CN109659138A - A kind of hollow carbon sphere/nickel sulfide of N doping/graphene ternary active multilayer/multi-factor structure composite material and preparation method - Google Patents
A kind of hollow carbon sphere/nickel sulfide of N doping/graphene ternary active multilayer/multi-factor structure composite material and preparation method Download PDFInfo
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- CN109659138A CN109659138A CN201811568172.3A CN201811568172A CN109659138A CN 109659138 A CN109659138 A CN 109659138A CN 201811568172 A CN201811568172 A CN 201811568172A CN 109659138 A CN109659138 A CN 109659138A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/20—Light-sensitive devices
- H01G9/2022—Light-sensitive devices characterized by he counter electrode
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/20—Light-sensitive devices
- H01G9/2059—Light-sensitive devices comprising an organic dye as the active light absorbing material, e.g. adsorbed on an electrode or dissolved in solution
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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
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/542—Dye sensitized solar cells
Abstract
The invention discloses a kind of hollow carbon sphere/nickel sulfide of N doping/graphene ternary active multilayer/multi-factor structure composite materials, the material is uniformly distributed loose porous nanometer nickel sulfide piece for surface and is anchored on hollow nitrogen-doped nanometer ball, and outermost layer encapsulates the multilayer multielement hollow structural material that redox graphene is formed.When the material is used as dye-sensitized solar cells to electrode, the battery has shown brilliant photoelectric conversion performance: under the same terms, the NHCS/NiS/RGO of assembling is up to 9.32% to the photoelectric conversion efficiency of the dye-sensitized solar cells of electrode material, respectively higher than the 8.06% of the 5.05% and Pt of 8.78%, the NHCS of NHCS/NiS.Also, the material also has excellent catalytic performance, can be effectively facilitated the redox reaction of the iodide ion pair at electrolyte/composite material interface.In addition, the material is prepared by the method for solvent heat, preparation process is simple, low in cost and no pollution to the environment.
Description
Technical field
The present invention relates to field of dye-sensitized solar cells and it is related to it to electrode material, and in particular to a kind of N doping
Hollow carbon sphere/nickel sulfide/graphene ternary active multilayer/multi-factor structure composite material and preparation method.
Background technique
The development process of human society is closely related with energy development and utilization rate.With the rapid development of economy, can not
The renewable sources of energy have been used close to exhaustion.On the other hand in order to solve the problems such as environmental pollution increasingly sharpens, various new energy
It explores, the research of new energy devices, the exploitation of new energy product is just in progress like a raging fire, including solar energy, wind energy, biology
Produced by mass-energy, geothermal energy, nuclear fusion energy, water energy and ocean energy and the bio-fuel and hydrogen that are derived as renewable energy
Energy.Relative to traditional energy, new energy generally have the characteristics that pollution less, reserves it is big.Solar energy be both non-renewable energy and
It is renewable energy.It is resourceful, not only can freely use, but also without transport, to environment without any pollution, creates for the mankind
A kind of new lifestyle, it is exhausted for solving the serious problem of environmental pollution in the world today and resource (especially fossil energy)
Problem is of great significance.As third generation novel organic solar cell, dye-sensitized solar cells (DSSC) has ring
The advantages that border is friendly, preparation flow is simple, low in cost, polychrome is transparent and photoelectric conversion performance is excellent is respectively ground by countries in the world
Study carefully personnel's concern.Wherein, the important component to electrode as dye-sensitized solar cells turns the photoelectricity of entire battery
Changing efficiency has tremendous contribution, occurs in the reducing/regenerating process (I to the electrolyte on electrode3 -+2e-=3I-) it is equally dye
Expect one of most important reaction of sensitization solar battery.Effect to electrode is: first returning the electronics transfer come from external circuit
Into redox system, followed by catalytic oxidation-reduction electricity is to (I3 -/I-) reducing/regenerating.Platinum (Pt) is gone out in noble metal with it
The electric conductivity and chemical property of color are considered as the optimal reference material to electrode all the time.Unfortunately, due to Pt
The limited and high cost of resources reserve is unfavorable for industrialized production, and another aspect Pt is easily polluted by components certain in air
Catalytic capability is reduced, and is easily corroded in iodide ion solution system as platinum diiodide (PtI4), to reduce the service life of battery.
Therefore, exploitation deposit is abundant, price is low, excellent performance material substitutes Pt as dye-sensitized solar cells to electrode
It is the necessary Research approach that this field obtains important breakthrough.
There are many forms to exist for the sulfide of nickel, common are NiS, NiS2, Ni3S2, Ni3S4, Ni3+xS2, Ni7S6,
Ni9S8, Ni4S3+x.Nickel sulfide (NiS) is one to be of wide application in Nie Liu family as a kind of form of nickel sulfide
Member, nontoxic and source is sufficient, and this material all has in fields such as semiconductor field, optics battery, lithium ion battery and catalysis
There is huge application potential.
C-base composte material has performance of the very superior dye-sensitized solar cells to electrode material, huge ratio
Surface area, good chemical stability, brilliant chemical property etc..The new a member of graphene as carbon-based material, from
Discovery in 2004 so far, becomes very popular material and is used in lithium ion battery, field effect transistor, gas sensing
The fields such as device, absorbing material and catalyst.Hollow structure carbon material is also the common used material for improving electrocatalysis characteristic.These researchs
It is concentrated mainly on the connection of the structure and structure of electro-catalysis field nano grade inorganic material.Therefore, with different levels structure
Hollow structure causes the great interest of researcher due to being widely used in the fields such as energy conversion and storage.Many institute's weeks
Know, nanocarbon/metal sulfide/carbon component effectively integrates and these components mutually act synergistically, for the property to electrode material
There can be leaping for certain matter.
In recent years, the normal someone's report of research about N doping hollow carbon sphere and nickel sulfide and graphene three, such as Zuo
Et al, (Journal ofMaterials Science:Materials in Electronics, 2015,26 (10):
It 8176-8181.) reports and nanometer nickel sulfide piece is anchored on redox graphene with simple hydro-thermal method, and this
Compound as dye-sensitized solar cells to electrode, under equal conditions, the incident photon-to-electron conversion efficiency of the compound
(7.67%) than platinum (7.21%) as also high by 0.46% to electrode；Yao et al.(Nanoscale. 10(17)(2018)
Hollow carbon sphere 7946-7956.) is prepared with hydro-thermal method, and compound with ferriferrous oxide material, too as dye sensitization
Positive energy counter electrode of battery.Under equal conditions, which makees than noble metal platinum (7.63%)
For to electrode it is high 25%；Yang et al. (Nano Energy, 2014,5:74-81.) reports nickel sulfide and graphene
It is compound, and apply to supercapacitor, produce excellent charge-discharge performance；NiS et al, (Journal ofMaterials
Chemistry, 2012,22 (6): 2395-2397.) nickel sulfide/nickel composite material has successfully been prepared, and applied to lithium
Ion battery, it is shown that outstanding chemical property；Liu et al, (Journal ofMaterials ChemistryA,
2017,5 (40): 21257-21265) nickel sulfide/N doping hollow carbon sphere has successfully been prepared, and apply to asymmetric super
Grade capacitor, under equal conditions, compound has better electrochemical properties than single material.These are mixed about nickel sulfide, nitrogen
The report of miscellaneous hollow carbon sphere and graphene all shows them as energy conversion, a part of material tool in energy storage field
The performance for having its special and excellent.It but is that substrate has been anchored vulcanization by the carbon ball that hydro-thermal method prepares N doping hollow structure
Nickel nano film, hollow carbon sphere/nickel sulfide/graphene ternary active multilayer/multi-factor structure of the N doping of outer envelope graphene
Composite material (NHCS/NiS/RGO), and electrode is had not been reported for dye-sensitized solar cells.
Summary of the invention
It is an object of the invention to: provide hollow carbon sphere/nickel sulfide/graphene ternary active multilayer of N doping a kind of/
Multi-factor structure composite material and preparation method, and the composite material having to electrode material as dye-sensitized solar cells
There is good photoelectric conversion performance, performance has been even more than as the noble metal platinum for generally acknowledging reference electrode, and the composite material
Preparation method it is simple, it is environmental-friendly pollution-free, it is cheap, be suitable for a large amount of exploitation.
To achieve the goals above, the invention provides the following technical scheme:
A kind of hollow carbon sphere/nickel sulfide of N doping/graphene ternary active multilayer/multi-factor structure composite material, it is special
Sign is: the composite material is uniformly distributed loose porous nanometer nickel sulfide piece for surface and is anchored on hollow nitrogen-doped nanometer ball
On, outermost layer encapsulates the multilayer multielement hollow structural material that redox graphene is formed.
A kind of hollow carbon sphere/nickel sulfide of N doping/graphene ternary active multilayer/multi-factor structure composite material preparation
Method, comprising the following steps:
(1) tetraethyl orthosilicate and Dopamine hydrochloride are successively slowly poured into mixed solution, and continues to stir 35-
37h is sufficiently mixed to it；Wherein, the mixed solution is made of dehydrated alcohol, 25% ammonium hydroxide, deionized water；
(2) it is cooled to room temperature, step (1) solution is subjected to high speed centrifugation, by obtained sediment deionized water
Washing is centrifuged repeatedly until supernatant is in as clear as crystal liquid, resulting final product is put into freeze drier dry；
(3) step (2) products therefrom is entered into high temperature process furnances, 890-910 DEG C of reaction 0.9- under stream of nitrogen gas is set
1.1h, obtained silica/N doping hollow carbon sphere black powder sample are spare；
(4) product of step (3) is added in deionized water, by being ultrasonically treated 0.8-1.2h, keeps its full and uniform；
(5) by dichloride sodium, ammonium chloride, urea and 25% ammonium hydroxide, be successively slowly added into step (4) solution, and
And magnetic agitation 0.8-1.2h；
(6) product of step (5) is poured into using polytetrafluoroethylene (PTFE) as in the Teflon autoclave of liner, and by Teflon
Imperial autoclave is put into blast dry oven, and 155-165 DEG C of reaction 11-13h is arranged；
(7) it is cooled to room temperature, (6) resulting solution is subjected to high speed centrifugation, by obtained sediment deionization
Water is centrifuged repeatedly washing until supernatant is in as clear as crystal liquid, and gained final product is put into vacuum freeze drier and is dried to obtain
Nickle silicide/N doping hollow carbon sphere mixture, it is spare；
(8) stannic oxide/graphene nano piece is synthesized according to brave marfan's method；
(9) stannic oxide/graphene nano piece is put into deionized water, and carries out high speed magnetic stirring, it is then sonicated
25-35min is added nickle silicide/N doping hollow carbon sphere mixture obtained by step (7) with forming evenly dispersed mixed solution
Enter into above-mentioned mixed solution, and high speed magnetic stirring 55-65min；
(10) step (9) solution is poured into using polytetrafluoroethylene (PTFE) as in the Teflon autoclave of liner, and by Teflon
Imperial autoclave is put into blast dry oven, and 155-165 DEG C of reaction 11-13h is arranged；
(11) be cooled to room temperature, (10) resulting solution be subjected to high speed centrifugation, by obtained sediment spend from
Sub- water is centrifuged repeatedly washing until supernatant is in as clear as crystal liquid, and sample is put into vacuum freezing drying oven dry formation
N doping hollow carbon sphere/nickle silicide/graphene of 3D frame structure, it is spare；
(12) product of step (11) and polyvinylpyrrolidone are add to deionized water, and are ultrasonically treated 25-
35min；
(13) by Na2S is added in the product of step (12) and magnetic agitation 25-35min；
(14) step (13) acquired solution is poured into using polytetrafluoroethylene (PTFE) as in the Teflon autoclave of liner, and will
Teflon autoclave is put into blast dry oven, and 155-165 DEG C of reaction 11-13h is arranged；
(15) it is cooled to room temperature, the resulting solution of step (14) is subjected to high speed centrifugation, obtained sediment is used
Deionized water is centrifuged repeatedly washing until supernatant is dry in being put into vacuum freezing drying oven after as clear as crystal liquid；
(16) step (15) products therefrom is put into high-temperature annealing furnace, 280-320 DEG C of annealing 1.8- under stream of nitrogen gas is set
2.2h obtains hollow carbon sphere/nickel sulfide/graphene ternary active multilayer of the N doping of three layers of multiple solutions hollow structure/polynary
Structural composite material.
Preferably, dehydrated alcohol in mixed solution described in step (1), 25% ammonium hydroxide, deionized water volume ratio be
5:1:8。
Preferably, centrifugal rotational speed is 8000-10000r/min in step (2), and centrifugal washing times are 3-4 times；Step (7)
Middle centrifugal rotational speed is 8000-10000r/min, and centrifugal washing times are 3-4 times；Centrifugal rotational speed is 8000- in step (11)
10000r/min, centrifugal washing times are 3-4 times；Centrifugal rotational speed is 8000-10000r/min, centrifuge washing in step (15)
Number is 3-4 times.
Preferably, dichloride sodium in step (5), ammonium chloride, urea, 25% ammonium hydroxide usage ratio be 0.5mmol:
0.5mmol:0.1g:0.5mL.
Preferably, the weight ratio of the product and polyvinylpyrrolidone of step (11) is 2:5 in step (12).
Preferably, Na in step (13)2The weight ratio of S and the product of step (12) is 5:1.
Preferably, the time being freeze-dried in step (2) is 9-11h, and temperature is -75 DEG C, vacuum degree be maintained at 500Pa with
Down；The time being freeze-dried in step (7) is 9-11h, and temperature is -75 DEG C, and vacuum degree is maintained at 500Pa or less；
The time being freeze-dried in step (11) is 11-13h, and temperature is -75 DEG C, and vacuum degree is maintained at 500Pa or less；Step
(15) time being freeze-dried in is 11-13h, and temperature is -75 DEG C, and vacuum degree is maintained at 500Pa or less.
The beneficial effects of the present invention are:
Exploitation and design have good catalytic activity and stability to pole material to further increasing the dye sensitization sun
The power conversion efficiency of energy battery (DSSCs) has a very important significance.We are it is highly desirable to be able to effectively living by ternary
Property component composite material apply to dye-sensitized solar cells in electrode, and give full play between ternary active component
Reciprocal effect has the raising of matter to photoelectric conversion performance.
Here, we use a kind of Multi-step conversion method, nickel sulfide (NiS) nanometer sheet is anchored on the hollow carbon of N doping
The surface ball (NHCS) is then formed hollow carbon sphere/nickel sulfide/graphene ternary active of N doping by graphene (RGO) encapsulation
Multilayer/multi-factor structure composite material (NHCS/NiS/RGO).
The modification of graphene overcomes the defect of the composite material bad dispersibility to a certain extent, and graphene encapsulation
N doping hollow carbon sphere/nickel sulfide possesses chemical property more outstanding, the RGO of interface charge polarization and large specific surface area
Absorption and transfer electronics；The void coalescence on the surface NiS, the electronics aggregation in NHCS, forms strong interface coupling.Be conducive to electricity simultaneously
Lotus transfer resistance and teriodide redox, electrode activity are significant.Turned using the photovoltaic that the equipment of NHCS/NiS/RGO generates
It is higher than the PCE (8.06%) obtained using Pt to change efficiency PCE (9.32%).
The composite material played between synergistic effect, this composite material also substantially increase light induced electron and
The separating effect in hole, and recombination probability can be reduced, so that catalytic activity is greatly improved, therefore, composite material of the invention
A kind of specific function catalyst material of function admirable, for electrode material in Energy device research provide it is wide before
Scape.And according to 30 continuously cyclic voltammetry curves, compared to NHCS/NiS composite material and NHCS, NHCS/
NiS/RGO has better electrochemical stability.The PhotoelectrocatalytiPerformance Performance of the NHCS/NiS/RGO composite material is already higher than together
The correlated performance of precious metals pt Deng under the conditions of.
Additionally it should prepare, it is emphasized that composite material of the invention is prepared by the method for solvent heat
Journey is simple, low in cost and no pollution to the environment.
Detailed description of the invention
Fig. 1 is hollow carbon sphere/nickel sulfide/graphene ternary active multilayer/multi-factor structure composite wood of the N doping of preparation
The X-ray diffractogram (XRD) for expecting (NHCS/NiS/RGO), such as Fig. 1,23.5 ° of broad peak is the characteristic peak of NHCS and RGO, is shown
Existing defects in its structure.(110), (101), (300), (021), (401) in NHCS/NiS and NHCS/NiS/RGO and
(012) crystal face (JCPDF:86-2281) is located at 19.4 °, 30.3 °, 32.7 °, 35.9 °, 53.5 °, 59.8 °, shows gained
Sample is NiS component.
Fig. 2 is hollow carbon sphere/nickel sulfide/graphene ternary active multilayer/multi-factor structure composite wood of the N doping of preparation
Expect the Raman figure of (NHCS/NiS/RGO).The figure shows that the Raman spectrum of NHCS, NHCS/NiS and NHCS/NiS/RGO exist
1348cm-1And 1596cm-1There are two main peak, corresponding typical D and G-bands at place.Intensity rate (the I of D wave band and G-bandD/
IG) can be used to assess the defect density in carbon material, ID/IGRatio is bigger, and defect sites are more.As it can be seen that NHCS/NiS is compound
The I of objectD/IGRatio is larger, the I of NHCS/NiS/RGOD/IGRatio is smaller, shows that the defect concentration of the latter is obtained than the former low
More, this shows that RGO's is successfully introduced into the defect concentration for reducing carbon material.
Fig. 3 is hollow carbon sphere/nickel sulfide/graphene ternary active multilayer/multi-factor structure composite wood of the N doping of preparation
Expect the scanning electron microscope (SEM) and transmission electron microscope (TEM) figure of (NHCS/NiS/RGO).By them, NHCS/ can be clearly identified
The microstructure and pattern of NiS and NHCSNiS/RGO.It is NHCS/NiS and NHCS/NiS/RGO in figure in different amplification
Under typical SEM, TEM pattern, it is seen then that the NHCS/NiS of preparation have the uniform layered hollow structure of high levels of three-dimensional, bulb diameter
About 400nm, while also confirming that the surface of NHCS/NiS is made of nanometer sheet interconnected, higher specific surface can be provided
Product, bigger Kong Rong, shorter ion and electron transport path.It is worth noting that, NHCS/NiS is wrapped in graphene layer
In, it means that the efficient assembling between NHCS/NiS and graphene layer.This Multifunction sandwiched-type structure is conducive to exist to electrode
Application in DSSCs is expected to effectively prevent the collapsing of hollow structure.
Fig. 4,5 be preparation N doping hollow carbon sphere/nickel sulfide/graphene ternary active multilayer/multi-factor structure it is compound
The associated cyclic VA characteristic curve figure (CV) of material (NHCS/NiS/RGO).By cyclic voltammetry measurement, can detect immediately
It is various to electrode redox I in the electrolyte3 -Kinetics and electro catalytic activity, can also clearly help us
Solution is to electrode to the absorption of iodide ion, dissociation and desorption.CV curve has two pairs of oxidation peaks and reduction peak, is respectively
The peak Ox1/Redl and Ox2/Red2.Iodide ion catalysis reaction can be disclosed by redox peaks (Ox1/Red1 and Ox2/Red2)
Principle is explained entirely to electrode interface to the redox circular response of Triiodide ion pair.Peak strength (Ox1 and Red1)
Value is followed successively by NHCS < Pt < NHCS/NiS < NHCS/NiS/RGO, illustrates that NHCS/NiS/RGO is preferable to the absorption of electronics, long-range
In Pt.The other is the potential difference between Ox1 and Red1, is denoted as Epp, lesser EppShow the oxidation to electrode to Triiodide ion
Reduction catalysts speed is higher.The E of NHCS/NiS/RGOppFor 0.26V, it is less than NHCS/NiS (0.28V) and Pt (0.35V), shows
Electronics can shift rapidly, promote Triiodide ion to mutually converting.
Fig. 6 is hollow carbon sphere/nickel sulfide/graphene ternary active multilayer/multi-factor structure composite wood of the N doping of preparation
Expect the photoelectric conversion efficiency curve graph (J-V) of (NHCS/NiS/RGO).The photoelectric conversion efficiency of NHCS/NiS/RGO reaches
9.32%, transformation efficiency value (6.98%), NHCS/NiS (8.78%) and Pt (8.06%) much higher than NHCS.
Specific embodiment
In order to further appreciate that the present invention and can preferably be compared to the specimen material and its performance, below with reference to
Specific embodiment explains to the present invention.It should be appreciated that these examples of implementation are merely to illustrate the present invention and are not limited to
The scope of the present invention.
Embodiment 1
A kind of hollow carbon sphere/nickel sulfide of N doping/graphene ternary active multilayer/multi-factor structure composite material preparation
Method: the following steps are included:
(1) by 2mL tetraethyl orthosilicate (C8H20O4) and the Dopamine hydrochloride (C of 0.04g Si8H11NO2HCl) successively delay
Slow pours into mixed solution, and continues to stir 36h and be sufficiently mixed to it；
The mixed solution is dehydrated alcohol (C2H6), O ammonium hydroxide (NH3·H2O, 25%) and deionized water (H2O), three
Volume ratio is 5:1:8.
(2) it is cooled to room temperature, step (1) solution is subjected to high speed centrifugation, control centrifugal rotational speed is 8000-10000r/
Obtained sediment is centrifuged repeatedly washing 3-4 times with deionized water, until supernatant is in as clear as crystal liquid, gained by min
Final product be put into freeze drier dry 10h, freeze drier temperature is controlled at -75 DEG C, and vacuum degree is maintained at 500Pa
Below.
(3) step (2) products therefrom is entered into high temperature process furnances, the lower 900 DEG C of reactions 1h of stream of nitrogen gas, obtained dioxy is set
SiClx/N doping hollow carbon sphere (SiO2/ N-doped carbon spheres) black powder sample, it is spare；
(4) product of step (3) is added in 40mL deionized water, by being ultrasonically treated 1h, keeps its full and uniform；
(5) by the dichloride sodium (NiCl of 0.5mmol2), the ammonium chloride (NH of 5mmol4Cl), the urea (CH of 0.1g4N2O)
With the ammonium hydroxide (NH of 0.5mL3·H2O, 25%) it is successively slowly added into step (4) solution, and magnetic agitation 1h.
(6) product of step (5) is poured into using polytetrafluoroethylene (PTFE) as in the Teflon autoclave of liner, and by Teflon
Imperial autoclave is put into blast dry oven, and 160 DEG C of reaction 12h are arranged；
(7) it is cooled to room temperature, (6) resulting solution is subjected to high speed centrifugation, control centrifugal rotational speed is 8000-
Obtained sediment is centrifuged repeatedly washing 3-4 times with deionized water, until supernatant is in as clear as crystal liquid by 10000r/min
Body, gained final product are put into the dry 10h of vacuum freeze drier, and at -75 DEG C, vacuum degree is kept the control of freeze drier temperature
In 500Pa or less, nickle silicide/N doping hollow carbon sphere mixture is obtained, it is spare；
(8) stannic oxide/graphene nano piece (GO sheet) is synthesized according to brave marfan's method (Hummers)；
(9) 250mg stannic oxide/graphene nano piece is put into 40mL deionized water, and carries out high speed magnetic stirring, then
Sonicated 30min, to form evenly dispersed mixed solution, by nickle silicide/N doping hollow carbon sphere obtained by 1g step (7)
Mixture (NHCS/NiSi) is add to the above mixed solution, and high speed magnetic stirring 60min；
(10) step (9) solution is poured into using polytetrafluoroethylene (PTFE) as in the Teflon autoclave of liner, and by Teflon
Imperial autoclave is put into blast dry oven, and 160 DEG C of reaction 12h are arranged；
(11) it is cooled to room temperature, (10) resulting solution is subjected to high speed centrifugation, control centrifugal rotational speed is 8000-
Obtained sediment is centrifuged repeatedly washing 3-4 times with deionized water, until supernatant is in as clear as crystal liquid by 10000r/min
Body, and sample is put into vacuum freezing drying oven dry 12h, freeze drier temperature is controlled at -75 DEG C, and vacuum degree is maintained at
500Pa or less forms N doping hollow carbon sphere/nickle silicide/graphene (NHCS/NiSi/RGO) of 3D frame structure, standby
With；
(12) product of 40mg step (11) and 100mg polyvinylpyrrolidone (PVP) are added to 60mL deionized water
In, and it is ultrasonically treated 30min；
(13) by 0.1gNa2S is added in the product of step (12) and magnetic agitation 30min；
(14) step (13) acquired solution is poured into using polytetrafluoroethylene (PTFE) as in the Teflon autoclave of liner, and will
Teflon autoclave is put into blast dry oven, and 160 DEG C of reaction 12h are arranged；
(15) it is cooled to room temperature, the resulting solution of step (14) is subjected to high speed centrifugation, control centrifugal rotational speed is 8000-
Obtained sediment is centrifuged repeatedly washing 3-4 times with deionized water, until supernatant is in as clear as crystal liquid by 10000r/min
After body, dry 12h is put into vacuum freezing drying oven, and freeze drier temperature is controlled at -75 DEG C, and vacuum degree is maintained at 500Pa
Below；
(16) step (15) products therefrom is put into high-temperature annealing furnace, the lower 300 DEG C of annealing 2h of stream of nitrogen gas is set, obtains three
Hollow carbon sphere/nickel sulfide/graphene ternary active multilayer/multi-factor structure composite material of the N doping of layer multiple solutions hollow structure
(NHCS/NiS/RGO)。
The composite material is uniformly distributed loose porous nickel sulfide (NiS) nanometer sheet for surface and is anchored on hollow N doping
On nanosphere (NHCS), outermost layer encapsulates the multilayer multielement hollow structural material nitrogen that one layer of redox graphene (RGO) is formed
Hollow carbon sphere/nickel sulfide of doping/multiple graphene (NHCS/NiS/RGO).
Embodiment 2
A kind of silica/N doping hollow carbon sphere (SiO2/ N-doped carbon spheres) preparation method: packet
Include following steps:
(1) by 2mL tetraethyl orthosilicate (C8H20O4) and the Dopamine hydrochloride (C of 0.04g Si8H11NO2HCl) successively delay
Slow pours into mixed solution, and continues to stir 36h and be sufficiently mixed to it；
The mixed solution is dehydrated alcohol (C2H6), O ammonium hydroxide (NH3·H2O, 25%) and deionized water (H2O), three
Volume ratio is 5:1:8.
(2) it is cooled to room temperature, step (1) solution is subjected to high speed centrifugation, control centrifugal rotational speed is 8000-10000r/
Obtained sediment is centrifuged repeatedly washing 3-4 times with deionized water, until supernatant is in as clear as crystal liquid, gained by min
Final product be put into freeze drier dry 10h, freeze drier temperature is controlled at -75 DEG C, and vacuum degree is maintained at 500Pa
Below.
(3) step (2) products therefrom is entered into high temperature process furnances, the lower 900 DEG C of reactions 1h of stream of nitrogen gas, obtained dioxy is set
SiClx/N doping hollow carbon sphere (SiO2/ N-doped carbon spheres) black powder sample.
Embodiment 3
A kind of preparation method of nickle silicide/N doping hollow carbon sphere mixture (NHCS/NiSi composites): including
Following steps:
(1) by 2mL tetraethyl orthosilicate (C8H20O4) and the Dopamine hydrochloride (C of 0.04g Si8H11NO2HCl) successively delay
Slow pours into mixed solution, and continues to stir 36h and be sufficiently mixed to it；
The mixed solution is dehydrated alcohol (C2H6), O ammonium hydroxide (NH3·H2O, 25%) and deionized water (H2O), three
Volume ratio is 5:1:8.
(2) it is cooled to room temperature, step (1) solution is subjected to high speed centrifugation, control centrifugal rotational speed is 8000-10000r/
Obtained sediment is centrifuged repeatedly washing 3-4 times with deionized water, until supernatant is in as clear as crystal liquid, gained by min
Final product be put into freeze drier dry 10h, freeze drier temperature is controlled at -75 DEG C, and vacuum degree is maintained at 500Pa
Below.
(3) step (2) products therefrom is entered into high temperature process furnances, the lower 900 DEG C of reactions 1h of stream of nitrogen gas, obtained dioxy is set
SiClx/N doping hollow carbon sphere (SiO2/ N-doped carbon spheres) black powder sample, it is spare；
(4) product of step (3) is added in 40mL deionized water, by being ultrasonically treated 1h, keeps its full and uniform；
(5) by the dichloride sodium (NiCl of 0.5mmol2), the ammonium chloride (NH of 5mmol4Cl), the urea (CH of 0.1g4N2O)
With the ammonium hydroxide (NH of 0.5mL3·H2O, 25%) it is successively slowly added into step (4) solution, and magnetic agitation 1h.
(6) product of step (5) is poured into using polytetrafluoroethylene (PTFE) as in the Teflon autoclave of liner, and by Teflon
Imperial autoclave is put into blast dry oven, and 160 DEG C of reaction 12h are arranged；
(7) it is cooled to room temperature, (6) resulting solution is subjected to high speed centrifugation, control centrifugal rotational speed is 8000-
Obtained sediment is centrifuged repeatedly washing 3-4 times with deionized water, until supernatant is in as clear as crystal liquid by 10000r/min
Body, gained final product are put into the dry 10h of vacuum freeze drier, and at -75 DEG C, vacuum degree is kept the control of freeze drier temperature
In 500Pa or less, nickle silicide/N doping hollow carbon sphere mixture is obtained.
The composite material is nickle silicide/N doping hollow carbon sphere mixture (NHCS/NiSi composites), and surface is equal
Loose porous nickle silicide (NiSi) nanometer sheet of even distribution is anchored on hollow N doping hollow Nano carbon balls (NHCS).
Embodiment 4
A kind of N doping hollow carbon sphere/nickle silicide/graphene (NHCS/NiSi/RGO) preparation side of 3D frame structure
Method: the following steps are included:
(1) by 2mL tetraethyl orthosilicate (C8H20O4) and the Dopamine hydrochloride (C of 0.04g Si8H11NO2HCl) successively delay
Slow pours into mixed solution, and continues to stir 36h and be sufficiently mixed to it；
The mixed solution is dehydrated alcohol (C2H6), O ammonium hydroxide (NH3·H2O, 25%) and deionized water (H2O), three
Volume ratio is 5:1:8.
(2) it is cooled to room temperature, step (1) solution is subjected to high speed centrifugation, control centrifugal rotational speed is 8000-10000r/
Obtained sediment is centrifuged repeatedly washing 3-4 times with deionized water, until supernatant is in as clear as crystal liquid, gained by min
Final product be put into freeze drier dry 10h, freeze drier temperature is controlled at -75 DEG C, and vacuum degree is maintained at 500Pa
Below.
(3) step (2) products therefrom is entered into high temperature process furnances, the lower 900 DEG C of reactions 1h of stream of nitrogen gas, obtained dioxy is set
SiClx/N doping hollow carbon sphere (SiO2/ N-doped carbon spheres) black powder sample, it is spare；
(4) product of step (3) is added in 40mL deionized water, by being ultrasonically treated 1h, keeps its full and uniform；
(5) by the dichloride sodium (NiCl of 0.5mmol2), the ammonium chloride (NH of 5mmol4Cl), the urea (CH of 0.1g4N2O)
With the ammonium hydroxide (NH of 0.5mL3·H2O, 25%) it is successively slowly added into step (4) solution, and magnetic agitation 1h.
(6) product of step (5) is poured into using polytetrafluoroethylene (PTFE) as in the Teflon autoclave of liner, and by Teflon
Imperial autoclave is put into blast dry oven, and 160 DEG C of reaction 12h are arranged；
(7) it is cooled to room temperature, (6) resulting solution is subjected to high speed centrifugation, control centrifugal rotational speed is 8000-
Obtained sediment is centrifuged repeatedly washing 3-4 times with deionized water, until supernatant is in as clear as crystal liquid by 10000r/min
Body, gained final product are put into the dry 10h of vacuum freeze drier, and at -75 DEG C, vacuum degree is kept the control of freeze drier temperature
In 500Pa or less, nickle silicide/N doping hollow carbon sphere mixture is obtained, it is spare；
(8) stannic oxide/graphene nano piece (GO sheet) is synthesized according to brave marfan's method (Hummers)；
(9) 250mg stannic oxide/graphene nano piece is put into 40mL deionized water, and carries out high speed magnetic stirring, then
Sonicated 30min, to form evenly dispersed mixed solution, by nickle silicide/N doping hollow carbon sphere obtained by 1g step (7)
Mixture (NHCS/NiSi) is add to the above mixed solution, and high speed magnetic stirring 60min；
(10) step (9) solution is poured into using polytetrafluoroethylene (PTFE) as in the Teflon autoclave of liner, and by Teflon
Imperial autoclave is put into blast dry oven, and 160 DEG C of reaction 12h are arranged；
(11) it is cooled to room temperature, (10) resulting solution is subjected to high speed centrifugation, control centrifugal rotational speed is 8000-
Obtained sediment is centrifuged repeatedly washing 3-4 times with deionized water, until supernatant is in as clear as crystal liquid by 10000r/min
Body, and sample is put into vacuum freezing drying oven dry 12h, freeze drier temperature is controlled at -75 DEG C, and vacuum degree is maintained at
500Pa or less forms N doping hollow carbon sphere/nickle silicide/graphene (NHCS/NiSi/RGO) of 3D frame structure.
Claims (8)
1. a kind of hollow carbon sphere/nickel sulfide of N doping/graphene ternary active multilayer/multi-factor structure composite material, feature
Be: the composite material is uniformly distributed loose porous nanometer nickel sulfide piece for surface and is anchored on hollow nitrogen-doped nanometer ball
On, outermost layer encapsulates the multilayer multielement hollow structural material that redox graphene is formed.
2. a kind of hollow carbon sphere/nickel sulfide of N doping/graphene ternary active multilayer/multi-factor structure composite material preparation side
Method, it is characterised in that: the following steps are included:
(1) tetraethyl orthosilicate and Dopamine hydrochloride are successively slowly poured into mixed solution, and continues to stir 35-37h extremely
It is sufficiently mixed；Wherein, the mixed solution is made of dehydrated alcohol, 25% ammonium hydroxide, deionized water；
(2) it is cooled to room temperature, step (1) solution is subjected to high speed centrifugation, repeatedly with deionized water by obtained sediment
Until supernatant is in as clear as crystal liquid, resulting final product is put into freeze drier dry centrifuge washing；
(3) step (2) products therefrom is entered into high temperature process furnances, 890-910 DEG C of reaction 0.9-1.1h under stream of nitrogen gas is set, is obtained
Silica/N doping hollow carbon sphere black powder sample, it is spare；
(4) product of step (3) is added in deionized water, by being ultrasonically treated 0.8-1.2h, keeps its full and uniform；
(5) by dichloride sodium, ammonium chloride, urea and 25% ammonium hydroxide, be successively slowly added into step (4) solution, and magnetic
Power stirs 0.8-1.2h；
(6) product of step (5) is poured into using polytetrafluoroethylene (PTFE) as in the Teflon autoclave of liner, and by Teflon height
Pressure reaction kettle is put into blast dry oven, and 155-165 DEG C of reaction 11-13h is arranged；
(7) it is cooled to room temperature, (6) resulting solution is subjected to high speed centrifugation, obtained sediment deionized water is anti-
Until supernatant is in as clear as crystal liquid, gained final product is put into vacuum freeze drier and is dried to obtain silication multiple centrifuge washing
Nickel/N doping hollow carbon sphere mixture, it is spare；
(8) stannic oxide/graphene nano piece is synthesized according to brave marfan's method；
(9) stannic oxide/graphene nano piece is put into deionized water, and carries out high speed magnetic stirring, subsequent sonicated 25-
Nickle silicide/N doping hollow carbon sphere mixture obtained by step (7) is added to by 35min with forming evenly dispersed mixed solution
In above-mentioned mixed solution, and high speed magnetic stirring 55-65min；
(10) step (9) solution is poured into using polytetrafluoroethylene (PTFE) as in the Teflon autoclave of liner, and by Teflon height
Pressure reaction kettle is put into blast dry oven, and 155-165 DEG C of reaction 11-13h is arranged；
(11) it is cooled to room temperature, (10) resulting solution is subjected to high speed centrifugation, by obtained sediment deionized water
Washing is centrifuged repeatedly until supernatant is in as clear as crystal liquid, and sample is put into drying in vacuum freezing drying oven and forms 3D frame
N doping hollow carbon sphere/nickle silicide/graphene of frame structure, it is spare；
(12) product of step (11) and polyvinylpyrrolidone are add to deionized water, and are ultrasonically treated 25-35min；
(13) by Na2S is added in the product of step (12) and magnetic agitation 25-35min；
(14) step (13) acquired solution is poured into using polytetrafluoroethylene (PTFE) as in the Teflon autoclave of liner, and by Teflon
Imperial autoclave is put into blast dry oven, and 155-165 DEG C of reaction 11-13h is arranged；
(15) be cooled to room temperature, the resulting solution of step (14) be subjected to high speed centrifugation, by obtained sediment spend from
Sub- water is centrifuged repeatedly washing until supernatant is dry in being put into vacuum freezing drying oven after as clear as crystal liquid；
(16) step (15) products therefrom is put into high-temperature annealing furnace, 280-320 DEG C of annealing 1.8-2.2h under stream of nitrogen gas is set,
Hollow carbon sphere/nickel sulfide/graphene ternary active multilayer/the multi-factor structure for obtaining the N doping of three layers of multiple solutions hollow structure is multiple
Condensation material.
3. hollow carbon sphere/nickel sulfide of a kind of N doping according to claim 2/graphene ternary active multilayer/polynary
The preparation method of structural composite material, it is characterised in that: dehydrated alcohol in mixed solution described in step (1), 25% ammonium hydroxide,
The volume ratio of deionized water is 5:1:8.
4. hollow carbon sphere/nickel sulfide of a kind of N doping according to claim 2/graphene ternary active multilayer/polynary
The preparation method of structural composite material, it is characterised in that: centrifugal rotational speed is 8000-10000r/min, centrifuge washing in step (2)
Number is 3-4 times；Centrifugal rotational speed is 8000-10000r/min in step (7), and centrifugal washing times are 3-4 times；In step (11)
Centrifugal rotational speed is 8000-10000r/min, and centrifugal washing times are 3-4 times；Centrifugal rotational speed is 8000- in step (15)
10000r/min, centrifugal washing times are 3-4 times.
5. hollow carbon sphere/nickel sulfide of a kind of N doping according to claim 2/graphene ternary active multilayer/polynary
The preparation method of structural composite material, it is characterised in that: the use of dichloride sodium, ammonium chloride, urea, 25% ammonium hydroxide in step (5)
Amount ratio is 0.5mmol:0.5mmol:0.1g:0.5mL.
6. hollow carbon sphere/nickel sulfide of a kind of N doping according to claim 2/graphene ternary active multilayer/polynary
The preparation method of structural composite material, it is characterised in that: the product and polyvinylpyrrolidone of step (11) in step (12)
Weight ratio is 2:5.
7. hollow carbon sphere/nickel sulfide of a kind of N doping according to claim 2/graphene ternary active multilayer/polynary
The preparation method of structural composite material, it is characterised in that: Na in step (13)2The weight ratio of S and the product of step (12) is 5:
1。
8. hollow carbon sphere/nickel sulfide of a kind of N doping according to claim 2/graphene ternary active multilayer/polynary
The preparation method of structural composite material, it is characterised in that: the time being freeze-dried in step (2) is 9-11h, and temperature is -75 DEG C,
Vacuum degree is maintained at 500Pa or less；The time being freeze-dried in step (7) is 9-11h, and temperature is -75 DEG C, and vacuum degree is protected
It holds in 500Pa or less；The time being freeze-dried in step (11) is 11-13h, and temperature is -75 DEG C, and vacuum degree is maintained at
500Pa or less；The time being freeze-dried in step (15) is 11-13h, and temperature is -75 DEG C, and vacuum degree is maintained at 500Pa
Below.
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