WO2024031867A1 - 氮掺杂石墨烯包覆硅碳复合材料及其制备方法和应用 - Google Patents

氮掺杂石墨烯包覆硅碳复合材料及其制备方法和应用 Download PDF

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WO2024031867A1
WO2024031867A1 PCT/CN2022/133358 CN2022133358W WO2024031867A1 WO 2024031867 A1 WO2024031867 A1 WO 2024031867A1 CN 2022133358 W CN2022133358 W CN 2022133358W WO 2024031867 A1 WO2024031867 A1 WO 2024031867A1
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silicon
nitrogen
composite material
doped
graphene
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French (fr)
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丁伟涛
邢显博
刘登华
陈英楠
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Shinghwa Advanced Material Group Co Ltd
Shinghwa Advanced Material Technology Meishan Co Ltd
Shinghwa Amperex Technology Dongying Co Ltd
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Shinghwa Advanced Material Group Co Ltd
Shinghwa Advanced Material Technology Meishan Co Ltd
Shinghwa Amperex Technology Dongying Co Ltd
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Priority to EP22884776.0A priority Critical patent/EP4567920A4/en
Priority to JP2023522505A priority patent/JP7685591B2/ja
Priority to KR1020237016112A priority patent/KR102655588B1/ko
Publication of WO2024031867A1 publication Critical patent/WO2024031867A1/zh
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    • C08F12/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F12/02—Monomers containing only one unsaturated aliphatic radical
    • C08F12/04—Monomers containing only one unsaturated aliphatic radical containing one ring
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    • 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
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    • 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
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
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    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the invention belongs to the field of lithium-ion battery preparation, and specifically relates to a nitrogen-doped graphene-coated silicon-carbon composite material.
  • the invention also relates to the preparation and application of the nitrogen-doped graphene-coated silicon-carbon composite material.
  • lithium-ion batteries With the emergence of emerging markets such as electric vehicles (EV) and hybrid electric vehicles (HEV), there is a huge demand for lithium-ion batteries (LIB).
  • commercial anode materials for lithium-ion batteries are mainly carbon materials such as graphite carbon, whose maximum theoretical specific capacity is only 372mAh/g, thus restricting the further improvement of lithium battery capacity.
  • the lithiation platform voltage of silicon-based electrodes is higher than that of graphite electrodes.
  • the platform voltage is high, which can effectively avoid the formation of lithium dendrites, thereby improving the safety of lithium-ion batteries.
  • the volume of the silicon-based electrode will expand (about 300%), which will lead to the destruction of the silicon-based electrode structure and the peeling and powdering of the electrode, as well as the decrease in conductivity.
  • the capacity of ion batteries decays rapidly, and their rate performance is also relatively poor due to the poor electronic conductivity of silicon.
  • the purpose of the present invention is to provide a nitrogen-doped graphene-coated silicon-carbon composite material and its preparation method and application, which can significantly improve the liquid retention performance, reduce the expansion of silicon during charging and discharging, and can reduce impedance as well as improving the cycle and power performance of the battery in which it is applied.
  • a nitrogen-doped graphene-coated silicon-carbon composite material including at least a silicon-based matrix as a core and a coating layer as an outer shell; wherein the coating layer includes nitrogen-doped amorphous carbon and graphene, and the Graphene is coated on the outer surface of the nitrogen-doped amorphous carbon and/or doped in the nitrogen-doped amorphous carbon.
  • the mass ratio between the silicon-based substrate and the cladding layer is 100:1-8; and/or the mass ratio between nitrogen-doped amorphous carbon and graphene in the cladding layer is 10:0.5-4.
  • the silicon-based matrix includes nano-silicon
  • the nitrogen-doped amorphous carbon includes nitrogen-doped porous carbon in a porous network structure.
  • a method for preparing a nitrogen-doped graphene-coated silicon-carbon composite material as described above involves electrochemical polymerization of a carbon source and a nitrogen source coupling agent with a carboxylated silicon-based matrix (i.e., using an electrochemical deposition method ) to obtain a silicon-based precursor, and after subjecting the silicon-based precursor and graphene oxide dispersion to hydrothermal reaction, hydrogen reduction reaction and carbonization treatment, the nitrogen-doped graphene-coated silicon-carbon composite material is obtained.
  • step S40 perform a hydrogen reduction reaction with hydrogen and then carbonize the composite material obtained through the above step S30) to obtain the nitrogen-doped graphene-coated silicon-carbon composite material.
  • the silicon-based matrix includes nano-silicon, and the nano-silicon is carboxylated through an acid solution;
  • the carbon source includes polystyrene, and the nitrogen source coupling agent includes an aminosilane coupling agent.
  • the electrochemical polymerization includes: using saturated calomel as a reference electrode, scanning for 10-100 cycles in a voltage range of -2V to 2V at a scanning rate of 0.5-5mV/s, to complete
  • the electrochemically polymerized working electrode is washed and filtered to obtain a nitrogen-doped silicon/polystyrene microsphere composite material as a silicon-based precursor.
  • the weight proportion of graphene oxide in the graphene oxide dispersion is 0.5-8wt%;
  • the hydrothermal reaction includes: setting the temperature range to 100-200°C and the pressure range to 1-5Mpa The hydrothermal reaction is carried out under the conditions for at least 1 hour;
  • the hydrogen reduction reaction includes: passing in hydrogen and inert gas with a volume ratio of 1-5:10 in a vacuum state, and performing it under the condition that the temperature range is set to 250-350°C
  • the hydrogen reduction reaction takes at least 1 hour;
  • the carbonization treatment includes: carbonizing at a temperature range of 700-1100°C for at least 1 hour.
  • the mass ratio of the silicon-based precursor to graphene oxide is 100:1-8;
  • the binder includes asphalt and/or polyvinyl alcohol and/or CMC cellulose binder and/or LA133 type binder.
  • an application of the nitrogen-doped graphene-coated silicon-carbon composite material as described above is used as an active material raw material for preparing battery pole pieces.
  • the nano-Si involved in this application refers to crystalline silicon particles with a diameter less than 20 nanometers, which can be purchased directly from the market.
  • the rod-shaped silicon-based composite referred to throughout this application may be rod-shaped, sheet-shaped, or other shapes that can be used as working electrodes in electrochemical deposition methods. These changes in shapes all belong to the rod-shaped silicon-based composites described in this application. The scope of the base complex.
  • the coating layer in the nitrogen-doped graphene-coated silicon-carbon composite material provided by this application includes nitrogen-doped amorphous carbon and graphene, and the graphene is coated on the outer surface of the nitrogen-doped amorphous carbon and/or doped In nitrogen-doped amorphous carbon, it can significantly improve the liquid retention performance and reduce the expansion of silicon during charge and discharge. Moreover, the amorphous carbon in nitrogen-doped graphene-coated silicon-carbon composites contains nitrogen atoms, which can reduce the impedance. And the isotropy of carbon is excellent, which can improve the power performance of its applied battery.
  • the graphene in the nitrogen-doped graphene-coated silicon-carbon composite material is coated on the outer surface of amorphous carbon and/or doped in amorphous carbon.
  • the impedance can be further reduced, thereby improving the cycle and power performance of the battery in which it is applied.
  • the preparation of this application it is proposed to first use the electrochemical deposition method to establish chemical bond connections on the surface of the silicon-based substrate through chemical bonds, and deposit a porous network structure composed of a nitrogen source and a carbon source on the surface of the working electrode based on the silicon-based substrate. After carbonization, the porous carbon structure formed can significantly reduce the expansion of silicon and significantly reduce the impedance.
  • the preparation process is stable, reliable and efficient, and is suitable as a preparation route for mass production of nitrogen-doped graphene-coated silicon-carbon composite materials.
  • Figure 1 is an SEM image of the nitrogen-doped graphene-coated silicon-carbon composite material in Example 1 of the present invention.
  • This embodiment discloses a nitrogen-doped graphene-coated silicon-carbon composite material, which at least includes a silicon-based matrix as a core and a coating layer as an outer shell; wherein the coating layer includes nitrogen-doped amorphous carbon and graphene.
  • graphene is coated on the outer surface of nitrogen-doped amorphous carbon and/or doped in nitrogen-doped amorphous carbon; preferably, in this embodiment, the mass ratio between the silicon-based substrate and the coating layer It is 100:1-8, more preferably 100:1-6, further preferably 100:1-5; and/or, the mass ratio between nitrogen-doped amorphous carbon and graphene in the coating layer is 10: 0.5-4, more preferably 10:0.5-3, even more preferably 10:0.5-2.
  • the silicon-based matrix includes nano-silicon
  • the nitrogen-doped amorphous carbon includes nitrogen-doped porous carbon with a porous network structure, which can significantly reduce the expansion of silicon and significantly reduce the impedance.
  • this embodiment also proposes a nitrogen-doped graphene-coated silicon-carbon composite material as described above.
  • the preparation method of the composite material includes electrochemical polymerization of a carbon source and a nitrogen source coupling agent with a carboxylated silicon-based matrix to obtain a silicon-based precursor.
  • the silicon-based precursor and graphene oxide dispersion are subjected to hydrothermal reaction and hydrogen gas. After reduction reaction and carbonization treatment, nitrogen-doped graphene-coated silicon-carbon composite material is obtained.
  • the preparation method of nitrogen-doped graphene-coated silicon-carbon composite material includes the following steps:
  • the silicon-based composite includes nano-silicon, and the nano-silicon is carboxylated with an acid solution to obtain carboxylated nano-silicon; specifically, preferably, the nano-silicon is placed in a mixed solution of concentrated sulfuric acid/concentrated nitric acid, and the temperature is 25-80°C.
  • the binder includes asphalt and/or polyvinyl alcohol and/or CMC cellulose binder and/or LA133 binder and/or SBR styrene-butadiene latex binder and/or LA136D binder, other suitable known binders can also be used, specifically preferably carboxylated
  • the mass ratio between nano silicon and binder is 80-90:10-20;
  • the carbon source includes polystyrene
  • the nitrogen source coupling agent includes an aminosilane coupling agent
  • the solvent is chloroform
  • the mass ratio between polystyrene: aminosilane coupling agent: chloroform is 1-5: 1-5:100;
  • other well-known substances with similar effects can also be used as carbon source or nitrogen source coupling agents, and this embodiment does not limit this;
  • the electrochemical polymerization includes: using saturated calomel as the reference electrode, scanning for 10-100 cycles at a scan rate of 0.5-5mV/s in the voltage range of -2V to 2V, to complete the electrochemical polymerization. The working electrode is washed and filtered to obtain a nitrogen-doped silicon/polystyrene microsphere composite material as a silicon-based precursor;
  • the hydrothermal reaction is performed under heating and pressurizing conditions, and then dried and crushed; preferably, in this step S30), the silicon-based precursor
  • the mass ratio of graphene oxide to graphene oxide is 100:1-8, more preferably 100:1-5; preferably, the weight proportion of graphene oxide in the graphene oxide dispersion is 0.5-8wt%, more preferably 0.5-6wt%, more preferably 0.5-5wt%;
  • the hydrothermal reaction includes: performing the hydrothermal reaction for at least 1 hour under the conditions of setting the temperature range to 100-200°C and the pressure range to 1-5Mpa, and more Preferably it is 1-8 hours, further preferably 1-6 hours;
  • step S40 perform a hydrogen reduction reaction with hydrogen and then carbonize the composite material obtained through the above step S30) to obtain a nitrogen-doped graphene-coated silicon-carbon composite material; preferably, in this step S40), hydrogen reduction
  • the reaction includes: introducing hydrogen and inert gas (i.e. mixed gas) with a volume ratio of 1-5:10 in a vacuum state, performing a hydrogen reduction reaction at a temperature range of 250-350°C for at least 1 hour, and more Preferably it is 1-8 hours, further preferably 1-6 hours; the carbonization treatment includes: carbonizing at a temperature range of 700-1100°C for at least 1 hour, more preferably 1-8 hours, further preferably 1- 6 hours.
  • inert gas i.e. mixed gas
  • this embodiment also proposes an application of the nitrogen-doped graphene-coated silicon-carbon composite material as described above, using the nitrogen-doped graphene-coated silicon-carbon composite material as an active material raw material for preparing battery pole sheets;
  • Silicon-carbon composite materials are used as active material raw materials for preparing battery electrode sheets; specifically, they can be used as battery negative electrode sheets, which can be selected according to actual requirements; during specific implementation, the process for preparing battery negative electrode sheets can adopt any well-known process, and this part does not It belongs to the innovative content of this application, and this application does not impose any restrictions on it; it should also be noted that when this application is implemented, the battery can be a button battery, a soft pack battery or other well-known batteries. Those skilled in the art can The application is carried out according to actual needs, and this application does not impose any special restrictions on this.
  • Step 1 Place the nano-silicon into a mixture of concentrated sulfuric acid/concentrated nitric acid, soak it at a temperature of 50°C for 12 hours, and then wash it with deionized water to obtain carboxylated nano-silicon;
  • Step 2 Mix 85g of carboxylated nano-silica and 15g of asphalt binder evenly, place it in a hot press, and press it at a temperature of 100°C to obtain a rod-shaped silicon-based composite;
  • Step 3 Implement electrochemical deposition method (cyclic voltammetry) for electrochemical polymerization, which specifically includes: using a rod-shaped silicon-based composite as the working electrode, using saturated calomel as the reference electrode, in the voltage range of -2V to 2V , scan for 50 cycles at a scan rate of 1 mV/s, wash and filter the working electrode with deionized water to obtain a nitrogen-doped silicon/polystyrene microsphere composite material, which is used as a silicon-based precursor.
  • the body wherein, the electrolyte in the electrochemical polymerization adopts a solution prepared by dissolving 3g polystyrene and 3g aminosilane coupling agent in 100ml chloroform solvent (mass concentration is 6%);
  • Step 4 Add 100g of nitrogen-doped silicon/polystyrene microsphere composite material into 300ml of graphene oxide dispersion with a mass concentration of 1wt%, disperse it evenly, and then transfer it to a high-pressure reactor at a temperature of 150°C. , after reacting for 3 hours at a pressure of 3Mpa, vacuum dry and pulverize;
  • Step 5 transfer to the tubular carbonization furnace. First, introduce argon inert gas to eliminate the air in the tube, and then introduce a hydrogen gas mixture (the volume ratio between hydrogen and argon in the gas mixture is 3:10). Carry out hydrogen reduction reaction at a temperature of 300°C for 3 hours;
  • Step 6 Then, the temperature is raised to 950°C and carbonized for 3 hours to obtain the nitrogen-doped graphene-coated silicon-carbon composite material of Example 1.
  • This application conducted an SEM (scanning electron microscope) test on the nitrogen-doped graphene-coated silicon-carbon composite material obtained in Example 1.
  • SEM scanning electron microscope
  • Step 1 Place the nano-silicon into a mixture of concentrated sulfuric acid/concentrated nitric acid, soak it at a temperature of 25°C for 24 hours, and then wash it with deionized water to obtain carboxylated nano-silicon;
  • Step 2 Mix 80g of carboxylated nano-silica and 29g of polyvinyl alcohol binder evenly, place it in a hot press, and press it at a temperature of 100°C to obtain a rod-shaped silicon-based composite;
  • Step 3 Implement electrochemical deposition method (cyclic voltammetry) for electrochemical polymerization, which specifically includes: using a rod-shaped silicon-based composite as the working electrode, using saturated calomel as the reference electrode, in the voltage range of -2V to 2V , scan for 10 cycles at a scan rate of 0.5mV/s, wash and filter the working electrode with deionized water to obtain a nitrogen-doped silicon/polystyrene microsphere composite material as a silicon-based Precursor; wherein, the electrolyte in electrochemical polymerization is a mixed solution composed of 1g polystyrene and 1g aminosilane coupling agent dissolved in 100ml chloroform solvent;
  • Step 4 Add 100g of nitrogen-doped silicon/polystyrene microsphere composite material into 20ml of graphene oxide dispersion with a mass concentration of 0.5wt%, disperse it evenly, and then transfer it to a high-pressure reactor at a temperature of 100 °C, after reacting for 6 hours at a pressure of 5Mpa, vacuum dry and pulverize;
  • Step 5 transfer to the tubular carbonization furnace. First, introduce argon inert gas to eliminate the air in the tube, and then introduce hydrogen mixed gas (the volume ratio between hydrogen and argon in the mixed gas is 1:10). Carry out hydrogen reduction reaction at a temperature of 250°C for 6 hours;
  • Step 6 The temperature is then raised to 700°C and carbonized for 6 hours to obtain the nitrogen-doped graphene-coated silicon-carbon composite material of Example 2.
  • Step 1 Place nano-silica into a mixture of concentrated sulfuric acid/concentrated nitric acid, soak at a temperature of 80°C for 1 hour, and then wash with deionized water to obtain carboxylated nano-silica;
  • Step 2 Mix 90g of carboxylated nano-silica and 10g of CMC cellulose binder evenly, place it in a hot press, and press it at a temperature of 100°C to obtain a rod-shaped silicon-based composite;
  • Step 3 Implement electrochemical deposition method (cyclic voltammetry) for electrochemical polymerization, which specifically includes: using a rod-shaped silicon-based composite as the working electrode, using saturated calomel as the reference electrode, in the voltage range of -2V to 2V , scan for 100 cycles at a scan rate of 5 mV/s, wash and filter the working electrode with deionized water to obtain a nitrogen-doped silicon/polystyrene microsphere composite material, which is used as a silicon-based precursor. body; wherein, the electrolyte in the electrochemical polymerization adopts a mixed solution composed of 5g polystyrene and 5g aminosilane coupling agent dissolved in 100ml chloroform solvent;
  • Step 4 Add 100g of nitrogen-doped silicon/polystyrene microsphere composite material to 100ml of graphene oxide dispersion with a mass concentration of 5wt%, disperse it evenly, and then transfer it to a high-pressure reactor at a temperature of 200°C. , after reacting for 1 hour at a pressure of 1Mpa, vacuum dry and pulverize;
  • Step 5 transfer to the tubular carbonization furnace. First, introduce argon inert gas to eliminate the air in the tube, and then introduce hydrogen mixed gas (the volume ratio between hydrogen and argon in the mixed gas is 5:10). Carry out hydrogen reduction reaction at a temperature of 350°C for 1 hour;
  • Step 6 Then, the temperature is raised to 1100°C and carbonized for 1 hour to obtain the nitrogen-doped graphene-coated silicon-carbon composite material of Example 3.
  • Comparative Example 1 The technical solution of this Comparative Example 1 is the same as that of Example 1. The difference is that in this Comparative Example 1, 100g of the carboxylated nano-silicon in Example 1 (obtained by step 1 of Example 1), 5g of poly Styrene and 5g of aminosilane coupling agent were dissolved in 100ml of chloroform solvent and evenly dispersed, and then spray-dried to obtain a silicon-based precursor, which was used to replace the nitrogen-doped silicon/polystyrene microsphere composite material in Example 1 to obtain Silicon carbon composite material in Comparative Example 1.
  • Comparative Example 2 The technical solution of Comparative Example 2 is the same as that of Example 1. The difference is that step four in Example 1 is cancelled, and 100 g of nitrogen-doped silicon/polystyrene microspheres obtained in step three in Example 1 are directly compounded. The material is transferred to a tubular carbonization furnace, and steps five and six are carried out with reference to Example 1 to obtain the silicon-carbon composite material in Comparative Example 1.
  • this application uses the silicon carbon composite materials obtained in Examples 1-3 and the silicon carbon composite materials in Comparative Examples 1-2 as active materials for the negative electrode sheets of lithium ion batteries.
  • Raw materials are assembled into 5 button batteries through the following methods:
  • the correspondingly prepared pole piece is used as the negative electrode, and the metal lithium piece as the counter electrode, the electrolyte and the separator are assembled into a button cell in a glove box with an oxygen and water content of less than 0.1 ppm.
  • Example 1 and Example 2 the corresponding prepared button batteries are marked as A-1, B-1, C-1, D-1, and E-1; wherein, The separator is specifically selected from celegard 2400; the electrolyte is specifically selected from a solution of LiPF 6.
  • the concentration of LiPF 6 is 1.2mol/L, and the solvent is ethylene carbonate (EC) and diethyl carbonate (DMC) (weight ratio is 1:1) mixed solution;
  • test results are shown in Table 2.
  • the corresponding silicon-carbon composite material is doped with 90wt% (accounting for the weight percentage of the negative electrode sheet) artificial graphite as the negative electrode material to prepare the negative electrode sheet, and the ternary material (Li(Ni 0.6 Co 0.2 Mn 0.2 )O 2 ) is used as the positive electrode.
  • the material uses Celgard 2400 membrane as the separator, LiPF 6 as the electrolyte, and a mixture of ethylene carbonate (EC) and diethyl carbonate (DEC) with a volume ratio of 1:1 as the solvent.
  • the concentration of LiPF 6 is 1.3mol/L; a 5Ah soft pack battery was prepared.
  • the corresponding soft-pack batteries prepared are marked A-2, B-2, C-2, and D- 2.
  • E-2 the corresponding soft-pack batteries prepared are marked A-2, B-2, C-2, and D- 2.
  • Soft pack battery D1( ⁇ m) D2( ⁇ m) Expansion rate A-2 112 159.5 42.4% B-2 111 159.0 43.2% C-2 112 161.5 44.20% D-2 114 182.5 60.1% E-2 112 183.6 63.9%
  • the cycle performance of the soft-packed lithium-ion battery prepared using the silicon-carbon composite material provided in Examples 1-3 of the present invention is significantly better than that of Comparative Examples 1-2, which further confirms that:
  • the silicon-carbon composite material provided has the characteristics of low expansion and low impedance, so that it has lower expansion during the cycle, reducing the lithium ion consumption problem caused by SEI, thereby improving the cycle performance; at the same time, the silicon provided by the embodiment of the present invention
  • Carbon composite materials have lower impedance, thereby improving the rate performance of lithium-ion batteries, that is, they have a higher constant current ratio.

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Abstract

本发明公开了一种氮掺杂石墨烯包覆硅碳复合材料及其制备方法和应用，至少包括作为内核的硅基基体以及作为外壳的包覆层；其中，包覆层包括氮掺杂无定形碳和石墨烯，石墨烯包覆在氮掺杂无定形碳的外表面和/或掺杂在氮掺杂无定形碳中；本发明可以显著提升保液性能，并降低充放电过程中硅的膨胀，且可以降低阻抗以及提升其应用电池的循环和功率性能。

Description

氮掺杂石墨烯包覆硅碳复合材料及其制备方法和应用
本申请要求于2022年08月10日提交中国国家知识产权局专利局，申请号为2022109539619、发明名称为“氮掺杂石墨烯包覆硅碳复合材料及其制备方法和应用”的中国专利申请优先权，其全部内容通过引用结合在本申请中。
技术领域
本发明属于锂离子电池制备领域，具体涉及一种氮掺杂石墨烯包覆硅碳复合材料，本发明还涉及了该氮掺杂石墨烯包覆硅碳复合材料的制备及其应用。
背景技术
随着电动汽车(EV)、混合动力电动汽车(HEV)等新兴市场出现，对锂离子电池(LIB)产生巨大需求。目前锂离子电池的商用负极材料主要为石墨碳素类的碳材料，其最大理论比容量仅为372mAh/g，因而制约了锂电池容量的进一步提高。
由于硅的高理论容量(例如Li4.4Si合金的理论容量大约为4200mAh/g)，且其资源丰富，是新一代最有希望的电极材料，其中，硅基电极的锂化平台电压比石墨电极的平台电压高，能有效避免锂枝晶的形成，进而可以提升锂离子电池的安全性。但是硅基电极在嵌锂脱锂过程中，会导致硅基电极体积的膨胀(约300％)，从而导致硅基电极结构的破坏及其电极的剥落、粉化、电导率的下降，进而锂离子电池的容量迅速衰减，此外由于硅的电子导电率差造成其倍率性能也相对较差。
基于以上现状，本申请人基于发明人同时具有在硅基材料以及锂离子电池领域的多年专注研究经验，决定寻求技术方案来对解决以上技术问题。
发明内容
有鉴于此，本发明的目的在于提供一种氮掺杂石墨烯包覆硅碳复合材料及其制备方法和应用，可以显著提升保液性能，并降低充放电过程中硅的膨胀，且可以降低阻抗以及提升其应用电池的循环和功率性能。
本发明采用的技术方案如下：
一种氮掺杂石墨烯包覆硅碳复合材料，至少包括作为内核的硅基基体以及作为外壳的包覆层；其中，所述包覆层包括氮掺杂无定形碳和石墨烯，所述石墨烯包覆在所述氮掺杂无定形碳的外表面和/或掺杂在所述氮掺杂无定形碳中。
优选地，所述硅基基体与所述包覆层之间的质量比为100:1-8；和/或，所述包覆层中氮掺杂无定形碳和石墨烯之间的质量比为10:0.5-4。
优选地，所述硅基基体包括纳米硅，所述氮掺杂无定形碳包括呈多孔网络结构的氮掺杂多孔碳。
优选地，一种如上所述氮掺杂石墨烯包覆硅碳复合材料的制备方法，通过碳源和氮源偶联剂与羧酸化的硅基基体进行电化学聚合(即采用电化学沉积法)得到硅基前驱体，将该硅基前驱体和氧化石墨烯分散液进行水热反应、氢气还原反应和碳化处理后，得到所述氮掺杂石墨烯包覆硅碳复合材料。
优选地，包括如下操作步骤：
S10)、将所述羧酸化的硅基基体与粘结剂混合均匀后，将其压制成型得到棒状硅基复合体；
S20)、将溶于溶剂中的碳源和氮源偶联剂作为电解液，将所述棒状硅基复合体作为工作电极，经过电化学聚合制作得到硅基前驱体；
S30)、将所述硅基前驱体置于氧化石墨烯分散液中分散均匀后，在加热加压条件下进行水热反应后，进行干燥、破碎；
S40)、将经上述步骤S30)得到的复合材料与氢气进行氢气还原反应后再进行碳化处理，得到所述氮掺杂石墨烯包覆硅碳复合材料。
优选地，所述硅基基体包括纳米硅，通过酸溶液对所述纳米硅进行羧酸化处理；所述碳源包括聚苯乙烯，所述氮源偶联剂包括氨基硅烷偶联剂。
优选地，所述电化学聚合包括：采用饱和甘汞为参比电极，在-2V至2V的电压范围内，以扫描速率为0.5-5mV/s的条件下扫描10-100个周期，对完成电化学聚合的工作电极进行洗涤、过滤，得到作为硅基前驱体的氮掺杂硅/聚苯乙烯微球复合材料。
优选地，所述氧化石墨烯分散液中氧化石墨烯的重量份占比为0.5-8wt％；所述水热反应包括：在温度范围设置为100-200℃，压强范围设置为1-5Mpa的条件下进行水热反应至少1小时；所述氢气还原反应包括：在真空状态下通入体积比为1-5:10的氢气与惰性气体，在温度范围设置为250-350℃的条件下进行氢气还原反应至少1小时；所述碳化处理包括：在温度范围设置为700-1100℃的条件下进行碳化至少1小时。
优选地，所述硅基前驱体与氧化石墨烯的质量比为100:1-8；所述粘结剂包括沥青和/或聚乙烯醇和/或CMC纤维素粘结剂和/或LA133型粘结剂和/或SBR丁苯胶乳粘结剂和/或LA136D型粘结剂。
优选地，一种如上所述氮掺杂石墨烯包覆硅碳复合材料的应用，将所述氮掺杂石墨烯包覆硅碳复合材料作为制备电池极片的活性物质原料。
需要说明的是，本申请涉及的纳米Si是指其直径小于20纳米的晶体硅颗粒，可以直接从市场上购买得到。还需要说明的是，本申请全文涉及的棒状硅基复合体具体可以为棒状、片状或其他可用于作为电化学沉积法中工作电极的形状，这些形状的变化都属于本申请所述棒状硅基复合体的范围。
本申请提供的氮掺杂石墨烯包覆硅碳复合材料中的包覆层包括氮掺杂无定形碳和石墨烯，石墨烯包覆在氮掺杂无定形碳的外表面和/或掺杂在氮掺杂 无定形碳中，可以显著提升保液性能，并降低充放电过程中硅的膨胀，而且氮掺杂石墨烯包覆硅碳复合材料中的无定形碳含有氮原子，可以降低阻抗且碳的各向同性表现优异，可以提升其应用电池的功率性能，同时氮掺杂石墨烯包覆硅碳复合材料中的石墨烯包覆在无定形碳外表面和/或掺杂在无定形碳中，可以进一步降低阻抗，进而提升其应用电池的循环和功率性能。
本申请在制备时，提出首先利用电化学沉积法通过化学键在硅基基体表面建立化学键连接，在基于硅基基体制作的工作电极表面沉积复合有氮源和碳源的多孔网络结构，在复合石墨烯后进行碳化，形成的多孔碳结构可以明显降低硅的膨胀，同时明显降低阻抗，而且制备工艺稳定可靠且高效，适合作为批量生产氮掺杂石墨烯包覆硅碳复合材料的制备路线。
附图说明
图1是本发明实施例1中氮掺杂石墨烯包覆硅碳复合材料的SEM图。
具体实施方式
本实施例公开了一种氮掺杂石墨烯包覆硅碳复合材料，至少包括作为内核的硅基基体以及作为外壳的包覆层；其中，包覆层包括氮掺杂无定形碳和石墨烯，石墨烯包覆在氮掺杂无定形碳的外表面和/或掺杂在氮掺杂无定形碳中；优选地，在本实施方式中，硅基基体与包覆层之间的质量比为100:1-8，更优选为100:1-6，进一步优选为100:1-5；和/或，包覆层中氮掺杂无定形碳和石墨烯之间的质量比为10:0.5-4，更优选为10:0.5-3，进一步优选为10:0.5-2。
优选地，在本实施方式中，硅基基体包括纳米硅，氮掺杂无定形碳包括呈多孔网络结构的氮掺杂多孔碳，可以明显降低硅的膨胀，同时明显降低阻抗。
为了可以高效且可靠稳定地获得本实施例以上所述的氮掺杂石墨烯包覆 硅碳复合材料，优选地，本实施例还提出了一种如上所述氮掺杂石墨烯包覆硅碳复合材料的制备方法，通过碳源和氮源偶联剂与羧酸化的硅基基体进行电化学聚合得到硅基前驱体，将该硅基前驱体和氧化石墨烯分散液进行水热反应、氢气还原反应和碳化处理后，得到氮掺杂石墨烯包覆硅碳复合材料。
进一步优选地，在本实施方式中，氮掺杂石墨烯包覆硅碳复合材料的制备方法包括如下操作步骤：
S10)、将羧酸化的纳米硅与粘结剂混合均匀后，将其压制成型(可以放置在热压中进行)得到棒状硅基复合体；其中优选地，在本步骤S10)中，硅基基体包括纳米硅，通过酸溶液对纳米硅进行羧酸化处理得到羧酸化的纳米硅；具体优选地，将纳米硅放置到浓硫酸/浓硝酸的混合液中，在温度为25-80℃的条件下浸泡1-24小时，之后采用去离子水洗涤，得到本步骤S10)中的羧酸化的纳米硅；优选地，在本步骤S10)中，粘结剂包括沥青和/或聚乙烯醇和/或CMC纤维素粘结剂和/或LA133型粘结剂和/或SBR丁苯胶乳粘结剂和/或LA136D型粘结剂，也可以采用其他合适的公知粘结剂，具体优选地，羧酸化的纳米硅与粘结剂之间的质量比为80-90:10-20；
S20)、将溶于溶剂中的碳源和氮源偶联剂作为电解液，将棒状硅基复合体作为工作电极，经过电化学聚合制作得到硅基前驱体；优选地，在本步骤S20)中，碳源包括聚苯乙烯，氮源偶联剂包括氨基硅烷偶联剂，溶剂采用氯仿，具体优选地，聚苯乙烯：氨基硅烷偶联剂：氯仿之间的质量比为1-5:1-5:100；在其他实施方式中，也可以采用其他具有类似效果的公知物质作为碳源或氮源偶联剂，本实施例对此不做唯一限定；优选地，在本步骤S20)中，电化学聚合包括：采用饱和甘汞为参比电极，在-2V至2V的电压范围内，以扫描速率为0.5-5mV/s的条件下扫描10-100个周期，对完成电化学聚合的工作电极进行洗涤、过滤，得到作为硅基前驱体的氮掺杂硅/聚苯乙烯微球复合材料；
S30)、将硅基前驱体置于氧化石墨烯分散液中分散均匀后，在加热加压条件下进行水热反应后，进行干燥、破碎；优选地，在本步骤S30)中，硅基前驱体与氧化石墨烯的质量比为100:1-8，更优选为100:1-5；优选地，氧化石墨烯分散液中氧化石墨烯的重量份占比为0.5-8wt％，更优选为0.5-6wt％，更优选为0.5-5wt％；优选地，水热反应包括：在温度范围设置为100-200℃，压强范围设置为1-5Mpa的条件下进行水热反应至少1小时，更优选为1-8小时，进一步优选为1-6小时；
S40)、将经上述步骤S30)得到的复合材料与氢气进行氢气还原反应后再进行碳化处理，得到氮掺杂石墨烯包覆硅碳复合材料；优选地，在本步骤S40)中，氢气还原反应包括：在真空状态下通入体积比为1-5:10的氢气与惰性气体(即为混合气体)，在温度范围设置为250-350℃的条件下进行氢气还原反应至少1小时，更优选为1-8小时，进一步优选为1-6小时；碳化处理包括：在温度范围设置为700-1100℃的条件下进行碳化至少1小时，更优选为1-8小时，进一步优选为1-6小时。
需要特别说明的是，本申请通过大量实验通过以上实施例例举了各个优先范围参数，本领域技术人员可以根据实际情况来在这些优选参数范围(包括端点值和中间值)内来选择，为了节约说明书篇幅，本实施例不再一一展开。
优选地，本实施例还提出一种如上所述氮掺杂石墨烯包覆硅碳复合材料的应用，将氮掺杂石墨烯包覆硅碳复合材料作为制备电池极片的活性物质原料；将硅碳复合材料作为制备电池极片的活性物质原料；具体可以作为电池负极片，可以根据实际要求来进行选择；在具体实施时，制备电池负极片的工艺可以采用任意公知的工艺，该部分不属于本申请的创新内容，本申请对其不做任何限制；还需要说明的是，本申请在实施应用时，电池可以为扣式电池、软包电池或其他公知的电池，本领域技术人员可以根据实际需要来进 行应用，本申请对此不做特别限制。
为了使本技术领域的人员更好地理解本发明中的技术方案，下面将结合本发明实施例中的附图，对本发明实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例仅仅是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都应当属于本发明保护的范围。
实施例1：按如下步骤进行操作：
步骤一、将纳米硅放置到浓硫酸/浓硝酸的混合液中，置于温度为50℃浸泡12小时，之后采用去离子水洗涤，得到羧酸化的纳米硅；
步骤二、将85g羧酸化纳米硅、15g沥青粘结剂混合均匀后，置于热压机中，在温度为100℃的条件下进行压制，得到棒状硅基复合体；
步骤三、实施电化学沉积法(循环伏安法)进行电化学聚合，具体包括：以棒状硅基复合体作为工作电极，以饱和甘汞作为参比电极，在-2V至2V的电压范围内，以扫描速率为1mV/s的条件下扫描50个周期，对完成电化学聚合的工作电极进行去离子水洗涤、过滤，得到氮掺杂硅/聚苯乙烯微球复合材料，作为硅基前驱体；其中，电化学聚合中的电解液采用由3g聚苯乙烯、3g氨基硅烷偶联剂溶于100ml氯仿溶剂配置而成的溶液(质量浓度为6％)；
步骤四、将100g氮掺杂硅/聚苯乙烯微球复合材料添加到300ml，质量浓度为1wt％的氧化石墨烯分散液中，分散均匀，之后转移到高压反应釜中，在温度为150℃，压强为3Mpa的条件下反应3小时后，真空干燥、粉碎；
步骤五、之后转移到管式碳化炉中，首先通入氩气惰性气体排除管内的空气，然后通入氢气混合气(混合气中的氢气与氩气之间的体积比为3:10)，在温度为300℃的条件下进行氢气还原反应3小时；
步骤六、之后升温到950℃进行碳化处理3小时，得到本实施例1的氮掺杂石墨烯包覆硅碳复合材料。
本申请对实施例1得到的氮掺杂石墨烯包覆硅碳复合材料进行了SEM(即为扫描电镜)测试，测试结果如图1所示，我们通过图1可知，实施例1得到的硅碳复合材料颗粒粒径大小为5-10μm，且有少量片状结构的石墨烯掺杂在硅碳复合材料之间。
实施例2：按如下步骤进行操作：
步骤一、将纳米硅放置到浓硫酸/浓硝酸的混合液中，置于温度为25℃浸泡24小时，之后采用去离子水洗涤，得到羧酸化的纳米硅；
步骤二、将80g羧酸化纳米硅、29g聚乙烯醇粘结剂混合均匀后，置于热压机中，在温度为100℃的条件下进行压制，得到棒状硅基复合体；
步骤三、实施电化学沉积法(循环伏安法)进行电化学聚合，具体包括：以棒状硅基复合体作为工作电极，以饱和甘汞作为参比电极，在-2V至2V的电压范围内，以扫描速率为0.5mV/s的条件下扫描10个周期，对完成电化学聚合的工作电极进行去离子水洗涤、过滤，得到氮掺杂硅/聚苯乙烯微球复合材料，作为硅基前驱体；其中，电化学聚合中的电解液采用由1g聚苯乙烯、1g氨基硅烷偶联剂溶于100ml氯仿溶剂配置而成的混合溶液；
步骤四、将100g氮掺杂硅/聚苯乙烯微球复合材料添加到20ml，质量浓度为0.5wt％的氧化石墨烯分散液中，分散均匀，之后转移到高压反应釜中，在温度为100℃，压强为5Mpa的条件下反应6小时后，真空干燥、粉碎；
步骤五、之后转移到管式碳化炉中，首先通入氩气惰性气体排除管内的空气，然后通入氢气混合气(混合气中的氢气与氩气之间的体积比为1:10)，在温度为250℃的条件下进行氢气还原反应6小时；
步骤六、之后升温到700℃进行碳化处理6小时，得到本实施例2的氮掺杂石墨烯包覆硅碳复合材料。
实施例3：按如下步骤进行操作：
步骤一、将纳米硅放置到浓硫酸/浓硝酸的混合液中，置于温度为80℃浸 泡1小时，之后采用去离子水洗涤，得到羧酸化的纳米硅；
步骤二、将90g羧酸化纳米硅、10gCMC纤维素粘结剂混合均匀后，置于热压机中，在温度为100℃的条件下进行压制，得到棒状硅基复合体；
步骤三、实施电化学沉积法(循环伏安法)进行电化学聚合，具体包括：以棒状硅基复合体作为工作电极，以饱和甘汞作为参比电极，在-2V至2V的电压范围内，以扫描速率为5mV/s的条件下扫描100个周期，对完成电化学聚合的工作电极进行去离子水洗涤、过滤，得到氮掺杂硅/聚苯乙烯微球复合材料，作为硅基前驱体；其中，电化学聚合中的电解液采用由5g聚苯乙烯、5g氨基硅烷偶联剂溶于100ml氯仿溶剂配置而成的混合溶液；
步骤四、将100g氮掺杂硅/聚苯乙烯微球复合材料添加到100ml，质量浓度为5wt％的氧化石墨烯分散液中，分散均匀，之后转移到高压反应釜中，在温度为200℃，压强为1Mpa的条件下反应1小时后，真空干燥、粉碎；
步骤五、之后转移到管式碳化炉中，首先通入氩气惰性气体排除管内的空气，然后通入氢气混合气(混合气中的氢气与氩气之间的体积比为5:10)，在温度为350℃的条件下进行氢气还原反应1小时；
步骤六、之后升温到1100℃进行碳化处理1小时，得到本实施例3的氮掺杂石墨烯包覆硅碳复合材料。
为了验证本申请实施例所取得的技术效果，本申请还特别设置了如下对比例：
对比例1：本对比例1的技术方案同实施例1，区别在于，在本对比例1中，将100g实施例1中羧酸化的纳米硅(通过实施例1的步骤一得到)，5g聚苯乙烯、5g氨基硅烷偶联剂溶于100ml氯仿溶剂中分散均匀后，喷雾干燥，得到硅基前驱体，用于替代实施例1中的氮掺杂硅/聚苯乙烯微球复合材料，得到对比例1中的硅碳复合材料。
对比例2：本对比例2的技术方案同实施例1，区别在于，取消实施例1 中的步骤四，直接将100g实施例1中步骤三得到的氮掺杂硅/聚苯乙烯微球复合材料转移到管式碳化炉中，参照实施例1实施步骤五、步骤六，得到对比例1中的硅碳复合材料。
为了对以上实施例和对比例进行效果对比验证，本申请分别按照国家标准GBT-245332019《锂离子电池石墨类负极材料》中的方法对实施例1-3获得的硅碳复合材料以及对比例1-2中的硅碳复合材料进行了理化性能测试(粉体电导率，振实密度、比表面积、粒度)，测试结果如表1所示：
表1实施例1-3与对比例1-2的理化性能比较
Figure PCTCN2022133358-appb-000001
通过参见上表1可知：本发明实施例1-3的硅碳复合材料与对比例1-2相比，硅碳复合材料的粉体电导率得到明显提升，这是有本申请实施例采用了电化学沉积法在其纳米硅表面沉积了聚苯乙烯及其氨基偶联剂，经石墨烯包覆、碳化处理后形成无定形碳，具有致密度高、结构稳定可靠等特性，从而降低阻抗，提升硅碳复合材料的振实密度，且氨基偶联剂可以形成网络结构从而进一步提升硅碳复合材料的振实密度。
为了进一步对以上实施例和对比例进行效果对比验证，本申请将实施例1-3获得的硅碳复合材料以及对比例1-2中的硅碳复合材料分别作为锂离子电池负极片的活性物质原料，分别通过如下方法组装得到5个扣式电池：
将9g活性物质(即为对应实施例或对比例的硅碳复合材料)、0.5g导电 剂SP、0.5g LA133粘结剂加入到220mL去离子水中搅拌均匀，得到浆料；将该浆料涂膜于铜箔集流体上，即得极片；
将对应制得的极片作为负极，作为对电极的金属锂片、电解液以及隔膜，在氧气和水含量均低于0.1ppm的手套箱中组装成扣式电池，按照实施例1、实施例2、实施例3、对比例1、对比例2的顺序，分别将其对应制备得到的扣式电池标记为A-1，B-1，C-1、D-1、E-1；其中，隔膜具体选用celegard 2400；电解液具体选用LiPF 6的溶液，LiPF 6的浓度为1.2mol/L，其溶剂为碳酸乙烯酯(EC)和碳酸二乙酯(DMC)(重量比为1：1)的混合溶液；
然后采用蓝电测试仪测试扣式电池的性能，所采用的测试条件为：0.1C的倍率充放电，电压范围为0.005～2V，循环3个周期后停止,之后测试其负极片的满电膨胀，测试结果如表2所示。
表2各扣式电池的性能测试对比结果
扣式电池 首次放电容量(mAh/g) 首次效率 满电膨胀
A-1 2080 89.9％ 88.5％
B-1 2040 89.3％ 89.4％
C-1 1920 89.1％ 90.9％
D-1 1720 85.5％ 112.4％
E-1 1710 84.9％ 115.5％
由表2可知，采用本发明实施例1-3提供硅碳复合材料制得的扣式电池与对比例1-2相比，扣式电池的首次放电容量和首次效率得到明显提升，且明显降低了电池的满电膨胀。
为了进一步对以上实施例和对比例进行效果对比验证，本申请还将以上实施例1-3及对比例1-2中得到的硅碳复合材料作为锂离子电池负极材料的活性物质原料，分别通过如下方法组装得到5个规格为5Ah的软包电池：
在其对应的硅碳复合材料中掺杂90wt％(占负极片重量百分比)的人造石墨作为负极材料制得负极片，以三元材料(Li(Ni 0.6Co 0.2Mn 0.2)O 2)为正极材料，以Celgard 2400膜为隔膜，电解液采用LiPF 6为电解质，并以体积比为1:1的碳酸乙烯酯(EC)和碳酸二乙酯(DEC)的混合物为溶剂，LiPF 6的浓度为1.3mol/L；制备得到5Ah的软包电池。按照实施例1、实施例2、实施例3、对比例1、对比例2的顺序，分别将其对应制备得到的软包电池对应标记为A-2、B-2、C-2、D-2、E-2：
本申请将以上实施例1-3及对比例1-2对应制作得到软包电池分别进行了如下性能测试：
(1)对定容后的各软包电池进行解剖后测试其负极极片的厚度D1，然后将各软包电池循环100次(循环测试条件为：1C/1C@25±3℃@2.5-4.2V)后对软包电池进行满电充电，然后再次解剖测试循环后负极极片的厚度D2，然后计算膨胀率(膨胀率为
Figure PCTCN2022133358-appb-000002
)，测试结果请参见下表3所示：
表3各软包电池负极片的膨胀率测试结果
软包电池 D1(μm) D2(μm) 膨胀率
A-2 112 159.5 42.4％
B-2 111 159.0 43.2％
C-2 112 161.5 44.20％
D-2 114 182.5 60.1％
E-2 112 183.6 63.9％
由表3可知，采用本发明实施例1-3提供的硅碳复合材料制得的软包锂离子电池，其负极片的膨胀率明显低于对比例1-2。由此可证实，本发明实施例提供的的硅碳复合材料可以有效降低其应用电池在充放电过程中的膨胀。
(2)对各软包电池进行循环性能测试和倍率测试，测试条件为：充放电 电压范围为2.5～4.2V，温度为25±3.0℃，充放电倍率为1.0C/1.0C。倍率测试：测试其材料在2C条件下的恒流比，其测试结果如表4所示。
表4各软包电池的性能测试结果
Figure PCTCN2022133358-appb-000003
由表4可知，采用本发明实施例1-3提供的硅碳复合材料制得的软包锂离子电池在循环性能上明显优于对比例1-2，由此可进一步证实：本发明实施例提供的硅碳复合材料中具有膨胀低、阻抗低等特性，使其在循环过程中具有较低的膨胀，减少SEI造成的锂离子消耗问题，从而提升循环性能；同时本发明实施例提供的硅碳复合材料阻抗较低，从而提升锂离子电池的倍率性能，即具有较高的恒流比。
对于本领域技术人员而言，显然本发明不限于上述示范性实施例的细节，而且在不背离本发明的精神或基本特征的情况下，能够以其他的具体形式实现本发明。因此，无论从哪一点来看，均应将实施例看作是示范性的，而且是非限制性的，本发明的范围由所附权利要求而不是上述说明限定，因此旨在将落在权利要求的等同要件的含义和范围内的所有变化囊括在本发明内。不应将权利要求中的任何附图标记视为限制所涉及的权利要求。
此外，应当理解，虽然本说明书按照实施方式加以描述，但并非每个实施方式仅包含一个独立的技术方案，说明书的这种叙述方式仅仅是为清楚起 见，本领域技术人员应当将说明书作为一个整体，各实施例中的技术方案也可以经适当组合，形成本领域技术人员可以理解的其他实施方式。

Claims (10)

  1. 一种氮掺杂石墨烯包覆硅碳复合材料，其特征在于，至少包括作为内核的硅基基体以及作为外壳的包覆层；其中，所述包覆层包括氮掺杂无定形碳和石墨烯，所述石墨烯包覆在所述氮掺杂无定形碳的外表面和/或掺杂在所述氮掺杂无定形碳中。
  2. 根据权利要求1所述的氮掺杂石墨烯包覆硅碳复合材料，其特征在于，所述硅基基体与所述包覆层之间的质量比为100:1-8；和/或，所述包覆层中氮掺杂无定形碳和石墨烯之间的质量比为10:0.5-4。
  3. 根据权利要求1或2所述的氮掺杂石墨烯包覆硅碳复合材料，其特征在于，所述硅基基体包括纳米硅，所述氮掺杂无定形碳包括呈多孔网络结构的氮掺杂多孔碳。
  4. 一种根据权利要求1-3之一所述氮掺杂石墨烯包覆硅碳复合材料的制备方法，其特征在于，通过碳源和氮源偶联剂与羧酸化的硅基基体进行电化学聚合得到硅基前驱体，将该硅基前驱体和氧化石墨烯分散液进行水热反应、氢气还原反应和碳化处理后，得到所述氮掺杂石墨烯包覆硅碳复合材料。
  5. 根据权利要求4所述的制备方法，其特征在于，包括如下操作步骤：
    S10)、将所述羧酸化的硅基基体与粘结剂混合均匀后，将其压制成型得到棒状硅基复合体；
    S20)、将溶于溶剂中的碳源和氮源偶联剂作为电解液，将所述棒状硅基复合体作为工作电极，经过电化学聚合制作得到硅基前驱体；
    S30)、将所述硅基前驱体置于氧化石墨烯分散液中分散均匀后，在加热加压条件下进行水热反应后，进行干燥、破碎；
    S40)、将经上述步骤S30)得到的复合材料与氢气进行氢气还原反应后再进行碳化处理，得到所述氮掺杂石墨烯包覆硅碳复合材料。
  6. 根据权利要求4或5所述的制备方法，其特征在于，所述硅基基体包 括纳米硅，通过酸溶液对所述纳米硅进行羧酸化处理；所述碳源包括聚苯乙烯，所述氮源偶联剂包括氨基硅烷偶联剂。
  7. 根据权利要求5所述的制备方法，其特征在于，所述电化学聚合包括：采用饱和甘汞为参比电极，在-2V至2V的电压范围内，以扫描速率为0.5-5mV/s的条件下扫描10-100个周期，对完成电化学聚合的工作电极进行洗涤、过滤，得到作为硅基前驱体的氮掺杂硅/聚苯乙烯微球复合材料。
  8. 根据权利要求4或5所述的制备方法，其特征在于，所述氧化石墨烯分散液中氧化石墨烯的重量份占比为0.5-8wt％；所述水热反应包括：在温度范围设置为100-200℃，压强范围设置为1-5Mpa的条件下进行水热反应至少1小时；所述氢气还原反应包括：在真空状态下通入体积比为1-5:10的氢气与惰性气体，在温度范围设置为250-350℃的条件下进行氢气还原反应至少1小时；所述碳化处理包括：在温度范围设置为700-1100℃的条件下进行碳化至少1小时。
  9. 根据权利要求5或7所述的制备方法，其特征在于，所述硅基前驱体与氧化石墨烯的质量比为100:1-8；所述粘结剂包括沥青和/或聚乙烯醇和/或CMC纤维素粘结剂和/或LA133型粘结剂和/或SBR丁苯胶乳粘结剂和/或LA136D型粘结剂。
  10. 一种根据权利要求1-3之一所述氮掺杂石墨烯包覆硅碳复合材料的应用，将所述氮掺杂石墨烯包覆硅碳复合材料作为制备电池极片的活性物质原料。
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