High pressure electrolysis cell for hydrogen production from water
09534303 ยท 2017-01-03
Assignee
Inventors
- Nelson A. Kelly (Sterling Heights, MI)
- Thomas L. Gibson (Washington Township, MI, US)
- David B. Ouwerkerk (Torrance, CA, US)
Cpc classification
Y02E60/36
GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
C25B9/00
CHEMISTRY; METALLURGY
International classification
C25B9/00
CHEMISTRY; METALLURGY
Abstract
Exemplary embodiments include a method or apparatus for improving the electrolysis efficiency of high-pressure electrolysis cells by decreasing the current density at the anode and reducing an overvoltage at the anode while decreasing the amount of hydrogen permeation through the cell membrane from the cathode chamber to the anode chamber as the high-pressure electrolysis cell is operated.
Claims
1. A method for increasing the efficiency of a high-pressure electrolysis cell having an anode and a cathode defining an interior portion there between, the method comprising: providing a high-pressure electrolysis cell configured such that the electrode area of the anode is substantially larger than the electrode area of the cathode; providing a liquid electrolyte comprising water in said interior portion; electrolyzing the water by operating said cell by connecting said anode and cathode to a direct current power source having a positive terminal and a negative terminal; wherein the negative terminal is connected to the cathode and the positive terminal is connected to the anode; and the anode has a substantially larger electrode area than the electrode area of the cathode to produce hydrogen gas at said cathode and oxygen gas at said anode, and wherein said cell further comprises a cell membrane disposed between the anode and the cathode to define an anode chamber between the anode and the membrane, and a cathode chamber between the cathode and the membrane, and wherein the volume of the anode chamber is substantially larger than that of the cathode chamber.
2. The method of claim 1 wherein the surface of the anode is scored or etched.
3. The method of claim 1, wherein the anode includes a mesh-like network.
4. The method of claim 1, wherein the anode comprises a catalyst disposed on the surface of the anode, said catalyst being selected from the group consisting of finely divided platinum and ruthenium oxide.
5. A method comprising: providing an electrolysis cell comprising a pressure vessel cylinder having a conductive center post; an anode disposed on the inner cylindrical surface of the vessel, a cathode disposed on the outer cylindrical surface of the post, an annular cell membrane disposed between the anode and the cathode to define a cathode chamber between the cathode and the membrane and an anode chamber between the anode and the membrane, and a liquid electrolyte comprising water provided in the cathode chamber and the anode chamber; electrolyzing the water by operating said cell by connecting the anode and cathode to a direct current power source having a positive terminal and a negative terminal and wherein the negative terminal is connected to the cathode and the positive terminal is connected to the anode; said anode having a substantially larger electrode area than the electrode area of the cathode to produce hydrogen gas at said cathode and oxygen gas at said anode; wherein the cell is configured to provide an anode chamber volume substantially larger than the cathode chamber volume.
6. The method as set forth in claim 5, wherein said anode further comprises a catalyst disposed on its surface, and wherein said catalyst comprises a finely divided platinum or ruthenium oxide.
7. The method as set forth in claim 5, wherein the ratio of the anode chamber volume to the cathode chamber volume is about 1.41 to 1.
8. The method as set forth in claim 5, where the ratio of the anode electrode area to the cathode electrode area is about 2.45 to 1.
9. A method for increasing the efficiency of a high-pressure electrolysis cell having an anode and a cathode defining an interior portion there between, the method comprising: providing a high-pressure electrolysis cell configured such that the electrode area of the anode is substantially larger than the electrode area of the cathode; providing a liquid electrolyte comprising water in said interior portion; electrolyzing the water by operating said cell by connecting said anode and cathode to a direct current power source having a positive terminal and a negative terminal and wherein the negative terminal is connected to the cathode and the positive terminal is connected to the anode; said anode having a substantially larger electrode area than the electrode area of the cathode to produce hydrogen gas at said cathode and oxygen gas at said anode, operating said cell at a pressure between 5000 and 10000 Psig; wherein said cell further comprises a cell membrane disposed between the anode and the cathode to define an anode chamber between the anode and the membrane, and a cathode chamber between the cathode and the membrane, and wherein the volume of the anode chamber is substantially larger than that of the cathode chamber and the membrane surface area in the cathode chamber is about 14% smaller than the membrane area in the anode chamber.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
(1) Exemplary embodiments of the invention will become more fully understood from the detailed description and the accompanying drawings, wherein:
(2)
(3)
(4)
(5)
(6)
DETAILED DESCRIPTION OF EXEMPLARY EMBODIMENTS
(7) The following description of the embodiment(s) is merely exemplary (illustrative) in nature and is in no way intended to limit the invention, its application, or uses.
(8) The exemplary embodiments provide a method and apparatus for improving the electrolysis efficiency and hydrogen purity of high-pressure alkaline-electrolysis cells such as that shown in
(9) Referring first to
(10) The cell 10 may include an outer pressure vessel cylinder, which serves as a cathode 12, having a water inlet 14 leading to an interior portion 20, a hydrogen gas outlet 15 and an oxygen gas outlet 16. An electrolyte level sensor 19 may be coupled within the interior portion 20 that maintains the level of water entering the cell through the water inlet 14 at a desired level. A pump (not shown) may be electronically coupled to the electrolyte level sensor 19 and physically coupled water inlet 14 to aid in controlling the introduction of water into the interior portion 20.
(11) A liquid electrolyte 17 is contained within the interior portion 20 that aids in increasing the electrical conductivity of the water. One exemplary liquid electrolyte 17 used in the high-pressure alkaline-electrolysis cell 10 may be a 28% by weight solution of potassium hydroxide (KOH) in water.
(12) The cell 10 may also include a conductive center post, or anode 18, at least partially contained within the interior portion 20 of the cathode 12 and insulated from the cathode 12 with an insulator material 24. The cathode 12 and anode 18 may each be electrically coupled to each other via a direct current (DC) power source 11, through positive (shown as + on
(13) An annular cell membrane 32, typically made of plastic, separates the interior portion 20 into an inner compartment (i.e. an anode chamber) 34 and an outer compartment (i.e. a cathode chamber) 36, wherein the total volume of the inner compartment 34 is less than the total volume of the outer compartment 36.
(14) The inner cylindrical surface 12a of the cathode 12 is where, in basic media, H.sub.2 is produced via the reduction half reaction (Eq. 1):
2H.sub.2O+2e.sup..fwdarw.H.sub.2+2OH.sup.(Eq. 1)
(15) The outer cylindrical surface 18a is where, in basic media, O.sub.2 is produced via the oxidation half reaction (Eq. 2):
2OH.sup..fwdarw.O.sub.2+H.sub.2O+2e.sup.(Eq. 2)
(16) Combining the half-reactions for the hydrogen evolution reaction (HER) and the oxygen evolution reaction (OER), results in the overall reaction (Eq. 3):
H.sub.2O.sub.(I).fwdarw.H.sub.2+O.sub.2(Eq. 3)
(17) For the equations as above, water is in the liquid state (the H.sub.2 and O.sub.2 are gases under standard conditions, i.e. 25 C.).
(18) A parameter for analyzing any electrolyzer apparatus, including the electrolysis cell 10, is its efficiency, in this case the efficiency with which the cell 10 converts electrical energy into the chemical energy of hydrogen and oxygen. Since only the chemical energy in the hydrogen is subsequently used as a fuel for hydrogen powered devices such as vehicles, the electrolyzer efficiency may simply be expressed as the chemical energy in the hydrogen. The electrolyzer efficiency is directly proportional to the operating voltage as expressed in Equation 4:
Electric to hydrogen efficiency=100%1.254 V[V.sub.oper](Eq. 4)
(19) wherein [V.sub.oper] is the electrolyzer operating voltage and 1.254 V is the LHV (lower heating value) of hydrogen (enthalpy for the reverse of the reaction in Eq. 3, but with gaseous water rather than liquid water production).
(20) While the H.sub.2 LHV is illustrated as being used in the numerator for Eq. 4 (1.254 V), the HHV (higher heating value) may alternatively be utilized in the numerator of Eq. 4 (1.485 V, the so-called thermo neutral voltage, which is the enthalpy for the reverse of the reaction in Eq. 3 at 25 C.). Alternatively, the Gibbs free energy (1.23 V) which is the chemical value of the hydrogen in an H.sub.2O.sub.2 fuel cell at standard conditions, is often used in the numerator of the electrolysis efficiency equation. Any of the three values may be justified, and it is easy to interconvert efficiencies based on different standards as long as the standard is stated with the efficiency.
(21) The electrolyzer operating voltage is a function of several variables, including the hydrogen production rate (current), the electrolyzer temperature, and the catalysis of the half reactions. The factors that reduce the electrolyzer efficiency (i.e. increase the electrolyzer operating voltage) are generally discussed as overvoltagesvoltages over the ideal thermodynamic value.
(22) There are many factors that may influence the overvoltage in an electrolyzer cell. The ideal thermodynamic limit for the water splitting voltage, 1.23 V at standard conditions (the Gibbs free energy), is never reached in practice because it is the reversible voltage, V.sub.rev, for an infinitely slow process. In a real system, the water splitting voltage includes an overvoltage, , due to kinetic effects, that is required to drive the reaction at a finite rate as shown in Equation 5:
V=V.sub.rev+Eq. 5
(23) The overvoltage, , has three components. They are illustrated in Equation 6:
=.sub.a+.sub.c+.sub.irEq. 6
(24) where .sub.a is the activation overvoltage caused by rate limiting steps (activation energy barriers), .sub.c is the concentration overvoltage caused by the decrease in concentration at the electrode surface relative to the bulk phase because of mass transport limitations, and .sub.ir is the ohmic overvoltage caused mainly by resistance in the electrolyte and also at the electrode surfaces. The .sub.ir term is minimized by using an electrolyte with the maximum conductivity. The .sub.a term is minimized by using electrodes that catalyze the reactions of interest. The .sub.c term is often minimized by stirring. Another way to minimize the overvoltage is to operate at lower current density; at low current density both .sub.a and .sub.c will be reduced since is requires less energy to drive the system through rate-limiting steps and the concentration overvoltage will be reduced. At zero current the potential difference (voltage) across two electrodes in an electrochemical cell is equal to the reversible potential, V.sub.rev, i.e., there is no overvoltage (this is the thermodynamic limit for the system).
(25) The exemplary embodiments herein provide a method and apparatus for improving the electrolysis efficiency and hydrogen purity of a high-pressure alkaline-electrolysis cell, such as the electrolysis cell 10 shown in
(26) In one exemplary embodiment, as shown schematically in
(27) The new cathode 112 includes an outer cylindrical surface 112a. Similarly, the new anode 118 includes an inner cylindrical surface 118a, wherein the surface area of the inner cylindrical surface 118a may be substantially greater than the surface area of the outer cylindrical surface 112a. This therefore decreases the current density and overvoltage on the new anode 118. As it is known that anodic oxygen evolution is the rate limiting step in the electrolysis of water, an increased efficiency may therefore be realized as a result of the increased anode surface area.
(28) In addition, the total volume of the new anode chamber 134 (i.e. the former cathode chamber 36 in
(29) In another related exemplary embodiment to
(30) In still another related exemplary embodiment to
(31) To fully appreciate the increases in cell efficiencies as described in the exemplary embodiment of
Example 1
(32) To illustrate the increase in cell efficiency in the cell 110 of the exemplary embodiment of
(33) Thus, the length (I) of the cells 10, 110 may be set to approximately 1219 millimeters. The inner diameter of the outer pressure vessel cylinder (i.e. the inner cylindrical surface 12a of the cathode 12 in
(34) Also, wherein the thickness of the annular plastic cell membrane 32 is about 4 millimeters, an inner compartment size volume (i.e. the volume of the cathode chamber 36 in
(35) Using a model of alkaline electrolyzers developed by Ulleberg (Modeling of advance alkaline electrolyzers: a system simulation approach, Ulleberg, O., International Journal of Hydrogen Energy, 2003, 28: 21-33), the operating voltage as a function on the operating current density can be calculated, and the components of the overvoltage can be separated. The operative equation to describe the electrolyzer operating voltage, V.sub.oper, is:
V.sub.oper=V.sub.rev+((r1+r2*T)*J)+s*log((t1+t2/T+t3/T.sup.2)*J)+1)Eq. 7
(36) where V.sub.rev is the reversible voltage (1.23 V), J is the current density (mA/cm.sup.2), r1 and r2 are terms describing the ohmic overvoltage and S, t1, t2, and t3 are terms describing the activation and concentration overvoltages, and T is the electrolyzer temperature. Using the values of the constants derived by Aurora (Modeling and control of a solar hydrogen fuel system for remote locations, P. Aurora, Master's Thesis, University of Massachusetts, Lowell, Mass. 2003) and listed in Table 2,
(37) TABLE-US-00001 TABLE 2 Values of the coefficients in Eq. 7, from Aurora. Parameter Value Units r1 8.15E05 ohm m.sup.2 r2 2.75E07 ohm m.sup.2 C..sup.1 s 0.167 V t1 0.372 A.sup.1 m.sup.2 t2 7.424 A.sup.1 m.sup.2 C. t3 245.5 A.sup.1 m.sup.2 C..sup.2 V.sub.rev 1.23 V T 60 C.
(38)
(39) At an anode current density of 120 mA/cm.sup.2 (roughly believed to correspond to the design maximum for the Avalence electrolyzer cell of
(40) At reduced current densities, such as would occur with a reversal in the wiring that we propose, the activation and concentration overvoltage (polarization) would be reduced, increasing the efficiency. Using Eq. 4 one can compute how reducing the overvoltage would affect the electrolyzer electric to hydrogen efficiency.
(41) The electrolyzer V.sub.oper at a current density, J, of 120 mA/cm.sup.2 would be predicted to be 1.78 V, corresponding to an efficiency of 70.4% (based on the H.sub.2 LHV). Decreasing the current density at the anode to 50 mA/cm.sup.2 by increasing reversing the cell polarity (increasing the anode surface area by a factor of 2.45) would be expected to decrease the operating voltage to 1.715 V corresponding to an efficiency of 73.1%. Thus, this simple operation would be expected to increase the electrolyzer efficiency from 70.4% to a value of 73.1%. This improvement is relatively insensitive to changes in the electrolyzer temperature. For example, at a temperature of 20 C., the efficiency will increase form a value of 67.6% to 70.0% for the original and reversed electrode assemblies.
(42) One potential issue with the Avalence electrolysis cell 10 similar in configuration to
(43) The hoses (not shown) exiting the tops of the cells 10 through outlets 15, 16 and transporting the gases out of the cell must be non-metallic so that current does not flow around the cell (a short circuit between the anode and cathode) which would result in no electrolysis in the cell. A person of ordinary skill recognizes that allowing higher operation pressures as well as higher turn-down ratios (operation over wider range of hydrogen production rates) may be achieved if the gas permeation through the cell membrane could be reduced.
(44) The Avalence Hydrofiller 50-6500-50RG system similar to
(45) The mechanism and driving force for the permeation phenomenon is as follows. First, a small quantity of each gas dissolves into the porous membrane 32, H.sub.2 on one side, O.sub.2 on the other. It could come from the gas bubbles in the cell membrane 32 or from the gas that dissolves into the electrolyte 17. The permeation of hydrogen through the cell membrane 32 is driven by the concentration gradient across the membrane. There is little or no H.sub.2 on the O.sub.2 side of the cell and vice versa there is little or no O.sub.2 on the H.sub.2 side of the cell (
(46) From Barbir (PEM Fuel Cells: Theory and Practice, Associated Press 2005), the gas permeation rate is:
R.sub.gas=P*A*p/tEq. 8
(47) where R.sub.gas is the permeation rate, P is the membrane permeability for a given gas, A is the membrane area, p is the gas pressure, and t is the membrane thickness. The permeability, P, is the product of the gas diffusivity, D, and solubility, S, in the membrane:
P=D*SEq. 9
(48) Thus, permeability is the product of a kinetic factor (the diffusion coefficient) and a thermodynamic factor (the solubility coefficient). The diffusion of a gas through a membrane is driven by an irreversible process (the transfer of the gas) which leads to an increase in entropy. Gases spontaneously diffuse from regions of high concentration (chemical potential) to regions of low concentration. In summary, even though the Avalence Hydrofiller 50-6500-50RG system balances the H.sub.2 and O.sub.2 pressures so that the membrane does not have to support a high pressure differential, there will still be the potential for gas diffusion through the membrane leading to contamination of the respective gas compartments. Due to the high diffusion rate of hydrogen, it is not surprising that the H.sub.2 passes through the cell membrane and contaminates the O.sub.2, rather than vice versa (O.sub.2 crossover into the H.sub.2).
(49) From an analysis of Eq. 8, one can deduce that the permeation rate of the gas through the cell membrane will increase with increasing pressure differential (p) across the membrane. In addition, the permeation rate of the gas will decrease with increasing cell membrane thickness (t). Also, the permeation rate of the gas will increase with an increasing cell membrane area (A).
(50) Reversing the cell polarity (
(51) The above description of embodiments of the invention is merely exemplary in nature and, thus, variations thereof are not to be regarded as a departure from the spirit and scope of the invention.