WO1998036466A1 - Electronic method for controlling charged particles to obtain optimum electrokinetic behavior - Google Patents
Electronic method for controlling charged particles to obtain optimum electrokinetic behavior Download PDFInfo
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- WO1998036466A1 WO1998036466A1 PCT/US1998/003216 US9803216W WO9836466A1 WO 1998036466 A1 WO1998036466 A1 WO 1998036466A1 US 9803216 W US9803216 W US 9803216W WO 9836466 A1 WO9836466 A1 WO 9836466A1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/44—Methods for charging or discharging
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/425—Structural combination with electronic components, e.g. electronic circuits integrated to the outside of the casing
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- Y—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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Definitions
- This invention relates to physical, biological, and electrochemical processes that depend on the electrokinetic behavior of charged particles, and in particular, an improved method for controlling the electrokinetic behavior in such processes.
- FIG. 1 is a perspective plot of the applied emf or electromotive force and the resulting charged particle displacement versus time, illustrating one preferred-embodiment of the invention.
- FIGS. 2A and 2B illustrate waveforms for the applied electromotive force and the resulting charged particle displacement with and without a DC offset.
- FIGS. 3A and 3B illustrate the electromotive force and resulting displacement waveforms when the frequency of oscillation is changed.
- FIG. 4 is a plot used to illustrate the three different concepts of reactive amplification occurring at system resonance, the effect of damping on circuit transient response, and the ability to manipulate the peak amplitude of the injected signal.
- FIG. 5 illustrates two alternate waveform emf embodiments and shows both with positive and negative DC offset.
- FIG. 6 is a system block diagram illustrating the essential elements of the invention.
- FIG. 7 is a simplified system schematic diagram of the one preferred-embodiment of this invention.
- FIG. 8 is a simplified system schematic diagram illustrating a preferred alternate- embodiment.
- FIG. 9 is a simplified system schematic diagram of a third preferred alternate-embodiment of the invention.
- FIG. 10 is a simplified system schematic diagram of an alternate-embodiment of the invention.
- FIG. 11 is a perspective drawing illustrating the dynamic nature of the electrical double layer at the solid-solution junction and the resulting potential gradient.
- FIG. 12 is a perspective drawing of charged particle Brownian movement with and without a DC field applied.
- FIG. 13 is a perspective plot of activation overpotential versus distance from the surface to illustrate the influence of transient concentrations on the reaction rate.
- FIG. 14 is a perspective plot of surface charge density versus activation overpotential to illustrate the influence of transient concentrations on the surface charge density.
- FIG. 15 is a plot of current versus ion displacement representative of typical pulsed DC methods in many prior art processes.
- FIG. 16 is a comparative plot of the preferred waveform and resulting displacement versus the displacement from an equivalent DC electromotive force.
- FIG. 17 is a comparative plot of the preferred waveform versus the pulsed DC (step function) waveform described in prior art illustrating the energy loss resulting from DC.
- FIG. 18 gives a plot of an alternate-embodiment emf waveform for high current applications.
- FIGS. 19A and 19B illustrate the electrokinetic behavior of electrons in flourescent and phosphorescence materials.
- FIGS. 20 A and 20B illustrate the structure of a parallel plate capacitor, dielectric polarization, and dielectric loss from the application of an alternating field.
- FIG. 21 is an impedance versus frequency plot for several types of battery systems.
- FIGS. 22 A and 22B are perspective drawings illustrating the mass-transport flow in a plane-parallel electrode system used to compare prior art with the advantages of this invention.
- FIG. 23 is a perspective illustration of a porous electrode to illustrate the disadvantages of using DC electromotive forces and the advantages of this invention.
- FIG. 24A is an equivalent circuit for an electrochemical cell and illustrates the classical view of a static cell with DC field applied, as described in prior art.
- FIG. 24B is an enhanced equivalent circuit for an electrochemical cell depicting the dynamic electrokinetic behavior of the cell when operated as described in this invention.
- FIG. 25 illustrates the effect of the preferred-embodiment waveform on the electrical double layer capacitor.
- a key to electrochemical reaction rates is the ability to manipulate an additional electrical potential that results in much greater control of the reaction process.
- a one volt change at the surface of the electrode can result in an eight-order-of-magnitude increase in the reaction rate.
- the Butler- Volmer equation expresses the electrode kinetics by relating the current-overpotential relationship to the exchange current density and the anode and cathode transfer coefficients. For large overpotential values, a simplification of the Butler-Volmer equation results in the Tafel equation:
- the Tafel equation can be solved directly to find current density i and activation or surface overpotential ⁇ s .
- the term iriz is the exchange current, ⁇ a being the anode transfer coefficient, F is Faraday's constant, R is the universal gas constant, and T is the temperature in degrees Kelvin.
- the potential developed across the cell is equal to:
- V r s (anode) + ⁇ c (anode) + IR - ⁇ c (cathode) - ⁇ . (cathode)
- ⁇ c is the concentration overpotential and the term IR represents the ohmic losses.
- the cathode overpotentials are negative by convention so that the five components are added to define the potential across the cell. The five elements are not energy sources and represent losses.
- the reaction rate is dominated by the activation overpotential ⁇ s that results from the occurrence of an electrical double layer structure that is present at the solid-liquid (surface- solution) interface.
- This electrical double layer or double layer acts as a capacitor in parallel with the reaction process.
- the activation or surface overpotential acts to impede the electrical field that is driving the reaction rate.
- the activation overpotential is a parasitic energy loss and results in the production of heat.
- electrochemical systems have been powered with DC voltages and currents. Driving the reaction with DC, whether continuous or pulsed, also means that a significant portion of the energy is consumed by charging the double layer.
- Stern described the electrical double layer structure as two double layers, one immobile near the surf ⁇ ce and the other a diffuse region extending into the solution.
- Fnmikin added a correction to the Stern model to account for the changes in the double layer structure caused by localized variations in the concentration of the reactants and reaction products.
- FIG. 24B illustrates the electrical circuit configuration.
- C gc When the Helmholtz region is highly concentrated, C gc is large compared with C h so the effective capacitance C s is approximately equal to C h . With a dilute concentration, C s will be approximately equal to C gc .
- FIG. 11 illustrates the theoretical physical arrangement of the double layer at an active solid- solution junction.
- IHP inner Helmholtz plane
- OHP outer Helmholtz plane.
- the distance from the surface to the IHP is roughly one nanometer (nm) and the distance from the surface to the OHP is about 3 run.
- the typical capacitance developed over this region can be between 10 ⁇ F/cm 2 and 50 ⁇ F/cm 2 . If the potential across the IHP (1 nm) is 100 mV then the field strength across the region is very large at lxl 0 8 V/ra The potential can be viewed as a kinetic resistance.
- the potential energy of an ion in the electric field is based on the formula ze ⁇ , with z equal to the valence of the ion and e equal to the charge on the electron.
- the plane at d coincides with the effective thickness of the diffuse layer and can be as small as 3 nm at low concentrations and at ⁇ 0 less than 25 mV.
- the potential ⁇ 0 can easily be hundreds of millivolts.
- FIGS. 13 and 14 are derived from the Gouy-Chapman equations and have limitations at large potentials but are useful to illustrate two important properties. As illustrated in FIG. 13, the decrease in potential ⁇ , over distance, occurs more rapidly if the concentration is increasing. FIG. 14 shows that the surface charge density ⁇ , for a given potential ⁇ 0 , increases with increasing concentration.
- the rate of the electrode reaction is controlled by the kinetics of the reaction as discussed. In addition, it is also dependent on the rate of mass- transport of reactants and reaction products to and from the reaction site.
- the three types of transport are convection, diffusion, and migration. Diffusion is the process where particles disperse from a region of high concentration to a region of lower concentration. Migration is the process where a particle moves from one region to another under the influence of a force, such as electromigration resulting from the application of an electric field.
- a reaction is diffusion controlled if a high probability exists that the two species will react if they come into contact.
- a reaction is activation controlled if the reaction is highly dependent on the activation energy of the reaction itself. Historically, a system with mass-transport limits could be improved with electrolyte agitation. Similarly, high activation energy barriers were overcome with the addition of a catalyst or an increase in operating temperature.
- FIG. 11 illustrates this action.
- a reaction may slow because the reactants attempting to reach the reaction site must compete with other molecules there plus any reaction products ⁇ cumulating at the site. Irreversible losses result from transport limitations and these factors are responsible for ohmic losses and heating. Vigorous mechanical stirring of the solution can increase the rate of mass-transport in such systems.
- Nernst defined a diffusion layer thickness ⁇ (not to be confused with the double layer effective thickness) that extends into the solution.
- the thickness of this layer is a convenient measure of the resistance of the system to mass-transport of reactants.
- the thickness of the diffusion layer can range roughly 0.01 mm to 0.5 mm. The thickness depends on the system hydrodynamics, such that, the thinner the layer the greater the fluid agitation and thus the better the mass-transport process. If a process is well stirred, the deposition or dissolution of material will not affect the hydrodynamics and thus ⁇ .
- the limiting current density is inversely proportional to ⁇ . Since the value of ⁇ can range 50:1, the limiting current can vary over the same magnitude in response to changing conditions in the cell.
- An electrochemical system operated at the limiting current density is operating under mass-transport control.
- the rate of the electrode reaction is the rate that species are deposited or dissolved as a function of the current density.
- Current density depends on the driving force and is greatly influenced by the activation or surface overpotential and the concentration of the solution at the reaction site. Again, the reaction rate is dependent on the conditions prevailing at the interface. With a high stirring rate and turbulent flow, the limiting current density will be higher because the turbulent flow or mass-transport perturbation affects the limiting factors. However, for most electrochemical systems, mechanical stirring is not practical because of economical or physical restrictions.
- the drift velocity of an ion is the average velocity in the direction of the applied field.
- the vectors shown in FIG. 12 crudely show the result of the collision if the ion had not been under the influence of the electric field: Note that FIG. 12 is a two-dimensional representation in the x and y plane only and an ion is free to move in the z plane as well.
- the effective viscosity in the diffuse layer is affected by the application of the electric field and the resulting drift or electromigration of the ions in the field. This change in viscosity results in an electrophoretic effect or retardation.
- the retardation causes an ionic atmosphere to move in a direction opposite to the motion of the central ion thus reducing the ion's natural velocity.
- the Helmholtz layer is very immobile because the forces are so strong that the lifetime, in this layer, of an ion or polarized molecule is long. Any reactant species entering the double layer region have to compete for access to the surface. But the electric field suppresses the reactant ion's natural three-dimensional Brownian motion.
- the ion Without the applied electric force, the ion is free to move laterally or in a reverse direction until it can find a suitable reaction site. Suppression of the Brownian motion can severely limit the ion's ability to move to an available site. The combination of these factors contributes to the development of a time lag in the ion's response to transient changes in the electromotive force. The result is an increase in the activation overpotential caused by the effects on the double layer structure and an increase in concentration overpotential caused by the localized depletions of ions. Depending on the electrochemical process involved other negative effects can result, such as parasitic gas evolution, passivation of electrodes, dendrite growth, and or poor electroplating or electrocrystallization.
- the electric mobility u (m 2 /Vs) of an ion is its drift velocity (m/s) in the field (V/m).
- the values of u can be found in various chemical reference books.
- the current density is expressed as J and the conductivity as K.
- FIG. 4 illustrates this concept.
- the porous electrode can be characterized as a distribution or gradient of reaction rates averaged over a large structure. This type of electrode can increase the effective surface area being exposed for reaction by a factor of 10 3 to 10 5 .
- FIG. 23 shows an illustrative porous electrode.
- reaction rates are applicable to the porous electrode but are complicated by the physical structure of the electrode.
- the ratio of the electrode and electrolyte conductivities can vary over the structure so that the current density is rarely uniform and is usually highest at the interfaces.
- the electrolyte permeates the porous structure but the problem of localized concentration polarization can be highly amplified.
- Non-uniform current density can lead to localized depletion of reactants and accumulation of reaction products; parasitic side reactions; poor material utilization; irregular shaped deposition; and morphological changes in the crystal structure.
- Potential and concentration gradients that exist promote non- uniform current density. Because diffusive processes are slow, the porous electrode is usually mass-transport limited.
- FIG. 23 can help visualize the effect of a long duration DC emf on the porous electrode.
- the ions will be forced to migrate toward the metal current collector for long periods. As seen, this makes it difficult for the hydrated ions to deposit on surfaces that are parallel to and facing the current collector. Deposition or electrocrystallization can be poor because solidification requires good nucleation and growth but the structure and the applied DC electric field increase the chances for poor nucleation. Poor nucleation can result in the formation of dendrite at the interfaces.
- the localized polarization problems have been recognized for a long time and many techniques have been developed to limit the undesired polarization. It is well-known that using pulsed DC improves the efficiency of electroplating. The theory is that the pulse is applied for a duration of time that is shorter than the time it takes for any significant concentration polarization to develop.
- FIG. 15 illustrates a waveform typical of prior art inventions.
- the use of DC causes a polarization overpotential to develop that reduces the charge acceptance and this polarization must be dealt with to achieve reasonable charge acceptance.
- the overpotential that develops is a combination of activation and concentration overpotentials.
- an overpotential is a deviation in the electrode potential necessary to cause a given reaction. The losses that result are irreversible and lead to the generation of heat. All of the prior art processes cause a polarization build-up.
- the DC pulses described can be analyzed as a DC step function.
- a Fourier analysis of an ideal step function would yield harmonics out to infinity.
- the step functions are far from ideal but the rise times are very fast and the harmonic energy generated extends to very high frequencies.
- the 2 nd comer frequency f 2 would be about 3 MHz.
- the envelope amplitude decreases after f, at the rate of -20 dB/decade and -40 dB/decade after f 2 .
- FIG. 21 is a plot of the impedance versus frequency, plotted on a log-log scale, for several types of batteries.
- a pulse can rise fester than the ions can deliver the charge. If a pulse's rate-of-rise exceeds the ions' transient response time, the system must (by definition) be mass-transport limited. Under this condition, the limiting current density is momentarily exceeded and the energy in the pulse must be converted to heat by some undesired process.
- FIGS. 20 A and 20B show the physical structure of a parallel plate capacitor.
- the capacitance developed by a parallel plate capacitor is:
- the permittivity of the dielectric is represented by e, the plate area by A, and the distance between the plates as d. From the equation the capacitance is obviously directly related to the permittivity of the dielectric.
- the polarized water dipoles form the dielectric material.
- FIG. 11 shows the structure of the electrode-electrolyte junction that forms the double layer capacitor and the physical relationship of the water dipoles to the electrode. In a liquid the dipoles are easily polarized. In the IHP, the surface charge causes the dipoles to be highly polarized. However, in the OHP the dipoles are more highly influenced by the ions than the surface charge. If the concentration of ions increases, the dielectric constant (permittivity) decreases thus the capacitance decreases. Likewise, if ion concentration decreases then capacitance increases. The current required to charge the capacitance with DC follows the equation:
- FIG. 24A shows an equivalent circuit for a typical battery cell and is compatible with the equivalent circuit described in the GE Nickel-Cadmium Battery handbook and other battery texts.
- a double layer structure will form at the solid-solution interfaces in an electrochemical system under the influence of an elecUOmotive force.
- C p would be charged to 63.2 % or discharged to 36.8% of its final value.
- Charging a cell with a pulse duration on the order of one time constant and a short duration discharge pulse will charge the capacitor in a little more than 5 times constants.
- the depolarizing pulses slightly discharge the capacitor.
- the wait periods allow the ions outside the Helmholtz region to diffuse freely but the potential across the region holds the double layer structure essentially intact.
- the combination of short duration depolarization pulses and wait periods have little effect on the structure of the double layer capacitor and the activation overpotential that develops.
- the double layer structure at one electrode will dominate the overall reaction. If a particular electrode dominates the reaction with current flowing in a given direction then the other electrode dominates when the direction of current is reversed. With few exceptions, cations do not enter the inner Helmholtz plane because of Gibbs free energy restrictions. This fact means that the dielectric constant is very high and the capacitance is therefore very large. The effective capacitance of the cell is therefore dominated by the opposite electrode with the smaller capacitance. Claims that the depolarization pulses and wait periods breakup or eliminate the double layer ignore the physics of the structure.
- Battery chargers that use 120 Hz rectified DC pulses, typical of the 1960's and as described in the GE Nickel-Cadmium handbook, are effectively pulsed DC to the double layer capacitor.
- the rest or off periods are of longer duration than newer technologies but short enough that the capacitor reaches full charge in a short time. However, the rest periods are of sufficient duration that they waste significant energy in the charge and discharge of the double layer. Because the rest period is of relatively short duration, the measurement of the 'trough' voltage during the off period is not the true open-circuit voltage of the cell, as often claimed.
- the newer techniques discussed above, suffer because the rest periods are too short, compared with the time constant of the capacitance, to discharge the overpotential. The measurements are free from the instantaneous 'IR' losses associated with the concentration overpotential but still have an overpotential error.
- FIG. 11 shows the water dipole's relationship to the positive electrode. The longer the DC potential holds the water dipole tightly to the surface the greater the chance that the water will dissociate into H + , O "2 , and OH " . Because of the strong attraction, oxygen may adsorb at the positive electrode and hydrogen may be adsorbed at the negative. The rernaining elements (by-products) may impede the overall reaction or cause other problems such as gas pressure build-up.
- the process can be analyzed as continuous DC. It is well-known and documented that transient response techniques can be applied to electrochemical systems to separate out the various overpotentials for individual analysis and measurement. Other than pulsed DC, techniques that take advantage of the ion's natural transient responses have not been applied to electrochemical processes to optimize the overall reaction rate.
- a battery is an example of an electrochemical system that can be used in either an electrolytic (energy corouming) or galvanic (energy producing) process. Batteries are often charged with pulsed DC and a depolarizing pulse. The application of the depolarizing (energy consuming) pulses momentarily converts the battery to a galvanic cell but the intended operation is an electrolytic process. Except as noted, transient response techniques are used to improve the reaction rates for electrolytic processes but not for galvanic processes.
- Battery packs often integrate a control circuit, such as a microprocessor, into the pack to monitor the battery's charge and discharge cycles.
- a control circuit such as a microprocessor
- US Patent 4,289,836, issued to Lemelson integrated a microprocessor into a pack for sensing and controlling the battery charging.
- the control circuitry usually monitors the current entering or leaving the battery.
- the control may combine the charge and discharge current with an estimate of self-discharge, including a temperature compensation factor, to predict the available charge capacity of the pack.
- charge te ⁇ nination can be made via the control circuit by sending a control signal to the external power source to terminate charge.
- the internal control circuitry communicates with an external programmable power supply via a serial bus.
- US Patent 5,572,110 issued to Dunstan, describes this type of system.
- the control can specify the power supply's current and voltage levels to match the battery chemistry. This last technique allows the programmable power supply to be safely used with various battery chemistries.
- US Patent 5,471,128, issued to Patino et al a battery undervoltage protection circuit is described.
- US Patent 5,569,550 issued to Garrett et al, overvoltage protection for the battery is added.
- US Patent 5,218,284 issued to Burns et al, a switching power supply is included to control both the charge and discharge current levels. Except as noted, the control circuitry does not actively enhance the discharge performance of the battery in a galvanic mode of operation.
- Electrons transfer the charge in metals and semiconductors whereas ions transfer charge between a metal and a solution of its ions.
- the three forms of t ⁇ __r_smission are electron flow, ion flow, and charge transfer reactions at the electrode- electrolyte interface.
- the equations relating the charge transfer steps of ions and electrons are very similar.
- FIGS. 19A and 19B Two systems that rely on electron charge transfer are illustrated in FIGS. 19A and 19B. These systems have historically relied on an alternating current electromotive force to provide activation energy.
- a flourescent system is shown in FIG 19 A.
- E g energy gap
- E g energy gap
- the valence band and conduction band are separated by an energy gap, shown as E g
- E g energy gap
- the electron gains sufficient energy to jump to the conduction band. Obeying the natural tendency to return to the lowest energy level available, the electron gives up the extra energy and drops down to the valence band.
- a photon is emitted.
- the wavelength of the light emitted depends on the width of the energy gap. In this situation, the wavelength is emitted in the visible band so useful light results. The emission of light stops when the electrical stimulus is removed.
- a phosphorescence system is shown in FIG 19B. Again, an energy gap separates the valence and conduction bands. An additional energy level, shown as E t , results from the introduction of a donor (impurity) into the material. When the electrical stimulus is applied, the electron gains the necessary energy to jump to the conduction band. When the electron drops back down, it emits a photon but then becomes trapped in the donor trap level. The electron will remain in the donor trap level temporarily before dropping back to the valence band. A photon will be emitted when the electron leaves the donor trap level. Because the electron is temporarily trapped in donor trap level, the phosphorescent material will continue to emit light for a short time after the electrical stimulus is removed. Historically, this type of system has been powered with complex ac power sources.
- One phosphorescent light system of interest is the electroluminescent lighting strip.
- the light output efficiency of the strips is low and they can experience short operational life. Increasing the ac voltage's amplitude (up to 380 Vrms) and frequency (up to 8 kHz) can increase the light output. The conflict is that the operational life is inversely proportional to the ac voltage's amplitude and frequency.
- the physical structure of the material is similar to a parallel plate capacitor so that the impedance of the system is largely capacitive. Low-cost inverters are available for powering small strips, up to 20 VA. The technology for producing very large or very long strips is now available. However, the cost of 150 VA to 500 VA ac power supplies is prohibitively high and is hindering the acceptance of the systems.
- FIG. 20 is an illustrative drawing of a dielectric system similar to the elecfroluminescent strip.
- Current texts on the subject explain that the electroluminescent strips cannot be driven with DC and the upper operating range for ac is 8 kHz.
- the application of an electromotive force polarizes the molecular dipoles in the dielectric material. If the potential is reversed as occurs with alternating current, the molecular dipoles must reverse 180°. The rotation introduces a dipole-friction and a displacement current flows. The result is that the dielectric loss increases with frequency. Molecular dipoles experience the highest dielectric loss at roughly 10 kHz. Corona discharge is a problem at the present levels of ac voltage. The corona can cause the plastic insulating materials to deteriorate rapidly. Being able to control the light output is highly desirable but the cost of dimming circuitry for the larger strips is prohibitively high.
- an object of this invention to provide an electromotive force (emf) that effectively utilizes the natural resonance or other physical properties of a system to optimize the electrokinetic behavior of the charged particles, and further, utilizes the reactive energy or amplification at resonance to increase the effectiveness of the process without an increase in the applied input average or DC power.
- emf electromotive force
- the emf should maximize the natural Brownian movement of an ion and the prevailing diffusion process in a solution.
- the displacement, in time, of ions should be normalized to the physical distances of the electrical double layer.
- An object of this invention is to produce an electronic catalytic effect in an electrochemical process by effectively reducing the activation overpotential, concentration overpotential, and energy loss in the electrical double layer thus reducing the activation energy needed for the reaction to occur. Further, it is an object of the electronic catalytic effect to increase the exchange current in the system's process thereby increasing the limiting current density with the result being an improvement in efficiency and throughput for the process.
- An object of this invention is to provide an electronic method for providing mass-transport perturbation, especially including the electrical double layer, and further, to create an electromotive perturbation that is perpendicular to the electrodes that optimize the natural processes of Brownian movement, diffusion, and convection. Further, it is an object of the perturbation to optimize the concentration of reactants at the reaction sites and reduce the development of concentration gradients over the surface while maximizing the penetration within the porous electrodes, if applicable, thereby increasing the effective surface area of the electrodes. Still further, it is an object of the perturbation to improve the electrodissolution, electrodeposition, or electrocrystallization at the surfaces.
- An object of this invention is to provide a process that utilizes the impedance of an active electrochemical system to control the amplitude of the applied emf, and particularly, to allow the system impedance to naturally damp the amplitude of the applied electromotive force thereby allowing automatic process control of the emf amplitude. Still further, it is an object to adjust the DC offset, peak currents, duty-cycle, and frequency of the control process to match the changing conditions of the system.
- An object of this invention is to provide process control, via transient-response and integral- transform techniques, that can be used to improve the reaction rate of both electrolytic and galvanic systems, and in particular, to provide a method that can be used to control battery performance during both electrolytic or galvanic modes of operation.
- a further object of this invention is to provide a low-cost process for powering luminescent systems that provides low-cost circuitry for diniming, and particularly in electroluminescent lighting systems, a DC emf waveform that: (a) effectively eliminates dielectric loss; (b) reduces corona discharge; (c) extends the operational frequency limit above 8 kHz; (d) increases output brightness; and (e) extends the operational life.
- EMI electromagnetic interference
- Electrokinetic behavior is the resulting charged particle motion caused by changes in the applied electric field.
- This method can be applied to a very broad field of applications that include physical, biological, and electrochemical systems, such as, electrolysis, batteries, and flourescent and electroluminescent lighting (photochemical) systems.
- This method can be applied to batteries to improve both electrolytic and galvanic modes of operation.
- An unexpected benefit of the method is that the circuitry needed to provide the optimized electrokinetic behavior is lower in cost than the existing circuitry.
- FIG. 1 illustrates an electromotive force (emf) of the method that produces a desired charged particle displacement for optimized electrokinetic behavior.
- the emf takes the shape of an ideal damped sinusoidal waveform superimposed on a DC potential. Practical implementations of this method will deviate from the ideal shape shown.
- the value A establishes the amplitude
- B defines the rate of decay
- C sets the frequency of oscillation.
- the function h(x) defines the offset and takes the form:
- Value D is an offset multiplier and value R sets the rate of approach to the offset.
- a first positive peak causes an initial positive displacement of the charged particle.
- the slope of the displacement approaches zero.
- the potential becomes negative and the charged particle displacement also becomes negative.
- the negative displacement is roughly 1/3 of the initial positive displacement.
- the emf waveform again approaches zero potential, the slope of the charged particle displacement again approaches zero.
- the emf continues to increase positively and the displacement again becomes positive.
- the positive displacement of the 2 nd positive peak is roughly 2/3 of the initial first positive displacement.
- the slope of the charged particle displacement approaches zero for a third time.
- a second negative emf peak causes a negative charged particle displacement that is roughly 1/3 of the positive displacement caused by the second positive emf peak.
- FIGS. 2A and 2B depict the effect of a DC offset on a damped sinusoidal emf.
- the emf waveform follows the format described for FIG. 1.
- FIG. 2 A shows a damped sinusoidal emf with no DC offset. A positive net displacement will result because the emf s leading positive peaks have greater amplitude than the following negative peaks.
- FIG. 2B shows a damped sinusoidal waveform with a DC offset applied that is similar to FIG. 1 but with different peak amplitudes.
- FIG. 2 A shows greater negative charged particle displacement per unit of time than FIG. 2B.
- FIG. 2B shows roughly a 5 to 1 increase in net positive displacement per unit of time than FIG. 2A.
- FIGS. 3A and 3B show two damped sinusoidal waveforms with identical peak values and DC offset but operated at different frequencies of oscillation to illustrate the effect on charged particle displacement.
- FIG. 3 A shows an emf at base (lx) frequency and a resulting charged particle displacement in time.
- FIG. 3B shows an emf at twice the base frequency and a resulting charged particle displacement in time.
- FIG. 4 shows a damped sinusoidal waveform with different peak amplitudes.
- FIG. 6 shows a block diagram of the essential elements needed to implement this method.
- System 50 consists of injection-means 1, waveform-generator 2, control-circuit 3, process 4, power-source 5, and control-signals 6, 7, and 8.
- Process 4 is the physical process to be optimized.
- Injection-means 1 couples the outputs from waveform-generator 2 and power-source 5 then supplies the resulting emf to process 4.
- Waveform-generator 2 is a conventional waveform-generator used to develop the emf signal supplied to injection-means 1.
- Control-circuit 3 generates control-signal 6 to control the output of waveform-generator 2.
- Control-circuit 3 is conventional in implementation and can be as simple as an operational amplifier circuit or as complex as a microcontroller or full computer system.
- Power-source 5 is conventional and could range from the ac mains to a programmable power supply.
- Control-signal 6 can be a single signal or a plurality of signals, including voltage, current, frequency, duty-cycle, and/or damping ratio, used to control the output from waveform-generator 2.
- Control- signal 7 can be a single signal or a plurality of signals and can be unidirectional or bidirectionaL Control-signal 7 can be used by control-circuit 3 to monitor and/or control process
- Control-circuit 3 controls process 4 indirectly via waveform-generator 2, injection- means 1, and (possibly) power-source 5.
- Control-circuit 3 could control certain parameters of process 4, such as temperature, directly via control-signal 7.
- Control-signal 7 can be used as process feedback from process 4 for voltage, current, impedance, temperature, pH (hydrogen-ion activity), pressure, and/or other statistical process control (SPC) parameter.
- SPC statistical process control
- Control-signal 7 is optional if system 50 is operated open-loop (without feedback from process 4).
- Control-signal 8 is used optionally by control-circuit 3 to monitor and or control power-source 5.
- Control- signal 8 can be a single signal or a plurality of signals and can be unidirectional or bidirectional. Control- signal 8 could be used to control the output parameters of voltage, current, and frequency from power-source 5.
- FIG. 7 is a simplified schematic diagram of system 51 derived from the block diagram in FIG. 6.
- System 51 consists of the same essential elements described in system 50.
- Control-circuit 3, process 4, power-source 5, and control-signals 6, 7, and 8 are identical in function and description to system 50.
- Injection-means 1 is further clarified in FIG. 7 as a coupled-inductor 9.
- the circuit symbol for coupled-inductor 9 is unfortunately identical to the symbol used to identify a transformer.
- the construction and operation of coupled-inductor 9 are very similar to a conventional transformer.
- the primary winding (injection winding) of coupled-inductor 9 is connected between process 4 and power-source 5 while the secondary winding is connected to waveform-generator 2.
- coupled-inductor 9 and a transformer is the importance of the inductance in the winding.
- the primary winding of coupled-inductor 9 must act as a current-source (inductor) to match the impedances of power- source 5 and process 4.
- an essential feature for proper operation of coupled-inductor 9 is the inclusion of a capacitor in the output of power-source 5. This capacitor completes the current path for the primary winding of coupled-inductor 9 and process 4 through system 51 ground.
- Waveform-generator 2 is shown in FIG. 7 to consist of switch 12, inductor 11, capacitor 10, and diode 13.
- Waveform-generator 2 in system 51 is a conventional LC-tuned oscillator.
- Control-signal 6 activates switch 12 to initiate an oscillation cycle.
- Inductor 11, secondary winding of coupled-inductor 9, capacitor 10, and diode 13 form a conventional LC tank circuit used to generate the desired emf waveform.
- the waveform developed on capacitor 10 is applied directly to the secondary winding of coupled-inductor 9.
- Coupled-inductor 9 superimposes (couples) the emf waveform from the secondary winding onto the DC current supplied by power- source 5.
- Switch 12 is shown as a pnp transistor but can be any switch suitable for the application.
- FIGS. 5A, 5B, 5C, and 5D show four different but similar emf waveforms.
- FIGS. 5 A and 5B waveforms take the form:
- FIG. 5 A shows the waveform with a positive DC offset and FIG. 5B shows the waveform with a negative DC offset.
- FIG. 5C shows the waveform with a positive DC offset
- FIG. 5D shows the waveform with a negative DC offset. Practical implementations of this method will deviate from the ideal shapes shown.
- FIG. 18 shows an emf waveform developed from a current-source with a limited rate-of-rise. Practical implementations of this method will deviate from the ideal shape shown.
- This alternate waveform is a modified pulsed DC emf.
- the current is ramped from the 0 value to a positive peak value at a rate-of-rise that matches the operational performance needed.
- the positive amplitude is maintained at the positive DC rate for a specified time.
- the current is then ramped down at a controlled rate until the negative peak is reached then the current is reversed and ramped back to the positive peak value.
- the percentages of time are shown as a reference and can be adjusted to match the application.
- the dwell time at zero crossing is shown as zero but it could be set for a period greater than or equal to 5 time constants.
- the example shown is based on 50 cycles of 60 Hz ac power and the ramp time from one peak to the other peak being equal to 8.333 milliseconds.
- FIG. 10 shows system 54 with an alternate circuit implementation for injection-means 1 and waveform-generator 2.
- Control-circuit 3, process 4, power-source 5, and control-signals 6, 7, and 8 are identical in description and operation as system 50.
- the functional operation of system 54 is identical to the descriptions given for system 50 with the exception that injection-means 1 is implemented as a conventional linear amplifier circuit and waveform-generator 2 is implemented as oscillator 32.
- Oscillator 32 is a conventional circuit used to generate either a sinewave, triangular, or squarewave signal.
- the output of oscillator 32 is supplied to switch 31.
- Switch 31 is shown as a npn transistor but can be any switching device suitable for the application.
- the output of oscillator 32 would normally be capacitively coupled to the base of switch 31.
- Resistors 27 and 28 are used to set the Q point for switch 31.
- Resistor 29 is an emitter resistor used to generate feedback to control the stability of switch 31.
- Resistor 30 is the collector resistor used to control the current for switch 31.
- FIG. 8 shows module 52 and external-circuit 23 that comprise the essential elements described in system 50.
- Module 52 consists of injection-means 1, waveform-generator 2, control-circuit 3, process 4, switches 14 and 15, capacitor 16, connections 20, 21, and 22, and control-signals 6, 7, 8, 17, and 18.
- Injection-means 1 and waveform-generator 2 are shown in detail for clarity and are identical in function and description as given in system 50.
- Process 4 is further defined as battery 19.
- Capacitor 16 is an essential element for the proper operation of coupled-inductor 9 with the addition of switches 14 and 15. Capacitor 16 completes the current path for the primary winding of coupled-inductor 9 and battery 19 through module 52 ground.
- Control-circuit 3 is identical in function as given in system 50 but in module 52 the function is better defined than the global description given in system 50.
- Control circuit 3 is normally implemented with a microcontroller integrated circuit.
- Control-signals 17 and 18 control the direction of current flow, via either switch 14 or switch 15, for external-circuit 23, coupled-inductor 9, and battery 19.
- Control-signal 18 is used to charge battery 19 via switch 15 and control-signal 17 is used to apply power to external-circuit 23 via switch 14.
- Switches 14 and 15 are shown as pnp transistors but any switch could be used that is suitable for the application. Switch 15 may also be a diode if control of charge is not desired or necessary.
- control-circuit 3 monitors the condition of battery 19 through control-signal 7.
- control-signal 7 can be a single signal or a plurality of signals that include measurements of voltage, current, impedance, temperature, and pressure from battery 19.
- Control-signal 6 is identical in function and description as given in system 50.
- External-circuit 23 can be either an external power-source similar to power-source 5 or an external system that operates from the power developed by battery 19.
- Control-signal 8 is optional.
- Control-signal 8 can be a single signal or plurality of signals and can be unidirectional or bidirectional. Control-signal 8 may be used to control the output of external-circuit 23 when it is a programmable power-source or to communicate with external-circuit 23 if applicable. Connections 20, 21, and 22 are connection points shown to emphasize the difference in module 52 and system 51.
- FIG. 9 shows module 53 that is essentially identical to module 52 except for the addition of inductor 24, capacitor 25, and diode 26.
- Switch 14, inductor 24, capacitor 25, and diode 26 are configured as a switching power supply.
- Control-signal 17 is now a pulse-width-modulator (PWM) control-signal to control the duty-cycle of switch 14.
- Control-signal 8 must include the function of feedback for proper regulation of the output voltage at connection 20. Although not shown, feedback would be provided from connection 20 to control-circuit 3 with or without external-circuit 23 being connected at connections 20, 21, and 22. This configuration allows control-circuit 3 to provide a fixed or programmable output voltage at connection 20.
- PWM pulse-width-modulator
- External- circuit 23 can provide a programming signal, at connection 21 , via a serial bus communication or a simple voltage or resistance setting.
- the configuration shown (buck) can only provide a voltage that is less than the voltage of battery 19.
- the components of switch 14, inductor 24, capacitor 25, and diode 26 can be rearranged (buck/boost) to provide a voltage greater or equal to the voltage on battery 19.
- Switch 15's emitter is again shown connected at connection 20 but it could be wired separately. Although very difficult to implement because of the conflicting requirements, coupled-inductor 9 could also be used to form the switching power supply. Switch
- switch 14 would be connected with the emitter to coupled-inductor 9 and the collector to the positive electrode of battery 19.
- Diode 26 would be connected to the emitter of switch 14 and module 53 ground.
- Inductor 24 and capacitor 25 would be eliminated.
- switch 14 coupled-inductor 9, capacitor 16, and diode 26 would form the switching power supply.
- the response to the stimulus will be maximum. This maximum response occurs if the stimulus (at ⁇ f ) approaches the natural response (at ⁇ n ).
- a system may have more than one resonant point.
- the charged particles can be controlled using the reactive amplification and the reactive energy drives the process more effectively than the DC or average (real) power applied.
- the reactive amplification at resonance is illustrated in FIG. 4. Determination of the ⁇ n frequency is an important first step in the process to optimize the electrokinetic behavior of the charged particles. The determination of the resonant point in a physical system is generally straightforward but it is more complicated with an electrochemical system. Other factors may dictate that the system is operated away from resonance but resonance must be understood to optimize the system performance.
- Non-reactant ions in an aqueous solution form encounter pairs that have a lifetime of 10 "12 to 10 "8 seconds. During this time they experience 10 to 100,000 collisions before separating from each other.
- Theory describes one ion as a sink and the other ion can be viewed as moving in the electric field of the stationary ion. This theory can be applied a priori to the case of an encounter of a surface and a non-reacting ion.
- the lifetime of the encounter (in the double layer region) is governed by the strong forces exerted by the double layer on the ion.
- the diameter of a hydrated ion is on the order of 1 nm, the effective thickness of the double layer region is roughly 3 to 10 nm, and the Helmholtz plane is on the order of 3 nm. If the ion transient response is determined to be limited at 10 ⁇ s, for example, a priori it takes 10 ⁇ s for ions to overcome the electrophoretic retardation and time lag associated with the double layer.
- the driving force should therefore be normalized to produce ion drift on the order of nanometers in an interval that maximizes the natural ion encounter lifetimes but is not faster than the ion response time. In effect, this is optimizing the ion movement to the physical parameters.
- the first pulse would strongly drive the ions 6 nm toward the electrode then pause to allow the ions to diffuse freely.
- the next pulse would pull the ions away from the electrode 2 nm then pause to allow the ions to diffuse.
- a 2nd less strong pulse would push the ions 4 nm toward the electrode and then pause. This would be followed by a pull that moved the ions 1 nm from the electrode followed with a pause.
- a 3 rd push of 2 nm and then a pause would follow. This third push would be followed by a very low intensity drive (slight push) that essentially allowed the ions to diffuse freely.
- FIG. 1 An emf that can cause this ion displacement is shown in FIG. 1.
- the waveform is that of a damped sinusoidal function with a DC offset.
- the frequency of oscillation in this example would be less than 100 kHz to match resonance and transient response times.
- the damped sinusoidal waveform is a waveform that occurs throughout nature. It is also the output response of an underdamped system.
- FIG. 1 it can be seen that each time the emf waveform crosses the zero line, the slope of the displacement over a small period is essentially zero which corresponds to a time that the ions are free to diffuse naturally.
- the sinusoidal nature of the waveform will not charge the double layer capacitor.
- the potential across the double layer structure is zero and then the potential is reversed.
- a very significant effect is that the double layer structures at the electrodes are reversed and reformed with a major perturbation of the Helmholtz region as well as the diffuse regions.
- FIG. 25 illustrates the effect of the emf on the double layer structure.
- five time intervals are illustrated.
- the inner Helmholtz plane (IHP) at both electrodes is well ordered and the cell is in a galvanic mode.
- Time interval B shows that the potential across the electrodes is zero and the IHP is disrupted.
- the ions are released from the force of the IHP and free to diffuse.
- the water dipoles are reoriented by the ions.
- time interval C the cell is in an electrolytic mode and the IHP at each electrode is again well-ordered but in a reverse direction.
- Time interval D again shows the potential at zero and the IHP disrupted.
- time interval E the cell is back in the galvanic mode and the IHP at each electrode is well-ordered but reversed for a second time.
- the first law of kinetics describes how the overpotential n. varies exponentially with the current density. Therefore, the waveform n. usually rises or decays exponentially.
- the damped sinusoidal waveform also follows an exponential rise or decay so the emf exponential shape follows the natural response of the system. Ions are delivered and allowed to diffuse naturally so the effective concentration is maximized and ri j . is rriinimized.
- the current density is directly proportional to the exchange current as represented in the Tafel equation.
- the exchange current is a measure of the freedom from kinetic limitations. A large value of exchange current means the reaction will proceed with a low overpotential at high current density. Optimizing the kinetics at the interface therefore effectively lowers n.. If the frequency of oscillation approaches the natural resonance of the ion drift and double layer structure the reaction rate will be rraximized and the parasitic elements minimized.
- the DC offset shown in FIG. 1 is the normal DC emf that would be used to drive the system in prior art inventions.
- the reactive power allows a more effective force without an increase in the average or DC energy supplied to the system.
- FIG. 16 depicts the displacement with the new method versus the equivalent DC current.
- the damped sinusoidal waveform shown completes three oscillations each cycle with 5 direction changes and 5 diffusion periods.
- the first peak in the example is nearly 5 times the amplitude of the DC value and results in a large initial displacement that is equal to one-half of the total displacement each cycle.
- the displacement resulting from the DC does not reach the same value until roughly 60% of the cycle is completed.
- the last diffusion period lasts roughly 20% of the cycle.
- the net straight-line displacement from the equivalent DC is only 80% of the displacement from the damped sinusoidal waveform over the same period.
- FIG. 24B shows the dynamic nature of an electrochemical cell to contrast the static view depicted in FIG. 24A.
- the electrochemical cell is in a constant state of change. Many factors affect the cell and include current, voltage, temperature, state-of-charge, and previous operating conditions. Even with DC operation, the cell is constantly changing and should be viewed as a dynamic system.
- FIG. 17 A comparison of a damped sinusoidal waveform and a DC step function is shown in FIG. 17.
- the comparison is intended to quantify the other parasitic losses associated with DC versus the sinusoidal waveform.
- FIG. 22A illustrates one method, of prior art, to provide mass-transport perturbation using a flow channel. Other methods exist for mechanical stirring with various resulting flow patterns. One common factor is that the stirred solution develops a laminar flow over the electrodes that is parallel with the plane of the electrodes.
- FIG. 22 A The resulting flow- velocity distribution is shown in FIG. 22 A.
- the velocity of the flow approaches zero at the surfaces.
- the concentration of reactants is greatest at the leading edge of the electrode and lowest at the trailing edge, such that, the reaction rate is greatest at the leading edge and decreases across the electrode surface.
- FIG. 22B shows the relative advantage of the perpendicular electromotive mass-transport perturbation created by this method.
- the electromotive perturbation combined with mechanical stirring will improve the concentration distribution across the surface of the electrodes.
- Many industrial processes are operated at or near the limiting current density for maximum throughput, since the limiting current density will increase with the perpendicular perturbation, the throughput will increase.
- a primary cause of self-discharge in a battery is the morphological structural change in the crystal structure. If a battery is subjected to a waveform as depicted in FIG. 1, but with zero DC offset, during inactive periods a priori the self- discharge process will be reduced.
- the energy-density in a battery is a function of the total mass of active material and effective surface area of the electrodes.
- the peak current density is a function of the surface area at the interface of the electrodes.
- the physical construction of a battery is a compromise between thick electrodes (large mass) and interfacial surface area. If both modes of electrolytic and galvanic operation were controlled in a battery by a process, with the waveform (peak 5x DC offset) depicted in FIG. 1 superimposed on the DC current, a priori thicker electrodes could be used to increase energy-density yet maintain the peak current capability.
- the drift velocity that an ion can achieve is based on the ionic mobility of the ion and the force applied.
- the ionic mobility of the hydrogen ion H + is roughly 4.5 to 8 times faster than a typical metal ion and the hydroxide ion OH " is about 3 to 5 times faster.
- Hydrogen gas evolution is often a product of a parasitic side reaction caused by inefficient charging and discharging.
- the hydrogen generated at one electrode often migrates to the other electrode and causes permanent damage to the active materials.
- the build-up of hydrogen gas also increases the pressure in a cell and can lead to permanent damage.
- a log-log plot of impedance versus frequency would yield a plot with -45° slope (-20 dB/decade) approaching the ⁇ iimum impedance point at resonance ⁇ n , a cusp at ⁇ n , and a +45° slope (+20 dB/decade) after the resonant point.
- the phase would be -90° until the point 0.1 ⁇ n then the phase would ramp up at 90° per decade (2 nd order system) before leveling off at +90° at 10 ⁇ ⁇ .
- the initial slope is very gradual and is followed by a very wide, nearly zero slope plateau that extends for 3 to 5 decades before increasing.
- phase and impedance relationships indicate a complex, multiple order system with multiple resonance points.
- the electrochemical system can maintain a relatively flat response over a very wide frequency span. The only means of maintaining a flat response is for the reactive components to change in value as the frequency increases. Experimentation confirms that the capacitance decreases with increasing frequency below ⁇ n . This means that the cell is effective until the ion transport or reaction is no longer able to respond to external demands.
- the electrochemical system has a critically damped response to a stimulus based on the time-domain transient response measurements. The voltage rises and falls to external loads with an exponential response. Charge acceptance decreases with increasing temperature and/or overpotentials. Thus, the generation of heating and overpotentials provides external parameters for process control of charge acceptance. If active control, with feedback, is used on an electrochemical process, the peak current, DC offset, and frequency of the charge waveform can be matched to the changing conditions in the cell to maximize the charge acceptance.
- the resistance value will determine the damping ratio.
- a very low value of R will yield an underdamped system and a very large value will result in an overdamped system.
- a forcing function such as the waveform depicted in FIG. 1
- the response to the stimulus will depend on the value of R. If the cell impedance is low then the response will be underdamped. In this way, the process in this system is naturally damped by the effective resistance of the electrochemical system. For example, if the impedance of a deeply discharged battery is initially high then the peak current values will be naturally damped (reduced). As the charge level increases and the effective resistance decreases, the peak current will increase. This natural damping effect can be seen in FIG. 4.
- FIG. 1 shows an electromotive force (emf) capable of causing optimized charged particle electrokinetic movement or displacement in an electrochemical system.
- emf electromotive force
- the initial peak of the emf causes a displacement in time of the ions toward one electrode.
- the slope of the ion displacement is essentially zero.
- the ions are free to diffuse without the influence of the emf.
- the emf waveform continues negatively, the ions are pulled away from the electrode. As the waveform again approaches zero, the ions are again allowed to diffuse freely.
- each cycle of oscillation has a decreasing displacement, positive and negative, in time.
- the frequency of oscillation for the emf is selected to match closely the system's natural resonance frequency.
- the displacement in time of the ions can be further controlled by changing the peak emf amplitude and the DC offset.
- the displacement in time should be optimized to match the natural physical structure of the system and here that structure is the electrical double layer that forms at the solid-solution interfaces. The goal is to optimize or normalize the ion's electrokinetic behavior (movement) to the process, in this case cause a displacement of nanometers per time. Operating at or near system resonance allows the use of reactive energy or amplification to improve the system response without increasing the applied average or DC energy.
- FIGS. 2A and 2B show the effect of DC offset on the emf and resulting displacement.
- the DC offset affects more than the net displacement in time. If no DC offset is applied, the ions will receive greater positive and negative perturbation (displacement) in time but with a small net positive displacement, as shown in FIG. 2A. If the DC offset is set greater than the value shown in FIG. 2B, the net displacement will be greater but the positive and negative perturbation of the ions will be further reduced and also the time and frequency of the diffusion periods will be reduced. Increasing the DC too much has an adverse effect on the perturbation of the ions, assuming that the peak amplitude remains constant.
- FIGS. 3 A and 3B The effect of frequency-of-oscillation is shown in FIGS. 3 A and 3B.
- FIGS. 3 A and 3B are plotted on the same time base and FIG. 3B is allowed to continue to oscillate over the total time. With the same peak current and DC offset, increasing the frequency of oscillation reduces the ion displacement over the same time.
- FIG. 4 shows three different ac peak amplitudes for the emf. Adjusting the peak amplitude will result in more useful oscillation cycles being developed, as seen in FIG. 4.
- the adjective 'useful' is used to relate the number of negative displacements per cycle to the desired ion perturbation.
- the peak amplitude and DC offset resulted in about three useful oscillation cycles. Increasing the peak amplitude in FIG. 3B would result in more useful oscillations and greater ion perturbation.
- FIG. 4 also illustrates the concept of reactive energy or amplification at resonance. The closer the frequency of the emf is to the natural resonance of the system the greater the response of the system.
- FIG. 4 also shows how the system's impedance can control the emf. If the system impedance is high at the beginning of the process, this impedance will damp the response to the emf and the peak current will be reduced. As the process proceeds and the impedance decreases, the response will increase.
- FIG. 6 is a system block diagram of the essential elements needed to implement this method.
- system 50 controls the reaction rate of process 4.
- Injection-means 1 superimposes (injects) the emf waveform generated by waveform-generator 2 on the DC offset current generated by power-source 5.
- Control-circuit 3 monitors process 4 and adjusts the emf waveform and DC offset current to optimize the electrochemical process.
- Control-circuit 3 can optionally monitor the process parameters of process 4, including voltage, current, impedance, temperature, pressure, pH (hydrogen-ion activity), and/or other statistical process control (SPC) parameters. Changes in the impedance of process 4 automatically adjust the peak amplitude of the emf.
- SPC statistical process control
- Control-circuit 3 could override the damping factor separately from process 4 thus increasing or decreasing the peak amplitude of the emf.
- Control-circuit 3 can effectively control the reaction rate of process 4 by controlling the emf characteristics, which include voltage, current, frequency, duty-cycle, and damping ratio.
- Control-circuit 3 also can control how many damped oscillations are allowed per cycle. The number of damped oscillations can range from a one cycle to a practical limit of maybe 10.
- Control-circuit 3 can optionally control the output parameters of power-source 5, including voltage, current, and frequency.
- injection-means 1 is coupling a forcing function ⁇ f onto the DC offset that can be independent of the natural resonance ⁇ instruct.
- FIG. 7 shows one preferred-embodiment, system 51, for applying the emf waveform in this method.
- System 51 deviates from the global operation of system 50 by the implementation of injection-means 1.
- Injection-means 1 is implemented as coupled-inductor 9.
- Coupled-inductor 9 superimposes the emf signal, from waveform-generator 2, on the DC current from power- source 5.
- An important design characteristic of coupled-inductor 9 is the turns ratio of the primary and secondary windings. The turns ratio determines the relative amplitude of the coupled emf from the secondary to the primary winding.
- a very important and less obvious parameter is the coupling coefficient. Tightly coupled windings result in a high coupling coefficient and loosely coupled windings result in a low coupling coefficient.
- the coupling coefficient of coupled- inductor 9 is high then the emf will be injected in phase with the primary current. With a low coupling coefficient, energy will be stored in the core and a time delay (phase lag) will occur before the energy is delivered to the primary.
- phase lag time delay
- process 4 were an electroluminescent system, the highly capacitive system would be matched to a coupled-inductor 9 with a low coupling coefficient. If process 4 were a battery, the low impedance battery would be matched to a coupled-inductor 9 with a high coupling coefficient. The coupling coefficient allows the emf to be matched to low and high impedance loads.
- FIGS. 5A, 5B, 5C, and 5D are typical of the voltage emf that results with a high impedance or reactive load and a low coupling coefficient.
- FIGS. 1, 2A, 2B, 3 A, 3B, and 4 are typical of the current emf that results with low impedance loads and high coupling coefficients.
- FIG. 18 shows an emf waveform suitable for very high current applications that exceed the current capability of injection-means 1 implemented with coupled-inductor 9. Many electrochemical processes operate at very high currents that could benefit from higher efficiency and ion perturbation, as depicted in FIGS. 22A and 22B.
- FIG. 18 illustrates a pulsed DC emf with limited rate-of-rise and this waveform is therefore developed by a current-source with a limited rate-of-rise.
- FIG. 18 is compatible with system 50, as shown in FIG. 6. Waveform- generator 2 and control-signal 6 would be eliminated.
- Injection-means 1 (inductor or current-source) controls the rate-of-rise of the emf current applied to process 4. Injection-means 1 limits the rate- of-rise to a practical value that minimizes the DC energy loss.
- Process 4 is driven by the DC emf for a period that matches the application and then control-circuit 3 initiates a negative current cycle by turning-off the positive current output of power-source 5. At the zero-crossing point, control-circuit 3 could initiate a wait period of greater than 5 time constants or initiate the negative current output of power-source 5. When initiated the current will then continue to ramp to the negative peak. At the negative peak, control-circuit 3 turns-off the negative current output of power-source 5 and then current begins to ramp to zero. At the zero-crossing point, control- circuit 3 will start the next positive DC cycle.
- This high current emf embodiment could also be implemented in a low-cost, low-current configuration.
- This low-cost implementation could be used when acquisition costs are more important than the operational benefits and energy-savings derived from the preferred- embodiment of system 50 implemented with the emf waveform depicted in FIG. 1.
- FIG. 8 shows a practical application of system 51 in the form of module 52.
- the operation of module 52 is essentially identical to system 51 with the inclusion of external-circuit 23.
- module 52 is intended as an integration of battery 19, control-circuit 3, waveform-generator 2, coupled-inductor 9, and switches 14 and 15 into a single package.
- the preferred- embodiment of module 52 is the packaging of control-circuit 3, waveform-generator 2, coupled-inductor 9, and switches 14 and 15 into an assembly that is roughly the size of a single cell of battery 19. The resulting assembly and battery 19 would then be packaged together as an integral battery assembly, module 52.
- Control-circuit 3 is typically a microcontroller circuit that regulates all aspects of the charge and discharge of battery 19.
- Switches 14 and 15 can be used to protect battery 19 from external short-circuits and overcharge currents.
- Switch 15 controls the charge current being applied to battery 19 by a power-source at external-circuit 23.
- Switch 15 could be implemented to operate in the linear mode or as a current-source to regulate the DC current supplied to battery 19. If switch 15 is operated in this mode then the power supply in external-circuit 23 can be a very low-cost, unregulated supply.
- Module 52 eliminates the need for an external battery charger and lowers the overall system cost.
- Switch 14 is used to control the discharge current drawn from battery 19. Switch 14 can terminate the discharge of battery 19 to ensure a temperature-compensated safe depth-of-discharge as determined by control-circuit 3.
- Coupled-inductor 9 will continue to inject battery 19 with the emf waveform, no dc offset, when switches 14 and 15 are bothturned-off.
- the current path is through capacitor 16, coupled- inductor 9, battery 19 and module 52 ground.
- the emf pulses, with no DC offset, are applied to battery 19 to ⁇ iinimize the amount of inactive material and reduce memory and self-discharge effects.
- the repetition rate of the pulses is determined by control-circuit 3 based on battery 19 usage (history) and ambient temperature.
- Switches 14 and 15 are connected at connection 20 but could easily be connected to individual connections points for separate connection to external- circuit 23.
- Typical feedback signals, from battery 19, supplied by control-signal 7 would be battery-voltage, battery-center-tap voltage, and battery-temperature.
- the battery-center-tap voltage can be used to monitor imbalances in individual cells.
- Control-circuit 3 can optionally communicate with external-circuit 23 via control-signal 8.
- the communication may be as simple as logic level status signals, such as, enable and status.
- the communication could be via a serial bus that transmits battery 19's state-of-charge data to a host system that is operating from the power supplied by module 52.
- a user could signal control-circuit 3, via control- signal 8, to override the safe depth-of-discharge protection.
- Control-circuit 3 would also record battery 19 usage and this data could be used to determine warranty issues. This information could be retrieved via control-signal 8 if the proper codes are supplied by (the host) external-circuit 23.
- FIG. 9 shows module 53 as a further extension of the lower-cost and smaller module 52.
- the major distinction between module 52 and module 53 is the inclusion of a regulated power supply in the output of module 53.
- the power supply can optionally be programmable.
- Switch 14, inductor 24, capacitor 25, and diode 26 form a regulated power supply, shown in the buck configuratioa
- the components could also be arranged in a buck-boost arrangement if a voltage higher than the voltage of battery 19 is needed.
- Switch 14 could also be implemented as a low- cost linear regulator power supply and inductor 24 and diode 26 could be eludinated.
- Module 53 could eliminate the need for the internal power supply typical of the host system located in external-circuit 23.
- This method allows this process to be applied to a very broad base of physical and electrochemical systems beyond the examples discussed.
- this method has been experimentally applied to other electrolysis processes and the use of this method in many industrial processes is contemplated.
- This method can be applied immediately to processes such as the in-situ electrokinetic remediation of contaminated soils, electrophoresis, electrodecantation, electroplating, electrodissolution, electrodialysis, electrodischarge or electrolytic machining, electrorefining, electropolishing, electroforming, electroextraction, electrostatic precipitation, electroendosmosis, electrocapillarity, electrostatic separation, and the formation of new batteries.
- the types of charged particles contemplated extends beyond molecules, ions, and electrons to include biological systems.
Abstract
Description
Claims
Priority Applications (6)
Application Number | Priority Date | Filing Date | Title |
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JP53602398A JP2001511942A (en) | 1997-02-18 | 1998-02-18 | Electronic method of controlling charged particles for optimal electrokinetic behavior |
CA002280732A CA2280732A1 (en) | 1997-02-18 | 1998-02-18 | Electronic method for controlling charged particles to obtain optimum electrokinetic behavior |
EP98908599A EP0970532A4 (en) | 1997-02-18 | 1998-02-18 | Electronic method for controlling charged particles to obtain optimum electrokinetic behavior |
AU66597/98A AU720246B2 (en) | 1997-02-18 | 1998-02-18 | Electronic method for controlling charged particles to obtain optimum electrokinetic behavior |
BR9807310-9A BR9807310A (en) | 1997-02-18 | 1998-02-18 | Electronic method to control charged particles to obtain optimal electro-kinetic functioning |
NO993946A NO993946L (en) | 1997-02-18 | 1999-08-17 | Electronic method for controlling charged particles to achieve optimal electrokinetic behavior |
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US08/802,032 US5872443A (en) | 1997-02-18 | 1997-02-18 | Electronic method for controlling charged particles to obtain optimum electrokinetic behavior |
US08/802,032 | 1997-02-18 |
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EP (1) | EP0970532A4 (en) |
JP (1) | JP2001511942A (en) |
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AU (1) | AU720246B2 (en) |
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- 1998-02-18 CA CA002280732A patent/CA2280732A1/en not_active Abandoned
- 1998-02-18 CN CN98802620A patent/CN1248347A/en active Pending
- 1998-02-18 WO PCT/US1998/003216 patent/WO1998036466A1/en not_active Application Discontinuation
- 1998-02-18 EP EP98908599A patent/EP0970532A4/en not_active Withdrawn
- 1998-02-18 JP JP53602398A patent/JP2001511942A/en active Pending
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Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
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EP1021858A1 (en) * | 1997-03-27 | 2000-07-26 | Todd Taricco | An apparatus and method for recharging a battery |
EP1021858A4 (en) * | 1997-03-27 | 2003-03-19 | Todd Taricco | An apparatus and method for recharging a battery |
US6440837B1 (en) * | 2000-07-14 | 2002-08-27 | Micron Technology, Inc. | Method of forming a contact structure in a semiconductor device |
US8362625B2 (en) | 2000-07-14 | 2013-01-29 | Round Rock Research, Llc | Contact structure in a memory device |
US8786101B2 (en) | 2000-07-14 | 2014-07-22 | Round Rock Research, Llc | Contact structure in a memory device |
Also Published As
Publication number | Publication date |
---|---|
JP2001511942A (en) | 2001-08-14 |
CN1248347A (en) | 2000-03-22 |
AU6659798A (en) | 1998-09-08 |
US5872443A (en) | 1999-02-16 |
BR9807310A (en) | 2000-05-02 |
EP0970532A4 (en) | 2000-10-04 |
EP0970532A1 (en) | 2000-01-12 |
CA2280732A1 (en) | 1998-08-20 |
NO993946L (en) | 1999-10-15 |
AU720246B2 (en) | 2000-05-25 |
NO993946D0 (en) | 1999-08-17 |
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