CN105329874B - A kind of carbosphere of Heteroatom doping and preparation method thereof - Google Patents
A kind of carbosphere of Heteroatom doping and preparation method thereof Download PDFInfo
- Publication number
- CN105329874B CN105329874B CN201410390273.1A CN201410390273A CN105329874B CN 105329874 B CN105329874 B CN 105329874B CN 201410390273 A CN201410390273 A CN 201410390273A CN 105329874 B CN105329874 B CN 105329874B
- Authority
- CN
- China
- Prior art keywords
- carbosphere
- emulsion
- acid
- alkyl
- macromolecule
- 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.)
- Active
Links
Abstract
The present invention relates to a kind of carbospheres of Heteroatom doping, the carbosphere is made of the carbon nano-particle with hierarchical porous structure, the mesoporous and aperture that the carbon nano-particle has micropore of the aperture less than 2nm, aperture is 2-50nm is greater than the macropore of 50nm, and the BET specific surface area of the carbon nano-particle is 300-1000m2/ g, the content of heteroatoms in the carbon nano-particle are 2-25wt%, and the hetero atom is selected from least one of nitrogen phosphate and sulfur and boron.The invention also discloses a kind of production methods of carbon microspheres.
Description
Technical field
The invention belongs to the preparation fields of carbon material, are to be related to a kind of being received by the carbon with hierarchical porous structure furtherly
The Heteroatom doping carbosphere and preparation method thereof with hierarchical porous structure of rice grain composition.
Background technique
Porous carbon materials usually have that large specific surface area, thermal stability and chemical stability are good, resistance is low, surface hydrophobic
The excellent property such as good, in poison gas absorption, wastewater treatment, lithium ion battery, supercapacitor, CO2Capture, catalyst and catalysis
Agent carrier etc. has good application prospect.Nearest researcher has found electronic structure, crystalline texture and the hydrophily of carbon material
It can be changed by Heteroatom doping.The specific capacitance of carbon material compared with undoped carbon material after chemical doping would generally
It improves.Recent years, the elements such as phosphorus, sulphur, boron, nitrogen are used to doping carbon material all to improve the chemical property of carbon material.Its
The electronegativity (3.0) of middle nitrogen is than carbon (2.5) height, and atomic diameter is smaller, by nitrogen-doping carbon material with
The interaction of lithium ion is stronger, is more advantageous to the insertion of lithium ion, in addition, the hydrophilic of carbon material can be improved in nitrogen-doping
Property, therefore nitrogen is even more to be concerned in numerous doped chemicals.The carbon material of N doping can be rich by direct thermal cracking
Nitrogenous presoma or polymer, such as acrylonitrile, melamine, gelatin, but the product porosity that Direct Pyrolysis obtains is very
It is low, therefore usually need to introduce additional sacrifice template (such as Nano-meter CaCO33And SiO2) improve the porosity of product
(Energy Environ.Sci.2012,5:7950-7955；Electrochim.Acta.2012,78:147-153；
Micropor Mesopor Mat.2012,163:140-146).If not using the template of sacrifice, the product after charing is just needed
The porous carbon materials of N doping can be just obtained by high-temperature activation.The method of activation has physically activated and chemical activation.Physics
Activating usually using CO2, air or vapor is activator, and chemical activation is usually using KOH, ZnCl2、K2CO3、H3PO4Deng
For activator.Such as Long Qie (Adv.Mater.2012,24:2047-2050) has studied with polypyrrole nano line as forerunner
Body is activator by using KOH, and high-temperature activation has obtained the porous carbon fiber material of N doping, which is used as lithium ion
The electrode material of battery has high capacitor and good large current discharging capability.But the addition of a large amount of highly basic KOH, after needing
Neutralization washing is carried out using a large amount of acid when processing, preparation process is made to become complicated.As it can be seen that making to be prepared with simple method miscellaneous original
The porous carbon materials of son doping are still a challenge, prepare while having micropore, mesoporous and macropore Heteroatom doping carbon materials
Material is even more difficulty.Intrinsically conducting macromolecule is due to usually having big conjugatedπbond structure and five-membered ring, hexa-atomic on its molecular backbone
The cyclic structures such as ring, and intermolecular π-π interaction is big, therefore under an inert atmosphere, in high temperature pyrolysis, is easy to happen charcoal
Change.In addition, intrinsically conducting macromolecule, including polypyrrole, polyaniline and polythiophene etc., all contain the hetero atoms such as N, S in molecule,
It is the excellent presoma for preparing Heteroatom doping carbon material.
Summary of the invention
In order to provide a kind of simple method preparation by the hetero atom that is made of the carbon nano-particle with hierarchical porous structure
Carbosphere is adulterated, spy proposes the present invention.
One embodiment of the invention is related to a kind of carbosphere of Heteroatom doping, and the carbosphere is by with multi-stage porous
The carbon nano-particle of structure forms, the carbon nano-particle have aperture less than the micropore of 2nm, aperture be the mesoporous of 2-50nm and
Aperture is greater than the macropore of 50nm, and the BET specific surface area of the carbon nano-particle is 300-1000m2/ g, the carbon nano-particle
In content of heteroatoms be 2-25wt%, the hetero atom be selected from least one of nitrogen phosphate and sulfur and boron.The hetero atom is mixed
Miscellaneous carbosphere is spherical or spherical.
In a preferred embodiment of the present invention, the carbon nano-particle is in P/P0Aperture at=0.97 is 70nm
The single-point absorption total pore volume in hole below is 0.2-0.7cm3g-1, the Kong Rongwei 0.1-0.3cm of the micropore3g-1, mesoporous and big
The total pore volume in hole is 0.2-1.1cm3g-1。
In a preferred embodiment of the present invention, the BET specific surface area of the nano particle is 450-600m2/g。
In a preferred embodiment of the present invention, the partial size of the carbosphere be 0.5-20 μm, preferably 1-15 μm, more
It is preferred that 1-10 μm.Preferably, the partial size of the nano particle is 10-500nm, preferably 20-300nm, more preferable 30-100nm.
In a preferred embodiment of the present invention, the hetero atom is nitrogen-atoms, and the content of the nitrogen-atoms is
2-23%, preferably 3-15%, more preferable 4-10%.
In a preferred embodiment of the present invention, the hetero atom is sulphur atom, and the content of the sulphur atom is
2-25%, preferably 3-15%, more preferable 4-10%.
First embodiment of the invention is related to the production method of carbosphere described in one kind, comprising:
1) under the conditions of existing for oxidant, dopant and the stabilizer, conducting polymer list is carried out in macromolecule emulsion
The in-situ oxidizing-polymerizing of body obtains macromolecule-conducting polymer lotion；
2) it by being spray-dried the macromolecule-conducting polymer lotion, prepares by macromolecule-conducting polymer emulsion particle
Molecular conductive micro-balloons；
3) high temperature carbonization of the microballoon prepared in step 2) is carried out under an inert atmosphere, and obtain being made of hollow sphere has
The Heteroatom doping carbosphere of hierarchical porous structure.
In a preferred embodiment of the present invention, conducting polymer used in step 1) is selected from by following monomer
At least one of constitute conducting polymer: pyrroles, aniline, thiophene, 3,4- ethene dioxythiophene, indoles, carbazole, furans etc.
And the derivative of these monomers, when reaction, can be a kind of monomer, be also possible to the composition of several monomers.In these monomers
It is preferred that one or more of pyrroles, aniline, thiophene and 3,4- ethene dioxythiophene.
In present invention further optimization embodiment, the structure of the pyrroles, thiophene and their derivative are such as
Shown in Formulas I:
Wherein, X N-R2Or S；R2For C1-C20Alkyl, the aryl that either replaces of aryl, preferably H or C1-
C12Alkyl；More preferably H or C1-C8Alkyl, most preferably H；
Existing 4 R1It may be the same or different, H, alkyl, naphthenic base, alkenyl, aryl, alkane can be each independently selected from
Base aromatic radical, hydroxyl, alkoxy, halogen or nitro, wherein at least two R1Selected from H, halogen or alkoxy；Preferably,
Each R1It is each independently selected from H, C1-C20Alkyl, hydroxyl, C1-C4Alkoxy, chlorine or nitro, wherein at least at the ortho position X
Two R1H, halogen or alkoxy must be separately selected from；It is further preferred that each R1It can be respectively H, first
Base, hydroxyl, chlorine or nitro, wherein at least in two R at the ortho position X1It is H.
The derivative of pyrroles and thiophene includes N- methylpyrrole, N- N-ethyl pyrrole N, N- n-propyl pyrroles, N- normal-butyl pyrrole
It coughs up, N- phenylpyrrole, N- benzyl pyrroles, N- naphthylpyrrole, N- carboxy pyrrole, 3- methylpyrrole, 3- carboxy pyrrole, 3,4- bis-
Methylpyrrole, 3- N-ethyl pyrrole N, 3- n-propyl pyrroles, 3- normal-butyl pyrroles, 3- phenylpyrrole, 3- benzyl pyrroles, 3- naphthalene
Pyrroles, 3- methoxypyrrole, 3- ethyoxyl pyrroles, 3- propoxyl group pyrroles, 3- phenoxy group pyrroles, 3,4- dimethoxy pyrroles, 3-
Methyl-N-methyl pyrroles, 3- methoxy-. N-methyl pyrroles, 3- chlorine pyrroles, 3- bromine pyrroles, 3- alkylthrophene such as 3 methyl thiophene,
3- ethylthiophene, 3- propyl thiophene, 3- hexyl thiophene etc., 2,2 '-Dithiophenes, 3- methyl -2,2 '-Dithiophene, 3,3 '-diformazans
Base -2,2 '-Dithiophene, 3,4- dimethyl -2,2 '-Dithiophene, 3,4- dimethyl -3 ', 4 '-dimethyl -2,2 '-Dithiophene, 3-
Methoxyl group -2,2 '-Dithiophene, 3,3 '-dimethoxys -2,2 '-Dithiophene, 2,2 ', 5,5 '-three thiophene, 3- methyl -2,2 ', 5 ',
2 "-three thiophene, 3,3 '-dimethyl -2,2 ', 5 ', 2 "-three thiophene etc..Most preferably pyrroles and thiophene.
The structural formula of aniline and its derivatives is as shown in Formula II in step 1:
Wherein, R3For H, C1-C20Alkyl, aryl or substituted aryl；Preferably H or C3-C12Alkyl；More preferably
For H or C4-C8Alkyl；Most preferably H；
Existing 4 R4It may be the same or different, be each independently selected from H, alkyl, naphthenic base, alkenyl, aryl, alkyl
Substituted aryl, hydroxyl, alkoxy, halogen or nitro, wherein at least one R4It is necessary for H, halogen or alkoxy；It is preferred that
Ground, existing 4 R4It can be independently selected from H, C1-C4Alkyl, hydroxyl, C1-C4Alkoxy, chlorine or nitro, and extremely
Less in NHR3The R of contraposition4It is H, halogen or alkoxy；It is further preferred that existing 4 R4It can be independently selected from H, methyl, second
Base, hydroxyl, chlorine, bromine or nitro, and NHR3The R of contraposition4For H；Most preferably, all R4It is all H.
The monomer of anil includes 2-aminotoluene, 2- ethyl aniline, 2- propyl aniline, 2- aminoanisole, 2-
Phenetidine, 3- methylaniline, 3- ethyl aniline, 3- propyl aniline, 3- aminoanisole, 3- phenetidine, 3- hexyl
Aniline, methylphenylamine, N propyl aniline, N- butylaniline.Most preferably aniline.
Quality of the conductive high polymer monomer described in step 1) in step 1) is the 1- of macromolecule latex fluid solid content
30wt%, preferable amount 2-20wt%, preferred dosage are 5-15wt%.
Macromolecule emulsion used in step 1) be selected from it is all under an inert atmosphere can be complete at 450 DEG C or 450 DEG C or less
All macromolecule emulsions of full decomposition or resolution ratio > 50%, such as: styrene-acrylic emulsion, polystyrene emulsion, polyacrylate cream
Liquid, styrene-butadiene emulsion, carboxyl styrene emulsion, butyronitrile emulsion, carboxyl butyronitrile lotion, ethylene-vinyl acetate lotion, butadiene-styrene-vinyl pyridine rubber
Lotion, neoprene latex, polybutadiene rubber lotion and nature rubber latex.It is preferred that styrene-acrylic emulsion, polystyrene emulsion, poly-
Acrylic acid ester emulsion, butyronitrile emulsion, carboxyl butyronitrile lotion, ethylene-vinyl acetate lotion.More preferable styrene-acrylic emulsion, polyphenyl second
Alkene lotion, polyacrylate dispersion, butyronitrile emulsion, carboxyl butyronitrile lotion.
In a preferred embodiment of the present invention, there is no particular limitation for oxidant used in step 1), can be with
Use iron (III) salt of inorganic acid, copper (II) salt of inorganic acid, persulfate, periodate, hydrogen peroxide, ozone, the conjunction of six cyanogen
Iron (III) potassium, two hydrated sulfuric acids, four ammonium cerium (IV), bromine, iodine, iron (III) salt and metal ion and hydrogen peroxide of organic acid
Compound one or more of oxidation system.It is preferred that iron (III) salt, persulfate and the metal ion of inorganic acid or organic acid with
Hydrogen peroxide compounds one or more of oxidation system.More preferable metal ion compounds oxidation system with hydrogen peroxide.
In further preferred embodiment, iron (III) salt of the inorganic acid includes anhydrous ferric chloride (III), six
Ferric Chloride Hydrated (III), nine water ferric nitrates (III), anhydrous nitric acid iron (III), n ferric sulfate hydrate (III) (n=3 to 12), ten
Two hydrated sulfuric acid ammonium iron (III), n perchloric acid hydrate iron (III) (n=1,6), tetrafluoro boric acid iron etc., more preferable six chloride hydrate
Iron (III)；Copper (II) salt of the inorganic acid include copper chloride (II), copper sulphate (II), copper nitrate (II), copper acetate (II),
Copper tetrafluoroborate (II) etc., more preferable copper chloride (II)；The persulfate includes ammonium persulfate, potassium peroxydisulfate and sodium peroxydisulfate
Deng more preferable ammonium persulfate；The periodate includes potassium metaperiodate etc.；Iron (III) salt of the organic acid includes to toluene
Sulfonic acid iron (III) etc.；It includes Fe that the metal ion, which compounds oxidation system with hydrogen peroxide,2+-H2O2、Fe3+-H2O2、Cu2+-H2O2
Deng more preferable Fe3+-H2O2。
In a preferred embodiment of the present invention, oxidant/conductive high polymer monomer molar ratio is in step 1)
0.1-10, preferred molar ratio 0.2-5, more preferable molar ratio are 0.5-2.
In a preferred embodiment of the present invention, dopant can be inorganic acid, lewis acid, organic in step 1)
Acid and their derivative or iron (III) salt, alkyl sulfonic acid, benzene sulfonic acid, naphthalene sulfonic acids, anthraquinone sulfonic acid and its derivative, four cyanogen second
Alkene, one or more of trifluoromethanesulfonic acid.It is preferred that one of inorganic acid and alkyl sulfonic acid, benzene sulfonic acid and its derivative or several
Kind.
In further preferred embodiment, the inorganic acid includes HCl, H2SO4、HNO3、HClO4, chlorosulfonic acid
Deng；Lewis acid includes BF3、PCl5、AlCl3、SnCl4、WCl6、MoCl5Deng；Organic acid includes alkyl sulfonic acid, benzene sulfonic acid, anthraquinone
Sulfonic acid, camphorsulfonic acid and their derivative or their iron (III) salt；Sulfonic acid includes single sulfonic acid, disulfonic acid or three sulphurs
Acid；The derivative of alkyl sulfonic acid includes 2- acrylamide-2-methyl propane sulfonic etc.；The derivative of benzene sulfonic acid include phenolsulfonic acid,
Styrene sulfonic acid, p-methyl benzenesulfonic acid, to ethyl phenenyl azochlorosulfonate acid, dodecyl benzene sulfonic acid etc.；The derivative of naphthalene sulfonic acids includes 1- naphthalene sulphur
Acid, 2- naphthalene sulfonic acids, 1,3- naphthalenedisulfonic acid, 1,3,6- naphthalene trisulfonic acid and 6- ethyl -1-naphthalene sulfonic aicd etc.；The derivative of anthraquinone sulfonic acid
Example includes anthraquinone-1-sulfonic acid, anthraquinone-2-sulfonic acid, anthraquinone 2,6 disulfonic acid and 2-methylanthraquinone -6- sulfonic acid etc..It is preferred that HCl,
One or more of p-methyl benzenesulfonic acid, camphorsulfonic acid, dodecyl benzene sulfonic acid.More preferable p-methyl benzenesulfonic acid.
In a preferred embodiment of the present invention, dopant/conductive high polymer monomer molar ratio is in step 1)
0.05-10, preferred molar ratio 0.1-5, more preferable molar ratio are 0.2-2.
In a preferred embodiment of the present invention, there is no particular limitation for stabilizer used in step 1), can be with
Use all stabilizers disclosed in the prior art, including ionic emulsifying agent, nonionic emulsifier and various macromolecular stabilizers
Agent and polyanion.But the selection of stabilizer needs to be adjusted according to the emulsification system of selected rubber latex itself.It is excellent
Select one or more of anionic emulsifier and macromolecular stabilizer agent.One of more preferable macromolecular stabilizer agent is several
Kind.
The anionic emulsifier include lauryl sodium sulfate, neopelex, dodecyl benzene sulfonic acid,
Disodium 4-dodecyl-2,4 '-oxydibenzenesulfonate etc..Cationic emulsifier includes dodecyl trimethyl ammonium bromide, cetyl front three
Base ammonium bromide etc..Nonionic emulsifier has OP series, NP series, Trixon series, Span series and TWEEN Series etc..Big point
Sub- stabilizer includes polyoxyethylene (PEO), polyvinylpyrrolidone (PVP), polyvinyl acetate (PVAc, degree of hydrolysis: 70-
99%), poly 4 vinyl pyridine, poly 2 vinyl pyridine, poly- (4-vinylpridine-co- butyl methacrylate), polypropylene
Amide, methylcellulose, cyclodextrin etc..Polyanion includes Sodium Polyacrylate, poly (sodium 4-styrenesulfonate) etc..Wherein preferably ten
One of dialkyl benzene sulfonic acids sodium, dodecyl benzene sulfonic acid, PVP, PVA, methylcellulose and poly (sodium 4-styrenesulfonate) or
It is several.One or more of more preferable dodecyl benzene sulfonic acid, PVP and PVA.
The molecular weight ranges of macromolecular stabilizer agent used in step 1 are 5000-5000000, and preferred molecular weight range is
8000-2500000, more preferable molecular weight ranges are 10000-1000000.
In a preferred embodiment of the present invention, the quality meter of stabilizer macromolecule latex fluid solid content in step 1)
For 1wt%-25wt%, preferably 3wt%-22wt%, more preferable 6wt%-20wt%
In a preferred embodiment of the present invention, range of reaction temperature used in step 1) is about from -10 DEG C -80
DEG C, preferable reaction temperature is 0-50 DEG C, and more preferable reaction temperature is 0-30 DEG C.
In a preferred embodiment of the present invention, the reaction time used in step 1) need according to oxidation polymerization into
Depending on capable reaction condition, the condition of polymerization reaction is different, and the rate of polymerization reaction can also occur to change accordingly, generally several
Between a hour to several days.
In a preferred embodiment of the present invention, the inert atmosphere for polymer charing being carried out in step 3) includes nitrogen
With argon gas etc..
In a preferred embodiment of the present invention, the temperature range that polymer charing is carried out in step 3) is 400-
2300 DEG C, it is contemplated that heteroatomic content can be reduced with the raising of carbonization temperature, and preferred temperature range is 500-1500 DEG C,
Preferred carbonization temperature is 500-1000 DEG C.
Beneficial effects of the present invention:
The carbosphere of Heteroatom doping provided by the invention has hierarchical porous structure, while having micropore, mesoporous or even big
Pore structure, Heteroatom doping amount is high, and higher specific surface area can be obtained by not needing activation, in CO2Trapping, battery, super electricity
Container, catalyst, catalyst carrier etc. have application prospect.Hole is divided into three classes according to the size in aperture by IUPAC, is respectively
The micropore in aperture<2nm, the mesoporous and aperture>50nm that aperture is 2-50nm macropore.According to this scheme of classification, the present invention is obtained
To carbosphere in existing size<2nm micropore, and have size in the mesoporous of 2-50nm, there are also size>50nm macropore, because
This is with hierarchical porous structure.
The method of the carbosphere provided by the invention has the characteristics that simple process, easily operated, and directly charing can
To obtain the porous carbon nano-particle of Heteroatom doping, avoids in art methods and lacked using a large amount of templates are wasting
Point also avoids the process activated using substances such as alkali, simplifies preparation process, and carbon nano-particle performance obtained
It is all very stable with structure.
The preparation method is that the oxidation polymerization of intrinsically conducting high polymer monomer is carried out in macromolecule emulsion, at
The surface deposition intrinsic type conducting polymer clad in high molecular emulsion particle of function prepares the high score with core-shell structure
Son-intrinsically conducting high molecular emulsion particle, has obtained stable macromolecule-intrinsically conducting macromolecule emulsion.It is of the invention first
The secondary method using spray drying is prepared by macromolecule-molecular conductive micro-balloons of intrinsically conducting polymer colloidal particles.Pass through
Direct high temperature carbonization conductive micro-balloons under an inert atmosphere, wherein the common macromolecule of stratum nucleare due to thermal stability it is poor, it is substantially complete
It is complete to decompose, and the intrinsically conducting polymeric PTC materials layer of shell is carbonized at high temperature, is converted into layer of charcoal, pattern obtains
It keeps well.Because the partial size of common high molecular emulsion particle is usually all in 50-500nm, we can be obtained greatly
Hole.Intrinsically conducting macromolecule usually will form a large amount of micropore during charing, and the accumulation of latex particle will form Jie
The accumulation hole of hole grade, therefore obtained carbosphere has hierarchical porous structure.Have heteroatomic intrinsically conducting high by selection
Molecule can obtain the carbosphere with hierarchical porous structure of Heteroatom doping.
Detailed description of the invention
The SEM photograph for the Heteroatom doping carbosphere with hierarchical porous structure that Fig. 1 is made of hollow carbon sphere is embodied
Method
Specific embodiment
The present invention is further described with embodiment below, but the scope of the present invention is not restricted by the embodiments.This
The range of invention is determined by appended claims.
In an embodiment of the present invention:
Scanning electron microscope (SEM): the shape and surface topography of product are by S-4800 type Flied emission scanning electron
Microscope (Hitachi, Japan) is directly observed under 1kV voltage, and the electric conductivity of product itself is preferable, and not needing metal spraying can be straight
Connect observation.
N2Adsorption desorption isothermal curve: on Micrometritics ASAP2020 adsorbent equipment, under the conditions of -196 DEG C into
Row N2The test of adsorption desorption isothermal curve.Before test, place is de-gassed to sample under 180 DEG C, high vacuum condition first
Manage at least 6h.The specific surface area of product is calculated by the method for Brunauer-Emmett-Teller (BET).
Micropore size and distribution are obtained by Horvath-Kawazoe (HK) calculating method.
Mesoporous pore size and distribution are obtained by Barrett-Joyner-Halenda (BJH) calculating method.
Total pore volume is by relative pressure P/P0It is calculated for the adsorbance at 0.97.
Micropore volume is calculated by t-plot model.
X- photoelectron spectroscopy (XPS): the surface of product is carried out on the Sigma Probe instrument of ThermoFisher company
Elemental analysis.
Elemental analysis: by the EA1112 instrument of Thermo company of the U.S. to the content of nitrogen and element sulphur in product
It is analyzed.
In the present invention, the conducting polymer refers to intrinsically conducting macromolecule or other kinds of conductive polymer
Son refers to intrinsically conducting macromolecule under the preferred conditions.
Embodiment 1
Step 1) prepares phenylpropyl alcohol-polypyrrole nuclear-shell emulsion: taking a certain amount of styrene-acrylic emulsion (BC-991, Beijing Orient subfamily
Power Chemical Industry Science Co., Ltd), it is added in the reaction vessel equipped with mechanical stirring device, it is styrene-acrylic resin that quality, which is then added,
10% pyrrole monomer starts to be swollen styrene-acrylic latex particle, after being swollen 1h, sequentially adds polyvinylpyrrolidone (K30, molecule
Amount about 10,000, Xilong Chemical Co., Ltd), p-methyl benzenesulfonic acid and ferric chloride hexahydrate (III) aqueous solution, system is put
After carrying out cooling in ice water cooling bath, 30% aqueous hydrogen peroxide solution is added and starts to react, the solid content of system is 5%, most
Polyvinylpyrrolidone in whole system, p-methyl benzenesulfonic acid, ferric chloride hexahydrate (III) and hydrogen peroxide concentration be respectively
60mM, 40mM, 0.1mM and 120mM stop obtaining phenylpropyl alcohol-polypyrrole nuclear-shell emulsion after reacting 48h.
Step 2) is spray-dried phenylpropyl alcohol-polypyrrole lotion, has obtained micro- by the molecular conduction of phenylpropyl alcohol-polypyrrole emulsion particle
Ball.
Sample obtained in step 2 is carried out high temperature carbonization by step 3) in a nitrogen atmosphere, and carbonization temperature is 800 DEG C, is obtained
To product SEM photograph as shown in Figure 1, it is observed that microballoon is made of many compact arranged nano-scale spheres, and
These bead surfaces have some more than ten nanometer of duck eyes, it can thus be appreciated that being hollow structure in fact inside these beads.It produces
The BET specific surface areas of product, aperture, Kong Rong and nitrogen element content data be shown in Table 1.It is to be noted that due to macropore in product
Aperture and styrene-acrylic latex particle are closely sized to, and are 100nm or so, are had exceeded N2The test scope of adsorption desorption experiment, therefore by N2
The total pore volume that adsorption desorption characterizes can be less than normal.
Embodiment 2
Step 1) phenylpropyl alcohol-polypyrrole nuclear-shell emulsion prepares same as Example 1.
The drying of step 2) phenylpropyl alcohol-polypyrrole lotion is also same as Example 1.
The high temperature carbonization of step 3) product is to carry out in a nitrogen atmosphere, and carbonization temperature is 700 DEG C.The BET of product compares table
Area, aperture, Kong Rong and nitrogen element content data be shown in Table 1.
Embodiment 3
Step 1) phenylpropyl alcohol-polypyrrole nuclear-shell emulsion prepares same as Example 1.
The drying of step 2) phenylpropyl alcohol-polypyrrole lotion is also same as Example 1.
The high temperature carbonization of step 3) product is to carry out in a nitrogen atmosphere, and carbonization temperature is 600 DEG C.The BET of product compares table
Area, aperture, Kong Rong and nitrogen element content data be shown in Table 1.
Embodiment 4
Step 1) phenylpropyl alcohol-polypyrrole nuclear-shell emulsion prepares same as Example 1.
The drying of step 2) phenylpropyl alcohol-polypyrrole lotion is also same as Example 1.
The high temperature carbonization of step 3) product is to carry out in a nitrogen atmosphere, and carbonization temperature is 500 DEG C.The BET of product compares table
Area, aperture, Kong Rong and nitrogen element content data be shown in Table 1.
Embodiment 5
Step 1) phenylpropyl alcohol-polypyrrole nuclear-shell emulsion preparation method is same as Example 1, only the addition of pyrrole monomer
1 ten thousand) and ferric chloride hexahydrate amount is reduced to 5% styrene-acrylic resin, and (domestic K30, molecular weight are about to polyvinylpyrrolidone
(III) concentration is same as Example 1, respectively 60mM and 0.1mM, and phase has occurred in the concentration of p-methyl benzenesulfonic acid and hydrogen peroxide
The reduction answered, respectively 20mM and 60mM.
Step 2) and step 3) are same as Example 1.
Embodiment 6
Step 1) phenylpropyl alcohol-polypyrrole nuclear-shell emulsion preparation method is same as Example 1, only the addition of pyrrole monomer
It is 15% styrene-acrylic resin that amount, which increases, and it is still 0.1mM that the concentration of ferric chloride hexahydrate (III) is same as Example 1, polyvinyl
Pyrrolidones (domestic K30, molecular weight be about 1 ten thousand), the concentration of p-methyl benzenesulfonic acid and hydrogen peroxide all improve, respectively
120mM, 60mM and 180mM.
Step 2) and step 3) are same as Example 1.The BET specific surface area of product, aperture, Kong Rong and nitrogen element content
Data are shown in Table 1.
Embodiment 7
Step 1) phenylpropyl alcohol-polypyrrole nuclear-shell emulsion prepares same as Example 6.
The drying of step 2) phenylpropyl alcohol-polypyrrole lotion is also same as Example 1.
The high temperature carbonization of step 3) product is to carry out in a nitrogen atmosphere, and carbonization temperature is 1500 DEG C.The BET of product compares table
Area, aperture, Kong Rong and nitrogen element content data be shown in Table 1.
Embodiment 8
Step 1) phenylpropyl alcohol-polypyrrole nuclear-shell emulsion prepares same as Example 1.
The drying of step 2) phenylpropyl alcohol-polypyrrole lotion is also same as Example 1.
The high temperature carbonization of step 3) product is to carry out in a nitrogen atmosphere, and carbonization temperature is 2300 DEG C.
Table 1
Wherein: SBETFor the specific surface area calculated by Brunauer-Emmett-Teller (BET) method；
SmicroFor the micropore specific area obtained by t-plot；
VmicroFor the Micropore volume analyzed by t-plot；
VtotFor P/P0Single-point for pore size at 0.97 less than 70nm adsorbs total pore volume；
DmesoFor the mesoporous average pore size calculated by Barrett-Joyner-Halenda (BJH) method；
DmicroFor the micropore size calculated by Horvath-Kawazoe (HK) method；
CN1N element content for the product surface obtained by XPS；
CN2For the N element content in the product ontology that is obtained by elemental analysis.
Claims (51)
1. a kind of carbosphere of Heteroatom doping, which is characterized in that the carbosphere is by the carbon nanometer with hierarchical porous structure
Grain composition, the mesoporous and aperture that the carbon nano-particle has micropore of the aperture less than 2nm, aperture is 2-50nm is greater than 50nm's
Macropore, and the BET specific surface area of the carbon nano-particle is 300-1000m2/ g, the content of heteroatoms in the carbon nano-particle
For 2-25wt%, the hetero atom is selected from least one of nitrogen phosphate and sulfur and boron.
2. carbosphere according to claim 1, which is characterized in that the carbon nano-particle is in P/P0Aperture at=0.97
It is 0.2-0.7cm for the single-point absorption total pore volume in the hole below 70nm3g-1, the Kong Rongwei 0.1-0.3cm of the micropore3g-1, it is situated between
The total pore volume of hole and macropore is 0.2-1.1cm3g-1。
3. carbosphere according to claim 2, which is characterized in that the BET specific surface area of the nano particle is 450-
600m2/g。
4. carbosphere according to any one of claim 1-3, which is characterized in that the partial size of the carbosphere is 0.5-20
μm；The partial size of nano particle is 10-500nm.
5. carbosphere according to claim 4, which is characterized in that the partial size of the carbosphere is 1-15 μm；Nano particle
Partial size be 20-300nm.
6. carbosphere according to claim 5, which is characterized in that the partial size of the carbosphere is 1-10 μm；Nano particle
Partial size be 30-100nm.
7. carbosphere according to any one of claim 1-3, which is characterized in that the hetero atom is nitrogen-atoms, and institute
The content for stating nitrogen-atoms is 2-23wt%.
8. carbosphere according to claim 7, which is characterized in that the content of the nitrogen-atoms is 3-15wt%.
9. carbosphere according to claim 8, which is characterized in that the content of the nitrogen-atoms is 4-10wt%.
10. carbosphere according to any one of claim 1-3, which is characterized in that the hetero atom is sulphur atom, and sulphur is former
The content of son is 2-25wt%.
11. carbosphere according to claim 10, which is characterized in that the content of the sulphur atom is 3-15wt%.
12. carbosphere according to claim 11, which is characterized in that the content of the sulphur atom is 4-10wt%.
13. a kind of production method of carbosphere described in any one of -12 according to claim 1, comprising:
1) under the conditions of existing for oxidant, dopant and the stabilizer, conductive high polymer monomer is carried out in macromolecule emulsion
In-situ oxidizing-polymerizing obtains macromolecule-conducting polymer lotion；
2) it by being spray-dried the macromolecule-conducting polymer lotion, prepares by macromolecule-conducting polymer emulsion particle subgroup
At conductive micro-balloons；
3) high temperature carbonization of the microballoon prepared in step 2) is carried out under an inert atmosphere, and obtain being made of hollow sphere has multistage
The Heteroatom doping carbosphere of pore structure；
Wherein, the oxidant is selected from least one of following substance: the copper (II) of iron (III) salt of inorganic acid, inorganic acid
Salt, persulfate, periodate, hydrogen peroxide, ozone, six cyanogen close iron (III) potassium, two hydrated sulfuric acids, four ammonium cerium (IV), bromine,
Iodine, iron (III) salt of organic acid and metal ion compound oxidation system with hydrogen peroxide；
The dopant is selected from least one of following substance: inorganic acid, lewis acid, organic acid and its derivative or iron
(III) salt, alkyl sulfonic acid, benzene sulfonic acid, naphthalene sulfonic acids, anthraquinone sulfonic acid and its derivative and tetracyanoethylene and trifluoromethanesulfonic acid；
The stabilizer is selected from least one of following substance: anionic emulsifier, nonionic emulsifier, macromolecular are steady
Determine agent and polyanion；
The macromolecule emulsion is under an inert atmosphere can be in 450 DEG C or less complete decomposition or the macromolecule of resolution ratio > 50%
Lotion；
The conducting polymer is selected from the conducting polymer being made of at least one of following monomer: pyrroles, thiophene, benzene
Amine, indoles, carbazole, furans and these monomers derivative.
14. according to the method for claim 13, which is characterized in that the conducting polymer be selected from pyrroles, aniline and its
Derivative and at least one of 3,4- ethene dioxythiophene and carbazole.
15. according to the method for claim 13, which is characterized in that the conducting polymer be selected from pyrroles, aniline and 3,
One or more of 4- ethene dioxythiophene and its derivative.
16. according to the method for claim 13, which is characterized in that the pyrroles, thiophene and derivatives structure such as Formulas I
It is shown:
Wherein, X N-R2Or S；R2For H or C1-C20Alkyl, aryl either replace aryl；
Existing 4 R1It is identical or different, be each independently selected from H, alkyl, naphthenic base, alkenyl, aryl, alkylaryl,
Hydroxyl, alkoxy, halogen or nitro, wherein at least two R1Selected from H, halogen or alkoxy.
17. according to the method for claim 16, which is characterized in that R2For H or C1-C12Alkyl；Each R1It is respectively independent
Ground is selected from H, C1-C20Alkyl, hydroxyl, C1-C4Alkoxy, chlorine or nitro, wherein at least in two R at the ortho position X1It must divide
Not independently selected from H, halogen or alkoxy.
18. according to the method for claim 17, which is characterized in that R2For H or C1-C8Alkyl；Each R1All it is respectively
H, methyl, hydroxyl, chlorine or nitro, wherein at least in two R at the ortho position X1It is H.
19. according to the method for claim 18, which is characterized in that R2For H.
20. method according to claim 14 or 15, which is characterized in that the structural formula of the aniline and its derivatives such as formula
Shown in II:
Wherein, R3For H, C1-C20Alkyl, aryl or substituted aryl；
Existing 4 R4It is identical or different, it is each independently selected from H, alkyl, naphthenic base, alkenyl, aryl, alkyl and replaces virtue
Base, hydroxyl, alkoxy, halogen or nitro, wherein at least one R4It is necessary for H, halogen or alkoxy.
21. according to the method for claim 20, which is characterized in that R3For H or C3-C12Alkyl；Existing 4 R4All solely
On the spot it is selected from H, C1-C4Alkyl, hydroxyl, C1-C4Alkoxy, chlorine or nitro, and at least in NHR3The R of contraposition4It is H, halogen
Or alkoxy.
22. according to the method for claim 21, which is characterized in that R3For H or C4-C8Alkyl；Existing 4 R4It is all independent
Ground is selected from H, methyl, ethyl, hydroxyl, chlorine, bromine or nitro, and NHR3The R of contraposition4For H.
23. according to the method for claim 22, which is characterized in that R3For H；All R4It is all H.
24. method described in any one of 3-19 according to claim 1, which is characterized in that the conductive high polymer monomer is in step
It is rapid 1) in quality be macromolecule latex fluid solid content 1-30%.
25. according to the method for claim 24, which is characterized in that quality of the conductive high polymer monomer in step 1)
For the 2-20% of macromolecule latex fluid solid content.
26. according to the method for claim 25, which is characterized in that quality of the conductive high polymer monomer in step 1)
For the 5-15% of macromolecule latex fluid solid content.
27. method described in any one of 3-19 according to claim 1, which is characterized in that the macromolecule emulsion is selected from following
At least one of substance: styrene-acrylic emulsion, polystyrene emulsion, polyacrylate dispersion, styrene-butadiene emulsion, carboxyl styrene emulsion,
Butyronitrile emulsion, carboxyl butyronitrile lotion, ethylene-vinyl acetate lotion, butadiene-styrene-vinyl pyridine rubber lotion, neoprene latex, polybutadiene
Alkene rubber latex and nature rubber latex.
28. according to the method for claim 27, which is characterized in that the macromolecule emulsion is selected from styrene-acrylic emulsion, polyphenyl second
At least one of alkene lotion, polyacrylate dispersion, butyronitrile emulsion, carboxyl butyronitrile lotion, ethylene-vinyl acetate lotion.
29. according to the method for claim 28, which is characterized in that the macromolecule emulsion is selected from styrene-acrylic emulsion, polyphenyl second
At least one of alkene lotion, polyacrylate dispersion, butyronitrile emulsion and carboxyl butyronitrile lotion.
30. method described in any one of 3-19 according to claim 1, which is characterized in that the oxidant is selected from using inorganic
Iron (III) one or more of salt and persulfate of acid or organic acid.
31. according to the method for claim 30, which is characterized in that the oxidant is persulfate.
32. according to the method for claim 30, which is characterized in that the molar ratio of the oxidant and conductive high polymer monomer
Range is 0.1-10.
33. according to the method for claim 32, which is characterized in that the molar ratio of the oxidant and conductive high polymer monomer
Range is 0.3-5.
34. according to the method for claim 33, which is characterized in that the molar ratio of the oxidant and conductive high polymer monomer
Range is 0.5-2.
35. method described in any one of 3-19 according to claim 1, which is characterized in that the stabilizer is selected from anionic
At least one of emulsifier and/or macromolecular stabilizer agent.
36. according to the method for claim 35, which is characterized in that the stabilizer in macromolecular stabilizer agent at least
It is a kind of.
37. according to the method for claim 36, which is characterized in that the molecular weight of the macromolecular stabilizer agent is 5000-
5000000。
38. according to the method for claim 37, which is characterized in that the molecular weight of the macromolecular stabilizer agent is 10000-
2500000。
39. according to the method for claim 38, which is characterized in that the molecular weight of the macromolecular stabilizer agent is 10000-
1000000。
40. method described in any one of 3-19 according to claim 1, which is characterized in that the dopant is selected from inorganic acid, road
One or more of Lewis acid, alkyl sulfonic acid, benzene sulfonic acid and its derivative.
41. according to the method for claim 40, which is characterized in that the dopant is selected from HCl, p-methyl benzenesulfonic acid, camphor
At least one of sulfonic acid and dodecyl benzene sulfonic acid.
42. according to the method for claim 41, which is characterized in that the dopant is p-methyl benzenesulfonic acid.
43. method described in any one of 3-19 according to claim 1, which is characterized in that the Can Za Ji ︰ conducting polymer list
The molar ratio of body is 0.05-10.
44. according to the method for claim 43, which is characterized in that the molar ratio of the Can Za Ji ︰ conductive high polymer monomer
For 0.1-5.
45. according to the method for claim 44, which is characterized in that the molar ratio of the Can Za Ji ︰ conductive high polymer monomer
For 0.2-2.
46. method described in any one of 3-19 according to claim 1, which is characterized in that the temperature of reaction used in step 1)
Spending range is -10 DEG C -80 DEG C.
47. according to the method for claim 46, which is characterized in that the temperature range of reaction used in step 1) is 0-50
℃。
48. according to the method for claim 47, which is characterized in that the temperature range of reaction used in step 1) is 0-30
℃。
49. method described in any one of 3-19 according to claim 1, which is characterized in that the temperature range of charing is 400-
2300℃。
50. according to the method for claim 49, which is characterized in that the temperature range of charing is 500-1500 DEG C.
51. according to the method for claim 50, which is characterized in that the temperature range of charing is 500-1000 DEG C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410390273.1A CN105329874B (en) | 2014-08-08 | 2014-08-08 | A kind of carbosphere of Heteroatom doping and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410390273.1A CN105329874B (en) | 2014-08-08 | 2014-08-08 | A kind of carbosphere of Heteroatom doping and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105329874A CN105329874A (en) | 2016-02-17 |
| CN105329874B true CN105329874B (en) | 2018-12-28 |
Family
ID=55280682
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410390273.1A Active CN105329874B (en) | 2014-08-08 | 2014-08-08 | A kind of carbosphere of Heteroatom doping and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105329874B (en) |
Families Citing this family (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106229157A (en) * | 2016-08-17 | 2016-12-14 | 哈尔滨万鑫石墨谷科技有限公司 | A kind of polyatom co-doped nano carbon fiber and one one step preparation method and purposes |
| CN107045944B (en) * | 2017-01-19 | 2019-07-16 | 江西科技师范大学 | High capacitance polybenzazole class nitrogen-doped porous carbon material and preparation method thereof |
| CN107082411B (en) * | 2017-05-18 | 2019-12-06 | 厦门大学 | nitrogen and boron co-doped carbon nano-microsphere and preparation method thereof |
| CN107180974B (en) * | 2017-05-18 | 2020-02-11 | 厦门大学 | Porous carbon/noble metal nano hybrid material and preparation method thereof |
| CN107200324A (en) * | 2017-06-27 | 2017-09-26 | 东莞理工学院 | A kind of activated carbon, its preparation method and application |
| CN108557803B (en) * | 2018-05-08 | 2021-10-29 | 闽南师范大学 | Carbon nanosphere doped with nitrogen and sulfur and synthesized by solid-phase microwave method, and preparation method and application thereof |
| CN108808019B (en) * | 2018-08-02 | 2021-09-07 | 临沂大学 | Oxygen reduction catalyst of heteroatom-doped carbon microsphere loaded iron phosphide nanoparticles and preparation method thereof |
| CN111453712A (en) * | 2019-01-21 | 2020-07-28 | 金华晨阳科技有限公司 | Hollow carbon ball with multistage pore structure and preparation method thereof |
| CN109830378B (en) * | 2019-01-21 | 2021-08-06 | 贵阳学院 | Sulfur-doped porous carbon material, preparation and application thereof, and electrode material and supercapacitor containing sulfur-doped porous carbon material |
| CN110526227B (en) * | 2019-08-29 | 2021-02-12 | 中国科学院福建物质结构研究所 | Carbon material and preparation method and application thereof |
| CN112705186B (en) * | 2019-10-24 | 2023-09-29 | 中国石油化工股份有限公司 | 2, 5-dichlorotoluene isomerization catalyst, preparation method and application thereof |
| CN112357906A (en) * | 2020-11-12 | 2021-02-12 | 同济大学 | Nitrogen-doped monomodal ultramicropore carbon nanosheet synthesized by in-situ amorphous cobalt template method, and method and application thereof |
| CN113443625B (en) * | 2021-06-30 | 2023-01-24 | 华东理工大学 | Preparation method of polystyrene resin-based spherical activated carbon |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009149540A1 (en) * | 2008-06-10 | 2009-12-17 | National Research Council Of Canada | Controllable synthesis of porous carbon spheres, and electrochemical applications thereof |
| CN102718205A (en) * | 2012-06-27 | 2012-10-10 | 北京科技大学 | Method for preparing three-dimensional hierarchical porous carbon |
| CN103545523A (en) * | 2013-10-30 | 2014-01-29 | 北京化工大学 | Porous carbon microsphere, preparation method and lithium ion battery negative electrode material |
| CN103871756A (en) * | 2012-12-18 | 2014-06-18 | 中国科学院兰州化学物理研究所 | Preparation method of submicron porous carbon bead |
| CN103964412A (en) * | 2013-01-30 | 2014-08-06 | 北京化工大学 | Preparation method of nitrogen-doped porous-structure carbon material |
-
2014
- 2014-08-08 CN CN201410390273.1A patent/CN105329874B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009149540A1 (en) * | 2008-06-10 | 2009-12-17 | National Research Council Of Canada | Controllable synthesis of porous carbon spheres, and electrochemical applications thereof |
| CN102718205A (en) * | 2012-06-27 | 2012-10-10 | 北京科技大学 | Method for preparing three-dimensional hierarchical porous carbon |
| CN103871756A (en) * | 2012-12-18 | 2014-06-18 | 中国科学院兰州化学物理研究所 | Preparation method of submicron porous carbon bead |
| CN103964412A (en) * | 2013-01-30 | 2014-08-06 | 北京化工大学 | Preparation method of nitrogen-doped porous-structure carbon material |
| CN103545523A (en) * | 2013-10-30 | 2014-01-29 | 北京化工大学 | Porous carbon microsphere, preparation method and lithium ion battery negative electrode material |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105329874A (en) | 2016-02-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105329874B (en) | A kind of carbosphere of Heteroatom doping and preparation method thereof | |
| Cui et al. | Polyarylimide and porphyrin based polymer microspheres for zinc ion hybrid capacitors | |
| Ma et al. | Facile fabrication of Ag/PANI/g-C3N4 composite with enhanced electrochemical performance as supercapacitor electrode | |
| CN105439115B (en) | The carbon nano-particle and its production method of a kind of Heteroatom doping | |
| Wang et al. | Interfacial synthesis of mesoporous MnO2/polyaniline hollow spheres and their application in electrochemical capacitors | |
| Shen et al. | Supercapacitor electrodes based on nano-polyaniline deposited on hollow carbon spheres derived from cross-linked co-polymers | |
| Jo et al. | 3 D Network‐Structured Crumpled Graphene/Carbon Nanotube/Polyaniline Composites for Supercapacitors | |
| Lei et al. | Soft template interfacial growth of novel ultralong polypyrrole nanowires for electrochemical energy storage | |
| Wang et al. | Synthesis and morphology evolution of ultrahigh content nitrogen‐doped, micropore‐dominated carbon materials as high‐performance supercapacitors | |
| Liu et al. | PVP-assisted synthesis of nitrogen-doped hollow carbon spheres for supercapacitors | |
| Moreno-Castilla | Colloidal and micro-carbon spheres derived from low-temperature polymerization reactions | |
| CN101407575A (en) | High dispersibility nano-scale poly (3,4-ehtylene dioxythiophene), preparation and use thereof | |
| Tang et al. | Green synthesis of silver nanoparticles embedded in polyaniline nanofibers via vitamin C for supercapacitor applications | |
| Gizdavic-Nikolaidis et al. | Enhanced microwave synthesis: Fine-tuning of polyaniline polymerization | |
| Majumder et al. | Aluminum based metal-organic framework integrated with reduced graphene oxide for improved supercapacitive performance | |
| CN106582817A (en) | Simple and convenient method for preparing three-dimensional nitrogen-doped graphene | |
| He et al. | Development of g-C3N4 activated hollow carbon spheres with good performance for oxygen reduction and selective capture of acid gases | |
| Cai et al. | Phenol–formaldehyde carbon with ordered/disordered bimodal mesoporous structure as high-performance electrode materials for supercapacitors | |
| Yoruk et al. | Design and assembly of supercapacitor based on reduced graphene oxide/TiO2/polyaniline ternary nanocomposite and its application in electrical circuit | |
| Zhu et al. | Synthesis of γ-MnO2/PANI composites for supercapacitor application in acidic electrolyte | |
| Bao et al. | Pseudo-capacitive performance enhancement of α-MnO2 via in situ coating with polyaniline | |
| Dhibar et al. | Copper chloride‐doped polyaniline/multiwalled carbon nanotubes nanocomposites: Superior electrode material for supercapacitor applications | |
| Peng et al. | Template-confined growth of poly (4-aminodiphenylamine) nanosheets as positive electrode toward superlong-life asymmetric supercapacitor | |
| Soni et al. | Synthesis of Ultrathin PEDOT on Carbon Nanotubes and Shear Thinning Xanthan Gum‐H2SO4 Gel Electrolyte for Supercapacitors | |
| Kong et al. | Soft-to-hard templating to well-dispersed N-doped mesoporous carbon nanospheres via one-pot carbon/silica source copolymerization |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |