Classifications

• • 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
  • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
  • C01B21/00—Nitrogen; Compounds thereof
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
  • C01B21/00—Nitrogen; Compounds thereof
  • C01B21/06—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron
  • C01B21/0607—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron with alkali metals
  • C01B21/061—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron with alkali metals with lithium
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
  • C01B21/00—Nitrogen; Compounds thereof
  • C01B21/06—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron
  • C01B21/0615—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron with transition metals other than titanium, zirconium or hafnium
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
  • C01G3/00—Compounds of copper
  • C01G3/006—Compounds containing copper, with or without oxygen or hydrogen, and containing two or more other elements
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
  • C01G45/00—Compounds of manganese
  • C01G45/20—Compounds containing manganese, with or without oxygen or hydrogen, and containing one or more other elements
  • C01G45/22—Compounds containing manganese, with or without oxygen or hydrogen, and containing two or more other elements
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
  • C01G49/00—Compounds of iron
  • C01G49/009—Compounds containing iron, with or without oxygen or hydrogen, and containing two or more other elements
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
  • C01G51/00—Compounds of cobalt
  • C01G51/80—Compounds containing cobalt, with or without oxygen or hydrogen, and containing one or more other elements
  • C01G51/82—Compounds containing cobalt, with or without oxygen or hydrogen, and containing two or more other elements
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
  • C01G53/00—Compounds of nickel
  • C01G53/80—Compounds containing nickel, with or without oxygen or hydrogen, and containing one or more other elements
  • C01G53/82—Compounds containing nickel, with or without oxygen or hydrogen, and containing two or more other elements
• • 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
  • H01M10/052—Li-accumulators
  • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
• • 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
• • 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
  • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
  • H01M2004/027—Negative electrodes
• • 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

• TITLE Process for the delithiation of at least one nitride of transition metal(s) and lithium
• the present invention relates to a process for the delithiation of a particular material, the nitride of transition metal (or metals) and lithium.
• the present invention also relates to the use of the material obtained by said process as a material for a negative electrode for a lithium-ion battery.
• Li-ion batteries comprise one or more positive electrodes, one or more negative electrodes, an electrolyte and a separator.
• Li-ion batteries are increasingly used as a stand-alone power source, especially in applications related to electric mobility. This trend is explained in particular by mass and volume energy densities significantly higher than those of conventional nickel cadmium (Ni-Cd) and nickel-metal hydride (Ni-MH) batteries, absence of memory effect, low self-discharge compared to other accumulators and also by lower costs per kilowatt-hour linked to this technology.
• Ni-Cd nickel cadmium
• Ni-MH nickel-metal hydride
• Li-ion batteries include active electrode materials that allow insertion and de-insertion of lithium ions during charging and discharging processes. These insertions and desinsertions must be reversible so that the accumulator can store energy over several cycles.
• the positive electrode materials used in Li-ion batteries are lithiated transition metal oxides, such as LiCoCL, LiNio.6Mno.2Coo.2O2, LiFePO-t, or even LiMn2Ü4.
• Electrode materials negative are insertion materials, such as graphite or lithium titanate (I ⁇ TisOn).
• the lithium Li + ions will be deintercalated from the positive electrode material and intercalated in the layers (in the case of graphite) or in the crystallographic sites (in the case of lithium titanate) of the electrode material negative.
• Lithium titanate is an attractive material for high power batteries due to its high work potential (1.5 V vs Li+/Li) to avoid lithium plating. However, its capacity is still limited compared to that of graphite. Indeed, the capacity of graphite is more than twice that of lithium titanate.
• Nitride-based electrode materials have also been developed, and in particular transition metal and lithium nitrides such as Li?MnN4 and LhFeNi. These materials exhibit almost twice the capacitance of lithium titanate while having a working potential of 1.18V vs. Li+/Li for Li?MnN4 and 1.25V vs. Li+/Li for LhFeNi, respectively, and good high current withstand.
• the object of the present invention is to develop a process for the delithiation of a nitride of transition metal(s) and lithium making it possible to obtain a material which can be used as an active material for a negative electrode for lithium ion battery. Disclosure of Invention
• the subject of the present invention is therefore a process for the delithiation of at least one transition metal(s) and lithium nitride comprising the following steps: a) mixing at least one oxidizing agent with said transition metal(s) nitride and lithium; b) recovering the material obtained at the end of step a).
• the process according to the invention makes it possible to obtain a delithiated material.
• a delithiated material makes it possible to avoid the initial discharge step which is conventionally carried out in a cell with the materials usually used in the prior art, such as for example the materials of formula Ei?MnN4 or even LhFeNi. Indeed, these materials are not delithiated materials. Therefore, when these materials are used in cells, an initial discharge step of the battery cell is required.
• a subject of the invention is also the use of the material obtained by the process according to the invention, as an active material for a negative electrode for a lithium-ion battery.
• FIG. 1 represents diffractograms of the Ei?MnN4 material and of the material obtained at the end of the process according to the invention
• FIG 2A is a photograph of the Ei?MnN4 material observed under a scanning electron microscope
• FIG 2B is a snapshot of a material obtained at the end of the process according to the invention, observed under a scanning electron microscope;
• FIG 3 is a graph representing the galvanostatic curve of a material obtained at the end of the process according to the invention against Fi metal.
• At least one oxidizing agent is mixed with the transition metal(s) and lithium nitride.
• the transition metal or metals are chosen from Mn, Fe, Co, Ni, Cu and mixtures thereof.
• said lithium transition metal(s) nitride is chosen from the materials of formula Li 2 .
• said lithium transition metal(s) nitride is of formula Li?MnN4 or of formula LiFeN2.
• said oxidizing agent is chosen from those belonging to the family of metallocenes in oxidized form.
• said oxidizing agent is chosen from cobaltocenium salts, preferably from cobaltocenium hexafluorophosphate, cobaltocenium tetrafluoroborate, bis(pentamethylcyclopentadienyl)cobalt hexafluorophosphate, bis(pentamethylcyclopentadienyl)cobalt hexafluorophosphate tetrafluoroborate and mixtures thereof.
• cobaltocenium salts preferably from cobaltocenium hexafluorophosphate, cobaltocenium tetrafluoroborate, bis(pentamethylcyclopentadienyl)cobalt hexafluorophosphate, bis(pentamethylcyclopentadienyl)cobalt hexafluorophosphate tetrafluoroborate and mixtures thereof.
• said oxidizing agent is chosen from cobaltocenium hexafluorophosphate.
• the molar ratio between said oxidizing agent and said nitride of transition metal(s) and lithium ranges from 0.5 to 3, preferably from 1 to 2.
• step a) is carried out in the presence of at least one solvent.
• the solvent is chosen from aprotic organic solvents, preferably from acetonitrile, tetrahydrofuran, dimethylformamide, dichloromethane, ethyl acetate and mixtures thereof, preferably from acetonitrile.
• any solvent that can be used in a Li-ion battery electrolyte can also be used, preferably the solvent is chosen from ethylene carbonate (denoted “EC”), propylene carbonate (denoted “PC”), dimethyl carbonate (denoted “DMC”), diethyl carbonate (denoted “DEC”) and ethyl and methyl carbonate (denoted “EMC”) and mixtures thereof.
• EC ethylene carbonate
• PC propylene carbonate
• DMC dimethyl carbonate
• DEC diethyl carbonate
• EMC ethyl and methyl carbonate
• the solvent chosen from aprotic organic solvents can be mixed with the solvent that can be used in a Li-ion battery electrolyte, such as those mentioned above. .
• the solvent is acetonitrile.
• step b) of the process according to the invention the material obtained at the end of step a) is recovered.
• the material can be recovered by centrifugation or by filtration.
• the material can then be rinsed with solvent, preferably chosen from the solvents mentioned above, possibly several times.
• the material can be vacuum dried.
• a subject of the invention is also the use of the material obtained by the process according to the invention, as an active material for a negative electrode for a lithium-ion battery.
• the process according to the invention is a process for the delithiation of at least one nitride of transition metal(s) and of lithium.
• a protocol for the delithiation of at least one nitride of transition metal(s) and lithium can be described according to one embodiment below.
• an oxidizing agent such as those mentioned above, can first be added to a solvent, such as those mentioned above, to obtain a solution comprising said oxidizing agent.
• transition metal(s) and lithium nitride such as for example Li?MnN4 or LFFeNy, can be added to said solution.
• Said lithium transition metal(s) nitride may be in powder form.
• the amount of transition metal(s) and lithium nitride can be adjusted such that the molar ratio between said oxidizing agent and said transition metal(s) and lithium nitride can range from 0.5 to 3, preferably from 1 to 2.
• transition metal(s) and lithium nitride can then be mixed in said solution comprising said oxidizing agent.
• the temperature can then be adjusted to a temperature ranging from -5°C to 50°C.
• All of these steps can be performed in a controlled environment such as a glove box.
• the oxidizing agent used can be a cobaltocenium salt.
• the color of the solvent may change during the reaction. This is then a signal that the reaction is in progress.
• the material obtained can be recovered.
• the material can be separated from the solution by centrifugation or filtration.
• the material can then be rinsed with solvent several times in order to eliminate any possible undesirable products. Then the material can be vacuum dried.
• Example 1 process according to the invention
• the lithium transition metal(s) nitride of formula Li?MnN4 is used.
• a diffractogram of the material in the initial state is produced, as shown in Figure 1 (curve A, material A).
• curve A material A
• the characteristic peaks of Li?MnN4 can be identified on this diffractogram.
• Delithiation is carried out in a glove box at a temperature of 20°C.
• the molar ratio between said oxidizing agent and said lithium transition metal(s) nitride is 1.5.
• the mixture is then decanted and transferred to a centrifuge tube. Centrifugation was carried out at a speed of 5000 rpm for 5 minutes using a centrifuge. After centrifugation, powder and solution were separated.
• the delithiated material is obtained after drying.
• a diffractogram of the material obtained is then produced, as shown in FIG. 1 (curve B, material B).
• Example 2 use of the material obtained in example 1 in a half-cell
• the active material obtained in example 1 was prepared in the form of a composite electrode and tested with a piece of metallic lithium in a CR2032 button battery.
• the composite electrode was prepared by mixing 70% by weight of active material obtained in Example 1 with 22% by weight of acetylene black and 8% by weight of polytetrafluoroethylene (PTFE).
• the separator used is a CAT No. 1823-070® glass microfiber separator marketed by Whatman.
• the electrolyte used is 1 mol/L lithium hexafluorophosphate dissolved in a mixture of carbonate solvents with a 1:1:1 volume ratio of ethylene carbonate (EC), diethyl carbonate (DEC) and sodium carbonate. dimethyl (DMC).
• EC ethylene carbonate
• DEC diethyl carbonate
• DMC sodium carbonate. dimethyl
• a half-cell was assembled.
• the assembly of the half-cell was carried out in a glove box.
• Galvanostatic cycling was performed using a VMP3 potentiostat from BioLogic at a cycling regime of C/20, as shown in Figure 3.
• the potential window is between 1.6V and 0.9V .
• This material can be used as active material for Li-ion battery negative electrode.

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• 2021
  • 2021-12-23 FR FR2114373A patent/FR3131452B1/fr active Active
• 2022
  • 2022-12-23 EP EP22850736.4A patent/EP4454028A1/de active Pending
  • 2022-12-23 JP JP2024538386A patent/JP2025500502A/ja active Pending
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