CN116130642A - Hierarchical porous silicon-carbon negative electrode material, silicon-containing negative electrode sheet and lithium ion battery - Google Patents
Hierarchical porous silicon-carbon negative electrode material, silicon-containing negative electrode sheet and lithium ion battery Download PDFInfo
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- CN116130642A CN116130642A CN202310095400.4A CN202310095400A CN116130642A CN 116130642 A CN116130642 A CN 116130642A CN 202310095400 A CN202310095400 A CN 202310095400A CN 116130642 A CN116130642 A CN 116130642A
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- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a graded porous silicon-carbon anode material, which comprises a core layer and an edge layer positioned on the outer side of the core layer; the core layer and the edge layer comprise a carbon matrix, nano silicon particles and pores; wherein the pores in the core layer comprise nano macropores and nano mesopores, the diameter of the nano macropores is 500-1600 nm, and the diameter of the nano mesopores is 100-500 nm; the pore in the edge layer comprises a nano pore and a nano micropore, the diameter of the nano pore is 20-100 nm, and the diameter of the nano micropore is less than 20nm. The invention also provides a silicon negative electrode plate prepared from the graded porous silicon-carbon negative electrode material and a lithium ion battery. The graded porous silicon-carbon anode material effectively reduces the expansion and contraction stress of the silicon-based electrode material in the circulation process, slows down the capacity attenuation of the battery and improves the circulation performance of the battery.
Description
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to a hierarchical porous silicon-carbon negative electrode material, a silicon-containing negative electrode plate and a lithium ion battery.
Background
With the rapid development of portable electronic devices and electric vehicles, there is an unprecedented demand for lithium ion batteries having high energy density and long lifetime. Compared with the traditional commercial graphite anode material, the silicon-based anode material has the characteristics of high theoretical specific capacity, low discharge platform, environmental friendliness and the like, so that the silicon-based anode material becomes one of the most promising materials of next-generation high-energy-density lithium ion batteries. However, silicon-based anode materials have the following disadvantages: (1) poor conductivity; (2) The tremendous volume increase (300%) during charge-discharge causes electrode pulverization and repeated formation of an unstable Solid Electrolyte (SEI) film accompanied by continuous consumption of electrolyte, eventually leading to rapid cycle decay of the battery, and low Coulombic Efficiency (CE).
Therefore, how to improve the volume expansion effect of the silicon-based anode material in the charge and discharge process and the conductivity of the silicon-based anode material system is still a technical problem to be solved.
Disclosure of Invention
The invention aims to solve the technical problem of providing the graded porous silicon-carbon anode material, which effectively reduces the expansion and contraction stress of the silicon-based electrode material in the circulation process, slows down the capacity attenuation of a battery and improves the circulation performance of the battery.
In order to solve the technical problems, the invention provides the following technical scheme:
the first aspect of the invention provides a graded porous silicon-carbon anode material, which comprises a core layer and an edge layer positioned outside the core layer; the core layer and the edge layer comprise a carbon matrix, nano silicon particles and pores;
wherein the pores in the core layer comprise nano macropores and nano mesopores, the diameter of the nano macropores is 500-1600 nm, and the diameter of the nano mesopores is 100-500 nm;
the pores in the edge layer comprise nano pores and nano micropores, the diameter of the nano pores is 20-100 nm, and the diameter of the nano micropores is less than 20nm.
Further, the diameter of the core layer is 2.1-23.4 μm, and the thickness of the edge layer is 0.15-8.6 μm.
Further, the surface of the graded porous silicon carbon cathode material is coated with a compact outer carbon layer, and compact inner carbon layers are deposited on the pore walls of the nano macropores, the nano mesopores and the nano micropores.
Further, the thicknesses of the outer carbon layer and the inner carbon layer are 5-200 nm; the thickness of the inner carbon layer is smaller than that of the outer carbon layer.
Further, the nano silicon particles comprise elemental silicon and SiO x (0＜x＜2)。
Further, in the hierarchical porous silicon-carbon anode material, the mass ratio of silicon is 5-90%, and the mass ratio of O is 3-55%.
Further, the median particle diameter D50 of the graded porous silicon-carbon anode material is 3.0-22.0 mu m, and the tap density is 0.65-1.35 g/cm 3 The specific surface area is 0.95-6.5 m 2 /g。
The second aspect of the invention provides a preparation method of a graded porous silicon-carbon anode material, which comprises the following steps:
s1, mixing a silicon source, a binder carbon source and a pore-forming agent, heating once, and cooling to obtain a mixed solid;
s2, the mixed solid is heated for the second time and then crushed to obtain a porous silicon precursor;
s3, introducing acetylene mixed gas taking non-oxidizing gas as carrier gas into the porous silicon precursor to carry out vapor deposition reaction, and then carrying out heat preservation treatment to obtain the graded porous silicon-carbon anode material.
Further, in step S1The silicon source is monocrystalline silicon, amorphous silicon or SiO with the grain diameter of 20-200 nm x (0 < x < 2);
and/or the carbon source of the binder is one or more of polyethylene, polyacrylic acid, polypropylene, polyvinylpyrrolidone and phenolic resin;
and/or the pore-forming agent is one or more of ammonium bicarbonate, ammonium carbonate and ammonium oxalate;
and/or the mass ratio of the silicon source, the binder carbon source and the pore-forming agent is 100: 5-80: 0.01 to 0.5;
and/or the temperature of the primary heating is 60-200 ℃.
Further, in the step S2, the temperature of the secondary heating is 600-1300 ℃;
and/or the particle diameter of the crushed particles is 0.6-50 μm.
In step S3, the volume ratio of the non-oxidizing gas in the acetylene mixed gas using the non-oxidizing gas as the carrier gas is 50-98%;
and/or the non-oxidizing gas is one or more of nitrogen, helium, neon, argon and krypton;
and/or the temperature of the vapor deposition reaction is 500-1300 ℃, and the time of the vapor deposition reaction is 3 min-10 h;
and/or the temperature of the heat preservation treatment is 300-600 ℃, and the time of the heat preservation treatment is 1-8 h.
The third aspect of the invention provides a silicon-containing negative electrode sheet, which comprises a negative electrode current collector and a negative electrode material layer formed on at least one side surface of the negative electrode current collector, wherein the negative electrode material layer comprises a negative electrode active material, a conductive agent and a binder, and the negative electrode active material comprises a graphite negative electrode material and the graded porous silicon-carbon negative electrode material.
Further, in the negative electrode material layer, the mass percentages of the negative electrode active material, the conductive agent and the binder are 75-99%, 0.5-8% and 0.6-15.0%, respectively.
Further, in the anode active material, the mass ratio of the graded porous silicon-carbon anode material is 1-80%.
The fourth aspect of the invention provides a lithium ion battery, comprising a positive plate, a negative plate, a diaphragm and electrolyte, wherein the diaphragm is arranged to isolate the positive plate from the negative plate, and the negative plate is the silicon-containing negative plate.
Compared with the prior art, the invention has the beneficial effects that:
1. in the hierarchical porous silicon-carbon anode material, nano macropores and nano mesopores are formed in the core layer, nano micropores and nano micropores are attached in the edge layer, nano silicon particles are embedded in the carbon matrix, and nano silicon, nano macropores, nano mesopores, nano micropores and carbon are distributed in a dispersed manner, so that silicon cluster aggregation in the charge-discharge cycle process of the battery can be effectively relieved, and the expansion stress is reduced.
2. In the graded porous silicon-carbon anode material, the outer surface of the edge layer is coated by the outer carbon layer, the pore walls of the nano macropores, the nano mesopores and the nano pinholes are coated by the inner carbon layer, and the inner carbon layer and the outer carbon layer can isolate the nano silicon from contacting with electrolyte in the outer and inner porous layers, so that side reactions with the electrolyte are reduced, and the cycle performance of the battery is improved.
Drawings
FIG. 1 is a schematic cross-sectional view of a graded porous silicon carbon anode material in an embodiment of the invention;
FIG. 2 is a cross-sectional SEM of a graded porous silicon-carbon anode material according to one embodiment of the invention;
wherein: 1. a core layer; 2. an edge layer; 3. a carbon matrix; 4. nano silicon particles; 5. a nano macroporous; 6. a nano-mesopore; 7. a nano-aperture; 8. a nano-micropore; 9. an outer carbon layer; 10. an inner carbon layer.
Detailed Description
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. The term "and/or" as used herein includes any and all combinations of one or more of the associated listed items.
For silicon anode materials, it has a theoretical specific capacity as high as 4200mAh/g, which is the next generation anode material most likely to replace graphite. However, in the working process of the silicon negative electrode battery, a large amount of lithium ions are intercalated and deintercalated along with the volume expansion and shrinkage of the silicon negative electrode material, so that the particles of the negative electrode material are broken, the electrical contact is poor, and the SEI film is unstable, and finally, the efficiency of the silicon negative electrode material is reduced and the cycle capacity is fast attenuated. The problems limit the wide application of silicon materials in lithium ion battery cathode materials.
In order to solve the technical problem, the inventor provides a silicon-carbon anode material with a hierarchical porous structure, and through the design of hierarchical porous and inner and outer carbon layers, the expansion and contraction stress of the electrode material in the circulation process is slowed down, the capacity attenuation of a battery can be effectively controlled, and the battery can keep ultra-high circulation times.
Referring to fig. 1, the graded porous silicon-carbon anode material provided by the invention is spherical in shape, and comprises an inner core layer and an edge layer 2 positioned outside the core layer 1. The core layer 1 and the edge layer 2 comprise a carbon matrix 3, nano silicon particles 4 and pores.
In the present invention, the pores in the core layer 1 mainly include two types of pores of nano macropores 5 and nano mesopores 6, wherein "nano macropores" refers to pores having a diameter in the range of 500 to 1600nm (excluding 500 nm), for example, pores having a diameter in the range of 500 to 600nm, 600 to 700nm, 700 to 800nm, 800 to 900nm, 900 to 1000nm, 1000 to 1100nm, 1100 to 1200nm, 1200 to 1300nm, 1300 to 1400nm, 1400 to 1500nm or 1500 to 1600 nm. "nanometer mesopore" refers to a pore having a diameter in the range of 100 to 500nm, such as a pore having a diameter in the range of 100 to 200nm, 200 to 300nm, 300 to 400nm, or 400 to 500 nm.
The pores in the edge layer 2 mainly include two types of pores, nano-pores 7 and nano-micropores 8, wherein "nano-pores" refers to pores having a diameter in the range of 20 to 100nm, for example, pores having a diameter in the range of 20 to 30nm, 30 to 40nm, 40 to 50nm, 50 to 60nm, 60 to 70nm, 70 to 80nm, 80 to 90nm, or 90 to 100 nm. "nanopore" refers to a pore having a diameter of less than 20nm (excluding 20 nm), such as a pore having a diameter in the range of 1-5 nm, 5-10 nm, 10-15 nm, or 15-20 nm.
It should be noted that since the pore shapes in the core layer and the edge layer are not regular spheres, but may be a variety of irregular shapes, the "diameter" herein refers to the "volume equivalent diameter" of the pores, i.e. the diameter of a sphere having the same volume as the pores.
The core layer may contain other types of pores, such as micro-pores, nano-micropores, etc. with a pore diameter of more than 1600nm, in addition to the two types of pores of the nano-macropores 5 and the nano-mesopores 6. These "other types of pores" should account for less than 5% of the pores in the core layer, e.g., the ratio may be less than 5%, less than 4%, less than 3%, less than 2%, less than 1%, etc. Likewise, in the edge layer, the "other types of holes" should also account for less than 5% of the pores in the edge layer.
In the invention, the nano macropores and nano mesopores can be distributed in the core layer, namely, can be positioned at the central position, the position close to the center or the edge part of the core layer. Similarly, the nanopores and nanopores may be distributed in the edge layer, i.e., at a location near the core layer, at the center of the edge layer, with the outermost side of the edge layer being a dense carbon layer having no or little porosity.
In the present invention, the diameter of the core layer is preferably 2.1 to 23.4. Mu.m, and may be, for example, 2.1 to 4. Mu.m, 4 to 6. Mu.m, 6 to 8. Mu.m, 8 to 10. Mu.m, 10 to 12. Mu.m, 12 to 14. Mu.m, 14 to 16. Mu.m, 16 to 18. Mu.m, 18 to 20. Mu.m, 20 to 22. Mu.m, 22 to 23.4. Mu.m, or any range between these values. The thickness of the edge layer is preferably 0.15 to 8.6. Mu.m, and may be, for example, 0.15 to 0.5. Mu.m, 0.5 to 1. Mu.m, 1 to 2. Mu.m, 2 to 3. Mu.m, 3 to 4. Mu.m, 4 to 5. Mu.m, 5 to 6. Mu.m, 6 to 7. Mu.m, 7 to 8.6. Mu.m, or any range between these values. It should be noted that the core layer in the present invention is not necessarily regular spherical, and the surface may have an uneven shape, so that the "diameter" of the core layer herein refers to the "volume equivalent diameter" of the core layer. Also, the edge layer may vary in thickness throughout, so "thickness" of the edge layer herein refers to the average thickness.
In some embodiments of the invention, the outer surface of the graded porous silicon carbon anode material has an outer carbon layer, which is a dense carbon layer that is tightly wrapped around the surface of the edge layer. The outer carbon layer may be obtained by conventional coating methods in the art including, but not limited to, CVD vapor deposition, liquid deposition, solid phase coating, liquid phase coating, and the like, followed by high temperature carbonization.
In other embodiments of the present invention, there is also an inner carbon layer on the walls of the nano-macropores, nano-mesopores, and nano-micropores, the inner carbon layer also being a dense carbon layer that is tightly deposited on the walls of the pores.
In the invention, the compact outer carbon layer isolates the electrolyte from the inner core of the silicon-carbon anode material from the outside, so that the contact between the nano silicon and the electrolyte is avoided, the side reaction with the electrolyte is reduced, and the cycle performance of the battery is improved. The inner carbon layer can separate the electrolyte in the pores from the nano-silicon from the inside, so that the technical effect of avoiding contact between the nano-silicon and the electrolyte can be further achieved.
In the present invention, the thickness of the outer carbon layer and the inner carbon layer may be 5 to 200nm, for example, 5nm, 6nm, 12nm, 18nm, 30nm, 35nm, 50nm, 60nm, 90nm, 100nm, 120nm, 150nm, 160nm, 180nm, 190nm, 200nm, or any thickness between these values. Preferably, the thickness of the inner carbon layer is less than the thickness of the outer carbon layer.
In the invention, nano silicon particles are distributed in the carbon matrix of the core layer and the edge layer, and the pure silicon is taken as the main material, and partial Si is combined with O to form silicon oxide SiO x (0 < x < 2). Preferably, si comprises 5-90% by mass of the graded porous silicon carbon anode material, such as 5%, 5.5%, 6%, 7%, 8%, 10%, 12%, 13%, 15%, 16%, 17%, 18%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, or any mass fraction between these values; o occupies the mass of the graded porous silicon-carbon anode materialFor example 3%, 3.5%, 4%, 5%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, or any mass fraction between these values.
In the present invention, the median particle diameter D50 of the hierarchical porous silicon-carbon anode material is 3.0 to 22.0. Mu.m, more preferably 5.2 to 12. Mu.m, still more preferably 6.5 to 15. Mu.m, for example, 6.5 to 7.0. Mu.m, 7 to 7.5. Mu.m, 7.5 to 7.8. Mu.m, 7.8 to 8.7. Mu.m, 8.7 to 9.6. Mu.m, 9.6 to 10. Mu.m, 10 to 10.5. Mu.m, 10.5 to 11. Mu.m, 11 to 11.6. Mu.m, 11.6 to 12.5. Mu.m, 12.5 to 13.5. Mu.m, 13.5 to 14. Mu.m, 14 to 15. Mu.m, or any range between these values.
In the invention, the tap density of the graded porous silicon-carbon anode material is 0.65-1.35 g/cm 3 More preferably 0.68 to 1.05g/cm 3 More preferably 0.70 to 0.95g/cm 3 For example 0.72g/cm 3 、0.75g/cm 3 、0.76g/cm 3 、0.78g/cm 3 、0.80g/cm 3 、0.85g/cm 3 、0.82g/cm 3 、0.85g/cm 3 、0.88g/cm 3 、0.90g/cm 3 、0.92g/cm 3 、0.95g/cm 3 Or any density between these values.
In the invention, the Specific Surface Area (SSA) of the graded porous silicon-carbon anode material is 0.95-6.5 m 2 Preferably 1.1 to 55m 2 Preferably 1.5 to 5m 2 /g, e.g. 1.5m 2 /g、1.55m 2 /g、1.6m 2 /g、1.7m 2 /g、1.8m 2 /g、1.9m 2 /g、2.0m 2 /g、2.5m 2 /g、3.0m 2 /g、3.5m 2 /g、4.0m 2 /g、4.5m 2 /g、5.0m 2 /g, or any specific surface area between these values.
It should be noted that, in addition to the shape shown in fig. 1, the graded porous silicon-carbon anode material of the present invention may also have shapes such as ellipsoids, blocks, long strips, sheets, etc. after being crushed, sieved, sanded, etc. during the preparation process.
The invention also provides a preparation method of the graded porous silicon-carbon anode material, which comprises the following steps:
s1, mixing a silicon source, a binder carbon source and a pore-forming agent, drying and heating, stabilizing, and cooling to obtain a mixed solid;
s2, heating the mixed solid at a high temperature and then crushing the mixed solid to obtain a porous silicon precursor;
s3, introducing the porous silicon precursor into acetylene mixed gas with non-oxidizing gas as carrier gas to carry out vapor deposition reaction, and then carrying out high-temperature heat preservation treatment to obtain the reaction product of the graded porous silicon-carbon anode material.
In the step S1, after the binder carbon source, the silicon source and the pore-forming agent are mixed, the binder carbon source wraps the silicon source and the pore-forming agent, part of the pore-forming agent is decomposed in the heating process, the pore-forming agent wrapped by the binder carbon source is stored, the pore-forming agent wrapped in the center is more, and the edge is less.
The silicon source is monocrystalline silicon, amorphous silicon or SiO with the grain diameter of 20-200 nm x (0 < x < 2);
the carbon source of the binder is one or more of polyethylene, polyacrylic acid, polypropylene, polyvinylpyrrolidone and phenolic resin;
the pore-forming agent is one or more of ammonium bicarbonate, ammonium carbonate and ammonium oxalate;
the mass ratio of the silicon source to the binder carbon source to the pore-forming agent is 100: 5-80: 0.01 to 0.5;
the heating temperature is 60 to 200℃and may be 60℃80℃100℃120℃150℃160℃180℃200℃or the like.
In the step S2, the pore-forming agent is decomposed by high-temperature heating, so that different pores are generated, the pore-forming agent in the central area is more, the generated pores are larger, and the pore-forming agent in the edge area is less, so that the generated pores are smaller; and because the pore-forming agent contains carbon, part of the carbon is distributed on the pore wall in the high-temperature heating process, and a compact inner carbon layer is deposited.
The high-temperature heating temperature is 600 to 1300 ℃, and can be 600 ℃, 650 ℃, 700 ℃, 750 ℃, 800 ℃, 850 ℃, 900 ℃, 950 ℃, 1000 ℃, 1050 ℃, 1100 ℃, 1150 ℃, 1200 ℃, 1250 ℃, 1300 ℃ and the like;
the particle diameter of the pulverized particles may be 0.6 to 50. Mu.m, for example, 0.6 to 1. Mu.m, 1 to 2. Mu.m, 2 to 5. Mu.m, 5 to 8. Mu.m, 8 to 10. Mu.m, 10 to 15. Mu.m, 15 to 20. Mu.m, 20 to 30. Mu.m, 30 to 40. Mu.m, 40 to 50. Mu.m, etc.
In the step S3, an outer carbon layer is formed on the surface of the particles after vapor deposition.
In the acetylene mixed gas using the non-oxidizing gas as the carrier gas, the non-oxidizing gas accounts for 50-98% by volume, for example, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95%, 98% or the like;
the non-oxidizing gas is one or more of nitrogen, helium, neon, argon and krypton;
the vapor deposition reaction may be carried out at a temperature of 500 to 1300 ℃, for example, 500 ℃, 550 ℃, 600 ℃, 650 ℃, 700 ℃, 750 ℃, 800 ℃, 850 ℃, 900 ℃, 950 ℃, 1000 ℃, 1050 ℃, 1100 ℃, 1150 ℃, 1200 ℃, 1250 ℃, 1300 ℃, etc.; the time of the vapor deposition reaction is 3 min-10 h, for example, 3min, 5min, 10min, 20min, 30min, 1h, 2h, 3h, 5h, 6h, 8h, 10h and the like;
the high temperature heat-preserving treatment is carried out at a temperature of 300 to 600 ℃, for example, 300 ℃, 350 ℃, 400 ℃, 450 ℃, 500 ℃, 550 ℃, 600 ℃ and the like; the high temperature treatment time is 1 to 8 hours, and may be, for example, 1 hour, 2 hours, 3 hours, 4 hours, 5 hours, 6 hours, 7 hours, 8 hours, or the like. The high-temperature heat preservation treatment is favorable for stabilizing silicon and carbon.
On the basis of the graded porous silicon-carbon negative electrode material, the invention further provides a silicon-containing negative electrode plate. The silicon-containing negative electrode sheet includes a negative electrode current collector and a negative electrode material layer, and the negative electrode material layer is formed on at least one side surface of the negative electrode current collector. The anode material layer comprises an anode active material, a conductive agent and a binder, wherein the anode active material comprises a graphite anode material and the graded porous silicon carbon anode material.
In the invention, the preparation method of the cathode slurry comprises the following steps: mixing the anode active material, the conductive agent and the binder according to a certain proportion, adding water, stirring, and adjusting the viscosity to obtain anode homogenate. The negative electrode slurry is coated or otherwise formed on at least one side surface of the negative electrode current collector to form a negative electrode material layer. Preferably, when preparing the slurry, the viscosity of the slurry is regulated to 1200-9500 mPa.s, and the solid content of the anode homogenate is controlled to be 40-86%.
In some embodiments, the anode active material, the conductive agent, and the binder may be mixed in a ratio of 75 to 99%, 0.5 to 8%, and 0.6 to 15.0%. For example, the proportion of the negative electrode active material may be varied from 75 to 76%, 76 to 78%, 78 to 81%, 81 to 82%, 82 to 83%, 83 to 84%, 84 to 85%, 85 to 86%, 86 to 87%, 87 to 88%, 88 to 89%, 89 to 90%, 90 to 91%, 91 to 92%, 92 to 93%, 93 to 94%, 94 to 95%, 95 to 96%, 96 to 97%, 97 to 98%, 98 to 99%.
In the present invention, the negative electrode active material includes the above-mentioned graded porous silicon carbon negative electrode material and graphite negative electrode material, wherein the graphite negative electrode material may be graphite material commonly used in the art, including but not limited to at least one of natural graphite and artificial graphite. Graphite materials are the most widely used negative electrode active materials, which have good conductivity properties, and not only can promote the conductivity of silicon materials, but also can contribute to capacity. Preferably, the graphite negative electrode material is one or more of the graphite negative electrode materials which are subjected to surface treatment such as spheroidization or structural modification, oxidation, etching and the like, doping such as nitrogen, phosphorus, sulfur, iron, cobalt, nickel, aluminum, zinc and the like, or modification treatment such as amorphous carbon layer coating and the like.
In the present invention, the mass ratio of the graded porous silicon-carbon anode material in the anode active material is 1 to 80%, for example, 1 to 5%, 5 to 10%, 10 to 20%, 20 to 30%, 30 to 40%, 40 to 50%, 50 to 60%, 60 to 70%, 70 to 80%, or any range between these values.
In the invention, the negative electrode current collector may be one or more of copper foil, porous copper foil, nickel/copper foam, zinc-plated copper foil, nickel-plated copper foil, carbon-coated copper foil, nickel foil, titanium foil and carbon-containing porous copper foil. Preferably copper foil, zinc-plated copper foil, nickel-plated copper foil, and carbon-coated copper foil.
In the present invention, the binder may be a monomer, polymer, copolymer of acrylonitrile, vinylidene fluoride, vinyl alcohol, carboxymethyl cellulose, lithium carboxymethyl cellulose, sodium carboxymethyl cellulose, methacryloyl, acrylic acid, lithium acrylate, acrylamide, amide, imide, acrylate, styrene-butadiene rubber, sodium alginate, chitosan, ethylene glycol, or guar gum.
In the invention, the conductive agent can be at least one of conductive carbon black, acetylene black, graphite, graphene, carbon micro-nano linear conductive material and carbon micro-nano tubular conductive material.
Further, the invention provides a lithium ion battery, which comprises the silicon-containing negative plate. The preparation method is as follows: and winding the silicon negative plate, the isolating film and the positive plate to obtain a battery core, then packaging the battery core into a battery shell, and drying, injecting electrolyte, packaging, forming, separating the volume and the like to obtain the lithium ion battery.
In the positive electrode sheet, the positive electrode active material may be at least one of lithium cobaltate, lithium nickelate, lithium manganate, lithium nickelate aluminate, lithium manganese phosphate, lithium iron manganese phosphate, and lithium iron phosphate.
The present invention will be further described with reference to specific examples, which are not intended to be limiting, so that those skilled in the art will better understand the present invention and practice it.
The experimental methods used in the following examples are conventional methods unless otherwise specified.
Example 1
1. Preparation method of graded porous silicon-carbon anode material
S1, according to 100:55: mixing monocrystalline silicon with the particle size of 20-200 nm, phenolic resin and ammonium bicarbonate according to the mass ratio of 0.5, heating at 80 ℃, and cooling after stabilizing to obtain a mixed solid;
s2, heating the mixed solid at 700 ℃, and then crushing the mixed solid to the particle size of 1.4-35 mu m to obtain a porous silicon precursor;
s3, carrying out heat preservation treatment on the porous silicon precursor for 1-8 hours at the temperature of 300-600 ℃, then introducing acetylene mixed gas (the volume ratio of acetylene is 70%) taking krypton as carrier gas, and carrying out vapor deposition for 8 hours at the temperature of 550 ℃ to obtain the graded porous silicon-carbon anode material.
2. Structure of graded porous silicon-carbon anode material
The graded porous silicon carbon anode material prepared in this example includes a core layer and an edge layer.
The core layer consists of four parts of silicon and carbon, namely nano macropores and nano mesopores, the silicon is dispersed in the carbon or at the edge of the carbon, and the nano macropores and the nano mesopores of the core region divide the silicon and the carbon into small units;
the nano macropores and nano mesopores are positioned at the center of the core layer and near the center or the edge part;
the diameter of the nano macropores is 630-1500 nm, and a plurality of nano mesopores, nano micropores and netty structural carbon formed by the pores are arranged near the nano macropores;
the diameter of the nanometer mesopore is 145-300 nm, and a plurality of nanometer macropores, nanometer micropores and netty structural carbon formed by the multiple holes are arranged near the nanometer mesopore.
The edge layer consists of four parts of silicon, carbon, nano small holes and nano micro holes, wherein the silicon is dispersed in the carbon, the carbon edge and the compact carbon layer, and the nano small holes and the nano micro holes of the core region divide the silicon and the carbon into small units;
the diameter of the nanometer small holes is 24-75 nm, and a plurality of nanometer mesopores, nanometer micropores and netty structural carbon formed by the multiple holes are arranged near the nanometer small holes;
the diameter of the nanometer micropore is less than 15nm, and a plurality of nanometer pinholes and a nonporous compact carbon layer are arranged near the nanometer micropore;
the median diameter D50 of the graded porous silicon-carbon anode material is 15.6 mu m, and the tap density is 0.83g/cm 3 Specific Surface Area (SSA) of 3.2m 2 /g。
As shown in fig. 2, the silicon-carbon anode material prepared in this example has pore distribution with various pore diameters on the section, that is, the silicon-carbon anode material prepared in this invention has a hierarchical porous structure.
3. Preparation of silicon-containing negative electrode sheet
Mixing the anode active material, the conductive agent and the binder according to the mass percentages of 91%, 3% and 6%, adding deionized water, stirring, controlling the solid content to be 46.7%, and adjusting the viscosity to be 1520mpa.s, thus obtaining the mixed anode slurry. And coating the mixed negative electrode slurry on a nickel-plated copper foil of a negative electrode current collector, and drying and tabletting to obtain the silicon-containing negative electrode sheet. The negative electrode active material is 10% of graded porous silicon-carbon negative electrode material+90% of carbon coated artificial graphite, the conductive agent is 5% of conductive carbon black+95% of carbon micro-nano tubular conductive material, and the binder is 33% of styrene-butadiene rubber+67% of polyacrylamide.
4. Preparation of lithium ion batteries
And winding the silicon-containing negative electrode sheet, the isolating film and the nickel cobalt lithium manganate positive electrode sheet to obtain a battery core, packaging the battery core into a battery shell, drying, injecting electrolyte, packaging, forming and separating the battery core to obtain the lithium ion battery.
Example 2
Example 2 differs from example 1 in that:
the preparation method of the silicon-containing negative plate comprises the following steps: mixing 92%, 2.5% and 5.5% of mixed anode materials, a conductive agent and a binder in percentage by mass, adding deionized water, stirring, controlling the solid content to be 48.3% and the viscosity to be 2540mPa.s, obtaining mixed anode slurry, coating the mixed anode slurry on a nickel-plated copper foil of an anode current collector, drying and tabletting to obtain the silicon-containing anode sheet.
Example 3
Example 3 differs from example 1 in that:
the preparation method of the silicon-containing negative plate comprises the following steps: mixing the mixed anode material, the conductive agent and the binder according to the mass percentages of 94%, 2% and 4%, adding deionized water, stirring, controlling the solid content to be 53.6%, adjusting the viscosity to 4540mPa.s, obtaining mixed anode slurry, coating the mixed anode slurry on a nickel-plated copper foil of an anode current collector, drying and tabletting to obtain the silicon-containing anode sheet.
Example 4
1. Preparation method of graded porous silicon-carbon anode material
S1, according to 100:55: mixing monocrystalline silicon with the particle size of 20-200 nm, phenolic resin and ammonium bicarbonate according to the mass ratio of 0.5, heating at 80 ℃, and cooling after stabilizing to obtain a mixed solid;
s2, heating the mixed solid at 700 ℃, and then crushing the mixed solid to the particle size of 1.4-35 mu m to obtain a porous silicon precursor;
s3, carrying out heat preservation treatment on the porous silicon precursor for 1-8 hours at the temperature of 300-600 ℃, then introducing acetylene mixed gas (the volume ratio of acetylene is 70%) taking krypton as carrier gas, and carrying out vapor deposition for 8 hours at the temperature of 550 ℃ to obtain the graded porous silicon-carbon anode material.
2. Structure of graded porous silicon-carbon anode material
The graded porous silicon carbon anode material prepared in this example includes a core layer and an edge layer.
The core layer consists of four parts of silicon and carbon, namely nano macropores and nano mesopores, the silicon is dispersed in the carbon or at the edge of the carbon, and the nano macropores and the nano mesopores of the core region divide the silicon and the carbon into small units;
the nano macropores and nano mesopores are positioned at the center of the core region and near the center or the edge part;
the diameter of the nano macropores is 730-1350 nm, and a plurality of nano mesopores, nano micropores and netty structural carbon formed by the pores are arranged near the nano macropores;
the diameter of the nanometer mesopore is 110-320 nm, and a plurality of nanometer macropores, nanometer micropores and netty structural carbon formed by the multiple holes are arranged near the nanometer mesopore.
The edge layer consists of four parts of silicon, carbon, nano small holes and nano micro holes, wherein the silicon is dispersed in the carbon, the carbon edge and the compact carbon layer, and the nano small holes and the nano micro holes of the core region divide the silicon and the carbon into small units;
the diameter of the nanometer small holes is 24-73 nm, and a plurality of nanometer mesopores, nanometer micropores and netty structural carbon formed by the multiple holes are arranged near the nanometer small holes;
the diameter of the nanometer micropore is less than 15nm, and a plurality of nanometer pinholes and a nonporous compact carbon layer are arranged near the nanometer micropore;
the median particle diameter D50 of the graded porous silicon-carbon anode material is 14.6 mu m, and the tap density is 0.78g/cm 3 Specific Surface Area (SSA) of 2.7m 2 /g。
3. Preparation of silicon-containing negative electrode sheet
Mixing the anode active material, the conductive agent and the binder according to the mass percentage of 91%, 3% and 6%, adding deionized water, stirring, controlling the solid content at 43.7% and adjusting the viscosity to 1440mPa.s, thus obtaining the mixed anode slurry. And coating the mixed negative electrode slurry on a nickel-plated copper foil of a negative electrode current collector, and drying and tabletting to obtain the silicon-containing negative electrode sheet. The negative electrode active material is 30% of graded porous silicon-carbon negative electrode material+70% of carbon coated artificial graphite, the conductive agent is 5% of conductive carbon black+95% of carbon micro-nano tubular conductive material, and the binder is 33% of styrene-butadiene rubber+67% of polyacrylamide.
4. Preparation of lithium ion batteries
And winding the silicon-containing negative electrode sheet, the isolating film and the nickel cobalt lithium manganate positive electrode sheet to obtain a battery core, packaging the battery core into a battery shell, drying, injecting electrolyte, packaging, forming and separating the battery core to obtain the lithium ion battery.
Example 5
Example 5 differs from example 4 in that:
the preparation method of the silicon-containing negative plate comprises the following steps: mixing 92%, 2.5% and 5.5% of mixed anode materials, conductive agents and binders by mass percent, adding deionized water, stirring, controlling the solid content to be 53.6% and the viscosity to be 2840mPa.s, obtaining mixed anode slurry, coating the mixed anode slurry on a nickel-plated copper foil of an anode current collector, drying and tabletting to obtain the silicon-containing anode sheet.
Example 6
Example 6 differs from example 4 in that:
the preparation method of the silicon-containing negative plate comprises the following steps: mixing the mixed anode material, the conductive agent and the binder according to the mass percentages of 94%, 2% and 4%, adding deionized water, stirring, controlling the solid content to be 54.1%, adjusting the viscosity to be 5110mPa.s, obtaining mixed anode slurry, coating the mixed anode slurry on a nickel-plated copper foil of an anode current collector, drying and tabletting to obtain the silicon-containing anode sheet.
Comparative example 1
Comparative example 1 differs from example 1 in that: in step S1, no ammonium bicarbonate as a pore-forming agent is added, so that the core region cannot form graded pores.
Comparative example 2
Comparative example 2 differs from example 1 in that: the absence of step S3 results in no formation of an outer carbon layer in the graded porous silicon carbon negative electrode material.
Performance testing
1. Swelling condition of silicon-containing negative electrode sheet
Measuring the thickness of the silicon-containing negative electrode sheet after tabletting by using a ten-thousandth screw ruler; the 100% soc of the examples and comparative examples was disassembled to obtain a silicon-containing negative electrode sheet, and the thickness of the silicon-containing negative electrode sheet of the 100% soc was measured with a ten-thousandth screw scale, and the expansion ratio of the silicon negative electrode sheet= (thickness of the battery electrode sheet under 100% soc-thickness of the silicon negative electrode sheet after tabletting)/thickness of the negative electrode sheet after tabletting was 100%.
2. Battery electrical performance detection
At 25 ℃, under the conditions that the initial and cut-off voltages are 2.8V and 4.35V, 1C is charged to 4.35V, then 4.35V is charged at constant voltage until the current is reduced to 0.05C, then 0.5C is discharged to 2.8V, then 1C is charged to 4.35V, then 4.35V is charged until the current is reduced to 0.05C, then 0.5C is discharged to 2.8V, and the battery is circularly charged and discharged. The first coulomb efficiency of the 1 st turn of the battery charge and discharge and the capacity retention rate were recorded.
TABLE 1 swelling behavior of silicon-containing negative electrode sheets
| Expansion ratio | |
| Example 1 | 46.7％ |
| Example 2 | 46.1％ |
| Example 3 | 41.7％ |
| Example 4 | 41.2％ |
| Example 5 | 42.6％ |
| Example 6 | 43.8％ |
| Comparative example 1 | 56.7％ |
| Comparative example 2 | 50.4％ |
Referring to table 1, the expansion rates of the silicon-containing negative electrode sheets of comparative examples 1 to 2 were 56.7% and 50.4%, respectively, and the expansion rate of comparative example 1 was the highest, indicating that the hierarchical porous structure had the greatest effect on the expansion rate of the silicon negative electrode material. Therefore, the invention utilizes the hierarchical porous structure and the inner carbon layer and the outer carbon layer to share the expansion of the internal silicon, and can effectively slow down the expansion of the silicon anode material in the circulation process.
TABLE 2 initial coulombic efficiency, capacity retention for batteries
Referring to Table 2, the capacity fading of 100 th, 500 th and 800 th turns of comparative examples 1-2 is remarkable as compared with examples 1-6, which shows that the capacity retention rate can be greatly improved and the cycling stability of the battery can be improved by increasing the hierarchical porous structure and isolating the contact between the nano-silicon surface and inner porous and the electrolyte through the outer carbon layer and the inner carbon layer.
The above-described embodiments are merely preferred embodiments for fully explaining the present invention, and the scope of the present invention is not limited thereto. Equivalent substitutions and modifications will occur to those skilled in the art based on the present invention, and are intended to be within the scope of the present invention. The protection scope of the invention is subject to the claims.
Claims (11)
1. The graded porous silicon-carbon anode material is characterized by comprising a core layer and an edge layer positioned outside the core layer; the core layer and the edge layer comprise a carbon matrix, nano silicon particles and pores;
wherein the pores in the core layer comprise nano macropores and nano mesopores, the diameter of the nano macropores is 500-1600 nm, and the diameter of the nano mesopores is 100-500 nm;
the pores in the edge layer comprise nano pores and nano micropores, the diameter of the nano pores is 20-100 nm, and the diameter of the nano micropores is less than 20nm.
2. The graded porous silicon-carbon anode material according to claim 1, wherein the diameter of the core layer is 2.1 to 23.4 μm;
and/or the thickness of the edge layer is 0.15-8.6 mu m.
3. The graded porous silicon-carbon anode material of claim 1, wherein the surface of the graded porous silicon-carbon anode material is coated with an outer carbon layer;
and/or an inner carbon layer is deposited on the pore walls of the nano macropores, the nano mesopores and the nano pinholes.
4. The graded porous silicon-carbon anode material of claim 3, wherein the thickness of the outer carbon layer and the inner carbon layer are each 5-200 nm;
and/or the thickness of the inner carbon layer is smaller than the thickness of the outer carbon layer.
5. The hierarchical porous silicon-carbon anode material according to claim 1, wherein the nano silicon particles comprise elemental silicon and SiO x (0＜x＜2)；
And/or in the hierarchical porous silicon-carbon anode material, the mass ratio of silicon is 5-90%, and the mass ratio of O is 3-55%.
6. The graded porous silicon-carbon anode material according to claim 1, wherein the graded porous silicon-carbon anode material has a median particle diameter D50 of 3.0 to 22.0 μm;
and/or the tap density of the graded porous silicon-carbon anode material is 0.65-1.35 g/cm 3 ；
And/or the specific surface area of the graded porous silicon-carbon anode material is 0.95-6.5 m 2 /g。
7. The preparation method of the graded porous silicon-carbon anode material is characterized by comprising the following steps of:
s1, mixing a silicon source, a binder carbon source and a pore-forming agent, heating once, and cooling to obtain a mixed solid;
s2, the mixed solid is heated for the second time and then crushed to obtain a porous silicon precursor;
s3, introducing acetylene mixed gas taking non-oxidizing gas as carrier gas into the porous silicon precursor to carry out vapor deposition reaction, and then carrying out heat preservation treatment to obtain the graded porous silicon-carbon anode material.
8. The method for preparing a hierarchical porous silicon-carbon anode material according to claim 7, wherein in step S1: the silicon source is monocrystalline silicon with the grain diameter of 20-200 nm,Amorphous silicon or SiO x (0 < x < 2);
and/or the carbon source of the binder is one or more of polyethylene, polyacrylic acid, polypropylene, polyvinylpyrrolidone and phenolic resin;
and/or the pore-forming agent is one or more of ammonium bicarbonate, ammonium carbonate and ammonium oxalate;
and/or the mass ratio of the silicon source, the binder carbon source and the pore-forming agent is 100: 5-80: 0.01 to 0.5;
and/or, the temperature of the primary heating is 60-200 ℃;
in step S2: the temperature of the secondary heating is 600-1300 ℃;
and/or the particle size of the crushed particles is 0.6-50 mu m;
in step S3: in the acetylene mixed gas taking non-oxidizing gas as carrier gas, the volume ratio of the non-oxidizing gas is 50-98%;
and/or the non-oxidizing gas is one or more of nitrogen, helium, neon, argon and krypton;
and/or the temperature of the vapor deposition reaction is 500-1300 ℃, and the time of the vapor deposition reaction is 3 min-10 h;
and/or the temperature of the heat preservation treatment is 300-600 ℃, and the time of the heat preservation treatment is 1-8 h.
9. A silicon-containing negative electrode sheet comprising a negative electrode current collector and a negative electrode material layer formed on at least one side surface of the negative electrode current collector, characterized in that the negative electrode material layer comprises a negative electrode active material comprising a graphite negative electrode material and the graded porous silicon-carbon negative electrode material according to any one of claims 1 to 6 or the graded porous silicon-carbon negative electrode material prepared by the method according to claim 7 or 8, a conductive agent and a binder.
10. The silicon-containing negative electrode sheet according to claim 9, wherein in the negative electrode material layer, the mass percentages of the negative electrode active material, the conductive agent and the binder are 75 to 99%, 0.5 to 8% and 0.6 to 15.0%, respectively;
and/or, in the anode active material, the mass ratio of the graded porous silicon-carbon anode material is 1-80%.
11. A lithium ion battery comprising a positive electrode sheet, a negative electrode sheet, a separator, and an electrolyte, the separator being configured to isolate the positive electrode sheet from the negative electrode sheet, wherein the negative electrode sheet is the silicon-containing negative electrode sheet of claim 9 or 10.
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