CN109979762A - A kind of preparation method of porous ferroferric oxide/carbon composite electrode material - Google Patents

A kind of preparation method of porous ferroferric oxide/carbon composite electrode material Download PDF

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CN109979762A
CN109979762A CN201910330462.2A CN201910330462A CN109979762A CN 109979762 A CN109979762 A CN 109979762A CN 201910330462 A CN201910330462 A CN 201910330462A CN 109979762 A CN109979762 A CN 109979762A
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porous
electrode material
ferroferric oxide
carbon composite
fecl
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樊新
张文瑞
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Guilin University of Technology
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Guilin University of Technology
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01GCAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22Electrodes
    • H01G11/30Electrodes characterised by their material
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01GCAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22Electrodes
    • H01G11/30Electrodes characterised by their material
    • H01G11/32Carbon-based
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01GCAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22Electrodes
    • H01G11/30Electrodes characterised by their material
    • H01G11/46Metal oxides
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/13Energy storage using capacitors

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  • Engineering & Computer Science (AREA)
  • Power Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Electric Double-Layer Capacitors Or The Like (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

The invention discloses a kind of preparation methods of porous ferroferric oxide/carbon composite electrode material.Porous Fe is prepared with hydro-thermal method3O4, then in Fe3O4On the basis of with oxidizing process polymerization aniline prepare porous core-shell particles Fe3O4/ C composite.The method of the present invention preparation process is simple, reliable, environmentally protective, and obtained ferroferric oxide/carbon composite material has regular space structure, good dispersibility, high-energy density and power density, outstanding cycle performance, it is a kind of ideal electrode material for super capacitor, is especially suitable for industrialized production.

Description

A kind of preparation method of porous ferroferric oxide/carbon composite electrode material
Technical field
The invention belongs to new energy field of material technology, in particular to a kind of porous ferroferric oxide/carbon composite electrode The preparation method of material.
Background technique
Supercapacitor is due to high-energy density and power density and outstanding cycle performance etc. and as quick With the primary selection in high-power energy stocking system field.Electrode material in supercapacitor plays the performance of supercapacitor To vital effect, therefore, realize that the widely applied most important thing of supercapacitor is to prepare and develop high performance electricity Pole material.
Transition metal oxide and carbon material are the common two kinds of materials of electrode material for super capacitor.Utilize both materials The advantageous characteristic of material and to overcome deficiency existing for homogenous material to prepare combination electrode material be current electrode material for super capacitor One of hot spot of research.
The invention proposes a kind of preparation method of porous ferroferric oxide/carbon composite electrode material, supercapacitor with The features such as its high power density, short charge and discharge time, long circulation life and be concerned, promoting its energy density is currently to need One of difficult point captured.Many transition metal oxides specific capacity generally with higher, such as RuO2, Fe3O4In metal oxygen Among compound, ferroso-ferric oxide have the characteristics that it is cheap, without environmental toxicity, Yi Fasheng redox reaction, be considered as pole Has the electrode material for super capacitor of potentiality.The present invention is prepared for porous Fe by hydro-thermal method3O4/ C composite, passes through The means such as XRD, FTIR are characterized, it was demonstrated that the pyrolysismethod can synthesize porous Fe really3O4/ C nano composite material.To the material Carry out cyclic voltammetry, curve approximation rectangle the result shows that the composite material have fake capacitance characteristic.Li et al. proposes one Kind carbon shell protection scheme, and a kind of iron oxide-carbon nano rod array cathode of binder free is reported, which has preferable Cyclical stability.It provides high energy and power density, has been more than many flexible super capacitors reported recently.Highest Energy density values even close to Li hull cell, be several times of 5.5 V/100 mF supercapacitors of business.Especially this is mixed It attaches together and sets in the case where being significantly bent, mechanical pressure being big, temperature increases (reaching as high as 80 degrees Celsius), be still able to maintain good Chemical property, environmental suitability is strong.(Li R, Wang Y, Zhou C, et al. Carbon-Stabilized High‐Capacity Ferroferric Oxide Nanorod Array for Flexible Solid‐State Alkaline Battery–Supercapacitor Hybrid Device with High Environmental Suitability [J] Advanced Functional Materials, 2015,25 (33): 5384-5394.).Wang Chemical activation is carried out to coal-tar residue Deng using potassium hydroxide, then carries out carbonization treatment, is prepared for that there is tridimensional network Oxygen-enriched active carbon.Nanostructure Fe is prepared for using simple chemical coprecipitation3O4/ AC composite material, as supercapacitor Active electrode material.With pure Fe3O4It is compared with AC, Fe3O4Significantly improving for/AC nanocomposite chemical property can close Reason ground is attributed to Fe3O4Positive synergistic effect between AC.(Wang Y, He P, Zhao X, et al. Coal tar residues-based nanostructured activated carbon/Fe3O4 composite electrode materials for supercapacitors[J]. Journal of Solid State Electrochemistry, 2014,18 (3): 665-672.).
Therefore high-performance super capacitor electrode material is prepared for it in electrochemical energy storage using simple synthetic technology The application in field is of great significance.The present invention is with FeCl3It is raw material with aniline, porous core-shell particles is prepared using hydro-thermal method Fe3O4/ C composite.
Summary of the invention
The object of the present invention is to provide a kind of preparation methods of porous ferroferric oxide/carbon composite electrode material.
Thinking of the present invention: porous Fe is prepared with hydro-thermal method3O4, then in Fe3O4On the basis of polymerization aniline prepare it is porous Core-shell particles Fe3O4/ C composite.
Specific steps are as follows:
(1) by 2.03 g Fe3O4·6H2O、1.85 g CH3COONa and 0.09 g Nano-meter SiO_22It is dissolved in 50 mL solvents, 30 min of magnetic agitation, is allowed to form uniform clear solution, then heats 8 h in 180 DEG C of reaction kettles, is cooled to room temperature Afterwards, it with deionized water and ethanol washing, is finally dried at 80 DEG C, intermediate product is made.
(2) the HF solution that intermediate product mass percent concentration made from step (1) is 2% is impregnated into 60 min, then It is cleaned 6 times with deionized water, it is finally dry at 80 DEG C, porous Fe is made3O4
(3) porous Fe made from 0.5 g step (2) is taken3O4It is dissolved in 40 mL deionized waters, 30 min of ultrasound add 0.1g lauryl sodium sulfate, stirs evenly, and adds 0.5 ~ 2mL aniline monomer, 20 min is stirred under the conditions of ice-water bath, dropwise It is added and contains 3.1 ~ 12.4 g FeCl3FeCl3Solution reacts 3 h, and Magneto separate goes out magnetic substance, with ethyl alcohol and deionization Water washing, products therefrom is dry at 80 DEG C, obtains Fe3O4/ PANI presoma.
(4) by Fe made from step (3)3O4/ PANI presoma is heated to 600 under Ar atmosphere with the rate of 3 DEG C/min DEG C heat preservation 3 h, obtain porous ferroferric oxide/carbon composite electrode material.
The solvent is the mixture of ethylene glycol or deionized water or both.
The method of the present invention preparation process is simple, reliable, environmentally protective, and obtained ferroferric oxide/carbon composite material has There are regular space structure, good dispersibility, high-energy density and power density, outstanding cycle performance, is a kind of ideal Electrode material for super capacitor, be especially suitable for industrialized production.
Specific embodiment
Embodiment 1:
(1) by 2.03 g Fe3O4·6H2O、1.85 g CH3COONa and 0.09 g Nano-meter SiO_22It is dissolved in 33 mL ethylene glycol In 17 mL deionized waters, 30 min of magnetic agitation is allowed to form uniform clear solution, then in 180 DEG C of reaction kettles 8 h are heated, after being cooled to room temperature, with deionized water and ethanol washing, is finally dried at 80 DEG C, intermediate product is made.
(2) the HF solution that intermediate product mass percent concentration made from step (1) is 2% is impregnated into 60 min, then It is cleaned 6 times with deionized water, it is finally dry at 80 DEG C, porous Fe is made3O4
(3) porous Fe made from 0.5 g step (2) is taken3O4It is dissolved in 40 mL deionized waters, 30 min of ultrasound add 0.1g lauryl sodium sulfate, stirs evenly, and adds 1 mL aniline monomer, stirs 20 min under the conditions of ice-water bath, dropwise plus Enter to contain 6.2 g FeCl3FeCl3Solution reacts 3 h, and Magneto separate goes out magnetic substance, washed with ethyl alcohol and deionized water, Products therefrom is dry at 80 DEG C, obtains Fe3O4/ PANI presoma.
(4) by Fe made from step (3)3O4/ PANI presoma is heated to 600 under Ar atmosphere with the rate of 3 DEG C/min DEG C heat preservation 3 h, obtain porous ferroferric oxide/carbon composite electrode material.
Embodiment 2:
(1) by 2.03 g Fe3O4·6H2O、1.85 g CH3COONa and 0.09 g Nano-meter SiO_22It is dissolved in 25 mL ethylene glycol In 25 mL deionized waters, 30 min of magnetic agitation is allowed to form uniform clear solution, then in 180 DEG C of reaction kettles 8 h are heated, after being cooled to room temperature, with deionized water and ethanol washing, is finally dried at 80 DEG C, intermediate product is made.
(2) the HF solution that intermediate product mass percent concentration made from step (1) is 2% is impregnated into 60 min, then It is cleaned 6 times with deionized water, it is finally dry at 80 DEG C, porous Fe is made3O4
(3) porous Fe made from 0.5 g step (2) is taken3O4It is dissolved in 40 mL deionized waters, 30 min of ultrasound add 0.1g lauryl sodium sulfate, stirs evenly, and adds 1 mL aniline monomer, stirs 20 min under the conditions of ice-water bath, dropwise plus Enter to contain 6.2 g FeCl3FeCl3Solution reacts 3 h, and Magneto separate goes out magnetic substance, washed with ethyl alcohol and deionized water, Products therefrom is dry at 80 DEG C, obtains Fe3O4/ PANI presoma.
(4) by Fe made from step (3)3O4/ PANI presoma is heated to 600 under Ar atmosphere with the rate of 3 DEG C/min DEG C heat preservation 3 h, obtain porous ferroferric oxide/carbon composite electrode material.
Embodiment 3:
(1) by 2.03 g Fe3O4·6H2O、1.85 g CH3COONa and 0.09 g Nano-meter SiO_22It is dissolved in 50 mL ethylene glycol In, 30 min of magnetic agitation is allowed to form uniform clear solution, then heats 8 h in 180 DEG C of reaction kettles, is cooled to room Wen Hou is finally dried at 80 DEG C with deionized water and ethanol washing, and intermediate product is made.
(2) the HF solution that intermediate product mass percent concentration made from step (1) is 2% is impregnated into 60 min, then It is cleaned 6 times with deionized water, it is finally dry at 80 DEG C, porous Fe is made3O4
(3) porous Fe made from 0.5 g step (2) is taken3O4It is dissolved in 40 mL deionized waters, 30 min of ultrasound add 0.1g lauryl sodium sulfate, stirs evenly, and adds 1 mL aniline monomer, stirs 20 min under the conditions of ice-water bath, dropwise plus Enter to contain 6.2 g FeCl3FeCl3Solution reacts 3 h, and Magneto separate goes out magnetic substance, washed with ethyl alcohol and deionized water, Products therefrom is dry at 80 DEG C, obtains Fe3O4/ PANI presoma.
(4) by Fe made from step (3)3O4/ PANI presoma is heated to 600 under Ar atmosphere with the rate of 3 DEG C/min DEG C heat preservation 3 h, obtain porous ferroferric oxide/carbon composite electrode material.
Embodiment 4:
The step of repeating embodiment 1, the additional amount for only changing the step aniline monomer in (5) is 0.5 mL and FeCl3Solution (contains 3.1 g FeCl3).
Embodiment 5:
The step of repeating embodiment 1, the additional amount for only changing the step aniline monomer in (5) is 2 mL and FeCl3Solution (contains 12.4 g FeCl3).
Embodiment 6:
The step of repeating embodiment 2, the additional amount for only changing the step aniline monomer in (5) is 0.5 mL and FeCl3Solution (contains 3.1 g FeCl3).
Embodiment 7:
The step of repeating embodiment 2, the additional amount for only changing the step aniline monomer in (5) is 2 mL and FeCl3Solution (contains 12.4 g FeCl3).
Embodiment 8:
The step of repeating embodiment 3, the additional amount for only changing the step aniline monomer in (5) is 0.5 mL and FeCl3Solution (contains 3.1 g FeCl3).
Embodiment 9:
The step of repeating embodiment 2, the additional amount for only changing the step aniline monomer in (5) is 2 mL and FeCl3Solution (contains 12.4 g FeCl3).

Claims (1)

1. a kind of preparation method of porous ferroferric oxide/carbon composite electrode material, it is characterised in that specific steps are as follows:
(1) by 2.03 g Fe3O4·6H2O、1.85 g CH3COONa and 0.09 g Nano-meter SiO_22It is dissolved in 50 mL solvents, 30 min of magnetic agitation, is allowed to form uniform clear solution, then heats 8 h in 180 DEG C of reaction kettles, is cooled to room temperature Afterwards, it with deionized water and ethanol washing, is finally dried at 80 DEG C, intermediate product is made;
(2) the HF solution that intermediate product mass percent concentration made from step (1) is 2% is impregnated into 60 min, then spent Ionized water cleans 6 times, finally dry at 80 DEG C, and porous Fe is made3O4
(3) porous Fe made from 0.5 g step (2) is taken3O4It is dissolved in 40 mL deionized waters, 30 min of ultrasound add 0.1g ten Sodium dialkyl sulfate stirs evenly, and adds 0.5 ~ 2mL aniline monomer, 20 min are stirred under the conditions of ice-water bath, is added dropwise and contains 3.1~12.4 g FeCl3FeCl3Solution reacts 3 h, and Magneto separate goes out magnetic substance, washed with ethyl alcohol and deionized water, Products therefrom is dry at 80 DEG C, obtains Fe3O4/ PANI presoma;
(4) by Fe made from step (3)3O4/ PANI presoma is heated to 600 DEG C of guarantors under Ar atmosphere with the rate of 3 DEG C/min 3 h of temperature, obtain porous ferroferric oxide/carbon composite electrode material;
The solvent is the mixture of ethylene glycol or deionized water or both.
CN201910330462.2A 2019-04-23 2019-04-23 A kind of preparation method of porous ferroferric oxide/carbon composite electrode material Pending CN109979762A (en)

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Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102718279A (en) * 2012-06-05 2012-10-10 陕西科技大学 Method for removing humic acid pollutants from water by magnetic polyaniline adsorbent
CN103506078A (en) * 2013-10-14 2014-01-15 陕西盛迈石油有限公司 Preparation method of Fe3O4/ C nanoparticles
CN103613760A (en) * 2013-12-10 2014-03-05 兰州理工大学 Method for preparing polyaniline/ferroferric oxide electromagnetic composite material
CN103611479A (en) * 2013-12-04 2014-03-05 江南大学 Preparation method of Fe3O4/SiO2/PANI (Polyaniline) nano particle with core-shell structure
CN103980691A (en) * 2014-06-02 2014-08-13 吉林大学 Polyaniline/carbon/ferroferric oxide hollow microsphere and polyaryletherketone composite material, preparation method and application thereof
CN105253920A (en) * 2015-09-24 2016-01-20 桂林理工大学 Preparation method of ferriferrous oxide@nitrogen doped carbon compound
CN108039257A (en) * 2017-12-27 2018-05-15 山东大学 A kind of three-dimensional porous sheet ferroferric oxide/carbon nano electromagnetic ripple absorbing material and preparation method thereof
CN108827929A (en) * 2018-04-17 2018-11-16 华东理工大学 A kind of SERS probe and preparation method thereof based on MOFs

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102718279A (en) * 2012-06-05 2012-10-10 陕西科技大学 Method for removing humic acid pollutants from water by magnetic polyaniline adsorbent
CN103506078A (en) * 2013-10-14 2014-01-15 陕西盛迈石油有限公司 Preparation method of Fe3O4/ C nanoparticles
CN103611479A (en) * 2013-12-04 2014-03-05 江南大学 Preparation method of Fe3O4/SiO2/PANI (Polyaniline) nano particle with core-shell structure
CN103613760A (en) * 2013-12-10 2014-03-05 兰州理工大学 Method for preparing polyaniline/ferroferric oxide electromagnetic composite material
CN103980691A (en) * 2014-06-02 2014-08-13 吉林大学 Polyaniline/carbon/ferroferric oxide hollow microsphere and polyaryletherketone composite material, preparation method and application thereof
CN105253920A (en) * 2015-09-24 2016-01-20 桂林理工大学 Preparation method of ferriferrous oxide@nitrogen doped carbon compound
CN108039257A (en) * 2017-12-27 2018-05-15 山东大学 A kind of three-dimensional porous sheet ferroferric oxide/carbon nano electromagnetic ripple absorbing material and preparation method thereof
CN108827929A (en) * 2018-04-17 2018-11-16 华东理工大学 A kind of SERS probe and preparation method thereof based on MOFs

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Application publication date: 20190705