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What is a ternary lithium battery? Three element materials? Perhaps you didn't understand before, but after reading this article, you will become an expert

In recent years, ternary materials as positive electrode materials have gradually gained an increasingly important position in the power battery industry due to their important advantages such as high capacity, good cycling stability, and moderate cost.

In new energy vehicles, the market share of ternary lithium batteries has surpassed that of lithium iron phosphate batteries, becoming a major highlight. Most mainstream domestic car companies, including Geely, Chery, Changan, Zotye, Zhonghua, etc., have launched new energy models using ternary power batteries. For example, the BAIC EV series, Chery eQ, Arrizo 3EV, Jianghuai iEV4, Zotye Cloud 100, including Geely Emgrand EV, etc. So what is the reason why ternary material batteries are becoming increasingly dominant?

The performance of lithium-ion batteries mainly depends on their positive electrode materials, and lithium-ion batteries are usually named after positive electrode materials. The ternary material batteries mentioned in the market mostly refer to lithium-ion batteries with nickel cobalt manganese as the positive electrode material.

People have found that the nickel cobalt manganese ratio in nickel cobalt manganese ternary cathode materials can be adjusted within a certain range, and its performance varies with the different ratios of nickel cobalt manganese. Therefore, in order to further reduce the content of high cost transition metals such as cobalt and nickel, and improve the performance of positive electrode materials, countries around the world have done a lot of work in the research and development of nickel cobalt manganese ternary materials, proposing multiple ternary material systems with different nickel cobalt manganese ratios, including the 333523811 system. Some systems have successfully achieved industrial production and application.

Next, I will take you into the depths of the three elements.

1、 Structural characteristics of nickel cobalt manganese ternary cathode materials

The ternary material of nickel cobalt manganese can usually be represented as LiNixCoyMnzO2, where x+y+z=1. According to the different molar ratios (x: y: z ratio) of the three elements, they are referred to as different systems, such as the ternary material with a nickel cobalt manganese molar ratio (x: y: z) of 1:1:1 in the composition, abbreviated as 333 type; The system with a molar ratio of 5:2:3 is called the 523 system, etc. The 333, 523, and 811 ternary materials all belong to the hexagonal NaFeO2 layered rock salt structure.

In nickel cobalt manganese ternary materials, the main valence states of the three elements are+2,+3, and+4, with Ni being the main active element. Generally speaking, the higher the content of active metal components, the larger the material capacity. However, when the content of Ni is too high, it can cause Ni2+to occupy the Li+position, exacerbating cation mixing and resulting in a decrease in capacity. Co is also an active metal, but it can inhibit cation mixing and thus stabilize the layered structure of the material; Mn does not participate in electrochemical reactions, providing safety and stability while reducing costs.

2、 Characteristics of nickel cobalt manganese ternary lithium-ion batteries with different systems

There are many nickel cobalt manganese ternary system batteries on the current market, such as 523111811 system, etc. As a vehicle power battery, the market has put forward increasingly stringent requirements for its energy density. But you can't have both fish and bear's paw. If you want to obtain a high energy density and safe stable power battery, you must increase the proportion of Ni and Co in the ternary material. Accompanying this are safety hazards caused by the active nature of Ni and cost increases due to the lack of Co resources. Here is also a brief introduction to nickel cobalt manganese ternary batteries for various systems.

(1) 523 type ternary material is currently the most widely used ternary material due to its high specific capacity and thermal stability, as well as the continuous improvement of process maturity and stability, leading to a rapid expansion of its domestic market share. The 523 ternary material pursues high volume and high specific capacity (high compaction density), followed by a balance between cycling performance, rate performance, thermal stability, and self discharge. As a power battery, it can greatly improve the endurance of electric tools.

(2) The 111 type ternary material has advantages in energy, rate, cycling, and safety performance. However, the first charge discharge efficiency of the 111 type material is low, and the mixed discharge of cations in the lithium layer affects the stability of the material, and the discharge voltage platform is relatively low. At present, improving the tap density, cycling stability at high and low temperatures, and rate performance of LiNi1/3Co1/3Mn1/302 material has become a hot research topic in this material. The power battery prepared from 111 type ternary material has a high specific capacity, and can meet the requirements of EV (electric vehicle) and HEV (hybrid electric vehicle) for power batteries in terms of cycling, rate performance, low-temperature discharge, charge retention ability, and safety performance.

(3) The 811 type material has advantages such as high capacity and low price due to its high Ni content and low Co content, but it is also more difficult to achieve stability like the 111 system. Due to the high Ni content, its manufacturing cost will also increase, and this Ni based material has relatively high environmental requirements for battery production. 811 battery production requires the coordination of high-voltage electrolytes. Therefore, the manufacturing and processing technology of 811 series materials is currently a research focus. At present, high Ni materials such as 811 are well made in Japan and South Korea, such as Sumitomo Corporation in Japan. There are many domestic manufacturers, such as Bangpu and Dahua, most of which are only in the experimental stage and have not yet formed mass production scale.

(4) The higher the Ni content in the 622 ternary material, the higher the specific capacity. When the Ni content reaches over 60%, the importance of the material gradually becomes apparent. The 622 type nickel cobalt manganese ternary lithium battery has a higher specific capacity than the 523 type, with a gram capacity of over 160 milliampere hours, and even up to 180 milliampere hours under high voltage conditions, and has good processing performance. The development of 622 class materials is currently a key focus of industrial development and is also highly suitable for high energy density EV batteries.

3、 The current situation and development of ternary lithium batteries

On January 24, 2016, the Ministry of Industry and Information Technology's "suspension of subsidies" policy for ternary batteries was a blow to ternary lithium battery manufacturers, but it also imposed certain constraints on this market.

Starting from June 2016, the ban gradually lifted and returned to the list of policy subsidies. With the introduction of another series of new energy vehicle subsidy policies, ternary batteries may also experience explosive growth.

Data shows that in 2016, the production of ternary materials increased by about 50%. Research institution Monita expects a year-on-year growth rate of 110% to 120% in the production of ternary lithium batteries in 2017.

In contrast, since the fourth quarter of last year, the number of enterprises investing in lithium iron phosphate power batteries has significantly decreased, making it difficult for the upstream material lithium carbonate prices to rise. Since April last year, the decline in lithium carbonate has reached 30%. In January of this year, some companies raised their prices for lithium carbonate by 1000 to 3000 yuan, but the market did not see any transactions.

The new policy for new energy vehicles introduced at the end of 2016 clearly links the subsidy amount to battery energy density, with higher energy density receiving more subsidies. And ternary batteries have higher energy density potential, especially high nickel ternary batteries. Therefore, many companies have switched to ternary lithium batteries.

At present, the market share of lithium iron phosphate batteries and ternary batteries is 70% and 25% respectively.

From 2016, overcapacity in power battery production began to emerge, and companies that were the first to switch to ternary lithium batteries are expected to benefit from a new round of increasing demand for new energy vehicles, "said industry experts.

Public information shows that lithium iron phosphate "giants" represented by BYD, CATL, Guoxuan High tech, and AVIC Lithium Battery will expand their production capacity of ternary lithium batteries. According to relevant sources, BYD will add 5-6GWh of ternary batteries in 2017. In the next two years, the proportion of lithium iron phosphate and ternary production capacity of CATL will gradually shift from the current 2:1 to 1:1. AVIC Lithium Battery (Jiangsu) Co., Ltd., a subsidiary of Chengfei Integration, plans to build a ternary lithium battery production line with an annual output of 5 billion watt hours. Guangxi Zhuoneng New Energy Technology Co., Ltd., a subsidiary of Zhuoneng Group, plans to expand its production of 5 billion ampere hours of ternary power batteries in Guangxi.

In the field of lithium batteries, ternary materials that are superior to other materials in terms of energy density, low-temperature characteristics, power characteristics, and high-temperature storage performance will definitely become an undeniable force in the positive electrode materials of lithium batteries. In addition, taking the ternary route is also beneficial for upstream mining, especially nickel, cobalt, manganese, and lithium mines.

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