CN110171822A - A kind of porous hollow bowl-type graphite material and preparation method thereof - Google Patents
A kind of porous hollow bowl-type graphite material and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to field of inorganic material preparing technology, a kind of porous hollow bowl-type graphite material and preparation method thereof is provided.The material is the bowl shaped structure particle of graphite, and inside is in hollow structure, and pattern is in recess bowl structure.Bowl wall is graphite, and degree of graphitization is controllable, and porosity is presented, and hole is micropore and mesoporous.Particle has polymolecularity, and particle size and distribution are controllable.Steps are as follows for the preparation method of porous hollow bowl-type graphite material: the hollow bowl-type carbon of hydro-thermal carbonaceous being mixed with containing certain density iron ion salting liquid, is stirred evenly, and be dried；Powder after drying is fitted into quartz boat and is placed in tube furnace under protective atmosphere with certain heating rate to certain temperature and keeps the temperature a period of time；Calcined powder is put into certain time in certain density acid solution, carries out pickling, ferro element is removed, and be dried, obtains porous hollow bowl-type graphite material.The invention has the advantages that providing a kind of method of functional carbon material for converting the biological waste of low economic value to high economic value, preparation-obtained carbon material has the unique features of bowl-type hollow material, graphitization and porous feature are had both simultaneously, it is expected to be applied in fields such as energy storage, catalysis, coating, composite material, powder metallurgy, and forms industrialization.
Description
Technical field
The invention belongs to technical field of preparation for inorganic material, and in particular to a kind of new porous hollow bowl-type graphite material and
Preparation method.
Background technique
Graphite has special nature: heat-resisting quantity, electrical and thermal conductivity, lubricity, change due to its special layer structure
Stability, plasticity, thermal shock resistance etc. are learned, therefore, the graphite material of different structure and pattern has become investigation of materials field
Research emphasis.
Hollow structure powder body material is received more and more attention with the unique texture of its internal cavities.Hollow bowl-type material
Material, is the material further designed based on hollow sphere, and not only the large specific surface area with hollow ball structure, specific gravity are small, it is interior to contain
The advantages that portion space, nano effect, and bowl-type material has weak symmetry, therefore storehouse behavior can occur, to improve
Its tap density.In addition, its inner concave can effectively regulate and control light, electron beam, the field-effect of fluid etc..In conjunction with graphite material
Characteristic, porous hollow bowl-type graphite material are expected to realize broad application prospect in fields such as sensor, energy storage, electrode materials.
Currently, having no the report for preparing porous hollow bowl-type graphite material.
Jia Baorui etc. (a kind of preparation method CN201910032940.1 of hollow bowl-shape carbon material) by by hydrothermal carbonization,
The technique of soft template method and microemulsion method combines, and to prepare hollow hydro-thermal carbon bowl material, overcomes hard template method complex process
Defect reduce pollution environment and waste of material it is not necessary that aggressive solvent removal hard template is added.
Based on above-mentioned consideration, the invention proposes a kind of new porous hollow bowl-type graphite materials and preparation method thereof.
Summary of the invention
Object of the present invention is to prepare a kind of porous hollow bowl-type graphite material, the method step is simple, low in cost, fits
Close industrialized production.
A kind of porous hollow bowl-type graphite material, it is characterised in that:
The material is the bowl shaped structure particle of graphite, and inside is in hollow structure, and pattern is in recess bowl structure；Bowl wall is
Graphite, degree of graphitization is controllable, and porosity is presented, and hole is micropore and mesoporous；Particle have polymolecularity, particle size and point
Cloth is controllable.
A kind of preparation method of porous hollow bowl-type graphite material as described above, it is characterised in that its preparation step is as follows:
1) the hollow bowl-type carbon of hydro-thermal carbonaceous, is prepared；
2) the hollow bowl-type carbon is mixed with containing certain density iron ion salting liquid, is stirred evenly, and done
It is dry；
3), the powder after drying is fitted into quartz boat and is placed in tube furnace under protective atmosphere with certain heating rate extremely
Certain temperature simultaneously keeps the temperature a period of time；
4) calcined powder, is put into certain time in certain density acid solution, carries out pickling, removal iron member
Element, and be dried, obtain porous hollow bowl-type graphite material.
Further, the preparation step of the hollow bowl-type carbon of step 1) the hydro-thermal carbonaceous is (referring to patent
201910032940.1 :)
A, raw material: including carbon source, solvent, soft template；Carbon source is biological raw material and waste material；Biological raw material include apple,
Pears, grape, peach, lichee, sugarcane, biological waste include eating surplus apple core, pears core and their pericarp, further include grape
Pericarp, bagasse and can not human consumption the apple to addle, pears, grape, peach, lichee, sugarcane；Soft template is by yin
Ionic surface active agent and nonionic surfactant are collectively formed, and solvent is deionized water；
B, it squeezes the juice, filters to biological raw material or waste material, washing finally obtains limpid juice；
C, it configures precursor liquid: two kinds of surfactants is dissolved in deionized water respectively, form solution, it is then former with biology
Material or the mixing of waste material juice, and stir evenly；
D, hydrothermal carbonization: the above-mentioned mixed solution is put into hydrothermal reaction kettle heat preservation, holding temperature is 50-250 DEG C, heat preservation
Time is 0.5-80 hours；
E, reaction kettle is taken out, after being cooled to room temperature, container is opened, pours out precipitating, washed repeatedly, obtained repeatedly with water and alcohol
To product.
Further, molysite described in step 2) includes one of ferric nitrate, iron chloride, ferric oxalate or a variety of, molten
Agent is one of water, alcohol or a variety of, and the concentration of molysite is 0.1-10mol/L, and mixing time is 0.5-48 hours, dry temperature
Degree is 30-80 DEG C, and drying time is 1-48 hours.
Further, protective atmosphere described in step 3) is nitrogen, argon gas or vacuum, heating rate 0.05-10
DEG C/min, holding temperature is 500-2000 DEG C, and soaking time is 0.5-20 hours
Further, acid solution described in step 4) is hydrochloric acid, sulfuric acid, nitric acid；The concentration of acid solution is 1-98%, acid
Washing the time is 0.5-48 hours, and drying temperature is 30-80 DEG C, and drying time is 1-48 hours.
The invention has the advantages that providing a kind of function of converting the biological waste of low economic value to high economic value
Change the method for carbon material, preparation-obtained carbon material has the unique features of bowl-type hollow material, while have both graphitization and
Porous feature is expected to be applied in fields such as energy storage, catalysis, coating, composite material, powder metallurgy, and forms industrialization,
Promote green circulation economy.
Specific embodiment
Embodiment 1:
By the 20 ml deionized water solution containing 3 grams of rotten apple juice, 5 milliliters of sodium oleate solution (10mmol/L)
P123 solution (1mmol/L) with 5 milliliters mixes, and stirs to being uniformly mixed, which is put into 50 milliliters and is gathered
In the stainless steel hydro-thermal tank of tetrafluoroethene liner, after tightening lid, hydro-thermal tank is put into 150 DEG C of baking ovens, after heat preservation 10 hours,
Hydro-thermal tank is taken out into baking oven, is placed in air and is cooled to room temperature, then open hydro-thermal jar, pours out the mixture of the inside,
It is centrifuged, is precipitated in 8000 revs/min of centrifuge, then cleaned repeatedly with water and ethyl alcohol, obtain hollow carbon bowl.By 1 gram
Hollow bowl-type hydro-thermal carbon is put into 10 milliliters of iron nitrate solution (1mol/L), is uniformly dispersed by sonic oscillation, and in room temperature
Lower stirring 12 hours, is then dried in vacuum oven, and 50 DEG C keep the temperature 12 hours；Powder after drying is packed into quartz
It is placed in tube furnace in boat, calcining carbonization is carried out under nitrogen protection atmosphere, with the heating rate of 5 DEG C/min, be warming up to 1000
DEG C, and 5 hours are kept the temperature, then stop heating, cooled to room temperature is taken out；Calcined powder is put into 20 milliliters of salt
Pickling is carried out in acid solution (1mol/L), is uniformly dispersed by sonic oscillation, is centrifuged, obtains in 9000 revs/min of centrifuge
To precipitating, repeat pickling, until ferro element is removed completely, obtains porous hollow bowl-type graphite.
Embodiment 2:
By the 20 ml deionized water solution containing 5 grams of grape juice, 10 milliliters of neopelex solution
(10mmol/L) and 10 milliliters of F127 solution (1mmol/L) mixing, and stir to being uniformly mixed, which is put
Enter in the stainless steel hydro-thermal tank of 80 milliliters of polytetrafluoroethyllining linings, after tightening lid, hydro-thermal tank is put into 130 DEG C of baking ovens, protects
Temperature takes out baking oven after 20 hours, by hydro-thermal tank, is placed in air and is cooled to room temperature, then opens hydro-thermal tank, pours out the inside
Mixture is centrifuged in 8000 revs/min of centrifuge, is precipitated, and is then cleaned repeatedly with water and ethyl alcohol, obtains hollow carbon
Bowl.3 grams of hollow bowl-type hydro-thermal carbon are put into 10 milliliters of ferric chloride solution (2mol/L), are uniformly dispersed by sonic oscillation,
And be stirred at room temperature 6 hours, it is then dried in vacuum oven, 60 DEG C keep the temperature 12 hours；By the powder after drying
It is fitted into quartz boat and is placed in tube furnace, calcining carbonization is carried out under argon atmosphere, with the heating rate of 2 DEG C/min, rise
Temperature keeps the temperature 10 hours to 800 DEG C, then stops heating, and cooled to room temperature is taken out；Calcined powder is put into 20
Pickling is carried out in the sulfuric acid solution (1mol/L) of milliliter, is uniformly dispersed by sonic oscillation, in 9000 revs/min of centrifuge
Centrifugation, is precipitated, repeats pickling, until ferro element is removed completely, obtains porous hollow bowl-type graphite.
Embodiment 3:
By the 20 ml deionized water solution containing 3 grams of juice from sugar cane, 20 milliliters of sodium stearate solution (10mmol/L)
Polysorbate40 solution (1mmol/L) with 20 milliliters mixes, and stirs to being uniformly mixed, which is put into 80 milliliters
In the stainless steel hydro-thermal tank of polytetrafluoroethyllining lining, after tightening lid, hydro-thermal tank is put into 120 DEG C of baking ovens, keeps the temperature 48 hours
Afterwards, hydro-thermal tank is taken out into baking oven, is placed in air and is cooled to room temperature, then opens hydro-thermal jar, pour out the mixture of the inside,
It is centrifuged, is precipitated in 8000 revs/min of centrifuge, then cleaned repeatedly with water and ethyl alcohol, obtain hollow carbon bowl.By 1
Gram hollow bowl-type hydro-thermal carbon is put into 10 milliliters of oxalic acid ferrous solution (1mol/L), is uniformly dispersed by sonic oscillation, and in room
It temperature lower stirring 12 hours, is then dried in vacuum oven, 70 DEG C keep the temperature 4 hours；Powder after drying is packed into stone
Ying Zhouzhong is placed in tube furnace, carries out calcining carbonization under vacuum conditions, with the heating rate of 10 DEG C/min, is warming up to 1500
DEG C, and 2 hours are kept the temperature, then stop heating, cooled to room temperature is taken out；Calcined powder is put into 20 milliliters of salt
Pickling is carried out in acid solution (1mol/L), is uniformly dispersed by sonic oscillation, is centrifuged, obtains in 9000 revs/min of centrifuge
To precipitating, repeat pickling, until ferro element is removed completely, obtains porous hollow bowl-type graphite.
Embodiment 4:
The juicing of apple, three kinds of pears, grape mixed fruit pericarps takes 4 grams of 20 ml deionized waters of addition, with 8 milliliters
Fatty alcohol sulphuric acid sodium solution (10mmol/L) and the mixing of 8 milliliters of polyvinylether solution (1mmol/L), and stir equal to mixing
It is even, which is put into the stainless steel hydro-thermal tank of 50 milliliters of polytetrafluoroethyllining linings, after tightening lid, by hydro-thermal
Tank is put into 200 DEG C of baking ovens, after heat preservation 8 hours, hydro-thermal tank is taken out baking oven, is placed in air and is cooled to room temperature, then by water
Hot jar is opened, and is poured out the mixture of the inside, is centrifuged, is precipitated in 8000 revs/min of centrifuge, and water and second are then used
Alcohol cleans repeatedly, obtains hollow carbon bowl.5 grams of hollow bowl-type hydro-thermal carbon are put into 10 milliliters of iron nitrate solution (3mol/L),
It is uniformly dispersed, and is stirred at room temperature 10 hours by sonic oscillation, is then dried in vacuum oven, 50 DEG C of heat preservations
12 hours；Powder after drying is fitted into quartz boat and is placed in tube furnace, calcining carbonization is carried out under nitrogen protection atmosphere, with
The heating rate of 2 DEG C/min is warming up to 1200 DEG C, and keeps the temperature 2 hours, then stops heating, and cooled to room temperature is taken out；
Calcined powder is put into 20 milliliters of nitric acid solution (0.5mol/L) and carries out pickling, is uniformly dispersed by sonic oscillation,
It is centrifuged, is precipitated in 9000 revs/min of centrifuge, repeat pickling, until ferro element is removed completely, obtain more
The hollow bowl-type graphite in hole.
Claims (6)
1. a kind of porous hollow bowl-type graphite material, it is characterised in that:
The material is the bowl shaped structure particle of graphite, and inside is in hollow structure, and pattern is in recess bowl structure；Bowl wall is graphite
Matter, degree of graphitization is controllable, and porosity is presented, and hole is micropore and mesoporous；Particle has polymolecularity, and particle size and distribution can
Control.
2. the preparation method of porous hollow bowl-type graphite material according to claim 1, it is characterised in that its preparation step is such as
Under:
1) the hollow bowl-type carbon of hydro-thermal carbonaceous, is prepared；
2) the hollow bowl-type carbon is mixed with containing certain density iron ion salting liquid, is stirred evenly, and be dried；
3), the powder after drying is fitted into quartz boat and is placed in tube furnace under protective atmosphere with certain heating rate to certain
Temperature simultaneously keeps the temperature a period of time；
4) calcined powder, is put into certain time in certain density acid solution, carries out pickling, removes ferro element, and
It is dried, obtains porous hollow bowl-type graphite.
3. the preparation method of porous hollow bowl-type graphite material according to claim 2, it is characterised in that step 1) is described
The preparation step of the hollow bowl-type carbon of hydro-thermal carbonaceous are as follows:
A, raw material: including carbon source, solvent, soft template；Carbon source is biological raw material and waste material；Biological raw material includes apple, pears, Portugal
Grape, peach, lichee, sugarcane, biological waste include eating surplus apple core, pears core and their pericarp, further include grape pomace,
Bagasse and can not human consumption the apple to addle, pears, grape, peach, lichee, sugarcane；Soft template is by anion table
Face activating agent and nonionic surfactant are collectively formed, and solvent is deionized water；
B, it squeezes the juice, filters to biological raw material or waste material, washing finally obtains limpid juice；
C, configure precursor liquid: two kinds of surfactants are dissolved in deionized water respectively, formed solution, then with biological raw material or
The mixing of waste material juice, and stir evenly；
D, hydrothermal carbonization: the above-mentioned mixed solution is put into hydrothermal reaction kettle heat preservation, holding temperature is 50-250 DEG C, soaking time
It is 0.5-80 hours；
E, reaction kettle is taken out, after being cooled to room temperature, container is opened, pours out precipitating, washed repeatedly, produced repeatedly with water and alcohol
Object.
4. the preparation method of porous hollow bowl-type graphite material according to claim 2, it is characterised in that institute in step 2)
The molysite stated includes one of ferric nitrate, iron chloride, ferric oxalate or a variety of, and solvent is one of water, alcohol or a variety of, iron
The concentration of salt is 0.1-10mol/L, and mixing time is 0.5-48 hours, and drying temperature is 30-80 DEG C, and drying time is that 1-48 is small
When.
5. the preparation method of porous hollow bowl-type graphite material according to claim 2, it is characterised in that institute in step 3)
The protective atmosphere stated is nitrogen, argon gas or vacuum, and heating rate is 0.05-10 DEG C/min, and holding temperature is 500-2000 DEG C,
Soaking time is 0.5-20 hours.
6. the preparation method of porous hollow bowl-type graphite material according to claim 2, it is characterised in that institute in step 4)
The acid solution stated is hydrochloric acid, sulfuric acid, nitric acid；The concentration of acid solution is 1-98%, and pickling time is 0.5-48 hours, drying temperature
It is 30-80 DEG C, drying time is 1-48 hours.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115142083A (en) * | 2022-08-13 | 2022-10-04 | 台州学院 | Preparation method of iron-cobalt-nickel-copper alloy composite oxide |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101012058A (en) * | 2007-02-07 | 2007-08-08 | 中国科学院山西煤炭化学研究所 | Method for preparing medium pore carbon of narrow aperture and high degree of graphitization |
| US20090041653A1 (en) * | 2007-08-08 | 2009-02-12 | Hyundai Motor Company | Method for the preparation of porous graphite carbon with high crystallinity using sucrose as a carbon precursor |
| CN107611440A (en) * | 2017-08-14 | 2018-01-19 | 中国石油大学(北京) | A kind of bowl-type carbon material, it is prepared and point-line-surface three-phase composite electrocondution slurry |
| CN109368632A (en) * | 2018-12-17 | 2019-02-22 | 新奥石墨烯技术有限公司 | Graphitized carbon material and preparation method thereof |
| CN109553082A (en) * | 2019-01-14 | 2019-04-02 | 北京科技大学 | A kind of preparation method of hollow bowl-shape carbon material |
-
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- 2019-05-27 CN CN201910447234.3A patent/CN110171822A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101012058A (en) * | 2007-02-07 | 2007-08-08 | 中国科学院山西煤炭化学研究所 | Method for preparing medium pore carbon of narrow aperture and high degree of graphitization |
| US20090041653A1 (en) * | 2007-08-08 | 2009-02-12 | Hyundai Motor Company | Method for the preparation of porous graphite carbon with high crystallinity using sucrose as a carbon precursor |
| CN107611440A (en) * | 2017-08-14 | 2018-01-19 | 中国石油大学(北京) | A kind of bowl-type carbon material, it is prepared and point-line-surface three-phase composite electrocondution slurry |
| CN109368632A (en) * | 2018-12-17 | 2019-02-22 | 新奥石墨烯技术有限公司 | Graphitized carbon material and preparation method thereof |
| CN109553082A (en) * | 2019-01-14 | 2019-04-02 | 北京科技大学 | A kind of preparation method of hollow bowl-shape carbon material |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115142083A (en) * | 2022-08-13 | 2022-10-04 | 台州学院 | Preparation method of iron-cobalt-nickel-copper alloy composite oxide |
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