CN113479871A - Preparation method of in-situ self-growth-based ultra-small metal oxide nanoparticle modified graphene - Google Patents
Preparation method of in-situ self-growth-based ultra-small metal oxide nanoparticle modified graphene Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical class [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 100
- 239000002105 nanoparticle Substances 0.000 title claims abstract description 49
- 229910044991 metal oxide Inorganic materials 0.000 title claims abstract description 47
- 150000004706 metal oxides Chemical class 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims abstract description 33
- 238000011065 in-situ storage Methods 0.000 title claims abstract description 20
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 49
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 36
- 229910052742 iron Inorganic materials 0.000 claims abstract description 23
- -1 iron ions Chemical class 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 15
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- 238000001354 calcination Methods 0.000 claims abstract description 8
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- 239000000243 solution Substances 0.000 claims description 20
- 239000007864 aqueous solution Substances 0.000 claims description 15
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- 239000007789 gas Substances 0.000 claims description 13
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- 239000011259 mixed solution Substances 0.000 claims description 8
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 8
- 239000006185 dispersion Substances 0.000 claims description 7
- 239000005457 ice water Substances 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
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- 239000000047 product Substances 0.000 claims description 5
- FFRBMBIXVSCUFS-UHFFFAOYSA-N 2,4-dinitro-1-naphthol Chemical compound C1=CC=C2C(O)=C([N+]([O-])=O)C=C([N+]([O-])=O)C2=C1 FFRBMBIXVSCUFS-UHFFFAOYSA-N 0.000 claims description 4
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 4
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- 238000010438 heat treatment Methods 0.000 claims description 4
- 238000000703 high-speed centrifugation Methods 0.000 claims description 4
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 4
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- 239000012286 potassium permanganate Substances 0.000 claims description 4
- 239000000843 powder Substances 0.000 claims description 4
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
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- 125000005842 heteroatom Chemical group 0.000 description 1
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- 238000009830 intercalation Methods 0.000 description 1
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- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- MHEBVKPOSBNNAC-UHFFFAOYSA-N potassium;bis(fluorosulfonyl)azanide Chemical compound [K+].FS(=O)(=O)[N-]S(F)(=O)=O MHEBVKPOSBNNAC-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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Abstract
本发明属于材料领域，具体涉及一种基于原位自生长的超小金属氧化物纳米颗粒改性石墨烯的制备方法，先利用静电吸附和配位络合作用在氧化石墨烯上均匀吸附铁离子，然后通过在保护气氛围下煅烧使铁离子原位自生长为嵌入在石墨烯层间的超小氧化铁纳米颗粒，精确控制石墨烯层间距的同时提高其亲液性。本发明优点：制备方法简单，原料廉价易得，制备过程能耗低，制备的改性石墨烯层间距具有可控性和优异亲液性。
The invention belongs to the field of materials, and in particular relates to a method for preparing ultra-small metal oxide nanoparticles modified graphene based on in-situ self-growth. , and then through calcination in a protective gas atmosphere, the iron ions are in-situ self-grown into ultra-small iron oxide nanoparticles embedded in the graphene layers, and the graphene layer spacing is precisely controlled while improving its lyophilicity. The invention has the advantages that the preparation method is simple, the raw materials are cheap and easy to obtain, the energy consumption in the preparation process is low, and the prepared modified graphene layer spacing has controllability and excellent lyophilicity.
Description
Technical Field
The invention belongs to the field of materials, and particularly relates to a preparation method of in-situ self-growth-based ultra-small metal oxide nanoparticle modified graphene.
Background
With the increasing demand for low-cost and high-power energy storage systems such as electric vehicles, mobile electronic products, and power grids, the Lithium Ion Battery (LIB) widely used at present faces a serious challenge of lithium resource scarcity. As a promising alternative, Potassium Ion Batteries (PIB) show great potential because they possess redox potentials similar to lithium. However, since the size of potassium ions is large relative to lithium ions, this increases the diffusion barrier of ions and slows down the electrochemical kinetics of potassium ion batteries, and causes excessive volume expansion and structural collapse of the electrode material during ion intercalation/deintercalation, thereby causing the electrode material to be detached from the electrode, and the battery performance to be greatly affected. In order to promote the development of potassium ion batteries, various strategies including introduction of hierarchical porosity, heteroatom doping, construction of complex nanostructures, and the like have recently been developed to precisely control the structure of carbon materials and improve the electrochemical performance of potassium ion batteries. However, for PIB, the current modification strategy is at capacity (below 400mAh g)-1) Satisfactory progress has not been made in rate performance and cycle stability. Therefore, it remains a great challenge to develop high performance electrode materials that can be used as potassium ion batteries.
Due to the advantages of large specific surface area, high conductivity, excellent chemical stability and the like, the graphene can be widely applied to a plurality of fields such as water body treatment, flexible wearable devices, super capacitors, batteries and the like. In the field of batteries in particular, as far as current progress is concerned, precise control of the microstructure of materials at the molecular and nano-level is the key to advance the development of electrochemical properties and to discover new energy storage mechanisms, but there is still much room for exploration.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a preparation method of ultra-small metal oxide nanoparticle modified graphene based on in-situ self-growth, which starts from the angle of regulating and controlling the distance between graphene layers, and successfully embeds metal oxide nanoparticles between the graphene layers by utilizing an in-situ self-growth strategy to prepare the ultra-small metal oxide nanoparticle modified graphene aerogel, so that the graphene has excellent lyophilic property while the distance between layers is expanded.
In order to achieve the technical purpose, the technical scheme of the invention is as follows:
a preparation method of in-situ self-growth based ultra-small metal oxide nanoparticle modified graphene comprises the following steps:
The preparation method in the step 1 adopts an improved Hummers method for preparation, and specifically comprises the following steps: a1, adding concentrated sulfuric acid and sodium nitrate powder into natural crystalline flake graphite powder, slowly adding potassium permanganate into a cold water bath, and stirring in a constant-temperature water bath for 0.5-3 h; 2, continuously reacting a small amount of distilled water for 10-30min, adding a large amount of distilled water, reacting for 5-20min, and adding a hydrogen peroxide solution until the solution is golden yellow; a3, removing supernatant after the solution is kept stand and settled, then adding 10% hydrochloric acid, removing supernatant after high-speed centrifugation, and then washing with water to be neutral to obtain a precipitate; a4, adding the precipitation product into deionized water for ultrasonic dispersion, then centrifuging at low speed, and taking supernatant to obtain the graphene oxide aqueous solution.
The preparation method of the step 2 comprises the steps of mixing ferric chloride solution and graphene oxide dispersion liquid drop by drop in an ice-water bath; and centrifuging the mixed solution at low temperature, washing the solution for 3 to 5 times by using deionized water, and freeze-drying the solution for 12 to 48 times to obtain the iron ion/graphene oxide precursor aerogel.
The preparation method of the step 3 comprises the following steps: and putting the iron ion/graphene oxide precursor aerogel into a tubular furnace, and calcining for 1-10h in a protective gas atmosphere to obtain the ultra-small metal oxide nanoparticle modified graphene aerogel. The protective gas is nitrogen, argon or nitrogen-argon mixture gas. The temperature of the tubular furnace is 100-1000 ℃, and the heating rate of the tubular furnace is 5-15 ℃/min.
The ultra-small metal oxide nanoparticle modified graphene aerogel is used as a raw material for a negative electrode material.
The anode material does not need additional conductive additives and binders.
The ultra-small metal oxide nanoparticle modified graphene electrode material is applied to an alkali metal ion battery.
From the above description, it can be seen that the present invention has the following advantages:
1. the preparation method starts from the angle of regulating the graphene layer spacing, and utilizes an in-situ self-growth strategy to successfully embed the metal oxide nanoparticles between the graphene layers to prepare the ultra-small metal oxide nanoparticle modified graphene aerogel, so that the graphene has excellent lyophilic property while having the expanded layer spacing.
2. According to the method, based on the fact that positively charged metal ions can be adsorbed with oxygen-containing functional groups on the surface of graphene oxide, iron ions are tightly adsorbed on the graphene, and the graphene is freeze-dried to obtain Fe3+GO aerogel.
3. In the invention, Fe3+And calcining the/GO aerogel in a protective gas environment to promote the in-situ self-growth of iron ions into iron oxide nanoparticles embedded between graphene layers.
4. The preparation method is simple, the raw materials are cheap and easy to obtain, the prepared metal oxide nanoparticles are small in size and controllable in graphene layer spacing, and have excellent lyophilic property, meanwhile, the metal oxide nanoparticles are used as self-supporting flexible electrodes and show excellent rate performance and cycle stability, and a basis is provided for reasonable design of high-performance electrode materials.
Drawings
Fig. 1 is a transmission electron microscope picture of ultra-small metal oxide nanoparticle modified graphene.
Fig. 2 is a high-resolution transmission electron microscope picture of ultra-small metal oxide nanoparticle modified graphene.
FIG. 3 shows a half-cell assembly of ultra-small metal oxide nanoparticle modified graphene and potassium sheets at 0.1A g-1The specific capacity of the charge-discharge curve at current density was calculated based on the total electrode mass.
FIG. 4 shows the assembly of ultra-small metal oxide nanoparticles modified graphene and potassium sheets into a half-cell at 1A g-1The following cyclic charge and discharge capacity retention curves, the specific capacities were calculated based on the total electrode mass.
Detailed Description
An embodiment of the present invention is described in detail with reference to fig. 1 to 4, but the present invention is not limited in any way by the claims.
A preparation method of ultra-small metal oxide nanoparticle modified graphene comprises the following specific steps:
(1) preparing a graphene oxide aqueous solution by using an improved Hummers method:
the preparation method is an improved Hummers method, namely 1-3g of 325-mesh natural crystalline flake graphite powder is taken, 0.5-2g of sodium nitrate powder and 25-120ml of concentrated sulfuric acid are added, 3-9g of potassium permanganate are slowly added in a cold water bath, the mixture is stirred for 0.5-3h in a water bath at the temperature of 30-40 ℃, then a small amount of water is added, the reaction is continued for 10-30min, more than 100ml of a large amount of water is added, the reaction is carried out for 5-20min, and then a proper amount of hydrogen peroxide is added until the solution turns golden yellow;
standing the solution, settling, then separating out to remove supernatant, adding a proper amount of 10% hydrochloric acid, subpackaging the solution into a centrifuge tube, performing high-speed centrifugation (10000 plus 12000r/min), discarding the supernatant, subsequently washing the solution to neutrality by deionized water, collecting products after washing, adding a proper amount of deionized water, performing ultrasonic dispersion, and performing low-speed centrifugation (2000 plus 5000r/min) to obtain supernatant, namely the Graphene Oxide (GO) aqueous solution;
(2) preparation of iron ion/graphene oxide (Fe)3+GO) aerogels:
5-20mL FeCl was added at low temperature (in an ice-water bath)3Aqueous solution (0.01-0.2mol L)-1) With 4-40mL GO dispersion (0.1-2mg mL)-1) Dropwise mixing; centrifuging and washing the mixed solution with deionized water at low temperature for 3-5 times, and freeze-drying for 12-48 hours to obtain iron ion/graphene oxide precursor (Fe)3+/GO) aerogels.
(3) Preparing an ultra-small metal oxide nanoparticle modified graphene (OM-G) aerogel:
raising the temperature of the tubular furnace to 100-1000 ℃, simultaneously opening the protective gas valve, and calcining the Fe obtained in the step (2) at the temperature of 100-1000 ℃ in the protective gas atmosphere3+the/GO aerogel is used for 1-10h to obtain the ultra-small metal oxide nanoparticle modified graphene (OM-G) aerogel. The protective gas is nitrogen, argon or a nitrogen-argon mixed gas. The temperature rise rate of the tubular furnace is 5-15 ℃/min.
Example 1
In-situ self-growth-based ultra-small metal oxide nanoparticle modified graphene aerogel
(1) Preparing a graphene oxide precursor:
the preparation method is an improved Hummers method, namely 3g of 325-mesh graphite powder is taken, 2g of sodium nitrate powder and 120mL of concentrated sulfuric acid are added, 9g of potassium permanganate is slowly added in a cold water bath, the mixture is stirred for-3 h in a water bath at the temperature of 40 ℃, then a small amount of water is added, the reaction is continued for 30min, a large amount of 100mL of water is added, the reaction is carried out for 20min, and then a proper amount of hydrogen peroxide is added until the solution turns golden yellow.
Standing the solution, settling, then, removing supernatant, adding a proper amount of 10% hydrochloric acid, subpackaging the solution into a centrifuge tube, performing high-speed centrifugation (12000r/min), removing the supernatant, then, washing the solution to be neutral by deionized water, collecting products after washing, adding a proper amount of deionized water, performing ultrasonic dispersion, and performing low-speed centrifugation (5000r/min) to obtain supernatant, namely, a Graphene Oxide (GO) aqueous solution;
(2) preparation of iron ion/graphene oxide (Fe)3+GO) aerogels:
20mL FeCl was added at low temperature (in an ice water bath)3Aqueous solution (0.2mol L)-1) With 40mL GO dispersion (2mg mL)-1) Dropwise mixing; the mixed solution was centrifuged and washed 5 times with deionized water at low temperature, and then freeze-dried for 12 hours to obtain iron ions/graphite oxideAlkene precursor (Fe)3+/GO) aerogels.
(3) Preparing an ultra-small metal oxide nanoparticle modified graphene (OM-G) aerogel:
raising the temperature of the tube furnace to 1000 ℃, simultaneously opening a protective gas valve, and calcining the Fe obtained in the step (2) at the temperature of 1000 ℃ in a protective gas atmosphere3+the/GO aerogel is used for 10h to obtain the ultra-small metal oxide nanoparticle modified graphene (OM-G) aerogel.
FIG. 1 is a transmission electron microscope picture of ultra-small metal oxide nanoparticle modified graphene, from which it can be seen that Fe with a particle size of 3nm2O3The nanoparticles are uniformly distributed on the graphene. FIG. 2 is a high resolution TEM image of ultra-small metal oxide nanoparticle modified graphene, which can be seen from Fe2O3The graphene layer spacing after nanoparticle modification can be as high as 0.407 nm.
(4) The obtained ultra-small metal oxide nanoparticle modified graphene aerogel is used as a negative electrode material and is assembled with a potassium sheet in a glove box to form a half cell, a CR2032 coin-type cell shell is used, the potassium sheet is used as a negative electrode, the prepared material is used as a positive electrode, a mixed solution of 1M KFSI Ethylene Carbonate (EC) and diethyl carbonate (DEC) (volume ratio of 1:1) is used as an electrolyte, and glass fiber is used as a diaphragm to assemble the potassium ion half cell. During assembly, the water oxygen value of the glove box is less than 0.01ppm
FIG. 3 shows the half cell at a current density of 0.1A g-1Constant current charging and discharging curve, 0.1A g-1The specific discharge capacity reaches 530.0mAh g-1. FIG. 4 shows a half cell at 1A g-1The specific capacity retention rate after 2000 cycles is 96.3 percent according to a cyclic charge-discharge capacity retention curve.
Example 2:
1.5mg/mL GO aqueous solution was obtained as in example 1 above, and 15mL of 0.1M FeCl was added in an ice-water bath3The aqueous solution was mixed dropwise with 40mL GO dispersion (1.5mg/mL), the mixed solution was centrifuged and washed 3-5 times with deionized water at low temperature, and then the purified mixture was freeze-dried for 24h to obtain iron ions/graphene oxide precursor (Fe)3+/GO) aerogels. Iron ion/graphene oxide precursor (Fe)3+/GO) aerogel in a tube furnace at N2At 10 deg.C for min in atmosphere-1The heating rate is annealed for 2 hours at 400 ℃ to obtain the ultra-small metal oxide nanoparticle modified graphene (OM-G).
Example 3:
1.0mg/mL GO aqueous solution was obtained as in example 1 above, and 15mL of 0.1M FeCl was added in an ice-water bath3The aqueous solution was mixed dropwise with 40mL GO dispersion (1.5mg/mL), the mixed solution was centrifuged and washed 3-5 times with deionized water at low temperature, and then the purified mixture was freeze-dried for 24h to obtain iron ions/graphene oxide precursor (Fe)3+/GO) aerogels. Iron ion/graphene oxide precursor (Fe)3+/GO) aerogel in a tube furnace at N2At 10 deg.C for min in atmosphere-1The heating rate is annealed for 2 hours at 400 ℃ to obtain the ultra-small metal oxide nanoparticle modified graphene (OM-G).
Example 4:
1.0mg/mL GO aqueous solution was obtained as in example 1 above, and 15mL of 0.1M FeCl was added in an ice-water bath3The aqueous solution was mixed dropwise with 40mL GO dispersion (1.5mg/mL), the mixed solution was centrifuged and washed 3-5 times with deionized water at low temperature, and then the purified mixture was freeze-dried for 24h to obtain iron ions/graphene oxide precursor (Fe)3+/GO) aerogels. Iron ion/graphene oxide precursor (Fe)3+/GO) aerogel in a tube furnace at N2At 10 deg.C for min in atmosphere-1Annealing at 300 ℃ for 2h to obtain the ultra-small metal oxide nanoparticle modified graphene (OM-G).
It should be understood that the detailed description of the invention is merely illustrative of the invention and is not intended to limit the invention to the specific embodiments described. It will be appreciated by those skilled in the art that the present invention may be modified or substituted equally as well to achieve the same technical result; as long as the use requirements are met, the method is within the protection scope of the invention.
Claims (9)
1. A preparation method of in-situ self-growth based ultra-small metal oxide nanoparticle modified graphene is characterized by comprising the following steps: the method comprises the following steps:
step 1, preparing graphene oxide: preparing a graphene oxide aqueous solution by taking natural crystalline flake graphite powder as a raw material;
step 2, preparing the iron ion/graphene oxide aerogel: preparing iron ions/graphene oxide aerogel at low temperature by taking ferric chloride solution and graphene oxide as raw materials.
Step 3, preparing the ultra-small metal oxide nanoparticle modified graphene aerogel: and calcining the iron ion/graphene oxide aerogel to form the ultra-small metal oxide nanoparticle modified graphene aerogel.
2. The preparation method of in-situ self-growth based ultra-small metal oxide nanoparticle modified graphene according to claim 1, wherein the preparation method comprises the following steps: the preparation method in the step 1 adopts an improved Hummers method for preparation, and specifically comprises the following steps: a1, adding concentrated sulfuric acid and sodium nitrate powder into natural crystalline flake graphite powder, slowly adding potassium permanganate into a cold water bath, and stirring in a constant-temperature water bath for 0.5-3 h; 2, continuously reacting a small amount of distilled water for 10-30min, adding a large amount of distilled water, reacting for 5-20min, and adding a hydrogen peroxide solution until the solution is golden yellow; a3, removing supernatant after the solution is kept stand and settled, then adding 10% hydrochloric acid, removing supernatant after high-speed centrifugation, and then washing with water to be neutral to obtain a precipitate; a4, adding the precipitation product into deionized water for ultrasonic dispersion, then centrifuging at low speed, and taking supernatant to obtain the graphene oxide aqueous solution.
3. The preparation method of in-situ self-growth based ultra-small metal oxide nanoparticle modified graphene according to claim 1, wherein the preparation method comprises the following steps: the preparation method of the step 2 comprises the steps of mixing ferric chloride solution and graphene oxide dispersion liquid drop by drop in an ice-water bath; and centrifuging the mixed solution at low temperature, washing the solution for 3 to 5 times by using deionized water, and freeze-drying the solution for 12 to 48 times to obtain the iron ion/graphene oxide precursor aerogel.
4. The preparation method of in-situ self-growth based ultra-small metal oxide nanoparticle modified graphene according to claim 1, wherein the preparation method comprises the following steps: the preparation method of the step 3 comprises the following steps: and putting the iron ion/graphene oxide precursor aerogel into a tubular furnace, and calcining for 1-10h in a protective gas atmosphere to obtain the ultra-small metal oxide nanoparticle modified graphene aerogel.
5. The method for preparing in-situ self-growth based ultra-small metal oxide nanoparticle modified graphene according to claim 4, wherein the method comprises the following steps: the protective gas is nitrogen, argon or nitrogen-argon mixture gas.
6. The method for preparing in-situ self-growth based ultra-small metal oxide nanoparticle modified graphene according to claim 4, wherein the method comprises the following steps: the temperature of the tubular furnace is 100-1000 ℃, and the heating rate of the tubular furnace is 5-15 ℃/min.
7. The preparation method of in-situ self-growth based ultra-small metal oxide nanoparticle modified graphene according to claim 1, wherein the preparation method comprises the following steps: the ultra-small metal oxide nanoparticle modified graphene aerogel is used as a raw material for a negative electrode material.
8. The method for preparing in-situ self-growth based ultra-small metal oxide nanoparticle modified graphene according to claim 7, wherein the method comprises the following steps: the anode material does not need additional conductive additives and binders.
9. The preparation method of in-situ self-growth based ultra-small metal oxide nanoparticle modified graphene according to claim 1, wherein the preparation method comprises the following steps: the ultra-small metal oxide nanoparticle modified graphene electrode material is applied to an alkali metal ion battery.
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