Lithium solid electrolyte, primary

Primary batteries, mercury-zinc, silver-zinc, lithium solid electrolyte types. 

Duracell Deutschland Technical Division, D-5020 Frechen, Hermann-Seger-Strasse 13 Primary batteries, mercury—zinc, silver—zinc, lithium solid electrolyte types. 

Duracell UK Technical Division Duracell House Gatwick Road, Crawley RHIO 2PA Primary batteries, mercury-zinc, silver-zinc, lithium solid electrolyte types, nickel-cadmium, lithium-sulphur dioxide, lithium-manganese dioxide, zinc-air. See also Duracell (US)... 

Primary batteries, mereury-zinc, silver-zinc, lithium solid electrolyte types secondary nickel-metal hydnde. See also Duracell (UK). 

Li2S204 being the SEI component at the Li anode and the solid discharge product at the carbon cathode. The Li—SOCI2 and Li—SO2 systems have excellent operational characteristics in a temperature range from —40 to 60 °C (SOCI2) or 80 °C (SO2). Typical applications are military, security, transponder, and car electronics. Primary lithium cells have also various medical uses. The lithium—silver—vanadium oxide system finds application in heart defibrillators. The lithium—iodine system with a lithium iodide solid electrolyte is the preferred pacemaker cell. 

Usually, in a given electrolyte solution, there is a similarity in the mechanism of SEI formation on carbon and metallic lithium.285 353 354 The mechanisms of SEI formation on lithium in numerous electrolytes are investigated since about three decades. In about the last 15 years, the focus continuously shifted from metallic lithium to carbon. There are a huge number of publications covering manifold aspects of the carbon s reactivity with the electrolytes and/or the SEI formation. The reader of this chapter is referred to the books published in this field recently and especially to the primary literature listed therein. Examples include Nonaqueous Electrochemistry from 1999 edited by Aurbach,355 Advances in Lithium-Ion Batteries from 2002 edited by van Schalkwijk and Scrosati,356 and Lithium-Ion Batteries Solid-Electrolyte Interphase from 2004 edited by Balbuena and Wang.281... 

Solid electrolytes for lithium-ion batteries are expected to offer several advantages over traditional, nonaqueous liquid electrolytes. A solid electrolyte would give a longer shelf life, along with an enhancement in specific energy density. A solid electrolyte may also eliminate the need for a distinct separator material, such as the polypropylene or polyethylene microporous separators commonly used in contemporary liquid electrolyte-based batteries. Solid electrolytes are also desirable over liquid electrolytes in certain specialty applications where bulk lithium-ion batteries as weU as thin-film lithium-ion batteries are needed for primary and backup power supplies for systems, devices, and individual integrated circuit chips. 

If GO is used as a host lattice for Li+ in aprotic electrolytes, reversibility is improved [577]. The potential level is distinctly more positive than with donor GIC, at about —1 V vs. SHE. An all-solid-state Li/GO battery with PE0/LiC104 as solid electrolyte was reported by Mermoux and Touzain [578], but rechargeability is poor. Recently, the structure of graphite oxide was studied by its fluorination at 50-2()0 °C [579]. C-OH bonds were transformed into C-F bonds. The examples, in conjunction with Section 2, show that the formation or cleavage of covalent C-O (C-F) bonds makes the whole electrochemical process irreversible. Application was attempted in lithium primary batteries, which have a voltage of 2-2.5 V. Really reversible electrodes are only possible, however, with graphite intercalation compounds, which are characterized by weak polar bonds. 

A variety of dimensionally stable solid electrolytes consisting of a mixture of organic plasticizers such as EC, PC etc., along with structurally stable polymers such as poly( acrylonitrile) (PAN) or poly( vinyl sulfone) (PVS), or polyvinyl pyrrolidine (PVP) or polyvinyl chloride (PVC) and several lithium salts have been tested and found to have excellent ionic conductivities at ambient temperatures [155-156]. In these gel type electrolytes the primary role of the polymers PAN, PVS, PVP or PVC is to immobilize the lithium salt solvates of the organic plasticizer liquids. However, with polymers such as PAN a coordination interaction with Li+ is also quite likely. 

The rate of this process in aprotic electrolytes is rather high the exchange current density is fractions to several mA/cm. As pointed out already, the first contact of metallic lithium with electrolyte results in practically the instantaneous formation of a passive film on its surface conventionally denoted as solid electrolyte interphase (SEI). The SEI concept was formulated yet in 1979 and this film still forms the subject of intensive research. The SEI composition and structure depend on the composition of electrolyte, prehistory of the lithium electrode (presence of a passive film formed on it even before contact with electrode), time of contact between lithium and electrolyte. On the whole, SEI consists of the products of reduction of the components of electrolyte. In lithium thionyl chloride cells, the major part of SEI consists of lithium chloride. In cells with organic electrolyte, SEI represents a heterogeneous (mosaic) composition of polymer and salt components lithium carbonates and alkyl carbonates. It is essential that SEI features conductivity by lithium ions, that is, it is solid electrolyte. The SEI thickness is several to tens of nanometers and its composition is often nonuniform a relatively thin compact primary film consisting of mineral material is directly adjacent to the lithium surface and a thicker loose secondary film containing organic components is turned to electrolyte. It is the ohmic resistance of SEI that often determines polarization of the lithium electrode. 

Solid Electrolytes. A protected Lithium anode is under development for both primary and secondary batteries that promise much larger capacities. This strategy is illustrated by the Li/seawater primary battery in which a Lithium anode is immersed in a nonaqueous electrolyte, the anolyte, that is separated from seawater contacting a cathode current collector by a Li -ion solid-electrolyte separator. The seawater acts as a liquid cathode. Except for contact with a negative post, the Lithium anode and its anolyte are sealed in a compartment containing a Li -ion solid-electrolyte wall that interfaces the seawater. The anolyte is chemically stable to both the Lithium and the solid electrolyte the solid electrolyte must not be reduced on contact with the Li anode. Moreover, eiflier the seal or the compartment must be compliant to allow for the change in volume of the Lithium on discharge. The seawater is not ccmtained in an open cell, it is contained within a battery in a closed cell. The LF ions from the anode react with water at the cathode current collector ... 

Lithium-Metal Salt secondary batteries are analogous to the Lithium-seawater primary battery [3]. A Li -ion solid electrolyte separates a nonaqueous anolyte and an aqueous cathode. For example, a Lithium anode with a carbonate anolyte and an aqueousFe(CN)g /Fe(CN)g cathode has been shown to give aflat voltage F 3.4 V with an efficiency that increases with the molar ratio of iron cyanide in the cathode solution [27]. This promising approach requires development of a Li-ion solid electrolyte having a (Tli > 10 8/cm at room temperature that is stable to an acidic cathode solution and is not reduced by contact with a Li° dendrite on the anode side. 

Lithium-air batteries [28] may also use a solid separator that will block dendrite growth from the anode to the cathode but allows permeation of the Li" ion between an anolyte and a catholyte. The simplest such separator would be a solid Li -ion solid electrolyte, but a porous glass containing the liquid electrolyte has been used where the anolyte and the catholyte are identical. As in the Zn-air primary battery, a porous carbon containing an oxygen-reduction catalyst on the pore walls and the liquid electrolyte in the pores provides the structure needed to facilitate the catalytic reaction of Li" ions with the gaseous O2 cathode. The cathodic reaction... 

Primary batteries have existed for over 100 years, but up to 1940, the zinc-carbon battery was the only one in wide use. During World War II and the postwar period, significant advances were made, not only with the zinc-carbon system, but with new and superior types of batteries. Capacity was improved from less than 50 Wh/kg with the early zinc-carbon batteries to more than 400 Wh/kg now obtained with lithium batteries. The shelf life of batteries at the time of World War n was limited to about 1 year when stored at moderate temperatures the shelf life of present-day conventional batteries is from 2 to 5 years. The shelf life of the newer lithium batteries is as high as 10 years, with a capability of storage at temperatures as high as 70°C. Low-temperature operation has been extended from 0 to -40C, and the power density has been improved manyfold. Special low-drain batteries using a solid electrolyte have shelf lives in excess of 20 years. 

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