CN103043729B - Cobalt molybdate-graphene nano compound and preparation method thereof - Google Patents
Cobalt molybdate-graphene nano compound and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a cobalt molybdate-graphene nano compound and a preparation method thereof. The method comprises steps of putting the oxidation graphite into water and ultrasonic dispersing; putting the cobalt salt into the system, stirring and dissolving; later putting the ammonium molybdate into the system and adjusting the pH; then transferring the mixture system into a water heating kettle to perform reaction; and when the reaction is ended, the product passes through separation, washing and dryness, and the cobalt molybdate-graphene nano compound is gained. The material is provided with broad application prospects in the field of energy and other electronic device fields.
Description
Technical field
The invention belongs to Nano-composite materials field, specifically relate to and a kind ofly take Graphene as propping material, and in the preparation method of finely dispersed cobalt molybdate nano particle, particularly cobalt molybdate-graphene nanometer composite of its surface deposition.This material has broad application prospects in the energy, sensing and other field of electronic devices.
Background technology
As the important member-cobalt molybdate of molybdate, because it has good chemical property, excellent stability, has started to be applied to the fields such as ultracapacitor, lithium ion battery.Up to the present, cobalt molybdate is also rarely had to report for the research of super capacitor.The methods such as the vertical strong people of grade of wheat first passage " self-assembly-orientation overlaps " cobalt molybdate of growing in manganese molybdate nanometer rod, and obtain cobalt molybdate (Mai LiQiang, the Yang Fan of nano-scale, Zhao YunLong, Xu Xu, Xu Lin, Luo YanZhu, S Hierarchical MnMoO
4/ CoMoO
4heterostructured nanowires with enhanced supercapacitor performance, Nature communications 2 (2011) 381).The method obtains the high area/volume ratio that material has, and is applied to electrical condenser, has obtained the electrode materials of the super capacitor of excellent performance.Graphene is SP
2the two-dimension graphite sheet existing with an atomic thickness that hydridization carbon atom forms according to honeycomb arrangement.Because its excellent electroconductibility (its electric transmission speed is than the fast decades of times of silicon), large specific surface area, thermal conductivity and mechanicalness etc. attract wide attention rapidly.Particularly, due to excellent conductivity and large specific surface area, Graphene is widely used in the research of ultracapacitor aspect.Both are compound to together, give full play to both advantages, thereby obtain the material of chemical property excellence, therefore prepare Graphene/cobalt molybdate matrix material very important, this material will be of great immediate significance and using value in ultracapacitor, lithium ion battery equal energy source field and other field of electronic devices.
Summary of the invention
The object of the present invention is to provide a kind of cobalt molybdate-graphene nanometer composite, and synthesis technique is simple, lower-cost hydrothermal method is prepared the preparation method of cobalt molybdate-graphene nanocomposite material.
The technical solution that realizes the object of the invention is: a kind of cobalt molybdate-graphene nanometer composite, massfraction 5 ~ 50 wt% of Graphene in described mixture.
A preparation method for cobalt molybdate-graphene nanometer composite, comprises the following steps:
The first step, by graphite oxide ultrasonic graphene oxide solution that disperses to obtain in water;
Second step, adds cobalt salt stirring and dissolving in the solution of the first step;
The 3rd step, joins molybdate in the mixed solution of second step, and stirs, and regulates pH value;
The 4th step, is transferred to the mixing solutions of the 3rd step in water heating kettle and reacts;
The 5th step, obtains cobalt molybdate-graphene nanometer composite by the 4th step product filtering separation and after washing, being dried.
Ultrasonic time described in step 1 is 60-120min, and described graphite oxide adopts Hummer legal system standby.
Cobalt salt described in step 2 is Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES, Cobaltous diacetate, cobalt chloride or rose vitriol, and described churning time is 30-90min.
Molybdate described in step 3 is ammonium paramolybdate, and the mol ratio of described molybdate and cobalt salt is 1:7, and churning time is 30-90min, described pH=6-11.
Temperature of reaction described in step 4 is 140-200 ℃, and the described reaction times is 6-16h.
Massfraction 5 ~ 50 wt% of Graphene in cobalt molybdate-graphene nanocomposite material described in step 5.
Compared with prior art, its advantage is in the present invention: (1) adopts Graphene is propping material, at the finely dispersed cobalt molybdate nano particle of its surface deposition, provides larger surface-area; (2) by hydro-thermal reaction, graphite oxide is reduced into Graphene, has avoided using other reductive agents, environmentally safe; (3) cobalt molybdate-Graphene of preparing of application the present invention, combines the characteristic of Graphene and cobalt molybdate, can be at ultracapacitor, lithium ion battery equal energy source material, and there are good application prospect and economic benefit in the field such as environment, life science.
Accompanying drawing explanation
Accompanying drawing 1 is route schematic diagram prepared by cobalt molybdate-graphene nanometer composite of the present invention.
Accompanying drawing 2 is TEM photos (a-embodiment 1, b-embodiment 2, c-embodiment 3, d-embodiment 4, e-embodiment 5) of example 1-5 gained cobalt molybdate-graphene nanocomposite material of the present invention.
Accompanying drawing 3 is example 3 gained cobalt molybdate-Graphenes of the present invention (27 wt%) nano-complex (G/CoMoO
4-1) with pure CoMoO
4cyclic voltammetric (a), alternating-current impedance (b), 0.5A/g constant current charge-discharge (c) and specific storage and sweep fast graph of a relation (d).
Embodiment
By reference to the accompanying drawings 1, cobalt molybdate-Graphene (5 ~ 50 wt%) nano-complex, by following steps, prepare and obtain:
The first step, by ultrasonic minute 60 ~ 120min during graphite oxide is in water, obtains graphene oxide solution;
Second step, adds Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES stirring and dissolving in the solution of the first step, churning time 30 ~ 90min;
The 3rd step, joins ammonium paramolybdate (mol ratio of paramolybdate and cobalt salt is 1:7) in the mixed solution of second step, and stirs 30 ~ 90min, regulates pH(6-11) value;
The 4th step, is transferred to the mixing solutions of the 3rd step in water heating kettle and reacts, and temperature of reaction is 140 ~ 200 ℃, reaction times 6 ~ 16h;
The 5th step, obtains cobalt molybdate-Graphene (5 ~ 50 wt%) nano-complex by the 4th step product filtering separation and after washing, being dried.
embodiment 1:the preparation method of cobalt molybdate-Graphene of the present invention (50 wt%) nano-complex, comprises the following steps:
The first step, adopts Hummer legal system for graphite oxide.10 g Graphite Powder 99s are joined to the Potassium Persulphate (5 g) of 80 ℃, in the concentrated sulfuric acid solution (15mL) of Vanadium Pentoxide in FLAKES (5g), preoxidation 6 hours, cool to room temperature, filters afterwards, and washing is to neutral.The Graphite Powder 99 of preoxidation (10 g) is joined in the 230 mL concentrated sulfuric acid solutions of 0 ℃, the careful potassium permanganate that adds 30g afterwards, afterwards in 35 ℃ of reaction 2h, in the most backward reaction solution, add 30% the hydrogen peroxide of 1L deionized water and 25mL to make reaction terminating, filter, washing, dialysis, makes graphite oxide; The graphite oxide of 80 mg is placed in to the ultrasonic dispersion of 80mL water 120min;
Second step, adds 0.366mmol Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES stirring and dissolving in the solution of the first step, stirs 50min;
The 3rd step, joins 0.052mmol ammonium paramolybdate in the mixed solution of second step, and stirs 90min, regulates pH=11 value;
The 4th step, is transferred to the mixing solutions of the 3rd step in water heating kettle and reacts, and temperature of reaction is 160 ℃, reaction times 12h;
The 5th step, obtains cobalt molybdate-Graphene (50 wt%) nano-complex by the 4th step product filtering separation and after washing, being dried.Its TEM photo is as Fig. 2 a.
embodiment 2:the preparation method of cobalt molybdate-Graphene of the present invention (42 wt%) nano-complex, comprises the following steps:
The first step, graphite oxide is prepared with embodiment 1, and the graphite oxide of 80 mg is placed in to the ultrasonic dispersion of 80mL water 60min;
Second step, adds 0.5mmol Cobaltous diacetate stirring and dissolving in the solution of the first step, stirs 90min;
The 3rd step, joins 0.071mmol ammonium paramolybdate in the mixed solution of second step, and stirs 30min, regulates pH=7 value;
The 4th step, is transferred to the mixing solutions of the 3rd step in water heating kettle and reacts, and temperature of reaction is 140 ℃, reaction times 16h;
The 5th step, obtains cobalt molybdate-Graphene (42 wt%) nano-complex by the 4th step product filtering separation and after washing, being dried.Its TEM photo is as Fig. 2 b.
embodiment 3:the preparation method of cobalt molybdate-Graphene of the present invention (27 wt%) nano-complex, comprises the following steps:
The first step, graphite oxide is prepared with embodiment 1, and the graphite oxide of 80 mg is placed in to the ultrasonic dispersion of 80mL water 90min;
Second step, adds 1mmol Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES stirring and dissolving in the solution of the first step, stirs 40min;
The 3rd step, joins 0.142mmol ammonium paramolybdate in the mixed solution of second step, and stirs 60min, regulates pH=7 value;
The 4th step, is transferred to the mixing solutions of the 3rd step in water heating kettle and reacts, and temperature of reaction is 180 ℃, reaction times 12h;
The 5th step, obtains cobalt molybdate-Graphene (27 wt%) nano-complex by the 4th step product filtering separation and after washing, being dried.Its TEM photo is as Fig. 2 c.
Gained matrix material is labeled as G/CoMoO
4-1, as electrode materials, under same test condition, the performance (accompanying drawing 3-c) of its electrochemistry cyclic voltammetric (accompanying drawing 3-a), alternating-current impedance (accompanying drawing 3-b), constant current charge-discharge and pure CoMoO
4compare, have higher ratio electric capacity, less internal resistance, longer discharge performance; The relation of its specific storage and scanning speed is as shown in accompanying drawing 3-d.
embodiment 4:the preparation method of cobalt molybdate-Graphene of the present invention (8 wt%) nano-complex, comprises the following steps:
The first step, graphite oxide is prepared with embodiment 1, and the graphite oxide of 80 mg is placed in to the ultrasonic dispersion of 80mL water 90min;
Second step, adds 4.203mmol rose vitriol stirring and dissolving in the solution of the first step, stirs 90min;
The 3rd step, joins 0.6mmol ammonium paramolybdate in the mixed solution of second step, and stirs 70min, regulates pH=9 value;
The 4th step, is transferred to the mixing solutions of the 3rd step in water heating kettle and reacts, and temperature of reaction is 160 ℃, reaction times 14h;
The 5th step, obtains cobalt molybdate-Graphene (8 wt%) nano-complex by the 4th step product filtering separation and after washing, being dried.Its TEM photo is as Fig. 2 d.
embodiment 5:the preparation method of cobalt molybdate-Graphene of the present invention (5 wt%) nano-complex, comprises the following steps:
The first step, graphite oxide is prepared with embodiment 1, and the graphite oxide of 80 mg is placed in to the ultrasonic dispersion of 80mL water 100min;
Second step, adds 6.945mmol cobalt chloride stirring and dissolving in the solution of the first step, stirs 30min;
The 3rd step, joins 0.992mmol ammonium paramolybdate in the mixed solution of second step, and stirs 90min, regulates pH(pH=6) value;
The 4th step, is transferred to the mixing solutions of the 3rd step in water heating kettle and reacts, and temperature of reaction is 200 ℃, reaction times 6h;
The 5th step, obtains cobalt molybdate-Graphene (5 wt%) nano-complex by the 4th step product filtering separation and after washing, being dried.Its TEM photo is as Fig. 2 d.
Claims (8)
1. cobalt molybdate-graphene nanometer composite, is characterized in that massfraction 5 ~ 50 wt% of Graphene in described mixture, and described mixture is prepared according to the following steps:
The 1st step, will adopt the standby graphite oxide ultrasonic graphene oxide solution that disperses to obtain in water of Hummer legal system;
The 2nd step, adds cobalt salt stirring and dissolving in the solution of the 1st step, and wherein, cobalt salt is Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES, Cobaltous diacetate, cobalt chloride or rose vitriol;
The 3rd step, joins molybdate in the mixed solution of the 2nd step, and stirs, and regulates pH value to 6-11, and wherein, molybdate is ammonium paramolybdate, and the mol ratio of molybdate and cobalt salt is 1:7;
The 4th step, is transferred to the mixing solutions of the 3rd step in water heating kettle and reacts 6-16h at 140-200 ℃;
The 5th step, obtains cobalt molybdate-graphene nanometer composite by the 4th step product filtering separation and after washing, being dried.
2. cobalt molybdate-graphene nanometer composite according to claim 1, is characterized in that the ultrasonic time described in step 1 is 60-120min.
3. cobalt molybdate-graphene nanometer composite according to claim 1, is characterized in that the churning time described in step 2 is 30-90min.
4. cobalt molybdate-graphene nanometer composite according to claim 1, is characterized in that the churning time described in step 3 is 30-90min.
5. a preparation method for cobalt molybdate-graphene nanometer composite, is characterized in that said method comprising the steps of:
The first step, will adopt the standby graphite oxide ultrasonic graphene oxide solution that disperses to obtain in water of Hummer legal system;
Second step, adds cobalt salt stirring and dissolving in the solution of the first step, and wherein, cobalt salt is Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES, Cobaltous diacetate, cobalt chloride or rose vitriol;
The 3rd step, joins molybdate in the mixed solution of second step, and stirs, and regulating pH value is 6-11, and wherein, molybdate is ammonium paramolybdate, and the mol ratio of molybdate and cobalt salt is 1:7;
The 4th step, is transferred to the mixing solutions of the 3rd step in water heating kettle and reacts 6-16h at 140-200 ℃;
The 5th step, obtains cobalt molybdate-graphene nanometer composite by the 4th step product filtering separation and after washing, being dried.
6. the preparation method of cobalt molybdate-graphene nanometer composite according to claim 5, is characterized in that the ultrasonic time described in step 1 is 60-120min.
7. the preparation method of cobalt molybdate-graphene nanometer composite according to claim 5, is characterized in that the churning time described in step 2 is 30-90min; Churning time described in step 3 is 30-90min.
8. the preparation method of cobalt molybdate-graphene nanometer composite according to claim 5, is characterized in that massfraction 5 ~ 50 wt% of Graphene in the cobalt molybdate-graphene nanocomposite material described in step 5.
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| CN103539210B (en) * | 2013-10-30 | 2015-10-28 | 渤海大学 | A kind of preparation method of cobalt molybdate crystallite |
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| CN103811189B (en) * | 2014-02-12 | 2016-08-17 | 东华大学 | A kind of cobalt molybdate and the preparation method of graphene nanocomposite material |
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| CN108336335B (en) * | 2018-02-05 | 2020-07-07 | 福州大学 | Cobalt molybdate/molybdenum disulfide composite material used as lithium ion battery negative electrode material and preparation thereof |
| CN108400319B (en) * | 2018-02-09 | 2021-02-05 | 厦门大学 | Preparation method of nano-structure cobalt molybdate electrode material |
| CN110544588A (en) * | 2019-08-22 | 2019-12-06 | 上海第二工业大学 | Cobalt molybdate/nitrogen functionalized graphene nanocomposite and preparation method thereof |
| CN111422855B (en) * | 2019-12-31 | 2021-08-27 | 北京理工大学 | Foam graphene-based metal azide compound and preparation method thereof |
| CN112875756B (en) * | 2021-02-19 | 2022-09-06 | 苏州科技大学 | Manganese molybdate nanoflower/graphene three-dimensional structure and high-specific-volume supercapacitor performance improvement method |
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