The first commercial lithium-ion battery launched by Sony in 1991, Sony was also trying to develop a Li/MnO2 battery, but this technical solution was destined to end in failure due to the defects of the Li metal cathode itself, and Sony was not the only one engaged in Li metal cathode research at that time, including Exxon Group (Li/TiS2) and Bell Labs (Li/NbSe3). The top international research groups, including Exxon Group (Li/TiS2) and Bell Labs (Li/NbSe3), were all working on the development of Li-metal cathode batteries, but they all faltered on the safety of Li-metal cathodes.
The reason why Li metal cathode can attract so much attention is precisely because of its high specific capacity (3860mAh/g), good electrical conductivity and low potential (-3.04V vs. standard hydrogen electrode), etc. Li metal cathode is indeed an excellent cathode material when applied to primary batteries, but its disadvantages are exposed when applied to secondary batteries. In serious cases, Li dendrites will even pierce the diaphragm between the positive and negative electrodes, causing a short circuit between the positive and negative electrodes, so the Li metal negative electrode battery developed in the early stage often suddenly fires and explodes under unpredictable circumstances, just like a time bomb that does not show time.
Since the Li metal negative electrode had a safety problem that seemed insurmountable at that time, Aki Yoshino, who was working at Asahi Kasei, turned his attention to graphite material. Unlike lithium metal negative electrode, Li would be embedded on the surface of graphite negative electrode, thus avoiding the generation of metallic Li and solving the problem of Li dendrite growth. However, the application of graphite materials is not smooth, as the graphite material embeds Li+ and also embeds solvent molecules in the electrolyte into the graphite, resulting in the flaking of the graphite layer, so the early research on graphite materials at Bell Labs was not successful until Akira Yoshino, Fong, Von Sacken and Dahn found that low temperature graphite (e.g. petroleum coke) could inhibit this co-embedding reaction well. However, since Akira Yoshino published his patent earlier and used a system that is closer to the current lithium-ion battery, he is now generally considered the father of the lithium-ion battery.
In this groundbreaking patent by Akira Yoshino, low-temperature graphite (petroleum coke) was used for the negative electrode, and the LiCoO2 material developed by Goodenough at Oxford University for the positive electrode (with a little treatment), the prototype of the modern lithium-ion battery was formally born. Because Li+ is embedded in both the positive and negative electrodes, the lithium-ion battery is also known as a "rocking chair" battery. The concept of "rocking chair" battery was first proposed by Armand et al. in the 1970s, which realized energy storage by embedding and disembedding Li+ between positive and negative electrode materials with different potentials. This battery design concept was really developed until the combination of LiCoO2 material with high voltage characteristics developed by Goodenough and low temperature graphite material.
After Aki Yoshino published his patent, Asahi Kasei established the A&T Battery Group to manufacture lithium-ion batteries, and now A&T has become a subsidiary of Toshiba. Although Aki Yoshino completed most of the development of the lithium-ion battery material system, how to commercialize it, especially how to compete with the then popular NiCd and the newly invented NiMH batteries was still a complex task. At that time, Sony was the leading company in the field of 3C consumer electronics, and had carried out the development of primary alkali metal batteries in the early days, and started to shift to secondary batteries in 1985, and soon shifted again from the initial Ni-Cd batteries to lithium secondary batteries. As a big brother in the field of consumer electronics, Sony had a strong desire to develop a new market that had never been seen before, which was an important reason for Sony's eventual success.
In the early days, due to the good resistance to solvent co-embedding ability of low temperature coke, so although its capacity is relatively low, but still in the first generation of lithium-ion battery has been widely used, in the second generation of lithium-ion battery, low temperature coke was replaced by higher capacity, better performance of hard carbon, but hard carbon still has a lot of problems, so in the third generation of lithium-ion battery has been used in the current widely used intermediate phase carbon microspheres (MCMB).
As for the cathode material, LiCoO2 developed by Goodenough is the most successful cathode material, which is still widely used in the field of consumer electronics until recent years in the field of power batteries, ternary materials, lithium iron phosphate materials have gradually replaced the traditional LiCoO2 material.
As for the binder, the early PVDF had poor adhesion on the cathode side, which had a certain impact on lithium-ion batteries, until Kureha Chemical Ind. Co. introduced carboxylic anhydride into PVDF, which significantly improved the adhesion of PVDF on the surface of Al foil.
Although the lithium-ion battery shell is not insignificant, it still plays a crucial role in the success of lithium-ion batteries. Early on, Sony thought that there was a trace of HF in the electrolyte, so it chose stainless steel as the shell of lithium-ion batteries, but the application found that the shell impedance of stainless steel was too high, so the solution of Ni plating on the surface of iron shell was finally chosen.
After Sony's unremitting efforts, the first commercial lithium-ion battery was successfully introduced to the market in 1991. Sony's first-generation battery had a volumetric energy density of 200Wh/L and a weight energy density of 80Wh/L (4.1V), and after the second-generation lithium-ion battery used hard carbon cathode material, the energy density of the battery was raised to 295Wh/L and 120Wh/kg (4.2V) The energy density of the third generation lithium-ion battery reached 400W/L and 155Wh/kg after adopting MCMB as the negative electrode, Sony became the leader in the field of lithium-ion battery at that time, but the fierce competition from other manufacturers made Sony's lithium-ion battery business shrink and finally transferred the battery business to Murata Foundation.
Today, after 28 years of development, lithium-ion batteries are no longer limited to the traditional 3C consumer electronics field, we power tools, electric vehicles and many other fields can see the lithium-ion battery, and the size of the lithium-ion battery is no longer limited to 18650, with more sizes and structures. The biggest change is still in the improvement of battery performance, we take the traditional 18650 battery as an example, at present Panasonic and other companies launched the energy type 18650 battery capacity can reach more than 3.3Ah, energy density can reach more than 240Wh/kg, compared to the initial generation of lithium-ion battery energy density has been increased by more than three times.
Compared with the traditional graphite material, the specific capacity of silicon material can reach more than 3000mAh/g, which is ten times of graphite material, and the addition of a small amount of silicon material can significantly improve the specific capacity of negative electrode.
The application of ternary materials (LiNix Mny Co1-x-y O2 or LiNi0.80 Co0.15Al0.05) is another booster for the improvement of energy density of Li-ion batteries. The specific capacity of ternary materials can reach up to 190mAh/g or more, which is more than 30% higher than LCO materials. Data from Pillot shows that as of 2015, although LCO demand still reached 45,000 tons, but has shown a downward trend, while NCM material usage has reached 35,000 tons, still continuing to grow, NCA material is 0.9 million tons, a high growth state.
Lithium-ion batteries in recent years in the large-scale application of power batteries to put forward higher requirements for its safety, and therefore also gave birth to a variety of technologies to enhance the safety of lithium-ion batteries, such as coated diaphragm technology, as well as cathode coating technology, etc. can help reduce the risk of short circuit within the battery due to internal defects in lithium-ion batteries, improve the thermal stability of lithium-ion batteries, especially the diaphragm coating technology in recent years has been Widely used, so compared to the original lithium-ion battery current lithium-ion battery in the safety has also been greatly improved.
The rise of lithium-ion batteries stemmed from the safety problems that could not be overcome by lithium metal batteries, in the efforts of the old generation of lithium people such as Yoshino Chang, through the application of graphite anode successfully solved the problem of dendrite growth of lithium metal anode, Sony's pioneering spirit of innovation has successfully commercialized lithium-ion batteries, which has laid the in and out of the development of modern lithium-ion batteries, after nearly 30 years of development, in the lithium people's After nearly 30 years of development, the lithium-ion battery, whether in energy density, power performance, or in cost compared to the initial lithium-ion battery products have been a very huge improvement, and the application areas of lithium-ion batteries from the initial 3C consumer electronics, expanded to today's power batteries and energy storage and other fields, I believe that under the efforts of the majority of lithium-ion battery developers, lithium-ion batteries in the next decade can also I believe that with the efforts of the majority of lithium-ion battery developers, lithium-ion batteries in the next decade can create brilliant.
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