Characteristics, application and production technology of carbon nanotubes
Characteristics, application and production technology of carbon nanotubes
Carbon nanotubes (CNTS) are perfect 1D cylinders composed of one (single-walled carbon nanotube, SWCNT) or multiple graphene sheets (multi-walled carbon nanotube, MWCNT) rolled up and have become the focus of research due to their unique geometry and excellent properties. Both experimental and theoretical analyses show that single-walled carbon nanotubes (SWCNT) and multi-walled carbon nanotubes (MWCNT) have high mechanical strength, high aspect ratio (> 1000), high thermal conductivity, high melting point and low density (1.2-2.6 g/cc). In addition, CNT has a larger surface area (approximately 1000 m²/g), showing excellent hydrogen storage capacity, significant biological properties, and higher corrosion resistance. CNTS also have unique electrical conductivity, and depending on their structure (diameter and helicity), they can exhibit the electronic properties of metals or semiconductors. It is precisely because of its excellent physical and chemical properties that carbon nanotubes have initially blossomed in the field of new materials, gradually realizing industrialization, and are also widely used in the lithium battery industry, attracting more and more attention from the industry.Domestic carbon nanotubes as a conductive agent used in power batteries, its market with the rapid growth of the power battery industry, the scale has reached billions of yuan per year, there are a number of domestic and foreign companies and listed companies have been involved in the field of carbon nanotubes conductive, such as Dow Technology, German nano, Cabot and other companies. With the expansion of the application scale of new technologies such as high-nickel positive lithium batteries, silicon-based negative batteries and solid-state batteries, the market for carbon nanotubes will also grow explosively, and it will become an annual market of 10 billion in the field of lithium batteries alone.In addition to excellent electrical conductivity, carbon nanotubes also have a huge potential market for development such as ultra-high mechanical and thermal properties. The 1996 Nobel Prize winner in Chemistry, the Honourable Richard E. Smalley (the discoverer of fullerenes), once said: "Carbon nanotubes are the strongest, toughest and hardest molecules that can be made, and are the best molecular conductors of heat and electricity." It sounds like this is the good prediction and desire of scientists, but this is the original intention of Juyuan Material Technology (Zunyi) Co., Ltd. to intervene in the carbon nanotube industry, and it is also the goal of industrialization. The application of lithium battery conductive agent is only the "tip of the iceberg" of the industrialization of carbon nanotubes, and it is the first step for capital and traditional chemical new material enterprises to understand carbon nanotubes. Carbon nanotubes in the touch screen, transistors, biomedical, solar photovoltaic cells, tires, fuel cells, drug delivery, hydrogen storage, polymer materials, capacitors, composite materials and other fields will have a broader market, will continue to break through more than 10 billion of the market, become a 100 billion market industry.The huge carbon nanotube application market requires sufficient carbon nanotube production capacity to support and a sustainable supply of low-cost high-quality carbon nanotubes in order to open a huge downstream potential application market. The early tonnage production of carbon nanotubes was achieved by fixed bed/moving bed equipment, and the continuous addition of catalysts and hydrocarbon raw materials and the continuous output of carbon nanotube products in a horizontally placed tube furnace through a sophisticated device can realize the production of the first generation of carbon nanotube plants with tons to tens of tons per year in a single device. Up to now, there is still some market space for some special types of carbon nanotubes, or some special raw materials for carbon nanotube production, using fixed bed/moving bed first-generation carbon nanotube factories.In order to achieve larger scale carbon nanotube production, the second-generation carbon nanotube factory with fluidized bed reactor solves the larger scale production problem to a certain extent, and the annual production capacity of a single reactor can reach 100 tons to hundreds of tons. At present, the large-scale production of carbon nanotubes in China, many production companies are basically based on fluidized bed reactors. With the emergence of larger production requirements, fluidized bed reactors have the following characteristics: 1. They cannot be scaled up; 2, easy carbon deposition, coking plugging reactor; 3, the boiler shutdown and cleaning of the reactor is difficult, the time-consuming period is long and other problems, which seriously restricts the expansion of the single production capacity of the fluidized bed reactor. At present, the inner diameter of the fluidized bed reactor in the industry is basically 500mm\600mm\800mm, and it is difficult to further expand.
READ MORE
Research status of all-solid-state lithium-ion batteries
Research status of all-solid-state lithium-ion batteries
Due to its advantages of high energy density, long cycle life, low self-discharge rate, and no memory effect, lithium-ion batteries stand out from many energy storage technologies and become the most important part of the electrochemical energy storage field at present. In recent years, the application scenarios of lithium-ion batteries have expanded rapidly, from portable electronic products to electric vehicles, home energy storage, industrial energy storage, etc., lithium-ion batteries have penetrated into all aspects of society, which also puts higher requirements on the safety and energy density of lithium-ion batteries.Traditional lithium-ion batteries mainly rely on organic liquid electrolyte to conduct lithium ions, and the flammable and volatile characteristics of the electrolyte lead to thermal runaway, fire, explosion and other safety risks in the case of overheating, short circuit, overcharge, and mechanical damage. New energy vehicle safety accidents occur from time to time, and ensuring the safe operation of new energy vehicles is the primary task of the current development of the industry. In recent years, through the innovation of battery system structure, the safety of power battery operation has been improved to a certain extent. Facing the future, the development of battery structure innovation to material system innovation is an inevitable trend of power batteries.Therefore, the development of high safety and high energy density energy storage technology to make up for the shortage of liquid lithium-ion batteries is an important development direction of lithium-ion batteries in the future.The use of solid electrolytes to replace liquid electrolytes and the development of all-solid-state lithium batteries can solve the energy density bottleneck and safety risks faced by the current liquid ion batteries, and become the most potential next-generation lithium-ion battery follow-up technology. As shown in Figure 1, the structure and working principle of the all-solid lithium battery is similar to that of the liquid lithium ion battery, but the solid electrolyte has high thermal stability and chemical stability, and will not leak, burn or explode, thereby reducing the risk of thermal runaway and improving the intrinsic safety of the battery. At the same time, the solid electrolyte has a high Young's modulus, which can effectively inhibit the growth of lithium dendrites, and is expected to realize the application of metal lithium anode, which greatly improves the energy density of the battery. In addition, the packaging of all-solid-state batteries is easier. The use of bipolar stacking technology in solid-state batteries can reduce the use of inactive materials such as pole ears and leads, and the battery module does not require a cooling system, which is expected to further improve the volume and mass energy density of the system.
READ MORE
The gold standard for battery adiabatic calorimeter: traceable battery adiabatic calorimeter calibration scheme
The gold standard for battery adiabatic calorimeter: traceable battery adiabatic calorimeter calibration scheme
As an important instrument for the measurement of adiabatic thermal runaway of batteries, the core technical index of the battery adiabatic calorimeter is the self-exothermic detection sensitivity of the sample, that is, the ability to identify the weak exothermic heat of the sample. This index directly determines the measurement accuracy of the instrument for the characteristic temperature points such as the initial temperature of the battery self-exothermic heat. In order to achieve high detection sensitivity, the instrument is required to have ideal structural design, accurate temperature measurement technology and efficient temperature control algorithm, so as to achieve excellent adiabatic performance.At present, there is a lack of measurement and calibration specifications for the whole battery adiabatic calorimeter in the industry, so there is no unified, scientific and reasonable method to verify the core indicators of the instrument, which is not conducive to objectively evaluating the performance of the instrument and regulating the instrument standards, and the data measured by the instrument with poor adiabatic performance will directly affect the relevant enterprises to carry out the safety design of the battery system, and have a negative impact on the development of the lithium battery related industries.Some manufacturers and users use lithium batteries with empirical data as standard samples for instrument evaluation. There are some problems in this method: (1) The same batch of batteries may have slight differences in internal structure and materials, and the consistency of thermal runaway experimental data cannot be guaranteed, which will introduce additional uncertainty; (2) The thermal runaway process of some lithium batteries is severe, causing obvious pollution and even damage to instruments and equipment, and at the same time, high requirements for the test site.
READ MORE
Prelithium technology of lithium ion battery
Prelithium technology of lithium ion battery
Lithium-ion battery (LIBs) has become one of the widely used electrochemical energy storage systems due to its high energy density, high operating voltage and no memory effect, and its commonly used graphite negative electrode is difficult to fully meet the increasing market demand due to its relatively low capacity (372 mAh g-1). Over the past few decades, researchers have proposed a variety of new anode materials, which generally exhibit the advantages of ideal potential range, higher capacity, excellent magnification performance, and long cycle life, but have the disadvantage of large initial active lithium loss (ALL). Therefore, how to eliminate ALL before full battery assembly is critical to achieving high-performance LIBs. In the course of development in recent years, new anode materials for the next generation of LIBs have gradually begun to be commercialized, so the research of pre-lithium technology, which is crucial to the elimination of ALL, has become an important research direction.Causes of loss of high initial active lithium in negative electrodeThe high initial ALL of the negative electrode occurs in the first few cycles and the coulomb efficiency is low (CE < 100%), which indicates that some Li+ remains in the negative electrode, resulting in a decrease in the amount of Li+ that can be cycled in the LIBs. When matched with the positive electrode, the reduced recyclable Li+ will inevitably lead to a reduction in the energy density of the entire battery. Figure 1 shows the typical intercalation/insertion, conversion and alloying lithium storage mechanisms of negative electrode materials, which mainly exhibit relatively low potential and much higher capacity than commercial graphite and Li4Ti5O12, but the first loop coulomb efficiency of these materials is usually less than 80%, resulting in a low coulomb efficiency mechanism. The causes of initial negative ALL can usually be divided into the formation of SEI, the loss of active material and the appearance of dead lithium.Effect of negative active lithium lossIn practical applications of LIBs, some of the recyclable Li+ is consumed to form SEI on the negative surface, resulting in a lower first turn of CE, which in turn leads to a rapid capacity decay of the battery. As shown in Figure 2, the reversible capacity of the electrode is not reduced during this process, and when additional lithium sources are added to the system, the specific capacity of the battery will be restored to the ideal situation. The introduction of additional lithium sources will offset the specific energy gain brought by the pre-embedded lithium, and the effect of higher initial ALL on the specific capacity loss of the whole battery can be elaborated through theoretical calculation and analysis, and the specific energy based on the total mass of the negative electrode, the positive electrode and the lithium source can be obtainedFigure  shows the effect of different additional lithium sources on contrast energy. The specific capacity function of R with respect to the lithium source (cls) is shown for different negative lithium sources with initial CE of 50%, 70% and 90%, respectively. It can be seen that with the increase of cls, the R factor increases, while the decrease of CE will lead to a lower R factor. It can also be seen that when cls is greater than cc, it is necessary to use lithium sources to effectively improve the energy density. The analysis of these results can add more detailed parameters for different systems.A lithium source is added to the negative electrodeInitial ALL is caused by irreversible electrochemical processes on the negative electrode, so the most direct strategy for eliminating initial ALL is to prepare the pre-embedded lithium negative electrode by electrochemical and/or chemical strategies prior to pairing with the positive electrode. The positive electrode strategies can be divided into three categories: the half cell electrochemical method (HC-EM), the short circuit electrochemical method (SC-EM) and the chemical method (CM) as shown in the figure. After the negative electrode is pre-embedded with lithium, the initial ALL problems can be solved well, and the Coulomb efficiency of the entire battery first circle can be effectively improved.
READ MORE
Capacity attenuation mechanism of thick electrode of lithium ion battery
Capacity attenuation mechanism of thick electrode of lithium ion battery
At present, the need of high-endurance new energy vehicles forces the energy density of batteries to become higher and higher, and the use of thick electrodes with high load density active materials is one of the most practical strategies. However, their long cycle use process is accompanied by serious attenuation of electrochemical performance, power performance is not satisfied, and the capacity retention rate is getting worse and worse. So what exactly is causing the bottleneck of poor performance?Kyu-Young Park et al. explored the key processes that restrict battery decay by designing thick electrodes with different area degrees.1. Experimental designUsing NCM622: carbon black: PVDF 97:1.5:1.5 ratio and NMP mixed into pulp, after coating, drying and roller pressing, two kinds of electrodynamic half cells (2032) with different surface densities (20 and 28mg/cm-2) were prepared, and the pressure was between 2.8 and 2.9, in order to ensure better porosity. The charge and discharge cycle of the multi-channel device was carried out with the charge and discharge interval of 2.8-4.3V and the rate 1C was about 150mA/g. EIS, chemical composition and morphology were analyzed after every 20 cycles.2. Results and discussionThe following is the cross-section diagram of the electrodes of two thickths, respectively 70 and 100μm(standard electrode, thick electrode), the rest of the porosity, 1C current density and other design parameters are basically the same, and then the 1C cycle test is carried out. It is found in Figure c that although the capacity of the thick electrode of 100μm is only 40% higher than that of 70μm, but after 100 battery cycles, The thick electrode has a capacity retention rate of only 36%, while the standard electrode has a capacity retention rate of 76%. Even taking into account the volume specific capacity, the thick electrode after attenuation in Figure c is still much lower than the electrode. Interestingly, in Figure c, even in the initial cycle process, the circulation curves of the thick electrode and the standard electrode are close, and the attenuation degree is similar. Thick electrodes are getting worse.In illustrating the poor electrochemical performance observed, the authors note that thick electrodes may be subject to kinetic limitations caused by how fast or slow charge carriers migrate, which in electrochemical processes is either controlled by lithium-ion transport or by the transport of electrons that accumulate along the electrode. And, in each case, assuming that the main source of supply of electrons and lithium ions to the electrode is carried out from the electrode/collector interface and the electrode/electrolyte interface, in each case there will be a clear spatial distribution of both after the reaction.3. ConclusionBy using batteries designed with different electrode thickness, the authors verify that lithium ion diffusion is the limiting factor of charge transfer, but not electron transfer. This is also the reason why SOC at different locations is uneven, voltage drop IR increases, particle breakage and even battery diving under charge and discharge in batteries designed with thick electrodes. The electrode plate is designed according to the ion transport characteristics to avoid the phenomenon of excessive local current density, so as to improve the battery life
READ MORE
What is the side voltage of a lithium battery? How to control side voltage!
What is the side voltage of a lithium battery? How to control side voltage!
The side voltage of the lithium battery refers to the voltage of the aluminum layer between the positive ear of the soft-pack battery and the aluminum-plastic film.In theory, the aluminum layer between the positive electrode and the aluminum-plastic film is insulated, that is, their voltage should be 0In fact, during the processing of the aluminum-plastic film, the PP layer of the inner layer will be locally damaged, resulting in local conduction (including electronic channels and ion channels) between them, forming a microbattery, and thus a potential difference (voltage).The side voltage standard varies from manufacturer to manufacturer, but most of the industry is set below 1.0V, and the standard voltage is based on the dissolution potential of aluminum lithium alloy!Why control the side voltage?Because if the inner PP film of the aluminum-plastic film is damaged, the capacity will be corroded.The conditions for corrosion must have two points: 1, the electronic path, the negative electrode and the aluminum layer of the aluminum-plastic film form the electronic path; 2, the ion path, the aluminum layer of the aluminum-plastic film and the electrolyte form an ion path; Without either one, corrosion doesn't work.After the two conditions are established, the lithium ion will react with the aluminum layer of the aluminum-plastic film to generate lithium aluminum alloy; Lithium aluminum alloy is a powdery substance, resulting in aluminum-plastic film penetration; That is, we often see some black spots inside the aluminum-plastic film; These dark spots will become more and more obvious with time and the number of charges and discharges.How to choose?The current statistical detection methods are:1, test the resistance between the aluminum plastic film and the negative ear, greater than 5M ohms is relatively safe, some companies define the relatively low, look at the final PPm of bad products we endure, you can measure some data and then define their own standards can also; This resistance test is mainly to pick out the electronic path;2, test the current between the positive electrode and the aluminum film, you can use the DC source test, it is generally believed that the current is greater than 0.001mA, it is defective, need to be picked out;3. Test the voltage between the positive electrode and the aluminum film, which is generally considered to be greater than 1V for defective products.You can test 1 and 2, or 1 and 3 together.
READ MORE
Cutting-edge technology in new energy vehicles: Conductive carbon black
Cutting-edge technology in new energy vehicles: Conductive carbon black
Conductive carbon black is a type of conductive agent and an important auxiliary material in lithium batteries.Compared to other conductive agents, conductive carbon black has better overall performance and is currently the mainstream conductive agent. Benefiting from the continuous growth in demand for downstream new energy vehicles, we expect the global market space for conductive carbon black to be around 7.6 billion yuan by 2027. In terms of production process, the main barrier for conductive carbon black lies in the design of reaction furnace equipment. In terms of production cost, the main cost components of this product include raw materials such as coal tar. In terms of market landscape, this product has mainly relied on imports in the past, but is currently accelerating domestic substitution. Domestic companies mainly include Black Cat Corporation, Jiaozuo Hexiong, Yongdong Corporation, and Wuxi Dongheng. Looking at future trends, conductive carbon black is suitable for the trend of composite conductive agents. Conductive carbon black is the mainstream lithium battery conductive agent, with core technology creating barriers Conductive agents are important auxiliary materials for improving the conductivity of lithium batteries, which can compensate for the poor conductivity of positive electrode materials and maintain the conductivity performance of negative electrode materials after repeated expansion and contraction. Conductive carbon black performs well when considering factors such as the degree of improvement in electrode conductivity, slurry dispersion performance, formulation dosage, and cost. According to GGII data, conductive carbon black accounted for 65% of China's power battery conductive agents in 2022. The performance of conductive carbon black is mainly determined by its structural characteristics, specific surface area, and magnetic impurity content. The performance requirements for lithium-grade conductive carbon black are higher than for ordinary carbon black, and the product performance can be classified from low to high as acetylene black, SP, and Ketjen black. The reaction furnace is an important reaction equipment and a core barrier for the production of conductive carbon black, with components such as the oil nozzle in the furnace head being crucial for accuracy. Localization and cost reduction are the trend, with potential for small and beautiful new energy tracks In terms of cost composition, raw materials such as coal tar account for approximately 80% of the cost of conductive carbon black. The price of imported conductive carbon black has long been high, with shipping costs accounting for a certain proportion.Domestic substitution can eliminate shipping costs, while domestic raw material costs are lower than overseas costs, making it cost-effective. Assuming that the proportions of conductive carbon black added to ternary positive electrode materials, lithium iron phosphate and other positive electrode materials, and negative electrode materials are 2%, 3%, and 1% respectively, and the penetration rates of conductive carbon black from 2023 to 2027 are 56%, 54%, 52%, 51%, and 50%, the global market demand for conductive carbon black from 2023 to 2027 is estimated to be 48,000 tons, 66,000 tons, 89,000 tons, 118,000 tons, and 152,000 tons, corresponding to market spaces of 3.14 billion yuan, 3.94 billion yuan, 4.87 billion yuan, 6.15 billion yuan, and 7.60 billion yuan. Domestic substitution is underway, with efforts to promote expansion In the past, due to the dispersed scale of domestic carbon black companies and their focus on the tire market, as well as insufficient core research and development technology for reaction furnaces, domestic conductive carbon black was almost entirely dependent on imports. Major companies included France's Orion Stone, the United States' Cabot Corporation, Japan's Lion King, and Japan's Denka Corporation. With the accelerated penetration of downstream new energy vehicles and the significant increase in demand for lithium batteries, overseas supply of conductive carbon black has been unable to meet demand and prices have been high. Domestic companies have begun to initiate domestic production, gradually achieving technological breakthroughs. Major companies include Black Cat Corporation, Jiaozuo Hexiong, Yongdong Corporation, and Wuxi Dongheng.Risk warning: Lower-than-expected sales of downstream new energy vehicles, slower-than-expected industrialization progress, technological innovations, and the mention of companies in the industry chain do not represent coverage or investment recommendations for the company.
READ MORE
Enter Amp New Energy Technology Co., Ltd. | Experience the practical application of "protecting the blue sky with fluorine chemistry"
Enter Amp New Energy Technology Co., Ltd. | Experience the practical application of "protecting the blue sky with fluorine chemistry"
Global warming, depletion and destruction of the ozone layer, reduction of biodiversity...With the pace of human development, global environmental issues are becoming increasingly severe, and environmental protection has become a common topic for the international community.With the proposal of the "dual carbon" target, promoting the green and low-carbon transformation of the economy and society has become a major systemic project, and enterprises will undoubtedly become the vanguard of global environmental governance. Adhering to the concept of "science first", Amp New Energy Technology Co., Ltd. has undertaken the construction of national key laboratories for fluorine greenhouse gas substitution and control treatment, as well as the national ODS substitute engineering technology research center and other national level innovation platforms.They have developed a new generation of green refrigerants, foaming agents, and other products, with the annual elimination of ODS accounting for about 10% globally and contributing to a reduction of 460 million tons of CO2 equivalent, equivalent to the average annual absorption of CO2 by 40 billion trees. This is the low-carbon vision that China Blue Sky is painting. On World Environment Day on June 5th, at the media open day event held by China Blue Sky, we understood the original intention of a fluorine chemical enterprise to "protect the blue sky" for 72 years and the beautiful belief of promoting world high-quality development through technological innovation. Amp New Energy Technology Co., Ltd. is truly a "sky protector".As early as 1999, the Zhejiang Chemical Research Institute under Amp New Energy Technology Co., Ltd. was approved to establish the only "National ODS Substitute Engineering Technology Research Center" in China, being the first research institution in the country to engage in ODS replacement research. Today, the center has developed a large number of influential ODS substitute varieties and technologies, winning awards such as the "Ozone Layer Protection Contribution Award" from the National Environmental Protection Bureau, making significant contributions to China's compliance with the Montreal Protocol and product upgrades. Currently, the national key laboratory for fluorine greenhouse gas substitution and control treatment has achieved a series of innovative results in the development of fluorine greenhouse gas substitutes, green process development, and fluorine gas capture and conversion, providing strong technical support for reducing emissions at the source, process control, and end-of-pipe treatment of fluorine greenhouse gases. During the open day, journalists experienced a magical "water" where a tablet computer could function normally when submerged in it, and a light bulb could be powered on safely when placed in it. Researcher Wang Fei explained that this was the "miraculous fire extinguishing agent" called perfluorohexanone, developed by the company's national key laboratory. This fire extinguishing agent has excellent insulation, compatibility, and efficiency, but most notably, its environmental friendliness. Perfluorohexanone is currently one of the ideal replacements for halon, with an ODP value of 0 and a GWP value of only 1, compared to the GWP value of 3500 for the currently used fire extinguishing agent, heptafluoropropane. This means that for the same fire extinguishing effect, the greenhouse gas emissions released into the atmosphere are only 1/3500 of the original amount! With an atmospheric residence time of 5 days, it is truly a green and environmentally friendly fire extinguishing agent.
READ MORE