CN109524627B - SiOx negative electrode material with controllable oxygen content, preparation method and lithium ion battery - Google Patents
SiOx negative electrode material with controllable oxygen content, preparation method and lithium ion battery Download PDFInfo
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- CN109524627B CN109524627B CN201710840080.5A CN201710840080A CN109524627B CN 109524627 B CN109524627 B CN 109524627B CN 201710840080 A CN201710840080 A CN 201710840080A CN 109524627 B CN109524627 B CN 109524627B
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Abstract
The invention relates to the technical field of lithium ion batteries, in particular to a SiOx negative electrode material with controllable oxygen content, a preparation method thereof and a lithium ion battery, which is characterized by comprising the following processing steps: carrying out solid phase ball milling to obtain powder of amorphous silicon and amorphous silicon dioxide which are uniformly contacted; kneading; preliminary carbonization and crushing; surface modification; and (5) hydrogen protection heat treatment. Compared with the prior art, the prepared SiOx negative electrode material contains partially crystallized SiOx grains and a uniform buffer structure in the grains; controllable oxygen content, good conductivity and effective synthesis means; the obtained SiOx material has the characteristics of high specific capacity (more than 1400mAh/g), high first charge-discharge efficiency (more than 78%), high production efficiency, low cost and convenience for industrial production; the method is suitable for batch preparation of the high-capacity lithium ion battery cathode material.
Description
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to a SiOx negative electrode material with controllable oxygen content, a preparation method thereof and a lithium ion battery.
Background
The novel high-capacity power battery cathode material can be developed and researched to solve the problem of short endurance mileage of the conventional Electric Vehicle (EV), and is favorable for further popularization of new energy vehicles. Since Si has a high theoretical lithium intercalation capacity (about 4200mAh/g) and a moderate lithium intercalation/deintercalation potential, research on Si as a lithium storage matrix has become a hot spot for developing a negative electrode material. The major problems of powdered silicon currently used as an electrode active material are its poor conductivity and severe volume effects, resulting in poor charge and discharge stability.
In order to improve the first efficiency and cycle characteristics of the silicon material when used as a negative electrode, it is necessary to optimize parameters such as the crystal form, particle size, formulation, and surface properties of silicon.
Scientific article "A high tap density secondary silicon particulate boiler fabric flexible for lithium-ion batteries (Energy)& Environmental Science 2015, 8, 2371) "describes the obtaining of nano Si outer coated SiO by hydrolysis of tetraethyl orthosilicate (TEOS) in solvent2And then, the anode material is obtained by profiling, crushing and coating. Although Si and SiO are obtained by the method2The composite material needs to obtain a silicon raw material with the particle size less than 100nm, hydrolysis of TEOS and agglomeration control of nano silicon are challenging during batch and uniform preparation, silicon particles are easy to agglomerate in a high-pressure forming process, and finally carbon coating relates to polymerization reaction of phenol and formaldehyde polymerization under the regulation and control of hexadecyl trimethyl ammonium bromide. The oxygen content in the obtained cathode material is uncertain, the cost and the process requirement of the whole set of method are extremely high, and the industrial production is difficult to carry out.
Compared with crystalline silicon, amorphous silicon has smaller volume change in the charge and discharge process (Nano Lett.2013, 13, 758-. The first charging specific capacity is 1137mAh/g and the first efficiency is 74 percent through the button cell test. Although the amorphous silicon cathode material can be obtained by the method, the obtained structure is that the monocrystalline silicon is embedded in the amorphous silicon matrix, so that the huge volume expansion effect of the silicon material is still difficult to solve, the first-time efficiency is low, and meanwhile, the preparation method comprises an etching process and is high in cost.
Scientific article "Investigation of the interactive mechanism and the interactive trigger on SiO inorganic material for lithium-ion battery (Journal of the Ceramic Society of Japan 119[11]855 Amplified 8602011) "proved to be in contact with crystalline SiO2The difference in comparison is that amorphous SiO2Can react with lithium ions during charging and discharging. In Si and SiO2In a composite system of (A), SiO2Li formed by reaction with lithium4SiO4Can be used as a buffer material to improve the cycle of the silicon cathode. SiO 22The content of (a) directly determines the oxygen content and the overall electrochemical performance of the material, which is of great significance for downstream applications. The prior method can not effectively regulate and control SiOx materials, so that the prior method is urgently needed to be suitable for large-scale productionThe preparation method can adjust and control the oxygen content.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a preparation method of a SiOx negative electrode material, which has controllable oxygen content and stable performance and is easy to industrialize.
In order to achieve the purpose, the preparation method of the SiOx negative electrode material for the lithium ion battery with controllable oxygen content is designed, and is characterized by comprising the following processing steps:
step one, solid phase ball milling: putting amorphous silicon with the average particle size of 1-20 mu m and the purity of more than 99.9 percent, amorphous silicon dioxide with the average particle size of 1-20 mu m and the purity of more than 99.9 percent and cyclohexane into a high-speed ball mill for ball milling until the average particle size is 0.5-2 mu m, and drying to obtain powder material in which the amorphous silicon and the amorphous silicon are in uniform contact; the weight ratio of the amorphous silicon to the amorphous silicon dioxide is 5: 1-1: 1;
step two, kneading: adding the ball-milled powder and the binder into a kneading machine, uniformly mixing, and heating and extruding at 50-200 ℃ to obtain a block; the binder accounts for 3-15% of the weight of the powder after ball milling;
step three, preliminary carbonization and crushing: primarily carbonizing the obtained block at 500-600 ℃ for 5-10 hours, and then crushing to carbonized powder of 3-10 mu m;
step four, surface modification: putting the pulverized carbonized powder with the particle size of 3-10 microns and asphalt into a stirring type heating kettle for fully mixing, wherein the added asphalt accounts for 1-10 wt% of the mixture, heating to 400-650 ℃ for reaction for 1-10 h to soften and decompose the asphalt, cooling to room temperature, discharging, sieving, and selecting a screen mesh with the particle size of 250-500 meshes;
step five, hydrogen protection heat treatment: and (3) carbonizing the modified and sieved discharged material in an atmosphere furnace at 700-1050 ℃ for 1-6 h, wherein the protective atmosphere selected during carbonization is any one of helium, argon or nitrogen, and the SiOx negative electrode material is obtained, wherein x is a real number of 0-2.
The cyclohexane in the first step accounts for 3-20% of the total weight of the amorphous silicon and the amorphous silicon dioxide.
In the step one, the ball milling time is 1-10 h.
And the binder in the step two is one or more of kerosene asphalt, petroleum asphalt, coumarone resin, epoxy resin, phenolic resin, acrylic resin and furfural resin.
And in the second step, the kneading temperature is 50-200 ℃, the kneading time is 1-10 h, and after the kneading, the shape of the obtained pressed product is a cylinder or a square block.
In the third step, the preliminary carbonization is carried out in a box type furnace for 1-6 h at 400-650 ℃; the protective atmosphere in the box type furnace during the primary carbonization is any one of helium, argon or nitrogen.
In the third step, the pulverization adopts one or a combination of a plurality of air flow pulverizer, mechanical mill and roller pair.
In the fourth step, the asphalt is one or more of kerosene and petroleum asphalt.
The SiOx negative electrode material is of a core-shell structure, the surface layer of the SiOx negative electrode material is composed of an amorphous conductive carbon layer, the core is formed by embedding a plurality of monocrystalline silicon crystal nuclei in an amorphous silicon dioxide structure, and a part of carbon buffer layers and a small number of microporous structures are arranged between silicon active ingredients.
The lithium ion battery containing the SiOx negative electrode material.
Compared with the prior art, the prepared SiOx negative electrode material contains partially crystallized SiOx grains and a uniform buffer structure in the grains; controllable oxygen content, good conductivity and effective synthesis means; the obtained SiOx material has the characteristics of high specific capacity (more than 1400mAh/g), high first charge-discharge efficiency (more than 78%), high production efficiency, low cost and convenience for industrial production; the method is suitable for batch preparation of the high-capacity lithium ion battery cathode material.
Drawings
FIG. 1 is an XRD pattern of a sample obtained in example 1 of the present invention.
FIG. 2 is a SEM photograph of a sample obtained in example 1 of the present invention.
FIG. 3 is a charging/discharging curve of the sample obtained in example 1 of the present invention.
FIG. 4 is a charging/discharging curve of the sample obtained in example 2 of the present invention.
Detailed Description
The following specific examples describe the present invention in detail, however, the present invention is not limited to the following examples.
The kneading device in the present invention is any of a high-speed kneader, a pressure kneader or a continuous kneader.
The heating kettle can adopt a vertical cone shape, and the interior of the heating kettle contains three layers of scrapers.
Example 1
According to the mol ratio of Si to SiO22.0kg of amorphous silicon (purity > 99.9%) with a particle size (D50) of 3 μm, 4.284kg of amorphous silica (purity > 99.9%) with a particle size (D50) of 5 μm and 600ml of cyclohexane are put into a high-speed ball mill to be ball-milled to a particle size of 1 μm, and the mixture is transferred into an air-blast drying oven to be dried for 10 hours at 80 ℃;
and putting the ball-milled materials and the ball-milled material binder into a high-speed kneading machine, uniformly mixing, mixing at 150 ℃ for 2h, and performing extrusion forming.
The block obtained after extrusion molding was preliminarily carbonized at 550 degrees for 10 hours, and then pulverized with air until D50 becomes 4 μm.
And putting the crushed powder and asphalt into a conical stirring type heating kettle, fully mixing, heating to 700 ℃, reacting for 10 hours to soften and decompose the asphalt, then cooling to room temperature, and sieving with a 350-mesh sieve. Wherein the asphalt comprises 5 wt% of the mixture.
After the material is discharged after being modified and sieved, the obtained material is heated to 1050 ℃ at the speed of 2 ℃/min under the nitrogen protection atmosphere, and the temperature is kept for 2h and then is naturally cooled. XRD and SEM results of the prepared material are shown in figures 1 and 2.
Example 2
According to the mol ratio of Si to SiO2Amorphous silicon (purity > 99.9%) 3.0kg with a particle size (D50) of 3 μm, amorphous silica (> 99.9%) 3.214g with a particle size (D50) of 5 μm, and 150ml of cyclohexane were put into a high-speed ball mill and ball-milled to a particle size of 2 μm, and the mixture was transferred to an air-blast drying oven and dried at 80 degrees for 10 hours at 2: 1.
And putting the ball-milled materials and a binder accounting for 7 wt% of the ball-milled materials into a high-speed kneading machine, uniformly mixing, mixing at 110 ℃ for 5 hours, and performing extrusion forming.
After extrusion forming, the obtained block is carbonized primarily for 10 hours at 550 ℃, and then treated by air flow powder until D50 is 4 μm.
And putting the crushed powder and asphalt into a conical stirring type heating kettle, fully mixing, heating to 700 ℃, reacting for 10 hours to soften and decompose the asphalt, then cooling to room temperature, and sieving with a 350-mesh sieve. Wherein the asphalt comprises 5 wt% of the mixture.
And (4) carbonizing the modified and sieved material in an atmosphere furnace at 1050 ℃ for 5 hours.
The final silicon-carbon composite materials obtained in the embodiments 1 and 2 are respectively used as the negative active materials of the button lithium ion battery, and the preparation steps are as follows:
1. mixing and stirring according to the ratio of active substance, conductive agent, CMC and SBR (80: 10: 5), and stirring to obtain thick paste;
2. coating the slurry on a copper foil to manufacture a pole piece, rolling after coating, and then baking at 120 ℃ for 4 hours;
3. assembling the battery: the button cell is assembled by adding electrolyte into the lithium sheet as the negative electrode and the polypropylene as the diaphragm.
And evaluating the electrochemical performance of the material by adopting an Aribin test cabinet, wherein the voltage range is 0.01-1.5V, and the multiplying power is 0.1C. The button charge and discharge curves of the materials obtained in examples 1 and 2 are shown in FIGS. 3 and 4. Table 1 shows the results of the sample-making electrification tests obtained in examples 1 and 2.
Table 1. oxygen content and electrification test results for samples obtained in examples 1 and 2.
The oxygen content (a) in the table indicates the oxygen content in the sample obtained by the Leco ON836 test.
Claims (9)
1. The SiOx negative electrode material is characterized in that the preparation method comprises the following processing steps:
step one, solid phase ball milling: putting amorphous silicon with the average particle size of 1-20 mu m and the purity of more than 99.9 percent, amorphous silicon dioxide with the average particle size of 1-20 mu m and the purity of more than 99.9 percent and cyclohexane into a high-speed ball mill for ball milling until the average particle size is 0.5-2 mu m, and drying to obtain powder material in which the amorphous silicon and the amorphous silicon are in uniform contact; the amorphous silicon: the weight ratio of the amorphous silica is 5: 1-1: 1;
step two, kneading: adding the ball-milled powder and the binder into a kneading machine, uniformly mixing, and heating and extruding at 50-200 ℃ to obtain a block; the binder accounts for 3-15% of the weight of the powder after ball milling;
step three, preliminary carbonization and crushing: primarily carbonizing the obtained block body at 500-600 ℃ for 5-10 hours, and then crushing the block body into carbonized powder with the particle size of 3-10 microns;
step four, surface modification: putting the pulverized carbonized powder with the particle size of 3-10 microns and asphalt into a stirring type heating kettle for fully mixing, wherein the added asphalt accounts for 1-10 wt% of the mixture, heating to 400-650 ℃ for reaction for 1-10 h to soften and decompose the asphalt, cooling to room temperature, discharging, sieving, and selecting a screen mesh with the particle size of 250-500 meshes;
step five, hydrogen protection heat treatment: carbonizing the modified and sieved material in an atmosphere furnace at 700-1050 ℃ for 1-6 h, wherein the protective atmosphere selected during carbonization is any one of helium, argon or nitrogen, and the SiOx negative electrode material is obtained, wherein x is a real number of 0-2;
the SiOx negative electrode material is of a core-shell structure, the surface layer of the SiOx negative electrode material is composed of an amorphous conductive carbon layer, the core is formed by embedding a plurality of monocrystalline silicon crystal nuclei in an amorphous silicon dioxide structure, and a part of carbon buffer layers and a small number of microporous structures are arranged between silicon active ingredients.
2. The SiOx negative electrode material according to claim 1, wherein cyclohexane is present in an amount of 3 to 20% by weight based on the total weight of amorphous silicon and amorphous silicon dioxide in step one.
3. The SiOx negative electrode material according to claim 1, wherein said ball milling time in step one is 1 to 10 hours.
4. The SiOx negative electrode material of claim 1, wherein the binder in the second step is one or more of kerosene pitch, petroleum pitch, coumarone resin, epoxy resin, phenol resin, acrylic resin, and furfural resin.
5. The SiOx negative electrode material according to claim 1, wherein said kneading temperature in step two is 50-200 ℃ and kneading time is 1-10 hours, and after kneading, the shape of the obtained compact is cylindrical or cubic.
6. The SiOx negative electrode material according to claim 1, wherein said preliminary carbonization in step three is carried out in a box furnace at 550 ℃ for 10 hours; the protective atmosphere in the box type furnace during the primary carbonization is any one of helium, argon or nitrogen.
7. The SiOx negative electrode material according to claim 1, wherein said pulverization in step three is carried out by one or more of jet mill, mechanical mill, and roll-to-roll method.
8. The SiOx negative electrode material according to claim 1, wherein said pitch in step four is one or more selected from kerosene and petroleum pitch.
9. A lithium ion battery containing the SiOx negative electrode material according to any one of claims 1 to 8.
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007016293A (en) * | 2005-07-08 | 2007-01-25 | Kyoto Univ | Method for producing metal by suspension electrolysis |
| EP2595222A1 (en) * | 2011-11-15 | 2013-05-22 | Shin-Etsu Chemical Co., Ltd. | Non-aqueous electrolyte secondary battery |
| CN103187556A (en) * | 2011-12-27 | 2013-07-03 | 宁波杉杉新材料科技有限公司 | Lithium ion battery and anode material thereof, preparation method |
| CN103474636A (en) * | 2013-09-18 | 2013-12-25 | 上海交通大学 | Silicon-based lithium ion battery negative electrode material and preparation method thereof |
| US8796121B1 (en) * | 2013-11-19 | 2014-08-05 | Translucent, Inc. | Stress mitigating amorphous SiO2 interlayer |
| CN104701509A (en) * | 2013-12-06 | 2015-06-10 | 奇瑞汽车股份有限公司 | Lithium ion battery cathode material and preparation method thereof, and lithium ion battery |
| CN106299318A (en) * | 2016-10-28 | 2017-01-04 | 合肥国轩高科动力能源有限公司 | silicon-based lithium ion battery cathode material and preparation method thereof |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100851969B1 (en) * | 2007-01-05 | 2008-08-12 | 삼성에스디아이 주식회사 | Anode active material, method of preparing the same, anode and lithium battery containing the material |
| JP4883323B2 (en) * | 2008-08-26 | 2012-02-22 | 信越化学工業株式会社 | Non-aqueous electrolyte secondary battery negative electrode material, Si-O-Al composite manufacturing method, non-aqueous electrolyte secondary battery negative electrode and non-aqueous electrolyte secondary battery |
| CN103730644B (en) * | 2013-12-12 | 2016-03-09 | 天津巴莫科技股份有限公司 | Silicon-silicon oxide-carbon composite negative pole material of lithium ion battery preparation method |
| CN105789594B (en) * | 2016-04-25 | 2018-03-02 | 中国科学院化学研究所 | A kind of silicon/oxidative silicon/carbon composite and its preparation method and application |
| CN106058179A (en) * | 2016-07-06 | 2016-10-26 | 湖南大学 | Preparation method of carbon nanotube/silica/carbon composite cathode material |
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Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007016293A (en) * | 2005-07-08 | 2007-01-25 | Kyoto Univ | Method for producing metal by suspension electrolysis |
| EP2595222A1 (en) * | 2011-11-15 | 2013-05-22 | Shin-Etsu Chemical Co., Ltd. | Non-aqueous electrolyte secondary battery |
| CN103187556A (en) * | 2011-12-27 | 2013-07-03 | 宁波杉杉新材料科技有限公司 | Lithium ion battery and anode material thereof, preparation method |
| CN103474636A (en) * | 2013-09-18 | 2013-12-25 | 上海交通大学 | Silicon-based lithium ion battery negative electrode material and preparation method thereof |
| US8796121B1 (en) * | 2013-11-19 | 2014-08-05 | Translucent, Inc. | Stress mitigating amorphous SiO2 interlayer |
| CN104701509A (en) * | 2013-12-06 | 2015-06-10 | 奇瑞汽车股份有限公司 | Lithium ion battery cathode material and preparation method thereof, and lithium ion battery |
| CN106299318A (en) * | 2016-10-28 | 2017-01-04 | 合肥国轩高科动力能源有限公司 | silicon-based lithium ion battery cathode material and preparation method thereof |
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