CN110803698A - Oxidized microcrystalline graphite-based nano Si/SiOxPreparation method of lithium ion battery cathode material - Google Patents
Oxidized microcrystalline graphite-based nano Si/SiOxPreparation method of lithium ion battery cathode material Download PDFInfo
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Abstract
The invention discloses an oxidized microcrystal graphite-based nano Si/SiOxThe preparation method of the lithium ion battery cathode material takes natural smokeless coal-based microcrystalline graphite as a raw material and comprises the steps of jaw crushing and impact hammer crushingPerforming horizontal stirring mill-dry cyclone classification to obtain superfine powder, performing primary coarse separation and five times fine separation with one or two inhibitors, self-made emulsified kerosene collecting agent and 2# oil foaming agent, and using NH4F and excessive HCl and HNO of environment-friendly materials3Mixing one or two acids to prepare high-purity microcrystalline graphite, and preparing the high-purity microcrystalline graphite into oxidized microcrystalline graphite by a Hummers method; preparation of Si/SiO by sol-gel method-inert atmosphere roasting methodxMixing the nano material with microcrystalline graphite oxide in an inert atmosphere high-energy ball mill to prepare microcrystalline graphite-based nano Si/SiOxA lithium ion battery cathode material. The invention not only improves the metastable state SiOxThe structure stability and the reaction controllability are improved, and the reversible capacity and the cycling stability of the smokeless coal-based microcrystalline graphite serving as the lithium ion battery are obviously improved.
Description
Technical Field
The invention belongs to the technical field of new material preparation and new energy, and particularly relates to an oxidized microcrystalline graphite-based nano Si/SiOxA preparation method of a lithium ion battery cathode material and application thereof in a lithium ion battery.
Background
The purification process of the graphite mainly comprises five kinds, the flotation method has low energy consumption, but part of impurities have small sizes and are difficult to separate from the graphite, so the obtained graphite has low purity, the alkali-acid method has high purity, but the equipment is seriously corroded, the hydrofluoric acid method has good purification effect, but is easy to combine with oxide impurities in the graphite to generate fluoride precipitates, so the fixed carbon content of the microcrystalline graphite is reduced, the recovery rate of the chloride roasting method graphite is highest, but the operation controllability is poor, chlorine is toxic, the high-temperature method has highest purity, but the raw material requirement is high, the equipment is expensive, and the investment is huge.
The graphite oxidation mode mainly comprises a gas phase method and a liquid phase method, the gas phase oxidation is low in cost, but can only occur on the surface which is in direct contact with air, hydrogen peroxide, nitric acid, sulfuric acid, perchloric acid and the like can be used as oxidants in the liquid phase oxidation, and because the microcrystalline graphite is prepared into superfine powder through mechanical damage and is small in size, the volume expansion effect is small when the oxidants are used independently, a more effective oxidation mode needs to be adopted, the space between microcrystalline graphite layers is increased, and the reversible capacity of the microcrystalline graphite-based lithium ion battery is improved.
Silicon is used as the lithium ion battery cathode material, has higher theoretical capacity, but has poorer cycle performance due to larger volume change when lithium is deintercalated, and SiOxIs a research hotspot in recent years, because the volume expansion is smaller during charging and discharging, the cycling stability is obviously improved compared with that of simple substance silicon, but the cyclic stability belongs to a metastable state, the synthesis technical requirement is higher, and scholars calcine SiO in an inert atmosphere at 850 ℃ at high temperature to prepare SiOxCN 110311118' disproportionated SiO for lithium ion batteryxMaterial and process for preparing the same, SiO is prepared from silicon powder and silicon dioxide powderxThe generation condition and the structural stability of the metastable state silicon oxygen compound are not easy to control, CN 106975439' is Si/SiO for adsorbing volatile organic pollutantsxA nano-class composite material is prepared from natural clay mineral powder, metallic reducer and salt through preparing Si/SiOxThe composite material is used for adsorbing volatile organic pollutants and is not applied to a lithium ion battery cathode material.
Disclosure of Invention
The invention aims to solve the problems of the prior graphite purification technology, the microcrystalline graphite oxidation technology and the metastable SiOxThe defects of the preparation technology provide the oxidized microcrystalline graphite-based nano Si/SiO with higher purification purity, more sufficient oxidation, more stable structure for preparing the metastable state silicon oxygen compound and stronger reaction controllabilityxThe preparation method of the lithium ion battery cathode material is applied to the lithium ion battery cathode material.
In order to achieve the purpose, the invention is realized by the following technical scheme: oxidized microcrystalline graphite-based nano Si/SiOxThe preparation method of the 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 using a jaw crusher with the particle size of 50mm and a jaw crusher with the particle size of 10mm, hammering by using a counter-impact hammer crusher with the particle size of 1mm, then crushing the microcrystalline graphite with the particle size of less than 1mm by using alumina balls of a horizontal stirring mill with the mass ratio of large, medium and small balls of 2:3:5 in a dry method, carrying out cyclone classification, and carrying out ball milling on the material with the particle size of more than 10 mu m again, wherein the material with the particle size of less than 10 mu m is used as a flotation feed;
then carrying out a primary roughing flotation process and a quintic concentration flotation process, putting a flotation feed material into a flotation tank, adding a proper amount of water, controlling the concentration of slurry to be 15% -25%, selecting one or two inhibitors of sodium silicate and sodium carboxymethylcellulose, 300-500 g/t of sodium silicate and 100-200 g/t of sodium carboxymethylcellulose, stirring for 3-5 min, mixing an emulsifier AEO-7 and kerosene according to the mass ratio of 1: 9-3: 7, mixing in a high-speed stirrer at a high speed of 800-1000 r/min for 3-5 min to form emulsified kerosene as a collecting agent, adding 1000-3000 g/t of the collecting agent, stirring for 1-2 min, adding 200-500 g/t of foaming agent 2# oil, stirring for 1min, aerating, blowing at the air flow rate of 100-300L/h, scraping for 3-5 min, collecting concentrate, drying at 60 ℃ for 6-8 h, adding the concentrate into the flotation tank, adding water, carrying out 1 st concentration, scraping and foaming to collect concentrate, repeating the 1 st concentration process for the 2 nd concentration, supplementing one or two inhibitors in the 3 rd concentration, 150-250 g/t of sodium silicate, 50-100 g/t of sodium carboxymethylcellulose, 500-1500 g/t of collector emulsified kerosene, 100-250 g/t of foaming agent 2# oil, repeating the 1 st 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 percent as flotation separation;
then, in a constant-temperature water bath kettle at 65-85 ℃, flotation and environment-friendly material NH are added4F and excessive HCl and HNO3One or two kinds of acid are mixed, the flotation quality and the environment-friendly material NH are obtained4F is 1:1, NH4The mass ratio of the F to the acid solution is 1: 1.5-1: 3, the volume ratio of the two acids is 1:1, stirring is carried out for 2-4 h, then ultrasonic treatment is carried out for 60-90 min at room temperature, the mixture is washed by water until the pH value is 7, then suction filtration is carried out, drying is carried out for 3-5 h in a forced air drying oven at 110 ℃, and the fixed carbon content of the purified high-purity microcrystalline graphite is not lower than 99.0%;
(2) taking the high-purity microcrystalline graphite prepared in the step (1) as a raw material, preparing oxidized microcrystalline graphite by using a Hummers method, sequentially adding 3-5 g of sodium nitrate and 125-185 mL of concentrated sulfuric acid into a round-bottomed flask acting in an ice bath at a low-temperature reaction stage, adding 5-15 g of the purified high-purity microcrystalline graphite while stirring, controlling the temperature to be 0-4 ℃, removing the ice bath, adding 20-30 g of potassium permanganate into the round-bottomed flask within 20-30 min, mechanically stirring for 60-90 min, controlling the temperature to be 10-15 ℃, controlling a medium-temperature reaction stage in a constant-temperature water bath at 50-80 ℃, keeping the temperature of the round-bottomed flask at 35-40 ℃, stirring for 30min, adding 100-200 mL of room-temperature distilled water and 200-400 mL of distilled water at a temperature higher than 90 ℃ within 30 min-1.5 h at a high-temperature reaction stage, maintaining the temperature at 90-93 ℃, and adding 5-10% of hydrogen peroxide in volume fraction, until no air bubbles are generated, performing suction filtration while hot, washing for multiple times by using dilute hydrochloric acid with the volume fraction of 5-10%, taking several drops of supernatant, adding barium chloride until no precipitate exists, washing by using distilled water until the pH value is 6-7, and drying the product in a blast drying oven at the temperature of 60-80 ℃ for 8-12 hours to prepare oxidized microcrystalline graphite;
(3) uniformly mixing 20mL of ethanol, 20mL of deionized water and 10mL of tetraethoxysilane, stirring for 1-2 h in a constant-temperature water bath kettle at 50-70 ℃, adding one of 0.63g, 1.26g, 1.89g and 2.52g of nano Si, adjusting the pH value to 8-9 with ammonia water, carrying out ultrasonic treatment for 1-2 h to obtain uniform sol, drying the obtained sol for 1-2 h in a forced air drying oven at 50-80 ℃ to form gel, standing for 1-2 days at room temperature, drying for 6-12 h at 50-80 ℃, grinding to obtain a powder sample, heating the powder material in a tubular furnace at 5 DEG/min, heating for 3-5 h at 200 ℃ under the protection of nitrogen, heating to one of 400 ℃, 500 ℃ and 600 ℃ for 6-8 h, and preparing Si/SiOxA nanocomposite;
(4) introducing one of argon or nitrogen, and placing the oxidized microcrystalline graphite prepared in the step (2) and the Si/SiO prepared in the step (3) in a high-energy ball millxNanocomposite blend, Si/SiOxThe mass fraction of the nano composite material is 10-40%, the ball milling time is 30 min-1 h, the rotating speed is 400-600 r/min, and the oxidized microcrystalline graphite-based nano Si/SiO is preparedxThe composite material is used as a lithium ion battery cathode material.
Compared with the prior art, the invention has the following technical advantages:
the invention takes natural smokeless coal-based microcrystalline graphite as a raw material, the fixed carbon content of ore is higher than that of other coal types, the ore is mechanically crushed to prepare an ultrafine powder material, the ultrafine powder material is easier to float during flotation and more fully reacts during acid washing, the self-made emulsified kerosene enhances the dispersibility due to the action of an emulsifier on the surface of the kerosene, the microcrystalline graphite can be better collected, and flotation and NH are carried out4F andamount of HCl, HNO3By mixing one or two acids of (A) with (B), not only NH4F can be completely reacted to form HF, which removes most of the mineral oxide impurities, and excess HCl or HNO3The catalyst can continuously react with the generated fluoride precipitates such as calcium, magnesium, iron and the like to generate soluble salt which is effectively separated from microcrystalline graphite, so that the purification effect is further improved, HF is not directly added, the catalyst is more environment-friendly, and the corrosivity to equipment is reduced;
the microcrystalline graphite purified by the method has small size, and oxidants such as hydrogen peroxide, nitric acid, sulfuric acid, perchloric acid and the like are used, so the volume expansion effect is not obvious, the Hummers method is adopted to prepare the oxidized microcrystalline graphite, the reaction is more violent, the space between microcrystalline graphite layers can be effectively increased, the microcrystalline graphite can be better used as a matrix, and more prepared Si/SiO are contained in the interlayer and the corrosion pit after oxidationxThe nano composite material improves the reversible capacity of the material as the cathode material of the lithium ion battery;
the invention takes nano-silicon and tetraethoxysilane as raw materials and adopts a sol-gel method to prepare Si/SiOxThe nano composite material has simple process, strong reaction controllability and nitrogen protection, and can be used for roasting Si/SiO at the step temperaturexCan enhance metastable SiOxStructural stability of (a);
in order to improve the electrical property of the smokeless coal-based microcrystalline graphite serving as the lithium ion battery cathode material, the prepared high-purity microcrystalline graphite is oxidized and then mixed with Si/SiO prepared by a sol-gel methodxCompounding in a high-energy ball mill under the protection of inert atmosphere, high mixing efficiency, and not only refining microcrystalline graphite grains and preventing nano Si/SiOxThe crystal grains are agglomerated and Si/SiO can be allowed to flowxBetter dispersed among the layers and on the surface of the microcrystalline graphite matrix.
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 diagram of the preparation of microcrystalline graphite-based Si/SiOxThe microstructure appearance of the composite material is that white nano Si/SiO is distributed on a black micro-scale oxidized microcrystalline graphite substratexAnd (3) granules.
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:
(1) taking natural smokeless coal-based microcrystalline graphite as a raw material, sequentially crushing by using a jaw crusher with the particle size of 50mm and a jaw crusher with the particle size of 10mm, hammering by using a counter-impact hammer crusher with the particle size of 1mm, then crushing the microcrystalline graphite with the particle size of less than 1mm by using alumina balls of a horizontal stirring mill with the mass ratio of large, medium and small balls of 2:3:5 in a dry method, carrying out cyclone classification, and carrying out ball milling on the material with the particle size of more than 10 mu m again, wherein the material with the particle size of less than 10 mu m is used as a flotation feed;
then carrying out a primary roughing flotation process and a five-time concentration flotation process, putting a flotation feed material into a flotation tank, adding a proper amount of water, controlling the concentration of slurry to be 25%, selecting one or two of inhibitor sodium silicate and sodium carboxymethyl cellulose, 500g/t sodium silicate and 100g/t sodium carboxymethyl cellulose, stirring for 5min, mixing emulsifier AEO-7 and kerosene according to the mass ratio of 2:8, mixing at a high speed of 800r/min for 5min in a high-speed stirrer to form emulsified kerosene serving as a collecting agent, adding 3000g/t collecting agent, stirring for 2min, adding 300g/t foaming agent 2# oil, stirring for 1min, inflating, having the airflow velocity of 200L/h, scraping for 5min, collecting concentrate, drying at 60 ℃ for 6h, adding water, carrying out 1 st concentration, scraping and collecting concentrate, repeating the 1 st concentration process for 2 nd concentration, adding one or two inhibitors, namely 150g/t of sodium silicate, 50g/t of sodium carboxymethylcellulose, 1500g/t of collecting agent emulsified kerosene and 150g/t of foaming agent 2# oil during the 3 rd concentration, repeating the 1 st concentration process for the 4 th and 5 th concentration, and finally collecting the concentrate with the fixed carbon content of not less than 90.0 percent as flotation separation;
then floating ore and an environment-friendly material NH are put into a constant-temperature water bath kettle at 85 DEG C4F and excess HNO3Mixing, the volume ratio of the flotation quality to the environment-friendly material is 1:1, and NH4Stirring the mixture for 3h with the mass ratio of F to the acid solution of 1:1.5, then performing ultrasonic treatment at room temperature for 70min, and mixing with waterWashing until the pH value is 7, performing suction filtration, drying for 5 hours in a forced air drying oven at 110 ℃, and purifying to obtain high-purity microcrystalline graphite with the fixed carbon content of not less than 99.0%;
(2) taking the high-purity microcrystalline graphite prepared in the step (1) as a raw material, preparing oxidized microcrystalline graphite by using a Hummers method, sequentially adding 5g of sodium nitrate 155mL of concentrated sulfuric acid into a round-bottomed flask acting in an ice bath at a low-temperature reaction stage, adding 15g of the purified high-purity microcrystalline graphite while stirring, controlling the temperature to be 0-4 ℃, removing the ice bath, adding 25g of potassium permanganate into the round-bottomed flask within 30min, mechanically stirring for 90min, controlling the temperature to be 10-15 ℃, keeping the temperature of the round-bottomed flask to be 35-40 ℃ in a constant-temperature water bath at 70 ℃ at a medium-temperature reaction stage, stirring for 30min, adding 200mL of room-temperature distilled water and 200mL of distilled water at the temperature of more than 90 ℃ within 1.5h at a high-temperature reaction stage, finally maintaining the temperature to be 90-93 ℃, adding hydrogen peroxide with the volume fraction of 10% until no bubbles are generated, and performing suction filtration while hot, washing with 10% dilute hydrochloric acid for multiple times, taking several drops of supernatant, adding barium chloride until no precipitate exists, washing with distilled water until the pH value is 6-7, and drying the product in a forced air drying oven at 80 ℃ for 12h to prepare microcrystalline graphite oxide;
(3) uniformly mixing 20mL of ethanol, 20mL of deionized water and 10mL of tetraethoxysilane, stirring for 2h in a constant-temperature water bath kettle at 70 ℃, adding 2.52g of nano Si, adjusting the pH value to 8-9 with ammonia water, carrying out ultrasonic treatment for 2h to obtain uniform sol, drying the obtained sol for 2h in a blast drying oven at 70 ℃ to form gel, standing for 1 day at room temperature, drying for 12h at 70 ℃, grinding to obtain a powder sample, putting the powder material in a tubular furnace to heat at 5 ℃/min, heating for 5h at 200 ℃ under the protection of nitrogen, heating to 500 ℃ for 8h to prepare Si/SiOxA nanocomposite;
(4) introducing one of argon or nitrogen, and placing the oxidized microcrystalline graphite prepared in the step (2) and the Si/SiO prepared in the step (3) in a high-energy ball millxNanocomposite blend, Si/SiOxThe mass fraction of the nano composite material is 10 percent, the ball milling time is 30min, the rotating speed is 600r/min, and the oxidized microcrystalline graphite-based nano Si/SiO is preparedxThe composite material is used as a negative electrode material of a lithium ion battery as shown in FIG. 1.
Comparative example 1: the flotation method (1) in example 1 was followed without adding sodium silicate.
Comparative example 2: the flotation method (1) in example 1 was followed without adding sodium carboxymethylcellulose.
Comparative example 3: according to the flotation method (1) in the example 1, the collecting agent is kerosene which is not subjected to emulsification treatment.
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: (1) taking natural smokeless coal-based microcrystalline graphite as a raw material, sequentially crushing by using a jaw crusher with the particle size of 50mm and a jaw crusher with the particle size of 10mm, hammering by using a counter-impact hammer crusher with the particle size of 1mm, then crushing the microcrystalline graphite with the particle size of less than 1mm by using alumina balls of a horizontal stirring mill with the mass ratio of large, medium and small balls of 2:3:5 in a dry method, carrying out cyclone classification, and carrying out ball milling on the material with the particle size of more than 10 mu m again, wherein the material with the particle size of less than 10 mu m is used as a flotation feed;
then carrying out a primary roughing flotation process and a five-time concentration flotation process, putting a flotation feed material into a flotation tank, adding a proper amount of water, controlling the concentration of slurry to be 15%, selecting one or two of inhibitor sodium silicate and sodium carboxymethyl cellulose, 300g/t sodium silicate and 100g/t sodium carboxymethyl cellulose, stirring for 3min, mixing emulsifier AEO-7 and kerosene according to the mass ratio of 1:9, mixing at a high speed of 1000r/min for 5min in a high-speed stirrer to form emulsified kerosene serving as a collecting agent, adding 1000g/t collecting agent, stirring for 1min, adding 200g/t foaming agent 2# oil, stirring for 1min, aerating, having the airflow velocity of 200L/h, scraping for 3min, collecting concentrate, drying at 60 ℃ for 6h, adding the concentrate into the flotation tank, adding water, carrying out the 1 st concentration, scraping for collecting concentrate, repeating the 1 st concentration process for the 2 nd concentration, adding one or two inhibitors, namely 150g/t of sodium silicate, 100g/t of sodium carboxymethylcellulose, 500g/t of emulsified kerosene of a collecting agent and 100g/t of foaming agent 2# oil during the 3 rd concentration, repeating the 1 st concentration process for the 4 th and 5 th concentrations, and finally collecting the concentrate with the fixed carbon content of not less than 90.0 percent as flotation;
then floating ore and an environment-friendly material NH are put into a constant-temperature water bath kettle at the temperature of 75 DEG C4F and excessive HCl are mixed, the volume ratio of the flotation quality to the environment-friendly material is 1:1, and NH is adopted4Stirring for 2h when the mass ratio of F to the acid solution is 1:3, then carrying out ultrasonic treatment at room temperature for 60min, washing the mixture until the pH value is 7, carrying out suction filtration, drying for 3h in a forced air drying oven at 110 ℃, and purifying to obtain the high-purity microcrystalline graphite with the fixed carbon content of not less than 99.0%;
(2) taking the high-purity microcrystalline graphite prepared in the step (1) as a raw material, preparing oxidized microcrystalline graphite by using a Hummers method, sequentially adding 3g of sodium nitrate and 125mL of concentrated sulfuric acid into a round-bottomed flask acting in an ice bath at a low-temperature reaction stage, adding 5g of the purified high-purity microcrystalline graphite while stirring, controlling the temperature to be 0-4 ℃, removing the ice bath, adding 20g of potassium permanganate into the round-bottomed flask within 20min, mechanically stirring for 60min, controlling the temperature to be 10-15 ℃, keeping the temperature of the round-bottomed flask to be 35-40 ℃ in a constant-temperature water bath at 60 ℃ at a medium-temperature reaction stage, stirring for 30min, adding 100mL of room-temperature distilled water and 200mL of distilled water at a temperature of more than 90 ℃ within 30min at a high-temperature reaction stage, finally maintaining the temperature to be 90-93 ℃, adding hydrogen peroxide with a volume fraction of 5% until no bubbles are generated, performing suction filtration while hot, washing with dilute hydrochloric acid with the volume fraction of 5% for multiple times, taking several drops of supernatant, adding barium chloride until no precipitate exists, washing with distilled water until the pH value is 6-7, and drying the product in a forced air drying oven at 60 ℃ for 10 hours to prepare microcrystalline graphite oxide;
(3) mixing 20mL of ethanol, 20mL of deionized water and 10mL of ethyl orthosilicate uniformly, and stirring the mixture in a stirring deviceStirring in a constant-temperature water bath kettle at 60 ℃ for 1h, adding 0.63g of nano Si, adjusting the pH value to 8-9 with ammonia water, carrying out ultrasonic treatment for 1h to obtain uniform sol, drying the obtained sol in a blast drying oven at 60 ℃ for 1h to form gel, standing at room temperature for 2 days, drying at 60 ℃ for 8h, grinding to obtain a powder sample, heating the powder material in a tubular furnace at 5 DEG/min, heating at 200 ℃ for 3h under the protection of nitrogen, heating to 400 ℃, heating for 6h to prepare Si/SiOxA nanocomposite;
(4) introducing one of argon or nitrogen, and placing the oxidized microcrystalline graphite prepared in the step (2) and the Si/SiO prepared in the step (3) in a high-energy ball millxNanocomposite blend, Si/SiOxThe mass fraction of the nano composite material is 40 percent, the ball milling time is 1h, the rotating speed is 500r/min, and the oxidized microcrystalline graphite-based nano Si/SiO is preparedxThe composite material is used as a lithium ion battery cathode material.
Comparative example 4: the acid washing method of example 2 was followed (1), and HCl was replaced with HNO3。
Comparative example 5: the acid washing method of example 2 was followed to change HCl to HCl and HNO3。
As shown in Table 2, comparative example 2 and comparative example 4, indicating HCl or HNO3And NH4F generates HF after reaction, so that impurities of the smokeless coal-based microcrystalline graphite can be effectively removed, the fixed carbon content of the high-purity microcrystalline graphite is higher than 99.0 percent, the high-purity microcrystalline graphite serving as a negative electrode material of a lithium ion battery has a first reversible capacity higher than 500mAh/g, and the reversible capacity retention rate is higher than 80.0 percent after 100 cycles; comparative example 2 and comparative example 5 show equal volumes of the two acids mixed with NH4The F reaction also achieves the purification effect and electrical properties of an acid.
Fixed carbon content and electrical properties of the samples of Table 2
Example 3: (1) taking natural smokeless coal-based microcrystalline graphite as a raw material, sequentially crushing by using a jaw crusher with the particle size of 50mm and a jaw crusher with the particle size of 10mm, hammering by using a counter-impact hammer crusher with the particle size of 1mm, then crushing the microcrystalline graphite with the particle size of less than 1mm by using alumina balls of a horizontal stirring mill with the mass ratio of large, medium and small balls of 2:3:5 in a dry method, carrying out cyclone classification, and carrying out ball milling on the material with the particle size of more than 10 mu m again, wherein the material with the particle size of less than 10 mu m is used as a flotation feed;
then carrying out a primary roughing flotation process and a five-time concentration flotation process, putting a flotation feed material into a flotation tank, adding a proper amount of water, controlling the concentration of slurry to be 20%, selecting one or two of inhibitor sodium silicate and sodium carboxymethyl cellulose, 400g/t sodium silicate, 150g/t sodium carboxymethyl cellulose, stirring for 4min, mixing emulsifier AEO-7 and kerosene according to the mass ratio of 3:7, mixing for 4min at a high speed of 900r/min in a high-speed stirrer to form emulsified kerosene serving as a collecting agent, adding 2000g/t collecting agent, stirring for 2min, adding 300g/t foaming agent 2# oil, stirring for 1min, inflating, having the airflow velocity of 200L/h, scraping for 4min, collecting concentrate, drying for 7h at 60 ℃, adding the concentrate into the flotation tank, adding water, carrying out the 1 st concentration, scraping for collecting the concentrate, repeating the 1 st concentration process for the 2 nd concentration, adding one or two inhibitors, namely 200g/t of sodium silicate, 100g/t of sodium carboxymethylcellulose, 1000g/t of collecting agent emulsified kerosene and 250g/t of foaming agent 2# oil during the 3 rd concentration, repeating the 1 st concentration process for the 4 th and 5 th concentration, and finally collecting the concentrate with the fixed carbon content of not less than 90.0 percent as flotation separation;
then in a constant temperature water bath kettle at 65 ℃, flotation and environment-friendly material NH are added4F and excessive HCl are mixed, the volume ratio of the flotation quality to the environment-friendly material is 1:1, and NH is adopted4Stirring the mixture for 3 hours at a mass ratio of F to the acid solution of 1:2, then performing ultrasonic treatment at room temperature for 80min, washing the mixture until the pH value is 7, performing suction filtration, drying the mixture for 4 hours in a forced air drying oven at 110 ℃, and purifying the purified high-purity microcrystalline graphite to obtain the high-purity microcrystalline graphite with the fixed carbon content of not less than 99.0 percent;
(2) taking the high-purity microcrystalline graphite prepared in the step (1) as a raw material, preparing oxidized microcrystalline graphite by using a Hummers method, sequentially adding 4g of sodium nitrate and 156mL of concentrated sulfuric acid into a round-bottomed flask acting in an ice bath at a low-temperature reaction stage, adding 10g of the purified high-purity microcrystalline graphite while stirring, controlling the temperature to be 0-4 ℃, removing the ice bath, adding 25g of potassium permanganate into the round-bottomed flask within 25min, mechanically stirring for 80min, controlling the temperature to be 10-15 ℃, keeping the temperature of the round-bottomed flask to be 35-40 ℃ in a constant-temperature water bath at 80 ℃ at a medium-temperature reaction stage, stirring for 30min, adding 150mL of room-temperature distilled water and 300mL of distilled water at the temperature of more than 90 ℃ within 1.5h at a high-temperature reaction stage, finally maintaining the temperature to be 90-93 ℃, adding hydrogen peroxide with the volume fraction of 10%, filtering while hot until no bubbles are generated, washing with dilute hydrochloric acid with the volume fraction of 5% for multiple times, taking several drops of supernatant, adding barium chloride until no precipitate exists, washing with distilled water until the pH value is 6-7, and drying the product in a forced air drying oven at 80 ℃ for 10 hours to prepare microcrystalline graphite oxide;
(3) uniformly mixing 20mL of ethanol, 20mL of deionized water and 10mL of tetraethoxysilane, stirring for 2h in a constant-temperature water bath kettle at 50 ℃, adding 1.26g of nano Si, adjusting the pH value to 8-9 with ammonia water, carrying out ultrasonic treatment for 1.5h to obtain uniform sol, drying the obtained sol for 1h in a blast drying oven at 80 ℃ to form gel, standing for 1 day at room temperature, drying for 8h at 80 ℃, grinding to obtain a powder sample, heating the powder material in a tubular furnace at 5 DEG/min, heating for 4h at 200 ℃ under the protection of nitrogen, heating to 600 ℃ for 7h to prepare Si/SiOxA nanocomposite;
(4) introducing one of argon or nitrogen, and placing the oxidized microcrystalline graphite prepared in the step (2) and the Si/SiO prepared in the step (3) in a high-energy ball millxNanocomposite blend, Si/SiOxThe mass fraction of the nano composite material is 20 percent, the ball milling time is 45min, the rotating speed is 400r/min, and the oxidized microcrystalline graphite-based nano Si/SiO is preparedxThe composite material is used as a lithium ion battery cathode material.
Comparative example 6: according to the sol-gel method (3) in example 3, the mass of the nano-silicon is changed from 1.26g to 2.52 g.
Comparative example 7: according to the sol-gel method (3) in example 3, the mass of nano-silicon is changed from 1.26g to 1.89 g.
Comparative example 8: according to the sol-gel method (3) in example 3, the mass of nano-silicon is changed from 1.26g to 0.63 g.
Comparative example 9: the gel baking process of (3) in example 3 was followed, and the second temperature rise was changed from 600 ℃ to 400 ℃.
Comparative example 10: the gel baking process of (3) in example 3 was followed, and the second temperature rise was changed from 600 ℃ to 500 ℃.
As shown in Table 3, the comparative example 3 and the comparative example 6, 7 or 8 show that when the nano-silicon is 0.63 g-2.52 g in mass, the reversible capacity is higher than 500mAh/g for the first time and the reversible capacity retention rate is higher than 80.0% after 100 cycles when the nano-silicon is used as the negative electrode material of the lithium ion battery; the comparison between the example 3 and the comparative example 9 or 10 shows that the lithium ion battery cathode material prepared at the roasting temperature of 400-600 ℃ can also achieve the electrical properties.
Fixed carbon content and electrical properties of the samples of Table 3
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. Oxidized microcrystalline graphite-based nano Si/SiOxThe preparation method of the lithium ion battery cathode material is characterized by comprising the following steps:
(1) taking natural smokeless coal-based microcrystalline graphite as a raw material, sequentially crushing by using a jaw crusher with the particle size of 50mm and a jaw crusher with the particle size of 10mm, hammering by using a counter-impact hammer crusher with the particle size of 1mm, then crushing the microcrystalline graphite with the particle size of less than 1mm by using alumina balls of a horizontal stirring mill with the mass ratio of large, medium and small balls of 2:3:5 in a dry method, carrying out cyclone classification, and carrying out ball milling on the material with the particle size of more than 10 mu m again, wherein the material with the particle size of less than 10 mu m is used as a flotation feed;
then carrying out a primary roughing flotation process and a five-time concentration flotation process, putting a flotation feed material into a flotation tank, adding a proper amount of water, controlling the concentration of slurry to be 15% -25%, selecting one or two inhibitors of sodium silicate and sodium carboxymethylcellulose, 300-500 g/t of sodium silicate and 100-200 g/t of sodium carboxymethylcellulose, stirring for 3-5 min, mixing emulsifier AEO-7 and kerosene at a mass ratio of 1: 9-3: 7, mixing in a high-speed mixer at a high speed of 800-1000 r/min for 3-5 min to serve as a collecting agent, adding 1000-3000 g/t of the collecting agent, stirring for 1-2 min, adding foaming agent 2# oil 200-500 g/t, stirring for 1min, aerating, carrying out air flow rate of 100-300L/h, scraping for 3-5 min, collecting concentrate, drying at 60 ℃ for 6-8 h, adding the concentrate into the flotation tank, adding water, carrying out 1 st concentration, scraping and foaming to collect concentrate, repeating the 1 st concentration process for the 2 nd concentration, supplementing one or two inhibitors in the 3 rd concentration, wherein the sodium silicate accounts for 150-250 g/t, the sodium carboxymethylcellulose accounts for 50-100 g/t, the collector emulsified kerosene accounts for 500-1500 g/t, the foaming agent 2# oil accounts for 100-250 g/t, repeating the 1 st 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 separation;
then, in a constant-temperature water bath kettle at 65-85 ℃, flotation and environment-friendly material NH are added4F and excessive HCl and HNO3One or two kinds of acid are mixed, the flotation quality and the environment-friendly material NH are obtained4F is 1:1, NH4The mass ratio of the F to the acid solution is 1: 1.5-1: 3, the volume ratio of the two acids is 1:1, stirring is carried out for 2-4 h, then ultrasonic treatment is carried out for 60-90 min at room temperature, the mixture is washed by water until the pH value is 7, then suction filtration is carried out, drying is carried out for 3-5 h in a forced air drying oven at 110 ℃, and the fixed carbon content of the purified high-purity microcrystalline graphite is not lower than 99.0%;
(2) taking the high-purity microcrystalline graphite prepared in the step (1) as a raw material, preparing oxidized microcrystalline graphite by using a Hummers method, sequentially adding 3-5 g of sodium nitrate and 125-185 mL of concentrated sulfuric acid into a round-bottomed flask acting in an ice bath at a low-temperature reaction stage, adding 5-15 g of the purified high-purity microcrystalline graphite while stirring, controlling the temperature to be 0-4 ℃, removing the ice bath, adding 20-30 g of potassium permanganate into the round-bottomed flask within 20-30 min, mechanically stirring for 60-90 min, controlling the temperature to be 10-15 ℃, controlling a medium-temperature reaction stage in a constant-temperature water bath at 50-80 ℃, keeping the temperature of the round-bottomed flask at 35-40 ℃, stirring for 30min, adding 100-200 mL of room-temperature distilled water and 200-400 mL of distilled water at a temperature higher than 90 ℃ within 30 min-1.5 h at a high-temperature reaction stage, maintaining the temperature at 90-93 ℃, and adding 5-10% of hydrogen peroxide in volume fraction, until no air bubbles are generated, performing suction filtration while hot, washing for multiple times by using dilute hydrochloric acid with the volume fraction of 5-10%, taking several drops of supernatant, adding barium chloride until no precipitate exists, washing by using distilled water until the pH value is 6-7, and drying the product in a blast drying oven at the temperature of 60-80 ℃ for 8-12 hours to prepare oxidized microcrystalline graphite;
(3) uniformly mixing 20mL of ethanol, 20mL of deionized water and 10mL of tetraethoxysilane, stirring for 1-2 h in a constant-temperature water bath kettle at 50-70 ℃, adding one of 0.63g, 1.26g, 1.89g and 2.52g of nano Si, adjusting the pH value to 8-9 with ammonia water, carrying out ultrasonic treatment for 1-2 h to obtain uniform sol, drying the obtained sol for 1-2 h in a forced air drying oven at 50-80 ℃ to form gel, standing for 1-2 days at room temperature, drying for 6-12 h at 50-80 ℃, grinding to obtain a powder sample, heating the powder material in a tubular furnace at 5 DEG/min, heating for 3-5 h at 200 ℃ under the protection of nitrogen, heating to one of 400 ℃, 500 ℃ and 600 ℃ for 6-8 h, and preparing Si/SiOxA nanocomposite;
(4) introducing one of argon or nitrogen, and placing the oxidized microcrystalline graphite prepared in the step (2) and the Si/SiO prepared in the step (3) in a high-energy ball millxNanocomposite blend, Si/SiOxThe mass fraction of the nano composite material is 10-40%, the ball milling time is 30 min-1 h, the rotating speed is 400-600 r/min, and the oxidized microcrystalline graphite-based nano Si/SiO is preparedxAnd (3) a negative electrode material.
2. Oxidized microcrystalline graphite-based nanosi/SiO according to claim 1xThe preparation method of the lithium ion battery cathode material is characterized in that the prepared microcrystalline graphite oxide-based nano Si/SiOxThe application of the negative electrode material in the negative electrode material of the lithium ion battery.
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