CN115483385A - A kind of preparation method of three-dimensional composite silicon carbon negative electrode material - Google Patents

A kind of preparation method of three-dimensional composite silicon carbon negative electrode material Download PDF

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CN115483385A
CN115483385A CN202211238038.3A CN202211238038A CN115483385A CN 115483385 A CN115483385 A CN 115483385A CN 202211238038 A CN202211238038 A CN 202211238038A CN 115483385 A CN115483385 A CN 115483385A
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谢煜
马浩
蒋颉
贾莉伟
李新华
夏建超
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Abstract

本发明提供一种三维复合硅碳负极材料的制备方法，包括以下步骤：S1.将炭黑活化，得到多孔炭黑；S2.将1‑10份膨胀石墨加入1‑300份的去离子水中，分散1‑5h得到悬浮液；S3.将悬浮液中加入1‑40份多孔炭黑分散0.2‑1h得到分散液，之后将分散液干燥，得到复合结构碳；S4.将硅源通过CVD分解沉积在复合结构碳上，得到三维多孔硅碳；S5.将三维多孔硅碳和无定形碳混合，之后碳化即得到三维复合硅碳负极材料。本发明的三维复合硅碳负极材料的制备方法，独特的三维结构设计，通过在多孔炭黑和石墨烯纳米片内部沉积超薄纳米硅层，并以多孔碳材料空间来缓解硅造成的体积膨胀，保证了材料的高储锂容量及长循环稳定性。

Figure 202211238038

The invention provides a preparation method of a three-dimensional composite silicon-carbon negative electrode material, comprising the following steps: S1. activating carbon black to obtain porous carbon black; S2. adding 1-10 parts of expanded graphite to 1-300 parts of deionized water, Disperse for 1-5h to obtain a suspension; S3. Add 1-40 parts of porous carbon black to the suspension and disperse for 0.2-1h to obtain a dispersion, then dry the dispersion to obtain a composite structure carbon; S4. Decompose and deposit the silicon source by CVD On the composite structure carbon, three-dimensional porous silicon carbon is obtained; S5. Mix three-dimensional porous silicon carbon and amorphous carbon, and then carbonize to obtain a three-dimensional composite silicon-carbon negative electrode material. The preparation method of the three-dimensional composite silicon-carbon negative electrode material of the present invention has a unique three-dimensional structure design, by depositing an ultra-thin nano-silicon layer inside the porous carbon black and graphene nanosheets, and using the porous carbon material space to alleviate the volume expansion caused by silicon , ensuring the high lithium storage capacity and long-term cycle stability of the material.

Figure 202211238038

Description

一种三维复合硅碳负极材料的制备方法A kind of preparation method of three-dimensional composite silicon carbon negative electrode material

技术领域technical field

本发明涉及锂离子电池技术领域，尤其是一种三维复合硅碳负极材料的制备方法。The invention relates to the technical field of lithium ion batteries, in particular to a preparation method of a three-dimensional composite silicon-carbon negative electrode material.

背景技术Background technique

随着新能源技术的发展，逐步摆脱对化石能源的依赖已成为共识，电动汽车领域及各类储能***对高能量密度锂离子电池的需求也日益增加；在众多负极材料当中，硅有着十倍于当前石墨负极的理论比容量及合适的嵌锂电位，因而被视为极具应用前景的下一代锂离子电池负极材料，但硅基材料在充放电过程中往往伴随着巨大的体积膨胀，导致材料碎裂粉化，与集流体失去电接触，同时，材料表面的SEI膜不断地破碎与再生消耗了大量来自正极的活性锂，严重影响了电池的循环稳定性及倍率性能。With the development of new energy technology, it has become a consensus to gradually get rid of the dependence on fossil energy. The demand for high-energy-density lithium-ion batteries in the field of electric vehicles and various energy storage systems is also increasing; among many negative electrode materials, silicon has a very important role. It is twice the theoretical specific capacity of the current graphite anode and has a suitable lithium intercalation potential, so it is regarded as a very promising next-generation lithium-ion battery anode material. However, silicon-based materials are often accompanied by huge volume expansion during charge and discharge. As a result, the material is fragmented and pulverized, and loses electrical contact with the current collector. At the same time, the SEI film on the surface of the material is continuously broken and regenerated, consuming a large amount of active lithium from the positive electrode, which seriously affects the cycle stability and rate performance of the battery.

当前移动电子设备、电动汽车等领域的快速发展对锂离子电池的性能提出了更高的需求，锂离子电池发展的短期目标需要将能量密度提高至300Wh/kg以上，锂电池正极材料容量短期内难有重大的突破，但负极的容量尚有巨大的提高潜力，因此发展高容量的新型负极材料是进一步提高锂电池能量密度的必然选择。The current rapid development of mobile electronic devices, electric vehicles and other fields puts higher demands on the performance of lithium-ion batteries. The short-term goal of lithium-ion battery development needs to increase the energy density to more than 300Wh/kg. It is difficult to make a major breakthrough, but the capacity of the negative electrode still has great potential for improvement. Therefore, the development of new high-capacity negative electrode materials is an inevitable choice to further increase the energy density of lithium batteries.

硅具有极高的理论容量4200mAh/g，超过现有商业石墨负极材料容量的10倍)和合适的电化学锂化电位，是最具前景的下一代锂电池负极材料；直接使用硅粉制成的电极存在循环稳定性差的问题，但近年来的研究表明，颗粒尺寸在100nm以下的纳米硅结合电极的整体结构设计以及合适的粘结剂可以有效改善硅的循环稳定性；目前基于纳米硅的高容量锂电负极得到学术界和产业界的高度关注。Silicon has a very high theoretical capacity of 4200mAh/g, more than 10 times the capacity of existing commercial graphite anode materials) and a suitable electrochemical lithiation potential, is the most promising next-generation lithium battery anode material; directly made of silicon powder However, studies in recent years have shown that the overall structural design of nano-silicon-bonded electrodes with a particle size below 100nm and a suitable binder can effectively improve the cycle stability of silicon; current nano-silicon-based High-capacity lithium battery anodes have attracted great attention from academia and industry.

中国专利CN 103682287A一种锂离子电池硅基复合负极材料、制备方法及电池，该方法将5.0-40.0μm的硅颗粒通过机械研磨得到10-500nm的纳米硅，采用的湿法研磨，如砂磨机等；这种制备纳米硅的工艺成本高、收率低；而且即使在有机溶剂中研磨，所得纳米硅也容易氧化；之后与空心石墨复合喷雾造粒；由于空心石墨是采用天然石墨、人造石墨等机械加工得到，纳米硅很难均匀分散到空心石墨的间隙中；而且掺杂更多的纳米硅，空心石墨的结构也承接不了；纳米硅团聚，难分散；综上，这种方法成本高、工艺复杂；也不利于产业化；中国专利CN 106207180A一种多孔空心石墨材料的制备方法，该方法将石墨、强碱、碳源高速搅拌混合，之后还需要2800-3000摄氏度的高温石墨化，强碱腐蚀性强，高温石墨化周期长、成本高、能耗高，更不适合产业化。Chinese patent CN 103682287A discloses a silicon-based composite negative electrode material for a lithium-ion battery, a preparation method, and a battery. In this method, silicon particles of 5.0-40.0 μm are mechanically ground to obtain nano-silicon of 10-500 nm, and wet grinding is adopted, such as sand grinding. Machines, etc.; this process for preparing nano-silicon has high cost and low yield; and even if it is ground in an organic solvent, the obtained nano-silicon is also easily oxidized; it is then combined with hollow graphite for spray granulation; since the hollow graphite is made of natural graphite, artificial It is difficult to uniformly disperse nano-silicon into the gaps of hollow graphite obtained by mechanical processing such as graphite; more nano-silicon is doped, and the structure of hollow graphite cannot undertake; nano-silicon is agglomerated and difficult to disperse; in summary, the cost of this method High, complex process; also unfavorable for industrialization; Chinese patent CN 106207180A a preparation method of porous hollow graphite material, the method mixes graphite, strong alkali, and carbon source at high speed, and then requires high-temperature graphitization at 2800-3000 degrees Celsius , strong alkali is highly corrosive, the high-temperature graphitization cycle is long, the cost is high, the energy consumption is high, and it is not suitable for industrialization.

因此为解决以上问题，需要低成本制备纳米硅，还需要一种多孔的碳材料来与纳米硅复合，来解决高容量硅碳复合材料的长循环技术瓶颈。Therefore, in order to solve the above problems, it is necessary to prepare nano-silicon at low cost, and a porous carbon material is needed to compound with nano-silicon to solve the long-cycle technology bottleneck of high-capacity silicon-carbon composite materials.

发明内容Contents of the invention

本发明的目的是在于克服、补充现有技术中存在的不足，提供一种三维复合硅碳负极材料的制备方法，通过将炭黑活化制备多孔炭黑，多孔碳黑与膨胀石墨超声分散得到二者复合的多孔结构材料，炭黑提供多孔结构，采用硅烷、和/或氯硅烷(如单氯、二、三和四氯硅烷)来低成本制备纳米硅，通过在多孔炭黑和石墨烯纳米片内部沉积超薄纳米硅层，并以大孔层隙的碳材料空间来缓解硅造成体积膨胀，保证了材料的高储锂容量及长循环稳定性。本发明采用的技术方案是：The purpose of the present invention is to overcome and supplement the deficiencies in the prior art, and to provide a preparation method for a three-dimensional composite silicon-carbon negative electrode material. The porous carbon black is prepared by activating the carbon black, and the porous carbon black and expanded graphite are ultrasonically dispersed to obtain two Or composite porous structure materials, carbon black provides porous structure, using silane, and/or chlorosilane (such as monochloro, di, tri and tetrachlorosilane) to prepare nano-silicon at low cost, through porous carbon black and graphene nano The ultra-thin nano-silicon layer is deposited inside the chip, and the volume expansion caused by silicon is relieved by the carbon material space with large pores, which ensures the high lithium storage capacity and long-term cycle stability of the material. The technical scheme adopted in the present invention is:

一种三维复合硅碳负极材料的制备方法，其中：包括以下步骤：A method for preparing a three-dimensional composite silicon-carbon negative electrode material, wherein: comprising the following steps:

S1.将炭黑活化，得到多孔炭黑；S1. Activate carbon black to obtain porous carbon black;

S2.将1-10份膨胀石墨加入1-300份的去离子水中，分散1-5h得到悬浮液；S2. Add 1-10 parts of expanded graphite into 1-300 parts of deionized water, and disperse for 1-5 hours to obtain a suspension;

S3.将悬浮液中加入1-40份多孔炭黑分散0.2-1h得到分散液，之后将分散液干燥，得到复合结构碳；S3. Add 1-40 parts of porous carbon black to the suspension and disperse for 0.2-1 h to obtain a dispersion, then dry the dispersion to obtain a composite structure carbon;

S4.将硅源通过CVD分解沉积在复合结构碳上，得到三维多孔硅碳；S4. Decomposing and depositing the silicon source on the composite structure carbon by CVD to obtain a three-dimensional porous silicon carbon;

S5.将三维多孔硅碳和无定形碳混合，之后碳化即得到三维复合硅碳负极材料。S5. Mix three-dimensional porous silicon carbon and amorphous carbon, and then carbonize to obtain a three-dimensional composite silicon carbon negative electrode material.

优选的是，所述的三维复合硅碳负极材料的制备方法，其中：所述步骤S1中的炭黑是通过水蒸气或者二氧化碳活化的，活化温度为600-900℃，活化时间为1-6h。Preferably, the preparation method of the three-dimensional composite silicon-carbon negative electrode material, wherein: the carbon black in the step S1 is activated by water vapor or carbon dioxide, the activation temperature is 600-900°C, and the activation time is 1-6h .

优选的是，所述的三维复合硅碳负极材料的制备方法，其中：所述步骤S1中的炭黑孔径为10-150nm，D50＜25μm，比表面积为10-100m2/g，孔隙率为10-70％。Preferably, the preparation method of the three-dimensional composite silicon-carbon negative electrode material, wherein: the carbon black in the step S1 has a pore diameter of 10-150 nm, D50<25 μm, a specific surface area of 10-100 m 2 /g, and a porosity of 10-70%.

优选的是，所述的三维复合硅碳负极材料的制备方法，其中：所述步骤S2中膨胀石墨的膨胀倍率为30-120mL/g。Preferably, the preparation method of the three-dimensional composite silicon-carbon negative electrode material, wherein: the expansion ratio of the expanded graphite in the step S2 is 30-120mL/g.

优选的是，所述的三维复合硅碳负极材料的制备方法，其中：所述所述步骤S3中干燥温度为100-200℃，干燥时间为0.5-4h。Preferably, the method for preparing a three-dimensional composite silicon-carbon anode material, wherein: in the step S3, the drying temperature is 100-200° C., and the drying time is 0.5-4 hours.

优选的是，所述的三维复合硅碳负极材料的制备方法，其中：所述步骤S4中的硅源为硅烷和氯硅烷的一种或多种。Preferably, in the preparation method of the three-dimensional composite silicon-carbon anode material, wherein: the silicon source in the step S4 is one or more of silane and chlorosilane.

优选的是，所述的三维复合硅碳负极材料的制备方法，其中：所述氯硅烷为单氯硅烷、二氯硅烷、三氯硅烷和四氯硅烷的一种或多种。Preferably, the preparation method of the three-dimensional composite silicon-carbon negative electrode material, wherein: the chlorosilane is one or more of monochlorosilane, dichlorosilane, trichlorosilane and tetrachlorosilane.

优选的是，所述的三维复合硅碳负极材料的制备方法，其中：所述步骤S4硅源通过CVD分解沉积在复合结构碳上具体工艺为：将复合结构碳放置在回转炉中，并通入硅源和载气进行沉积，控制沉积温度为400℃-850℃，沉积时间为0.1-8h；所述载气为氮气或氩气。Preferably, the preparation method of the three-dimensional composite silicon-carbon negative electrode material, wherein: in the step S4, the silicon source is decomposed and deposited on the composite structure carbon by CVD. The specific process is: placing the composite structure carbon in a rotary furnace, and passing Introduce silicon source and carrier gas for deposition, control the deposition temperature to 400°C-850°C, and deposit time to 0.1-8h; the carrier gas is nitrogen or argon.

优选的是，所述的三维复合硅碳负极材料的制备方法，其中：所述步骤S5的无定形碳为中温煤沥青、高温煤沥青、石油沥青、煤焦油、石油重质渣油、重质芳香烃和中间相沥青的一种或多种。Preferably, the preparation method of the three-dimensional composite silicon-carbon negative electrode material, wherein: the amorphous carbon in the step S5 is medium-temperature coal tar pitch, high-temperature coal tar pitch, petroleum pitch, coal tar, petroleum heavy residue, heavy One or more of aromatic hydrocarbons and mesophase pitch.

优选的是，所述的三维复合硅碳负极材料的制备方法，其中：所述步骤S5的碳化温度为800-950℃，碳化时间为0.5-3h。Preferably, the preparation method of the three-dimensional composite silicon-carbon negative electrode material, wherein: the carbonization temperature in the step S5 is 800-950°C, and the carbonization time is 0.5-3h.

本发明的优点：Advantages of the present invention:

(1)本发明的三维复合硅碳负极材料的制备方法，多孔碳材料的原料炭黑来源广泛，成本低廉，制备多孔炭黑采用的是物理法活化，环保无污；纳米硅的制备采用硅烷CVD沉积，工艺流程短，纳米硅的尺寸可控，成本低，易于产业化。(1) The preparation method of the three-dimensional composite silicon-carbon negative electrode material of the present invention, the raw material carbon black of porous carbon material has a wide range of sources, and the cost is low, and what the preparation porous carbon black adopts is physical method activation, environmental protection is pollution-free; The preparation of nano-silicon adopts silane CVD deposition, short process flow, controllable nano-silicon size, low cost, and easy industrialization.

(2)本发明的三维复合硅碳负极材料的制备方法，在多孔炭黑和石墨烯纳米片复合材料表面均匀沉积一层纳米硅，而后在三维多孔硅碳外壳包覆一层无定形碳，从而避免多孔三维多孔硅碳直接与电解液接触，降低其副反应的发生，包覆的碳层提高了其导电性，这种三维复合硅碳负极材料的结构有利于提高倍率性能，多孔碳为硅膨胀提供了足够的体积，并允许锂离子的快速传输，而包覆碳层的存在允许改善固体/电解质界面的形成，提高了材料的结构完整性和导电性；因此，多孔碳复合硅碳负极可以在循环时保持优异的循环稳定性，这对于工业应用极为重要。(2) The preparation method of the three-dimensional composite silicon-carbon negative electrode material of the present invention uniformly deposits a layer of nano-silicon on the surface of the porous carbon black and graphene nanosheet composite material, and then coats one layer of amorphous carbon on the three-dimensional porous silicon-carbon shell, In order to avoid the direct contact of porous three-dimensional porous silicon carbon with the electrolyte, reduce the occurrence of side reactions, and the coated carbon layer improves its conductivity. The structure of this three-dimensional composite silicon carbon negative electrode material is conducive to improving the rate performance. The porous carbon is Silicon expansion provides sufficient volume and allows rapid transport of lithium ions, while the presence of the encapsulating carbon layer allows for improved solid/electrolyte interface formation, enhancing the structural integrity and electrical conductivity of the material; thus, the porous carbon-composite silicon-carbon The anode can maintain excellent cycle stability during cycling, which is extremely important for industrial applications.

(3)本发明的三维复合硅碳负极材料的制备方法，独特的三维结构设计，通过在多孔炭黑和石墨烯纳米片内部沉积超薄纳米硅层，并以多孔碳材料空间来缓解硅造成的体积膨胀，保证了材料的高储锂容量及长循环稳定性。(3) The preparation method of the three-dimensional composite silicon-carbon negative electrode material of the present invention has a unique three-dimensional structure design, by depositing an ultra-thin nano-silicon layer inside the porous carbon black and graphene nanosheets, and using the porous carbon material space to alleviate the formation of silicon. The volume expansion ensures the high lithium storage capacity and long-term cycle stability of the material.

(4)本发明的三维复合硅碳负极材料的制备方法，制备的三维复合硅碳负极材料循环性能优异且具有较高的比容量，工业化成本低，具有较大的市场竞争力。(4) According to the preparation method of the three-dimensional composite silicon-carbon negative electrode material of the present invention, the prepared three-dimensional composite silicon-carbon negative electrode material has excellent cycle performance, high specific capacity, low industrialization cost, and great market competitiveness.

附图说明Description of drawings

图1为本发明三维复合硅碳负极材料的制备方法的工艺流程图。Fig. 1 is a process flow chart of the preparation method of the three-dimensional composite silicon-carbon anode material of the present invention.

图2为本发明实施例1的三维复合硅碳负极材料的扫描电镜图。Fig. 2 is a scanning electron microscope image of the three-dimensional composite silicon-carbon anode material of Example 1 of the present invention.

图3为本发明实施例1的三维复合硅碳负极材料的扣式电池循环测试曲线图。Fig. 3 is a graph showing a cycle test curve of a button battery of the three-dimensional composite silicon-carbon negative electrode material of Example 1 of the present invention.

图4为本发明实施例1的三维复合硅碳负极材料的扣式电池首圈循环曲线图。Fig. 4 is a first-cycle cycle graph of the button battery of the three-dimensional composite silicon-carbon anode material of Example 1 of the present invention.

具体实施方式detailed description

下面结合具体附图和实施例对本发明作进一步说明。The present invention will be further described below in conjunction with specific drawings and embodiments.

实施例1Example 1

如图1所示，一种三维复合硅碳负极材料的制备方法，其中：包括以下步骤：As shown in Figure 1, a method for preparing a three-dimensional composite silicon-carbon negative electrode material, wherein: comprising the following steps:

S1.将10kg炭黑放入卧式活化炉中，采用水蒸气在600℃活化1h，得到多孔炭黑；S1. Put 10kg of carbon black into a horizontal activation furnace and activate it with water vapor at 600°C for 1 hour to obtain porous carbon black;

S2.将2kg膨胀石墨加入60kg的去离子水，在1000W工业型超声波分散机超声分散3h得到悬浮液；S2. Add 2kg of expanded graphite to 60kg of deionized water, and ultrasonically disperse for 3 hours in a 1000W industrial ultrasonic disperser to obtain a suspension;

S3.将悬浮液中加入10kg的多孔炭黑再分散0.5h得到分散液，之后将分散液在回转窑炉中120℃干燥1h，即得到多孔炭黑和石墨烯纳米片复合的复合结构碳；S3. Add 10kg of porous carbon black to the suspension and disperse it for 0.5h to obtain a dispersion, then dry the dispersion at 120°C for 1h in a rotary kiln to obtain a composite structure carbon composed of porous carbon black and graphene nanosheets;

S4.在回转炉中硅烷以60L/h，载气为氩气180L/h，通入上述制备的多孔炭黑和石墨烯纳米片复合的多孔碳中，硅烷沉积温度为450℃，沉积时间为2h，即得到纳米硅沉积复合的三维多孔硅碳，硅烷沉积得到的纳米硅颗粒的粒径为90±5nm，三维多孔硅碳孔径100nm，比表面积30m2/g；孔隙率85％；S4. in the rotary kiln, silane is with 60L/h, and carrier gas is argon gas 180L/h, passes in the porous carbon of the porous carbon black of above-mentioned preparation and graphene nanosheet composite, and silane deposition temperature is 450 ℃, and deposition time is After 2 hours, three-dimensional porous silicon carbon composited by nano-silicon deposition is obtained. The particle size of nano-silicon particles obtained by silane deposition is 90±5nm, the pore diameter of three-dimensional porous silicon carbon is 100nm, the specific surface area is 30m 2 /g, and the porosity is 85%;

S5.三维多孔硅碳和高温煤沥青一起加入VC混合机均匀混合包覆，混合30min，之后900℃碳化2h，即得到三维复合硅碳负极材料。S5. Three-dimensional porous silicon carbon and high-temperature coal tar pitch were added to a VC mixer for uniform mixing and coating, mixed for 30 minutes, and then carbonized at 900°C for 2 hours to obtain a three-dimensional composite silicon-carbon negative electrode material.

实施例2Example 2

如图1所示，一种三维复合硅碳负极材料的制备方法，其中：包括以下步骤：As shown in Figure 1, a method for preparing a three-dimensional composite silicon-carbon negative electrode material, wherein: comprising the following steps:

S1.将40kg炭黑放入卧式活化炉中，采用二氧化碳在800℃活化2h，制备得到多孔炭黑；S1. Put 40kg of carbon black into a horizontal activation furnace and activate it with carbon dioxide at 800°C for 2 hours to prepare porous carbon black;

S2.将8Kg膨胀石墨200kg的去离子水，膨胀石墨在1000W工业型超声波分散机超声分散3h得到悬浮液；S2. With 8Kg of expanded graphite and 200kg of deionized water, the expanded graphite is ultrasonically dispersed in a 1000W industrial ultrasonic disperser for 3 hours to obtain a suspension;

S3.将悬浮液中加入40kg的多孔炭黑再分散1h得到分散液，之后将分散液放在回转窑炉中150℃干燥1h，即得到多孔炭黑和石墨烯纳米片复合的复合结构碳；S3. Add 40kg of porous carbon black to the suspension and disperse it for 1 hour to obtain a dispersion, then place the dispersion in a rotary kiln and dry it at 150°C for 1 hour to obtain a composite structure carbon composed of porous carbon black and graphene nanosheets;

S4.在回转炉中四硅烷以80L/h，载气为氩气200L/h，通入上述制备的复合结构碳中，硅烷沉积温度550℃，沉积时间1.5h，硅烷沉积得到的纳米硅颗粒60±5nm，得到三维多孔硅碳的孔径为110nm，比表面积为40m2/g，孔隙率为90％；S4. In a rotary furnace, 80 L/h of tetrasilane and 200 L/h of argon as the carrier gas are passed into the composite structure carbon prepared above. The silane deposition temperature is 550 ° C and the deposition time is 1.5 h. The nano-silicon particles obtained by silane deposition 60±5nm, the obtained three-dimensional porous silicon carbon has a pore diameter of 110nm, a specific surface area of 40m 2 /g, and a porosity of 90%;

S5.将三维多孔硅碳和石油沥青一起加入VC混合机均匀混合包覆，混合10min，之后800℃碳化0.5h，即得到三维复合硅碳负极材料。S5. Add the three-dimensional porous silicon carbon and petroleum pitch into the VC mixer for uniform mixing and coating, mix for 10 minutes, and then carbonize at 800°C for 0.5 hours to obtain the three-dimensional composite silicon carbon negative electrode material.

实施例3Example 3

一种三维复合硅碳负极材料的制备方法，其中：包括以下步骤：A method for preparing a three-dimensional composite silicon-carbon negative electrode material, wherein: comprising the following steps:

S1.将10kg炭黑放入卧式活化炉中，采用水蒸气在700℃活化2h，制备得到多孔炭黑；S1. Put 10kg of carbon black into a horizontal activation furnace and activate it with water vapor at 700°C for 2 hours to prepare porous carbon black;

S2.将2kg膨胀石墨加入60kg去离子水，在1000W工业型超声波分散机超声分散4h得到悬浮液；S2. Add 2kg of expanded graphite to 60kg of deionized water, and ultrasonically disperse for 4 hours in a 1000W industrial ultrasonic disperser to obtain a suspension;

S3.将悬浮液中加入10kg的多孔炭黑再分散1h得到分散液，之后将分散液在回转窑炉中150℃干燥1h，即得到多孔炭黑和石墨烯纳米片复合的复合结构碳；S3. Add 10 kg of porous carbon black to the suspension and disperse for 1 hour to obtain a dispersion, then dry the dispersion in a rotary kiln at 150° C. for 1 hour to obtain a composite structure carbon composed of porous carbon black and graphene nanosheets;

S4.在回转炉中硅烷以60L/h，载气为氩气120L/h，通入上述制备的复合结构碳中，硅烷沉积温度为700℃，沉积时间为3h得到三维多孔硅碳，硅烷沉积得到的纳米硅颗粒50±5nm，三维多孔硅碳孔径为100nm，比表面积为25m2/g，孔隙率为88％；S4. In the rotary furnace, 60L/h of silane and 120L/h of argon as the carrier gas are passed into the composite structure carbon prepared above. The silane deposition temperature is 700°C and the deposition time is 3h to obtain three-dimensional porous silicon carbon. Silane deposition The obtained nano-silicon particles are 50±5nm, the pore diameter of the three-dimensional porous silicon carbon is 100nm, the specific surface area is 25m 2 /g, and the porosity is 88%;

S5.三维多孔硅碳和中间相沥青一起加入VC混合机均匀混合包覆，混合30min，之后900℃碳化2h，即得到三维复合硅碳负极材料。S5. Three-dimensional porous silicon carbon and mesophase pitch were added to a VC mixer for uniform mixing and coating, mixed for 30 minutes, and then carbonized at 900°C for 2 hours to obtain a three-dimensional composite silicon carbon negative electrode material.

实施例4Example 4

S1.将40kg炭黑放入卧式活化炉中，采用二氧化碳在900℃活化6h，制备得到多孔炭黑；S1. Put 40kg of carbon black into a horizontal activation furnace and activate it with carbon dioxide at 900°C for 6 hours to prepare porous carbon black;

S2.将8Kg膨胀石墨加入200kg的去离子水中，在1000W工业型超声波分散机超声分散5h得到悬浮液；S2. Add 8Kg of expanded graphite into 200kg of deionized water, and ultrasonically disperse for 5 hours in a 1000W industrial ultrasonic disperser to obtain a suspension;

S3.将悬浮液中加入40kg的多孔炭黑再分散1h得到分散液，之后将分散液在回转窑炉中200℃干燥4h，即得到多孔炭黑和石墨烯纳米片复合的复合结构碳；S3. Add 40kg of porous carbon black to the suspension and disperse it for 1 hour to obtain a dispersion, then dry the dispersion at 200° C. for 4 hours in a rotary kiln to obtain a composite structure carbon composed of porous carbon black and graphene nanosheets;

S4.在回转炉中四硅烷以80L/h，载气为氩气240L/h，通入上述制备的复合结构碳中，硅烷沉积温度为850℃，沉积时间为6h，即得到纳米硅沉积复合的三维多孔硅碳，硅烷沉积得到的纳米硅颗粒为40±5nm，三维多孔硅碳孔径为120nm，比表面积为50m2/g，孔隙率为90％；S4. In the rotary furnace, 80L/h of tetrasilane and 240L/h of argon as the carrier gas are passed into the composite structure carbon prepared above. The silane deposition temperature is 850°C and the deposition time is 6h, and the nano-silicon deposition composite is obtained. The three-dimensional porous silicon carbon, the nano-silicon particles obtained by silane deposition are 40±5nm, the pore diameter of the three-dimensional porous silicon carbon is 120nm, the specific surface area is 50m 2 /g, and the porosity is 90%;

S5.三维多孔硅碳和中温沥青一起加入VC混合机均匀混合包覆，混合10min，之后900℃碳化3h，即得到三维复合硅碳负极材料。S5. Three-dimensional porous silicon carbon and medium-temperature asphalt were added to a VC mixer for uniform mixing and coating, mixed for 10 minutes, and then carbonized at 900°C for 3 hours to obtain a three-dimensional composite silicon-carbon negative electrode material.

对比例1Comparative example 1

一种三维复合硅碳负极材料的制备方法，其中：包括以下步骤：A method for preparing a three-dimensional composite silicon-carbon negative electrode material, wherein: comprising the following steps:

S1.将2kg膨胀石墨先在1000W工业型超声波分散机超声分散3h得到悬浮液；S1. Ultrasonic disperse 2kg of expanded graphite in a 1000W industrial ultrasonic disperser for 3 hours to obtain a suspension;

S2.将10kg炭黑加入悬浮液中再分散0.5h，之后在回转窑炉中120℃干燥1h，即得到多孔炭黑和石墨烯纳米片复合的复合结构碳；S2. Add 10kg of carbon black into the suspension and disperse for 0.5h, then dry at 120°C for 1h in a rotary kiln to obtain a composite structure carbon composed of porous carbon black and graphene nanosheets;

S3.在回转炉中硅烷以60L/h，载气为氩气180L/h，通入上述制备的多孔炭黑和石墨烯纳米片复合的复合结构碳中，硅烷沉积温度为450℃，沉积时间为2h，即得到纳米硅沉积复合的三维多孔硅碳，硅烷沉积得到的纳米硅颗粒90±5nm，三维多孔硅碳孔径为60nm，比表面积为20m2/g，孔隙率为65％，三维多孔硅碳和高温煤沥青一起加入VC混合机均匀混合包覆，混合30min，之后900℃碳化2h，即得到三维复合硅碳负极材料。S3. In the rotary furnace, 60L/h of silane and 180L/h of argon as the carrier gas are passed into the composite structure carbon of the porous carbon black and graphene nanosheets prepared above. The silane deposition temperature is 450 ° C, and the deposition time is For 2 hours, the three-dimensional porous silicon carbon composited by nano-silicon deposition is obtained. The nano-silicon particles obtained by silane deposition are 90±5nm, the pore diameter of the three-dimensional porous silicon carbon is 60nm, the specific surface area is 20m 2 /g, the porosity is 65%, and the three-dimensional porous Silicon carbon and high-temperature coal tar pitch were added together into a VC mixer for uniform mixing and coating, mixed for 30 minutes, and then carbonized at 900°C for 2 hours to obtain a three-dimensional composite silicon carbon negative electrode material.

对比例2Comparative example 2

对比例2的步骤和实施例2区别在于不对炭黑进行活化，也不对膨胀石墨超声处理，而是炭黑直接与膨胀石墨复合，其他步骤均相同。The difference between the steps of Comparative Example 2 and Example 2 is that the carbon black is not activated, and the expanded graphite is not ultrasonically treated, but the carbon black is directly compounded with the expanded graphite, and the other steps are the same.

实施例1-4极片制作以及电池组装，Embodiment 1-4 pole piece making and battery assembly,

1、极片制作：将实施例1-4制备的三维复合硅碳负极材料、导电炭黑(SP)、聚丙烯酸(PAA)粘结剂按照70:15:15的比例混合，放入行星式混浆机中，加入去离子水调节粘度；将混合好的浆料倾倒在9μm厚度的铜箔上，调节自动涂膜器上刮刀厚度，使浆料均匀涂覆在铜箔上；将涂布好的极片自然晾干后转移到80℃鼓风干燥箱中烘；将烘干好的极片用辊压机辊压，使活性物质与集流体的结合紧密，控制辊压机的辊压厚度，使极片的面密度控制在1g/cm3以下；将压实的极片用12或14cm直径的冲压模具切成圆片，烘干、称量、得到硅碳负极材料电极。1. Electrode production: Mix the three-dimensional composite silicon-carbon negative electrode material prepared in Example 1-4, conductive carbon black (SP), and polyacrylic acid (PAA) binder according to the ratio of 70:15:15, and put it into a planetary In the mixer, add deionized water to adjust the viscosity; pour the mixed slurry on the copper foil with a thickness of 9 μm, adjust the thickness of the scraper on the automatic film applicator, so that the slurry is evenly coated on the copper foil; After the good pole piece is dried naturally, it is transferred to an 80°C blast drying oven for drying; the dried pole piece is rolled with a roller press to make the active material and the current collector tightly combined, and the roll pressure of the roller press is controlled Thickness, so that the areal density of the pole piece is controlled below 1g/cm 3 ; the compacted pole piece is cut into circular slices with a stamping die with a diameter of 12 or 14cm, dried, weighed, and a silicon carbon negative electrode material electrode is obtained.

2、电池组装：将极片放入氩气气氛下的手套箱中，以CR2032电池壳为模具制作扣式电池，将上述步骤制成的硅碳负极材料电极和锂对电极，添加120微升1mol/L LiPF6电解液(溶剂为EC：DMC：EMC体积比1:1:1，并含10％质量含量的添加剂FEC)，并将隔膜置于硅碳负极材料电极和对电极中间，在手套箱中组装成密封完好的复合电极体系的半电池。2. Battery assembly: Put the pole piece in a glove box under an argon atmosphere, use the CR2032 battery case as a mold to make a button battery, and add 120 microliters to the silicon-carbon negative electrode material electrode and lithium counter electrode made in the above steps 1mol/L LiPF 6 electrolyte (solvent is EC:DMC:EMC volume ratio 1:1:1, and the additive FEC that contains 10% mass content), and separator is placed between silicon carbon negative electrode material electrode and counter electrode, in A half-cell assembled into a well-sealed composite electrode system in a glove box.

3、电池测试：将组装好的电池以0.1C的电流密度在0.005V-1.5V电压区间进行充放电测试。记录充电比容量与放电比容量数据。3. Battery test: The assembled battery is charged and discharged in the voltage range of 0.005V-1.5V at a current density of 0.1C. Record charge specific capacity and discharge specific capacity data.

实施例1-4和对比例1-2的电池性能测试结果如表1The battery performance test results of Examples 1-4 and Comparative Examples 1-2 are shown in Table 1

表1性能比对结果表Table 1 performance comparison result table

Figure BDA0003883770280000061
Figure BDA0003883770280000061

从表1可以看出，实施例1-4是采用炭黑多孔化之后与石墨烯纳米片复合，之后再硅烷CVD沉积，无定形碳包覆，首次效率、首次充电容量和循环保保持率均高于对比例的1-2。As can be seen from Table 1, Examples 1-4 are composited with graphene nanosheets after carbon black is made porous, then silane CVD deposition, amorphous carbon coating, first-time efficiency, first-time charge capacity and cycle retention rate are all average. Higher than 1-2 of the comparative example.

图2为实施例1的三维复合硅碳负极材料的扫描电镜图片，从图2可以清晰的看到多孔复合结构内的空隙上纳米硅颗粒沉积在复合材料的表面上。Fig. 2 is a scanning electron microscope picture of the three-dimensional composite silicon-carbon anode material of Example 1. It can be clearly seen from Fig. 2 that nano-silicon particles are deposited on the surface of the composite material on the voids in the porous composite structure.

图3为实施例1的三维复合硅碳负极材料的扣式电池循环测试曲线充放电的循环曲线，可以看到300次循环之后容量衰减很少。Fig. 3 is the cycle curve of charging and discharging of the button battery cycle test curve of the three-dimensional composite silicon-carbon negative electrode material of Example 1, and it can be seen that the capacity fades little after 300 cycles.

图4为实施例1的首次充放电曲线，可以看出首次效率高。Fig. 4 is the first charge and discharge curve of embodiment 1, it can be seen that the first time efficiency is high.

最后所应说明的是，以上具体实施方式仅用以说明本发明的技术方案而非限制，尽管参照实例对本发明进行了详细说明，本领域的普通技术人员应当理解，可以对本发明的技术方案进行修改或者等同替换，而不脱离本发明技术方案的精神和范围，其均应涵盖在本发明的权利要求范围当中。Finally, it should be noted that the above specific embodiments are only used to illustrate the technical solutions of the present invention without limitation, although the present invention has been described in detail with reference to examples, those of ordinary skill in the art should understand that the technical solutions of the present invention can be carried out Modifications or equivalent replacements without departing from the spirit and scope of the technical solution of the present invention shall be covered by the claims of the present invention.

Claims (10)

1.一种三维复合硅碳负极材料的制备方法，其特征在于：包括以下步骤：1. A preparation method for a three-dimensional composite silicon-carbon negative electrode material, characterized in that: comprise the following steps: S1.将炭黑物理活化，得到多孔炭黑；S1. Activate carbon black physically to obtain porous carbon black; S2.将1-10份膨胀石墨加入1-300份的去离子水中，分散1-5h得到悬浮液；S2. Add 1-10 parts of expanded graphite into 1-300 parts of deionized water, and disperse for 1-5 hours to obtain a suspension; S3.将悬浮液中加入1-40份多孔炭黑分散0.2-1h得到分散液，之后将分散液干燥，得到复合结构碳；S3. Add 1-40 parts of porous carbon black to the suspension and disperse for 0.2-1 h to obtain a dispersion, then dry the dispersion to obtain a composite structure carbon; S4.将硅源通过CVD分解并沉积在复合结构碳上，得到三维多孔硅碳；S4. Decomposing the silicon source by CVD and depositing it on the composite structure carbon to obtain a three-dimensional porous silicon carbon; S5.将三维多孔硅碳和无定形碳混合，之后碳化即得到三维复合硅碳负极材料。S5. Mix three-dimensional porous silicon carbon and amorphous carbon, and then carbonize to obtain a three-dimensional composite silicon carbon negative electrode material. 2.如权利要求1所述的三维复合硅碳负极材料的制备方法，其特征在于：步骤S1中的炭黑是通过水蒸气或者二氧化碳活化的，活化温度为600-900℃，活化时间为1-6h。2. The method for preparing a three-dimensional composite silicon-carbon negative electrode material according to claim 1, wherein the carbon black in step S1 is activated by water vapor or carbon dioxide, the activation temperature is 600-900°C, and the activation time is 1 -6h. 3.如权利要求1所述的三维复合硅碳负极材料的制备方法，其特征在于：步骤S1中的炭黑孔径为10-150nm，D50＜25μm，比表面积为10-100m2/g，孔隙率为10-70%。3. The method for preparing a three-dimensional composite silicon-carbon negative electrode material according to claim 1, characterized in that: the carbon black in step S1 has a pore diameter of 10-150 nm, D50<25 μm, a specific surface area of 10-100 m 2 /g, and a pore size of 10-150 nm. The rate is 10-70%. 4.如权利要求1所述的三维复合硅碳负极材料的制备方法，其特征在于：步骤S2中膨胀石墨的膨胀倍率为30-120mL/g。4 . The method for preparing a three-dimensional composite silicon-carbon negative electrode material according to claim 1 , wherein the expansion ratio of the expanded graphite in step S2 is 30-120 mL/g. 5.如权利要求1所述的三维复合硅碳负极材料的制备方法，其特征在于：步骤S3中的干燥温度为100-200℃，干燥时间为0.5-4h。5 . The method for preparing a three-dimensional composite silicon-carbon anode material according to claim 1 , wherein the drying temperature in step S3 is 100-200° C., and the drying time is 0.5-4 hours. 6.如权利要求1所述的三维复合硅碳负极材料的制备方法，其特征在于：步骤S4中的硅源为硅烷和氯硅烷的一种或多种。6. The method for preparing a three-dimensional composite silicon-carbon negative electrode material according to claim 1, characterized in that: the silicon source in step S4 is one or more of silane and chlorosilane. 7.如权利要求6所述的三维复合硅碳负极材料的制备方法，其特征在于：所述氯硅烷为单氯硅烷、二氯硅烷、三氯硅烷和四氯硅烷的一种或多种。7. The method for preparing a three-dimensional composite silicon-carbon negative electrode material according to claim 6, wherein the chlorosilane is one or more of monochlorosilane, dichlorosilane, trichlorosilane and tetrachlorosilane. 8.如权利要求1所述的三维复合硅碳负极材料的制备方法，其特征在于：所述步骤S4硅源通过CVD分解并沉积在复合结构碳上具体工艺为：将复合结构碳放置在回转炉中，并通入硅源和载气进行沉积，控制沉积温度为400℃-850℃，沉积时间为0.1-8h，所述载气为氮气或氩气。8. The preparation method of three-dimensional composite silicon-carbon negative electrode material as claimed in claim 1, characterized in that: the step S4 silicon source is decomposed by CVD and deposited on the composite structure carbon. The specific process is: the composite structure carbon is placed in the In a converter, the silicon source and carrier gas are fed to deposit, the deposition temperature is controlled to be 400°C-850°C, the deposition time is 0.1-8h, and the carrier gas is nitrogen or argon. 9.如权利要求1所述的三维复合硅碳负极材料的制备方法，其特征在于：步骤S5的无定形碳为中温煤沥青、高温煤沥青、石油沥青、煤焦油、石油重质渣油、重质芳香烃和中间相沥青的一种或多种。9. The method for preparing a three-dimensional composite silicon-carbon negative electrode material as claimed in claim 1, wherein the amorphous carbon in step S5 is medium-temperature coal tar pitch, high-temperature coal tar pitch, petroleum pitch, coal tar, heavy petroleum residue, One or more of heavy aromatic hydrocarbons and mesophase pitch. 10.如权利要求1所述的三维复合硅碳负极材料的制备方法，其特征在于：步骤S5的碳化温度为800-950℃，碳化时间为0.5-3h。10 . The method for preparing a three-dimensional composite silicon-carbon negative electrode material according to claim 1 , wherein the carbonization temperature in step S5 is 800-950° C., and the carbonization time is 0.5-3 h. 11 .
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