There are three main routes for solid-state battery electrolyte materials, which are polymers, oxides and sulfides. Each of the three products has advantages and disadvantages, and different companies choose different paths, but at present, no one can fully achieve the balance of technology and mass production costs.1: European and American companies mainly use polymer routesThe advantage of the polymer is that its conductivity is similar to that of a liquid electrolyte. However, the shortcomings are also obvious, the mechanical strength is insufficient, and there is still the problem of lithium dendrite piercing. In other words, the internal conduction problem of polymer solid-state batteries still exists, and safety cannot be effectively guaranteed. At present, European and American companies mainly use the polymer route.2: Japanese and Korean enterprises adopt the sulfide routeThe sulfide has high conductivity, close to the liquid electrolyte, and the interface is relatively stable, with both strength and processing properties, and high interface compatibility. However, the air stability of sulfur is poor, and when it is exposed to the air, it is easy to react with water and oxygen in the air to produce hydrogen sulfide toxic gas. Therefore, the synthesis, storage, transportation and post-treatment of sulphide electrolytes need to rely heavily on inert gases or drying chambers. As a result, the preparation process is extremely complicated and the cost is high. In addition, the sulfide electrolyte itself is also expensive. At present, mainly Japanese and South Korean companies adopt the sulfide route.3: Chinese enterprises are more likely to adopt the oxide routeIts advantages are high density, high mechanical strength, and it is not easy to puncture, so it can effectively improve safety. However, it is also its high density that causes the internal impedance to be too large, resulting in poor conductivity. "Its internal impedance is very large, and even affects the actual performance of internal charging and discharging, which is not as good as liquid products."In all the current solid electrolyte technology routes, the polymer is not so prominent, short board, while the industry maturity is higher.Long board, due to the high flexibility of polymer electrolyte material, easy processing, the price is only slightly higher than the liquid; The production is compatible with the existing battery process, the equipment cost is not different, and the mass production cost is low. In terms of performance, the polymer material has good contact with the positive and negative electrode material interface, which is conducive to the extension of battery cycle life.

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.

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.

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.

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.

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

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.

The development of all-solid-state batteries began in the 1970s. Only later, with the technological innovation and large-scale commercial use of lithium-ion batteries in the early 2000s, the industry's attention to all-solid-state batteries has declined. Thirty years to the east, thirty years to the west, a new round of battery innovation cycle may be opened in 2030.Compared with liquid batteries, the core change of solid-state batteries is the introduction of solid electrolytes. According to the material type of solid electrolyte, the current solid state battery mainly includes oxides, sulfides, polymers and halides and other technical routes, and each route has its own advantages and disadvantages. For example, the oxide has high safety, but its easy brittleness leads to its complicated preparation process; Sulfide has high ionic conductivity, but the air stability is poor and H2S toxic gas is formed, and the cost is high. The polymer is relatively soft, the solid contact is the best, but the conductivity is low; However, halides are still mainly in the laboratory research stage.The whole industry placed the hope of the "next generation battery" on solid-state batteries, and even believed that this is the terminator of liquid lithium batteries, mainly due to the perfect properties of solid-state batteries.First, high security.Secondly, the energy density of all-solid-state batteries should also exceed that of liquid batteries, and the theoretical upper limit can reach 500 Wh/kg.Thirdly,Increased energy density means increased endurance.Lastly, the ion conduction mode of the liquid battery needs to go through solvation, desolvation and other processes, and the charging power is therefore limited.However, good all have a price, so far no manufacturer can produce solid-state batteries on a large scale, which actually reflects the difficulty of high.Since solid-state batteries still have so many challenges, why are so many companies insisting on developing solid-state batteries?1.the product characteristics of solid-state batteries can solve the safety and mileage anxiety of current new energy vehicle usersDue to the use of non-flammable, high and low temperature non-vaporization and non-solidification of solid electrolyte, solid-state batteries show strong high temperature safety, and maintain good low temperature characteristics to avoid low temperature battery life greatly reduced; In addition, solid-state batteries, due to their higher voltage window, can be further adapted to high-capacity positive and negative materials, such as lithium-rich manganese anode, silicon-based negative electrode and lithium metal negative electrode, so as to achieve higher energy density and increase the battery life under the same power.2.In the context of global competition for new energy vehicles, the competition for solid-state batteries is being staged around the worldIn the face of the industrial advantages formed by China in the development of global new energy vehicles, especially in the field of power batteries, which makes countries in Europe and the United States that need to transition to new energy urgently need to find new solutions, so the research and development of solid-state batteries has risen to become the national strategy of major countries in the world. For example, Japan is making national efforts to develop sulfide solid-state batteries, and strive to achieve 450Wh/L and 6C (@25 ° C) by 2027; The EU has also built a complete battery system from policy, innovation, and business, and plans to achieve polymer or composite solid-state batteries to break through 400-500Wh/kg and 800-1000+Wh/L during 2027-2030. The United States DOE plans to develop a solid-state battery in 2030 in 2021, with a production cost of less than $60 /kWh and an energy density of 500Wh/kg; Based on its K-Battery strategy, South Korea has also explicitly invested 40.6 trillion won to promote the commercial use of 400Wh/kg solid-state batteries in 2025-2028 and the loading of vehicles in 2030; China also set up the solid-state battery industry innovation consortium and the all-solid-state battery industry-university-research collaborative innovation platform in this half year to accelerate the breakthrough of (all) solid-state batteries and maintain the leading edge.