WO2020007911A1 - Batterie à ion de fer rechargeable - Google Patents

Batterie à ion de fer rechargeable Download PDF

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Publication number
WO2020007911A1
WO2020007911A1 PCT/EP2019/067845 EP2019067845W WO2020007911A1 WO 2020007911 A1 WO2020007911 A1 WO 2020007911A1 EP 2019067845 W EP2019067845 W EP 2019067845W WO 2020007911 A1 WO2020007911 A1 WO 2020007911A1
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WIPO (PCT)
Prior art keywords
battery cell
electrolyte
cathode
anode
battery
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PCT/EP2019/067845
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English (en)
Inventor
Yanhong ZHAO
Yingpeng Zhen
Tobias BOSTRÖM
Stefano Passerini
Dominic BRESSER
Arianna Moretti
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Universitetet I Tromsø - Norges Arktiske Universitet
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Publication of WO2020007911A1 publication Critical patent/WO2020007911A1/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
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • 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
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
    • 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
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0569—Liquid materials characterised by the solvents
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/134—Electrodes based on metals, Si or alloys
    • 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
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0025—Organic electrolyte
    • H01M2300/0045—Room temperature molten salts comprising at least one organic ion
    • 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 present invention relates to a rechargeable iron-ion battery cell. Background
  • Li based batteries are important as energy storage devices nowadays.
  • Li based batteries have many disadvantages such as high cost, low safety, low Li abundance in the earth, etc.
  • a shortage of Li is possible in the near future, possibly within 65 years. Therefore, many researchers try to develop new types of batteries to replace Li based batteries, including sodium (Na) battery, and magnesium (Mg) battery.
  • Na battery sodium
  • Mg magnesium
  • the cost of the Na battery and Mg battery is still high.
  • iron (Fe) is the cheapest metal among all the metallic materials.
  • there are plenty of mineable Fe in the earth ca. 230 billion tons, which is about 15 000 times as high as the amount of mineable Li in the earth.
  • Fe-ion battery fabrication If the consumption of the amount of Fe is the same as the amount of Li, the nowadays mineable Fe can be utilized for as long as ca. 1 million years for iron- ion (Fe-ion) battery fabrication if it replaces all the Li-ion batteries.
  • the element abundance of Fe ranks number 1 in the universe and number 2 in the earth among the metallic elements. It means that there is plenty of Fe in the nature for Fe-ion battery fabrication.
  • Ionic liquids are types of salts and many of them are liquid at room temperature. Furthermore, many ionic liquids are liquid at temperatures as low as -60 °C and can be utilized in cold climate areas. The phase behavior of ionic liquids can be controlled by polarity modulation and they have a favorable solubility in inorganic and organic chemicals. Their chemical and functional groups can be designed to form task-specific ionic liquids.
  • Ionic liquids are regarded as green solvents, and are widely utilized in C0 2 capture and storage, extraction and separation processes, catalysis, nanoscience, petroleum science, cellulose science and biotechnology. Ionic liquids have a number of favorable characteristics including: (1) a vapor pressure that is either nonexistent or very low, (2) non-flammability or fire- retarding properties, (3) ionic conductivity, (4) a higher decomposition voltage than water, (5) a broader liquid temperature range than water, and (6) handleability in air.
  • Such characteristics are put to good use by employing these ionic liquids as electrolytes capable of being utilized at room temperature or lower in a variety of applications, including the electrodeposition of metals or alloys, electrolytic plating baths and as solvents for organic synthesis electrolytes for energy storing electrochemical devices including solar cells, batteries and supercapacitors.
  • US 20140342249 Al discloses a rechargeable Li-ion cell comprising a cathode having a cathode active material and/or a conductive supporting structure, an anode having an anode active material and/or a conductive supporting nanostructure, a porous separator electronically separating the anode and the cathode, a highly concentrated electrolyte in contact with the cathode active material and the anode active material, wherein the electrolyte contains a lithium salt dissolved in an ionic liquid solvent.
  • WO 2017/106337 Al discloses a non-magnetic metal-ion battery which comprises an anode including a metal such as aluminum, a cathode and an ionic liquid electrolyte disposed between the anode and cathode.
  • the ion battery charging method nowadays involves ion movement under an external electric field or an external electric voltage by ion diffusion.
  • the battery charging speed cannot be very fast.
  • the main reason is that the battery charging voltage cannot be very high during the battery charging process avoiding damaging the battery.
  • the battery charging speed cannot be improved by increasing the charging voltage.
  • the battery charging process in these batteries can only be realized by the ion diffusion under the maximum battery charging voltage, which leads to a low or limited battery charging speed.
  • the main object of the present invention is to overcome the limitation of conventional batteries.
  • One object of the present invention is to provide a battery that can replace the existing Li-based batteries and which can improve the performance of batteries, supercapacitors and concentration cells.
  • Another object of the present invention is to provide a battery with improved charging speed of ion batteries.
  • Another object of the present invention is to provide ionic liquids based magnetic electrolytes. Another object of the present invention is to increase the utilization degree of intermitted renewable energy sources.
  • Another object of the present invention is to provide a low-cost and high safety battery.
  • Another object of the present invention is to provide an energy storage battery for wireless charging smart road utilizing magnetic charging of batteries.
  • the present invention provides an iron-ion (Fe-ion) battery, a magnetic battery and a magnetic supercapacitor.
  • the Fe-ion battery can be utilized in stationary energy storage devices in buildings, railways, roads, and large scale renewable energy storage systems.
  • Fe-ion batteries with high capacity such as a specific charge/discharge capacity being higher than 200 mAh/g, can be utilized in inter alia wireless charging smart road, electrical cars, electric ships, mobile devices, and space technology.
  • Fe-ion battery is a highly safe battery, which is much safer than Li-ion battery.
  • the present invention concerns a rechargeable or secondary Fe-ion battery comprising an iron-containing electrolyte allowing magnetic charging.
  • the iron-ion can be obtained from the electrolyte itself and/or from the anode or the cathode.
  • the Fe-ion battery cell according to the present invention comprises:
  • an electrolyte interposed between the anode and the cathode, wherein the electrolyte transports Fe-ions between said anode and cathode.
  • Fe-ion should be interpreted as an ion containing Fe element, such as Fe 2+ , Fe 3+ , FeCU , FeCl 2 + , Fe0 4 2 , Fe0 4 3 , FeCh , etc.
  • the Fe-ion battery Due to plenty of Fe-element in the earth and the universe, the Fe-ion battery is a low-cost battery.
  • the Fe-ion batteries of the present invention are safe batteries compared to for example existing Li-ion batteries.
  • the anode and cathode are selected from materials that are not oxygen or water sensitive.
  • the electrolyte separates the anode and the cathode preventing short-circuit of the battery cell. Further, the electrolyte contains Fe-ions itself or comprises Fe-ions dissolved in the electrolyte during use. The electrolyte does not allow a significant flow of electrons causing the electrons to flow in an external circuit with electrons following the same direction as the positive Fe-ions to maintain charge neutrality.
  • the positive Fe-ions move from the negative electrode, anode, and enters the positive electrode, cathode, through the electrolyte.
  • potential energy builds up by applying a voltage to the cell, and the complete opposite process occurs being that the positive Fe-ions move from the cathode to the anode.
  • the anode comprises carbon which may be in the form of graphite, graphene or nanotube carbon, such as multi -walled carbon nanotube.
  • Fe-ions undergo chemical intercalation within the anode creating iron intercalated graphite, graphene or nanotube carbon depending on the selected material of the anode.
  • the anode has no or very little iron in it.
  • a current collector which is usually a metal grid or sheet, to provide a conducting path to minimize the resistance of the battery.
  • the current collector also acts as a substrate being a physical support for the anode material which often is a brittle structure.
  • the anode material may be a coating material arranged on the surface of a substrate material.
  • the substrate material is preferably a current collector.
  • the substrate material is not in contact with the electrolyte.
  • the current collector material is selected according to its electrical stability window, and chemical and electrochemical stability.
  • the current collector should be chosen from materials that will not react significantly with the electrolyte, thereby avoiding destruction of the battery cell if they come into contact.
  • the current collector is chosen from one of Ni-foil, Fe-foil and Co-foil.
  • the current collector is Ni-foil, which does not undergo any significant chemical reaction with an electrolyte comprising Fe-ions.
  • the cathode of the battery cell comprises a Fe-containing material which may be selected from at least one of Fe-foil, Fe powder, FeO, Fe 2 0 3 -powder, Fe 3 0 4 - powder, carbon coated with Fe nanoparticles (C-Fe), Fe3C, FeS0 4 , Fe(Cl0 4 ) 2 , Fe(C 5 H5) 2 , Fe(I0 3 ) 3, Ferrate, Ferrite, Fe (-II) compound, Fe (-1), Fe (0) compound, Fe (I) compound, Fe (II) compound, Fe (III) compound, Fe (IV) compound, Fe (V) compound, Fe (VI) compound, or other Fe element-containing materials.
  • the Fe-containing material is selected from Fe-foil, Fe 2 C>3-powder or carbon coated with Fe nanoparticles (C-Fe),
  • the cathode may be a coating material arranged on the surface of a substrate material preferably being a current collector. Further, the substrate should preferably not come into contact with the electrolyte.
  • the current collector may be the same as described for the substrate/current collector of the anode comprising nickel, such as Ni-foil.
  • the current collector substrate of the anode and cathode comprises a Ni-foil of pure nickel having a thickness in the range from 0.05 to 1.5 mm, preferably from 0.07 to 1.0 mm, more preferably from 0.09 to 0.5 mm, for example 0.1 mm thickness.
  • Pure nickel or Ni-foil should be understood as a composition having from 50 to 100 wt% Ni.
  • Fe-foil comprises from 50 to 100 wt% Fe.
  • Co-foil comprises from 50 to 100 wt% Co.
  • the electrolyte is a so-called conventional electrolyte such as an aqueous solution electrolyte or organic electrolyte.
  • the conventional electrolyte must be able to transfer Fe-ions between the cathode and anode.
  • the electrolyte solution may comprise the Fe-ions itself, or the Fe-ions may arrive from the cathode or anode being subjected to a redox reaction.
  • the electrolyte should be operable over the entire range of temperatures the battery is exposed to.
  • the electrolyte should be selected from electrolytes being liquid in the temperature range from 5 °C to 25 °C, preferably in the range from -20 °C to 30 °C, more preferably in the range from -40°C to 50 °C, even more preferably in the range from -60 °C to 100 °C. If the electrolyte is not in a liquid state during the operation of the battery, the battery will not work, as the electrolyte will not be able to transfer the Fe-ions between the anode to the cathode.
  • the electrolyte comprises an ionic liquid.
  • An ionic liquid electrolyte is not flammable, and not oxygen or water sensitive. Therefore, there is almost no risk of explosion for the Fe-ion battery using ionic liquid based electrolyte.
  • ionic liquids can be utilized for electrolyte preparation to further improve the safety of Fe-ion battery.
  • the electrolyte is selected from ionic liquids having a high thermal stability/decomposition temperature.
  • the decomposition temperature is higher than 250 °C, more preferably higher than 300 °C, even more preferably higher than 400 °C, for example 459 °C.
  • the ionic liquid electrolyte is selected from ionic liquids having a low viscosity in the range from 0.01 to 100 mPa-s at 20 °C, preferably from 5 to 60 mPa-s at 20 °C, more preferably from 10 to 50 mPa-s at 20 °C, even more preferably from 20 to 40 mPa-s at 20°C, for example about 35 mPa-s at 20 °C.
  • the ionic liquid electrolyte should have a viscosity from 0.01 to 90 mPa-s within the operable temperature range of the battery. A low viscosity allows for faster transportation of ions in the liquid.
  • the ionic liquid electrolyte is selected from ionic liquids having a high density thereby providing an electrolyte that will take smaller space with the same mass.
  • the density should be in the range from 1.0 to 1.5 g/cm 3 at 20 °C, preferably from 1.1 to 1.4 g/cm 3 at 20 °C, more preferably from 1.2 to 1.4 g/cm 3 at 20 °C, for example about 1.37 g/cm 3 at 20 °C.
  • the ionic liquid electrolyte is selected from ionic liquids having a high ionic conductivity, which is above 0.01 mS/cm at 20 °C, preferably above 0.1 mS/cm at 20 °C, more preferably above 0.5 mS/cm at 20 °C, even more preferably above 1.0 mS/cm at 20 °C, for example 8 mS/cm at 20 °C.
  • the ionic liquid electrolyte is selected from ionic liquids having an electric window of at least 2 V, preferably of at least 3 V, more preferably of at least 3.5 V, for example 4V.
  • the electrolyte comprises a pure ionic liquid containing one ionic liquid.
  • the electrolyte comprises a mixture of different pure ionic liquids. In another embodiment the electrolyte comprises one or more pure ionic liquid(s) mixed with other solvent(s).
  • the solvent can be selected from at least one of vinyl carbonate, propylene carbonate, diethyl carbonate, dimethyl carbonate and methyl ethyl carbonate.
  • the ionic liquid is selected from an ionic liquid having at least one of the following anions: Cl , Br, N0 3 , S0 4 2 , COO-, Cl0 4 , BF 4 , PF 6 , CFsCOCr, CF3SO3-, Tf 2 N and MeSCV; and at least one of the following cations:
  • An ionic liquid according to the present invention may have only one kind of anion and cation, or several kinds of anions or cations.
  • the ionic liquid may comprise ions that are ferromagnetic, giving the ionic liquid magnetic properties.
  • An ionic liquid electrolyte with magnetic properties is hereinafter referred to as a magnetic ionic liquid electrolyte.
  • Magnetic electrolytes change properties and behavior when exposed to an external magnetic field and may improve the magnetic charging efficiency of Fe-ion batteries.
  • the ionic liquid electrolyte is a magnetic ionic liquid electrolyte which comprises a cation selected from the group consisting of imidazolium, ammonium, pyridinium, phosphonium, pyrrolidinium, and triazolium, and an anion selected from [MCU] and/or [MB ] , wherein M is selected from at least one of Fe, Co, Ni, Mn and Gd.
  • the magnetic ionic liquid electrolyte can be selected from 1 -butyl-3 -methylimidazolium tetrachloroferrate (BmimFcCU) or 1 -methyl-3 -octylimidazolium tetrachloroferrate (OmimFeCU).
  • BmimFeCU and OmimFeCU both have magnetic properties due to the presence of Fe-ions.
  • BmimFeCU is chosen as the preferred magnetic ionic electrolyte having a low cost, easy to obtain in a single step synthesis method, is not flammable, not oxygen or water sensitive as most ionic liquid electrolytes.
  • BmimFeCU has the most suitable electrical window, when compared to other ionic liquid electrolytes as well as having a high thermal stability, high ionic conductivity and low viscosity.
  • Fe containing material such as FeCU or other kinds of low viscosity electrolytes, including low viscosity ionic liquid electrolytes, low viscosity aqueous electrolyte, or low viscosity organic electrolyte, can be added to the magnetic ionic electrolyte to increase the number of ions able to migrate to the electrodes.
  • Low viscosity electrolytes will decrease the concentration of for example BmimFeCU or OmimFeCU, in order to increase the ionic conductivity of electrolyte.
  • Adding Fe element containing ion for example, forming a Fe 3+ /Fe 2+ redox
  • the Fe-ion battery according to the present invention is a magnetic battery. This property has the potential to change the current battery market due to the low cost.
  • the Fe-ion magnetic battery can reduce the battery charge time when using a magnetic ionic liquid because the magnetic ionic liquid electrolyte can serve as“ion transport vehicle” (ITV) carrying Fe-ions fast and effectively from the cathode to the anode during the charging process under an external magnetic field. The added external magnetic field increases the battery charging speed.
  • ITV ion transport vehicle
  • Fe-ions will move due to the electric field between anode and cathode, which is the method for Fe-ion transport in Fe-ion batteries not being exposed to an external magnetic field.
  • Fe-ions will move not only by the normal electric ion transport method but also move together with the magnetic ionic liquid from the cathode to the anode during the charge process when magnetic ionic liquid moves under magnetic field force.
  • the magnetic ionic liquid electrolyte in the Fe-ion battery can thus also work as ITV to carry Fe ions fast and effectively from the cathode to the anode under an external magnetic field.
  • the Fe-ions After the Fe-ions are transported to the anode by ITV, the Fe-ions will be unloaded from ITV by the strong electrostatic attraction of the anode surface. Subsequently, the magnetic field direction can be reversed to move the Fe unloaded ITV from the anode to the cathode side.
  • the ITV can load Fe-ions again. Subsequently, by reversing the magnetic field direction again the ITV loaded with Fe-ions will move to the anode side.
  • this Fe-ion transport process can alternate from the cathode to the anode by reversing the magnetic field direction and loading/unloading Fe-ions using ITV.
  • the magnetic field direction can be increased by alternating the frequency, thus the Fe-ion loading/unloading rate can be increased significantly.
  • the magnetic charging method can also be utilized in other types ion batteries charging process, for example, Li-ion battery, to improve the battery charging speed.
  • the battery cell is exposed to an external magnetic field during charge of the battery cell, and the direction of the external magnetic field may in an embodiment of the invention alternate.
  • the charge-discharge speed, the specific capacity, ion transport behaviour, electrolyte properties and behaviour, anode properties and behaviour, cathode properties and behaviour, and/or structure of magnetic battery/supercapacitor can change with the external magnetic field.
  • the battery cell further comprises a separator arranged between the anode and the cathode.
  • the separator must be chemically stable to the electrolyte and to the active materials at the temperatures of operation. It is also necessary for the separator to have the correct qualities of wettability, selectivity, resistivity and flexibility for the particular battery system.
  • the separator must however be permeable allowing the Fe-ions to pass through, but must not allow a significant amount of electrons to pass therethrough, thereby avoiding that the battery cell short-circuits or self-discharges.
  • the separator may comprise polyolefin, filtering paper, nylon, cellophane or glass fibre.
  • Fe-ion should be interpreted as an ion containing Fe element, such as Fe 2+ , Fe 3+ , FeCU , FeCl 2 + , Fe0 4 2 , Fe0 4 3 , FeCh , etc.
  • Fe-ion batteries with high specific capacity can be utilized in electric cars, electric ships, mobile devices (such as cell phones and laptops), and space technology due to the excellent performance and properties of this kind of battery. Further, Fe-ion batteries can be utilized in stationary energy storage device in buildings, railways, and large scale renewable energy storage systems.
  • Fe-ion batteries can also be utilized for new supercapacitor development.
  • Supercapacitor is a safe and durable electrical energy storage device with fast charge-discharge capability.
  • Supercapacitors store energy by accumulating charges to form electrical double layers at the interface between the electrode surface and the electrolyte.
  • Aqueous electrolyte or organic electrolyte can be utilized for supercapacitor fabrication.
  • Ionic liquid electrolytes can also be utilized to improve the double layer capacitance of a carbon electrode and increase the operational voltage range.
  • ionic liquid electrolyte based supercapacitors have the potential to be utilized in cold climate, such as climates below -30 °C.
  • Magnetic supercapacitors Due to the “smart” magnetic property of magnetic ionic liquid electrolytes, they are utilized for magnetic supercapacitor fabrication. Magnetic supercapacitors have the magnetic property compared with the conventional supercapacitors since magnetic supercapacitors can be produced using magnetic ionic liquids in order to improve the energy storage capacity.
  • Fe-ion batteries can be utilized as energy storage devices to wireless charge electric cars on“smart roads”.
  • Wireless charging smart roads can for example be built by solar panel, wind turbine, Fe-ion batteries, and a wireless charging system.
  • the wind turbines and solar panels can be installed on both sides of the road.
  • Road surface can also be built by solar panel. Electric power from the solar panel and wind turbine can be transferred to the batteries along the smart road. Then, the electric car driving on a smart road can be charged by the wireless charging system under the smart road using the electric power from the batteries, solar panels, and wind turbines.
  • the rechargeable supercapacitor has the same structure as the Le-ion battery:
  • an electrolyte interposed between the anode and the cathode, wherein the electrolyte transports Le-ions between said anode and cathode.
  • Lig. 1 illustrates the structure of a Le-ion battery cell according to the invention.
  • Lig. 2 illustrates the structure of a Le-ion battery cell according to the invention exposed to an external magnetic field.
  • Fig. 3 is showing the density of a selection of ionic liquids as a function of temperature.
  • Fig. 4(a) is showing the viscosity of a selection of ionic liquids
  • fig. 4(b) shows the viscosity of BmimFeCU at various temperatures
  • Fig. 5(a) to (i) show DSC curves of a selection of ionic liquids.
  • Fig. 6 shows TGA curves of a selection of ionic liquids
  • Fig. 7(a) and (b) show Rahman analysis of BmimFeCU and OmimFeCU respectively.
  • Fig. 8 shows ionic conductivity measurements of a selection of ionic liquids.
  • Fig. 9(a) to (f) show the electrochemical windows measurement of a selection of ionic liquids.
  • Fig. 10(a) to (c) show the CV tests of a Cu - Cu symmetric cell.
  • Fig. 11(a) to (d) show the CV tests of an Al - Al symmetric cell.
  • Fig. 12(a) to (d) show the CV tests of a Ni - Ni symmetric cell.
  • Fig. 13(a) to (c) show the CV tests of a graphite-graphite symmetric cell.
  • Fig. 14(a) and (b) show a corrosion test of BmimFeCU on Cu, Al, and Ni.
  • Fig. 15(a) and (b) show the stripping and plating results of a Fe-foil - Fe-foil symmetric cell.
  • Fig. 16(a) to (c) show the stripping and plating results of a C-Fe - C-Fe symmetric cell.
  • Fig. 17 shows the CV test of a Fe-foil - graphite full cell.
  • Fig. 18(a) and (b) shows the CV test of a C-Fe - graphite full cell.
  • Fig. 19 shows the capacity of a Fe-foil - graphite battery using BmimFeCU as electrolyte and Cu as current collector.
  • Fig. 20 shows the capacity of a Fe-foil - graphite battery using OmimFeCU as electrolyte and Cu as current collector.
  • Fig. 21 shows the capacity of a Fe-foil - graphite battery using BmimFeCU as electrolyte and Ni as current collector.
  • Fig. 22(a) to (c) shows the charge -discharge test of C-Fe - graphite battery in a Swage-type cell.
  • Fig. 23(a) to (c) shows the charge-discharge test of C-Fe - graphite battery in coin cell.
  • Fig. 24(a) to (d) show SEM images of an unused C-Fe cathode.
  • Fig 25(a) to (c) show SEM images of a used C-Fe electrode from a Fe-ion Swage- type cell (with C-Fe electrode as working electrode and graphite as counter electrode) after charge and discharge cycles.
  • Fig. 26(a) to (d) show SEM images of a used C-Fe electrode from a Fe-ion Swage- type cell (with C-Fe electrode as counter electrode and graphite as working electrode) after charge and discharge cycles.
  • Fig. 27(a) shows XRD characterization result of an unused graphite anode
  • Fig. 27(b) a shows XRD characterization result of used a graphite anode
  • fig. 27(c) shows XRD characterization results of both a new and used C-Fe cathode.
  • Fig 28(a) and (b) shows charge-discharge test of a Fe-ion battery (with C-Fe electrode as working electrode and graphite as counter electrode) using electrochemical instrument VMP. (a) start with discharge; (b) start with charge.
  • Fig. 29(a) and (b) shows charge-discharge test of a Fe-ion battery (with C-Fe electrode as counter electrode and graphite as working electrode) using electrochemical instruments VMP and Maccor, respectively.
  • Fig. 30 illustrates a structure of a wireless charging smart road built of Fe-ion batteries, solar panels, wind turbines, and a wireless charging system. Detailed description of the invention
  • Fig. 1 illustrates the Fe-ion battery cell 1 having an anode 2, a cathode 3 and an electrolyte 4 interposed between the anode and the cathode.
  • the electrolyte separates the anode and the cathode preventing short-circuit of the battery cell.
  • a separator 5 is also inserted into the electrolyte 4 preventing electrons from being transported therethrough thereby protecting the battery cell 1 from short-circuit.
  • the electrolyte 4 is a magnetic ionic liquid 10 carrying Fe 3+ -ions 1 1.
  • the electrolyte 4 may contain the Fe-ions itself, and/or it may obtain Fe-ions from anode or cathode during the redox reaction. Since neither the electrolyte 4 nor the separator 5 allow a significant flow of electrons, the electrons are forced to flow in an external circuit 8. The electrons are following the same direction as the positive Fe-ions to maintain charge neutrality within the battery cell 1.
  • the positive Fe 3+ -ions 11 are moved within the electrolyte from the negative electrode, anode 2, to the the positive electrode, cathode 3, and the electrons flow in the same directions in the external circuit 8.
  • the built up potential energy produced is spent powering a device such as a cell phone, laptop or electric car.
  • Fig. 2 illustrates the same battery cell 1 as shown in Fig. 1, where the battery cell 1 is exposed to an external magnetic field by the magnet 9.
  • the applied magnetic field forces the magnetic ionic liquid 10 comprising Fe 3+ -ions 11 to be transported from the cathode 3 to the anode 2.
  • the external magnetic field is particularly useful during charge of the battery.
  • the Fe 3+ -ions 11 will move from cathode to anode due to the applied electric field, which forces the Fe 3+ -ion 1 1 transport in the Fe-ion battery cell.
  • magnetic ionic liquids can be utilized as“ion transport vehicle” (ITV) to transport Fe-ions from the cathode to anode in the presence of the external magnetic field during the charge process.
  • ITV ion transport vehicle
  • FIG. 2 The working mechanism of magnetic ionic liquids 10 in Fe-ion batteries is shown in Fig. 2.
  • Fe 3+ -ions 1 1 will move due to the electric field between anode and cathode, which is the method for Fe-ion transport in Fe-ion batteries not being exposed to an external magnetic field.
  • the Fe- ions will move not only by the normal ion transport method but also move together with the magnetic ionic liquid from the cathode to the anode during the charging process when the magnetic ionic liquid 10 moves under magnetic field force.
  • the magnetic ionic liquid electrolyte in the Fe-ion battery cells can thus work as ITV to carry Fe 3+ -ions fast and effectively from the cathode to the anode under an external magnetic field.
  • the Fe 3+ -ions After the Fe 3+ -ions are transported to the anode by ITV, the Fe 3+ -ions will be unloaded from ITV by the strong electrostatic attraction of the anode surface. Subsequently, the magnetic field direction is reversed in order to move the Fe unloaded ITV from anode to cathode side. After arriving the cathode side, the ITV can load Fe 3+ -ions again. And then, by reversing the magnetic field direction the ITV loaded with Fe-ions will move to the anode side.
  • this Fe 3+ -ion transport process can alternate from the cathode to the anode by reversing the magnetic field direction and loading/unloading Fe-ions using ITV.
  • the magnetic field direction can be increased by alternating the frequency, thus the Fe 3+ -ion loading/unloading rate can be increased significantly.
  • the electrolyte may be a conventional electrolyte or a non-magnetic ionic liquid which will the not be utilized as an ITV since conventional electrolytes and the non-magnetic ionic liquid will not be influenced by the external magnetic field.
  • the battery will still be able to charge faster than conventional batteries under the application of magnetic field as the Fe-ions will be influenced by an applied magnetic field.
  • Fig. 30 illustrate a structure of a wireless charging of a car using smart road built of Fe-ion batteries, solar panels, wind turbines, and a wireless charging system.
  • Wireless charging smart roads can for example be built by solar panel and /or wind turbine, Fe-ion batteries, and a wireless/inductive charging system.
  • the wind turbines and solar panels can be installed on both sides of the road.
  • Road surface can also or alternatively be built by solar panel. Electric power from the solar panel and wind turbine can be transferred to the batteries along the smart road. Then, the electric car driving on the smart road can be charged by the wireless charging system under the smart road using the electric power from the batteries, solar panels, and wind turbines.
  • All the ionic liquids, BmimFeCU, OmimFeCU, BmimPF 6 , OmimBF 4 , OmimPFe, Bmiml, OmimCl, and BmimCl, were dried using a vacuum pump in a dry room having a water content of ⁇ 25 ppm before they were studied.
  • the drying process was as follows: The ionic liquids were dried in the dry room using the membrane pump for at least 2 days. The vacuum pressure of the final dried ionic liquids was ca. 10 3 mbar. Subsequently, the pre-dried ionic liquid were dried further using a high vacuum pressure pump for at least 3 days until the final vacuum pressure of the dried ionic liquids were ca. 10 7 - 10 8 mbar.
  • the densities of the ionic liquids BmimFeCU, OmimFeCU, BmimPF 6 , OmimPFe and OmimBF 4 were measured using a density meter (Anton Paar DMA 4100, Anton Paar Co., Austria). The temperature was between 20 °C and 80 °C, at 5 °C intervals. The temperature error was ⁇ 0.01 °C. The measurement was performed in the dry room (water content of the dry room was ⁇ 25 ppm). The absolute room pressure was approximately 101 kPa during the measurement.
  • Fig. 3 illustrates that the density of the ionic liquids decreases with the increasing temperature ranging from 20 °C to 80 °C. It also shows that BmimFeCU has a higher density than the other ionic liquids.
  • Viscosity and rheological property of the ionic liquids BmimFeCU, OmimFeCU, OmimBF 4 , OmimPFe, and OmimCl, were measured using a rheometer (MCR 102, Anton Paar Modular Compact Rheometer) at temperature of 20 °C.
  • the viscosity of the ionic liquids was measured at shear rates ranging from 1 s 1 to 100 s 1 .
  • the viscosity of BmimFeCU is measured at various temperatures ranging from 10 °C to 50 °C.
  • Fig. 4a it is shown that BmimFeCU has lower viscosity than other ionic liquids. It illustrates that BmimFeCU has excellent viscosity to utilize as electrolyte, being as low as about 38 mPa-s at 20 °C.
  • the viscosity of BmimFeCU decreases with the increasing of temperatures ranging from 10 °C to 50 °C, which is in agreement with the viscosity versus temperature trend of conventional ionic liquids.
  • the melting point of the ionic liquids were measured using DSC (TA instruments, USA) and DSC (Netzsch, Germany). The measurement procedure was carried out by loading a sample in a pan, and cooling the sample to -150 °C followed by keeping the sample at -150 °C for 5 minutes. Afterwards, the sample was heated to -120 °C at a cooling rate of 5 °C/min and maintained at -120 °C for 5 min. Subsequently, the sample was heated to 20 °C at a heating rate of 1 °C/min and heat flow was measured during the process.
  • the DSC curve of BmimFeCU is shown in Fig. 5(a). It illustrates that BmimFeCU has a very low melting point, namely ca. -85 °C. That means that this ionic liquid electrolyte can be utilized in very low temperature areas, such as the arctic area.
  • Fig. 5(b) to 5(i) show the DSC curves of OmimBF 4 , OmimPFe, Bmiml, BmimBF 4 , BmimPF 6 , BmimCl, OmimCl, and OmimFeCU respectively.
  • the melting point of BmimCl is very high, being around about 70 °C.
  • Thermal stability of ionic liquid electrolytes was measured using TGA (TA instruments, USA). A sample was loaded in a pan. Subsequently, the sample was maintained at 35 °C for 10 min. The sample was heated to 600 °C at a heating rate of 5 °C/min from 35 °C. Heat flow was measured during the heating process. The weight of pan and sample were needed for the experiments.
  • TGA curves are shown in Fig. 6. It is shown that BmimFeCU has high thermal stability compared to the other ionic liquids, having a decomposition temperature of ca. 459 °C.
  • Fig. 7 (a) and (b) illustrates that there is an FeCU-function group in the two ionic liquids BmimFeCU and OmimFeCU respectively being the reason for their magnetic properties.
  • Ionic conductivity of the ionic liquids OmimFeCU, BmimPF 6 and OmimBF 4 was measured using conductivity meter at temperatures ranging from -30 °C to 80 °C.
  • the ionic conductivity of BmimFeCU was measured at temperatures ranging from -30 °C to 100 °C. The results are shown in Fig. 8, which shows that the BmimFeCU has a higher ionic conductivity than the other ionic liquids.
  • the electrochemical windows of the ionic liquids BmimFeCU, OmimFeCB, OmimBF 4 , OmimPFe, Bmiml, and BmimPF 6 were measured using VMP (Bio-Logic, France). The experiments were performed at potential versus Ag/Ag + (using Ag/AgCl as standard electrode) ranging from -5.0 V to 5.0 V with scanning rate of 0.5 mV/s.
  • the working electrode was Pt wire with cross sectional area of 0.0078 cm 2 . Counter electrode was Ni (cross sectional area: 1.13 cm 2 ).
  • the reference electrode was silver wire.
  • the electrochemical windows of the ionic liquids were measured using VMP. The results are shown in Fig.
  • FIG. 9(a) shows that the electrochemical window of BmimFeCU is ca. 4 V, from -2.1 V to 1.9 V versus Ag/Ag + (using Ag/AgCl as standard electrode).
  • BmimFeCU has wide electrochemical windows. Therefore, BmimFeCU was the preferred electrolytes in the examples of Fe-ion battery cells below.
  • Fe-foil being a pure iron cathode
  • carbon coated with Fe nanoparticles C-Fe NPs cathode
  • Fe 2 0 3 -powder which is carbon reduced Fe 2 0 3 (Fe2 cathode).
  • Fe-foil Fe-foil having a thickness of 0.25 mm and a purity of ⁇ 99.99% trace metals basis was utilized as cathode for Fe-ion battery directly.
  • C-Fe cathode The C-Fe cathode was prepared by the following steps: 1) dissolving carboxymethyl cellulose (CMC), which is a kind of binder, in H 2 0 forming a gel-like sample by stirring for at least 2 hours; 2) adding carbon coated with Fe nanoparticles (CAS number 7439-89-6, nanopowder, 25 nm average particle size, 99.5% trace metals basis) and carbon 45 (C45 conductive carbon black) was added into the gel-like sample.
  • CMC carboxymethyl cellulose
  • the sample was stirred for at least 12 hours to obtain a slurry; 3) coating the slurry on a surface of a Ni foil (having a thickness of 0.1 mm and a purity of ⁇ 99.99% trace metals basis) using doctor blade to form a 200 pm thin film; 4) heating the Ni foil comprising the thin film 80 C for at least 12 hours to remove the water; and 5) Cutting the Ni foil comprising the thin film to obtain the C-Fe electrodes. Afterwards, the C-Fe electrodes were further dried using high vacuum pump. Finally, the C-Fe electrodes were utilized in the Fe-ion battery cell.
  • Fe2 cathode The Fe2 cathode was prepared by a method similar to the method for C-Fe NPs cathode preparation. However, in step 2), the Fe powder reduced from Fe 2 0 3 by carbon 45 was added into the gel-like sample where the reduced Fe powder was prepared by burning a mixture of Fe 2 0 3 nanoparticles (CAS number 1309-37-1, having an average size ⁇ 50 nm), sucrose (CAS number 57-50-1), and super C65 carbon black at 1000 C for 1 hour providing a powder. The other remaining steps of the Fe2 cathode preparation was similar to that of C-Fe cathode preparation.
  • a Fe-foil symmetric cell and C-Fe symmetric cell were studied in a stripping and plating test.
  • the electrolyte in the symmetric cells is BmimFeCU.
  • the stripping and plating test of the two symmetric cells was performed using VMP.
  • the reference electrode was Ag.
  • the test results of Fe-foil symmetric cell are shown in fig. 15(a) showing voltage vs. time and fig. 15(b) showing current change vs. time.
  • the test results of the C-Fe symmetric cell are shown in fig. 16(a) showing voltage vs. time, fig. 16(b) showing current change vs. time and fig. 16(c) showing efficiency vs. cycle number. It can be seen that C-Fe symmetric cell has good stripping and plating results, and that C-Fe has a better performance than Fe-foil as electrode in the Fe-ion battery.
  • the graphite electrode was prepared by the following steps: 1) CMC was dissolved in H 2 0 forming a gel- like sample by stirring for at least 2 hours; 2) adding graphite and carbon 45 into the gel-like sample. Afterwards, the sample was stirred for at least 12 hours to obtain a slurry; 3) coating the slurry as a 150mih thin film on the surface of a Ni foil using doctor blade; 4) heating the Ni foil comprising the thin graphite film at 80 C for at least 12 hours to remove the water; and 5) cutting the Ni foil comprising the thin graphite film into the graphite electrodes. Afterwards, the graphite electrode was further dried using high vacuum pump. Finally, the graphite electrodes were obtained for battery preparation.
  • the current collector for electrodes preparation were investigated among Cu foil, Ni foil, and Al foil.
  • a Ni-Ni symmetric cell, Cu-Cu symmetric cell, and Al-Al symmetric cell were prepared.
  • the electrolyte utilized in the cells was BmimFeCU. All the symmetric cells were fabricated in a glovebox (MBraun UNIlab; H 2 0 content ⁇ 0.1 ppm, 0 2 content ⁇ 0.1 ppm) filled with ultrapure Argon.
  • the cyclic voltammetry (CV) test of the three symmetric cells was performed using galvanostat/potentiostat VMP (Bio-Logic, France).
  • a graphite-graphite symmetric cell was prepared.
  • the electrolyte in the cell was BmimFeCU. Subsequently, the CV test of the graphite -graphite cell was performed.
  • Cu test CV test of the Cu symmetric cell is performed. The CV curves are shown in Fig. 10 (a) to (c). It is shown that Cu symmetric cell is irreversible at the scanning voltage ranging from -1.0 V to 1 V, -1.5 V to 1.5 V, and -2.0 V to 2.0 V. That means Cu foil cannot be utilized as current collector for the cell using BmimFeCU as electrolyte.
  • Ni test CV test of Ni symmetric cell is performed. The CV curves are shown in Fig. 12(a) to (d). It is shown that the BmimFeCU is reversible in the Ni symmetric cell. Therefore, Ni foil may be utilized as current collector in Fe- ion battery cells.
  • Graphite test Graphite symmetric cell is prepared. The electrolyte in the cell is BmimFeCU. Subsequently, CV test of graphite symmetric cell is performed. CV curves of the symmetric cell are shown in Fig. 13(a) to (c). It is shown that graphite symmetric cell is reversible at the voltage ranging from -1 V to 1 V, and -1.5 V to 1.5 V, which means graphite can be utilized as anode in the Fe-ion battery.
  • Fig. 14(a) shows the Ni, Cu and Al foils before testing
  • fig. 14(b) shows the Ni, Cu and Al foil after the 4 months period of corrosion testing. It is shown that the BmimFeCU has a chemical reaction with Cu or Al. However, for Ni foil, there is no significant chemical reaction than can be seen.
  • Ni-foil was preferred as current collector in the following Fe-ion battery experiments.
  • Glass fiber is utilized as separator in the following Fe-ion battery experiments.
  • the first battery cell was using Fe-foil as cathode and graphite as anode while the other cell used C-Fe cathode and graphite anode.
  • Reference electrode was Ag.
  • the electrolyte in both cells was BmimFeCU.
  • the CV test results Fe-foil - graphite cell is shown in Fig. 17 illustrating that Fe-foil as cathode will not be as good as C-Fe as cathode.
  • Fig 18(a) shows the results of the C-Fe graphite cell at a voltage ranging from -1 V to 1 V
  • fig. 18(b) shows the same cell at the voltage ranging from -1.5 V to 1.5 V. It is shown that C-Fe graphite full cell is completely reversible at -1.5 V to 1.5 V.
  • Fe-ion battery cells having different compositions were prepared, and charge and discharge tests were performed.
  • Electrolyte BmimFeCU The charge and discharge test results are shown in Fig. 19. It is found the cell was dead after 10 cycles. The reason is that the Cu current collect has had a chemical reaction with the BmimFeCU electrolyte, which leads to the cell destruction not allowing the cell to continue to be charged or discharged.
  • the second composition is very similar to the first composition, except for the electrolyte being a OmimFeCU electrolyte.
  • the charge discharge test results of this cell are shown in Fig. 20.
  • the second cell is also dead after 10 charge discharge cycles. This means that Cu current collector cannot utilized for neither BmimFeCU nor OmimFeCU.
  • Ni-foil was utilized as current collector for the third cell, and BmimFeCU as electrolyte.
  • the charge and discharge test results of the cell is shown in Fig 21. It was found that the cell still works after 40 cycles. That means Ni can be utilized as current collector for the Fe graphite full cells using IF BmimFeCU as electrolyte.
  • Electrolyte BmimFeCU The charge and discharge test of battery cell (Swaglok-type, T-cell) was performed. The results are shown in Fig. 22(a) showing capacity vs. cycle number, fig. 22(b) showing voltage vs. capacity in the first 5 cycles, and fig. 22(c) showing voltage vs. capacity in the l0 th , l5 th and 20 th cycle. As shown in fig. 22(a), the discharge and charge capacity of the Swaglok-type cell is very high, around 262 mAh/g charge capacity 262 mAh/g and 245 mAh/g discharge specific capacity at the potential range from -0.4 V to 0.8 V vs. Ag/Ag + after 15 cycles.
  • Figs 22(b) and 22(c) show the specific capacity versus potential profiles. It is found the cell is not stable at the first 5 cycles. However, after the 5 th cycle, the cell become more and more stable. As shown in Fig 22(c), the stable specific capacity versus potential profiles are obtained.
  • the morphology of the cathode was investigated using scanning electrochemical microscopy (SEM, ZEISS 1550VP Field Emission Scanning Electron Microscope operated at 5 kV).
  • FIG. 24(a) to (d) show SEM images of an unused C-Fe cathode magnified 10 000 times, 30 000 times, 50 000 times and 100 000 times respectively. As shown the C-Fe nanoparticles is found on the surface of the cathode.
  • Figs. 25(a) to (c) shows the C-Fe cathode from the Swagelok type battery cell (with C-Fe electrode as working electrode and graphite as counter electrode) composition after 5 charge-discharge cycles.
  • the SEM image in in figs. 25(a) to (c) are magnified 1000 times, 5000 times and 10 000 times respectively.
  • the images show that the C-Fe nanoparticles of the cathode are broken and forming a large size structure. That means the Fe in the C-Fe cathode take actively function in the charge and discharge process.
  • Figs. 26(a) to (d) show images of the surface of a C-Fe anode used as in the Swagelok-type cell (with C-Fe electrode as counter electrode and graphite as working electrode).
  • the SEM image in in figs. 26(a) to (d) are magnified 1000 times, 5000 times, 10 000 times and 20 000 times respectively.
  • the images show that the C-Fe cathode hardly changes after the charge-discharge cycles.
  • C-Fe electrode should be the working electrode and graphite should be the counter electrode.
  • X-ray diffraction analysis was conducted using a Bruker D8 Advance diffractometer (Bruker, Germany) with Cu-Ka. XRD is conducted ranging from 10° to 90° with a step size of 0.02°.
  • Fig. 27(a) showing a fresh graphite anode
  • Fig. 27(b) showing a used graphite anode
  • Fig. 27(c) showing both a new and used C-Fe cathode.
  • the chemical composition of the fresh graphite electrode and used graphite electrode changes significantly, showing that the Fe-ions undergo chemical intercalation with the graphite during the charge/discharge process.
  • Fig. 27(c) it is shown that the chemical composition of the fresh C-Fe electrode and used C-Fe electrode did not change significantly.
  • a charge-discharge test was performed using electrochemical instrument VMP of an Fe-ion battery having a C-Fe cathode, graphite anode and BmimFeCF 4 electrolyte. It means that in the test C-Fe electrode is working electrode and graphite is counter electrode. Glass fiber was used as separator. Characterization results are shown in Fig. 28 (a) showing discharge first and then charge. Fig. 28 (b) shows charge first and then discharge. As shown in Fig. 28 (a) and (b) the charge and discharge performance of the battery is similar. Experiment 4
  • a charge discharge test was performed using electrochemical instruments Maccor and VMP (an electrochemical instrument for battery test) in a Swagelok-type cell with graphite as working electrode and C-Fe as counter electrode.
  • BmimFeCU was used as electrolyte.
  • the results are shown in Fig. 29(a) showing data from VMP and Fig. 29(b) showing data from Maccor.
  • the results show that C-Fe cannot be utilized as counter electrode in the cell but should be utilized as working electrode.
  • the graphite should be utilized as counter electrode.

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Abstract

La présente invention concerne une cellule de batterie à ion de fer (ion Fe) rechargeable comprenant une anode, une cathode et un électrolyte intercalé entre l'anode et la cathode, et son utilisation. L'électrolyte même peut comprendre les ions Fe, et/ou peut obtenir les ions Fe de l'anode ou de la cathode. Un ion Fe fait référence à un élément Fe contenant un ion. La cathode est de préférence faite de matériaux contenant des éléments Fe. L'électrolyte aqueux et l'électrolyte organique peuvent être utilisés comme électrolyte pour la fabrication de batteries à ion Fe. Afin d'améliorer encore les performances de la batterie à ion Fe, un liquide ionique peut être utilisé comme électrolyte, l'électrolyte liquide ionique transportant des ions Fe entre ladite anode et ladite cathode.
PCT/EP2019/067845 2018-07-03 2019-07-03 Batterie à ion de fer rechargeable WO2020007911A1 (fr)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20140342249A1 (en) 2013-05-16 2014-11-20 Hui He Lithium secondary batteries containing lithium salt-ionic liquid solvent electrolyte
US20160028117A1 (en) * 2014-07-25 2016-01-28 Korea Institute Of Science And Technology Electrolyte for magnesium rechargeable battery and preparation method thereof
WO2017106337A1 (fr) 2015-12-15 2017-06-22 The Board Of Trustees Of The Leland Stanford Junior University Électrolytes améliorés, collecteurs de courant, et liants pour batteries à ions métalliques rechargeables
EP3246981A1 (fr) * 2016-05-17 2017-11-22 Industrial Technology Research Institute Batterie à ions métalliques

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20140342249A1 (en) 2013-05-16 2014-11-20 Hui He Lithium secondary batteries containing lithium salt-ionic liquid solvent electrolyte
US20160028117A1 (en) * 2014-07-25 2016-01-28 Korea Institute Of Science And Technology Electrolyte for magnesium rechargeable battery and preparation method thereof
WO2017106337A1 (fr) 2015-12-15 2017-06-22 The Board Of Trustees Of The Leland Stanford Junior University Électrolytes améliorés, collecteurs de courant, et liants pour batteries à ions métalliques rechargeables
EP3246981A1 (fr) * 2016-05-17 2017-11-22 Industrial Technology Research Institute Batterie à ions métalliques

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
CHEMICAL ABSTRACTS, Columbus, Ohio, US; abstract no. r 244193-52-0
GUO ZHIHUI ET AL: "Electrochemical Behavior of Iron-based Imidazolium Chloride Ionic Liquids", ELECTROCHIMICA ACTA, ELSEVIER, AMSTERDAM, NL, vol. 142, 7 August 2014 (2014-08-07), pages 132 - 143, XP029062781, ISSN: 0013-4686, DOI: 10.1016/J.ELECTACTA.2014.07.110 *
YANRONG WANG ET AL: "Emerging non-lithium ion batteries", ENERGY STORAGE MATERIALS, vol. 4, 1 July 2016 (2016-07-01), pages 103 - 129, XP055612010, ISSN: 2405-8297, DOI: 10.1016/j.ensm.2016.04.001 *
Z. ZHAOJ.H. HANSENT. BOSTROM: "Extraction of magnetic nanoparticles using magnetic ionic liquids", vol. 11, 2016, IET MICRO & NANO LETTERS

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