CN106935826B - Preparation method of nano copper oxide graphene composite material for lithium ion battery - Google Patents
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 87
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 68
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 239000005751 Copper oxide Substances 0.000 title claims abstract description 28
- 229910000431 copper oxide Inorganic materials 0.000 title claims abstract description 28
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 16
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 16
- 239000002131 composite material Substances 0.000 title claims abstract description 15
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 61
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims abstract description 32
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 25
- QKSIFUGZHOUETI-UHFFFAOYSA-N copper;azane Chemical compound N.N.N.N.[Cu+2] QKSIFUGZHOUETI-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000006243 chemical reaction Methods 0.000 claims abstract description 19
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- 150000002910 rare earth metals Chemical class 0.000 claims description 45
- 239000010949 copper Substances 0.000 claims description 15
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 13
- 239000006185 dispersion Substances 0.000 claims description 13
- -1 rare earth compound Chemical class 0.000 claims description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 12
- 229910001868 water Inorganic materials 0.000 claims description 12
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 8
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 8
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 6
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 6
- 235000019270 ammonium chloride Nutrition 0.000 claims description 6
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- 229910017604 nitric acid Inorganic materials 0.000 claims description 6
- 239000002699 waste material Substances 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 3
- 229910052779 Neodymium Inorganic materials 0.000 claims description 3
- 229910052777 Praseodymium Inorganic materials 0.000 claims description 3
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 claims description 3
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 claims description 3
- 238000002791 soaking Methods 0.000 claims description 2
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- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 2
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(2+);cobalt(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 description 2
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- 229910052746 lanthanum Inorganic materials 0.000 description 2
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 2
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- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
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- 230000015556 catabolic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
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- 150000001768 cations Chemical class 0.000 description 1
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- 229910052739 hydrogen Inorganic materials 0.000 description 1
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- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
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- 230000014759 maintenance of location Effects 0.000 description 1
- GEYXPJBPASPPLI-UHFFFAOYSA-N manganese(III) oxide Inorganic materials O=[Mn]O[Mn]=O GEYXPJBPASPPLI-UHFFFAOYSA-N 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
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- 231100000956 nontoxicity Toxicity 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
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- 230000002195 synergetic effect Effects 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
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- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
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Abstract
The invention discloses a preparation method of a nano copper oxide graphene composite material for a lithium ion battery. Mixing the modified graphene solution and the copper ammonia solution according to the proportion of 1: 2-1: 5, magnetically stirring and carrying out ultrasonic treatment. And then transferring the mixture into a reaction kettle, keeping the temperature constant at 120-200 ℃ for 8-12h, naturally cooling, washing with deionized water, and putting the washed solid into a vacuum drying oven to finally obtain the product. The addition of the trace rare earth elements improves the surface structure of the graphene, reduces the agglomeration of the graphene, and obviously improves the capacitance performance of the nano copper oxide/graphene electrode material. The problems of poor conductivity, easy crushing, large charge-discharge volume change and poor cycle performance of the copper oxide/graphene electrode are effectively solved.
Description
Technical Field
The invention belongs to the technical field of lithium ion batteries, and relates to a preparation method of a nano copper oxide graphene composite material for a lithium ion battery.
Background
With the rapid development of global science and technology and economy, the human society has more and more demands on energy, especially fossil energy, and the energy economy faces serious examination. Meanwhile, environmental pollution caused by such fossil energy and global warming have attracted high attention from the international society. Improving energy utilization efficiency, optimizing energy structure, and reasonably developing and utilizing renewable energy sources will become a necessary choice for energy development. Electrochemical energy storage systems play a vital role in this process, such as batteries and supercapacitors. The lithium ion battery has the advantages of small volume, light weight, no memory effect, no environmental pollution, long cycle life, high working voltage, strong charge retention capacity, wide working temperature range and the like, and becomes a hot spot of new energy research of various countries in the world at present.
The key for improving and enhancing the performance of the lithium ion battery is to select a positive electrode material and a negative electrode material with good charge and discharge performance, and the traditional negative electrode material uses graphite, so that the requirement of the high-capacity battery is difficult to meet due to the low theoretical capacity of the graphite. In order to overcome the above defects, research on the negative electrode material of the lithium ion battery is mainly focused on non-carbon negative electrode materials, such as tin oxide, iron oxide, cobaltosic oxide, nickel oxide, manganic oxide and copper oxide. Wherein the theoretical capacity of copper oxide (670mAh g)-1) The material is high, is close to twice of a commercial graphite cathode, has high safety, low cost and environmental friendliness, is used as a cathode material of a lithium ion battery for a long time, and has wide application prospect. However, the main disadvantages of copper oxide are poor electrochemical activity and severe volume deformation during charge and discharge, which causes the copper oxide active material to be gradually crushed, resulting in rapid degradation of battery capacity.
Graphene is used as a two-dimensional nano material, and has the advantages of good dispersibility, high electron mobility, no toxicity, large specific surface area and the like, the composite material formed by the graphene and the metal oxide loaded on the graphene can show a synergistic effect under certain conditions, and when the composite material is applied to a negative electrode material of a lithium ion battery or a sodium ion battery, the copper oxide/graphene composite material can utilize the interface effect of the composite material to increase the storage density and the cycle stability of lithium (sodium) ions; in addition, the graphene has high carrier mobility, so that the graphene is very favorable for charge migration, and the charge and discharge rate of the battery is improved. However, graphene with a high specific surface area is easy to laminate and agglomerate due to high surface activity, strong intermolecular acting force and strong chemical bond action, so that the specific surface area is remarkably reduced, and the performance advantages of the graphene material such as high specific surface, high electric conductivity and high thermal conductivity cannot be fully exerted, which limits further application of the graphene material in lithium ion batteries to a certain extent.
Disclosure of Invention
In order to achieve the purpose, the invention provides a preparation method of a nano copper oxide/graphene composite material for a lithium ion battery, which solves the problems of poor conductivity, easy crushing, large charge-discharge volume change and poor cycle performance of a copper oxide/graphene electrode, improves the surface structure of graphene, reduces the agglomeration of graphene, and remarkably improves the capacitance performance of the nano copper oxide/graphene electrode material.
The technical scheme adopted by the invention is that the preparation method of the nano copper oxide graphene composite material for the lithium ion battery specifically comprises the following steps:
heating the rare earth solution in a water bath, and then adjusting the pH value of the rare earth solution to 5-6 to obtain a rare earth modified solution;
immersing graphene oxide into the rare earth modified solution at the temperature of 18-22 ℃ according to the proportion of 200-500 mg/mL, and performing ultrasonic dispersion to obtain a modified graphene oxide dispersion solution;
step 2, mixing (CH)3COO)2Cu·H2Mixing O with deionized water, and magnetically stirring for 10-30 minClock until (CH)3COO)2Cu·H2Completely dissolving O, wherein the mass concentration of the prepared copper acetate solution is 8-15%;
step 4, mixing the modified graphene oxide dispersion liquid prepared in the step 1 and a copper ammonia solution according to the mass ratio of 1: 2-1: 5, magnetically stirring for 1-3 hours, and then carrying out ultrasonic treatment;
step 5, transferring the solution obtained in the step 4 into a reaction kettle, keeping the temperature constant at 120-200 ℃ for 8-12 hours, naturally cooling to 18-22 ℃, taking out a sample, and washing with deionized water for multiple times until the pH of the washed waste liquid is neutral;
and 6, putting the washed solid into a vacuum drying oven for drying to obtain the catalyst.
Further, in the step 1, the rare earth solution is heated to 75-85 ℃ in a water bath, and the temperature is kept for 5-10 minutes.
Further, in the step 1, the pH value of the rare earth solution is adjusted to 5-6 by nitric acid.
Further, in the step 1, ultrasonic dispersion is performed for 3-6 hours, the power of the ultrasonic is 900-2000W, and the frequency is 20-75 KHz.
Further, in the step 1, the rare earth compound is a chloride of lanthanum, cerium, praseodymium or neodymium.
Further, in the step 3, the mass concentration of the ammonia water is 20-30%.
Further, in the step 4, ultrasonic treatment is carried out for 0.5-1 h, the ultrasonic power is 900-2000W, and the frequency is 20-75 KHz.
Further, in the step 6, the drying temperature is 60-80 ℃, and the drying time is 6-10 h.
The invention has the beneficial effects that:
(1) multiple experiments prove that the nano copper oxide/graphene electrode material prepared by the method is not broken after charging and discharging, and has good volume elastic buffering, so that the stability of the battery cathode is enhanced.
(2) The nano copper oxide/graphene electrode material prepared by the method solves the problem that graphene oxide is easy to agglomerate, can improve the cycle capacity and reversible capacity of a lithium ion battery, and can still keep the reversible capacity at 750mAhg after 100 cycles under the current density of 100mA/g-1And the coulombic efficiency is more than 95 percent, and the good cycling stability is shown.
(3) The nano copper oxide/graphene electrode material prepared by the method has the advantages of simple and feasible preparation process, environmental protection, rich raw materials, low price and good market prospect.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
Fig. 1 is an SEM image of graphene oxide before modification.
Fig. 2 is an SEM image of rare earth modified graphene oxide.
Fig. 3 is a graph of the cycling capacity of the copper oxide/graphene composite.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The preparation method of the nano copper oxide graphene composite material for the lithium ion battery specifically comprises the following steps:
The triethanolamine is added to mainly play a complexing role, and the component is selected according to the complexing effect.
And heating the rare earth solution to 75-85 ℃ in a water bath, preserving the heat for 5-10 minutes, and then adjusting the pH of the rare earth solution to 5-6 by using nitric acid to obtain the rare earth modified solution.
And (2) immersing graphene oxide into the rare earth modified solution at the temperature of 18-22 ℃ according to the proportion of 200-500 mg/mL, and performing ultrasonic dispersion for 3-6 hours at the ultrasonic power of 900-2000W and the frequency of 20-75 KHz to obtain the modified graphene oxide dispersion solution.
The selection of various components in the rare earth solution is obtained through a plurality of tests, and how to make the components out of the range, the modified graphene oxide has poor dispersibility. The water bath controls the temperature and time, on one hand, the decomposition of the organic solvent in the modifier is prevented, on the other hand, the stable water-soluble complex is formed by the ethylene diamine tetraacetic acid and the rare earth ions, and the chelation efficiency is higher. Ultrasonic dispersion pilot tests show that the reaction is not very complete, less than this parameter. Above this power range and time, the dispersion of the graphene is unchanged; when the power of the ultrasonic wave reaches a certain degree, the ultrasonic wave can play a role in catalyzing some chemical reactions.
Step 2, mixing (CH)3COO)2Cu·H2Mixing O and deionized water, and magnetically stirring for 10-30 minutes until (CH)3COO)2Cu·H2And (3) completely dissolving the O, wherein the mass concentration of the prepared copper acetate solution is 8-15%.
And 3, under the condition of continuously stirring by a magnetic stirrer, slowly dropwise adding strong ammonia water into the copper acetate solution obtained in the step 2 to generate a copper ammonia solution, and adjusting the pH value of the copper ammonia solution to 8-10.
And 4, mixing the modified graphene oxide dispersion liquid prepared in the step 1 with a copper ammonia solution according to a mass ratio of 1: 2-1: 5, magnetically stirring for 1-3 hours, and then carrying out ultrasonic treatment for 0.5-1 hour, wherein the ultrasonic power is 900-2000W, and the frequency is 20-75 KHz.
And 5, transferring the solution obtained in the step 4 into a reaction kettle, keeping the temperature of 120-200 ℃ for 8-12 hours, naturally cooling to 18-22 ℃, taking out a sample, and washing with deionized water for multiple times until the pH of the washed waste liquid is neutral.
And 6, putting the washed solid into a vacuum drying oven, and drying for 6-10 hours at the temperature of 60-80 ℃ to finally obtain the nano copper oxide/graphene electrode material.
Wherein, the rare earth compound in the step 1 is chloride of lanthanum, cerium, praseodymium or neodymium.
The graphene is in any one of a powder form, a flake form and a solution form. The purity of the graphene is more than or equal to 99.5%, the thickness of the graphene is 0.4-1.5 nm, and the size of the graphene is 1-8 mu m.
And 3, the mass concentration of the concentrated ammonia water in the step 3 is 20-30%.
Wherein, the mass concentration of the copper acetate solution in the step 2 is too large, the difficulty of magnetic stirring is increased, and the reaction is not thorough; the concentration is too low, and the concentration of the obtained copper ammonia solution cannot meet the requirement. In step 4, the graphene oxide contains a large amount of functional groups such as hydroxyl, carboxyl and oxygen-containing groups on the surface, and when the graphene oxide is dispersed and dissolved in a solvent such as water, the surface of a sheet layer of the graphene oxide is negatively charged. Cu (NH) can be converted according to the principle of electrostatic attraction3)+Cations are adsorbed on the surface of graphene oxide, and then oxygen-containing groups carried by graphene oxide are Cu (NH) which has certain oxidizability and reducibility with the graphene oxide3)+Under heating, Cu (NH)3)+And (3) generating CuO nanocrystalline in situ, and reducing the graphene oxide under the high-temperature reaction condition to remove a large amount of oxygen-containing functional groups on the surface of the graphene oxide to form graphene. In the step 5, the reaction in the reaction kettle has more factors, the reaction temperature is different according to the reaction time and the reaction type, and finally the reaction temperature is determined to be 120-200 ℃ through numerous experiments, and the reaction time is 8-12 h. In the step 6, the drying time is influenced by the drying temperature, the drying temperature is too low, the required drying time is correspondingly longer, and the drying effect does not necessarily meet the requirement; the drying temperature is too high, and the copper oxide is easily oxidized again.
The rare earth elements have a special electronic structure (-4 f)0-14) The determined chemical property is that in a complex system composed of typical nonmetal elements such as hydrogen, oxygen, nitrogen, carbon and the like, the atom size is required to be changed greatly due to the exchange of electrons and the polarization effect among atoms, and the rare earth is polarized to become an active element and can be used as a surfactant and a shallow infiltration element. The rare earth has low electronegativity and high activity, can not only clean the surface of graphene, but also form Re-C bonds or mix hybridization to ensure that the state of the graphene is more stable. The rare earth element serving as the surface active center can continue to perform a coordination chemical reaction with an organic active group in the rare earth modifier due to the high coordination number of the rare earth element, so that some organic active groups are introduced to the surface of the graphene oxide. In addition, ionized rare earth can penetrate into the defect position of graphene to generate a distortion region, and C is adsorbed in the distortion region, so that the dispersibility of the graphene can be improved, the reaction of the graphene and active groups can be promoted, and the bonding strength of the graphene and other substrates can be improved.
Example 1
Preparing a rare earth solution with ethanol as a solvent, wherein the mass fraction of each component of the rare earth solution is as follows: 0.05% of rare earth compound, 2.0% of ammonium chloride, 0.01% of urea and 0.4% of triethanolamine. And heating the rare earth solution to 75 ℃ in a water bath, preserving the heat for 10 minutes, and then adjusting the pH of the rare earth solution to 5 by using nitric acid to obtain the rare earth modified solution. And (3) immersing graphene oxide into the rare earth modified solution at the temperature of 18 ℃ according to the proportion of 200mg/mL, and performing ultrasonic dispersion for 3 hours at the ultrasonic power of 2000W and the frequency of 20KHz to obtain the modified graphene oxide dispersion solution. Will (CH)3COO)2Cu·H2O is mixed with deionized water and magnetically stirred for 10 minutes until (CH)3COO)2Cu·H2And O is completely dissolved, and the mass concentration of the prepared copper acetate solution is 8 percent. Under the condition of continuously stirring by a magnetic stirrer, slowly dropwise adding concentrated ammonia water with the mass concentration of 20% into the copper acetate solution to generate a copper ammonia solution, and adjusting the pH value of the copper ammonia solution to 8. Mixing the modified graphene oxide dispersion liquid and the copper ammonia solution according to the mass ratio of 1:2, and magnetically stirring for 1 hourThen ultrasonic treatment is carried out for 0.5h, the ultrasonic power is 900W, and the frequency is 75 KHz. And transferring the obtained solution into a reaction kettle, keeping the temperature of 120 ℃ for 12 hours, naturally cooling to 18 ℃, taking out a sample, and washing with deionized water for multiple times until the pH of the washed waste liquid is neutral. And (3) putting the washed solid into a vacuum drying oven, and drying at 60 ℃ for 10h to finally obtain the nano copper oxide/graphene electrode material.
Example 2
Preparing a rare earth solution with ethanol as a solvent, wherein the mass fraction of each component of the rare earth solution is as follows: 5.0 percent of rare earth compound, 0.1 percent of ammonium chloride, 2.0 percent of urea and 0.1 percent of triethanolamine. And heating the rare earth solution to 85 ℃ in a water bath, preserving the heat for 5 minutes, and then adjusting the pH of the rare earth solution to 6 by using nitric acid to obtain the rare earth modified solution. And (3) soaking the graphene oxide into the rare earth modified solution at the temperature of 22 ℃ according to the proportion of 500mg/mL, and performing ultrasonic dispersion for 6 hours at the ultrasonic power of 900W and the frequency of 75KHz to obtain the modified graphene oxide dispersion solution. Will (CH)3COO)2Cu·H2O is mixed with deionized water and magnetically stirred for 30 minutes until (CH)3COO)2Cu·H2And O is completely dissolved, and the mass concentration of the prepared copper acetate solution is 15%. Under the condition of continuously stirring by a magnetic stirrer, slowly dropwise adding concentrated ammonia water with the mass concentration of 30% into the copper acetate solution to generate a copper ammonia solution, and adjusting the pH value of the copper ammonia solution to 10. And mixing the modified graphene oxide dispersion liquid and the copper ammonia solution according to the mass ratio of 1:5, magnetically stirring for 3 hours, and then carrying out ultrasonic treatment for 0.5 hour, wherein the ultrasonic power is 2000W, and the frequency is 20 KHz. And transferring the obtained solution into a reaction kettle, keeping the temperature of the reaction kettle at 200 ℃ for 8 hours, naturally cooling the reaction kettle to 22 ℃, taking out a sample, and washing the sample for multiple times by using deionized water until the pH of the washed waste liquid is neutral. And (3) putting the washed solid into a vacuum drying oven, and drying for 6h at 80 ℃ to finally obtain the nano copper oxide/graphene electrode material.
Example 3
Preparing a rare earth solution with ethanol as a solvent, wherein the mass fraction of each component of the rare earth solution is as follows: 3% of rare earth compound, 1% of ammonium chloride, 1% of urea and 0.2% of triethanolamine. Subjecting the rare earth solution to waterHeating the bath to 80 ℃, preserving the heat for 7 minutes, and then adjusting the pH of the rare earth solution to 6 by using nitric acid to obtain the rare earth modified solution. And (3) immersing graphene oxide into the rare earth modified solution at the temperature of 20 ℃ according to the proportion of 300mg/mL, and performing ultrasonic dispersion for 4 hours at the ultrasonic power of 1500W and the frequency of 60KHz to obtain the modified graphene oxide dispersion solution. Will (CH)3COO)2Cu·H2O is mixed with deionized water and magnetically stirred for 20 minutes until (CH)3COO)2Cu·H2And O is completely dissolved, and the mass concentration of the prepared copper acetate solution is 12 percent. Under the condition of continuously stirring by a magnetic stirrer, slowly dropwise adding 25% concentrated ammonia water into the copper acetate solution to generate a copper ammonia solution, and adjusting the pH value of the copper ammonia solution to 9. And mixing the modified graphene oxide dispersion liquid and the copper ammonia solution according to the mass ratio of 1:3, magnetically stirring for 2 hours, and then carrying out ultrasonic treatment for 45 minutes, wherein the ultrasonic power is 1500W, and the frequency is 50 KHz. And transferring the obtained solution into a reaction kettle, keeping the temperature at 160 ℃ for 10 hours, naturally cooling to 20 ℃, taking out a sample, and washing with deionized water for multiple times until the pH of the washed waste liquid is neutral. And (3) putting the washed solid into a vacuum drying oven, and drying at 70 ℃ for 8h to finally obtain the nano copper oxide/graphene electrode material.
Fig. 1 is an SEM image of graphene oxide before modification, and it can be seen from the SEM image that graphene oxide without rare earth modification is relatively severely agglomerated, and a large number of graphene sheets are aggregated into a sphere.
Fig. 2 is an SEM image of rare earth modified graphene oxide in example 3, and it can be seen from the SEM image that after rare earth modification, a large number of graphene sheets are not aggregated together, but are dispersed uniformly, and exhibit good dispersibility.
FIG. 3 is a graph of the cycling capacity of the copper oxide/graphene composite at 100mAg-1Under the current density, after the circulation is carried out for 100 times, the reversible circulation capacity of the copper oxide/graphene composite material can still be kept at 750mAhg-1And the coulombic efficiency is more than 95 percent, and the stability is good.
The above description is only for the preferred embodiment of the present invention, and is not intended to limit the scope of the present invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention shall fall within the protection scope of the present invention.
Claims (1)
1. The preparation method of the nano copper oxide graphene composite material for the lithium ion battery is characterized by comprising the following steps of:
preparing a rare earth solution with ethanol as a solvent, wherein the mass fraction of each component of the rare earth solution is as follows: 3% of rare earth compound, 1% of ammonium chloride, 1% of urea and 0.2% of triethanolamine; the rare earth compound is a chloride of praseodymium or neodymium; heating the rare earth solution to 80 ℃ in a water bath, preserving the heat for 7 minutes, and then adjusting the pH of the rare earth solution to 6 by using nitric acid to obtain a rare earth modified solution; soaking graphene oxide into the rare earth modified solution at the temperature of 20 ℃ according to the proportion of 300mg/mL, and performing ultrasonic dispersion for 4 hours at the ultrasonic power of 1500W and the frequency of 60KHz to obtain a modified graphene oxide dispersion solution; will (CH)3COO)2Cu·H2O is mixed with deionized water and magnetically stirred for 20 minutes until (CH)3COO)2Cu·H2The O is completely dissolved, and the mass concentration of the prepared copper acetate solution is 12 percent; under the condition of continuously stirring by a magnetic stirrer, slowly dropwise adding 25% strong ammonia water to the copper acetate solution to generate a copper ammonia solution, and adjusting the pH value of the copper ammonia solution to 9; mixing the modified graphene oxide dispersion liquid and the copper ammonia solution according to the mass ratio of 1:3, magnetically stirring for 2 hours, and then carrying out ultrasonic treatment for 45 minutes, wherein the ultrasonic power is 1500W, and the frequency is 50 KHz; transferring the obtained solution into a reaction kettle, keeping the temperature at 160 ℃ for 10 hours, naturally cooling to 20 ℃, taking out a sample, and washing with deionized water for multiple times until the pH of the washed waste liquid is neutral; the washed solid was placed in a vacuum oven and dried at 70 ℃ for 8 h.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102584334A (en) * | 2012-01-13 | 2012-07-18 | 上海交通大学 | Method for preparing graphene composite thin film on surface of silicon slice |
| CN102765715A (en) * | 2012-07-12 | 2012-11-07 | 上海大学 | Graphene-loaded lamellar cupric oxide composite material and hydro-thermal synthesis method thereof |
| CN103474257A (en) * | 2013-09-16 | 2013-12-25 | 哈尔滨工程大学 | Preparation method for graphene oxide load cupric oxide lithium ion capacitor electrode materials |
| CN105944721A (en) * | 2016-05-11 | 2016-09-21 | 中国计量大学 | Hydrothermal preparation method of flaky nano copper oxide/graphene composite materials |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9663369B2 (en) * | 2011-12-16 | 2017-05-30 | International Business Machines Corporation | Cerium (IV) salts as effective dopant for carbon nanotubes and graphene |
| CN103956473B (en) * | 2014-05-20 | 2016-08-24 | 浙江师范大学 | A kind of CuO-Cu2o/ graphene nanocomposite material and preparation method thereof |
| CN106252675B (en) * | 2016-10-14 | 2019-02-19 | 济南大学 | A kind of CuO-NiO/rGO composite material having efficient electric catalytic oxidation-reduction performance |
-
2017
- 2017-03-23 CN CN201710179887.9A patent/CN106935826B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102584334A (en) * | 2012-01-13 | 2012-07-18 | 上海交通大学 | Method for preparing graphene composite thin film on surface of silicon slice |
| CN102765715A (en) * | 2012-07-12 | 2012-11-07 | 上海大学 | Graphene-loaded lamellar cupric oxide composite material and hydro-thermal synthesis method thereof |
| CN103474257A (en) * | 2013-09-16 | 2013-12-25 | 哈尔滨工程大学 | Preparation method for graphene oxide load cupric oxide lithium ion capacitor electrode materials |
| CN105944721A (en) * | 2016-05-11 | 2016-09-21 | 中国计量大学 | Hydrothermal preparation method of flaky nano copper oxide/graphene composite materials |
Non-Patent Citations (1)
| Title |
|---|
| "Graphene–CuO Nanocomposite";Nan Li等;《Journal of Nanoscience and Nanotechnology》;20101031;第10卷;第6690-6693页 * |
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