CN113213493B - Granati-shaped silicon oxide-nitrogen doped carbon composite material, synthesis method thereof and lithium ion capacitor - Google Patents
Granati-shaped silicon oxide-nitrogen doped carbon composite material, synthesis method thereof and lithium ion capacitor Download PDFInfo
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- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
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Abstract
The invention discloses a garnet-like silicon oxide-nitrogen doped carbon composite material, a synthesis method thereof and a lithium ion capacitor, wherein the synthesis method comprises the following steps: step a): mixing lysine with water, adding tetrapropyl orthosilicate, and stirring to obtain silica-based dispersion; step b): adding melamine and formaldehyde into water, and stirring to obtain a precursor solution; step c): pouring silica-based dispersion liquid into the precursor solution to obtain a mixed solution; step d): adjusting the pH value of the mixed solution to 4.5-5, filtering, washing and drying; step e): solidifying in air, carbonizing in nitrogen atmosphere to obtain the garnet-like silicon oxide-nitrogen doped carbon composite material. The surface of the silicon oxide garnet-shaped body of the composite material prepared by the synthesis method is coated by a layer of carbon material, so that the silicon oxide garnet-shaped body is prevented from directly contacting electrolyte, only lithium ions are allowed to pass through, the cycle performance is greatly improved, and the capacity of the lithium ion capacitor prepared by adopting the composite material as a negative electrode material is not obviously attenuated.
Description
Technical Field
The invention belongs to the technical field of lithium ion capacitors, and particularly relates to a garnet-like silicon oxide-nitrogen doped carbon composite material, a synthesis method thereof and a lithium ion capacitor.
Background
With the widespread use of various mobile electronic devices, such as smartphones, notebook computers, and the like, lithium ion capacitors have received a great deal of attention. However, the energy density and the power density of the commercial lithium ion capacitor at present are difficult to meet the requirements of technological development on the energy storage device. Therefore, development of an electrode material with high capacity is urgent.
For the lithium ion capacitor, the theoretical specific capacity of the graphite serving as the traditional negative electrode material is only 372mAh/g, and the actual capacity of the graphite is very close to the theoretical capacity of the graphite in terms of the current technical level and the process conditions, so that the specific capacity of the graphite is difficult to be greatly improved through process optimization and technical progress.
Compared with the graphite anode materials which are commercially used at present, the silicon oxide-based anode material has obvious advantages such as high specific capacity, low lithium intercalation potential, stable circulation, rich content and the like, so the silicon oxide-based anode material is considered as a high-capacity anode material with great development potential. However, there are problems associated with simple silicon oxide materials as negative electrode materials for lithium ion capacitors, in which: on the one hand, the inherent poor conductivity of the conductive material limits the use of the conductive material in a large amount; on the other hand, when the lithium ion battery is directly contacted with electrolyte, obvious volume expansion and contraction are generated in the charge and discharge process, the volume change can lead to structural rupture and then failure, or excessive SEI films are generated, lithium ions are consumed, the capacity is reduced, in addition, the capacity of the lithium ion battery is attenuated in the circulation process due to the fact that electrons caused by the volume expansion lose contact, and specifically: the volume expansion effect (200%) of the silicon oxide-based anode material in the charge-discharge process easily causes capacity attenuation, wherein the important point is an active material island effect caused by the loss of electron contact between active material particles due to volume expansion-contraction, and once the active material loses the electron contact, lithium can not be removed/intercalated any more, and finally the capacity attenuation of the material is caused.
Currently, in order to solve the problems of poor conductivity of a silicon oxide-based anode material and capacity attenuation caused by electron loss contact among active material particles due to volume change, researchers propose to construct a three-dimensional conductive network by using a one-dimensional nano material, such as physically mixing a carbon nano tube with a silicon oxide material [ Facile Synthesis and High Anode Performance of Carbon FiberInterwoven Amorphous Nano-SiOx/Graphene for Rechargeable Lithium Batteries, ACS appl. Mater. Interfaces 2013,5,11234]; however, the simple physical mixing method cannot combine the silicon oxide particles with the one-dimensional nano material, and the phenomenon that electrons of the active material lose contact is still easy to cause after a plurality of charge and discharge cycles. Then, synthesizing a Silicon-based anode material with a sea urchin-like structure in the high-temperature treatment process by utilizing metal platinum catalysis of Yoo et al, wherein nanowires with a Silicon/Silicon oxide core-shell structure grow on the surfaces of Silicon particles with micrometer dimensions and protrude, and a three-dimensional network is formed between the nanowires [ Helical Silicon/Silicon Oxide Core Shell Anodes Grown onto the Surface ofBulkSilicon, nano Letters,2011,11,4324]; however, the preparation process of the method is complex, the catalysis is needed by means of noble metals such as platinum, the preparation cost is high, and the practical production and application are difficult to realize. The prior art also discloses the direct preparation of one-dimensional silicon nano-materials as negative electrode materials [ Self-sacrificed synthesis of carbon-coated SiOxnanowires for high capacity lithiumion battery anodes, J.Mater.chem.A,2017,5,4183]; however, the method mainly uses noble metal for catalysis, has complex preparation process and high cost, cannot realize practical industrial application, and has low tap density of the electrode prepared by the silicon nanowire, thereby seriously affecting the volume energy density in practical application.
Disclosure of Invention
The invention aims to overcome the defects and the shortcomings of the prior art, and provides a garnet-like silicon oxide-nitrogen doped carbon composite material, a synthesis method thereof and a lithium ion capacitor.
In order to achieve the above purpose, the invention adopts the following technical scheme:
a synthesis method of a garnet-like silicon oxide-nitrogen doped carbon composite material comprises the following steps:
step a): mixing lysine and water to obtain a lysine water solution, adding a certain amount of tetrapropyl orthosilicate into the lysine water solution, and stirring to obtain silica-based dispersion;
step b): adding melamine and formaldehyde into water, and stirring until a clear precursor solution is obtained;
step c): pouring the silica-based dispersion liquid obtained in the step a) into the precursor solution obtained in the step b) to obtain a mixed solution;
step d): adjusting the pH value of the mixed solution obtained in the step c) to 4.5-5, filtering, washing and drying;
step e): solidifying in air, and carbonizing in nitrogen atmosphere to obtain the garnet-like silicon oxide-nitrogen doped carbon composite material.
Further, in the step a), the mass ratio of lysine to water is 1:1; the tetrapropyl orthosilicate is added in two times, the mass ratio of the lysine aqueous solution to the tetrapropyl orthosilicate added for the first time is 100:2.5-5.7, and the mass of the tetrapropyl orthosilicate added for the second time is 2.5-3 times of the mass of the tetrapropyl orthosilicate added for the first time.
Further, after the first addition of tetrapropyl orthosilicate, stirring at a speed of 1000-1500 rpm for 30 minutes at room temperature, stirring at a speed of 300-500 rpm for 24 hours at 90 ℃, slowly adding the second addition of tetrapropyl orthosilicate, and stirring at a speed of 300-500 rpm for 24 hours at 90 ℃ to obtain the silica-based dispersion.
Further, in said step b), the ratio of melamine to formaldehyde in the water is such that 35-75mmol melamine and 100-150mmol formaldehyde are added per 10-40ml water, the formaldehyde used is preferably 37% formaldehyde solution by mass, and the three are mixed and stirred at a speed of 800-1000 rpm for 20-30 minutes at 85 ℃.
Further, in the step c), the precursor solution obtained in the step b) is cooled to 35-45 ℃, and the silica-based dispersion obtained in the step a) is poured into the mixture solution with stirring at a speed of 300-500 rpm, wherein the silica-based dispersion accounts for 4.5-6.5% of the mass ratio of the mixture solution.
Further, in the step d), the mixed solution is subjected to pH adjustment by using 2mol/l HCl solution, then is left at room temperature for 5 hours, is filtered, is washed by water and ethanol, and is dried in air at 60 ℃ for 12 hours.
Further, in the step e), the garnet-like silicon oxide-nitrogen doped carbon composite material is obtained by curing for 24 hours in air at 170-190 ℃ and then carbonizing for 2 hours in nitrogen atmosphere at 800 ℃.
The garnet-like silicon oxide-nitrogen doped carbon composite material is prepared by the synthesis method.
A lithium ion capacitor comprises a positive electrode, a negative electrode, a diaphragm and electrolyte; the negative electrode comprises the garnet-like silicon oxide-nitrogen doped carbon composite material or the garnet-like silicon oxide-nitrogen doped carbon composite material prepared by the synthesis method.
Further, the preparation method of the negative electrode comprises the following steps: uniformly mixing the garnet-like silicon oxide-nitrogen doped carbon composite material, the conductive carbon black and the adhesive according to a certain mass ratio, adding NMP (N-methyl pyrrolidone) to mix the materials and form uniform slurry, coating the uniform slurry on a copper foil, and drying and rolling the uniform slurry.
Still further, the mass ratio of the garnet-like silicon oxide-nitrogen doped carbon composite material, the conductive carbon black and the binder is 9:0.6:0.4.
The invention has the beneficial effects that: the garnet-shaped silicon oxide-nitrogen doped carbon composite material prepared by the synthesis method disclosed by the invention has the advantages that the surface of the garnet-shaped silicon oxide is coated by a layer of carbon material, and the silicon oxide garnet-shaped sphere can be prevented from being directly contacted with electrolyte when being used as a negative electrode material for preparing a lithium ion capacitor, and only lithium ions are allowed to pass through, so that the cycle performance is greatly improved, and the capacity of the lithium ion capacitor is not obviously attenuated. In addition, the synthesis method does not adopt noble metal catalysis, has simple preparation process and low cost, and can realize practical industrial application.
Drawings
FIG. 1 is an SEM characterization of a garnet-like silica-nitrogen doped carbon composite according to example 1 of the present invention;
FIG. 2 is a TEM characterization of the garnet-like silica-nitrogen doped carbon composite of example 1 of the present invention;
FIG. 3 is a graph showing the cycle performance of a lithium ion capacitor prepared from the garnet-like silica-nitrogen doped carbon composite material of example 1 of the present invention at a current density of 1A/g.
Detailed Description
The invention will be further described with reference to specific examples for better illustrating the objects, technical solutions and advantages of the invention. This invention may be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the concept of the invention to those skilled in the art, and the present invention will only be defined by the appended claims.
A synthesis method of a garnet-like silicon oxide-nitrogen doped carbon composite material comprises the following steps:
step a): equal weights of lysine and water were mixed to give an aqueous lysine solution, which was stirred for 10 to 20 minutes. To this solution was added a certain amount of tetrapropyl orthosilicate (aqueous lysine solution: tetrapropyl orthosilicate=100:2.5-5.7), and after intense stirring at room temperature for 30 minutes (1000-1500 rpm), stirring was continued at a medium-low speed at 90 ℃ for 24 hours (300-500 rpm). Then a quantity of tetrapropyl orthosilicate (2.5-3 times the quantity of tetrapropyl orthosilicate added as before) is slowly added. The mixture was kept under continuous stirring (300-500 rpm) at a medium-low speed at 90℃for 24 hours to obtain a silica-based dispersion.
Step b): a solution of 35-75mmol melamine and 100-150mmol formaldehyde (37 wt%) is added to 10-40ml water and stirred at 85℃for 20-30 minutes at 800-1000 rpm until a clear precursor solution is obtained.
Step c): the resulting precursor solution was cooled to 35-45℃and poured into the aforementioned silica-based dispersion (about 4.5-6.5. 6.5 wt%) with stirring at medium-low speed (300-500 rpm).
Step d): the pH of the mixture was adjusted to 4.5-5 with 2mol/l HCl solution. After standing at room temperature for 5 hours, filtering, washing with water and ethanol, and drying in air at 60 ℃ for 12 hours.
Step e): solidifying in air at 170-190 deg.C for 24 hr, and carbonizing at 800 deg.C in nitrogen atmosphere for 2 hr to obtain the garnet-like silicon oxide-nitrogen doped carbon composite material.
A lithium ion capacitor comprises a positive electrode, a negative electrode, a diaphragm and electrolyte; the negative electrode comprises the garnet-like silicon oxide-nitrogen doped carbon composite material prepared by the synthesis method.
The preparation method of the negative electrode comprises the following steps: uniformly mixing the garnet-like silicon oxide-nitrogen doped carbon composite material, the conductive carbon black and the adhesive according to a certain mass ratio, adding NMP (N-methyl pyrrolidone) to mix the materials and form uniform slurry, coating the uniform slurry on a copper foil, and drying and rolling the uniform slurry. Wherein, the mass ratio of the garnet-like silicon oxide-nitrogen doped carbon composite material, the conductive carbon black and the adhesive is 9:0.6:0.4.
Example 1:
a synthesis method of a garnet-like silicon oxide-nitrogen doped carbon composite material comprises the following steps:
step a): equal weights of lysine and water were mixed to give an aqueous lysine solution, which was stirred for 10 minutes. To this solution was added a further amount of tetrapropyl orthosilicate (aqueous lysine solution: tetrapropyl orthosilicate=100:2.5), and after stirring vigorously at room temperature for 30 minutes (1000 rpm), stirring was continued at a medium and low speed at 90℃for 24 hours (300 rpm). Then a quantity of tetrapropyl orthosilicate (2.5 times the quantity of tetrapropyl orthosilicate added previously) was slowly added. The mixture was kept at 90℃with continuous stirring (300 rpm) at a medium-low speed for 24 hours to obtain a silica-based dispersion.
Step b): a solution of 35mmol melamine and 100mmol formaldehyde (37 wt%) was added to 10ml water and stirred at 85℃for 20 minutes at 800 rpm until a clear precursor solution was obtained.
Step c): the resulting precursor solution was cooled to 35℃and poured into the aforementioned silica-based dispersion (about 4.5 wt%) with stirring at medium-low speed (300 rpm).
Step d): the pH of the mixture was adjusted to 4.5 with 2mol/l HCl solution. After standing at room temperature for 5 hours, filtering, washing with water and ethanol, and drying in air at 60 ℃ for 12 hours.
Step e): curing for 24 hours in air at 170 ℃, and carbonizing for 2 hours in nitrogen atmosphere at 800 ℃ to obtain the garnet-like silicon oxide-nitrogen doped carbon composite material.
The preparation method of the lithium ion capacitor by adopting the obtained garnet-like silicon oxide-nitrogen doped carbon composite material comprises the following steps of:
1. preparing a negative electrode plate: uniformly mixing the garnet-like silicon oxide-nitrogen doped carbon composite material, the conductive carbon black and the adhesive according to the mass ratio of 9:0.6:0.4, adding NMP to mix the materials and form uniform slurry, coating the uniform slurry on copper foil, drying the copper foil for 30 minutes in a 100 ℃ vacuum drying oven, rolling the copper foil for standby after drying the copper foil for 12 hours at 60 ℃ in the vacuum drying oven, and controlling the compaction density to be 1.5-1.7g/cm 3 。
2. Preparing a positive electrode plate: uniformly mixing Kurary active carbon, conductive carbon black and an adhesive according to the mass ratio of 8.5:1:0.5, adding NMP to mix the mixture and form uniform slurry, coating the uniform slurry on aluminum foil, drying the aluminum foil for 30 minutes in a vacuum drying oven at 100 ℃, drying the aluminum foil at 60 ℃ for 12 hours in the vacuum drying oven, rolling the aluminum foil for later use, and controlling the compaction density to be 0.45-0.65g/cm 3 。
3. The electrolyte was a 1.0M lithium hexafluorophosphate solution with a solvent of 2:1:2 (volume ratio) EC: DEC: DMC+10wt% FEC (fluoroethylene carbonate).
4. The membrane is a celgard2400 membrane.
5. And sequentially stacking the positive plate, the diaphragm and the negative plate, soaking the electrolyte, and packaging the electrolyte into a 2032 button battery shell.
It can be seen from fig. 1 and 2 that the surface of the silicon oxide garnet is coated by a layer of carbon material, so that the silicon oxide garnet sphere is prevented from directly contacting with electrolyte and only allows lithium ions to pass through, thus greatly improving the cycle performance, and the capacity is not obviously attenuated in the 3000-circle cycle process as can be seen from fig. 3.
Example 2:
a synthesis method of a garnet-like silicon oxide-nitrogen doped carbon composite material comprises the following steps:
step a): equal weights of lysine and water were mixed to give an aqueous lysine solution, which was stirred for 15 minutes. To this solution was added a further amount of tetrapropyl orthosilicate (aqueous lysine solution: tetrapropyl orthosilicate=100:4), and after intense stirring at room temperature for 30 minutes (1200 rpm), stirring was continued at a medium and low speed at 90 ℃ for 24 hours (400 rpm). Then a quantity of tetrapropyl orthosilicate (2.5-3 times the quantity of tetrapropyl orthosilicate added as before) is slowly added. The mixture was kept at 90℃with continuous stirring (400 rpm) at a medium-low speed for 24 hours to obtain a silica-based dispersion.
Step b): a solution of 50mmol melamine and 120 mmol formaldehyde (37 wt%) was added to 25ml water and stirred at 85℃for 25 minutes at 900 rpm until a clear precursor solution was obtained.
Step c): the resulting precursor solution was cooled to 40℃and poured into the aforementioned silica-based dispersion (about 5 wt%) with stirring at medium-low speed (400 rpm).
Step d): the pH of the mixture was adjusted to 4.8 with 2mol/l HCl solution. After standing at room temperature for 5 hours, filtering, washing with water and ethanol, and drying in air at 60 ℃ for 12 hours.
Step e): curing for 24 hours in air at 180 ℃, and carbonizing for 2 hours in nitrogen atmosphere at 800 ℃ to obtain the garnet-like silicon oxide-nitrogen doped carbon composite material.
Example 3:
a synthesis method of a garnet-like silicon oxide-nitrogen doped carbon composite material comprises the following steps:
step a): equal weights of lysine and water were mixed to give an aqueous lysine solution, which was stirred for 20 minutes. To this solution was added a certain amount of tetrapropyl orthosilicate (aqueous lysine solution: tetrapropyl orthosilicate=100:5.7), and after stirring vigorously at room temperature for 30 minutes (1500 rpm), stirring was continued at a medium and low speed at 90℃for 24 hours (500 rpm). Then a quantity of tetrapropyl orthosilicate (3 times the quantity of tetrapropyl orthosilicate added previously) was slowly added. The mixture was kept at 90℃with continuous stirring (500 rpm) at a medium-low speed for 24 hours to obtain a silica-based dispersion.
Step b): a solution of 75mmol melamine and 150mmol formaldehyde (37 wt%) was added to 40ml water and stirred at 1000 rpm for 30 minutes at 85℃until a clear precursor solution was obtained.
Step c): the resulting precursor solution was cooled to 45℃and the silica-based dispersion (about 6.5. 6.5 wt%) was poured under medium-low speed stirring (500 rpm).
Step d): the pH of the mixture was adjusted to 5 with 2mol/l HCl solution. After standing at room temperature for 5 hours, filtering, washing with water and ethanol, and drying in air at 60 ℃ for 12 hours.
Step e): curing for 24 hours in air at 190 ℃, and carbonizing for 2 hours in nitrogen atmosphere at 800 ℃ to obtain the garnet-like silicon oxide-nitrogen doped carbon composite material.
It is apparent that the above examples are given by way of illustration only and are not limiting of the embodiments. Other variations or modifications of the above teachings will be apparent to those of ordinary skill in the art. It is not necessary here nor is it exhaustive of all embodiments. While still being apparent from variations or modifications that may be made by those skilled in the art are within the scope of the invention.
Claims (10)
1. A synthesis method of a garnet-like silicon oxide-nitrogen doped carbon composite material is characterized by comprising the following steps: the method comprises the following steps:
step a): mixing lysine and water to obtain a lysine water solution, adding a certain amount of tetrapropyl orthosilicate into the lysine water solution, and stirring to obtain silica-based dispersion;
step b): adding melamine and formaldehyde into water, and stirring until a clear precursor solution is obtained;
step c): pouring the silica-based dispersion liquid obtained in the step a) into the precursor solution obtained in the step b) to obtain a mixed solution;
step d): adjusting the pH value of the mixed solution obtained in the step c) to 4.5-5, filtering, washing and drying;
step e): solidifying in air, and carbonizing in nitrogen atmosphere to obtain the garnet-like silicon oxide-nitrogen doped carbon composite material.
2. The synthesis method according to claim 1, wherein: in the step a), the mass ratio of lysine to water is 1:1; the tetrapropyl orthosilicate is added in two times, the mass ratio of the lysine aqueous solution to the tetrapropyl orthosilicate added for the first time is 100:2.5-5.7, and the mass of the tetrapropyl orthosilicate added for the second time is 2.5-3 times of the mass of the tetrapropyl orthosilicate added for the first time.
3. The synthesis method according to claim 2, characterized in that: after the first time of adding tetrapropyl orthosilicate, stirring at the speed of 1000-1500 rpm for 30 minutes at room temperature, stirring at the speed of 300-500 rpm for 24 hours at 90 ℃, slowly adding tetrapropyl orthosilicate for the second time, and stirring at the speed of 300-500 rpm for 24 hours at the temperature of 90 ℃ to obtain the silica-based dispersion.
4. The synthesis method according to claim 1, wherein: in the step b), the melamine and formaldehyde are added into water in a proportion of 35-75mmol of melamine and 100-150mmol of formaldehyde in every 10-40ml of water, and the three are mixed and stirred for 20-30 minutes at a speed of 800-1000 rpm at 85 ℃.
5. The synthesis method according to claim 1, wherein: in the step c), the precursor solution obtained in the step b) is cooled to 35-45 ℃, and the precursor solution is poured into the silica-based dispersion liquid obtained in the step a) under the stirring of the speed of 300-500 r/min, wherein the silica-based dispersion liquid accounts for 4.5-6.5% of the mass ratio of the mixed solution.
6. The synthesis method according to claim 1, wherein: in the step e), the garnet-like silicon oxide-nitrogen doped carbon composite material is obtained by solidifying the mixture in the air for 24 hours at 170-190 ℃ and then carbonizing the mixture for 2 hours in a nitrogen atmosphere at 800 ℃.
7. A garnet-like silicon oxide-nitrogen doped carbon composite material is characterized in that: prepared by the synthetic method of any one of claims 1-6.
8. A lithium ion capacitor comprises a positive electrode, a negative electrode, a diaphragm and electrolyte; the method is characterized in that: the negative electrode comprises the garnet-like silicon oxide-nitrogen-doped carbon composite material of claim 7 or the garnet-like silicon oxide-nitrogen-doped carbon composite material prepared by the synthesis method of any one of claims 1 to 6.
9. The lithium ion capacitor of claim 8, wherein: the preparation method of the negative electrode comprises the following steps: uniformly mixing the garnet-like silicon oxide-nitrogen doped carbon composite material, the conductive carbon black and the adhesive according to a certain mass ratio, adding NMP (N-methyl pyrrolidone) to mix the materials and form uniform slurry, coating the uniform slurry on a copper foil, and drying and rolling the uniform slurry.
10. The lithium ion capacitor of claim 9, wherein: the mass ratio of the garnet-like silicon oxide-nitrogen doped carbon composite material, the conductive carbon black and the adhesive is 9:0.6:0.4.
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