WO2024144725A1 - Rechargeable batteries containing naymn0.5-xcoxfe0.43m0.07o2 cathode active - Google Patents
Rechargeable batteries containing naymn0.5-xcoxfe0.43m0.07o2 cathode active Download PDFInfo
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- WO2024144725A1 WO2024144725A1 PCT/TR2023/051767 TR2023051767W WO2024144725A1 WO 2024144725 A1 WO2024144725 A1 WO 2024144725A1 TR 2023051767 W TR2023051767 W TR 2023051767W WO 2024144725 A1 WO2024144725 A1 WO 2024144725A1
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- 239000000463 material Substances 0.000 claims abstract description 23
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 11
- 239000012528 membrane Substances 0.000 claims abstract description 10
- 239000003792 electrolyte Substances 0.000 claims abstract description 8
- 239000000843 powder Substances 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 16
- 229910001415 sodium ion Inorganic materials 0.000 claims description 12
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims description 11
- 150000001875 compounds Chemical class 0.000 claims description 11
- 229910052723 transition metal Inorganic materials 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- 150000003624 transition metals Chemical class 0.000 claims description 5
- 229910052783 alkali metal Inorganic materials 0.000 claims description 4
- 150000001340 alkali metals Chemical class 0.000 claims description 4
- 229910045601 alloy Inorganic materials 0.000 claims description 4
- 239000000956 alloy Substances 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 239000013078 crystal Substances 0.000 claims description 4
- 239000007772 electrode material Substances 0.000 claims description 4
- 229910001092 metal group alloy Inorganic materials 0.000 claims description 4
- 150000002739 metals Chemical class 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 230000000737 periodic effect Effects 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 4
- 239000011230 binding agent Substances 0.000 claims description 3
- 239000010408 film Substances 0.000 claims description 3
- 229910052755 nonmetal Inorganic materials 0.000 claims description 3
- 239000010409 thin film Substances 0.000 claims description 3
- 239000002482 conductive additive Substances 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 230000002542 deteriorative effect Effects 0.000 claims 1
- 238000007493 shaping process Methods 0.000 claims 1
- 230000005923 long-lasting effect Effects 0.000 abstract description 3
- 238000000926 separation method Methods 0.000 abstract description 3
- 238000004146 energy storage Methods 0.000 abstract 1
- 238000002441 X-ray diffraction Methods 0.000 description 10
- 238000002484 cyclic voltammetry Methods 0.000 description 10
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 6
- 239000011888 foil Substances 0.000 description 6
- 229910021385 hard carbon Inorganic materials 0.000 description 6
- 239000006229 carbon black Substances 0.000 description 5
- 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 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- UPWOEMHINGJHOB-UHFFFAOYSA-N oxo(oxocobaltiooxy)cobalt Chemical compound O=[Co]O[Co]=O UPWOEMHINGJHOB-UHFFFAOYSA-N 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 239000002033 PVDF binder Substances 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 150000001721 carbon Chemical class 0.000 description 2
- 239000006182 cathode active material Substances 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Inorganic materials O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 235000017550 sodium carbonate Nutrition 0.000 description 2
- 238000003746 solid phase reaction Methods 0.000 description 2
- 238000010671 solid-state reaction Methods 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- 229910032387 LiCoO2 Inorganic materials 0.000 description 1
- 229910052493 LiFePO4 Inorganic materials 0.000 description 1
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 description 1
- 229910021225 NaCoO2 Inorganic materials 0.000 description 1
- 229910021312 NaFePO4 Inorganic materials 0.000 description 1
- 229910019338 NaMnO2 Inorganic materials 0.000 description 1
- 229910019398 NaPF6 Inorganic materials 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910021525 ceramic electrolyte Inorganic materials 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011245 gel electrolyte Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 239000002241 glass-ceramic Substances 0.000 description 1
- 239000008240 homogeneous mixture Substances 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 239000011244 liquid electrolyte Substances 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000005518 polymer electrolyte Substances 0.000 description 1
- 229920005597 polymer membrane Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- IKULXUCKGDPJMZ-UHFFFAOYSA-N sodium manganese(2+) oxygen(2-) Chemical compound [O-2].[Mn+2].[Na+] IKULXUCKGDPJMZ-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 238000003786 synthesis reaction Methods 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
- 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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
-
- 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 invention aims to produce a rechargeable sodium ion battery; NayMn0.5- xCoxFe0.43M0.07O2 (y varies between zero and 1 , x varies between zero and 1.
- the phase mentioned is selected among single crystal, thin film, thick film and polycrystalline phases suitable for battery construction.
- said binder mentioned in the processing step contains one or more of polyvinylidene fluoride (PVDF), Styrene butadiene rubber (SBR), Carboxy methyl cellulose (CMC) powders.
- PVDF polyvinylidene fluoride
- SBR Styrene butadiene rubber
- CMC Carboxy methyl cellulose
- PVDF polyvinylidene fluoride
- SBR Styrene butadiene rubber
- CMC Carboxy methyl cellulose
- the rechargeable battery cell mentioned in the process step is a pouch cell, prismatic cell or cylindrical cell.
- the electrolyte is selected from liquid electrolytes, gel electrolytes, polymer electrolytes or ceramic electrolytes.
- the separation membrane is polymer-based with a porous structure. Structures containing different salts such as NaCIO4 and NaPF6 at different molarity values and containing ethylene carbonate, dimethyl carbonate, ethyl methyl carbonate, and propylene carbonate in different proportions are used as electrolytes. Celgrad type polymer membranes, glass fiber membranes and their derivatives with different pore structures can be used as membranes.
- the active material to be synthesized it is mixed with Na2CO3, Mn02, Fe2O3, Co2O3, TiO and AI2O3 powders at 99% purity and stoichiometric ratios.
- the resulting sludge is then laid on a current collector foil (copper or aluminum), preferably aluminum foil, to form a layer with a thickness of 50-250 pm, approximately 200 pm.
- a current collector foil copper or aluminum
- the aluminum foil with mud on it is dried in an oven at approximately 110 oC to evaporate the NMP liquid and cathode electrode materials for disposable sodium batteries are obtained.
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention aims to provide high capacity and long-lasting use in batteries that can fall into the category of rechargeable batteries among energy storage systems; NayMn0.5- xCoxFe0.43M0.07O2 (y varies between zero and 1, x varies between zero and 1. M=Al and It is related to the active use of Ti) material as cathode. This invention aims to produce batteries from cells containing a separation membrane and electrolyte, in which the material NayMn0.5-xCoxFe0.43M0.07O2 (y varies between zero and 1, x varies between zero and 1. M = Al and Ti) is used as a cathode against an anode. Contains. It has been determined that the produced battery cell has a capacity value of 205 mAh/g and is suitable for commercial and technological uses.
Description
DESCRIPTION
RECHARGEABLE BATTERIES CONTAINING NAYMN0.5-XCOXFE0.43M0.0702 CATHODE ACTIVE
Technical Field
The invention is about the production of high capacity and long-lasting batteries by using the compound NayMn0.5-xCoxFe0.43M0.0702 (y=0-1 ; x=0-1 ; M=AI, Ti) as the cathode electrode in rechargeable sodium ion batteries.
Background Art
With increasing technological developments, the use of mobile devices that make our daily lives easier is increasing. It is seen that such mobile devices are lighter in weight and smaller in volume. As such devices become more widespread, battery systems, which are the power source of the devices, also need to keep up with this technology. Efforts to develop high-capacity and long-life batteries for Na-ion batteries, which can replace Li-ion batteries, are being intensively carried out.
Batteries are systems that store electrochemical energy and convert it into electrical energy when desired. They are systems consisting of a cathode, separation membrane and anode, and a liquid called an ionic electrolyte.
Rechargeable batteries Li-ion battery systems are very common in our daily lives and preferred in electric vehicle technology. Examples of basic cathode materials are LiCoO2, LiMn2O4, LiNi0.8Co0.15AI0.0502 and LiFePO4. The abundance of sodium compared to lithium reduces the cost of sodium ion batteries. Sodium is the second lightest and smallest alkaline element, has similar physical and chemical properties to
lithium, and is a cathode active substance that is cheap, environmentally friendly, and easier to produce. For example, NaCoO2, NaMnO2, NaFePO4, which have similar chemical properties, are known to have cathodic properties. In particular studies are being carried out to improve battery performance by partially replacing the Mn element with different transition metals in the basic structure of sodium manganese oxide, which has a P2 type crystal structure. Although different methods are preferred in the production of such materials, there are methods developed using a combination of the solid-state reaction method and the sudden cooling method.
Studies are continuing to increase the capacity of sodium ion batteries and prevent their losses. For example, the national patent application no. TR2021/014298 describes NTP powder produced to provide a high-performance sodium ion battery. In the national patent application no. TR2021/003028, air-stable metal oxides to be used as cathode active materials for sodium ion batteries are described.
As a result, today, studies on cathode active materials are continuing in sodium ion batteries to produce high-capacity and long-lasting batteries, but due to the inadequacy of existing solutions on the subject, it has become necessary to make a development in the relevant technical field.
Summary of Invention
The invention is inspired by current situations and aims to solve the above-mentioned drawbacks.
The invention is based on the material NayMn0.5-xCoxFe0.43M0.0702 (y varies between zero and 1 , x varies between zero and 1. M=AI and Ti), which can give an average starting potential of 2-3 volts after the first battery is created; It is aimed to produce battery cells between 1.5 volts and 4.3 volts. It has been determined that the produced battery cell has a capacity value of 205 mAh/g and is suitable for commercial and technological uses.
An aim of the invention is to produce a cathode active compound NayMn0.5- xCoxFe0.43M0.07O2 (y varies between zero and 1 , x varies between zero and 1. M = Al and Ti) that can be used in sodium ion batteries.
An aim of the invention is to use the material NayMn0.5-xCoxFe0.43M0.0702 (y varies between zero and 1 , x varies between zero and 1 . M = Al and Ti) as the cathode and the battery designed as the cathode/separating membrane/anode. It involves producing rechargeable batteries by stacking cells.
In order to fulfill the above objectives, the invention aims to produce a rechargeable sodium ion battery; NayMn0.5-xCoxFe0.43M0.0702 (y varies between zero and 1 , x varies between zero and 1. M=AI and Ti) material; Metal alloys with the formula AxBy, specified in the periodic table, oxide compounds based on the formula AxByOz (A: Earth and/or Alkali Metal, B: Transition metal or metals, 0: oxygen | 0<x,y,z<5), nonmetal-based alloys or They are used as anode or cathode electrode material against oxide compounds and are rechargeable batteries produced as a result of this use.
The structural and characteristic features and all the advantages of the invention will be more clearly understood thanks to the figures given below and the detailed description written with references to these figures, and therefore the evaluation should be made by taking these figures and the detailed explanation into consideration.
Brief Description of Drawings
Figure-1.1 : X-ray diffraction pattern of NayMn0.5-xCoxFe0.43AI0.0702
material.
Figure-1.2: X-ray diffraction pattern of NayMn0.5-xCoxFe0.43AI0.0702
material.
Figure-1.3: X-ray diffraction pattern of NayMn0.5-xCoxFe0.43AI0.0702
material.
Figure-1.4: X-ray diffraction pattern of NayMn0.5-xCoxFe0.43AI0.0702 (x=0.08) material.
Figure-1.5: X-ray diffraction pattern of NayMn0.5-xCoxFe0.43AI0.0702 (x=0.1) material.
Figure-1.6: X-ray diffraction pattern of NayMn0.5-xCoxFe0.43Ti0.0702 (x=0.02) material.
Figure-1.7: X-ray diffraction pattern of NayMn0.5-xCoxFe0.43Ti0.0702 (x=0.04) material.
Figure-1.8: X-ray diffraction pattern of NayMn0.5-xCoxFe0.43Ti0.0702 (x=0.06) material.
Figure-1.9: X-ray diffraction pattern of NayMn0.5-xCoxFe0.43Ti0.0702 (x=0.08) material.
Figure-1.10: X-ray diffraction pattern of NayMn0.5-xCoxFe0.43Ti0.0702 (x=0.1) material.
Figure-2.1 : CV measurements of NayMn0.5-xCoxFe0.43AI0.0702 (x=0.02) Battery.
Figure-2.2: CV measurements of NayMn0.5-xCoxFe0.43AI0.0702 (x=0.04) Battery.
Figure-2.3: CV measurements of the NayMn0.5-xCoxFe0.43AI0.0702 (x=0.06) battery.
Figure-2.4: CV measurements of the NayMn0.5-xCoxFe0.43AI0.0702 (x=0.08) battery.
Figure-2.5: CV measurements of NayMn0.5-xCoxFe0.43AI0.0702 (x=0.1) Battery.
Figure-2.6: CV measurements of the NayMn0.5-xCoxFe0.43Ti0.0702 (x=0.02) battery.
Figure-2.7: CV measurements of the NayMn0.5-xCoxFe0.43Ti0.0702 (x=0.04) battery.
Figure-2.8: CV measurements of the NayMn0.5-xCoxFe0.43Ti0.0702 (x=0.06) battery.
Figure-2.9: CV measurements of the NayMn0.5-xCoxFe0.43Ti0.0702 (x=0.08) battery.
Figure-2.10: CV measurements of the NayMn0.5-xCoxFe0.43Ti0.0702 (x=0.1) battery.
Figure-3.1 : Charge/discharge speed-rate measurements of NayMn0.5- xCoxFe0.43AI0.07O2 (x=0.02, 0.04, 0.06, 0.08, 0.10) batteries under different current values.
Figure-3.2: NayMn0.5-xCoxFe0.43Ti0.0702 (x=0.02, 0.04, 0.06, 0.08, 0.10) batteries
Charge/discharge speed-rate measurements under different current values.
Figure-4.1 : Charge/discharge measurements of NayMn0.5-xCoxFe0.43AI0.0702 (x=0.02, 0.04, 0.06, 0.08, 0.10) batteries under constant current values under 100 cycles.
Figure-4.2: Charge/discharge measurements of NayMn0.5-xCoxFe0.43Ti0.0702 (x=0.02, 0.04, 0.06, 0.08, 0.10) batteries under constant current values under 100 cycles.
Detailed Description of the Invention
In this detailed description, the rechargeable sodium ion batteries and their preferred embodiments, which are the subject of the invention, are explained only for a better understanding of the subject.
The invention aims to produce a rechargeable sodium ion battery; NayMn0.5- xCoxFe0.43M0.07O2 (y varies between zero and 1 , x varies between zero and 1. M=AI and Ti) material; Metal alloys with the formula AxBy, specified in the periodic table, oxide compounds based on the formula AxByOz (A: Earth and/or Alkali Metal, B: Transition metal or metals, 0: oxygen | 0<x,y,z<5), nonmetal-based alloys or It is also related to its use as an anode or cathode electrode material against oxide compounds.
The NayMn0.5-xCoxFe0.43M0.0702 (y=0-1 ; x=0-1 ; M=AI,Ti) material mentioned here is suitable for battery construction without damaging its structural properties; single crystal, thin film (coatings less than 1 um thick using systems such as e-beam, electroplating, atomic layer coating, sputter, thermal evaporator), thick film (coatings more than 1 um thick produced by methods such as dipping, sol-gel, spraying) and It has a structure that can be converted into polycrystalline (powders produced from solid state synthesis, hydrothermal methods, glass ceramic methods) phases.
Within the scope of the invention, rechargeable (secondary) sodium battery production with NayMn0.5-xCoxFe0.43M0.0702 (y=0-1 ; x=0-1 ; M=AI, Ti) material is carried out in its most basic form with the following steps:
I. Preparation of cathode elemental powders in the desired phase in accordance with the stoichiometry of NayMn0.5-xCoxFe0.43M0.0702 (y=0-1 ; x=0-1 ; M=AI,Ti); ii. Preparation of electrode mud by adding binder and conductor additives in powder form to the prepared cathode powders and mixing them in a solvent; iii. coating the prepared electrode mud on both surfaces of a current collector conductive layer, subjecting it to heat treatment and forming it into an electrode form; iv. Bringing the chemical powders selected as the opposite electrode anode into electrode form by following process steps ii and iii; v. stacking the obtained cathode electrodes and anode electrodes in the form of cells with an insulating membrane between them; vi. assembly of cells in the selected battery type in the presence of an electrolyte.
In the process step (i), the phase mentioned is selected among single crystal, thin film, thick film and polycrystalline phases suitable for battery construction.
(ii) the conductive additive mentioned in the process step contains one or more chemical powders selected from hard carbon (HC), carbon black (CB) or other carbon derivatives. Preferably carbon black is used.
(ii) said binder mentioned in the processing step; It contains one or more of polyvinylidene fluoride (PVDF), Styrene butadiene rubber (SBR), Carboxy methyl cellulose (CMC) powders. Preferably Polyvinylidene fluoride is used.
(ii) The current collector conductive layer mentioned in the process step is a metal foil such as aluminum, copper, etc. Preferably aluminum foil is used.
(iv) In the process step, the anode electron contains one or more of the chemical powders mentioned among the chemical powders of hard carbon (HC), carbon black (CB) or other carbon derivatives. Preferably hard carbon is used.
(vii) the rechargeable battery cell mentioned in the process step is a pouch cell, prismatic cell or cylindrical cell. The electrolyte is selected from liquid electrolytes, gel electrolytes, polymer electrolytes or ceramic electrolytes. The separation membrane is polymer-based with a porous structure. Structures containing different salts such as NaCIO4 and NaPF6 at different molarity values and containing ethylene carbonate, dimethyl carbonate, ethyl methyl carbonate, and propylene carbonate in different proportions are used as electrolytes. Celgrad type polymer membranes, glass fiber membranes and their derivatives with different pore structures can be used as membranes.
For example, in battery production, NayMn0.5-xCoxFe0.43M0.0702 (y=0-1 ; x=0-1 ; M=AI,Ti) powders are used to prepare the polycrystalline phase by solid state reaction and sudden cooling; In NayMn0.5- xCoxFe0.43M0.07O2 (y=0-1 ; x=0-1 ; M=AI,Ti) compounds, molar Al, Ti and Co elements are added. For the active material to be synthesized, it is mixed with Na2CO3, Mn02, Fe2O3, Co2O3, TiO and AI2O3 powders at 99% purity and stoichiometric ratios. It is then turned into tablets, heat treated at 900
OC for 12 hours, then cooled suddenly and cathode powders are produced at room temperature. Here, different x and y values are determined, and the doping process is carried out by calculating Na2CO3, Mn02, Fe2O3, Co2O3, TiO and AI2O3 materials in accordance with the chemical formula.
Powdered NayMn0.5-xCoxFe0.43M0.0702 (y=0-1 ; It is weighed in ratios such as: 10%: 10% and mixed mechanically until a homogeneous mixture is obtained.
The resulting sludge is then laid on a current collector foil (copper or aluminum), preferably aluminum foil, to form a layer with a thickness of 50-250 pm, approximately 200 pm. Following this process, the aluminum foil with mud on it is dried in an oven at approximately 110 oC to evaporate the NMP liquid and cathode electrode materials for disposable sodium batteries are obtained.
NayMn0.5-xCoxFe0.43M0.0702 (y=0-1 ; In an oxygen-free environment filled with Ar (Argon) gas; battery bottom cover, NayMn0.5-xCoxFe0.43M0.0702 (y=0-1 ; x=0-1 ; M=AI,Ti) electrode as cathode, electrolyte liquid, membrane, electrolyte liquid, hard carbon and derivatives as anode and separator membrane, rechargeable battery is formed in the battery top cover configuration. Metal foils such as Aluminum, copper etc. are used as current collectors for the anode and cathode.
The invention also includes serial or parallel connection of similar types of electrodes produced by the method described above in a battery container.
It can be seen from the XRD diffraction pattern of the samples produced with the invention figures 1.1-1.10 that their structures are formed in the P63/mmc phase. Figures 2.1-2.10 are the CV analysis results obtained when the produced cathode materials are used in cylindrical, prismatic, bladder type and CT2032 type batteries in the cathode-electrolyte-anode composition. Figures 3.1 and 3.2 show the capacity values obtained at different current densities of the battery cells to be produced, and Figures 4.1 and 4.1 show the change in capacities over 100 cycles.
Claims
1. In order to produce rechargeable sodium ion batteries; NayMn0.5- xCoxFe0.43M0.07O2 (y varies between zero and 1 , x varies between zero and 1. M=AI and Ti) material; Metal alloys with the formula AxBy, specified in the periodic table, oxide compounds based on the formula AxByOz (A: Earth and/or Alkali Metal, B: Transition metal or metals, 0: oxygen | 0<x,y,z<5), nonmetalbased alloys or Its use as an anode or cathode electrode material against oxide compounds.
2. It is a use in accordance with claim 1 ; feature; NayMn0.5-xCoxFe0.43M0.0702 (y varies between zero and 1 , x varies between zero and 1. M=AI and Ti) material; It can be converted into single crystal, thin film, thick film and polycrystalline phases suitable for battery production, without deteriorating its structural properties.
3. It is a rechargeable battery containing cathode electrode NayMn0.5- xCoxFe0.43M0.07O2 (y varies between zero and 1 , x varies between zero and 1. M = Al and Ti).
4. NayMn0.5-xCoxFe0.43M0.0702 (y varies between zero and 1 , x varies between zero and 1. M=AI and Ti) material; Metal alloys with the formula AxBy, specified in the periodic table, oxide compounds based on the formula AxByOz (A: Earth and/or Alkali Metal, B: Transition metal or metals, 0: Oxygen | 0<x,y,z<5), nonmetal-based alloys or It is a rechargeable battery production in which oxide anode compounds are used as cathode electrodes, and its feature is; It includes the following process steps: i. preparation of cathode elemental powders in the desired phase in accordance with the stoichiometry of NayMn0.5-xCoxFe0.43M0.0702 (y=0-1 ; x=0-1 ; M=AI, Ti); ii. preparation of electrode mud by mixing binder and conductive additive in powder form to the prepared cathode powders and adding a solvent; iii. laying the prepared electrode mud on a current collector conductive layer, subjecting it to heat treatment to form an electrode, shaping it to the desired size;
iv. bringing the chemical powders selected as the opposite electrode anode into electrode form by following process steps ii and iii; v. stacking the obtained cathode electrodes and anode electrodes in the form of cells with an insulating membrane between them; vi. assembly of cells in the selected battery type in the presence of an electrolyte.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| TR2022021841 | 2022-12-30 | ||
| TR2022/021841 TR2022021841A2 (en) | 2022-12-30 | Rechargeable Batteries Containing NayMn0.5-xCoxFe0.43M0.07O2 Cathode Active |
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| Publication Number | Publication Date |
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| WO2024144725A1 true WO2024144725A1 (en) | 2024-07-04 |
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| Application Number | Title | Priority Date | Filing Date |
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| PCT/TR2023/051767 WO2024144725A1 (en) | 2022-12-30 | 2023-12-28 | Rechargeable batteries containing naymn0.5-xcoxfe0.43m0.07o2 cathode active |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1999053556A1 (en) * | 1998-04-09 | 1999-10-21 | Danionics A/S | Rechargeable lithium electrochemical cell |
| US20170222224A1 (en) * | 2014-12-23 | 2017-08-03 | Sharp Kabushiki Kaisha | Layered oxide materials for batteries |
| CN112886084A (en) * | 2021-01-13 | 2021-06-01 | 上海紫剑化工科技有限公司 | Method for repairing layered oxide positive electrode material of sodium ion battery |
| CN114477233A (en) * | 2022-02-16 | 2022-05-13 | 温州大学碳中和技术创新研究院 | Preparation method of high-entropy polymetallic Prussian blue and analogues thereof and sodium-ion battery |
| CN115395083A (en) * | 2022-07-04 | 2022-11-25 | 浙江超威创元实业有限公司 | Novel battery pack |
-
2023
- 2023-12-28 WO PCT/TR2023/051767 patent/WO2024144725A1/en unknown
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1999053556A1 (en) * | 1998-04-09 | 1999-10-21 | Danionics A/S | Rechargeable lithium electrochemical cell |
| US20170222224A1 (en) * | 2014-12-23 | 2017-08-03 | Sharp Kabushiki Kaisha | Layered oxide materials for batteries |
| CN112886084A (en) * | 2021-01-13 | 2021-06-01 | 上海紫剑化工科技有限公司 | Method for repairing layered oxide positive electrode material of sodium ion battery |
| CN114477233A (en) * | 2022-02-16 | 2022-05-13 | 温州大学碳中和技术创新研究院 | Preparation method of high-entropy polymetallic Prussian blue and analogues thereof and sodium-ion battery |
| CN115395083A (en) * | 2022-07-04 | 2022-11-25 | 浙江超威创元实业有限公司 | Novel battery pack |
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