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WO2016178187A1 - Zinc-electrode forming and formatting - Google Patents

Zinc-electrode forming and formatting Download PDF

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Publication number
WO2016178187A1
WO2016178187A1 PCT/IB2016/052595 IB2016052595W WO2016178187A1 WO 2016178187 A1 WO2016178187 A1 WO 2016178187A1 IB 2016052595 W IB2016052595 W IB 2016052595W WO 2016178187 A1 WO2016178187 A1 WO 2016178187A1
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WIPO (PCT)
Prior art keywords
zinc
binder
preparing
electrode
porous
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Ceased
Application number
PCT/IB2016/052595
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French (fr)
Inventor
Suren Martirosyan
Didier Guillonnet
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Individual
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Publication of WO2016178187A1 publication Critical patent/WO2016178187A1/en
Anticipated expiration legal-status Critical
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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
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60L—PROPULSION OF ELECTRICALLY-PROPELLED VEHICLES; SUPPLYING ELECTRIC POWER FOR AUXILIARY EQUIPMENT OF ELECTRICALLY-PROPELLED VEHICLES; ELECTRODYNAMIC BRAKE SYSTEMS FOR VEHICLES IN GENERAL; MAGNETIC SUSPENSION OR LEVITATION FOR VEHICLES; MONITORING OPERATING VARIABLES OF ELECTRICALLY-PROPELLED VEHICLES; ELECTRIC SAFETY DEVICES FOR ELECTRICALLY-PROPELLED VEHICLES
    • B60L50/00—Electric propulsion with power supplied within the vehicle
    • B60L50/50—Electric propulsion with power supplied within the vehicle using propulsion power supplied by batteries or fuel cells
    • B60L50/60—Electric propulsion with power supplied within the vehicle using propulsion power supplied by batteries or fuel cells using power supplied by batteries
    • B60L50/64—Constructional details of batteries specially adapted for electric vehicles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60L—PROPULSION OF ELECTRICALLY-PROPELLED VEHICLES; SUPPLYING ELECTRIC POWER FOR AUXILIARY EQUIPMENT OF ELECTRICALLY-PROPELLED VEHICLES; ELECTRODYNAMIC BRAKE SYSTEMS FOR VEHICLES IN GENERAL; MAGNETIC SUSPENSION OR LEVITATION FOR VEHICLES; MONITORING OPERATING VARIABLES OF ELECTRICALLY-PROPELLED VEHICLES; ELECTRIC SAFETY DEVICES FOR ELECTRICALLY-PROPELLED VEHICLES
    • B60L58/00—Methods or circuit arrangements for monitoring or controlling batteries or fuel cells, specially adapted for electric vehicles
    • B60L58/10—Methods or circuit arrangements for monitoring or controlling batteries or fuel cells, specially adapted for electric vehicles for monitoring or controlling batteries
    • B60L58/18—Methods or circuit arrangements for monitoring or controlling batteries or fuel cells, specially adapted for electric vehicles for monitoring or controlling batteries of two or more battery modules
    • B60L58/21—Methods or circuit arrangements for monitoring or controlling batteries or fuel cells, specially adapted for electric vehicles for monitoring or controlling batteries of two or more battery modules having the same nominal voltage
    • 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
    • H01M4/24—Electrodes for alkaline accumulators
    • H01M4/244—Zinc electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2220/00—Batteries for particular applications
    • H01M2220/20—Batteries in motive systems, e.g. vehicle, ship, plane
    • 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
    • Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
    • Y02T10/00—Road transport of goods or passengers
    • Y02T10/60—Other road transportation technologies with climate change mitigation effect
    • Y02T10/70—Energy storage systems for electromobility, e.g. batteries

Definitions

  • the present invention is concerned with electrically rechargeable batteries, metal-air batteries, zinc-electrodes for such batteries and especially electrically rechargeable Zinc-Air batteries.
  • Zinc-Air batteries are famous for their energy density comparable to Li-ion batteries (at least 3 to 6 times more than Lead-Acid batteries) and their low cost per kWh (comparable or cheaper than Lead-Acid batteries and 5 to 10 times cheaper than Li-ion batteries).
  • the minimum requirement for Electric Scooters would be something like: at least 70 Wh/kg Energy Density; 15 W/kg average Power Density and 6 months service life with 200 cycles.
  • the present invention relates to a method for preparing a porous Zinc-electrode for electrically rechargeable electrochemical cell such as Nickel-Zinc, Zinc-Silver, secondary Zn-MnO2 or Zinc-Air includes at least the steps of:
  • Step 1) Preparing an homogeneous Paste including at least:
  • a binder for instance PVB or the same
  • a binder solvent ethyl-alcohol 90-96% in case of PVB binder
  • Step 2) Pouring the said Paste into a mold
  • the “Binder-Solvent Containing Electrode” is then dried and placed into the final cell casing and then soaked with electrolyte.
  • the mold is closed by a thin membrane letting the solvent and Water Based Solution go through before placing such closed “Binder-Solvent Containing Electrode” into the bath of the said Water Based Solution.
  • the said thin membrane can be a membrane dissolving in strongly electrolyte (for ex. filter paper, ⁇ 0.1mm thick)
  • the Water Based Solution is either:
  • the Water Based Solution is a electrolyte WHEREBY helping the precipitation of the binder and making the electrode more rigid.
  • the invention also relates to a method of preparing a porous Zinc-electrode gives especially good results when the following additional Step4 is included after Step3, before Cell Assembly :
  • the electrode for example at 10mA/cm2
  • an electrolyte bath for example KOH 4M
  • Step4 is followed by the additional Step5 of having a first discharge operation, discharging totally or even preferably almost totally the electrode, to the stage that about 95% of Zn mass has been oxidized into ZnO.
  • the said first discharge operation is ended when the potential of the zinc-electrode is as low as approximately 0.25V vs a amalgamated Zn reference electrode, thus leaving some zinc particles around the current collector and in case a zinc amalgam is covering the current collector avoiding said zinc amalgam disintegration.
  • a first method (FDO-a) to perform the said First Discharge Operation is done by placing the electrode in O2 containing environment.
  • the reaction rate is regulated by measuring the electrode’s temperature and or reducing oxygen supply (for example with a screen) and or cooling the electrode (for example by bathing it into a water based bath) when it is above a temperature such as 55C, this procedure can last up to 50 days.
  • the reaction rate is adjusted so that the temperature of the electrode is maintained around 50 0C.
  • a second method (FDO-b) to perform the said first discharge operation starts by partially discharging the electrode with a cathode counter electrode in an electrolyte bath down to about a State Of Charge of 75% of the total Zn+ZnO powder theoretical capacity)
  • the surface of the electrode is getting white (color of Zinc-oxide) and the electrode becomes less reactive, can be manipulated more easily and the said first oxidation step discharge operation can be continued till its end in the air such as described above.
  • the said cathode counter electrode used to discharge the zinc electrode is preferably non reacting so that it can be used to successively discharge several zinc-electrodes.
  • the said first discharge operation is performed with sequences of the methods (FDO-a) and (FDO-b), such as discharging till 70% SOC with method (FDO-a) and continuing to discharge down to 5% SOC with method (FDO-b), WHEREBY preventing the risk of having the zinc-electrode self-igniting and burning in the O2 containing environment.
  • O2 containing environment is plain air WHEREBY simplifying the preparation process or zinc-electrode.
  • the electrode is so active that (i) zinc is depositing uniformly during charging and the surface facing the charging electrode is remaining flat and smooth (without any change) after cycling, and (ii) very little volume change occurs during charging-discharging cycles;
  • the electrode is so active that it reduces dendrite growth
  • concentrations of binder, binder solvent are chosen to adjust the final electrode porosity and ZnO mass ratio in the foam/sponge (conveniently a 55%-65%-80% porosity and ca 0.7-1.5g of ZnO/cc) (for example 0.2-0.3ml PVB dissolved into 3-4-5ml C2H5OH 90-96% then mixed with 4-5g of ZnO to get an homogeneous paste).
  • Active Mass it is meant the total mass of Zn, ZnO, binder and additives if any.
  • the “final electrode porosity” is defined as volume of solvent divided by the volume of Active Mass
  • the invention relates to a method for the preparation (first charging or “formatting”) of a zinc electrode newly made (never charged yet), thereafter the not-formatted zinc-electrode, whose active mass advantageously includes less than 20% in mass of zinc particles compared to the mass of zinc-oxide powder, to obtain a highly active zinc electrode,
  • said method comprising a step of totally charging in an electrolyte bath to a charging level of at least 95% of the theoretical capacity of the Zn-oxide + Zn powder contained in said not-formatted zinc-electrode.
  • the invention relates to the method defined above, wherein the said charging level is less than 100% of the said theoretical capacity.
  • the invention relates to the method defined above, wherein the said charging level is at least 120% of the said theoretical capacity.
  • the invention relates to the method defined above, wherein, further to the step of totally charging, the said method includes a step of oxidation of said electrode to a stage wherein at least about 95% of the Zn mass has been oxidized into ZnO.
  • the invention relates to the method defined above, wherein, the oxidation step is carried out in an environment containing dioxygen gas, advantageously rarefied air containing less than 18% of dioxygen gas.
  • the invention relates to the method defined above, the discharge step is carried out by part in a gas containing oxygen and by part by discharging in an electrolyte bath.
  • the invention relates to the method defined above, the discharge step is partially carried out with a cathode counter electrode in an electrolyte bath down to a State Of Charge of about 50% of the said theoretical capacity.
  • the invention relates to the method defined above, the said environment containing dioxygen gas is air.
  • the invention relates to a formatted electrode prepared with a method according to the above description.
  • the invention also relates to a Zinc-air cell comprising a formatted electrode as defined above.
  • the invention also relates to a Zinc-air battery comprising a Zinc-air cell as defined above.
  • the invention further relates to a vehicle comprising a zinc-air battery as defined above.

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  • Engineering & Computer Science (AREA)
  • Sustainable Energy (AREA)
  • Mechanical Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Power Engineering (AREA)
  • Sustainable Development (AREA)
  • Transportation (AREA)
  • Manufacturing & Machinery (AREA)
  • Hybrid Cells (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Charge And Discharge Circuits For Batteries Or The Like (AREA)
  • Secondary Cells (AREA)

Abstract

The invention relates to A method for preparing a porous Zinc electrode comprising the following steps: a) a step of preparing a paste comprising i) a mixture of Zinc-oxide powder and Zinc powder, ii) a binder; and iii) a binder solvent; b) a step of pouring the paste obtained in step a) in a recipient containing a current collector to obtain a poured paste containing said current collector; said method comprising further c) a step of contacting said poured paste containing said current collector obtained in step b) with binder immiscible solution.

Description

Zinc-electrode forming and formatting
The present invention is concerned with electrically rechargeable batteries, metal-air batteries, zinc-electrodes for such batteries and especially electrically rechargeable Zinc-Air batteries.
Electrically rechargeable Zinc-Air batteries are famous for their energy density comparable to Li-ion batteries (at least 3 to 6 times more than Lead-Acid batteries) and their low cost per kWh (comparable or cheaper than Lead-Acid batteries and 5 to 10 times cheaper than Li-ion batteries).
These batteries would be very useful for many applications including Electric Vehicles and Stationary Electricity Storage if they could offer a sufficient service life. However so far nobody could offer this type of batteries with characteristics suitable for an application.
For example, considering the low cost of these batteries, we estimate that the minimum requirement for Electric Scooters would be something like: at least 70 Wh/kg Energy Density; 15 W/kg average Power Density and 6 months service life with 200 cycles.
According to a first aspect, the present invention relates to a method for preparing a porous Zinc-electrode for electrically rechargeable electrochemical cell such as Nickel-Zinc, Zinc-Silver, secondary Zn-MnO2 or Zinc-Air includes at least the steps of:
Step 1) Preparing an homogeneous Paste including at least:
a. A mixture of Zinc-oxide powder + Zinc powder in which advantageously the share of Zinc powder represents less than 20% in weight of the Zinc-oxide powder
b. A binder (for instance PVB or the same)
c. A binder solvent (ethyl-alcohol 90-96% in case of PVB binder)
Step 2) Pouring the said Paste into a mold
including at least a Current Collector ; conveniently with a tab on which an electrical lead is connected ; conveniently the mold has a flat rectangular form with the Current Collector in the middle of the electrode thickness, this ensemble forming an “Binder-Solvent Containing Electrode”
Step 3) Forming the Zinc-electrode
At this step, classically the “Binder-Solvent Containing Electrode” is then dried and placed into the final cell casing and then soaked with electrolyte.
However, the inventor got much better results by directly bathing the “Binder-Solvent Containing Electrode” into a bath of Water Based Solution or plain water, usually heated, whereby the binder solvent is diffusing into the bath and progressively replaced by the said Water Based Solution, its concentration is decreasing and the binder is precipitating “in-situ” forming a ZnO-binder homogeneous solid structure, rigid or like a gel, with millimeter long pores, making quite homogeneous active mass and pore distribution along the thickness and length of the electrode.
Conveniently, the mold is closed by a thin membrane letting the solvent and Water Based Solution go through before placing such closed “Binder-Solvent Containing Electrode” into the bath of the said Water Based Solution.
Conveniently the said thin membrane can be a membrane dissolving in strongly electrolyte (for ex. filter paper, <0.1mm thick)
Preferably the Water Based Solution is either:
a. plane water
b. KOH solution, 1-8M.
Preferably the Water Based Solution is a electrolyte WHEREBY helping the precipitation of the binder and making the electrode more rigid.
The invention also relates to a method of preparing a porous Zinc-electrode gives especially good results when the following additional Step4 is included after Step3, before Cell Assembly :
totally charge the electrode (for example at 10mA/cm2) in an electrolyte bath (for example KOH 4M), with at least 95%, preferably with at least 100% , and even preferably with at least 120% of theoretical capacity of the Zn-oxide powder it contains
WHEREBY all the Zinc-oxide powder is reduced to Zinc and the electrode becomes greyish and extremely active ; also, Zn being of higher density than ZnO, this operation creates a porous structure electrode and the zinc-oxide powder form nano-pores while being reduced.
In a preferred way of the present invention, Step4 is followed by the additional Step5 of having a first discharge operation, discharging totally or even preferably almost totally the electrode, to the stage that about 95% of Zn mass has been oxidized into ZnO. In a preferred way according to the present invention, the said first discharge operation is ended when the potential of the zinc-electrode is as low as approximately 0.25V vs a amalgamated Zn reference electrode, thus leaving some zinc particles around the current collector and in case a zinc amalgam is covering the current collector avoiding said zinc amalgam disintegration.
In a preferred way of the invention, a first method (FDO-a) to perform the said First Discharge Operation is done by placing the electrode in O2 containing environment. According to a preferred way, during this operation the reaction rate is regulated by measuring the electrode’s temperature and or reducing oxygen supply (for example with a screen) and or cooling the electrode (for example by bathing it into a water based bath) when it is above a temperature such as 55C, this procedure can last up to 50 days. During this operation preferably the reaction rate is adjusted so that the temperature of the electrode is maintained around 50 0C.
In another preferred way of the invention, a second method (FDO-b) to perform the said first discharge operation starts by partially discharging the electrode with a cathode counter electrode in an electrolyte bath down to about a State Of Charge of 75% of the total Zn+ZnO powder theoretical capacity)
WHEREBY the surface of the electrode is getting white (color of Zinc-oxide) and the electrode becomes less reactive, can be manipulated more easily and the said first oxidation step discharge operation can be continued till its end in the air such as described above. In this method, the said cathode counter electrode used to discharge the zinc electrode is preferably non reacting so that it can be used to successively discharge several zinc-electrodes.
In a third and preferred way according to the invention, the said first discharge operation is performed with sequences of the methods (FDO-a) and (FDO-b), such as discharging till 70% SOC with method (FDO-a) and continuing to discharge down to 5% SOC with method (FDO-b), WHEREBY preventing the risk of having the zinc-electrode self-igniting and burning in the O2 containing environment.
In a preferred way, O2 containing environment is plain air WHEREBY simplifying the preparation process or zinc-electrode.
These methods allow the preparation of especially active Zinc-electrodes which is improving many factors:
- charging overpotential decrease (with PVB overpotential is below 4mV while with PTFE overpotential it was below 10mV at the 3rd cycle at 15 mA/cm2 current density value);
- the electrode is so active that (i) zinc is depositing uniformly during charging and the surface facing the charging electrode is remaining flat and smooth (without any change) after cycling, and (ii) very little volume change occurs during charging-discharging cycles;
- the electrode is so active that it reduces dendrite growth;
In a preferred embodiment of the present invention, concentrations of binder, binder solvent are chosen to adjust the final electrode porosity and ZnO mass ratio in the foam/sponge (conveniently a 55%-65%-80% porosity and ca 0.7-1.5g of ZnO/cc) (for example 0.2-0.3ml PVB dissolved into 3-4-5ml C2H5OH 90-96% then mixed with 4-5g of ZnO to get an homogeneous paste).
In the present invention, by Active Mass it is meant the total mass of Zn, ZnO, binder and additives if any.
The “final electrode porosity” is defined as volume of solvent divided by the volume of Active Mass
In other words, the invention relates to a method for the preparation (first charging or “formatting”) of a zinc electrode newly made (never charged yet), thereafter the not-formatted zinc-electrode, whose active mass advantageously includes less than 20% in mass of zinc particles compared to the mass of zinc-oxide powder, to obtain a highly active zinc electrode,
said method comprising a step of totally charging in an electrolyte bath to a charging level of at least 95% of the theoretical capacity of the Zn-oxide + Zn powder contained in said not-formatted zinc-electrode.
Advantageously, the invention relates to the method defined above, wherein the said charging level is less than 100% of the said theoretical capacity.
Advantageously, the invention relates to the method defined above, wherein the said charging level is at least 120% of the said theoretical capacity.
Advantageously, the invention relates to the method defined above, wherein, further to the step of totally charging, the said method includes a step of oxidation of said electrode to a stage wherein at least about 95% of the Zn mass has been oxidized into ZnO.
Advantageously, the invention relates to the method defined above, wherein, the oxidation step is carried out in an environment containing dioxygen gas, advantageously rarefied air containing less than 18% of dioxygen gas.
Advantageously, the invention relates to the method defined above, the discharge step is carried out by part in a gas containing oxygen and by part by discharging in an electrolyte bath.
Advantageously, the invention relates to the method defined above, the discharge step is partially carried out with a cathode counter electrode in an electrolyte bath down to a State Of Charge of about 50% of the said theoretical capacity.
Advantageously, the invention relates to the method defined above, the said environment containing dioxygen gas is air.
The invention relates to a formatted electrode prepared with a method according to the above description.
The invention also relates to a Zinc-air cell comprising a formatted electrode as defined above.
The invention also relates to a Zinc-air battery comprising a Zinc-air cell as defined above.
The invention further relates to a vehicle comprising a zinc-air battery as defined above.

Claims (10)

  1. A method for preparing a porous Zinc electrode comprising the following steps:
    a) a step of preparing a paste comprising
    i) a mixture of Zinc-oxide powder and Zinc powder,
    ii) a binder; and
    iii) a binder solvent;
    b) a step of pouring the paste obtained in step a) in a recipient containing a current collector to obtain a poured paste containing said current collector;
    said method comprising further
    c) a step of contacting said poured paste containing said current collector obtained in step b) with binder immiscible solution.
  2. The method for preparing a porous Zinc electrode according to claim 1, wherein said binder-immiscible solution is plain water or an alkaline solution, more preferably a solution from 0 to 8 M of KOH,
  3. The method for preparing a porous Zinc electrode according to claim 1 or 2, wherein said binder is, or Polyvinyl butyral (PVB).
  4. The method for preparing a porous Zinc electrode according to claim 3, wherein said binder is PVB and said binder solvent is ethyl-alcohol 90-96.
  5. The method for preparing a porous Zinc electrode according to anyone of claims 1 to 4, wherein said mixture comprising less than 20% of said Zinc powder in weight compared to the weight of said Zinc-oxide powder;
  6. The method for preparing a porous Zinc electrode according to anyone of claims 1 to 5, wherein further to step b) and before step c) said poured paste containing said current collector is covered with a thin membrane, said thin membrane being permeable to both said binder solvent and said aqueous solution.
  7. The method for preparing a porous Zinc electrode according to claim 6, wherein said thin membrane is a membrane dissolving in strong alkaline electrolyte, such as KOH 4M or stronger.
  8. The method for preparing a porous Zinc electrode according to anyone of claims 1 to 7, said method comprising a step of drying the resulting porous Zn-electrode.
  9. A Zinc-air battery comprising a porous electrode according to anyone of claims 1 to 8.
  10. A vehicle comprising a zinc-air battery according to claim 9.
PCT/IB2016/052595 2015-05-06 2016-05-06 Zinc-electrode forming and formatting Ceased WO2016178187A1 (en)

Applications Claiming Priority (2)

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US201562157848P 2015-05-06 2015-05-06
US62/157,848 2015-05-06

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PCT/IB2016/052593 Ceased WO2016178185A1 (en) 2015-05-06 2016-05-06 Battery management system for bi-cathode discharging-cells
PCT/IB2016/052592 Ceased WO2016178184A1 (en) 2015-05-06 2016-05-06 Partitioned zinc electrode
PCT/IB2016/052594 Ceased WO2016178186A1 (en) 2015-05-06 2016-05-06 Zinc-air cell with airlift pump

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PCT/IB2016/052592 Ceased WO2016178184A1 (en) 2015-05-06 2016-05-06 Partitioned zinc electrode
PCT/IB2016/052594 Ceased WO2016178186A1 (en) 2015-05-06 2016-05-06 Zinc-air cell with airlift pump

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EP (1) EP3292577A1 (en)
CN (1) CN107836052A (en)
WO (4) WO2016178187A1 (en)

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