Method for preparing sodium ion battery positive electrode materials with different crystal forms through lithium doping regulation and control

Abstract

The invention discloses a method for preparing sodium ion battery positive electrode materials with different crystal forms through lithium doping regulation and control. The chemical formula of the positive electrode materials is Na<0.7>Ni<x> Fe<y>Mn<1-x-y-z>Li O<2>, wherein x + y is more than 0 and less than or equal to 0.4, z is more than 0 and less than or equal to 0.4. The obtained material is a P2 phase material, a P2 / O3 mixed phase material or an O3 phase material by regulating the value of z, namely regulating the doping amount of Li. According to the invention, lithium is doped in a transition metal layer, so that a Na-O-Li structure can be formed to activate the oxidation-reduction reaction of oxygen, thereby providing additional capacity. The structure of the sodium-ion battery positive electrode material can be regulated and controlled by changing the lithium doping ratio, so that P2 phase, O3 phase and P2 / O3 mixed phase materials are obtained. The adopted co-precipitation method is simple and easy to implement, a material with regular morphology and uniform size can be obtained, and the obtained material has good electrochemical performance within the voltage range of 1.5-4.5 V.

Description

technical field

[0001] The invention belongs to the field of positive electrode materials for sodium ion batteries, and in particular relates to a method for preparing different crystal forms of Na through lithium doping regulation. 0.7 Ni x Fe y mn 1-x-y o 2 methods for cathode materials. Background technique

[0002] With the development of renewable energy and the urgent needs of the information age, people have higher and higher requirements for energy storage devices. Among them, lithium-ion batteries are widely used in various energy storage devices because of their advantages such as high energy density, high working voltage, and long cycle life. However, problems such as rising lithium prices and insufficient reserves have prompted people to look for new energy storage systems with abundant resources and low prices. Sodium-ion battery was first proposed in 1980. Due to its rich source of raw materials, relatively low price and environmental friendliness, it has...

Examples

Embodiment 1

[0021] Embodiment 1: P2 type sodium ion battery Na 0.7 Ni 0.1 Fe 0.1 mn 0.6 Li 0.2 o 2 preparation of

[0022] (1) Dissolve 0.102g of lithium acetate, 0.735g of manganese acetate, 0.124g of nickel acetate and 0.202g of ferric nitrate in a mixture of 10mL of water and 50mL of ethanol to obtain a metal salt solution. Dissolve 0.946g of oxalic acid in a mixed solution of 10mL of water and 50mL of ethanol to obtain a precipitant solution. The precipitating agent solution was quickly poured into the metal salt solution and continued to stir for 6 hours, and the obtained suspension was dried in an oven at 80°C for 15 hours to obtain a precursor.

[0023] (2) Fully grind and mix the precursor with 0.185g of sodium carbonate, calcinate at 450°C for 4h in air atmosphere, and then calcinate at 800°C for 12h to obtain P2 type Na 0.7 Ni 0.1 Fe 0.1 mn 0.6 Li 0.2 o 2 Cathode material.

[0024] Mix the positive electrode material obtained in this example with acetylene black and...

Embodiment 2

[0025] Embodiment 2: P2 / O3 type sodium ion battery Na 0.7 Ni 0.1 Fe 0.1 mn 0.5 Li 0.3 o 2 preparation of

[0026] (1) Dissolve 0.153g of lithium acetate, 0.613g of manganese acetate, 0.124g of nickel acetate and 0.202g of ferric nitrate in a mixture of 10mL of water and 50mL of ethanol to obtain a metal salt solution. Dissolve 0.946g of oxalic acid in a mixed solution of 10mL of water and 50mL of ethanol to obtain a precipitant solution. The precipitating agent solution was quickly poured into the metal salt solution and continued to stir for 6 hours, and the obtained suspension was dried in an oven at 80°C for 15 hours to obtain a precursor.

[0027] (2) Fully grind and mix the precursor with 0.185g sodium carbonate, calcinate at 450°C for 4h in the air atmosphere, and then calcinate at 800°C for 12h to obtain P2 / O3 type Na 0.7 Ni 0.1 Fe 0.1 mn 0.5 Li 0.3 o 2 Cathode material.

[0028]Mix the positive electrode material obtained in this example with acetylene bla...

Embodiment 3

[0029] Embodiment 3: O3 type sodium ion battery Na 0.7 Ni 0.1 Fe 0.1 mn 0.4 Li 0.4 o 2 preparation of

[0030] (1) Dissolve 0.204g of lithium acetate, 0.490g of manganese acetate, 0.124g of nickel acetate and 0.202g of ferric nitrate in a mixture of 10mL of water and 50mL of ethanol to obtain a metal salt solution. Dissolve 0.946g of oxalic acid in a mixed solution of 10mL of water and 50mL of ethanol to obtain a precipitant solution. The precipitating agent solution was quickly poured into the metal salt solution and continued to stir for 6 hours, and the obtained suspension was dried in an oven at 80°C for 15 hours to obtain a precursor.

[0031] (2) Fully grind and mix the precursor with 0.185g of sodium carbonate, calcinate at 450°C for 4h in the air atmosphere, and then calcinate at 800°C for 12h to obtain O3 type Na 0.7 Ni 0.1 Fe 0.1 mn 0.4 Li 0.4 o 2 Cathode material.

[0032] Mix the positive electrode material obtained in this example with acetylene black...

technical field

[0001] The invention belongs to the field of positive electrode materials for sodium ion batteries, and in particular relates to a method for preparing different crystal forms of Na through lithium doping regulation. 0.7 Ni x Fe y mn 1-x-y o 2 methods for cathode materials. Background technique

[0002] With the development of renewable energy and the urgent needs of the information age, people have higher and higher requirements for energy storage devices. Among them, lithium-ion batteries are widely used in various energy storage devices because of their advantages such as high energy density, high working voltage, and long cycle life. However, problems such as rising lithium prices and insufficient reserves have prompted people to look for new energy storage systems with abundant resources and low prices. Sodium-ion battery was first proposed in 1980. Due to its rich source of raw materials, relatively low price and environmental friendliness, it has...

Examples

Embodiment 1

[0021] Embodiment 1: P2 type sodium ion battery Na 0.7 Ni 0.1 Fe 0.1 mn 0.6 Li 0.2 o 2 preparation of

[0022] (1) Dissolve 0.102g of lithium acetate, 0.735g of manganese acetate, 0.124g of nickel acetate and 0.202g of ferric nitrate in a mixture of 10mL of water and 50mL of ethanol to obtain a metal salt solution. Dissolve 0.946g of oxalic acid in a mixed solution of 10mL of water and 50mL of ethanol to obtain a precipitant solution. The precipitating agent solution was quickly poured into the metal salt solution and continued to stir for 6 hours, and the obtained suspension was dried in an oven at 80°C for 15 hours to obtain a precursor.

[0023] (2) Fully grind and mix the precursor with 0.185g of sodium carbonate, calcinate at 450°C for 4h in air atmosphere, and then calcinate at 800°C for 12h to obtain P2 type Na 0.7 Ni 0.1 Fe 0.1 mn 0.6 Li 0.2 o 2 Cathode material.

[0024] Mix the positive electrode material obtained in this example with acetylene black and...

Embodiment 2

[0025] Embodiment 2: P2 / O3 type sodium ion battery Na 0.7 Ni 0.1 Fe 0.1 mn 0.5 Li 0.3 o 2 preparation of

[0026] (1) Dissolve 0.153g of lithium acetate, 0.613g of manganese acetate, 0.124g of nickel acetate and 0.202g of ferric nitrate in a mixture of 10mL of water and 50mL of ethanol to obtain a metal salt solution. Dissolve 0.946g of oxalic acid in a mixed solution of 10mL of water and 50mL of ethanol to obtain a precipitant solution. The precipitating agent solution was quickly poured into the metal salt solution and continued to stir for 6 hours, and the obtained suspension was dried in an oven at 80°C for 15 hours to obtain a precursor.

[0027] (2) Fully grind and mix the precursor with 0.185g sodium carbonate, calcinate at 450°C for 4h in the air atmosphere, and then calcinate at 800°C for 12h to obtain P2 / O3 type Na 0.7 Ni 0.1 Fe 0.1 mn 0.5 Li 0.3 o 2 Cathode material.

[0028]Mix the positive electrode material obtained in this example with acetylene bla...

Embodiment 3

[0029] Embodiment 3: O3 type sodium ion battery Na 0.7 Ni 0.1 Fe 0.1 mn 0.4 Li 0.4 o 2 preparation of

[0030] (1) Dissolve 0.204g of lithium acetate, 0.490g of manganese acetate, 0.124g of nickel acetate and 0.202g of ferric nitrate in a mixture of 10mL of water and 50mL of ethanol to obtain a metal salt solution. Dissolve 0.946g of oxalic acid in a mixed solution of 10mL of water and 50mL of ethanol to obtain a precipitant solution. The precipitating agent solution was quickly poured into the metal salt solution and continued to stir for 6 hours, and the obtained suspension was dried in an oven at 80°C for 15 hours to obtain a precursor.

[0031] (2) Fully grind and mix the precursor with 0.185g of sodium carbonate, calcinate at 450°C for 4h in the air atmosphere, and then calcinate at 800°C for 12h to obtain O3 type Na 0.7 Ni 0.1 Fe 0.1 mn 0.4 Li 0.4 o 2 Cathode material.

[0032] Mix the positive electrode material obtained in this example with acetylene black...

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