CN114388757A - Prussian white material for positive electrode of sodium-ion battery and preparation method thereof - Google Patents
Prussian white material for positive electrode of sodium-ion battery and preparation method thereof Download PDFInfo
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- CN114388757A CN114388757A CN202111627009.1A CN202111627009A CN114388757A CN 114388757 A CN114388757 A CN 114388757A CN 202111627009 A CN202111627009 A CN 202111627009A CN 114388757 A CN114388757 A CN 114388757A
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- 239000000463 material Substances 0.000 title claims abstract description 58
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 229910001415 sodium ion Inorganic materials 0.000 title claims abstract description 15
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 title claims abstract description 9
- 239000000243 solution Substances 0.000 claims abstract description 69
- 239000007864 aqueous solution Substances 0.000 claims abstract description 62
- 239000011734 sodium Substances 0.000 claims abstract description 45
- 159000000000 sodium salts Chemical class 0.000 claims abstract description 42
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910052751 metal Inorganic materials 0.000 claims abstract description 17
- 239000002184 metal Substances 0.000 claims abstract description 17
- 150000003839 salts Chemical class 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 10
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 32
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 28
- 239000007789 gas Substances 0.000 claims description 21
- 238000006243 chemical reaction Methods 0.000 claims description 18
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 16
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 14
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 14
- 229910021645 metal ion Inorganic materials 0.000 claims description 12
- 239000002244 precipitate Substances 0.000 claims description 11
- 230000001681 protective effect Effects 0.000 claims description 11
- 239000000126 substance Substances 0.000 claims description 11
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 10
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 10
- 235000002867 manganese chloride Nutrition 0.000 claims description 10
- 239000011565 manganese chloride Substances 0.000 claims description 10
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 10
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 8
- 238000011049 filling Methods 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 4
- 229910002651 NO3 Inorganic materials 0.000 claims description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 4
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 239000007774 positive electrode material Substances 0.000 claims description 4
- 229910052723 transition metal Inorganic materials 0.000 claims description 4
- 229910001428 transition metal ion Inorganic materials 0.000 claims description 4
- 150000003624 transition metals Chemical class 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 2
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 2
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 2
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 2
- 229960003280 cupric chloride Drugs 0.000 claims description 2
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 claims description 2
- 229910000397 disodium phosphate Inorganic materials 0.000 claims description 2
- 235000019800 disodium phosphate Nutrition 0.000 claims description 2
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 2
- 239000011790 ferrous sulphate Substances 0.000 claims description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 2
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 2
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 2
- 229910000403 monosodium phosphate Inorganic materials 0.000 claims description 2
- 235000019799 monosodium phosphate Nutrition 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- 239000001632 sodium acetate Substances 0.000 claims description 2
- 235000017281 sodium acetate Nutrition 0.000 claims description 2
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 claims description 2
- 229910000162 sodium phosphate Inorganic materials 0.000 claims description 2
- 239000001488 sodium phosphate Substances 0.000 claims description 2
- 235000011008 sodium phosphates Nutrition 0.000 claims description 2
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 abstract description 8
- 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 abstract description 6
- 238000005056 compaction Methods 0.000 abstract description 6
- 230000008569 process Effects 0.000 abstract description 5
- 238000012545 processing Methods 0.000 abstract description 4
- 230000002035 prolonged effect Effects 0.000 abstract description 3
- 230000035484 reaction time Effects 0.000 abstract description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 31
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 18
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 12
- 229910052744 lithium Inorganic materials 0.000 description 12
- 229910017053 inorganic salt Inorganic materials 0.000 description 10
- 239000001257 hydrogen Substances 0.000 description 9
- 229910052739 hydrogen Inorganic materials 0.000 description 9
- 229910052757 nitrogen Inorganic materials 0.000 description 9
- 239000011572 manganese Substances 0.000 description 8
- 229940099596 manganese sulfate Drugs 0.000 description 8
- 239000011702 manganese sulphate Substances 0.000 description 8
- 235000007079 manganese sulphate Nutrition 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 238000001035 drying Methods 0.000 description 7
- 230000002572 peristaltic effect Effects 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- 150000002431 hydrogen Chemical class 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 238000007789 sealing Methods 0.000 description 4
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 description 3
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 3
- 229910021577 Iron(II) chloride Inorganic materials 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 3
- 229960002089 ferrous chloride Drugs 0.000 description 3
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 3
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 3
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 3
- 229910021592 Copper(II) chloride Inorganic materials 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 150000001879 copper Chemical class 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000002000 Electrolyte additive Substances 0.000 description 1
- 229910020657 Na3V2(PO4)3 Inorganic materials 0.000 description 1
- 229910019398 NaPF6 Inorganic materials 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- CNLWCVNCHLKFHK-UHFFFAOYSA-N aluminum;lithium;dioxido(oxo)silane Chemical compound [Li+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O CNLWCVNCHLKFHK-UHFFFAOYSA-N 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000005234 chemical deposition Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 150000003388 sodium compounds Chemical class 0.000 description 1
- 229910052642 spodumene Inorganic materials 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention relates to the field of batteries, in particular to a Prussian white material for a sodium ion battery anode and a preparation method thereof, wherein inorganic sodium salt aqueous solution and Na are mixed4Fe(CN)6The solution and inorganic metal salt water solution react under 0.2-10MPa and 50-100 deg.C anaerobic or oxygen-free atmosphere. Compared with the traditional process, the reaction time of the technical scheme of the invention is greatly shortened; the Prussian white material has high crystallinity, less coordinated water and sodium content close to a theoretical value, and the electrical property of the corresponding battery is remarkably improved, particularly the cycle life is prolonged; the Prussian white material has high compaction density, good processing performance and obviously improved volume energy density and mass energy density.
Description
Technical Field
The invention relates to the field of batteries, in particular to a Prussian white material for a sodium-ion battery anode and a preparation method thereof.
Background
In the 21 st century, lithium batteries are used in a variety of fields such as mobile phones, computers, wearable devices, electric automobiles, two-wheel bicycles, electric tools, street lamps and the like. In recent years, consumption of lithium resources has been a phenomenon that consumption is large and consumption speed is fast, and the increase in the amount of production of lithium cannot satisfy the increase in consumption: this is because lithium resources are limited, which exist mainly in the states of spodumene ore and lithium in salt lake, and lithium in salt lake cannot be extracted in winter.
In contrast, sodium is widely available and abundant, the storage capacity of sodium is 420 times that of lithium, and the price is far lower than that of lithium. In recent years, with the rapid increase of lithium price, the sodium ion battery is expected to be widely paid attention to with the cost 30-50% lower than that of the lithium ion battery, and particularly has attractive application prospect in the fields of energy storage, hybrid power and lead-acid battery replacement.
Sodium is a second light alkali metal and has chemical properties similar to that of lithium, but the atomic radius of sodium is 34.2% larger than that of lithium, so that sodium compounds used as positive electrode materials of lithium cobaltate, lithium iron phosphate, ternary materials, lithium manganate and the like in lithium ions have poor electrochemical properties, such as low capacity, low discharge voltage, high charge voltage and low charge-discharge efficiency.
At present, the sodium ion anode material with higher value is Na3V2(PO4)3、NaFe1/3Ni1/3Mn1/3O3Prussian white; compared with other two materials, the Prussian white material has attracted more attention due to the fact that the Prussian white material does not contain precious metals, and has higher gram capacity and voltage platform.
However, prussian white materials are generally synthesized under low temperature aqueous conditions. The synthesis method has the following three problems: firstly, the reaction process is long in time, generally 6-10 h; secondly, the crystallinity is low, more lattice defects exist, and the Na content of the obtained product is lower than the theoretical value; thirdly, the rapid chemical deposition usually generates a large amount of Fe (CN)6 4-The material has the advantages that the material has ultra-small crystal grains and low-crystallinity crystal grains of vacancies, and the vacancies are occupied by coordinated water which is difficult to remove, so that the electrochemical properties of the material are reduced, such as the rate capability is deteriorated and the cycle life is reduced; meanwhile, rapid deposition also causes the electrode density compaction reduction of the material, the material processing performance deterioration and the limitationIts volumetric energy density and mass energy density are shown.
Disclosure of Invention
In order to solve the problems, the invention provides a prussian white material and a preparation method thereof.
The first purpose of the invention is to provide a preparation method of a prussian white material, which comprises the following steps: mixing inorganic sodium salt aqueous solution and Na4Fe(CN)6Reacting the solution with inorganic metal salt water solution under 0.2-10MPa and 50-100 deg.C in anaerobic or oxygen-free atmosphere to obtain white precipitate;
wherein, in the inorganic sodium salt aqueous solution, the concentration of sodium ions is 2-10 mol/L; in the presence of Na4Fe(CN)6In solution, Fe (CN)6 4-The concentration is 0.01-0.2 mol/L; in the inorganic metal salt aqueous solution, the metal ions are divalent transition metal ions, and the concentration of the metal ions is 0.01-0.5 mol/L.
Preferably, the reaction is carried out at a pressure of 2 to 5 MPa.
The invention discovers that when the reaction is carried out under the high-pressure condition, the crystallinity of the product is high, the coordinated water is reduced, the Na content of the obtained product is close to a theoretical value, the electrical property of the corresponding battery is obviously improved, and particularly the cycle life is prolonged; in addition, the reaction under high pressure condition is favorable for the growth of material grains, so that the compaction density of the material is 0.2-0.4g/cm higher than that of the conventional process3The processing performance of the material is improved, and the volume energy density and the mass energy density are obviously improved.
Preferably, the concentration of sodium ions in the aqueous solution of inorganic sodium salt is 5 to 8 mol/L.
The invention adopts high sodium salt concentration, which is beneficial to the synthesis of high-sodium Prussian white material under high pressure.
Preferably, the compound is represented by the formula Na4Fe(CN)6In solution, Fe (CN)6 4-The concentration of (A) is 0.05-0.12 mol/L; and/or, in the above-mentioned inorganic metal salt aqueous solution, the metal ion concentration is 0.1-0.3 mol/L.
Preferably, the aqueous solution of inorganic sodium salt is a mixed solution of one or more of an aqueous solution of sodium carbonate, an aqueous solution of sodium bicarbonate, an aqueous solution of sodium acetate, an aqueous solution of sodium phosphate, an aqueous solution of sodium hydrogen phosphate, and an aqueous solution of sodium dihydrogen phosphate.
More preferably, the inorganic sodium salt aqueous solution is a mixed solution of a sodium carbonate aqueous solution and a sodium bicarbonate aqueous solution, wherein the molar ratio of sodium carbonate to sodium bicarbonate is 2: 1.
The sodium salt has strong alkali, weak acidity and high sodium salt concentration, and is more beneficial to the synthesis of high-sodium Prussian white under high pressure.
Preferably, in the aqueous solution of an inorganic metal salt, the metal ion is selected from Fe2+、Mn2+、Cu2+One or more of; wherein Mn is2+One or more of manganous chloride, manganous sulfate and manganous nitrate; cu2+One or more of copper dichloride, copper sulfate and copper nitrate; fe2+Derived from one or more of ferric chloride, ferrous sulfate, and ferrous nitrate.
Preferably, the chemical formula of the Prussian white material is NaxM[Fe(CN)6]y￡1-y·zH2O, wherein x is more than or equal to 0 and less than or equal to 2, y is more than or equal to 0 and less than or equal to 1, z is more than or equal to 0 and represents Fe (CN)6 4-A vacancy, M is a divalent transition metal. More preferably, M is one or more of Fe, Mn and Cu.
Preferably, the raw materials of the preparation method comprise the following components in parts by volume: 2-4 parts of inorganic sodium salt aqueous solution and Na4Fe(CN)61-2 parts of solution and 1-2 parts of inorganic metal salt aqueous solution.
The prussian white material of the present invention can be obtained by those skilled in the art according to the above conditions in further preferred combinations.
As a most preferred preparation method, the method comprises the following steps:
(1) adding an inorganic sodium salt aqueous solution, and then filling protective gas into the closed system, wherein the gas pressure is set to be 2-5 MPa; the concentration of sodium ions in the inorganic sodium salt aqueous solution is 5-8 mol/L; the inorganic sodium salt aqueous solution is a mixed solution of a sodium carbonate aqueous solution and a sodium bicarbonate aqueous solution, wherein the molar ratio of sodium carbonate to sodium bicarbonate is 2: 1;
(2) Mixing Na4Fe(CN)6Adding the solution and an inorganic metal salt aqueous solution into the inorganic sodium salt aqueous solution for reaction to prepare a white precipitate; the Na is4Fe(CN)6Fe (CN) in solution6 4-The concentration is 0.05-0.12 mol/L; in the inorganic metal salt aqueous solution, the metal ions are divalent transition metal ions, and the concentration of the metal ions is 0.01-0.5 mol/L; the reaction temperature is 50-100 ℃.
Preferably, the closed system may be a closed autoclave, and the protective gas may be one or a mixture of nitrogen, hydrogen, argon, and helium.
Preferably, step (2) is carried out by pumping Na with a peristaltic pump4Fe(CN)6Adding the solution and the aqueous solution of inorganic metal salt into the aqueous solution of inorganic sodium salt for reaction for 2-4 h.
Preferably, the white precipitate is washed with water, centrifuged, filtered and dried at 100 ℃ and 120 ℃ for 10-12 hours.
The drying condition can effectively remove the adsorbed water and the crystal water in the material, and further improve the electrochemical performance of the material.
The second purpose of the invention is to provide a Prussian white material which is prepared by the preparation method and has the chemical general formula of NaxM[Fe(CN)6]y￡1-y·zH2O, wherein x is more than or equal to 0 and less than or equal to 2, y is more than or equal to 0 and less than or equal to 1, z is more than or equal to 0 and represents Fe (CN)6 4-A vacancy, M is a divalent transition metal. Preferably, M is one or more of Fe, Mn and Cu.
Furthermore, the Prussian white material provided by the invention can be applied to a positive electrode material of a sodium-ion battery.
The third purpose of the invention is to provide a positive electrode material of a sodium-ion battery, which contains the Prussian white material.
Compared with the prior art, the invention has the following advantages:
firstly, compared with the traditional process, the reaction time is greatly shortened from 6-10h to 2-4 h; secondly, the reaction is carried out under high pressure, the crystallinity of the product is high, and the coordinated water is reduced, soThe Na content of the obtained product is close to a theoretical value, and the electrical property of the corresponding battery is remarkably improved, particularly the cycle life is prolonged; thirdly, the reaction is carried out under high pressure, which is beneficial to the growth of material particles, so that the compaction density of the material is 0.2-0.4g/cm higher than that of the conventional process3The processing performance of the material is improved, and the volume energy density and the mass energy density are obviously improved.
Detailed Description
The following examples are intended to illustrate the invention but are not intended to limit the scope of the invention.
The specific techniques or conditions not indicated in the examples are all conventional methods or techniques or conditions described in the literature of the field or according to the product specifications. The reagents and instruments used are conventional products which are available from normal commercial vendors, not indicated by manufacturers.
Example 1
This example provides a prussian white material, which is prepared as follows:
1. preparing a solution A: na (Na)+An inorganic sodium salt aqueous solution with the concentration of 6mol/L, wherein the sodium salt is sodium carbonate and sodium bicarbonate, and the molar ratio of the sodium salt to the sodium bicarbonate is 2: 1;
2. preparing a solution B: fe (CN)6 4-Na in a concentration of 0.10mol/L4Fe(CN)6A solution;
3. preparing a solution C: mn2+0.15mol/L of inorganic salt water solution, manganese dichloride and manganese sulfate, wherein the molar ratio of the inorganic salt water solution to the manganese dichloride to the manganese sulfate is 3: 1;
4. adding 3L of the solution A into a 10L high-pressure autoclave, sealing the high-pressure autoclave, and filling protective gas, wherein the gas pressure is set to be 3MPa, the protective gas is a mixed gas of nitrogen and hydrogen, and the molar ratio of the nitrogen to the hydrogen is 9: 1;
5. setting the temperature of the autoclave at 60 ℃, adding 2L of the solution B and 2L of the solution C into the autoclave through a peristaltic pump for 3.5 hours;
6. washing the white precipitate obtained in the step 5 with water, centrifuging, filtering, drying at 120 deg.C for 10h to obtain Prussian white material, and determining by XRD and FTIR that the synthesized material has chemical formula of Na1.92Mn[Fe(CN)6]0.96￡0.04·1.35H2O。
Example 2
This example provides a prussian white material, which is prepared as follows:
1. preparing a solution A: na (Na)+An inorganic sodium salt aqueous solution with the concentration of 6mol/L, wherein the sodium salt is sodium carbonate and sodium bicarbonate, and the molar ratio of the sodium salt to the sodium bicarbonate is 2: 1;
2. preparing a solution B: fe (CN)6 4-Na in a concentration of 0.10mol/L4Fe(CN)6A solution;
3. preparing a solution C: fe2+0.15mol/L of inorganic salt aqueous solution, iron dichloride and ferric sulfate, wherein the molar ratio of the iron dichloride to the ferric sulfate is 3: 1;
4. adding 3L of the solution A into a 10L high-pressure autoclave, sealing the high-pressure autoclave, and filling protective gas, wherein the gas pressure is set to be 3MPa, the protective gas is a mixed gas of nitrogen and hydrogen, and the molar ratio of the nitrogen to the hydrogen is 9: 1;
5. setting the temperature of the autoclave at 60 ℃, adding 2L of the solution B and 2L of the solution C into the autoclave through a peristaltic pump for 3.5 hours;
6. washing the white precipitate obtained in the step 5 with water, centrifuging, filtering, drying at 120 deg.C for 10h to obtain Prussian white material, and determining by XRD and FTIR that the synthesized material has chemical formula of Na1.96Fe[Fe(CN)6]0.97￡0.03·1.26H2O。
Example 3
This example provides a prussian white material, which is prepared as follows:
1. preparing a solution A: na (Na)+An inorganic sodium salt aqueous solution with the concentration of 6mol/L, wherein the sodium salt is sodium carbonate and sodium bicarbonate, and the molar ratio of the sodium salt to the sodium bicarbonate is 2: 1;
2. preparing a solution B: fe (CN)6 4-Na in a concentration of 0.10mol/L4Fe(CN)6A solution;
3. preparing a solution C: mn2+0.15mol/L of inorganic salt water solution, manganese dichloride and manganese sulfate, wherein the molar ratio of the inorganic salt water solution to the manganese dichloride to the manganese sulfate is 3:1；Cu2+the concentration is 0.01mol/L, and the copper salt is CuCl2；
4. Adding 3L of the solution A into a 10L high-pressure autoclave, sealing the high-pressure autoclave, and filling protective gas, wherein the gas pressure is set to be 3MPa, the protective gas is a mixed gas of nitrogen and hydrogen, and the molar ratio of the nitrogen to the hydrogen is 9: 1;
5. setting the temperature of the autoclave at 60 ℃, adding 2L of the solution B and 2L of the solution C into the autoclave through a peristaltic pump for 3.5 hours;
6. washing the white precipitate obtained in the step 5 with water, centrifuging, filtering, drying at 120 deg.C for 10h to obtain Prussian white material, and determining by XRD and FTIR that the synthesized material has chemical formula of Na1.94Cu0.08Mn0.92[Fe(CN)6]0.96￡0.04·1.30H2O。
Comparative example 1
The present comparative example provides a prussian white material, the preparation method of which is as follows:
1. preparing a solution A: na (Na)+An inorganic sodium salt aqueous solution with the concentration of 6mol/L, wherein the sodium salt is sodium carbonate and sodium bicarbonate, and the molar ratio of the sodium salt to the sodium bicarbonate is 2: 1;
2. preparing a solution B: fe (CN)6 4-Na in a concentration of 0.10mol/L4Fe(CN)6A solution;
3. preparing a solution C: mn2+0.15mol/L of inorganic salt water solution, manganese dichloride and manganese sulfate, wherein the molar ratio of the inorganic salt water solution to the manganese dichloride to the manganese sulfate is 3: 1;
4. adding 3L of the solution A into a 10L common reaction kettle;
5. setting the temperature of the reaction kettle in the step 4 to be 60 ℃, and adding 2L of the solution B and 2L of the solution C into the reaction kettle through a peristaltic pump for 8 hours;
6. washing the white precipitate obtained in the step 5 with water, centrifuging, filtering, drying at 120 deg.C for 10h to obtain Prussian white material, and determining by XRD and FTIR that the synthesized material has chemical formula of Na1.38Mn[Fe(CN)6]0.85￡0.15·3.02H2O。
Comparative example 2
The present comparative example provides a prussian white material, the preparation method of which is as follows:
1. preparing a solution A: na (Na)+The concentration of the inorganic sodium salt aqueous solution is 6mol/L, the sodium salt is sodium carbonate and sodium bicarbonate, and the molar ratio of the sodium salt to the sodium bicarbonate is 2: 1;
2. preparing a solution B: fe (CN)6 4-Na in a concentration of 0.10mol/L4Fe(CN)6A solution;
3. preparing a solution C: fe2+The concentration of the inorganic salt aqueous solution is 0.15mol/L, and the molar ratio of iron dichloride to ferric sulfate is 3: 1;
4. adding 3L of the solution A into a 10L common reaction kettle;
5. setting the temperature of the reaction kettle in the step 4 to be 60 ℃, and adding 2L of the solution B and 2L of the solution C into the reaction kettle through a peristaltic pump for 8 hours;
6. washing the white precipitate obtained in step 5 with water, centrifuging, filtering, drying at 120 deg.C for 10h to obtain Prussian white material, and determining by XRD and FTIR that the synthesized material has chemical formula of Na1.33Fe[Fe(CN)6]0.84￡0.16·3.27H2O。
Comparative example 3
The present comparative example provides a prussian white material, the preparation method of which is as follows:
1. preparing a solution A: na (Na)+An inorganic sodium salt aqueous solution with the concentration of 6mol/L, wherein the sodium salt is sodium carbonate and sodium bicarbonate, and the molar ratio of the sodium salt to the sodium bicarbonate is 2: 1;
2. preparing a solution B: fe (CN)6 4-Na in a concentration of 0.10mol/L4Fe(CN)6A solution;
3. preparing a solution C: mn2+0.15mol/L of inorganic salt water solution, manganese dichloride and manganese sulfate, wherein the molar ratio of the inorganic salt water solution to the manganese dichloride to the manganese sulfate is 3: 1; cu2+The concentration is 0.01mol/L, and the copper salt is CuCl2；
4. Adding 3L of the solution A into a 10L high-pressure autoclave, sealing the high-pressure autoclave, and filling protective gas, wherein the gas pressure is set to be 3MPa, the protective gas is a mixed gas of nitrogen and hydrogen, and the molar ratio of the nitrogen to the hydrogen is 9: 1;
5. setting the temperature of the autoclave at 60 ℃, adding 2L of the solution B and 2L of the solution C into the autoclave through a peristaltic pump for 3.5 hours;
6. washing the white precipitate obtained in the step 5 with water, centrifuging, filtering, drying at 120 deg.C for 10h to obtain Prussian white material, and determining by XRD and FTIR that the synthesized material has chemical formula of Na1.36Cu0.05Mn0.95[Fe(CN)6]0.83￡0.17·3.56H2O。
Performance verification
Preparing a half cell: prussian white materials prepared in the above examples and comparative examples are used as a positive electrode, metal sodium is used as a negative electrode, a PP/PE/PP diaphragm with the diameter of 20 mu m, and NaPF6The Ethylene Carbonate (EC)/dimethyl carbonate (DEC) solution of (D) was used as the electrolyte, fluoroethylene carbonate (FEC) was used as the electrolyte additive (the molar ratio of FEC to EC + DMC was 1: 20). And (3) assembling a battery in the glove box filled with argon, and performing charge and discharge tests (with the voltage range of 2-4V). The mass percentage of the Prussian white, the binder PVDF and the conductive agent SP in the positive electrode is 94:3: 3.
Determination of powder compaction Density: 10g of the powder was charged into a die having a diameter of 12.8mm, a pressure of 10 tons was applied for 1min, and the volume of the powder after pressing was measured to calculate the powder compacted density.
Capacity retention ratio: cycle N discharge capacity/cycle first discharge capacity 100%
The test results are shown in table 1.
TABLE 1
As can be seen from Table 1, the Prussian white material provided by the invention has the advantages that the mass energy density is remarkably improved, and the compaction density of the material is 0.2-0.4g/cm higher than that of the material obtained by the conventional process3The cycle life of the battery is significantly improved.
Although the invention has been described in detail hereinabove with respect to a general description and specific embodiments thereof, it will be apparent to those skilled in the art that modifications or improvements may be made thereto based on the invention. Accordingly, such modifications and improvements are intended to be within the scope of the invention as claimed.
Claims (10)
1. A preparation method of a Prussian white material is characterized by comprising the following steps:
mixing inorganic sodium salt aqueous solution and Na4Fe(CN)6Reacting the solution with inorganic metal salt water solution under 0.2-10MPa and 50-100 deg.C in anaerobic or oxygen-free atmosphere to obtain white precipitate;
wherein, in the inorganic sodium salt aqueous solution, the concentration of sodium ions is 2-10 mol/L; in the presence of Na4Fe(CN)6In solution, Fe (CN)6 4-The concentration is 0.01-0.2 mol/L; in the inorganic metal salt aqueous solution, the metal ions are divalent transition metal ions, and the concentration of the metal ions is 0.01-0.5 mol/L.
2. The production method according to claim 1, wherein the reaction is carried out at 2 to 5 MPa.
3. The production method according to claim 1 or 2, wherein the concentration of sodium ions in the aqueous solution of an inorganic sodium salt is 5 to 8 mol/L.
4. The method according to any one of claims 1 to 3, wherein Na is added to the solution4Fe(CN)6In solution, Fe (CN)6 4-The concentration of (A) is 0.05-0.12 mol/L;
and/or, in the inorganic metal salt aqueous solution, the metal ion concentration is 0.1-0.3 mol/L.
5. The preparation method according to any one of claims 1 to 4, wherein the inorganic sodium salt aqueous solution is a mixed solution of one or more of a sodium carbonate aqueous solution, a sodium bicarbonate aqueous solution, a sodium acetate aqueous solution, a sodium phosphate aqueous solution, a sodium hydrogen phosphate aqueous solution, and a sodium dihydrogen phosphate aqueous solution;
preferably a mixed solution of an aqueous solution of sodium carbonate and an aqueous solution of sodium bicarbonate, wherein the molar ratio of sodium carbonate to sodium bicarbonate is 2: 1.
6. The method according to any one of claims 1 to 5, wherein in the aqueous solution of an inorganic metal salt, a metal ion is selected from Fe2+、Mn2+、Cu2+One or more of; wherein Mn is2+One or more of manganous chloride, manganous sulfate and manganous nitrate; cu2+One or more of copper dichloride, copper sulfate and copper nitrate; fe2+Derived from one or more of ferric chloride, ferrous sulfate, and ferrous nitrate.
7. The preparation method according to claims 1 to 6, wherein the Prussian white material has a chemical general formula of
Wherein x is more than or equal to 0 and less than or equal to 2, y is more than or equal to 0 and less than or equal to 1, z is more than or equal to 0,
represents Fe (CN)6 4-A vacancy, M is a divalent transition metal;
the raw materials comprise the following components in parts by volume: 2-4 parts of inorganic sodium salt aqueous solution, and Na4Fe(CN)61-2 parts of solution and 1-2 parts of inorganic metal salt aqueous solution.
8. The method according to claim 1 to 7, comprising the steps of:
(1) adding an inorganic sodium salt aqueous solution, and then filling protective gas into the closed system, wherein the gas pressure is set to be 2-5 MPa; the concentration of sodium ions in the inorganic sodium salt aqueous solution is 5-8 mol/L; the inorganic sodium salt aqueous solution is a mixed solution of a sodium carbonate aqueous solution and a sodium bicarbonate aqueous solution, wherein the molar ratio of sodium carbonate to sodium bicarbonate is 2: 1;
(2) mixing Na4Fe(CN)6Adding the solution and an inorganic metal salt aqueous solution into the inorganic sodium salt aqueous solution for reaction to prepare a white precipitate; the Na is4Fe(CN)6Fe (CN) in solution6 4-The concentration is 0.05-0.12 mol/L; in the inorganic metal salt aqueous solution, the metal ions are divalent transition metal ions, and the concentration of the metal ions is 0.01-0.5 mol/L; the reaction temperature is 50-100 ℃.
9. A Prussian white material prepared by the preparation method of claims 1-8 and having a chemical general formula
Wherein x is more than or equal to 0 and less than or equal to 2, y is more than or equal to 0 and less than or equal to 1, z is more than or equal to 0,
represents Fe (CN)6 4-A vacancy, M is a divalent transition metal.
10. A positive electrode material for a sodium-ion battery, which contains the prussian white material according to claim 9.
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| DE112022000978T5 (en) | 2022-08-15 | 2024-04-04 | Guangdong Brunp Recycling Technology Co., Ltd. | METHOD FOR REGULATING THE PARTICLE SIZE OF PRUSSIAN SWEAT |
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| CN111377462A (en) * | 2019-07-05 | 2020-07-07 | 上海交通大学 | Prussian blue positive electrode material, sodium ion battery and preparation method and application of prussian blue positive electrode material and sodium ion battery |
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| CN107364874A (en) * | 2017-06-22 | 2017-11-21 | 全球能源互联网研究院 | A kind of Prussian blue method for preparing anode material and sodium-ion battery |
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