Sundar Mayavan Lead Acid Battery Group CSIR- Central Electrochemical Research Institute Karaikudi, INDIA. 22/9/ th Asian Battery Conference 1

Transcription

1 Influence of Carbon Nanotubes, Glycine, Boron-Carbon- Nitride and Molybdenum disulfide as Negative-Plate Additives on the Performance of Lead Acid Batteries Sundar Mayavan Lead Acid Battery Group CSIR- Central Electrochemical Research Institute Karaikudi, INDIA 22/9/ th Asian Battery Conference 1

2 Presentation Outline 1. Introduction 2. About CSIR-CECRI 3. Sulfation 4. Effect of CNT, BCN, MoS 2, Glycine in NAM 5. Concluding Remarks 22/9/ th Asian Battery Conference 2

3 CSIR-Central Electrochemical Research Institute (A premier R&D Institute in Electrochemistry) 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 Modelling Bio-sensors Nanomaterials Electrohydro Metallurgy Industrial Metal Finishing Pollution Control LEAD ACID BATTERIES - Since /9/ th Asian Battery Conference 3

4 CECRI XRD, BET, Mercury Porisometry, FE-SEM, TEM, Raman Material Characterization NABL ISO Lead System Lithium Redox Flow Battery Test Facility Potentiostat Impedance Analyser CV EIS Polarization Corrosion Electrochemical Characterization Structure Property Correlation Our Select CLIENTS TVS Motors; Reliance Industries; Mahindra Reva; Livguard.

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

6 Major Issue Sulfation 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) Source: JC 22/9/ th Asian Battery Conference

7 CNT BCN NAM Additives MoS 2 Glycine HSA Carbon 22/9/ th Asian Battery Conference 7

8 Carbon Black vs. MWCNTs 10h Cycle 0.25%CB 0.25%CNT 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. 22/9/ th Asian Battery Conference 8

9 HRPSoC Performance HRPSoC Profile D. Pavlov Et al. J Power Sources (2009) S.No NAM Additive Capacity@ 20 h HRPSoC Cycle-Sets completed Number of micro-cycles completed 1 CB 2.25 Ah MWNT 2.41 Ah J. Electrochem. Soc. 2013, 160, A70-A76 22/9/ th Asian Battery Conference 9

10 Carbon Nanotube NAM (Formed) SEM images of (d) CNT added NAM SEM images of (a) CB added NAM Schematic of a tentative mechanism for the formation of conducting network with MWCNTs added NAM. No conductive network exists in CB-NAM 22/9/ th Asian Battery Conference 10

11 Tear-Down Analysis FE-SEM of Cycled NAM MWCNT Carbon Black 10 µm 10 µm 2 µm 2 µm 200 nm 200 nm MWNT 22/9/ th Asian Battery Conference 11

12 Glycine incorporated LO as NAM RAMAN SPECTRA ANALYSIS Control NAM Formed Glycine+ LO 250 C Glycine NAM Cycled Gly-LO Intensity Glycine NAM Formed Intensity Glycine NAM Formed In-situ Carbon formation deg Graphitic carbon Raman shift (cm -1 ) Wave number(cm-1) 22/9/ th Asian Battery Conference 12

13 TEM images of 250 C Morphology of Gly & Gly-NAM FE-SEM image of formed Gly-NAM 22/9/ th Asian Battery Conference 13

14 Glycine incorporated LO as NAM Active Mass Cyclic Voltammetry HER VS. MSE The over potential for hydrogen gas evolution also increased (Figure a). Hence, with the addition of Gly suppression of hydrogen gas evolution is achieved. Carbon in-situ generated 22/9/ th Asian Battery Conference 14

15 Tear Down Analysis 800 RAMAN SPECTRA Control NAM cycled PbSO 4 Peak Intensity Glycine NAM Cycled Small PbSO 4 Peak 0 FE-SEM : Cycled NAM-Gly Raman shift (cm -1 ) 22/9/ th Asian Battery Conference 15

16 BCN incorporated NAM TEM image of BCN NAM FE-SEM image of FORMED BCN-NAM Figure (a) 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. 22/9/ th Asian Battery Conference 16

17 Tear Down Analysis FE-SEM image of cycled NAM with and without BCN BCN-NAM, the dominating elementary process is the formation of PbO instead of PbSO 4. No PbSO 4 Peak XRD of cycled NAM-BCN Raman Spectra of cycled NAM-BCN 22/9/ th Asian Battery Conference 17

18 Molybdenum di sulphide MoS 2 in NAM Graphene-like two-dimensional (2D) transition metal dichalcogenides (TMDCs) have been attracting a wide range of research interests. Molybdenum disulfide (MoS 2 ) is one of the most typical TMDCs MoS 2 is a semiconductor with a direct band gap of 1.8 ev 22/9/ th Asian Battery Conference 18

19 Performance comparison of MoS 2 vs CB vs HSA CB (Both Battery tested as per IS: 13369) Additives Supplier Amount added in % m 2 / g Type Carbon Black X Conductive High Surface Area CB Y Conductive MoS 2 Sigma Aldrich Semiconductor 100 g of Additives added to 100 Kg of Leady Oxide in Sigma Mixture 1. Battery with 0.1 % CB 2. Battery with 0.1 % CB % MoS 2 3. Battery with 0.1 % HSA CB 22/9/ th Asian Battery Conference 19

20 Morphology of Carbon Additives (FE-SEM) MoS 2 HSA CB CB 22/9/ th Asian Battery Conference 20

21 TEM Images HSA CARBON CB MoS 2 1. Battery with 0.1 % HSA CB 2. Battery with 0.1 % MoS % CB 3. Battery with 0.1 % CB 22/9/ th Asian Battery Conference 21

22 Performance comparison as per IS 13369: Battery with 0.1 % CB 2. Battery with 0.1 % CB % MoS 2 3. Battery with 0.1 % HSA CB 150 Ah Tubular Battery 22/9/ th Asian Battery Conference 22

23 Loss of capacity before and after 28 days Battery (12 V/150 Ah) No of Cycle Before 28 Days battery capacity (Ah) Time (hours) After 28 days battery capacity (Ah) Time (hours) Loss of capacity (%) (minimum 10%) 0.1 % CB :26:06 10:27: :00:33 4- Passed 0.1 % CB % MoS % HSA CB :57:04 10:58:49 10:13:06 10:16: :53: Failed Self-discharge with addition of MoS :13: Failed 22/9/ th Asian Battery Conference 23

24 Endurance Test MoS 2 shows better performance than others but only under continuous charging

25 Concluding remarks (Points to be considered for additive selection) MWNT clearly improves the performance of LAB. The utilization of nanocarbon materials will become inevitable towards development of Advanced lead acid batteries. High Surface Area is not the only criteria for performance; Structure/ Morphology/Affinity also plays a vital role. Under our test conditions, CB performs much better than engineered high surface area carbon. Wrong Additive in small quantity (in this case 0.1 % MoS 2 ) is sufficient to offset the performance of LAB. MoS 2 shows much better performance only under continuous charging conditions. (Sheet + Particle)/(conductor + Semiconductor) 22/9/ th Asian Battery Conference 25

26 Acknowledgement 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 Director CSIR-CECRI 22/9/ th Asian Battery Conference 26

27 THANK YOU 22/9/ th Asian Battery Conference 27