The development of lithium titanate battery technology at home and abroad

Since the industrialization of lithium ion batteries in 1991, graphite has unified the whole country of battery anode materials. Lithium titanate as a new type of lithium ion battery cathode materials, it grabbed the attention because of its many excellent properties in the late 1990 s. For example, lithium titanate material in lithium ion Mosaic and crystal structure in the process of embedding off to maintain the stability of the lattice constant change is very small (volume change < l %).

The zero strain electrode materials greatly extended lithium titanate battery cycle life. Lithium titanate with spinel structure of three-dimensional lithium ion diffusion channels, excellent power characteristics and the advantages of high and low temperature performance better. Compared with the carbon anode materials, high potential of lithium titanate (1.55 V) higher than the potential of metallic lithium, as a result, usually in the electrolyte with carbon negative growth on the surface of solid liquid layer on the surface of the lithium titanate basically formed.

What is more important in the normal lithium battery voltage range dendrite on lithium titanate surface is difficult to produce. This is eliminated by lithium dendrite, in large part and the possibility of short circuit is formed within the cell. So lithium titanate as the safety of the cathode of lithium ion battery is now the author saw the highest safety among various types of lithium ion battery.

The personage inside course of study most of them are heard by the lithium titanate to replace graphite as the li-ion battery cathode material of li-ion battery cycle life can reach tens of thousands of times, far higher than common traditional lithium-ion batteries, the end of the cycle of thousands of times alone.

Because most lithium electricity professionals never really make lithium titanate battery products, or just made several difficulties. So they couldn't calm down and think carefully, why most perfect traditional lithium-ion battery usually only finished 1000 ~ 2000 times charging and discharging cycle life?

Traditional root cause of the short cycle life of lithium ion batteries is derived from one of these basic components - graphite anode and stumble? Once the graphite anode replacing spinel lithium titanate cathode, lithium ion batteries are essentially the same chemical system can cycle to tens of thousands or even hundreds of thousands of times.

In addition, a lot of people relish talk about lithium titanate battery energy density is low, but ignores the fact that a simple but important: it is lithium titanate battery super long cycle life, outstanding power characteristics of safety, excellent and good economy. These features will be the achievement is the rise of mass cornerstone of li-ion battery energy storage industry.

In recent 10 years, the study of lithium titanate battery technology at home and abroad is now re-emerging. Its industry chain can be divided into lithium titanate material preparation, lithium titanate battery production and lithium titanate battery systems integration and its application in the electric vehicle and energy storage market.

1. The lithium titanate material

International lithium titanate materials research and industrialization in the United States are leading the titanium nanometer science and technology company, Japan ishihara industry co., LTD, UK Johnson matthey (jm) company, etc. Including the United States the titanium production of lithium titanate material in ratio, safety, long life and high and low temperature performance. But the production cost is high due to too long fine production methods, make it difficult on the commercialization.

Ishihara industry is one of Asia's largest manufacturer of titanium pigment, companies in Japan, Singapore, Taiwan has the production base. Ishihara industry make full use of its abundant raw material resources, to wet process successfully developed a low cost, high ratio, number of different granularity of lithium titanate products. The performance of similar products in the price to compare the titanium material of lithium titanate has the advantage of larger, but less than China's domestic products. Johnson matthey (jm) took over the southern German chemical company with materials such as lithium iron phosphate, but in terms of the research and development and production of the lithium titanate material investment insufficient, the product quality stability.

Domestic in lithium titanate material has several production aspects, such as Sichuan xing to new materials co., LTD., Zhuhai silver long new energy co., LTD., Huzhou micro macro power co., LTD., Shenzhen bay, new energy materials co., LTD., hunan shanshan new material co., LTD. And Anhui province Shenzhen is around several smaller lithium titanate manufacturers.

Sichuan xing is a professional manufacturer of lithium titanate material, annual production capacity of 3000 t, lithium titanate production process with customer adaptability and stability, but without changing the existing production lines and equipment under the condition of flexible adjustment, to produce lithium titanate for different customer requirements, and maintain the stability of the product specifications. Hing can rely on the upstream of the lithium and titanium mineral resources, which can realize coordinated from ore to the final material production, which can realize the lithium titanate product performance improvement and cost reduction, avoid the effects of raw material market fluctuations.

Zhuhai silver long to the United States in 2011 completed the titanium nanometer technology companies 53.6% of equity acquisition so as to become one of the few domestic a with lithium titanate material preparation, batteries, lithium titanate electric vehicles, energy storage system, FM load applications such as a number of core technologies and more than 30 patents, enterprises.

Now the north the titanium nanometer technology co., LTD. (hereinafter referred to as "the north titanium") of annual capacity of 100 t lithium titanate materials and to the north of titanium and Zhuhai silver long provides the high quality of nanoscale titanium acid lithium. Zhuhai silver long new energy and ishihara industry also be new lithium titanate materials research and development carried out strategic cooperation, the cost of materials will be increased with the increase of its production decline, the next few years is expected to be close to the cost price of graphite anode materials at present.

Huzhou micro macro is currently in the domestic industry to promote lithium titanate battery technology and other types of quick charge battery one of the most successful companies.

Huzhou micro macro production of lithium titanate material is mainly used in the production of lithium titanate battery products. Huzhou micro macro lithium titanate battery products in the domestic and foreign market expanding of lithium titanate technology applications in electric vehicle and energy storage market has played a good demonstration effect.

Shenzhen bay, is currently the world's largest lithium electrical carbon cathode supplier. The company has a strong R&D team, is also one of lithium titanate drafter of industry standard. Shenzhen bay, strong sales network will also be in lithium titanate marketing advantage, has introduced carbon coated titanium acid lithium and no carbon coated titanium acid lithium 2 product. However, the current lithium titanate material is not the terry's flagship product. In lithium titanate battery market has not yet been rolled out, the company is not in the production of lithium titanate material on a long-term plan.

2. Lithium titanate battery and its application in the field of electric vehicle and energy storage

International to batch production of lithium titanate battery manufacturers, mainly in the titanium and Toshiba group represented by the United States. The application of lithium titanate battery market mainly include electric vehicles, energy storage market and industrial application.

American President titanium acid lithium battery manufacturing has its unique core technology, large size titanium acid lithium battery in the world manufacturing is still in the leading position, and has solved the problems of the so-called "bloating". The 4th generation of 65 ah single lithium titanate battery has been used for energy storage system, in 65 ℃ circulating tens of thousands of times still no obvious capacity attenuation.

Lithium titanate battery system applications, the titanium for California hybrid electric bus has been put into operation in 2008.The fuel economy index is 106.4 kg/L is much higher than ordinary diesel generator of 23.8 kg/L. Company for Hawaii natural energy of 10.5 MW wind farm provides 1 MW storage system and with the local power grid interconnection, at the same time provide a three-year technical support services. The lithium titanate battery energy storage system is mainly used to regulate the voltage fluctuation of renewable energy, and to control the load rate of the unit 1 mw/min or less.

The titanium 1 mw large capacity high power energy storage unit is currently the only get more than two years in the grid field business operations and performance of the quality inspection by the large capacity of lithium titanate battery products. Energy storage system cycle number more than 500000 times, more than 3300 MWH, charge and discharge's electricity system capacity loss is less than 2%, and there is no obvious attenuation of power.

The "SCiB" is the brand of Toshiba batch production of lithium titanate battery.3.2 Ah Ah, 10 and 20 Ah square aluminum shell battery is mainly used for electric scooters, electric cars and auto stop the battery. SCiB has quick charge and the advantages of long life battery, 10 minutes can be charged by more than 90%, repeated 3000 times charging and discharging power capacity attenuation of less than 10%, has been used in "EV - neo bulk electric scooters.

In terms of energy storage, Toshiba by Japan's new sunshine program of Dongfeng are the applications of lithium titanate battery to large-scale energy storage power station and household energy storage system. Another corporate Japan murata has been developed using 5 v nickel manganese acid lithium titanate as the anode new lithium battery. The voltage difference is 3.2 V, the energy density can reach 130 wh/K song, more than at present lithium iron phosphate batteries levels.

Domestic in lithium titanate battery production has already had several, such as huzhou micro macro, Zhuhai silver long, Shenzhen bo lei gateway power industrial co., LTD., Tianjin, Sichuan xing can, citic groupama solid power supply technology co., LTD., Hunan Shanshan and Anhui and several smaller around Shenzhen lithium titanate battery manufacturers。

Huzhou micro macro since it was founded in 2006 has been committed to lithium titanate technology development. Company for its lithium titanate battery production need lithium titanate materials, membrane, electrolyte and cathode material for vertical integration. In recent years, in order to adapt to market demand, the Huzhou micro macro with the nissan 80000 10 ah titanate capacity of lithium battery and 2 times the lithium titanate battery multiple positive capacity of lithium battery.

By the end of 2014, Huzhou micro macro 10 minutes of quick charge battery system is equipped with more than 3000 hybrid electric bus, mainly exported to Britain, the Netherlands and China Chongqing and other places. In terms of energy storage market, Huzhou micro macro respectively in vermont in the United States and China Chongqing installed for power grid frequency modulation and power demand management of lithium titanate battery energy storage system.

Zhuhai silver long the current production of lithium battery products have 20 ah titanate and 65 ah battery soft packages and 25 ah 55ah, 30 ah and cylindrical battery, performance indicators have reached the United States the production of titanium titanium acid lithium battery. Battery 100% DOD cycles of more than 16000 times, 10% DOD has reached 1.6 million times. These a few batteries have passed north automobile quality supervision and inspection qualification (201) by the third party inspection.

In applications, silver long new pure electric bus using cylindrical, long life and fast charging and discharging lithium titanate battery, the battery can reach 30 ~ 80 km, quick charge only for 6 ~ 10 minutes, can also be used at night valley electricity charge 30 ~ 60 minutes slow. This series of models have been successfully put on the Guangdong Zhanjiang, Hebei Handan, Shijiazhuang and other places the public transport system.

Silver long designed for Beijing public transport development of archaize dang dang car put into commercial operation in September 2014.The car has also been designated as the APEC meeting in Beijing officially designated car. In energy storage market, silver long cooperation with state grid and southern grid respectively responsible for storage of 863 national projects, for Zhang Bei scenery storage demonstration station and the Shenzhen Baoqing battery energy storage station respectively provided 2 2 MWH and 1 600 KWH lithium titanate system part of the module, battery box design, and system solutions.

Shenzhen bo lei da through unique material processing method, can get good performance of Li4Ti5O12 materials preparation, and through technical research projects, from lithium titanate battery production technology, the design and preparation of high-performance Li4Ti5O12 has made significant progress, the current production of products has 17 ah, ah, and 20 ah cylindrical battery, solve the problems of the lithium titanate battery easily bilge gas, obtained the high performance of lithium titanate battery products, and obtained the authority of the third party test report.

Bo lei da company from the design of high power Li4Ti5O12 electrode materials research Li4Ti5O12 materials reveal interface reaction mechanism of gas and solution mechanism for large-scale application in power battery Li4Ti5O12 electrode materials and made significant breakthrough.

Tianjin gateway got us the titanium titanium acid lithium battery production technology transfer, and combined with their years in polymer soft package power battery production technology accumulation and lives alone. Company successfully broke through the bilge gas problem, have the batch production of large size single lithium titanate battery technology and capacity, battery capacity reaches 60 Ah, accumulative total shipments of 20 million Ah.

Can withstand more than 10 c continuous charge and discharge the battery, life of more than 20000 times, temperature range is - 40 ~ 60 ℃, is mainly used in quick charge bus and FM energy storage power station.

Lithium titanate battery technology development and its development direction

1. The development of lithium titanate battery technology in China

Lithium titanate battery technology in our country, the competition of various energy storage battery should possess the advantage of, geographical and human conditions. Light in terms of life, and lithium titanate battery long cycle life is far better than the various types of lead-acid batteries; Its efficiency, cost, and electrochemical performance is better than sodium sulfur and flow vanadium battery system.

Li-ion battery products in major markets are portable appliances such as mobile phones and laptops. The amount of China's mobile phone and laptop is big, but most do not belong to domestic brands. Domestic lithium electricity in portable electronics because lithium electricity sales ability to lose in Japan and South Korea product.

However, the application of the technology of lithium titanate is a hybrid electric vehicle market, special industrial application and energy storage applications such as FM and grid voltage support, etc. These markets in the world are still in its infancy, who was unknown perfectly. Lithium titanate technology is expected to be a major player in these markets.

China's population accounts for about 1/5 of all over the world. Due to the large population, China's electric vehicles, energy storage and industrial application market is a huge market multinational companies in many countries covet. In recent years, the Chinese government attaches great importance to the development of electric vehicle and energy storage industry, all kinds of the state encourages the policy are introduced. Chinese lithium titanate battery system in Chongqing and European hybrid electric bus, Zhang Bei scenery storage demonstration Baoqing station and the Shenzhen energy storage power station has been in the commercial application of data accumulated for years.

In addition, the lithium electricity industry chain upstream and downstream small already, in addition to the complete supply of battery materials and equipment manufacturing capacity, production capacity of lithium battery and Japan and Korea three points. This makes the lithium-ion battery manufacturers in China from traditional lithium electricity production transition to lithium titanate battery production has the congenital conditions.

In lithium titanate material production in China has already had a can like Sichuan xing, Zhuhai silver lung, Huzhou micro macro, etc. There are both strength and experience of the enterprise. In respect of lithium titanate battery production stand out on behalf of the enterprise silver long Huzhou micro macro, Zhuhai, Shenzhen bo lei da, Tianjin gateway, etc.

These companies have been at home and abroad, electric vehicle and energy storage preliminary set up his own market sales channels. Especially worth pointing out is Shenzhen bo lei has produced from material production to the battery and system integration of a series of proprietary technology and intellectual property rights, is a rare Chinese lithium electricity industry with independent intellectual property rights of the manufacturer.

2. Lithium titanate materials, batteries and battery production bottlenecks

Now that technology has many other lithium battery lithium titanate incomparable superiority, why so far a few applications in the field of China's energy industry and even the world energy? Reason has the following three aspects:

1) Lithium titanate material in the production of lithium titanate materials production in principle is not complicated. But to anode materials for lithium ion batteries, not only need to pay attention to material has appropriate specific surface area, particle size, density, and the electrochemical properties, etc., must also be able to adapt to mass production technology of lithium battery. Lithium titanate material in many traditional Li-ion battery production line can't normal production is one of the reasons of the pH value of the material for 11 or 12, strong moisture absorption.

(2) lithium titanate battery production in a matter of fact, the conventional lithium-ion battery production line directly used to produce titanium acid lithium battery products are not like just replace graphite with lithium titanate material. Because lithium titanate material requirement for the humidity is much higher than conventional lithium ion battery production. In order to control the humidity, some preparation needs to be done to adjust to adapt to the special requirements of lithium titanate battery production. In addition, some production equipment also need to make a corresponding improvement. If conditional word, best can specially designed for lithium titanate battery products to a compact structure, small volume, fully enclosed the automation of the production line.

(3) lithium titanate battery pack, unlike conventional lithium-ion batteries, the production of lithium titanate battery at home and abroad put into application in group after a period of time often see soft package of monomer battery with trace gases. These are gases and fumes, fresh batteries into different. The former can through production process to remove the battery. But the latter is in the process of our battery, or under the condition of the current process is hard to avoid.

The author thinks that, to study the chemical reaction mechanism of cycle gas produces should be a good research topic. In addition, due to the lithium titanate battery technology is one of the advantages of its high power performance. Although the battery itself can bear large current charge and discharge, but the thickness of the monomer battery is still not suitable for high power applications because the battery is too thick will cause the large current generated as difficult to heat. So for high power lithium titanate battery, size large, thin, soft package cell structure is still a reasonable choice.

3. The future development direction of lithium titanate technology

Finally, the necessary comprehensive summarize lithium titanate material as the advantages and disadvantages of li-ion battery cathode, advantage: high security, long life, high and low temperature working range wide, high power, low cost, and green environmental protection. Disadvantage: lithium titanate material energy density low, water imbibition is strong, the battery produced by high environmental requirements, the production process to do the corresponding update, the new process need to invest the necessary equipment and higher requirement of humidity control, as well as the application of lithium titanate battery market has not fully open.

Conclusion

In the current development of new energy has been heavily promoted by the Chinese government and its relevant industries of environment, how to promote the lithium titanate battery technology and its application in electric vehicle and energy storage in the market for lithium titanate battery industry in China is now or never, like the present. For domestic Zhuhai silver lung, Huzhou micro macro, Shenzhen bo lei can reach, Sichuan xing, Shenzhen bay, and so on have the advantage of a part of the independent intellectual property rights and enterprise sales channels should be advantageous. A lot of people don't realize is that China's intellectual property in lithium titanate technology advantage, which is mainly composed of the lithium iron phosphate battery is the so-called "mainstream chemical" did not have.

Development of high capacity, high potential cathode material in order to improve the energy density of lithium titanate battery is catch up with Japan and South Korea a clever move. Of course, at the same time, the lithium ion battery chemistry system must be researched, such as high potential electrolyte and antioxidant diaphragm, such as research. Lithium titanate battery lithium electricity industry development and technology of China's efforts will be rising electric vehicles, energy storage and industrial application market attractive returns.

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