History of Lithium Battery Development – Semco University

Introduction

All batteries use this same basic configuration – Anode, cathode and electrolyte Lithium batteries and are different – Lithium batteries use lithium metal anodes (usually non rechargeable) – graphite or other material. It provides portable electricity, back-up of electricity during power loss and fluctuation and it is a source of power to electric vehicles which is in good demand in the automotive industry. And, in this article we will learn about the history of lithium battery.

1. Lithium Battery Concept and Development of Lithium Primary Battery (1960 ~ 1970)

• 1960~1970 The oil crisis of the 1990s forced people to look for new alternative energy sources, At the same time, military, aviation, medicine and other fields also put forward new requirements for power supply. Batteries at that time could no longer meet the needs of high energy density power sources.
• Due to the small proportion of lithium among all metals, the electrode potential is extremely low, it is a metal with high energy density, Lithium battery system can theoretically obtain the maximum energy density, so it logically entered the field of vision of battery designers.
• But lithium metal reacts with water at room temperature.

1.1 Li/CuCl₂ System: First Try

• 1958 year, Harris It is proposed to use organic electrolytes as electrolytes for lithium metal primary batteries.
• 1962 year, at the fall meeting of the Electrochemical Society in Boston, from the US military Lockheed Missile and Space Co. of Chilton Jr. and Cook The idea of “lithium non-aqueous electrolyte system” is proposed.
• Chilton and Cook A new type of battery is designed using lithium metal as the negative electrode, Ag, Cu, Ni etc. halide as positive electrode, low melting point metal
• SaltLiCl-AlCl3 Dissolved in acrylic carbonate as electrolyte. Although the battery has many problems that make it only a concept, not commoditized, but Chilton and Cook His work opened the prelude to lithium battery research.

1.2 Li/(CF)n System: First Glimpse

• 1970 year, Japan’s Matsushita Electric Company and the U.S. military independently synthesized a new cathode material almost at the same time–Fluorocarbons. Panasonic successfully prepared the molecular expression as (CFx)n (0.5 ≤x ≤ 1) crystalline fluorocarbon, Use it as the positive electrode of a lithium primary battery. U.S. military researchers designed (CxF)n (x = 3.5-7.5). Inorganic lithium salt Organic Solvent Electrochemical System, Intended for space exploration.
• 1973-year, Mass production of lithium carbon fluoride primary batteries at Panasonic, The first installation on a fishing boat.

1.3 Li/MnO₂ System: Harvest Success

1975 year, Sanyo makes breakthrough in transition metal oxide electrode materials, Li/MnO2 successful development, used inCS-8176L type calculator. 1977 year, Articles on the design ideas and battery performance of the system were published in the Japanese magazine “Electrical Chemistry and Industrial Physical Chemistry” in two consecutive issues. 1978-year, Mass production of lithium manganese dioxide batteries, Sanyo’s first-generation lithium battery entered the market.

1.4 Li/Ag₂V₄O₁₁ System: A Leader in the Medical Field

1976-year, Lithium-iodine primary batteries appeared. then, many special lithium batteries for the medical field came into being, among them lithium silver vanadium oxide (Li/Ag₂V₄O₁₁) The best-selling battery, It holds the majority of the market share for batteries used in implantable cardiac devices. The battery consists of composite metal oxides, during discharge due to the reduction of the two ions, The lithium storage capacity of the cathode reaches 300mAh/g. The addition of silver not only greatly enhances the conductivity of the battery system, and improved capacity utilization. Li/Ag₂V₄O₁₁ the system is a major breakthrough in the special field of lithium batteries.

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2. Lithium Metal Secondary Battery (1972-1984)

• The success of lithium primary batteries has stimulated a research boom in secondary batteries. Academia has begun to focus on how to make the battery reaction reversible.
• When lithium primary batteries are rapidly being used in fields such as watches, calculators, and implantable medical instruments due to their high energy density, The reactions of many inorganic substances with alkali metals show good reversibility. The discovery of these compounds that were later identified as having a layered structure, It plays a crucial role in the development of lithium secondary batteries.

2.1 Intercalation compound: The key to the success of lithium secondary batteries

• 60 end of the era, Bell Labs Broadhead intercalation of iodine or sulfur into binary sulphides (likeNbS2) The interlayer structure of, at low depth of discharge, the reaction has good reversibility.
• Meanwhile, Stanford University’s Armand found that a series of electron-rich molecules and ions can intercalate into the interlayer structure of layered di-sulphides, such as tantalum disulfide (TaS2), in addition, they also studied the reaction of alkali metal intercalation in the graphite lattice, it is pointed out that the mixed conductor of graphite intercalated with alkali metal can be used in secondary battery.
• 1972 year, at an academic conference, Steel and Arm and Theoretical basis for the concept of Electrolyte.

2.2 The first lithium secondary battery was born

• With the deepening of intercalation compound chemistry research, the goal of finding useful electrode materials in this class of compounds has gradually become clear.
• Exxon Company R&D personnel continue research by Stanford University team, they intercalate hydrated alkali metal ions into tantalum disulfideTaS2middle, when analyzing the resulting compound, The researchers found it to be very stable. All this foreshadows: It will be very possible to select materials with application value in the layered binary sulfide as the positive electrode of lithium secondary battery. final titanium disulfide (TiS2) It is favored by battery designers for its excellent performance.

• 1972 year, Exxon designed AT iS2 as the positive electrode, lithium metal as the negative electrode, LiClO4 /A battery system in which dioxane is the electrolyte. Experiments show, the performance of this battery is good, with a deep cycle close to1000 Second-rate, the loss per cycle is less than 0.05%.

• During charging, Due to the uneven surface of the metal lithium electrode, Differences in electrodeposition rates cause uneven deposition, this leads to the formation of dendritic lithium crystals at the negative electrode. When the dendrite grows to a certain extent, it will break, produces “dead lithium”, irreversible lithium, Reduce the actual capacity of the battery.
• 70end of the era, Exxon the researchers at the beginning of research on lithium aluminium alloy electrodes.
• 1977-1979 year, Exxon Launched button-type lithium alloy secondary battery, For watches and small devices.
• 1979 year, Exxon Shown at the Auto Electronics Show in ChicagoTiS2 Large lithium single cell system for the positive electrode, and later Exxon company for security reasons, The lithium secondary battery system has not been commercialized.
• 1983 year, Peled proposed a solid electrolyte interface membrane (referred to as SEI) Model. research shows, Properties of this film (Interfacial Properties between Electrode and Electrolyte) It directly affects the reversibility and cycle life of lithium batteries.
• 20 century 80 mid-era, Researchers begin a series of modifications to the “interface”, including finding new electrolytes, add various additives and purifiers, and use various mechanical processing methods, The growth of lithium dendrites is suppressed by changing the physical properties of the electrode surface
• 80 ends of the decade, Canada Moli Developed by energy companies Li/Mo2 Lithium metal secondary batteries are

2.3 The pause in research and development of lithium secondary batteries

1989 year, because Li /Mo2 Secondary battery catches fire, Except for a few companies, most companies have withdrawn from the development of metal lithium secondary batteries. Lithium metal secondary battery research and development basically stopped; the key reason is that the security problem has not been fundamentally solved.

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3. Lithium Ion Battery (1980-1990)

• Given that various improvements have not worked, Lithium metal secondary battery research stagnates, the researchers opted for a disruptive approach.
• The first option is to ditch the lithium metal, Choose another intercalation compound in place of lithium. The battery of this concept is vividly called a rocking chair battery (Rocking Chair Battery, short name RCB). productize the concept, It took ten years, The first to reach the other side of success was Japan’s Sony Corporation, They named the technology Li-ion (Lithium-ion technology).

3.1 Rocking Chair Battery Concept

• The first concept of rocking chair battery was proposed by Armand 70early s, Armand began to study graphite intercalation compounds,1977 year, He applied for a patent for lithium intercalated graphite compounds,1980year, He proposed the concept of rocking chair battery, Both the positive and negative electrodes of the lithium secondary battery are made of intercalation compounds.
• But to make the concept a reality, three problems need to be overcome: First, to find a suitable lithium intercalation cathode material, The second is to find suitable lithium intercalation anode materials, The third is to find an electrolyte that can form a stable interface on the surface of the negative electrode. It took a lot of time for rocking chair batteries to go from concept to reality 10 time of year.

3.2 LiMO2 Progress in Compound Research

• 70 the end of the era, Murphy studies reveal similar V6O13 It has excellent electrochemical properties like the oxides, which laid the foundation for the later research on spinel-like intercalation compounds.
• With continuous efforts, researchers found LixMO2 (represent Co, Ni, Mn) family of compounds, they have with LiTiS2 The similar rhombohedral structure makes it easy to intercalate and de intercalate lithium ions.
• 1980 year, Mizushima and Good enough put forward LixCoO2 or LixNiO2 Possible application value, but due to the prevailing view at the time that high operating voltage is not good for the stability of organic electrolytes, The work has not received enough attention. With the application of carbonate electrolytes, LixCoO2 First to become the cathode material for commercial lithium-ion batteries.

Table 1. Cooperation material of some key ion battery manufactures in the early days

Cathode material	Anode material	Battery Manufacture
LCoO2	Coke	Sony
LCoO2	Graphite	Panasonic Battery, Sanyo Electric, Hitachi Wansheng, Japan
LN iO2	Stone	Battery French Saft Panasonic Battery, Sanyo Electric, Japanese
LM n204	Graphite	Battery Japan NEC, Canada Moli
LCoO2	Tin Amorp house oxide	Fuji Corporation
LNiO2	Carbon Material	Polystor

*Excerpted From Zu Xijun hog (ED). New type of secondary battery material. Shenyang: out of north esteem University

• LixNiO2 Has a high specific capacity, cost more than LixCoO2 Low, but it is very difficult to synthesize, Fast capacity decay, low thermal stability, Not widely used in commercial batteries.
• L ixMnO2 Has a theoretical capacity similar to that of cobalt nickel, but during the cycle LixMnO2 gradually changing structure, split into two phases, poor circulation, cannot be used as electrode material of choice.
• spinel structure LiMn2O4 Due to its four characteristics of low cost, high thermal stability, good overcharge resistance and high operating voltage, its modification has been a research hotspot for many years. The disadvantage is that the cycle performance at high temperature is poor. At present, this material is the main object of research on power lithium batteries in the United States, Japan and other countries.
• 1997year Good enough et al pioneered the olivine structure LiFePO4 work. LiFePO4Has a more stable oxidation state, good safety performance, Good high temperature performance, the advantages of a wide range of raw materials and low prices, L iFePO4 It is considered to be a new generation of cathode materials with great potential to replace existing materials. The disadvantage is that the conductivity is low and the specific capacity is low.

4. Lithium Polymer Battery: (1978-1999)

• In addition to the first solution of discarding metal lithium electrodes, the developers also made another choice, That’s the second option for ditching liquid electrolytes, An ion-conducting polymer electrolyte was chosen to replace the liquid electrolyte. The polymer electrolyte also acts as a separator in liquid lithium-ion batteries. According to different applications in lithium batteries, it can be roughly divided into two types: (1) solid polymer electrolyte, short name SPEs; (2) Gel polymer electrolyte, short name GPEs.

Soled Polymer Electrolyte Battery

• 19 end of the century, Warburg Some solid-state compounds are found to be pure ionic conductors.
• 1975year, W right found that polyethylene oxide PEO Able to dissolve inorganic salts and exhibit ionic conductivity at room temperature.
• 1978 year, Armand This polymer electrolyte was studied for the first time as a lithium battery electrolyte. SPEs The electrolyte layer can be made very thin, Batteries can be made in any shape and are leak-proof, and prevents the formation of lithium dendrites, Improve battery cycle performance. But SPE The ionic conductivity is not high, and in addition to the problem of electrode surface chemistry, so SPEs development is not optimistic. Gel Link polymer electrolyte battery GPES
• The researchers found that when excess organic solvent was added as a plasticizer to SPE in electrolyte, original solid SPE the electrolyte becomes a frozen gel-like electrolyte GPEs. In addition to ionic conductivity, the electrochemical stability, safety, and mechanical resistance of the interface with the positive and negative electrode materials are better than SPEs excellent, the tolerance of the battery when overcharged is also better than SPEs good.
• 1990year Abraham Published a paper on the study of lithium-ion conductivity in gel-like electrolyte systems with plasticizers added, Improves Li-ion conductivity at room temperature to10-3 Ω-lcm-1 At the time, this indicator is considered insurmountable.
• 1994year, Bell core company Tarascon Group patent application, It was the first to propose the use of ionically conductive polymers as electrolytes to manufacture lithium polymer secondary batteries.
• 1996year, Tarasco al reported Bell core/Telcordia commoditization GPE Battery performance and fabrication process.
• 1999year, Lithium-ion polymer battery officially put into commercial production, led by Panasonic 8 Every company has a product launch, therefore, 1999 The year is known by the

Conclusion

In conclusion this Article states that Lithium Ion Battery is the best source of power to EV Vehicles and for other related components also and it is in good demand. Lithium – ion batteries is much greener than other fuels like diesel, gasoline etc. Hence adoption of Lithium – ion batteries can reduce environmental impact also.

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