Abstract In recent years, China's graphite industry has received more and more attention from the government, especially in terms of technological innovation, and has received strong support from some experts and academicians. The “Grade Industry Access Conditions†issued at the end of last year stipulated that new high-purity graphite projects should be built, rebuilt and expanded, and energy-saving and environmental protection...
In recent years, China's graphite industry has received more and more attention from the government, especially in technological innovation, and has received strong support from some experts and academicians. The “Grade Industry Access Conditions†issued at the end of last year stipulated that new high-purity graphite projects should be built, rebuilt and expanded, and advanced technological routes of energy conservation and environmental protection should be adopted; new and expanded expansion and expansion graphite projects should be adopted, and electrolytic oxidation processes or strong acid impregnation process routes should be adopted; Newly built and rebuilt and expanded flexible graphite projects, using continuous expansion, calendering molding process and equipment. Under the joint promotion of all parties, graphite companies have rushed to deep processing projects to compete for the production of deep-processed products. However, due to the late start, lack of technology, lack of funds, shortage of talents, etc., some graphite enterprises' deep processing projects either suffer from no technology or can't find the way to technological innovation, leading to lagging development. Then, what is the current status of China's graphite industry technology development? What technologies and products are needed by enterprises? What are the promising development directions in the future? This reporter interviewed.
Technology upgrades and initial results
At the beginning of August, the annual meeting of the graphite industry technology innovation strategic alliance was held in Jixi City, Heilongjiang Province. The reporters and representatives of the participants visited the Jixi Graphite Industrial Park and several graphite enterprises. The reporter saw that with the support of the resources, with the support of the policy, the graphite industrial park here has been continuously constructed and expanded. The graphite project has been stationed one after another. The entrepreneurs of the park have newly developed deep processing projects, and introduced advanced technology and equipment. Develop new projects and develop new products.
The picture shows a researcher from the Chongqing Institute of Green and Intelligent Technology of the Chinese Academy of Sciences showing the super light transmission of single-layer graphene products (right). (CFP for the picture)
"These achievements are unimaginable decades ago. Just a few years ago, we did not expect the graphite industry to develop so fast." A local graphite company executive’s speech triggered a meeting. The resonance of the representative.
According to Shen Wanci, a professor of materials science and engineering at Tsinghua University, until the 1980s, China's graphite industry only had mining, mineral processing and a small amount of purification technology. The technology still used the level of foreign countries 30 or 40 years ago. In the late 1980s and early 1990s, the “black storm†appeared in the graphite market driven by the market trend of export earnings. The graphite industry in China occupied most of the world market at the expense of resource waste and environmental pollution. Vicious competition leads to low prices of graphite resources, and there is basically no improvement in mining technology. Since the end of the 1990s, driven by the lithium-ion battery industry, China has developed spherical graphite and anode materials, which basically reached the technical level of foreign countries in the 1990s.
At the beginning of August, the annual meeting of the graphite industry technology innovation strategic alliance was held in Jixi. The picture shows the meeting site.
In July 2011, 10 academicians including the former vice president of the Chinese Academy of Engineering, Wang Dianzuo, co-authored the State Council and submitted the “Proposal on Establishing the National High-tech Graphite Product Development Industrialization and Trading Base (International Graphite Valley) in Heilongjiang Provinceâ€. The instructions of Premier Wen Jiabao of the State Council.
The Ministry of Science and Technology implemented the spirit of leadership and decided to lead the research on the development plan and implementation plan of the national graphite new materials industry by Heilongjiang Province, and launched the national science and technology support plan with a total budget of about 150 million yuan, and approved the establishment of the Heilongjiang graphite industry technology innovation service platform. The Heilongjiang Torch Plan Science and Technology Industrial Base was identified. At the same time, China's graphite industry technology innovation strategic alliance was also established.
A stone stirred up a thousand waves. Under the guidance and care of the leaders of the State Council, under the support of governments at all levels and relevant departments, and supported by the Strategic Alliance for Technology Innovation and the National Science and Technology Support Program, a number of enterprises that are developing towards the deep processing of the graphite industry have sprung up.
Heilongjiang Aoyu Graphite Group is a typical enterprise that takes graphite deep processing roads. Cui Guanghong, general manager of Aoyu Graphite Group Deep Processing Co., told reporters: "At present, the Group's deep processing project is progressing smoothly, and conventional products are in normal production. Through two years of practice and independent research and development, it has developed its own core products. Among them, deep processing companies and The ultra-fine spherical graphite jointly developed by a Taiwanese company was put into operation in May this year. The intermediate particles of conventional spherical graphite are 16 to 18 microns, and the intermediate particles of this ultra-fine spherical graphite are less than 8 microns. Large, crushing, purification, drying and other aspects have a high technical content. At present, the company has produced more than 30 tons of ultra-fine spherical graphite, the products are direct sales to Japan, South Korea and the United States."
In the field of independent innovation, Jixihao New Energy Materials Co., Ltd. has also gained. Wang Guoli, assistant general manager of the company, said that the current temperature of the domestic production of anode materials is 2800 ° C, and their company has improved the production technology, the furnace temperature can reach 3100 ° C, and the process temperature is stable, achieving the graphitization furnace in the super Stable operation under high temperature conditions greatly meets the production requirements of anode materials. According to relevant experts, this technology is currently at the advanced level in the domestic industry. The products have passed the test of the authoritative organization, and the carbon content has reached 99.995%. It has reached the relevant standards of high-purity graphite in Germany and the United States. The company currently has 4 patents and 3 patents in the filing process.
In recent years, some graphite advanced practical technologies and outstanding scientific and technological achievements have been transformed. The “Twelfth Five-Year Plan†for the development of the graphite industry science and technology, the establishment of the national graphite product inspection and testing center, the high thermal conductivity research and development academician workstation, and the graphite deep processing product research and development center have further promoted the transformation of graphite technology achievements into productivity. The development of high-purity graphite materials and their typical applications, the development of natural spherical graphite specific capacity research and development, and the development of key technologies for the production of lithium-ion battery anodes for natural graphite have been officially implemented. The graphite technology cooperation agreement of the school-enterprise alliance and the government-enterprise alliance was successively signed. Some enterprises independently research and develop patent technology, and the tooling equipment related to Hubei Yichang Xincheng Graphite Co., Ltd. is leading in the national industry. It has applied for 7 national utility model patents, and has authorized 4 projects to innovate and develop ultra-thin graphite heat conduction. New membrane product; Zhuzhou Vlad's natural microcrystalline graphite ultra-high temperature continuous purification equipment, the pilot line once purified the medium-high carbon flake graphite and microcrystalline graphite ore to 99%-99.99%, this year will have industrial equipment available, can Consumption ≤ 3500 kWh / ton, and is expected to replace chemical purification.
"At present, the country has initially possessed graphite deep processing, fine processing and surface treatment technology, composite technology of metal, plastic and graphite, ultra-fine nano graphite, graphite alloy powder, liquid graphite, graphite sol preparation technology, etc. These technologies can be used as Lithium-ion battery electrodes, combustion battery plates, conductive graphite paper, conductive rubber, water-oil adsorption materials, electromagnetic shielding materials, graphite conductive latex paints, graphite foam materials, catalyst carriers, graphite alloy bearings, etc. "Graphite industry technology Han Yufeng, chairman of the Innovation Strategy Alliance, said.
With the development of the graphite industry, more and more people of insight point out that graphite is an important strategic resource of China. It should protect China's own unique resources and take the innovative route of graphite deep processing technology.
In July 2011, 10 academicians including the former vice president of the Chinese Academy of Engineering, Wang Dianzuo, co-authored the State Council and submitted the “Proposal on Establishing the National High-tech Graphite Product Development Industrialization and Trading Base (International Graphite Valley) in Heilongjiang Provinceâ€. The instructions of Premier Wen Jiabao of the State Council.
The Ministry of Science and Technology implemented the spirit of leadership and decided to lead the research on the development plan and implementation plan of the national graphite new materials industry by Heilongjiang Province, and launched the national science and technology support plan with a total budget of about 150 million yuan, and approved the establishment of the Heilongjiang graphite industry technology innovation service platform. The Heilongjiang Torch Plan Science and Technology Industrial Base was identified. At the same time, China's graphite industry technology innovation strategic alliance was also established.
A stone stirred up a thousand waves. Under the guidance and care of the leaders of the State Council, under the support of governments at all levels and relevant departments, and supported by the Strategic Alliance for Technology Innovation and the National Science and Technology Support Program, a number of enterprises that are developing towards the deep processing of the graphite industry have sprung up.
If graphite tailings are not used and treated, it is easy to cause environmental pollution. The picture shows the graphite tailings of a company.
Heilongjiang Aoyu Graphite Group is a typical enterprise that takes graphite deep processing roads. Cui Guanghong, general manager of Aoyu Graphite Group Deep Processing Co., told reporters: "At present, the Group's deep processing project is progressing smoothly, and conventional products are in normal production. Through two years of practice and independent research and development, it has developed its own core products. Among them, deep processing companies and The ultra-fine spherical graphite jointly developed by a Taiwanese company was put into operation in May this year. The intermediate particles of conventional spherical graphite are 16 to 18 microns, and the intermediate particles of this ultra-fine spherical graphite are less than 8 microns. Large, crushing, purification, drying and other aspects have a high technical content. At present, the company has produced more than 30 tons of ultra-fine spherical graphite, the products are direct sales to Japan, South Korea and the United States."
In the field of independent innovation, Jixihao New Energy Materials Co., Ltd. has also gained. Wang Guoli, assistant general manager of the company, said that the current temperature of the domestic production of anode materials is 2800 ° C, and their company has improved the production technology, the furnace temperature can reach 3100 ° C, and the process temperature is stable, achieving the graphitization furnace in the super Stable operation under high temperature conditions greatly meets the production requirements of anode materials. According to relevant experts, this technology is currently at the advanced level in the domestic industry. The products have passed the test of the authoritative organization, and the carbon content has reached 99.995%. It has reached the relevant standards of high-purity graphite in Germany and the United States. The company currently has 4 patents and 3 patents in the filing process.
Aoyu Graphite Group actively responded to the national call for new environmental protection and energy-saving tailings sand hollow bricks and other deep processing projects. With an annual output of 40 million bricks, the annual sales income can reach 20 million yuan. The picture shows the hollow brick produced by Aoyu Guangsha New Material Brick Factory.
In recent years, some graphite advanced practical technologies and outstanding scientific and technological achievements have been transformed. The “Twelfth Five-Year Plan†for the development of the graphite industry science and technology, the establishment of the national graphite product inspection and testing center, the high thermal conductivity research and development academician workstation, and the graphite deep processing product research and development center have further promoted the transformation of graphite technology achievements into productivity. The development of high-purity graphite materials and their typical applications, the development of natural spherical graphite specific capacity research and development, and the development of key technologies for the production of lithium-ion battery anodes for natural graphite have been officially implemented. The graphite technology cooperation agreement of the school-enterprise alliance and the government-enterprise alliance was successively signed. Some enterprises independently research and develop patent technology, and the tooling equipment related to Hubei Yichang Xincheng Graphite Co., Ltd. is leading in the national industry. It has applied for 7 national utility model patents, and has authorized 4 projects to innovate and develop ultra-thin graphite heat conduction. New membrane product; Zhuzhou Vlad's natural microcrystalline graphite ultra-high temperature continuous purification equipment, the pilot line once purified the medium-high carbon flake graphite and microcrystalline graphite ore to 99%-99.99%, this year will have industrial equipment available, can Consumption ≤ 3500 kWh / ton, and is expected to replace chemical purification.
"At present, the country has initially possessed graphite deep processing, fine processing and surface treatment technology, composite technology of metal, plastic and graphite, ultra-fine nano graphite, graphite alloy powder, liquid graphite, graphite sol preparation technology, etc. These technologies can be used as Lithium-ion battery electrodes, combustion battery plates, conductive graphite paper, conductive rubber, water-oil adsorption materials, electromagnetic shielding materials, graphite conductive latex paints, graphite foam materials, catalyst carriers, graphite alloy bearings, etc. "Graphite industry technology Han Yufeng, chairman of the Innovation Strategy Alliance, said.
There is still a need for the road to innovation.
Although China's natural graphite deep processing technology has made rapid progress, there are still many shortcomings. Compared with developed countries, China's graphite deep processing industry is relatively backward, the industrial chain is short, the product technology content is low, and high-tech products are few. At present, raw material production and processing of flake graphite are still the main products.
At present, China's flexible graphite is still in the trial production stage, there are 20 or 30 production lines, but there are not many advanced; lithium-ion batteries are still in the small test stage; silicon-impregnated graphite is still blank. This phenomenon is extremely incompatible with the status of China's graphite production power. The reason is that there are still some problems in China's graphite deep processing technology, and the investment in technology development is not enough.
It is understood that the deep processing technology of graphite in Germany, France, the United States, Switzerland, Japan and other countries is quite mature. These developed countries have basically monopolized the advanced technology and intellectual property of graphite deep processing, using our cheap raw materials and deep processing into advanced graphite materials. Extremely high prices occupy the international market and are sold back to China. At present, the flexible graphite industry in the United States, Japan and other countries is the world leader; Japan's nuclear energy-grade ultra-low sulfur (S <500ppm) and high-purity sulfur (S <50ppm) products are the world's leading technology; the United States, Japan's lithium ion The use of modified graphite as anode material in the battery has formed a scale industry; currently immersed silicon graphite can be produced only in Germany, the United States and Russia.
The former Secretary-General of China Graphite Industry Association, Qi Zhixiang, believes that the graphite industry is working hard in the direction of deep processing. The key is in raw materials. It is necessary to select a large amount of large scale graphite as raw material to produce high-carbon high-purity graphite through technical means. From the current point of view, China still has great difficulty in selecting scale graphite, mainly because it is not enough to protect graphite resources. The United States, Russia, Britain, Germany and other countries have used their own graphite resources as strategic resources to reserve and limit the exploitation of graphite resources. Compared with developed countries, China's graphite resources have not received the attention it deserves. Large-scale disorderly mining of graphite resources and long-term low-cost exports have led to the massive loss of rare strategic resources. In addition, China's graphite industry production layout is relatively scattered, lack of specialized collaborative division of labor and scale effect, coupled with weak corporate technology, no formal mining design, mining imbalance. In particular, the protection of large scale graphite is not conducive to the future development of the industry.
Shen Wanci believes that there are still some technical difficulties in the production of high-quality anode materials, especially materials related to power and energy storage batteries, and high-heat-conducting materials. In the long run, the current problem of preparing graphene powder in bulk is not a big problem, but finding a suitable use, and then forming a product and industry, has a large technical difficulty and requires a certain amount of time.
Han Yufeng believes that the main common problem faced by graphite enterprises is technical problems, mainly in the areas of new products, environmental protection, mining, tailings treatment, etc., which need to improve the level of technology, technology and equipment. One is spherical graphite technology. It is necessary to break through the spherical spheroidization technology of small particle scale graphite in spherical graphite production and improve the recovery rate. The second is mineral processing technology. To solve the problem of poor ore selectivity, the sorting effect is not good, leading to the improvement of concentrate taste and the large breakage rate of graphite scales during grinding. The third is the comprehensive utilization of tailings sand. A large amount of tailings sand is accumulated, causing environmental pollution, seeking comprehensive utilization technology of tailings sand, and preparing high-tech products. The fourth is the preparation technology of graphite superconducting materials. At present, the preparation process of graphite superconducting materials is very complicated, the output ratio is very low, the consumption of raw materials is large, the production cost is high, and the superconducting performance is unstable. The fifth is the graphite catalyst column and diamond composite production technology. The technique of reducing the synthetic pressure and temperature conditions of diamond and increasing the growth rate of diamond by adding appropriate metal elements is studied.
Transforming new materials is the direction of development
Relevant experts have put forward their own views on how to break the situation that China's graphite industry technology is seriously backward.
Liu Qiyan, deputy director of the research office of the General Office of the Ministry of Science and Technology, believes that China should use graphite as the basic material to think in all directions. Thinking from a full carbon perspective, the graphite industry technology innovation strategic alliance was raised to the carbon materials alliance. To the transformation of carbon-related industries and technologies, the industry should accelerate the industrialization of carbon materials, realize large-scale applications at an early date, and take the initiative in the development of new carbon materials.
For the technical upgrading roadmap of the graphite industry, Shen Wanci suggested: First, the powerful mineral design and research institutes combined with mining and selection enterprises, introduced advanced mining and mineral processing technology equipment of other minerals, designed and built advanced graphite mining and ore dressing production line, Significant improvements in technical and economic indicators such as consumption, recovery, large scale protection, water use, and tailings treatment. Second, China has already advanced environmentally-friendly and energy-saving advanced acid-base purification and energy-saving high-temperature purification technology. The advanced acid-base method greatly reduces the water consumption. 80% of industrial water is recycled or used in medium water; high-temperature purification energy consumption is 3,500 kWh/ton, which basically consumes no water. It is recommended that the government guide, combine production, study and research, and build different types of large-scale graphite purification production lines according to the characteristics of resources, and strictly limit the use of hydrofluoric acid that seriously pollutes the environment in chemical purification. Third, relying on resources, the industrial scale of natural graphite lithium-ion battery anode materials, and the development of different quality anode materials for different grades of battery requirements, so that the product serialization. Develop a safe, long-life natural graphite power battery negative electrode material. Fourth, the natural graphite-based isotropic graphite is industrialized. Fifth, the enterprise is the main body of the implementation of major engineering and technology projects. The selection of projects must be based on the characteristics of their own resources, their own technology, capital, and market capabilities to select projects.
Luo Chengwang, general manager of Hubei Yichang Xincheng Co., Ltd. told reporters that some deep processing enterprises still use traditional production techniques. The so-called deep processing projects are only newer equipments and more processes than before. However, such an approach can easily destroy large scale graphite. Now, the price of large scale graphite above 90 mesh is nearly 10,000 yuan / ton, and the graphite of 80 mesh scale is 6000 yuan / ton. Therefore, it is recommended that some institutions, experts, and enterprises jointly research new technologies to protect large scale graphite and improve its value. "In the future, the development direction of graphite materials should be the development of flexible graphite in the direction of high purity, high density and ultra-thin, the development of expanded graphite to high-expansion expanded graphite, and the development of flake graphite to the research of fine-grained flake graphite. Only in this way can deep processing projects continue In addition, spherical graphite is not an ideal lithium-ion battery material. The main drawback is that it is difficult to charge easily, and the life is limited due to repeated charging. The ideal material should be carbon material or graphene. The development of carbon materials," Luo Chengwang said.
Han Yufeng also put forward his own views. First, relevant departments and organizations should further cooperate with the China Science and Technology Development Strategy Research Institute and other departments and institutions to do a targeted, strategic and practical development of the graphite industry in view of the actual development of China's graphite industry. Technical route planning, focusing on two directions: high-purity graphite and its preparation; advocating the development and production of graphene, and realizing the industrial production of graphene as soon as possible. Second, the industry should extend the industrial chain, change the graphite industry to select and produce the primary product structure of primary raw materials, and gradually adjust the product structure to high-tech content, high value-added graphite deep processing products, graphite emerging materials and products. Utilizing the geographical advantages of the graphite industry bases such as Jixi and Luobei in Heilongjiang, we will focus on the development of six industrial chains, namely mineral processing and purification, graphite new energy supporting materials, flexible graphite and products, graphite micropowder and products, special graphite materials, and vein industry. The complete industrial chain promotes the transformation of the graphite industry from resource advantages to economic advantages and technological advantages.
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