CN110589796B - A kind of molten salt chemically synthesized carbon powder and its preparation method and application - Google Patents

A kind of molten salt chemically synthesized carbon powder and its preparation method and application Download PDF

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CN110589796B
CN110589796B CN201910927347.3A CN201910927347A CN110589796B CN 110589796 B CN110589796 B CN 110589796B CN 201910927347 A CN201910927347 A CN 201910927347A CN 110589796 B CN110589796 B CN 110589796B
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宋秋实
谢志刚
谢宏伟
宁志强
尹华意
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Northeastern University China
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Abstract

A fused salt chemical synthesis carbon powder and a preparation method and application thereof belong to the field of carbon material chemical synthesis. The preparation method of the fused salt chemical synthesis carbon powder comprises weighing dry CaC according to the proportion2Powdered, dried CaCO3Putting the powder and the dehydrated molten salt raw material into a crucible, putting the crucible into a closed reactor, and introducing inert gas for protection; heating the closed reactor to the reaction temperature, and preserving the temperature for 5 min-10 h to carry out carbonization reaction to obtain a carbon product; and (3) carrying out ultrasonic cleaning on the carbon product, carrying out solid-liquid separation, removing molten salt, and drying to obtain carbon powder. The carbon powder material is used as a negative electrode carbon material of a lithium ion electrode, and has the advantages of improving the battery capacity and the cycle performance. The product of the method only generates calcium oxide except carbon, does not generate other toxic and harmful substances, and has green and environment-friendly process, and simple and easy operation.

Description

一种熔盐化学合成碳粉体及其制备方法和应用A kind of molten salt chemically synthesized carbon powder and its preparation method and application

技术领域technical field

本发明属于碳材料化学合成领域,特别涉及一种熔盐化学合成碳粉体及其制备方法和应用。The invention belongs to the field of chemical synthesis of carbon materials, and particularly relates to a molten salt chemically synthesized carbon powder and a preparation method and application thereof.

背景技术Background technique

碳材料有石墨、无定形碳、金刚石、纳米碳管、石墨烯等多种形式,制备相应的碳材料也需要使用不同的合成方法,如天然石墨高温烧结、有机碳高温裂解、气相沉积、外延生长、电解等。以上方法都具有一定的优势,但是也存在一些技术问题需要克服。例如,天然石墨高温烧结和有机碳高温裂解一般都需要1800℃以上的高温,对加热设备要求较高,且能耗也很高;气相沉积、外延生长需要精密、昂贵的设备以及复杂的操作;电解法效率较低,副反应也较多。因此,开发一种简单、易行、且低成本的碳材料制备方法具有很好的实际意义。Carbon materials include graphite, amorphous carbon, diamond, carbon nanotubes, graphene and other forms. The preparation of corresponding carbon materials also requires different synthesis methods, such as high temperature sintering of natural graphite, high temperature cracking of organic carbon, vapor deposition, epitaxy growth, electrolysis, etc. The above methods all have certain advantages, but there are also some technical problems to be overcome. For example, high-temperature sintering of natural graphite and high-temperature pyrolysis of organic carbon generally require a high temperature above 1800 °C, which requires high heating equipment and high energy consumption; vapor deposition and epitaxial growth require sophisticated and expensive equipment and complex operations; Electrolysis is less efficient and has more side reactions. Therefore, it is of great practical significance to develop a simple, feasible, and low-cost preparation method for carbon materials.

碳化钙被广泛应用于PVC、醋酸乙烯、橡胶、乙炔等化工领域。碳化钙是天然电石的主要成分。另外,工业碳化钙主要通过焦炭和氧化钙高温反应生成。碳酸钙也是一种重要的无机化工原料,经常用于涂料、橡胶、塑料和造纸等许多行业。碳酸钙可以由天然石灰石经过机械研磨、破碎等工序获得(重质碳酸钙);也可通过煅烧、分离、沉淀等化学方法制备(轻质碳酸钙、活性碳酸钙和纳米碳酸钙)。Calcium carbide is widely used in PVC, vinyl acetate, rubber, acetylene and other chemical fields. Calcium carbide is the main component of natural calcium carbide. In addition, industrial calcium carbide is mainly formed by the high temperature reaction of coke and calcium oxide. Calcium carbonate is also an important inorganic chemical raw material and is often used in many industries such as coatings, rubber, plastics and paper making. Calcium carbonate can be obtained from natural limestone through mechanical grinding, crushing and other processes (heavy calcium carbonate); it can also be prepared by chemical methods such as calcination, separation, and precipitation (light calcium carbonate, activated calcium carbonate and nano-calcium carbonate).

锂离子电池(LIBs)具有能量密度高、无记忆效应、循环寿命长、环境友好等优点,在便携式机械、电子、汽车、航空等领域得到广泛应用,是目前为止被应用最广泛的几种二次电池之一。负极材料是锂离子电池的一个主要组成部分,在电池充、放电过程中发生Li+离子的嵌入和脱嵌反应。常用的锂离子电池负极材料有碳基、硅基、锡基、钛基氧化物、过渡金属氧化物和过渡金属硫化物等。其中以石墨为代表的碳基负极材料是典型的嵌入型材料,具有良好的导电性、嵌锂电位低、价格低廉等特点,是被应用最早和最广泛的商业化负极材料。虽然,石墨的理论比容量是372mAh·g-1,虽然低于硅等其它一些负极材料(硅为4200mAh·g-1),但也具有体积膨胀小、稳定性好等优势。目前,锂离子电池的电池碳负极的主要包括石墨类(包括改性石墨、人工石墨等)、无定型碳类(包括软碳、硬碳等)、和纳米碳类(包括纳米碳管、石墨烯、C60等)。然而,制备这些碳材料普遍需要复杂的合成工艺,需要高温、高真空等苛刻条件。Lithium-ion batteries (LIBs) have the advantages of high energy density, no memory effect, long cycle life, and environmental friendliness. They are widely used in portable machinery, electronics, automobiles, aviation and other fields. one of the secondary batteries. The negative electrode material is a major component of Li-ion batteries, and the intercalation and deintercalation reactions of Li + ions occur during the charging and discharging of the battery. Commonly used anode materials for lithium-ion batteries include carbon-based, silicon-based, tin-based, titanium-based oxides, transition metal oxides, and transition metal sulfides. Among them, the carbon-based negative electrode material represented by graphite is a typical intercalation material, which has the characteristics of good electrical conductivity, low lithium intercalation potential, and low price. It is the earliest and most widely used commercial negative electrode material. Although the theoretical specific capacity of graphite is 372mAh·g -1 , which is lower than that of other anode materials such as silicon (silicon is 4200mAh·g -1 ), it also has the advantages of small volume expansion and good stability. At present, the carbon negative electrodes of lithium-ion batteries mainly include graphite (including modified graphite, artificial graphite, etc.), amorphous carbon (including soft carbon, hard carbon, etc.), and nanocarbon (including carbon nanotubes, graphite, etc.) alkene, C 60 , etc.). However, the preparation of these carbon materials generally requires complex synthesis processes and harsh conditions such as high temperature and high vacuum.

发明内容SUMMARY OF THE INVENTION

基于现有技术,本发明的目的是提供一种熔盐化学合成碳粉体及其制备方法和应用,该熔盐化学合成碳粉体是一种多形貌、多结构复合的碳粉体。本发明以碳化钙和碳酸钙为原料,以熔融态Ca基卤化物熔盐作为反应介质,在一定温度和时间下进行碳化反应,制备碳粉体材料。将反应后的产物及熔盐混合物从熔体中移出后冷却,并经过超声水洗、干燥,得到碳粉材料。将此碳粉材料用于作为锂离子电极负极碳材料,具有提高电池容量和循环性能的优点。该方法的产物除了碳外,只有氧化钙生成,不产生其他有毒有害物质,工艺绿色环保,简单易行。Based on the prior art, the purpose of the present invention is to provide a molten salt chemically synthesized carbon powder, a preparation method and application thereof, and the molten salt chemically synthesized carbon powder is a multi-morphological and multi-structure composite carbon powder. In the invention, calcium carbide and calcium carbonate are used as raw materials, and molten Ca-based halide molten salt is used as reaction medium, and carbonization reaction is carried out at a certain temperature and time to prepare carbon powder material. The reacted product and the molten salt mixture are removed from the melt, cooled, washed with ultrasonic water, and dried to obtain a carbon powder material. Using this carbon powder material as a negative electrode carbon material for lithium ion electrodes has the advantages of improving battery capacity and cycle performance. In addition to carbon, the product of the method only generates calcium oxide, and does not generate other toxic and harmful substances, and the process is environmentally friendly, simple and easy to implement.

本发明的一种熔盐化学合成碳粉体的制备方法,包括以下步骤:A preparation method of a molten salt chemically synthesized carbon powder of the present invention comprises the following steps:

步骤1:熔盐脱水处理Step 1: Molten Salt Dehydration Treatment

将熔盐的原料,真空干燥,随炉冷却至室温,得到脱水后的熔盐原料;所述的熔盐为钙基卤化物熔盐,当熔盐为混合物时,其混合比例为混合的物质形成共晶盐的混合比例;The raw material of the molten salt is vacuum-dried, and cooled to room temperature with the furnace to obtain the dehydrated molten salt raw material; the molten salt is a calcium-based halide molten salt, and when the molten salt is a mixture, the mixing ratio is a mixed material the mixing ratio to form the eutectic salt;

步骤2:碳化钙、碳酸钙的准备Step 2: Preparation of calcium carbide and calcium carbonate

(1)称取CaC2,在惰性气氛下破碎,干燥,得到粒径为1μm-5mm的干燥CaC2粉末;(1) Weigh the CaC 2 , crush it under an inert atmosphere, and dry it to obtain a dry CaC 2 powder with a particle size of 1 μm-5mm;

(2)称取CaCO3粉体,干燥,得到干燥CaCO3粉体;( 2 ) take by weighing CaCO powder, dry, obtain dry CaCO powder ;

步骤3:熔盐化学合成碳粉体Step 3: Molten salt chemical synthesis of carbon powder

(1)按配比,称量干燥CaC2粉末、干燥CaCO3粉体、脱水后的熔盐原料,置于坩埚中,在放入密闭反应器中,通入惰性气体保护;其中,按CaCO3完全反应,CaCO3+2CaC2→3CaO+5C的化学公式,CaC2加入量按化学计量比过量1~100wt.%,CaCO3的质量占脱水后的熔盐原料中卤化钙的质量百分比为0.1~20%,优选为5~10%;(1) According to the proportion, weigh the dry CaC 2 powder, the dry CaCO 3 powder, the dehydrated molten salt raw material, place it in a crucible, put it into a closed reactor, and pass it into an inert gas for protection; wherein, according to CaCO 3 Complete reaction, the chemical formula of CaCO 3 +2CaC 2 →3CaO+5C, the amount of CaC 2 added is 1-100wt.% in excess of the stoichiometric ratio, the mass of CaCO 3 accounts for the mass percentage of calcium halide in the dehydrated molten salt raw material is 0.1 ~20%, preferably 5~10%;

(2)将密闭反应器升温至反应温度,保温5min~10h进行碳化反应,得到碳产物;其中,反应温度大于脱水后的熔盐原料的熔点;(2) heating the closed reactor to the reaction temperature, keeping the temperature for 5min~10h to carry out carbonization reaction to obtain a carbon product; wherein, the reaction temperature is greater than the melting point of the dehydrated molten salt raw material;

步骤4:后处理Step 4: Post-processing

将碳产物进行超声清洗,固液分离,去除熔盐,干燥,得到碳粉体。The carbon product is subjected to ultrasonic cleaning, solid-liquid separation, removal of molten salt, and drying to obtain carbon powder.

所述的步骤1中,真空干燥的工艺为:干燥温度为200~400℃,干燥时间为24~48h。In the step 1, the vacuum drying process is as follows: the drying temperature is 200-400° C., and the drying time is 24-48 h.

所述的步骤1中,钙基卤化物熔盐为卤化钙、卤化钙和碱金属卤族化合物的混合物、或卤化钙和碱土金属卤族化合物的混合物、或卤化钙和碱土金属卤族化合物和碱金属卤族化合物的混合物中的一种。In the described step 1, the calcium-based halide molten salt is calcium halide, a mixture of calcium halide and an alkali metal halide compound, or a mixture of calcium halide and an alkaline earth metal halide compound, or a calcium halide and an alkaline earth metal halide compound and One of a mixture of alkali metal halide compounds.

钙基卤化物熔盐中,钙基卤化物优选为CaCl2、CaBr2、CaF2中的一种或几种,优选为CaCl2In the calcium-based halide molten salt, the calcium-based halide is preferably one or more of CaCl 2 , CaBr 2 and CaF 2 , preferably CaCl 2 .

所述的碱金属卤族化合物为NaCl、KCl、LiCl、NaBr、KBr、LiBr、NaF、KF、LiF中的一种或几种。The alkali metal halide compound is one or more of NaCl, KCl, LiCl, NaBr, KBr, LiBr, NaF, KF and LiF.

所述的碱土金属卤族化合物为MgCl2、MgF2、CaCl2、CaF2、SrCl2、SrF2、BaCl2、BaF2中的一种或几种。The alkaline earth metal halide compound is one or more of MgCl 2 , MgF 2 , CaCl 2 , CaF 2 , SrCl 2 , SrF 2 , BaCl 2 , and BaF 2 .

所述的步骤2(1)中,CaC2为分析纯碳化钙或工业电石,优选为分析纯碳化钙。In the step 2(1), CaC 2 is analytically pure calcium carbide or industrial calcium carbide, preferably analytically pure calcium carbide.

所述的步骤2(1)中,CaC2破碎方式为手工破碎和机械研磨,优选为机械破碎。In the step 2(1), the crushing methods of CaC 2 are manual crushing and mechanical grinding, preferably mechanical crushing.

所述的步骤2(1)中,干燥CaC2粉末粒径优选为50μm-200μm。In the step 2(1), the particle size of the dried CaC 2 powder is preferably 50 μm-200 μm.

所述的步骤2(1)中,干燥温度为80-120℃。In the step 2(1), the drying temperature is 80-120°C.

所述的步骤2(2)中,所述的CaCO3为重质碳酸钙、轻质碳酸钙、活性碳酸钙和纳米碳酸钙,优选为轻质碳酸钙和纳米碳酸钙。In the step 2(2), the CaCO 3 is heavy calcium carbonate, light calcium carbonate, active calcium carbonate and nano-calcium carbonate, preferably light calcium carbonate and nano-calcium carbonate.

所述的步骤2(2)中,所述的CaCO3粉体粒径为0.05μm-200μm,优选为0.1-20μm。In the step 2(2), the particle size of the CaCO 3 powder is 0.05 μm-200 μm, preferably 0.1-20 μm.

所述的步骤2(2)中,干燥温度为100-300℃,优选为120-150℃。In the step 2(2), the drying temperature is 100-300°C, preferably 120-150°C.

所述的步骤3(1)中,作为优选,按摩尔比,CaCO3:CaC2=(1~2):(2~4)。In the step 3(1), preferably, in a molar ratio, CaCO 3 :CaC 2 =(1~2):(2~4).

所述的步骤3(1)中,干燥CaC2粉末、干燥CaCO3粉体、脱水后的熔盐原料置于坩埚中,选用以下五种方式:In the described step 3(1), the dry CaC 2 powder, the dry CaCO 3 powder, and the dehydrated molten salt raw material are placed in the crucible, and the following five methods are selected:

第一种:将所有原料混合均匀后置于坩埚中;The first: mix all the raw materials evenly and place them in a crucible;

第二种,将每种原料逐层平铺后置于坩埚中;逐层平铺优选为从坩埚底部向上逐层分布顺序为干燥CaC2粉末、脱水后的熔盐原料和干燥CaCO3粉体的平铺方式;The second is to lay each raw material layer by layer and place it in the crucible; the layer-by-layer tiling is preferably from the bottom of the crucible to the top and the distribution order is dry CaC 2 powder, dehydrated molten salt raw material and dry CaCO 3 powder tiling method;

第三种,其中两种原料混合均匀后,与另外一种原料逐层平铺;The third type, in which two kinds of raw materials are mixed evenly, and then spread layer by layer with another raw material;

第四种,将部分原料逐层重复平铺后置于坩埚中;The fourth method is to repeatedly lay some raw materials layer by layer and place them in the crucible;

第五种,采用以上四种中至少两种混合方式置于坩埚中。The fifth method is to use at least two of the above four mixing methods to be placed in the crucible.

所述的步骤3(2)中,升温的升温速率为0.5~15℃/min。In the step 3(2), the temperature increase rate is 0.5-15°C/min.

所述的步骤3(2)中,所述的反应温度大于脱水后的熔盐原料的熔点,反应温度优选为600℃~1000℃。In the step 3(2), the reaction temperature is higher than the melting point of the dehydrated molten salt raw material, and the reaction temperature is preferably 600°C to 1000°C.

所述的步骤4中,所述的超声清洗,采用现用盐酸清洗去除未反应的CaC2,再用清水清洗,去除反应后的熔盐,超声波频率为10~30KHz。In the step 4, in the ultrasonic cleaning, the unreacted CaC 2 is removed by cleaning with hydrochloric acid, and then the molten salt after the reaction is removed by cleaning with water, and the ultrasonic frequency is 10-30 KHz.

所述的清水的pH值为5~7,所述的盐酸为物质的量浓度为0.5~2mol/L的盐酸溶液。The pH value of the clear water is 5-7, and the hydrochloric acid is a hydrochloric acid solution with a substance concentration of 0.5-2 mol/L.

所述的步骤4中,所述的固液分离,优选为离心分离,离心分离的转速优选为200~1000r/min。In the step 4, the solid-liquid separation is preferably centrifugal separation, and the rotational speed of the centrifugal separation is preferably 200-1000 r/min.

一种熔盐化学合成碳粉体,采用上述制备方法制得。A molten salt chemically synthesized carbon powder is prepared by the above-mentioned preparation method.

本发明制备的熔盐化学合成碳粉体,其平均粒径为0.1~50μm,随着反应温度的升高,碳粉体从具有花状、管状、片状、球状中至少两种形貌的复合结构趋向于球状形貌的单一结构。The molten salt chemically synthesized carbon powder prepared by the invention has an average particle size of 0.1-50 μm. With the increase of the reaction temperature, the carbon powder has at least two morphologies of flower shape, tube shape, flake shape and spherical shape. The composite structure tends towards a single structure with spherical morphology.

本发明的熔盐化学合成碳粉体的应用,为将熔盐化学合成碳粉体作为锂离子电池负极碳材料,其制备的锂离子电池,其循环充放电比容量大于400mAh g-1,其循环充放电比容量优于普通石墨材料(普通石墨理论容量为372mAh g-1)。The application of the molten salt chemically synthesized carbon powder of the present invention is to use the molten salt chemically synthesized carbon powder as the negative electrode carbon material of the lithium ion battery, and the lithium ion battery prepared by the molten salt chemically synthesized carbon powder has a cyclic charge-discharge specific capacity greater than 400mAh g -1 , and The specific capacity of cycle charge and discharge is better than that of ordinary graphite material (theoretical capacity of ordinary graphite is 372mAh g -1 ).

一种锂离子电池负极材料,包括上述熔盐化学合成碳粉体。A lithium ion battery negative electrode material, comprising the above-mentioned molten salt chemically synthesized carbon powder.

一种电极极片,采用上述锂离子电池负极材料制备。An electrode pole piece is prepared by using the above-mentioned negative electrode material of a lithium ion battery.

一种锂离子电池,包括上述电极极片。A lithium ion battery, comprising the above-mentioned electrode pole piece.

本发明一种熔盐化学合成碳粉体及其制备方法和应用,其原理如下:A kind of molten salt chemical synthesis carbon powder of the present invention and its preparation method and application, its principle is as follows:

碳酸钙和碳化钙分别是两种含有碳元素的无机物,也是常用的化工原料。其中,碳酸钙中的碳元素为氧化态,正四价;碳化钙中的碳元素为还原态,呈负一价。通过热力学计算可知,在600~1000℃范围内,碳酸钙和碳化钙能够发生反应,生成单质碳和氧化钙。该反应的标准吉布斯自由能均小于-400kJ/mol。然而,由于反应物和生成物都为纯固态,在接触反应后,生成物扩散单质碳和碳化钙会阻断反应物的接触,妨碍反应充分进行。利用钙基卤化物熔盐作为反应介质,其对于生成物CaO具有很大的溶解度,使生成的氧化钙迅速溶解,且液态熔盐可以使用碳单质悬浮在其中,从而移除了反应物碳化钙和碳酸钙之间的障碍,使反应迅速进行。另外,碳酸钙和氧化钙在钙基卤化物熔盐中具有较高的溶解度,可以使

Figure BDA0002219267950000041
离子和
Figure BDA0002219267950000042
以溶解态存在于熔盐中,可通过控制反应物浓度、比例和分布、熔盐组成、反应时间等方式对反应过程进行有效调控,从而控制产物结构和形貌。Calcium carbonate and calcium carbide are two kinds of inorganic substances containing carbon, and they are also commonly used chemical raw materials. Among them, the carbon element in calcium carbonate is in an oxidized state and has a positive tetravalence; the carbon element in calcium carbide is in a reduced state and has a negative univalent valence. It can be seen from thermodynamic calculations that in the range of 600-1000 °C, calcium carbonate and calcium carbide can react to generate elemental carbon and calcium oxide. The standard Gibbs free energies of this reaction are all less than -400kJ/mol. However, since both the reactants and the products are pure solids, after the contact reaction, the diffusion of elemental carbon and calcium carbide in the products will block the contact of the reactants and prevent the reaction from proceeding fully. The calcium-based halide molten salt is used as the reaction medium, which has a great solubility for the product CaO, so that the generated calcium oxide can be rapidly dissolved, and the liquid molten salt can be suspended in it with carbon element, thereby removing the reactant calcium carbide The barrier between calcium carbonate and calcium carbonate makes the reaction proceed rapidly. In addition, calcium carbonate and calcium oxide have high solubility in calcium-based halide molten salts, which can make
Figure BDA0002219267950000041
ions and
Figure BDA0002219267950000042
Existing in molten salt in a dissolved state, the reaction process can be effectively regulated by controlling the concentration, proportion and distribution of reactants, composition of molten salt, reaction time, etc., thereby controlling the structure and morphology of the product.

本发明一种熔盐化学合成碳粉体及其制备方法,其有益效果在于:The present invention is a molten salt chemically synthesized carbon powder and a preparation method thereof, and the beneficial effects are as follows:

1、采用本发明的方法可以实现碳粉体在较低温度下的高效、高质量制备,且设备操作简单。1. The method of the present invention can realize the efficient and high-quality preparation of carbon powder at a lower temperature, and the equipment is easy to operate.

2、使用工业原料碳酸钙和碳化钙作为反应原料,可以拓宽碳材料的来源,也可减少天然石墨的过渡消耗以及高温裂解的复杂工艺,并且能够制备出结构和形貌可控的碳粉体材料,其原料丰富易得,反应过程中不产生有毒、有害物质,利于回收。2. The use of industrial raw materials calcium carbonate and calcium carbide as reaction raw materials can broaden the source of carbon materials, reduce the transition consumption of natural graphite and the complex process of high temperature cracking, and can prepare carbon powder with controllable structure and morphology The raw materials are abundant and readily available, and no toxic and harmful substances are produced during the reaction, which is beneficial to recycling.

3、钙基卤化物熔盐的熔融环境对于生成物之一的氧化钙有很高的溶解度,从而使得反应产物及时去除,能够为反应充分进行提供动力学条件。3. The melting environment of calcium-based halide molten salt has a high solubility for calcium oxide, one of the products, so that the reaction product can be removed in time, which can provide kinetic conditions for the reaction to proceed fully.

4、熔融能够将反应物中的含碳离子赋存在熔盐中,从而实现化学反应和产物的调控。4. Melting can endow the carbon-containing ions in the reactants in the molten salt, so as to realize the regulation of chemical reactions and products.

5、本发明以碳化钙和碳酸钙为原料,利用熔融盐介质环境,使用化学方法制备碳粉体材料,能够在较低温度下制备出高质量的碳粉体材料。反应产物为除了碳外,只有氧化钙生成,不产生其他有毒有害物质,具有低成本、工艺绿色环保、对环境友好、产物质量高等特点,并且本发明利用碳酸钙和碳化钙在钙基熔盐中具有一定的溶解度,将碳化反应由固相转变为液相反应,使得反应更容易进行。5. The present invention uses calcium carbide and calcium carbonate as raw materials, uses the molten salt medium environment, and uses chemical methods to prepare carbon powder materials, and can prepare high-quality carbon powder materials at lower temperatures. The reaction product is that in addition to carbon, only calcium oxide is generated, and other toxic and harmful substances are not produced, and it has the characteristics of low cost, green process, environmental friendliness, and high product quality, and the present invention utilizes calcium carbonate and calcium carbide in calcium-based molten salt. It has a certain solubility in the carbonation reaction, which changes the carbonization reaction from the solid phase to the liquid phase reaction, making the reaction easier to carry out.

附图说明Description of drawings

图1为本发明实施例1中熔盐化学合成碳粉体的XRD图;Fig. 1 is the XRD pattern of carbon powder body chemically synthesized by molten salt in Example 1 of the present invention;

图2为本发明实施例1中熔盐化学合成碳粉体的SEM图;Fig. 2 is the SEM image of molten salt chemically synthesized carbon powder in Example 1 of the present invention;

图3为本发明实施例2中熔盐化学合成碳粉体的XRD图;Fig. 3 is the XRD pattern of molten salt chemically synthesized carbon powder in Example 2 of the present invention;

图4为本发明实施例2中熔盐化学合成碳粉体的SEM图Fig. 4 is the SEM image of the carbon powder body chemically synthesized by molten salt in Example 2 of the present invention

图5为本发明实施例15中熔盐化学合成锂离子电池碳负极材料的流程图;Fig. 5 is the flow chart of the chemical synthesis of lithium ion battery carbon negative electrode material by molten salt in the embodiment 15 of the present invention;

图6为本发明实施例15中熔盐化学合成锂离子电池碳负极材料的循环性能;6 is the cycle performance of the chemically synthesized lithium-ion battery carbon negative electrode material by molten salt in Example 15 of the present invention;

图7为本发明实施例15中熔盐化学合成锂离子电池碳负极材料的倍率性能;7 is the rate performance of the chemically synthesized lithium-ion battery carbon negative electrode material in molten salt in Example 15 of the present invention;

具体实施方式Detailed ways

下面结合实施例对本发明作进一步的详细说明。The present invention will be further described in detail below in conjunction with the examples.

本发明实施例中采用钙基卤化物熔盐为分析纯,纯度为99%;In the embodiment of the present invention, the calcium-based halide molten salt is analytically pure, and the purity is 99%;

本发明实施例中采用的氧化铝坩埚为市购产品,纯度为99%,直径为40~200mm,本实施例中采用的为50mm和100mm;The alumina crucible used in the embodiment of the present invention is a commercially available product, the purity is 99%, and the diameter is 40-200 mm, and the alumina crucible used in this embodiment is 50 mm and 100 mm;

本发明实例中采用的Ar氩气为市购高纯氩,纯度为99.999%;The Ar argon used in the example of the present invention is commercially available high-purity argon with a purity of 99.999%;

本发明实施例中采用熔盐为CaCl2、CaCl2-NaCl、CaCl2-LiCl、CaCl2-LiCl-KCl熔盐体系,CaCl2的工作温度800±5℃-1000±5℃;CaCl2-NaCl熔盐体系中,按摩尔比,CaCl2:NaCl=52:48,工作温度为600±5℃-1000±5℃;CaCl2-LiCl熔盐体系中,按摩尔比CaCl2:LiCl=36:64;CaCl2-LiCl-KCl体系中,按摩尔比CaCl2:LiCl:KCl=35:52:13,工作温度为500±5℃-950±5℃。In the embodiment of the present invention, the molten salt used is CaCl 2 , CaCl 2 -NaCl, CaCl 2 -LiCl, CaCl 2 -LiCl-KCl molten salt system, and the working temperature of CaCl 2 is 800±5°C-1000±5°C ; In the NaCl molten salt system, the molar ratio is CaCl 2 : NaCl=52:48, and the working temperature is 600±5°C-1000±5°C; in the CaCl 2 -LiCl molten salt system, the molar ratio CaCl 2 : LiCl=36 : 64; in the CaCl 2 -LiCl-KCl system, the molar ratio of CaCl 2 : LiCl : KCl=35:52:13, and the working temperature is 500±5℃-950±5℃.

本发明实施例中采用熔盐质量为50-1000g;In the embodiment of the present invention, the mass of molten salt used is 50-1000g;

本发明实施例中施加超声场频率为10-30KHz;In the embodiment of the present invention, the applied ultrasonic field frequency is 10-30KHz;

本发明实施例中超声波清洗采用的水pH在5和7之间;In the embodiment of the present invention, the pH of the water used for ultrasonic cleaning is between 5 and 7;

本发明实施例中超声波清洗频率为10~30KHZ;In the embodiment of the present invention, the frequency of ultrasonic cleaning is 10-30KHZ;

本发明实施例中离心分离转速为600r/min。In the embodiment of the present invention, the centrifugal separation speed is 600 r/min.

对比例1Comparative Example 1

一种熔盐化学合成碳粉体的制备方法,包括以下步骤:A preparation method of molten salt chemically synthesized carbon powder, comprising the following steps:

步骤1、碳化钙、碳酸钙原料的准备和反应装置的组装Step 1. Preparation of calcium carbide and calcium carbonate raw materials and assembly of the reaction device

称取10gCaCO3,并在300℃下烘干24h。称取13gCaC2,在惰性气氛中破碎,80℃下干燥。10g CaCO 3 was weighed and dried at 300°C for 24h. 13g CaC 2 was weighed, crushed in an inert atmosphere, and dried at 80°C.

步骤2、碳粉体合成反应Step 2. Carbon powder synthesis reaction

(1)按照从坩埚底部开始CaC2、CaCO3的顺序逐层平铺到直径为50mm的坩埚中,封闭反应器,通入高纯氩气,同时向密闭反应器的密封法兰处通入循环冷却水。(1) Spread CaC 2 and CaCO 3 into a crucible with a diameter of 50mm layer by layer in the order starting from the bottom of the crucible, close the reactor, pass high-purity argon gas, and at the same time pass into the sealing flange of the closed reactor Circulating cooling water.

(2)按照3℃/min升温,温度升到850℃,保温4h,得到反应产物。(2) The temperature is raised at 3°C/min, the temperature is raised to 850°C, and the temperature is maintained for 4 hours to obtain a reaction product.

步骤3、后处理Step 3. Post-processing

将降温后的产物移出反应器,用pH为7的清水反复超声清洗去盐,超声波振荡频率为20kHZ。然后,使用2mol/L的盐酸清洗,并用清水清洗掉余酸,经过离心、干燥后得到产物。反应后,坩埚中的黑色物很少,清洗回收后发现碳元素收率低于10%,表明反应物基本上没有反应。The cooled product was removed from the reactor, and the salt was removed by repeated ultrasonic cleaning with clean water with a pH of 7, and the ultrasonic oscillation frequency was 20kHZ. Then, use 2 mol/L hydrochloric acid to wash, and use clean water to wash off the residual acid, and obtain the product after centrifugation and drying. After the reaction, there were very few black substances in the crucible, and the yield of carbon elements was found to be less than 10% after cleaning and recovery, indicating that the reactants basically did not react.

实施例1Example 1

一种熔盐化学合成碳粉体的制备方法,包括以下步骤:A preparation method of molten salt chemically synthesized carbon powder, comprising the following steps:

步骤1、熔盐脱水处理Step 1, molten salt dehydration treatment

称取50gCaCl2熔盐,在300℃坩埚炉中干燥24h,得到干燥脱水后的熔盐;Weigh 50g of CaCl 2 molten salt, and dry it in a 300°C crucible furnace for 24 hours to obtain a dried and dehydrated molten salt;

步骤2、碳化钙、碳酸钙原料的准备和反应装置的组装Step 2. Preparation of calcium carbide and calcium carbonate raw materials and assembly of the reaction device

称取10gCaCO3,并在300℃下烘干24h,得到干燥熔盐。称取13gCaC2,在惰性气氛中破碎,80℃下干燥。Weigh 10 g of CaCO 3 , and dry it at 300° C. for 24 h to obtain dry molten salt. 13g CaC 2 was weighed, crushed in an inert atmosphere, and dried at 80°C.

步骤3、碳粉体合成反应Step 3. Carbon powder synthesis reaction

(1)按照从坩埚底部开始CaC2、CaCl2和CaCO3的顺序逐层平铺到直径为50mm的坩埚中,封闭反应器,通入高纯氩气,同时向密闭反应器的密封法兰处通入循环冷却水。(1) Spread CaC 2 , CaCl 2 and CaCO 3 layer by layer into a crucible with a diameter of 50 mm in the order starting from the bottom of the crucible, close the reactor, pass high-purity argon gas, and at the same time to the sealing flange of the closed reactor Introduce circulating cooling water.

(2)按照3℃/min升温,温度升到700℃,保温4h,得到反应产物。(2) the temperature is increased at 3°C/min, the temperature is increased to 700°C, and the temperature is maintained for 4 hours to obtain a reaction product.

步骤4、后处理Step 4. Post-processing

将降温后的产物移出反应器,用pH为7的清水反复超声清洗去盐,超声波振荡频率为20kHZ。然后,使用2mol/L的盐酸清洗CaO等不溶物,并用清水清洗掉余酸,经过离心、干燥后得到产品。得到的产物物相和形貌分别见图1和图2。反应得到的产物为主要是无定型碳组成,产物形貌为管状、片状和粒状结构组成。碳元素收率在85%以上。The cooled product was removed from the reactor, and the salt was removed by repeated ultrasonic cleaning with clean water with a pH of 7, and the ultrasonic oscillation frequency was 20kHZ. Then, use 2 mol/L hydrochloric acid to wash insolubles such as CaO, and wash off residual acid with clean water, and obtain the product after centrifugation and drying. The phase and morphology of the obtained product are shown in Figure 1 and Figure 2, respectively. The product obtained by the reaction is mainly composed of amorphous carbon, and the morphology of the product is composed of tubular, flaky and granular structures. The yield of carbon element is above 85%.

实施例2Example 2

一种熔盐化学合成碳粉体的制备方法,同实施例1,不同点在于:A preparation method of molten salt chemically synthesized carbon powder, the same as Embodiment 1, the difference is:

(1)步骤2中使用的温度为900℃。(1) The temperature used in step 2 was 900°C.

得到的产物结构为包含无定形碳和石墨相的复合结构,其XRD见图3,其SEM为图4,从图4中可以看出,其形貌为均匀的球状颗粒。The structure of the obtained product is a composite structure comprising amorphous carbon and graphite phases, its XRD is shown in Figure 3, and its SEM is shown in Figure 4, it can be seen from Figure 4 that its morphology is uniform spherical particles.

实施例3Example 3

一种熔盐化学合成碳粉体的制备方法,同实施例1,不同点在于:A preparation method of molten salt chemically synthesized carbon powder, the same as Embodiment 1, the difference is:

(1)步骤1中使用的熔盐为CaCl2-NaCl共晶混合熔盐,质量为500g,干燥前两种熔盐均匀混合;(1) the molten salt used in the step 1 is CaCl 2 -NaCl eutectic mixed molten salt, the quality is 500g, and the two kinds of molten salts before drying are evenly mixed;

(2)步骤2中CaCO3质量为70g,CaC2质量为91g;( 2 ) in step 2 , CaCO quality is 70g, CaC quality is 91g;

(3)步骤3(1)中刚玉坩埚直径为100mm;(3) in step 3 (1), the diameter of corundum crucible is 100mm;

(4)步骤3(1)中CaC2、CaCl2-NaCl和CaCO3的混合方式为均匀混合;(4) in step 3 (1), the mixing mode of CaC 2 , CaCl 2 -NaCl and CaCO 3 is uniform mixing;

(4)步骤3(2)中反应温度为650℃,反应时间为6h。(4) In step 3 (2), the reaction temperature is 650° C., and the reaction time is 6 h.

实施例4Example 4

一种熔盐化学合成碳粉体的制备方法,同实施例1,不同点在于:A preparation method of molten salt chemically synthesized carbon powder, the same as Embodiment 1, the difference is:

(1)步骤1中使用的熔盐为CaCl2-LiCl共晶混合熔盐,干燥前熔盐均匀混合;(1) The molten salt used in step 1 is CaCl 2 -LiCl eutectic mixed molten salt, and the molten salt is evenly mixed before drying;

(2)步骤2中CaCO3质量为2g,CaC2质量为2.6g;(2) in step 2 , CaCO quality is 2g , CaC quality is 2.6g;

(3)步骤3(1)中CaC2、CaCl2-LiCl和CaCO3从坩埚底部逐层平铺。(3) In step 3(1), CaC 2 , CaCl 2 -LiCl and CaCO 3 are spread layer by layer from the bottom of the crucible.

(4)步骤3(2)中反应温度为750℃,反应时间为4h。(4) In step 3 (2), the reaction temperature is 750° C., and the reaction time is 4 h.

实施例5Example 5

一种熔盐化学合成碳粉体的制备方法,同实施例1,不同点在于:A preparation method of molten salt chemically synthesized carbon powder, the same as Embodiment 1, the difference is:

(1)步骤1中使用的熔盐为CaCl2-LiCl-KCl共晶混合熔盐,质量为100g,干燥前熔盐均匀混合;(1) the molten salt used in step 1 is CaCl 2 -LiCl-KCl eutectic mixed molten salt, the quality is 100g, and the molten salt is evenly mixed before drying;

(2)步骤2中CaCO3为3.5g,CaC2为4.55g;(2) in step 2 , CaCO 3.5g, CaC 4.55g ;

(3)步骤3(1)中CaC2、CaCl2-LiCl-KCl和CaCO3均匀混合。(3) In step 3(1), CaC 2 , CaCl 2 -LiCl-KCl and CaCO 3 are uniformly mixed.

(4)步骤3(2)中反应温度为700℃,反应时间为5h。(4) In step 3 (2), the reaction temperature is 700° C., and the reaction time is 5 h.

实施例6Example 6

一种熔盐化学合成碳粉体的制备方法,同实施例1,不同点在于:A preparation method of molten salt chemically synthesized carbon powder, the same as Embodiment 1, the difference is:

(1)步骤1中使用的熔盐质量为1000g;(1) the molten salt quality used in step 1 is 1000g;

(2)步骤2中CaCO3为40g,CaC2为64g;( 2 ) in step 2 , CaCO is 40g, and CaC is 64g;

(3)步骤3(1)中刚玉坩埚直径为150mm;(3) in step 3 (1), the diameter of corundum crucible is 150mm;

(3)步骤3(1)中CaC2、CaCl2和CaCO3均匀混合。(3) In step 3(1), CaC 2 , CaCl 2 and CaCO 3 are uniformly mixed.

实施例7Example 7

一种熔盐化学合成碳粉体的制备方法,同实施例1,不同点在于:A preparation method of molten salt chemically synthesized carbon powder, the same as Embodiment 1, the difference is:

(1)步骤3(1)中CaCO3、CaCl2和CaC2从坩埚底部开始逐层平铺。(1) In step 3 (1), CaCO 3 , CaCl 2 and CaC 2 are laid out layer by layer from the bottom of the crucible.

实施例8Example 8

一种熔盐化学合成碳粉体的制备方法,同实施例1,不同点在于:A preparation method of molten salt chemically synthesized carbon powder, the same as Embodiment 1, the difference is:

(1)步骤3(1)中从坩埚底部开始以CaC2(0.5份总质量)、CaCl2(三分之一份总质量)、CaCO3(0.5份总质量)、CaCl2(三分之一份总质量)、CaC2(0.5份总质量)、CaCl2(三分之一份总质量)和CaCO3(0.5份总质量)的次序逐层平铺。(1) Starting from the bottom of the crucible in step 3 (1), add CaC 2 (0.5 part of the total mass), CaCl 2 (one-third part of the total mass), CaCO 3 (0.5 part of the total mass), CaCl 2 (one-third part of the total mass) One part total mass), CaC2 (0.5 part total mass), CaCl2 ( one- third total mass) and CaCO3 (0.5 part total mass) were tiled layer by layer.

实施例9Example 9

一种熔盐化学合成碳粉体的制备方法,同实施例3,不同点在于:A preparation method of molten salt chemically synthesized carbon powder, the same as in Embodiment 3, the difference is:

(1)步骤3(1)中CaCO3、CaCl2-NaCl和CaC2从坩埚底部开始逐层平铺。(1) In step 3 (1), CaCO 3 , CaCl 2 -NaCl and CaC 2 are laid out layer by layer from the bottom of the crucible.

实施例10Example 10

一种熔盐化学合成碳粉体的制备方法,同实施例3,不同点在于:A preparation method of molten salt chemically synthesized carbon powder, the same as in Embodiment 3, the difference is:

(1)步骤3(1)中从坩埚底部开始以CaC2(0.5份总质量)、CaCl2-NaCl(三分之一份总质量)、CaCO3(0.5份总质量)、CaCl2-NaCl(三分之一份总质量)、CaC2(0.5份总质量)、CaCl2-NaCl(三分之一份总质量)和CaCO3(0.5份总质量)的次序逐层平铺。(1) In step 3 (1), starting from the bottom of the crucible, add CaC 2 (0.5 part of the total mass), CaCl 2 -NaCl (one-third part of the total mass), CaCO 3 (0.5 part of the total mass), CaCl 2 -NaCl (one-third total mass), CaC2 (0.5 total mass), CaCl2 - NaCl (one- third total mass), and CaCO3 (0.5 total mass) were tiled in the order.

实施例11Example 11

一种熔盐化学合成碳粉体的制备方法,同实施例4,不同点在于:A preparation method of molten salt chemically synthesized carbon powder, the same as in Example 4, the difference is:

(1)步骤3(1)中CaCO3、CaCl2-LiCl和CaC2从坩埚底部开始逐层平铺。(1) In step 3 (1), CaCO 3 , CaCl 2 -LiCl and CaC 2 are laid out layer by layer from the bottom of the crucible.

实施例12Example 12

一种熔盐化学合成碳粉体的制备方法,同实施例4,不同点在于:A preparation method of molten salt chemically synthesized carbon powder, the same as in Example 4, the difference is:

(1)步骤3(1)中从坩埚底部开始以CaC2(0.5份总质量)、CaCl2-LiCl(三分之一份总质量)、CaCO3(0.5份总质量)、CaCl2-LiCl(三分之一份总质量)、CaC2(0.5份总质量)、CaCl2-LiCl(三分之一份总质量)和CaCO3(0.5份总质量)的次序逐层平铺。(1) In step 3(1), starting from the bottom of the crucible, add CaC 2 (0.5 part of the total mass), CaCl 2 -LiCl (one third of the total mass), CaCO 3 (0.5 part of the total mass), CaCl 2 -LiCl (one-third total mass), CaC2 (0.5 total mass), CaCl2 - LiCl (one- third total mass), and CaCO3 (0.5 total mass) were tiled layer by layer in the order.

实施例13Example 13

一种熔盐化学合成碳粉体的制备方法,同实施例3,不同点在于:A preparation method of molten salt chemically synthesized carbon powder, the same as in Embodiment 3, the difference is:

(1)步骤3(1)中CaCO3、CaCl2-LiCl-KCl和CaC2从坩埚底部开始逐层平铺。(1) In step 3 (1), CaCO 3 , CaCl 2 -LiCl-KCl and CaC 2 are laid out layer by layer from the bottom of the crucible.

实施例14Example 14

一种熔盐化学合成碳粉体的制备方法,同实施例3,不同点在于:A preparation method of molten salt chemically synthesized carbon powder, the same as in Embodiment 3, the difference is:

(1)步骤3(1)中从坩埚底部开始以CaC2(0.5份总质量)、CaCl2-LiCl-KCl(三分之一份总质量)、CaCO3(0.5份总质量)、CaCl2-LiCl-KCl(三分之一份总质量)、CaC2(0.5份总质量)、CaCl2-LiCl-KCl(三分之一份总质量)和CaCO3(0.5份总质量)的次序逐层平铺。(1) In step 3(1), starting from the bottom of the crucible, add CaC 2 (0.5 part of the total mass), CaCl 2 -LiCl-KCl (one-third part of the total mass), CaCO 3 (0.5 part of the total mass), CaCl 2 - LiCl-KCl (one-third total mass), CaC2 (0.5 total mass), CaCl2 - LiCl-KCl (one- third total mass) and CaCO3 (0.5 total mass) in order Layer tiling.

实施例15Example 15

一种熔盐中制备锂离子电池碳负极材料的方法,工艺流程为图5,包括如下步骤A method for preparing a lithium ion battery carbon negative electrode material in molten salt, the process flow is shown in Figure 5, including the following steps

步骤1:取实施例1中得到的碳粉末作为碳材料;Step 1: take the carbon powder obtained in Example 1 as the carbon material;

步骤2:电池的组装和测试Step 2: Assembly and Testing of Batteries

所得碳材料与乙炔黑和PVDF按8:1:1的质量比在NMP介质中制成浆料,得到锂离子电池负极材料;The obtained carbon material, acetylene black and PVDF are made into a slurry in NMP medium at a mass ratio of 8:1:1 to obtain a lithium ion battery negative electrode material;

将锂离子电池负极材料,涂布于铜箔上,在80℃真空中干燥12h,得到电极极片。The negative electrode material of the lithium ion battery was coated on the copper foil and dried in a vacuum at 80° C. for 12 hours to obtain an electrode pole piece.

以电极极片和锂片为对电极,聚丙烯膜为隔膜,电解液为1MLLiPF6/(EC:DEC=1:1),电池壳型号为2025,以0.5C电流密度充放电,在1~2.5V的电压范围内进行循环寿命测试。The electrode pole piece and lithium piece are used as the counter electrode, the polypropylene film is used as the separator, the electrolyte is 1MLLiPF6/(EC:DEC=1:1), the battery shell model is 2025, and the battery is charged and discharged at a current density of 0.5C. The cycle life test is carried out within the voltage range of V.

图6和图7分别是该碳负极材料的循环性能和倍率性能。可见,该材料具有很好的循环和倍率性能,容量明显高于普通石墨(普通石墨理论容量为372mAh g-1)。虽然电池稳定性有待提高,但由于材料目前为无定型碳和石墨和复合体,且微观形貌是纤维、球状和花瓣等多种颗粒混杂,该问题可通过对于反应的调控来调整最终产物的结构和形貌,获得循环性能高和稳定性更好的材料。Figure 6 and Figure 7 are the cycle performance and rate performance of the carbon anode material, respectively. It can be seen that the material has good cycle and rate performance, and the capacity is significantly higher than that of ordinary graphite (the theoretical capacity of ordinary graphite is 372mAh g -1 ). Although the stability of the battery needs to be improved, because the materials are currently amorphous carbon, graphite and composites, and the microscopic morphology is a mixture of various particles such as fibers, spheres, and petals, this problem can be adjusted by regulating the reaction. structure and morphology to obtain materials with high cycle performance and better stability.

实施例16Example 16

一种熔盐中制备锂离子电池碳负极材料的方法,同实施例15,不同点在于:A method for preparing a carbon negative electrode material for a lithium ion battery in a molten salt is the same as in Example 15, except that:

(1)步骤1(1)中使用的熔盐为CaCl2-NaCl共晶混合熔盐,质量为200g,干燥前CaCl2、NaCl均匀混合;(1) The molten salt used in step 1 (1) is CaCl 2 -NaCl eutectic mixed molten salt, the quality is 200g, and CaCl 2 and NaCl are uniformly mixed before drying;

(2)步骤1(2)中CaCO3为纳米CaCO3,质量为14g;(2) in step 1 (2), CaCO 3 is nano-CaCO 3 , and the quality is 14g;

(3)步骤1(3)中CaC2质量为18.2g;( 3 ) CaC mass is 18.2g in step 1 (3);

(4)步骤2(1)中CaC2、CaCl2-NaCl和CaCO3的混合方式为均匀混合;(4) in step 2 (1), the mixing mode of CaC 2 , CaCl 2 -NaCl and CaCO 3 is uniform mixing;

(4)步骤2(2)中反应温度为650℃,反应时间为6h。(4) In step 2 (2), the reaction temperature is 650° C., and the reaction time is 6 h.

实施例17Example 17

一种熔盐中制备锂离子电池碳负极材料的方法,同实施例15,不同点在于:A method for preparing a carbon negative electrode material for a lithium ion battery in a molten salt is the same as in Example 15, except that:

(1)步骤1(1)中使用的熔盐为CaCl2-LiCl共晶混合熔盐,干燥前熔盐均匀混合;(1) The molten salt used in step 1 (1) is CaCl 2 -LiCl eutectic mixed molten salt, and the molten salt is uniformly mixed before drying;

(2)步骤1(2)中轻质CaCO3质量为2g,(2) in step 1 ( 2 ), light CaCO mass is 2g,

(3)步骤1(3)中CaC2质量为2.6g;( 3 ) CaC mass is 2.6g in step 1 (3);

(4)步骤2(1)中CaC2、CaCl2-LiCl和CaCO3从坩埚底部逐层平铺;(4) in step 2 (1), CaC 2 , CaCl 2 -LiCl and CaCO 3 are tiled layer by layer from the bottom of the crucible;

(4)步骤2(2)中反应温度为750℃,反应时间为4h。(4) In step 2 (2), the reaction temperature is 750° C., and the reaction time is 4 h.

实施例18Example 18

一种熔盐中制备锂离子电池碳负极材料的方法,同实施例15,不同点在于:A method for preparing a carbon negative electrode material for a lithium ion battery in a molten salt is the same as in Example 15, except that:

(1)步骤1(1)中使用的CaCl2质量为800g;(1) CaCl used in step 1 ( 1 ) Quality is 800g;

(2)步骤1(2)中CaCO3为重质碳酸钙,质量为160g,(2) CaCO in step 1 ( 2 ) is heavy calcium carbonate, and the quality is 160g,

(3)步骤1(3)中CaC2质量为60g;(3) in step 1 ( 3 ), CaC quality is 60g;

(4)步骤2(1)中刚玉坩埚直径为150mm;(4) in step 2 (1), the diameter of corundum crucible is 150mm;

(5)步骤2(1)中CaC2、CaCl2和CaCO3均匀混合。(5) In step 2(1), CaC 2 , CaCl 2 and CaCO 3 are uniformly mixed.

(6)步骤2(2)中反应温度为950℃,反应时间为8h。(6) In step 2 (2), the reaction temperature is 950° C., and the reaction time is 8 h.

实施例19Example 19

一种熔盐中制备锂离子电池碳负极材料的方法,同实施例15,不同点在于:A method for preparing a carbon negative electrode material for a lithium ion battery in a molten salt is the same as in Example 15, except that:

(1)步骤1(1)中使用的CaCl2质量为800g;(1) CaCl used in step 1 ( 1 ) Quality is 800g;

(2)步骤1(2)中CaCO3为重质碳酸钙,质量为160g,(2) CaCO in step 1 ( 2 ) is heavy calcium carbonate, and the quality is 160g,

(3)步骤1(3)中CaC2质量为60g;(3) in step 1 ( 3 ), CaC quality is 60g;

(4)步骤2(1)中刚玉坩埚直径为150mm;(4) in step 2 (1), the diameter of corundum crucible is 150mm;

(5)步骤2(1)中CaCl2和CaCO3均匀混合,然后按照CaC2和混合物从坩埚底部从下至上逐层平铺。(5) In step 2 (1), CaCl 2 and CaCO 3 are uniformly mixed, and then spread layer by layer from bottom to top from the bottom of the crucible according to the CaC 2 and the mixture.

(6)步骤2(2)中反应温度为1000℃,反应时间为4h。(6) In step 2 (2), the reaction temperature is 1000° C., and the reaction time is 4 h.

实施例20Example 20

一种熔盐中制备锂离子电池碳负极材料的方法,同实施例15,不同点在于:A method for preparing a carbon negative electrode material for a lithium ion battery in a molten salt is the same as in Example 15, except that:

(1)步骤2(1)中从坩埚底部开始以CaC2(0.5份总质量)、CaCl2(三分之一份总质量)、CaCO3(0.5份总质量)、CaCl2(三分之一份总质量)、CaC2(0.5份总质量)、CaCl2(三分之一份总质量)和CaCO3(0.5份总质量)的次序逐层平铺。(1) In step 2(1), starting from the bottom of the crucible, add CaC 2 (0.5 part of the total mass), CaCl 2 (one-third part of the total mass), CaCO 3 (0.5 part of the total mass), CaCl 2 (one-third part of the total mass) One part total mass), CaC2 (0.5 part total mass), CaCl2 ( one- third total mass) and CaCO3 (0.5 part total mass) were tiled layer by layer.

(2)步骤2(2)中反应温度为900℃,反应时间为2h。(2) In step 2 (2), the reaction temperature is 900° C., and the reaction time is 2 h.

实施例21Example 21

一种熔盐中制备锂离子电池碳负极材料的方法,同实施例16,不同点在于:A method for preparing a carbon negative electrode material for a lithium ion battery in a molten salt is the same as in Example 16, except that:

(1)步骤1(1)中使用的熔盐为CaCl2-NaCl共晶混合熔盐质量为1000g;(1) the molten salt used in step 1 (1) is CaCl 2 -NaCl eutectic mixed molten salt quality is 1000g;

(2)步骤1(2)中纳米CaCO3,质量为280g;(2) nano-CaCO 3 in step 1 (2), the quality is 280g;

(3)步骤1(3)中CaC2质量为109.2g;( 3 ) CaC mass is 109.2g in step 1 (3);

(4)步骤2(1)中CaC2、CaCl2-NaCl和CaCO3以逐层平铺方式混合;(4) in step 2(1), CaC 2 , CaCl 2 -NaCl and CaCO 3 are mixed in a layer-by-layer tiling manner;

(4)步骤2(2)中反应温度为800℃,反应时间为10h。(4) In step 2 (2), the reaction temperature is 800° C., and the reaction time is 10 h.

实施例22Example 22

一种熔盐中制备锂离子电池碳负极材料的方法,同实施例16,不同点在于:A method for preparing a carbon negative electrode material for a lithium ion battery in a molten salt is the same as in Example 16, except that:

(1)步骤2(1)中CaCl2-NaCl和CaCO3均匀混合,然后按照CaC2和混合物从坩埚底部从下至上逐层平铺。(1) In step 2 (1), CaCl 2 -NaCl and CaCO 3 are uniformly mixed, and then spread layer by layer from bottom to top according to the CaC 2 and the mixture from the bottom of the crucible.

(2)步骤2(2)中反应温度为900℃,反应时间为7h。(2) In step 2 (2), the reaction temperature is 900° C., and the reaction time is 7 h.

实施例23Example 23

一种熔盐中制备锂离子电池碳负极材料的方法,同实施例16,不同点在于:A method for preparing a carbon negative electrode material for a lithium ion battery in a molten salt is the same as in Example 16, except that:

(1)步骤2(1)中从坩埚底部开始以CaC2(0.5份总质量)、CaCl2(三分之一份总质量)、CaCO3(0.5份总质量)、CaCl2(三分之一份总质量)、CaC2(0.5份总质量)、CaCl2(三分之一份总质量)和CaCO3(0.5份总质量)的次序逐层平铺。(1) In step 2(1), starting from the bottom of the crucible, add CaC 2 (0.5 part of the total mass), CaCl 2 (one-third part of the total mass), CaCO 3 (0.5 part of the total mass), CaCl 2 (one-third part of the total mass) One part total mass), CaC2 (0.5 part total mass), CaCl2 ( one- third total mass) and CaCO3 (0.5 part total mass) were tiled layer by layer.

(2)步骤2(2)中反应时间为3h。(2) The reaction time in step 2 (2) is 3h.

实施例24Example 24

一种熔盐中制备锂离子电池碳负极材料的方法,同实施例17,不同点在于:A method for preparing a carbon negative electrode material for a lithium ion battery in a molten salt is the same as in Example 17, except that:

(1)步骤1(1)中使用的熔盐为CaCl2-LiCl共晶混合熔盐质量为500g;(1) the molten salt used in step 1 (1) is CaCl 2 -LiCl eutectic mixed molten salt quality is 500g;

(2)步骤1(2)中活性CaCO3,质量为140g;(2) the active CaCO 3 in step 1 (2), the mass is 140g;

(3)步骤1(3)中CaC2质量为65g;(3) in step 1 ( 3 ), CaC quality is 65g;

(4)步骤2(1)中CaC2、CaCl2-LiCl和CaCO3均匀混合;(4) in step 2(1), CaC 2 , CaCl 2 -LiCl and CaCO 3 are uniformly mixed;

(4)步骤2(2)中反应温度为850℃,反应时间为8h。(4) In step 2 (2), the reaction temperature is 850° C., and the reaction time is 8 h.

实施例25Example 25

一种熔盐中制备锂离子电池碳负极材料的方法,同实施例17,不同点在于:A method for preparing a carbon negative electrode material for a lithium ion battery in a molten salt is the same as in Example 17, except that:

(1)步骤2(1)中CaCl2-LiCl和CaCO3均匀混合,然后按照CaC2和混合物从坩埚底部从下至上逐层平铺。(1) In step 2 (1), CaCl 2 -LiCl and CaCO 3 are uniformly mixed, and then spread layer by layer from bottom to top according to CaC 2 and the mixture from the bottom of the crucible.

(2)步骤2(2)中反应时间为5h。(2) The reaction time in step 2 (2) is 5h.

实施例26Example 26

一种熔盐中制备锂离子电池碳负极材料的方法,同实施例17,不同点在于:A method for preparing a carbon negative electrode material for a lithium ion battery in a molten salt is the same as in Example 17, except that:

(1)步骤2(1)中从坩埚底部开始以CaC2(0.5份总质量)、CaCl2-LiCl(三分之一份总质量)、CaCO3(0.5份总质量)、CaCl2-LiCl(三分之一份总质量)、CaC2(0.5份总质量)、CaCl2-LiCl(三分之一份总质量)和CaCO3(0.5份总质量)的次序逐层平铺。(1) In step 2(1), starting from the bottom of the crucible, add CaC 2 (0.5 part of the total mass), CaCl 2 -LiCl (one-third of the total mass), CaCO 3 (0.5 part of the total mass), CaCl 2 -LiCl (one-third total mass), CaC2 (0.5 total mass), CaCl2 - LiCl (one- third total mass), and CaCO3 (0.5 total mass) were tiled layer by layer in the order.

(2)步骤2(2)中反应时间为2h。(2) In step 2 (2), the reaction time is 2h.

Claims (10)

1.一种熔盐化学合成碳粉体的制备方法,其特征在于,包括以下步骤:1. a preparation method of molten salt chemical synthesis carbon powder, is characterized in that, comprises the following steps: 步骤1:熔盐脱水处理Step 1: Molten Salt Dehydration Treatment 将熔盐的原料,真空干燥,随炉冷却至室温,得到脱水后的熔盐原料;所述的熔盐为卤化钙、卤化钙和碱金属卤族化合物的混合物、或卤化钙和碱土金属卤族化合物的混合物、或卤化钙和碱土金属卤族化合物和碱金属卤族化合物的混合物中的一种;当熔盐为混合物时,其混合比例为混合的物质形成共晶盐的混合比例;The raw material of the molten salt is vacuum-dried, and cooled to room temperature with the furnace to obtain the dehydrated molten salt raw material; the molten salt is a mixture of calcium halide, calcium halide and alkali metal halide compound, or calcium halide and alkaline earth metal halide One of the mixture of calcium halide and alkaline earth metal halide compound and the mixture of alkali metal halide compound; when the molten salt is a mixture, its mixing ratio is the mixing ratio of the mixed substances to form a eutectic salt; 步骤2:碳化钙、碳酸钙的准备Step 2: Preparation of calcium carbide and calcium carbonate (1)称取CaC2,在惰性气氛下破碎,干燥,得到粒径为1μm-5mm的干燥CaC2粉末;(1) Weigh the CaC 2 , crush it under an inert atmosphere, and dry it to obtain a dry CaC 2 powder with a particle size of 1 μm-5mm; (2)称取CaCO3粉体,干燥,得到干燥CaCO3粉体;( 2 ) take by weighing CaCO powder, dry, obtain dry CaCO powder ; 步骤3:熔盐化学合成碳粉体Step 3: Molten Salt Chemical Synthesis of Carbon Powder (1)按配比,称量干燥CaC2粉末、干燥CaCO3粉体、脱水后的熔盐原料,置于坩埚中,在放入密闭反应器中,通入惰性气体保护;其中,按CaCO3完全反应,CaCO3+2CaC2→3CaO+5C的化学公式,CaC2加入量按化学计量比过量1~100 wt.%,CaCO3的质量占脱水后的熔盐原料中卤化钙的质量百分比为0.1~20%;(1) According to the proportion, weigh the dry CaC 2 powder, the dry CaCO 3 powder, the dehydrated molten salt raw material, place it in a crucible, put it into a closed reactor, and pass it into an inert gas for protection; wherein, according to CaCO 3 Complete reaction, the chemical formula of CaCO 3 +2CaC 2 →3CaO+5C, the amount of CaC 2 added is 1~100 wt.% in excess of the stoichiometric ratio, and the mass of CaCO 3 accounts for the mass percentage of calcium halide in the dehydrated molten salt raw material: 0.1~20%; (2)将密闭反应器升温至反应温度,保温5min~10h进行碳化反应,得到碳产物;其中,反应温度大于脱水后的熔盐原料的熔点;(2) the airtight reactor is heated up to the reaction temperature, and the thermal insulation is carried out for 5min~10h to carry out the carbonization reaction to obtain a carbon product; wherein, the reaction temperature is greater than the melting point of the dehydrated molten salt raw material; 步骤4:后处理Step 4: Post-processing 将碳产物进行超声清洗,固液分离,去除熔盐,干燥,得到碳粉体。The carbon product is subjected to ultrasonic cleaning, solid-liquid separation, removal of molten salt, and drying to obtain carbon powder. 2.根据权利要求1所述的熔盐化学合成碳粉体的制备方法,其特征在于,熔盐中,卤化钙为CaCl2、CaBr2、CaF2中的一种或几种;2. The preparation method of chemically synthesized carbon powder in molten salt according to claim 1, characterized in that, in the molten salt, calcium halide is one or more of CaCl 2 , CaBr 2 , CaF 2 ; 所述的碱金属卤族化合物为NaCl、KCl、LiCl、NaBr、KBr、LiBr、NaF、KF、LiF中的一种或几种;Described alkali metal halide compound is one or more in NaCl, KCl, LiCl, NaBr, KBr, LiBr, NaF, KF, LiF; 所述的碱土金属卤族化合物为MgCl2、MgF2、CaCl2、CaF2、SrCl2、SrF2、BaCl2、BaF2中的一种或几种。The alkaline earth metal halide compound is one or more of MgCl 2 , MgF 2 , CaCl 2 , CaF 2 , SrCl 2 , SrF 2 , BaCl 2 , and BaF 2 . 3.根据权利要求1所述的熔盐化学合成碳粉体的制备方法,其特征在于,所述的步骤2(1)中,CaC2为分析纯碳化钙或工业电石;干燥温度为80-120℃。3. the preparation method of molten salt chemical synthesis carbon powder body according to claim 1, is characterized in that, in described step 2 (1), CaC 2 is analytically pure calcium carbide or industrial calcium carbide; drying temperature is 80- 120°C. 4.根据权利要求1所述的熔盐化学合成碳粉体的制备方法,其特征在于,所述的步骤2(2)中,所述的CaCO3为重质碳酸钙、轻质碳酸钙、活性碳酸钙和纳米碳酸钙;所述的CaCO3粉体粒径为0.05μm-200μm;干燥温度为100-300℃。4. the preparation method of molten salt chemical synthesis carbon powder body according to claim 1, is characterized in that, in described step 2 (2), described CaCO 3 is heavy calcium carbonate, light calcium carbonate, Activated calcium carbonate and nano-calcium carbonate; the particle size of the CaCO 3 powder is 0.05 μm-200 μm; the drying temperature is 100-300° C. 5.根据权利要求1所述的熔盐化学合成碳粉体的制备方法,其特征在于,所述的步骤3(2)中,反应温度为600℃~1000℃。5 . The method for preparing carbon powder by molten salt chemical synthesis according to claim 1 , wherein, in the step 3 (2), the reaction temperature is 600° C.˜1000° C. 6 . 6.一种熔盐化学合成碳粉体,其特征在于,采用权利要求1~5任意一项所述的制备方法制得。6. A molten salt chemically synthesized carbon powder, characterized in that, it is obtained by the preparation method described in any one of claims 1 to 5. 7.根据权利要求6所述的熔盐化学合成碳粉体,其特征在于,制备的熔盐化学合成碳粉体,其平均粒径为0.1~50μm,随着反应温度的升高,熔盐化学合成碳粉体从具有花状、管状、片状、球状中至少两种形貌的复合结构趋向于球状形貌的单一结构。7. The molten salt chemically synthesized carbon powder according to claim 6, wherein the prepared molten salt chemically synthesized carbon powder has an average particle size of 0.1 to 50 μm. The chemically synthesized carbon powder tends to have a single structure with a spherical shape from a composite structure with at least two morphologies among flower-like, tubular, flake-like and spherical. 8.一种锂离子电池负极材料,其特征在于,该锂离子电池负极材料包括权利要求6所述的熔盐化学合成碳粉体。8 . A negative electrode material for lithium ion batteries, characterized in that the negative electrode material for lithium ion batteries comprises the chemically synthesized carbon powder of molten salt according to claim 6 . 9.一种电极极片,其特征在于,采用权利要求8所述的锂离子电池负极材料制备。9 . An electrode pole piece, characterized in that, it is prepared by using the negative electrode material of a lithium ion battery according to claim 8 . 10.一种锂离子电池,其特征在于,该锂离子电池包括权利要求9所述的电极极片,制备的锂离子电池的循环充放电比容量大于400mAh g-110 . A lithium ion battery, characterized in that the lithium ion battery comprises the electrode plate of claim 9 , and the prepared lithium ion battery has a specific capacity of cyclic charge and discharge greater than 400 mAh g −1 .
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