CN108963215B - N-doped graphene flexible substrate fixed porous MoS with three-dimensional structure2Nano material and preparation method and application thereof - Google Patents

N-doped graphene flexible substrate fixed porous MoS with three-dimensional structure2Nano material and preparation method and application thereof Download PDF

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CN108963215B
CN108963215B CN201810718132.6A CN201810718132A CN108963215B CN 108963215 B CN108963215 B CN 108963215B CN 201810718132 A CN201810718132 A CN 201810718132A CN 108963215 B CN108963215 B CN 108963215B
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许占位
王天
席乔
杨军
黄剑锋
曹丽云
刘鑫悦
段欣彤
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Shaanxi University of Science and Technology
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    • HELECTRICITY
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    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • HELECTRICITY
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    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • H01M4/58Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
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    • H01M4/58Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H01M4/587Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
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Abstract

The invention discloses an N-doped graphene flexible substrate fixed porous MoS with a three-dimensional structure2A nano material and a preparation method and application thereof belong to the technical field of preparation of electrode materials of lithium and sodium ion batteries, and the pure phase MoO is prepared by decomposing ammonium molybdate3Uniformly mixing with graphene to prepare MoO3And carrying out in-situ reaction on the graphene precursor and thiourea according to a certain proportion under the inert atmosphere condition. N produced by pyrolysis of thiourea2As a nitrogen source, SOXIs a sulfur source, N atoms and C atoms in graphene are exchanged to realize doping through a solid phase method, and SO is addedXWith MoO3The reaction is carried out to obtain MoS with a porous structure2The graphene can grow on the surface of the N-doped graphene in situ. According to the invention, the N-doped graphene flexible substrate fixed porous MoS with a three-dimensional structure is prepared in one step by using a solid-phase method in-situ synthesis technology2The nano material has the advantages of simple preparation, easily controlled process, short period, high product repeatability, suitability for large-scale production and the like.

Description

N-doped graphene flexible substrate fixed porous MoS with three-dimensional structure2Nano material and preparation method and application thereof
Technical Field
The invention belongs to the technical field of preparation of electrode materials of lithium and sodium ion batteries, and particularly relates to an N-doped graphene flexible substrate fixed porous MoS2A nano material and a preparation method and application thereof.
Background
With the large exploitation and utilization of non-renewable resources, there is an increasing interest and research on clean and sustainable energy storage systems. In the field of advanced energy storage system technology, researchers have conducted more and more research into the fields of rechargeable batteries, liquid batteries, super capacitors, and the like. In these fields, lithium ion batteries and sodium ion batteries are considered to be the most likely energy storage systems due to their high energy density, long service life and environmental friendliness. [ Larcher D, Tarascon J M. Towards greener and more stable 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 has high crystallinity and a layered structure. Most commercial lithium ion batteries use graphite as their negative electrode material. When the material is used as a negative electrode material of a secondary battery, the theoretical capacity of the material in a lithium ion battery is 372mAh g-1And for sodium ion batteries, the theoretical capacity is about 20mAh g-1. It is difficult to meet the current demand. [ Qian J, Wu X, Cao Y, et al. high and rate capability of Amorphous phosphate for sodium 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.]。MoS2Is a typical laminated structure material, and the spacing between layers is about0.615 nm, significantly higher than graphite (0.335 nm). This provides conditions for the intercalation and deintercalation of sodium ions. However, MoS2The layers are mainly connected with each other by virtue of Van der Waals force, the structure is easy to collapse in the process of sodium insertion/removal, so that active substance aggregation and large volume change occur, and the capacity is obviously attenuated as the cycle number of the sodium ion battery is increased.
Disclosure of Invention
The invention aims to provide an N-doped graphene flexible substrate fixed porous MoS with a three-dimensional structure2The preparation method has the advantages of simple operation, controllable reaction process, short reaction period, low energy consumption, high repeatability, high yield and the like; MoS prepared by the method of the invention2The nano material has the advantages of high discharge specific capacity, good cycling stability and the like, and can be used as a negative electrode material of a lithium/sodium ion battery.
The invention is realized by the following technical scheme:
the invention discloses an N-doped graphene flexible substrate fixed porous MoS with a three-dimensional structure2The preparation method of the nano material comprises the following steps:
1) taking ammonium molybdate as a raw material, grinding, heating, cooling, washing and drying to obtain pure-phase MoO3
2) Dispersing graphene in deionized water, and adding pure-phase MoO3Stirring and evaporating to dryness to obtain MoO3A graphene precursor;
3) adding MoO3Graphene precursor and thiourea according to 0.5: (1.0-5.0), uniformly grinding, heating to 150-350 ℃ from room temperature in an inert atmosphere, carrying out heat preservation reaction for 0.5-2 h, then continuously heating to 600-800 ℃, carrying out heat preservation reaction for 0.5-2 h, cooling to room temperature, cleaning and drying a reaction product, and thus obtaining the N-doped graphene flexible substrate fixed porous MoS with the three-dimensional structure2And (3) nano materials.
Preferably, in the step 1), the heating treatment is to uniformly grind the ammonium molybdate at 5-10 ℃ for min in an air atmosphere-1Temperature rising rate of from room temperatureRaising the temperature to 400-600 ℃, and keeping the temperature for 1-3 h.
Preferably, in the step 1), after cooling the reaction product to room temperature, washing the reaction product with deionized water for 3-6 times, and then freeze-drying the reaction product for 8-12 hours.
Preferably, in step 2), the graphene is mixed with pure-phase MoO3The mass ratio is (0.06-0.14): (1.0-1.8). Preferably, argon is selected as the inert atmosphere, and the flow rate of the introduced argon is controlled in the reaction process, and the specific operation is as follows:
when the reaction starts, the volume flow of the gas introduced with argon is 100 sccm;
when the temperature is increased from room temperature to 100 ℃, controlling the gas volume flow of argon to be 0-50 sccm;
and after the heat preservation reaction is finished, adjusting the gas volume flow of the argon gas to be 100-200 sccm.
Preferably, in the step 3), the temperature rise rate in the temperature rise process is 5-10 ℃ min-1
Preferably, in the step 3), the reaction product is washed with deionized water for 3-6 times, and then freeze-dried for 8-12 hours.
The invention also discloses the N-doped graphene flexible substrate fixed porous MoS with the three-dimensional structure prepared by the preparation method2And (3) nano materials.
The invention also discloses the N-doped graphene flexible substrate fixed porous MoS with the three-dimensional structure2The application of the nano material as a negative electrode material of a lithium/sodium ion battery.
Compared with the prior art, the invention has the following beneficial technical effects:
the invention discloses a method for preparing N-doped graphene flexible substrate fixed porous MoS with a three-dimensional structure2Method for producing nanomaterial, pure phase MoO produced by decomposition of ammonium molybdate3Uniformly mixing with graphene to prepare MoO3And carrying out in-situ reaction on the graphene precursor and thiourea according to a certain proportion under the inert atmosphere condition. N produced by pyrolysis of thiourea2As a nitrogen source, SOXIs a sulfur source, N atoms and C atoms in graphene are exchanged to realize doping through a solid phase method, and simultaneouslySOXWith MoO3The reaction is carried out to obtain MoS with a porous structure2The graphene can grow on the surface of the N-doped graphene in situ. The preparation method is novel, and the N-doped graphene flexible substrate fixed porous MoS with the three-dimensional structure is prepared in one step by the solid-phase method in-situ synthesis technology2And (3) nano materials. Therefore, the method has the advantages of simple preparation, easily controlled process, short period, high product repeatability, contribution to large-scale production and the like.
Further, argon is selected as inert atmosphere, the gas flow of the introduced argon is controlled at different stages of heat preservation in the reaction process, and the flow speed of the argon gas is controlled to ensure that the reaction realizes high-concentration N in the reaction environment through the argon gas with small gas volume flow2And SOX
The N-doped graphene flexible substrate fixed porous MoS with the three-dimensional structure prepared by the method2The nano material has excellent conductivity, cycling stability and high specific discharge capacity, so that the nano material can be widely used as a negative electrode material of a lithium/sodium ion battery.
Drawings
FIG. 1 shows a prepared N-doped graphene flexible substrate fixed porous MoS with a three-dimensional structure2XRD pattern of the nanomaterial;
FIG. 2 shows a prepared N-doped graphene flexible substrate fixed porous MoS with a three-dimensional structure2SEM images of nanomaterials;
FIG. 3 shows a prepared N-doped graphene flexible substrate fixed porous MoS with a three-dimensional structure2The nano material is used as a cycle test chart of the lithium ion battery cathode material;
FIG. 4 shows a prepared N-doped graphene flexible substrate fixed porous MoS with a three-dimensional structure2And (3) taking the nano material as a cycle test chart of the cathode material of the sodium-ion battery.
Detailed Description
The present invention will now be described in further detail with reference to specific examples, which are intended to be illustrative, but not limiting, of the invention.
Example 1
N-doped graphene flexible substrate fixed porous MoS with three-dimensional structure2The preparation method of the nano material comprises the following steps:
step 1: pure phase MoO3Preparation of
1) Taking ammonium molybdate, putting the ammonium molybdate into a mortar for full grinding, putting the ground sample into a porcelain boat, and putting the porcelain boat in a tube furnace at 5 ℃ for min-1The temperature rise rate is increased to 400 ℃, and after heat preservation is carried out for 1h, the high temperature cracking is carried out under the air atmosphere condition to obtain MoO3
2) Cooling to room temperature after the reaction is finished, washing the product for 3 times by using deionized water, and freeze-drying for 8 hours to obtain pure-phase MoO3
Step 2: MoO3Preparation of graphene precursor
0.06g of graphene was dispersed in deionized water, and 1.0g of pure phase MoO was added3Preparing MoO by stirring and evaporating3A graphene precursor.
And step 3: n-doped graphene flexible substrate fixed porous MoS2Preparation of nanomaterials
1) Adding MoO3Graphene precursor and thiourea according to 0.5: 1.0, placing the ground sample in a porcelain boat, and reacting in a tubular atmosphere furnace under the condition of argon atmosphere;
2) ar gas is introduced at the beginning of the reaction at a flow rate of 100sccm to ensure that the reaction is carried out under inert conditions. At 5 ℃ for min-1The temperature rising rate is increased from room temperature to 100 ℃, the gas flow rate of argon is controlled to be 0sccm, the temperature is continuously raised to 150 ℃, and the heat preservation reaction is carried out for 0.5 h;
3) then at 5 deg.C for min-1The temperature is continuously increased to 600 ℃ at the temperature increasing rate, the temperature is maintained for 0.5h again, and the flow rate of argon gas is adjusted to be 100sccm after the reaction is finished so as to discharge the excessive N and S in the reaction environment;
4) washing the reaction product with deionized water for 3 times, and then freeze-drying for 8 hours to prepare the N-doped graphene flexible substrate fixed porous MoS with the three-dimensional structure2And (3) nano materials.
Example 2
Is provided withPorous MoS fixed on N-doped graphene flexible substrate with three-dimensional structure2The preparation method of the nano material comprises the following steps:
step 1: pure phase MoO3Preparation of
1) Taking ammonium molybdate, putting the ammonium molybdate into a mortar for full grinding, putting the ground sample into a porcelain boat, and putting the porcelain boat in a tube furnace at 6 ℃ for min-1The temperature rise rate is increased to 450 ℃, and after heat preservation is carried out for 1.5h, the MoO is obtained by pyrolysis under the air atmosphere condition3
2) Cooling to room temperature after the reaction is finished, washing the product with deionized water for 4 times, and freeze-drying for 9 hours to obtain pure-phase MoO3
Step 2: MoO3Preparation of graphene precursor
0.08g of graphene was dispersed in deionized water, and 1.2g of pure phase MoO was added3Preparing MoO by stirring and evaporating3A graphene precursor.
And step 3: n-doped graphene flexible substrate fixed porous MoS2Preparation of nanomaterials
1) Adding MoO3Graphene precursor and thiourea according to 0.5: 2.0, placing the ground sample in a porcelain boat, and reacting in a tubular atmosphere furnace under the condition of argon atmosphere;
2) ar gas is introduced at the beginning of the reaction at a flow rate of 100sccm to ensure that the reaction is carried out under inert conditions. At 6 ℃ for min-1The temperature rising rate is increased from room temperature to 100 ℃, the gas flow rate of argon is controlled to be 10sccm, the temperature is continuously increased to 200 ℃, and the heat preservation reaction is carried out for 0.8 h;
3) then at 6 deg.C for min-1The temperature is continuously increased to 650 ℃ at the temperature increasing rate, the temperature is maintained for 0.8h again, and the flow rate of argon gas is adjusted to 120sccm after the reaction is finished so as to discharge the excessive N and S in the reaction environment;
4) washing the reaction product with deionized water for 4 times, and then freeze-drying for 9 hours to prepare the N-doped graphene flexible substrate fixed porous MoS with the three-dimensional structure2And (3) nano materials.
Example 3
N doping with three-dimensional structureGraphene flexible substrate fixed porous MoS2The preparation method of the nano material comprises the following steps:
step 1: pure phase MoO3Preparation of
1) Taking ammonium molybdate, and fully grinding in a mortar. Placing the ground sample in a porcelain boat, and placing in a tube furnace at 7 deg.C for min-1The temperature rise rate is increased to 500 ℃, and after heat preservation is carried out for 2.0 hours, the MoO is obtained by pyrolysis under the air atmosphere condition3
2) Cooling to room temperature after the reaction is finished, washing the product with deionized water for 4 times, and freeze-drying for 10 hours to obtain pure-phase MoO3
Step 2: MoO3Preparation of graphene precursor
0.1g of graphene was dispersed in deionized water, and 1.4g of pure phase MoO was added3Preparing MoO by stirring and evaporating3A graphene precursor.
And step 3: n-doped graphene flexible substrate fixed porous MoS2Preparation of nanomaterials
1) Adding MoO3Graphene precursor and thiourea according to 0.5: 3.0, placing the ground sample in a porcelain boat, and reacting in a tube type atmosphere furnace under the condition of argon atmosphere;
2) ar gas is introduced at the beginning of the reaction at a flow rate of 100sccm to ensure that the reaction is carried out under inert conditions. At 7 ℃ for min-1The temperature rising rate is increased from room temperature to 100 ℃, the gas flow rate of argon is controlled to be 30sccm, the temperature is continuously increased to 250 ℃, and the reaction is carried out for 1.2 hours with heat preservation;
3) then at 7 ℃ for min-1The temperature is continuously raised to 7000 ℃, the temperature is maintained for 1.2h again, and the flow rate of argon gas is adjusted to 150sccm after the reaction is finished so as to discharge the excessive N and S in the reaction environment;
4) washing the reaction product with deionized water for 5 times, and then freeze-drying for 10 hours to prepare the N-doped graphene flexible substrate fixed porous MoS with the three-dimensional structure2And (3) nano materials.
Example 4
N-doped graphene flexible substrate with three-dimensional structureFixed porous MoS2The preparation method of the nano material comprises the following steps:
step 1: pure phase MoO3Preparation of
1) Taking ammonium molybdate, and fully grinding in a mortar. Placing the ground sample in a porcelain boat, and placing in a tube furnace at 8 deg.C for min-1The temperature rise rate is increased to 550 ℃, and after heat preservation is carried out for 2.5 hours, the MoO is obtained by pyrolysis under the air atmosphere condition3
2) Cooling to room temperature after the reaction is finished, washing the product for 5 times by using deionized water, and freeze-drying for 11 hours to obtain pure-phase MoO3
Step 2: MoO3Preparation of graphene precursor
0.12g of graphene was dispersed in deionized water, and 1.6g of pure phase MoO was added3Preparing MoO by stirring and evaporating3A graphene precursor.
And step 3: n-doped graphene flexible substrate fixed porous MoS2Preparation of nanomaterials
1) Adding MoO3Graphene precursor and thiourea according to 0.5: 4.0, placing the ground sample in a porcelain boat, and reacting in a tube type atmosphere furnace under the condition of argon atmosphere;
2) ar gas is introduced at the beginning of the reaction at a flow rate of 100sccm to ensure that the reaction is carried out under inert conditions. At 8 ℃ for min-1The temperature rising rate is increased from room temperature to 100 ℃, the gas flow rate of argon is controlled to be 40sccm, the temperature is continuously increased to 300 ℃, and the reaction is carried out for 1.5 hours in a heat preservation way;
3) then at 8 ℃ for min-1The temperature is continuously increased to 700 ℃ at the temperature increasing rate, the temperature is maintained for 1.5h again, and the flow rate of argon gas is adjusted to be 180sccm after the reaction is finished so as to discharge the excessive N and S in the reaction environment;
4) washing the reaction product with deionized water for 5 times, and freeze-drying for 11h to obtain the N-doped graphene flexible substrate fixed porous MoS with the three-dimensional structure2And (3) nano materials.
Example 5
N-doped graphene flexible substrate fixed porous MoS with three-dimensional structure2The preparation method of the nano material comprises the following steps:
step 1: pure phase MoO3Preparation of
1) Taking ammonium molybdate, and fully grinding in a mortar. Placing the ground sample in a porcelain boat, and placing in a tube furnace at 10 deg.C for min-1The temperature rise rate is increased to 600 ℃, and after heat preservation is carried out for 3.0 hours, the high temperature cracking is carried out under the air atmosphere condition to obtain MoO3
2) Cooling to room temperature after the reaction is finished, washing the product with deionized water for 6 times, and freeze-drying for 12 hours to obtain pure-phase MoO3
Step 2: MoO3Preparation of graphene precursor
0.14g of graphene was dispersed in deionized water, and 1.8g of pure phase MoO was added3Preparing MoO by stirring and evaporating3A graphene precursor.
And step 3: n-doped graphene flexible substrate fixed porous MoS2Preparation of nanomaterials
1) Adding MoO3Graphene precursor and thiourea according to 0.5: 5.0, placing the ground sample in a porcelain boat, and reacting in a tubular atmosphere furnace under the condition of argon atmosphere;
2) ar gas is introduced at the beginning of the reaction at a flow rate of 100sccm to ensure that the reaction is carried out under inert conditions. At 10 ℃ for min-1The temperature rising rate is increased from room temperature to 100 ℃, the gas flow rate of argon is controlled to be 50sccm, the temperature is continuously raised to 350 ℃, and the reaction is carried out for 2.0 hours under the condition of heat preservation;
3) then at 10 deg.C for min-1The temperature is continuously increased to 800 ℃ at the temperature increasing rate, the temperature is maintained for 2.0 hours again, the flow rate of argon gas is adjusted to 200sccm after the reaction is finished, and the excessive N and S in the reaction environment are discharged;
4) washing the reaction product with deionized water for 6 times, and then freeze-drying for 12 hours to prepare the N-doped graphene flexible substrate fixed porous MoS with the three-dimensional structure2And (3) nano materials.
Referring to FIG. 1, it can be seen from FIG. 1 that MoS can be prepared by the in situ synthesis method2Nanomaterial (red curve) in XRD diffraction patternEach diffraction peak can be associated with MoS2The diffraction peaks of the standard card corresponded, indicating better crystallinity and higher purity.
Referring to FIG. 2, it can be seen that the prepared product exhibits a three-dimensional structure, MoS2Has a size of nanometer order, MoS2A porous structure is represented and the size is uniform.
In addition, the prepared N-doped graphene flexible substrate with the three-dimensional structure is used for fixing porous MoS2The nano material is applied to a lithium/sodium ion battery cathode material, and the performance of the nano material is tested as follows:
referring to fig. 3, a porous MoS is fixed for an N-doped graphene flexible substrate having a three-dimensional structure2The electrical properties of the nano material serving as the lithium ion battery cathode material are shown, and it can be seen that the porous MoS is fixed on the N-doped graphene flexible substrate with the three-dimensional structure2The nano material has excellent cycle stability and specific discharge capacity, and is used in a lithium ion battery at 100mA g-1The capacity can still be kept at 750mAh g after 70 cycles-1The above. This shows that the porous MoS is fixed on the N-doped graphene flexible substrate with the three-dimensional structure2The lithium ion battery cathode has good discharge specific capacity and cycling stability.
Fixing porous MoS on N-doped graphene flexible substrate with three-dimensional structure2The results of the nanomaterial used in the sodium ion battery are shown in FIG. 4, from which it can be seen that the battery voltage is 5000mA g-1The capacity can still be maintained at 162mAh g after 500 cycles-1. This shows that the porous MoS is fixed on the N-doped graphene flexible substrate with the three-dimensional structure2The lithium ion battery anode is applied to a sodium ion battery cathode and has good discharge specific capacity and cycling stability.
In summary, the porous MoS is fixed by in-situ synthesis of the N-doped graphene flexible substrate by the solid phase method2. MoS of N-doped graphene and porous structure realized by the method2The two reactions occur simultaneously in situ growth on the surface of the N-doped graphene. The method has the advantages of simple and easily-controlled preparation process and reactionShort period, low energy consumption, high repeatability, high yield and the like. Meanwhile, the method also solves the problems of preparation of N-doped graphene and MoS in the prior art2The two reactions are separately carried out in the in-situ growth on the surface of the graphene. N-doped graphene flexible substrate fixed porous MoS with three-dimensional structure prepared by using method2The nano material has the characteristics of high discharge specific capacity, good cycle stability and the like.

Claims (7)

1. N-doped graphene flexible substrate fixed porous MoS with three-dimensional structure2The preparation method of the nano material is characterized by comprising the following steps:
1) taking ammonium molybdate as a raw material, grinding, heating, cooling, washing and drying to obtain pure-phase MoO3
2) Dispersing graphene in deionized water, and adding pure-phase MoO3Stirring and evaporating to dryness to obtain MoO3A graphene precursor; graphene and pure phase MoO3The mass ratio is (0.06-0.14): (1.0-1.8);
3) adding MoO3Graphene precursor and thiourea according to 0.5: (1.0-5.0), uniformly grinding, heating to 150-350 ℃ from room temperature in an inert atmosphere, carrying out heat preservation reaction for 0.5-2 h, then continuously heating to 600-800 ℃, carrying out heat preservation reaction for 0.5-2 h, cooling to room temperature, cleaning and drying a reaction product, and thus obtaining the N-doped graphene flexible substrate fixed porous MoS with the three-dimensional structure2A nanomaterial;
wherein, the inert atmosphere selects argon, controls the flow rate of the introduced argon in the reaction process, and the specific operation is as follows:
when the reaction starts, the volume flow of the gas introduced with argon is 100 sccm;
when the temperature is increased from room temperature to 100 ℃, controlling the gas volume flow of argon to be 0-50 sccm;
and after the heat preservation reaction is finished, adjusting the gas volume flow of the argon gas to be 100-200 sccm.
2. Having three dimensions according to claim 1N-doped graphene flexible substrate fixed porous MoS with structure2The preparation method of the nano material is characterized in that in the step 1), the heating treatment is to grind the uniformly ground ammonium molybdate for 5-10 ℃ min in the air atmosphere-1The temperature rising rate is increased from room temperature to 400-600 ℃, and the temperature is kept for 1-3 h.
3. The N-doped graphene flexible substrate fixed porous MoS with a three-dimensional structure according to claim 12The preparation method of the nano material is characterized in that in the step 1), the reaction product is cooled to room temperature, then is washed for 3-6 times by deionized water, and then is freeze-dried for 8-12 hours.
4. The N-doped graphene flexible substrate fixed porous MoS with a three-dimensional structure according to claim 12The preparation method of the nano material is characterized in that in the step 3), the heating rate in the heating process is 5-10 ℃ for min-1
5. The N-doped graphene flexible substrate fixed porous MoS with a three-dimensional structure according to claim 12The preparation method of the nano material is characterized in that in the step 3), the reaction product is washed for 3-6 times by using deionized water, and then is frozen and dried for 8-12 hours.
6. N-doped graphene flexible substrate fixed porous MoS with three-dimensional structure prepared by adopting preparation method of any one of claims 1-52And (3) nano materials.
7. The N-doped graphene flexible substrate with a three-dimensional structure of claim 6 for immobilizing porous MoS2The application of the nano material as a negative electrode material of a lithium/sodium ion battery.
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