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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.

Jin Jun, associate researcher of Shanghai Silicate Research Institute, Chinese Academy of Sciences, attended the meeting and delivered a report entitled "Application of Solid Electrolyte Batteries and Energy Storage". The following is the full text of the speech:

Jin Jun: Good morning, leaders and experts. I'm Jin Jun from Shanghai Institute of Silicic Acid, Chinese Academy of Sciences. Today, I'd like to report some work of our laboratory in solid electrolyte batteries. This is my outline. We know that safety is the first consideration in energy storage application, because if a power plant has a safety problem, it will cause very serious consequences. Taking the power battery as an example, it can be seen from the figure that these are some of the situations about Tesla electric vehicles in the past two years. There have been a lot of safety accidents in electric vehicles in the past two years. In recent two months, there have been reports of combustion accidents in electric vehicles in Zhuhai and Hefei. Although it cannot be said 100% that auto ignition or combustion is caused by batteries, However, the proportion of combustion accidents in electric vehicles is higher than that in fuel vehicles, indicating that there are still some problems in the battery or system of electric vehicles. Maybe the battery itself or the system has some defects.

If the impact of electric vehicle safety accidents is relatively small, then the impact of a power storage station, if a safety accident occurs in a power station of several megawatt hours, is very huge. This is a recent accident at a power station in South Korea. We can see that the economic, environmental and other losses caused by the safety trial of the power station are very huge. Therefore, when designing or applying energy storage power plants, special consideration should be given to security. Therefore, in the energy storage battery we make, more attention is paid to solving its safety problems in terms of electrolyte. The existing mature lithium ion battery systems are mainly organic electrolyte systems, and such batteries are also widely used in the market. We have also done a lot of work in the battery of organic electrolyte system, while in the solid electrolyte, our laboratory is more mature in β- Alumina is used as solid electrolyte for solid sodium battery.

Solid state batteries have become a global hotspot. Both academia and industry pay great attention to this aspect. We can reduce the combustibility of batteries by using solid electrolyte. It can be seen from the comparison that traditional organic battery system batteries burn violently. If we use solid electrolyte, it will not burn. Although there are some combustion components in the battery, solid electrolyte can prevent combustion. At present, solid state battery R&D institutions in the world are mainly concentrated in the United States, China, Europe, Japan and South Korea, and some enterprises in China are also doing well. Domestic R&D is mainly done by some R&D teams represented by battery enterprises, Chinese Academy of Sciences, universities, etc.

In terms of materials, the core of solid state battery is solid electrolyte. Now there are many solid electrolyte systems, including polymer systems, inorganic systems, and organic inorganic composite systems,. However, these electrolyte systems have made great breakthroughs in some indicators. Sulfide electrolytes have high conductivity, close to the level of liquid electrolytes, but need to make breakthroughs in stability and cost. In terms of the oxide electrolyte system, Mr. Li mentioned just now that the conductivity can basically reach 10-3S/cm and the stability is also good, but there are problems such as poor mechanical properties and difficult film preparation technology. At present, the application of solid state battery in energy storage is still blank. These are some representative battery systems developed at home and abroad. We can see that Bosch is dominated by polymer systems, while Japanese enterprises are dominated by sulfide systems. Although Toyota has previously reported that it operates on the vehicle, it is still in the demonstration stage. At the same time, it has also proposed a time plan for the use of solid state batteries in vehicles. In China, the development of large capacity solid state batteries is mainly carried out by Weilan, Ganfeng Lithium and other battery enterprises.

There are still some key problems in the development of solid state batteries. Long life, safety and other factors should be considered when they are used in the energy storage field. In addition to electrolyte materials, the interface problem in solid batteries is very critical. In addition, the volume effect, stability, and interface compatibility in the long-term cycle process also need to be solved. In addition to several key materials, positive and negative electrode materials and electrolytes, there are many different interfaces in solid state batteries. For these interfaces, the key core issues also need more detailed research. At present, we are carrying out these research work.

For solid state batteries, we need to research from the most basic materials, interfaces, monomers to the final system modules, because only by fundamentally solving the key materials and interface problems, can we carry out systematic process research, so as to meet the performance requirements of single batteries. So we have made five plans for solid state batteries. Based on our previous research, we successfully applied for the national key research and development plan this year. In order to establish an intrinsically safe, ultra long life and low-cost solid state battery energy storage system for smart grid applications, we have studied the key materials, interface feature units, failures, and system demonstrations of solid state batteries. Put forward some specific indicators, which are also the goals we need to work hard to achieve in the future. We have established a relatively strong R&D team with the participation of many efficient research institutes and enterprises. Our laboratory has also accumulated a lot of experience in sodium sulfur battery and ZEBRA battery. Now it mainly develops ZEBRA battery, and has made improvements based on the safety problems of sodium sulfur battery. At present, ZEBRA battery has established a company and is establishing a production line. At the same time, our unit has already done demonstration projects in the park in terms of water system sodium batteries.

For solid sodium battery, we have accumulated a lot of experience from making sodium sulfur battery, and developed a new system of sodium chloride battery for its existing problems. Fiamn and GE companies abroad have successfully developed it and applied it to electric vehicles, renewable energy, communications and other fields. The special underwater life-saving products imported from China are sodium chloride batteries., At present, there are MW energy storage power plants in operation. Our laboratory has been working on sodium nickel battery for many years, and has a mature preparation technology of solid electrolyte tubes. The single battery prepared has been able to achieve hundreds of cycles, and is still being tested. In terms of lithium sulfur battery, our laboratory has also carried out research for more than 10 years. In the initial stage, it was mainly based on the liquid electrolyte system. In recent years, it has mainly developed a lithium sulfur battery system using solid electrolyte.

After the lithium metal is modified with solid electrolyte, it can be found that the cycle stability of the battery has been greatly improved. During the discharge process, it can be found that there is basically no degradation after standing for three days. However, if the battery is not modified, obvious self discharge will occur, and the curves will not completely coincide.. On this basis, we propose a concept of lithium sulfur battery with double electrolyte system. We use LAGP as the solid electrolyte, and use a small amount of liquid electrolyte to wet the interface between the positive and negative electrodes. The test results show that the specific capacity of the first discharge can reach more than 80% of the theoretical capacity, which is greatly improved compared with the ordinary liquid lithium sulfur battery. In particular, the charge and discharge efficiency is basically close to 100%, There is no shuttle effect problem in liquid lithium sulfur battery. In order to further improve the battery life, the interface was further improved by using polyfluoroether additives with insoluble polysulfides to modify the interface. The cycle performance of lithium sulfur battery was still very good at minus five degrees centigrade. After 1200 cycles at room temperature, the capacity did not degrade significantly. This interface modification is very helpful to the battery cycle life.

In order to further solve the safety problem of the battery, we gelatinize this interface to ensure that there is no flowing electrolyte inside. If the polymer is modified, it can also buffer the volume effect during the cycle. After the self discharge test of the battery, there is basically no degradation problem. After 300 cycles at 0.5C room temperature, there is basically no degradation. This structural design has greatly improved the battery performance.

LLZO solid electrolyte system has many advantages, including its stability to metals. It can use metal lithium as the negative electrode to improve the energy density of the battery. Powder preparation and ceramic sintering can be prepared in air, which has better structural stability and chemical stability than sulfide electrolyte. The disadvantage is that ceramics still have some weak side reactions in wet air, and there are still some processes to be optimized for sintering.. At present, the solid electrolyte developed by us can basically reach 10-3, and the density is above 97%. This picture shows some solid electrolyte products made by our laboratory. At present, the laboratory can produce 100kg of electrolyte powder annually. The size of solid electrolyte film is 1-6cm, and the thickness can be controlled to 200-300 microns. We have conducted some performance tests on the battery assembled with ceramic membrane. By modifying the negative electrode interface to prepare a layer of alloy layer to improve the interface stability, and the positive electrode uses sulfide additives to effectively convert the discharge products, we can see that the battery has a good cycle. After 200 cycles at 0.5C and 500 cycles at 1C magnification, it still has good performance.

Our laboratory has done some exploration work in solid state battery, but there are still some problems, including battery design, assembly, safety performance, etc.. For solid state batteries, we believe that they are intrinsically safe, but because there is no standard for the safety test of solid state batteries, there is no way to define what is safe. As for the specific energy of battery, some published papers and reports may have different opinions on calculation. For a battery, the final calculation is based on the results of actual samples tested according to certain standards. To improve the specific energy of solid state batteries, it is necessary to consider the loading capacity, thickness, electrode structure design, etc., so there are still some basic work to explore. For the specific power of solid state batteries, more consideration should be given to some interface design issues. At present, there are many academic researches and viewpoints on solid-state battery research. However, in terms of industrialization, because some key technologies involve core technologies of various enterprises that cannot be obtained, there may still be a lot of technologies based on engineering applications that need to be explored. This is the content of my report. Please comment and correct.

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