技术领域technical field
本发明涉及一种碳系活性复合物，尤其是涉及一种多维结构高容量能源储存材料及其制作方法，该多维碳系纳米级活性复合物，可用以制造高能量密度的能源储存装置，特别是锂离子二次电池芯及以利用其所制得的电池组。The present invention relates to a carbon-based active compound, in particular to a multi-dimensional structure high-capacity energy storage material and a manufacturing method thereof. The multi-dimensional carbon-based nanoscale active compound can be used to manufacture high-energy-density energy storage devices, especially It is a lithium-ion secondary battery core and a battery pack made by using it.
背景技术Background technique
在现今科技革命与环保意识抬头的二十一世纪，为了因应新世代的科技与绿能产品快速演进，消费者对储能产品效能要求与需求也同步成长。对于例如携带型的3C产品，例如手机、掌上型计算机(PDA)、智能型手机(Smartphone)、笔记型(平板)计算机、数字相机等，或是电动车、油电混合车等等大型交通工具来说，储能装置的电容量、寿命甚至是输出功率等要求都日趋严苛，同时因环保意识的抬头，消费者同时对产品生产过程也投以关注，因此一种可大量生产的绿色化学制程，对于生产者与消费者双方而言都是不可或缺的。以锂离子电池为例，目前商业化的高能量电池负极多为石墨，然而其理论电容量仅止于372mAh/g。为了突破此容量限制，对于新兴负极的研究正广泛地展开，其中尤其以锡基材料(Sn：998mAh/g、SnO2：780mAh/g)与硅基材料(4200mAh/g)两者的合金系统最具发展潜力。然而不管是锡基或是硅基的负极材料，其在充放电过程中的锂离子迁入迁出都伴随着剧烈的体积膨胀与收缩，因而致使合金材料崩解并大幅降低电池循环寿命，而使其成为目前负极合金材料在商业化上最大的阻碍。In the 21st century, when the technological revolution and environmental awareness are on the rise, in order to cope with the rapid evolution of the new generation of technology and green energy products, consumers' performance requirements and demands for energy storage products are also growing simultaneously. For example, portable 3C products, such as mobile phones, PDAs, Smartphones, notebook (tablet) computers, digital cameras, etc., or large vehicles such as electric vehicles, hybrid vehicles, etc. In terms of energy storage devices, the requirements for capacity, lifespan and even output power are becoming increasingly stringent. At the same time, due to the rising awareness of environmental protection, consumers are also paying attention to the production process of products. Therefore, a green chemical that can be mass-produced Manufacturing process is indispensable for both producers and consumers. Taking lithium-ion batteries as an example, most of the negative electrodes of commercialized high-energy batteries are graphite, but their theoretical capacity is only 372mAh/g. In order to break through this capacity limitation, research on emerging negative electrodes is being carried out extensively, especially the alloy system of tin-based materials (Sn: 998mAh/g, SnO2 : 780mAh/g) and silicon-based materials (4200mAh/g) The most potential for development. However, regardless of whether it is a tin-based or silicon-based negative electrode material, the migration of lithium ions during charging and discharging is accompanied by severe volume expansion and contraction, which leads to the disintegration of the alloy material and greatly reduces the cycle life of the battery. This makes it the biggest obstacle to the commercialization of negative electrode alloy materials.
为了解决及缓和负极合金材料的体积变化，目前已有文献或专利公开许多种解决方案。例如美国专利号US6,143,448(1999年4月15日)便公开以金属盐类作为前驱物，经由蒸发干燥加热与后续多道步骤来合成多孔性高表面积电极材料，并通过多孔性材料合成时所预留下的空间来容纳锂离子迁入后造成的体积膨胀。然而高比表面积电极材料对于某些电化学应用来说并不恰当，特别是锂离子二次电池负极，而且若以例如氯化盐、硫酸盐等金属盐类作为前驱物，将使得原子利用率(atomutilization)仅只有40%至60%，此与绿色化学概念背道而驰。In order to solve and alleviate the volume change of the negative electrode alloy material, there are currently many solutions disclosed in literature or patents. For example, U.S. Patent No. US6,143,448 (April 15, 1999) discloses the use of metal salts as precursors to synthesize porous high-surface-area electrode materials through evaporative drying and heating and subsequent multi-channel steps. The reserved space is to accommodate the volume expansion caused by the migration of lithium ions. However, high specific surface area electrode materials are not suitable for some electrochemical applications, especially lithium-ion secondary battery negative electrodes, and if metal salts such as chlorides and sulfates are used as precursors, the atomic utilization rate will be reduced. (atomutilization) is only 40% to 60%, which runs counter to the concept of green chemistry.
美国专利号US6,103,393(1998年8月27日)公开以气凝胶合成法来制作出碳/金属复合微粒材料，该制程使用商业化多孔碳材作为基材，并在吸收金属盐类前驱物后，再以喷出制程使金属触媒被镶嵌于碳材内部，于此实例中的碳材系主要作为载体，负载金属有铂、银、钯、钌、锇等等，而适用于例如燃料电池的应用的电化学触媒反应。由于此前案是以例如氯化盐、硫酸盐等金属盐类作为前驱物，同样将使得原子利用率(atomutilization)仅只有40%至60%，而与绿色化学概念背道而驰。U.S. Patent No. US6,103,393 (August 27, 1998) discloses the production of carbon/metal composite particle materials by airgel synthesis. This process uses commercial porous carbon materials as substrates, and absorbs metal salt precursors After that, the metal catalyst is embedded in the carbon material by the spraying process. In this example, the carbon material is mainly used as a carrier, and the loaded metals include platinum, silver, palladium, ruthenium, osmium, etc., and are suitable for, for example, fuel Electrochemical catalytic reactions for battery applications. Since the previous proposal uses metal salts such as chloride salts and sulfates as precursors, the atom utilization rate (atomutilization) is only 40% to 60%, which runs counter to the concept of green chemistry.
美国专利号US7,094,499(2003年6月10日)则公开了以多款不同的碳材(如纳米碳管、碳纤维、石墨片等)作为基材，并使用金属盐溶液来进行化学沉积处里，后续再使用酸液来清洗材料表面的不稳定沉积层，从而制成碳/金属复合材料，并将此材料进行锂离子电池应用测试。但其各款材料所具电容量皆少于400mAh/g。此外，在此制程中也使用了大量强酸与金属氯化物，二者皆不属于对环境友善的原料。U.S. Patent No. US7,094,499 (June 10, 2003) discloses that a variety of different carbon materials (such as carbon nanotubes, carbon fibers, graphite sheets, etc.) are used as substrates, and metal salt solutions are used for chemical deposition. Afterwards, the acid solution is used to clean the unstable deposition layer on the surface of the material to make a carbon/metal composite material, and this material is tested for lithium-ion battery applications. However, the capacitance of each material is less than 400mAh/g. In addition, a large amount of strong acids and metal chlorides are also used in this process, both of which are not environmentally friendly raw materials.
美国专利号US7,745,047(2007年11月15日)公开了以化学剥离2~90重量百分比的微米级氧化石墨烯作为基材，并以固态球磨法、化学蒸气沉积法或过滤混合堆栈等方式，来制作出各式金属/合金碳复合电极，其是由例如由硅、锗、锡、铅、铋、铝、锌等与其各式合金的多种材料所组成。虽然复合电极在锂离子二次电池上有不错的电化学表现，但此篇专利的材料的合成原料须使用大量的氧化石墨烯基材。此外，即使利用美国专利号US2,798,878(1954年7月19日)的技术仍难以大量制造出合成的氧化石墨烯，而且大量强氧化剂与强酸的使用，将致使制造过程极不环保。故若要将其电极产品投入量产，降低氧化石墨烯的使用量是绝对必要的。U.S. Patent No. US7,745,047 (November 15, 2007) discloses that chemically exfoliated micron-scale graphene oxide of 2 to 90 weight percent is used as a substrate, and is processed by solid-state ball milling, chemical vapor deposition, or filter mixed stacking. , to produce various metal/alloy carbon composite electrodes, which are composed of various materials such as silicon, germanium, tin, lead, bismuth, aluminum, zinc, etc. and their various alloys. Although the composite electrode has good electrochemical performance in lithium-ion secondary batteries, the synthetic raw material of the material in this patent must use a large amount of graphene oxide substrate. In addition, even using the technology of US Patent No. US2,798,878 (July 19, 1954), it is still difficult to produce synthetic graphene oxide in large quantities, and the use of a large amount of strong oxidizing agents and strong acids will make the manufacturing process extremely environmentally unfriendly. Therefore, it is absolutely necessary to reduce the amount of graphene oxide used in order to put its electrode products into mass production.
郑M.Y.等人(ChengMY,HwangCL,PanCJ,ChengJH,YeYS,RickJFandHwangBJ,J.Mater.Chem.,2011,21,10705-10710)于2011年提出以葡萄糖水热法佐以金属锡作为前驱物，以制造出能应用于锂离子电池阳极的纳米级二氧化锡/碳复合材料。此篇文献指出微米金属锡粒子在葡萄糖参与下，将被氧化并缩减为2～5纳米尺寸，并且均匀散布于母体碳材内的纳米级二氧化锡。此材料在锂离子电池的应用上可以具有521mAh/g的电容量，但由于热碳还原温度与锡金属低熔点的双重限制，此材料的热处理温度范围被局限在低于400℃以下烧结，而热碳还原出的金属锡粒会脱离碳材并聚集为数微米的大小，且电性衰退快速。而仅400℃的煅烧温度并不足以将碳系基质完全碳化，以致使该材料的导电性不佳，且此碳系基质无法有效抑制还原活性物质的聚集，因此无法进行二氧化锡还原，同时也导致该材料的首圈不可逆电容量无法有效降低。Zheng M.Y. et al. (ChengMY, HwangCL, PanCJ, ChengJH, YeYS, RickJFandHwangBJ, J.Mater.Chem., 2011, 21, 10705-10710) proposed in 2011 to use the glucose hydrothermal method with metallic tin as a precursor to A nanoscale tin dioxide/carbon composite material that can be applied to the anode of lithium-ion batteries has been produced. This document points out that micron metal tin particles will be oxidized and reduced to a size of 2-5 nanometers under the participation of glucose, and will be uniformly dispersed in the nanoscale tin dioxide in the matrix carbon material. This material can have a capacity of 521mAh/g in the application of lithium-ion batteries, but due to the dual limitations of thermal carbon reduction temperature and low melting point of tin metal, the heat treatment temperature range of this material is limited to sintering below 400 °C, while The metal tin particles reduced by hot carbon will separate from the carbon material and aggregate to a size of a few microns, and the electrical properties will decline rapidly. However, the calcination temperature of only 400°C is not enough to completely carbonize the carbon-based matrix, so that the electrical conductivity of the material is not good, and the carbon-based matrix cannot effectively inhibit the aggregation of reducing active substances, so the reduction of tin dioxide cannot be performed. It also leads to the inability to effectively reduce the first-cycle irreversible capacitance of the material.
总结以上各款电极材料的效能与其制作方法皆有其缺点。因此，如何研发一款具高循环寿命、高容量的电极材料以及兼备可量产的绿色制程，将会是目前储能产业所极为迫切需要的技术。To sum up, the performance of the above electrode materials and their fabrication methods all have their disadvantages. Therefore, how to develop an electrode material with high cycle life and high capacity and a green manufacturing process that can be mass-produced will be an extremely urgent technology for the current energy storage industry.
本案申请人鉴于现有技术中的不足，经过悉心试验与研究，并以锲而不舍的精神，终于构思出本案，能够克服先前技术的不足，以下为本案的简要说明。In view of the deficiencies in the prior art, the applicant of this case finally conceived this case after careful experimentation and research, and with perseverance, which can overcome the deficiencies of the prior art. The following is a brief description of this case.
发明内容Contents of the invention
为了有效避免制备过程中活性物质的聚集或充放电过程中活性物质的崩解、提升材料导电度及活性物质的利用率、降低活性材料在充放电过程中体积剧烈变化所导致的材料崩解及其氧化物与高比表面积纳米材料所带来的不可逆电容量，以及减少对环境不友好的化学物质的使用及废弃物产生。本发明以微米级活性的粒子(如硅、锡、锰、铁、钴、镍、铜、锗、锑、铋、锌、铝、镉)配合醣类(如葡萄醣、蔗糖、乳糖、寡糖等)作为前驱物，经添加零维或一维或二维碳材，并通过水热法合成多维碳材/纳米级活性粒子复合材料。In order to effectively avoid the aggregation of the active material during the preparation process or the disintegration of the active material during the charging and discharging process, improve the conductivity of the material and the utilization rate of the active material, reduce the material disintegration and The irreversible capacitance brought by its oxide and high specific surface area nanomaterials, and the reduction of the use of environmentally unfriendly chemical substances and waste generation. In the present invention, micron-scale active particles (such as silicon, tin, manganese, iron, cobalt, nickel, copper, germanium, antimony, bismuth, zinc, aluminum, cadmium) are combined with sugars (such as glucose, sucrose, lactose, oligosaccharides, etc.) ) as a precursor, by adding zero-dimensional or one-dimensional or two-dimensional carbon materials, and synthesizing multi-dimensional carbon materials/nano-scale active particle composite materials by hydrothermal method.
因此，本发明提供一种碳系活性复合物，包括：若干个碳同素异形体；若干个具活性的粒子；以及若干个醣类分子组成的一种三维黏着碳材，其分别与该些具活性的粒子耦合，以使得各所述具活性的粒子耦合至各个所述碳同素异形体，并使得所述碳同素异形体彼此堆栈成为该碳系活性复合物。Therefore, the present invention provides a carbon-based active compound, including: several carbon allotropes; several active particles; The active particles are coupled so that each of the active particles is coupled to each of the carbon allotropes, and the carbon allotropes are stacked with each other to form the carbon-based active complex.
较佳地，其中所述碳同素异形体，是选自于由零维碳同素异形体、一维碳同素异形体、二维碳同素异形体以及其中任意两种以上的组合所组成的群组，其中该零维碳同素异形体选自于由纳米碳球、碳黑及活性碳粉所组成的群组，该一维碳同素异形体选自于由纳米碳管、石墨碳管及碳纤维所组成的群组，以及该二维碳同素异形体为石墨烯或天然石墨。Preferably, the carbon allotrope is selected from zero-dimensional carbon allotrope, one-dimensional carbon allotrope, two-dimensional carbon allotrope and any combination of two or more thereof The group consisting of, wherein the zero-dimensional carbon allotrope is selected from the group consisting of carbon nanospheres, carbon black and activated carbon powder, and the one-dimensional carbon allotrope is selected from the group consisting of carbon nanotubes, A group composed of graphite carbon tubes and carbon fibers, and the two-dimensional carbon allotrope is graphene or natural graphite.
较佳地，其中该二维碳同素异形体的含量中最多占该碳系活性复合物5%的重量百分比。Preferably, the content of the two-dimensional carbon allotrope accounts for at most 5% by weight of the carbon-based active compound.
较佳地，该碳系活性复合物中的该碳同素异形体可源自于天然或人工合成石墨片、碳纤维、石墨碳管、石墨碳球、中间相碳球、沥青、石油焦炭、碳黑及结晶性高分子碳材，以剥离或分离方法得到，厚度或直径小于50纳米，长宽为1至10微米。Preferably, the carbon allotrope in the carbon-based active compound can be derived from natural or synthetic graphite sheets, carbon fibers, graphite carbon tubes, graphite carbon spheres, mesophase carbon spheres, pitch, petroleum coke, carbon Black and crystalline polymer carbon materials obtained by exfoliation or separation, with a thickness or diameter of less than 50 nanometers and a length and width of 1 to 10 microns.
较佳地，其中所述具活性的粒子选自于由硅、锡、锰、铁、钴、镍、铜、锗、锑、铋、锌、铝、镉金属以及其中任意两种以上的合金、氧化物、碳化物、碳酸盐、磷酸盐与复合元素所组成的群组。Preferably, the active particles are selected from silicon, tin, manganese, iron, cobalt, nickel, copper, germanium, antimony, bismuth, zinc, aluminum, cadmium metals and alloys of any two or more thereof, A group consisting of oxides, carbides, carbonates, phosphates, and compound elements.
较佳地，其中所述具活性的粒子，嵌入在该三维黏着碳材的内部，或是分布在该若干个碳同素异形体的表面上，且所述具活性的粒子具有1~100纳米的粒径，并在该碳系活性复合物的含量中占20%至97%的重量百分比。Preferably, the active particles are embedded in the three-dimensionally bonded carbon material, or distributed on the surfaces of the several carbon allotropes, and the active particles have a diameter of 1-100 nanometers particle size, and account for 20% to 97% by weight in the content of the carbon-based active compound.
较佳地，其中该些醣类分子为具有多元环的结构，且是选自于由单醣、双醣、寡醣、多醣及其中任意两种以上的组合所组成的群组，该单醣是选自于由核糖、脱氧核糖、葡萄糖、果糖、半乳糖及其中任意两种以上的组合所组成的群组，该双醣是选自于由蔗糖、乳果糖、乳糖、麦芽糖及其中任意两种以上的组合所组成的群组。Preferably, the carbohydrate molecules have a multi-ring structure and are selected from the group consisting of monosaccharides, disaccharides, oligosaccharides, polysaccharides and any combination of two or more thereof, the monosaccharide It is selected from the group consisting of ribose, deoxyribose, glucose, fructose, galactose and any combination of two or more thereof, and the disaccharide is selected from the group consisting of sucrose, lactulose, lactose, maltose and any two of them A group consisting of more than one combination.
较佳地，该碳系活性复合物中的该若干个醣类分子与该若干个具活性的粒子耦合，使该若干个具活性的粒子耦合该若干个碳同素异形体，并与该若干个碳同素异形体耦合，使该若干个碳同素异形体彼此堆栈。Preferably, the several sugar molecules in the carbon-based active complex are coupled with the several active particles, so that the several active particles are coupled with the several carbon allotropes, and with the several The carbon allotropes are coupled so that the several carbon allotropes are stacked on top of each other.
本发明还提出一种碳系活性复合物，包括：一导电物质；一具活性的粒子；以及一碳系基质，其与该具活性的粒子耦合，以使得该具活性的粒子耦合至该导电物质，并使得该具活性的粒子的尺寸最小化及稳定化。The present invention also proposes a carbon-based active composite, including: a conductive substance; an active particle; and a carbon-based substrate coupled to the active particle so that the active particle is coupled to the conductive substances, and minimize and stabilize the size of the active particles.
较佳地，其中该导电物质是选自于由零维碳同素异形体、一维碳同素异形体、二维碳同素异形体，以及三维碳同素异形体所组成的群组，且该碳系基质的前趋物为若干个醣类分子。Preferably, wherein the conductive substance is selected from the group consisting of zero-dimensional carbon allotrope, one-dimensional carbon allotrope, two-dimensional carbon allotrope, and three-dimensional carbon allotrope, And the precursors of the carbon-based matrix are several carbohydrate molecules.
本发明还提出一种纳米级碳系活性复合物的制造方法，其包含下列步骤：(a)将碳同素异形体、醣类溶液与微米级具活性的粒子加以混合，以形成混合溶液；(b)在密封环境下反应该混合溶液，以形成一中间产物；以及(c)将该中间产物加以煅烧，以产生该纳米级碳系活性复合物。The present invention also proposes a method for manufacturing a nanoscale carbon-based active compound, which includes the following steps: (a) mixing carbon allotropes, carbohydrate solutions, and micron-scale active particles to form a mixed solution; (b) reacting the mixed solution in a sealed environment to form an intermediate product; and (c) calcining the intermediate product to produce the nanoscale carbon-based active compound.
较佳地，其中该步骤(b)还包含：(b1)将该醣类碳化成为碳系基质，并将该微米级具活性的粒子，氧化成为一嵌入在该碳系基质的纳米级具活性的粒子；该步骤(c)还包含：(c1)导入一气体，以在400℃以上将该中间产物还原，其中该气体是选自于由氮气、氩气、一氧化碳、氢气、联胺、锂、钠、钾、镁蒸气及其中任意两种以上的组合所组成的群组。Preferably, the step (b) further comprises: (b1) carbonizing the sugar into a carbon-based matrix, and oxidizing the micron-sized active particles into a nano-sized active particle embedded in the carbon-based matrix the particles; the step (c) also includes: (c1) introducing a gas to reduce the intermediate product above 400°C, wherein the gas is selected from nitrogen, argon, carbon monoxide, hydrogen, hydrazine, lithium , sodium, potassium, magnesium vapor and any combination of two or more of them.
较佳地，其中该步骤(b)是在100℃~350℃的温度范围，以及1巴~150巴的压力范围下进行反应。Preferably, the step (b) is carried out at a temperature ranging from 100° C. to 350° C. and a pressure ranging from 1 bar to 150 bar.
较佳地，其中该步骤(b)是在150℃~250℃的温度范围，以及4巴~25巴的压力范围下进行反应。Preferably, the step (b) is carried out at a temperature range of 150° C. to 250° C. and a pressure range of 4 bar to 25 bar.
较佳地，该制造方法中该碳系基质可将该纳米级具活性的粒子包覆于该碳同素异形体表层，并使该碳同素异形体形成导电网络。Preferably, in the manufacturing method, the carbon-based matrix can coat the nano-scale active particles on the surface of the carbon allotrope, and make the carbon allotrope form a conductive network.
较佳地，该制造方法中添加该碳同素异形体，可降低低熔点的该具活性的粒子的团聚现象。Preferably, adding the carbon allotrope in the manufacturing method can reduce the agglomeration of the active particles with low melting point.
较佳地，该制造方法中添加该碳同素异形体，可抑制该复合材料在充放电过程的活性材料崩解或材料表面钝化膜的成长。Preferably, adding the carbon allotrope in the manufacturing method can inhibit the disintegration of the active material or the growth of the passivation film on the surface of the material during the charging and discharging process of the composite material.
附图说明Description of drawings
图1为本发明的碳系活性复合物的扫描式电子显微镜(SEM)图像。Fig. 1 is a scanning electron microscope (SEM) image of the carbon-based active composite of the present invention.
图2(a)及图2(b)分别为反应初始的示意图及SEM图像。Figure 2(a) and Figure 2(b) are the schematic diagram and SEM image of the initial reaction, respectively.
图3(a)及图3(b)分别为经水热处理后的示意图及SEM图像。Figure 3(a) and Figure 3(b) are the schematic diagram and SEM image after hydrothermal treatment, respectively.
图4(a)及图4(b)分别为经还原煅烧后的示意图及SEM图像。Figure 4(a) and Figure 4(b) are the schematic diagram and SEM image after reduction calcination, respectively.
图5中：(a)为金属锡、氧化锡及二氧化锡的X-ray衍射图；(b)为在煅烧过程前复合材料X-ray衍射图；(c)至(e)分别为不同时间煅烧后的锡粉末X-ray衍射图。Among Fig. 5: (a) is the X-ray diffractogram of metallic tin, tin oxide and tin dioxide; (b) is the X-ray diffractogram of composite material before the calcination process; (c) to (e) are respectively different X-ray diffraction pattern of tin powder after time calcination.
图6(a)及图6(b)分别为煅烧1小时后的(a)SEM图像及(b)锡粒子的粒径大小分布图。Figure 6(a) and Figure 6(b) are (a) SEM images and (b) particle size distribution diagrams of tin particles after calcination for 1 hour, respectively.
图6(c)及图6(d)分别为煅烧4小时后的(c)SEM图像及(d)锡粒子的粒径大小分布图。Figure 6(c) and Figure 6(d) are (c) SEM images and (d) particle size distribution diagrams of tin particles after calcination for 4 hours, respectively.
图7(a)及图7(b)为(a)水热处理后及(b)还原煅烧后的SEM图像。Figure 7(a) and Figure 7(b) are SEM images of (a) after hydrothermal treatment and (b) after reduction calcination.
图8中：(a)及(b)分别为(a)碳酸锰及(b)氧化锰的锰粒子的X-ray衍射图；(c)至(d)分别为(c)煅烧前及(d)煅烧后的锰粉末X-ray衍射图。Among Fig. 8: (a) and (b) are respectively the X-ray diffractogram of the manganese particle of (a) manganese carbonate and (b) manganese oxide; (c) to (d) are respectively (c) before calcining and ( d) X-ray diffraction pattern of calcined manganese powder.
主要组件符号说明Explanation of main component symbols
10碳活性复合物20石墨烯锡复合材料10 Carbon Active Composite 20 Graphene Tin Composite
11三维黏着碳材21石墨烯水溶液11 Three-dimensional adhesive carbon material 21 Graphene aqueous solution
12石墨烯平板22葡萄糖12 graphene plates 22 glucose
13纳米活性粒子23锡粉。13 nanometer active particles 23 tin powder.
具体实施方式detailed description
本案所提出的发明将可由以下的实施例说明而得到充分了解，并使得本领域普通技术人员可以据以完成，然而本案的实施例并非可由下列实施例而限制其实施型态，本领域普通技术人员仍可依据所公开的实施例的精神推演出其它实施例，该些实施例皆当属于本发明的范围。The invention proposed in this case will be fully understood by the description of the following examples, and enables those of ordinary skill in the art to complete it. However, the examples of this case are not limited to its implementation form by the following examples. Those of ordinary skill in the art Personnel can still deduce other embodiments according to the spirit of the disclosed embodiments, and these embodiments all belong to the scope of the present invention.
请参阅图1，其为本发明的碳系活性复合物10的扫描式电子显微镜图像。在图1中，碳系活性复合物包括三维黏着碳材11、石墨烯平板12及纳米活性粒子13。其中三维黏着碳材11可通过将多个石墨烯平板12彼此堆栈，也可使平均分散在三维黏着碳材11中的纳米金属活性粒子13，黏着在石墨烯平板12的表面上，以形成本发明的碳系活性复合物10。Please refer to FIG. 1 , which is a scanning electron microscope image of the carbon-based active compound 10 of the present invention. In FIG. 1 , the carbon-based active compound includes a three-dimensionally bonded carbon material 11 , a graphene plate 12 and nano active particles 13 . Among them, the three-dimensional adhesive carbon material 11 can be formed by stacking a plurality of graphene flat plates 12 on each other, and the nano-metal active particles 13 evenly dispersed in the three-dimensional adhesive carbon material 11 can be adhered to the surface of the graphene flat plate 12 to form the present invention. Invented carbon-based active composite 10.
在水热法的过程中，首先微米级活性粒子会逐渐与葡萄糖溶液发生氧化反应，并转化成纳米级活性化合物粒子，其后纳米级活性化合物粒子可通过三维黏着碳材，而持续聚合成约200纳米的碳中间产物，其中纳米活性化合物粒子会均匀分散在碳中间产物中。在添加氧化石墨烯之后，碳中间产物会附着在氧化石墨烯表面，并黏合至数组氧化石墨烯平板，并呈现出微米等级层状再堆栈的独特表面形态。将此材料经钝性气体以400℃~900℃热处理后，少量添加的氢气或材料本身的碳，可将活性化合物还原成纳米活性粒子，以增加材料导电性，同时降低首圈不逆电容量。少量添加的氧化石墨烯在活性化合物还原过程中扮演重要角色，其是因为氧化石墨烯可有效抑制活性化合物还原时的团聚现象，进而达到可控制活性物质粒径的独特能力，再者较大的活性复合物，较容易与溶液及黏着剂均匀混合，并在直接涂布于电极极板时可有较佳的黏着性，故能增加电池的循环寿命，最后石墨烯特有的sp2结构电子传导骨干，也可进一步提升电池的高速充放电能力。In the process of the hydrothermal method, firstly, the micron-sized active particles will gradually oxidize with the glucose solution and transform into nano-sized active compound particles, and then the nano-sized active compound particles can be continuously aggregated into about 200 nanometer carbon intermediate product, wherein the nano active compound particles will be uniformly dispersed in the carbon intermediate product. After the addition of graphene oxide, carbon intermediates will attach to the surface of graphene oxide and bond to arrays of graphene oxide plates, presenting a unique surface morphology of micron-scale layered re-stacking. After the material is heat-treated with inert gas at 400°C~900°C, a small amount of added hydrogen or the carbon of the material itself can reduce the active compound into nano-active particles, so as to increase the conductivity of the material and reduce the first-cycle non-reversing capacitance. . A small amount of added graphene oxide plays an important role in the reduction process of active compounds, because graphene oxide can effectively inhibit the agglomeration of active compounds during reduction, and then achieve the unique ability to control the particle size of active materials, and the larger The active compound is easier to mix evenly with the solution and the adhesive, and it can have better adhesion when directly coated on the electrode plate, so it can increase the cycle life of the battery. Finally, the unique sp2 structure of graphene conducts electrons The backbone can also further improve the high-speed charge and discharge capabilities of the battery.
实施例1Example 1
首先，将2.5克石墨(Graphite)、2.5克硝酸钠(Sodiumnitrate,NaNO3)与115毫升硫酸(Sulfuricacid,H2SO4)，在500毫升冰浴反应瓶中均匀混合，并以磁石搅拌。接着在搅拌下缓缓加入7.5克高锰酸钾(PotassiumPermanganate,KMnO4)并避免反应温度超过20℃。然后将反应瓶移至35℃水浴反应30分钟，反应完成后向瓶中缓缓加入115毫升去离子水，并使反应温度升温至98℃后反应15分钟。后续再注入350毫升去离子水与23毫升35%过氧化氢(Hydrogenperoxide,H2O2)，并等待自然冷却后将反应物以透析水洗方式洗至中性，以制备出氧化石墨烯水溶液21(如图2(a)及2(b)所示)。取10毫升1wt%的氧化石墨烯水溶液21，并添加3.6克葡萄糖22(>99.5%；较佳地为D(+)葡萄糖)，同时以磁石搅拌90分钟，以让葡萄糖充分溶解。后续加入1克微米级锡粉23(>99%；Sigma-Aldrich)并搅拌半小时。在其等混和均匀后将混合溶液移入100毫升的反应釜，并以压力为10巴(bar)温度为180℃(若压力为5巴，温度为150℃；若压力为24巴，则温度为220℃)下，以油浴锅持续加热搅拌5小时。待反应釜自然冷却后，将黑色粉末取出以500毫升去离子水冲洗，并在80℃烘箱中干燥过夜，所得到的干燥粉末如图3(a)及3(b)所示。将干燥完成的粉末(约2.25克)移至含钝性混合气体(5%H2&95%Ar)的环境下，以每分钟5℃升温速率升温至550℃，并在550℃下煅烧0至4小时，以得到不同金属粒径大小的复合材料(如图4(a)及4(b)所示)，其中，该氧化石墨烯最多占总复合材料的5%重量百分比。First, 2.5 grams of graphite (Graphite), 2.5 grams of sodium nitrate (Sodiumnitrate, NaNO3 ) and 115 milliliters of sulfuric acid (Sulfuricacid, H2 SO4 ) were uniformly mixed in a 500 milliliter ice-bathed reaction flask and stirred with a magnet. Then, 7.5 g of potassium permanganate (Potassium Permanganate, KMnO4 ) was slowly added under stirring and the reaction temperature should not exceed 20°C. Then the reaction bottle was moved to a 35°C water bath for 30 minutes of reaction. After the reaction was completed, 115 ml of deionized water was slowly added to the bottle, and the reaction temperature was raised to 98°C for 15 minutes of reaction. Then inject 350 ml of deionized water and 23 ml of 35% hydrogen peroxide (H2 O2 ), wait for natural cooling, and wash the reactant to neutrality by dialysis water washing to prepare a graphene oxide aqueous solution 21 (As shown in Figure 2(a) and 2(b)). Take 10 ml of 1wt% graphene oxide aqueous solution 21, add 3.6 g of glucose 22 (>99.5%; preferably D(+) glucose), and stir with a magnet for 90 minutes to fully dissolve the glucose. Subsequently, 1 g of micron-sized tin powder 23 (>99%; Sigma-Aldrich) was added and stirred for half an hour. After they are mixed evenly, the mixed solution is transferred into a 100 ml reaction kettle, and the pressure is 10 bar (bar) and the temperature is 180°C (if the pressure is 5 bar, the temperature is 150°C; if the pressure is 24 bar, the temperature is 180°C). 220° C.), the oil bath was continuously heated and stirred for 5 hours. After the reactor was naturally cooled, the black powder was taken out, washed with 500 ml of deionized water, and dried in an oven at 80°C overnight. The obtained dry powder is shown in Figure 3(a) and Figure 3(b). Move the dried powder (about 2.25g) to an environment containing an inert gas mixture (5%H2 &95%Ar), raise the temperature to 550°C at a rate of 5°C per minute, and calcinate at 550°C from 0 to 4 hours, to obtain composite materials with different metal particle sizes (as shown in Figure 4 (a) and 4 (b)), wherein, the graphene oxide accounts for at most 5% by weight of the total composite material.
请参阅图5,由X光绕射分析仪(X-rayDiffraction,XRD)图谱可以确定在煅烧的过程中,煅烧前复合材料中包含了二氧化锡(如图5中的(b)所示)。煅烧1小时后,复合材料中包含了金属锡、氧化锡及二氧化锡,但是金属锡的含量增多,及二氧化锡的含量减少(如图5中的(c)所示)。而煅烧4小时后,复合材料中则仅有金属锡(如图5中的(e)所示)。由上述实验证实,纳米级二氧化锡晶相系被转换成为纳米级金属锡相,这将可大幅降低了二氧化锡之不可逆电容量。Please refer to Figure 5, it can be determined from the X-ray Diffraction (XRD) spectrum that during the calcination process, the composite material before calcination contains tin dioxide (as shown in (b) in Figure 5) . After calcination for 1 hour, the composite material contained metal tin, tin oxide and tin dioxide, but the content of metal tin increased and the content of tin dioxide decreased (as shown in (c) in Figure 5). After calcination for 4 hours, there is only metallic tin in the composite (as shown in (e) in Figure 5). It is confirmed by the above experiments that the nano-scale tin dioxide crystal phase system is transformed into a nano-scale metal tin phase, which will greatly reduce the irreversible capacitance of tin dioxide.
请参阅图6(a)~6(d)，其为上述复合材料经煅烧的结果。在钝性混和气体(5%H2&95%Ar)的环境下，以550℃煅烧1小时后，锡粒子的平均粒径为28.73nm(如图6(a)及6(b)所示)。而在经过煅烧4小时后，该锡粒子的平均粒径增为56.91nm(如图6(c)及6(d)所示)。同时，随着平均粒径的增大，进而将使其涂布于电极板时可有较佳的黏着性。Please refer to Figures 6(a)-6(d), which are the results of the above-mentioned composite materials being calcined. After calcination at 550°C for 1 hour in an environment of inert mixed gas (5%H2 &95%Ar), the average particle size of tin particles is 28.73nm (as shown in Figure 6(a) and 6(b)) . After calcination for 4 hours, the average particle size of the tin particles increased to 56.91 nm (as shown in Figures 6(c) and 6(d)). At the same time, as the average particle size increases, it will have better adhesion when coated on the electrode plate.
实施例2Example 2
在10毫升去离子水中加入3.6克葡萄糖(>99.5%；较佳为D(+)葡萄糖)，同时以磁石搅拌90分钟让葡萄糖充分溶解，接着加入1克微米级锡粉(>99%；Sigma-Aldrich)搅拌半小时。在混和均匀后将混合溶液移入100毫升的反应釜中，以压力为10巴(Bar)温度为180℃的油浴锅持续加热搅拌5小时。等反应釜自然冷却后将黑色粉末取出，再以500毫升的去离子水冲洗，并在80℃烘箱中干燥过夜。将2.25克干燥完成的粉末移至含钝性气体(N2)中，并控制在400℃下煅烧4小时，以制造出纳米级二氧化锡碳复合材料。Add 3.6 g of glucose (>99.5%; preferably D(+) glucose) to 10 mL of deionized water, and stir with a magnet for 90 minutes to fully dissolve the glucose, then add 1 g of micron tin powder (>99%; Sigma -Aldrich) stirred for half an hour. After mixing evenly, the mixed solution was transferred into a 100 ml reaction kettle, and the pressure was 10 bar (Bar) and the temperature was 180° C., and the oil bath was continuously heated and stirred for 5 hours. After the reactor was naturally cooled, the black powder was taken out, rinsed with 500 ml of deionized water, and dried overnight in an oven at 80°C. 2.25 g of the dried powder was transferred to an inert gas (N2 ), and calcined at 400° C. for 4 hours to produce a nanoscale tin dioxide carbon composite material.
实施例3Example 3
在10毫升去离子水中添加3.6克葡萄糖(>99.5%；较佳为D(+)葡萄糖)，同时以磁石搅拌90分钟让葡萄糖充分溶解，后续加入1克微米级锡粉(>99%；Sigma-Aldrich)搅拌半小时。在混和均匀后将混合液移入100毫升的反应釜中，以压力为10巴(Bar)温度为180℃的油浴锅持续加热搅拌5小时。等待反应釜自然冷却后将黑色粉末取出后，再以500毫升去离子水冲洗，并在80℃烘箱下隔夜干燥。将干燥完成的粉末(约2.25克)移至含钝性混合气体(5%H2&95%Ar)的环境下，以600℃煅烧4小时，以制造出纳米级金属锡/碳复合材料。Add 3.6 g of glucose (>99.5%; preferably D(+) glucose) to 10 ml of deionized water, and stir with a magnet for 90 minutes to fully dissolve the glucose, followed by adding 1 g of micron tin powder (>99%; Sigma -Aldrich) stirred for half an hour. After mixing evenly, the mixture was transferred into a 100 ml reaction kettle, and the mixture was continuously heated and stirred for 5 hours in an oil bath with a pressure of 10 bar (Bar) and a temperature of 180°C. After waiting for the reactor to cool down naturally, the black powder was taken out, rinsed with 500 ml of deionized water, and dried overnight in an oven at 80°C. The dried powder (about 2.25 g) was moved to an environment containing an inert gas mixture (5%H2 &95%Ar), and calcined at 600°C for 4 hours to produce a nanoscale metal tin/carbon composite material.
实施例4Example 4
首先，将2.5克石墨(Graphite)、2.5克硝酸钠(Sodiumnitrate,NaNO3)与115毫升硫酸(Sulfuricacid,H2SO4)，在500毫升的冰浴反应瓶中均匀混合，并以磁石搅拌。接着在搅拌下缓缓加入7.5克高锰酸钾(PotassiumPermanganate,KMnO4)并避免反应温度超过20℃。然后将反应瓶移至35℃水浴反应30分钟，反应完成后于瓶中缓缓加入115毫升去离子水，并使反应温度升温至98℃反应15分钟。后续再注入350毫升去离子水与23毫升35%过氧化氢(Hydrogenperoxide,H2O2)，等待自然冷却后，将反应物以透析水洗方式洗至中性，以制备出氧化石墨烯水溶液。取10毫升1wt%的氧化石墨烯水溶液，并添加3.6克葡萄糖(>99.5%；较佳为D(+)葡萄糖)，与1.2g尿素(>99.5%；ACROS)，再以磁石搅拌90分钟让葡萄糖充分溶解。后续加入1克微米级(50μm)锰金属(>99%；Sigma-Aldrich)搅拌半小时。在混和均匀后将混合液移入100毫升的反应釜中，以压力为10巴(Bar)温度为180℃(若压力为5巴，温度为150℃；若压力为24巴，温度为220℃)的油浴锅持续加热搅拌5小时。等待反应釜自然冷却后，将黑色粉末取出以500毫升去离子水冲洗，并在80℃烘箱下隔夜干燥。干燥完成的粉末由XRD鉴定为纳米级碳酸锰结构。再将约2.25克干燥完成的粉末(如图7(a)所示)，移至钝性气体(N2)的环境下，以400℃煅烧4至10小时，此复合材料在煅烧后可以成功地将碳酸锰，转变成具电化学活性的氧化锰(如图7(b)所示)。First, 2.5 grams of graphite (Graphite), 2.5 grams of sodium nitrate (Sodiumnitrate, NaNO3 ) and 115 milliliters of sulfuric acid (Sulfuricacid, H2 SO4 ) were uniformly mixed in a 500 milliliter ice-bathed reaction flask and stirred with a magnet. Then, 7.5 g of potassium permanganate (Potassium Permanganate, KMnO4 ) was slowly added under stirring and the reaction temperature should not exceed 20°C. Then the reaction bottle was moved to a 35° C. water bath for 30 minutes of reaction. After the reaction was completed, 115 ml of deionized water was slowly added to the bottle, and the reaction temperature was raised to 98° C. for 15 minutes. Subsequently, 350 ml of deionized water and 23 ml of 35% hydrogen peroxide (H2 O2 ) were injected, and after natural cooling, the reactant was washed to neutrality by dialysis water to prepare a graphene oxide aqueous solution. Take 10 ml of 1wt% graphene oxide aqueous solution, add 3.6 g of glucose (>99.5%; preferably D(+) glucose), and 1.2 g of urea (>99.5%; ACROS), and then stir with a magnet for 90 minutes to let Glucose is fully dissolved. Subsequently, 1 g of micron-sized (50 μm) manganese metal (>99%; Sigma-Aldrich) was added and stirred for half an hour. After mixing evenly, transfer the mixture into a 100ml reaction kettle with a pressure of 10 bar (Bar) and a temperature of 180°C (if the pressure is 5 bar, the temperature is 150°C; if the pressure is 24 bar, the temperature is 220°C) The oil bath was continuously heated and stirred for 5 hours. After waiting for the reactor to cool naturally, the black powder was taken out and rinsed with 500 ml of deionized water, and dried overnight in an oven at 80°C. The dried powder was identified by XRD as a nanoscale manganese carbonate structure. Then about 2.25 grams of the dried powder (as shown in Figure 7(a)) was moved to an inert gas (N2 ) environment and calcined at 400°C for 4 to 10 hours. After calcination, the composite material can be successfully Manganese carbonate is converted into electrochemically active manganese oxide (as shown in Figure 7(b)).
请参阅图8，其为上述复合材料经煅烧后的XRD鉴定结果。其中(c)说明，在煅烧前，复合材料中的锰皆以碳酸锰的形式存在，经过400℃煅烧4至10小时后，复合材料中的锰从碳酸锰转变成氧化锰(如图8中的(d)所示)。Please refer to FIG. 8 , which is the XRD identification result of the above-mentioned composite material after being calcined. (c) shows that before calcination, the manganese in the composite material exists in the form of manganese carbonate, and after calcination at 400°C for 4 to 10 hours, the manganese in the composite material changes from manganese carbonate to manganese oxide (as shown in Figure 8 as shown in (d)).
本发明属难能可贵的创新发明，深具产业价值，故依法提出申请。此外，本发明可以由本领域普通技术人员做任何修改，但不脱离如所附权利要求所要保护的范围。The present invention is a commendable innovative invention with great industrial value, so the application is filed according to law. In addition, the present invention may be modified by those skilled in the art without departing from the scope of protection as set forth in the appended claims.
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210257208.2ACN103579625B (en) | 2012-07-24 | 2012-07-24 | Carbon-based/active material composite and manufacturing method thereof |
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210257208.2ACN103579625B (en) | 2012-07-24 | 2012-07-24 | Carbon-based/active material composite and manufacturing method thereof |
| Publication Number | Publication Date |
|---|---|
| CN103579625A CN103579625A (en) | 2014-02-12 |
| CN103579625Btrue CN103579625B (en) | 2016-07-06 |
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| CN201210257208.2AExpired - Fee RelatedCN103579625B (en) | 2012-07-24 | 2012-07-24 | Carbon-based/active material composite and manufacturing method thereof |
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