CN113104841B - Method for preparing few-layer three-dimensional graphene high-performance anode composite carbon material - Google Patents
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- C—CHEMISTRY; METALLURGY
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- C01B32/00—Carbon; Compounds thereof
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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
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Abstract
The invention provides a method for preparing a few-layer three-dimensional graphene high-performance anode composite carbon material. The preparation process of the high-performance few-layer three-dimensional graphene composite material for the lithium battery anode is simple, the preparation cost is effectively reduced, the preparation method is suitable for large-scale production, the problems that the existing graphene preparation process is complex, the volume production is difficult, the yield is low, the cost is high and the like are solved, and the preparation method is an economical and efficient preparation method of the high-performance few-layer three-dimensional graphene composite material.
Description
Technical Field
The invention relates to the technical field of production of a high-performance three-dimensional graphene lithium battery anode composite carbon material.
Background
With the development of new energy electric vehicles, the demand for power batteries has increased significantly, and in the coming years to decades, the demand for power batteries in the automotive industry in our country may also increase at an extremely high rate. At present, the electrode of the automobile battery is made of common commercial graphite. The ordinary commercial graphite itself has a low electric storage capacity (theoretical capacity: 372 mAh/g). The modified graphite material can greatly improve the charge capacity and is very important for the development of new energy electric automobiles and other application battery industries. In addition, with the development of the automobile industry, the requirements for power batteries are also improved, and the graphene composite material has greater advantages than common commercial graphite in meeting the electrode materials required by high-performance batteries. Graphene is an electrode material of a high-performance lithium battery which is generally recognized at present, has the characteristics of excellent strength, specific surface area, surface chemical properties, high theoretical capacity and the like, and has a very wide application prospect in the fields of high-performance batteries, advanced materials, biotechnology, electronic device production and the like.
Disclosure of Invention
The invention aims to solve the problems of complex preparation process, difficult mass production, low yield, high cost and the like of the existing graphene, and provides a method for preparing a few-layer three-dimensional graphene high-performance anode composite carbon material.
In order to achieve the purpose, the invention is realized by the following technical scheme:
(1) the method takes any one or a mixture of several of biomass, coal, semi-coke and active carbon as a carbonaceous raw material, and obtains the few-layer three-dimensional graphene high-performance anode composite carbon material through catalyst implantation and microwave catalytic graphitization.
(2) The invention is realized by the following technical steps:
1) implanting a catalyst into the carbonaceous raw material by an impregnation method or a coprecipitation method, wherein the implantation amount of the catalyst is 1.0 wt.% or 20wt.% or 50 wt.% in terms of mass percentage;
2) placing the material obtained in the step 1) in microwave heating equipment, heating to 500-1800 ℃ at a heating rate of 100-120 ℃/min, and keeping for 0.25-2 hours to obtain a product G-AC;
3) taking G-AC and NaNO according to the mass ratio of 1:1:53And KMnO4Successively, the solution was slowly added to 95 wt.% H in mass percentage immersed in an ice-water bath2SO4In (H)2SO4The mass ratio of the raw materials to the G-AC is 1.5:1, the raw materials are continuously stirred for 3 to 3.2 hours, then the raw materials are heated to 35 to 37 ℃, and the mixture is stirred for 45 to 50 minutes; then heating to 80-82 ℃, and keeping the temperature for 1-1.2 h; keeping the temperature unchanged, dropwise adding deionized water into the mixture, wherein the mass ratio of the deionized water to the G-AC is 3:1, and then dropwise adding H with the mass percentage of 30 wt%2O2，H2O2The mass ratio of the raw material to the G-AC is 0.25: 1;
4) centrifuging the material obtained in step 3), removing clear liquid, and washing the residual solid with 1M HCl solution and deionized water until the pH value of the solution is neutral;
5) adding the material obtained in the step 4) into deionized water for ultrasonic treatment for 20-40 minutes, and then carrying out freeze drying to obtain graphene oxide, which is marked as Ox-MG;
6) placing the Ox-MG obtained in the step 5) into a corundum crucible with a cover, then placing the corundum crucible into a muffle furnace preheated to 900-920 ℃, heating the corundum crucible for 10-20 minutes in a nitrogen atmosphere, and cooling to obtain few-layer graphene, namely MG.
The catalyst comprises one or more transition metal salts or one or more transition metals in ionic form; the transition metal includes Fe, Ni, Co, Zn, Mn.
The one or more transition metal salts are obtained by reacting transition metal ions with the valence less than 3 with nitric acid or hydrochloric acid.
The one or more transition metals in ionic form should have a valence of less than 3.
The carbon atoms of the few-layer three-dimensional graphene high-performance anode composite carbon material are in a hexagonal arrangement, such as a sheet shape, a spherical shape, a cage shape or an irregular shape, the number of layers of graphene is 2-50, and the structure comprises one or more of the following characteristics:
(1) the X-ray diffraction peak mirror surfaces were { 002 }, { 101 }, { 100 } and { 004 };
(2) the interlayer spacing is between 0.333nm and 0.345 nm;
(3) the crystallinity, namely the graphene degree is between 50 and 100 percent;
(4) the crystal size is more than or equal to 0.246 nm.
Compared with the prior art, the invention has the beneficial effects that:
the preparation process of the high-performance few-layer three-dimensional graphene composite material for the lithium battery anode is simple, the preparation cost is effectively reduced, and the preparation method is suitable for large-scale production and is an economical and efficient preparation method of the high-performance few-layer three-dimensional graphene composite material.
Drawings
FIG. 1 is an X-ray diffraction pattern of G-AC, Ox-MG and MG.
FIG. 2 is a photograph of an MG transmission electron microscope.
Fig. 3 is a MG constant current charge-discharge characteristic curve.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It is to be understood that the specific embodiments described herein are merely illustrative of the invention and are not to be considered in a limiting sense, the invention being thus defined which, to the extent possible, is intended to be within the scope of the appended claims.
The invention provides a method for preparing a few-layer three-dimensional graphene high-performance anode composite carbon material. The method is realized by the following technical scheme:
(1) implanting a catalyst into the carbonaceous raw material by an impregnation method or a coprecipitation method, wherein the implantation amount of the catalyst is 1.0 wt.% or 20wt.% or 50 wt.% in terms of mass percentage;
(2) placing the material obtained in the step (1) in microwave heating equipment, heating to 500-1800 ℃ at a heating rate of 100-120 ℃/min, and keeping for 0.25-2 hours to obtain a product G-AC;
(3) taking G-AC and NaNO according to the mass ratio of 1:1:53And KMnO4Successively, the solution was slowly added to 95 wt.% H in mass percentage immersed in an ice-water bath2SO4In (H)2SO4The mass ratio of the raw materials to the G-AC is 1.5:1, the raw materials are continuously stirred for 3 to 3.2 hours, then the raw materials are heated to 35 to 37 ℃, and the mixture is stirred for 45 to 50 minutes; then heating to 80-82 ℃, and keeping the temperature for 1-1.2 h; keeping the temperature unchanged, dropwise adding deionized water into the mixture, wherein the mass ratio of the deionized water to the G-AC is 3:1, and then dropwise adding H with the mass percentage of 30 wt%2O2，H2O2The mass ratio of the mixed solution to G-AC is 0.25:1；
(4) centrifuging the material obtained in the step (3), removing clear liquid, and washing the residual solid with 1M HCl solution and deionized water until the pH value of the solution is neutral;
(5) adding the material obtained in the step (4) into deionized water for ultrasonic treatment for 20-40 minutes, and then carrying out freeze drying to obtain graphene oxide, which is marked as Ox-MG;
(6) and (3) placing the Ox-MG obtained in the step (5) into a corundum crucible with a cover, then placing the corundum crucible into a muffle furnace preheated to 900-920 ℃, heating the corundum crucible for 10-20 minutes in a nitrogen atmosphere, and cooling to obtain few-layer graphene, namely MG.
The catalyst comprises one or more transition metal salts or one or more transition metals in ionic form; the transition metal includes Fe, Ni, Co, Zn, Mn.
The one or more transition metal salts are obtained by reacting transition metal ions with the valence less than 3 with nitric acid or hydrochloric acid.
The one or more transition metals in ionic form should have a valence of less than 3.
The carbon atoms of the few-layer three-dimensional graphene high-performance anode composite carbon material are in a hexagonal arrangement, such as a sheet shape, a spherical shape, a cage shape or an irregular shape, the number of layers of graphene is 2-50, and the structure comprises one or more of the following characteristics:
(1) the X-ray diffraction peak mirror surfaces were { 002 }, { 101 }, { 100 } and { 004 };
(2) the interlayer spacing is between 0.333nm and 0.345 nm;
(3) the crystallinity, namely the graphene degree is between 50 and 100 percent;
(4) the crystal size is more than or equal to 0.246 nm.
The method comprises the following specific implementation steps:
(1) 20.0 wt.% catalyst was implanted into carbonaceous feedstock by impregnation. 5.9g of Ni (NO)3)2Adding the catalyst into 15mL of deionized water, stirring until the catalyst is completely dissolved, adding 6 g of coconut shell Activated Carbon (AC) into the solution, carrying out ultrasonic treatment for 30 minutes,drying in a 105 ℃ oven for 12 h.
(2) And (2) placing the material obtained in the step (1) in a microwave oven, heating to 1400 ℃ at the heating rate of 100 ℃/min, and keeping for 15 minutes to obtain a product G-AC. The X-ray diffraction pattern of G-AC is shown in FIG. 1.
(3) Taking 3gG-AC and 3gNaNO according to the mass ratio of 1:1:53And 15gKMnO4Sequentially, slowly add to 130mL 95 wt.% H immersed in an ice-water bath2SO4Continuously stirring for 3 hours, heating to 35 ℃, and stirring for 45 minutes; then heating to 80 ℃, and keeping the temperature for 1 h; while maintaining the temperature, 260mL of deionized water was added dropwise, followed by 50mL of 30 wt.% H2O2。
(4) And (4) centrifuging the material obtained in the step (3), removing a clear liquid, and washing the residual solid with 1M HCl solution and deionized water until the pH value of the solution is neutral.
(5) And (4) adding the material obtained in the step (4) into deionized water for ultrasonic treatment for 30 minutes, and then carrying out freeze drying to obtain graphene oxide, which is recorded as Ox-MG. The X-ray diffraction spectrum of Ox-MG is shown in figure 1.
(6) And (3) placing the Ox-MG obtained in the step (5) into a corundum crucible with a cover, then placing the corundum crucible into a muffle furnace preheated to 900-920 ℃, heating for 10 minutes in a nitrogen atmosphere, and cooling to obtain few-layer graphene, namely MG. The X-ray diffraction pattern of MG is shown in FIG. 1, and the transmission electron micrograph is shown in FIG. 2.
The constant current charge-discharge characteristic curve of the prepared MG three-dimensional few-layer graphene composite material product is shown in figure 3. At 100mA/g, the capacity of MG reaches more than 1500mAh/g, which is far better than the theoretical value (372mAh/g) of commercial graphite, and has good electrochemical performance and charge-discharge capacity.
Claims (5)
1. A method for preparing a few-layer three-dimensional graphene high-performance anode composite carbon material is characterized in that the method takes any one or a mixture of more of biomass, coal, semicoke and activated carbon as a carbonaceous raw material, and the few-layer three-dimensional graphene high-performance anode composite carbon material is obtained by implanting a catalyst and carrying out microwave catalytic graphitization; the method is realized by the following technical steps:
(1) implanting a catalyst into the carbonaceous raw material by an impregnation method or a coprecipitation method, wherein the implantation amount of the catalyst is 1 wt.% or 20wt.% or 50 wt.% in terms of mass percentage;
(2) placing the material obtained in the step (1) in microwave heating equipment, heating to 500-1800 ℃ at a heating rate of 100-120 ℃/min, and keeping for 0.25-2 hours to obtain a product G-AC;
(3) taking G-AC and NaNO according to the mass ratio of 1:1:53And KMnO4Successively, the solution was slowly added to 95 wt.% H in mass percentage immersed in an ice-water bath2SO4In (H)2SO4The mass ratio of the raw materials to the G-AC is 1.5:1, the raw materials are continuously stirred for 3 to 3.2 hours, then the raw materials are heated to 35 to 37 ℃, and the mixture is stirred for 45 to 50 minutes; then heating to 80-82 ℃, and keeping the temperature for 1-1.2 h; keeping the temperature unchanged, dropwise adding deionized water into the mixture, wherein the mass ratio of the deionized water to the G-AC is 3:1, and then dropwise adding H with the mass percentage of 30 wt%2O2，H2O2The mass ratio of the raw material to the G-AC is 0.25: 1;
(4) centrifuging the material obtained in the step (3), removing clear liquid, and washing the residual solid with 1M HCl solution and deionized water until the pH value of the solution is neutral;
(5) adding the material obtained in the step (4) into deionized water for ultrasonic treatment for 20-40 minutes, and then carrying out freeze drying to obtain graphene oxide, which is marked as Ox-MG;
(6) and (3) placing the Ox-MG obtained in the step (5) into a corundum crucible with a cover, then placing the corundum crucible into a muffle furnace preheated to 900-920 ℃, heating the corundum crucible for 10-20 minutes in a nitrogen atmosphere, and cooling to obtain few-layer graphene, namely MG.
2. The method of claim 1, wherein the catalyst comprises one or more transition metal salts or one or more transition metals in ionic form; the transition metal includes Fe, Ni, Co, Zn, Mn.
3. The method for preparing the few-layer three-dimensional graphene high-performance anode composite carbon material according to claim 2, wherein the one or more transition metal salts are obtained by reacting transition metal ions with a valence of less than 3 with nitric acid or hydrochloric acid.
4. The method for preparing the few-layer three-dimensional graphene high-performance anode composite carbon material according to claim 2, wherein the one or more transition metals are in an ionic form, and the valence number of the transition metal is less than 3.
5. The method for preparing the few-layer three-dimensional graphene high-performance anode composite carbon material according to claim 1, wherein carbon atoms of the few-layer three-dimensional graphene high-performance anode composite carbon material are in a hexagonal arrangement and are in a sheet shape, a spherical shape, a cage shape or an irregular shape, the number of graphene layers is 2-50, and the structure comprises one or more of the following characteristics:
(1) the X-ray diffraction peak mirror surfaces were { 002 }, { 101 }, { 100 } and { 004 };
(2) the interlayer spacing is between 0.333nm and 0.345 nm;
(3) the crystallinity, namely the graphene degree is between 50% and 100%;
(4) the crystal size is more than or equal to 0.246 nm.
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