CN109336196A - Three-dimensional fine and close macroscopic body of metal sulfide porous framework/graphene and preparation method thereof, application - Google Patents
Three-dimensional fine and close macroscopic body of metal sulfide porous framework/graphene and preparation method thereof, application Download PDFInfo
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- CN109336196A CN109336196A CN201811319178.7A CN201811319178A CN109336196A CN 109336196 A CN109336196 A CN 109336196A CN 201811319178 A CN201811319178 A CN 201811319178A CN 109336196 A CN109336196 A CN 109336196A
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- C01G53/11—Sulfides
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- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/184—Preparation
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- 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
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Abstract
The present invention relates to technical field of composite materials, to solve the problems, such as that conventional electrode materials volume capacity is low, provide three-dimensional fine and close macroscopic body of metal sulfide porous framework/graphene and preparation method thereof, application.The three-dimensional fine and close macroscopic body of the metal sulfide porous framework/graphene is made with MOF crystal powder by compound, vulcanizing treatment by graphene oxide.The three-dimensional fine and close macroscopic body of metal sulfide porous framework of the invention/graphene remains the structural intergrity of graphene and the metal sulfide porous framework obtained using MOF crystal as template, the excellent properties of graphene and metal sulfide porous framework are had both, with excellent mechanical performance, high density, high volume capacity and high volume energy density, it can be used as application of the new electrode materials in the energy, environment or flexible device field, while also having broad application prospects in fields such as sensing, catalysis, energy storage, absorption.
Description
Technical field
It is three-dimensional fine and close that the present invention relates to technical field of composite materials more particularly to metal sulfide porous framework/graphene
Macroscopic body and preparation method thereof, application.
Background technique
With the quick exhausted of fossil fuel and to the continuous of wearable and portable electronic device and electric vehicle
The problem of exploitation of the demand of growth, high-performance energy storage device has become global concern.In the past few decades, extensively
Explore the lithium ion battery (LIB) with high-energy density.However, the reality that safety problem and high cost limit them is answered
With.On the other hand, Zn base aqueous batteries cause many concerns due to its high security, environment friendly and low cost.?
In these aqueous rechargeable batteries, due to high working voltage (~1.8V) and safety, Ni-Zn battery is considered as having for LIB
The substitute of future.Currently, the major defect of Ni-Zn battery is that cyclical stability difference and energy density are low.
The Ni base cathode material of various nanostructures, such as Ni (OH), NiO, Ni are devised3S2And NiCo2O4, with
Improve the capacity and stability of Ni-Zn battery.In addition, can be further improved speed by by them and carbon nanomaterial hydridization
Rate performance.It has been proved that building porous nanometer structure is the good strategy of Ni-Zn battery, because they have big surface area,
Short ion diffusion length and the transmission of quick charge.However, the strategy can not since hole is abundant and electrode material density is low
Reduce their volume capacity with avoiding.Volume energy density is one of most important Consideration in practical application, especially
It is in small-sized and portable electronic device.To meet this demand, there is an urgent need to develop close with high weight and volume energy
The new electrode material of degree.
It discloses " a kind of preparation method of Ni base NiO nano-chip arrays membrane electrode ", announces in Chinese patent literature
It number is CN102800488A, the invention is using the mixed aqueous solution of lanthanum nitrate and glucose to Ni base crystalloid NiO nano-chip arrays
Membrane electrode is impregnated, and after drying and heat treatment, lanthanum is introduced into the form of ion, and occupies the part lattice of NiO
Site position, the effective activation lattice structure of NiO, so that NiO shows better capacitive property and multiplying power property.But
It is that the performance of the two-dimensional material has certain limitation.Therefore, a kind of mild, simple, pervasive method is developed, group is constructed
Part is evenly distributed, and the fine and close macroscopical composite material of the three-dimensional of pattern and structure-controllable has a very important significance.
Summary of the invention
The present invention is low in order to overcome the problems, such as conventional electrode materials volume capacity, provides a kind of with excellent mechanicalness
Energy, high density, the three-dimensional fine and close macroscopic view of metal sulfide porous framework/graphene of high volume capacity and high volume energy density
Body.
The present invention also provides a kind of preparation method of the three-dimensional fine and close macroscopic body of metal sulfide porous framework/graphene,
This method is easy to operate, being capable of large-scale industrial production to equipment without particular/special requirement.
The present invention also provides a kind of three-dimensional fine and close macroscopic bodies of metal sulfide porous framework/graphene, as Novel electric
Application of the pole material in the energy, environment or flexible device field.
To achieve the goals above, the invention adopts the following technical scheme:
The three-dimensional fine and close macroscopic body of metal sulfide porous framework/graphene, the metal sulfide porous framework/graphene are three-dimensional
Fine and close macroscopic body is made with MOF crystal powder by compound, vulcanizing treatment by graphene oxide.
Preferably, the complex method is that graphene oxide coats MOF crystal powder or MOF crystal powder uniform load
One or two in surface of graphene oxide, specifically depending on MOF crystal powder nature and additional amount.
Metal-organic framework materials (Metal-organic frameworks, MOF) are that a kind of multidimensional is periodically porous
Framework material is mainly coordinated with organic ligand by complexing by transition metal ions.Using MOF as precursor preparation
Obtained porous carbon, metal oxide composite etc. are also widely used for clean energy resource storage and conversion system, such as lithium electricity
Pond, fuel cell and supercapacitor etc..Graphene possesses the advantages that high theoretical surface, high conductivity, is ideal
Electrode material.Metal oxide is compound with graphene, and obtained water system Ni-Zn cell negative electrode material can be effectively solved gold
Belong to oxide, sulfide poorly conductive, metal oxide in charge and discharge process, the problems such as sulfide grain is easy to reunite.Porous gold
The structural advantage of each component can be had both by belonging to the three-dimensional fine and close macroscopic body of oxide/graphene, while can be produced in enormous quantities, in ring
The fields such as border, the energy, flexible device have a good application prospect.
Preferably, the MOF crystal powder is selected from Ni-MOF, Fe-MOF, Mo-MOF, Zn-MOF, Co-MOF and Cu-
One of MOF or a variety of.The present invention is almost all suitable for all MOF crystal, and the preparation method of MOF crystal can pass through document
It consults and obtains, such as Fe-MOF, ZIF-8, Co-MOF, Ni-MOF, Cu-MOF crystal can be synthesized by the method for solvent heat；?
During mixing with graphene oxide, a kind of MOF can be added, two or more MOF can also be added.
The preparation method of the three-dimensional fine and close macroscopic body of metal sulfide porous framework/graphene, comprising the following steps:
(1) graphene oxide dispersion and MOF crystal powder are obtained into hydrogel in being mixed evenly under confined conditions；It is close
The condition of closing is preferably the container of polytetrafluoroethylene (PTFE)；
(2) hydrogel for obtaining step (1) is dried in vacuo, and it is three-dimensional fine and close macro that metal sulfide porous framework/graphene is made
See body presoma；
(3) the three-dimensional fine and close macroscopic body presoma vulcanizing treatment of the metal sulfide porous framework for obtaining step (2)/graphene,
Up to the three-dimensional fine and close macroscopic body of metal sulfide porous framework/graphene；The metal sulfide porous framework/graphene is three-dimensional
The diameter control of fine and close macroscopic body is in 1mm~10cm.
For the present invention by the property of graphene oxide liquid crystal, the colloid liquid crystal based on classics is theoretical, not of the same race by being added
The MOF crystal of class, vacuum drying prepare the three-dimensional fine and close macroscopic body presoma of graphene/metal organic frame, calcine vulcanizing treatment
After be prepared into three-dimensional fine and close macroscopic body.The uniform adhesion metal sulfide in the graphene film surface of the macroscopic body.Prepared MOF spreads out
The three-dimensional fine and close macroscopic body of green material metal sulfide has porous structure, and three-dimensional densification macroscopic body is by nano metal sulfide particle
The porous structure and redox graphene that grain is assembled into form, and in the synthesis process, remain graphene and are with MOF crystal
The structural intergrity for the metal sulfide porous framework that template obtains has both the excellent of graphene and metal sulfide porous framework
Performance can play the excellent of both graphene and porous metals sulfide simultaneously in the fields such as sensing, catalysis, energy storage, absorption
Anisotropic energy, and the three-dimensional fine and close macroscopic body of metal sulfide porous framework/graphene has certain mechanical performance, in energy storage device
There is bright application prospect in anti-fight.
Preferably, in step (3), the process conditions of vulcanizing treatment are as follows: lead to nitrogen, first with the heating of 5~10 DEG C/min
Rate is warming up to 450~600 DEG C, calcines 0.5~1.5h, then Temperature fall is to 300~350 DEG C, at this time by 100~200mg
Sulphur powder push-in, calcines 0.5~1.5h, last Temperature fall in nitrogen atmosphere.
Preferably, the mass ratio of the graphene oxide and MOF crystal powder is 1:(1~10 in step (1)).
Preferably, the concentration of the graphene oxide dispersion is controlled in 6~10mg/mL in step (1).
Preferably, in step (1), in step (1), the graphene oxide dispersion be graphene oxide water solution,
Graphene oxide DMF solution, graphene oxide ethanol solution or graphene oxide methanol solution, it is specific to regard selected MOF crystal sheet
Body property is stablized in which kind of solution；
Preferably, contained graphene oxide is sheet in the graphene oxide dispersion, lateral dimension is 1~50 μm；It is excellent
Be selected in is 20~30 μm.
Preferably, at 25~110 DEG C, the time is controlled in 10~36h for vacuum drying temperature control in step (2).
The three-dimensional fine and close macroscopic body of metal sulfide porous framework/graphene is as electrode material in the energy, environment or energy storage
The application of devices field.
Therefore, the invention has the following beneficial effects:
(1) the three-dimensional fine and close macroscopic body of metal sulfide of the invention porous framework/graphene remains graphene and with MOF crystal
For the structural intergrity for the metal sulfide porous framework that template obtains, graphene and metal sulfide porous framework have been had both
Excellent properties have excellent mechanical performance, high density, high volume capacity and high volume energy density；
(2) preparation method is easy to operate, mild condition, pattern is adjustable, structure-controllable, uniform component distribution, can mass or
Industrialized production；
(3) the three-dimensional fine and close macroscopic body of metal sulfide of the invention porous framework/graphene can be used as new electrode materials in energy
Application in source, environment or flexible device field, while also there is wide application in fields such as sensing, catalysis, energy storage, absorption
Prospect.
Detailed description of the invention
Fig. 1 is the SEM figure of Ni-MOF crystal powder made from embodiment 1.
Fig. 2 is the pictorial diagram of the fine and close macroscopic body of three-dimensional made from comparative example (a) and embodiment 1-5 (b-f): comparative example (a)；
Embodiment 1 (d)；Embodiment 2 (c)；Embodiment 3 (b)；Embodiment 4 (e)；Embodiment 5 (f).
Fig. 3 is the three-dimensional fine and close macroscopic body (a) of graphene oxide made from embodiment 1/Ni-MOF and porous NiS2/ graphene
The SEM figure of three-dimensional densification macroscopic body (b).
Fig. 4 is the three-dimensional fine and close macroscopic body (a) of graphene oxide made from embodiment 1/Ni-MOF and porous NiS2/ graphene
The TEM figure of three-dimensional densification macroscopic body (b).
Fig. 5 is the XRD spectra of sample made from each step of embodiment 1: Ni-MOF crystal powder (a)；Graphene oxide/
The three-dimensional fine and close macroscopic body (b) of Ni-MOF；Porous NiS2The three-dimensional fine and close macroscopic body (c) of/graphene.
Fig. 6 is the Raman spectrogram of the fine and close macroscopic body of three-dimensional made from embodiment 1: graphene oxide/Ni-MOF three-dimensional causes
Close macroscopic body (a)；Porous NiS2The three-dimensional fine and close macroscopic body (b) of/graphene.
Fig. 7 is porous NiS made from embodiment 12The XPS figure of the three-dimensional fine and close macroscopic body of/graphene.
Fig. 8 is the three-dimensional fine and close macroscopic body (a) of graphene oxide made from embodiment 1-5/Ni-MOF and porous NiS2/ graphite
The density comparison diagram of three-dimensional fine and close macroscopic body (b) the different quality ratio of alkene.
Fig. 9 is porous NiS made from embodiment 12The density for the material that the three-dimensional fine and close macroscopic body of/graphene and document are recorded
Comparison diagram.
Figure 10 is oxygen made from the three-dimensional fine and close macroscopic body of Ni-MOF/ graphene oxide made from embodiment 1-5 and comparative example
The compression curve comparison diagram of the three-dimensional fine and close macroscopic body of graphite alkene: comparative example (a)；Embodiment 1 (d)；Embodiment 2 (c)；Embodiment
3(b)；Embodiment 4 (e)；Embodiment 5 (f).
Figure 11 is NiS made from embodiment 12The three-dimensional fine and close macroscopic body (a) of/graphene and zinc (b) sweeping in 1M KOH
Retouching rate is respectively 2 and 5mV s-1CV curve.
Figure 12 is the NiS made from the embodiment 1 in 1M KOH under different scanning rates2The three-dimensional fine and close macroscopic view of/graphene
The CV curve of body: 1mV s-1(a)；2mV s-1(b)；5mV s-1(c)；10mV s-1(d)；20mV s-1(e)。
Figure 13 is NiS made from embodiment 1 under different current densities2The GD curve of the three-dimensional fine and close macroscopic body of/graphene: 2A
g-1(a)；4Ag-1(b)；8Ag-1(c)；16Ag-1(d)；32Ag-1(e)。
Figure 14 is to use Zn as reference electrode respectively, in 2mV s-1,5mV s-1Sweep speed under, in 1M KOH and
Zinc (a) in 20mM Zn (Ac) 2, NiS2The CV curve of/rGO electrode (b).
Figure 15 is NiS under different scanning rates2The CV curve of/rGO electrode: 5mV s-1(a)；3mV s-1(b)；2mV s-1
(c)。
Figure 16 is NiS under different current densities2The GD curve of/rGO electrode: 1A g-1(a)；2A g-1(b)；4A g-1(c)；
6A g-1(d)；8A g-1(e)。
Figure 17 is the NiS as made from the present embodiment 12The three-dimensional fine and close macroscopic body of/graphene is as cathode, commercial Zn plate conduct
The Ni-Zn battery of anode, assembling is lighted as flexible energy storage device rotation electric fan (a) and lightening LED lamp (b), 120 ° of bending
The effect picture of LED light (c).
Figure 18 is NiS2/ rGO//Zn battery uses 12 minutes effect pictures of lightening LED lamp as flexible energy storage device.
Specific embodiment
Below by specific embodiment, and in conjunction with attached drawing, the technical solutions of the present invention will be further described.
In the present invention, if not refering in particular to, all devices and raw material is commercially available or the industry is common are following
Method in embodiment is unless otherwise instructed conventional method in that art.
Embodiment 1
(1) preparation of Ni-MOF crystal powder:
The water of 40mL is added in the beaker of 100mL, 2.6g Nickel dichloride hexahydrate and 6g potassium oxalate, stirring are successively added thereto
It makes it completely dissolved to obtain the clear solution of green.Separately taking a capacity is the beaker of 100mL, and 2.6g six is added thereto and is hydrated
Nickel chloride makes it be laid in beaker bottom, is then slowly dropped into the ethylenediamine solution of 3mL thereto, makes itself and NiCl2Sufficiently connect
It touches and reacts, sample is dark purple at this time.Above two solution is mixed, is vigorously stirred and makes it completely dissolved, continues to stir
48h.After reaction, low-speed centrifugal (room temperature, 10min, 6000rpm), remove supernatant, then washed repeatedly with methanol, from
The heart 3 times, products therefrom is final to obtain Ni-MOF crystal powder after 60 DEG C of vacuum drying 12h；
(2) porous NiS2The preparation of the three-dimensional fine and close macroscopic body of/graphene:
Graphene oxide water solution, Ni-MOF crystal powder are sequentially added in 10mL beaker, control the initial throwing of each raw material
Expect that ratio is as follows: 2mL graphene oxide solution, concentration 10mg/mL, monolithic graphene oxide sheet lateral dimension are 20 μm；Ni-MOF
Crystal powder 100mg, the dispensing mass ratio for controlling graphene oxide and Ni-MOF crystal powder is 1:5；Gained mixture is in close
It is persistently stirred 30min under the conditions of closing, obtains GO/Ni-MOF plural gel, this gel is poured into the container of polytetrafluoroethylene (PTFE)
In, it is dried in vacuo for 24 hours under the conditions of 60 DEG C, obtains the three-dimensional fine and close macroscopic body of graphene oxide/Ni-MOF, i.e., porous NiS2/ stone
The three-dimensional fine and close macroscopic body presoma of black alkene；
Again by porous NiS2The three-dimensional fine and close macroscopic body presoma of/graphene is calcined, is vulcanized, specifically: lead to nitrogen, first with 10
DEG C/min rate is warming up to 450 DEG C, after calcining 1h, 100mg sulphur powder is pushed by Temperature fall at this time to 350 DEG C,；In nitrogen
Calcining two hours, last Temperature fall, the diameter obtained are the porous NiS of 1mm~10cm2The three-dimensional fine and close macroscopic view of/graphene (rGO)
Body.
The pattern of material made from each step of the present embodiment is characterized: it will be seen from figure 1 that the Ni-MOF crystal obtained
It is bar-like crystal, lateral dimension is several microns.Fig. 2 (d) is that graphene/metal organic frame mass ratio is that the three-dimensional of 1:5 causes
The pictorial diagram of close macroscopic body.Fig. 3 (a) is graphene oxide and Ni-MOF mass ratio is the microgram of 1:5, and is inserted into a part
Enlarged drawing, from 3 (a) partial enlarged views this it appears that GO piece be it is transparent have fold, thus prove GO piece there is no group
It is poly-, further illustrate that the porous structure of this self-supporting is constructed by a large amount of single layer GO pieces；GO wraps up the surface Ni-MOF
Get up, and be linked to be a continuous conductive network, Ni-MOF, GO there is no reuniting, intuitively demonstrate Ni-MOF crystalline substance
Body and GO piece successfully obtain three-dimensional macro body by uniform compound.After two step calcine technologies, GO is reduced to rGO, and
NiS is converted by Ni-MOF2.Fig. 3 (b) clearly illustrates after curing, NiS2/ rGO keep the fine and close fine and close macroscopic body of three-dimensional and
There is no structure collapses, and NiS2Show porous club shaped structure.
TEM image in Fig. 4 (a) further demonstrates porous club shaped structure by the NiS having a size of~20nm2Nano particle
Composition.NiS in Fig. 4 (b)2High-resolution TEM (HRTEM) image of stick show the lattice of 0.17,0.29 and 0.33nm away from
From corresponding respectively to NiS2(200), (311) and (321) crystal face.
Fig. 5 gives the XRD spectra of made sample in embodiment 1, and XRD spectra demonstrates the vulcanization of the metal in embodiment 1
The three-dimensional fine and close macroscopic body of object porous framework/graphene is by NiS2And rGO composition.Shown in Fig. 6, pass through Ni-MOF/GO and NiS2/
The Raman spectrum of the three-dimensional fine and close macroscopic body of rGO demonstrates the presence of graphene, wherein observing D band in 1350cm-1The feature at place
Peak and in 1597cm-1The G band at place.In addition, NiS2The intensity ratio (ID/IG) of/rGO is higher than the intensity ratio (ID/ of Ni-MOF/GO
IG), show that GO is heat-treated during calcining vulcanization as rGO.
In addition, carrying out XPS analysis to study NiS obtained2The chemical composition and electronics of the three-dimensional fine and close macroscopic body of/rGO
State.Measurement scanning optical spectrum in Fig. 7 (a) discloses Ni, S, the presence of C and O element.High-resolution Ni 2p in Fig. 7 (b)
Spectrum shows that two peaks, center are located at 854.36eV (2p3/2) and 872.24eV (2p1/2), there are three corresponding satellites, table
It is bright that there are Ni2+And Ni3+.S2p spectrum is shown respectively with 162.8eV (2p in Fig. 7 (c)3/2), 163.95eV (2p1/2),
168.7eV(2p1/2) and 169.75eV centered on four peaks.Fig. 7 (d) high-resolution C 1s spectrum shows two apparent peaks,
Combination energy corresponding to 284.6eV (C-C and C=C) and 285.8eV (C-O).NiS manufactured in the present embodiment2/ rGO is three-dimensional fine and close
Macroscopic body (Ni-MOF/GO for being 5 derived from weight ratio) is used as the cathode material of Ni-Zn battery.By using saturation calomel electricity
Pole (SCE) is as reference electrode and Pt foil as, to electrode, NiS being tested in three-electrode system in 1M KOH2/ rGO electrode
Electrochemical properties.Figure 11 shows that in sweep speed be 5mV s-1When NiS2/ rGO and Zn electrode is in 2mV s-1Under sweep speed
Cyclic voltammetry curve (CV) curve.For NiS2/ rGO electrode observes a pair positioned at 0.2 to 0.4V (relative to SCE)
Redox peaks correspond to NiS2With the redox reaction of OH-ion.Figure 12 shows NiS under different scanning rates2/rGO
The CV curve of electrode.Constant current discharge curve in Figure 13 under various current densities is shown and the consistent result of CV curve.?
Current density is 2Ag-1When, NiS2/ rGO electrode reaches 200.6mAh g-1High capacity.Even if in 32Ag-1High current density
Under, capacity still reaches 156.4mAh g-1, show excellent high rate performance.
Using NiS2/ rGO electrode, as anode, assembles the chargeable Ni-Zn battery of water system as cathode and commercialization Zn plate
(it is expressed as NiS2/rGO//Zn).Contain 1M KOH and 20mM Zn (CH3COO)2Electrolyte.Figure 14 and Figure 15 are respectively illustrated
The NiS under different scanning rates in 1.5-2.1V voltage range2The CV curve of/rGO//Zn battery.NiS2/ rGO//Zn battery exists
Different current density ranges are 1-8Ag-1When discharge curve show the discharge platform at 1.75V, as shown in figure 16.NiS2/
RGO//Zn battery is in 1Ag-1Current density under provide 215.8mAh g-1Specific capacity.
NiS2/ rGO//Zn battery is also used as flexible energy storage device, and Figure 17 is NiS made from the present embodiment 12/ graphite
The three-dimensional fine and close macroscopic body of alkene is as cathode, and commercial Zn plate is as anode, and the Ni-Zn battery of assembling is as flexible energy storage device rotation
Electric fan (Figure 17 a) and lightening LED lamp (Figure 17 b), the effect picture for being bent 120 ° of (more than 90 °) lightening LED lamps (Figure 17 c).Figure
18 show the device can lightening LED lamp be up to 12 minutes, show that porous metals sulfide produced by the present invention/graphene is three-dimensional
Fine and close macroscopic body is used as safety as electrode material in practical applications, and inexpensively, simple power supply has huge potentiality.This
Outside, Ni-Zn battery can be worked normally in the case where bending is more than 90 °, and it is wide to further illustrate that it has in flexible battery
Wealthy application prospect.
Embodiment 2
Embodiment 2 the difference from embodiment 1 is that: in step (2), the additional amount of Ni-MOF crystal powder is 60mg, controls oxygen
The dispensing mass ratio of graphite alkene and Ni-MOF crystal powder is 1:3；Remaining process conditions is identical.
Embodiment 3
Embodiment 3 the difference from embodiment 1 is that: in step (2), the additional amount of Ni-MOF crystal powder is 20mg, controls oxygen
The dispensing mass ratio of graphite alkene and Ni-MOF crystal powder is 1:1；Remaining process conditions is identical.
Embodiment 4
Embodiment 4 the difference from embodiment 1 is that: in step (2), the additional amount of Ni-MOF crystal powder is 150mg, controls oxygen
The dispensing mass ratio of graphite alkene and Ni-MOF crystal powder is 1:7.5；Remaining process conditions is identical.
Embodiment 5
Embodiment 5 the difference from embodiment 1 is that: in step (2), the additional amount of Ni-MOF crystal powder is 200mg, controls oxygen
The dispensing mass ratio of graphite alkene and Ni-MOF crystal powder is 1:10；Remaining process conditions is identical.
Embodiment 6
Embodiment 6 the difference from embodiment 1 is that: in step (2), the additive amount of sulphur powder is 200mg；Remaining process conditions is complete
It is identical.
Embodiment 7
Embodiment 7 the difference from embodiment 1 is that: in step (2), the additive amount of sulphur powder is 150mg；Remaining process conditions is complete
It is identical.
Comparative example
The graphene oxide solution of 2mL concentration 10mg/mL is added in 10mL beaker, monolithic graphene oxide sheet lateral dimension is
20μm；In being persistently stirred 30min under confined conditions, GO gel is obtained, this gel is poured into the container of polytetrafluoroethylene (PTFE),
It is dried in vacuo under the conditions of 60 DEG C for 24 hours to get the three-dimensional fine and close macroscopic body of graphene oxide.
Fig. 2 illustrates the pictorial diagram of the fine and close macroscopic body of three-dimensional made from comparative example (a) and embodiment 1-5 (b-f)；To implementation
The three-dimensional fine and close macroscopic body of graphene oxide/Ni-MOF and porous NiS made from example 1-52The three-dimensional fine and close macroscopic view of/graphene (rGO)
The density of body compares, and result figure is shown in Fig. 8: by the fine and close macroscopic body of Ni-MOF/GO three-dimensional that shown in Fig. 8 (a), weight ratio is 1:1
High-tap density is 1.61g cm-3.It is worth noting that, even if after calcine technology, NiS2The three-dimensional fine and close macroscopic body of/rGO
Also very high level has been reached.Tap density is up to 1.51g cm-3, higher than the energy storage material of most of reports (see Fig. 9).Also survey
It has measured by NiS2The tap density of electrode made of/rGO can be up to 1.48g cm-3.In addition, Figure 10 gives embodiment
The three-dimensional fine and close macroscopic view of graphene oxide made from the three-dimensional fine and close macroscopic body of Ni-MOF/ graphene oxide made from 1-5 and comparative example
The compression curve comparison diagram of body.Mechanical measurement shows the three-dimensional fine and close macroscopic body of HD Ni-MOF/GO also pressure resistance with higher
(the three-dimensional fine and close macroscopic body of Ni-MOF/GO is 103.63Mpa to degree, and MOF/GO ratio is 5), it is three-dimensional fine and close to be higher than pure Ni-MOF and pure GO
Macroscopic body.
The NiS of 2-5 of embodiment of the present invention preparation2The performance and embodiment 1 of the three-dimensional fine and close macroscopic body of/rGO are suitable, herein not
It repeats again.
The foregoing is merely presently preferred embodiments of the present invention, is not intended to limit the present invention in any form, and is not surpassing
There are also other variations and modifications under the premise of technical solution documented by claim out.
Claims (9)
1. the three-dimensional fine and close macroscopic body of metal sulfide porous framework/graphene, which is characterized in that the porous frame of metal sulfide
The three-dimensional fine and close macroscopic body of frame/graphene is made with MOF crystal powder by compound, vulcanizing treatment by graphene oxide.
2. the three-dimensional fine and close macroscopic body of metal sulfide porous framework according to claim 1/graphene, which is characterized in that
The MOF crystal powder is selected from one of Ni-MOF, Fe-MOF, Mo-MOF, Zn-MOF, Co-MOF and Cu-MOF or a variety of.
3. the preparation method of the three-dimensional fine and close macroscopic body of metal sulfide porous framework as claimed in claim 1 or 2/graphene,
Characterized by comprising the following steps:
(1) graphene oxide dispersion and MOF crystal powder are obtained into hydrogel in being mixed evenly under confined conditions；
(2) hydrogel for obtaining step (1) is dried in vacuo, and it is three-dimensional fine and close macro that metal sulfide porous framework/graphene is made
See body presoma；
(3) the three-dimensional fine and close macroscopic body presoma vulcanizing treatment of the metal sulfide porous framework for obtaining step (2)/graphene,
Up to the three-dimensional fine and close macroscopic body of metal sulfide porous framework/graphene.
4. the preparation method of the three-dimensional fine and close macroscopic body of metal sulfide porous framework according to claim 3/graphene,
It is characterized in that, in step (3), the process conditions of vulcanizing treatment are as follows: first lead to nitrogen, heated up with the heating rate of 5~10 DEG C/min
To 450~600 DEG C, 0.5~1.5h is calcined, then sulphur powder is pushed by Temperature fall at this time to 300~350 DEG C, in nitrogen atmosphere
0.5~1.5h of middle calcining, last Temperature fall.
5. the preparation method of the three-dimensional fine and close macroscopic body of metal sulfide porous framework according to claim 3/graphene,
It is characterized in that, in step (1), the mass ratio of the graphene oxide and MOF crystal powder is 1:(1~10).
6. the preparation method of the three-dimensional fine and close macroscopic body of metal sulfide porous framework according to claim 3/graphene,
It is characterized in that, in step (1), the concentration of the graphene oxide dispersion is controlled in 6~10mg/mL.
7. the preparation method of the three-dimensional fine and close macroscopic body of metal sulfide porous framework according to claim 3/graphene,
Be characterized in that, in step (1), the graphene oxide dispersion be graphene oxide water solution, graphene oxide DMF solution,
Graphene oxide ethanol solution or graphene oxide methanol solution；Contained graphene oxide is in the graphene oxide dispersion
Sheet, lateral dimension are 1~50 μm.
8. the preparation method of the three-dimensional fine and close macroscopic body of metal sulfide porous framework according to claim 3/graphene,
It is characterized in that, in step (2), at 25~110 DEG C, the time is controlled in 10~36h for vacuum drying temperature control.
9. the three-dimensional fine and close macroscopic body of metal sulfide porous framework as claimed in claim 1 or 2/graphene is as electrode material
In the application of the energy, environment or energy storage device field.
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| CN110380062A (en) * | 2019-07-16 | 2019-10-25 | 运城学院 | The preparation method of the difunctional VPO catalysts of sulfur doping based on ZIF-67 and conductive graphene |
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| CN114787081A (en) * | 2019-10-11 | 2022-07-22 | 普世物料公司 | Device and method for synthesizing graphene, and carbon pellet |
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| CN110380062A (en) * | 2019-07-16 | 2019-10-25 | 运城学院 | The preparation method of the difunctional VPO catalysts of sulfur doping based on ZIF-67 and conductive graphene |
| CN110634688A (en) * | 2019-08-12 | 2019-12-31 | 江苏大学 | Preparation method and application of composite film electrode with CoZn-S nano particles inserted in graphene |
| CN114787081A (en) * | 2019-10-11 | 2022-07-22 | 普世物料公司 | Device and method for synthesizing graphene, and carbon pellet |
| CN111816867A (en) * | 2020-07-01 | 2020-10-23 | 广西壮族自治区分析测试研究中心 | Sea urchin-shaped NiCo with mesoporous structure2O4Preparation method and application of three-dimensional construction graphene microsphere composite material |
| CN111816867B (en) * | 2020-07-01 | 2022-11-18 | 广西壮族自治区分析测试研究中心 | Sea urchin-shaped NiCo with mesoporous structure 2 O 4 Preparation method and application of three-dimensional construction graphene microsphere composite material |
| CN112062165A (en) * | 2020-08-19 | 2020-12-11 | 浙江工业大学 | Regulation and control FeS2Method for reducing graphene oxide compact assembly structure |
| CN113708005A (en) * | 2021-08-16 | 2021-11-26 | 电子科技大学 | Lithium-intercalated MOF/graphene composite modified functional membrane and preparation method thereof |
| CN113708005B (en) * | 2021-08-16 | 2022-10-14 | 电子科技大学 | Lithium-intercalated MOF/graphene composite modified functional membrane and preparation method thereof |
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