheng Yizhi is carried out in air atmosphere；After heat preservation, bead is separated from silicone oil, and with solvent washes clean；
Step 3: product is put into high temperature carbonization furnace, and 800-1600 DEG C is heated in nitrogen atmosphere, is finally produced
Object.
Material asphalt substance is selected from one or more of selected from coal tar pitch and petroleum asphalt, synthetic asphalts and coal liquefaction residue.
The surfactant in BY125, polyoxyethylene sorbitan monoleate, neopelex, F127, sorbester p17 one
Kind.
The dosage relation of raw material bitumen and silicone oil in step 1: the corresponding 100ml-300ml of every 10g bitumen
Silicone oil；The quality of surfactant is the 8-15% of material asphalt substance quality.
It is 0.1-1 microns that the microballoon that the method for the present invention obtains, which obtains partial size,.
The further preferred embodiment of the present invention is: determining suitable holding temperature and soaking time.Temperature is too low, and the time is too
Short, the bead surface degree of oxidation of formation is too low, will appear in further carbonization process and melts simultaneously.Temperature is too high, and soaking time is too
It is long, small club's excessive oxidation of formation, to will affect service performance of its later period as electrode material.
The further preferred embodiment of the present invention is: the obtained Pitch-based Carbon microballoon of this method is born as sodium-ion battery
Pole material.
The present invention prepares Pitch-based Carbon microballoon using emulsion process, the emulsification system of the invention unlike conventional emulsification method
It is the heating and thermal insulation in air atmosphere, rather than nitrogen atmosphere.Common coal tar pitch has been selected to replace centre in terms of raw material
On the one hand asphalt phase reduces costs, it is often more important that, in air atmosphere, material asphalt emulsifies balling-up and surface oxidation is same
Shi Fasheng forms regular appearance, is not easy to melt asphaltic base bead simultaneously, is able to maintain during the high temperature carbonization in the later period
Good ball looks, and this Pitch-based Carbon microballoon has higher unordered degree than mesocarbon microspheres, shows in sodium electricity
Higher reversible capacity and high rate performance out: in 50mA g-1Current density under show 250-450mA h g-1Electric discharge ratio
Capacity, 1A g-1Current density under circulation 100 circle still have 140-250mA h g-1Capacity.
Detailed description of the invention
Attached drawing 1 be 240 DEG C of heat preservation 2h, then 1200 DEG C charing after obtained by Pitch-based Carbon microballoon scanning electron microscope (SEM) photograph.
Specific embodiment
The present invention is described in detail with reference to the accompanying drawings and examples, but the present invention is not limited to following embodiments.
The condition of electrode test when being used as anode material of lithium-ion battery in following embodiment: the electrode group becomes 80% present invention
Pitch-based Carbon microballoon, 10% acetylene black, 10% PVDF, electrolyte group become 1mol NaClO4Being dissolved in volume ratio is
In the EC/DEC solvent of 1:1.
Embodiment 1
Raw material pitch powder is broken, and sieving takes 10g to be added in 200ml high temperature resistant silicone oil, while 1g dodecyl is added
Benzene sulfonic acid sodium salt.Under the stirring rate of 100r/min, system is heated to 240 DEG C, keeps the temperature 2h, the process is always in air
It is carried out in atmosphere.After heat preservation, bead is separated from silicone oil, washes clean.Product is put into high temperature carbonization furnace, in nitrogen
Atmosphere is heated to 1200 DEG C in enclosing, and obtains final product.
The Pitch-based Carbon microballoon pattern as shown in 1 scanning electron microscope of attached drawing (SEM) remains intact.
The electrode material is in 0.05mA g-1Specific discharge capacity under current density can achieve 265mA h g-1；In 1A g-1Current density under specific discharge capacity remain to be maintained at 142mA h g-1。
Embodiment 2
Raw material asphalt is crushed, is sieved, takes 10g to be added in 200ml high temperature resistant silicone oil, while 1g dodecane is added
Base benzene sulfonic acid sodium salt.Under the stirring rate of 100r/min, system is heated to 240 DEG C, keeps the temperature 2h, the process is always in sky
Atmosphere encloses middle progress.After heat preservation, bead is separated from silicone oil, washes clean.Product is put into high temperature carbonization furnace, In
It is heated to 1200 DEG C in nitrogen atmosphere, obtains final product.
Electrochemical property test the result shows that, the electrode material is in 0.05mA g-1Specific discharge capacity under current density can
To reach 312mA h g-1；In 1A g-1Current density under specific discharge capacity remain to be maintained at 184mA h g-1。
Embodiment 3
Raw material pitch powder is broken, and sieving takes 10g to be added in 200ml high temperature resistant silicone oil, while 1g sorbester p17 is added.
Under the stirring rate of 100r/min, system is heated to 240 DEG C, keeps the temperature 2h, the process always in air atmosphere into
Row.After heat preservation, bead is separated from silicone oil, washes clean.Product is put into high temperature carbonization furnace, in nitrogen atmosphere
1200 DEG C are heated to, final product is obtained.
Electrochemical property test the result shows that, the electrode material is in 0.05mA g-1Specific discharge capacity under current density can
To reach 271mA h g-1；In 1A g-1Current density under specific discharge capacity remain to be maintained at 144mA h g-1。
Embodiment 4
Raw material pitch powder is broken, and sieving takes 10g to be added in 200ml high temperature resistant silicone oil, while 1g dodecyl is added
Benzene sulfonic acid sodium salt.Under the stirring rate of 100r/min, system is heated to 280 DEG C, keeps the temperature 2h, the process is always in air
It is carried out in atmosphere.After heat preservation, bead is separated from silicone oil, washes clean.Product is put into high temperature carbonization furnace, in nitrogen
Atmosphere is heated to 1200 DEG C in enclosing, and obtains final product.
Electrochemical property test the result shows that, the electrode material is in 0.05mA g-1Specific discharge capacity under current density can
To reach 294mA h g-1；In 1A g-1Current density under specific discharge capacity remain to be maintained at 160mA h g-1。
Embodiment 5
Raw material pitch powder is broken, and sieving takes 10g to be added in 200ml high temperature resistant silicone oil, while 1g dodecyl is added
Benzene sulfonic acid sodium salt.Under the stirring rate of 100r/min, system is heated to 240 DEG C, keeps the temperature 6h, the process is always in air
It is carried out in atmosphere.After heat preservation, bead is separated from silicone oil, washes clean.Product is put into high temperature carbonization furnace, in nitrogen
Atmosphere is heated to 1200 DEG C in enclosing, and obtains final product.
Electrochemical property test the result shows that, the electrode material is in 0.05mA g-1Specific discharge capacity under current density can
To reach 265mA h g-1；In 1A g-1Current density under specific discharge capacity remain to be maintained at 148mA h g-1。
Embodiment 6
Raw material pitch powder is broken, and sieving takes 10g to be added in 200ml high temperature resistant silicone oil, while 1g dodecyl is added
Benzene sulfonic acid sodium salt.Under the stirring rate of 100r/min, system is heated to 240 DEG C, keeps the temperature 2h, the process is always in air
It is carried out in atmosphere.After heat preservation, bead is separated from silicone oil, washes clean.Product is put into high temperature carbonization furnace, in nitrogen
Atmosphere is heated to 1600 DEG C in enclosing, and obtains final product.
Electrochemical property test the result shows that, the electrode material is in 0.05mA g-1Specific discharge capacity under current density can
To reach 254mA h g-1；Specific discharge capacity remains to be maintained at 141mA h g-1 under the current density of 1A g-1.
Presently preferred embodiments of the present invention is illustrated above, but the present invention is not limited to the embodiment,
Those skilled in the art can also make various equivalent variation or replacement on the premise of without prejudice to spirit of the invention,
These equivalent variation or replacement are all included in the scope defined by the claims of the present application.
Claims (7)
1. a kind of preparation method of Pitch-based Carbon microballoon, which is characterized in that be made as follows:
Step 1: material asphalt substance is crushed, sieving, take it is a certain amount of be added in high temperature resistant silicone oil, while surface is added
Activating agent；
Step 2: under certain stirring rate, system is heated to 200~300 DEG C, keeps the temperature 1~10h, the process one
Directly carried out in air atmosphere；After heat preservation, bead is separated from silicone oil, and with solvent washes clean；
Step 3: product is put into high temperature carbonization furnace, and 800-1600 DEG C is heated in nitrogen atmosphere, obtains final product.
2. according to the method for claim 1, which is characterized in that material asphalt substance is selected from selected from coal tar pitch and petroleum asphalt, closes
At one or more of pitch and coal liquefaction residue.
3. according to the method for claim 1, which is characterized in that the surfactant be selected from BY125, polyoxyethylene sorbitan monoleate,
One of neopelex, F127, sorbester p17.
4. according to the method for claim 1, which is characterized in that the dosage of raw material bitumen and silicone oil is closed in step 1
System: every 10g bitumen corresponds to 100ml-300ml silicone oil；The quality of surfactant is material asphalt substance quality
8-15%.
5. according to the method for claim 1, which is characterized in that it is 0.1-1 microns that obtained microballoon, which obtains partial size,.
6. the Pitch-based Carbon microballoon obtained according to the described in any item methods of claim 1-5.
7. being used for sodium-ion battery according to the application for the Pitch-based Carbon microballoon that the described in any item methods of claim 1-5 obtain
Electrode material.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111732098A (en) * | 2020-07-01 | 2020-10-02 | 河南开炭新材料设计研究院有限公司 | Preparation method of asphalt-based carbon microspheres for lithium battery negative electrode material |
| CN112694080A (en) * | 2020-12-28 | 2021-04-23 | 北京化工大学 | Carbon microsphere with embedded conductive network structure, preparation method and energy storage application thereof |
| CN114368739A (en) * | 2021-12-28 | 2022-04-19 | 上海杉杉科技有限公司 | Hard carbon material, preparation method thereof, electrode, battery and application |
| CN114430030A (en) * | 2022-01-14 | 2022-05-03 | 北京化工大学 | Soft carbon with multi-interface structure, preparation method and energy storage application thereof |
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| CN112694080A (en) * | 2020-12-28 | 2021-04-23 | 北京化工大学 | Carbon microsphere with embedded conductive network structure, preparation method and energy storage application thereof |
| CN112694080B (en) * | 2020-12-28 | 2022-08-19 | 北京化工大学 | Carbon microsphere with embedded conductive network structure, preparation method and energy storage application thereof |
| CN114368739A (en) * | 2021-12-28 | 2022-04-19 | 上海杉杉科技有限公司 | Hard carbon material, preparation method thereof, electrode, battery and application |
| CN114430030A (en) * | 2022-01-14 | 2022-05-03 | 北京化工大学 | Soft carbon with multi-interface structure, preparation method and energy storage application thereof |
| CN114430030B (en) * | 2022-01-14 | 2024-03-26 | 北京化工大学 | Soft carbon with multi-interface structure, preparation method and energy storage application thereof |
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