Phosphate positive electrode material and preparation method and application thereof

A cathode material, phosphate technology, applied in the field of phosphate cathode material and its preparation, can solve the problems of large amount of metal vanadium, poor conductivity, cumbersome process, etc., and achieves the improvement of conductivity, rate performance, and discharge voltage. Effect

Inactive Publication Date: 2021-02-26
INST OF PROCESS ENG CHINESE ACAD OF SCI
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

The composite material has excellent electrochemical properties as a positive electrode material for a sodium ion battery, but the amount of alum used in the sodium vanadium manganese phosphate composite material is large, which will lead to problems such as high cost and high toxicity.
[0006] The phosphate cathode material prepared by the above method has the characteristics of poor intrinsic conductivity, cumbersome process and large amount of expensive and toxic metal vanadium.

Method used

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  • Phosphate positive electrode material and preparation method and application thereof
  • Phosphate positive electrode material and preparation method and application thereof
  • Phosphate positive electrode material and preparation method and application thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0063] This embodiment provides a phosphate cathode material, and the specific preparation steps are as follows:

[0064] Add manganese acetate, vanadium acetylacetonate, aluminum isopropoxide, sodium acetate and phosphoric acid with a molar composition ratio of 1:0.8:0.2:4:3 to the ethanol solution containing citric acid, wherein the substance of citric acid and aluminum isopropoxide The volume ratio is 2:1. Then the mixed solution was placed in a water bath at 100°C with magnetic stirring until the ethanol evaporated completely. Grind the obtained precursor to a powder state, place it in a tube furnace with an argon atmosphere and sinter at 800 °C for 12 h to obtain Na 4 V 0.8 al0.2 Mn(PO 4 ) 3 Cathode material.

[0065] The Na coated with carbon coating layer 4 V 0.8 Al 0.2 Mn(PO 4 ) 3 The XRD pattern of the positive electrode material is as follows figure 1 shown by figure 1 It can be seen that the diffraction peaks of the prepared material correspond to the st...

Embodiment 2

[0072] This embodiment provides a kind of preparation steps of phosphate cathode material as follows:

[0073] Add manganese acetate, ammonium metavanadate, magnesium acetate, sodium carbonate and phosphoric acid with a composition ratio of 1:0.9:0.1:4.1:3 to the solution containing glucose, wherein the substance ratio of the total content of glucose and metal ions is 1.5: 1. Then the mixed solution was placed in a water bath at 120° C. and magnetically stirred until the water evaporated completely. Grind the obtained precursor to a powder state, place it in a tube furnace with an argon atmosphere and sinter at 700°C for 10 hours to obtain a carbon-coated Na 4.1 V 0.9 Mg 0.1 Mn(PO 4 ) 3 Cathode material.

[0074] The Na coated with carbon coating layer 4.1 V 0.9 Mg 0.1 Mn(PO 4 ) 3 The first charge and discharge curve of the positive electrode material at 0.2C is as follows: Figure 7 shown.

Embodiment 3

[0076] This embodiment provides a kind of preparation steps of phosphate cathode material as follows:

[0077] Add manganese acetate, vanadium acetylacetonate, ferrous acetylacetonate, sodium carbonate and ammonium dihydrogen phosphate with a composition ratio of 1:0.6:0.4:0.2:4.4:3 to the solution containing citric acid, wherein the total of citric acid and transition metal The quantity ratio of quantity to substance is 1.2:1. Then the mixed solution was placed in a water bath at 110°C with magnetic stirring until the water evaporated completely. Grind the obtained precursor to a powder state, place it in a tube furnace with an argon atmosphere and sinter at 650°C for 10 hours to obtain a carbon-coated Na 4.4 V 0.6 Fe 0.4 Mn(PO 4 ) 3 Cathode material.

[0078] The Na coated with carbon coating layer 4.4 V 0.6 Fe 0.4 Mn(PO 4 ) 3 The first charge and discharge curve of the positive electrode material at 0.2C is as follows: Figure 8 shown.

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Abstract

The invention provides a phosphate positive electrode material and a preparation method and application thereof. The phosphate positive electrode material comprises an inner core and a carbon coatinglayer formed on the surface of the inner core, wherein the inner core comprises Na4+deltaV1-xMxMn(PO4)3. The chelating effect between an organic carbon source and metal ions is utilized to realize uniform mixing of raw materials and in-situ introduction of a carbon coating layer, so the overall conductivity of the material is improved; half of manganese is introduced to replace vanadium, so that the working voltage of the material is increased while the use amount of vanadium is reduced; then a trace amount of stable metal elements are doped to replace part of vanadium, the use amount of vanadium is further reduced, meanwhile, a solid solution structure is formed by vanadium and manganese, ginger Taylor structure distortion caused by manganese ions is reduced, the three-dimensional sodiumsuper-ion conductor structure of the material can be maintained, and the rate capability of the material is improved.

Description

technical field [0001] The invention belongs to the field of sodium ion batteries, and relates to a phosphate cathode material and a preparation method and application thereof. Background technique [0002] The world is facing two major problems of environmental pollution and energy depletion. Therefore, the development of new green energy sources and corresponding energy storage devices has become a research hotspot in the world today. Secondary rechargeable lithium-ion batteries have been widely studied as an energy storage device because of their high conversion efficiency and energy density. However, the shortage and uneven distribution of lithium resources limit its future development. With the rise of large-scale energy storage, and considering the high abundance and low price of sodium resources, sodium-ion batteries have become an important supplementary part of lithium-ion batteries. Phosphate cathode materials for sodium superionic conductors with three-dimensio...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): H01M4/62H01M4/58H01M4/136H01M10/054
CPCH01M4/5825H01M4/625H01M4/628H01M4/136H01M10/054H01M2004/028H01M2004/021Y02E60/10
Inventor 赵君梅徐春柳刘会洲
Owner INST OF PROCESS ENG CHINESE ACAD OF SCI
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