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As a "king of new materials" that has allowed discoverers to win the Nobel Prize, while domestic companies frequently launch "revolutionary products", why are they unanimously accused by the industry of being a lie?
As the end of the year approaches, Li Yichun is becoming more and more hasty - within more than a month, his itinerary covers Suzhou, Anhui, Dezhou, Shandong, Deyang, Sichuan, Tangshan, Hebei, as well as Beijing, Shanghai, Chongqing and other places.
As the secretary-general of the "China Graphene Industry Technology Innovation Strategic Alliance", he goes to various parts of the country to conduct research or participate in various forums almost every day, and cooperates with local governments or research schools to jointly build a graphene industrial zone, trying to make the graphene industry blossom throughout the country.
Compared with the slightly low-key secretary-general, other news is quite high-profile: First, on November 26, 2015, "Huawei Mate8" intentionally or unintentionally said on Weibo that the highlight of the press conference was "using a brand new graphene battery"; then at the end of December, the Shanghai Institute of Silicate of the Chinese Academy of Sciences announced that it can be used as an electric vehicle "the "graphene super battery" that can be used as an electric vehicle was released - it only takes 7 seconds to charge and can last 35 kilometers; and the latest news is that a research institute in Qingdao announced on January 19 that it had developed the internationally leading graphene lithium electronic capacitor.
"All the above are just to show that graphene has become the hottest industrial topic." An observer told reporters that from being discovered in 2004 to the discoverer being awarded the Nobel Prize in 2010, graphene has been lukewarm. In the past year, it has been arguing with the slogans of "universal revolutionary materials" and has become the gold rush industry that many local governments, research institutions, enterprises and even the capital market are most keen to get involved in. Behind the "gold rush" of
is the increasing doubts about graphene application: Is the electric car with a range of 35 kilometers in 7 seconds of charging and the "5-minute call to 10 hours" true or false? Does this kind of universal new material that seems to be almost invincible to use bring about revolutionary subversion or "painting a cake to fill your hunger"? And when will this seemingly bright industrial prospect be truly fulfilled?
Behind the "world's leading graphene"
If it weren't for the relationship with graphene, "Huawei Mate8" would definitely not cause such great controversy.
On November 26, 2015, before Huawei released the Mate8, Sina Weibo "Huawei Mate8" released such a trailer-Huawei Mate8 will use a brand new graphene battery.
"This shocked me." As a graphene research enthusiast, Zhong Chuming noticed that among the copy circulating on the Internet, this is almost a revolutionary product: the
3000 mAh battery can be charged to 48% in 5 minutes. This is the largest commercial graphene operation in China and even the world... The battery revolution may indeed be facing a critical point. "
If the news is true, this will be the first time graphene has made a brilliant debut in the form of industrial products. In Zhong Chuming's impression, graphene, known as the "king of new materials", has received great attention from Huawei. On October 23, 2015, on the day President Xi Jinping visited the National Graphene Research Institute of the University of Manchester, the UK, Huawei announced a joint research on the field of ICT (information, communication, technology) with the University of Manchester to study how to apply graphene to consumer electronic products and mobile communication devices.
A earlier seminar held in Japan, Huawei said that graphene-related technologies will be commercially available; Ren Zhengfei, the founder of Huawei, has also talked about graphene many times before, believing that "this time The biggest disruption in the future is that the graphene era will subvert the silicon era, and a technological revolution will break out in the next 10 to 20 years.
Therefore, the outside world has great hope for Huawei Mate8. Unfortunately, in the official press conference, Huawei did not mention the direct use of graphene materials, which also made the outside world question the relationship between "Huawei Mate8" and graphene is hype.
On December 18, 2015, Xinhua News Agency's report shocked people again. The Shanghai Institute of Silicate of the Chinese Academy of Sciences has developed a high-performance supercapacitor electrode material - nitrogen-doped ordered mesoporous graphene. This material has excellent electrochemical energy storage characteristics and can be used as a "super battery" for electric vehicles: can last 35 kilometers in just 7 seconds to charge.Related research results have been published in the world's top journal Science.
At present, electric cars can run about 300 kilometers per charge, but it takes 2 hours to charge them once. It is hard to imagine what kind of revolution the "graphene super battery" brings.
However, some people later discovered that the paper published in Science does not mention graphene, but carbon material, and supercapacitors are called "batteries".
This also cannot slow down other companies or research institutes to develop "world-leading graphene": On January 18, Qingdao Energy Storage Industry Technology Research Institute announced that it had successfully developed graphene lithium battery capacitors, and the expert identification generally reached the international advanced level.
For the general public, in the past year, we have also seen many dazzling graphene introductions on the Internet: As the thinnest, hardest, and most powerful universal material found at present, graphene "recharges 1,000 times that of ordinary batteries", "can run 1,000 kilometers in ten minutes of charging", "can charge 5 minutes, and can talk for 10 hours"... etc., which are enough to subvert all traditions.
The king of new materials that revolutionizes the 21st century
Normally, tape will not be regarded as a scientific breakthrough progress. But in 2004, when physicists Andre Geim and Konstantin Novoselov, a University of Manchester physicists from the UK, published their research in Science - a single-atomic sheet of carbon atoms that were stripped from a piece of graphene with transparent tape, this research slowly kicked off the materials science revolution.
Source and uses
Graphene thus opens up a new horizon for two-dimensional materials. In a sense, two-dimensional materials are not a completely new technology. Researchers have used molecular epitaxial machines to develop thin-filled materials in atomic form since the 1960s.
Condensed matter physicist Zhang Yuanbo of Shanghai Fudan University in China said:
Graphene is different, it is more like a page in a book. "
What is little known to the outside world is that in the journal Nature, a famous paper published by Gaim, an article about graphene by Zhang Yuanbo and his collaborators was published, but the 2010 Nobel Prize in Physics did not favor the latter. At that time, this was regarded as the closest domestic scholars to Nobel.
11, research results in graphene-related fields have increased exponentially. In 2014, global researchers published super research results on graphene More than 15,000 projects. More than 200 institutions and more than 1,000 researchers have been engaged in the development and research of graphene technology, including Samsung and IBM. In the past five years alone, developers and manufacturers have applied for 13,000 technology patents in graphene, of which China has applied for the largest number of patents, with more than 2,200, accounting for one-third of the world.
This phenomenon is reasonable: because it is the thinnest, lightest, strongest, and best conductivity of nanomaterials, stone Once methylene was released, it was recognized as the most promising new material in the 21st century. It can be widely used in microelectronics, physics, energy materials, chemistry, biomedicine, aerospace, environmental protection and other fields.
For example, after adding graphene to the manufacturing process, the touch screen of smartphones may be thinner, lighter, and the least fragile; the charging of mobile phones may only take a few seconds; the running speed of computer processors may be hundreds of times, etc.
In 2011, scientists from IBM Watson Research Center in "Sc Ience announced that they had successfully developed the first integrated circuit made of graphene wafers. This achievement was rated as one of the top ten scientific news in the world in 2011, marking a big step forward in the application of graphene on computer chips. The reason is that this chip may enable mobile phones to work where they are usually considered unable to receive signals.
"In the past, we were 100% dependent on oil, but now through mixing graphene, human dependence on oil may be reduced to 50% as originally."Gordon Chiu, founder of Grafoid in Canada, believes that graphene may even replace certain metals and other natural resources in the manufacturing process," Graphene has the ability to fundamentally influence our lifestyle and advanced nature as a species on Earth. "
Why is graphene a lie in China?
However, although the application prospects of graphene are becoming more and more optimistic, another completely different statement is also firmly determined: graphene is a scam in China.
In March 2015, the Chongqing Green Intelligent Technology Institute of the Chinese Academy of Sciences announced the launch of a "Xingchi SETTLER" According to the publicity at that time, the graphene phone with α" had a light transmittance of up to 97%, the charging rate of the mobile phone was increased by 40%, the battery life was extended by 50%, and the battery's energy density also increased by 10%. Because it was related to graphene, although this phone was only equivalent to a thousand yuan configuration, the price was as high as 2,499 yuan.
8 months passed, and although this graphene phone announced the first batch of 30,000 units, it has not been sold in the market.
, people can buy other graphene products that can be used to produce various types of graphene products. For example, the new third board listed company Shengquan Group has launched graphene socks and underwear on the market. According to the promotion of the company, they added biomass graphene "internal warm" fiber to the product, which is a new intelligent multifunctional composite fiber, "with activation of immune cells and protection. Ultraviolet rays, improving microcirculation, antibacterial and antibacterial, increasing heat and yang, etc., can also deodorize.
According to the company's promotion, they use plant straw to carbonize graphene and use graphene's superconductivity as the raw material for producing clothes. They plan to launch smart bras to measure subtle changes in the temperature of women's breasts through built-in sensors to effectively prevent tumors and breast cancer. They also plan to apply them to military uniforms - At present, these so-called graphene products are expensive, a pair of socks cost more than 50 yuan, a pair of underwear costs nearly 300 yuan, a graphene belt cost nearly 600 yuan, and a heating suit is sold for more than 1,700 yuan.
"In the past few years, when nanomaterials were hotly hyped, there were many concepts of 'nano+' in China, and this time the same is true for 'graphene'. Many graphene products are a scam. "Qilu, the head of the National 863 project, materials scientist, and professor at the School of Chemistry and Molecular Engineering, Peking University, said. Due to its contribution to new material energy, Qilu is also known as the main founder of the positive electrode materials of lithium cobalt oxide and lithium manganate battery in my country.
According to the reporter's understanding, graphene is currently divided into two types: single-atom thin film graphene and graphene powder. The former is mainly prepared by methane, acetylene and other carbon-containing gases, and is synthesized by chemical vapor deposition, which has nothing to do with graphite or straw.
Graphene powder is made of natural graphite , using concentrated acid and strong oxidizing agents for oxidation, and then reducing it by expansion heat treatment. As for graphene extracted from straw, it is said that 15 kilograms of graphene can be extracted by one kilogram of graphene, which is unheard of in the eyes of many industry insiders.
In addition to the obvious scam, graphene batteries and "graphene lithium batteries" that are keen on developing for many research institutes and enterprises are also accused of lying.
At present, the method of graphene application in the battery field is generally to add graphene materials to the positive and negative electrodes of lithium batteries. "This approach is obviously misleading. "Recently, an article about Tsinghua Energy Internet Researcher Liu Guanwei questioning "graphene battery" has been widely circulated online.
In this article titled "The Legendary "graphene battery" technology, is it a big lie?", Liu Guanwei gave a clear view from the beginning:
graphene battery" technology is close to non-existence. Graphene can only increase the charging and discharge rate in theory, but it has basically no help in the increase in capacity (energy) (people who expect "graphene battery" can solve the problem of mobile phone/electric vehicle battery life will be disappointed). Its gimmick is far more important than its practical value.
Liu Guanwei said that according to the classic electrochemical nomenclature, the lithium-ion battery used in general smartphones should be named "Lithium Cobalt Oxide-Graphite Battery".The reason why it is called a "lithium ion battery" is because lithium ions play a major role in it. "Strictly speaking, graphene is only used as an auxiliary function in the battery, so the battery that uses graphene cannot be directly called a 'graphene battery'."
In Liu Guanwei's view, only graphene is used as a "conductive additive" to lithium batteries. But even the application of "additive" is questioned.
Graphene can be used as a conductive agent to promote fast charging and discharging of lithium batteries, which can theoretically improve the rate performance, but if the dispersion process is not in place and the mixture is uneven, everything is a castle in the air; in addition, there are many materials that are good and cheap, and it is not necessary to use expensive graphene. "
The reporter noticed that Liu Guanwei's views were recognized by many senior industry experts such as Zhang Yuanbo, Qilu, Lu Hongbin, Professor of the Department of Polymer Sciences of Fudan University, and Yuan Guohui, Professor of Applied Chemistry, School of Chemical Engineering, Harbin Institute of Technology.
"Who can come up with data until now? Who made such a battery? "Qilu also believes that "the positive electrode and negative electrode of lithium batteries are both layered structures, so the migration from the positive electrode to the negative electrode can be formed under certain external conditions. Graphene is a single-layer carbon atom ring structure, which is determined by its own chemical and physical properties, and will not form a separate negative electrode material for lithium batteries. "
Many people are wasting their lives for this?
Regarding the doubts of industry experts, as the secretary-general of the "China Graphene Industry Technology Innovation Strategic Alliance", Li Yichun said: "Although there is controversy in the industry, scientific and technological innovation can happen. Many things that some experts think are impossible have been achieved, and some experts are too arbitrary, but we must have an open mind. "
As of now, it is impossible to know the true face of Qingdao's latest "world's leading graphene lithium battery". Huawei's reply is "There is research on graphene, but it will not be used commercially so quickly. "As the head of the "Graphene Super Electric Vehicle Battery" team of the Shanghai Institute of Silicate, Chinese Academy of Sciences, Huang Fuqiang's defense is that "Everyone will draw different conclusions from different angles, but the essence is the same. "
In fact, even Andre Gaim, who won the 2010 Nobel Prize for discovering graphene, does not understand the graphene that is currently crazily hyped in China. At the end of October 2015, when attending a graphene product exhibition held in Qingdao, Gaim clearly stated that "many application products, including graphene batteries, may be suspected of hype at present. "
On the day Gaim attended the meeting, the "2015 Global Graphene Industry Research Report" first published by China Graphene Industry Technology Innovation Strategic Alliance was also released. It shows that China not only ranked first in the world in the number of published papers studying graphene at the end of 2012, but also rose to the first place in the past three years.
However, Gaim also pointed out in an interview with Chinese media that many published graphene papers , Half of the research will be discarded. On the other hand, many patents, especially those produced from universities, 90% of which are of no value, 99% of them will eventually be invalidated, and maintaining these patents will also cost a lot of money, and many people are wasting their lives for this.
"Although China ranks first in the world in the number of graphene papers published, many scientific research institutes do not know what the industry really wants, and the disconnection between scientific research and application is prominent. "Kang Feiyu, dean of the Shenzhen Graduate School of Tsinghua University and an expert in carbon materials, publicly stated.
These doubts cannot allow Chinese graphene practitioners to stop. On January 16, Changzhou Xitaihu Science and Technology Industrial Park held a signing ceremony for the entry and entry of graphene projects, and 21 graphene projects collectively settled in Changzhou. Liu Zhifeng, secretary of the Party Working Committee of Changzhou Xitaihu Science and Technology Industrial Park, said that Changzhou's graphene industry is moving towards the goal of "building a characteristic industry of tens of billions of scale".
There are already many graphene industrial parks like Changzhou in China. According to reporters, a considerable scale of graphene industrial parks have been formed in Chongqing, Wuxi, Qingdao, Tangshan and other places.More graphene industrial parks are expected to bloom one after another in 2016.
In Changzhou, an insider of Two-dimensional Carbon Technology Co., Ltd. told reporters that they were established in Changzhou in 2011 and have grown to a scale of 200 people. In 2012, they produced the world's first capacitive graphene touch screen. In the past two years, they have also used the high thermal radiation efficiency of graphene films to develop some heatable clothing. Their research and development directions also include graphene composite materials, solar cells, wearable sensors, etc. However, he admitted that these products actually have little to do with graphene.
The capital market is the capital market earlier than industrial parks, research institutes, universities, and enterprises. Relevant data shows that a total of 60 listed companies in Shanghai and Shenzhen have deployed graphene business. In mid-August 2015, Del Home Furnishing, located in Jiangsu, announced its investment in projects such as graphene super lithium batteries. After drawing a blueprint of "annual revenue increased by 2.8 billion yuan and annual net profit increased by 450 million yuan", the company, which has built on the concept of "graphene battery", has a stock price as if it was on the Rockets, with an increase of 158.4% in more than two months.
The road to commercialization of the industry is long and unrestrained
"Now there are few graphene applications in China. There are actually not many companies that really make graphene. Many of them are companies that used to make carbon materials such as graphite. Even completely unrelated companies are under the banner of graphene, or hype stocks or seek national funds. There are almost no companies that really make graphene and can really make money." Zhu Hongwei, professor at the Micronano Mechanics Center of the School of Materials, Tsinghua University, said.
In Liu Guanwei's view, not only many graphenes in China are scams, but many foreign projects are also hyped. In his article questioning graphene batteries, Liu Guanwei said that "Spanish Graphenano company with graphene batteries" cannot find any valid information whether it is the three German automobile companies that claim to be cooperated with or on the Patent Office website.
So, why is the "king of all-purpose new materials" that is highly anticipated in such an embarrassing and controversial situation?
According to the reporter's understanding, there are three reasons: on the one hand, both at home and abroad, no industrial synthesis method is found to obtain large-area single crystal graphene in technology. On the other hand, the downstream graphene industrial chain has not yet been formed in the market, and the largest demand for graphene is only major scientific research institutes and laboratories, and there is no large amount of graphene invested in industrial operations.
As early as 2010, researchers from Sungkyunkwan University and Samsung Corporation in South Korea made a transparent bendable display consisting of multi-layer graphene and polyester sheet substrates. At that time, Hong Bingxi, a corresponding author of the paper and professor at Sung Kyoto University, proposed that their method could be used to manufacture graphene-based solar cells, touch sensors and flat panel displays. But he also admitted at the time that it was too early to manufacture and commercialize on a large scale - five years later, Hong Byung-hee's method was still in the laboratories of Samsung and Sungkyunkwan University in South Korea.
The last aspect is the cost of graphene preparation. Due to the inability to mass production, the cost of graphene preparation has always remained high, and the high cost has also hindered the pace of industrialization in the downstream market. Previously, the price of graphene was as high as 5,000 yuan per gram, which was more than 10 times more expensive than gold. "Things that are not astonishingly beautiful than gold. A few grams of graphene powder are worth hundreds of thousands of yuan. When we fly, we ship them separately, for fear of being confiscated by security checks." A startup company doing graphene research once described it like this.
In Canada, Grafoid and the National University of Singapore established the world's largest graphene research center (NUS), and launched a new production base in Ontario in 2014. This base of about 20,000 square meters mainly produces graphene powder. At that time, the company's head said they could produce high-quality graphene at a low price. However, more than a year has passed, and there is no new news about this base.
Therefore, the main thing that really hinders the large-scale application of graphene is the technical problem. Among them, the consistency of low-cost, large-scale, and high-quality graphene and the development of repeatable synthesis methods are the biggest difficulties.
An interesting thing that people are familiar with is that Andre Gaim obtained graphene with transparent tape.But what people don’t know is that the graphene obtained in this method is very small in size, generally between 10 microns and 100 microns, and there are shortcomings in low yield and high cost, which cannot meet the requirements of industrialization and large-scale production.
Later, graphite oxide reduction method is one of the most commonly used methods for preparing graphene. However, this method mainly produces graphene powder, and it has many defects, poor electrical and mechanical properties, and requires concentrated sulfuric acid to oxide graphite. The treatment of waste liquid in the industry is a difficult problem.
After that, people thought that graphite was not necessary to prepare graphene, they just needed to try to make carbon atoms form a thin film. Chemical vapor deposition (CVD) came into being, which is to introduce gases such as ethylene or acetylene into a reaction chamber, allowing these gases to decompose at high temperatures. After cooling, carbon atoms are deposited on the substrate surface to form graphene. Although CVD can meet the requirements of large-area and high-quality graphene on a large scale, the problem is that due to its disadvantages such as high cost and complex process, the application of this method in graphene preparation is limited.
Due to the huge differences in preparation methods, the prices between graphene powder and CVD film are also thousands of times different. For example, 1 gram of graphene powder costs less than 10 yuan, while 1 square meter of graphene film costs tens to hundreds of yuan, and its weight is actually less than 1 mg.
There is another main method - solvent peeling method. Since the entire liquid phase peeling process does not introduce any defects on the surface of graphene, it provides broad application prospects for its application in microelectronics, multifunctional composite materials and other fields, the disadvantage is that its yield is also very low.
Therefore, from the perspective of application, graphene is currently in the storytelling stage at home and abroad. "In addition, the current industrial standards such as size, uniformity and reliability of graphene in consumer electronic products have not been determined, so the actual use of graphene in consumer electronic products has not been shown." Zhu Hongwei believes that graphene can currently make small-scale devices in the laboratory, but the quality of mass production and integration cannot be guaranteed. "At least there is no hope yet."
In fact, even Gaim himself has reservations about the current commercialization method of graphene. Gaim believes that graphene is an introduction, which has driven the development of a wider range of two-dimensional materials. But for graphene, from the perspective of physics, it has reached a bottleneck. Unless there is a greater breakthrough in the future, it is difficult to make further improvements.
Major events in the development of graphene
2004: Andrei Geim and Konstantin Novosholov obtained graphene by a simple mechanical peeling method of tape. The two won the 2010 Nobel Prize in Physics.
December 2009: Fujitsu Institute in Japan announced the successful use of graphene to make transistors.
February 2010: IBM develops graphene FET (field effect transistor).
June 2010: Samsung and Sumio Iijima, a professor at Sungkyunkwan University in South Korea, used graphene to make flexible transparent electrodes.
January 2012: Jiangnan Graphene Research Institute and two-dimensional carbon companies have claimed to jointly develop the world's first graphene capacitor touch screen for mobile phones.
August 2012: Nokia disclosed that its R&D department is studying graphene photoelectric sensors.
September 2012: Sony claims to develop a roll-to-roll process to make graphene.
January 2013: The Chongqing Institute of the Chinese Academy of Sciences announced the development of the first 15-inch single-layer graphene in China.
May 2013: Jiangsu Changzhou Two-dimensional Carbon Technology Co., Ltd. said that the world's largest graphene transparent conductive film production line has officially started production, with an annual production capacity of 30,000 square meters.
November 2013: Changzhou Sixth Element Materials Technology Co., Ltd. produces 100 tons of graphene oxide and graphene powder production line to be put into production.
April 2014: Samsung claims to develop the technology to form single crystal graphene on semiconductor wafers.
July 2014: IBM announced that it will invest US$3 billion in graphene development over the next five years.
2015: "Made in China 2025" was officially promulgated by the State Council, and once again put graphene as a new energy source on the agenda.
Related link: The past and present life of the king of new materials
Carbon is one of the most important elements. It has unique properties and is the basis of all life on earth. Pure carbon can be hard diamonds or soft graphite.
Because this material is made from graphite and contains the basic characteristic of olefinic substances - double bonds between carbon atoms, it is called graphene. In fact, graphene exists in nature, but it is difficult to peel off the single-layer structure. Graphene layer by layer is graphite, and graphite 1 mm thick contains about 3 million layers of graphene. The adhesion between layers is loose and easy to slide, making the graphite very soft and easy to peel off. The pencil gently strokes the paper, and the traces left may be several layers of graphene.
Scientists conducted theoretical research on graphene-like structures in the 1940s, but for a long time since then, efforts to make monolayer graphene have not been successful. Some people believe that such two-dimensional materials cannot exist stably at room temperature. In October 2004, a paper published in the American journal Science overturned this perception. Andrei Heim and Konstantin Novosholov, who worked at the University of Manchester in the UK, completed their "magic" with ordinary tape.
They use tape to stick flakes from the graphite, which still contain many layers of graphene. But after repeated sticking on 10 to 20 times, the flakes become thinner and thinner, eventually producing some single-layer graphene. This method, which seems very simple and not high-tech at all, is not their first creation. Someone tried it before, but failed to identify a single layer of graphene.
Heim and Novosholov placed the peeled flakes on the silicon oxide substrate. The interference effect of light makes the flakes appear colorful stripes under the microscope, just like the effect of an oil film on the water surface. Using this effect, they observed a monolayer of graphene. In this way, the first two-dimensional crystal material officially appeared. Afterwards, some other two-dimensional materials, such as two-dimensional crystals of boron nitride and molybdenum disulfide, were prepared.
Graphene has special significance for basic research in physics. It enables some quantum effects that can only be discussed on paper before can be verified through experiments, such as electronics being ignored and ghostly traveling. But what is more interesting is its many "extreme" application prospects. However, even researchers who have won the Nobel Prize for this two-dimensional carbon will bring to the human world, cannot predict what kind of changes this two-dimensional carbon will bring to the human world.
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