CN112186188B - Silicon-based negative electrode material and preparation method and application thereof - Google Patents

Silicon-based negative electrode material and preparation method and application thereof Download PDF

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CN112186188B
CN112186188B CN202011053174.6A CN202011053174A CN112186188B CN 112186188 B CN112186188 B CN 112186188B CN 202011053174 A CN202011053174 A CN 202011053174A CN 112186188 B CN112186188 B CN 112186188B
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silicon
coating layer
precursor
lithium
negative electrode
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CN112186188A (en
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谌庆春
彭果戈
夏振宇
蔡志炬
何凤荣
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Dongguan HEC Tech R&D Co Ltd
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    • H—ELECTRICITY
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    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
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Abstract

The invention discloses a silicon-based negative electrode material and a preparation method and application thereof, wherein the silicon-based negative electrode material comprises the following components: the core comprises a silicon-based material; the lithium silicate coating layer comprises Li2Si2O5The lithium silicate coating layer is arranged at the periphery of the inner core, pores are formed on the lithium silicate coating layer, and a distance exists between the lithium silicate coating layer and the inner core; the carbon coating layer is coated on the lithium silicate coating layer. Therefore, the silicon-based negative electrode material has high first-effect and cycling stability, and the first-effect and cycling performance of the lithium battery can be improved by loading the negative electrode prepared from the silicon-based negative electrode material in the lithium battery.

Description

Silicon-based negative electrode material and preparation method and application thereof
Technical Field
The invention belongs to the field of batteries, and particularly relates to a silicon-based negative electrode material, and a preparation method and application thereof.
Background
The silicon-based negative electrode material mainly comprises simple substance nano silicon and silicon oxide, and has the advantages of rich resources and high specific capacity, and has the defects of huge volume expansion in the charge-discharge process, the simple substance silicon reaches 300 percent, and the silicon oxide is slightly lower and also reaches 150 percent, so that the cycle performance of the silicon-based negative electrode material is extremely poor, and the silicon-based negative electrode material is not beneficial to commercial application.
At present, the mainstream carbon coating means can effectively improve the cycle performance of the silicon-based negative electrode material, but no matter what carbon coating means (gas phase coating, liquid phase coating and solid phase coating) is adopted, the carbon source is the physical pyrolysis of an organic carbon source, which belongs to the physical modification range, and the cycle performance of the silicon-based negative electrode material is more general due to the risk of high probability damage in the long-term cycle process because the strength of a carbon layer is limited.
Therefore, a special coating means is urgently needed to enhance the cycle performance of the silicon-based negative electrode material.
Disclosure of Invention
The present invention is directed to solving, at least to some extent, one of the technical problems in the related art. Therefore, an object of the present invention is to provide a silicon-based negative electrode material, a preparation method and an application thereof, wherein the silicon-based negative electrode material has high first efficiency and cycle stability, and the first efficiency and cycle performance of a lithium battery can be improved by loading a negative electrode prepared from the silicon-based negative electrode material in the lithium battery.
In one aspect of the invention, a silicon-based anode material is provided. According to an embodiment of the invention, the silicon-based anode material comprises:
a core comprising a silicon-based material;
a lithium silicate coating layer comprising Li2Si2O5The lithium silicate coating layer is arranged at the periphery of the inner core, pores are formed in the lithium silicate coating layer, and a distance exists between the lithium silicate coating layer and the inner core;
and the carbon coating layer is coated on the lithium silicate coating layer.
According to the silicon-based anode material provided by the embodiment of the invention, the silicon-based anode material comprises Li by forming on the periphery of the inner core2Si2O5When the silicon-based negative electrode material is charged and discharged, the expansion stress is relatively low, and the strength of the lithium silicate coating layer is greater than that of the physical pyrolytic carbon layer, so that the cycling stability of the material is improved, and the lithium silicate coating layer only contains Li2Si2O5Due to crystalline Li2Si2O5Does not react with water, does not have the negative problems of dissolution and the like in the subsequent homogenization process, has a plurality of pores on the lithium silicate coating layer, is convenient for the conduction of lithium ions, reduces the polarization of materials, and is coated with a carbon coating layer on the surface of the lithium silicate coating layerThe coating layer can effectively avoid the direct contact of the cathode silicon-based material and electrolyte, reduce the occurrence of side reactions and improve the first effect, and the carbon coating layer also has the function of limiting the expansion of the silicon-based core, thereby further improving the cycle performance of the material. Therefore, the silicon-based negative electrode material with the structure has high first effect and circulation stability, and the negative electrode prepared by the silicon-based negative electrode material is loaded in the lithium battery, so that the first effect and the circulation performance of the lithium battery can be improved.
In addition, the silicon-based anode material according to the above embodiment of the present invention may further have the following additional technical features:
in some embodiments of the present invention, the silicon-based material comprises at least one of elemental nano-silicon and silicon oxide.
In some embodiments of the present invention, the particle diameter D50 of the elemental nano-silicon is 5 to 100nm, and preferred ranges include 5 to 20nm, 20 to 30nm, 30 to 50nm, 50 to 80nm, 80 to 100nm, 30 to 80nm, 30 to 100nm, 50 to 100nm, and the like.
In some embodiments of the invention, the silicon oxide has the chemical formula SiOxAnd x is 0.5 to 1.5.
In some embodiments of the present invention, the particle size D50 of the silicon oxide is 100nm to 15 μm, and preferable ranges include 100nm to 1 μm, 1 to 15 μm, and the like.
In some embodiments of the present invention, the lithium silicate coating layer has a thickness of 10 to 100 nm. Therefore, the cycle performance of the silicon-based negative electrode material can be improved. Examples thereof include 10 to 50nm and 50 to 100 nm.
In some embodiments of the present invention, the lithium silicate coating layer is 5 to 30% by mass based on the total mass of the silicon-based anode material. Therefore, the cycle performance of the silicon-based negative electrode material can be improved. Examples thereof include 5 to 10%, 10 to 15%, 15 to 30%, etc.
In some embodiments of the present invention, the thickness of the carbon coating layer is 1 to 50 nm. Therefore, the first efficiency and the cycle performance of the silicon-based negative electrode material can be improved. Examples thereof include 5 to 18nm, 18 to 35nm, and 35 to 50 nm.
In some embodiments of the invention, the mass percentage of the carbon coating layer is 1-20% based on the total mass of the silicon-based negative electrode material. Therefore, the first efficiency and the cycle performance of the silicon-based negative electrode material can be improved. Examples thereof include 5 to 10%, 10 to 15%, 15 to 20%, etc.
In still another aspect of the present invention, the present invention provides a method for preparing the above silicon-based anode material. According to an embodiment of the invention, the method comprises:
(1) coating silicon dioxide on the surface of a silicon-based material to obtain a first precursor;
(2) coating a water-soluble lithium source on the first precursor to obtain a second precursor;
(3) sintering the second precursor under inert atmosphere, so that a part of the silicon dioxide reacts with the water-soluble lithium source to form Li-containing silicon on the surface of the silicon-based material2Si2O5To obtain a third precursor;
(4) etching the third precursor to remove the other part of the silicon dioxide and remove Li in the lithium silicate coating layer2Si2O5Lithium silicate except the lithium silicate so as to obtain a fourth precursor which is provided with pores on the lithium silicate coating layer and has a hollow core-shell structure;
(5) and coating a carbon coating layer on the surface of the fourth precursor so as to obtain the silicon-based negative electrode material.
According to the method for preparing the silicon-based negative electrode material, silicon dioxide is coated on the surface of the silicon-based material, then the silicon-based material with the silicon dioxide is coated with the water-soluble lithium source, and the silicon-based material is roasted in the inert atmosphere, so that part of the silicon dioxide reacts with the water-soluble lithium source to generate different types of lithium silicate (the water-soluble lithium source takes lithium carbonate as an example, SiO is taken as the water-soluble lithium source)2+1/2Li2CO3→1/2Li2Si2O5+1/2CO2，SiO2+Li2CO3→Li2SiO3+CO2，SiO2+2Li2CO3→Li4SiO4+2CO2) That is, the surface of the core of the silicon-based material is formed with silicon dioxide and Li2Si2O5、Li2SiO3And Li4SiO4Then etching the precursor obtained from the lithium silicate coating layer, removing the other part of silicon dioxide in the precursor and removing Li in the lithium silicate coating layer2Si2O5With lithium silicates other than, i.e. formed to include Li at the periphery of the silicon-based material2Si2O5The lithium silicate coating layer is separated from the inner core due to the removal of another part of silicon dioxide, an expansion space is reserved for the expansion of the inner core, when the silicon-based anode material is charged and discharged, the expansion stress is relatively low, the strength of the lithium silicate coating layer is greater than that of the physical pyrolytic carbon layer, and therefore the cycling stability of the material is improved, and only Li is contained in the lithium silicate coating layer2Si2O5Due to crystalline Li2Si2O5The lithium silicate coating layer is provided with a plurality of pores, so that the conduction of lithium ions is facilitated, the polarization of the material is reduced, and finally the carbon coating layer is coated on the surface of the lithium silicate coating layer, so that the carbon coating layer can effectively avoid the direct contact of a negative silicon-based material and electrolyte, the occurrence of side reactions is reduced, the first effect is improved, and the carbon coating layer also has the effect of limiting the expansion of a silicon-based core, thereby further improving the cycle performance of the material. Therefore, the silicon-based negative electrode material with higher first-effect and cycling stability can be obtained by adopting the method, and the first-effect and cycling performance of the lithium battery can be improved by loading the negative electrode prepared by adopting the silicon-based negative electrode material in the lithium battery.
In addition, the method for preparing the silicon-based anode material according to the embodiment of the invention may further have the following additional technical features:
in some embodiments of the present invention, in the step (1), the silicon dioxide is amorphous silicon dioxide, and the amorphous silicon dioxide coating layer formed on the surface of the silicon-based material has a thickness of 30 to 150 nm. Examples thereof include 30 to 80nm, 80 to 100nm, and 100 to 150 nm.
In some embodiments of the present invention, in the step (1), the amorphous silicon dioxide coating layer has a mass ratio of 5 to 20% based on the total mass of the first precursor. Examples thereof include 5 to 10%, 10 to 20%, etc.
In some embodiments of the invention, in step (2), the water-soluble lithium source is coated on the first precursor by spray drying.
In some embodiments of the invention, in step (2), the water-soluble lithium source comprises at least one of lithium carbonate, lithium oxalate, lithium nitrate, and lithium acetate.
In some embodiments of the invention, in step (2), the molar ratio of lithium in the water-soluble lithium source to oxygen in the silica is 0.08 to 0.2.
In some embodiments of the invention, in the step (3), the sintering temperature is 700-900 ℃, the heating rate is 0.5-10 ℃/min, and the sintering time is 1-36 h.
In some embodiments of the present invention, in step (4), the precursor obtained in step (3) is etched with hydrofluoric acid.
In some embodiments of the invention, in the step (4), the concentration of the hydrofluoric acid is 0.5-1.0 mol/L, and the etching time is 1-120 min.
In a third aspect of the invention, a negative electrode is presented. According to the embodiment of the invention, the negative electrode is prepared from the silicon-based negative electrode material or the silicon-based negative electrode material obtained by the method. Therefore, the cathode is made of the silicon-based cathode material with high first-effect and excellent cycling stability, so that the cathode has high first-effect and cycling performance.
In a fourth aspect of the present invention, a lithium battery is provided. According to an embodiment of the present invention, the lithium battery includes the negative electrode described above. Therefore, the lithium battery has high first-effect and cycle performance by loading the negative electrode with high first-effect and cycle performance prepared by the silicon-based negative electrode material.
Additional aspects and advantages of the invention will be set forth in part in the description which follows and, in part, will be obvious from the description, or may be learned by practice of the invention.
Drawings
The above and/or additional aspects and advantages of the present invention will become apparent and readily appreciated from the following description of the embodiments, taken in conjunction with the accompanying drawings of which:
fig. 1 is a schematic cross-sectional structure of a silicon-based anode material according to an embodiment of the present invention;
fig. 2 is a schematic flow diagram of a method for preparing a silicon-based anode material according to an embodiment of the invention;
fig. 3 is a schematic view of a silicon-based material structure in a method for preparing a silicon-based anode material according to an embodiment of the present invention;
fig. 4 is a schematic cross-sectional structure of an amorphous silicon dioxide layer coated on the surface of a silicon-based material in a method for preparing a silicon-based negative electrode material according to an embodiment of the present invention;
fig. 5 is a schematic cross-sectional structure of a coated aqueous lithium source precursor in a method for preparing a silicon-based negative electrode material according to an embodiment of the present invention;
fig. 6 is a schematic cross-sectional structure of a precursor coated with a lithium silicate coating layer in a method for preparing a silicon-based anode material according to an embodiment of the present invention;
fig. 7 is a schematic cross-sectional structural view of a precursor of a hollow core-shell structure in a method for preparing a silicon-based anode material according to an embodiment of the present invention;
fig. 8 is a schematic cross-sectional structure of a silicon-based anode material obtained by a method for preparing a silicon-based anode material according to an embodiment of the present invention.
Detailed Description
Reference will now be made in detail to embodiments of the present invention, examples of which are illustrated in the accompanying drawings, wherein like or similar reference numerals refer to the same or similar elements or elements having the same or similar function throughout. The embodiments described below with reference to the drawings are illustrative and intended to be illustrative of the invention and are not to be construed as limiting the invention.
In the description of the present invention, it is to be understood that the terms "central," "longitudinal," "lateral," "length," "width," "thickness," "upper," "lower," "front," "rear," "left," "right," "vertical," "horizontal," "top," "bottom," "inner," "outer," "clockwise," "counterclockwise," "axial," "radial," "circumferential," and the like are used in the orientations and positional relationships indicated in the drawings for convenience in describing the invention and to simplify the description, and are not intended to indicate or imply that the referenced device or element must have a particular orientation, be constructed and operated in a particular orientation, and are not to be considered limiting of the invention.
Furthermore, the terms "first", "second" and "first" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include at least one such feature. In the description of the present invention, "a plurality" means at least two, e.g., two, three, etc., unless specifically limited otherwise.
In one aspect of the invention, a silicon-based anode material is provided. According to an embodiment of the present invention, referring to fig. 1, the silicon-based anode material includes a core 100, a lithium silicate coating layer 200, and a carbon coating layer 300.
According to an embodiment of the present invention, referring to fig. 1, the core 100 includes a silicon-based material, preferably, the silicon-based material includes at least one of elemental nano-silicon and silicon oxide; wherein the particle size D50 of the simple substance nano silicon is 5-100 nm; the chemical formula of the silicon oxide is SiOxX is 0.5 to 1.5, and the particle diameter D50 of the silicon oxide is 100nm to 15 μm.
According to an embodiment of the present invention, referring to FIG. 1, the lithium silicate cladding layer 200 includes Li2Si2O5Silicon ofThe lithium silicate coating layer 200 is disposed on the outer periphery of the core 100, the lithium silicate coating layer 200 has pores, and there is a distance between the lithium silicate coating layer 200 and the core 100. The inventors found that by forming the outer periphery of the core 100 to include Li2Si2O5The lithium silicate coating layer 200 has a distance between the lithium silicate coating layer 200 and the inner core 100, that is, an expansion space is reserved for the expansion of the inner core 100, when the silicon-based negative electrode material is charged and discharged, the expansion stress is relatively low, and the strength of the lithium silicate coating layer is greater than that of the physical pyrolytic carbon layer, so that the cycling stability of the material is improved, and the lithium silicate coating layer 200 only contains Li2Si2O5Due to crystalline Li2Si2O5Does not react with water, has no negative problems such as dissolution and the like in the subsequent homogenization process, and has a plurality of pores on the lithium silicate coating 200, thereby facilitating the conduction of lithium ions and reducing the polarization of the material. Further, the lithium silicate coating layer 200 has a thickness of 10 to 100 nm. The inventors have found that when the thickness of the lithium silicate coating layer 200 is less than 10nm, the lithium silicate coating layer has a limited effect on the expansion limitation of the core of the silicon-based material, and when the thickness of the lithium silicate coating layer 200 is more than 100nm, the specific capacity of the material may be greatly reduced because lithium silicate is an inactive substance. Meanwhile, based on the total mass of the silicon-based anode material, the mass proportion of the lithium silicate coating layer 200 is 5-30%. Therefore, the cycling stability of the silicon-based anode material can be improved.
According to an embodiment of the present invention, referring to fig. 1, a carbon coating layer 300 is coated on the lithium silicate coating layer 200. The inventor finds that the carbon coating layer can effectively avoid the direct contact between the silicon-based material of the negative electrode and the electrolyte by coating the carbon coating layer on the surface of the lithium silicate coating layer, reduce the occurrence of side reactions and improve the first effect, and the carbon coating layer also has the effect of limiting expansion, thereby further improving the cycle performance of the material. Further, the thickness of the carbon coating layer 300 is 1 to 50 nm. The inventors found that when the thickness of the carbon coating layer 300 is less than 1nm, the effect of the carbon coating layer on the barrier electrolyte is insignificant, and when the thickness of the carbon coating layer 300 is more than 50nm, the deintercalation path of lithium ions becomes long, which is not favorable for the exertion of rate capability. Meanwhile, based on the total mass of the silicon-based negative electrode material, the mass ratio of the carbon coating layer 300 is 1-20%. The inventors found that when the mass ratio of the carbon coating layer 300 is less than 1%, the effect of the carbon coating layer on the separation of the electrolyte is insignificant due to its low thickness, and when the mass ratio of the carbon coating layer 300 is more than 20%, the intrinsic specific capacity of the carbon coating layer is low, which results in a significant decrease in the specific capacity of the material, while on the other hand, the carbon coating layer is too thick, which results in a longer deintercalation path of lithium ions, which is not favorable for the exertion of rate capability.
According to the silicon-based anode material provided by the embodiment of the invention, the silicon-based anode material comprises Li by forming on the periphery of the inner core2Si2O5When the silicon-based negative electrode material is charged and discharged, the expansion stress is relatively low, and the strength of the lithium silicate coating layer is greater than that of the physical pyrolytic carbon layer, so that the cycling stability of the material is improved, and the lithium silicate coating layer only contains Li2Si2O5Due to crystalline Li2Si2O5The lithium silicate coating has a plurality of pores, so that the conduction of lithium ions is facilitated, the polarization of the material is reduced, in addition, the carbon coating layer is coated on the surface of the lithium silicate coating layer, the carbon coating layer can effectively avoid the direct contact of a silicon-based material of a negative electrode and electrolyte, the occurrence of side reactions is reduced, the first effect is improved, and the carbon coating layer also has the effect of limiting expansion, so that the cycle performance of the material is further improved. Therefore, the silicon-based negative electrode material with the structure has high first effect and circulation stability, and the negative electrode prepared by the silicon-based negative electrode material is loaded in the lithium battery, so that the first effect and the circulation performance of the lithium battery can be improved.
In still another aspect of the present invention, the present invention provides a method for preparing the above silicon-based anode material. Referring to fig. 2-8, the method includes, in accordance with an embodiment of the present invention:
s100: coating silicon dioxide on the surface of silicon-based material
In the step, silicon dioxide is coated on the surface of a silicon-based material to obtain a first precursor, and the silicon dioxide is coated on the surface of the silicon-based material by hydrolyzing and polymerizing tetraethoxysilane and/or sodium silicate on the surface of the silicon-based material. Specifically, the silicon dioxide coated on the surface of the silicon-based material is amorphous silicon dioxide, and the thickness of the amorphous silicon dioxide coating layer formed on the surface of the silicon-based material is 30-150 nm; and the mass ratio of the amorphous silicon dioxide coating layer is 5-20% based on the total mass of the first precursor, so that sufficient lithium silicate phase is generated in the subsequent sintering process. Meanwhile, an amorphous silicon dioxide layer (refer to fig. 4) is formed on the surface of a silicon-based material (refer to fig. 3) by mixing tetraethoxysilane and/or sodium silicate with the silicon-based material, and then placing it in a solvent including water and ethanol with controlling pH, so that the tetraethoxysilane and/or sodium silicate is hydrolyzed and polymerized. It should be noted that the process of coating silicon dioxide on the surface of a silicon-based material by hydrolytic polymerization of tetraethoxysilane and/or sodium silicate is the conventional technology, and the process conditions are not described herein again.
S200: coating a water-soluble lithium source on the first precursor
In this step, referring to fig. 5, a water-soluble lithium source is coated on the first precursor obtained in step S100 by a spray drying method, preferably, the water-soluble lithium source is at least one of lithium carbonate, lithium oxalate, lithium nitrate and lithium acetate, the inlet temperature of the spray drying is 160 to 230 ℃, the outlet temperature is 100 to 120 ℃, and the spray drying equipment may be pressure type, two-fluid, four-fluid or centrifugal spray drying. Compared with the method adopting metallic simple substance lithium, lithium hydride and strong alkaline lithium hydroxide, the metallic simple substance lithium can react with moisture in the air violently and can be oxidized in the air quickly; lithium hydride reacts violently with water to generate corrosive lithium hydroxide and flammable and explosive gaseous hydrogen; the strong-alkaline lithium hydroxide can react with the material, and the like, the lithium source has special requirements on the actual use environment, such as air humidity, inert atmosphere and the like, so that the large-scale use of the lithium source is limited, and the water-soluble lithium source is selected, has no special requirements on the use environment, and is friendly and harmless to operators.
Further, the molar ratio of lithium in the water-soluble lithium source coated on the first precursor obtained in step S100 to oxygen in the amorphous silicon dioxide layer on the first precursor obtained in step S100 is 0.08 to 0.2. The inventors have found that when the molar ratio of lithium to oxygen is too low, the formation of lithium silicate itself is limited, and the coating effect of the lithium silicate coating layer is deteriorated, while the molar ratio of the lithium silicate phase formed by the reaction to oxygen is large, and specifically, the molar ratio of lithium to lithium is large, taking lithium carbonate as an example, and SiO is a specific example2+1/2Li2CO3→1/2Li2Si2O5+1/2CO2，SiO2+Li2CO3→Li2SiO3+CO2，SiO2+2Li2CO3→Li4SiO4+2CO2In order to obtain the lithium silicate Li2Si2O5Mainly, the molar ratio of the balance lithium to the oxygen is 0.5, and the molar ratio of the lithium to the oxygen is not higher than 0.2 because excessive silicon dioxide needs to be introduced in the structural design of the invention, and the redundant silicon dioxide is etched by hydrofluoric acid to obtain a hollow core-shell structure.
S300: sintering the second precursor under inert atmosphere
In this step, the second precursor obtained in step S200 is sintered in an inert atmosphere, so that a part of the silica in the amorphous silica layer in the second precursor reacts with a water-soluble lithium source (the water-soluble lithium source is SiO, for example, lithium carbonate) to generate different types of lithium silicate2+1/2Li2CO3→1/2Li2Si2O5+1/2CO2，SiO2+Li2CO3→Li2SiO3+CO2，SiO2+2Li2CO3→Li4SiO4+2CO2) Forming a silicon-based material core containing another part of silicon dioxide and Li2Si2O5、Li2SiO3And Li4SiO4Lithium silicate coating layer (ginseng)See fig. 6), which is the third precursor.
Further, the sintering temperature in the sintering process is 700-900 ℃, the heating rate is 0.5-10 ℃/min, and the sintering time is 1-36 h.
S400: etching the third precursor
In the step, hydrofluoric acid (the concentration of the hydrofluoric acid is 0.5-1.0 mol/L) is adopted to etch the third precursor obtained in the step S300 (the etching time is 1-120 min), and the other part of silicon dioxide in the amorphous silicon dioxide layer in the third precursor and Li in the lithium silicate coating layer are removed2Si2O5Except lithium silicate, obtaining a fourth precursor with a hollow core-shell structure and pores on the lithium silicate coating layer, namely forming Li on the periphery of the silicon-based material2Si2O5And due to the removal of another part of silicon dioxide, there will be a distance between the formed lithium silicate coating layer and the inner core (refer to fig. 7), an expansion space is reserved for the expansion of the inner core, when the silicon-based anode material is charged and discharged, the expansion stress is relatively low, and the strength of the lithium silicate coating layer is greater than that of the physical pyrolytic carbon layer, thereby improving the cycling stability of the material, and the lithium silicate coating layer of the present application only contains Li2Si2O5Due to crystalline Li2Si2O5The method has the advantages that the method does not react with water, negative problems such as dissolution and the like do not exist in the subsequent homogenization process, and simultaneously, along with the etching of other types of lithium silicate and residual silicon dioxide, the lithium silicate coating has a plurality of pores, so that the conduction of lithium ions is facilitated, the polarization of the material is reduced, and the precursor with the hollow core-shell structure is obtained.
S500: coating a carbon coating layer on the surface of the fourth precursor
In this step, a carbon coating layer (refer to fig. 8) is coated on the surface of the lithium silicate coating layer of the fourth precursor of the hollow core-shell structure obtained in step S400, so as to obtain the silicon-based negative electrode material, the carbon coating layer can effectively avoid direct contact between the negative electrode silicon-based material and the electrolyte, reduce side reactions, improve the first effect, and the carbon coating layer itself has an effect of limiting expansion, thereby further improving the cycle performance of the material. Specifically, the surface-coated carbon coating layer on the fourth precursor of the hollow core-shell structure obtained in step S400 may be a gas-phase coating layer, a liquid-phase coating layer, or a solid-phase coating layer, for example, the gas-phase coating layer is coated with an organic carbon-containing gas such as methane or acetylene; the liquid phase coating is performed using glucose, sucrose, a phenol resin solution, or the like, and the solid phase coating is performed using asphalt powder or the like.
According to the method for preparing the silicon-based negative electrode material, silicon dioxide is coated on the surface of the silicon-based material, then the silicon-based material with the silicon dioxide is coated with the water-soluble lithium source, and the silicon-based material is roasted in the inert atmosphere, so that part of the silicon dioxide reacts with the water-soluble lithium source to generate different types of lithium silicate (the water-soluble lithium source takes lithium carbonate as an example, SiO is taken as the water-soluble lithium source)2+1/2Li2CO3→1/2Li2Si2O5+1/2CO2，SiO2+Li2CO3→Li2SiO3+CO2，SiO2+2Li2CO3→Li4SiO4+2CO2) That is, the surface of the core of the silicon-based material is formed with silicon dioxide and Li2Si2O5、Li2SiO3And Li4SiO4Then etching the precursor obtained from the lithium silicate coating layer, removing the other part of silicon dioxide in the precursor and removing Li in the lithium silicate coating layer2Si2O5With lithium silicates other than, i.e. formed to include Li at the periphery of the silicon-based material2Si2O5The lithium silicate coating layer is separated from the inner core due to the removal of another part of silicon dioxide, an expansion space is reserved for the expansion of the inner core, when the silicon-based anode material is charged and discharged, the expansion stress is relatively low, the strength of the lithium silicate coating layer is greater than that of the physical pyrolytic carbon layer, and therefore the cycling stability of the material is improved, and only Li is contained in the lithium silicate coating layer2Si2O5Due to crystalline Li2Si2O5Does not react with water, afterThe negative problems of dissolution and the like do not exist in the continuous homogenizing process, and simultaneously along with the etching of the rest types of lithium silicate and the rest silicon dioxide, the lithium silicate coating has a plurality of pores, so that the conduction of lithium ions is facilitated, the polarization of the material is reduced, and finally, a carbon coating layer is coated on the surface of the lithium silicate coating layer, so that the carbon coating layer can effectively avoid the direct contact of a silicon-based material of a negative electrode and electrolyte, the occurrence of side reactions is reduced, the first effect is improved, and the carbon coating layer also has the effect of limiting expansion, thereby further improving the cycle performance of the material. Therefore, the silicon-based negative electrode material with higher first-effect and cycling stability can be obtained by adopting the method, and the first-effect and cycling performance of the lithium battery can be improved by loading the negative electrode prepared by adopting the silicon-based negative electrode material in the lithium battery.
It should be noted that the features and advantages described above for the silicon-based anode material are also applicable to the method for preparing the silicon-based anode material, and are not described herein again.
In a third aspect of the invention, a negative electrode is presented. According to the embodiment of the invention, the negative electrode is prepared from the silicon-based negative electrode material or the silicon-based negative electrode material obtained by the method. Therefore, the cathode is made of the silicon-based cathode material with high first-effect and excellent cycling stability, so that the cathode has high first-effect and cycling performance. It should be noted that the features and advantages described above for the silicon-based anode material and the preparation method thereof are also applicable to the anode, and are not described herein again.
In a fourth aspect of the present invention, a lithium battery is provided. According to an embodiment of the present invention, the lithium battery includes the negative electrode described above. Therefore, the lithium battery has high first-effect and cycle performance by loading the negative electrode with high first-effect and cycle performance prepared by the silicon-based negative electrode material. It should be noted that the features and advantages described above for the negative electrode are also applicable to the lithium battery, and are not described in detail here.
The following embodiments of the present invention are described in detail, and it should be noted that the following embodiments are exemplary only, and are not to be construed as limiting the present invention. In addition, all reagents used in the following examples are commercially available or can be synthesized according to methods herein or known, and are readily available to those skilled in the art for reaction conditions not listed, if not explicitly stated.
Example 1
(1) Takes tetraethoxysilane as raw material, and forms amorphous SiO by coating on the surface of a simple substance silicon with the thickness of 50nm2Obtaining a first precursor, wherein the amorphous SiO2The thickness of the layer was 30nm, the amorphous SiO being based on the total mass of the first precursor2The mass percentage of the layer is 5%;
(2) coating lithium carbonate on the surface of the first precursor by using two-fluid spray drying to obtain a second precursor, wherein the molar ratio of Li in the lithium carbonate coated on the first precursor to O in the amorphous silicon dioxide layer is 0.12;
(3) sintering the second precursor in a tube furnace in a protective atmosphere of nitrogen, heating to 830 ℃ at a speed of 3 ℃/min, preserving heat for 6h, and naturally cooling to room temperature to obtain a third precursor;
(4) pickling the third precursor with 0.5mol/L hydrofluoric acid for 60min, drying, and sieving with 400 mesh sieve to obtain a fourth precursor (lithium silicate (Li)2Si2O5) The thickness of the coating layer was 10nm, based on the total mass of the silicon-based negative electrode material, lithium silicate (Li)2Si2O5) The mass ratio of the coating layer is 15%);
(5) taking sucrose as a raw material, carrying out liquid-phase carbon coating treatment on the fourth precursor (based on the total mass of the silicon-based negative electrode material, the mass ratio of the carbon coating layer is 10%), and finally obtaining the silicon-based negative electrode material with the hollow core-shell structure (the carbon coating thickness is 35 nm).
Example 2
(1) Takes tetraethoxysilane as raw material, and forms amorphous SiO by coating on the surface of a simple substance silicon with the thickness of 50nm2Obtaining a first precursor, wherein the amorphous SiO2The thickness of the layer is 35nm,the amorphous SiO is based on the total mass of the first precursor2The mass percentage of the layer is 5.5%;
(2) coating lithium carbonate on the surface of the first precursor by using two-fluid spray drying to obtain a second precursor, wherein the molar ratio of Li in the lithium carbonate coated on the first precursor to O in the amorphous silicon dioxide layer is 0.12;
(3) sintering the second precursor in a tube furnace in a protective atmosphere of nitrogen, heating to 830 ℃ at a speed of 3 ℃/min, preserving heat for 6h, and naturally cooling to room temperature to obtain a third precursor;
(4) pickling the third precursor with 0.5mol/L hydrofluoric acid for 60min, drying, and sieving with 400 mesh sieve to obtain a fourth precursor (lithium silicate (Li)2Si2O5) The thickness of the coating layer was 10nm, based on the total mass of the silicon-based negative electrode material, lithium silicate (Li)2Si2O5) The mass ratio of the coating layer is 15%);
(5) and (3) performing solid-phase carbon coating treatment on the fourth precursor by taking asphalt as a raw material (the mass ratio of the carbon coating layer is 10% based on the total mass of the silicon-based negative electrode material), and finally obtaining the silicon-based negative electrode material with the hollow core-shell structure (the carbon coating thickness is 30 nm).
Example 3
(1) Sodium silicate is used as a raw material, and the surface of SiO with the thickness of 3 mu m is coated to form amorphous SiO2Obtaining a first precursor, wherein the amorphous SiO2The thickness of the layer is 50nm, the amorphous SiO being based on the total mass of the first precursor2The mass ratio of the layer is 7%;
(2) lithium oxalate is used as a raw material, and two-fluid spray drying is adopted to coat lithium carbonate on the surface of the first precursor to obtain a second precursor, wherein the molar ratio of Li in the lithium carbonate coated on the first precursor to O in the amorphous silicon dioxide layer is 0.1;
(3) sintering the second precursor in a tube furnace in a protective atmosphere of nitrogen, heating to 820 ℃ at a speed of 3 ℃/min, preserving heat for 6h, and naturally cooling to room temperature to obtain a third precursor;
(4) pickling the third precursor with 1mol/L hydrofluoric acid for 60min, drying, and sieving with 400 mesh sieve to obtain a fourth precursor (lithium silicate (Li)2Si2O5) The thickness of the coating layer was 20nm, based on the total mass of the silicon-based negative electrode material, lithium silicate (Li)2Si2O5) The mass percentage of the coating layer is 10%);
(5) and (3) carrying out gas-phase carbon coating treatment on the fourth precursor by taking acetylene as a raw material (based on the total mass of the silicon-based negative electrode material, the mass ratio of a carbon coating layer is 5%), and finally obtaining the silicon-based negative electrode material with the hollow core-shell structure (the carbon coating thickness is 18 nm).
Example 4
(1) Sodium silicate is used as a raw material, and the surface of SiO with the thickness of 5 mu m is coated to form amorphous SiO2Obtaining a first precursor, wherein the amorphous SiO2The thickness of the layer was 80nm, the amorphous SiO being based on the total mass of the first precursor2The mass ratio of the layer is 10 percent;
(2) lithium oxalate is used as a raw material, and two-fluid spray drying is adopted to coat lithium carbonate on the surface of the first precursor to obtain a second precursor, wherein the molar ratio of Li in the lithium carbonate coated on the first precursor to O in the amorphous silicon dioxide layer is 0.1;
(3) sintering the second precursor in a tube furnace in a protective atmosphere of nitrogen, heating to 840 ℃ at the speed of 3 ℃/min, preserving heat for 6h, and naturally cooling to room temperature to obtain a third precursor;
(4) pickling the third precursor with 1mol/L hydrofluoric acid for 60min, drying, and sieving with 400 mesh sieve to obtain a fourth precursor (lithium silicate (Li)2Si2O5) The thickness of the coating layer was 50nm, based on the total mass of the silicon-based negative electrode material, lithium silicate (Li)2Si2O5) The mass percentage of the coating layer is 10%);
(5) and (3) carrying out gas-phase carbon coating treatment on the fourth precursor by taking acetylene as a raw material (the mass ratio of the carbon coating layer is 7% based on the total mass of the silicon-based negative electrode material), and finally obtaining the silicon-based negative electrode material with the hollow core-shell structure (the carbon coating thickness is 24 nm).
Comparative example 1
Acetylene is used as a raw material, and amorphous carbon is coated on the surface of a 50nm simple substance silicon (based on the total mass of a silicon-based negative electrode material, the mass percentage of the amorphous carbon is 10%).
Comparative example 2
The method is characterized in that high-temperature asphalt is used as a raw material, and amorphous carbon is coated on the surface of SiO with the thickness of 5 mu m (the mass percentage of the amorphous carbon is 7 percent based on the total mass of the silicon-based negative electrode material).
Respectively mixing the silicon-based negative electrode materials obtained in examples 1-4 and comparative examples 1-2 according to the mass ratio of active substances, acetylene black and an adhesive (the mass ratio of CMC to SBR is 1:1) of 80: 5: 15 to prepare slurry, coating the slurry on copper foil to prepare a negative pole piece, wherein the loading capacity is 3mg/cm2Taking a metal lithium sheet as a counter electrode, a polypropylene microporous membrane (celgard2400) as a diaphragm, and 1mol/L LiPF6The solution (DC, DEC, EMC volume ratio 1:1:1) was used as electrolyte and assembled into 2016 button cell in glove box, the electrical performance test results are shown in Table 1, the charge and discharge schedule: the charge-discharge range is 0.005-1.5V, the 1 st cycle is 0.1C for charge-discharge, and the 2 nd to 200 th cycles are 0.2C for charge-discharge.
Electrical performance results for corresponding cells of examples 1-4 and comparative examples 1-2
Figure BDA0002710146960000111
Figure BDA0002710146960000121
The silicon-based materials of examples 1-2 and comparative example 1 are all nano silicon which is characterized by high specific capacity but poor cycle performance, the silicon-based negative electrode material of comparative example 1 only has a carbon coating layer and no lithium silicate coating layer, and the lithium silicate is an inactive substance and does not contribute to the comparative capacity, so the specific capacity of comparative example 1 is higher than that of examples 1-2, and the first efficiency and cycle performance of the corresponding batteries of examples 1-2 are better than those of the corresponding batteries of comparative example 1.
The silicon-based materials of examples 3 to 4 and comparative example 2 were each targeted for silicon oxide, which was characterized by a specific capacity lower than that of nano-silicon and a cycle performance better than that of nano-silicon, and thus the specific capacities of the corresponding batteries of examples 3 to 4 and comparative example 2 were lower than those of the corresponding batteries of examples 1 to 2, but the cycle performances of the corresponding batteries of examples 3 to 4 and comparative example 2 were better than those of the corresponding batteries of examples 1 to 2.
In the description herein, references to the description of the term "one embodiment," "some embodiments," "an example," "a specific example," or "some examples," etc., mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above are not necessarily intended to refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, various embodiments or examples and features of different embodiments or examples described in this specification can be combined and combined by one skilled in the art without contradiction.
Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention, and that variations, modifications, substitutions and alterations can be made to the above embodiments by those of ordinary skill in the art within the scope of the present invention.

Claims (19)

1. A silicon-based anode material, comprising:
a core comprising a silicon-based material;
a lithium silicate coating layer containing only Li2Si2O5The lithium silicate coating layer is arranged at the periphery of the inner core, pores are formed in the lithium silicate coating layer, and a distance exists between the lithium silicate coating layer and the inner core;
a carbon coating layer coated on the lithium silicate coating layer,
wherein the thickness of the lithium silicate coating layer is 10 to 100nm,
the method for preparing the silicon-based anode material comprises the following steps:
(1) coating silicon dioxide on the surface of a silicon-based material to obtain a first precursor;
(2) coating a water-soluble lithium source on the first precursor to obtain a second precursor;
(3) sintering the second precursor under inert atmosphere, so that a part of the silicon dioxide reacts with the water-soluble lithium source to form Li-containing silicon on the surface of the silicon-based material2Si2O5To obtain a third precursor;
(4) etching the third precursor to remove the other part of the silicon dioxide and remove Li in the lithium silicate coating layer2Si2O5Lithium silicate except the lithium silicate so as to obtain a fourth precursor which is provided with pores on the lithium silicate coating layer and has a hollow core-shell structure;
(5) and coating a carbon coating layer on the surface of the fourth precursor so as to obtain the silicon-based negative electrode material.
2. The silicon-based anode material according to claim 1, wherein the silicon-based material comprises at least one of elemental nano-silicon and silicon oxide.
3. The silicon-based anode material as claimed in claim 2, wherein the elemental nano-silicon has a particle size D50 of 5-100 nm.
4. The silicon-based negative electrode material as claimed in claim 2, wherein the silicon oxide has a chemical formula of SiOxAnd x is 0.5 to 1.5.
5. The silicon-based negative electrode material as claimed in claim 2, wherein the silicon oxide has a particle size D50 of 100nm to 15 μm.
6. The silicon-based anode material according to claim 1, wherein the lithium silicate coating layer is 5-30% by mass based on the total mass of the silicon-based anode material.
7. The silicon-based negative electrode material as claimed in claim 1, wherein the carbon coating layer has a thickness of 1 to 50 nm.
8. The silicon-based anode material according to claim 1, wherein the mass percentage of the carbon coating layer is 1-20% based on the total mass of the silicon-based anode material.
9. A method for preparing a silicon-based anode material according to any one of claims 1 to 8, comprising:
(1) coating silicon dioxide on the surface of a silicon-based material to obtain a first precursor;
(2) coating a water-soluble lithium source on the first precursor to obtain a second precursor;
(3) sintering the second precursor under inert atmosphere, so that a part of the silicon dioxide reacts with the water-soluble lithium source to form Li-containing silicon on the surface of the silicon-based material2Si2O5To obtain a third precursor;
(4) etching the third precursor to remove the other part of the silicon dioxide and remove Li in the lithium silicate coating layer2Si2O5Lithium silicate except the lithium silicate so as to obtain a fourth precursor which is provided with pores on the lithium silicate coating layer and has a hollow core-shell structure;
(5) and coating a carbon coating layer on the surface of the fourth precursor so as to obtain the silicon-based negative electrode material.
10. The method according to claim 9, wherein in the step (1), the silica is amorphous silica, and the amorphous silica coating layer formed on the surface of the silicon-based material has a thickness of 30 to 150 nm.
11. The method according to claim 10, wherein in the step (1), the amorphous silica coating layer has a mass ratio of 5 to 20% based on the total mass of the first precursor.
12. The method according to claim 9, wherein in step (2), the water-soluble lithium source is coated on the first precursor by spray drying.
13. The method of claim 9, wherein in step (2), the water-soluble lithium source comprises at least one of lithium carbonate, lithium oxalate, lithium nitrate, and lithium acetate.
14. The method according to claim 9, wherein in the step (2), the molar ratio of lithium in the water-soluble lithium source to oxygen in the silica is 0.08 to 0.2.
15. The method according to claim 9, wherein in the step (3), the sintering temperature is 700-900 ℃, the heating rate is 0.5-10 ℃/min, and the sintering time is 1-36 h.
16. The method of claim 9, wherein in step (4), the third precursor is etched with hydrofluoric acid.
17. The method according to claim 16, wherein in the step (4), the concentration of the hydrofluoric acid is 0.5-1.0 mol/L, and the etching time is 1-120 min.
18. A negative electrode, characterized in that it is prepared from a silicon-based negative electrode material according to any one of claims 1 to 8 or obtained by a method according to any one of claims 9 to 17.
19. A lithium battery comprising the negative electrode as claimed in claim 18.
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