Advantages and challenges of lithium ferromanganese phosphate

1.1 Lithium manganese iron: Insufficient energy density drives the upgrading trend of lithium iron and manganese

From the perspective of positive electrode material segmentation, lithium iron phosphate and ternary materials are the two most used materials in the field of power batteries. Before 2017, lithium iron phosphate first occupied the commercial vehicle market with its low cost advantage. From 2017 to 2019, ternary materials under the energy density incentive policy counterattacked and became the mainstream technical direction. From 2020 to 2023, subsidies will decline, the market demand for cost reduction is urgent, and lithium iron phosphate will again gain favor, accounting for 64.9% of the installed capacity in November 2023.

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Insufficient energy density is always a pain point problem of lithium iron, and the upgrading trend of lithium iron phosphate doped manganese is clear. The energy density of the mainstream lithium ferromanganese phosphate battery is below 200Wh/kg, and the energy density of the ternary lithium battery is between 200-300Wh/kg. In the context of the continuous improvement of the endurance requirements of new energy vehicles, insufficient energy density has always been a pain point for lithium iron phosphate cathode materials. Lithium manganese iron phosphate effectively improves battery life by improving the platform voltage. Under the game of cost and performance, the upgrading trend of lithium iron phosphate doped manganese is clear.

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1.2 Advantage 1: Energy density + low temperature performance + safety three performance advantages are significant

Lithium ferromanganese phosphate has significant performance advantages, as follows:

? Better energy density compared with lithium iron phosphate. The energy density of the cathode material directly affects the comprehensive performance of the power battery, and the capacity and voltage jointly determine the energy density of the material. Manganese itself has the characteristics of high voltage, after iron lithium manganese, the voltage platform can be increased from 3.4V to 3.8-4.1V, thereby increasing the theoretical energy density by 10%-20%, which can provide higher driving range for electric vehicles than lithium iron phosphate batteries.

? Compared lithium iron phosphate, low temperature performance is better. At -20℃, the low temperature retention rate of LFP material is only about 48%, while LMFP can reach 77-78%. The low temperature performance of lithium manganese iron phosphate is superior mainly due to the Mn platform capacity at low temperature. The research shows that at -20℃, the capacity play of Fe platform accounts for about 50% of the capacity of Fe platform, and the low temperature capacity play of Mn platform accounts for about 95% of the capacity of Mn platform.

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? Compared ternary materials, better safety. Lithium ferromanganese phosphate has a hexagonal close-packed structure, in which Li and Fe (Mn) atoms occupy the octahedral 4a and 4c sites, respectively, and P atoms occupy the tetrahedral 4c sites. The FeO6 (MnO6) octahedron and PO4 tetrahedron are cross-connected, and even if the lithium ions are all removed during the charging process, there will be no structural collapse problem. At the same time, the P atoms in the material form PO4 tetrahedra through the strong covalent bond of PO, and the O atoms are difficult to get out of the structure, so the material has a very high safety and stability.

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1.3 Advantage 2: Extremely high cost performance + high gross profit drives the development of lithium ferromanganese phosphate

From the perspective of anode material manufacturers, the cost of lithium manganese iron per ton has increased slightly. According to the weekly average price of raw materials from December 11 to 15, 2023 (the price of a single ton of lithium carbonate is nearly 110,000 yuan), the BOM cost of a single ton of NCM523/NCM811/ lithium iron phosphate/lithium iron manganese phosphate is 9.59/11.39/2.97/30,300 yuan, plus manufacturing costs, The total cost per ton is 11.74/14.27/3.58/37,700 yuan respectively, and the cost per ton of lithium manganese is about 4% higher than that of lithium iron.

? BOM cost: Taking Germanfang nano hydrothermal method as an example, compared with lithium iron phosphate, the BOM cost of lithium iron phosphate increases the manganese source and reduces the iron source, which is nearly 2% higher;

? Manufacturing costs: short-term research and development investment is more, amortization leads to higher manufacturing costs per ton, and each process is different. In the long run, the manufacturing cost is about 10% higher than that of lithium iron after mass production, mainly because the equipment price of lithium iron production line is higher than that of lithium iron; ② The manufacturing complexity of lithium manganese iron is higher than that of lithium iron.

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From the perspective of anode material manufacturers, compared with lithium iron, lithium manganese iron business gross profit increased. According to the weekly average price from December 11 to 15, 2023 (the price of lithium carbonate per ton is nearly 110,000 yuan), the price of lithium manganese iron is 10% higher than that of lithium iron, the yield is 98%, and the lithium carbonate inventory is one week. The gross profit per ton of NCM523/NCM811/ lithium iron phosphate/lithium iron manganese phosphate is 1.12/1.68/0.53/0.81 million yuan, respectively, and the gross profit per ton of lithium iron manganese is 52% higher than that of lithium iron. In the long run, with the gradual mass production of lithium ferromanganese, the competition of cathode material manufacturers has intensified, and the price of lithium ferromanganese is likely to decline. According to estimates, the price has dropped from 10% higher than lithium iron to 5% higher, and the gross profit per ton is still 8% higher, indicating that its profits are considerable. At present, the downstream battery manufacturers have the absolute right to speak, the gross profit of the lithium iron phosphate track has reached the bottom, and the lithium manganese iron can achieve a single ton of gross profit improvement on the basis of lithium iron phosphate, driving the transformation and upgrading of positive electrode material manufacturers.

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1.4 Challenge: Modification becomes a key part of industrialization

The difficulty of lithium manganese iron material increases the technical threshold. It mainly includes: ① the conductivity of manganese is poor and the conductivity is low, which has an impact on the battery life and stability; ② Manganese dissolution will reduce battery cycle life and cycle stability; (3) There are two voltage platforms in the charge and discharge curves. The platform near 3.5V is Fe2+ converted to Fe3+, while LiMn0.4Fe0.6PO4/C can effectively improve the energy density of such materials at a high potential platform of 4.0V. Different charging and discharging voltages of ferro manganese lead to dual voltage platform in LMFP, which increases the difficulty of late battery management system (BMS) management.

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Modification has become a key part of industrialization. In order to achieve industrialization, cathode material manufacturers and battery manufacturers have proposed modification plans, as follows:

Nanometer: nanometer refers to the reduction of material size to nano-sized particles by mechanical milling, controlling the calcination temperature, using superconducting particles as nuclear accelerators and other ways. Nano-sized particles can shorten the diffusion path of lithium ion, improve the efficiency of lithium ion migration, reduce the electrode polarization, and thus improve the low-temperature performance of the magnification performance. At the same time, the specific surface area of the material is improved to improve the electronic conductivity.

Carbon coating: The conductive material coated on the surface of lithium ferradenophosphate can improve the new conductive energy of the material, avoid particle agglomeration, improve uniformity and improve magnification performance. At the same time, the surface coating can inhibit the dissolution of manganese ions to a certain extent, so as to improve the cycle life of the material.

? Doping: ion doping is to change the conductivity and ion diffusion properties of the material from the inside of the lattice, doped ions can cause defects in the lattice, and can inhibit the ginger Taylor effect, thereby improving the material performance.

? and ternary reuse: LMFP composite coating with ternary materials can improve the specific capacity of the material, low temperature capacity retention rate, compaction density, etc. At present, the mainstream scheme is that the ratio of ternary and lithium ferromanganese is 6/4 and 7/3, which is mainly pure lithium ferromanganese phosphate, and the conductivity of materials with high manganese proportion is reduced, and the problem of manganese dissolution is prominent.

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2

Development trend of lithium manganese iron

2.1 Development Path

Cost factors determine that mixing is only a transitional scheme, and pure use is expected to replace mixing as the main application scheme in the future. At present, the mainstream solution in the market is the mixing of ternary materials and ferromanganese lithium, and the mixing ratio is 70%/60%. When the composite material is NCM523, the single kilogram cost of the positive electrode material is 114/105 yuan, higher than the pure 123%/105%, and the single kWh cell cost is 436/425 yuan, higher than the pure 22%/19%. When the composite material is NCM811, the single kilogram cost of the positive electrode material is 134/122 yuan, which is higher than the pure use of 163%/139%, and the single kWh cell cost is 463/448 yuan, which is higher than the pure use of 29%/25%, which is relatively different from the cost of the pure use program.

After mass production, the scale effect is prominent, and the cost of materials is further reduced. At present, lithium ferromanganese is still in the early stage, with the development of lithium ferromanganese, production and capacity utilization will be significantly improved, the scale effect is highlighted, the yield is improved, and the cost is expected to continue to decline.

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2.2 Market space: It is expected that China's demand for ferromanganese lithium will exceed 200,000 tons in 2025

The future incremental space of lithium ferromanganese phosphate is mainly concentrated in the new energy vehicle power battery market. In the short term, Tesla, Chery and other head car companies gradually play a demonstration role, and lithium manganese iron is expected to enter some mid-end models and usher in volume. In the medium term, lithium manganese iron to pure use program evolution, with cost advantages, is more expected to replace nickel (5 series, 6 series) ternary materials and some lithium iron in the power cell market. In the long run, lithium manganese iron has better low temperature characteristics, leading anode material manufacturers such as Germany has started the development of the second generation of lithium manganese iron products with better cycle life, and LMFP batteries are expected to penetrate the energy storage market.

In 2025, the shipment of lithium ferromanganese phosphate in the Chinese market is expected to exceed 200,000 tons. According to GGII, in 2022, China's shipments of lithium ferromanganese phosphate are only 2,000 tons, mainly used in the field of electric two-wheeled vehicles, and in 2023, the main volume comes from the mixed program of terpolymer and lithium ferromanganese, with the acceleration of research and development of head battery enterprises and the downstream electric vehicle sales continue to increase. In 2025, China's lithium ferradenophosphate cathode material shipments are expected to exceed 200,000 tons, and the market size is expected to exceed 10 billion yuan.

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3

Iron manganese lithium industry chain situation

3.1 Industrial chain: downstream car companies drive manganese iron lithium volume, midstream positive/battery manufacturers have layout

Lithium manganese iron, the upstream manganese source benefits, the middle stream cathode material manufacturers have expanded production, battery manufacturers have layout. The details are as follows:

? Upstream: Compared with LFP, LMFP increases manganese, and the manganese source in lithium batteries is generally manganese dioxide or manganese sulfide. Manganese source enterprises mainly have Esokai, Green beauty and so on.

? Midstream: mainly includes positive material manufacturers and battery manufacturers, of which positive material manufacturers can be divided into iron lithium manufacturers and ternary manufacturers. Among the cathode material manufacturers, the production capacity of iron lithium manufacturers is generally ferromanganese lithium and iron lithium collinear, leading enterprises have switched to production expansion, and at present, Germanfang Nano and Hunan Yuleng are leading; Some teryuan manufacturers expanded the lithium manganese iron business, among which the leading enterprise, Junbai Technology acquired Skland to achieve corner overtaking. Among the battery manufacturers, the leading enterprise Ningde Times has taken the lead and launched the M3P ferromanganese lithium battery, which has been installed on the Smart S7 model that has been sold. Guoxuan Hi-tech released the lithium iron manganese phosphate system L600 Qichun battery and battery pack, with a pure battery life of more than 1,000 kilometers, and mass production in 2024.

? At present, Chery Intelligence S7 has been listed, Tesla has a lithium manganese model ready to be listed, other car companies have followed the layout.

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3.2 Downstream: The first lithium manganese iron model has been sold, and the Tesla lithium manganese iron model is about to land

Chery and Tesla are ahead of schedule, and other car companies are currently in the test sample stage and are expected to follow the footsteps of the head car companies in the layout of lithium manganese models.

? Chery: In August 2023, in the 374th batch of new energy vehicle product catalog of the Ministry of Industry and Information Technology, the two models of the pure electric brand Wisdom S7 launched by Chery and Huawei, as well as the two models of Chery's pure electric brand Star Road, will be equipped with the "ternary + lithium iron manganese phosphate" battery combination of Ningde era, which is the M3P that has attracted much attention in the industry. At present, the wisdom of S7 has opened the pre-sale.

? Tesla: Tesla's domestic Model 3 model will continue to upgrade the battery pack, especially the basic rearwheel drive version of the power will be upgraded from 60kWh (degree) to 66kWh, using the new M3P lithium iron phosphate battery in the era of Ning De. Considering that Tesla's export proportion is large, Northern Europe and other regions have higher requirements for low-temperature battery performance, and the United States considers the characteristics of new energy vehicles with long endurance, lithium manganese iron as an alternative to lithium iron phosphate is the future focus of Tesla's layout.

3.3 Midstream battery manufacturers: car companies drive each layout of manganese iron lithium, Ningde Time leads

Battery manufacturers have laid out lithium manganese iron, downstream car companies to help accelerate the industrialization of the landing. In addition to the Ningde era, BYD, billion Wei lithium energy, Guoxun high-tech, Funeng technology, Beehive energy, Rupu Lanjun, Star power and other battery companies are competing to layout.

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3.4 Middle anode material manufacturers: to the transformation and upgrading of manganese iron lithium, Germany, Rong Bai lead

3.4.1 Technical Route

The solid phase method and liquid phase method coexist, and the iron lithium manufacturers are easier to migrate. Solid phase method includes high temperature solid phase method and carbon thermal reduction method, which is mainly characterized by high energy consumption and relatively low equipment requirements, but product purity is difficult to ensure. Unlike LFP, the mixing process requires the use of mechanical ball milling of iron and manganese sources or the addition of liquid phase to fully mix the raw materials. Liquid phase method includes solvothermal method, sol-gel method and co-precipitation method, which is mainly characterized by superior product performance, but it is difficult, the process is more complex, and the equipment is higher.

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3.4.2 Manufacturers of positive electrode materials have transformed and upgraded, and lithium manganese iron is progressing smoothly

Positive manufacturers to iron manganese lithium transformation and upgrading. Germanfang Nano earlier layout of iron manganese lithium material, that is, in 2021 research and development success, has at least 110,000 tons of production capacity, becoming the only production capacity to meet the industrialization of iron manganese lithium manufacturers. In addition, Rongbai Technology, Hunan Yuleng and other accelerated layout.

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