CN107978463A - A kind of preparation method of the ultracapacitor compound porous nanofiber of carbon@manganese dioxide - Google Patents

A kind of preparation method of the ultracapacitor compound porous nanofiber of carbon@manganese dioxide Download PDF

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Publication number
CN107978463A
CN107978463A CN201711312496.6A CN201711312496A CN107978463A CN 107978463 A CN107978463 A CN 107978463A CN 201711312496 A CN201711312496 A CN 201711312496A CN 107978463 A CN107978463 A CN 107978463A
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carbon
manganese dioxide
nanofiber
porous
compound porous
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程博闻
鞠敬鸽
康卫民
刘雍
闫静
邓南平
庄旭品
赵义侠
李磊
王利媛
梁跃耀
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Tianjin Polytechnic University
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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
    • H01G11/84Processes for the manufacture of hybrid or EDL capacitors, or components thereof
    • H01G11/86Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B82NANOTECHNOLOGY
    • B82YSPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00Nanotechnology for materials or surface science, e.g. nanocomposites
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B82NANOTECHNOLOGY
    • B82YSPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00Manufacture or treatment of nanostructures
    • 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
    • H01G11/24Electrodes 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
    • 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
    • H01G11/36Nanostructures, e.g. nanofibres, nanotubes or fullerenes
    • 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)
  • Chemical & Material Sciences (AREA)
  • Power Engineering (AREA)
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  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Composite Materials (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)
  • Electric Double-Layer Capacitors Or The Like (AREA)

Abstract

A kind of preparation method the present invention relates to ultracapacitor with the compound porous nanofiber of carbon@manganese dioxide, this method comprise the following steps:Using the porous carbon nanofiber of honeycomb structure as basis material, potassium permanganate is reduced into manganese dioxide nano-plates layer using the reproducibility of carbon itself and is filled in porous carbon nanofiber.Carbon@manganese dioxide composite materials produced by the present invention exist in the form of porous nano-fibre; manganese dioxide lamella is uniformly grown on cellular nano carbon fiber skeleton; improve the specific surface area of composite material; it is effective to avoid coming off for manganese dioxide during use; and preparation method is simple and practicable, reaction condition is gentle, cost is low, reproducible, is easy to large-scale production.

Description

A kind of preparation of the ultracapacitor compound porous nanofiber of carbon@manganese dioxide Method
Technical field
A kind of preparation method the present invention relates to ultracapacitor with the compound porous nanofiber of carbon@manganese dioxide, especially It is to provide a kind of on carbon nano-fiber matrix with through hole, aperture structure is controllable, manganese dioxide is in flaky nanometer structure , uniform intussusception growth in the interior bone structure of cellular carbon nano-fiber, specific surface area is big, binding ability between material By force, stability is good, and it is simple and practicable, environmentally friendly, can volume production the compound porous nanofiber of carbon@manganese dioxide preparation side Method.
Background technology
Manganese dioxide is a kind of oxide with essential industry purposes, because of excellent Molecular Adsorption performance, ion exchange It is performance, electro-magnetic wave absorption performance and chemical property (theoretical specific capacity is up to 1370F/g), rich reserves, cheap, right Advantages of environment protection and receive much concern, its catalysis, inhale ripple, the field such as electrochemistry shows superior application prospect.So And manganese dioxide has the relatively low (~10-6Scm of electronic conductivity-1), the defects of cycle performance is poor, limit its application. And carbon-based material has the advantages that high effective ratio area, electron conductivity are high, both are combined and is expected to acquisition and has two concurrently The high fake capacitance performance of manganese oxide electrode material simultaneously has the stability of carbon-based material, the composite material of electric conductivity.
Carbon-based material in common manganese dioxide/carbon composite material includes carbon fiber, graphene, carbon nanotubes, activity Charcoal etc..Wherein, carbon fiber specific surface area is smaller, can not provide enough activity in the application;And graphene and carbon nanotubes Preferably, but using higher price, volume production difficulty, large-scale application can be limited;Activated carbon cost is relatively low, abundance, and compares Surface area is big, the characteristics of due to it containing miscellaneous more, easy dusting, carrier can not be used as to provide application strongly to manganese dioxide.Porous carbon Nanofiber is a kind of One-dimensional nanoreticular carbon materials with abundant hole, have the characteristics that specific surface area greatly, good conductivity, with reference to The electrostatic reported is molten to blow efficient preparation method (Chinese invention patent CN105161722A), can realize low cost, high yield Amount, can become the excellent carrier material of manganese dioxide.
The preparation method of manganese dioxide/carbon composite material include embedded absorption method, direct blending, electrochemical deposition method, Situ Hydrothermal reduction method etc..S.Chen et al. (.Graphene Oxide-MnO such as Chen S., Zhu J.W., Wu X.D.2 Nanocomposites for Supercapacitors [J] .ACS Nano, 2010,4 (5):2822-2930.) by manganese ion GO lamellas are mixed into a manner of embedded adsorb, obtain manganese dioxide/graphene composite material, but manganese dioxide is in graphene film Uniformity and stability on layer is poor.(the carbon of the easy synthesis of the such as Bian Damin, Han Sheng, Zhang Xiaochen method of electrostatic spinning such as Bian Damin Preparation and research [J] the physics and engineering of nanofiber --- manganese dioxide electrode material for super capacitor, 26 (5):62-65, 74) by MnO2Particle is directly blended into the spinning solution containing carbon matrix precursor, is obtained after electrostatic spinning, pre-oxidation, carbonization treatment The carbon nano-fiber doped with MnO2 particles was obtained, but uniformity is poor, and MnO2Exist in granular form, part handles fiber Internal manganese dioxide particle can not provide its activity.(Liu J.W.Essner J., the Li J.Hybrid such as J.Liu Supercapacitor Based on Coaxially Coated Manganese Oxide on Vertically Aligned Carbon Nanofiber Arrays [J] .Chemistry Materials, 2010,22 (17):5022- 5030.) by the method for cathodic electrochemical deposition by nanoscale MnO2Film is uniformly wrapped in carbon fiber surface, M.S.Wu (Wu M.S., Guo Z.S., Jow J.J.Highly Regulated Electrodeposition of Needle-Like Manganese Oxide Nanofibers on Carbon Fiber Fabric for Electrochemical Capacitors [J] .Journal of Physical Chemistry C.2010,114 (49):21961-21867.) by pin Shape MnO2Nanofibres deposit has obtained good effect, but technique is cumbersome on conductive fibers, it is difficult to realizes rule Modelling produces.In contrast, Situ Hydrothermal method is due to easy to operate, and the reproducibility that carbon possesses in itself can be reduced directly KMnO4, And attract wide attention a kind of (such as Han Jinlei, Rong Changru, Zhang Kejin ultracapacitor manganese dioxide/carbon composite materials Preparation method:China, CN103545122A [P] .2014-01-29).Patent of the invention based on this seminar:A kind of lithium sulphur electricity Pond positive electrode porous carbon nanofiber film and preparation method thereof (application number:201510675761.1) on the basis of, with bee The porous carbon nanofiber of nest shape through-hole structure utilizes the reproducibility of its own as carbon skeleton, and potassium permanganate is reduced to Manganese dioxide is simultaneously grown in the honeycomb porous carbon nanofiber interior bone structure with sheet form, can effectively prevent reality The obscission of manganese dioxide in application process.In addition, the porous carbon nanofiber of bigger serface is as carbon skeleton so that carbon Skeleton and MnO2Compound site is more, helps to improve its chemical property.
The content of the invention
The object of the present invention is to provide a kind of method that can continuously prepare the compound porous nanofiber of carbon@manganese dioxide, Using the porous carbon nanofiber with cellular through-hole structure as carbon skeleton, and the reproducibility of its own is utilized, by Gao Meng Sour potassium is reduced to manganese dioxide and is grown on sheet form in the honeycomb porous carbon nanofiber interior bone structure, cost It is low, technique is simple, environmentally safe.The compound porous nanofiber of carbon@manganese dioxide prepared using the present invention, draw ratio Greatly, a large amount of holes are contained in surface and inside, and manganese dioxide lamella and porous carbon nanofiber skeleton binding ability are strong, and preparation side Method compared with conventional method have it is simple and practicable, reaction condition is gentle, cost is low, be easy to large-scale production.
A kind of ultracapacitor provided by the present invention compound porous nanofiber of carbon@manganese dioxide, it is characterised in that Cellular porous carbon nano-fiber basis material diameter range includes middle aperture model between 150~500nm in the corpus fibrosum Enclose for the continuous through holes of 30~100nm;The manganese dioxide is continuous inside porous carbon nanofiber in sheet homoepitaxial In through hole.
The preparation method of the compound porous nanofiber of carbon@manganese dioxide, its feature include the following steps:With cellular Carbon nano-fiber is dispersed in distilled water as basis material, the potassium permanganate powder of certain mass is added, one Determine to stir the regular hour at temperature, using the reproducibility of carbon itself in porous carbon fiber nanometer, potassium permanganate is reduced into two Manganese oxide so that manganese dioxide with the uniform intussusception growth of lamellar structure on porous carbon nanofiber skeleton, then through repeatedly washing, Absolute ethyl alcohol is washed and filtered, after vacuum drying, obtains the compound porous nanofiber of carbon@manganese dioxide.
Preferably, the detailed process of step (2) is:Cellular carbon nano-fiber basis material is passed through into stirring or ultrasound side Formula is dispersed in distilled water, using potassium permanganate: cellular carbon nano-fiber basis material mass ratio is added as 1: 20-5: 2 Potassium permanganate powder, and be heated to 50-90 DEG C, after stirring 2-24h, that is, obtains and is dispersed with that carbon@manganese dioxide is compound porous to be received The solution of rice fiber, through filtering, washing, ethanol is washed, and removes excess surface impurity, after vacuum drying, obtains carbon@manganese dioxide Compound porous nanofiber.
The compound porous nanofiber of carbon@manganese dioxide, it is characterised in that the manganese dioxide is lamella nano junction The manganese dioxide of structure, lamellar spacing 5-10nm.
Brief description of the drawings
Fig. 1 is the schematic diagram for preparing the compound porous nanofiber of carbon@manganese dioxide
Fig. 2 is porous carbon nanofiber scanning electron microscopic picture
Fig. 3 is the compound porous nanofiber scanning electron microscopic picture of carbon@manganese dioxide
Fig. 4 is porous carbon nanofiber transmission electron microscope picture
Fig. 5 is the compound porous nanofiber transmission electron microscope picture of carbon manganese dioxide
Fig. 6 is the compound porous nanofiber Elemental redistribution picture of carbon manganese dioxide
Embodiment
The present invention is described in further detail below in conjunction with the drawings and specific embodiments.
Embodiment 1
The present invention is first according to the patent of invention that this seminar has applied:A kind of lithium sulfur battery anode material is received with porous carbon Rice tunica fibrosa and preparation method thereof (application number:201510675761.1), based on this, prepare cellular porous carbon nanometer Fiber-based material 1.
Cellular carbon nano-fiber basis material is dispersed in distilled water by stirring or ultrasonic power, with honeycomb Shape carbon nano-fiber basis material: potassium permanganate mass ratio adds potassium permanganate powder for 3: 2, and is heated to 80 DEG C, stirs 6h Afterwards, that is, obtain the solution 2 for being dispersed with the compound porous nanofiber of carbon@manganese dioxide, through filter, wash three times, ethanol wash three It is secondary, remove excess surface impurity, after vacuum drying, obtain the compound porous nanofiber 3 of carbon@manganese dioxide.After tested, dioxy Change manganese lamellar spacing 7nm, the compound porous nanofiber specific surface area of carbon@manganese dioxide is 281.413m2/ g, conductivity are 6.28S/cm;After assembling them into ultracapacitor, its specific capacity is 421mAh/g, and capacity retention ratio reaches after 3000 circulations 81.2%.
Embodiment 2
The present invention is first according to the patent of invention that this seminar has applied:A kind of lithium sulfur battery anode material is received with porous carbon Rice tunica fibrosa and preparation method thereof (application number:201510675761.1), based on this, prepare cellular porous carbon nanometer Fiber-based material.
Cellular carbon nano-fiber basis material is dispersed in distilled water by stirring or ultrasonic power, with honeycomb Shape carbon nano-fiber basis material: potassium permanganate mass ratio adds potassium permanganate powder for 3: 4, and is heated to 80 DEG C, stirs 6h Afterwards, that is, obtain the solution for being dispersed with the compound porous nanofiber of carbon@manganese dioxide, through filter, wash three times, ethanol wash three It is secondary, remove excess surface impurity, after vacuum drying, obtain the compound porous nanofiber of carbon@manganese dioxide.After tested, dioxy Change manganese lamellar spacing 10nm, the compound porous nanofiber specific surface area of carbon@manganese dioxide is 236.586m2/ g, conductivity are 2.50S/cm;After assembling them into ultracapacitor, its specific capacity is 434mAh/g, and capacity retention ratio is after 3000 circulations 77.2%.
Embodiment 3
The present invention is first according to the patent of invention that this seminar has applied:A kind of lithium sulfur battery anode material is received with porous carbon Rice tunica fibrosa and preparation method thereof (application number:201510675761.1), based on this, prepare cellular porous carbon nanometer Fiber-based material.
Cellular carbon nano-fiber basis material is dispersed in distilled water by stirring or ultrasonic power, with honeycomb Shape carbon nano-fiber basis material: potassium permanganate mass ratio adds potassium permanganate powder for 4: 1, and is heated to 80 DEG C, stirs 6h Afterwards, that is, obtain the solution for being dispersed with the compound porous nanofiber of carbon@manganese dioxide, through filter, wash three times, ethanol wash three It is secondary, remove excess surface impurity, after vacuum drying, obtain the compound porous nanofiber of carbon@manganese dioxide.After tested, dioxy Change manganese lamellar spacing 5nm, the compound porous nanofiber specific surface area of carbon@manganese dioxide is 313.147m2/ g, conductivity are 19.08S/cm;After assembling them into ultracapacitor, its specific capacity is 358mAh/g, and capacity retention ratio is after 3000 circulations 85.7%.

Claims (3)

  1. A kind of 1. ultracapacitor compound porous nanofiber of carbon@manganese dioxide, it is characterised in that cellular porous carbon nanometer Fiber-based material diameter range connects in the corpus fibrosum between 150~500nm comprising middle pore diameter range for 30~100nm Continuous through hole;The manganese dioxide is in continuous through hole of the sheet homoepitaxial inside the porous carbon nanofiber.
  2. 2. a kind of preparation method of the compound porous nanofiber of@manganese dioxide of carbon according to claim 1, its feature include with Lower step:Cellular carbon nano-fiber basis material is dispersed in distilled water, adds the potassium permanganate powder of certain mass End, potassium permanganate quality are 1: 20-5: 2 with cellular carbon nano-fiber basis material mass ratio, anti-when temperature is 50-90 DEG C 2-24h is answered, using the reproducibility of carbon itself in porous carbon fiber nanometer, potassium permanganate is reduced into manganese dioxide so that dioxy Change manganese with continuous through hole of the lamellar structure homoepitaxial inside the porous carbon nanofiber, then through repeatedly washing, absolute ethyl alcohol Wash and filter, after vacuum drying, obtain the compound porous nanofiber of carbon@manganese dioxide.
  3. 3. the compound porous nanofiber of carbon@manganese dioxide according to claim 1, it is characterised in that the manganese dioxide is The manganese dioxide of lamella nanostructured, lamellar spacing 5-10nm.
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Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108793257A (en) * 2018-07-19 2018-11-13 江苏理工学院 A kind of porous MnO2The preparation method of/graphite composite
CN108899519A (en) * 2018-07-04 2018-11-27 范凝睿 A kind of biomass-based manganese dioxide-carbon fibre composite and preparation method thereof
CN109309216A (en) * 2018-08-20 2019-02-05 中国航发北京航空材料研究院 A kind of preparation method of lithium sulfur battery anode material
CN109647538A (en) * 2018-12-11 2019-04-19 天津工业大学 A kind of preparation method of manganese dioxide load type catalyst
CN110136977A (en) * 2019-05-23 2019-08-16 福建工程学院 A kind of preparation method of the ordered mesopore carbon load manganese dioxide core-shell type nanobelt for electrode material for super capacitor
CN110706940A (en) * 2019-10-17 2020-01-17 福建工程学院 Three-dimensional porous carbon-manganese oxide core-shell structure material and preparation method and application thereof
CN111048324A (en) * 2018-10-14 2020-04-21 天津大学 Manganese dioxide-porous carbon composite material and preparation method and application thereof
CN112086292A (en) * 2019-06-14 2020-12-15 苏州盟维动力科技有限公司 Nano-composite fiber electrode, all-solid-state fiber super capacitor and preparation method
CN112466840A (en) * 2020-11-24 2021-03-09 复旦大学 TSV structure and preparation method thereof
CN114899385A (en) * 2022-06-10 2022-08-12 江西省纳米技术研究院 Carbon/manganese dioxide composite material and preparation method and application thereof
CN115295324A (en) * 2022-01-14 2022-11-04 青岛大学 Method for preparing composite nanofiber electrode material based on deposition method, product and application thereof

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Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108899519A (en) * 2018-07-04 2018-11-27 范凝睿 A kind of biomass-based manganese dioxide-carbon fibre composite and preparation method thereof
CN108793257A (en) * 2018-07-19 2018-11-13 江苏理工学院 A kind of porous MnO2The preparation method of/graphite composite
CN109309216A (en) * 2018-08-20 2019-02-05 中国航发北京航空材料研究院 A kind of preparation method of lithium sulfur battery anode material
CN109309216B (en) * 2018-08-20 2022-11-29 北京石墨烯技术研究院有限公司 Preparation method of lithium-sulfur battery positive electrode material
CN111048324A (en) * 2018-10-14 2020-04-21 天津大学 Manganese dioxide-porous carbon composite material and preparation method and application thereof
CN109647538A (en) * 2018-12-11 2019-04-19 天津工业大学 A kind of preparation method of manganese dioxide load type catalyst
CN110136977A (en) * 2019-05-23 2019-08-16 福建工程学院 A kind of preparation method of the ordered mesopore carbon load manganese dioxide core-shell type nanobelt for electrode material for super capacitor
CN112086292A (en) * 2019-06-14 2020-12-15 苏州盟维动力科技有限公司 Nano-composite fiber electrode, all-solid-state fiber super capacitor and preparation method
CN110706940A (en) * 2019-10-17 2020-01-17 福建工程学院 Three-dimensional porous carbon-manganese oxide core-shell structure material and preparation method and application thereof
CN110706940B (en) * 2019-10-17 2021-09-28 福建工程学院 Three-dimensional porous carbon-manganese oxide core-shell structure material and preparation method and application thereof
CN112466840A (en) * 2020-11-24 2021-03-09 复旦大学 TSV structure and preparation method thereof
CN112466840B (en) * 2020-11-24 2022-10-21 复旦大学 TSV structure and preparation method thereof
CN115295324A (en) * 2022-01-14 2022-11-04 青岛大学 Method for preparing composite nanofiber electrode material based on deposition method, product and application thereof
CN115295324B (en) * 2022-01-14 2023-09-08 青岛大学 Method for preparing composite nanofiber electrode material based on deposition method, product and application thereof
CN114899385A (en) * 2022-06-10 2022-08-12 江西省纳米技术研究院 Carbon/manganese dioxide composite material and preparation method and application thereof

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Application publication date: 20180501