CN109935472A - A kind of multiform looks Fe-Mn compound carbon nanofiber and its preparation and application - Google Patents
A kind of multiform looks Fe-Mn compound carbon nanofiber and its preparation and application Download PDFInfo
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Abstract
It include Fe the present invention relates to a kind of multiform looks Fe-Mn compound carbon nanofiber and its preparation and application, the carried by nano carbon fiber3O4And Mn3O4, wherein Fe3O4It is distributed in fibrous inside, Mn3O4It is grown in fiber surface, is cannula-like or roe granular texture by the pattern that Fe content regulates and controls compound carbon nanofiber.The present invention uses electrostatic spinning technique and MnOxSelf-limiting growth method obtains Fe-Mn compound carbon nanofiber.Production produced by the present invention is convenient, and at low cost, stability is good, and MnOxAdjustable in Fe-C nanofiber surface growth structure, the material is high for electrode of super capacitor electric conductivity, and specific capacitance is had excellent performance.
Description
Technical field
The invention belongs to electrode material and its preparation and application field, in particular to a kind of multiform looks Fe-Mn composite carbon is received
Rice fiber and its preparation and application.
Background technique
Since environmental pollution is got worse in Fossil fuel consumption and growth course, exploitation is cleaned, is efficiently and alternative
The energy is extremely urgent.Supercapacitor is as a kind of indispensable energy-storage travelling wave tube, since its power/energy density is high, charge and discharge
Electric speed is fast, the advantages that having extended cycle life, and can make up the gap between traditional dielectric capacitor and rechargeable battery.Many institute's weeks
Know, many transition metal oxides have fake capacitance characteristic, i.e., anti-by the way that reversible faraday's redox occurs in electrode surface
It answers and stores charge.
Mn oxide is because of the advantages that its specific capacitance is high, and advantage of lower cost is environmental-friendly, ABUNDANT NATUREAL RESOURSES and corrosion resistance
It is considered as one of most promising electrode material in supercapacitor applications.However since manganese oxide electric conductivity is poor, structure
Stability and long-term recyclability can be weaker, lower so as to cause available capacity, limit the ultracapacitor energy storage of manganese oxide
Further development.
The performance of Mn oxide is largely influenced by its pattern, structure, especially the knot of different shape Mn oxide
The influence of structure and varying topography to its performance, research finds that the manganese of multivalent state has good oxidation-reduction quality, to electron-transport
There is facilitation.Therefore the research to manganese oxide electrode material should focus on the structural behaviour for improving manganese oxide, be manganese oxide
Growth provide suitable substrate to prepare the adjustable Mn oxide combination electrode material of high performance structural, and then for super
The energy storage of capacitor.
In transition metal oxide, Fe3O4As another ideal capacitance material, theoretical storage with higher is held
Amount, has become the common electrode material of supercapacitor.
The carbon nano-fiber of load Mn oxide etc. has been reported that more, but leads to since potassium permanganate is reacted with the limit certainly that carbon occurs
It is often quickly and violent, it will lead to the excessive load of Mn oxide.[Flexible ultra-thin Fe3O4/MnO2core-
shell decorated CNT composite with enhanced electromagnetic wave absorption
performance,Composites Part B,144(2018)111–117.]。
Summary of the invention
Technical problem to be solved by the invention is to provide a kind of multiform looks Fe-Mn compound carbon nanofiber and its preparation and
Using, the defect that MnO load capacity is excessive in the prior art is overcome, passes through the invention provides one kind and regulates and controls Fe content, building
The multiform looks Fe-Mn compound carbon nanofiber electrode material of the adjustable high electrochemical activity of structure, in order to improve composite carbon nanometer
The electric conductivity of fiber introduces certain iron in electrospinning precursor liquid, not only increases the specific surface area of carbon nano-fiber, Er Qieqi
Electron conduction is significantly improved, and promotes the electron-transport in electrode, and the diffusion transport of ion and the insertion of ion are embedding
Process out improves the fake capacitance performance of material.
A kind of multiform looks Fe-Mn compound carbon nanofiber of the invention, the carried by nano carbon fiber includes Fe3O4With
Mn3O4(Fe3O4And Mn3O4It is nano material), wherein Fe3O4It is mainly distributed on fibrous inside, Mn3O4Mainly it is grown in fiber table
Face is cannula-like or roe granular texture by the pattern that Fe content regulates and controls compound carbon nanofiber.
The roe granular texture includes that structure is comparatively dense in loosely organized composite fibre or pipe with microchannel in pipe
The composite fibre of consolidation；Fe-Mn compound carbon nanofiber outer diameter is 200-400nm, internal diameter 150-250nm.
Multiform looks Fe-Mn compound carbon nanofiber preparation of the present invention: synthesizing Fe-C nanofiber by electrostatic spinning process,
Then MnO is grown in fibrous external by way of in-situ depositionx, compound carbon nanofiber is stablized finally by annealing
Fe-Mn compound carbon nanofiber is prepared in activation, is effectively improved the capacitive property of material, be can be used for supercapacitor field.
A kind of preparation method of multiform looks Fe-Mn compound carbon nanofiber of the invention, comprising:
(1) high molecular polymer is dissolved in organic solvent, heating water bath stirring obtains uniform faint yellow blend spinning
Then precursor liquid is added Fe salt and is mixed evenly, pre-oxidized after electrostatic spinning, be then carbonized under an inert atmosphere, obtained
To Fe-C nanofiber；Wherein mass percent of the Fe salt in spinning solution is 0-50%；
(2) above-mentioned Fe-C nanofiber is put into KMnO4In solution, stirring is impregnated, and is taken out after reaction, is washed, and is done
It is dry, obtain MnOxThe Fe-C nanofiber of processing, annealing, obtains Fe-Mn compound carbon nanofiber.
Wherein MnOxFor Mn oxide, the existing forms multiplicity of Mn oxide, is not single Mn oxide, final
It is Mn after the annealing arrived3O4。
The preferred embodiment of above-mentioned preparation method is as follows:
High molecular polymer is polyacrylonitrile, in polyvinylpyrrolidone, polyvinyl alcohol, polyamide in the step (1)
One or more, preferred polyacrylonitrile, average molecular weight 150000.
In the step (1) organic solvent be n,N-Dimethylformamide, dimethyl sulfoxide, -2 pyrrolidones of 1- methyl,
One or more of tetrahydrofuran, preferably n,N-Dimethylformamide.
Fe salt is ferric acetyl acetonade, FeCl in the step (1)3, ferric acetate, ferric nitrate, ferrocene, one in ferric sulfate
Kind is several, preferably ferric acetyl acetonade.
The mass percentage concentration of spinning precursor liquid is 5-15wt% in the step (1)；The content of Fe salt is 5-35%.
Electrostatic spinning process parameter in the step (1) are as follows: voltage 10-20kV, plug-flow speed are 0.5-1.2mL/h,
Spray head to reception device distance be 10-20cm, relative humidity 30-40%.
Pre-oxidation in the step (1) are as follows: it is pre-oxidized in Muffle furnace, wherein Pre oxidation is 200-400 DEG C, when
Between be 30-90min；Preferably, Pre oxidation is 260 DEG C.
It is 500-1200 DEG C that carbonization, which is temperature, in the step (1), time 60-120min, it is preferable that carburizing temperature
800 DEG C, time 90min.
KMnO in the step (2)4The concentration of solution is 2-50mmol/L.
Stirring soaking time is 0.5-24h, preferably 6h in the step (2).
Annealing temperature is 200-400 DEG C in the step (2), time 60-120min, it is preferable that annealing temperature 300
DEG C, time 90min.
The pattern of the regulation by Fe content, compound carbon nanofiber is obvious with the increase variation tendency of Fe content, Fe
Presence in the carbon fibers inhibits the oxidation of carbon, and the annealing process in material preparation can further speed up the oxidation of carbon, to turning
The form and structure for becoming Mn oxide have important influence, play the role of activation stable to compound carbon nanofiber, to material
The promotion of material chemical property plays apparent facilitation.
The present invention also provides a kind of multiform looks Fe-Mn compound carbon nanofiber electrode material, electrode material raw material includes institute
State multiform looks Fe-Mn compound carbon nanofiber, conductive agent, binder；Wherein multiform looks Fe-Mn compound carbon nanofiber, it is conductive
The mass ratio of agent and binder is (7-9): (0.5-2): (0.5-1).
Specifically prepared by following method: by multiform looks Fe-Mn compound carbon nanofiber, conductive agent, binder is sufficiently mixed
Uniformly, it is scattered in solvent, obtains sticky fluid mixture.Then obtained fluid mixture is uniformly coated on conductive collection
It is dried on fluid and in vacuum oven at 60 DEG C.
The conductive agent includes acetylene black, one or more of Super-P and electrically conductive graphite；Binder includes PTFE,
One or more of PVDF and CMC；Solvent includes one or more of -2 pyrrolidones of 1- methyl, ethyl alcohol.
The present invention also provides a kind of applications of multiform looks Fe-Mn compound carbon nanofiber electrode material.
Beneficial effect
(1) present invention has prepared the Fe-Mn compound carbon nanofiber of high conductivity；
(2) the method for the present invention is simple and easy, by adjusting Fe content in electrostatic spinning liquid, i.e., controllable Fe-Mn composite carbon
The pattern of nanofiber adjusts manganese oxide in the growth structure and existing forms of substrate surface using the oxidation-reduction quality of Fe；
(3) introducing of Fe improves electronics transfer in the present invention, improves the redox active of Mn in electrode material, promotees
The diffusion transport of ion and the embedding process out of the insertion of ion, improve the fake capacitance performance of material in into electrode；(fake capacitance
Stronger redox peaks can be can be seen that by the comparison of cyclic voltammetry curve to occur)；
(4) annealing has larger improvement to the capacitive property of compound carbon nanofiber in the present invention；(before annealing in Fig. 8
Whether the corresponding surround the area size of cyclic voltammetry curve afterwards is used to indicate the improvement of capacitive property)；
(5) Fe-Mn compound carbon nanofiber has preferable prospect in the application of supercapacitor in the present invention, due to Fe-
Mn oxide it is compound, the specific capacitance performance of material has obtained biggish improvement, when current density be 0.2A/g when, specific capacitance can
Reach 300F/g.
Detailed description of the invention
Fig. 1 (a) is the MnO being prepared in comparative example 1xThe scanning electron microscope (SEM) photograph of compound carbon nanofiber AMF0；Fig. 1 (b)
It is the scanning electron microscope (SEM) photograph for the Fe-Mn compound carbon nanofiber AMF1 being prepared in embodiment 1；Fig. 1 (c) is made in embodiment 2
The scanning electron microscope (SEM) photograph of standby obtained Fe-Mn compound carbon nanofiber AMF3；Fig. 1 (d) is the Fe-Mn being prepared in embodiment 3
The scanning electron microscope (SEM) photograph of compound carbon nanofiber AMF5.
Fig. 2 (a) is the MnO being prepared in comparative example 1xThe transmission electron microscope picture of compound carbon nanofiber AMF0 and corresponding
Distribution diagram of element；Fig. 2 (b) is the transmission electron microscope picture of the Fe-Mn compound carbon nanofiber AMF1 being prepared in embodiment 1 and right
The distribution diagram of element answered；Fig. 2 (c) is the transmission electron microscope picture for the Fe-Mn compound carbon nanofiber AMF3 being prepared in embodiment 2
And corresponding distribution diagram of element；Fig. 2 (d) is the transmission electricity for the Fe-Mn compound carbon nanofiber AMF5 being prepared in embodiment 3
Mirror figure and corresponding distribution diagram of element；Wherein the scale size in transmission electron microscope picture is 100nm.
Fig. 3 (a) is the MnO being prepared in comparative example 1xThe X-ray diffractogram of compound carbon nanofiber AMF0；Fig. 3 (b)
It is the X-ray diffractogram for the Fe-Mn compound carbon nanofiber AMF1 being prepared in embodiment 1；Fig. 3 (c) is made in embodiment 2
The X-ray diffractogram of standby obtained Fe-Mn compound carbon nanofiber AMF3；Fig. 3 (d) is the Fe-Mn being prepared in embodiment 3
The X-ray diffractogram of compound carbon nanofiber AMF5.
Fig. 4 (a) is the MnO being prepared in comparative example 1xThe cyclic voltammetry curve of compound carbon nanofiber AMF0；Fig. 4
(b) be the Fe-Mn compound carbon nanofiber AMF1 being prepared in embodiment 1 cyclic voltammetry curve；Fig. 4 (c) is embodiment 2
In the cyclic voltammetry curve of Fe-Mn compound carbon nanofiber AMF3 that is prepared；Fig. 4 (d) is prepared in embodiment 3
The cyclic voltammetry curve of Fe-Mn compound carbon nanofiber AMF5.
Fig. 5 (a) is the MnO being prepared in comparative example 1xThe impedance plot of compound carbon nanofiber AMF0；Fig. 5 (b)
It is the impedance plot for the Fe-Mn compound carbon nanofiber AMF1 being prepared in embodiment 1；Fig. 5 (c) is made in embodiment 2
The impedance plot of standby obtained Fe-Mn compound carbon nanofiber AMF3；Fig. 5 (d) is the Fe-Mn being prepared in embodiment 3
The impedance plot of compound carbon nanofiber AMF5.
Fig. 6 (a) is the MnO being prepared in comparative example 1xThe charging and discharging curve of compound carbon nanofiber AMF0；Fig. 6 (b)
It is the charging and discharging curve for the Fe-Mn compound carbon nanofiber AMF1 being prepared in embodiment 1；Fig. 6 (c) is made in embodiment 2
The charging and discharging curve of standby obtained Fe-Mn compound carbon nanofiber AMF3；Fig. 6 (d) is the Fe-Mn being prepared in embodiment 3
The charging and discharging curve of compound carbon nanofiber AMF5.
Fig. 7 (a) is the MnO being prepared in comparative example 1xThe energy density and power density of compound carbon nanofiber AMF0
Comparison diagram；Fig. 7 (b) be the Fe-Mn compound carbon nanofiber AMF1 being prepared in embodiment 1 energy density and power it is close
The comparison diagram of degree；Fig. 7 (c) is the energy density and power for the Fe-Mn compound carbon nanofiber AMF3 being prepared in embodiment 2
The comparison diagram of density；Fig. 7 (d) is the energy density and function for the Fe-Mn compound carbon nanofiber AMF5 being prepared in embodiment 3
The comparison diagram of rate density.
The cyclic voltammetry curve for the Fe-C nanofiber F3 being prepared in Fig. 8 (a) comparative example 2；Fig. 8 (b) comparison is implemented
The cyclic voltammetry curve for the unannealed Fe-Mn compound carbon nanofiber MF3 being prepared in example 3；It is made in Fig. 8 (c) embodiment 2
The cyclic voltammetry curve of standby obtained Fe-Mn compound carbon nanofiber AMF3.
Specific embodiment
Present invention will be further explained below with reference to specific examples.It should be understood that these embodiments are merely to illustrate the present invention
Rather than it limits the scope of the invention.In addition, it should also be understood that, after reading the content taught by the present invention, those skilled in the art
Member can make various changes or modifications the present invention, and such equivalent forms equally fall within the application the appended claims and limited
Range.It is supplemented in embodiment relative to test method condition of attached drawing etc..
Embodiment 1
(1) 1g polyacrylonitrile (PAN) is dissolved in 10mL n,N-Dimethylformamide (DMF), heating water bath stirring obtains
The faint yellow blend spinning precursor liquid for being 10wt% to finely dispersed mass fraction is then added 0.1g ferric acetyl acetonade and (contains
Amount is 9%) to be mixed evenly.Electrospinning conditions are that voltage is 15kV, and plug-flow speed is 1mL/h, spray head to reception device
Distance is 15cm, relative humidity 30-40%.The first step pre-oxidizes the precursor obtained after spinning, from room temperature with 2 DEG C/
Min is warming up to 260 DEG C, cools to room temperature with the furnace after stablizing 60min.Second step by the sample after pre-oxidation in an inert atmosphere from
Room temperature is warming up to 800 DEG C with 5 DEG C/min, cools to room temperature with the furnace after stablizing 90min, obtains Fe-C nanofiber F1.
(2) the Fe-C nanofiber in step (1) is put into 10mmol/LKMnO4In solution, 6h, reaction knot are impregnated in stirring
It takes out, washs after beam, it is dry, obtain unannealed Fe-Mn compound carbon nanofiber MF1.
(3) Fe-Mn compound carbon nanofiber unannealed in step (2) is placed in Muffle furnace and is annealed, it is annealed
Journey is warming up to 300 DEG C from room temperature with 5 DEG C/min, cools to room temperature with the furnace after stablizing 90min, obtains Fe-Mn composite carbon Nanowire
Tie up AMF1.
The hollow structure of cannula-like is presented in Fe-Mn compound carbon nanofiber AMF1 in the present embodiment, such as Fig. 1 (b)；Fiber
Internal structure and Elemental redistribution such as Fig. 2 (b).
Shown in XRD spectrum such as Fig. 3 (b) of Fe-Mn compound carbon nanofiber AMF1 in the present embodiment, 35.6 °,
Occur apparent diffraction maximum at 43.3 °, 57.2 ° and 62.8 °, these diffraction maximums correspond respectively to crystrallographic plane (311), (400),
(511), the Fe of (440)3O4(No. JCPDS: 19-0629) and Mn3O4(No. JCPDS: 13-0162).
Cyclic voltammetry curve of the Fe-Mn compound carbon nanofiber AMF1 under 20mV/s sweep speed in the present embodiment is such as
Shown in Fig. 4 (b), wherein two pairs of apparent redox reaction spike potentials are respectively near 0.1V, 1.0V, -0.1V and 0.9V.
Shown in AC impedance figure such as Fig. 5 (b) of Fe-Mn compound carbon nanofiber AMF1 in the present embodiment, due to hollow
Carbon content in structure is lower, and charge transfer resistance is larger, and the diffusion of ion also will receive certain influence in the electrolytic solution.
Embodiment 2
(1) 1g polyacrylonitrile (PAN) is dissolved in 10mL n,N-Dimethylformamide (DMF), heating water bath stirring obtains
The faint yellow blend spinning precursor liquid for being 10wt% to finely dispersed mass fraction is then added 0.3g ferric acetyl acetonade and (contains
Amount is 23%) to be mixed evenly.Electrospinning conditions are that voltage is 15kV, and plug-flow speed is 1mL/h, spray head to reception device
Distance is 15cm, relative humidity 30-40%.The first step pre-oxidizes the precursor obtained after spinning, from room temperature with 2 DEG C/
Min is warming up to 260 DEG C, cools to room temperature with the furnace after stablizing 60min.Second step by the sample after pre-oxidation in an inert atmosphere from
Room temperature is warming up to 800 DEG C with 5 DEG C/min, cools to room temperature with the furnace after stablizing 90min, obtains Fe-C nanofiber F3.
(2) the Fe-C nanofiber in step (1) is put into 10mmol/LKMnO4In solution, 6h, reaction knot are impregnated in stirring
It takes out, washs after beam, it is dry, obtain unannealed Fe-Mn compound carbon nanofiber MF3.
(3) Fe-Mn compound carbon nanofiber unannealed in step (2) is placed in Muffle furnace and is annealed, it is annealed
Journey is warming up to 300 DEG C from room temperature with 5 DEG C/min, cools to room temperature with the furnace after stablizing 90min, obtains Fe-Mn composite carbon Nanowire
Tie up AMF3.
Fe-Mn compound carbon nanofiber AMF3 fiber outer wall in the present embodiment collapses fold, and internal structure is more loose
It is sparse, part hollow structure is still presented in fiber, there are some microchannels, roe granular texture are presented, such as Fig. 1 (c)；Fiber it is interior
Portion's structure and Elemental redistribution such as Fig. 2 (c).
Shown in XRD spectrum such as Fig. 3 (c) of Fe-Mn compound carbon nanofiber AMF3 in the present embodiment, 35.6 °,
Occur apparent diffraction maximum at 43.3 °, 57.2 ° and 62.8 °, these diffraction maximums correspond respectively to crystrallographic plane (311), (400),
(511), the Fe of (440)3O4(No. JCPDS: 19-0629) and Mn3O4(No. JCPDS: 13-0162).
Cyclic voltammetry curve of the Fe-Mn compound carbon nanofiber AMF3 under 20mV/s sweep speed in the present embodiment is such as
Shown in Fig. 4 (c), wherein two pairs of apparent redox reaction spike potentials are respectively near 0.1V, 1.0V, -0.1V and 0.9V.?
Shown in cyclic voltammetry curve such as Fig. 8 (c) under 50mV/s sweep speed.
Shown in AC impedance figure such as Fig. 5 (c) of Fe-Mn compound carbon nanofiber AMF3 in the present embodiment, electric conductivity
Reach with Ionic diffusion best.The Fe-C of roe granular texture, which exists, in witness tube has electron transmission and ion diffusion
It improves significantly.
The specific capacitance of 2 resulting materials of embodiment, when current density is 0.2A/g, specific capacitance 300F/g.
Embodiment 3
(1) 1g polyacrylonitrile (PAN) is dissolved in 10mL n,N-Dimethylformamide (DMF), heating water bath stirring obtains
The faint yellow blend spinning precursor liquid for being 10wt% to finely dispersed mass fraction is then added 0.5g ferric acetyl acetonade and (contains
Amount is 33%) to be mixed evenly.Electrospinning conditions are that voltage is 15kV, and plug-flow speed is 1mL/h, spray head to reception device
Distance is 15cm, relative humidity 30-40%.The first step pre-oxidizes the precursor obtained after spinning, from room temperature with 2 DEG C/
Min is warming up to 260 DEG C, cools to room temperature with the furnace after stablizing 60min.Second step by the sample after pre-oxidation in an inert atmosphere from
Room temperature is warming up to 800 DEG C with 5 DEG C/min, cools to room temperature with the furnace after stablizing 90min, obtains Fe-C nanofiber F5.
(2) the Fe-C nanofiber in step (1) is put into 10mmol/L KMnO4In solution, 6h, reaction are impregnated in stirring
After take out, wash, it is dry, obtain unannealed Fe-Mn compound carbon nanofiber MF5.
(3) Fe-Mn compound carbon nanofiber unannealed in step (2) is placed in Muffle furnace and is annealed, it is annealed
Journey is warming up to 300 DEG C from room temperature with 5 DEG C/min, cools to room temperature with the furnace after stablizing 90min, obtains Fe-Mn composite carbon Nanowire
Tie up AMF5.
Fe-Mn compound carbon nanofiber AMF5 fiber outer wall support in the present embodiment is preferable, and fibrous inside is shown
Comparatively dense solid roe granular texture, such as Fig. 1 (d)；Internal structure and Elemental redistribution such as Fig. 2 (d) of fiber.
Shown in XRD spectrum such as Fig. 3 (d) of Fe-Mn compound carbon nanofiber AMF5 in the present embodiment, 35.6 °,
Occur apparent diffraction maximum at 43.3 °, 57.2 ° and 62.8 °, these diffraction maximums correspond respectively to crystrallographic plane (311), (400),
(511), the Fe of (440)3O4(No. JCPDS: 19-0629) and Mn3O4(No. JCPDS: 13-0162).
Cyclic voltammetry curve of the Fe-Mn compound carbon nanofiber AMF5 under 20mV/s sweep speed in the present embodiment is such as
Shown in Fig. 4 (d), wherein two pairs of apparent redox reaction spike potentials are respectively near 0.1V, 1.0V, -0.1V and 0.9V.
Shown in AC impedance figure such as Fig. 5 (d) of Fe-Mn compound carbon nanofiber AMF5 in the present embodiment, solid construction
AMF5 will lead to ion and be obstructed in solution exchange process, thus the transmission of its ion and diffusion process occur it is slower.
Embodiment 4
(1) 0.5g polyacrylonitrile (PAN) is dissolved in 10mL n,N-Dimethylformamide (DMF), heating water bath stirring,
The faint yellow blend spinning precursor liquid that finely dispersed mass fraction is 5wt% is obtained, 0.3g ferric acetyl acetonade is then added and (contains
Amount is 37.5%) to be mixed evenly.Electrospinning conditions are that voltage is 15kV, and plug-flow speed is 1mL/h, and spray head is filled to reception
Setting distance is 15cm, relative humidity 30-40%.The first step pre-oxidizes the precursor obtained after spinning, from room temperature with 2
DEG C/min is warming up to 260 DEG C, room temperature is cooled to the furnace after stablizing 60min.Second step is by the sample after pre-oxidation in inert atmosphere
In from room temperature with 5 DEG C/min be warming up to 800 DEG C, cool to room temperature with the furnace after stablizing 90min, obtain Fe-C nanofiber.
(2) the Fe-C nanofiber in step (1) is put into 10mmol/LKMnO4In solution, 6h, reaction knot are impregnated in stirring
It takes out, washs after beam, it is dry, obtain unannealed Fe-Mn compound carbon nanofiber.
(3) Fe-Mn compound carbon nanofiber unannealed in step (2) is placed in Muffle furnace and is annealed, it is annealed
Journey is warming up to 300 DEG C from room temperature with 5 DEG C/min, cools to room temperature with the furnace after stablizing 90min, obtains Fe-Mn composite carbon Nanowire
Dimension.
Embodiment 5
(1) 1g polyacrylonitrile (PAN) is dissolved in 10mL n,N-Dimethylformamide (DMF), heating water bath stirring obtains
The faint yellow blend spinning precursor liquid for being 10wt% to finely dispersed mass fraction, 0.3g ferric acetate is then added, and (content is
23%) it is mixed evenly.Electrospinning conditions are that voltage is 15kV, and plug-flow speed is 1mL/h, spray head to reception device distance
For 15cm, relative humidity 30-40%.The first step pre-oxidizes the precursor obtained after spinning, from room temperature with 2 DEG C/min liter
Temperature cools to room temperature with the furnace after stablizing 60min to 260 DEG C.Second step is by the sample after pre-oxidation in an inert atmosphere from room temperature
800 DEG C are warming up to 5 DEG C/min, room temperature is cooled to the furnace after stablizing 90min, obtains Fe-C nanofiber.
(2) the Fe-C nanofiber in step (1) is put into 10mmol/LKMnO4In solution, 6h, reaction knot are impregnated in stirring
It takes out, washs after beam, it is dry, obtain unannealed Fe-Mn compound carbon nanofiber.
(3) Fe-Mn compound carbon nanofiber unannealed in step (2) is placed in Muffle furnace and is annealed, it is annealed
Journey is warming up to 300 DEG C from room temperature with 5 DEG C/min, cools to room temperature with the furnace after stablizing 90min, obtains Fe-Mn composite carbon Nanowire
Dimension.
Embodiment 6
(1) 1g polyacrylonitrile (PAN) is dissolved in 10mL n,N-Dimethylformamide (DMF), heating water bath stirring obtains
The faint yellow blend spinning precursor liquid for being 10wt% to finely dispersed mass fraction is then added 0.3g ferric acetyl acetonade and (contains
Amount is 23%) to be mixed evenly.Electrospinning conditions are that voltage is 15kV, and plug-flow speed is 1mL/h, spray head to reception device
Distance is 15cm, relative humidity 30-40%.The first step pre-oxidizes the precursor obtained after spinning, from room temperature with 2 DEG C/
Min is warming up to 260 DEG C, cools to room temperature with the furnace after stablizing 60min.Second step by the sample after pre-oxidation in an inert atmosphere from
Room temperature is warming up to 800 DEG C with 5 DEG C/min, cools to room temperature with the furnace after stablizing 90min, obtains Fe-C nanofiber.
(2) the Fe-C nanofiber in step (1) is put into 5mmol/LKMnO4In solution, 6h, reaction knot are impregnated in stirring
It takes out, washs after beam, it is dry, obtain unannealed Fe-Mn compound carbon nanofiber.
(3) Fe-Mn compound carbon nanofiber unannealed in step (2) is placed in Muffle furnace and is annealed, it is annealed
Journey is warming up to 300 DEG C from room temperature with 5 DEG C/min, cools to room temperature with the furnace after stablizing 90min, obtains Fe-Mn composite carbon Nanowire
Dimension.
Comparative example 1
(1) 1g polyacrylonitrile (PAN) is dissolved in 10mL n,N-Dimethylformamide (DMF), heating water bath stirring obtains
The faint yellow blend spinning precursor liquid for being 10wt% to finely dispersed mass fraction.Electrospinning conditions are that voltage is 15kV,
Plug-flow speed is 1mL/h, and spray head to reception device distance is 15cm, relative humidity 30-40%.The first step will obtain after spinning
Precursor pre-oxidized, be warming up to 260 DEG C from room temperature with 2 DEG C/min, cool to room temperature with the furnace after stablizing 60min.Second step
Sample after pre-oxidation is warming up to 800 DEG C from room temperature with 5 DEG C/min in an inert atmosphere, is cooled to the furnace after stablizing 90min
Room temperature obtains carbon nano-fiber F0.
(2) carbon nano-fiber in step (1) is put into 10mmol/LKMnO4In solution, 6h is impregnated in stirring, and reaction terminates
After take out, wash, it is dry, obtain unannealed MnOxCompound carbon nanofiber MF0.
(3) by the unannealed MnO in step (2)xCompound carbon nanofiber is placed in Muffle furnace and anneals, annealed
Journey is warming up to 300 DEG C from room temperature with 5 DEG C/min, cools to room temperature with the furnace after stablizing 90min, obtains MnOxCompound carbon nanofiber
AMF0。
MnO in the present embodimentxHalfpipe is presented in compound carbon nanofiber AMF0 fiber, such as Fig. 1 (a)；Fiber
Internal structure and Elemental redistribution such as Fig. 2 (a).
MnO in the present embodimentxShown in the XRD spectrum of compound carbon nanofiber AMF0 such as Fig. 3 (a), the oxide of AMF0
Main Morphology is potassium manganese ore structure (No. JCPDS: 16-0205), K2Mn4O8Appearance often along with α-MnO2Formation, the master of Mn
It is+4 valences there are valence state.
MnO in the present embodimentxCyclic voltammetry curve of the compound carbon nanofiber AMF0 under 20mV/s sweep speed is such as
Shown in Fig. 4 (a), wherein two pairs of apparent redox reaction spike potentials are respectively near 0.1V, 1.0V, -0.1V and 0.9V, peak
It is strong weaker.
MnO in the present embodimentxShown in AC impedance figure such as Fig. 5 (a) of compound carbon nanofiber AMF0, the resistance of AMF0
It is larger, illustrate that material itself results in the electric conductivity of difference due to the disappearance of carbon.
Comparative example 2
Using step (1) preparation Fe-C nanofiber (F3) in embodiment 2.
The cyclic voltammetry curve such as Fig. 8 (a) of Fe-C nanofiber (F3) under 50mV/s sweep speed in the present embodiment
Shown, no apparent redox reaction peak occurs.
Comparative example 3
Unannealed Fe-Mn compound carbon nanofiber (MF3) is obtained using step (1)-(2) in embodiment 2.
Circulation of the unannealed Fe-Mn compound carbon nanofiber (MF3) under 50mV/s sweep speed in the present embodiment
Shown in volt-ampere curve such as Fig. 8 (b), there is faint redox signal to occur, embody Mn fake capacitance in the composite
Performance shows.
Claims (11)
1. a kind of multiform looks Fe-Mn compound carbon nanofiber, which is characterized in that the carried by nano carbon fiber includes Fe3O4With
Mn3O4, wherein Fe3O4It is distributed in fibrous inside, Mn3O4It is grown in fiber surface, compound carbon nanofiber is regulated and controled by Fe content
Pattern be cannula-like or roe granular texture.
2. compound carbon nanofiber according to claim 1, which is characterized in that the Fe-Mn compound carbon nanofiber outer diameter
For 200-400nm, internal diameter 150-250nm.
3. compound carbon nanofiber according to claim 1, which is characterized in that the roe granular texture includes structure pine in managing
The composite fibre of the comparatively dense consolidation of structure in dissipating the composite fibre with microchannel or managing.
4. the preparation method of multiform looks Fe-Mn compound carbon nanofiber described in a kind of claim 1, comprising:
(1) high molecular polymer is dissolved in organic solvent, heating water bath stirring obtains spinning precursor liquid, Fe salt is then added
It is mixed evenly, is pre-oxidized after electrostatic spinning, is then carbonized under an inert atmosphere, obtain Fe-C nanofiber；Wherein
Mass percent of the Fe salt in spinning solution is 0-50%；
(2) above-mentioned Fe-C nanofiber is put into KMnO4In solution, stirring is impregnated, and is taken out after reaction, is washed, dry, is obtained
To MnOxThe Fe-C nanofiber of processing, annealing, obtains Fe-Mn compound carbon nanofiber.
5. preparation method according to claim 4, which is characterized in that high molecular polymer is polypropylene in the step (1)
One or more of nitrile, polyvinylpyrrolidone, polyvinyl alcohol, polyamide；Organic solvent is n,N-Dimethylformamide, two
One or more of methyl sulfoxide, -2 pyrrolidones of 1- methyl, tetrahydrofuran；Fe salt is ferric acetyl acetonade, FeCl3, acetic acid
One or more of iron, ferric nitrate, ferrocene, ferric sulfate.
6. preparation method according to claim 4, which is characterized in that the quality percentage of spinning precursor liquid in the step (1)
Concentration is 5-15wt%；The content of Fe salt is 5-35%.
7. preparation method according to claim 4, which is characterized in that electrostatic spinning process parameter in the step (1) are as follows: electricity
Pressure is 10-20kV, and plug-flow speed is 0.5-1.2mL/h, and spray head to reception device distance is 10-20cm, relative humidity 30-
40%；Pre-oxidation are as follows: pre-oxidized in Muffle furnace, wherein Pre oxidation is 200-400 DEG C, time 30-90min；Carbon
Turning to temperature is 500-1200 DEG C, time 60-120min.
8. preparation method according to claim 4, which is characterized in that KMnO in the step (2)4The concentration of solution is 2-
50mmol/L。
9. preparation method according to claim 4, which is characterized in that stirring soaking time is 0.5- in the step (2)
24h；Annealing temperature is 200-400 DEG C, time 60-120min.
10. a kind of multiform looks Fe-Mn compound carbon nanofiber electrode material, which is characterized in that electrode material raw material includes right
It is required that the 1 multiform looks Fe-Mn compound carbon nanofiber and conductive agent, binder.
11. the application of multiform looks Fe-Mn compound carbon nanofiber electrode material described in a kind of claim 10.
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