WO2022191721A1 - Procédés et système de fonctionnement de batterie assisté acoustiquement - Google Patents

Procédés et système de fonctionnement de batterie assisté acoustiquement Download PDF

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Publication number
WO2022191721A1
WO2022191721A1 PCT/PH2022/050002 PH2022050002W WO2022191721A1 WO 2022191721 A1 WO2022191721 A1 WO 2022191721A1 PH 2022050002 W PH2022050002 W PH 2022050002W WO 2022191721 A1 WO2022191721 A1 WO 2022191721A1
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Prior art keywords
battery
battery cell
energy
input
electrical energy
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PCT/PH2022/050002
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English (en)
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WO2022191721A4 (fr
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Drandreb Earl JUANICO
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Juanico Drandreb Earl
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Priority to KR1020237034454A priority Critical patent/KR20230156741A/ko
Priority to JP2023555214A priority patent/JP2024509913A/ja
Publication of WO2022191721A1 publication Critical patent/WO2022191721A1/fr
Publication of WO2022191721A4 publication Critical patent/WO2022191721A4/fr

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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
    • 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
    • H01M10/06—Lead-acid accumulators
    • 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
    • H01M10/4214—Arrangements for moving electrodes or electrolyte
    • 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
    • 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
    • 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
    • H01M2010/4278—Systems for data transfer from batteries, e.g. transfer of battery parameters to a controller, data transferred between battery controller and main controller
    • 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

  • the invention disclosed herein relates to rechargeable battery operation (i.e. discharging, charging, recharging, or a sequential combination thereof) and specifically to the lengthening of the battery cycle life through the mitigation, minimization or prevention of the formation of discharge byproducts that degrade the battery’s capacity to store electrical charge (i.e., capacity fade) over time.
  • a battery is a form of electrochemical storage that works on the quasi-reversibility of the chemical change processes among certain materials, holding an electrical charge in one form and mobilizing those charges as electric current into another form.
  • the chemical storage processes are the half-cell reactions that produce or require electrons to happen.
  • the equations that represent such electrochemical processes are written with the implicit assumption of a well-mixed reactor.
  • batteries are typically designed with low mixing capabilities because of the countervailing preferences in favor of portability and mechanical stability.
  • RE renewable energy
  • RE sources are becoming a rising component of the energy mix as countries worldwide are migrating away from fossil- fuel-based power generation technology known for greenhouse gas emissions that adversely affect the Earth’s climate.
  • RE-generating facilities typically put out a fluctuating, non-dispatchable electrical output.
  • variable RE generation is seen in the power fluctuations in solar PV generation due to cloud movements and wind power generation due to wind velocity variability.
  • Excess RE generation curtailment which happens during high RE intensities, but low demand, results in a missed opportunity to assimilating clean energy into the energy mix.
  • BESS Utility-scale battery energy storage systems
  • batteries can quickly absorb, hold, and reinject electricity.
  • electrochemical degradation shortens the cycle life of batteries, regardless of battery chemistry.
  • One form of degradation is sulfation in lead-acid batteries. Sulfation happens when the battery gets insufficient charge, such as in RE applications, wherein the energy sources like sunlight and wind are intermittent. It could also occur when the battery sits excessively long between charges, as short as 24 hours in hot climates.
  • the discharge byproduct known as lead sulfate (PbS0 4 ) forms during the discharge phase when the battery supplies electric current to a load or spontaneously. This material accumulates due to its partial reconversion during recharging.
  • batteries are designed to be portable and durable, implying lesser room to incorporate the mixing functionality, e.g., batteries with solid-state electrolytes, which must be as thin as the diffusion layer.
  • the mixing is induced by deliberately boiling the electrolyte by over-charging, which also causes thermal runaway and long-term damage to the battery.
  • the liquid electrolyte is replaced by a gel- type electrolyte, which is more durable but to which mixing by thermal action or mechanical motion is even less feasible.
  • a potential non-invasive method to induce mixing in the battery is by exposure to sound or acoustic waves.
  • Sound waves will potentially generate a reconfigured pressure distribution especially to the porous components of the battery that might enhance mass transfer through the electrodes.
  • sound waves may also potentially generate bubbles, especially to a liquid electrolyte, through a mechanism known as atomization or nebulization. This effect can lead to the misting of the electrolyte in addition to those generated from over charging the battery.
  • sulfuric acid the acid mist could be harmful to the lungs and even carcinogenic if inhaled. Therefore, any means of acoustic excitation must consider the tradeoff between misting and mixing.
  • US Patent 7592094B2 also European Patent 1639672B1
  • US Patent Application 20200020990A1 disclosed methods of vibrating the solid electrode of the cell element either by embedding or stacking a piezoelectric transducer.
  • the transducer s mechanical vibrations would consequently agitate the surrounding, less rigid components (e.g., liquid or solid-state electrolyte), which may cause discharge byproducts to disentangle from or not form at all on (due to constant excitation) the electrode surface.
  • an added layer of protection coated on the embedded piezoelectric material may reduce the electrodes’ porosity to ion transfer for more in- depth interaction between electrolyte and electrode.
  • the piezoelectric material is necessarily brittle so that the strain from colliding with a rigid material during vibrations could cause mechanical breakage or thermal cracking thereof.
  • the high accelerations caused by this layer’s vibration could also induce nebulization and transfer heat to the electrolyte with continued operation. All these effects could be detrimental to the long-term battery capacity and cycle life as the buildup of discharge byproducts, which both solutions attempted to address.
  • a group from the University of California in San Diego took a different approach to induce mixing using acoustic waves by taking advantage of the electrolyte’s fluid nature.
  • a patent US 1115889B2 was granted to an invention for the acoustic manipulation of batteries.
  • This invention pertained to the procedure for the input of electrical energy that effectively injects a stirring effect to the electrolyte.
  • the consequent stirring as taught by the disclosure, supposedly melts out and dissolves any trace of solid deposits (i.e., dendrites) forming on the interface between solid parts of lithium anode batteries.
  • the stirring effect taught by this disclosure also presupposes the presence of solid electrochemical byproducts (e.g., dendrites), which the said intervention is targeting to disintegrate.
  • the acoustic energy input must also be accompanied by engineered manipulations of the electrical input requires complex controls that may be sensitive to the slightest deviations from precision.
  • This secondary form of deliberate energy input herein disclosed is sound or acoustic energy.
  • the sound energy is transmitted as a pressure wave of a frequency between 36 and 3600 kHz.
  • This frequency range is in the ultrasonic regime and could be generated by devices known as ultrasonic transducers, which are industrially available in many variations and for numerous purposes.
  • devices known as ultrasonic transducers which are industrially available in many variations and for numerous purposes.
  • common purposes to which such devices are applied include fluid atomization, nebulization, cleaning, and electroplating. None of those purposes include the application of such ultrasound- producing devices for assisting the operation of a battery, such as in the storage (extraction) of electrical energy to (from) the battery or its modular components known as cells.
  • This disclosure also draws attention to the mechanisms that facilitate the mass transfer of active ions resulting in the dynamic optimization of charge capacity.
  • the interaction of the sound waves with the battery cell structure and materials generates the bulk longitudinal waves or BLW.
  • the effect of the BLW manifests in the pressure variations that pervade the interior of the battery cell, not only across the fluid portion but also even within the solid material and the interfaces between them.
  • the pressure variations can take the form of a reconfigured pore-pressure distribution over the cross-section of the porous materials in the battery cell.
  • the pressure variations can be visualized, at least through computational multiphysics simulations, as a distribution pattern of high and low pressure. This pattern is akin to an atmospheric pressure map typically shown by weather forecast reports.
  • the low pressure areas correspond to regions of high relative velocity.
  • ions can cross the spot with high mobility.
  • This effect on mobility can be interpreted as a facilitation of the mass transfer between the porous solid materials making up the battery electrodes and separator, which is a requirement for the recovery of active material on recharge.
  • the present disclosure further draws attention to an embodiment of the acoustically assisted battery operation at the cell element level.
  • This embodiment illustrates the attachment of the sound sources to the enclosure of the battery cell module for the smallest commercially available size of the battery.
  • the overall design can be expanded for bigger battery sizes.
  • the attachment of the sound sources are akin, in principle, to bulkhead fittings.
  • Results from the computational simulation and laboratory experiments of this embodiment corroborate with one another, supporting the research hypothesis that the input of sound energy to supplement the electrical energy input optimizes the charge capacity of the battery cell.
  • the corroboration of the said results imply that the empirical evidence agrees with the perceived theory of the interaction between acoustic energy and the battery’s internal structure and materials. While this agreement was confirmed through the embodiment disclosed, it is an anticipated that this corroboration will likewise be applicable for other battery sizes.
  • this disclosure draws attention to a method of non-invasive estimation of the battery state of health (SoH) using the same form of secondary energy input, i.e., sound.
  • This method requires that the sound is used both as an emitted and received signal across the internal structure of the battery during its operation.
  • the emitted acoustic signal serves as the reference signal, whereas the received acoustic signal serves as the diagnosis.
  • This diagnosis is supplied as input to a computational software that has been programmed to perform an automated pattern classification.
  • the result of the pattern classification is a decision to classify the diagnosis as one corresponding to a cell state above a threshold SoH and one below the said threshold.
  • This decision is then supplied as input to a programmed control circuit that switches the level of electrical input to charge any particular battery cell.
  • the invention can be implemented as a temporary or permanent add-on attachment to the battery casing.
  • the piezoceramic elements can be embedded to the case using methods known to those skilled in the art of plumbing, such as bulkhead fittings.
  • the embedding ensures an efficient energy transfer as the piezoceramic element directly radiates acoustic waves to the electrolyte rather than through a solid material.
  • the distributed transducer configuration creates an intricate mixing pattern that maximizes the bulk coverage of mass transfer.
  • the waveforms, phase differences, and frequency differences among the transducers and the acoustic interaction with the micropores of the porous components would make the mixing flow dynamic instead of steady, giving rise to turbulence and vortices while simultaneously reconfiguring pore-pressure distributions of the porous components.
  • the acoustic transducers are activated on recharge and a possibly non-zero duration after that, e.g., while idling or discharging.
  • the acoustically forced convection will mobilize the electroactive species at the electrode-separator and electrolyte- electrolyte interfaces.
  • Pb 2+ ions are generated from an electron- transfer step followed by the precipitation of PbSC>4 - the discharge byproduct.
  • the Pb 2+ ions are generated by a dissolution of PbS0 4 followed by the precipitation of PbC>2 or Pb by an electron-transfer step. Mobility may assist the dissolution of solvated Pb 2+ ions produced while recharging.
  • the activation of the transducer may be automated using a microcontroller. If placed at the bottom, the transducer generates upward fluid momentum that may oppose the gradients tending toward electrolyte stratification, for which electrolyte concentration increases toward the bottom due to gravity. Stratification, or the presence of a vertical concentration gradient, is also known to promote the accumulation of discharge byproducts. It seems to be caused by the non-uniformity in the vertical distribution of current.
  • a transducer may be placed such that its vibrating face is about parallel to the normal vector of the face of the separator/electrode. A gap between the transducer surface and the cell element can be adjusted. This gap will optimize the flow patterns resulting from the nonlinear interaction between the sound wave and he interior setup (i.e., material, geometry, interfacial microstructure, etc.) of the cell.
  • Frequencies are high but not beyond a cutoff frequency that generates median droplet sizes in the order of 10 -6 meter or less. Very small droplets of this size will easily be ejected through any opening dissipating to the air rather than falling back to the bulk and recombine. Bigger droplets will tend to have a higher rate of droplet recombination to the bulk and recombine. Bigger droplets will tend to have a higher rate of droplet recombination to the bulk electrolyte by means of gravity.
  • the narrow droplet size distribution centered at around 10 -6 meter is achievable with piezoceramic disks. Other piezoceramic geometries could shift the center but maintain the narrow width of the distribution.
  • the mixing flow would be generated directly by the bulk longitudinal waves (BLWs) originating from the plurality of vibrating piezoceramic elements.
  • BLWs cause Faraday waves to the surface of the fluid supported by a vibrating solid.
  • porous materials such as the electrodes and separators, contribute flow resistance, the pores may induce turbulence to the flow patterns, which is rather advantageous.
  • the intricate flow pattern resulting from the forced convection driven by the BLWs would mix the electrolyte.
  • the mixing flow would circulate the electroactive species, allowing those to sweep out hotspots of electrochemical interaction.
  • the route to capacity fade of battery cells includes hindrances to the completion of idealized half-cell reaction equations.
  • the discharge byproducts would accumulate gradually along with the depletion of electroactive materials.
  • the mixing flows resulting from BLWs may assist the discharge byproduct’s dissolution into forms that are readily convertible to active material during the recharge phase.
  • the manufacturing of piezoceramic elements may utilize the same core material, e.g., Pb, as those found in the battery’s components.
  • Pb e.g.
  • Other lead-free piezoceramic materials e.g., potassium-sodium niobate (KNN) with nickel inner electrodes (Kawada et al., 2009), will be suitable for nickel-based batteries.
  • KNN potassium-sodium niobate
  • Known lithium substitution methods in KNN while remaining to be manufacturable by conventional sintering techniques (Wang et al., 2011 ), may be appropriate for lithium- based batteries.
  • the effect of acoustic wave injection to the basic electrochemical cell, i.e., the fundamental unit of the battery, is simulated computationally and confirmed experimentally.
  • the multi-physics simulation expresses the best mathematical representation of the hypothetical mechanism of the interaction between sound and the battery cell structure and material during a recharge and/or discharge.
  • the laboratory experiments validate the results implied by the computational simulations. The agreement between experiment and simulation results indicate that the theoretical principles underlying the interaction between sound waves and the internal battery cell structure and materials are adequately captured.
  • the simulation results are presented for a cell element unit subjected to a control condition without sound input and for the experimental condition with sound input.
  • the control case serves as the reference to test whether or not any apparent deviation indicated by the results from the experimental case are statistically significant.
  • the simulations incorporate the same charge-discharge sequence executed by a real potentiostat.
  • the relevant physics are identified and coupled with one another as a systematic representation of the sound-matter interaction occurring inside the battery cell.
  • the results indicate that the injected sound waves effectively slow down the factors of degradation, especially at the innermost portion of the cell element unit where the degradation rate seems the highest. Arresting the degradation factors by sound directly lengthens the cycle life of the cell element, as the results suggest.
  • the results of confirmatory experiments are also presented in this disclosure.
  • the BOO laboratory experiments were conducted in a controlled environment with an average temperature of 25 deg C and relative humidity of 50%. For every trial, a control and experimental case were run simultaneously to eliminate temporal effects and ensuring consistency in the ambient conditions, such as temperature and humidity, that could affect the results.
  • the charge-discharge cycles were administered by an automated 305 battery potentiostat (Biologic VSP-3e system) through its Charge Efficiency Determination (CED) test protocol. This test protocol drained the cells all the way to 100% depth of discharge, which is equivalent to performing a torture test of accelerated degradation.
  • the ultrasonic transducers operated only when the battery was charging.
  • An experiment terminated at the second cycle in which the charge 310 capacity failed to exceed 70%.
  • the experimental results indeed confirmed what the simulations predicted.
  • the sound input assisted the battery cell to achieve longer cycling by as much as 200% on average.
  • the use of sound to improve the cycle life of the battery is not only for the passive intervention of battery operation, but also for active intervention. Sound can be used 315 as a signal to detect any developments of the internal structure of the battery, such as the formation of sulfate deposits along its lifetime. Also disclosed herein is a method and apparatus of implementing active intervention that influences the charging process of the entire battery. This intervention implies a novel procedure of charging in parallel rather than in series, which is the conventional way. In parallel charging, 320 each cell element of the battery may receive a different amount of current than the other cell elements charging at the same time. This setup is motivated by the observation that the cells in the battery do not perform in synchrony all the time. Some cells discharge earlier than others, which eventually determines the entire battery’s state of charge.
  • the patterns of the received sound contain information of the internal structure of the battery cell that can be used to deduce SoH.
  • SoH internal structure of the battery cell
  • the assumption that the pattern contains relevant information of the battery SoH is motivated by the fact that sulfates are solid and typically originate at the interfaces between the electrode and separators. The solid sulfates accumulating at these interfaces can induce delays to the propagating sound waves, which then changes the cross-correlations between the emitted and the received sound.
  • the extraction of the information embedded in the patterns of the received sound is then used to control the amount of current dispensed to a cell element when the battery is charging.
  • This “customized” current input would enable the battery to reach a state of balance among its component cells after recharging. This balance should lengthen the lifespan of the battery because overcharging (which causes heating and boiling) and undercharging (which accelerates sulfation) can be mitigated, minimized or prevented.
  • FIGURE 1 Multiview of the battery cell with emphasis on the part excluding the top lid (displayed in the axonometric view), showing sound wave sources embedded in the battery case, the cell element consisting of a plurality of electrodes (both positive and negative), and interelectrode spacing with or without separators.
  • FIGURE 2 Lateral view of the battery cell showing the gap between each sound wave source and the nearest edge of the cell element, which is immersed in the electrolyte.
  • FIGURE 3 Lateral view of the battery cell with emphasis on the flow field lines depicting the mixing of the electrolyte due to the sound waves generated by the sound wave sources that induce momentum on the electrolyte.
  • FIGURE 4 The conceptual diagram of the connectivity of the battery cell and the charging system supplying power to the battery terminals and the embedded sound wave source FIGURE 5. Mass transfer of electroactive species as a result of the acoustic mixing generated by a distributed transducer configuration.
  • FIGURE 6 Detailed view of the cell element unit inside an enclosure with embedded ultrasonics (top row). 3D view of the cell element unit for the control with no sound (left, bottom row) and experiment with sound (right, bottom row)
  • FIGURE 7 Basic geometry of the multi-physics model of the cell element unit of the battery, showing the experimental (top, left) and control (top, right) see-through views.
  • the cell element unit is an alternating stack of positive, separator, and negative electrodes until each side presents the outer face of a positive and negative electrode.
  • the experimental setup includes embedded transducers (disc-shaped objects attached to the lateral and bottom faces of the cell enclosure.
  • FIGURE 8 Block diagram of the computational multi-physics model showing the different kinds of physics hypothetically governing the underlying mechanism of the interaction between sound and the battery cell internal structure and material.
  • FIGURE 9 Charge-discharge cycling protocol as implemented by an automated potentiostat (left) and simulated using a computational multi-physics software (right).
  • FIGURE 10 Comparison of simulated concentration of the active battery material across the entire cell element after 10 charge-discharge cycles: control (no sound), and various frequencies at the same driving voltage, 18 Vpp.
  • FIGURE 11 Simulated progression of the concentration of the active battery material along an axis normal to face of the stacked cell plates from Cycle 1 through 4 (Top to bottom).
  • FIGURE 12 Simulated progression of the concentration of the active battery material along an axis normal to the face of the stacked cell plates in Cycle 8 (top) and 10 (bottom).
  • FIGURE 13 Simulated progression of the state of health (SoH) of the electrodes through several cycles superimposing the result at different conditions: control (no sound), and with sound at different frequencies (top). The SoH progression of different electrodes across a cell element unit for each condition (bottom).
  • FIGURE 14 Simulated scans of the pressure (top panel set) and mass transfer velocity (bottom panel set) on the different electrode plates of the cell element unit at a sound frequency of 110 kHz driven by a peak-to-peak voltage of 18 V.
  • FIGURE 15 Simulated scans of the pressure (top panel set) and mass transfer velocity (bottom panel set) on the different electrode plates of the cell element unit at a sound frequency of 1700 kHz driven by a peak-to-peak voltage of 18 V.
  • FIGURE 16 Simulated scans of the pressure (top panel set) and mass transfer velocity (bottom panel set) on the different electrode plates of the cell element unit at a sound frequency of 2400 kHz driven by a peak-to-peak voltage of 18 V.
  • FIGURE 17a Typical course of the laboratory experiments for the control setup, with no sound. The corresponding charge-discharge cycling performance are shown at the bottom row, plotting the voltage curves and the charge/discharge capacity lines progressing through the cycles.
  • FIGURE 17b Typical course of the laboratory experiments for the hypothetical setup with embedded ultrasonics. The corresponding charge-discharge cycling performance are shown at the bottom row, plotting the voltage curves and the charge/discharge capacity lines progressing through the cycles.
  • FIGURE 18 Consolidated cycling performance for numerous experiments compared among different conditions, including the control with no sound, and experimental with sound at different frequencies and driving voltages (peak-to-peak).
  • FIGURE 19 3D view of an embodiment of a cell-level parallel charger with SoH estimation using non-invasive acoustic diagnostics.
  • FIGURE 20 Schematic view of the cell-level parallel charging of a battery using information from the acoustic diagnostics.
  • the battery case 101 is the least innovated part of the battery because of its non active participation in the battery’s electrochemistry.
  • the present disclosure points to the use of sound waves to induce, in a non-destructive way, the mixing of the electroactive species of the battery cell in the hopes of maximizing the yield and rate of essential electrochemical reactions that are analyzed under the assumption of a well-mixed battery cell.
  • a solution to the mixing problem through the reconfiguring of the pore pressure distribution forms the core subject matter of this disclosure.
  • Sound wave sources e.g., in the form of piezoceramic transducers, which can be placed at the bottom 103 and non-bottom portions/faces 102, 104 of the battery case 101.
  • the non-bottom transducers may include the top portion of the cell, as long as there are no hindrances (e.g., terminals, vents) place on lid covering the battery cell compartment.
  • a cell element 105 found inside the case 101 may, in some variations, be arranged in a stacking configuration consisting of electrodes 107 and interelectrode spacing 106, which may or may not include an electrically insulating but porous separator material.
  • the stacking of the electrodes 107 may, in some variations, consist of the alternative placing of positive and negative electrodes.
  • Each electrode is, in some variations, a plate consisting of metallic material with or without non-metallic active material coating and may or may not be porous.
  • the entire cell element is fixed in position inside the cell compartment 101 to achieve mechanical stability or durability in anticipation of the motion of platforms on which the batteries are applied.
  • the sound wave sources may be piezoceramic transducers 102, 103, 104 and placed at strategic positions relative to the cell element 105.
  • the number of transducers portrayed in the diagrams does not, in any way, be interpreted as a limitation, but only as a means for illustration of the concept.
  • the attachment of a transducer to the battery case must be sealed to prevent the leakage of electrolyte 201 and other active materials from inside the cell while allowing the transducer to directly interact with the interior of the cell, such as with the electrolyte 201.
  • the attachment may be fabricated using standard fittings, such as bulkhead fittings. The fittings may be integrated as part of the design so that the manufacture of the battery case 101 includes provisions for the fitting.
  • the attachment may be retrofitted to an existing battery cases that do not provide the access point for the transducer to the interior of the cell.
  • the direct interaction between the sound wave source and the cell interior will enhance the efficiency of the energy and momentum transfer so that mixing 301 will take place with minimal input power and/or losses due to thermal and/or viscous heating.
  • the leak-proof fitting will isolate the interior from the exterior part, where electrical wiring 405, 406, 407 may be present to connect the sound transducers 102, 103, 104 to a power supply for their operation.
  • the sound transducers may be driven by a battery management module 404, which is connected via a supply line 408 to an external energy source 409.
  • the energy source 409 may be a solar PV system, wind turbine system, alternator, or any other means for generating electricity.
  • the microcontroller 404 diverges into supply lines 403, 405, 406, 407 to the different parts of the battery cell.
  • the supply line 403 directs electrical charge to the battery terminals 401 and 402 during charging/recharging.
  • the operation of the charging and activation of the sound transducers is managed by the battery management module 404, which may include an on-board computer to cause variations to the procedure through which the transducers are driven and battery charge is dispensed.
  • the management module 404 may receive feedback through the supply lines 403, 405, 406, 407 to estimate a state relating to the battery health for monitoring and control purposes. This management module 404 will ensure to minimize the instances of over-charging and under-charging the battery, or over-driving and under-driving the sound transducers.
  • the acoustic transducers 102, 103, 104 may therefore consist of the ability to sense changes related to the battery health through the sound waves that may carry the information related to the interaction of sound to the dynamic changes taking place within the battery cell, e.g., formation of deposit byproducts, temperature increase, or fine mist formation.
  • the acoustic interaction is based on the generation of bulk longitudinal waves (BLW) to the electrolyte and through the porous structures in the battery cell.
  • the acoustic transducer vibrates at a frequency and produces pressure variations in the fluid that forces convection.
  • the porosity of the cell element contributes resistance to flow, which the forced convection overcomes through the momentum arising from the acceleration near the transducer surface.
  • the acceleration causes a high rate of density changes that propagate through the bulk. Due to the bulk resistance, the density waves propagate up to an effective length that depends on the viscosity, surface tension, and density of the bulk fluid and F of the transducer.
  • the acoustic wave propagation could drive the mass transfer of solvated ions or the electroactive species dissolved in the bulk electrolyte through a mixing process 301 that can take place through the interelectrode spacing 106.
  • the resulting mass transfer 501 could pass through the pores of the cell element 105, enabling an equalized distribution of the said ionic species throughout the container.
  • the BLW imparts momentum to the fluid electrolyte, which attunes the operation of the cell to well-mixed reactor as implied by the half-cell reaction equations used to represent the underlying electrochemical mechanism of the battery.
  • the actual enhancement of the mass transfer 501 of electroactive species due to the acoustically induced mixing mediated by poroacoustics in the cell provides a dynamic means by which the yield of the half cell reactions could be maximized throughout the cycle life of the battery.
  • the invigorated flow momentum caused by the direct interaction of sound wave sources and the interior of the cell, especially a fluid electrolyte, is also the underlying reason behind the conversion of such electrolyte into aerosol droplets capable of escaping and be evaporated away from the cell.
  • Atomization or nebulization takes place because of capillary (or Faraday) waves that form on the fluid surface that is supported by a solid platform that vibrates at a frequency F.
  • the Faraday wavelength can be estimated from the following expression in which ais the surface tension of the electrolyte and p is its density.
  • the amplitude of the vibrations is sufficiently long to cause droplets to detach from the bulk.
  • the median diameter of such droplets is a factor of the Faraday wavelength.
  • higher frequencies are expected to generate smaller droplets.
  • microscopic droplets, which collectively appear as mists are formed at ultrasonic frequencies.
  • the atomization threshold is a mathematical relation first expressed by Pohlman and Stamm (cited in Pohlman et al., 1974). It relates the amplitude A of the transducer vibration and the onset of atomization to the viscosity h of the electrolyte fluid and its surface tension and density, and the Faraday wavelength l.
  • misting is beneficial for medical nebulizers (e.g., as a means to more effectively deliver certain therapeutics through aerosol inhalation), for batteries it is rather not preferable.
  • Electrolyte mists especially the acidic variety, are known to be carcinogenic. Indeed, battery factories are required to clean up acid mists as a health precaution for workers who are exposed to the inhalation of the mists that could eventually ulcerate their lungs to fatal levels.
  • the distributed transducer configuration optimizes the tradeoff between misting and mixing. No individual transducer must be driven with substantial power input.
  • any single transducer in the configuration can be driven with a power input of less than 10 mW/cm 2 .
  • This low power would limit the extent to which the pressure variations caused by the acceleration of the vibrating transducer.
  • the distributed configuration compensates for this limited influence by ensuring that the scope of the mixing effect, i.e., mass transfer 501 , is extensive.
  • the strategic positioning of the transducers relies on the three-dimensional structure of the cell and the generic stacking setup of the cell element.
  • the interelectrode spacing which are sufficiently narrow, to act as bridge for ionic transfer between electrodes, doubly serves as a poroacoustic channel (in the presence of a separator) that causes turbulent flows in the mixing pattern.
  • the complex mixing pattern would effectively inject an ample intensity of randomness to the forced convection, which increases the chances that the electroactive species will sweep out any available site of chemical interaction at any given time.
  • This enhanced probability of chemical interactions would defer the stagnation of the battery’s underlying mechanism, i.e., the formation of discharge byproducts that do not anymore participate in the electrochemical reactions.
  • the so-called dissolution-precipitation mechanism would keep on operating in the presence of acoustically assisted mixing despite subjecting the battery to conditions that would otherwise hasten its capacity fade, e.g., deep cycle charging in RE storage applications.
  • the production of piezoceramic transducers could be co-located within the battery factory because of the possibility of utilizing the same raw materials.
  • This co-location may reduce the total cost of fabrication of the battery with the capability for acoustically assisted charging such that the additional cost is outweighed by the benefit in terms of longer cycle life.
  • This benefit will likewise make batteries more suitable for RE storage without extensive modifications nor the use of any novel chemistry that is less understood than the existing one operating within mature battery technology.
  • the increase in cycle life by at least 25% will already be sufficient to increase the economic viability of storing RE, thereby increasing the utilization of cleaner forms of energy and easing society’s disentanglement from fossil fuels as the primary energy source.
  • the cell element unit of a lead-acid battery consist of a stack 602 of electrodes and separators bounded together by a bracket 601.
  • the relationship between the cell element unit 602 and the enclosure is illustrated in three dimensional views.
  • the control cell shows the terminal lugs 603 serving another role of securing the cell element to the lid of the enclosure 606.
  • the experimental cell now includes at least one ultrasonic transducer 604 attached by a fitting 605 to a face of the enclosure 607 that is facing the interelectrode spacings of the cell element unit 602.
  • each fitting 605 Inside each fitting 605 is a mechanical element that enhances the mechanical efficiency of the transducer’s vibrations, keeping it from heating up when producing sound. This fitting also incorporates sealants to prevent any form of battery fluid from leaking out through them. Through this hermetic sealing, only the vibrating side of the transducer 604 is exposed to the interior of the battery cell.
  • the geometry of the cell element for both control and experimental setups 701 are shown are similar except for the presence of transducers 703 in the latter.
  • the position of the transducers 703 are visualized in relation to the cell element unit 702.
  • the electrodes of this cell element are labeled with “SU(n)” where n progresses from “1” on one side to “n” on the opposite side.
  • the most internal of the electrodes are labeled SU3 and SU4. These are the electrodes least exposed to the electrolyte because they are well within the bulk of the cell element unit.
  • Each SU is actually a “sandwich unit” representing the electrochemical cell consisting of a positive electrode, separator, and negative electrode immersed in a fluid electrolyte.
  • This geometry of the cell element originated from Camille Alphonse Faure, whose flat-plate design became the successful standard implemented in today’s car batteries.
  • the flat-plate design is also the most economical to manufacture in mass production.
  • the performance of the cell element unit can be anticipated from proper computational simulations that incorporate multiple physics governing relevant aspects of the cell’s operation.
  • the transducer multiphysics 801 incorporate the electrical circuit used to drive the sinusoidal vibration. The conversion from electricity to vibration is handled by the electrostatics and solid mechanics module, while the pressure acoustics considers the transmission of the vibration energy to the fluid as pressure waves.
  • the electrolyte multiphysics 802 considers the fluid dynamics arising from the effect of the pressure waves and the heat transfer due to the dissipation of thermal energy generated by the electrochemical reactions from the electrodes to the electrolyte.
  • the electrolyte multiphysics 802 is coupled with the electrochemistry group 803.
  • the electrochemistry group 803 accounts for the electrochemical reactions that produce byproducts that flow through the electrolyte via mass transfer.
  • the multiphysics computational simulations are driven at a rate 901 by the Coloumbic Efficiency Determination (CED) protocol that of the real potentiostat,.
  • CED Coloumbic Efficiency Determination
  • the CED protocol is the sequence of charging and discharging 902 to which the cell element unit is subjected across time until a termination condition 903 is met (i.e., charge capacity failing to exceed 70% for two consecutive cycles).
  • the concentration of the active material is an important indicator of what happens to the electrode composition after every cycle of charge and discharge.
  • the color bar in Figure 10 indicates the surface concentration of this active material after ten cycles elapsed. Note that at the beginning of the simulation, the concentration of active material is uniform over the entire cell element. After 10 cycles of the control 1001, the interior of the cell element unit (consisting of SU3 and SU4) is brighter than the rest of the SUs. This brightness indicates that the active material in SU3 and SU4 did not recover its initial levels for the control. In the experimental cases with different sound frequencies and 18 Vpp driving voltage, the relative concentration of the interiors are less affected than the control, suggesting that sound waves have to do with such effect.
  • the relative concentration at the interior was least affected at 110 kHz (1002) than at 1700 kHz (1003) and 2400 kHz (1004), suggesting the 110 kHz (1002) could be generating acoustic wave patterns that are suitable for this geometry of the cell element.
  • the runaway deviation of relative performance at the interiors is most apparent from the profile graphs 1101, 1102, 1103, 1201, and 1202 of the concentration. From cycle 1 (1101) through 10 (1202), the concentration of active material at the interior, SU 3 and SU 4, deviated the most in the control.
  • the simulation results can visualize quantities that are not easy to measure in experiments, and these visualizations provide further hints to the performance gain induced by sound waves at 110 kHz.
  • the pore pressure 1401 and velocity distributions 1402 can indicate the manner of redistribution of active material exerted by the pressure variations induced by BLW propagation inside the battery cell.
  • the darker portions of the pore pressure distribution imply low pressure spots, while the brighter portions of the velocity distribution imply higher momenta of the active ions. It appears that 110 kHz offers the most uniform redistribution across the SUs of the cell element.
  • a uniform redistribution implies that the surface area of the electrodes are maximized, which also indicate the maximization of charge capacity.
  • corresponding pore-pressure 1501 and mass transfer velocity 1502 distributions are appreciably even with higher contrast between highs and lows.
  • corresponding pore-pressure 1601 and mass transfer velocity 1602 distributions are apparently imbalance over the cross section of the porous interfaces, which may not be preferable for long-term sustainability of the active material recovery on recharge.
  • the laboratory procedure runs the hypothetical 1702 and control 1712 samples simultaneously while being connected to the same potentiostat system. This simultaneous manner of running the control with the hypothetical sample aims to minimize the influence of temporal effects of environment and electrical fluctuations.
  • the graph of the cycling performance for the hypothetical 1701 and control 1711 is recorded live during the course of the experiment trial.
  • the voltage of the cell element is monitored while the charge capacity is traced during the charging and discharging stages.
  • the capacity trace is as an increasing line that terminates at the time when the mode switches from discharging to charging, or vice versa.
  • the SoH is a percentage quantity that corresponds to the maximum level reached by a capacity trace at a given cycle divided by the maximum level at cycle 1.
  • the box-and-whisker plot 1801 shows the median performance of the cell element subjected to accelerated degradation for different cases.
  • the control case has a median cycle life of 4 cycles, but could reach as high as 6 cycles. This dispersion can be a result of the factory variations among the cell components, which is expected in mass production.
  • the median cycle life is significantly higher than the control and even with respect to the other tested frequencies. Higher driving voltages also appear to enhance the cycle life at this frequency, although this trend is less conclusive for the other tested frequencies.
  • Sound can also be used in a standalone, or integrated, technology to implement an active balancing of the state of charge of the cells in the recharging stage.
  • An embodiment of such an apparatus consists of an array of diagnostic subsystems 1904, one for each cell compartment 1906.
  • diagnostic subsystems 1904 there are six subsystems 1904, one for each of the six cell compartments 1906 of this six-cell battery.
  • Each diagnostic subsystem consists of at least one ultrasound receiver 1905. This diagnostic subsystem would capture the information relating to changes happening inside the cell compartment in relation to the formation of electrochemical byproducts that could impair the long term capacity of the cell.
  • the diagnostic subsystems feed information to a central controller drawing power from the source 1901 via a regulator 1903 that relays the supply of electric current to a cell via a switching voltage regulator 1902.
  • the value of the current relayed to the cell matches the SoH of the given cell.
  • Cells with low SoH may require higher current rates, while those that have high SoH may only require a relatively lower current rate.
  • the high current rates for low SoH cells is meant to make them catch up in charge capacity with neighboring cells that have higher SoH.
  • This variability of the current supplied among the cells imply that the charging must proceed in parallel as implemented by the device 2001.
  • the parallel connection of subsystems 2004 ensures that each cell element only gets the amount of charge it needs to restore its previous SoH.
  • the device 2001 also features a display 2002 and control knob 2003 to accommodate different sizes and models of the battery. This parallel charging strategy is a way of ensuring balance across the entire battery. A balanced battery will tend to last longer because the stresses from overcharging and sulfation are minimized. Indeed, any imbalance of SoH can shorten the battery’s lifespan.
  • WO 2021026043A1 (2021). Acoustic wave driven mixing for suppression of dendrite formation and ion depletion in batteries.

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  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Secondary Cells (AREA)

Abstract

L'invention démontre qu'un fonctionnement de batterie avec une forme auxiliaire d'énergie d'entrée autre que de l'électricité prolonge efficacement la durée de vie de la batterie. La reconfiguration non invasive en fonctionnement de la distribution de pression de pores sur la section transversale des électrodes poreuses immergées dans un électrolyte fluide prolonge la durée de vie de l'élément de batterie. Une entrée secondaire d'énergie sonore avec une configuration de transducteur distribuée intégrée sur le boîtier de batterie dirige des ondes longitudinales en vrac à travers l'électrolyte qui induit une reconfiguration bénéfique de la distribution de pression de pores. La distribution de pression de pores reconfigurée facilite la pénétration d'ions électro-actifs sur la matrice d'électrodes poreuses, ce qui permet d'arrêter l'accumulation de sous-produits de décharge qui provoquent un affaiblissement de capacité. Enfin, une entrée secondaire d'énergie sonore aide à l'équilibrage de charge de tous les éléments de batterie par une estimation de l'état de santé de chaque élément. La recharge équilibrée permet de maintenir l'état de santé global de la batterie, prolongeant par conséquent sa durée de vie utile.
PCT/PH2022/050002 2021-03-08 2022-02-22 Procédés et système de fonctionnement de batterie assisté acoustiquement WO2022191721A1 (fr)

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JP2023555214A JP2024509913A (ja) 2021-03-08 2022-02-22 バッテリーの動作を音響的に補助する方法及びシステム

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0834946B1 (fr) * 1996-10-02 2002-09-11 Japan Storage Battery Company Limited Batterie au plomb-acide régulée par une vanne et procédé de fabrication
CN104577193A (zh) * 2015-01-09 2015-04-29 潘珊 一种提高锂离子动力电池的能量密度的方法及锂离子动力电池
CN105024097A (zh) * 2014-05-02 2015-11-04 广州捷力新能源科技有限公司 变温变压超声消除锂离子电池析锂的方法
US20190072614A1 (en) * 2017-09-01 2019-03-07 Feasible, Inc. Determination of characteristics of electrochemical systems using acoustic signals
US20200136198A1 (en) * 2017-09-13 2020-04-30 Farida Kasumzade Method and device for increasing battery life and prevention of premature battery failure

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0834946B1 (fr) * 1996-10-02 2002-09-11 Japan Storage Battery Company Limited Batterie au plomb-acide régulée par une vanne et procédé de fabrication
CN105024097A (zh) * 2014-05-02 2015-11-04 广州捷力新能源科技有限公司 变温变压超声消除锂离子电池析锂的方法
CN104577193A (zh) * 2015-01-09 2015-04-29 潘珊 一种提高锂离子动力电池的能量密度的方法及锂离子动力电池
US20190072614A1 (en) * 2017-09-01 2019-03-07 Feasible, Inc. Determination of characteristics of electrochemical systems using acoustic signals
US20200136198A1 (en) * 2017-09-13 2020-04-30 Farida Kasumzade Method and device for increasing battery life and prevention of premature battery failure

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