War between solid lithium-ion battery industries

In December 2016, Energy Energy Science(Energy and Environmental Science), one of Britain's leading academic journals, published a paper entitled Alternatestryforasaferchareablebattery.

A team led by Professor Yuehan·gudinafu of the Cochrane Institute of Technology at the University of Texas in Austin has developed a low-cost, fast-charging all-solid battery that addresses many of the pain points currently plaguing the battery industry, the paper said. It has many advantages such as not easy to burn, high volume energy density, long cycle life, and fast charging and discharging speed. For example, this type of battery has only minimal loss after 1200 recharge cycles and can ensure normal operation at a temperature range of 60 °C to -20 °C.

As soon as this article was published, it immediately caused an uproar in the energy, chemistry, physics, and entire battery industries around the world.

There are two reasons:

1, the fourth author of the article, Professor Gudinafu's special identity: He is the "father of lithium batteries", the inventor of lithium rechargeable batteries, and the champion of the global battery industry. He is called the current scientific community "towering" level. The 95-year-old professor has so far been active in the forefront of teaching and research, and as a top expert in the battery field, every move has attracted the attention of the industry.

2, Gudinafu's research results turned out to be wrong! Its theoretical basis even violates the most basic first law of thermodynamics! But strangely, all the people in the industry, out of extreme respect for Gudinafu, chose to keep a clear and confused attitude and collectively chose to remain silent when they knew it.

Silence was broken a year later. Danielle Steingart, a researcher at Princeton University in the United States, also published an article entitled "Common" in Energy and Environmental Science, which openly questioned the results of the old-timer's research. And tit-for-tat proposed that the reaction mechanism proposed by Gudinafu is wrong, "from the thermodynamic point of view this is obviously impossible."

The first bird called, in exchange for a sound in the academic community. Gudinafu's position in the lithium industry can be said to be unmatched. To this end, the grandfather is only a subtle "We have not violated the first law of thermodynamics" to show his response.

The elderly man, who developed the world's first commercially rechargeable lithium-ion battery in partnership with Sony in 1991, helped drive the social electronic revolution in humans and eventually died in the age of mackerel.

According to a person close to the truth, the old man who has lived a lifetime of fame and fortune was first author of the controversial paper, M. H. Braga(a female scholar from Portugal).

The above academic debate is only the tip of the iceberg in the lithium battery industry today. In fact, the academic battle is far less exciting than the war in commercial reality.

Since its inception, practitioners in the rechargeable lithium-ion battery industry, considered to be as important as the transistor invention, have faced two major challenges in the past, present and future: safety and energy density.

For many years, the main application of lithium batteries was consumer electronics. However, this situation began to reverse in 2013. With the rapid rise of new energy vehicles around the world, the power battery industry suddenly became hot and full of temptation.

In the future, new energy vehicles will be the most important area of lithium battery application.

Analysis has predicted that the global power lithium battery market will continue to grow rapidly. It is expected that by 2022, total demand and market size will reach 54.9 GWh and 26.7 billion U.S. dollars, respectively, and the annual average growth rate in the next decade will reach 37.0 and 31.6 respectively.

In China, 60.5 billion yuan of power cells were sold in 2016 alone, and by 2020 the figure will be another 3. If the average price of 1.5-yuan / Wh is measured, the market size of the new energy vehicle power battery in China will reach 336.3 billion yuan in the next five years.

Forbes expects the global market for power cells to reach $240 billion in 20 years.

However, the lithium iron phosphate batteries and lithium ternary batteries that enjoyed dividends in this round of new energy vehicles have gradually revealed embarrassment. Due to the influence of the existing system architecture and key positive materials, the energy density of the lithium battery of the existing system is basically difficult to break through 300 W/kg. Among them, the single energy density of lithium iron phosphate batteries is difficult to exceed 140Wh / kg, and the single energy density of large-scale triplet lithium batteries is up to 220Wh / kg. The upper limit in the laboratory is 300Wh / kg.

In the future, the main contradiction in the development of the new energy automotive industry will focus on the contradiction between people's increasing aspiration for increasing mileage and the slow growth of power cell energy density.

In China, the government has set the technical target for power batteries in the next few years to achieve a single energy density of 300 W/kg ~ 400 W/kg from 2020 to 202. Obviously, whether it is lithium iron phosphate or lithium ternary, it is difficult to do so.

In the United States, the U.S. Department of Energy has established a new generation of battery research and development organization, the Energy Storage Joint Research Center(JCESR). JCESR said with ambition that "like the Manhattan project, it will concentrate on talent and funds to develop batteries with a energy density of five times and a price of 1/5 within five years."

The traditional lithium battery technology(lithium iron phosphate and ternary) is subject to liquid electrolytes and is difficult to be compatible with metal lithium negative poles and newly developed high-potential positive electrode materials, thus causing bottlenecks in the rise of energy density. In terms of safety, it will also cause problems such as short-circuit ignition, ion concentration difference, internal resistance of the battery, and continuous consumption of electrode materials.

So at this time, as the "next-generation lithium battery technology," solid-state batteries have high Ionic conductivity and mechanical strength, wide electrochemical Windows, and working temperature ranges. It has become an ideal object with high energy density, strong circulation, high security, and short charging time.

The in-sight solid-state batteries, while seemingly reliable, still have many technical challenges to overcome and will take some time for mass production.

But it is still difficult to extinguish the enthusiasm of hundreds of institutions around the world to rush into solid-state batteries. These include traditional car giants, new car makers, auto parts giants, battery-making companies and upstream raw materials companies, as well as academic research institutes, government-backed research institutes, and even military-funded mysterious institutions.

In any case, hundreds of top experts in physics, chemistry, and electricity around the world, supported by tens of millions of dollars in research and development funds, have surrounded the strategic commanding height of solid-state batteries, from technology development to commercial production. Mass production, a battle began.

Japan

Headed by Toyota, Japan is ahead of the rest of the world in solid-state batteries, with companies including Honda and Panasonic claiming to focus on the development of next-generation batteries.

However, special attention should be paid to the fact that because of the closed thinking of the Japanese island countries, they are reluctant to share their own research results and choose to maximize the commercial benefits of their own technology routes(for example, the time window for the opening of fuel cell patents is only a few years. Just enough for other countries and companies to develop products, and they will come to harvest when they are mass-produced.)

With the "historical lessons" in this regard, China will generally choose not to follow the Japanese route, such as the mobile communication system and the HEV technical route. China has clearly demonstrated its intention to avoid the Japanese technical route.

Toyota: a fan of solid-state batteries

In July, the Japanese media reported heavy news that Toyota planned to launch a mass-produced solid-state battery car in 2022. Subsequently, a Toyota spokesman said there would be no immediate comment on the matter.

In December, five months later, Toyota suddenly announced that it plans to launch 10 electric vehicles by 2020 and commercialize the next generation of solid-state batteries. The news was later confirmed by Toyota's material engineering executive Shigekizuki: Toyota will commercialize all-solid batteries by 2020.

This means that Toyota has unilaterally commercialized solid-state batteries two years earlier.

This is quite a bold move, especially for the cautious and conservative Toyota. It is even more incredible.

According to the industry, with Toyota's past personality, if it is optimistic about the solid-state battery route, it basically means that Toyota has overcome most of the difficulties in this technology route and is relatively confident of mass production.

In fact, at least a dozen or 20 years ago, Toyota had secretly organized a team of hundreds of top talents to develop solid-state batteries and air batteries. This team includes expert teams such as Tianjing, Yukio Otani, Yukio Ueno, Hamanishi, Nakamoto Bowen, Laihao, Masahiro Kamiya, Bulaien·haideng, Legaier, Dengken·shimisi, and Christopher Lee. The team quietly developed In more than a decade, as many as 30 patents have been filed for Toyota(Toyota has so far led the way in the number of patents on solid-state batteries).

Due to commercial secrecy, the outside world is not aware of Toyota's specific progress in this area. Although Toyota has been low-key and mysterious, the industry still recognizes that its technology progress should be ranked first in the world.

According to the electrolyte form, solid-state batteries are divided into all-solid and quasi-solid States(a compromise route between solid and liquid). According to the material of the electrolyte, the whole solid state is divided into oxides, sulphides, and polymers, and Toyota takes the sulphide material route in the whole solid state.

What is currently known is that Toyota has not only obtained patents for solid electrolyte materials, solid cell manufacturing technology, etc., but also developed a complete set of technical routes and recovery processes for the recovery of positive and sulphide solid electrolyte materials.

In 2010, Toyota officially introduced sulphide solid-state batteries. By 2014, the energy density of solid-state batteries in its laboratory has reached 400 W/kg.

Europe

Europe's developed countries, which have long held the top of the global industrial chain and made big profits, have long regarded the lithium battery industry as a low-value-added industry(a low-end industry that should be done by Asians), without paying enough attention to the battery industry. This has led to the lack of large-scale lithium power companies in Europe today, and the lithium power industry chain has not been able to establish it(however, Belgium's Umicore beauty company has always been the world's leading material giant, which is an exception).

So, in this round of power batteries, the fate of Europe was already doomed. But as a gathering place for traditional car powers and giants, European giants can only catch up. For example, Volkswagen plans to invest 50 billion euros in the development of solid-state batteries. BMW also chose to cooperate with the US battery manufacturer Solid Power to develop a new generation of solid-state battery technology and set the production time to 2026.

The biggest feature of Europe's solid battery landscape is that it lacks the support of a weak local industrial chain, so most companies have to work with places in Asia or the United States, or simply start buying and buying models.

French Bolloré.

In Europe, BatScap, a subsidiary under the control of the French family Bolloré(Boluolei) family, is recognized in the world as a representative of a deep layout in the solid state battery field, but unlike Toyota, BatScap chooses a full-solid polymer technology route. BatScap's solid-state battery is also known as a metallic lithium polymer battery because the negative electrode material uses metallic lithium and the electrolyte uses a polymer film.

The biggest advantage of BatScap's batteries is that it has been subjected to field testing of mass production and markets, thanks to the long-term layout of the Boloré Group, which was established in 1822 and does not include investment in transportation, transportation, and energy. This allows BatScap's battery to land quickly.

As early as October 2011, Bolloré began to use the self-developed electric vehicle "Bluecar" and the electric bus "Bluebus" to provide auto sharing services "Aurelib" in Paris, France and its suburbs. Over the past few years, a total of 3,000 BatSap solid-state batteries have been installed with 30kWh, and 900 service stations and 4500 charging devices have been set up in the area. The cumulative number of users is nearly 200,000, and the number of daily utilization is approximately 18,000. As a result, a large amount of data and operational experience has been accumulated.

However, it should be noted in particular that Bolloré has become the first company to commercialize the scale of solid state batteries, but the actual output energy density is still low, and its energy density is only 100Wh / kg, which is far below its theoretical level.

America

The United States and Europe share the same problem, but things are slightly better. There is no possibility of a revival in Europe's power cell industry, but the US has come to realize earlier that its local lithium-ion industry is very weak, and it has made an early layout.

For example, in 2008, the U.S. government changed its strategic direction from hydrogen energy and fuel cells to lithium batteries. On the one hand, it established as many as hundreds of battery-related venture companies. On the other hand, it actively expanded and deployed the global lithium industry chain.

Sakti3: One of the Big Three

The United States Sakti3 is recognized in the industry as one of the three giants that can compete with Japan's Toyota and Europe's Bolloré for higher technological maturity and deeper technology development of solid-state batteries. It is also the third technology route for solid-state batteries, the oxide electrolyte material route in the whole solid state.

The oxide technical route is the most difficult of the three.

In 2008, Mali·saisiteli founded Sakti3. It is worth mentioning that the former professor of engineering at the University of Michigan is still a somewhat sentimental person. This can be seen from her name for the new company: Sakti means Sanskrit "energy" and 3 represents the number of atoms of lithium.

Sakti3's best asset may be founder Saisiteli, a strong woman who has worked more than 100 hours a week for 20 years studying battery technology and has more than 70 patents.

Sakti3 claims to have developed a solid-state battery with an energy density of 1,000 W/kg, and said that after commercial mass production in the future, the cost is only 20 % of the current lithium battery, which can control the cost of electric vehicles equipped with its battery at 25,000 US dollars.

After its founding, the company in Ann Arbor, Michigan, received a total of 30 million U.S. dollars in investment from General Motors, Japanese industrial giant Ito Merchants, the Michigan government, and venture capital companies. However, it was eventually acquired by British tycoon Zhanmusi·daisen, the inventor of Dyson vacuum cleaner and hairdryer, in 2015.

Dyson's acquisition of Sakti3 is clearly more ambitious than being able to access the building and use Sakti3's solid-state battery first on hair dryers and vacuum cleaners. Dyson has made it clear that he has invested $1.4 billion in building a factory that churns out solid-state batteries in August with the ultimate aim of creating a "Dyson" brand of electric car.

The biggest problem with Sakti3 is its manufacturing technology using thin film sedimentation technology. In short, the thin film is piled up in layers. This results in high costs, and the likelihood of reducing costs in the future is not too great.

Seeo: Back to Bosch to enjoy the cool

The acquisition of Seeo in 2016 by German auto parts giant Bosch brought the US solid state battery startup into the limelight.

In 2007, Seeo was officially established as the famous U.S. Department of Energy Lawrence Berkeley National Laboratory startup project in the solid state battery field. Seeo was born with a gold spoon because he is the only battery company authorized by Lawrence Berkeley National Laboratory to have a core patent. Just one thing to know about the strength of the Lawrence Berkeley National Laboratory: 13 scientists and organizations involved in the development of America's first atomic and hydrogen bombs won Nobel prizes.

Seeo is based on a battery technology invented by chemical engineer Hani·aituoni at the Lawrence Berkeley National Laboratory. Aituoni said he invented the solid battery as the size of a briefcase, storing two to three times the amount of electricity per unit weight of today's liquid lithium batteries.

Aituoni showed Seeo's core competitiveness in this field. Seeo's dry polymer thin film solid-state cell has already taken out a sample battery battery energy density of 130-150Wh / kg, which is obviously not a very good number. However, it claims that this figure can be raised to 300 W/kg this year.

Seeo also became the darling of the capital markets at the beginning of its creation. It has experienced several rounds of financing. The investors even included Google and Samsung until it was acquired by Bosch last year.

Here's a little bit more about Bosch's placement in solid-state batteries, as the world's largest auto parts giant has in recent years seen a surge in new energy vehicles.

After the acquisition of Seeo, Bosch established a new factory with Japan's GSYUASA Battery Company and Mitsubishi Heavy Industries. The main product is also solid-state batteries. Among them, GSYUASA Battery Company is a merger of two Japanese battery giants GS(Unified) and YUASA(Yuasa), and its strength can not be underestimated.

The question is, how can China, which has placed the new energy industry at the forefront of national economy and people's livelihood development, be willing to be a spectator when Europe, the United States and Japan are all struggling to grab strategic heights in the solid state battery field.

There has been a research on lithium battery technology for many years. Chinese professors who teach at universities in the United States have elaborated the following views on the evaluation of the contract car, which made the author burst into national pride in the moment. As follows:

1, in the United States, the main research and development force in the battery front-end technology, including solid-state batteries, is still dominated by Chinese;

Although the United States has a large number of research and development institutions for all types of lithium batteries and research and development capabilities are relatively strong, the professor said that the industry is often able to deeply appreciate that there is still a gap between China and China, and even the gap is still widening. This is mainly reflected in the entire battery industry chain in the United States is far less sound and perfect than China.

The world's most robust and developed power cell industry chain is concentrated in China, providing the most fertile soil for the development of power cell technology.

China

The booming new energy industry offers the best historical opportunity for the rise of China's domestic power battery industry. Just as China has the opportunity to overtake the curve in the next era of the automotive industry, China's power battery technology will most likely break the blockade from abroad. Become the decisive force leading the development of cutting-edge technology.

In China, both national research institutes and battery companies have added solid battery power to seize the future power battery track.

Li Feng Li: The first to eat crabs

On August 18 this year, a message was released that almost shocked the entire domestic lithium battery industry. Solid state battery expert, Dr. Xuxiaoxiong, former researcher of the Institute of Materials of the Chinese Academy of Sciences, reached a strategic cooperation agreement with Lifeng Lithium, a listed company in China, to promote the testing of solid state battery technology in Ningbo. The goal is to achieve the industrialization of solid state batteries within three years.

What I want to say is that Xuxiaoxiong, as the head of the "All-solid Lithium-ion Storage energy battery" project in the "Twelfth Five-Year Plan" new energy field of the Ministry of Science and Technology, has long been committed to the development of solid-state battery technology. Public information shows that It has so far applied for more than 30 patents(6 international patents and 27 Chinese patents), of which 11 patents have been authorized.

He and other members of the Ningbo Institute of Materials Technology and Engineering of the Chinese Academy of Sciences, Several members, including Yaoxiayin, Ten Thousand Diviels, Yangjing, Huangzhen, Yaoxiayin, Zhaofengdong, Zhu Jun, etc., have developed composite cathode materials for all-solid sodium batteries, all-solid sodium battery electrolytes, and a all-solid sodium battery. Preparation methods and theories And ...

Four months after Xuxiaoxiong's team issued a cooperation agreement with Li Feng, Li Feng Li announced on December 5 that it will set up a wholly-owned subsidiary, Zhejiang Feng Li, with its own capital of no more than 250 million yuan. Investment in the construction of a first-generation solid lithium battery R&D pilot production line with an annual output of billions of watt-hours, The project construction period is 2 years.

The so-called test is the test before the product is officially put into production. It is a smaller scale test of the product before mass production. Before the company determines a project, after conducting laboratory tests, small tests, and medium tests, it can basically be mass-produced.

The Li Feng industry dared to invest 250 million yuan and let Xuxiaoxiong be the legal representative of the company, which to a large extent means that the solid state battery technology of the Xuxiaoxiong team has basically matured.

According to calculations, the energy density of the first-generation solid lithium battery core produced by the Lifeng lithium industry can reach 240Wh / kg. According to the estimate of 500 kg battery pack for bicycles, the power of 80KWh can achieve 480 km of endurance, and The maximum amount of electricity after the thousand cycles is still 90 <UNK>, Charging takes only 12 minutes to fill.

Chenliquan: Forerunner

Chenliquan, an academician of the Chinese Academy of Engineering, has always been an active promoter of domestic solid-state batteries. He believes that only all-solid batteries can be qualified to further increase the battery energy density to 500Wh / kg of historical tasks, and calls for the start of all-solid batteries as soon as possible. R&D industrialization work.

In 1978, Chenliquan first initiated and advocated the research of solid metal lithium batteries and related basic research on solid ions; In 1980, China's first laboratory in the field of solid-state batteries was established, the Solid Ion Laboratory of the Institute of Physics of the Chinese Academy of Sciences; Until 2000, the research focus of the Institute of Physics of the Chinese Academy of Sciences shifted to nanocrystagnetism, and at the same time began to vigorously study the key technical problems of conquering solid-state batteries; In 2016, Beijing Weilan New Energy Technology Co., Ltd., which focuses on research and development of solid state batteries, was established.

In addition to Chenliquan, Beijing Wei Lan also includes a group of top domestic experts, including Chenliquan's old partner Lihong, a researcher at the Institute of Physics, Chinese Academy of Sciences. It has participated in the research and development of several national-level projects including the development of silicon-based negative electrode materials for high-energy density lithium-ion batteries, lithium metal and solid-state battery technology research.

At present, Beijing Weilan has developed and mastered many key technologies in the field of solid-state battery technology. Including metal lithium surface treatment, in situ formation of SEI membrane technology, solid electrolyte, lithium ion fast conductor preparation technology and Gaodianya battery integration technology, ceramic membrane optimization technology and collection fluid solution.

Ningde era: active reserve preparation

In December, Guoyongsheng, the R&D manager of the Ningde era, said at an event that the Ningde era has begun to actively deploy the next generation of power battery technology, which is more focused on solid lithium batteries, but also from the perspective of a battery manufacturing company. A focus of research and development has been placed on the manufacturing process of solid-state batteries.

As a domestic power battery giant, the Ningde era has been laid out in the development of solid state battery reserves. Its solution in solid state batteries is to do some protection for positive electrode materials, which can improve compatibility.

At the same time, the manufacturing process is facing considerable challenges due to the air sensitivity of sulphides. The entire manufacturing process of solid-state batteries is completely different from that of traditional lithium batteries. Therefore, during the development of solid-state batteries in the Ningde era, the manufacturing of solid-state batteries was synchronized with the development of production equipment and processes.

As far as is currently known, the Ningde era has currently designed and manufactured polymer cores with a capacity of 325 mAh, and has demonstrated better high-temperature cycle performance: the remaining 82 <UNK> above the 300 cycle.

The page contains the contents of the machine translation.