CN114188532A - Graphene negative electrode material and preparation method and application thereof - Google Patents
Graphene negative electrode material and preparation method and application thereof Download PDFInfo
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- 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
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1393—Processes of manufacture of electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
-
- 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
- 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
Abstract
The invention provides a graphene negative electrode material and a preparation method and application thereof, and a Raman spectrum I of the graphene negative electrode materialD/IGSatisfies the condition that I is more than or equal to 0.1D/IGLess than or equal to 2, and the average grain diameter of the graphene negative electrode material is 500 nm-2500 nm. The graphene material can be directly used as a negative active material, and can remarkably improve the performances such as the cyclicity of a negative electrode and a battery.
Description
Technical Field
The invention relates to a graphene negative electrode material and a preparation method and application thereof, and belongs to the field of carbon materials and application thereof.
Background
The lithium ion battery has the advantages of high energy density, long cycle life, strong adaptability to external environment and the like, and is widely applied to the fields of portable electronic equipment, new energy automobiles and the like. The lithium ion battery mainly comprises a positive electrode, a negative electrode and electrolyte, wherein the common positive electrode material is mainly lithium transition metal oxide, such as lithium iron phosphate (LiFePO)4) Lithium cobaltate (LiCoO)2) Ternary materials, etc., the common cathode material is mainly graphite, such as naturalGraphite, and the like. For the negative electrode, the graphite can provide lower and stable working voltage, has long cycle life and high coulombic efficiency, but has lower theoretical capacity of only 372mA h g-1The improvement of the electrochemical performance of the lithium ion battery is greatly limited (Journal of Energy Chemistry 2020; 49; 233-. Therefore, the research and development of the high-performance negative electrode material are effective ways for optimizing the performance of the lithium ion battery and promoting the application and development of the lithium ion battery to the electric equipment.
Graphene is a novel carbon nano material with a two-dimensional structure, is considered to be the thinnest and the highest strength material at present, and has a large application potential in the aspect of electrode materials. For example, patent document CN102306757A discloses a silicon graphene composite negative electrode material for a lithium ion battery, which is composed of silicon powder, graphene and amorphous carbon, wherein the graphene forms a three-dimensional conductive network with an internal cavity, and the silicon powder is wrapped in the internal cavity to form spherical or spheroidal composite particles; CN109592674A discloses a graphene negative electrode material, which includes graphene, soluble mesophase pitch, and mesophase micron-sized carbon microspheres, wherein the surface of the mesophase micron-sized carbon microspheres is coated with the soluble mesophase pitch to form core-shell particles, and the core-shell particles are distributed inside the graphene. Therefore, it is an important subject faced by those skilled in the art to develop a novel graphene material to improve the performance of the graphene material as a negative electrode active material, and to have an important significance in improving the performances of negative electrodes and batteries, such as cyclability.
Disclosure of Invention
The invention provides a graphene negative electrode material, a preparation method and application thereof.
In one aspect of the invention, a graphene negative electrode material is provided, and the Raman spectrum I of the graphene negative electrode materialD/IGSatisfies the condition that I is more than or equal to 0.1D/IGLess than or equal to 2; the stoneThe average particle size of the graphene negative electrode material is 500 nm-2500 nm.
According to an embodiment of the present invention, the X-ray diffraction (XRD) analysis result of the graphene negative electrode material shows that: (002) the diffraction angle 2 theta of the interlayer spacing is 23-25 degrees; and/or the specific surface area of the graphene anode material is 1m2/g～5m2(ii)/g; and/or the carbon content of the graphene negative electrode material is not lower than 99.99%; and/or the graphene negative electrode material comprises 1-10 layers of graphene.
In another aspect of the present invention, a preparation method of the graphene negative electrode material is provided, which includes: and (3) crushing the graphene raw material by using a jet mill to obtain the graphene negative electrode material.
According to an embodiment of the present invention, in the pulverizing process, the rotation speed of the jet mill is 100-; and/or the time of the crushing treatment is 1-48 h.
According to an embodiment of the present invention, the method further includes a preparation process of the graphene raw material, where the preparation process of the graphene raw material includes: adding a graphite raw material into a reaction kettle, introducing gas into the reaction kettle until the gas introduced into the reaction kettle is in a supercritical state, and performing intercalation reaction on the graphite raw material in the supercritical state; and after the reaction is finished for 120 +/-50 min, releasing the pressure of the reaction kettle to strip the reacted graphite raw material to obtain the graphene raw material.
In another aspect of the present invention, a negative electrode sheet is provided, which includes a negative electrode current collector and a negative electrode active material layer on a surface of the negative electrode current collector, where the negative electrode active material layer includes a negative electrode active material, a conductive agent, and a binder, and the negative electrode active material includes the graphene negative electrode material.
According to one embodiment of the present invention, the negative electrode active material layer contains 50% to 94% by mass of the negative electrode active material.
According to an embodiment of the present invention, the conductive agent includes carbon black; and/or, in the negative electrode active material layer, the mass content of the conductive agent is 1.5-45.5%; and/or, the binder comprises polyvinylidene fluoride; in the negative electrode active material layer, the mass content of the binder is 4.5-45.5%.
In another aspect of the present invention, a preparation method of the negative electrode sheet is provided, which includes: mixing the negative electrode active material, a conductive agent, a binder and a dispersing agent to prepare slurry; the dispersant comprises N-methyl pyrrolidone; and coating the slurry on the surface of a current collector, and drying and rolling to form a negative active material layer to obtain the negative plate.
In another aspect of the present invention, a lithium ion battery is provided, which includes the above negative electrode sheet.
In the invention, I of the graphene negative electrode materialD/IGSatisfies the condition that I is more than or equal to 0.1D/IGThe lithium ion battery cathode material has the advantages of wide voltage platform and excellent multiplying power performance, can provide lower and stable working voltage, and has high reversible capacity (at 200 mAg) under different current densities (at 200 mAg), and simultaneously has small particle size characteristics, superfine graphene (namely graphene cathode material) with the characteristics is introduced into the cathode sheet to be used as a cathode active material, so that the lithium ion battery cathode material is beneficial to the embedding and the releasing of lithium ions, has good storage capacity for the lithium ions, and has the advantages of good conductivity, mechanical property, high capacity and the like, can be directly used as the cathode active material, is not required to be compounded with materials such as silicon and the like, is more convenient to use, and can remarkably improve the capacities, the cyclicity and the like of the cathode and the battery-1Under the condition, the reversible capacity can be up to 542mA h g-1The above); in addition, the graphene negative electrode material disclosed by the invention also has the advantages of simple preparation process, high efficiency and the like, and has important significance for practical industrial application.
Drawings
Fig. 1 is a scanning electron microscope image of the graphene negative electrode material prepared in example 1;
FIG. 2 is a graph of rate performance of the lithium ion battery of example 1;
FIG. 3 shows that the lithium ion battery of example 1 is operated at 400mA g-1Cyclic performance curve under currentA drawing;
fig. 4 is a rate performance graph of a lithium ion battery using the graphene negative electrode material of example 2, graphite, and conventional graphene as negative electrode active materials, respectively;
FIG. 5 shows the lithium ion battery using the graphene negative electrode material, graphite and conventional graphene of example 2 as negative electrode active materials at 200mA g-1A charge-discharge curve diagram under the current density of (a);
fig. 6 is a transmission electron microscope image of the graphene negative electrode material prepared in example 3;
FIG. 7 is a graph of rate performance for the lithium ion battery of example 3;
FIG. 8 shows that the lithium ion battery of example 3 is operated at 600mA g-1A lower charge-discharge curve chart;
FIG. 9 shows that the lithium ion battery of example 3 is operated at 800mA g-1A lower charge-discharge curve chart;
fig. 10 is a raman spectrum of the graphene negative electrode material prepared in example 3;
fig. 11 is an X-ray diffraction (XRD) pattern of the graphene negative electrode material prepared in example 2.
Detailed Description
The present invention is described in further detail below in order to enable those skilled in the art to better understand the aspects of the present invention. The following detailed description is merely illustrative of the principles and features of the present invention, and the examples are intended to be illustrative of the invention and not limiting of the scope of the invention. All other embodiments obtained by a person of ordinary skill in the art based on the embodiments of the present invention without any creative effort belong to the protection scope of the present invention.
The invention provides a graphene negative electrode material and a Raman spectrum I of the graphene negative electrode materialD/IGSatisfies the condition that I is more than or equal to 0.1D/IGLess than or equal to 2; the average particle size of the graphene negative electrode material is 500 nm-2500 nm.
In particular, Raman Spectroscopy ID/IGIs 1350cm in Raman spectrum of graphene cathode material-1Peak height of (I)1350(ID) And 1580cm-1Peak height of (I)1580(IG) The ratio of (a) to (b). For example, ID/IGFor example, the amount is in the range of 0.1, 0.3, 0.5, 0.7, 0.9, 1.2, 1.5, 1.8, 2 or any two thereof, and I is generally preferredD/IG＜2。
For example, the average particle size of the graphene anode material may be in a range of 500nm, 1000nm, 1500nm, 2000nm, 2500nm, or any two thereof. In specific implementation, the average particle size of the graphene negative electrode material can be determined by using a conventional particle size tester in the field, such as a nanometer laser particle size analyzer.
In general, the X-ray diffraction (XRD) analysis result of the graphene negative electrode material shows that the diffraction angle 2 θ of the (002) interlayer spacing is 5 ° to 90 ° (i.e., the XRD ray diffraction range is 5 ° to 90 °), for example, a range consisting of 5 °, 10 °, 15 °, 20 °, 23 °, 25 °, 30 °, 40 °, 50 °, 60 °, 70 °, 80 °, 90 °, or any two thereof.
Through further research, the graphene negative electrode material has good crystallinity, and the X-ray diffraction (XRD) analysis result shows that the graphene negative electrode material has the diffraction angle of ultrafine graphene, namely the diffraction angle 2 theta of (002) interlamellar spacing is 23-25 degrees, so that the performance of the graphene negative electrode material as a negative active material is further improved by adopting the graphene negative electrode material.
In some embodiments, the graphene anode material has a specific surface area of 1m2/g～5m2G, e.g. 1m2/g、2m2/g、3m2/g、4m2/g、5m2(ii)/g or any two thereof.
In some embodiments, the carbon content of the graphene anode material is not less than 99.99%, and the rest can be hydrogen element and the like. In specific implementation, elemental analysis may be performed on the graphene negative electrode material to determine the carbon content therein, and the elemental analysis may be performed by using apparatuses and methods that are conventional in the art, which is not particularly limited.
The graphene is composed of a single carbon atom layer and belongs to a two-dimensional crystal structure, the graphene negative electrode material provided by the invention specifically comprises 1-10 layers of graphene (namely the graphene has a layered structure formed by 1-10 layers of single-layer graphene), namely the graphene negative electrode material comprises at least one of 1 layer of graphene, 2 layers of graphene, 3 layers of graphene, 4 layers of graphene, 5 layers of graphene, 6 layers of graphene, 7 layers of graphene, 8 layers of graphene, 9 layers of graphene and 10 layers of graphene, and most of the graphene layers are concentrated in 1-4 layers.
Specifically, the graphene anode material may be graphene with n number of layers (i.e., composed of n layers of single-layer graphite), 1 ≦ n ≦ 10, n being, for example, in the range of 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, or any two thereof, preferably 1 ≦ n ≦ 7. The graphene negative electrode material is graphene with n layers, which means that most of graphene in the graphene negative electrode material has n layers, that is, most of graphene is graphene with n layers, and due to factors such as preparation process errors, a small number or a very small number of graphene with n layers may exist.
The preparation method of the graphene negative electrode material comprises the following steps: and (3) crushing the graphene raw material by using a jet mill to obtain the graphene negative electrode material. According to the research of the invention, the preparation method can crush the graphene raw material to obtain the graphene with smaller particle size (namely the graphene negative electrode material), and meanwhile, the preparation method has a certain stripping effect to reduce the number of layers and the thickness of the obtained graphene with small particle size, more importantly, the surface smoothness of the obtained graphene can be ensured, so that the graphene negative electrode material has proper defect density, and meanwhile, the integrity of the lamellar structure of the graphene negative electrode material is ensured. In addition, the preparation method also has the advantages of simple operation, low cost and the like.
Generally, in the crushing process, the rotation speed of the jet mill is 100-. The rotational speed of the jet mill is, for example, 100r/min, 1000r/min, 3000r/min, 5000r/min, 7000r/min, 10000r/min, 20000r/min, 30000r/min, 40000r/min, 50000r/min or a range consisting of any two thereof. The time for the pulverization treatment may be generally 1 to 48 hours, for example, 1 hour, 5 hours, 10 hours, 20 hours, 30 hours, 40 hours, 48 hours or a range of any two of them.
In some embodiments, the number of times of the crushing treatment may be 5-15, which is more beneficial to obtaining the graphene anode material with a small particle size. In specific implementation, the graphene raw material can be added into a jet mill for crushing, then the crushed product is sieved to remove large-particle substances, the obtained small-particle product is added into the jet mill for crushing, and the crushing-sieving process is repeated for 5-15 times to obtain the graphene negative electrode material. The mesh number of the screen used for sieving can be generally 200-10000 meshes, in the crushing-sieving process, firstly, a screen with the mesh number of m1 is adopted for sieving to remove large particles, the obtained first-level small particles are crushed again, then, a screen with the mesh number of m2 is adopted for sieving to remove large particles, the obtained second-level small particles are crushed again, then, a screen with the mesh number of m3 is adopted for sieving … …, and the like, until the crushing-sieving process is repeated, the graphene cathode material is obtained, wherein the m1, the m2 and the m3 … … are sequentially increased (namely, the aperture of the used screen is sequentially reduced).
In addition, during specific implementation, the material to be crushed (such as the graphene raw material) can be added into the jet mill for crushing 3-6 times, that is, the material to be crushed can be averagely divided into 3-6 parts, and the material to be crushed is added into the jet mill for crushing treatment.
In the present invention, the graphene raw material may be prepared by using a supercritical fluid, and in some preferred embodiments, the graphene raw material is prepared by a process including: adding a graphite raw material into a reaction kettle, introducing gas into the reaction kettle until the gas introduced into the reaction kettle is in a supercritical state, and performing intercalation reaction on the graphite raw material in the supercritical state; and after the reaction is finished, the pressure of the reaction kettle is relieved to strip the reacted graphite raw material to obtain the graphene raw material. Alternatively, the temperature in the supercritical state may be 50 ± 5 ℃, and the pressure may be such that the gas is in the supercritical state, the gas may include carbon dioxide, and the graphite raw material may specifically include natural graphite.
In the preparation process, the number of layers of the used graphene raw materials can be 1-10, and the carbon content of the graphene raw materials can be not less than 99.9% (generally, the carbon content of the prepared graphene negative electrode material is basically equal to that of the used graphene raw materials).
The negative plate comprises a negative current collector and a negative active material layer positioned on the surface of the negative current collector, wherein the negative active material layer comprises a negative active material, a conductive agent and a binder, and the negative active material comprises the graphene negative material. The negative electrode active material may be entirely a graphene negative electrode material.
In some embodiments, the negative electrode active material layer may have a mass content of the negative electrode active material of 50% to 94%, for example, in a range of 50%, 60%, 70%, 80%, 90%, 94%, or any two thereof, the conductive agent may have a mass content of 1.5% to 45.5%, and the binder may have a mass content of 4.5% to 45.5%.
Specifically, the conductive agent may include carbon black, and the binder may include polyvinylidene fluoride (PVDF), so as to facilitate the coordination with the graphene negative electrode material and optimize the performance of the negative electrode sheet. However, the invention is not limited thereto, and other materials such as conductive agents and adhesives that are conventional in the art may be used.
Specifically, in the above negative electrode sheet, both the front and back surfaces of the negative electrode current collector may be provided with the negative electrode active material layer, or one surface of the negative electrode current collector may be provided with the negative electrode active material layer, which may be selected as required in specific implementation. The negative electrode current collector may be a copper foil or the like which is conventional in the art, and the present invention is not particularly limited thereto.
The preparation method of the negative plate comprises the following steps: mixing a negative electrode active material, a conductive agent, a binder and a dispersant to prepare slurry, wherein the dispersant comprises N-methylpyrrolidone (NMP); and coating the slurry on the surface of the current collector, drying and rolling to form a negative electrode active material layer to obtain the negative electrode sheet. According to the process, the negative plate is prepared through a coating method, NMP is used as a dispersing agent (or called solvent), so that the uniform dispersion of components such as a graphene negative electrode material and a conductive agent is facilitated, the occurrence of phenomena such as particle aggregation is avoided, and the negative plate with excellent performance is prepared. In specific implementation, the binder may be dissolved in a solvent, and then the obtained binder solution may be mixed with materials such as a negative electrode active material, a conductive agent, a dispersing agent, and the like to prepare a slurry, where the mass concentration of the binder in the binder solution may be generally 5 to 9%, and the solvent for dissolving the binder may include NMP and the like.
The slurry can be coated on the surface of the negative current collector by adopting a blade coater and other conventional coating devices in the field, the slurry can be dried at 80-120 ℃ after being coated on the surface of the negative current collector, then the slurry is rolled and cut into sheets meeting the requirements of shape and size by adopting a tablet press, and the sheets can be further dried at 80-120 ℃ to obtain the negative electrode sheet.
The lithium ion battery comprises the negative plate. The lithium ion battery may be, for example, a button cell battery, but is not limited thereto, and may be manufactured according to a conventional method in the art.
The lithium ion battery also comprises a positive plate and a diaphragm, wherein the diaphragm is positioned between the positive plate and the negative plate and used for separating the positive plate from the negative plate. The present invention may employ commercially available or self-made positive electrode sheets and separators that are conventional in the art, such as lithium sheets, and separators such as commercially available celgard2400 separators and the like.
In addition, the lithium ion battery also contains an electrolyte, and the electrolyte used can comprise an organic solvent and a lithium salt, wherein the organic solvent can comprise ethylene phosphate and/or dimethyl carbonate, and the lithium salt can comprise lithium hexafluorophosphate (LiPF)6) The concentration of the lithium salt in the electrolyte is, for example, 0.8 to 1.5mol/L, but the composition of the electrolyte is not limited thereto.
To make the objects, technical solutions and advantages of the present invention clearer, the technical solutions of the present invention will be clearly and completely described below with reference to specific embodiments, and it is obvious that the described embodiments are some, but not all embodiments of the present invention. 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.
In the following examples, a new Verley charge-discharge tester was used to test the battery performance, including rate performance test, charge-discharge characteristic test, and cycle performance test, the voltage range of the constant current charge-discharge test was 0.01-3V, and the current density range was 200-1000mA g-1。
Example 1
1. Preparing a graphene raw material by using a supercritical fluid: adding natural graphite into a reaction kettle, introducing carbon dioxide into the reaction kettle, heating to about 50 ℃, controlling the pressure to enable the carbon dioxide introduced into the reaction kettle to be in a supercritical state, enabling the graphite raw material to perform intercalation reaction in the supercritical state, after reaction for about 120min, after the reaction is finished, enabling the reaction kettle to be decompressed, and stripping the reacted graphite raw material to obtain the graphene raw material.
2. Preparation of graphene anode material
(1) Adding 30g of graphene raw material into a jet mill for 5-6 times, and stirring and crushing at the rotating speed of 500-3000r/min for 24-30h to obtain a crushed product;
(2) sieving the crushed product, wherein the mesh number of the used sieve is 2000-6000 meshes, and collecting the small-particle product passing through the sieve;
(3) and (3) repeating the step (1) and the step (2) on the small-particle product, and repeating the step (1) and the step (2) for 9 times (namely, crushing for 10 times) to obtain the graphene anode material.
Through testing, the Raman spectrum I of the graphene materialD/IG0.9, the average particle size was about 2600nm, and XRD analysis showed: diffraction angle with ultrafine graphene, i.e., diffraction angle 2 θ of (002) interlayer spacing, 25.9 °; the specific surface area is 1.8m2The number of layers is 4, and the carbon content is more than 99.99 percent.
In addition, the graphene negative electrode material is analyzed by a Scanning Electron Microscope (SEM), and the result is shown in fig. 1, and it can be seen that the graphene has the characteristics of smooth and flat surface, uniform distribution and the like.
3. Preparation of negative plate
Mixing the graphene negative electrode material, carbon black, a PVDF solution (7 mass concentration of PVDF) and NMP, and uniformly stirring the mixture by a magnetic stirrer (the stirring time is about 9 hours) to prepare slurry;
coating the slurry on the surface of a copper foil by using a blade coater, then drying the copper foil in an oven at 100 ℃, then rolling and cutting the copper foil into sheets with the diameter of 13mm by using a tablet machine, and then drying the sheets in a vacuum oven at 80 ℃ for 12 hours to obtain the negative plate.
4. Preparation of lithium ion batteries
A lithium plate is used as a positive plate (reference electrode), the positive plate, a celgard2400 diaphragm and a negative plate are combined into a button cell in a glove box filled with argon, and electrolyte used by the button cell is composed of ethylene phosphate, dimethyl carbonate and LiPF6Composition of, wherein LiPF6The concentration of (2) is 1 mol/L.
5. Lithium ion battery performance testing
(1) The graph of the rate performance of the lithium ion battery is shown in fig. 2, and it can be seen that the lithium ion battery is 200mA g-1Capacity at current density of about 542mA hr g-1。
(2) The lithium ion battery is measured to be 400mA g-1The graph of the cycle performance under current is shown in FIG. 3, and it can be seen that the lithium ion battery is 400mA g-1The capacity of circulating 100 circles under the current density is 431mA h g-1And the capacity is not attenuated after circulation, and the good circulation performance is shown.
Example 2
Example 2 is different from example 1 in that, in the step (3) of preparing the graphene anode material, the steps (1) and (2) are repeated 12 times (i.e., the total pulverization is 13 times), and the rest of the conditions are the same as example 1.
Through testing, the Raman spectrum I of the graphene anode materialD/IG0.6, average particle size about 800 nm; XRD analysis results show that: a diffraction angle 2 θ having a diffraction angle of ultrafine graphene, that is, a (002) interlayer spacing of 25.4 ° (an XRD pattern thereof is shown in fig. 11); the specific surface area is 2.7m2The number of layers is 3, and the carbon content is more than 99.99 percent.
The rate capability curve of the lithium ion battery of example 2 was measuredThe line is shown in fig. 4 (see the corresponding curve of graphene anode material in fig. 4), which is at 200mA g-1The charge and discharge curve under the current density condition of (a) is shown in fig. 5 (see the curve corresponding to the graphene negative electrode material in fig. 5);
in addition, the conventional coarse graphene is used to replace the graphene negative electrode material in example 1, the lithium ion battery is prepared according to the process of the example, and the rate performance curve is shown in fig. 4 (see the curve corresponding to the conventional graphene in fig. 4), which is measured at 200mA g-1The charge and discharge curves under the current density condition of (a) are shown in fig. 5 (see the corresponding curve of the conventional graphene in fig. 5); wherein the Raman spectrum I of the crude grapheneD/IG2, the average particle size is about 3000 nm-30000 nm, and XRD analysis results show that: it has the diffraction angle of coarse graphene, i.e. the diffraction angle 2 θ of (002) interlayer spacing is 26 °; the specific surface area is 1.5m2The number of layers is 8-15, and the carbon content is 99.99%;
the commercial graphite is used to replace the graphene negative electrode material in example 1, the lithium ion battery is prepared according to the process of example 1, and the rate performance curve is shown in fig. 4 (see the curve corresponding to the graphite in fig. 4), and is measured to be 200mA g-1The charge/discharge curve under the current condition of (2) is shown in fig. 5 (see the curve corresponding to graphite in fig. 5).
As can be seen from fig. 4 and 5, the capacity of the lithium ion battery of example 2 under different current density conditions and different cycle times is significantly higher than that of the lithium ion battery using graphite and conventional graphite, and the lithium ion battery of example 2 is 200mA g-1Has a wider plateau at a voltage of 0.5V under the current condition of (a).
Example 3
Example 2 is different from example 1 in that, in the step (3) of preparing the graphene anode material, the steps (1) and (2) are repeated 14 times (i.e., co-pulverization is performed 15 times), and the rest of the conditions are the same as example 1.
The Raman spectrum of the graphene material is shown in figure 10 through testing, and the Raman spectrum I thereofD/IG0.2, average particle size of about 500nm, XRD analysis showed: diffraction angle with ultrafine graphene, i.e. diffraction angle 2 θ of (002) interlayer spacing, 25 °; specific surface areaIs 3.9m2The number of layers is 2, and the carbon content is more than 99.99 percent.
A Transmission Electron Microscope (TEM) image of the graphene negative electrode material of example 3 is shown in fig. 6, and as can be seen from fig. 6, the surface of the graphene negative electrode material is flat and has an integral lamellar structure (the structures of the graphene negative electrode materials of examples 1 and 2 are similar to those of the graphene negative electrode material of example 3).
The rate performance curve of the lithium ion battery of example 3 is shown in FIG. 7, and the lithium ion battery is measured at 600mA g-1The charge/discharge curve under the current density condition of (2) is shown in FIG. 8, and is at 800mA g-1The charge/discharge curve under the current density condition of (2) is shown in FIG. 9, which is 600mA g-1、800mA g-1The specific capacity under the current is about 135mA h g-1And 107mA h g-1It is shown that there is still a broad 0.5V voltage plateau at high current.
The embodiments of the present invention have been described above. However, the present invention is not limited to the above embodiment. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. The graphene negative electrode material is characterized in that the Raman spectrum I of the graphene negative electrode materialD/IGSatisfies the condition that I is more than or equal to 0.1D/IGLess than or equal to 2; the average particle size of the graphene negative electrode material is 500 nm-2500 nm.
2. The graphene anode material according to claim 1,
the X-ray diffraction (XRD) analysis result of the graphene negative electrode material shows: (002) the diffraction angle 2 theta of the interlayer spacing is 23-25 degrees; and/or the presence of a gas in the gas,
the specific surface area of the graphene negative electrode material is 1m2/g～5m2(ii)/g; and/or the presence of a gas in the gas,
the carbon content of the graphene negative electrode material is not lower than 99.99%; and/or the presence of a gas in the gas,
the graphene negative electrode material comprises 1-10 layers of graphene.
3. The preparation method of the graphene anode material of claim 1, characterized by comprising: and (3) crushing the graphene raw material by using a jet mill to obtain the graphene negative electrode material.
4. The method as claimed in claim 3, wherein the rotational speed of the jet mill is 100-50000r/min during the pulverizing treatment; and/or the time of the crushing treatment is 1-48 h.
5. The method according to claim 3 or 4, further comprising a graphene raw material preparation process, wherein the graphene raw material preparation process comprises: adding a graphite raw material into a reaction kettle, introducing gas into the reaction kettle until the gas introduced into the reaction kettle is in a supercritical state, and performing intercalation reaction on the graphite raw material in the supercritical state; and after the reaction is finished for 120 +/-50 min, releasing the pressure of the reaction kettle to strip the reacted graphite raw material to obtain the graphene raw material.
6. A negative electrode sheet comprising a negative electrode current collector and a negative electrode active material layer on a surface of the negative electrode current collector, wherein the negative electrode active material layer comprises a negative electrode active material, a conductive agent and a binder, and the negative electrode active material comprises the graphene negative electrode material according to claim 1 or 2.
7. The negative electrode sheet according to claim 6, wherein the negative electrode active material layer contains 50 to 94% by mass of the negative electrode active material.
8. Negative electrode sheet according to claim 6 or 7,
the conductive agent includes carbon black; and/or the presence of a gas in the gas,
in the negative electrode active material layer, the mass content of the conductive agent is 1.5-45.5%; and/or the presence of a gas in the gas,
the binder comprises polyvinylidene fluoride;
in the negative electrode active material layer, the mass content of the binder is 4.5-45.5%.
9. The negative electrode sheet preparation method of any one of claims 6 to 8, comprising:
mixing the negative electrode active material, a conductive agent, a binder and a dispersing agent to prepare slurry; the dispersant comprises N-methyl pyrrolidone;
and coating the slurry on the surface of a current collector, and drying and rolling to form a negative active material layer to obtain the negative plate.
10. A lithium ion battery comprising the negative electrode sheet according to any one of claims 6 to 8.
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Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012250880A (en) * | 2011-06-03 | 2012-12-20 | Semiconductor Energy Lab Co Ltd | Graphene, electric storage device and electric equipment |
| WO2014087992A1 (en) * | 2012-12-04 | 2014-06-12 | 昭和電工株式会社 | Graphene sheet composition |
| CN105110326A (en) * | 2015-09-10 | 2015-12-02 | 朱振业 | Method adopting a liquid phase stripping method to prepare grapheme and grapheme |
| CN106423485A (en) * | 2016-10-21 | 2017-02-22 | 成都新柯力化工科技有限公司 | Device and method for preparing graphene through jet milling |
| CN106629687A (en) * | 2016-09-20 | 2017-05-10 | 成都新柯力化工科技有限公司 | Method for preparing graphene by jet mill and graphene |
| US20170346098A1 (en) * | 2014-10-10 | 2017-11-30 | Toray Industries, Inc. | Graphene powder, electrode paste for lithium ion battery and electrode for lithium ion battery |
| CN108063253A (en) * | 2016-11-07 | 2018-05-22 | 苏州宝时得电动工具有限公司 | Graphene and preparation method thereof, the Anode and battery containing graphene |
| CN108298530A (en) * | 2018-01-17 | 2018-07-20 | 中国石油大学(北京) | A kind of form the few-layer graphene alkene and the preparation method and application thereof |
| CN109179383A (en) * | 2018-01-17 | 2019-01-11 | 中原大学 | Graphene structure, method for preparing graphene and lithium ion battery electrode |
| CN111252757A (en) * | 2019-10-10 | 2020-06-09 | 中国科学院生态环境研究中心 | Method for preparing graphene by using waste lithium ion power battery |
| KR20200103603A (en) * | 2018-09-06 | 2020-09-02 | 한국과학기술원 | Graphene-based compound and manufacturing method thereof and composition for graphene-based manufacturing compound and graphene quantum dot |
| CN112978722A (en) * | 2019-12-17 | 2021-06-18 | 山东海科创新研究院有限公司 | Small-diameter graphene powder, graphene conductive paste, and preparation methods and applications thereof |
-
2021
- 2021-11-09 CN CN202111318097.7A patent/CN114188532A/en active Pending
Patent Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012250880A (en) * | 2011-06-03 | 2012-12-20 | Semiconductor Energy Lab Co Ltd | Graphene, electric storage device and electric equipment |
| WO2014087992A1 (en) * | 2012-12-04 | 2014-06-12 | 昭和電工株式会社 | Graphene sheet composition |
| US20170346098A1 (en) * | 2014-10-10 | 2017-11-30 | Toray Industries, Inc. | Graphene powder, electrode paste for lithium ion battery and electrode for lithium ion battery |
| CN105110326A (en) * | 2015-09-10 | 2015-12-02 | 朱振业 | Method adopting a liquid phase stripping method to prepare grapheme and grapheme |
| CN106629687A (en) * | 2016-09-20 | 2017-05-10 | 成都新柯力化工科技有限公司 | Method for preparing graphene by jet mill and graphene |
| CN106423485A (en) * | 2016-10-21 | 2017-02-22 | 成都新柯力化工科技有限公司 | Device and method for preparing graphene through jet milling |
| CN108063253A (en) * | 2016-11-07 | 2018-05-22 | 苏州宝时得电动工具有限公司 | Graphene and preparation method thereof, the Anode and battery containing graphene |
| CN108298530A (en) * | 2018-01-17 | 2018-07-20 | 中国石油大学(北京) | A kind of form the few-layer graphene alkene and the preparation method and application thereof |
| CN109179383A (en) * | 2018-01-17 | 2019-01-11 | 中原大学 | Graphene structure, method for preparing graphene and lithium ion battery electrode |
| KR20200103603A (en) * | 2018-09-06 | 2020-09-02 | 한국과학기술원 | Graphene-based compound and manufacturing method thereof and composition for graphene-based manufacturing compound and graphene quantum dot |
| CN111252757A (en) * | 2019-10-10 | 2020-06-09 | 中国科学院生态环境研究中心 | Method for preparing graphene by using waste lithium ion power battery |
| CN112978722A (en) * | 2019-12-17 | 2021-06-18 | 山东海科创新研究院有限公司 | Small-diameter graphene powder, graphene conductive paste, and preparation methods and applications thereof |
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