A simple history, read lithium battery spring and autumn!

A simple history, read lithium battery spring and autumn!

The history of lithium-ion batteries can be traced back to the first commercial lithium-ion battery launched in Sony in 1991. The LI / MOS2 battery launched by Molienergy has occurred because of the excellent energy density, but due to design defects. There are many fire events, so you have to conduct a large-scale recall, and finally lead to Molienergy.

. At that time, Sony was also trying to develop a Li / MnO2 battery, but due to the defects of the LI metal negative itself, this technical approach was destined to fail, while the LI metal negative studies were engaged in the Sony Company, including Exxon Group ( LI / TIS2) and Bell Lab (Li / NBSE3), etc. are the development of lithium metal negative electrode batteries, but they are on the security problem of Li metal negatives.

. The lithium metal negative electrode can attract so much attention, is due to its advantages such as high-specific capacity (3860mAh / g), good conductivity and low potential (-3.04VVS standard hydrogen electrode), if lithium metal negative electrode is used in the original battery It is indeed an excellent negative electrode material, but if the disadvantage of the application on the secondary battery is also leak, the growing Li dendrite will not only cause the electrode volume expansion, but the efficiency of Kurun is low, Li Zhi in severe cases The crystal even pierces the diaphragm between the positive and negative poles, causing a short circuit between the positive and negative poles, so early development of Li metal negative electrode batteries often suddenly fires explosion in the case of unpredictable, like a no display Time bomb.

Since there is a safety problem that the Li metal negative electrode is that it seems to be overcome, Jiye, who is working in Asahi, turns his eyes to graphite materials, different metal lithium negative electrodes, and Li is embedded in graphite negative surface, thereby preventing metal Li Generation, completely solve the problem of li dendrites growth. However, the application of graphite material is not a fan, and the graphite material is embedded in the electrolytic solution together into graphite while embedding Li +, resulting in the peeling of the graphite layer, and therefore the early Bell laboratory on graphite materials It is not successful until Ji Ni, FONG, VONSACKEN and DAHN, etc., it is found that low-temperature graphite (such as petroleum coke) can inhibit this co-embedded reaction, which lays the foundation for the development of modern lithium-ion batteries, but due to Ji Na I published relevant patents earlier, and the system used is also closer to the current lithium-ion battery.

Therefore, it is generally believed that Yoshino is a father of lithium-ion battery.. In the patented patented patented in Jiye, the negative electrode adopts low temperature graphite (oil-focus).

The positive electrode uses lithium-eaten GooNough, LicoO2 materials (slightly treated), the prototype of modern lithium-ion batteries is formally born. Since Li + is embedded in the positive and negative poles, the lithium ion battery is also referred to as “rocked” battery..

The concept of “rocking chair” battery was earliered by Armand et al. In the 1970s, the reaction is embedded and out of the reaction between the positive and negative electrode materials different from the potential, and the early tread is not suitable for positive and negative materials. Therefore, most of the battery voltage is less than 2V, not attracting enough attention until Ji Naki will combine the high voltage characteristics of Goodenough development, and the low-temperature graphite material, this battery design concept is really carried forward.

. After the publication of Yoshino, Xuhua became an AT Battery Group for lithium-ion battery production. At present, AT has become a subsidiary of Toshiba.

. Although Yoshino has completed the development of most lithium-ion battery materials, how to commercialize, especially how and new nickel-cadmium and new inventions of nickel-based cells at the time are still a complex work..

At that time, Sony was the leadership company in 3C consumer electronics, and the development of alkali metal raw batteries was carried out in 1985, and the secondary battery will be turned from the original Ni-CD battery. Daddy in the consumer electronics, Sony has a strong desire to develop a new market that has never had passed, which is an important reason for Sony finally succeed..

In the early days, due to the good anti-solvent of low temperature coke, although the capacity is relatively low, it is still widely used in the first-generation lithium ion battery. In the second generation lithium ion battery, low temperature coke is more capacity. High and better performance of hard carbon, but hard carbon still has a lot of problems, so in the third-generation lithium-ion battery has adopted the current intermediate phase carbon microspheres (MCMB).

In terms of positive electrode materials, the Licoo2 developed by Godenough is the most successful positive material until it is still widely used in the construction of consumer electronics. It has gradually replaced in the field of power lithium battery, and lithium iron phosphate materials in recent years. Traditional licoo2 materials.

Early PVDF in terms of binder is poor in the positive side, and there is a certain effect on the lithium ion battery until the company introduces carboxylic acid anhydride in PVDF, significantly improved PVDF on Al foil surface Adhesiveness. Although the lithium-ion battery case does not look at, the success of the lithium-ion battery still has a crucial use, and the early Sony believes that there is a trace HF in the electrolyte, so the stainless steel is selected as the outer casing of the lithium ion battery, but in the application It is found that the housing impedance of stainless steel is too large, so the solution to the surface of the iron shell surface is selected..

After Sony’s unremitting efforts, the first commercial lithium-ion battery in 1991 successfully pushed the market, Sony’s first battery volume energy density was 200Wh / L, and the weight energy density was 80Wh / L (4.1V), in the first After the second-generation lithium ion battery uses a hard carbon negative electrode material, the energy density of the battery is raised to 295WH / L and 120WH / kg (4.2V), and the energy density of the third generation of lithium ion batteries after the negative electrode is used to reach 400W / L.

And 155WH / kg, Sony has become a leader in the field of lithium-ion batteries at that time, but fierce competition from other manufacturers makes Sony’s lithium-ion battery business constantly shrinks, and finally transfer battery service to Village Film Group.. Today, the lithium-ion battery has been developed for 28 years, which is not limited to the traditional 3C consumer electronic field, our electric tools, electric vehicles, etc.

, many areas, and lithium-ion batteries, while lithium-ion batteries The size is no longer limited to 18650, with more sizes and structures. Maximum change is on battery performance, we use traditional 18650 batteries as an example, the energy type 18650 battery capacity launched by Panasonic and other companies can reach 3.3ah, energy density can reach 240Wh / kg or more, compared to the initial generation The energy density of the lithium ion battery has been increased by more than 3 times.

Lithium-ion battery energy density is largely benefited from the application of high-capacity silicon carbon material and high nickel-based material, compared to conventional graphite materials, the specific capacity of silicon materials can reach 3000 mAh / g above, and graphite Ten times, small amount of silicon material, can significantly increase the specific capacity of the negative electrode. Application of Trimetic Material (LiniXmnyco1-x-YO2 or LINI0.80CO0.

15Al0.0.05) is another flush for lithium-ion battery energy density, and the specific capacity of the ternary material can be up to 190mAh / g above, than LCO.

Material increases more than 30%. Data from Pillot shows that although the demand for LCO is still 45,000 tons, it has shown a downward trend, but the NCM material has reached 35,000 tons, still ongoing up, NCA material is 0.9 million tons, high-speed rise condition.

Lithium-ion batteries have put forward higher requirements for the large-scale application of the power lithium battery in recent years, and therefore, various techniques for improving lithium ion battery safety, such as coating diaphragm technology, and positive coating technology Also help reduce short-circuit risks in batteries due to internal defects of lithium-ion batteries, and improve the thermal stability of lithium ion batteries, especially diaphragm coating technology, has been widely used in recent years, so compared to the initial lithium-ion battery The current lithium-ion battery has also been greatly improved.. The rise of the lithium-ion battery is from the safety problem that the metal lithium ion battery cannot be overcome.

Under the efforts of the old generation of lithium-e-commerce, the application of the graphite negative electrode is successfully solved by the application of graphite negative electrode, Sony’s company The development of innovative spirit successfully enabled lithium-ion batteries to realize commercialization, laying and exporting for the development of modern lithium-ion batteries, after nearly 30 years of development, under the unremitting efforts of lithium eco, either in energy density, power Performance, or a very huge increase in the initial lithium-ion battery products, while the application field of lithium-ion batteries is also expanded from the first 3C consumer electronics field, and it has expanded today’s power lithium batteries and storage. The field, I believe that under the efforts of the majority of lithium-ion batteries, the lithium-ion battery can also create brilliant in the next decade.

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