Article Review: Lithium Transition Metal Oxides as Battery Cathode

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Lithium Transition Metal Oxides as Battery Cathode

"Although the basics of electricity were established in 600 B.C. By the Greek philosopher

Thales of Miletus and then refined by scientist William Gilbert of England in 1600,

the first battery actually dates back to the 18th century"

(Millard, N.d., p.2).

Modern Miniaturization

Contrary to the contemporary trend to supersize fast food portions, which Jennifer O. Fisher and Tanja V.E. Kral (2007) note in the article, "Super-size me...," manufacturers routinely reduce the size of electronic components. As this practice of downsizing electronic components contributed to improvements in integrated circuit technology and fabrication processes, it simultaneously led to electronic devices and related peripherals becoming miniaturized. According to Burtrand Insung Lee and Sridhar Komarneni (2005) in the book, Chemical Processing of Ceramics, "the consumer market has readily embraced the miniaturization of products and manufacturers have continuously come up with new products and marketing concepts. All… ubiquitous miniaturized devices… need…efficient, lightweight, and rechargeable power sources" (p. 668). The bulk lithium-ion battery depicts one power source that matches each of these particular requirements that the contemporary consumer craves.

The lithium-ion battery, initially introduced as replacement for the heavier, older nickel-metal hydride (NiMH) battery, provided superior energy density and weighed less than the NiMH. As the lithium-ion battery technology has spread through the consumer electronic field, one finds the lithium-ion battery ubiquitous. A traditional lithium battery contains a lithium anode, a cathode made of a transition metal oxide and an organic electrolyte that contains lithium ions. Transition metal oxides, electrode materials, prove useful in various types of batteries, including rechargeable and lithium. In the journal article, "Vanadium-doped manganese oxides as cathode materials for rechargeable lithium batteries," Charles J. Capozzi and Jun John Xu (2002), both with the Department of Ceramic and Materials Engineering, Rutgers University, explain that in the past, researchers believed "the reaction of lithium metal and a transition metal oxide yielded lithium oxide due to reduction of the transition metal oxide. However, emf values were not consistent with thermodynamically expected values" (Introduction section, ¶ 1). Some studies, according to Capozzi and Xu report, conclude that lithium intercalated into the transition metal oxide structure by expanding the volume of the transition metal oxide structure. Through the examination of related literature, the researcher relates a number of advantages, disadvantages, future prospects, fabrication methods and challenges for lithium transition metal oxide, one type ceramic, as a battery cathode and simultaneously introduces the lithium transition metal oxides as the battery cathode.

Time Refines Batteries

Count Alessandro Volta of Italy developed the first battery, according to the article, "Battery power," (2008). In a paper Volta submitted to the Royal Society in 1799, he described his battery, which "comprised alternating discs of zinc and copper with pieces of cardboard soaked in brine between the metals" ("Battery power," ¶ 2). In time, this battery became known as Volta's pile. A number of individuals introduced and manufactured additional various cell chemistries. During 1836, John Frederic Daniell, a British chemist, invented the Daniell cell (Ibid.). In the article "Gassner, Carl," Cutler J. Cleveland and Tom Lawrence (2008) report that Carl Gassner, a German scientist, invented the first commercially successful dry cell battery in1881. Gassner's battery became the contemporary, general-purpose, carbon-zinc battery. Gassner added zinc chloride to the electrolyte. This significantly increased the cell's useful life and reduced the corrosion of zinc when the cell idled. In1899, Waldmar Jungner, a Swede, developed the first nickel-cadmium (NiCd) battery (Ibid.). Figure 1 depicts the chemistry of the Daniell cell.

Figure 1: The Daniell Cell's Chemistry (Battery Power, 2010, Further Reading Section).

When the circuit is complete, electrons flow from the zinc to the copper, owing to the electrical potential. Conventional current flows from the positive (anode) to the negative (cathode): this is the opposite to the direction of electron flow.

The porous separator prevents bulk mixing of the electrolytes but allows aqueous ions to pass through to maintain the ionic balance.

Anode: Zn(s) Zn2+(aq) + 2e-

Cathode: Cu2+(aq) + 2e- Cu(s)

For a copper-zinc cell under standard conditions (25°C, 1 mol dm-3, 1 atmosphere) the cell voltage may be calculated from the oxidation and reduction half reactions.

Zn(s) 1/2 Zn2+ | Cu2+(aq) 1/2 Cu(s)

E Zn2++ 2e- Zn E = -0.76V

E Cu2+ + 2e- Cu E = +0.34V

E for the cell = +0.34 - (-0.76) = 1.10V. (Battery Power, 2010, Further Reading Section)

Batteries consist of three separate parts, an anode (-) which comprises that negative side, a cathode (+) positive side, and the electrolyte. In a traditional battery, the cathode and anode connect to an electrical circuit. The Northwestern State University article, "How do batteries work?"(2010), explains that "the chemical reactions in the battery causes a buildup of electrons at the anode. This results in an electrical difference between the anode and the cathode. & #8230;[One may] think of this difference as an unstable build-up of the electrons" (¶ 3). As a result the electrons rearrange themselves by repelling each other and finding a place with fewer electrons.

In batteries, these electrons can only travel to the cathode, as the electrolyte stops the electrons from reaching the anode and end up at the cathode. "When the circuit closes (a wire connects the cathode and the anode) the electrons will be able to get to the cathode. In the picture above, the electrons go through the wire, lighting the light bulb along the way" (How do batteries…, 2010, ¶ 4). Electrochemical processes changes the chemicals in the cathode and anode to ensure they do not supply electrons, this explains why there is limited power available from batteries. When recharging a battery, the flow of electrons is reversed by using a different power source, perhaps solar panels, allowing the anode and cathode to be restored to their full power. Figure 2 depicts this process.

Figure 2: Depicts Currency of a Battery (How do batteries…, 2010).

A myriad of items, including, but not limited to, cars; cell phones; computers; microchips; etc. may use energy batteries provide. M. Armand and J.-M. Tarascon (2008), with the Universite de Picardie Jules Verne, Amiens, France, assert in the journal article, "Building better batteries," that variations of the combustion reaction fueled the past few centuries' technological revolution. During the majority of the 20th century, several generations of disposable dry cell batteries as well as Jungner's rechargeable nickel-cadmium served as the primary power sources for portable electric and electronic equipment. A number of inherent problems challenged the dry cell batteries and the nickel cadmium batteries as they not only contained lead, mercury and cadmium, they proved to have high toxicity when individuals disposed them. The nickel-cadmium batteries also became known for "memory effect." When one charged one of these batteries prior to it being completely expended, the battery would only hold the charge from the point the individual charged it. In regard to the lithium ion battery,

Metallic lithium, which is used in lithium primary cells, is unsuitable for rechargeable cells owing to dendritic crystal growth of the metal in the recharge phase which can damage the cell. Instead lithiated graphite is used as the anode.

Anode: Lithiated graphite (LiC6)

Cathode: LiCoO2

Electrolyte: LiPF6 in aprotic solvent

Overall reaction: Li 1-x CoO2 + CLix LiCoO2 + CE = 3.7V

Lithium atoms in the lithiated graphite are intercalated between the hexagonal layer molecular structure of the graphite and are free to move around. On discharge these atoms migrate from the graphite to the lithium cobalt oxide. This technology was developed by the British company AEA Technology and commercialised by Sony under licence from AEA. Currently Quallion in the U.S. uses this technology in microbatteries (the size of a grain of rice) in medical implants for neurological disorders. The batteries have a 10-year life. (Battery Power, 2010, Secondary Cells Section, ¶ 12).

In 1980, Mizushima et al. initially examined LiCoO2. At that time, a number of researchers projected LiCoO2 to comprise a potential positive electrode for lithium-ion rechargeable batteries. Sony Corporation commercialized the first lithium-ion battery in 1991. Sony used lithium cobalt oxide for the positive electrode and graphite (carbon) for the negative electrode. Since 1991, manufactures have generally used LiCoO2 as the primary cathode in commercial lithium-ion batteries. LiCoO2 continues to claim a significant stance as a cathode material. Lithium oxide used as a flux in ceramic glaze, also serves as a replacement for lithium cobalt oxide as the cathode in the lithium ion batteries used ... lithium (element, metal -- in chemistry Merriam Webster Dictionary defines "flux' (2010) as a substance used to promote fusion (as of metals or minerals); especially: one (as rosin) applied to surfaces to be joined by soldering, brazing, or welding to clean and free them from oxide and promote their union" (p. 1).

Lee and Komarneni (2005) assert that currently, manufacturers use three intercalation materials as positive electrode materials to produce commercial lithium-ion rechargeable batteries: LiCoO2, LiNiO2, and LiMn2O4. Armand and Tarascon (2008) explain:

The lithium-ion battery, first commercialized by Sony in 1991, owes its name to the exchange… [END OF PREVIEW]

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