CN107123790B - Porous silicon-based composite anode material, preparation method and lithium ion battery - Google Patents
Porous silicon-based composite anode material, preparation method and lithium ion battery Download PDFInfo
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Abstract
The invention provides a porous silicon-based composite negative electrode material, a preparation method thereof and a lithium ion battery, wherein the porous material comprises a porous amorphous carbon matrix; silicon-containing nanoparticles and metal microparticles supported on the porous amorphous carbon matrix; the metal fine particles include one or more of Sn, Cu, and Mn. The porous structure in the porous material is beneficial to the rapid exchange of lithium ions on a contact surface, and the cycling stability is good; the metal particles and the porous amorphous carbon are used as a supporting framework of the composite porous negative electrode material, so that a stable SEI film can be formed on the surface of the negative electrode composite material, the advantage of high lithium storage capacity of the silicon material can be fully exerted, and the electrode can stably release reversible capacity, therefore, the nano silicon-based composite porous material has high reversible capacity and excellent cycle performance.
Description
Technical Field
The invention relates to the technical field of lithium ion battery cathode materials, in particular to a porous silicon-based composite cathode material, a preparation method thereof and a lithium ion battery.
Background
A lithium ion battery is a secondary battery (rechargeable battery) that mainly operates by movement of lithium ions between a positive electrode and a negative electrode. During charging and discharging, Li+Li is inserted and extracted back and forth between two electrodes+The lithium ion battery is extracted from the positive electrode and is inserted into the negative electrode through the electrolyte, and the negative electrode is in a lithium-rich state; the opposite is true during discharge. The battery generally adopts a material containing lithium element as an electrode, and is a representative of modern high-performance batteries. The basic components of a lithium ion battery include a positive electrode, a separator, a negative electrode, an electrolyte, and a battery case.
The excellent lithium ion battery cathode material is favored by researchers as an important factor capable of improving the battery and the cycle life thereof. The silicon material can be used as a lithium ion battery negative electrode material due to the fact that the silicon material has high theoretical specific capacity (4200 mAh/g), but the silicon material has a huge volume effect (> 300%) in the charge-discharge cycle process, so that active substance particles are pulverized and lose efficacy, the capacity attenuation is fast, and the practicability of the silicon negative electrode is hindered. Research shows that if the silicon particles are reduced to the micron or nanometer level, the cycle performance can be obviously improved, and the porous composite material has excellent lithium intercalation and deintercalation performance.
At present, the research on the aspect of porosity is mainly carried out on silicon nanowires, and although the silicon nanowires have excellent lithium intercalation performance, the reversible capacity and the cycle performance of the silicon nanowires are still poor.
Disclosure of Invention
In view of the above, the present invention provides a porous silicon-based composite anode material, a preparation method thereof, and a lithium ion battery, wherein the porous silicon-based composite anode material has high reversible capacity and excellent cycle performance.
The present invention provides a porous amorphous carbon substrate;
silicon-containing nanoparticles and metal microparticles supported on the porous amorphous carbon matrix;
the metal fine particles include one or more of Sn, Cu, and Mn.
Preferably, the specific surface area of the porous silicon-based composite negative electrode material is 10-100 m2The pore diameter is 5 nm-4 mu m.
Preferably, the metal fine particles have a particle diameter of 5nm to 4 μm;
the particle size of the silicon-containing nano-particles is 5 nm-500 nm.
Preferably, the silicon-containing nanoparticles comprise silicon, SiO2And SiOxOne or more of;
the SiOxWherein x is 0<x<2。
The invention provides a preparation method of the porous silicon-based composite anode material in the technical scheme, which comprises the following steps:
mixing silicon-containing nano particles with a solvent, and carrying out ball milling to obtain slurry;
mixing the slurry with metal particles, a carbon source and an auxiliary agent, spray-drying and sintering to obtain a porous silicon-based composite anode material; the metal fine particles include one or more of Sn, Cu, and Mn.
Preferably, the mass content ratio of the silicon-containing nanoparticles to the carbon source to the metal particles is 10-70: 30-90: 3-10.
Preferably, the auxiliary agent is selected from one or more of sodium-containing inorganic salt, potassium-containing inorganic salt, ammonium salt, polyvinyl alcohol, povidone and polyethylene glycol.
Preferably, the carbon source is selected from one or more of sodium carboxymethylcellulose, polyvinylidene fluoride, polyvinyl alcohol, phenolic resin, epoxy resin, melamine formaldehyde resin, povidone, sucrose, glucose and starch.
Preferably, the sintering temperature is 450-1200 ℃; the sintering time is 4-10 h.
The invention provides a lithium ion battery, which comprises the porous silicon-based composite anode material or the porous silicon-based composite anode material prepared by the preparation method.
The invention provides a porous silicon-based composite anode material, which comprises a porous amorphous carbon matrix; silicon-containing nanoparticles and metal microparticles supported on the porous amorphous carbon matrix; the metal fine particles include one or more of Sn, Cu, and Mn. In the porous silicon-based composite negative electrode material provided by the invention, the porous structure of the porous amorphous carbon matrix can provide space for the volume expansion of silicon-containing nanoparticles, the contact surface between the negative electrode material and electrolyte is increased, the rapid exchange of lithium ions on the contact surface is facilitated, and the cycling stability is good; the metal particles and the porous amorphous carbon matrix are used as a supporting framework of the composite porous material, the integrity of an electrode conductive network can be maintained while the cycle stability of the composite material is maintained, a stable SEI film can be formed on the surface of the cathode composite material with the structure, the advantage of high lithium storage capacity of the silicon material can be fully exerted, and the electrode can stably release reversible capacity, so that the nano silicon-based composite porous material has high reversible capacity and excellent cycle performance. The experimental results show that: the porous silicon-based composite negative electrode material provided by the invention is assembled into a 2032 button cell, the first discharge capacity is 1600-2620 mAh/g, the charge-discharge efficiency is 84-99%, and the capacity retention rate is 84-89% after 100 times.
Drawings
Fig. 1 is a schematic structural diagram of a porous spherical nano silicon-based negative electrode material for a lithium ion battery provided in an embodiment of the present invention;
fig. 2 is an XRD pattern of the porous spherical nano silicon-based negative electrode material for the lithium ion battery prepared in example 1 of the present invention;
fig. 3 is a TEM image of the porous spherical nano silicon-based negative electrode material for a lithium ion battery prepared in example 1 of the present invention;
fig. 4 is an SEM image of the porous spherical nano silicon-based negative electrode material for a lithium ion battery prepared in example 1 of the present invention, at 1200 times magnification;
fig. 5 is an SEM image of 5000 times magnification of the porous spherical nano silicon-based negative electrode material for lithium ion battery prepared in example 1 of the present invention;
fig. 6 is a first circle and a second circle of charge-discharge curves of the porous spherical nano silicon-based negative electrode material for the lithium ion battery prepared in example 1 of the present invention;
fig. 7 is a cycle performance diagram of the porous spherical nano silicon-based negative electrode material for the lithium ion battery prepared in example 1 of the present invention.
Detailed Description
The invention provides a porous silicon-based composite anode material, which comprises a porous amorphous carbon matrix;
silicon-containing nanoparticles and metal microparticles supported on the porous amorphous carbon matrix;
the metal fine particles include one or more of Sn, Cu, and Mn.
The porous silicon-based composite negative electrode material provided by the invention comprises a porous amorphous carbon matrix. In the present invention, the porous amorphous carbon matrix is made by sintering a carbon source; the carbon source is preferably selected from one or more of sodium carboxymethylcellulose (CMC), polyvinylidene fluoride (PVDF), polyvinyl alcohol, phenolic resins, epoxy resins, melamine formaldehyde resins, povidone, sucrose, glucose and starch, more preferably from one or more of phenolic resins, glucose, sodium carboxymethylcellulose, polyvinyl alcohol and starch, most preferably from phenolic resins and/or glucose. The source of the carbon source is not particularly limited in the present invention, and any carbon source known to those skilled in the art can be used, and commercially available carbon sources can be used. In the invention, the temperature of the porous amorphous carbon matrix obtained by sintering the carbon source is preferably 450-1200 ℃; the time for sintering the carbon source to obtain the porous amorphous carbon matrix is preferably 4-10 h. In the porous amorphous carbon matrix, the porous structure can provide space for the volume expansion of the silicon-containing nanoparticles, the contact surface between the silicon-containing nanoparticles and an electrolyte is increased, the rapid exchange of lithium ions on the contact surface is facilitated, and the cycling stability is good.
The porous silicon-based composite anode material provided by the invention comprises silicon-containing nanoparticles loaded on the porous shaped carbon matrix. In the present invention, the silicon-containing nanoparticles preferably comprise silicon, SiO2And SiOxOne or more of; the SiOxWherein x is preferably 0<x<More preferably, x is 1, x is 0.5, or x is 1.5. In the invention, the particle size of the silicon-containing nano-particles is preferably 5 nm-500 nm, and more preferably 100-400 nm; in the embodiment of the invention, the particle size of the silicon-containing nanoparticles is specifically 100-200 nm, 100-500 nm or 5-100 nm.
The porous silicon-based composite negative electrode material provided by the invention comprises metal particles loaded on a porous amorphous carbon matrix; the metal fine particles include one or more of Sn, Cu, and Mn. In the present invention, the particle diameter of the metal fine particles is preferably 5nm to 4 μm, more preferably 100nm to 3 μm, and most preferably 500nm to 1000 nm; in a specific embodiment of the present invention, the metal fine particles have a particle size of 500 nm.
In the invention, the metal particles and the porous amorphous carbon matrix are used as a supporting framework of the composite porous material, the integrity of an electrode conductive network can be maintained while the cycle stability of the composite material is maintained, a stable SEI film can be formed on the surface of the cathode composite material with the structure, the advantage of high lithium storage capacity of a silicon material can be fully exerted, and the reversible capacity can be stably released by the electrode.
Fig. 1 is a schematic structural diagram of a porous silicon-based composite anode material provided in an embodiment of the present invention, where 1 is a silicon-containing nanoparticle, 2 is a metal particle, 3 is a porous structure, and 4 is amorphous carbon.
In the present invention, silicon-containing nanoparticles 1 and metal microparticles 2 are in a porous structure 3 of amorphous carbon 4. In the present invention, the porous structure can be a porous structure containingThe volume expansion of the silicon nano particles provides space, the contact surface between the silicon nano particles and electrolyte is increased, the rapid exchange of lithium ions on the contact surface is facilitated, and the cycling stability is good. The porous silicon-based composite negative electrode material provided by the invention is in an ellipsoid shape or a sphere-like shape. In the invention, the specific surface area of the porous silicon-based composite anode material is 10-100 m2Preferably 20 to 95 m/g2(ii)/g; the aperture of the silicon-based negative electrode composite porous material is 5 nm-4 μm, preferably 100 nm-1 μm.
In the invention, the D50 of the silicon-based negative electrode composite porous material is preferably 5-45 μm, and more preferably 10-35 μm.
The invention provides a preparation method of the porous silicon-based composite anode material in the technical scheme, which comprises the following steps:
mixing silicon-containing nano particles with a solvent, and carrying out ball milling to obtain slurry;
mixing the slurry with metal particles, a carbon source and an auxiliary agent, spray-drying and sintering to obtain a porous silicon-based composite anode material;
the metal fine particles include one or more of Sn, Cu, and Mn.
The invention mixes silicon-containing nano particles with a solvent, and ball-mills to obtain slurry. In the present invention, the silicon-containing nanoparticles preferably comprise silicon, SiO2And SiOxOne or more of; the SiOxWherein x is preferably 0<x<More preferably, x is 1, x is 0.5, or x is 1.5. In the invention, the particle size of the silicon-containing nano-particles is preferably 5 nm-500 nm, and more preferably 100-400 nm; in the embodiment of the invention, the particle size of the silicon-containing nanoparticles is specifically 100-200 nm, 100-500 nm or 5-100 nm. In the present invention, the solvent is preferably selected from one or more of water, ethanol, glycerol, tetrahydrofuran, benzene, toluene, xylene, and dimethylamide, more preferably from one or more of water, ethanol, and dimethylamide, and most preferably water. The present invention is not particularly limited with respect to the sources of the silicon-containing nanoparticles and the solvent, and the above-mentioned silicon-containing nanoparticles and solvents known to those skilled in the art can be used, for example, commercially available silicon-containing nanoparticles and solvents can be usedA commercial product. In the present invention, the volume ratio of the silicon-containing nanoparticles to water is preferably 1 g: (100-1000) mL, more preferably 1 g: (200-800) mL.
In the invention, the silicon-containing nano particles and water are preferably mixed, and the obtained mixture is subjected to high-energy ball milling and then ball milling in a sand mill to obtain slurry. In the invention, the rotation speed of the high-energy ball mill is preferably 400-2000 r/min, and more preferably 500-1800 r/min; the high-energy ball milling time is preferably 3-10 h, and more preferably 5-9 h; in the specific embodiment of the invention, the rotating speed of the high-energy ball mill is 1800 rpm, 2000 rpm and 1500 rpm; the time of the high-energy ball milling is 8 h. In the invention, the rotation speed of the sand mill during ball milling in the sand mill is preferably 1500-2500 rpm, and more preferably 1700-2400 rpm; the time of ball milling in the sand mill is preferably 4-10 h, more preferably 4-8 h, and most preferably 4 h.
After slurry is obtained, the slurry is mixed with metal particles, a carbon source and an auxiliary agent, and the mixture is sintered after spray drying to obtain the porous silicon-based composite anode material; the metal fine particles include one or more of Sn, Cu, and Mn.
In the present invention, the metal fine particles include one or more of Sn, Cu, and Mn; the particle size of the metal fine particles is preferably 5nm to 4 μm, more preferably 100nm to 3 μm, and most preferably 500nm to 1000 nm. The source of the metal fine particles is not particularly limited in the present invention, and the above metal fine particles known to those skilled in the art may be used, and commercially available products thereof may be used.
In the present invention, the carbon source is preferably selected from one or more of sodium carboxymethylcellulose, polyvinylidene fluoride, polyvinyl alcohol, phenol resin, epoxy resin, melamine formaldehyde resin, povidone, sucrose, glucose and starch; more preferably one or more selected from glucose, phenolic resin, polyvinyl alcohol and starch; most preferably selected from glucose and/or phenolic resins. In one embodiment of the present invention, the carbon source is specifically a phenolic resin, which is purchased from national pharmaceutical group chemical agents, ltd; in another embodiment of the invention, the carbon source is in particular glucose; the glucose was purchased from national drug group chemical agents limited.
In the present invention, the auxiliary is preferably selected from one or more of sodium-containing inorganic salts, potassium-containing inorganic salts, ammonium salts, polyvinyl alcohol, povidone, and polyethylene glycol; more preferably one or more selected from polyvinyl alcohol, povidone, polyethylene glycol, ammonium bicarbonate, ammonium carbonate, sodium chloride, sodium nitrate, potassium chloride and potassium nitrate; most preferably one or more selected from ammonium carbonate, sodium chloride and sodium sulphate.
The invention preferably mixes the slurry with the metal particles, the carbon source and the auxiliary agent in the form of ultrasonic dispersion. In the invention, the mixing time of the slurry, the metal particles, the carbon source and the auxiliary agent is preferably 3 to 6 hours, and more preferably 4 to 5 hours.
In the invention, the mass ratio of the silicon-containing nanoparticles to the carbon source to the metal particles is preferably 10-70: 30-90: 3-10, and more preferably 10-70: 35-90: 4-9; in a specific embodiment of the invention, the mass ratio of the silicon-containing nanoparticles, the carbon source and the metal particles is specifically 10:40:3, 70:90:10, 15:35:4 or 65:85: 9. The mass ratio of the silicon-containing nanoparticles to the auxiliary agent is preferably 1: 1-1: 10, and more preferably 1: 2-1: 5.
The invention mixes the slurry with metal particles, carbon source and auxiliary agent to obtain a mixture, and then the mixture is sintered after spray drying. In the invention, the temperature of the air inlet is preferably 220-280 ℃ during spray drying; the temperature of the air outlet during spray drying is preferably 90-120 ℃; the rotation speed of the atomizer during spray drying is preferably 19000-21000 r/min, and more preferably 20000 r/min; at the above rotation speed, the purpose is to uniformly mix the slurry with the metal particles, the carbon source and the auxiliary agent. The tap density of the spherical material obtained after spray drying is 0.6-2.2 g/cm3. The mixture is spray dried to obtain spherical material with ellipsoidal and/or spheroidal shape.
The sintering is preferably carried out in a resistance furnace known to those skilled in the art. The invention preferably carries out sintering under the protective atmosphere; the protective atmosphere comprises one or more of nitrogen, argon and hydrogen. In the invention, the sintering temperature is preferably 450-1200 ℃, more preferably 500-1100 ℃, and in the specific embodiment of the invention, the sintering temperature is specifically 800 ℃; the sintering time is preferably 4-10 h, and more preferably 5-10 h; in a particular embodiment of the invention, the sintering time is in particular 5h, 8h or 10 h.
According to the invention, the sintered product is preferably washed, dried and screened in sequence to obtain the porous silicon-based composite anode material. The washing method of the present invention is not particularly limited, and washing techniques well known to those skilled in the art may be used. The invention preferably adopts a centrifugal washing mode for washing; the solvent used for centrifugal washing is preferably deionized water or an aqueous alcohol solution.
The method for drying the washed sintering product is not particularly limited, and a drying technical scheme well known to those skilled in the art can be adopted. In the invention, the temperature for drying the washed sintering product is preferably 50-120 ℃.
The method of screening is not particularly limited in the present invention, and screening techniques well known to those skilled in the art may be used. In the invention, the D50 of the silicon-based negative electrode composite porous material obtained after screening is preferably 5-45 μm, and more preferably 10-35 μm.
The invention provides a lithium ion battery, which comprises the porous silicon-based composite anode material or the porous silicon-based composite anode material prepared by the preparation method.
The invention makes the silicon-based negative electrode composite porous material described in the technical scheme into the 2030 button cell for electrochemical performance test, and the manufacturing process of the 2030 button cell specifically comprises the following steps:
weighing a silicon-based negative electrode composite porous material, acetylene black and polyvinylidene fluoride in a mass ratio of 80:10: 10; mixing polyvinylidene fluoride and N-methyl pyrrolidone to prepare a polyvinylidene fluoride solution with the mass concentration of 0.02 g/mL; uniformly mixing the weighed silicon-based negative electrode composite porous material with acetylene black, and then adding the polyvinylidene fluoride solutionCoating the solution on a Cu foil, performing vacuum drying in a vacuum drying oven at 120 ℃ for 8 hours, taking an electrode plate with the diameter of 1.6 cm as a working electrode, taking a metal lithium plate as a counter electrode, and taking an electrolyte as LiPF6the/EC-DMC-EMC (where EC is ethylene carbonate, DMC is dimethyl carbonate, EMC is methyl ethyl carbonate, volume ratio is 1:1:1) was assembled into 2032 coin cell in a glove box filled with Ar gas.
The experimental results show that: the porous silicon-based composite negative electrode material provided by the invention is assembled into a 2032 button cell, the first discharge capacity is 1600-2620 mAh/g, the charge-discharge efficiency is 84-99%, and the capacity retention rate is 84-89% after 100 times.
In order to further illustrate the present invention, the following examples are provided to describe the porous silicon-based composite anode material, the preparation method thereof and the lithium ion battery in detail, but they should not be construed as limiting the scope of the present invention.
Example 1
Silicon powder and 50mL of aqueous solution are subjected to high-energy ball milling for 8 hours at 2000 rpm under inert atmosphere, and then the silicon powder and the aqueous solution are transferred to a sand mill for ball milling for 4 hours at 1000 rpm; mixing 2.5g of silicon slurry with the particle size of 5-100 nm, the mass ratio of silicon powder to glucose to Sn being 10:40:3, the mass ratio of silicon powder to sodium chloride being 1:1, carrying out ultrasonic dispersion for 5 hours, carrying out spray drying for granulation, rotating the atomizer at 20000 revolutions for achieving the purpose of uniform particles, drying at 220 ℃ of an air inlet and 110 ℃ of an air outlet, sintering the obtained spherical material in a resistance furnace at 800 ℃ for 5 hours in an inert atmosphere, washing the obtained spherical material with centrifugal water, drying, and screening to obtain the porous spherical nano silicon-based negative electrode material for the lithium ion battery, namely the porous silicon-based composite negative electrode material.
The porous spherical nano silicon-based negative electrode material for the lithium ion battery prepared in this embodiment is subjected to crystal phase analysis and morphology analysis, as shown in fig. 2 and 3, respectively: as shown in fig. 2, which is an XRD pattern of the porous spherical nano silicon-based negative electrode material for the lithium ion battery prepared in example 1 of the present invention, it can be seen from fig. 2 that the porous spherical nano silicon-based negative electrode material prepared in example 1 is a pure phase silicon composite material. Fig. 3 is a TEM image of the porous spherical nano silicon-based negative electrode material for the lithium ion battery prepared in example 1 of the present invention, and it can be seen from fig. 3 that the black particles are silicon particles, the size of the black particles is between 100nm and 150nm, and the interior and the surface of the black particles have a pore structure, and the size of the pores is between 100nm and 200 nm. Fig. 4 and 5 are SEM images of the porous spherical nano silicon-based negative electrode material for the lithium ion battery prepared in example 1, and fig. 4 is an SEM image of the porous spherical nano silicon-based negative electrode material for the lithium ion battery prepared in example 1 of the present invention at 1200 times magnification; fig. 5 is an SEM image with 5000 times magnification of the porous spherical nano silicon-based negative electrode material for lithium ion battery prepared in example 1 of the present invention; as can be seen from FIGS. 4 and 5, a large number of pores are also present on the surface of the particles, and the size of the pores is between 100nm and 1 μm.
The porous spherical nano silicon-based negative electrode material for the lithium ion battery prepared in the embodiment is subjected to electrochemical performance test. 2030 button cell manufacturing and electrochemical performance testing are as follows, the mass ratio of the porous spherical nano silicon-based negative electrode material for the lithium ion cell, acetylene black and PVDF (polyvinylidene fluoride) is 80:10:10, the porous spherical nano silicon-based negative electrode material for the lithium ion cell and the acetylene black are uniformly mixed, then a solution containing PVDF (the solution containing PVDF is a prepared 0.02g/mL PVDF/NMP solution) is added, the solution is coated on a Cu foil, the solution is dried in a vacuum drying oven at 120 ℃ for 8 hours in vacuum, an electrode slice with the diameter of 1.6 cm is taken as a working electrode, a metal lithium slice is taken as a counter electrode, and an electrolyte is LiPF6the/EC-DMC-EMC (volume ratio 1:1:1) was assembled into 2032 coin cell battery in a glove box filled with Ar gas. The charge-discharge voltage range is 2.0-0.005V, the charge-discharge current of the first circle is 200mA/g (0.1C), and the charge-discharge current density of the first circle and the later circle is 400mA/g (0.2C). Through testing, the test chart is as shown in fig. 6, fig. 6 is a charge-discharge curve diagram of the first ring and the second ring of the porous spherical nano silicon-based negative electrode material for the lithium ion battery prepared in the embodiment 1 of the present invention, and it can be seen from fig. 6 that: the first discharge capacity is 2618.7mAh/g, the first charge capacity is 2253.9mAh/g, the first charge-discharge efficiency is 86.1%, the second discharge capacity is 2229mAh/g, the charge capacity is 2167.8mAh/g, and the charge-discharge efficiency is 97.3%. FIG. 7 shows porous spherical nanoparticles for lithium ion batteries prepared in example 1 of the present inventionThe cycle performance curve of the silicon-based anode material can be seen from fig. 7: under the multiplying power of 0.2C, after 100 cycles, the discharge capacity is 1897.4mAh/g, the charge capacity is 1874.2mAh/g, the charge-discharge efficiency is 99.0%, and the capacity retention rate is 86%.
Example 2
Silicon powder and 50mL of aqueous solution are subjected to high-energy ball milling for 8 hours at 1800 rpm under inert atmosphere, and then are transferred to a sand mill for ball milling for 4 hours at 1500 rpm; 2.5g of silicon slurry with the particle size of 100-500 nanometers is obtained, the mass ratio of silicon powder to phenolic resin to Sn is 70:90:10, and the silicon powder to (NH)4)2CO3Mixing the (ammonium carbonate) according to the mass ratio of 1:10, performing ultrasonic dispersion for 5 hours, performing spray drying for granulation, wherein the rotating speed of an atomizer is 20000 revolutions per minute to achieve the purpose of uniform particles, and the temperature of a drying air inlet is 220 ℃ and the temperature of an air outlet is 110 ℃. And sintering the obtained spherical material in a resistance furnace at 800 ℃ for 10h in an inert atmosphere, washing the obtained spherical material with centrifugal water, drying, and screening to obtain the porous spherical nano silicon copper anode material for the lithium ion battery, namely the porous silicon-based composite anode material.
The porous spherical nano silicon copper anode material for the lithium ion battery prepared in the embodiment is subjected to electrochemical performance test. 2030 button cell manufacturing and electrochemical performance testing are as follows, the mass ratio of the porous spherical nano silicon copper negative electrode material for the lithium ion cell, acetylene black and PVDF (polyvinylidene fluoride) is 80:10:10, the porous spherical nano silicon copper negative electrode material for the lithium ion cell and the acetylene black are uniformly mixed, then a solution containing PVDF is added, the solution containing PVDF is a prepared 0.02g/mL PVDF/NMP solution, the solution is coated on a Cu foil, the solution is dried in a vacuum drying oven at 120 ℃ for 8 hours, an electrode slice with the diameter of 1.6 cm is taken as a working electrode, a metal lithium slice is taken as a counter electrode, and an electrolyte is LiPF6the/EC-DMC-EMC (volume ratio 1:1:1) was assembled into 2032 coin cell battery in a glove box filled with Ar gas. The charge-discharge voltage range is 2.0-0.005V, the charge-discharge current of the first circle is 200mA/g (0.1C), and the charge-discharge current density of the first circle and the later circle is 400mA/g (0.2C). Through tests, the first discharge capacity is 2300mAh/g, the charge-discharge efficiency is 85%, and the capacity retention rate is 84% after 100 times.
Example 3
Silicon powder and 50mL of aqueous solution are subjected to high-energy ball milling for 8 hours at 1500 revolutions per minute in an inert atmosphere, and then are transferred to a sand mill for ball milling for 4 hours at 2000 revolutions per minute; 2.5g of silicon slurry with the grain diameter of 100 nm-200 nm is obtained, the mass ratio of the silicon powder, the phenolic resin and the copper powder is 65:85:9, and the silicon powder and the Na are added2SO4Mixing the sodium sulfate with the mass ratio of 1:5, performing ultrasonic dispersion for 5 hours, performing spray drying for granulation, wherein the rotation speed of an atomizer is 20000 revolutions to achieve the purpose of uniform granules, and the drying air inlet temperature is 220 ℃ and the air outlet temperature is 110 ℃. And sintering the obtained spherical material in a resistance furnace at 800 ℃ for 8h in an inert atmosphere, washing the obtained spherical material with centrifugal water, drying, and screening to obtain the porous spherical nano silicon copper anode material for the lithium ion battery, namely the porous silicon-based composite anode material.
The porous spherical nano silicon-aluminum anode material for the lithium ion battery prepared in the embodiment is subjected to electrochemical performance test. 2030 button cell is manufactured and tested in electrochemical performance, wherein the mass ratio of the high-capacity spherical porous silicon-based composite negative electrode material to acetylene black to PVDF (polyvinylidene fluoride) is 80:10:10, the porous spherical nano silicon-aluminum negative electrode material for the lithium ion battery is uniformly mixed with B and B, then a solution containing PVDF is added, the solution containing PVDF is a prepared 0.02g/mL PVDF/NMP solution, the solution is coated on a Cu foil and is dried in a vacuum drying oven at 120 ℃ for 8 hours, an electrode slice with the diameter of 1.6 cm is taken as a working electrode, a metal lithium slice is taken as a counter electrode, and an electrolyte is LiPF6the/EC-DMC-EMC (volume ratio 1:1:1) was assembled into 2032 coin cell battery in a glove box filled with Ar gas. The charge-discharge voltage range is 2.0-0.005V, the charge-discharge current of the first circle is 200mA/g (0.1C), and the charge-discharge current density of the first circle and the later circle is 400mA/g (0.2C). Through tests, the first discharge capacity is 2000mAh/g, the charge-discharge efficiency is 83%, and the capacity retention rate is 89% after 100 times of tests.
Example 4
Carrying out high-energy ball milling on SiO powder and 50mL of aqueous solution at 1800 rpm for 8 hours under inert atmosphere, and then transferring the SiO powder and the aqueous solution to a sand mill for ball milling at 1500 rpm for 4 hours; 2.5g of the obtained particle size 10nm ℃100nm of SiO slurry, the mass ratio of silicon powder, phenolic resin and Mn is 15:35:4, and the mass ratio of silicon powder to Na2SO4Mixing the materials according to the mass ratio of 1:2, performing ultrasonic dispersion for 5 hours, performing spray drying for granulation, rotating an atomizer at the speed of 20000 revolutions to achieve the purpose of uniform particles, drying at the air inlet temperature of 220 ℃ and the air outlet temperature of 110 ℃, sintering the obtained spherical material in a resistance furnace at the temperature of 800 ℃ for 5 hours in an inert atmosphere, centrifuging, washing, drying and screening the obtained spherical material to obtain the porous spherical nano SiO negative electrode material for the lithium ion battery, namely the porous silicon-based composite negative electrode material.
The porous spherical nano SiO negative electrode material for the lithium ion battery prepared in the embodiment is subjected to electrochemical performance test. 2030 button cell manufacturing and electrochemical performance testing are that the mass ratio of porous spherical nano SiO negative material for lithium ion battery, acetylene black and PVDF (polyvinylidene fluoride) is 80:10:10, the porous spherical nano SiO negative material for lithium ion battery and B: block black are mixed uniformly, then a solution containing PVDF is added, (the solution containing PVDF is 0.02g/mL PVDF/NMP solution prepared, the solution is coated on Cu foil, vacuum drying is carried out in a vacuum drying box at 120 ℃ for 8 hours, an electrode slice with the diameter of 1.6 cm is taken as a working electrode, a metal lithium slice is a counter electrode, an electrolyte is Li PF 6/EC-EMC (volume ratio is 1:1:1), the button cell is assembled in a glove box filled with Ar gas, the charging and discharging voltage range is 2.0-0.005V, the charging and discharging current of a first circle is 200mA/g (0.1C), the charge-discharge current density after the first turn was 400mA/g (0.2C). Tests show that the first discharge capacity is 1600mAh/g, the charge-discharge efficiency is 84%, and the capacity retention rate is 89% after 100 times.
From the above embodiments, the present invention provides a porous silicon-based composite negative electrode material, including a porous amorphous carbon matrix; silicon-containing nanoparticles and metal microparticles supported on the porous amorphous carbon matrix; the metal fine particles include one or more of Sn, Cu, and Mn. In the porous amorphous carbon matrix of the porous silicon-based composite negative electrode material, the porous structure can provide space for the volume expansion of silicon-containing nanoparticles, the contact surface between the negative electrode material and electrolyte is increased, the rapid exchange of lithium ions on the contact surface is facilitated, and the cycling stability is good; the metal particles and the porous amorphous carbon are used as a supporting framework of the composite porous material, the integrity of an electrode conductive network can be maintained while the cycle stability of the composite material is maintained, a stable SEI film can be formed on the surface of the cathode composite material with the structure, the advantage of high lithium storage capacity of a silicon material can be fully exerted, and the electrode can stably release reversible capacity, so that the nano silicon-based composite porous material has high reversible capacity and excellent cycle performance. The experimental results show that: the porous silicon-based composite negative electrode material provided by the invention is assembled into a 2032 button cell, the first discharge capacity is 1600-2620 mAh/g, the charge-discharge efficiency is 84-99%, and the capacity retention rate is 84-89% after 100 times.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (6)
1. A porous silicon-based composite anode material comprises a porous amorphous carbon matrix;
silicon-containing nanoparticles and metal microparticles supported on the porous amorphous carbon matrix;
the metal fine particles include one or more of Sn, Cu, and Mn;
the specific surface area of the porous silicon-based composite anode material is 10-100 m2Per gram, the aperture is 5nm to 4 mu m;
the particle size of the metal particles is 5 nm-4 mu m;
the particle size of the silicon-containing nano particles is 5 nm-500 nm;
the silicon-containing nanoparticles comprise silicon and SiO2And SiOxOne or more of;
the SiOxWherein x is 0<x<2；
The porous amorphous carbon matrix is prepared by sintering a carbon source; the carbon source is selected from one or more of phenolic resin, glucose, sodium carboxymethyl cellulose, polyvinyl alcohol and starch.
2. A preparation method of the porous silicon-based composite anode material of claim 1 comprises the following steps:
mixing silicon-containing nano particles with a solvent, and carrying out ball milling to obtain slurry;
mixing the slurry with metal particles, a carbon source and an auxiliary agent, spray-drying and sintering to obtain a porous silicon-based composite anode material; the metal fine particles include one or more of Sn, Cu, and Mn;
the auxiliary agent is selected from one or more of sodium-containing inorganic salt, potassium-containing inorganic salt, ammonium salt, polyvinyl alcohol, povidone and polyethylene glycol.
3. The preparation method according to claim 2, wherein the mass ratio of the silicon-containing nanoparticles to the carbon source to the metal particles is 10-70: 30-90: 3-10.
4. The preparation method according to claim 2, wherein the auxiliary agent is selected from one or more of sodium-containing inorganic salt, potassium-containing inorganic salt, ammonium salt, polyvinyl alcohol, povidone, and polyethylene glycol.
5. The preparation method according to claim 2, wherein the sintering temperature is 450-1200 ℃; the sintering time is 4-10 h.
6. A lithium ion battery is characterized by comprising the porous silicon-based composite anode material of claim 1 or the porous silicon-based composite anode material prepared by the preparation method of any one of claims 2 to 5.
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| CN109309220B (en) * | 2018-10-10 | 2021-03-23 | 成都爱敏特新能源技术有限公司 | Lithium-supplementing porous silicon monoxide negative electrode material for lithium ion battery and preparation method thereof |
| CN109585834A (en) * | 2018-12-10 | 2019-04-05 | 包头市石墨烯材料研究院有限责任公司 | A kind of mesoporous silicon-tin composite electrode material and its preparation method and application |
| CN112310357B (en) * | 2019-07-29 | 2022-02-11 | 宁德时代新能源科技股份有限公司 | Silicon-oxygen compound and secondary battery containing same |
| CN110844910B (en) * | 2019-11-19 | 2021-08-17 | 北京卫蓝新能源科技有限公司 | Preparation method of silicon-based negative electrode material of lithium ion battery |
| CN113644239B (en) * | 2020-04-27 | 2023-10-13 | 比亚迪股份有限公司 | Silica composite material and preparation method thereof |
| CN112635744B (en) * | 2021-03-09 | 2021-05-25 | 河南电池研究院有限公司 | Carbon-silicon-tin composite cathode material and preparation method thereof |
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