CN114464799B - Iron oxide nanoparticle/flaky iron hydroxide/multilayer graphene composite material and preparation method thereof - Google Patents
Iron oxide nanoparticle/flaky iron hydroxide/multilayer graphene composite material and preparation method thereof Download PDFInfo
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- CN114464799B CN114464799B CN202111645542.0A CN202111645542A CN114464799B CN 114464799 B CN114464799 B CN 114464799B CN 202111645542 A CN202111645542 A CN 202111645542A CN 114464799 B CN114464799 B CN 114464799B
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 81
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 72
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 title claims abstract description 67
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 title claims abstract description 44
- 235000014413 iron hydroxide Nutrition 0.000 title claims abstract description 42
- 239000002131 composite material Substances 0.000 title claims abstract description 35
- 239000002105 nanoparticle Substances 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000002245 particle Substances 0.000 claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 25
- 238000006243 chemical reaction Methods 0.000 claims description 17
- 239000000243 solution Substances 0.000 claims description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 16
- 239000012046 mixed solvent Substances 0.000 claims description 13
- 239000012153 distilled water Substances 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- 239000011259 mixed solution Substances 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 12
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 11
- ZGTMUACCHSMWAC-UHFFFAOYSA-L EDTA disodium salt (anhydrous) Chemical compound [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 claims description 9
- 229910002804 graphite Inorganic materials 0.000 claims description 8
- 239000010439 graphite Substances 0.000 claims description 8
- 239000000843 powder Substances 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 8
- 238000005119 centrifugation Methods 0.000 claims description 6
- 239000011521 glass Substances 0.000 claims description 6
- 238000009210 therapy by ultrasound Methods 0.000 claims description 6
- 238000005303 weighing Methods 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 5
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 2
- IEECXTSVVFWGSE-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Fe+3] IEECXTSVVFWGSE-UHFFFAOYSA-M 0.000 abstract description 20
- 229960004887 ferric hydroxide Drugs 0.000 abstract description 19
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 abstract description 8
- 229920001021 polysulfide Polymers 0.000 abstract description 8
- 239000005077 polysulfide Substances 0.000 abstract description 8
- 150000008117 polysulfides Polymers 0.000 abstract description 8
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 7
- 229910052717 sulfur Inorganic materials 0.000 abstract description 7
- 239000011593 sulfur Substances 0.000 abstract description 7
- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 abstract description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 4
- 238000001179 sorption measurement Methods 0.000 abstract description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 12
- 229940031182 nanoparticles iron oxide Drugs 0.000 description 8
- 235000019441 ethanol Nutrition 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 239000000126 substance Substances 0.000 description 3
- 238000003917 TEM image Methods 0.000 description 2
- 241000276425 Xiphophorus maculatus Species 0.000 description 2
- 230000006978 adaptation Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
Classifications
-
- 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
-
- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
Abstract
The invention discloses an iron oxide nanoparticle/flaky iron hydroxide/multilayer graphene composite material and a preparation method thereof. The multi-layer graphene in the composite material can well improve the conductivity of the composite material, the hydroxyl groups in the flaky ferric hydroxide have strong polysulfide adsorption capacity, and the porous structure formed by the flaky ferric hydroxide can adsorb more sulfur. The nano ferric oxide particles increase the conductivity of ferric hydroxide and increase the specific surface area of the composite material. The composite material is suitable for constructing a high-performance lithium sulfur battery anode.
Description
Technical Field
The invention belongs to the technical field of materials, and particularly relates to an iron oxide nanoparticle/flaky iron hydroxide/multilayer graphene composite material and a preparation method thereof.
Background
With the rapid development of electric automobiles and portable electronic devices, research on energy storage systems has received more and more attention from students. The lithium-sulfur battery has the advantages of low cost, rich and nontoxic, and the like, and is a main source of a portable power supply. However, sulfur itself has poor conductivity, and the shuttling effect of soluble polysulfides during discharge/charge results in rapid capacity decay of lithium sulfur batteries. In order to overcome these drawbacks, research and preparation of sulfur hosts has been very popular in recent years. Among them, carbon materials have been widely used because of their high conductivity, abundant structure, large specific surface area, etc. The graphene is used as a conductive carrier of the sulfur anode, so that the defect of poor sulfur conductivity can be effectively overcome, and the graphene can inhibit polysulfide dissolution through reasonable surface modification. Studies have shown that the introduction of hydroxyl groups (OH) into the electrode - ) Can effectively improve the electrochemical performance of the lithium-sulfur battery, and utilizes the hydrophilicity and polysulfide of hydroxylThe strong interaction between the substances can anchor polysulfide well.
Disclosure of Invention
Aiming at the problems in the background art, the invention provides an iron oxide nano-particle/flaky iron hydroxide/multilayer graphene composite material and a preparation method thereof, which can uniformly attach the iron oxide nano-particle/flaky iron hydroxide particles to the multilayer graphene.
In order to solve the technical problems in the prior art, the technical scheme of the invention is as follows:
in the composite material, flaky ferric hydroxide grows on the bottom surface of a multilayer graphene base prepared by an ultrasonic method, the flaky ferric hydroxide forms a porous structure, and nano ferric oxide is uniformly distributed on the surfaces of the multilayer graphene and the flaky ferric hydroxide.
Further, the flaky ferric hydroxide and the nano ferric oxide particles on the surface of the multilayer graphene are decomposed by part of ferric hydroxide.
The invention also discloses a preparation method of the iron oxide nanoparticle/flaky iron hydroxide/multilayer graphene composite material, which comprises the following steps:
(1) Preparing a multi-layer graphene solution. Weighing a proper amount of expanded graphite, adding the expanded graphite into a glass bottle, adding DMF and distilled water which are measured by a measuring cylinder in a ratio of 8:2 into the bottle, standing for 12 hours at room temperature, and carrying out ultrasonic treatment for 4 hours to obtain the multilayer graphene solution. The concentration of the multilayer graphene relative to the mixed solvent of DMF and water is 2g/L.
(2) Preparing the iron oxide nano-particle/flaky iron hydroxide particle composite material. Weighing EDTA-2Na 2g/L and FeCl 10g/L of the relative mixed solvent 2 And 1g/L to 5g/L of CH 3 And (3) adding COONa into the multilayer graphene solution, adding alcohol with the volume of 1/500 relative to the volume of the mixed solvent, and magnetically stirring for 10min to obtain a uniform mixed solution.
(3) The mixed solution is put into a water bath kettle and magnetically stirred for reaction for 2 hours at the constant temperature of 90 ℃.
(4) After the reaction was completed, the mixture was cooled to room temperature, and centrifuged 3 times with absolute ethanol and distilled water. And (3) putting the solid powder obtained by centrifugation into a drying box, and drying for 24 hours at 70 ℃ to obtain the iron oxide nano-particle/flaky iron hydroxide/multi-layer graphene composite material.
In the technical proposal, a proper amount of EDTA-2Na and CH are added into the reaction liquid simultaneously 3 COONa. And when a proper amount of the iron is added, the complex formed by the iron can be self-assembled into a sheet, and finally the sheet-shaped ferric hydroxide is formed. When added alone, only iron oxide nanoparticles can be formed.
The preparation principle of the invention is as follows: the reaction system adopts the mixture of DMF and water, when a proper amount of EDTA-2Na and CH are added at the same time 3 In COONa, the complex formed by iron can self-assemble into a sheet. As the reaction proceeds, part of the flake Fe (OH) 3 Decomposition into Fe 2 O 3 While adding CH alone 3 In the case of COONa, only iron oxide nanoparticles can be formed.
Compared with the prior art, the invention has the following beneficial effects:
1. the preparation of the iron oxide nano-particle/flaky iron hydroxide/multilayer graphene composite material adopts a low-temperature water bath reaction, and the preparation process is simple and safe.
2. The composite material consists of three phases of multilayer graphene, flaky ferric hydroxide and ferric oxide nano particles. The multi-layer graphene in the composite material can well improve the conductivity of the composite material, the hydroxyl groups in the flaky ferric hydroxide have strong polysulfide adsorption capacity, and the porous structure formed by the flaky ferric hydroxide can adsorb more sulfur. The nano ferric oxide particles increase the conductivity of ferric hydroxide and increase the specific surface area of the composite material. The layered structure is beneficial to constructing the high-performance lithium sulfur battery anode material.
3. The multilayer graphene is prepared by an ultrasonic method, and the preparation process is simple. However, the carbon ring structure of the surface of the multilayer graphene is complete, the chemical activity is low, and the direct deposition of oxides and hydroxides on the surface of the multilayer graphene is difficult. The invention solves the technical approach that the prior art needs to prepare the composite material after activating the graphite surface.
Drawings
FIG. 1 shows a low-magnification SEM image (a) and a high-magnification SEM image (b) of the iron oxide nanoparticles/flaky iron hydroxide/multi-layered graphene obtained in example 1 of the present invention;
FIG. 2 is an XRD characterization of iron oxide nanoparticles/platy iron hydroxide/multi-layered graphene obtained in example 1 of the present invention;
FIG. 3 is a TEM image of iron oxide nanoparticles/platy iron hydroxide/multi-layered graphene obtained in example 1 of the present invention;
FIG. 4 shows a low-magnification SEM image (a) and a high-magnification SEM image (b) of the iron oxide nanoparticles/flaky iron hydroxide/multi-layered graphene obtained in example 2 of the present invention;
FIG. 5 a low-magnification SEM image (a) and a high-magnification SEM image (b) of the iron oxide nanoparticles/flaky iron hydroxide/multi-layered graphene obtained in example 3 of the present invention;
Detailed Description
The invention adopts the multilayer graphene prepared by ultrasonic as a substrate, and iron oxide nano particles/flaky iron hydroxide particles are prepared on the surface of the substrate. Wherein, the multilayer graphene well improves the defect of low conductivity of sulfur, the specific surface area of the flaky ferric hydroxide is large, the flaky ferric hydroxide can be fully contacted with electrolyte, and hydroxyl in the flaky ferric hydroxide can adsorb polysulfide, so that the polysulfide is more easily fixed on the nano particles. The nano ferric oxide particles increase the conductivity of ferric hydroxide and increase the specific surface area of the composite material. Can be used for constructing high-performance lithium sulfur battery positive electrode. The method specifically comprises the following steps:
step S1: weighing expanded graphite, taking DMF and distilled water with the volume ratio of 8:2 as mixed solvents, sequentially adding the mixed solvents into a reaction glass bottle, standing for 12 hours at room temperature, and then carrying out ultrasonic treatment for 4 hours to obtain a multilayer graphene solution A; the concentration of the multilayer graphene relative to the mixed solvent of DMF and water is 2g/L;
step S2: weighing EDTA-2Na of 2g/L and CH of 1-5 g/L of the relative mixed solvent 3 COONa and 20g/L FeCl 2 Measuring absolute ethyl alcohol of which the volume is 1/500 of that of the mixed solvent, adding the absolute ethyl alcohol into the multilayer graphene solution A, and magnetically stirring the absolute ethyl alcohol for 10 minutes to obtain a uniform mixed solution B;
step S3: putting the mixed solution B into a water bath kettle, and magnetically stirring and reacting for 2 hours at the constant temperature of 90 ℃;
step S4: after the reaction is finished, cooling to room temperature, and centrifuging for 3 times by using absolute ethyl alcohol and distilled water respectively to obtain solid powder C;
step S5: and (3) putting the solid powder C obtained by centrifugation into a drying box, and drying for 24 hours at 70 ℃ to obtain the iron oxide nano-particle/flaky iron hydroxide/multi-layer graphene composite material.
According to the iron oxide nanoparticle/flaky iron hydroxide/multilayer graphene composite material prepared by the method, flaky iron hydroxide grows on the bottom surface of the multilayer graphene prepared by an ultrasonic method, the flaky iron hydroxide forms a porous structure, and nano iron oxide is uniformly distributed on the surfaces of the multilayer graphene and the flaky iron hydroxide.
The technical scheme of the invention is further described through specific examples.
Specific example 1:
(1) Preparing a multi-layer graphene solution. 20mg of expanded graphite is weighed and added into a glass bottle, 8mL of DMF and 2mL of distilled water are measured by a cylinder and added into the bottle, the mixture is kept stand for 12 hours at room temperature, and the multi-layer graphene solution is obtained after ultrasonic treatment for 4 hours.
(2) Preparing the iron oxide nano-particle/flaky iron hydroxide particle composite material. 20mg of EDTA-2Na,100mg of FeCl were weighed out 2 And 10mg of CH 3 COONa is added into the multi-layer graphene solution, 20 mu L of alcohol is added, and the mixture is magnetically stirred for 10min to obtain a uniform mixed solution.
(3) The mixed solution is put into a water bath kettle and magnetically stirred for reaction for 2 hours at the constant temperature of 90 ℃.
(4) After the reaction was completed, the mixture was cooled to room temperature, and centrifuged 3 times with absolute ethanol and distilled water.
(5) And (3) putting the solid powder obtained by centrifugation into a drying box, and drying for 24 hours at 70 ℃ to obtain the iron oxide nano-particle/flaky iron hydroxide/multi-layer graphene composite material.
A scan of the nano-iron oxide particles/flake iron hydroxide/multi-layered graphene obtained in example 1 is shown in fig. 1, in which fig. 1 (a) is a low-magnification SEM image thereof, and fig. 1 (b) is a high-magnification SEM image thereof. From the figure, it can be seen thatAnd the flaky ferric hydroxide is uniformly covered on the surface of the multilayer graphene. The XRD patterns of the nano-iron oxide particles/platelet-shaped iron hydroxide/multi-layered graphene obtained in example 1 are shown in FIG. 2, from which it can be seen that Fe (OH) appears at 14.2 °, 36.4 °, 38.0 °, 46.9 °, 60.2 ° 3 Diffraction peaks with matched crystal faces (PDF#38-0032) indicate that Fe (OH) is generated on the surface of graphene 3 . The TEM image of the nano-iron oxide particles/flaky iron hydroxide/multi-layered graphene obtained in example 1 is shown in FIG. 3, and it can be seen that two substances with different morphologies are attached to the surface of graphene, one of which is fine granular Fe 2 O 3 The lattice spacing is about 0.30nm as shown in FIG. 3 (b); the other material is flaky Fe (OH) 3 The lattice spacing is about 0.25nm as shown in FIG. 3 (c).
Specific example 2:
(1) Preparing a multi-layer graphene solution. 20mg of expanded graphite is weighed and added into a glass bottle, 8mL of DMF and 2mL of distilled water are measured by a cylinder and added into the bottle, the mixture is kept stand for 12 hours at room temperature, and the multi-layer graphene solution is obtained after ultrasonic treatment for 4 hours.
(2) Preparing the iron oxide nano-particle/flaky iron hydroxide particle composite material. 20mg of EDTA-2Na,100mg of FeCl were weighed out 2 And 30mg of CH 3 COONa is added into the multi-layer graphene solution, 20 mu L of alcohol is added, and the mixture is magnetically stirred for 10min to obtain a uniform mixed solution.
(3) The mixed solution is put into a water bath kettle and magnetically stirred for reaction for 2 hours at the constant temperature of 90 ℃.
(4) After the reaction was completed, the mixture was cooled to room temperature, and centrifuged 3 times with absolute ethanol and distilled water.
(5) And (3) putting the solid powder obtained by centrifugation into a drying box, and drying for 24 hours at 70 ℃ to obtain the iron oxide nano-particle/flaky iron hydroxide/multi-layer graphene composite material.
A scan of the nano-iron oxide particles/platelet-shaped iron hydroxide/multi-layered graphene obtained in example 2 is shown in fig. 4, where fig. 4 (a) is a low-magnification SEM image thereof, and fig. 4 (b) is a high-magnification SEM image thereof. From the figure, it can be seen that the graphene surface consists of ferric oxide nano particles and flaky ferric hydroxide, and flaky Fe (OH) 3 The gap between them is larger. Specific example 3:
(1) Preparing a multi-layer graphene solution. 20mg of expanded graphite is weighed and added into a glass bottle, 8mL of DMF and 2mL of distilled water are measured by a cylinder and added into the bottle, the mixture is kept stand for 12 hours at room temperature, and the multi-layer graphene solution is obtained after ultrasonic treatment for 4 hours.
(2) Preparing the iron oxide nano-particle/flaky iron hydroxide particle composite material. 20mg of EDTA-2Na,100mg of FeCl were weighed out 2 And 50mg of CH 3 COONa is added into the multi-layer graphene solution, 20 mu L of alcohol is added, and the mixture is magnetically stirred for 10min to obtain a uniform mixed solution.
(3) The mixed solution is put into a water bath kettle and magnetically stirred for reaction for 2 hours at the constant temperature of 90 ℃.
(4) After the reaction was completed, the mixture was cooled to room temperature, and centrifuged 3 times with absolute ethanol and distilled water.
(5) And (3) putting the solid powder obtained by centrifugation into a drying box, and drying for 24 hours at 70 ℃ to obtain the iron oxide nano-particle/flaky iron hydroxide/multi-layer graphene composite material.
A scan of the nano-iron oxide particles/platelet-shaped iron hydroxide/multi-layered graphene obtained in example 3 is shown in fig. 5, in which fig. 5 (a) is a low-magnification SEM image thereof and fig. 5 (b) is a high-magnification SEM image thereof. From the figure, it can be seen that the graphene surface consists of ferric oxide nano particles and flaky ferric hydroxide, and flaky Fe (OH) 3 The gap between them is larger.
The above description of the embodiments is only for aiding in the understanding of the method of the present invention and its core ideas. It should be noted that it will be apparent to those skilled in the art that various modifications and adaptations of the invention can be made without departing from the principles of the invention and these modifications and adaptations are intended to be within the scope of the invention as defined in the following claims.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (5)
1. The preparation method of the iron oxide nanoparticle/flaky iron hydroxide/multilayer graphene composite material is characterized by comprising the following steps of:
step S1: weighing expanded graphite, taking DMF and distilled water with the volume ratio of 8:2 as mixed solvents, sequentially adding the mixed solvents into a reaction glass bottle, standing for 12 hours at room temperature, and then carrying out ultrasonic treatment for 4 hours to obtain a multilayer graphene solution A; the concentration of the multilayer graphene relative to the mixed solvent of DMF and water is 2g/L;
step S2: weighing EDTA-2Na of 2g/L and CH of 1-5 g/L of the relative mixed solvent 3 COONa and 20g/L FeCl 2 Measuring absolute ethyl alcohol of which the volume is 1/500 of that of the mixed solvent, adding the absolute ethyl alcohol into the multilayer graphene solution A, and magnetically stirring the absolute ethyl alcohol for 10 minutes to obtain a uniform mixed solution B;
step S3: putting the mixed solution B into a water bath kettle, and magnetically stirring and reacting for 2 hours at the constant temperature of 90 ℃;
step S4: after the reaction is finished, cooling to room temperature, and centrifuging for 3 times by using absolute ethyl alcohol and distilled water respectively to obtain solid powder C;
step S5: and (3) putting the solid powder C obtained by centrifugation into a drying box, and drying for 24 hours at 70 ℃ to obtain the iron oxide nano-particle/flaky iron hydroxide/multi-layer graphene composite material.
2. The method for preparing iron oxide nanoparticle/flaky iron hydroxide/multi-layer graphene composite material according to claim 1, wherein a proper amount of EDTA-2Na and CH are added simultaneously into the reaction solution 3 COONa, the complex formed by iron self-assembles into a sheet, and finally forms a sheet iron hydroxide.
3. The method for preparing the iron oxide nanoparticle/flaky iron hydroxide/multi-layer graphene composite material according to claim 1, wherein the flaky iron hydroxide and the nano iron oxide particles on the surfaces of the multi-layer graphene are decomposed by iron hydroxide.
4. The method for preparing the iron oxide nanoparticle/flaky iron hydroxide/multi-layer graphene composite material according to claim 1, wherein a reaction system adopts a mixture of DMF and water, and the volume ratio of the DMF to the water is 8:2.
5. The method for preparing the iron oxide nanoparticle/flaky iron hydroxide/multi-layer graphene composite material according to claim 1, wherein flaky iron hydroxide grows on the bottom surface of the multi-layer graphene prepared by an ultrasonic method in the composite material prepared by the method, the flaky iron hydroxide forms a porous structure, and nano iron oxide is uniformly distributed on the surfaces of the multi-layer graphene and the flaky iron hydroxide.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106356525A (en) * | 2016-08-25 | 2017-01-25 | 陕西科技大学 | Method for preparing graphene in-situ growth FeOOH nano array lithium ion battery cathode material |
| CN107452943A (en) * | 2017-07-13 | 2017-12-08 | 陕西科技大学 | A kind of preparation method of graphene-supported ferriferous oxide self assembly class mulberries structure lithium ion battery negative material |
| CN108365192A (en) * | 2018-01-25 | 2018-08-03 | 陕西科技大学 | A kind of α-Fe2O3The preparation method of@alpha-feoohs/rGO composite cathode material for lithium ion cell |
| CN110474048A (en) * | 2019-07-24 | 2019-11-19 | 盐城师范学院 | A kind of preparation method of di-iron trioxide/fold graphene film material |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106356525A (en) * | 2016-08-25 | 2017-01-25 | 陕西科技大学 | Method for preparing graphene in-situ growth FeOOH nano array lithium ion battery cathode material |
| CN107452943A (en) * | 2017-07-13 | 2017-12-08 | 陕西科技大学 | A kind of preparation method of graphene-supported ferriferous oxide self assembly class mulberries structure lithium ion battery negative material |
| CN108365192A (en) * | 2018-01-25 | 2018-08-03 | 陕西科技大学 | A kind of α-Fe2O3The preparation method of@alpha-feoohs/rGO composite cathode material for lithium ion cell |
| CN110474048A (en) * | 2019-07-24 | 2019-11-19 | 盐城师范学院 | A kind of preparation method of di-iron trioxide/fold graphene film material |
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