20 Nickel Metal Hydride No. 5 battery material companies compete in innovative technology

In the competition for innovative materials products/technologies, material companies from all aspects such as positive electrode materials, negative electrode materials, diaphragms, electrolytes and auxiliary materials have demonstrated their expertise. Driven by the trend of high energy density and high safety of power lithium batteries, the upstream material innovation goals are also developed around this. This article introduces the innovative materials products of 20 Nickel Metal Hydride No. 5 battery companies: 1. Positive electrode materials 1. Chengdu Bamo: Mass production of ternary materials and long-life high-nickel materials for high-safety power batteries Chengdu Bamo has successfully mass-produced ternary materials for high-safety power batteries and long-cycle life high-nickel materials and successfully achieved mass production, entering the domestic and foreign high-end passenger car market. At the same time, in order to meet the demand for high-quality ternary materials and high-nickel materials for power batteries, Chengdu Bamo adopts a fully automated production line design, introduces foreign high-end manufacturing equipment, and realizes fully automated production of materials. Chengdu Bamo introduced that the ternary/high-nickel materials independently developed and produced by the company have the characteristics of high energy density, excellent high-temperature cycle, small DCR, taking into account low-temperature rate and high-temperature storage performance, and outstanding safety performance. At the same time, the electrochemical performance of the product, the synthesis process of the material, and the convenience of processing at the battery end are fully considered from the design stage. 2. Shanshan Energy: The world's first 4.45V high-voltage lithium cobalt oxide mass production Shanshan Energy's high-voltage lithium cobalt oxide series positive electrode materials have excellent comprehensive performance, and have obvious advantages in capacity, high-temperature storage and DCR cycle performance. It adopts automated and intelligent production lines for stable batch production, reducing unit product energy consumption and unit product manufacturing costs. At the same time, the consistency and reliability of the product are effectively guaranteed. Among them, the 4.45V lithium cobalt oxide material is the world's first mass-produced 4.45V high-voltage lithium cobalt oxide material with independent intellectual property rights. The product's various technical indicators are stable, and the yield and yield rate meet the production technology requirements, and it has successfully achieved industrialization. The top six customers currently using it in batches are Samsung SDI, LGC, ATL, BYD, Lishen, and Zhuhai Guangyu. 4.45V lithium cobalt oxide material innovatively developed related technologies to solve the problem that lithium cobalt oxide materials become unstable under high voltage charging conditions, easily release oxygen, and have cobalt dissolution, causing battery performance degradation and safety issues. Successfully developed a lithium cobalt composite oxide positive electrode material with a charging cut-off voltage of 4.45V, good cycle performance, high temperature performance and thermal stability. 3. Weitego: Low-cost lithium iron phosphate positive electrode material The company's low-cost lithium iron phosphate positive electrode material production technology has been tested and used by customers such as Sichuan Nanguang New Energy, Haiying Technology, and Guizhou Huadis New Energy. The specific highlights are as follows: ? Self-produced low-cost iron phosphate precursor, the total cost is 6000-7000 yuan/ton, which is 30% lower than the market price of 8000-10000 yuan/ton, and the quality is above the market level; ? Self-produced low-cost lithium source, the cost price of the lithium source required for production is 25,000 yuan/ton through lithium extraction from brine, which is much lower than the market price of 60,000-80,000 yuan/ton; ? The cost price of lithium iron phosphate synthesized from the above raw materials is much lower than the market price; ? The wastewater discharge of the iron phosphate production technology of this project is 5-8 tons per ton of product, and the pH of the wastewater is between 6.5-7. The solutes in the wastewater can be recycled as nitrogen fertilizer, which is relatively environmentally friendly; ?, Lithium extraction from brine uses lithium extraction agents to adsorb and desorb lithium ions, does not generate wastewater, and other elements in the brine can continue to be recycled. 4. Jingmen GEM: High-nickel ternary precursor manufacturing method and equipment technology The products of Jingmen GEM competing for the "Annual Technology Innovation Award" are: high-nickel ternary precursor manufacturing method and equipment technology. According to the introduction, this technology has achieved three innovations: ? Designed and implemented the continuous and intermittent automatic control procedures for the precursor, realized the program control of the reaction process of the high-nickel ternary material precursor, increased the production efficiency by 50%, and improved the consistency of the product; ? Comprehensive filter press, centrifuge and other cleaning methods, saving 50% of water per ton of product, reducing production costs; ? Designed and implemented a fully pipelined and fully automated logistics and transportation system, avoiding the introduction of foreign matter caused by the handling process, improving product quality, and improving the safety of positive electrode materials. Due to the use of the above innovative technologies, the magnetic foreign matter content of the high-nickel ternary precursor produced is controlled within 20 PPb, and the tap density reaches 1.6g/cm3. At present, the high-nickel ternary precursor produced by this technology has been applied to actual production, mass production has been achieved, and the product has been certified by many mainstream power battery companies in China, forming a batch supply. 5. Meidari: The total residual lithium content of the high-nickel positive electrode water-free washing process is less than 0.15%. The high-nickel positive electrode material has a high specific capacity and can effectively improve the battery energy density, and has a wide range of application prospects. However, a more prominent problem of high-nickel materials at present is the high total residual lithium content. During the production and preparation of batteries, it is easier to absorb water and carbon dioxide in the air to react, forming lithium carbonate and lithium hydroxide on the surface of the material, causing capacity decay, hindering the diffusion of lithium, affecting battery performance, and adversely affecting the battery production process and processing performance. At present, most domestic high-nickel material manufacturers use water washing to reduce the amount of residual lithium, but this method is prone to produce a series of negative effects. For example, due to the deterioration of high-temperature storage performance caused by the destruction of the surface structure of the material, if not handled properly, it will also lead to reduced capacity and decreased cycle performance; in addition, reducing the amount of residual lithium by water washing will further increase production costs. Meidari said that the company prepares high-nickel positive electrode materials through a process that does not require water washing, and the total residual lithium content can be controlled within 0.15%. In addition to effectively reducing the residual lithium on the surface of the material through the water-free preparation process, while reducing production costs, it also avoids a series of negative effects brought about by water-washed materials. Second negative electrode material 6. Zhengtuo Energy: Ultra-high energy density silicon-carbon negative electrode ZT-SC-600 Compared with the mainstream silicon-carbon products in the market, Zhengtuo Energy's ultra-high energy density silicon-carbon negative electrode ZT-SC-600 uses nano-silicon as silicon material. The unique process makes the cost of raw materials lower, forming a high cost-effective advantage in the market, and improving the versatility of the product through equipment selection and process improvement. The full battery design capacity (mAh/g) of this silicon-carbon material is ≥600, the cycle performance is 500 weeks 0.5C ≥80%, and the pole piece compaction density (g/cm3) is ≥1.60. Zhengtuo Energy expects to achieve an annual production capacity of 2,000 tons this year. At present, the equipment installation of this product project has been completed and it has entered the small-scale trial production stage. 7. Snow: Solving the problem of silicon-carbon negative electrode expansion. The capacity is 500mAh/g. At present, silicon-carbon negative electrode materials are expected by everyone as a new star to improve the energy density of power batteries, but they have not been commercialized due to problems such as low first coulomb efficiency and lithium insertion/extraction expansion. SiO itself has a high capacity (2600mA?h/g), and will irreversibly form Li2O and Li4SiO4 during the first charge and discharge process, which leads to a low first coulombic efficiency of SiO, which is only 50%-53%. Moreover, after SiO-based materials are prepared into electrodes, there are still problems such as low conductivity and large volume changes during the insertion/extraction of lithium (the volume expands by 260% when fully embedded with lithium). Through independent research and development, Snow uses SiO nano-crystallization technology, carbon coating technology, disproportionation technology, and graphite composite technology to prepare carbon-coated SiOx/graphite composite materials, while reducing the SiO volume effect and achieving simultaneous improvement in energy density and cycle performance. At present, Snow's SiO product has a gram capacity of more than 500mAh/g, an initial coulombic efficiency of more than 89%, and can achieve a cycle retention rate of more than 800 cycles of more than 80%. Different from the simple mixing or compounding process of SiO and graphite in traditional preparation technology, the carbon-coated SiOx/graphite composite negative electrode material prepared by Snow Silicon Carbon Products has a unique material production process, which technically solves the expansion effect of SiO during charging, greatly improves safety performance, and significantly improves cycle performance. 8. Luoyang Yuexing: The gram capacity of graphite materials has reached 400mAh/g. The gram capacity of current market graphite negative electrode materials is close to the theoretical value of 372mAh/g, which is difficult to meet the current and future energy density requirements; although the research on silicon-carbon negative electrode materials is very hot, its large expansion, low first efficiency, short cycle, high cost and other problems still limit its application. Luoyang Yuexing introduced that the high-energy-density graphite negative electrode material technology developed by the company increases lithium storage nano-micropores on the surface coating layer of the material particles, improves the low first efficiency caused by the increase of micropores, and achieves a gram capacity exceeding the theoretical value of 372mAh/g. In 2013, the gram capacity reached more than 380mAh/g, and in 2018, the gram capacity reached 400mAh/g. At the same time, the application of this technology can also improve the performance in high and low temperature, rate, cycle and other aspects to varying degrees. It can be comparable to silicon-carbon materials when used alone. In addition, the nano-microporous characteristics of high-energy-density graphite provide space for pole piece expansion, which is particularly suitable for use with silicon-based materials. Three diaphragms 9. Cangzhou Mingzhu: Developing a series of coated modified diaphragms As of 2018, Cangzhou Mingzhu has accumulated many years of manufacturing technology and experience in polyolefin diaphragms. With its own technology and product strength, it has won the favor of a number of mainstream domestic power battery companies such as BYD, Lishen, Guoxuan High-tech, and AVIC Nickel Metal Hydride No. 5 battery. In July of this year, Cangzhou Mingzhu also passed the product certification of CATL and entered the subsequent introduction period. With the upgrading of customer demands of battery enterprises, Cangzhou Mingzhu has developed a series of coating and modification products to address the shortcomings of traditional polyolefin diaphragms, including ① ceramic coated diaphragms and aramid coated diaphragms: improving high temperature resistance; ② PVDF coated diaphragms: improving the bonding performance between diaphragms and pole pieces; ③ ceramic coated adhesive diaphragms: products with both temperature resistance and adhesion. These coated products can be combined with customer requirements to select substrates and coatings, and carry out targeted product design and development. 10. Xingyuan Materials: Achieving a technological breakthrough in the production of PP/PE/PP three-layer films. At present, the company's products mainly include three series: dry-process diaphragms, wet-process diaphragms, and coated diaphragms. It has in-depth cooperation with well-known domestic and foreign power battery companies such as LG Chem, Lishen, Guoxuan High-tech, Wanxiang, and BYD. The person in charge of Xingyuan Materials revealed that the company independently developed dry-process high-toughness diaphragms, dry-process anti-wrinkle diaphragms, dry-process low-temperature closed-cell diaphragms, dry-process high-strength diaphragms, wet-process high-strength, wet-process low-strength, wet-process low-temperature closed-cell diaphragms, coated low-shrinkage diaphragms, coated low-water diaphragms, coated glue-coated diaphragms and other functional diaphragms to meet the different usage needs of customers. It is particularly worth mentioning that the company's products have excellent consistency. With the independently developed composite-stretching integrated equipment, the CPK values of various performance indicators are all over 1.67, which can fully meet the needs of different customers and different product types at home and abroad. In addition, the company broke the foreign monopoly and achieved a breakthrough in the production technology of PP/PE/PP three-layer film. 11. Zhongke Technology: The puncture strength of the new dry-process double-stretched ultra-thin product reaches 330gf. Zhongke Technology's new dry-process double-stretched ultra-thin series products are based on the existing GRE-12P products. According to the market and the needs of each household, the products are optimized and upgraded, and the GRE-12PS series and GRE-12PH series of ultra-thin products are newly developed. Among them, the S series focuses on the strength advantage of its products. Through improvements in raw materials and process methods, the strength of the 12μm diaphragm products has been significantly improved. The tensile strength in the MD direction can reach 1600kgf/cm2, and the puncture strength can reach 330gf, which further improves the safety performance of the product and can replace wet-process products of the same thickness. The GRE-12PH series focuses on the rate advantage of its products. By optimizing and improving the product pore structure and pore size distribution, the product has a higher porosity ratio and a higher battery energy density. At the same time, it can also better meet the charging and discharging requirements of rate-type batteries. Zhongke Technology said that the company's new ultra-thin S and H series products are more excellent in physical properties and strength, especially the tensile strength in the MD direction, which has reached the standard of the same type of wet-process diaphragms; the puncture resistance is also far superior to other dry products, and can contribute higher energy density at a lower cost and under the premise of ensuring safety. Compared with wet-process base film, Zhongke Technology's new dry-process double-drawn ultra-thin series products have the same performance while reducing costs by 50%, providing a new way to reduce costs for ternary power batteries; compared with ordinary dry-process diaphragms, the strength is increased by nearly 50%, which can replace 16 and 20 ordinary diaphragms, providing a better choice for improving the energy density of lithium iron phosphate power batteries. 12. Newmi Technology: 5μm wet-process diaphragms are mass-produced to prepare for H-HP4um. As the first diaphragm company in China to achieve import substitution of 5um ultra-thin diaphragm products, Newmi Technology has achieved stable production and stable supply. The sales of ultra-thin diaphragms account for more than 50% of the annual sales, contributing to the localization of domestic first-line digital battery companies. In 2018, Newmi Technology independently developed and mass-produced the ultra-thin H-HP4um, which is the thinnest lithium-ion battery diaphragm in China. At the same time, according to market demand, it developed and mass-produced HL (low-transmittance) products. 13. Jinli Co., Ltd.: Mass production of aramid coated diaphragms Jinli Co., Ltd. achieved mass production of meta-aramid coated diaphragms in December 2017, and finalized the research and development of para-aramid coated diaphragms in October 2018, and has now obtained relevant patents. During the development process of this product, the difficulties of aramid synthesis, storage and transportation were overcome; the key technologies of aramid film formation and pore-making processing were broken through, and the bottleneck of thermal stability was solved. Finally, an overall technological breakthrough was achieved, and mass production was achieved first in China. Compared with traditional polyolefin diaphragms and their derived inorganic and organic coating diaphragms, this product has the advantages of anti-oxidation, acid and alkali resistance, flame retardancy, abrasion resistance, and tear resistance; the thermomechanical strength is much higher than that of the current diaphragms on the market, which can play a key protective role in resisting battery failure and greatly improve the safety of the battery; the film breaking temperature exceeds 260°C, which is an ideal ultra-durable lithium-ion battery diaphragm, which can greatly improve the safety of high-energy-density batteries. At the same time, this product can reduce its cost to the same level as the oil-based PVDF diaphragm sold on the market through independently developed production equipment and process flow, and can control the selling price to less than half of similar foreign products, making a significant contribution to the localization of key Nickel Metal Hydride No. 5 battery materials and reducing costs. Jinli Co., Ltd. stated that during the development of this product, full consideration was given to environmental protection, low cost, and localization of equipment. It can achieve 100% localization of equipment, 100% recycling of organic solvents, and zero wastewater and waste gas emissions, which greatly reduces manufacturing costs and is environmentally friendly. At present, more than 50% of the top 10 Nickel Metal Hydride No. 5 battery manufacturers at home and abroad are conducting small or medium tests on this product. Four electrolytes 14. Xinzhoubang: The test data comparison of the ternary power battery electrolyte using the independently developed new low-impedance negative electrode film-forming additive LDY269 shows that LDY269 has the advantages of low impedance, good low-temperature charging, and good cycle life compared with the traditional negative electrode film-forming additive VC. When LDY269 and LiPO2F2 are combined together, the effect is more significant. The combination can effectively reduce the internal resistance of the battery and improve the high temperature performance and cycle life of the battery. When LDY269 is used in the electrolyte of ternary power batteries, it has obvious advantages: 1. It improves the rate performance and high-temperature cycle performance of ternary high-voltage batteries, and improves the use characteristics of power batteries in high-temperature environments; 2. This product is suitable for power batteries with a positive electrode of ternary conventional voltage or ternary high-voltage materials and a negative electrode of graphite or silicon-carbon materials, including 4.2V, 4.35V, 4.4V, etc. The applicable battery types are cylindrical, square, soft pack, etc.It has high compatibility and has wide promotion value. It is worth mentioning that LDY269 is independently developed and synthesized by Xinzhoubang, with completely independent intellectual property rights. Its raw materials are cheap and easy to obtain, and the cost is controllable. The cost of electrolyte products using this type of additive can be controlled at no more than 20% of the cost of existing electrolytes, which has a high cost performance. In fact, the series of electrolytes using LDY269 additives have been maturely applied to ternary power batteries of high-end customers at home and abroad, and can meet the power, low temperature, high temperature and cycle life requirements of the battery. 15. Tianci Materials: Electrolyte Products for High-Nickel Batteries The company has conducted in-depth research on the performance attenuation mechanism of high-nickel batteries, and found a way for electrolytes to solve the performance attenuation of high-nickel batteries. It has developed a series of new positive electrode film-forming additives and new lithium salts, and developed a series of electrolyte products suitable for high-nickel batteries, which have good customer feedback in the high-nickel battery market. The electrolyte products for high-nickel batteries can meet the capacity retention rate of ≥80% for 3000 cycles at room temperature, ≥80% for 2000 cycles at high temperature of 45℃, and ≥80% for -20℃ discharge. The performance is at the forefront of similar electrolyte products in the industry, and has achieved large-scale mass production and shipment. It is worth mentioning that the company's independently developed additive A231 has excellent performance in high-nickel batteries, can replace DTD, and has the performance advantages of room temperature storage and high and low temperature performance. Our company has opened up the A231 synthesis route, and the purity of self-produced A231 is >99.5%, which is better than the market average, and has significant market competitiveness in terms of performance and price. Two related electrolyte patents have been applied for, and they are in the PCT international stage. Taking the high-specific-energy high-nickel ternary power battery electrolyte TC-E8630 as an example, it is suitable for square aluminum shell/soft-pack power batteries with high-nickel ternary materials (Ni>80%) as the positive electrode and graphite as the negative electrode. This product innovatively developed positive electrode film-forming additives to inhibit the oxidation of the high-nickel positive electrode to the electrolyte and the dissolution of transition metal ions, so that the high-nickel battery has excellent comprehensive performance, especially high-temperature performance. 16. Shandong Hairong: The electrolyte has a high-temperature 45-degree cycle life of 2,000 times. Compared with other electrolyte products, Shandong Hairong's power electrolyte product indicators are higher than the industry standard. The graphite system has a room temperature cycle life of more than 5,000 times and a high-temperature 45-degree cycle of up to 2,000 times. It has excellent safety performance and high cost performance. It has been widely used in pure electric buses, pure electric minibuses and passenger cars. Shandong Hairong stated that the company's products are positioned in the mid-to-high-end market, focusing on supporting the power and energy storage battery market. With its excellent product quality, stable performance, and high safety, it has been recognized by power and energy storage battery customers. At present, it has formed a long-term and stable cooperative relationship with well-known domestic Nickel Metal Hydride No. 5 battery companies such as Tianjin Lishen, Zhuhai Yinlong, and Aoyou Battery. 17. Chaowei New Materials: New lithium salt additives for lithium batteries. The company competing for the "Customer Trusted Product of the Year" at this year's Golden Globe Awards is a new lithium salt additive for lithium batteries, including CF1101 (LiTFSI, lithium bistrifluorosulfonyl imide), CF1302 (LiDFP, lithium difluorophosphate), CF1109 (LiODFB, lithium difluorooxalatoborate), CF1205 (LiTFS, lithium trifluoromethanesulfonate), etc. From the perspective of technology, quality, production capacity, price and other aspects, Chaowei New Materials has outstanding competitiveness. In fact, Chaowei New Materials has been widely recognized in the global market. Among the top ten domestic electrolyte companies, the company's customer coverage rate has reached 100%; among the top six foreign electrolyte companies, the company's customer coverage rate exceeds 70%. The products have been applied on a large scale in BMW and other internationally renowned car companies. Five auxiliary materials 18. Nord shares: Achieve mass production of perforated copper foil. At present, with the improvement of the technical level of power batteries, the current collector foil is becoming more and more lightweight. For example, the material thickness of Nickel Metal Hydride No. 5 battery copper foil has gone from 9um and 8um to 6um. Nord shares judge that the application of Nickel Metal Hydride No. 5 battery copper foil to 6um in power batteries has reached its limit, and there is no greater improvement in the performance of power batteries such as charging and discharging and rate. In the future, to meet the needs of battery companies, perforated copper foil will be the market trend. In the future, the application opportunities of perforated copper foil in the field of power batteries will mainly focus on high-rate and high-specific energy power batteries and all-solid-state lithium batteries doped with silicon and carbon. Especially in silicon-carbon power batteries, perforated copper foil can solve three technical difficulties: one is the peeling problem of silicon-carbon negative electrode after multiple cycles; the second is the problem of pre-embedded lithium in silicon-carbon negative electrode; the third is the problem of ion transmission channel. At present, Nord shares have achieved mass production of perforated copper foil, and have completed sample delivery to domestic battery companies and automobile factories, and customers are interested in feedback. 19. Lingzhi New Materials: LZ7626 low-density liquid silicone rubber for power battery packaging protection LZ7626 is a low-density liquid silicone rubber used for power battery packaging protection. Its density is as low as 0.60g/cm3. It will not significantly increase the weight of the battery box when used for Nickel Metal Hydride No. 5 battery packaging protection. Compared with the mainstream silicone potting glue in the market, the density of this product is only 1/2 to 1/3 of conventional products, which provides good support for the lightweight of the battery and is an upgraded version of the previous potting glue. This low-density liquid silicone rubber has two main functions: ① It has V0-level flame retardant performance. When individual cells of the battery pack are out of control, it can effectively prevent high temperature and flames from spreading to other cells, thereby effectively preventing the expansion of the accident and providing valuable time for accident handling and personnel escape; ② The product is soft and elastic, which can provide excellent shock absorption for the battery module, and can also absorb a lot of energy during violent collisions, thereby providing protection for the battery pack. 20. Bolin Technology: FPC solution for power battery pack Compared with traditional wiring harnesses, FPC has many advantages such as high integration, automated assembly, assembly accuracy, ultra-thin thickness, ultra-softness, and lightweight. The FPC solution can help the power battery pack achieve a regular layout and compact structure. The "Power Battery Pack FPC Solution" that Bolin Technology participated in this time mainly solves the problems of messy wiring harnesses, temperature collection, circuit protection, etc. of the battery pack. It has the following advantages and characteristics: 1. Safe and reliable; 2. High space utilization; 3. High temperature resistance; 4. Chemical corrosion resistance; 5. Electrical insulation; 6. Easy installation, automated production, and reduced costs.

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