Hybrid battery and electrolyser
11552352 · 2023-01-10
Assignee
Inventors
Cpc classification
H01M2010/4271
ELECTRICITY
Y02P70/50
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
H01M16/003
ELECTRICITY
H01M16/00
ELECTRICITY
Y02E60/10
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
Y02E60/50
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
H01M50/60
ELECTRICITY
International classification
H01M16/00
ELECTRICITY
H01M50/60
ELECTRICITY
Abstract
The invention provides a method of storing varying or intermittent electrical energy and one or more of hydrogen (H.sub.2) and oxygen (O.sub.2) with an energy apparatus, the method comprising: providing the first cell aqueous liquid, the second cell aqueous liquid, and electrical power from an external power source to the functional unit thereby providing an electrically charged functional battery unit and one or more of hydrogen (H.sub.2) and oxygen (O.sub.2) stored in said storage system, wherein during at least part of a charging time the functional unit is charged at a potential difference between the first cell electrode and the second cell electrode of more than 1.37 V.
Claims
1. An energy apparatus having battery functionality and hydrogen and oxygen generation funtionality, the energy apparatus comprising one or more functional units, each functional unit comprising: a first cell comprising one or more first cell openings for a first cell aqueous liquid and for a first cell gas; a second cell comprising one or more second cell openings for a second cell aqueous liquid and for a second cell gas; and a separator, wherein the first cell and the second cell share the separator, wherein the separator is configured to block transport of one or more of O.sub.2 and H.sub.2 from one cell to another while having permeability for at least one or more of hydroxide ions (OH.sup.−) monovalent sodium (Na.sup.+), monovalent lithium (Li.sup.+), and monovalent potassium (K.sup.+); wherein the energy apparatus further comprises an electrical element, wherein (i) the first cell comprises two or more first cell electrodes, the second cell comprises a second cell electrode, and the electrical element is configured for applying one or more potential differences between the two or more first cell electrodes; or (ii) the first cell comprises a first cell electrode, the second cell comprises two or more second cell electrodes, and the electrical element is configured for applying one or more potential differences between the two or more second cell electrodes; or (iii) the first cell comprises the two or more first cell electrodes, the second cell comprises the two or more second cell electrodes, and the electrical element is configured for applying one or more of (a) one or more potential differences between two or more first cell electrodes and (b) one or more potential differences between two or more second cell electrodes, wherein first cell electrodes of a first subset comprise iron-based electrodes, and wherein the one or more second cell electrodes comprise nickel-based electrodes.
2. The energy apparatus according to claim 1, wherein at least one of the functional units comprises two or more first cell electrodes, and wherein said electrical element is configured for applying a potential difference between the first subset of the two or more first cell electrodes and a second subset of the two or more first cell electrodes.
3. The energy apparatus according to claim 2, wherein the first cell electrodes of the second subset comprise iron-based electrodes.
4. The energy apparatus according to claim 2, wherein the first cell electrodes of the second subset comprise hydrogen gas generating electrodes.
5. The energy apparatus according to claim 1, wherein the one or more functional units comprise a functional unit that comprises two or more first cell electrodes and one or more second cell electrodes.
6. The energy apparatus according to claim 1, wherein the one or more functional units comprise at least two functional units, wherein a first electrode of a first functional unit and a second electrode of a second functional unit are separated from each other by a bipolar plate, and wherein the bipolar plate is electrically conductive.
7. The energy apparatus according to claim 6, wherein the bipolar plate comprises at least two bipolar plate sections that are configured electrically separated from each other, wherein one or more first cell electrodes are associated with a first bipolar plate section, wherein one or more first cell electrodes are associated with a second bipolar plate section, wherein one or more second cell electrodes are associated with said first bipolar plate section, and wherein one or more second cell electrodes are associated with said second bipolar plate section.
8. The energy apparatus according to claim 1, comprising the first cell, the second cell, and a further cell, comprising either a further first electrode, to provide the two or more first cell electrodes, or a further second electrode, to provide the two or more second cell electrodes.
9. The energy apparatus according to claim 1, wherein said electrical element comprises a variable voltage supply.
10. The energy apparatus according to claim 9, further comprising a source of energy configured to generate a voltage difference and/or a different current between (a) the second electrode and the first electrodes of the first subset and (b) the second electrode and the first electrodes of the second subset in the second setting.
11. The energy apparatus according to claim 1, wherein at least one functional unit comprises: a first cell comprising a plurality of first cell electrodes and one or more first cell openings for said first cell aqueous liquid and for said first cell gas, wherein the plurality of first electrodes comprise iron-based electrodes, wherein the plurality of first cell electrodes comprise a first subset of the first cell electrodes and a second subset of the first cell electrodes; a second cell comprising said second cell electrode and one or more second cell openings for said second cell aqueous liquid and for said second cell gas, wherein the second electrode comprises a nickel-based electrode; said separator, wherein the first cell and the second cell share the separator, wherein the separator is configured to block transport of one or more of O.sub.2 and H.sub.2 from one cell to another while having permeability for at least one or more of hydroxide ions (OH.sup.−) monovalent sodium (Na.sup.+), monovalent lithium (Li.sup.+) and monovalent potassium (K.sup.+); a first electrical connection in electrical connection with a first subset of the first cell electrodes, a second electrical connection in electrical connection with a second subset of the first cell electrodes, and a third electrical connection in electrical connection with the second cell electrode; and a connector element, comprising said electrical element, switchable in a first setting wherein the first electrodes of the first subset and the first electrodes of the second subset are short circuited, and a second setting wherein different voltage differences can exist and/or different electrical currents can flow between (a) the second electrode and the first electrodes of the first subset and (b) the second electrode and the first electrodes of the second subset.
12. The energy apparatus according to claim 1, wherein the second electrode has a second electrode capacity (Ah2), and wherein the plurality of first electrodes has an integrated first subset electrode capacity (Ah11) of all first electrodes within the first subset and an integrated second subset electrode capacity (Ah12) of all first electrodes within the second subset, wherein Ah11/Ah2≥2, wherein Ah11/Ah12≥1, and Ah11+Ah12≥Ah2.
13. The energy apparatus according to claim 1, further comprising a first electrical connection in electrical connection with the first cell electrode, and a second electrical connection in electrical connection with the second cell electrode.
14. The energy apparatus according to claim 1, further comprising an aqueous liquid control system configured to control introduction of one or more of the first cell aqueous liquid and the second cell aqueous liquid into the functional unit, wherein the first cell aqueous liquid and the second cell aqueous liquid comprise at least 3 mol/l OH.
15. The energy apparatus according to claim 14, further comprising a pressure system configured to control one or more of (a) the pressure of the first cell gas in the functional unit, (b) the pressure of the first cell gas in the storage system, (c) the pressure of the second cell gas in the functional unit, and (d) the pressure of the second cell gas in the storage system.
16. The energy apparatus according to claim 1, further comprising a storage system configured to store one or more of the first cell gas and the second cell gas external from said functional unit.
17. The energy apparatus according to claim 1, further comprising a first electrical connection in electrical connection with the first cell electrode and a second electrical connection in electrical connection with the second cell electrode; an aqueous liquid control system configured to control introduction of one or more of the first cell aqueous liquid and the second cell aqueous liquid into the functional unit; a storage system configured to store one or more of the first cell gas and the second cell gas external from said functional unit; a pressure system configured to control one or more of (a) the pressure of the first cell gas in the functional unit, (b) the pressure of the first cell gas in the storage system, (c) the pressure of the second cell gas in the functional unit, and (d) the pressure of the second cell gas in the storage system; a charge control unit configured to receive electrical power from an external electrical power source and configured to provide said electrical power to said functional unit during at least part of a charging time at a potential difference between the first cell electrode and the second cell electrode selected from the range of 1.37-2.0 V; a first connector unit for functionally coupling to a receiver to be electrically powered and the electrical connection, and a second connector unit for functionally connecting a device to be provided with one or more of the first cell gas and the second cell gas with said storage system; and a control system configured to control the aqueous liquid control system, the storage system, the pressure system, and the charge control unit.
18. The energy apparatus according to claim 1, wherein the first electrode has a first capacity and wherein the second electrode has a second capacity, wherein the second capacity is less than 90% of the first capacity.
19. An energy system comprising the energy apparatus according to claim 1 and an external power source.
20. A method of storing electrical energy and one or more of hydrogen (H.sub.2) and oxygen (O.sub.2) with the energy apparatus according to claim 1, the method comprising: providing the first cell aqueous liquid, the second cell aqueous liquid, and electrical power from an external power source to the functional unit thereby providing an electrically charged functional unit and one or more of hydrogen (H.sub.2) and oxygen (O.sub.2) stored in said storage system, wherein during at least part of a charging time the functional unit is charged at a potential difference between the first cell electrode and the second cell electrode of more than 1.37 V.
21. The method according to claim 20, wherein during at least part of a charging time a potential difference between the first cell electrode and the second cell electrode is selected from the range of 1.6-2.0 V, said method further comprising maintaining a first pressure in the first cell and a second pressure in the second cell at a pressure of at least 30 bar.
22. The method according to claim 20, further comprising simultaneously discharging the energy apparatus and generating hydrogen (H.sub.2) by applying one or more of (a) one or more potential differences between two or more first cell electrodes and (b) one or more potential differences between two or more second cell electrodes.
23. The method according to claim 22, further comprising applying a potential difference selected from the range of 0.001-0.5 V between at least two first cell electrodes in a first cell.
24. The method according to claim 20, further comprising applying a potential difference between a first subset of one or more first cell electrodes and a second subset of one or more first cell electrodes, wherein said potential difference is selected from the range of 0.001-0.5 V.
25. The method according to claim 20, further comprising providing one or more of electrical power, hydrogen (H.sub.2), and oxygen (O.sub.2) to a receiver.
26. The method according to claim 25, further comprising providing one or more of electrical power, hydrogen (H.sub.2), and oxygen to (i) a motorized vehicle comprising an engine deriving its propulsion energy from one or more of a hydrogen source and an electrical power source, or (ii) a device comprised by an industrial object that is configured to utilize one or more of electrical power, hydrogen and oxygen.
27. The method according to claim 25, further comprising simultaneously generating hydrogen (H.sub.2) and providing or storing electrical energy.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
(1) Embodiments of the invention will now be described, by way of example only, with reference to the accompanying schematic drawings in which corresponding reference symbols indicate corresponding parts, and in which:
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(6) Top (I): observed potential during constant current charge insertion during increasing durations, followed by a full discharge to 1.1V; curve a indicates the voltage (left y-axis) resulting from the applied currents during the indicated times (days) on the x-axis; curve b indicates the applied currents (right axis) with charge rate C/5 and discharge rate C/10 over time (days) (same x-axis);
(7) middle (II): resulting normalized hydrogen and oxygen evolution; curve c indicates oxygen (O.sub.2); and curve d indicates hydrogen (H.sub.2); “GP” (y-axis) indicates normalized gas production over time (days) (x-axis);
(8) bottom (III): temperature (T) in ° C. development for a thermally insulated cell over time (days) (x-axis);
(9) lowest (IV) battolyser utilization of charge in the battery and the H.sub.2 production (expressed in amount of charge required to generate the H.sub.2) divided by the nominal battery discharge capacity of C=10 Ah (measured at constant temperature of T=30° C.); CU/CB indicates charge utilization divided by the nominal battery discharge capacity; CI/CB indicates charge insertion divided by the nominal battery discharge capacity; curve a indicates the battery charge+H.sub.2 yield; curve b indicates the H.sub.2 yield; curve c indicates the battery charge; reference d indicates the flexible H.sub.2 production; reference e indicates the nominal battery charge capacity;
(10)
(11) Top (I): test of a battery-electrolyser cell for many cycles with on the x-axis the cycle numbers (CN). A cycle is counted from full discharge to full discharge with various full or partial (over/dis)charge programs in between; the y-axis indicates CC/CB which is charge divided by nominal battery discharge capacity; curve a is the charge used for electrolysis, curve b displays the inserted charge which is subsequently discharged from the battery and curve c displays the total inserted charge divided by the nominal battery discharge capacity;
(12) middle (II): overall energy efficiency as sum of partial battery plus hydrogen gas production efficiency (see also below) (with on the x-axis the cycle numbers (CN)). Depending on charge insertion amounts the H.sub.2 production ranges from much higher to much lower than the battery charge. Consistently the overall efficiency adds up to above 80 to 90%; curve d displays the overall efficiency; curve e indicates the partial battery efficiency and curve f displays the partial electrolyzer efficiency; PE/OE indicates partial and overall efficiency;
(13) bottom (III): cumulative inserted charge and breakdown in battery charge and electrolysis, and the cumulative H.sub.2O mass to replenish the electrolyte expressed with respect to the battery capacity with on the x-axis the cycle numbers (CN)); the y-axis indicates CC/CB cumulative charge added up for the different cycles divided by the nominal battery discharge capacity; curve g indicates the cumulative inserted charge, curve h indicates the cumulative discharge from the battery, an curves i (at cycle number over about 150 slightly higher than) j indicate the added H.sub.2O mass expressed in charge equivalent and the electrolysis yield expressed in charge equivalent, respectively;
(14)
(15) Top (I): sequence of intermittent charge, discharge and rest steps that shows the switching capabilities of current insertion followed by immediate current withdrawal, rests and electrolytic gas evolution; with on the y-axis the voltage (left) or the current (A) (right), and curve a indicating the voltage and curve b indicating the current;
(16) middle (II): the measured normalized hydrogen and oxygen yields, with curve c indicating the oxygen and curve d indicating hydrogen generation, with on the y-axis the normalized gas production (GP);
(17) bottom (III): the temperature (T in ° C.) of the thermally insulated cell following the instantaneous heating from residual overpotential losses due to Ohmic resistances, with curve e indicating the temperature curve.
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(32) The schematic drawings are not necessarily on scale.
DETAILED DESCRIPTION OF THE EMBODIMENTS
(33)
(34) The separator 30 and the respective electrodes 120,220 may substantially have the same surfaces areas, i.e. external surface areas, and may thereby form a stack (with especially the spacers in between). Hence, the electrodes and the separator may substantial have the same heights (as depicted here) and the same width (here the plane perpendicular to the plane of drawing).
(35) Especially, the functional unit 2 is an integrated unit substantially entirely enclosed by pressure containment. As will be further also described below, the functional unit may comprise a plurality of first cells and second cells.
(36) During charging, the following reaction may take place at the first electrode 120: Fe(OH).sub.2+2e.sup.− Fe+2OH.sup.− (−0.877 V vs. SHE), followed by 2H.sub.2O+2 e.sup.−
H.sub.2+OH.sup.− (−0.83 vs. SHE). Hence, when the battery is charged, Fe may act as a catalyst for H.sub.2 formation. Further, during charging at the second electrode 220, the following reaction may take place: Ni(OH).sub.2+OH.sup.−
NiOOH+H.sub.2O+e.sup.− (+0.49 V vs. SHE), followed by 4 OH.sup.−
O.sub.2+2 H.sub.2O+4e.sup.− (0.40 vs. SHE). When the battery is charged, the NiOOH acts as O.sub.2 evolution catalyst with some overpotential with respect to the O.sub.2 evolution equilibrium potential.
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(39) Further, a first electrical connection 51 in electrical connection with the first cell electrode 120, and a second electrical connection 52 in electrical connection with the second cell electrode 220, are depicted. These may be used to provide electrical contact of the electrodes 120,220 with the external of the unit 2.
(40) The energy apparatus 1 further comprises an aqueous liquid control system 60 configured to control introduction of one or more of the first cell aqueous liquid 11 and the second cell aqueous liquid 21 into the functional unit 2. The liquid control system 60 by way of example comprises a first liquid control system 60a and a second liquid control system 60b. The former is functionally connected with a first inlet 110a of the first cell 100; the latter is functionally connected with a first inlet 210a of the second cell 200. The aqueous liquid control system 60 may include recirculation of the aqueous liquid (and also supply with fresh aqueous liquid (not shown in detail)).
(41) More in general, reference 60 indicates a control system, that may be configured to control one or more processing parameters, such as when the energy apparatus is in use. The control system 60 may be functionally coupled with one or more sensors (not depicted) which monitor such one or more processing parameters. The control system 60 may be configured to control potential differences, H.sub.2 generation, storage capacity, etc.
(42) Yet further, the apparatus 1 comprises a storage system 70 configured to store one or more of the first cell gas 12 and the second cell gas 22 external from said functional unit 2. The storage by way of example comprises a first storage 70a and a second storage 70b. the former is functionally connected to a first outlet 110b of the first cell 100; the latter is functionally connected to a first outlet 210b of the second cell 200. Note that e.g. only the first storage 70a may be available, i.e. a storage for hydrogen gas. Separation between gas and liquid, upstream of the storage and/or downstream from the first cell 100 or the second cell 200 may be executed with a H.sub.2 valve and/or a H.sub.2O dryer and an O.sub.2 deoxidiser as they are known in the art, or with a O.sub.2 valve and/or a H.sub.2O/H.sub.2 condenser, respectively.
(43) The energy apparatus 1 further comprises a pressure system 300 configured to control one or more of a the pressure of the first cell gas 12 in the functional unit 2, b the pressure of the first cell gas 12 in the storage system 70, c the pressure of the second cell gas 22 in the functional unit 2, and d the pressure of the second cell gas 22 in the storage system 70. The pressure system may e.g. include different pressure systems, which may be independent from each other or may be connected. By way of example a first pressure system 300a is depicted, especially configured to provide one or more of the first liquid 11 and the second liquid 21 under pressure to the first cell 100 and second cell 200, respectively. Further, another pressure system 300b may be configured to control the pressure of the storage for the first gas 12. Yet, another pressure system 300c may be configured to control a pressure of the storage for the second gas 22. Further, the pressure system 300 may be configured to control the pressure in the first cell 100 and/or second cell 200. To this end, the pressure system may include one or more pumps, one or more valves, etc.
(44) Yet, the apparatus in this embodiment also comprises a charge control unit 400 configured to receive electrical power from an external electrical power source (reference 910, see further below) and configured to provide said electrical power to said functional unit 2 during at least part of a charging time at a potential difference between the first cell electrode 120 and the second cell electrode 220 of especially more than 1.37 V during the first battery charge and larger than 1.48V and up to 2.0V during electrolysis when the battery is already fully charged.
(45) Schematically depicted are also a first connector unit 510 for functionally coupling a device 930 to be electrically powered and the electrical connection 51,52, as well as a second connector unit 520 for functionally connecting a device to be provided with one or more of the first cell gas 12 and the second cell gas 22 with said storage system 70. Here, in fact two second connectors 520 are depicted, a first second connector 520a, functionally connected with the first storage 70a, and a second second connector 520b, functionally connected with the second storage 70b.
(46) The apparatus may be controlled by a control system 80, which may be especially configured to control at least one of the aqueous liquid control system 60, the storage system 70, the pressure system 300, and the charge control unit 400, and especially all of these.
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(50) An advantage of arranging the units 2 in series is that application of the electrical connections is much easier. For instance, when using bipolar plates configured between units, one may only need a first electrical connection 51 with a first cell electrode (not depicted) of first cell 100 of a first unit 2, and a second electrical connection 52 with a second cell electrode (not depicted) of second cell 100 of a last unit 2. Current may then travel through a bipolar plate 4 from one (electrode from one) unit 2 to another (electrode from another) unit 2 (see arrow through bipolar plate 4). A further advantage of the series arrangement is that battery management may be easier than in the case of parallel, as providing charge beyond full capacity of one of the cells results in the (desired) generation of H.sub.2 somewhat earlier than in the other cells, without adverse effects. Discharge beyond the full capacity of an individual cell the voltage drop can be monitored not to go below 1.1V per individual cell and also O.sub.2 can be made available for reduction in the electrolyte at the Ni based electrode, e.g. by inserting O.sub.2 from the bottom water entrance of the cell, bubbling and diffusing into the electrode. The O.sub.2 can be produced and stored during the preceding charge periods of the device.
(51) The plurality of functional units may be configured as stacks. Especially referring to the stack in series, a construction may be provided comprising [ABACADAE]n, wherein A refers to an electrolyte and dissolved gas distribution sheet (such as shaped porous propylene), B refers to the first electrode or the second electrode, C refers to a bipolar plate, such as a Ni-coated bipolar plate, D refers to the second or the first electrode (with B≠D), E refers to a gas separation membrane, and n refers to an integer of 1 or larger. Note that equally well the stack may be defined as [CADAEABA]n or [ADAEABAC]n, etc. The whole stack may be contained in a pressure containment.
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(53) If desired, part of the O.sub.2 may also be reintroduced into the functional unit (during discharge)(into the second cell).
(54) Three functional units were built. These consisted of 4 Ni(OH).sub.2 based electrodes electrically connected parallel to each other as the positive pole, with also electrically parallel connected 3 Fe(OH).sub.2 based electrodes in between the 4 Ni electrodes as the negative pole. Each electrode is made with the active material in nickel plated steel pockets with small perforations to allow the electrolyte entrance and gas release. The surface area is 30 mm×100 mm, and the complete electrode thickness 3 mm. In between the Ni and Fe electrodes the Zirfon separator is present to separate the produced gasses and to electrically separate the electrodes. The electrical insulation of the contacts is performed using polyethylene parts.
(55) The results obtained were nearly identical for each of these three functional units. The following was realized in a ˜13 Ah battery capacity battery electrolyser: Potential during 13 Ah battery charge ˜mostly around 1.52V (overpotential 1.52−1.37=0.15V, efficiency ˜1.37/1.52=0.90) Potential during 13 Ah discharge: ˜mostly around 1.2V (overpotential 1.37−1.2=0.17V, efficiency ˜1.2/1.37=0.88) Battery part efficiency=0.90×0.88=0.79. Potential during 10 Ah H.sub.2 production: 1.65V (overpotential 1.65−1.48=0.17V, efficiency ˜0.90) Overall efficiency: (13 Ah×1.2+10 Ah×1.48)/(13 Ah×1.52V+10 Ah×1.65V)=0.838 (assuming that the stored H.sub.2 has its full HHV=1.48 eV/H atom)
(56) As separator, Zirfon Perl UTP 500 (Agfa) was used. Features of Zirfon Perl UTP 500 are: Permanently hydrophilic by incorporated metal oxide particles, perfectly wettable in water and most common electrolytes; No hydrophylization by surfactants needed; Lots of OH-groups at alkaline pH due to amphoteric character of ZrO.sub.2; Dimensionally stable (no shrinkage effects); Very robust (reinforced with a fabric); Stable in strong alkaline (up to 6M KOH) and up to 110° C.; Low ionic resistance, enables electrolysis at high current densities; 0.3 Ω.Math.cm.sup.2 (at 30° C., in 30 wt. % KOH); Gas pressure resistance can be up to 200 bar when filled up with electrolyte; Symmetrical internal pore structure; Porosity 50±10%; Double safety by double skin layer; Pore size 0.15±0.05 μm; and thickness 500±50 μm.
(57) The amount of hydrogen (and oxygen) produced adds up to the total weight of water lost during H.sub.2 production: this indicates no other side reactions are detected.
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(60) The overall efficiency is defined as the energy in the higher heating value of the hydrogen generated plus the electrical energy stored in the battery divided by the total input of electrical power. The battery efficiency is calculated from the average electrical output potential of the reversible battery capacity divided by the average input potential starting from the discharged state (so including the hydrogen generation). Remarkably the overall efficiency reaches >80%, which is higher than the Ni—Fe battery alone reaches (˜70%) because now the hydrogen losses during battery charge are captured. The efficiency of a single alkaline electrolyser is also about 65-70%, so here too a benefit in higher electrolysis efficiency is found (due to lower required potentials in the battery electrolyser). The indications C1O, C2O and C3O indicate the overall efficiency cell results for the cells 1-3; the indications C1B, C2B and C3B indicate the battery efficiency for the three different cells.
(61) During cycles 33-38, only a low amount of gas was made; i.e. in total less charge input, and a relative large fraction of the charge was therefore stored in the battery. During cycles 61-67, the temperatures is 40° C. there, a higher overall efficiency is found. Five cycles thereafter, the temperature is 35° C., and 8 cycles thereafter, the temperature is 30° C. For cycles with a battery efficiency indicated as about 20%, the battery was fully charged and in addition about four times more H.sub.2 was produced than there is capacity in the battery.
(62) Overpotentials for hydrogen and oxygen production were determined at different battery-electrolyser applied currents, after the battery capacity was reached fully. For currents between 0.1 A and 4 A in the test cells there is a linear relation between the required Voltage and the .sup.10log of the current. The slope corresponds to about 155 mV per decade in current increase at 20° C. Lower overpotentials were realised at 40° C. due to lower internal resistances and faster kinetics, this corresponds to a further overall efficiency increase to ˜86%.
(63) Many more cycles were performed on three different cells, with different charge rates, total amounts of current and also with switching the charge and discharge each 15 minute. Overall efficiencies remained high above 81% also during switching, and in fact because the overpotential of charge and discharge of the battery functionality were smaller (possibly due to diminishing gradients in OH.sup.− concentration in the electrolyte) the efficiency increased slightly during switching.
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(68) Hence, the invention provides electricity storage with an integrated alkaline Ni—Fe battery and electrolyser (“battolyser”). We have developed an integrated nickel-iron battery-electrolyser (“battolyser”) that combines the durability of Ni—Fe batteries and alkaline electrolysis, while their integration leads to higher efficiency. When charged the battery electrodes consisting of nanostructured NiOOH and reduced Fe act as efficient oxygen and hydrogen evolution catalysts respectively, enabling current insertion without degradation far beyond the battery capacity. Furthermore, our results demonstrate a remarkable constant high efficiency and fast current switching capabilities in the integrated device. We anticipate the result to be a starting point for an efficient robust grid scale energy storage solution with a low cost, abundant element based, intrinsically flexible device that has close to full time applicability: as unlimited switchable power storage and hydrogen fuel and feedstock producer.
(69) In a renewable energy future similar daily volumes of electricity storage in batteries' and in the production of hydrogen fuels may be required to come to adequate energy storage on both daily, and seasonal timescales. We show here that the integration of the Ni—Fe battery and the alkaline electrolyser leads to a device concept as sketched in
(70) First, the integrated battolyser device is based on the Ni—Fe battery as introduced by Jungner and Edison. The Ni—Fe battery is known for its robustness during intensive deep discharges and overcharging, and its extreme longevity. The battery has a negative electrode in which Fe(OH).sub.2 is reduced to Fe upon charge: Fe(OH).sub.2+2 e.sup.−.fwdarw.Fe+2OH.sup.− (−0.877V vs SHE), considering only the Fe/Fe.sup.2+ discharge plateau. The positive electrode contains Ni(OH).sub.2 that upon charge releases a proton: Ni(OH).sub.2+OH.sup.−.fwdarw.NiOOH+H.sub.2O+e.sup.− (+0.49V vs SHE). The open circuit potential (OCV) of the battery is 1.37V, which is higher than the minimum potential required to split water from the aqueous electrolyte. Ni—Fe batteries have been known for their relatively low energy efficiency (˜50-70%).sup.7,5, their limited charge rate capabilities, and an historically reduced market potential as a result of that. In the battolyser, however, hydrogen becomes a regular product of operation improving the energy efficiency and enabling that higher charging rates with higher overpotentials and (higher) associated gas evolution can be used.
(71) Second, the battolyser is based on alkaline electrolysers; mature technologies at industrial scales for the generation of hydrogen and oxygen at a typical efficiency of 71% that is calculated from the higher heating value (HHV) of the produced hydrogen divided by the applied electrical energy. At the positive electrode the oxygen generation takes place: 4OH.sup.−.fwdarw.O.sub.2 (g)+2H.sub.2O+4e.sup.− (1.23−0.059×pH vs SHE) and at the negative electrode hydrogen generation: 2H.sub.2O+2e.sup.−.fwdarw.H.sub.2 (g)+2OH.sup.− (0.00−0.059×pH vs SHE). The main active components are a Ni metal based positive electrode, a Ni (or Ni coated Fe) negative electrode, and a gas separator or diaphragm with alkaline electrolyte in between. The diaphragm separates the hydrogen from oxygen while transmitting the OH.sup.− ions between the electrodes. In the normal electrolyser hydrogen production at currents of 400 mA/cm.sup.2 electrode surface and typical temperatures of 65-150° C. are required and precious metals like Pt or Pt—Ru can be incorporated in the negative electrode to come to high enough efficiency and production levels. The diaphragm can be a ceramic polymer composite, while the electrolyte is again a strongly alkaline KOH solution.
(72) In the battolyser for the first time the clear synergy of materials choices of the durable Ni—Fe battery electrodes and the alkaline electrolyser are explored. For separation of hydrogen and oxygen the battolyser has a commercial diaphragm as used in alkaline electrolysers, which is known for its low resistance for ionic transport and stability up to 110° C. (Zirfon-Perl-UTP500). The battolyser is operated near room temperature and with currents matching the battery active mass and surface area, reaching up to 20 mA/cm.sup.2. These same moderate currents split water efficiently at higher states of charge, without any precious metal catalysts and near RT. The moderate conditions will mean prolonged lifetime for all components.
(73) Hence, in embodiments during charge the Ni—Fe electrodes stores electricity from the electricity source, converting the electrode materials (Fe(OH).sub.2+2e.sup.−.fwdarw.Fe+2OH.sup.−) and Ni(OH).sub.2+OH.sup.−.fwdarw.NiOOH+H.sub.2O+e.sup.−, and when charged generate hydrogen (2H.sub.2O+2e.sup.−.fwdarw.H.sub.2 (g)+2OH.sup.−) and oxygen (4OH.sup.−.fwdarw.O.sub.2(g)+2H.sub.2O+4e.sup.−) by splitting water. The diaphragm transmits OH.sup.− and separates O.sub.2 and H.sub.2. The battolyser may be applied as sink and source for stabilising the electricity grid, for supplying electricity as well as H.sub.2 as fuel, and for H.sub.2 as chemical feedstock.
(74) In
(75) We designed a test-series to simulate various real life situations with partial and full (dis)charging, rapid switching, continuous overcharging, as well as the around the clock cycling for months ( ). The results are shown in
(76) The remarkable finding in
(77) The electrolysis potential as a function of current and temperature is shown in
(78) As a further test of the operation of the battolyser we applied various rapidly changing charge—discharge cycles (
(79) The findings of durability and flexibility are remarkable since other types of batteries will be rapidly destroyed by overcharging and/or deep discharging. Lithium ion batteries suffer from electrolyte decomposition during overcharging, while nickel-metal hydride and lead-acid batteries suffer mainly from detrimental corrosion effects during overcharge and deep discharge. The remarkable stability will be related to the fact that the Ni and Fe based electrodes are operating between the thermodynamically stable phases in their Pourbaix diagrams. Apparently during the electrolysis mode at the negative electrode one can only reduce water to H.sub.2 or reactivate iron oxides (when formed during deep discharge) to become Fe, while at the positive electrode any Ni(OH).sub.2 which is oxidised to NiOOH or overcharged to γ-NiOOH will readily go back to Ni(OH).sub.2 during discharge. Such intrinsic stable points of return during charge (Fe) or discharge (Ni(OH).sub.2) enhance the stability of the electrodes during prolonged electrolysis operation and deep discharge.
(80) Next to the materials and energy efficiency the relevance of an integrated long living battery and electrolyser can be found in economic factors. The integrated battolyser fits in the merit order of using renewable electricity: 1.sup.st using it directly, 2.sup.nd storing the surplus in efficient batteries for the short time, and 3.sup.rd storing it for longer times in hydrogen fuels at the expense of conversion losses when generating electricity afterwards. The integrated battolyser combines the 2.sup.nd and 3.sup.rd step in the merit order and in that way has as advantage that it reaches high capacity factors and efficiency, storing in the battery, producing gas, or delivering electricity.
(81) In an example, an integrated battery electrolyser or battolyser was made. The electrodes are separated from each other using state of the art membranes (Zirfon from Agfa; ref Agfa Specialty Products (www.agfa.com); Vermeiren, P., Moreels, J. P., Claes, A. & Beckers, H. Electrode diaphragm electrode assembly for alkaline water electrolysers. International Journal of Hydrogen Energy 34, 9305-9315 (2009)) that have a low ionic resistance in the current density regime that is used, leading to an additional overpotential of 20-30 mV between the electrodes. The limited current density likely also means a prolonged lifetime of the membranes, which is subject of further tests.
(82) We performed intensive charge insertion and withdrawal experiments, see
(83)
V.sub.c, I.sub.c are the applied cell voltage and current during the charge and electrolysis cycle with duration t.sub.c, V.sub.dc and I.sub.dc are the discharge voltage and current during the discharge time t.sub.dc, I.sub.el the current for electrolysis (and hydrogen evolution induced battery self-discharge) with an energy yield corresponding to the thermo neutral potential H.sub.el. The H.sub.el equals 1.48 V at RT while 2eH.sub.el equals the higher heating value of hydrogen of −286 kJ/mol H.sub.2. I.sub.el results from the difference between the total current inserted in the battery electrolyser and the subsequent integrated current during discharge:
∫.sub.0.sup.t.sup.
Note that the electrolysis yield also includes the gas production during (self) discharge (if any). Self-discharge is relevant since one can observe in
(84) The separate channels of hydrogen and oxygen were analysed during operation using a calibrated quantitative gas analysis system with a sensitive Hiden 3F-PIC series Quadrupolar Mass Spectrometer for the detection. There is hardly any detectible O.sub.2 in the hydrogen channel, while there is a small amount of H.sub.2 detected in the O.sub.2 channel. This is more commonly observed in electrolysers. In view of the low ionic resistance of the membrane additional thickness can be afforded to increase the gas separation quality further where necessary.
(85) In an embodiment, after charging the apparatus (“battery”) and producing the reduced iron in the negative electrode, the aqueous liquid, especially at least the aqueous liquid in the first cell, may be at least partly, even more especially substantially entirely removed from the functional unit. This may prevent self-discharge via the reactions Fe+2H.sub.2O.fwdarw.Fe(OH).sub.2+H.sub.2(g) at the negative electrode and 2NiOOH+H.sub.2O.fwdarw.2Ni(OH).sub.2+½O.sub.2(g). Yet further, the functional unit, especially the first cell, may be filled with an inert gas, such as e.g. N.sub.2. Hence, in embodiments the aqueous liquid control system 60 may also be configured to remove one or more of the first cell aqueous liquid 11 and the second cell aqueous liquid 21 from the functional unit 2. Yet further, the aqueous liquid control system 60 may also be configured to replace one or more of the first cell aqueous liquid 11 and the second cell aqueous liquid 21 from the functional unit 2 by an inert gas. Yet further, the aqueous liquid control system 60 may also be configured to replace the inert gas in one or more of the first cell and the second cell from the functional unit 2 by the first cell aqueous liquid 11 and the second cell aqueous liquid 21, respectively. Such embodiments, wherein e.g. temporarily the cell aqueous liquid is removed from the apparatus may especially be of relevance when the first electrode especially Fe comprising electrode has a larger active Fe mass (proportional to the current storage capacity expressed in [Ah]) than the second electrode, especially having a active mass at least twice as large, such as at least 10 times as large, even at least 50 times as large, as the active mass of the second electrode, such as even up to 150 times.
(86) In yet a further embodiment, the one or more of the first cell aqueous liquid 11 and the second cell aqueous liquid 21 may further comprise a catalyst, especially a catalyst for generating water from H.sub.2 and O.sub.2. This may cure the problem of cross-over from gasses, which may not always completely be prevented by the separator. Especially, the second cell aqueous liquid 21 may comprise such catalyst. A suitable catalyst may e.g. be LaNi.sub.5 or equivalently a modified LaNi.sub.5 material as is used in nickel metal hydride batteries as anode. The catalyst may be provided as particles in a filter in the exhaust of the liquid or bound to the diaphragm (for the negative electrode compartment) or bound to the separating diaphragm (near the positive electrode, but not in electrical contact).
(87) Alternatively or additionally, the separator may include a hollow separator with liquid within. For instance, a sandwich type of membrane may be provided between which an electrolyte may flow independently, taking away any crossed over H.sub.2 or O.sub.2. This may also reduce possible cross-over of gasses.
(88) The battolyser especially needs to combine the current storage density of the Ni—Fe battery (mAh/cm.sup.3), with the current density of the alkaline electrolyser (mA/cm.sup.2 on the electrode and diaphragm surface).
(89) The charge storage density is determined by the density of the materials. The energy density also depends on the potential difference of the reactions taking place at the negative and positive electrodes:
Negative electrode: Fe(OH).sub.2+2 e.sup.−.fwdarw.Fe+2OH.sup.− (−0.877V vs SHE) [1]
Positive electrode: Ni(OH).sub.2+OH.sup.−.fwdarw.NiOOH+H.sub.2O+e.sup.− (+0.49V vs SHE) [2]
Open circuit potential=0.49+0.877=1.37V.
(90) Below the table indicates charge storage densities as resulting from the battery chemical reactions. In the table β-Ni(OH).sub.2 is indicated, which is the thermodynamically most stable form of nickel hydroxide. Another structure, α-Ni(OH).sub.2, can also be formed (partially) during electrochemical cycling. This has a lower density and needs some space for expansion (the porosity of practical electrodes makes that possible). The thickness of the electrodes in the direction perpendicular to the separator determines the current density per electrode surface unit (in A/cm.sup.2) that is required to (dis-)charge the battery electrode capacity per electrode surface unit (in Ah/cm.sup.2) in a certain time.
(91) TABLE-US-00001 Fe(OH).sub.2 β-Ni(OH).sub.2 Density [g/cm.sup.3] 3.4 4.10 Molar mass [g/mol] 89.8597 92.708 Charge storage density [C/cm.sup.3] 7298 4268 Charge storage density [Ah/cm.sup.3] 2.027 1.186 Minimal electrode thickness* at 0.40 0.68 0.8 Ah/cm.sup.2: [cm] Practical electrode thickness** at 1.1 1.8 0.8 Ah/cm.sup.2: [cm] Minimal electrode thickness*** at 0.40 (Z/0.8) 0.68 (Z/0.8) Z Ah/cm.sup.2: [cm] Practical electrode thickness at 1.1 (Z/0.8) 1.8 (Z/0.8) Z Ah/cm.sup.2: [cm] *800 mAh/cm.sup.2 of the electrode surface both satisfies battery needs (a chosen capacity of 2 h charge with maximal current density of 400 mA/cm.sup.2) and electrolysis needs (400 mA/cm.sup.2 continuous, the state of the art for alkaline electrolysers). In a solar powered future on average 1-2 h peak electricity storage in the battery is required plus 2-3 times longer electrolysis at peak power in summer (3-8 h charge insertion in total at day time). Discharge at night could be done at lower rates e.g. in 6-8 h. **Literature electrode densities in practice: 37%, i.e. less than theoretical maximum, so the electrodes are porous and would become thicker accordingly. Thicknesses for ‘old Edison battery’ electrodes: 6 mm = 0.6 cm. The porosity can vary. ***The value Z indicates an arbitrary charge capacity in [Ah]. The equation relates thickness of electrode. Z can range from 0.01 (10 mAh very thin battery electrode) to 4 (4000 mAh very thick), and can have a larger value for the Fe than for the Ni electrode as discussed previously.
(92) Energy storage density [Wh/cm.sup.3] of a basic anode-cathode-electrolyte configuration: this is the product of the charge storage densities times the potential between the electrodes. At OCV the ‘single cell battery energy density’ would be ˜1.37V×0.8 Ah/(1.1+1.8+0.3 cm.sup.3)=0.343 Wh/cm.sup.3=343 Wh/L. The (1.1+1.8+0.3 cm.sup.3) is the sum of practical anode, cathode and some electrolyte plus diaphragm thicknesses. Note: this is a very high volumetric energy density for any battery, thanks to the high volumetric storage capacity of alkaline batteries and the Fe and Ni electrodes in particular.
(93)
(94) The energy apparatus 1 comprises one or more of (a) at least two or more first cell electrodes 120 and (b) at least two or more second cell electrodes 220. Here, the apparatus comprises a single second cell electrode 220 and a plurality of first cell electrodes 120.
(95) The energy apparatus 1 further comprises an electrical element 7 configured for applying one or more of (a) one or more potential differences between two or more first cell electrodes 120 and (b) one or more potential differences between two or more second cell electrodes 220. Here, the electrical element 7 is configured for applying a potential difference between two types of first cell electrodes 120 and run a current between them. Hence, the electrical element 7 is configured for applying a potential difference between a first subset 1211 of one or more first cell electrodes 120 and a second subset 1212 of one or more first cell electrodes 120. Note that not always this potential difference has to be applied. During a stage there may be applied such potential difference; however in other stages, such as when there is enough H2, no potential difference needs to be applied.
(96) For instance, the first cell electrodes 120 of the first subset 1211 and the second subset 1212 comprise iron based electrodes.
(97)
(98) Hence,
(99)
(100) In
(101)
(102)
(103)
(104) V.sub.cell is the voltage necessary to operate the individual cell in the stack, so above 1.37V for charging, and below 1.37V for discharging. In this stack the first (indicated with Ni.sub.OH) and second (indicated with Ni.sub.O) subset of electrodes of the second electrode can be brought to potentials of respectively (m+1)×V.sub.cell and (m+1)×V.sub.cell+(0.0 up to 0.3) V within the m.sup.th cell of the bipolar plate configured stack where m=0, 1, 2, . . . n−1 for a certain stack of n cells.
(105) One can indicate the subsets as follows by their name, potential, and the reactions taking place:
Ni.sub.O at (m+1)×V.sub.cell+(0.0 up to 0.3) V: 2OH.sup.−.fwdarw.½O.sub.2+H.sub.2O+2e.sup.−
Fe.sub.OH at (0.0+m×V.sub.cell):: Fe+2OH.sup.−.fwdarw.Fe(OH).sub.2+2e.sup.−
Ni.sub.OH at (m+1)×V.sub.cell: 2NiOOH+2H.sub.2O+2e.sup.−.fwdarw.2Ni(OH).sub.2+2OH.sup.−
Fe.sub.H at (0.0+m×V.sub.cell)+(0.0 up to −0.3) V: 2H.sub.2O+2e.sup.−.fwdarw.H.sub.2+2OH.sup.−
These subsets of electrodes are indicated in
(106) In a variant on
(107)
(108) DC-DC Transformers: V.sub.in×I.sub.in=V.sub.outI.sub.out (when ignoring losses) so 0.1n×1.37×I=0.3×AI.sub.in; Current for discharge of battery: I.sub.in; Current for H2 production: A×I.sub.in; and System Voltage output: e.g. 1.37V×n×0.8; Discharge power usable as electricity: P=n×1.37×0.8×Iin; Used for H.sub.2 generation to overcome overpotentials: n×1.37×0.2×I.sub.in; The value of 0.2 is chosen because 0.3V/1.37V˜0.2 about right ratio between measured overpotential and battery cell potential. Further, the reference ** refers to the fact that V.sub.in is adjustable.
(109)
(110)
(111)
(112)
(113)
(114)
(115) In an example, as second electrodes Ni is applied, and as first electrodes a Fe comprising electrode with a relatively thick layer (large capacity) and a Fe comprising electrode with a relatively thin layer (smaller capacity) is applied. In this way a monopolar cell may be provided with an additional H2 functionality (with the thin Fe comprising electrode). In a further example, a plurality of such monopolar cells may be configured parallel. The difference in layer thickness may be at least a factor 2.
(116) In an example, the first electrode or second electrode comprise an electrode material, and additionally a catalyst. For instance, an iron comprising electrode may further comprise a catalyst. The catalyst may be available as nano particles. The nano particles may be embedded in an electrically conductive matrix (especially electrode material). Alternatively or additionally, the catalyst can be applied as coating to the electrode material. Suitable catalysts may be selected from platinum, NiMo, NiFe, FeMo, NiCoFe, a LaNi.sub.5 type compound indicated with MmNi.sub.5-x-yCo.sub.xAl.sub.y where Mm stands for a mix of lanthanides, tungsten sulfide (WS.sub.x) or selenide (WSe.sub.x), and molybdenum sulfide (MoS.sub.x).
(117) In an example, a first cell has Fe (negative) electrodes and a second cell has one or more Ni (positive) electrodes. Ni may be a relative expensive component and may determine the battery capacity. Fe is relatively inexpensive and can therefore possibly be dimensioned to have greater capacity. Hence, a larger capacity and area Fe comprising electrode can be reduced. Later, against another (small) Fe comprising electrode the larger electrode can be discharged and H.sub.2 is produced. When discharging, one or more of the Fe comprising electrodes can be discharged to provide H.sub.2 and meanwhile one or more other Fe comprising electrodes can also be discharged against the Ni in order to supply power. In the case where the Fe electrode used for discharging (Fe.sub.OH) are much larger in capacity than the Ni electrodes, e.g. 2-5 or 5-20 or even up to 100 times larger in capacity the possibility is opened to store energy in the form of reduced Fe in the large capacity Few electrodes and H.sub.2O, that can release hydrogen when demanded. Such configuration may additionally be designed to enable the removal of the electrolyte, replacing it with inert gas such as nitrogen or argon. That will be relevant to limit the spontaneous self discharge of the electrodes following the reaction Fe+2H.sub.2O.fwdarw.Fe(OH).sub.2+H.sub.2. When hydrogen is subsequently required the electrolyte is re-entered in the cells and the Fe.sub.OH can be discharged against the Fe.sub.H electrodes to generate H.sub.2. In this way also longer duration storage of energy becomes possible, e.g. with durations up to 100 days. Alternatively the very large capacity electrodes can also be kept under electrolyte and the large battolyser cells can be used for generating H.sub.2 more slowly as a result of this self discharge. The self-discharge can be promoted also by administering available (waste) heat to the cell. Depending on the requirements for electricity storage and conversion to hydrogen, also different battolysers can be arranged together to provide the electricity storage and supply and hydrogen and oxygen generation.
(118) In
(119)
(120) The electrodes in the series of
(121) Renewable energy systems have the potential to replace fossil fuels, but inherently confront us with the major challenge of storage. Fossil fuels, such as gas, oil, or coal are easy to store, and make for very easy energy production. Renewable energy, on the other hand, is only available when the wind is blowing or the sun is shining while private consumption follows characteristic diurnal and seasonal fluctuations. In a renewable energy future, similar quantities of electricity storage, in batteries and in the production of hydrogen fuels, may be required on an annual basis, to allow adequate short-term and long-term energy storage. Batteries are characterized by a high conversion efficiency, stored electricity comes back as electricity, which makes them appropriate for short-term energy storage. Producing hydrogen is considered to be the best opportunity for long-term energy storage. Hydrogen can be stored directly or it can be synthesized to produce synthetic fuels. Furthermore, hydrogen production enables ‘greening’ of chemical processes and production of effectively carbon neutral fuels since hydrogen acts as a feedstock for subsequent processes, like the Sabatier CH.sub.4 from H.sub.2 and CO.sub.2), Fischer-Tropsch (alkanes from CO/CO.sub.2 and H.sub.2), and the Haber-Bosch process (NH.sub.3 from N.sub.2 to H.sub.2).
(122) Nickel-Iron batteries were invented by Edison and Jungner and are known for their extreme durability. Conventional nickel-iron batteries suffer from low energy efficiency, unwanted hydrogen is produced and charge is lost. Therefore we assembled and designed the battolyzer, a combined battery and electrolyzer. Hydrogen is now a product, and no charge is lost which makes the Nickel-Iron system energy efficient. However, the hydrogen production follows the renewable intermittency while industry favors continuous operation. Moreover, storage facilities are required to buffer fluctuations. The new configuration of the battolyser allows for controlled hydrogen production and hydrogen storage, features necessary for continuous industrial operation and long-term energy storage. The new configuration of the battolyzer is depicted in
(123) The new battolyser configuration consist of a positive “Nickel” electrode and two negative “Iron” electrodes, one for storage and one for hydrogen production. The Nickel electrode utilizes the nickel-hydroxide (Ni(OH).sub.2)/nickel-oxyhydroxide (NiOOH) couple and the Iron “storage” electrodes the iron-hydroxide (Fe(OH).sub.2)/iron (Fe) couple. Only one “Iron-storage” electrode participates in the battery operation while the “Additional iron-electrode” is hold under anodic potential controlling the hydrogen production rate. Iron is thus the active hydrogen evolution reaction (HER) catalyst. Applying an iron-electrode for the HER is no necessity, other more efficient HER catalysts could serve for this purpose which could increase the efficiency.
(124) The overall reaction for battery operation is given by:
(125)
(126) In the discharged state one iron atom stores two hydroxyl ions (OH−) and one Nickel atom stores a proton. Upon charge water is released and the catalysts for the HER (Fe) and the oxygen evolution reaction (OER, NiOOH) are formed. The positive electrode is usually the limiting electrode and stoichiometry defines the ratio for Nickel to Iron as two for Nickel-Iron batteries. Certainly Iron is more abundant and lower-priced than Nickel. Supersizing the capacity of the iron electrode causes that upon charge insertion NiOOH is formed, going alone with oxygen evolution when the storage capacity for the Nickel electrode is reached, while at the iron electrode Fe(OH)2 is still reduced to iron (Fe). The following reaction takes place:
(127)
(128) Adding a third electrode for hydrogen production to the system allows for controlled hydrogen production. While hydrogen is produced at this electrode the “supersized” iron storage electrode is discharged:
(129)
(130) Hydrogen evolution and oxygen evolution are uncoupled, hydrogen is stored in the “supersized” iron electrode together with water from the electrolyte. Furthermore hydrogen can be produced, even when discharging the battery. Hence, the “supersized” iron electrode provides for electricity and hydrogen storage. An equivalent setup with a “supersized” Nickel-electrode and additional oxygen evolution electrode is feasible to control oxygen production.
(131) The battolyser setup allows for electrical energy storage and for electrolysis. The new setup with this specific configuration consisting of the storage and the electrolysis electrodes at the hydrogen site enables controlled hydrogen production and hydrogen storage. The storage electrode will always produce a certain amount of hydrogen upon charge insertions. The fraction of electrons contributing to hydrogen production increases with increasing the state of charge of the electrode and charge rate. No hydrogen will be released upon discharge.
(132) Hence, referring to the battery system wherein a battery can be charged (see
(133) Therefore, whereas in a normal electrolyser these gasses are produced when charge is running through the system, in the presently proposed configuration(s), first the battery electrodes may be charged. When the electrodes are fully charged, oxygen and hydrogen evolve. The third electrode allows that the iron electrode can be “supersized” with respect to the nickel electrode. The third electrode enables to use this extra capacity to store hydrogen in the supersized iron electrode and to release it when wanted in the electrolysis electrode. Without the third electrode supersizing would not be (very) useful, because the stored hydrogen cannot be retrieved. Without third electrode only electricity can be retrieved and the capacity is limited to the lower capacity of the existing electrodes. Only the electrolysis electrode allows for utilisation of the stored hydrogen in the supersized electrode. The total concept makes for easy storage and production of hydrogen. So far the setup is tested with an iron electrode as electrolysis electrode. But this electrode can be exchange with another more efficient electrode for hydrogen evolution to increase the overall efficiency.
(134) In
(135) Hence, the invention may bridge intermittent renewable electricity generation and efficient energy storage.
(136) Note that the (−|+) voltage signs herein are only displayed to indicate the presence of an electrical element that may impose a voltage difference, irrespective of the sign of such voltage difference. An arrow through such sign stresses the possibility that such electrical element may impose different voltage differences (such as a variable voltage difference) (irrespective of the sign of such difference).
(137) The term “substantially” herein, such as in “substantially consists”, will be understood by the person skilled in the art. The term “substantially” may also include embodiments with “entirely”, “completely”, “all”, etc. Hence, in embodiments the adjective substantially may also be removed. Where applicable, the term “substantially” may also relate to 90% or higher, such as 95% or higher, especially 99% or higher, even more especially 99.5% or higher, including 100%. The term “comprise” includes also embodiments wherein the term “comprises” means “consists of”. The term “and/or” especially relates to one or more of the items mentioned before and after “and/or”. For instance, a phrase “item 1 and/or item 2” and similar phrases may relate to one or more of item 1 and item 2. The term “comprising” may in an embodiment refer to “consisting of” but may in another embodiment also refer to “containing at least the defined species and optionally one or more other species”.
(138) Furthermore, the terms first, second, third and the like in the description and in the claims, are used for distinguishing between similar elements and not necessarily for describing a sequential or chronological order. It is to be understood that the terms so used are interchangeable under appropriate circumstances and that the embodiments of the invention described herein are capable of operation in other sequences than described or illustrated herein.
(139) The devices herein are amongst others described during operation. As will be clear to the person skilled in the art, the invention is not limited to methods of operation or devices in operation.
(140) It should be noted that the above-mentioned embodiments illustrate rather than limit the invention, and that those skilled in the art will be able to design many alternative embodiments without departing from the scope of the appended claims. In the claims, any reference signs placed between parentheses shall not be construed as limiting the claim. Use of the verb “to comprise” and its conjugations does not exclude the presence of elements or steps other than those stated in a claim. The article “a” or “an” preceding an element does not exclude the presence of a plurality of such elements. The invention may be implemented by means of hardware comprising several distinct elements, and by means of a suitably programmed computer. In the device claim enumerating several means, several of these means may be embodied by one and the same item of hardware. The mere fact that certain measures are recited in mutually different dependent claims does not indicate that a combination of these measures cannot be used to advantage.
(141) The invention further applies to a device comprising one or more of the characterizing features described in the description and/or shown in the attached drawings. The invention further pertains to a method or process comprising one or more of the characterizing features described in the description and/or shown in the attached drawings.
(142) The various aspects discussed in this patent can be combined in order to provide additional advantages. Further, the person skilled in the art will understand that embodiments can be combined, and that also more than two embodiments can be combined. Furthermore, some of the features can form the basis for one or more divisional applications.