Lithium batteries are mainly composed of four main materials, including positive electrode, negative electrode, electrolyte and separator. Lithium batteries can be divided into cylinders, squares, soft bags, etc.

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positive electrode material is an important part of lithium batteries

Lithium batteries are mainly composed of four main materials, including positive electrode, negative electrode, electrolyte and separator. Lithium batteries can be divided into cylinders, squares, soft bags, etc. In addition, it is also commonly divided according to the types of positive electrode materials used, including lithium cobalt oxide battery , ternary battery, lithium iron phosphate battery, etc. In 2021, my country's installed power battery capacity will be 154.5GWh, mainly lithium iron phosphate battery and ternary batteries. Among them, the ternary battery has a capacity of 74.35GWh, accounting for 48.1%.

ternary positive electrode market has grown rapidly

With the rapid growth of sales of new energy vehicles and the steady growth of markets such as power tools, the shipment of ternary positive electrode materials continues to maintain a high growth. In 2021, the total shipment of domestic positive electrode materials exceeded 1 million tons, reaching 1.094 million tons, and increased by 8.5% year-on-year. In 2021, domestic shipments of ternary positive electrode materials were 422,000 tons, an increase of 79.6% year-on-year.

ternary positive electrode material accounts for more than half of the battery cost

positive electrode material is a core component of lithium batteries and has a direct impact on many core performance indicators of lithium batteries, including capacity, life, magnification, safety, etc. Usually, the deintercalable lithium ions in lithium batteries are derived from positive electrode active substances. In terms of cost, positive electrode accounts for more than half. We use the 5-series ternary battery as a model and combine the main material quotations of Shanghai Nonferrous Network to split the cost of the 5-series ternary battery. Currently, the positive electrode material accounts for about 60% of the cost of battery cells.

positive electrode material multiple technical routes coexist with

positive electrode material according to crystal structure , it can be divided into three categories: spinel, peridot and layered structure. In the power battery market, iron phosphate lithium , lithium manganese iron phosphate, and Ningde 's new technology route M3P positive electrode all belong to the olivine structure. NCM, NCA, etc. used in the commercial application of power battery market all belong to a layered structure. Judging from the gram capacity index, the ternary positive electrode has relatively great advantages over lithium iron phosphate and lithium manganate .

ternary positive electrode performance still has a lot of room for improvement

lithium iron phosphate positive electrode material theoretical capacity is 170mAh/g. At present, industrialization can exceed 156mAh/g, and the actual value/theoretical value reaches 92%. Lithium iron phosphate will continue to strive for excellence. Currently, the commercial ternary 5 Series and 6 Series have a gram capacity of about 180mAh/g, and the actual/theoretical value is only 65%. Currently, the commercial tertiary 8-Series positive electrode capacity is about 200mAh/g, and the actual/theoretical value is only 72%.

accelerates product iteration

ternary positive electrode material companies are constantly innovating on the basis of existing products. Among the companies that mainly engage in ternary positive electrode materials, the R&D expenses of Rongbai Technology and Dangsheng Technology in 2021 exceeded 300 million yuan. Among the companies that mainly engage in lithium iron phosphate, Defang Nano's R&D expenses in 2021 will be 164 million yuan.

Three major trends of ternary positive electrode

Trend 1: Single crystallization (advantages)

positive electrode materials can be divided into polycrystalline and single crystal . Generally, polycrystalline materials exist in the form of agglomerates at the micron level. There are a large number of grain boundaries inside the agglomerates. During the battery charging and discharging process, due to the anisotropic lattice changes, polycrystalline materials are prone to grain boundary cracking, resulting in the breaking of secondary particles. This leads to rapid increase in side reactions, increase in impedance , rapid decrease in performance, etc. Using single crystal particles can reduce grain boundary , reduce the occurrence of side reactions, and increase the compaction density, thereby increasing the energy density. Compared with polycrystalline materials, the cycling performance of single crystal materials is generally much better.

Trend 2: High voltage (advantages)

The second development trend of ternary positive electrode materials is high voltage, which is equivalent to increasing the charging cutoff voltage of lithium batteries. Generally, the charging cut-off voltage of a ternary battery is 4.2V to 4.3V. National standard GB/T 37201-2018 points out that when testing a ternary battery, it is generally charged to 4.2V at a constant current of 0.2C and then charged at a constant voltage.Taking the 5-Series Triple as an example, when the charging cut-off voltage is increased from 4.2V to 4.4V, the discharge capacity of the positive electrode material can be increased from 158.4mAh/g to 188.6mAh/g, an increase of 19%. And when the charging cut-off voltage reaches 4.5V, the cathode capacity can exceed 200mAh/g.

Trend 3: High nickelization (advantages)

The third largest trend of ternary positive electrode: High nickelization. The main purpose of high nickelization is to increase energy density. From the perspective of electronic structure, the eg orbit of cobalt (Co) is an empty orbit, and the t2g orbit and the 2p orbit of oxygen (O) overlap greatly. It is easy to analyze oxygen during deep deliquefaction, and structural collapse occurs. In addition, the t2g orbit of cobalt forms a π bond with the 2p orbit of oxygen, which has weak force and is easy to transfer electrons. The eg orbit of nickel (Ni) overlaps very little with the 2p orbit of oxygen, so in theory, electrons can be completely lost on the eg orbit of nickel, and the effective capacity of lithium nickelate is higher. For manganese, when the nickel content exceeds manganese, manganese will change to a quadruple form, which is very stable. Generally speaking, in NCM systems, the higher the cobalt content, the better the rate performance; the higher the nickel content, the higher the capacity of grams; the higher the manganese content, the more stable the structure. Generally, the gram capacity of the 8-Series 3-way unit can exceed 200mAh/g.

implementation path: doping and surface modification have a significant impact on the performance of positive electrode materials

Whether it is an ordinary positive electrode material or when developing towards single crystal, high voltage, and high nickel, doping and surface modification are effective methods to improve the comprehensive performance of positive electrode materials. In addition, the doping and modification methods are also one of the core competitiveness of cathode material companies. Doping elements include Al, Mg, Cr, etc., and the improvement mechanism includes stabilizing the main structure, increasing the spacing of lithium ion , segregation at grain boundaries, etc.

Commonly used coating agents include Al2O3, V2O5, ZnO, ZrO2, TiO2, MgO, etc. Taking the alumina coating method as an example, the first generation technology uses aluminum isopropoxide in the organic system, the second generation uses alumina nitrate or aluminum carboxylate in the water system, and the third generation uses nanoscale alumina or aluminum hydroxide.

Comparison of two major domestic directions: medium nickel high voltage, high nickel

There is certain competition in the two development directions of domestic ternary positive electrodes: medium nickel high voltage and high nickel (regular voltage). From the perspective of energy density indicators, for medium-nickel high-voltage 6-series products, the charging cut-off voltage is 4.4V, and the energy density of the 6-series positive electrode material can be close to that of nickel 83. Judging from the thermal stability indicator, medium-nickel high voltage products are generally better than high-nickel. 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.

Overseas: core-shell structure + NCMA

ternary positive electrode In addition to the conventional single crystals, medium-nickel high voltage, high nickel, etc. in China, core-shell structure and quaternary NCMA are also being promoted overseas. The surface modification of the positive electrode material is generally coated, but ordinary coats are prone to lose grams of capacity and can be upgraded to a core-shell structure or further upgraded to a gradient material. The new structural system puts higher requirements on production processes and production costs. LG launches NCMA. According to the results released by Hanyang University in South Korea, (1) From NCA89 to NCM90, the cobalt content dropped from 10% to 5%, and the circulation performance was better. (2) NCMA89 can be understood as modifying NCM90, with an aluminum doping ratio of 1%. (Report source: Future Think Tank)

Next-generation technology of ternary positive electrode

ternary positive electrode direction technology is constantly iterating. As the technology of ternary positive electrode materials matures in the high voltage and high nickel directions, the next generation of ternary positive electrode products may be cobalt-free or lithium-rich manganese-based.

Cobalt-free: Nickel-manganese oxide (NM, spinel type + layered structure)

Nickel-manganese oxide can be divided into two categories from the crystal structure: spinel type and layered structure. The first type: Nickel doping of spinel-type lithium manganese oxide (LiMn2O4) can form spinel-type lithium nickel-manganese oxide, and its common chemical formula structure is LiNi0.5Mn1.5O4. Compared with lithium manganate, the theoretical capacity remains unchanged and requires high voltage to perform performance. Another type of lithium nickel manganate has a layered structure, which is equivalent to not adding cobalt sources during the preparation of the existing ternary NCM positive electrode, including medium nickel cobalt-free, high nickel cobalt-free, ultra-high nickel cobalt-free, etc.

Lithium-rich manganese base: higher gram capacity (layered structure)

Lithium-rich manganese base has higher gram capacity, which can exceed 250mAh/g. The crystal structure is mainly a layered phase, and lithium ions further replace elements in the transition metal layer. Its composition can be understood as the mixture of Li2MnO3 and ternary positive electrode NCM (solid solution/nanoscale mixing). Preparation process: Lithium-rich manganese-based is similar to the existing ternary positive electrode, with precursor + high-temperature sintering. Challenge: (1) Low first efficiency, Li2MnO3 component activation requires the first charge voltage to exceed 4.4V, Li and O are released in the form of Li2O and O2, and only one Li+ is embedded during discharge, and redox reaction of lattice oxygen is difficult to control. (2) Low rate performance. (3) Discharge voltage The platform decays faster. (4) High voltage, charging voltage is higher than 4.6V, and the current commercial electrolyte decomposition voltage is usually below 4.4V.

The three-yuan positive electrode industry is developing rapidly, and the technology iteration is the leader, and the leader is the best

Due to the high energy density of the three-yuan positive electrode, it firmly occupies the mid-to-high-end market in the new energy vehicle market. In 2021, the domestic production of ternary positive electrode materials was 398,100 tons, an increase of 89.5% year-on-year; the global output was 729,700 tons, an increase of 79.3% year-on-year. As ternary positive electrode materials further develop towards single crystal, high voltage and high nickel, the industry's technical threshold is constantly increasing. The leading companies in the industry rely on their technical strength to continuously launch new products and maintain their leading advantages. It is difficult for new entrants to shake the status of leading companies in the industry.

Rongbai Technology: The leading ternary high-nickel high-nickel leading

Rongbai Technology is a leading enterprise in domestic high-nickel ternary positive electrode materials. In 2021, the proportion of high-nickel in the company's shipments reached 90%. The company's high nickel product market share has ranked first in the country for many years. At present, the company's high-nickel 9-series precursor and 9-series single-crystal positive electrode have both 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 growth compared with 120,000 tons at the beginning of the year. As the company further expands rapidly, the company is expected to rank first in the world in the three-yuan cathode material market.

Dangsheng Technology: The overseas market is dominant

Dangsheng Technology's main product is the three-yuan positive electrode, mainly exported overseas. The company's international customers mainly include power battery companies and car companies such as SK on, LG Chem , AESC, and Northvolt. The company's products are exported to Japan, South Korea, Europe and the United States. The company's domestic customers include 00 , AVIC, and Honeycomb. Compared with the domestic market, overseas certification cycle is longer and requires higher product quality, stability, etc. And after passing overseas certification, it is more guaranteed in terms of shipments and profits. The company's high-nickel products are in the leading position in the industry. The agglomerated high-nickel type is rapidly increasing in volume, and the single crystal high-nickel type is entering multiple vehicle models for evaluation. The agglomerated single crystal composite high-nickel type continues to iterate, and the ultra-high-nickel Ni95 has completed international customer certification.

Changyuan Lithium Science: Integrated creation of core advantages

Changyuan Lithium Science main products are ternary positive electrode materials, and the proportion of self-supply of precursor is relatively high. In 21 years, the company's ternary precursor produced 28,900 tons, all of which were used for their own use, and the ternary cathode material produced 44,700 tons, which is equivalent to the self-supply ratio of precursors ~ 65%. The company's medium-nickel high-voltage products are in the leading position in the industry. The company's new generation of medium-nickel high-voltage 65-series single crystal products adopt low-cost coarse lithium source, which can reduce costs and improve production efficiency. In terms of high nickel, the company's new generation of nickel 83 single crystal products have passed the CATL ton sample test. The company's ultra-high nickel 9 series single crystal products, downstream customers have entered the trial production stage of ton.

Zhenhua New Materials: The three-sintering process industry is leading

Zhenhua New Materials mainly sells ternary positive electrode materials. The company has conducted in-depth research on single crystal positive electrodes. The company launched the first generation of 5-series single crystal 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 sintering process in three times. The three-sintering process has certain advantages in precursor selection and high-nickel material preparation. In 2021, the company's high-nickel 8 series products were mass-produced, and the revenue of the 8 series products reached 38.08%. In addition, the company's ultra-high nickel 9 series ternary cathode material has started to deliver tons of samples to some customers in 2021.

Xia Tungsten New Energy: the world's leading lithium cobalt oxide , medium nickel high voltage rapid advancement

Xia Tungsten New Energy is the world's leading lithium cobalt oxide positive electrode material company. In 21, the company's lithium cobalt oxide sales volume reached 45,000 tons, an increase of 35% year-on-year. The company's high-voltage 4.48V lithium cobalt oxide products will be shipped in large quantities starting from 2020. According to Xinli Information statistics, the company's global market share of lithium cobalt oxide products in 21 years reached 42%, an increase of 8.5pct year-on-year. In terms of ternary positive electrodes, the new generation of medium-nickel high-voltage 6-series products developed by the company have been successfully applied to electric vehicles with a range of more than 1,000 kilometers. In terms of high nickel, the company's 8 Series polycrystalline and single crystal products have been mass-produced, while the 9 Series is in the mass testing stage.

Betre: the world's leading negative electrode, the three-yuan positive electrode begins to increase in volume

Betre is the world's leading negative electrode material company. In 21 years, the company's sales of negative electrode materials were 166,000 tons, an increase of 121% year-on-year. According to Xinli Information Statistics, the company's global market share of negative electrode materials in 21 years has been 19%, ranking first in the world. The company has high R&D investment. In 21 years, the company's R&D expenses were 590 million yuan, accounting for 5.6% of its revenue. In terms of positive electrodes, the company's three-yuan positive electrode sales in 21 years were 18,300 tons, a year-on-year increase of 452%, achieving breakthrough progress. In addition, the company's ultra-high nickel cathode material development project has completed a small trial and entered the pilot stage.

ternary precursor: The key raw material for realizing the performance of ternary positive electrode materials

ternary positive electrode develops towards single crystal, high voltage, and high nickel. The upstream raw material ternary precursor also has an important impact on the final performance of ternary positive electrode materials. At present, my country has already taken the lead in the research and development and production of ternary precursors. Among the global ternary precursor production in 2021, Zhongwei Co., Ltd. , Greenmei and Huayou Cobalt Industry ranked among the top three in the world. In addition, Fangyuan Co., Ltd.'s precursor products mainly supply Panasonic , Betre, Dangsheng Technology, etc., and its technical strength is also in the leading position in the industry.

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selected report source: [Future Think Tank]. Future Think Tank - Official Website