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Fundamental Studies of Lignin Derivatives in Lead Acid Batteries

Fundamental Studies of Lignin Derivatives in Lead Acid Batteries. Sep. 4, (2009), 13ABC in Macau Associate Professor, Osaka University, JAPAN Nobumitsu Hirai Forestry and Forest Product Research Institute, JAPAN Satoshi Kubo, Tsutomu Ikeda, Kengo Magar a. Osaka University.

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Fundamental Studies of Lignin Derivatives in Lead Acid Batteries

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  1. Fundamental Studies of Lignin Derivatives in Lead Acid Batteries Sep. 4, (2009), 13ABC in Macau Associate Professor, Osaka University, JAPAN Nobumitsu Hirai Forestry and Forest Product Research Institute, JAPAN Satoshi Kubo, Tsutomu Ikeda, Kengo Magara Osaka University Forestry and Forest Products Institute

  2. Background – What is natural “lignin”? Cellulose, Hemi-cellulose and Lignin *One of the 3 main components of woods or plants Typical structure of natural lignin Typical unit structure of natural lignin C C C C C C C C C OCH3 CH3O OCH3 OH OH OH (1) (2) (3) Hard Wood:(2), Soft Wood:(1)+(2) Other Plants:(1)+(2)+(3)

  3. Background – “lignin” in lead acid battery *Lignin used in lead acid battery, lignin derivatives, called “Expander”, is recovered from an effluent of a sulfite pulping process. *One of the additives in negative active materials (NAM) Ex.) (Partially desulfonated) Lignosulfonate (Vanisperse A, Vanillex N…), Kraftlignin (Indulin AT…), etc. *Typical effect of lignin derivatives on NAM in lead acid battery They affect the properties of NAM (porosity, surface area, etc) They affect discharging and charging behaviors and so on.

  4. Objective * In order to adapt increasing the variety of the application field of lead acid battery for environmental friendly society, fundamental studies of lignin derivatives in lead acid batteries are indispensable. * Because lignin derivatives affect not only discharging and charging behaviors but also the properties of NAM (porosity, surface area, etc), investigation of electrochemical behavior of flat Pb electrode in sulfuric acid solution with lignin derivatives is still interesting from a viewpoint of analytical understanding of the effect of lignin derivative. Investigation of electrochemical behavior of flat Pb electrode in sulfuric acid solution with lignin derivatives

  5. Experimental in this presentation Electrode: Flat Pb electrodes (purity: 99.999%) Electrolyte: 1-7M (s.g.=1.06-1.40) sulfuric acid solution + lignin derivative initially dissolved in water (or NaOH solution) Experimental tools for analysis: *CV(cyclic voltammogram) *in-situ EC-AFM (Electrochemical Atomic Force Microscopy) *RRDE (Rotating ring disk electrode)

  6. Outlines of today’s presentation 0. Combined in-situ Electrochemical Atomic Force Microscopy (EC-AFM) and Cyclic Voltammetry (CV) of Pb flat electrodes in sulfuric acid solution with or without lignosulfonate (LS) 1. CV of Pb flat electrodes in sulfuric acid solution with partially desulfonatedlignosulfonate (DLS) 2. CV of Pb flat electrodes in sulfuric acid solution with Sulfomethyl Lignin (SML) 3. CV of Pb flat electrodes in sulfuric acid solution with new lignin derivatives (in progress).

  7. Outlines of today’s presentation 0. Combined in-situ Electrochemical Atomic Force Microscopy (EC-AFM) and Cyclic Voltammetry (CV) of Pb flat electrodes in sulfuric acid solution with or without lignosulfonate (LS) C C 1. CV of Pb flat electrodes in sulfuric acid solution with partially desulfonatedlignosulfonate (DLS) C SO3Na 2. CV of Pb flat electrodes in sulfuric acid solution with Sulfomethyl Lignin (SML) OCH3 CH3O or H OH 3. CV of Pb flat electrodes in sulfuric acid solution with new lignin derivatives (in progress). Typical unit structure of LS

  8. CV with or without LS LS used: sodium salt of lignosulfonic acid (Aldrich, No. 47103-8) CV of Pb flat electrode in 1M (s.g.1.06), 3M (1.18), or 7M (1.40) H2SO4 solution with or without LS x 300 Reference Electrode: Hg / Hg2SO4 Reference Electrode: Hg / Hg2SO4

  9. Anodic capacity of CV (=roughly corresponding discharge capacity of NAM) 7M (s.g.1.40) 3M (s.g.1.18) 1M (s.g.1.06)

  10. 10m EC-AFM with CV No additive (with 0ppm of LS) • In 1M H2SO4 solution • (s.g.1.06) 10 Current density, I / Am-2 No additive 10ppm Scan rate : 10mVmin-1 100ppm -10 1000ppm Pb PbO PbSO4? Dissolution of PbSO4 is rapid. Potential, E / V

  11. 10m EC-AFM with CV With 1000ppm of LS • In 1M H2SO4 solution • (s.g.1.06) 10 Current density, I / Am-2 No additive 10ppm Scan rate : 10mVmin-1 100ppm -10 1000ppm Dissolution-precipitation reaction! The dissolution of PbSO4 crystal delays with addition of LS. Potential, E / V

  12. 10m EC-AFM with CV With 10ppm of LS • In 1M H2SO4 solution • (s.g.1.06) 10 Current density, I / Am-2 No additive 10ppm Scan rate : 10mVmin-1 100ppm -10 1000ppm Also dissolution-precipitation reaction. The dissolution of PbSO4 crystal delays with higher concentration of LS. Potential, E / V

  13. Rotating ring disk electrode (RRDE) – Up-takes of Pb2+ ions by LS – 4mm 5mm 7mm Dissolved Pb2+ ions decrease with LS addition With LS Without LS Ring current decreases Disc current = 30uA (full charge)  -3uA (discharging)  Capture of Pb2+ ions also occurs by the ion exchange reactions with mainly sulfonic groups in LS in the solution with sulfuric acid under potential control.

  14. Proposed function of LS proposed from present and previous works of ours + a lot works of previous researchers 1. Absorption of lignin (not only LS but also other lignin) on Pb surface 2. Temporal (not permanent) up-takes of Pb2+ ions by sulfonic groups in LS

  15. Outlines of today’s presentation 0. Combined in-situ Electrochemical Atomic Force Microscopy (EC-AFM) and Cyclic Voltammetry (CV) of Pb flat electrodes in sulfuric acid solution with or without lignosulfonate (LS) C C 1. CV of Pb flat electrodes in sulfuric acid solution with partially desulfonatedlignosulfonate (DLS) C SO3Na or H 2. CV of Pb flat electrodes in sulfuric acid solution with Sulfomethyl Lignin (SML) OCH3 CH3O or H OH Typical unit structure of DLS 3. CV of Pb flat electrodes in sulfuric acid solution with new lignin derivatives (in progress).

  16. Experimental for DLS Lignin derivative used: DLS (partially desulfonatedLS) LS used: sodium salt of lignosulfonic acid (Aldrich, No. 47103-8) Electrolyte: 5M (s.g.=1.29) sulfuric acid solution + DLS initially dissolved in water How to obtain DLS used here : *Hydrothermal treatment of LS in 20wt% NaOHaqueous solution at 150C for 0.5-2 hours.

  17. CV with DLS Scan rate: 10mVmin-1

  18. Outlines of today’s presentation 0. Combined in-situ Electrochemical Atomic Force Microscopy (EC-AFM) and Cyclic Voltammetry (CV) of Pb flat electrodes in sulfuric acid solution with or without lignosulfonate (LS) C C 1. CV of Pb flat electrodes in sulfuric acid solution with partially desulfonatedlignosulfonate (DLS) C 2. CV of Pb flat electrodes in sulfuric acid solution with Sulfomethyl Lignin (SML) CH2SO3Na CH3O or H OH Typical unit structure of SML 3. CV of Pb flat electrodes in sulfuric acid solution with new lignin derivatives (in progress).

  19. Experimental for SML Chemical used: A) Lignin, Hydrolytic (Aldrich, No. 37107-6) (Lignin extracted from “bagasse”) B) HCHO C) Na2SO3 How to obtain SML used here * Hydrothermal treatment of A+B+C.

  20. CV for SML Scan rate: 10mVmin-1

  21. Outlines of today’s presentation 0. Combined in-situ Electrochemical Atomic Force Microscopy (EC-AFM) and Cyclic Voltammetry (CV) of Pb flat electrodes in sulfuric acid solution with or without lignosulfonate (LS) 1. CV of Pb flat electrodes in sulfuric acid solution with partially desulfonatedlignosulfonate (DLS) 2. CV of Pb flat electrodes in sulfuric acid solution with Sulfomethyl Lignin (SML) 3. CV of Pb flat electrodes in sulfuric acid solution with new lignin derivatives (in progress).

  22. Trial for improvement of charge acceptance Ex. Cyclic Voltammograms (CVs) of Pb plate 10mVmin-1 25% Up 10mVmin-1 60% Up Prof. Pavlov’s group also found another additive which improve charge acceptance (in LABAT2008). Our proceeding target is a “combination” of lignin derivatives and these additives which improve charge acceptance and keep the other performance.

  23. Acknowledgements This study was partly supported by Industrial Technology Research Grant Programs (ID: 05A48006d) from New Energy and Industrial Technology Development Organization (NEDO) of Japan.

  24. Thank you for your attention!

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