EP3863974A1 - Positive electrode active material for sodium-ion battery - Google Patents
Positive electrode active material for sodium-ion batteryInfo
- Publication number
- EP3863974A1 EP3863974A1 EP19813925.5A EP19813925A EP3863974A1 EP 3863974 A1 EP3863974 A1 EP 3863974A1 EP 19813925 A EP19813925 A EP 19813925A EP 3863974 A1 EP3863974 A1 EP 3863974A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- sodium
- positive electrode
- varies
- cell
- active material
- 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
Links
- 229910001415 sodium ion Inorganic materials 0.000 title claims abstract description 32
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 title claims abstract description 14
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 6
- 239000011149 active material Substances 0.000 claims description 37
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 24
- 230000001351 cycling effect Effects 0.000 claims description 24
- 239000000203 mixture Substances 0.000 claims description 20
- 239000003792 electrolyte Substances 0.000 claims description 17
- 229910052799 carbon Inorganic materials 0.000 claims description 15
- 239000000463 material Substances 0.000 claims description 15
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 14
- 150000001875 compounds Chemical class 0.000 claims description 14
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 11
- 239000006229 carbon black Substances 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- 239000011734 sodium Substances 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 5
- -1 transition metal salts Chemical class 0.000 claims description 5
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 4
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 239000013528 metallic particle Substances 0.000 claims description 3
- 239000002243 precursor Substances 0.000 claims description 3
- 229910052723 transition metal Inorganic materials 0.000 claims description 3
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 2
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 2
- 239000004917 carbon fiber Substances 0.000 claims description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 2
- 239000002041 carbon nanotube Substances 0.000 claims description 2
- 229910002804 graphite Inorganic materials 0.000 claims description 2
- 239000010439 graphite Substances 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 239000002077 nanosphere Substances 0.000 claims description 2
- 239000002070 nanowire Substances 0.000 claims description 2
- 239000001632 sodium acetate Substances 0.000 claims description 2
- 235000017281 sodium acetate Nutrition 0.000 claims description 2
- 235000017550 sodium carbonate Nutrition 0.000 claims description 2
- 239000004317 sodium nitrate Substances 0.000 claims description 2
- 235000010344 sodium nitrate Nutrition 0.000 claims description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 2
- 235000011152 sodium sulphate Nutrition 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 description 9
- 238000003786 synthesis reaction Methods 0.000 description 9
- 230000015556 catabolic process Effects 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 238000006731 degradation reaction Methods 0.000 description 6
- 229920001410 Microfiber Polymers 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 239000003658 microfiber Substances 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 4
- 159000000000 sodium salts Chemical class 0.000 description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 2
- 229910020650 Na3V2 Inorganic materials 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 238000000840 electrochemical analysis Methods 0.000 description 2
- 229910021385 hard carbon Inorganic materials 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 229910020808 NaBF Inorganic materials 0.000 description 1
- 229910021201 NaFSI Inorganic materials 0.000 description 1
- 229910019398 NaPF6 Inorganic materials 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- 230000000712 assembly Effects 0.000 description 1
- 238000000429 assembly Methods 0.000 description 1
- 238000003421 catalytic decomposition reaction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 238000005553 drilling Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000003411 electrode reaction Methods 0.000 description 1
- 230000016507 interphase Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000000615 nonconductor Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- VCCATSJUUVERFU-UHFFFAOYSA-N sodium bis(fluorosulfonyl)azanide Chemical compound FS(=O)(=O)N([Na])S(F)(=O)=O VCCATSJUUVERFU-UHFFFAOYSA-N 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical class [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- YLKTWKVVQDCJFL-UHFFFAOYSA-N sodium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Na+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F YLKTWKVVQDCJFL-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
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
- H01M4/48—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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/40—Nickelates
- C01G53/42—Nickelates containing alkali metals, e.g. LiNiO2
- C01G53/44—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese
- C01G53/50—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese of the type [MnO2]n-, e.g. Li(NixMn1-x)O2, Li(MyNixMn1-x-y)O2
-
- 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
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/44—Methods for charging or discharging
-
- 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
- H01M4/0471—Processes of manufacture in general involving thermal treatment, e.g. firing, sintering, backing particulate active material, thermal decomposition, pyrolysis
-
- 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
-
- 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
-
- 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
- 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
-
- 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
- the invention relates to the general field of rechargeable sodium-ion (Na-ion) batteries.
- the invention relates more specifically to active materials of positive electrode for Na-ion batteries, and to positive electrodes comprising them.
- the invention also relates to a method for cycling Na-ion batteries.
- Na-ion batteries represent one of the most promising alternative solutions to lithium-ion batteries, sodium being more interesting than lithium economically, in particular because of its abundance and its low cost.
- Na-ion battery cell assemblies can only be considered as prototypes, since only tests have been carried out.
- the first category contains polyanionic compounds.
- the compound Na3V2 (P0 4 ) 2F3 has been identified as being suitable for use within Na-ion batteries. Indeed, it is characterized in particular by ease of synthesis, stability when used in wet conditions, or even high specific energy, as the document WO 2014/009710 describes it.
- the presence of vanadium within the electrode can be problematic during the use of the Na-ion battery in the medium / long term, given its toxic nature.
- the specific capacity of the latter is limited due to its relatively high molecular weight.
- the second category contains lamellar oxides of sodium.
- Na3V2 (P0 4 ) 2F3 (approximately 4.5 g / cm 3 vs approximately 3 g / cm 3 ).
- NaNio, 5Mno, 502 has a theoretical capacity of about 240 mAh / g, as described in the document "Study on the reversible electrode reaction of Nai-xNio.sMno.sCh for a rechargeable sodium ion battery", S. Komaba, N. Yabuuchi, T. Nakayama, A. Ogata, T. Ishikawa, I. Nakai, J. Inorg Chem. 5 1, 621 1 -6220 (2012). However, it turns out that the capacity of this material deteriorates during the charge and discharge cycles of the Na-ion battery.
- the subject of the invention is therefore an active material of a positive electrode for a sodium-ion battery of formula (I) below:
- x varies from 0.9 to 1;
- - y varies from 0.05 to 0.1;
- - z varies from 0.1 to 0.3.
- Another object of the invention is a process for preparing the active material according to the invention.
- the invention also has for its object and a positive electrode comprising the active material according to the invention.
- Another object of the invention is a Na-ion battery cell, comprising the electrode according to the invention.
- the invention also relates to a Na-ion battery comprising at least one cell according to the invention.
- the invention also relates to a particular cycling method for Na-ion batteries comprising an active material with a particular positive electrode.
- FIG 1 is a graph representing the capacity of a Naion battery cell, as a function of the number of charge and discharge cycles;
- FIG 2 is a graph representing the voltage of a Naion battery cell, as a function of capacity
- FIG 3 is a graph representing the capacity of a Naion battery cell, as a function of the number of charge and discharge cycles;
- FIG 4 is a graph representing the voltage of a Naion battery cell, as a function of capacity
- FIG 5 is a graph representing the voltage of a Naion battery cell, as a function of capacity
- FIG 6 is a graph representing the voltage of a Naion battery cell, as a function of capacity
- FIG 7 is a graph representing the voltage of a Naion battery cell, as a function of capacity
- FIG 8 is a graph representing the voltage of a half-cell of Na-ion battery, according to the capacity.
- Fe active material of positive electrode for Na-ion battery according to the invention corresponds to formula (I) as mentioned above.
- y varies from 0.06 to 0.1, preferably y is equal to 0.1.
- z varies from 0.2 to 0.3.
- x varies from 0.95 to 1, preferably x is equal to 1.
- the subject of the invention is also a process for preparing the active material according to the invention comprising the following steps:
- step (b) heating the mixture obtained at the end of step (a) to a temperature ranging from 800 to 1000 ° C;
- the compound is chosen from oxides.
- the oxide is chosen from NiO, CuO, M Cb, Mn0 2 , Ti0 2 and their mixtures.
- the precursor is sodium carbonate.
- an oxide chosen from NiO, CuO, Mn 2 ⁇ 3 , Mn0 2 , Ti0 2 and their mixtures is mixed with sodium carbonate.
- the mixture obtained at the end of step (a) is heated to a temperature ranging from 850 to 950 ° C.
- step (b) takes place over a period ranging from 6 hours to 20 hours, preferably from 9 hours to 15 hours, more preferably from 11 to 13 hours, more preferably from 12 hours.
- step (b) is followed by a cooling and drying step.
- the mixture is heated to 900 ° C in an oven for 12 hours, then cooled to 300 ° C, then removed from the oven.
- Another object of the invention is a positive electrode comprising the active material according to the invention.
- the positive electrode according to the invention further comprises at least one conductive compound.
- the conductive compound is chosen from metallic particles, carbon, and their mixtures, preferably carbon.
- Said metallic particles can be particles of silver, copper or nickel.
- the carbon can be in the form of graphite, carbon black, carbon fibers, carbon nanowires, carbon nanotubes, carbon nanospheres, preferably carbon black.
- the positive electrode according to the invention advantageously comprises the carbon black SuperC65® sold by Timcal.
- the content of active material according to the invention varies from 50 to 90% by weight, preferably from 70 to 90% by weight, relative to the total weight of the positive electrode.
- the content of conductive compound varies from 10 to 50% by weight, preferably from 10 to 30% by weight, more preferably from 15 to 25% by weight, relative to the total weight of the positive electrode.
- the present invention also relates to a battery cell
- Na-ion comprising a positive electrode comprising the active material according to the invention, a negative electrode, a separator and an electrolyte.
- the battery cell comprises a separator located between the electrodes and playing the role of electrical insulator.
- separators are generally composed of porous polymers, preferably polyethylene and / or polypropylene. They can also be made of glass microfibers.
- the separator used is a separator made of glass microfibers CAT No. 1823-070® sold by Whatman.
- said electrolyte is liquid.
- This electrolyte can comprise one or more sodium salts and one or more solvents.
- the sodium salt or salts may be chosen from NaPF6, NaCl0 4 , NaBF 4 , NaTFSI, NaFSI, and NaODFB.
- the sodium salt or salts are preferably dissolved in one or more solvents chosen from aprotic polar solvents, for example, ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, and the methyl and ethyl carbonate.
- aprotic polar solvents for example, ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, and the methyl and ethyl carbonate.
- the electrolyte comprises propylene carbonate in admixture with the sodium salt NaPFô at 1 M.
- the present invention also relates to a Naion battery comprising at least one cell as described above.
- the present invention also relates to a method for cycling a sodium-ion battery comprising a negative electrode, a separator, an electrolyte and a positive electrode comprising an active material of formula (II) below:
- - r varies from 0.05 to 0.1;
- the upper voltage ranging from 4.2 to 4.7 V, preferably 4.4 to 4.6 V, more preferably equal to 4.5 V
- the lower voltage ranging from 0.5 to 2.5, preferably from 1.5 to 2.5, more preferably equal to 2 V
- the cycles being carried out at a cycling regime ranging from C / 20 to C, C denoting the cycling regime of the sodium-ion battery.
- a solid and stable layer called "Cathode Electrolyte Interphase” (CEI) more protective is generated, by compared to an application of a lower higher voltage, for example less than 4, IV.
- This IEC located between the cathode and the electrolyte, is an essential element for proper functioning Na-ion battery, because not only does it conduct sodium ions very well but it also has the advantage of stopping the catalytic decomposition of the electrolyte.
- the active material of formula (II) is of formula (I).
- the cycling regime is C / 10.
- the positive electrodes EN-A and EN-B are comparative electrodes.
- the electrodes EN-C to EN-F are electrodes according to the invention.
- the EN-A positive electrode is made by mixing 80% by weight of the active material A, which has been directly transferred to a glove box from the oven without exposure to air, and 20% by weight of the carbon black SuperC65® , the mixture then being ground for 30 minutes using a SPEX 8000M mixer.
- the other positive electrodes EN-B to EN-F are produced by mixing 80% by weight of the active material, respectively B to F, and 20% by weight of the carbon black SuperC65®, the mixtures then being ground in the same way as for the positive electrode EN-A.
- active materials B to F were transferred directly into a glove box from the oven without exposure to air.
- the cells were then prepared respectively comprising the positive electrodes EN-A to EN-F.
- the cells are respectively named CE-A, CE-B, CE-C, CE-D, CE-E and CE-F.
- the assembly of the electrochemical cells is carried out in a glove box using a device consisting of a button cell of the type 2032.
- Each of the cells comprises a separator, a negative electrode and an electrolyte.
- 1823-070® are used to avoid any short circuit between the positive electrode and the negative electrode during the charge and discharge cycles. These separators are cut to a diameter of 16.6 mm and a thickness of 400 qm.
- An electrode of 1 cm 2 is obtained by drilling hard carbon discs coated on a film with an aluminum current collector.
- the active material of hard carbon is approximately 5. 20 mg / cm 2 .
- the electrolyte used comprises a solution composed of 1 M
- Electrodes EN-B to EN-F A mass of 8.50, 9.35, 9.36, 9.35 and 8.75 mg of each of the electrodes EN-B to EN-F, respectively, in the form of a powder, is then spread over a aluminum sheet placed in cells CE-B to CE-F, respectively.
- the separators, negative electrodes and electrolytes are identical to those used in the CE-A cell.
- Galvanostatic cycling is carried out using a BioLogic cycler at a cycling speed of C / 20, C denoting the cell capacity, at voltages ranging from 4.2 to 1.5 V.
- CE-A was measured as a function of the number of cycles, as shown in Figure 1. The change in capacity is observed on curve A.
- a capacity of approximately 130 mAh.g 1 is measured after 30 cycles.
- Galvanostatic cycling is carried out using a BioLogic cycler at a cycling regime of C / 20, C denoting the cell capacity, at voltages ranging from 4.4 to 1.2 V.
- curve B l corresponds to the first charge and discharge cycle.
- Curve B2 corresponds to the second charge and discharge cycle, and so on until curve B5 which corresponds to the fifth charge and discharge cycle.
- Galvanostatic cycling is carried out using a BioLogic cycler at a cycling speed of C / 20, C denoting the capacity of the cell, at voltages ranging from 4.4 to 1.2 V.
- the capacity of the CE-C cell was measured as a function of the number of cycles, as shown in FIG. 3. The evolution of the capacity is observed on curve C.
- the capacity of the CE-C cell according to the invention is higher and more stable over the charge and discharge cycles.
- the capacity of the cell comprising the active material according to the invention is improved.
- the voltage of the CE-C cell was measured as a function of the capacity, as shown in Figure 4.
- Curves C l to C5 are more linear than curves B l to B5.
- the degradation of the capacity of the CE-C cell is not observed as was the case for the CE-B cell. Indeed, the capacity of the CE-C cell is more stable.
- Galvanostatic cycling is carried out using a BioLogic cycler at a cycling regime of C / 20, C denoting the cell capacity, at voltages ranging from 4.4 to 1.2 V.
- the voltage of the CE-D cell was measured as a function of capacity, as shown in Figure 5.
- Curves D l to D5 are more linear than curves B l to B5.
- CE-E cell according to the invention is a cell according to the invention
- Galvanostatic cycling is carried out using a BioLogic cycler at a cycling regime of C / 20, C denoting the cell capacity, at voltages ranging from 4.4 to 1.2 V.
- the voltage of the CE-E cell was measured as a function of capacity, as shown in Figure 6.
- Curves E l to E5 are more linear than curves B l to B5.
- the degradation of the capacity of the CE-E cell is not observed as it was the case for the CE-B cell. Indeed, the capacity of the CE-E cell is more stable.
- Galvanostatic cycling is carried out using a BioLogic cycler at a cycling regime of C / 20, C denoting the cell capacity, at voltages ranging from 4.4 to 1.2 V.
- the voltage of the CE-F cell was measured as a function of capacity, as shown in Figure 7.
- curve F l corresponds to the first charge and discharge cycle, and so on until curve F5 which corresponds to the fifth charge and discharge cycle.
- Curves F l to F5 are more linear than curves B l to B5.
- the degradation of the capacity of the CE-F cell is not observed as was the case for the CE-B cell. Indeed, the capacity of the CE-F cell is more stable.
- the positive electrode is made by mixing 80% by weight of the active material NaNio, 45Cuo, o5Mno, 4 Tio, i02, which was directly transferred into a glove box from the oven without exposure to air, and 20% by weight SuperC65® carbon black, the mixture then being ground for 30 minutes using a SPEX 8000M mixer.
- a half cell was then prepared comprising the above-mentioned positive electrode.
- the assembly of the half-cell is carried out in a glove box using a device consisting of a Swagelok® connector 12 mm in diameter.
- the half cell includes a separator, a negative electrode and an electrolyte.
- Two layers of CAT No. 1823-070® glass microfiber separator are used to prevent short circuits between the positive and negative electrodes during the charge and discharge cycles. These separators are cut to a diameter of 12 mm and a thickness of 500 qm.
- 11 mm diameter pellets are cut from a sodium metal sheet. The pellet obtained is then bonded by pressure on a stainless steel current collector. This collector is then deposited on the separating membrane in the cell.
- the electrolyte used comprises a solution composed of 1 M NaPFô dissolved in propylene carbonate.
- Electrochemical test A cycling process comprising applying a plurality of charge and discharge cycles at voltages ranging from 2 to 4.5V, was carried out, at a cycling rate of C / 10.
- the half-cell voltage was measured as a function of capacity, as shown in Figure 8.
- the curve G designates the plurality of charge and discharge cycles which has been carried out.
- the capacity of the half-cell is stable with the repetition of the charge and discharge cycles.
Abstract
Description
Claims
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR1859417A FR3087299B1 (en) | 2018-10-11 | 2018-10-11 | POSITIVE ELECTRODE ACTIVE MATERIAL FOR SODIUM-ION BATTERY |
PCT/FR2019/052414 WO2020074836A1 (en) | 2018-10-11 | 2019-10-10 | Positive electrode active material for sodium-ion battery |
Publications (1)
Publication Number | Publication Date |
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EP3863974A1 true EP3863974A1 (en) | 2021-08-18 |
Family
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Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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EP19813925.5A Pending EP3863974A1 (en) | 2018-10-11 | 2019-10-10 | Positive electrode active material for sodium-ion battery |
Country Status (7)
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US (1) | US20220013772A1 (en) |
EP (1) | EP3863974A1 (en) |
JP (1) | JP2022504568A (en) |
KR (1) | KR20210116433A (en) |
CN (1) | CN113454031A (en) |
FR (1) | FR3087299B1 (en) |
WO (1) | WO2020074836A1 (en) |
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GB2503898A (en) | 2012-07-10 | 2014-01-15 | Faradion Ltd | Nickel doped compound for use as an electrode material in energy storage devices |
GB2503896A (en) * | 2012-07-10 | 2014-01-15 | Faradion Ltd | Nickel doped compound for use as an electrode material in energy storage devices |
CH706725A2 (en) | 2012-07-12 | 2014-01-15 | Matthias Scheibmayr | Projectile and a method of subjecting it. |
PL3311434T3 (en) * | 2015-06-19 | 2020-05-18 | Centre National De La Recherche Scientifique | Method for producing a positive electrode composite material for na ion battery |
EP3332437B1 (en) * | 2015-07-15 | 2020-09-02 | Toyota Motor Europe | Sodium layered oxide as cathode material for sodium ion battery |
GB2543831A (en) * | 2015-10-30 | 2017-05-03 | Sharp Kk | Method of passive voltage control in a sodium-ion battery |
CN106673075B (en) * | 2017-01-03 | 2019-05-21 | 中国科学院化学研究所 | A kind of modified O3 type sodium-ion battery layered cathode material and its preparation method and application |
-
2018
- 2018-10-11 FR FR1859417A patent/FR3087299B1/en active Active
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2019
- 2019-10-10 JP JP2021519643A patent/JP2022504568A/en active Pending
- 2019-10-10 KR KR1020217014056A patent/KR20210116433A/en unknown
- 2019-10-10 WO PCT/FR2019/052414 patent/WO2020074836A1/en unknown
- 2019-10-10 US US17/284,202 patent/US20220013772A1/en active Pending
- 2019-10-10 CN CN201980073913.7A patent/CN113454031A/en active Pending
- 2019-10-10 EP EP19813925.5A patent/EP3863974A1/en active Pending
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Publication number | Publication date |
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US20220013772A1 (en) | 2022-01-13 |
JP2022504568A (en) | 2022-01-13 |
WO2020074836A1 (en) | 2020-04-16 |
CN113454031A (en) | 2021-09-28 |
FR3087299B1 (en) | 2020-10-30 |
KR20210116433A (en) | 2021-09-27 |
FR3087299A1 (en) | 2020-04-17 |
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