CN114162807B - Three-dimensional porous graphene material and preparation method thereof - Google Patents
Three-dimensional porous graphene material and preparation method thereof Download PDFInfo
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Abstract
The invention relates to aThe three-dimensional porous graphene material has a multi-level pore structure, surface graphene is in a sheet structure, and the sheet structure coats the internal three-dimensional porous structure; the preparation method of the graphene material comprises the following steps: cation exchange resin is used as a carbon source, potassium carbonate and calcium carbonate are used as an activating agent, and the three-dimensional porous graphene material with high specific surface area and high pore volume is generated by high-temperature sintering. The graphene material has high specific surface area and high pore volume, and the specific surface area is more than or equal to 2500m 2 Per gram, pore volume is not less than 0.85cm 3 And/g, the lamellar structure coating is beneficial to improving the structural stability, the thermal conductivity and the electrical conductivity of the graphene.
Description
Technical Field
The invention relates to the technical field of graphene, in particular to a three-dimensional porous graphene material and a preparation method thereof.
Background
Graphene is widely applied to the fields of gas adsorption, water treatment, catalyst carriers, energy storage and the like by virtue of its excellent physicochemical characteristics, including chemical inertness, ultrahigh conductivity, light weight, large surface area and the like. However, the successful application of graphene materials depends largely on achieving the desired structural characteristics to meet the specific requirements of the respective devices. Therefore, in order to meet the demands of various devices, the feasibility of the synthesis method and the ability to precisely control structural characteristics are critical in the synthesis process of graphene materials.
Currently, synthetic graphene is synthesized mainly by template methods, i.e., by incorporating various templates, such as MgO, caO, tiO 2 、NiO、SiO 2 Or other template material to create a porous structure. Although the method can obtain the graphene with a porous structure, and the pore size distribution and the pore volume can be adjusted by the size of the template, the wide application of the method is limited by complex pre-synthesis of a special template, longer synthesis time, higher energy consumption and the like, so that the synthetic material of the method has longer period and relative costHigher. Another main route is to chemically or physically activate the preparation of graphene, e.g. with KOH, znCl 2 、H 3 PO 4 Water vapor, etc. as activators.
As patent CN106927451B discloses that a three-dimensional graphene structure is synthesized by high-temperature sintering with a large network resin as a carbon source, a calcium salt as a transitional mold cavity filler, and hydroxide as a pore-expanding agent, the three-dimensional graphene structure has a high specific surface area, but the hydroxide is mainly used for generating micropores (< 2 nm), and medium and large pores are difficult to realize; and only a limited specific surface area and pore volume can be obtained; from the application point of view, the graphene doped with nitrogen, sulfur and other elements has wider application range due to the more excellent characteristics, but the use of hydroxide greatly reduces the content of hetero atoms in the graphene, which is not beneficial to practical application. In addition, from an environmental and economic point of view, corrosion and environmental problems of equipment caused by the use of a large amount of strong base have made urgent demands for the replacement of hydroxides in the production of porous graphene.
Disclosure of Invention
The invention aims to solve the technical problem of providing a three-dimensional porous graphene material and a preparation method thereof aiming at the defects in the prior art.
In order to solve the technical problems, the present invention provides, in a first aspect, a three-dimensional porous graphene material (abbreviated as three-dimensional porous graphene), wherein a surface layer of the three-dimensional porous graphene material is a sheet-shaped structure, an inside of the three-dimensional porous graphene material is a three-dimensional porous structure, and the three-dimensional porous structure is covered by the sheet-shaped structure; specifically, for example, the three-dimensional porous graphene material of the present invention has a hierarchical pore structure, and the surface layer of the three-dimensional porous graphene has a lamellar structure, and is preferably a continuous film shape; the sheet-shaped structure coats the three-dimensional porous structure; in the invention, the coating of the lamellar structure is beneficial to improving the structural stability, the thermal conductivity and the electrical conductivity of the graphene material; the three-dimensional porous graphene material has excellent thermal conductivity, and the electrical conductivity is more than or equal to 10 4 S/m is applied to the field of lithium ion batteries, and can effectively improve the electrochemical properties of the lithium ion batteries, such as energy density, cycle life and the likeCan be used.
Preferably, the three-dimensional porous structure comprises micropores with a pore diameter of <2nm, mesopores with a pore diameter of 2-50nm and macropores with a pore diameter of > 50nm, i.e. the three-dimensional porous structure comprises micropores (< 2 nm), mesopores (2-50 nm) and macropores (> 50 nm).
Preferably, the number ratio of the micropores, the mesopores, and the macropores is (10 to 30): (20-40): (20-50).
Preferably, the surface layer of the three-dimensional porous graphene material is of a compact lamellar structure; more preferably, the pore diameter of the three-dimensional porous graphene material gradually decreases from inside to outside until the surface layer is of a compact lamellar structure.
Preferably, the porosity of the three-dimensional porous graphene material is 50-95%.
Preferably, the three-dimensional porous graphene material has one or more of the following properties:
(a) The specific surface area of the three-dimensional porous graphene material is more than or equal to 2500m 2 Preferably not less than 2800m 2 /g；
(b) The pore volume (total pore volume) of the three-dimensional porous graphene material is more than or equal to 0.85cm 3 Preferably the pore volume (total pore volume) is ≡2 cm/g 3 /g；
(c) In the XRD diffraction pattern of the three-dimensional porous graphene material, the peaks Jiang Bi of the peaks (002) and (110) are 2: (0.2-1);
(d) The three-dimensional porous graphene material is 1300cm in Raman spectrum test -1 -1400cm -1 Peak intensity D versus at 1500cm -1 -1700cm -1 The ratio of the peak intensities G of (1): (0.5-2), i.e., a peak intensity ratio (D/G) of 1: (0.5-2);
(e) In Raman spectrum test, the three-dimensional porous graphene material is 2600cm in length -1 - 2900cm -1 The peak intensity is present at 2D, preferably at 2600cm -1 -2900cm -1 Peak intensity 2D versus at 1300cm -1 -1400cm -1 The ratio of the peak intensities D of (1) is (0.1-1): 1, namely, the peak intensity ratio (2D/D) is (0.1-1): 1; the invention discovers that the XRD diffraction pattern of the three-dimensional porous graphene materialThe peak intensity ratios shown in the Raman spectrum test spectrograms can indicate that the three-dimensional porous graphene material has high graphitization degree and good comprehensive performance, and is beneficial to improving the application in lithium ion batteries and the like.
Preferably, the thickness of the platelet structure is 0.2-50nm, more preferably 0.35-10nm.
Preferably, the surface layer of the three-dimensional porous graphene material is of a fold structure.
Preferably, the sheet structure is in the form of a continuous dense film.
Preferably, the three-dimensional porous graphene material is doped with at least one of nitrogen element and sulfur element.
Preferably, the mass percentage of the nitrogen element doped in the three-dimensional porous graphite material is 0-15%, more preferably 0.5-15%.
Preferably, the mass percentage of the sulfur element doped in the three-dimensional porous graphite material is 0-10%, and more preferably 0.5-10%.
Preferably, at least one of the nitrogen element and the sulfur element is uniformly distributed in the pores of the three-dimensional porous graphene material.
The invention also provides a preparation method of the three-dimensional porous graphene in the second aspect, which comprises the following steps:
(1) Uniformly mixing cation exchange resin and an activating agent to obtain a precursor;
(2) Placing the precursor in an inert atmosphere, heating and sintering at 750-1200 ℃ (such as 750 ℃, 800 ℃, 850 ℃, 900 ℃, 950 ℃, 1000 ℃, 1050 ℃, 1100 ℃, 1150 ℃ or 1200 ℃) for 0.1-5 hours (such as 0.5, 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5 or 5 hours), cooling to room temperature (such as cooling to room temperature 15-35 ℃), and then washing and drying to obtain the three-dimensional porous graphene material, preferably, the three-dimensional porous graphene material according to the first aspect of the invention; wherein the activator is a mixture of potassium carbonate and calcium carbonate; in the present invention, the washing is, for example: the acid soaking method is adopted to carry out acid pickling firstly, then deionized water is adopted to carry out centrifugal washing, the acid soaking time can be 1-3 h, the acid used in the acid soaking can be one or more of hydrochloric acid, sulfuric acid, nitric acid, hypochlorous acid, acetic acid and the like, the acid concentration adopted in the acid soaking is not particularly required, preferably, the pH value is regulated to be 2-4 during the acid soaking, and thus potassium salt, calcium salt and unreacted carbonate in the system can be removed to improve the purity of the three-dimensional porous graphene material; in the invention, the drying is performed, for example, at 80 to 150℃for 8 to 16 hours.
According to the invention, the mixture of potassium carbonate and calcium carbonate is used as an activating agent, and the activating agent is found that the potassium carbonate can be formed in the heat treatment process, the melting point of the formed potassium carbonate is lower than that of carbonate, the solid-liquid reaction of solid-phase resin-liquid-phase potassium carbonate can occur in the high-temperature activation process, the reaction activity and pore-forming function are improved, the sintering temperature and time are reduced, the volatilization of nitrogen and sulfur elements in the cation exchange resin is avoided, the doping of nitrogen or sulfur elements is facilitated, the conductivity of graphene can be effectively improved, the active sites can be increased, the defects of graphene can be increased, and the adsorption performance of graphene can be improved; the invention adopts the mixture of potassium carbonate and calcium carbonate as the active agent, can avoid the corrosion of other alkaline salts or acid salts to equipment, reduces the cost and is beneficial to industrialization; at the same time, the carbonate can decompose to form CO in the sintering process 2 Therefore, the purpose of secondary pore forming is achieved, other impurities are not introduced, and the purity of the graphene is improved.
The type of the cation exchange resin is not particularly limited in the present invention, and preferably the cation exchange resin is a sulfonic acid group (-SO) 3 H) Cation exchange resin, carboxyl (-COOH) cation exchange resin, phenol (-C) 6 H 4 OH) at least one of the cation exchange resins.
Preferably, the cation exchange resin is at least one of a styrene gel type strong acid cation exchange resin, a styrene macroporous type strong acid cation exchange resin, an acrylic gel type weak acid cation exchange resin, a macroporous type weak acid cation exchange resin and a nuclear grade cation exchange resin; the source of these preferred cation exchange resins is not particularly limited in the present invention, and products which can be directly purchased in the market are adopted; specifically, the cation exchange resin is at least one of a D001 type cation exchange resin, a D113 type cation exchange resin, a D002 type cation exchange resin, a D301 type cation exchange resin, a D280 type cation exchange resin, a D201 type cation exchange resin, a D301 type cation exchange resin, a D151 type cation exchange resin and a D152 type cation exchange resin, and in the invention, the cation exchange resins of specific types can be directly purchased from the market.
Preferably, the cation exchange resin is a cation exchange resin loaded with metal ions, and in the present invention, the cation exchange resin loaded with metal ions may be referred to as a cation exchange resin containing metal ions; in the preparation process of the organic carbon source, the supported metal ions can serve as a catalyst, and in the preparation process, the potassium calcium carbonate can also serve as a catalyst, but the relative sintering temperature is higher, the cation exchange resin containing the metal ions has good catalytic effect and the sintering temperature is lower.
Preferably, the cation exchange resin loaded with metal ions is prepared by the following method: soaking the cation exchange resin in a metal salt solution, and then heating until a solvent evaporates to obtain the cation exchange resin loaded with metal ions; specifically, for example, the cation exchange resin is soaked in a metal salt solution, stirred and mixed uniformly, and then heated until the solvent evaporates to dryness, so that the cation exchange resin loaded with metal ions is obtained.
Preferably, the metal ions contained in the metal salt solution are one or more of nickel, cobalt and iron; the metal salt solution may be, for example, one or more of ferric trichloride solution, ferrous ammonium sulfate solution, ferric sulfate solution, potassium ferricyanide solution, potassium ferrocyanide solution, sodium nitrosoferricyanide solution, ferric nitrate solution, ferric citrate solution, ferrous sulfide solution, ferric oxalate solution, cobalt chloride solution, cobalt sulfate solution, cobalt nitrate solution, sodium cobalt nitrite solution, cobalt acetate solution, potassium cobalt nitrite solution, nickel acetate solution, nickel sulfate solution, nickel ammonium sulfate solution, nickel chloride solution, nickel nitrate solution, nickel oxalate solution, nickel bromide solution.
Preferably, the metal salt solution contains 1-75% of metal salt by mass.
Preferably, the metal salt solution contains a metal salt in an amount ratio of (0.04 to 3.2) mol to the cation exchange resin: 1kg.
Preferably, the solvent evaporates at a temperature of 80-150 ℃; the time for evaporating the solvent is not particularly limited in the present invention, and the solvent may be evaporated to dryness.
Preferably, the cation exchange resin is one or more of a porous network structure, a honeycomb structure, a three-dimensional structure, and the like.
Preferably, the mass ratio of potassium carbonate to calcium carbonate is 1 (0.3-5) (e.g., 1:0.3, 1:0.5, 1:0.8, 1:1, 1:1.2, 1:1.5, 1:1.8, 1:2, 1:2.5, 1:3, 1:3.5, 1:4, 1:4.5, or 1:5); in the present invention, it is preferable that the mass ratio of the potassium carbonate to the calcium carbonate is 1: (0.3-5), which is favorable for the generation of potassium calcium carbonate.
Preferably, the mass ratio of the cation exchange resin to the activator is 1 (0.1-10), more preferably 1: (1-4) (e.g., 1:1, 1:1.5, 1:2, 1:2.5, 1:3, 1:3.5, or 1:4).
Preferably, in step (1), the mixing mode of the cation exchange resin and the activator is any one of mechanical mixing, ball milling mixing, spray drying, plate and frame filtering and liquid phase mixing.
Preferably, in step (1), the mixing mode of the cation exchange resin and the activator adopts any one of the following modes:
(a) Ball milling and mixing, wherein the ball milling and mixing are as follows: ball milling the cation exchange resin and the activator for 0.2 to 6 hours at a speed of 500 to 3000 rpm;
(b) Liquid phase mixing, wherein the liquid phase mixing is as follows: dissolving cation exchange resin and active agent in solvent, and evaporating solvent under stirring at stirring speed of 200-3000 rpm;
(c) Spray drying, the spray drying is: the cation exchange resin, the active agent and the organic solvent are mixed and then spray-dried.
Preferably, in step (2), the temperature rise rate of the sintering temperature heated to 750-1200 ℃ is 1-10 ℃/min.
Preferably, the heating mode of the heating sintering is natural heating, microwave heating or plasma heating.
Preferably, the precursor is heated and sintered by any one of the following modes:
(a) Natural heating, preferably, the precursor is placed in a crucible, and the natural heating is performed in a tube furnace, a box furnace or a muffle furnace according to a set heating program;
(b) Preferably, the microwave heating power is 500-1500W, and the heating time is 0.1-1h;
(c) Preferably, the plasma heating is performed at an ion power of 100-1000W and a steam concentration of 10 3 /cm 3 ～10 7 /cm 3 Is carried out under the condition of (2).
The implementation of the invention has the following beneficial effects:
(1) The surface layer of the three-dimensional porous graphene material is of a lamellar structure and is of a continuous film shape, and the three-dimensional porous structure is coated inside the three-dimensional porous graphene material, so that the graphitization degree and stability of graphene can be effectively improved, and meanwhile, the three-dimensional porous graphene material has excellent heat conductivity and electric conductivity, and the application prospect of the graphene is expanded.
(2) The three-dimensional porous graphene material has a three-dimensional porous structure, and the specific surface area can reach 2500m 2 Above/g, pore volume of 0.85cm 3 Preferably at least/g, more preferably at least 2800m 2 Per gram, pore volume is not less than 2cm 3 And/g, which is beneficial to widening the application field of the graphene.
(3) According to the method, the mixture of the potassium carbonate and the calcium carbonate is used as an activating agent, the formed potassium carbonate and calcium carbonate can be formed in the heat treatment process, the melting point of the formed potassium carbonate and calcium carbonate is lower than that of carbonate, the solid-liquid reaction of solid-phase resin-liquid-phase potassium carbonate and calcium carbonate can occur in the high-temperature activation process, the reaction activity and pore-forming function are improved, the sintering temperature and time are reduced, the volatilization of nitrogen elements in the cation exchange resin is avoided, the doping of nitrogen or sulfur elements is facilitated, the conductivity of graphene can be effectively improved, the active sites are increased, the defects of graphene are increased, and the adsorption performance of graphene is improved.
(4) The method adopts the mixture of the potassium carbonate and the calcium carbonate as the active agent, can avoid corrosion of other alkaline salts or acid salts to equipment, reduces the cost and is beneficial to industrialization; at the same time, the carbonate can decompose to form CO in the sintering process 2 The purpose of secondary pore-forming is achieved, other impurities are not introduced, and the purity of the graphene is improved.
(5) The three-dimensional porous graphene material has excellent thermal conductivity, and the electrical conductivity is more than or equal to 10 4 S/m is applied to the field of lithium ion batteries, and can effectively improve the electrochemical properties of the lithium ion batteries, such as energy density, cycle life and the like.
Drawings
FIG. 1 is a schematic diagram of a preparation process of a three-dimensional porous graphene material in the present invention;
FIG. 2 is an XRD pattern of the precursor of example 1 of the present invention, which is not washed after sintering;
FIG. 3 is a TEM image of a three-dimensional porous graphene material prepared in example 1 of the present invention;
in the drawing, the drawing (b) is an enlarged schematic view of the part A in the drawing (a); FIG. (c) is an enlarged schematic view of part B of FIG. (B); in the graph (c), the "Microproes" represents micropores, the "Graphic laminates" represents graphite layers, from the graph, the graphite layers with the interlayer spacing of 0.334nm can be seen, and the graphite layers are in a stacking state of 2-5 layers, and the surface layer of the three-dimensional porous graphene material in the invention can be seen to be a sheet structure, the sheet structure is a continuous compact film, and the inside of the three-dimensional porous graphene material is a three-dimensional porous structure;
FIG. 4 is an XRD pattern of graphene materials prepared in example 1, comparative example 1, and comparative example 2 of the present invention;
FIG. 5 is a Raman diagram of graphene materials prepared in example 1, comparative example 1 and comparative example 2 of the present invention;
FIG. 6 is an XPS diagram of a three-dimensional porous graphene material prepared in example 1 of the present invention;
FIG. 7 is an adsorption graph of graphene materials prepared in example 1 and comparative examples 1-5 of the present invention;
fig. 8 is an adsorption graph of a three-dimensional porous graphene material prepared in example 7 of the present invention.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention, and it is apparent that the described embodiments are some embodiments of the present invention, but not all embodiments of the present invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1:
(1) Taking 60g of D113 type cation exchange resin, and uniformly mixing with 30g of calcium carbonate and 30g of potassium carbonate by ball milling to obtain a precursor;
(2) Sintering the precursor for 1h at 800 ℃ in a nitrogen protection atmosphere, and naturally cooling to room temperature to obtain a product;
(3) And soaking the obtained product in hydrochloric acid for 2 hours, adjusting the pH value to 2-3 during soaking, centrifugally washing with deionized water, and drying at 120 ℃ for 10 hours to obtain the target three-dimensional porous graphene material.
TEM image of the three-dimensional porous graphene material prepared in the embodiment is shown in FIG. 3; XRD patterns of the three-dimensional porous graphene material prepared in the embodiment are shown in FIG. 4; as can be seen from the results of fig. 4, in the XRD diffractogram of the three-dimensional porous graphene material prepared in this embodiment, the peak intensity ratio of peak (002) to peak (110) is 2: (0.2-1); the raman diagram of the three-dimensional porous graphene material prepared in the embodiment is shown in fig. 5; as can be seen from the results of FIG. 5, the temperature is 1300cm -1 -1400cm -1 Peak intensity D versus at 1500cm -1 -1700cm -1 The ratio of the peak intensities G is 1: (0.5-2); at 2600cm -1 -2900cm -1 The peak intensity 2D exists, and the peak intensity ratio 2D/D is between (0.1 and 1): 1; from the results of fig. 4 and 5, it is demonstrated that graphene materials were successfully prepared and graphitized to a high degree.
According to the invention, the nitrogen element mass percentage content of the three-dimensional porous graphene material prepared by the embodiment is 4.3% as measured by XPS; in addition, the conductivity was measured to be 25640S/m, and the specific surface area of the three-dimensional porous graphene material prepared in the present example was 2980m by BET test 2 Per gram, total pore volume of 1.55cm 3 And/g, the results are shown in tables 1 and 2, respectively.
Example 2:
(1) Taking 60g of D113 type cation exchange resin, and carrying out ball milling and mixing uniformly with 60g of calcium carbonate and 60g of potassium carbonate to obtain a precursor;
(2) Sintering the precursor for 1h at 750 ℃ in a nitrogen protection atmosphere, and naturally cooling to room temperature to obtain a product;
(3) And soaking the obtained product in hydrochloric acid for 2 hours, adjusting the pH value to 2-3 during soaking, centrifugally washing with deionized water, and drying at 120 ℃ for 10 hours to obtain the target three-dimensional porous graphene material.
Example 3:
this example differs from example 1 in that the sintering temperature is 750 ℃, and the other processes and preparation flows are the same as example 1.
Example 4:
(1) Taking 60g of D113 type cation exchange resin, and carrying out ball milling and mixing uniformly with 60g of calcium carbonate and 60g of potassium carbonate to obtain a precursor;
(2) Sintering the precursor for 1h at 900 ℃ in a nitrogen protection atmosphere, and naturally cooling to room temperature to obtain a product;
(3) And soaking the obtained product in hydrochloric acid for 2 hours, adjusting the pH value to 2-3 during soaking, centrifugally washing with deionized water, and drying at 120 ℃ for 10 hours to obtain the target three-dimensional porous graphene material.
Example 5:
(1) Taking 60g of D113 type cation exchange resin, and carrying out ball milling and mixing uniformly with 120g of calcium carbonate and 120g of potassium carbonate to obtain a precursor;
(2) Sintering the precursor for 0.5h at 900 ℃ in a nitrogen protection atmosphere, and naturally cooling to room temperature to obtain a product;
(3) And soaking the obtained product in hydrochloric acid for 2 hours, adjusting the pH value to 2-3 during soaking, centrifugally washing with deionized water, and drying at 120 ℃ for 10 hours to obtain the target three-dimensional porous graphene material.
Example 6:
(1) Taking 60g of D113 type cation exchange resin, and carrying out ball milling and mixing uniformly with 90g of calcium carbonate and 90g of potassium carbonate to obtain a precursor;
(2) Sintering the precursor for 2 hours at 900 ℃ in a nitrogen protection atmosphere, and naturally cooling to room temperature to obtain a product;
(3) And soaking the obtained product in hydrochloric acid for 2 hours, adjusting the pH value to 2-3 during soaking, centrifugally washing with deionized water, and drying at 120 ℃ for 10 hours to obtain the target three-dimensional porous graphene material.
Example 7:
(1) Taking 60g of D113 type cation exchange resin, and carrying out ball milling and mixing uniformly with 90g of calcium carbonate and 90g of potassium carbonate to obtain a precursor;
(2) Sintering the precursor for 1h at 1200 ℃ in a nitrogen protection atmosphere, and naturally cooling to room temperature to obtain a product;
(3) And soaking the obtained product in hydrochloric acid for 2 hours, adjusting the pH value to 2-3 during soaking, centrifugally washing with deionized water, and drying at 120 ℃ for 10 hours to obtain the target three-dimensional porous graphene material.
Example 8:
(1) Taking 60g of D113 type cation exchange resin, and carrying out ball milling and mixing uniformly with 60g of calcium carbonate and 60g of potassium carbonate to obtain a precursor;
(2) Sintering the precursor for 3 hours at 1000 ℃ in a nitrogen protection atmosphere, and naturally cooling to room temperature to obtain a product;
(3) And soaking the obtained product in hydrochloric acid for 2 hours, adjusting the pH value to 2-3 during soaking, centrifugally washing with deionized water, and drying at 120 ℃ for 10 hours to obtain the target three-dimensional porous graphene material.
Example 9:
this example differs from example 1 in that the amount of calcium carbonate used is 15g and the amount of potassium carbonate used is 45g, the other processes and preparation schemes being the same as example 1.
Example 10:
this example differs from example 1 in that the amount of calcium carbonate used was 20g and the amount of potassium carbonate used was 40g, and the other processes and preparation schemes were the same as in example 1.
Example 11:
this example differs from example 1 in that the amount of calcium carbonate used is 40g and the amount of potassium carbonate used is 20g, the other processes and preparation schemes being the same as example 1.
Comparative example 1:
this comparative example differs from example 1 in that the sintering temperature was 700 ℃, and the other processes and preparation procedures were the same as example 1.
Comparative example 2:
this comparative example differs from example 1 in that 30g of potassium carbonate and 30g of calcium carbonate were replaced with 60g of potassium carbonate, and the other processes and preparation schemes were the same as in example 1.
Comparative example 3:
this comparative example differs from example 1 in that 30g of potassium carbonate and 30g of calcium carbonate were replaced with 60g of calcium carbonate, and the other processes and preparation schemes were the same as in example 1.
Comparative example 4:
this comparative example differs from example 1 in that 30g of potassium carbonate and 30g of calcium carbonate were replaced with 60g of potassium hydroxide, and the other processes and preparation procedures were the same as in example 1.
Comparative example 5:
this comparative example differs from example 1 in that 30g of potassium carbonate and 30g of calcium carbonate were replaced with 30g of potassium hydroxide and 30g of calcium hydroxide, and the other processes and preparation schemes were the same as in example 1.
Comparative example 6:
this comparative example differs from example 1 in that 30g of potassium carbonate and 30g of calcium carbonate were replaced with 30g of potassium hydroxide and 30g of calcium oxide, and the other processes and preparation schemes were the same as in example 1.
Comparative example 7:
this comparative example differs from example 1 in that 30g of potassium carbonate and 30g of calcium carbonate were replaced with 30g of potassium hydroxide and 30g of calcium carbonate, and the other processes and preparation schemes were the same as in example 1.
Table 1: nitrogen element content and conductivity test results of example 1 and comparative examples 2 to 4.
Table 2: specific surface area and total pore volume results for each example and each comparative example.
In conclusion, the invention adopts the mixture of potassium carbonate and calcium carbonate as the activating agent, can effectively improve the specific surface area, effectively avoid volatilization of nitrogen element, and can prepare the nitrogen-doped three-dimensional porous graphene material.
The invention is not described in detail in a manner known to those skilled in the art.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and are not limiting; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit and scope of the technical solutions of the embodiments of the present invention.
Claims (20)
1. The three-dimensional porous graphene material is characterized in that:
the surface layer of the three-dimensional porous graphene material is of a sheet structure, the inside of the three-dimensional porous graphene material is of a three-dimensional porous structure, and the three-dimensional porous structure is coated by the sheet structure;
the preparation method of the three-dimensional porous graphene material comprises the following steps:
(1) Uniformly mixing cation exchange resin and an activating agent to obtain a precursor; the activator is a mixture of potassium carbonate and calcium carbonate; the mass ratio of the potassium carbonate to the calcium carbonate is 1 (0.3-5);
(2) Placing the precursor in an inert atmosphere, heating and sintering at 750-1200 ℃ for 0.1-5 hours, cooling to room temperature, and then washing and drying to obtain the three-dimensional porous graphene material; the three-dimensional porous graphene material is doped with at least one of nitrogen element and sulfur element.
2. The three-dimensional porous graphene material of claim 1, wherein:
the three-dimensional porous structure comprises micropores with the aperture less than 2nm, mesopores with the aperture of 2-50nm and macropores with the aperture more than 50nm; and/or
The surface layer of the three-dimensional porous graphene material is of a compact lamellar structure; and/or
The porosity of the three-dimensional porous graphene material is 50-95%.
3. The three-dimensional porous graphene material of claim 2, wherein:
the number ratio of the micropores to the mesopores to the macropores is (10-30): (20-40): (20-50).
4. The three-dimensional porous graphene material of claim 2, wherein:
the pore diameter of the three-dimensional porous graphene material gradually decreases from inside to outside until the surface layer is of a compact sheet structure.
5. The three-dimensional porous graphene material of claim 1, wherein: the three-dimensional porous graphene material has one or more of the following properties:
(a) The specific surface area of the three-dimensional porous graphene material is more than or equal to 2500m 2 /g；
(b) The pore volume of the three-dimensional porous graphene material is more than or equal to 0.85cm 3 /g；
(c) In the XRD diffraction pattern of the three-dimensional porous graphene material, the peaks Jiang Bi of the peaks (002) and (110) are 2: (0.2-1);
(d) The three-dimensional porous graphene material is 1300cm in Raman spectrum test -1 -1400cm -1 Peak intensity D versus at 1500cm -1 -1700cm -1 The ratio of the peak intensities G of (1): (0.5-2);
(e) In Raman spectrum test, the three-dimensional porous graphene material is 2600cm in length -1 -2900cm -1 There is a peak intensity of 2D.
6. The three-dimensional porous graphene material of claim 5, wherein:
the specific surface area of the three-dimensional porous graphene material is more than or equal to 2800m 2 /g。
7. The three-dimensional porous graphene material of claim 5, wherein:
the pore volume of the three-dimensional porous graphene material is more than or equal to 2cm 3 /g。
8. The three-dimensional porous graphene material of claim 5, wherein:
at 2600cm -1 -2900cm -1 Peak intensity 2D versus at 1300cm -1 -1400cm -1 The ratio of the peak intensities D of (1) is (0.1-1): 1.
9. the three-dimensional porous graphene material of claim 1, wherein:
the thickness of the flaky structure is 0.2-50nm; and/or
The surface layer of the three-dimensional porous graphene material is of a fold structure; and/or
The sheet structure is a continuous compact film.
10. The three-dimensional porous graphene material of claim 9, wherein:
the thickness of the lamellar structure is 0.35-10nm.
11. The three-dimensional porous graphene material of claim 1, wherein:
the mass percentage of the nitrogen element doped in the three-dimensional porous graphite material is 0-15%, and/or the mass percentage of the sulfur element doped in the three-dimensional porous graphite material is 0-10%.
12. The three-dimensional porous graphene material of claim 1, wherein:
at least one of the nitrogen element and the sulfur element is uniformly distributed in the holes of the three-dimensional porous graphene material.
13. A preparation method of a three-dimensional porous graphene material is characterized by comprising the following steps: the method comprises the following steps:
(1) Uniformly mixing cation exchange resin and an activating agent to obtain a precursor; the activator is a mixture of potassium carbonate and calcium carbonate; the mass ratio of the potassium carbonate to the calcium carbonate is 1 (0.3-5);
(2) Placing the precursor in an inert atmosphere, heating and sintering at 750-1200 ℃ for 0.1-5 hours, cooling to room temperature, and then washing and drying to obtain the three-dimensional porous graphene material; the three-dimensional porous graphene material is doped with at least one of nitrogen element and sulfur element.
14. The method of manufacturing according to claim 13, wherein:
the cation exchange resin is at least one of sulfonic cation exchange resin, carboxyl cation exchange resin and phenol cation exchange resin; and/or
The cation exchange resin is at least one of styrene gel type strong acid cation exchange resin, styrene macroporous type strong acid cation exchange resin, acrylic gel type weak acid cation exchange resin and macroporous type weak acid cation exchange resin, and nuclear grade cation exchange resin.
15. The method of manufacturing according to claim 13, wherein:
the mass ratio of the cation exchange resin to the activator is 1 (0.1-10).
16. The method of claim 13, wherein the cation exchange resin and the activator are mixed in any one of the following ways:
(a) Ball milling the cation exchange resin and the activator for 0.2 to 6 hours at a speed of 500 to 3000 rpm;
(b) Dissolving cation exchange resin and active agent in solvent, and evaporating solvent under stirring at stirring speed of 200-3000 rpm;
(c) The cation exchange resin, the active agent and the organic solvent are mixed and then spray-dried.
17. The method according to claim 13, wherein the precursor is heated and sintered by any one of the following methods:
(a) Naturally heating;
(b) Heating by microwaves;
(c) And (5) heating the plasma.
18. The method of manufacturing according to claim 17, wherein:
the natural heating is carried out by placing the precursor in a crucible, and then carrying out the heating in a tube furnace, a box furnace or a muffle furnace according to a set heating program.
19. The method of manufacturing according to claim 17, wherein:
the microwave heating power is 500-1500W, and the heating time is 0.1-1h.
20. The method of manufacturing according to claim 17, wherein:
the plasma is heated to ion power of 100-1000W, and the concentration of steam is 10 3 /cm 3 ～10 7 /cm 3 Is carried out under the condition of (2).
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