CN109559898A - A kind of preparation method of the carbon sponge flexible composite of cobalt sulfide iron nanotube load - Google Patents

A kind of preparation method of the carbon sponge flexible composite of cobalt sulfide iron nanotube load Download PDF

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CN109559898A
CN109559898A CN201811330816.5A CN201811330816A CN109559898A CN 109559898 A CN109559898 A CN 109559898A CN 201811330816 A CN201811330816 A CN 201811330816A CN 109559898 A CN109559898 A CN 109559898A
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carbon sponge
cobalt
cobalt sulfide
sponge
preparation
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黄云鹏
崔芬
华明清
赵岩
李华明
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Jiangsu University
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Jiangsu University
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    • 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
    • H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
    • B01J27/04—Sulfides
    • B01J27/043—Sulfides with iron group metals or platinum group metals
    • B01J35/33—
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    • B82—NANOTECHNOLOGY
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    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
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    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
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    • H01M4/64—Carriers or collectors
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    • Y02E60/10—Energy storage using batteries

Abstract

The invention belongs to functionalization porous nanometer material fields, are related to a kind of preparation method of the carbon sponge flexible composite of cobalt sulfide iron nanotube load；Specific steps are as follows: commercial melamine sponge is cut, distilled water and washes of absolute alcohol are then used, after dry, under nitrogen or argon atmosphere, melamine sponge is calcined by temperature programming, carbonization treatment is carried out, obtains carbon sponge after cooling；Prepare the mixed solution containing molysite and cobalt salt, carbon sponge is immersed in mixed solution, and pH auxiliary agent is added, carry out hydro-thermal reaction, obtain ferro-cobalt oxygen presoma-carbon sponge composite material, it is then immersed in sulfur agent solution, carries out secondary hydro-thermal reaction, obtain the carbon sponge composite material of cobalt sulfide iron nanotube load；The present invention successfully solves the problems, such as that nano material is easy to reunite using flexible, porous, self-supporting carbon sponge as growth templates；And obtained composite material has largely exposed active site, hole abundant and good electric conductivity.

Description

A kind of preparation method of the carbon sponge flexible composite of cobalt sulfide iron nanotube load
Technical field
The invention belongs to functionalization porous nanometer material fields, and in particular to a kind of carbon sea of cobalt sulfide iron nanotube load The preparation method of continuous flexible composite.
Background technique
In recent years, increasingly depleted with non-renewable energy resources, demand of the people to new energy sharply increases.Solar energy, The clean energy resourcies such as wind energy and tide energy have the shortcomings that interval is discontinuous, therefore need the new energy of exploitation efficiently, economic and deposit Storage and switch technology.Supercapacitor, fuel cell, lithium ion battery are considered as three kinds of electrifications most with prospects at present Learn energy storage and converting system.And in order to enhance the energy storage efficiency of three of the above energy storage and converting system and manufacture at This, to promote the industrialization of this kind of new energy technology, researchers are devoted to find and develop efficient, low cost Base metal base electrode material.
Transient metal sulfide is because have electro-chemical activity more higher than oxide and higher theoretical specific capacitance to form For research hotspot.Wherein, the bimetallic sulfide being made of different transition metal elements can be by the different valence state of two kinds of metals Between redox reaction and metallic element between synergistic effect and obtain higher specific capacitance.In this kind of bimetallic In sulfide, the two kinds of metallic elements vulcanized in ferro-cobalt all have higher oxygen reduction activation, and redox more abundant Valence state can provide superior capacitive property.However, the lower electric conductivity of bimetallic sulfide still become restrict its performance mention The key factor risen.
In recent years, with the fast development of wearable electronic product, people propose the flexibility and lightweight performance of energy storage device More requirements are gone out.But common traditional energy storage device is all rigid and non-lightweight, this is just to electrode material and electrode base The design at bottom proposes bigger challenge.
Summary of the invention
In view of the deficiencies of the prior art, present invention seek to address that one of above problem；The present invention provides a kind of three-dimensional, certainly branch The preparation method of the carbon sponge flexible composite of the cobalt sulfide iron nanotube load of support；The carbon of preparation is handled using high temperature cabonization Sponge is conductive, self-supporting template, and the carbon sponge flexible compound material of cobalt sulfide iron nanotube load is synthesized by two one-step hydrothermals Material.
In order to achieve the goal above, the specific steps of the present invention are as follows:
(1) take commercial melamine sponge into spare after dry with distilled water and washes of absolute alcohol；
(2) under nitrogen or argon atmosphere, the melamine sponge obtained by temperature programming calcining step (1) is carried out Carbonization treatment obtains carbon sponge after cooling；
(3) mixed solution of certain density molysite and cobalt salt is prepared；Carbon sponge obtained in step (2) is immersed and is mixed In solution, and pH auxiliary agent is added, carries out hydro-thermal reaction, obtain ferro-cobalt oxygen presoma-carbon sponge composite material；
(4) certain density sulfur agent solution is prepared, ferro-cobalt oxygen presoma-carbon sponge obtained in step (3) is compound Material immerses in sulfur agent solution, carries out secondary hydro-thermal reaction, obtains the carbon sponge composite material of cobalt sulfide iron nanotube load.
Preferably, the size of melamine sponge described in step (1) is 5cm × 2cm × 0.5cm.
Preferably, the design parameter of the calcining of temperature programming described in step (2) are as follows: 5~10 DEG C/min of heating rate, temperature 500~800 DEG C, 0.5~3h of time.
Preferably, molysite described in step (3) is Fe (NO3)3, the cobalt salt is Co (NO3)2, the mixed solution Solvent be deionized water.
Preferably, molysite molar concentration is 10~60mM in step (3) described mixed solution.
Preferably, in step (3) described mixed solution cobalt salt 20~120mM of molar concentration.
Preferably, the molar concentration of pH auxiliary agent described in step (3) is 30~180mM；The pH auxiliary agent is urea and fluorine The molar concentration rate of change ammonium, urea and ammonium fluoride is 1:1.
Preferably, the temperature of hydro-thermal reaction described in step (3) is 100~140 DEG C, and the reaction time is 8~12h.
Preferably, the molar concentration of sulfur agent solution described in step (4) is 20~50mM, and the vulcanizing agent is sulphur Change sodium.
Preferably, the temperature of secondary hydro-thermal reaction described in step (4) is 100~140 DEG C, and the reaction time is 8~12h.
The present invention relates to two basic principles:
(1) by melamine sponge high temperature cabonization at carbon sponge can retain the porous structure of sponge, good flexibility and While three-dimensional network, substantially enhance its electric conductivity, to establish to construct the flexible electrode material with excellent electrochemical performance Fixed basis.
(2) molecular formula of iron cobalt oxide presoma is FeCo2(C2O4)3, pattern, which is vulcanized by acicular texture as tubular structure, is By S2-And C2O4 2-Between anion exchange reaction caused by.
Beneficial effect
(1) preparation process of the present invention is simple, easily operated, safety and environmental protection, and reagent used will not be to human body and environment Cause adverse effect.
(2) mentality of designing of the present invention is ingenious, using flexible, porous, self-supporting carbon sponge as growth templates, successfully solves Nano material problem easy to reunite；And present invention selection carbon sponge substrate can also enhance the electric conductivity of composite material.
(3) the carbon sponge flexible composite of the cobalt sulfide iron nanotube load prepared by the present invention has largely exposure Active site, hole abundant and good electric conductivity, can be used as electrochemical catalyst, electrode material for super capacitor and The electrode material of the new energy devices such as lithium ion battery.
Detailed description of the invention
Fig. 1 is iron cobalt oxide presoma-carbon sponge composite material electromicroscopic photograph prepared by embodiment 1；The wherein electricity that A is 20 μm Mirror photo；The electromicroscopic photograph that B is 1 μm.
Fig. 2 is the electromicroscopic photograph of the carbon sponge of cobalt sulfide iron nanotube load prepared by embodiment 2；Wherein A is 10 μm Electromicroscopic photograph；B is the electromicroscopic photograph of 200nm.
Fig. 3 is the carbon sponge of ferro-cobalt oxygen presoma-carbon sponge prepared by embodiment 2 and the load of cobalt sulfide iron nanotube XRD spectra.
Specific embodiment
Below with reference to specific example, the present invention is further explained, these embodiments be merely to illustrate the present invention rather than It limits the scope of the invention.It will be appreciated by those persons skilled in the art that still can modify to the present invention or Equivalent replacement；And all do not depart from the technical solution and its improvement of the spirit and scope of the present invention, should all cover in the present invention Scope of the claims in.
Embodiment 1:
(1) commercial melamine sponge is divided into 5cm × 2cm × 0.5cm strip, and with distilled water and anhydrous second Alcohol cleans up, and is subsequently dried overnight, spare；
(2) clean melamine sponge is placed in temperature programmed control tube furnace, in a nitrogen atmosphere, with 5 DEG C/min's Heating rate is warming up to 500 DEG C from 25 DEG C, and keeps 0.5h, and carbon sponge is obtained after natural cooling；
(3) using deionized water as solvent, ferric nitrate and cobalt nitrate is added, obtains mixed solution；Wherein nitre in mixed solution Sour concentration of iron is 10mM, and nitric acid cobalt concentration is 20mM；Carbon sponge is added, and urea and ammonium fluoride is added；In the mixed solution made Urea concentration is 30mM, and fluorination ammonium concentration is 30mM；It is transferred in the reaction kettle of polytetrafluoroethyllining lining, under the conditions of 100 DEG C 12h is reacted, cleaned, drying obtains iron cobalt oxide presoma-carbon sponge composite material；
(4) again by obtained iron cobalt oxide presoma-carbon sponge composite material be dipped into 30mL concentration be 20mM vulcanized sodium it is molten It in liquid, and is transferred in reaction kettle, is taken out after reacting 8h under the conditions of 100 DEG C, product is cleaned, is dried, is finally obtained The carbon sponge composite material of the cobalt sulfide iron nanotube load of low carrying capacity.
Embodiment 2:
(1) commercial melamine sponge is divided into 5cm × 2cm × 0.5cm strip, and with distilled water and anhydrous second Alcohol cleans up, and is subsequently dried overnight, spare；
(2) clean melamine sponge is placed in temperature programmed control tube furnace, in a nitrogen atmosphere, with 8 DEG C/min's Heating rate is warming up to 700 DEG C from 25 DEG C, and keeps 1.5h, and carbon sponge is obtained after Temperature fall；
(3) using deionized water as solvent, ferric nitrate and cobalt nitrate is added, obtains mixed solution；Wherein nitre in mixed solution Sour concentration of iron is 30mM, and nitric acid cobalt concentration is 60mM；Carbon sponge is added, and urea and ammonium fluoride is added；In the mixed solution made Urea concentration is 80mM, and fluorination ammonium concentration is 80mM；It is transferred in the reaction kettle of polytetrafluoroethyllining lining, under the conditions of 120 DEG C 10h is reacted, cleaned, drying obtains iron cobalt oxide presoma-carbon sponge composite material；
(4) obtained forerunner's composite material is dipped into the sodium sulfide solution that 30mL concentration is 40mM again, and be transferred to In reaction kettle, is taken out after reacting 10h in 120 DEG C of baking ovens, product is cleaned, is dried, the sulphur of medium carrying capacity is finally obtained Change the nano tube supported carbon sponge composite material of ferro-cobalt.
By the carbon sponge composite material of obtained cobalt sulfide iron nanotube load directly as super capacitor anode material, The nickel foam coated using acetylene black is as negative electrode material, using the KOH of 5M concentration as electrolyte, assembles Asymmetric Supercapacitor Device, and assess the capacitive property of device.
Embodiment 3:
(1) commercial melamine sponge is divided into 5cm × 2cm × 0.5cm strip, and with distilled water and anhydrous second Alcohol cleans up, and is subsequently dried overnight, spare；
(2) clean melamine sponge is placed in temperature programmed control tube furnace, in a nitrogen atmosphere, with 10 DEG C/min's Heating rate is warming up to 800 DEG C from 25 DEG C, and keeps 3h, and carbon sponge is obtained after Temperature fall；
(3) using deionized water as solvent, ferric nitrate and cobalt nitrate is added, obtains mixed solution；Wherein nitre in mixed solution Sour concentration of iron is 60mM, and nitric acid cobalt concentration is 120mM；Carbon sponge is added, and urea and ammonium fluoride is added；In the mixed solution made Urea concentration is 180mM, and fluorination ammonium concentration is 180mM；It is transferred in the reaction kettle of polytetrafluoroethyllining lining, in 140 DEG C of conditions Lower reaction 12h, cleaned, drying, obtains iron cobalt oxide presoma-carbon sponge composite material；
(4) obtained forerunner's composite material is dipped into the sodium sulfide solution that 30mL concentration is 50mM again, and be transferred to In reaction kettle, is taken out after reacting 12h in 140 DEG C of baking ovens, product is cleaned, is dried, the vulcanization of big carrying capacity is finally obtained The nano tube supported carbon sponge composite material of ferro-cobalt.
Present invention vulcanization ferro-cobalt obtained is characterized using scanning electron microscope (SEM) and X-ray diffraction (XRD) to receive The pattern and composition of the carbon sponge flexible composite of mitron load, result are as follows；
Fig. 1 is iron cobalt oxide presoma-carbon sponge composite material electromicroscopic photograph prepared by embodiment 1；As shown in Figure 1, first After secondary hydro-thermal reaction, iron cobalt oxide presoma is grown on carbon sponge vertically in the form of nanoneedle, and it distributes very evenly, Apparent reunion is not observed；Nanoneedle length is 5-8 μm, diameter 400-500nm；Moreover, iron cobalt oxide presoma-carbon sponge Composite material still has three-dimensional net structure abundant.
Fig. 2 is the electromicroscopic photograph of the carbon sponge of cobalt sulfide iron nanotube load prepared by embodiment 2；As shown in Fig. 2, second After secondary hydro-thermal reaction, iron cobalt oxide presoma nanoneedle is converted into the cobalt sulfide iron nanotube with uniform hollow structure, institute The carbon sponge composite material of cobalt sulfide iron nanotube load maintain the three dimensional skeletal structure of carbon sponge and porous well Characteristic.
Fig. 3 is the carbon sponge of ferro-cobalt oxygen presoma-carbon sponge prepared by embodiment 2 and the load of cobalt sulfide iron nanotube XRD spectra；It is as shown in Figure 3: structural characterization being carried out to resulting composite material using XRD, can obviously observe and belong to iron cobalt oxide A series of diffraction maximums of presoma and vulcanization ferro-cobalt, it was confirmed that the successful preparation of composite material.
The carbon sponge flexible composite of the load of cobalt sulfide iron nanotube prepared by the present invention has largely exposed work Property site, hole abundant and good electric conductivity, can be used as electrochemical catalyst, electrode material for super capacitor and lithium The electrode material of the new energy devices such as ion battery.

Claims (10)

1. a kind of preparation method of the carbon sponge flexible composite of cobalt sulfide iron nanotube load, which is characterized in that specific step It is rapid as follows:
(1) commercial melamine sponge is taken, it is spare after dry with distilled water and washes of absolute alcohol；
(2) it under nitrogen or argon atmosphere, is carried out at carbonization by the melamine sponge that temperature programming calcining step (1) obtains Reason obtains carbon sponge after cooling；
(3) mixed solution of certain density molysite and cobalt salt is prepared；Carbon sponge obtained in step (2) is immersed into mixed solution In, and pH auxiliary agent is added, hydro-thermal reaction is carried out, ferro-cobalt oxygen presoma-carbon sponge composite material is obtained；
(4) certain density sulfur agent solution is prepared, by ferro-cobalt oxygen presoma-carbon sponge composite material obtained in step (3) It immerses in sulfur agent solution, carries out secondary hydro-thermal reaction, obtain the carbon sponge composite material of cobalt sulfide iron nanotube load.
2. a kind of preparation side of the carbon sponge flexible composite of cobalt sulfide iron nanotube load according to claim 1 Method, which is characterized in that the design parameter of the calcining of temperature programming described in step (2) are as follows: 5~10 DEG C/min of heating rate, temperature 500~800 DEG C, 0.5~3 h of time.
3. a kind of preparation side of the carbon sponge flexible composite of cobalt sulfide iron nanotube load according to claim 1 Method, which is characterized in that molysite molar concentration is 10~60 mM in step (3) described mixed solution, the molar concentration 20 of cobalt salt~ 120 mM。
4. a kind of preparation of the carbon sponge flexible composite of cobalt sulfide iron nanotube load according to claim 1 or 3 Method, which is characterized in that the molysite is Fe (NO3)3；The cobalt salt is Co (NO3)2。
5. a kind of preparation side of the carbon sponge flexible composite of cobalt sulfide iron nanotube load according to claim 1 Method, which is characterized in that the molar concentration of pH auxiliary agent described in step (3) is 30~180 mM；The pH auxiliary agent is urea and fluorine The molar concentration rate of change ammonium, urea and ammonium fluoride is 1:1.
6. a kind of preparation side of the carbon sponge flexible composite of cobalt sulfide iron nanotube load according to claim 1 Method, which is characterized in that the temperature of hydro-thermal reaction described in step (3) is 100~140 DEG C, and the reaction time is 8~12 h.
7. a kind of preparation side of the carbon sponge flexible composite of cobalt sulfide iron nanotube load according to claim 1 Method, which is characterized in that the molar concentration of sulfur agent solution described in step (4) is 20~50 mM.
8. a kind of preparation of the carbon sponge flexible composite of cobalt sulfide iron nanotube load according to claim 1 or claim 7 Method, which is characterized in that the vulcanizing agent is vulcanized sodium.
9. a kind of preparation side of the carbon sponge flexible composite of cobalt sulfide iron nanotube load according to claim 1 Method, which is characterized in that the temperature of secondary hydro-thermal reaction described in step (4) is 100~140 DEG C, and the reaction time is 8~12 h.
10. the carbon sponge flexible compound material of the cobalt sulfide iron nanotube load of preparation method preparation according to claim 1 Material is applied to the electrode material of supercapacitor.
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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110483049A (en) * 2019-09-23 2019-11-22 四川大学 Resilient magnetic carbon foam and preparation method thereof
CN110600278A (en) * 2019-08-22 2019-12-20 江苏大学 Pinecone-shaped MnO2Ball/foam carbon composite material and preparation method thereof
CN110875474A (en) * 2019-11-26 2020-03-10 侯丁茜 Polyacrylonitrile-Fe doped CoS-carbon nanotube negative electrode material and preparation method thereof
CN110885069A (en) * 2019-10-21 2020-03-17 山东科技大学 Three-dimensional macroporous ultralight carbon nitride material and preparation method thereof
CN111333041A (en) * 2020-02-24 2020-06-26 河北科技大学 Framework-supported aluminum nitride non-crystallized modified lithium negative electrode material and preparation method and application thereof
CN114525539A (en) * 2022-03-17 2022-05-24 山东大学 High-catalytic-activity and high-stability marynoite sulfide electrocatalyst, preparation method thereof and application thereof in electrolyzed water
CN114614027A (en) * 2022-02-18 2022-06-10 三峡大学 Preparation method of CoFe-S @3D-S-NCNT electrode and quasi-solid zinc-air battery
CN114843112A (en) * 2022-05-18 2022-08-02 广州大学 Preparation method of compressible pseudocapacitance electrode material with autocatalytic induced growth

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105280896A (en) * 2015-09-12 2016-01-27 复旦大学 Cobalt-nickel sulfide/carbon nanofiber composite material and preparation method and application thereof
CN106206078A (en) * 2016-07-27 2016-12-07 河南师范大学 A kind of manufacture method of ultracapacitor

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105280896A (en) * 2015-09-12 2016-01-27 复旦大学 Cobalt-nickel sulfide/carbon nanofiber composite material and preparation method and application thereof
CN106206078A (en) * 2016-07-27 2016-12-07 河南师范大学 A kind of manufacture method of ultracapacitor

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
YUNPENG HUANG等: "Hierarchical FeCo2S4 Nanotube Arrays Deposited on 3D Carbon Foam as Binder-free Electrodes for High-performance Asymmetric Pseudocapacitors", 《CHEMISTRY - AN ASIAN JOURNAL》 *

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* Cited by examiner, † Cited by third party
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CN110600278B (en) * 2019-08-22 2022-03-22 江苏大学 Pinecone-shaped MnO2Ball/foam carbon composite material and preparation method thereof
CN110483049A (en) * 2019-09-23 2019-11-22 四川大学 Resilient magnetic carbon foam and preparation method thereof
CN110483049B (en) * 2019-09-23 2020-06-16 四川大学 Resilient magnetic carbon foam and method of making same
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CN110875474A (en) * 2019-11-26 2020-03-10 侯丁茜 Polyacrylonitrile-Fe doped CoS-carbon nanotube negative electrode material and preparation method thereof
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