CN107681124A - A kind of three-dimensional grapheme/MoS2The preparation method of composite - Google Patents

A kind of three-dimensional grapheme/MoS2The preparation method of composite Download PDF

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CN107681124A
CN107681124A CN201610622616.1A CN201610622616A CN107681124A CN 107681124 A CN107681124 A CN 107681124A CN 201610622616 A CN201610622616 A CN 201610622616A CN 107681124 A CN107681124 A CN 107681124A
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dimensional grapheme
composite
preparation
mos
dimensional
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杨与畅
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Fujian Xinfeng Two Mstar Technology Ltd
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Fujian Xinfeng Two Mstar Technology Ltd
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Priority to PCT/CN2017/095365 priority patent/WO2018024183A1/en
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • 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
    • H01M4/364—Composites as mixtures
    • 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
    • H01M4/58—Selection 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
    • H01M4/581—Chalcogenides or intercalation compounds thereof
    • H01M4/5815—Sulfides
    • 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
    • H01M4/58—Selection 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
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention discloses a kind of three-dimensional grapheme/MoS2The preparation method of composite, methods described include step：1) three-dimensional grapheme is prepared；2) reaction solution is prepared：Molybdate and deionization solution are configured, then fully forms uniform reaction solution after dissolving toward thioacetamide is added in solution again；3) hydro-thermal reaction and annealing：Three-dimensional grapheme is impregnated into reaction solution, reaction solution is subjected to hydro-thermal reaction；After reaction terminates, take out three-dimensional grapheme and rinse repeatedly；Three-dimensional grapheme is put into the environment full of inert gas shielding after rinsing, annealed, obtains uniform load MoS on three-dimensional grapheme surface2Composite.The three-dimensional grapheme used in the present invention, its specific surface area are higher by hundreds of thousands times than two-dimensional graphene, with the composite of its preparation, MoS2Three-dimensional grapheme surface is uniformly distributed in, good dispersion, both avoids MoS2Nano-particle is assembled in cyclic process, also effectively prevents the accumulation again of graphene, improves cyclical stability.

Description

A kind of three-dimensional grapheme/MoS2The preparation method of composite
Technical field
The present invention relates to a kind of preparation of lithium ion battery negative material, more particularly to a kind of three-dimensional grapheme/MoS2It is multiple The preparation method of condensation material.
Background technology
Lithium ion battery has that voltage is high, memory-less effect higher than energy, has extended cycle life, the features such as non-environmental-pollution, It is current most popular chargeable portable power source, up to now, it has been widely used in mobile phone, notebook computer, number Mechanical, electrical sub- translater of code-phase etc..Lithium ion battery electrode material is the core of current Study on Li-ion batteries, wherein for The research of negative material focuses primarily upon the following aspects：Relatively low electrode potential, higher specific capacity and good circulation Stability, formed with electrolyte stable SEI films, with the good compatibility of battery part such as electrolyte and adhesive, Relatively low production cost and the environment friendly of safety non-pollution.The negative material of commercial Li-ion batteries is mostly graphite material Material.Graphite has the layer structure of crystallization, is easy to the insertion and deintercalation of lithium ion wherein, forms interlayer compound L iC6, is A kind of negative material of stable performance.But graphite cathode theoretical specific capacity is only 372mAh/g, entering for lithium ion battery is limited One step develops.
MoS2It is hexagonal crystal system inorganic layered compounds, it forms stratiform by S-Mo-S element stacks, in layer between atom By stable covalent key connection, and then combined between layers by weaker Van der Waals force.As lithium ion battery negative material, MoS2Theoretical capacity reach 800mAh/g, its special layer structure be beneficial to lithium ion insertion and abjection.However, due to it Low electrons/ions electrical conductivity itself and serious volumetric expansion during removal lithium embedded make it that its cyclical stability is extremely low.This Outside, during cell reaction, MoS2With Li+React and generate the Li of indissoluble2S, Li2S has been catalyzed the decomposition of electrolyte again So as to the reason for polymeric layer for foring thick result in irreversible capacitance loss, and this is also its cyclical stability difference.
Therefore, it is necessary to research and develop a kind of composite for the advantages that cyclical stability is high, performance is good.
The content of the invention
Object of the present invention is to provide a kind of three-dimensional grapheme/MoS2The preparation method of composite, it can be solved Certainly graphene easily reunites, is difficult scattered, being difficult the problem of obtaining high-specific surface area, and solves MoS2Particle holds in cyclic process Easily aggregation and its volumetric expansion during lithium deintercalation the problems such as.
To achieve the above object, the invention provides following technical scheme：
A kind of three-dimensional grapheme/MoS2The preparation method of composite, the described method comprises the following steps：
1) three-dimensional grapheme is prepared；
2) reaction solution is prepared：
Uniform reaction solution will be formed after point dissolving of molybdate, deionization and thioacetamide；
3) hydro-thermal reaction and annealing：
Three-dimensional grapheme is impregnated into reaction solution, reaction solution is subjected to hydro-thermal reaction；After reaction terminates, three are taken out Dimension graphene rinses repeatedly；Three-dimensional grapheme is put into the environment full of inert gas shielding after rinsing, annealed, is obtained Uniform load MoS on three-dimensional grapheme surface2Composite.
Preferably, the concentration of the molybdate and deionized water solution is 1-5mg/ml, the thioacetamide and molybdic acid The mass ratio of salt is=1：1-1：5.
Preferably, it is described by reaction solution carry out hydro-thermal reaction be specifically by reaction solution at a temperature of 200-250 DEG C water Thermal response 20-30h.
Preferably, the annealing is the 1-5h that annealed at a temperature of 320-400 DEG C.
Preferably, the molybdate is sodium molybdate or ammonium molybdate.
Preferably, the inert gas is argon gas, nitrogen, or argon gas and nitrogen mixed gas.
Preferably, the three-dimensional grapheme for preparing comprises the following steps that：
1) substrate is provided；
2) under the conditions of protection gas and hydrogen, 800~1300 DEG C of temperature, carbon is passed through again after removing substrate surface oxide skin(coating) Source gas, 2-10 close carbon-source gas after minute, and obtained sample is rapidly cooled into room temperature, closes protection gas and hydrogen；
3) PMMA in the coating of the surface of obtained sample, then puts it into metal etch liquid and removes metallic substrates, Rinsed again with deionized water；
4) above-mentioned sample is put into acetone or toluene, removes PMMA, then soaked successively clearly with ethanol, deionized water Wash；
5) finally the sample cleaned up is freeze-dried, obtains the three-dimensional grapheme of structural integrity.
Preferably, described carbon-source gas be methane, methanol, ethanol or ethane in one or more, described protection Gas is argon gas or neon.
Preferably, metal etch liquid is FeCl in the step 3)3Solution, ammonium persulfate or HCl and H2O2Mixing it is molten Liquid.
Preferably, protection air-flow speed is 300-600s.c.c.m. in the step 1), and described cooldown rate is 200- 300℃/min。
Beneficial effects of the present invention：(1) three-dimensional grapheme used in the present invention, its specific surface area are higher than two-dimensional graphene Go out hundreds of thousands times, with the composite of its preparation, MoS2Three-dimensional grapheme surface is uniformly distributed in, good dispersion, is so both kept away MoS is exempted from2Nano-particle is assembled in cyclic process, also effectively prevent the accumulation again of graphene, so as to improve its circulation Stability；(2) composite produced by the present invention first charge-discharge circulation in, coulombic efficiency reaches 85% or so, aftereffect Rate is stable 97% or so, does not occur being decreased obviously phenomenon by more than 200 cyclic discharge capacities, shows excellent circulation Stability；(3) even if the composite has discharge and recharge under the conditions of high current, electrode remains to keep stable circulation behavior, performance Go out excellent high rate capability；(4) the lithium ion battery charging interval that prepared by the composite is short, discharge time length, identical The discharge and recharge time is reproducible under current density.
Brief description of the drawings
Fig. 1 is the schematic flow sheet of preparation method of the present invention；
Fig. 2 is three-dimensional grapheme/MoS prepared by the present invention2First three the circle circulation volt of composite in the case where sweeping fast 0.5mV/s Pacify curve map；
Fig. 3 is three-dimensional grapheme/MoS prepared by the present invention2The charging and discharging curve figure of first three circle of composite；
Fig. 4 is three-dimensional grapheme/MoS prepared by the present invention2Composite and contrast material three-dimensional grapheme, MoS2 materials The cycle performance comparison diagram of three and the coulombic efficiency curve map of the composite；
Fig. 5 is three-dimensional grapheme/MoS prepared by the present invention2The charge and discharge cycles of composite different multiplying current density Curve map；
Fig. 6 is three-dimensional grapheme/MoS prepared by the present invention2Cyclic curve figure of the composite in current density 1A/g；
Fig. 7 is three-dimensional grapheme/MoS prepared by the present invention2Composite applies the discharge and recharge on lithium ion battery to follow The discharge and recharge time comparison diagram of ring process；
Fig. 8 is the stereoscan photograph that graphene is loaded on nickel screen prepared by the present invention.
Embodiment
In order to make the purpose , technical scheme and advantage of the present invention be clearer, it is right below in conjunction with drawings and examples The present invention is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, and It is not used in the restriction present invention.
Three-dimensional grapheme material prepared by the present invention, the graphene of two dimension is structurally different from, it has three-dimensional hollow Porous network structure, net wall are graphene, are the graphite of layer structure and porous graphitic carbon foam, have extremely-low density table The advantages that area, high heat conduction, high temperature resistant, corrosion-resistant, ductility, good pliability, single-layer and transparent and quality is higher are prepared Composite both avoids MoS2Nano-particle is assembled in cyclic process, also effectively prevent the accumulation again of graphene, so as to Improve its cyclical stability.
As shown in figure 1, preparation method preparation of the present invention is as follows：
S101：Prepare three-dimensional grapheme；
S102：Prepare reaction solution；
S103：Three-dimensional grapheme is impregnated into reaction solution and carries out hydro-thermal reaction and annealing.
The specific present invention can use implementation below：
Embodiment 1
1) three-dimensional grapheme is prepared：
Nickel screen (aperture 0.01mm) is placed in horizontal pipe furnace, is passed through argon gas (flow velocity 500s.c.c.m) and hydrogen (200s.c.c.m.), under the conditions of 1000 DEG C, heat 10 minutes, after removing oxide layer, then be passed through methane gas (5s.c.c.m.), after 5 minutes, methane gas is closed, keep the flow velocity of argon gas and hydrogen constant, by sample with 200 DEG C/min's Speed is quickly cooled to room temperature, closes argon gas and hydrogen, and individual layer three-dimensional grapheme is made, and is applied on nickel screen/graphene-structured surface PMMA on cloth；Then HCl and H are put it into2O2Volume ratio is 1：Metallic nickel is removed in 3 solution, one is rinsed with deionized water Under；Then graphene/PMMA samples are put into acetone, PMMA is removed；Again with ethanol, deionized water successively soaking and washing 10min；Finally the three-dimensional grapheme cleaned up is freeze-dried, obtains the three-dimensional grapheme of structural integrity；
2) reaction solution is prepared
By 30mg sodium molybdates (Na2MoO4·2H2) and 60mg thioacetamides (C O2H5NS) it is dissolved in 30ml deionized water In, form uniform reaction solution；
3) three-dimensional grapheme is impregnated into reaction solution and carries out hydro-thermal reaction and annealing
The three-dimensional grapheme that step 1) is obtained is impregnated into the reaction solution that step 2) obtains, and solution is moved into polytetrafluoro In the stainless steel cauldron of ethene inner bag, hydro-thermal reaction 28h is carried out at 200 DEG C；It is anti-with distilled water and ethanol after reaction terminates Xian is floated again 3 times, sample is then put into 360 DEG C of annealing 3h in the environment full of argon gas；Finally give three-dimensional grapheme/MoS2It is multiple Condensation material.
Embodiment 2
1) three-dimensional grapheme is prepared
Nickel screen (aperture 0.01mm) is placed in horizontal pipe furnace, is passed through argon gas (flow velocity 600s.c.c.m) and hydrogen (250s.c.c.m.), under the conditions of 900 DEG C, heat 20 minutes, after removing oxide layer, then be passed through methane gas (10s.c.c.m.), after 5 minutes, methane gas is closed, keep the flow velocity of argon gas and hydrogen constant, by sample with 250 DEG C/min Speed be quickly cooled to room temperature, close argon gas and hydrogen, individual layer three-dimensional grapheme be made, on nickel screen/graphene-structured surface PMMA in coating；Then HCl and H are put it into2O2Volume ratio is 1：Metallic nickel is removed in 3 solution, rinsed with deionized water Once；Then graphene/PMMA samples are put into acetone, PMMA is removed；Again with ethanol, deionized water successively soaking and washing 10min；Finally the three-dimensional grapheme cleaned up is freeze-dried, obtains the three-dimensional grapheme of structural integrity；
2) reaction solution is prepared
By 30mg sodium molybdates (Na2MoO4·2H2) and 90mg thioacetamides (C O2H5NS) it is dissolved in 30ml deionized water In, form uniform reaction solution；
3) three-dimensional grapheme is impregnated into reaction solution and carries out hydro-thermal reaction and annealing
The three-dimensional grapheme that step 1) is obtained is impregnated into the reaction solution that step 2) obtains, and solution is moved into polytetrafluoro In the stainless steel cauldron of ethene inner bag, hydro-thermal reaction 26h is carried out at 200 DEG C；It is anti-with distilled water and ethanol after reaction terminates Xian is floated again 5 times, sample is then put into 350 DEG C of annealing 4h in the environment full of argon gas；Finally give three-dimensional grapheme/MoS2It is multiple Condensation material.
Embodiment 3
1) three-dimensional grapheme is prepared
Nickel screen (aperture 0.1mm) is placed in horizontal pipe furnace, is passed through neon (flow velocity 300s.c.c.m) and hydrogen (100s.c.c.m.), under the conditions of 800 DEG C, heat 10 minutes, after removing oxide layer, then be passed through ethane gas (1s.c.c.m.), after 10 minutes, ethane gas are closed, keep the flow velocity of neon and hydrogen constant, by sample with 200 DEG C/min Speed be quickly cooled to room temperature, close neon and hydrogen, individual layer three-dimensional grapheme be made, on nickel screen/graphene-structured surface PMMA in coating；Then HCl and H are put it into2O2Volume ratio is 1：Metallic nickel is removed in 3 solution, rinsed with deionized water Once；Then graphene/PMMA samples are put into acetone, PMMA is removed；Again with ethanol, deionized water successively soaking and washing 10min；Finally the three-dimensional grapheme cleaned up is freeze-dried, obtains the three-dimensional grapheme of structural integrity；
2) reaction solution is prepared
By 40mg sodium molybdates (Na2MoO4·2H2) and 60mg thioacetamides (C O2H5NS) it is dissolved in 20ml deionized water In, form uniform reaction solution；
3) three-dimensional grapheme is impregnated into reaction solution and carries out hydro-thermal reaction and annealing
The three-dimensional grapheme that step 1) is obtained is impregnated into the reaction solution that step 2) obtains, and solution is moved into polytetrafluoro In the stainless steel cauldron of ethene inner bag, hydro-thermal reaction 23 is carried out at 230 DEG C；It is anti-with distilled water and ethanol after reaction terminates Xian is floated again 4 times, sample is then put into 380 DEG C of annealing 1h in the environment full of argon gas；Finally give three-dimensional grapheme/MoS2It is multiple Condensation material.
Comparative example 1
It is the material of comparative example 1 that three-dimensional grapheme, which is prepared, in step 1) in embodiment 1.
Comparative example 2
30mg sodium molybdates and 60mg thioacetamides are dissolved in 20ml deionized waters, what is be uniformly mixed is transparent molten Liquid, then solution is moved into the reactor of polytetrafluoroethylliner liner, hydro-thermal reaction 28h is carried out at 200 DEG C；Reaction terminates Afterwards, sample distilled water and ethanol rinse 3 times, are dried in vacuo 8h at 60 DEG C, obtained molybdenum disulfide is the material of comparative example 2.
Circulate contrast test：
As shown in Fig. 2 cyclic voltammogram, to the three-dimensional grapheme/MoS of the invention prepared2The storage lithium electrification of composite Learn performance and carry out cyclic voltammetric and first three circle charge-discharge test.It can be seen that occur during first time cathodic scan 0.45V and Two reduction peaks of 0.95V, there is a less oxidation peak in 1.7V during subsequent anodic scan, shows in 2.35V The oxidation peak of work；In the cathodic scan enclosed, there are two reduction peaks in 1V and 1.82V in second and the 3rd.As Fig. 3 can be seen Go out, three-dimensional grapheme/MoS prepared by the present invention2The first discharge specific capacity of composite is 630mAh/g, and charge specific capacity is 539mAh/g, coulombic efficiency reach 85.56%；
As shown in figure 4, change lithium ion battery negative material, the material that comparative example 1,2 is obtained and the embodiment of the present invention 1 Obtained material contrasts three's charge and discharge cyclical stability, as figure shows, the three of comparative example 1 as lithium ion battery negative material Graphene good cycling stability is tieed up, but specific capacity is low (only 200mAh/g or so)；The MoS of comparative example 22Discharge first specific capacitance It is higher, but cyclical stability is poor, and by 100 circulations, capacity drops to 200mAh/g or so from 1000mAh/g or so；The present invention The three-dimensional grapheme of embodiment 1/composite first charge-discharge efficiency reaches 85%, and its stable circulation performance is excellent, passes through 100 circulations, capability retention reach 97%.
As shown in figure 5, three-dimensional grapheme/MoS prepared by the present invention2Composite has good high rate performance, not With under current density by 60 multi-turns circulation after, remained under 1000mA/g current density keep mAh/g more than 400 capacity and Cyclic process is unattenuated.When current density returns to 100mA/g from 1000mA/g, three-dimensional grapheme/MoS2Reversible capacity Capability value during initial 100mA/g circulations can be almost promptly restored to, and capacity is not decayed in later loop test, dimension Hold in 800mAh/g or so.
As shown in fig. 6, three-dimensional grapheme/MoS prepared by the present invention2Composite passes through 200 in current density 1A/g Multiple charge and discharge cycles, specific capacity do not decay, and show excellent cyclical stability.
As shown in fig. 7, three-dimensional grapheme/the MoS prepared2Composite applies the charge and discharge cycles on lithium ion battery The discharge and recharge time of process, the charging interval is all very short under different current densities, and from more than ten to dozens of minutes, and discharge time exists Specific capacity relatively low discharge time is shorter under high magnification current density, under low range current density specific capacity higher discharge time compared with Length reaches more than 200 minutes, while constantly converts current density in cyclic process, when charging, discharging under identical current density Between the uniformity all done well, illustrate three-dimensional grapheme/MoS2The stable circulation performance of composite is good.
As can be seen here, three-dimensional grapheme/MoS that prepared by the present invention2Composite has higher reversible capacity, preferably Cyclical stability and high rate performance.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all essences in the present invention All any modification, equivalent and improvement made within refreshing and principle etc., should be included in the scope of the protection.

Claims (10)

  1. A kind of 1. three-dimensional grapheme/MoS2The preparation method of composite, it is characterised in that the described method comprises the following steps：
    1) three-dimensional grapheme is prepared；
    2) reaction solution is prepared：
    Uniform reaction solution will be formed after molybdate, deionized water and thioacetyl amine solvent；
    3) hydro-thermal reaction and annealing：
    Three-dimensional grapheme is impregnated into reaction solution, reaction solution is subjected to hydro-thermal reaction；After reaction terminates, three-dimensional stone is taken out Black alkene rinses repeatedly；Three-dimensional grapheme is put into the environment full of inert gas shielding after rinsing, annealed, obtains three-dimensional Uniform load MoS on graphenic surface2Composite.
  2. 2. three-dimensional grapheme/MoS according to claim 12The preparation method of composite, it is characterised in that the molybdic acid The concentration of salt and deionized water solution is 1-5mg/ml, and the mass ratio of the thioacetamide and molybdate is 1：1-1：5.
  3. 3. three-dimensional grapheme/MoS according to claim 12The preparation method of composite, it is characterised in that：It is described to incite somebody to action instead Answer solution carry out hydro-thermal reaction be specifically by reaction solution at a temperature of 200-250 DEG C hydro-thermal reaction 20-30h.
  4. 4. three-dimensional grapheme/MoS according to claim 12The preparation method of composite, it is characterised in that：The annealing It is the 1-5h that annealed at a temperature of 320-400 DEG C.
  5. 5. three-dimensional grapheme/MoS according to claim 12The preparation method of composite, it is characterised in that：The molybdic acid Salt is sodium molybdate or ammonium molybdate.
  6. 6. three-dimensional grapheme/MoS according to claim 12The preparation method of composite, it is characterised in that：The inertia Gas is argon gas, nitrogen, or argon gas and nitrogen mixed gas.
  7. 7. three-dimensional grapheme/MoS according to claim 12The preparation method of composite, it is characterised in that the preparation Three-dimensional grapheme comprises the following steps that：
    1) substrate is provided；
    2) under the conditions of protection gas and hydrogen, 800~1300 DEG C of temperature, carbon source gas is passed through again after removing substrate surface oxide skin(coating) Body, 2-10 close carbon-source gas after minute, and obtained sample is rapidly cooled into room temperature, closes protection gas and hydrogen；
    3) PMMA in the coating of the surface of obtained sample, then puts it into metal etch liquid and removes metallic substrates, then use Deionized water rinses；
    4) above-mentioned sample is put into acetone or toluene, PMMA is removed, then with ethanol, deionized water successively soaking and washing；
    5) finally the sample cleaned up is freeze-dried, obtains the three-dimensional grapheme of structural integrity.
  8. 8. three-dimensional grapheme/MoS according to claim 72The preparation method of composite, it is characterised in that described carbon Source gas is the one or more in methane, methanol, ethanol or ethane, and described protection gas is argon gas or neon.
  9. 9. three-dimensional grapheme/MoS according to claim 72The preparation method of composite, it is characterised in that the step 3) metal etch liquid is FeCl in3Solution, ammonium persulfate or HCl and H2O2Mixed solution.
  10. 10. three-dimensional grapheme/MoS according to claim 72The preparation method of composite, it is characterised in that the step It is rapid 1) in protection air-flow speed be 300-600s.c.c.m., described cooldown rate is 200-300 DEG C/min.
CN201610622616.1A 2016-08-01 2016-08-01 A kind of three-dimensional grapheme/MoS2The preparation method of composite Pending CN107681124A (en)

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CN110556530A (en) * 2019-10-23 2019-12-10 扬州大学 preparation method of molybdenum sulfide/three-dimensional macroporous graphene and lithium ion battery cathode material
CN113410459A (en) * 2021-06-11 2021-09-17 天津大学 Embedded MoSxThree-dimensional ordered macroporous graphene carbon material of nanosheet, preparation and application
CN113622055A (en) * 2021-08-17 2021-11-09 四川轻化工大学 Sodium-ion battery negative electrode material and preparation method thereof

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CN108493409B (en) * 2018-03-12 2021-02-26 安徽大学 Preparation method of nitrogen-doped carbon-coated flower-shaped nano molybdenum disulfide
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