EP3729552A1 - Composition d'électrolyte pour élément électrochimique de type lithium-ion - Google Patents
Composition d'électrolyte pour élément électrochimique de type lithium-ionInfo
- Publication number
- EP3729552A1 EP3729552A1 EP18830272.3A EP18830272A EP3729552A1 EP 3729552 A1 EP3729552 A1 EP 3729552A1 EP 18830272 A EP18830272 A EP 18830272A EP 3729552 A1 EP3729552 A1 EP 3729552A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- lithium
- electrolyte composition
- group
- salt
- mass
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
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Classifications
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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
- 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
- H01M10/0568—Liquid materials characterised by the solutes
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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
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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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
- 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
- H01M10/0567—Liquid materials characterised by the additives
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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
- 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
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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
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/44—Methods for charging or discharging
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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
- 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
- H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
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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
- 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
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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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
- 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
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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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
- 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
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
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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
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0025—Organic electrolyte
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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
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0025—Organic electrolyte
- H01M2300/0028—Organic electrolyte characterised by the solvent
- H01M2300/0037—Mixture of solvents
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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
- 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
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
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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
- 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
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
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- 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 technical field of the invention is that of electrolyte compositions for rechargeable electrochemical cells of lithium-ion type.
- Rechargeable electrochemical elements of the lithium-ion type are known from the state of the art. Because of their high density and high energy density, they are a promising source of electrical energy. They comprise at least one positive electrode, which may be a lithiated transition metal oxide, and at least one negative electrode which may be based on graphite. Such elements nevertheless have a limited life when used at a temperature of at least 80 ° C. Their constituents deteriorate rapidly resulting in either a short circuit of the element or an increase in its internal resistance. It is observed, for example, that after about 100 charge / discharge cycles carried out at 85 ° C., the loss of capacity of such elements can reach 20% of their initial capacity. In addition, it has also been found that these elements have a limited life when used at a temperature below -10 ° C.
- these new electrochemical elements are capable of operating in cycling at very low temperature, that is to say at a temperature that can go down to about -20 ° C.
- the subject of the invention is therefore an electrolyte composition comprising:
- LiFSI lithium bis (fluorosulfonyl) imide salt LiFSI lithium bis (fluorosulfonyl) imide salt
- At least one organic solvent selected from the group consisting of cyclic or linear carbonates, cyclic or linear esters, cyclic or linear ethers and a mixture thereof.
- This electrolyte can be used in an electrochemical element of lithium-ion type. It allows it to operate at high temperature, for example at least 80 ° C. It also allows it to operate at low temperatures, for example about -20 ° C.
- the tetrafluoro or hexafluorinated lithium salt is chosen from lithium hexafluorophosphate LiPF 6 , lithium hexafluoroarsenate LiAsF 6 , lithium hexafluoroantimonate LiSbF 6 and lithium tetrafluoroborate LiBF 4 .
- lithium ions derived from lithium bis (fluorosulfonyl) imide salt represent at least 30 mol% of the total amount of lithium ions present in the electrolyte composition.
- the lithium ions derived from the tetrafluoro or hexafluorinated lithium salt represent up to 70 mol% of the total amount of lithium ions present in the electrolyte composition.
- the mass percentage of vinylene carbonate represents from 0.1 to 5% by weight of the mass of the group consisting of the said at least one tetrafluoro or hexafluorinated lithium salt, the bis (fluorosulfonyl) salt. lithium imide and said at least one organic solvent.
- the mass percentage of ethylene sulphate represents from 0.1 to 5% by weight of the mass of the group consisting of the said at least one tetrafluoro or hexafluorinated lithium salt, the bis (fluorosulfonyl) salt. LiFSI lithium imide and said at least one organic solvent.
- the ethylene sulphate represents from 20 to 80% by weight of the mass of the group consisting of ethylene sulphate and vinylene carbonate and the vinylene carbonate represents from 80 to 20% by weight. mass of the mass of the group consisting of ethylene sulphate and vinylene carbonate.
- said at least one organic solvent is selected from the group consisting of cyclic carbonates, linear carbonates and mixtures thereof.
- the cyclic carbonates represent from 10 to 40% by weight of the mass of said at least one organic solvent and the linear carbonates represent from 90 to 60% of the mass of said at least one organic solvent.
- the cyclic carbonates are chosen from ethylene carbonate (EC) and propylene carbonate (PC).
- the linear carbonates are selected from dimethyl carbonate (DMC) and methyl ethyl carbonate (EMC).
- the invention also relates to a lithium-ion electrochemical element comprising:
- the negative electrode comprises a carbon-based active material, preferably graphite.
- the positive active material comprises one or more of the compounds i) to v):
- M, M ', M "and M" being different from each other; with 0.8 ⁇ x ⁇ 1.4; 0 ⁇ y ⁇ 0.5; 0 ⁇ z ⁇ 0.5; 0 ⁇ w ⁇ 0.2 and x + y + z + w ⁇ 2.2;
- compound iv) of the formula Li x Fei y M y PO 4 wherein M is selected from the group consisting of B, Mg, Al, Si, Ca, Ti, V, Cr, Mn, Co, Ni, Cu, Zn , Y, Zr, Nb and Mo; and 0.8 ⁇ x ⁇ 1.2; 0 ⁇ y ⁇ 0.6;
- the positive active material comprises compound ii) and M is Ni;
- M '" is selected from the group consisting of B, Mg, Al, Si, Ca, Ti, V, Cr, Fe, Cu, Zn, Y, Zr, Nb and Mo;
- the invention also relates to the use of the electrochemical element as described above, in storage, charge or discharge at a temperature of at least 80 ° C.
- the subject of the invention is the use of the electrochemical element as described above, in storage, in charge or in discharge at a temperature of less than or equal to -20 ° C.
- FIG. 1 represents an impedance diagram produced at -40 ° C. on the reference element A and the element B according to the invention.
- FIG. 2 represents the variation of the viscosity of the reference electrolyte composition A and that of the electrolyte composition B according to the invention, as a function of the temperature ranging from -20 ° C. to 60 ° C.
- Figure 3 shows at the top the gas chromatographic spectrum of the reference electrolyte composition A after it has been stored for 15 days at 85 ° C.
- the bottom spectrum is that of the electrolyte composition B according to the invention after it has been stored under the same conditions.
- Figure 4 shows the variation of the capacity of element A and that of element B during cycling at 85 ° C.
- FIG. 5 shows the variation of the capacity of element A and that of element B during cycling at temperatures of 20 ° C., 0 ° C., -20 ° C., 25 ° C. and 85 ° C. .
- Figure 6 shows the variation of the capacity of the elements C, D and E, during a cycling at 25 ° C and 60 ° C.
- Figure 7 shows the variation of the capacity of the elements C, F and G during cycling at 25 ° C and 60 ° C.
- FIG. 8 represents at the top the spectrum of gas chromatography of the electrolyte composition D at the end of the cycling at 60 ° C. of the element containing it.
- the spectrum of bottom is that of the electrolyte composition E at the end of the cycling at 60 ° C of the element containing it.
- FIG. 9 represents at the top the spectrum of gas chromatography of the electrolyte composition F at the end of the cycling at 60 ° C. of the element containing it.
- the bottom spectrum is that of the electrolyte composition G at the end of the cycling at 60 ° C of the element containing it.
- Figure 10 shows the variation of the capacity of the elements H, I, J, K and L during cycling at 85 ° C.
- Figure 11 shows the variation of the capacity of the elements M, N, O, P and Q during cycling at 85 ° C.
- Figure 12 shows the variation of the capacity of elements H, I, J, K and L during cycling at temperatures of 20 ° C, 0 ° C, -20 ° C, 25 ° C and 85 ° C.
- Figure 13 shows the variation of the capacity of the elements M, N, O, P and Q during cycling at temperatures of 20 ° C, 0 ° C, -20 ° C, 25 ° C and 85 ° C.
- electrolyte composition according to the invention as well as the various constituents of an electrochemical element comprising the electrolyte composition according to the invention will be described in the following.
- Electrolyte composition :
- the electrolyte composition comprises at least one organic solvent in which the following compounds are dissolved:
- the at least one organic solvent is selected from the group consisting of cyclic or linear carbonates, cyclic or linear esters, cyclic or linear ethers or a mixture thereof.
- cyclic carbonates are ethylene carbonate (EC), propylene carbonate (PC) and butylene carbonate (BC). Ethylene carbonate (EC) and propylene carbonate (PC) are particularly preferred.
- the electrolyte composition may be free of cyclic carbonates other than EC and PC.
- linear carbonates examples include dimethyl carbonate (DMC), diethyl carbonate (DEC), methyl ethyl carbonate (EMC) and methyl propyl carbonate (PMC).
- DMC dimethyl carbonate
- DEC diethyl carbonate
- EMC methyl ethyl carbonate
- PMC methyl propyl carbonate
- DMC dimethyl carbonate
- EMC methyl ethyl carbonate
- PMC methyl propyl carbonate
- the electrolyte composition may be free of linear carbonates other than DMC and EMC.
- the cyclic or linear carbonate (s) and the cyclic or linear ester (s) may be substituted by one or more halogen atoms, such as fluorine.
- linear esters are ethyl acetate, methyl acetate, propyl acetate, ethyl butyrate, methyl butyrate, propyl butyrate, ethyl propionate, propionate methyl and propyl propionate.
- cyclic esters examples include gamma-butyrolactone and gamma-valerolactone.
- linear ethers are dimethoxyethane and ethyl propyl ether.
- An example of a cyclic ether is tetrahydrofuran.
- the electrolyte composition comprises one or more cyclic carbonates, one or more cyclic ethers and one or more linear ethers.
- the electrolyte composition comprises one or more cyclic carbonates, one or more linear carbonates and at least one linear ester.
- the electrolyte composition comprises one or more cyclic carbonates, one or more linear carbonates and does not comprise linear ester.
- the electrolyte composition does not comprise other solvent compounds other than the cyclic or linear carbonates.
- the cyclic carbonates can represent up to 50% by weight of the sum of the masses of the carbonates and the linear carbonate or carbonates. can represent at least 50% by mass of the sum of the masses of the carbonates.
- the cyclic carbon or carbonates represent from 10 to 40% by weight of the mass of the carbonates and the linear carbonate or carbonates represent from 90 to 60% of the mass of the carbonates.
- a mixture of preferred organic solvents is the mixture of EC, PC, EMC and DMC.
- EC can represent from 5 to 15% by weight of the mass of the organic solvent mixture.
- PC can represent from 15 to 25% by weight of the mass of the organic solvent mixture.
- EMC can represent from 20 to 30% by weight of the mass of the organic solvent mixture.
- DMC can represent from 40 to 50% by weight of the mass of the organic solvent mixture.
- At least one tetrafluoro or hexafluorinated lithium salt and the lithium bis (fluorosulfonyl) imide LiFSI salt in said at least one organic solvent are initially dissolved.
- the nature of the tetrafluoro or hexafluorinated lithium salt is not particularly limited. Mention may be made of lithium hexafluorophosphate LiPF 6 , lithium hexafluoroarsenate LiAsF 6 , lithium hexafluoroantimonate LiSbF 6 and lithium tetrafluoroborate LiBF 4 . Lithium hexafluorophosphate LiPF 6 will preferably be chosen.
- the electrolyte composition contains no other lithium salts other than the tetrafluoro or hexafluorinated lithium salt or lithium bis (fluorosulfonyl) imide LiFSI salt.
- the electrolyte composition contains no other lithium salts other than the tetrafluoro or hexafluorinated lithium salt or lithium bis (fluorosulfonyl) imide LiFSI salt.
- it does not contain lithium difluorophosphate L1PO2F2 or lithium difluoro (oxalato) borate LiBF 2 (C 2 O 4 ) (LiDFOB).
- L1PO2F2 is weakly dissociated.
- Li + PO2F2 is almost non-existent.
- a resulting electrolyte using this salt would have a conductivity far too low to be used in a Li-ion type battery. Due to its low ionicity, L1PO2F2 is very poorly soluble in the electrolyte. Its concentration can not therefore exceed 0.1 mol.L 1 . On the other hand, the presence of LiDFOB can lead to an excessive generation of gases during its decomposition in reduction and oxidation.
- the electrolyte incorporating this salt also has a low ionic conductivity.
- the only lithium salts in the electrolyte composition are LiPF 6 and LiFSI.
- the total concentration of lithium ion in the electrolyte composition is generally between 0.1 and 3 mol.L 1 , preferably between 0.5 and 1.5 mol.L 1 , more preferably about 1 mol.L 1 .
- the lithium ions derived from the tetrafluoro or hexafluorinated lithium salt generally represent up to 70% of the total amount of lithium ions present in the electrolyte composition. They may also represent from 1 to 70% of the total amount of lithium ions present in the electrolyte composition. They may also represent from 10 to 70% of the total amount of lithium ions present in the electrolyte composition.
- the lithium ions derived from lithium bis (fluorosulfonyl) imide salt generally represent at least 30% of the total amount of lithium ions present in the electrolyte composition. They can still represent from 30 to 99% of the total amount of lithium ions present in the electrolyte composition. They may also represent from 30 to 90% of the total amount of lithium ions present in the electrolyte composition.
- the mixture containing said at least one organic solvent and the lithium salts, vinylene carbonate and ethylene sulphate are added. These compounds act as an additive contributing to the stabilization of the passivation layer that forms on the surface of the negative electrode of the electrochemical element during the first charge / discharge cycles of the element. Additives other than vinylene carbonate and ethylene sulphate may also be added to the mixture.
- the electrolyte composition contains no other additives than vinylene carbonate and ethylene sulphate.
- the electrolyte composition does not contain sultone (s).
- sultone (s) has a disadvantage with respect to ethylene sulphate in that the passivation layer (SEI) at the surface of the negative electrode is less conductive for cold applications than when ethylene sulphate is present.
- SEI passivation layer
- the passivation layer on the surface of the negative electrode is more robust and less soluble in the electrolyte when ethylene sulfate is present than when a sultone is present.
- the quantity of additive introduced into the mixture is measured in mass relative to the mass of the group consisting of the lithium salt (s) tetrafluoro or hexafluoro (s), the salt of bis (fluorosulfonyl) LiFSI lithium imide and said at least one organic solvent.
- the mass percentage of vinylene carbonate represents from 0.1 to 5%, preferably from 0.5 to 3%, more preferably from 1 to 2% by weight of the mass of the assembly consisting of by the tetrafluoro or hexafluorinated lithium salt (s), the lithium bis (fluorosulfonyl) imide salt and the said at least one organic solvent.
- the mass percentage of ethylene sulphate represents from 0.1 to 5%, preferably from 0.5 to 2%, more preferably from 1 to 2% by weight of the mass. of the group consisting of the tetrafluoro or hexafluorinated lithium salt (s), the lithium bis (fluorosulfonyl) imide salt and the said at least one organic solvent.
- the ethylene sulphate may represent from 20 to 80% or from 30 to 50% by weight of the mass of the group consisting of ethylene sulphate and vinylene carbonate.
- the vinylene carbonate may represent from 80 to 20% or from 50 to 30% by weight of the mass of the group consisting of ethylene sulphate and vinylene carbonate.
- a preferred electrolyte composition comprises:
- LiFSI lithium bis (fluorosulfonyl) imide salt
- vinylene carbonate from 1 to 3% by weight of vinylene carbonate, preferably 2% by weight of the mass of the group consisting of the lithium or tetrafluoro or hexafluorinated salt (s), the salt of lithium bis (fluorosulfonyl) imide and said at least one organic solvent;
- ethylene sulphate from 0.5 to 2% by mass of ethylene sulphate, preferably 1% by weight of the mass of the group consisting of the lithium or tetrafluoro or hexafluorinated salt (s), lithium bis (fluorosulfonyl) imide salt and said at least one organic solvent.
- Another preferred electrolyte composition comprises:
- LiFSI lithium bis (fluorosulfonyl) imide salt LiFSI lithium bis (fluorosulfonyl) imide salt
- vinylene carbonate from 1 to 3% by weight of vinylene carbonate, preferably 2% by weight of the mass of the group consisting of the lithium or tetrafluoro or hexafluorinated salt (s), the salt of lithium bis (fluorosulfonyl) imide and said at least one organic solvent;
- ethylene sulphate from 0.5 to 2% by mass of ethylene sulphate, preferably 1% by weight of the mass of the group consisting of the lithium or tetrafluoro or hexafluorinated salt (s), lithium bis (fluorosulfonyl) imide salt and said at least one organic solvent.
- Another preferred electrolyte composition comprises:
- LiFSI lithium bis (fluorosulfonyl) imide salt from 0.8 to 0.95 mol.L 1 of LiFSI lithium bis (fluorosulfonyl) imide salt
- Another preferred electrolyte composition comprises:
- LiFSI lithium bis (fluorosulfonyl) imide salt
- ethylene sulphate 1% by weight of ethylene sulphate relative to the weight of the group consisting of the lithium or tetrafluoro or hexafluorinated salt (s), the lithium bis (fluorosulfonyl) imide salt; and said at least one organic solvent.
- Another preferred electrolyte composition comprises:
- ethylene sulphate 1% by weight of ethylene sulphate relative to the weight of the group consisting of the lithium or tetrafluoro or hexafluorinated salt (s), the lithium bis (fluorosulfonyl) imide salt; and said at least one organic solvent.
- the active material of the negative electrode (anode) of the electrochemical element is preferably a carbonaceous material which can be selected from graphite, coke, carbon black and vitreous carbon.
- the active material of the negative electrode contains a silicon-based compound.
- the positive active material of the positive electrode (cathode) of the electrochemical element is not particularly limited. It can be chosen from the group consisting of: - a i) compound of formula Li x Mni- yz M 'y M' 'z P0 4 (LMP), where M' and M "are different from one another and are selected from the group consisting of B, Mg, Al, Si, Ca, Ti, V, Cr, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb and Mo, with 0.8 ⁇ x ⁇ l, 2; 0 ⁇ y ⁇ 0.6 0 ⁇ z ⁇ 0.2;
- An example of compound i) is LiMni- y Fe y P0 4.
- a preferred example is LiMnPO 4 .
- the compound ii) can have the formula Li x M 2-xyzw M 'y M' 'z M''' w 0 2, where ⁇ x ⁇ l, l5; M is Ni; M 'denotes Mn; M "refers to Co and M" is selected from the group consisting of B, Mg, Al, Si, Ca, Ti, V, Cr, Fe, Cu, Zn, Y, Zr, Nb, Mo or a mixture thereof. this ; 2-xyzw>0;y>0;z>0;w> 0.
- Compound ii) can have the formula LiNii / 3 Mn / 3 Co / 3 0 2 .
- Compound ii) can also have the formula Li x M2- xyzw M'yM''zM ''' w 02, where 1 ⁇ x ⁇ 1.15; M is Ni; M 'denotes Co; M "is Al and M" is selected from the group consisting of B, Mg, Si, Ca, Ti, V, Cr, Fe, Cu, Zn, Y, Zr, Nb, Mo or a mixture thereof; 2-xyzw>0;y>0;z>0;w> 0.
- Compound ii) may also be selected from LiNiCh, LiCoCh, LiMnCh, Ni, Co and Mn may be substituted by one or more of the members selected from the group consisting of Mg, Mn (except for LiMnCh), Al, B, Ti, V, Si, Cr, Fe, Cu, Zn, Zr.
- the positive active material may be at least partially covered by a layer of carbon.
- the positive and negative active materials of the lithium ion electrochemical element are generally mixed with one or more binder (s), the function of which is to bind the particles of active material together and to bind them to the current collector on which they are deposited.
- the binder may be chosen from carboxymethylcellulose (CMC), a butadiene-styrene copolymer (SBR), polytetrafluoroethylene (PTFE), polyamideimide (P AI), polyimide (PI), styrene-butadiene rubber (SBR), Polyvinyl alcohol, polyvinylidene fluoride (PVDF) and a mixture thereof.
- CMC carboxymethylcellulose
- SBR butadiene-styrene copolymer
- PTFE polytetrafluoroethylene
- P AI polyamideimide
- PI polyimide
- SBR styrene-butadiene rubber
- PVDF polyvinyl alcohol
- PVDF polyvinylidene fluoride
- the current collector of the positive and negative electrodes is in the form of a solid or perforated metal strip.
- the strip can be made from different materials. These include copper or copper alloys, aluminum or aluminum alloys, nickel or nickel alloys, steel and stainless steel.
- the current collector of the positive electrode is generally an aluminum strip or an alloy comprising predominantly aluminum.
- the current collector of the negative electrode is generally a copper strip or an alloy mainly comprising copper.
- the thickness of the positive electrode strip may be different of that of the strip of the negative electrode.
- the strip of the positive or negative electrode has a thickness generally between 6 and 30 mhi.
- the aluminum collector of the positive electrode is covered with a conductive coating, such as carbon black, graphite.
- the negative active material is mixed with one or more binders mentioned above and optionally a good electronically conductive compound, such as carbon black.
- An ink is obtained which is deposited on one or both faces of the current collector.
- the ink-coated current collector is laminated to adjust its thickness. A negative electrode is thus obtained.
- composition of the ink deposited on the negative electrode can be the following:
- binder preferably 5%
- composition of the ink deposited on the positive electrode may be the following:
- binder preferably 10%
- the material of the separator may be chosen from the following materials: a polyolefin, for example polypropylene, polyethylene, a polyester, glass fibers bonded together by a polymer, polyimide, polyamide, polyaramid, polyamideimide and cellulose.
- the polyester may be selected from polyethylene terephthalate (PET) and polybutylene terephthalate (PBT).
- PET polyethylene terephthalate
- PBT polybutylene terephthalate
- the polyester or polypropylene or polyethylene contains or is coated with a material selected from the group consisting of a metal oxide, a carbide, a nitride, a boride, a silicide and a sulfide. This material can be S1O2 or AI2O3.
- An electrochemical beam is formed by interposing a separator between at least one positive electrode and at least one positive electrode.
- the electrochemical bundle is inserted into the container of the element.
- the container of the element may be of parallelepipedal or cylindrical format. In the latter case, the electrochemical bundle is spiraled to form a cylindrical arrangement of the electrodes.
- the container provided with the electrochemical bundle is filled with the electrolyte composition as described above.
- An element according to the invention typically comprises the combination of the following constituents:
- At least one positive electrode whose active material is a lithiated oxide of transition metals comprising nickel, manganese and cobalt;
- the Applicant has found that the combination of the two lithium salts, that is to say the tetrafluoro or hexafluorinated lithium salt and lithium bis (fluorosulfonyl) imide LiFSI salt with the two additives, that is to say ie vinylene carbonate and ethylene sulphate, provided the following advantages:
- the electrochemical element can operate over a wide temperature range, that is to say from -10.degree. C. to -20.degree. C., up to a temperature of up to 80.degree. lOO ° C.
- the electrochemical element has good cold power down to -40 ° C.
- the electrochemical element may be subjected to cycling with significant variations in the ambient temperature.
- the electrochemical element loses its capacity less rapidly when used under cycling conditions.
- the invention therefore makes it possible to extend the service life of an element operating under the cycling conditions, whether it is a cycling at low temperature or at high temperature. Gas formation in the case of elements comprising a graphite-based anode is reduced.
- the electrolyte prefferably contains no lithium salt other than the tetrafluoro or hexafluorinated lithium salt or the lithium bis (fluorosulfonyl) imide LiFSI salt and to contain no other additive than vinylene carbonate and the ethylene sulphate.
- Electrochemical lithium-ion elements have been manufactured. They comprise a negative electrode whose active material is graphite and a positive electrode whose active ingredient has the formula LiNii / 3 Mni / 3 Co / 3 0 2 .
- the separator is made of polypropylene.
- the containers of the elements were filled with an electrolyte whose composition is referenced from A to Q. Table 1 below indicates the various electrolyte compositions A to Q. For convenience, the electrochemical elements will be designated in the following with reference to the electrolyte composition they contain.
- Element A comprises a reference electrolyte comprising LiPF 6 at a concentration of 1 mol.L 1 and 3% by weight of vinylene carbonate.
- Element B comprises an electrolyte according to the invention which differs from that of element A in that a portion of LiPF 6 has been substituted by LiFSI and that part of the vinylene carbonate has been substituted with ethylene sulphate. 90% of the molar amount of LiPF 6 salt was substituted with LiFSI and one third of the vinylene carbonate mass was substituted with ethylene sulfate.
- Elements A and B underwent an electrochemical formation cycle at 60 ° C including a load at the C / 10 rate, followed by a C / 10 discharge, where C is the rated capacity of the elements.
- the electrochemical impedance spectra of the open circuit elements A and B were then plotted in a frequency range from 1 kHz to 10 mHz at a temperature of -40 ° C.
- Figure 1 shows the impedance spectra obtained. It can be seen that for a frequency of less than approximately 0.01 Hz, the impedance of element B is lower than that of element A, which is beneficial for the lifetime of the element.
- the viscosity of the electrolyte compositions A and B was measured for a temperature of -20 ° C to 60 ° C.
- the variation of the viscosity as a function of temperature is shown in FIG. 2. This figure shows that the viscosity of the electrolyte composition B is lower than that of the electrolyte composition A. This reduction in viscosity has the advantage significantly reduce the fill time of an element.
- Electrolyte compositions A and B were stored at a temperature of 85 ° C for two weeks. At the end of this storage period, they were analyzed by gas chromatography. The spectra obtained are shown in FIG. 3. The upper spectrum is that of composition A, the lower spectrum is that of composition B.
- the spectrum obtained on composition A reveals the peaks corresponding to DMC, EMC, VC, PC and EC at the respective retention times of 11, 14, 32, 41 and 44 min. It also shows two peaks of high intensity at retention times of 39 and 42 min, as well as low intensity peaks at retention times of 18 and 29 min. The peaks at retention times 18, 29, 39 and 42 minutes are attributed to products formed by the decomposition of the electrolyte during the 85 ° C storage period. In comparison, the spectrum of composition B does not show any of the peaks at the retention times of 18, 29, 39 and 42 minutes. This indicates that the electrolyte composition B decomposes less rapidly than the composition A.
- Elements A and B were cycled at a temperature of 85 ° C. Each cycle has a charging phase at the C / 3 regime followed by a discharge phase at from C / 3 to a discharge depth of 100%.
- the capacity discharged by the elements is measured during cycling. Its variation is shown in Figure 4. This figure shows that in cycle 50, the loss of capacity of element A is 10% while it is only 5% for element B. At cycle 90, element A lost 20% of its initial capacity. He therefore reached the end of life criterion after 90 cycles. In comparison, at the same cycle number, element B lost only 8% of its initial capacity. Element B has a reduced loss of capacity because after 235 cycles, it remains less than 20%.
- FIG. 5 represents the variation of the discharged capacity of the elements A and B. It shows on the one hand that whatever the cycling temperature, the capacity discharged by the element B is greater than that of the element A. shows on the other hand that at -20 ° C, the element B loses less quickly than the element A. Indeed, the loss of capacity of the element B is -2,5 mAh per cycle while it is -4.2 mAh per cycle for element A. The life of element B is greater than that of element A. The loss of capacity of element B to -20 ° C over 200 cycles is 0.5 Ah, which represents a loss of 12% of its initial capacity, below the limit of 20% fixed. The objective sought by the present invention is therefore well achieved.
- Figures 1 to 5 illustrate the benefit provided by the combination of the two lithium salts, that is to say the lithium hexafluoride salt and lithium bis (fluorosulfonyl) imide LiFSI salt with the two additives that is, vinylene carbonate and ethylene sulphate.
- the two additives that is, vinylene carbonate and ethylene sulphate.
- Figure 6 shows the variation of the discharged capacity of the elements C, D and E during cycling.
- the comparison between the D element curve and the C element curve shows that the addition of 5% vinylene carbonate helps to slow the loss of capacity during cycling.
- the comparison between the curve of the element E and that of the element C shows that the addition of 5% of ethylene sulphate has almost no effect on the slowdown of the loss of capacity of the element.
- Figure 7 shows the variation of the discharged capacity of the elements C, F and G during cycling. Comparing the curve of element F with that of element C shows that the addition of 2% of vinylene carbonate helps to slow down the loss of capacity during cycling but to a lesser extent than for an addition of 5% vinylene carbonate (element D).
- the Applicant has found, surprisingly, that when 2% of ethylene sulphate is added to the composition of the element F containing 2% of vinylene carbonate, an increase in the discharged capacity and an increase in on the other hand a slowing down of the loss of capacity of the element during cycling (element G).
- the Applicant is of the opinion that the combination of vinylene carbonate with ethylene sulphate makes it possible to stabilize the passivation layer on the surface of the negative electrode.
- the passivation layer forms a shield which prevents the electrolyte from contacting the negative electrode and decompose.
- the passivation layer being made more stable, it protects more against the decomposition of the electrolyte.
- the bottom spectrum of FIG. 8 is that of element E, the electrolyte composition of which comprises 5% of ethylene sulphate as sole additive. It shows three peaks attributable to DMC, EMC, and DEC. This indicates that during cycling, EMC, which was the only organic solvent in the electrolyte composition, decomposed to DMC and DEC. The amounts of DMC and DEC are similar to those obtained for an electrolyte composition comprising EMC and LiPF 6 , without additive (element C). The presence of ethylene sulphate alone does not make it possible to obtain a stable passivation layer.
- the top spectrum of Figure 8 is that of element D containing 5% vinylene carbonate as an additive.
- This spectrum shows that the peaks attributed to DMC and DEC have almost disappeared, indicating that the addition of 5% vinylene carbonate is sufficient to stabilize the passivation layer and prevent the decomposition of EMC into DMC and DEC. 96.4% of the initial amount of vinylene carbonate was consumed by the formation of the passivation layer.
- the comparison of the spectra of Figure 9 demonstrates the effect provided by the presence of ethylene sulphate in combination with vinylene carbonate in the electrolyte.
- the top spectrum of Figure 9 is that of element F comprising 2% vinylene carbonate. It shows three peaks attributed to DMC, EMC and DEC. 100% of the initial amount of vinylene carbonate was consumed by the formation of the passivation layer. This is why the peak of vinylene carbonate does not appear on the spectrum.
- the bottom spectrum of Figure 9 is that of element G comprising 2% vinylene carbonate and 2% ethylene sulfate. It shows a significant decrease in the intensity of the peaks attributed to DMC and DEC.
- Electrolyte compositions having different levels of LiPF 6 substitution by LiFSI were prepared. These are compositions H, I, J, K and L in which the molar substitution rate of LiPF 6 by LiFSI is 0%, 30%, 50%, 70% and 90%, respectively.
- the additive used is vinylene carbonate in a weight percentage of 1%.
- Electrolyte compositions having different levels of LiPF 6 substitution by LiFSI were prepared. These are compositions M, N, O, P and Q in which the molar substitution rate of LiPF 6 by LiFSI is 0%, 30%, 50%, 70% and 90%, respectively.
- the additives used in these compositions are vinylene carbonate and ethylene sulphate, in a weight percentage of 1% each.
- Figure 12 shows the variation of the discharged capacity of the elements H to L during cycling.
- Figure 13 shows the variation of the discharged capacity of the elements M to Q during cycling.
- the elements N to Q which are according to the invention and which contain, as additives, vinylene carbonate combined with ethylene sulphate, have a discharged capacity greater than that of elements I to L which contain only vinylene carbonate. as the only additive. It can also be seen that the advantage of the addition of ethylene sulphate mixed with vinylene carbonate occurs mainly during a high temperature cycling phase, when it follows a low cycling phase. temperature.
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Abstract
Description
Claims
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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FR1763010A FR3076083B1 (fr) | 2017-12-22 | 2017-12-22 | Composition d'electrolyte pour element electrochimique lithium-ion |
PCT/EP2018/086539 WO2019122314A1 (fr) | 2017-12-22 | 2018-12-21 | Composition d'électrolyte pour élément électrochimique de type lithium-ion |
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EP3729552A1 true EP3729552A1 (fr) | 2020-10-28 |
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EP18830272.3A Pending EP3729552A1 (fr) | 2017-12-22 | 2018-12-21 | Composition d'électrolyte pour élément électrochimique de type lithium-ion |
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US (1) | US20210376384A1 (fr) |
EP (1) | EP3729552A1 (fr) |
CN (1) | CN111886744A (fr) |
FR (1) | FR3076083B1 (fr) |
WO (1) | WO2019122314A1 (fr) |
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FR3102889B1 (fr) * | 2019-10-30 | 2023-04-21 | Accumulateurs Fixes | Electrolyte gelifie pour element electrochimique lithium-ion |
KR102585596B1 (ko) * | 2019-12-24 | 2023-10-05 | 컨템포러리 엠퍼렉스 테크놀로지 씨오., 리미티드 | 이차 전지 및 이를 포함하는 장치 |
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JP5678539B2 (ja) * | 2009-09-29 | 2015-03-04 | 三菱化学株式会社 | 非水系電解液電池 |
US8734668B2 (en) * | 2011-06-09 | 2014-05-27 | Asahi Kasei Kabushiki Kaisha | Materials for battery electrolytes and methods for use |
KR101586139B1 (ko) * | 2013-02-20 | 2016-01-15 | 주식회사 엘지화학 | 비수성 전해액 및 이를 포함하는 리튬 이차 전지 |
KR101582043B1 (ko) * | 2013-05-23 | 2015-12-31 | 주식회사 엘지화학 | 출력 및 사이클 특성이 우수한 리튬 이차 전지 |
KR102253219B1 (ko) * | 2013-09-26 | 2021-05-17 | 우베 고산 가부시키가이샤 | 축전 디바이스용 폴리이미드 바인더, 그것을 이용한 전극 시트 및 축전 디바이스 |
CN103682443B (zh) * | 2013-12-31 | 2016-03-16 | 东莞市杉杉电池材料有限公司 | 一种含双氟磺酰基亚胺锂的锂离子电池电解液 |
CN105514483A (zh) * | 2014-05-26 | 2016-04-20 | 宁德时代新能源科技股份有限公司 | 锂离子电池及其电解液 |
WO2016086182A2 (fr) * | 2014-11-26 | 2016-06-02 | Johnson Controls Technology Company | Électrolytes lithium-ion avec lifsi pour améliorer une plage de températures de fonctionnement étendue |
CN105304936B (zh) * | 2015-12-10 | 2018-05-15 | 微宏动力系统(湖州)有限公司 | 一种锂离子二次电池 |
CN105826607B (zh) * | 2016-05-25 | 2019-05-14 | 宁德新能源科技有限公司 | 一种电解液以及包括该电解液的锂离子电池 |
HUE056425T2 (hu) * | 2016-06-23 | 2022-02-28 | 6K Inc | Lítium-ion akkumulátor anyagok |
CN106099171A (zh) * | 2016-07-13 | 2016-11-09 | 东莞市凯欣电池材料有限公司 | 一种锂离子动力电池电解液及锂离子动力电池 |
CN106129456B (zh) * | 2016-07-21 | 2019-04-23 | 中航锂电(洛阳)有限公司 | 一种电解液用功能添加剂,长循环锂离子电池电解液及锂离子电池 |
US20190036171A1 (en) * | 2017-07-31 | 2019-01-31 | Tesla Motors Canada ULC | Novel battery systems based on two-additive electrolyte systems |
-
2017
- 2017-12-22 FR FR1763010A patent/FR3076083B1/fr active Active
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2018
- 2018-12-21 EP EP18830272.3A patent/EP3729552A1/fr active Pending
- 2018-12-21 CN CN201880081800.7A patent/CN111886744A/zh active Pending
- 2018-12-21 WO PCT/EP2018/086539 patent/WO2019122314A1/fr unknown
- 2018-12-21 US US16/772,060 patent/US20210376384A1/en active Pending
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WO2019122314A1 (fr) | 2019-06-27 |
FR3076083B1 (fr) | 2022-10-28 |
CN111886744A (zh) | 2020-11-03 |
FR3076083A1 (fr) | 2019-06-28 |
US20210376384A1 (en) | 2021-12-02 |
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