Lead-based systems as suitable anode materials for Li-ion batteries

Abstract

Three lead-based materials formed by PbO 2 , PbO and Pb as main phases were prepared by following different synthetic procedures and tested as anodic materials in Li-ion batteries by using potentiostatic and galvanostatic methods. While the reduction of Pb(IV) to Pb(II) takes place in a single step, that of Pb(II) to Pb is a complex process involving several steps. Both reduction reactions are irreversible. Lead, whether electrochemically or chemically formed, undergoes an electrochemical reaction with lithium that over the 1.0 Á/0.0 V potential range yields Li x Pb alloys (0 5/x 5/4.4). The anodic and cathodic potentiostatic curves exhibit various signals that account for: (i) the formation of different intermediates with variable lithium contents; (ii) the reversibility of the alloying/de-alloying processes; (iii) the increase in complexity of such processes as the oxidation state of lead in them decreases. This results in capacity fading with cycling, particularly in the samples having Pb as the main component. One way of avoiding the capacity loss on cycling involves depositing the active material on lead sheets from spraying suspensions. These coatings exhibit a good capacity retention, which can be ascribed to the formation of a Li x Pb layer at the active material/substrate interface that facilitates electron and ion transfer across the electrode. #

Alloy Negative Electrodes for Li-Ion Batteries

“…86 Few studies of the lithiation of Pb have been reported. 28,46,95 This may be due to the relatively low specific capacity of Pb as compared to other active elements (550 mAh/g for Li 17 Pb 4 ). Nevertheless, Pb's low average voltage (∼380 mV) 28 and high volumetric capacity (1937 Ah/L for Li 17 Pb 4 ) are attractive.…”

Reaction of SbPO4 with lithium in non-aqueous electrochemical cells: preliminary study and evaluation of its electrochemical performance in anodes for lithium ion batteries

“…This is fairly unsurprising as the intercalation process should promote the reduction of M(II) and a subsequent decrease in M-O binding energy, which destabilizes the structure. The basic scheme of the reaction of lithium with other tin/lead salts or oxides involves the formation of metallic atoms and a lithium compound [5,6,10,11]. Liu et al have suggested that the reaction with lithium destroys the Pb 3 (PO 4 ) 2 structure and results in the formation of lithium phosphate and lead particles in the electrode, according to…”

“…This reaction is interesting with a view to obtain negative electrode materials as in situ formed metallic particles can react reversibly with lithium to form the Li 4.4 Pb alloy [10,11] (or the Li 22 Sn 5 alloy [12,13] with tin phosphate) at a potential close to 0.0 V. However, the capacity of these phosphates has been shown to decline after a few cycles. Such a capacity loss can be ascribed to the formation of large lead or tin clusters during cycling that reduce the percolation paths associated to electron and lithium diffusion [14].…”

Alloy-Based Anode Materials

“…[94]. Because Pb-based anodes tend to degrade rapidly upon cycling (see e.g., Ref [101]), as with Sn, most studies have concentrated on decreasing particle size and dispersing them into a buffering inactive matrix. For instance, lead oxides have been investigated [101] and compared with tin oxide [102].…”

“…Because Pb-based anodes tend to degrade rapidly upon cycling (see e.g., Ref [101]), as with Sn, most studies have concentrated on decreasing particle size and dispersing them into a buffering inactive matrix. For instance, lead oxides have been investigated [101] and compared with tin oxide [102]. More recently, PbO-C composites have been studied [103], as well as Pb-sandwiched nanoparticles (i.e., SiC-Pb-C core-shell1-shell2 nanoparticles) [104], but the gravimetric capacity is rather low (*200 mAh/g after 200 charge-discharge cycles) although the volumetric capacity is about twice that of graphite, at 1580 mAh/cm 3 (i.e., *60 % of the theoretical Pb volumetric capacity) after 600 cycles [104].…”