Editor's Note
Understanding the patent application status of ternary materials is of great significance to China's new energy vehicles and even sustainable development strategies. The positive electrode material is the most critical component in lithium-ion batteries, significantly influencing their energy density, cycle life, and safety. In 1990, Sony Corporation used layered lithium cobaltate as the cathode material for commercial lithium-ion batteries. Later, other materials such as layered lithium nickelate, lithium manganate, lithium nickel cobalt manganese oxide (NCM), and spinel-type lithium manganese oxide were also widely used. In 1999, Liu et al. first proposed ternary layered materials with different NCM ratios like 7:2:1, 6:2:2, and 5:2:3. In 2001, Ohzuku and Makimura introduced a ternary material with a Ni:Co:Mn ratio of 1:1:1, namely Li(Niâ‚/₃Coâ‚/₃Mnâ‚/₃)Oâ‚‚. Broadly speaking, ternary materials also include nickel-cobalt-aluminum ternary materials and multi-layered structures.
Ternary materials offer better driving ranges due to their high energy density and are widely applied in new energy vehicles. For instance, Tesla’s electric vehicles use the nickel-cobalt-aluminum (NCA) battery system developed by Panasonic. With the rapid growth of global new energy vehicle markets, the market share of ternary materials is expected to increase further. Therefore, analyzing the patent landscape of ternary materials is crucial for China's new energy vehicle industry and broader sustainable development goals.
This paper analyzes domestic and foreign patents related to ternary materials using databases such as the Derwent World Patent Index (DWPI) and China Patent Abstracts Database (CNABS). It examines the patent layouts of key applicants to provide guidance for Chinese applicants in this field.
**1. Patent Application Development Trends**
Using the State Intellectual Property Office's patent search system, the study covers data up to March 18, 2016, counting applications in units of “pieces.†Patents from the same family are counted as one application. Lithium-ion battery cathode materials are categorized into five types: polyanion, layered materials, spinel type, composite type, and others. Among these, layered materials include LCO, LMO, LNO, and NCM. Global patent applications related to cathode materials reached 10,005, with 3,425 focused on layered materials, accounting for 34%. Within this category, NCM made up 39% of applications, followed by LCO at 18%, LNO at 14%, and LMO at 10%. The remaining 19% included other layered materials.
Figure 1 shows that NCM dominates the layered material segment, highlighting its importance globally. Figure 2 illustrates the global trend of cathode material patents over time, while Figure 3 focuses on NCM applications. After 2013, some patents had not been published yet, leading to a slight drop. Layered cathode materials were among the first commercialized, with steady growth from 1983 to 1990, followed by a rapid rise between 1991 and 1997. From 2008 onward, the growth slowed until 2008, when polyanionic materials gained traction due to their higher discharge capacity and good cycle performance. Since 2005, NCM applications have grown rapidly, driven by the demand for power batteries. By 2013, NCM applications surged, entering a phase of rapid development.
Figure 4 highlights the delayed start of domestic NCM patents, with the first appearing in 1996. Between 1996 and 2008, domestic applications grew slowly, lagging behind global trends. However, after 2009, due to the influence of the global NCM market, domestic applications increased rapidly. Despite this, foreign applications to China did not grow significantly, suggesting limited breakthroughs in safety technology. This has led to a lack of core patents in China, with many peripheral applications. Since 2013, some patents have not been published, causing a slight decline in statistics.
Figure 5 reveals that NCM remains the primary focus of ternary material research, with applications far exceeding other types. While NCA applications have grown due to Tesla's adoption, their volume has remained relatively stable.
**2. Preparation Methods and Technical Efficacy Analysis**
Common synthesis methods for ternary materials include co-precipitation, solid-state, sol-gel, spray pyrolysis, and others. Co-precipitation is the preferred method for mass production, involving the synthesis of precursors followed by high-temperature calcination. Solid-state methods include high-temperature and low-temperature variants. Sol-gel methods offer advantages in reaction uniformity and lower temperatures. Newer methods like spray pyrolysis, template, solution-phase, solvothermal, and electrospinning are mostly used in small-scale lab settings.
Figure 6 shows that co-precipitation, solid-state, solution-phase, and spray pyrolysis are the main preparation methods, with 510, 235, 134, and 60 patents respectively. The sol-gel method has 53 applications, mainly for NCM materials. Emerging methods such as templates and electrospinning are gaining attention but are not yet widely adopted.
Current challenges with ternary materials include poor cycle performance, gas generation, and high costs due to cobalt scarcity. Solutions include atomic doping, surface coating, and mixing with other active materials. Patent applications often combine multiple improvements, focusing on enhancing electrochemical performance.
Figure 7 indicates that the majority of patent applications aim to improve electrochemical performance, reflecting the industry's focus on increasing energy density and replacing lithium iron phosphate in power batteries. However, safety and cost reduction remain underdeveloped areas. Fewer patents address these issues, indicating a need for further innovation.
**3. Analysis of Ternary Material Technology Patent Applicants**
Table 2 lists top global and domestic applicants for ternary materials, with seven of the top ten being foreign entities, including Japanese companies like Toyota and South Korean firms like LG and Samsung. Domestic applicant Jiangsu Kejie ranks fourth, followed by BYD. However, domestic applications are scattered, with low industry concentration and limited R&D investment. Compared to foreign competitors, domestic enterprises lack core patents and rely more on peripheral applications.
Figure 8 shows that Japanese and Korean companies, such as Toyota, Samsung, and Sanyo, started early in ternary material R&D. While some companies saw a slowdown in patent activity, others like LG and Toyota maintained steady growth. Domestic companies like BYD began filing patents later, resulting in fewer core patents and weaker competitive positions.
**4. Development Roadmap of Ternary Material Technology**
Figure 9 outlines the technical development roadmap of ternary materials, showing the evolution of preparation and modification methods. Early patents, such as those from Japan Battery Co., Ltd. in 1997, laid the foundation. Subsequent advancements included solid-state methods and atomic doping. U.S. Patent No. 6,964,828 B2 became a core patent, improving performance and restricting Chinese development.
New methods like spray drying and sol-gel emerged, along with coating modifications and doping techniques. Companies like Samsung SDI pioneered aluminum phosphate coatings, enhancing capacity and stability. Core-shell structures and gradient materials also gained traction, pushing the field toward more advanced production processes.
**5. Core Patent Analysis of Ternary Materials**
Key players like 3M and Argonne National Laboratory hold foundational patents for ternary materials. 3M's PCT application (WO02/089234A1) covers a wide range of countries and includes 26 family applications. Strategic collaborations with Umicore and others highlight the importance of patent licensing in the industry.
The dispute between BASF and Umicore over ANL's patents underscores the significance of intellectual property protection. Although lithium-rich materials are less common commercially, patent disputes continue to rise, emphasizing the need for domestic companies to invest in R&D and IP protection.
**6. Conclusion**
Domestic applicants face challenges in R&D investment, industry concentration, and core leadership compared to foreign counterparts. To enhance competitiveness, they should focus on safety improvements through coating and doping techniques. Exploring niche areas like battery recycling offers opportunities for "corner overtaking." Additionally, strengthening IP protection and improving patent quality will be essential for international expansion.
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