技术领域：Technical field:
本发明涉及锂离子电池电极材料技术领域，具体涉及一种锂离子电池极片制备方法。The invention relates to the technical field of lithium-ion battery electrode materials, in particular to a method for preparing lithium-ion battery pole pieces.
背景技术：Background technique:
锂电池是一种以锂金属或锂合金为负极材料，使用非水电解质溶液的一次电池，与可充电电池锂离子电池跟锂离子聚合物电池是不一样的。锂电池的发明者是爱迪生。由于锂金属的化学特性非常活泼，使得锂金属的加工、保存、使用，对环境要求非常高。所以，锂电池长期没有得到应用。随着二十世纪末微电子技术的发展，小型化的设备日益增多，对电源提出了很高的要求。锂电池随之进入了大规模的实用阶段。磷酸铁锂系正极反应：放电时锂离子嵌入，充电时锂离子脱嵌。充电时：LiFePO4→Li1-xFePO4+xLi++ xe-放电时：Li1-xFePO4+xLi++xe-→LiFePO4负极，负极材料：多采用石墨。新的研究发现钛酸盐可能是更好的材料。负极反应：放电时锂离子脱插，充电时锂离子插入。充电时：xLi++xe-+6C→LixC6放电时：LixC6→xLi++ xe-+6C。磷酸铁锂电池具有安全性好、能量密度较高等特点，现已成为动力电池中的主流电池。然而，低温环境下，锂离子从正极材料中脱出及在电解液中迁移所受到的阻力增大，磷酸铁锂电池的充放电性能及循环性能急剧降低，因此，提高磷酸铁锂电池在低温环境下的充放电性能及循环性能具有重要意义。A lithium battery is a primary battery that uses lithium metal or lithium alloy as the negative electrode material and uses a non-aqueous electrolyte solution. It is different from a rechargeable battery. Lithium-ion batteries are different from lithium-ion polymer batteries. The inventor of the lithium battery is Edison. Due to the very active chemical properties of lithium metal, the processing, storage and use of lithium metal have very high environmental requirements. Therefore, lithium batteries have not been used for a long time. With the development of microelectronics technology at the end of the 20th century, miniaturized equipment is increasing day by day, which puts forward high requirements for power supply. Lithium batteries have entered a large-scale practical stage. Lithium iron phosphate positive electrode reaction: Lithium ions are intercalated during discharge, and lithium ions are deintercalated during charging. Charging: LiFePO4→Li1-xFePO4+xLi++ xe-discharging: Li1-xFePO4+xLi++xe-→LiFePO4 negative electrode, negative electrode material: graphite is mostly used. New research finds that titanates may be a better material. Negative electrode reaction: lithium ions are deintercalated during discharge, and lithium ions are inserted during charging. When charging: xLi++xe-+6C→LixC6 When discharging: LixC6→xLi++xe-+6C. Lithium iron phosphate batteries have the characteristics of good safety and high energy density, and have become the mainstream batteries in power batteries. However, in a low temperature environment, the resistance of lithium ions to escape from the positive electrode material and migrate in the electrolyte increases, and the charge and discharge performance and cycle performance of the lithium iron phosphate battery decrease sharply. Therefore, to improve the lithium iron phosphate battery in a low temperature environment The charge-discharge performance and cycle performance are of great significance.
目前，磷酸铁锂材料的合成方法主要分成固相法和液相法。固相法主要是利用铁盐、锂盐和磷酸盐，在高温烧结实现磷酸铁锂的合成。液相法是将可溶性铁盐、锂盐和磷酸盐溶解在溶剂中，利用离子反应制成磷酸铁锂或其前驱体，再通过高温烧结制成成品。固相法反应简便，原料容易处理，产率高，但是原料形貌不容易控制，产品振实密度和压实密度低。例如，发明专利CN101200289、CN1762798、CN101140985等都是采用固相合成工艺路线。一些新的合成方法，如微波合成法(CN101172597、CN101807692A)、超声共沉淀法(CN101800311A)，都可以归结到固相合成法中。而液相法需要利用反应釜进行前期处理，同时也需要干燥、过滤等过程，工艺比较复杂。但是产品球形度一般较好，振实密度较高，容量和高倍率性能出色。发明专利 CN101172599、CN101047242、CN101121509都是采用以上工艺路线。磷酸铁材料的成功应用在于其表面包覆有导电碳层。实际是一种磷酸铁锂/碳复合材料。只有包覆了碳的磷酸铁锂材料才能正常发挥其电化学性能。但是，一般的工艺加入的碳由于质地疏松，且在磷酸铁锂颗粒间呈松散分布，严重降低了磷酸铁锂材料的堆积密度。负极材料是锂离子电池的关键材料之一，目前商品化使用的锂离子电池负极材料主要是炭类负极材料。它具有高比容量 (200～400mAh/g)、低电极电位(＜1.0V vs Li+/Li)、高循环效率(＞95％)以及长循环寿命等优点。炭类负极材料中有中间相碳微球(MCMB)、石墨以及无定形碳，其中，石墨因其导电性好、结晶度高，具有良好的层状结构，可逆比容量可达300mah/g以上，Chen等人发明了一种超细度石墨负极材料，采用高端石墨生产后的辅料为该产品的主要原料，经过精碎使粒度降低到5um为基准，再进行表面处理，经过1200°炭化后，再进行3000°石墨化烧结，再进行粗碎过筛获得到相应产品，此产品具有良好的导电作用，电阻低，在锂离子电池生产过程中加工性能良好，性能稳定，性价比高，是倍率型锂电池的最佳负极材料。但缺点是石墨材料结构稳定性差，与电解液的相容性差，且Li离子在其有序层状结构中的扩散速度慢，导致该材料不能大倍率充放电。而软碳结晶度低，晶粒尺寸小，晶面间距大，与电解液相容性好，但首次充放电不可逆容量较好，应用范围较小，对以上人造石墨作为锂离子电池负极材料本身的一些结构缺陷，为了获得高电化学性能的负极材料，必须对其进行深一步表面的改性和修饰。At present, the synthesis methods of lithium iron phosphate materials are mainly divided into solid-phase method and liquid-phase method. The solid-phase method mainly uses iron salt, lithium salt and phosphate to sinter at high temperature to realize the synthesis of lithium iron phosphate. The liquid phase method is to dissolve soluble iron salts, lithium salts and phosphates in a solvent, use ion reactions to make lithium iron phosphate or its precursors, and then sinter at high temperature to make finished products. The solid-phase method has simple reactions, easy handling of raw materials, and high yield, but the morphology of the raw materials is not easy to control, and the tap density and compacted density of the product are low. For example, invention patents CN101200289, CN1762798, CN101140985, etc. all adopt solid-phase synthesis process routes. Some new synthesis methods, such as microwave synthesis (CN101172597, CN101807692A), ultrasonic co-precipitation (CN101800311A), can all be attributed to solid phase synthesis. The liquid phase method requires the use of a reactor for pre-treatment, and also requires drying, filtration and other processes, and the process is more complicated. However, the sphericity of the product is generally good, the tap density is high, and the capacity and high rate performance are excellent. Invention patents CN101172599, CN101047242, and CN101121509 all adopt the above process route. The successful application of iron phosphate material is that its surface is coated with a conductive carbon layer. It is actually a lithium iron phosphate/carbon composite material. Only carbon-coated lithium iron phosphate materials can perform their electrochemical performance normally. However, the carbon added in the general process is loose in texture and loosely distributed among the lithium iron phosphate particles, which seriously reduces the packing density of the lithium iron phosphate material. The anode material is one of the key materials of lithium-ion batteries, and the anode materials for lithium-ion batteries currently commercially used are mainly carbon-based anode materials. It has the advantages of high specific capacity (200～400mAh/g), low electrode potential (<1.0V vs Li+/Li), high cycle efficiency (>95%) and long cycle life. Carbon anode materials include mesocarbon microspheres (MCMB), graphite and amorphous carbon. Among them, graphite has a good layered structure due to its good conductivity and high crystallinity, and its reversible specific capacity can reach more than 300mah/g , Chen et al. invented an ultra-fine graphite anode material. The auxiliary material produced by high-end graphite is used as the main raw material of the product. After fine crushing, the particle size is reduced to 5um as the benchmark, and then the surface is treated. , and then 3000 ° graphitization and sintering, and then coarse crushing and sieving to obtain the corresponding product. This product has good electrical conductivity, low resistance, good processing performance in the production process of lithium-ion batteries, stable performance, high cost performance, and is the magnification The best anode material for lithium batteries. However, the disadvantage is that the graphite material has poor structural stability, poor compatibility with the electrolyte, and the slow diffusion rate of Li ions in its ordered layered structure, which makes the material unable to charge and discharge at a high rate. However, soft carbon has low crystallinity, small grain size, large interplanar spacing, and good compatibility with electrolyte, but its irreversible capacity for the first charge and discharge is good, and its application range is small. The above artificial graphite is used as the negative electrode material of lithium ion battery itself. In order to obtain anode materials with high electrochemical performance, it is necessary to carry out further surface modification and modification.
发明内容：Invention content:
本发明克服现有技术的缺陷，提供一种一种锂离子电池极片制备方法。The invention overcomes the defects of the prior art, and provides a method for preparing lithium-ion battery pole pieces.
本发明所要解决的技术问题采用以下的技术方案来实现：一种锂离子电池极片制备方法，按重量份计，包括正极/负极活性物质70～80份、造孔剂1～3 份、导电剂2～3份、粘接剂1～2份、溶剂40～60份；The technical problem to be solved by the present invention is realized by the following technical solutions: a preparation method of lithium-ion battery pole piece, which comprises 70-80 parts of positive electrode/negative electrode active material, 1-3 parts of pore-forming agent, conductive 2-3 parts of agent, 1-2 parts of adhesive, 40-60 parts of solvent;
并经由以下步骤制备所述锂离子电池极片：And prepare described lithium-ion battery pole piece through the following steps:
(1)制备正极活性物质和负极活性物质；(1) prepare positive electrode active material and negative electrode active material;
(2)将步骤(1)中的正极/负极活性物质分别与造孔剂、导电剂、粘接剂以及溶剂混合，并制备形成浆料A、浆料B；(2) Mix the positive electrode/negative electrode active material in step (1) with pore-forming agent, conductive agent, binder and solvent respectively, and prepare slurry A and slurry B;
(3)所述步骤(2)中的浆料A、B涂覆在集流体上，在50～55℃、65～ 75℃、80～85℃、75～80℃下干燥处理，辊压，分切，得到所述锂离子电池极片。(3) The slurry A and B in the step (2) are coated on the current collector, dried at 50-55°C, 65-75°C, 80-85°C, and 75-80°C, and rolled, cutting to obtain the lithium ion battery pole piece.
优选的，本申请中，所述造孔剂为聚苯乙烯球，所述造孔剂的粒径≤ 2.0um，所述导电剂为乙炔黑，所述溶剂为无水乙醇。Preferably, in the present application, the pore-forming agent is polystyrene balls, the particle size of the pore-forming agent is ≤ 2.0um, the conductive agent is acetylene black, and the solvent is absolute ethanol.
优选的，本申请中，所述正极活性物质经由以下步骤制备：Preferably, in the present application, the positive electrode active material is prepared through the following steps:
(1)将质量比2：1石墨烯和碳纳米管投入到乙醇中，并通过超声初步粉碎处理后，在常温下混合搅拌4～6分钟，然后在惰性气体保护的环境下以2～4℃ /min的速度升温至40～60℃，再保温4～6h，然后自然冷却至室温，得到混合溶液；(1) Graphene and carbon nanotubes with a mass ratio of 2:1 are put into ethanol, and after being preliminarily crushed by ultrasonic waves, they are mixed and stirred at room temperature for 4 to 6 minutes, and then mixed with 2 to 4 The temperature is raised to 40-60°C at a rate of ℃/min, and then kept for 4-6 hours, and then naturally cooled to room temperature to obtain a mixed solution;
所述石墨烯为多层石墨烯，所述多层石墨烯的内部呈三维立体导电网络结构，所述碳纳米管插嵌在该三维立体导电网络内，多层石墨烯和碳纳米管作用后形成的颗粒粒径为700nm～22um；The graphene is multi-layer graphene, and the inside of the multi-layer graphene is a three-dimensional conductive network structure, and the carbon nanotubes are embedded in the three-dimensional conductive network. The particle size formed is 700nm～22um;
(2)将磷酸铁锂粉碎到粒径3～6um，并将磷酸铁锂投入到搅拌釜中，按照磷酸铁锂和蒸馏水的质量比＝1：2～7的比例缓慢添加蒸馏水，并添加偶联剂和乙炔黑，快速搅拌10～16min后，将步骤(1)中的混合溶液添加至搅拌釜中，搅拌均匀，得到改性中间体；(2) Crush lithium iron phosphate to a particle size of 3-6um, put lithium iron phosphate into a stirred tank, slowly add distilled water according to the mass ratio of lithium iron phosphate to distilled water = 1:2-7, and add even The coupling agent and acetylene black are stirred rapidly for 10 to 16 minutes, then the mixed solution in step (1) is added to the stirring tank, and stirred evenly to obtain a modified intermediate;
(3)将步骤(2)制备的改性中间体加入雾化器中进行喷雾干燥处理，该过程中是在保护气体作用下吹入气态碳源，使所述气态碳源在改性中间体表面裂解形成无定形碳，该无定型碳包覆在改性中间体的表面并形成均匀的包覆层；(3) Add the modified intermediate prepared in step (2) into the atomizer and carry out spray drying treatment. In this process, the gaseous carbon source is blown into under the effect of protective gas, so that the gaseous carbon source is blown into the modified intermediate The surface cracks to form amorphous carbon, which is coated on the surface of the modified intermediate and forms a uniform coating layer;
(4)将步骤(3)中得到的粉末颗粒在真空烘干，在250～350℃和保护气体作用下煅烧3～4小时，得到改性磷酸铁锂正极材料。(4) Drying the powder particles obtained in step (3) in a vacuum, and calcining at 250-350° C. under the action of a protective gas for 3-4 hours to obtain a modified lithium iron phosphate positive electrode material.
优选的，本申请中，所述偶联剂为γ-巯丙基三甲氧基硅烷、甲基异丁基酮肟基硅烷或乙烯基三乙氧基硅烷，所述偶联剂：乙炔黑：混合溶液的质量比为：(0.1～2：1～1.6：100)；Preferably, in this application, the coupling agent is γ-mercaptopropyltrimethoxysilane, methylisobutylketoximosilane or vinyltriethoxysilane, and the coupling agent: acetylene black: The mass ratio of the mixed solution is: (0.1～2:1～1.6:100);
所述步骤(3)中是将改性中间体投入到雾化器中，并在氮气保护的状态下升温至500～700℃进行退火处理，然后由保护气体载入24～26％的气态碳源，气体流速50～1000ml/min，同时开启雾化器，保护气体将雾化器中雾化的细小成分带到高温炉中，保温1～12小时，使所述气态碳源在改性中间体表面裂解形成无定形碳，该无定型碳包覆在改性中间体的表面并形成均匀的包覆层，其厚度为0.3nm～30nm。In the step (3), the modified intermediate is put into the atomizer, and the temperature is raised to 500-700 ° C under the protection of nitrogen for annealing treatment, and then 24-26% of gaseous carbon is loaded by the protection gas source, the gas flow rate is 50-1000ml/min, and the atomizer is turned on at the same time, and the protective gas will bring the fine components atomized in the atomizer to the high-temperature furnace, and keep it warm for 1-12 hours, so that the gaseous carbon source is in the middle of the modification. The surface of the body is cracked to form amorphous carbon, and the amorphous carbon is coated on the surface of the modified intermediate to form a uniform coating layer with a thickness of 0.3nm to 30nm.
优选的，本申请中，所述负极活性物质经由以下步骤制备：Preferably, in the present application, the negative electrode active material is prepared through the following steps:
(1)将质量比2：1石墨烯和碳纳米管投入到无水乙醇中，并通过超声初步粉碎处理后，在常温下混合搅拌4～6分钟，然后在惰性气体保护的环境下以 2～4℃/min的速度升温至40～60℃，再保温4～6h，然后自然冷却至室温，得到混合溶液；(1) Graphene and carbon nanotubes with a mass ratio of 2:1 were put into absolute ethanol, and after being preliminarily pulverized by ultrasonic waves, they were mixed and stirred at room temperature for 4 to 6 minutes, and then in an environment protected by an inert gas with 2 Raise the temperature to 40-60°C at a rate of ~4°C/min, then keep it warm for 4-6 hours, and then naturally cool to room temperature to obtain a mixed solution;
所述石墨烯为多层石墨烯，所述多层石墨烯的内部呈三维立体导电网络结构，所述碳纳米管插嵌在该三维立体导电网络内，多层石墨烯和碳纳米管作用后形成的颗粒粒径为600nm～20um。The graphene is multi-layer graphene, and the inside of the multi-layer graphene is a three-dimensional conductive network structure, and the carbon nanotubes are embedded in the three-dimensional conductive network. The particle size of the formed particles is 600nm-20um.
(2)采用石油沥青为基料，将该基料进行粉碎和球磨处理至粒径为120～140um，再将处理后的颗粒投入至反应釜中进行改性处理，其步骤包括：(2) Using petroleum asphalt as the base material, crushing and ball milling the base material until the particle size is 120-140um, and then putting the treated particles into the reactor for modification treatment, the steps include:
(2.1)采用流速为80～120每小时的空速通入氮气，然后进行升温至 300～420℃，升温速度为40～60℃/h，保温2～6h；(2.1) Nitrogen gas is introduced at a space velocity of 80-120 hours per hour, then the temperature is raised to 300-420°C, the temperature rise rate is 40-60°C/h, and the temperature is kept for 2-6 hours;
(2.2)取部分步骤(2.1)中的沥青粉碎至粒径在20um以下，并测量软化点，并在此温度下保温4～6h，直至测得的软化点在180～380℃的沥青基料；(2.2) Take part of the asphalt in the step (2.1) and crush it until the particle size is below 20um, measure the softening point, and keep it at this temperature for 4-6 hours until the measured softening point is 180-380°C. ;
(2.3)将步骤(2.2)中的沥青基料自然冷却至室温，然后将沥青基料粉碎至粒径为18～20um，即为改性沥青基料；(2.3) Naturally cool the asphalt base material in the step (2.2) to room temperature, then pulverize the asphalt base material to a particle size of 18-20um, which is the modified asphalt base material;
(3)将步骤(2)中得到的沥青筛基料溶解于四氢呋喃中得到沥青的四氢呋喃溶液，并将制备的沥青的四氢呋喃溶液倒入混合溶液中，搅拌 20～40min，得到混合料浆，然后加入溶剂调节混合料浆的固体质量百分含量至10～20％；(3) dissolving the asphalt sieve base material obtained in step (2) in tetrahydrofuran to obtain a tetrahydrofuran solution of asphalt, and pouring the prepared asphalt tetrahydrofuran solution into the mixed solution, stirring for 20 to 40 minutes to obtain a mixed slurry, and then Adding a solvent to adjust the solid mass percentage of the mixed slurry to 10-20%;
(4)将步骤(3)中的混合浆料通过闭式循环喷雾干燥机进行干燥，闭式循环喷雾干燥机的进口温度和出口温度分别为120～140℃和70～60℃，闭式循环喷雾干燥机的雾化器的转速为24000～26000r/min，得到所述锂电池负极活性物质。(4) Dry the mixed slurry in step (3) by a closed cycle spray dryer. The inlet temperature and outlet temperature of the closed cycle spray dryer are 120-140°C and 70-60°C respectively. The rotation speed of the atomizer of the spray dryer is 24000-26000r/min, and the lithium battery negative electrode active material is obtained.
优选的，本申请中，所述步骤(1)中石墨烯、碳纳米管的重量份数和无水乙醇的重量份数之比为1：1～1：5。Preferably, in the present application, the ratio of the parts by weight of graphene and carbon nanotubes to the parts by weight of absolute ethanol in the step (1) is 1:1˜1:5.
一种锂离子电池极片所述锂离子电池极片经由上述的锂离子电池极片制备方法制备而成。A lithium-ion battery pole piece. The lithium-ion battery pole piece is prepared by the above-mentioned lithium-ion battery pole piece preparation method.
与现有技术相比，本发明的有益效果是：Compared with prior art, the beneficial effect of the present invention is:
1、本申请中，在制备正极活性物质时，是通过使用碳纳米管及石墨烯作为改性添加剂，形成一种磷酸铁锂正极材料在内，无定型碳包覆在外的结构。一方面，石墨烯和碳纳米管的加入有利于过渡磷酸铁锂的活化，而磷酸铁锂又可阻止石墨烯以及碳纳米管团聚，更容易获得均匀稳定的改性磷酸铁锂，另一方面，磷酸铁锂在放电过程中会形成富锂的化合物，具有很好的离子导电率，同时这些富锂的化合物能够对磷酸锂的表面结构进行修饰，从而使得磷酸酸锂表面的电子电导率提高；1. In this application, when preparing the positive electrode active material, carbon nanotubes and graphene are used as modifying additives to form a structure in which the lithium iron phosphate positive electrode material is contained and amorphous carbon is coated on the outside. On the one hand, the addition of graphene and carbon nanotubes is beneficial to the activation of transition lithium iron phosphate, and lithium iron phosphate can prevent graphene and carbon nanotubes from agglomerating, making it easier to obtain uniform and stable modified lithium iron phosphate. , lithium iron phosphate will form lithium-rich compounds during the discharge process, which has good ionic conductivity. At the same time, these lithium-rich compounds can modify the surface structure of lithium phosphate, thereby improving the electronic conductivity of the lithium phosphate surface. ;
2、本申请中，在制备正极活性物质时，所述包覆层为均匀致密的无定型碳，该无定型碳包覆在改性中间体的表面并形成均匀的包覆层，其厚度为 0.3nm～30nm，这使其除了具备传统包覆层的优点外，纳米量级厚度的超薄包覆层还有利于降低锂离子在包覆层中的迁移路径，进一步提高材料的倍率性能，使其具有良好的锂离子传导特性。2. In the present application, when preparing the positive electrode active material, the coating layer is uniform and dense amorphous carbon, which is coated on the surface of the modified intermediate and forms a uniform coating layer with a thickness of 0.3nm to 30nm, which makes it not only have the advantages of the traditional cladding layer, but the ultra-thin cladding layer with nanometer thickness is also conducive to reducing the migration path of lithium ions in the cladding layer, further improving the rate performance of the material, It has good lithium ion conductivity.
3、本申请中，在制备正极/负极活性物质时，利用石墨烯和碳纳米管的高电导率，所述石墨烯为多层石墨烯，多层石墨烯的内部呈三维立体导电网络结构，进而提升锂电子在包覆层中的迁移速度，碳纳米管插嵌在该三维立体导电网络内，多层石墨烯和碳纳米管作用后形成的颗粒粒径为700nm～22um，该过程是在常温下混合搅拌4～6分钟，然后在惰性气体保护的环境下以2～4℃ /min的速度升温至40～60℃，再保温4～6h，然后自然冷却至室温，得到混合溶液，这样能够进一步排走多层石墨烯和纳米碳管之间的微小气泡，形成稳定的结合层，有利于更好的发挥石墨烯和碳纳米管的导电特性；3. In this application, when preparing positive/negative active materials, the high conductivity of graphene and carbon nanotubes is utilized. The graphene is multilayer graphene, and the interior of multilayer graphene is a three-dimensional conductive network structure. Further, the migration speed of lithium electrons in the cladding layer is increased, carbon nanotubes are inserted into the three-dimensional conductive network, and the particle size formed by the action of multilayer graphene and carbon nanotubes is 700nm~22um. Mix and stir at room temperature for 4-6 minutes, then raise the temperature to 40-60°C at a rate of 2-4°C/min in an inert gas-protected environment, keep the temperature for 4-6 hours, and then cool naturally to room temperature to obtain a mixed solution. It can further remove the tiny bubbles between multi-layer graphene and carbon nanotubes to form a stable bonding layer, which is conducive to better utilizing the conductive properties of graphene and carbon nanotubes;
4、通过本申请提供的工艺，石墨烯和碳纳米管完整地分布在磷酸铁锂材料表面，形成了具有极高导电能力的表面碳层，并不会产生疏松大块碳层，有效地增加了磷酸铁锂正极材料的堆积密度和压实密度，有利于降低锂离子在正极材料表面脱出和嵌入过程的极化电阻；4. Through the process provided by this application, graphene and carbon nanotubes are completely distributed on the surface of lithium iron phosphate material, forming a surface carbon layer with extremely high conductivity, and will not produce loose and large carbon layers, effectively increasing Improve the bulk density and compaction density of the lithium iron phosphate cathode material, which is conducive to reducing the polarization resistance of lithium ions in the process of extraction and insertion on the surface of the cathode material;
5、本申请在制备负极活性物质时，首先是将纳米碳管和石墨烯进行修饰处理，利用石墨烯和碳纳米管的高电导率，石墨烯为多层石墨烯，多层石墨烯的内部呈三维立体导电网络结构，进而提升锂电子在包覆层中的迁移速度，碳纳米管插嵌在该三维立体导电网络内，多层石墨烯和碳纳米管作用后形成的颗粒粒径为700nm～22um，该过程是在常温下混合搅拌4～6分钟，然后在惰性气体保护的环境下以2～4℃/min的速度升温至40～60℃，再保温4～6h，然后自然冷却至室温，得到混合溶液，这样能够进一步排走多层石墨烯和纳米碳管之间的微小气泡，形成稳定的结合层，有利于更好的发挥石墨烯和碳纳米管的导电特性，然后使用闭式循环喷雾干燥的方式制备前驱体，改性沥青均匀分散在石墨烯表面上，经过高温热处理后，沥青碳化后形成一层无定形的炭，紧紧包裹着石墨烯表面，形成一种“核—壳”结构的复合材料，包覆层的存在不仅减低了材料的比表面积，阻止了有机溶剂的进入，达到获得均匀、致密的SEI膜的目的，同时，表面炭材料能固定石墨片，防止石墨表层的脱落，使得材料的首次效率、比容量和循环稳定性得到一定的提高。5. When preparing the negative electrode active material, the present application firstly modifies carbon nanotubes and graphene, utilizes the high conductivity of graphene and carbon nanotubes, graphene is multilayer graphene, and the interior of multilayer graphene It has a three-dimensional conductive network structure, thereby increasing the migration speed of lithium electrons in the coating layer. Carbon nanotubes are embedded in the three-dimensional conductive network. The particle size of the particles formed by the interaction of multilayer graphene and carbon nanotubes is 700nm ~22um, the process is to mix and stir at room temperature for 4-6 minutes, then raise the temperature to 40-60°C at a rate of 2-4°C/min under the protection of inert gas, keep it warm for 4-6 hours, and then cool naturally to At room temperature, a mixed solution is obtained, which can further remove the tiny bubbles between the multilayer graphene and carbon nanotubes, and form a stable bonding layer, which is beneficial to better play the conductive properties of graphene and carbon nanotubes, and then use the closed The precursor is prepared by means of circular spray drying, and the modified pitch is uniformly dispersed on the surface of graphene. After high-temperature heat treatment, the pitch is carbonized to form a layer of amorphous carbon, which tightly wraps the surface of graphene, forming a "nucleus". For composite materials with “shell” structure, the existence of the coating layer not only reduces the specific surface area of the material, prevents the entry of organic solvents, and achieves the purpose of obtaining a uniform and dense SEI film. At the same time, the surface carbon material can fix the graphite sheet and prevent The exfoliation of the graphite surface improves the initial efficiency, specific capacity and cycle stability of the material to a certain extent.
6、本申请中，添加造孔剂在分段干燥处理的过程中受热分解为气体，气体从浆料中溢出过程中在浆料内部产生大量的气孔，干燥后留下均匀的孔隙，干燥后获得的锂离子电池电极经过辊压，不但压实密度不受影响，而且锂离子电池电极内部孔隙分别均匀，而且孔隙率比普通电极高。6. In this application, the added pore-forming agent is heated and decomposed into gas during the staged drying process. When the gas overflows from the slurry, a large number of pores are generated inside the slurry, and uniform pores are left after drying. The obtained lithium-ion battery electrode is rolled, not only the compaction density is not affected, but also the internal pores of the lithium-ion battery electrode are uniform, and the porosity is higher than that of ordinary electrodes.
具体实施方式：Detailed ways:
为了使本发明实现的技术手段、创作特征、达成目的与功效易于明白了解，下面结合具体实施例，进一步阐述本发明。In order to make the technical means, creative features, goals and effects achieved by the present invention easy to understand, the present invention will be further described below in conjunction with specific embodiments.
实施例1Example 1
一种锂离子电池极片制备方法，包括正极/负极活性物质75kg、造孔剂 2kg、导电剂2.5kg、粘接剂1.5kg、溶剂50kg；A method for preparing a lithium-ion battery pole piece, comprising 75kg of positive electrode/negative electrode active material, 2kg of pore-forming agent, 2.5kg of conductive agent, 1.5kg of adhesive, and 50kg of solvent;
并经由以下步骤制备所述锂离子电池极片：And prepare described lithium-ion battery pole piece through the following steps:
(1)制备正极活性物质和负极活性物质；(1) prepare positive electrode active material and negative electrode active material;
(2)将步骤(1)中的正极/负极活性物质分别与造孔剂、导电剂、粘接剂以及溶剂混合，并制备形成浆料A、浆料B；(2) Mix the positive electrode/negative electrode active material in step (1) with pore-forming agent, conductive agent, binder and solvent respectively, and prepare slurry A and slurry B;
(3)所述步骤(2)中的浆料A、B涂覆在集流体上，在50～55℃、65～ 75℃、80～85℃、75～80℃下干燥处理，辊压，分切，得到所述锂离子电池极片。(3) The slurry A and B in the step (2) are coated on the current collector, dried at 50-55°C, 65-75°C, 80-85°C, and 75-80°C, and rolled, cutting to obtain the lithium ion battery pole piece.
本实施例中，所述造孔剂为聚苯乙烯球，所述造孔剂的粒径≤2.0um，所述导电剂为乙炔黑，所述溶剂为无水乙醇。In this embodiment, the pore-forming agent is polystyrene balls, the particle size of the pore-forming agent is ≤2.0um, the conductive agent is acetylene black, and the solvent is absolute ethanol.
本实施例中，所述正极活性物质经由以下步骤制备：In this embodiment, the positive electrode active material is prepared through the following steps:
(1)将质量比2：1石墨烯和碳纳米管投入到乙醇中，并通过超声初步粉碎处理后，在常温下混合搅拌4～6分钟，然后在惰性气体保护的环境下以2～4℃ /min的速度升温至40～60℃，再保温4～6h，然后自然冷却至室温，得到混合溶液；(1) Graphene and carbon nanotubes with a mass ratio of 2:1 are put into ethanol, and after being preliminarily crushed by ultrasonic waves, they are mixed and stirred at room temperature for 4 to 6 minutes, and then mixed with 2 to 4 The temperature is raised to 40-60°C at a rate of ℃/min, and then kept for 4-6 hours, and then naturally cooled to room temperature to obtain a mixed solution;
所述石墨烯为多层石墨烯，所述多层石墨烯的内部呈三维立体导电网络结构，所述碳纳米管插嵌在该三维立体导电网络内，多层石墨烯和碳纳米管作用后形成的颗粒粒径为700nm～22um；The graphene is multi-layer graphene, and the inside of the multi-layer graphene is a three-dimensional conductive network structure, and the carbon nanotubes are embedded in the three-dimensional conductive network. The particle size formed is 700nm～22um;
(2)将磷酸铁锂粉碎到粒径3～6um，并将磷酸铁锂投入到搅拌釜中，按照磷酸铁锂和蒸馏水的质量比＝1：2～7的比例缓慢添加蒸馏水，并添加偶联剂和乙炔黑，快速搅拌10～16min后，将步骤(1)中的混合溶液添加至搅拌釜中，搅拌均匀，得到改性中间体；(2) Crush lithium iron phosphate to a particle size of 3-6um, put lithium iron phosphate into a stirred tank, slowly add distilled water according to the mass ratio of lithium iron phosphate to distilled water = 1:2-7, and add even The coupling agent and acetylene black are stirred rapidly for 10 to 16 minutes, then the mixed solution in step (1) is added to the stirring tank, and stirred evenly to obtain a modified intermediate;
(3)将步骤(2)制备的改性中间体加入雾化器中进行喷雾干燥处理，该过程中是在保护气体作用下吹入气态碳源，使所述气态碳源在改性中间体表面裂解形成无定形碳，该无定型碳包覆在改性中间体的表面并形成均匀的包覆层；(3) Add the modified intermediate prepared in step (2) into the atomizer and carry out spray drying treatment. In this process, the gaseous carbon source is blown into under the effect of protective gas, so that the gaseous carbon source is blown into the modified intermediate The surface cracks to form amorphous carbon, which is coated on the surface of the modified intermediate and forms a uniform coating layer;
(4)将步骤(3)中得到的粉末颗粒在真空烘干，在250～350℃和保护气体作用下煅烧3～4小时，得到改性磷酸铁锂正极材料。(4) Drying the powder particles obtained in step (3) in a vacuum, and calcining at 250-350° C. under the action of a protective gas for 3-4 hours to obtain a modified lithium iron phosphate positive electrode material.
本实施例中，所述偶联剂为γ-巯丙基三甲氧基硅烷、甲基异丁基酮肟基硅烷或乙烯基三乙氧基硅烷，所述偶联剂：乙炔黑：混合溶液的质量比为： (0.1～2：1～1.6：100)；In this embodiment, the coupling agent is γ-mercaptopropyl trimethoxysilane, methyl isobutyl ketoximino silane or vinyl triethoxysilane, the coupling agent: acetylene black: mixed solution The mass ratio is: (0.1～2:1～1.6:100);
所述步骤(3)中是将改性中间体投入到雾化器中，并在氮气保护的状态下升温至500～700℃进行退火处理，然后由保护气体载入24～26％的气态碳源，气体流速50～1000ml/min，同时开启雾化器，保护气体将雾化器中雾化的细小成分带到高温炉中，保温1～12小时，使所述气态碳源在改性中间体表面裂解形成无定形碳，该无定型碳包覆在改性中间体的表面并形成均匀的包覆层，其厚度为0.3nm～30nm。In the step (3), the modified intermediate is put into the atomizer, and the temperature is raised to 500-700 ° C under the protection of nitrogen for annealing treatment, and then 24-26% of gaseous carbon is loaded by the protection gas source, the gas flow rate is 50-1000ml/min, and the atomizer is turned on at the same time, and the protective gas will bring the fine components atomized in the atomizer to the high-temperature furnace, and keep it warm for 1-12 hours, so that the gaseous carbon source is in the middle of the modification. The surface of the body is cracked to form amorphous carbon, and the amorphous carbon is coated on the surface of the modified intermediate to form a uniform coating layer with a thickness of 0.3nm to 30nm.
本实施例中，所述负极活性物质经由以下步骤制备：In this embodiment, the negative electrode active material is prepared through the following steps:
(1)将质量比2：1石墨烯和碳纳米管投入到无水乙醇中，并通过超声初步粉碎处理后，在常温下混合搅拌4～6分钟，然后在惰性气体保护的环境下以 2～4℃/min的速度升温至40～60℃，再保温4～6h，然后自然冷却至室温，得到混合溶液；(1) Graphene and carbon nanotubes with a mass ratio of 2:1 were put into absolute ethanol, and after being preliminarily pulverized by ultrasonic waves, they were mixed and stirred at room temperature for 4 to 6 minutes, and then in an environment protected by an inert gas with 2 Raise the temperature to 40-60°C at a rate of ~4°C/min, then keep it warm for 4-6 hours, and then naturally cool to room temperature to obtain a mixed solution;
所述石墨烯为多层石墨烯，所述多层石墨烯的内部呈三维立体导电网络结构，所述碳纳米管插嵌在该三维立体导电网络内，多层石墨烯和碳纳米管作用后形成的颗粒粒径为600nm～20um。The graphene is multi-layer graphene, and the inside of the multi-layer graphene is a three-dimensional conductive network structure, and the carbon nanotubes are embedded in the three-dimensional conductive network. The particle size of the formed particles is 600nm-20um.
(2)采用石油沥青为基料，将该基料进行粉碎和球磨处理至粒径为 120～140um，再将处理后的颗粒投入至反应釜中进行改性处理，其步骤包括：(2) Using petroleum asphalt as the base material, crushing and ball milling the base material until the particle size is 120-140um, and then putting the treated particles into the reactor for modification treatment, the steps include:
(2.1)采用流速为80～120每小时的空速通入氮气，然后进行升温至 300～420℃，升温速度为40～60℃/h，保温2～6h；(2.1) Nitrogen gas is introduced at a space velocity of 80-120 hours per hour, then the temperature is raised to 300-420°C, the temperature rise rate is 40-60°C/h, and the temperature is kept for 2-6 hours;
(2.2)取部分步骤(2.1)中的沥青粉碎至粒径在20um以下，并测量软化点，并在此温度下保温4～6h，直至测得的软化点在180～380℃的沥青基料；(2.2) Take part of the asphalt in the step (2.1) and crush it until the particle size is below 20um, measure the softening point, and keep it at this temperature for 4-6 hours until the measured softening point is 180-380°C. ;
(2.3)将步骤(2.2)中的沥青基料自然冷却至室温，然后将沥青基料粉碎至粒径为18～20um，即为改性沥青基料；(2.3) Naturally cool the asphalt base material in the step (2.2) to room temperature, then pulverize the asphalt base material to a particle size of 18-20um, which is the modified asphalt base material;
(3)将步骤(2)中得到的沥青筛基料溶解于四氢呋喃中得到沥青的四氢呋喃溶液，并将制备的沥青的四氢呋喃溶液倒入混合溶液中，搅拌 20～40min，得到混合料浆，然后加入溶剂调节混合料浆的固体质量百分含量至10～20％；(3) dissolving the asphalt sieve base material obtained in step (2) in tetrahydrofuran to obtain a tetrahydrofuran solution of asphalt, and pouring the prepared asphalt tetrahydrofuran solution into the mixed solution, stirring for 20 to 40 minutes to obtain a mixed slurry, and then Adding a solvent to adjust the solid mass percentage of the mixed slurry to 10-20%;
(4)将步骤(3)中的混合浆料通过闭式循环喷雾干燥机进行干燥，闭式循环喷雾干燥机的进口温度和出口温度分别为120～140℃和70～60℃，闭式循环喷雾干燥机的雾化器的转速为24000～26000r/min，得到所述锂电池负极活性物质。(4) Dry the mixed slurry in step (3) by a closed cycle spray dryer. The inlet temperature and outlet temperature of the closed cycle spray dryer are 120-140°C and 70-60°C respectively. The rotation speed of the atomizer of the spray dryer is 24000-26000r/min, and the lithium battery negative electrode active material is obtained.
所述步骤(1)中石墨烯、碳纳米管的重量份数和无水乙醇的重量份数之比为1：1～1：5。In the step (1), the ratio of the parts by weight of graphene and carbon nanotubes to the parts by weight of absolute ethanol is 1:1˜1:5.
一种锂离子电池极片，所述锂离子电池极片经由上述的锂离子电池极片制备方法制备而成。A lithium-ion battery pole piece, which is prepared by the above-mentioned lithium-ion battery pole piece preparation method.
实施例2：Example 2:
本实施例内容和实施例1内容基本相同，相同之处不再重述，不同之处在于：包括正极/负极活性物质70kg、造孔剂1kg、导电剂2kg、粘接剂1kg、溶剂40kg。The content of this example is basically the same as that of Example 1, and the similarities will not be repeated. The difference is that it includes 70 kg of positive/negative active materials, 1 kg of pore-forming agent, 2 kg of conductive agent, 1 kg of binder, and 40 kg of solvent.
实施例3：Example 3:
本实施例内容和实施例1内容基本相同，相同之处不再重述，不同之处在于：包括正极/负极活性物质80kg、造孔剂3kg、导电剂3kg、粘接剂2kg、溶剂60kg。The content of this example is basically the same as that of Example 1, and the similarities will not be repeated. The difference is that it includes 80kg of positive electrode/negative electrode active material, 3kg of pore-forming agent, 3kg of conductive agent, 2kg of adhesive, and 60kg of solvent.
对比例1：Comparative example 1:
本对比例采用申请号CN201210380360.X制备形成的电极极片及其锂离子电池进行测试。In this comparative example, the electrode pole piece and the lithium-ion battery prepared by the application number CN201210380360.X were used for testing.
电池性能测试Battery Performance Test
在同样的压实密度的条件下，通过使用压汞仪测量电极的孔隙率，在干燥的手套箱内滴加电解液测量渗液时间，并对实施例1至实施例3以及对比1中制备的锂离子电池进行电池循环和自放电测试，结果如下表1：Under the condition of the same compaction density, by using a mercury porosimeter to measure the porosity of the electrode, the electrolyte was dripped in a dry glove box to measure the seepage time, and prepared in Example 1 to Example 3 and Comparative 1 The lithium-ion battery was tested for battery cycle and self-discharge, and the results are shown in Table 1:
表1电极物理性能、电化学性能对比结果Table 1 Comparison results of electrode physical properties and electrochemical properties
以上显示和描述了本发明的基本原理和主要特征和本发明的优点。本行业的技术人员应该了解，本发明不受上述实施例的限制，上述实施例和说明书中描述的只是说明本发明的原理，在不脱离本发明精神和范围的前提下，本发明还会有各种变化和改进，这些变化和改进都落入要求保护的本发明范围内。本发明要求保护范围由所附的权利要求书及其等效物界定。The basic principles and main features of the present invention and the advantages of the present invention have been shown and described above. Those skilled in the art should understand that the present invention is not limited by the above-mentioned embodiments, and that described in the above-mentioned embodiments and the specification only illustrates the principles of the present invention, and the present invention will also have other functions without departing from the spirit and scope of the present invention. Variations and improvements all fall within the scope of the claimed invention. The protection scope of the present invention is defined by the appended claims and their equivalents.
| Application Number | Priority Date | Filing Date | Title |
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| CN201810601004.3ACN108682787B (en) | 2018-06-12 | 2018-06-12 | A kind of lithium ion battery pole piece and preparation method thereof |
| Application Number | Priority Date | Filing Date | Title |
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| CN201810601004.3ACN108682787B (en) | 2018-06-12 | 2018-06-12 | A kind of lithium ion battery pole piece and preparation method thereof |
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| CN201810601004.3AActiveCN108682787B (en) | 2018-06-12 | 2018-06-12 | A kind of lithium ion battery pole piece and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109449413A (en)* | 2018-11-01 | 2019-03-08 | 北京理工大学 | A kind of lithium phosphate class additive, lithium-rich manganese-based anode and lithium battery |
| CN109698338A (en)* | 2018-12-26 | 2019-04-30 | 湖北锂诺新能源科技有限公司 | A kind of powerful graphene-based LiFePO4 pole piece of low cost and preparation method |
| CN111554898A (en)* | 2020-05-11 | 2020-08-18 | 珠海冠宇电池股份有限公司 | Negative electrode material and preparation method and application thereof |
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| CN114899369A (en)* | 2022-04-08 | 2022-08-12 | 西部诚业科技发展(深圳)有限公司 | Conductive composition and preparation method thereof |
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| CN115911378A (en)* | 2022-11-17 | 2023-04-04 | 汇洋世纪新能源科技有限公司 | Positive electrode conductive slurry and preparation method thereof, lithium iron phosphate positive electrode material and preparation method thereof |
| CN117069155A (en)* | 2023-08-21 | 2023-11-17 | 深圳珈钠能源科技有限公司 | Preparation method of low specific surface sulfate sodium ion battery positive electrode material |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20110121240A1 (en)* | 2009-11-23 | 2011-05-26 | Khalil Amine | Coated electroactive materials |
| CN102931378A (en)* | 2012-10-09 | 2013-02-13 | 东莞市创明电池技术有限公司 | Lithium ion battery electrode, preparation method thereof and lithium ion battery |
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| WO2017222113A1 (en)* | 2016-06-24 | 2017-12-28 | 삼성에스디아이 주식회사 | Negative electrode active material for lithium secondary battery, method for manufacturing same, and lithium secondary battery including same |
| CN107785549A (en)* | 2017-10-10 | 2018-03-09 | 中航锂电（洛阳）有限公司 | The preparation method and carbon compound cathode materials of a kind of carbon compound cathode materials |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20110121240A1 (en)* | 2009-11-23 | 2011-05-26 | Khalil Amine | Coated electroactive materials |
| CN102931378A (en)* | 2012-10-09 | 2013-02-13 | 东莞市创明电池技术有限公司 | Lithium ion battery electrode, preparation method thereof and lithium ion battery |
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| CN107785549A (en)* | 2017-10-10 | 2018-03-09 | 中航锂电（洛阳）有限公司 | The preparation method and carbon compound cathode materials of a kind of carbon compound cathode materials |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109449413A (en)* | 2018-11-01 | 2019-03-08 | 北京理工大学 | A kind of lithium phosphate class additive, lithium-rich manganese-based anode and lithium battery |
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