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Sundar Mayavan, S. Mithin kumar, C. Arul, S. Arun, V. Muthumani

Lead Acid Battery Section CSIR- Central Electrochemical Research Institute

Karaikudi, INDIA

EFFECT OF GLYCINE INCORPORATED LEADY OXIDE AND NON-CONVENTIONAL NANOSTRUCTURED ADDITIVES ON THE

PERFORMANCE OF LEAD ACID BATTERY

Presentation Outline

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1. Introduction

2. What we do at CSIR-CECRI

3. Sulfation

4. Ways to target sulfation – Lead Carbon Electrodes

5. Concluding Remarks

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CSIR-Central Electrochemical Research Institute (A premier R&D Institute in Electrochemistry)

•Modelling •Bio-sensors •Nanomaterials •Electrohydro Metallurgy •Industrial Metal Finishing •Pollution Control

•Chlor-Alkali •Corrosion & Material Protection •Electrochemical Materials Science •Electroplating & Metal Finishing Technology •Electropyro Metallurgy

•Fuel Cells •Lead Acid Batteries •Lithium Batteries •Electro Organic •Functional Materials •Electro Inorganic

LEAD ACID BATTERIES

CSIR- Battery Performance Testing Evaluation Centre (ISO/IEC 17025:2005)

What we do at CSIR-CECRI ? LAB battery Department established in 1960 @ CSIR-CECRI

Battery testing and Evaluation centre equipped with state of the

art Battery test equipment, Mercury porosimeter, Scanning Electron Microscope, XRD, Raman, XPS,.(Facility to test all battery chemistry : Flooded, VRLA, Lithium, Redox-Flow)

Structure - Property correlation studies

New additive evaluation and process optimization

Undertakes sponsored projects towards development of advanced LAB system

Our Major CLIENTS 1. TVS Motors; Reliance Industries; Exide India, Hosur; Indian

Railways

Major Issue – Sulfation

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A variety of applications ranging from micro-hybrid cars to solar energy storage require lead acid battery (LAB) to operate under partial state of charge conditions (PSoC). However, the main failure mode for batteries operating under PSoC is formation of irreversible lead sulfation in negative active material (NAM), which leads to reduced capacity and cycle life.

Micro hybrid – Batteries operate under high rate partial state of charge conditions (HRPSoC).

In renewable energy applications where sulfation can result from operating in a

partial state of charge (POSC)

Summary of the negative plate variants used in this study and of the types of tests performed.

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Sulfation : Lead Carbon Electrodes

(Effect of Nano-structured carbon additives in NAM?) SWNT MWNT Graphene

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Additive Supplier Ave. Length Size Purity Surface area SWNT Nano shell, USA 3-8 µm 1-2 nm (diameter) > 98% 350-450 m2/g

MWNT SRL, India 5-15 µm 40-50 nm (diameter) > 99% -

Graphene Nano shell, USA 1-10 µm 0.5-0.6 nm (thickness) > 99.9% 250 m2/gm

Characteristics (as specified by the supplier) of the Nano-structured Carbon materials used as additive to NAM in the present study.

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2µm 2µm 5µm

2µm 2µm 2µm

200 nm

200 nm

200 nm

GRAPHENE MWNT SWNT FE-SEM images of Formed NAM

10h Cycle

0.25%CB 0.25%CNT

0.25% CB

0.25% CNT 0.25% CNT

Carbon black vs. MWCNTs NAM under HRPSoC

HRPSoC Profile

SEM images of (a) CB added NAM, (b) Pristine MWCNTs and (c) & (d) nanoscale networked NAM with MWCNTs

Figure : a) Comparative cycling (10-h rate) performance of CB and MWCNTs added cell. (b) The rate capability of CB and MWCNT added cell at different current densities. (c-d) The comparison of the discharge curves of cells with CB and MWCNTs added cells at 10-h rate.

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Tear-Down Analysis – FE-SEM of Cycled NAM Graphene SWNT MWNT

PbO

SWNT

MWNT

10 µm 10 µm 10 µm

2 µm 2 µm 2 µm

200 nm 200 nm 200 nm

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Major Issues with Carbon Addition (Gassing) How to supress it..????

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MoS2 Boron Carbon Nitride Glycine

Hollow silica microspheres

With MWNT performance enhanced....but gassing is an issue

In NAM In NAM In NAM

In PAM

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Glycine incorporated LO as NAM

0 500 1000 1500 2000 2500 3000 3500 4000

0

2000

4000

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5000

10000

15000

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20000

40000

Wave number(cm-1)

Glycine @250 deg

Inte

nsity

Glycine NAM Formed

Glycine NAM Cycled

0 500 1000 1500 2000 25000

5000

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15000

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1000

2000

3000

4000

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nsity

Raman shift (cm-1)

Glycine NAM Formed

Control NAM FormedGlycine+ LO Gly-LO

250 °C

RAMAN SPECTRA ANALYSIS

Graphitic carbon

Morphology of Gly & Gly-NAM

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TEM images of Glycine @ 250 °C

FE-SEM image of formed Gly-NAM

Glycine incorporated LO as NAM Active Mass

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The over potential for hydrogen gas evolution also increased (Figure a). Hence, with the addition of Gly suppression of hydrogen gas evolution is achieved.

Cyclic Voltammetry HER

VS. MSE

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Tear Down Analysis

Small PbSO4 Peak

PbSO4 Peak

FE-SEM : Cycled NAM-Gly

RAMAN SPECTRA

0 200 400 600 800 1000 1200 1400

0

1000

2000

30000

200

400

600

800

Inte

nsity

Raman shift (cm-1)

Glycine NAM Cycled

Control NAM cycled

Molybdenum di sulphide MoS2 in NAM

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Graphene-like two-dimensional (2D) transition metal dichalcogenides (TMDCs) have been attracting a wide range of research interests. Molybdenum disulfide (MoS2) is one of the most typical TMDCs

MoS2 is a semiconductor with a direct bandgap of 1.8 eV

Morphology of MoS2

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FE-SEM images of MoS2

TEM images of MoS2

MoS2 in NAM

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The CV curves shows anodic peak corresponding to the oxidation of Pb to PbSO4 and the cathodic peak relates to reduction of as-formed PbSO4 to spongy Pb.

Incorporation of MoS2 in NAM also reduces the over potential for hydrogen evolution reaction (HER) significantly.

CV of formed NAM with and without MoS2

VS. MSE

Using non conducting Molybdenum di sulfide (MoS2) as NAM additive

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Unformed NAM Formed NAM with MoS2

Cycled NAM with carbon X

Cycled NAM with carbon Y

Hollow Silica in PAM (Porosity enhancer)

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Glass bubbles K15 from 3M Particle size : 105 microns

VS. MSE

Capacity @ various rates

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MCM 41 Silica in PAM (Porosity enhancer)

FE-SEM of MCM-41

VS. MSE

BCN incorporated NAM

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NAM FE-SEM image of FORMED BCN-NAM

TEM image of BCN

Cycling performance of a BCN added cell. (b) Completed HRPSoC cycles per set for a cell with BCN. (c) Cell capacity after each HRPSoC cycle set.

Tear Down Analysis

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BCN-NAM, the dominating elementary process is the formation of PbO instead of PbSO4.

No PbSO4 Peak

XRD of cycled NAM-BCN Raman Spectra of cycled NAM-BCN

FE-SEM image of cycled NAM with and without BCN

Concluding remarks MWNT/Nano carbons CLEARLY improves the performance of

LAB

Utilization of high surface area carbon/nanocarbon materials will become inevitable in the development of Advanced lead acid batteries.

To offset issues with HSA carbon (GASSING) the usage of hybrid additives will become inevitable.

Hybrid functional additives holds the KEY for advanced LAB rather than a normal simple additives.

BMS for lead acid battery system.

Acknowledgement

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Director CSIR-CECRI

Ph.D Students : Mr. Mithin Kumar, Mr. Arun Project Assistants: Mr. C.Arul, Mr. Arun & Saravanakumar Technical officers: Mr. P.Seenichamy, Mr. V.muthumani, Mr. E.Sekar Funding : DST-SERB, TVS Motors, CSIR-CECRI, Jazz Batteries

Thank You

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