CN109065874A - A kind of MoO3/ rGO-N nanocomposite and its preparation method and application - Google Patents
A kind of MoO3/ rGO-N nanocomposite and its preparation method and application Download PDFInfo
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- CN109065874A CN109065874A CN201810957464.XA CN201810957464A CN109065874A CN 109065874 A CN109065874 A CN 109065874A CN 201810957464 A CN201810957464 A CN 201810957464A CN 109065874 A CN109065874 A CN 109065874A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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- H—ELECTRICITY
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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
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Abstract
The present invention relates to technical field of nano material, specially a kind of MoO3/ rGO-N nanocomposite and preparation method thereof and its application in lithium ion battery.MoO of the invention3In/rGO-N nanocomposite, three-dimensional N doping redox graphene compound lamella provides substrate for the growth of molybdenum trioxide, and molybdenum trioxide can be made to be uniformly dispersed, be grown in the surface of three-dimensional N doping redox graphene, the MoO of this structure3/ rGO-N nanocomposite combines three-dimensional N doping redox graphene good conductivity and MoO3Nanometer sheet ion, electron-transport are apart from short advantage, both the electric conductivity of material entirety can be improved, volume change and aggregation of the molybdenum trioxide nano particle in charge/discharge process can also effectively be alleviated, keep good structural intergrity, with good chemical property, can be used as the negative electrode material of lithium battery.Preparation method simple process of the present invention, yield be high, easy expanding production.
Description
Technical field
The present invention relates to technical field of nano material more particularly to a kind of MoO3/ rGO-N nanocomposite and its preparation
Method and its application in lithium ion battery.
Background technique
The negative electrode material of lithium ion battery is mainly graphite type material at present, but the energy density of graphite type material is low, sternly
The high speed development of lithium electricity industry is constrained again.Transition metal oxide is because its theoretical capacity is high, is easy to largely prepare, environmental-friendly
The advantages that, and it is considered as very promising lithium ion battery negative material.Up to the present, it has successfully been prepared for big
The different-shape of amount, different sizes, different structure transition metal oxide, including molybdenum oxide, cobalt oxide, iron oxide,
Nickel oxide, manganese oxide, zinc oxide etc. all show the storage lithium performance of superelevation as lithium ion battery negative material.At this
In a little transition metal oxides, MoO3Possess higher theoretical capacity (1117mA h g-1), and cause grinding for researcher
Study carefully interest.But MoO3Electronic conductivity it is low, serious polarization, and huge volume can be generated in charge and discharge process and become
Change, seriously constrains MoO3Practical application.This kind of in order to solve the problems, such as, researchers have done a large amount of exploration, always
It include mainly following two points for knot, first is that by MoO3Particle size drop to Nano grade.MoO3Nanosizing not only can be bright
Increase MoO aobviously3With the contact area of electrolyte, and electronics can be reduced in MoO3Internal transmission range.Second is that by MoO3
It is compound with the better carbon material of electric conductivity.Carbon material is not only able to promote the electric conductivity of electrode, and can alleviate MoO3It is filling
Volume change in discharge process, and then promote MoO3Stable circulation performance and high rate performance.
Graphene as a kind of advanced carbon material, due to its conductivity height, large specific surface area, high thermal conductivity the advantages that by
It is considered the ideal composition of lithium-ion battery composite-electrode material.But graphene be one kind by carbon atom with sp2Hybridized orbit
The two-dimentional carbon nanomaterial that hexangle type is in honeycomb lattice is formed, surface is comparatively stable, is unfavorable for and transiting metal oxidation
The stable chemical bond of the formation such as object, sulfide, phosphide, thus compound tense is being carried out with lithium electric material, it can be only formed a kind of mixed
The requirement of ideal composite material is not achieved in condensation material.
Summary of the invention
The present invention in view of the above-mentioned problems existing in the prior art, provide a kind of molybdenum trioxide can it is evenly dispersed, be grown in three
Tie up the MoO on N doping redox graphene surface or inside3/ rGO-N composite material；And utilize raw material system cheap and easy to get
Standby MoO3The method of/rGO-N composite material, the preparation method simple process, yield height, easy expanding production；MoO of the invention3/
RGO-N composite material possesses good electric conductivity, and good structural intergrity, Neng Gouzuo can be kept in charge and discharge process
It is used for the negative electrode material of lithium battery.
To achieve the above object, the present invention uses following technical scheme.
A kind of MoO3/ rGO-N composite material, redox graphene including N doping and the oxidation for being grown in N doping
The sheet MoO on reduced graphene surface3, the composite material is with three-dimensional porous structure.
A kind of MoO3The preparation method of/rGO-N composite material, comprising the following steps:
S1,2- is heated to reflux in the environment of the aqueous solution of graphene oxide, molybdate and ammonium salt is placed in 100-160 DEG C
6h obtains evenly dispersed mixed solution；The mass ratio of the graphene oxide, molybdate and ammonium salt is 1:(4-8): (20-
60)。
Preferably, the aqueous solution of graphene oxide, molybdate and ammonium salt is placed in 100-160 DEG C of oil bath and is heated back
Stream.
Preferably, the concentration of graphene oxide is 0.5-2.5mg/mL in aqueous solution.
Preferably, molybdate is selected from least one of ammonium molybdate, sodium molybdate, potassium molybdate.
Preferably, the ammonium salt is selected from least one of ammonium chloride, ammonium nitrate, ammonium bromide.
S2, mixed solution is heated to 150-210 DEG C, reacts 16-24h.
S3, it filters the mixed solution after step S2 reaction and washs filter cake, dry cake obtains black powder.
Preferably, dry cake is dried in the vacuum oven for be placed in filter cake 80 DEG C.
S4, black powder carry out high-temperature calcination under an inert atmosphere, obtain composite material.
Preferably, the calcination temperature of high-temperature calcination is 550-800 DEG C, calcination time 4-8h.
Graphene oxide described above the preparation method is as follows:
Natural graphite powder is added in the concentrated sulfuric acid that mass fraction is 98%, and addition sodium nitrate is stirred at room temperature；So
It continuously adds potassium permanganate under stiring afterwards, and keeps suspension temperature at 20 DEG C or less during adding potassium permanganate；Then it hangs
18-22h is stirred at room temperature to form underflow in supernatant liquid；Followed by water is added into underflow and stirs, hydrogen peroxide is then added
So that mixture color is become yellow from brown and continues to stir 0.5h or more；Mixture and filter cake and drying are washed followed by coming
Afterwards, graphene oxide is obtained.
The quality of the natural graphite powder and the volume ratio of the concentrated sulfuric acid are 1g:30mL；The natural graphite powder, sodium nitrate and
The mass ratio of potassium permanganate is 1:0.75:20；The quality of the natural graphite powder and the volume ratio of water are 1g:128mL.
MoO described above3/ rGO-N composite material is used as lithium ion battery negative material.
Compared with prior art, the beneficial effects of the present invention are:
The present invention prepares three-dimensional graphene oxide using raw material cheap and easy to get, by graphene oxide, molybdate and ammonium salt
The relatively low level-one of the advanced trip temperature of aqueous solution heat reaction, and the dosage by changing molybdate and ammonium salt, to regulate and control
The adhesion amount of molybdate and ammonium root in surface of graphene oxide；Then it carries out the relatively high second level of temperature and heats reaction, make ammonium
Nitrogen-atoms in radical ion replaces the oxygen-containing functional group in graphene oxide, forms nitrogen-doped graphene, in addition molybdate is in height
Molybdenum trioxide is resolved under warm high pressure, forms MoO3/ rGO-N nanocomposite, make molybdenum trioxide can it is evenly dispersed, be grown in
Three-dimensional N doping redox graphene surface obtains the MoO of storage lithium function admirable then through high-temperature calcination3/rGO-N
Nanocomposite.Compared to pure graphene, three-dimensional N doping redox graphene possesses more functional groups and makes its property
Matter is more active, can be compound with molybdenum trioxide, forms MoO with high performance3/ rGO-N nanocomposite.In MoO3/rGO-
In N nanocomposite, three-dimensional N doping redox graphene lamella provides substrate for the growth of molybdenum trioxide, can make
Molybdenum trioxide is uniformly dispersed, is grown in the surface of three-dimensional N doping redox graphene, the MoO of this structure3/rGO-N
Nanocomposite combines three-dimensional N doping redox graphene good conductivity and MoO3Nanometer sheet ion, electron-transport away from
From short advantage, the electric conductivity of material entirety both can be improved, can also effectively alleviate molybdenum trioxide nano particle charging/
Volume change and aggregation in discharge process, keep good structural intergrity, have good chemical property, being capable of conduct
The negative electrode material of lithium battery uses.
Preparation method simple process of the present invention, yield be high, easy expanding production.
Figure of description
Fig. 1 is MoO in embodiment 13/ rGO-N nanocomposite A1 amplifies the scanning electron microscope (SEM) photograph under 10,000 times；
Fig. 2 is MoO in embodiment 13The X-ray diffraction spectra figure of/rGO-N nanocomposite A1；
Fig. 3 is MoO in embodiment 13The constant current of/rGO-N nanocomposite A1 recycles figure；
Fig. 4 is MoO in embodiment 23/ rGO-N nanocomposite A2 amplifies the scanning electron microscope (SEM) photograph under 10,000 times；
Fig. 5 is MoO in embodiment 33/ rGO-N nanocomposite A3 amplifies the scanning electron microscope (SEM) photograph under 10,000 times.
Specific embodiment
In order to more fully understand technology contents of the invention, combined with specific embodiments below to technical solution of the present invention
It is described further and illustrates.
Embodiment 1
The present embodiment provides a kind of MoO3/ rGO-N composite material and this kind of MoO3The preparation side of/rGO-N composite material
Method.
MoO described in the present embodiment3/ rGO-N composite material includes the redox graphene of N doping and is grown in nitrogen
The sheet MoO of the redox graphene surface of doping3, composite material is with three-dimensional porous structure, and specific preparation process is as follows:
(1) the 150mL concentrated sulfuric acid (mass fraction w=the preparation of graphene oxide (GO): is added in 5g natural graphite powder
98%) in, lower addition 3.75g sodium nitrate is stirred at room temperature.With vigorous stirring, it is slowly added into 20g potassium permanganate, is during which kept
For the temperature of suspension at 20 DEG C hereinafter, reaction system is then transferred to room temperature, stir about 20h forms underflow.At the uniform velocity stirring
In the case where, it is slowly added to the deionized water of 640mL, is then slowly added into the hydrogen peroxide (mass fraction w=30%) of 30mL,
The color of solution becomes yellow from brown, continues after stirring 0.5h, mixture is filtered, is rinsed with deionized water, remove metal
The impurity such as ion obtain graphene oxide after dry.
(2) 125mg GO is taken to be added in 50ml deionized water, magnetic agitation 30min and ultrasound 6h (40 DEG C of water temperature of control
Below), it is completely dispersed graphene oxide in aqueous solution.0.75g ammonium molybdate and 3.75g ammonium chloride are then added thereto,
The heating stirring 4h in 120 DEG C of oil bath.Gained mixed solution is transferred in reaction kettle, in 180 DEG C of reaction 20h, wait react
Kettle is cooled to room temperature, and is filtered mixed solution and is washed with a large amount of deionized water to product, and product is dry in 80 DEG C of vacuum
It is dry in dry case, obtain black powder.Gained black powder is transferred in porcelain boat, is forged in the tube furnace of 750 DEG C of nitrogen atmospheres
Burn 6h, products therefrom MoO3/ rGO-N nanocomposite, is denoted as A1.
To MoO manufactured in the present embodiment3/ rGO-N composite A 1 carries out following test and test result is as follows:
(1) Electronic Speculum detection, the result is shown in Figure 1 are scanned to A1 by Hitachi S-4800.As shown in Figure 1, A1 is
MoO3With the composite material of three-dimensional N doping redox graphene.
(2) X-ray diffraction spectra detection is carried out to A1 by D8 Advance X-ray power diffactometer,
As a result see Fig. 2, Fig. 2 is compareed into the MoO it is found that in A1 with standard card3For the MoO of hexagonal phase3。
(3) Mikrouna, Super (1220/750/900) glove box (H are utilized2O < 0.1ppm, O2< 0.1ppm) assembling button
Formula half-cell then uses new prestige cell tester to A1 sample in 200mA g-1Current density under carried out 50 constant currents
Charge-discharge test, as a result such as Fig. 3, from the figure 3, it may be seen that the capacity of A1 still retains 565mAh g after circulation 50 times-1, illustrate the material
With good cyclical stability.
Embodiment 2
The present embodiment provides a kind of MoO3/ rGO-N composite material and this kind of MoO3The preparation side of/rGO-N composite material
Method.
MoO described in the present embodiment3/ rGO-N composite material includes the redox graphene of N doping and is grown in nitrogen
The sheet MoO of the redox graphene surface of doping3, composite material is with three-dimensional porous structure, and specific preparation process is as follows:
(1) preparation of graphene oxide (GO) is as in embodiment 1.
(2) 125mg GO is taken to be added in 50ml deionized water, magnetic agitation 30min and ultrasound 6h (40 DEG C of water temperature of control
Below), it is completely dispersed graphene oxide in aqueous solution.0.75g sodium molybdate and 3.75g ammonium chloride are then added thereto,
The heating stirring 4h in 120 DEG C of oil bath.Gained mixed solution is transferred in reaction kettle, in 180 DEG C of reaction 20h, wait react
Kettle is cooled to room temperature, and is filtered mixed solution and is washed with a large amount of deionized water to product, and product is dry in 80 DEG C of vacuum
It is dry in dry case, obtain black powder.Gained black powder is transferred in porcelain boat, is forged in the tube furnace of 750 DEG C of nitrogen atmospheres
Burn 6h, products therefrom MoO3/ rGO-N nanocomposite, is denoted as A2.
By Hitachi S-4800 to MoO manufactured in the present embodiment3/ rGO-N composite A 2 is scanned Electronic Speculum inspection
It surveys, as a result sees Fig. 4.As shown in Figure 4, A2 MoO3With the composite material of three-dimensional N doping redox graphene.
Embodiment 3
The present embodiment provides a kind of MoO3/ rGO-N composite material and this kind of MoO3The preparation side of/rGO-N composite material
Method.
MoO described in the present embodiment3/ rGO-N composite material includes the redox graphene of N doping and is grown in nitrogen
The sheet MoO of the redox graphene surface of doping3, composite material is with three-dimensional porous structure, and specific preparation process is as follows:
(1) preparation of graphene oxide (GO) is as in embodiment 1.
(2) 125mg GO is taken to be added in 50ml deionized water, magnetic agitation 30min and ultrasound 6h (40 DEG C of water temperature of control
Below), it is completely dispersed graphene oxide in aqueous solution.0.75g potassium molybdate and 3.75g ammonium chloride are then added thereto,
The heating stirring 4h in 120 DEG C of oil bath.Gained mixed solution is transferred in reaction kettle, in 180 DEG C of reaction 20h, wait react
Kettle is cooled to room temperature, and is filtered mixed solution and is washed with a large amount of deionized water to product, and product is dry in 80 DEG C of vacuum
It is dry in dry case, obtain black powder.Gained black powder is transferred in porcelain boat, is forged in the tube furnace of 750 DEG C of nitrogen atmospheres
Burn 6h, products therefrom MoO3/ rGO-N nanocomposite, is denoted as A3.
By Hitachi S-4800 to MoO manufactured in the present embodiment3/ rGO-N composite A 3 is scanned Electronic Speculum inspection
It surveys, as a result sees Fig. 5.As shown in Figure 5, A3 MoO3With the composite material of three-dimensional N doping redox graphene.
Embodiment 4
The present embodiment provides a kind of MoO3/ rGO-N composite material and this kind of MoO3The preparation side of/rGO-N composite material
Method.
MoO described in the present embodiment3/ rGO-N composite material includes the redox graphene of N doping and is grown in nitrogen
The sheet MoO of the redox graphene surface of doping3, composite material is with three-dimensional porous structure, and specific preparation process is as follows:
(1) preparation of graphene oxide (GO) is as in embodiment 1.
(2) 125mg GO is taken to be added in 50ml deionized water, magnetic agitation 30min and ultrasound 6h (40 DEG C of water temperature of control
Below), it is completely dispersed graphene oxide in aqueous solution.0.75g ammonium molybdate and 3.75g ammonium nitrate are then added thereto,
The heating stirring 4h in 120 DEG C of oil bath.Gained mixed solution is transferred in reaction kettle, in 180 DEG C of reaction 20h, wait react
Kettle is cooled to room temperature, and is filtered mixed solution and is washed with a large amount of deionized water to product, and product is dry in 80 DEG C of vacuum
It is dry in dry case, obtain black powder.Gained black powder is transferred in porcelain boat, is forged in the tube furnace of 750 DEG C of nitrogen atmospheres
Burn 6h, products therefrom MoO3/ rGO-N nanocomposite, is denoted as A4.
Embodiment 5
The present embodiment provides a kind of MoO3/ rGO-N composite material and this kind of MoO3The preparation side of/rGO-N composite material
Method.
MoO described in the present embodiment3/ rGO-N composite material includes the redox graphene of N doping and is grown in nitrogen
The sheet MoO of the redox graphene surface of doping3, composite material is with three-dimensional porous structure, and specific preparation process is as follows:
(1) preparation of graphene oxide (GO) is as in embodiment 1.
(2) 125mg GO is taken to be added in 50ml deionized water, magnetic agitation 30min and ultrasound 6h (40 DEG C of water temperature of control
Below), it is completely dispersed graphene oxide in aqueous solution.0.75g ammonium molybdate and 3.75g ammonium bromide are then added thereto,
The heating stirring 4h in 120 DEG C of oil bath.Gained mixed solution is transferred in reaction kettle, in 180 DEG C of reaction 20h, wait react
Kettle is cooled to room temperature, and is filtered mixed solution and is washed with a large amount of deionized water to product, and product is dry in 80 DEG C of vacuum
It is dry in dry case, obtain black powder.Gained black powder is transferred in porcelain boat, is forged in the tube furnace of 750 DEG C of nitrogen atmospheres
Burn 6h, products therefrom MoO3/ rGO-N nanocomposite, is denoted as A5.
Embodiment 6
The present embodiment provides a kind of MoO3/ rGO-N composite material and this kind of MoO3The preparation side of/rGO-N composite material
Method.
MoO described in the present embodiment3/ rGO-N composite material is denoted as A6, redox graphene and life including N doping
Grow the sheet MoO in the redox graphene surface of N doping3, composite material has three-dimensional porous structure, specific to prepare step
Suddenly essentially identical with embodiment 1, the difference is that the dosage of ammonium molybdate and ammonium chloride is changed, ammonium molybdate in the present embodiment
Dosage be 0.5g, the dosage of ammonium chloride is 2.5g.
Embodiment 7
The present embodiment provides a kind of MoO3/ rGO-N composite material and this kind of MoO3The preparation side of/rGO-N composite material
Method.
MoO described in the present embodiment3/ rGO-N composite material is denoted as A7, redox graphene and life including N doping
Grow the sheet MoO in the redox graphene surface of N doping3, composite material has three-dimensional porous structure, specific to prepare step
Suddenly essentially identical with embodiment 1, the difference is that the dosage of ammonium molybdate and ammonium chloride is changed, ammonium molybdate in the present embodiment
Dosage be 0.5g, the dosage of ammonium chloride is 7.5g.
Embodiment 8
The present embodiment provides a kind of MoO3/ rGO-N composite material and this kind of MoO3The preparation side of/rGO-N composite material
Method.
MoO described in the present embodiment3/ rGO-N composite material is denoted as A8, redox graphene and life including N doping
Grow the sheet MoO in the redox graphene surface of N doping3, composite material has three-dimensional porous structure, specific to prepare step
Suddenly essentially identical with embodiment 1, the difference is that the dosage of ammonium molybdate and ammonium chloride is changed, ammonium molybdate in the present embodiment
Dosage be 1g, the dosage of ammonium chloride is 2.5g.
Embodiment 9
The present embodiment provides a kind of MoO3/ rGO-N composite material and this kind of MoO3The preparation side of/rGO-N composite material
Method.
MoO described in the present embodiment3/ rGO-N composite material is denoted as A9, redox graphene and life including N doping
Grow the sheet MoO in the redox graphene surface of N doping3, composite material has three-dimensional porous structure, specific to prepare step
Suddenly essentially identical with embodiment 1, the difference is that:
1, the concentration of graphene oxide is that 0.5mg/mL takes 125mg GO to be added to that is, in step (2) in aqueous solution
In 250ml deionized water, magnetic agitation 30min and ultrasound 6h (40 DEG C of water temperature of control or less) are completely dispersed graphene oxide
In aqueous solution.
2, the dosage of ammonium molybdate and ammonium chloride is changed, the dosage of ammonium molybdate is 1g, the dosage of ammonium chloride in the present embodiment
For 7.5g.
Embodiment 10
The present embodiment provides a kind of MoO3/ rGO-N composite material and this kind of MoO3The preparation side of/rGO-N composite material
Method.
MoO described in the present embodiment3/ rGO-N composite material is denoted as A10, the redox graphene including N doping and
It is grown in the sheet MoO of the redox graphene surface of N doping3, composite material has three-dimensional porous structure, specific to prepare
Step is essentially identical with embodiment 1, the difference is that changing in step (2) in the time and temperature, reaction kettle of oil bath
It is the time and temperature of the time of reactant and temperature and high-temperature calcination, specific as follows: oil bath of the mixture solution at 160 DEG C
Middle heating stirring 2h；After mixture solution is transferred to reaction kettle, in 210 DEG C of reaction 16h；Black powder is transferred in porcelain boat,
4h is calcined in the tube furnace of 800 DEG C of nitrogen atmospheres.
Embodiment 11
The present embodiment provides a kind of MoO3/ rGO-N composite material and this kind of MoO3The preparation side of/rGO-N composite material
Method.
MoO described in the present embodiment3/ rGO-N composite material is denoted as A11, the redox graphene including N doping and
It is grown in the sheet MoO of the redox graphene surface of N doping3, composite material has three-dimensional porous structure, specific to prepare
Step is essentially identical with embodiment 1, the difference is that changing in step (2) in the time and temperature, reaction kettle of oil bath
It is the time and temperature of the time of reactant and temperature and high-temperature calcination, specific as follows: oil bath of the mixture solution at 100 DEG C
Middle heating stirring 6h；After mixture solution is transferred to reaction kettle, reacted for 24 hours at 150 DEG C；Black powder is transferred in porcelain boat,
8h is calcined in the tube furnace of 550 DEG C of nitrogen atmospheres.
The MoO of embodiment 2-11 preparation is tested respectively3The chemical property of/rGO-N composite A 2-A11, test side
Method is identical as the method for A1 prepared by testing example 1, shows from test result, and the A2-A11 of embodiment 2-11 preparation all has
Preferable chemical property has good cyclical stability, and the capacity of A2-A11 remains in 500mAh after circulation 50 times
g-1More than.
In addition, being also scanned Electronic Speculum inspection to the A4-A11 of embodiment 4-11 preparation respectively by Hitachi S-4800
It surveys, by testing result it is found that A2-A11 is MoO3With the composite material of three-dimensional N doping redox graphene.
In other embodiments, when preparing graphene oxide, the suspension after potassium permanganate is added is stirred at room temperature
About 20h (18-22h) is to form underflow.
It is described above that technology contents of the invention are only further illustrated with embodiment, in order to which reader is easier to understand,
But embodiments of the present invention are not represented and are only limitted to this, any technology done according to the present invention extends or recreation, is sent out by this
Bright protection.
Claims (10)
1. a kind of MoO3/ rGO-N composite material, it is characterised in that: redox graphene including N doping and be grown in nitrogen and mix
The sheet MoO of miscellaneous redox graphene surface3, the composite material is with three-dimensional porous structure.
2. a kind of MoO3The preparation method of/rGO-N composite material, which comprises the following steps:
S1, it is heated to reflux 2-6h in the environment of the aqueous solution of graphene oxide, molybdate and ammonium salt is placed in 100-160 DEG C, obtained
To evenly dispersed mixed solution；The mass ratio of the graphene oxide, molybdate and ammonium salt is 1:(4-8): (20-60)；
S2, mixed solution is heated to 150-210 DEG C, reacts 16-24h；
S3, it filters the mixed solution after step S2 reaction and washs filter cake, dry cake obtains black powder；
S4, black powder carry out high-temperature calcination under an inert atmosphere, obtain composite material.
3. MoO according to claim 23The preparation method of the preparation method of/rGO-N composite material, it is characterised in that: institute
It states in step S1, the aqueous solution of graphene oxide, molybdate and ammonium salt is placed in 100-160 DEG C of oil bath and is heated to reflux.
4. MoO according to claim 23The preparation method of the preparation method of/rGO-N composite material, it is characterised in that: institute
It states in step S3, dry cake is dried in the vacuum oven for be placed in filter cake 80 DEG C.
5. MoO according to claim 23The preparation method of the preparation method of/rGO-N composite material, it is characterised in that: institute
It states in step S4, the calcination temperature of high-temperature calcination is 550-800 DEG C, calcination time 4-8h.
6. MoO according to claim 23The preparation method of the preparation method of/rGO-N composite material, which is characterized in that institute
State graphene oxide the preparation method is as follows:
Natural graphite powder is added in the concentrated sulfuric acid that mass fraction is 98%, and addition sodium nitrate is stirred at room temperature；Then exist
Potassium permanganate is continuously added under stirring, and keeps suspension temperature at 20 DEG C or less during adding potassium permanganate；Then suspension
18-22h is stirred at room temperature to form underflow；Followed by water is added into underflow and stirs, hydrogen peroxide, which is then added, to be made to mix
Closing object color becomes yellow from brown and continues to stir 0.5h or more；Followed by come mixture and wash filter cake and it is dry after,
Obtain graphene oxide；
The quality of the natural graphite powder and the volume ratio of the concentrated sulfuric acid are 1g:30mL；The natural graphite powder, sodium nitrate and Gao Meng
The mass ratio of sour potassium is 1:0.75:20；The quality of the natural graphite powder and the volume ratio of water are 1g:128mL.
7. MoO according to claim 1-63The preparation method of the preparation method of/rGO-N composite material, feature
It is: in step S1, in the aqueous solution of the graphene oxide, molybdate and ammonium salt, the concentration of graphene oxide in aqueous solution
For 0.5-2.5mg/mL.
8. MoO according to claim 1-63The preparation method of the preparation method of/rGO-N composite material, feature
Be: molybdate is selected from least one of ammonium molybdate, sodium molybdate, potassium molybdate.
9. MoO according to claim 1-63The preparation method of the preparation method of/rGO-N composite material, feature
Be: the ammonium salt is selected from least one of ammonium chloride, ammonium nitrate, ammonium bromide.
10. a kind of MoO as described in claim 13/ rGO-N composite material is used as lithium ion battery negative material.
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| CN109988411A (en) * | 2019-03-13 | 2019-07-09 | 台州博尔特塑胶电子有限公司 | Flame-retardant smoke inhibition thermoplastic polyurethane anti-static composite material and preparation method thereof |
| CN113571842A (en) * | 2021-06-28 | 2021-10-29 | 惠州锂威新能源科技有限公司 | Diaphragm, preparation method thereof and lithium ion battery |
| CN115286039A (en) * | 2022-08-24 | 2022-11-04 | 陕西理工大学 | Preparation method of molybdenum oxide-graphene antibacterial material |
| CN115799459A (en) * | 2023-02-06 | 2023-03-14 | 昆山美淼新材料科技有限公司 | Production process of graphene modified metal electrode |
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| CN105591077A (en) * | 2015-12-17 | 2016-05-18 | 中南大学 | Preparation method of molybdenum carbide/nitrogen-sulfur codoped spongy graphene cathode composite for sodium-ion battery |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109988411A (en) * | 2019-03-13 | 2019-07-09 | 台州博尔特塑胶电子有限公司 | Flame-retardant smoke inhibition thermoplastic polyurethane anti-static composite material and preparation method thereof |
| CN109988411B (en) * | 2019-03-13 | 2021-07-16 | 台州博尔特塑胶电子有限公司 | Flame-retardant smoke-suppression thermoplastic polyurethane antistatic composite material and preparation method thereof |
| CN113571842A (en) * | 2021-06-28 | 2021-10-29 | 惠州锂威新能源科技有限公司 | Diaphragm, preparation method thereof and lithium ion battery |
| CN115286039A (en) * | 2022-08-24 | 2022-11-04 | 陕西理工大学 | Preparation method of molybdenum oxide-graphene antibacterial material |
| CN115799459A (en) * | 2023-02-06 | 2023-03-14 | 昆山美淼新材料科技有限公司 | Production process of graphene modified metal electrode |
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