Positive electrode material for pure-phase polyanionic sodium sulfate ion battery and method for manufacturing the same

Abstract

A pure-phase polyanionic sulfate sodium-ion battery cathode material is disclosed. The general formula of the pure-phase polyanionic sulfate sodium-ion battery cathode material is NaxMyAzSO4, where M is one or more of Mn, Fe, Co, Ni, Cu, and / or Zn, A is one or more of Li, K, and / or Na, and the range of values that each variable can take is 0.75 ≦ x ≦ 0.85, 0.52 ≦ y ≦ 0.58, 0 < z ≦ 0.1, and x + 2y + z = 2. The pure-phase polyanionic sulfate sodium-ion battery cathode material has the characteristics of good structural stability, excellent rate performance, good cycle performance, and a simple and low-cost manufacturing method.

Claims

1. A positive electrode material for a pure-phase polyanionic sodium sulfate ion battery, wherein the general formula of the positive electrode material for the pure-phase polyanionic sodium sulfate ion battery is Na ｘ M ｙ A ｚ SO ４ A pure-phase polyanionic sodium sulfate ion battery cathode material characterized in that, where M is one or more of Mn, Fe, Co, Ni, Cu and / or Zn, A is one or more of Li, K and / or Na, and the possible ranges for each variable are 0.75 ≤ x ≤ 0.85, 0.52 ≤ y ≤ 0.58, 0 < z ≤ 0.1, and x + 2y + z = 2.

2. The pure-phase polyanionic sodium sulfate ion battery cathode material according to claim 1, characterized in that the pure-phase polyanionic sodium sulfate ion battery cathode material is a triclinic P21 / c space group.

3. In site partitioning, Na, S, and O are located at site 4e, and M and A are located at site 8f, and Na / S-O ４ is a tetrahedron, M / A-O ６ The positive electrode material for a pure-phase polyanionic sodium sulfate battery according to claim 2, characterized in that the tetrahedron and the octahedron are connected by common points / common faces.

4. In the triclinic P21 / c space group, the range of change for the crystal lattice parameters is 11.10 angstroms ≤ a ≤ 12.20 angstroms, 11.40 angstroms ≤ b ≤ 12.60 angstroms, 5.20 angstroms ≤ c ≤ 6.90 angstroms, and 910.01 angstroms. ３ ≤V ≤ 940.4 angstroms ３ The positive electrode material for a pure-phase polyanionic sodium sulfate battery according to feature 3.

5. A method for producing a pure-phase polyanionic sodium sulfate cathode material according to any one of claims 1 to 4, the method comprising the steps of uniformly mixing a sodium source, a metal source, an alkali metal source, an anion source, and a carbon source in stoichiometric ratios and sintering them in an inert atmosphere to produce a corresponding pure-phase polyanionic sodium sulfate cathode material.

6. A method for producing a pure-phase polyanionic sodium sulfate ion battery cathode material according to claim 5, characterized in that the sodium source is an inorganic sodium source and / or an organic sodium source, the inorganic sodium source is one or more of sodium hydroxide, sodium chloride, sodium sulfate, sodium nitrate and / or sodium carbonate, and the organic sodium source is one or more of sodium formate, sodium acetate, sodium ethoxide and / or sodium benzoate salt.

7. The metal sources are manganese sources, iron sources, cobalt sources, nickel sources, copper sources and / or zinc sources. The manganese source is one or more of the following: manganese sulfate, manganese carbonate, manganese chloride, and / or manganese acetate. The iron source is one or more of ferrous sulfate, iron chloride, ferrous oxide, and / or iron acetate. The cobalt source is one or more of the following: cobalt sulfate, cobalt nitrate, cobalt chloride, and / or cobalt acetate. The nickel source is one or more of nickel sulfate, nickel nitrate, nickel chloride, and / or nickel acetate. The copper source is one or more of copper sulfate, copper chloride, and / or copper acetate. The method for producing a pure-phase polyanionic sodium sulfate ion battery cathode material according to claim 5, characterized in that the zinc source is one or more of zinc sulfate, zinc chloride, and / or zinc acetate.

8. Alkali metal sources are sodium sources, lithium sources and / or potassium sources. The sodium source is an inorganic sodium source and / or an organic sodium source, the inorganic sodium source is one or more of sodium hydroxide, sodium chloride, sodium sulfate, sodium nitrate and / or sodium carbonate, and the organic sodium source is one or more of sodium formate, sodium acetate, sodium ethoxide and / or sodium benzoate salts. The lithium source is one or more of lithium sulfate, lithium carbonate, and / or lithium hydroxide. The method for producing a pure-phase polyanionic sodium sulfate ion battery cathode material according to claim 5, characterized in that the potassium source is one or more of potassium sulfate, potassium hydroxide, potassium chloride, potassium nitrate, and / or potassium carbonate.

9. The anion source is one or more of sulfuric acid, sodium sulfate, ferrous ammonium sulfate, ferrous sulfate and / or ammonium sulfate. The method for producing a pure-phase polyanionic sodium sulfate cathode material for a battery according to claim 5, characterized in that the carbon source is one or more of SurpP, KB, carbon nanotubes, graphene, glucose, citric acid, and / or sucrose.

10. The method for producing a pure-phase polyanionic sodium sulfate cathode material for a battery, as described in claim 5, characterized in that the method for uniform mixing is a liquid-phase mixing method or a solid-phase mixing method, the inert atmosphere is argon, nitrogen, or a mixed gas of argon-hydrogen or nitrogen-hydrogen, and the sintering temperature is 200 to 400°C.

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