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Development history of sodium ion battery

Sodium ion battery has the natural advantages of lithium battery complementary method

Sodium element reserves are rich and evenly distributed, which is a promising complementary method for lithium batteries. Lithium batteries began to be commercialized earlier, mainly because of its small relative atomic mass, low standard electrode potential and high specific capacity. The sodium element is rich in reserves, more evenly distributed, and compatible with existing lithium battery production lines. From the perspective of resource supply guarantee and cost, sodium ion battery is the preferred complementary method for lithium battery.

The research of sodium ion battery has been initiated for a long time, and is about to enter an explosive period

The embryonic stage: in 1967, it started from the high-temperature sodium sulfur battery. Stagnant period: after Armand of France put forward the concept of rocking chair battery in 1979, due to the lack of sodium storage capacity of graphite anode, which is widely used in lithium battery system, the research on sodium ion battery almost stopped. Restart period: until Canadian Dahn and others found that hard carbon anode had excellent reversible sodium storage capacity in 2000, the academic community continued to promote. Revitalization period: by 2010, with the lithium battery research and industrial chain construction becoming mature, and the concern about lithium resources, the research and industrialization process of sodium ion battery has entered the renaissance period, with the emergence of industrial companies and sporadic commercial applications at home and abroad. Outbreak period: until July 2021, CATL announced the first generation of sodium ion batteries and announced that it planned to form a basic industrial chain in 2023. The price of lithium superposed increased rapidly from the end of 2021 to the beginning of 2022, triggering the whole industrial chain to attach great importance to complementary and alternative methods of sodium ion batteries, and dozens of companies promoting the mass production of sodium ion batteries and raw materials emerged. At present, the price of lithium carbonate has exceeded 600000 yuan/ton, further accelerating the industrialization process of sodium ion batteries.

Comparison of battery and material technology routes

Battery: process is similar to lithium battery

The production process of sodium ion battery is basically similar to that of lithium battery, and the traditional lithium battery production line can be adjusted and converted into production. The production process of sodium ion battery mainly includes the production of electrode (pulping - coating - rolling - die-cutting) and the assembly of cell (winding/laminating, shelling, packaging, formation, and volume separation). The overall production process is similar to that of lithium battery, and only aluminum foil is used on the negative current collector and formula adjustment. At present, lithium battery production line can be switched to sodium ion battery production line after commissioning, without additional equipment investment. Similar to lithium battery, sodium ion battery can also be made into soft package, cylinder and square shell.

Positive electrode: the three routes have their own merits, and layered oxide is expected to be the first to be applied

Layered oxide (basically conquered, the preferred method for mass production): the structure is similar to lithium battery three-element cathode material, with relatively high specific capacity and good comprehensive performance. By adjusting the selection and proportion of transition metal elements, the power, energy storage and other multi-scenario requirements can be considered. The process is mature (the process flow and equipment are similar to lithium battery ternary materials), and the supporting company is basically a mature ternary cathode material manufacturer, which can supply samples with good consistency and stable performance and mass production raw materials, which is the preferred method for recent industrialization.

Prussian blue-white (under attack): transition metal can only use Fe or Mn with low cost. The theoretical energy density is high, and the synthesis temperature is low (energy consumption cost is low). It is a hot route at the initial stage. However, due to the difficulty in controlling crystal water during mass production (affecting circulation and safety), the current stability is poor, and it is expected to become a high energy density+low cost optimization method when the future process control is mature.

Polyanion (storage method): Chart: The technical route of sodium ion battery cathode is similar to the olivine structure of lithium iron phosphate, with high structural stability, which has the longest theoretical cycle life and is more suitable for energy storage market. However, the conductivity is poor and the energy density is low. Vanadium-doped route has high cost and poor energy density, which is currently important as a reserve method.

Layered oxide: the process flow is similar to that of ternary anode, and the formula is highly adjustable

There are two common arrangements: octahedral position (O3, higher initial sodium content, higher capacity) and triangular prism position (P2, larger layer spacing, improved transmission rate (magnification) and structural stability). Because sodium is easier to separate from transition metal to form layered structure than lithium, only lithium layered oxide formed by nickel, cobalt and manganese can be reversible charged and discharged at present, and the selection of sodium also includes Ti, V, Cr, Fe, Cu, etc. Different formulations have a great impact on the structure. In addition to the physical characterization of the synthesized material to determine its specific configuration, there is no method that can directly predict the stacking structure of layered materials, and then guide the design and preparation. Industrialization progress: The important production steps are divided into precursor mixing and positive electrode sintering. The modification measures include coating, doping, etc., which are basically compatible with the three-element positive electrode production line of lithium battery. The sintering atmosphere does not require pure oxygen, and the airtightness requirement is low. The sintering frequency is generally 2 times. The medium and low nickel production line basically meets the requirements. The production line designed according to the requirements of high nickel has an over-production ratio (the output elasticity comes from the sintering time and times).

Prussian: high specific capacity, low theoretical cost, but difficult process

Prussian materials have a three-dimensional cube structure, Na+has a suitable diffusion channel, and theoretical magnification performance and cycle performance are good (voltage and specific capacity can be regulated by selecting different transition metals, with high material design flexibility). According to the content of Na+, x<1 is called Prussian blue, x≥ 1 Become Prussian white. Due to the high sodium content of Prussian white, the specific capacity is also higher. Because of the low solubility product constant, it can be used as the cathode material of aqueous solution system. Development process: The original use is glaze and oil painting dye, which can be traced back to 1704. When Heinrich Disbach, a German, produced a red pigment in the laboratory, he obtained dark blue precipitate due to experimental pollution, and Picasso and Van Gogh paintings were frequently used. Preparation method: Prussian materials are usually prepared by coprecipitation method and hydrothermal method at 70-120 ℃, without high temperature sintering and low cost; At present, the actual specific capacity can reach 150-160mAh/g, and the working voltage can reach 3.3-3.4V. Because the structure of ferrocyanide is stable and the precursor is easy to obtain, most of the research focuses on it. Processing difficulty: the bottleneck of Prussian materials is that it is easy to absorb water and difficult to process. There will be a certain amount of crystalline water in the production process, and there is a risk that the battery will be short-circuited and HF will occur in the reaction with the electrolyte due to the removal. Large-scale mass production has high requirements for water control, and there are great difficulties in the process of large-scale mass production.

Negative electrode: switch from graphite to amorphous carbon, and both hard carbon and soft carbon have development potential

At present, graphite is generally not used as negative electrode of sodium ion battery, and amorphous carbon is mostly used in carbon-based system. In the early view, the diameter of Na+is 1.3 times that of Li+and can not migrate freely between graphite layers, but K, Rb and Cs still have high reversible specific capacity. In essence, due to thermodynamic problems, the interaction between sodium ion and graphite layer is weak, and it is difficult to form stable intercalation compounds in current common electrolyte (unless replaced with ether solvent). The sodium ion battery can not directly use graphite anode, and mostly uses amorphous carbon with low graphitization degree, and the layer spacing is higher than that of graphite, which lays the foundation for realizing lossless high magnification. The specific capacity of hard carbon is high, but there are still disadvantages in cost and scale. The hard carbon precursor is a thermosetting material, which is difficult to graphitize at high temperature, with more disordered structure, rich micropores, larger material gap, higher specific capacity and smaller expansion coefficient. However, too many holes lead to large specific surface area and low efficiency for the first time. In addition, hard carbon generally uses biomass, starch, resin and other precursors, with low carbon production efficiency and relatively high cost. The sodium storage capacity of soft carbon is low, but the carbon production rate of precursor is higher, which has cost advantages. The soft carbon precursor is a thermoplastic material, which is easy to graphitize at high temperature, with more orderly structure, shorter interlayer spacing and lower sodium storage capacity. The precursor generally uses coal, asphalt, petroleum coke and other petrochemical industry by-products. The industrial chain is more mature, and the carbon production efficiency can reach more than 90%. In addition, alloys, metal oxides or metal sulfides generally have high specific capacity, but there are problems such as low coulomb efficiency for the first time and electrode pulverization. Titanium-based anode has good air stability and reserve potential.

Negative electrode production process: carbonization consumes less energy than graphitization, and the process presents diversity

The preparation temperature of sodium-ion carbon-based anode is lower: amorphous carbon processing only needs about 1000-1500C carbonization heating, while the graphitization temperature of graphite anode should be at least 3000C, which is more economical from the perspective of energy consumption and cost. The production process is similar, and some processes have special requirements for equipment: the equipment is mainly ball mill and mixer for crushing and mixing, kiln and carbonization furnace for heating, etc. Some heating processes need special atmosphere (sealing requirements), in addition, some pretreatment processes have requirements for corrosion resistance, and hard carbon precursor powder needs dust control. Technical development and optional modification methods: The main purpose of early research on soft carbon and hard carbon is to dope/coat graphite anode system of lithium battery to achieve modification (increase magnification, etc.). Most mainstream anode companies have relevant layout. In the sodium ion battery system, due to the performance defects of both soft carbon and hard carbon materials, in order to improve the comprehensive performance, modification treatments such as pre-activation, pre-oxidation, mixed doping and coating can be carried out. For example, the selection of carbon source can mix soft carbon and hard carbon; Can be doped with N, S, metal oxides, alloys, etc; Three-dimensional core-shell structure is formed by coating, which can improve the surface conductivity while forming rich microporous sodium storage. In addition, there are also rich means to improve the sintering process and the negative electrode plate manufacturing process. In general, there is technical diversity in the selection, processing technology and modification means of cathode precursors, and the cost splitting and pricing model are not transparent. The anode manufacturers are more likely to form technical barriers and bargaining advantages.

Electrolyte: sodium hexafluorophosphate can use the existing production line, which is the preferred method for mass production

The electrolyte of sodium ion battery is similar to that of lithium battery and consists of solute, solvent and additive. The solute must be replaced by lithium salt and sodium salt. The solvent and additive can basically reuse the mature system of lithium battery, but the formula should also be adjusted according to the characteristics of sodium ion to improve the performance. The Stokes diameter of sodium ion is smaller than that of lithium ion. The sodium salt electrolyte with low concentration has higher ionic conductivity. In theory, the electrolyte with low concentration can be used to save costs. The solute sodium salt is mainly divided into organic sodium salt and inorganic sodium salt. The structure of the NaPF6 production process in the inorganic sodium salt is similar to that of the lithium hexafluorophosphate process used in the lithium battery system. It is considered as the most promising sodium salt for industrialization, but its thermal stability is poor. NaFSI in organic sodium salt has high conductivity but narrow electrochemical window, and NaTFSI has good thermal stability but is easy to corrode the collector at low concentration.

BOM cost calculation of sodium ion battery

Cost calculation of sodium ion battery

There is still much room for the price to fall against the standard lithium iron phosphate. Since the market scale of raw materials such as anode and cathode has not yet formed, most companies choose to supply by themselves, and there is no stable market quotation. We predict that at the initial stage of industrialization, the manufacturing cost per kwh of sodium ion batteries will be between 600 and 700 yuan. After the industrial chain forms large-scale production, it is expected to fall below 500 yuan/kwh. Assuming that the price of lithium carbonate falls back to 150000 yuan/ton and the price of LFP falls back to about 73500 yuan/ton, the total cost of LFP cells is about 700 yuan/kWh, and the sodium ion battery will still have obvious cost advantages.

Output sorting and demand calculation

The planned output of sodium ion cell exceeds 100GWh

According to public statistics, the total planned output of sodium ion battery head manufacturers exceeds 100GWh. It is mainly divided into the transformation of traditional lithium battery manufacturers and the specialization of sodium ion battery manufacturers. Due to the high similarity between the equipment of the sodium ion cell production line and the lithium ion cell production line, there is the possibility of switching from the technical transformation of the lithium ion cell production line. In fact, the output elasticity is large. In terms of investment intensity, sodium battery and lithium battery process equipment are basically similar, and the investment intensity is close to that of lithium battery; The positive electrode is divided into Prussian type and layered oxide. According to the company's announcement data, the Prussian type investment intensity is between 140 million yuan and 200 million yuan. The layered oxide and ternary oxide are collinear, and the investment cost is close; The investment in anode and electrolyte solute is expected to be lower than the current lithium level.

Calculation of demand for sodium ion battery

Looking forward to A00 electric vehicles, electric two-wheeled vehicles and energy storage, the demand for batteries will be about 441GWh by 2025. Assuming that the penetration rate of sodium ion batteries is 16%, the corresponding demand for sodium ion batteries will be 71.2GWh. Looking forward to 2030, the demand for sodium ion batteries is expected to reach 439GWh. Here we emphasize that the supply side capacity determines the penetration rate. If the performance and cost of the sodium ion battery exceed the expectation, the actual demand space will be larger.

Analysis of key companies in the industrial chain

CATL: the global leader in lithium battery, piloting the mass production of sodium ion battery

In July 2021, CATL officially announced the first generation of sodium ion batteries, planned to form a basic industrial chain in 2023, and announced that the energy density of the second generation of sodium ion batteries will reach 200Wh/kg, and the system energy density will reach 160Wh/kg. At the same time, the innovative lithium-sodium hybrid battery pack (high-performance lithium+low-cost sodium complement each other to promote industrial application) was presented.

Zhongke Haina: Incubated by the Institute of Physics of the Chinese Academy of Sciences, deeply cultivated the sodium ion battery, cooperated with Huayang, Three Gorges Capital, Dofluoro, etc., and won the Huawei War Investment

The Institute of Physics of the Chinese Academy of Sciences has been committed to the development of sodium ion battery technology since 2011. In 2017, relying on its technology, the Chinese Academy of Sciences was founded. The founding team includes core technical personnel such as Hu Yongsheng and Chen Liquan. The test line was built in Liyang, Jiangsu Province. In 2020, Zhongke Haina's Pre-A round of financing was invested by wutong Tree Capital, a subsidiary of Huayang New Material Group, and then deeply cooperated with Huayang Co., Ltd., which has rich anthracite resources, to jointly build a positive and negative electrode material production line in Shanxi and provide technical support for its sodium ion battery production line. In addition, Sino-Kehai Sodium and Three Gorges Jiangsu Energy Investment Co., Ltd. and Fuyang State-owned Assets Co., Ltd. jointly build a sodium ion battery production base.

Zhejiang Nachuang&Weike Technology: led by the scientific research team of Jiaotong University, cooperating with New Zebang, Huaihai Holdings, etc

Zhejiang Nachuang was founded in 2018. The core technology of the team comes from the team of Professor Ma Zifeng of Shanghai Jiaotong University. The actual controller is its student Dr. Che Haiying (an intermediate researcher of Shanghai Electrochemical Energy Device Engineering Technology Research Center), and Zhejiang Pharmaceutical Strategic Investment participates. Huaihai Holdings will participate in its Pre-A round of financing in 2021, and Weike Technology will participate in its A-round financing in 2022. The current valuation has exceeded 2.4 billion yuan.

Vico Technology entered the battery industry in 2004. In 2019, it and LG Chemical jointly built a battery factory in Nanchang. It has technology and process accumulation in the polymer lithium battery and aluminum shell lithium battery industries. The first phase of 2GWh sodium ion battery production line is currently planned and is expected to be put into operation in 2023.

New Zebang (one of the leading lithium battery electrolyte companies) and Shanghai Zijian Chemical, the controlling shareholder of Nachuang, jointly applied for the patent of "Sodium Ion Electrolyte, Secondary Battery and Preparation Method and Application" in 2019.

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