Report on ternary cathode materials industry
- Ternary Cathode: the core of lithium battery
- Three development directions of ternary cathode
- The way of improving the performance of cathode materials
- Comparison of the development of ternary cathode materials in China and other countries
- Next-generation technology of ternary cathode
- Analysis of key companies in the ternary cathode industry chain
Ternary lithium battery material industry is the upstream of China’s lithium battery industry. The ternary cathode materials are the core material of lithium batteries and is widely used in the fields of new energy power batteries, 3C digital product batteries and energy storage batteries.
1.Ternary Cathode: the core of lithium battery
Lithium batteries are mainly composed of four main materials: positive electrode, negative electrode, electrolyte and separator. Lithium batteries can be divided into cylinders, squares, soft packs, etc. according to their shapes. In addition, It is often divided by the type of positive electrode material used, including lithium cobalt oxide battery, ternary battery, lithium iron phosphate battery, etc. In 2021, the installed capacity of power batteries in China will be 154.5GWh, mainly lithium iron phosphate batteries and ternary batteries. Among them, the installed capacity of ternary batteries was 74.35GWh, accounting for 48.1%.
① Ternary cathode market is growing rapidly
With the rapid growth of sales of new energy vehicles and the steady growth of power tools and other markets, the shipments of ternary cathode materials continued to maintain rapid growth. In 2021, the total shipments of cathode materials in China will exceed 1 million tons, reaching 1.094 million tons, with a year-on-year increase of 98.5%. In 2021, the shipment of ternary cathode materials will be 422,000 tons, with a year-on-year increase of 79.6%.
② Ternary cathode materials account for more than half of the cost of the cell
The cathode material is the core component of the lithium battery, and has a direct impact on many core performance indicators of the lithium battery, including capacity, life, rate, safety, etc. Usually, the lithium ions that can be deintercalated in lithium batteries are derived from positive active materials. In terms of cost, the positive electrode accounts for more than half. We take the 5-series ternary battery as a model, and combine the main material quotations from Shanghai Nonferrous Network to split the cost of the 5-series ternary battery. At present, the cathode material accounts for about 60% of the cost of the cell.
③ Coexistence of multiple technical routes for cathode materials
According to the crystal structure, cathode materials can be divided into three categories: spinel, olivine and layered structure. In the power battery market, lithium iron phosphate, lithium iron manganese phosphate, and Ningde’s new technology route M3P cathode all belong to the olivine structure. The NCM, NCA, etc. commercialized in the power battery market belong to the layered structure. From the gram capacity index, the ternary cathode materials have a relatively large advantage over lithium iron phosphate and lithium manganate.
④There is still a lot of space for improvement in the performance of the ternary cathode
The theoretical capacity of the lithium iron phosphate cathode material is 170mAh/g, the current industrialization has been able to achieve more than 156mAh/g, and the actual value/theoretical value reaches 92%. Lithium iron phosphate will continue to strive for excellence. The current commercialized ternary 5-series and 6-series have a gram capacity of about 180mAh/g, and the actual/theoretical value is only 65%. The gram capacity of the currently commercialized ternary 8-series cathode is about 200mAh/g, and the actual/theoretical value is only 72%.
⑤ Accelerate product iteration
On the basis of existing products, ternary cathode materials companies continue to innovate. Among the companies specializing in ternary cathode materials, the R&D expenses of Rongbai Technology and Dangsheng Technology will both exceed 300 million RMB in 2021. Among the companies mainly engaged in lithium iron phosphate, German Nano’s R&D expenses in 2021 will be 164 million RMB.
2. Three development directions of ternary cathode
Trend 1: Single Crystallization (Advantages)
Cathode materials can be divided into polycrystalline and single crystal. Generally polycrystalline materials exist in the form of micron-scale agglomerates. There are a lot of grain boundaries inside the agglomerates. During the charging and discharging process of the battery, due to the anisotropic lattice change, the polycrystalline material is prone to grain boundary cracking, resulting in the fragmentation of the secondary particles. This results in a rapid increase in side reactions, a rise in impedance, and a rapid decline in performance. The use of single crystal particles can reduce grain boundaries, reduce the occurrence of side reactions, and increase the compaction density, thereby increasing the energy density. Compared with polycrystalline, the cycle performance of single crystal materials is generally much better.
Trend 2: High voltage (advantage)
The second development trend of ternary cathode materials is high voltage, which is equivalent to increasing the charging cut-off voltage of lithium batteries. Generally, the charge cut-off voltage of a ternary battery is 4.2V to 4.3V. The national standard GB/T 37201-2018 points out that the ternary battery is generally charged with a constant current of 0.2C to 4.2V, and then charged with a constant voltage. Taking the 5-series ternary as an example, when the charge cut-off voltage is increased from 4.2V to 4.4V, the discharge gram capacity of the cathode material can be increased from 158.4mAh/g to 188.6mAh/g, an increase of 19%. And when the charge cut-off voltage reaches 4.5V, the gram capacity of the positive electrode can exceed 200mAh/g.
Trend 3: High nickelization (advantage)
The third major trend of ternary cathodes: high nickelization. The main purpose of high nickelization is to increase the energy density. From the point of view of the electronic structure, the eg orbital of cobalt (Co) is an empty orbital, and the t2g orbital has a large overlap with the 2p orbital of oxygen (O). In addition, the t2g orbital of cobalt forms a π bond with the 2p orbital of oxygen, the force is weak, and the electrons are easily transferred. The eg orbital of nickel (Ni) overlaps very little with the 2p orbital of oxygen, so theoretically the electrons on the eg orbital of nickel can be completely lost, and the effective capacity of lithium nickelate is higher. For manganese, when the nickel content exceeds that of manganese, manganese will transform into a tetravalent form, which is very stable. In general, in the NCM system, the higher the cobalt content, the better the rate performance; the higher the nickel content, the higher the gram capacity; the higher the manganese content, the more stable the structure. Generally, the gram capacity of the 8-series ternary can exceed 200mAh/g.
3.The way of improving the performance of cathode materials
Doping and surface modification have a significant impact on the performance of cathode materials.
Whether it is an ordinary cathode material, or in the direction of single crystal, high voltage, and high nickel, doping and surface modification are effective methods to improve the overall performance of cathode materials. And the method of doping and modification is also one of the core competitiveness of cathode material enterprises. Doping elements include Al, Mg, Cr, etc., and the improvement mechanisms include stabilizing the main structure, increasing the interlayer spacing of lithium ions, and segregation at grain boundaries.
Commonly used coating agents include Al2O3, V2O5, ZnO, ZrO2, TiO2, MgO, etc. Just taking the alumina coating method as an example, the first generation technology uses aluminum isopropoxide of organic system, the second generation uses aluminum nitrate or aluminum carboxylate of water system, and the third generation uses nano-scale alumina or aluminum hydroxide.
4.Comparison of the development of ternary cathode materials in China and other countries
There are two major directions: medium nickel high voltage, high nickel.There is a certain competition in the two development directions of ternary cathodes: medium nickel high voltage and high nickel (conventional voltage). From the perspective of energy density index, for medium-nickel high-voltage 6-series products, the charge cut-off voltage is 4.4V, and the energy density of 6-series cathode materials can be close to the level of nickel 83. From the point of view of thermal stability, medium nickel and high voltage products are generally better than high nickel products. The charging voltage of 622 is 4.5V, the thermal decomposition temperature is higher than that of 811, and the heat release is smaller than that of 811.
Around the world: core-shell structure + NCMA
In addition to the Chinese conventional single crystal, medium nickel high voltage, high nickel, etc., the ternary cathode is also pushing the core-shell structure and quaternary NCMA around the world. The surface modification of the positive electrode material is generally coating, but ordinary coating is easy to lose gram capacity, which can be upgraded to a core-shell structure, or can be further upgraded to a gradient material. The new structural system puts forward higher requirements for the production process and production cost. LG launches NCMA. According to the results released by Hanyang University in South Korea, (1) from NCA89 to NCM90, the cobalt content decreased from 10% to 5%, and the cycle performance was better. (2) NCMA89 can be understood as the modification of NCM90, and the aluminum doping ratio is 1%.
5.Next-generation technology of ternary cathode
The ternary cathode materials direction technology continues to iterate. With the maturity of ternary cathode materials in the direction of high voltage and high nickel, the next-generation products of ternary cathode materials may be cobalt-free, or lithium-rich manganese-based.
Cobalt Free: Lithium Nickel Manganate (NM, Spinel + Layered Structure)
Lithium nickel manganate can be divided into two categories from the crystal structure: spinel type and layered structure. The first one: Doping spinel-type lithium manganate (LiMn2O4) with nickel can form spinel-type lithium manganate. Its common chemical formula is LiNi0.5Mn1.5O4. Compared with lithium manganate, the theoretical gram capacity is unchanged, and high voltage is required for performance. Another lithium nickel manganate has a layered structure, which is equivalent to not adding a cobalt source in the preparation process of the existing ternary NCM positive electrode, including medium nickel without cobalt, high nickel without cobalt, ultra-high nickel without cobalt, etc.
Lithium-rich manganese-based gram capacity is higher, which can exceed 250mAh/g. The crystal structure is mainly a layered phase, and lithium ions further replace the elements in the transition metal layer. Its composition can be understood as the mixture of Li2MnO3 and ternary cathode NCM (solid solution/nanoscale mixture). Preparation process: Lithium-rich manganese base is similar to the existing ternary cathode, precursor + high temperature sintering.
Challenges: (1) The first effect is low, the activation of the Li2MnO3 component requires a first charge voltage exceeding 4.4V, Li and O are extracted in the form of Li2O and O2, only one Li+ is inserted back during discharge, and the redox reaction of lattice oxygen is difficult to control . (2) Low rate performance. (3) The discharge voltage platform decays faster. (4) High voltage, the charging voltage is higher than 4.6V, and the decomposition voltage of the current commercial electrolyte is usually below 4.4V.
6.Analysis of key companies in the ternary cathode industry chain
Due to the high energy density of the ternary cathode, it has steadily occupied the mid-to-high-end market in the new energy vehicle market. In 2021, the output of ternary cathode materials in China will be 398,100 tons, a year-on-year increase of 89.5%; the global output will be 729,700 tons, a year-on-year increase of 79.3%. With the further development of ternary cathode materials in the direction of single crystal, high voltage and high nickel, the technical threshold of the industry continues to increase.
Rongbai Technology is a leading enterprise in Chinese high-nickel ternary cathode materials. In 2021, the proportion of high nickel in the company’s shipments will reach 90%. The market share of the company’s high nickel products has ranked first in the country for many years. At present, the company’s high nickel 9 series precursor and 9 series single crystal cathode have achieved mass production. In terms of production capacity, the company expects to expand production to 250,000 tons by the end of this year, more than double the 120,000 tons at the beginning of the year. With the further rapid expansion of the company, the company is expected to rank first in the world in the ternary cathode materials market.
The main product of Dangsheng Technology is the ternary cathode, which is mainly exported around the world. The company’s international customers mainly include SK on, LG Chem, AESC, Northvolt and other power battery companies and car companies. The company’s products are exported to Japan, South Korea, Europe and the United States. The company’s Chinese customers include Yiwei, AVIC, Honeycomb, etc. Compared with Chinese market, the certification cycle around the world is longer, and the requirements for product quality and stability are higher. And after the certification is passed, it is also more secure in terms of shipments and profitability. The company’s high-nickel products are in a leading position in the industry. The agglomerated high-nickel products are rapidly increasing, and the single-crystal high-nickel products have entered the evaluation of multiple models. The agglomerated single-crystal composite high-nickel products continue to iterate, and the ultra-high nickel Ni95 has completed international customer certification.
The main product of Changyuan Lithium is the ternary cathode material, and the proportion of self-supplied precursors is relatively high. In 2021, the company’s output of ternary precursors was 28,900 tons, all for self-use, and the output of ternary cathode materials was 44,700 tons, which is equivalent to the proportion of self-supplied precursors to 65%. The company’s nickel high-voltage products are in a leading position in the industry. The company’s new-generation medium-nickel high-voltage 65 series single crystal products use low-cost coarse-grained lithium sources, which can reduce costs and improve production efficiency. In terms of high nickel, the company’s new generation of nickel 83 single crystal products has passed the Ningde era ton-level sample test. The company’s ultra-high nickel 9-series single crystal products, downstream customers have entered the ton-level trial production stage.
Zhenhua New Materials is mainly engaged in ternary cathode materials field. The company has very deep research on single crystal cathodes. The company launched the first-generation 5-series monocrystalline products as early as 2009. Since 2018, the company has gradually launched 6-series and 8-series single crystal products. The company’s single crystal products are mainly based on the three-time sintering process. The three-sintering process has certain advantages in the selection of precursors and the preparation of high-nickel materials. In 2021, the company’s high-nickel 8-series products will be supplied in batches, and the revenue of 8-series products will account for 38.08%. In addition, the company’s ultra-high nickel 9 series ternary cathode materials have begun to send ton-level samples to some customers in 2021.
Xtc New Energy is a global leader in lithium cobalt oxide cathode materials. In 2021, the company sold 45,000 tons of lithium cobalt oxide, an increase of 35%. The company’s high-voltage 4.48V lithium cobalt oxide products will be shipped in large quantities from 2020. According to the statistics of Xinyu Information, the global market share of the company’s lithium cobalt oxide products reached 42% in 21 years, an increase of 8.5pct year-on-year. In terms of ternary cathodes, the company developed a new generation of medium-nickel high-voltage 6-series products, which have been successfully applied to electric vehicles with a cruising range of more than 1,000 kilometers. In terms of high nickel, the company’s 8-series polycrystalline and single-crystalline products have been mass-produced, and the 9-series is in the stage of mass testing.
Btr New Energy is a leading company in anode materials in the world. In 2021, the company sold 166,000 tons of anode materials, a year-on-year increase of 121%. According to the statistics of Xinyu Information, the global market share of the company’s anode materials in 2021 was 19%, ranking first in the world. The company invests heavily in R&D. In 2021, the company’s research and development expenses were 590 million yuan, accounting for 5.6% of revenue. In terms of positive electrodes, the company sold 18,300 tons of ternary positive electrodes in 2021, a year-on-year increase of 452%, achieving a breakthrough. And the company’s ultra-high nickel cathode material development project has completed the small test and entered the pilot test stage.
The ternary cathode materials develops in the direction of single crystal, high voltage and high nickel, and the upstream raw material ternary precursor also has an important influence on the final performance of the ternary cathode material. At present, China is in a leading position in the world in the research and development and production of ternary precursors. In the global output of ternary precursors in 2021, CNGR Advanced Material, Gem and Huayou Cobalt will rank among the top 100 lithium ion battery manufacturers in the world. In addition, the precursor products of Fangyuan Co., Ltd. are mainly supplied to Panasonic, Btr, Dangsheng Technology, etc., and its technical strength is also in a leading position in the industry.