CN110429264B - Method for preparing rice hull-based negative electrode material - Google Patents
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Abstract
A method for preparing a rice hull-based negative electrode material belongs to the field of biomass energy chemical industry, and comprises the following specific steps: (1) crushing rice hulls, and hydrolyzing with dilute acid at 100-120 ℃ for 0.5-1 h to prepare xylose solution and hydrolysis residues; (2) impregnating hydrolysis residues with zinc chloride, and activating to prepare a primary negative electrode material; (3) and preparing the C/SiO2 porous negative electrode material by electrode asphalt modification treatment. Compared with the prior art, the method has the following advantages: (1) the method has the advantages that the rice hulls which are agricultural and sideline products are used as raw materials, diluted acid hydrolysis pretreatment is adopted, and the proportion of carbon and silicon is regulated and controlled, so that the problems that silicon dioxide and carbon on the inner layer and the outer layer in pyrolytic carbon are not uniformly distributed, large carbon on the inner layer exists, and lithium insertion and lithium removal are asynchronous to reduce specific capacity due to different microstructures are solved; (2) the asphalt is used for treating the primary cathode material, so that the conductivity is improved; the carbon structure is reinforced, and the pulverization resistance is improved; the surface functional groups are covered, the leakage current is avoided, and the cycle stability is improved.
Description
Technical Field
The invention belongs to the field of biomass energy chemical industry, and particularly discloses a method for preparing a rice hull-based negative electrode material.
Background
Currently, due to the shortage of petroleum fuels, environmental crisis and energy consumption are increasing, prompting researchers to find cleaner and better electrochemical energy conversion systems. Among these systems, Lithium Ion Batteries (LIBs), a new type of energy source, have attracted general attention due to their high energy density, good cycle performance and long cycle life. Therefore, LIBs can satisfy the development of electric vehicles and plug-in hybrid electric vehicles.
From the perspective of negative electrode materials, as LIBs negative electrodes, the theoretical specific capacity of current commercial graphite is low, 372mah.g-1, which has been a limitation to its wider application.
Silicon Si has received extensive attention over the last few years because of its abundance on earth, its lower operating potential and its known highest theoretical specific capacity (4200 mah.g-1). However, during the lithium intercalation and deintercalation process, the volume expansion of silicon Si is severe (300% or more), which leads to cracks inside the electrode, loss of electrical contact and thus increased resistance, which leads to rapid capacity fade, which significantly limits the commercial application of LIBs.
Recently, nano silicon dioxide (SiO2) has been proposed as a negative electrode material because it has a high theoretical specific capacity of 1961mAh.g-1 and a low discharge voltage close to that of silicon Si. However, during the initial lithiation process, lithium ions (Li)+) Intercalation into SiO2 produces inert Li2O and Li4SiO4, which may act as buffer components to some extent to mitigate the volume expansion effect. Therefore, the SiO2 anode material exhibits better cycling stability than the Si anode material.
However, the most important drawback limiting the commercial application of SiO2 is its poor electrical conductivity. Therefore, researchers have conducted a great deal of research in the preparation of carbon and silica composites. CN105633406A discloses a method for preparing a silicon dioxide/porous carbon lithium ion battery cathode material, which comprises the steps of dissolving sodium silicate, glucose and sodium chloride in deionized water according to the mass ratio; and drying the prepared solution, grinding the solution into fine powder, calcining the fine powder to obtain a sodium silicate/carbon precursor, putting the sodium silicate/carbon precursor into concentrated hydrochloric acid, drying the precursor in an oven at 170 ℃, and washing the dried precursor to obtain the silicon dioxide/porous carbon composite material. CN105977470A discloses a silicon dioxide activated carbon composite material, a preparation method thereof and application of a lead-carbon battery. The preparation method comprises the following steps: 1) soaking rice hull in strong inorganic acid solution, and purifying; 2) drying, carbonizing and activating the purified rice hulls for one time, wherein the heating system is divided into three sections to obtain carbonized rice hulls; 3) putting the carbonized rice hulls into an inorganic strong base solution, then slowly adding a dilute inorganic strong acid solution, stirring, filtering and washing to obtain a precursor; 4) And drying and activating the precursor again to obtain the silicon dioxide activated carbon composite material. CN105280879A discloses a silica/carbon composite porous electrode and a preparation method thereof. Mixing silicon dioxide with a dispersing agent to prepare uniform silicon dioxide sol; then uniformly mixing the silica sol and the graphite additive to prepare mixed slurry; and drying and crushing the mixed slurry into powder, and preparing the powder into a formed blank. CN107634190A discloses a method for preparing a silica-carbon nanocomposite by high-temperature heat treatment, wherein the silica-carbon nanocomposite is formed by compounding carbon-coated silica nanoparticles.
CN103035917A discloses a preparation method of a silicon dioxide/carbon composite negative electrode material for a lithium ion battery, which comprises the steps of preparing porous silicon dioxide with a xerogel or aerogel structure by using tetraethoxysilane as a silicon source and adopting a sol-gel method and a normal pressure drying process, carrying out ball milling treatment on the porous silicon dioxide, and preparing the nano silicon dioxide/carbon composite negative electrode material through carbon coating and heat treatment. CN103730662A discloses a silicon dioxide/carbon composite material for a lithium ion battery cathode and a preparation method thereof. Catalytically hydrolyzing a silicon-containing compound in a solution containing an organic template under an alkaline condition to prepare porous silicon dioxide containing the organic template; then carrying out suction filtration and washing on the porous silicon dioxide containing the organic template agent; and (3) placing the crude product in an inert atmosphere for heat treatment to obtain the silicon dioxide/carbon composite material. CN105742600A discloses a preparation method of a silica/carbon nano composite aerogel for lithium ion batteries, which can inhibit the problems of volume effect and particle agglomeration of silica in the circulation process by carbon coating of silica aerogel. CN104953097A discloses a silicon dioxide carbon composite nanofiber lithium ion battery cathode material and a preparation method thereof. Firstly, weighing an organic block polymer surfactant as a forming agent, and dissolving the organic block polymer surfactant in a liquid solvent to form a first solution; weighing a silicon source and dissolving the silicon source in the liquid solvent to form a second solution; adding the second solution into the first solution, stirring uniformly at constant temperature to form a third solution, and evaporating the third solution at constant temperature to form gel; and finally, carrying out heat treatment on the gel. CN105895880A A preparation method of a silicon dioxide composite material for a lithium ion battery cathode comprises three processes of preparation of a [ carbon nano tube/silicon dioxide ] composite material, preparation of a silicon dioxide precursor and preparation of the silicon dioxide composite material. CN104300124A discloses a preparation method of a silica/carbon composite and its application in lithium/sodium ion battery, firstly, crushing biomass ash into particles smaller than centimeter grade; then, carrying out heat treatment for 4-20 h at the temperature of 800-1500 ℃ in the atmosphere of argon, nitrogen, carbon monoxide, hydrogen or steam; finally, the obtained product is washed in water or dilute acid, separated and dried to obtain the silicon dioxide/carbon composite. CN103474636A discloses a silicon-based lithium ion battery cathode material and a preparation method thereof, wherein at room temperature, a surfactant is added into deionized water and stirred; then adding the silicon powder suspension and stirring; heating the mixed solution to 40-50 ℃, respectively dripping 3-aminopropyltriethoxysilane and ethyl orthosilicate, and stirring; then heating to 70-90 ℃, and preserving heat for 15-48 hours; collecting reaction products in a centrifugal mode, washing the reaction products with ethanol and deionized water respectively, and drying the reaction products; and adding the obtained product into an acetonitrile hydrochloric acid mixed solution, stirring for 4-8 hours, then washing again by using deionized water, and drying to obtain the material.
CN105098183A discloses a preparation method of a microporous carbon negative electrode material of a lithium ion battery, which comprises the steps of carbonizing rice hulls, pickling, activating and removing silicon dioxide to prepare the porous carbon negative electrode material. CN103647043A discloses a preparation method of a lithium ion secondary battery cathode material, which takes rice hulls as raw materials, and the raw materials are carbonized at 200-700 ℃ and treated at 700-1000 ℃ under the atmosphere of hydrogen or/and argon to prepare the electrode material. CN106848249A discloses a preparation method of a SiO2@ C core-shell composite lithium ion battery cathode material, which is prepared by carbonizing rice hulls, pickling and ball-milling.
The preparation method of the carbon and silicon dioxide composite material is researched by the scheme, the preparation process is complex, and the distribution of silicon dioxide and carbon is controlled by reaction conditions. Thus, so far, there have been problems as follows:
(1) although lithium ions have a smaller expansion coefficient than silicon during intercalation into silicon dioxide, a certain expansion space is still required.
(2) Compared with graphite, both carbon and silicon dioxide have the defect of poor conductivity, and the application of the carbon and silicon dioxide composite material as a negative electrode material is restricted.
There is therefore a need in the art for a new solution to these problems.
Disclosure of Invention
The invention aims to provide a method for preparing a rice hull-based negative electrode material, which takes rice hulls which are agricultural and sideline products as raw materials, adopts dilute acid hydrolysis pretreatment, regulates and controls the proportion of carbon and silicon, and solves the problems that silicon dioxide and carbon on the inner layer and the outer layer in pyrolytic carbon are not uniformly distributed, and lithium insertion and lithium removal are asynchronous to reduce specific capacity due to different microstructures; then, zinc chloride is used as an activating agent to prepare a porous ion channel, so that a buffer space is provided for the volume expansion of the silicon dioxide in the charge and discharge processes; meanwhile, in order to solve the main defect problem of limiting the commercial application of silicon dioxide as the cathode material: the conductivity is poor, and the electrode asphalt is adopted to modify the modified porous C/SiO2 negative electrode material.
In order to achieve the purpose, the invention provides a method for preparing a rice hull-based negative electrode material, which is characterized by comprising the following steps of:
the method comprises the following steps: screening raw material rice hulls to remove impurities, and crushing to obtain rice hull powder with the particle size of 10-20 mm for later use;
step two: adding the crushed rice hulls into a reaction kettle, and mixing the rice hulls in a dry basis of 1Kg: (5-10) adding 1-10 wt% sulfuric acid solution according to the proportion of L, heating to 100-120 ℃, and performing catalytic hydrolysis for 0.5-2 h to prepare xylose aqueous solution and hydrolysis residues; conveying the xylose solution to a furfural workshop to produce furfural;
step three: according to the dry weight ratio of 1:2, uniformly mixing the hydrolysis residue obtained in the step two with zinc chloride, adding the mixture into a sagger, placing the sagger in a tubular furnace, heating to 500-600 ℃, activating for 1-2 h, cooling to room temperature, discharging, soaking for 2-6 h by using a hydrochloric acid solution with the concentration of 0.5M, filtering, washing by using water until no chloride ion exists, and drying at 110 ℃ to prepare a primary cathode material;
step four: uniformly mixing and dispersing the primary cathode material and the electrode asphalt in the third step for 0.5h-1h to prepare asphalt/primary cathode material mixed powder;
step five: and transferring the mixed powder in the fourth step into a tubular furnace, heating to 150-250 ℃ under the protection of nitrogen, carrying out constant-temperature heat treatment for 1-2 h, heating to 600-1000 ℃ again, carrying out constant-temperature heat treatment for 1-2 h, cooling, and scattering to prepare the C/SiO2 porous cathode material.
Preferably, the asphalt/primary negative electrode material mixed powder in the fourth step is prepared by the following method: adding electrode asphalt powder into a solvent, and stirring and dispersing for 0.5-2 h to obtain an asphalt suspension or solution; adding the primary negative electrode material into the asphalt suspension or solution, stirring and dispersing for 0.5-1 h, heating to recover the solvent, placing the solid in a drying box, and drying at 85 ℃ for 5-12 h to prepare asphalt/primary negative electrode material mixed powder.
The solvent is one or a mixture of two of cyclohexanol, absolute ethyl alcohol, acetone, tetrahydrofuran, cyclohexane and n-hexane.
Preferably, the asphalt/primary anode material mixed powder prepared in the fourth step is prepared by: uniformly mixing the electrode asphalt powder and the primary negative electrode material, and crushing and dispersing the mixture by using a jet mill until the particle size of the primary negative electrode material is 10-15 mu m to prepare asphalt/primary negative electrode material mixed powder.
The mass ratio of the electrode asphalt to the primary cathode material in the fourth step is (10-30): 100.
the solid-liquid ratio of the asphalt to the solvent is (1-15) Kg: 100L.
Through the design scheme, the invention can bring the following beneficial effects:
1. after the rice hulls are carbonized under proper conditions, the silicon dioxide is uniformly coated by amorphous carbon without any complex carbon coating technology. Therefore, the porous C/SiO2 composite material prepared by using the rice hulls as the raw material is used as the cathode material of the LIBs, and has great development potential.
2. The hydrolysis temperature and time are regulated, the proportion of silicon dioxide and carbon in the precursor is regulated, the proportion and distribution of C/SiO2 in the negative electrode material are controlled, and the coulombic efficiency is improved.
3. The method adopts zinc chloride ZnCl2 as an activator to carry out carbonization activation on hydrolyzed rice hulls, controls the activation temperature and the activation time, and changes the pore diameter and the pore volume of the negative electrode material to obtain the porous C/SiO2 negative electrode material with high specific surface area, and the main purpose of the method is to increase the contact area of electrolyte and the C/SiO2 negative electrode material so as to promote Li+Rapidly diffusing at its interface.
4. The discharge specific capacity of the obtained porous C/SiO2 negative electrode material under the current density of 0.1A.g-1 can be more than 1100mAh/g, which is higher than that of a porous C/SiO2 negative electrode material prepared by taking a chemical reagent as a raw material (635.7 mAh/g under 0.1A/g). The method is simple, efficient, energy-saving, high in operability, low in raw material cost and capable of realizing large-scale industrial production.
5. The silicon dioxide silicon negative electrode material can generate larger volume change in the charging and discharging processes, so that the electrode is cracked and pulverized, particularly, rice husk pyrolytic carbon is used as the negative electrode material, wherein the carbon has a loose structure and poor pulverization resistance, and the cycle stability is reduced. The electrode asphalt is uniformly permeated to the surface of the particles, and the internal binding force of the carbon is greatly improved and the anti-pulverization capability is improved after heat treatment.
6. In order to solve the problem of limiting the commercial application of SiO2 as a cathode material, namely the problem of poor conductivity, the invention adopts electrode asphalt to modify and modify C/SiO2, thereby improving the cycle stability, preventing side reaction and solving the problem of leakage current.
7. The hydrolysis liquid is used for preparing the furfural, so that hydrolysis waste water is treated, a furfural product with high added value is produced, and meanwhile, the cost of the cathode material is reduced.
Detailed Description
In order to more clearly illustrate the invention, the invention is further described below in connection with preferred embodiments. As will be appreciated by those skilled in the art. The following detailed description is illustrative rather than limiting in nature and is not intended to limit the scope of the invention.
Example 1
The method comprises the following steps: screening raw material rice hulls to remove impurities, and crushing to obtain particles with the particle size of 10-20 mm for later use;
step two: adding the crushed rice hulls into a reaction kettle, adding a 3 wt% sulfuric acid solution according to the proportion of 1Kg of dry basis to 10L of dry basis, heating to 120 ℃, and carrying out catalytic hydrolysis for 1h to prepare a xylose water solution with the concentration of 12 wt% and hydrolysis residues;
step three: adding 2mol/L of catalyst sulfuric acid solution into a reactor, introducing nitrogen at 200 ℃ into the bottom of the reactor, heating until the catalyst solution flows back, adding NaCl until the solution is saturated, stirring to form a rotating liquid surface with a catalyst and a cocatalyst with fixed concentrations, then spraying the obtained xylose solution with the concentration of 12 wt% into the reactor at a certain speed, and carrying out xylose dehydration reaction on a liquid surface layer to generate furfural;
example 2
The method comprises the following steps: uniformly mixing the hydrolysis residue obtained in the second step in the example 1 with zinc chloride according to the dry basis weight ratio of 1:2, adding the mixture into a sagger, placing the sagger into a tubular furnace, heating the sagger to 600 ℃, activating the sagger for 1.5h, cooling the sagger to room temperature, discharging the materials, soaking the materials in 0.5M hydrochloric acid solution for 6h, filtering the materials, washing the materials with water until no chloride ions exist, and drying the materials at 110 ℃ to prepare a primary cathode material;
step two: mixing the primary negative electrode material with the electrode asphalt/ethanol suspension, stirring and dispersing for 0.5-1 h, heating to recover liquid, placing the solid in a drying oven, and drying at 85 ℃ for 5-12 h to prepare asphalt/primary negative electrode material mixed powder;
step three: and transferring the asphalt/primary cathode material mixed powder into a tube furnace, heating to 200 ℃ under the protection of nitrogen, carrying out constant-temperature heat treatment for 1h, heating to 800 ℃ again, carrying out constant-temperature heat treatment for 1h, cooling, and scattering to prepare the C/SiO2 porous cathode material.
Example 3
Uniformly mixing the primary negative electrode material prepared in the first step in the example 2 with electrode asphalt powder according to the mass ratio of 2:10, crushing and dispersing the mixture by using a jet mill until the particle size of the primary negative electrode material is 10-15 microns, preparing uniformly mixed asphalt/primary negative electrode material mixed powder, transferring the uniformly mixed asphalt/primary negative electrode material mixed powder into a tube furnace, heating to 200 ℃ under the protection of nitrogen, carrying out constant-temperature heat treatment for 1h, then heating to 800 ℃ for 1h, cooling, and scattering to prepare the asphalt modified negative electrode material.
It should be apparent that the above description of the embodiments is only for the purpose of helping understanding the method of the present invention and the core idea thereof, but it should be apparent to those skilled in the art that various changes, modifications and substitutions can be made to the embodiments without departing from the spirit and principle of the present invention described in the claims, and those improvements and modifications also fall within the protection scope of the claims of the present invention.
Claims (6)
1. A method for preparing a rice hull-based negative electrode material is characterized by comprising the following steps:
the method comprises the following steps: screening raw material rice hulls to remove impurities, and crushing to obtain particles with the particle size of 10-20 mm for later use;
step two: adding the crushed rice hulls into a reaction kettle, and mixing the rice hulls in a dry basis of 1Kg: (5-10) adding 1-10 wt% sulfuric acid solution according to the proportion of L, heating to 100-120 ℃, and performing catalytic hydrolysis for 0.5-2 h to prepare xylose aqueous solution and hydrolysis residues; conveying the xylose solution to a furfural workshop to produce furfural;
step three: according to the dry weight ratio of 1:2, uniformly mixing the hydrolysis residue obtained in the step two with zinc chloride, adding the mixture into a sagger, placing the sagger in a tubular furnace, heating to 500-600 ℃, activating for 1-2 h, cooling to room temperature, discharging, soaking for 2-6 h by using a hydrochloric acid solution with the concentration of 0.5M, filtering, washing by using water until no chloride ion exists, and drying at 110 ℃ to prepare a primary cathode material;
step four: uniformly mixing and dispersing the primary cathode material and the electrode asphalt in the third step for 0.5h-1h to prepare asphalt/primary cathode material mixed powder;
step five: and transferring the asphalt/primary cathode material mixed powder obtained in the fourth step into a tubular furnace, heating to 150-250 ℃ under the protection of nitrogen, carrying out constant-temperature heat treatment for 1-2 h, heating to 600-1000 ℃ again, carrying out constant-temperature heat treatment for 1-2 h, cooling, and scattering to obtain the C/SiO2 porous cathode material.
2. The method for preparing the rice hull-based negative electrode material according to claim 1, wherein the asphalt/primary negative electrode material mixed powder in the fourth step is prepared by: adding electrode asphalt powder into a solvent, and stirring and dispersing for 0.5-2 h to obtain an asphalt suspension or solution; adding the primary negative electrode material into the asphalt suspension or solution, stirring and dispersing for 0.5-1 h, heating to recover the solvent, placing the solid in a drying box, and drying at 85 ℃ for 5-12 h to prepare asphalt/primary negative electrode material mixed powder.
3. The method for preparing the rice hull-based negative electrode material is characterized in that the solvent is one or a mixture of two of cyclohexanol, absolute ethyl alcohol, acetone, tetrahydrofuran, cyclohexane and n-hexane.
4. The method for preparing the rice hull-based negative electrode material according to claim 1, wherein the asphalt/primary negative electrode material mixed powder in the fourth step is prepared by: uniformly mixing the electrode asphalt powder and the primary negative electrode material, and crushing and dispersing the mixture by using a jet mill until the particle size of the primary negative electrode material is 10-15 mu m to prepare asphalt/primary negative electrode material mixed powder.
5. The method for preparing the rice hull-based negative electrode material according to claim 1, 2 or 4, wherein the mass ratio of the electrode pitch to the primary negative electrode material in the fourth step is (10-30): 100.
6. the method for preparing the rice hull-based negative electrode material is characterized in that the solid-to-liquid ratio of the electrode asphalt to the solvent is (1-15) Kg: 100L.
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| CN113178564B (en) * | 2021-04-25 | 2023-01-03 | 陈庆 | Silicon dioxide-carbon composite material and preparation method and application thereof |
| CN114874527A (en) * | 2022-05-19 | 2022-08-09 | 合肥略邦信息技术有限公司 | Bio-based controllable degradable mulching film and production method thereof |
| CN118588915A (en) * | 2024-07-31 | 2024-09-03 | 宁波广科新材料有限公司 | Preparation method of high-rate lithium battery composite silicon-carbon anode material |
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