CN112687898A - Electrode material, preparation method and application thereof, and sodium-air battery - Google Patents
Electrode material, preparation method and application thereof, and sodium-air battery Download PDFInfo
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- 239000007772 electrode material Substances 0.000 title claims abstract description 60
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- DCYOBGZUOMKFPA-UHFFFAOYSA-N iron(2+);iron(3+);octadecacyanide Chemical group [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 claims abstract description 27
- 239000003792 electrolyte Substances 0.000 claims abstract description 15
- 230000002950 deficient Effects 0.000 claims abstract description 4
- 229910052751 metal Inorganic materials 0.000 claims description 29
- 239000002184 metal Substances 0.000 claims description 29
- 150000003839 salts Chemical class 0.000 claims description 25
- 239000007800 oxidant agent Substances 0.000 claims description 19
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 17
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 17
- 150000001875 compounds Chemical class 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 11
- GTSHREYGKSITGK-UHFFFAOYSA-N sodium ferrocyanide Chemical compound [Na+].[Na+].[Na+].[Na+].[Fe+2].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] GTSHREYGKSITGK-UHFFFAOYSA-N 0.000 claims description 10
- 239000000264 sodium ferrocyanide Substances 0.000 claims description 10
- 235000012247 sodium ferrocyanide Nutrition 0.000 claims description 10
- 230000007547 defect Effects 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 9
- 239000007784 solid electrolyte Substances 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical group [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 8
- 239000005708 Sodium hypochlorite Substances 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- 230000001590 oxidative effect Effects 0.000 claims description 8
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- 239000002105 nanoparticle Substances 0.000 claims description 7
- AEBYJSOWHQYRPK-UHFFFAOYSA-N 1,1'-biphenyl;sodium Chemical compound [Na].C1=CC=CC=C1C1=CC=CC=C1 AEBYJSOWHQYRPK-UHFFFAOYSA-N 0.000 claims description 6
- 239000000276 potassium ferrocyanide Substances 0.000 claims description 6
- XOGGUFAVLNCTRS-UHFFFAOYSA-N tetrapotassium;iron(2+);hexacyanide Chemical compound [K+].[K+].[K+].[K+].[Fe+2].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] XOGGUFAVLNCTRS-UHFFFAOYSA-N 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 5
- 239000002244 precipitate Substances 0.000 claims description 5
- 229960003351 prussian blue Drugs 0.000 claims description 5
- 239000013225 prussian blue Substances 0.000 claims description 5
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 4
- 239000011734 sodium Substances 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 3
- 229910002651 NO3 Inorganic materials 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 3
- 150000001868 cobalt Chemical class 0.000 claims description 3
- 229910017052 cobalt Inorganic materials 0.000 claims description 3
- 239000010941 cobalt Substances 0.000 claims description 3
- 229910052593 corundum Inorganic materials 0.000 claims description 3
- 239000010416 ion conductor Substances 0.000 claims description 3
- 150000002505 iron Chemical class 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N nitrate group Chemical group [N+](=O)([O-])[O-] NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 3
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 230000007797 corrosion Effects 0.000 abstract description 3
- 238000005260 corrosion Methods 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 27
- 230000000052 comparative effect Effects 0.000 description 19
- 239000003054 catalyst Substances 0.000 description 7
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 6
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 238000011161 development Methods 0.000 description 5
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 239000002228 NASICON Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- -1 optionally Substances 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000012266 salt solution Substances 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 238000000024 high-resolution transmission electron micrograph Methods 0.000 description 2
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 2
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000003756 stirring Methods 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
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001447 alkali salts Chemical class 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 1
- 229940044175 cobalt sulfate Drugs 0.000 description 1
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 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 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 150000002815 nickel Chemical class 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- ZBNMBCAMIKHDAA-UHFFFAOYSA-N sodium superoxide Chemical compound [Na+].O=O ZBNMBCAMIKHDAA-UHFFFAOYSA-N 0.000 description 1
- 229910000144 sodium(I) superoxide Inorganic materials 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229910021653 sulphate ion Inorganic materials 0.000 description 1
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Abstract
The invention discloses an electrode material, a preparation method and application thereof, and a sodium-air battery. The electrode material has a unit cell structure of [ Fe (CN)6]Vacancy-deficient prussian blue structure. The electrode material is used as an air electrode material to prepare the sodium-air battery, so that the discharge platform, the energy density and the discharge capacity of the sodium-air battery can be effectively improved, higher conductivity can be provided to a certain extent, the internal resistance of the battery is reduced, and meanwhile, the corrosion of electrolyte to the electrode is effectively reduced, so that the performance of the battery is improved, and the electrode material has important significance for the commercialization of the sodium-air battery.
Description
Technical Field
The invention relates to the technical field of air batteries, in particular to an electrode material, a preparation method and application thereof and a sodium-air battery.
Background
With the rapid development of the automobile industry, energy crisis and air pollution become major problems restricting the sustainable development of the global economy, and in order to improve the competitiveness of the automobile industry, guarantee the energy safety and develop low-carbon economy, the industrialization of new energy automobiles becomes a strategic consensus in the international automobile industry and a major strategic demand in the scientific and technological development of China. Although the power and energy storage system of the current new energy automobile mainly uses a lithium ion battery, the market acceptance is low due to the facts that the initial acquisition cost is high, the charging time is long (3-4) hours, the specific energy density is low (150-200 watt-hour/kilogram), the cruising mileage of the electric automobile is short, the number of charging equipment facilities is small, and commercial bottlenecks such as potential safety hazards exist. Therefore, the development of a high energy density battery system suitable for an electric vehicle is an urgent task for researchers.
Metal-air batteries are currently the focus of research because they have an energy density 3 to 10 times higher than that of the lithium ion batteries already commercialized, and are promising energy storage devices that can compete with petroleum in the power supply system of new energy vehicles. Among them, lithium-air batteries are widely noticed due to their high energy density, but since the global storage of metal lithium resources is limited, the large-scale application of lithium-air batteries will bring about a cost problem. In addition, lithium-air batteries have a higher overpotential than sodium-air batteries, resulting in lower energy efficiency. While lithium-air batteries are theoretically more energy dense, sodium-air batteries have achieved higher energy densities than lithium-air batteries in experiments. In a word, the sodium-air battery has the advantages of high energy efficiency (lower overpotential), good cycle performance (better stability of sodium superoxide), lower price (rich reserve of sodium element) and the like, and has a wide application prospect in electric vehicles. Therefore, the development of research related to the application of sodium-air batteries is of great significance to solve energy crisis and environmental pollution.
However, the current sodium-air battery has a general challenge that the catalytic efficiency and stability of the air electrode are not good. The concrete expression is as follows: firstly, the catalytic efficiency of the existing catalyst is poor, and the energy efficiency of the battery in the charging and discharging process cannot be met; second, the catalyst is not stable enough, and most of the oxides and carbon materials are easily corroded in an acid-base solution, thereby causing a decrease in the catalytic efficiency and stability of the catalyst.
Therefore, an air electrode material with high catalytic efficiency and good stability is needed.
In view of this, the invention is particularly proposed.
Disclosure of Invention
The object of the present invention is to provide an electrode material, a method for the production thereof, and a use thereof, and a sodium-air battery, which are capable of improving at least one of the above technical problems.
The invention is realized by the following steps:
in a first aspect, the present invention provides an electrode material having a unit cell structure of [ Fe (CN)6]Vacancy-deficient prussian blue structure.
Alternatively, [ Fe (CN)6]The vacant site is Fe2+A vacancy.
Optionally, the electrode material is nanoparticles, and preferably, the particle size of the electrode material is 1-100 nm.
In a first aspect, the present invention provides a method for preparing the electrode material, which comprises: and oxidizing the compound with the unit cell structure of the Prussian blue structure to obtain the compound with the defect Prussian blue structure.
Alternatively, the compound with the unit cell structure of the Prussian blue structure is mainly prepared by the following steps: reacting the metal salt with the ferrocyanide.
Alternatively, the metal salt and the ferrocyanide are reacted in a solution system.
Optionally, the metal salt is dissolved in a solvent, and then the ferrocyanide is added for reaction to obtain a precipitate.
Optionally, the metal salt is a nickel salt, a cobalt salt or an iron salt; alternatively, the metal salt is a nitrate, sulphate or chloride of nickel, cobalt, iron.
Optionally, the ferrocyanide comprises at least one of potassium ferrocyanide and sodium ferrocyanide.
Optionally, the molar ratio of the metal salt to the ferrocyanide is 1-4: 1.
optionally, when the reaction is carried out in a solution system, the concentration of the metal salt in the solution is 0.1-10 mol/L, and the concentration of the ferrocyanide in the solution is 0.1-10 mol/L.
Alternatively, the oxidation of the compound having a prussian blue unit cell structure is carried out by dispersing the compound having a prussian blue unit cell structure in a solvent and then adding an oxidizing agent to the solution to carry out the reaction.
Optionally, the oxidizing agent comprises at least one of hydrogen peroxide and sodium hypochlorite, optionally, the oxidizing agent is hydrogen peroxide or sodium hypochlorite; optionally, the oxidant is added in the form of a solution, and optionally, the concentration of the solution of the oxidant is 0.1-10 mol/L.
In a third aspect, the invention also provides application of the electrode material in preparation of a sodium-air battery.
In a fourth aspect, the invention also provides a sodium-air battery comprising an air cathode of the above electrode material, and a liquid anode, a solid electrolyte and an aqueous electrolyte.
Optionally, the liquid anode is a sodium biphenyl solution, and the solid electrolyte is Al2O3Or Na3Si2Zr2PO12The fast ion conductor and the water system electrolyte are NaOH.
The technical scheme of the invention has the following beneficial effects: with a unit cell structure [ Fe (CN)6]The electrode material with the vacancy Prussian blue structure is used as an air electrode material, so that the air electrode can effectively improve the discharge platform, the energy density and the discharge capacity of the sodium-air battery, can also provide higher conductivity to a certain extent, reduce the internal resistance of the battery, and effectively reduce the corrosion of electrolyte to the electrode, thereby improving the performance of the battery, and has important significance for the commercialization of the sodium-air battery.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the embodiments will be briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope, and for those skilled in the art, other related drawings can be obtained according to the drawings without inventive efforts.
FIG. 1 is an SEM image of the electrode material D-Co-PBA prepared in example 1;
FIG. 2 is a TEM image of the electrode material D-Co-PBA prepared in example 1;
FIG. 3 is a HRTEM image of the electrode material D-Co-PBA prepared in example 1;
FIG. 4 is a HADDF image of the electrode material D-Co-PBA prepared in example 1;
FIG. 5 is an oxygen evolution comparative image of different electrode materials in example 1, comparative example 1, and comparative example 3;
fig. 6 is a structure of the sodium-air battery prepared in example 3 and comparative examples 2 to 3;
fig. 7 is a charge-discharge comparative image of the sodium-air batteries prepared in example 3 and comparative examples 2 to 3;
fig. 8 is a battery cycle image in example 3.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
The following provides a specific description of the electrode material, the preparation method and application thereof, and the sodium-air battery.
Some embodiments of the present invention provide an electrode material having a unit cell structure of [ Fe (CN)6]Vacancy-deficient prussian blue structure.
The inventors have conducted extensive studies and practices on the basis of the air electrode of the existing sodium-air battery, and have creatively found that the unit cell structure is [ Fe (CN) ]6]The material with the vacancy Prussian blue structure is used as an air electrode material, so that the discharge platform, the energy density and the discharge capacity of the sodium-air battery can be improved, the conductivity can be improved, the resistance of the battery can be reduced, and the electricity can be reducedThe electrolyte corrodes the electrode, thereby obviously improving the performance of the sodium-air battery.
In particular, in some embodiments, the defect structures are randomly coated on at least one surface of the electrode material.
Further, in some embodiments, [ Fe (CN) in the unit cell structure6]The vacancy is Fe in Prussian blue structure2+A vacancy.
The particle size of the electrode material determines the contact degree with the electrolyte, and further affects the charge and discharge performance, so in some embodiments, the electrode material is nanoparticles, and in a preferred embodiment, the particle size of the electrode material may be 1 to 100nm, for example, 1 to 10nm or 1 to 5 nm.
Some embodiments of the present invention also provide a method for preparing the above electrode material, which includes:
s1, preparing a compound with a unit cell structure of a Prussian blue structure.
The specific preparation process comprises the following steps: reacting the metal salt with the ferrocyanide. In the reaction process, the ferrocyanide ions and the metal ions react to generate precipitates.
In some embodiments, to enable the reaction of the metal salt and the ferrocyanide, the metal salt and the ferrocyanide are typically reacted in a solution system.
Specifically, the metal salt is dissolved in a solvent, and then the ferrocyanide is added for reaction to obtain a precipitate. Wherein the solvent is generally water.
Wherein the metal salt can be nickel salt, cobalt salt or iron salt; in some embodiments, the metal salt is a nitrate, sulfate, or chloride of nickel, cobalt, or iron. For example, the above metal salt may be nickel nitrate, cobalt nitrate, ferric nitrate, nickel sulfate, cobalt sulfate, ferric sulfate, nickel chloride, cobalt chloride, ferric chloride, or the like. In some preferred embodiments, the metal salt is a cobalt salt, more specifically, it may be cobalt nitrate.
Ferrocyanide includes, but is not limited to, at least one of potassium ferrocyanide and sodium ferrocyanide. That is, the ferrocyanide is typically potassium ferrocyanide or sodium ferrocyanide, although in some embodiments, the ferrocyanide can also be a mixture of potassium ferrocyanide and sodium ferrocyanide.
Further, in order to enable the metal salt and the ferrocyanide to react sufficiently and to react well to form a prussian blue structure compound, the ratio of the reaction raw materials needs to be controlled. When the ferrocyanide is potassium ferrocyanide or sodium ferrocyanide, in some embodiments, the molar ratio of the metal salt to the ferrocyanide is 1-4: 1, for example, may be 1: 1, may be 2: 1. 3: 1 or 4: 1, etc.
Further, when the reaction is carried out in a solution system, first, a metal salt is dissolved in a solvent to obtain a metal salt solution, and the concentration of the metal salt solution is 0.1 to 10mol/L, for example, 0.1mol/L, 0.5mol/L, 1mol/L, 2mol/L, 3mol/L, 4mol/L, 5mol/L, 6mol/L, 7mol/L, 8mol/L, 9mol/L, or 10 mol/L. The ferrocyanide is added to the metal salt solution as a solution, and therefore, in some embodiments, the concentration of the solution of ferrocyanide is 0.1 to 10mol/L, for example, 0.1mol/L, 0.5mol/L, 1mol/L, 2mol/L, 3mol/L, 4mol/L, 5mol/L, 6mol/L, 7mol/L, 8mol/L, 9mol/L, or 10 mol/L.
S2, oxidizing the compound with the unit cell structure of the Prussian blue structure to obtain the compound with the defect Prussian blue structure.
Specifically, in some embodiments, the oxidation of the compound having a prussian blue unit cell structure is performed by dispersing the compound having a prussian blue unit cell structure in a solvent and adding an oxidizing agent. It is noted that, after the addition of the oxidizing agent, Fe is mainly contained in the Prussian blue structure2+Oxidation reaction is carried out to generate precipitate, and then Fe is generated2+Leaving vacancies from the prussian blue structure.
Further, in some embodiments, the oxidizing agent includes, but is not limited to, at least one of hydrogen peroxide and sodium hypochlorite. Hydrogen peroxide and sodium hypochlorite are common oxidants, and have low cost and good reactivity. In the embodiment of the present invention, the oxidizing agent may be hydrogen peroxide alone or sodium hypochlorite alone, or a mixture thereof, and the mixing ratio thereof may be any ratio.
In a preferred embodiment, the oxidizing agent is hydrogen peroxide or sodium hypochlorite. In order to enable the oxidizing agent to react with the prussian blue structure compound more effectively, in some embodiments, the oxidizing agent is added in the form of a solution, specifically, the concentration of the solution of the oxidizing agent is 0.1 to 10mol/L, and for example, the concentration may be 0.1mol/L, 0.5mol/L, 1mol/L, 2mol/L, 3mol/L, 4mol/L, 5mol/L, 6mol/L, 7mol/L, 8mol/L, 9mol/L, or 10 mol/L.
Some embodiments of the invention also provide applications of the electrode material in preparing sodium-air batteries.
Some embodiments of the present invention also provide a sodium-air battery comprising an air cathode of the above-described electrode material, and a liquid anode, a solid electrolyte, and an aqueous electrolyte.
In a preferred embodiment, the liquid anode is a sodium biphenyl solution, and the solid electrolyte is Al2O3Or Na3Si2Zr2PO12The fast ion conductor and the water system electrolyte are NaOH.
The electrode material with the defect Prussian blue structure is used as an air electrode of the sodium-air battery, so that the performance of the sodium-air battery can be remarkably improved.
The features and properties of the present invention are described in further detail below with reference to examples.
Example 1
The embodiment provides a preparation method of an electrode material, which specifically comprises the following steps:
cobalt nitrate and sodium ferrocyanide are used as raw materials to synthesize the Co-PBA Prussian blue structure. Specifically, 6mmol of cobalt nitrate is dissolved in 50ml of deionized water to obtain a solution A, and 4mmol of sodium ferrocyanide is dissolved in another 50ml of deionized water and stirred uniformly to obtain a solution B. Solution A was added dropwise to solution B and stirred for 30 min. The obtained solid was washed, centrifuged and dried to obtain a defect-free Co-PBA Prussian blue structure, named Co-PBA. Dispersing the obtained solid material in 50ml of deionized water, adding 5ml of hydrogen peroxide solution, stirring for 0.3h, and stirring and centrifuging to obtain the defect-rich nano-particles named D-Co-PBA.
Example 2
The embodiment provides a sodium-air battery, which is assembled by taking sodium biphenyl as a liquid anode, NASICON as a solid electrolyte, 0.1mol/L NaOH as an aqueous electrolyte and D-Co-PBA + Pt/C as a catalyst.
Comparative example 1
The comparative example provides a preparation method of an electrode material, which specifically comprises the following steps:
cobalt nitrate and sodium ferrocyanide are used as raw materials to synthesize the Co-PBA Prussian blue structure. Specifically, 6mmol of cobalt nitrate is dissolved in 50ml of deionized water to obtain a solution A, and 4mmol of sodium ferrocyanide is dissolved in another 50ml of deionized water and stirred uniformly to obtain a solution B. Solution A was added dropwise to solution B and stirred for 30 min. The obtained solid was washed, centrifuged and dried to obtain a defect-free Co-PBA Prussian blue structure, named Co-PBA.
Comparative example 2
The comparative example provides a sodium-air battery, which is assembled by taking sodium biphenyl as a liquid anode, NASICON as a solid electrolyte, 0.1mol/L NaOH as an aqueous electrolyte and Co-PBA + Pt/C as a catalyst.
Comparative example 3
The comparative example provides a sodium-air battery, which is assembled by taking sodium biphenyl as a liquid anode, NASICON as a solid electrolyte, 0.1mol/L NaOH as an aqueous electrolyte and Ir/C + Pt/C as a catalyst.
Test example 1
The electrode material obtained in example 1 is subjected to scanning electron microscopy for observation, and the appearance of the electrode material is shown in fig. 1, wherein the SEM image of the electrode material is shown in fig. 1, and the electrode material has a nanoparticle structure.
Further, the electrode material obtained in example 1 was subjected to TEM observation to obtain a TEM image as shown in fig. 2. As can also be seen from fig. 2, the electrode material is of a nanoparticle structure.
HRTEM observation was performed on the electrode material in example 1, and HRTEM images as shown in fig. 3 were obtained. As can be seen from fig. 3, the electrode material has a rich defect structure.
High angle annular dark field imaging (HADDF) was performed on the electrode material of example 1, resulting in a HADDF image as shown in fig. 4. As can be seen from FIG. 4, the particle diameter is 1 to 5 nm.
Test example 2
The electrode materials of example 1, comparative example 1 and comparative example 3 were subjected to an oxygen evolution test, respectively, and the results thereof are shown in fig. 5. As can be seen from fig. 5, the D-Co-PBA material in example 1 has better oxygen evolution performance, while the defect-free Co-PBA nanoparticle catalyst in comparative example 1 and the Ir/C material in comparative example 3 have poorer oxygen evolution performance.
Test example 3
The structure of the sodium-air batteries of example 2 and comparative examples 2 to 3 is shown in fig. 6. At 0.1mA cm for sodium-air batteries in example 2, comparative example 2 and comparative example 3-2The charge/discharge performance at the discharge density of (a) was measured, and a charge/discharge curve thereof is shown in fig. 7. As can be seen from FIG. 7, at 0.1mA cm-2The discharge density of the electrode is lower than that of a D-Co-PBA + Pt/C electrode.
Among them, the cycle chart of the sodium-air battery of example 3 is shown in fig. 8, and it can be seen from fig. 8 that the battery using the D-Co-PBA + Pt/C material has a high discharge efficiency and stable cycle performance.
In summary, compared with the prior art, the embodiment of the invention creatively provides an electrode material based on a defect prussian blue structure and a mixed system sodium-air battery based on the electrode material. The air electrode comprises a defect Prussian blue structure, the aqueous electrolyte comprises alkali and sodium salt with certain composition and proportion, the discharge platform, the energy density and the discharge capacity of the battery can be effectively improved by using the electrode, higher conductivity can be provided to a certain extent, the internal resistance of the battery can be reduced, meanwhile, the electrode can effectively reduce the corrosion of the electrolyte to the electrode, so that the performance of the battery is improved, and the air electrode has important significance for commercialization of a mixed system sodium-air battery.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. An electrode material characterized in that it has a unit cell structure of [ Fe (CN)6]Vacancy-deficient prussian blue structure.
2. The electrode material of claim 1, wherein [ Fe (CN)6]The vacant site is Fe2+A vacancy.
3. The electrode material according to claim 1 or 2, wherein the electrode material is a nanoparticle, preferably wherein the particle size of the electrode material is 1-100 nm, preferably 1-10 nm.
4. A method for producing an electrode material according to any one of claims 1 to 3, comprising: and oxidizing the compound with the unit cell structure of the Prussian blue structure to obtain the compound with the defect Prussian blue structure.
5. The method for preparing an electrode material according to claim 4, wherein the compound having a unit cell structure of Prussian blue is prepared mainly by the steps of: reacting a metal salt with ferrocyanide;
preferably, the metal salt and the ferrocyanide are reacted in a solution system;
more preferably, the metal salt is dissolved in a solvent, and then ferrocyanide is added for reaction to obtain a precipitate;
preferably, the metal salt is a nickel salt, a cobalt salt or an iron salt; preferably, the metal salt is a nitrate, sulfate or chloride of nickel, cobalt, iron;
preferably, the ferrocyanide comprises at least one of potassium ferrocyanide and sodium ferrocyanide.
6. The method for preparing the electrode material according to claim 5, wherein the molar ratio of the metal salt to the ferrocyanide is 1-4: 1;
preferably, when the reaction is carried out in a solution system, the concentration of the metal salt in the solution is 0.1-10 mol/L, and the concentration of the ferrocyanide in the solution is 0.1-10 mol/L.
7. The method for preparing an electrode material according to any one of claims 4 to 6, wherein the step of oxidizing the compound having a unit cell structure of Prussian blue is carried out by dispersing the compound having a unit cell structure of Prussian blue in a solvent and then adding an oxidizing agent to the solution to carry out a reaction.
8. The method for preparing the electrode material according to claim 7, wherein the oxidizing agent comprises at least one of hydrogen peroxide and sodium hypochlorite, preferably the oxidizing agent is hydrogen peroxide or sodium hypochlorite; preferably, the oxidant is added in the form of a solution, and further preferably, the concentration of the solution of the oxidant is 0.1-10 mol/L.
9. Use of the electrode material according to any one of claims 1 to 3 for the preparation of a sodium-air battery.
10. A sodium-air battery comprising an air cathode of the electrode material according to any one of claims 1 to 3, and a liquid anode, a solid electrolyte and an aqueous electrolyte;
preferably, the liquid anode is a biphenyl sodium solution, and the solid electrolyte is Al2O3Or Na3Si2Zr2PO12The fast ion conductor, the water system electrolyte is NaOH.
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| CN105836762A (en) * | 2016-03-16 | 2016-08-10 | 西北大学 | Preparation method and application of hollow Prussian-blue nanometer cube |
| CN109065883A (en) * | 2018-07-27 | 2018-12-21 | 张五星 | A kind of Prussian blue and the like method of modifying and sodium-ion battery |
| CN110010892A (en) * | 2019-03-29 | 2019-07-12 | 华中科技大学 | A kind of aluminium ion cell positive material, preparation method and application |
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| CN105836762A (en) * | 2016-03-16 | 2016-08-10 | 西北大学 | Preparation method and application of hollow Prussian-blue nanometer cube |
| CN109065883A (en) * | 2018-07-27 | 2018-12-21 | 张五星 | A kind of Prussian blue and the like method of modifying and sodium-ion battery |
| CN110010892A (en) * | 2019-03-29 | 2019-07-12 | 华中科技大学 | A kind of aluminium ion cell positive material, preparation method and application |
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