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Anion valence-varying layer oxide material, and preparation method and application thereof

A technology of oxides and anions, applied in the field of materials, to achieve the effects of low manufacturing cost, great practical value, and simple material preparation

Inactive Publication Date: 2019-04-02
INST OF PHYSICS - CHINESE ACAD OF SCI
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

[0006] However, sodium-ion batteries are still in the research stage at present, and there is no commercialized sodium-ion battery cathode material. Now researchers are mainly focusing on the layered structure oxide cathode material NaxMO2 (M stands for 3d transition metal elements. , can contain one or more, such as Ti, V, Cr, Fe, Mn, Co, Ni, Cu, Nb, Ru, Mo, Zn, etc.)

Method used

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  • Anion valence-varying layer oxide material, and preparation method and application thereof
  • Anion valence-varying layer oxide material, and preparation method and application thereof
  • Anion valence-varying layer oxide material, and preparation method and application thereof

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Embodiment 1

[0065] Embodiment 1 of the present invention provides an anion-variable layered oxide material, characterized in that the general chemical formula of the layered oxide material is: Na a [Li b mn c m d ]O 2+β ;

[0066] Among them, M is an element for doping and replacing the transition metal site, specifically Ni 2+ ,Cu 2+ ,Mg 2+ ,Mn 2+ ,Zn 2+ ,Mn 3 + ,Al 3+ , Fe 3+ ,B 3+ ,Zr 4+ , Ti 4+ ,Sn 4+ ,Si 4+ one or more of

[0067] The a, b, c, d, β are respectively the molar percentages of the corresponding elements; wherein the relationship between a, b, c, d, β satisfies b+c+d=1, and a+b+4c +md=2(2+β); where 0.6≤a≤1; 0<b≤0.4; 0.5≤c≤0.8; 0≤d≤0.3; -0.02≤β≤0.02; m is the valence state of M ;

[0068] The space group of the layered oxide material is P63 / mmc or R-3m, and the corresponding structure is P2 phase or P3 phase.

[0069] exist figure 1 The X-ray diffraction (X-raydiffraction, XRD) collection of graphs of a plurality of layered oxide materials of differen...

Embodiment 2

[0074] This embodiment provides a method for preparing a layered oxide material, specifically a solid phase method, such as figure 2 shown, including:

[0075] Step 201, mixing sodium carbonate with a stoichiometric amount of required sodium of 100wt% to 108wt% and required stoichiometric amounts of lithium carbonate / lithium hydroxide, manganese dioxide and M oxides in proportion to form a precursor;

[0076] Specifically, the M is specifically Ni 2+ ,Cu 2+ ,Mg 2+ ,Mn 2+ ,Zn 2+ ,Mn 3+ ,Al 3+ , Fe 3+ ,B 3+ ,Zr 4+ , Ti 4+ ,Sn 4+ , Si 4+ one or more of.

[0077] Step 202, using a ball milling method to uniformly mix the precursor to obtain a precursor powder;

[0078] Step 203, placing the precursor powder in a muffle furnace, and heat-treating it in an air atmosphere at 700° C. to 1000° C. for 2 to 24 hours;

[0079] Step 204, grinding the heat-treated precursor powder to obtain the layered oxide material.

[0080] The preparation method of the layered oxide mat...

Embodiment 3

[0082] This embodiment provides a preparation method of a layered oxide material, specifically a spray drying method, such as image 3 shown, including:

[0083] Step 301, dissolving sodium acetate or sodium nitrate or sodium carbonate or sodium sulfate, nitrate or sulfate containing lithium, manganese, and doping element M with a stoichiometric ratio of 100wt% to 108wt% of required sodium in water according to the stoichiometric ratio Or dissolve in ethanol and mix to form a precursor solution;

[0084] Specifically, the M can be Ni 2+ ,Cu 2+ ,Mg 2+ ,Mn 2+ ,Zn 2+ ,Mn 3+ ,Al 3+ , Fe 3+ ,B 3+ ,Zr 4+ , Ti 4+ ,Sn 4+ , Si 4+ one or more of.

[0085] Step 302, adding ethanol or water to the precursor and stirring evenly to form a slurry;

[0086] Step 303, spray-drying the slurry to obtain a precursor powder;

[0087] Step 304, placing the precursor powder in a muffle furnace, and heat-treating in an air atmosphere at 650° C. to 1000° C. for 2 to 24 hours;

[0088]...

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Abstract

The invention discloses an anion valence-varying layer oxide material, and a preparation method and application thereof. The chemical formula of the material is: Naa[LibMncMd]O2+[beta]; M is an element which is doped and substituted for a transition metal site; a, b, c , d and [beta] are the mole percentages of the corresponding elements respectively; the relationship between a, b, c, d and [beta]satisfies the formula: b+c+d=1, and a+b+4c+md=2(2+[beta]); 0.6<=a<=1, 0<=b<=0.4, 0.5<=c<=0.8, 0<=d<=0.3, and -0.02<=[beta]<=0.02; m is the valence state of M; and the space group of materials is P63 / mmc or R-3m, the corresponding structure is P2 phase or P3 phase, and the anion valence-varying layer oxide material is used for the positive electrode active material of sodium ion secondary battery.When charging is performed in the first week, the lattice oxygen ion is converted from a negative bivalence to a higher valence state, electrons are completely provided by the oxygen ions to achieveactivation of the material; when discharge is performed in the first week, the oxygen ions losing electrons regain electrons from the high valence state to the negative bivalence, and the manganese metal is converted from a tetravalence to a tervalence, and the charging and discharging process after two weeks has the valence varying of the oxygen ions and the valence varying of the manganese.

Description

technical field [0001] The invention relates to the technical field of materials, in particular to an anion-variable layered oxide material, a preparation method, and its application to pole pieces and secondary batteries. Background technique [0002] With the development and progress of society, human beings have an increasing demand for energy. However, due to the depletion of traditional fossil energy such as coal, oil, and natural gas, coupled with the increasingly severe problems of urban environmental pollution and greenhouse effect, Its application is gradually restricted in many ways, so the development of sustainable clean energy has always been the direction of attention of all countries. However, in the process of converting wind energy, solar energy, and tidal energy into electrical energy, these renewable energy sources are greatly restricted by natural conditions, and have the characteristics of obvious time discontinuity and spatial distribution, which lead t...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): H01M4/36H01M4/48H01M4/50H01M4/52H01M10/054
CPCH01M4/366H01M4/483H01M4/502H01M4/523H01M10/054Y02E60/10
Inventor 胡勇胜容晓晖陈立泉
Owner INST OF PHYSICS - CHINESE ACAD OF SCI
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