WO2024016900A1 - 复合材料及其制备方法、二次电池和电子设备 - Google Patents

复合材料及其制备方法、二次电池和电子设备 Download PDF

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WO2024016900A1
WO2024016900A1 PCT/CN2023/099975 CN2023099975W WO2024016900A1 WO 2024016900 A1 WO2024016900 A1 WO 2024016900A1 CN 2023099975 W CN2023099975 W CN 2023099975W WO 2024016900 A1 WO2024016900 A1 WO 2024016900A1
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composite material
porous carbide
silicon material
carbide support
silicon
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PCT/CN2023/099975
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English (en)
French (fr)
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雷丹
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Oppo广东移动通信有限公司
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Publication of WO2024016900A1 publication Critical patent/WO2024016900A1/zh

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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
    • 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
    • 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
    • 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
    • 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
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • 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 the field of energy, and in particular, to composite materials and preparation methods thereof, secondary batteries, and electronic devices.
  • graphite is usually used as anode active material to store and release lithium during the charge and discharge process.
  • the theoretical specific capacity of graphite anode material is 372mAh/g, and the current development of graphite is close to its theoretical value.
  • silicon As a new negative electrode material, silicon itself has an ultra-high theoretical specific capacity (about 4200mAh/g) and has the potential to effectively increase the energy density of the battery.
  • the application proposes a composite material, including: a porous carbide carrier, the porous carbide carrier includes a carbon element and at least one first element; a silicon material, the silicon material is supported on the There are pores in the pores of the porous carbide carrier that are not filled with the silicon material.
  • the application proposes a method for preparing the aforementioned composite material, including: providing a porous carbide carrier precursor, the porous carbide carrier precursor including a carbon element and at least one first element; Part of the first element in the porous carbide carrier precursor is removed to obtain a porous carbide carrier; and a silicon material deposition process is performed on the porous carbide carrier to obtain the composite material.
  • the present application proposes a secondary battery, including a negative electrode sheet.
  • the negative electrode sheet includes the aforementioned composite material, and/or a composite material prepared using the aforementioned method.
  • the present application proposes an electronic device, including the aforementioned secondary battery.
  • Figure 1 shows a schematic structural diagram of a composite material according to an embodiment of the present application
  • Figure 2 shows a schematic structural diagram of a composite material according to yet another embodiment of the present invention.
  • Figure 3 shows a schematic structural diagram of a composite material according to another embodiment of the present invention.
  • Figure 4 shows a schematic flow chart of a method for preparing composite materials according to an embodiment of the present invention.
  • SEI film Solid Electrolyte Interphase, solid electrolyte interface film
  • This application aims to alleviate or solve the above-mentioned problems at least to a certain extent.
  • the present application proposes a composite material, with reference to Figures 1 and 2, including: a porous carbide carrier 100, which includes a carbon element and at least one first element; a silicon material 200, The silicon material 200 is supported in the pores 110 of the porous carbide carrier, and the pores 110 of the porous carbide carrier 100 have pores that are not filled with the silicon material 200 .
  • the excellent conductivity of the porous carbide carrier provides a conductive network for the silicon material, improves the conductivity of the composite material, thereby ensuring the effective transmission of electrons.
  • the pore structure inside the porous carbide carrier also provides a space for the shrinkage of the silicon material during lithium insertion and delithiation. The expansion provides expansion space, thereby improving the structural stability of the silicon material and reducing the expansion of the composite material, making the composite material have a more stable structure and better cycle stability when used as electrode materials.
  • the carbon-silicon composite material is used as an electrode material, it is prone to damage during the cycle, resulting in poor cycle performance of the carbon-silicon composite material. Poor.
  • the porous carbon material used as a carrier has an internal pore structure with a larger pore diameter (about 5nm-20nm) and poor pore size distribution uniformity. Problems such as this will cause the silicon deposited in the pores to be larger in size, and the volume ratio of silicon to pores in different pores will be less uniform. Carbon-silicon composite materials are more likely to be damaged when used as electrode materials, and due to the porous carbon materials Its own conductivity is poor, which will hinder the electron conduction in the carbon-silicon composite material, causing the polarization of the carbon-silicon composite material to increase, making it more likely to undergo lithium precipitation and other deterioration reactions.
  • a porous carbide carrier is used as the substrate for silicon material deposition to support the silicon material, thereby maintaining structural integrity and inhibiting the expansion of the overall composite material particles when the silicon material expands.
  • the good conductivity of the porous carbide carrier to provide a conductive network for the silicon material, the effective transmission of electrons is improved.
  • the pore structure inside the carbide carrier that is not filled with silicon material provides space for the silicon material to expand, reducing the expansion of the composite material particles, thereby reducing the expansion of the composite material when it is applied to the battery pole piece.
  • the structure of the porous carbide support is not particularly limited, as long as the porous carbide support has better conductivity than the porous carbon material through the addition of the first element, for example, when the chemical formula of the porous carbide support is X ⁇ Y ⁇ C ⁇ , where X and Y are the first elements, ⁇ 0, ⁇ 0, ⁇ >0, and when ⁇ and ⁇ are not 0 at the same time, X and Y They may each independently include at least one of V, Ti, Si, W, Ta, Nb, Zr, B, Mo, Fe and Al, and X and Y are different.
  • the porous carbide carrier When the chemical formula of the porous carbide carrier satisfies the above conditions, the porous carbide carrier has good electrical conductivity and lower resistivity than amorphous carbon and graphite, thereby providing a conductive network for the silicon material and improving the electronics transmission efficiency.
  • the pore size distribution of the porous carbide support is not particularly limited.
  • the D90 pore size of the porous carbide support may be 1 nm-10 nm.
  • the D90 pore size of the porous carbide support may be 0.1 nm- 3nm.
  • the size of the pores of the unfilled silicon material in the pores is also relatively uniform, so that the volume ratio of the volume of the silicon material in different pores to the volume of the unfilled silicon material is narrower, maintaining the uniformity of the internal expansion performance of the material, and effectively improving the circulation of the material performance.
  • the pore size distribution of the porous carbide carrier is not within the above range, the pore size distribution of the porous carbide carrier is uneven, resulting in a smaller volume of the silicon material in the larger pores compared with the volume of the pores not filled with silicon material.
  • the space in the pores of the porous carbide carrier cannot be fully utilized to deposit more silicon material, reducing the specific capacity of the material; the volume of the silicon material in the smaller pores is larger than the volume of the pores that are not filled with silicon material, making the pores
  • the space for expansion of the inner silicon material is small, and it is easy to squeeze the porous carbide carrier skeleton structure or the structure of the surrounding silicon material during the expansion process, causing damage to the internal structure of the composite material and reducing cycle stability.
  • the volume porosity of the porous carbide support is not particularly limited.
  • the volume porosity of the porous carbide support may be no less than 50%.
  • the total pore volume of the porous carbide support may be 0.1 cm 3 /g-5.5cm 3 /g.
  • the size of the silicon material in the pores of the porous carbide carrier is not particularly limited.
  • the thickness of the silicon material in the direction from the pore wall to the center of the hole, can be 0.1nm-10nm, preferably Ground, the thickness of silicon material can be 0.1nm-3nm.
  • the nanoscale size of the silicon material can reduce its crushing or structural damage when lithium is embedded and expands, ensuring its cycle stability, and can also increase its amorphous degree, thereby reducing Its expansion when lithium is embedded improves cycle performance.
  • the thickness of the silicon material is the same as the wall thickness of the hollow sphere when the wall of the hole points in the direction of the center of the hole; referring to Figure 2, when the silicon material is in the shape of a sphere, In the direction from the hole wall to the hole center, the thickness of the silicon material is the same as the diameter of the silicon material.
  • the mass fraction of the silicon material in the composite material is not particularly limited.
  • the mass fraction of the silicon material in the composite material may be 20wt%-90wt%.
  • the mass fraction of silicon material in the composite material is less than 20wt%, the volume ratio of the volume of silicon material in the pores of the porous carbide carrier to the pores not filled with silicon material is too small, and the content of silicon material in the pores of the porous carbide carrier is too low.
  • Composite materials have lower specific capacities.
  • the mass fraction of silicon material in the composite material is greater than 90wt%, the volume ratio of the volume of silicon material in the pores of the porous carbide carrier to the pores not filled with silicon material is too large, and the content of silicon material in the pores of the porous carbide carrier is too large. As a result, the volume of the pores that are not filled with silicon material in the pores is too small, which makes the space for the silicon material in the pores to expand. During the expansion process, it is easy to squeeze the porous carbide carrier skeleton structure or the structure of the surrounding silicon material, resulting in internal damage to the composite material. Structural damage.
  • the volume ratio of the volume of the silicon material in the pores of the porous carbide carrier to the volume of the pores that are not filled with silicon material is not particularly limited, as long as the pores of the porous carbide carrier have The pores of the silicon material are not filled.
  • the relationship between V 1 and V 2 can satisfy: V 1 ⁇ V 2 ⁇ 4V 1 .
  • the silicon material in the pores of the porous carbide carrier does not completely fill the pores of the porous carbide carrier, but leaves certain pores.
  • the pores serve as buffer spaces and can play a buffering role when the silicon material expands and contracts, making the silicon When the material expands, it will not squeeze and destroy the porous carbide carrier skeleton, thereby causing expansion and destruction of the composite material, greatly reducing the expansion rate of the composite material, thereby ensuring its structural stability and integrity when used in battery negative electrodes.
  • the shape of the silicon material is not particularly limited.
  • the shape of the silicon material can be spherical or hollow spherical.
  • the structure of the composite material is not particularly limited.
  • the composite material may further include: a carbon coating layer 300 covering the outer surface of the porous carbide carrier 100, This can reduce the specific surface area of the composite material, reduce the exposure of silicon on the surface of the composite material, improve the conductivity of the composite material, and prevent the structural damage of the composite material caused by the expansion of the silicon material.
  • the thickness of the carbon coating layer is not particularly limited.
  • the thickness of the carbon coating layer may be 5 nm-2000 nm.
  • this application proposes a method for preparing the aforementioned composite material, so that the aforementioned composite material can be prepared by a relatively simple method. Specifically, with reference to Figure 4, it includes:
  • a porous carbide carrier precursor is provided in this step.
  • the type of the porous carbide carrier precursor is not particularly limited, as long as the porous carbide carrier precursor includes a carbon element and at least one first element.
  • the porous carbide support precursor may include VC, TiC, SiC, WC, TaC, NbC, ZrC, V 2 C, W 2 C, B 4 C, Mo 2 C, Fe 3 C, Ta 2 C, At least one of Nb 2 C, Ti 2 AlC, Ti 3 SiC 2 and Ti 3 AlC 2 .
  • part of the first element in the porous carbide carrier precursor is removed to obtain a porous carbide carrier.
  • removing part of the first element in the porous carbide carrier precursor may include:
  • the porous carbide carrier precursor is placed in a chlorine atmosphere and heated.
  • the chlorine gas reacts with the non-carbon elements in the porous carbide carrier precursor to be released, thereby forming a porous carbide carrier.
  • the porous carbide carrier precursor After etching, the porous carbide carrier precursor maintains ⁇ 0 , ⁇ 0 and ⁇ and ⁇ in The etched pure carbon skeleton has better electrical conductivity, thereby utilizing the uniform distribution of X, Y and C in the porous carbide carrier X ⁇ Y ⁇ C ⁇ , and the X element and Y element can be formed by etching the Nanoscale, narrow pore size distribution pore structure, subsequent silicon material deposition can control the size of the deposited silicon material to the nanoscale, and the volume ratio of the silicon material in different pores to the volume of the pores not filled with silicon material is narrowly distributed , to maintain the uniformity of expansion performance within the composite material.
  • the non-carbon element removal reaction will not completely remove the non-carbon elements in the porous carbide support precursor, so that there are still some non-carbon elements.
  • the carbon element is retained within the porous carbide support.
  • the porous carbide support is subjected to a silicon material deposition process to obtain a composite material.
  • the silicon material deposition process may include chemical vapor deposition.
  • the deposition gas of chemical vapor deposition is not particularly limited as long as it is a silicon-containing gas.
  • the deposition gas of the silicon material deposition process may include a mixture of silane and argon. gas.
  • Silicon-containing gas can deposit silicon material in the pores of porous carbide carriers at high temperatures. By controlling the deposition process and reaction parameters, partial filling of the silicon material in the pores can be easily achieved, so that a certain amount of silicon material is retained in the pores. The pore structure of unfilled silicon material.
  • the silicon material deposition process may further include: carbon coating the porous carbide support.
  • the carbon coating process may Including chemical vapor deposition, the deposition gas of chemical vapor deposition may include alkane gas.
  • the present application proposes a secondary battery, including a negative electrode piece.
  • the negative electrode piece includes the aforementioned composite material, and/or a composite material prepared by the aforementioned method. Therefore, the secondary battery has all the features and advantages of the aforementioned composite materials and methods for preparing the composite materials, which will not be described again here.
  • the aforementioned composite material has a small expansion rate and a high specific capacity.
  • the structure of the battery and the SEI film (solid electrolyte) can be effectively improved.
  • the stability of the membrane) is of great significance to the improvement of cycle stability.
  • the present application proposes an electronic device, including the aforementioned secondary battery. Therefore, the electronic device has all the features and advantages of the aforementioned secondary battery, which will not be described again here.
  • the method for preparing composite materials is as follows:
  • Embodiment 3 is consistent with Embodiment 1, except that the carbon coating layer is formed after the silicon material deposition reaction. Specifically, methane gas is passed into the silicon-deposited material, and it is maintained at 800°C for pyrolysis for 2 hours to obtain a composite material with a carbon coating layer.
  • Example 4 is consistent with Example 1, except that the porous carbide precursor used is Mo 2 C to obtain a porous carbide carrier.
  • Example 5 is consistent with Example 1, except that the porous carbide precursor used is Fe 3 C to obtain a porous carbide carrier.
  • Example 6 is consistent with Example 1, except that the time for introducing chlorine gas is 2 hours to obtain a porous carbide carrier.
  • Comparative Example 1 is consistent with Example 1, except that the time for introducing chlorine gas is 5 hours to obtain a porous carbon support.
  • Comparative Example 2 remains the same as Example 1, except that 3% (v/v) silane gas (mixed argon gas) was introduced and maintained for 4 hours to obtain a porous carbon support.
  • Test method Mix the composite material with CMC, SBR, and SP in a ratio of 80:4:6:10 to make a negative electrode sheet and assemble it into a button half cell. Test the specific capacity and first effect of the first charge and discharge and after 50 cycles. capacity retention rate.
  • Example 1 The test results show that compared with Example 1, the chlorine reaction time of Comparative Example 1 is too long, and the non-carbon elements in the carbide are removed more completely.
  • the powder resistivity of the composite material obtained in Comparative Example 1 is 6.18 ⁇ cm, which is worse in electrical conductivity than the composite material obtained in Example 1; the 50-cycle retention rate is 86%, compared with the 94% retention rate in Example 1 The decline is obvious.
  • the silicon deposition time of Comparative Example 2 is too long, and the surface silicon content is 36.7%.
  • the silicon content has increased significantly, indicating that excessive silicon deposition has occurred, and the powder resistivity has significantly increased to 2.86. ⁇ cm, the 50-cycle cycle retention rate dropped to 82%, and the cycle performance dropped significantly.
  • references to the terms “one embodiment,” “another embodiment,” etc. means that a particular feature, structure, material, or characteristic described in connection with the embodiment is included in at least one embodiment of the present application. .
  • the schematic expressions of the above terms are not necessarily directed to the same embodiment or example.
  • the specific features, structures, materials or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
  • those skilled in the art may combine and combine different embodiments or examples and features of different embodiments or examples described in this specification unless they are inconsistent with each other.

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Abstract

本公开提供了复合材料及其制备方法、二次电池和电子设备，复合材料包括多孔碳化物载体，所述多孔碳化物载体包括碳元素以及至少一个第一元素；硅材，所述硅材负载在所述多孔碳化物载体的孔内，所述多孔碳化物载体的孔内具有未填充所述硅材的孔隙。

Description

复合材料及其制备方法、二次电池和电子设备 技术领域
本公开涉及能源领域，具体地，涉及复合材料及其制备方法、二次电池和电子设备。
背景技术
相关技术中通常使用石墨作为负极活性材料，用于在充放电过程中存储和释放锂，石墨负极材料的理论比容量为372mAh/g，目前石墨的开发已接近其理论值。为了进一步提升电池的能量密度，需要开发新型的具有更高比容量的负极材料。硅作为新型的负极材料，其本身具有超高理论比容量(约4200mAh/g)，具有有效提高电池的能量密度的潜能。
因此，目前的复合材料及其制备方法、二次电池和电子设备仍有待改进。
申请内容
在本申请的一个方面，本申请提出了一种复合材料，包括：多孔碳化物载体，所述多孔碳化物载体包括碳元素以及至少一个第一元素；硅材，所述硅材负载在所述多孔碳化物载体的孔内，所述多孔碳化物载体的孔内具有未填充所述硅材的孔隙。
在本申请的另一个方面，本申请提出了一种制备前述的复合材料的方法，包括：提供多孔碳化物载体前驱体，所述多孔碳化物载体前驱体包括碳元素以及至少一个第一元素；去除所述多孔碳化物载体前驱体中的部分所述第一元素，以获得多孔碳化物载体；对所述多孔碳化物载体进行硅材沉积处理，以获得所述复合材料。
在本申请的又一个方面，本申请提出了一种二次电池，包括负极极片，所述负极极片包括前述的复合材料，和/或，采用前述的方法制备得到的复合材料。
在本申请的又一个方面，本申请提出了一种电子设备，包括前述的二次电池。
附图说明
本申请的上述和/或附加的方面和优点从结合下面附图对实施例的描述中将变得明显和容易理解，其中：
图1显示了根据本申请一个实施例的复合材料的结构示意图；
图2显示了根据本发明又一个实施例的复合材料的结构示意图；
图3显示了根据本发明又一个实施例的复合材料的结构示意图；
图4显示了根据本发明一个实施例的制备复合材料的方法的流程示意图。
具体实施方式
下面详细描述本申请的实施例，所述实施例的示例在附图中示出，其中自始至终相同或类似的标号表示相同或类似的元件或具有相同或类似功能的元件。下面通过参考附图描述的实施例是示例性的，仅用于解释本申请，而不能理解为对本申请的限制。
本申请是基于发明人对于以下事实和问题的发现和认识做出的：
发明人发现，硅材料作为电极材料时，其在充放电嵌锂、脱锂的过程中会产生巨大的膨胀和收缩，容易导致硅材料的结构破坏、SEI膜(Solid Electrolyte Interphase，固体电解质界面膜)的损坏及反复生成，进而电池循环性能较差。
本申请旨在至少一定程度上缓解或解决上述提及问题。
在本申请的一个方面，本申请提出了一种复合材料，参考图1和图2，包括：多孔碳化物载体100，多孔碳化物载体100包括碳元素以及至少一个第一元素；硅材200，硅材200负载在多孔碳化物载体的孔110内，多孔碳化物载体100的孔110内具有未填充硅材200的孔隙。多孔碳化物载体的优良导电性为硅材提供导电网络，提高复合材料的导电性，从而保证电子的有效传输，多孔碳化物载体内部的孔隙结构同时也为硅材在嵌锂、脱锂的收缩膨胀提供了膨胀空间，进而提高硅材的结构稳定性，减小了复合材料的膨胀，使得复合材料应用为电极材料时具有较为稳定的结构以及较好的循环稳定性。
为了便于理解，下面对于本申请中的复合材料具有上述有益效果的原理进行说明：
发明人发现，当将纳米硅颗粒嵌在颗粒状石墨孔隙之间或附着在其表面时，形成的碳硅材料中硅颗粒尺寸较大(约20nm-250nm)，且由于硅颗粒分布于石墨孔隙之间或表面，并未均匀分散在石墨结构内部，使得碳硅复合材料的膨胀率较大，碳硅复合材料在作为电极材料使用时，在循环过程中容易发生破坏，导致碳硅复合材料的循环性能较差。
进一步地，发明人发现，相关技术中的将硅设置在多孔碳材料内部时，由于作为载体的多孔碳材料存在内部孔结构的孔径较大(约5nm-20nm)、孔尺寸分布均一性较差等问题，会使得孔内所沉积的硅尺寸较大，并且不同孔内的硅与孔隙的体积比均一性较差，碳硅复合材料在作为电极材料使用时更易发生破坏，且由于多孔碳材料自身导电性较差，从而会阻碍碳硅复合材料中的电子传导，使得碳硅复合材料的极化增大，更容易发生析锂等劣化反应。
在本申请中，通过采用多孔碳化物载体作为硅材沉积的基底，对硅材起到支撑作用，从而可以在硅材膨胀时起到保持结构完整、抑制整体复合材料颗粒膨胀的作用。通过利用多孔碳化物载体良好的导电性为硅材提供导电网络，提高电子的有效传输。通过利用多孔 碳化物载体内部的未被硅材填充的孔隙结构，为硅材膨胀提供了空间，减小了复合材料颗粒的膨胀，进而减小复合材料应用于电池极片时的膨胀。
根据本申请的一些实施例，多孔碳化物载体的结构不受特别限制，只要多孔碳化物载体通过第一元素的加入相较于多孔碳材料而言具有更好的导电性即可，例如，当多孔碳化物载体的化学式为XαYβCγ时，其中，X和Y为第一元素，α≥0、β≥0、γ>0，且α和β不同时为0时，X和Y可以分别独立地包括V、Ti、Si、W、Ta、Nb、Zr、B、Mo、Fe和Al中的至少之一，X与Y不相同。当多孔碳化物载体的化学式满足上述条件时，多孔碳化物载体具有良好的导电性，相比于无定形碳和石墨而言具有更低的电阻率，从而可以为硅材提供导电网络，提高电子的传输效率。
根据本申请的一些实施例，多孔碳化物载体的孔径分布不受特别限制，例如，多孔碳化物载体的D90孔径可以为1nm-10nm，优选地，多孔碳化物载体的D90孔径可以为0.1nm-3nm。当多孔碳化物载体的孔径分布位于上述范围内时，通过利用多孔碳化物载体的纳米孔结构，在进行后续的硅材沉积时，在尺寸均一的孔内沉积形成的硅材尺寸也较为均一，孔内未填充硅材的孔隙大小也较为均一，从而使得不同孔内硅材的体积与未填充硅材的孔隙的体积比分布较窄，保持材料内部膨胀表现的均一性，有效提高材料的循环性能。当多孔碳化物载体的孔径分布不位于上述范围内时，多孔碳化物载体的孔尺寸分布不均，从而导致体积较大的孔内硅材的体积与未填充硅材的孔隙的体积比较小，使得多孔碳化物载体孔内空间不能充分被利用来沉积更多的硅材，降低材料的比容量；体积较小的孔内硅材的体积与未填充硅材的孔隙的体积比较大，使得孔内硅材可膨胀的空间较小，在膨胀过程中容易挤压多孔碳化物载体骨架结构或周边硅材的结构，导致复合材料内部结构破坏，降低循环稳定性。
根据本申请的一些实施例，多孔碳化物载体的体积孔隙率不受特别限制，例如，多孔碳化物载体的体积孔隙率可不小于50％，进一步地，多孔碳化物载体的总孔容积可以为0.1cm3/g-5.5cm3/g，当多孔碳化物载体的体积孔隙率和总孔容积位于上述范围内时，复合材料中的硅材含量较高，从而可以有效提高电池的比容量以及能量密度。
根据本申请的一些实施例，多孔碳化物载体孔内的硅材的尺寸不受特别限制，例如，自孔的孔壁指向孔中心的方向上，硅材的厚度可以为0.1nm-10nm，优选地，硅材的厚度可以为0.1nm-3nm。当硅材的厚度位于上述范围内时，纳米级的硅材尺寸可减小其在嵌锂膨胀时的粉碎或结构破坏，保证其循环的稳定性，还可增加其无定形程度，进而减小其在嵌锂时的膨胀，提升循环性能。
进一步地，参考图1，当硅材为中空球状时，自孔的孔壁指向孔中心的方向上，硅材的厚度与中空球体的壁厚相同；参考图2，当硅材为球状时，自孔的孔壁指向孔中心的方向上，硅材的厚度与硅材的直径相同。
在本申请的描述中，需要理解的是，术语“厚度”等指示的方位或位置关系为基于附图所示的方位或位置关系，仅是为了便于描述本申请和简化描述，而不是指示或暗示所指的装置或元件必须具有特定的方位、以特定的方位构造和操作，因此不能理解为对本申请的限制。
根据本申请的一些实施例，复合材料中硅材的质量分数不受特别限制，例如，复合材料中硅材的质量分数可以为20wt％-90wt％。当复合材料中硅材的质量分数小于20wt％时，多孔碳化物载体孔内硅材的体积与未填充硅材的孔隙的体积比过小，多孔碳化物载体孔内的硅材含量过低，复合材料的比容量较低。当复合材料中硅材的质量分数大于90wt％时，多孔碳化物载体孔内硅材的体积与未填充硅材的孔隙的体积比过大，多孔碳化物载体孔内的硅材含量过大，导致孔内未填充硅材的孔隙的体积过小，使得孔内硅材可膨胀的空间较小，在膨胀过程中容易挤压多孔碳化物载体骨架结构或周边硅材的结构，导致复合材料内部结构破坏。
根据本申请的一些实施例，参考图1和图2，多孔碳化物载体的孔内硅材的体积与未填充硅材的孔隙的体积比不受特别限制，只要多孔碳化物载体的孔内具有未填充硅材的孔隙即可，例如，以硅材的总体积为V1，多孔碳化物载体的孔的总体积为V2为例，V1与V2之间的关系可以满足：V1<V2≤4V1。由此，多孔碳化物载体孔内的硅材并未完全填充该多孔碳化物载体的孔，而是留有一定的孔隙，孔隙作为缓冲空间可以在硅材膨胀收缩时起到缓冲作用，使得硅材膨胀时不会挤压破坏多孔碳化物载体骨架，从而导致复合材料的膨胀和破坏，极大地减小复合材料的膨胀率，进而保证其应用于电池负极时的结构稳定性和完整性。
在本申请中，无论是否使用“大约”或“约”等字眼，所有在此公开了的数字均为近似值。每一个数字的数值有可能会出现10％以下的差异或者本领域人员认为的合理的差异，如1％、2％、3％、4％或5％的差异。
根据本申请的一些实施例，硅材的形状不受特别限制，例如，参考图1和图2，硅材的形状可以为球状或中空球状。
根据本申请的一些实施例，复合材料的结构不受特别限制，例如，参考图3，复合材料可以进一步包括：碳包覆层300，碳包覆层300覆盖多孔碳化物载体100的外表面，从而可以降低复合材料比表面积、减小复合材料表面硅暴露、提高复合材料的导电性，还可以防止硅材膨胀导致的复合材料结构破坏。根据本申请的一些实施例，碳包覆层的厚度不受特别限制，例如，碳包覆层的厚度可以为5nm-2000nm。
在本申请的另一个方面，本申请提出了一种制备前述的复合材料的方法，从而可以通过较为简便的方法制备得到前述的复合材料，具体地，参考图4，包括：
S100：提供多孔碳化物载体前驱体
根据本申请的一些实施例，在该步骤提供多孔碳化物载体前驱体，多孔碳化物载体前驱体的种类不受特别限制，只要多孔碳化物载体前驱体包括碳元素以及至少一个第一元素即可，具体地，多孔碳化物载体前驱体可以包括VC、TiC、SiC、WC、TaC、NbC、ZrC、V2C、W2C、B4C、Mo2C、Fe3C、Ta2C、Nb2C、Ti2AlC、Ti3SiC2和Ti3AlC2中的至少之一。
S200：去除多孔碳化物载体前驱体中的部分第一元素
根据本申请的一些实施例，在该步骤去除多孔碳化物载体前驱体中的部分第一元素以获得多孔碳化物载体，具体地，去除多孔碳化物载体前驱体中的部分第一元素可以包括：将多孔碳化物载体前驱体置于氯气气氛中，并进行加热处理。通过选取合适的多孔碳化物载体前驱体在氯气氛围中进行加热，使得氯气与多孔碳化物载体前驱体中的非碳元素反应脱出，进而形成多孔碳化物载体。多孔碳化物载体前驱体在刻蚀后保持多孔碳化物载体的XαYβCγ中的α≥0、β≥0且α和β不同时为零，以保证多孔碳化物载体结构相比完全刻蚀后的纯碳骨架具有更好的导电性，从而利用多孔碳化物载体XαYβCγ中均一的X、Y和C均一分布的特征，通过刻蚀其中X元素和Y元素可形成纳米级、较窄孔径分布的孔结构，在后续进行硅材沉积可使沉积的硅材尺寸控制在纳米级，并且不同孔内硅材的体积和未填充硅材的孔隙的体积比分布较窄，保持复合材料内部膨胀表现的均一性。
可以理解的是，为了使得多孔碳化物载体骨架保持较好的导电性，该非碳元素的去除反应中不会完全除去多孔碳化物载体前驱体中的非碳元素，从而可使得仍有部分非碳元素保留在多孔碳化物载体内。
S300：对多孔碳化物载体进行硅材沉积处理
根据本申请的一些实施例，在该步骤对多孔碳化物载体进行硅材沉积处理以获得复合材料。具体地，硅材沉积处理可以包括化学气相沉积，化学气相沉积的沉积气体不受特别限制，只要其为含硅气体即可，例如，硅材沉积处理的沉积气体可以包括硅烷与氩气的混合气体。含硅气体高温下可以在多孔碳化物载体的孔内进行硅材的沉积反应，通过调控沉积的过程及反应参数，可以较为简便地实现孔内硅材的部分填充，从而使得孔内保留一定的未填充硅材的孔隙结构。
根据本申请的一些实施例，为了进一步提高复合材料的导电性和结构稳定性，在硅材沉积处理之后可以进一步包括：对多孔碳化物载体进行碳包覆处理，具体地，碳包覆处理可以包括化学气相沉积，化学气相沉积的沉积气体可以包括烷烃类气体。
在本申请的又一个方面，本申请提出了一种二次电池，包括负极极片，负极极片包括前述的复合材料，和/或，采用前述的方法制备得到的复合材料。由此，该二次电池具有前述复合材料以及制备复合材料的方法的全部特征及优点，在此不再赘述。
总言之，前述的复合材料具有较小的膨胀率和较高的比容量，通过采用前述复合材料作为二次电池的负极极片中的活性材料可以有效提高电池的结构和SEI膜(固态电解质膜)的稳定性，对于循环稳定性的提升具有重要意义。
在本申请的又一个方面，本申请提出了一种电子设备，包括前述的二次电池。由此，该电子设备具有前述二次电池的全部特征及优点，在此不再赘述。
下面通过具体的实施例对本申请的方案进行说明，需要说明的是，下面的实施例仅用于说明本申请，而不应视为限定本申请的范围。实施例中未注明具体技术或条件的，按照本领域内的文献所描述的技术或条件或者按照产品说明书进行。所用试剂或仪器未注明生产厂商者，均为可以通过市购获得的常规产品。
实施例1：
采用Ti3SiC2粉末作为多孔碳化物载体前驱体，制备复合材料的方法如下：
1、将Ti3SiC2粉末放置于管式炉中，在加热前和加热时通入氩气以排出空气，加热至700℃，通入氯气3小时使其与Ti3SiC2粉末进行反应，生成的SiCl4和TiCl4气体被排出，反应结束后通入氩气以排出氯气和反应后气体产物，以获得多孔碳化物载体。
2、将管式炉温度调整至500℃，通入3％(v/v)硅烷气体(混合氩气)并保持2h进行硅材沉积反应后即获得复合材料。
实施例2：
采用TiC粉末作为多孔碳化物载体前驱体，制备复合材料的方法如下：
1、将TiC粉末放置于管式炉中，在加热前和加热时通入氩气以排出空气，加热至600℃，通入氯气3小时使其与TiC粉末进行反应，生成的TiCl4气体被排出，反应结束后通入氩气以排出氯气和反应后气体产物，以获得多孔碳化物载体。
2、将管式炉温度调整至500℃，通入3％(v/v)硅烷气体(混合氩气)并保持1.5h进行硅材沉积反应后即获得复合材料。
实施例3：
实施例3与实施例1保持一致，所不同的是，在硅材沉积反应之后进行碳包覆层的设 置，具体地，对硅材沉积后的材料通入甲烷气体，保持在800℃进行热解2h即获得具有碳包覆层的复合材料。
实施例4：
实施例4与实施例1保持一致，所不同的是，所采用的多孔碳化物前驱体为Mo2C，以获得多孔碳化物载体。
实施例5：
实施例5与实施例1保持一致，所不同的是，所采用的多孔碳化物前驱体为Fe3C，以获得多孔碳化物载体。
实施例6：
实施例6与实施例1保持一致，所不同的是，通入氯气的时间为2h，以获得多孔碳化物载体。
对比例1：
对比例1与实施例1保持一致，所不同的是，通入氯气的时间为5h，以获得多孔碳载体。
对比例2：
对比例2与实施例1保持一致，所不同的是，通入3％(v/v)硅烷气体(混合氩气)并保持4h，以获得多孔碳载体。
测试方法：将复合材料与CMC、SBR、SP按照80：4:6:10的比例混合制成负极片并组装成扣式半电池，测试首次充放电的比容量和首效以及循环50周后的容量保持率。
测试结果如下：

测试结果表明，对比例1相比于实施例1而言氯气反应时间过长，碳化物中的非碳元素去除更完全。对比例1所得复合材料的粉末电阻率为6.18Ω·cm，相比于实施例1所得复合材料导电性能更差；50周循环保持率为86％，相比于实施例1的94％保持率下降明显。对比例2相比于实施例1的而言硅沉积时间过长，表面硅含量为36.7％，相比于实施例1硅含量增加明显，表明产生过量的硅沉积，粉末电阻率显著增加至2.86Ω·cm，50周循环保持率下降至82％，循环性能显著下降。
除非另外说明，本申请所使用的所有科技术语具有与本申请所属领域技术人员的通常理解相同的含义。本申请涉及的所有专利和公开出版物通过引用方式整体并入本申请。术语“包含”或“包括”为开放式表达，即包括本申请所指明的内容，但并不排除其他方面的内容。
在本说明书的描述中，参考术语“一个实施例”、“另一个实施例”等的描述意指结合该实施例描述的具体特征、结构、材料或者特点包含于本申请的至少一个实施例中。在本说明书中，对上述术语的示意性表述不必须针对的是相同的实施例或示例。而且，描述的具体特征、结构、材料或者特点可以在任一个或多个实施例或示例中以合适的方式结合。此外，在不相互矛盾的情况下，本领域的技术人员可以将本说明书中描述的不同实施例或示例以及不同实施例或示例的特征进行结合和组合。
尽管上面已经示出和描述了本申请的实施例，可以理解的是，上述实施例是示例性的，不能理解为对本申请的限制，本领域的普通技术人员在本申请的范围内可以对上述实施例进行变化、修改、替换和变型。

Claims (20)

  1. 一种复合材料，其中，包括：
    多孔碳化物载体，所述多孔碳化物载体包括碳元素以及至少一个第一元素；
    硅材，所述硅材负载在所述多孔碳化物载体的孔内，
    所述多孔碳化物载体的孔内具有未填充所述硅材的孔隙。
  2. 根据权利要求1所述的复合材料，其中，所述多孔碳化物载体的化学式为XαYβCγ，其中，所述X和所述Y为所述第一元素，α≥0、β≥0、γ>0，且所述α和所述β不同时为0，所述X和所述Y分别独立地包括V、Ti、Si、W、Ta、Nb、Zr、B、Mo、Fe和Al中的至少之一，所述X与所述Y不相同。
  3. 根据权利要求1或2所述的复合材料，其中，所述多孔碳化物载体的D90孔径为1nm-10nm。
  4. 根据权利要求3所述的复合材料，其中，所述多孔碳化物载体的D90为0.1nm-3nm。
  5. 根据权利要求1-4任一项所述的复合材料，其中，所述多孔碳化物载体的体积孔隙率不小于50％。
  6. 根据权利要求1-5任一项所述的复合材料，其中，-所述多孔碳化物载体的总孔容积为0.1cm3/g-5.5cm3/g。
  7. 根据权利要求1-6任一项所述的复合材料，其中，自所述孔的孔壁指向所述孔中心的方向上，所述硅材的厚度为0.1nm-10nm。
  8. 根据权利要求1-7任一项所述的复合材料，其中，自所述孔的孔壁指向所述孔中心的方向上，所述硅材的厚度为0.1nm-3nm。
  9. 根据权利要求1-8任一项所述的复合材料，其中，所述复合材料中所述硅材的质量分数为20wt％-90wt％。
  10. 根据权利要求1-9任一项所述的复合材料，其中，所述硅材的总体积为V1，所述多孔碳化物载体的所述孔的总体积为V2，V1<V2≤4V1。
  11. 根据权利要求1-10任一项所述的复合材料，其中，所述硅材的形状为球状或中空球状。
  12. 根据权利要求1-11任一项所述的复合材料，其中，进一步包括：碳包覆层，所述碳包覆层覆盖所述多孔碳化物载体的外表面。
  13. 根据权利要求12所述的复合材料，其中，所述碳包覆层的厚度为5nm-2000nm。
  14. 一种制备权利要求1-13任一项所述的复合材料的方法，其中，包括：
    提供多孔碳化物载体前驱体，所述多孔碳化物载体前驱体包括碳元素以及至少一个第一元素；
    去除所述多孔碳化物载体前驱体中的部分所述第一元素，以获得多孔碳化物载体；
    对所述多孔碳化物载体进行硅材沉积处理，以获得所述复合材料。
  15. 根据权利要求14所述的方法，其中，所述多孔碳化物载体前驱体包括VC、TiC、SiC、WC、TaC、NbC、ZrC、V2C、W2C、B4C、Mo2C、Fe3C、Ta2C、Nb2C、Ti2AlC、Ti3SiC2和Ti3AlC2中的至少之一。
  16. 根据权利要求14或15所述的方法，其中，所述去除所述多孔碳化物载体前驱体中的部分所述第一元素包括：将所述多孔碳化物载体前驱体置于氯气气氛中，并进行加热处理。
  17. 根据权利要求14-16任一项所述的方法，其中，所述硅材沉积处理包括化学气相沉积，所述化学气相沉积的沉积气体包括硅烷与氩气的混合气体。
  18. 根据权利要求14-17任一项所述的方法，其中，在所述硅材沉积处理之后进一步包括：对所述多孔碳化物载体进行碳包覆处理，所述碳包覆处理包括化学气相沉积，所述化学气相沉积的沉积气体包括烷烃类气体。
  19. 一种二次电池，其中，包括负极极片，所述负极极片包括权利要求1-13任一项所述的复合材料，和/或，采用权利要求14-18任一项所述的方法制备得到的复合材料。
  20. 一种电子设备，其中，包括权利要求19所述的二次电池。
PCT/CN2023/099975 2022-07-21 2023-06-13 复合材料及其制备方法、二次电池和电子设备 WO2024016900A1 (zh)

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KR20200100557A (ko) * 2019-02-18 2020-08-26 에스케이이노베이션 주식회사 리튬 이차 전지용 음극 활물질, 이의 제조방법, 및 이를 포함하는 리튬 이차 전지
US20220055906A1 (en) * 2020-08-18 2022-02-24 Group14 Technologies, Inc. Particulate composite materials
WO2022129941A1 (en) * 2020-12-18 2022-06-23 Nexeon Limited Electroactive materials for metal-ion batteries
CN115117327A (zh) * 2022-08-25 2022-09-27 溧阳天目先导电池材料科技有限公司 一种低膨胀硅基复合材料及其制备方法和应用

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KR20200100557A (ko) * 2019-02-18 2020-08-26 에스케이이노베이션 주식회사 리튬 이차 전지용 음극 활물질, 이의 제조방법, 및 이를 포함하는 리튬 이차 전지
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WO2022129941A1 (en) * 2020-12-18 2022-06-23 Nexeon Limited Electroactive materials for metal-ion batteries
CN115117327A (zh) * 2022-08-25 2022-09-27 溧阳天目先导电池材料科技有限公司 一种低膨胀硅基复合材料及其制备方法和应用

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