CN110048101B - Silicon-oxygen-carbon microsphere composite negative electrode material and preparation method and application thereof - Google Patents
Silicon-oxygen-carbon microsphere composite negative electrode material and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a silicon-oxygen-carbon microsphere composite negative electrode material and a preparation method and application thereof. The silicon-oxygen-carbon microsphere is of a core-shell structure, and the diameter of the silicon-oxygen-carbon microsphere is 200-300 nm. The preparation method comprises the following steps: adding an ethanol solution of silane into a mixed solution of ethanol, deionized water and ammonia water, and stirring; adding resorcinol and formaldehyde into the mixed solution and stirring; then transferring the mixture into a high-pressure reaction kettle for reaction; cooling to room temperature, washing with ethanol and deionized water after centrifugal separation, and then drying in vacuum to obtain a silicon dioxide/phenolic resin composite material; and (3) carrying out high-temperature heat treatment on the silicon dioxide/phenolic resin composite material to obtain the silicon-oxygen-carbon microsphere composite negative electrode material. The silicon-oxygen-carbon microsphere composite negative electrode material is applied to a lithium ion battery, can improve the first coulombic efficiency and the cycle life of the lithium battery, is simple in process, good in reproducibility and easy to implement, and is suitable for large-scale production.
Description
Technical Field
The invention relates to the technical field of lithium ion battery cathode materials, in particular to a silicon-oxygen-carbon microsphere composite cathode material and a preparation method thereof.
Background
In recent years, with the continuous development of lithium ion battery technology, the lithium ion battery plays an increasingly important role in the fields of military, aerospace, civil use and the like, is widely applied in the fields of electronic equipment, power automobiles, static energy storage and the like, and the demand of the lithium ion battery is rapidly increased. Particularly, under the encouragement of the national policy for vigorously developing new energy electric vehicles, the market of the lithium ion battery enters a rapid development channel, and simultaneously, along with the rapid development of the new energy electric vehicles, the energy density of the power lithium ion battery must be greatly improved. The cathode material, as an important component of the lithium ion battery, determines the performance and safety of the lithium ion battery. The capacity of the most widely applied graphite carbon negative electrode material in the current market is close to the theoretical capacity 372mAh/g, the promotion space is very limited, and the low capacity density seriously inhibits the wide application of the lithium ion battery.
The silicon-based negative electrode material is considered to be a negative electrode material with great application prospect in next generation lithium ion batteries due to the advantages of high specific capacity (4200 mAh/g), low lithium removal potential and the like. However, the high production cost of silicon negative electrode materials and the large volume change (over 300%) during the lithium extraction process lead to pulverization, shedding and capacity fading of silicon particles; the continuous growth of Solid Electrolyte Interface (SEI) films on the surface of silicon particles limits their widespread use as negative electrode materials due to irreversible consumption of electrolyte and lithium source from the positive electrode. On the other hand, oxides of silicon, e.g. Silica (SiO) x ) Compared with crystalline silicon nanoparticles, the method has more advantages, such as high theoretical capacity (more than 1500 mAh/g); has small volume change in the charge-discharge process, and can generate silicon and Li in the charge-discharge process 2 O and Li 4 Si 4 O 4 . The in-situ generated silicon is uniformly dispersed in Li 2 O and Li 4 Si 4 O 4 In the matrix, the volume expansion in the process of Si lithium intercalation and deintercalation can be buffered to a certain degree, the agglomeration of Si particles can be prevented, the volume change of the silicon lithium alloy can be buffered, and the like. Currently Silica (SiO) x ) The anode material is a new generation of high-capacity silicon-based anode material which is considered to be most promising to be industrialized in the industry. Despite SiO x These advantages exist, but SiO x The low conductivity and the first coulombic efficiency and the non-negligible volume change limit the wide application of the material as a negative electrode material in the field of power lithium batteries. In addition, the commercial silica production conditions that are widely used at present are severe, making it relatively expensive.
Aiming at the problems of the silicon oxide (SiOx) negative electrode material, the current main modification method is to prepare a silicon oxide/carbon composite material by adopting methods such as ball milling, chemical vapor deposition and the like; however, the method is complex in process, and the cycle performance and the first coulombic efficiency of the material are not high enough.
Disclosure of Invention
In view of the above problems, an object of the present invention is to provide a silicon-oxygen-carbon microsphere composite anode material.
In order to achieve the purpose of the invention, the technical scheme adopted by the invention is as follows:
a silicon-oxygen-carbon microsphere composite negative electrode material is prepared from silane, resorcinol, formaldehyde, ethanol, ammonia water and deionized water; the diameter of the silicon-oxygen-carbon microsphere is 200-300 nm, the structure of the microsphere is a silica inner core-carbon shell, and the thickness of the carbon shell is 20-80nm.
Preferably, the silane is one or a mixture of more than two of tetra (2-methoxyethoxy) silane, tetramethoxysilane and tetraethoxysilane.
The invention also aims to provide a preparation method of the silicon-oxygen-carbon microsphere composite negative electrode material. The specific technical scheme is as follows:
the preparation method of the silicon-oxygen-carbon microsphere composite negative electrode material comprises the following steps:
(1) Adding silane into ethanol, and stirring until the silane is completely dissolved, wherein the concentration of the silane in the ethanol is 0.05-0.1 g/L, so as to obtain a solution A;
(2) Mixing ethanol, deionized water and ammonia water with the concentration of 25-28% according to the volume ratio of 1.5-3;
(3) Adding the solution A obtained in the step (1) into the solution B obtained in the step (2) according to the volume ratio of 1;
(4) Adding resorcinol and formaldehyde with the concentration of 36-38 wt% into the solution C obtained in the step (3) and stirring for 24-36 hours, wherein the concentration of the resorcinol in the solution C is 6.25-17.5 g/L, and the mass ratio of the resorcinol to the formaldehyde is 2.05-2.82: 1; then transferring the mixture into a high-pressure reaction kettle and keeping the temperature at 90-110 ℃ for 20-30 hours; then cooling to room temperature, carrying out centrifugal separation at the rotating speed of 5000-8000 r/min, washing the obtained precipitate with ethanol and deionized water for 2-3 times in sequence, and then carrying out vacuum drying at the temperature of 70-90 ℃ for 20-30 hours to obtain the silicon dioxide/phenolic resin composite material;
(5) And (3) placing the silicon dioxide/phenolic resin composite material in the step (4) into a tubular furnace, introducing nitrogen or argon or nitrogen-argon mixed gas in any proportion into the tubular furnace, heating to 800-1100 ℃ at the speed of 2-5 ℃/min under the protection of atmosphere, keeping for 3-5 hours, and naturally cooling to room temperature to obtain the silicon-oxygen-carbon microsphere composite negative electrode material.
The invention also aims to provide application of the silicon-oxygen-carbon microsphere composite negative electrode material. The specific technical scheme is as follows:
the silicon-oxygen-carbon microsphere composite negative electrode material is applied to a negative electrode of a lithium ion battery.
Preferably, the method is specifically applied to CR2032 button lithium ion batteries and comprises the following steps:
(A) Uniformly mixing a silicon-oxygen-carbon microsphere composite negative electrode material, a conductive agent Super P and a binder polyvinylidene fluoride according to a mass ratio of 7;
(B) Mixing the solid mixture obtained in the step (A) with N-methyl pyrrolidone, wherein the solid mixture accounts for 18-25 wt%, and uniformly stirring to obtain slurry;
(C) Coating the slurry obtained in the step (B) on copper foil, drying and rolling to obtain a lithium ion battery electrode plate with the thickness of 13-23 mu m;
(D) Taking the electrode plate of the lithium ion battery obtained in the step (C) as an electrode negative plate, taking a lithium plate as an electrode positive plate, adopting a microporous polypropylene membrane as a diaphragm, and adopting 1mol/L LiPF 6 And the solvent is electrolyte, and the CR2032 button type lithium ion battery is assembled in a glove box filled with argon.
Preferably, the solvent in step (D) is a mixture of equal volumes of dimethyl carbonate and dipropyl carbonate.
The invention has the advantages and beneficial effects that:
the silicon-oxygen-carbon microspheres prepared by the invention are used as the lithium ion battery cathode material, and the carbon can relieve the volume change of the silicon oxide cathode material in the charging and discharging processes, and is beneficial to improving the conductivity of the material so as to improve the rate capability, so that the first coulombic efficiency (reaching about 80%) and the cycle life (the capacity retention rate exceeds 86% after 100 cycles) of the lithium battery are improved, the process is simple, the reproducibility is good, the implementation is easy, and the silicon-oxygen-carbon microspheres are suitable for large-scale production. Can be applied to CR2032 button lithium ion batteries and other lithium ion batteries.
Drawings
FIG. 1 shows XRD of a silicon-oxygen-carbon (SiOx/C) microsphere composite anode material prepared in example 1 of the present invention.
FIG. 2 is a scanning electron microscope image of the silica-carbon microsphere composite anode material prepared in example 1 of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Example 1
A preparation method of a silicon-oxygen-carbon microsphere composite negative electrode material comprises the following specific steps:
(1) Adding 3.0mg of tetraethoxysilane into 30mL of ethanol, and stirring until the tetraethoxysilane is completely dissolved to obtain a solution A;
(2) Mixing and uniformly stirring 20mL of ethanol, 12mL of deionized water and 8mL of ammonia water (36-38 wt%) to obtain a solution B;
(3) Adding the solution A obtained in the step (1) into the solution B obtained in the step (2) according to the volume ratio of 1;
(4) Adding 1.04g of resorcinol and 1.69mL of formaldehyde (mass fraction: 36-38%; density: 0.82 g/mL) into the solution C obtained in the step (3), stirring for 24-36 hours, and then transferring into a high-pressure reaction kettle at 100 ℃ for 20 hours; then cooling to room temperature, and carrying out centrifugal separation at the rotating speed of 5000 r/min; then washing the obtained precipitate with ethanol and deionized water for 3 times, and then drying in vacuum at 70 ℃ for 20 hours to obtain a silicon dioxide/phenolic resin composite material;
(5) And (3) placing the silicon dioxide/phenolic resin composite material in the step (4) into a tubular furnace, introducing nitrogen into the tubular furnace, heating to 1100 ℃ at the speed of 2 ℃/min under the protection of atmosphere, keeping for 3 hours, and naturally cooling to room temperature to obtain the silicon-oxygen-carbon microsphere composite negative electrode material. The diameter of the obtained microsphere is about 250nm, the microsphere has a core-shell structure of a silica inner core-carbon shell, and the thickness of the carbon shell is about 20-50 nm, as shown in figure 1.
(6) Assembling and testing the performance of the lithium ion battery, namely uniformly mixing the silicon-oxygen-carbon microsphere composite negative electrode material, the conductive agent Super P and the adhesive polyvinylidene fluoride according to the mass ratio of 70; and then according to the mass ratio of 20:80, mixing the uniformly mixed solid mixture (a mixture of a silicon-oxygen-carbon microsphere composite negative electrode material, super P and polyvinylidene fluoride) with N-methyl pyrrolidone, and uniformly stirring to prepare slurry; and then coating the slurry on copper foil, and drying and rolling to obtain the lithium ion battery electrode negative plate with the thickness of 13-23 mu m. Then, a lithium plate is used as an electrode positive plate, a microporous polypropylene film is used as a diaphragm, and 1mol/L LiPF 6 (the solvent is dimethyl carbonate and dipropyl carbonate with equal volume) as electrolyte, and the electrode negative plate is assembled into a CR2032 button type lithium ion battery in a glove box filled with argon. And (3) after the lithium ion battery is kept stand for 24 hours, respectively carrying out charge and discharge tests under the current of 0.1C, wherein the charge and discharge voltage is between 0.01 and 3.0V.
The lithium battery performance results of this example are shown in table 1.
Example 2
(1) Adding 1.54mg of tetramethoxysilane into 30mL of ethanol, and stirring until the tetramethoxysilane is completely dissolved to obtain a solution A;
(2) Mixing and uniformly stirring 20mL of ethanol, 12mL of deionized water and 8mL of ammonia water (36-38 wt%) to obtain a solution B;
(3) Adding the solution A obtained in the step (1) into the solution B obtained in the step (2) according to the volume ratio of 1;
(4) Adding 0.39g of resorcinol and 0.58mL of formaldehyde (mass fraction: 36-38%; density: 0.82 g/mL) into the solution C obtained in step (3), stirring for 24-36 hours, and then transferring into a high-pressure reaction kettle to keep at 100 ℃ for 20 hours; then cooling to room temperature, and carrying out centrifugal separation at the rotating speed of 5000 r/min; then washing the obtained precipitate with ethanol and deionized water for 3 times, and then drying in vacuum at 70 ℃ for 20 hours to obtain a silicon dioxide/phenolic resin composite material;
(5) And (3) placing the silicon dioxide/phenolic resin composite material in the step (4) into a tubular furnace, introducing nitrogen into the tubular furnace, heating to 1000 ℃ at the speed of 2 ℃/min under the protection of atmosphere, keeping for 3 hours, and naturally cooling to room temperature to obtain the silicon-oxygen-carbon microsphere composite negative electrode material.
(6) Assembling and testing the lithium ion battery, namely uniformly mixing a silicon-oxygen-carbon microsphere composite negative electrode material, a conductive agent Super P and a binding agent polyvinylidene fluoride according to the mass ratio of 70; and then according to the mass ratio of 20:80 mixing the uniformly mixed solid mixture (a mixture of a silica-carbon microsphere composite negative electrode material, super P and polyvinylidene fluoride) with N-methylpyrrolidone, and uniformly stirring to prepare slurry; and then coating the slurry on copper foil, and drying and rolling to obtain the lithium ion battery electrode negative plate with the thickness of 13-23 mu m. Then, a lithium plate is used as an electrode positive plate, a microporous polypropylene film is used as a diaphragm, and 1mol/L LiPF 6 (the solvent is dimethyl carbonate and dipropyl carbonate with equal volume) as electrolyte, and the electrode negative plate is assembled into a CR2032 button type lithium ion battery in a glove box filled with argon. And (3) after the lithium ion battery is kept stand for 24 hours, respectively carrying out charge and discharge tests under the current of 0.1C, wherein the charge and discharge voltage is between 0.01 and 3.0V.
The lithium battery performance results of this example are shown in table 1.
Example 3
(1) Adding 2.1mg of tetra (2-methoxyethoxy) silane into 30mL of ethanol, and stirring until the silane is completely dissolved to obtain a solution A;
(2) Mixing and uniformly stirring 20mL of ethanol, 12mL of deionized water and 8mL of ammonia water (36-38 wt%) to obtain a solution B;
(3) Adding the solution A obtained in the step (1) into the solution B obtained in the step (2) according to the volume ratio of 1;
(4) Adding 0.62g of resorcinol and 0.72mL of formaldehyde (mass fraction: 36-38%; density: 0.82 g/mL) into the solution C obtained in the step (3), stirring for 24-36 hours, and then transferring into a high-pressure reaction kettle at 100 ℃ and keeping for 20 hours; then cooling to room temperature, and carrying out centrifugal separation at the rotating speed of 5000 r/min; then washing the obtained precipitate with ethanol and deionized water for 3 times in sequence, and then drying the precipitate for 20 hours in vacuum at the temperature of 70 ℃ to obtain a silicon dioxide/phenolic resin composite material;
(5) And (5) placing the silicon dioxide/phenolic resin composite material in the step (4) into a tubular furnace, introducing nitrogen into the tubular furnace, heating to 800 ℃ at a speed of 2 ℃/min under the atmosphere protection, keeping for 3 hours, and naturally cooling to room temperature to obtain the silicon-oxygen-carbon microsphere composite negative electrode material.
(6) Assembling and testing the lithium ion battery, namely uniformly mixing a silicon-oxygen-carbon microsphere composite negative electrode material, a conductive agent Super P and a binding agent polyvinylidene fluoride according to the mass ratio of 70; and then according to the mass ratio of 20:80 mixing the uniformly mixed solid mixture (a mixture of a silica-carbon microsphere composite negative electrode material, super P and polyvinylidene fluoride) with N-methylpyrrolidone, and uniformly stirring to prepare slurry; and then coating the slurry on a copper foil, and drying and rolling to obtain the lithium ion battery electrode negative plate with the thickness of 13-23 mu m. Then, a lithium plate is used as an electrode positive plate, a microporous polypropylene film is used as a diaphragm, and 1mol/L LiPF 6 And (the solvent is dimethyl carbonate and dipropyl carbonate with the same volume) as the electrolyte, and the electrode negative plate is assembled into the CR2032 button lithium ion battery in a glove box filled with argon. And (3) after the lithium ion battery is kept stand for 24 hours, respectively carrying out charge and discharge tests under the current of 0.1C, wherein the charge and discharge voltage is between 0.01 and 3.0V.
The lithium battery performance results of this example are shown in table 1.
Table 1 shows the capacities obtained in the first and 100 th cycles of the charge and discharge test of the lithium ion batteries of examples 1 to 3 at a current of 0.1C.
TABLE 1
As can be seen from table 1, when the silicon-oxygen-carbon microspheres of the invention are used as an electrode negative electrode material and applied to a lithium ion battery, the charging capacity is more than 896mAh/g after 100 cycles of circulation, the capacity retention rate is more than 86%, the silicon-oxygen-carbon microspheres have good circulation performance, and are still far higher than the current commercialized graphite negative electrode material.
The foregoing is only a preferred embodiment of the present invention. The present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof, and it is therefore intended that all such equivalent changes and modifications as would be obvious to one skilled in the art be included herein are deemed to be within the scope and spirit of the present invention as defined by the appended claims.
Claims (1)
1. An application method of a silica-carbon microsphere composite cathode material is characterized in that the silica-carbon microsphere is a silica core-carbon shell structure, the diameter of the silica-carbon microsphere is 200-300 nm, and the thickness of the carbon shell is 20-80nm; the silicon-oxygen-carbon microsphere is prepared from silane, resorcinol, formaldehyde, ethanol, ammonia water and deionized water; and is prepared by the following steps:
(1) Adding silane into ethanol, and stirring until the silane is completely dissolved, wherein the concentration of the silane in the ethanol is 0.05-0.1 g/L, so as to obtain a solution A; the silane is one or a mixture of more than one of tetra (2-methoxyethoxy) silane, tetramethoxysilane and tetraethoxysilane in any mass ratio;
(2) Mixing ethanol, deionized water and 25-28% ammonia water according to a volume ratio of 1.5-3;
(3) Adding the solution A obtained in the step (1) into the solution B obtained in the step (2) according to the volume ratio of 1;
(4) Adding resorcinol and formaldehyde with the concentration of 36-38 wt% into the solution C obtained in the step (3) and stirring for 24-36 hours, wherein the concentration of the resorcinol in the solution C is 6.25-17.5 g/L, and the mass ratio of the resorcinol to the formaldehyde is 2.05-2.82: 1; then transferring the mixture into a high-pressure reaction kettle and keeping the temperature at 90-110 ℃ for 20-30 hours; then cooling to room temperature, carrying out centrifugal separation at the rotating speed of 5000-8000 r/min, washing the obtained precipitate with ethanol and deionized water for 2-3 times in sequence, and then carrying out vacuum drying at the temperature of 70-90 ℃ for 20-30 hours to obtain the silicon dioxide/phenolic resin composite material;
(5) Placing the silicon dioxide/phenolic resin composite material in the step (4) into a tubular furnace, introducing nitrogen or argon or nitrogen-argon mixed gas in any proportion into the tubular furnace, heating to 800-1100 ℃ at the speed of 2-5 ℃/min under the protection of atmosphere, keeping for 3-5 hours, and then naturally cooling to room temperature to obtain the silicon-oxygen-carbon microsphere composite negative electrode material;
the method and the steps applied to the CR2032 button lithium ion battery are as follows:
(A) Uniformly mixing a silicon-oxygen-carbon microsphere composite negative electrode material, a conductive agent SuperP and a binder polyvinylidene fluoride according to a mass ratio of 7;
(B) Mixing the solid mixture obtained in the step (A) with N-methylpyrrolidone, wherein the solid mixture accounts for 18-25 wt%, and uniformly stirring to obtain slurry;
(C) Coating the slurry obtained in the step (B) on copper foil, drying and rolling to obtain an electrode plate of the lithium ion battery with the thickness of 13-23 mu m;
(D) Taking the electrode plate of the lithium ion battery obtained in the step (C) as an electrode negative plate, taking a lithium plate as an electrode positive plate, adopting a microporous polypropylene membrane as a diaphragm, and adopting 1mol/L LiPF 6 And the solvent is electrolyte, and the electrolyte is assembled into a CR2032 button type lithium ion battery in a glove box filled with argon; the solvent is a mixture of equal volumes of dimethyl carbonate and dipropyl carbonate.
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| CN110756177B (en) * | 2019-10-24 | 2022-08-30 | 齐鲁工业大学 | Preparation method and application of functionalized nano silicon dioxide/resorcinol-formaldehyde microspheres |
| CN111509212B (en) * | 2020-04-30 | 2022-07-01 | 厦门高容纳米新材料科技有限公司 | Silicon-carbon composite negative electrode material, negative electrode plate, preparation method of negative electrode plate and lithium ion battery |
| CN111600005B (en) * | 2020-06-16 | 2022-04-22 | 广西师范大学 | Preparation method of lithium ion battery negative electrode material porous Si/C composite material |
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| CN112652758B (en) * | 2020-12-14 | 2022-06-17 | 云帆(镇江)新能源材料有限公司 | Silicon oxide/carbon microsphere composite negative electrode material for lithium ion battery and preparation method thereof |
| CN113213493B (en) * | 2021-04-13 | 2023-05-26 | 武汉纽赛儿科技股份有限公司 | Granati-shaped silicon oxide-nitrogen doped carbon composite material, synthesis method thereof and lithium ion capacitor |
| CN113611864A (en) * | 2021-07-30 | 2021-11-05 | 江苏泛亚微透科技股份有限公司 | Carbon aerogel coated silica hollow microsphere negative electrode material |
| CN113921783A (en) * | 2021-09-27 | 2022-01-11 | 天津市捷威动力工业有限公司 | Long-cycle high-rate silicon-carbon negative electrode material and preparation method thereof |
| CN114122370B (en) * | 2021-10-29 | 2023-12-19 | 西安交通大学 | Porous carbon double bond modified silane deposition-induced negative electrode material and preparation method and application thereof |
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| CN108598395A (en) * | 2018-03-30 | 2018-09-28 | 武汉理工大学 | The magnanimity preparation method of monodisperse silica/nitrogen-doped carbon composite Nano ball or microballoon |
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