CN110745820A - Purification method of smokeless coal-based microcrystalline graphite for preparing lithium ion battery negative electrode material - Google Patents
Purification method of smokeless coal-based microcrystalline graphite for preparing lithium ion battery negative electrode material Download PDFInfo
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- CN110745820A CN110745820A CN201911224741.7A CN201911224741A CN110745820A CN 110745820 A CN110745820 A CN 110745820A CN 201911224741 A CN201911224741 A CN 201911224741A CN 110745820 A CN110745820 A CN 110745820A
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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
- C01B32/215—Purification; Recovery or purification of graphite formed in iron making, e.g. kish graphite
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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
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
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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 purification method of smokeless coal-based microcrystalline graphite for preparing a lithium ion battery cathode material, which comprises the following steps: the method comprises the following steps of preparing ultrafine powder with the granularity of less than 10 mu m by two-section jaw crushing, one-section impact hammer crushing, horizontal stirring mill-dry cyclone classification, and simultaneously performing primary roughing and five-time fine separation by adopting two inhibitors, a self-made emulsified kerosene collecting agent and a 2# oil foaming agent to collect concentrate with the fixed carbon content of not less than 90.0% as flotation separation; putting the flotation ore into a mixed solution of one or more acids in a constant-temperature water bath kettle at the temperature of 60-90 ℃, stirring, carrying out ultrasonic treatment for 30-60 min, washing the mixture until the pH value is 7, carrying out suction filtration, drying at the temperature of 110 ℃ for 2-5 h, and purifying to obtain the microcrystalline graphite with the fixed carbon content of not less than 99.0%. The prepared smokeless coal-based microcrystalline graphite is used as a lithium ion battery cathode material, the first reversible capacity is not lower than 400mAh/g and is higher than the theoretical capacity of graphite, after 100 times of circulation, the reversible capacity retention rate is not lower than 90.0%, and the electrical property is obviously improved compared with that of microcrystalline graphite before purification.
Description
Technical Field
The invention belongs to a purification technology of high-purity smokeless coal-based microcrystalline graphite, and the purified microcrystalline graphite is applied to a lithium ion battery cathode material, in particular to a mechanical crushing, emulsified kerosene flotation and acid washing process and application of the material in new energy materials, which are cross technologies in the fields of physics, chemistry and chemical power supplies.
Background
The smokeless coal-based microcrystalline graphite is low in crystallinity and high in ore grade, ultrafine powder prepared by two sections of jaws, one section of counterattack hammer breakage and horizontal stirring mill-dry cyclone classification is isotropic, microcrystalline graphite grains are fine and serve as a lithium ion battery cathode material, the theoretical specific capacity is higher than that of crystalline flake graphite, but the impurity content of natural microcrystalline graphite is high, so that the structural stability and the electrical property of the lithium ion battery are reduced, the purity of the lithium ion battery is improved through deep processing of the microcrystalline graphite, and the problem that the structure of the lithium ion battery is urgently required to be solved is solved.
The purification process of the microcrystalline graphite mainly comprises five processes, namely the recovery rate of the graphite by a chloride roasting method is highest, but the operation controllability is poor, chlorine is toxic, the purity of the graphite by a high-temperature method is highest, but the requirement on raw materials is high, equipment is expensive, the investment is huge, the purity of the graphite by an alkaline-acid method is higher, but the equipment is seriously corroded, part of impurities in a flotation method are impregnated in the graphite in an extremely fine particle shape and cannot be completely dissociated by monomers, so that the purity of the obtained graphite is not high, the purification effect of the hydrofluoric acid method is better, but the impurities are easily combined with oxide impurities in the graphite to generate fluoride precipitates, and the fixed.
Disclosure of Invention
The invention aims to provide a low-cost and high-efficiency purification method of smokeless coal-based microcrystalline graphite for preparing a lithium ion battery cathode material by an emulsified kerosene flotation-mixed acid method, and the smokeless coal-based microcrystalline graphite which is subjected to ultrafine grinding and purification is applied to the lithium ion battery cathode material.
In order to achieve the purpose, the invention is realized by the following technical scheme: a purification method of smokeless coal-based microcrystalline graphite for preparing a lithium ion battery negative electrode material comprises the following steps:
(1) taking natural smokeless coal-based microcrystalline graphite as a raw material, sequentially crushing by a jaw crusher of 50mm and a jaw crusher of 10mm, hammering by a counterattack hammer crusher of 1mm, crushing the microcrystalline graphite of less than 1mm by a dry method by using alumina balls of a horizontal stirring mill, performing cyclone classification, performing ball milling on the material with the particle size of more than 10 mu m again, and taking the material with the particle size of less than 10 mu m as a flotation feed;
(2) firstly adding 400-600 g/t of two inhibitor sodium silicate and 100-300 g/t of sodium carboxymethylcellulose, stirring for 3-5 min, mixing an emulsifier MOA-3B and kerosene at a mass ratio of 1: 9-2: 8, mixing for 3-5 min at a high speed of 800-1000 r/min in a high-speed stirrer to serve as a collecting agent, wherein the adding amount of the collecting agent is 1000-3000 g/t, stirring for 1-2 min, adding 200-400 g/t of foaming agent 2 oil, stirring for 1min, aerating, blowing at an air flow rate of 150-250L/h, scraping for 5min, collecting concentrate, drying at 60 ℃ for 6-8 h, adding the concentrate into a flotation tank, adding water, performing 1 st concentration, scraping for collecting concentrate, repeating the 1 st concentration process for the 2 nd concentration, supplementing 100-200 g/t of inhibitor sodium silicate, 50-100 g/t of sodium carboxymethylcellulose, 500-1000 g/t of collector emulsified kerosene and 100-200 g/t of foaming agent 2# oil during the 3 rd concentration, repeating the 2 nd concentration process for the 4 th and 5 th concentrations, and finally collecting the concentrate with the fixed carbon content not lower than 90.0% as flotation;
(3) placing the flotation ore into HF, HCl and H in a constant-temperature water bath kettle at the temperature of 60-90 DEG C2SiF6、HNO3In the mixed solution of one or more acids, the mass ratio of the volume of the mixed acid to the microcrystalline graphite is 2: 1-4: 1, the volume of HF accounts for 50% of the volume of the mixed acid, the volume fractions of other acids are equal, stirring is carried out for 3-5 h, then ultrasonic treatment is carried out for 30-60 min at room temperature, the mixture is washed until the pH value is 7, then suction filtration is carried out, a forced air drying oven is carried out at 110 ℃ for drying for 2-5 h, and the fixed carbon content of the purified high-purity smokeless coal-based microcrystalline graphite is not lower than 99.9%.
Compared with the prior art, the invention has the following technical advantages:
the natural smokeless coal-based microcrystalline graphite ore has high grade and low crystallinity, ultrafine powder with the granularity less than 10 mu m is prepared by an ultrafine grinding process and is used as a flotation feed material, the flotation feed material is more fully combined with mixed acid, the purification effect of the microcrystalline graphite is improved, the natural smokeless coal-based microcrystalline graphite ore is applied to a lithium ion battery cathode material, and as the grains are fine and isotropic, lithium ion diffusion channels are increased, and the reversible lithium storage capacity is higher than that of crystalline flake graphite.
After the smokeless coal-based microcrystalline graphite is subjected to ultrafine grinding, a flotation process is utilized to remove part of impurities, two inhibitors, namely sodium silicate and sodium carboxymethylcellulose are adopted at the same time, the effect is more ideal than that of one inhibitor, and the floating of impurity minerals can be effectively prevented; under the action of an emulsifier, the kerosene is self-prepared into emulsion, the stabilization time is longer, the dynamic viscosity is obviously reduced, the dispersion performance of kerosene drops in a water phase is improved, microcrystalline graphite can be more effectively collected, and the condition that the gangue such as kaolinite group minerals or micro-fine particle quartz on the surfaces of mineral particles are adsorbed together is prevented.
After flotation, the microcrystalline graphite is subjected to first-step impurity removal by using strong acid HF, but HF and oxides of calcium, magnesium, iron and the like undergo chemical reaction to generate fluoride precipitate, and the fluoride precipitate is mixed in the microcrystalline graphite, so that HCl and H are added2SiF6、HNO3The one or more acids react with the fluoride precipitates to generate soluble salt compounds, and the effect of preparing the high-purity smokeless coal-based microcrystalline graphite is achieved through water washing and suction filtration.
The prepared smokeless coal-based microcrystalline graphite is used as a lithium ion battery cathode material, the first reversible capacity is not lower than 400mAh/g and is higher than the theoretical capacity of graphite, after 100 times of circulation, the reversible capacity retention rate is not lower than 90.0%, and the electrical property is obviously improved compared with that of microcrystalline graphite before purification. The invention not only improves the purity of the smokeless coal-based natural microcrystalline graphite, but also uses the mineral material as the negative electrode material of the new energy lithium ion battery, increases the functionality of the material and improves the application potential of the material.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings of the embodiments will be briefly described below.
FIG. 1 is a flow chart of the present invention using mechanical crushing and emulsified kerosene flotation process;
FIG. 2 is a flow chart of the mixed acid purification process of the present invention.
Detailed Description
Other aspects, features and advantages of the present invention will become apparent from the following detailed description, taken in conjunction with the accompanying drawings, which form a part of this specification, and which illustrate, by way of example, the principles of the invention.
Example 1: taking natural smokeless coal-based microcrystalline graphite as a raw material, sequentially crushing by a jaw crusher of 50mm and a jaw crusher of 10mm, hammering by a counterattack hammer crusher of 1mm, and preparing a flotation feed material with the particle size of less than 10 microns by a horizontal stirring mill-dry method; performing primary roughing and five times of fine concentration on a flotation feed material in a flotation tank, controlling the concentration of slurry to be 20%, firstly adding 400g/t of inhibitor sodium silicate and 200g/t of sodium carboxymethyl cellulose, stirring for 3min, mixing an emulsifier MOA-3B and kerosene according to the mass ratio of 1:9, mixing for 3min at a high speed of 800r/min in a high-speed stirrer to serve as a collecting agent, wherein the adding amount of the collecting agent is 1000g/t, stirring for 1min, then adding 250g/t of foaming agent 2# oil, stirring for 1min, aerating, wherein the airflow speed is 200L/h, scraping for 5min, collecting concentrate, performing fine concentration for 5 times in sequence, supplementing 100g/t of inhibitor sodium silicate, 50g/t of sodium carboxymethyl cellulose, 1000g/t of self-made emulsified kerosene of the collecting agent and 200g/t of foaming agent 2# oil during the 3 rd fine concentration, and collecting the concentrate to be used as the microcrystalline graphite cathode material of the lithium ion battery.
Comparative example 1: the flotation process of example 1 was followed without sodium silicate.
Comparative example 2: the flotation process of example 1 was followed without the addition of sodium carboxymethylcellulose.
Comparative example 3: according to the flotation process of example 1, the collector was kerosene which had not been emulsified.
As shown in table 1, comparative example 1 and comparative example 1 or 2 showed that the purification effect was better by adding two kinds of depressants than by adding only one kind of depressants, and comparative example 1 and comparative example 3 showed that the flotation effect was remarkably improved by adding home-made emulsified kerosene than by using general kerosene. The electrical property data result in table 1 shows that the higher the fixed carbon content in the microcrystalline graphite is, the higher the first reversible specific capacity is when the microcrystalline graphite is used as a negative electrode material of a lithium ion battery, and the higher the reversible capacity retention rate of the battery is after 100 cycles.
Fixed carbon content and electrical properties of the samples of Table 1
Example 2: taking natural smokeless coal-based microcrystalline graphite as a raw material, sequentially crushing by a jaw crusher of 50mm and a jaw crusher of 10mm, hammering by a counterattack hammer crusher of 1mm, and preparing a flotation feed material with the particle size of less than 10 microns by a horizontal stirring mill-dry method; performing primary roughing and five times of fine concentration on a flotation feed material in a flotation tank, controlling the concentration of slurry to be 20%, firstly adding 500g/t of inhibitor sodium silicate and 300g/t of sodium carboxymethyl cellulose, stirring for 5min, mixing an emulsifier MOA-3B and kerosene according to the mass ratio of 2:8, mixing for 5min at a high speed of 1000r/min in a high-speed stirrer to serve as a collecting agent, wherein the adding amount of the collecting agent is 3000g/t, stirring for 1min, then adding 200g/t of foaming agent 2# oil, stirring for 1min, aerating, wherein the airflow speed is 250L/h, scraping for 5min, collecting concentrate, performing fine concentration for 5 times in sequence, supplementing 200g/t of inhibitor sodium silicate, 100g/t of sodium carboxymethyl cellulose, 800g/t of self-made emulsified kerosene of the collecting agent and 150g/t of foaming agent 2# oil during the 3 rd fine concentration, using the concentrate with the collected fixed carbon content not less than 90.0 percent as flotation separation; placing the flotation ore into HF and H in a constant temperature water bath kettle at 70 DEG C2SiF6In the mixed solution, the mass ratio of the mixed acid volume to the microcrystalline graphite is 2:1, and HF and H are mixed2SiF6Stirring for 5h at a volume ratio of 1:1, then performing ultrasonic treatment at room temperature for 30min, washing the mixture until the pH value is 7, performing suction filtration, and drying for 4h in a forced air drying oven at 110 ℃ to obtain high-purity microcrystalline graphite serving as a microcrystalline graphite cathode material of the lithium ion battery.
Comparative example 4: the flotation and acid washing process of example 1 was followed without addition of H2SiF6。
Comparative example 5: the flotation and acid washing method of example 1 was followedMethod H2SiF6The reaction was changed to HCl.
Comparative example 6: following the flotation and acid washing procedure of example 1, H2SiF6By replacement with HNO3。
Comparative example 7: following the flotation and acid washing procedure of example 1, H2SiF6Change to H2SiF6And HCl.
Comparative example 8: following the flotation and acid washing procedure of example 1, H2SiF6Change to HCl and HNO3。
Comparative example 9: following the flotation and acid washing procedure of example 1, H2SiF6Change to H2SiF6HCl and HNO3。
As shown in table 2, comparative example 2 and comparative example 4 showed that the purification effect was better than that of HF alone by adding two acids, comparative example 2 and comparative example 5 or 6 showed that the fixed carbon content of microcrystalline graphite after purification by adding two acids was more than 99.0%, comparative example 2 and comparative example 7 or 8 showed that the fixed carbon content of microcrystalline graphite after purification by adding three acids was more than 99.0%, and comparative example 2 and comparative example 9 showed that the fixed carbon content of microcrystalline graphite after adding four acids was more than 99.0%. The electrical property data result in table 2 shows that the microcrystalline graphite is subjected to impurity removal only by using HF as the lithium ion battery cathode material, the initial reversible specific capacity is the worst, the battery reversible capacity retention rate is the lowest after 100 times of circulation, if impurity removal is performed by using two or more acids, the initial reversible capacity retention rate is higher than 400mAh/g, and the battery reversible capacity retention rate is higher than 90.0% after 100 times of circulation.
Fixed carbon content and electrical properties of the samples of Table 2
While the foregoing is directed to the preferred embodiment of the present invention, other and further embodiments of the invention may be devised without departing from the basic scope thereof, and the scope thereof is determined by the claims that follow.
Claims (2)
1. A purification method of smokeless coal-based microcrystalline graphite for preparing a lithium ion battery negative electrode material is characterized by comprising the following steps:
(1) taking natural smokeless coal-based microcrystalline graphite as a raw material, sequentially crushing by a jaw crusher of 50mm and a jaw crusher of 10mm, hammering by a counterattack hammer crusher of 1mm, crushing the microcrystalline graphite of less than 1mm by a dry method by using alumina balls of a horizontal stirring mill, performing cyclone classification, performing ball milling on the material with the particle size of more than 10 mu m again, and taking the material with the particle size of less than 10 mu m as a flotation feed;
(2) firstly adding 400-600 g/t of two inhibitor sodium silicate and 100-300 g/t of sodium carboxymethylcellulose, stirring for 3-5 min, mixing an emulsifier MOA-3B and kerosene at a mass ratio of 1: 9-2: 8, mixing for 3-5 min at a high speed of 800-1000 r/min in a high-speed stirrer to serve as a collecting agent, wherein the adding amount of the collecting agent is 1000-3000 g/t, stirring for 1-2 min, adding 200-400 g/t of foaming agent 2 oil, stirring for 1min, aerating, blowing at an air flow rate of 150-250L/h, scraping for 5min, collecting concentrate, drying at 60 ℃ for 6-8 h, adding the concentrate into a flotation tank, adding water, performing 1 st concentration, scraping for collecting concentrate, repeating the 1 st concentration process for the 2 nd concentration, supplementing 100-200 g/t of inhibitor sodium silicate, 50-100 g/t of sodium carboxymethylcellulose, 500-1000 g/t of collector emulsified kerosene and 100-200 g/t of foaming agent 2# oil during the 3 rd concentration, repeating the 2 nd concentration process for the 4 th and 5 th concentrations, and finally collecting concentrate with the fixed carbon content not lower than 90.0% as flotation separation;
(3) placing the flotation ore into HF, HCl and H in a constant-temperature water bath kettle at the temperature of 60-90 DEG C2SiF6、HNO3In the mixed solution of one or more acids, the mass ratio of the mixed acid volume to the microcrystalline graphite is 2: 1-4: 1, and the HF volume accounts forStirring for 3-5 h when the volume percentage of the mixed acid is 50% and the volume percentages of other acids are equal, then performing ultrasonic treatment for 30-60 min at room temperature, washing the mixture until the pH value is 7, performing suction filtration, drying for 2-5 h in a forced air drying oven at 110 ℃, and purifying to obtain the high-purity smokeless coal-based microcrystalline graphite with the fixed carbon content of not less than 99.0%.
2. The purification method of the smokeless coal-based microcrystalline graphite for preparing the lithium ion battery negative electrode material according to claim 1, wherein the prepared smokeless coal-based microcrystalline graphite is applied to the lithium ion battery negative electrode material.
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| CN113753885A (en) * | 2021-09-03 | 2021-12-07 | 黑龙江省宝泉岭农垦溢祥石墨有限公司 | Chemical purification and wastewater treatment process for natural spherical graphite |
| CN114425487A (en) * | 2022-01-21 | 2022-05-03 | 湖南有色金属研究院有限责任公司 | Method for separating microcrystalline graphite from anthracite |
| CN117819541A (en) * | 2024-03-04 | 2024-04-05 | 矿冶科技集团有限公司 | Method for purifying graphite by high-temperature drying-free raw materials and simple acid-base method |
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| CN117819541A (en) * | 2024-03-04 | 2024-04-05 | 矿冶科技集团有限公司 | Method for purifying graphite by high-temperature drying-free raw materials and simple acid-base method |
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