History of lithium batteries

In the early 1970s, the research work on lithium-ion batteries was promoted due to the energy crisis. Li or Li-Al alloys were used as anode materials, including Li/MnO2, Li/I2, Li/SOCl2, Li/FeS2, etc. Lithium primary batteries have appeared one after another. In 1970, Panasonic Corporation of Japan obtained a patent for Li/(CF)n battery in the United States. During the discharge process, (CF)n was lithiated to form C and LiF, and the reaction was not reversible, so the lithium primary battery at that time It is a disposable battery. In 1977, Sanyo, the world's largest manufacturer of lithium-ion batteries, designed the Li/MnO2 battery, which was immediately applied to the company's solar-powered rechargeable electronic calculator. In the initial research, General Motors (GM) and Argonne National Laboratory (ANL) in the United States focused on lithium-ion battery systems using molten salts as electrolytes. The raw material of the pole is lithium and sulfur in a molten state, and the electrolyte is melted with a mixed lithium salt such as LiCl or KCl. The molten salt electrolyte battery requires a high temperature of 45 ° C when working. However, such batteries cannot suppress damage to the environment during use, and the capacity is quickly degraded. In the next study, the researchers abandoned lithium and sulfur, switching to lithium aluminum alloy (LiAl) and iron sulfide (FeS and FeS2), although this improved cycle performance, but due to organic electrolyte lithium-ion battery The rapid development of the research work on high-temperature molten lithium-ion batteries around 1990 has basically ended.

The true meaning of lithium-ion batteries was first proposed by Exxon's Whittingham in 1976. The so-called lithium-ion battery means that there is no elemental lithium in the battery. The source of lithium is provided by lithium ion compounds. Whittingham found that at room temperature, layered TiS2 can electrochemically react with metallic lithium and combine organic energy storage and insertion reactions for the first time. The Li/TiS2 battery has an operating voltage of about 2V, and the cycle performance is very good. In 1000 cycles, the capacity attenuation is only 0.05%/time. Exxon was introduced to the market in 1977 using LiAl alloys instead of metallic lithium as the negative electrode for lithium-ion batteries for watches and small electronic devices. Thereafter, compounds which can be reversibly decoupled with lithium, represented by VSe2, MoO3, CuTi2S4, V2O5, V6O3, and LiV3O8, appear one after another. In 1980, MoliEnergy of Canada chemically inserted 1 mol of lithium into 1 mol of MoS2 to form LiMoS2 to improve the electrochemical cycle performance of MoS2 and industrialize it. This is also the closest to the prototype of modern lithium-ion batteries.

After the 1980s, the research on lithium-ion batteries made breakthroughs: in 1980, the Goodenough group made LiCoO2 cathode materials; in 1981, Bell Labs used graphite for anode materials of lithium-ion batteries. In 1983, the Goodenough group made the positive electrode material LiMn2O4; in 1989, Manthiram and Goodenough reported that the induction effect of polyanions (such as SO42-) can improve the working voltage of metal oxides; in 1990, Sony's commercial lithium the ion secondary battery (C/LiCoO2) becomes a true lithium ion battery. A lithium secondary battery having a graphitized carbon material as a negative electrode is realized, and its composition is: lithium and a transition metal composite oxide/electrolyte/graphitized carbon material. In 1994, Tarascon and Guyomard made an electrolyte system based on ethylene carbonate and dimethyl carbonate; in 1997, Goodenough reported a cathode material, LiFePO4. At this point, the lithium ion battery is fully formed.

Since the potential difference between the metal lithium and the graphitized carbon material and lithium intercalating compound LiC6 is less than 0.3 V, the negative electrode material of the rechargeable lithium ion battery can be used without lithium metal. During the charging of the secondary lithium ion battery, lithium first enters the graphite. In the graphite, lithium is stored in the interlaminar spaces in the middle of the layered structure, and the subsequent discharge process is deintercalated by the layers. This method has good reversibility, so this way is rechargeable. Lithium-ion battery cycle performance has been improved. In addition, the carbon material is inexpensive, non-toxic, and has a relatively stable discharge state in the air. It can not only use the metal lithium which is free of performance, but also can prevent the generation of lithium crystal branches, and the service life has been greatly improved. The fundamental improvement in the safety of lithium-ion batteries is fundamentally improved.

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