WO2022262096A1 - 一种均匀改性的硅基复合材料及其制备方法和应用 - Google Patents

一种均匀改性的硅基复合材料及其制备方法和应用 Download PDF

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WO2022262096A1
WO2022262096A1 PCT/CN2021/111677 CN2021111677W WO2022262096A1 WO 2022262096 A1 WO2022262096 A1 WO 2022262096A1 CN 2021111677 W CN2021111677 W CN 2021111677W WO 2022262096 A1 WO2022262096 A1 WO 2022262096A1
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silicon
composite material
based composite
carbon
mass
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French (fr)
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罗飞
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Tianmulake Excellent Anode Materials Co Ltd
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Tianmulake Excellent Anode Materials Co Ltd
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Priority to KR1020237043936A priority Critical patent/KR20240010040A/ko
Priority to JP2023577186A priority patent/JP7709787B2/ja
Priority to EP21945677.9A priority patent/EP4358181A4/en
Priority to US18/567,522 priority patent/US20250125352A1/en
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Definitions

  • the invention relates to the field of material technology, in particular to a uniformly modified silicon-based composite material and a preparation method and application thereof.
  • the negative electrode material is one of the four main materials of lithium-ion batteries, and its capacity largely affects the energy density of lithium-ion batteries. Silicon and lithium form an alloy at a lower potential, and react to form Li 3.75 Si. At this time, the specific capacity can reach 3975mAh/g. However, the huge volume change of up to 300% in the process of lithium intercalation and deintercalation of silicon severely limits the application of this material.
  • the volume expansion of silicon oxide (SiO x ) in the lithium intercalation state is about 150%, and its specific capacity ( ⁇ 1700mAh/g) is lower than that of silicon materials, but still much higher than the current Commercial graphite (372mAh/g) has therefore become one of the research hotspots of negative electrode materials.
  • the first cycle efficiency of silicon oxide is low ( ⁇ 78%), and the volume change of 150% still faces the problem of material pulverization.
  • Carbon coating is a relatively common modification method. On the one hand, it can avoid the direct contact between the electrolyte and SiO x , reduce the formation of solid electrolyte interface (SEI) film, and improve the reversible capacity of the material; It can buffer the volume change of SiO x particles in the process of lithium intercalation and deintercalation, thereby improving the cycle performance of the material; it can also improve the electronic conductivity of the material surface, thereby improving the rate performance of the material.
  • SEI solid electrolyte interface
  • carbon coating can only change the surface conductivity. In order to achieve fast charging performance, the conductivity inside the particles also needs to be improved.
  • the embodiment of the present invention provides a uniformly modified silicon-based composite material and its preparation method and application. Through the bulk doping distribution of carbon elements and A elements, the conductivity of the material and the cycle stability of lithium-ion batteries are improved.
  • the embodiment of the present invention provides a uniformly modified silicon-based composite material.
  • the general formula of the silicon-based composite material is SiC x A y O z ; 0 ⁇ x ⁇ 20;0 ⁇ y ⁇ 10;0 ⁇ z ⁇ 10;
  • A is one or more of B, Al, Mg, Ca, Fe, Co, Ni, Cu, Zn, Ge, Sn, Li, and C is uniformly dispersed in the particles of the silicon-based composite material at the atomic scale. , and there is no agglomeration of carbon elements above 20nm; some or all of the carbon atoms combine with silicon atoms to form disordered Si-C bonds; in the focused ion beam-transmission electron microscope FIB-TEM test of silicon-based composite materials, the energy Spectrum scanning shows that silicon, carbon, A, and oxygen are evenly distributed inside the particles;
  • the microstructure of the silicon-based composite material is a multiphase dispersed structure
  • the average particle diameter D50 of the silicon-based composite material particles is 1nm-100 ⁇ m, and the specific surface area is 0.5m 2 /g-40m 2 /g; the mass of the carbon atoms accounts for 0.1%-40% of the mass of the silicon-based composite material. %; the mass of the A element accounts for 3%-40% of the mass of the composite particles.
  • the silicon-based composite material also has a carbon coating layer on the outside; the mass of the carbon coating layer accounts for 0-20% of the mass of the silicon-based composite material.
  • the mass of the carbon atoms accounts for 0.5%-10% of the mass of the silicon-based composite material; the mass of the carbon coating layer accounts for 0-10% of the mass of the silicon-based composite material.
  • an embodiment of the present invention provides a method for preparing the uniformly modified silicon-based composite material described in the first aspect above, and the preparation method includes a one-step vapor deposition method or a two-step vapor deposition method.
  • the one-step vapor deposition method specifically includes:
  • the material obtained from the gas-phase mixing reaction is cooled to room temperature, and the material is crushed and sieved to obtain a SiC x A y O z silicon-based composite material in which carbon elements are uniformly dispersed on an atomic scale.
  • the two-step vapor deposition method specifically includes:
  • the material obtained by the gas phase mixing reaction is cooled to room temperature, and discharged, pulverized and sieved to obtain a SiC x O z composite material in which carbon elements are uniformly dispersed on an atomic scale;
  • SiC x O z with elemental A powder and/or A oxide powder evenly, place in a high-temperature furnace, and heat-treat at 600°C-1500°C for 2-24 hours to obtain SiC with uniform dispersion of carbon elements on the atomic scale x A y O z silicon matrix composites.
  • the carbon-containing gas source includes: one or more of methane, propane, butane, acetylene, ethylene, propylene, butadiene or carbon monoxide.
  • the preparation method further includes: carbon-coating the screened material, and obtaining the negative electrode material after classification.
  • the preparation method further includes: carbon coating the sieved material; wherein, the carbon coating includes: At least one of gas phase coating, liquid phase coating and solid phase coating.
  • an embodiment of the present invention provides a negative electrode sheet comprising the uniformly modified silicon-based composite material described in the first aspect.
  • an embodiment of the present invention provides a lithium battery comprising the negative electrode sheet described in the third aspect above.
  • the uniformly modified silicon-based composite material SiC x A y O z provided by the present invention improves the bulk phase conductivity of the silicon-based material through the bulk phase doping distribution of the C element and the A element, which is the volume expansion of the silicon-based material It provides a buffer space where the bulk phase is uniformly distributed, and improves the fast charging performance, first-time Coulombic efficiency and cycle stability of the material.
  • Fig. 1 is a flow chart of a method for preparing a silicon-based composite material provided by an embodiment of the present invention
  • Fig. 2 is the flowchart of the preparation method of the silicon-based composite material of the embodiment of the present invention
  • Fig. 3 is a FIB-TEM energy spectrum scan of a silicon-based negative electrode material with internal carbon atoms uniformly and dispersedly distributed at the atomic level provided by Example 1 of the present invention.
  • the uniformly modified silicon-based composite material proposed by the present invention has a general formula of SiC x A y O z , wherein 0 ⁇ x ⁇ 20;0 ⁇ y ⁇ 10;0 ⁇ z ⁇ 10;
  • A is one or more of B, Al, Mg, Ca, Fe, Co, Ni, Cu, Zn, Ge, Sn, Li, and C is uniformly dispersed in the particles of the silicon-based composite material at the atomic scale, and There is no agglomeration of carbon elements above 20nm; some or all of the carbon atoms combine with silicon atoms to form disordered Si-C bonds; in the focused ion beam-transmission electron microscope (FIB-TEM) test of silicon-based composite materials, the energy of the particle section Spectrum scanning shows that silicon, carbon, A, and oxygen are evenly distributed inside the particles;
  • FIB-TEM focused ion beam-transmission electron microscope
  • the microstructure of the silicon-based composite material is a multi-phase dispersed structure
  • the average particle diameter D50 of the silicon-based composite material particles is 1nm-100 ⁇ m, and the specific surface area is 0.5m 2 /g-40m 2 /g; the mass of the carbon atoms accounts for 0.1%-40% of the mass of the silicon-based composite material, preferably 0.5%-10%; the mass of element A accounts for 3%-40% of the mass of the composite particle.
  • the outer layer of the above materials can also be coated with a carbon coating layer, and the quality of the carbon coating layer accounts for 0-20% of the quality of the silicon-based composite material.
  • the quality of the carbon coating layer accounts for 0% of the quality of the silicon-based composite material. 0-10%.
  • the uniformly modified silicon-based composite material of the present invention can be obtained by one-step vapor deposition or two-step vapor deposition.
  • Step 110 uniformly mixing silicon powder, silicon dioxide powder, elemental A powder and/or A oxide powder according to the required amount, and placing them in a vacuum furnace;
  • Step 120 after depressurizing in the vacuum furnace, heating to 1200°C-1700°C to obtain a mixed vapor containing silicon element, oxygen element, and A element;
  • the vacuum furnace is depressurized to below 300Pa.
  • Step 130 under a protective atmosphere, pass a carbon-containing gas source into the vacuum furnace, and perform a gas-phase mixing reaction with the mixed steam for 1-24 hours;
  • the protective atmosphere can be N2 or Ar atmosphere.
  • the carbon-containing gas source includes: one or more of methane, propane, butane, acetylene, ethylene, propylene, butadiene or carbon monoxide.
  • step 140 the material obtained from the gas phase mixing reaction is cooled to room temperature, and the material is crushed and sieved to obtain a SiC x A y O z silicon-based composite material in which carbon elements are uniformly dispersed on an atomic scale.
  • Step 210 uniformly mixing silicon powder and silicon dioxide powder according to the required amount, and placing them in a vacuum furnace;
  • Step 220 after depressurizing in the vacuum furnace, heating to 1200°C-1700°C to obtain a mixed vapor containing silicon and oxygen;
  • the vacuum furnace is depressurized to below 300Pa.
  • Step 230 under a protective atmosphere, feed a carbon-containing gas source into the vacuum furnace, and perform a gas-phase mixing reaction with the mixed steam for 1-24 hours;
  • the protective atmosphere can be N2 or Ar atmosphere.
  • the carbon-containing gas source includes: one or more of methane, propane, butane, acetylene, ethylene, propylene, butadiene or carbon monoxide.
  • Step 240 cooling the material obtained from the gas-phase mixing reaction to room temperature, and discharging, pulverizing and sieving to obtain a SiC x O z composite material in which carbon elements are uniformly dispersed on an atomic scale;
  • Step 250 uniformly mix SiC x Oz with elemental A powder and/or A oxide powder, place in a high-temperature furnace, and heat-treat at 600°C-1500°C for 2-24 hours to obtain uniform dispersion of carbon elements on an atomic scale Distributed SiC x A y O z silicon matrix composites.
  • the silicon-based composite material with a carbon-coated layer is prepared on the outside, the silicon-based composite material can also be obtained by carbon-coating and classifying the pulverized material.
  • the specific method of carbon coating may include at least one of gas phase coating, liquid phase coating and solid phase coating. The above method is a commonly used coating method in the process of preparing battery materials, and will not be described here.
  • the silicon-based composite material provided by the invention has carbon elements uniformly dispersed and distributed inside the particles at the atomic scale. Through the bulk phase doping distribution of C element and A element, the bulk phase conductivity of the silicon-based material is improved, and it is a silicon-based material.
  • the volume expansion provides a buffer space for the uniform distribution of the bulk phase, which improves the fast charging performance, first-time Coulombic efficiency and cycle stability of the material.
  • the silicon-based composite material proposed by the invention can be used to prepare negative pole sheets and be used in lithium batteries.
  • Figure 3 is a surface scan of the FIB-TEM energy spectrum. From the elemental surface scan of the energy spectrum in Figure 2, it can be seen that the four elements Si, C, Cu, and O are evenly distributed in the particles.
  • the above-mentioned silicon-based composite material containing carbon coating layer is used as the negative electrode material, and the conductive additive conductive carbon black (SP), and the binder polyvinylidene fluoride (PVDF) are weighed according to the ratio of 95%: 2%: 3%. , at room temperature, slurry preparation in a beater. Spread the prepared slurry evenly on the copper foil. After drying for 2 hours in a blast drying oven at 50°C, cut them into 8 ⁇ 8mm pole pieces, and vacuum-dry them in a vacuum drying oven at 100°C for 10 hours. The dried pole pieces were immediately transferred into the glove box for battery assembly.
  • SP conductive additive conductive carbon black
  • PVDF binder polyvinylidene fluoride
  • the solution is used as the electrolyte and assembled into a battery.
  • the cut-off voltage for discharge is 0.005V, and the cut-off voltage for charge is 1.5V.
  • the charge-discharge test is performed at a current density of C/10 in the first week, and the discharge test is performed at a current density of C/10 in the second week. under density.
  • the initial efficiency, 0.1C reversible capacity, and cycle performance test results at 0.1C rate are listed in Table 1.
  • the above materials are then carbon coated. Put 2kg of silicon-based composite material in a rotary furnace and raise the temperature to 1000°C under the protective gas argon, and then pass in argon and propylene at a volume ratio of 1:1 for gas phase coating, keep it warm for 2 hours and turn off the organic gas source. After the material is cooled and classified, a carbon-coated silicon-based composite material is obtained, wherein the total carbon content is 4.6%.
  • silicon powder 3kg of silicon dioxide, and 1kg of boron oxide mixed powder in a vacuum furnace, evacuate to 100Pa, heat up to 1350°C to become a vapor, and slowly feed 23.4L of propane under an argon flow to react8 hours, cooled to room temperature. After the material is discharged and pulverized, the silicon-based composite material in which the internal carbon and boron elements are evenly dispersed at the atomic level can be obtained.
  • the carbon content is 2.0% when tested with a carbon-sulfur analyzer.
  • the obtained silicon-based composite material with internal carbon elements uniformly dispersed at the atomic level and metal aluminum are uniformly mixed at a molar ratio of 2:1, and then heat-treated at 1200°C for 4 hours to obtain a silicon-based composite material containing internal carbon elements and copper elements. Material.
  • the mixed powder of 2kg silicon, 3kg silicon dioxide and 0.5kg metal iron in a vacuum furnace, evacuate to 100Pa, heat up to 1600°C and turn it into a vapor, and slowly inject 1L of butane gas under the argon flow. React for 3 hours and cool to room temperature. After the material is discharged and pulverized, the silicon-based composite material in which the internal carbon and iron elements are evenly dispersed at the atomic level can be obtained. The carbon content is 2% when tested with a carbon-sulfur analyzer.
  • the above-mentioned silicon-based composite material containing carbon coating layer is used as the negative electrode material, and the conductive additive conductive carbon black (SP), and the binder polyvinylidene fluoride (PVDF) are weighed according to the ratio of 95%: 2%: 3%. .
  • Slurry preparation was carried out in a beater at room temperature. Spread the prepared slurry evenly on the copper foil. After drying for 2 hours in a blast drying oven at 50°C, cut them into 8 ⁇ 8mm pole pieces, and vacuum-dry them in a vacuum drying oven at 100°C for 10 hours. The dried pole pieces were immediately transferred into the glove box for battery assembly.
  • the assembly of the simulated battery was carried out in a glove box containing a high-purity Ar atmosphere.
  • the above electrode was used as the negative electrode
  • the ternary positive electrode material NCM811 was used as the counter electrode
  • the garnet-type Li 7 La 3 Zr 2 O 12 (LLZO) was used as the solid electrolyte.
  • LLZO garnet-type Li 7 La 3 Zr 2 O 12
  • the charge-discharge test is performed at a current density of C/10 in the first week, and the discharge test is performed at a current density of C/10 in the second week. under density.
  • the initial efficiency, 0.1C reversible capacity, and cycle performance test results at 0.1C rate are listed in Table 1.
  • the above-mentioned silicon-based composite material containing carbon coating layer is used as the negative electrode material, and the conductive additive conductive carbon black (SP), and the binder polyvinylidene fluoride (PVDF) are weighed according to the ratio of 95%: 2%: 3%. .
  • Slurry preparation was carried out in a beater at room temperature. The prepared slurry is evenly coated on the copper foil. After drying in a blast oven for 2 hours at a temperature of 50 degrees Celsius, cut them into pole pieces of 8 ⁇ 8 mm, and dry them in a vacuum oven at a temperature of 100 degrees Celsius for 10 hours under vacuum. The dried pole pieces were immediately transferred into the glove box for battery assembly.
  • the assembly of the simulated battery was carried out in a glove box containing a high-purity Ar atmosphere.
  • the above electrode was used as the negative electrode
  • the ternary positive electrode material NCM811 was used as the counter electrode
  • the polyolefin-based gel polymer electrolyte membrane was used as the semi-solid electrolyte.
  • a semi-solid button battery was assembled in the medium, charged and evaluated for electrochemical performance.
  • the cut-off voltage for discharge is 0.005V, and the cut-off voltage for charge is 1.5V.
  • the charge-discharge test is performed at a current density of C/10 in the first week
  • the discharge test is performed at a current density of C/10 in the second week. under density.
  • the initial efficiency, 0.1C reversible capacity, and cycle performance test results at 0.1C rate are listed in Table 1.
  • silicon powder and 5kg of silicon dioxide mixed powder in a vacuum furnace, evacuate to 150Pa, heat up to 1500°C and turn into steam. Under an argon flow, 1.7 L of methane and 1.5 L of propylene mixed gas were slowly passed through to react for 3 hours, and then cooled to room temperature. After the material is discharged and pulverized, the silicon-based material powder in which the internal carbon element is uniformly dispersed at the atomic level is obtained. The carbon content is 1.5% when tested with a carbon-sulfur analyzer.
  • silicon powder and 5kg of silicon dioxide mixed powder in a vacuum furnace, evacuate to 150Pa, heat up to 1500°C and turn into steam. Under an argon flow, 2 L of butadiene gas was slowly introduced into the mixture for 4 hours, and then cooled to room temperature. After the material is discharged and pulverized, silicon-based material powder in which internal carbon elements are uniformly dispersed at the atomic level is obtained. The carbon content is 0.5% when tested with a carbon-sulfur analyzer.
  • Comparative Example 2 doped silicon oxide with copper element, which significantly improved the initial efficiency compared with Comparative Example 1, but the cycle performance was inferior.
  • silicon oxide was doped with carbon elements, which significantly improved the cycle capacity retention rate compared with Comparative Example 1, but the first-time efficiency was slightly inferior.
  • bulk phase doping of carbon and A elements increases the electrical conductivity inside the particles, provides a buffer space for the expansion of the material, and improves the first-time efficiency and cycle life of the material.

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Abstract

一种均匀改性的硅基复合材料及其制备方法和应用，硅基复合材料的通式为SiC xA yO z；0＜x＜20；0＜y＜10；0＜z＜10；其中，A为B、Al、Mg、Ca、Fe、Co、Ni、Cu、Zn、Ge、Sn、Li中的一种或多种，C以原子尺度均匀弥散分布在硅基复合材料的颗粒内部，且无20nm以上的碳原子团聚；部分或所有碳原子与硅原子结合形成无序的Si-C键；在硅基复合材料的聚焦离子束-透射电镜FIB-TEM测试中，颗粒切面的能谱面扫显示颗粒内部硅元素、碳元素、A元素、氧元素均匀分布；所述硅基复合材料的微观结构为多相弥散结构；所述硅基复合材料颗粒的平均粒径D 50为1nm-100μm，比表面积为0.5m 2/g-40m 2/g；所述碳原子的质量占硅基复合材料质量的0.1％-40％；所述A元素的质量占复合颗粒质量的3％-40％。

Description

一种均匀改性的硅基复合材料及其制备方法和应用
本申请要求于2021年06月16日提交中国专利局、申请号为202110668605.8、发明名称为“一种均匀改性的硅基复合材料及其制备方法和应用”的中国专利申请的优先权。
技术领域
本发明涉及材料技术领域，尤其涉及一种均匀改性的硅基复合材料及其制备方法和应用。
背景技术
随着锂离子电池应用的快速发展，以及对高能量密度需求的不断增加，开发具有高比容量的电极材料成为目前锂电池领域的研究重点。负极材料作为锂离子电池四大主材之一，其容量的高低在很大程度上影响着锂离子电池能量密度的高低。硅与锂在较低的电位下形成合金，反应生成Li 3.75Si，此时比容量可达3975mAh/g。然而，硅在脱嵌锂过程中高达300％的巨大体积变化，严重限制了该材料的应用。
相比于硅的巨大体积变化，氧化亚硅(SiO x)在嵌锂状态下的体积膨胀在150％左右，其比容量(～1700mAh/g)虽然低于硅材料，但仍然远高于目前商业化的石墨(372mAh/g)，因此成为负极材料的研究热点之一。然而氧化亚硅的首圈效率低(～78％)，且150％的体积变化仍然面临材料粉化的问题。
碳包覆是一种比较常见的改性方式，一方面可以避免电解液与SiO x的直接接触，减少固态电解质界面(SEI)膜的生成，提升材料的可逆容量；并且表面碳的力学作用还可缓冲SiO x颗粒在脱嵌锂过程中的体积变化，从 而提升该材料的循环性能；还可以提高材料表面的电子电导率，从而提升材料的倍率性能。但是碳包覆只能改变表面导电性，为了实现快充性能，颗粒内部的导电性也需要改善。
发明内容
本发明实施例提供了一种均匀改性的硅基复合材料及其制备方法和应用。通过碳元素和A元素的体相掺杂分布，改善了材料的导电性和锂离子电池的循环稳定性。
第一方面，本发明实施例提供了一种均匀改性的硅基复合材料，硅基复合材料的通式为SiC xA yO z；0＜x＜20；0＜y＜10；0＜z＜10；
其中，A为B、Al、Mg、Ca、Fe、Co、Ni、Cu、Zn、Ge、Sn、Li中的一种或多种，C以原子尺度均匀弥散分布在硅基复合材料的颗粒内部，且无20nm以上的碳元素团聚；部分或所有碳原子与硅原子结合形成无序的Si-C键；在硅基复合材料的聚焦离子束-透射电镜FIB-TEM测试中，颗粒切面的能谱面扫显示颗粒内部硅元素、碳元素、A元素、氧元素均匀分布；
所述硅基复合材料的微观结构为多相弥散结构；
所述硅基复合材料颗粒的平均粒径D 50为1nm-100μm，比表面积为0.5m 2/g-40m 2/g；所述碳原子的质量占硅基复合材料质质量的0.1％-40％；所述A元素的质量占复合颗粒质量的3％-40％。
优选的，硅基复合材料的外部还具有碳包覆层；所述碳包覆层的质量占所述硅基复合材料质量的0-20％。
进一步优选的，所述碳原子的质量占所述硅基复合材料质量的0.5％-10％；所述碳包覆层的质量占所述硅基复合材料质量的0-10％。
第二方面，本发明实施例提供了上述第一方面所述的均匀改性的硅基复合材料的制备方法，制备方法包括一步气相沉积法或两步气相沉积法。
优选的，所述一步气相沉积法具体包括：
按所需用量将硅粉末、二氧化硅粉末、单质A粉末和/或A的氧化物粉末混合均匀，并置于真空炉中；
真空炉减压后，加热至1200℃-1700℃，得到含硅元素、氧元素、A元素的混合蒸气；
在保护气氛下，向真空炉中通入含碳气源，与所述混合蒸气进行气相混合反应1-24小时；
将所述气相混合反应得到的物料冷却至室温，并出料粉碎筛分，即得到碳元素以原子尺度均匀弥散分布的SiC xA yO z硅基复合材料。
优选的，所述两步气相沉积法具体包括：
按所需用量将硅粉末、二氧化硅粉末混合均匀，并置于真空炉中；
真空炉减压后，加热至1200℃-1700℃，得到含硅元素、氧元素的混合蒸气；
在保护气氛下，向真空炉中通入含碳气源，与所述混合蒸气进行气相混合反应1-24小时；
将所述气相混合反应得到的物料冷却至室温，并出料粉碎筛分，即得到碳元素以原子尺度均匀弥散分布的SiC xO z复合材料；
将SiC xO z与单质A粉末和/或A的氧化物粉末混合均匀，置于高温炉中，在600℃-1500℃热处理2-24小时，即得到碳元素以原子尺度均匀弥散分布的SiC xA yO z硅基复合材料。
进一步优选的，含碳气源包括：甲烷、丙烷、丁烷、乙炔、乙烯、丙烯、丁二烯或一氧化碳中的一种或多种。
优选的，在将所述物料冷却至室温并出料粉碎筛分之后，所述制备方法还包括：对所述筛分后的物料进行碳包覆，分级后即得所述负极材料。
进一步优选的，在将所述物料冷却至室温，并出料粉碎筛分之后，所述制备方法还包括：对所述筛分后的物料进行碳包覆；其中，所述碳包覆包括：气相包覆、液相包覆、固相包覆中的至少一种。
第三方面，本发明实施例提供了一种包括上述第一方面所述的均匀改性的硅基复合材料的负极片。
第四方面，本发明实施例提供了一种包括上述第三方面所述的负极片的锂电池。
本发明提供的均匀改性的硅基复合材料SiC xA yO z，通过C元素与A元素的体相掺杂分布，改善了硅基材料的体相导电性，为硅基材料的体积膨胀提供了体相均匀分布的缓冲空间，提高了材料的快充性能、首次库伦效率和循环稳定性。
附图说明
下面通过附图和实施例，对本发明实施例的技术方案做进一步详细描述。
图1为本发明实施例提供的一种硅基复合材料的制备方法的流程图；
图2为本发明实施例的硅基复合材料的制备方法的流程图；
图3为本发明实施例1提供的内部碳原子以原子级均匀弥散分布的硅基负极材料的FIB-TEM能谱面扫图。
具体实施方式
下面通过附图和具体的实施例，对本发明进行进一步的说明，但应当理解为这些实施例仅仅是用于更详细说明之用，而不应理解为用以任何形式限制本发明，即并不意于限制本发明的保护范围。
本发明提出的均匀改性的硅基复合材料，通式为SiC xA yO z，其中0＜x＜20；0＜y＜10；0＜z＜10；
A为B、Al、Mg、Ca、Fe、Co、Ni、Cu、Zn、Ge、Sn、Li中的一种或多种，C以原子尺度均匀弥散分布在硅基复合材料的颗粒内部，且无20nm以上的碳元素团聚；部分或所有碳原子与硅原子结合形成无序的Si-C键；在硅基复合材料的聚焦离子束-透射电镜(FIB-TEM)测试中，颗粒切面的 能谱面扫显示颗粒内部硅元素、碳元素、A元素、氧元素均匀分布；
硅基复合材料的微观结构为多相弥散结构；
硅基复合材料颗粒的平均粒径D 50为1nm-100μm，比表面积为0.5m 2/g-40m 2/g；所述碳原子的质量占硅基复合材料质量的0.1％-40％，优选为0.5％-10％；A元素的质量占复合颗粒质量的3％-40％。
在以上材料的外层还可以包覆有碳包覆层，碳包覆层的质量占硅基复合材料质量的0-20％，优选的，碳包覆层的质量占硅基复合材料质量的0-10％。
本发明上述均匀改性的硅基复合材料，可以通过一步气相沉积法或两步气相沉积法获得。
一步气相沉积法的步骤如图1所示，包括：
步骤110，按所需用量将硅粉末、二氧化硅粉末、单质A粉末和/或A的氧化物粉末混合均匀，并置于真空炉中；
步骤120，真空炉减压后，加热至1200℃-1700℃，得到含硅元素、氧元素、A元素的混合蒸气；
其中，真空炉减压至300Pa以下。
步骤130，在保护气氛下，向真空炉中通入含碳气源，与所述混合蒸气进行气相混合反应1-24小时；
其中，保护气氛可以为N 2或Ar气氛。含碳气源包括：甲烷、丙烷、丁烷、乙炔、乙烯、丙烯、丁二烯或一氧化碳中的一种或多种。
步骤140，将气相混合反应得到的物料冷却至室温，并出料粉碎筛分，即得到碳元素以原子尺度均匀弥散分布的SiC xA yO z硅基复合材料。
两步气相沉积法的步骤如图2所示，包括：
步骤210，按所需用量将硅粉末、二氧化硅粉末混合均匀，并置于真空炉中；
步骤220，真空炉减压后，加热至1200℃-1700℃，得到含硅元素、氧元 素的混合蒸气；
其中，真空炉减压至300Pa以下。
步骤230，在保护气氛下，向真空炉中通入含碳气源，与所述混合蒸气进行气相混合反应1-24小时；
其中，保护气氛可以为N 2或Ar气氛。含碳气源包括：甲烷、丙烷、丁烷、乙炔、乙烯、丙烯、丁二烯或一氧化碳中的一种或多种。
步骤240，将气相混合反应得到的物料冷却至室温，并出料粉碎筛分，即得到碳元素以原子尺度均匀弥散分布的SiC xO z复合材料；
步骤250，将SiC xO z与单质A粉末和/或A的氧化物粉末混合均匀，置于高温炉中，在600℃-1500℃热处理2-24小时，即得到碳元素以原子尺度均匀弥散分布的SiC xA yO z硅基复合材料。在以上两种方法的基础上，进一步的，如果是制备外部还具有碳包覆层的硅基复合材料，则还可通过对粉碎后的物料进行碳包覆、分级，得到硅基复合材料。碳包覆的具体方法可以包括气相包覆、液相包覆、固相包覆中的至少一种。以上方法为制备电池材料过程中常用的包覆方法，在此不再展开说明。
本发明提供的具有碳元素以原子尺度均匀弥散分布在颗粒内部的硅基复合材料，通过C元素与A元素的体相掺杂分布，改善了硅基材料的体相导电性，为硅基材料的体积膨胀提供了体相均匀分布的缓冲空间，提高了材料的快充性能、首次库伦效率和循环稳定性。
本发明提出的硅基复合材料可用于制备负极片应用在锂电池中。
为更好的理解本发明提供的技术方案，下述以多个具体实例分别说明应用本发明上述实施例提供的方法制备硅基复合材料的具体过程，以及将其应用于锂二次电池的方法和特性。
实施例1
将1kg硅粉、1kg二氧化硅和0.3kg氧化铜的混合粉末置于高温反应 炉内，抽真空至50Pa,加热升温至1500℃变为蒸气。在氩气气流下同时缓慢通入1.6L甲烷进行反应3小时，冷却至室温。出料粉碎后即得到内部碳元素、铜元素以原子级均匀弥散分布的硅基复合材料。用碳硫分析仪测试其中碳含量为1.5％。
将得到的硅基复合材料进行FIB-TEM测试，通过能谱检测观察颗粒内部元素分布情况。图3为FIB-TEM能谱面扫图。从图2能谱元素面扫可知，Si、C、Cu、O四种元素在颗粒中均匀分布。
之后对硅基复合材料进行碳包覆，将2kg物料置于回转炉在保护气氩围下升温至1000℃，按体积比1：1通入氩气和丙烯进行气相包覆，保温2小时关闭有机气源，降温出料分级后，即得到含碳包覆层的硅基复合材料，其中总含碳量为4.5％。
将上述的含碳包覆层的硅基复合材料作为负极材料，与导电添加剂导电炭黑(SP)，粘接剂聚偏氟乙烯(PVDF)按照比例95％：2％：3％称量好，在室温下，打浆机中进行浆料制备。将制备好的浆料均匀涂布于铜箔上。50℃下在鼓风干燥箱中烘干2小时后，裁剪为8×8mm的极片，在真空干燥箱中100℃下抽真空烘干10个小时。将烘干后的极片，随即转移入手套箱中备用用以组装电池。
模拟电池的装配是在含有高纯Ar气氛的手套箱内进行，用金属锂作为对电极，1摩尔的LiPF 6在碳酸乙烯酯/碳酸二甲酯(EC/DMCv:v＝1：1)中的溶液作为电解液，装配成电池。使用充放电仪进行恒流充放电模式测试，放电截至电压为0.005V，充电截至电压为1.5V，第一周充放电测试C/10电流密度下进行，第二周放电测试在C/10电流密度下进行。初始效率、0.1C可逆容量、0.1C倍率下循环性能测试结果列于表1中。
实施例2
将1kg硅粉和1kg二氧化硅混合粉末置于真空炉中，抽真空至50Pa,加热升温至1500℃变为蒸气。随后在氩气气流下同时缓慢通入1.6L甲烷 进行反应3小时，冷却至室温。出料粉碎后即得到内部碳元素以原子级均匀弥散分布的硅基材料粉末。用碳硫分析仪测试其中碳含量为1.8％。
将得到的内部碳元素以原子级均匀弥散分布的硅基材料粉末和氧化铜按照摩尔比1：0.4混合均匀，之后在1000℃下热处理4小时，得到内部含碳元素、铜元素的硅基复合材料。
之后对上述材料进行碳包覆。将2kg硅基复合材料置于回转炉在保护气氩围下升温至1000℃，按体积比1：1通入氩气和丙烯进行气相包覆，保温2小时关闭有机气源。降温出料分级后，即得到含碳包覆层的硅基复合材料，其中总含碳量为4.6％。
负极极片的制备过程，电池装配以及电池测试同实施例1。初始效率、0.1C可逆容量、0.1C倍率下循环性能测试结果列于表1中。
实施例3
将3kg硅粉、3kg二氧化硅、1kg氧化硼的混合粉末置于真空炉中，抽真空至100Pa,加热升温至1350℃变为蒸气,在氩气流下同时缓慢通入23.4L丙烷进行反应8小时，冷却至室温。出料粉碎后即得到内部碳元素、硼元素以原子级均匀弥散分布的硅基复合材料。用碳硫分析仪测试其中碳含量为2.0％。
之后对其进行碳包覆，将2kg物料置于回转炉中，在保护气氩围下升温至900℃，按体积比1：1通入氩气和与氩气等量的丙烯和甲烷混合气体进行气相包覆，其中丙烯和甲烷体积比为2：3。保温3小时关闭有机气源，降温出料分级后，即得到含碳包覆层的硅基复合材料，其中总含碳量为4.7％。
负极极片的制备过程，电池装配以及电池测试同实施例1。初始效率、0.1C可逆容量、0.1C倍率下循环性能测试结果列于表1中。
实施例4
将2kg硅粉和2kg二氧化硅混合粉末置于真空炉内，抽真空至150Pa, 加热升温至1400℃变为蒸气。在氩气流下同时缓慢通入1L丙烯进行反应5小时，冷却至室温。出料粉碎后即得到内部碳元素以原子级均匀弥散分布的硅基复合材料。用碳硫分析仪测试其中碳含量为2.0％。
将得到的内部碳元素以原子级均匀弥散分布的硅基复合材料和金属铝按照摩尔比2：1混合均匀，之后在1200℃下热处理4小时，得到内部含碳元素、铜元素的硅基复合材料。
负极极片的制备过程，电池装配以及电池测试同实施例1。初始效率、0.1C可逆容量、0.1C倍率下循环性能测试结果列于表1中。
实施例5
将3kg硅、3kg二氧化硅、1kg金属镁的混合粉末置于真空炉中，抽真空至150Pa,加热升温至1400℃变为蒸气,在氩气流下同时缓慢11.7L乙炔和5L甲烷的混合气进行反应4小时，冷却至室温。出料粉碎后即得到内部碳元素、镁元素以原子级均匀弥散分布的硅基复合材料。用碳硫分析仪测试其中碳含量为1.8％。
之后对其进行碳包覆，将2kg物料置于回转炉在保护气氩围下升温至1100℃，按体积比1：1通入氩气和与氩气等量的丙烯和甲烷混合气体进行气相包覆，其中丙烯和甲烷体积比为2：3。保温3小时关闭有机气源，降温出料分级后，即得到含碳包覆层的硅基复合材料，其中总含碳量为6.5％。
负极极片的制备过程，电池装配以及电池测试同实施例1。初始效率、0.1C可逆容量、0.1C倍率下循环性能测试结果列于表1中。
实施例6
将5kg硅粉和5kg二氧化硅混合粉末置于真空炉内，抽真空至150Pa,加热升温至1400℃变为蒸气。在氩气流下同时缓慢通入1L的乙炔气体进行反应5小时，冷却至室温。出料粉碎后即得到内部碳元素以原子级均匀弥散分布的硅基材料粉末。用碳硫分析仪测试其中碳含量为0.8％。
将得到的内部碳元素以原子级均匀弥散分布的硅基材料粉末和氧化 钙按照摩尔比3：1混合均匀，之后在1200℃下热处理4小时，得到内部含碳元素、钙元素的硅基复合材料。
之后对其进行碳包覆，将1.5kg物料置于回转炉在保护气氩围下升温至850℃，按体积比1：1通入氩气和与氩气等量的丙烷进行气相包覆，保温1.5小时关闭有机气源，降温出料分级后，即得到含碳包覆层的硅基复合材料，其中总含碳量为5.5％。
负极极片的制备过程，电池装配以及电池测试同实施例1。初始效率、0.1C可逆容量、0.1C倍率下循环性能测试结果列于表1中。
实施例7
将2kg硅、3kg二氧化硅、0.5kg金属铁的混合粉末置于真空炉中，抽真空至100Pa,加热升温至1600℃变为蒸气,在氩气流下同时缓慢通入1L的丁烷气体进行反应3小时，冷却至室温。出料粉碎后即得到内部碳元素、铁元素以原子级均匀弥散分布的硅基复合材料。用碳硫分析仪测试其中碳含量为2％。
之后对其进行碳包覆，将2kg物料置于回转炉在保护气氩围下升温至700℃，按体积比1：2通入氩气和乙炔进行气相包覆。保温2小时关闭有机气源，降温出料分级后，即得到含碳包覆层的硅基复合材料，其中总含碳量为4.5％。
负极极片的制备过程，电池装配以及电池测试同实施例1。初始效率、0.1C可逆容量、0.1C倍率下循环性能测试结果列于表1中。
实施例8
将3kg硅粉和5kg二氧化硅混合粉末置于真空炉内，抽真空至150Pa,加热升温至1400℃变为蒸气。在氩气流下同时缓慢通入1.5L的丁二烯气体进行反应6小时，冷却至室温。出料粉碎后即得到内部碳元素以原子级均匀弥散分布的硅基材料粉末。用碳硫分析仪测试其中碳含量为1.3％。
将得到的内部碳元素以原子级均匀弥散分布的硅基材料粉末和金属钴 按照摩尔比5：1混合均匀，之后在1200℃下热处理4小时，得到内部含碳元素、钴元素的硅基复合材料。
之后对其进行碳包覆，将1.5kg物料置于回转炉在保护气氩围下升温至850℃，按体积比1：1通入氩气和与氩气等量的乙炔丙烷进行气相包覆。其中乙炔和丙烷体积比为3：1，保温3小时关闭有机气源，降温出料分级后，即得到含碳包覆层的硅基复合材料，其中总含碳量为5.5％。
负极极片的制备过程，电池装配以及电池测试同实施例1。初始效率、0.1C可逆容量、0.1C倍率下循环性能测试结果列于表1中。
实施例9
将5kg硅、4kg二氧化硅、1kg金属镍的混合粉末置于真空炉中，抽真空至100Pa,加热升温至1700℃变为蒸气,在氩气流下同时缓慢通入1.4L的一氧化碳气体进行反应12小时，冷却至室温。出料粉碎后即得到内部碳元素、铁元素以原子级均匀弥散分布的硅基复合材料。用碳硫分析仪测试其中碳含量为0.6％。
之后对其进行碳包覆，将2kg物料置于回转炉在保护气氩围下升温至600℃，按体积比1：3通入氩气和乙炔进行气相包覆。保温2小时关闭有机气源，降温出料分级后，即得到含碳包覆层的硅基复合材料，其中总含碳量为3.5％。
负极极片的制备过程，电池装配以及电池测试同实施例1。初始效率、0.1C可逆容量、0.1C倍率下循环性能测试结果列于表1中。
实施例10
将5kg硅粉和5kg二氧化硅混合粉末置于真空炉内，抽真空至150Pa,加热升温至1400℃变为蒸气。在氩气流下同时缓慢通入2.0L的一氧化碳和1.2L的乙炔混合气体进行反应10小时，冷却至室温。出料粉碎后即得到内部碳元素以原子级均匀弥散分布的硅基材料粉末。用碳硫分析仪测试其中碳含量为3％。
将得到的内部碳元素以原子级均匀弥散分布的硅基材料粉末和金属锌按照摩尔比2：1混合均匀，之后在1200℃下热处理4小时，得到内部含碳元素、锌元素的硅基负极材料。
之后对其进行碳包覆，将2kg物料与石油沥青按照10:1的质量比进行混合，置于高温炉中，氮气氛围900℃热处理2小时，降温出料分级后，即得到含碳包覆层的硅基复合材料，其中总含碳量为4.2％。
将上述的含碳包覆层的硅基复合材料作为负极材料，与导电添加剂导电炭黑(SP)，粘接剂聚偏氟乙烯(PVDF)按照比例95％：2％：3％称量好。在室温下，打浆机中进行浆料制备。将制备好的浆料均匀涂布于铜箔上。50℃下在鼓风干燥箱中烘干2小时后，裁剪为8×8mm的极片，在真空干燥箱中100℃下抽真空烘干10个小时。将烘干后的极片，随即转移入手套箱中备用用以组装电池。
模拟电池的装配是在含有高纯Ar气氛的手套箱内进行，以上述电极作为负极，三元正极材料NCM811为对电极，以石榴石型Li 7La 3Zr 2O 12(LLZO)作为固态电解质，在手套箱中组装成全固态纽扣电池，对其进行充电，评价电化学性能。使用充放电仪进行恒流充放电模式测试，放电截至电压为0.005V，充电截至电压为1.5V，第一周充放电测试C/10电流密度下进行，第二周放电测试在C/10电流密度下进行。初始效率、0.1C可逆容量、0.1C倍率下循环性能测试结果列于表1中。
实施例11
将4kg硅、4kg二氧化硅、2kg氧化铜的混合粉末置于真空炉中，抽真空至100Pa,加热升温至1700℃变为蒸气,在氩气流下同时缓慢通入0.9L的甲烷、1.2L的丙烯、1.7L的丙烷混合气体进行反应6小时，冷却至室温。出料粉碎后即得到内部碳元素、铜元素以原子级均匀弥散分布的硅基复合材料。用碳硫分析仪测试其中碳含量为3.6％。
之后对其进行碳包覆，将粉碎后的3kg样品与酚醛树脂按照20:1的比 例溶于酒精溶剂，搅拌6小时形成均匀浆料。之后将浆料直接烘干，并置于高温炉中，在900℃，氮气保护气氛下将混合料烧结2小时，冷却后，进行分级、筛分，即得到含碳包覆层的硅基复合材料，其中总含碳量为6.5％。
将上述的含碳包覆层的硅基复合材料作为负极材料，与导电添加剂导电炭黑(SP)，粘接剂聚偏氟乙烯(PVDF)按照比例95％：2％：3％称量好。在室温下，打浆机中进行浆料制备。将制备好的浆料均匀涂布于铜箔上。50摄氏度温度下在鼓风干燥箱中烘干2小时后，裁剪为8×8mm的极片，在真空干燥箱中100摄氏度温度下抽真空烘干10个小时。将烘干后的极片，随即转移入手套箱中备用用以组装电池。
模拟电池的装配是在含有高纯Ar气氛的手套箱内进行，以上述电极作为负极，三元正极材料NCM811为对电极，以聚烯烃基凝胶聚合物电解质膜作为半固态电解质，在手套箱中组装成半固态纽扣电池，对其进行充电，评价电化学性能。使用充放电仪进行恒流充放电模式测试，放电截至电压为0.005V，充电截至电压为1.5V，第一周充放电测试C/10电流密度下进行，第二周放电测试在C/10电流密度下进行。初始效率、0.1C可逆容量、0.1C倍率下循环性能测试结果列于表1中。
实施例12
将3kg硅粉和5kg二氧化硅混合粉末置于真空炉内，抽真空至150Pa,加热升温至1500℃变为蒸气。在氩气流下同时缓慢通入1.7L的甲烷、1.5L的丙烯混合气体进行反应3小时，冷却至室温。出料粉碎后即得到内部碳元素以原子级均匀弥散分布的硅基材料粉末。用碳硫分析仪测试其中碳含量为1.5％。
将得到的内部碳元素以原子级均匀弥散分布的硅基材料粉末和金属锗按照摩尔比5：1混合均匀，之后在1200℃下热处理4小时，得到内部含碳元素、锌元素的硅基复合材料。
负极极片的制备过程，电池装配以及电池测试同实施例1。初始效率、0.1C可逆容量、0.1C倍率下循环性能测试结果列于表1中。
实施例13
将4kg硅、4kg二氧化硅、2kg氧化锡的混合粉末置于真空炉中，抽真空至100Pa,加热升温至1700℃变为蒸气,在氩气流下缓慢通入5L乙炔和5L乙烯的混合气，混合反应6小时后冷却至室温。出料粉碎后即得到内部碳元素、锡元素以原子级均匀弥散分布的硅基复合材料。用碳硫分析仪测试其中碳含量为3％。
负极极片的制备过程，电池装配以及电池测试同实施例1。初始效率、0.1C可逆容量、0.1C倍率下循环性能测试结果列于表1中。
实施例14
将5kg硅粉和5kg二氧化硅混合粉末置于真空炉内，抽真空至150Pa,加热升温至1500℃变为蒸气。在氩气流下同时缓慢通入2L丁二烯气体进行反应4小时，冷却至室温。出料粉碎后即得到内部碳元素以原子级均匀弥散分布的硅基材料粉末。用碳硫分析仪测试其中碳含量为0.5％。
将得到的内部碳元素以原子级均匀弥散分布的硅基材料粉末和氧化锂按照摩尔比5：1混合均匀，之后在1000℃下热处理2小时，得到内部含碳元素、锂元素的硅基复合材料。
负极极片的制备过程，电池装配以及电池测试同实施例1。初始效率、0.1C可逆容量、0.1C倍率下循环性能测试结果列于表1中。
对比例1
将1kg硅粉和1kg二氧化硅混合粉末置于真空炉中，抽真空至50Pa,加热升温至1500℃变为蒸气。出料粉碎后即得氧化亚硅负极材料。之后对其进行碳包覆。将2kg物料置于回转炉在保护气氩围下升温至1000℃，按体积比1：1通入氩气和丙烯进行气相包覆，保温2小时关闭有机气源。降温出料分级后，即得到含碳包覆层的硅基负极材料，其中碳含量为3％。
负极极片的制备过程，电池装配以及电池测试同实施例1。初始效率、0.1C可逆容量、0.1C倍率下循环性能测试结果列于表1中。
对比例2
将1kg硅粉、1kg二氧化硅和0.3kg氧化铜的混合粉末置于真空炉中，抽真空至50Pa,加热升温至1500℃变为蒸气，反应3小时后，冷却至室温。出料粉碎后即得到内部铜元素以原子级均匀弥散分布的氧化亚硅负极材料。之后对其进行碳包覆。将2kg物料置于回转炉在保护气氩围下升温至1000℃，按体积比1：1通入氩气和丙烯进行气相包覆，保温2小时关闭有机气源。降温出料分级后，即得到含碳包覆层的氧化亚硅负极材料，其中总含碳量为3％。
负极极片的制备过程，电池装配以及电池测试同实施例1。初始效率、0.1C可逆容量、0.1C倍率下循环性能测试结果列于表1中。
对比例3
将1kg硅粉和1kg二氧化硅的混合粉末置于真空炉中，抽真空至50Pa,加热升温至1500℃变为蒸气。随后在氩气气流下同时缓慢通入1.6L甲烷进行反应3小时，冷却至室温。出料粉碎后即得到内部碳元素以原子级均匀弥散分布的氧化亚硅负极材料。用碳硫分析仪测试其中碳含量为1.7％。之后对其进行碳包覆。将2kg物料置于回转炉在保护气氩围下升温至1000℃，按体积比1：1通入氩气和丙烯进行气相包覆，保温2小时关闭有机气源。降温出料分级后，即得到含碳包覆层的氧化亚硅负极材料，其中总含碳量为4.7％。
负极极片的制备过程，电池装配以及电池测试同实施例1。初始效率、0.1C可逆容量、0.1C倍率下循环性能测试结果列于表1中。
将实施例1-14以及对比例1-3中的负极材料分别进行初始效率、0.1C可逆容量、0.1C倍率下循环性能等测试结果如下：
Figure PCTCN2021111677-appb-000001
表1
由表中对比例1-3的数据可以看出，对比例2对氧化亚硅进行了铜元素掺杂，相较于对比例1明显提升了首次效率，但是循环性能出现了劣势。对比例3对氧化亚硅进行了碳元素的掺杂，相较于对比例1明显提升了循环容量保持率，但是首次首次效率出现了略微的劣势。实施例1-14通过对材料进行碳元素、A元素的体相掺杂，增加了颗粒内部的导电性，为材料的膨胀提供了缓冲空间，同时提升了材料的首次效率和循环寿命。
以上所述的具体实施方式，对本发明的目的、技术方案和有益效果进行了进一步详细说明，所应理解的是，以上所述仅为本发明的具体实施方式而已，并不用于限定本发明的保护范围，凡在本发明的精神和原则之内，所做的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。

Claims (10)

  1. 一种均匀改性的硅基复合材料，其特征在于，所述硅基复合材料的通式为SiC xA yO z；0＜x＜20；0＜y＜10；0＜z＜10；
    其中，A为B、Al、Mg、Ca、Fe、Co、Ni、Cu、Zn、Ge、Sn、Li中的一种或多种，C以原子尺度均匀弥散分布在硅基复合材料的颗粒内部，且无20nm以上的碳元素团聚；部分或所有碳原子与硅原子结合形成无序的Si-C键；在硅基复合材料的聚焦离子束-透射电镜FIB-TEM测试中，颗粒切面的能谱面扫显示颗粒内部硅元素、碳元素、A元素、氧元素均匀分布；
    所述硅基复合材料的微观结构为多相弥散结构；
    所述硅基复合材料颗粒的平均粒径D 50为1nm-100μm，比表面积为0.5m 2/g-40m 2/g；所述碳原子的质量占硅基复合材料质量的0.1％-40％；所述A元素的质量占复合颗粒质量的3％-40％。
  2. 根据权利要求1所述的硅基复合材料，其特征在于，所述硅基复合材料的外部还具有碳包覆层；所述碳包覆层的质量占所述硅基复合材料质量的0-20％。
  3. 根据权利要求2所述的硅基复合材料，其特征在于，所述碳原子的质量占所述硅基复合材料质量的0.5％-10％；所述碳包覆层的质量占所述硅基复合材料质量的0-10％。
  4. 一种上述权利要求1-3任一所述的均匀改性的硅基复合材料的制备方法，其特征在于，所述制备方法包括一步气相沉积法或两步气相沉积法。
  5. 根据权利要求4所述的制备方法，其特征在于，所述一步气相沉积法具体包括：
    按所需用量将硅粉末、二氧化硅粉末、单质A粉末和/或A的氧化物粉末混合均匀，并置于真空炉中；
    真空炉减压后，加热至1200℃-1700℃，得到含硅元素、氧元素、A元素的混合蒸气；
    在保护气氛下，向真空炉中通入含碳气源，与所述混合蒸气进行气相混合反应1-24小时；
    将所述气相混合反应得到的物料冷却至室温，并出料粉碎筛分，即得到碳元素以原子尺度均匀弥散分布的SiC xA yO z硅基复合材料。
  6. 根据权利要求4所述的制备方法，其特征在于，所述两步气相沉积法具体包括：
    按所需用量将硅粉末、二氧化硅粉末混合均匀，并置于真空炉中；
    真空炉减压后，加热至1200℃-1700℃，得到含硅元素、氧元素的混合蒸气；
    在保护气氛下，向真空炉中通入含碳气源，与所述混合蒸气进行气相混合反应1-24小时；
    将所述气相混合反应得到的物料冷却至室温，并出料粉碎筛分，即得到碳元素以原子尺度均匀弥散分布的SiC xO z复合材料；
    将SiC xO z与单质A粉末和/或A的氧化物粉末混合均匀，置于高温炉中，在600℃-1500℃热处理2-24小时，即得到碳元素以原子尺度均匀弥散分布的SiC xA yO z硅基复合材料。
  7. 根据权利要求5或6所述的制备方法，其特征在于，所述含碳气源包括：甲烷、丙烷、丁烷、乙炔、乙烯、丙烯、丁二烯或一氧化碳中的一种或多种。
  8. 根据权利要求5或6所述的制备方法，其特征在于，在将所述物料冷却至室温，并出料粉碎筛分之后，所述制备方法还包括：对所述筛分后的物料进行碳包覆；其中，所述碳包覆包括：气相包覆、液相包覆、固相包覆中的至少一种。
  9. 一种包括上述权利要求1-3任一所述的均匀改性的硅基复合材料的负极片。
  10. 一种包括上述权利要求9所述的负极片的锂电池。
PCT/CN2021/111677 2021-06-16 2021-08-10 一种均匀改性的硅基复合材料及其制备方法和应用 Ceased WO2022262096A1 (zh)

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