CN108963215A - The fixed porous MoS of N doped graphene flexible substrates with three-dimensional structure2Nano material and its preparation method and application - Google Patents
The fixed porous MoS of N doped graphene flexible substrates with three-dimensional structure2Nano material and its preparation method and application Download PDFInfo
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Abstract
The fixed porous MoS of a kind of N doped graphene flexible substrates with three-dimensional structure disclosed by the invention2Nano material and its preparation method and application belongs to lithium, sodium ion battery electrode material preparation technical field, and the pure phase MoO of preparation is decomposed by ammonium molybdate3It is first uniformly mixed with graphene, prepares MoO3Then reaction in-situ under inert atmosphere conditions with thiocarbamide according to a certain percentage in it by/graphene presoma occurs.The N generated using thiocarbamide pyrolysis2For nitrogen source, SOXFor sulphur source, C atom in N atom and graphene is made to exchange realization doping, while SO by solid phase methodXWith MoO3It reacts to obtain the MoS with porous structure2The graphene surface growth in situ that can be adulterated in N.The fixed porous MoS of the N doped graphene flexible substrates with three-dimensional structure is made by one step of solid phase method situ synthesis techniques in the present invention2Nano material has preparation simple, and process is easily-controllable, and the period is short, and the repeatability of product is high and the advantages that being conducive to large-scale production.
Description
Technical field
The invention belongs to lithiums, sodium ion battery electrode material preparation technical field, and in particular to a kind of N doped graphene is soft
Property substrate fixed porous MoS2Nano material and its preparation method and application.
Background technique
With a large amount of exploitations and utilization of non-renewable resources, people have more cleaning and sustainable energy storage system
Come more concerns and research.In terms of advanced energy storage systems technology, researchers to rechargeable battery, liquid cell and
There are more and more researchs in the fields such as supercapacitor.In these areas, since lithium ion battery, sodium-ion battery have
High energy density and it is longer using birthday noodle and it is environmental-friendly the features such as, by it is believed that being most possibly to become energy
The system of source storage.[Larcher D, Tarascon J M.Towards greener and more sustainable
batteries for electrical energy storage[J].Nature Chemistry,2015,7(1):19-29],
[Choi J W,Aurbach D.Promise and reality of post-lithium-ion batteries with
High energy densities [J] .Nature Reviews Materials, 2016,1 (4): 16013] graphite crystallinity
Height, the structure with stratiform.Commercial li-ion battery mostly uses graphite as its negative electrode material.When it is used for secondary battery negative pole
Material, theoretical capacity is 372mAh g in lithium ion battery-1, and it is used for sodium-ion battery, theoretical capacity is about 20mAh
g-1.Therefore, it is difficult to meet the needs of current.[Qian J,Wu X,Cao Y,et al.High capacity and rate
capability of amorphous phosphorus for sodium ion batteries[J].Angewandte
Chemie, 2013,125 (17): 4731-4734.], [Zhu Y, Han X, Xu Y, et al.Electrospun Sb/C
fibers for a stable and fast sodium-ion battery anode[J].ACS nano,2013,7(7):
6378-6386.]。MoS2A typical layer structure material, between layers be spaced about 0.615 nm, it is significantly high
In graphite (0.335nm).This provides condition for the insertion and abjection of sodium ion.However, MoS2Interlayer relies primarily on Van der Waals
Power is connected with each other, and easily causes structure collapses during embedding/removing sodium, so that active material aggregation and big volume change occurs,
As sodium-ion battery cycle-index increases, capacity also occurs obviously to decay.
Summary of the invention
The fixed porous MoS of the N doped graphene flexible substrates with three-dimensional structure that the purpose of the present invention is to provide a kind of2
Nano material and its preparation method and application, the preparation method have it is easy to operate, reaction process is controllable, and reaction time is short, energy
Consume low, the advantages that repeatability is high, and yield is big；Through MoS made from the method for the present invention2Nano material has specific discharge capacity high, follows
The advantages that ring stability is good can be used as lithium/anode material of lithium-ion battery.
The present invention is to be achieved through the following technical solutions:
The fixed porous MoS of the N doped graphene flexible substrates with three-dimensional structure that the invention discloses a kind of2Nano material
Preparation method, comprising the following steps:
1) using ammonium molybdate as raw material, after ground, heat treatment, cooling, washing, dry, obtained pure phase MoO3；
2) pure phase MoO in deionized water by graphene dispersion, is added3, it is evaporated while stirring, MoO is made3/ graphene
Presoma；
3) by MoO3/ graphene presoma and thiocarbamide are according to 0.5:(1.0~5.0) mass ratio, grinding uniformly after, lazy
Property atmosphere under, from room temperature to 150~350 DEG C, 0.5~2h of insulation reaction then proceedes to be warming up to 600~800 DEG C, heat preservation
0.5~2h is reacted, is cooled to room temperature, reaction product is cleaned, is dry, it is flexible that the N doped graphene with three-dimensional structure is made
The fixed porous MoS of substrate2Nano material.
Preferably, in step 1), heat treatment is will to grind uniform ammonium molybdate, in air atmosphere, with 5~10 DEG C
min-1Heating rate rise to 400~600 DEG C from room temperature, keep the temperature 1~3h.
Preferably, it in step 1), after reaction product is cooled to room temperature, is cleaned 3~6 times with deionized water, is then freezed
Dry 8~12h.
Preferably, in step 2), graphene and pure phase MoO3Mass ratio is (0.06~0.14): (1.0~1.8).It is preferred that
Ground, inert atmosphere select argon gas, control in reaction process the argon gas flow velocity being passed through, concrete operations are as follows:
When reaction starts, the volumetric flow of gas for being passed through argon gas is 100sccm；
When temperature rises to 100 DEG C by room temperature, the volumetric flow of gas for controlling argon gas is 0~50sccm；
The volumetric flow of gas that argon gas is adjusted after insulation reaction is 100~200sccm.
Preferably, in step 3), the heating rate of temperature-rise period is 5~10 DEG C of min-1。
Preferably, in step 3), reaction product is cleaned 3~6 times with deionized water, is then freeze-dried 8~12h.
The invention also discloses using the N doped graphene flexibility base made from above-mentioned preparation method with three-dimensional structure
The fixed porous MoS in bottom2Nano material.
The fixed porous MoS of the N doped graphene flexible substrates with three-dimensional structure that the invention also discloses above-mentioned2Nanometer
Material is as the application of lithium/anode material of lithium-ion battery.
Compared with prior art, the invention has the following beneficial technical effects:
Preparation disclosed by the invention has the fixed porous MoS of the N doped graphene flexible substrates of three-dimensional structure2Nano material
Method, pass through ammonium molybdate decompose preparation pure phase MoO3It is first uniformly mixed with graphene, prepares MoO3/ graphene presoma, so
Reaction in-situ is occurred into thiocarbamide in it under inert atmosphere conditions according to a certain percentage afterwards.The N generated using thiocarbamide pyrolysis2For nitrogen
Source, SOXFor sulphur source, C atom in N atom and graphene is made to exchange realization doping, while SO by solid phase methodXWith MoO3Occur
Reaction obtains the MoS with porous structure2The graphene surface growth in situ that can be adulterated in N.Preparation method of the present invention is novel,
The fixed porous MoS of the N doped graphene flexible substrates with three-dimensional structure is made by one step of solid phase method situ synthesis techniques2It receives
Rice material.Therefore, the present invention has preparation simple, and process is easily-controllable, and the period is short, and the repeatability of product is high and is conducive to scale metaplasia
The advantages that production.
Further, inert atmosphere selects argon gas, gas of the different phase in reaction process in heat preservation to the argon gas being passed through
Body flow is controlled, by control argon gas flow speed, with guarantee reaction by the argon gas of small volumetric flow of gas come
Realize the N of reaction environment middle and high concentration2And SOX。
Through the fixed porous MoS of N doped graphene flexible substrates made from the method for the present invention with three-dimensional structure2Nanometer material
Material, has excellent electric conductivity, cyclical stability and high specific discharge capacity, therefore can be used as lithium/sodium-ion battery cathode
Material is widely used.
Detailed description of the invention
Fig. 1 is the fixed porous MoS of the N doped graphene flexible substrates with three-dimensional structure of preparation2The XRD of nano material
Figure；
Fig. 2 is the fixed porous MoS of the N doped graphene flexible substrates with three-dimensional structure of preparation2The SEM of nano material
Figure；
Fig. 3 is the fixed porous MoS of the N doped graphene flexible substrates with three-dimensional structure of preparation2Nano material conduct
The loop test figure of lithium ion battery negative material；
Fig. 4 is the fixed porous MoS of the N doped graphene flexible substrates with three-dimensional structure of preparation2Nano material conduct
The loop test figure of anode material of lithium-ion battery.
Specific embodiment
Below with reference to specific embodiment, the present invention is described in further detail, it is described be explanation of the invention and
It is not to limit.
Embodiment 1
A kind of fixed porous MoS of the N doped graphene flexible substrates with three-dimensional structure2The preparation method of nano material,
The following steps are included:
Step 1: pure phase MoO3Preparation
1) ammonium molybdate is taken, is put into mortar and is fully ground, the sample after grinding is placed in porcelain boat, with 5 in tube furnace
℃min-1Heating rate rise to 400 DEG C, after keeping the temperature 1h, Pintsch process obtains MoO under the conditions of air atmosphere3；
2) it is cooled to room temperature after reaction, product is cleaned 3 times with deionized water, be freeze-dried 8h, can be obtained pure
Phase MoO3。
Step 2:MoO3The preparation of/graphene presoma
In deionized water by 0.06g graphene dispersion, 1.0g pure phase MoO is added3, method by being evaporated while stirring
Prepare MoO3/ graphene presoma.
The fixed porous MoS of step 3:N doped graphene flexible substrates2The preparation of nano material
1) by MoO3/ graphene presoma and thiocarbamide are ground according to the mass ratio of 0.5:1.0 uniformly, by the sample after grinding
It is placed in porcelain boat, reacts under the conditions of tube-type atmosphere furnace argon atmosphere；
2) it is 100sccm that Ar gas flow rate is passed through when reaction starts, it is ensured that reaction carries out under inert conditions.With 5 DEG C
min-1Heating rate from room temperature to 100 DEG C, the gas flow rate for controlling argon gas is 0sccm, is continuously heating to 150 DEG C, is protected
Temperature reaction 0.5h；
3) again with 5 DEG C of min-1Heating rate be continuously heating to 600 DEG C, keep the temperature 0.5h again, adjust argon after reaction
Gas gas flow rate is 100sccm, N and S superfluous in reaction environment is discharged；
4) reaction product is cleaned 3 times with deionized water, is then freeze-dried 8h, the N with three-dimensional structure is made and adulterates
The fixed porous MoS of graphene flexible substrates2Nano material.
Embodiment 2
A kind of fixed porous MoS of the N doped graphene flexible substrates with three-dimensional structure2The preparation method of nano material,
The following steps are included:
Step 1: pure phase MoO3Preparation
1) ammonium molybdate is taken, is put into mortar and is fully ground, the sample after grinding is placed in porcelain boat, with 6 in tube furnace
℃min-1Heating rate rise to 450 DEG C, after keeping the temperature 1.5h, Pintsch process obtains MoO under the conditions of air atmosphere3；
2) it is cooled to room temperature after reaction, product is cleaned 4 times with deionized water, be freeze-dried 9h, can be obtained pure
Phase MoO3。
Step 2:MoO3The preparation of/graphene presoma
In deionized water by 0.08g graphene dispersion, 1.2g pure phase MoO is added3, method by being evaporated while stirring
Prepare MoO3/ graphene presoma.
The fixed porous MoS of step 3:N doped graphene flexible substrates2The preparation of nano material
1) by MoO3/ graphene presoma and thiocarbamide are ground according to the mass ratio of 0.5:2.0 uniformly, by the sample after grinding
It is placed in porcelain boat, reacts under the conditions of tube-type atmosphere furnace argon atmosphere；
2) it is 100sccm that Ar gas flow rate is passed through when reaction starts, it is ensured that reaction carries out under inert conditions.With 6 DEG C
min-1Heating rate from room temperature to 100 DEG C, the gas flow rate for controlling argon gas is 10sccm, is continuously heating to 200 DEG C, is protected
Temperature reaction 0.8h；
3) again with 6 DEG C of min-1Heating rate be continuously heating to 650 DEG C, keep the temperature 0.8h again, adjust argon after reaction
Gas gas flow rate is 120sccm, N and S superfluous in reaction environment is discharged；
4) reaction product is cleaned 4 times with deionized water, is then freeze-dried 9h, the N with three-dimensional structure is made and adulterates
The fixed porous MoS of graphene flexible substrates2Nano material.
Embodiment 3
A kind of fixed porous MoS of the N doped graphene flexible substrates with three-dimensional structure2The preparation method of nano material,
The following steps are included:
Step 1: pure phase MoO3Preparation
1) ammonium molybdate is taken, is put into mortar and is fully ground.Sample after grinding is placed in porcelain boat, with 7 in tube furnace
℃min-1Heating rate rise to 500 DEG C, after keeping the temperature 2.0h, Pintsch process obtains MoO under the conditions of air atmosphere3；
2) it is cooled to room temperature after reaction, product is cleaned 4 times with deionized water, be freeze-dried 10h, can be obtained pure
Phase MoO3。
Step 2:MoO3The preparation of/graphene presoma
In deionized water by 0.1g graphene dispersion, 1.4g pure phase MoO is added3, method by being evaporated while stirring
Prepare MoO3/ graphene presoma.
The fixed porous MoS of step 3:N doped graphene flexible substrates2The preparation of nano material
1) by MoO3/ graphene presoma and thiocarbamide are ground according to the mass ratio of 0.5:3.0 uniformly, by the sample after grinding
It is placed in porcelain boat, reacts under the conditions of tube-type atmosphere furnace argon atmosphere；
2) it is 100sccm that Ar gas flow rate is passed through when reaction starts, it is ensured that reaction carries out under inert conditions.With 7 DEG C
min-1Heating rate from room temperature to 100 DEG C, the gas flow rate for controlling argon gas is 30sccm, is continuously heating to 250 DEG C, is protected
Temperature reaction 1.2h；
3) again with 7 DEG C of min-1Heating rate be continuously heating to 7000 DEG C, keep the temperature 1.2h again, adjust argon after reaction
Gas gas flow rate is 150sccm, N and S superfluous in reaction environment is discharged；
4) reaction product is cleaned 5 times with deionized water, is then freeze-dried 10h, the N with three-dimensional structure is made and adulterates
The fixed porous MoS of graphene flexible substrates2Nano material.
Embodiment 4
A kind of fixed porous MoS of the N doped graphene flexible substrates with three-dimensional structure2The preparation method of nano material,
The following steps are included:
Step 1: pure phase MoO3Preparation
1) ammonium molybdate is taken, is put into mortar and is fully ground.Sample after grinding is placed in porcelain boat, with 8 in tube furnace
℃min-1Heating rate rise to 550 DEG C, after keeping the temperature 2.5h, Pintsch process obtains MoO under the conditions of air atmosphere3；
2) it is cooled to room temperature after reaction, product is cleaned 5 times with deionized water, be freeze-dried 11h, can be obtained pure
Phase MoO3。
Step 2:MoO3The preparation of/graphene presoma
In deionized water by 0.12g graphene dispersion, 1.6g pure phase MoO is added3, method by being evaporated while stirring
Prepare MoO3/ graphene presoma.
The fixed porous MoS of step 3:N doped graphene flexible substrates2The preparation of nano material
1) by MoO3/ graphene presoma and thiocarbamide are ground according to the mass ratio of 0.5:4.0 uniformly, by the sample after grinding
It is placed in porcelain boat, reacts under the conditions of tube-type atmosphere furnace argon atmosphere；
2) it is 100sccm that Ar gas flow rate is passed through when reaction starts, it is ensured that reaction carries out under inert conditions.With 8 DEG C
min-1Heating rate from room temperature to 100 DEG C, the gas flow rate for controlling argon gas is 40sccm, is continuously heating to 300 DEG C, is protected
Temperature reaction 1.5h；
3) again with 8 DEG C of min-1Heating rate be continuously heating to 700 DEG C, keep the temperature 1.5h again, adjust argon after reaction
Gas gas flow rate is 180sccm, N and S superfluous in reaction environment is discharged；
4) reaction product is cleaned 5 times with deionized water, is then freeze-dried 11h, the N with three-dimensional structure is made and adulterates
The fixed porous MoS of graphene flexible substrates2Nano material.
Embodiment 5
A kind of fixed porous MoS of the N doped graphene flexible substrates with three-dimensional structure2The preparation method of nano material,
The following steps are included:
Step 1: pure phase MoO3Preparation
1) ammonium molybdate is taken, is put into mortar and is fully ground.Sample after grinding is placed in porcelain boat, with 10 in tube furnace
℃min-1Heating rate rise to 600 DEG C, after keeping the temperature 3.0h, Pintsch process obtains MoO under the conditions of air atmosphere3；
2) it is cooled to room temperature after reaction, product is cleaned 6 times with deionized water, be freeze-dried 12h, can be obtained pure
Phase MoO3。
Step 2:MoO3The preparation of/graphene presoma
In deionized water by 0.14g graphene dispersion, 1.8g pure phase MoO is added3, method by being evaporated while stirring
Prepare MoO3/ graphene presoma.
The fixed porous MoS of step 3:N doped graphene flexible substrates2The preparation of nano material
1) by MoO3/ graphene presoma and thiocarbamide are ground according to the mass ratio of 0.5:5.0 uniformly, by the sample after grinding
It is placed in porcelain boat, reacts under the conditions of tube-type atmosphere furnace argon atmosphere；
2) it is 100sccm that Ar gas flow rate is passed through when reaction starts, it is ensured that reaction carries out under inert conditions.With 10 DEG C
min-1Heating rate from room temperature to 100 DEG C, the gas flow rate for controlling argon gas is 50sccm, is continuously heating to 350 DEG C, is protected
Temperature reaction 2.0h；
3) again with 10 DEG C of min-1Heating rate be continuously heating to 800 DEG C, keep the temperature 2.0h again, adjust argon after reaction
Gas gas flow rate is 200sccm, N and S superfluous in reaction environment is discharged；
4) reaction product is cleaned 6 times with deionized water, is then freeze-dried 12h, the N with three-dimensional structure is made and adulterates
The fixed porous MoS of graphene flexible substrates2Nano material.
Referring to Fig. 1, it will be seen from figure 1 that MoS can be prepared by in-situ synthesis2Nano material (red curve),
Each diffraction maximum can be with MoS in the diffracting spectrum of its XRD2The diffraction maximum of standard card is corresponding, shows it preferably
Crystallinity and higher purity.
Referring to fig. 2, as can be seen from the figure three-dimensional structure, MoS is presented in prepared product2Size be nanoscale, MoS2Table
Reveal a kind of porous structure, and of uniform size.
In addition, by the fixed porous MoS of the N doped graphene flexible substrates obtained above with three-dimensional structure2Nanometer material
Material is applied in lithium/anode material of lithium-ion battery, and it is as follows to test its performance:
Referring to Fig. 3, for the fixed porous MoS of the N doped graphene flexible substrates with three-dimensional structure2Nano material is as lithium
Its electric property of ion battery cathode material is shown, it can be seen that the N doped graphene flexible substrates with three-dimensional structure are solid
Fixed porous MoS2Nano material has excellent cyclical stability and specific discharge capacity, is used in lithium ion battery,
100mA g-1Current density under, recycled by 70 circles, capacity still may remain in 750mAh g-1More than.This shows three-dimensional knot
The fixed porous MoS of the N doped graphene flexible substrates of structure2It is steady in specific discharge capacity and circulation applied to negative electrode of lithium ion battery
Qualitative aspect is preferable.
By the fixed porous MoS of the N doped graphene flexible substrates with three-dimensional structure2Nano material is used for sodium-ion battery
In, as a result as shown in figure 4, it can be seen from the figure that in 5000mA g-1Current density under, by 500 circle recycle, capacity is still
It may remain in 162mAh g-1.This shows the fixed porous MoS of the N doped graphene flexible substrates of three-dimensional structure2Applied to sodium
Ion battery cathode, in terms of specific discharge capacity and cyclical stability preferably.
In conclusion the present invention fixes porous MoS by solid phase method fabricated in situ N doped graphene flexible substrates2。
The MoS of N doped graphene and porous structure is realized by this method2In this two step of the growth in situ on N doped graphene surface
It reacts while occurring.This method has preparation process simple, easily-controllable, and reaction time is short, and low energy consumption, and repeatability is high, and yield is big etc.
Feature.Meanwhile this method also solves the preparation of N doped graphene and MoS in the prior art2Original position on the surface of graphene
Grow the problem of this two-step reaction separately carries out.Through having the N doped graphene flexible substrates of three-dimensional structure made from this method
Fixed porous MoS2Nano material has the features such as specific discharge capacity is high, good cycling stability.
Claims (9)
1. a kind of fixed porous MoS of the N doped graphene flexible substrates with three-dimensional structure2The preparation method of nano material, it is special
Sign is, comprising the following steps:
1) using ammonium molybdate as raw material, after ground, heat treatment, cooling, washing, dry, obtained pure phase MoO3；
2) pure phase MoO in deionized water by graphene dispersion, is added3, it is evaporated while stirring, MoO is made3/ graphene forerunner
Body；
3) by MoO3/ graphene presoma and thiocarbamide are according to 0.5:(1.0~5.0) mass ratio, grinding uniformly after, in indifferent gas
Under atmosphere, from room temperature to 150~350 DEG C, 0.5~2h of insulation reaction, then proceed to be warming up to 600~800 DEG C, insulation reaction
0.5~2h is cooled to room temperature, and reaction product is cleaned, is dry, the N doped graphene flexible substrates with three-dimensional structure are made
Fixed porous MoS2Nano material.
2. the fixed porous MoS of the N doped graphene flexible substrates with three-dimensional structure according to claim 12Nano material
Preparation method, which is characterized in that in step 1), heat treatment is will to grind uniform ammonium molybdate, in air atmosphere, with 5
~10 DEG C of min-1Heating rate rise to 400~600 DEG C from room temperature, keep the temperature 1~3h.
3. the fixed porous MoS of the N doped graphene flexible substrates with three-dimensional structure according to claim 12Nano material
Preparation method, which is characterized in that in step 1), after reaction product is cooled to room temperature, clean 3~6 times with deionized water, so
It is freeze-dried 8~12h afterwards.
4. the fixed porous MoS of the N doped graphene flexible substrates with three-dimensional structure according to claim 12Nano material
Preparation method, which is characterized in that in step 2), graphene and pure phase MoO3Mass ratio is (0.06~0.14): (1.0~
1.8)。
5. the fixed porous MoS of the N doped graphene flexible substrates with three-dimensional structure according to claim 12Nano material
Preparation method, which is characterized in that in step 3), inert atmosphere selects argon gas, in reaction process to the argon gas flow velocity being passed through into
Row control, concrete operations are as follows:
When reaction starts, the volumetric flow of gas for being passed through argon gas is 100sccm；
When temperature rises to 100 DEG C by room temperature, the volumetric flow of gas for controlling argon gas is 0~50sccm；
The volumetric flow of gas that argon gas is adjusted after insulation reaction is 100~200sccm.
6. the fixed porous MoS of the N doped graphene flexible substrates with three-dimensional structure according to claim 52Nano material
Preparation method, which is characterized in that in step 3), the heating rate of temperature-rise period is 5~10 DEG C of min-1。
7. the fixed porous MoS of the N doped graphene flexible substrates with three-dimensional structure according to claim 12Nano material
Preparation method, which is characterized in that in step 3), reaction product is cleaned 3~6 times with deionized water, be then freeze-dried 8~
12h。
8. using the N doped graphene obtained with three-dimensional structure of preparation method described in any one of claim 1~7
The fixed porous MoS of flexible substrates2Nano material.
9. the fixed porous MoS of the N doped graphene flexible substrates with three-dimensional structure according to any one of claims 82Nano material conduct
The application of lithium/anode material of lithium-ion battery.
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