Although there are many patents in China's graphene industry, more than three-quarters of the patents come from academic institutions. The participation of enterprises in the research and development of graphene needs to be further improved. There are not many high-value patents, and the supply and demand between technology and market are still Mismatch, technology development, transfer diffusion and the first commercialization chain have yet to be opened.
As a new type of carbon material, graphene has received wide attention from scientists around the world since its discovery. Graphene has outstanding physical and chemical properties such as structural stability, high electrical conductivity, high toughness and high strength. It is known as the “king of new materials†and has been applied in many fields such as electronics, energy storage, composite materials, and aerospace. In the process of China's manufacturing industry becoming bigger and stronger, the development of graphene industry will drive the technological progress of relevant downstream industries, enhance innovation capability, accelerate the transformation and upgrading of manufacturing industry, seize the new round of competition in manufacturing, and activate potential consumption. It is of great significance.
Introduction to the graphene industry chain
The overall graphene industrial chain is divided into upper, middle and lower reaches. The upstream is mainly the raw material industry for preparing graphene, the middle reaches are mainly various types of graphene products, and the downstream is the application fields of graphene such as semiconductors, electronic devices, environmental protection fields, medical biology and heat dissipation fields.
To date, thousands of companies around the world have been involved in graphene-related research and development, including IBM, Intel, US Saucer, Dow Chemical, GM, DuPont, Xerox, Samsung, Lockheed Martin, Boeing, Sony, Huawei, etc. Technology giant. The 2017 Global Graphene Industry Research Report released by the China Graphene Industry Technology Innovation Strategic Alliance in 2017 shows that by 2020, the global market value of graphene will reach 100 billion yuan. From the perspective of the scale of the whole industry chain market and the compound annual growth rate in the past years, graphene is expected to reach the scale of trillions of production capacity in the future, especially in the next 5 to 10 years. With the continuous expansion of the graphene application market, graphene raw materials and Downstream applications will continue to show significant market prospects and generate promising economic value in many areas.
Current status of graphene materials development
After 2009, the number of patent applications for graphene technology in the world increased rapidly. Among them, China has the largest number of patent applications for graphene technology in the world, with a total of 24,942 applications and 22,418 public, an increase of 59.46% (as of September 2015). The number of disclosures is 14,098), which is the first echelon country with the United States. South Korea and Japan are the second echelon countries. Germany, the United Kingdom, France and Russia also have a number of patent applications filed for the third echelon countries. China and the United States are leading the way in patent applications for graphene technology.
Status of international graphene development
At present, the countries engaged in the research of graphene industry in the world include the United Kingdom, the United States, the European Union, South Korea and Japan, and the development status of each country is different.
UK: As the birthplace of graphene, the UK is a global leader in the basic research and development of graphene, but there are fewer graphene companies engaged in commercial development, so it is not a strength in graphene applications. In order to accelerate the research and development and application of the graphene industry in the UK, the UK government has also invested heavily in accelerating the development of the graphene industry. The industrial layout is mainly carried out around the University of Manchester. The National Graphene Research Institute and the Graphene Engineering Innovation Center were established at the University of Manchester. Accelerate the basic research and application development of graphene.
United States: The United States invested in graphene research earlier, graphene industrialization and application process is relatively fast, its industrial layout is also diversified, the industrial chain is relatively complete, and basically covers the preparation and application of research - graphene production — The entire process of downstream applications. Not only IBM, Intel, Boeing and many other large companies with strong R&D capabilities, but also many small graphene companies. The US Department of Defense and the National Natural Science Foundation have also invested heavily in supporting the research and development and industrialization of the graphene industry in areas such as graphene transistors, energy storage, and supercapacitors.
EU: The graphene research in the EU started early and systematically, and the graphene research was upgraded to a strategic height. The financial support was strong and the basic research was solid. However, due to the small number of companies involved in downstream applications, the industrialization process has been slower. The Graphene Flagship Research Project is one of the first technology flagship projects selected by the European Union with a total investment of 1 billion Euros. The core content of the project is to propose 13 key R&D areas, including standardization, biosensors and bio-interfaces, thin film technology, Catalysts for energy applications, functional materials for composite and energy applications, functional coatings and interfaces, integration of GRM and semiconductor devices, new layered materials and heterostructures, passive components for RF applications, silicon photonics Prototype research on integration, graphene and related two-dimensional crystals and hybrid systems, updating of technology roadmaps and open topics for graphene and related two-dimensional crystal and hybrid systems.
At present, there are about 50 companies in the EU to carry out the research and development, industrialization and application of graphene, including not only industrial giants such as Nokia, BASF and Bayer, but also many small specialized graphene enterprises. The industrial distribution is mainly concentrated in Germany, France, Spain and other places.
South Korea: Korea's graphene industry development is closely integrated with industry, education and research, and its development in basic research and industrialization is relatively balanced, and the overall development speed is relatively fast. From the government level, the Korean government has increased its support through providing financial support and integrating research power. From the research level, South Korea's Sungkyunkwan and Korea Science and Technology Institute have strong strength in graphene research; from the enterprise level Mainly based on South Korea's Samsung Group and LG, among which South Korea's Samsung Group invested a large amount of research and development to ensure its international leading position in the field of graphene flexible display, touch screen and chip, and provide support for the development of graphene industry in Korea. At the same time, Korea attaches great importance to the protection and application of graphene patents. Currently, the number of patents ranks third in the world, second only to the United States and China, and far higher than other European countries.
Japan: Japan relies on its good carbon material industry base and is one of the first countries in the world to conduct graphene research. The combination of production, study and research is relatively close, and the overall development is more comprehensive. A number of universities, including Tohoku University, Tokyo University, and Nagoya University, as well as Hitachi, Sony, Toshiba, and many other companies have invested heavily in the basic research and application development of graphene. The research focuses on graphene. Applications in thin films, new energy batteries, semiconductors, composites, and conductive materials.
Domestic development status of graphene
In terms of the number of patents, the number of patent applications in China's domestic graphene field is mainly concentrated in the Yangtze River Delta region, of which Jiangsu's application volume ranks first (4,102), Guangdong (2,537) and Beijing (2,333), followed by Northeast and The number of patent applications in the western region is low.
From the perspective of industrial agglomeration, most of the current graphene companies in China are located in the eastern coastal areas, especially in the Yangtze River Delta, Pearl River Delta, and Beijing-Tianjin-Jiulu polymerization areas. Among them, Jiangsu, as a province with early development of graphene in China, has formed a “1+1+4†industrial innovation pattern, that is, the Jiangsu Province Graphene Industry Technology Innovation Strategic Alliance is the carrier of industry-university-research cooperation, with Jiangnan Graphene Research Institute and Jiangsu Province Industry. The Institute of Graphene Materials of the Institute of Technology is an industrial innovation base, and the industrial innovation layout of the graphene industrial cluster is formed in Changzhou, Wuxi, Taizhou and Nanjing. Ningbo, Zhejiang Province, as one of the earliest regions in China to develop and industrialize graphene, has a significant first-mover advantage, deep foundation and good environment in graphene technology innovation and industrial development, in graphene microchips and graphite. There are many breakthroughs in the preparation and application of olefinic films, forming a full chain development model.
In December 2015, the Beijing-Tianjin-Hebei Graphene Industry Alliance was established in Beijing to integrate the resources of the three regions, accelerate the industrialization of low-cost graphene and equipment technology, and form a strategic emerging industrial highland in Beijing, Tianjin and Hebei. In 2016, there were more than 200 graphene-related companies in the region, and more than 60 companies formed graphene business.
The Pearl River Delta region is centered on Shenzhen and has the best graphene application market in the country. It is well-developed in many fields such as energy, new materials, electronic information, wearable devices and electric vehicles. The Shenzhen Municipal Government attaches great importance to the graphene industry and has been actively promoting the research and development and industrialization of graphene technology. At present, more than 10 internationally influential R&D teams have been nurtured and introduced, more than 10 related research and innovation carriers have been built, and more than 20 graphene-related enterprises have been cultivated.
The graphene industry in Shandong is mainly concentrated in Qingdao and Jining. After several years of development, Shandong Province has initially formed a prototype of the industrial chain from graphene raw materials, equipment to application fields.
Development of graphene materials
High quality and low cost scale preparation problems
After long-term independent research and development, China's graphene production technology, process equipment and product quality have made major breakthroughs, but the maturity of graphene scale production technology is still low, and the quality of different batches of graphene products is unstable and the nature is different. Great question. Although the graphene powder production line above the tons is already built, there are problems such as low quality and pollution in the preparation process, which cannot reflect the various excellent properties of graphene, which seriously hinders the large-scale application of graphene. In terms of graphene powder, the current commercial graphene products generally have problems such as uneven size and number of layers, low single-layer graphene content, specific surface area far lower than the theoretical value, no classification and other quality instability and high cost; graphene In terms of thin films, existing products have unavoidable structural defects caused by growth processes and surface contamination caused by transfer processes, and generally have high resistance and cannot be applied in fields that should be suitable for matching their excellent electrical properties, such as electronic devices and semiconductors. Industrial and other high-tech fields. The existence of these problems is not only a reason for the poor breakthrough of downstream applications, but also the cause of the killer-level application. It also leads to the production capacity of graphene materials manufacturers without production.
Problems in graphene applications
There are also a number of challenges in graphene applications, including coatings, composites, conductive inks, and the like.
Functional coating
The unique sheet structure and properties of graphene make it a great application prospect in functional coatings. However, graphene has poor compatibility with water, organic solvents and polymers, and the modification process and operating conditions are complicated, which limits its application in industrial coatings. Therefore, there is an urgent need to innovate the graphene functional modification method, and to study the mechanism of graphene in the coating material, and provide a theoretical basis for the large-scale application of graphene composite functional coating.
Composite material
Graphene has a high Young's modulus and intrinsic strength, and can be used to adjust the interface properties of graphene, such as hydrophilicity, to improve the mechanical properties and wear resistance of polymer materials. However, the biggest problem of graphene application in the field of composite materials is that the structurally intact graphene surface does not contain any groups, the surface energy is low and inert, and the interaction with other media is weak. Moreover, there is a strong van der Waals force between the graphene sheets, which results in the layers being easily agglomerated and difficult to disperse, difficult to dissolve in a solvent, and more difficult to be uniformly compounded with other organic or inorganic materials. Therefore, the future development direction of graphene application in the field of composite materials is to meet the specific surface performance requirements of graphene for different composite substrate systems, and to obtain specific surface properties of graphene products by covalently functionalizing and regulating different functional groups on graphene surface. The problem of dispersibility and interfacial compatibility of graphene in the composite material is solved, and the continuous network structure of graphene in the matrix is ​​realized, and the excellent performance of graphene is effectively exerted.
Conductive ink
Compared with the currently used metal (gold, silver, copper) conductive fillers, graphene conductive fillers are more stable, less susceptible to oxidation, and have stronger adhesion. Graphene fillers have greater advantages in terms of conductivity. Foreign graphene conductive inks are in the experimental development stage and are undergoing industrial layout. At present, the electrical properties of graphene conductive inks are between the silver paste and carbon paste resistance values, which can only meet the field of lower conductivity. The long-term development direction is to obtain graphene conductive ink with higher conductivity, taking into account the flexibility of graphene to meet the requirements of electronic components such as flexible screens and flexible printed circuit boards.
Energy storage and conversion
Graphene has great application prospects in energy storage and conversion of lithium ion batteries and lithium-sulfur batteries due to its extremely large specific surface area, excellent electrical conductivity, good chemical stability and excellent mechanical properties. Researchers at Northwestern University used self-assembly methods to prepare FeF3/graphene cathode materials. The material still has a specific capacity of 260 mAh·g-1 over 100 cycles, which is twice that of commercial cathode materials. They prepared a silicon/porous graphene film anode material by means of a vacuum method, and the material still has a capacity of 1500 mAh·g-1 over 200 cycles. However, due to the large specific surface area of ​​the graphene, the lithium salt electrolyte forms a passivation film (SEI film) on the surface of the graphene, consuming up to 30% to 50% of the first discharge capacity, resulting in a low efficiency of the first cycle coulombic. In addition, the current graphene preparation technology has bottlenecks such as few single layers, small size and uneven distribution, difficulty in stable mass production, and difficulty in precise control, and there is still a considerable distance from commercialization. Therefore, the future development direction is mainly to construct a highly structured graphene composite structure with uniformly distributed nanopores with uniform pores on the surface, and the layers are in close contact to improve the capacity, power and cycle life of the positive and negative materials.
semiconductor
The conductive and thermal conductivity of graphene far exceeds that of silicon and other traditional semiconductor materials. With the continuous improvement of integrated circuit manufacturing technology, the size of transistors made of silicon is approaching the limit (15nm or even below 10nm), and graphene is expected to replace silicon. Become a new generation of electronic components materials. At present, the biggest problem in the application of graphene film in the semiconductor information industry is that a large area of ​​graphene film is a zero-gap material, and it is difficult to turn off the transistor as a channel. It is difficult to obtain a high switching ratio of the graphene transistor. achieve.
In the future, the direction of graphene is mainly to develop a method of replacing carbon atoms in a lattice structure, constructing a multi-dimensional nanostructure or forming a heterojunction by doping, and overcome the problem of zero band gap to achieve a high switching ratio.
Application challenges in the graphene industry
Although the graphene industry has achieved amazing results, from the stage of the development of the graphene industry, it is still in the "eve eve" of large-scale industrialization, and there are still some problems that need to be solved as a whole:
Key technologies need to be broken
After years of independent research and development, the scale production technology, process equipment and product quality of graphene have made major breakthroughs, but the maturity of graphene scale production technology is still low, and the quality of different batches of graphene products is unstable and nature. The problem of big differences.
In terms of graphene powder, the current commercial graphene products generally have problems of uneven size and number of layers, low single-layer graphene content, specific surface area far lower than the theoretical value, no classification, high cost, etc., and cannot truly represent graphene. Various excellent properties; the structurally intact graphene surface does not contain any groups, has weak interaction with other media, is difficult to disperse in a solvent, and is more difficult to uniformly recombine with other organic or inorganic materials.
In terms of graphene film, the existing products have unavoidable structural defects caused by the growth process and surface contamination caused by the transfer process, and the general resistance is high, and it cannot be applied in the field which should be suitable for matching the excellent electrical properties.
From the perspective of forward-looking technology, most of the graphene technology patents in China are local patent applications. The foreign patent technology layout is relatively weak, and very few can be cited by foreign patents. The patent quality is generally not high, and the basic core patent is lacking.
In the strategic high-tech fields such as electronic information, biomedicine, energy conservation and environmental protection, it has basically been monopolized by the United States, Europe, South Korea and Japan. In particular, China's graphene enterprises are mainly small and micro enterprises and start-up enterprises, lack of capital investment, weak research and development capabilities, and weak market development capabilities. They are cracking the bottleneck of graphene technology, promoting the application of graphene materials, and expanding the scale of graphene industry. The aspect is stretched. Without good technological innovation research and development and results transfer and diffusion mechanisms, it will lead to long-term development weakness.
Application market needs to be expanded
Graphene has been a "young" material since its discovery for only 10 years. From the application status quo, graphene mainly achieves preliminary application. Most products belong to the combination of graphene and original materials to improve product performance. The technical threshold is relatively low, and the homogenization situation is more serious. Although the downstream application of graphene has been initially industrialized, the real “killer†application has not yet been born. Although there are many patents in China's graphene industry, more than three-quarters of the patents come from academic institutions. The participation of enterprises in the research and development of graphene needs to be further improved. There are not many high-value patents, and the supply and demand between technology and market are still Mismatch, technology development, transfer diffusion and the first commercialization chain have yet to be opened.
Standard system needs to be built
Graphene standard system, graphene and related industries are increasingly becoming the hottest concept in the capital market, but lack of national standards such as graphene material classification, terminology, detection methods, and group standards or industry standards for graphene products, resulting in the market. The graphene-related products are mixed with fish, and the quality of the products is very uneven. Many enterprises do not have the scale production capacity of graphene at all. With the excessive speculation of graphene concept, it has seriously affected the benign development of graphene industry. Therefore, China needs to establish a graphene standard system to regulate the development of graphene industry.
In the future, the development of graphene industry should focus on the following aspects:
First, vigorously strengthen the innovation of graphene and innovation system construction, focus on cultivating technical innovation talents in graphene industry, and use the platform of graphene innovation center and graphene research institute to carry out top-level design and overcome common key technologies, and apply graphite for application. Key technologies such as stable preparation and dispersion technology of olefin materials are included in major research projects, supporting joint research and development of graphene upstream and downstream enterprises and scientific research units. According to the development characteristics and advantages of local graphene industry, select key application breakthroughs, especially in chips and microelectronics. And other high-end applications.
Second, actively promote the breakthrough of downstream application technology. According to the application difficulty of graphene materials, downstream affordability, potential application scale, and local advantageous industries, select a batch of graphite with good industrial prospects, mature technology and large amount of graphite. The olefin products are docked for downstream applications to form an application demonstration.
The third is the joint advantage of enterprises, research institutes, etc., according to the development status of the graphene industry and downstream applications, select a group of more mature graphene and its application products, from product definition, performance, graphene form and dosage Formulate a number of national and industry standards and improve the graphene standard system. Research and develop the specifications of graphene industry, and put forward the threshold for the graphene industry from the aspects of industrial layout, production process and equipment, clean production, quality management, etc., to prevent low-level redundant construction and strengthen environmental protection.
The fourth is to establish a graphene industry development fund, adopting a model of policy support and social capital to participate in key technologies.
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