Heavyweight! Are positive and negative electrodes of Sodium-ion battery industrialized?

As the ballast stone to promote the development of new energy industry, new batteries such as lithium ion batteries and Sodium-ion battery are the important foundation to support the wide application of new energy in the fields of power, transportation, industry, communication, construction, military, etc., and also one of the key supports to achieve the goal of carbon peak and carbon neutrality.

In recent years, relevant domestic departments have actively promoted the development of new batteries. The Ministry of Industry and Information Technology stated that relevant departments in China attach great importance to the development of the new battery industry, and take a series of measures to promote the healthy and orderly development of the new battery industry from the perspectives of strengthening industry management, coordinating industry planning, supporting technological innovation, and accelerating standard construction. And has been actively promoting the development of the new battery industry for a long time.
First, the Information Industry Development Guide (2016-2020) was formulated and released to promote the technological progress and innovation upgrading of new batteries and support the development of new battery industries such as Sodium-ion battery and Flow battery.
The second is to actively carry out the research and development of relevant standards in the battery field, promote the transformation of technological innovation achievements into standards, standardize and lead the high-quality development of the industry.
The third is to support the construction of battery testing platforms, guide the establishment of domestic power battery manufacturing innovation centers, coordinate resources to promote industrial technology progress, and support key technology breakthroughs and industrialization such as new positive electrode materials.
At the same time, according to the industrial development process, timely improve the relevant product catalogue, and promote the application of Sodium-ion battery with excellent performance and conditions in new energy power stations, transportation tools, communication base stations and other fields; Promote the commercialization of all Sodium-ion battery through collaborative innovation of industry, university and research.
This means that Sodium-ion battery is expected to receive domestic policy support, and the commercialization process is expected to receive policy support. Up to now, the number of Sodium-ion battery industry enterprises in China is relatively small, and Sodium-ion battery industry chain companies with relevant patent technologies mainly include CATL (300750), Zhongke Haina, sodium innovative energy, Penghui Energy (300438), Xinwangda (300207), China Great Wall (000066), Shengyang Shares (002580), Greenmei (002340), etc.

In the negative electrode material family, there are currently four mainstream routes, namely metal compounds, alloy materials, non-metallic elemental materials, and carbon based materials:

1) Metal compounds: metal oxides, sulfides and Selenide are the main representatives. Metal alloy materials have alloying reaction with sodium at low potential in the discharge process, and dealloying reaction at high potential in the charging process. These materials tend to have high theoretical reversible specific capacity and low output potential (<1v), but their volume changes greatly (often>200%) during the reaction process, which makes them easy to crack during the cycle and affect the performance.
2) Alloy materials: rely on the interaction between negative electrode materials and lithium or sodium to form alloys, which in turn generate electrochemical reactions to ensure the normal operation of the battery. The obvious difference between lithium ion battery and sodium ion battery is that sodium ion itself has a larger Ionic radius than lithium ion, so the volume expansion caused by the formation of alloy between metal sodium and anode material is more obvious.
3) Non metallic elements: Elements of the same group as carbon, phosphorus and silicon have become the emerging directions in recent years, and the research maturity is not yet high. Purple phosphorus can easily form white phosphorus when heated, and white phosphorus has unstable chemical properties. Neither purple phosphorus nor white phosphorus can be used as electrode materials; The low conductivity and volume expansion of red phosphorus are difficult to solve; Black phosphorus has a wrinkled layered structure and high conductivity, but its preparation is difficult.
4) Carbon based materials: Hard carbon is preferred for negative electrode carbon based materials, and its structure is more stable, corresponding to a longer battery cycle life. Usually, hard carbon is used instead of graphite as the negative electrode active material. Graphite has poor storage capacity for sodium ions, and due to its structural relationship, graphite materials cannot provide sufficient space for sodium ions to move.

Performance comparison of negative electrode materials for Sodium-ion battery
As a sodium ion anode material, hard carbon is superior to soft carbon in terms of specific capacity, first charge discharge efficiency, potential stability, etc. Its specific capacity can reach more than 350mAh/g. Therefore, hard carbon is more suitable as the anode material of Sodium-ion battery, while soft carbon is mainly used as the raw material of artificial graphite, or as the doping and coating materials to modify natural graphite, alloy and other anode materials.
In the design of negative electrodes, improving sodium storage capacity and first cycle Coulombic efficiency are key considerations, and both precursor selection and microporous structure regulation need to be considered. Biomass based hard carbon has the advantages of low cost and high performance, making it one of the attractive precursors for sodium negative electrodes.
It is estimated that with the rapid penetration of Sodium-ion battery in the energy storage market and the two wheeled vehicle market, the demand for negative electrodes will be nearly 400000 tons in 2030. From the supply side, there is sufficient supply of biomass based materials such as coconut shells and apricot shells; The supply of polymer industries such as phenolic resins exceeds demand, and the new demand for sodium electricity is expected to accelerate the clearance of the industry; Anthracite, as the main precursor raw material of soft carbon, is cheap and has a large quantity. Sodium power is expected to help cutting-edge enterprises explore new opportunities.

Performance comparison of negative electrode materials for Sodium-ion battery
As a sodium ion anode material, hard carbon is superior to soft carbon in terms of specific capacity, first charge discharge efficiency, potential stability, etc. Its specific capacity can reach more than 350mAh/g. Therefore, hard carbon is more suitable as the anode material of Sodium-ion battery, while soft carbon is mainly used as the raw material of artificial graphite, or as the doping and coating materials to modify natural graphite, alloy and other anode materials.
In the design of negative electrodes, improving sodium storage capacity and first cycle Coulombic efficiency are key considerations, and both precursor selection and microporous structure regulation need to be considered. Biomass based hard carbon has the advantages of low cost and high performance, making it one of the attractive precursors for sodium negative electrodes.
It is estimated that with the rapid penetration of Sodium-ion battery in the energy storage market and the two wheeled vehicle market, the demand for negative electrodes will be nearly 400000 tons in 2030. From the supply side, there is sufficient supply of biomass based materials such as coconut shells and apricot shells; The supply of polymer industries such as phenolic resins exceeds demand, and the new demand for sodium electricity is expected to accelerate the clearance of the industry; Anthracite, as the main precursor raw material of soft carbon, is cheap and has a large quantity. Sodium power is expected to help cutting-edge enterprises explore new opportunities.

Other raw materials include manganese, iron, cobalt, copper, nickel, etc. as positive electrode materials, carbon, titanium, phosphorus, etc. as negative electrode materials, and aluminum as current collector materials.

Mid stream of the industrial chain:
Working principle of Sodium-ion battery:
Mainly relying on the movement of sodium ions between the positive and negative electrodes for operation: during charging, sodium ions detach from the positive electrode and swim through the separator in the electrolyte to embed into the negative electrode, leaving the negative electrode in a sodium rich state; When discharging, the opposite is true.
Battery type: The types of battery cells mainly include soft pack batteries and cylindrical batteries in terms of structure; According to the material system, it includes solid Sodium-ion battery, Sodium–sulfur battery, room temperature Sodium-ion battery, zebra battery, etc.
Battery production: Due to the working principle of Sodium-ion battery and the high similarity between battery materials and lithium ion batteries, the battery production process and equipment can be reused.
Battery system: As the commercialization level of Sodium-ion battery is only in its infancy, the research on battery system is relatively small. CATL has developed the AB battery system solution in terms of battery system integration, that is, Sodium-ion battery and lithium ion battery are mixed in a certain proportion, integrated into the same battery system, and balanced control of different battery systems is carried out through the correct algorithm of BMS.

Downstream of the industrial chain:
Application Market
In the current secondary battery market, lithium-ion batteries are the main force and core. Based on the continuous growth of the demand for new energy vehicles, the source of raw materials such as Lithium carbonate and lithium cobalate is becoming more and more difficult, although there is no obvious performance limitation for lithium-ion batteries. After 2010, with the increase in battery pack size and installation quantity, lithium resources have become increasingly difficult to meet demand. Because Sodium-ion battery has the potential to match the performance of lithium ion battery in essence, the research on sodium ion has been carried out again.
Although the original intention of Sodium-ion battery research and development is to supplement and replace the application of lithium ion battery in the field of power battery, the leading position of lithium ion battery in the field of high-speed electric vehicles cannot be shaken because the energy density of Sodium-ion battery is lower than that of lithium ion battery at present; In terms of fixed energy storage, Sodium-ion battery have broad prospects due to low requirements on volume and quality.
As the commercialization of Sodium-ion battery is in its infancy, the analysis of the downstream of the industrial chain is more about prediction and outlook.

Market share analysis of negative electrode materials
Chinese manufacturers hold 86% of the global market share for negative electrode materials. According to EVTank statistics, the global proportion of China's negative electrode production in 2021 has further increased from 77.7% in 2020 to over 86.1%. Among them, Beiterui, a leading player in the industry, has a global market share of 19% in terms of shipment volume, while Shanshan Group, Putai Lai, and Kaijin Energy have similar shipments, each accounting for over 10% of the global market share. Domestic second tier manufacturers mainly include Shangtai Technology, Zhongke Electric, and Xiangfenghua, with global market share of 8%, 7%, and 4% in 2021, respectively.
Since 2018, the industry concentration has declined, and it is expected that in the future, with the large-scale expansion of top manufacturers, the concentration will rebound. With the rapid increase in downstream demand, leading manufacturers have limited production capacity and are able to harvest more orders and occupy a portion of the market share due to full production and full sales. In the 21st year, industry CR3 decreased, while CR6 improved, mainly due to the shortage of graphitization supply in the industry, prioritizing supply to Top6 manufacturers, and reducing the utilization rate of small and medium-sized enterprises' production capacity, which pushed up industry CR6. In the future, leading manufacturers will actively expand production and mainly build integrated production bases including graphitization capacity to ensure their own capacity utilization. It is expected that the industry concentration will increase.
Compared to other aspects of lithium batteries, domestic manufacturers have a higher global market share in negative electrode materials. Horizontal comparison of the proportion of domestic production of various lithium battery materials in the global market in 2021 shows that negative electrode materials are higher than other links, reflecting the strong position of Chinese negative electrode manufacturers in the global lithium battery supply chain. However, the concentration of negative electrode materials in the domestic market is relatively low, with a market share of 22% for major manufacturers and 47% for CR3; Compared to the cutting-edge market share of 42% and the CR3 market share of 66%, there is still room for improvement.
Top manufacturers are better at expanding international customers than second tier and below manufacturers. Betray has covered international mainstream customer groups including Panasonic, CATL, BYD, Samsung SDI, LG Chem, South Korea SK, etc. In 2021, it will achieve 2.667 billion yuan of overseas revenue, accounting for 25.4% of the overall revenue, and the scale and proportion of overseas revenue will rank first in the industry. In addition to leading domestic battery manufacturers, Putai has entered the supply chain of international customers LG New Energy and Samsung SDI. In recent years, the scale of overseas revenue has increased year by year, from 179 million yuan in 2017 to 1.767 billion yuan in 21. Kaijin Energy and Suntech mainly supply CATL. According to their respective prospectus announcements, the sales amount of the two enterprises to CATL in 2019-2021H1 accounted for more than 50% of the total revenue.
There is a significant differentiation in the sales unit price of negative electrodes among various manufacturers. Pu Tai Lai specializes in high-end artificial graphite, with a sales unit price significantly higher than other manufacturers; Betray is at the forefront of the global natural graphite industry, and its product prices are inherently lower than those of artificial graphite; Shanshan Co., Ltd. is involved in both high, medium, and low-end products of artificial graphite. Second tier enterprises generally focus on mid to low end products, with lower price bands compared to top manufacturers. The profitability of negative electrode manufacturers in 2021 is mainly affected by the self-sufficiency rate of graphitization. Affected by the shortage of graphitization capacity in 2021 and the rise of processing costs, the Gross margin of negative materials such as Beiteri, Zhongke Electric and Xiangfenghua with relatively low graphitization self-sufficiency rate declined significantly by 5.47/7.64/2.66 pct respectively; Putailai (negative Gross margin -1.6 pct) and Shanshan (negative Gross margin+0.9 pct) with high graphitization self-sufficiency rate are less affected. However, Suntech, which can achieve full self-sufficiency in graphitization, ranked first among all manufacturers in terms of Gross margin in 18-20 years.

Looking Forward to the Future
Achieving "2030 carbon peak" and "2060 carbon neutrality" is a major strategic decision made by China to address the challenges posed by global climate change and environmental pollution, and is also the future development direction of China's energy technology. The subsequent Action Plan pointed out that "by 2030, new energy will be added, the proportion of clean energy power will reach 40%, and the electrification of vehicle equipment in civil transportation airports will be achieved. One of the core technologies of new energy lies in breakthroughs in battery technology, but currently, lithium-ion batteries, which are gradually increasing in cost and lacking in resources, are no longer able to meet the growing demand in the energy field. Therefore, it is imperative to develop Sodium-ion battery with low cost, rich resources and high safety. Hard carbon, as the only potential negative electrode material for commercial application, has received widespread attention. Therefore, the design and synthesis of hard carbon anode materials for Sodium-ion battery and the study of its sodium storage mechanism are of great significance for promoting the industrial application of Sodium-ion battery and the development of new generation energy storage and conversion. The following are the main focus of subsequent research:
(1) The sodium storage performance of hard carbon is usually closely related to its precursor and high-temperature pyrolysis process. Although the synthesis and selection of precursors, pre oxidation, high-temperature carbonization processes, and other processing methods (such as ball milling and freeze-drying) can regulate the microstructure and physicochemical properties of hard carbon materials, there is currently no clear and unified understanding. Therefore, studying the internal relationship between synthesis and pyrolysis processes and sodium storage performance is very important, and can also effectively guide the design and synthesis of hard carbon materials.
(2) At present, the cost issue of hard carbon materials remains one of the bottlenecks limiting their commercial applications. Therefore, reducing the cost of using hard carbon materials while ensuring their electrochemical performance is an urgent issue that needs to be addressed in regulating the synthesis of hard carbon materials.
(3) Although the sodium storage mechanism of hard carbon has made significant progress with the continuous deepening of research in recent years, the poor rate performance of hard carbon materials, slow ion diffusion in the low-pressure platform region, and unclear sodium storage mechanism have greatly affected their practical applications. Therefore, further research and development of high-performance hard carbon materials are needed, and a clear understanding of the sodium storage mechanism of hard carbon is also beneficial for the further development and practical application of hard carbon negative electrode materials.
(4) Electrolyte, as an important reaction medium in battery systems, greatly affects the performance of batteries. Compared to ester electrolyte systems, hard carbon negative electrode materials have higher rate performance and cycling stability in ether electrolyte systems, which is attributed to the formation of thin and stable SEI films. Therefore, it is necessary to further study the mechanism of its action through a combination of electrochemistry, diffusion kinetics, and one principle, in order to provide guidance for the preparation of high-performance electrolyte systems.

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