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ELECTROCHEMISTRY
LITHIUM ION BATTERIES
SAIFUL ISLAM
CONTENTSI
Lithium ion Batteries (LIB)
IAnode materials for LIB
II
1.Insertion (Intercalation/de-intercalation)-type materials.
2.Alloy/de-alloy materials.
3.Conversion materials.
Cathode Materials for LIB
1.Triclinic structured Materials
2. Spinal type Materials
3. Layered Materials
4. Olivine structured Materials
5. Rhombohedral structured Materials
Lithium Ion Battery
Current lithium ion technology is based on a layered LiCoO2 cathode and graphite
anode
Lithium Ion Battery
Anode Material for Lithium ion Batteries
Find alternative material for lithium ion batteries
Graphite Exfoliation
Reduce cycle life of battery
Low capacity (372 mah/g)
Can accommodate only one Li-ion with six Carbon
Easy exfoliation
Anode Material for Lithium ion Batteries
Anode material for lithium ion batteries
Schematic illustration of active anode materials for the next generation
of lithium batteries. Potential vs. Li/Li+ and the corresponding capacity
density are shown.
S. Goriparti et al. / Journal of Power Sources 257 (2014) 421-443
Insertion-type Materials for Lithium ion Battery
Titanium Based Oxides
Li4Ti5O12 is considered the most appropriate titanium based oxide
material for lithium storage purposes because
1. It exhibits excellent Li-ion reversibility at the high operating potential
of 1.55 V vs. Li/Li+.
2. Lithium insertion/extraction in LTO occurs by the lithiation of spinel
Li4Ti5O12 yielding rock salt type Li7Ti5O12.
3. During the insertion process, the spinel symmetry and its structure
remain almost unaltered.
A.S. Prakash, P. Manikandan, K. Ramesha, M. Sathiya, J.M. Tarascon, A.K. Shukla, Chem. Mater. 22
(2010) 2857-2863.
The cation distribution in Li4Ti5O12
and Li7Ti5O12 phases during
electrochemical charge/discharge
processes could be written as
follows:
Limitation:
Its poor electronic conductivity (10-13 Scm-1) limits its full capacity at high charge
and discharge.
Growing of LTO nanowires on
titanium foil and an improvement in
the conductivity of LTO nanowires by
introducing Ti3+ ions through
hydrogenation
L. Shen, E. Uchaker, X. Zhang, G. Cao, Adv. Mater. 24 (2012) 6502-6506
These nanowires containing Ti foil
were directly used as electrodes
without any conductive additives and
binders, and they exhibited brilliant
rate performance by reaching a
capacity value close to the theoretical
one, i.e. 173 mAhg-1 at 0.2C rate with
good cycle life. Moreover, this value
became 121 mAh g-1 at 30C.
Insertion-type Materials for Lithium ion Battery
Alloy/De-Alloy Materials
Which can react with lithium to form alloys
The working voltage of Sn and Sn alloys at 0.6V vs lithium is 0.2V higher than
that of Si and Si alloys
Tin oxide (SnO2):
Reversible Sn-lithium alloying/ dealloying
reaction:
SnO2 + 4Li ↔ Sn + 2Li2O,
Sn + 4.4Li+ ↔ Li4.4Sn
This overall electrochemical process involves 8.4Li for one SnO2
formula unit.
Tin Based Anode Materials
various morphological structures of SnO2 have been widely
investigated such as nanowires, nanotubes, nanorod, nanoboxes
and nanosheets
Short size SnO2 nanotubes showed better electrochemical behavior
in terms of capacity and cycling life. The measured discharge
capacity was 468 mAh g-1 after 30 cycles
J. Ye, H. Zhang, R. Yang, X. Li, L. Qi, Small 6 (2010) 296-306
Tin Based Anode Materials
Conversion Materials
In this section we will provide an overview on the transition metal
compounds such as oxides, phosphides, sulphides and nitrides
(MxNy; M = Fe, Co, Cu, Mn, Ni and N = O, P, S and N) when
utilized as anodes in LIBs. Anodes based on these compounds
exhibit high reversible capacities (500-1000 mAhg-1 ) owing to the
participation of a high number of electrons in the conversion
reactions. The electrochemical conversions reactions can be
described as follows:
MxNy + zLi+ + ze- ↔ LizNy + xM
(Here M = Fe, Co, Cu, Mn, Ni & N = O, P, S and N)
Iron oxide
Iron based oxides have been extensively used for rechargeable
lithium batteries for the following Advantages:
Low cost
Non toxicity
High Natural Abundance
Limitation:
1.Poor cycle performance.
2.Low diffusion of Li-ions.
3. High Volume expansion during charging and discharging.
Very recently, nanoparticulate Fe2O3 tubes have been obtained from microporous organic
nanotubes (MONT) used as template. The prepared porous Fe2O3 nanotubes exhibited
excellent electrochemical performances with large capacities such as 918 and 882 mAhg-1 at
current densities of 500 and 1000 mAg-1 , respectively. These results indicate that low cost iron
based oxides with highly conductive carbon composites can be a valid alternative to graphite
anodes.
N. Kang, J.H. Park, J. Choi, J. Jin, J. Chun, I.G. Jung, J. Jeong, J.-G. Park, S.M. Lee, H.J. Kim, S.U. Son,
Angew. Chem. Int. Ed. 51 (2012) 6626-6630.
Iron oxide
Chemical Physics Letters 681 (2017) 44–49
Carbon-coated Rhombohedral Li2NaV2(PO4)3 -
Cathode
Chemical Physics Letters 681 (2017) 44–49
Carbon-coated Rhombohedral Li2NaV2(PO4)3 -
Cathode
COMPARISON OF RECHARGEABLE BATTERY TECHNOLOGIES
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