In the current Chinese government to vigorously promote the development of new energy and related industries under the environment, how to promote the lithium titanate battery technology and its application in the electric car and energy storage market for China's lithium titanate battery industry is a machine , No longer come
Development Status of Lithium Titanate Battery Technology at Home and Abroad
Since the lithium-ion battery in 1991 since the industrialization of the battery's anode material has been graphite in the dominate the world. Lithium titanate as a new type of lithium-ion battery anode material due to its many excellent performance and attention.
From the late 1990s, such as the lithium titanate material in the lithium ion mosaic and debonding process in the crystal structure to maintain a high degree of stability, lattice constant changes in small (volume change <l%).
This "zero strain" electrode material greatly extends the cycle life of lithium titanate batteries. Lithium titanate has a spinel structure unique to the three-dimensional lithium-ion diffusion channel, with excellent power characteristics and high and low temperature performance advantages.
Compared with the carbon negative electrode material, the potential of the lithium titanate is high (1.55 V higher than the potential of the lithium metal), which causes the solid solution layer normally grown on the surface of the electrolytic solution and the carbon negative electrode to be substantially not formed on the surface of the lithium titanate The
More importantly, it is difficult to generate lithium dendrites on the surface of lithium titanate in the voltage range used by the normal cells. This largely eliminates the possibility of a short circuit formed by lithium dendrites inside the battery. So the lithium titanate for the negative lithium-ion battery safety is the author to see the various types of lithium-ion battery safety in the highest.
Most of the industry have heard of lithium titanate instead of graphite as a lithium anode material lithium battery life of up to tens of thousands of times, much higher than the traditional traditional lithium-ion battery, only a few thousand times the cycle of life.
As most professional lithium people have never really hands-on production of lithium titanate battery products, or just do a few times encountered difficulties on hasty end. So they did not stop and carefully think about why most of the production of the traditional traditional lithium-ion battery is usually only completed 1000 ~ 2000 times charge and discharge cycle life?
Traditional lithium-ion battery cycle life is the root cause of the root cause of one of the basic components - graphite negative embarrassing it? Once the graphite anode replaced by spinel-type lithium titanate negative, the same basic lithium-ion battery chemical system can be recycled to tens of thousands or even hundreds of thousands of times.
In addition, many people talked about the low density of lithium titanate battery energy, but ignored a simple and important fact: that is lithium battery long life cycle, extraordinary security, excellent The power characteristics and good economy. These features will be the achievements of the current rise of large-scale lithium battery energy industry is an important cornerstone.
Nearly 10 years, domestic and foreign research on lithium titanate battery technology can be described as surging. Its industrial chain can be divided into lithium titanate material preparation, lithium titanate battery production and lithium titanate battery system integration and its application in the electric vehicle and energy storage market.
Lithium titanate material
International research and industrialization of lithium titanate materials are more leading the United States Austrian titanium nanotechnology companies, Japan's Ishihara Industry Co., Ltd., the United Kingdom Zhuangxin Wanfeng company. Which the United States Austrian titanium production of lithium titanate material in terms of magnification, safety, long life and high and low temperature performance. However, due to the production method is too lengthy and fine lead to high production costs, so that it is more difficult in commercial promotion.
Ishihara is one of the largest producers of titanium dioxide in Asia. The company has production bases in Japan, Singapore and Taiwan. Ishihara industry to make full use of its abundant raw material resources to wet process successfully developed a variety of low-cost, high magnification, different granularity of lithium titanate products. Its performance similar products in the price comparison of the United States Austrian titanium lithium titanate material has a greater advantage, but less than China's domestic products are inferior. Johnson Matthey took over the original German Southern Chemical Company has lithium iron phosphate and other materials, but in the lithium titanate research and development and production of inadequate, product quality is difficult to stabilize.
Domestic production of lithium titanate materials have been more than, such as Sichuan Xingneng New Materials Co., Ltd., Zhuhai Yinlong New Energy Co., Ltd., Huzhou Micro-Hong Power Co., Ltd., Shenzhen Beitui New Energy Materials Co., Ltd., Hunan Shanshan New Materials Co., Ltd. and Anhui and Shenzhen around a number of smaller manufacturers of lithium titanate.
Sichuan Xingneng is a professional manufacturer of lithium titanate materials, with an annual capacity of 3,000 tons, lithium titanate production process with customer adaptability and stability, can not change the existing production lines and equipment in the case of flexible adjustment, to produce Suitable for different customer requirements of lithium titanate, and to maintain product technical stability. Xing can rely on the upstream of the lithium and titanium resources, can be achieved from the original ore to the final material of the co-production, which can achieve lithium alloy product performance improvement and cost reduction, to avoid the impact of raw material market volatility.
Zhuhai Yin Long in 2011 completed the acquisition of 53.6% stake in the United States Austrian titanium nanotechnology company to become a rare one at the same time have a lithium titanate material preparation, battery production, lithium titanate electric vehicle, energy storage system, FM Peaking and other applications of a number of core technology and more than 30 patents of the enterprise.
At present, the annual production capacity of lithium titanate is 100 tons and the high quality nanometer grade lithium titanate is provided for the northern Austrian titanium and Zhuhai Yinlong. Zhuhai Yinlong New Energy has also carried out strategic cooperation with the research and development of new lithium titanate materials in the Ishihara industry. The cost of the materials will decrease with the increase of its output, which is expected to be close to the current price of graphite anode materials in the next few years.
Huzhou micro-macro is currently in the domestic industry to promote lithium titanate battery technology and other fast-charge battery one of the most successful enterprises.
Huzhou micro-production of lithium titanate materials are mainly used for their own production of lithium titanate battery products. Huzhou micro-macro lithium titanate battery products in domestic and foreign markets continue to expand the lithium titanate technology in the electric car and energy storage market has played a good role model.
Shenzhen Bei Terui is currently the world's largest supplier of lithium carbon anode. The company has a strong R & D team, is also one of the drafters of lithium titanate industry standards. Shenzhen Bettree strong sales network will also be in the sales of lithium titanate market in the first place, has introduced carbon coated lithium titanate and carbon-free coated lithium titanate 2 products. However, the current lithium titanate material is not Betty's flagship product. Lithium titanate battery market has not yet fully rolled out the case, the company has not yet in the production of lithium titanate materials to develop long-term plans.
Lithium Titanate Battery and Its Application in Electric Vehicles and Energy Storage
International can be mass production of lithium titanate battery manufacturers are not many, mainly to the United States Austrian titanium and Japan's Toshiba Group as the representative. Lithium titanate battery application market is mainly electric vehicles, energy storage market and industrial applications.
The United States Austrian titanium lithium titanate battery manufacturing has its unique core technology, in the international specifications of lithium titanate battery manufacturing is still in a leading position, and has solved the so-called "flatulence" problem. At present its fourth generation 65Ah single lithium titanate battery has been used for energy storage system, at 65 ℃ cycle tens of thousands of times still no significant capacity attenuation.
In the application of lithium titanate battery system, the Austrian titanium for the United States to provide hybrid electric buses in 2008 has been put into operation so far. Its fuel economy index of 106.4kg / L is much higher than the ordinary diesel generator 23.8kg / L. The company provides a 1MW storage system for the 10.5MW wind farm in Hawaii's Natural Energy Agency and is connected to the local grid and provides a three-year technical support service. This lithium titanate battery energy storage system is mainly used to control the voltage fluctuations of renewable energy, and the unit load change rate control in 1MW / min or less.
Austrian titanium 1MW high-capacity high-power energy storage unit is currently the only in the US power grid more than 2 years of field business operations and performance quality inspection through the large-capacity lithium titanate battery products. Energy storage system cycle more than 500000 times, charge and discharge total power more than 3300MWh, the system capacity loss is less than 2%, and the power and no significant attenuation.
Japan's Toshiba mass production to "SCiB" for the brand of lithium titanate batteries. Which 3.2Ah, 10Ah and 20Ah aluminum square battery is mainly used for electric motorcycles, electric vehicles and car start and stop the battery. SCiB battery has a fast charge and long life advantage, 10 minutes to charge more than 90%, repeated charge and discharge 3000 times the capacity of less than 10% attenuation, has been applied in bulk "EV-neo" electric motorcycle.
In terms of energy storage, Toshiba is using Japan's new solar program Dongfeng is the application of lithium titanate batteries to large-scale energy storage power plants and household energy storage systems. Another Japanese company Murata has developed a new type of lithium titanate battery using 5V lithium manganese oxide as the cathode. The voltage difference of 3.2V, the energy density can reach 130Wh / K song, more than the current level of lithium iron phosphate battery.
Lithium titanate battery production has been more than domestic, such as Huzhou micro-Hong, Zhuhai Yinlong, Shenzhen Bo Lei, Tianjin Jie Granville Power Industry Co., Ltd., Sichuan Xingneng, CITIC Guoan solid power Technology Co., Ltd., Hunan Shanshan and Anhui and Shenzhen around a number of smaller manufacturers of lithium titanate batteries.
Huzhou micro-macro since its inception in 2006 has been committed to the development of lithium titanate technology. The company's lithium titanate battery production needs of lithium titanate materials, diaphragms, electrolytes and cathode materials were vertically integrated. In recent years in order to meet market demand, Huzhou micro-macro with Nissan 80,000 10Ah lithium titanate battery product capacity and 2 times the lithium titanate battery is the capacity of multiple positive lithium battery products.
As of the end of 2014, Huzhou micro-macro 10-minute fast rechargeable battery system has been equipped with more than 3,000 hybrid-based electric buses, mainly sold to the United Kingdom, the Netherlands and China Chongqing and other places. In the energy storage market, Huzhou micro-macro, respectively, in the United States, Vermont and Chongqing, China installed for the grid regulation and power grid demand management of lithium titanate battery energy storage system.
Zhuhai Yinlong current production of lithium titanate battery products are 20Ah and 65Ah flexible battery and 25Ah, 30Ah and 55Ah cylindrical battery, performance indicators have reached the United States Austrian titanium production of lithium titanate batteries. Battery 100% DOD cycle more than 16,000 times, 10% DOD reached 1.6 million times. These batteries have been through the North Automotive Quality Supervision, Inspection and Testing Institute (201) of the third party testing.
In the application, Yinlong new pure electric bus using a cylindrical, long life, fast charge and discharge of lithium titanate battery, life mileage of up to 30 ~ 80km, fast charge only 6 to 10 minutes, can also be used at night Valley Slow charge 30 to 60 minutes full. The series of models have been successfully put in Guangdong Zhanjiang, Hebei Handan, Shijiazhuang and other public transport system.
Yinlong designed for the Beijing bus design and development of antique clams in September 2014 put into commercial operation. The car was also designated as the official designated car for the Beijing APEC meeting. In the energy storage market, Yin Long, respectively, with the State Grid and China Southern Power Grid to undertake the energy storage aspects of the 863 national projects for the Zhangbei scenery storage and demonstration stations and Shenzhen Baoqing battery energy storage stations were provided 2 2MWh and 1 600kWh lithium titanate system part of the module, battery box design and system solutions.
Shenzhen Bo Leida through a unique material handling methods, can be prepared to obtain good performance Li4Ti5O12 material, and through technical research projects, from the production of lithium titanate battery technology to start, high-performance Li4Ti5O12 design and preparation has made significant progress, the current Production products are 17Ah, 20Ah and 25Ah cylindrical battery, to solve the lithium titanate battery easy to flatulence problems, access to high-performance lithium titanate battery products, and made the authority of the third party test report.
From the high power Li4Ti5O12 electrode material design, Li4Ti5O12 material interface reaction reveals the gas production mechanism and the mechanism of Li4Ti5O12 electrode material in the power battery scale application and made a major breakthrough.
Tianjin Jie Wei has been the United States Austrian titanium lithium titanate battery production technology transfer, combined with their own years in the polymer soft pack battery production technology accumulation and living alone. The company successfully broke the problem of flatulence, has been mass production of large-scale single-cell lithium titanate battery technology and capacity, battery capacity reached 60Ah, the cumulative shipments of 20 million Ah.
The battery can withstand more than 10C continuous charge and discharge, life of more than 20,000 times, the temperature range of -40 ~ 60 ℃, mainly used in fast charge bus and FM energy storage power station.
Difficulties in the Development of Lithium Titanate Battery Technology and Its Development
1. The reasons for the development of lithium titanate battery technology in China
Lithium titanate battery technology in China's various energy storage battery competition should occupy the days, geography, and the advantages. In terms of service life, the long cycle life of lithium titanate batteries is much better than all kinds of lead-acid batteries; its efficiency, cost and electrochemical performance is better than sodium and liquid vanadium and other battery system.
Lithium products over the years the main market is portable appliances such as mobile phones and laptop computers. China's mobile phone and portable computer consumption is large, but most are not a domestic brand. So the domestic lithium manufacturers in the portable electrical lithium sales capacity lost in Japan and South Korea products.
However, the applicable market for lithium titanate technology is hybrid electric vehicles, special industrial applications and energy storage applications such as FM and grid voltage support. These markets in the world is still in its infancy, who is not yet known. Lithium titanate technology is expected to be the leader in these markets.
China's population base accounts for about 1/5 of the world. Due to the large population, China's electric car, energy storage and industrial applications market is a huge market for many multinational companies coveted. In recent years, the Chinese government attaches great importance to the development of electric vehicles and energy storage industry, various countries have encouraged the introduction of policies. China-made lithium titanate battery system in Chongqing and Europe, hybrid electric bus, Zhangbei of the wind storage model and Shenzhen Baoqing storage power station has a few years of commercial application data accumulation.
In addition, China's lithium industry chain upstream and downstream has long been a climate, in addition to a complete battery material supply and equipment manufacturing capacity, the lithium battery product production capacity and Japan and South Korea one-third of the world. Which makes China's lithium manufacturers from the traditional lithium battery production to the production of lithium titanate battery products with the inherent conditions.
China has long been in the production of lithium titanate materials like Sichuan Xingnong, Zhuhai Yinlong, Huzhou micro-macro, and so have the strength and experience of the enterprise. Lithium titanate battery production in the stand out on behalf of enterprises Huzhou micro-macro, Zhuhai Yinlong, Shenzhen Bo Lei, Tianjin Jie Wei and so on.
These enterprises have been in the domestic and international electric car and energy storage market initially established their own sales channels. In particular, it is worth noting that Shenzhen Bo Lei has from the production of materials to the battery production and system integration of a series of proprietary technology and intellectual property rights, China's lithium industry is still rare with independent intellectual property rights of the manufacturer.
2. Lithium titanate materials, batteries and battery pack production bottlenecks
Since the lithium titanate battery technology has many other lithium can not match the superiority, why so far in the Chinese energy industry and even the world's energy industry, few? There are three reasons:
① lithium titanate production of lithium titanate material production in principle is not complicated. But should be used as a negative electrode material for lithium-ion batteries, not only need to pay attention to the material with the appropriate surface area, particle size, density and electrochemical properties, etc., must also be able to adapt to large-scale lithium battery production process. Lithium titanate material in many traditional lithium production line can not be the normal production of one of the reasons is the material pH of 11 or 12, highly hygroscopic.
② production of lithium titanate batteries In fact, the conventional lithium-ion battery production line directly used to produce lithium titanate battery products is not just like graphite into lithium metal material as simple. Because the lithium titanate material on the humidity requirements than conventional lithium-ion battery production is much higher. In order to control the humidity, some of the preparation process needs to be adjusted accordingly to meet the special requirements of lithium titanate battery products. In addition, some production equipment also need to do the corresponding improvement. If conditions permit, it is best to specifically for the lithium titanate battery products to re-design a compact, small size, fully enclosed automated production lines.
③ lithium titanate battery battery and conventional lithium-ion battery is different from the current domestic and foreign production of lithium titanate batteries in groups put into use after a period of time will often see the soft package of single cells have a trace of gas generated. These gases are different from the gases produced when the fresh batteries are converted. The former can be removed by the battery production process. But the latter is in the battery used in the process of production, or in the current process conditions is difficult to avoid.
I believe that the study of the cycle of gas generated by the chemical reaction mechanism should be a good research topic. In addition, one of the advantages of lithium titanate battery technology is its high power performance. Although the battery itself can withstand high current charge and discharge, but the thick single battery is still not suitable for high power applications because the battery is too thick will cause high heat generated heat is difficult to distribute. So the high-power lithium titanate battery, the size of large and thin soft battery structure is still a reasonable choice.
3. Lithium titanate technology in the future direction of development
Finally, it is necessary to summarize the advantages and disadvantages of the lithium titanate material as the negative electrode.
Advantages: high safety, long life, high and low temperature wide range of work, high power, low cost and green.
Disadvantages: Lithium titanate material energy density is low, strong water absorption, the battery production environment is high, the production process to do the corresponding update, the new process needs to invest the necessary equipment and higher requirements of the humidity control, and lithium titanate battery The application market is not yet fully open.
In the current Chinese government to vigorously promote the development of new energy and related industries under the environment, how to promote the lithium titanate battery technology and its application in the electric car and energy storage market for China's lithium titanate battery industry is a machine , No longer come For the domestic Zhuhai Yinlong, Huzhou micro-Hong, Shenzhen Bo Lei, Sichuan Xing, Shenzhen Bei Terui, etc. have a part of the advantages of independent intellectual property rights and sales channels of the enterprise should be unique opportunities. Many people do not realize that China's lithium titanate technology in the intellectual property advantage is the current lithium iron phosphate-based so-called "mainstream chemistry" does not have.
The development of high-capacity high-potential cathode materials to improve the energy density of lithium titanate batteries is a way to catch up with Japan and South Korea. Of course, at the same time the entire lithium-ion battery chemical system must be studied, such as high-potential electrolyte and anti-oxidation membrane and other research. China's lithium industry development of lithium titanate battery technology efforts will be the rise of the electric car, energy storage and industrial applications market considerable returns.