Investigation of Yttrium and Polyvalent Ion Intercalation into Nanocrystalline Vanadium Oxide

Abstract

The electrochemical reactivity of cations such as Ca 2ϩ , Mg 2ϩ , and Y 3ϩ into crystalline V 2 O 5 materials was investigated. The ionic diffusion constant of Li ϩ and Y 3ϩ into microcrystalline and nanocrystalline V 2 O 5 was measured by the galvanostatic intermittent titration technique. The Y 3ϩ ion diffusion constant into a 500 nm crystalline V 2 O 5 was found to be approximately two orders of magnitude lower than for the Li ϩ ion. In order to enable practical intercalation of Y 3ϩ , a nanocrystalline V 2 O 5 was fabricated through a combustion flame synthesis technique. For the first time, reversible electrochemical intercalation of Y 3ϩ into a host structure was shown to be feasible. An asymmetric hybrid cell configuration was utilized in order to provide a reversible counter electrode during intercalation. Preliminary data indicates Y 3ϩ can be reversibly intercalated into V 2 O 5 with apparent gravimetric capacities exceeding that of Ca 2ϩ , Mg 2ϩ , or Li ϩ over the limited voltage range of 2.5 to 4.2 V (Li/Li ϩ ). The concept of polyvalent intercalation is discussed relative to intercalation, pseudocapacitance, apparent specific capacity, and practical energy storage systems.High energy density electrochemically rechargeable energy storage systems are the key to the future realization of a myriad of next generation applications ranging from biomedical to electric vehicles. Currently, there exist two commercialized single-ion room temperature secondary battery technologies utilizing at least one intercalation electrode, NiMeH ͑proton͒ and Li ion ͑lithium͒. NiMeH batteries utilize the reversible intercalation of a H ϩ guest cation into NiOOH and alloying reactions with rare earth or misch metal counter electrodes. The basic Li-ion battery utilizes intercalation reactions of Li ϩ into transition metal positive electrodes or carbonbased negative electrodes. Presently, the Li-ion battery is the highest energy density commercialized rechargeable battery technology. This technology has the future potential to far exceed the theoretical energy densities of the aqueous NiMeH technology. Although much research has focused on the improvement of the host electrodes for Li-ion guest cation intercalation, little work has focused on alternative guest cation species to replace the Li ϩ cation.The use of Na ϩ as a low cost, potentially less reactive cation for rocking chair intercalation batteries is the most prevalent of the reported research on alternative guest cation intercalation. 1-7 Na ϩ cells have seen little commercial success because of the lack of suitable electroactive negative electrode materials. Fewer papers have focused on polyvalent cation intercalation reactions in order to develop alternative rocking chair cells using guest cations with valences greater than one. 8 Of these, the development of Mg 2ϩ -based batteries and related electrolytes 9-12 are the most widely discussed. Electrochemical intercalation of Mg 2ϩ into a number of metal oxides and sulfides were investigated, 13 however, electrochemica...

Beyond Li-ion: electrode materials for sodium- and magnesium-ion batteries

“…Slow transport kinetics are manifest in the form of large overpotentials and low intercalation levels [103,115,116]. Enhanced electrostatic effects from the divalent ion are usually cited as the culprit, but may be mitigated by the host's ability to delocalize electrons and change valence states [100,117].…”

“…Amatucci et al [115] prepared a nanocrystalline V 2 O 5 powder with particle sizes in the range of 20-50 nm using a chemical vapor condensation technique. The powder had a large surface area (~90 m 2 g −1 ) and a high reversible capacity of 180 mA h g −1 , but showed a large voltage hysteresis indicative of slow kinetics (Fig.…”

Electrochemical Behaviour of V2O5Xerogel and V2O5Xerogel/C Composite in an Aqueous LiNO3and Mg(NO3)2Solutions

“…Crystalline V 2 O 5 is capable of electrochemical intercalation of Li + and Mg 2+ ions in organic electrolytes, with relatively fair cycling performance [6,8,12]. The amorphous, hydrated form of vanadium pentoxide (V 2 O 5 nH 2 O), has a higher intercalation capacity than its crystalline form, and this was explained by the fact that water molecules expend the interlayer distance of this compound [13].…”

Utilization of Ca K-Edge X-ray Absorption Near Edge Structure to Identify Intercalation in Potential Multivalent Battery Materials

“…• C. 21 In contrast to the conversion reactions used in primary batteries, the reversible intercalation of calcium into materials such as vanadium oxide, 23,24 …”

“…• C. 21 In contrast to the conversion reactions used in primary batteries, the reversible intercalation of calcium into materials such as vanadium oxide, 23,24 TiS 2 , 25 and Prussian blue analogues 26,27 has been previously observed using electrolytes such as Ca(ClO 4 ) 2 in acetonitrile or using chemical intercalation methods. Many of these studies, however, raised questions Additionally, these questions highlight the lack of characterization tools available to identify the true intercalation species, as solvent cointercalation or ion-pairing might exist in these beyond Li-ion battery systems.…”