CN113830755B - Method for electrochemically preparing cobalt simple substance-graphene intercalation compound by one-step method - Google Patents
Method for electrochemically preparing cobalt simple substance-graphene intercalation compound by one-step method Download PDFInfo
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- CN113830755B CN113830755B CN202111076773.4A CN202111076773A CN113830755B CN 113830755 B CN113830755 B CN 113830755B CN 202111076773 A CN202111076773 A CN 202111076773A CN 113830755 B CN113830755 B CN 113830755B
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/184—Preparation
- C01B32/19—Preparation by exfoliation
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
- C25C1/06—Electrolytic production, recovery or refining of metals by electrolysis of solutions or iron group metals, refractory metals or manganese
- C25C1/08—Electrolytic production, recovery or refining of metals by electrolysis of solutions or iron group metals, refractory metals or manganese of nickel or cobalt
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- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
Abstract
The invention discloses a method for electrochemically preparing a cobalt simple substance-graphene intercalation compound by a one-step method. According to the method, an anode electrochemical stripping method is adopted, firstly, hexanitrocobalt anions are intercalated into a graphite layer and then subjected to electrochemical reaction, so that stripped graphite particles are suspended in electrolyte and gradually migrate to a cathode to undergo reduction reaction, and finally cobalt ions in the layer are reduced into cobalt simple substances. Compared with the stripping mode of high-voltage excited plasmas in the prior art, the invention adopts double graphite sheets to replace noble metal pole pieces, and uses water electrolyte, thereby avoiding the use of expensive pollution solutions such as organic solvents, ionic liquids and the like. The electrolyte in the acidic environment can keep the stability of sodium hexanitrocobaltate anions; anionic surfactants can enhance the wettability and dispersibility of anions. The invention has the advantages of mild stripping conditions, low equipment requirement, low energy consumption, simple operation and short stripping time, and accords with a green chemical synthesis route.
Description
Technical field:
the invention belongs to the technical field of carbon composite material preparation, and particularly relates to a method for electrochemically preparing a cobalt simple substance-graphene intercalation compound (Co-GIC) by a one-step method.
The background technology is as follows:
with the increasing sharpness of energy problems and environmental pollution problems, people pursue a cheap, green and environment-friendly synthetic route in the preparation of materials. And the graphene intercalation compound has great potential application value in the fields of catalysts, magnetic materials, conductive materials, secondary batteries and the like, and the short plates are prepared. Thus, a preparation method of a cobalt simple substance-graphene intercalation compound (Co-GIC) has attracted a great deal of attention.
The current preparation method of Co-GIC is mainly a Co-reduction method, which requires that Graphene Oxide (GO) is prepared by a Hummer method, in order to introduce more oxygen-containing functional groups such as carboxyl, hydroxyl and the like on the surface of the graphene oxide so as to exchange ions with the cobalt salt added later, and finally, the graphene oxide is subjected to Co-reduction by a reducing agent or high-temperature reduction. The prepared material is easy to gather a large amount of cobalt particles at the edges of the graphene, and the preparation process is complex, high in risk coefficient, time-consuming and energy-consuming. Therefore, a brand new, more economical, rapid and green preparation method is particularly important.
The invention comprises the following steps:
the invention provides a method for electrochemically preparing a cobalt simple substance-graphene intercalation compound by a one-step method in order to solve the problems in the prior art.
The method for electrochemically preparing the cobalt simple substance-graphene intercalation compound by the one-step method comprises the following steps:
(1) Adding sodium hexanitrocobaltate, weak acid and anionic surfactant into deionized water to prepare electrolyte;
(2) Immersing one or more pairs of graphite sheets connected with a direct current power supply in pairs into electrolyte relatively and vertically, adopting constant current stripping of the direct current power supply for 2-4 hours, and adding ice bath during stripping, wherein the ice bath time is not less than two thirds of the stripping time;
(3) Vacuum filtering the reacted suspension with deionized water and washing; dispersing the cleaned product in DMF (dimethyl formamide) for water bath ultrasonic treatment; and standing after ultrasonic treatment, centrifuging by using a centrifuge, and taking out a lower-layer product and freeze-drying to obtain the cobalt simple substance-graphene intercalation compound.
And (3) calcining the cobalt simple substance-graphene intercalation compound obtained in the step (3) for 2-6h at 500-600 ℃ in an oxygen-free atmosphere. To improve the graphene quality and the fineness of cobalt particles.
The concentration of sodium hexanitrocobaltate in the electrolyte is 0.01-0.05mol/L.
The weak acid is one or more of acetic acid, boric acid, citric acid and nitrous acid; when the weak acid is liquid at normal temperature, the addition amount of the weak acid is 8-12% of the volume of the electrolyte; when the weak acid is solid at normal temperature, the addition amount of the weak acid is 20-40g/L.
The anionic surfactant is one or more of sodium dodecyl sulfate, sodium dodecyl benzene sulfonate, sodium dodecyl sulfate, sodium hexadecyl sulfate, sodium octadecyl sulfate, sodium dioctyl succinate sulfonate, ammonium dodecyl sulfate, ammonium hexadecyl sulfate, ammonium octadecyl sulfate and ammonium dioctyl succinate sulfonate; the addition amount of the anionic surfactant is 0.05-0.5g/L.
The thickness of the graphite sheets is 0.1-2mm, and the distance between every two pairs of graphite sheets connected with the direct current power supply is 2-4cm.
The constant current is 0.5-0.7A.
And (3) the cathode graphite sheet after stripping in the step (3) can be reused.
And standing for not less than 12 hours, and centrifuging at 3000-5000rpm for 20-40min.
The invention adopts an anode electrochemical stripping method, both the anode and the cathode use high-purity graphite sheets, firstly, hexanitrocobalt anions are intercalated into a graphite layer and then subjected to electrochemical reaction, so that exfoliated graphite particles are suspended in electrolyte and gradually migrate to a cathode to perform reduction reaction, and finally cobalt ions in the layer are reduced into cobalt simple substance. Compared with the stripping mode of high-voltage excited plasmas in the prior art, the invention adopts double graphite sheets to replace noble metal pole pieces, and uses water electrolyte, thereby avoiding the use of expensive pollution solutions such as organic solvents, ionic liquids and the like. The electrolyte in the acidic environment can keep the stability of sodium hexanitrocobaltate anions; anionic surfactants can enhance the wettability and dispersibility of anions. The invention has the advantages of mild stripping conditions, low equipment requirement, low energy consumption, simple operation and short stripping time, and accords with a green chemical synthesis route.
Description of the drawings:
FIG. 1 is an XRD pattern of the cobalt simple substance-graphene intercalation compound prepared in example 1 and the product of comparative example 1;
FIG. 2 is a scanning electron microscope image of the cobalt simple substance-graphene intercalation compound prepared in example 1;
FIG. 3 is a graph showing the blue shift contrast of the Raman G peak of the cobalt simple substance-graphene intercalation compound prepared in example 1 and the product of comparative example 1;
FIG. 4 is a XPS Co 2p high resolution graph of the elemental cobalt-graphene intercalation compound prepared in example 1;
fig. 5 is an XRD pattern of the elemental cobalt-graphene intercalation compound prepared in example 2.
The specific embodiment is as follows:
specific embodiments of the present invention will now be described in detail, with reference to the accompanying drawings of embodiments, in which the embodiments are shown, and in which the embodiments are not intended to be exhaustive.
Example 1
(1) 0.403g of sodium hexanitro cobaltate, 12mL of acetic acid, 0.01g of sodium dodecyl sulfonate and deionized water are added into a small beaker and stirred to prepare 100mL of electrolyte;
(2) 4X 2X 0.1cm 3 The two graphite sheets are connected with a direct current power supply, then are immersed in the electrolyte in parallel, the depth of immersion in the electrolyte is 2cm, and the distance between the two graphite sheets connected with the direct current power supply is 3cm; constant current stripping for 3.5h at 0.6A, and keeping an ice bath in the stripping process;
(3) Vacuum filtering the reacted suspension, washing with 300mL of deionized water, dispersing the obtained black filter cake in DMF, and carrying out water bath ultrasonic treatment for 30min to obtain black liquid; and standing the product after ultrasonic treatment overnight, centrifuging for 30min at 4000rpm by using a centrifuge, and taking the black product at the lower layer and freeze-drying to obtain the black powdered cobalt simple substance-graphene intercalation compound.
(4) Calcining the freeze-dried cobalt simple substance-graphene intercalation compound for 4 hours at 550 ℃ in a tubular furnace under the atmosphere of high-purity argon, so as to obtain the refined and low-oxygen-content cobalt simple substance-graphene intercalation compound.
Comparative example 1
The electrolyte of the step (1) in the above example 1 was removed to remove sodium hexanitrocobaltate, cobalt wire with a diameter of 1mm was wound on the anode graphite sheet, and the other conditions were the same as in the example 1, and finally the freeze-dried product was calcined in a tube furnace in an argon-hydrogen mixture containing 8% hydrogen at 550 ℃ for 4 hours to perform thermal reduction, thereby obtaining a product in which cobalt metal was supported on the surface of graphene.
The typical cobalt simple substance cubic structure of the cobalt simple substance-graphene intercalation compound prepared in example 1 and the (002) crystal plane of graphene can be seen from the X-ray diffraction (XRD) pattern of fig. 1.
From a Scanning Electron Microscope (SEM) of fig. 2, it can be seen that the example 1 prepared elemental cobalt-graphene intercalation compound has wrinkled graphene flakes, and no obvious cobalt particles are aggregated, indicating good dispersibility, and the size is less than two nanometers.
The Raman G peak blue shift comparison chart of example 1 and comparative example 1 of fig. 3 shows that the cobalt simple substance-graphene intercalation compound prepared in example 1 has obvious charge transfer phenomenon, has chemical action and accords with the characteristics of the donor graphene intercalation compound.
The high resolution Co 2p XPS spectrum of example 1 of fig. 4 can see that the peak position of cobalt shifts significantly towards high binding energy because of the chemical interaction of the elemental cobalt-graphene intercalation compound, which provides electrons to the graphene.
From the above characterization, the cobalt simple substance-graphene intercalation compound prepared by the electrochemical method is a donor intercalation compound, and the intercalation agent cobalt simple substance is required to provide electrons for parent graphene, so that the Raman G peak is obviously blue-shifted, and the XPS Co 2p also enables Co to be blue-shifted 0 The electron binding energy shifts higher but retains the original lattice structure of the elemental cobalt. The composite material is different from other supported cobalt simple substance/graphene composite materials, the supported composite material basically does not generate charge transfer, so the Raman G peak does not generate larger blue shift or red shift but can be influenced by doping effect to generate shift of a plurality of wave numbers, and a narrow spectrum of XPS Co 2p can generate obvious cobalt near 778-779 eVElemental peak. The characterization of example 1 proves that the solution of the invention is viable. In addition, the invention prepares the cobalt simple substance-graphene intercalation compound in the water-based electrolyte by a direct one-step method, thereby completely conforming to the economic benefit and the green and environment-friendly chemical synthesis route.
Example 2
(1) Stirring 0.403g of sodium hexanitro cobaltate, 3g of boric acid and 0.01g of sodium dodecyl sulfonate with deionized water in a small beaker to prepare 100mL of electrolyte;
(2) 4X 2X 0.1cm 3 The two graphite sheets are connected with a direct current power supply, then are immersed in the electrolyte in parallel, the depth of immersion in the electrolyte is 2cm, and the distance between the two graphite sheets connected with the direct current power supply is 3cm; constant current stripping for 3.5h at 0.6A, and keeping an ice bath in the stripping process;
(3) Vacuum filtering the reacted suspension, washing with 300mL of deionized water, dispersing the obtained black filter cake in DMF, and carrying out water bath ultrasonic treatment for 30min to obtain black liquid; and standing the product after ultrasonic treatment overnight, centrifuging for 30min at 4000rpm by using a centrifuge, and taking the black product at the lower layer and freeze-drying to obtain the black powdered cobalt simple substance-graphene intercalation compound.
(4) Calcining the freeze-dried cobalt simple substance-graphene intercalation compound for 4 hours at 550 ℃ in a tubular furnace under the atmosphere of high-purity argon, so as to obtain the refined and low-oxygen-content cobalt simple substance-graphene intercalation compound.
The XRD pattern of example 2 of fig. 5 shows that the elemental cobalt formed is of a hexagonal face-centered structure.
Claims (6)
1. A method for electrochemically preparing a cobalt simple substance-graphene intercalation compound by a one-step method is characterized by comprising the following specific steps of:
(1) Adding sodium hexanitrocobaltate, weak acid and anionic surfactant into deionized water to prepare electrolyte;
(2) Immersing one or more pairs of graphite sheets connected with a direct current power supply in the electrolyte relatively and vertically, adopting constant current stripping of the direct current power supply for 2-4h, and adding ice bath during stripping, wherein the ice bath time is not less than two thirds of the stripping time;
(3) Vacuum filtering the reacted suspension with deionized water and washing; dispersing the cleaned product in DMF (dimethyl formamide) for water bath ultrasonic treatment; standing after ultrasonic treatment, centrifuging by using a centrifuge, and taking out a lower-layer product and freeze-drying to obtain a cobalt simple substance-graphene intercalation compound;
the concentration of sodium hexanitrocobaltate in the electrolyte is 0.01-0.05 mol/L;
the weak acid is one or more of acetic acid, boric acid, citric acid and nitrous acid; when the weak acid is liquid at normal temperature, the addition amount of the weak acid is 8-12% of the volume of the electrolyte; when the weak acid is solid at normal temperature, the addition amount of the weak acid is 20-40g/L;
the addition amount of the anionic surfactant is 0.05-0.5g/L;
the constant current is 0.5-0.7. 0.7A.
2. The method according to claim 1, wherein the cobalt simple substance-graphene intercalation compound obtained in the step (3) is calcined at 500-600 ℃ for 2-6h in an oxygen-free atmosphere.
3. The method according to claim 1, wherein the anionic surfactant is one or more of sodium dodecyl sulfate, sodium dodecyl benzene sulfonate, sodium dodecyl sulfate, sodium hexadecyl sulfate, sodium octadecyl sulfate, sodium dioctyl succinate sulfonate, ammonium dodecyl benzene sulfonate, ammonium dodecyl sulfate, ammonium hexadecyl sulfate, ammonium octadecyl sulfate, and ammonium dioctyl succinate sulfonate.
4. The method of claim 1, wherein the graphite sheets have a thickness of 0.1 to 2mm and the spacing between each pair of two sheets connected to a dc power source is 2 to 4cm.
5. The method of claim 1, wherein the cathode graphite sheet after the stripping of step (3) is reusable.
6. The method according to claim 1, wherein the rest is not less than 12h, and the centrifuge is centrifuged at 3000-5000rpm for 20-40min.
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