fundamental studies of lignin derivatives in lead acid batteries
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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. - PowerPoint PPT PresentationTRANSCRIPT
Osaka University13ABC on Sep. 4, 2009 in Macau
Fundamental Studies of Lignin Derivatives in Lead Acid Batteries
Osaka University
Forestry and Forest Products Institute
Sep. 4, (2009), 13ABC in MacauAssociate Professor, Osaka University,
JAPANNobumitsu Hirai
Forestry and Forest Product Research Institute, JAPAN
Satoshi Kubo, Tsutomu Ikeda, Kengo Magara
Osaka UniversityBackground – What is natural “lignin”?
*One of the 3 main components of woods or plants
Typical structureof natural lignin
Typical structureof natural lignin
Cellulose, Hemi-cellulose and LigninTypical unit structure of natural
ligninTypical unit structure of natural
lignin
C
C
C
OH
OCH3
C
C
C
OH
CH3O
C
C
C
OH
OCH3
(1) (2) (3) Hard Wood:(2), Soft Wood:
(1)+(2) Other Plants:(1)+(2)+(3)
Osaka UniversityBackground – “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.
Osaka University
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
Investigation of electrochemical behavior of flat Pb
electrode in sulfuric acid solution with lignin derivatives
Osaka UniversityExperimental 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)
Osaka University
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 desulfonated lignosulfonate (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).
Osaka University
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 desulfonated lignosulfonate (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).
SO3Na
Typical unit structure of LS
Typical unit structure of LS
Osaka University
CV with or without LS
CV of Pb flat electrode in 1M (s.g.1.06), 3M (1.18), or 7M (1.40) H2SO4 solution with or without LS
CV of Pb flat electrode in 1M (s.g.1.06), 3M (1.18), or 7M (1.40) H2SO4 solution with or without LS
-1.2 -1.1 -1 -0.9 -0.8
0
10
1M-NA1M-LS100ppm3M-NA3M-LS100ppm7M-NA7M-LS100ppm
Scan Rate: 10mVmin -1
Potential, E / V vs. Hg/Hg2SO4
Cur
rent
den
sity
, i /
Am-2
-1.2 -1.1 -1 -0.9 -0.8 -0.7 -0.6
0
100
200
300
4001M-NA1M-LS100ppm3M-NA3M-LS100ppm7M-NA7M-LS100ppm
Scan Rate: 50mVsec -1
Potential, E / V vs. Hg/Hg2SO4
Cur
rent
den
sity
, i /
Am-2 Reference Electrode:
Hg / Hg2SO4
Reference Electrode: Hg / Hg2SO4
x 300
LS used: sodium salt of lignosulfonic acid (Aldrich, No. 47103-8)
Osaka University
1M (s.g.1.06
)
1M (s.g.1.06
)
7M (s.g.1.40
)
7M (s.g.1.40
)3M
(s.g.1.18)
3M (s.g.1.18
)
Anodic capacity of CV(=roughly corresponding discharge capacity of NAM)
1 10 100 10000
10
20
Concentration of LS, c / mgl-1
Ano
dic
Cap
acit
y, Q
/ C
m-2
0
10mVm -1
50mVm -1
10mVs -1
50mVs -11 10 100 1000
0
10
20
Concentration of LS, c / mgl-1A
nodi
c C
apac
ity,
Q /
Cm-2
0
10mVm -1
50mVm -1
10mVs -1
50mVs -1
1 10 100 10000
10
20
Concentration of LS, c / mgl-1
Ano
dic
Cap
acit
y, Q
/ C
m-2
0
10mVm -1
50mVm -1
10mVs -1
50mVs -1
Osaka University10m
-1.3 -1.2 -1.1 -1 -0.9 -0.8
-1
0
1
CV 無添加 1M 1212-2.TXTCV LS 100PPM 1M 1212.TXTCV LS 1000PM 1M 1214.TXT
10ppm100ppm1000ppm
Potential, E / V
No additive
Scan rate : 10mVmin-1
EC-AFM with CV No additive (with 0ppm of LS)
10
-10
Cur
rent
den
sity
, I /
Am
-2
In 1M H2SO4 solution (s.g.1.06)
Pb PbO PbSO4? Dissolution of PbSO4 is rapid.
Pb PbO PbSO4? Dissolution of PbSO4 is rapid.
Osaka University10m
-1.3 -1.2 -1.1 -1 -0.9 -0.8
-1
0
1
CV 無添加 1M 1212-2.TXTCV LS 100PPM 1M 1212.TXTCV LS 1000PM 1M 1214.TXT
10ppm100ppm1000ppm
Potential, E / V
No additive
Scan rate : 10mVmin-1
EC-AFM with CV With 1000ppm of LS
10
-10
Cur
rent
den
sity
, I /
Am
-2
In 1M H2SO4 solution (s.g.1.06)
Dissolution-precipitation reaction! The dissolution of PbSO4 crystal delays with addition of LS.
Dissolution-precipitation reaction! The dissolution of PbSO4 crystal delays with addition of LS.
Osaka University10m
-1.3 -1.2 -1.1 -1 -0.9 -0.8
-1
0
1
CV 無添加 1M 1212-2.TXTCV LS 100PPM 1M 1212.TXTCV LS 1000PM 1M 1214.TXT
10ppm100ppm1000ppm
Potential, E / V
No additive
Scan rate : 10mVmin-1
EC-AFM with CV With 10ppm of LS
10
-10
Cur
rent
den
sity
, I /
Am
-2
In 1M H2SO4 solution (s.g.1.06)
Also dissolution-precipitation reaction. The dissolution of PbSO4 crystal delays with higher concentration of LS.
Also dissolution-precipitation reaction. The dissolution of PbSO4 crystal delays with higher concentration of LS.
Osaka UniversityRotating ring disk electrode (RRDE) – Up-takes of Pb2+ ions by LS –
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.
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.
0 10 20 30 40-0.6
-0.4
-0.2
0
0.2
Time, t/ sec
Rin
g C
urre
nt C
hang
e,
i r`/
AWith LS
Without LS
4mm5mm 7mm
Disc current = 30uA (full charge)-3uA (discharging)
Dissolved Pb2+ ions decreasewith LS addition
Dissolved Pb2+ ions decreasewith LS addition
Ring currentdecreases
Osaka University
Proposed function of LSproposed 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
Osaka University
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)
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).
SO3Naor HTypical unit
structure of DLS
Typical unit structure of
DLS
1.CV of Pb flat electrodes in sulfuric acid solution with partially desulfonated lignosulfonate (DLS)
Osaka University
Experimental for DLS
Lignin derivative used: DLS (partially desulfonated LS)
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% NaOH
aqueous solution at 150C for 0.5-2 hours.
Osaka University
CV with DLS
-1.3 -1.2 -1.1 -1 -0.9 -0.8
0
5
10
15LS-control150-20-0.5150-20-1.0150-20-1.5150-20-2.0
Potential, E/ V vs.Hg/Hg 2SO4
Cur
rent
, I/
mA
NA
Sample Organic S (mol/g) Molecular Weight (MW)
LS-control 1.9x103 3.8x104
150-20-0.5 1.0x103 8.9x103
150-20-1.0 8.3x102 7.2x103
150-20-1.5 5.0x102 6.0x103
150-20-20 4.7x102 6.3x103
Scan rate: 10mVmin-1
Osaka University
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 desulfonated lignosulfonate (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).
Typical unit structure of
SML
Typical unit structure of
SML
Osaka University
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.
Osaka University
CV for SML
-1.3 -1.2 -1.1 -1 -0.9 -0.8
0
5
10
15SML(1:8)SML(1:4)SML(1:2)SML(1:1)SML(2:1)
Potential, E/ V vs.Hg/Hg2SO4
Cur
rent
, I/
mA
NA
Sample Organic S(mol/g) Molecular Weight (MW)
SML(1:8) 1.7x102 5.3x103
SML(1:4) 4.2x102 8.6x103
SML(1:2) 7.7x102 1.2x104
SML(1:1) 1.1x103 5.2x103
Scan rate: 10mVmin-1
Osaka University
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 desulfonated lignosulfonate (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).
Osaka UniversityTrial for improvement of charge acceptance
Ex. Cyclic Voltammograms (CVs) of Pb plate
-1.2 -1.1 -1 -0.9-2
0
2
4
6
Potential, E/V vs. Hg/Hg2SO4
Cur
rent
Den
sity
, i/A
m-2 No additiveAdditive1
DischargeCurrent
ChargeCurrent
-1.2 -1.1 -1 -0.9
-4
-2
0
2
4
6
Additive2
Potential, E/ V vs.Hg/Hg2SO4
Cur
rent
den
sity
, I/
Am-2 No additive
25% Up60% Up
10mVmin-1
10mVmin-1
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.
Osaka University
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.
Osaka University
Thank you for your attention!