fundamental studies of lignin derivatives in lead acid batteries

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.

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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)

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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).

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SO3Na

Typical unit structure of LS

Typical unit structure of LS

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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)

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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


10ppm100ppm1000ppm

Potential, E / V

No additive


EC-AFM with CV With 1000ppm of LS

10

-10

Cur

rent

den

sity

, I /

Am

-2


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


10ppm100ppm1000ppm

Potential, E / V

No additive


EC-AFM with CV With 10ppm of LS

10

-10

Cur

rent

den

sity

, I /

Am

-2


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

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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

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SO3Naor HTypical unit

structure of DLS

Typical unit structure of

DLS


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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.

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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

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SML


SML

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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.

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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

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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.

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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.

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Thank you for your attention!

fundamental studies of lignin derivatives in lead acid batteries

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