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15/6/2017 LABAT' 2017 CSIR-CECRI 1
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
15/6/2017 LABAT' 2017 CSIR-CECRI 2
1. Introduction
2. What we do at CSIR-CECRI
3. Sulfation
4. Ways to target sulfation – Lead Carbon Electrodes
5. Concluding Remarks
15/6/2017 LABAT' 2017 CSIR-CECRI 3
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
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.
15/6/2017 7 LABAT' 2017 CSIR-CECRI
Sulfation : Lead Carbon Electrodes
(Effect of Nano-structured carbon additives in NAM?) SWNT MWNT Graphene
15/6/2017 LABAT' 2017 CSIR-CECRI 8
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.
15/6/2017 LABAT' 2017 CSIR-CECRI 9
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.
10/6/2014 LABAT' 2014 CSIR-CECRI 10
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
LABAT' 2017 CSIR-CECRI 15/6/2017 11
Major Issues with Carbon Addition (Gassing) How to supress it..????
15/6/2017 LABAT' 2017 CSIR-CECRI 12
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
15/6/2017 LABAT' 2017 CSIR-CECRI 13
Glycine incorporated LO as NAM
0 500 1000 1500 2000 2500 3000 3500 4000
0
2000
4000
0
5000
10000
15000
0
20000
40000
Wave number(cm-1)
Glycine @250 deg
Inte
nsity
Glycine NAM Formed
Glycine NAM Cycled
0 500 1000 1500 2000 25000
5000
10000
15000
0
1000
2000
3000
4000
Inte
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
15/6/2017 LABAT' 2017 CSIR-CECRI 17
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
MoS2 in NAM
15/6/2017 LABAT' 2017 CSIR-CECRI 19
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)
15/6/2017 LABAT' 2017 CSIR-CECRI 21
Glass bubbles K15 from 3M Particle size : 105 microns
VS. MSE
BCN incorporated NAM
15/6/2017 LABAT' 2017 CSIR-CECRI 24
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
15/6/2017 LABAT' 2017 CSIR-CECRI 25
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
15/6/2017 LABAT' 2017 CSIR-CECRI 27
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