CN108155023A - A kind of preparation method of nitrogen-phosphor codoping biological carbon/manganese compound composite material - Google Patents
A kind of preparation method of nitrogen-phosphor codoping biological carbon/manganese compound composite material Download PDFInfo
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- CN108155023A CN108155023A CN201711416935.8A CN201711416935A CN108155023A CN 108155023 A CN108155023 A CN 108155023A CN 201711416935 A CN201711416935 A CN 201711416935A CN 108155023 A CN108155023 A CN 108155023A
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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
- H01G11/30—Electrodes characterised by their material
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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
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
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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
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
Abstract
The invention discloses the present invention relates to the preparation method and application of nitrogen-phosphor codoping biological carbon/manganese compound composite material, described method includes following steps：S1：Egg yolk and potassium permanganate uniformly mix by a certain percentage, and hydro-thermal reaction is for 24 hours in autoclave；S2：After reaction, it is cooled to room temperature and is washed with ethyl alcohol, precipitation drying is complete；S3：The drying sample is subjected to high-temperature process under inert gas shielding, so as to obtain the nitrogen-phosphor codoping biological carbon/manganese compound composite material.Nitrogen-phosphor codoping biological carbon/manganese compound the composite material has excellent electric property, so as to be applied to capacitor area, especially ultracapacitor field, have a good application prospect and industrialization potential.
Description
Technical field
More specifically a kind of composite material and preparation method thereof and purposes, provide a kind of available for ultracapacitor
Nitrogen-phosphor codoping biomass carbon/manganese compound composite material of material and preparation method thereof and purposes, belong to inorganic functional material
And electrochemical energy technical field.
Background technology
As portable electronic product and electric vehicle are towards lightweight, the fast development of miniaturization, phase therewith is developed
The have both high volume energy density and the long-life ultracapacitor of high power density matched become current active demand.However,
The electrode material using activated carbon as ultracapacitor has very high power density and long circulating stability at present, and also there are energy
The defects of metric density is relatively low, large-scale application and industrialization this greatly limits ultracapacitor.
Therefore, the carbon nanomaterial of the Heteroatom doping of new structure is found (such as：Nitrogen phosphate and sulfur etc.) it is ground as current
Study carefully hot spot.Although these new materials can effectively improve energy density, there are still this is of high cost, building-up process is complicated etc.
Many defects can not meet application request.And transition metal oxide such as NiO, MnO2Deng with high energy density,
But its power density is low, cyclical stability is poor.It is therefore, how that transition metal and the progress of the carbon material of low cost is effectively compound,
Obtain that existing high energy density has a high power density again and stability is numerous researchers pursue at present target.
At present, discarded biomass causes vast research work with its excellent characteristics such as inexpensive, renewable, pollution-free
The concern of person, such as：
Ma et al. (Advanced Energy Materials, 2016 (6) 1) is had studied using useless tealeaves as carbon source, 700
It is simply carbonized at DEG C, prepares the porous activated carbon of N doping.The material average pore size be 2.3~6.6nm, specific surface area 10.3
~1143.9m2/ g, power density 221W/Kg, energy density is smaller, is 13.5Wh/Kg, and after cycle 5000 is enclosed, capacitance is kept
Rate is 91%, but energy density is low.
Teo et al. (Journal of Power Sources, 2016 (330) 219) elaborates biomass rice husk as carbon
The application in source.It is activated at different temperatures, the material is under the current density of 1A/g, after 10000 circle of cycle, capacitance
Conservation rate is 85%, specific capacitance 147F/g, but energy density is smaller, is 5.1Wh/Kg.
Long et al. (Nano Energy, 2015 (12) 141) is synthesized using agaric as presoma by direct carborization
Porous carbon materials, the material circulation excellent in stability, after cycle-index 20000, capacitance remains at 100%, but energy is close
It spends low.
It is interrelated to have synthesized part using hemp bast fiber as carbon source by Wang et al. (ACS Nano, 2013 (7) 5131)
Unique nanometer sheet material, specific surface area is up to 2287m2·g-1, it is 100Ag in current density-1, temperature be 20 DEG C, 40
DEG C and 60 DEG C at, which respectively reaches 113Fg-1, 144Fg-1And 142Fg-1, but capacity retention only has
72-92%, stability are undesirable.
He et al. (Journal of Power Sources, 2015, (294) 150) is using flax fiber as carbon source, in carbon materials
Expect surface deposition MnO2, to improve performance.The material specific capacitance reaches 687.73Fg-1, energy density reaches 46.54wh
kg-1.In 300Ag-1Under, specific capacitance still has 269.04Fg-1, energy density still has 45.50whkg-1, but stable circulation
Property is poor.
A variety of the method for new material is prepared using biomass, and thus obtain as described above, disclosing in the prior art
A variety of new materials with excellent electrical properties, although these new materials can be by biomass by direct carbonization, work
Change and be provided with the performances such as porosity, high-specific surface area, but on electric property, there are still energy density it is relatively low the defects of, this
Seriously limit its practical application and industrialized production.
Therefore, how based on electrode material for super capacitor is prepared currently with biomass the defects of is carried using new method
Its high performance has a very important significance and the research hotspot and emphasis of current electrochemical energy source domain, and this is also exactly
It is leaned on where the basis that the present invention is accomplished with power.
Invention content
For overcome the deficiencies in the prior art, the purpose of the present invention is to provide a kind of nitrogen-phosphor codoping biological carbon/manganeses
The preparation method of compound composite material, can prepare novel electrochemical energy storage materials, especially obtain can be used for super capacitor
The composite material in device field.
The purpose of the present invention is realized using following technical scheme：
The present invention relates to a kind of preparation method of nitrogen-phosphor codoping biomass carbon/manganese compound composite material, the methods
Include the following steps：
S1：Egg yolk, manganese salt solution are reacted in high-pressure reactor；
S2：After reaction, cooled to room temperature, will be heavy by supernatant and precipitation absolute ethyl alcohol centrifuge washing
Shallow lake is placed in baking oven fully drying and completely, obtains crude product；
S3：The drying sample is subjected to high-temperature process under inert gas shielding, so as to obtain the nitrogen-phosphor codoping
Biomass carbon/manganese compound composite material.
In the preparation method of the nitrogen-phosphor codoping biomass carbon/manganese compound composite material of the present invention, in step
In S1, the egg yolk is Fresh Egg to be carried out the yellow and white separation, and dry yolk and obtain, such as its biodiversity content
Less than 10%.
In the preparation method of the nitrogen-phosphor codoping biomass carbon/manganese compound composite material of the present invention, in step
In S1, the manganese salt is potassium permanganate.
In the preparation method of the nitrogen-phosphor codoping biomass carbon/manganese compound composite material of the present invention, in step
In S1, the mass ratio of egg yolk and potassium permanganate is respectively (a-5:1、b-10:1、c-20:1、d-30:1、e-20:0 (nothing
KMnO4))。
In the preparation method of the nitrogen-phosphor codoping biomass carbon/manganese compound composite material of the present invention, in step
In S1, egg yolk is 5 with potassium permanganate mass ratio:1、10:1、20:1、30:1.
In the preparation method of the nitrogen-phosphor codoping biomass carbon/manganese compound composite material of the present invention, in step
In S1, reaction pressure 1-5MPa may be, for example, 1MPa, 2MPa, 3MPa, 4MPa or 5MPa.
In the preparation method of the nitrogen-phosphor codoping biomass carbon/manganese compound composite material of the present invention, in step
In S1, reaction temperature is 160-220 DEG C, may be, for example, 160 DEG C, 180 DEG C, 200 DEG C or 220 DEG C.
In the preparation method of the nitrogen-phosphor codoping biomass carbon/manganese compound composite material of the present invention, in step
In S1, the reaction time is 10-28 hours, may be, for example, 20 hours, 22 hours, 24 hours, 26 hours or 28 hours, preferably 20-
24 hours.
In the preparation method of the nitrogen-phosphor codoping biomass carbon/manganese compound composite material of the present invention, in step
In S2, obtained solid can be washed with deionized, and washing times can be 2-4 times.
In the preparation method of the nitrogen-phosphor codoping biomass carbon/manganese compound composite material of the present invention, in step
In S2, drying temperature is 80-120 DEG C, may be, for example, 80 DEG C, 100 DEG C or 120 DEG C；Drying time is 8-12 hours, be may be, for example,
8 hours, 10 hours or 12 hours.
In the preparation method of the nitrogen-phosphor codoping biomass carbon/manganese compound composite material of the present invention, in step
In S3, the temperature of the high-temperature process is 900-1100 DEG C, may be, for example, 900 DEG C, 950 DEG C, 1000 DEG C, 1050 DEG C or 1100
DEG C, preferably 950-1050 DEG C, most preferably 1000 DEG C.
In the preparation method of the nitrogen-phosphor codoping biomass carbon/manganese compound composite material of the present invention, in step
In S3, the high-temperature process time is 1-3 hours, be may be, for example, 1 hour, 2 hours or 3 hours.
In the preparation method of the nitrogen-phosphor codoping biomass carbon/manganese compound composite material of the present invention, in step
In S3, the inert gas is nitrogen or argon gas.
In the preparation method of the nitrogen-phosphor codoping biomass carbon/manganese compound composite material of the present invention, the step
High-temperature process in rapid 3, i.e., by the drying sample with being placed 1-3 hours in atmosphere of inert gases under above-mentioned temperature range,
So as to obtain the nitrogen-phosphor codoping biomass carbon/manganese compound composite material of the present invention.
The inventors discovered that when above-mentioned preparation method using the present invention certain optimizing technology parameters especially therein
When, the nitrogen-phosphor codoping biomass carbon/manganese compound composite material with excellent chemical property can be obtained, and work as and change certain
During a little technological parameters, performance is caused to significantly reduce.
The second aspect, the present invention relates to the nitrogen-phosphor codoping biomass carbon obtained by above-mentioned preparation method/manganeses to close
Object composite material.
The inventors discovered that the nitrogen-phosphor codoping biomass carbon/manganese compound composite material has excellent electrical property
Can, so as to be applied to capacitor area, especially ultracapacitor field, have a good application prospect and industrialize and is latent
Power.
Therefore, in terms of third, the present invention relates to the nitrogen-phosphor codoping biomass carbon/manganese compound composite materials to make
Purposes in standby capacitor.
In the purposes of the present invention, the nitrogen-phosphor codoping biomass carbon/manganese compound composite material can be used to make
Standby electrode for capacitors.
The preparation method of the electrode for capacitors specifically comprises the following steps：
(A) weighing composite material of the invention, acetylene black, PTFE (polytetrafluoroethylene (PTFE)) lotion, (three's mass ratio is 8:1:
1) ethanol in proper amount, is added in, is uniformly mixed, when being stirred continuously into starchiness, is uniformly coated onto in nickel foam；
(B) nickel foam for coating the composite material be dried, dried, tabletting is to get to the electrode for capacitors.
4th aspect, the present invention relates to one kind to include the nitrogen-phosphor codoping biomass carbon/manganese compound composite material
Electrode for capacitors, especially electrode of super capacitor.
Inventors discovered through research that include the capacitance of the nitrogen-phosphor codoping biomass carbon/manganese compound composite material
Device electrode has good chemical property, such as large capacity, high power, the long-life, stability is good, of low cost, environment is friendly
The superior performance such as good, so as to be applied to capacitor especially ultracapacitor field.
Compared with prior art, the beneficial effects of the present invention are：A kind of nitrogen-phosphor codoping biomass carbon/manganese compound is compound
Material and its preparation method and application, the nitrogen-phosphor codoping biomass carbon/manganese compound composite material have excellent electricity
Performance can be used to prepare electrode for capacitors especially electrode of super capacitor, so as to be used for capacitor especially super capacitor
In device, there is huge application potential and industrial value in electrochemical energy storage field.
Description of the drawings
Fig. 1 is the scanning electricity of nitrogen-phosphor codoping biomass carbon/manganese compound composite material obtained by the embodiment of the present invention 1
Mirror figure (SEM).
Fig. 2 is the XPS figures of nitrogen-phosphor codoping biomass carbon/manganese compound composite material obtained by the embodiment of the present invention 1.
Fig. 3 is nitrogen-phosphor codoping biomass carbon/manganese compound composite material different disposal obtained by the embodiment of the present invention 1
The Raman comparison diagrams of temperature.
Fig. 4-1,4-2 and 4-3 are nitrogen-phosphor codoping biomass carbon/manganese compound composite woods using the embodiment of the present invention 1
Material is by passing through 900 DEG C of (a), 1000 DEG C of (b), the N of (c) 1100 DEG C of processing2Adsorption/desorption curve and graph of pore diameter distribution (interpolation).
Fig. 5 is nitrogen-phosphor codoping biomass carbon/manganese compound composite material XRD spectrum using the embodiment of the present invention 1.
Fig. 6 is nitrogen-phosphor codoping biomass carbon/manganese compound composite material using the embodiment of the present invention 1 in different electric currents
Constant current charge-discharge curve under density.
Fig. 7 is nitrogen-phosphor codoping biomass carbon/manganese compound composite material using the embodiment of the present invention 1 in current density
For 1Ag-1Constant current charge-discharge curve (a-5 under different proportion:1、b-10:1、c-20:1、d-30:1、e-20:0 (nothing
KMnO4))。
It is respectively 1Ag in current density using the composite material of 1-3 of the embodiment of the present invention that Fig. 8, which is,-1Different heat treatment temperature
Constant current charge-discharge curve under degree.
The current density of Fig. 9 differential responses object component composite materials and capacitance relation figure (a-5:1、b-10:1、c-20:1、
d-30:1、e-20:0 (no KMnO4))。
The power of Figure 10 composite materials Mn-P-O-N-e-1000 and Mn-P-O-N-c-1000 under different current densities is close
Degree and energy density relationships figure.
It is respectively 10Ag in current density using the composite material of the embodiment of the present invention 1 that Figure 11, which is,-1Under stable circulation
Property test.
Figure 12 is tested using electrochemical impedance of the composite material of 1-3 of the embodiment of the present invention at a temperature of different heat treatment.
Specific embodiment
In the following, with reference to attached drawing and specific embodiment, the present invention is described further：
Embodiment 1
S1：It is c-20 to weigh egg yolk with potassium permanganate mass ratio with electronic balance:1 in beaker, add in 30mL go from
Sub- water.Ultrasonic agitation 30 minutes.Uniform turbid solution is obtained after dissolving, solution is transferred to 50mL politef liner high pressures
In kettle, and in baking oven, for 24 hours, temperature is set as 180 DEG C to hydro-thermal reaction；
S2：After reaction, cooled to room temperature, by supernatant and gained precipitation absolute ethyl alcohol centrifuge washing 3
It is secondary, precipitation is placed in baking oven fully drying completely, obtains crude product, temperature is 120 DEG C；
S3：The drying sample is subjected to high-temperature process under protection of argon gas, so as to obtain nitrogen-phosphor codoping biomass carbon/
Manganese compound composite material, is named Mn-P-O-N-c-1000；The temperature of wherein described high-temperature process is 1000 DEG C, processing
Time is 2 hours.
Embodiment 2-3：The investigation of step S3 high temperature treatment temperatures.
In addition to the high-temperature process temperature in step S3 is replaced with 900 DEG C and 1100 DEG C respectively, other operations are constant, from
And repetitive operation embodiment 1, so as to be carried out a 2-3 successively, gained composite material is named as Mn-P-O-N-c- successively
900 and Mn-P-O-N-c-1100.
Embodiment 4：Investigation during manganese compound is not added in step S1.
In addition to the potassium permanganate in step S1 is omitted, other operations are constant, thus repetitive operation embodiment 1,
Embodiment 4 is obtained, resulting materials are named into Mn-P-O-N-e-1000.
Embodiment 5-6：Change the investigation of egg yolk quality in step S1.
Except being respectively (a-5 by the egg yolk in step S1 and potassium permanganate mass ratio:1、b-10:1、d-30:1) outside,
Its operation is constant, so as to repetitive operation embodiment 1, obtains embodiment 5-6 successively, gained composite material is named as successively
Mn-P-O-N-a-1000, Mn-P-O-N-b-1000 and Mn-P-O-N-d-1000.
Microscopic sdIBM-2+2q.p.approach
To the nitrogen-phosphor codoping biomass carbon/manganese compound composite material Mn-P-O-N-c-1000 and reality of 1 gained of embodiment
The microscopic sdIBM-2+2q.p.approach that the material that example 4 obtains has carried out multiple and different means is applied, wherein, in following electrical performance testing, made
Electrode for capacitors is prepared according to step (A)-(B) in above-mentioned " preparation method of electrode for capacitors ".
As a result it is as follows：
As seen from Figure 1, the composite material has many layer structures.
It can be seen that in the Mn-P-O-N-c-1000 containing C element, N element, O elements, P element from the XRS figures of Fig. 2
Exist with Mn elements, and manganese exists in the form of oxide and phosphide.
Fig. 3 is Raman figures of the Mn-P-O-N-C-c-1000 Jing Guo different heat treatment temperature
The G peaks of 1 sample of table and D peak intensities ratio (ID/IG)
Fig. 3 is the Raman analysis spectrogram of Mn-P-O-N-C-c, is 900 DEG C, 1000 DEG C, 1100 DEG C of materials respectively from top to bottom
Material.Three kinds of composite materials are in 1340cm-1、1570cm-1Nearby there are two characteristic peaks of carbon, respectively D peaks, G peaks, from
It can be seen from the figure that, the D peaks of Mn-P-O-N-C-c-900 compare I with the intensity at G peaksD/IGFor 0.86, Mn-P-O-N-C-c-1000's
D peaks and the intensity at G peaks compare ID/IGCompare I for the D peaks of 1.05, Mn-P-O-N-C-c-1100 and the intensity at G peaksD/IGIt is 0.75, it can
To find out, with the intensity at G peaks than maximum, the surface defect of carbon material is most at the D peaks of material Mn-P-O-N-C-c-1000.
Ns of Fig. 4 Mn-P-O-N-C-c-1000 Jing Guo treatment of different temperature2Adsorption/desorption curve and graph of pore diameter distribution are (interior
It inserts):(a)900℃,(b)1000℃,(c)1100℃
The BET characterize datas of Mn-P-O-N-C-c at a temperature of 2 different heat treatment of table
Fig. 4 is BET collection of illustrative plates of the Mn-P-O-N-C-c Jing Guo treatment of different temperature.It can be seen from the figure that the composite material
Adsorption isotherm type be IV types of Type.Curve can be seen that in the relatively low part of relative pressure from figure, and absorption is relatively put down
Slow, which belongs to nitrogen molecule monolayer adsorption, but at elevated pressures, and adsorbance rising is very steep, this is capillary condensation phenomenon.
Pass through N2The specific surface area of absorption/desorption isotherm judgement Mn-P-O-N-C-c-900 is 104.33m2/ g, Mn-P-O-N-C-c-
1000 specific surface area is 127.36m2The specific surface area of/g, Mn-P-O-N-C-c-1100 are 13.28m/g, further according to absorption etc.
The Brunauer-Emment-Teller formula of warm line, the average pore size that Mn-P-O-N-C-c-900 can be calculated are
3.97nm, Mn-P-O-N-C-c-1000 average pore size are 4.15nm, and Mn-P-O-N-C-c-1100 average pore sizes are 16.40nm.
Conclusion：The specific surface area of further testimonial material Mn-P-O-N-C-c-1000 is maximum.
Fig. 5 is the XRD spectrum of sample Mn-P-O-N-C-c-1000, and as seen from the figure, 2 θ of the angle of diffraction is 26.3 ° and 43.8 ° points
(100) crystal face of (002) crystal face and graphitization C of oxidized form graphite C is not corresponded to.2 θ of the angle of diffraction for 25.7 °, 29.3 °, 30.9 °,
34.0 °, 39.4 °, 43.1 °, 45.5 °, 52.0 °, 52.9 °, 53.0 °, 69.8 °, 72.4 °, 77.4 °, 84.9 ° correspond to Mn respectively2P
(001), (110), (011), (200), (111), (021), (210), (300), (002), (211), (311), (212),
(302), (321) crystal face matches with standard card JCPDSNO.65-3545.2 θ of the angle of diffraction for 23.9 °, 31.5 °, 36.9 °,
46.7 ° of corresponding MnO2Crystal face, match with standard card JCPDS NO.12-0141.Conclusion：The further material of verification synthesis
Material has MnO2And Mn2P is formed.
The capacitance of Mn-P-O-N-C-c-1000 under the different current densities of table 3
Fig. 6 is respectively 1A/g, 2A/g, 5A/g in current density for Fe-P-O-N-C-1-5-1000, the perseverance electricity under 10A/g
Charging and discharging curve is flowed, corresponding quality specific capacitance is respectively 278.5F/g, 226.2F/g, 165.0F/g and 118.1F/g.With
The gradual continuous increase of current density, the time which completes a charge and discharge is gradually shortened, and constant current fills
Discharge curve also shows certain pseudo capacitance characteristic.
Constant current charge-discharge curve (a-5s of Fig. 7 Mn-P-O-N-C-1000 in the case where current density is 1A/g different proportion:1、
b-10:1、c-20:1、d-30:1、e-20:0 (no KMnO4))。
The capacitance of 4 differential responses object component Mn-P-O-N-C-1000 of table
Conclusion：Under same current density, same temperature, the performance of Mn-P-O-N-C-c-1000 is best.
Constant current charge-discharge curves of Fig. 8 Mn-P-O-N-C-c at a temperature of current density is 1A/g different heat treatment.
The capacitance of Mn-P-O-N-C-c at a temperature of 5 different heat treatment of table
Conclusion：Under same current density, the performance of Mn-P-O-N-C-c-1000 is best.Fig. 9 differential responses material components
The current density of Mn-P-O-N-C and capacitance relation figure (a-5:1、b-10:1、c-20:1、d-30:1、e-20:0 (no KMnO4))。
6 current density of table and capacitance relation table
Fig. 9 is current density and capacitance relation at the Mn-P-O-N-C of differential responses object component is 1000 DEG C in temperature
Figure.Found out by upper figure, when ratio, temperature are identical, with gradually increasing for current density, capacitance is gradually reduced, and Mn-P-
The capacitance of O-N-C-e-1000 materials is minimum, secondly Mn-P-O-N-C-d-1000, Mn-P-O-N-C-b-1000, Mn-P-
The capacitance of O-N-C-a-1000, Mn-P-O-N-C-c-1000 are maximum.Conclusion：In conclusion Fe-P-O-N-C-1-c-1000
Performance it is best.
The power density of table 8Mn-P-O-N-C-c-1000 and energy density relationships table
Figure 10 is that Mn-P-O-N-C-c-1000 power densities and energy are close under 1000 DEG C of temperature, different current densities
Spend relational graph.The power density of Mn-P-O-N-C-c-1000 is increased by the 0.2W/kg of current density 0.5A/g to 20A/g's
9.0KW/kg, energy density are increased to 38.4Wh/kg (0.5A/g) by 8.3Wh/kg (20A/g).Conclusion：The composite material have compared with
High energy density.
Cyclical stability tests of Figure 11 Mn-P-O-N-C-c-1000 in the case where current density is 10A/g.As seen from the figure, should
After electrode material charge and discharge cycles 15000 are enclosed, capacitance is held essentially constant.Conclusion：The composite material has stable electrochemistry
Energy.
Figure 12 is the electrochemical impedance test that Mn-P-O-N-C-c is carried out after 900 DEG C, 1000 DEG C, 1100 DEG C of processing respectively
By upper figure it is found that the resistance of Mn-P-O-N-C-c-900, Mn-P-O-N-C-c-1000, Mn-P-O-N-C-c-1100 material solution
All very littles, conclusion：Illustrate that the electric conductivity of the material is preferable.
As described above, the preparation method of the present invention passes through specific technique it can be seen from above-mentioned all embodiments
The synergistic combination and coordinative role of step, technological parameter and material selection etc., so as to obtain the nitrogen with excellent electric property
Phosphor codoping biomass carbon/manganese compound composite material, so as to may be used on capacitor area, have a good application prospect and
Industrialization potential and environmentally friendly electrode material, this is to be pursued in this century.
It should be appreciated that the purposes of these embodiments is merely to illustrate the present invention and is not intended to limitation protection model of the invention
It encloses.In addition, it should also be understood that, after reading the technical contents of the present invention, those skilled in the art can make the present invention each
Kind change, modification and/or variation, all these equivalent forms equally fall within the guarantor that the application the appended claims are limited
Within the scope of shield.
It will be apparent to those skilled in the art that technical solution that can be as described above and design, make other various
Corresponding change and deformation, and all these changes and deformation should all belong to the protection domain of the claims in the present invention
Within.
Claims (7)
1. a kind of preparation method of nitrogen-phosphor codoping biological carbon/manganese compound composite material, the preparation method includes specific step
Suddenly it is：
S1：Egg yolk and liquor potassic permanganate uniformly mix, and hydro-thermal reaction is for 24 hours in autoclave；
S2：After reaction, it is cooled to room temperature and is washed with ethyl alcohol, precipitation is dried；
S3：The drying sample is subjected to high-temperature process under inert gas shielding, so as to obtain the nitrogen-phosphor codoping biology
Carbon/manganese compound composite material.
2. preparation method as described in claim 1, which is characterized in that the egg yolk and potassium permanganate in the step S1 are mixed
Mass ratio during conjunction is 20:1.
3. preparation method as claimed in claim 3, which is characterized in that the reaction temperature in the step S1 is 160-220 DEG C.
4. the preparation method as described in any one of claim 1,2 or 3, which is characterized in that at the high temperature in the step S3
Temperature is managed at 900-1100 DEG C.
5. preparation method as claimed in claim 4, which is characterized in that the high-temperature process temperature is most preferably 1000 DEG C.
6. the purposes of composite material made from preparation method as described in claim 1, which is characterized in that the composite material is used for
The electrode of capacitor.
7. the manufacturing method of electrode for capacitors as claimed in claim 6, which is characterized in that the manufacturing method includes specific
Step is：
(A) weigh claim 1 preparation composite material, acetylene black, PTFE (polytetrafluoroethylene (PTFE)) lotion (three's mass ratio be 8:
1:1) ethanol in proper amount, is added in, is uniformly mixed, when being stirred continuously into starchiness, is coated onto in nickel foam；
(B) nickel foam for coating the composite material be dried, dried, tabletting is to get to the electrode for capacitors.
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