CN109167048B - Titanium and nitrogen co-doped carbon-coated silicon monoxide material and preparation method and application thereof - Google Patents

Titanium and nitrogen co-doped carbon-coated silicon monoxide material and preparation method and application thereof Download PDF

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CN109167048B
CN109167048B CN201811113310.9A CN201811113310A CN109167048B CN 109167048 B CN109167048 B CN 109167048B CN 201811113310 A CN201811113310 A CN 201811113310A CN 109167048 B CN109167048 B CN 109167048B
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nitrogen
titanium
silicon monoxide
ball milling
doped carbon
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CN109167048A (en
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许家齐
杨立铭
杨茂萍
曹勇
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Hefei Gotion High Tech Power Energy Co Ltd
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Hefei Guoxuan High Tech Power Energy Co Ltd
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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
    • H01M4/366—Composites as layered products
    • 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
    • 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
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • 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
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

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Abstract

The invention provides a titanium and nitrogen co-doped carbon-coated silicon monoxide material and a preparation method and application thereof. The preparation method comprises the following steps: and mixing the silicon oxide, tetrabutyl titanate and melamine in a ball milling manner, and performing gradient calcination in a nitrogen atmosphere to obtain the titanium and nitrogen co-doped carbon-coated silicon oxide composite material. The titanium and nitrogen co-doped carbon-coated silicon monoxide composite material can be used as a battery electrode to form a photovoltaic device. The photovoltaic device has high charge-discharge specific capacity, high charge capacity, high first efficiency and more stable cycle performance.

Description

Titanium and nitrogen co-doped carbon-coated silicon monoxide material and preparation method and application thereof
Technical Field
The invention relates to a composite material and a preparation method thereof, in particular to an in-situ titanium and nitrogen co-doped carbon-coated silicon monoxide composite material and a preparation method thereof, and belongs to the technical field of composite material preparation.
Background
Since the 90 s of the last century, since sony introduced commercial lithium batteries, graphite cathodes firmly occupied the dominant position, and the improvement of energy density of lithium batteries was severely restricted. Over the years, researchers around the world have attempted to develop high specific capacity negative electrode materials, such as silicon-based negative electrode materials, tin-based materials, etc., that can replace graphite.
The silicon-based negative electrode material is the only novel negative electrode material with high specific capacity for realizing commercial application at present. Among them, commercial silica composite negative electrode materials introduced by korea and japanese material manufacturers are carbon-coated, which improves the conductivity of the materials, and also prevents the silica material from directly contacting the electrolyte, improving the cycle performance of the materials.
However, the large-scale application of the silicon-based anode material still faces many challenges, such as environmental pollution and low first-pass efficiency, and further improvement of the cycle performance of the material and reduction of the production cost are needed.
Disclosure of Invention
In order to solve the above technical problems, an object of the present invention is to provide an electrode material having low cost, no environmental pollution, high initial efficiency and stable cycle performance.
In order to achieve the technical purpose, the invention firstly provides a preparation method of a titanium and nitrogen co-doped carbon-coated silicon monoxide composite material, which comprises the following steps:
and mixing the silicon oxide, tetrabutyl titanate and melamine in a ball milling mode, and performing gradient calcination in a nitrogen atmosphere to obtain the titanium and nitrogen co-doped carbon-coated silicon oxide composite material.
According to the preparation method, tetrabutyl titanate is used as a titanium source and a cross-linking agent, melamine is used as a carbon source and a nitrogen source, firstly, the silicon oxide and the tetrabutyl titanate are subjected to ball milling and mixing, then, the melamine is added for ball milling and mixing, and the in-situ titanium and nitrogen co-doped carbon-coated silicon oxide composite material is obtained through one-step solid phase gradient rotary calcination. The preparation method has the advantages of simple operation, cheap and easily obtained raw materials, low cost, no pollution to the environment and suitability for industrial large-scale production.
In the production method of the present invention, it is preferable that the mass ratio of the silica to the tetrabutyltitanate is 2:1 to 3: 1. For example, the mass ratio of silica to tetrabutyl titanate may be 2.5: 1.
In the production method of the present invention, the mass ratio of the silicon monoxide to the melamine is preferably 1:2 to 1: 3. For example, the mass ratio of silica to melamine may be 1: 2.5.
In the production process of the present invention, it is preferred that the particle size D50 of the silicon oxide used is < 10 μm and the iron content in the silicon oxide is < 50 ppm.
In the preparation method, when the silica, the tetrabutyl titanate and the melamine are subjected to ball milling and mixing, the preparation can be carried out in a ball milling tank; preferably, the method specifically comprises the following steps:
carrying out primary ball milling mixing on the silicon monoxide and tetrabutyl titanate to obtain a mixture;
and adding melamine into the mixture for secondary ball milling and mixing.
In the preparation method of the invention, preferably, the ball milling speed is 200rpm-400rpm when the ball milling mixing is carried out; for example, the ball milling speed may be 250rpm, 260rpm, 270rpm, 300rpm, 320rpm, 350rpm, 390rpm, or the like.
In the preparation method of the present invention, preferably, the time of each ball milling is 0.5h to 1h when the ball milling mixing is performed. For example, the ball milling time can be 0.7h, 0.8h, 0.9h, and the like. The ball milling time refers to the time for each ball milling, namely, the silica and the tetrabutyl titanate are mixed by ball milling for 0.5h-1h to obtain a mixture, and the mixture and the melamine are mixed by ball milling for 0.5h-1 h.
In the preparation method of the present invention, preferably, the sintering schedule of the gradient calcination employed is: calcining for 1h-2h at 300 ℃, calcining for 2h-4h at 650-750 ℃ and calcining for 2h-4h at 900 ℃.
In the production method of the present invention, it is preferable that the temperature is raised at a rate of 5 ℃/min to 10 ℃/min during the gradient calcination. For example, the temperature is raised from the normal temperature to 300 ℃ at the speed of 5 ℃/min-10 ℃/min, then the temperature is raised from 300 ℃ to 650-700 ℃ at the speed of 5 ℃/min-10 ℃/min, and finally the temperature is raised from 650-700 ℃ to 900 ℃ at the speed of 5 ℃/min-10 ℃/min.
In the production method of the present invention, preferably, the gradient calcination may be performed in a rotary kiln; for example, the adopted equipment can be a glass rotary kiln; more preferably, the rotation speed of the gradient calcination is 2 to 4 revolutions per minute; for example, the rotary speed of the rotary glass kiln may be 3 revolutions per minute.
The invention also provides a titanium and nitrogen co-doped carbon-coated silicon oxide composite material, which is prepared by the preparation method of the titanium and nitrogen co-doped carbon-coated silicon oxide composite material.
The titanium in the titanium and nitrogen co-doped carbon-coated silicon oxide composite material has the function of stabilizing graphite and silicon oxide structures, the nitrogen has the function of increasing ionic and electronic conductivity, and the carbon coating can stabilize the structure and mitigate volume expansion while improving the conductivity of the silicon oxide, so that the composite material has high discharge specific capacity, high first efficiency and more stable cycle performance, and has wide application prospects in the fields of high-specific-energy batteries, rear-end electric vehicles and energy storage base stations.
The invention also provides a battery electrode which is prepared from the titanium and nitrogen co-doped carbon-coated silicon monoxide composite material. The battery electrode herein may be, but is not limited to, a negative electrode tab of a battery, etc.
The invention also provides a photovoltaic device comprising a cell electrode of the invention. Photovoltaic devices herein include, but are not limited to, solar cells, lithium cells, and the like.
The invention provides an electric automobile which comprises the photovoltaic device.
According to the titanium and nitrogen co-doped carbon-coated silicon monoxide composite material, tetrabutyl titanate is used as a titanium source and a carbon source, melamine is used as the carbon source and a nitrogen source, the carbon, nitrogen and titanium co-coated SiO composite material is obtained, the composite material has high charge gram capacity (1200 mAh/g), and the composite material has high first effect under a certain discharge condition.
The preparation method of the titanium and nitrogen co-doped carbon-coated silicon monoxide composite material has the advantages of simple operation, cheap and easily-obtained raw materials, low cost and no pollution to the environment, and is suitable for industrial large-scale production.
The titanium and nitrogen co-doped carbon-coated silicon monoxide composite material has high charge-discharge specific capacity, high first efficiency and more stable cycle performance when being used as a battery electrode and applied to a photovoltaic device, and has wide application prospect in the fields of high-specific-energy batteries, rear-end electric vehicles and energy storage base stations.
Drawings
Fig. 1 is a scanning electron micrograph of the in situ titanium and nitrogen co-doped carbon-coated silica composite of example 1.
FIG. 2 is a charge-discharge curve of a tab sheet prepared from the composite material of example 1 and a material not coated with silica.
Fig. 3 is a cycle curve for coin cells made with the composite of example 1 and the material without silica coating.
Detailed Description
The technical solutions of the present invention will be described in detail below in order to clearly understand the technical features, objects, and advantages of the present invention, but the present invention is not limited to the practical scope of the present invention.
The gram capacity of a material, i.e., the specific capacity, refers to the capacity given by a battery (or active material) per unit mass or volume.
The first effect, i.e., the first coulombic efficiency, refers to the percentage of the charge released from the battery during the first discharge and the charge charged during the first charge under certain charge-discharge conditions.
The silicon oxide, the melamine and the tetrabutyl titanate adopted by the invention can be purchased from the market, and the purity grade of the tetrabutyl titanate is chemical purity.
Example 1
The embodiment provides a preparation method of an in-situ titanium and nitrogen co-doped carbon-coated silicon monoxide composite material, which specifically comprises the following steps:
taking the silicon monoxide and tetrabutyl titanate according to the mass ratio of 2:1, and ball-milling for 0.5h in a polytetrafluoroethylene ball-milling tank at the speed of 400rpm to obtain a mixture A;
adding melamine into the mixture A according to the mass ratio of the silicon monoxide to the melamine of 1:2, and continuously performing ball milling for 1h in a polytetrafluoroethylene ball milling tank at the speed of 400rpm to obtain a mixture B;
transferring the mixture B into a crucible, placing the crucible in a glass rotary kiln in nitrogen atmosphere, heating to 300 ℃ at the rotating speed of 2 revolutions per minute and the speed of 5 ℃/min, preserving heat for 2h, then heating to 750 ℃ and preserving heat for 2h, and heating to 900 ℃ and preserving heat for 4 h; and cooling to room temperature to obtain the in-situ titanium and nitrogen co-doped carbon-coated silicon monoxide composite material.
Example 2
The embodiment provides a preparation method of an in-situ titanium and nitrogen co-doped carbon-coated silicon monoxide composite material, which specifically comprises the following steps:
taking silicon monoxide and tetrabutyl titanate according to the mass ratio of 3:1, and ball-milling for 1h in a polytetrafluoroethylene ball-milling tank at the speed of 200rpm to obtain a mixture A;
adding melamine into the mixture A according to the mass ratio of the silicon monoxide to the melamine of 1:3, and continuously performing ball milling for 1h in a polytetrafluoroethylene ball milling tank at the speed of 200rpm to obtain a mixture B;
transferring the mixture B into a crucible, placing the crucible in a glass rotary kiln in nitrogen atmosphere, heating to 300 ℃ at the speed of 5 ℃/min at the speed of 4 revolutions per minute, preserving heat for 1h, then heating to 650 ℃ and preserving heat for 4h, and heating to 900 ℃ and preserving heat for 4 h; and cooling to room temperature to obtain the in-situ titanium and nitrogen co-doped carbon-coated silicon monoxide composite material.
Application example 1
The in-situ titanium and nitrogen co-doped carbon-coated silica composite prepared in example 1 was subjected to electron microscopy scanning, as shown in fig. 1. As can be seen from fig. 1, compared with the original smooth surface of the silicon oxide, the surface of the silicon oxide coated with the in-situ titanium-doped carbon has a uniform coating layer.
Application example 2
The in-situ titanium and nitrogen co-doped carbon-coated silica material prepared in the embodiment 1, the superconducting carbon black and the silicon-based adhesive are mixed according to the weight ratio of 91: 2: 7, adding proper amount of water to prepare slurry, uniformly mixing, coating the slurry on copper foil, drying at 80 ℃ for 12 hours to obtain a pole piece, and marking as a coated pole piece;
similarly, the uncoated silicon oxide piezoelectric ceramic is used for preparing a pole piece according to a phase synchronization step and is marked as an uncoated pole piece group.
Respectively taking the coated pole piece group and the uncoated pole piece group, taking metal lithium as a negative electrode and Celgard2400 as a diaphragm, and containing 1M LiPF6And 10% FEC EC + DMC (volume ratio 1: 1) solution as electrolyte inA2032 type button cell is assembled in an argon atmosphere glove box, and then an electrochemical performance test is carried out (the charging and discharging voltage interval is 0.005-1.5V).
Fig. 2 is a plot of charging and discharging curves of the pole piece of the in-situ titanium and nitrogen co-doped carbon-coated silica composite material of example 1 and the pole piece prepared from the uncoated silica material.
As can be seen from fig. 2, under the conditions of 0.05C rate (1C ═ 1700mA/g) and 0.05-1.5V of charge-discharge interval, the first discharge capacity of the pole piece prepared from the composite material of example 1 reaches 2224mAh/g, and the first discharge capacity of the pole piece prepared from the uncoated cuprous oxide material reaches 2222 mAh/g; under the condition of 0.1C charging rate, the first charging capacity of the pole piece prepared from the composite material in the embodiment 1 reaches 1700mAh/g, and the first charging capacity of the pole piece prepared from the material without silicon oxide reaches 1070 mAh/g; the first efficiency of the pole piece prepared by the composite material of the embodiment 1 is improved from 48.15% to 76.4%, and the coating material of the embodiment 1 shows smaller polarization as seen from the discharge curve potential, so that the composite material has higher specific discharge capacity and first efficiency compared with the uncoated cuprous oxide material. Meanwhile, as can be seen from the chartered cycle curve of fig. 3, the in-situ titanium and nitrogen co-doped carbon-coated silicon monoxide composite material of example 1 has more excellent electrochemical cycle performance under 0.1C (1C-1300 mA/g) rate charge and discharge conditions.

Claims (6)

1. A preparation method of a titanium and nitrogen co-doped carbon-coated silicon monoxide composite material is characterized by comprising the following steps:
mixing silicon monoxide, tetrabutyl titanate and melamine in a ball milling mode, and performing one-step solid phase gradient rotary calcination in a nitrogen atmosphere to obtain the titanium and nitrogen co-doped carbon-coated silicon monoxide composite material; wherein the mass ratio of the silicon monoxide to the tetrabutyl titanate is 2:1-3: 1; the mass ratio of the silicon monoxide to the melamine is 1:2-1: 3;
when the silicon oxide, the tetrabutyl titanate and the melamine are mixed in a ball milling mode, the method comprises the following steps:
performing first ball milling mixing on the silicon monoxide and the tetrabutyl titanate to obtain a mixture, wherein the ball milling speed is 200rpm-400rpm, and the ball milling time is 0.5h-1 h;
adding melamine into the mixture for secondary ball milling and mixing, wherein the ball milling speed is 200-400 rpm, and the ball milling time is 0.5-1 h;
the gradient rotary calcination is carried out in a rotary kiln; the rotation speed is 2-4 r/min;
the gradient rotary calcination comprises the following steps: heating from normal temperature to 300 ℃ at the speed of 5-10 ℃/min, calcining for 1h-2h at 300 ℃, heating from 300 ℃ to 650-750 ℃ at the speed of 5-10 ℃/min, calcining for 2h-4h at 650-750 ℃, and heating from 650-750 ℃ to 900 ℃ at the speed of 5-10 ℃/min, calcining for 2h-4 h.
2. The method according to claim 1, wherein the particle size D50 of the silicon monoxide is less than 10 μm, and the iron content in the silicon monoxide is less than 50 ppm.
3. A titanium and nitrogen co-doped carbon-coated silica composite material, characterized in that the titanium and nitrogen co-doped carbon-coated silica composite material is prepared by the method of claim 1 or 2.
4. A battery electrode prepared from the titanium and nitrogen co-doped carbon-coated silicon monoxide composite material according to claim 3.
5. A photovoltaic device comprising the cell electrode of claim 4.
6. An electric vehicle characterized in that it comprises a photovoltaic device according to claim 5.
CN201811113310.9A 2018-09-25 2018-09-25 Titanium and nitrogen co-doped carbon-coated silicon monoxide material and preparation method and application thereof Active CN109167048B (en)

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CN109888246B (en) * 2019-03-25 2022-03-11 合肥国轩高科动力能源有限公司 Silicon monoxide composite negative electrode material with gradient structure and preparation method and application thereof
CN110071270B (en) * 2019-04-01 2021-02-09 桂林电子科技大学 Nitrogen-doped silicon monoxide negative electrode material and preparation method and application thereof
CN110335999A (en) * 2019-06-19 2019-10-15 合肥国轩高科动力能源有限公司 The zinc co-doped carbon coating of nitrogen aoxidizes sub- silicon composite and its preparation method and application
CN115275209B (en) * 2022-09-28 2023-03-10 四川启睿克科技有限公司 High-first-efficiency silicon cathode with stable structure, preparation method and lithium ion battery

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CN105185975A (en) * 2015-07-20 2015-12-23 合肥国轩高科动力能源有限公司 Preparation method of hydroxyapatite-coated lithium titanate
CN107403919A (en) * 2017-07-29 2017-11-28 合肥国轩高科动力能源有限公司 A kind of nitrating carbon material cladding aoxidizes composite of sub- silicon and preparation method thereof
CN107706383A (en) * 2017-09-21 2018-02-16 合肥国轩高科动力能源有限公司 A kind of titanium doped carbon coating in situ aoxidizes sub- silicon/graphite material and preparation method thereof

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