Graphene is a honeycomb planar film formed by sp2 hybridization of carbon atoms with a thickness of less than one nanometer. It was firstly used by Nobel Prize winners - University of Manchester physicists AndreGeim and Konstantin Novoselov for micromechanical stripping. Separated from graphite. Graphene has very good tensile strength and light transmission, electrical and thermal conductivity, and is known as the "king of materials" in the new century.
In recent years, the concept of graphene has been highly sought after in the world, and governments, research institutes, enterprises and financial institutions have paid great attention to this. According to the latest research report of BCC Research, the global graphene market will reach 195 million US dollars in 2018 and more than 1.3 billion US dollars by 2023.
China's graphene industry is also developing rapidly. In 2015, the national graphene market was about 6.1 million US dollars, a year-on-year increase of more than 336%. The preliminary statistics have exceeded 20 million US dollars in 2016. However, at the same time of rapid development, China's graphene industry has also been controversial. Some people in the industry have questioned that it will become “the next photovoltaic industryâ€, which will hinder the subsequent development of the industry.
1. Development status of China's graphene industry
Due to technological advancement and the fact that the cost is not fast enough, the graphene industry in China has not yet experienced large-scale industrialization, and the government's industrial support policy system is also in the process of improvement. However, based on current market demand forecasts, China's graphene industrialization will make breakthroughs in a relatively short period of time.
The 2016 data released by the China Graphene Industry Technology Innovation Strategic Alliance shows that by 2020, the global graphene market will exceed 100 billion yuan, and the new energy industry's lithium battery and supercapacitor market will exceed 53.4 billion yuan, of which China accounted for More than 50%-80%.
(1) Status of industrial chain development
Divided according to product attributes, the graphene industry can be divided into three parts: upstream, midstream and downstream.
Upstream: the raw material industry of graphene, including graphite mining and hydrocarbon processing;
Midstream: Graphene production and processing industry, including processing of graphene film, graphene powder and other products;
Downstream: The application of graphene mainly includes semiconductor, flexible electronics, biomedicine, environmental protection and other fields.
1 graphite industry
The upstream graphite industry and other industries are relatively mature. First, the reserves of resources are large. According to the report of the China Geological Survey, China is the second largest graphite resource country in the world. The graphite base reserves account for about 33% of the world's total reserves. The resource reserves have been identified to be 260 million tons, and the predicted resource potential is 1.87 billion tons, mainly distributed in Heilongjiang. , Inner Mongolia and Shandong provinces.
China is the world's largest producer of graphite. In 2015, the national graphite production reached 860,000 tons, accounting for 67.7% of the world's total output. At present, there are 194 graphite mines in China, including 40 large mines, 19 medium-sized ones and 135 small ones, mainly distributed in Inner Mongolia, Heilongjiang, Hebei, Shandong, Hunan and Sichuan.
China is also the world's largest exporter and consumer of graphite. In 2015, its export volume was 251,000 tons, accounting for 79.0% of world trade; consumption was about 614,000 tons, accounting for 53.4% ​​of the world's total consumption.
2 graphene production and processing industry
At present, there are more than 400 related companies engaged in R&D, production and application of graphene in China, accounting for about 3/4 of the total graphene industry in the world.
From the perspective of geographical distribution of enterprises: Qingdao is mainly in Shandong in the north, Changzhou and Wuxi in Jiangsu in the east, Shenzhen and Dongguan in Guangdong in the south, and sporadic graphene enterprises in the central and western regions and northeastern provinces. However, no industrial cluster has been formed. Typical enterprises include Jiangnan Graphene Research Institute, Changzhou 2D Carbon Technology Co., Ltd., Shanghai Nanjiang Group, and Chongqing Branch Green Intelligent Technology Research Institute.
From the perspective of enterprise types, there are nearly 70 companies that have graphene as their main business, including more than 50 graphene powder related enterprises and nearly 10 graphene film related companies.
From the perspective of enterprise production technology: in the production technology of graphene, there are many enterprises using traditional techniques such as micro-mechanical stripping, chemical vapor deposition (CVD), epitaxial growth, etc., using sodium oxygen sulphide method and cutting carbon. There are fewer complex technologies such as nanotubes.
From the perspective of enterprise scale, more than 80% of the enterprises engaged in graphene production are small and medium-sized enterprises, and the annual sales are mostly at the level of one million yuan. However, some listed companies have begun to enter the graphene industry. According to preliminary statistics, as of September 14, 2016, a total of 18 listed companies participated in the graphene industrial chain layout, including 6 companies including Dongxu Optoelectronics and Lihe, and 5 companies including Kangdexin. And the other seven SMEs on the GEM and the New Third Board.
From the perspective of corporate profitability: the overall profitability of graphene producers is currently weak. Some production companies claiming to have a production capacity of 100 tons per year have far less than expected production value and profitability, and most companies are at a loss. According to the company's performance report for the middle of 2016, the net profit of Changzhou Sixth Element Materials Technology Co., Ltd. in the first half of the year was -13,367,700 yuan, and the net profit of Changzhou two-dimensional carbon materials was -52.14 million yuan. It is -28.38 million yuan.
3 downstream applications
The special planar two-dimensional structure of graphene is conducive to the transmission of electrons, and thus has many applications.
As a conductive additive, the internal resistance of the battery can be further reduced, and the battery rate performance and cycle life can be improved;
As a heat conductive material, the heat conductive fiber and the heat conductive plastic are modified to improve the heat dissipation capability of the material;
As a new conductive ink and plastic main filler, the electrical resistivity and adhesion properties of the conductive ink can be adjusted;
As an anti-corrosion paint film skeleton, it can improve the corrosion resistance of the film.
In addition, graphene has excellent antistatic, anti-radiation and swelling properties, hygroscopicity, antibacterial properties and other characteristics, making it possible to provide new materials for biomedical textile materials, antibacterial medical materials, flexible sensors and the like.
At present, China's graphene applications in composite materials, lithium batteries, and super capacitors are beginning to take off, and applications in flexible displays, sensors, supercapacitors , heat dissipating materials, semiconductor devices, and biomedicine are still under investigation. stage.
In the past two years, some domestic research institutions have made some breakthroughs in the application of graphene materials.
The Jiangnan Graphene Research Institute has realized the docking of graphene film materials and existing ITO module process lines, and successfully made a capacitive touch screen mobile phone prototype in the world;
The University of Science and Technology of China uses graphene to accurately and rapidly screen the function of ions to form a graphene oxide film for seawater desalination;
The Shanghai Institute of Ceramics of the Chinese Academy of Sciences has developed nitrogen-doped ordered mesoporous graphene, which is used as a high-performance supercapacitor electrode material, so that the car can only charge for 7s and the life can reach 35km.
However, from a holistic perspective, China's graphene industry chain is still fragile, and the complete and mature upstream and downstream industry chain needs to be consolidated. It can be said that most of the companies invest their money and energy in the production of graphene materials, while downstream applications focus on low value-added products. Some high value-added products have made little progress due to the lack of relevant talents and technologies.
(2) Graphene technology and patent
At present, international research hotspots on graphene are conductive, thermal conductivity, optimization of preparation methods, and preparation of nanomaterials;
The research hotspots of graphene in China focus on graphene preparation, graphene nanomaterials and composite materials, graphene in lithium ion and solar cell electrode materials and optoelectronic devices.
China's scientific research institutions pay more attention to the funding of graphene related technology research. Since 2009, the Chinese Academy of Sciences, the Ministry of Science and Technology, and the National Natural Science Foundation of China have successively launched a number of graphene research projects, including the 863 project “Controlled Preparation of Graphene and Its Application in Photovoltaics†and the 973 Program "Controllable preparation, physical properties and device research of graphene", as well as a series of natural science fund projects.
According to statistics, the National Natural Science Foundation of China has allocated more than 300 million yuan to fund graphene-related basic research projects, including 385 graphene-related research projects in 2014 and 396 graphene-related research projects in 2015.
At the same time as technological advances, patent applications in the field of graphene in China are also very hot. According to the "2017 Graphene Technology Patent Analysis Report", the graphene Chinese patent application is 18,931, the invention number is 17306, the utility model is 1616, and the appearance is 9. Among them, 737 invention patents were filed, and the data retrieval time was March 1, 2017.
At present, there are 2,152 invention patents involving graphene raw materials, preparation technology, production technology and detection technology.
Raw materials include powder-slurry, graphene film, graphene fiber, macroscopic assembly, quantum dots, porous graphene, etc.;
The preparation technology is divided into mechanical peeling, intercalation stripping, chemical redox, electrochemical preparation technology, and the like;
The production process is divided into separation-purification-dispersion, functional modification, detection, equipment and so on.
From the application field of graphene, a total of 12,316 patent applications for graphene application research are concentrated in the following six fields.
Energy storage: lithium ion batteries, super capacitors, solar energy, fuel cells, lead acid batteries, etc.;
Composite materials: conductive materials, thermal conductive materials, reinforced-toughened materials, anti-corrosion, alloys, etc.;
Electronic information: transparent conductive film, photoelectric material, flexible display, etc.;
Water-gas treatment: catalytic degradation, adsorption, air purification, etc.;
Medical-health: Antistatic-antibacterial-heating and other functional materials and products, drug carriers, DNA gene detection, artificial bones, etc.
(3) Industrial policy
At the beginning of this century, the Chinese government proposed to develop seven strategic emerging industries such as new energy and new materials. Graphene is a newcomer in new materials. Although the industry has just started, it has also received the attention of the competent authorities of the government and introduced some policies to support it.
In 2012, the Ministry of Industry and Information Technology released the “12th Five-Year Development Plan for New Materials Industryâ€, explicitly mentioning “actively developing materials such as nano-powders, carbon nanotubes, fullerenes, graphenes, etc.â€;
In 2014, the National Development and Reform Commission issued the “Implementation Plan for Key Materials Upgrade and Replacement Projectâ€, proposing “to promote the development of next-generation information technology, energy conservation and environmental protection, marine engineering and advanced rail transit equipment, etc. 20 kinds of key new materials such as wide bandgap semiconductors and devices, new flat panel display glass and graphene to achieve batch stable production and scale application";
In 2015, the Ministry of Industry and Information Technology and other departments jointly issued "Several Opinions on Accelerating the Innovation and Development of Graphene Industry", proposing "focusing on high-quality and stable production of graphene materials, focusing on standardization, serialization and cost reduction of graphene materials. Efforts will be made to build a demonstration application industry chain of graphene materials, and focus on improving the concentration of graphene materials, speeding up the application process of scale, and promoting the graphene industry to become bigger and stronger;
In 2015, the State Council issued “Made in China 2025†and proposed “to pay close attention to the impact of disruptive new materials on traditional materials, and to prepare and develop strategic frontier materials such as superconducting materials, nanomaterials, graphene and bio-based materials in advance. Upgrade of basic materials."
In 2017, the “Guidelines for the Development of New Materials Industry†issued by the four ministries and commissions clearly pointed out that breakthroughs in common technologies such as large-scale preparation of graphene materials and measurement and characterization of micro-nanostructures, development of large-scale graphene film preparation equipment and special measurement and inspection of graphene materials. The instrument realizes effective control of key parameters such as graphene layer number and size. Focusing on anti-corrosion coatings, composite materials, touch screens and other application fields, focusing on the development of graphene-modified energy storage devices, functional coatings, modified rubber, thermal products and special functional products, sensors and touch devices based on graphene materials, Electronic components, etc., to build a number of graphene industrial chains, forming a number of industrial clusters.
(4) Standard system
As the saying goes, randomness does not stand, and the perfection of the standard system is very important for the development of an industry. Since September 2014, China has officially started the development of national standards for graphene. On August 12, 2016, the pre-examination of the national standard “Terminology, definitions and codes for graphene materials†was held in Changzhou and is expected to be released soon.
In addition, the first graphene detection method standard drafted by the Jiangnan Graphene Research Institute, "Graphite Layer Measurement Scanning Probe Microscopy" (draft) has also been approved by the National Standards Committee.
In December 2016, Guangxi Quality and Technical Supervision Bureau officially released five local standards for graphene, including “Methods for the Detection and Characterization of Graphene Three-Dimensional Structure Powder Materials†and “Glossary Terms and Definitions for Graphene Three-Dimensional Structure Powder Materialsâ€, Graphene three-dimensional structure powder material production polymer", "graphene three-dimensional structure powder material production technology" and "graphene three-dimensional structure powder material production high temperature reactor design specifications" and so on.
2. Problems and risks in the graphene industry
The graphene industry has begun to take off in China, but there are also many problems that pose risks to the subsequent development of the industry.
(1) Raw material mining is disorderly
Graphite is an important raw material for the preparation of graphene. China has a large graphite reserves, but there are also more than 190 graphite mining enterprises, which produce over one million tons of crystalline graphite and cryptocrystalline graphite every year. Due to various reasons, some enterprises have indiscriminately dig, ploughed and abandoned poverty, resulting in a waste of a large amount of graphite resources.
According to the calculation of the China Graphite Industry Association, according to the current mining method and speed, up to 20 years, the proven graphite resources in China will be exhausted. At that time, China will import graphite from abroad at a high price, and the graphite country will become a graphite poor country. This brings serious hidden dangers to the sustainable development of China's graphene industry.
(2) Technology research and development are mixed
Although China holds nearly half of the world's total graphene patents, compared with developed countries, there are still many problems in technology research and development.
First, there are many basic researches and few original innovations. At present, the research on graphene in China is mostly concentrated in the basic fields of electricity and chemistry. Among them, cutting-edge original achievements are rare, and most of them are catching up with foreign innovation.
Second, the economic applicability of the technical focus is poor. At present, domestic research is mostly concentrated in basic research fields, such as the preparation of bottom-up method, the application of graphene in lithium ion battery electrodes, graphene composite materials, etc., while the research in developed economies in Europe and America mainly focuses on optoelectronic devices and sensors. High-end applications such as pharmaceuticals and environmentally friendly materials. In contrast, the future economic performance of China's graphene technology research and development results is relatively poor.
Third, the responsibility of enterprises as the main body of technology research and development is not reflected. An industry can only continue to move forward when its employees have strong R&D capabilities. Unfortunately, among the domestic researches on graphene, universities and research institutes account for the vast majority, and more attention is paid to theoretical basic research. The results show fragmentation and homogenization. The only companies with real R&D capabilities are Shenzhen Hon Hai and other few, but the number of patents they hold is far less than that of IBM, Intel, Dow Chemical, GM, DuPont, Toshiba and other multinational companies.
In the future world industrial technology competition pattern, Chinese companies are clearly at a disadvantage.
(3) Disorder of industrial development order
There are more than one hundred graphene companies in China, but unlike the overseas companies such as Samsung, IBM, Nokia, Intel, and Dow Chemical, which promote the industrial application of graphene materials, Chinese companies mainly use graphene materials as additives. Repairing traditional industries.
At present, there are less than 10 enterprises in China that can mass-produce single-layer graphene in large quantities. Some enterprises and institutions have blindly exaggerated the production capacity and output value of the industry because of the speculative psychology of gaining profits through capital speculation, which has caused the market to follow suit blindly.
Other companies confuse single-layer and multi-layer, and graphene microchips or graphene nanosheets with thicknesses far exceeding 10 atomic layers are also referred to as graphene, causing confusion in the industry.
Some local governments have also helped, regardless of the conditions, are eager to build a graphene industrial park. According to preliminary statistics, nearly 20 graphene industrial parks have been built or under construction in the country, but their functions are similar. There will be serious homogenization competition in the future. The low price pattern will lead to a decline in corporate profitability. Conducive to the development of the industry.
(4) The amount of funds supported by Xiaoliwei
The graphene industry is a typical “technical + capital-intensive industryâ€, which requires a large amount of capital investment for technology research and development and market expansion. However, the current graphene industry in China faces serious shortage of funds.
First, the investment in technology research and development funds is relatively weak. At present, more than 80 companies in more than 80 countries around the world have invested in the development of graphene materials, and the UK, Korea, and Europe have raised graphene research to a strategic level.
It is understood that the UK has invested at least 237 million US dollars in graphene research in 2011-2016. South Korea plans to provide a total of 250 million US dollars in subsidies to the graphene field in 2012, and the European Commission will use graphene. Listed as one of the “Future Emerging Technology Flagship Projects†and provided $1.05 billion in funding for graphene application research within 10 years from 2013. In contrast, the Chinese government's investment in graphene-related research is only about $0.5 billion, which is much less.
Second, corporate financing difficulties. At present, China's graphene-based enterprises are mainly small and medium-sized enterprises and start-up enterprises. Most of the backbones are researchers from research institutes. The market development and maintenance capabilities are not strong, resulting in low profitability and high risk factors. According to this, most financial institutions hold a wait-and-see attitude, and enterprises generally have difficulties in financing. If the follow-up is still lack of external capital, China's small and medium graphene companies will eventually withdraw from the market due to financial crisis.
In contrast, the situation in developed countries in Europe and America is much better, because most of their companies are Samsung, LG, IBM and other large multinational companies. The company itself has the strength to invest a lot of manpower and material resources, and conduct long-term systematic research on graphene. And the government also strongly supports this, the market for graphene is highly favored, and the financing channels are relatively smooth.
3. Countermeasures and recommendations
(1) Do a good job in industrial development planning
The graphene industry is a strategic emerging industry. To promote the healthy development of the industry, it is inseparable from good industrial planning. However, China does not have a national level macro plan in the field of graphene. It is recommended to do a medium- and long-term development plan for the graphene industry, clarify the stage objectives, key tasks and safeguard measures for industrial development, so that the overall development of the industry is orderly.
At present, we need to plan three aspects first:
First, we must do a good job in the development and deployment of upstream raw materials, and adhere to the principle of “intensive and efficientâ€, coordinate the development of graphite resources, change the current phenomenon of indiscriminate mining, and provide sufficient resources for the sustainable development of the graphene industry.
Second, we must do a good job in the market guidance of graphene processing and application, reduce the exaggeration and blind follow-up in the market, and ensure the smooth and orderly industry.
The third is to stand at the height of the national science and technology strategy, make reasonable arrangements for the research and development of graphene technology, change the "small, single-handed" technology research and development model, concentrate limited research funds and manpower, and high-end technology to graphene. The application field has entered a favorable position for China to compete in the global graphene industry competition.
(2) Optimize industrial policy design
The graphene industry is still in its infancy in China, and there is an urgent need for industrial policy support. It is recommended that the competent departments at all levels should do a thorough investigation of the development status of the graphene industry in the region, clarify the main direction of the development of the industry and the main bottlenecks, and introduce policies to encourage enterprises to take a differentiated development path.
Support in land use, electricity use, and scientific research investment, and reduce the financial pressure of the majority of small and medium-sized enterprises, so that they can be lightly loaded. At the same time, we must also pay attention to the improvement of the financial subsidy mechanism. We must learn from the experience and lessons of the development of China's photovoltaic industry, aim at cultivating enterprise clusters that can “turn awkward and walkâ€, gradually reduce the dependence of enterprises on financial subsidies, and finally form their own. The core competitiveness, the tide of market development, has become the backbone of industrial development.
(3) Breaking through the bottleneck of industrial constraints
China's graphene industry is in the process of moving from laboratory to industrialization. The development direction and profit model of the industry are still unclear, and there are many constraints. The government should promptly intervene and guide the industry to help the industry break through the bottleneck.
First, break through the bottleneck of small market size. It is necessary to cultivate leading enterprises, and implement the concept of “putting, managing, and serving†to find out the key minority, provide precise support, help them grow bigger and stronger, and produce leading role in industry demonstration, and promote the overall scale of the market.
The second is to break through the constraints of high-end talent shortage. It is necessary to pay attention to attracting wisdom, gathering wisdom and cultivating wisdom. On the one hand, in the implementation process of the “Thousand Talents Plan†of the country, we will increase the introduction of international first-class graphene technology research and development talents; on the other hand, we must cultivate local top talents. Through the vigorous implementation of the "Innovative Talent Promotion Plan", etc., we will cultivate young talents and gradually establish a world-leading graphene technology research and development echelon with strong research and development capabilities and innovation.
The third is to break through the obstacles of funding shortages. It is necessary to build a good financing development platform, use policy measures to stimulate market enthusiasm, develop financial products and services that meet the characteristics of graphene industry, and make new financial formats such as angel investment, technology insurance, and technology small loans become powerful funds for the development of graphene industry. channel.
(4) Improve the industrial order environment
The development of any industry is inseparable from a good market environment and a sound standard and technical service system. The government should play a leading role in building a good development environment for the graphene industry.
First, establish and improve industry norms, set up entry barriers, strengthen industry self-discipline, eliminate the “traversal†in the market, purify the market development environment, and enhance the confidence of the industry.
Second, it is necessary to rely on relevant industry associations such as associations and associations to speed up the improvement of the industry standard system and make the development of the industry follow the rules. At the same time, we must actively participate in the division of labor in the development of graphene international standards, so that China's cumulative advantages in graphene research and development will be converted into standard advantages, and strive to grasp the leading role in the development of the global graphene industry.
4, the conclusion
China's graphene industry has started, but the industrial chain is still fragile. There are many problems and risks such as “disorderly mining of raw materials, weak development of high-end application technology, industrial disorder and financing difficultiesâ€, which affects the subsequent healthy development of the industry. Relevant departments should "do a good job in industrial development planning, improve relevant policies, focus on breaking the market size, high-end talent shortage and insufficient development funds, and focus on building a good market development order environment" to promote the sustainable development of China's graphene industry.
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