技术领域technical field
本发明涉及锂离子电池正极材料制备领域，具体地指一种磷酸铁锂/三维碳架/碳复合材料的制备方法。The invention relates to the field of preparation of positive electrode materials of lithium ion batteries, in particular to a preparation method of lithium iron phosphate/three-dimensional carbon frame/carbon composite material.
背景技术Background technique
自1991年sony公司首次推出商品锂离子电池以来，锂离子电池已经以其开路电压高、循环寿命长、能量密度高、自放电低、无记忆效应、对环境友好等优点广泛应用于人们工作、学习、生活的各个方面。近年来，随着动力电池及大型电力储能装置的市场需求不断增加，陆续出现了以锂离子电池作为载体的动力及储能电源。Since Sony first launched commercial lithium-ion batteries in 1991, lithium-ion batteries have been widely used in people's work, All aspects of study and life. In recent years, with the increasing market demand for power batteries and large-scale power energy storage devices, power and energy storage power sources using lithium-ion batteries as carriers have emerged one after another.
LiFePO4作为锂二次电池正极材料中的一员，因其廉价、环境友好、电压平台平坦、安全性好等优点被认为是最有前途的锂离子电池正极材料之一。但由于LiFePO4不具有层状LiCoO2、LiMnO2和尖晶石状LiMn2O4的二维或三维Li+迁移通道，其离子传导率和电子电导率均偏低，其中离子传导率为10-11cm2/S电子电导率为10-9S/cm，大电流充放电时容量不能全部发挥而影响其应用。LiFePO4 , as one of the cathode materials for lithium secondary batteries, is considered to be one of the most promising cathode materials for lithium-ion batteries because of its cheapness, environmental friendliness, flat voltage platform, and good safety. However, since LiFePO4 does not have two-dimensional or three-dimensional Li+ migration channels of layered LiCoO2 , LiMnO2 and spinel-like LiMn2 O4 , its ionic conductivity and electronic conductivity are both low, and the ionic conductivity is 10-11 cm2 /S The electronic conductivity is 10-9 S/cm, and the capacity cannot be fully utilized during high current charging and discharging, which affects its application.
为解决上述两个缺点人们做了多方面的研究，如包覆导电剂、金属离子掺杂、通过不同合成方法减小颗粒尺寸等。其中碳包覆就是一种重要改性手段。碳包覆能够有效的提高LiFePO4颗粒的导电性。但是LiFePO4表面包覆的碳是非活性物质，碳加入量过多不但会影响材料的振实密度和加工性能，同时在一定程度上减小了LiFePO4与电解液的接触面积，阻碍了Li+的运动。而采用多孔碳材料进行开放式包覆既可以提高材料电子电导率又不影响Li+运动，目前对包覆碳材料进行多孔化的研究还较少，将包覆碳多孔化是提高材料性能很有发展前景的一个方向。目前，在碳包覆工艺方面已做了大量工作。例如，中国专利(公布号CNIO5390682A，公布日2016.03.09)公开一种磷酸铁锂微球/三维石墨烯复合电极材料的制备方法，步骤是：称取1g磷酸铁和1g葡萄糖分散于80ml去离子水中，置于100ml水热反应釜中120℃反应5h，洗涤干燥制得“球形铁源”多羟基磷酸铁微球。将2g多羟基磷酸铁微球(按铁金属质量)、0.3g醋酸锂(按锂金属质量)和0.6g氧化石墨烯分散于去离子水中，干燥；将上述混合物放置高温管式炉中，在氮气气氛下进行高温热反应，反应温度为750℃，反应时间为8h，升温速度为2℃/min；即制得“LiFePO4微/三维石墨烯”复合材料。上述方法采用氧化石墨烯作为三维导电骨架的原料首先氧化石墨烯价格较贵不利于工业化应用，另外上述方法构建三维石墨烯的基本原理是层状氧化石墨烯在水热反应中进行自组装由层状结构组装成三维孔状结构，但是上述方法是一步法即氧化石墨烯水热自组装时会受到溶液中其他离子的影响，极易导致得到的三维石墨烯结构不完整。中国专利(公布CNIO557622OA，公开日2016.05.11)公开一种多孔状碳包覆磷酸铁锂正极材料的制备，步骤是：136.2g无水乙醇溶解于136.2g去离子中，倒入反应釜；称取157gLiFePO4、19.4g葡萄糖与88.2g碳酸氢铵混合均匀后放入反应釜中，混合物充分搅拌lh。搅拌均匀后的浆料放入真空冷冻干燥机中，-10℃下冻结lh，然后在真空13Pa环境下干燥5h。干燥后固体放入100℃烘箱，烘干lh，氮气保护氛围下750℃烧结2h。冷却至室温，研磨后过325目筛，得到多孔状碳包覆LiFePO4/C。上述方法制备多孔碳的原理是铵盐气相分解进行造孔得到了多孔状碳，但是多孔状碳与LiFePO4只是物理混合另外LiFePO4没有存在于多孔状碳的孔洞结构中，多孔状碳仅起到导电作用，并不能起到限制粒径的作用。In order to solve the above two shortcomings, people have done many researches, such as coating conductive agent, metal ion doping, reducing particle size through different synthesis methods, etc. Among them, carbon coating is an important modification method. Carbon coating can effectively improve the conductivity of LiFePO4 particles. However, the carbon coated on the surface of LiFePO4 is an inactive substance. Too much carbon will not only affect the tap density and processing performance of the material, but also reduce the contact area between LiFePO4 and the electrolyte to a certain extent, hindering the Li+ exercise. However, the open coating of porous carbon materials can improve the electronic conductivity of the material without affecting the movement of Li+ . At present, there are few studies on the porous coating of carbon materials. Porous coating of carbon materials is a great way to improve the performance of materials. A direction with development prospects. At present, a lot of work has been done on the carbon coating process. For example, Chinese patent (publication number CNIO5390682A, publication date 2016.03.09) discloses a preparation method of lithium iron phosphate microspheres/three-dimensional graphene composite electrode material. In water, put it in a 100ml hydrothermal reaction kettle to react at 120°C for 5h, wash and dry to obtain "spherical iron source" polyhydroxy iron phosphate microspheres. 2g polyhydroxy iron phosphate microspheres (by iron metal mass), 0.3g lithium acetate (by lithium metal mass) and 0.6g graphene oxide were dispersed in deionized water and dried; The high-temperature thermal reaction was carried out under nitrogen atmosphere, the reaction temperature was 750°C, the reaction time was 8h, and the heating rate was 2°C/min; the "LiFePO4 micro/three-dimensional graphene" composite material was obtained. The above method uses graphene oxide as the raw material of the three-dimensional conductive framework. Firstly, the price of graphene oxide is relatively expensive, which is not conducive to industrial application. In addition, the basic principle of the above method to construct three-dimensional graphene is that layered graphene oxide self-assembles in a hydrothermal reaction. However, the above method is a one-step method, that is, graphene oxide hydrothermal self-assembly will be affected by other ions in the solution, which can easily lead to incomplete three-dimensional graphene structure. Chinese patent (published CNIO557622OA, publication date 2016.05.11) discloses the preparation of a porous carbon-coated lithium iron phosphate positive electrode material, the steps are: 136.2g of absolute ethanol is dissolved in 136.2g of deionized, poured into the reactor; 157g LiFePO4 , 19.4g glucose and 88.2g ammonium bicarbonate were mixed evenly and put into the reaction kettle, and the mixture was fully stirred for 1 hour. The homogeneously stirred slurry was placed in a vacuum freeze dryer, frozen at -10°C for 1 hour, and then dried for 5 hours under a vacuum of 13 Pa. After drying, the solid was put into an oven at 100°C, dried for 1 hour, and then sintered at 750°C for 2 hours under a nitrogen atmosphere. Cool to room temperature, pass through a 325-mesh sieve after grinding, and obtain porous carbon-coated LiFePO4 /C. The principle of the preparation of porous carbon by the above method is that ammonium salt vapor phase is decomposed to form pores to obtain porous carbon, but porous carbon and LiFePO4 are only physically mixed. In addition, LiFePO4 does not exist in the pore structure of porous carbon, and porous carbon only acts To conduct electricity, and can not play the role of limiting particle size.
发明内容Contents of the invention
本发明针对当前技术中存在的LiFePO4材料电子导电性差，常规包碳是在材料表面包覆碳材料，这种包覆方式材料充放电过程中极化严重，大倍率性能差，提出了采用三维多孔碳架在LiFePO4颗粒间构建三维导电网络。本发明利用三维多孔碳架能三维传输电子的特性，增加电子在LiFePO4颗粒间传输通路，在提高材料电子电导率的同时确保较高的离子传导率。构建了部分开放不完全碳包覆的磷酸铁锂/三维碳架/碳复合材料，提高了材料的电化学性能。In view of the poor electronic conductivity of the LiFePO4 material existing in the current technology, the present invention proposes the use of a three-dimensional The porous carbon framework builds a three-dimensional conductive network between LiFePO4 particles. The invention utilizes the property that the three-dimensional porous carbon frame can transmit electrons three-dimensionally, increases the electron transmission path between LiFePO4 particles, and ensures higher ion conductivity while improving the electronic conductivity of the material. A partially open and incomplete carbon-coated lithium iron phosphate/three-dimensional carbon frame/carbon composite material was constructed, which improved the electrochemical performance of the material.
本发明技术方案为：Technical scheme of the present invention is:
一种磷酸铁锂/三维碳架/碳复合材料的制备方法，包括以下步骤：A preparation method of lithium iron phosphate/three-dimensional carbon frame/carbon composite material, comprising the following steps:
①将硫酸亚铁、磷酸、抗坏血酸溶解于混合溶剂中得到A液；将三维碳架分散在含有氢氧化锂的混合溶剂中，经过磁力搅拌2-12h得到B液，然后将B液15-20min滴加至A液中得到磷酸铁锂的前驱体溶液，然后将其置于高温高压反应釜中，加热至160-300℃，反应时间为1-20h，待反应斧自然冷却至室温后，分别用蒸馏水、乙醇离心洗涤，真空干燥后制得磷酸铁锂前驱体；① Dissolve ferrous sulfate, phosphoric acid, and ascorbic acid in a mixed solvent to obtain liquid A; disperse the three-dimensional carbon frame in a mixed solvent containing lithium hydroxide, and stir magnetically for 2-12 hours to obtain liquid B, and then dissolve liquid B for 15-20 minutes Add dropwise to liquid A to obtain a precursor solution of lithium iron phosphate, then place it in a high-temperature and high-pressure reactor, heat it to 160-300°C, and the reaction time is 1-20h. After the reaction ax is naturally cooled to room temperature, separate Centrifugal washing with distilled water and ethanol, and vacuum drying to obtain a lithium iron phosphate precursor;
其中，所述的离子摩尔比为锂离子:铁离子:磷酸根离子＝3-3.3:1:1；前驱体溶液中锂离子浓度为0.1-1mol/L；前驱体溶液中抗坏血酸浓度为0.03-0.2mol/L；质量比理论量磷酸铁锂:三维碳架＝1:0.1-0.005；体积比A液:B液＝5:3；A液和B液中的混合溶剂均为水和乙二醇的混合物，体积比为水:乙二醇＝1:2；Wherein, the ion molar ratio is lithium ion: iron ion: phosphate ion=3-3.3:1:1; the concentration of lithium ion in the precursor solution is 0.1-1mol/L; the concentration of ascorbic acid in the precursor solution is 0.03- 0.2mol/L; mass ratio theoretical amount of lithium iron phosphate: three-dimensional carbon frame = 1:0.1-0.005; volume ratio A liquid: B liquid = 5:3; the mixed solvents in A liquid and B liquid are water and ethylene glycol The mixture of alcohol, the volume ratio is water: ethylene glycol=1:2;
②将步骤①所得磷酸铁锂前驱体与葡萄糖混合后用球磨研磨，助剂为乙醇得到混合物；其中，每克前驱体加入0.5-10ml乙醇；②Mix the lithium iron phosphate precursor obtained in step ① with glucose and grind it with a ball mill, and the auxiliary agent is ethanol to obtain the mixture; wherein, 0.5-10ml of ethanol is added to each gram of the precursor;
其中，质量比为磷酸铁锂前驱体:葡萄糖＝1-10:1，球磨转速200-500r/min，球磨时间2-10h；Wherein, the mass ratio is lithium iron phosphate precursor: glucose=1-10:1, ball milling speed 200-500r/min, ball milling time 2-10h;
③将步骤②所得混合物干燥后放入管式炉中，在保护气氛氛围下，先在240-390℃条件下预烧1-5h，随炉冷却至室温，然后将其研磨破碎，再加入管式炉中，同样在保护气氛下，450-780℃烧结3-12h，随炉冷却至室温，最后得到磷酸铁锂/三维碳架/碳复合材料；③Dry the mixture obtained in step ② and put it into a tube furnace. Under the protective atmosphere, first pre-fire it at 240-390°C for 1-5h, cool it to room temperature with the furnace, then grind it to pieces, and then add it to the tube In the type furnace, also under the protective atmosphere, sinter at 450-780°C for 3-12h, and cool down to room temperature with the furnace, and finally obtain lithium iron phosphate/three-dimensional carbon frame/carbon composite material;
所述的步骤①中前驱体溶液的体积为反应釜容积的30-90％。The volume of the precursor solution in the step ① is 30-90% of the volume of the reactor.
所述的保护气氛为氮气、氩气、氢气中一种或多种混合气气氛。The protective atmosphere is one or more mixed gas atmospheres of nitrogen, argon, and hydrogen.
最终产物中含碳量为磷酸铁锂质量的5-30％，所含碳分别来自水热过程中加入的三维碳架与前驱体球磨过程加入的葡萄糖碳化后的碳。The carbon content in the final product is 5-30% of the mass of lithium iron phosphate, and the carbon contained comes from the three-dimensional carbon frame added in the hydrothermal process and the carbonized carbon of glucose added in the precursor ball milling process.
所述三维碳架的制备方法，包括以下步骤：The preparation method of the three-dimensional carbon frame comprises the following steps:
1)将碳源、催化剂加入到乙醇中搅拌，然后于30-90℃真空干燥，得到混合物A；1) adding carbon source and catalyst to ethanol and stirring, then vacuum drying at 30-90°C to obtain mixture A;
其中，质量比碳源:催化剂＝5-50:1；每克碳源加1-3ml乙醇；所述的碳源为葡萄糖、蔗糖、淀粉、草酸、纤维素、葡萄酸亚铁、草酸亚铁中一种或多种；催化剂为硫酸亚铁、氯化铁、氯化亚铁、硫酸镍、氯化镍和硫酸钴中的一种或多种；Wherein, mass ratio carbon source: catalyst=5-50:1; Every gram of carbon source adds 1-3ml ethanol; Described carbon source is glucose, sucrose, starch, oxalic acid, cellulose, ferrous gluconate, ferrous oxalate One or more in; Catalyst is one or more in ferrous sulfate, ferric chloride, ferrous chloride, nickel sulfate, nickel chloride and cobalt sulfate;
2)将步骤1)所得混合物A与制孔剂混合后球磨研磨1-9h，质量比为混合物A:制孔剂＝1:100-5000；得到混合物B；球磨转速100-500r/min；2) Mix the mixture A obtained in step 1) with the pore forming agent and then ball mill for 1-9 hours, the mass ratio is mixture A: pore forming agent = 1:100-5000; obtain mixture B; the ball milling speed is 100-500r/min;
3)将步骤2)所得混合物B用红外压片机在1-50MPa压力下压制为1-2g大小的压成药片；3) Compress the mixture B obtained in step 2) into a tablet of 1-2g size with an infrared tablet press under a pressure of 1-50MPa;
4)将步骤3)所得药片在保护气氛中烧结，包括以下步骤：4) sintering the tablet obtained in step 3) in a protective atmosphere, comprising the following steps:
A、从室温以2-5℃/min升温速率在保护气氛下升温到350-400℃，终点温度称为T1；并在T1温度下保温60-120min；A. From room temperature to 350-400°C under a protective atmosphere at a heating rate of 2-5°C/min, the end point temperature is called T1; and kept at T1 temperature for 60-120min;
B、从T1以1-4℃/min升温速率在保护气氛下升温到600-700℃，终点温度称为T2；在T2温度下保温60-180min；B. From T1 to 600-700°C under a protective atmosphere at a heating rate of 1-4°C/min, the end point temperature is called T2; keep at T2 temperature for 60-180min;
C、从T2以1-3℃/min升温速率在保护气氛下升温到700-900℃，终点温度称为T3；在T3温度下保温120-240min；C. From T2 to 700-900°C under a protective atmosphere at a heating rate of 1-3°C/min, and the end point temperature is called T3; keep at T3 for 120-240min;
D、从T3以0.2-1℃/min降温速率在保护气氛下降温到600-700℃，终点温度为T4；D. Drop the temperature from T3 to 600-700°C in a protective atmosphere at a cooling rate of 0.2-1°C/min, and the end point temperature is T4;
E、从T4以0.2-1℃/min降温速率在保护气氛下降温到500-600℃，终点温度为T5；E. Drop the temperature from T4 to 500-600°C in a protective atmosphere at a cooling rate of 0.2-1°C/min, and the end point temperature is T5;
F、从T5以1-1.5℃/min降温速率在保护气氛下降温到350-450℃，终点温度为T6；F. Drop the temperature from T5 to 350-450°C in a protective atmosphere at a cooling rate of 1-1.5°C/min, and the end point temperature is T6;
G、从T6在保护气氛下自然降温到室温，得到混合物C；G. From T6 to naturally cool down to room temperature under a protective atmosphere to obtain mixture C;
其中，步骤A-F中的保护气氛为氮气或氩气气氛。Wherein, the protective atmosphere in steps A-F is nitrogen or argon atmosphere.
5)将4)得到的混合物C投入蒸馏水中，待制孔剂完全溶解，捞出固体，真空干燥后得到三维碳架。5) Put the mixture C obtained in 4) into distilled water, wait until the pore-forming agent is completely dissolved, remove the solid, and dry it in vacuum to obtain a three-dimensional carbon frame.
所述步骤2)中制孔剂为氯化钠、氯化钾、氯化钙、氯化锂、碳酸钠、碳酸钙中一种或多种。The pore-forming agent in the step 2) is one or more of sodium chloride, potassium chloride, calcium chloride, lithium chloride, sodium carbonate, and calcium carbonate.
本发明的实质性特点为：Substantive features of the present invention are:
本发明通过对三维碳架制备(其工艺简单、易行优于当前三维有序大孔、三维介孔材料的制备)，然后将其用作水热反应的基体，在一定程度上三维碳架上的孔洞限制了水热过程中粒径的生长。另一方面三维碳架与材料表面常规包覆的一维碳层相比具有三维导电的能力。The present invention prepares a three-dimensional carbon frame (its process is simpler and easier than the preparation of current three-dimensional ordered macropores and three-dimensional mesoporous materials), and then uses it as a substrate for hydrothermal reaction, to a certain extent the three-dimensional carbon frame The pores on the surface restrict the growth of the particle size during the hydrothermal process. On the other hand, the three-dimensional carbon frame has three-dimensional electrical conductivity compared with the conventional one-dimensional carbon layer coated on the surface of the material.
现有技术中，水热法制备的前驱体采用碳源在材料表面包覆一层无定型碳(无定型碳导电性差)，电子传导只能通过颗粒之间的点到点接触传导。或者将前驱体与石墨烯等片层导电物复合，这样实现电子点到面的传导。而本发明可以实现电子由点到三维空间的传导，可以提高正极材料颗粒间的电子传导能力减小极化进而增强正极材料电化学性能。In the prior art, the precursor prepared by the hydrothermal method uses a carbon source to coat a layer of amorphous carbon on the surface of the material (amorphous carbon has poor conductivity), and electron conduction can only be conducted through point-to-point contact between particles. Or compound the precursor with sheet-layer conductors such as graphene, so as to realize the conduction of electrons from point to surface. However, the present invention can realize the conduction of electrons from a point to a three-dimensional space, can improve the electron conduction ability between the particles of the positive electrode material, reduce polarization, and thus enhance the electrochemical performance of the positive electrode material.
本发明的有益效果为：The beneficial effects of the present invention are:
本发明公开了一种磷酸铁锂/三维碳架/碳复合材料的制备方法。首先混合葡萄糖、硫酸亚铁，然后将混合物与氯化钠球磨，再采用红外压片机压片，经烧结碳化后洗去氯化钠制得三维碳架。将得到的三维碳架作为磷酸铁锂水热反应的基体，制备出磷酸铁锂/三维碳架/碳复合材料。The invention discloses a preparation method of lithium iron phosphate/three-dimensional carbon frame/carbon composite material. Firstly, glucose and ferrous sulfate are mixed, then the mixture is ball-milled with sodium chloride, and then compressed by an infrared tablet machine, and after sintering and carbonization, the sodium chloride is washed away to obtain a three-dimensional carbon frame. The obtained three-dimensional carbon frame is used as a substrate for the hydrothermal reaction of lithium iron phosphate, and a lithium iron phosphate/three-dimensional carbon frame/carbon composite material is prepared.
在制备三维碳架时采用的碳源、催化剂、制孔剂为工业中常见的葡萄糖、硫酸亚铁、氯化钠，以上原料的选择均可降低生产成本。The carbon source, catalyst, and pore-forming agent used in the preparation of the three-dimensional carbon frame are glucose, ferrous sulfate, and sodium chloride, which are common in the industry. The selection of the above raw materials can reduce the production cost.
在制备三维碳架时采用硫酸亚铁有两个目的：首先硫酸亚铁的微量加入随着烧结过程被碳单质还原成Fe单质，高温下为一种“纳米岛”的结构，烧结时中随着管式炉程序升温与程序缓慢降温过程无定型碳在这种“纳米岛”结构中溶解再析出机制可以提高碳的石墨化程度，进而增强三维碳架的导电性。其次硫酸亚铁转化为Fe单质后可以增强碳架的导电性。The use of ferrous sulfate in the preparation of three-dimensional carbon frame has two purposes: first, the trace addition of ferrous sulfate is reduced to Fe by simple carbon during the sintering process. The dissolution and re-precipitation mechanism of amorphous carbon in this "nano-island" structure during the temperature-programmed heating and slow-cooling process of the tube furnace can improve the degree of graphitization of carbon, thereby enhancing the conductivity of the three-dimensional carbon framework. Secondly, the conversion of ferrous sulfate into Fe elemental substance can enhance the conductivity of the carbon frame.
在水热过程中磷酸铁锂在吉布斯自由能的作用下首先在三维碳架的孔壁上成核生长，最终形成磷酸铁锂/三维碳架结构，由于在孔径中生长，三维碳架可以起到控制粒径的作用。另外由于三维碳架的存在在放电过程中从磷酸铁锂中传导出的电子实现由点到三维空间的传输，这种有效的电子传输机制可以减小材料充放电过程中的极化现象。In the hydrothermal process, lithium iron phosphate nucleates and grows on the pore wall of the three-dimensional carbon frame under the action of Gibbs free energy, and finally forms a lithium iron phosphate/three-dimensional carbon frame structure. Due to the growth in the pore, the three-dimensional carbon frame Can play a role in controlling particle size. In addition, due to the existence of the three-dimensional carbon frame, the electrons conducted from the lithium iron phosphate during the discharge process can be transported from the point to the three-dimensional space. This effective electron transport mechanism can reduce the polarization phenomenon during the charging and discharging process of the material.
如实施例1所述，当加入三维碳架质量为磷酸铁锂3％时，材料在0.2C倍率下比容量为156.7mAh/g达到理论比容量170mAh/g的92.18％。优于相同碳含量但不加三维碳架材料的0.2C倍率下的151.6mAh/g。As described in Example 1, when the mass of the three-dimensional carbon frame is 3% of lithium iron phosphate, the material has a specific capacity of 156.7mAh/g at a rate of 0.2C, reaching 92.18% of the theoretical specific capacity of 170mAh/g. It is better than 151.6mAh/g at 0.2C rate with the same carbon content but no three-dimensional carbon frame material.
附图说明Description of drawings
图1为实施例1中得到的磷酸铁锂/三维碳架/碳复合材料的SEM图；Fig. 1 is the SEM figure of the lithium iron phosphate/three-dimensional carbon frame/carbon composite material that obtains in embodiment 1;
图2为实施例1中得到的磷酸铁锂/三维碳架/碳复合材料与实施例3中得到的磷酸铁锂/碳复合材料循环充放电曲线图；Fig. 2 is the lithium iron phosphate/three-dimensional carbon frame/carbon composite material obtained in embodiment 1 and the lithium iron phosphate/carbon composite material obtained in embodiment 3 cycle charge and discharge curve;
图3为实施例1中的得到的磷酸铁锂/三维碳架/碳复合材料的XRD谱图。3 is the XRD spectrum of the lithium iron phosphate/three-dimensional carbon frame/carbon composite material obtained in Example 1.
具体实施方式:Detailed ways:
下面结合附图和实施例对本发明进一步说明。The present invention will be further described below in conjunction with the accompanying drawings and embodiments.
本发明的水热过程中的反应方程式为：The reaction equation in the hydrothermal process of the present invention is:
3LiOH+FeSO4+H3PO4→LiFePO4+Li2SO4+3H2O3LiOH+FeSO4 +H3 PO4 →LiFePO4 +Li2 SO4 +3H2 O
实施例1：Example 1:
①硫酸亚铁(0.048mol)、磷酸(0.048mol)、抗坏血酸(0.014mol)，称量后溶解于200ml水与乙二醇按体积比＝1:2组成的混合溶剂中，称为A液；按照理论量磷酸铁锂:三维碳架＝1:0.03的质量比，将三维碳架分散在120ml含有氢氧化锂(0.144mol)的水和乙二醇按体积比＝1:2混合溶剂中，磁力搅拌12h得到B液，然后将B液20min滴加至A液中得到磷酸铁锂的前驱体溶液，将其置于高温高压反应釜中，前驱体溶液中锂离子浓度为0.45mol/L；前驱体溶液的体积为反应釜容积的80％，加热至240℃，反应时间为4h，待反应釜自然冷却至室温后用蒸馏水、乙醇各离心洗涤三次真空干燥后制得磷酸铁锂前驱体；① Ferrous sulfate (0.048mol), phosphoric acid (0.048mol), ascorbic acid (0.014mol), weighed and dissolved in a mixed solvent of 200ml of water and ethylene glycol in a volume ratio = 1:2, called A liquid; According to the theoretical amount of lithium iron phosphate: the mass ratio of the three-dimensional carbon frame=1:0.03, the three-dimensional carbon frame is dispersed in 120ml of water containing lithium hydroxide (0.144mol) and ethylene glycol in a volume ratio=1:2 mixed solvent, Stir magnetically for 12 hours to obtain liquid B, then add liquid B dropwise to liquid A for 20 minutes to obtain a precursor solution of lithium iron phosphate, which is placed in a high-temperature and high-pressure reactor, and the concentration of lithium ions in the precursor solution is 0.45mol/L; The volume of the precursor solution is 80% of the volume of the reaction kettle, heated to 240 ° C, and the reaction time is 4 hours. After the reaction kettle is naturally cooled to room temperature, it is washed with distilled water and ethanol for three times and vacuum-dried to obtain a lithium iron phosphate precursor;
②按前驱体磷酸铁锂:葡萄糖＝15:2的质量比称取葡萄糖0.4320g，以5ml乙醇为助剂300r/min球磨6h。②Weigh 0.4320g of glucose according to the mass ratio of precursor lithium iron phosphate:glucose=15:2, and use 5ml of ethanol as auxiliary agent for ball milling at 300r/min for 6h.
③将步骤②所得混合物干燥后放入管式炉中，在保护气氛氛围下烧结，先在350℃条件下预烧3h，随炉冷却至室温，然后将其研磨破碎(直到无明显团聚在一起的块状颗粒，以下实施例同)，再加入管式炉中，同样在保护气氛下烧结，烧结工艺分别为650℃，6h，随炉冷却至室温，最后得到以三维碳架和碳构成三维导电网络的磷酸铁锂复合材料；③Dry the mixture obtained in step ②, put it into a tube furnace, and sinter it under a protective atmosphere. block particles, the following examples are the same), and then put into a tube furnace, and sintered under a protective atmosphere. Lithium iron phosphate composite material with conductive network;
其中，保护气氛为氮气气氛。Wherein, the protective atmosphere is a nitrogen atmosphere.
最终产物中含碳量为磷酸铁锂质量的6％，6％碳分别来自水热过程中加入的3％三维碳架与前驱体球磨过程加入的葡萄糖碳化后的碳3％。The carbon content in the final product is 6% of the mass of lithium iron phosphate, and 6% of the carbon comes from 3% of the three-dimensional carbon frame added in the hydrothermal process and 3% of the carbon after carbonization of glucose added in the precursor ball milling process.
所述三维碳架的制备方法，包括以下步骤：The preparation method of the three-dimensional carbon frame comprises the following steps:
1)将葡萄糖、硫酸亚铁按质量比22:1，充分搅拌分散于乙醇(每克碳源对应1.5ml乙醇)中，60℃真空干燥，得到混合物A；1) Glucose and ferrous sulfate were dispersed in ethanol (each gram of carbon source corresponds to 1.5ml ethanol) according to the mass ratio of 22:1, and vacuum-dried at 60°C to obtain mixture A;
2)将步骤1)所得混合物A与氯化钠按质量比1:240，300r/min球磨6h，得到混合物B；2) Mixture A obtained in step 1) and sodium chloride were ball milled at 300 r/min for 6 hours at a mass ratio of 1:240 to obtain mixture B;
3)将步骤2)所得混合物B用红外压片机在20MPa压力下一次1g压成药片；3) The mixture B obtained in step 2) is compressed into tablets by 1 g at a time under a pressure of 20 MPa with an infrared tablet press;
4)将步骤3)所得药片在保护气氛中烧结，其工艺步骤为：4) sintering the tablet obtained in step 3) in a protective atmosphere, the process steps are:
A、升温工艺，从室温以4℃/min升温速率在保护气氛下升温到400℃，终点温度称为T1；并在T1温度下保温60min；A. Heating process, from room temperature to 400°C under a protective atmosphere at a heating rate of 4°C/min, the end point temperature is called T1; and kept at T1 temperature for 60 minutes;
B、升温工艺，从T1以2℃/min升温速率在保护气氛下升温到650℃，终点温度称为T2；并在T2温度下保温120min；B. Heating process, from T1 to 650°C under a protective atmosphere at a heating rate of 2°C/min, and the end point temperature is called T2; and kept at T2 for 120 minutes;
C、升温工艺，从T2以1℃/min升温速率在保护气氛下升温到750℃，终点温度称为T3；并在T3温度下保温180min；C. Heating process, from T2 to 750°C under a protective atmosphere at a heating rate of 1°C/min, and the end point temperature is called T3; and kept at T3 for 180 minutes;
D、降温工艺，从T3以0.5℃/min降温速率在保护气氛下降温到650℃，终点温度为T4；D. Cooling process, from T3 to 650°C in a protective atmosphere at a cooling rate of 0.5°C/min, and the end point temperature is T4;
E、降温工艺，从T4以1℃/min降温速率在保护气氛下降温到550℃，终点温度为T5；E. Cooling process, from T4 to 550°C in a protective atmosphere at a cooling rate of 1°C/min, and the end point temperature is T5;
F、降温工艺，从T5以1.5℃/min降温速率在保护气氛下降温到400℃，终点温度为T6；F. Cooling process, from T5 to 400°C in a protective atmosphere at a cooling rate of 1.5°C/min, and the end point temperature is T6;
G、降温工艺，从T6在保护气氛下自然降温到室温，得到混合物C；G, cooling process, naturally cool down to room temperature from T6 under protective atmosphere, obtain mixture C;
其中步骤A-F中的保护气氛为氮气气氛。Wherein the protective atmosphere in steps A-F is nitrogen atmosphere.
5)将4)得到的混合物C投入蒸馏水中，待制孔剂完全溶解(中途更换新的蒸馏水，取少量浸泡三维碳架的蒸馏水滴入AgNO3溶液，无白色沉淀产生，证明制孔剂完全溶解)，捞出固体，真空干燥后得到三维碳架。5) Put the mixture C obtained in 4) into distilled water, and wait until the pore-forming agent is completely dissolved (replace with new distilled water midway, take a small amount of distilled water soaked in the three-dimensional carbon frame and drop it into the AgNO3 solution, no white precipitation occurs, which proves that the pore-forming agent is completely dissolved), the solid was removed, and the three-dimensional carbon framework was obtained after vacuum drying.
从图1中的可以看出本发明所制备的三维碳架呈现出不规则的三维孔层结构，孔径在100nm-1μm之间，水热反应中磷酸铁锂颗粒在三维碳架孔洞中生长。磷酸铁锂被能够多通路导电的三维碳架不完全包覆，构建了部分开放不完全碳包覆的磷酸铁锂/三维碳架/碳复合材料，三维碳架的加入一方面限制了水热过程中磷酸铁锂材料颗粒的过度生长，另一方面增强了材料颗粒间的导电性。It can be seen from Figure 1 that the three-dimensional carbon frame prepared by the present invention presents an irregular three-dimensional pore layer structure with a pore size between 100nm and 1 μm, and lithium iron phosphate particles grow in the pores of the three-dimensional carbon frame during the hydrothermal reaction. Lithium iron phosphate is incompletely covered by a three-dimensional carbon frame capable of multi-channel conduction, and a partially open and incomplete carbon-coated lithium iron phosphate/three-dimensional carbon frame/carbon composite material is constructed. The addition of a three-dimensional carbon frame limits the hydrothermal The excessive growth of lithium iron phosphate material particles during the process, on the other hand, enhances the conductivity between material particles.
图2为利用CT2001A型LAND测试仪对电池进行充放电测试性能曲线，电压范围为2.5-4.2V，测试温度25℃。可以看出用在0.2C倍率下加入3％三维碳架+3％碳(葡萄糖碳化而来)的磷酸铁锂比容量能达到156.7mAh/g，而采用相同制备工艺只是加入6％碳(葡萄糖碳化而来-实施例3)的磷酸铁锰锂0.2C倍率下比容量为151.6mAh/g。Figure 2 is the performance curve of the charge and discharge test of the battery using the CT2001A LAND tester, the voltage range is 2.5-4.2V, and the test temperature is 25°C. It can be seen that the specific capacity of lithium iron phosphate with 3% three-dimensional carbon frame+3% carbon (from glucose carbonization) can reach 156.7mAh/g at 0.2C magnification, while the same preparation process only adds 6% carbon (glucose The specific capacity of lithium iron manganese phosphate obtained from carbonization-Example 3) is 151.6mAh/g at a rate of 0.2C.
图3可以看出，本方法制备出的磷酸铁锂的XRD谱图与标准谱图相吻合，且峰型尖锐无杂质峰出现，说明用本方法能够制备出晶型完整的磷酸铁锂材料。It can be seen from Figure 3 that the XRD spectrum of the lithium iron phosphate prepared by this method is consistent with the standard spectrum, and the peak shape is sharp and no impurity peaks appear, indicating that the method can be used to prepare lithium iron phosphate materials with complete crystal forms.
实施例2：Example 2:
①硫酸亚铁(0.048mol)、磷酸(0.048mol)、抗坏血酸(0.018mol)，称量后溶解于200ml水与乙二醇按体积比＝1:2组成的混合溶剂中，称为A液；按照理论量磷酸铁锂:三维碳架＝1:0.1的质量比将三维碳架分散在120ml含有氢氧化锂(0.1584mol)的水和乙二醇按体积比＝1:2混合溶剂中，磁力搅拌10h得到B液，然后将B液15min滴加至A液中得到磷酸铁锂的前驱体溶液，将其置于高温高压反应釜中，前驱体溶液中锂离子浓度为0.495mol/L；前驱体溶液的体积为反应釜容积的60％，加热至200℃，反应时间为6h，待反应釜自然冷却至室温后用蒸馏水、乙醇各离心洗涤三次真空干燥后制得磷酸铁锂前驱体；① Ferrous sulfate (0.048mol), phosphoric acid (0.048mol), ascorbic acid (0.018mol), weighed and dissolved in a mixed solvent of 200ml water and ethylene glycol in a volume ratio = 1:2, called A liquid; According to the theoretical amount of lithium iron phosphate: the mass ratio of the three-dimensional carbon frame=1:0.1, the three-dimensional carbon frame is dispersed in 120ml of water containing lithium hydroxide (0.1584mol) and ethylene glycol in a mixed solvent with a volume ratio=1:2, magnetic force Stir for 10 hours to obtain liquid B, then add liquid B dropwise to liquid A for 15 minutes to obtain a precursor solution of lithium iron phosphate, which is placed in a high-temperature and high-pressure reactor, and the lithium ion concentration in the precursor solution is 0.495mol/L; The volume of the solid solution is 60% of the volume of the reaction kettle, heated to 200 ° C, and the reaction time is 6 hours. After the reaction kettle is naturally cooled to room temperature, it is washed with distilled water and ethanol for three times and vacuum-dried to obtain a lithium iron phosphate precursor;
②按前驱体磷酸铁锂:葡萄糖＝15:8的质量比称取葡萄糖0.8640g以8ml乙醇为助剂400r/min球磨1h。②Weigh 0.8640g of glucose according to the mass ratio of precursor lithium iron phosphate:glucose=15:8, and use 8ml of ethanol as auxiliary agent to ball mill at 400r/min for 1h.
③将步骤②所得混合物干燥后放入管式炉中，在保护气氛氛围下烧结，先在390℃条件下预烧2h，随炉冷却至室温，然后将其研磨破碎，再加入管式炉中，同样在保护气氛下烧结，烧结工艺分别为700℃，4h，随炉冷却至室温，最后得到以三维碳架和碳构成三维导电网络的磷酸铁锂复合材料；③Dry the mixture obtained in step ②, put it into a tube furnace, and sinter it in a protective atmosphere. First, it is pre-fired at 390°C for 2 hours, and then it is cooled to room temperature with the furnace, and then it is ground and crushed, and then put into the tube furnace , also sintered in a protective atmosphere, the sintering process was 700 ° C, 4h, and cooled to room temperature with the furnace, and finally obtained a three-dimensional lithium iron phosphate composite material with a three-dimensional carbon frame and carbon to form a three-dimensional conductive network;
其中，保护气氛为氢气气氛。Wherein, the protective atmosphere is a hydrogen atmosphere.
最终产物中含碳量为磷酸铁锂质量的22％，22％碳分别来自水热过程中加入的10％碳架与前驱体球磨过程加入的葡萄糖碳化后的碳12％。。The carbon content in the final product is 22% of the mass of lithium iron phosphate, and 22% of the carbon comes from 10% of the carbon frame added in the hydrothermal process and 12% of the carbon after carbonization of glucose added in the precursor ball milling process. .
所述三维碳架的制备方法，包括以下步骤：The preparation method of the three-dimensional carbon frame comprises the following steps:
1)将葡萄糖酸亚铁、硫酸钴按质量比10:1，充分搅拌分散于乙醇(每克碳源对应2ml乙醇)中，50℃真空干燥，得到混合物A；1) Ferrous gluconate and cobalt sulfate are dispersed in ethanol (each gram of carbon source corresponds to 2ml of ethanol) according to the mass ratio of 10:1, and vacuum-dried at 50°C to obtain mixture A;
2)将步骤1)所得混合物A与碳酸钠按质量比1:1000，200r/min球磨4h，得到混合物B；2) Mixture A obtained in step 1) and sodium carbonate were ball milled at 200 r/min for 4 hours at a mass ratio of 1:1000 to obtain mixture B;
3)将步骤2)所得混合物B用红外压片机在10MPa压力下一次1.5g压成药片；3) The mixture B obtained in step 2) is pressed into tablets at a time of 1.5 g under a pressure of 10 MPa with an infrared tablet press;
4)将步骤3)所得药片在保护气氛中烧结，其工艺步骤为：4) sintering the tablet obtained in step 3) in a protective atmosphere, the process steps are:
A、升温工艺，从室温以5℃/min升温速率在保护气氛下升温到350℃，终点温度称为T1；并在T1温度下保温120min；A. Heating process, from room temperature to 350°C under a protective atmosphere at a heating rate of 5°C/min, the end point temperature is called T1; and kept at T1 temperature for 120min;
B、升温工艺，从T1以1℃/min升温速率在保护气氛下升温到700℃，终点温度称为T2；并在T2温度下保温180min；B. Heating process, from T1 to 700°C under a protective atmosphere at a heating rate of 1°C/min, and the end point temperature is called T2; and kept at T2 for 180 minutes;
C、升温工艺，从T2以2℃/min升温速率在保护气氛下升温到800℃，终点温度称为T3；并在T3温度下保温240min；C. Heating process, from T2 to 800°C under a protective atmosphere at a heating rate of 2°C/min, and the end point temperature is called T3; and kept at T3 for 240min;
D、降温工艺，从T3以0.2℃/min降温速率在保护气氛下降温到700℃，终点温度为T4；D. Cooling process, from T3 to 700°C in a protective atmosphere at a cooling rate of 0.2°C/min, and the end point temperature is T4;
E、降温工艺，从T4以0.5℃/min降温速率在保护气氛下降温到600℃，终点温度为T5；E. Cooling process, from T4 to 600°C in a protective atmosphere at a cooling rate of 0.5°C/min, and the end point temperature is T5;
F、降温工艺，从T5以1℃/min降温速率在保护气氛下降温到350℃，终点温度为T6；F. Cooling process, from T5 to 350°C in a protective atmosphere at a cooling rate of 1°C/min, and the end point temperature is T6;
G、降温工艺，从T6在保护气氛下自然降温到室温，得到混合物C；G, cooling process, naturally cool down to room temperature from T6 under protective atmosphere, obtain mixture C;
其中步骤A-F中的保护气氛为氩气气氛。Wherein the protective atmosphere in steps A-F is argon atmosphere.
5)将4)得到的混合物C投入蒸馏水中，待制孔剂完全溶解(中途更换新的蒸馏水，取少量浸泡三维碳架的蒸馏水滴入AgNO3溶液，无沉淀产生，证明制孔剂完全溶解)，捞出固体，真空干燥后得到三维碳架。5) Put the mixture C obtained in 4) into distilled water until the pore-forming agent is completely dissolved (replace with new distilled water halfway, take a small amount of distilled water soaked in the three-dimensional carbon frame and drop it into the AgNO3 solution, no precipitation occurs, which proves that the pore-forming agent is completely dissolved ), the solid was removed, and the three-dimensional carbon framework was obtained after vacuum drying.
实施例3：Example 3:
①硫酸亚铁(0.048mol)、磷酸(0.048mol)、抗坏血酸(0.014mol)，称量后溶解于200ml水与乙二醇按体积比＝1:2组成的混合溶剂中，称为A液；将氢氧化锂(0.144mol)分散在120ml含有的水和乙二醇按体积比＝1:2混合溶剂中，得到B液，然后将B液20min滴加至A液中得到磷酸铁锂的前驱体溶液，将其置于高温高压反应釜中，前驱体溶液中锂离子浓度为0.45mol/L；前驱体溶液的体积为反应釜容积的80％，加热至240℃，反应时间为4h，待反应釜自然冷却至室温后用蒸馏水、乙醇各离心洗涤三次真空干燥后制得磷酸铁锂前驱体；① Ferrous sulfate (0.048mol), phosphoric acid (0.048mol), ascorbic acid (0.014mol), weighed and dissolved in a mixed solvent of 200ml of water and ethylene glycol in a volume ratio = 1:2, called A liquid; Lithium hydroxide (0.144mol) was dispersed in 120ml of mixed solvent containing water and ethylene glycol at a volume ratio = 1:2 to obtain liquid B, and then liquid B was added dropwise to liquid A for 20 minutes to obtain a precursor of lithium iron phosphate The precursor solution is placed in a high-temperature and high-pressure reactor, and the lithium ion concentration in the precursor solution is 0.45mol/L; the volume of the precursor solution is 80% of the volume of the reactor, heated to 240°C, and the reaction time is 4h. After the reaction kettle was naturally cooled to room temperature, it was centrifuged and washed three times with distilled water and ethanol, and vacuum-dried to obtain a lithium iron phosphate precursor;
②按前驱体磷酸铁锂:葡萄糖＝15:4的质量比称取葡萄糖0.8640g以5ml乙醇为助剂300r/min球磨6h。② Weigh 0.8640 g of glucose according to the mass ratio of the precursor lithium iron phosphate: glucose = 15:4, and use 5 ml of ethanol as an auxiliary agent for ball milling at 300 r/min for 6 h.
③将步骤②所得混合物干燥后放入管式炉中，在保护气氛氛围下烧结，先在350℃条件下预烧3h，随炉冷却至室温，然后将其研磨破碎，再加入管式炉中，同样在保护气氛下烧结，烧结工艺分别为650℃，6h，随炉冷却至室温，最后得到磷酸铁锂/碳复合材料；③Dry the mixture obtained in step ②, put it into a tube furnace, and sinter it under a protective atmosphere. First, it is pre-fired at 350°C for 3 hours, and then it is cooled to room temperature with the furnace, and then it is ground and crushed, and then put into the tube furnace , also sintered in a protective atmosphere, the sintering process is 650 ° C, 6h, and cooled to room temperature with the furnace, and finally the lithium iron phosphate/carbon composite material is obtained;
其中，保护气氛为氮气气氛。Wherein, the protective atmosphere is a nitrogen atmosphere.
最终产物中含碳量为磷酸铁锂质量的6％。The carbon content in the final product is 6% of the mass of lithium iron phosphate.
本发明未尽事宜为公知技术。Matters not covered in the present invention are known technologies.
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