CN112661163B - Silica-based composite anode material, preparation method thereof and lithium ion battery - Google Patents

Silica-based composite anode material, preparation method thereof and lithium ion battery Download PDF

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CN112661163B
CN112661163B CN202011565055.9A CN202011565055A CN112661163B CN 112661163 B CN112661163 B CN 112661163B CN 202011565055 A CN202011565055 A CN 202011565055A CN 112661163 B CN112661163 B CN 112661163B
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stirring
micron
silica
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CN112661163A (en
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张正裕
付炳杰
邓铭声
黄新萍
李军
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Guangdong University of Technology
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    • Y02E60/10—Energy storage using batteries

Abstract

The invention provides a silica-based composite negative electrode material, a preparation method thereof and a lithium ion battery. The preparation method of the silica-based composite anode material provided by the invention comprises the following steps: a) Mixing micron-sized SiO and carbonic acidMixing magnesium, polyvinylpyrrolidone and water to obtain a mixture; b) Under the condition of stirring, carrying out heat treatment on the mixture to obtain SiO-MgCO 3 -a PVP solid composite cluster; c) Calcining the solid composite cluster in a protective gas atmosphere to obtain the three-dimensional honeycomb SiO x ‑MgSiO 3 -C nanocomposites, wherein 0 < x < 2. The preparation method is simple and easy to implement, and can effectively improve the first coulombic efficiency, obtain high specific capacity and good cycle performance.

Description

Silica-based composite anode material, preparation method thereof and lithium ion battery
Technical Field
The invention relates to the field of lithium ion battery materials, in particular to a silica-based composite negative electrode material, a preparation method thereof and a lithium ion battery.
Background
The lithium ion battery is considered as a battery energy storage system with the best comprehensive performance in recent years, and is the most important in applications such as portable electronic products, electric automobiles, smart grid energy storage and the like. The performance of the electrode material significantly affects the performance of the lithium ion battery, and the development of the electrode material with high energy density is particularly important in order to meet the development requirements of high-tech devices.
For high energy density anode materials, silicon based anode materials are certainly the best candidates. The silicon-based anode material comprises simple substance silicon and silicon oxide; wherein, the capacity advantage of the simple substance silicon is obvious, and the theoretical specific capacity can reach 4200mAh g to the maximum -1 Is a graphite negative electrode (372 mAh g) commercially available at present -1 ) More than 10 times. Silica (SiO) in contrast to elemental silicon x X is more than 0 and less than 2), still keeps higher theoretical specific capacity, and has lower price and obvious commercial value. Therefore, the silicon oxide has a certain positive effect on accelerating the industrialization process of the silicon-based negative electrode material.
The SiO is now hindered x The most critical problem for the application of the material is its low first coulombic efficiency, which is caused by SiO x SiO present in the material 2 The component reacts with lithium ions in the first charge-discharge process to generate Li 2 O and Li 4 SiO 4 This irreversible reaction consumes large amounts of lithium, resulting in an irreversible loss of material capacity. At the same time, compared with simple substance silicon, siO x The volume expansion of the material is due to Li 2 O and Li 4 SiO 4 Can be relieved to a certain extent, but the problem of volume expansion is still not completely solved, and the volume expansion can cause the structural collapse of the electrode material and influence the capacity and the service life of the battery. Furthermore, siO x The low conductivity of the material can cause the rate capability of the electrode material to be poor, thereby affecting the performance of the battery.
For SiO x The problem of low coulombic efficiency of the material for the first time is solved by the prior method, namely, the material is pre-lithiated, an external lithium source is added into the pre-lithiation, and the negative electrode reacts with the external lithium source firstly to avoid the large consumption of the positive electrode lithium source and reduce the loss of irreversible capacity. SiO 2 x The first coulombic efficiency of the material is also influenced by the oxygen content, and the lower the oxygen content is, the higher the first coulombic efficiency is, so that the material can also be used in SiO x The first coulombic efficiency of the material is improved by regulating and controlling the oxygen content in the preparation of the material. For SiO x The problems of volume expansion and low conductivity of the material are solved by the prior methods, such as nano-crystallization and composite of the material, wherein the carbon-coated SiO with the nano-structure is prepared x Materials are currently the simplest and most efficient method.
In patent application CN110620223A, a pre-lithiation silicon-carbon multilayer composite negative electrode material is obtained by mixing and sintering a silicon oxide and a lithium-containing ionic liquid, then growing a graphene material on the surface of the material through chemical vapor deposition, and finally, performing homogeneous fusion with a carbon source and performing heat treatment. Patent application CN111342030A uses a multicomponent composite method, in which a multicomponent conductive layer is coated with a silicon oxide to form a multicomponent composite material, and the prelithiation is achieved by doping with a lithium salt. However, the above prior art has the following disadvantages: the preparation process is complex, the required raw materials are more, the cost is higher, and the like.
Disclosure of Invention
In view of the above, the present invention provides a silica-based composite anode material, a preparation method thereof, and a lithium ion battery. The preparation method is simple and easy to implement, and can effectively improve the first coulombic efficiency, obtain high specific capacity and good cycle performance.
The invention provides a preparation method of a silica-based composite anode material, which comprises the following steps:
a) Mixing micron-sized SiO, magnesium carbonate, polyvinylpyrrolidone and water to obtain a mixture;
b) Under the condition of stirring, carrying out heat treatment on the mixture to obtain SiO-MgCO 3 -a PVP solid composite cluster;
c) Calcining the solid composite cluster in protective gas atmosphere to obtain three-dimensional honeycomb SiO x -MgSiO 3 -C nanocomposites, wherein 0 < x < 2.
Preferably, in the step a), the mass ratio of the micron-sized SiO to the magnesium carbonate to the polyvinylpyrrolidone is 1: 0.1-0.3: 0.15-0.3;
the dosage ratio of the micron-sized SiO to the water is 1g to (25-100) mL;
the water is deionized water.
Preferably, in the step a), the mixing is stirring mixing;
the stirring speed is 100-400 r/min, and the stirring time is 1-2 h.
Preferably, in the step b), the temperature of the heat treatment is 70 to 85 ℃.
Preferably, in the step b), the stirring speed under the stirring condition is 100 to 400r/min.
Preferably, in the step c), the calcining temperature is 800-1000 ℃, and the holding time is 2-6 h.
Preferably, in the step c), the temperature rise rate of the calcination is 2 to 6 ℃/min.
Preferably, the micron-sized SiO is SiO subjected to ball milling;
the ball milling conditions are as follows: the rotating speed is 300-500 r/min, the time is 2-4 h, and the ball material ratio is (20-40) to 1;
before ball milling, the granularity of the micron-sized SiO is 5-10 mu m, and after ball milling, the granularity of the obtained SiO is 1-5 mu m.
The invention also provides the silica-based composite anode material prepared by the preparation method in the technical scheme.
The invention also provides a lithium ion battery, and the negative electrode material in the lithium ion battery is the silica-based composite negative electrode material in the technical scheme.
The invention provides a preparation method of a silica-based composite negative electrode material, which comprises the steps of mixing micron-sized SiO, magnesium carbonate, polyvinylpyrrolidone and water, carrying out heat treatment on the obtained mixture to remove moisture, uniformly solidifying the material, and obtaining SiO-MgCO 3 -a PVP solid composite cluster; then carrying out calcination treatment, wherein during the calcination process, mgCO 3 Pyrolysis will produce CO 2 The three-dimensional honeycomb structure can relieve the volume expansion problem of the silicon oxide, improve the circulation stability of the material, and the carbon honeycomb wall can also improve the multiplying power performance of the material. Simultaneously, siO disproportionation reaction is carried out at high temperature to generate Si and SiO 2 ，SiO 2 Will react with MgO to generate MgSiO 3 Thereby achieving the regulation and control of the oxygen content in the silicon monoxide and further improving the first coulombic efficiency of the material. Electrochemically inert MgSiO 3 And the material is cooperated with a three-dimensional honeycomb structure to further improve the cycling stability of the material.
The nano-scale three-dimensional honeycomb structure silicon oxide composite cathode material is prepared by using simpler raw materials and adopting a simpler method; the content of the silica oxide is regulated and controlled through the chemical reaction among the raw materials, and the first coulombic efficiency of the material is improved; the electrochemical inert substance generated by the chemical reaction between the raw materials and the three-dimensional honeycomb structure have synergistic effect, so that the problem of volume expansion of the silicon monoxide is relieved, and the circulation stability of the material is improved.
Experimental results show that the silica-based composite negative electrode material prepared by the invention can enable the first coulombic efficiency of a battery to reach more than 84%, and the first charge specific capacity to be 1000 mAh.g -1 Above, the capacity retention rate after 50 cycles reaches more than 85%.
Detailed Description
The invention provides a preparation method of a silica-based composite anode material, which comprises the following steps:
a) Mixing micron-sized SiO, magnesium carbonate, polyvinylpyrrolidone and water to obtain a mixture;
b) Under the condition of stirring, carrying out heat treatment on the mixture to obtain SiO-MgCO 3 -a PVP solid composite cluster;
c) Calcining the solid composite cluster in protective gas atmosphere to obtain three-dimensional honeycomb SiO x -MgSiO 3 -C nanocomposites, wherein 0 < x < 2.
Mixing micron-sized SiO, magnesium carbonate, polyvinylpyrrolidone and water, and then carrying out heat treatment on the obtained mixture to remove moisture so as to uniformly solidify the material to obtain SiO-MgCO 3 -a PVP solid composite cluster; then carrying out calcination treatment, wherein MgCO is generated in the calcination process 3 Pyrolysis will produce CO 2 The three-dimensional honeycomb structure can relieve the volume expansion problem of the silicon oxide, improve the circulation stability of the material, and the carbon honeycomb wall can also improve the multiplying power performance of the material. Simultaneously, siO is subjected to disproportionation reaction at high temperature to generate Si and SiO 2 ，SiO 2 Will react with MgO to generate MgSiO 3 Thereby achieving the regulation and control of the oxygen content in the silicon monoxide and further improving the first coulombic efficiency of the material. Electrochemically inert MgSiO 3 And the material is cooperated with a three-dimensional honeycomb structure to further improve the cycling stability of the material.
With respect to step a): mixing the micron-sized SiO, magnesium carbonate, polyvinylpyrrolidone and water to obtain a mixture.
In the present invention, the micron-sized SiO (i.e., siO) preferably has a particle size of 1 to 5 μm. In the invention, the micron-sized SiO is preferably obtained by ball milling, and particularly, the micron-sized SiO raw material is ball milled to form the micron-sized SiO with smaller granularity. In the present invention, the micron-sized SiO raw material preferably has a particle size of 5 to 10 μm before ball milling. The conditions of the ball milling are preferably as follows: the ball milling speed is 300-500 r/min, in some embodiments of the invention, the ball milling speed is 450r/min, 500r/min; the ball milling time is 2-4 h, in some embodiments of the invention, 2h or 4h; the ball-material ratio of ball milling is (20-40) to 1; in some embodiments of the invention, the ball to feed ratio is 20: 1 or 40: 1. The SiO material has the advantages that the volume expansion phenomenon in the charging and discharging processes can cause the electrode structure to be seriously damaged, so that the capacity is sharply attenuated, and the cycle performance is poor; meanwhile, a larger specific surface area can be obtained, the absorption of electrolyte is promoted, and the charge transfer of the electrode is promoted.
In the present invention, magnesium carbonate is used, which decomposes to produce MgO, mgO and SiO 2 React to form MgSiO 3 The method realizes the regulation and control of the oxygen content in the silicon monoxide, further improves the first coulombic efficiency of the material, and simultaneously has the electrochemical inertia of MgSiO 3 And the material is cooperated with a three-dimensional honeycomb structure to further improve the cycling stability of the material. When other carbonate is substituted, the above-mentioned effects are hardly obtained.
In the invention, polyvinylpyrrolidone (PVP) is also introduced, and is mixed with the other raw materials, so that composite agglomeration is more favorably formed after heat treatment, and then the mixture is carbonized in high-temperature calcination and matched with MgCO 3 The gas generated by decomposition escapes, a honeycomb structure similar to a hexagon is formed, and a 3D conductive network is constructed.
In the invention, the mass ratio of the micron-sized SiO to the magnesium carbonate to the polyvinylpyrrolidone is preferably 1 to (0.1-0.3) to (0.15-0.3); if the mass ratio of magnesium carbonate is too low, the first coulombic efficiency of the product is not facilitated, and if the mass ratio of magnesium carbonate is too high, the specific capacity of the product is influenced; if the mass ratio of the polyvinylpyrrolidone is too low or too high, the carbon layer outside the product is too thin or too thick, which is not beneficial to forming a honeycomb structure, and in addition, the carbon layer is too thin and is also not beneficial to the cycling stability of the product, and the carbon layer is too thick, which can affect the specific capacity of the product. In some embodiments of the invention, the mass ratio is 1: 0.1: 0.2, 1: 0.2, 1: 0.3: 0.15, or 1: 0.3: 0.2.
In the invention, the water is preferably deionized water, and if other water such as common tap water is adopted, impurities in the water can influence the product performance. In the invention, the dosage ratio of the water to the micron-sized SiO is preferably (25-100) mL: 1g.
In the present invention, the mixing is preferably stirring mixing; the stirring speed is 100-400 r/min, and the stirring and mixing time is 1-2 h. The temperature of the mixing is not particularly limited, and the mixing can be carried out at room temperature, and specifically can be 20-30 ℃. And mixing to obtain a mixture.
With respect to step b): under the condition of stirring, carrying out heat treatment on the mixture to obtain SiO-MgCO 3 -PVP solid composite clusters.
In the invention, after the mixed material is obtained in the step a), the mixed material is heated to evaporate water, and stirring is continuously carried out in the process. In the present invention, the stirring rate is preferably 100 to 400r/min.
In the invention, the temperature of the heat treatment is preferably 70-85 ℃; in some embodiments of the invention, the temperature of the heat treatment is 80 ℃ or 85 ℃. In the present invention, the heat treatment is preferably performed for a time until moisture in the mixture is evaporated. After the stirring, heating and evaporation treatment, the mixture is uniformly mixed and solidified to form SiO-MgCO 3 -PVP solid composite clusters.
With respect to step c): calcining the solid composite cluster in protective gas atmosphere to obtain three-dimensional honeycomb SiO x -MgSiO 3 -C nanocomposites, wherein 0 < x < 2.
In the present invention, the kind of the protective gas is not particularly limited, and may be a conventional inert gas known to those skilled in the art, such as nitrogen or argon.
In the invention, the calcination temperature is preferably 800-1000 ℃, if the temperature is too low, the disproportionation reaction of SiO can not be initiated, and the target product of the invention can not be obtained, and if the temperature is too highThe material is damaged to a certain extent, the performance of the material is influenced, and the energy consumption is wasted. In some embodiments of the invention, the temperature of the calcination is 800 ℃ or 1000 ℃. In the invention, the heating rate of the calcination is preferably 2-6 ℃/min; in some embodiments of the invention, the ramp rate is 2 ℃/min or 4 ℃/min. In the invention, the calcination heat preservation time is preferably 2-6 h; in some embodiments of the invention, the calcination is held for 2 hours or 4 hours. After the calcination treatment, the three-dimensional honeycomb SiO is obtained x -MgSiO 3 -C nanocomposites, wherein 0 < x < 2.
During the calcination process, mgCO 3 Pyrolysis will produce CO 2 The three-dimensional honeycomb structure can relieve the volume expansion problem of the silicon oxide, improve the circulation stability of the material, and the carbon honeycomb wall can also improve the multiplying power performance of the material. Simultaneously, siO disproportionation reaction is carried out at high temperature to generate Si and SiO 2 ，SiO 2 Will react with MgO to generate MgSiO 3 Thereby achieving the regulation and control of the oxygen content in the silicon monoxide and further improving the first coulombic efficiency of the material. Electrochemically inert MgSiO 3 And the material is cooperated with a three-dimensional honeycomb structure to further improve the cycling stability of the material. The particle size of the nano composite material particles obtained by the invention is 100-500 nm, the nano composite material particles are of a honeycomb structure, the C honeycomb wall is used as a shell, and the generated MgSiO is 3 With SiO x Mixing in the honeycomb, i.e. the walls of C honeycomb are wrapped with MgSiO 3 With SiO x . SiO 2 x With amorphous Si phase and amorphous SiO phase inside 2 Phase, x is through SiO therein 2 The reaction with MgO.
According to the preparation method provided by the invention, the nano-scale three-dimensional honeycomb structure silicon oxide composite negative electrode material is prepared by using simpler raw materials and adopting a simpler mode; the content of the silica oxide is regulated and controlled through chemical reaction among the raw materials, and the first coulombic efficiency of the material is improved; the electrochemical inert substance generated by the chemical reaction between the raw materials and the three-dimensional honeycomb structure have synergistic effect, so that the problem of volume expansion of the silicon monoxide is relieved, and the circulation stability of the material is improved.
The invention also provides the silica-based composite anode material prepared by the preparation method in the technical scheme.
The invention also provides a lithium ion battery, and the negative electrode material in the lithium ion battery is the silica-based composite negative electrode material in the technical scheme.
Experimental results show that the protoxide-based composite negative electrode material prepared by the invention can enable the first coulombic efficiency of a battery to reach more than 84%, and the first charge specific capacity to be 1000 mAh.g -1 Above, the capacity retention rate after 50 cycles reaches 85% or more.
For a further understanding of the invention, reference will now be made to the preferred embodiments of the invention by way of example, and it is to be understood that the description is intended to further illustrate features and advantages of the invention, and not to limit the scope of the claims.
Example 1
S1, ball milling SiO with the particle size of 5-10 microns by using a planetary ball mill, wherein the ball-material ratio is 20: 1, the rotating speed is 450r/min, and the ball milling time is 4 hours, so that refined SiO with the particle size of 1.5 microns is obtained.
S2, ball-milled micron-sized SiO and MgCO 3 Adding PVP and PVP into deionized water according to the mass ratio of 1: 0.1: 0.2 (the dosage ratio of the micron-sized SiO to the water is 1 g: 50 mL), and continuously stirring (the speed is 300 r/min), wherein the stirring time is 2h; heating the mixture at 85 deg.C in oil bath to evaporate water, stirring continuously during evaporation (speed of 200 r/min), mixing the mixture by evaporation, and solidifying to obtain SiO/MgCO 3 the/PVP compound cluster.
S3, mixing SiO/MgCO 3 Calcining the/PVP composite cluster in a tube furnace in argon atmosphere at 800 ℃ for 4h at the heating rate of 2 ℃/min to obtain the three-dimensional honeycomb nano SiO x /MgSiO 3 @ C composite material.
Example 2
Pressing to realThe preparation of example 1 was carried out, except that SiO, mgCO in micron order were mixed 3 The mass ratio of the PVP to the PVP is adjusted to be 1: 0.2.
Example 3
The procedure is as in example 1, except that SiO, mgCO are present in micron size 3 The mass ratio of the PVP to the PVP is adjusted to be 1: 0.3: 0.2.
Example 4
S1, ball milling SiO with the particle size of 5-10 microns by using a planetary ball mill, wherein the ball-material ratio is 40: 1, the rotating speed is 500r/min, and the ball milling time is 2 hours, so that refined SiO with the particle size of 2.0 microns is obtained.
S2, ball-milled micron-sized SiO and MgCO 3 PVP is added into deionized water according to the mass ratio of 1: 0.3: 0.15 (the dosage ratio of the micron-sized SiO to the water is 1 g: 50 mL) and is continuously stirred (the speed is 300 r/min), and the stirring time is 2h; heating the mixture in an oil bath at 80 deg.C to evaporate water, stirring continuously during evaporation (speed of 200 r/min), mixing the mixture by evaporation, and solidifying to obtain SiO/MgCO 3 the/PVP compound cluster.
S3, mixing SiO/MgCO 3 Calcining the/PVP composite cluster in a tube furnace in argon atmosphere at 1000 ℃ for 2h at the heating rate of 4 ℃/min to obtain the three-dimensional honeycomb nano SiO x /MgSiO 3 @ C composite material.
Comparative example 1
The procedure of example 3 was followed except that PVP was not added.
Comparative example 2
The procedure is as in example 3, except that MgCO is not added 3 。
Example 5
1.1 Battery Assembly
Preparing a negative pole piece: the prepared active material, acetylene black (conductive agent) and Styrene Butadiene Rubber (SBR) (binder) are mixed and dissolved in deionized water according to the mass ratio of 80. The slurry was uniformly coated on a battery-grade copper foil to a thickness of 10 μm, and then dried in a vacuum oven at 85 ℃ for 12 hours, taken out of the roll, and die-cut into a negative electrode sheet with a diameter of 14mm with a die cutter.
Assembling the battery: the prepared cathode plate is a working electrode, a lithium plate is a counter electrode, a Celgard 2400 polypropylene microporous membrane is a diaphragm, and 1M LiPF 6 EC/DMC/DEC dissolved in a volume ratio of 1.
1.2 Performance testing
Electrochemical performance tests were performed on the batteries assembled with the negative electrode materials of examples 1 to 4 and comparative examples 1 to 2, respectively.
And (3) performing charge and discharge tests on the assembled CR2032 button half-cell by adopting a CT-4008T cell test system of New Wille electronics Limited, shenzhen, at room temperature, wherein the test voltage range is 0.01-3.0V, and the current density is 150mAh/g.
The test results are shown in table 1:
TABLE 1 electrochemical Properties of the materials obtained in examples 1 to 4 and comparative examples 1 to 2
Figure BDA0002861572270000091
According to the test results, the three-dimensional honeycomb nano SiO prepared by the invention x /MgSiO 3 The @ C composite material can effectively improve the first coulombic efficiency, specific capacity and cycle performance of the material. The comparison of the effects with those of comparative examples 1-2 proves that PVP and MgCO are simultaneously adopted in the invention 3 The method can generate a synergistic effect and obviously improve the electrochemical performance of the material.
The above description of the embodiments is only intended to facilitate the understanding of the method of the invention and its core idea. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.

Claims (9)

1. The preparation method of the silica-based composite anode material is characterized by comprising the following steps of:
a) Mixing micron-sized SiO, magnesium carbonate, polyvinylpyrrolidone and water to obtain a mixture;
the mass ratio of the micron-sized SiO to the magnesium carbonate to the polyvinylpyrrolidone is 1: 0.1 to 0.3: 0.15 to 0.3;
b) Under the condition of stirring, carrying out heat treatment on the mixture to obtain SiO-MgCO 3 -a PVP solid composite cluster;
the temperature of the heat treatment is 70 to 85 ℃;
c) Calcining the solid composite cluster in protective gas atmosphere to obtain hexagonal-like three-dimensional honeycomb SiO x -MgSiO 3 -C nanocomposites with C honeycomb walls as the shell, mgSiO produced 3 With SiO x Mixing in the honeycomb, i.e. the walls of C honeycomb are coated with MgSiO 3 With SiO x (ii) a Wherein x is more than 0 and less than 2.
2. The preparation method according to claim 1, wherein in the step a), the usage ratio of the micron-sized SiO to the water is 1g to (25 to 100) mL;
the water is deionized water.
3. The method according to claim 1, wherein in the step a), the mixing is stirring mixing;
the stirring speed is 100 to 400r/min, and the stirring time is 1 to 2h.
4. The preparation method according to claim 1, wherein in the step b), the stirring rotation speed under the stirring condition is 100 to 400r/min.
5. The method according to claim 1, wherein in the step c), the calcining temperature is 800 to 1000 ℃, and the holding time is 2 to 6h.
6. The method according to claim 1 or 5, wherein in step c), the temperature increase rate of the calcination is 2 to 6 ℃/min.
7. The method of claim 1, wherein the micron-sized SiO is ball-milled SiO;
the ball milling conditions are as follows: the rotating speed is 300 to 500r/min, the time is 2 to 4h, and the ball-to-feed ratio is (20 to 40) to 1;
before ball milling, the granularity of the micron-sized SiO is 5 to 10 mu m, and after ball milling, the granularity of the obtained SiO is 1 to 5 mu m.
8. A silica-based composite negative electrode material prepared by the preparation method of any one of claims 1 to 7.
9. A lithium ion battery, wherein the negative electrode material in the lithium ion battery is the silica-based composite negative electrode material according to claim 8.
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