CN111435733A - Silicon-carbon composite material, preparation method thereof, negative electrode, power battery and electric automobile - Google Patents

Silicon-carbon composite material, preparation method thereof, negative electrode, power battery and electric automobile Download PDF

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CN111435733A
CN111435733A CN201911354572.9A CN201911354572A CN111435733A CN 111435733 A CN111435733 A CN 111435733A CN 201911354572 A CN201911354572 A CN 201911354572A CN 111435733 A CN111435733 A CN 111435733A
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silicon
carbon
core
composite material
solid electrolyte
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CN111435733B (en
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段瑞杰
马忠龙
邓素祥
蔡挺威
赵晓宁
邵玲
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Svolt Energy Technology Co Ltd
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Svolt Energy Technology 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
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention provides a silicon-carbon composite material, a preparation method thereof, a negative electrode, a power battery and an electric automobile. The silicon-carbon composite material is a core-shell structure microsphere, the core-shell structure microsphere is provided with a core and a shell, and the shell coats the core, wherein the core comprises a solid electrolyte, a linear first carbon material and a silicon-containing nanoparticle coated by a second carbon material; the shell layer includes the solid electrolyte coated with the first carbon material and the second carbon material. The silicon-carbon composite material has the advantages of good conductivity, high capacity, good rate capability, difficult expansion, difficult pulverization, strong stability and good cyclicity.

Description

Silicon-carbon composite material, preparation method thereof, negative electrode, power battery and electric automobile
Technical Field
The invention relates to the technical field of materials, in particular to a silicon-carbon composite material, a preparation method thereof, a negative electrode, a power battery and an electric automobile.
Background
In the related art, the silicon-carbon composite material is mainly prepared by a mechanical ball milling mode or chemical methods such as a chemical vapor deposition technology, a thermal magnesium reduction technology and the like. However, the carbon nanotube, which is a carbon material commonly used in the silicon-carbon composite material, is easy to be entangled and agglomerated due to its high specific surface area and high aspect ratio, so that the nano-silicon particles cannot be uniformly distributed in the conductive framework of the carbon nanotube, which is not favorable for the electrochemical performance of the silicon-carbon composite material. Secondly, the interface effect between the nano silicon particles and the solid electrolyte is severe, and the diffusion of lithium ions is severely inhibited by the pores of the particles and the gaps between the particles, which affects the performance of the battery. Thirdly, in the lithiation process of the nano silicon particles, the generated stress causes mechanical pulverization of the nano silicon particles, so that the structure of the silicon-carbon composite material is damaged, the collapse of a conductive network is caused, and the capacity of the power battery is rapidly attenuated; repeatedly, the volume expansion of the nano silicon particles can cause the contact surface between the nano silicon particles and the electrolyte to be continuously changed, so that the SEI film on the surface of the silicon-carbon composite material is very unstable, the coulombic efficiency is reduced, and the electrolyte is consumed, so that the cycle performance of the power battery is poor; finally, the electronic conductivity and the ionic conductivity of the nano silicon particles are low, so that the rate performance of the power battery is poor.
Thus, the related art of the existing silicon carbon composite material still needs to be improved.
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, the invention aims to provide a silicon-carbon composite material which has good conductivity, high capacity, good rate capability, difficult expansion, difficult pulverization, strong stability or good cyclicity.
In one aspect of the invention, a silicon carbon composite is provided. According to the embodiment of the invention, the silicon-carbon composite material is a core-shell structure microsphere, the core-shell structure microsphere is provided with a core and a shell, and the shell coats the core, wherein the core comprises a solid electrolyte, a linear first carbon material and a silicon-containing nanoparticle coated by a second carbon material; the shell layer includes the solid electrolyte coated with the first carbon material and the second carbon material. The inventor finds that the silicon-carbon composite material has the advantages of good conductivity, high capacity, good rate capability, difficult expansion, difficult pulverization, strong stability and good cyclicity.
According to an embodiment of the invention, the first carbon material comprises carbon nanotubes; the second carbon material includes amorphous carbon.
According to an embodiment of the present invention, the carbon nanotubes include at least one of single-walled carbon nanotubes and multi-walled carbon nanotubes.
According to an embodiment of the present invention, the solid electrolyte includes at least one of an oxide solid electrolyte and a sulfide solid electrolyte.
According to an embodiment of the present invention, the oxide solid state electrolyte comprises at least one of lithium lanthanum zirconium oxygen, lithium lanthanum titanium oxygen, lithium lanthanum zirconium titanium oxygen, lithium aluminum titanium oxygen, lithium titanium aluminum lithium phosphate, germanium aluminum lithium phosphate, and lithium nitrogen phosphate.
According to an embodiment of the present invention, the particle size of the oxide solid electrolyte is 0.01 μm to 5 μm.
According to an embodiment of the invention, the sulphide solid state electrolyte comprises at least one of lithium germanium phosphorus sulphur, lithium phosphorus sulphur iodide and lithium phosphorus sulphur chloride.
According to an embodiment of the present invention, the particle size of the sulfide solid electrolyte is 0.01 μm to 5 μm.
According to an embodiment of the invention, the solid-state electrolyte further comprises at least one of anatase titanium dioxide and lithium titanate.
According to an embodiment of the invention, the silicon-containing nanoparticles comprise at least one of nano-silicon particles and nano-silica particles.
According to an embodiment of the present invention, the nano-silicon particles include at least one of single crystal silicon, polycrystalline silicon, and amorphous silicon.
According to an embodiment of the invention, the silicon-containing nanoparticles have a particle size of 0.01 μm to 5 μm.
According to the embodiment of the invention, in the core-shell structure microsphere, the mass ratio of the core to the shell is (1-4): (16-19).
According to an embodiment of the present invention, in the core, a mass ratio of the solid electrolyte, the first carbon material, the second carbon material, and the silicon-containing nanoparticles is (10 to 40): (1-35): (1-35): (20-60).
According to an embodiment of the present invention, in the shell layer, a mass ratio of the first carbon material, the solid electrolyte, and the second carbon material is (1 to 7): (6-12): (1-7).
In another aspect of the invention, the invention provides a method of making the aforementioned silicon carbon composite. According to an embodiment of the invention, the method comprises: mixing a carbonaceous surfactant, the solid electrolyte, the first carbon material, the silicon-containing nanoparticles, and a solvent to obtain a first dispersion; carrying out spray drying treatment on the first dispersion liquid to obtain a first prefabricated object; calcining the first prefabricated object to obtain the core; mixing the core, the first carbon material, the carbonaceous surfactant, the solid electrolyte, and the solvent to obtain a second dispersion; carrying out spray drying treatment on the second dispersion liquid to obtain a second prefabricated object; and calcining the second prefabricated object to obtain the silicon-carbon composite material. The inventor finds that the method is simple and convenient to operate, easy to implement and easy for industrial production, the silicon-carbon composite material can be effectively prepared, and the prepared silicon-carbon composite material is good in conductivity, high in capacity, good in rate capability, not easy to expand and pulverize, strong in stability and good in cyclicity.
According to an embodiment of the present invention, the carbon-containing surfactant comprises at least one of polyvinylpyrrolidone and polycarboxymethyl methacrylate.
According to an embodiment of the present invention, the solvent includes at least one of deionized water, tetrahydrofuran, dimethyl sulfoxide, and toluene.
According to an embodiment of the present invention, when the first dispersion is obtained, the mass ratio of the carbon-containing surfactant, the solid electrolyte, the first carbon material, and the silicon-containing nanoparticles is (2 to 30): (5-30): (1-30): (20-60).
According to an embodiment of the present invention, when the second dispersion liquid is obtained, the mass ratio of the core, the first carbon material, the carbonaceous surfactant, and the solid electrolyte is (20 to 60): (1-30): (2-30): (5-30).
According to an embodiment of the invention, the spray drying process satisfies at least one of the following conditions: the temperature of the air inlet is 110-200 ℃; wind speed of 0.1m3/min～0.5m3The speed of the peristaltic pump is 0.005L/min-0.033L/min, the ejector is automatically dredged within 20 s-80 s, and the flow rate of the spraying gas is 5N L/min-20N L/min.
According to the embodiment of the invention, the calcination treatment is carried out in the atmosphere of inert gas, the gas flow is 10m L/min-80 m L/min, the heating rate is 5 ℃/min-20 ℃/min, the temperature is 850-950 ℃, and the time is 1-3 h.
According to an embodiment of the invention, the inert gas is argon.
In yet another aspect of the invention, a negative electrode is provided. According to an embodiment of the invention, the negative electrode comprises the aforementioned silicon carbon composite. The inventor finds that the negative electrode has high capacity, good rate capability, strong stability and good cyclicity.
In yet another aspect of the invention, a power cell is provided. According to an embodiment of the invention, the power cell comprises the aforementioned negative electrode. The inventor finds that the power battery has good electrochemical performance and long service life.
In yet another aspect of the present invention, an electric vehicle is provided. According to an embodiment of the invention, the electric vehicle comprises the power battery. The inventor finds that the electric automobile has strong driving force and good commercial prospect.
Drawings
Fig. 1 shows a schematic cross-sectional structure of a silicon carbon composite material according to an embodiment of the present invention.
Fig. 2 shows a schematic flow diagram of a method for preparing a silicon carbon composite material according to an embodiment of the present invention.
FIG. 3 shows a scanning electron micrograph (scale bar 200nm) of a core prepared in example 1 of the present invention.
FIG. 4 shows SEM pictures of the silicon-carbon composite material prepared in example 1 of the present invention at different magnifications (scale bar of 2 μm in a picture; scale bar of 200nm in a picture).
Fig. 5 shows a charge-discharge curve of the negative electrode sheet manufactured in example 1 of the present invention.
Fig. 6 shows the result of the rate performance test of the negative electrode sheet manufactured in example 1 of the present invention.
Reference numerals:
10: silicon-carbon composite materials 100a, 100 b: solid electrolytes 200a, 200 b: first carbon materials 300a, 300 b: second carbon material 400: silicon-containing nanoparticles
Detailed Description
The following describes embodiments of the present invention in detail. The following examples are illustrative only and are not to be construed as limiting the invention. The examples, where specific techniques or conditions are not indicated, are to be construed according to the techniques or conditions described in the literature in the art or according to the product specifications. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products commercially available.
In one aspect of the invention, a silicon carbon composite is provided. According to an embodiment of the present invention, referring to fig. 1, the silicon-carbon composite material 10 is a core-shell structure microsphere having a core and a shell, wherein the shell coats the core, wherein the core includes a solid electrolyte 100a, a silicon-containing nanoparticle 400 coated with a linear first carbon material 200a and a linear second carbon material 300 a; the shell layer includes the solid electrolyte 100b coated with the first carbon material 200b and the second carbon material 300 b. The inventors found that, in the silicon-carbon composite material 10, the first carbon materials 200a and 200b having a linear shape have good electrical conductivity, and can be used as an electronic conductive framework of the whole silicon-carbon composite material 10, so that the silicon-carbon composite material 10 has excellent electronic conductivity, and at the same time, has good mechanical properties, and can structurally support the whole silicon-carbon composite material 10, and the solid electrolytes 100a and 100b have strong electrical conductivity, and can be used as an ionic conductive framework of the whole silicon-carbon composite material 10, so that the silicon-carbon composite material 10 has excellent ionic conductivity; moreover, in the core of the silicon-carbon composite material 10, the silicon-containing nanoparticles 400 coated with the solid electrolyte 100a, the first carbon material 200a and the second carbon material 300a are uniformly distributed, and the shell layer coats the core, so that the shell layer forms an artificial SEI film in the whole silicon-carbon composite material 10, and when the silicon-carbon composite material 10 is used as a negative electrode material of a power battery, the silicon-carbon composite material can further isolate the direct contact between the silicon-containing nanoparticles 400 and an electrolyte, and provides a lithium ion and electron channel; meanwhile, the second carbon material 300a coating the silicon-containing nanoparticles 400 provides a certain buffer space for the volume expansion phenomenon of the silicon-containing nanoparticles 400, and the shell layer coats the entire core, which in turn provides a more sufficient buffer space for the volume expansion phenomenon of the silicon-containing nanoparticles 400. In conclusion, the silicon-carbon composite material provided by the invention has a good structure, and all components in the silicon-carbon composite material are matched with each other to play a synergistic effect, so that the silicon-carbon composite material provided by the invention has the advantages of good 10 conductivity, high capacity, good rate capability, difficulty in expansion, difficulty in pulverization, strong stability and good cyclicity.
Further, according to an embodiment of the present invention, the first carbon material 200a, 200b comprises carbon nanotubes; the second carbon material 300a, 300b comprises amorphous carbon. Thus, the carbon nanotubes have high electrical conductivity and are soft, which can alleviate the expansion of the silicon-containing nanoparticles 400 when the silicon-carbon composite material 10 undergoes an electrode reaction; meanwhile, the silicon-containing nanoparticles 400 can be further connected with each other, and more electrons are transmitted to the surface of the silicon-containing nanoparticles 400 after electrode reaction occurs, so that the reaction activity and the structural stability of the whole silicon-carbon composite material 10 are improved, and the cycle performance of the power battery cathode comprising the silicon-carbon composite material is better; in addition, the amorphous carbon can be directly obtained by carbonizing organic matters, and the forming process is simple and convenient and is easy to industrialize.
According to an embodiment of the present invention, further, the carbon nanotube may include a single-walled carbon nanotube, a multi-walled carbon nanotube, and the like. Therefore, the material source is wide and easy to obtain, the cost is low, and the electronic conductivity in the silicon-carbon negative electrode material 10 and the electronic conductivity on the surface can be improved well.
Further, according to an embodiment of the present invention, the solid electrolytes 100a, 100b may include an oxide solid electrolyte or a sulfide solid electrolyte, or the like. In some embodiments of the present invention, specifically, the oxide solid electrolyte may specifically include lithium lanthanum zirconium oxygen, lithium lanthanum titanium oxygen, lithium lanthanum zirconium titanium oxygen, lithium aluminum titanium oxygen, lithium titanium aluminum lithium phosphate, germanium aluminum lithium phosphate, lithium nitrogen phosphate, and the like; in other embodiments of the present invention, the sulfide solid state electrolyte may specifically include lithium germanium phosphorus sulfide, lithium phosphorus sulfur iodide, lithium phosphorus sulfur chloride, and the like. Thus, since the solid electrolytes 100a and 100b have high conductivity, the silicon-carbon composite material 10 can have high ionic conductivity; meanwhile, the materials are wide in source, easy to obtain and low in cost, and have better matching degree with other components in the silicon-carbon composite material 10, so that the components in the silicon-carbon composite material 10 can better play a synergistic effect, the conductivity of the silicon-carbon composite material 10 is further improved, the capacity is further improved, the rate capability is further improved, the expansion is more difficult to occur, the pulverization is more difficult, the stability is further enhanced, and the cyclicity is further improved.
According to an embodiment of the present invention, further, the particle size of the solid electrolytes 100a and 100b may be 0.01 μm to 5 μm. In some embodiments of the present invention, the particle size of the solid electrolyte 100a, 100b may be specifically 0.01 μm, 0.02 μm, 0.05 μm, 0.1 μm, 0.2 μm, 0.5 μm, 1 μm, 2 μm, 3 μm, 4 μm, 5 μm, or the like. Therefore, the particle size of the solid electrolytes 100a and 100b is in the above range, so that the solid electrolytes 100a and 100b can be better and uniformly mixed with the silicon-containing nanoparticles 400 in the silicon-carbon composite material 10, so that the solid electrolytes 100a and 100b can be better present in the silicon-carbon composite material 10, and the components in the silicon-carbon composite material 10 can better perform their respective functions to make the silicon-carbon composite material have good conductivity, high capacity and good rate capability.
In other embodiments of the present invention, the solid electrolyte 100a, 100b may further include anatase titanium dioxide or lithium titanate. Therefore, a stable artificial SEI film can be further formed on the outer surface of the silicon carbon composite material 10, thereby further improving the stability of the silicon carbon composite material 10.
Further, according to the embodiment of the present invention, the silicon-containing nanoparticles 400 may specifically include nano silicon particles, nano silicon oxide particles, and the like. Still further, in some embodiments of the present invention, the nano-silicon particles may include single crystal silicon, polycrystalline silicon, amorphous silicon, and the like. Therefore, the material source is wide and easy to obtain, and the cost is lower.
According to an embodiment of the present invention, still further, the silicon-containing nanoparticles 400 may have a particle size of 0.01 μm to 5 μm. In some embodiments of the present invention, the particle size of the silicon-containing nanoparticles 400 may be specifically 0.01 μm, 0.02 μm, 0.05 μm, 0.1 μm, 0.2 μm, 0.5 μm, 1 μm, 2 μm, 3 μm, 4 μm, or 5 μm, and the like. Therefore, the particle size of the silicon-containing nanoparticles 400 is in the above range, so that the silicon-containing nanoparticles 400 can be better and uniformly mixed with the solid electrolytes 100a and 100b in the silicon-carbon composite material 10, so that the silicon-containing nanoparticles 400 can be better present in the silicon-carbon composite material 10, and further, each component in the silicon-carbon composite material 10 can better exert respective function to enable the silicon-carbon composite material to have good conductivity, high capacity and good rate capability; in addition, the particle size of the silicon-containing nanoparticles 400 in the above range makes it possible to increase the specific surface area inside the silicon-carbon composite material 10 and to increase the contact surface area between the silicon-containing nanoparticles 400 inside the silicon-carbon composite material and the solid electrolytes 100a and 100b, thereby achieving higher ionic conductivity.
According to the embodiments of the present invention, the inventors have further studied the ratio between the core and the shell in the core-shell structure microsphere, and surprisingly found that, in the core-shell structure microsphere, when the mass ratio between the core and the shell is (1-4): (16-19), specifically, the ratio of 1: 16. 1: 17. 1: 18. 1: 19. 1: 8. 2: 17. 1: 9. 2: 19. 3: 16. 3: 17. 1: 6. 3: 19. 1: 4. 4: 17. 2: 9 or 19, the ratio between the core and the shell in the core-shell structure microsphere is proper, so that the conductivity of the outer surface of the core-shell structure microsphere is good, and the shell can be better matched with the core, so that when the silicon-carbon composite material is used as a negative electrode of a power battery, compared with the related technology, more electrons are transmitted to the surface of the nano silicon particles after electrode reaction occurs, and further the reactivity and the structural stability of the whole silicon-carbon composite material are improved.
Further according to an embodiment of the present invention, in the core, a mass ratio of the solid electrolyte 100a, the first carbon material 200a, the second carbon material 300a, and the silicon-containing nanoparticles 400 may be (10 to 40): (1-35): (1-35): (20-60). In some embodiments of the present invention, the solid electrolyte 100a, the first carbon material 200a, and the second carbon have better internal electrical conductivity in the core, and when the silicon-carbon composite material 10 is used as a negative electrode material of a power battery, in the core of the silicon-carbon composite material 10, the silicon-containing nanoparticles 400 coated by the solid electrolyte 100a, the first carbon material 200a, and the second carbon material 300a are distributed more uniformly, so that the electrical conductivity of the silicon-carbon composite material 10 is further improved, the capacity is further improved, the rate capability is further improved, and the silicon-carbon composite material is less prone to swelling, is less prone to pulverization, has further improved stability, and has further improved cyclicity.
According to an embodiment of the present invention, further, in the shell layer, a mass ratio of the first carbon material 200b, the solid electrolyte 100b, and the second carbon material 300b is (1 to 7): (6-12): (1-7). In some embodiments of the present invention, in the shell layer, the mass ratio of the first carbon material 200b, the solid electrolyte 100b, and the second carbon material 300b may be specifically 1: 6: 1. 4: 9: 4 or 7: 12: 7, and the like. Therefore, the components in the shell layer are in proper proportion, so that the conductivity of the outer surface of the core-shell structure microsphere is better, when the silicon-carbon composite material 10 is used as a negative electrode material of a power battery, the silicon-carbon composite material can further better isolate the direct contact between the silicon-containing nanoparticles 400 and an electrolyte, and better provides channels for lithium ions and electrons; at the same time, the shell layer covers the entire core, which in turn better provides more sufficient buffer space for the volume expansion phenomenon of the silicon-containing nanoparticles 400.
In another aspect of the invention, the invention provides a method of making the aforementioned silicon carbon composite. According to an embodiment of the invention, referring to fig. 2, the method comprises the steps of:
s100: mixing a carbon-containing surfactant, a solid electrolyte, a first carbon material, silicon-containing nanoparticles, and a solvent to obtain a first dispersion.
According to an embodiment of the present invention, the carbon-containing surfactant may include polyvinylpyrrolidone, polycarboxymethyl methacrylate, and the like. Therefore, the material source is wide and easy to obtain, the cost is low, the second carbon material can be well formed on the surface of the silicon-containing nano particle, the operation is simple and convenient, the realization is easy, and the industrial production is easy.
According to an embodiment of the present invention, the solvent may include deionized water, tetrahydrofuran, dimethyl sulfoxide, toluene, and the like. Therefore, the material source is wide and easy to obtain, and the cost is lower.
According to the embodiment of the present invention, the specific types and particle sizes of the solid electrolyte, the first carbon material, and the silicon-containing nanoparticles are the same as those described above, and therefore, the description thereof is omitted.
According to an embodiment of the present invention, when the first dispersion is obtained, the mass ratio of the carbon-containing surfactant, the solid electrolyte, the first carbon material, and the silicon-containing nanoparticles is (2 to 30): (5-30): (1-30): (20-60). In some embodiments of the present invention, the mass ratio of the carbonaceous surfactant, the solid-state electrolyte, the first carbon material, and the silicon-containing nanoparticles when the first dispersion is obtained may be specifically 2: 5: 1: 20. 16: 17.5: 16.5: 40 or 1: 1: 1: 2, etc. Therefore, the quality is relatively proper, and the silicon-carbon composite material can be effectively prepared.
S200: and carrying out spray drying treatment on the first dispersion liquid to obtain a first prefabricated object.
According to the embodiment of the present invention, the specific process conditions, parameters, etc. of the spray drying treatment are not particularly limited, and those skilled in the art can flexibly select the conditions, parameters, etc. according to the actual needs as long as the requirements are met. In some embodiments of the present invention, the inventors have optimized process conditions and parameters of the spray drying process, and found that, when the process parameters of the spray drying process satisfy at least one of the following conditions, the spray drying process is effective, and the foregoing silicon-carbon negative electrode material can be effectively prepared, where the foregoing process conditions are: the temperature of the air inlet is 110-200 ℃; wind speed of 0.1m3/min～0.5m3The speed of the peristaltic pump is 0.005L/min-0.033L/min, the ejector is automatically dredged within 20 s-80 s, and the flow rate of the spraying gas is 5N L/min-20N L/min.
According to an embodiment of the present invention, specifically, the inlet temperature may be 110 ℃, 120 ℃, 130 ℃, 140 ℃, 150 ℃, 160 ℃, 170 ℃, 180 ℃, 190 ℃, or 200 ℃ or the like; the wind speed may be 0.1m3/min、0.2m3/min、0.3m3/min、0.4m3Min or 0.5m3A peristaltic pump speed of 0.005L/min, 0.01L/min, 0.02L/min, 0.03L/min, or 0.033L/min, etc., and at 20s, 3 s, etcThe flow rate of the spraying gas can be 5N L/min, 10N L/min, 15N L/min or 20N L/min, and the like, so that the silicon-carbon composite material prepared by the process conditions and parameters can better transport more electrons to the surface of the silicon-containing nanoparticles when electrode reaction occurs, and further the reaction activity and the structural stability of the whole silicon-carbon composite material are improved.
S300: and calcining the first prefabricated object to obtain the core.
According to the embodiments of the present invention, the process conditions and parameters of the calcination treatment are optimized by the inventors, and the inventors found that the calcination treatment has a good effect and can effectively prepare the aforementioned silicon-carbon negative electrode material when the process parameters of the calcination treatment satisfy at least one of the following conditions, wherein the calcination treatment is performed in an inert gas atmosphere, the gas flow is 10m L/min-80 m L/min, the temperature rise rate is 5 ℃/min-20 ℃/min, the temperature is 850 ℃ to 950 ℃, and the time is 1 h-3 h.
According to the embodiment of the invention, the calcination treatment is carried out in the atmosphere of inert gas, the inert gas can be argon, the gas flow can be 10m L/min, 20m L/min, 30m L/min, 40m L/min, 50m L/min, 60m L/min, 70m L/min or 80m L/min, the temperature rise rate can be 5 ℃/min, 8 ℃/min, 10 ℃/min, 12 ℃/min, 15 ℃/min or 20 ℃/min and the like, the temperature can be 850 ℃, 900 ℃ or 950 ℃, and the time can be 1h, 2h or 3h and the like, so that the silicon-carbon composite material prepared by the process conditions and parameters can better transmit more electrons to the surface of the silicon-containing nanoparticles when the electrode reaction occurs, and further the reaction activity and the structural stability of the whole silicon-carbon composite material are improved.
S400: the core, the first carbon material, the carbonaceous surfactant, the solid electrolyte, and the solvent are mixed to obtain a second dispersion.
According to an embodiment of the present invention, when the second dispersion liquid is obtained, the mass ratio of the core, the first carbon material, the carbonaceous surfactant, and the solid electrolyte is (20 to 60): (1-30): (2-30): (5-30). In some embodiments of the present invention, the mass ratio of the core, the first carbon material, the carbonaceous surfactant, and the solid electrolyte when obtaining the second dispersion may be specifically 20: 1: 2: 5. 40: 15.5: 16: 17.5 or 2: 1: 1: 1, etc. Therefore, the quality is relatively proper, and the silicon-carbon composite material can be effectively prepared.
S500: and carrying out spray drying treatment on the second dispersion liquid to obtain a second prefabricated object.
According to the embodiment of the present invention, the specific process conditions of the spray drying treatment are the same as those described above, and therefore, redundant description is omitted.
S600: and calcining the second prefabricated object to obtain the silicon-carbon composite material.
According to the embodiment of the present invention, the specific process conditions of the calcination treatment are the same as those described above, and will not be described in detail herein.
According to the embodiment of the invention, the prepared silicon-carbon composite material has the advantages that the first linear carbon material has good conductivity and can be used as an electronic conductive framework of the whole silicon-carbon composite material, so that the silicon-carbon composite material has excellent electronic conductivity and good mechanical property, the silicon-carbon composite material can be structurally supported, the solid electrolyte has strong conductivity and can be used as an ionic conductive framework of the whole silicon-carbon composite material, and the silicon-carbon composite material has excellent ionic conductivity; in addition, in the core of the silicon-carbon composite material, the silicon-containing nanoparticles coated by the solid electrolyte, the first carbon material and the second carbon material are uniformly distributed, and the shell coats the core, so that the shell forms an artificial SEI film in the whole silicon-carbon composite material, and when the silicon-carbon composite material is used as a negative electrode material of a power battery, the silicon-carbon composite material can further isolate the direct contact between the silicon-containing nanoparticles and an electrolyte, and provides a lithium ion and electron channel; meanwhile, the second carbon material coating the silicon-containing nanoparticles provides a certain buffer space for the volume expansion phenomenon of the silicon-containing nanoparticles, and the shell layer coats the whole core, which further provides a more sufficient buffer space for the volume expansion phenomenon of the silicon-containing nanoparticles.
In yet another aspect of the invention, a negative electrode is provided. According to an embodiment of the invention, the negative electrode comprises the aforementioned silicon carbon composite. The inventor finds that the negative electrode has high capacity, good rate capability, strong stability and good cyclicity.
According to the embodiment of the invention, the material forming the negative electrode can also comprise conductive carbon black, and can be Super-P and the like; the binder may specifically be PVDF (polyvinylidene fluoride), and the mass ratio of the aforementioned silicon-carbon negative electrode material, the conductive carbon black, and the binder may be (6-8.5): (0.5-2): (0.5 to 1). Specifically, it may be 6: 2: 2. 7: 1: 0.8 or 8.5, 0.5, 1, etc. Therefore, the proportion is better, so that the performance of the negative electrode is better.
According to the embodiment of the invention, the specific preparation method of the negative electrode can be that the material for forming the negative electrode is mixed in the solvent and stirred, then the mixed slurry is coated on the electrode substrate, the electrode substrate is kept warm for 2-8 h in a vacuum drying oven at 40-70 ℃, and is placed in the vacuum drying oven at 40-70 ℃ again after the steps of forming, tabletting and the like. The method is simple and convenient to operate, easy to realize and easy for industrial production.
In yet another aspect of the invention, a power cell is provided. According to an embodiment of the invention, the power cell comprises the aforementioned negative electrode. The inventor finds that the power battery has good electrochemical performance and long service life.
The shape, configuration, manufacturing process, etc. of other structures and components of the power cell may be conventional according to embodiments of the present invention, which may be a lithium ion battery in some embodiments of the present invention. Those skilled in the art will appreciate that the power cell includes the structure and components of a conventional power cell in addition to those described above, and will not be described in any greater detail herein.
According to an embodiment of the invention, the power battery may specifically be a lithium ion battery.
In yet another aspect of the present invention, an electric vehicle is provided. According to an embodiment of the invention, the electric vehicle comprises the power battery. The inventor finds that the electric automobile has strong driving force and good commercial prospect.
According to the embodiment of the invention, the shape, the structure, the manufacturing process and the like of the electric vehicle can be the shape, the structure and the manufacturing process of a conventional electric vehicle, and a person skilled in the art can understand that besides the power battery, the electric vehicle also comprises the structure and the components of the conventional electric vehicle, and the connection relationship between the structure and the components is also the connection relationship between the structures and the components in the conventional electric vehicle, and redundant description is not repeated here.
According to an embodiment of the present invention, the kind of the electric vehicle is not particularly limited, and may include, for example, but not limited to, an electric car, an electric bicycle, an electric motorcycle, and the like.
The following describes embodiments of the present invention in detail.
Example 1
Method for preparing silicon-carbon composite material
Dispersing 0.3g of single-walled carbon nanotubes into 500m L of deionized water to form a uniform solution, then adding 2.0g of nano silicon particles and 0.5g of oxide solid electrolyte LL ZTO into the uniform solution, fully stirring and carrying out high-energy ultrasonic dispersion for 2 hours to obtain a first dispersion liquid, carrying out spray drying treatment on the first dispersion liquid to obtain a first prefabricated object, and calcining the first prefabricated object at 900 ℃ for 2 hours under the argon atmosphere to obtain a core (a scanning electron microscope picture is shown in figure 3).
Dispersing 0.1g of single-walled carbon nanotubes into 300m L of deionized water to form a uniform solution, then adding 2.0g of the core and 0.2g of oxide solid electrolyte LL ZTO into the uniform solution, fully stirring and dispersing for 2 hours by high-energy ultrasound to obtain a second dispersion liquid, carrying out spray drying treatment on the second dispersion liquid to obtain a second prefabricated object, and calcining the second prefabricated object at 900 ℃ for 2 hours under the argon atmosphere to obtain the silicon-carbon composite material (the scanning electron microscope picture is shown in figure 4).
The silicon-carbon composite material is manufactured into a negative electrode and assembled into a battery, and a charging and discharging curve of the battery is tested (see fig. 5), so that the battery has a relatively obvious charging platform in a charging stage, and is favorable for smooth discharging in a full battery; in addition, the capacity retention rate of the battery assembled by the silicon-carbon composite material under different charge and discharge rates is as follows: 100% (0.1C), 98% (0.33C), 95% (0.5C), and 91% (1C) (see fig. 6, which is a comparative graph of the capacity retention rates of the silicon-carbon composite material and the silicon particle negative electrode in the present embodiment, and the capacity retention rates of the silicon particle negative electrode are 100% (0.1C), 91% (0.33C), 78% (0.5C), and 60% (1C), it is obvious that the rate performance of the silicon-carbon composite material in the present embodiment is far better than that of the silicon particle.
Example 2
Method for preparing silicon-carbon composite material
Dispersing 0.3g of multi-walled carbon nanotubes into 500m L of tetrahydrofuran to form a uniform solution, then adding 2.0g of nano silicon particles and 0.5g of oxide solid electrolyte LL ZO into the uniform solution, fully stirring and carrying out high-energy ultrasonic dispersion for 2 hours to obtain a first dispersion liquid, carrying out spray drying treatment on the first dispersion liquid to obtain a first prefabricated object, and calcining the first prefabricated object at 900 ℃ for 2 hours in an argon atmosphere to obtain a core.
Dispersing 0.1g of multi-walled carbon nanotubes into 300m L of tetrahydrofuran to form a uniform solution, then adding 2.0g of the core and 0.2g of oxide solid electrolyte LL ZO into the uniform solution, fully stirring and carrying out high-energy ultrasonic dispersion for 2 hours to obtain a second dispersion liquid, carrying out spray drying treatment on the second dispersion liquid to obtain a second prefabricated object, and calcining the second prefabricated object at 900 ℃ for 2 hours in an argon atmosphere to obtain the silicon-carbon composite material.
The charge and discharge curve test results and rate capability test results of this example are similar to those of example 1.
Example 3
Method for preparing silicon-carbon composite material
Dispersing 0.3g of multi-walled carbon nanotubes into 600m L of toluene to form a uniform solution, then adding 2.0g of nano silica particles and 0.5g of sulfide solid electrolyte L GPS into the uniform solution, fully stirring and carrying out high-energy ultrasonic dispersion for 2 hours to obtain a first dispersion liquid, carrying out spray drying treatment on the first dispersion liquid to obtain a first prefabricated object, and then calcining the first prefabricated object at 900 ℃ for 2 hours in an argon atmosphere to obtain a core.
Dispersing 0.1g of multi-walled carbon nanotubes into 300m L of toluene to form a uniform solution, then adding 2.0g of the core and 0.2g of sulfide solid electrolyte L GPS into the uniform solution, fully stirring and carrying out high-energy ultrasonic dispersion for 2 hours to obtain a second dispersion liquid, carrying out spray drying treatment on the second dispersion liquid to obtain a second prefabricated object, and calcining the second prefabricated object at 900 ℃ for 2 hours in an argon atmosphere to obtain the silicon-carbon composite material.
The charge and discharge curve test results and rate capability test results of this example are similar to those of example 1.
In the description of the present invention, it is to be understood that the terms "first", "second" and the like are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implying any number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include one or more of that feature. In the description of the present invention, "a plurality" means two or more unless specifically defined otherwise.
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 (10)

1. The silicon-carbon composite material is characterized in that the silicon-carbon composite material is a core-shell structure microsphere, the core-shell structure microsphere is provided with a core and a shell, the shell coats the core,
wherein the core comprises a solid electrolyte, a first carbon material in a wire form, and silicon-containing nanoparticles coated with a second carbon material; the shell layer includes the solid electrolyte coated with the first carbon material and the second carbon material.
2. The silicon-carbon composite of claim 1, wherein the first carbon material comprises carbon nanotubes; the second carbon material comprises amorphous carbon,
optionally, the carbon nanotubes comprise at least one of single-walled carbon nanotubes and multi-walled carbon nanotubes.
3. The silicon-carbon composite material according to claim 1, wherein the solid electrolyte comprises at least one of an oxide solid electrolyte and a sulfide solid electrolyte,
optionally, the oxide solid state electrolyte comprises at least one of lithium lanthanum zirconium oxygen, lithium lanthanum titanium oxygen, lithium lanthanum zirconium titanium oxygen, lithium aluminum titanium oxygen, titanium aluminum lithium phosphate, germanium aluminum lithium phosphate, and lithium nitrogen phosphate,
optionally, the particle size of the oxide solid electrolyte is 0.01-5 μm,
optionally, the sulfide solid state electrolyte includes at least one of lithium germanium phosphorus sulfide, lithium phosphorus sulfur iodide, and lithium phosphorus sulfur chloride,
optionally, the particle size of the sulfide solid electrolyte is 0.01-5 μm,
optionally, the solid state electrolyte further comprises at least one of anatase titanium dioxide and lithium titanate.
4. The silicon-carbon composite of claim 1, wherein the silicon-containing nanoparticles comprise at least one of nano-silicon particles and nano-silica particles,
optionally, the nano-silicon particles comprise at least one of single crystal silicon, polycrystalline silicon and amorphous silicon,
optionally, the silicon-containing nanoparticles have a particle size of 0.01 to 5 μm.
5. The silicon-carbon composite material according to claim 1, wherein in the core-shell structure microsphere, the mass ratio of the core to the shell is (1-4): (16-19) of a first step,
optionally, in the core, the mass ratio of the solid electrolyte, the first carbon material, the second carbon material and the silicon-containing nanoparticles is (10-40): (1-35): (1-35): (20 to 60) of the total amount of the organic silicon,
optionally, in the shell layer, the mass ratio of the first carbon material, the solid electrolyte and the second carbon material is (1-7): (6-12): (1-7).
6. A method of preparing the silicon-carbon composite material according to any one of claims 1 to 5, comprising:
mixing a carbonaceous surfactant, the solid electrolyte, the first carbon material, the silicon-containing nanoparticles, and a solvent to obtain a first dispersion;
carrying out spray drying treatment on the first dispersion liquid to obtain a first prefabricated object;
calcining the first prefabricated object to obtain the core;
mixing the core, the first carbon material, the carbonaceous surfactant, the solid electrolyte, and the solvent to obtain a second dispersion;
performing the spray drying treatment on the second dispersion to obtain a second prefabricated object;
and carrying out the calcination treatment on the second prefabricated object so as to obtain the silicon-carbon composite material.
7. The method of claim 6, wherein the carbon-containing surfactant comprises at least one of polyvinylpyrrolidone and poly (methyl carboxymethyl methacrylate),
optionally, the solvent comprises at least one of deionized water, tetrahydrofuran, dimethyl sulfoxide, and toluene,
optionally, the mass ratio of the carbon-containing surfactant, the solid electrolyte, the first carbon material, and the silicon-containing nanoparticles when the first dispersion is obtained is (2-30): (5-30): (1-30): (20 to 60) of the total amount of the organic silicon,
optionally, the mass ratio of the core, the first carbon material, the carbonaceous surfactant and the solid electrolyte when the second dispersion is obtained is (20-60): (1-30): (2-30): (5-30) of a solvent,
optionally, the spray drying process satisfies at least one of the following conditions:
the temperature of the air inlet is 110-200 ℃;
wind speed of 0.1m3/min～0.5m3/min；
The speed of the peristaltic pump is 0.005L/min-0.033L/min;
the ejector is automatically dredged within 20 s-80 s;
the flow rate of the spraying gas is 5N L/min-20N L/min,
optionally, the calcination treatment satisfies at least one of the following conditions:
the calcination treatment is carried out under an inert gas atmosphere, preferably, the inert gas is argon;
the gas flow is 10m L/min-80 m L/min;
the heating rate is 5 ℃/min to 20 ℃/min;
the temperature is 850-950 ℃;
the time is 1 h-3 h.
8. A negative electrode comprising the silicon-carbon composite material according to any one of claims 1 to 5.
9. A power cell comprising the negative electrode of claim 8.
10. An electric vehicle characterized by comprising the power battery according to claim 9.
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