CN114883540A - Iron-based phosphate sodium-ion battery positive electrode material and preparation method thereof - Google Patents
Iron-based phosphate sodium-ion battery positive electrode material and preparation method thereof Download PDFInfo
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- CN114883540A CN114883540A CN202210352225.8A CN202210352225A CN114883540A CN 114883540 A CN114883540 A CN 114883540A CN 202210352225 A CN202210352225 A CN 202210352225A CN 114883540 A CN114883540 A CN 114883540A
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 108
- 229910019142 PO4 Inorganic materials 0.000 title claims abstract description 42
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 title claims abstract description 39
- 239000010452 phosphate Substances 0.000 title claims abstract description 39
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 37
- 229910001415 sodium ion Inorganic materials 0.000 title claims abstract description 35
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 239000002243 precursor Substances 0.000 claims abstract description 49
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 claims abstract description 47
- 229910000398 iron phosphate Inorganic materials 0.000 claims abstract description 46
- 229920000767 polyaniline Polymers 0.000 claims abstract description 33
- 238000000034 method Methods 0.000 claims abstract description 25
- 239000000463 material Substances 0.000 claims abstract description 17
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000002245 particle Substances 0.000 claims abstract description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 10
- 159000000000 sodium salts Chemical class 0.000 claims abstract description 6
- 239000013543 active substance Substances 0.000 claims abstract description 3
- 239000002131 composite material Substances 0.000 claims abstract description 3
- 239000011734 sodium Substances 0.000 claims description 49
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 15
- 238000005245 sintering Methods 0.000 claims description 15
- 229910052786 argon Inorganic materials 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 10
- 238000000227 grinding Methods 0.000 claims description 9
- 238000010532 solid phase synthesis reaction Methods 0.000 claims description 9
- 238000001694 spray drying Methods 0.000 claims description 9
- 239000007789 gas Substances 0.000 claims description 8
- 238000000576 coating method Methods 0.000 claims description 7
- 239000010405 anode material Substances 0.000 claims description 6
- 239000011248 coating agent Substances 0.000 claims description 6
- 239000010406 cathode material Substances 0.000 claims description 5
- 239000002105 nanoparticle Substances 0.000 claims description 5
- 238000003980 solgel method Methods 0.000 claims description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000003575 carbonaceous material Substances 0.000 claims description 4
- 239000011258 core-shell material Substances 0.000 claims description 4
- 239000007772 electrode material Substances 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 229910044991 metal oxide Inorganic materials 0.000 claims description 4
- 150000004706 metal oxides Chemical class 0.000 claims description 4
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical group O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 4
- 239000003570 air Substances 0.000 claims description 3
- 239000012298 atmosphere Substances 0.000 claims description 3
- 229910002804 graphite Inorganic materials 0.000 claims description 3
- 239000010439 graphite Substances 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 229910003481 amorphous carbon Inorganic materials 0.000 claims description 2
- 239000006229 carbon black Substances 0.000 claims description 2
- 238000000975 co-precipitation Methods 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052737 gold Inorganic materials 0.000 claims description 2
- 239000010931 gold Substances 0.000 claims description 2
- 229910021385 hard carbon Inorganic materials 0.000 claims description 2
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 239000007800 oxidant agent Substances 0.000 claims description 2
- 230000001590 oxidative effect Effects 0.000 claims description 2
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 claims description 2
- 238000006116 polymerization reaction Methods 0.000 claims description 2
- 229910052709 silver Inorganic materials 0.000 claims description 2
- 239000004332 silver Substances 0.000 claims description 2
- 239000004408 titanium dioxide Substances 0.000 claims description 2
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical class [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 claims 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 abstract description 8
- 229910052799 carbon Inorganic materials 0.000 abstract description 7
- 238000009792 diffusion process Methods 0.000 abstract description 7
- 150000002500 ions Chemical class 0.000 abstract description 6
- 238000003837 high-temperature calcination Methods 0.000 abstract description 3
- 239000011149 active material Substances 0.000 abstract description 2
- 150000003839 salts Chemical class 0.000 abstract description 2
- 230000001737 promoting effect Effects 0.000 abstract 1
- 235000021317 phosphate Nutrition 0.000 description 23
- 239000000843 powder Substances 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 238000001354 calcination Methods 0.000 description 7
- 239000010410 layer Substances 0.000 description 7
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 6
- 229930006000 Sucrose Natural products 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 239000011259 mixed solution Substances 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 239000005720 sucrose Substances 0.000 description 6
- 230000001351 cycling effect Effects 0.000 description 5
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 239000012300 argon atmosphere Substances 0.000 description 3
- 238000000498 ball milling Methods 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- 238000007605 air drying Methods 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 239000011889 copper foil Substances 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 239000007773 negative electrode material Substances 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 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 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- 229910021383 artificial graphite Inorganic materials 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- DCYOBGZUOMKFPA-UHFFFAOYSA-N iron(2+);iron(3+);octadecacyanide Chemical compound [Fe+2].[Fe+2].[Fe+2].[Fe+3].[Fe+3].[Fe+3].[Fe+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] DCYOBGZUOMKFPA-UHFFFAOYSA-N 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- -1 natural graphite Chemical compound 0.000 description 1
- 229910021382 natural graphite Inorganic materials 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 229920000447 polyanionic polymer Polymers 0.000 description 1
- 229960003351 prussian blue Drugs 0.000 description 1
- 239000013225 prussian blue Substances 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000005549 size reduction Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/054—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
- H01M4/04—Processes of manufacture in general
- H01M4/0471—Processes of manufacture in general involving thermal treatment, e.g. firing, sintering, backing particulate active material, thermal decomposition, pyrolysis
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention belongs to the technical field of sodium ion batteries, and particularly relates to an iron-based phosphate sodium ion battery positive electrode material and a preparation method thereof. The preparation method comprises the following steps: preparing a polyaniline-coated iron phosphate composite material; adding sodium salt and phosphate into iron phosphate coated by polyaniline as a precursor to prepare an iron-based phosphate sodium-ion battery positive electrode material; the preparation method of the polyaniline-coated iron phosphate precursor comprises the following steps: adding ferric salt into a solution containing phosphate and aniline to generate iron phosphate active substance particles with nanometer sizes, and promoting aniline to polymerize on the surface of iron phosphate to obtain polyaniline-coated nanometer iron phosphate. The material has excellent electronic and ionic conductivity and excellent electrochemical performance. The polyaniline shell of the iron phosphate precursor can be carbonized into a conductive carbon layer in the high-temperature calcination process, so that the electronic conductivity of the material is enhanced, and the increase of active material particles in the high-temperature process is inhibited, so that the ion diffusion is enhanced.
Description
Technical Field
The invention belongs to the technical field of sodium ion batteries, and particularly relates to an iron-based phosphate sodium ion battery positive electrode material and a preparation method thereof.
Background
With the further development of human society, the requirements for future energy storage systems are further increased, and the development of novel secondary batteries is urgently needed due to the current situations that lithium ion batteries have potential safety hazards and the lithium resource storage capacity is low. The sodium resource reserves are abundant, the extraction is simple, and the sodium ion battery has obvious cost advantage, so the sodium ion battery is widely concerned and researched.
The main factor influencing the performance of the sodium ion battery is the positive/negative electrode material, so that the design of the positive/negative electrode material with excellent synthesis performance is very important. The positive electrode material of the sodium-ion battery mainly comprises three materials, namely layered transition metal oxide, Prussian blue and polyanion materials. The iron-based phosphate has high structural stability and low cost, and is a widely researched positive electrode material. In addition, nanoscale electrode materials can achieve faster ion diffusion, but the larger electrolyte/electrode interface due to size reduction can lead to more side reactions, affecting cycling stability. The synthesis of highly crystalline nanomaterials coated with conductive carbon is therefore an effective means to eliminate these problems.
The invention provides a preparation method of an iron-based phosphate sodium-ion battery positive electrode material based on a polyaniline-coated nano iron phosphate precursor. The nano iron phosphate precursor has a core-shell structure of an iron phosphate core and a polyaniline shell, and sodium salt and phosphate in stoichiometric ratio are added to synthesize a certain iron-based phosphate. The polyaniline shell is carbonized into a conductive carbon layer in the subsequent high-temperature calcination process, and the size of the material can be effectively inhibited from being enlarged, so that the synthesis of carbon-coated high-crystallization nano iron-based phosphate becomes possible.
Disclosure of Invention
The invention aims to provide an iron-based phosphate sodium ion battery positive electrode material with excellent electrochemical performance and a preparation method thereof.
The iron-based phosphate sodium-ion battery positive electrode material provided by the invention is prepared by taking nano iron phosphate coated by polyaniline as a precursor, namely the precursor is in a core-shell structure with the iron phosphate as an inner core and the polyaniline as a shell.
The invention provides a preparation method of an iron-based phosphate sodium ion battery anode material, which comprises the following specific steps:
(1) preparing a polyaniline-coated iron phosphate composite material;
(2) adding sodium salt and phosphate according to the stoichiometric ratio of various elements in the electrode material by taking iron phosphate coated by polyaniline as a precursor to prepare an iron-based phosphate sodium-ion battery anode material;
(3) pre-sintering the iron-based phosphate precursor, grinding and mixing uniformly, and then formally sintering to obtain the iron-based phosphate sodium-ion battery anode material.
Wherein:
in the step (1), the polyaniline-coated iron phosphate precursor is a core-shell structure material with iron phosphate as an inner core and polyaniline as a shell; the preparation method comprises the following steps: in the presence of phosphate (PO 4) 3- ) And aniline to a solution of ferric (Fe) 3+ ），Fe 3+ On the one hand as PO 4 3- To generate nano-sized iron phosphate active substance particles; and on the other hand, the polyaniline-coated nano iron phosphate is obtained by using the polyaniline-coated nano iron phosphate as an oxidant to promote the polymerization of aniline on the surface of the iron phosphate.
Further, a phosphate solution (PO 4) of iron phosphate precursor was synthesized 3- ) Including but not limited to NH 4 H 2 PO 4 、(NH 4 ) 2 HPO 4 Or (NH) 4 ) 3 PO 4 。
Further, ferric (Fe) salts 3+ ) Including but not limited to Fe (NO) 3 ) 3 、FeCl 3 、Fe 2 (SO 4 ) 3 。
Further, the average particle diameter of the iron phosphate precursor is 5 to 1000 nm.
In the step (2), the sodium salt may be selected from Na 2 CO 3 、NaHCO 3 、Na 2 C 2 O 4 、CH 3 COONa、Na 3 PO 4 、Na 2 HPO 4 、NaH 2 PO 4 And the like.
The phosphate may be selected from NH 4 H 2 PO 4 、(NH 4 ) 2 HPO 4 、(NH 4 ) 3 PO 4 、Na 3 PO 4 、Na 2 HPO 4 、NaH 2 PO 4 And the like.
Further, the preparation of the iron-based phosphate sodium ion battery positive electrode material adopts one or more of the following methods in combination: high temperature solid phase method, sol-gel method, coprecipitation method, spray drying method, hydrothermal method.
Further, the molecular formula of the iron-based phosphate sodium ion battery positive electrode material can be NaFePO 4 , Na 2 FePO 4 F, Na 2 FeP 2 O 7 , Na 3.12 Fe 2.44 (P 2 O 7 ) 2 , Na 3 Fe 2 (PO 4 )P 2 O 7 , Na 4 Fe 3 (PO 4 ) 2 P 2 O 7 , Na 3 Fe 2 (PO 4 ) 3 Or Na 3 Fe 2 (PO 4 ) 2 F 3 。
In the step (3), the pre-sintering temperature and time, and the sintering temperature and time are different according to different sodium ion battery anode materials. The presintering temperature ranges from 300 ℃ to 500 ℃, and the presintering time ranges from 3 h to 6 h. The sintering temperature is 500-800 ℃, and the sintering time is 6-18 h.
Further, the atmosphere at the time of the calcination and the sintering may be air, nitrogen, argon, a mixed gas of hydrogen and argon, or the like, depending on the material characteristics.
The average particle diameter of the positive electrode material of the sodium-ion battery is 5-1000 nm.
Furthermore, the surface of the positive electrode material of the sodium-ion battery can be coated by a coating simple substance or a compound.
Further, the coating material has high electron conductivity or high ion diffusion rate or excellent stability, and the coating layer of the coating material may be a carbon material, a metal oxide or a metal.
The carbon material is amorphous carbon, hard carbon, carbon black or graphite (such as natural graphite, artificial graphite, expanded graphite) and the like.
The metal oxide can be tin dioxide, titanium dioxide, ferroferric oxide or ferric oxide and the like.
The metal can be gold, silver, copper or aluminum.
The coating method is one or combination of the following methods: chemical Vapor Deposition (CVD), hybrid ball milling, sol-gel, hydrothermal, in-situ reduction.
The precursor material prepared by the invention has excellent electronic and ionic conductivity, namely excellent electrochemical performance. The polyaniline layer is coated on the outer layer of the iron phosphate particles in situ, so that the growth of the iron phosphate particles can be inhibited, which is a precondition for preparing the nano iron-based phosphate. The polyaniline shell of the iron phosphate precursor can be carbonized into a conductive carbon layer in the high-temperature calcination process, so that the electronic conductivity of the material is enhanced, and the increase of active material particles in the high-temperature process is inhibited, so that the ion diffusion is enhanced. The iron-based phosphate sodium ion battery anode material prepared by the method not only has a nano-scale size and is beneficial to rapid diffusion of ions, but also coats a uniform conductive carbon layer and is beneficial to charge transfer, so that the material has excellent ionic and electronic conductivity, and excellent electrochemical properties of the material are achieved. In addition, the spray drying method, the mixed ball milling method and the high-temperature solid phase method in the preparation method can treat samples in large scale and meet the requirement of large-scale production.
Drawings
FIG. 1 shows polyaniline-coated iron phosphate nanoparticle precursor (FePO) in accordance with the present invention 4 @ PANI).
Fig. 2 is SEM and TEM images of iron-based phosphates prepared according to the present invention. Wherein (a) Na 4 Fe 3 (PO 4 ) 2 P 2 O 7 SEM image of (a); (b) na (Na) 4 Fe 3 (PO 4 ) 2 P 2 O 7 TEM image of (a).
Fig. 3 is an XRD spectrum of the iron-based phosphate sodium-ion battery cathode material prepared in the present invention.
Fig. 4 is a charge-discharge curve at 0.1C for various iron-based phosphate sodium-ion battery positive electrode materials prepared in the examples of the present invention.
Detailed Description
Example 1: preparation of Na by combining sol-gel method with high-temperature solid phase method 2 FeP 2 O 7 。
2.62 g of NH 4 H 2 PO 4 And 1 ml of aniline in 200 ml of deionized water, 5.51 g of Fe (NO) were slowly added dropwise with stirring 3 ) 3 Dissolving the polyaniline-coated iron phosphate precursor in 100 ml of deionized water to obtain an aqueous solution, and stirring the aqueous solution at room temperature for 5 hours to obtain the polyaniline-coated iron phosphate precursor;
then, 3.04 g of Na was added to the mixed solution containing the iron phosphate precursor 2 C 2 O 4 And 2.61 g NH 4 H 2 PO 4 Then adding sucrose accounting for 15 percent of the mass of all the raw materials, and continuously stirring for 20 min. Drying in a forced air drying oven at 80 deg.C for 48 hr to obtain mixed gel precursor;
and grinding the precursor, putting the ground precursor into a tube furnace, presintering the ground precursor for 4 hours at 350 ℃ in an argon atmosphere containing 5% of hydrogen, and then grinding and uniformly mixing the ground precursor. Calcining the mixture in hydrogen-argon mixed gas at the temperature of 550 ℃ for 12 hours to obtain Na with the nanometer size 2 FeP 2 O 7 。
Will be at the topThe prepared Na 2 FeP 2 O 7 The positive electrode powder, a conductive agent Super P and an N-methyl-2-pyrrolidone (NMP, mass fraction of 8%) solution of polyvinylidene fluoride (PVDF) as a binder are mixed according to a mass ratio of 8: 1: 1, fully and uniformly mixing, and coating the slurry on a copper foil. The copper foil is put into a vacuum oven at 80 ℃ to be dried overnight to remove NMP, and then is rolled into a pole piece, and the pole piece is cut into pole pieces with the diameter of 12 mm.
In a glove box filled with argon, with Na 2 FeP 2 O 7 As positive electrode, lithium sheet as counter electrode, 1M LiPF 6 Dissolving in Ethylene Carbonate (EC), dimethyl carbonate (DMC), Ethyl Methyl Carbonate (EMC) according to the volume ratio of 1: 1: 1 is used as electrolyte, and a commercial lithium ion battery diaphragm is adopted to assemble the CR2016 button cell. The current density is 10 mA g in the voltage range of 1.5-4.2V -1 The specific discharge capacity of the electrode is 94 mAh g -1 (see fig. 4), the magnification and cycling performance are shown in table 1.
Example 2: preparation of Na by combining sol-gel method with high-temperature solid phase method 4 Fe 3 (PO 4 ) 2 P 2 O 7 。
The polyaniline-coated nano iron phosphate precursor was prepared as in example 1;
2.49 g of CH was further added to the above mixed solution 3 COONa，0.87 g NH 4 H 2 PO 4 And sucrose accounting for about 15 percent of the total mass of the raw materials, and continuously stirring for 30 min. Drying in a forced air drying oven at 80 ℃ for 48 h to obtain a mixed gel precursor;
presintering for 4 h at 400 ℃ in an argon atmosphere containing 5% of hydrogen, and then grinding and uniformly mixing. Calcining the mixture in hydrogen-argon mixed gas at the temperature of 550 ℃ for 12 hours to obtain Na with the nanometer size 4 Fe 3 (PO 4 ) 2 P 2 O 7 。
Mixing the above prepared Na 4 Fe 3 (PO 4 ) 2 P 2 O 7 The positive electrode powder was formed into electrode tabs as described in example 1 and then assembled into CR2016 button cells. The current density is 1 in the voltage range of 2.0-4.0V0 mA g -1 The battery can provide 126mAh g -1 The specific discharge capacity (see fig. 4), rate and cycle performance of (a) are shown in table 1.
Example 3: preparation of Na by combining spray drying method with high-temperature solid phase method 3 Fe 2 (PO 4 )P 2 O 7 。
The iron phosphate precursor was prepared as in example 1. To the mixed solution containing the iron phosphate precursor, 2.29 g of Na was added 2 C 2 O 4 、1.31 g NH 4 H 2 PO 4 And sucrose accounting for about 15 percent of the total mass of the raw materials, continuously stirring for 30min, and then carrying out spray drying to obtain a precursor.
Presintering the precursor in hydrogen-argon mixed gas (containing 5% of hydrogen) at 400 ℃ for 4 h, ball-milling for 2 h, and calcining at 550 ℃ for 12 h to obtain nano-sized Na 3 Fe 2 (PO 4 )P 2 O 7 And (3) a positive electrode material.
The prepared positive electrode material was prepared into an electrode sheet according to the method in example 1, and the battery was assembled and then tested. The voltage range is 1.5-4.2V, and the current density is 10 mA g -1 The specific discharge capacity of the battery is 109mAh g -1 (see fig. 4), the magnification and cycling performance are shown in table 1.
Example 4: preparation of Na by combining spray drying method with high-temperature solid phase method 2 FePO 4 F。
The polyaniline-coated iron phosphate precursor was prepared as in example 1. To the mixed solution containing the iron phosphate precursor, 1.87 gCH was added 3 COONa and 0.96 g NaF, adding sucrose accounting for 15 percent of the total mass of all the raw materials, continuously stirring for 30min, and then carrying out spray drying to obtain a precursor.
Placing the precursor powder in a tube furnace, presintering the precursor powder in hydrogen-argon mixed gas containing 5% of hydrogen at 350 ℃ for 5 h, grinding the powder for 2 h after cooling to room temperature, and then placing the powder in the hydrogen-argon mixed gas at 600 ℃ for calcining for 6 h to obtain the product of nano Na 2 FePO 4 F。
Electrode sheets were prepared and batteries were assembled as described in example 1, at a voltage ranging from 2.0 to 4.0V and 10 mA g -1 Current density ofThen, Na 2 FePO 4 The F electrode can provide 118mAh g -1 The specific capacity (see fig. 4), rate and cycling performance are shown in table 1.
Example 5: preparation of Na by combining sol-gel method with high-temperature solid phase method 3.12 Fe 2.44 (P 2 O 7 ) 2 。
The polyaniline-coated iron phosphate precursor was prepared as in example 1. To the mixed solution containing the iron phosphate precursor, 1.55g of Na was added 2 CO 3 、1.92 g (NH 4 ) 2 HPO 4 And sucrose accounting for 15 percent of the total mass of the raw materials. Continuously stirring for 30min, and then putting the mixture into an air-blast drying oven at 80 ℃ for drying for 48 h to obtain a mixed gel precursor;
grinding the precursor, putting the ground precursor into a tube furnace, presintering the precursor for 6 h at 450 ℃ in an argon atmosphere containing 5% of hydrogen, grinding and mixing the precursor uniformly, and calcining the precursor for 12 h in a hydrogen-argon mixed gas at 600 ℃ to obtain the Na with the nano size 3.12 Fe 2.44 (P 2 O 7 ) 2 。
Mixing the above prepared Na 3.12 Fe 2.44 (P 2 O 7 ) 2 The positive electrode powder was formed into electrode tabs as described in example 1 and then assembled into CR2016 button cells. The current density is 10 mA g in the voltage range of 1.7-4.0V -1 The battery can provide 124mAh g -1 The specific discharge capacity, rate and cycle performance of (A) are shown in Table 1.
Example 6: na synthesis by combining spray drying method with high-temperature solid phase method 3 Fe 2 (PO 4 ) 3 。
The polyaniline-coated iron phosphate precursor was prepared as in example 1. To the mixed solution containing the iron phosphate precursor, 2.80g of CH was added 3 COONa、1.50 g (NH 4 ) 2 HPO 4 And sucrose accounting for 15 percent of the total mass of the raw materials. Continuously stirring for 30min, and spray drying to obtain precursor.
Putting the precursor into a tube furnace, presintering for 2 h at 550 ℃ in air atmosphere, grinding and mixing uniformly, and calcining for 12 h at 650 ℃ to obtain nano-sized Na 3 Fe 2 (PO 4 ) 3 。
Mixing the above prepared Na 3 Fe 2 (PO 4 ) 3 The positive electrode powder was formed into electrode tabs as described in example 1 and then assembled into CR2016 button cells. The current density is 10 mA g in the voltage range of 1.5-4.0V -1 The battery can provide 108mAh g -1 The specific discharge capacity, rate and cycle performance of (A) are shown in Table 1.
TABLE 1 electrochemical Properties of various iron-based phosphate cathode materials
Table 1 shows the electrochemical performance of various iron-based phosphate anodes that use polyaniline-coated iron phosphate as a precursor. The actual specific capacity of various iron-based phosphate anodes is close to the theoretical specific capacity, and the iron-based phosphate anodes have excellent rate capability and cycling stability. Therefore, the iron-based phosphate synthesized by the method has a nano-scale size, can ensure the rapid diffusion of lithium ions in the material, and in addition, the conductive carbon layer uniformly coated on the outer layer of the material particles is also beneficial to the transfer of electrons. The rapid ion diffusion and electron transfer in the electrode material ensure that the iron-based phosphate sodium ion battery cathode material prepared by the method has excellent electrochemical performance.
Claims (10)
1. A preparation method of an iron-based phosphate sodium-ion battery positive electrode material is characterized by comprising the following specific steps:
(1) preparing a polyaniline-coated iron phosphate composite material;
(2) adding sodium salt and phosphate according to the stoichiometric ratio of various elements in the electrode material by taking iron phosphate coated by polyaniline as a precursor to prepare an iron-based phosphate sodium-ion battery anode material;
(3) pre-sintering an iron-based phosphate precursor, grinding and mixing uniformly, and then formally sintering to obtain an iron-based phosphate sodium-ion battery positive electrode material;
in the step (1), the polyaniline-coated iron phosphate precursorThe core-shell structure material takes iron phosphate as an inner core and polyaniline as a shell; the preparation method comprises the following steps: in the presence of phosphate PO4 3- Adding ferric iron salt Fe into the solution of aniline 3+ ，Fe 3+ On the one hand as PO 4 3- To generate nano-sized iron phosphate active substance particles; and on the other hand, the polyaniline-coated nano iron phosphate is used as an oxidant to promote the polymerization of aniline on the surface of the iron phosphate, so that the polyaniline-coated nano iron phosphate is obtained.
2. The method according to claim 1, wherein the phosphate PO4 in step (1) is 3- Is NH 4 H 2 PO 4 、(NH 4 ) 2 HPO 4 Or (NH) 4 ) 3 PO 4 (ii) a The ferric iron salt (Fe) 3+ ) Is Fe (NO) 3 ) 3 、FeCl 3 Or Fe 2 (SO 4 ) 3 。
3. The method according to claim 2, wherein the sodium salt in the step (2) is Na 2 CO 3 、NaHCO 3 、Na 2 C 2 O 4 、CH 3 COONa、Na 3 PO 4 、Na 2 HPO 4 、NaH 2 PO 4 (ii) a The phosphate is selected from NH 4 H 2 PO 4 、(NH 4 ) 2 HPO 4 、(NH 4 ) 3 PO 4 、Na 3 PO 4 、Na 2 HPO 4 、NaH 2 PO 4 。
4. The preparation method according to claim 1, 2 or 3, wherein the iron-based phosphate sodium-ion battery cathode material in the step (2) is prepared by one or more of the following methods: high temperature solid phase method, sol-gel method, coprecipitation method, spray drying method, hydrothermal method.
5. The preparation method of claim 1, 2 or 3, wherein the iron-based phosphate sodium-ion battery positive electrode material has a molecular formula as follows:
NaFePO 4 , Na 2 FePO 4 F, Na 2 FeP 2 O 7 , Na 3.12 Fe 2.44 (P 2 O 7 ), Na 3 Fe 2 (PO 4 )P 2 O 7 , Na 4 Fe 3 (PO 4 ) 2 P 2 O 7 , Na 3 Fe 2 (PO 4 ) 3 or Na 3 Fe 2 (PO 4 ) 2 F 3 。
6. The preparation method according to claim 1, wherein in the step (3), the pre-sintering temperature is 300-500 ℃, and the pre-sintering time is 3-6 h; the sintering temperature is 500-800 ℃, and the sintering time is 6-18 h; the atmosphere during pre-sintering and sintering is air, nitrogen, argon or hydrogen-argon mixed gas.
7. The method for preparing the iron-based phosphate sodium-ion battery positive electrode material according to claim 1, wherein the average particle diameter of the iron-based phosphate sodium-ion battery positive electrode material is 5-1000 nm.
8. The method according to claim 1, wherein the surface of the positive electrode material for a sodium-ion battery is coated with a coating element or compound.
9. The production method according to claim 8, wherein the coating material is a carbon material, a metal oxide, or a metal; wherein:
the carbon material is amorphous carbon, hard carbon, carbon black or graphite;
the metal oxide is tin dioxide, titanium dioxide, ferroferric oxide or ferric oxide;
the metal is gold, silver, copper or aluminum.
10. The iron-based phosphate sodium-ion battery cathode material prepared by the preparation method of any one of claims 1 to 9.
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