CN108666151B - Cobalt disulfide nanocrystalline/graphene composite electrode material and preparation method thereof - Google Patents
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Abstract
The invention discloses a cobalt disulfide nanocrystalline/graphene composite electrode material and a preparation method thereof. According to the cobalt disulfide nanocrystalline/graphene composite electrode material and the preparation method thereof, the two substances are compounded to obtain the novel composite electrode material with good structure optimization performance, the electrode material is low in cost, efficient to manufacture, uniform in crystal grain distribution and high in electrochemical capacity, and the electrode material has excellent conductivity, high specific surface area and good stability.
Description
Technical Field
The invention relates to the field of high-specific-capacity composite materials of lithium ion batteries, in particular to a cobalt disulfide nanocrystal/graphene composite electrode material and a preparation method thereof.
Background
The energy density of the traditional lithium ion battery can not meet the power consumption requirements of various electronic devices in daily life of human beings. Therefore, it is urgently required to improve the performance of the electrode material for lithium batteries.
Cobalt disulfide has low resistivity, good catalytic activity and chemical stability, but is easy to generate self-aggregation, and active sites cannot be fully exposed, so that the catalytic property and the cycling stability of energy storage are influenced. In the prior art, cobalt disulfide has the advantages of high specific capacity, easily available raw materials and rich sources, but the stability is poor, and the nanocrystalline with high conductivity and uniform distribution cannot be prepared. In the existing method for preparing the nanocrystalline, the size of the nanocrystalline is in the range of 1-10 nanometers, complex solution control is mostly involved, various organic and inorganic control ligands need to be added, and the crystalline form of the nanocrystalline is improved by a high-temperature calcination process of over 700 ℃ in the preparation method, so that the process is complex and the manufacturing cost is high.
In addition, the currently mature anode material is mainly iron disulfide. The greatest disadvantage of iron disulfide in thermal battery applications is its low thermal stability, which typically undergoes thermal decomposition at 550 ℃ to produce sulfur vapor, which readily reacts exothermically with the lithium alloy in the negative electrode to generate more heat, resulting in accelerated decomposition of iron disulfide and ultimately premature battery failure.
Therefore, the existing high specific capacity composite material technology of the lithium ion battery is still to be improved and developed.
Disclosure of Invention
The invention aims at the technical problems, and provides a cobalt disulfide nanocrystal/graphene composite electrode material and a preparation method thereof.
In a first aspect, the technical solution provided by the embodiments of the present invention is: the electrode material comprises a load framework of single-layer graphene, and a cobalt disulfide nanocrystalline layer and a single-layer graphene layer which are stacked on the upper and lower two-dimensional surfaces of the load framework layer by layer at intervals.
Wherein the cobalt disulfide nanocrystalline layer has cobalt disulfide nanocrystalline grains with a size of 1-10 nm.
In a second aspect, the technical solution provided by the embodiment of the present invention is: the preparation method of the cobalt disulfide nanocrystal/graphene composite electrode material comprises the following specific steps:
1) ultrasonically dispersing the prepared graphite oxide into deionized water to obtain a graphene oxide aqueous solution;
2) stirring and mixing ethanol and polyvinyl alcohol according to a set volume ratio to obtain a mixed solution, and dissolving cobalt dichloride in the mixed solution; stirring until the cobalt dichloride is completely dissolved to obtain a cobalt dichloride solution;
3) dropwise adding the graphene oxide aqueous solution obtained in the step 1) into the cobalt dichloride solution obtained in the step 2), stirring for a preset time, standing, and collecting a precipitate;
4) drying and grinding the precipitate obtained in the step 3) to obtain a precursor of the powdery compound;
5) annealing the precursor obtained in the step 4) at low temperature in a high vacuum environment to obtain the cobalt disulfide nanocrystalline/graphene composite electrode material.
Preferably, the graphite oxide prepared in step 1) is prepared by a modified Hummers method, and comprises the following steps:
uniformly mixing a certain amount of concentrated sulfuric acid and potassium persulfate, heating, adding 3 g of graphite powder to obtain a dark blue mixture, performing suction filtration and washing until the pH value is 5-12, and performing vacuum drying at 110 ℃ overnight;
weighing 2.5 g of pre-oxidized graphite, adding concentrated sulfuric acid under ice bath, slowly adding 10.5 g of potassium permanganate into the mixed solution, keeping the temperature below 20 ℃, stirring for 5 hours, adding deionized water, and adding 30% hydrogen peroxide until the reaction is finished; and
the obtained product is washed for 3 times by dilute hydrochloric acid and deionized water respectively, and is frozen and dried to obtain the graphite oxide.
Wherein the volume ratio of the ethanol to the polyvinyl alcohol in the mixed solvent obtained in the step 2) is 6: 1-1: 8.
Preferably, in the step 2), cobalt dichloride is dissolved in the mixed solvent, and the concentration of the cobalt dichloride is 0.08-0.2 g/ml.
In a preferred embodiment, the preparation method of the cobalt disulfide nanocrystal/graphene composite electrode material further comprises the step 2) of dissolving the propanetriamine and the thiourea in the mixed solution, wherein the molar concentration ratio of the propanetriamine and the thiourea is 0.5-50 when the propanetriamine and the thiourea are dissolved in the ethanol mixed solution.
Specifically, the stirring in step 3) is one or more of stirring mixing or ultrasonic treatment mixing, and the preset period of time of the stirring in step 3) is 0.5 to 20 hours of stirring.
Wherein, when the graphene oxide aqueous solution is dropwise added into the cobalt dichloride solution obtained in the step 2) in the step 3), the mass ratio of the graphene oxide to the cobalt dichloride is 3: 1-6: 1.
In specific implementation, the drying in the step 4) is one or more of freeze drying or vacuum drying; the annealing in the step 5) is to store the glass at a low temperature of less than 550 ℃ for 5 to 240 minutes in a vacuum environment with a vacuum degree of less than 100 pascals.
The beneficial effects of the embodiment of the invention are as follows: according to the cobalt disulfide nanocrystal/graphene composite electrode material and the preparation method, the cobalt disulfide nanocrystal/graphene composite electrode material with the size of 1-10 nanometers is prepared through vacuum low-temperature calcination. The composite electrode material and the preparation method compound the two substances, and the novel composite electrode material with optimized structure and good performance is obtained under a special process.
In addition, the thermal stability of the monomer cobalt disulfide is high and can reach more than 650 ℃, the resistivity of the monomer cobalt disulfide is 0.002 ohm cm and is far lower than that of iron disulfide, so that the ohmic polarization of the electrode can be reduced, and the specific surface area of the monomer cobalt disulfide can be increased due to the porous structure, so that the electrochemical polarization can be reduced. Compared with a cobalt disulfide monomer, the nanocrystalline/graphene composite electrode material prepared by the method has the following characteristics:
the preparation process is simple and economic, the cobalt disulfide nanocrystalline/graphene composite electrode material is prepared by a special process of wet chemical precipitation and low-temperature vacuum annealing, the cost is low, the synthesis process is simple, the preparation period is short, the efficiency is high, and the composite electrode material is green and non-toxic and has little environmental pollution.
The prepared cobalt disulfide nanocrystalline/graphene composite electrode material is structurally characterized in that a cobalt disulfide nanocrystalline layer is uniformly inlaid on a graphene layer through crystal grains, agglomeration of cobalt disulfide is inhibited, the material has a high specific surface area and uniform material distribution, and high-performance electrochemical performance is facilitated. Meanwhile, the graphene has excellent electrical conductivity, good thermal conductivity and mechanical properties, so that the structural stability and the electrical conductivity of the composite electrode material can be obviously improved, and the electrochemical performance of the material can be improved.
According to the cobalt disulfide nanocrystalline/graphene composite electrode material, 1-10 nanometer cobalt disulfide nanocrystalline grains are embedded on a two-dimensional material of a graphene layer, so that a material structure which is uniformly stacked and compounded at intervals is formed. The composite electrode material has excellent conductivity and high specific surface area, and meanwhile, the cobalt disulfide nano-crystal particles on the surface can enable the composite electrode material to have the performances of high electrochemical capacity, rapid rate energy storage, cycle stability and the like.
Drawings
Fig. 1 is a schematic view of a microscopic enlarged structure of a cobalt disulfide nanocrystal/graphene composite electrode material according to an embodiment of the invention;
fig. 2 is a schematic flow chart of a preparation method of a cobalt disulfide nanocrystal/graphene composite electrode material according to an embodiment of the invention;
FIG. 3 is a transmission electron microscope image of a cobalt disulfide nanocrystal/graphene composite electrode material according to an embodiment of the invention; and
fig. 4 is a charge and discharge performance diagram of the cobalt disulfide nanocrystal/graphene composite electrode material loaded with the graphene composite electrode material at an ambient temperature of 25 ℃ in the preparation method of the cobalt disulfide nanocrystal/graphene composite electrode material according to the embodiment of the invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the embodiments of the present invention are further described in detail below with reference to the accompanying drawings. The exemplary embodiments and descriptions of the present invention are provided to explain the present invention, but not to limit the present invention.
Example 1
The embodiment relates to a preparation method of a cobalt disulfide nanocrystalline/graphene composite electrode material, which is used for preparing the electrode material compounded by cobalt disulfide nanocrystalline particles and graphene, wherein the size of the electrode material is 1-10 nanometers through vacuum low-temperature calcination. The preparation method of the composite electrode material compounds two substances, namely cobalt disulfide nano-crystalline particles and single-layer graphene. The graphene is a single-layer graphite and is formed by hexagonal arrangement of carbon atoms, and has high internal carrier mobility, good thermal conductivity, high specific surface area and excellent mechanical strength. The graphene sheets have strong pi-pi interaction, and the sheets are easy to be stacked again to form a graphite-like structure. Pure cobalt disulfide has low resistivity, good catalytic activity and chemical stability, but is easy to generate self-aggregation, and active sites cannot be fully exposed, so that the catalytic property and the cycling stability of energy storage are influenced. The cobalt disulfide nano-crystalline and single-layer graphene composite electrode material has excellent conductivity, high porosity, high specific surface area and good stability, and can compound two substances and well combine the two substances.
Referring to fig. 2, the embodiment relates to a method for preparing a cobalt disulfide nanocrystal/graphene composite electrode material, which specifically comprises the following steps:
step 1: ultrasonically dispersing the prepared graphite oxide into deionized water to obtain a graphene oxide aqueous solution;
step 2: stirring and mixing ethanol and polyvinyl alcohol according to a set volume ratio to obtain a mixed solution, and dissolving cobalt dichloride in the mixed solution; stirring until the cobalt dichloride is completely dissolved to obtain a cobalt dichloride solution;
and step 3: dropwise adding the graphene oxide aqueous solution obtained in the step 1 into the cobalt dichloride solution obtained in the step 2, stirring for a preset time, standing, and collecting a precipitate;
and 4, step 4: drying and grinding the precipitate obtained in the step 3 to obtain a precursor of the powdery compound;
and 5: and (4) annealing the precursor obtained in the step (4) at a low temperature in a high vacuum environment to obtain the cobalt disulfide nanocrystalline/graphene composite electrode material.
The stirring in step 3) is one or more of stirring mixing or ultrasonic treatment mixing, and the preset stirring time of step 3) is 0.5-20 hours.
At present, there are mainly the following methods for preparing graphite oxide: the Brodie method, Staudenmier method and Hummers method. In this example, a modified Hummers method was used to prepare graphite oxide. The preparation of graphite oxide by the modified Hummers method comprises the following steps:
uniformly mixing a certain amount of concentrated sulfuric acid and potassium persulfate, heating, adding 3 g of graphite powder to obtain a dark blue mixture, performing suction filtration and washing until the pH value is 5-12, and performing vacuum drying at 110 ℃ overnight;
weighing 2.5 g of pre-oxidized graphite, adding concentrated sulfuric acid under ice bath, slowly adding 10.5 g of potassium permanganate into the mixed solution, keeping the temperature below 20 ℃, stirring for 5 hours, adding deionized water, and adding 30% hydrogen peroxide until the reaction is finished; and
the obtained product is washed for 3 times by dilute hydrochloric acid and deionized water respectively, and is frozen and dried to obtain the graphite oxide.
In a preferred embodiment, the preparation method of the cobalt disulfide nanocrystal/graphene composite electrode material further comprises the steps of dissolving the propanetriamine and the thiourea in the mixed solution in the step 2), and stirring until the propanetriamine and the thiourea are completely dissolved to obtain the cobalt dichloride solution; when the triamine and the thiourea are dissolved in the ethanol mixed solution, the molar concentration ratio is 0.5-50.
In specific implementation, the volume ratio of the ethanol to the polyvinyl alcohol in the mixed solvent obtained in the step 2) is 6: 1-1: 8.
In the step 2), cobalt dichloride is dissolved in the mixed solvent, wherein the concentration of the cobalt dichloride is 0.08-0.2 g/ml.
Wherein, when the graphene oxide aqueous solution is dropwise added into the cobalt dichloride solution obtained in the step 2) in the step 3), the mass ratio of the graphene oxide to the cobalt dichloride is 3: 1-6: 1.
In specific implementation, the drying in the step 4) is one or more of freeze drying or vacuum drying; the annealing in the step 5) is to store the glass at a low temperature of less than 550 ℃ for 5 to 240 minutes in a vacuum environment with a vacuum degree of less than 100 pascals.
Preparation method example 1
Preparing the cobalt disulfide nanocrystalline/graphene composite electrode material with the mass ratio of graphene oxide to cobalt dichloride being 3: 1.
Stirring and mixing the absolute ethyl alcohol and the polyvinyl alcohol uniformly according to the volume ratio of 6:1 to obtain a mixed solution. Taking 2 ml of mixed solution, dissolving 0.04 g of cobalt dichloride in the mixed solution, uniformly stirring, and slowly dripping 10 ml of graphene oxide, wherein the concentration of the graphene oxide is as follows: 3 mg/ml. Ultrasonically stirring for 1 hour, standing, centrifuging, collecting precipitate, washing with deionized water for several times, such as three times, and freeze drying to obtain composite precursor. And finally, preserving the heat for 0.5 hour at 350 ℃ in a vacuum environment of 40 pascals to obtain the cobalt disulfide nanocrystalline/graphene composite electrode material.
And adding carbon black and an adhesive into the collected product, grinding and uniformly mixing, coating the slurry on a copper foil, drying for 8 hours at 100 ℃, and then testing the electrochemical performance of the copper foil. Tests show that the cobalt disulfide nanocrystal/graphene composite electrode material has the specific capacity of 1000 mAh/g at 100 mA/g.
Preparation method example two
Preparing the cobalt disulfide nanocrystalline/graphene composite electrode material with the mass ratio of graphene oxide to cobalt dichloride being 5: 1.
Stirring and mixing the absolute ethyl alcohol and the polyvinyl alcohol uniformly according to the volume ratio of 1:1, and taking 4 ml of mixed solution. Then 0.2 g of cobalt dichloride is dissolved in the mixed solution, and after stirring for 5 hours, 40 ml of graphene oxide is slowly added dropwise, wherein the concentration of the graphene oxide is as follows: stirring the mixture for 2 hours by ultrasonic waves at a concentration of 25 m/ml, standing the mixture, centrifugally collecting precipitates, washing the precipitates for 3 times by using deionized water, and drying the precipitates in vacuum to obtain a precursor of the compound. And finally, preserving the heat for 2 hours at 300 ℃ in a vacuum atmosphere of 10 pascals to obtain the cobalt disulfide nanocrystalline/graphene composite electrode material.
And adding carbon black and an adhesive into the collected product, grinding and uniformly mixing, coating the slurry on a copper foil, drying for 8 hours at 100 ℃, and then testing the electrochemical performance of the copper foil. Tests show that the cobalt disulfide nanocrystal/graphene composite electrode material has specific capacity of 800 mAh/g at 200 mA/g.
Example 2
Referring to fig. 1 and fig. 3, the cobalt disulfide nanocrystal/graphene composite electrode material of the present embodiment includes a load skeleton 10 of single-layer graphene, and a cobalt disulfide nanocrystal layer 20 and a single-layer graphene layer 12 stacked on an upper and a lower two-dimensional surfaces of the load skeleton 10 at intervals layer by layer. The cobalt disulfide nanocrystalline layer 20 and the single graphene layer 12 are repeatedly stacked with the load skeleton 10 as the center, forming a novel composite electrode material.
Wherein the cobalt disulfide nanocrystalline layer has cobalt disulfide nanocrystalline grains with a size of 1-10 nm.
As shown in fig. 4, in the cobalt disulfide nanocrystal/graphene composite electrode material and the preparation method of the present embodiment, the cobalt disulfide nanocrystal/graphene composite electrode material with a size of 1-10 nm is prepared by vacuum low-temperature calcination. The composite electrode material and the preparation method compound the two substances, and the novel composite electrode material with optimized structure and good performance is obtained under a special process. The preparation process is simple and economic, the cobalt disulfide nanocrystalline/graphene composite electrode material is prepared by a special process of wet chemical precipitation and low-temperature vacuum annealing, the cost is low, the synthesis process is simple, the preparation period is short, the efficiency is high, and the composite electrode material is green and non-toxic and has little environmental pollution. The prepared cobalt disulfide nanocrystalline/graphene composite electrode material is structurally characterized in that a cobalt disulfide nanocrystalline layer is uniformly inlaid on a graphene layer through crystal grains, agglomeration of cobalt disulfide is inhibited, the material has a high specific surface area and uniform material distribution, and high-performance electrochemical performance is facilitated. Meanwhile, the graphene has excellent electrical conductivity, good thermal conductivity and mechanical properties, so that the structural stability and the electrical conductivity of the composite electrode material can be obviously improved, and the electrochemical performance of the material can be improved. According to the cobalt disulfide nanocrystalline/graphene composite electrode material, 1-10 nanometer cobalt disulfide nanocrystalline grains are embedded on a two-dimensional material of a graphene layer, so that a material structure which is uniformly stacked and compounded at intervals is formed. The composite electrode material has excellent conductivity and high specific surface area, and meanwhile, the cobalt disulfide nano-crystal particles on the surface can enable the composite electrode material to have the performances of high electrochemical capacity, rapid rate energy storage, cycle stability and the like.
The above description is only an embodiment of the present invention, and not intended to limit the scope of the present invention, and all modifications of equivalent structures and equivalent processes performed by the present specification and drawings, or directly or indirectly applied to other related technical fields, are included in the scope of the present invention.
Claims (7)
1. A preparation method of a cobalt disulfide nanocrystal/graphene composite electrode material is characterized by comprising the following specific steps:
1) ultrasonically dispersing the prepared graphite oxide into deionized water to obtain a graphene oxide aqueous solution;
2) stirring and mixing ethanol and polyvinyl alcohol according to a set volume ratio to obtain a mixed solution, dissolving the propanetriamine and the thiourea in the mixed solution, then dissolving the cobalt dichloride in the mixed solution, and stirring until the cobalt dichloride and the thiourea are completely dissolved to obtain a cobalt dichloride solution, wherein the molar concentration ratio of the propanetriamine and the thiourea is 0.5-50 when the propanetriamine and the thiourea are dissolved in the mixed solution;
3) dropwise adding the graphene oxide aqueous solution obtained in the step 1) into the cobalt dichloride solution obtained in the step 2), stirring for a preset time, standing, and collecting a precipitate;
4) drying and grinding the precipitate obtained in the step 3) to obtain a precursor of the powdery compound;
5) annealing the precursor obtained in the step 4) at low temperature in a high vacuum environment to obtain the cobalt disulfide nanocrystalline/graphene composite electrode material.
2. The preparation method of the cobalt disulfide nanocrystal/graphene composite electrode material as claimed in claim 1, wherein the graphite oxide prepared in step 1) is prepared by a modified Hummers method, and comprises the following steps:
uniformly mixing a certain amount of concentrated sulfuric acid and potassium persulfate, heating, adding 3 g of graphite powder to obtain a dark blue mixture, performing suction filtration and washing until the pH value is 5-12, and performing vacuum drying at 110 ℃ overnight;
weighing 2.5 g of pre-oxidized graphite, adding concentrated sulfuric acid under ice bath, slowly adding 10.5 g of potassium permanganate into the mixed solution, keeping the temperature below 20 ℃, stirring for 5 hours, adding deionized water, and adding 30% hydrogen peroxide until the reaction is finished; and
the obtained product is washed for 3 times by dilute hydrochloric acid and deionized water respectively, and is frozen and dried to obtain the graphite oxide.
3. The preparation method of the cobalt disulfide nanocrystal/graphene composite electrode material as claimed in claim 2, wherein the volume ratio of ethanol to polyvinyl alcohol in the mixed solvent obtained in step 2) is 6: 1-1: 8.
4. The preparation method of the cobalt disulfide nanocrystal/graphene composite electrode material as claimed in claim 3, wherein in step 2), cobalt dichloride is dissolved in the mixed solvent, and the concentration of the cobalt dichloride is 0.08-0.2 g/ml.
5. The method for preparing the cobalt disulfide nanocrystal/graphene composite electrode material as claimed in any one of claims 1 to 4, wherein the stirring in step 3) is one or more of stirring mixing or ultrasonic treatment mixing, and the preset stirring time in step 3) is 0.5 to 20 hours.
6. The preparation method of the cobalt disulfide nanocrystal/graphene composite electrode material as claimed in claim 5, wherein when the aqueous solution of graphene oxide is dropwise added into the cobalt dichloride solution obtained in step 2) in step 3), the mass ratio of graphene oxide to cobalt dichloride is 3: 1-6: 1.
7. The method for preparing a cobalt disulfide nanocrystal/graphene composite electrode material as claimed in claim 6, wherein the drying in step 4) is one or more of freeze drying or vacuum drying; the annealing in the step 5) is to store the glass at a low temperature of less than 550 ℃ for 5 to 240 minutes in a vacuum environment with a vacuum degree of less than 100 pascals.
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| Title |
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| "A free template strategy for the synthesis of CoS2-reduced graphene oxide nanocomposite with enhanced electrode performance for supercapacitors";Jianhua Tang等;《Ceramics International》;20140717;第40卷(第10期);第15411-15419页 * |
| "CoS2–graphene composite as efficient catalytic counter electrode for dye-sensitized solar cell";Xiaoli Duan等;《Electrochimica Acta》;20131022;第114卷;第173-179页 * |
| "Flaky CoS2 and graphene nanocomposite anode materials for sodium-ion batteries with improved performance";Zhiwei Li等;《RSC Advances》;20160721;第6卷(第74期);第70632-70637页 * |
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