Classifications

• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M10/00—Secondary cells; Manufacture thereof
  • H01M10/05—Accumulators with non-aqueous electrolyte
  • H01M10/058—Construction or manufacture
• • 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
  • H01M10/00—Secondary cells; Manufacture thereof
  • H01M10/04—Construction or manufacture in general
  • H01M10/049—Processes for forming or storing electrodes in the battery container
• • 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
  • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
  • H01M10/44—Methods for charging or discharging
  • H01M10/446—Initial charging measures
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M10/00—Secondary cells; Manufacture thereof
  • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
  • H01M10/52—Removing gases inside the secondary cell, e.g. by absorption
• • 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
  • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
• • 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
  • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
  • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
• • 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
  • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
• • 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
  • H01M10/04—Construction or manufacture in general
  • H01M10/0436—Small-sized flat cells or batteries for portable equipment
• • 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
  • H01M2004/028—Positive electrodes
• • 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
  • H01M2300/0065—Solid electrolytes
  • H01M2300/0068—Solid electrolytes inorganic
  • H01M2300/0071—Oxides
• • 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
  • H01M2300/0065—Solid electrolytes
  • H01M2300/0068—Solid electrolytes inorganic
  • H01M2300/0071—Oxides
  • H01M2300/0074—Ion conductive at high temperature
  • H01M2300/0077—Ion conductive at high temperature based on zirconium oxide
• • 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
  • H01M2300/0088—Composites
• • 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
  • H01M2300/0088—Composites
  • H01M2300/0091—Composites in the form of mixtures
• • 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
  • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
  • H01M4/624—Electric conductive fillers
  • H01M4/625—Carbon or graphite
• • 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
  • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
  • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
  • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

• Electrochemical energy storage systems have important applications in portable electronics and electric vehicles.
• One of the most widely used battery technologies is based on the use of lithium ions.
• the quality of the S EI determines the life of the battery and training is therefore an important step.
• the solid electrolyte is incorporated directly into the electrodes in powder form during their coating, and is called catholyte in the cathode and anolyte in the anode.
• these polymers are not stable at high potential.
• PEO is only stable up to a potential of 3.6V.
• the potential required for the active materials forming the electrodes to reach the desired energy densities for automotive applications is between 3.7V and 5V.
• Document US 201 8/0006326 describes an all-solid Li-ion battery comprising a polymer material.
• a battery electrode comprising PEO and an oxide of the formula L16.5La3Zr2i .5 Tao.s O n.
• the aim of the invention is therefore to remedy these drawbacks and to propose a method for forming an all-solid Li-ion battery cell comprising a solid electrolyte PEO-LLZO which gives the polymer stability at high potentials, of between 3 , 7V and 5 V.
• a method of forming a Li-ion battery cell comprising a cathode material, an anode material, and a solid electrolyte, the electrolyte comprising a mixture of a polyethylene oxide and an oxide. of formula LbLasZ O n.
• the method comprises the following successive cycling steps: (a) at least two successive charging and discharging cycles of the cell at a first cycling rate C / x, the charging / discharging steps being limited in time to x / 2; (b) at least two successive charge and discharge cycles of the cell at a second charge rate C / y, different from the first cycling regime, where y is less than x, the charge / discharge steps being limited in time to y / 2; and (c) at least two successive charge and discharge cycles of the cell at a third C / z cycling rate different from the first and second charge regimes, where z is less than x and y, the charge / discharge steps being time limited to z / 2.
• charge and discharge cycle is meant a step comprising a charge and then a discharge. Therefore, successive charge and discharge cycles represent a cycle comprising a charge and then a discharge, followed by one or more other cycles also each including a charge and a discharge.
• FIG 1 shows the change in voltage as a function of the capacity of the cell having received no preconditioning during five successive cycles of charging and discharging at a cycling rate of C / 20.
• FIG 5 represents the change in the capacity of the cell having received a preconditioning according to the first embodiment as a function of the number of charge and discharge cycles, at different cycling regimes.
• FIG 6 shows the change in voltage as a function of the capacity of the cell during the preconditioning cycling steps according to a second embodiment.
• FIG 7 shows the change in voltage as a function of the capacity of the cell having received preconditioning according to the second embodiment, at different cycling regimes.
• FIG 8 shows the change in the capacity of the cell having received preconditioning according to the second embodiment as a function of the number of charge and discharge cycles, at different cycling regimes.
• All-solid Li-ion batteries typically include a cathode, an anode, and a solid electrolyte.
• the forming method according to the invention relates to a Li-ion battery cell comprising a solid electrolyte comprising a mixture of polyethylene oxide (PEO) and oxide of the formula Li7La3Zr20 i2 (LLZO).
• PEO polyethylene oxide
• LLZO Li7La3Zr20 i2
• the anode comprises lithium metal.
• the electrolyte comprises a lithium salt, for example lithium bis (trifluoromethanesulfonyl) imide (LiTFSI).
• LiTFSI lithium bis (trifluoromethanesulfonyl) imide
• the cathode is prepared by mixing an active material, a catholyte and a charge of active material.
• the active material comprises a material of formula LiNiMnCoCh corresponding to a mixture of nickel, manganese and cobalt such as, for example, NMC622.
• the charge of active material may comprise carbon black, for example C65 carbon black.
• the catholyte preferably comprises a mixture of polyethylene oxide and of oxide of formula LLLasZ O n .
• Step (a) comprises at least two successive charge and discharge cycles of the cell at a first cycling regime C / x each charge / discharge step being limited in time to x / 2
• step (b) comprises at least two successive charge and discharge cycles of the cell at a second charge rate C / y different from the first cycling rate, where y is less than x, each charge / discharge step being limited in time to y / 2
• step (c) comprises at least two successive cycles of charging and discharging the cell at a third C / z cycling regime different from the first and second charging regimes, where z is less than x and y, each step charge / discharge being limited in time to z / 2.
• the preconditioning of the cells comprising at least the three steps (a), (b) and (c) as described above allows the formation of an S EI on the surface of the cells of which the quality contributes to stabilizing the polymer with which the cell is provided.
• the successive cycling steps are carried out at an increasing cycling rate.
• the cycling speed during the cycling step (a) is C / 40 and the cycling speed during the cycling step (b) is C / 20.
• the cycling rate or "charge or discharge rate” is denoted C / n, where C is the capacity of the battery in A. h, that is to say the quantity of electrical energy that it is capable of. to restore after receiving a full charge and where n refers to a duration in h.
• the method of forming the Li-ion battery cell further comprises a successive step (d) comprising at least two successive charge and discharge cycles of the cell at a fourth cycling regime different from the first, second and third charging regimes.
• the method of forming the Li-ion battery cell further comprises a successive step (e) comprising at least two successive charging and discharging cycles of the cell at a fifth cycling regime different from the first. , second, third and fourth load regimes.
• the cycling speed during the cycling step (e) is C / 2.
• one or more of the cycling steps (a), (b), (c), (d) and (e) comprise at least five successive charge and discharge cycles of the cell.
• the duration of each charging and discharging cycle carried out at a cycling rate of C / n is preferably equal to n / 2.
• the present invention is illustrated in a non-limiting manner by the following examples of the method of forming a Li-ion cell.
• the solid electrolyte used is prepared by mixing polyethylene oxide (PEO), the oxide of formula LbLasZ O n (LLZO) and a lithium salt, lithium bis (trifluoromethanesulfonyl) imide (LiTFS I).
• PEO polyethylene oxide
• LLZO oxide of formula LbLasZ O n
• LiTFS I lithium bis (trifluoromethanesulfonyl) imide
• the volume percentage of PEO-LiTFS I is 90 vol% and the volume percentage of LLZO oxide is 10 vol%.
• the anode is formed by lithium metal.
• the cathode is prepared by mixing an active material, a catholyte and an electronic conductor.
• NMC622 of formula LiNio . 6Mno . 2Coo . 2O2 is chosen as active material and corresponds to a nickel-manganese-cobalt mixture comprising 60 mol% of nickel, 20 mol% of manganese and 20 mol% of cobalt.
• Carbon black C65 is chosen as the electronic conductor.
• the cathode includes a catholyte comprising polyethylene oxide, the oxide of formula LLLasZ O n and lithium bis (trifluoromethanesulfonyl) imide to form a PEO-LiTFS I: LLZO mixture.
• the proportions of NMC622, of C65 carbon black and of catholyte in the cathode are reported in Table 1.
• the amount of NMC622 present at the cathode is adjusted in order to obtain a surface capacity of 1.6 + 0.6. mAh.cm 2 , considering a theoretical capacity of 166 mAh / g for the NMC622.
• step (a) Each charge and discharge cycle of step (a) is carried out for 20 hours.
• a second step (b) two cycles of charging and discharging are carried out at a second cycling speed of C / 20 where each cycle is carried out for 10 hours.
• An average capacity of 120 mA.hg 1 is obtained at the discharge at the C / 20 cycling speed, ie 73% of the expected experimental capacity. This therefore represents a significant increase in capacity compared to a cell that has not been preconditioned.
• Example 2 The preconditioning as described in Example 2 thus made it possible to improve the performance of the cell.
• Example 1 The cell preparation process detailed in Example 1 is reproduced for the cell preparation process of Example 3. In addition, a cell preconditioning step, developed below, is performed.
• the cell is prepared according to a second embodiment of preconditioning. Five charge and discharge cycles are carried out at a first cycling rate of C / 40 according to a first step (a). Each charge and discharge cycle of step (a) is carried out for 20 hours.
• a second step (b) five charging and discharging cycles are carried out at a second cycling rate of C / 20 where each cycle is carried out for 10 hours.
• a third step (c) five charging and discharging cycles are carried out at a third cycling rate of C / 10 where each cycle is carried out for 5 hours.
• a fourth step (d) five charging and discharging cycles are carried out at a fourth cycling rate of C / 5 where each cycle is carried out for 2 hours.
• a fifth step (e) five charging and discharging cycles are carried out at a fifth cycling rate of C / 2 where each cycle is carried out for 1 hour.
• the potential of the cell can reach 4.2V under load whatever the charging regime, C / 20 to C / 2, the polarization increasing for the charging regime I C.

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• Engineering & Computer Science (AREA)
• Manufacturing & Machinery (AREA)
• Inorganic Chemistry (AREA)
• Materials Engineering (AREA)
• Secondary Cells (AREA)
• Battery Electrode And Active Subsutance (AREA)

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• 2019
  • 2019-04-25 FR FR1904343A patent/FR3095552B1/fr active Active
• 2020
  • 2020-04-02 US US17/605,317 patent/US20220216504A1/en active Pending
  • 2020-04-02 JP JP2021562828A patent/JP7520881B2/ja active Active
  • 2020-04-02 CN CN202080029894.0A patent/CN113728480A/zh active Pending
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  • 2020-04-02 KR KR1020217037430A patent/KR20220005015A/ko unknown
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