WO2018094783A1 - 锂离子电池用硅基锡基复合颗粒、其制备方法、包含其的负极和锂离子电池 - Google Patents

锂离子电池用硅基锡基复合颗粒、其制备方法、包含其的负极和锂离子电池 Download PDF

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WO2018094783A1
WO2018094783A1 PCT/CN2016/109594 CN2016109594W WO2018094783A1 WO 2018094783 A1 WO2018094783 A1 WO 2018094783A1 CN 2016109594 W CN2016109594 W CN 2016109594W WO 2018094783 A1 WO2018094783 A1 WO 2018094783A1
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tin
silicon
oxide
particles
hollow
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French (fr)
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邱新平
马天翼
余向南
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Tsinghua University
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/386—Silicon or alloys based on silicon
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/387—Tin or alloys based on tin
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present disclosure relates to a silicon-based tin-based composite particle for a lithium ion battery, a preparation method thereof, a negative electrode including the material, and a lithium ion battery, and more particularly, the present invention relates to a hollow composite particle for a lithium ion battery, and a preparation method thereof A negative electrode and a lithium ion battery comprising the composite particles.
  • the working principle of lithium-ion battery is that lithium is transferred between the positive and negative electrodes of the battery in the form of ions, so that the battery completes the process of charging and discharging. Therefore, the lithium ion battery is also called "rocking chair battery".
  • the choice of cathode material for lithium ion batteries has a crucial impact on the energy density and cycle life of the battery.
  • a graphite-based carbon material having a lamellar structure is most suitable as a commercial lithium ion battery negative electrode material.
  • graphite materials can no longer meet the needs of the development of lithium-ion batteries.
  • Silicon is the second most abundant element in the earth's crust, which constitutes 25.7% of the total mass of the earth's crust. Its abundant reserves make it a source of sufficient raw materials.
  • the theoretical specific capacity of silicon (4212 mAh/g) is very high, and the silicon negative electrode material has a significant specific capacity advantage compared to the conventional graphite negative electrode material.
  • the problem with the silicon negative electrode is that in the electrochemical lithium storage process, an average of 4.4 lithium atoms per silicon atom is obtained to obtain a Li 22 Si 5 alloy phase, and the volume change of the material reaches 300% or more.
  • the mechanical force generated by such a large volume effect causes the electrode active material to gradually disengage from the current collector, and the silicon active phase itself also pulverizes, thereby losing electrical contact with the current collector, resulting in a rapid decline in electrode cycle performance.
  • silicon itself is a semiconductor material, and the intrinsic conductivity is low, only 6.7 ⁇ 10 -4 S / cm, and a conductive agent is added to increase the electronic conductance of the electrode.
  • Tin-based lithium storage materials have the advantages of higher specific capacity, convenient preparation, and lower price.
  • the theoretical capacities of stannous oxide (SnO), tin oxide (SnO 2 ) and tin are 875mAh/g and 782mAh/g and 990mAh/ respectively.
  • the main problem of tin-based materials is that the material structure is unstable, and the first cycle of coulombic efficiency is so low that the cycle performance is poor when used as a battery anode material.
  • the nanocrystallization of the material can alleviate the problem, but its large specific surface area makes the material prone to agglomeration during the preparation process.
  • the present disclosure provides a high-performance silicon-silicon composite lithium ion battery anode material.
  • the present disclosure provides a nanoscale silicon coated tin hollow material.
  • the material is coated with a tin-based material by using a metal oxide as a template, and a tin-based nano hollow material is prepared by a template removal method.
  • the surface of the tin-based nano-hollow material is coated with a silicon-based anode material layer by chemical vapor deposition and liquid phase in-situ deposition to form a silicon-tin composite nano-hollow structure.
  • the hollow structure can effectively accommodate the volume expansion of the silicon-based and tin-based materials during the lithium intercalation process, thereby maintaining the stability of the electrode structure.
  • the external silicon-based material can effectively prevent the agglomeration of the nano tin particles, and maintain the stability of the tin-based material, thereby obtaining a lithium ion battery negative electrode composite material with high specific capacity and good cycle performance.
  • a silicon-based tin-based composite particle for a lithium ion battery comprising:
  • the silicon-based tin-based composite particles have a particle diameter of between 15 nm and 250 nm, and the hollow tin particles or the hollow tin oxide particles have a hollow diameter of between 5 nm and 200 nm.
  • the silicon-based tin-based composite particles may be spherical, polyhedral, or rod-shaped, and when they are rod-shaped, the aspect ratio may be from 2:1 to 10:1.
  • the thickness of the coated silicon layer is from 10 nm to 50 nm, more preferably from 10 nm to 20 nm.
  • a method for preparing a silicon-based tin-based composite particle for a lithium ion battery includes the following steps:
  • the surface of the hollow particles obtained in the step (3) is coated with a silicon layer by a chemical vapor deposition method or an in-situ deposition method to form the silicon-based tin-based hollow composite particles.
  • the method comprises the steps of:
  • the oxide template is prepared by any one of a hydrolysis method or a sol-gel method and a decomposition method or directly using the nanoparticles as an oxide template.
  • the preparation process of the hydrolysis method is: mixing water, alcohol and alkali solution according to the volume ratio of (5-40): (94-55): (1 ⁇ 5), adding the hydrolysis precursor, and reacting at 5-50 ° C for 10 min to 3 h. Thereafter, the obtained suspension was separated by centrifugation, and after washing with water, a particle template was obtained.
  • the preparation process of the sol-gel method is: adding a metal ion-containing salt solution to a certain amount of an organic solvent to prepare a solution having a concentration of 1 to 3 mol/L, and then adding a gelling agent and surface activity at 60 to 80 degrees.
  • the agent forms a gel, and the gel is aged for 2 to 24 hours, and then heat treated at 600 to 800 degrees for 1 to 3 hours to obtain a particle template;
  • the preparation process of the decomposition method is: heat treatment of the nano-scale metal salt at 600 to 800 degrees for 1 to 3 hours in an inert atmosphere to obtain an oxide template.
  • the oxide template in the step (1) is coated with a tin-based material by an in-situ deposition method.
  • the specific steps are as follows: the particle template obtained in the step (1) is dispersed in 50-100 ml of deionized water, and 0.5-100 ml of 0.5 to 50 is added. 2 mol/L of stannate is reacted in a temperature range of 60 to 80 degrees for 1-5 hours, and the product is washed with water to obtain tin oxide-coated particles.
  • Silicon is coated on the surface of the hollow particles obtained in the step (3) by chemical vapor deposition and in situ deposition.
  • the chemical vapor deposition method comprises the steps of: taking 0.1 to 1 g of the hollow particles prepared in the step (3), and depositing silicon on the surface thereof by a silane gas cracking or a silicon chloride hydrogenation method.
  • the in-situ deposition step of silicon is: depositing silicon on the surface of the hollow particles prepared in the step (3) by hydrogenating the liquid phase silicon chloride in the reaction vessel.
  • the alcohol in the step (1) is methanol, ethanol, propanol, butanol or pentanol;
  • the hydrolysis precursor is a silicate such as butyl silicate, methyl silicate, ethyl silicate or silicate.
  • the lye is one or more of urea and ammonia.
  • the salt of the metal ion is a nitrate, a sulfate, a phosphate, a carbonate, a silicate or a chlorate of Al, Mg, Ca, Ti, Mn, Fe, Co, Ni, Cu, Zn or Zr.
  • the organic solvent contains one or more of ethylene glycol methyl ether and ethylene glycol diethyl ether.
  • the surfactant includes one or more of sodium dodecyl sulfate, stearic acid, and lecithin.
  • the gelling agent comprises one or more of butyl titanate and ethyl silicate.
  • the oxide template particles formed include alumina Al 2 O 3 , magnesium oxide MgO, calcium oxide CaO, titanium dioxide TiO 2 , manganese oxide MnO and manganese dioxide MnO 2 , ferrous oxide FeO, ferroferric oxide Fe 3 O 4 Cobalt oxide CoO, cobalt trioxide Co 3 O 4 , nickel oxide NiO, cuprous oxide Cu 2 O, copper oxide CuO, zinc oxide ZnO and zirconium oxide ZrO 2 .
  • the synthesized oxide template has a particle size between 5 nm and 200 nm.
  • the stannate of the step (2) includes sodium stannate, potassium stannate, magnesium stannate, and calcium stannate.
  • the tin oxide includes stannous oxide SnO and tin dioxide SnO 2 .
  • the lye used in the step (3) includes potassium hydroxide and sodium hydroxide.
  • the formed hollow tin particles or hollow tin oxide particles have a hollow diameter of between 5 nm and 200 nm.
  • the hollow composite particles obtained in the step (4) have a particle diameter of from 15 nm to 250 nm.
  • the thickness of the coated silicon layer is from 10 nm to 50 nm, more preferably from 10 nm to 20 nm.
  • a silicon-based tin-based composite particle prepared according to the preparation method.
  • a negative electrode for a lithium ion secondary battery comprising the above-described silicon-based tin-based composite particles.
  • the negative electrode further includes a conductive agent, a binder; wherein the conductive agent is at least one or a mixture of carbon black, acetylene black, natural graphite, carbon nanotubes, graphene, carbon fibers;
  • the bonding agent is polytetrafluoroethylene, polyvinylidene fluoride, polyurethane, polyacrylic acid, polyamide, polypropylene, polyvinyl ether, polyimide, styrene-butadiene copolymer, sodium carboxymethyl cellulose
  • the ratio of the anode active material, the conductive agent, and the binder is: the mass fraction of the anode active material is 50 to 99.5 wt%, the conductive agent is 0.1 to 40 wt%, and the binder is 0.1 to
  • a secondary battery including the above negative electrode; preferably, the secondary battery further includes a positive electrode, a separator, and an electrolyte; wherein the positive electrode is a commonly used lithium
  • the active material contained in the battery positive electrode include: lithium cobaltate, lithium manganate, lithium nickelate, lithium iron phosphate, lithium titanate, nickel-cobalt-manganese ternary system, or composite metal oxidation of lithium
  • the separator includes one of an aramid membrane, a non-woven membrane, a polyethylene microporous membrane, a polypropylene membrane, a polypropylene polyethylene double layer or a three-layer composite membrane, and a ceramic coating layer separator;
  • the electrolyte comprises an electrolyte and a solvent; the electrolyte is at least one or a mixture of LiPF 6 , LiBF 4 , LiClO 4 , LiAsF 6 , LiCF 3 SO 3 , LiN(CF 3 SO 2
  • the composite particles may be spherical, polyhedral granular, or rod-shaped, and when they are rod-shaped, the aspect ratio may be from 2:1 to 10:1.
  • the particle diameter of the composite particles, and the hollow diameter of the oxide particles of the hollow tin particles or hollow tin are measured or calculated by electron microscopic analysis, nitrogen adsorption pore volume analysis or laser particle size analysis. of.
  • the silicon-based tin-based composite particles prepared by the present disclosure are simple in preparation method and rich in material sources. Moreover, due to the hollow structure, the particles can effectively accommodate the volume expansion of the silicon-based and tin-based materials during the lithium intercalation process, thereby maintaining the stability of the electrode structure. Moreover, the external silicon-based material can effectively prevent the agglomeration of the nano tin particles, and maintain the stability of the tin-based material, thereby obtaining a lithium ion battery negative electrode composite material with high specific capacity and good cycle performance.
  • FIG. 1 is a schematic view showing the structure of a silicon-based tin-based composite particle prepared according to the present disclosure.
  • a represents a prepared template
  • b represents a template coated with a tin-based material
  • c represents a hollow tin-based material from which a template is removed
  • d represents a hollow composite particle from which a template is removed.
  • FIG 3 is a schematic view showing changes in lithium insertion and delithiation of the spherical hollow composite particles of the present disclosure, wherein the left side is in an original state, the middle is in a state after lithium insertion, and the right side is in a state after delithiation.
  • Fig. 6 is a graph showing the cycle performance of the hollow composite particles prepared in Example 1 of the present disclosure as a negative electrode material, wherein a circular dot indicates a charge specific capacity, a square dot indicates a discharge specific capacity, and a triangular dot indicates a coulombic efficiency.
  • Figure 7 is a transmission electron micrograph of hollow composite particles prepared in Example 2 of the present disclosure.
  • Fig. 8 is a graph showing the cycle performance of the hollow composite particles prepared in Example 2 of the present disclosure as a negative electrode material, wherein solid dots indicate discharge specific capacity, and hollow dots indicate coulombic efficiency.
  • Figure 9 is a transmission electron micrograph of hollow composite particles prepared in Example 3 of the present disclosure.
  • Figure 10 is a graph showing the cycle performance of the hollow composite particles prepared in Example 3 of the present disclosure as a negative electrode material, wherein the upper data points represent coulombic efficiencies and the lower data points represent discharge specific capacities.
  • Figure 11 is a transmission electron micrograph of a hollow composite particle prepared in Example 4 of the present disclosure.
  • Figure 12 is a graph showing the cycle performance of the hollow composite particles prepared in Example 4 of the present disclosure as a negative electrode material, wherein the data points of the triangles represent the coulombic efficiency, and the data points of the circle represent the discharge specific capacity.
  • FIG. 13 is a cycle performance diagram of a solid silicon/tin dioxide composite particle prepared in Comparative Example 1 of the present disclosure as a negative electrode material, wherein the solid square data points above represent Coulomb efficiency, and the data points of the lower circular and open squares respectively Indicates the charge and discharge specific capacity.
  • Figure 14 is a graph showing the cycle performance of the tin dioxide hollow sphere prepared in Comparative Example 2 of the present disclosure as a negative electrode material, wherein the circular and square data points represent the charge and discharge specific capacity, respectively.
  • FIG. 1 shows an exemplary particle structure of the present disclosure, which is spherical, polyhedral, and rod-shaped from left to right, wherein the outer layer represents a silicon layer, the middle represents a tin-based material, and the interior is hollow.
  • FIG. 2 and FIG. 3 show the preparation method of the spherical hollow composite material as an example, and the preparation methods of the materials of other shapes are similar, and will not be described herein.
  • FIG. 4 is a schematic view showing changes in lithium insertion and delithiation of the spherical hollow composite particles of the present disclosure, wherein the left side is in an original state, the middle is in a state after lithium insertion, and the right side is in a state after delithiation, and materials of other shapes are The changes in lithium insertion and delithiation are similar, and will not be described here.
  • the hollow composite particles of the present disclosure have a small volume change during lithium insertion and delithiation (ie, charge and discharge processes).
  • step (g) of the step 0.5g was placed in a tube furnace, and subjected to a silane gas cracking method at a flow rate of 100 sccm at 450 °C for 2 hours under argon gas protection.
  • a silicon/tin dioxide hollow sphere having a particle diameter of 170 nm was obtained.
  • the prepared active material, conductive carbon black and binder polyacrylic acid are uniformly mixed at a mass ratio of 85:10:5, and a negative electrode slurry is prepared by using deionized water as a solvent, and is coated on a copper foil to form a negative electrode. Tablets were dried overnight at 60 ° C under vacuum.
  • the electrochemical test was carried out using a CR2025 coin cell battery, the counter electrode was an analytically pure lithium metal plate, and the electrolyte was 1M LiPF 6 ethylene carbonate (EC) / dimethyl carbonate (DMC) (1:1 by volume) solution.
  • the battery separator is Celgard-2320 (microporous polypropylene film).
  • the assembly of the battery was carried out in an argon-filled glove box. As shown in Fig. 6, the material prepared by this method was stabilized at a current density of 600 mA/g and the capacity was stabilized at about 900 mAh/g, and the capacity retention rate was 100 cycles. About 81%.
  • step (2) 2 g of the product of step (1) was added to 100 ml of deionized water and ultrasonically dispersed for 30 min. 30 ml of a 1 mol/L potassium stannate solution was added, stirred, and reacted at 60 degrees for 2 hours. Centrifugation and washing with deionized water gave the product.
  • step (g) of step 1g is placed in a reaction vessel, and silicon tetrachloride is used as a silicon source to deposit silicon on the surface of the hollow particles of tin dioxide by catalytic hydrogenation to form silicon having a particle diameter of 80 nm. / tin composite hollow particles.
  • the prepared active material, conductive carbon black and binder polyacrylic acid are uniformly mixed at a mass ratio of 85:10:5, and a negative electrode slurry is prepared by using deionized water as a solvent, and is coated on a copper foil to form a negative electrode. Tablets were dried overnight at 60 ° C under vacuum.
  • the electrochemical test was carried out using a CR2025 coin cell battery, the counter electrode was an analytically pure lithium metal plate, and the electrolyte was 1M LiPF 6 ethylene carbonate (EC) / dimethyl carbonate (DMC) (1:1 by volume) solution.
  • the battery separator is Celgard-2320 (microporous polypropylene film).
  • the assembly of the battery was carried out in an argon-filled glove box. As shown in Fig. 8, the material prepared by this method was stabilized at a current density of 600 mA/g and the capacity was stabilized at about 1300 mAh/g, and the capacity retention rate at 100 cycles was obtained. About 83%.
  • step (3) 1 g of the product of step (3) is placed in a reaction vessel, and silicon tetrachloride is used as a silicon source to deposit silicon on the surface of the hollow particles of tin dioxide by catalytic hydrogenation to form silicon having a particle diameter of 150 nm/ Stannous oxide composite hollow sphere.
  • the prepared active material, conductive carbon black and binder polyacrylic acid are uniformly mixed at a mass ratio of 85:10:5, and a negative electrode slurry is prepared by using deionized water as a solvent, and is coated on a copper foil to form a negative electrode. Tablets were dried overnight at 60 ° C under vacuum.
  • the electrochemical test was carried out using a CR2025 coin cell battery, the counter electrode was an analytically pure lithium metal plate, and the electrolyte was 1M LiPF 6 ethylene carbonate (EC) / dimethyl carbonate (DMC) (1:1 by volume) solution.
  • the battery separator is Celgard-2320 (microporous polypropylene film).
  • the assembly of the battery was carried out in an argon-filled glove box, as shown in Fig. 10, the material prepared by this method was stabilized at a current density of 600 mA/g and the capacity was stabilized at about 900 mAh/g, and the capacity retention rate at 100 cycles was obtained. About 90%.
  • step (3) The product of the step (3) was placed in a tube furnace and reacted at 450 ° C for 1.5 h at a flow rate of 200 sccm under argon gas protection. A silicon/tin dioxide hollow sphere having a particle diameter of 140 nm was obtained.
  • the prepared active material, conductive carbon black and binder polyacrylic acid are uniformly mixed at a mass ratio of 85:10:5, and a negative electrode slurry is prepared by using deionized water as a solvent, and is coated on a copper foil to form a negative electrode. Tablets were dried overnight at 60 ° C under vacuum.
  • the electrochemical test was carried out using a CR2025 coin cell battery, the counter electrode was an analytically pure lithium metal plate, and the electrolyte was 1M LiPF 6 ethylene carbonate (EC) / dimethyl carbonate (DMC) (1:1 by volume) solution.
  • the battery separator is Celgard-2320 (microporous polypropylene film).
  • the assembly of the battery was carried out in an argon-filled glove box. As shown in Fig. 12, the material prepared by this method was stabilized at a current density of 600 mA/g at a capacity of about 850 mAh/g, and the capacity retention rate at 100 cycles was obtained. About 77%.
  • Solid silicon/tin dioxide particles were obtained in the same manner as in Example 1 except that steps (1) and (3) were not carried out, and a battery was prepared and tested according to the same method as in Example 1 for preparing a battery. Electrochemical performance, the results are shown in Figure 13. As can be seen from Fig. 13, due to the lack of space for accommodating expansion, the material is broken and the cycle performance is poor. After 100 cycles at a current density of 600 mA/g, the specific capacity of the battery drops from about 600 mAh/g to about 100 mAh/g, 100. The capacity retention rate under the secondary cycle was only about 16.7%.
  • a hollow tin dioxide particle was obtained by the same method as in Example 1 except that the step (4) was not carried out, and a battery was prepared and tested for electrochemical performance according to the same procedure as in Example 1.
  • the result was as follows.
  • Figure 14 shows. As can be seen from Fig. 14, since the tin agglomerates during the cycle and loses the hollow structure, the cycle performance of the battery at a current density of 600 mA/g drops from about 800 mAh/g to about 400 mAh/g, under 100 cycles. The capacity retention rate is only about 50%.
  • the initial specific capacity of the hollow composite particles provided according to the present disclosure is significantly higher than the corresponding values in the comparative examples.
  • the hollow composite particles provided by the present disclosure can effectively accommodate the volume expansion of the silicon-based and tin-based materials during the lithium intercalation process, thereby maintaining the stability of the electrode structure and obtaining high specific capacity and cycle performance.

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Abstract

一种锂离子电池用硅基锡基复合颗粒、其制备方法、包含其的负极和锂离子电池。所述硅基锡基复合颗粒包括：中空的锡颗粒或中空的锡的氧化物颗粒，以及在中空的锡颗粒或中空的锡的氧化物颗粒的外表面包覆的硅层。还提供了包含所述复合颗粒的用于锂离子二次电池的负极和包含该负极的锂离子二次电池。该复合颗粒的制备方法简单，由于其中空结构，该颗粒能够有效的容纳硅基和锡基材料在嵌锂过程中的体积膨胀，从而保持电极结构的稳定。而且，外部硅基材料能够有效阻止纳米锡颗粒的团聚，保持锡基材料的稳定，从而可以获得比容量高，循环性能好的锂离子电池负极复合材料。

Description

锂离子电池用硅基锡基复合颗粒、其制备方法、包含其的负极和锂离子电池 技术领域
本公开涉及一种锂离子电池用硅基锡基复合颗粒，其制备方法，包含该材料的负极和锂离子电池，具体而言，本公开涉及一种锂离子电池用中空复合颗粒，其制备方法，包含该复合颗粒的负极和锂离子电池。
背景技术
锂离子电池的工作原理是锂以离子的形式在电池正负极之间转移，使电池完成充放电的过程，因此锂离子电池又被称为“摇椅电池”。锂离子电池正极负极材料的选择对于电池的能量密度和循环寿命有着至关重要的影响。目前，在各种碳材料中，具有片层状结构的石墨类碳材料是最适宜作为商业化的锂离子电池负极材料。但随着电动汽车和大规模储能的发展，石墨材料已经不能满足锂离子电池发展的需要。
硅是地壳中第二丰富的元素，构成地壳总质量的25.7％，丰富的储量使其原料来源充足。硅的理论比容量(4212mAh/g)很高，相比传统的石墨负极材料，硅负极材料具有明显的比容量优势。但硅负极的问题在于，在电化学储锂过程中，平均每个硅原子结合4.4个锂原子得到Li22Si5合金相，同时材料的体积变化达到300％以上。如此巨大的体积效应产生的机械作用力会使电极活性物质与集流体之间逐渐脱开，并且硅活性相自身也会粉化，从而丧失与集流体的电接触，造成电极循环性能迅速下降。另外，硅本身是半导体材料，本征电导率低，仅有6.7×10-4S/cm，需加入导电剂以提高电极的电子电导。
锡基储锂材料具有比容量较高、制备方便、价格便宜等优点，氧化亚锡(SnO)、氧化锡(SnO2)以及锡单质的理论容量分别为875mAh/g和782mAh/g和990mAh/g。锡基材料的主要问题为：材料结构不稳定，首次循环库仑效率低，以至于在用作电池负极材料时循环性能较差。材料的纳米化可使问题有所缓解，但其较大的比表面积使得材料在制备过程中容易产生团聚。
仍然需要一种具有高比容量、循环性能良好的负极材料。
发明内容
针对现有硅基、锡基复合材料的体积膨胀、锡团聚、电极结构不稳定以及循环性能差的问题，本公开提供了一种高性能硅锡复合锂离子电池负极材料。
具体而言，本公开提供了一种纳米级硅包覆锡的中空材料。所述材料以金属氧化物作为模板，在其上包覆锡基材料，并通过去模板法制备锡基纳米中空材料。再通过化学气相沉积、液相原位沉积的方法在锡基纳米中空材料表面包覆硅基负极材料层，形成硅锡复合纳米中空结构。所述中空结构能够有效的容纳硅基和锡基材料在嵌锂过程中的体积膨胀，从而保持电极结构的稳定。而且，外部硅基材料能够有效阻止纳米锡颗粒的团聚，保持锡基材料的稳定，从而可以获得比容量高，循环性能好的锂离子电池负极复合材料。
根据本公开的一个技术方案，其提供了一种锂离子电池用硅基锡基复合颗粒，其包括：
中空的锡颗粒或中空的锡的氧化物颗粒，以及
在中空的锡颗粒或中空的锡的氧化物颗粒的外表面包覆的硅层。
优选地，所述硅基锡基复合颗粒的粒径在15nm至250nm之间，所述中空的锡颗粒或中空的锡的氧化物颗粒的中空直径在5nm-200nm之间。
优选地，所述硅基锡基复合颗粒可以是球形，多面体形，或棒状，其为棒状时，长径比可以为2：1至10：1。
优选地，所述包覆的硅层的厚度是10nm至50nm，更优选10nm至20nm。
根据本公开的另一个技术方案，其提供了一种锂离子电池用硅基锡基复合颗粒的制备方法，包括如下步骤：
(1)通过水解法、溶胶-凝胶法和分解法中的任何一种制备氧化物模板或者直接采用纳米颗粒作为氧化物模板；
(2)通过原位沉积法对步骤(1)中所述氧化物模板包覆锡基材料：
(3)在碱液中去除步骤(2)得到的材料中的模板，并经过非必须的还原过程以得到中空的锡的氧化物颗粒或者中空的锡颗粒；
(4)通过化学气相沉积法或原位沉积法在步骤(3)所得的中空颗粒的表面包覆硅层以形成所述硅基锡基中空复合颗粒。
优选地，该方法包括以下步骤：
(1)制备模版
通过水解法或溶胶-凝胶法和分解法中的任何一种制备氧化物模板或者直接采用纳米颗粒作为氧化物模板。
水解法制备过程为：将水、醇和碱液按照(5～40)：(94～55)：(1～5)的体积比例混合，加入水解前驱体，在5-50℃下反应10min～3h后，得到的悬浊液经离心分离，水洗后获得颗粒模板。
溶胶-凝胶法制备过程为：将含金属离子的盐溶液加入一定量有机溶剂中，制备成浓度为1～3mol/L的溶液，然后在60～80度下滴加凝胶剂和表面活性剂，形成凝胶，将凝胶保温陈化2～24h后，在600～800度下热处理1～3h，得到颗粒模板；
分解法制备过程为：在惰性气氛中对纳米级金属盐在600～800度下热处理1～3h，得到氧化物模板。
(2)包覆锡基材料
通过原位沉积法对步骤(1)中的氧化物模板包覆锡基材料，具体步骤为：将步骤(1)获得的颗粒模板分散在50～100ml去离子水中，加入50～100ml的0.5～2mol/L的锡酸盐，在60度到80度温度范围内反应1-5小时，将产物离心水洗后得到锡的氧化物包覆的颗粒。
(3)除去模板
配制0.5～3mol/L的碱液，将步骤(2)的产物在70度到90度下在碱液中反应0.5～2h，离心水洗后得到中空的锡的氧化物颗粒，在所述中空的复合颗粒中包括中空的锡颗粒时，通过镁热反应或氢气还原的方法将中空的锡的氧化物颗粒还原为中空的锡颗粒。
(4)包覆硅层
通过化学气相沉积法和原位沉积法将硅包覆在步骤(3)所得的中空颗粒的表面。
化学气相沉积法步骤为：取0.1～1g的步骤(3)制备的中空颗粒，通过硅烷气裂解或硅氯化物加氢的方法在其表面沉积硅。
硅的原位沉积法步骤为：将步骤(3)制备的中空颗粒在反应釜中通过液相硅氯化物加氢的方法在其表面沉积硅。
步骤(1)所述醇为甲醇、乙醇、丙醇、丁醇或戊醇；所述水解前驱体为硅酸酯，如硅酸丁酯、硅酸甲酯、硅酸乙酯、硅酸二乙酯中的一种或几种。所述碱液为尿素、氨水中的一种或几种。所述金属离子的盐为Al、Mg、Ca、 Ti、Mn、Fe、Co、Ni、Cu、Zn或Zr的硝酸盐、硫酸盐、磷酸盐、碳酸盐、硅酸盐或氯酸盐。所述有机溶剂包含乙二醇甲醚和乙二醇乙醚中的一种或几种。所述表面活性剂包括十二烷基磺酸钠，硬脂酸，卵磷脂中的一种或几种。所述凝胶剂包含钛酸丁酯和硅酸乙酯中的一种或几种。所形成的氧化物模板颗粒包括氧化铝Al2O3、氧化镁MgO、氧化钙CaO、二氧化钛TiO2、氧化锰MnO和二氧化锰MnO2、氧化亚铁FeO、四氧化三铁Fe3O4、氧化钴CoO、四氧化三钴Co3O4、氧化镍NiO、氧化亚铜Cu2O、氧化铜CuO、氧化锌ZnO和氧化锆ZrO2。优选地，合成的氧化物模板粒径在5nm～200nm之间。
步骤(2)所述锡酸盐包括锡酸钠、锡酸钾、锡酸镁、锡酸钙。所述锡的氧化物包括氧化亚锡SnO和二氧化锡SnO2。
步骤(3)所采用的碱液包括氢氧化钾和氢氧化钠。优选地，形成的中空的锡颗粒或中空的锡的氧化物颗粒的中空直径在5nm～200nm之间。
步骤(4)所得中空的复合颗粒的粒径在15nm～250nm之间。优选地，所述包覆的硅层的厚度是10nm至50nm，更优选10nm至20nm。
根据本公开的另一个技术方案，其提供了根据所述制备方法制备的硅基锡基复合颗粒。
根据本公开的另一个技术方案，其提供了一种用于锂离子二次电池的负极，其包括上述的硅基锡基复合颗粒。优选地，所述负极还包括导电剂、粘结剂；其中，所述导电剂为炭黑、乙炔黑、天然石墨、碳纳米管、石墨烯、碳纤维中的至少一种或混合物；所述粘结剂为聚四氟乙烯、聚偏二氟乙烯、聚氨酯、聚丙烯酸、聚酰胺、聚丙烯、聚乙烯基醚、聚酰亚胺、苯乙烯-丁二烯共聚物、羧甲基纤维素钠中的至少一种或混合物；优选地，负极活性材料、导电剂、粘结剂的比例为：负极活性材料的质量分数为50～99.5wt％，导电剂为0.1～40wt％，粘结剂为0.1～40wt％。
根据本公开的另一个技术方案，其提供了一种二次电池，其包括上述的负极；优选地，所述二次电池还包括正极、隔膜、电解液；其中，所述正极为常用的锂电池正极，其中包含的活性材料的非限制性例子包括：钴酸锂、锰酸锂、镍酸锂、磷酸铁锂、钛酸锂、镍-钴-锰三元体系、或锂的复合金属氧化物等；所述隔膜包括芳纶隔膜、无纺布隔膜、聚乙烯微孔膜、聚丙烯膜、聚丙烯聚乙烯双层或三层复合膜及其陶瓷涂覆层隔膜中的一种；所述电解液包含电解质和溶剂；电解质为LiPF6、LiBF4、LiClO4、LiAsF6、LiCF3SO3、LiN(CF3SO2)、LiBOB、LiCl、LiBr、LiI中的至少一种或者混合物；溶剂包 括丙烯碳酸酯(PC)、碳酸二甲酯(DMC)、碳酸甲乙酯(EMC)、1,2-二甲氧基乙烷(DME)、碳酸乙烯酯、碳酸丙烯酯、碳酸丁烯酯、碳酸二乙酯、碳酸甲丙酯、乙腈、乙酸乙酯、亚硫酸乙烯酯中的至少一种或几种混合物。
在本公开中，除非另有限定，所述的数值范围包括其中的任意子范围，并且可以认为是公开了其中的任意数值。
在本公开中，所述复合颗粒可以是球形，多面体颗粒形，或棒状，其为棒状时，其长径比可以为2：1至10：1。在本公开中，所述复合颗粒的粒径，以及所述中空的锡颗粒或中空的锡的氧化物颗粒的中空直径是通过电镜分析、氮气吸附孔体积分析或激光粒度分析测量或计算得出的。
本公开制备的硅基锡基复合颗粒，制备方法简单，材料来源丰富。而且由于其中空结构，该颗粒能够有效的容纳硅基和锡基材料在嵌锂过程中的体积膨胀，从而保持电极结构的稳定。而且，外部硅基材料能够有效阻止纳米锡颗粒的团聚，保持锡基材料的稳定，从而可以获得比容量高，循环性能好的锂离子电池负极复合材料。
附图说明
图1为本公开制备的硅基锡基复合颗粒的结构示意图。
图2为本公开制备的球形纳米颗粒的制备方法，其中a表示制备的模板，b表示包覆了锡基材料的模板，c表示去除模板的中空锡基材料，d表示去除模板的中空复合颗粒。
图3为本公开的球形中空复合颗粒嵌锂和脱锂时的变化的示意图，其中左侧为原始状态，中间为嵌锂后的状态，右侧为脱锂后的状态。
图4和图5为本公开的实施例1制备的中空复合颗粒的扫描电子显微镜照片。
图6为本公开的实施例1制备的中空复合颗粒作为负极材料时的循环性能图，其中圆形点表示充电比容量，方块点表示放电比容量，三角形点表示库伦效率。
图7为本公开的实施例2制备的中空复合颗粒的透射电子显微镜照片。
图8为本公开的实施例2制备的中空复合颗粒作为负极材料时的循环性能图，其中实心点表示放电比容量，空心点表示库伦效率。
图9为本公开的实施例3制备的中空复合颗粒的透射电子显微镜照片。
图10为本公开的实施例3制备的中空复合颗粒作为负极材料时循环性能图，其中上方的数据点表示库伦效率，下方的数据点表示放电比容量。
图11为本公开的实施例4制备的中空复合颗粒的透射电子显微镜照片。
图12为本公开的实施例4制备的中空复合颗粒作为负极材料时循环性能图，其中三角形的数据点表示库伦效率，圆形的数据点表示放电比容量。
图13为本公开的对比实施例1制备的实心硅/二氧化锡复合颗粒作为负极材料时循环性能图，其中上方的实心方块数据点表示库伦效率，下方的圆形和空心方块的数据点分别表示充电和放电比容量。
图14为本公开的对比实施例2制备的二氧化锡空心球作为负极材料时的循环性能图，其中，圆形和方块数据点分别表示充电和放电比容量。
具体实施方式
以下将通过具体实施方式详细描述本公开，但应注意的是，以下实施方式仅用于理解本公开，而不是为了限制本公开的范围。
图1显示出本公开的示例性的颗粒结构，从左到右分别为球形、多面体型、棒状，其中外层表示硅层，中间表示锡基材料，内部是中空的。
图2和图3以球形中空复合材料为例，显示出其制备方法，其他形状的材料的制备方法与之类似，在此不再赘述。
图4是本公开的球形中空复合颗粒嵌锂和脱锂时的变化的示意图，其中左侧为原始状态，中间为嵌锂后的状态，右侧为脱锂后的状态，其他形状的材料的嵌锂和脱锂时的变化与之类似，在此不再赘述。由图4可以看出，本公开的中空复合颗粒在嵌锂和脱锂(即充放电过程)时体积变化小。
以下通过实施例详细描述复合材料的制备过程，本领域技术人员能够根据以下制备过程得到本公开的方案。
实施例1
(1)在烧杯中混合60ml去离子水，150ml乙醇和15ml的25％的氨水，加入10ml正硅酸乙酯并在室温下搅拌50min。离心并用去离子水洗涤得到粒径为130nm的二氧化硅模板。
(2)将1g步骤(1)中的产物加入到100ml去离子水中，超声分散30min。加入1mol/L的锡酸钠溶液50ml，搅拌并在70度下反应2h。离心并用去离子水洗涤得到产物。
(3)配制1.5mol/L的氢氧化钾溶液，加入步骤(2)中的产物，搅拌并在75度下反应1h。离心并用去离子水洗涤得到粒径为150nm的二氧化锡中空球。
(4)将步骤0.5g步骤(3)的产物放到管式炉中，在氩气保护下通过硅烷气裂解法以100sccm的流量在450度反应2h。得到粒径为170nm的硅/二氧化锡中空球。
将所制备的活性物质、导电炭黑及粘结剂聚丙烯酸按85：10：5的质量比混合均匀，以去离子水为溶剂制得负极浆料，将其涂于铜箔上制成负极片，并在60℃下真空隔夜干燥。电化学测试使用CR2025型纽扣电池进行，对电极为分析纯的金属锂片，电解液为1M LiPF6的碳酸乙烯酯(EC)/碳酸二甲酯(DMC)(体积比为1：1)溶液，电池隔膜为Celgard-2320(微孔聚丙烯膜)。在充满氩气的手套箱中进行电池的装配，如图6所示，此方法制备的材料化成后在600mA/g的电流密度下容量稳定在约900mAh/g，100次循环下的容量保持率约81％。
实施例2
(1)以乙二醇甲醚为溶剂，配置2mol/L的硝酸铁溶液100ml。搅拌并在70度下分别加入10ml的十二烷基磺酸钠、钛酸丁酯和硅酸乙酯。形成均匀、稳定的棕色溶胶后，在70度下陈化溶胶2h，并在90度下减压干燥3h。取出产物，在马弗炉中600度下煅烧3h，得到粒径为50nm的三氧化二铁的纳米块状颗粒。
(2)将2g步骤(1)中的产物加入到100ml去离子水中，超声分散30min。加入1mol/L的锡酸钾溶液30ml，搅拌并在60度下反应2h。离心并用去离子水洗涤得到产物。
(3)配制1mol/L的氢氧化钾溶液，加入步骤(2)中的产物，搅拌并在80度下反应2h。离心并用去离子水洗涤得到粒径为60nm的二氧化锡中空颗粒。将中空颗粒与镁粉混合，置于管式炉中，在惰性气体氛围下载700度反应3h，用醋酸除去氧化镁，离心并用去离子水洗涤后得到粒径为60nm的锡中空颗粒。
(4)将步骤1g步骤(3)的产物放到反应釜中，以四氯化硅为硅源，通过催化加氢的方法沉积硅在二氧化锡中空颗粒表面，形成粒径为80nm的硅/锡复合中空颗粒。
将所制备的活性物质、导电炭黑及粘结剂聚丙烯酸按85：10：5的质量比混合均匀，以去离子水为溶剂制得负极浆料，将其涂于铜箔上制成负极片，并在60℃下真空隔夜干燥。电化学测试使用CR2025型纽扣电池进行，对电极为分析纯的金属锂片，电解液为1M LiPF6的碳酸乙烯酯(EC)/碳酸二甲酯(DMC)(体积比为1：1)溶液，电池隔膜为Celgard-2320(微孔聚丙烯膜)。在充满氩气的手套箱中进行电池的装配，如图8所示，此方法制备的材料化成后在600mA/g的电流密度下容量稳定在约1300mAh/g，100次循环下的容量保持率约83％。
实施例3
(1)以乙二醇甲醚为溶剂，配置2mol/L的硝酸锌溶液100ml。搅拌并在80度下分别加入20ml的十二烷基磺酸钠、钛酸丁酯和硅酸乙酯。形成均匀、稳定的棕色溶胶后，在80度下陈化溶胶2h，并在90度下减压干燥3h。取出产物，在马弗炉中600度下煅烧3h，得到粒径为100nm的氧化锌的纳米球状颗粒。
(2)将3g步骤(1)中的产物加入到100ml去离子水中，超声分散30min。加入1mol/L的锡酸钠溶液40ml，搅拌并在60度下反应0.5h。离心并用去离子水洗涤得到产物。
(3)配制2mol/L的氢氧化钾溶液，加入步骤(2)中的产物，搅拌并在80度下反应2h。离心并用去离子水洗涤得到粒径为120nm的氧化亚锡中空球。
(4)将1g步骤(3)的产物放到反应釜中，以四氯化硅为硅源，通过催化加氢的方法沉积硅在二氧化锡中空颗粒表面，形成粒径为150nm的硅/氧化亚锡复合中空球。
将所制备的活性物质、导电炭黑及粘结剂聚丙烯酸按85：10：5的质量比混合均匀，以去离子水为溶剂制得负极浆料，将其涂于铜箔上制成负极片，并在60℃下真空隔夜干燥。电化学测试使用CR2025型纽扣电池进行，对电极为分析纯的金属锂片，电解液为1M LiPF6的碳酸乙烯酯(EC)/碳酸二甲酯(DMC)(体积比为1：1)溶液，电池隔膜为Celgard-2320(微孔聚丙烯膜)。在充满氩气的手套箱中进行电池的装配，如图10所示，此方法制备的材料化成后在600mA/g的电流密度下容量稳定在约900mAh/g，100次循环下的容量保持率约90％。
实施例4
(1)取3g粒径为80nm的氧化铝颗粒加入到100ml去离子水中，超声分散30min。加入1mol/L的锡酸钾溶液50ml，搅拌并在70度下反应2h。离心并用去离子水洗涤得到产物。
(3)配制2mol/L的氢氧化钾溶液，加入步骤(2)中的产物，搅拌并在80度下反应2h。离心并用去离子水洗涤得到粒径为100nm的二氧化锡中空球。
(4)将步骤(3)的产物放到管式炉中，在氩气保护下通过硅烷气裂解法以200sccm的流量在450度反应1.5h。得到粒径为140nm的硅/二氧化锡中空球。
将所制备的活性物质、导电炭黑及粘结剂聚丙烯酸按85：10：5的质量比混合均匀，以去离子水为溶剂制得负极浆料，将其涂于铜箔上制成负极片，并在60℃下真空隔夜干燥。电化学测试使用CR2025型纽扣电池进行，对电极为分析纯的金属锂片，电解液为1M LiPF6的碳酸乙烯酯(EC)/碳酸二甲酯(DMC)(体积比为1：1)溶液，电池隔膜为Celgard-2320(微孔聚丙烯膜)。在充满氩气的手套箱中进行电池的装配，如图12所示，此方法制备的材料化成后在600mA/g的电流密度下容量稳定在约850mAh/g，100次循环下的容量保持率约77％。
对比实施例1
除了不进行步骤(1)和(3)以外，按照与实施例1相同的制备颗粒的方法得到实心硅/二氧化锡颗粒，并根据与实施例1相同的制备电池的方法制备电池并测试其电化学性能，结果如图13所示。从图13可以看出，由于缺乏容纳膨胀的空间，材料破碎，循环性能差，在600mA/g的电流密度下100次循环后，电池比容量从大约600mAh/g下降到大约100mAh/g，100次循环下的容量保持率仅为约16.7％。
对比实施例2
除了不进行步骤(4)以外，按照与实施例1相同的制备颗粒的方法得到空心二氧化锡颗粒，并根据与实施例1相同的制备电池的方法制备电池并测试其电化学性能，结果如图14所示。从图14中可以看出，由于锡在循环过程中团聚，失去空心结构，在600mA/g的电流密度下的电池的循环性能从大约800mAh/g下降到大约400mAh/g，100次循环下的容量保持率仅为约50％。
根据图6-14可以看出，根据本公开提供的中空复合颗粒的初始比容量、100次循环后的比容量和100次循环后的容量保持率都大大高于对比实施例中的相应值。
根据以上的实验结果可以看出，本公开提供的中空复合颗粒能够有效的容纳硅基和锡基材料在嵌锂过程中的体积膨胀，从而保持电极结构的稳定，并获得比容量高，循环性能好的锂离子电池负极复合材料。

Claims (10)

  1. 一种锂离子电池用硅基锡基复合颗粒，其特征在于，所述硅基锡基复合颗粒包括：
    中空的锡颗粒或中空的锡的氧化物颗粒，以及
    在所述中空的锡颗粒或中空的锡的氧化物颗粒的外表面包覆的硅层。
  2. 根据权利要求1所述的硅基锡基复合颗粒，其中，
    所述硅基锡基复合颗粒的粒径在15nm至250nm之间，所述中空的锡颗粒或中空的锡的氧化物颗粒的空腔的尺寸在5nm-200nm之间。
  3. 根据权利要求1所述的硅基锡基复合颗粒，其中，
    所述硅基锡基复合颗粒是球形，多面体形，或棒状，其为棒状时，长径比为2：1至10：1。
  4. 根据权利要求1所述的硅基锡基复合颗粒，其中，
    所述包覆的硅层的厚度是10nm至50nm。
  5. 一种锂离子电池用硅基锡基复合颗粒的制备方法，包括如下步骤：
    (1)通过水解法、溶胶-凝胶法和分解法中的任何一种制备氧化物模板或者直接采用纳米颗粒作为氧化物模板；
    (2)通过原位沉积法对步骤(1)中所述氧化物模板包覆锡基材料：
    (3)在碱液中去除步骤(2)得到的材料中的模板，并经过非必须的还原过程以得到中空的锡的氧化物颗粒或者中空的锡颗粒；
    (4)通过化学气相沉积法或原位沉积法在步骤(3)所得的中空颗粒的表面包覆硅层以形成所述硅基锡基复合颗粒。
  6. 根据权利要求5所述的制备方法，包括如下步骤：
    (1)通过水解法、溶胶-凝胶法和分解法中的任何一种制备氧化物模板或者直接采用纳米颗粒作为氧化物模板；
    水解法制备过程为：将水、醇和碱液按照(5～40)：(94～55)：(1～5)的体积比混合，加入水解前驱体，在5-50℃下反应10min～3h后，得到的悬浊液经离心分离，水洗后获得氧化物模板；
    溶胶-凝胶法制备过程为：将含金属离子的盐溶液加入有机溶剂中，制备成浓度为1～3mol/L的溶液，然后在60～80度下滴加凝胶剂和表面活性剂至形成凝胶，将凝胶保温陈化2～24h后，在600～800度下热处理1～3h，得到氧化物模板；
    分解法制备过程为：在惰性气氛中对纳米级金属盐在600～800度下热处理1～3h，得到氧化物模板；
    (2)包覆锡基材料
    通过原位沉积法对步骤(1)中的所述氧化物模板包覆锡基材料，包括：将步骤(1)得到的氧化物模板分散在50～100ml去离子水中，加入50～100ml的0.5～2mol/L的锡酸盐，在60度到80度温度范围内反应1-5小时，将产物离心水洗后得到锡的氧化物包覆的颗粒；
    (3)除去模板
    配制0.5～3mol/L的碱液，将步骤(2)得到的锡的氧化物包覆的颗粒在70度到90度下在碱液中反应0.5～2h，离心水洗后得到中空的锡的氧化物颗粒，在所述硅基锡基中空复合颗粒中包括中空的锡颗粒时，通过镁热反应或氢气还原的方法将中空的锡的氧化物颗粒还原为所述中空的锡颗粒；
    (4)包覆硅层
    通过化学气相沉积法或原位沉积法在步骤(3)所得的中空颗粒的表面包覆硅层以形成所述硅基锡基复合颗粒；
    化学气相沉积法步骤为：取0.1～1g的步骤(3)制备的中空颗粒，通过硅烷气裂解或硅氯化物加氢的方法在其表面沉积硅层；
    硅的原位沉积法步骤为：将步骤(3)制备的中空颗粒在反应釜中通过液相硅氯化物加氢的方法在其表面沉积硅层；
    其中，步骤(1)所述醇为甲醇、乙醇、丙醇、丁醇或戊醇；所述水解前驱体为硅酸酯，如硅酸丁酯、硅酸甲酯、硅酸乙酯、硅酸二乙酯中的一种或几种；所述碱液为尿素、氨水中的一种或几种；所述金属离子的盐为Al、Mg、Ca、Ti、Mn、Fe、Co、Ni、Cu、Zn或Zr的硝酸盐、硫酸盐、磷酸盐、碳酸盐、硅酸盐或氯酸盐；所述有机溶剂包含乙二醇甲醚和乙二醇乙醚中的一种或几种；所述表面活性剂包括十二烷基磺酸钠，硬脂酸，卵磷脂中的一种或几种；所述凝胶剂包含钛酸丁酯和硅酸乙酯中的一种或几种；所形成的氧化物模板颗粒包括氧化铝Al2O3、氧化镁MgO、氧化钙CaO、二氧化钛TiO2、氧化锰MnO和二氧化锰MnO2、氧化亚铁FeO、四氧化三铁Fe3O4、氧化钴CoO、四氧化三钴Co3O4、氧化镍NiO、氧化亚铜Cu2O、氧化铜CuO、氧化锌ZnO和氧化锆ZrO2；
    步骤(2)所述锡酸盐包括锡酸钠、锡酸钾、锡酸镁、锡酸钙；所述锡的氧化物包括氧化亚锡SnO和二氧化锡SnO2；
    步骤(3)所采用的碱液包括氢氧化钾和氢氧化钠；
    步骤(4)所得的硅基锡基复合颗粒的粒径在15nm～250nm之间。
  7. 根据权利要求5或6所述的制备方法制备的硅基锡基复合颗粒。
  8. 一种用于锂离子电池的负极，其包括根据权利要求1-4或7中任一项所述的硅基锡基复合颗粒。
  9. 根据权利要求8所述的用于锂离子电池的负极，所述负极还包括导电剂、粘结剂；其中，所述导电剂为炭黑、乙炔黑、天然石墨、碳纳米管、石墨烯、碳纤维中的至少一种或混合物；所述粘结剂为聚四氟乙烯、聚偏二氟乙烯、聚氨酯、聚丙烯酸、聚酰胺、聚丙烯、聚乙烯基醚、聚酰亚胺、苯乙烯-丁二烯共聚物、羧甲基纤维素钠中的至少一种或混合物；优选地，负极活性材料、导电剂、粘结剂的比例为：负极活性材料的质量分数为50～99.5wt％，导电剂为0.1～40wt％，粘结剂为0.1～40wt％。
  10. 一种锂离子电池，其包括根据权利要求8或9所述的负极。
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CN115207354B (zh) * 2022-07-06 2025-06-27 杭州力奥科技有限公司 一种锂电池复合导电剂及其制备方法
CN115763822B (zh) * 2023-01-06 2023-08-04 碳佳(北京)科技有限公司 一种硅碳负极复合材料、应用及锂电池

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101428847A (zh) * 2008-12-15 2009-05-13 吉林大学 纳米结构二氧化锡锂离子电池负极材料的制备方法
WO2010059749A1 (en) * 2008-11-18 2010-05-27 Cornell University Carbon coated anode materials
CN103193263A (zh) * 2013-03-27 2013-07-10 东北师范大学 SnO2@C空心纳米球的制备方法及其在锂离子电池中的应用
CN103346299A (zh) * 2013-06-08 2013-10-09 上海大学 原位刻蚀制备中空锡基氧化物/碳复合纳米材料的方法
CN103848456A (zh) * 2012-12-05 2014-06-11 中国科学院理化技术研究所 一种空心结构的二氧化锡微纳米颗粒的制备方法
CN105576207A (zh) * 2016-01-28 2016-05-11 天津大学 一种中空锡铜合金二氧化硅核壳纳米复合材料的制备方法和应用

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4992128B2 (ja) * 2004-06-02 2012-08-08 パイオニクス株式会社 リチウム二次電池用負極活物質粒子および負極の製造方法
US8080335B2 (en) * 2006-06-09 2011-12-20 Canon Kabushiki Kaisha Powder material, electrode structure using the powder material, and energy storage device having the electrode structure
CN101465424B (zh) * 2008-12-29 2010-12-01 武汉市力诚科技有限公司 锂离子电池负极粉体碳素复合材料及其制备方法
CN101510601B (zh) * 2009-03-27 2011-02-09 广州鸿森材料有限公司 一种锂离子电池中硅锡合金负极材料的制备方法
CN102983309A (zh) * 2012-11-12 2013-03-20 天津大学 电流置换法制备中空锡纳米颗粒的方法及其应用
CN104319378B (zh) * 2014-10-09 2016-06-15 西安中科新能源科技有限公司 氧化物包覆锡合金/石墨烯纳米复合材料的制备方法及应用

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010059749A1 (en) * 2008-11-18 2010-05-27 Cornell University Carbon coated anode materials
CN101428847A (zh) * 2008-12-15 2009-05-13 吉林大学 纳米结构二氧化锡锂离子电池负极材料的制备方法
CN103848456A (zh) * 2012-12-05 2014-06-11 中国科学院理化技术研究所 一种空心结构的二氧化锡微纳米颗粒的制备方法
CN103193263A (zh) * 2013-03-27 2013-07-10 东北师范大学 SnO2@C空心纳米球的制备方法及其在锂离子电池中的应用
CN103346299A (zh) * 2013-06-08 2013-10-09 上海大学 原位刻蚀制备中空锡基氧化物/碳复合纳米材料的方法
CN105576207A (zh) * 2016-01-28 2016-05-11 天津大学 一种中空锡铜合金二氧化硅核壳纳米复合材料的制备方法和应用

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111948542A (zh) * 2019-05-14 2020-11-17 宝山钢铁股份有限公司 一种硅负极材料电化学性能的快速评价方法
CN113497217A (zh) * 2020-03-19 2021-10-12 香港理工大学深圳研究院 电极及其制备方法、电池
CN113497217B (zh) * 2020-03-19 2024-02-23 香港理工大学深圳研究院 电极及其制备方法、电池
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CN111847501B (zh) * 2020-06-09 2022-06-03 杭州师范大学 一种偏锡酸锌量子点的制备方法
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CN116210097A (zh) * 2020-11-12 2023-06-02 宁德时代新能源科技股份有限公司 硅基材料、其制备方法及其相关的二次电池、电池模块、电池包和装置
CN113782734B (zh) * 2021-08-24 2023-04-07 南昌大学 一种氧化亚硅负极极片的制备方法
CN113782734A (zh) * 2021-08-24 2021-12-10 南昌大学 一种氧化亚硅负极极片的制备方法
CN114166902A (zh) * 2021-12-07 2022-03-11 上海大学 一种限域型氢气传感器制备方法
CN114166902B (zh) * 2021-12-07 2023-10-20 上海大学 一种限域型氢气传感器制备方法
CN114530590B (zh) * 2022-01-27 2024-03-12 南京邮电大学 含铋锡锑的高熵氧化物负极储能材料及其制备方法与应用
CN114530590A (zh) * 2022-01-27 2022-05-24 南京邮电大学 含铋锡锑的高熵氧化物负极储能材料及其制备方法与应用
CN114649508A (zh) * 2022-04-07 2022-06-21 中国科学院长春应用化学研究所 一种锑基一体化电极及其制备方法和应用
CN114725381A (zh) * 2022-05-20 2022-07-08 洛阳师范学院 一种锡基有机金属框架材料及其制备方法和在锂离子电池负极材料中的应用
CN115295778A (zh) * 2022-07-28 2022-11-04 陕西科技大学 一种三维互联双碳限域硫化锡纳米结构制备及应用
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