WO2020174487A1 - Microwave assisted sol-gel process for preparing in-situ carbon coated electrode materials and the product thereof - Google Patents
Microwave assisted sol-gel process for preparing in-situ carbon coated electrode materials and the product thereof Download PDFInfo
- Publication number
- WO2020174487A1 WO2020174487A1 PCT/IN2020/050143 IN2020050143W WO2020174487A1 WO 2020174487 A1 WO2020174487 A1 WO 2020174487A1 IN 2020050143 W IN2020050143 W IN 2020050143W WO 2020174487 A1 WO2020174487 A1 WO 2020174487A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- sodium
- precursor
- electrode materials
- carbon coated
- coated electrode
- Prior art date
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 59
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 55
- 239000007772 electrode material Substances 0.000 title claims abstract description 53
- 238000011065 in-situ storage Methods 0.000 title claims abstract description 32
- 238000003980 solgel method Methods 0.000 title claims abstract description 24
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 43
- 239000002243 precursor Substances 0.000 claims abstract description 43
- 150000002500 ions Chemical class 0.000 claims abstract description 38
- 239000003513 alkali Substances 0.000 claims abstract description 37
- 239000011734 sodium Substances 0.000 claims abstract description 31
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 20
- 229910000319 transition metal phosphate Inorganic materials 0.000 claims abstract description 18
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 17
- 150000003624 transition metals Chemical class 0.000 claims abstract description 17
- 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 claims abstract description 16
- 238000001879 gelation Methods 0.000 claims abstract description 12
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 12
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 12
- 229910052742 iron Inorganic materials 0.000 claims abstract description 11
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 11
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 11
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 9
- DWYMPOCYEZONEA-UHFFFAOYSA-L fluoridophosphate Chemical compound [O-]P([O-])(F)=O DWYMPOCYEZONEA-UHFFFAOYSA-L 0.000 claims abstract description 8
- 230000005855 radiation Effects 0.000 claims abstract description 8
- 239000002904 solvent Substances 0.000 claims abstract description 8
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 5
- 238000001035 drying Methods 0.000 claims abstract description 5
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 5
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000008367 deionised water Substances 0.000 claims abstract description 4
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 4
- 239000011737 fluorine Substances 0.000 claims abstract description 4
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 3
- 238000000227 grinding Methods 0.000 claims abstract description 3
- 229910001415 sodium ion Inorganic materials 0.000 claims description 34
- ZMVMBTZRIMAUPN-UHFFFAOYSA-H [Na+].[V+5].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O Chemical compound [Na+].[V+5].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O ZMVMBTZRIMAUPN-UHFFFAOYSA-H 0.000 claims description 31
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims description 29
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 25
- 239000000203 mixture Substances 0.000 claims description 20
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 18
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 claims description 18
- CHQMXRZLCYKOFO-UHFFFAOYSA-H P(=O)([O-])([O-])F.[V+5].[Na+].P(=O)([O-])([O-])F.P(=O)([O-])([O-])F Chemical compound P(=O)([O-])([O-])F.[V+5].[Na+].P(=O)([O-])([O-])F.P(=O)([O-])([O-])F CHQMXRZLCYKOFO-UHFFFAOYSA-H 0.000 claims description 14
- 229910020650 Na3V2 Inorganic materials 0.000 claims description 13
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- 239000012298 atmosphere Substances 0.000 claims description 8
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 7
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 7
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- RGHNJXZEOKUKBD-SQOUGZDYSA-N D-gluconic acid Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 claims description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- 229910021541 Vanadium(III) oxide Inorganic materials 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 6
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical group [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 6
- 229910000403 monosodium phosphate Inorganic materials 0.000 claims description 6
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- KFAFTZQGYMGWLU-UHFFFAOYSA-N oxo(oxovanadiooxy)vanadium Chemical compound O=[V]O[V]=O KFAFTZQGYMGWLU-UHFFFAOYSA-N 0.000 claims description 6
- 229920001223 polyethylene glycol Polymers 0.000 claims description 6
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical group [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- WQEVDHBJGNOKKO-UHFFFAOYSA-K vanadic acid Chemical compound O[V](O)(O)=O WQEVDHBJGNOKKO-UHFFFAOYSA-K 0.000 claims description 6
- 239000002228 NASICON Substances 0.000 claims description 5
- 229910000148 ammonium phosphate Inorganic materials 0.000 claims description 5
- 229910000162 sodium phosphate Inorganic materials 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- 229910000388 diammonium phosphate Inorganic materials 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- FSJSYDFBTIVUFD-SUKNRPLKSA-N (z)-4-hydroxypent-3-en-2-one;oxovanadium Chemical compound [V]=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O FSJSYDFBTIVUFD-SUKNRPLKSA-N 0.000 claims description 3
- 239000004254 Ammonium phosphate Substances 0.000 claims description 3
- RGHNJXZEOKUKBD-UHFFFAOYSA-N D-gluconic acid Natural products OCC(O)C(O)C(O)C(O)C(O)=O RGHNJXZEOKUKBD-UHFFFAOYSA-N 0.000 claims description 3
- 239000005696 Diammonium phosphate Substances 0.000 claims description 3
- 239000002202 Polyethylene glycol Substances 0.000 claims description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 3
- 235000019289 ammonium phosphates Nutrition 0.000 claims description 3
- 239000003125 aqueous solvent Substances 0.000 claims description 3
- 239000011668 ascorbic acid Substances 0.000 claims description 3
- 235000010323 ascorbic acid Nutrition 0.000 claims description 3
- 229960005070 ascorbic acid Drugs 0.000 claims description 3
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims description 3
- 238000009835 boiling Methods 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 235000015165 citric acid Nutrition 0.000 claims description 3
- 239000011247 coating layer Substances 0.000 claims description 3
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- 238000009826 distribution Methods 0.000 claims description 3
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- 235000006408 oxalic acid Nutrition 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- ZNCPFRVNHGOPAG-UHFFFAOYSA-L sodium oxalate Chemical compound [Na+].[Na+].[O-]C(=O)C([O-])=O ZNCPFRVNHGOPAG-UHFFFAOYSA-L 0.000 claims description 3
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- ASTWEMOBIXQPPV-UHFFFAOYSA-K trisodium;phosphate;dodecahydrate Chemical compound O.O.O.O.O.O.O.O.O.O.O.O.[Na+].[Na+].[Na+].[O-]P([O-])([O-])=O ASTWEMOBIXQPPV-UHFFFAOYSA-K 0.000 claims description 3
- GZCGUPFRVQAUEE-UHFFFAOYSA-N 2,3,4,5,6-pentahydroxyhexanal Chemical compound OCC(O)C(O)C(O)C(O)C=O GZCGUPFRVQAUEE-UHFFFAOYSA-N 0.000 claims description 2
- AEMOLEFTQBMNLQ-UHFFFAOYSA-N 3,4,5,6-tetrahydroxyoxane-2-carboxylic acid Chemical compound OC1OC(C(O)=O)C(O)C(O)C1O AEMOLEFTQBMNLQ-UHFFFAOYSA-N 0.000 claims description 2
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- 230000002708 enhancing effect Effects 0.000 description 1
- 238000000445 field-emission scanning electron microscopy Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 230000016507 interphase Effects 0.000 description 1
- 230000037427 ion transport Effects 0.000 description 1
- 239000003273 ketjen black Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000000877 morphologic effect Effects 0.000 description 1
- 229910021382 natural graphite Inorganic materials 0.000 description 1
- 239000011356 non-aqueous organic solvent Substances 0.000 description 1
- 239000010450 olivine Substances 0.000 description 1
- 229910052609 olivine Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 229910001414 potassium ion Inorganic materials 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
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- CMZUMMUJMWNLFH-UHFFFAOYSA-N sodium metavanadate Chemical compound [Na+].[O-][V](=O)=O CMZUMMUJMWNLFH-UHFFFAOYSA-N 0.000 description 1
- 229910001495 sodium tetrafluoroborate Inorganic materials 0.000 description 1
- 229910000693 sodium vanadium oxide Inorganic materials 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 229910052566 spinel group Inorganic materials 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- 238000004627 transmission electron microscopy Methods 0.000 description 1
- 230000032258 transport Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/45—Phosphates containing plural metal, or metal and ammonium
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/455—Phosphates containing halogen
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for 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
- H01M4/139—Processes of manufacture
- H01M4/1397—Processes of manufacture of electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
-
- 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
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- 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
-
- 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
- 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
-
- 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 present invention relates method for preparing electrode materials of alkali ion transition metal phosphates and the product thereof especially a method for preparing in-situ carbon coated sodium vanadium phosphate and sodium vanadium fluorophosphates and its derivatives by microwave assisted sol-gel process. They can be used as electrode materials for “supercabattery” due to their dual characteristics of high specific capacity and high specific capacitance. They can also be used as electrode material for sodium ion battery and sodium ion capacitors.
- Lithium ion batteries possess the highest specific energy among all other commercial battery systems. LIBs were successfully commercialized by Sony in 1990 for various applications such as portable electronic devices and electric/hybrid electric vehicles etc. [M. S. Whittingham, “Lithium Batteries and Cathode Materials”, Chem. Rev. (2004) 104, 4271-4302]
- Lithium resources are fast depleting and are expected to last for about few more years.
- the cost of Lithium makes the LIBs not suitable for large scale grid storage application.
- the low cost, on-par specific energy and large abundance of Sodium make sodium ion batteries (SIBs) as a suitable alternative to LIBs.
- SIBs sodium ion batteries
- Similar working principle, such as the reversible shuttling of sodium ions between electrode materials through electrolyte, to that of LIBs adds to its credentials [J. Y. Hwang, S.T. Myung, Y.K. Sun,“Sodium-ion batteries: present and future”, Chem. Soc. Rev. (2017) 46, 3529-3614; C.
- Phosphate based materials are known to be structurally and thermally stable and can be used as potential electrode materials for SIBs.
- NASCION-type structure which has open 3D ion transport channels to facilitate faster ion transportation, are widely studied as electrode materials.
- Na3V2(PC>4)3 of NASICON-type structure is an example of promising cathode material with a flat voltage plateau at ⁇ 3.4 V vs. Na/Na + and high reversible capacity of 1 18 mAh/g. Flowever, the poor electronic conductivity associated with it causes capacity degradation.
- microwave assisted solid state synthesis route has been adopted to prepare a composite of phosphodiesterase sodium vanadium oxide/ alkenyl and graphite (CN104078676B, CN104078676A) and different metal containing compounds for lithium, sodium and potassium ion batteries (KR20150080652A), as reported elsewhere.
- microwave assisted solid state synthesis has been adopted to prepare these electrode active materials in bulk quantities, it may lead to electrode materials of lesser phase purity, inhomogeneity and non-stoichiometric in compositions compared to solution-based synthesis routes such as, hydrothermal, solvothermal and sol-gel synthesis etc.
- Solution based microwave assisted sol-gel synthesis has various advantages over other synthesis routes, such as a) Volumetric heating: Generally solvent and solute components of the solution absorb the microwave radiation rather than transmitting or reflecting as in case of gases and solids respectively. This leads to the uniform and rapid heating of the solution components, which results in faster reaction rates. b) Uniform gelation: Especially in a solution mode, microwaves generate rapid charging fields such as dipoles in the solvent which will be aligned continuously in the field direction to produce the heat. This heat will be uniformly distributed to get the localized superheating, which will reduce the defects/impurities by enhancing the purity of the material.
- the objective of the present invention is to provide a quicker synthesis route for the preparation of in-situ carbon coated alkali ion transition metal phosphates and their derivatives as potential electrode materials.
- the main objective of the present invention is, therefore to prepare in-situ carbon coated sodium vanadium phosphate/fluorophosphates embedded in mesoporous carbon network via microwave assisted sol-gel route with high storage performance.
- Another objective of the present invention is to provide uniform carbon coated sodium vanadium phosphate/fluorophosphates with controlled particle size.
- Yet another objective of the present invention is to provide large scale synthesis of uniform carbon coated sodium vanadium phosphate/fluorophosphates with controlled particle size.
- Yet another objective of the present invention is to provide the use of prepared electrode active materials in sodium ion battery, sodium ion capacitor and sodium ion supercabattery.
- the present invention relates method for preparing in-situ carbon coated electrode materials by microwave assisted sol-gel process and the product thereof.
- the electrode material is selected from alkali ion transition metal phosphates and alkali ion transition metal fluorophosphate having the general formula [A3M2(P04)3] and [A3M2(P04)2F3] wherein‘A’ is an alkali ion selected from Li, Na and K ; M is a transition metal selected from Fe, Ni, Co, V, Mn, Ti, and Cr.
- the process of synthesis comprising the following steps: a) mixing by adding an alkali ion precursor, a transition metal precursor, a phosphorus precursor, and a gelating / chelating agent in a ratio of 3:2:3:2 b) while alkali ion precursor, the phosphorus precursor and the chelating agent are taken based on corresponding molar ratios considering the amount of the transition metal precursor in an deionized water or non- aqueous solvent selected from ethylene glycol, polyethylene glycol, tetraethylene glycol and solvents which have relatively low to moderate boiling point in vessel; c) stirring the said mixture in the vessel for a period of so as to obtain a homogenous mixture; d) subjecting to microwave radiation in an open vessel, with constant stirring at a fixed temperature resulting homogenous gelation at a temperature range from 80 to 170 °C under atmospheric pressure; e) drying the resultant gel at a temperature range from 100 to 120 °C in air; f) grinding the dried gel
- the alkali ion transition metal phosphates is sodium vanadium phosphate [Na3V2(PC>4)3] and the constituents added in the mix of step a) are sodium precursor is selected from the group consisting of sodium dihydrogen phosphate (NaH2PC>4), sodium acetate dihydrate (CH3C00Na.2H20), sodium hydroxide monohydrate (Na0H.H20), sodium hydroxide (NaOH), sodium carbonate (Na2CC>3), sodium phosphate (Na3PC>4), sodium phosphate dodecahydrate (Na3P04.12H20), sodium oxalate (Na2C2C>4), and a mixture thereof; vanadium precursor selected from the group consisting of, vanadium (V) oxide (V2O5), ammonium metavanadate (NH4VO3), vanadium (III) oxide (V2O3), vanadyl acetylacetonate [V0(CsH702)2], tri
- One aspect of the invention also involves drying the gel formed during microwave synthesis in an ambient atmosphere at a fixed temperature and further subjecting it to a two-stage heat treatment under inert atmosphere.
- Another aspect of this invention is the drastic reduction in the reaction time for the gel formation.
- Another aspect of this invention includes the formation of in-situ carbon coating onto sodium vanadium phosphate and sodium vanadium fluorophosphate electrode material, obtained through microwave assisted sol-gel method.
- Another aspect of this invention is the synthesis of uniform and controlled particle size via microwave assisted sol-gel route.
- Another aspect of this invention focuses on the scalability of this process. This route facilitates large scale synthesis of desired electrode materials.
- Another aspect of this invention is the application of the synthesized electrode material in a sodium ion battery, sodium ion symmetric cell and hybrid supercapacitors due to their long-term cycling stability and high specific energy.
- Another aspect of this invention is the application of the synthesized electrode materials in“Supercabattery” owing to their high power density at high specific energy compared to conventional supercapacitors.
- microwave sol- gel is an efficient method to prepare homogeneous gel within a very short reaction time.
- a long time for gelation is overruled to reduce the cost.
- sodium vanadium phosphate and sodium vanadium fluorophosphate with uniform and controlled particle size distribution may be easily achieved.
- This carbon coated electrode materials have wide industrial applications. It is used in the manufacturing of sodium ion cells/ battery, supercabattery and sodium ion capacitors.
- Fig.1 a is an X-ray diffraction (XRD) pattern of carbon coated sodium vanadium phosphate.
- Fig.1 b is an X-ray diffraction (XRD) pattern of carbon coated sodium vanadium fluorophosphate prepared according to an embodiment of the present invention (Example 1 and 2).
- XRD X-ray diffraction
- Fig. 2a is a photographic image of a scanning electron microscope (SEM) of carbon coated sodium vanadium phosphate.
- Fig. 2b is a photographic image of a scanning electron microscope (SEM) of carbon coated sodium vanadium fluorophosphate prepared according to an embodiment of the present invention (Example 1 and 2).
- SEM scanning electron microscope
- Fig. 3 is a photographic image of a transmission electron microscope (TEM) of carbon coated sodium vanadium phosphate prepared according to an embodiment of the present invention (Example 1 ).
- TEM transmission electron microscope
- Fig. 4 represents the cyclic voltammogram (CV) of carbon coated sodium vanadium phosphate at a constant scan rate (100 pV/s) in the voltage window of 2.3-3.9 V vs. Na/Na + .
- Fig. 6 is the comparison of the specific capacity vs. cycle number plots for carbon coated sodium vanadium phosphate at 0.1 C-rate in different voltage windows.
- Fig. 7 represents the galvanostatic charge/discharge cycling plots for carbon coated sodium vanadium phosphate symmetrical cells cycled at 0.1 and 1.0 A/g in the voltage window of 0 -3 V.
- Fig. 8 represents the specific capacity vs. cycle number plots for carbon coated sodium vanadium phosphate symmetrical cells at 0.1 A/g up to 100 cycles and at 1 A/g up to 1400 cycles in the voltage window of 0-3 V.
- Fig. 9a represents the galvanostatic charge-discharge cycling plots for carbon coated sodium vanadium phosphate supercapacitor at various current densities in the potential window of 0-3 V.
- Fig.9b shows specific capacitance vs. current density plots for carbon coated sodium vanadium phosphate supercapacitor.
- Fig. 10 represents the cyclic voltammogram (CV) of carbon coated sodium vanadium fluorophosphate at a constant scan rate (100 pV/s) in the voltage window of 2.5-4.5 V vs. Na/Na + .
- Fig. 12. represents specific capacity vs. cycle number plot for carbon coated sodium vanadium fluorophosphate at 1 C-rate in the potential window of 2.5-4.5 V vs. Na/Na + .
- the present invention focuses on a novel Microwave assisted sol-gel process for preparing in-situ carbon coated alkali ion transition metal phosphate electrode active materials and its derivatives such as alkali ion transition metal phosphates and alkali ion transition metal fluorophosphate having the general formula [A3M2(PC>4)3] and [A3M2(PC>4)2F3] respectively wherein‘A’ is an alkali ion selected from Li, Na and K ; M is a transition metal selected from Fe, Ni, Co, V, Mn, Ti, Cr.
- This method addresses the safety issue, prolonged reaction time, formation of phase pure materials and also the reduction in the cost compared to other synthesis routes, such as solid-state reaction, hydrothermal, conventional sol-gel, electrospinning and freeze drying etc.
- a synthesis route involves (a) preparing a homogeneous solution by adding an alkali ion precursor, a transition metal precursor, a phosphorus precursor, a gelating/ chelating agent in an aqueous/non-aqueous solvent; (b) A stirring step may be additionally carried out to achieve the homogeneous solution of added precursors such as, alkali ion precursor, transition metal precursor, the phosphorus precursor and the gelating agent (c) The mixture solution may be put into an open vessel and exposed to microwave radiation to prepare the gel under ambient pressure (d) The vessel used may be an open vessel. No specific pressure conditions are required unlike the hydrothermal synthesis, supercritical hydrothermal synthesis or solvothermal synthesis, where a pressure-resistant vessel is compulsory in order to perform the reaction successfully.
- reaction solvents may be either aqueous such as deionized H2O or non-aqueous such as ethylene glycol, polyethylene glycol, tetraethylene glycol and solvents which have relatively low to moderate boiling point.
- the gelation may be carried out in a temperature range from 80 to 170 °C under atmospheric pressure.
- the obtained gel may be dried at a temperature range from 100 to 120 °C in air. The dried gel is then grinded and subjected to a two-stage heat treatment.
- the heat treatment is not specifically limited and may be conducted by calcining the gel at a temperature range from 600 to 800 °C for a period of 8 to 10 hours under an inert atmosphere with an intermediate calcination temperature of 300 to 500 Q C for 3 to 5 hours.
- the inert atmosphere may be but not limited to Argon and N2.
- an in-situ carbon coating layer may be formed on the alkali ion transition metal phosphate along with formation of mesoporous carbon network.
- sodium vanadium phosphate [Na3V2(PC>4)3] active cathode material has been synthesized using the microwave-assisted sol-gel process.
- the sodium precursor thus added may be at least one selected from the group consisting of sodium dihydrogen phosphate (NaF PC ), sodium acetate dihydrate (CH3C00Na.2H20), sodium hydroxide monohydrate (NaOH.FteO), sodium hydroxide (NaOH), sodium carbonate (Na2CC>3), sodium phosphate (Na3PC>4), sodium phosphate dodecahydrate (Na3P04.12H20), sodium oxalate (Na2C2C>4), and a mixture thereof.
- NaF PC sodium dihydrogen phosphate
- CH3C00Na.2H20 sodium acetate dihydrate
- NaOH.FteO sodium hydroxide monohydrate
- NaOH sodium carbonate
- Na2CC>3 sodium phosphate
- Na3PC>4 sodium phosphate dodecahydrate
- Na2C2C>4 sodium oxalate
- the vanadium precursor added may be at least one selected from the group consisting of, vanadium (V) oxide (V2O5), ammonium metavanadate (NH4VO3), vanadium (III) oxide (V2O3), vanadyl acetylacetonate [ VO (C5H 702)2], trihydroxy (oxo) vanadium (H3VO4) and a mixture thereof.
- the phosphorus precursor added may be at least one selected from the group consisting of ammonium phosphate [(NH4)3P04], diammonium phosphate [(NH4)2HP04], ammonium dihydrogen phosphate (NH4H2PO4), phosphoric acid (H3PO4), sodium dihydrogen phosphate (NaH2P04) and a mixture thereof.
- the gelating/chelating precursor which is used as source for in-situ carbon coating and mesoporous carbon network. It may be at least one selected from the group consisting of citric acid, ascorbic acid, oxalic acid, gluconic acid etc.
- organic precursors which may be used for in-situ carbon coating.
- organic precursors are not specifically limited and may be at least one selected from the group consisting of glucose, sucrose, galactose, fructose, lactose, starch, mannose, ribose, aldohexose, ketohexose, and a combination thereof.
- the mixing ratio of the sodium precursor, the vanadium precursor, the phosphorus precursor and the chelating agent during the solution preparation is maintained at 3:2:3:2.
- the sodium precursor, the phosphorus precursor and the chelating agent may be added by corresponding molar ratios considering the amount of the vanadium precursor.
- the gelation for sodium vanadium phosphate may be carried out at a temperature 80 °C.
- the obtained gel maybe dried at 120 °C in an ambient atmosphere.
- the final calcination may be carried out at a temperature of 800 °C for 10 hrs under argon atmosphere with an intermediate calcination at 400 Q C for 4 hrs.
- sodium vanadium flourophosphate [Na3V2(P04)2F3] as an active cathode material may be synthesized using the microwave-assisted sol-gel process.
- the fluorine precursor added may be at least one selected from the group consisting of NaF, NFUF and NFl4FIF2 and a mixture thereof.
- the above-mentioned process steps may be extended for the preparation of cation doped alkali ion transition metal phosphates with general formula A3M2-xCx(PC>4)3; 0 ⁇ x ⁇ 2, where C may be any one of Mg, Al, Ti, Ca, Sc etc.
- the above-mentioned process steps may be extended for the preparation of anion doped alkali ion transition metal phosphates with general formula A3M2(P04)3-yN3y; 0 ⁇ y ⁇ 1 and A3M2- xCx(P04)3-yl ⁇ l3y; 0 ⁇ x ⁇ 2, 0 ⁇ y ⁇ 1 where N may be any one of these Cl, Br, I etc.
- the sodium vanadium phosphate/fluorophosphate particles prepared through the series of the above described steps may have a NASICON (Na Super Ionic CONductor) type of rhombohedral/tetragonal crystal structure as confirmed from the X-ray diffraction patterns ( Figurel (a) & (b)) ⁇
- NASICON Na Super Ionic CONductor
- the particle size and its distribution may be controlled by changing the content of gelating/chelating agent, or regulating process parameters such as reaction temperature and reaction time, etc.
- the sodium vanadium phosphate and sodium vanadium fluorophosphate prepared through the above stated method may possess particle size in the range of 300-500 and 30-50 nm respectively, as shown in Figure 2.
- the thickness of the carbon coating formed on the surface of the sodium vanadium phosphate and sodium vanadium fluorophosphate is not limited and may be ⁇ 10 nm as shown in Figure 3.
- the electrode material is a composite which includes cathode active material, conductive agent and a binder in appropriate ratios.
- the conductive agent may include any material having good electronic conductivity such as graphite in form of natural graphite and synthetic graphite; amorphous carbon in form of carbon black, acetylene black, ketjen black; carbon fibers, carbon nanotubes and graphene etc.
- the conductive agent may be added by 1 to 15 wt. % based on the total amount of the mixture including the cathode active material.
- the binder may be any component that gives mechanical stiffness and helps to bind the active material particles together and also with the current collector, may include polyvinylidene fluoride, polyvinyl alcohol, carboxymethyl cellulose, polyvinyl pyrrolidone, tetrafluoroethylene, etc.
- the binder may be added by 1 to 15 wt. % based on the total amount of a mixture including the cathode active material.
- the electrode for the sodium ion battery may be fabricated by, for example, dissolving the cathode active material, conducting agent and binder in a solvent, e.g. non-aqueous NMP (N-methyl-2- pyrrolidone)/aqueous (H2O) solvent to prepare slurry and coating the slurry onto the current collector followed by drying and calendaring.
- a solvent e.g. non-aqueous NMP (N-methyl-2- pyrrolidone)/aqueous (H2O) solvent
- the current collector may be any material having good electronic conductivity and may include stainless steel, aluminum, copper, nickel, carbon film or a surface treated material such as aluminum or stainless steel with carbon etc.
- fabrication of a sodium ion battery may include a cathode, an anode (may be Na metal, but not limited), a separator and a non-aqueous electrolyte containing a sodium salt.
- the non-aqueous organic solvent for electrolyte may include aprotic organic solvents such as propylene carbonate, ethylene carbonate, dimethyl carbonate, diethyl carbonate and their derivatives, etc.
- the sodium salt materials which are preferably soluble in the non-aqueous electrolyte may include NaCIC , NaBF4, NaPF6, NaCF3SC>3, NaCF3CC>2, CF3S03Na, and (CF3S02)2NNa etc.
- aqueous electrolytes may also be used in the fabrication of the sodium ion battery.
- a sodium ion battery containing the prepared sodium vanadium phosphate as cathode active material displays high specific capacity and cyclic stability ( Figure 4, 5 and 6).
- a sodium ion capacitor containing the prepared sodium vanadium phosphate as cathode and anode shows high specific capacity, specific capacitance and cyclic stability ( Figure 7, 8 and 9).
- a sodium ion battery containing the prepared sodium vanadium fluorophosphate as cathode active material displays high specific capacity and cyclic stability. ( Figure 10, 1 1 and 12).
- the active materials developed through microwave assisted sol-gel method finds its application as an electrode active material for alkali ion batteries, alkali ion capacitors and in supercabattery devices.
- NaFl2P04.2Fl20 [99%, Sigma Aldrich], NFI4VO3 [98%, Loba Chemie] and citric acid (ObHIdOz) [99.5%, Sigma Aldrich] NaFl2P04.2Fl20 was added to de-ionized water and ultra-sonicated for 5 minutes until it was completely dissolved to form a clear solution.
- Sodium vanadium fluorophosphate, Na3V2(PC>4)2F3 was prepared by the microwave assisted sol-gel route similar to that of Na3V2(PC>4)3 using NaF [Merck 99%], NH4H2PO4 [Sigma Aldrich 98.5%], NH4VO3 [Loba Chemie 98%] and Citric acid [Merck 99.5%] as the precursors. Stoichiometric amounts of the precursors were mixed in Dl water and transferred to an open vessel and subjected to microwave reaction at constant temperature (80°C) and stirring rate until the gel was formed. The above-mentioned gel was then washed and dried in a hot air oven under ambient air, at 120 °C.
- the dried gel was crushed, ground and then subjected to a two-step heat treatment under argon atmosphere, i) 350 °C for 4 h and ii) 650°C for 6 h to obtain the phase pure, Na3V2(P04)2F3.
- various structural and morphological studies were carried out using X-Ray diffractometer (Rigaku Smartlab X-ray diffractometer with Cu-Ka radiation), scanning electron microscopy (FE-SEM; Zeiss merlin Compact) and transmission electron microscopy (TEM; Technai G20) etc.
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Abstract
The present invention relates to Microwave assisted sol-gel process for preparing in-situ carbon coated electrode materials selected from alkali ion transition metal phosphates and alkali ion transition metal fluorophosphate having the general formula [A3M2(PO4)3] and [A3M2(PO4)2F3] wherein 'A' is an alkali ion selected from Li, Na and K; 'M' is a transition metal selected from Fe, Ni, Co, V, Mn, Ti, Cr. The steps involved in the synthesis starts with preparation of a homogenous aqueous solution containing sodium precursor, vanadium precursor and phosphorous precursor using deionized water as a solvent. Fluorine precursor is used in case of 10 fluorophosphate preparation. Exposing the homogenous solution to microwave radiation in an open vessel for gelation under ambient pressure at a temperature of 80 to 170 °C under atmospheric pressure followed by drying at 100 to 120 °C in air; grinding and subjecting the formed gel to a two-stage heat-treatment to achieve phase pure sodium vanadium 15 phosphate/fluorophosphate.
Description
DESCRIPTION
FIELD OF INVENTION
The present invention relates method for preparing electrode materials of alkali ion transition metal phosphates and the product thereof especially a method for preparing in-situ carbon coated sodium vanadium phosphate and sodium vanadium fluorophosphates and its derivatives by microwave assisted sol-gel process. They can be used as electrode materials for “supercabattery” due to their dual characteristics of high specific capacity and high specific capacitance. They can also be used as electrode material for sodium ion battery and sodium ion capacitors.
BACKGROUND OF THE INVENTION
Batteries are the most preferred option as energy storage devices in terms of specific energy and power density. Lithium ion batteries (LIBs) possess the highest specific energy among all other commercial battery systems. LIBs were successfully commercialized by Sony in 1990 for various applications such as portable electronic devices and electric/hybrid electric vehicles etc. [M. S. Whittingham, “Lithium Batteries and Cathode Materials”, Chem. Rev. (2004) 104, 4271-4302]
However, Lithium resources are fast depleting and are expected to last for about few more years. In addition, the cost of Lithium makes the LIBs not suitable for large scale grid storage application. The low cost, on-par specific energy and large abundance of Sodium (being one of the primary elements in sea-water) make sodium ion batteries (SIBs) as a suitable alternative to LIBs. In addition, similar working principle, such as the reversible shuttling of sodium ions between electrode materials through electrolyte, to that of LIBs adds to its credentials [J. Y. Hwang, S.T. Myung, Y.K. Sun,“Sodium-ion batteries: present and future”, Chem. Soc. Rev. (2017) 46, 3529-3614; C. Delmas, “Sodium and Sodium-Ion Batteries: 50 Years of research”, Adv. Energy Mater. (2018) 1703137]
The sodium containing electrode materials are more stable compared to their lithium counterpart, which makes them suitable for variety of applications. The intercalation chemistry being same for both lithium and sodium, allows using similar type of compounds for SIBs. The differences between these two systems would be that sodium ions are larger compared to lithium ions, affecting the phase stability, transport properties, and solid electrolyte interphase (SEI) formation [B. Dunn, H. Kamath, J. M. Tarascon,“Electrical Energy Storage for the Grid: A battery of choices”, Science (2011 ) 334, 928-935] Various cathode materials such as layered sodium transition metal oxides, NaxMC (M= Co, Mn, Fe and Ni etc.) (0.44<x<1 ), olivine NaMP04 (M = Fe, Mn, Ni and Co), spinels NaMn2C>4 and NASICON-type (Na Super-Ionic CONductor) Na3V2(PC>4)3 have been investigated and are currently being used as electrode materials for SIBs. Oxide materials are prone to undergo oxygen evolution during charging at high states of charge (SoC), which causes severe capacity degradation. In addition, poor thermal stability of the oxide materials inhibits their use at elevated temperature [N. Yabuuchi, K. Kubota, M. Dahbi, S. Komaba,“Research Development on Sodium-Ion Batteries”, Chem. Rev. (2014) 114, 11636-1 1682] Phosphate based materials are known to be structurally and thermally stable and can be used as potential electrode materials for SIBs. In particular, NASCION-type structure, which has open 3D ion transport channels to facilitate faster ion transportation, are widely studied as electrode materials. Na3V2(PC>4)3 of NASICON-type structure is an example of promising cathode material with a flat voltage plateau at ~3.4 V vs. Na/Na+ and high reversible capacity of 1 18 mAh/g. Flowever, the poor electronic conductivity associated with it causes capacity degradation.
Further, increase in voltage and specific capacity is seen with fluorine doping to the phosphate framework in sodium vanadium phosphate
resulting in the chemical composition of Na3V2(PC>4)3-xF3x (0<x < 1 ). The resulting compound shows a high voltage of ~3.7 V vs. Na/Na+ and specific capacity of ~128 mAh/g for x=1.
Initially, researchers focused on various methods or a combination of methods such as electrically conductive coatings on particle surfaces and element doping to improve the conductivity of the material. Various synthesis routes explored to prepare these materials were solid-state reactions, sol-gel, electrospinning, hydrothermal and solvothermal method. However, these synthesis routes involved formation of materials with secondary phases (solid-state route), or low yield and expensive (hydrothermal, electrospinning and freeze drying), or inhomogeneous gelation with prolonged reaction time (conventional sol-gel).
Related prior art:
There are a number of prior art patents/ application method for the preparation of electrode materials of alkali ion transition metal phosphates especially sodium vanadium phosphate and sodium vanadium fluorophosphates and the product thereof. Some of them, related to the present invention of ours are discussed below to explain how our invention is different and superior from the prior art disclosures. The microwave radiation has been extensively used as a source of heat during materials synthesis. In literature, there are various reports of using microwave radiation during solid state as well as solution-based synthesis. In 2004, Barker et al. reported the synthesis of transition metal-based compounds as cathode active materials using electromagnetic radiation such as microwave, infrared and radio wave assisted solid state route (US2004016632A1 ). Similarly, microwave assisted solid state synthesis route has been adopted to prepare a composite of phosphodiesterase sodium vanadium oxide/ alkenyl and graphite (CN104078676B, CN104078676A) and different metal containing compounds for lithium,
sodium and potassium ion batteries (KR20150080652A), as reported elsewhere. Though microwave assisted solid state synthesis has been adopted to prepare these electrode active materials in bulk quantities, it may lead to electrode materials of lesser phase purity, inhomogeneity and non-stoichiometric in compositions compared to solution-based synthesis routes such as, hydrothermal, solvothermal and sol-gel synthesis etc. The low purity, inhomogeneity and non-stoichiometric in compositions may lead to poor electrochemical performance when used as electrode materials for different battery chemistries. Further to address these issues, various solution-based synthesis routes were adopted to prepare different electrode materials. In 2017, Ikejeri et al. proposed the synthesis of composite materials as electrodes for sodium ion batteries via different chemical routes such as sol-gel, mechanochemical and chemical vapour deposition (US20170005337A1 ). These methods involve inhomogeneity (in case of sol-gel and mechanochemical routes), defects in materials (in case of mechanochemical route) and low yield (in case of chemical vapour deposition). In another report, conventional sol-gel method has been used to prepare the sodium vanadium phosphate cathode material for sodium ion battery and sodium hybrid capacitor applications (CN10632891 1 A, KR101783435B1 ). The disadvantages of the conventional sol-gel process involve longer gelation time (24- 36 hours) and non-uniform gelation due to inhomogeneous mixing of precursors. Microwave assisted high pressure hydrothermal reaction has been adopted as another effective route to synthesize the electrode materials such as sodium/lithium transition metal phosphates (US9809456B2, JP5623821 B2, US200901 17020A1 ).
However, the synthesis of electrode materials in large scale will lead to safety issues as well as high cost.
In the present invention, we disclose the microwave assisted sol-gel synthesis of alkali ion transition metal phosphates and their derivatives.
Solution based microwave assisted sol-gel synthesis has various advantages over other synthesis routes, such as a) Volumetric heating: Generally solvent and solute components of the solution absorb the microwave radiation rather than transmitting or reflecting as in case of gases and solids respectively. This leads to the uniform and rapid heating of the solution components, which results in faster reaction rates. b) Uniform gelation: Especially in a solution mode, microwaves generate rapid charging fields such as dipoles in the solvent which will be aligned continuously in the field direction to produce the heat. This heat will be uniformly distributed to get the localized superheating, which will reduce the defects/impurities by enhancing the purity of the material. This localized superheating will create chemical homogeneity and results in the uniform gelation which further affects the properties of the final product when compared to that of conventional sol-gel product. In addition, in-situ carbon coating with uniform thickness can be achieved unlike conventional sol-gel route. c) Ambient pressure synthesis: The use of open vessel-based microwave- assisted sol-gel synthesis reduces the risk of high pressure unlike microwave irradiated high pressure hydrothermal reaction while allowing the evaporated species to escape out easily. d) Highly economical: For large scale synthesis of electrode materials, lower processing time is most important than any other parameters as it can influence the productivity of the industry. So, the process involves the formation of uniform gelation within minutes rather than hours as in conventional sol-gel making microwave assisted sol-gel as highly efficient process to synthesize the electrode active materials.
These above stated advantages involved in microwave assisted sol-gel route lead to the synthesis of efficient electrode materials with excellent
storage performance compared to the electrode materials synthesized via other synthesis routes.
Patents cited:
US20040016632A1 ; CN105552328A; CN104078676B; CN107425190A; CN107492635A; KR101783435B1 ; CN105140468A; US2017005337A1 ; CN105098179A; CN106058202A; CN106410193A; CN106328911 A; and CN107871865A.
Non-patent cited (publications):
1. M. S. Whittingham,“Lithium Batteries and Cathode Materials”, Chem. Rev. (2004) 104, 4271 -4302.
2. J. Y. Hwang, S.T. Myung, Y.K. Sun,“Sodium-ion batteries: present and future”, Chem. Soc. Rev. (2017) 46, 3529-3614.
3. C. Delmas,“Sodium and Sodium-Ion Batteries: 50 Years of research”, Adv. Energy Mater. (2018) 8, 1703137.
4. B. Dunn, H. Kamath, J. M. Tarascon,“Electrical Energy Storage for the
Grid: A battery of choices”, Science (201 1 ) 334, 928-935.
5. N. Yabuuchi, K. Kubota, M. Dahbi, S. Komaba,“Research Development on Sodium-Ion Batteries”, Chem. Rev. (2014) 114, 11636-1 1682.
6. Y.J. Zhu, F. Chen, “Microwave Assissted Preparation of Inorganic Nanostructures in Liquid Phase”, Chem. Rev. (2014) 1 14, 6462-6555.
OBJECTIVES OF THE INVENTION
The objective of the present invention is to provide a quicker synthesis route for the preparation of in-situ carbon coated alkali ion transition metal phosphates and their derivatives as potential electrode materials. The main objective of the present invention is, therefore to prepare in-situ carbon coated sodium vanadium phosphate/fluorophosphates embedded
in mesoporous carbon network via microwave assisted sol-gel route with high storage performance.
Another objective of the present invention is to provide uniform carbon coated sodium vanadium phosphate/fluorophosphates with controlled particle size.
Yet another objective of the present invention is to provide large scale synthesis of uniform carbon coated sodium vanadium phosphate/fluorophosphates with controlled particle size.
Yet another objective of the present invention is to provide the use of prepared electrode active materials in sodium ion battery, sodium ion capacitor and sodium ion supercabattery.
SUMMARY OF THE INVENTION:
Accordingly, the present invention relates method for preparing in-situ carbon coated electrode materials by microwave assisted sol-gel process and the product thereof. The electrode material is selected from alkali ion transition metal phosphates and alkali ion transition metal fluorophosphate having the general formula [A3M2(P04)3] and [A3M2(P04)2F3] wherein‘A’ is an alkali ion selected from Li, Na and K ; M is a transition metal selected from Fe, Ni, Co, V, Mn, Ti, and Cr. The process of synthesis comprising the following steps: a) mixing by adding an alkali ion precursor, a transition metal precursor, a phosphorus precursor, and a gelating / chelating agent in a ratio of 3:2:3:2 b) while alkali ion precursor, the phosphorus precursor and the chelating agent are taken based on corresponding molar ratios considering the amount of the transition metal precursor in an deionized water or non- aqueous solvent selected from ethylene glycol, polyethylene glycol,
tetraethylene glycol and solvents which have relatively low to moderate boiling point in vessel; c) stirring the said mixture in the vessel for a period of so as to obtain a homogenous mixture; d) subjecting to microwave radiation in an open vessel, with constant stirring at a fixed temperature resulting homogenous gelation at a temperature range from 80 to 170 °C under atmospheric pressure; e) drying the resultant gel at a temperature range from 100 to 120 °C in air; f) grinding the dried gel and g) calcining the dried gel at a temperature range from 600 to 800 °C for a period of 8 to 10 hours under an inert atmosphere with an intermediate calcination temperature of 300 to 500 QC for 3 to 5 hours resulting an in-situ carbon coating layer formation on the electrode material along with formation of mesoporous carbon network.
Here the alkali ion transition metal phosphates is sodium vanadium phosphate [Na3V2(PC>4)3] and the constituents added in the mix of step a) are sodium precursor is selected from the group consisting of sodium dihydrogen phosphate (NaH2PC>4), sodium acetate dihydrate (CH3C00Na.2H20), sodium hydroxide monohydrate (Na0H.H20), sodium hydroxide (NaOH), sodium carbonate (Na2CC>3), sodium phosphate (Na3PC>4), sodium phosphate dodecahydrate (Na3P04.12H20), sodium oxalate (Na2C2C>4), and a mixture thereof; vanadium precursor selected from the group consisting of, vanadium (V) oxide (V2O5), ammonium metavanadate (NH4VO3), vanadium (III) oxide (V2O3), vanadyl acetylacetonate [V0(CsH702)2], trihydroxy (oxo) vanadium (H3VO4) and a mixture thereof; phosphorus precursor is selected from the group consisting of ammonium phosphate [(NH4)3PC>4] diammonium phosphate
[(NH HRO^, ammonium dihydrogen phosphate (NH4H2PO4), phosphoric acid (H3PO4), sodium dihydrogen phosphate (NahtePC ) and a mixture thereof; and gelating/chelating precursor, used as source for in-situ carbon coating and mesoporous carbon network is selected from the group consisting of citric acid, ascorbic acid, oxalic acid, and gluconic acid.
One aspect of the invention also involves drying the gel formed during microwave synthesis in an ambient atmosphere at a fixed temperature and further subjecting it to a two-stage heat treatment under inert atmosphere.
Another aspect of this invention is the drastic reduction in the reaction time for the gel formation.
Another aspect of this invention includes the formation of in-situ carbon coating onto sodium vanadium phosphate and sodium vanadium fluorophosphate electrode material, obtained through microwave assisted sol-gel method. Another aspect of this invention is the synthesis of uniform and controlled particle size via microwave assisted sol-gel route.
Another aspect of this invention focuses on the scalability of this process. This route facilitates large scale synthesis of desired electrode materials.
Another aspect of this invention is the application of the synthesized electrode material in a sodium ion battery, sodium ion symmetric cell and hybrid supercapacitors due to their long-term cycling stability and high specific energy.
Another aspect of this invention is the application of the synthesized electrode materials in“Supercabattery” owing to their high power density at high specific energy compared to conventional supercapacitors.
When compared to a conventional sol-gel synthesis route, microwave sol- gel is an efficient method to prepare homogeneous gel within a very short
reaction time. Thus, a long time for gelation is overruled to reduce the cost. In addition, sodium vanadium phosphate and sodium vanadium fluorophosphate with uniform and controlled particle size distribution may be easily achieved. This carbon coated electrode materials have wide industrial applications. It is used in the manufacturing of sodium ion cells/ battery, supercabattery and sodium ion capacitors.
BRIEF DESCRIPTION OF THE DRAWING:
Fig.1 a is an X-ray diffraction (XRD) pattern of carbon coated sodium vanadium phosphate.
Fig.1 b is an X-ray diffraction (XRD) pattern of carbon coated sodium vanadium fluorophosphate prepared according to an embodiment of the present invention (Example 1 and 2).
Fig. 2a is a photographic image of a scanning electron microscope (SEM) of carbon coated sodium vanadium phosphate.
Fig. 2b is a photographic image of a scanning electron microscope (SEM) of carbon coated sodium vanadium fluorophosphate prepared according to an embodiment of the present invention (Example 1 and 2).
Fig. 3 is a photographic image of a transmission electron microscope (TEM) of carbon coated sodium vanadium phosphate prepared according to an embodiment of the present invention (Example 1 ).
Fig. 4 represents the cyclic voltammogram (CV) of carbon coated sodium vanadium phosphate at a constant scan rate (100 pV/s) in the voltage window of 2.3-3.9 V vs. Na/Na+.
Fig. 5 is the comparison of the galvanostatic charge-discharge cycling plots for the carbon coated sodium vanadium phosphate at 0.1 C-rate (1 C = 1 18 mA/g) w.r.t. Na/Na+ at various potential windows.
Fig. 6 is the comparison of the specific capacity vs. cycle number plots for carbon coated sodium vanadium phosphate at 0.1 C-rate in different voltage windows.
Fig. 7 represents the galvanostatic charge/discharge cycling plots for carbon coated sodium vanadium phosphate symmetrical cells cycled at 0.1 and 1.0 A/g in the voltage window of 0 -3 V.
Fig. 8 represents the specific capacity vs. cycle number plots for carbon coated sodium vanadium phosphate symmetrical cells at 0.1 A/g up to 100 cycles and at 1 A/g up to 1400 cycles in the voltage window of 0-3 V.
Fig. 9a represents the galvanostatic charge-discharge cycling plots for carbon coated sodium vanadium phosphate supercapacitor at various current densities in the potential window of 0-3 V.
Fig.9b shows specific capacitance vs. current density plots for carbon coated sodium vanadium phosphate supercapacitor.
Fig. 10 represents the cyclic voltammogram (CV) of carbon coated sodium vanadium fluorophosphate at a constant scan rate (100 pV/s) in the voltage window of 2.5-4.5 V vs. Na/Na+.
Fig. 1 1 represents the galvanostatic charge-discharge cycling plot for the carbon coated sodium vanadium fluorophosphate at 1 C-rate (1 C = 128 mA/g) in the potential window of 2.5 - 4.5 V vs. Na/Na+.
Fig. 12. represents specific capacity vs. cycle number plot for carbon coated sodium vanadium fluorophosphate at 1 C-rate in the potential window of 2.5-4.5 V vs. Na/Na+.
DETAILED DESCRIPTION OF THE PRESENT INVENTION: The present invention focuses on a novel Microwave assisted sol-gel process for preparing in-situ carbon coated alkali ion transition metal phosphate electrode active materials and its derivatives such as alkali ion transition metal phosphates and alkali ion transition metal fluorophosphate having the general formula [A3M2(PC>4)3] and [A3M2(PC>4)2F3] respectively wherein‘A’ is an alkali ion selected from Li, Na and K ; M is a transition
metal selected from Fe, Ni, Co, V, Mn, Ti, Cr. This method addresses the safety issue, prolonged reaction time, formation of phase pure materials and also the reduction in the cost compared to other synthesis routes, such as solid-state reaction, hydrothermal, conventional sol-gel, electrospinning and freeze drying etc.
In an embodiment to achieve an aspect of preparing the gel, a synthesis route involves (a) preparing a homogeneous solution by adding an alkali ion precursor, a transition metal precursor, a phosphorus precursor, a gelating/ chelating agent in an aqueous/non-aqueous solvent; (b) A stirring step may be additionally carried out to achieve the homogeneous solution of added precursors such as, alkali ion precursor, transition metal precursor, the phosphorus precursor and the gelating agent (c) The mixture solution may be put into an open vessel and exposed to microwave radiation to prepare the gel under ambient pressure (d) The vessel used may be an open vessel. No specific pressure conditions are required unlike the hydrothermal synthesis, supercritical hydrothermal synthesis or solvothermal synthesis, where a pressure-resistant vessel is compulsory in order to perform the reaction successfully.
In another embodiment, the reaction solvents may be either aqueous such as deionized H2O or non-aqueous such as ethylene glycol, polyethylene glycol, tetraethylene glycol and solvents which have relatively low to moderate boiling point.
In an embodiment of the present invention, the gelation may be carried out in a temperature range from 80 to 170 °C under atmospheric pressure. In another embodiment of the present invention, the obtained gel may be dried at a temperature range from 100 to 120 °C in air. The dried gel is then grinded and subjected to a two-stage heat treatment.
In another embodiment, the heat treatment is not specifically limited and may be conducted by calcining the gel at a temperature range from 600 to
800 °C for a period of 8 to 10 hours under an inert atmosphere with an intermediate calcination temperature of 300 to 500 QC for 3 to 5 hours. The inert atmosphere may be but not limited to Argon and N2. During the heat- treatment, an in-situ carbon coating layer may be formed on the alkali ion transition metal phosphate along with formation of mesoporous carbon network.
In an embodiment of the present invention, the alkali ion transition metal phosphate [A3M2(P04)3] in which alkali ion ‘A’ may be Li, Na and K; transition metal M may be Fe, Ni, Co, V, Mn, Ti, Cr etc.
In an embodiment to achieve an aspect of the invention, sodium vanadium phosphate [Na3V2(PC>4)3] active cathode material has been synthesized using the microwave-assisted sol-gel process.
The sodium precursor thus added may be at least one selected from the group consisting of sodium dihydrogen phosphate (NaF PC ), sodium acetate dihydrate (CH3C00Na.2H20), sodium hydroxide monohydrate (NaOH.FteO), sodium hydroxide (NaOH), sodium carbonate (Na2CC>3), sodium phosphate (Na3PC>4), sodium phosphate dodecahydrate (Na3P04.12H20), sodium oxalate (Na2C2C>4), and a mixture thereof.
The vanadium precursor added may be at least one selected from the group consisting of, vanadium (V) oxide (V2O5), ammonium metavanadate (NH4VO3), vanadium (III) oxide (V2O3), vanadyl acetylacetonate [ VO (C5H 702)2], trihydroxy (oxo) vanadium (H3VO4) and a mixture thereof.
The phosphorus precursor added may be at least one selected from the group consisting of ammonium phosphate [(NH4)3P04], diammonium phosphate [(NH4)2HP04], ammonium dihydrogen phosphate (NH4H2PO4), phosphoric acid (H3PO4), sodium dihydrogen phosphate (NaH2P04) and a mixture thereof.
The gelating/chelating precursor, which is used as source for in-situ carbon coating and mesoporous carbon network. It may be at least one
selected from the group consisting of citric acid, ascorbic acid, oxalic acid, gluconic acid etc.
In addition to the gelating/chelating agent, there are certain organic precursors which may be used for in-situ carbon coating. These organic precursors are not specifically limited and may be at least one selected from the group consisting of glucose, sucrose, galactose, fructose, lactose, starch, mannose, ribose, aldohexose, ketohexose, and a combination thereof.
The mixing ratio of the sodium precursor, the vanadium precursor, the phosphorus precursor and the chelating agent during the solution preparation is maintained at 3:2:3:2. The sodium precursor, the phosphorus precursor and the chelating agent may be added by corresponding molar ratios considering the amount of the vanadium precursor.
In an embodiment of the present invention, the gelation for sodium vanadium phosphate may be carried out at a temperature 80 °C. The obtained gel maybe dried at 120 °C in an ambient atmosphere.
In another embodiment to achieve sodium vanadium phosphate of the present invention, the final calcination may be carried out at a temperature of 800 °C for 10 hrs under argon atmosphere with an intermediate calcination at 400 QC for 4 hrs.
In another embodiment of the present invention, sodium vanadium flourophosphate [Na3V2(P04)2F3] as an active cathode material may be synthesized using the microwave-assisted sol-gel process.
The fluorine precursor added may be at least one selected from the group consisting of NaF, NFUF and NFl4FIF2 and a mixture thereof.
In an embodiment, the above-mentioned process steps may be extended for the preparation of cation doped alkali ion transition metal phosphates
with general formula A3M2-xCx(PC>4)3; 0<x<2, where C may be any one of Mg, Al, Ti, Ca, Sc etc.
In another embodiment, the above-mentioned process steps may be extended for the preparation of anion doped alkali ion transition metal phosphates with general formula A3M2(P04)3-yN3y; 0<y<1 and A3M2- xCx(P04)3-yl\l3y; 0<x<2, 0<y<1 where N may be any one of these Cl, Br, I etc.
In another embodiment of the present invention, the microwave assisted sol-gel synthesis process may be extended to prepare the multi polyanionic compounds with general formula, Na4M3(P04)2P20z (M= Fe, Mn, Co and Ni etc.) and layered sodium transition metal oxides with general formula, NaxM02, 0.44<x<1 (M= Fe, Mn, Co, Ni, Ti etc.) as electrode active materials.
The sodium vanadium phosphate/fluorophosphate particles prepared through the series of the above described steps may have a NASICON (Na Super Ionic CONductor) type of rhombohedral/tetragonal crystal structure as confirmed from the X-ray diffraction patterns (Figurel (a) & (b))·
The particle size and its distribution may be controlled by changing the content of gelating/chelating agent, or regulating process parameters such as reaction temperature and reaction time, etc.
The sodium vanadium phosphate and sodium vanadium fluorophosphate prepared through the above stated method may possess particle size in the range of 300-500 and 30-50 nm respectively, as shown in Figure 2. The thickness of the carbon coating formed on the surface of the sodium vanadium phosphate and sodium vanadium fluorophosphate is not limited and may be <10 nm as shown in Figure 3.
Preparation of sodium ion battery
In the present invention, the electrode material is a composite which includes cathode active material, conductive agent and a binder in appropriate ratios.
The conductive agent may include any material having good electronic conductivity such as graphite in form of natural graphite and synthetic graphite; amorphous carbon in form of carbon black, acetylene black, ketjen black; carbon fibers, carbon nanotubes and graphene etc. The conductive agent may be added by 1 to 15 wt. % based on the total amount of the mixture including the cathode active material.
The binder may be any component that gives mechanical stiffness and helps to bind the active material particles together and also with the current collector, may include polyvinylidene fluoride, polyvinyl alcohol, carboxymethyl cellulose, polyvinyl pyrrolidone, tetrafluoroethylene, etc.
The binder may be added by 1 to 15 wt. % based on the total amount of a mixture including the cathode active material.
The electrode for the sodium ion battery may be fabricated by, for example, dissolving the cathode active material, conducting agent and binder in a solvent, e.g. non-aqueous NMP (N-methyl-2- pyrrolidone)/aqueous (H2O) solvent to prepare slurry and coating the slurry onto the current collector followed by drying and calendaring.
The current collector may be any material having good electronic conductivity and may include stainless steel, aluminum, copper, nickel, carbon film or a surface treated material such as aluminum or stainless steel with carbon etc.
In another embodiment of the present invention, fabrication of a sodium ion battery may include a cathode, an anode (may be Na metal, but not limited), a separator and a non-aqueous electrolyte containing a sodium salt.
The non-aqueous organic solvent for electrolyte may include aprotic organic solvents such as propylene carbonate, ethylene carbonate, dimethyl carbonate, diethyl carbonate and their derivatives, etc.
The sodium salt materials which are preferably soluble in the non-aqueous electrolyte may include NaCIC , NaBF4, NaPF6, NaCF3SC>3, NaCF3CC>2, CF3S03Na, and (CF3S02)2NNa etc.
In addition, aqueous electrolytes may also be used in the fabrication of the sodium ion battery.
In an embodiment of the present invention, a sodium ion battery containing the prepared sodium vanadium phosphate as cathode active material displays high specific capacity and cyclic stability (Figure 4, 5 and 6).
In an embodiment of the present invention, a sodium ion capacitor containing the prepared sodium vanadium phosphate as cathode and anode shows high specific capacity, specific capacitance and cyclic stability (Figure 7, 8 and 9).
In an embodiment of the present invention, a sodium ion battery containing the prepared sodium vanadium fluorophosphate as cathode active material displays high specific capacity and cyclic stability. (Figure 10, 1 1 and 12).
The active materials developed through microwave assisted sol-gel method finds its application as an electrode active material for alkali ion batteries, alkali ion capacitors and in supercabattery devices.
Experimental Example 1
Sodium vanadium phosphate, Na3V2(PC>4)3 was synthesized via microwave assisted sol-gel method. Stoichiometric amounts of each precursor were taken to prepare the Na3V2(PC>4)3. The precursors used were NaFl2P04.2Fl20 [99%, Sigma Aldrich], NFI4VO3 [98%, Loba Chemie] and citric acid (ObHIdOz) [99.5%, Sigma Aldrich] NaFl2P04.2Fl20 was
added to de-ionized water and ultra-sonicated for 5 minutes until it was completely dissolved to form a clear solution. To the above solution, NFI4VO3 and citric acid were added, and the solution was continuously stirred at 80 °C, until a dark orange colored transparent solution was formed. The solution was then transferred to a microwave synthesizer and it was maintained at 80 °C for 10 minutes to obtain a dark blue gel. The gel was then washed and dried at 120 °C in ambient atmosphere. The dried gel was grinded and then preheated at 400 °C for 4 h under argon atmosphere. Finally, the preheated sample was subjected to calcination at 800 °C for 10 h under argon atmosphere to get the single phase
Na3V (P04)3.
Experimental Example 2
Sodium vanadium fluorophosphate, Na3V2(PC>4)2F3 was prepared by the microwave assisted sol-gel route similar to that of Na3V2(PC>4)3 using NaF [Merck 99%], NH4H2PO4 [Sigma Aldrich 98.5%], NH4VO3 [Loba Chemie 98%] and Citric acid [Merck 99.5%] as the precursors. Stoichiometric amounts of the precursors were mixed in Dl water and transferred to an open vessel and subjected to microwave reaction at constant temperature (80°C) and stirring rate until the gel was formed. The above-mentioned gel was then washed and dried in a hot air oven under ambient air, at 120 °C. The dried gel was crushed, ground and then subjected to a two-step heat treatment under argon atmosphere, i) 350 °C for 4 h and ii) 650°C for 6 h to obtain the phase pure, Na3V2(P04)2F3. After the synthesis of both Na3V2(P04)3/Na3V2(PC>4)2F3, various structural and morphological studies were carried out using X-Ray diffractometer (Rigaku Smartlab X-ray diffractometer with Cu-Ka radiation), scanning electron microscopy (FE-SEM; Zeiss merlin Compact) and transmission electron microscopy (TEM; Technai G20) etc.
We have brought out the novel features of the invention by explaining some of the preferred embodiments under the invention, enabling a person in the art to understand and visualize our invention. It is also to be understood that the invention is not limited in its application to the details set forth in the above description or illustrated in the drawings. Although the invention has been described in considerable detail with reference to certain preferred embodiments thereof, various modifications can be made without departing from the spirit and scope of the invention as described herein above and as defined in the following Claims.
Claims
1. Microwave assisted sol-gel process for preparing in-situ carbon coated electrode materials wherein the electrode material is selected from alkali ion transition metal phosphates and alkali ion transition metal fluorophosphate having the general formula
[A3M2(P04)3] and [A3M2(P04)2F3] wherein ‘A’ is an alkali ion selected from Li, Na and K; M is a transition metal selected from Fe, Ni, Co, V, Mn, Ti, and Cr, comprising the steps of:
a) mixing by adding an alkali ion precursor, a transition metal precursor, a phosphorus precursor, and a gelating/ chelating agent in appropriate molar ratio.
b) while alkali ion precursor, the phosphorus precursor and the chelating agent are taken based on corresponding molar ratios considering the amount of the transitional precursor in deionized water or non-aqueous solvent selected from ethylene glycol, polyethylene glycol, tetraethylene glycol and solvents which have relatively low to moderate boiling point in vessel; c) stirring the said mixture in the vessel for a period of so as to obtain a homogenous mixture;
d) subjecting to microwave radiation in an open vessel, with constant stirring at a fixed temperature resulting homogenous gelation at a temperature range from 80 to 170 °C under atmospheric pressure;
e) drying the resultant gel at a temperature range from 100 to 120 °C in air;
f) grinding the dried gel and
g) calcining the dried gel at a temperature range from 600 to 800 °C for a period of 8 to 10 hours under an inert atmosphere with an intermediate calcination temperature of 300 to 500 QC for 3 to 5 hours resulting an in-situ carbon coating layer formation on the
electrode material along with formation of mesoporous carbon network.
2) The microwave assisted sol-gel process for preparing in-situ carbon coated electrode materials as claimed in claim 1 , wherein the alkali ion precursor, transition metal precursor, a phosphorus precursor, and a gelating/ chelating agent are mixed in the ratio of 3:2:3:2
3) The microwave assisted sol-gel process for preparing in-situ carbon coated electrode materials as claimed in claim 1 , wherein alkali ion transition metal phosphates is sodium vanadium phosphate [Na3V2(PC>4)3] and the constituents added in the mix of step a) are sodium precursor is selected from the group consisting of sodium dihydrogen phosphate, sodium acetate dihydrate (CH3C00Na.2H20), sodium hydroxide monohydrate (NaOH.hteO), sodium hydroxide (NaOH), sodium carbonate (Na2CC>3), sodium phosphate (Na3PC>4), sodium phosphate dodecahydrate (Na3P04.12H20), sodium oxalate (Na2C2C>4), and a mixture thereof; vanadium precursor selected from the group consisting of, vanadium (V) oxide (V2O5), ammonium metavanadate (NH4VO3), vanadium (III) oxide (V2O3), vanadyl acetylacetonate [ VO (CsH 702)2], trihydroxy (oxo) vanadium (H3VO4) and a mixture thereof; phosphorus precursor is selected from the group consisting of ammonium phosphate [(NH4)3P04], diammonium phosphate [(NH )2HP04], ammonium dihydrogen phosphate (NH4H2PO4), phosphoric acid (H3PO4), sodium dihydrogen phosphate (NaH2P04) and a mixture thereof; and gelating/chelating precursor, used as source for in-situ carbon coating and mesoporous carbon network is selected from the group consisting of citric acid, ascorbic acid, oxalic acid, and gluconic acid.
4) The microwave assisted sol-gel process for preparing in-situ carbon coated electrode materials as claimed in claim 1 , wherein organic precursors are additionally added in step a) selected from the group consisting of glucose, sucrose, galactose, fructose, lactose, starch, mannose, ribose, aldohexose, ketohexose, and a combination thereof as additional agent for in-situ carbon coating.
5) The microwave assisted sol-gel process for preparing in-situ carbon coated electrode materials as claimed in claim 1 , wherein in step g) calcining the dried gel under the inert gas, selected from Argon or Nitrogen. 6) The microwave assisted sol-gel process for preparing in-situ carbon coated electrode materials as claimed in claim 1 , wherein alkali ion transition metal fluorophosphate is [Na3V2(PC>4)2F3] and the Alkali ion and fluorine precursor is added in step a) consisting of NaF, and the remaining steps being the same. 7) The microwave assisted sol-gel process for preparing in-situ carbon coated electrode materials as claimed in claim 1 , wherein the particle size and its distribution are controlled by changing the content of gelating/chelating agent, or regulating process parameters based on the requirement. 8) The microwave assisted sol-gel process for preparing in-situ carbon coated electrode materials as claimed in claim 1 , wherein cation doped alkali ion transition metal phosphates with general formula A3M2-XCX(P04)3; in which 0<x<2, where C is any one of Mg, Al, Ti, Ca, and Sc, is additionally added in step a) and the remaining steps being the same.
9) The microwave assisted sol-gel process for preparing in-situ carbon coated electrode materials as claimed in claim 1 , wherein anion doped alkali ion transition metal phosphates with general formula
A3M2(P04)3-yN3y; in which 0<y<1 and A3M2-xCx(P04)3-yN3y, in which 0<x<2, 0<y<1 where N is any one of these Cl, Br, and I, is additionally added in step a) and the remaining steps being the same. 10)The microwave assisted sol-gel process for preparing in-situ carbon coated electrode materials as claimed in claim 1 , wherein the multi polyanionic compounds with general formula, Na4M3(P04)2P20z in which M= Fe, Mn, Co and Ni and layered sodium transition metal oxides with general formula, NaxMC , in which 0.44<x<1 , M= Fe, Mn, Co, Ni, and Ti, also can be prepared by selecting appropriate precursor in the required molar ratio in step a)
11 ) In-situ carbon coated electrode materials are prepared by the microwave assisted sol-gel process as claimed in claim 1 to 10.
12)The in-situ carbon coated electrode materials as claimed in claim 3 and 6 have a NASICON (Na Super Ionic CONductor) type of rhombohedral and tetragonal crystal structure, respectively.
13)The in-situ carbon coated electrode materials as claimed in claim 6, wherein the sodium vanadium phosphate and sodium vanadium fluorophosphate prepared possess particle size in the range of 300- 500 and 30-50 nm respectively.
14)The in-situ carbon coated electrode materials as claimed in claim 3 and 6, wherein the thickness of the carbon coating formed on the surface of said carbon coated electrode materials is <10 nm.
15) Sodium ion cells/ battery, supercabattery and sodium ion capacitors having in-situ carbon coated electrode materials are prepared by the microwave assisted sol-gel process as claimed in claim 1.
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| EP20763813.1A EP3749609A4 (en) | 2019-02-28 | 2020-02-13 | Microwave assisted sol-gel process for preparing in-situ carbon coated electrode materials and the product thereof |
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| EP3749609A4 (en) | 2021-11-17 |
| EP3749609A1 (en) | 2020-12-16 |
| KR102497808B1 (en) | 2023-02-10 |
| JP7074870B2 (en) | 2022-05-24 |
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| KR20200138198A (en) | 2020-12-09 |
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