WO2018158725A1 - Nickel based energy storage system - Google Patents

Nickel based energy storage system Download PDF

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Publication number
WO2018158725A1
WO2018158725A1 PCT/IB2018/051315 IB2018051315W WO2018158725A1 WO 2018158725 A1 WO2018158725 A1 WO 2018158725A1 IB 2018051315 W IB2018051315 W IB 2018051315W WO 2018158725 A1 WO2018158725 A1 WO 2018158725A1
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WIPO (PCT)
Prior art keywords
nickel
rect
pid
signal
storage system
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Application number
PCT/IB2018/051315
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French (fr)
Inventor
Antonio La Gatta
Original Assignee
Protonstar Sagl
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Publication date
Application filed by Protonstar Sagl filed Critical Protonstar Sagl
Priority to EP18713010.9A priority Critical patent/EP3590142A1/en
Publication of WO2018158725A1 publication Critical patent/WO2018158725A1/en

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Classifications

    • 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
    • H01M10/24—Alkaline accumulators
    • H01M10/30—Nickel accumulators
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/02—Hydrogen or oxygen
    • C25B1/04—Hydrogen or oxygen by electrolysis of water
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B5/00—Electrogenerative processes, i.e. processes for producing compounds in which electricity is generated simultaneously
    • 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
    • H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M12/00—Hybrid cells; Manufacture thereof
    • H01M12/08—Hybrid cells; Manufacture thereof composed of a half-cell of a fuel-cell type and a half-cell of the secondary-cell type
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H01M4/0402—Methods of deposition of the material
    • H01M4/0404—Methods of deposition of the material by coating on electrode collectors
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H01M4/0402—Methods of deposition of the material
    • H01M4/0421—Methods of deposition of the material involving vapour deposition
    • H01M4/0423—Physical vapour deposition
    • H01M4/0426—Sputtering
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0002—Aqueous electrolytes
    • 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
    • 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
    • Y02E60/30—Hydrogen technology
    • Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis

Definitions

  • High efficiency metal matrix storage system which can be used in all technical sectors requiring electric power and/or hydrogen with high efficiency and low environmental impact.
  • Supercapacitors are composed of two plates called electrodes, which can be polarized and separated by an insulator, and an electrolyte. These storage devices are characterized by their high power density, by their large number of cycles and by their long useful life. Their disadvantage is related to the amount of charge accumulated which depends on the interface surface between electrolyte and electrode.
  • Hydrogen based storage systems are representative of a chemical storage system. Hydrogen is stored in large tanks that can be specially built or available in nature such as salt mines, exhausted gas wells, etc. The most significant problem is that in order to separate hydrogen from water and to compress it, large quantities of electricity are needed. In general, the capacity of a battery is expressed in Ah (ampere/hour) and represents the maximum amount of electrical charge stored in it.
  • this capacity is not fixed but is a variable value dependent on many factors, not least the temperature at which the battery operates.
  • the greatest limits that must currently be overcome are the charge density, the lifespan, or the number of charge and discharge cycles that a battery can withstand, the discharge current, which due to the Joule effect subjects the battery itself to considerable thermal stresses, and last but not least, when a battery reaches the end of its useful life it must undergo a costly industrial process for its disposal.
  • Another important limitation of these storage systems is the fact that at certain low temperatures the electrolyte (a fluid made up mostly of water) tends to freeze, making the battery unusable given that the electrochemical process cannot take place. Similar problems occur in cases where the temperature is too high which causes the vaporization of the electrolyte and thus affects its concentration, which in turn negatively impacts the exact stoichiometric relationships required for the reaction itself to occur.
  • the system is able to store energy in the nanometrically deposited Nickel matrix on an alumina support.
  • the nickel matrix deposited by means of the sputtering technique has a thickness of 40nm and a specific roughness defined as explained below.
  • the two-dimensional spatial spectral power density (2DPSD) must have a peak around 5nm. This value is obtained experimentally by controlling the exposure times, the temperature of the crude nickel support, the vacuum levels, and the plasma generator current.
  • Pc is the forcing power
  • wl is the angular pulsation of the sinusoidal signal
  • rect (w2,t) is the rectangular function with amplitude 1 frequency equal to w2/2pi.
  • Pmax depends on the nickel surface and the storage system power. Typically it can have values up to lOW/cm .
  • W2 is at least 10 times wl.
  • the rectangular signal widens the line spectrum of the sinusoidal signal in its surroundings, improving the charging performance. A greater than 20% reduction of the charging time was achieved in the experimental phase.
  • the signal is naturally unidirectional and must have the negative connected to the nickel.
  • Discharge occurs simply by disconnecting the charging system, then an overvoltage occurs, the potential of which depends on the solute in the electrolyte and the release of gaseous hydrogen which is collected.
  • a more effective way of discharging is the use of an inverted potential signal (positive on nickel) of considerably lower intensity (typically 100 times), this time at constant current and proportional to the amount of hydrogen to be extracted.
  • a feedback mechanism for example a PID controller.
  • Is Imax 3 ⁇ 4: PID(H2) :!: (l+sen(wl :!: t)) :!: (l+0,l :!: rect(w2,t)),
  • Is is the current to the nickel
  • wl is the angular pulsation of the sinusoidal signal
  • rect (w2,t) is the rectangular function with amplitude 1 frequency equal to w2/2pi
  • PID(H2) is the feedback signal from the PID controller in operation as a function of the amount of hydrogen required (it has a value between 0 and 1).
  • Imax has values up to lA/cm .
  • W2 is also at least 10 times wl.
  • the system is then immersed in a liquid electrolyte composed of water and lithium or another metal element with low electrochemical competitiveness with nickel.
  • the neutral electrode always immersed in the electrolyte can be composed of nickel or another noble metal, for example platinum.
  • Alumina is essential for the morphology of the sputtered nickel substrate.
  • Figure 1 shows the essential components of the storage system, comprising a generator G and a PID controller P, and the cell C containing a liquid electrolyte E, an element N made of Nickel or other metal, a layer made of sputtered Nickel and a support made of Allumina containe din the cell.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Engineering & Computer Science (AREA)
  • General Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Secondary Cells (AREA)

Abstract

Energy storage system composed of an electric generator, an electrochemical cell inside which an insulating substrate is inserted and onto which a nickel matrix is deposited, the roughness of which has a peak of about 5nm.

Description

NICKEL BASED ENERGY STORAGE SYSTEM"
TECHNICAL SECTOR
High efficiency metal matrix storage system which can be used in all technical sectors requiring electric power and/or hydrogen with high efficiency and low environmental impact.
PRIOR ART
Currently there are fundamentally three energy storage systems on the market, that is, chemically based (hydrogen), electrochemically based (batteries), and electrically based (supercapacitors). Batteries differ according to the chemical combinations used; they may use lead, lithium-ion, nickel-cadmium, etc.
All batteries contain some degree of toxic elements for human health and the environment, the manufacturing process and subsequent disposal of which require costly investments.
Supercapacitors are composed of two plates called electrodes, which can be polarized and separated by an insulator, and an electrolyte. These storage devices are characterized by their high power density, by their large number of cycles and by their long useful life. Their disadvantage is related to the amount of charge accumulated which depends on the interface surface between electrolyte and electrode. Hydrogen based storage systems are representative of a chemical storage system. Hydrogen is stored in large tanks that can be specially built or available in nature such as salt mines, exhausted gas wells, etc. The most significant problem is that in order to separate hydrogen from water and to compress it, large quantities of electricity are needed. In general, the capacity of a battery is expressed in Ah (ampere/hour) and represents the maximum amount of electrical charge stored in it. However, this capacity is not fixed but is a variable value dependent on many factors, not least the temperature at which the battery operates. The greatest limits that must currently be overcome are the charge density, the lifespan, or the number of charge and discharge cycles that a battery can withstand, the discharge current, which due to the Joule effect subjects the battery itself to considerable thermal stresses, and last but not least, when a battery reaches the end of its useful life it must undergo a costly industrial process for its disposal. Another important limitation of these storage systems is the fact that at certain low temperatures the electrolyte (a fluid made up mostly of water) tends to freeze, making the battery unusable given that the electrochemical process cannot take place. Similar problems occur in cases where the temperature is too high which causes the vaporization of the electrolyte and thus affects its concentration, which in turn negatively impacts the exact stoichiometric relationships required for the reaction itself to occur.
The following is a summary table of some typical features of the aforementioned storage systems.
Comparative table
Figure imgf000005_0001
DESCRIPTION OF THE INVENTION
The system is able to store energy in the nanometrically deposited Nickel matrix on an alumina support.
The nickel matrix deposited by means of the sputtering technique has a thickness of 40nm and a specific roughness defined as explained below.
The two-dimensional spatial spectral power density (2DPSD) must have a peak around 5nm. This value is obtained experimentally by controlling the exposure times, the temperature of the crude nickel support, the vacuum levels, and the plasma generator current.
The charging system is at constant power with a forcing function made using a sinusoid translated in the positive half-plane added to a rectangular signal according to the following formula: Pc=Pmax*(l+sen(wl*t))*(l+0.1*rect(w2,t)),
where Pc is the forcing power, wl is the angular pulsation of the sinusoidal signal, rect (w2,t) is the rectangular function with amplitude 1 frequency equal to w2/2pi. Pmax depends on the nickel surface and the storage system power. Typically it can have values up to lOW/cm .
W2 is at least 10 times wl.
The rectangular signal widens the line spectrum of the sinusoidal signal in its surroundings, improving the charging performance. A greater than 20% reduction of the charging time was achieved in the experimental phase.
In the experimental phases Wl worked well if set between 10,000 and 50,000 rad/sec. Higher frequencies lead to emissions in the radio signal environment and do not improve performance.
The signal is naturally unidirectional and must have the negative connected to the nickel.
Discharge occurs simply by disconnecting the charging system, then an overvoltage occurs, the potential of which depends on the solute in the electrolyte and the release of gaseous hydrogen which is collected.
A more effective way of discharging is the use of an inverted potential signal (positive on nickel) of considerably lower intensity (typically 100 times), this time at constant current and proportional to the amount of hydrogen to be extracted. In this case, since the hydrogen extracted is not linearly directly proportional to the magnitude of the current, it is necessary to equip the discharge system with a feedback mechanism, for example a PID controller.
Therefore, the discharge function will be:
Is= Imax¾:PID(H2):!:(l+sen(wl:!:t)):!:(l+0,l:!:rect(w2,t)),
where Is is the current to the nickel, wl is the angular pulsation of the sinusoidal signal, rect (w2,t) is the rectangular function with amplitude 1 frequency equal to w2/2pi, PID(H2) is the feedback signal from the PID controller in operation as a function of the amount of hydrogen required (it has a value between 0 and 1). Imax has values up to lA/cm .
In this case W2 is also at least 10 times wl.
The system is then immersed in a liquid electrolyte composed of water and lithium or another metal element with low electrochemical competitiveness with nickel.
The neutral electrode always immersed in the electrolyte can be composed of nickel or another noble metal, for example platinum.
Alumina is essential for the morphology of the sputtered nickel substrate.
Figure 1 shows the essential components of the storage system, comprising a generator G and a PID controller P, and the cell C containing a liquid electrolyte E, an element N made of Nickel or other metal, a layer made of sputtered Nickel and a support made of Allumina containe din the cell.

Claims

1. Energy storage system comprising an electric generator in which an electrochemical cell and an insulating substrate inserted on which is deposited a nickel matrix whose roughness has a peak in the neighborhood of 5nm.
2. System according to claim 1 wherein the nickel matrix has a thickness between lOnm and lOOnm and the substrate is alumina.
3. System according to claim 1 wherein the loading system is a constant power system with a forcing function made by a shifted sine wave in the positive half-plane added to a rectangular signal in accordance with the following relation:
Pc = Pmax * (1 + sin (wl * t)) * (1 + 0.1 * rect (w2, t)).
where Pc is the forcing power, wl is the angular pulsation of the sinusoidal signal, rect (w2, t) is the rectangular function with amplitude 1 and a frequency of w2 / 2pi. Pmax depends on the nickel area and the power storage system typically can have values up to 10W / cm2.
4. System according to claim 1 wherein the download is simply performed by disconnecting the loading system, so it produces an overvoltage and release of hydrogen in gaseous form which is collected.
5. System according to claim 1 wherein the release takes place with the use of a reversed potential signal (positive on nickel) at constant current and proportional to the amount of hydrogen that you want to extract.
6. System according to claim 5 wherein the control is done through the use of a controller of the PID type of download.
7. System according to claim 5 wherein the download function is: Is = Imax * PID (H2) * (1 + sin (wl * t)) * (1 + 0.1 * rect (w2, t)). where Is is the current to the nickel, and wl is the angular pulsation of the sinusoidal signal, rect (w2, t) is the rectangular function with amplitude 1 frequency equal to w2 / 2pi, PID (H2) is the feedback signal from the pid controller.
PCT/IB2018/051315 2017-03-02 2018-03-01 Nickel based energy storage system WO2018158725A1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP18713010.9A EP3590142A1 (en) 2017-03-02 2018-03-01 Nickel based energy storage system

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CH00257/17A CH713537A2 (en) 2017-03-02 2017-03-02 Energy storage system in a nickel matrix.
CH257/17 2017-03-02

Publications (1)

Publication Number Publication Date
WO2018158725A1 true WO2018158725A1 (en) 2018-09-07

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CH (1) CH713537A2 (en)
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2010333A (en) * 1977-12-19 1979-06-27 Kernforschungsanlage Juelich Process and Apparatus for the Production of Hydrogen and Oxygen
US20050175894A1 (en) * 2004-02-06 2005-08-11 Polyplus Battery Company Protected active metal electrode and battery cell structures with non-aqueous interlayer architecture
US20080190781A1 (en) * 2005-04-28 2008-08-14 Chao Huang Electrochemical Method for Producing and Storing Hydrogen by the Redox of Zinc and Water

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2010333A (en) * 1977-12-19 1979-06-27 Kernforschungsanlage Juelich Process and Apparatus for the Production of Hydrogen and Oxygen
US20050175894A1 (en) * 2004-02-06 2005-08-11 Polyplus Battery Company Protected active metal electrode and battery cell structures with non-aqueous interlayer architecture
US20080190781A1 (en) * 2005-04-28 2008-08-14 Chao Huang Electrochemical Method for Producing and Storing Hydrogen by the Redox of Zinc and Water

Also Published As

Publication number Publication date
EP3590142A1 (en) 2020-01-08
CH713537A2 (en) 2018-09-14

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