CN112125294A - Coal-based silicon-carbon composite negative electrode material and preparation method thereof - Google Patents

Coal-based silicon-carbon composite negative electrode material and preparation method thereof Download PDF

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CN112125294A
CN112125294A CN202010997901.8A CN202010997901A CN112125294A CN 112125294 A CN112125294 A CN 112125294A CN 202010997901 A CN202010997901 A CN 202010997901A CN 112125294 A CN112125294 A CN 112125294A
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王夏阳
曹新龙
田占元
张长安
曹国林
白杨芝
薛孟尧
胥鑫
霍林智
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Shaanxi Coal and Chemical Technology Institute Co Ltd
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Abstract

本发明公开的一种煤基硅碳复合负极材料及其制备方法，以无烟煤为碳源，以硅藻土为硅源，无烟煤低温炭化得到的无定型多孔碳，可以促进锂离子有序脱嵌，提高材料比容量，硅藻土本身的多孔结构实现预留膨胀空间，有效改善硅基负极的膨胀问题，同时硅藻土提纯得到的多孔SiO2与金属锂进行热还原，实现了SiOx的制备和煤基硅碳复合负极材料的预锂，进一步提高负极材料的循环稳定性；本发明公开的一种煤基硅碳复合负极材料及其制备方法，旨在解决硅基负极材料的膨胀，在不降低导电性的基础上提高材料首次库伦效力，同时以无烟煤为碳源、以硅藻土为硅源，降低材料制备成本，有利于实现硅基负极材料的工业化生产。

Figure 202010997901

The invention discloses a coal-based silicon-carbon composite negative electrode material and a preparation method thereof. Anthracite is used as a carbon source, diatomite is used as a silicon source, and the amorphous porous carbon obtained by low-temperature carbonization of anthracite can promote the orderly de-intercalation of lithium ions. , to improve the specific capacity of the material, the porous structure of diatomite itself realizes the reserved expansion space, which effectively improves the expansion problem of the silicon - based negative electrode. The preparation and pre-lithium of the coal-based silicon-carbon composite negative electrode material further improve the cycle stability of the negative electrode material; a coal-based silicon-carbon composite negative electrode material and a preparation method thereof disclosed in the invention aim to solve the expansion of the silicon-based negative electrode material, On the basis of not reducing the electrical conductivity, the first Coulomb efficiency of the material is improved. At the same time, anthracite is used as the carbon source and diatomite as the silicon source, which reduces the material preparation cost and is beneficial to the industrialized production of silicon-based negative electrode materials.

Figure 202010997901

Description

一种煤基硅碳复合负极材料其制备方法A kind of coal-based silicon carbon composite negative electrode material and preparation method thereof

技术领域technical field

本发明属于锂离子电池负极材料技术领域，具体涉及一种煤基硅碳复合负极材料其制备方法。The invention belongs to the technical field of negative electrode materials for lithium ion batteries, and in particular relates to a preparation method of a coal-based silicon-carbon composite negative electrode material.

背景技术Background technique

能量密度的提升一直是锂离子电池技术发展的主旋律，一种是通过优化电池结构，如宁德时代CPT技术、比亚迪“刀片电池”等思路；另一种着力于突破高容量材料的技术壁垒，这也是目前电池厂家采取的主流方式。正负极材料是提升锂离子电池能量密度的关键，虽然正极材料在电池中占据核心地位，但石墨类负极材料的理论克容量为372mAh/g，成为其能量进一步提升的限制条件，硅作为锂电池负极材料的理论克容量为4200mAh/g，硅基复合材料具有较高的比容量及较低的脱嵌锂电位，被认为是最具潜力的新一代锂电池负极材料。The improvement of energy density has always been the main theme of the development of lithium-ion battery technology. One is to optimize the battery structure, such as the CPT technology of the Ningde era, BYD's "blade battery" and other ideas; the other is to break through the technical barriers of high-capacity materials. It is also the mainstream method adopted by battery manufacturers at present. Positive and negative electrode materials are the key to improving the energy density of lithium-ion batteries. Although the positive electrode material occupies the core position in the battery, the theoretical gram capacity of the graphite-based negative electrode material is 372mAh/g, which has become the limiting condition for further improvement of its energy. The theoretical gram capacity of the battery anode material is 4200mAh/g, and the silicon-based composite material has high specific capacity and low lithium-deintercalation potential, and is considered to be the most potential new-generation lithium battery anode material.

硅基材料在充放电过程中会产生约300％体积变化，从而引发电极开裂、剥离和粉化，最终造成电极容量衰减甚至完全失效，为了改善硅基负极材料的循环稳定性，通常将硅材料纳米化或与碳材料进行复合，通常对碳源、硅源材料要求比较高，制造成本高。Silicon-based materials will produce about 300% volume change during the charge and discharge process, which will cause electrode cracking, peeling and pulverization, and eventually lead to electrode capacity attenuation or even complete failure. In order to improve the cycle stability of silicon-based anode materials, silicon materials are usually Nanoization or compounding with carbon materials usually requires relatively high carbon source and silicon source materials, and the manufacturing cost is high.

发明内容SUMMARY OF THE INVENTION

为了解决现有技术中存在的问题，本发明提出一种煤基硅碳复合负极材料及其制备方法，旨在解决硅基负极材料的膨胀，在不降低导电性的基础上提高材料首次库伦效力，同时以无烟煤为碳源、以硅藻土为硅源，降低材料制备成本，有利于实现硅基负极材料的工业化生产。In order to solve the problems existing in the prior art, the present invention proposes a coal-based silicon-carbon composite negative electrode material and a preparation method thereof, aiming at solving the expansion of the silicon-based negative electrode material and improving the first Coulomb efficiency of the material on the basis of not reducing the electrical conductivity At the same time, anthracite is used as the carbon source and diatomite is used as the silicon source, which reduces the cost of material preparation and is beneficial to the industrialized production of silicon-based negative electrode materials.

为实现上述目的，本发明提供如下技术方案：一种煤基硅碳复合负极材料的制备方法，包括以下步骤：In order to achieve the above purpose, the present invention provides the following technical solutions: a preparation method of a coal-based silicon-carbon composite negative electrode material, comprising the following steps:

步骤一，无烟煤预处理得到无定型多孔碳，硅藻土预处理得到纯化的多孔SiO2粉末；Step 1, anthracite pretreatment to obtain amorphous porous carbon, and diatomite pretreatment to obtain purified porous SiO2 powder;

步骤二，将锂粉与步骤一中得到的多孔SiO2粉末混合，在保护气氛下进行反应，得到多孔的SiOx/Si/Li2SiOy复合物；In step 2, the lithium powder is mixed with the porous SiO2 powder obtained in the first step, and the reaction is carried out under a protective atmosphere to obtain a porous SiOx/Si/Li2SiOy composite;

步骤三，将分散剂、步骤一得到的无定型多孔碳和步骤二得到的多孔的SiOx/Si/Li2SiOy复合物分散在溶剂中后进行研磨，得到前驱体浆液；Step 3, dispersing the dispersant, the amorphous porous carbon obtained in step 1 and the porous SiOx/Si/Li2SiOy composite obtained in step 2 in a solvent and then grinding to obtain a precursor slurry;

步骤四，将步骤三中得到的前驱体浆液进行喷雾干燥、融合、造粒后进行高温碳化和气相包覆，即得到煤基硅碳复合负极材料。In step 4, the precursor slurry obtained in step 3 is spray-dried, fused, and granulated, and then subjected to high-temperature carbonization and gas-phase coating to obtain a coal-based silicon-carbon composite negative electrode material.

进一步的，所述步骤一中，无烟煤预处理的具体步骤为：将无烟煤先进行第一热处理，对经过第一热处理后的无烟煤进行破碎、酸洗、水洗或醇洗、烘干后进行第二热处理，然后进行粉碎，得到无定型多孔碳；所述硅藻土预处理具体步骤为：将硅藻土进行第三热处理，然后破碎、酸洗、水洗、烘干、粉碎，得到纯化的多孔SiO2粉末。Further, in the first step, the specific steps of the anthracite pretreatment are as follows: the anthracite is first subjected to a first heat treatment, and the anthracite after the first heat treatment is crushed, pickled, washed with water or alcohol, dried, and then subjected to a second heat treatment. heat treatment, and then pulverizing to obtain amorphous porous carbon; the specific steps of the diatomite pretreatment are: subjecting the diatomite to a third heat treatment, then crushing, pickling, washing, drying, and pulverizing to obtain purified porous SiO2 powder.

进一步的，所述酸洗时采用质量分数＞70％的硫酸，在70℃-100℃、液固比为(2-5):1的情况下下酸洗1h-4h；所述酸洗和水洗或醇洗交替进行多次，直至洗液的pH在6-8之间；所述第一热处理温度600℃-800℃，所述第二热处理为温度为800℃-1200℃，所述第三热处理温度为400℃-750℃，所述第一热处理、第二热处理和第三热处理的保温时间均为1h-4h。Further, sulfuric acid with a mass fraction > 70% is used in the acid washing, and the acid washing is carried out at 70° C.-100° C. and the liquid-solid ratio is (2-5): 1 for 1h-4h; the acid washing and Washing with water or alcohol is performed alternately for many times until the pH of the lotion is between 6 and 8; the temperature of the first heat treatment is 600°C-800°C, the temperature of the second heat treatment is 800°C-1200°C, and the temperature of the first heat treatment is 800°C-1200°C. The temperature of the third heat treatment is 400° C.-750° C., and the holding time of the first heat treatment, the second heat treatment and the third heat treatment is 1h-4h.

进一步的，所述步骤二中，所述锂粉和多孔SiO2粉末混合时的质量比为1:(0.5-3)，所述锂粉和多孔SiO2粉末在温度为600℃-900℃反应条件下进行热还原。Further, in the second step, the mass ratio of the lithium powder and the porous SiO2 powder when mixed is 1:(0.5-3), and the lithium powder and the porous SiO2 powder are reacted at a temperature of 600°C-900°C. Perform thermal reduction.

进一步的，所述步骤三中，所述多孔SiOx/Si/Li2SiOy复合物与无定型多孔碳的质量比为1:(1-4)；所述溶剂为醇类、酮类、烷类、脂类中的至少一种，所述研磨采用湿法研磨，研磨时间为1-12h。Further, in the step 3, the mass ratio of the porous SiOx/Si/Li2SiOy composite to the amorphous porous carbon is 1:(1-4); the solvent is alcohols, ketones, alkanes, lipids At least one of the class, the grinding adopts wet grinding, and the grinding time is 1-12h.

进一步的，所述步骤四中，所述高温碳化为惰性气氛下的两段升温，首先在200-450℃下保温1-4h，然后升至750-950℃，保温1-6h。Further, in the fourth step, the high temperature carbonization is a two-stage heating under an inert atmosphere, firstly, the temperature is kept at 200-450°C for 1-4 hours, and then the temperature is raised to 750-950°C for 1-6 hours.

进一步的，所述气相包覆为在750-950℃下通入有机碳源气体，反应1-6h；所述有机碳源气体为甲烷、乙炔、天然气之中的至少一种或甲烷、乙炔、天然气之中的至少一种与氢气的组合。Further, the gas phase coating is to introduce organic carbon source gas at 750-950 ° C, and react for 1-6h; the organic carbon source gas is at least one of methane, acetylene, natural gas or methane, acetylene, A combination of at least one of natural gas and hydrogen.

进一步的，对所述步骤四得到的煤基硅碳复合负极材料进行破碎、筛分、除磁。Further, the coal-based silicon-carbon composite negative electrode material obtained in the fourth step is crushed, screened and demagnetized.

进一步的，包括内核(1)和外壳(3)以及在内核(1)与外壳(3)之间的多孔中间层(2)，所以内核(1)无定型多孔碳，所述多孔中间层(2)为多孔SiOx/Si/Li2SiOy复合。Further, the inner core (1) and the outer shell (3) and the porous intermediate layer (2) between the inner core (1) and the outer shell (3) are included, so the inner core (1) is amorphous porous carbon, and the porous intermediate layer ( 2) It is a composite of porous SiOx/Si/Li2SiOy.

本发明还提供一种煤基硅碳复合负极材料，无定型多孔碳由无烟煤低温炭化得到，所述多孔中间层(2)以硅藻土为硅源，所述外壳(3)为碳包覆层。The present invention also provides a coal-based silicon-carbon composite negative electrode material. The amorphous porous carbon is obtained by low-temperature carbonization of anthracite coal. Floor.

与现有技术相比，本发明至少具有以下有益效果：Compared with the prior art, the present invention at least has the following beneficial effects:

本发明以无烟煤为碳源，以硅藻土为硅源，无烟煤低温炭化得到的无定型多孔碳，可以促进锂离子有序脱嵌，提高材料比容量；本发明采用无烟煤为碳源，提到了传统以石墨为碳源的技术方案，因为无烟煤的价格远低于石墨，因此采用无烟煤作物碳源降低了原材料的成本；进一步的，本发明利用硅藻土本身的多孔结构实现预留膨胀空间，有效改善硅基负极的膨胀问题；硅藻土经一系列处理得到多孔SiO2，得到的多孔SiO2与金属锂进行热还原反应，金属锂为还原剂，对反应程度进行合理控制，在不引入其他杂质的情况下，实现了SiOx的制备和煤基硅碳复合负极材料的预锂，进一步提高负极材料的循环稳定性；本发明采用硅藻土提纯得到多孔SiO2，进一步降低了原材料的成本。The invention uses anthracite as the carbon source, diatomite as the silicon source, and the amorphous porous carbon obtained by the low-temperature carbonization of the anthracite can promote the orderly de-intercalation of lithium ions and improve the specific capacity of the material; the anthracite is used as the carbon source, and the In the traditional technical scheme of using graphite as the carbon source, because the price of anthracite is far lower than that of graphite, the use of anthracite crop carbon source reduces the cost of raw materials; further, the present invention utilizes the porous structure of diatomite itself to realize the reserved expansion space, The expansion problem of the silicon-based negative electrode is effectively improved; the porous SiO 2 is obtained by a series of treatments on diatomite, and the obtained porous SiO 2 undergoes thermal reduction reaction with metallic lithium. In the case of other impurities, the preparation of SiO x and the pre-lithiation of the coal-based silicon-carbon composite negative electrode material are realized, and the cycle stability of the negative electrode material is further improved; the present invention adopts diatomite to purify to obtain porous SiO 2 , which further reduces the amount of raw materials. cost.

进一步，本发明得到的煤基硅碳复合负极材料在进行气相碳包覆之前还进行了高温碳化，高温碳化可以将碳基体中的杂质和制备过程中添加的反应物质碳化，还可以使内核与外壳的物理包覆结构更加稳固；本发明中采用气相包覆在多孔中间层外包覆碳包覆层，有利于提高材料机械加工性能、导电性及其在充放电过程中的循环稳定性。Further, the coal-based silicon carbon composite negative electrode material obtained in the present invention is also subjected to high-temperature carbonization before being coated with gas phase carbon, and the high-temperature carbonization can carbonize the impurities in the carbon matrix and the reaction substances added in the preparation process, and can also make the inner core and the inner core carbonized. The physical coating structure of the shell is more stable; in the present invention, the porous intermediate layer is coated with a carbon coating layer by gas phase coating, which is beneficial to improve the machinability, electrical conductivity and cycle stability of the material during charging and discharging.

本发明提供的一种煤基硅碳复合负极材料，包括内核、多孔中间层、外壳，内核为无定型多孔碳，有利于锂离子传输，提高材料比容量；多孔中间层为多孔SiOx/Si/Li2SiOy复合物，其中Si-SiOx可以提高负极材料的比容量和首效，同时在负极材料中引入Li可以提高材料循环稳定性，多孔中间层的多孔结构为硅材料预留了膨胀空间；外壳为碳包覆层，提高材料机械加工性能及导电性。A coal-based silicon-carbon composite negative electrode material provided by the invention comprises an inner core, a porous intermediate layer, and an outer shell, wherein the inner core is amorphous porous carbon, which is beneficial to the transport of lithium ions and improves the specific capacity of the material; the porous intermediate layer is porous SiO x /Si /Li 2 SiO y composite, in which Si-SiO x can improve the specific capacity and the first effect of the negative electrode material, while the introduction of Li into the negative electrode material can improve the cycle stability of the material, and the porous structure of the porous intermediate layer is reserved for the silicon material. Expansion space; the outer shell is a carbon cladding layer, which improves the machinability and electrical conductivity of the material.

附图说明Description of drawings

图1为本发明煤基硅碳复合负极材料结构示意图。FIG. 1 is a schematic structural diagram of the coal-based silicon-carbon composite negative electrode material of the present invention.

附图中：1为内核；2为多孔中间层；3为外壳。In the drawings: 1 is the inner core; 2 is the porous intermediate layer; 3 is the outer shell.

具体实施方式Detailed ways

下面结合附图和具体实施方式对本发明作进一步的说明。The present invention will be further described below with reference to the accompanying drawings and specific embodiments.

以下实施例旨在进一步说明本发明内容，而不是限制本发明权利要求的保护范围。The following examples are intended to further illustrate the content of the present invention, rather than limit the protection scope of the claims of the present invention.

实施例1Example 1

(1)无烟煤炭化：将无烟煤在600℃下，保温4h，然后破碎、酸洗、水洗、烘干，其中酸洗采用质量分数＞70％的硫酸，在70℃、液固比5:1下酸洗2h，酸洗和水洗交替进行多次，至洗液pH在6-8之间时停止清洗；然后烘干、粉碎，在800℃下，保温4h后退火、粉碎，得到无定形多孔碳。(1) Anthracite coalification: The anthracite was kept at 600°C for 4h, then crushed, pickled, washed with water, and dried. The pickling was carried out with sulfuric acid with a mass fraction of >70%, at 70°C and a liquid-solid ratio of 5:1. Pickling for 2 hours, pickling and water washing are performed alternately for several times, and the cleaning is stopped when the pH of the washing solution is between 6-8; then it is dried and pulverized, annealed and pulverized at 800 ° C for 4 hours, and then amorphous porous carbon is obtained. .

(2)硅藻土提纯：将硅藻土在400℃下保温4h，去除有机质；然后破碎、酸洗、水洗，其中酸洗采用质量分数＞70％的浓硫酸，在70℃、液固比5:1下酸洗2h，酸洗和水洗交替进行多次，至洗液液pH为6-8之间时停止清洗；然后烘干、粉碎，得到纯化的多孔SiO2粉末。(2) Purification of diatomite: The diatomite was kept at 400°C for 4 hours to remove organic matter; then crushed, pickled and washed with water, wherein the pickling used concentrated sulfuric acid with a mass fraction > 70%, at 70°C, liquid-solid ratio Pickling at 5:1 for 2h, pickling and water washing are carried out alternately for many times, and the washing is stopped when the pH of the washing solution is between 6-8; then dried and pulverized to obtain purified porous SiO 2 powder.

(3)SiOx/Si/Li2SiOy复合物制备：将质量比为1:0.5的锂粉和多孔SiO2粉末均匀混合，在氮气气氛下，750℃进行热还原反应，得到多孔的SiOx/Si/Li2SiOy复合物，因锂粉和多孔SiO2粉末进行不完全反应，得到的SiOx/Si/Li2SiOy复合物中1≤x≤2，3≤y≤5。(3) Preparation of SiO x /Si/Li 2 SiO y composite: Lithium powder and porous SiO 2 powder with a mass ratio of 1:0.5 were uniformly mixed, and a thermal reduction reaction was performed at 750 °C in a nitrogen atmosphere to obtain porous SiO For x /Si/Li 2 SiO y composite, due to incomplete reaction between lithium powder and porous SiO 2 powder, 1≤x≤2, 3≤y≤5 in the obtained SiOx/Si/Li 2 SiOy composite.

(4)前驱体浆液制备：将多孔SiOx/Si/Li2SiOy复合物、无定形多孔碳、分散剂分别加入丙酮中，进行湿法研磨6h，得到均匀分散的前驱体浆液，其中多孔SiOx/Si/Li2SiOy复合物、无定形多孔碳的质量比为1:4。(4) Preparation of precursor slurry: porous SiO x /Si/Li 2 SiO y composite, amorphous porous carbon, and dispersant were added to acetone, respectively, and subjected to wet grinding for 6 h to obtain a uniformly dispersed precursor slurry, in which porous The mass ratio of SiO x /Si/Li 2 SiO y composite and amorphous porous carbon is 1:4.

(5)负极材料制备：将所得前驱体浆液进行喷雾干燥、融合、造粒后进行高温碳化，首先在450℃下，保温1h，然后升至750℃，保温6h；然后进行气相包覆，在750℃条件下通入甲烷与乙炔的混合气体，反应6h，即得到煤基硅碳复合负极材料。(5) Preparation of negative electrode material: The obtained precursor slurry is spray-dried, fused, granulated, and then carbonized at high temperature. First, it is kept at 450 °C for 1 h, then raised to 750 °C, and kept for 6 h; A mixed gas of methane and acetylene was introduced at 750°C and reacted for 6 hours to obtain a coal-based silicon-carbon composite negative electrode material.

实施例2Example 2

(1)无烟煤炭化：将无烟煤在800℃下，保温1h，然后破碎、酸洗、醇洗、烘干，其中酸洗采用质量分数＞70％的硫酸，在100℃、液固比2:1下酸洗1h，酸洗和醇洗交替进行，至洗液pH在6-8之间时停止清洗；然后烘干、粉碎，在1200℃下保温1h后退火、粉碎，得到无定形多孔碳。(1) Anthracite coalification: The anthracite is kept at 800 °C for 1 hour, then crushed, pickled, alcohol washed, and dried. The pickling adopts sulfuric acid with a mass fraction of more than 70%, and the liquid-solid ratio is 2:1 at 100 °C. Under acid washing for 1 hour, acid washing and alcohol washing are carried out alternately, and the washing is stopped when the pH of the washing solution is between 6-8; then it is dried and pulverized, kept at 1200 ° C for 1 h, annealed and pulverized to obtain amorphous porous carbon.

(2)硅藻土提纯：将硅藻土在750℃下，保温1h，去除有机质；然后破碎、酸洗、水洗，其中酸洗采用质量分数＞70％的硫酸，在100℃、液固比2:1下酸洗1h，酸洗和水洗交替，至洗液pH在6-8之间时停止清洗；然后烘干、粉碎，得到纯化的多孔SiO2粉末。(2) Purification of diatomite: The diatomite was kept at 750°C for 1 h to remove organic matter; then crushed, pickled, and washed with water, wherein the acid washing was carried out with sulfuric acid with a mass fraction > 70%, at 100°C, liquid-solid ratio Pickling at 2:1 for 1 h, alternating with acid washing and water washing, and stopping when the pH of the washing solution is between 6-8; then drying and pulverizing to obtain purified porous SiO 2 powder.

(3)SiOx/Si/Li2SiOy复合物制备：将质量比为1:3的锂粉和多孔SiO2粉末均匀混合，在氮气气氛下，600℃进行热还原反应，得到多孔的SiOx/Si/Li2SiOy复合物，因锂粉和多孔SiO2粉末进行不完全反应，得到的SiOx/Si/Li2SiOy复合物中1≤x≤2，3≤y≤5。(3) Preparation of SiO x /Si/Li 2 SiO y composite: Lithium powder and porous SiO 2 powder with a mass ratio of 1:3 were uniformly mixed, and a thermal reduction reaction was performed at 600 °C in a nitrogen atmosphere to obtain porous SiO For x /Si/Li 2 SiO y composite, due to incomplete reaction between lithium powder and porous SiO 2 powder, 1≤x≤2, 3≤y≤5 in the obtained SiOx/Si/Li 2 SiOy composite.

(4)前驱体浆液制备：将多孔SiOx/Si/Li2SiOy复合物、无定形多孔碳和软碳的复合物、分散剂加入异丙醇和丙酮的混合物中进行湿法研磨12h，得到均匀分散的前驱体浆液，其中多孔SiOx/Si/Li2SiOy复合物、无定形多孔碳的质量比为1:1。(4) Preparation of precursor slurry: the porous SiO x /Si/Li 2 SiO y composite, the composite of amorphous porous carbon and soft carbon, and the dispersant were added to the mixture of isopropanol and acetone for wet grinding for 12 h to obtain A uniformly dispersed precursor slurry, wherein the mass ratio of porous SiO x /Si/Li 2 SiO y composite and amorphous porous carbon is 1:1.

(5)负极材料制备：将所得前驱体浆液进行喷雾干燥、融合、造粒后进行高温碳化，首先在200℃下保温4h，然后升温至950℃，保温1h；然后进行气相包覆，在950℃条件下通入乙炔和氢气混合气体，反应2h，即得到煤基硅碳复合负极材料。(5) Preparation of negative electrode material: the obtained precursor slurry is spray-dried, fused, and granulated, and then carbonized at high temperature. First, it is kept at 200 °C for 4 h, then heated to 950 °C and kept at 950 °C for 1 h; A mixed gas of acetylene and hydrogen was introduced under the condition of ℃ and reacted for 2 h to obtain a coal-based silicon-carbon composite negative electrode material.

实施例3Example 3

(1)无烟煤炭化：将无烟煤在700℃下，保温2h，然后破碎、酸洗、醇洗、烘干，其中酸洗采用质量分数＞70％的硫酸，在85℃、液固比3:1下酸洗4h，酸洗和醇洗交替进多次，至洗液pH在6-8之间时停止清洗；然后烘干、粉碎，在1000℃下，保温2h后退火、粉碎，得到无定形多孔碳。(1) Anthracite coalification: The anthracite is kept at 700 °C for 2 hours, then crushed, pickled, alcohol washed, and dried. The pickling adopts sulfuric acid with a mass fraction > 70%, and the liquid-solid ratio is 3:1 at 85 °C. Under acid washing for 4 hours, acid washing and alcohol washing are alternated for several times, and the cleaning is stopped when the pH of the washing solution is between 6-8; then it is dried and pulverized, and at 1000 ° C, it is annealed and pulverized after holding for 2 hours to obtain amorphous Porous carbon.

(2)硅藻土提纯：将硅藻土在600℃下，保温2h，去除有机质；然后破碎、酸洗、水洗，其中酸洗采用质量分数＞70％的浓硫酸，在85℃、液固比3:1下酸洗4h，酸洗和水洗交替进多次，至洗液pH在6-8之间时停止清洗；然后烘干、粉碎，得到纯化的多孔SiO2粉末。(2) Purification of diatomite: The diatomite was kept at 600°C for 2 hours to remove organic matter; then crushed, pickled and washed with water, wherein the pickling used concentrated sulfuric acid with a mass fraction > 70%, at 85°C, liquid-solid Pickling at a ratio of 3:1 for 4 hours, and alternately performing acid washing and water washing for several times, stopping when the pH of the washing solution is between 6-8; then drying and pulverizing to obtain purified porous SiO 2 powder.

(3)SiOx/Si/Li2SiOy复合物制备：将质量比为1:1的锂粉和多孔SiO2粉末均匀混合，在氮气气氛下、900℃进行热还原反应，得到多孔的SiOx/Si/Li2SiOy复合物，因锂粉和多孔SiO2粉末进行不完全反应，得到的SiOx/Si/Li2SiOy复合物中1≤x≤2，3≤y≤5。(3) Preparation of SiO x /Si/Li 2 SiO y composite: Lithium powder and porous SiO 2 powder with a mass ratio of 1:1 were uniformly mixed, and a thermal reduction reaction was carried out at 900 °C in a nitrogen atmosphere to obtain porous SiO For x /Si/Li 2 SiO y composite, due to incomplete reaction between lithium powder and porous SiO 2 powder, 1≤x≤2, 3≤y≤5 in the obtained SiOx/Si/Li 2 SiOy composite.

(4)前驱体浆液制备：将多孔SiOx/Si/Li2SiOy复合物、无定形多孔碳、分散剂分别加入乙醇中进行湿法研磨1h，得到均匀分散的前驱体浆液，其中多孔SiOx/Si/Li2SiOy复合物、无定形多孔碳的质量比为1:2。(4) Preparation of precursor slurry: The porous SiO x /Si/Li 2 SiO y composite, amorphous porous carbon, and dispersant were added to ethanol for wet grinding for 1 h to obtain a uniformly dispersed precursor slurry, in which porous SiO The mass ratio of x /Si/Li 2 SiO y composite to amorphous porous carbon is 1:2.

(5)负极材料制备：将所得前驱体浆液进行喷雾干燥、融合、造粒后进行高温碳化，首先在350℃下保温2h，然后升温至850℃，保温2h；然后进行气相包覆，在850℃条件下通入天然气与氢气的混合气体，反应1h，即得到煤基硅碳复合负极材料，对得到的煤基硅碳复合负极材料进行破碎、筛分、除磁。(5) Preparation of negative electrode material: the obtained precursor slurry was spray-dried, fused, and pelletized, and then carbonized at high temperature. First, it was kept at 350 °C for 2 h, then heated to 850 °C, and kept at 850 °C for 2 h; The mixed gas of natural gas and hydrogen was introduced under the condition of ℃ and reacted for 1 h to obtain the coal-based silicon-carbon composite negative electrode material, and the obtained coal-based silicon-carbon composite negative electrode material was crushed, screened and demagnetized.

以上述实施例1-3所得硅基负极材料为负极进行制浆、涂布、烘干得到负极极片，以金属锂片为对电极组装电池并进行电化学测试，具体测试方法为：1mol/L的LiPF6/EC+DMC+EMC(V/V＝1:1:1)电解液、Celgard2400隔膜，组装成2025扣式电池。采用武汉金诺电子有限公司LAND电池测试***常温测试，测试条件：首次充放电I＝0.1C，循环I＝0.1C，电压范围0.005-2.0V，测试结果如表1所示。Using the silicon-based negative electrode material obtained in the above-mentioned embodiment 1-3 as the negative electrode, slurrying, coating, and drying were carried out to obtain a negative electrode pole piece, and the lithium metal piece was used as the counter electrode to assemble the battery and carry out an electrochemical test. The specific test method is: 1mol/ L of LiPF 6 /EC+DMC+EMC (V/V=1:1:1) electrolyte, Celgard2400 separator, assembled into a 2025 button cell. Use Wuhan Jinnuo Electronics Co., Ltd. LAND battery test system to test at room temperature, test conditions: first charge and discharge I = 0.1C, cycle I = 0.1C, voltage range 0.005-2.0V, the test results are shown in Table 1.

表1负极材料电化学性能测试结果Table 1 Electrochemical performance test results of negative electrode materials

技术指标Technical indicators 首次可逆容量/mAh·g<sup>-1</sup>First reversible capacity/mAh·g<sup>-1</sup> 首效/％First effect/% 200<sup>th</sup>容量保持率/％200<sup>th</sup> capacity retention rate/% 实施例1Example 1 11581158 92.792.7 91.491.4 实施例2Example 2 18731873 91.291.2 88.588.5 实施例3Example 3 15201520 92.092.0 90.390.3

从表1所示的测试结果可以看出，无烟煤经低温碳化后作为多孔性碳基体、硅藻土经纯化后作为硅源，制得的煤基硅碳复合负极材料在不同的Si和C配比下均表现为较好的首次比容量，首次效率在90％以上，1C循环100圈容量保持率在90％以上，说明本发明的硅碳复合材料在选用低品质原材料的情况下仍能保持较好的电化学性能。From the test results shown in Table 1, it can be seen that anthracite is carbonized at low temperature as a porous carbon matrix, and diatomite is purified as a silicon source. In comparison, the first specific capacity is better, the first efficiency is above 90%, and the capacity retention rate for 100 cycles at 1C is above 90%, indicating that the silicon-carbon composite material of the present invention can still maintain the low-quality raw materials. better electrochemical performance.

如图1所示为本发明制得的煤基硅碳复合负极材料的具体结构示意图，内核为无定型多孔碳，无定型多孔碳由无烟煤低温炭化得到，多孔中间层以硅藻土为硅源制得多孔SiOx/Si/Li2SiOy复合物，外壳为碳包覆层，本发明的煤基硅碳复合负极材料的结构可以很好抑制硅基材料的膨胀。As shown in Figure 1 is the concrete structural representation of the coal-based silicon-carbon composite negative electrode material made by the present invention, the inner core is amorphous porous carbon, the amorphous porous carbon is obtained by low-temperature carbonization of anthracite, and the porous intermediate layer uses diatomite as the silicon source The porous SiO x /Si/Li 2 SiO y composite is prepared, the outer shell is a carbon coating layer, and the structure of the coal-based silicon-carbon composite negative electrode material of the present invention can well suppress the expansion of the silicon-based material.

Claims (10)

1. The preparation method of the coal-based silicon-carbon composite negative electrode material is characterized by comprising the following steps of:
firstly, pretreating anthracite to obtain amorphous porous carbon, and pretreating diatomite to obtain purified porous SiO2 powder;
step two, mixing lithium powder with the porous SiO2 powder obtained in the step one, and reacting in a protective atmosphere to obtain a porous SiOx/Si/Li2SiOy compound;
dispersing a dispersing agent, the amorphous porous carbon obtained in the step one and the porous SiOx/Si/Li2SiOy compound obtained in the step two in a solvent, and then grinding to obtain precursor slurry;
and step four, performing spray drying, fusion and granulation on the precursor slurry obtained in the step three, and then performing high-temperature carbonization and gas phase coating to obtain the coal-based silicon-carbon composite negative electrode material.
2. The preparation method of the coal-based silicon-carbon composite anode material according to claim 1, wherein in the first step, the anthracite coal is pretreated by the following specific steps: firstly, carrying out first heat treatment on anthracite, carrying out second heat treatment after crushing, acid washing, water washing or alcohol washing and drying on the anthracite subjected to the first heat treatment, and then crushing to obtain amorphous porous carbon; the diatomite pretreatment comprises the following specific steps: and (3) carrying out third heat treatment on the diatomite, crushing, acid washing, water washing, drying and crushing to obtain purified porous SiO2 powder.
3. The preparation method of the coal-based silicon-carbon composite anode material according to claim 2, characterized in that sulfuric acid with the mass fraction of more than 70% is adopted during acid washing, and the acid washing is carried out for 1h to 4h at the temperature of 70 ℃ to 100 ℃ and the liquid-solid ratio of (2-5): 1; the acid washing and the water washing or the alcohol washing are alternately carried out for a plurality of times until the pH value of the washing liquid is between 6 and 8; the first heat treatment temperature is 600-800 ℃, the second heat treatment temperature is 800-1200 ℃, the third heat treatment temperature is 400-750 ℃, and the heat preservation time of the first heat treatment, the second heat treatment and the third heat treatment is 1-4 h.
4. The preparation method of the coal-based silicon-carbon composite negative electrode material as claimed in claim 1, wherein in the second step, the mass ratio of the lithium powder to the porous SiO2 powder is 1 (0.5-3), and the lithium powder and the porous SiO2 powder are thermally reduced under the reaction condition that the temperature is 600-900 ℃.
5. The method for preparing the coal-based silicon-carbon composite anode material according to claim 1, wherein in the third step, the mass ratio of the porous SiOx/Si/Li2SiOy composite to the amorphous porous carbon is 1 (1-4); the solvent is at least one of alcohols, ketones, alkanes and lipids, and the grinding adopts wet grinding for 1-12 h.
6. The method for preparing the coal-based silicon-carbon composite anode material as claimed in claim 1, wherein in the fourth step, the high temperature carbonization is a two-stage temperature rise under an inert atmosphere, and the temperature is first maintained at 200-450 ℃ for 1-4h, then increased to 750-950 ℃ and maintained for 1-6 h.
7. The method for preparing a coal-based silicon-carbon composite anode material as claimed in claim 1, wherein the gas phase coating is performed by introducing an organic carbon source gas at 750-950 ℃ for reaction for 1-6 h; the organic carbon source gas is at least one of methane, acetylene and natural gas or the combination of at least one of methane, acetylene and natural gas and hydrogen.
8. The preparation method of the coal-based silicon-carbon composite negative electrode material according to claim 1, wherein the coal-based silicon-carbon composite negative electrode material obtained in the fourth step is crushed, sieved and demagnetized.
9. The coal-based silicon-carbon composite anode material obtained by the preparation method according to any one of claims 1 to 8, comprising an inner core (1) and an outer shell (3) and a porous intermediate layer (2) between the inner core (1) and the outer shell (3), wherein the inner core (1) is amorphous porous carbon, and the porous intermediate layer (2) is a porous SiOx/Si/Li2SiOy composite.
10. The coal-based silicon-carbon composite negative electrode material as claimed in claim 1, wherein amorphous porous carbon is obtained by low-temperature carbonization of anthracite, the porous intermediate layer (2) uses diatomite as a silicon source, and the shell (3) is a carbon coating layer.
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113889605A (en) * 2021-09-11 2022-01-04 四川星耀新能源科技有限公司 Hard carbon-dopant coated anthracite composite negative electrode material, preparation method thereof and lithium ion battery
CN115991473A (en) * 2022-12-12 2023-04-21 湖南钠方新能源科技有限责任公司 Modified amorphous material, preparation method thereof, negative plate and sodium ion battery
CN116462183A (en) * 2023-03-10 2023-07-21 中国科学院宁波材料技术与工程研究所 A soft carbon material with a diatomite-like structure and its preparation method and application

Citations (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101710617A (en) * 2009-05-12 2010-05-19 大连丽昌新材料有限公司 High-energy silicon-carbon composite negative electrode material for lithium ion battery and manufacturing process thereof
CN102208636A (en) * 2011-05-12 2011-10-05 北京科技大学 Method for preparing porous silicon/carbon composite material by using diatomite as raw material and application
CN102903896A (en) * 2012-10-22 2013-01-30 深圳清华大学研究院 Silicon-carbon composite negative electrode material for lithium ion battery, its preparation method and application
CN103022446A (en) * 2012-12-19 2013-04-03 深圳市贝特瑞新能源材料股份有限公司 Silicon oxide/carbon cathode material of lithium ion battery and preparation method of material
CN103337613A (en) * 2013-07-04 2013-10-02 奇瑞汽车股份有限公司 Silicon-carbon composite material and preparation method thereof, and lithium ion battery
CN103730644A (en) * 2013-12-12 2014-04-16 天津巴莫科技股份有限公司 Preparation method of silicon-silicon oxide-carbon composite negative pole material of lithium ion battery
US20150162617A1 (en) * 2013-12-09 2015-06-11 Nano And Advanced Materials Institute Limited Si@C core/shell Nanomaterials for High Performance Anode of Lithium Ion Batteries
CN104979540A (en) * 2015-07-09 2015-10-14 东北师范大学 Preparation method and application of bicontinuous-structural nanocomposite material
CN105680026A (en) * 2016-04-21 2016-06-15 苏州协鑫集成科技工业应用研究院有限公司 Carbon composite material, preparation method for carbon composite material and battery
CN108269979A (en) * 2017-12-28 2018-07-10 合肥国轩高科动力能源有限公司 Silicon monoxide/silicon/lithium metasilicate composite anode material and preparation method thereof
JP2018152161A (en) * 2017-03-09 2018-09-27 株式会社豊田自動織機 Negative electrode material
CN109835900A (en) * 2019-03-21 2019-06-04 哈尔滨工业大学 A kind of preparation method of the coal base porous carbon based on potassium carbonate cyclic activation and the preparation method of biomass-based porous carbon
CN111362269A (en) * 2020-03-09 2020-07-03 上海电气集团股份有限公司 Preparation method of SEI (solid electrolyte interphase) film of lithium ion battery cathode, lithium ion battery cathode material and application of lithium ion battery cathode material

Patent Citations (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101710617A (en) * 2009-05-12 2010-05-19 大连丽昌新材料有限公司 High-energy silicon-carbon composite negative electrode material for lithium ion battery and manufacturing process thereof
CN102208636A (en) * 2011-05-12 2011-10-05 北京科技大学 Method for preparing porous silicon/carbon composite material by using diatomite as raw material and application
CN102903896A (en) * 2012-10-22 2013-01-30 深圳清华大学研究院 Silicon-carbon composite negative electrode material for lithium ion battery, its preparation method and application
CN103022446A (en) * 2012-12-19 2013-04-03 深圳市贝特瑞新能源材料股份有限公司 Silicon oxide/carbon cathode material of lithium ion battery and preparation method of material
CN103337613A (en) * 2013-07-04 2013-10-02 奇瑞汽车股份有限公司 Silicon-carbon composite material and preparation method thereof, and lithium ion battery
US20150162617A1 (en) * 2013-12-09 2015-06-11 Nano And Advanced Materials Institute Limited Si@C core/shell Nanomaterials for High Performance Anode of Lithium Ion Batteries
CN103730644A (en) * 2013-12-12 2014-04-16 天津巴莫科技股份有限公司 Preparation method of silicon-silicon oxide-carbon composite negative pole material of lithium ion battery
CN104979540A (en) * 2015-07-09 2015-10-14 东北师范大学 Preparation method and application of bicontinuous-structural nanocomposite material
CN105680026A (en) * 2016-04-21 2016-06-15 苏州协鑫集成科技工业应用研究院有限公司 Carbon composite material, preparation method for carbon composite material and battery
JP2018152161A (en) * 2017-03-09 2018-09-27 株式会社豊田自動織機 Negative electrode material
CN108269979A (en) * 2017-12-28 2018-07-10 合肥国轩高科动力能源有限公司 Silicon monoxide/silicon/lithium metasilicate composite anode material and preparation method thereof
CN109835900A (en) * 2019-03-21 2019-06-04 哈尔滨工业大学 A kind of preparation method of the coal base porous carbon based on potassium carbonate cyclic activation and the preparation method of biomass-based porous carbon
CN111362269A (en) * 2020-03-09 2020-07-03 上海电气集团股份有限公司 Preparation method of SEI (solid electrolyte interphase) film of lithium ion battery cathode, lithium ion battery cathode material and application of lithium ion battery cathode material

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
XIE, LZ 等: "Modified SiO hierarchical structure materials with improved initial coulombic efficiency for advanced lithium-ion battery anodes", 《RSC ADVANCES》 *
於洪将: "硅/碳和Li4Ti5O12负极材料的研究", 《中国优秀硕士学位论文全文数据库》 *
沈晓辉 等: "锂离子电池硅碳负极材料研究进展", 《硅酸盐学报》 *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113889605A (en) * 2021-09-11 2022-01-04 四川星耀新能源科技有限公司 Hard carbon-dopant coated anthracite composite negative electrode material, preparation method thereof and lithium ion battery
CN113889605B (en) * 2021-09-11 2024-04-26 四川星耀新能源科技有限公司 Hard carbon-dopant coated anthracite composite anode material, preparation method thereof and lithium ion battery
CN115991473A (en) * 2022-12-12 2023-04-21 湖南钠方新能源科技有限责任公司 Modified amorphous material, preparation method thereof, negative plate and sodium ion battery
CN116462183A (en) * 2023-03-10 2023-07-21 中国科学院宁波材料技术与工程研究所 A soft carbon material with a diatomite-like structure and its preparation method and application

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