p.m. (maarten) biesheuvel wageningen, the netherlands wetsus, leeuwarden, the netherlands

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P.M. (Maarten) Biesheuvel Wageningen, the Netherlands Wetsus, Leeuwarden, the Netherlands - - - - + + + + Porouselectrode Porouselectrode - - - - - - - + + + + + + + -------- + + + + + + + + Capacitive Porous Electrodes

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Capacitive Porous Electrodes. P.M. (Maarten) Biesheuvel Wageningen, the Netherlands Wetsus, Leeuwarden, the Netherlands. Capacitive Deionization. A close relative …. Supercapacitors. Capacitive Deionization (CDI). Flow-through. Static. 3. “Capacitive Deionization” – Web of Science. - PowerPoint PPT Presentation

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Page 1: P.M. (Maarten) Biesheuvel Wageningen, the Netherlands Wetsus, Leeuwarden, the Netherlands

P.M. (Maarten) BiesheuvelWageningen, the NetherlandsWetsus, Leeuwarden, the Netherlands

non-faradaic=capacitive

Capacitive Deionization

Porous electrode

Porous electrode- --

-

---

+ + +

++

++

- - - - - - - -

+ + + + + + + +

Porous electrode

Porous electrode- --

-

---

+ + +

++

++

- - - - - - - -

+ + + + + + + +

Capacitive Porous Electrodes

Page 2: P.M. (Maarten) Biesheuvel Wageningen, the Netherlands Wetsus, Leeuwarden, the Netherlands

Capacitive Deionization

non-faradaic=capacitive

Capacitive Deionization

Porous electrode

Porous electrode- --

-

---

+ + +

++

++

- - - - - - - -

+ + + + + + + +

Porous electrode

Porous electrode- --

-

---

+ + +

++

++

- - - - - - - -

+ + + + + + + +

Page 3: P.M. (Maarten) Biesheuvel Wageningen, the Netherlands Wetsus, Leeuwarden, the Netherlands

Capacitive Deionization

(CDI)Supercapacitors

Static Flow-throughnon-faradaic=capacitive

Capacitive Deionization

Porous electrode

Porous electrode- --

-

---

+ + +

++

++

- - - - - - - -

+ + + + + + + +

Porous electrode

Porous electrode- --

-

---

+ + +

++

++

- - - - - - - -

+ + + + + + + +

3

A close relative …

Page 4: P.M. (Maarten) Biesheuvel Wageningen, the Netherlands Wetsus, Leeuwarden, the Netherlands

“Capacitive Deionization” – Web of Science

Page 5: P.M. (Maarten) Biesheuvel Wageningen, the Netherlands Wetsus, Leeuwarden, the Netherlands

(Membrane) Capacitive Deionization

with ion-exchange membranes

without ion-exchange membranes

Page 6: P.M. (Maarten) Biesheuvel Wageningen, the Netherlands Wetsus, Leeuwarden, the Netherlands

Porous electrode

Porous electrode

Capacitive Deionization

- ----- -+ + + + + + +

- - - - - - - -

+ + + + + + + +

Adsorption

Vcell

6

macroporenanopore

++

+ +++

+

-

ci(x,t)f(x,t)

f1(t)Stern layer,DfSt

-

-

- --

-

-

Dfd+

Page 7: P.M. (Maarten) Biesheuvel Wageningen, the Netherlands Wetsus, Leeuwarden, the Netherlands

Capacitive Deionization

Porous electrode

Porous electrode- ----- -

+ + + + + + +- - - - - - - -

+ + + + + + + +

Releaseshort-circuit

7

macroporenanopore

++

+ +++

+

-

ci(x,t)f(x,t)

f1(t)Stern layer,DfSt

-

-

- --

-

-

Dfd+

Page 8: P.M. (Maarten) Biesheuvel Wageningen, the Netherlands Wetsus, Leeuwarden, the Netherlands

Models for the Electrical Double Layer

Page 9: P.M. (Maarten) Biesheuvel Wageningen, the Netherlands Wetsus, Leeuwarden, the Netherlands

Salt adsorption and Charge in Microporous Carbons

Equilibrium, @ Vcell=1.2 V

Page 10: P.M. (Maarten) Biesheuvel Wageningen, the Netherlands Wetsus, Leeuwarden, the Netherlands

New system designs

FreshwaterFreshwater

Page 11: P.M. (Maarten) Biesheuvel Wageningen, the Netherlands Wetsus, Leeuwarden, the Netherlands

Flowable electrodes

Page 12: P.M. (Maarten) Biesheuvel Wageningen, the Netherlands Wetsus, Leeuwarden, the Netherlands

Desalination with Wires

FreshwaterFreshwater

Page 13: P.M. (Maarten) Biesheuvel Wageningen, the Netherlands Wetsus, Leeuwarden, the Netherlands

Results published in: Porada, S., B.B. Sales, H.V.M. Hamelers, and P.M. Biesheuvel (2012) The Journal of Physical Chemistry Letters 3: 1613-1618

Desalination with Wires

Page 14: P.M. (Maarten) Biesheuvel Wageningen, the Netherlands Wetsus, Leeuwarden, the Netherlands

Ion transport phenomena in realistic systems:

Instead of “Na+ Cl-” also H+ OH- HCO3- etc.

Page 15: P.M. (Maarten) Biesheuvel Wageningen, the Netherlands Wetsus, Leeuwarden, the Netherlands

Three examples for amphoteric ionic systems

e.g., CO32-HCO3

- H2CO3

Capacitive Deionization

Current-induced membrane discharge

CO2 energy

Page 16: P.M. (Maarten) Biesheuvel Wageningen, the Netherlands Wetsus, Leeuwarden, the Netherlands

CDI – pH effects

Page 17: P.M. (Maarten) Biesheuvel Wageningen, the Netherlands Wetsus, Leeuwarden, the Netherlands

Example 2. Overlimiting current in Ion-exchange membranes

water in membrane pores membrane discharge

Page 18: P.M. (Maarten) Biesheuvel Wageningen, the Netherlands Wetsus, Leeuwarden, the Netherlands

Example 2. Overlimiting current in Ion-exchange membranes

Current Induced Membrane Discharge

Page 19: P.M. (Maarten) Biesheuvel Wageningen, the Netherlands Wetsus, Leeuwarden, the Netherlands

Example 3. “CO2 energy” from power plant off-gas

AEM CEM

H+HCO3

-

Anode Cathode

RNH3+

RNHCOO-

CO2-flushed

e-

270 µm 270 µm200 µm40 µm 40 µm

OH-

CO32-

H2CO3

--

-

-

++++

++

++

++++

++

+

++

+

-

-

--

--

Flow channel

PCE PCE

-

-

AEM CEM

H+HCO3

-

Anode Cathode

RNH3+

RNHCOO-

CO2-flushed

e-

270 µm 270 µm200 µm40 µm 40 µm

OH-

CO32-

H2CO3

--

-

-

++++

++

++

++++

++

+

++

+

-

-

--

--

Flow channel

PCE PCEAEM CEM

H+HCO3

-

Anode Cathode

RNH3+

RNHCOO-

CO2-flushed

e-

270 µm 270 µm200 µm40 µm 40 µm

OH-

CO32-

H2CO3

--

-

-

++++

++

++

++++

++

+

++

+

-

-

--

--

Flow channel

PCE PCE

-

-

Page 20: P.M. (Maarten) Biesheuvel Wageningen, the Netherlands Wetsus, Leeuwarden, the Netherlands
Page 21: P.M. (Maarten) Biesheuvel Wageningen, the Netherlands Wetsus, Leeuwarden, the Netherlands

Modeling of ion transport in amphoteric systems

e.g., CO32- + H+ HCO3

-

Page 22: P.M. (Maarten) Biesheuvel Wageningen, the Netherlands Wetsus, Leeuwarden, the Netherlands

JOH-(aq)

JNH3(g)

JH+(aq)

JNH4+(aq)

Advantages of fast ion equilibration

• By addition of balances, for each “group” such as for CO2/HCO3

-/CO32-, only one balance per group remains

• and, all dummy parameters R disappear !

• very elegant to include now reactions at solid surfaces, or evaporation

liquid gasJNH3(aq)

Page 23: P.M. (Maarten) Biesheuvel Wageningen, the Netherlands Wetsus, Leeuwarden, the Netherlands

Thank you !