CN108807935B - Silicon-based tin-based composite particles for lithium ion battery, preparation method thereof, negative electrode comprising the same, and lithium ion battery - Google Patents
Silicon-based tin-based composite particles for lithium ion battery, preparation method thereof, negative electrode comprising the same, and lithium ion batteryDownload PDFInfo
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Abstract
Translated fromChinese
Description
The invention relates to a split application of an invention patent application with the application number of 2016110373036, the application date of 2016, 11 and 23, and the name of the invention is 'silicon-based tin composite particles for a lithium ion battery, a preparation method thereof, a negative electrode containing the silicon-based tin composite particles and the lithium ion battery'.
Technical Field
The disclosure relates to a silicon-based tin-based composite particle for a lithium ion battery, a preparation method thereof, a negative electrode containing the material and the lithium ion battery, and particularly relates to a hollow composite particle for the lithium ion battery, a preparation method thereof, a negative electrode containing the composite particle and the lithium ion battery.
Background
The working principle of the lithium ion battery is that lithium is transferred between the positive electrode and the negative electrode of the battery in the form of ions, so that the battery completes the charging and discharging processes, and therefore the lithium ion battery is also called as a rocking chair battery. The selection of the anode and cathode materials of a lithium ion battery has a crucial influence on the energy density and cycle life of the battery. At present, among various carbon materials, graphite-based carbon materials having a lamellar structure are most suitable as negative electrode materials for commercial lithium ion batteries. However, with the development of electric vehicles and large-scale energy storage, graphite materials have not been able to meet the development requirements of lithium ion batteries.
Silicon is the second most abundant element in the crust, making up 25.7% of the total crust mass, and the abundant reserves make its raw material sources sufficient. The theoretical specific capacity (4212mAh/g) of silicon is very high, and compared with the traditional graphite anode material, the silicon anode material has obvious specific capacity advantage. However, the silicon negative electrode has a problem in that, in the electrochemical lithium storage process, an average of 4.4 lithium atoms are bonded to each silicon atom to obtain Li22Si5Alloy phase, and the volume change of the material reaches more than 300 percent. The mechanical force generated by such a large volume effect gradually releases the electrode active material from the current collector, and the silicon active phase itself is pulverized, thereby losing electrical contact with the current collector, resulting in rapid degradation of electrode cycle performance. In addition, silicon itself is a semiconductor material, and the intrinsic conductivity is low and is only 6.7 × 10-4S/cm, a conductive agent is added to improve the electronic conductivity of the electrode.
The tin-based lithium storage material has the advantages of higher specific capacity, convenient preparation, low price and the like, and is stannous oxide (SnO) or stannic oxide (SnO)2) And the theoretical capacities of the simple substance tin are 875mAh/g, 782mAh/g and 990mAh/g respectively. The main problems of tin-based materials are: the material structure is unstable, the first cycle coulombic efficiency is low, and the cycle performance is poor when the material is used as a battery cathode material. The nanocrystallization of the material can relieve the problem, but the large specific surface area of the material enables the material to easily generate agglomeration in the preparation process.
There is still a need for a negative electrode material with high specific capacity and good cycling performance.
Disclosure of Invention
The disclosure provides a high-performance silicon-tin composite lithium ion battery cathode material, aiming at the problems of volume expansion, tin agglomeration, unstable electrode structure and poor cycle performance of the existing silicon-based and tin-based composite materials.
Specifically, the present disclosure provides a nanoscale silicon-coated tin hollow material. The material takes metal oxide as a template, tin-based material is coated on the metal oxide, and the tin-based nano hollow material is prepared by a template removing method. And then coating a silicon-based negative electrode material layer on the surface of the tin-based nano hollow material by using a chemical vapor deposition and liquid phase in-situ deposition method to form the silicon-tin composite nano hollow structure. The hollow structure can effectively accommodate the volume expansion of silicon-based and tin-based materials in the lithium intercalation process, thereby keeping the stability of the electrode structure. In addition, the external silicon-based material can effectively prevent the nano tin particles from agglomerating, and the stability of the tin-based material is kept, so that the lithium ion battery cathode composite material with high specific capacity and good cycle performance can be obtained.
According to one embodiment of the present disclosure, there is provided a silicon-based tin-based composite particle for a lithium ion battery, including:
hollow tin particles or hollow tin oxide particles, and
and a silicon layer coated on the outer surface of the hollow tin particles or the hollow tin oxide particles.
Preferably, the silicon-based tin-based composite particles have a particle size of 15nm to 250nm, and the hollow tin particles or hollow tin oxide particles have a hollow diameter of 5nm to 200 nm.
Preferably, the silicon-based tin-based composite particle may have a spherical shape, a polyhedral shape, or a rod shape, and when the silicon-based tin-based composite particle has a rod shape, the aspect ratio may be 2: 1 to 10: 1.
preferably, the thickness of the coated silicon layer is 10nm to 50nm, more preferably 10nm to 20 nm.
According to another technical scheme of the present disclosure, a preparation method of a silicon-based tin-based composite particle for a lithium ion battery is provided, which includes the following steps:
(1) preparing an oxide template by any one of a hydrolysis method, a sol-gel method and a decomposition method or directly using nanoparticles as the oxide template;
(2) coating the oxide template in the step (1) with a tin-based material by an in-situ deposition method:
(3) removing the template in the material obtained in the step (2) in alkali liquor, and performing an optional reduction process to obtain hollow tin oxide particles or hollow tin particles;
(4) and (3) coating a silicon layer on the surface of the hollow particles obtained in the step (3) by a chemical vapor deposition method or an in-situ deposition method to form the silicon-based tin-based hollow composite particles.
Preferably, the method comprises the steps of:
(1) preparation of a template
The oxide template is prepared by a hydrolysis method or any one of a sol-gel method and a decomposition method or nanoparticles are directly used as the oxide template.
The preparation process of the hydrolysis method comprises the following steps: mixing water, alcohol and alkali liquor according to the ratio of (5-40): (94-55): (1-5), adding a hydrolysis precursor, reacting at 5-50 ℃ for 10 min-3 h, centrifuging the obtained suspension, and washing with water to obtain the particle template.
The preparation process of the sol-gel method comprises the following steps: adding a salt solution containing metal ions into a certain amount of organic solvent to prepare a solution with the concentration of 1-3 mol/L, then dropwise adding a gelling agent and a surfactant at 60-80 ℃ to form gel, carrying out heat preservation aging on the gel for 2-24 h, and then carrying out heat treatment at 600-800 ℃ for 1-3 h to obtain a particle template;
the decomposition method comprises the following preparation processes: and carrying out heat treatment on the nanoscale metal salt at 600-800 ℃ for 1-3 h in an inert atmosphere to obtain the oxide template.
(2) Coated tin-based material
Coating the tin-based material on the oxide template in the step (1) by an in-situ deposition method, which comprises the following specific steps: dispersing the particle template obtained in the step (1) in 50-100 ml of deionized water, adding 50-100 ml of 0.5-2 mol/L stannate, reacting for 1-5 hours at the temperature of 60-80 ℃, and centrifugally washing the product to obtain the tin oxide coated particles.
(3) Removing the template
Preparing 0.5-3 mol/L alkali liquor, reacting the product obtained in the step (2) in the alkali liquor at 70-90 ℃ for 0.5-2 h, centrifugally washing to obtain hollow tin oxide particles, and reducing the hollow tin oxide particles into hollow tin particles by a magnesium thermal reaction or hydrogen reduction method when the hollow composite particles comprise the hollow tin particles.
(4) Silicon-coated layer
Coating silicon on the surfaces of the hollow particles obtained in the step (3) by a chemical vapor deposition method and an in-situ deposition method.
The chemical vapor deposition method comprises the following steps: and (3) taking 0.1-1 g of the hollow particles prepared in the step (3), and depositing silicon on the surfaces of the hollow particles by a silane gas cracking or silicon chloride hydrogenation method.
The in-situ deposition method of the silicon comprises the following steps: and (4) depositing silicon on the surface of the hollow particles prepared in the step (3) in a reaction kettle by a liquid-phase silicon chloride hydrogenation method.
The alcohol in the step (1) is methanol, ethanol, propanol, butanol or pentanol; the hydrolysis precursor is silicate ester, such as one or more of butyl silicate, methyl silicate, ethyl silicate and diethyl silicate. The alkali liquor is one or more of urea and ammonia water. The salt of the metal ion is nitrate or sulfate of Al, Mg, Ca, Ti, Mn, Fe, Co, Ni, Cu, Zn or ZrPhosphate, carbonate, silicate or chlorate. The organic solvent comprises one or more of ethylene glycol methyl ether and ethylene glycol ethyl ether. The surfactant comprises one or more of sodium dodecyl sulfate, stearic acid and lecithin. The gel comprises one or more of butyl titanate and ethyl silicate. The oxide template particles formed comprise aluminum oxide Al2O3Magnesium oxide MgO, calcium oxide CaO, titanium dioxide TiO2Manganese oxide MnO and manganese dioxide MnO2FeO, Fe ferrite, Fe ferroferric oxide3O4CoO, CoCo oxide, CoCo tetraoxide3O4NiO, CuO, and Cu2O, copper oxide CuO, zinc oxide ZnO and zirconium oxide ZrO2. Preferably, the synthesized oxide template has a particle size of between 5nm and 200 nm.
The stannate in the step (2) comprises sodium stannate, potassium stannate, magnesium stannate and calcium stannate. The tin oxide includes stannous oxide SnO and stannic oxide SnO2。
The alkali liquor adopted in the step (3) comprises potassium hydroxide and sodium hydroxide. Preferably, the hollow tin particles or hollow tin oxide particles are formed with a hollow diameter between 5nm and 200 nm.
The particle size of the hollow composite particles obtained in the step (4) is 15 nm-250 nm. Preferably, the thickness of the coated silicon layer is 10nm to 50nm, more preferably 10nm to 20 nm.
According to another technical scheme of the present disclosure, there is provided silicon-based tin-based composite particles prepared according to the preparation method.
According to another aspect of the present disclosure, there is provided a negative electrode for a lithium ion secondary battery, including the above silicon-based tin-based composite particle. Preferably, the negative electrode further comprises a conductive agent and a binder; the conductive agent is at least one or a mixture of carbon black, acetylene black, natural graphite, carbon nanotubes, graphene and carbon fibers; the binder is at least one or a mixture of polytetrafluoroethylene, polyvinylidene fluoride, polyurethane, polyacrylic acid, polyamide, polypropylene, polyvinyl ether, polyimide, styrene-butadiene copolymer and sodium carboxymethylcellulose; preferably, the proportions of the negative electrode active material, the conductive agent and the binder are as follows: the mass fraction of the negative electrode active material is 50-99.5 wt%, the mass fraction of the conductive agent is 0.1-40 wt%, and the mass fraction of the binder is 0.1-40 wt%.
According to another aspect of the present disclosure, there is provided a secondary battery including the above-described negative electrode; preferably, the secondary battery further includes a positive electrode, a separator, an electrolyte; wherein the positive electrode is a commonly used positive electrode for lithium batteries, and non-limiting examples of active materials contained therein include: lithium cobaltate, lithium manganate, lithium nickelate, lithium iron phosphate, lithium titanate, a nickel-cobalt-manganese ternary system, or a lithium composite metal oxide; the diaphragm comprises one of an aramid diaphragm, a non-woven fabric diaphragm, a polyethylene microporous film, a polypropylene-polyethylene double-layer or three-layer composite film and a ceramic coating diaphragm thereof; the electrolyte comprises an electrolyte and a solvent; the electrolyte is LiPF6、LiBF4、LiClO4、LiAsF6、LiCF3SO3、LiN(CF3SO2) At least one of LiBOB, LiCl, LiBr and LiI or a mixture thereof; the solvent comprises at least one or more of Propylene Carbonate (PC), dimethyl carbonate (DMC), Ethyl Methyl Carbonate (EMC), 1, 2-Dimethoxyethane (DME), ethylene carbonate, propylene carbonate, butylene carbonate, diethyl carbonate, methyl propyl carbonate, acetonitrile, ethyl acetate and ethylene sulfite.
In the present disclosure, unless otherwise limited, the stated range of values includes any subrange therein and can be considered to disclose any value therein.
In the present disclosure, the composite particle may be spherical, polyhedral, or rod-shaped, and when it is rod-shaped, its aspect ratio may be 2: 1 to 10: 1. in the present disclosure, the particle diameter of the composite particles, and the hollow diameter of the hollow tin particles or hollow tin oxide particles are measured or calculated by electron microscope analysis, nitrogen adsorption pore volume analysis, or laser particle size analysis.
The silicon-based tin-based composite particles prepared by the method are simple in preparation method and rich in material source. And due to the hollow structure, the particle can effectively accommodate the volume expansion of silicon-based and tin-based materials in the lithium intercalation process, thereby keeping the electrode structure stable. In addition, the external silicon-based material can effectively prevent the nano tin particles from agglomerating, and the stability of the tin-based material is kept, so that the lithium ion battery cathode composite material with high specific capacity and good cycle performance can be obtained.
Drawings
Fig. 1 is a schematic structural diagram of a silicon-based tin-based composite particle prepared according to the present disclosure.
Fig. 2 is a method for preparing spherical nanoparticles according to the present disclosure, in which a denotes a prepared template, b denotes a template coated with a tin-based material, c denotes a template-removed hollow tin-based material, and d denotes a template-removed hollow composite particle.
Fig. 3 is a schematic diagram of the change of the spherical hollow composite particle according to the present disclosure during lithium intercalation and lithium deintercalation, wherein the left side is an original state, the middle is a state after lithium intercalation, and the right side is a state after lithium deintercalation.
Fig. 4 and 5 are scanning electron microscope photographs of the hollow composite particles prepared in example 1 of the present disclosure.
Fig. 6 is a graph of cycle performance of the hollow composite particles prepared in example 1 of the present disclosure as an anode material, in which the circular dots represent the charge specific capacity, the square dots represent the discharge specific capacity, and the triangular dots represent the coulombic efficiency.
Fig. 7 is a transmission electron micrograph of hollow composite particles prepared according to example 2 of the present disclosure.
Fig. 8 is a graph of cycle performance of the hollow composite particles prepared in example 2 of the present disclosure as a negative electrode material, in which the solid dots represent specific discharge capacity and the hollow dots represent coulombic efficiency.
Fig. 9 is a transmission electron micrograph of hollow composite particles prepared according to example 3 of the present disclosure.
Fig. 10 is a graph of cycle performance of hollow composite particles prepared in example 3 of the present disclosure as an anode material, wherein upper data points represent coulombic efficiency and lower data points represent specific discharge capacity.
Fig. 11 is a transmission electron micrograph of hollow composite particles prepared according to example 4 of the present disclosure.
Fig. 12 is a graph of cycle performance of hollow composite particles prepared in example 4 of the present disclosure as an anode material, where triangular data points represent coulombic efficiency and circular data points represent specific discharge capacity.
Fig. 13 is a graph of cycling performance of solid silicon/tin dioxide composite particles prepared in comparative example 1 of the present disclosure as a negative electrode material, where the upper solid square data points represent coulombic efficiency and the lower round and open square data points represent specific charge and discharge capacities, respectively.
Fig. 14 is a graph of cycling performance of tin dioxide hollow spheres prepared in comparative example 2 of the present disclosure as a negative electrode material, wherein the circle and square data points represent the specific charge and discharge capacities, respectively.
Detailed Description
The present disclosure will be described in detail below by way of specific embodiments, but it should be noted that the following embodiments are only for understanding the present disclosure, and are not intended to limit the scope of the present disclosure.
Fig. 1 shows an exemplary particle structure of the present disclosure, which is spherical, polyhedral, and rod-shaped, respectively, from left to right, wherein the outer layer represents a silicon layer, the middle represents a tin-based material, and the inside is hollow.
Fig. 2 and 3 show the preparation method of the spherical hollow composite material, and the preparation method of the material with other shapes is similar to the spherical hollow composite material, and is not repeated here.
Fig. 4 is a schematic diagram of changes of the spherical hollow composite particles during lithium intercalation and lithium deintercalation according to the disclosure, where the left side is an original state, the middle is a state after lithium intercalation, and the right side is a state after lithium deintercalation, and changes of materials with other shapes during lithium intercalation and lithium deintercalation are similar, and are not repeated herein. As can be seen from fig. 4, the hollow composite particles of the present disclosure have a small volume change upon lithium intercalation and lithium deintercalation (i.e., charge and discharge processes).
The following examples illustrate the preparation of the composite material in detail, and those skilled in the art will be able to obtain the embodiments of the present disclosure based on the following preparation procedures.
Example 1
(1) 60ml of deionized water, 150ml of ethanol and 15ml of 25% aqueous ammonia were mixed in a beaker, 10ml of ethyl orthosilicate was added and stirred at room temperature for 50 min. Centrifuging and washing with deionized water to obtain the silica template with the particle size of 130 nm.
(2) 1g of the product of step (1) was added to 100ml of deionized water and ultrasonically dispersed for 30 min. 50ml of a 1mol/L sodium stannate solution was added, stirred and reacted at 70 ℃ for 2 hours. Centrifugation and washing with deionized water gave the product.
(3) Preparing 1.5mol/L potassium hydroxide solution, adding the product obtained in the step (2), stirring and reacting for 1h at 75 ℃. Centrifuging and washing with deionized water to obtain the tin dioxide hollow ball with the particle size of 150 nm.
(4) Step 0.5g of the product of step (3) was placed in a tube furnace and reacted by silane gas cracking under argon at 450 ℃ for 2h at a flow rate of 100 sccm. Obtaining the silicon/stannic oxide hollow spheres with the particle size of 170 nm.
Mixing the prepared active substance, conductive carbon black and polyacrylic acid serving as a binder according to a ratio of 85: 10: 5, preparing a negative electrode slurry by taking deionized water as a solvent, coating the negative electrode slurry on a copper foil to prepare a negative electrode sheet, and drying the negative electrode sheet at 60 ℃ in vacuum overnight. The electrochemical test is carried out by using a CR2025 type button cell, the counter electrode is an analytically pure metal lithium sheet, and the electrolyte is 1M LiPF6The volume ratio of Ethylene Carbonate (EC) to dimethyl carbonate (DMC) is 1: 1, and the battery diaphragm is Celgard-2320 (microporous polypropylene film). The assembly of the cell was performed in a glove box filled with argon, and as shown in fig. 6, the capacity of the material prepared by this method was stabilized at about 900mAh/g at a current density of 600mA/g after formation, and the capacity retention rate was about 81% at 100 cycles.
Example 2
(1) 100ml of 2mol/L ferric nitrate solution is prepared by taking ethylene glycol methyl ether as a solvent. 10ml of sodium dodecyl sulfate, butyl titanate and ethyl silicate are added with stirring and at 70 ℃. After a uniform, stable brown sol was formed, the sol was aged at 70 ℃ for 2h and dried at 90 ℃ under reduced pressure for 3 h. And taking out the product, and calcining the product for 3 hours in a muffle furnace at the temperature of 600 ℃ to obtain the nano blocky iron trioxide particles with the particle size of 50 nm.
(2) 2g of the product of step (1) was added to 100ml of deionized water and dispersed by sonication for 30 min. 30ml of a 1mol/L potassium stannate solution was added, stirred and reacted at 60 ℃ for 2 hours. Centrifugation and washing with deionized water gave the product.
(3) Preparing 1mol/L potassium hydroxide solution, adding the product obtained in the step (2), stirring and reacting for 2 hours at 80 ℃. Centrifuging and washing with deionized water to obtain the tin dioxide hollow particles with the particle size of 60 nm. Mixing the hollow particles with magnesium powder, placing the mixture in a tubular furnace, carrying out 700 ℃ reaction for 3h in an inert gas atmosphere, removing magnesium oxide by using acetic acid, centrifuging, and washing by using deionized water to obtain the tin hollow particles with the particle size of 60 nm.
(4) And (3) putting the product obtained in the step (1 g) in a reaction kettle, and depositing silicon on the surface of the tin dioxide hollow particles by using silicon tetrachloride as a silicon source through a catalytic hydrogenation method to form silicon/tin composite hollow particles with the particle size of 80 nm.
Mixing the prepared active substance, conductive carbon black and polyacrylic acid serving as a binder according to a ratio of 85: 10: 5, preparing a negative electrode slurry by taking deionized water as a solvent, coating the negative electrode slurry on a copper foil to prepare a negative electrode sheet, and drying the negative electrode sheet at 60 ℃ in vacuum overnight. The electrochemical test is carried out by using a CR2025 type button cell, the counter electrode is an analytically pure metal lithium sheet, and the electrolyte is 1M LiPF6The volume ratio of Ethylene Carbonate (EC) to dimethyl carbonate (DMC) is 1: 1, and the battery diaphragm is Celgard-2320 (microporous polypropylene film). The cell was assembled in a glove box filled with argon, and as shown in fig. 8, the capacity of the material prepared by this method was stabilized at about 1300mAh/g at a current density of 600mA/g after formation, and the capacity retention rate was about 83% at 100 cycles.
Example 3
(1) 100ml of zinc nitrate solution with the concentration of 2mol/L is prepared by using ethylene glycol methyl ether as a solvent. 20ml of sodium dodecyl sulfate, butyl titanate and ethyl silicate are added with stirring and at 80 ℃. After a uniform, stable brown sol was formed, the sol was aged at 80 degrees for 2h and dried at 90 degrees under reduced pressure for 3 h. And taking out the product, and calcining the product for 3 hours in a muffle furnace at the temperature of 600 ℃ to obtain the zinc oxide nano spherical particles with the particle size of 100 nm.
(2) 3g of the product of step (1) are added to 100ml of deionized water and dispersed ultrasonically for 30 min. 40ml of a 1mol/L sodium stannate solution was added, stirred and reacted at 60 ℃ for 0.5 h. Centrifugation and washing with deionized water gave the product.
(3) Preparing 2mol/L potassium hydroxide solution, adding the product obtained in the step (2), stirring and reacting for 2 hours at 80 ℃. Centrifuging and washing with deionized water to obtain stannous oxide hollow spheres with the particle size of 120 nm.
(4) And (3) putting 1g of the product obtained in the step (3) into a reaction kettle, taking silicon tetrachloride as a silicon source, and depositing silicon on the surfaces of the stannic oxide hollow particles by a catalytic hydrogenation method to form silicon/stannous oxide composite hollow spheres with the particle size of 150 nm.
Mixing the prepared active substance, conductive carbon black and polyacrylic acid serving as a binder according to a ratio of 85: 10: 5, preparing a negative electrode slurry by taking deionized water as a solvent, coating the negative electrode slurry on a copper foil to prepare a negative electrode sheet, and drying the negative electrode sheet at 60 ℃ in vacuum overnight. The electrochemical test is carried out by using a CR2025 type button cell, the counter electrode is an analytically pure metal lithium sheet, and the electrolyte is 1M LiPF6The volume ratio of Ethylene Carbonate (EC) to dimethyl carbonate (DMC) is 1: 1, and the battery diaphragm is Celgard-2320 (microporous polypropylene film). The assembly of the cell was performed in a glove box filled with argon, and as shown in fig. 10, the capacity of the material prepared by this method was stabilized at about 900mAh/g at a current density of 600mA/g after formation, and the capacity retention rate was about 90% at 100 cycles.
Example 4
(1) 3g of alumina particles with the particle size of 80nm are added into 100ml of deionized water, and ultrasonic dispersion is carried out for 30 min. 50ml of a 1mol/L potassium stannate solution was added, stirred and reacted at 70 ℃ for 2 hours. Centrifugation and washing with deionized water gave the product.
(2) Preparing 2mol/L potassium hydroxide solution, adding the product obtained in the step (1), stirring and reacting for 2 hours at 80 ℃. Centrifuging and washing with deionized water to obtain the tin dioxide hollow ball with the particle size of 100 nm.
(3) The product of step (2) was placed in a tube furnace and reacted by silane gas cracking at 450 ℃ for 1.5h under argon protection at a flow rate of 200 sccm. Obtaining the silicon/stannic oxide hollow spheres with the particle size of 140 nm.
Mixing the prepared active substance, conductive carbon black and polyacrylic acid serving as a binder according to a ratio of 85: 10: 5, preparing a negative electrode slurry by taking deionized water as a solvent, coating the negative electrode slurry on a copper foil to prepare a negative electrode sheet, and drying the negative electrode sheet at 60 ℃ in vacuum overnight. The electrochemical test is carried out by using a CR2025 type button cell, the counter electrode is an analytically pure metal lithium sheet, and the electrolyte is 1M LiPF6The volume ratio of Ethylene Carbonate (EC) to dimethyl carbonate (DMC) is 1: 1, and the battery diaphragm is Celgard-2320 (microporous polypropylene film). The assembly of the cell was performed in a glove box filled with argon, and as shown in fig. 12, the capacity of the material prepared by this method was stabilized at about 850mAh/g at a current density of 600mA/g after formation, and the capacity retention rate was about 77% at 100 cycles.
Comparative example 1
Solid silicon/tin dioxide particles were obtained in the same manner as in example 1 except that steps (1) and (3) were not performed, and batteries were manufactured and tested for electrochemical properties according to the same method as in example 1 for manufacturing batteries, and the results are shown in fig. 13. As can be seen from fig. 13, due to the lack of space to accommodate expansion, material fracture, and poor cycle performance, the specific capacity of the battery decreased from about 600mAh/g to about 100mAh/g after 100 cycles at a current density of 600mA/g, and the capacity retention rate at 100 cycles was only about 16.7%.
Comparative example 2
Hollow tin dioxide particles were obtained in the same manner as in example 1 except that the step (4) was not performed, and batteries were manufactured and tested for electrochemical properties in the same manner as in example 1, and the results are shown in fig. 14. As can be seen from fig. 14, since tin agglomerated during the cycling process, and lost the hollow structure, the cycling performance of the battery at a current density of 600mA/g dropped from about 800mAh/g to about 400mAh/g, and the capacity retention at 100 cycles was only about 50%.
As can be seen from fig. 6-14, the initial specific capacity, the specific capacity after 100 cycles, and the capacity retention rate after 100 cycles of the hollow composite particles provided according to the present disclosure are all much higher than the corresponding values in the comparative examples.
According to the experimental results, the hollow composite particles provided by the disclosure can effectively accommodate the volume expansion of silicon-based and tin-based materials in the lithium intercalation process, so that the stability of the electrode structure is maintained, and the lithium ion battery cathode composite material with high specific capacity and good cycle performance is obtained.
Claims (10)
1. A preparation method of silicon-based tin-based composite particles for lithium ion batteries comprises the following steps:
(a1) mixing 60ml deionized water, 150ml ethanol and 15ml 25% ammonia water in a beaker, adding 10ml ethyl orthosilicate and stirring for 50min at room temperature, centrifuging and washing with deionized water to obtain a silica template with the particle size of 130nm,
(a2) adding 1g of the product obtained in the step (a1) into 100ml of deionized water, performing ultrasonic dispersion for 30min, adding 50ml of 1mol/L sodium stannate solution, stirring and reacting at 70 ℃ for 2h, centrifuging and washing with deionized water to obtain a product,
(a3) preparing 1.5mol/L potassium hydroxide solution, adding the product obtained in the step (a2), stirring and reacting for 1h at 75 ℃, centrifuging and washing with deionized water to obtain tin dioxide hollow spheres with the particle size of 150nm,
(a4) placing 0.5g of the product of the step (a3) into a tube furnace, and reacting for 2h at 450 ℃ by a silane gas cracking method under the protection of argon at a flow rate of 100sccm to obtain silicon/tin dioxide hollow spheres with the particle size of 170nm, or
(b1) Preparing 100ml of 2mol/L ferric nitrate solution by taking ethylene glycol monomethyl ether as a solvent, stirring, respectively adding 10ml of sodium dodecyl sulfate, butyl titanate and ethyl silicate at 70 ℃ to form uniform and stable brown sol, aging the sol for 2h at 70 ℃, drying under reduced pressure for 3h at 90 ℃, taking out a product, calcining for 3h at 600 ℃ in a muffle furnace to obtain nano blocky ferric oxide particles with the particle size of 50nm,
(b2) adding 2g of the product obtained in the step (b1) into 100ml of deionized water, performing ultrasonic dispersion for 30min, adding 30ml of 1mol/L potassium stannate solution, stirring and reacting at 60 ℃ for 2h, centrifuging and washing with deionized water to obtain a product,
(b3) preparing 1mol/L potassium hydroxide solution, adding the product obtained in the step (b2), stirring and reacting for 2h at 80 ℃, centrifuging and washing with deionized water to obtain tin dioxide hollow particles with the particle size of 60nm, mixing the hollow particles with magnesium powder, placing in a tubular furnace, reacting for 3h at 700 ℃ in an inert gas atmosphere, removing magnesium oxide with acetic acid, centrifuging and washing with deionized water to obtain tin hollow particles with the particle size of 60nm,
(b4) putting 1g of the product obtained in the step (b3) into a reaction kettle, taking silicon tetrachloride as a silicon source, depositing silicon on the surfaces of the tin dioxide hollow particles by a catalytic hydrogenation method to form silicon/tin composite hollow particles with the particle size of 80nm, or
(c1) Preparing 100ml of 2mol/L zinc nitrate solution by taking ethylene glycol monomethyl ether as a solvent, stirring, respectively adding 20ml of sodium dodecyl sulfate, butyl titanate and ethyl silicate at 80 ℃ to form uniform and stable brown sol, aging the sol for 2h at 80 ℃, drying under reduced pressure for 3h at 90 ℃, taking out a product, calcining for 3h at 600 ℃ in a muffle furnace to obtain zinc oxide nano spherical particles with the particle size of 100nm,
(c2) adding 3g of the product obtained in the step (c1) into 100ml of deionized water, performing ultrasonic dispersion for 30min, adding 40ml of 1mol/L sodium stannate solution, stirring and reacting at 60 ℃ for 0.5h, centrifuging and washing with deionized water to obtain a product,
(c3) preparing 2mol/L potassium hydroxide solution, adding the product obtained in the step (c2), stirring and reacting for 2h at 80 ℃, centrifuging and washing with deionized water to obtain stannous oxide hollow spheres with the particle size of 120nm,
(c4) putting 1g of the product obtained in the step (c3) into a reaction kettle, taking silicon tetrachloride as a silicon source, depositing silicon on the surfaces of the stannic oxide hollow particles by a catalytic hydrogenation method to form silicon/stannous oxide composite hollow spheres with the particle size of 150nm, or
(d1) Adding 3g of alumina particles with the particle size of 80nm into 100ml of deionized water, performing ultrasonic dispersion for 30min, adding 50ml of 1mol/L potassium stannate solution, stirring, reacting at 70 ℃ for 2h, centrifuging, washing with deionized water to obtain a product,
(d2) preparing 2mol/L potassium hydroxide solution, adding the product obtained in the step (d1), stirring and reacting for 2h at 80 ℃, centrifuging and washing with deionized water to obtain tin dioxide hollow spheres with the particle size of 100nm,
(d3) and (d2) putting the product of the step (d2) into a tubular furnace, and reacting for 1.5h at 450 ℃ by a silane gas cracking method under the protection of argon at the flow rate of 200sccm to obtain the silicon/tin dioxide hollow spheres with the particle size of 140 nm.
2. A silicon-based tin-based composite particle for a lithium ion battery, the silicon-based tin-based composite particle comprising:
hollow tin particles or hollow tin oxide particles, and
a silicon layer coated on the outer surface of the hollow tin particles or hollow tin oxide particles,
wherein the silicon-based tin-based composite particles are prepared using the method of claim 1.
3. The silicon-based tin-based composite particle of claim 2,
the silicon-based tin-based composite particles have a particle size of 15nm to 250nm, and the hollow tin particles or hollow tin oxide particles have a cavity size of 5nm to 200 nm.
4. The silicon-based tin-based composite particle of claim 2,
the silicon-based tin-based composite particles are spherical, polyhedral or rod-shaped, and when the silicon-based tin-based composite particles are rod-shaped, the length-diameter ratio is 2: 1 to 10: 1.
5. the silicon-based tin-based composite particle of claim 2,
the thickness of the clad silicon layer is 10nm to 50 nm.
6. A negative electrode for a lithium ion battery comprising the silicon-based tin-based composite particles according to any one of claims 2 to 5.
7. The anode for a lithium ion battery according to claim 6, further comprising a conductive agent and a binder; wherein the conductive agent is one or a mixture of carbon black, natural graphite, carbon nanotubes, graphene and carbon fibers; the binder is one or a mixture of polytetrafluoroethylene, polyvinylidene fluoride, polyurethane, polyacrylic acid, polyamide, polypropylene, polyvinyl ether, polyimide, styrene-butadiene copolymer and sodium carboxymethylcellulose.
8. The negative electrode for a lithium ion battery according to claim 7,
the carbon black is acetylene black.
9. The negative electrode for a lithium ion battery according to claim 7 or 8, wherein the proportions of the negative electrode active material, the conductive agent, and the binder are: the mass fraction of the negative electrode active material is 50-99.5 wt%, the mass fraction of the conductive agent is 0.1-40 wt%, and the mass fraction of the binder is 0.1-40 wt%.
10. A lithium ion battery comprising the anode of any one of claims 7-9.
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