CN106252091B - A kind of Fe3O4/ graphene composite material and preparation method thereof - Google Patents
A kind of Fe3O4/ graphene composite material and preparation method thereof Download PDFInfo
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- CN106252091B CN106252091B CN201610785271.1A CN201610785271A CN106252091B CN 106252091 B CN106252091 B CN 106252091B CN 201610785271 A CN201610785271 A CN 201610785271A CN 106252091 B CN106252091 B CN 106252091B
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 126
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 104
- 239000002131 composite material Substances 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 239000006210 lotion Substances 0.000 claims abstract description 30
- 239000007788 liquid Substances 0.000 claims abstract description 16
- 239000000463 material Substances 0.000 claims abstract description 8
- 238000000926 separation method Methods 0.000 claims abstract description 6
- 239000011261 inert gas Substances 0.000 claims abstract description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 75
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 60
- 229910002804 graphite Inorganic materials 0.000 claims description 30
- 239000010439 graphite Substances 0.000 claims description 30
- 229960004887 ferric hydroxide Drugs 0.000 claims description 18
- IEECXTSVVFWGSE-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Fe+3] IEECXTSVVFWGSE-UHFFFAOYSA-M 0.000 claims description 18
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 18
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 16
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 15
- 239000004202 carbamide Substances 0.000 claims description 15
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 11
- 238000001914 filtration Methods 0.000 claims description 10
- 239000012286 potassium permanganate Substances 0.000 claims description 10
- 235000010344 sodium nitrate Nutrition 0.000 claims description 9
- 239000004317 sodium nitrate Substances 0.000 claims description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 9
- 238000002604 ultrasonography Methods 0.000 claims description 7
- 230000003647 oxidation Effects 0.000 claims description 5
- 238000007254 oxidation reaction Methods 0.000 claims description 5
- 238000009833 condensation Methods 0.000 claims description 2
- 230000005494 condensation Effects 0.000 claims description 2
- 235000014413 iron hydroxide Nutrition 0.000 claims description 2
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 claims description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims 1
- 239000005864 Sulphur Substances 0.000 claims 1
- 239000002253 acid Substances 0.000 claims 1
- 229910052799 carbon Inorganic materials 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 claims 1
- 239000000839 emulsion Substances 0.000 claims 1
- 239000012467 final product Substances 0.000 claims 1
- 239000002245 particle Substances 0.000 abstract description 8
- 238000002156 mixing Methods 0.000 abstract description 6
- 239000002105 nanoparticle Substances 0.000 abstract description 5
- 239000002114 nanocomposite Substances 0.000 abstract description 4
- 238000004146 energy storage Methods 0.000 abstract description 3
- 238000005516 engineering process Methods 0.000 abstract description 3
- 241000446313 Lamella Species 0.000 abstract description 2
- 238000005253 cladding Methods 0.000 abstract description 2
- 230000000717 retained effect Effects 0.000 abstract description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 28
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 22
- 239000000243 solution Substances 0.000 description 20
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 16
- 239000000843 powder Substances 0.000 description 14
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 13
- 229910001416 lithium ion Inorganic materials 0.000 description 13
- 238000003756 stirring Methods 0.000 description 13
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 12
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- -1 Graphite alkene Chemical class 0.000 description 10
- 238000013019 agitation Methods 0.000 description 10
- 239000001301 oxygen Substances 0.000 description 10
- 229910052760 oxygen Inorganic materials 0.000 description 10
- 239000000725 suspension Substances 0.000 description 10
- 235000019441 ethanol Nutrition 0.000 description 9
- 229910021529 ammonia Inorganic materials 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 8
- 239000000416 hydrocolloid Substances 0.000 description 8
- 150000001336 alkenes Chemical class 0.000 description 7
- 239000000084 colloidal system Substances 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 238000001338 self-assembly Methods 0.000 description 6
- 239000010405 anode material Substances 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 239000003990 capacitor Substances 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 239000004575 stone Substances 0.000 description 5
- 239000006228 supernatant Substances 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 4
- 239000007772 electrode material Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 238000003760 magnetic stirring Methods 0.000 description 2
- 230000001376 precipitating effect Effects 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000012983 electrochemical energy storage Methods 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 230000009881 electrostatic interaction Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-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
- H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-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
- H01G11/32—Carbon-based
- H01G11/36—Nanostructures, e.g. nanofibres, nanotubes or fullerenes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-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
- H01G11/46—Metal oxides
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-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
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
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- 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
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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- 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
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Abstract
The present invention relates to a kind of Fe3O4/ graphene composite material and preparation method thereof belongs to energy storage device electrode field of material technology.The Fe of the present invention3O4The preparation method of/graphene composite material includes the following steps：By graphene oxide lotion and Fe (OH)3Colloidal sol is uniformly mixed, and is separated by solid-liquid separation, and Fe (OH) is made3/ graphene oxide composite material；By Fe obtained (OH)3/ graphene oxide composite material under inert gas protection, at 200 500 DEG C heat 1 5h to get.The preparation method of the present invention realizes Fe (OH) by the electrostatic force between colloidal particle3Combining closely between colloidal particle and GO lamellas only can be achieved with Fe (OH) by simply mixing3Effective cladding of the nano-particle to graphene.Then by being heat-treated to the nanocomposite, Fe (OH)3It is converted into Fe3O4, while the pattern of sandwich structure is retained.
Description
Technical field
The present invention relates to a kind of Fe3O4/ graphene composite material and preparation method thereof belongs to energy storage device electrode material skill
Art field.
Background technology
In recent years, with the fast development of green energy resource industry, electrochemical energy storage technology is sent out in human society and life
Increasingly important role is waved, various electrochemical energy storing devices are in fields such as electric vehicle, energy storage, communication power supply and electronic products
Using also more and more extensive.Wherein, lithium ion battery and ultracapacitor are with energy density is big, power density is high, the cycle longevity
Life is long, self-discharge rate is low and many merits such as " green " environmental protection, becomes the hot spot of application.
As the application field of lithium ion battery and ultracapacitor is more and more extensive, each application field is to lithium ion battery
And the performance requirement of ultracapacitor is also higher and higher, and still, due to the limitation of lithium ion battery and ultracapacitor itself,
Performance raising encounters larger bottleneck, and the bottleneck of electrode material performance is that restriction lithium ion battery and performance of the supercapacitor carry
High key factor.Therefore, high performance new electrode materials are developed to solving lithium ion battery and performance of the supercapacitor bottle
Seem for neck significant.
Fe3O4It is high with theoretical specific capacity, raw material resources are abundant, relative low price and environmentally safe etc. many excellent
Point all has wide application prospect as lithium ion battery and super capacitor anode material.But its initial coulomb efficiency
Low, cyclical stability is poor, and high rate performance is poor.Prepare the Fe of nanostructure3O4With construct Fe3O4/ C composite can be one
Determine to solve the above problems in degree.
Graphene has become and Fe because having high theoretical specific surface and good electric conductivity3O4The best carbon materials of composite wood
Material.Studies have shown that significantly increasing Fe with graphene recombination energy3O4Chemical property.However, since graphene is easy to reunite,
It is difficult to prepare Fe3O4The composite material of uniform, stable dispersion on the surface of graphene, and it has been reported that preparation method technique it is multiple
It is miscellaneous, high energy consumption, to the more demanding of synthesis device, to improve production cost, it is difficult to realize industrialization.
Invention content
The purpose of the present invention is to provide one kind capable of making Fe3O4The Fe of uniform, stable dispersion on the surface of graphene3O4/
The preparation method of graphene composite material.
The present invention also aims to provide Fe made from the above method3O4/ graphene composite material.
The present invention solves Fe used by above-mentioned technical problem3O4The technical solution of the preparation method of/graphene composite material
It is as follows：
A kind of Fe3O4The preparation method of/graphene composite material, includes the following steps：
1）By graphene oxide lotion and Fe (OH)3Colloidal sol mixes, and is separated by solid-liquid separation, and Fe (OH) is made3/ graphene oxide is multiple
Condensation material；
2）By Fe obtained (OH)3/ graphene oxide composite material heats under inert gas protection, at 200-500 DEG C
1-5h to get.
The mass ratio of the iron hydroxide in graphene oxide and ferric hydroxide sol in graphene oxide lotion is 1:10-
30。
Step 1）Middle graphene oxide lotion and Fe (OH)3Mechanical agitation is carried out after colloidal sol mixing.When the mechanical agitation
Between be 5-12h.
Step 1）Middle Fe (OH)3The preparation method of colloidal sol includes：By precipitating reagent and FeCl3It mixes, stands, so in a solvent
Afterwards at 50-90 DEG C react 0.5-10h to get.
The precipitating reagent is one or two kinds of in urea, ammonium hydroxide.
The solvent is the one or several kinds in water, ethyl alcohol, acetone.
Step 1）Middle Fe (OH)3The preparation method of colloidal sol is preferably：By urea and FeCl3It mixes, stands, then in water
At 70-90 DEG C react 0.5-10h to get.The urea and FeCl3Mixing is that FeCl is added in urea liquid in water3Solution
In.
A concentration of 0.001-1mol/L of the urea liquid, the FeCl3A concentration of 0.0005-0.5mol/ of solution
L.The time of the standing is 0.5-10h.Urea liquid and FeCl3The volume ratio of solution is 1：5-10.
Step 1）Middle Fe (OH)3Colloidal sol can also use the method included the following steps to be made：
The ethanol solution of ammonia is added into the ethanol solution of ferric trichloride or is added into the acetone soln of ferric trichloride
The acetone soln of ammonia, the pH for adjusting solution is 6, at 50 DEG C, reacts 0.5-3h, is separated by solid-liquid separation, obtains hydrocolloid powder；By colloid
Powder is added to the water mixing to get ferric hydroxide colloid solution.
A concentration of 0.1mol/L of the ethanol solution of ferric trichloride.A concentration of 0.1mol/ of the acetone soln of ferric trichloride
L.A concentration of 0.6mol/L of the ethanol solution of ammonia.A concentration of 0.6mol/L of the acetone soln of ammonia.
The ethanol solution of ammonia is added into the ethanol solution of ferric trichloride or is added into the acetone soln of ferric trichloride
When the acetone soln of ammonia by the way of dropwise addition.
It is described to be separated by solid-liquid separation as filtering.It is washed with absolute ethyl alcohol or acetone after filtering.Washing times are 3-5 times.
It is separated by solid-liquid separation obtained solid and dries 3h in 90 DEG C of baking oven, obtain hydrocolloid powder.
The mass ratio that hydrocolloid powder is added to the water to the hydrocolloid powder and water used in mixing is 1-10：1000.
Step 1）Middle graphene oxide lotion can in water be disperseed to be made by graphene oxide.
Preferably, step 1）The preparation method of middle graphene oxide lotion includes：
It by graphite, sodium nitrate, the concentrated sulfuric acid under the conditions of 0 DEG C, is uniformly mixed, potassium permanganate is then added, react 2h, be added
Water and hydrogen peroxide are stood, and filtering is washed up to graphite oxide；By graphite oxide, graphene oxide is made in ultrasound stripping in water
Lotion.The mass percent concentration of the hydrogen peroxide is 30%.The mass percent concentration of the concentrated sulfuric acid is 98%.
In the above method, corresponded to using 2g graphite, 2g sodium nitrate, 12g potassium permanganate per the 100mL concentrated sulfuric acids.
The water that is added is that the water that 184mL temperature is 25 DEG C and the water that 560mL temperature is 50 DEG C is added.The 184mL temperature
The water that degree is 25 DEG C is used and is slowly added dropwise, time for adding 15min.
It refers to stirring 15min to be uniformly mixed.
After potassium permanganate is added, 30min is stood at 0 DEG C, stirs 2h.
Washing is washed successively using dilute hydrochloric acid and deionized water.A concentration of 1-10% of the dilute hydrochloric acid.
The Fe of the present invention3O4The technical solution of/graphene composite material is as follows：
The Fe of the present invention3O4/ graphene composite material is made using the above method.
The Fe of the present invention3O4The preparation method of/graphene composite material realizes Fe by the electrostatic force between colloidal particle
(OH)3Combining closely between colloidal particle and GO lamellas only can be achieved with Fe (OH) by simply mixing3Nano-particle pair
Effective cladding of graphene.In the complex sol system being formed by, the positively charged Fe in surface (OH)3Colloidal particle and surface
Electronegative GO pieces carry out self assembly by electrostatic interaction, have obtained the Fe (OH) of the stratiform with similar sandwich structure3/
GO/ Fe(OH)3Nanocomposite.Then by being heat-treated to the nanocomposite, oxygen during heat treatment
Graphite alkene is reduced to graphene, Fe (OH)3It is converted into Fe3O4, while the pattern of sandwich structure is retained.The present invention
Method have preparation method simple, the characteristics of process costs are low, and low energy consumption, be very suitable for commercial application.
The Fe of the present invention3O4Fe made from the preparation method of/graphene composite material3O4/ graphene composite material can be used as
The negative material of lithium ion battery and ultracapacitor, wherein Fe3O4Nano-particle stores charge, graphite by electrochemical reaction
Alkene provides the channel of electron-transport and stable structure skeleton, three-dimensional porous structure are conducive to the free migration of electrolyte ion,
To give full play to Fe3O4Synergistic effect between nano-particle and graphene obtains having both high power density and high-energy density
Lithium ion battery and super capacitor anode material.
Description of the drawings
Fig. 1 is the Fe of the embodiment of the present invention 13O4The XRD spectrum of/graphene composite material；
Fig. 2 is the Fe of the embodiment of the present invention 13O4The SEM image of/graphene composite material；
Fig. 3 is the Fe of the embodiment of the present invention 23O4The SEM image of/graphene composite material；
Fig. 4 is the Fe of the embodiment of the present invention 13O4Multiplying power of/the graphene composite material as lithium ion battery negative material
Cyclic curve；
Fig. 5 is the Fe of the embodiment of the present invention 13O4Cycle of/the graphene composite material as super capacitor anode material
Curve.
Specific implementation mode
In order to make the technical problems, technical solutions and beneficial effects solved by the present invention be easier to understand, with reference to attached
The present invention is described in detail for figure and specific implementation mode.
Embodiment 1
The Fe of the present embodiment3O4The preparation method of/graphene composite material, includes the following steps：
1）Compound concentration is the ferric chloride aqueous solutions of 0.01mol/L, and compound concentration is that the urea of 0.02mol/L is water-soluble
The aqueous solution of urea of 20mL is added drop-wise in the liquor ferri trichloridi of 100mL by liquid, is carried out magnetic agitation during being added dropwise, is added dropwise
It stands 1h at room temperature after the completion, then reacts 5h under 80 DEG C of condition of water bath heating, the Fe (OH) of azarin brown is made3It is molten
Glue, wherein ferric hydroxide colloid particle surface are positively charged；
2g graphite powders, 2g sodium nitrate are weighed, and is added in the concentrated sulfuric acid of 100mL a concentration of 98%, in 0 DEG C of condition of ice bath
Under, stirring 15min makes it be uniformly mixed, and 12g potassium permanganate is then added, and cooling 30min is stood under 0 DEG C of condition of ice bath,
Then it is stirred to react 2h under condition of ice bath, obtains suspension；184mL25 DEG C of water is added in above-mentioned suspension, 15min adds
It is complete, the hydrogen peroxide of water and 40mL a concentration of 30% that 560mL temperature is 50 DEG C is then sequentially added thereto, is stood 30min, is abandoned
Supernatant is removed, is filtered, the hydrochloric acid and deionized water that filter residue is 10% with mass concentration wash successively, are drying to obtain graphite oxide；
Obtained graphene oxide is dispersed in water, and ultrasound stripping 1h removes the graphene oxide of stratiform the graphite oxide at monolithic
The graphene oxide lotion of a concentration of 0.1g/L is made in alkene；
2）Take step 1）In graphene oxide lotion obtained and ferric hydroxide sol will aoxidize stone under agitation
Black alkene lotion is added to Fe (OH)3In colloidal sol, the Fe in graphene oxide and ferric hydroxide sol in graphene oxide lotion
(OH)3Mass ratio be 1:20, then ultrasonic disperse 1h, stirring 50min make graphene oxide and Fe (OH)3It is anti-that self assembly occurs
It answers, filters, obtain Fe (OH)3/ graphene oxide composite material；In the tube furnace for being passed through nitrogen, by Fe obtained (OH)3/ oxygen
Graphite alkene composite material heated at 200 DEG C 3h to get.
Embodiment 2
The Fe of the present embodiment3O4The preparation method of/graphene composite material, includes the following steps：
1）Compound concentration is the ferric chloride aqueous solutions of 0.2mol/L, and compound concentration is the aqueous solution of urea of 0.5mol/L,
The aqueous solution of urea of 10mL is added drop-wise in the liquor ferri trichloridi of 100mL, magnetic agitation is carried out during being added dropwise, is added dropwise to complete
It is being stored at room temperature 5h afterwards, is then reacting 10h under 70 DEG C of condition of water bath heating, the Fe (OH) of azarin brown is made3Colloidal sol,
Middle ferric hydroxide colloid particle surface is positively charged；
2g graphite powders, 2g sodium nitrate are weighed, and is added in the concentrated sulfuric acid of 100mL a concentration of 98%, in 0 DEG C of condition of ice bath
Under, stirring 15min makes it be uniformly mixed, and 12g potassium permanganate is then added, and cooling 30min is stood under 0 DEG C of condition of ice bath,
Then it is stirred to react 2h under condition of ice bath, obtains suspension；The water that 184mL temperature is 25 DEG C is added in above-mentioned suspension,
15min is added, and is then sequentially added the hydrogen peroxide of water and 40mL a concentration of 30% that 560mL temperature is 50 DEG C thereto, is stood
30min discards supernatant liquid, filtering, and the hydrochloric acid and deionized water that filter residue is 5% with mass concentration wash successively, are drying to obtain oxidation
Graphite；Obtained graphene oxide is dispersed in water, ultrasound stripping 1h removes the graphene oxide of stratiform the oxygen at monolithic
The graphene oxide lotion of a concentration of 0.1g/L is made in graphite alkene；
2）Take step 1）In graphene oxide lotion obtained and ferric hydroxide sol will aoxidize stone under agitation
Black alkene lotion is added to Fe (OH)3In colloidal sol, the Fe in graphene oxide and ferric hydroxide sol in graphene oxide lotion
(OH)3Mass ratio be 1:30, then ultrasonic disperse 1h, stirring 50min make graphene oxide and Fe (OH)3It is anti-that self assembly occurs
It answers, filters, obtain Fe (OH)3/ graphene oxide composite material；In the tube furnace for being passed through nitrogen, by Fe obtained (OH)3/ oxygen
Graphite alkene composite material heated at 300 DEG C 2h to get.
Embodiment 3
The Fe of the present embodiment3O4The preparation method of/graphene composite material, includes the following steps：
1）Compound concentration is the ferric chloride aqueous solutions of 0.5mol/L, and compound concentration is the aqueous solution of urea of 1mol/L, will
The aqueous solution of urea of 12.5mL is added drop-wise in the liquor ferri trichloridi of 100mL, is carried out magnetic agitation during being added dropwise, is added dropwise to complete
It stands 10h at room temperature afterwards, then reacts 0.5h under 90 DEG C of condition of water bath heating, the Fe (OH) of azarin brown is made3It is molten
Glue, wherein ferric hydroxide colloid particle surface are positively charged；
2g graphite powders, 2g sodium nitrate are weighed, and is added in the concentrated sulfuric acid of 100mL a concentration of 98%, in 0 DEG C of condition of ice bath
Under, stirring 15min makes it be uniformly mixed, and 12g potassium permanganate is then added, and cooling 30min is stood under 0 DEG C of condition of ice bath,
Then it is stirred to react 2h under condition of ice bath, obtains suspension；It is that 25 DEG C of water are added in above-mentioned suspension by 184mL temperature,
15min is added, and is then sequentially added the hydrogen peroxide of water and 40mL a concentration of 30% that 560mL temperature is 50 DEG C thereto, is stood
30min discards supernatant liquid, filtering, and the hydrochloric acid and deionized water that filter residue is 3% with mass concentration wash successively, are drying to obtain oxidation
Graphite；Obtained graphene oxide is dispersed in water, ultrasound stripping 1h removes the graphene oxide of stratiform the oxygen at monolithic
The graphene oxide lotion of a concentration of 0.1g/L is made in graphite alkene；
2）Take step 1）In graphene oxide lotion obtained and ferric hydroxide sol will aoxidize stone under agitation
Black alkene lotion is added to Fe (OH)3In colloidal sol, the Fe in graphene oxide and ferric hydroxide sol in graphene oxide lotion
(OH)3Mass ratio be 1:24, then ultrasonic disperse 1h, stirring 50min make graphene oxide and Fe (OH)3It is anti-that self assembly occurs
It answers, filters, obtain Fe (OH)3/ graphene oxide composite material；In the tube furnace for being passed through nitrogen, by Fe obtained (OH)3/ oxygen
Graphite alkene composite material heated at 500 DEG C 2h to get.
Embodiment 4
The Fe of the present embodiment3O4The preparation method of/graphene composite material, includes the following steps：
1）Under magnetic stirring, the ammonia of 0.6mol/L is added dropwise into the ethanol solution of the ferric trichloride of a concentration of 0.1mol/L
Ethanol solution, controlled at 50 DEG C, the pH for adjusting solution is 6, reacts 3h, and filtering, filter residue washs 3 times with absolute ethyl alcohol,
Obtained solid is dried into 3h in 90 DEG C of baking oven, obtains hydrocolloid powder；10g hydrocolloid powders are added in 1000g distilled water
Stirring is to get ferric hydroxide colloid solution；
2g graphite powders, 2g sodium nitrate are weighed, and is added in the concentrated sulfuric acid of 100mL a concentration of 98%, in 0 DEG C of condition of ice bath
Under, stirring 15min makes it be uniformly mixed, and 12g potassium permanganate is then added, and cooling 30min is stood under 0 DEG C of condition of ice bath,
Then it is stirred to react 2h under condition of ice bath, obtains suspension；The water that 184mL temperature is 25 DEG C is added in above-mentioned suspension,
15min is added, and is then sequentially added the hydrogen peroxide of water and 40mL a concentration of 30% that 560mL temperature is 50 DEG C thereto, is stood
30min discards supernatant liquid, filtering, and the hydrochloric acid and deionized water that filter residue is 5% with mass concentration wash successively, are drying to obtain oxidation
Graphite；Obtained graphene oxide is dispersed in water, ultrasound stripping 1h removes the graphene oxide of stratiform the oxygen at monolithic
The graphene oxide lotion of a concentration of 0.1g/L is made in graphite alkene；
2）Take step 1）In graphene oxide lotion obtained and ferric hydroxide sol will aoxidize stone under agitation
Black alkene lotion is added to Fe (OH)3In colloidal sol, the Fe in graphene oxide and ferric hydroxide sol in graphene oxide lotion
(OH)3Mass ratio be 1:20, then ultrasonic disperse 1h, stirring 50min make graphene oxide and Fe (OH)3It is anti-that self assembly occurs
It answers, filters, obtain Fe (OH)3/ graphene oxide composite material；In the tube furnace for being passed through nitrogen, by Fe obtained (OH)3/ oxygen
Graphite alkene composite material heated at 300 DEG C 2h to get.
Embodiment 5
The Fe of the present embodiment3O4The preparation method of/graphene composite material, includes the following steps：
1）Under magnetic stirring, the ammonia of 0.6mol/L is added dropwise into the acetone soln of the ferric trichloride of a concentration of 0.1mol/L
Acetone soln, controlled at 50 DEG C, the pH for adjusting solution is 6, reacts 5h, and filtering, filter residue wash 5 times with acetone, general
To solid dry 4h in 90 DEG C of baking oven, obtain hydrocolloid powder；3g hydrocolloid powders are added in 1000g distilled water and are stirred,
Up to ferric hydroxide colloid solution；
2g graphite powders, 2g sodium nitrate are weighed, and is added in the concentrated sulfuric acid of 100mL a concentration of 98%, in 0 DEG C of condition of ice bath
Under, stirring 15min makes it be uniformly mixed, and 12g potassium permanganate is then added, and cooling 30min is stood under 0 DEG C of condition of ice bath,
Then it is stirred to react 2h under condition of ice bath, obtains suspension；The water that 184mL temperature is 25 DEG C is added in above-mentioned suspension,
15min is added, and is then sequentially added the hydrogen peroxide of water and 40mL a concentration of 30% that 560mL temperature is 50 DEG C thereto, is stood
30min discards supernatant liquid, filtering, and the hydrochloric acid and deionized water that filter residue is 5% with mass concentration wash successively, are drying to obtain oxidation
Graphite；Obtained graphene oxide is dispersed in water, ultrasound stripping 1h removes the graphene oxide of stratiform the oxygen at monolithic
The graphene oxide lotion of a concentration of 0.1g/L is made in graphite alkene；
2）Take step 1）In graphene oxide lotion obtained and ferric hydroxide sol will aoxidize stone under agitation
Black alkene lotion is added to Fe (OH)3In colloidal sol, the Fe in graphene oxide and ferric hydroxide sol in graphene oxide lotion
(OH)3Mass ratio be 1:20, then ultrasonic disperse 1h, stirring 50min make graphene oxide and Fe (OH)3It is anti-that self assembly occurs
It answers, filters, obtain Fe (OH)3/ graphene oxide composite material；In the tube furnace for being passed through nitrogen, by Fe obtained (OH)3/ oxygen
Graphite alkene composite material heated at 500 DEG C 2h to get.
Test example
1）Object is mutually tested
By Fe obtained in embodiment 13O4/ graphene composite material carries out XRD detections, and the results are shown in Figure 1.
As shown in Figure 1, sample made from embodiment 1 has sharp diffraction maximum, peak position and standard card（PDF NO.
88-0866）Each diffraction maximum corresponds to, and belongs to Fe3O4Diffraction maximum.
2）Pattern test
By Fe obtained in embodiment 1 and embodiment 23O4/ graphene composite material carries out SEM detections respectively, as a result distinguishes
As shown in Figures 2 and 3.
By Fig. 2 and Fig. 3 it is found that in Fe3O4In/graphene composite material, Fe3O4Nano particle uniform adsorption is in graphene
Both side surface, and form the Fe of similar sandwich structure3O4/ graphene/Fe3O4Nanocomposite.
3）Electrochemical property test
By Fe obtained in embodiment 13O4/ graphene composite material is as lithium ion battery negative material, supplemented by lithium piece
Electrode and reference electrode are helped, simulation lithium ion battery is made, carries out charge and discharge under 0.2C, 0.5C, 1C, 2C, 10C multiplying power respectively
Electricity, and loop test is carried out, test results are shown in figure 4.
By Fe obtained in embodiment 13O4/ graphene composite material is as super capacitor anode material, with commercialization
Activated carbon is positive electrode, ultracapacitor is made, respectively under the current density of 1A/g, 2A/g, 5A/g, 10A/g, 20A/g
Charge and discharge are carried out, and carry out loop test, test results are shown in figure 5.
As shown in Figure 4, the composite material prepared by embodiment 1 is as lithium ion battery negative material, in the charge and discharge of 0.2C
Under electric multiplying power for the first time discharge capacity up to 1100 mAh/g.
As shown in Figure 5, electric discharge of the composite material prepared by embodiment 1 as super capacitor anode material in 1A/g is electric
Specific capacitance is up to 624 F/g under current density, and has good multiplying power discharging property.
It is above disclosed to be merely a preferred embodiment of the present invention, the right of the present invention cannot be limited with this certainly
Range, therefore, the equivalent variations done in the scope of the invention still fall within the range that the present invention is covered.
Claims (5)
1. a kind of Fe3O4The preparation method of/graphene composite material, which is characterized in that include the following steps：
1）By graphene oxide lotion and Fe (OH)3Colloidal sol is uniformly mixed, and is separated by solid-liquid separation, and Fe (OH) is made3/ graphene oxide is multiple
Condensation material；
2）By Fe obtained (OH)3/ graphene oxide composite material under inert gas protection, 1-5h is heated at 200-500 DEG C,
To obtain the final product；
The mass ratio of graphene oxide and the iron hydroxide in ferric hydroxide sol is 1 in graphene oxide lotion:10-30；
Step 1）Middle Fe (OH)3The preparation method of colloidal sol is：By urea and FeCl3It mixes, stands, then at 70-90 DEG C in water
Lower reaction 0.5-10h to get；
A concentration of 0.001-1mol/L of the urea liquid, the FeCl3A concentration of 0.0005-0.5mol/L of solution；
The time of the standing is 0.5-10h；
Urea liquid and FeCl3The volume ratio of solution is 1：5-10.
2. Fe as described in claim 13O4The preparation method of/graphene composite material, which is characterized in that step 1）Middle oxidation
The preparation method of graphene emulsion includes：
By graphite, sodium nitrate, the concentrated sulfuric acid under the conditions of 0 DEG C, be uniformly mixed, be then added potassium permanganate, react 2h, be added water and
Hydrogen peroxide is stood, and graphite oxide is washed to obtain in filtering；By graphite oxide, graphene oxide lotion is made in ultrasound stripping in water.
3. Fe as claimed in claim 23O4The preparation method of/graphene composite material, which is characterized in that per the dense sulphur of 100mL
Acid is corresponding using 2g graphite, 2g sodium nitrate, 12g potassium permanganate.
4. Fe as claimed in claim 23O4The preparation method of/graphene composite material, which is characterized in that the addition water is
The water that 184mL temperature is 25 DEG C and the water that 560mL temperature is 50 DEG C is added.
5. a kind of using Fe made from preparation method as described in claim 13O4/ graphene composite material.
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| CN108493003A (en) * | 2018-03-28 | 2018-09-04 | 江苏大学 | A kind of preparation method and application of ferroferric oxide nano granules |
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