CN109638231B - Silicon monoxide composite negative electrode material, preparation method thereof and lithium ion battery - Google Patents

Silicon monoxide composite negative electrode material, preparation method thereof and lithium ion battery Download PDF

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CN109638231B
CN109638231B CN201710928595.0A CN201710928595A CN109638231B CN 109638231 B CN109638231 B CN 109638231B CN 201710928595 A CN201710928595 A CN 201710928595A CN 109638231 B CN109638231 B CN 109638231B
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negative electrode
electrode material
shell
composite negative
silicon
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CN109638231A (en
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钟辉
张伟
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Cabot High Performance Materials Zhuhai 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • 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
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/386—Silicon or alloys based on silicon
    • 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
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • 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
    • 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
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • 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
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    • 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

Abstract

The invention relates to the technical field of lithium ion battery cathode materials, and particularly provides a silicon oxide composite cathode material, a preparation method thereof and a lithium ion battery. The silicon monoxide composite negative electrode material is a material with a core-shell structure; the core part comprises nano-silicon and has a chemical formula of SiOxWherein x is not less than 0.6 and not more than 1.1, and the nano-silicon is uniformly distributed in the SiOxPerforming the following steps; the shell part comprises a first shell and a second shell, the first shell is coated on the surface of the core, and the first shell is of a chemical formula of SiOyWherein y is not less than 1.5 and not more than 2.0; the second shell is coated on the surface of the first shell, and the second shell is made of conductive carbon. The silicon monoxide composite negative electrode material provided by the invention has the advantages of good structure stability and small expansion rate, and when the silicon monoxide composite negative electrode material is used for a lithium ion battery negative electrode, the lithium ion battery shows good electrochemical performance.

Description

Silicon monoxide composite negative electrode material, preparation method thereof and lithium ion battery
Technical Field
The invention belongs to the technical field of lithium ion battery cathode materials, and particularly relates to a silicon monoxide composite cathode material, a preparation method thereof and a lithium ion battery.
Background
With the development of society, the demand for the operation time of electronic products (mobile phones, computers, portable electronic products, etc.) and electric tools (electric bicycles, electric automobiles, etc.) after the batteries are charged once is longer and longer, and the energy density of the used lithium ion batteries is required to be higher and higher.
At present, the silicon-based negative electrode material is considered to be a material which is very effective for improving the energy density of the lithium ion battery, mainly because the theoretical capacity (3580mAh/g) of silicon is far higher than that (372mAh/g) of the conventional graphite negative electrode material. However, when the silicon-based negative electrode material is made into a lithium ion battery, the silicon-based negative electrode material expands/contracts greatly in the charge-discharge cycle process, so that the stability of the material and a pole piece is poor, an active substance is easy to be pulverized and lose electric contact activity, and even falls off from the surface of the pole piece, so that the cycle performance of the lithium ion battery is finally poor.
The expansion/contraction amplitude of the silicon oxide negative electrode material generated during charge and discharge is smaller than that of other silicon-based negative electrode materials (silicon alloy, silicon film, silicon/carbon and the like), so that relatively good cycle performance can be obtained to a certain extent, but the expansion/contraction of the silicon oxide negative electrode material is still greatly higher than that of the graphite negative electrode material, and the conductivity is lower, so that the application of the silicon oxide in the lithium ion battery is restricted.
Chinese patent with application number 201410268192.4 discloses a silicon monoxide composite negative electrode material of a lithium ion battery, a preparation method and application thereof. The silicon oxide composite negative electrode material consists of micron-sized silicon oxide powder and a carbon layer uniformly and densely coated on the surface of the silicon oxide powder, wherein the carbon layer mainly takes high molecules as precursors and is formed on the surface of the silicon oxide powder by a solid-phase coating method. The solid-phase coating carbon layer is carried out on the surfaces of the micron-sized particles, the carbon layer is difficult to uniformly coat the surfaces of the micron-sized particles, and partial surfaces of the particles are still exposed outside. The exposed silicon monoxide is easy to contact with electrolyte, and more irreversible reactions are generated during charging and discharging, so that the cycle performance is poor.
Chinese patent with application number 201510026862.6 discloses a silicon monoxide composite negative electrode material of a lithium ion battery, a preparation method and application thereof. The silicon monoxide composite cathode material has a chemical formula of SiOx(0.9<x<1.1) and a conductive carbon coating layer, wherein the conductive carbon coating layer is generated through vapor deposition, the carbon layer has good uniformity for coating the silicon oxide powder, but data in the patent show that the capacity retention rate is lower than 70% after 50 cycles of the silicon oxide composite material half-cell test, and the cycle performance is poor. This may be related to the internal structure of the conductive carbon layer and the silicon oxide, such as the low conductivity of the conductive carbon layer, the large size and uneven distribution of nano-silicon in the silicon oxide.
Disclosure of Invention
The invention provides a silicon oxide composite negative electrode material and a preparation method thereof, aiming at the problems of poor cycle performance of a lithium ion battery and the like caused by large expansion rate, poor material conductivity and the like in the charging and discharging processes of the existing silicon oxide composite negative electrode material.
Furthermore, the invention also provides a lithium ion battery.
The invention is realized by the following steps:
the silicon oxide composite negative electrode material is a material with a core-shell structure;
the core part comprises nano-silicon and has a chemical formula of SiOxWherein x is not less than 0.6 and not more than 1.1, and the nano-silicon is uniformly distributed in the SiOxPerforming the following steps;
the shell part comprises a first shell and a second shell, the first shell is coated on the surface of the core, and the first shell is of a chemical formula of SiOyWherein y is not less than 1.5 and not more than 2.0; the second shell is coated on the surface of the first shell, and the second shell is made of conductive carbon.
Correspondingly, the preparation method of the silicon monoxide composite negative electrode material at least comprises the following steps:
step S01, providing a chemical formula of SiOxWherein x is not less than 0.6 and not more than 1.1;
step S02, heating and oxidizing the silicon oxide powder obtained in the step S01 in an oxidizing agent atmosphere to make part of the silicon oxide powder have a chemical formula of SiOxIs converted into SiOyWherein y is not less than 1.5 and not more than 2.0;
and S03, performing surface carbon coating treatment on the product obtained in the step S02 to obtain the silicon oxide composite negative electrode material.
Furthermore, the lithium ion battery comprises a negative electrode material, wherein the negative electrode material is the silicon oxide composite negative electrode material or the silicon oxide composite negative electrode material prepared by the preparation method of the silicon oxide composite negative electrode material.
Compared with the prior art, the silicon oxide composite negative electrode material provided by the invention has the advantages that the nano silicon in the silicon oxide composite negative electrode material is dispersed in the SiO corex(0.6. ltoreq. x. ltoreq.1.1) in the core tableThe surface is formed with two layers of shell, the first shell is SiOy(y is more than or equal to 1.5 and less than or equal to 2.0), the second shell is a conductive carbon layer, and the two shells can thoroughly avoid direct contact of the silicon monoxide and the electrolyte on one hand, and can effectively buffer expansion/contraction of the core during charge and discharge, ensure the stability of the structure of the silicon monoxide composite negative electrode material, and inhibit the cracking of a Solid Electrolyte Interface (SEI) film on the surface of the silicon monoxide composite negative electrode material during charge and discharge; and the conductivity of the second shell conductive carbon layer is higher, so that the particle of the silicon oxide composite negative electrode material has good electrical contact activity, and therefore, when the silicon oxide composite negative electrode material is prepared into a lithium ion battery, the lithium ion battery shows excellent cycle performance.
According to the preparation method of the silicon oxide composite negative electrode material, the prepared silicon oxide composite negative electrode material forms a core double-layer shell structure, and the preparation method is simple and rapid and is suitable for large-scale industrial production.
The silicon monoxide composite negative electrode material provided by the invention has the characteristics of small expansion rate, good structural stability, good conductivity and the like, and when the silicon monoxide composite negative electrode material is used as a negative electrode material of a lithium ion battery, the lithium ion battery shows excellent cycle performance.
Drawings
In order to more clearly illustrate the technical solutions in the embodiments of the present invention, the drawings needed to be used in the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art that other drawings can be obtained according to these drawings without creative efforts.
FIG. 1 is a schematic structural view of a cross section of a silicon oxide composite negative electrode material of the present invention;
FIG. 2 is an SEM image of a SiOx composite negative electrode material obtained in example 1 of the present invention;
FIG. 3 is an XRD pattern of a silica composite negative electrode material obtained in example 1 of the present invention;
FIG. 4 is a graph of powder conductivity at different compaction densities for a composite negative electrode material of silica made in example 1 of the present invention;
FIG. 5 is a first charge-discharge curve diagram of the SiOx composite negative electrode material obtained in example 1 of the present invention;
FIG. 6 is a TG curve of the SiOx composite negative electrode material obtained in example 1 of the present invention, which is raised from room temperature to 800 ℃ at 10 ℃/min in an air atmosphere.
Wherein, in FIG. 1, 1-nanometer silicon; 2-SiOx；3-SiOy(ii) a 4-conductive carbon.
Detailed Description
In order to make the technical problems, technical solutions and advantageous effects to be solved by the present invention more clearly understood, the present invention is further described in detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Referring to fig. 1, an embodiment of the present invention provides a silicon oxide composite negative electrode material.
The silicon monoxide composite negative electrode material is a material with a core-shell structure, wherein the core part of the core-shell structure contains nano-silicon and has a chemical formula of SiOxWherein x is not less than 0.6 and not more than 1.1;
the shell part of the core-shell structure comprises a first shell and a second shell, the first shell is coated on the surface of the core, and the first shell is SiOyWherein y is not less than 1.5 and not more than 2.0; the second shell is coated on the surface of the first shell, and the second shell is made of conductive carbon.
The silica composite anode material of the present invention is further explained below.
In any embodiment, the silicon monoxide composite negative electrode material is composed of a core, a first shell and a second shell which are sequentially formed from the core to the outside, the first shell and the second shell are used for completely coating the core, and the second shell coats the first shell, so that direct contact between the silicon monoxide and an electrolyte is avoided, and irreversible reaction of negative electrodes in some lithium ion batteries is avoided. The core is partially covered by a first shell and a second shellAnd the body is coated, so that the structure of the silicon monoxide composite negative electrode material is stable. The nano-silicon in the core is uniformly distributed in the chemical formula of SiOxIn the silica powder of (3).
Preferably, the particle size of the silicon oxide composite negative electrode material is 0.5-20 μm, and the D50 is 4-8 μm.
In the silicon monoxide composite negative electrode material, the SiOyAccounting for 2 to 6 percent of the mass of the silicon monoxide composite negative electrode material; the conductive carbon accounts for 1-10% of the mass of the silicon monoxide composite negative electrode material, and the balance of nano silicon and SiOxThe content of (b) is not particularly limited, but cannot be zero. When SiO is presentyWhen the ratio is less than 2 percent, the chemical formula is SiOyThe silicon monoxide does not play a role in buffering the expansion of the core, and when the content is higher than 6 percent, the capacity and the first-week coulombic efficiency of the silicon monoxide composite material are reduced; when the conductive carbon content is less than 1%, the outermost layer of the particles is difficult to be coated with the conductive carbon, and when the conductive carbon content is more than 10%, the capacity and the first-cycle coulombic efficiency of the silicon monoxide composite material are reduced.
Preferably, the particle size of the nano silicon is 3 nm-8 nm, the particle size of the nano silicon is less than 3nm, the disproportionation reaction is insufficient, and the improvement of the cycle performance is not facilitated; the particle size of the nano silicon is larger than 8nm, the structural stability is poor during charge-discharge circulation, and the circulation performance is poor.
Further preferably, in the silicon oxide composite negative electrode material, when the conductive carbon accounts for 5% of the mass of the silicon oxide composite negative electrode material and the compacted density of the silicon oxide composite negative electrode material is 1.5g/cm3The specific conductivity range is 2S/cm-6S/cm, when the specific conductivity is lower than 2S/cm, the polarization is large, and the prepared lithium ion battery has low capacity and poor cycle electrochemical performance; when the conductivity is higher than 6S/cm, the crystallinity of the conductive carbon is too high, which is not beneficial to the entering of lithium ions, and is not beneficial to the buffer expansion and contraction, and the cycle performance is poor.
The nano silicon has the chemical formula of SiOxWherein x is more than or equal to 0.6 and less than or equal to 1.1, and the silicon monoxide powder is obtained by disproportionation reaction.
The embodiment of the invention provides a silicon monoxide composite negative electrodeThe nano silicon in the electrode material, the silicon oxide composite cathode material is dispersed in the SiO corex(x is more than or equal to 0.6 and less than or equal to 1.1), two shells are formed on the surface of the core, and the first shell is of a chemical formula of SiOyY is more than or equal to 1.5 and less than or equal to 2.0, the second shell is a conductive carbon layer, and the two shells can thoroughly avoid the direct contact of the silicon oxide and the electrolyte on one hand, and can effectively buffer the expansion/contraction of the core during charge and discharge, thereby ensuring the stability of the structure of the silicon oxide composite negative electrode material and inhibiting the cracking of a Solid Electrolyte Interface (SEI) film on the surface of the silicon oxide composite negative electrode material during charge and discharge; and the conductivity of the second shell conductive carbon layer is higher, so that the particle of the silicon oxide composite negative electrode material has good electrical contact activity, and therefore, when the silicon oxide composite negative electrode material is prepared into a lithium ion battery, the lithium ion battery shows excellent cycle performance.
On the premise of providing the silicon monoxide composite negative electrode material, the invention further provides a preparation method of the silicon monoxide composite negative electrode material.
In one embodiment, the preparation method of the silicon monoxide composite negative electrode material at least comprises the following steps:
step S01, providing a chemical formula of SiOxWherein x is not less than 0.6 and not more than 1.1;
step S02, heating and oxidizing the silicon oxide powder obtained in the step S01 in an oxidizing agent atmosphere to make part of the silicon oxide powder have a chemical formula of SiOxIs converted into SiOyWherein y is not less than 1.5 and not more than 2.0;
and S03, performing surface carbon coating treatment on the product obtained in the step S02 to obtain the silicon oxide composite negative electrode material.
In order to better understand the preparation method, the preparation method is further explained below.
Chemical formula is SiOxThe raw material of the silicon monoxide powder can be the existing material with x being more than or equal to 0.6 and less than or equal to 1.1, and the chemical formula with the particle size distribution of 1mm-60mm is SiOxThe above-mentioned silica powder is obtained by grinding.
In the grinding, one or more of a planetary ball mill, a jaw crusher, a roller crusher, a low-temperature crusher and a jet mill may be used.
Whether using existing materials or grinding, the final chemical formula is SiOxWherein x is more than or equal to 0.6 and less than or equal to 1.1 is 0.5-20 μm, and D50 is 4-8 μm.
The chemical formula of the invention is SiOxWherein 0.6. ltoreq. x.ltoreq.1.1, as a core, is subjected to thermal oxidation treatment to obtain a silicon oxide powder having a chemical formula of SiOxIs converted into SiOyWherein y is 1.5. ltoreq. y.ltoreq.2.0, the part of the silica powder becoming the first shell; chemical formula is SiOxThe temperature of the disproportionation reaction of the silicon monoxide to generate the nano silicon is over 800 ℃, and the chemical formula of the uniformly distributed nano silicon in the interior is SiOxThe silicon oxide of (a) is a core part of the silicon oxide composite negative electrode material. Therefore, the temperature of the heating oxidation treatment is preferably 300 to 1000 ℃ and the time is preferably 1 to 100 min. If nano-silicon is not generated in the thermal oxidation treatment stage, nano-silicon is also generated in the subsequent carbon coating as long as the temperature of the carbon coating exceeds 800 ℃.
Preferably, the oxidant is any one of air, oxygen, and carbon dioxide.
And (4) obtaining a second shell by surface carbon coating in the step (S03), so that in the obtained silicon oxide composite cathode material, the silicon oxide is completely coated by the coated conductive carbon, and the silicon oxide is prevented from being exposed, thereby preventing the silicon oxide from directly contacting with the electrolyte to generate irreversible reaction when the lithium ion battery is manufactured.
Preferably, the carbon-coated carbon source on the surface is CnHn+2(n-1, 2, 3) or toluene.
In the coating process, a chemical vapor deposition method is preferable. The chemical vapor deposition method can realize the uniform carbon coating on the surface of the first shell and avoid the formation of a non-uniform second shell layer.
Preferably, the temperature of the chemical vapor deposition is 700-1100 ℃, the deposition time is 10-300 min, and the deposition ambient pressure of the chemical vapor deposition method is 50-120000 Pa. In order to ensure that nano-silicon is generated in the silicon monoxide, when the temperature of the thermal oxidation treatment does not exceed 800 ℃, the temperature of chemical vapor deposition for a period of time is ensured to exceed 800 ℃ during the carbon coating process, because the temperature exceeds 800 ℃, the nano-silicon is generated, and the higher the temperature is, the faster the nano-silicon is generated, and the faster the grain size of the nano-silicon is grown.
Further preferably, the chemical vapor deposition method adopts one of a rotary kiln and a fluidized bed.
In order to avoid introducing impurities such as iron in the preparation process, after the silicon monoxide composite negative electrode material is obtained, the magnetic field removal and sieving treatment should be carried out.
According to the preparation method of the silicon monoxide composite negative electrode material, the prepared silicon monoxide composite negative electrode material forms a core double-layer shell structure, the core is spherical, and the nano silicon in the core is uniformly dispersed, so that the large expansion caused by the aggregation of the nano silicon is avoided; the preparation method is simple and quick, and is suitable for large-scale industrial production.
Correspondingly, still further provide a lithium ion battery.
In an embodiment, the lithium ion battery comprises a negative electrode material, and the negative electrode material is the silicon oxide composite negative electrode material or the silicon oxide composite negative electrode material prepared by the preparation method of the silicon oxide composite negative electrode material.
Other positive electrode materials, separators and electrolytes of the lithium ion battery are well known in the art, and will not be described in detail herein for the sake of brevity.
The silicon monoxide composite negative electrode material provided by the invention has the characteristics of small expansion rate, good structural stability and the like, so that when the silicon monoxide composite negative electrode material is used as a negative electrode material of a lithium ion battery, the obtained lithium ion battery shows excellent cycle performance.
In order to better explain the technical solution of the present invention, the following description is made with reference to a plurality of specific examples.
Example 1
The silicon monoxide composite negative electrode material with the core-shell structure is characterized in that the core part comprises nano silicon and SiOxWherein x is not less than 0.6 and not more than 1.1, and the nano-silicon is uniformly distributed in the SiOxPerforming the following steps;
the shell part comprises a first shell and a second shell, the first shell is coated on the surface of the core, and the first shell is of a chemical formula of SiOyWherein y is not less than 1.5 and not more than 2.0; the second shell is coated on the surface of the first shell, and the second shell is made of conductive carbon.
The preparation method of the silicon oxide composite negative electrode material comprises the following steps:
(1) 500g of SiO with the grain diameter of 1mm-60mm and the chemical formulax(x is more than or equal to 0.6 and less than or equal to 1.1) treating the silicon oxide powder by a jaw crusher, and then carrying out air crushing by a jet mill to obtain the silicon oxide powder with the granularity range of 0.5-20 mu m;
(2) placing the silicon monoxide powder obtained in the step (1) in a rotary furnace, heating to 300 ℃, introducing oxygen with the oxygen flow of 200mL/min, keeping the temperature for 20min, stopping introducing oxygen, and cooling to room temperature;
(3) placing the product obtained in the step (2) in a rotary furnace, heating to 1100 ℃, charging methane with the methane flow of 1L/min, keeping the temperature for 60min, stopping charging methane, and cooling to room temperature;
(4) and (4) carrying out demagnetization treatment on the product obtained in the step (3), and screening the product by using a 320-mesh screen to obtain the silicon monoxide composite negative electrode material.
And performing electron microscope scanning, XRD and TG tests, powder conductivity tests under different compaction densities and first charge and discharge tests after the obtained silicon monoxide composite negative electrode material is prepared into a lithium ion battery, wherein the test results are shown in figures 2-6.
Wherein FIG. 2 is an SEM image of the negative electrode material of the composite silica prepared in example 1, and it can be seen from FIG. 2 that the particle size of the negative electrode material of the composite silica is in the range of 1 μm to 15 μm.
FIG. 3 is an XRD pattern of a silica composite anode material prepared in example 1. As can be seen from fig. 3, the nano-silicon size in the negative silica composite electrode material was calculated to be 6.2nm from the half-peak width of the characteristic peak of silicon (111 plane) by the scherrer equation D ═ k λ/β cos θ.
FIG. 4 is a graph of powder conductivity at different compaction densities for the siliconoxide composite anode material prepared in example 1. As can be seen from FIG. 4, the concentration of the compound is 1.5g/cm3The electrical conductivity of the negative electrode material of the silicon oxide composite prepared in the following example 1 was 2.86S/cm.
FIG. 5 is a first cycle charge and discharge curve of the negative electrode material of the silicon oxide composite obtained in example 1. As can be seen from fig. 5, the first reversible capacity of the negative electrode material of the composite of silica prepared in example 1 was 1656mAh/g, and the first coulombic efficiency was 75.2%.
FIG. 6 is a TG curve of the SiOx composite negative electrode material obtained in example 1, which is raised from room temperature to 800 ℃ at 10 ℃/min in an air atmosphere. As can be seen from fig. 6, the conductive carbon content of the negative electrode material of the silicon oxide composite obtained in example 1 was about 4.8% by mass.
Example 2
The silicon monoxide composite negative electrode material with the core-shell structure is characterized in that the core part comprises nano silicon and SiOxWherein x is not less than 0.6 and not more than 1.1, and the nano-silicon is uniformly distributed in the SiOxPerforming the following steps;
the shell part comprises a first shell and a second shell, the first shell is coated on the surface of the core, and the first shell is of a chemical formula of SiOyWherein y is not less than 1.5 and not more than 2.0; the second shell is coated on the surface of the first shell, and the second shell is made of conductive carbon.
The preparation method of the silicon oxide composite negative electrode material comprises the following steps:
(1) 1kg of SiO with the grain diameter of 1 mm-20 mm and the chemical formulax(x is more than or equal to 0.6 and less than or equal to 1.1) treating the raw material of the silicon oxide powder by a planet ball mill, and then carrying out air crushing by a jet mill to obtain the silicon oxide powder with the granularity range of 0.5-20 mu m;
(2) placing the silicon monoxide powder obtained in the step (1) in a box-type furnace, heating to 450 ℃, filling air with the air flow rate of 100mL/min, keeping the temperature for 10min, stopping filling the air, and cooling to room temperature;
(3) putting the product obtained in the step (2) into a rotary furnace, heating to 950 ℃, filling methane, keeping the methane flow at 1.5L/min, keeping the temperature for 120min, stopping filling methane, and cooling to room temperature;
(4) and (4) carrying out demagnetization treatment on the obtained product in the step (3), and screening the product by using a 320-mesh screen to obtain the silicon monoxide composite negative electrode material.
Example 3
The silicon monoxide composite negative electrode material with the core-shell structure is characterized in that the core part comprises nano silicon and SiOxWherein x is not less than 0.6 and not more than 1.1, and the nano-silicon is uniformly distributed in the SiOxPerforming the following steps;
the shell part comprises a first shell and a second shell, the first shell is coated on the surface of the core, and the first shell is of a chemical formula of SiOyWherein y is not less than 1.5 and not more than 2.0; the second shell is coated on the surface of the first shell, and the second shell is made of conductive carbon.
The preparation method of the silicon oxide composite negative electrode material comprises the following steps:
(1) 10kg of a material with the grain diameter of 1 mm-3 mm and the chemical formula of SiOx(x is more than or equal to 0.6 and less than or equal to 1.1) performing gas crushing on the raw material of the silicon oxide powder by a jet mill to obtain the silicon oxide powder with the granularity range of 0.5-20 mu m;
(2) placing the silicon monoxide powder obtained in the step (1) in a push plate furnace, heating to 400 ℃, charging air with the air flow rate of 200mL/min, keeping the temperature for 60min, stopping charging air, and cooling to room temperature;
(3) putting the product obtained in the step (2) into a rotary furnace, heating to 900 ℃, filling ethane with the ethane flow rate of 0.5L/min, keeping the temperature for 300min, stopping filling ethane, and cooling to room temperature;
(4) and (4) carrying out demagnetization treatment on the product obtained in the step (3), and screening the product by using a 320-mesh screen to obtain the silicon monoxide composite negative electrode material.
Example 4
The silicon monoxide composite negative electrode material with the core-shell structure is characterized in that the core part comprises nano silicon and SiOxWherein x is not less than 0.6 and not more than 1.1, and the nano-silicon is uniformly distributed in the SiOxPerforming the following steps;
the shell part comprises a first shell and a second shell, the first shell is coated on the surface of the core, and the first shell is of a chemical formula of SiOyWherein y is not less than 1.5 and not more than 2.0; the second shell is coated on the surface of the first shell, and the second shell is made of conductive carbon.
The preparation method of the silicon oxide composite negative electrode material comprises the following steps:
(1) 2kg of SiO with the grain diameter of 20-60 mm and the chemical formulax(x is more than or equal to 0.6 and less than or equal to 1.1) treating the raw material of the silicon powder of the silicon oxide by a jaw crusher, a roller crusher and a jet mill in sequence to obtain the silicon oxide powder with the granularity range of 0.5 to 20 mu m;
(2) placing the silicon monoxide powder obtained in the step (1) in a rotary furnace, heating to 1000 ℃, introducing carbon dioxide with the carbon dioxide flow of 100mL/min, keeping the temperature for 100min, stopping introducing the carbon dioxide, and cooling to room temperature;
(3) placing the product obtained in the step (2) in a rotary furnace, heating to 700 ℃, filling toluene by taking nitrogen as carrier gas, keeping the flow rate of the carrier gas at 0.2L/min, keeping the temperature for 150min, stopping filling propane, and cooling to room temperature;
(4) and (4) carrying out demagnetization treatment on the product obtained in the step (3), and screening the product by using a 320-mesh screen to obtain the silicon monoxide composite negative electrode material.
Example 5
The silicon monoxide composite negative electrode material with the core-shell structure is characterized in that the core part comprises nano silicon and SiOxWherein x is not less than 0.6 and not more than 1.1, and the nano-silicon is uniformly distributed in the SiOxPerforming the following steps;
the housing portions include a first housing and a second housing,the first shell is coated on the surface of the core, and the chemical formula of the first shell is SiOyWherein y is not less than 1.5 and not more than 2.0; the second shell is coated on the surface of the first shell, and the second shell is made of conductive carbon.
The preparation method of the silicon oxide composite negative electrode material comprises the following steps:
(1) 50kg of SiO with the grain diameter of 20-60 mm and the chemical formulax(x is more than or equal to 0.6 and less than or equal to 1.1) treating the raw material of the silicon oxide powder by a jaw crusher and a jet mill in sequence to obtain the silicon oxide powder with the granularity range of 0.5-20 mu m;
(2) placing the silicon monoxide powder obtained in the step (1) in a rotary furnace, heating to 900 ℃, introducing carbon dioxide with the carbon dioxide flow rate of 300mL/min, keeping the temperature for 90min, stopping introducing the carbon dioxide, and cooling to room temperature;
(3) placing the product obtained in the step (2) in a fluidized bed, heating to 800 ℃, increasing the pressure of a reaction chamber to 120000Pa, filling propane, keeping the flow rate of the propane at 1L/min, keeping the temperature for 80min, stopping filling the propane, and cooling to room temperature;
(4) and (4) carrying out demagnetization treatment on the product obtained in the step (3), and screening the product by using a 320-mesh screen to obtain the silicon monoxide composite negative electrode material.
Example 6
The silicon monoxide composite negative electrode material with the core-shell structure is characterized in that the core part comprises nano silicon and SiOxWherein x is not less than 0.6 and not more than 1.1, and the nano-silicon is uniformly distributed in the SiOxPerforming the following steps;
the shell part comprises a first shell and a second shell, the first shell is coated on the surface of the core, and the first shell is of a chemical formula of SiOyWherein y is not less than 1.5 and not more than 2.0; the second shell is coated on the surface of the first shell, and the second shell is made of conductive carbon.
The preparation method of the silicon oxide composite negative electrode material comprises the following steps:
(1) 100kg of a material with the grain diameter of 1mm-60mm and the chemical formula of SiOx(x is more than or equal to 0.6 and less than or equal to 1.1)Treating the raw material of the silicon oxide powder by a jaw crusher and a low-temperature crusher in sequence to obtain the silicon oxide powder with the granularity range of 0.5-20 mu m;
(2) placing the silicon monoxide powder obtained in the step (1) in a roller kiln, heating to 350 ℃, charging air with the air flow rate of 500mL/min, keeping the temperature for 20min, stopping charging air, and cooling to room temperature;
(3) placing the product obtained in the step (2) in a fluidized bed, heating to 1100 ℃, reducing the pressure of a reaction chamber to 50Pa, filling methane with the flow rate of 2L/min, keeping the temperature for 200min, stopping filling methane, and reducing the temperature to room temperature;
(4) and (4) carrying out demagnetization treatment on the product obtained in the step (3), and screening the product by using a 320-mesh screen to obtain the silicon monoxide composite negative electrode material.
Comparative example 1
A preparation method of a silica composite negative electrode material with a core-shell structure comprises the following steps:
(1) treating 10kg of a silicon monoxide raw material with the particle size of 1-60 mm by a jaw crusher, a roller crusher and a jet mill in sequence to obtain silicon monoxide powder with the particle size range of 0.5-20 microns;
(2) placing the silicon monoxide powder in a rotary furnace, heating to 1000 ℃, introducing nitrogen with the flow rate of 100mL/min, keeping the temperature for 100min, stopping introducing the nitrogen, and cooling to room temperature;
(3) putting the product obtained in the step (2) into a rotary furnace, heating to 700 ℃, filling propane, keeping the propane flow at 0.2L/min, keeping the temperature for 150min, stopping filling propane, and cooling to room temperature;
(4) and (4) carrying out demagnetization treatment on the product obtained in the step (3), and screening the product by using a 320-mesh screen to obtain the silicon monoxide composite negative electrode material.
Comparative example 2
The preparation method of the silica composite anode material with the core-shell structure comprises the following steps
(1) 500g of a silica raw material with the grain diameter of 1mm-60mm is firstly treated by a jaw crusher and then is subjected to air crushing by a jet mill, so as to obtain silica powder with the grain size range of 0.5 mu m-20 mu m;
(2) putting the silicon monoxide obtained in the step (1) into a rotary furnace, heating to 1000 ℃, charging methane with the methane flow of 1L/min, keeping the temperature for 60min, stopping charging methane, and cooling to room temperature to obtain a product 3;
(3) and (3) carrying out demagnetization treatment on the product obtained in the step (2), and screening the product by using a 320-mesh screen to obtain the silicon monoxide composite negative electrode material.
In order to verify the electrochemical performance of the negative electrode materials of the silicon oxide composite prepared in examples 1 to 6 and comparative examples 1 to 2, the negative electrode materials of the silicon oxide composite prepared in examples 1 to 6 and comparative examples 1 to 2 were prepared into batteries, and the batteries were manufactured as follows:
the silicon oxide composite negative electrode material comprises the following components in percentage by weight: CMC: SBR: weighing the components of the conductive agent Super-P (86: 3:5: 6), adding a proper amount of deionized water as a dispersing agent, mixing into slurry, coating the slurry on a copper foil, and preparing a pole piece through vacuum drying, rolling and punching;
counter electrode: a metallic lithium plate;
electrolyte solution: 1.2mol/L LiPF6The three-component mixed solvent of (1), wherein the volume ratio of the three-component mixed solvent is EC: DMC: FEC ═ 4:5.5: 0.5;
a diaphragm: a polypropylene microporous membrane;
the battery model is as follows: a CR2016 button cell;
the test method comprises the following steps: in the cycle performance test, constant current discharge is carried out to 0.01V by using a current density of 150mA/g, constant voltage is carried out to 15mA/g by using 0.01V, and then constant current charging is carried out to 1.5V by using 150 mA/g;
expansion ratio test method: the expansion rate is (thickness of pole piece after 50 cycles-thickness of pole piece before cycle)/(thickness of pole piece before cycle-thickness of copper foil) x 100%.
Table 1 is a table of electrochemical properties of the negative electrode materials of the silicon oxide composite prepared in the examples and comparative examples
Figure BDA0001428173440000141
As can be seen from table 1, the lithium ion battery prepared from the material of example 1 maintains 82.4% of capacity and 165% of expansion of the pole piece after 50 cycles;
after 50 cycles, the capacity retention rate of the lithium ion battery prepared from the material in the embodiment 2 is 83.6%, and the expansion of the pole piece is 163%;
after 50 cycles, the capacity retention rate of the lithium ion battery prepared from the material in the embodiment 3 is 83.7%, and the expansion of the pole piece is 161%;
after 50 cycles, the capacity retention rate of the lithium ion battery prepared from the material in the embodiment 4 is 84.8%, and the expansion of the pole piece is 168%;
after 50 cycles, the capacity retention rate of the lithium ion battery prepared from the material in the embodiment 5 is 83.4%, and the expansion of the pole piece is 160%;
after 50 cycles, the capacity retention rate of the lithium ion battery prepared from the material in the embodiment 6 is 83.1%, and the expansion of the pole piece is 174%;
after 50 cycles, the capacity retention rate of the lithium ion battery prepared from the material of the comparative example 1 is 73.1%, and the expansion rate of the pole piece is 182%;
the capacity retention rate of the lithium ion battery prepared from the material of the comparative example 2 is 70.3 percent after 50 times of circulation, and the expansion of the pole piece is 186 percent;
it is clear that examples 1 to 6 all exhibited excellent cycle performance and small expansion ratio, while comparative examples 1 to 2 exhibited poor cycle performance and large expansion ratio.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.

Claims (9)

1. A silicon oxide composite negative electrode material is characterized in that: the silicon oxide composite negative electrode material is a material with a core-shell structure, and consists of a core, a first shell and a second shell which are sequentially formed from the core to the outside;
the core part comprises nano-silicon and has a chemical formula of SiOxWherein x is not less than 0.6 and not more than 1.1, and the nano-silicon is uniformly distributed in the SiOxPerforming the following steps;
the shell part comprises a first shell and a second shell, the first shell is coated on the surface of the core, and the first shell is of a chemical formula of SiOyWherein y is not less than 1.5 and not more than 2.0; the second shell is coated on the surface of the first shell, and the second shell is made of conductive carbon;
the SiOyAccounting for 2 to 6 percent of the mass of the silicon monoxide composite negative electrode material; the conductive carbon accounts for 1-10% of the mass of the silicon monoxide composite negative electrode material.
2. The silica composite negative electrode material according to claim 1, wherein: when the conductive carbon accounts for 5% of the mass of the silicon oxide composite negative electrode material and the compaction density of the silicon oxide composite negative electrode material is 1.5g/cm3The range of the conductivity is 2S/cm to 6S/cm.
3. The silica composite negative electrode material according to claim 1, wherein: the particle size of the silicon monoxide composite negative electrode material is 0.5-20 μm, and the D50 is 4-8 μm; and/or the particle size of the nano silicon is 3 nm-8 nm.
4. A method for preparing the negative electrode material of silicon oxide composite according to any one of claims 1 to 3, characterized in that: at least comprises the following steps:
step S01, providing a chemical formula of SiOxWherein x is not less than 0.6 and not more than 1.1;
step S02, heating and oxidizing the silicon oxide powder obtained in the step S01 in an oxidizing agent atmosphere to make part of the silicon oxide powder have a chemical formula of SiOxIs converted into SiOyWherein y is not less than 1.5 and not more than 2.0;
and S03, performing surface carbon coating treatment on the product obtained in the step S02 to obtain the silicon oxide composite negative electrode material.
5. The negative electrode of claim 4, wherein the negative electrode is a silicon oxide composite negative electrodeThe preparation method of the material is characterized by comprising the following steps: the chemical formula is SiOxThe particle size of the silicon oxide powder is 0.5-20 μm; and/or the temperature of the heating oxidation treatment is 300-1000 ℃ and the time is 1-100 min.
6. The method for producing the silica composite negative electrode material according to claim 4, characterized in that: the oxidant is any one of air, oxygen and carbon dioxide.
7. The method for producing the silica composite negative electrode material according to claim 4, characterized in that: the surface carbon is coated with CnHn+2Wherein n is 1, 2, 3, or toluene, and the product of step S02 is coated by using a chemical vapor deposition method.
8. The method for producing the silica composite negative electrode material according to claim 7, wherein: the temperature of the chemical vapor deposition is 700-1100 ℃, the deposition time is 10-300 min, and the deposition pressure of the chemical vapor deposition method is 50-120000 Pa.
9. A lithium ion battery comprising an anode material, characterized in that: the negative electrode material is the silicon oxide composite negative electrode material as defined in any one of claims 1 to 3 or the silicon oxide composite negative electrode material prepared by the preparation method of the silicon oxide composite negative electrode material as defined in any one of claims 4 to 8.
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