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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