CN102544502A - Anode and cathode conductive additive for secondary lithium battery, method for preparing conductive additive, and method for preparing secondary lithium battery - Google Patents
Anode and cathode conductive additive for secondary lithium battery, method for preparing conductive additive, and method for preparing secondary lithium batteryDownload PDFInfo
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Translated fromChinese技术领域technical field
本发明属于储能材料领域，具体涉及一种用于锂二次电池的导电添加剂及其制备方法和相关的电池技术领域。 The invention belongs to the field of energy storage materials, and in particular relates to a conductive additive for lithium secondary batteries, a preparation method thereof and related battery technology fields. the
背景技术Background technique
自从上世纪90年代初首个商品化锂二次电池产品问世以来，锂二次电池就因其高容量、高电压平台、长寿命和高安全性而在便携式电子产品中获得了广泛的应用。随着化石能源枯竭及全球气候变暖等关乎人类生存发展的问题日益突出，人们对于清洁能源的需求不断扩大，由此产生的新能源产业具有极为巨大的发展前景和市场规模。人们普遍预期锂二次电池在该产业中将大有作为，尤其在大型储能设备和以电动汽车为代表的动力电池中的应用前景更是吸引了全球的目光。为此，世界各国都投入了大量的人力物力进行新型高性能锂二次电池的研发，以满足大型动力电池和储能电池在能量密度、功率密度、循环寿命和安全性等方面提出的更高的要求。 Since the first commercial lithium secondary battery products came out in the early 1990s, lithium secondary batteries have been widely used in portable electronic products due to their high capacity, high voltage platform, long life and high safety. With the depletion of fossil energy and global warming and other issues related to human survival and development becoming increasingly prominent, people's demand for clean energy continues to expand, and the resulting new energy industry has extremely huge development prospects and market size. It is generally expected that lithium secondary batteries will play a big role in this industry, especially the application prospects in large-scale energy storage equipment and power batteries represented by electric vehicles have attracted global attention. To this end, countries around the world have invested a lot of manpower and material resources in the research and development of new high-performance lithium secondary batteries to meet the higher requirements of large-scale power batteries and energy storage batteries in terms of energy density, power density, cycle life and safety. requirements. the
作为电池的一种，锂二次电池自然要求其电极具有良好的导电性。目前常用的磷酸铁锂、锰酸锂、三元材料等正极活性材料本身的电导率均不是很高，同时正极材料颗粒间存在较大接触电阻。因此，在正极制备中均需要加入具有高电导率的添加剂以提高正极内的电子迁移速率。负极中常用的石墨类活性材料，虽然本身具有良好的导电性，但为了克服颗粒间的接触电阻，尤其是要实现大倍率放电时，仍然需要通过添加导电剂来改善其导电性，使其的电子导电能力与锂离子从石墨中脱嵌的能力达至平衡。因此，导电添加剂在锂二次电池中发挥着重要的作用，也是该产业的一个不可或缺的组成部分。 As a kind of battery, lithium secondary battery naturally requires its electrodes to have good conductivity. Currently commonly used positive electrode active materials such as lithium iron phosphate, lithium manganese oxide, and ternary materials do not have very high electrical conductivity, and at the same time, there is a large contact resistance between the particles of the positive electrode material. Therefore, it is necessary to add additives with high conductivity in the preparation of positive electrodes to increase the electron transfer rate in the positive electrode. Graphite-based active materials commonly used in negative electrodes have good electrical conductivity, but in order to overcome the contact resistance between particles, especially to achieve high-rate discharge, it is still necessary to add a conductive agent to improve its electrical conductivity. The ability to conduct electrons is balanced with the ability to deintercalate lithium ions from graphite. Therefore, conductive additives play an important role in lithium secondary batteries and are an integral part of the industry. the
目前，商品化的导电剂以碳材料为主，主要包括低端的导电石墨、乙炔黑、Super P-Li等，和高端的碳纳米管导电添加剂。前者虽然价格便宜，但难以满足电池在高倍率下的 持续充放电；后者尽管性能出色，尤其适用于高功率电池，但其昂贵的价格限制了其在锂二次电池中的实际应用。因此，开发新型廉价的高性能导电添加剂刻不容缓。 At present, commercial conductive agents are mainly carbon materials, mainly including low-end conductive graphite, acetylene black, Super P-Li, etc., and high-end carbon nanotube conductive additives. Although the former is cheap, it is difficult to meet the continuous charge and discharge of the battery at a high rate; although the latter has excellent performance, especially suitable for high-power batteries, its expensive price limits its practical application in lithium secondary batteries. Therefore, it is urgent to develop new and cheap high-performance conductive additives. the
石墨烯是2004年发现的一类新型碳材料，它具有独特的二维纳米结构和新颖的物理化学性质，因此受到了科学界和产业界的广泛关注，应用前景十分广阔。石墨烯具有极高的电导率，这为其成为一款成功的导电添加剂奠定了基础。其次，石墨烯的二维纳米结构既不同于导电石墨或Super P-Li等三维导电颗粒，也不同于一维的碳纳米管。如薄膜般“柔韧”的石墨烯很容易包裹于电极活性材料颗粒周围，形成面接触，并很容易形成三维的导电网络。另一方面，石墨烯良好的导热性能对于电池高温性能和循环稳定性的提升也是大有益处的。在我们之前申请的国家发明专利(申请号201010514810.0)中，通过改进的方法，已经可以实现高质量石墨烯的大规模制备，并且成本低廉(显著低于碳纳米管)。因此，石墨烯导电添加剂相比于其他导电剂产品具有明显的优势。 Graphene is a new type of carbon material discovered in 2004. It has a unique two-dimensional nanostructure and novel physical and chemical properties, so it has attracted extensive attention from the scientific and industrial circles, and its application prospects are very broad. Graphene has extremely high electrical conductivity, which lays the foundation for its success as a conductive additive. Secondly, the two-dimensional nanostructure of graphene is not only different from three-dimensional conductive particles such as conductive graphite or Super P-Li, but also different from one-dimensional carbon nanotubes. The "flexible" graphene like a film is easy to wrap around the electrode active material particles, forming surface contact, and easily forming a three-dimensional conductive network. On the other hand, the good thermal conductivity of graphene is also of great benefit to the improvement of battery high temperature performance and cycle stability. In the national invention patent (application number 201010514810.0) we applied for before, through the improved method, large-scale preparation of high-quality graphene has been achieved, and the cost is low (significantly lower than that of carbon nanotubes). Therefore, graphene conductive additives have obvious advantages over other conductive agent products. the
发明内容Contents of the invention
本发明所要解决的首要技术问题是针对上述技术现状提供一种用于锂二次电池的正极负极导电添加剂，它实现电子在电极中的快速迁移，利于高倍率充放电，同时能够提升电池的高温性能和循环寿命。 The primary technical problem to be solved by the present invention is to provide a positive and negative conductive additive for lithium secondary batteries in view of the above-mentioned technical status, which realizes the rapid migration of electrons in the electrodes, is beneficial to high-rate charge and discharge, and can improve the high temperature of the battery at the same time. performance and cycle life. the
本发明所要解决的另一个技术问题是针对上述技术现状提供一种用于锂二次电池的正极负极导电添加剂的制备方法，其方法简单，容易实施。 Another technical problem to be solved by the present invention is to provide a method for preparing conductive additives for positive and negative electrodes of lithium secondary batteries, which is simple and easy to implement. the
本发明所要解决的再一个技术问题是针对上述技术现状提供一种相关的锂二次电池的制备方法。 Another technical problem to be solved by the present invention is to provide a related lithium secondary battery preparation method in view of the above technical status. the
本发明为解决上述首要技术问题所采用的技术方案为：一种用于锂二次电池的正极负极导电添加剂，其特征在于采用石墨烯导电添加剂，为纯石墨烯或者石墨烯与其它导电材料的混合物，所述的石墨烯与其它导电材料的混合物中，石墨烯所占的质量百分比在1％-99％之间。 The technical solution adopted by the present invention to solve the above-mentioned primary technical problems is: a positive and negative conductive additive for lithium secondary batteries, which is characterized in that the graphene conductive additive is used, which is a combination of pure graphene or graphene and other conductive materials. For the mixture, in the mixture of graphene and other conductive materials, the mass percentage of graphene is between 1% and 99%. the
作为改进，所述的石墨烯导电添加剂为粉体，或者为分散于水或有机溶剂中的石墨烯导电添加剂浆料，或者为分散于含有分散剂的水或有机溶剂中的石墨烯导电添加剂浆料，所述的石墨烯导电添加剂浆料中石墨烯或石墨烯与其它导电材料的混合物的质量百分比为0.5％-30％，所述的分散剂在石墨烯导电添加剂浆料中的质量百分含量为 0.1％-10％。 As an improvement, the graphene conductive additive is a powder, or a graphene conductive additive slurry dispersed in water or an organic solvent, or a graphene conductive additive slurry dispersed in water or an organic solvent containing a dispersant Material, the mass percent of graphene or the mixture of graphene and other conductive materials in the described graphene conductive additive slurry is 0.5%-30%, the mass percent of described dispersant in the graphene conductive additive slurry The content is 0.1%-10%. the
优选，所述的石墨烯为单原子层石墨，或原子层数在2-15层之间的石墨烯纳米片，其片层横向尺寸在0.1-100μm之间。 Preferably, the graphene is monoatomic layer graphite, or graphene nanosheets with 2-15 atomic layers, and the lateral size of the sheets is between 0.1-100 μm. the
优选，所述的其它导电材料至少为导电石墨、导电碳黑、乙炔黑、Super P-Li、碳纳米管(CNTs)、碳纳米纤维、气相生长碳纤维(VGCF)、导电银颗粒、导电铜颗粒、导电铝颗粒、导电银纤维、导电铜纤维、导电铝纤维中的一种，或几种的组合。 Preferably, said other conductive materials are at least conductive graphite, conductive carbon black, acetylene black, Super P-Li, carbon nanotubes (CNTs), carbon nanofibers, vapor-phase grown carbon fibers (VGCF), conductive silver particles, conductive copper particles , conductive aluminum particles, conductive silver fibers, conductive copper fibers, conductive aluminum fibers, or a combination of several. the
优选，所述的有机溶剂为N-甲基吡咯烷酮、乙醇、丙酮、吡啶、苯胺、环戊烷、环己烷、正丁基环戊环烷、2，2-二甲基己烷、2，3-二甲基己烷、2，4-二甲基戊烷、五甲基庚烷中的一种或几种的组合。 Preferably, the organic solvent is N-methylpyrrolidone, ethanol, acetone, pyridine, aniline, cyclopentane, cyclohexane, n-butylcyclopentane, 2,2-dimethylhexane, 2,3- One or a combination of dimethylhexane, 2,4-dimethylpentane, and pentamethylheptane. the
优选，所述的分散剂至少为聚乙烯吡咯烷酮、聚乙烯醇、Pluoronic F127、Pluoronic P123、Pluronic F68、聚氧乙烯月桂醚中的一种，或几种的组合。 Preferably, the dispersant is at least one of polyvinylpyrrolidone, polyvinyl alcohol, Pluoronic F127, Pluoronic P123, Pluronic F68, polyoxyethylene lauryl ether, or a combination of several. the
本发明为解决上述另一个技术问题所采用的技术方案为：一种用于锂二次电池的正极负极导电添加剂的制备方法，其特征在于该方法按以下各自步骤选择进行： The technical solution adopted by the present invention to solve the above-mentioned another technical problem is: a kind of preparation method for positive and negative electrode conductive additives of lithium secondary battery, it is characterized in that the method is selected and carried out according to the following respective steps:
1)石墨烯导电添加剂粉体通过如下两种方法的一种制备： 1) The graphene conductive additive powder is prepared by one of the following two methods:
a)将石墨烯粉体与其它导电材料粉体通过机械混合得到复合物粉体，使所述的石墨烯与其它导电材料的混合物，其石墨烯所占的质量百分比在1％-99％之间； a) Graphene powder is mechanically mixed with other conductive material powder to obtain composite powder, so that the mass percentage of graphene in the mixture of graphene and other conductive materials is between 1% and 99%. between;
或者是， or it could be,
b)是将石墨烯，或者石墨烯与其它导电材料的混合物加入水或有机溶剂，或者是将石墨烯，或者石墨烯与其它导电材料的混合物加入含有分散剂的水或有机溶剂中，通过超声处理或机械混合，或上述超声处理或机械混合组合形成均匀分散的胶体，再通过离心、抽滤或压滤中的一种方法得到浓缩的导电添加剂浆料，进一步干燥除去残余水或溶剂及分散剂，得到石墨烯导电添加剂粉体材料，使所述的石墨烯与其它导电材料的混合物，其石墨烯所占的质量百分比在1％-99％之间； b) adding graphene, or a mixture of graphene and other conductive materials to water or an organic solvent, or adding graphene, or a mixture of graphene and other conductive materials to water or an organic solvent containing a dispersant, through ultrasonic Treatment or mechanical mixing, or the combination of the above-mentioned ultrasonic treatment or mechanical mixing to form a uniformly dispersed colloid, and then obtain a concentrated conductive additive slurry by one of the methods of centrifugation, suction filtration or pressure filtration, and then dry to remove residual water or solvent and disperse agent to obtain a graphene conductive additive powder material, so that the mixture of graphene and other conductive materials has a mass percentage of graphene between 1% and 99%;
2)分散于水或有机溶剂中的导电添加剂浆料通过以下方法制备： 2) The conductive additive slurry dispersed in water or organic solvent is prepared by the following method:
将石墨烯，或者石墨烯与其它导电材料的混合物加入水或有机溶剂中，所述的石墨烯与其它导电材料的混合物中，石墨烯所占的质量百分比在1％-99％之间，通过超声处理或机械混合，或者上述超声处理或机械混合法的组合形成均匀分散的胶体，再通过离心、抽滤或压滤中的一种方法浓缩后得到导电添加剂浆料，所述的石墨烯导电添加剂浆料中石墨烯或石墨烯与其它导电材料的混合物的质量百分比为0.5％-30％； Graphene, or a mixture of graphene and other conductive materials is added to water or an organic solvent, and in the mixture of graphene and other conductive materials, the mass percentage of graphene is between 1% and 99%. Ultrasonic treatment or mechanical mixing, or a combination of the above-mentioned ultrasonic treatment or mechanical mixing methods to form a uniformly dispersed colloid, and then concentrated by one of the methods in centrifugation, suction filtration or pressure filtration to obtain a conductive additive slurry, the graphene conductive The mass percentage of graphene or the mixture of graphene and other conductive materials in the additive slurry is 0.5%-30%;
3)分散于含有分散剂的水或有机溶剂中的石墨烯导电添加剂浆料通过以下方法制备：3) the graphene conductive additive slurry dispersed in water containing dispersant or organic solvent is prepared by the following method:
先将分散剂溶解于水或有机溶剂中，随后加入石墨烯，或者石墨烯与其它导电材料的混合物，所述的石墨烯与其它导电材料的混合物中，石墨烯所占的质量百分比在1％-99％之间，通过超声处理或机械混合，或这上述超声处理或机械混合的组合形成均匀分散的胶体，再通过离心、抽滤或压滤中的一种方法浓缩后得到导电添加剂浆料，所述的石墨烯导电添加剂浆料中石墨烯或石墨烯与其它导电材料的混合物的质量百分比为0.5％-30％，所述的分散剂在石墨烯导电添加剂浆料中的质量百分含量为0.1％-10％。 First dissolve the dispersant in water or an organic solvent, then add graphene, or a mixture of graphene and other conductive materials, and in the mixture of graphene and other conductive materials, the mass percentage of graphene is 1% Between -99%, uniformly dispersed colloids are formed by ultrasonic treatment or mechanical mixing, or a combination of the above-mentioned ultrasonic treatment or mechanical mixing, and then concentrated by one of the methods of centrifugation, suction filtration or pressure filtration to obtain conductive additive slurry , the mass percent of graphene or the mixture of graphene and other conductive materials in the graphene conductive additive slurry is 0.5%-30%, and the mass percent of the dispersant in the graphene conductive additive slurry 0.1%-10%. the
优选，机械混合对于粉体采用球磨、砂磨或干法搅拌中的一种。 Preferably, mechanical mixing adopts one of ball milling, sand milling or dry stirring for the powder. the
优选，机械混合对于液相采用高能搅拌、高速剪切或砂磨中的一种。 Preferably, mechanical mixing employs one of high energy agitation, high shear or sand milling for the liquid phase. the
优选，超声处理采用探头式超声设备或超声清洗器，功率100-3000W，超声时间5-60分钟。 Preferably, the ultrasonic treatment adopts a probe-type ultrasonic device or an ultrasonic cleaner with a power of 100-3000W and an ultrasonic time of 5-60 minutes. the
优选，干燥采用常压干燥、真空干燥、喷雾干燥或冷冻干燥中的一种。 Preferably, one of normal pressure drying, vacuum drying, spray drying or freeze drying is used for drying. the
本发明为解决上述再一个技术问题所采用的技术方案为：一种使用正极负极导电添加剂的锂二次电池制备方法，其特征在于按以下步骤进行： The technical solution adopted by the present invention for solving the above-mentioned another technical problem is: a kind of lithium secondary battery preparation method using positive electrode and negative electrode conductive additive, it is characterized in that following steps are carried out:
将石墨烯导电添加剂粉体或浆料与粘结剂按一定比例分散于水或者有机溶剂中，搅拌均匀后，加入锂二次电池正极或负极活性材料，高速搅拌分散至呈均匀浆料，随后按照锂二次电池电极制备的常规方法制备正极或负极片，并组装成锂二次电池； Disperse the graphene conductive additive powder or slurry and the binder in water or an organic solvent in a certain proportion, stir evenly, add the positive or negative active material of the lithium secondary battery, stir at a high speed to form a uniform slurry, and then Prepare the positive electrode or negative electrode sheet according to the conventional method for lithium secondary battery electrode preparation, and assemble it into a lithium secondary battery;
所述石墨烯导电添加剂采用粉体时，为纯石墨烯或者石墨烯与其它导电材料的混合物，所述的石墨烯与其它导电材料的混合物中，石墨烯所占的质量百分比在1％-99％之间；采用浆料时，为分散于水或有机溶剂中的石墨烯导电添加剂浆料，或者为分散于含有分散剂的水或有机溶剂中的石墨烯导电添加剂浆料，所述的石墨烯导电添加剂浆料中石墨烯或石墨烯与其它导电材料的混合物的质量百分比为0.5％-30％，所述的分散剂在石墨烯导电添加剂浆料中的质量百分含量为0.1％-10％； When the graphene conductive additive is powder, it is pure graphene or a mixture of graphene and other conductive materials. In the mixture of graphene and other conductive materials, the mass percentage of graphene is between 1% and 99%. %; when using slurry, it is the graphene conductive additive slurry dispersed in water or organic solvent, or the graphene conductive additive slurry dispersed in water or organic solvent containing dispersant, the graphite The mass percentage of graphene or the mixture of graphene and other conductive materials in the graphene conductive additive slurry is 0.5%-30%, and the mass percentage of the dispersant in the graphene conductive additive slurry is 0.1%-10% %;
所述的粘结剂为聚偏氟乙烯，或聚四氟乙烯中、聚乙烯醇、羧甲基纤维素钠、甲基纤维素、羟丙基甲基纤维素、羧甲基羟乙基纤维素或羟丙基纤维素中的一种，粘结剂在锂二次电池正极或负极中的质量百分比为1％-10％。 The binder is polyvinylidene fluoride, or polytetrafluoroethylene, polyvinyl alcohol, sodium carboxymethyl cellulose, methyl cellulose, hydroxypropyl methyl cellulose, carboxymethyl hydroxyethyl fiber One of cellulose or hydroxypropyl cellulose, the mass percentage of the binder in the positive or negative electrode of the lithium secondary battery is 1%-10%. the
所述的有机溶剂为N-甲基吡咯烷酮、乙醇或、丙酮、吡啶、苯胺、环戊烷、环己烷、正丁基环戊环烷、2，2-二甲基己烷、2，3-二甲基己烷、2，4-二甲基戊烷、五甲基庚烷 中的一种或几种的组合。 Described organic solvent is N-methylpyrrolidone, ethanol or, acetone, pyridine, aniline, cyclopentane, cyclohexane, n-butyl cyclopentane, 2,2-dimethylhexane, 2,3-bis One or a combination of methyl hexane, 2,4-dimethylpentane, and pentamethylheptane. the
石墨烯导电添加剂粉体或浆料中所含的石墨烯的质量或石墨烯与其它导电材料混合物的总质量与粘结剂的质量比为0.1～10∶1。 The mass ratio of the mass of graphene contained in the graphene conductive additive powder or slurry or the total mass of the mixture of graphene and other conductive materials to the binder is 0.1-10:1. the
石墨烯导电添加剂粉体或浆料中所含的石墨烯质量或石墨烯与其它导电材料混合物的总质量，加上粘结剂的质量之和，与有机溶剂的质量比为1∶3～50。 The mass ratio of the mass of graphene contained in the graphene conductive additive powder or slurry or the mixture of graphene and other conductive materials, plus the mass of the binder, to the organic solvent is 1:3-50 . the
优选，锂二次电池正极活性材料包括磷酸铁锂、磷酸铁锰锂、钴酸锂、尖晶石锰酸锂、层状锰酸锂、层状镍钴酸锂、尖晶石镍锰酸锂、层状富锂镍锰酸锂、层状镍钴锰酸锂三元材料或者钒酸锂；锂二次电池负极活性材料包括鳞片状石墨、改性天然石墨微球、人造石墨微球、中间相碳微球、钛酸锂、纳米硅或者硅碳复合材料。 Preferably, the positive electrode active material of the lithium secondary battery includes lithium iron phosphate, lithium iron manganese phosphate, lithium cobaltate, spinel lithium manganese oxide, layered lithium manganate, layered lithium nickel cobaltate, spinel lithium nickel manganese oxide , layered lithium-rich nickel manganese oxide lithium, layered nickel cobalt lithium manganese oxide ternary material or lithium vanadate; lithium secondary battery negative electrode active materials include scaly graphite, modified natural graphite microspheres, artificial graphite microspheres, intermediate Phase carbon microspheres, lithium titanate, nano-silicon or silicon-carbon composite materials. the
优选，石墨烯导电添加剂在锂二次电池正极中的添加量为0.5％-30％，质量百分含量，按照石墨烯或石墨烯与其它导电材料的混合物的固体质量计算；石墨烯导电添加剂在锂二次电池负极中的添加量为0.5％-10％，质量百分含量，按照石墨烯或石墨烯与乙炔黑混合物的固体质量计算。 Preferably, the addition amount of graphene conductive additive in lithium secondary battery positive electrode is 0.5%-30%, mass percentage content, calculates according to the solid mass of the mixture of graphene or graphene and other conductive materials; Graphene conductive additive is in The amount added to the negative electrode of the lithium secondary battery is 0.5%-10%, and the mass percentage is calculated according to the solid mass of graphene or a mixture of graphene and acetylene black. the
与现有技术相比，本发明的优点在于：与目前商品化的导电石墨、导电碳黑、Super P-Li及碳纳米管导电添加剂相比，石墨烯不仅具有极高的电导率，而且其独特的二维纳米结构能够极为有效地形成包裹于正负极活性材料周围的三维导电网络，同时二维片层状结构能够以面接触的方式与电极活性材料紧密接触，从而实现电子在电极中的快速迁移，利于高倍率充放电。同时，石墨烯良好的热导率对于快速传导充放电过程中产生的热量具有积极的意义，能够提升电池的高温性能和循环寿命。此外，石墨烯巨大的比表面积对于电解液良好的吸附与保持作用也有利于电池性能的提高。还需要指出的是，与高端的碳纳米管相比，石墨烯的制备成本更低，因此在实际应用中更具有优势。通过对多种不同锂二次电池正极、负极体系使用石墨烯导电剂后进行的充放电性能测试结果显示，石墨烯导电添加剂对于电池倍率性能的提升作用明显，并优于目前商品化的导电添加剂，是一款性能优越，且具有巨大市场前景的新型导电添加剂产品。 Compared with the prior art, the present invention has the advantages that: compared with current commercialized conductive graphite, conductive carbon black, Super P-Li and carbon nanotube conductive additives, graphene not only has extremely high electrical conductivity, but also has The unique two-dimensional nanostructure can effectively form a three-dimensional conductive network wrapped around the positive and negative active materials. The rapid migration is conducive to high-rate charge and discharge. At the same time, the good thermal conductivity of graphene has positive significance for the rapid conduction of heat generated during charge and discharge, which can improve the high temperature performance and cycle life of the battery. In addition, the huge specific surface area of graphene is good for the adsorption and retention of electrolyte, which is also conducive to the improvement of battery performance. It should also be pointed out that compared with high-end carbon nanotubes, graphene is cheaper to prepare, so it has more advantages in practical applications. The test results of charge and discharge performance after using graphene conductive agent on a variety of different lithium secondary battery positive and negative electrode systems show that the graphene conductive additive has a significant effect on improving the battery rate performance, and is better than the current commercialized conductive additives , is a new conductive additive product with superior performance and huge market prospects. the
附图说明Description of drawings
图1为添加石墨烯导电剂的磷酸铁锂正极材料的扫描电子显微镜图。 Figure 1 is a scanning electron microscope image of a lithium iron phosphate cathode material added with a graphene conductive agent. the
图2a、2b为在相同磷酸铁锂正极材料中分别添加同样质量百分含量(15％)的石墨 烯导电添加剂(左)和Super P-Li导电添加剂时(右)电池的放电曲线。结果显示，石墨烯导电添加剂对电池倍率性能的提升明显优于商品化的Super P-Li导电添加剂。 Figures 2a and 2b are the discharge curves of the battery when the same mass percentage (15%) of graphene conductive additive (left) and Super P-Li conductive additive (right) are added to the same lithium iron phosphate positive electrode material. The results show that the improvement of the battery rate performance by the graphene conductive additive is significantly better than that of the commercialized Super P-Li conductive additive. the
具体实施方式Detailed ways
以下结合实施例对本发明作进一步详细描述。 Below in conjunction with embodiment the present invention is described in further detail. the
实施例1 Example 1
称取0.2g聚偏氟乙烯(PVDF)粘结剂溶解于5克N-甲基吡咯烷酮中，再加入0.6g石墨烯粉体导电添加剂，搅拌均匀。随后加入3.2g磷酸铁锂正极活性材料，搅拌分散1小时。将所得浆料均匀涂布于铝箔上，于100℃真空下烘干，辊压后制成正极片。以LiPF6溶液为电解液，以Cellgard2400为隔膜，组装成锂离子电池。测得1C时放电容量为142mAh/g，10C时放电容量为110mAh/g，30C时放电容量为80mAh/g。电池在1C下充放电循环500次后，容量衰减小于5％。 Weigh 0.2g of polyvinylidene fluoride (PVDF) binder and dissolve it in 5 grams of N-methylpyrrolidone, then add 0.6g of graphene powder conductive additive, and stir evenly. Subsequently, 3.2 g of lithium iron phosphate positive electrode active material was added, stirred and dispersed for 1 hour. The obtained slurry was uniformly coated on an aluminum foil, dried under vacuum at 100° C., and rolled to form a positive electrode sheet. LiPF6 solution is used as the electrolyte and Cellgard2400 is used as the diaphragm to assemble a lithium-ion battery. The measured discharge capacity was 142mAh/g at 1C, 110mAh/g at 10C, and 80mAh/g at 30C. After the battery is charged and discharged 500 times at 1C, the capacity decay is less than 5%.
实施例2 Example 2
称取0.2g聚偏氟乙烯(PVDF)粘结剂溶解于5克N-甲基吡咯烷酮中，再加入0.2g石墨烯粉体导电添加剂，搅拌均匀。随后加入3.6g磷酸铁锂正极活性材料，搅拌分散1小时。将所得浆料均匀涂布于铝箔上，于100℃真空下烘干，辊压后制成正极片。以LiPF6溶液为电解液，以Cellgard2400为隔膜，组装成锂离子电池。测得1C时放电容量为140mAh/g，10C时放电容量为100mAh/g，30C时放电容量为60mAh/g。电池在1C下充放电循环500次后，容量衰减小于5％。 Weigh 0.2g of polyvinylidene fluoride (PVDF) binder and dissolve it in 5g of N-methylpyrrolidone, then add 0.2g of graphene powder conductive additive, and stir evenly. Subsequently, 3.6 g of lithium iron phosphate positive electrode active material was added, stirred and dispersed for 1 hour. The obtained slurry was uniformly coated on an aluminum foil, dried under vacuum at 100° C., and rolled to form a positive electrode sheet. LiPF6 solution is used as the electrolyte and Cellgard2400 is used as the diaphragm to assemble a lithium-ion battery. The measured discharge capacity was 140mAh/g at 1C, 100mAh/g at 10C, and 60mAh/g at 30C. After the battery is charged and discharged 500 times at 1C, the capacity decay is less than 5%.
实施例3 Example 3
称取1g石墨烯固体加入100gN-甲基吡咯烷酮中，超声处理15分钟得到均匀分散的石墨烯溶胶。采用离心将上述石墨烯溶胶浓缩至石墨烯质量浓度为5％的浆料。 Weighing 1g of graphene solids was added to 100g of N-methylpyrrolidone, and ultrasonically treated for 15 minutes to obtain a uniformly dispersed graphene sol. The above-mentioned graphene sol was concentrated to a slurry with a graphene mass concentration of 5% by centrifugation. the
称取0.2g聚偏氟乙烯(PVDF)粘结剂溶解于1克N-甲基吡咯烷酮中，再加入4g上一步中制得的质量浓度为5％的石墨烯浆料，搅拌均匀。随后加入3.6g磷酸铁锂正极活性材料，搅拌分散1小时。将所得浆料均匀涂布于铝箔上，于100℃真空下烘干，辊压后制成正极片。以LiPF6溶液为电解液，以Cellgard2400为隔膜，组装成锂离子电池。 测得1C时放电容量为140mAh/g，10C时放电容量为105mAh/g，30C时放电容量为69mAh/g。电池在1C下充放电循环500次后，容量衰减小于5％。 Weigh 0.2g of polyvinylidene fluoride (PVDF) binder and dissolve it in 1 gram of N-methylpyrrolidone, then add 4g of graphene slurry with a mass concentration of 5% prepared in the previous step, and stir evenly. Subsequently, 3.6 g of lithium iron phosphate positive electrode active material was added, stirred and dispersed for 1 hour. The obtained slurry was uniformly coated on an aluminum foil, dried under vacuum at 100° C., and rolled to form a positive electrode sheet. LiPF6 solution is used as the electrolyte and Cellgard2400 is used as the diaphragm to assemble a lithium-ion battery. The measured discharge capacity was 140mAh/g at 1C, 105mAh/g at 10C, and 69mAh/g at 30C. After the battery is charged and discharged 500 times at 1C, the capacity decay is less than 5%.
实施例4 Example 4
称取0.2g聚乙烯吡咯烷酮，溶解于100gN-甲基吡咯烷酮中，随后加入1g石墨烯固体，超声处理15分钟得到均匀分散的石墨烯溶胶。采用离心将上述石墨烯溶胶浓缩至石墨烯质量浓度为5％的浆料。 Weigh 0.2g of polyvinylpyrrolidone, dissolve it in 100g of N-methylpyrrolidone, then add 1g of graphene solid, and ultrasonicate for 15 minutes to obtain a uniformly dispersed graphene sol. The above-mentioned graphene sol was concentrated to a slurry with a graphene mass concentration of 5% by centrifugation. the
称取0.2g聚偏氟乙烯(PVDF)粘结剂溶解于1克N-甲基吡咯烷酮中，再加入4g上一步中制得的质量浓度为5％的石墨烯浆料，搅拌均匀。随后加入3.6g磷酸铁锂正极活性材料，搅拌分散1小时。将所得浆料均匀涂布于铝箔上，于100℃真空下烘干，辊压后制成正极片。以LiPF6溶液为电解液，以Cellgard2400为隔膜，组装成锂离子电池。测得1C时放电容量为141mAh/g，10C时放电容量为103mAh/g，30C时放电容量为66mAh/g。电池在1C下充放电循环500次后，容量衰减小于5％。 Weigh 0.2g of polyvinylidene fluoride (PVDF) binder and dissolve it in 1 gram of N-methylpyrrolidone, then add 4g of graphene slurry with a mass concentration of 5% prepared in the previous step, and stir evenly. Subsequently, 3.6 g of lithium iron phosphate positive electrode active material was added, stirred and dispersed for 1 hour. The obtained slurry was uniformly coated on an aluminum foil, dried under vacuum at 100° C., and rolled to form a positive electrode sheet. LiPF6 solution is used as the electrolyte and Cellgard2400 is used as the diaphragm to assemble a lithium-ion battery. The measured discharge capacity was 141mAh/g at 1C, 103mAh/g at 10C, and 66mAh/g at 30C. After the battery is charged and discharged 500 times at 1C, the capacity decay is less than 5%.
实施例5 Example 5
称取0.2g Pluoronic P123，溶解于100gN-甲基吡咯烷酮中，随后加入1g石墨烯固体，超声处理15分钟得到均匀分散的石墨烯溶胶。采用离心将上述石墨烯溶胶浓缩至石墨烯质量浓度为5％的浆料。 Weigh 0.2g of Pluoronic P123, dissolve it in 100g of N-methylpyrrolidone, then add 1g of graphene solid, and ultrasonicate for 15 minutes to obtain a uniformly dispersed graphene sol. The above-mentioned graphene sol was concentrated to a slurry with a graphene mass concentration of 5% by centrifugation. the
称取0.2g聚偏氟乙烯(PVDF)粘结剂溶解于1克N-甲基吡咯烷酮中，再加入4g上一步中制得的质量浓度为5％的石墨烯浆料，搅拌均匀。随后加入3.6g磷酸铁锂正极活性材料，搅拌分散1小时。将所得浆料均匀涂布于铝箔上，于100℃真空下烘干，辊压后制成正极片。以LiPF6溶液为电解液，以Cellgard2400为隔膜，组装成锂离子电池。测得1C时放电容量为141mAh/g，10C时放电容量为104mAh/g，30C时放电容量为65mAh/g。电池在1C下充放电循环500次后，容量衰减小于5％。 Weigh 0.2g of polyvinylidene fluoride (PVDF) binder and dissolve it in 1 gram of N-methylpyrrolidone, then add 4g of graphene slurry with a mass concentration of 5% prepared in the previous step, and stir evenly. Subsequently, 3.6 g of lithium iron phosphate positive electrode active material was added, stirred and dispersed for 1 hour. The obtained slurry was uniformly coated on an aluminum foil, dried under vacuum at 100° C., and rolled to form a positive electrode sheet. LiPF6 solution is used as the electrolyte and Cellgard2400 is used as the diaphragm to assemble a lithium-ion battery. The measured discharge capacity was 141mAh/g at 1C, 104mAh/g at 10C, and 65mAh/g at 30C. After the battery is charged and discharged 500 times at 1C, the capacity decay is less than 5%.
实施例6 Example 6
称取0.2g聚乙烯醇，溶解于100gN-甲基吡咯烷酮中，随后加入1g石墨烯固体，超声处理15分钟得到均匀分散的石墨烯溶胶。采用离心将上述石墨烯溶胶浓缩至石墨烯质量浓度为5％的浆料。 Weigh 0.2 g of polyvinyl alcohol, dissolve it in 100 g of N-methylpyrrolidone, then add 1 g of graphene solid, and perform ultrasonic treatment for 15 minutes to obtain a uniformly dispersed graphene sol. The above-mentioned graphene sol was concentrated to a slurry with a graphene mass concentration of 5% by centrifugation. the
称取0.2g聚偏氟乙烯(PVDF)粘结剂溶解于1克N-甲基吡咯烷酮中，再加入4g上一步中制得的质量浓度为5％的石墨烯浆料，搅拌均匀。随后加入3.6g磷酸铁锂正极活性材料，搅拌分散1小时。将所得浆料均匀涂布于铝箔上，于100℃真空下烘干，辊压后制成正极片。以LiPF6溶液为电解液，以Cellgard2400为隔膜，组装成锂离子电池。测得1C时放电容量为142mAh/g，10C时放电容量为102mAh/g，30C时放电容量为66mAh/g。电池在1C下充放电循环500次后，容量衰减小于5％。 Weigh 0.2g of polyvinylidene fluoride (PVDF) binder and dissolve it in 1 gram of N-methylpyrrolidone, then add 4g of graphene slurry with a mass concentration of 5% prepared in the previous step, and stir evenly. Subsequently, 3.6 g of lithium iron phosphate positive electrode active material was added, stirred and dispersed for 1 hour. The obtained slurry was uniformly coated on an aluminum foil, dried under vacuum at 100° C., and rolled to form a positive electrode sheet. LiPF6 solution is used as the electrolyte and Cellgard2400 is used as the diaphragm to assemble a lithium-ion battery. The measured discharge capacity was 142mAh/g at 1C, 102mAh/g at 10C, and 66mAh/g at 30C. After the battery is charged and discharged 500 times at 1C, the capacity decay is less than 5%.
实施例7 Example 7
称取0.2g聚氧乙烯月桂醚，溶解于100gN-甲基吡咯烷酮中，随后加入1g石墨烯固体，超声处理15分钟得到均匀分散的石墨烯溶胶。采用离心将上述石墨烯溶胶浓缩至石墨烯质量浓度为5％的浆料。 Weigh 0.2g of polyoxyethylene lauryl ether, dissolve it in 100g of N-methylpyrrolidone, then add 1g of graphene solid, and perform ultrasonic treatment for 15 minutes to obtain a uniformly dispersed graphene sol. The above-mentioned graphene sol was concentrated to a slurry with a graphene mass concentration of 5% by centrifugation. the
称取0.2g聚偏氟乙烯(PVDF)粘结剂溶解于1克N-甲基吡咯烷酮中，再加入4g上一步中制得的质量浓度为5％的石墨烯浆料，搅拌均匀。随后加入3.6g磷酸铁锂正极活性材料，搅拌分散1小时。将所得浆料均匀涂布于铝箔上，于100℃真空下烘干，辊压后制成正极片。以LiPF6溶液为电解液，以Cellgard2400为隔膜，组装成锂离子电池。测得1C时放电容量为141mAh/g，10C时放电容量为103mAh/g，30C时放电容量为66mAh/g。电池在1C下充放电循环500次后，容量衰减小于5％。 Weigh 0.2g of polyvinylidene fluoride (PVDF) binder and dissolve it in 1 gram of N-methylpyrrolidone, then add 4g of graphene slurry with a mass concentration of 5% prepared in the previous step, and stir evenly. Subsequently, 3.6 g of lithium iron phosphate positive electrode active material was added, stirred and dispersed for 1 hour. The obtained slurry was uniformly coated on an aluminum foil, dried under vacuum at 100° C., and rolled to form a positive electrode sheet. LiPF6 solution is used as the electrolyte and Cellgard2400 is used as the diaphragm to assemble a lithium-ion battery. The measured discharge capacity was 141mAh/g at 1C, 103mAh/g at 10C, and 66mAh/g at 30C. After the battery is charged and discharged 500 times at 1C, the capacity decay is less than 5%.
实施例8 Example 8
称取0.2g聚乙烯吡咯烷酮，溶解于100gN-甲基吡咯烷酮中，随后加入1g石墨烯固体和2g Super P-Li粉末，超声处理15分钟得到均匀分散的溶胶。采用离心将上述溶胶浓缩至固含量为10％(质量百分比)的浆料。 Weigh 0.2g of polyvinylpyrrolidone, dissolve it in 100g of N-methylpyrrolidone, then add 1g of graphene solid and 2g of Super P-Li powder, and ultrasonicate for 15 minutes to obtain a uniformly dispersed sol. The above sol was concentrated by centrifugation to a slurry with a solid content of 10% (mass percentage). the
称取0.2g聚偏氟乙烯(PVDF)粘结剂溶解于1克N-甲基吡咯烷酮中，再加入4g上一步中制得的质量浓度为10％的导电浆料，搅拌均匀。随后加入3.4g磷酸铁锂正极活性材料，搅拌分散1小时。将所得浆料均匀涂布于铝箔上，于100℃真空下烘干，辊压后制成正极片。以LiPF6溶液为电解液，以Cellgard2400为隔膜，组装成锂离子电池。测得1C时放电容量为141mAh/g，10C时放电容量为108mAh/g，30C时放电容量为76mAh/g。电池在1C下充放电循环500次后，容量衰减小于5％。 Weigh 0.2 g of polyvinylidene fluoride (PVDF) binder and dissolve it in 1 g of N-methylpyrrolidone, then add 4 g of the conductive paste with a mass concentration of 10% prepared in the previous step, and stir evenly. Subsequently, 3.4 g of lithium iron phosphate positive electrode active material was added, stirred and dispersed for 1 hour. The obtained slurry was uniformly coated on an aluminum foil, dried under vacuum at 100° C., and rolled to form a positive electrode sheet. LiPF6 solution is used as the electrolyte and Cellgard2400 is used as the diaphragm to assemble a lithium-ion battery. The measured discharge capacity was 141mAh/g at 1C, 108mAh/g at 10C, and 76mAh/g at 30C. After the battery is charged and discharged 500 times at 1C, the capacity decay is less than 5%.
实施例9 Example 9
称取0.2g聚乙烯吡咯烷酮，溶解于100gN-甲基吡咯烷酮中，随后加入1g石墨烯固体和2g乙炔黑粉末，超声处理15分钟得到均匀分散的溶胶。采用离心将上述溶胶浓缩至固含量为10％(质量百分比)的浆料。 Weigh 0.2g of polyvinylpyrrolidone, dissolve it in 100g of N-methylpyrrolidone, then add 1g of graphene solid and 2g of acetylene black powder, and ultrasonicate for 15 minutes to obtain a uniformly dispersed sol. The above sol was concentrated by centrifugation to a slurry with a solid content of 10% (mass percentage). the
称取0.2g聚偏氟乙烯(PVDF)粘结剂溶解于1克N-甲基吡咯烷酮中，再加入4g上一步中制得的质量浓度为10％的导电浆料，搅拌均匀。随后加入3.4g磷酸铁锂正极活性材料，搅拌分散1小时。将所得浆料均匀涂布于铝箔上，于100℃真空下烘干，辊压后制成正极片。以LiPF6溶液为电解液，以Cellgard2400为隔膜，组装成锂离子电池。测得1C时放电容量为140mAh/g，10C时放电容量为109mAh/g，30C时放电容量为78mAh/g。电池在1C下充放电循环500次后，容量衰减小于5％。 Weigh 0.2 g of polyvinylidene fluoride (PVDF) binder and dissolve it in 1 g of N-methylpyrrolidone, then add 4 g of the conductive paste with a mass concentration of 10% prepared in the previous step, and stir evenly. Subsequently, 3.4 g of lithium iron phosphate positive electrode active material was added, stirred and dispersed for 1 hour. The obtained slurry was uniformly coated on an aluminum foil, dried under vacuum at 100° C., and rolled to form a positive electrode sheet. LiPF6 solution is used as the electrolyte and Cellgard2400 is used as the diaphragm to assemble a lithium-ion battery. The measured discharge capacity was 140mAh/g at 1C, 109mAh/g at 10C, and 78mAh/g at 30C. After the battery is charged and discharged 500 times at 1C, the capacity decay is less than 5%.
实施例10 Example 10
称取0.4g聚乙烯吡咯烷酮，溶解于100gN-甲基吡咯烷酮中，随后加入2g石墨烯固体和1g碳纳米管，超声处理15分钟得到均匀分散的溶胶。采用离心将上述溶胶浓缩至固含量为5％(质量百分比)的浆料。 Weigh 0.4g of polyvinylpyrrolidone, dissolve it in 100g of N-methylpyrrolidone, then add 2g of graphene solids and 1g of carbon nanotubes, and ultrasonicate for 15 minutes to obtain a uniformly dispersed sol. The above sol was concentrated to a slurry with a solid content of 5% (mass percentage) by centrifugation. the
称取0.2g聚偏氟乙烯(PVDF)粘结剂溶解于1克N-甲基吡咯烷酮中，再加入4g上一步中制得的质量浓度为5％的导电浆料，搅拌均匀。随后加入3.6g磷酸铁锂正极活性材料，搅拌分散1小时。将所得浆料均匀涂布于铝箔上，于100℃真空下烘干，辊压后制成正极片。以LiPF6溶液为电解液，以Cellgard2400为隔膜，组装成锂离子电池。测得1C时放电容量为143mAh/g，10C时放电容量为112mAh/g，30C时放电容量为81mAh/g。电池在1C下充放电循环500次后，容量衰减小于5％。 Weigh 0.2 g of polyvinylidene fluoride (PVDF) binder and dissolve it in 1 g of N-methylpyrrolidone, then add 4 g of the conductive paste with a mass concentration of 5% prepared in the previous step, and stir evenly. Subsequently, 3.6 g of lithium iron phosphate positive electrode active material was added, stirred and dispersed for 1 hour. The obtained slurry was uniformly coated on an aluminum foil, dried under vacuum at 100° C., and rolled to form a positive electrode sheet. LiPF6 solution is used as the electrolyte and Cellgard2400 is used as the diaphragm to assemble a lithium-ion battery. The measured discharge capacity was 143mAh/g at 1C, 112mAh/g at 10C, and 81mAh/g at 30C. After the battery is charged and discharged 500 times at 1C, the capacity decay is less than 5%.
实施例11 Example 11
称取0.2g聚乙烯吡咯烷酮，溶解于100gN-甲基吡咯烷酮中，随后加入1g石墨烯固体、1g乙炔黑和1g碳纳米管，超声处理15分钟得到均匀分散的溶胶。采用离心将上述溶胶浓缩至固含量为5％(质量百分比)的浆料。 Weigh 0.2g of polyvinylpyrrolidone, dissolve it in 100g of N-methylpyrrolidone, then add 1g of graphene solid, 1g of acetylene black and 1g of carbon nanotubes, and ultrasonicate for 15 minutes to obtain a uniformly dispersed sol. The above sol was concentrated to a slurry with a solid content of 5% (mass percentage) by centrifugation. the
称取0.2g聚偏氟乙烯(PVDF)粘结剂溶解于1克N-甲基吡咯烷酮中，再加入4g上一步中制得的质量浓度为5％的导电浆料，搅拌均匀。随后加入3.6g磷酸铁锂正极活性材料，搅拌分散1小时。将所得浆料均匀涂布于铝箔上，于100℃真空下烘干，辊压 后制成正极片。以LiPF6溶液为电解液，以Cellgard2400为隔膜，组装成锂离子电池。测得1C时放电容量为141mAh/g，10C时放电容量为107mAh/g，30C时放电容量为73mAh/g。电池在1C下充放电循环500次后，容量衰减小于5％。 Weigh 0.2 g of polyvinylidene fluoride (PVDF) binder and dissolve it in 1 g of N-methylpyrrolidone, then add 4 g of the conductive paste with a mass concentration of 5% prepared in the previous step, and stir evenly. Subsequently, 3.6 g of lithium iron phosphate positive electrode active material was added, stirred and dispersed for 1 hour. The resulting slurry was uniformly coated on an aluminum foil, dried under vacuum at 100°C, and rolled to form a positive electrode sheet. LiPF6 solution is used as the electrolyte and Cellgard2400 is used as the diaphragm to assemble a lithium-ion battery. The measured discharge capacity was 141mAh/g at 1C, 107mAh/g at 10C, and 73mAh/g at 30C. After the battery is charged and discharged 500 times at 1C, the capacity decay is less than 5%.
实施例12 Example 12
称取0.2g聚乙烯吡咯烷酮，溶解于100gN-甲基吡咯烷酮中，随后加入1g石墨烯固体和1.5g乙炔黑和0.5g导电银颗粒，超声处理15分钟得到均匀分散的溶胶。采用离心将上述溶胶浓缩至固含量为5％(质量百分比)的浆料。 Weigh 0.2g of polyvinylpyrrolidone, dissolve it in 100g of N-methylpyrrolidone, then add 1g of graphene solid, 1.5g of acetylene black and 0.5g of conductive silver particles, and ultrasonicate for 15 minutes to obtain a uniformly dispersed sol. The above sol was concentrated to a slurry with a solid content of 5% (mass percentage) by centrifugation. the
称取0.2g聚偏氟乙烯(PVDF)粘结剂溶解于1克N-甲基吡咯烷酮中，再加入4g上一步中制得的质量浓度为5％的导电浆料，搅拌均匀。随后加入3.6g磷酸铁锂正极活性材料，搅拌分散1小时。将所得浆料均匀涂布于铝箔上，于100℃真空下烘干，辊压后制成正极片。以LiPF6溶液为电解液，以Cellgard2400为隔膜，组装成锂离子电池。测得1C时放电容量为140mAh/g，10C时放电容量为111mAh/g，30C时放电容量为77mAh/g。电池在1C下充放电循环500次后，容量衰减小于5％。 Weigh 0.2 g of polyvinylidene fluoride (PVDF) binder and dissolve it in 1 g of N-methylpyrrolidone, then add 4 g of the conductive paste with a mass concentration of 5% prepared in the previous step, and stir evenly. Subsequently, 3.6 g of lithium iron phosphate positive electrode active material was added, stirred and dispersed for 1 hour. The obtained slurry was uniformly coated on an aluminum foil, dried under vacuum at 100° C., and rolled to form a positive electrode sheet. LiPF6 solution is used as the electrolyte and Cellgard2400 is used as the diaphragm to assemble a lithium-ion battery. The measured discharge capacity was 140mAh/g at 1C, 111mAh/g at 10C, and 77mAh/g at 30C. After the battery is charged and discharged 500 times at 1C, the capacity decay is less than 5%.
实施例13 Example 13
称取0.2g聚乙烯吡咯烷酮，溶解于100gN-甲基吡咯烷酮中，随后加入1g石墨烯固体，超声处理15分钟得到均匀分散的石墨烯溶胶。采用离心将上述石墨烯溶胶浓缩至石墨烯质量浓度为5％的浆料。 Weigh 0.2g of polyvinylpyrrolidone, dissolve it in 100g of N-methylpyrrolidone, then add 1g of graphene solid, and ultrasonicate for 15 minutes to obtain a uniformly dispersed graphene sol. The above-mentioned graphene sol was concentrated to a slurry with a graphene mass concentration of 5% by centrifugation. the
称取0.2g聚偏氟乙烯(PVDF)粘结剂溶解于1克N-甲基吡咯烷酮中，再加入4g上一步中制得的质量浓度为5％的石墨烯浆料，搅拌均匀。随后加入3.6g钴酸锂正极活性材料，搅拌分散1小时。将所得浆料均匀涂布于铝箔上，于100℃真空下烘干，辊压后制成正极片。以LiPF6溶液为电解液，以Cellgard2400为隔膜，组装成锂离子电池。测得0.1C时放电容量为145mAh/g，1C时放电容量为138mAh/g。 Weigh 0.2g of polyvinylidene fluoride (PVDF) binder and dissolve it in 1 gram of N-methylpyrrolidone, then add 4g of graphene slurry with a mass concentration of 5% prepared in the previous step, and stir evenly. Subsequently, 3.6 g of lithium cobaltate positive electrode active material was added, stirred and dispersed for 1 hour. The obtained slurry was uniformly coated on an aluminum foil, dried under vacuum at 100° C., and rolled to form a positive electrode sheet. LiPF6 solution is used as the electrolyte and Cellgard2400 is used as the diaphragm to assemble a lithium-ion battery. The measured discharge capacity was 145mAh/g at 0.1C and 138mAh/g at 1C.
实施例14 Example 14
称取0.2g聚乙烯吡咯烷酮，溶解于100gN-甲基吡咯烷酮中，随后加入1g石墨烯固体，超声处理15分钟得到均匀分散的石墨烯溶胶。采用离心将上述石墨烯溶胶浓缩至石墨烯质量浓度为5％的浆料。 Weigh 0.2g of polyvinylpyrrolidone, dissolve it in 100g of N-methylpyrrolidone, then add 1g of graphene solid, and ultrasonicate for 15 minutes to obtain a uniformly dispersed graphene sol. The above-mentioned graphene sol was concentrated to a slurry with a graphene mass concentration of 5% by centrifugation. the
称取0.2g聚偏氟乙烯(PVDF)粘结剂溶解于1克N-甲基吡咯烷酮中，再加入4g上一步中制得的质量浓度为5％的石墨烯浆料，搅拌均匀。随后加入3.6g尖晶石锰酸锂正极活性材料，搅拌分散1小时。将所得浆料均匀涂布于铝箔上，于100℃真空下烘干，辊压后制成正极片。以LiPF6溶液为电解液，以Cellgard2400为隔膜，组装成锂离子电池。测得0.1C时放电容量为132mAh/g，1C时放电容量为111mAh/g。 Weigh 0.2g of polyvinylidene fluoride (PVDF) binder and dissolve it in 1 gram of N-methylpyrrolidone, then add 4g of graphene slurry with a mass concentration of 5% prepared in the previous step, and stir evenly. Subsequently, 3.6 g of spinel lithium manganate positive electrode active material was added, stirred and dispersed for 1 hour. The obtained slurry was uniformly coated on an aluminum foil, dried under vacuum at 100° C., and rolled to form a positive electrode sheet. LiPF6 solution is used as the electrolyte and Cellgard2400 is used as the diaphragm to assemble a lithium-ion battery. The measured discharge capacity was 132mAh/g at 0.1C and 111mAh/g at 1C.
实施例15 Example 15
称取0.2g聚乙烯吡咯烷酮，溶解于100gN-甲基吡咯烷酮中，随后加入1g石墨烯固体，超声处理15分钟得到均匀分散的石墨烯溶胶。采用离心将上述石墨烯溶胶浓缩至石墨烯质量浓度为5％的浆料。 Weigh 0.2g of polyvinylpyrrolidone, dissolve it in 100g of N-methylpyrrolidone, then add 1g of graphene solid, and ultrasonicate for 15 minutes to obtain a uniformly dispersed graphene sol. The above-mentioned graphene sol was concentrated to a slurry with a graphene mass concentration of 5% by centrifugation. the
称取0.2g聚偏氟乙烯(PVDF)粘结剂溶解于1克N-甲基吡咯烷酮中，再加入4g上一步中制得的质量浓度为5％的石墨烯浆料，搅拌均匀。随后加入3.6g镍钴酸锂正极活性材料，搅拌分散1小时。将所得浆料均匀涂布于铝箔上，于100℃真空下烘干，辊压后制成正极片。以LiPF6溶液为电解液，以Cellgard2400为隔膜，组装成锂离子电池。测得0.1C时放电容量为175mAh/g，1C时放电容量为155mAh/g。 Weigh 0.2g of polyvinylidene fluoride (PVDF) binder and dissolve it in 1 gram of N-methylpyrrolidone, then add 4g of graphene slurry with a mass concentration of 5% prepared in the previous step, and stir evenly. Subsequently, 3.6 g of lithium nickel cobaltate positive electrode active material was added, stirred and dispersed for 1 hour. The obtained slurry was uniformly coated on an aluminum foil, dried under vacuum at 100° C., and rolled to form a positive electrode sheet. LiPF6 solution is used as the electrolyte and Cellgard2400 is used as the diaphragm to assemble a lithium-ion battery. The measured discharge capacity was 175mAh/g at 0.1C and 155mAh/g at 1C.
实施例16 Example 16
称取0.2g聚乙烯吡咯烷酮，溶解于100gN-甲基吡咯烷酮中，随后加入1g石墨烯固体，超声处理15分钟得到均匀分散的石墨烯溶胶。采用离心将上述石墨烯溶胶浓缩至石墨烯质量浓度为5％的浆料。 Weigh 0.2g of polyvinylpyrrolidone, dissolve it in 100g of N-methylpyrrolidone, then add 1g of graphene solid, and ultrasonicate for 15 minutes to obtain a uniformly dispersed graphene sol. The above-mentioned graphene sol was concentrated to a slurry with a graphene mass concentration of 5% by centrifugation. the
称取0.2g聚偏氟乙烯(PVDF)粘结剂溶解于1克N-甲基吡咯烷酮中，再加入4g上一步中制得的质量浓度为5％的石墨烯浆料，搅拌均匀。随后加入3.6g镍钴锰酸锂三元正极活性材料，搅拌分散1小时。将所得浆料均匀涂布于铝箔上，于100℃真空下烘干，辊压后制成正极片。以LiPF6溶液为电解液，以Cellgard2400为隔膜，组装成锂离子电池。测得0.1C时放电容量为188mAh/g，1C时放电容量为169mAh/g。 Weigh 0.2g of polyvinylidene fluoride (PVDF) binder and dissolve it in 1 gram of N-methylpyrrolidone, then add 4g of graphene slurry with a mass concentration of 5% prepared in the previous step, and stir evenly. Subsequently, 3.6 g of lithium nickel cobalt manganese oxide ternary positive electrode active material was added, stirred and dispersed for 1 hour. The obtained slurry was uniformly coated on an aluminum foil, dried under vacuum at 100° C., and rolled to form a positive electrode sheet. LiPF6 solution is used as the electrolyte and Cellgard2400 is used as the diaphragm to assemble a lithium-ion battery. The measured discharge capacity was 188mAh/g at 0.1C and 169mAh/g at 1C.
实施例17 Example 17
称取1g石墨烯固体加入100gN-甲基吡咯烷酮中，超声处理15分钟得到均匀分散的石墨烯溶胶。采用离心将上述石墨烯溶胶浓缩至石墨烯质量浓度为5％的浆料。 Weighing 1g of graphene solids was added to 100g of N-methylpyrrolidone, and ultrasonically treated for 15 minutes to obtain a uniformly dispersed graphene sol. The above-mentioned graphene sol was concentrated to a slurry with a graphene mass concentration of 5% by centrifugation. the
称取0.2g聚偏氟乙烯(PVDF)粘结剂溶解于3克N-甲基吡咯烷酮中，再加入2g上一步中制得的质量浓度为5％的石墨烯浆料，搅拌均匀。随后加入3.7g改性天然石墨微球负极活性材料，搅拌分散1小时。将所得浆料均匀涂布于铜箔上，于100℃真空下烘干，辊压后制成负极片。以LiPF6溶液为电解液，以Cellgard2400为隔膜，组装成锂离子电池。测得0.1C时容量为355mAh/g，1C时容量为315mAh/g。 Weigh 0.2g of polyvinylidene fluoride (PVDF) binder and dissolve it in 3 grams of N-methylpyrrolidone, then add 2g of graphene slurry with a mass concentration of 5% prepared in the previous step, and stir evenly. Subsequently, 3.7 g of the modified natural graphite microsphere negative electrode active material was added, stirred and dispersed for 1 hour. The obtained slurry was uniformly coated on a copper foil, dried under vacuum at 100° C., and rolled to form a negative electrode sheet. LiPF6 solution is used as the electrolyte and Cellgard2400 is used as the diaphragm to assemble a lithium-ion battery. The measured capacity is 355mAh/g at 0.1C and 315mAh/g at 1C.
实施例18 Example 18
称取1g聚乙烯吡咯烷酮，溶解于100g水中，随后加入1g石墨烯固体，超声处理15分钟得到均匀分散的石墨烯溶胶。采用离心将上述石墨烯溶胶浓缩至石墨烯质量浓度为5％的浆料。 Weigh 1 g of polyvinylpyrrolidone, dissolve it in 100 g of water, then add 1 g of graphene solid, and perform ultrasonic treatment for 15 minutes to obtain a uniformly dispersed graphene sol. The above-mentioned graphene sol was concentrated to a slurry with a graphene mass concentration of 5% by centrifugation. the
称取0.2g聚偏氟乙烯(PVDF)粘结剂溶解于3克水中，再加入2g上一步中制得的质量浓度为5％的石墨烯浆料，搅拌均匀。随后加入3.7g改性天然石墨微球负极活性材料，搅拌分散1小时。将所得浆料均匀涂布于铜箔上，于100℃真空下烘干，辊压后制成负极片。以LiPF6溶液为电解液，以Cellgard2400为隔膜，组装成锂离子电池。测得0.1C时容量为353mAh/g，1C时容量为311mAh/g。 Weigh 0.2g polyvinylidene fluoride (PVDF) binder and dissolve it in 3 grams of water, then add 2g of graphene slurry with a mass concentration of 5% prepared in the previous step, and stir evenly. Subsequently, 3.7 g of the modified natural graphite microsphere negative electrode active material was added, stirred and dispersed for 1 hour. The obtained slurry was uniformly coated on a copper foil, dried under vacuum at 100° C., and rolled to form a negative electrode sheet. LiPF6 solution is used as the electrolyte and Cellgard2400 is used as the diaphragm to assemble a lithium-ion battery. The measured capacity was 353mAh/g at 0.1C and 311mAh/g at 1C.
实施例19 Example 19
称取1g石墨烯固体加入100gN-甲基吡咯烷酮中，超声处理15分钟得到均匀分散的石墨烯溶胶。采用离心将上述石墨烯溶胶浓缩至石墨烯质量浓度为5％的浆料。 Weighing 1g of graphene solids was added to 100g of N-methylpyrrolidone, and ultrasonically treated for 15 minutes to obtain a uniformly dispersed graphene sol. The above-mentioned graphene sol was concentrated to a slurry with a graphene mass concentration of 5% by centrifugation. the
称取0.2g聚偏氟乙烯(PVDF)粘结剂溶解于3克N-甲基吡咯烷酮中，再加入2g上一步中制得的质量浓度为5％的石墨烯浆料，搅拌均匀。随后加入3.7g中间相碳微球负极活性材料，搅拌分散1小时。将所得浆料均匀涂布于铜箔上，于100℃真空下烘干，辊压后制成负极片。以LiPF6溶液为电解液，以Cellgard2400为隔膜，组装成锂离子电池。测得0.1C时容量为359mAh/g，1C时容量为317mAh/g。 Weigh 0.2g of polyvinylidene fluoride (PVDF) binder and dissolve it in 3 grams of N-methylpyrrolidone, then add 2g of graphene slurry with a mass concentration of 5% prepared in the previous step, and stir evenly. Subsequently, 3.7 g of the mesophase carbon microsphere negative electrode active material was added, stirred and dispersed for 1 hour. The obtained slurry was uniformly coated on a copper foil, dried under vacuum at 100° C., and rolled to form a negative electrode sheet. LiPF6 solution is used as the electrolyte and Cellgard2400 is used as the diaphragm to assemble a lithium-ion battery. The measured capacity was 359mAh/g at 0.1C and 317mAh/g at 1C.
实施例20 Example 20
称取1g石墨烯固体加入100gN-甲基吡咯烷酮中，超声处理15分钟得到均匀分散的石墨烯溶胶。采用离心将上述石墨烯溶胶浓缩至石墨烯质量浓度为5％的浆料。 Weighing 1g of graphene solids was added to 100g of N-methylpyrrolidone, and ultrasonically treated for 15 minutes to obtain a uniformly dispersed graphene sol. The above-mentioned graphene sol was concentrated to a slurry with a graphene mass concentration of 5% by centrifugation. the
称取0.2g聚偏氟乙烯(PVDF)粘结剂溶解于3克N-甲基吡咯烷酮中，再加入2g 上一步中制得的质量浓度为5％的石墨烯浆料，搅拌均匀。随后加入3.7g钛酸锂负极活性材料，搅拌分散1小时。将所得浆料均匀涂布于铜箔上，于100℃真空下烘干，辊压后制成负极片。以LiPF6溶液为电解液，以Cellgard2400为隔膜，组装成锂离子电池。测得0.1C时容量为161mAh/g，1C时放电容量为153mAh/g，10C时放电容量为131mAh/g。 Weigh 0.2g of polyvinylidene fluoride (PVDF) binder and dissolve it in 3 grams of N-methylpyrrolidone, then add 2g of graphene slurry with a mass concentration of 5% prepared in the previous step, and stir evenly. Subsequently, 3.7 g of lithium titanate negative electrode active material was added, stirred and dispersed for 1 hour. The obtained slurry was uniformly coated on a copper foil, dried under vacuum at 100° C., and rolled to form a negative electrode sheet. LiPF6 solution is used as the electrolyte and Cellgard2400 is used as the diaphragm to assemble a lithium-ion battery. The measured capacity was 161mAh/g at 0.1C, 153mAh/g at 1C, and 131mAh/g at 10C.
实施例21 Example 21
称取1g石墨烯固体加入100gN-甲基吡咯烷酮中，超声处理15分钟得到均匀分散的石墨烯溶胶。采用离心将上述石墨烯溶胶浓缩至石墨烯质量浓度为5％的浆料。 Weighing 1g of graphene solids was added to 100g of N-methylpyrrolidone, and ultrasonically treated for 15 minutes to obtain a uniformly dispersed graphene sol. The above-mentioned graphene sol was concentrated to a slurry with a graphene mass concentration of 5% by centrifugation. the
称取0.2g聚偏氟乙烯(PVDF)粘结剂溶解于3克N-甲基吡咯烷酮中，再加入2g上一步中制得的质量浓度为5％的石墨烯浆料，搅拌均匀。随后加入3.7g纳米硅负极活性材料，搅拌分散1小时。将所得浆料均匀涂布于铜箔上，于100℃真空下烘干，辊压后制成负极片。以LiPF6溶液为电解液，以Cellgard2400为隔膜，组装成锂离子电池。测得50mA/g电流密度时比容量为1790mAh/g，500mA/g电流密度时的比容量为1231mAh/g。 Weigh 0.2g of polyvinylidene fluoride (PVDF) binder and dissolve it in 3 grams of N-methylpyrrolidone, then add 2g of graphene slurry with a mass concentration of 5% prepared in the previous step, and stir evenly. Subsequently, 3.7 g of nano-silicon negative electrode active material was added, stirred and dispersed for 1 hour. The obtained slurry was uniformly coated on a copper foil, dried under vacuum at 100° C., and rolled to form a negative electrode sheet. LiPF6 solution is used as the electrolyte and Cellgard2400 is used as the diaphragm to assemble a lithium-ion battery. When the current density of 50mA/g is measured, the specific capacity is 1790mAh/g, and when the current density is 500mA/g, the specific capacity is 1231mAh/g.
实施例22 Example 22
称取1g聚乙烯醇，溶解于100g水中，随后加入1g石墨烯固体，超声处理15分钟得到均匀分散的石墨烯溶胶。采用离心将上述石墨烯溶胶浓缩至石墨烯质量浓度为5％的浆料。 Weigh 1 g of polyvinyl alcohol, dissolve it in 100 g of water, then add 1 g of graphene solid, and perform ultrasonic treatment for 15 minutes to obtain a uniformly dispersed graphene sol. The above-mentioned graphene sol was concentrated to a slurry with a graphene mass concentration of 5% by centrifugation. the
称取0.2g聚偏氟乙烯(PVDF)粘结剂溶解于3克水中，再加入2g上一步中制得的质量浓度为5％的石墨烯浆料，搅拌均匀。随后加入3.7g改性天然石墨微球负极活性材料，搅拌分散1小时。将所得浆料均匀涂布于铜箔上，于100℃真空下烘干，辊压后制成负极片。以LiPF6溶液为电解液，以Cellgard2400为隔膜，组装成锂离子电池。测得0.1C时的容量为357mAh/g，1C时放电容量为313mAh/g。 Weigh 0.2g polyvinylidene fluoride (PVDF) binder and dissolve it in 3 grams of water, then add 2g of graphene slurry with a mass concentration of 5% prepared in the previous step, and stir evenly. Subsequently, 3.7 g of the modified natural graphite microsphere negative electrode active material was added, stirred and dispersed for 1 hour. The obtained slurry was uniformly coated on a copper foil, dried under vacuum at 100° C., and rolled to form a negative electrode sheet. LiPF6 solution is used as the electrolyte and Cellgard2400 is used as the diaphragm to assemble a lithium-ion battery. The measured capacity at 0.1C is 357mAh/g, and the discharge capacity at 1C is 313mAh/g.
实施例23 Example 23
称取0.2g聚乙烯吡咯烷酮，溶解于100gN-甲基吡咯烷酮中，随后加入1g石墨烯固体和2g Super P-Li粉末，先高速机械搅拌混合10分钟，再超声处理15分钟得到均匀分 散的溶胶。采用离心将上述溶胶浓缩至固含量为10％(质量百分比)的浆料。 Weigh 0.2g of polyvinylpyrrolidone, dissolve it in 100g of N-methylpyrrolidone, then add 1g of graphene solid and 2g of Super P-Li powder, first mix with high-speed mechanical stirring for 10 minutes, and then ultrasonicate for 15 minutes to obtain a uniformly dispersed sol . The above sol was concentrated by centrifugation to a slurry with a solid content of 10% (mass percentage). the
称取0.2g聚偏氟乙烯(PVDF)粘结剂溶解于1克N-甲基吡咯烷酮中，再加入4g上一步中制得的质量浓度为10％的导电浆料，搅拌均匀。随后加入3.4g磷酸铁锂正极活性材料，搅拌分散1小时。将所得浆料均匀涂布于铝箔上，于100℃真空下烘干，辊压后制成正极片。以LiPF6溶液为电解液，以Cellgard2400为隔膜，组装成锂离子电池。测得1C时放电容量为142mAh/g，10C时放电容量为107mAh/g，30C时放电容量为73mAh/g。 Weigh 0.2 g of polyvinylidene fluoride (PVDF) binder and dissolve it in 1 g of N-methylpyrrolidone, then add 4 g of the conductive paste with a mass concentration of 10% prepared in the previous step, and stir evenly. Subsequently, 3.4 g of lithium iron phosphate positive electrode active material was added, stirred and dispersed for 1 hour. The obtained slurry was uniformly coated on an aluminum foil, dried under vacuum at 100° C., and rolled to form a positive electrode sheet. LiPF6 solution is used as the electrolyte and Cellgard2400 is used as the diaphragm to assemble a lithium-ion battery. The measured discharge capacity was 142mAh/g at 1C, 107mAh/g at 10C, and 73mAh/g at 30C.
实施例24 Example 24
称取0.2g聚乙烯吡咯烷酮，溶解于100gN-甲基吡咯烷酮中，随后加入1g石墨烯固体和乙炔黑粉末，超声处理15分钟得到均匀分散的溶胶。采用离心将上述溶胶浓缩至固含量为10％(质量百分比)的浆料。 Weigh 0.2g of polyvinylpyrrolidone, dissolve it in 100g of N-methylpyrrolidone, then add 1g of graphene solid and acetylene black powder, and ultrasonicate for 15 minutes to obtain a uniformly dispersed sol. The above sol was concentrated by centrifugation to a slurry with a solid content of 10% (mass percentage). the
后续步骤与实施例8相同。 Subsequent steps are the same as in Example 8. the
实施例25 Example 25
称取0.2g聚乙烯吡咯烷酮，溶解于100gN-甲基吡咯烷酮中，随后加入1g石墨烯固体和2g导电碳黑粉末，先高速机械搅拌混合10分找，再超声处理15分钟得到均匀分散的溶胶。采用离心将上述溶胶浓缩至固含量为10％(质量百分比)的浆料。 Weigh 0.2g of polyvinylpyrrolidone, dissolve it in 100g of N-methylpyrrolidone, then add 1g of graphene solid and 2g of conductive carbon black powder, first mix with high-speed mechanical stirring for 10 minutes, and then ultrasonicate for 15 minutes to obtain a uniformly dispersed sol. The above sol was concentrated by centrifugation to a slurry with a solid content of 10% (mass percentage). the
后续步骤与实施例8相同。 Subsequent steps are the same as in Example 8. the
实施例26 Example 26
称取0.4g聚乙烯吡咯烷酮，溶解于100gN-甲基吡咯烷酮中，随后加入2g石墨烯固体和1g导电银颗粒，超声处理15分钟得到均匀分散的溶胶。采用离心将上述溶胶浓缩至固含量为5％(质量百分比)的浆料。 Weigh 0.4g of polyvinylpyrrolidone, dissolve it in 100g of N-methylpyrrolidone, then add 2g of graphene solids and 1g of conductive silver particles, and ultrasonicate for 15 minutes to obtain a uniformly dispersed sol. The above sol was concentrated to a slurry with a solid content of 5% (mass percentage) by centrifugation. the
后续步骤与实施例10相同。 Subsequent steps are the same as in Example 10. the
实施例27 Example 27
称取0.4g聚乙烯吡咯烷酮，溶解于100gN-甲基吡咯烷酮中，随后加入2g石墨烯固体和1g导电铜纤维，超声处理15分钟得到均匀分散的溶胶。采用离心将上述溶胶浓缩至固含量为5％(质量百分比)的浆料。 Weigh 0.4g of polyvinylpyrrolidone, dissolve it in 100g of N-methylpyrrolidone, then add 2g of graphene solid and 1g of conductive copper fiber, and ultrasonicate for 15 minutes to obtain a uniformly dispersed sol. The above sol was concentrated to a slurry with a solid content of 5% (mass percentage) by centrifugation. the
后续步骤与实施例10相同。 Subsequent steps are the same as in Example 10. the
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Cited By (76)
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|---|---|---|---|---|
| CN102751486A (en)* | 2012-07-18 | 2012-10-24 | 中国科学院福建物质结构研究所 | Method for preparing lithium cobalt oxide nanosheets |
| CN103035887A (en)* | 2012-12-17 | 2013-04-10 | 鸿纳（东莞）新材料科技有限公司 | High-concentration few-layer graphene composite material, component of lithium battery electrode and preparation |
| CN103050704A (en)* | 2012-12-28 | 2013-04-17 | 清华大学深圳研究生院 | Porous conductive additive and preparation method thereof, lithium ion battery |
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| CN105514407A (en)* | 2016-01-25 | 2016-04-20 | 张博 | Preparation method of cold-resistant lithium manganate-lithium titanate battery |
| CN105552376A (en)* | 2016-01-05 | 2016-05-04 | 厦门凯纳石墨烯技术股份有限公司 | Polyvinyl pyrrolidone/graphene conductive slurry, and preparation method and application thereof |
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| CN105655652A (en)* | 2016-01-25 | 2016-06-08 | 张博 | Preparation method of graphene low-temperature battery |
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| CN106450169A (en)* | 2016-08-31 | 2017-02-22 | 湖北宇电能源科技股份有限公司 | Manufacturing method of negative plate of safety lithium-ion battery |
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| CN109643823A (en)* | 2016-08-22 | 2019-04-16 | 日立化成株式会社 | Lithium ion secondary battery |
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| CN109888292A (en)* | 2019-04-03 | 2019-06-14 | 山东星火科学技术研究院 | A kind of graphene carbon black binary conductive additive and preparation method thereof |
| CN110120499A (en)* | 2019-05-10 | 2019-08-13 | 华瑞墨石丹阳有限公司 | A kind of graphite nano plate and its preparation method and application |
| CN110233266A (en)* | 2019-07-02 | 2019-09-13 | 宁夏汉尧石墨烯储能材料科技有限公司 | A kind of preparation method of graphene modification lithium-ion battery tertiary cathode material |
| TWI692441B (en)* | 2018-01-17 | 2020-05-01 | 中原大學 | Graphene structure, method of producing graphene and electrode of lithium-ion made of the same |
| CN111293278A (en)* | 2020-03-24 | 2020-06-16 | 东莞市智元电池新材料有限公司 | A kind of preparation method of water-based primer slurry for graphene lithium ion battery |
| CN111559739A (en)* | 2020-03-30 | 2020-08-21 | 桑顿新能源科技有限公司 | High-rate lithium ferric manganese phosphate composite material, preparation method thereof and lithium ion battery |
| CN111933949A (en)* | 2020-08-18 | 2020-11-13 | 东莞市海洲新材料科技有限公司 | Graphene conductive agent with adjustable sheet diameter distribution ratio, preparation method thereof, negative electrode and lithium ion battery |
| CN113809299A (en)* | 2021-09-14 | 2021-12-17 | 远景动力技术(江苏)有限公司 | Negative electrode active material, negative electrode sheet, preparation method and application of negative electrode sheet |
| CN114497561A (en)* | 2021-12-29 | 2022-05-13 | 天津先众新能源科技股份有限公司 | Positive electrode conductive additive for rate start battery and preparation method thereof |
| 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 |
| CN116532017A (en)* | 2023-04-21 | 2023-08-04 | 盐城工学院 | Homogenization method of battery anode material |
| CN116686117A (en)* | 2020-12-25 | 2023-09-01 | 大金工业株式会社 | Method for producing sheet for solid-state secondary battery, and binder for solid-state secondary battery |
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Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106058252A (en)* | 2016-08-17 | 2016-10-26 | 江苏金坛绿能新能源科技有限公司 | Lithium ion battery cathode slurry and preparation method thereof |
| JPWO2023140311A1 (en)* | 2022-01-21 | 2023-07-27 |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0222854A1 (en)* | 1985-05-13 | 1987-05-27 | Thomson Brandt Gmbh | Telecontrol unit for leisure electronic apparatuses. |
| CN1770515A (en)* | 2005-08-22 | 2006-05-10 | 中国科学院成都有机化学有限公司 | A kind of lithium-ion secondary battery positive electrode, negative electrode material conductive agent and preparation method thereof |
| CN101154723A (en)* | 2007-05-15 | 2008-04-02 | 唐旦超 | Method of producing anode composite material of nickel series secondary battery and products produced thereby |
| CN101710619A (en)* | 2009-12-14 | 2010-05-19 | 重庆大学 | Electrode plate for lithium ion battery and manufacturing method thereof |
- 2010
- 2010-12-09CNCN201010595726.6Apatent/CN102544502B/enactiveActive
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0222854A1 (en)* | 1985-05-13 | 1987-05-27 | Thomson Brandt Gmbh | Telecontrol unit for leisure electronic apparatuses. |
| CN1770515A (en)* | 2005-08-22 | 2006-05-10 | 中国科学院成都有机化学有限公司 | A kind of lithium-ion secondary battery positive electrode, negative electrode material conductive agent and preparation method thereof |
| CN101154723A (en)* | 2007-05-15 | 2008-04-02 | 唐旦超 | Method of producing anode composite material of nickel series secondary battery and products produced thereby |
| CN101710619A (en)* | 2009-12-14 | 2010-05-19 | 重庆大学 | Electrode plate for lithium ion battery and manufacturing method thereof |
Cited By (107)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103545525A (en)* | 2012-07-17 | 2014-01-29 | 南京宏德纳米材料有限公司 | Lithium ion battery nano composite positive-negative electrode material containing three-dimensional conductive network as well as preparation method thereof |
| CN103545525B (en)* | 2012-07-17 | 2016-02-24 | 南京宏德纳米材料有限公司 | Lithium ion cell nano compound positive and negative electrode material containing three dimensions conductive network and preparation method |
| CN102751486A (en)* | 2012-07-18 | 2012-10-24 | 中国科学院福建物质结构研究所 | Method for preparing lithium cobalt oxide nanosheets |
| CN102751486B (en)* | 2012-07-18 | 2015-12-16 | 中国科学院福建物质结构研究所 | A kind of preparation method of cobalt acid lithium nanometer sheet |
| CN103840164A (en)* | 2012-11-23 | 2014-06-04 | 中国科学院金属研究所 | Method for using carbon nano conductive agent in lithium ion battery aqueous slurry |
| CN103035887A (en)* | 2012-12-17 | 2013-04-10 | 鸿纳（东莞）新材料科技有限公司 | High-concentration few-layer graphene composite material, component of lithium battery electrode and preparation |
| CN103035887B (en)* | 2012-12-17 | 2015-08-19 | 鸿纳（东莞）新材料科技有限公司 | A kind of preparation method of electrode of lithium cell |
| CN103050704B (en)* | 2012-12-28 | 2015-04-01 | 清华大学深圳研究生院 | Porous conductive additive and preparation method thereof, lithium ion battery |
| CN103050704A (en)* | 2012-12-28 | 2013-04-17 | 清华大学深圳研究生院 | Porous conductive additive and preparation method thereof, lithium ion battery |
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| CN103247779A (en)* | 2013-04-16 | 2013-08-14 | 谭彬 | Production method of electrochemical active pole piece |
| CN103198935A (en)* | 2013-04-18 | 2013-07-10 | 山东大学 | Preparation method of graphene sheet modified spinel type lithium manganate or alpha type manganese dioxide electrode |
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| CN103311503A (en)* | 2013-05-17 | 2013-09-18 | 贵州航天电源科技有限公司 | Dispersion method of lithium-ion battery paste |
| CN103288075A (en)* | 2013-05-24 | 2013-09-11 | 大连理工大学 | Nitrogen-doped graphene nanoribbon and preparation method thereof |
| CN103296312A (en)* | 2013-06-05 | 2013-09-11 | 宜兴奕润新能源科技有限公司 | Preparation method of large-power high-magnification lithium iron phosphate battery |
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| CN103390780A (en)* | 2013-08-15 | 2013-11-13 | 刘洪� | Environment-friendly iron phosphate magnesium lithium battery and preparation method thereof |
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