CN108529578A - A kind of preparation method of high stable nanometer black phosphorus/three-dimensional graphene composite material - Google Patents
A kind of preparation method of high stable nanometer black phosphorus/three-dimensional graphene composite material Download PDFInfo
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- CN108529578A CN108529578A CN201810384545.5A CN201810384545A CN108529578A CN 108529578 A CN108529578 A CN 108529578A CN 201810384545 A CN201810384545 A CN 201810384545A CN 108529578 A CN108529578 A CN 108529578A
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- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims abstract description 125
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 99
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 93
- 239000002131 composite material Substances 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000006185 dispersion Substances 0.000 claims abstract description 93
- 239000007788 liquid Substances 0.000 claims abstract description 75
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 44
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 22
- 239000002114 nanocomposite Substances 0.000 claims abstract description 21
- 239000011261 inert gas Substances 0.000 claims abstract description 20
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 24
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 17
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 16
- -1 black phosphorus alkene Chemical class 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 13
- 239000002096 quantum dot Substances 0.000 claims description 13
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 10
- 235000019441 ethanol Nutrition 0.000 claims description 8
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 6
- AWSCOTJIASXILV-UHFFFAOYSA-O 3-butyl-2,4,5-trimethyl-1H-imidazol-3-ium Chemical compound CCCC[n+]1c(C)[nH]c(C)c1C AWSCOTJIASXILV-UHFFFAOYSA-O 0.000 claims description 5
- 229910052786 argon Inorganic materials 0.000 claims description 5
- 239000007789 gas Substances 0.000 claims description 5
- 238000000527 sonication Methods 0.000 claims description 5
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 239000001307 helium Substances 0.000 claims description 2
- 229910052734 helium Inorganic materials 0.000 claims description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 2
- 239000002070 nanowire Substances 0.000 claims description 2
- 150000002576 ketones Chemical class 0.000 claims 1
- 230000009471 action Effects 0.000 abstract description 6
- 238000002604 ultrasonography Methods 0.000 abstract description 6
- 230000003197 catalytic effect Effects 0.000 abstract description 2
- 238000011946 reduction process Methods 0.000 abstract description 2
- 238000004458 analytical method Methods 0.000 description 11
- 238000012360 testing method Methods 0.000 description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 8
- 239000001301 oxygen Substances 0.000 description 8
- 229910052760 oxygen Inorganic materials 0.000 description 8
- 238000006555 catalytic reaction Methods 0.000 description 7
- 150000001336 alkenes Chemical class 0.000 description 6
- 230000005611 electricity Effects 0.000 description 6
- 229910002804 graphite Inorganic materials 0.000 description 6
- 239000010439 graphite Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 238000012512 characterization method Methods 0.000 description 5
- 238000011056 performance test Methods 0.000 description 5
- 230000008859 change Effects 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 239000002023 wood Substances 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 241000209094 Oryza Species 0.000 description 2
- 235000007164 Oryza sativa Nutrition 0.000 description 2
- 239000010405 anode material Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 235000009566 rice Nutrition 0.000 description 2
- 239000004575 stone Substances 0.000 description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 2
- OXHNLMTVIGZXSG-UHFFFAOYSA-N 1-Methylpyrrole Chemical class CN1C=CC=C1 OXHNLMTVIGZXSG-UHFFFAOYSA-N 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000008246 gaseous mixture Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/02—Preparation of phosphorus
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/184—Preparation
Abstract
The present invention relates to a kind of preparation methods of high stable nanometer black phosphorus/three-dimensional graphene composite material, belong to technical field of composite materials.The present invention temperature be 5 ~ 30 DEG C, atmosphere of inert gases under the conditions of, nanometer black phosphorus dispersion liquid is mixed with graphene oxide dispersion, it is sonicated to obtain dispersion liquid A；Under the conditions of atmosphere of inert gases, dispersion liquid A is handled through liquid nitrogen and is freeze-dried up to nanometer black phosphorus/three-dimensional grapheme nanocomposite.For the present invention under the catalytic action of nanometer black phosphorus, graphene oxide can be reduced to graphene under ultrasound condition, and black phosphorus alkene forms strong bonding action with graphene in reduction process.
Description
Technical field
The present invention relates to a kind of preparation methods of high stable nanometer black phosphorus/three-dimensional graphene composite material, belong to composite wood
Expect technical field.
Background technology
Black phosphorus is a kind of two-dimensional layer material emerging in recent years, is similar to graphite.Due to the unique crystal knot of black phosphorus
Structure and band structure make it have good application prospect in fields such as energy storage, catalysis.Block black phosphorus is deposited compared to nanometer black phosphorus
The defects of ion, electronics conduct slowly, and reactivity area is small, therefore, need to block black phosphorus nanometer be subjected in practical application
Change, that is, prepares nanometer black phosphorus（Black phosphorus alkene or black phosphorus quantum dot）.Although nanometer black phosphorus has the distinctive advantage of nano material,
There is also the obstacles of essence in practical applications：Phosphorus based material electric conductivity is bad, it is oxidizable to meet ambient enviroment.Therefore, need by
Nanometer black phosphorus and the grapheme material of high conductivity carry out compound.On the one hand improve that single nanometer black phosphorus electric conductivity is bad to ask
On the other hand topic improves the stability of nanometer black phosphorus.The preparation method of nanometer black phosphorus/graphene composite material mainly has at present：
First, black phosphorus alkene and graphene are carried out physical mixed.Black phosphorus alkene only passes through with graphene in the composite material that this method obtains
Van der Waals force interacts, and cannot fundamentally solve the oxidizable defect of nanometer black phosphorus；Second is that by black phosphorus alkene and graphite oxide
Alkene is mixed, then the reduction of graphene oxide is realized by plasma sintering process, obtains black phosphorus alkene/graphene composite wood
Material.Although the obtained composite material black phosphorus alkene of this method and having strong bonding action between graphene oxide, plasma is burnt
Knot process is complex, high energy consumption, is unfavorable for industrialized production.And the nanometer black phosphorus/graphene composite material reported at present
It is two-dimensional structure.For the composite material of three-dimensional structure, the electrolyte of Two-dimensional Composites, ionic conduction performance compared with
Difference, active area smaller.
Invention content
The problem of existing for the above-mentioned prior art and deficiency, the present invention provide a kind of high stable nanometer black phosphorus/three-dimensional stone
The preparation method of black alkene composite material, under the catalytic action of nanometer black phosphorus, graphene oxide is the present invention under ultrasound condition
It can be reduced to graphene, black phosphorus alkene forms strong bonding action with graphene in reduction process；The method of the present invention is easy to operate,
Efficiently, reaction condition is mild.
A kind of preparation method of high stable nanometer black phosphorus/three-dimensional graphene composite material, is as follows：
（1）Temperature be 5 ~ 30 DEG C, atmosphere of inert gases under the conditions of, nanometer black phosphorus dispersion liquid is mixed with graphene oxide dispersion
It closes, it is sonicated to obtain dispersion liquid A；
（2）Under the conditions of atmosphere of inert gases, by step（1）Gained dispersion liquid A is handled and is freeze-dried through liquid nitrogen up to nanometer
Black phosphorus/three-dimensional grapheme nanocomposite；
The step（1）The mass ratio of nanometer black phosphorus and graphene oxide is 1:(1~4)；
The step（1）Nanometer black phosphorus is black phosphorus alkene, black phosphorus quantum dot or black phosphorus nano wire；The dispersion of nanometer black phosphorus dispersion liquid is molten
Agent is water, ethyl alcohol, dimethyl sulfoxide (DMSO), N-Methyl pyrrolidone, isopropanol, N,N-dimethylformamide, ethylene carbonate or 1-
Butyl-tri-methylimidazolium cdicynanmide；The dispersion solvent of graphene oxide dispersion is water, ethyl alcohol, dimethyl sulfoxide (DMSO), N- methyl pyrroles
Pyrrolidone, isopropanol, N,N-dimethylformamide, ethylene carbonate or 1- butyl-tri-methylimidazolium cdicynanmide；
The step（1）It is ultrasonically treated and ultrasonic pretreatment, ultrasound is carried out using supersonic cell washer and/or cell disruptor
The power of wave cell washer is 150W ~ 300W, and the power of cell disruptor is 500 ~ 1500W, sonication treatment time is 0.5 ~
3h；
The inert gas is the one or two of argon gas, nitrogen, helium；
The nanometer black phosphorus dispersion liquid is that nanometer black phosphorus is added in dispersion solvent, through supersonic cell washer and/or carefully
Born of the same parents' pulverizer carries out ultrasound pretreatment and obtains；
The graphene oxide aqueous dispersions are according to document " Large reversible capacity of high quality
Graphene sheets as an anode material for lithium-ion batteries " or document " Porous
SnO2@C/graphene nanocomposite with 3D carbon conductive network as a superior
Anode material for lithium-ion batteries " are prepared；
The beneficial effects of the invention are as follows：
（1）The present invention directly mixes nanometer black phosphorus with graphene oxide, under the action of nanometer black phosphorus, only with a step
The formation of the reduction and nanometer black phosphorus/graphene composite material of graphene oxide can be realized in ultrasound；
（2）The method of the present invention have the characteristics that quickly, efficiently, it is energy-saving and environmental protection, not high to equipment requirement, at low cost；
（3）For the present invention by ultrasound and liquid nitrogen frozen combination processing nanometer black phosphorus and graphene oxide, being formed has three-dimensional porous knot
Nanometer black phosphorus/three-dimensional graphene composite material of structure；This nanometer of black phosphorus/three-dimensional graphene composite material has larger active face
Long-pending, higher electric conductivity and ion transmission performance；Nanometer black phosphorus and graphene in this nanometer of black phosphorus/three-dimensional graphene composite material
Strong P-O-C keys are formd, solve the problems, such as that nano black phosphorus stabilizer is poor.
Description of the drawings
Fig. 1 is the scanning electron microscope (SEM) photograph of 1 nanometer of black phosphorus/three-dimensional graphene composite material of embodiment；
Fig. 2 is the distribution diagram of element of 1 nanometer of black phosphorus/three-dimensional graphene composite material of embodiment；
Fig. 3 is the C of 1 graphene oxide of embodiment1SSpectrogram；
Fig. 4 is the C of 1 nanometer of black phosphorus/three-dimensional graphene composite material of embodiment1SSpectrogram；
Fig. 5 is the P of 1 nanometer of black phosphorus of embodiment/three dimensional ink alkene composite material2PSpectrogram；
Fig. 6 is the linear voltammetric scan figure and illustration Tafel slope of 1 nanometer of black phosphorus/three-dimensional graphene composite material of embodiment
Figure.
Specific implementation mode
With reference to embodiment, the invention will be further described.
Embodiment 1：A kind of preparation method of high stable nanometer black phosphorus/three-dimensional graphene composite material, is as follows：
（1）It is 15 DEG C, inert gas in temperature（Argon gas）Under ambient conditions, by nanometer black phosphorus dispersion liquid（Nanometer black phosphorus dispersion liquid
For nanometer black phosphorus alkene/aqueous dispersions）With graphene oxide dispersion（Graphene oxide dispersion is graphene oxide/water-dispersed
Liquid）Mixing, it is sonicated to obtain dispersion liquid A；Wherein nanometer black phosphorus dispersion liquid（Nanometer black phosphorus alkene/aqueous dispersions）It is a concentration of
1mg/mL, graphene oxide dispersion（Graphene oxide/aqueous dispersions）A concentration of 4mg/mL, nanometer black phosphorus with oxidation stone
The mass ratio of black alkene is 1:4；It is ultrasonically treated to carry out ultrasonic pretreatment, supersonic cell cleaning using supersonic cell washer
The power of device is 200W, and the processing time of supersonic cell washer is 1h；
（2）In inert gas（Argon gas）Under ambient conditions, by step（1）Gained dispersion liquid A is handled through liquid nitrogen and is freeze-dried i.e.
Obtain nanometer black phosphorus/three-dimensional grapheme nanocomposite；
The scanning electron microscope (SEM) photograph of nanometer black phosphorus/three-dimensional grapheme nanocomposite is as shown in Figure 1, can from Fig. 1 obtained by the present embodiment
Know, black phosphorus alkene/three-dimensional graphene composite material is three-dimensional porous structure；
The distribution diagram of element of nanometer black phosphorus/three-dimensional grapheme nanocomposite is as shown in Fig. 2, can from Fig. 2 obtained by the present embodiment
Know, phosphorus, carbon are uniformly distributed；
The C of the present embodiment graphene oxide1SSpectrogram is as shown in figure 3, nanometer black phosphorus/three-dimensional grapheme nanometer obtained by the present embodiment
The C of composite material1SSpectrogram is as shown in figure 4, from Fig. 3 ~ 4 it is found that under the action of ultrasonic wave, nanometer black phosphorus, and graphene oxide is also
Original is at graphene；
The P of nanometer black phosphorus/three-dimensional grapheme nanocomposite obtained by the present embodiment2PSpectrogram as shown in figure 5, as can be seen from Figure 5,
Graphene and black phosphorus alkene have stronger bonding action, illustrate that a nanometer black phosphorus/three-dimensional grapheme is received through being ultrasonically formed P-O-C keys
Nano composite material will be with good stability；
The linear voltammetric scan figure and illustration Ta Feier of nanometer black phosphorus/three-dimensional grapheme nanocomposite obtained by the present embodiment
Slope figure is as described in Figure 6, and as can be seen from Figure 6, the take-off potential of the composite material is 0.56V, Tafel slope 105mv/dec,
Illustrate that there is nanometer black phosphorus/three-dimensional grapheme nanocomposite manufactured in the present embodiment good electro-catalysis to analyse oxygen performance.
Embodiment 2：A kind of preparation method of high stable nanometer black phosphorus/three-dimensional graphene composite material, is as follows：
（1）It is 25 DEG C, inert gas in temperature（Nitrogen）Under ambient conditions, by nanometer black phosphorus dispersion liquid（Nanometer black phosphorus dispersion liquid
For black phosphorus quantum dot/N-Methyl pyrrolidone dispersion liquid）With graphene oxide dispersion（Graphene oxide dispersion is oxidation
Graphene/N-Methyl pyrrolidone dispersion liquid）Mixing, it is sonicated to obtain dispersion liquid A；Wherein nanometer black phosphorus dispersion liquid（It is black
Phosphorus quantum dot/N-Methyl pyrrolidone dispersion liquid）A concentration of 1mg/mL, graphene oxide dispersion（Graphene oxide/N-
Methyl pyrrolidone dispersion liquid）A concentration of 4mg/mL, the mass ratio of nanometer black phosphorus and graphene oxide is 1:1；It is ultrasonically treated
To carry out ultrasonic pretreatment, cell disruptor 1500W, sonication treatment time 0.5h using cell disruptor；
（2）In inert gas（Nitrogen）Under ambient conditions, by step（1）Gained dispersion liquid A is handled through liquid nitrogen and is freeze-dried i.e.
Obtain nanometer black phosphorus/three-dimensional grapheme nanocomposite；
Electronic Speculum, XPS characterizations, and electricity are scanned to nanometer black phosphorus/three-dimensional grapheme nanocomposite made from the present embodiment
Catalysis analysis oxygen performance test, after testing analysis learn that the composite material of the present embodiment has three-dimensional net structure, and composite wood
Nanometer phosphorus forms P-O-C keys with graphene in material, and linear voltammetric scan test learns that there is the composite material good electricity to urge
Change performance.
Embodiment 3：A kind of preparation method of high stable nanometer black phosphorus/three-dimensional graphene composite material, is as follows：
（1）It is 25 DEG C, inert gas in temperature（Nitrogen）Under ambient conditions, by nanometer black phosphorus dispersion liquid（Nanometer black phosphorus dispersion liquid
For black phosphorus quantum dot/1- butyl-tri-methylimidazolium cdicynanmide dispersion liquid）With graphene oxide dispersion（Graphene oxide disperses
Liquid is graphene oxide 1- butyl-tri-methylimidazolium cdicynanmide dispersion liquid）Mixing, it is sonicated to obtain dispersion liquid A；Wherein receive
Rice black phosphorus dispersion liquid（Black phosphorus quantum dot/1- butyl-tri-methylimidazolium cdicynanmide dispersion liquid）A concentration of 1mg/mL, graphite oxide
Alkene dispersion liquid（Graphene oxide/1- butyl-tri-methylimidazolium cdicynanmide dispersion liquid）A concentration of 4mg/mL, nanometer black phosphorus and oxygen
The mass ratio of graphite alkene is 1:3；It is ultrasonically treated to carry out ultrasonic pretreatment using ultrasonic cleaner, ultrasonic cleaner
Power is 300W, and the processing time of ultrasonic cleaner is 2h；
（2）In inert gas（Nitrogen）Under ambient conditions, by step（1）Gained dispersion liquid A is handled through liquid nitrogen and is freeze-dried i.e.
Obtain nanometer black phosphorus/three-dimensional grapheme nanocomposite；
Electronic Speculum, XPS characterizations, and electricity are scanned to nanometer black phosphorus/three-dimensional grapheme nanocomposite made from the present embodiment
Catalysis analysis oxygen performance test, after testing analysis know that the present embodiment composite material has three-dimensional net structure, and in composite material
Nanometer phosphorus forms P-O-C keys with graphene；Linear voltammetric scan test knows that the composite material has good electrocatalysis characteristic.
Embodiment 4：A kind of preparation method of high stable nanometer black phosphorus/three-dimensional graphene composite material, is as follows：
（1）It is 30 DEG C, inert gas in temperature（Nitrogen）Under ambient conditions, by nanometer black phosphorus dispersion liquid（Nanometer black phosphorus dispersion liquid
For black phosphorus quantum dot/N,N-dimethylformamide dispersion liquid）With graphene oxide dispersion（Graphene oxide dispersion is oxidation
Graphene/N,N-dimethylformamide dispersion liquid）Mixing, it is sonicated to obtain dispersion liquid A；Wherein nanometer black phosphorus dispersion liquid
（Black phosphorus quantum dot/N,N-dimethylformamide dispersion liquid）A concentration of 1mg/mL, graphene oxide dispersion（Graphite oxide
Alkene/N,N-dimethylformamide dispersion liquid）A concentration of 4mg/mL, the mass ratio of nanometer black phosphorus and graphene oxide is 1:4；It is super
Sonication is to carry out ultrasonic pretreatment using ultrasonic cleaner, and the power of ultrasonic cleaner is 300W, and supersonic cell is clear
The processing time for washing device is 1h；
（2）In inert gas（The gaseous mixture of argon gas/nitrogen）Under ambient conditions, by step（1）Gained dispersion liquid A is handled through liquid nitrogen
And it is freeze-dried up to nanometer black phosphorus/three-dimensional grapheme nanocomposite；
Electronic Speculum, XPS characterizations, and electricity are scanned to nanometer black phosphorus/three-dimensional grapheme nanocomposite made from the present embodiment
Catalysis analysis oxygen performance test, after testing analysis know that the present embodiment composite material has three-dimensional net structure, and in composite material
Nanometer phosphorus forms P-O-C keys with graphene, and linear voltammetric scan test knows that the composite material has good electrocatalysis characteristic.
Embodiment 5：A kind of preparation method of high stable nanometer black phosphorus/three-dimensional graphene composite material, is as follows：
（1）It is 25 DEG C, inert gas in temperature（Nitrogen）Under ambient conditions, by nanometer black phosphorus dispersion liquid（Nanometer black phosphorus dispersion liquid
For black phosphorus quantum dot/alcohol dispersion liquid）With graphene oxide dispersion（Graphene oxide dispersion is graphene oxide ethyl alcohol point
Dispersion liquid）Mixing, it is sonicated to obtain dispersion liquid A；Wherein nanometer black phosphorus dispersion liquid（Black phosphorus quantum dot/alcohol dispersion liquid）It is dense
Degree is 1mg/mL, graphene oxide dispersion（Graphene oxide/alcohol dispersion liquid）A concentration of 4mg/mL, nanometer black phosphorus and oxygen
The mass ratio of graphite alkene is 1:3；It is ultrasonically treated to carry out ultrasonic pretreatment using ultrasonic cleaner and cell disruptor, surpasses
The power of sound wave washer is 150W, and the power of ultrasonic time 0.5h, cell disruptor are 1000W, ultrasonic time 0.5h；
（2）In inert gas（Nitrogen）Under ambient conditions, by step（1）Gained dispersion liquid A is handled through liquid nitrogen and is freeze-dried i.e.
Obtain nanometer black phosphorus/three-dimensional grapheme nanocomposite；
Electronic Speculum, XPS characterizations, and electricity are scanned to nanometer black phosphorus/three-dimensional grapheme nanocomposite made from the present embodiment
Catalysis analysis oxygen performance test, after testing analysis know that the present embodiment composite material has three-dimensional net structure, and in composite material
Nanometer phosphorus forms P-O-C keys with graphene, and linear voltammetric scan test knows that the composite material has good electrocatalysis characteristic.
Embodiment 6：A kind of preparation method of high stable nanometer black phosphorus/three-dimensional graphene composite material, is as follows：
（1）It is 25 DEG C, inert gas in temperature（Nitrogen）Under ambient conditions, by nanometer black phosphorus dispersion liquid（Nanometer black phosphorus dispersion liquid
For black phosphorus quantum dot/isopropanol dispersion liquid）With graphene oxide dispersion（Graphene oxide dispersion is graphene oxide isopropyl
Alcohol dispersion liquid）Mixing, it is sonicated to obtain dispersion liquid A；Wherein nanometer black phosphorus dispersion liquid（Black phosphorus quantum dot/isopropanol dispersion
Liquid）A concentration of 1mg/mL, graphene oxide dispersion（Graphene oxide/isopropanol dispersion liquid）A concentration of 4mg/mL, receive
The mass ratio of rice black phosphorus and graphene oxide is 1:1；It is ultrasonically treated to carry out ultrasonic pretreatment, cell powder using cell disruptor
Broken machine, sonication treatment time 2h；
（2）In inert gas（Nitrogen）Under ambient conditions, by step（1）Gained dispersion liquid A is handled through liquid nitrogen and is freeze-dried i.e.
Obtain nanometer black phosphorus/three-dimensional grapheme nanocomposite；
Electronic Speculum, XPS characterizations, and electricity are scanned to nanometer black phosphorus/three-dimensional grapheme nanocomposite made from the present embodiment
Catalysis analysis oxygen performance test, after testing analysis know that the present embodiment composite material has three-dimensional net structure, and in composite material
Nanometer phosphorus forms P-O-C keys with graphene, and linear voltammetric scan test knows that the composite material has good electrocatalysis characteristic.
The specific implementation mode of the present invention is explained in detail above, but the present invention is not limited to above-mentioned embodiment party
Formula can also be made without departing from the purpose of the present invention within the knowledge of a person skilled in the art
Go out various change.
Claims (5)
1. a kind of preparation method of high stable nanometer black phosphorus/three-dimensional graphene composite material, which is characterized in that specific steps are such as
Under：
（1）Temperature be 5 ~ 30 DEG C, atmosphere of inert gases under the conditions of, nanometer black phosphorus dispersion liquid is mixed with graphene oxide dispersion
It closes, it is sonicated to obtain dispersion liquid A；
（2）Under the conditions of atmosphere of inert gases, by step（1）Gained dispersion liquid A is handled and is freeze-dried through liquid nitrogen up to nanometer
Black phosphorus/three-dimensional grapheme nanocomposite.
2. the preparation method of high stable nanometer black phosphorus/three-dimensional graphene composite material, feature exist according to claim 1
In：Step（1）The mass ratio of nanometer black phosphorus and graphene oxide is 1:(1~4).
3. the preparation method of high stable nanometer black phosphorus/three-dimensional graphene composite material, feature exist according to claim 1
In：Step（1）Nanometer black phosphorus is black phosphorus alkene, black phosphorus quantum dot or black phosphorus nano wire；Nanometer black phosphorus dispersion liquid dispersion solvent be
Water, ethyl alcohol, dimethyl sulfoxide (DMSO), N-Methyl pyrrolidone, isopropanol, N,N-dimethylformamide, ethylene carbonate or 1- butyl-
Tri-methylimidazolium cdicynanmide；The dispersion solvent of graphene oxide dispersion is water, ethyl alcohol, dimethyl sulfoxide (DMSO), N- crassitudes
Ketone, isopropanol, N,N-dimethylformamide, ethylene carbonate or 1- butyl-tri-methylimidazolium cdicynanmide.
4. the preparation method of high stable nanometer black phosphorus/three-dimensional graphene composite material, feature exist according to claim 1
In：Step（1）It is ultrasonically treated and ultrasonic pretreatment is carried out using supersonic cell washer and/or cell disruptor, ultrasonic wave is thin
The power of born of the same parents' washer is 150W ~ 300W, and the power of cell disruptor is 500 ~ 1500W, and sonication treatment time is 0.5 ~ 3h.
5. the preparation method of high stable nanometer black phosphorus/three-dimensional graphene composite material, feature exist according to claim 1
In：Inert gas is the one or two of argon gas, nitrogen, helium.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810384545.5A CN108529578B (en) | 2018-04-26 | 2018-04-26 | Preparation method of high-stability nano black phosphorus/three-dimensional graphene composite material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810384545.5A CN108529578B (en) | 2018-04-26 | 2018-04-26 | Preparation method of high-stability nano black phosphorus/three-dimensional graphene composite material |
Publications (2)
| Publication Number | Publication Date |
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| CN109152113A (en) * | 2018-09-20 | 2019-01-04 | 广东烯创科技有限公司 | Electric radiant Heating Film based on graphene and preparation method thereof, Electric heat radiator and electric heating equipment |
| CN109592962A (en) * | 2019-01-28 | 2019-04-09 | 北京航空航天大学 | A kind of bionical ternary system graphene-black phosphorus nanocomposite films preparation method |
| CN110627049A (en) * | 2019-11-04 | 2019-12-31 | 青岛大学 | Preparation method and application of graphene-loaded black phosphorus quantum dot |
| CN111422840A (en) * | 2020-04-01 | 2020-07-17 | 东华理工大学 | Phosphorus/graphene three-dimensional aerogel material and preparation method and application thereof |
| CN111554908A (en) * | 2020-05-19 | 2020-08-18 | 上海健康医学院 | Three-dimensional porous black phosphorus alkene/graphene for magnesium ion battery and preparation method and application thereof |
| CN111892026A (en) * | 2020-07-30 | 2020-11-06 | 河南大学 | Preparation method of black phosphorus quantum dot and graphene composite nano material |
| CN113725425A (en) * | 2021-08-27 | 2021-11-30 | 昆明理工大学 | High-safety and high-performance battery negative electrode material |
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| CN110627049A (en) * | 2019-11-04 | 2019-12-31 | 青岛大学 | Preparation method and application of graphene-loaded black phosphorus quantum dot |
| CN111422840A (en) * | 2020-04-01 | 2020-07-17 | 东华理工大学 | Phosphorus/graphene three-dimensional aerogel material and preparation method and application thereof |
| CN111554908A (en) * | 2020-05-19 | 2020-08-18 | 上海健康医学院 | Three-dimensional porous black phosphorus alkene/graphene for magnesium ion battery and preparation method and application thereof |
| CN111892026A (en) * | 2020-07-30 | 2020-11-06 | 河南大学 | Preparation method of black phosphorus quantum dot and graphene composite nano material |
| CN113725425A (en) * | 2021-08-27 | 2021-11-30 | 昆明理工大学 | High-safety and high-performance battery negative electrode material |
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