CN104810161B - A kind of nitrogen oxygen doping hollow Nano charcoal ball preparation method and its electrochemical energy storage application - Google Patents

A kind of nitrogen oxygen doping hollow Nano charcoal ball preparation method and its electrochemical energy storage application Download PDF

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CN104810161B
CN104810161B CN201510139901.3A CN201510139901A CN104810161B CN 104810161 B CN104810161 B CN 104810161B CN 201510139901 A CN201510139901 A CN 201510139901A CN 104810161 B CN104810161 B CN 104810161B
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oxygen doping
hollow
nitrogen oxygen
nitrogen
ball
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CN104810161A (en
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宋怀河
刘海燕
陈晓红
马兆昆
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Changzhou Institute for Advanced Materials Beijing University of Chemical Technology
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Changzhou Institute for Advanced Materials Beijing University of Chemical Technology
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • 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
    • C01B32/15—Nano-sized carbon materials
    • C01B32/18—Nanoonions; Nanoscrolls; Nanohorns; Nanocones; Nanowalls
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/32—Carbon-based
    • H01G11/36—Nanostructures, e.g. nanofibres, nanotubes or fullerenes
    • 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
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2202/00—Structure or properties of carbon nanotubes
    • C01B2202/20—Nanotubes characterized by their properties
    • C01B2202/22—Electronic properties
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    • 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
    • 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
    • Y02E60/13—Energy storage using capacitors

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  • Nanotechnology (AREA)
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Abstract

The invention discloses a kind of nitrogen oxygen doping hollow Nano charcoal ball preparation method and its electrochemical energy storage application.Polyaniline hollow nanospheres are prepared as presoma by the use of the step of hydro-thermal method one, carbonize obtain the hollow carbon nanospheres of nitrogen oxygen doping, a diameter of 500 800nm of ball under nitrogen atmosphere, at a temperature of 600 800 DEG C, ball wall thickness is 80 100nm.The hollow carbon nanospheres have high nitrogen (4 8at%), oxygen (6 11at%) content, and specific surface area is 100 251m2 g‑1.The present invention shows high electrochemical energy storage performance when applied to ultracapacitor and lithium rechargeable battery.

Description

A kind of nitrogen oxygen doping hollow Nano charcoal ball preparation method and its electrochemical energy storage application
Technical field
The present invention relates to electrochemical energy storage electrode material field, more particularly to a kind of nitrogen oxygen doping hollow Nano charcoal ball electrode Material and preparation method thereof.
Background technology
With the development of science and technology, people's quality of life improves constantly, increasing electronic product turns into people's life institute An indispensable part.On the other hand, fossil fuel reserves consumption and problem of environmental pollution is on the rise, electric automobile it is general And as a big trend.In this context, energy storage device such as lithium ion battery and ultracapacitor are proposed higher Requirement.For energy storage device, its key is exactly electrode material.Therefore designing and developing the electrode material of excellent performance turns into Various countries' researcher's urgent problem.In numerous electrode materials, Carbon Materials have high specific surface area, conduction because of it Property, chemical stability and it is cheap and easy to get the features such as show one's talent.It is a kind of highly effective that the hetero atoms such as O, N are introduced in carbon skeleton Raising Carbon Materials capacity method.Appropriate Heteroatom doping can the tribute on the basis of the original electric double layer capacitance of Carbon Materials Fake capacitance is offered, and Heteroatom doping can also improve the polarity of electrode material, be advantageous to the infiltration of electrolyte, so as to improve electricity The performance of pole material.
Except Heteroatom doping, the nanostructured of material can also have an impact to the energy-storage property of material.Received in numerous In rice structure, spherical structure is counted as a kind of structure the most favourable, and the accumulation that spherical structure can improve electrode material is close Degree, electrolyte ion can enter material internal from all directions, and hollow ball structure is to improving high rate performance advantageously.
Conductive polymer polyanilinc is readily synthesized, environment-friendly, and N/C contents are high, are that the more satisfactory hetero atom for preparing is mixed The presoma of miscellaneous Carbon Materials.Polyaniline can by controlling synthesis condition to prepare different-shape, as nanotube, nanobelt, Nano wire, nanosphere etc..Such as Wan [Zhang L, Wan M.Adv.Funct.Mater.2003,13,815-820] have studied In bigcatkin willow acid system, one-dimensional polyaniline pipe and the three-dimensional hollow chou of polyaniline are prepared to realize by changing experiment condition Structure.Li etc. [Li G, Zhang C, Peng H et al.Macromol.Rapid Comm.2008,29,1954-1958.] is studied In metanilic acid system prepare polyaniline microsphere.By high-temperature process under an inert atmosphere, the pattern of polyaniline can To be maintained, therefore the polyaniline Carbon Materials with different-shape can be made.[H.Dou, the et al.J such as Dou Mater.Chem.A 2014,2,5352.] using polystyrene spheres it is template, polyaniline is that presoma is prepared for a kind of having sky The carbon nanospheres of core structure.Although template can obtain the homogeneous hollow ball shape structure of pattern, preparation process needs to make With template, and template is removed, preparation method is more complicated.
The content of the invention
It is an object of the invention to provide a kind of nitrogen oxygen doping hollow Nano charcoal ball, preparation method and applications.Before polyaniline Drive body to be made by one-step oxidation process, synthetic method is simple.It is super no matter the nitrogen oxygen doping hollow Nano charcoal ball of preparation is applied to Level capacitor or lithium rechargeable battery all show excellent chemical property.
The present invention provides a kind of preparation of the hollow carbon nanospheres electrode material of the nitrogen oxygen doping of new electrochemical performance Method, it is characterised in that comprise the following steps：
Step 1：Aniline monomer 0.5mL is dissolved in 0.15molL-1Sulfuric acid solution in stirring 30min be well mixed, then The hydrogenperoxide steam generator and 10mL ammonium persulfate solutions (0.01M) that 0.5mL volume ratios are 30% are added, continuing stirring 30min makes Well mixed, hydro-thermal reaction 1-10h, reaction temperature is 120-170 DEG C, and reaction end filters after being cooled to room temperature, and will production Thing is cleaned colourless to filtrate with absolute ethyl alcohol and deionized water, the drying of 50 DEG C of vacuum, obtains polyaniline hollow nanospheres；
Step 2：By polyaniline hollow nano-sphere in air atmosphere, oxidation processes 2h at 200 DEG C, it is empty to obtain pre-oxidation Bulbus cordis product；
Step 3：Pre-oxidation product obtained by step 2 is taken, is put into high temperature carbonization furnace, is separately heated under an inert atmosphere 600 DEG C, 700 DEG C, 800 DEG C and 900 DEG C, it is incubated 2-6h.
Further preferred scheme is the present invention：Hydro-thermal reaction 3-6h, reaction temperature are 140-160 DEG C, the charing temperature Spend for 600-800 DEG C, be incubated 2h.
Material prepared by the present invention has nano hollow structure, a diameter of 700-800nm of ball, ball wall thickness 80- 100nm；With high content of heteroatoms, nitrogen (4-8at%), oxygen (6-11at%).
Brief description of the drawings
Accompanying drawing 1 is the scanning electron microscope (SEM) photograph of the hollow carbon nanospheres of nitrogen oxygen doping.
Accompanying drawing 2 is the transmission electron microscope picture of the hollow carbon nanospheres of nitrogen oxygen doping.
Accompanying drawing 3 is that carbonization temperature is respectively that the hollow carbon nanospheres of nitrogen oxygen doping obtained by 600,700 and 800 DEG C are applied to surpass Capacitor charge and discharge capacity curve of the level capacitor under different current densities.
Accompanying drawing 4 is that the hollow carbon nanospheres of nitrogen oxygen doping that carbonization temperature is gained at 700 DEG C are applied to lithium ion secondary electricity Pond is in 0.05A g-1Cyclic curve under current density.
Embodiment
The present invention is described in detail with reference to the accompanying drawings and examples：
Embodiment 1
Aniline monomer 0.5mL is dissolved in 0.15molL-1Sulfuric acid solution in stirring 30min be well mixed, then add 0.5mL volume ratios are 30% hydrogenperoxide steam generator and 10mL ammonium persulfate solutions (0.01M), continue stirring 30min and are allowed to mixed Uniform, hydro-thermal reaction 6h is closed, reaction temperature is 150 DEG C, and reaction end filters after being cooled to room temperature, and by product absolute ethyl alcohol Cleaned with deionized water colourless to filtrate, the drying of 50 DEG C of vacuum, obtain polyaniline hollow nanospheres；By polyaniline hollow nano-sphere In air atmosphere, pre-oxidation treatment 2h at 200 DEG C, obtain pre-oxidizing hollow ball product；Above-mentioned gained pre-oxidation product is taken, is put Enter in high temperature carbonization furnace, be heated to 700 DEG C under an inert atmosphere, be incubated 2h.
Nitrogen oxygen doping Carbon Materials have homogeneous spherical structure as shown in the ESEM of accompanying drawing 1 (SEM)；As accompanying drawing 2 transmits Electronic Speculum, the Carbon Materials of nitrogen oxygen doping shown in picture have hollow-core construction, a diameter of 800nm, ball wall thickness 100nm；Such as accompanying drawing, 3 The test result of ultracapacitor shows that the hollow carbon nanospheres of nitrogen oxygen doping obtained by 700 DEG C of charing process are in current density 0.2A g-11000 capacity of lower circulation are 200F g-1.In current density 5A g-11000 capacity of circulation have 121F g-1.It is such as attached The test result of Fig. 4 lithium rechargeable batteries shows that the hollow carbon nanospheres of nitrogen oxygen doping obtained by 700 DEG C of charing process are in electricity Current density 0.05A g-150 capacity of lower circulation are 527mA h g-1。
Embodiment 2
The preparation method of polyaniline CNT obtains nitrogen oxygen and mixed with carbonization temperature being 600 DEG C unlike embodiment 1 Miscellaneous hollow carbon nanospheres.
The hollow carbon nanospheres of nitrogen oxygen doping that 600 DEG C of charing process obtain as shown in Figure 3 are in current density 0.2A g-1Under 1000 capacity of circulation have 142F g-1, in current density 5A g-11000 capacity of circulation have 63F g-1。
Embodiment 3
The preparation method of polyaniline Nano carbon balls, the difference is that carbonization temperature is 800 DEG C, obtains nitrogen oxygen and mixed with embodiment 1 Miscellaneous hollow carbon nanospheres.
The porous CNT of N doping that 800 DEG C of carbonization treatments obtain as shown in Figure 3 is in current density 0.2A g-1Under follow 1000 capacity of ring have 53F g-1, in current density 5A g-11000 capacity of circulation have 32F 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 a variety of equivalent modifications or replacement on the premise of without prejudice to spirit of the invention, These equivalent modifications or replacement are all contained in the application claim limited range.

Claims (4)

  1. A kind of 1. nitrogen oxygen doping hollow Nano charcoal ball material, it is characterised in that：The charcoal ball is by polyaniline presoma by carbonizing Form, there is nano hollow structure, a diameter of 700-800nm, ball wall thickness 80-100nm, high nitrogen, oxygen content, the nitrogen content For 4-8at%, the oxygen content is 6-11at%；Nitrogen oxygen doping hollow Nano charcoal ball is as ultracapacitor and lithium ion battery Electrode material is in use, show high electrochemical energy storage performance.
  2. A kind of 2. preparation method of the nitrogen oxygen doping hollow Nano charcoal ball material described in claim 1, it is characterised in that including with Lower step：
    Step 1：Aniline monomer 0.5mL is dissolved in 0.15molL-1Sulfuric acid solution in stirring 30min be well mixed, Ran Houjia Enter the hydrogenperoxide steam generator that 0.5mL volume ratios are 30% and the ammonium persulfate solution that 10mL concentration is 0.01M, continue to stir 30min is allowed to well mixed, in 120-170 DEG C of hydro-thermal reaction 1-10h, filters afterwards, and by product absolute ethyl alcohol and go from Sub- water clean it is colourless to filtrate, dry, obtain polyaniline hollow nanospheres；
    Step 2：By nitrogen oxygen doping hollow nano-sphere in air atmosphere, oxidation processes 2h at 200 DEG C, obtain pre-oxidizing hollow Ball product；
    Step 3：Pre-oxidation product obtained by step 2 is taken, is put into high temperature carbonization furnace, is heated to target temperature under an inert atmosphere Degree, insulation, produces polyaniline hollow ball sample.
  3. 3. the preparation method of nitrogen oxygen doping hollow Nano charcoal ball material according to claim 2, it is characterised in that：Carbonized Cheng Zhong, its target temperature carbonized are 600-900 DEG C.
  4. 4. the preparation method of nitrogen oxygen doping hollow Nano charcoal ball material according to claim 2, it is characterised in that：Carbonized Cheng Zhong, soaking time 2-6h.
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CN105129809A (en) * 2015-10-12 2015-12-09 上海第二工业大学 Sea-urchin-shaped nanometer nickel silicate hollow sphere and preparation method thereof
CN107359313A (en) * 2016-05-10 2017-11-17 北京化工大学 A kind of preparation method and its stored energy application of the hollow multi-cavity carbon nanospheres of polyaniline
CN107731557B (en) * 2017-08-23 2019-03-22 温州大学 Nitrogen oxygen codope porous carbon/ferriferrous oxide composite material preparation method and application
CN109110745A (en) * 2018-09-27 2019-01-01 北京长城华冠汽车科技股份有限公司 A kind of preparation method of the hollow Nano carbon balls composite material of N doping multi-pore channel
CN110342492B (en) * 2019-06-13 2021-03-09 陕西浦士达环保科技有限公司 Preparation method of nitrogen-oxygen doped carbon nano tube/porous carbon
CA3110367A1 (en) * 2021-02-25 2022-08-25 Sixring Inc. Modified sulfuric acid and uses thereof
CA3110388A1 (en) * 2021-02-25 2022-08-25 Sixring Inc. Arylsulfonic acid - modified sulfuric acide and uses thereof
CN113582161A (en) * 2021-08-10 2021-11-02 复旦大学 Small-size porous nitrogen-doped carbon nanoparticles and preparation method thereof

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