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On September 9, the second seminar on the development direction of energy storage battery technology was held in Beijing.
The meeting was jointly sponsored by the Energy Storage Application Branch of China Chemical and Physical Power Supply Industry Association and the Energy Storage Technology Research Group of the Institute of Electrical Engineering, Chinese Academy of Sciences, and supported by Beijing Haofeng Energy Storage Technology Co., Ltd., Zhejiang Nandu Power Supply Co., Ltd., Zhongtian Energy Storage Technology Co., Ltd., Changxing Taihu Energy Valley Technology Co., Ltd. and Hefei Boao Guoxing Energy Technology Co., Ltd.
Li Li, a professor of Beijing University of Technology, attended the meeting and delivered a report entitled "Recycling and Recycling Technology of Spent Lithium Ion Batteries". The following is the full text of the speech:
Li Li: Good afternoon, distinguished guests! My name is Li Li from Beijing University of Technology. First of all, I would like to thank the Association for its invitation. My topic today is about lithium ion battery recycling and regeneration technology. This is the content of today's report. First, let's take a brief look at the research background. From these two pieces of data, we can clearly see that it is from the National Laboratory and the Energy Information Center of the United States. It's his statistics on the global production of lithium-ion batteries for electric vehicles and lithium-ion batteries for electric bicycles. From this data, we can see that not only China, but also the global trend is very obvious. As far as China is concerned, from 2011 to 2017, let's take a look at the production of electric vehicles in China. At the beginning of 2011, there were less than 5000, about 4800. The number of new energy vehicles has reached 1.99 million by the end of June, accounting for more than 80%. From the Made in China 2025 Plan advocated by the Ministry of Science and Technology of the People's Republic of China, we can also know that the main three core technologies are low-carbon and intelligent.
We pay attention to the recycling of battery resources. First, we pay attention to its price. The distribution of nickel, manganese and other elements involved in lithium batteries in the sphere can be seen in these two figures. As far as we are concerned about the global distribution of nickel and cobalt, we have taken two major charts respectively. China's reserves of these two metals have reached 4% and 6%, which are very small. So we know that energy storage and demand are two aspects of obvious mismatch. So far, in addition to using renewable energy, most companies around the world still use nickel ore or cobalt ore as raw materials to produce composite materials.
We will track the price trend of each metal on the London Metal Exchange every year. We know that the price of cobalt has always been high, and there has been a slight fluctuation in the past two months. From the right side, we can see that the lithium battery for electric vehicles reached 3200 kWh in 2017, and we can see the column chart. It is very obvious from the color distribution of different systems, such as the ternary 111 type, 622523, and the metal proportion of various systems of lithium iron phosphate. The consumption of 111 type material, a 50kwh battery pack based on this material, consumes an amazing amount of cobalt, nickel and copper. If we observe the whole life cycle of lithium batteries, we should first reduce the cost of battery materials, and we need to start research and development from raw materials. The price of raw materials leads to the price of individual cells or battery packs. During the manufacturing process, the energy consumption and scale, as well as the final impact on the environment, play a key role to a certain extent. In the process of use, one of our topics today is long life, so extending the life can reduce the battery cost to a certain extent, and finally return to the recycling field. Then we hope that the recycling of raw materials can reduce the pressure of battery field or other material fields on the national raw ores to a certain extent.
At present, how to deal with and dispose of battery failure has become a very important topic. We have also learned about its harmfulness in many meetings. It mainly includes the discharge of organic matter, the discharge of water atmosphere and solid waste. Based on different battery parts, such as positive pole, negative pole, electrolyte and diaphragm, its material system, performance and environmental impact are very obvious in this table. For different battery components, we also have different recycling methods. We have given us a very intuitive guidance on which components can be recycled in the simplest way. At present, battery recycling technologies mainly include pretreatment process, living method and wet method.
The following is a brief introduction to the latest international frontier in every aspect. First of all, for pretreatment, many enterprises or research institutes pay more and more attention to this part. Crushing and screening are common pretreatment processes. How effective are they? In the process of disassembly and crushing, the main emission is the volatilization of electrolyte. We can see the emission of carbon dioxide. The column chart on the right shows the direct impact of the screening density of cobalt based lithium battery materials, or lithium iron phosphate, at the early stage on the leaching rate of various metals at the later stage.
In addition to crushing and splitting, flotation is also a very critical step in pretreatment. We know that the material is an interface reaction, so there must be a layer of animated material on the interface. We can clearly see that the surface is covered with a layer of organic matter, which may have a negative impact on the flotation efficiency of the material during flotation. Therefore, this work is used in flotation. Through this detection, it can be found that large molecular weight can be easily dispersed into small molecules. Some organic materials can be oxidized to form carbon dioxide and water for emission. In the flotation process, we used materials. Different materials have clear water properties. If we want to remove the organic substances on the surface of particles, later flotation will undoubtedly play a very positive role.
Now there are many reports in the past two years. We can see that this work is to grind with lithium cobalate material and iron powder. Because chlorine and lithium in PVC are combined, the product is lithium chloride, and water can be separated later. Just now, we talked about pretreatment. The second part is living method recycling. Living method people think that they must calcine at high temperature at least above 1000 ℃ under high temperature. This work is about the technical drill of in-situ vacuum. Under this special condition, for example, after mixing the mixed material, manganese acid and ternary material, they conduct a treatment under high temperature. It can be seen that the main product is lithium carbonate, Recycled. As for lithium iron phosphate, its value is a headache for many enterprises. How to control the cost and benefit of recycling. This work is actually to analyze the failure mechanism of lithium iron phosphate. We hope to adopt different methods for each material, because the structure of lithium iron phosphate is very stable, and the lithium position will be lost after charging. So we can see the function of lithium iron phosphate after failure or thousands of cycles through element analysis, Through card comparison, we can see that it is actually iron phosphate and iron oxide, which directly reduces the performance and capacity of iron phosphate. Based on this failure mechanism, lithium can be added to the mixture of later materials in the form of carbonate or aluminum hydroxide for high-temperature calcination, and the material performance can be restored to a certain extent.
The following is about the wet process technology, which is our preferred technology in China. It mainly uses the acid leaching part to separate the metal elements of materials from the solid image to the liquid image. On the left is a general treatment process. On the right, we can see what are the main acid systems around the current waste batteries. Our traditional systems are mainly the three strong acids, hydrochloric acid, sulfuric acid and nitric acid, which are often used in our laboratories or industries. We know that during the treatment, on the one hand, these strong acids cause serious social corrosion, which leads to increased costs; on the other hand, during the reaction process, some chlorine and nitrogen oxides are released, causing secondary pollution to the environment. Now many units are studying whether a treatment technology can be efficient and green. Our research group's work is mainly to replace this core system, which will be introduced in detail later.
In order to obtain products with high added value, we need to regenerate the leaching solution. What is shown here is to regenerate the leaching solution, for example, to generate some porcelain materials, which have high conductivity and can be used in many fields. Back to battery electrode materials, there are alternative solutions.
In addition to the positive electrode, this negative electrode and electrolyte are several aspects that we have ignored in the past few decades. Maybe because the negative electrode graphite is very cheap, we think it is not worth supplementing. At present, we hope to regenerate and recycle different parts in an all-round way. This is because after recycling the negative electrode material, we can see that it can generate graphene materials. In the battery field or other fields, graphene has a great attraction for high conductivity. The utilization mechanism is mainly due to the increase in spacing caused by the insertion and removal of graphite ions during the repeated charging of graphite, The performance of the whole battery system is significantly reduced. If the negative electrode layer spacing increases after failure, can we use a special way? This work introduces ultrasonic assisted liquid stripping, and after stripping, each graphite sheet is characterized and identified. More than 60% of graphene is about one micron thick and less than 15 nanometers thick, with very high conductivity.
There are few reports on electrolyte recovery. Teacher Dai used the carbon dioxide connection extraction method in this work. His final material is that after the electrolyte is matched again, his conductivity can meet the current commercial requirements. Here is a brief introduction to our research work in this field. We have presided over a number of national 863 plans or national key fund projects under the leadership of academic leader Wu Feng since the 1980s. During the research and development process, we mainly built two centers, one is the National Electric Vehicle Collaborative Innovation Center, and the other is the Beijing Power Battery and Chemical Energy Materials Work Center, On these two platforms, we have further developed the following experimental platforms. Focusing on the recycling technology of waste lithium-ion batteries that we are concerned about today, we started in 1999 and adhered to it through the National 863 Plan. Until 2002, we undertook the transformation from industrialization to basic laboratory, and undertook the rolling of 973 for three consecutive periods. It has been about 19 years since this year. We have a certain foundation in this regard and hope to make some progress with you. This article was just published online in the middle of August. Our work mainly summarizes the current sustainable development of secondary batteries, including those of other systems, or this relatively environment-friendly and efficient regeneration process. We mainly provide or review the systematic algebra of secondary battery recycling from the perspective of sustainability, and propose some foundations and technological progress at home and abroad. Through these aspects, further research is carried out.
Our characteristics are mainly to replace inorganic acids in the traditional market. Whether organic acids can be used, a large number of screening will be carried out in the early stage. Conductivity and all aspects of performance will be analyzed. The leaching kinetics, leaching method and regeneration process of leachate will be systematically analyzed in detail.
The last one is about the recovery of negative electrode. Today, we will briefly introduce our work published in recent two years. The first work uses a parallel technology. We can see that the leaching rate of these elements is more than 98%, and the laboratory leaching rate is relatively high, and the synthesis is carried out later. Second, we studied whether the mixed materials, lithium ferric phosphate ternary or other materials are suitable for this system. We can see that its reaction mechanism is basically consistent with what we had predicted before. Later, we can see that its basic leaching rates and its performance of materials synthesized by Weng Chengyuan are very good. We also test this material. The next work is our relatively good system. We often hear about this lactic acid. No scientist has ever applied this lactic acid to battery recovery. We also tried this system to find out that this leaching system has a good effect on our battery recovery. Here are some of our data.
As for the recovery of the negative electrode, the negative electrode material is not recycled back to the battery material for a new field of development. It is hoped that after recycling this material, we can see that this first work mixes this negative electrode material with magnesium hydroxide. Finally, this sewage can be recycled as a slow release fertilizer for this soil. We can see that the phosphorus adsorption capacity of this material is 588 mg. The other is that after the failure, the graphite cathode is compounded with manganese oxide to analyze its mechanism. Where is the material used for heavy metal adsorption? The lead and silver are nearly 100%. The treatment effect of the whole heavy metal is relatively good. We hope to improve the adsorption in the later process.
In the final summary and outlook, we just mentioned our three principles, namely, the three E principles. How to ensure the high leaching efficiency, high economy and environmental efficiency of valuable metals in batteries? We can see that the initial material design is very critical around the core content of recycling. Imagine if we can carry out the earliest design from the source if we deal with the battery at the end of recycling, This material is degradable at the beginning of design, which is also a new direction of our current vision, and we hope to make some breakthroughs in the next few years.
The second part is about the cascade utilization. The cascade utilization is more used to decompose or reorganize the capacity of retired batteries. We propose whether the capacity can be regenerated without damage, because some capacity losses are reversible, if not, they cannot be regenerated, and if the reversible capacity can be activated through external conditions. In this part, we hope to strictly control the "three wastes" and finally regenerate the materials. If there is an application value in different fields, we can return to the battery level or other fields. This is my report today. Thank you all.
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