CN115513445A - Double-layer coated silicon monoxide composite negative electrode material and preparation method thereof - Google Patents

Double-layer coated silicon monoxide composite negative electrode material and preparation method thereof Download PDF

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CN115513445A
CN115513445A CN202211465313.5A CN202211465313A CN115513445A CN 115513445 A CN115513445 A CN 115513445A CN 202211465313 A CN202211465313 A CN 202211465313A CN 115513445 A CN115513445 A CN 115513445A
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silicon
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titanium dioxide
negative electrode
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刘景博
霍锋
刘艳侠
刘凡
柴丰涛
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Institute of Process Engineering of CAS
Zhengzhou Institute of Emerging Industrial Technology
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Zhengzhou Institute of Emerging Industrial Technology
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    • H—ELECTRICITY
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    • 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
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • 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
    • 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
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
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    • 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
    • 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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Abstract

The invention provides a double-layer coated silicon monoxide composite negative electrode material and a preparation method thereof. The silicon oxide is a multilayer composite coating network cross-linked structure, the innermost layer is silicon oxide SiOx, the middle layer is a silicon-doped titanium dioxide coating layer, and the outer layer is amorphous carbon formed by polymerization and calcination of organic monomers. In the whole composite material, the middle layer is tightly connected with the surface of the micron-sized silicon monoxide inner layer through a formed Si-O-Ti bond chemical framework, so that the interface resistance is effectively reduced, and the binding force between the coating layer and the silicon monoxide is increased. The middle layer is doped with silicon, so that the overall capacity of the material is improved, hydrogen bonds are formed with the outer organic monomer, the polymer is guided to grow regularly and directionally, the polymer coating layer is more uniform and compact, the contact between the electrolyte and the surface of the electrode is improved, and the volume expansion is inhibited. The silicon monoxide composite negative electrode material provided by the invention has the advantages of high conductivity, good cycle performance, stable interface, simple process and suitability for industrialization.

Description

Double-layer coated silicon monoxide composite negative electrode material and preparation method thereof
Technical Field
The invention relates to the field of battery materials, in particular to a high-performance silicon-carbon negative electrode material for a lithium battery and a preparation method thereof.
Background
With the rapid development of mobile electronic products and new energy automobile industries, the requirements of the market on the energy density of lithium ion batteries are gradually increased, and the cathode material is used as a key material of the lithium ion batteries and plays a decisive role in the exertion of battery energy. The theoretical specific capacity of the traditional negative electrode material graphite is only 372 mAh/g, and the use requirement of the high-energy density lithium ion battery cannot be met. The theoretical capacity of silicon is up to 4200 mAh/g, which is more than ten times of the theoretical capacity of graphite. In order to achieve the goal of higher energy density, it is a common consensus in the industry to develop silicon-based negative electrodes for application in lithium ion battery systems.
Although the silicon-based negative electrode material has a wide application prospect, the silicon-based material still has technical barriers to be broken through in the actual use process, wherein the main problems are as follows: 1) The volume expansion reaches 320% after lithium intercalation, and the volume expansion further causes material pulverization, electrode structure change and continuous formation of a Solid Electrolyte Interface (SEI) film; 2) Intrinsic to the semiconductor material, is poorly conductive. Because of the limitation of the bottleneck problem, silicon materials are not used as anode materials alone, and at present, the battery material enterprises mainly use silicon together with graphite, a conductive agent and other carbon materials, and the introduction of the carbon materials can improve the conductivity of silicon-carbon anodes.
CN 1014022257B discloses a lithium ion battery silicon monoxide composite negative electrode material, a preparation method and uses thereof. A coating carbon layer is formed on the surface of the silicon oxide powder by a solid-phase coating method, the carbon layer is difficult to uniformly coat the surface of micron-sized particles, part of the surface of the particles is exposed and leaked, the carbon layer is in contact with electrolyte, more irreversible reactions are caused in the charging and discharging process, and the coulomb efficiency is low.
CN 107658455A discloses a method for preparing a conductive polymer-carbon-coated silica composite material, in which carbon is directly coated on the surface of silica particles, and the conductive polymer is coated on the surface of carbon by coupling agent, so as to reduce the volume expansion effect of the material, but the battery capacity is affected and the first effect is low.
Disclosure of Invention
Aiming at the technical problems, the invention provides the double-layer coated silica negative electrode material and the preparation method thereof, and the silica composite negative electrode material provided by the invention has the advantages of high conductivity, good cycle performance, stable interface, simple process and suitability for industrialization.
In order to solve the technical problem, the invention adopts the following technical scheme:
the double-layer coated silicon oxide composite negative electrode material is of a multi-layer composite coating cross-linked structure, wherein the innermost layer is silicon oxide, and the middle layer is a silicon-doped titanium dioxide coating layer (TiO coating layer) 2 @ Si), the outermost layer being an amorphous carbon coating produced by polymer cracking. Wherein, tiO 2 The formed Si-O-Ti bond chemical skeleton is tightly connected with the micron-sized silicon oxide surface to form a cross-linked structure, namely TiO 2 Silicon in the coating layer can form a Si-O bond, and the Si-O bond and an organic monomer form a hydrogen bond, so that the coating layer formed by monomer polymerization is more orderly and compact, and finally, the mixed double-layer coating effect is realized.
Furthermore, the mass fraction of the silica in the double-layer coated silica composite negative electrode material is 90-98%, the mass fraction of the silicon doped titanium dioxide coating layer in the middle layer is 1-8% of the mass of the silicon oxide composite negative electrode material, and the mass fraction of the amorphous carbon coating layer in the silicon oxide composite negative electrode material is 1-8%.
The preparation method of the double-layer coated silicon monoxide composite negative electrode material comprises the following steps:
(1) Mixing and stirring a titanium dioxide precursor, a silicon source substance and a solvent to obtain a solution A, and stirring acid, water and the solvent to obtain a solution B;
(2) Dropwise adding the solution B into the solution A, stirring, and sintering at high temperature in a muffle furnace to obtain Si-doped titanium dioxide;
(3) Adding the silicon oxide powder and Si-doped titanium dioxide into an ethanol solution, mixing a solid phase and a liquid phase at high energy, drying, and calcining at high temperature to obtain titanium dioxide-coated silicon oxide;
(4) And adding the coated silica and aniline monomer into dilute hydrochloric acid, stirring for reaction, dropwise adding ammonium persulfate, and filtering and calcining the product at high temperature to obtain the silica composite negative electrode material.
Further, the titanium dioxide precursor in the step (1) comprises one of tetrabutyl titanate, butyl titanate, propyl titanate and isopropyl titanate. The silicon source comprises one of tetraethoxysilane, propyl orthosilicate and methyl orthosilicate, and the solvent comprises one of ethanol, methanol, isopropanol and acetone.
Further, in the step (2), the stirring time is 0.5 to 2h, the muffle furnace sintering temperature is 400 to 600 ℃, the heating rate is 5 to 10 ℃/min, and the sintering time is 2 to 6h.
Further, in the step (3), the particle size of the silica powder is 3 to 6 μm, and the mixing mode of solid-liquid phase high-energy mixing comprises one of magnetic stirring, ball milling and ultrasonic oscillation; drying by adopting an air-blast drying oven at the temperature of 50 to 80 ℃; and (2) performing high-temperature calcination in an inert gas by using a tube furnace, wherein the inert gas is one of nitrogen and argon, the heating rate is 5 ℃/min, the sintering temperature is 700-900 ℃, the sintering time is 2-4 h, and the temperature is naturally cooled.
Further, in the step (4), aniline monomer accounts for 3-10% of the mass of the silica, the concentration of hydrochloric acid is 1-3M, the mass ratio of aniline to ammonium persulfate is 1 (3-5), high-temperature calcination is carried out in a tubular furnace in inert gas, the inert gas is one of nitrogen and argon, the heating rate is 5 ℃/min, the sintering temperature is 700-900 ℃, the sintering time is 2-4 h, and the temperature is naturally cooled.
The invention has the beneficial effects that:
（1）TiO 2 a Si-O-Ti bond chemical framework is formed with the silicon oxide, so that the inner layer and the middle layer are tightly connected, the interface resistance is effectively reduced, the binding force of the coating layer and the silicon oxide is increased, and the stability of the material is enhanced; (2) TiO2 2 The Si element is doped in the coating, so that the integral capacity of the material is improved, a Si-O bond can be formed, and the Si-O bond and an aniline monomer form a hydrogen bond to guide the polymer to grow regularly and directionally, so that a polymer coating layer is more uniform and compact, and the contact between electrolyte and the surface of an electrode is improved.
Drawings
Fig. 1 is a schematic structural view of a silica negative electrode material, wherein 1 is silica, 2 is a tio2@ si coating layer, and 3 is an amorphous carbon layer formed by a polymer.
FIG. 2 is a graph showing the cycle characteristics of a silica composite anode material obtained in example 1.
Detailed Description
The present invention will be further described with reference to the following examples. It is to be understood that the following examples are illustrative only and are not intended to limit the scope of the invention, which is to be given the full breadth of the appended claims and any and all insubstantial modifications and variations thereof which can be made by one skilled in the art based on the teachings of the invention as described above.
The silicon-oxygen cathode material prepared in the embodiment of the invention is assembled into a half cell and subjected to electrochemical performance test: silicon-carbon negative electrode material: super P: the binder is homogenized and smeared according to the mass ratio of 8. The binder is a solution prepared from sodium carboxymethylcellulose (CMC), styrene Butadiene Rubber (SBR) and polyacrylic acid (PAA) in a mass ratio of 1 6 A conventional electrolyte. The lithium plate is used as a counter electrode and assembled into a CR2025 button cell. Under the condition of normal temperature, a charge-discharge test is carried out by utilizing an LANHE CT2001A blue test system under the current density of 100 mA/g, and the voltage range is 0.005-2.0V.
Example 1
The preparation method of the double-layer coated silica composite negative electrode material of the embodiment comprises the following steps:
(1) Adding 10g of tetrabutyl titanate and 2g of ethyl orthosilicate into 200mL of absolute ethyl alcohol, and stirring for 30min; 10g of pure water and 200mL of absolute ethanol were added to 1M diluted hydrochloric acid, and the mixture was stirred for 30min. The latter is added into the latter drop by drop, stirred continuously and sintered for 2 hours at 500 ℃ in a muffle furnace to obtain Si-doped TiO 2 。
(2) 10g of silica and 1g of silicon-doped TiO 2 Adding into 200mL ethanol solution, stirring for 30min, sintering in muffle furnace at 500 deg.C for 2h, calcining in tubular furnace at 700 deg.C for 2h, introducing protective gas N during calcining 2 The heating rate is 5 ℃/min to obtain the composite material SiO 2 @TiO 2 。
(3) Mixing SiO 2 @TiO 2 Adding aniline monomer into dilute hydrochloric acid, stirring and reacting for 4h under ice bath condition, dropwise adding ammonium persulfate, filtering and drying the solution, calcining at 800 ℃ for 2h in a tubular furnace, and introducing protective gas N during calcination 2 Heating rate is 5 ℃/min to obtain silicon-oxygen cathode material SiO 2 @TiO 2 @C。
Example 2
The preparation method of the double-layer coated silica composite negative electrode material of the embodiment comprises the following steps:
(1) Adding 10g of tetrabutyl titanate and 2g of propyl orthosilicate into 200mL of absolute ethyl alcohol, and stirring for 30min; 10g of pure water and 200mL of absolute ethanol were added to 1M of dilute hydrochloric acid, and the mixture was stirred for 30min. Dropwise adding the latter into the latter, continuously stirring, and sintering in a muffle furnace at 500 ℃ for 2h to obtain Si-doped TiO 2 。
(2) Mixing 10g of SiO 2 And 1g of silicon-doped TiO 2 Adding into 200mL ethanol solution, stirring for 30min, sintering in muffle furnace at 500 deg.C for 2h, calcining in tubular furnace at 700 deg.C for 2h, introducing protective gas N during calcining 2 Heating rate is 5 ℃/min to obtain the composite material SiO 2 @TiO 2
(3) Mixing SiO 2 @TiO 2 Adding aniline monomer into dilute hydrochloric acid, stirring and reacting for 4h under ice bath condition, dropwise adding ammonium persulfate, filtering and drying the solution, and putting the solution into a tubular furnace 8Calcining at 00 ℃ for 2h, and introducing protective gas N during calcining 2 Heating rate is 5 ℃/min to obtain silicon-oxygen cathode material SiO 2 @TiO 2 @C。
Example 3
The preparation method of the double-layer coated silicon monoxide composite negative electrode material of the embodiment is as follows:
(1) Adding 10g of tetrabutyl titanate and 2g of ethyl orthosilicate into 200mL of absolute ethyl alcohol, and stirring for 30min; 10g of pure water and 200mL of absolute ethanol were added to 1M diluted hydrochloric acid, and the mixture was stirred for 30min. The latter is added into the latter drop by drop, stirred continuously and sintered for 2 hours at 500 ℃ in a muffle furnace to obtain Si-doped TiO 2 。
(2) 10g of SiO 2 And 1g of silicon-doped TiO 2 Adding into 200mL ethanol solution, stirring for 30min, sintering in muffle furnace at 500 deg.C for 2h, calcining in tube furnace at 700 deg.C for 2h, introducing protective gas N during calcining 2 Heating rate is 5 ℃/min to obtain the composite material SiO 2 @TiO 2
(3) Mixing SiO 2 @TiO 2 Adding aniline monomer into dilute hydrochloric acid, stirring and reacting for 4h under ice bath condition, dropwise adding ammonium persulfate, filtering and drying the solution, calcining at 800 ℃ for 2h in a tubular furnace, and introducing protective gas N during calcination 2 Heating rate is 5 ℃/min to obtain silicon-oxygen cathode material SiO 2 @TiO 2 @C。
Comparative example 1
(1) Adding 10g of tetrabutyl titanate and 2g of ethyl orthosilicate into 200mL of absolute ethyl alcohol, and stirring for 30min; 10g of pure water and 200mL of absolute ethanol were added to 1M diluted hydrochloric acid, and the mixture was stirred for 30min. The latter is added into the latter drop by drop, stirred continuously and sintered for 2 hours at 500 ℃ in a muffle furnace to obtain Si-doped TiO 2 。
(2) Mixing 10g of SiO 2 And 1g of silicon-doped TiO 2 Adding into 200mL ethanol solution, stirring for 30min, sintering in muffle furnace at 500 deg.C for 2h, calcining in tubular furnace at 700 deg.C for 2h, introducing protective gas N during calcining 2 Heating rate is 5 ℃/min to obtain the composite material SiO 2 @TiO 2 Si。
Comparative example 2
Mixing SiO 2 Adding aniline monomer into dilute hydrochloric acid, stirring and reacting for 4h under ice bath condition, dropwise adding ammonium persulfate, filtering and drying the solution, calcining at 800 ℃ for 2h in a tubular furnace, and introducing protective gas N during calcination 2 Heating rate is 5 ℃/min to obtain silicon-oxygen cathode material SiO 2 @C。
Comparative example 3 (comparing to example 1, the intermediate layer of this comparative example is TiO 2 ）
(1) Adding 10g of tetrabutyl titanate into 200mL of absolute ethyl alcohol, and stirring for 30min; 10g of pure water and 200mL of absolute ethanol were added to 1M diluted hydrochloric acid, and the mixture was stirred for 30min. The latter is added into the latter drop by drop, stirred continuously and sintered for 2 hours in a muffle furnace at 500 ℃ to obtain TiO 2 。
(2) Mixing 10g of SiO 2 And 1g of TiO 2 Adding into 200mL ethanol solution, stirring for 30min, sintering in muffle furnace at 500 deg.C for 2h, calcining in tubular furnace at 700 deg.C for 2h, introducing protective gas N during calcining 2 Heating rate is 5 ℃/min to obtain the composite material SiO 2 @TiO 2。
(3) Mixing SiO 2 @TiO 2 Adding aniline monomer into dilute hydrochloric acid, stirring and reacting for 4h under ice bath condition, dropwise adding ammonium persulfate, filtering and drying the solution, calcining at 800 ℃ for 2h in a tubular furnace, and introducing protective gas N during calcination 2 Heating rate is 5 ℃/min to obtain silicon-oxygen cathode material SiO 2 @TiO 2 @C。
Comparative example 4
Adding 10g of silica and 2g of tetrabutyl titanate into ethanol, stirring for pretreatment, and calcining at 800 ℃ for 4h in nitrogen atmosphere to obtain SiO 2 @TiO 2 A composite material.
Mixing SiO 2 @TiO 2 Adding aniline monomer into dilute hydrochloric acid, stirring and reacting for 4h under ice bath condition, dropwise adding ammonium persulfate, filtering and drying the solution, calcining at 800 ℃ for 2h in a tubular furnace, and introducing protective gas N during calcination 2 Heating rate of 5 deg.C/min to obtain silica anionElectrode material SiO 2 @TiO 2 @C。
Table 1 is a table of electrochemical properties of the silicon oxide negative electrode materials of examples 1 to 3 and comparative examples 1 to 4
Figure 489697DEST_PATH_IMAGE002
The foregoing shows and describes the general principles and features of the present invention, together with the advantages thereof. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are given by way of illustration of the principles of the present invention, but that various changes and modifications may be made without departing from the spirit and scope of the invention, and such changes and modifications are within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.

Claims (10)

1. A double-layer coated silicon monoxide composite negative electrode material is characterized in that: the silicon oxide negative electrode material is of a multilayer composite coating cross-linked structure, the innermost layer is silicon oxide, the middle layer is a silicon-doped titanium dioxide coating layer, and the outermost layer is an amorphous carbon coating layer generated by polymer cracking.
2. The double-coated silica composite anode material according to claim 1, wherein: the mass fraction of the silica in the double-layer coated silica composite negative electrode material is 90-98%, the mass fraction of the silicon-doped titanium dioxide coating layer in the middle layer accounts for 1-8% of the mass of the double-layer coated silica composite negative electrode material, and the mass fraction of the amorphous carbon coating layer accounts for 1-8% of the mass of the double-layer coated silica composite negative electrode material.
3. The preparation method of the double-layer coated silica composite anode material according to claim 1, characterized by comprising the steps of:
(1) Mixing and stirring a titanium dioxide precursor, a silicon source substance and a solvent to obtain a solution A, and mixing and stirring acid, water and the solvent to obtain a solution B;
(2) Dropwise adding the solution B into the solution A, uniformly stirring, and sintering at high temperature in a muffle furnace to obtain silicon-doped titanium dioxide;
(3) Adding the silicon oxide powder and the silicon-doped titanium dioxide into an ethanol solution, drying and calcining at high temperature after mixing solid and liquid phases at high energy to obtain silicon oxide coated with the silicon-doped titanium dioxide;
(4) Adding silicon-doped titanium dioxide coated silicon oxide and aniline monomer into dilute hydrochloric acid, stirring for reaction, dropwise adding ammonium persulfate, and filtering and calcining the product at high temperature to obtain the silicon-oxygen composite negative electrode material.
4. The method for preparing the double-layer coated silica composite anode material according to claim 1, wherein: in the step (1), the titanium dioxide precursor comprises tetrabutyl titanate, butyl titanate, propyl titanate or isopropyl titanate; the silicon source comprises ethyl orthosilicate, propyl orthosilicate or methyl orthosilicate; the solvent comprises ethanol, methanol, isopropanol or acetone.
5. The method for preparing the double-layer coated silica composite anode material according to claim 1, wherein: in the step (1), the mass ratio of the titanium dioxide to the silicon source is 10 (1 to 3).
6. The method for preparing the double-layer coated silica composite anode material according to claim 1, wherein: in the step (2), the stirring time is 0.5 to 2h, the sintering temperature is 400 to 600 ℃, the heating rate is 5 to 10 ℃/min, and the sintering time is 2 to 6h.
7. The method for preparing the double-layer coated silica composite anode material according to claim 1, wherein: in the step (3), the particle size of the silica powder is 3 to 6 mu m, and the mass ratio of the silica powder to the silicon-doped titanium dioxide is 10 (0.5 to 2).
8. The method for preparing the double-layer coated silica composite anode material according to claim 1, wherein: and (3) drying by adopting an air-blast drying box at the drying temperature of 50-80 ℃, calcining at high temperature in a tubular furnace in inert gas, wherein the inert gas is nitrogen or argon, the heating rate is 5 ℃/min, the sintering temperature is 700-900 ℃, the sintering time is 2-4 h, and naturally cooling.
9. The method for preparing the double-layer coated silica composite anode material according to claim 1, wherein: in the step (4), the mass of aniline monomer accounts for 3% -10% of that of the titanium dioxide coated silica, the concentration of hydrochloric acid is 1% -3M, and the mass ratio of aniline monomer to ammonium persulfate is 1 (3% -5).
10. The preparation method of the double-layer coated silica composite anode material according to claim 1, characterized in that: in the step (4), a tubular furnace is adopted to carry out high-temperature calcination in inert gas, the inert gas is nitrogen or argon, the heating rate is 5 ℃/min, the sintering temperature is 700 to 900 ℃, the sintering time is 2 to 4h, and the temperature is naturally cooled.
CN202211465313.5A 2022-11-22 2022-11-22 Double-layer coated silicon monoxide composite negative electrode material and preparation method thereof Pending CN115513445A (en)

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