CN112397701A - Rice husk-based silicon oxide/carbon composite negative electrode material and preparation method and application thereof - Google Patents
Rice husk-based silicon oxide/carbon composite negative electrode material and preparation method and application thereof Download PDFInfo
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- 235000007164 Oryza sativa Nutrition 0.000 title claims abstract description 77
- 235000009566 rice Nutrition 0.000 title claims abstract description 77
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- 239000002131 composite material Substances 0.000 title claims abstract description 48
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 46
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 229910052814 silicon oxide Inorganic materials 0.000 title claims abstract description 38
- 239000007773 negative electrode material Substances 0.000 title claims abstract description 34
- 239000010903 husk Substances 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 240000007594 Oryza sativa Species 0.000 title 1
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 29
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 29
- 238000000034 method Methods 0.000 claims abstract description 21
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- PWKWDCOTNGQLID-UHFFFAOYSA-N [N].[Ar] Chemical compound [N].[Ar] PWKWDCOTNGQLID-UHFFFAOYSA-N 0.000 claims description 4
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- 229910001290 LiPF6 Inorganic materials 0.000 claims description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 3
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- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 239000004698 Polyethylene Substances 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 2
- 229930006000 Sucrose Natural products 0.000 claims description 2
- AUEPDNOBDJYBBK-UHFFFAOYSA-N [Si].[C-]#[O+] Chemical compound [Si].[C-]#[O+] AUEPDNOBDJYBBK-UHFFFAOYSA-N 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
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- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 2
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- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
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- 230000000630 rising effect Effects 0.000 claims 2
- 239000002994 raw material Substances 0.000 abstract description 3
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- 229920005610 lignin Polymers 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
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- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical group COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- VUPKGFBOKBGHFZ-UHFFFAOYSA-N dipropyl carbonate Chemical compound CCCOC(=O)OCCC VUPKGFBOKBGHFZ-UHFFFAOYSA-N 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
本发明公开了一种稻壳基硅氧化物/碳复合负极材料，所述复合负极材料由稻谷壳、酸溶液、氯化锌、碳源、还原剂、乙醇和去离子水原料制备而成；硅氧化物颗粒直径为50～150nm；硅的质量分数为4.8～21.5％，氧的质量分数为5.2～18.5％，碳的质量分数为60～90％。本发明的稻壳基硅氧物/碳复合负极材料应用于锂离子电池，不仅能改善锂电池的首次库伦效率和循环寿命，而且工艺简单、重现性好、易于实施，适合大规模生产。本发明还公开了稻壳基硅氧化物/碳复合负极材料的制备方法与应用方法。
The invention discloses a rice husk-based silicon oxide/carbon composite negative electrode material, which is prepared from rice husk, acid solution, zinc chloride, carbon source, reducing agent, ethanol and deionized water raw materials; The diameter of the silicon oxide particles is 50-150 nm; the mass fraction of silicon is 4.8-21.5%, the mass fraction of oxygen is 5.2-18.5%, and the mass fraction of carbon is 60-90%. The rice husk-based silicon oxide/carbon composite negative electrode material of the present invention is applied to a lithium ion battery, which can not only improve the first coulombic efficiency and cycle life of the lithium battery, but also has a simple process, good reproducibility, easy implementation, and is suitable for large-scale production. The invention also discloses a preparation method and an application method of the rice husk-based silicon oxide/carbon composite negative electrode material.
Description
Technical Field
The invention belongs to the technical field of materials, relates to a lithium ion battery cathode material, and preparation and application thereof, and particularly relates to a rice hull-based silicon oxide/carbon composite cathode material, and a preparation method and application thereof.
Background
In recent decades, with the rapid increase of the application demand of small electronic devices and electric vehicles, higher requirements on the capacity and energy density of lithium ion batteries are put forward. The current commercial lithium ion battery has the theoretical specific capacity (372mAh g) of the negative electrode (graphite)-1) Relatively few and cannot meet the needs of people. Therefore, it becomes important to develop a new high-capacity lithium ion battery negative electrode material.
Silicon is an alloy type lithium ion battery cathode material with great potential. It not only has 4200mAh g-1Which is equivalent to tens of times that of graphite, and has a lower discharge potential plateau and rich crust reserves. However, the silicon-based material as a lithium ion negative electrode material has low conductivity and huge volume expansion, which hinders the popularization and application of the silicon-based material. The huge volume expansion in the charging and discharging process causes the serious powdering of the electrode material and the falling of the conductive network, and an unstable solid electrolyte interface is formed. The following methods are generally used to solve this problem: (1) the surface of the silicon-based material is coated with the carbon-based material, so that the conductivity of the silicon-based material can be improved, and the volume expansion of the silicon-based material in the charging and discharging processes can be effectively controlled. (2) The particle size is reduced, and the method is also an effective way for solving the problems of poor conductivity of the silicon-based material and large volume expansion in the charging and discharging process. The volume is small, the accumulated stress is small, the structure collapse can be prevented, and the long-term stability is realized.
The rice hull is an agricultural and sideline product with rich yield and mainly comprises silicate, lignin, cellulose and hemicellulose. The content of silicon dioxide in the rice hulls is as high as 15-20 wt%, which determines that the rice hulls can be used as silicon/carbon materials. Meanwhile, the particularity of the structure of the rice husk can be directly used for preparing the nano composite material.
The silicon-oxygen-carbon composite material is prepared by taking the rice hulls as the raw materials, so that the negative influence on the environment caused by burning and burying of the rice hulls is avoided, the cheap silicon-oxygen-carbon material can be obtained through modification, calcination and other treatments, the high-performance cheap silicon-oxygen-carbon material is taken as the negative electrode material and applied to the lithium ion battery, and the problem of energy shortage can be effectively relieved.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a rice hull-based silicon oxide/carbon composite negative electrode material and a preparation method and application thereof.
In order to achieve the purpose, the technical scheme of the invention is as follows:
a rice husk-based silicon oxide/carbon composite negative electrode material is prepared from rice husk, an acid solution, zinc chloride, a carbon source, a reducing agent, ethanol and deionized water; the diameter of the silicon oxide/carbon composite negative electrode material is 50-150 nm; the silicon oxide accounts for 10-40% by mass, and the carbon accounts for 60-90% by mass.
In order to achieve the purpose, the other technical scheme of the invention is as follows:
a preparation method of a rice husk-based silicon oxide/carbon composite negative electrode material comprises the following steps:
(1) cleaning rice hulls with ultrapure water, then soaking the rice hulls in an acid solution with the mass percent of 3-12%, continuously stirring and keeping for 24-36 h, then carrying out centrifugal separation, washing the rice hulls with ultrapure water until the pH value of supernatant liquid is 7, and then drying the rice hulls at the temperature of 60-80 ℃ to obtain a product A;
(2) mixing the product A and zinc chloride according to the mass ratio of 1: 1-4, ball-milling for 2-10 h, and drying at 60-80 ℃ to obtain a product B;
(3) the product B is paved in an alumina porcelain boat and is placed in a tubular furnace of inert gas to carry out high-temperature pre-carbonization for 1-5 h at 400-500 ℃ at the heating rate of 0.02-0.5 ℃/min to obtain a product C;
(4) mixing the product C and a carbon source according to the mass ratio of 1: 0.125-3.5, ball-milling for 0.5-8 h, paving the mixture in an alumina porcelain boat, and placing the alumina porcelain boat in a tubular furnace of inert gas to carry out high-temperature carbonization for 2-10 h at 700-1100 ℃ at the heating rate of 0.02-0.5 ℃/min to obtain a product D;
(5) mixing the product D and a reducing agent according to the mass ratio of 1: 1-5, grinding for 0.2-1 h, then paving the mixture in an alumina porcelain boat, placing the alumina porcelain boat in a tubular furnace of inert gas, keeping the temperature at 500-700 ℃ for 1-5 h at the heating rate of 0.02-0.5 ℃/min, and naturally cooling to room temperature to obtain a product E;
(6) and (3) soaking the product E in an acid solution, continuously stirring, repeatedly washing with ultrapure water until the pH value of the filtrate is 7, and drying the precipitate at 60-80 ℃ in vacuum to obtain the silicon oxide/carbon composite anode material.
Further, the acid solution in step 1 is one or a mixture of several of hydrochloric acid, sulfuric acid, nitric acid, acetic acid and citric acid in any proportion.
Further, the inert gas in the step 3 is one of nitrogen gas or argon gas or a nitrogen-argon mixed gas with any ratio.
Further, in the step 4, the carbon source is one of graphite, asphalt, sucrose, glucose and fructose.
Further, in the step 4, the inert gas is one of nitrogen gas or argon gas or a nitrogen-argon mixed gas with any ratio.
Further, in the step 5, the reducing agent is one or more of magnesium, aluminum, sodium, potassium and lithium mixed metal in any proportion.
Further, in the step 5, the inert gas is one of nitrogen gas or argon gas or a nitrogen-argon mixed gas with any ratio.
Further, in the step 6, the concentration of the acid is 1-3 mol/L, and the soaking time is 10-24 h.
In order to achieve the above object, a third technical solution of the present invention is:
the prepared silicon oxide/carbon composite negative electrode material is applied to a negative electrode of a lithium ion battery. Specifically, the method is applied to a CR2032 button type lithium ion battery, and comprises the following steps:
(A) uniformly mixing a silicon-carbon oxide composite material, a conductive agent Super P and a binder polyvinylidene fluoride according to a mass ratio of 70:20-x:10 (x is more than or equal to 0 and less than 20) to obtain a solid mixture;
(B) mixing the solid mixture with N-methyl pyrrolidone according to the mass ratio of 20-25: 75-80, and uniformly stirring to obtain slurry;
(C) coating the slurry on copper foil, drying and rolling to obtain an electrode plate of the lithium ion battery with the thickness of 11-25 mu m;
(D) taking an electrode plate of a lithium ion battery as a working electrode, a lithium plate as a counter electrode, a microporous polypropylene-polyethylene film as a diaphragm, and adopting 1mol/L LiPF6And (3) preparing the electrolyte into a CR2032 button type lithium ion battery in a glove box filled with argon.
The invention has the advantages and beneficial effects that:
1. the invention directly takes the rice hull which is the byproduct of rice as the raw material, realizes the reutilization of the crop byproduct, is beneficial to protecting the environment and saves the production cost. Meets the national requirement of rapidly developing natural waste crops for recycling, and improves the economic, social and ecological benefits of rice.
2. According to the invention, based on the fact that rich silicon elements are contained in the rice husks, the silicon elements are converted into the silicon monoxide through simple calcination, and then the silicon oxide/carbon composite material is formed by mixing the silicon oxide/carbon composite material with the carbon material, so that the conductivity of the silicon material is effectively improved, the volume expansion of the material in the charging and discharging processes is effectively inhibited, and the rate capability and the cycle performance of the composite material are improved.
Drawings
Fig. 1 is an SEM image of a silicon-oxygen-carbon composite anode material prepared in example 1 of the present invention.
FIG. 2 shows that the silicon-oxygen-carbon composite negative electrode material prepared in example 1 of the invention is 500mA g-1Cycle performance graph below.
Detailed Description
In order to make the present invention more fully understood, the technical solutions of the present invention will be described below in detail with reference to the embodiments of the present invention and the accompanying drawings. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
A preparation method of a rice hull-based silicon oxide/carbon composite negative electrode material comprises the following specific steps:
1) cleaning 1g of rice hulls with ultrapure water, then soaking the rice hulls in a hydrochloric acid solution with the mass percent of 10%, continuously stirring the rice hulls at room temperature and keeping the rice hulls for 24 hours, after soaking, centrifugally separating the rice hulls, washing the rice hulls with the ultrapure water until the pH value is 7, and drying the rice hulls in a vacuum drying oven at the temperature of 60 ℃ to obtain a product A;
2) the product A is reacted with ZnCl2Mixing the materials according to a mass ratio of 1:1, ball-milling for 8 hours, and drying at 60-80 ℃ to obtain a product B;
3) the product B is paved in an alumina porcelain boat and is placed in a nitrogen gas tube furnace to be pre-carbonized at high temperature for 1h at the temperature rise rate of 2 ℃/min at 450 ℃, so as to obtain a product C;
4) mixing the product C and graphite according to the mass ratio of 1:1, ball-milling for 5 hours, then paving the product C in an alumina porcelain boat, and placing the alumina porcelain boat in a tubular furnace of hydrogen-argon mixed gas at the temperature rise rate of 2 ℃/min and carrying out high-temperature carbonization at 1100 ℃ to obtain a product D;
5) mixing and grinding the product D and reducing agent Al powder according to the mass ratio of 1:1 for 0.5 hour, then paving the product D in an alumina porcelain boat, and calcining the product D in a tubular furnace of hydrogen-argon mixed gas at the temperature rise rate of 2 ℃/min at 700 ℃ to obtain a product E;
6) soaking the product E in 2mol L-1And (3) continuously stirring in a hydrochloric acid solution, then repeatedly washing with ultrapure water until the pH value of the filtrate is 7, and drying the precipitate in vacuum at 60 ℃ to obtain the rice-based siloxycarbon composite negative electrode material.
The prepared rice-based silicon oxide/carbon composite negative electrode material is applied to a CR2032 button lithium ion battery, and the specific method comprises the following steps:
uniformly mixing the silicon-oxygen-carbon composite negative electrode material, the conductive agent Super P and the adhesive polyvinylidene fluoride according to the mass ratio of 70:20: 10; and then according to the mass ratio of 20: 80 mixing the above materials uniformlyMixing the mixture (the mixture of silicon oxide/carbon microsphere composite material, Super P and polyvinylidene fluoride) with N-methyl pyrrolidone, 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 taken as an electrode positive plate, a microporous polypropylene film is taken as a diaphragm, and 1mol/L LiPF6And (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.
Performance testing
After the lithium ion battery is kept stand for 24 hours, a charge-discharge test is carried out on the lithium ion battery in the first circle at the current of 0.1 ℃, and the charge-discharge voltage interval is between 0.01 and 3.0V; and carrying out a charge-discharge test at 0.5C from the second circle, wherein the charge-discharge interval is between 0.01 and 3.0V. The test results are shown in fig. 2.
Taking the silicon-oxygen-carbon composite material prepared in example 1 as an example, the scanning of an electron microscope is performed, and the result is shown in fig. 1. As can be seen from the figure, the prepared silicon-oxygen-carbon composite material has the advantages of rough material structure surface, uneven pore size and more pores, and the occurrence of the structure on the surface is caused by that during the carbonization process of the rice husk, organic matters such as lignin, cellulose and hemicellulose in the rice husk are pyrolyzed, and released gas escapes from the surface of the rice husk.
FIG. 2 shows the current density at 0.5A g for large charge and discharge-1And (4) constant current charge-discharge circulation. It is clear from the figure that the initial discharge specific capacity is 1098.8mAh/g and then the specific capacity is maintained at about 700mAh/g in 70 cycles. The early-stage specific capacity of the cycle is very considerable, which is due to the excellent electrochemical properties of the silicon-oxygen-carbon composite material. The lithium battery can still maintain 437mAh/g at 100 cycles and is still far higher than the capacity of the graphite negative electrode of the current commercial lithium battery.
Example 2
A preparation method of a rice hull-based silicon oxide/carbon composite negative electrode material comprises the following specific steps:
1) cleaning 1g of rice hulls with ultrapure water, then soaking the rice hulls in a hydrochloric acid solution with the mass percent of 10%, continuously stirring the rice hulls at room temperature and keeping the rice hulls for 24 hours, after soaking, centrifugally separating the rice hulls, washing the rice hulls with the ultrapure water until the pH value is 7, and drying the rice hulls in a vacuum drying oven at 60 ℃ to obtain a product A;
2) the product A is reacted with ZnCl2Mixing the materials according to a mass ratio of 1:2, ball-milling and stirring for 8 hours, and drying in a vacuum drying oven at 60-80 ℃ to obtain a product B;
3) the product B is paved in an alumina porcelain boat and is placed in a nitrogen gas tube furnace to be pre-carbonized at high temperature for 1h at the temperature rise rate of 2 ℃/min at 450 ℃, so as to obtain a product C;
4) mixing the product C and graphite according to the mass ratio of 1:3.5, ball-milling for 5 hours, then paving the product C in an alumina porcelain boat, and placing the alumina porcelain boat in a tubular furnace of hydrogen-argon mixed gas at the temperature rise rate of 2 ℃/min for high-temperature carbonization at 1100 ℃ to obtain a product D;
5) mixing and grinding the product D and reducing metal Al for 0.5 hour according to the mass ratio of 1:1, then paving the product D in an alumina porcelain boat, and calcining the product D in a tubular furnace of hydrogen-argon mixed gas at the temperature rise rate of 2 ℃/min at 700 ℃ to obtain a product E;
6) soaking the product E in 2mol L-1And (3) continuously stirring in a hydrochloric acid solution, then repeatedly washing with ultrapure water until the pH value of the filtrate is 7, and drying the precipitate in vacuum at 60 ℃ to obtain the rice-based siloxycarbon composite negative electrode material.
The concrete steps of the method for applying the prepared rice-based silicon oxide/carbon composite negative electrode material to CR2032 button lithium ion batteries and performance tests are the same as those of the embodiment 1
Example 3
A preparation method of a rice hull-based silicon oxide/carbon composite negative electrode material comprises the following specific steps:
1) cleaning 1g of rice hulls with ultrapure water, then soaking the rice hulls in a hydrochloric acid solution with the mass percent of 10%, continuously stirring the rice hulls at room temperature and keeping the rice hulls for 24 hours, after soaking, centrifugally separating the rice hulls, washing the rice hulls with the ultrapure water until the pH value is 7, and drying the rice hulls in a vacuum drying oven at the temperature of 60 ℃ to obtain a product A;
2) the product A is reacted with ZnCl2Mixing according to the mass ratio of 1:1, ball-milling and stirring for 8h, placing in a vacuum drying ovenDrying at 60-80 ℃ to obtain a product B;
3) the product B is paved in an alumina porcelain boat and is placed in a nitrogen gas tube furnace to be pre-carbonized at high temperature for 1h at the temperature rise rate of 2 ℃/min at 450 ℃, so as to obtain a product C;
4) mixing the product C and graphite according to the mass ratio of 1:0.125, ball-milling for 5 hours, then paving the product C in an alumina porcelain boat, and placing the alumina porcelain boat in a tubular furnace of hydrogen-argon mixed gas at the temperature rise rate of 2 ℃/min for high-temperature carbonization at 1100 ℃ to obtain a product D;
5) mixing and grinding the product D and reducing metal Al for 0.5 hour according to the mass ratio of 1:1, then paving the product D in an alumina porcelain boat, and calcining the product D in a tubular furnace of hydrogen-argon mixed gas at the temperature rise rate of 2 ℃/min at 700 ℃ to obtain a product E;
6) soaking the product E in 2mol L-1And (3) continuously stirring in a hydrochloric acid solution, then repeatedly washing with ultrapure water until the pH value of the filtrate is 7, and drying the precipitate in vacuum at 60 ℃ to obtain the rice-based siloxycarbon composite negative electrode material.
The concrete steps of the method for applying the prepared rice-based silicon oxide/carbon composite negative electrode material to CR2032 button lithium ion batteries and performance tests are the same as those of the embodiment 1
Example 4
A preparation method of a rice hull-based silicon oxide/carbon composite negative electrode material comprises the following specific steps:
1) cleaning 1g of rice hulls with ultrapure water, then soaking the rice hulls in a hydrochloric acid solution with the mass percent of 10%, continuously stirring the rice hulls at room temperature and keeping the rice hulls for 24 hours, after soaking, centrifugally separating the rice hulls, washing the rice hulls with the ultrapure water until the pH value is 7, and drying the rice hulls in a vacuum drying oven at the temperature of 60 ℃ to obtain a product A;
2) the product A is reacted with ZnCl2Mixing the materials according to the mass ratio of 1:1, ball-milling for 8 hours, and drying in a vacuum drying oven at 60-80 ℃. Obtaining a product B;
3) the product B is paved in an alumina porcelain boat and is placed in a nitrogen gas tube furnace to be pre-carbonized at high temperature for 1h at the temperature rise rate of 2 ℃/min at 450 ℃, so as to obtain a product C;
4) mixing the product C and graphite according to the mass ratio of 1:2, ball-milling for 5 hours, then paving the product C in an alumina porcelain boat, and placing the alumina porcelain boat in a tubular furnace of hydrogen-argon mixed gas at the temperature rise rate of 2 ℃/min and carrying out high-temperature carbonization at 1100 ℃ to obtain a product D;
5) mixing and grinding the product D and reducing metal Al for 0.5 hour according to the mass ratio of 1:1, then paving the product D in an alumina porcelain boat, and calcining the product D in a tubular furnace of hydrogen-argon mixed gas at the temperature rise rate of 2 ℃/min at 700 ℃ to obtain a product E;
6) soaking the product E in 2mol L-1And (3) continuously stirring in a hydrochloric acid solution, then repeatedly washing with ultrapure water until the pH value of the filtrate is 7, and drying the precipitate in vacuum at 60 ℃ to obtain the rice-based siloxycarbon composite negative electrode material.
The concrete steps of the method for applying the prepared rice-based silicon oxide/carbon composite negative electrode material to CR2032 button lithium ion batteries and performance tests are the same as those of the embodiment 1
The electrical property test results of the rice silicon oxide/carbon composite negative electrode material applied to the CR2032 button lithium ion battery are shown in Table 1.
Table 1 shows the capacities obtained in the 2 nd and 100 th circles of the lithium ion batteries of examples 1 to 4 in the charge and discharge test at a current of 0.5C.
TABLE 1
From table 1, it can be seen that when the silicon oxide/carbon microspheres of the invention are applied to a lithium ion battery as an electrode negative electrode material, the charge capacity is more than 430mAh/g after 100 cycles of circulation, the capacity retention rate is more than 85.4%, the cycle performance is good, and the cycle performance is still far higher than that of the current commercial graphite negative electrode material.
TABLE 2 Mass and atomic percentages of Si, O and C in the silicon oxide/carbon microsphere composite material of example 1
| Kind of element | Wt％ | Atomic％ |
| C | 58.43 | 70.80 |
| O | 19.55 | 17.79 |
| Si | 22.02 | 11.41 |
| Total amount of | 100.00 | 100.00 |
It can be seen that the atomic number ratio of Si, O, C in the silicon oxide/carbon (SiOx/C) microsphere composite was 1:1.56: 6.21.
Claims (10)
1. A rice husk-based silicon oxide/carbon composite negative electrode material is prepared from rice husk, an acid solution, zinc chloride, a carbon source, a reducing agent, ethanol and deionized water; the diameter of the silicon oxide/carbon composite negative electrode material is 50-150 nm; the silicon oxide/carbon composite negative electrode material comprises 4.8-21.5% by mass of silicon, 5.2-18.5% by mass of oxygen and 60-90% by mass of carbon.
2. The rice husk-based silicon oxide/carbon composite anode material according to claim 1, wherein the silicon oxide particle diameter of the silicon oxide/carbon composite anode material is 50-150 nm.
3. The preparation method of the rice husk-based silicon oxide/carbon composite anode material according to claim 1, characterized by comprising the following steps:
(1) cleaning rice hulls with ultrapure water, then soaking the rice hulls in an acid solution with the mass percent of 3-12%, continuously stirring and keeping for 24-36 h, then carrying out centrifugal separation, washing the rice hulls with ultrapure water until the pH value of supernatant liquid is 7, and then drying the rice hulls at the temperature of 60-80 ℃ to obtain a product A;
(2) mixing the product A and zinc chloride according to a mass ratio of 1: 1-4, ball-milling for 2-10 h, and drying at 60-80 ℃ to obtain a product B;
(3) the product B is paved in an alumina porcelain boat, placed in a tubular furnace of inert gas at the temperature rising rate of 0.02-0.5 ℃/min and the temperature rising temperature of 400-500 ℃, calcined for 1-5 h, and cooled to the room temperature to obtain a product C;
(4) mixing the product C and a carbon source according to a mass ratio of 1: 0.125-3.5, ball-milling for 0.5-8 h, then paving the mixture in an alumina porcelain boat, placing the alumina porcelain boat in a tubular furnace of inert gas, and calcining for 2-10 h at a temperature rise rate of 0.02-0.5 ℃/min and a temperature rise temperature of 700-1100 ℃ to obtain a product D;
(5) mixing the product D and a reducing agent according to the mass ratio of 1: 1-5, grinding for 0.2-1 h, then paving the mixture in an alumina porcelain boat, placing the alumina porcelain boat in a tubular furnace of inert gas, heating at the rate of 0.02-0.5 ℃/min, wherein the heating temperature is 500-700 ℃, calcining for 1-5 h, and naturally cooling to the room temperature to obtain a product E;
(6) and soaking the product E in an acid solution, continuously stirring, repeatedly washing with ultrapure water until the pH value of the filtrate is 7, and then drying the precipitate at the temperature of 60-80 ℃ in vacuum to obtain the silicon oxide/carbon composite negative electrode material.
4. The method of claim 2, wherein: the acid solution in the step 1 is one or a mixture of several of hydrochloric acid, sulfuric acid, nitric acid, acetic acid and citric acid in any proportion.
5. The method of claim 2, wherein: the inert gas in the steps 3, 4 and 5 is one of nitrogen gas, argon gas or a nitrogen-argon mixed gas with any ratio.
6. The method of claim 2, wherein: the carbon source in the step 4 is one of graphite, asphalt, sucrose, glucose and fructose.
7. The method of claim 2, wherein: the reducing agent in the step 5 is one or a mixture of more of magnesium, aluminum, sodium, potassium and lithium in any proportion.
8. The method of claim 2, wherein: the acid concentration in the step 6 is 1-3 mol/L.
9. The silicon-oxygen-carbon composite material as defined in claim 2 is applied to a negative electrode of a lithium ion battery.
10. A method according to claim 9, characterized in that: the method is applied to the CR2032 button lithium ion battery and comprises the following steps:
(A) uniformly mixing a silicon-carbon oxide composite material, a conductive agent Super P and a binder polyvinylidene fluoride according to a mass ratio of 70:20-x:10, wherein x is more than or equal to 0 and less than 20 to obtain a solid mixture;
(B) mixing the solid mixture obtained in the step (A) with N-methyl pyrrolidone according to a mass ratio of 20-25: 75-80, and uniformly stirring to obtain slurry;
(C) coating the slurry obtained in the step (B) on copper foil, and drying and rolling to obtain an electrode plate of the lithium ion battery with the thickness of 11-25 mu m;
(D) and (C) taking the electrode plate of the lithium ion battery obtained in the step (C) as a working electrode, taking a lithium sheet as a counter electrode, taking a microporous polypropylene-polyethylene film as a diaphragm, taking 1mol/L LiPF6 as electrolyte, and assembling into a CR2032 button type lithium ion battery in a glove box filled with argon.
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