CN109830667B - Preparation method of mesoporous silicon/graphene composite lithium ion battery cathode material - Google Patents
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Abstract
The invention belongs to the field of electrode material preparation, and provides a preparation method of a mesoporous silicon/graphene composite lithium ion battery cathode material, which comprises the following steps: (1) preparing an Al-20Si-5Mg alloy, (2) preparing mesoporous silicon by treating the Al-Si alloy with an electron beam, (3) treating a mesoporous silicon material, and (4) compounding the mesoporous silicon/graphene negative electrode material. The invention successfully utilizes the holes and pits which appear in the electron beam treatment process and are regarded as defects, so that the Al-20Si-5Mg alloy becomes mesoporous silicon with a porous structure after being treated by the high-current pulsed electron beam, and finally the silicon cathode material which can effectively absorb the volume expansion of the silicon in the discharge process is obtained. The obtained mesoporous silicon material is compounded with graphene and applied to a lithium electronic cathode material, and finally, a novel lithium ion battery with excellent electrochemical performance and cycle performance, large capacity and high safety is obtained, thereby making a contribution to the development of the lithium ion battery.
Description
Technical Field
The invention belongs to the field of electrode material preparation, and particularly relates to a preparation method of a mesoporous silicon/graphene composite lithium ion battery cathode material
Background
With the increasing exhaustion of fossil fuels, the search for a new renewable clean energy source becomes a problem which needs to be solved urgently nowadays. Among all the renewable energy sources found, secondary batteries are occupying an increasingly important position, and one of the lithium ion batteries is receiving more and more attention from researchers due to its excellent properties such as long cycle life, small self-discharge rate, high energy conversion rate, and high energy density.
Suitable anode and cathode materials are the basis for ensuring the performance of the battery. Most commonly used positive and negative electrode materials of the lithium battery are carbon materials and silicon materials, however, the carbon materials are easy to collapse in the structure in the charging and discharging process under large current, so that the cycle performance of the lithium battery is affected, meanwhile, the theoretical specific capacity of the lithium battery is low, the capacity of the existing carbon is close to the theoretical capacity, and the development potential of the lithium battery is low. Compared with carbon materials, the silicon materials have larger theoretical capacity, but the volume expansion can occur in the charging and discharging process of the lithium battery, and the great change of the volume can cause the active substances to drop off rapidly, so that the contact between the battery materials and the current collector is lost, and the performance of the battery is directly influenced. It is therefore important to find a material that has good electrical conductivity and is able to effectively alleviate the problem of volume expansion.
The mesoporous silicon-like material can effectively solve the problem of volume expansion of the silicon material, and the change of the volume can be relieved by virtue of the loose structure of the mesoporous silicon-like material. However, the conductivity of the silicon material is inferior to that of the carbon material, and the graphene has good mechanical property and electrical property due to the special structure of the graphene, so that the advantages of the graphene material and the mesoporous silicon material can be combined if the graphene material and the mesoporous silicon material can be compounded, and the performance of the battery is greatly improved.
At present, methods and devices for preparing mesoporous silicon-like materials are various, and mainly include chemical etching methods, thermal reduction methods, template methods, electrochemical etching methods, and the like. Different preparation methods and devices have great influence on the performance and the structure of the prepared mesoporous silicon-like material, but the existing preparation methods have the defects of complex operation method, poor performance of the obtained material and the like.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a preparation method of a mesoporous silicon/graphene composite lithium ion battery cathode material, and aims to prepare the mesoporous silicon/graphene composite lithium ion battery cathode material by a simple method, obtain the mesoporous silicon/graphene composite material which has a porous structure and is difficult to pulverize, and apply the mesoporous silicon/graphene composite material to the lithium ion battery cathode material.
The technical scheme of the invention is as follows:
a preparation method of a mesoporous silicon/graphene composite lithium ion battery cathode material comprises the following specific steps:
(1) preparation of Al-20Si-5Mg alloy
High-purity silicon, high-purity aluminum and high-purity magnesium are mixed according to the proportion of 1: 20: 5, heating and melting at high temperature, controlling the temperature to be 700-850 ℃, and preparing Al-20Si-5Mg alloy; preparing Al-20Si-5Mg alloy into square blocks with the same size, and sealing the square blocks after surface treatment;
(2) preparation of mesoporous silicon by electron beam treatment of Al-20Si-5Mg alloy
Placing the Al-20Si-5Mg alloy square block prepared in the step (1) on a high-current pulse electron beam workbench, starting high-current pulse electron beam equipment, vacuumizing the equipment, setting the accelerating voltage of 15-30KV and the energy density of 2-3J/cm2The pulse frequency is 5-20 times, and the mesoporous silicon material subjected to strong current pulse is obtained;
(3) mesoporous silicon material treatment
Performing linear cutting on the mesoporous silicon material obtained in the step (2) to enable the thickness to reach 3-5mm, polishing to enable the thickness of the polished mesoporous silicon material to be 1-1.5mm, soaking the polished mesoporous silicon material in dilute hydrochloric acid for 30 minutes, and then filtering to obtain a mesoporous silicon wafer;
(4) compounding of mesoporous silicon/graphene anode material
Adding deionized water into the mesoporous silicon material, adding sodium carboxymethylcellulose (CMC), mechanically stirring and uniformly mixing until mesoporous silicon material particles are completely in a suspension state to obtain a mesoporous silicon particle suspension; adding sodium dodecyl sulfate and graphene into deionized water, mechanically stirring and uniformly mixing until the graphene is completely dissolved to obtain a graphene turbid liquid, mixing the mesoporous silicon particle suspension with the graphene turbid liquid, wherein the mesoporous silicon particle suspension and the graphene turbid liquid are 5-30% of mesoporous silicon and 70-95% of graphene in percentage by mass, mechanically stirring and uniformly mixing, then performing ultrasonic oscillation to obtain a mixed solution, performing suction filtration and washing on the mixed solution to neutrality, collecting a solid material, performing vacuum drying, placing the dried material in a tubular heating furnace, sintering at the temperature of 750-.
Further, the surface treatment in the step (1) is specifically: polishing the square block until the surface of the square block is smooth and has no scratch to obtain a metallographic sample Al-20Si-5Mg alloy square block; and (4) washing the polished metallographic sample with clear water to remove residual impurities on the surface, then washing with absolute ethyl alcohol, and drying.
Further, the mass concentration of the dilute hydrochloric acid in the step (3) is 5-10%.
The preparation method has the beneficial effects that the preparation process is simple, the prepared mesoporous silicon is loose and porous and has a better specific surface area, after the mesoporous silicon is applied to the negative electrode material of the lithium ion battery, the battery capacity is improved, and the electrochemical performance and the cycle performance are excellent. The invention successfully utilizes the holes and pits which appear in the electron beam treatment process and are regarded as defects, so that the Al-20Si-5Mg alloy becomes mesoporous silicon with a porous structure after being treated by the high-current pulsed electron beam, and finally the silicon cathode material which can effectively absorb the volume expansion of the silicon in the discharge process is obtained. The obtained mesoporous silicon material is compounded with graphene and applied to a lithium electronic cathode material, and finally, a novel lithium ion battery with excellent electrochemical performance and cycle performance, large capacity and high safety is obtained, thereby making a contribution to the development of the lithium ion battery.
Detailed Description
Example 1
The preparation method of the mesoporous silicon/graphene composite negative electrode material of the embodiment is carried out according to the following steps:
(1) preparation of Al-20Si-5Mg alloy
High-purity silicon, high-purity aluminum and high-purity magnesium are mixed according to the proportion of 1: 20: 5, heating and melting at high temperature, controlling the temperature at 700 ℃, and preparing Al-20Si-5Mg alloy; preparing an Al-20Si-5Mg alloy into square blocks with the same size, and polishing the square blocks until the surfaces of the square blocks are smooth and have no scratch to obtain metallographic samples of the Al-20Si-5Mg alloy square blocks; and washing the polished metallographic sample with clear water to remove residual impurities on the surface, washing with absolute ethyl alcohol, drying, and sealing in a vacuum bag.
(2) Preparation of mesoporous silicon by electron beam treatment of Al-20Si-5Mg alloy
Placing the Al-20Si-5Mg alloy metal block obtained in the step (1) on a high-current pulse electron beam workbench, starting high-current pulse electron beam equipment, vacuumizing the equipment, setting the accelerating voltage of 15KV and the energy density of 2J/cm2And the pulse frequency is 5 times, and finally the mesoporous silicon material subjected to strong current pulse is obtained.
(3) Mesoporous silicon material treatment
Performing linear cutting on the obtained mesoporous silicon material to enable the thickness to reach 4mm, polishing with abrasive paper to enable the thickness of the polished mesoporous silicon material to be about 1mm, soaking with dilute hydrochloric acid for 30min, and performing filtering operation to obtain the mesoporous silicon wafer.
The mass concentration of the dilute hydrochloric acid is 10%.
(4) Compounding of mesoporous silicon/graphene anode material
Adding deionized water into a mesoporous silicon material, adding sodium carboxymethylcellulose (CMC), mechanically stirring for 15min until mesoporous silicon material particles are completely suspended to obtain a mesoporous silicon particle suspension, adding sodium dodecyl sulfate and graphene into the deionized water, mechanically stirring for 10min until the graphene is completely dissolved to obtain a graphene suspension, mixing the mesoporous silicon particle suspension with the graphene suspension, wherein the mass percentages of the mesoporous silicon particles and the graphene are as follows: mechanically stirring 10% of mesoporous silicon and 90% of graphene for 10 minutes, then performing ultrasonic oscillation to obtain a mixed solution, performing suction filtration and washing on the mixed solution to neutrality, collecting a solid material, performing vacuum drying on the solid material, placing the dried material in a tubular heating furnace, sintering the material at 800 ℃ for 5 hours, and naturally cooling the sintered material to room temperature to obtain the mesoporous silicon/graphene composite lithium ion battery cathode material.
The application of the mesoporous silicon/graphene negative electrode material in the embodiment is to manufacture a button lithium battery, and the method specifically comprises the following steps:
(1) mixing the mesoporous silicon/graphene negative electrode material, superconducting graphite and a binder according to a mass ratio of 10:1:1, preparing slurry, coating the slurry on copper foil, drying and pressing to form an electrode plate, wherein the diameter of the electrode plate is 1.5 cm;
(2) the electrolyte takes EC (ethylene carbonate), EDC (diethyl carbonate) and EMC (ethyl methyl carbonate) in a volume ratio of 1:1:1 as solvents, and LiPF with the concentration of 1.0M6And (2) taking a metal lithium sheet as a positive electrode, taking a polypropylene microporous membrane as a diaphragm, taking the electrode sheet in the step (1) as a negative electrode, and assembling the lithium button cell in a vacuum glove box.
Example 2
The preparation method of the mesoporous silicon/graphene composite negative electrode material of the embodiment is carried out according to the following steps:
(1) preparation of Al-20Si-5Mg alloy
High-purity silicon, high-purity aluminum and high-purity magnesium are mixed according to the proportion of 1: 20: 5, heating and melting at high temperature, controlling the temperature at 800 ℃ and preparing Al-20Si-5Mg alloy; preparing an Al-20Si-5Mg alloy into square blocks with the same size, and polishing the square blocks until the surfaces of the square blocks are smooth and have no scratch to obtain metallographic samples of the Al-20Si-5Mg alloy square blocks; and washing the polished metallographic sample with clear water to remove residual impurities on the surface, washing with absolute ethyl alcohol, drying, and sealing in a vacuum bag.
(2) Preparation of mesoporous silicon by electron beam treatment of Al-20Si-5Mg alloy
Placing the Al-20Si-5Mg alloy metal block obtained in the step (1) on a high-current pulse electron beam workbench, starting high-current pulse electron beam equipment, vacuumizing the equipment, setting the accelerating voltage to be 20KV, and setting the energy density to be 2.5J/cm2And the pulse frequency is 10 times, and finally the mesoporous silicon material subjected to strong current pulse is obtained.
(3) Mesoporous silicon material treatment
Performing linear cutting on the obtained mesoporous silicon material to enable the thickness to reach 4mm, polishing with abrasive paper to enable the thickness of the polished mesoporous silicon material to be about 1mm, soaking with dilute hydrochloric acid for 30min, and performing filtering operation to obtain the mesoporous silicon wafer.
The mass concentration of the dilute hydrochloric acid is 5%.
(4) Compounding of mesoporous silicon/graphene anode material
Adding deionized water into the mesoporous silicon material, adding sodium carboxymethylcellulose (CMC), mechanically stirring for 20min until the mesoporous silicon material particles are completely suspended to obtain mesoporous silicon particle suspension, adding sodium dodecyl sulfate and graphene into deionized water, mechanically stirring for 15min until the graphene is completely dissolved to obtain a graphene turbid liquid, mixing the mesoporous silicon particle suspension with the graphene turbid liquid, wherein the mass percentage of the mesoporous silicon particles to the graphene is as follows: mechanically stirring 15% of mesoporous silicon and 85% of graphene for 10 minutes, then carrying out ultrasonic oscillation to obtain a mixed solution, filtering the mixed solution, washing to neutrality, collecting solid material, vacuum drying, sintering in a tubular heating furnace at 850 deg.c for 7 hr, and naturally cooling to room temperature after sintering to obtain the mesoporous silicon/graphene composite lithium ion battery cathode material.
The application of the mesoporous silicon/graphene negative electrode material in the embodiment is to manufacture a button lithium battery, and the method specifically comprises the following steps:
(1) mixing the mesoporous silicon/graphene negative electrode material, superconducting graphite and a binder according to a mass ratio of 10:1:1, preparing slurry, coating the slurry on copper foil, drying and pressing to form an electrode plate, wherein the diameter of the electrode plate is 2 cm;
(2) the electrolyte takes EC (ethylene carbonate), EDC (diethyl carbonate) and EMC (ethyl methyl carbonate) in a volume ratio of 1:1:1 as solvents, and LiPF with the concentration of 1.0M6And (2) taking a metal lithium sheet as a positive electrode, taking a polypropylene microporous membrane as a diaphragm, taking the electrode sheet in the step (1) as a negative electrode, and assembling the lithium button cell in a vacuum glove box.
Example 3
The preparation method of the mesoporous silicon/graphene composite negative electrode material of the embodiment is carried out according to the following steps:
(1) preparation of Al-20Si-5Mg alloy
High-purity silicon, high-purity aluminum and high-purity magnesium are mixed according to the proportion of 1: 20: 5, heating and melting at high temperature, controlling the temperature at 700 ℃, and preparing Al-20Si-5Mg alloy; preparing an Al-20Si-5Mg alloy into square blocks with the same size, and polishing the square blocks until the surfaces of the square blocks are smooth and have no scratch to obtain metallographic samples of the Al-20Si-5Mg alloy square blocks; and washing the polished metallographic sample with clear water to remove residual impurities on the surface, washing with absolute ethyl alcohol, drying, and sealing in a vacuum bag.
(2) Preparation of mesoporous silicon by electron beam treatment of Al-20Si-5Mg alloy
Placing the Al-20Si-5Mg alloy metal block obtained in the step (1) on a high-current pulse electron beam workbench, starting high-current pulse electron beam equipment, vacuumizing the equipment, setting the accelerating voltage to be 25KV and the energy density to be 3J/cm2And the pulse frequency is 15 times, and finally the mesoporous silicon material subjected to strong current pulse is obtained.
(3) Mesoporous silicon material treatment
Performing linear cutting on the obtained mesoporous silicon material to enable the thickness to reach 4mm, polishing with abrasive paper to enable the thickness of the polished mesoporous silicon material to be about 1mm, soaking with dilute hydrochloric acid for 30min, and performing filtering operation to obtain the mesoporous silicon wafer.
The mass concentration of the dilute hydrochloric acid is 10%.
(4) Compounding of mesoporous silicon/graphene anode material
Adding deionized water into the mesoporous silicon material, adding sodium carboxymethylcellulose (CMC), mechanically stirring for 25min until the mesoporous silicon material particles are completely suspended to obtain mesoporous silicon particle suspension, adding sodium dodecyl sulfate and graphene into deionized water, mechanically stirring for 20min until the graphene is completely dissolved to obtain a graphene turbid liquid, mixing the mesoporous silicon particle suspension with the graphene turbid liquid, wherein the mass percentage of the mesoporous silicon particles to the graphene is as follows: mechanically stirring 20% of mesoporous silicon and 80% of graphene for 10 minutes, then carrying out ultrasonic oscillation to obtain a mixed solution, filtering the mixed solution, washing to neutrality, collecting solid material, vacuum drying, sintering in a tubular heating furnace at 900 deg.c for 9 hr, and naturally cooling to room temperature after sintering to obtain the mesoporous silicon/graphene composite lithium ion battery cathode material.
The application of the mesoporous silicon/graphene negative electrode material in the embodiment is to manufacture a button lithium battery, and the method specifically comprises the following steps:
(1) mixing the mesoporous silicon/graphene negative electrode material, superconducting graphite and a binder according to a mass ratio of 10:1:1, preparing slurry, coating the slurry on copper foil, drying and pressing to form an electrode plate, wherein the diameter of the electrode plate is 1 cm;
(2) the electrolyte takes EC (ethylene carbonate), EDC (diethyl carbonate) and EMC (ethyl methyl carbonate) in a volume ratio of 1:1:1 as solvents, and LiPF with the concentration of 1.0M6And (2) taking a metal lithium sheet as a positive electrode, taking a polypropylene microporous membrane as a diaphragm, taking the electrode sheet in the step (1) as a negative electrode, and assembling the lithium button cell in a vacuum glove box.
Claims (3)
1. A preparation method of a mesoporous silicon/graphene composite lithium ion battery cathode material is characterized by comprising the following steps:
(1) preparation of Al-20Si-5Mg alloy
High-purity silicon, high-purity aluminum and high-purity magnesium are mixed according to the proportion of 1: 20: 5, heating and melting at high temperature, controlling the temperature to be 700-850 ℃, and preparing Al-20Si-5Mg alloy; preparing Al-20Si-5Mg alloy into square blocks with the same size, and sealing the square blocks after surface treatment;
(2) preparation of mesoporous silicon by electron beam treatment of Al-20Si-5Mg alloy
Placing the Al-20Si-5Mg alloy square block prepared in the step (1) on a high-current pulse electron beam workbench, starting high-current pulse electron beam equipment, vacuumizing the equipment, setting the accelerating voltage of 15-30KV and the energy density of 2-3J/cm2The pulse frequency is 5-20 times, and the mesoporous silicon material subjected to strong current pulse is obtained;
(3) mesoporous silicon material treatment
Performing linear cutting on the mesoporous silicon material obtained in the step (2) to enable the thickness to reach 3-5mm, polishing to enable the thickness of the polished mesoporous silicon material to be 1-1.5mm, soaking the polished mesoporous silicon material in dilute hydrochloric acid for 30 minutes, and then filtering to obtain a mesoporous silicon wafer;
(4) compounding of mesoporous silicon/graphene anode material
Adding deionized water into the mesoporous silicon material, adding sodium carboxymethylcellulose (CMC), mechanically stirring and uniformly mixing until mesoporous silicon material particles are completely in a suspension state to obtain a mesoporous silicon particle suspension; adding sodium dodecyl sulfate and graphene into deionized water, mechanically stirring and uniformly mixing until the graphene is completely dissolved to obtain a graphene turbid liquid, mixing the mesoporous silicon particle suspension with the graphene turbid liquid, wherein the mesoporous silicon particle suspension and the graphene turbid liquid are 5-30% of mesoporous silicon and 70-95% of graphene in percentage by mass, mechanically stirring and uniformly mixing, then performing ultrasonic oscillation to obtain a mixed solution, performing suction filtration and washing on the mixed solution to neutrality, collecting a solid material, performing vacuum drying, placing the dried material in a tubular heating furnace, sintering at the temperature of 750-.
2. The preparation method of the mesoporous silicon/graphene composite lithium ion battery anode material according to claim 1, wherein the surface treatment in the step (1) is specifically as follows: polishing the square block until the surface of the square block is smooth and has no scratch to obtain a metallographic sample Al-20Si-5Mg alloy square block; and (4) washing the polished metallographic sample with clear water to remove residual impurities on the surface, then washing with absolute ethyl alcohol, and drying.
3. The preparation method of the mesoporous silicon/graphene composite lithium ion battery anode material according to claim 1 or 2, wherein the mass concentration of the dilute hydrochloric acid in the step (3) is 5% -10%.
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