Main content:
Phosphate-based new energy materials are indispensable key materials for the development of the battery industry. This article will introduce the development status of new phosphorus energy materials such as lithium iron phosphate, lithium manganese iron phosphate, phosphate-based polyanion compounds, lithium hexafluorophosphate, sodium hexafluorophosphate, phosphate-based solid electrolytes, and phosphate-based negative electrode materials, and outlook their development prospects, and explain the opportunities and challenges faced by phosphorus chemical enterprises.
Positive electrode material
Lithium iron phosphate
Lithium iron phosphate cathode material has the advantages of high safety, high cost performance and long cycle life, and is one of the most widely used cathode materials. In the field of power batteries, the penetration rate of China's lithium iron phosphate batteries in 2023 is about 64%; In the field of energy storage, lithium iron phosphate battery energy storage accounts for more than 90% of China's new energy storage market.
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The development of the new energy market has led to rising shipments of lithium iron phosphate. From 2014 to 2023, shipments of lithium iron phosphate increased from 13,500 tons to 1.65 million tons, with a compound annual growth rate of 70.5%. In particular, after the shipment of lithium iron phosphate in 2021, the lithium iron phosphate industry has developed rapidly, and has formed two distinct characteristics: there are many participants and huge planning capacity. In terms of participants, in addition to traditional battery material manufacturers, it also involves battery manufacturers, phosphorus chemical enterprises, titanium dioxide enterprises and some cross-border enterprises, rough statistics announced the construction of lithium iron phosphate production capacity of more than 50 enterprises;
In terms of planning capacity, according to statistics, the actual production capacity of lithium iron phosphate has reached 4 million tons by the end of 2023, and the total production capacity has not yet been put into production and is under construction exceeds 10 million tons. In sharp contrast to the above production capacity, under the layout of enterprises and the rapid expansion of production capacity, the lithium iron phosphate industry has serious overcapacity. In the face of such difficulties, some listed companies have announced the cancellation of lithium iron phosphate projects to raise funds.
However, in any case, the consumption of huge production capacity has become an urgent problem for the lithium iron phosphate industry. Enterprises with no core technology and weak financial strength may be eliminated in the industry reshuffle.
Lithium ferromanganese phosphate
Lithium manganese iron phosphate is considered to be the "upgraded version of lithium iron phosphate", its cyclic performance and safety can be comparable to lithium iron phosphate, and the theoretical energy density is about 20% higher than lithium iron phosphate, which solves the pain point of insufficient energy density of lithium iron phosphate. However, there are also some problems, such as low conductivity and manganese dissolution affecting battery cycle stability.
In order to solve the above problems, it is necessary to modify the lithium ferromanganese phosphate, including carbon encapsulation, nano, doping, composite and so on. Therefore, although the production process of lithium iron phosphate is similar to that of lithium iron phosphate, and even some production lines can be shared, the processing process is more complex, and the production cost is between lithium iron phosphate and ternary batteries, there is still a certain cost reduction space.
In spite of this, lithium manganese iron phosphate has received higher attention from the market with its high cost performance, and is mainly used in the field of electric two-wheeled vehicles, and some are used in the field of power batteries by mixing with terpolymer materials.
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Although the current lithium ferromanganese phosphate shipments are very small, but under the joint promotion of positive electrode material companies, battery manufacturers and car companies, lithium ferromanganese phosphate is expected to achieve volume growth. According to public information, battery manufacturers and car companies have also laid out lithium ferromanganese phosphate batteries.
According to public information, Ningde Times New Energy Technology Co., Ltd. has launched M3P battery (ternary lithium ion + iron manganese phosphate lithium battery), and equipped with Chery Automobile Co., Ltd. and Huawei Technologies Co., Ltd. cooperation in the intelligent S7 and other related models; Zhongchuang Xinhang Technology Co., Ltd. released OS high manganese iron lithium battery, battery pack energy density of 180 W·h/kg.
Guoxuan High-tech Co., Ltd. released the lithium ferradenophosphate L600 Qichun battery and battery pack, the system energy density of 190 W·h/kg, and plans to start mass production in 2024. In the future, with the cost reduction of scale effect and the research and development of material modification, lithium ferromanganese phosphate is expected to be applied on a larger scale in the field of power batteries, and the market size is expected to grow.
Electrolytes
Lithium hexafluorophosphate
Lithium hexafluorophosphate has become the most widely used lithium battery electrolyte with the best comprehensive performance due to its strong conductivity, electrochemical stability and high matching degree of positive and negative electrode materials. At present, the production process of lithium hexafluorophosphate mainly includes hydrogen fluoride solvent method and organic solvent method. Among them, hydrogen fluoride solvent method is the current mainstream process, which can produce solid lithium hexafluorophosphate.
In recent years, the production capacity of lithium hexafluorophosphate has expanded rapidly, and there is a serious imbalance between supply and demand. According to EVTANK statistics, from 2020 to 2022, the global lithium hexafluorophosphate shipment will increase from 47,000 t/a to 134,000 t/a, an increase of nearly 185%. At the same time, the price of lithium hexafluorophosphate has also risen from a low of 80,000 yuan /t to nearly 600,000 yuan /t. Strong demand and rising prices have prompted relevant companies to increase the layout of lithium hexafluorophosphate.
Sodium hexafluorophosphate
Sodium hexafluorophosphate has become the mainstream sodium battery electrolyte because of its high conductivity and thermal stability, and the best comprehensive performance. Sodium hexafluorophosphate technology is mature, its production process is basically the same as lithium hexafluorophosphate, and the difficulty of mass production is low. At the same time, it replaces lithium salt with sodium salt at the raw material end, which has more cost advantages than lithium hexafluorophosphate.
Sodium hexafluorophosphate is in the initial stage of industrialization. According to public information statistics, lithium hexafluorophosphate production enterprises represented by polyfluorophosphate and Tianci materials have taken the lead in deploying sodium hexafluorophosphate projects relying on their technological and market advantages, of which polyfluorophosphate is the first commercial mass production of sodium hexafluorophosphate enterprises in China. China's actual production capacity of sodium hexafluorophosphate is about 1,000 tons, and the production capacity under construction and planning exceeds 44,000 t/a.
At the same time, sodium hexafluorophosphate is currently in limited demand. Polyfluoro disclosed that its sodium hexafluorophosphate supplies a number of sodium battery companies, but because the actual shipment of sodium batteries is very small, the market demand for sodium hexafluorophosphate is not large, and the subsequent development still needs to achieve large-scale commercial application of sodium batteries.
Phosphorus based solid electrolyte
Solid-state batteries have two significant advantages of high energy density and high safety, and are known as the next generation of high-performance batteries. Solid electrolyte is the key material of solid state battery, including polymer electrolyte, oxide electrolyte and sulfide electrolyte. Among them, LiM2 (PO4) 3 with NASICON type structure is the most used oxide electrolyte at present, which mainly includes lithium titanium phosphate, lithium zirconium phosphate, lithium germanium phosphate, lithium hafnium phosphate and other types.
In particular, lithium aluminum titanium phosphate modified by doping Al3+ has become the mainstream of oxide electrolytes. However, it can not be ignored that the low ionic conductivity and processability of LiM2 (PO4) 3 material still cause certain obstacles to its industrial application.
Solid electrolyte is in the near mass production stage. At present, the industrialization of all-solid-state batteries still faces a series of technical difficulties, but semi-solid-state batteries, as a transition technology for liquid batteries to all-solid-state batteries, will take the lead in entering the commercialization stage.
According to Gaogong lithium battery statistics, as of the end of 2023, China's semi-solid battery cumulative planned production capacity is close to 300 GW·h, landing production capacity is about 15 GW·h, shipments break through the GW·h level, and it is expected that shipments in 2024 are expected to reach 5 GW·h. The mainstream route of semi-solid batteries is oxide electrolytes, mainly titanium aluminum lithium phosphate and lithium lanthanum zirconium oxygen. With the commercialization of semi-solid batteries, the industrialization of phosphorUs-Based solid electrolytes will be further promoted.
Negative electrode material
With its low cost, high specific capacity and suitable sodium storage potential, phosphorus has become a kind of sodium ion anode materials with great potential. Phosphorus based negative electrode materials mainly include red phosphorus based negative electrode materials and black phosphorus based negative electrode materials. However, the electrical conductivity of red phosphorus is poor, and the volume expansion after sodium storage leads to poor structural stability, and the battery capacity decays quickly.
Black phosphorus has a graphite-like layered structure, and its conductivity and density are much higher than red phosphorus, showing better electrochemical performance than red phosphorus, which is an ideal electrode material for electrochemical energy storage, but it also has the problem of volume expansion after sodium storage. The above problems cause difficulties in the industrial application of phosphorus based anode materials.
In this regard, researchers have conducted a lot of research to improve the performance of phosphorus based anode materials, such as red phosphorus or black phosphorus with carbon materials, conductive polymer materials and two-dimensional materials. Although some research results have shown a good application prospect, there is still a certain gap from the actual application.
Prospects of new energy materials based on phosphorus
In the context of carbon neutrality, the new energy industry has broad prospects for development. Shell's 2060 Carbon Neutral Report on China's Energy System proposes that in order to decarbonize the power system, the share of solar and wind power generation should increase to 80% by 2060. The great development of wind power and optoelectronics will drive the outbreak of energy storage market demand. Everbright Securities predicts that by 2060, the annual global energy storage demand space will reach 10 TW·h, and the cumulative demand from 2020 to 2060 will reach 94 TW·h.
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Among them, the cumulative energy storage space of China's wind and solar power generation side is about 3.6 TW·h by 2060. At the same time, the development momentum of new energy vehicles is still rapid. The Overall Forecast Report on China's Automobile Market in 2024 released by the China Association of Automobile Manufacturers predicts that the total automobile sales in the Chinese market in 2024 will reach 31 million, of which the sales of new energy vehicles will reach 11.5 million, an increase of 20% year-on-year, and the penetration rate of new energy vehicles will further increase to 37%.
Conclusion
Phosphate-based new energy materials play a crucial role in the global energy transformation and electrification process. With the rapid growth of new energy demand, especially in the field of power batteries, energy storage systems and electric vehicles, phosphorus materials such as lithium iron phosphate, lithium manganese iron phosphate, hexafluorophosphate electrolytes and phosphate-based negative electrode materials have broad application prospects. In the future, the wide application of phosphate-based materials in the field of new energy will certainly make an important contribution to the realization of sustainable development goals.
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