ISSN 1070-4272, Russian Journal of Applied Chemistry, 2014, Vol. 87, No. 2, pp. 184−189. © Pleiades Publishing, Ltd., 2014.
Original Russian Text © V.V. Maslov, V.P. Yurkinskii, I.A. Samsonova, 2014, published in Zhurnal Prikladnoi Khimii, 2014, Vol. 87, No. 2, pp. 203−209.
INORGANIC SYNTHESIS AND INDUSTRIAL
Intercalation of Lithium into Porous Titanium
Oxide Produced by Anodic Oxidation
V. V. Maslov, V. P. Yurkinskii, and I. A. Samsonova
St. Petersburg State Polytechnic University, Polytechnicheskaya ul. 29, St. Petersburg, 195251 Russia
Received October 14, 2013
Abstract—Process of lithium intercalation in a 1 M anhydrous propylene carbonate solution of LiClO
titanium oxide produced by anodic oxidation of titanium in aqueous and nonaqueous electrolytes containing
ﬂ uoride ions was studied. It is shown that the mass of intercalated lithium, which determines the efﬁ ciency of
the cathodic reaction of lithium titanate formation, strongly depends on the speciﬁ c surface area of the oxide.
The results obtained make it possible to formulate approaches to solving the problem of raising the reversible
electrical capacity of a lithium power source.
Titanium oxide has been intensively studied in re-
cent years as a material for lithium power cells with
a nonaqueous electrolyte [1–5]. The theoretical speciﬁ c
capacity of TiO
, corresponding to the formation of the
stoichiometric compound LiTiO
, is 335 mA h g
exceeds the corresponding values for numerous cathode
materials used in lithium batteries. The reversible ca-
pacity achieved in practice for nanocrystalline TiO
150 mA h g
The problem of improving the reversible electrical
capacity of a lithium power source and the related prob-
lem associated with its low discharge current density can
be possibly solved by making higher the rate of lithium
intercalation into the oxide by raising its porosity and,
accordingly, the active surface of the cathode, involved
in the lithium intercalation process.
The goal of our present study was to perform a set of
analyses to reveal the inﬂ uence exerted by the conditions
of a preliminary porous anodic oxidation of titanium
and of the possible subsequent thermal treatment, which
determine the morphology and structure of the oxide
ﬁ lm, on the efﬁ ciency of the cathodic process of lithium
intercalation into titanium oxide (increase in the mass of
the intercalated lithium).
We studied various ways of porous oxidation of
titanium with different electrolytes containing ﬂ uoride
ions. To obtain the oxide layer porous to the greatest
extent with a large speciﬁ c surface area, we tested eight
different electrolytes for porous oxidation of titanium,
which contain additions of ﬂ uorine ions. We used aque-
ous solution of sulfuric and orthophosphoric acids with
addition of HF, nonaqueous electrolytes, and nonaqueous
electrolytes with a small addition of water, containing HF
or NaF additives.
The electrolytes mostly differed in the chemical activi-
ties of ﬂ uoride ions toward titanium oxide, which made
it possible to affect the rate of its dissolution and the
porosity of the oxide coating. It is known that replacing
the aqueous electrolyte with organic nonaqueous electro-
lytes (with ethylene glycol or glycerol) can substantially
reduce the dissolution rate of titanium oxide and yield
a well-pronounced nanotubular morphology of the oxide
layer, which enhances the porosity and makes larger the
speciﬁ c surface area of the oxide [1–5].
A 0.5-mm-thick titanium sheet (99.87%) with a natural
ﬁ lm (thickness 4–5 nm) served as the starting mate-