CN105140043A - Manganese oxide/N-doped carbon microsphere composite electrode materials and preparation and application thereof - Google Patents
Manganese oxide/N-doped carbon microsphere composite electrode materials and preparation and application thereof Download PDFInfo
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Abstract
The invention provides manganese oxide/N-doped carbon microsphere composite electrode materials and preparation and application thereof. The preparation method comprises steps of solving N-donor ligands and aldehyde in solution so as to carry out pre-condensation reaction; adding potassium permanganate for continuous reaction; carrying out crystallization, filtering, washing and drying so as to obtain manganese fictionalization N-containing polymeric microspheres; and carrying out carbonation reaction on the manganese fictionalization N-containing polymeric microspheres so as to obtain the manganese oxide/N-doped carbon microsphere composite electrode materials. The invention also provides the prepared manganese oxide/N-doped carbon microsphere composite electrode materials with the preparation method and the application thereof in a supercapacitor. The preparation method is simple in technology and economical raw materials are used. The prepared manganese oxide/N-doped carbon microsphere composite electrode materials have multi-stage structures with abundant microholes, mesoporouses and big holes; manganese oxide is uniformly dispersed in the N-doped carbon microspheres; and the materials have quite high specific capacitance and quite long service lifetime.
Description
Technical field
The present invention relates to a kind of Mn oxide/nitrogen-doped carbon microballoon combination electrode material and preparation and application thereof, belong to functionalized carbon combination electrode material preparing technical field and supercapacitor applications field.
Background technology
Ultracapacitor is a kind of novel energy-storing element between secondary cell and traditional capacitor, there is the advantages such as charge-discharge velocity is fast, power density is high, have extended cycle life, have broad application prospects in fields such as mobile communication, electronic technology, science and techniques of defence, and electrode material is the key determining ultracapacitor performance.
In numerous transition metal oxide, Mn oxide is cheap, environmental friendliness, theoretical ratio capacitance high (1370F/g), and it also receives the concern of more and more researcher.Owing to only having the Mn oxide on surface to have accumulate effect, the intrinsic ratio capacitance of bulk Mn oxide is often difficult to embody; And the cyclical stability of Mn oxide and poorly conductive, this causes its actual Application comparison difficulty.And the material with carbon element with high porosity can not only improve stability and the conductivity of Mn oxide as matrix, the dispersiveness of Mn oxide can also be improved, improve its utilance, and then improve its capacitive property.Therefore, Mn oxide and porous carbon materials are carried out compound and become study hotspot in recent years to improve electrode material performance.Various Mn oxide/porous carbon composite, such as MnO
2/ Graphene (LuMao, KaiZhang, HardySzeOnChan, JishanWu.NanostructuredMnO
2/ graphenecompositesforsupercapacitorelectrodes:theeffecto fmorphology, crystallinityandcomposition, JournalofMaterialsChemistry, 2012,22:1845-1851), MnO
x/ carbon nano-tube (QiLi, Xue-FengLu, HanXu, Ye-XiangTong, Gao-RenLi.Carbon/MnO
2double-wallednanotubearrayswithfastionandelectrontransmi ssionforhigh-performancesupercapacitors, ACSApplliedMaterialsandInterfaces, 2014,6:2726-2733), MnO
x/ carbon nano-fiber (YongsongLuo, JianJiang, WeiweiZhou, HuanpingYang, JingshanLuo, XiaoyingQi, HuaZhang, DenisY.W.Yu, ChangMingLi, TingYu.Self-assemblyofwell-orderedwhisker-likemanganeseo xidearraysoncarbonfiberpaperanditsapplicationaselectrode materialforsupercapacitors, JournalofMaterialsChemistry, 2012, 22:8634-864) etc. be produced out by multi-step synthetic methods, all there is higher ratio capacitance.In addition, the nitrogen-doped modified ratio capacitance being conducive to improving electrode material is carried out to material with carbon element.Such as carry out nitrogen-doped modified to Mn oxide/carbosphere, ratio capacitance brings up to 306F/g (LeiLi, RuminLi, ShiliGai, ShujiangDing, FeiHe, MilinZhang, PiaopingYang.MnO from 260F/g
2nanosheetsgrownonnitrogen-dopedhollowcarbonshellsasahigh-performanceelectrodeforasymmetricsupercapacitors, Chemistry-AEuropeanJournal, 2015,21:7119-7126).Therefore, porous carbon materials Mn oxide being introduced N doping can not only improve the dispersiveness of Mn oxide, can also the electronic property of modulation carbon carrier, is expected the capacitive property promoting Mn oxide further.
At present, Mn oxide/N doping porous carbon combination electrode material is prepared mainly through multistep processes, i.e. pre-synthesis porous carbon or N doping porous carbon support, and then flood manganese salt, combination electrode material (ZhongJieZhang is obtained after reduction, LiangXiaoCheng, XiangYingChen.Nitrogen/manganeseoxidesco-dopednanoporous carbonmaterials:structurecharacterizationandelectrochemi calperformancesforsupercapacitorapplications, ElectrochimicaActa, 2015, 161:84-94, XiangYingChen, ChongChen, ZhongJieZhang, DongHuaXie, JianWeiLiu.Nitrogen/manganeseoxidesdopedporouscarbonsder ivedfromsodiumbutylnaphthalenesulfonate, JournalofColloidandInterfaceScience, 2013,398:176-184).But, although the combination electrode material ratio capacitance that these preparation methods prepare improves a lot, but synthesis step is many, last long, cost is high, the more important thing is, the usual bad dispersibility of Mn oxide of load, low with carrier bond strength, these features limit the further raising of Mn oxide/N doping porous carbon combination electrode material capacitive property.
Summary of the invention
For solving the problems of the technologies described above, the object of the present invention is to provide a kind of Mn oxide/nitrogen-doped carbon microballoon combination electrode material.
The present invention also aims to the preparation method that a kind of above-mentioned Mn oxide/nitrogen-doped carbon microballoon combination electrode material is provided.
The present invention also aims to provide the above-mentioned Mn oxide/application of nitrogen-doped carbon microballoon combination electrode material in ultracapacitor.
The present invention also aims to the preparation method providing a kind of Mn oxide/nitrogen-doped carbon microballoon combination electrode material, the method comprises the following steps:
A, containing n-donor ligand and aldehyde are dissolved in solvent carry out condensation reaction in advance, then add potassium permanganate, continue reaction, then after crystallization, filtration, washing, drying, obtain the polymer with nitrogen microballoon of manganese functionalization;
B, again the polymer with nitrogen microballoon of described manganese functionalization is carried out carburizing reagent, obtain described Mn oxide/nitrogen-doped carbon microballoon combination electrode material.
According to method of the present invention, preferably, the mol ratio of described aldehyde, potassium permanganate, solvent and containing n-donor ligand is 10-20:2.0 × 10
-3-5.5 × 10
-3: 6-24:1.
In the preparation process of Mn oxide provided by the invention/nitrogen-doped carbon microballoon combination electrode material, the mol ratio of potassium permanganate and containing n-donor ligand is 2.0 × 10
-3-5.5 × 10
-3, the amount ranges of corresponding potassium permanganate is 8-22mg, and in preparation process of the present invention, too high potassium permanganate addition (30-60mg) can cause finally can not get spherical Mn oxide/nitrogen-doped carbon combination electrode material.
According to method of the present invention, preferably, the mol ratio of described aldehyde and containing n-donor ligand is 15:1.
According to method of the present invention, preferably, the baking temperature of described drying is 70-100 DEG C, and drying time is 4-8h.
According to method of the present invention, particularly, the washing in step a is the routine operation of this area, and the main purpose of washing is the potassium permanganate washing away aldehydes and the not firmly load not participating in condensation reaction; Use aldehydes detector is detected the aldehydes in filtrate in a preferred embodiment of the invention, when filtered fluid is colourless, and when aldehydes detector can't detect aldehydes, can stop washing; In some concrete execution modes of the present invention, washing solvent load used is 30-50mL, and washing solvent used is water and ethanol.
According to method of the present invention, preferably, described containing n-donor ligand comprises the combination of one or more in dicyanodiamine, melamine, urea and thiocarbamide.
According to method of the present invention, preferably, described aldehyde comprises the combination of one or more in formaldehyde, acetaldehyde, propionic aldehyde, benzaldehyde and glyoxal.
According to method of the present invention, preferably, described solvent comprises the combination of one or more in ethanol, acetone, water and DMF.
According to method of the present invention, preferably, the reaction temperature of described condensation reaction is in advance 50-100 DEG C, and the reaction time is 5-30min.
According to method of the present invention, preferably, first described condensation reaction is in advance carried out at 50 DEG C, is then warming up to 100 DEG C and proceeds condensation reaction in advance; Namely the condensation reaction in advance in step a needs segmentation to carry out, but the present invention is to the not requirement of concrete reaction time of this two-stage reaction, as long as this reaction time sum of two sections meets 5-30min.
According to method of the present invention, preferably, after adding potassium permanganate in step a, continue reaction 5-30min at 50-100 DEG C.
According to method of the present invention, preferably, described crystallization is at 150-200 DEG C of crystallization 5-10h.
According to method of the present invention, preferably, step b be by the polymer with nitrogen microballoon of described manganese functionalization under isolated air conditions, with the ramp of 1-10 DEG C/min to >=700 DEG C, and carry out carburizing reagent 1-8h at such a temperature, obtain described Mn oxide/nitrogen-doped carbon microballoon combination electrode material.
According to method of the present invention, preferably, step b is by the polymer with nitrogen microballoon of described manganese functionalization under isolated air conditions, with the ramp to 850 DEG C of 1 DEG C/min, and carry out carburizing reagent 3h at such a temperature, obtain described Mn oxide/nitrogen-doped carbon microballoon combination electrode material.In the preferred embodiment of the present invention, the polymer with nitrogen microballoon of manganese functionalization can be placed in inert gas atmosphere to realize carrying out carburizing reagent to it under isolated air conditions, the gas of described inertia comprises nitrogen, argon gas etc., but the economic factor of considering, this inert gas is preferably nitrogen.
Present invention also offers Mn oxide/nitrogen-doped carbon microballoon combination electrode material that above-mentioned Mn oxide/nitrogen-doped carbon microballoon combination electrode material preparation method prepares.
Present invention also offers the above-mentioned Mn oxide/application of nitrogen-doped carbon microballoon combination electrode material in ultracapacitor.
The Mn oxide that the present invention relates to/nitrogen-doped carbon microballoon combination electrode material preparation method does not use pore-forming reagent, second carbon source, do not need additional nitrogenous source, but transform the polymer with nitrogen microballoon of manganese functionalization by direct and then realize the original position preparation of Mn oxide/nitrogen-doped carbon microballoon combination electrode material yet.This preparation method's technique is simple, raw material economics, effectively can not only control dispersiveness and the content of Mn oxide, strengthen the bond strength of Mn oxide and nitrogen-doped carbon microballoon, and the dopant states of nitrogen can be controlled, be the high-efficiency synthesis method being different from conventional method, be expected to obtain important commercial Application.
The Mn oxide that preparation method of the present invention obtains/nitrogen-doped carbon microballoon combination electrode material has abundant micropore, mesoporous, macropore multilevel hierarchy, and Mn oxide is wherein uniformly dispersed in nitrogen-doped carbon microballoon, content is adjustable, high with nitrogen-doped carbon microballoon bond strength, in addition N doping is to effective modulation of carbosphere electronic property, thus makes this combination electrode material have high ratio capacitance.
Mn oxide the present invention prepared/nitrogen-doped carbon microballoon combination electrode material is used in ultracapacitor, in the preferred embodiment of the present invention, when in described Mn oxide/nitrogen-doped carbon microballoon combination electrode material, Mn content is 0.3wt%, when sweep speed is 1mV/s, ratio capacitance is up to 487F/g; And after the charge and discharge 5000 times of circulating, the retention of ratio capacitance is still up to 98%, this shows that Mn oxide/nitrogen-doped carbon microballoon combination electrode material that the present invention prepares has higher ratio capacitance and longer useful life, and its performance is better than the combination electrode material that prepared by mechanical agitation, impregnating post-synthesis, and (its ratio capacitance is respectively: 246F/g, 312F/g; Cycle charge-discharge number of times is all lower than 2000 times).
Accompanying drawing explanation
Fig. 1 a is the SEM figure of manganese functionalization melamino-formaldehyde microballoon (0.003Mn-MF) that embodiment 1 is synthesized;
Fig. 1 b is Mn oxide/nitrogen-doped carbon microballoon combination electrode material (0.003MnO that embodiment 1 prepares
x-NCS) SEM figure;
Fig. 1 c is the SEM figure of manganese functionalization melamino-formaldehyde microballoon (0.009Mn-MF) that comparative example 1 is synthesized;
Fig. 1 d is the Mn oxide/nitrogen-doped carbon combination electrode material (0.009MnO of the pattern breakage that comparative example 1 prepares
x-NCS) SEM figure;
Fig. 2 a, Fig. 2 b are the SEM-EDS figure of manganese functionalization melamino-formaldehyde microballoon (0.003Mn-MF) that embodiment 1 is synthesized;
Fig. 2 c, Fig. 2 d are Mn oxide/nitrogen-doped carbon microballoon combination electrode material (0.003MnO that embodiment 1 prepares
x-NCS) SEM-EDS figure;
Fig. 3 a is the TEM figure of manganese functionalization melamino-formaldehyde microballoon (0.003Mn-MF) that embodiment 1 is synthesized;
Fig. 3 b is Mn oxide/nitrogen-doped carbon microballoon combination electrode material (0.003MnO that embodiment 1 prepares
x-NCS) TEM figure;
Fig. 4 a is Mn oxide/nitrogen-doped carbon microballoon combination electrode material (0.003MnO that embodiment 1 prepares
x-NCS) X-ray absorption near edge structure (XANES) spectrogram;
Fig. 4 b is Mn oxide/nitrogen-doped carbon microballoon combination electrode material (0.003MnO that embodiment 1 prepares
x-NCS) radial distribution bond distance figure;
Fig. 5 a is Mn oxide/nitrogen-doped carbon microballoon combination electrode material (0.003MnO that embodiment 1 prepares
x-NCS) N
2isothermal suction/desorption curve figure;
Fig. 5 b is Mn oxide/nitrogen-doped carbon microballoon combination electrode material (0.003MnO that embodiment 1 prepares
x-NCS) mesoporous pore size distribution map;
Fig. 5 c is Mn oxide/nitrogen-doped carbon microballoon combination electrode material (0.003MnO that embodiment 1 prepares
x-NCS) micropore size distribution map;
Fig. 6 is Mn oxide/nitrogen-doped carbon microballoon combination electrode material (0.003MnO that embodiment 1 prepares
x-NCS) Raman characterize spectrogram;
Fig. 7 a is Mn oxide/nitrogen-doped carbon microballoon combination electrode material (0.003MnO that embodiment 1 prepares
x-NCS) cyclic voltammetry scan (sweep speed is respectively: 1,2,5,10,20,50,100mV/s) result figure;
Fig. 7 b is Mn oxide/nitrogen-doped carbon microballoon combination electrode material (0.003MnO that embodiment 1 prepares
x-NCS) constant current charge-discharge (current density is respectively: 0.25,0.50,1.0,2.0A/g) result figure;
Fig. 8 is Mn oxide/nitrogen-doped carbon microballoon combination electrode material (0.003MnO that embodiment 1 prepares
x-NCS) cycle charge-discharge the performance test results figure (current density is 5.0A/g).
Embodiment
The beneficial effect of implementation process of the present invention and generation will be explained by specific embodiment and Figure of description below, be intended to help reader to understand essence of the present invention and feature better, but not as can the restriction of practical range to this case.
Embodiment 1
Present embodiments provide the preparation method of a kind of Mn oxide/nitrogen-doped carbon microballoon combination electrode material, wherein, this preparation method comprises following concrete steps:
A, take 3.1g melamine, 30.0g formaldehyde (37wt%) mixes with 10.5g water, in 50 DEG C stir 5min; Then rise to 100 DEG C, and keep 10min, add 20mg potassium permanganate, Keep agitation 20min, then in 150 DEG C of crystallization 8h.Gained solid after filtration, water and ethanol washing, 80 DEG C of dry 4h, obtain the melamino-formaldehyde microballoon of manganese functionalization, be designated as 0.003Mn-MF;
B, take the melamino-formaldehyde microballoon of the above-mentioned manganese functionalization of 1g, at N
2under atmosphere, with the speed of 1 DEG C/min from room temperature to 850 DEG C, and keep 3h at such a temperature, obtain Mn oxide/nitrogen-doped carbon microballoon composite material, be designated as 0.003MnO
x(0.003 refers to MnO to-CNS
xthe weight percentage of manganese in-CNS composite material, be with the total weight of this composite material for benchmark obtains, it is obtained by ICP-AES method of testing).
By 0.003Mn-MF, 0.003MnO that embodiment 1 prepares
x-NCS composite material SEM, EDS, TEM, XAFS, low temperature N
2the technology such as suction/desorption, Raman spectrum characterizes.
0.003Mn-MF and 0.003MnO that embodiment 1 prepares
xrespectively as shown in Figure 1 a, 1 b, as can be seen from Fig. 1 a, Fig. 1 b, 0.003Mn-MF microballoon there occurs contraction to the SEM figure of-NCS composite material after carbonization, and microsphere diameter has been reduced to 2.5 μm from 5 μm, and inter-adhesive.
The SEM-EDS figure of the 0.003Mn-MF that embodiment 1 prepares as shown in Fig. 2 a, Fig. 2 b, the 0.003MnO that embodiment 1 prepares
xthe SEM-EDS figure of-NCS composite material is as shown in Fig. 2 c, Fig. 2 d, as can be seen from Fig. 2 a, Fig. 2 b, Fig. 2 c, Fig. 2 d, O, Mn content before carbonization rear difference is little, and after carbonization, N content reduces, C content increases, and shows that high temperature cabonization makes part itrogenous organic substance run off because of pyrolysis.Wherein, in Fig. 2 b, Fig. 2 d, ordinate KCnt is the Essential Terms of this area, and it refers to that X ray counts, and namely intensity level is relevant with constituent content, K=1000, Cnt=counts, Counts, count number.Unit is generally cps (count number per second).
0.003Mn-MF and 0.003MnO that embodiment 1 prepares
xthe TEM of-NCS composite material schemes respectively as shown in Figure 3 a, 3 b, as can be seen from Fig. 3 a, Fig. 3 b, 0.003Mn-MF and 0.003MnO
xboth-NCS composite materials all have uniform spherical morphology, but sample contrast after carbonization is clearly demarcated, shows that manganese oxide particle is uniformly dispersed on nitrogen-doped carbon microballoon.
The 0.003MnO that embodiment 1 prepares
xthe XANES spectrogram of-NCS composite material and radial distribution bond distance result figure respectively as shown in Fig. 4 a, Fig. 4 b, as can be seen from Fig. 4 a, Fig. 4 b, the relative MnO of ABSORPTION EDGE of manganese
2move to low energy direction, show to define Mn oxide at a low price; Show in Fig. 4 b and be positioned at
mn-O bond distance distribution, directly show the formation of Mn oxide.
The 0.003MnO that embodiment 1 prepares
xthe N of-NCS composite material
2suction/desorption isotherm figure as shown in Figure 5 a, as can be seen from Fig. 5 a, 0.003MnO
xthe thermoisopleth of-NCS composite material is II type composite curve, shows 0.003MnO
x-NCS composite material has macroporous structure;
The 0.003MnO that embodiment 1 prepares
xmesoporous, the micropore size distribution map of-NCS composite material respectively as shown in Fig. 5 b, Fig. 5 c, as can be seen from Fig. 5 b, Fig. 5 c, 0.003MnO
xthe mesoporous pore size of-NCS composite material is 2.3,2.8,3.8nm, micropore size is 1.2,1.4,1.5,1.7nm.Thus 0.003MnO
x-NCS has micropore, mesoporous, macropore multilevel hierarchy.
The 0.003MnO that embodiment 1 prepares
xthe Raman of-NCS composite material characterizes spectrogram as shown in Figure 6, as can be seen from Figure 6, is positioned at 1368cm in Fig. 6
– 1the D band at place is attributed to agraphitic carbon, is positioned at 1684cm
– 1the G band at place is attributed to graphitized carbon, and is positioned at 1530cm
– 1the A band at place is attributed to containing heteroatomic agraphitic carbon.The ratio of peak area of D band and G band is the ratio of the peak area that 2.5, A band and G are with is 1.0, and this shows the 0.003MnO that embodiment 1 prepares
x-NCS composite material the degree of order is higher, and has amorphous carbon structure that is nitrogenous or oxygen.
Above result shows, Mn oxide/nitrogen-doped carbon microballoon the composite material adopting the inventive method to prepare has abundant pore structure, Mn oxide is wherein uniformly dispersed, and the material degree of order is high, and these features are all conducive to the capacitive property improving composite material.
Embodiment 2
Present embodiments provide the preparation method of a kind of Mn oxide/nitrogen-doped carbon microballoon combination electrode material, wherein, this preparation method comprises following concrete steps:
A, take 3.1g melamine and 30.0g formaldehyde (37wt%) is dissolved in 10.5g ethanol and stirs, 5min is kept in 50 DEG C, then be warming up to 100 DEG C and keep 10min, then 20mg potassium permanganate is added, and keep 20min, then 180 DEG C of crystallization 8h, gained solid product after filtration, water and ethanol washing, obtain the polymer with nitrogen microballoon of manganese functionalization after 70 DEG C of dry 4.5h;
B, get the polymer with nitrogen microballoon of 1g manganese functionalization in N
2under atmosphere, with the speed of 2 DEG C/min from room temperature to 710 DEG C, and keep 5h at such a temperature, obtain Mn oxide/nitrogen-doped carbon microballoon composite material.
Embodiment 3
Present embodiments provide the preparation method of a kind of Mn oxide/nitrogen-doped carbon microballoon combination electrode material, wherein, this preparation method comprises following concrete steps:
A, take 1.5g urea and 30.0g formaldehyde (37wt%) is dissolved in 10.5g water and stirs, 5min is kept in 50 DEG C, then 100 DEG C are warming up to, keep 10min, add 10mg potassium permanganate, keep 10min, then 180 DEG C of crystallization 8h, gained solid product after filtration, water and ethanol washing, obtain the polymer with nitrogen microballoon of manganese functionalization after 85 DEG C of dry 5h;
B, get the polymer with nitrogen microballoon of 1g manganese functionalization in N
2under atmosphere, with the speed of 5 DEG C/min from room temperature to 850 DEG C, and keep 5h at such a temperature, obtain Mn oxide/nitrogen-doped carbon microballoon composite material.
Embodiment 4
Present embodiments provide the preparation method of a kind of Mn oxide/nitrogen-doped carbon microballoon combination electrode material, wherein, this preparation method comprises following concrete steps:
A, take 1.9g thiocarbamide and be dissolved in 10.5g acetone with 30.0g formaldehyde (37wt%) and mix, 10min is stirred in 50 DEG C, then 100 DEG C are warming up to, after continuing to stir 10min, add 20mg potassium permanganate, stir 5min again, then 200 DEG C of crystallization 8h, products therefrom after filtration, water and ethanol washing, obtain the polymer with nitrogen microballoon of manganese functionalization after 90 DEG C of dry 6h;
B, get the polymer with nitrogen microballoon of the above-mentioned manganese functionalization of 1g in N
2under atmosphere, with the speed of 5 DEG C/min from room temperature to 800 DEG C, and keep 3h at such a temperature, obtain Mn oxide/nitrogen-doped carbon microballoon composite material.
Embodiment 5
Present embodiments provide the preparation method of a kind of Mn oxide/nitrogen-doped carbon microballoon combination electrode material, wherein, this preparation method comprises following concrete steps:
A, take 3.1g melamine and 15g acetaldehyde is dissolved in 10.5g acetone, 10min is stirred in 50 DEG C, be warming up to 100 DEG C again and stir 20min, then 20mg potassium permanganate is added, continue again to stir 10min, in 150 DEG C of crystallization 8h, products therefrom after filtration, water and ethanol washing, obtain the polymer with nitrogen microballoon of manganese functionalization after 100 DEG C of dry 7h;
B, get the polymer with nitrogen microballoon of the above-mentioned manganese functionalization of 1g in N
2under atmosphere, with the speed of 8 DEG C/min from room temperature to 900 DEG C, and keep 5h at such a temperature, obtain Mn oxide/nitrogen-doped carbon microballoon composite material.
Embodiment 6
Present embodiments provide the preparation method of a kind of Mn oxide/nitrogen-doped carbon microballoon combination electrode material, wherein, this preparation method comprises following concrete steps:
A, take 3.1g melamine and 28g benzaldehyde is dissolved in 10.5g water, stir in 50 DEG C and keep 20min, be warming up to 100 DEG C again, stir 10min, then 20mg potassium permanganate is added, continue again to stir 10min, then 150 DEG C of crystallization 8h, products therefrom after filtration, water and ethanol washing, obtain the polymer with nitrogen microballoon of manganese functionalization after 80 DEG C of dry 8h;
B, get the polymer with nitrogen microballoon of the above-mentioned manganese functionalization of 1g in N
2under atmosphere, with the speed of 10 DEG C/min from room temperature to 800 DEG C, and keep 5h at such a temperature, obtain Mn oxide/nitrogen-doped carbon microballoon composite material.
Comparative example 1
This comparative example provides a kind of preparation method of Mn oxide/nitrogen-doped carbon combination electrode material of pattern breakage, and wherein, this preparation method comprises following concrete steps:
A, take 3.1g melamine, 30.0g formaldehyde (37wt%) mixes with 10.5g water, in 50 DEG C stir 5min; Then rise to 100 DEG C, and keep 10min, add 60mg potassium permanganate, Keep agitation 20min, then in 150 DEG C of crystallization 8h, gained solid after filtration, water and ethanol washing, 80 DEG C of dry 4h, obtain the melamino-formaldehyde microballoon of manganese functionalization, be designated as 0.009Mn-MF;
B, get the melamino-formaldehyde microballoon of the above-mentioned manganese functionalization of 1g in N
2under atmosphere, with the speed of 10 DEG C/min from room temperature to 800 DEG C, and keep 5h at such a temperature, obtain the Mn oxide/nitrogen-doped carbon composite material of pattern breakage, be designated as 0.009MnO
x(0.009 refers to MnO to-NCS
xthe weight percentage of manganese in-CNS composite material, be with the total weight of this composite material for benchmark obtains, it is obtained by ICP-AES method of testing).
By 0.009Mn-MF, 0.009MnO that comparative example 1 prepares
x-NCS composite material SEM technology characterizes.
0.009Mn-MF and 0.009MnO that comparative example 1 prepares
xthe SEM figure of-NCS composite material is respectively as shown in Fig. 1 c, Fig. 1 d, and as can be seen from Fig. 1 c, Fig. 1 d, the melamino-formaldehyde microballoon 0.009Mn-MF of the manganese functionalization that comparative example 1 prepares has spherical morphology, but its 0.009MnO obtained after carbonization
xthe spherical morphology of-NCS composite material is destroyed.This shows, too high potassium permanganate addition is unfavorable for obtaining spherical Mn oxide/nitrogen-doped carbon combination electrode material.
Application examples 1
Should provide the application that Mn oxide/nitrogen-doped carbon microballoon composite material that embodiment 1 prepares is used as electrode material for super capacitor by use-case, wherein, this application comprises following concrete steps:
First, by mass ratio be Mn oxide/nitrogen-doped carbon microballoon composite material, acetylene black, the polytetrafluoroethylene (60wt%) that the embodiment 1 of 7:2:1 prepares mix with ethanol, stir after be coated in the nickel foam of 1cm × 1cm, in 3MPa lower sheeting 1min, then after 80 DEG C of vacuumize 12h, obtain work electrode, and use 6MKOH soaked overnight.
Capacitive property evaluation adopts three-electrode system, using saturated calomel electrode as reference electrode, platinum electrode is done electrode, by carry out on CHI660EB14013 type electrochemical workstation cyclic voltammetric (scanning frequency is 1,2,5,10,20,50,100mV/s), constant current charge-discharge (current density is 0.25,0.5,1.0,2.0A/g) and life-span (current density is 5A/g) test realize.Wherein, average quality ratio capacitance calculates according to formula (1):
In formula (1): C
avgfor Average specific capacities (F/g), C is electric capacity (F), m is electrode material quality (g), I be charging and discharging currents (A) ， ⊿ t be discharge time (s) ， ⊿ V be charging/discharging voltage window (V).
The Mn oxide that embodiment 1 prepares/nitrogen-doped carbon microballoon combination electrode material (0.003MnO
x-NCS) cyclic voltammetry scan (sweep speed to be respectively: 1,2,5,10,20,50,100mV/s) result figure as shown in Figure 7a;
The Mn oxide that embodiment 1 prepares/nitrogen-doped carbon microballoon combination electrode material (0.003MnO
x-NCS) constant current charge-discharge (current density is respectively: 0.25,0.50,1.0,2.0A/g) result figure as shown in Figure 7b;
The Mn oxide that embodiment 1 prepares/nitrogen-doped carbon microballoon combination electrode material (0.003MnO
x-NCS) cycle charge-discharge the performance test results figure (current density is 5.0A/g) as shown in Figure 8.
As can be seen from Fig. 7 a, the cyclic voltammetry curve of the Mn oxide that embodiment 1 prepares/nitrogen-doped carbon microballoon combination electrode material presents the shape being similar to rectangle, shows 0.003MnO
x-NCS material has good ultracapacitor performance, simultaneously, the integral area that cyclic voltammetry curve surrounds increases with the reduction of sweep speed, illustrates that the ratio capacitance of Mn oxide/nitrogen-doped carbon microballoon combination electrode material that embodiment 1 prepares increases gradually.
As can be seen from Fig. 7 b, the constant current charge-discharge curve of the Mn oxide that embodiment 1 prepares/nitrogen-doped carbon microballoon combination electrode material presents leg-of-mutton shape, does not have obvious internal resistance to fall, shows 0.003MnO
xthe reversible charge-discharge performance of-NCS material is good, at higher current densities (2.0A/g), the Mn oxide that this embodiment 1 prepares/nitrogen-doped carbon microballoon combination electrode material can carry out quick charge, shows that this composite material is excellent electrode material for super capacitor.
As can be seen from Figure 8,0.003MnO
x-NCS material is after circulation charge and discharge 5000 times, and the retention of ratio capacitance is still up to 98%, and this shows that Mn oxide/nitrogen-doped carbon microballoon combination electrode material that the present invention prepares has longer useful life.
Claims (10)
1. a preparation method for Mn oxide/nitrogen-doped carbon microballoon combination electrode material, wherein, the method comprises the following steps:
A, containing n-donor ligand and aldehyde are dissolved in solvent carry out condensation reaction in advance, then add potassium permanganate, continue reaction, then after crystallization, filtration, washing, drying, obtain the polymer with nitrogen microballoon of manganese functionalization; Preferred described baking temperature is 70-100 DEG C, and drying time is 4-8h;
B, again the polymer with nitrogen microballoon of described manganese functionalization is carried out carburizing reagent, obtain described Mn oxide/nitrogen-doped carbon microballoon combination electrode material;
The mol ratio of preferred described aldehyde, potassium permanganate, solvent and containing n-donor ligand is 10-20:2.0 × 10
-3-5.5 × 10
-3: 6-24:1;
More preferably the mol ratio of described aldehyde and containing n-donor ligand is 15:1.
2. method according to claim 1, wherein, described containing n-donor ligand comprises the combination of one or more in dicyanodiamine, melamine, urea and thiocarbamide.
3. method according to claim 1, wherein, described aldehyde comprises the combination of one or more in formaldehyde, acetaldehyde, propionic aldehyde, benzaldehyde and glyoxal.
4. method according to claim 1, wherein, described solvent comprises the combination of one or more in ethanol, acetone, water and DMF.
5. method according to claim 1, wherein, the reaction temperature of described condensation reaction is in advance 50-100 DEG C, and the reaction time is 5-30min; Preferably, first condensation reaction is in advance carried out at 50 DEG C, is then warming up to 100 DEG C and proceeds condensation reaction in advance.
6. method according to claim 1, wherein, after adding potassium permanganate in step a, continues reaction 5-30min at 50-100 DEG C.
7. method according to claim 1, wherein, described crystallization is at 150-200 DEG C of crystallization 5-10h.
8. method according to claim 1, wherein, step b be by the polymer with nitrogen microballoon of described manganese functionalization under isolated air conditions, with the ramp of 1-10 DEG C/min to >=700 DEG C, and carry out carburizing reagent 1-8h at such a temperature, obtain described Mn oxide/nitrogen-doped carbon microballoon combination electrode material;
Be preferably under isolated air conditions, with the ramp to 850 DEG C of 1 DEG C/min, and carry out carburizing reagent 3h at such a temperature, obtain described Mn oxide/nitrogen-doped carbon microballoon combination electrode material.
9. Mn oxide/nitrogen-doped carbon microballoon combination electrode material that the Mn oxide described in any one of claim 1-8/nitrogen-doped carbon microballoon combination electrode material preparation method prepares.
10. the Mn oxide according to claim 9/application of nitrogen-doped carbon microballoon combination electrode material in ultracapacitor.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105914050A (en) * | 2016-04-13 | 2016-08-31 | 华中科技大学 | Preparation method of carbon electrode material and application thereof |
| CN106430146A (en) * | 2016-11-22 | 2017-02-22 | 重庆文理学院 | Nitrogen-manganese co-doped hierarchical porous carbon material preparation method |
| CN108389731A (en) * | 2018-03-28 | 2018-08-10 | 齐鲁工业大学 | A kind of melamine/thiocarbamide prepares electrode material for super capacitor with formaldehyde copolymer method |
| CN110853930A (en) * | 2018-08-21 | 2020-02-28 | Tcl集团股份有限公司 | Electrode material, preparation method thereof and super capacitor |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102637533A (en) * | 2012-04-27 | 2012-08-15 | 黑龙江大学 | Method for preparing nitrogenous graphitized hollow carbon microspheres |
| CN104192820A (en) * | 2014-07-14 | 2014-12-10 | 上海应用技术学院 | Mesoporous carbon sphere/manganese dioxide composite nano material and preparation method thereof |
-
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102637533A (en) * | 2012-04-27 | 2012-08-15 | 黑龙江大学 | Method for preparing nitrogenous graphitized hollow carbon microspheres |
| CN104192820A (en) * | 2014-07-14 | 2014-12-10 | 上海应用技术学院 | Mesoporous carbon sphere/manganese dioxide composite nano material and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| BETTING FRIEDEL等: ""Preparation of Monodisperse, Submicrometer Carbon Spheres by Pyrolysis of Melamine-Formaldehyde Resin"", 《SMALL》 * |
| LEI LI等: ""MnO2 Nanosheets Grown on Nitrogen-Doped Hollow Carbon Shells as a High-Performance Electrode for Asymmetric Supercapacitors"", 《CHEM. EUR. J.》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105914050A (en) * | 2016-04-13 | 2016-08-31 | 华中科技大学 | Preparation method of carbon electrode material and application thereof |
| CN106430146A (en) * | 2016-11-22 | 2017-02-22 | 重庆文理学院 | Nitrogen-manganese co-doped hierarchical porous carbon material preparation method |
| CN108389731A (en) * | 2018-03-28 | 2018-08-10 | 齐鲁工业大学 | A kind of melamine/thiocarbamide prepares electrode material for super capacitor with formaldehyde copolymer method |
| CN110853930A (en) * | 2018-08-21 | 2020-02-28 | Tcl集团股份有限公司 | Electrode material, preparation method thereof and super capacitor |
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