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In the current environment where the Chinese government vigorously advocates the development of new energy and related industries, how to promote the lithium titanate battery technology and its application in electric vehicles and energy storage markets is a must for China's lithium titanate battery industry.

Since the industrialization of lithium battery in 1991, graphite has been the anode material of the battery. Lithium titanate as a new anode material for lithium batteries has attracted much attention due to its many excellent properties.

Since the late 1990s, for example, the crystal structure of lithium titanate materials can maintain a high degree of stability in the process of lithium ion inlaying and de inlaying, and the lattice constant changes very little (volume change<1%).

This zero strain electrode material greatly extends the cycle life of lithium titanate battery. Lithium titanate has a unique three-dimensional lithium ion diffusion channel with spinel structure, which has excellent power characteristics and high and low temperature performance.

Compared with the carbon anode material, lithium titanate has a high potential (1.55V higher than the potential of metal lithium), which results in that the solid-liquid layer normally grown on the surface of electrolyte and carbon anode is basically not formed on the surface of lithium titanate.

More importantly, it is difficult to form lithium dendrites on the surface of lithium titanate within the voltage range of normal battery use. This largely eliminates the possibility of short circuit formed in the battery by lithium dendrites. Therefore, the safety of lithium batteries with lithium titanate as cathode is the highest among all types of lithium batteries that the author has seen.

Most people in the industry have heard that the lithium battery using lithium titanate as the anode material of lithium battery instead of graphite has a lithium cycle life of tens of thousands of times, which is far higher than the common traditional lithium battery. It will die after only a few thousand cycles.

Because most professional lithium battery users have never really made lithium titanate battery products, or they have only done it for a few times and met with difficulties. So they didn't calm down and think about it carefully. Why do most perfectly made traditional lithium batteries usually only have 1000 to 2000 charge discharge cycles?

Is the basic reason for the short cycle life of traditional lithium batteries due to the embarrassing burden of one of the basic components graphite anode? Once the graphite cathode is replaced by the spinel lithium titanate cathode, the basically same lithium battery chemical system can be recycled to tens of thousands or even hundreds of thousands of times.

In addition, when many people talk about the low energy density of lithium titanate batteries, they ignore a simple and important fact: the super long cycle life, remarkable safety, excellent power characteristics and good economy of lithium titanate batteries. However, these characteristics will be the important cornerstone of the emerging large-scale lithium battery energy storage industry.

In the past 10 years, the research on lithium titanate battery technology at home and abroad has been turbulent. Its industrial chain can be divided into lithium titanate material preparation, lithium titanate battery production, lithium titanate battery system integration and its application in electric vehicles and energy storage markets.

Lithium titanate material

The leading companies in the research and industrialization of lithium titanate materials in the world are Aoti Nanotechnology Co., Ltd. of the United States, Shihara Industry Co., Ltd. of Japan, Johnson Matthey Co., Ltd. of the United Kingdom, etc. Among them, the lithium titanate material produced by American Austrian Titanium has excellent performance in terms of magnification, safety, long life, high and low temperature, etc. However, because the production method is too long and delicate, resulting in high production costs, it is difficult to commercialize it.

Shiyuan Industry is one of the largest titanium dioxide manufacturers in Asia. The company has production bases in Japan and Singapore. The stone industry has made full use of its abundant raw material resources and successfully developed a number of lithium titanate products with low cost, high magnification and different particle sizes through wet process. The products with similar performance have greater advantages in price compared with the lithium titanate materials of Austria Titanium in the United States, but are inferior to domestic products. Johnson Matthey took over the lithium iron phosphate and other materials owned by the former German Southern Chemical Company, but the investment in the research, development and production of lithium titanate materials is insufficient, and the product quality is difficult to be stable.

There are many domestic lithium titanate materials in mass production, such as Sichuan Xingneng New Materials Co., Ltd., Zhuhai Yinlong New Energy Co., Ltd., Huzhou Weihong Power Co., Ltd., Shenzhen Beiterei New Energy Materials Co., Ltd., Hunan Shanshan New Materials Co., Ltd., and several small-scale lithium titanate manufacturers around Anhui and Shenzhen.

Sichuan Xingneng is a manufacturer specializing in the production of lithium titanate materials, with an annual output of 3000 tons. The lithium titanate production process has customer adaptability and stability, which can be flexibly adjusted without changing the existing production lines and equipment to produce lithium titanate suitable for different customer requirements, and maintain the stability of product technical indicators. Relying on the upstream lithium ore and titanium ore resources, Xingneng can realize the collaborative production from raw ore to final materials, thereby improving the performance and reducing the cost of lithium titanate products,

Prevent the impact of fluctuations in the raw material market.

In 2011, Zhuhai Yinlong completed the acquisition of 53.6% of the shares of American Altian Nanotechnology Co., Ltd., becoming one of the few companies in China that has a number of core technologies and more than 30 patents for lithium titanate material preparation, battery production, lithium titanate electric vehicles, energy storage systems, frequency modulation and peak shaving applications.

At present, North Aoti Nanotechnology Co., Ltd. (hereinafter referred to as North Aoti) has an annual output of 100 tons of lithium titanate materials and supplies high-quality nano lithium titanate to North Aoti and Zhuhai Yinlong. Zhuhai Yinlong New Energy has also carried out strategic cooperation with the Shiyuan Industry on the research and development of new lithium titanate materials. The cost of the materials will decrease with the increase of its output, and is expected to be close to the current cost price of graphite anode materials in the next few years.

Huzhou Micromacro is one of the most successful companies in promoting lithium titanate battery technology and other fast charging batteries in the domestic industry. The lithium titanate materials produced by Huzhou Micromacro are important for its own lithium titanate battery products. The continuous expansion of Huzhou micro macro lithium titanate battery products in domestic and international markets has also played a good demonstration role in the application of lithium titanate technology in electric vehicles and energy storage markets.

Shenzhen Betray is currently the world's largest supplier of lithium battery carbon cathode. The company has a strong R&D team and is also one of the drafters of lithium titanate industry standards. Shenzhen Betray's strong sales network will also take the lead in the lithium titanate market. It has launched two products, carbon coated lithium titanate and carbon free coated lithium titanate. However, lithium titanate materials are not the main products of Betterley at present. As the lithium titanate battery market has not been fully developed, the company has not made a long-term plan for the production of lithium titanate materials.

Lithium titanate battery and its application in electric vehicles and energy storage There are not many manufacturers that can produce lithium titanate battery in batches internationally, mainly represented by Alti and Toshiba. The important application markets of lithium titanate batteries include electric vehicles, energy storage markets and industrial applications.

Titania of the United States has its unique core technology in the manufacture of lithium titanate batteries. It is still in a leading position in the international manufacture of large-sized lithium titanate batteries, and has solved the so-called gas problem. At present, its fourth generation 65Ah single lithium titanate battery has been used in the energy storage system, and there is still no significant capacity degradation after tens of thousands of cycles at 65 ℃.

In terms of the application of lithium titanate battery system, Altian's hybrid electric bus for California has been put into operation since 2008. Its fuel economy index is 106.4kg/L, which is much higher than 23.8kg/L of ordinary diesel generator. The company has provided 1MW storage system for the 10.5MW wind farm of the Hawaii Natural Energy Institute and connected it to the local power grid, as well as technical support services for three years. This lithium titanate battery energy storage system is important for regulating the voltage fluctuation of renewable energy and controlling the load change rate of the unit within 1MW/min.

At present, the 1MW large capacity high-power energy storage unit of Altian is the only large capacity lithium titanate battery product that has passed the field commercial operation and performance quality inspection for more than two years in the US power grid. The number of cycles of the energy storage system exceeds 500000, the total charge and discharge capacity exceeds 3300MWh, the system capacity loss is less than 2%, and the power has no obvious attenuation.

Toshiba, Japan, mass produces lithium titanate batteries under the brand of SCiB. Among them, 3.2Ah, 10Ah and 20Ah aluminum shell square batteries are important for electric motorcycles, electric vehicles and car start stop batteries. The SCiB battery has the advantages of fast charging and long life. It can be charged for more than 90% in 10 minutes, and the capacity of the battery after 3000 times of repeated charging and discharging is less than 10%. It has been applied to EVneo electric motorcycles in batches.

In terms of energy storage, Toshiba is applying lithium titanate batteries to large-scale energy storage power plants and household energy storage systems by taking advantage of the Japanese New Sunshine Plan. Another Japanese company, Murata, has developed a new type of lithium titanate battery using 5V lithium nickel manganate as cathode. The voltage difference is 3.2V, and the energy density can reach 130Wh/Kge, exceeding

Current level of lithium iron phosphate battery.

There are many domestic lithium titanate battery manufacturers, such as Huzhou Weihong, Zhuhai Yinlong, Shenzhen Boleida, Tianjin Jiewei Power Industry Co., Ltd., Sichuan Xingneng, CITIC Guoan League Guli Power Technology Co., Ltd., Hunan Shanshan, and many smaller lithium titanate battery manufacturers around Anhui and Shenzhen. Huzhou Micromacro has been committed to the development of lithium titanate technology since its establishment in 2006. The company has vertically integrated lithium titanate materials, diaphragms, electrolytes and cathode materials for its lithium titanate battery production. In recent years, in order to meet the market demand, Huzhou Micromacro has the output of 80000 lithium titanate batteries with a daily output of 10Ah and the output of multiple positive lithium batteries with a daily output of twice that of lithium titanate batteries.

By the end of 2014, Huzhou Weihong's 10 minute fast charging battery system has been equipped with more than 3000 hybrid electric buses, which are mainly sold to Britain, the Netherlands and Chongqing, China. In terms of energy storage market, Huzhou Micromacro has installed lithium titanate battery energy storage systems for power grid frequency modulation and power grid demand management in Vermont of the United States and Chongqing of China respectively.

At present, Zhuhai Yinlong's mass produced lithium titanate battery products include 20Ah and 65Ah soft packed lithium batteries and 25Ah, 30Ah and 55Ah cylindrical batteries, and their performance indicators have reached those of lithium titanate batteries produced by American Austrian Titanium. The cycle times of 100% DOD of the battery exceed 16000, and the cycle times of 10% DOD reach 1.6 million. These batteries have passed the third-party inspection of the North Automobile Quality Supervision, Inspection and Appraisal Institute (201 institutes).

In terms of application, Yinlong new pure electric buses use cylindrical, long-life, fast charging and discharging lithium titanate batteries, with a range of 30-80km, fast charging only takes 6-10 minutes, and can also be fully charged by night valley charging for 30-60 minutes. This series of models has been successfully put into public transport systems in Zhanjiang, Guangdong, Handan, Hebei and Shijiazhuang.

The antique bell car specially designed and developed by Yinlong for Beijing public transport was put into commercial operation in September 2014. The vehicle was also designated as the official designated vehicle for the APEC meeting in Beijing. In the energy storage market, Yinlong cooperated with State Grid and China Southern Power Grid to undertake 863 national projects in energy storage, and provided two 2MWh and one 600kWh lithium titanate system modules, battery box design and system solutions for Zhangbei Wind Power Storage and Transmission Demonstration Station and Shenzhen Baoqing Battery Storage Station respectively.

Shenzhen Boleida can prepare Li4Ti5O12 materials with good performance through a unique material treatment method. Through the technical research project, from the improvement of the production process of lithium titanate batteries, significant progress has been made in the design and preparation of high-performance Li4Ti5O12. At present, the products in mass production include 17Ah, 20Ah and 25Ah cylindrical batteries, which solve the problem of easy inflation of lithium titanate batteries and obtain high-performance lithium titanate batteries, And obtained the authoritative third-party test report.

Starting from the design of high-power Li4Ti5O12 electrode materials, Boleida has made a major breakthrough in the large-scale application of Li4Ti5O12 electrode materials in power lithium batteries by studying the interface side reactions of Li4Ti5O12 materials, revealing the gas generation mechanism and solving mechanism.

Tianjin Jiewei has obtained the transfer of production technology of lithium titanate battery from Altian of the United States, and is unique in combination with its technological accumulation in the production of polymer soft package power lithium battery over the years. The company has successfully broken through the problem of gas expansion, and has the technology and ability to mass produce large single lithium titanate batteries. The battery capacity has reached 60Ah, and the cumulative shipment is 20 million Ah.

The battery can withstand continuous charging and discharging above 10C, with a service life of more than 20000 times and a temperature range of - 40~60 ℃. It is important for fast charging buses and FM energy storage power stations.

Difficulties and development direction of lithium titanate battery technology

1. Reasons for developing lithium titanate battery technology in China

The competition of lithium titanate battery technology in all kinds of energy storage batteries in China should have the advantages of favorable weather, favorable location and harmonious people. As far as the service life is concerned, the super long cycle life of lithium titanate batteries is far better than all kinds of lead-acid batteries; Its efficiency, cost and electrochemical performance are better than those of sodium sulfur and liquid vanadium battery systems.

The important market of lithium battery products over the years is portable appliances such as mobile phones and laptops. Although the amount of mobile phones and laptops in China is large, most of them are not domestic brands. Therefore, the sales capacity of domestic lithium battery manufacturers in portable electrical appliances is less than that of Japanese and Korean products.

However, the market for lithium titanate technology is hybrid electric vehicles, special industrial applications and energy storage applications such as frequency modulation and grid voltage support. These markets are still at the beginning stage in the world, and it is unknown who holds the upper hand. Lithium titanate technology is expected to become a leader in these markets.

China's population base accounts for about one fifth of the world's total. Due to the large population, China's electric vehicle, energy storage and industrial application market is a huge market coveted by multinational companies in many countries. In recent years, our government has attached great importance to the development of electric vehicles and energy storage industry, and various national incentive policies have been introduced. The domestic lithium titanate battery system has accumulated commercial application data for several years in Chongqing and Europe's hybrid electric buses, Zhangbei's wind and solar storage demonstration station and Shenzhen Baoqing Energy Storage Power Station.

In addition, the upstream and downstream of China's lithium battery industry chain has already become a hot topic. In addition to the complete battery material supply and equipment manufacturing capacity, the production capacity of lithium battery products is also three times that of Japan and South Korea. This makes it possible for Chinese lithium battery manufacturers to transform from traditional lithium battery production to lithium titanate battery production.

China has already had companies with both strength and relevant experience in the production of lithium titanate materials, such as Sichuan Xingneng, Zhuhai Yinlong and Huzhou Weihong. Representative companies that stand out in the production of lithium titanate batteries include Huzhou Weihong, Zhuhai Yinlong, Shenzhen Boleida, Tianjin Jiewei, etc.

These companies have initially established their own sales channels in the domestic and international electric vehicle and energy storage markets. It is particularly worth pointing out that Shenzhen Boleida has a series of proprietary technologies and intellectual property rights from material production to battery production and system integration. At present, China's lithium battery industry is still a rare manufacturer with independent intellectual property rights.

2. Bottleneck of lithium titanate material, battery and battery pack production Since lithium titanate battery technology has many advantages that other lithium batteries cannot match, why is it so far rarely used in China's energy industry and even in the world's energy field? The reasons are as follows:

① In principle, the production of lithium titanate is not complicated. However, in order to be used as the anode material of lithium battery, it is not only important to pay attention to the appropriate specific surface area, particle size, density and electrochemical performance of the material, but also must be able to adapt to the production process of large-scale lithium battery. One of the reasons why lithium titanate materials cannot be normally produced on many traditional lithium battery production lines is that the pH of the materials is 11 or 12, and the moisture absorption is extremely strong.

② In fact, it is not as simple to directly use the conventional lithium battery production line to produce lithium titanate battery products as just replacing graphite with lithium titanate materials. Because lithium titanate materials require much higher humidity than conventional lithium battery production. In order to control humidity, some preparation processes need to be adjusted to meet the special requirements of lithium titanate battery production. In addition, some production equipment should be improved accordingly. If conditions permit, it is better to redesign a compact, compact and fully enclosed automatic production line for lithium titanate battery products.

③ Lithium titanate battery pack is different from conventional lithium battery pack. At present, lithium titanate batteries produced at home and abroad are often seen to have trace gas in the soft packed single battery after being put into use in groups for a period of time. These gases are different from those that occur when fresh batteries are formed. The former can be removed through battery production process. However, the latter is in the process of battery use, or it is difficult to prevent under the current process conditions.

The author believes that it is a good scientific research topic to study the chemical reaction mechanism of gas during circulation. In addition, one of the advantages of lithium titanate battery technology is its high power performance. Although the battery itself can withstand high current charging and discharging, the thick single battery is still not suitable for high power applications because the battery is too thick, which will make it difficult to dissipate the heat generated by high current. Therefore, for high-power lithium titanate battery, the large and thin soft package lithium battery structure is still a reasonable choice.

3. Future development direction of lithium titanate technology

Finally, it is necessary to summarize the advantages and disadvantages of lithium titanate as a lithium cathode. Advantages: ultra-high safety, ultra-long life, wide working range of high and low temperature, high power, low cost and environmental protection.

Disadvantages: lithium titanate material has low energy density and strong water absorption,

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