Cathode material is the most critical lithium-ion battery materials, lithium-ion battery energy density, cycle life, safety, etc. In 1990, Sony company commercialized lithium-ion battery cathode material used for the layered lithium cobalt oxide Lithium nickelate, lithium manganate, lithium nickel cobalt and manganese oxide (ternary material), spinel lithium manganese oxide and olivine-type lithium iron phosphate have all become common cathode materials for lithium ion batteries. Et al. First proposed ternary layered materials with different components of NCM ratios of 7: 2: 1, 6: 2: 2 and 5: 2: 3, respectively. OHZUKU and MAKIMURA first proposed the amount of Ni: Co: Mn material The ratio of 1: 1: 1 ternary material 'Li (Ni1 / 3Co1 / 3Mn1 / 3) O2' material.In a broad sense, the ternary material also includes nickel cobalt cobalt ternary material, multi-layered material.
Due to its high energy density, ternary materials can achieve better mileage, which is well applied to new energy vehicles. For example, Tesla pure electric vehicles in the United States have successfully used lithium nickel-cobalt-lithium-aluminate (NCA) battery system manufactured by Panasonic in Japan In recent years, with the rapid development of global new energy vehicles, the market share of ternary materials will gradually increase.
Therefore, it is very important to understand the patent application situation of ternary materials to the new energy vehicles and even the strategy of sustainable development in our country.Based on the Derwent World Patent Index Database (DWPI) and China Patent Abstract Database (CNABS) In the field of domestic and foreign patent search and statistics, and the important applicant in the field of patent layout were analyzed in order to provide a reference for our country's patent applicants in the field of patent layout.
1 patent application development trend
This article uses the patent search and service system of the State Intellectual Property Office. The deadline for the search is March 18, 2016, in which the amount of application is counted as 'unit', and the number of patent applications as an application is counted as the total number of applicants in.
The lithium ion battery cathode materials are divided into polyanionic, layered materials, spinel, composite types and other types of five major categories, in which the layered material is divided into layered lithium cobaltate (LCO), layered manganic acid Lithium (LMO), Layered Lithium Nickel Oxide (LNO), Ternary Materials (NCM) and other types of patent applications in the global patent applications (Figure 1), cathode material technology-related patent applications for the 10005. Among them, 3,425 involved In the technical branch of the layered cathode material, the proportions of ternary, LCO, LNO and LMO accounted for 39% of the applications, respectively. The proportions of LCO 18%, LNO 14%, LMO 10% The other layered cathode material accounted for 19% of the amount of layered cathode material applications in various types of cathode materials, the largest number of applications, ternary materials and occupy the most layered materials, from the point of view, the world, ternary Materials play an important role in the cathode materials of lithium ion batteries.
Figure 2 shows the trend of global patent applications of cathode materials with years. Figure 3 shows the trend of patent applications of ternary materials in layered materials with years. Since 2013, some patents have not been published yet. Statistics The number decreased slightly.Laminar structure of the cathode material patent application started earlier, is the earliest commercialization of lithium-ion battery cathode material, which in 1983-1990, the steady increase in the number of applications, then usher in the first rapid growth period (1991-1997), and maintained the status of fluctuating growth until 2008. Due to the high specific discharge capacity and good cycling performance of the polyanionic cathode material (such as lithium iron phosphate), it has been well used in portable electronic devices From 2005 onwards, the application volume began to grow rapidly and began to exceed the layered cathode material around the year of 2008. Due to the high discharge capacity of the layered cathode material (such as ternary material), the applications of the powered vehicle Therefore, with the rapid development of new-energy vehicles in the world, annual applications for layered materials will also appear in the next five years (2009-2013) The trend of patent applications for ternary materials was basically the same as that for layered materials, with a slow start in 1990-1999 and a steady growth in 2000-2009, during which the magnitude of patent applications fluctuated Not; in 2009-2013, the application volume has leapt to enter the rapid development stage.
As shown in Figure 4, relative to the development trend of ternary materials in the world, domestic patent applications started relatively late, and related patent applications did not appear until 1996, and their development was relatively slow during 1996-2008. Compared with the applications for global patents Compared with the trend, the development lags behind.
Due to the energy density of lithium iron phosphate can not meet the needs of the growing electric car during the period of 2009-2013, the patent applications of domestic ternary materials are rapidly increasing into the rapid development stage due to the impact of the global ternary materials market. It is found that there is no significant increase in the number of applications from overseas during the period 2009-2013 compared with the substantial increase in the number of domestic applications, which may not have been related to the effective breakthrough by foreign applicants on the safety of ternary materials Therefore, the new core basic patent did not appear, and the corresponding layout in China has not yet fully developed. Since 2013, some patents have not been disclosed yet, and the statistics slightly decreased.
To better understand the patent application status of different types of ternary materials, Figure 5 shows the trend of patent applications of nickel, cobalt, manganese, nickel cobalt and aluminum, quaternary and other types of ternary materials, and it is obvious that the research and development of ternary materials still focuses Mainly on the NCM material, which far surpassed the applications of other types of ternary positive electrode materials and showed a rapid increase in the number of applications since 2009. Due to the demand for the development of the electric vehicle industry, nickel and cobalt Applications of aluminum (NCA) ternary materials on Tesla have also increased their applications in recent years, but the amount of application for NCA has not changed significantly.
2 preparation methods and technical efficacy analysis
Ternary material synthesis methods are coprecipitation, solid phase method, sol-gel method, spray pyrolysis method, etc. Coprecipitation method mainly synthesis of nickel, cobalt and manganese hydroxide precursor or carbonate precursor, and then Mixed with lithium salt, the use of high-temperature solid-state calcination of the final product synthesis is currently the preferred method of mass production; solid phase method is divided into high-temperature solid phase method and low-temperature solid phase method, high temperature solid phase method usually refers to more than 600 ℃ solid In contrast, low-temperature solid-phase method refers to the chemical reaction between the solid-phase compounds at room temperature or near room temperature; sol-gel method compared to the high temperature solid-phase method, with a low reaction temperature, the reaction mixture evenly ; Spray pyrolysis method, template method, solution phase method, solvothermal method and electrospinning and other new methods, the current large-scale production is not much, mostly for small-scale laboratory preparation.
Figure 6 shows the preparation of different ternary material distribution map of the world, we can see that the preparation of ternary materials are still mainly concentrated in the coprecipitation method, solid phase method, solution phase method, spray pyrolysis method, the patent application The quantities were 510, 235, 134 and 60 respectively. The sol-gel method also has a certain number of applications with a patent application of 53, and the types of ternary materials prepared by these methods are still mainly NCM ternary materials In addition to the above five methods, in order to improve the performance of ternary materials and to simplify the preparation process, a few patent applications on emerging methods such as template method, electrospinning method and microwave method have also appeared.
At present, the main problems of ternary materials are the following aspects.
① cycle performance is not high: mainly due to the increase in Ni content, the charge-discharge process occurred in many phase changes;
② gas production is more serious, less safe: mainly due to the presence of ternary material surface LiOH and Li2CO3 react with the electrolyte to produce gas;
③ due to the scarcity of cobalt resources, high prices, relative to lithium manganese oxide and lithium iron phosphate, ternary materials, higher costs.
In addition to the above aspects, including the rate performance and the first charge and discharge performance is not high, etc. At present, the main means to solve these problems are atomic doping, surface coating, mixed with other types of active materials, improved preparation methods and other means, the focus of this article Attention is paid to the patent applications of these three types of techniques, such as atom doping, coating and compounding / mixing, on the modification of ternary materials. Since the electrochemical properties such as cycle performance, rate performance and the first charge-discharge performance often appear together , We will improve the cycle performance of ternary materials, rate performance and the first charge and discharge performance collectively referred to as the increase of electrochemical performance statistics.
As can be seen from Figure 7, in each effect, the increase in the number of patent applications to improve the electrochemical properties accounted for an absolute advantage, indicating that the current development of ternary materials, the main focus is to improve the electrochemical properties of ternary materials Its energy density, see, the companies and research institutions committed to its application in the battery cathode material, in order to replace the lithium iron phosphate cathode material, which uses a variety of means to improve its electrochemical properties of the patent is also the patent Application focus.
Due to the crucial importance of the safety of the power battery and the low number of patent applications for the safety of ternary materials, no effective technological breakthrough has been achieved in improving safety; the number of patent applications for cost reduction is also low , On the one hand due to income problems, there is no active investment in the field of recycling, on the other hand, the key technologies involved in recycling and other aspects have not been effectively breakthroughs; simplify the process of application is less. , Doping and coating of the modified method in ternary material patent applications occupy the absolute mainstream position, the different types of cathode material compound or mixed to achieve functional complementation also have a certain amount of application.
Table 1 shows the tendency of ternary material modification with age, from which it can be seen that in each of the modified techniques, the number of patent applications also increased with the increase of the age, indicating that over time It is noteworthy that in the seven years from 2009 to 2015, the improvement of the electrochemical performance of ternary materials has been obviously increased because, as governments in all parts of the world Vigorously promote the new energy vehicles, many companies and research institutions extensively involved in the development of battery power, in order to meet the needs of people longer mileage, ternary materials to stand out with its high energy density.
In contrast to the rapid increase in electrochemical performance, the application volume of the ternary material is relatively slow in terms of safety and cost reduction. In the case where the investment in research and development of ternary materials is significantly increased and the battery safety is very important, It fully shows that the safety and cost of ternary materials have not been effectively solved.Therefore, in the future use of ternary materials, safety will become the bottleneck and the focus of future research and development.
3 ternary material technology patent applicant analysis
Table 2 shows the ranking of applicants and applicants for ternary materials globally and domestically. As can be seen, out of the top 10 applicants in the world for ternary materials, 7 are foreign applicants, of which Japan occupies 5 seats and Toyota applications Ranked first, which is related to Toyota's investment in power vehicles; South Korea occupy two seats, respectively, LG and Samsung.It is worth mentioning that the domestic applicants Jiangsu Kejie ranked fourth with 23, and at Domestic applicants ranked first in the list.China's domestic lithium battery BYD ranked the second among applicants in the country, the application is not much, with its current main lithium iron phosphate battery, but BYD's ternary material is about to invest Production, application of ternary materials is expected to gradually increase.China's major applicants, colleges and universities Jiangnan University, Central South University in the ternary material also has a certain amount of application.Overall, the domestic application of ternary materials more dispersed, Industry concentration is poor, and did not get enough development, especially the domestic lithium lead enterprises to get involved less, the overall research atmosphere is not strong, need to attract the attention of domestic applicants.
Figure 8 shows the annual filings of applicants for the top ten global applications of ternary materials and the number of applications declined after 2014 because some patent applications have not yet been made public, as can be seen from the figure Enterprises such as Toyota, Samsung, Qingmei and Sanyo had relevant research and development on ternary materials as early as 2000, and started early. Samsung had relevant patent applications for ternary materials as early as 1997, Propulsion, Toyota, LG, Samsung and ASAHI Asahi Metal's steady increase in the number of applications, research and development structural configuration is reasonable.
Specifically, LG from 2005 onwards appeared on a large scale patent application on ternary materials, each year has 3 to 8, indicating that its ternary material is networked layout, Toyota appeared in 2005-2008 ternary However, the research and development and production of ternary materials were intensified after 2009. In particular, the number of patent applications for ternary materials was as high as 12 in 2014; there was no obvious increase in the number of patent applications for pure and Sanyo Trend; Mitsubishi once interrupted the ternary material orientation of the patent layout.This also reflects the degree of importance of the ternary material in Japan and South Korea to some extent, the disagreement, the ternary material development prospects have some challenges, It may also be related to the strategic layout of individual enterprises.
Compared with Japan and South Korea, BYD domestic enterprises in 2002 only about the ternary material patent applications, 科 捷, Jiangnan University began to appear after 2010 on the ternary material patents, starting late than Japanese and Korean enterprises late 10 years, therefore, the domestic enterprises in the ternary material does not have the core patents, and as Japan and South Korea enterprises, 3M companies and other important foreign applicants early layout, at the same time master the core patents, domestic applicants in ternary materials patent application The basic are peripheral applications, and the method of patent application is too much, resulting in domestic applicants in the ternary material on the strength of competition is not strong.
However, due to the high energy density of ternary materials, it is believed that there will be more and more applications in new energy vehicles in the future. Based on the above analysis, there is a great room for development for the safety and cost issues of ternary materials. The layout of applicants is not perfect. If domestic applicants can increase their R & D investment in these areas and grasp the core patents as early as possible, they will surely catch up with and surpass the tertiary materials.
4 ternary material technology development route analysis
Figure 9 is a roadmap for the development of ternary materials technology, the application date (priority date) as the time axis, shows the ternary material in the main preparation methods, the means of modification technology development path. The earliest ternary material is Japan NiCoAl ternary material applied by Battery Co., Ltd. on Sep. 9, 1997, and prepared by coprecipitation method, and thereafter Central Japan Electric Industrial Co., Ltd. applied co-precipitation method on Nov. 5, 1999 to prepare cation-doped NiCoMn Ternary materials.
In 2001 the United States IIionTechnology company applied and the priority date of September 14, 2000 using solid state preparation of NiCoMn ternary material patents, so that ternary material preparation method from the coprecipitation method to the solid phase method Subsequently , Began to appear atomic doping modified ternary material patent applications, such as December 11, 2000 application of F atoms doping modification, followed by atomic doping has also developed rapidly, an important means of modified ternary materials.
US Patent No. US6964828B2 on Apr. 27, 2001 authorized by 3M Innovation Inc. on April 15, 2001 and its equivalent CN100403585C on the authorization of NiCoMn ternary materials and the like, which mainly defines the content of Ni in NiCoMn, Which significantly improved the performance of ternary materials and became the basic core patent of ternary materials, thus restricting the development of ternary materials in China's lithium battery industry.
Subsequently, new synthetic methods such as spray-drying and sol-gel methods continue to emerge. In order to further improve the electrochemical performance, safety performance and other properties of ternary materials, patent applications for the modification of ternary materials have also started to increase , Such as the Samsung SDI application priority date of May 13, 2002 using aluminum phosphate coated NiCoMn ternary material, greatly improving its capacity, cycle life and thermal stability, opened the ternary material coated modified New ideas, then, metal oxides such as alumina, metal fluorides such as aluminum fluoride have become a common means of coating ternary materials; cationic and anionic doping is also an important means for the modification of ternary materials; published in 2007 Korean Patent Application KR1020070049810A discloses a method for preparing a gradient material, that is, using different amounts of ternary material to form a core-shell structure. In general, from 2002 to 2014, the research methods of ternary materials and multiple materials are also constantly New methods, sol-gel method, solution phase method, magnetic field signal generation method, microwave method, hydrothermal method, template method, high pressure synthesis method, electrospinning method, etc., ternary materials and more Preparation of material to a new level.
At the same time, ternary materials and multi-material composite forms also continue to diversify, from 2002 to date, fluoride doping, silicon doping, carbon composite, core-shell composites, etc. For the improvement of ternary materials and multi-material capacity, Rate performance, cycle performance, safety performance played a decisive role.In addition, the structural stability and safety performance of ternary materials and multiple materials are the main factors that limit their large-scale production in a certain period of time, to solve the above technical problems We will continue to work hard in the future.
5 ternary material core patent analysis
After the above-mentioned systematic analysis of ternary materials, it can be found that the investment in R & D of ternary materials both at home and abroad has been in a rapid growth stage in recent years.The reason is that the rapid development of electric vehicle industry brings forward the capacity performance of power battery Higher requirements, although the lithium iron phosphate battery cycle stability and cost have greater advantages, but its capacity and energy density has limited its further development, compared to lithium iron phosphate, ternary materials in this respect even better As a result, more domestic and foreign enterprises began to switch to ternary materials research and development.According to the above analysis shows that the current research and development is still mainly concentrated in the nickel-cobalt-manganese (NCM), followed by nickel-cobalt-aluminum (NCA) Materials started relatively late, and foreign technology is still a big gap between the same time, to circumvent the barriers to intellectual property is also an important issue to be considered.Considering the aforementioned ternary material technology development route shows that the ternary material based patented technology is still in control In the hands of foreign applicants.Among them, the United States 3M innovation company, as the world's leading battery materials business, basic research and development strength.Test below related to ternary materials The core patent is described in detail.
(1) 3M company ternary material core patent patents in Table 3, the basic situation, the patent systemically illustrates the cathode composition and lithium ion batteries containing these compositions, the battery has a high initial capacity and after repeated charge and discharge cycles Has a good capacity retention In addition, the cathode composition does not generate a large amount of heat when used at unfavorable high temperatures, thereby improving the safety of the battery.In particular it is proposed for the first time that the composition has the general formula Li (NiyCo1-2yMny) O2, Of which 0.083< y< 0.5.
The application for the PCT application (WO02 / 089234A1), entered the United States, Japan, Korea, China, Europe, Australia, Austria, a total of 26 applications from the same family, and in China, Japan, the United States, Europe and other countries to obtain patents.
3M and Umicore reached a strategic cooperation agreement in 2012. 3M and Umicore will give priority to providing patent licenses and technical cooperation to each other. At the same time, 3M will withdraw its cathode material production and recommend its clients to Umicore. In addition, Under the general trend of ternary battery power, international lithium battery companies including LG and SK have all started to obtain the authorization of the core patent from 3M hand and increase the production layout of ternary cathode materials, as shown in Table 4. Among them, CN100403585C, US7078128B2, US6964828B2, US8241791B2 and US8685565B2 are patented by each other.
Although 3M is not involved in the production of cathode materials, but relies on technology research and development and patent licensing to achieve business development business model.For the domestic market, due to the late start of intellectual property, has not established a better mechanism for intellectual property protection , So the emergence of such a short period of 3M companies is very low.But from the above license information analysis, the patent licensing between enterprises, patent disputes will be more and more normalized, therefore, regardless of the domestic enterprises to take the patent license Or take a detour, accelerate the layout of patents are the necessary guarantee for sustainable development.
(2) The ternary material patents US6680143B2 and US6677082B2, which were applied to the Argonne National Laboratory (ANL) ternary material core patent ANL in 2001 and were authorized in 2004. US6677082B2 first proposed the concept of lithium enrichment xLiMO2 · (1 -x) Li2M'O3 (0 BASF in Germany and Toda Japan Co., Ltd. have commercialized the lithium-rich manganese-based cathode material by obtaining the above patents of ANL.
(3) Ternary patent dispute between BASF and Umicore On December 21, 2016, the International Trade Commission (ITC) made a final ruling ruled that Belgium Umicore violated the patent rights of BASF in Germany and the Argonne National Laboratory in US6677082B2 and US6680143B2. As described above, 3M authorized dozens of companies, Umicore is the current global leader in lithium cathode materials and operating in good condition, BASF has been Umicore as a direct competitor.
If the lawsuit succeeds, it not only wins a great reputation for BASF, but also a huge amount of infringement compensation is the main reason.The core of this patent dispute lies in the fact that UPR produces ternary materials with a two-phase structure rather than a single phase, Of the microstructure description.Ulimekote production of ternary materials are mainly NMC333, NMC532 and NMC622, rather than lithium-rich ternary material.The lithium-rich ternary material microstructure is very complex, there is no conclusive conclusion, although the beautiful The Section provided ITC with XRD and HRTEM photographs of related materials to prove the single-phase structure but was not adopted by the ITC. ITC finally decided that Umicore had infringed ANL's patent.
However, at present, the major commercialized ternary materials in the industry are still stoichiometric ternary materials, and the lithium-rich ternary materials do not occupy much space in the industry.Pharge materials are the key materials that affect the performance of lithium ion batteries, Patent disputes over cathode materials will also be more and more. Against this background, domestic enterprises should pay close attention to the research and development of cathode materials and the protection of intellectual property rights.
6 Conclusion
Based on the above analysis, on the whole, the domestic applicants for the relative lack of input of ternary materials, industry concentration is low, the lack of core leadership, compared with foreign applications also has a considerable gap, for which, the author from Patent point of view is given the following suggestions.
(1) pay attention to security issues ternary materials, enhance the core competitiveness from the earlier Tesla electric car spontaneous combustion to Samsung mobile phone Note7 recent frequent occurrence of explosion, are highly relevant to the events described above safety performance of lithium batteries have also been more An increasing number of attention can also be seen from the above analysis, there are not many patent applications for security ternary materials, especially foreign applicants focus around security patent portfolio ternary material has not formed a complete system , Great room for development, domestic applicants can triple ternary material safety as a key research direction.To address the issue of ternary material safety, can focus on coating modification, ion doping and other technical means.If the ternary An effective breakthrough in material safety will significantly enhance the core competitiveness of ternary materials.
(2) Developing blank areas and realizing overtaking in corners Due to some objective factors, although the number of patent applications in China has surpassed that of Japan, South Korea and other lithium power countries, in the competition of core technologies, at a disadvantage, the core base material of lithium battery patents mostly foreign giants control view of the above situation, on the one hand domestic enterprises should continue to strengthen R & D investment, enhance their core competitiveness, but also to look for other ways, less concerned with foreign counterparts in some of the fine sub-areas layout. currently, the new energy vehicle market is growing rapidly, at home and abroad are faced with the realities of power battery recycling, in particular, can reduce costs by recycling ternary materials scarce resources of cobalt can also be seen from the above analysis, ternary materials reduce the costs involved are very few patent applications, and currently specifically for battery recycling business is almost no correlation technology is lacking, therefore, for domestic enterprises, both major test on the path of development, but also a possible to achieve ' Corner overtaking 'a rare opportunity.
(3) Pay attention to the protection of intellectual property rights and improve the quality of patent applications An important applicant for domestic ternary materials Jiangsu Kejie can find that the patent applications involving ternary materials are mostly method type claims, with narrow protection scope and patent rights In this regard, domestic applicants should actively set up their own patent team to enhance the level of patent writing, and actively carry out the patent layout, especially the layout of overseas patents for the future development in the international market hit Good foundation.
