Market Analysis lithium-ion battery electrolyte
A lithium-ion battery electrolyte profile
The electrolyte is a lithium-ion battery four key materials (cathode, anode, separator, electrolyte), one known as lithium ion batteries, "blood" between the battery negative Chiang conduction electrons play the role of a lithium-ion battery for high voltage, high specific energy, etc. guarantee. Electrolyte generally of high purity organic solvents, lithium salt electrolyte (lithium hexafluorophosphate, LiPF6), the necessary additives and other raw materials, under certain conditions, the preparation made by a certain percentage.
Second, the type of lithium-ion battery electrolyte
1, the liquid electrolyte
Electrolyte used for lithium-ion battery performance is very large, it must be good chemical stability, especially at higher potentials and high temperature environment is not easy to decompose, a high ionic conductivity (> 10--3 s / cm), but also for the anode and cathode materials must be inert, they can not invade rot. Because lithium-ion battery charge and discharge potential and the anode material embedded in a higher chemical reactivity of lithium, so the electrolyte must not contain organic compounds and water. However, the ionic conductivity of organic matter is not good, so soluble in organic solvents, the conductivity of salt added to improve the ionic conductivity. Lithium-ion batteries are mainly used liquid electrolytes, the anhydrous organic solvent such as EC (ethyl carbonate), PC (propylenecarbonate), DMC (dimethyl carbonate), DEC (diethyl carbonate), the majority of mixed solvents, such as EC2DMC and PC2DMC . Conductive salt with L iClO4, LiPF6, LiBF6, LiA sF6 and LiOSO2CF3, their conductivity in the order of LiAsF6> LiPF6> LiClO4> LiBF6> LiOSO 2CF3. LiClO4 due to high oxidation prone to explosion and other safety issues, generally confined to experimental studies; LiAsF6 high ionic conductivity and good stability and easy purification, but contain toxic As, limited use; LiBF6 chemical and good thermal stability and conductivity is not high, LiO SO2CF3 poor conductivity and corrosion of the electrode, and less use; although LiPF6 will decompose, but with higher ionic conductivity, so the basic lithium-ion battery is used LiPF6. Current commercial lithium-ion battery electrolyte is mostly used LiPF6 of EC2DMC, it has a high ionic conductivity and good electrochemical stability.
2, solid electrolyte
Directly with lithium metal as anode materials with high reversible capacity, its theoretical capacity of up to 3862mAh g-1, is a graphite material 10 times, lower prices, is seen as a new generation of lithium-ion batteries of the most attractive anode material, but will produce lithium dendrites. Using solid electrolyte ionic conductivity as the lithium can inhibit the growth of dendrites, making it possible anode materials for lithium. In addition, use of solid electrolyte leakage of liquid electrolyte to avoid the shortcomings of the battery can be made thinner (thickness of only 0.1mm), higher energy density, smaller high-energy batteries. Destructive experiments show that solid-state lithium-ion battery safety is high, the nail wear, heating (200 C), short circuit and overcharge (600%) and other destructive experiments, the liquid electrolyte lithium-ion battery leakage occurs, explosion and other safety issues, and solid-state batteries within the temperature slightly higher than outside (<20 C) did not have any other security problems. Solid polymer electrolyte has good flexibility, film, stability, low cost, can use as a membrane between the positive and negative electrodes can be used as the electrolyte ions to pass.
Solid polymer electrolyte can be divided into dry form solid polymer electrolyte (SPE) and gel polymer electrolyte (GPE). SPE solid polymer electrolyte is mainly based on polyethylene oxide (PEO), the drawback is the low ionic conductivity, at 100 C can only reach 10-40cm. Ion conduction in the SPE is mainly in the amorphous region, with the movement of polymer chains pass migration. Because of its easy crystallization of PEO molecular chain of high regularity, and reduces the ionic conductivity of the crystal rate. Therefore, in order to improve the ionic conductivity on the one hand by reducing the crystallinity of the polymer to improve the chain mobility, on the other hand by increasing the conductivity of salt solubility in the polymer. The use of graft, block, cross-linking, copolymerization and other means to disrupt the crystallization properties of polymers can significantly improve the ionic conductivity. In addition, by adding inorganic salt compound can improve the ionic conductivity. In the solid polymer electrolyte by adding a high dielectric constant of the liquid low molecular weight organic solvents such as PC can greatly improve the conductivity of salt solubility, the composition of the electrolyte gel polymer electrolyte is the GPE, it is high at room temperature ionic conductivity, but will occur in the course of analysis of fluid and failure. Gel polymer lithium-ion batteries have been commercialized.
Third, the electrolyte materials, future trends
Lithium-ion battery with its own advantages of being integrated into a much larger group of industries - automotive battery in the field. To meet this huge industrial base, lithium-ion battery electrolyte materials, the development trend of the future will focus on new solvents, ionic liquids, additives, new lithium salt, etc., and new positive and negative electrode materials to match, so that the lithium-ion battery safer, higher power, more capacity, the ultimate safe and convenient way for electric vehicles, energy storage, aerospace and wider areas.
Lithium-ion battery industry in order to meet future development needs, we must develop a high-security, high environmental adaptability of battery electrolyte materials. Mainly from the electrolyte solvent, solute, and additives on the choice of consideration:
(1) to select a wide operating temperature range of solvents, solvent melting point preferably below -40 C, boiling point, preferably above 150 C or higher, wide electrochemical window solvents can better prevent the state of charge under the redox electrolyte, while improving battery cycle stability. For example, consider using ionic liquids, a new solvent, multi-component solvent, so as to solve the battery safety and environmental adaptability.
(2) select the appropriate solute to enhance the environmental adaptability of the battery. Now commonly used LiPF6 (lithium hexafluorophosphate) decomposition temperature is low, there is a small amount from 60 C start decomposition at high temperatures or harsh environments, decomposition increased substantially, resulting in HF (hydrofluoric acid) and other free acid, so that the acidification of the electrolyte, resulting in damage to the electrode material and a sharp deterioration in battery performance.
(3) may consider adding the right amount of flame retardant additives, redox shuttle additive to protect the positive and negative film-forming additives. The use of flame retardant additives to ensure thermal runaway when the internal battery, electrolyte will not burn a fire, so the battery safety can be guaranteed. Adopt the role of redox shuttle additive is to prevent the battery, especially when the battery power because in the course of abnormal conditions, the single cell will overcharge or over-frequent discharge, resulting in rapid deterioration of battery performance, thereby affecting the whole group performance and battery use, and even the occurrence of a security risk. The use of positive and negative film is the role of additives can effectively protect the anode and cathode materials and electrolyte in the charged state of the contact reaction, through the film in the form of the highly reactive negative electrode and the electrolyte is isolated to prevent the electrolyte reactions on the electrode surface.
Fourth, the development of the global status of lithium-ion battery electrolyte
In recent years, the global lithium-ion battery electrolyte industry developed steadily, the market mainly in Japan, Ube Corporation and ECOPRO (Korean Cheil City) company, the two companies account for about 50% of global market share. Ranked in the following companies were: Mitsubishi Chemical, Toyama Chemical, Mitsui Chemicals, Kishida Chemical, Zhangjiagang Guotai glory and other enterprises.
Figure 1: The global lithium-ion battery electrolyte market share of major producers
Market Analysis lithium-ion battery electrolyte
2008, expects the global demand for lithium-ion battery electrolyte increased by 38% year to reach 14,225 tons, the electrolyte 2009 is expected to demand an increase of 35%.
Fifth, the development of the domestic status of lithium-ion battery electrolyte
Made of electrolyte from entering the market in 2002 to gradually replace imported products, through continuous improvement and improved product quality has reached international advanced level. Domestic battery manufacturers supporting electrolyte has been basically achieved domestically, with imports only a small part of the electrolyte.
The main domestic production units electrolyte Jiangsu Guotai (002,091) Cathay Pacific's glory, Tianjin Taurus, Shanshan Dongguan, Shantou golden, Zhuhai race Wei Electronics, Guangzhou Heaven, Beijing hit Asia more than 10 chemical companies. Annual production capacity of 1000 tons and above are involved in high, medium and low-end of each market, China's lithium-ion batteries to meet production needs, and some exports.
Table 2: The major producers of domestic electrolyte
Company Name production capacity / t market share Remarks
Jiangsu Zhangjiagang Guotai Huarong 300,040% subsidiary of Cathay Pacific, the main face of the high-end customers
Dongguan Shanshan Shanshan 300,015 percent investment in 2005, mainly for mid-market customers
Zhuhai race Wei electronic 150,010 percent for high-end customers
Taurus 300015% Tianjin main face of relatively inexpensive low-end
Fluke (Suzhou) 35,005% foreign, primarily to high-end customers
State Chemical Shenzhen Universe 1000 15,005% Japanese-funded enterprises set up in 2002.
Guangzhou, the main face of heaven-sent 200,010% mid-market customers
Beijing Chemical Reagent Research Institute 200010%
Beijing Sunny 15002 create sub-3% was established in 2004, in addition to producing the electrolyte, anode material has an annual output of 1500 tons
5001% on Hai Tuer Industry Institute of Physics, Chinese Academy of Sciences used proprietary technology
Cathay Pacific Ronghua lithium-ion battery electrolyte industry leading enterprises, is the largest manufacturer of lithium-ion battery electrolyte. In 2008, Jiangsu Yangtze River Chemical Industrial Park in the new 5000 metric ton (also 5,000 tons of production capacity set aside to plant), plant construction has been completed, expected in June-July 2009, 10-trial production of the official production in November, after old factory 3000 tons production capacity shut down. 08/09 were expected annual output of 2700 tons / 4000 tons. Company's domestic market share is currently 30% -40%, and targeting high-end market. Taurus Tianjin, Dongguan Shanshan combined market share of 30% products are mainly targeted the low end.
Race Wei Electronics - Zhuhai race Wei Electronic Materials Co., Ltd. is located in Doumen District of Zhuhai City, Toyama Industrial Park, is a new high-tech private enterprise, an investment 10 million yuan annual output of 1,000 tons of new capacity lithium battery, Lithium-ion battery and super capacitor electrolyte production line, the factory covers an area of 3,000 square meters, mainly produces and sells functional electrolyte: lithium-ion batteries to improve high temperature performance, security and other low-temperature performance of lithium ion batteries and polymer electrolyte batteries, Tailor-made for lithium manganese oxide, lithium iron phosphate, ternary materials, modified natural graphite anode materials of the electrolyte.
Taurus Tianjin - Tianjin Taurus Power Material Co., Ltd. is Xingtai Mining (Group) Co. Ltd. and Tianjin Chemical Research Institute formed a joint venture of the R & D, production, operation and service of high-tech enterprises. Has been completed set of electrolyte salt production, solvent refining, electrolyte preparation and packaging production line, the main products are: lithium hexafluorophosphate (scale of 80 tons / year), high-purity solvents (scale of 500 tons / year), lithium ion batteries Battery electrolyte and related materials. Tianjin Taurus is currently the only one using self-developed technology, domestic raw materials and production equipment, lithium hexafluorophosphate business, but with the industry's feedback information, product quality and abroad, there are still a big gap.
Sixth, raw materials supply lithium hexafluorophosphate
The main raw material for the lithium salt electrolyte, the scientific name (lithium hexafluorophosphate LiPF6), accounting for about 50% of the cost of its production cost is 10 yuan / ton, priced at 40 yuan / ton, gross margin of 75%. Lithium salt of raw materials silica / lithium carbonate can be purchased in China to.
Lithium salt is now almost monopolized by Japanese a few companies. Among them, the annual production of Kanto Chemical LiPF6 electrician 950 tonnes (mainly for UBE), SUTERAKEMIFA 800 tons (mainly for ECOPRO), the world's largest manufacturer of lithium salts produce 960 tons of chemical Morita (mainly for Mitsubishi) The company in Jiangsu Yangtze River Chemical Industrial Park has an annual output of 600 tons production line, in which more than 300 tons supply company. There are also a golden Tech Co., Ltd., Tianjin Chemical Industry Design and Research Institute, Shandong Chemical Fertilizer Xingtai city, Tianjin, Taurus and other companies can produce, but the capacity is less quality and are a lot worse.
Because lithium hexafluorophosphate huge future market demand, domestic enterprises have begun to actively access other. Jiangsu Guotai (002,091) and a joint venture company owned subsidiary of Huarong established source of high-tech materials Zhangjiagang Asia Ltd., invest in a new 300 tons of lithium hexafluorophosphate product project, total investment of 83.3 million yuan, is expected before the end of 2009 test equipment to debug. Henan Fluoride Chemical Co., Ltd. started construction in 2009, annual production capacity of 200 tons of lithium hexafluorophosphate project
Figure 2: Lithium-ion battery electrolytes with LiPF6 supply capacity forecast
Market Analysis lithium-ion battery electrolyte
Lithium hexafluorophosphate in 2009 the overall market supply tensions.
Seven, the next major incremental market forecast electrolyte
1, the hybrid vehicle market
Hybrid electric vehicle (HEV) in the next few years, a major new energy vehicle development. In 2010, global production will reach 78 million vehicles, hybrid vehicle production will reach 2.1 million, accounting for 2.66%, each vehicle battery according to 50,000 yuan, and the whole vehicle battery market value will reach 105 billion yuan. Most auto manufacturers of hybrid cars to 85% Ni-MH battery energy storage device of a vehicle. However, major manufacturers have new models in the use of lithium batteries as the vehicle energy storage device. Li-ion battery to replace the current nickel-metal hydride battery is likely to speed faster than the market expected. (By Foton Motor, for example, received 800 new hybrid vehicles, and decided to use lithium batteries) in the lithium battery industry as a vehicle battery early penetration rate of 20% of the products calculated to reach 21 billion yuan market scale . Electrolyte corresponding market size of 25.2 billion yuan, the future large-scale commercial hybrid electric vehicle demand is expected after the explosive growth of the electrolyte.
2, the electric bicycle market
In 2008, global production of over 22.5 million electric bikes, of which 95% of Chinese production. In the current batteries used in electric bicycles, 84% of lead-acid batteries, only 14% use lithium batteries. According to estimates, by 2010 the global production of electric bicycles will be close to 30.82 million, the battery output value reached 61.64 billion yuan, if the penetration rate reached 10% of the lithium battery, the market scale will reach 6.164 billion yuan, the corresponding market size of 740 million of electrolyte dollars.
3, electric scooter and electric wheelchair market
Electric scooter, including golf carts, electric wheelchairs, 2007, the global electric scooter sales approaching one million, about 8% annual growth rate is expected to reach 1.2 million in 2010. The market is currently dominated by lead-acid batteries, but will also develop in the direction toward the lithium-ion battery. Expected to 2010, global demand for electric scooter more than 1.2 million, the battery output to nearly 33 billion if the penetration rate reached 10% of the lithium battery, the market scale will reach 2.975 billion yuan, the corresponding market size of the electrolyte $ 120 million.
4, the power tool market
Power Tools is a large-scale application of lithium battery market prospects. Currently, power tools, mainly nickel-cadmium batteries, lithium batteries with power tools can easily break through in the past to 18V voltage design limits, and become the power tool industry first product trends. 2005, E-ONE Moli and Miwaukee launch of the V28 used cathode material of lithium manganese battery in the power tool industry 26650 shakes session, officially declared the era of lithium power tools. In 2007, the world's largest power tool manufacturer B & D introduced the world's first use of lithium iron phosphate power tools (DCX6401 Combo Kit), this product in the market after the first two quarters, then its one hour high-speed charging, powerful , high security, and more than 2,000 times the battery cycle life, etc., a record $ 20 million in sales performance, breaking the B & G since the foundation of all records. In the big international companies, driven by the penetration of lithium batteries will continue to rise. The current global demand for power tools at an annual growth rate of around 5%, power tools battery for less than 10%, 85% for the nickel-cadmium batteries. As the nickel-cadmium battery pollution problems, European and American countries have gradually legislation to limit the scope. According to estimates, in 2010, the global power tool market will reach 182 million units, demand reached 730 million batteries, battery output value will reach 33 billion yuan, if the penetration rate reached 10% of the lithium battery, the market reached 3.3 billion corresponding to the size of the market electrolyte 396 million next year there will be steady growth.
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