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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Abstract
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. 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 has controllability and excellent lyophilic property.
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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Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101774574A (en) * | 2010-01-22 | 2010-07-14 | 湘潭大学 | Preparation method of graphene inorganic nanocomposite |
| CN102184781A (en) * | 2011-03-03 | 2011-09-14 | 上海大学 | Nano-nickel oxide/graphene composite material and preparation method thereof |
| CN102941042A (en) * | 2012-10-25 | 2013-02-27 | 北京理工大学 | Graphene/metal oxide hybrid aerogel, preparation method and applications thereof |
| CN103157809A (en) * | 2013-02-05 | 2013-06-19 | 西南科技大学 | Preparation method of graphene/metal nanoparticle composite material with sandwich structure |
| CN105390676A (en) * | 2015-11-02 | 2016-03-09 | 北京师范大学 | Quick preparation method for graphene base metal or metal oxide with sandwich structure |
| CN106099063A (en) * | 2016-07-28 | 2016-11-09 | 广东工业大学 | A kind of Hydrothermal Synthesis metal-oxide/graphene nanocomposite material and its preparation method and application |
| CN106876670A (en) * | 2016-12-28 | 2017-06-20 | 广东工业大学 | The metal oxide of a kind of flexible self-supporting/graphene nano composite membrane and its preparation method and application |
| CN106935805A (en) * | 2017-04-07 | 2017-07-07 | 哈尔滨工业大学 | A kind of preparation method of di-iron trioxide/Graphene self-supporting electrode |
| CN107046126A (en) * | 2017-02-28 | 2017-08-15 | 中山大学 | A kind of preparation method of the two-dimentional anode material of super-fine metal oxide/graphene |
| CN107910515A (en) * | 2017-11-07 | 2018-04-13 | 大连理工大学 | A kind of Fe available for negative electrode of lithium ion battery3O4The preparation method of/nitrogen-doped graphene material |
| CN108539144A (en) * | 2018-03-12 | 2018-09-14 | 复旦大学 | A kind of extra small metal organic frame is nanocrystalline and preparation method and application |
| CN109449390A (en) * | 2018-10-08 | 2019-03-08 | 浙江衡远新能源科技有限公司 | A kind of iron oxide/graphene aerogel composite negative pole material and preparation method thereof |
| CN111554929A (en) * | 2020-05-06 | 2020-08-18 | 青岛科技大学 | Uniformly dispersed ultra-small metal nano particle material and dispersing method thereof |
-
2021
- 2021-07-30 CN CN202110868132.6A patent/CN113479871B/en active Active
Patent Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101774574A (en) * | 2010-01-22 | 2010-07-14 | 湘潭大学 | Preparation method of graphene inorganic nanocomposite |
| CN102184781A (en) * | 2011-03-03 | 2011-09-14 | 上海大学 | Nano-nickel oxide/graphene composite material and preparation method thereof |
| CN102941042A (en) * | 2012-10-25 | 2013-02-27 | 北京理工大学 | Graphene/metal oxide hybrid aerogel, preparation method and applications thereof |
| CN103157809A (en) * | 2013-02-05 | 2013-06-19 | 西南科技大学 | Preparation method of graphene/metal nanoparticle composite material with sandwich structure |
| CN105390676A (en) * | 2015-11-02 | 2016-03-09 | 北京师范大学 | Quick preparation method for graphene base metal or metal oxide with sandwich structure |
| CN106099063A (en) * | 2016-07-28 | 2016-11-09 | 广东工业大学 | A kind of Hydrothermal Synthesis metal-oxide/graphene nanocomposite material and its preparation method and application |
| CN106876670A (en) * | 2016-12-28 | 2017-06-20 | 广东工业大学 | The metal oxide of a kind of flexible self-supporting/graphene nano composite membrane and its preparation method and application |
| CN107046126A (en) * | 2017-02-28 | 2017-08-15 | 中山大学 | A kind of preparation method of the two-dimentional anode material of super-fine metal oxide/graphene |
| CN106935805A (en) * | 2017-04-07 | 2017-07-07 | 哈尔滨工业大学 | A kind of preparation method of di-iron trioxide/Graphene self-supporting electrode |
| CN107910515A (en) * | 2017-11-07 | 2018-04-13 | 大连理工大学 | A kind of Fe available for negative electrode of lithium ion battery3O4The preparation method of/nitrogen-doped graphene material |
| CN108539144A (en) * | 2018-03-12 | 2018-09-14 | 复旦大学 | A kind of extra small metal organic frame is nanocrystalline and preparation method and application |
| CN109449390A (en) * | 2018-10-08 | 2019-03-08 | 浙江衡远新能源科技有限公司 | A kind of iron oxide/graphene aerogel composite negative pole material and preparation method thereof |
| CN111554929A (en) * | 2020-05-06 | 2020-08-18 | 青岛科技大学 | Uniformly dispersed ultra-small metal nano particle material and dispersing method thereof |
Non-Patent Citations (1)
| Title |
|---|
| SHAOXIONG LIU EL AL.: "Novel Composites of α-Fe 2 O 3 Tetrakaidecahedron", 《ADVANCED FUNCTIONAL MATERIALS》 * |
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