MANIFOLD COMPATIBLE ELECTROLYTIC CELL (EO CELL) WITH COPLANAR FLUIDIC AND ELECTRICAL CONNECTION SCHEME
20230340676 · 2023-10-26
Assignee
Inventors
Cpc classification
C25B9/65
CHEMISTRY; METALLURGY
C25B11/052
CHEMISTRY; METALLURGY
International classification
C25B11/052
CHEMISTRY; METALLURGY
C25B9/65
CHEMISTRY; METALLURGY
Abstract
An electrolytic ozone cell that a housing that includes an interfacial seal, a top plate, and bottom plate. The electrolytic ozone cell also includes an internal compartment that having a pair of contact plates, and a tolerance compressor. The tolerance compressor compresses an electrode-membrane-electrode stack that is disposed between the pair of contact plates and the tolerance compressor alters its shape in order to maintain compressive forces on the electrode-membrane-electrode stack.
Claims
1. An electrolytic ozone cell comprising: a housing including: an interfacial seal; a top plate; and bottom plate; and an internal compartment that includes at least: a pair of contact plates; a tolerance compressor that compresses an electrode-membrane-electrode stack which includes a pair of electrodes and at least one proton exchange membrane, wherein the electrode-membrane-electrode stack is disposed between the pair of contact plates and the tolerance compressor is configured to alter the dimensions of the tolerance compressor responsive to thinning of the proton exchange membrane, in order to maintain compressive forces on at least the electrode-membrane-electrode stack.
2. The electrolytic ozone cell of claim 1, wherein a housing of the electrolytic cell is configured to be coupled to a manifold assembly of an aqueous ozone ultrasonic scaler Systems such that it has a flush coplanar interface with the manifold surface.
3. The electrolytic ozone cell of claim 1, wherein the pair of contact plates are titanium (Ti) contact plates.
4. The electrolytic ozone cell of claim 1, wherein the pair of electrodes are boron dope diamond (BDD) electrodes.
5. The electrolytic ozone cell of claim 1, wherein an electrode of the pair of electrodes is a perforated silicon plate with a boron doped diamond coating.
6. The electrolytic ozone cell of claim 5, wherein the boron doped diamond coating has a thickness of between 1.00 nm up and 15 μm.
7. The electrolytic ozone cell of claim 1, wherein the pair of electrodes and the proton exchange membrane form an electrode-membrane-electrode stack and the tolerance compressor provides compression for the electrode-membrane-electrode stack over a range of between 2 to 50% of the thickness of the tolerance compressor.
8. The electrolytic ozone cell of claim 1, wherein the tolerance compressor is inert to ozone.
9. The electrolytic ozone cell of claim 1, wherein the tolerance compressor is made from a closed-cell ethylene propylene diene monomer (EPDM) foam material.
10. The electrolytic ozone cell of claim 1, wherein a path for water flow is based on a thickness and inner profile of a contact plate of the pair of contact plates.
11. The electrolytic ozone cell of claim 1, wherein the electrolytic ozone cell comprises more than one pair of pair of electrodes.
12. The electrolytic ozone cell of claim 1, wherein an electrical contact zone of a contact plate of the pair of contact plates is accessed through the top plate by a spring-loaded electrical contact so that the contact plate provides electrical current to an electrode of the pair of electrodes.
13. The electrolytic ozone cell of claim 1, wherein a contact plate and an electrode are integrated together to form an electrode unit that provide provides direct electrical contact for a spring-loaded electrical contact.
14. The electrolytic ozone cell of claim 1, wherein the cell is configured to control a velocity of water that flows over an area of bubble formation along triple phase boundaries (TPB) formed by an electrode-water-membrane intersection.
15. The electrolytic ozone cell of claim 12, wherein the electrolytic ozone cell further includes an inner bottom gasket wherein the inner bottom gasket and the tolerance compressor seal off one or more surfaces of the pair of contact plates to create one or more dry electrical contact zones on the tabs of the pair of contact plates.
17. The electrolytic ozone cell of claim 1, wherein the electrode-membrane-electrode stack includes one or more pairs of electrodes in the same cell.
18. The electrolytic ozone cell of claim 17, wherein the one or more pairs are each independently controlled.
19. An apparatus comprising: a water supply for delivering water to an electrolytic ozone cell; a gas separator disposed in a recirculation loop of a fluid pathway that also contains the electrolytic cell; and the electrolytic ozone cell; wherein the electrolytic ozone cell further comprises: a housing including: an interfacial seal; a top plate; and bottom plate; and an internal compartment that includes at least: a pair of contact plates; a tolerance compressor that compresses an electrode-membrane-electrode stack which includes a pair of electrodes and at least one proton exchange membrane, wherein the electrode-membrane-electrode stack is disposed between the pair of contact plates and the tolerance compressor is configured to alter the dimensions of the tolerance compressor responsive to thinning of the proton exchange membrane, in order to maintain compressive forces on at least the electrode-membrane-electrode stack.
20. (canceled)
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24. A computer system comprising: a processor configured to control an operation of an electrolytic ozone cell; and the electrolytic ozone cell; wherein the electrolytic ozone cell further comprises: a housing including: an interfacial seal; a top plate; and bottom plate; and an internal compartment that includes at least: a pair of contact plates; a tolerance compressor that compresses an electrode-membrane-electrode stack which includes a pair of electrodes and at least one proton exchange membrane, wherein the electrode-membrane-electrode stack is disposed between the pair of contact plates and the tolerance compressor is configured to alter the dimensions of the tolerance compressor responsive to thinning of the proton exchange membrane, in order to maintain compressive forces on at least the electrode-membrane-electrode stack.
25. (canceled)
26. (canceled)
Description
BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWINGS
[0031] To easily identify the discussion of any particular element or act, the most significant digit or digits in a reference number refer to the figure number in which that element is first introduced. Certain novel features believed characteristic of the invention are set forth in the appended claims. The invention itself, however, as well as a preferred mode of use, further objectives and advantages thereof, will best be understood by reference to the following detailed description of the illustrative embodiments when read in conjunction with the accompanying drawings, wherein:
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DETAILED DESCRIPTION
[0050] The illustrative embodiments described herein are directed to a manifold compatible electrolytic ozone (EO) cell with coplanar fluidic and electrical connection scheme. The illustrative embodiments recognize that a goal in conventional electrolysers is to produce pure hydrogen and high pressures, so a very robust structure is required. This design goal means is not suitable for low cost and portable devices. The illustrative embodiments further recognize that conventional electrolysers generally achieve very low levels of dissolved ozone in the solution, due to the requirement to avoid releasing excessive gaseous ozone, the absence of gas management components in the system, and their operation at ambient pressure.
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[0052] To support form factor and serviceability requirements, a low profile manifold compatible electrolytic ozone cell 104 is disclosed that minimizes space requirements while delivering an EO cell that can fully charge a dental system from, for example, 0 ppm to 6 ppm of ozonated water within a short period of time compared to conventional solutions (e.g., within 30 seconds). This ozone gas production rate and long life is achieved by maintaining a low current density on the membrane and efficiently releasing bubbles as the form at the triple phase boundary (electrode-membrane-water junction). The efficient bubble release is achieved by controlling the water velocity over the face of the electrodes. By controlling the cross-sectional area in the electrode region and maintaining both system pressure (e.g., 19-24 psi, typically 22 psi) and the flow rate through the cell. The velocity of the water in the cell can be controlled to help remove bubbles and replenish the TPB with fresh water to continue feeding the electrolytic process.
[0053] The system of the present disclosure comprises the following main elements. A housing made up of an interfacial seal 202, top plate 204, and bottom plate 216, when joined form the main body of the electrolytic ozone cell 104, defines the dimensions of the inner compartment of the electrolytic ozone cell 104, provides a means for securing the cell to a manifold surface, creates internal fluid paths, and provides a coplanar interface for connecting both fluid and electrical current. The electrolytic ozone cell 104 may have several internal components: Tolerance compressor 206, contact plates such as Ti contact plates 208 (Titanium contact plates), electrodes such as BDD electrodes 210(Boron Doped Diamond electrodes), proton exchange membranes 212, and inner bottom gasket/seal 214. BDD has the overpotential to create ozone. In alternative embodiments, materials that are suitable for medical devices may be used. For example, lead oxide makes ozone but may not be used as it is poisonous. These internal components establish the electrolytic cell, the distribution of current in the cell, seals for separating inner fluid and gas pathways (i.e., anolyte and catholyte) and a means for maintaining adequate compressive forces on the inner assembly. Additional elements may be added without changing the essentials of the system disclosed herein. Methods and embodiments for each of these elements are detailed herein.
[0054] Conventional cells may also produce some oxygen as a byproduct, which further increases the utility of the produced water for treatments targeting anaerobic organisms but does not decrease the value of the AO solution for the primary purpose of scaling. Cells may also produce some hydrogen peroxide, and this component of the solution is also beneficial for cleaning, bleaching, and antimicrobial effects. In some cases, a synergistic effect of ozone and hydrogen peroxide is known and can be advantageously used by the system.
[0055] The Electrolytic Cell
[0056] Electrochemical ozone generation by direct oxidation of water, in place of the formation of O3 from O2 as in the gas phase, is a complex electrochemical process in which the catalytic electrode surface is the site of a network of reactions via several different adsorbed intermediates. The network of reactions produces a mixture of oxygen and ozone. The chemical properties of the catalyst surface affect the proportion of ozone production, but the oxygen-forming pathway is energetically more favorable and typically at least half of the electrode current forms oxygen even on the most ozone-promoting surfaces. The microscopic physical chemistry of the process is not fully understood, even though the relative ozone vs oxygen forming rates of different catalysts have been extensively studied and large differences observed.
[0057] Conventionally, a goal has been to achieve as high a rate of oxygen evolution (and hence hydrogen production) as possible, at the lowest achievable cell voltage, because this directly influences the energy cost of the process. Much of the electrolysis is done directly, with a conductive electrolyte carrying the current between the electrodes. However, a proton-conductive membrane to carry a proton current but that does not allow other species to pass at appreciable rates can be used herein. This allows electrolysis of pure water to be achieved, with significant advantages in terms of chemical simplicity and absence of unwanted byproducts. The proton conductive membranes may be sulfonated derivatives of Teflon, such as Nafion, Aquivion, and similar products. These cells are usually called Proton Exchange Membrane Water Electrolysers (PEMWE).
[0058] Conventional PEMWE industrial cells in e.g., the Membrel process for oxygen/hydrogen production have cell voltages which when are increased and ozone-selective catalysts are used, have their achievable working lifetime decreasing considerably, due to membrane and electrode degradation in the extremely oxidizing environment, and in particular due to some free radical mediated reactions that effectively attack the membrane polymer.
[0059] The selective formation of ozone instead of oxygen has hydrogen as a waste product, and the target of the present disclosure is not necessarily the lowest energy cost but rather the combination of a high dissolved ozone concentration and a long working lifetime of the cell. To achieve this objective, electrodes of boron doped diamond can be used, to take advantage of this material's preferential ratio of ozone to oxygen formation. However, BDD as a material presents some practical challenges, as it is essentially equivalent to diamond in terms of mechanical properties and has to be made by direct synthesis of a doped diamond layer on a suitable substrate to form a layer of controlled conductivity. Thus, a BDD electrode may be relatively expensive and fragile. Though platinum may be used in some circumstances, platinum oxides may pollute the membrane over time.
[0060] In one embodiment, the cell 104 includes a pair of perforated silicon plates with a thin boron doped diamond coating, the thin boron doped diamond coating being from, for example, less than 100 nm up to 15 typically 5 and can be coated more than 25 μm with a layer of proton conducting membrane 212 between them, and flow passages for the water and released gases to pass over the perforated surfaces. This configuration provides the necessary 3-phase boundary regions at the edge of every hole in the plate. Thus, the BDD electrode may be a perforated silicon plate with a boron doped diamond coating.
[0061] System Level Polarity Switching
[0062] One embodiment of the system described herein includes a design where both the cathode recirculation path 118 and the anode recirculation path 116 of the electrolytic ozone cell 104 are symmetrical so that the gas separators 110b, 110a for the cathode and anode respectively are identical in size, construction, volume, and their ability to separate gas bubbles from the fluid. In addition, both sides may require a dissolved ozone sensor, such as either two UV sensors 108 or one sensor that can measure two separate fluid paths, or a single sensor that has a series of isolation valves that can redirect either side of the system through the sensor will provide the system with the ability to monitor ozone gas in either the cathode recirculation path 118 or the anode recirculation path 116. The potential to measure ozone gas in both paths simultaneously or alternating measurement from one side of the system to the other could provide added self-diagnostics. By monitoring both sides a decision can be made to maintain the anode as the anode or if ozone levels are acceptably low (less than 0.2 ppm or lower or undetectable) the system could reverse polarity. The polarity to the cell may be changed through an H-bridge and provides output flow from whichever side of the system is producing ozone. Another benefit to monitoring ozone levels in both the anode and cathode is to monitor for gas crossover. Ozone in the cathode recirculation path 118 could indicate early signs of cell membrane perforation or loss of fluid and or gas seals. This type of self-diagnostic may help to both mitigate safety concerns as well as alert the end users prior to a loss of functionality or performance.
[0063] The need to switch system polarity may come from a need to maintain fluid levels in the catholyte and two important system characteristics related to reliability. During operation water molecules are pulled through the membrane 212 via electro-osmosis. Overtime the catholyte separator may increase in its fluid level. Without a drain or reason to discharge from the cathode side of the system the cathode separator will fill up and eventually need to be drained. By switching the overall system polarity daily, the small increase in fluid level from a day of usage will be easily managed. The reliability requirements related to polarity switching stem from the electrolytic cells long-term performance objectives and the need to maintain the cleanliness of the water in the catholyte without the need for special startup or shutdown process steps. The membrane degradation that occurs from the interaction of ozone and other oxidative species (HO, H2O2, H3O . . . ) can be distributed over both sides of the cell extending the life of each membrane. Furthermore, the catholyte may be exchanged daily and each side of the system may be ozonated preventing stagnant water and eliminating the possibility for microbial contamination.
[0064] There are conventional optical methods for detecting the level of dissolved ozone in water taking advantage of the ultraviolet light absorbance of ozone. However, changes in the mechanics and optical path (i.e., debris, aging of the UV source) may require an offset correction. By implementing a daily polarity change to the system the previous days catholyte water, water with dissolved hydrogen, can be used for zeroing out any sensor offsets making a correction without the variable concentration of an absorbing constituent in the water.
[0065] Turning now to
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[0077] Spring loaded pogo pins 1302 extend down through the manifold and reach into the cell 104 to engage the contact plates (Ti contact plate 208) electrically. The pogo pins 1302 may generate the normal force required to produce a reliable electrical connection with the contact plates (e.g., Titanium contact plates), while also taking up variation in dimensional tolerances as they collapse during their compression between the EO cell contact plate and a pogo support structure on the opposite side of the manifold. In an illustrative embodiment, the pogo pins are terminated into a printed circuit board that is connected either directly or via a small board-to-board cable harness back to the main control board. The pogo pins deliver the electrical current that drives the electrolytic reaction in the EO cell. Wires may be soldered to the pogo pins 1302 at solder locations 1306 and pogo pins 1302 may make contact with the Ti contact plates 208 at top contact 1308 and bottom contact 1310.
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[0082] Having described the apparatus, reference will now be made to
[0083] In one example embodiment herein, at least some components of the aqueous ozone ultrasonic scaler system 100 in which the electrolytic ozone cell 104 is disposed may form or be included in the computer system 1800 of
[0084] The display interface 1808 (or other interface such) forwards text, video graphics, and other data from the communication infrastructure 1802 (or from a frame buffer (not shown)) for display on display unit 1814. For example, the display interface 1808 may include a video card with a graphics processing unit or may provide an operator with an interface for controlling the apparatus.
[0085] The computer system 1800 may also include an input unit 1810 that may be used, along with the display unit 1814 by an operator of the computer system 1800 to send information to the computer processor 1806, such as information to control the operation of the electrolytic ozone cell 104. The input unit 1810 may include for example, a touchscreen monitor. In one example, the display unit 1814, the input unit 1810, and the computer processor 1806 may collectively form a user interface.
[0086] One or more steps of providing ozonated water to an ultrasonic scaler handpiece may be stored on a non-transitory storage device in the form of computer-readable program instructions. To execute a procedure, the computer processor 1806 loads the appropriate instructions, as stored on storage device, into memory and then executes the loaded instructions.
[0087] The computer system 1800 may further comprise a main memory 1804, which may be a random-access memory (“RAM”), and also may include a secondary memory 1818. The secondary memory 1818 may include, for example, a hard disk drive 1820 and/or a removable-storage drive 1822 (e.g., a floppy disk drive, a magnetic tape drive, an optical disk drive, a flash memory drive, and the like). The removable-storage drive 1822 reads from and/or writes to a removable storage unit 1826 in a well-known manner. The removable storage unit 1826 may be, for example, a floppy disk, a magnetic tape, an optical disk, a flash memory device, and the like, which may be written to and read from by the removable-storage drive 1822. The removable storage unit 1826 may include a non-transitory computer-readable storage medium storing computer-executable software instructions and/or data.
[0088] In further illustrative embodiments, the secondary memory 1818 may include other computer-readable media storing computer-executable programs or other instructions to be loaded into the computer system 1800. Such devices may include removable storage unit 1828 and an interface 1824 (e.g., a program cartridge and a cartridge interface); a removable memory chip (e.g., an erasable programmable read-only memory (“EPROM”) or a programmable read-only memory (“PROM”)) and an associated memory socket; and other removable storage units 1828 and interfaces 1824 that allow software and data to be transferred from the removable storage unit 1828 to other parts of the computer system 1800.
[0089] The computer system 1800 may also include a communications interface 1812 that enables software and data to be transferred between the computer system 1800 and external devices. Such an interface may include a modem, a network interface (e.g., an Ethernet card or an IEEE 802.11 wireless LAN interface), a communications port (e.g., a Universal Serial Bus (“USB”) port or a FireWire® port), a Personal Computer Memory Card International Association (“PCMCIA”) interface, Bluetooth®, and the like. Software and data transferred via the communications interface 1812 may be in the form of signals, which may be electronic, electromagnetic, optical or another type of signal that may be capable of being transmitted and/or received by the communications interface 1812. Signals may be provided to the communications interface 1812 via a communications path 1816 (e.g., a channel). The communications path 1816 carries signals and may be implemented using wire or cable, fiber optics, a telephone line, a cellular link, a radio-frequency (“RF”) link, or the like. The communications interface 1812 may be used to transfer software or data or other information between the computer system 1800 and a remote server or cloud-based storage (not shown).
[0090] One or more computer programs or computer control logic may be stored in the main memory 1804 and/or the secondary memory 1818. The computer programs may also be received via the communications interface 1812. The computer programs include computer-executable instructions which, when executed by the computer processor 1806, cause the computer system 1800 to perform the methods as described hereinafter. Accordingly, the computer programs may control the computer system 1800 and other components of the aqueous ozone ultrasonic scaler system 100.
[0091] In another embodiment, the software may be stored in a non-transitory computer-readable storage medium and loaded into the main memory 1804 and/or the secondary memory 1818 using the removable-storage drive 1822, hard disk drive 1820, and/or the communications interface 1812. Control logic (software), when executed by the computer processor 1806, causes the computer system 1800, and more generally the apparatus, to perform the some or all of the methods described herein.
[0092] Lastly, in another example embodiment hardware components such as ASICs, FPGAs, and the like, may be used to carry out the functionality described herein. Implementation of such a hardware arrangement so as to perform the functions described herein will be apparent to persons skilled in the relevant art(s) in view of this description.