CN114956072A - Method for expanding natural graphite spherical tailing by steam pressure - Google Patents
Method for expanding natural graphite spherical tailing by steam pressure Download PDFInfo
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- CN114956072A CN114956072A CN202210646200.9A CN202210646200A CN114956072A CN 114956072 A CN114956072 A CN 114956072A CN 202210646200 A CN202210646200 A CN 202210646200A CN 114956072 A CN114956072 A CN 114956072A
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/20—Graphite
- C01B32/21—After-treatment
- C01B32/22—Intercalation
- C01B32/225—Expansion; Exfoliation
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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
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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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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- 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 discloses a water vapor modified natural graphite spherical tailing, which can be used as a raw material of a natural graphite-based high-rate lithium ion battery cathode material and belongs to the field of secondary resource utilization. The method can realize the efficient utilization of the solid waste of the graphite, and comprises the following steps: (1) weighing purified natural graphite spherical tailings, soaking the natural graphite spherical tailings in a solution A with a certain mass fraction for a period of time, and drying graphite after soaking to obtain graphite B; (2) and (2) placing the graphite B and deionized water in a pressure container according to a certain solid-liquid ratio, fully mixing to enable the pressure container to be in a closed state, heating at a specific temperature, releasing the pressure of the container instantly when the container reaches the specific pressure, collecting graphite C, namely the natural graphite spherical tailing after steam pressure expansion, and obtaining the graphite interlayer spacing of 0.3350-0.3958 nm. The rate capability of the product is obviously improved relative to the spherical tailing raw material. The method is green, simple in process and low in cost, and the lithium battery anode material prepared in a large scale has a wide prospect.
Description
Technical Field
The invention belongs to the technical field of lithium ion batteries, and discloses a water vapor pressure expansion method for natural graphite spherical tailings.
Background
Lithium ion batteries are widely applied to the fields of energy storage equipment, 3C products, power automobiles and the like as secondary batteries, and currently, carbon-based lithium ion negative electrode batteries still have great market potential. The natural graphite is used as a main raw material of the carbon-based lithium ion battery, and is paid much attention to the market due to the advantages of low charge-discharge platform, high graphitization degree, low price and the like, but the further development of the battery is limited due to the low theoretical specific capacity (the theoretical specific capacity is 372mA h/g) and easy polarization of the electrode. In addition, natural graphite is easy to generate preferred orientation due to complete crystal structure development, and the graphite has anisotropic characteristic, so that lithium ions cannot be uniformly and rapidly removed/inserted, and the rate capability of the natural graphite is influenced. The natural graphite can generate lamellar spherical tailing in the spheroidization process, the lamellar spherical tailing accounts for about 50% of the raw material, the natural graphite is generally regarded as solid waste, the effective utilization rate is low at present, and the natural graphite is mainly applied to the low-end fields of sealing rings, pencil lead manufacturing and the like. The carbon content of the spherical tailings is usually 92-95% by performing related phase analysis, and the carbon-based tailings can reach the grade of the raw materials of the carbon-based lithium ion battery after purification. The sheet structure of the spherical tailing layer is beneficial to the insertion and extraction of lithium ions, and the spherical tailing layer is a potential lithium battery negative electrode material. And the small size of the spherical tailings can reduce the influence of natural graphite crystal anisotropy after granulation, and the rapid lithium ion deintercalation is realized. However, the natural graphite carbon interlayer spacing is only 0.3354nm, and when the natural graphite carbon interlayer spacing is used as a negative electrode of a lithium battery, the large-current performance is poor, so that the development of the commercial rapid charging field is limited.
The traditional carbon-based lithium battery negative electrode rapid charging method mainly adopts a Hummer method for modification, graphite oxidation modification is carried out, an intercalation agent and the intercalation agent are added for high-temperature gasification, so that the graphite carbon interlayer distance is increased, and a more efficient lithium ion carbon layer diffusion channel is constructed. However, the traditional Hummer method usually uses a large amount of strong acid, strong oxidant and other chemical reagents, has long flow and high risk, and does not meet the requirements of low carbon and environmental protection.
Disclosure of Invention
Natural graphite inter-layer spacing is bonded with weak van der waals force, and carbon inter-layer bonding force spacing is easier to be damaged relative to the carbon atoms in the carbon layer with molecular force. Water also generates huge pressure during gasification, is a green low-cost 'intercalator', releases the pressure to destroy the van der Waals force action between carbon layers under certain conditions, and increases the distance between the carbon layers. The water vapor can generate huge impact force when the pressure is changed sharply, can damage the structure of the graphite carbon layer to a certain extent, and can also play a role in changing the spacing between the carbon layers under certain conditions. And the water has the advantages of greenness, low cost and the like, and the graphite modified by the water vapor has great market potential.
In order to solve the problem of poor rate capability of the natural graphite spherical tailing, the invention provides a method for expanding the natural graphite spherical tailing by steam pressure. The method is green and environment-friendly, has simple production process and strong practical application performance. The method comprises the following specific steps:
(1) weighing a certain mass of purified natural graphite spherical tailings, soaking in a solution A with a certain mass fraction for a period of time, and drying graphite after soaking to obtain graphite B;
(2) placing the graphite B and deionized water in a pressure container according to a certain solid-liquid ratio, fully mixing, keeping the pressure container in a closed state, heating the pressure container at a specific temperature, releasing the pressure of the container instantly when the pressure of the container reaches a specific pressure, and collecting graphite C, namely the natural graphite spherical tailing after steam pressure expansion;
further, the solution in the step (1) may be ammonium chloride solution (0.1-3 mol/L), hydrogen peroxide solution (0.1-5 wt.%), sodium hydroxide solution (0.1-3 mol/L), sulfuric acid solution (0.1-3 mol/L), polyvinylpyrrolidone solution (0.1-5 wt.%), nitric acid solution (0.1-3 mol/L), and soaking time is 0.5-12 h;
further, the solid-to-liquid ratio of the graphite B to the deionized water in the step (2) is (50:1) - (1:3), the heating temperature is 100-200 ℃, and the pressure expansion pressure of the pressure container is 0.1-3.5 MPa;
further, the carbon layer spacing of the graphite C in the step (2) is 0.3340nm to 0.3958 nm. The invention mainly uses the impact force generated by the instantaneous pressure change of water vapor to change the graphite carbon layer spacing from the perspective of graphite crystals to prepare the natural graphite-based lithium ion battery high-rate negative electrode material. The whole production process is green and environment-friendly, has no high energy consumption step, easily available raw materials and strong operability, is an effective spherical tailing modification method, and has very wide application prospect.
Drawings
FIG. 1 is a process flow diagram of the present invention.
Fig. 2 is an XRD pattern of natural graphite spherical tailings before and after modification in embodiment 1 of the present invention: a) XRD tests show that the 2 theta is 10-90 DEG diffraction angle corresponding to a peak intensity pattern; b) XRD partial magnification.
Fig. 3 is SEM images of natural graphite spherical tailings before and after modification in embodiment 1 of the present invention: a) purifying the SEM image of the spherical tailings under low magnification; b) SEM image of spherical tailing after steam modification at low magnification.
Fig. 4 is a blue test magnification diagram of the natural graphite spherical tailings before and after modification in embodiment 1 of the present invention.
Detailed Description
The present invention will be further described with reference to the following examples, but the present invention is not limited to the following examples.
The experimental methods described in the following examples are all conventional methods unless otherwise specified; the reagents and materials are commercially available, unless otherwise specified.
Example 1
And (3) soaking the purified natural graphite spherical tailings with a certain mass in 1mol/L ammonium chloride solution for 6 hours, and drying to obtain graphite B, wherein the solid-to-liquid ratio of the graphite B to deionized water is 20:1, the heating temperature is 150 ℃, the modification pressure is 1.5MPa, and the carbon-layer spacing of the graphite C after pressure expansion is 0.3420 nm.
An X-ray diffractometer (Rigaku SmartLab 9kW) was used to observe the d002 diffraction peak of the modified natural graphite spherical tailing negative electrode material crystal under the above conditions, as shown in FIG. 2. The corresponding sem image is shown in fig. 3.
The steam modified natural graphite spherical tailing prepared in the example 1 and coking coal granulation are used as lithium ion battery negative electrode materials, a metal lithium sheet is used as a counter electrode, Celgard2325 is used as a diaphragm, 1mol/L LiPF6 (solvent is a mixed solution of ethylene carbonate and dimethyl carbonate with the volume ratio of 1: 1) is used as electrolyte, and a CR2032 type button battery case is assembled into a button battery for assembly in an argon-protected glove box. And (3) performing charge and discharge tests, wherein in the test program, the charge and discharge current density is 0.1A/g, 0.2A/g, 0.5A/g, 1.0A/g, 2.0A/g, 5.0A/g, 2.0A/g, 1.0A/g, 0.5A/g, 0.2A/g and 0.1A/g, the number of charge and discharge cycles under the same current density is 10 circles, and the voltage charge and discharge interval is 0.01-3V. The battery charge-discharge rate cycle performance is shown in fig. 4, when the current density is 0.1A/g, the specific capacity of the spherical tailing-based negative electrode is 402.9mA h/g, the specific capacity of the modified spherical tailing-based negative electrode is 498.3mA h/g, and when the current density is 5.0A/g, the specific capacity of the spherical tailing-based negative electrode is 48.1mA h/g, the specific capacity of the modified spherical tailing-based negative electrode is 113.2mA h/g, the capacity retention rates are 11.93% and 22.72% respectively, and after heavy current discharge, the negative electrode can still well maintain the small-current charge-discharge performance.
Example 2
And (3) placing the purified natural graphite spherical tailings with a certain mass in 0.5 wt.% hydrogen peroxide solution for soaking for 12h, and drying to obtain graphite B, wherein the solid-to-liquid ratio of the graphite B to deionized water is 15:1, the heating temperature is 160 ℃, the modification pressure is 2.5MPa, and the carbon-layer spacing of the pressure-expanded graphite C is 0.3532 nm.
Example 3
And (3) soaking the purified natural graphite spherical tailings with a certain mass in 0.5mol/L nitric acid solution for 2 hours, and drying to obtain graphite B, wherein the solid-to-liquid ratio of the graphite B to deionized water is 10:1, the heating temperature is 120 ℃, the modification pressure is 0.6MPa, and the carbon-layer spacing of the graphite C after pressure expansion is 0.3422 nm.
Example 4
And (3) soaking the purified natural graphite spherical tailings with a certain mass in a 0.5mol/L sulfuric acid solution for 9 hours, and drying to obtain graphite B, wherein the solid-to-liquid ratio of the graphite B to deionized water is 1:1, the heating temperature is 160 ℃, the modification pressure is 2.0MPa, and the carbon-layer spacing of the graphite C after pressure expansion is 0.3528 nm.
Example 5
And (3) soaking the purified natural graphite spherical tailings with a certain mass in 0.5mol/L sodium hydroxide solution for 10 hours, and drying to obtain graphite B, wherein the solid-to-liquid ratio of the graphite B to deionized water is 5:1, the heating temperature is 130 ℃, the modification pressure is 2.0MPa, and the carbon-layer spacing of the graphite C after pressure expansion is 0.3620 nm.
In the description herein, references to the description of the term "one embodiment," "some embodiments," "an example," "a specific example," or "some examples" or the like, mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The foregoing is a more detailed description of the present invention that is presented in conjunction with specific embodiments, and the practice of the invention is not to be considered limited to those descriptions. It will be apparent to those skilled in the art that a number of simple derivations or substitutions can be made without departing from the inventive concept.
Claims (4)
1. A method for expanding natural graphite spherical tailing by steam pressure is characterized by comprising the following steps:
(1) weighing a certain mass of purified natural graphite spherical tailings, soaking the natural graphite spherical tailings in a solution A with a certain mass fraction for a period of time, and drying graphite after soaking to obtain graphite B;
(2) and (2) placing the graphite B and deionized water in a pressure container according to a certain solid-liquid ratio, fully mixing, keeping the pressure container in a closed state, heating the pressure container at a specific temperature, releasing the pressure of the container instantly when the pressure of the container reaches a specific pressure, and collecting graphite C, namely the natural graphite spherical tailing after steam pressure expansion.
2. The method for steam pressure expansion of spherical tailings of natural graphite as claimed in claim 1, wherein the solution in step (1) may be ammonium chloride solution (0.1mol/L-3mol/L), hydrogen peroxide solution (0.1 wt.% -5 wt.%), sodium hydroxide solution (0.1mol/L-3mol/L), sulfuric acid solution (0.1mol/L-3mol/L), polyvinylpyrrolidone solution (0.1 wt.% -5 wt.%), nitric acid solution (0.1mol/L-3mol/L) and soaking time is 0.5-12 h.
3. The method for steam pressure expansion of spherical tailings of natural graphite as claimed in claim 1, wherein the solid-to-liquid ratio of graphite B to deionized water in step (2) is (50:1) - (1:3), the heating temperature is 100-200 ℃, and the pressure expansion pressure of the pressure vessel is 0.1-3.5 MPa.
4. The method for steam pressure expansion of spherical tailings of natural graphite as claimed in claim 1, wherein the carbon-layer spacing of graphite C in the step (2) is 0.3340nm to 0.3958 nm.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN116495727A (en) * | 2023-05-19 | 2023-07-28 | 烟台大学 | Preparation method and application of expanded graphene material by using popcorn machine |
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