Hydrogen Production using PEM Water Electrolyzers

Numerical and Experimental Investigations

Project Supervisor Prof. Suddhasatwa Basu

Abhijay Awasthi 2005ch50101

Technology Overview
Advantages over conventional alkaline electrolyzers Higher production rate

High power density at low temperatures

Compact mass volume characteristics Greater safety Direct source of high purity hydrogen gas

Applications of PEM electrolyzers Hydrogen supply for fuel cells Regenerative fuel cell systems On board generation of oxygen in space applications Analytical chemistry (Gas chromatography) Manufacture of semiconductors for electronic industry

Outline

Modeling of PEM electrolyzer unit Analysis of PEMWE & PEMFC system with solar energy source Experimental investigations of PEMWE Multiphysics modeling of PEMWE

Part 1 Modeling and Simulation of a PEMWE

Objective
To develop a model for PEMWE and study its performance by simulating it

Why model ??
A good model can predict PEM water electrolyzer performance under a wide range of operating conditions eliminating the need to do experiments again and again.

Can be used to identify better materials and operating conditions for optimum performance.

Model
1. Anode Section 2. Cathode Section 3. PEM Section 4. Voltage Section

Simulations done on MATLAB/SIMULINK

Mass Transport
FH O
2 out

FO

2out

FH

2out

PEM

O2g

FH O
2

eod

H2g

H2Ocons

FH O
2

pe

FH O
2

Anode

Cathode

FH O
2

in

Mass Transport
Species generation and consumption using Faradays law

I O2g = nF
Mass transport through membrane - Electro osmotic drag - Diffusion - Due to pressure difference
Interaction with anode & cathode sections

Electro-osmotic Drag
H+ ions while conducting from anode to cathode side drag some water molecules with themselves.

FH2Oeod = nd . I / F nd = electro osmotic drag coefficient (mol H2O/mol H+) nd depends on the water content of the membrane. Values vary significantly in literature. Most of the data is for fuel cell operation.

Transport due to diffusion and P

Transport due to diffusion using Ficks law Darcy law used to find transport due to P

Species concentration required to calculate diffusion

Species Concentration

CO2,me CO2,ch CH2O,ch,an CH2,me CH2,ch

CH2O,me,cat CH2O,me,an CH2O,ch,cat

Anode Cathode

A Detailed mathematical formulation can be found here:

F.Marangio, M. Santarelli, M. Cali. Theoretical model and experimental analysis of a high pressure PEM water electrolyzer for hydrogen production

Voltage

Open Circuit Voltage

Ohmic Overvoltage

Activation Overvoltage

Overpotential
OCV Calculated using Nernst equation using a temperature dependent value for reversible cell voltage Activation Overvoltage

= charge transfer coefficient i = current density io = exchange current density

Ohmic Overvoltage Vohm = I. Rohm

Model Validation
2.5

Volatage, Volt

1.5

0.5

T=55 deg C, P=10 bar, exp T=55 deg C, P=10 bar, model T= 40 deg C, P=70 bar, exp T=40 deg C, P=70 bar, model

0 0 0.2 0.4 0.6 Current Density, A/cm2 0.8 1 1.2

Contribution of various overvoltages

i = 0.2 A/cm2

i = 1 A/cm2

Effect of Temperature and Pressure

2.5 2

Voltage, V

1.5

0.5

0 0 0.2 0.4 0.6 0.8 1 1.2 Current Density, A/cm2 T=80 deg C T=40 deg C

2.5

Voltage, V

1.5

0.5

0 0 0.2 0.4 0.6 0.8 1 1.2 Current Density, A/cm2 P = 1 Mpa P= 5 Mpa P = 10 Mpa

Effect of Temperature and Pressure

Transient response
45 40 35
Power, W

30 25 20 15 10 5 0

100

200

300
time,sec

400

500

600

700

0.009 0.008 0.007

Hydrogen outflow, mol/s

0.006 0.005 0.004 0.003 0.002 0.001 0

0 100 200 300 time, sec 400 500 600 700

Conclusions
A high temperature operation favors the electrolysis.

High pressure operation increases the polarization voltage but it is cost effective in terms of storage of hydrogen.
Model is control oriented and can be used to model a prototype. Model can capture the varying power conditions and can be used to couple electrolyzer with other renewable energy systems like solar energy, wind energy etc.

Part 2 Analysis of PEMWE & PEMFC system with solar energy source for residential power requirements

Background
Solar PV systems - sun dependent power supply - time dependent power demand of a residence Use of energy storage device in conjunction with PV array Rechargeable lead acid batteries most commonly used Another alternative Regenerative fuel cells

Model

PV power supply

Power Management

Residential power demand

Battery

RFC

Utility grid

Gas Storage

Power flow strategy

Excess power Residential power demand

PV power supply

Battery Gas Storage

Electrolyzer

Utility grid

Power flow strategy

Deficit power Residential power demand

PV power supply

Battery
Gas Storage

Fuel cell

Utility grid

PV array model
Input data to the model Time of the day Output Power supplied Time of the day gives solar irradiance (from look up table) which is fed to the PV array. Solar irradiance gets converted into the max. power supplied from the PV array based on a non linear Maximum power point tracking scheme (MPPT).

PV cell
I-V characteristics determined using a set of differential and algebraic equations with solar irradiance G (kW/m2) as the parameter

PV array solar irradiance

Output of a 4.5 kW PV array

1000 900 800 700 600 G, W/m2 500 400 300 200 100 0 0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 time (hour of day)

Battery empirical model

Data required - Battery voltage vs. state of charge (SOC) Charging and discharging rates selected to be constant

Continuous integration of SOC value of battery w.r.t. time Based on SOC, discharge voltage of the battery is selected from the lookup table Power supplied/consumed by battery is calculated using this discharge voltage value

PEMFC and PEMWE model

0.4
0.35 2 power density, W/cm2 Power density, W/cm2 0 0.2 0.4 0.6 0.8 1 0.3 0.25 0.2 0.15 0.1 0.05 0 current density, A/cm2 0 0 0.2 0.4 0.6 0.8 1 current density, A/cm2

2.5

1.5

0.5

Fuel cell

Electrolyzer

Hydrogen storage
Rate of H2 addition = generation by electrolyzer consumption by fuel cell Faradays law = I/nF Integration w.r.t. to time Moles of H2 updated with time

MATLAB/SIMULINK model

Electrolyzer

PV Source

Load

Battery

Grid

Fuel cell

Modes of operation

Grid parallel Standalone With/Without battery Variable battery, fuel cell and electrolyzer capacities

Load/Demand Profile
Data for village homes in Jammu

Ref. Jha A k, Saksena S. A. Novel analytical method for sizing of standalone PV system.2005, IE journal

Hydrogen generation in system

180 160 140 Moles of H2 generated 120 100 80 60 40

20
0 -1 -20

14 Time of day (Hour)

19

24

Battery : 500 A-Hr PEMWE & PEMFC : 5 kw

Results - Standalone
In 24 hour run % load powered by individual components

23% 39%

Pv fc
61% 16% 61%

pv
fc battery

Without battery

With battery

System Efficiency - Standalone

System efficiency: = kWh (load) + kWh(H2 produced) kWh (PV) + kWh(battery) Moles of H2 converted into kWh values by using Gibbs free energy value

85 170
80 120 Moles of H2 generated System efficiency

75

70

70

65

20

60 0 500 1000 1500 2000 2500 3000 Battery size, A-Hr Efficiency H2 moles

-30 3500

Results grid parallel

In 24 hour run % load powered by individual components
0% 14% 18%

pv fc
21% 61%

11%

pv fc

grid bat

14%

61%

grid bat

Without battery

With battery

System Efficiency grid parallel

System efficiency: = kWh (load + H2 produced + to grid)

kWh (PV +battery + from grid)

90
85 System efficiency 80 75 70 65 60 0 500 1000 1500 2000 2500 3000 Battery Size, A-Hr Efficiency H2 moles

180
160 moles of H2 generated 140 120 100 80 60 40 20 0 3500

RFC as primary energy storage device

RFC system used before battery in the power flow strategy
77 75 system efficiency 73 71 69 67 0.8 0.7 0.6 0.5 0.4 0.3 0.2 0.1 Battery final state of charge

65
0 500 1000 1500 2000 2500 3000 Battery size, A-Hr Efficiency SOC

0 3500

Effect of varying RFC size

85 system efficiency 80 75 70 65 60 0 1 2 3 4 5 6 Fuel cell/electrolyzer size 90 80 70 System efficiency 60 9 8 6 Power to/from grid 7

Standalone

50
40 30 20 10 0

5
4 3 2 1 0

Grid parallel

Fuel cell/electrolyzer capaicty, kW Efficiency to grid from grid

Conclusions
When RFC is employed in a standalone scenario, it has to operate at very high power densities which may cause irreversible damage to the cells . In a standalone scenario, battery inclusion increases the system efficiency to a large extent . It also decreases the load on fuel cell system.

Grid parallel scenario is much more beneficial.

A large increase in H2 storage is also achieved. Use of battery does not have a significant effect on system efficiency.

Part 3 Experimental Investigations on PEMWE using Pt black catalyst

Experiment
PEM electrolysis
Cathode catalyst: Pt black Anode catalyst: Pt black Electrolyte: Nafion 115/112 Current collector: Gold plated Ti mesh

Temperature range: 20-130 deg C Pressure range: 0.5 3 bar (gauge)

Catalyst loading: 1 mg/cm2 Active area: 1 cm2

Catalyst Coated Membrane

Catalyst ink preparation Pt black catalyst + Deionized water + solvent + Nafion solution Solvent: 1. Ethanol 2. Iso-propanol 3. Acetone Glycerol added as a thickening agent Nafion solution: 10-40 % by wt Catalyst ink sprayed directly over the membrane surface.

Solvents for Catalyst ink for CCM Solvents

Solvent Iso-propanol Ethanol Boiling point Viscosity, cP deg C 82 78 2.1 1.07 Swelling ratio, % 199 238

Acetone

56

0.31

154

Acetone spraying leaves the membrane surface cracked Iso-propanol and ethanol give smooth surfaces A thickening agent like glycerol can be added

Membrane preparation
Cleaned with 3% H2O2 solution to remove organic impurities Soaking in 0.5 M H2SO4 solution followed by washing in DI water All treatments at 70 deg C

PEMWE Cell

Experimental setup

Results: Effect of temperature

2.5

2.3

2.1

Voltage, V

20 deg 1.9 40 deg 60 deg 80 deg 1.7 100 deg

1.5

1.3 0 100 200 300 current density mA/cm2 400 500 600

Results: above 100 oC

2.5

2.3

2.1

Voltage, V

1.9

100 deg 120 deg 130 deg

1.7

1.5

1.3 0 100 200 300 current density mA/cm2 400 500 600

Effect of pressure

2.1

1.9

1.8

Voltage, V

1.7

120 deg 2 bar 120 deg 3 bar

1.6

1.5

1.4

1.3 0 100 200 300 current density, mA/cm2 400 500 600

Effect of membrane thickness

2.1 2 1.9 voltage 1.8 1.7 1.6 1.5 1.4 1.3 0 200 400 current density A/cm2 600 800 115 80 deg 112 80 deg

2.9 2.7

2.5
voltage 2.3 2.1 115 100 deg 112 100 deg

1.9
1.7 1.5 1.3 0 100 200 300 400 500 600 current density A/cm2

Effect of nafion content in catalyst ink

2.3 2.2 2.1 2 1.9

voltage

1.8 1.7 1.6 1.5 1.4

20% 30% 40%

1.3
0 100 200 300 current density, A/cm2 400 500 600

Conclusions
A high temperature operation is favorable At lower temperature, a low membrane thickness gives high performance At higher temperature, a higher membrane thickness is required Increasing the pressure at higher temperature increases the performance

A higher nafion content decreases the cell performance

Best performance is obtained with nafion 115 at 100 deg C and 3 bar pressure

Part 4 Multiphysics modeling of PEMWE unit

Model Formulation
Model divides electrolyzer unit in 5 divisions: Anode flow channel Anode electro catalyst and diffusion layer Membrane Cathode electro catalyst and diffusion layer Cathode flow channel

Model incorporates: Electronic and ionic charge balance Butler-Volmer charge transfer kinetics Flow distribution in channels (Navier stokes equation) Flow in porous media (Darcys law) Mass balance (Convection and diffusion) Membrane water transport: EOD, diffusion and pressure difference

Model Geometry - Grid

Model Validation

2.3 2.2 2.1 2 1.9

experimental 60 deg C
1.8 1.7 1.6 1.5 1.4 1.3 0 100 200 300 400 500 600 700 800 900 Model 60 deg C experimental 100 deg C model 100 deg C

Current Density distribution

Hydrogen production rate

Ohmic overvoltage distribution

Water flow inside the channels

Conclusion
Current density distribution is very skewed inside the cell leading to non uniform catalyst usage Gas generation rate over the surface of MEA is non uniform Low water flow rates lead to incomplete use of catalyst layer

Model can be used to study over-potential distribution inside the cell Model can successfully predict mass transfer inside various sections of electrolyzer cell Model can be used as the basis for optimum designing of flow fields of the electrolyzer cell Model needs improvement in terms of including operational problems while running the unit

Thank you