CN115621454A - Cathode material and preparation method and application thereof - Google Patents

Cathode material and preparation method and application thereof Download PDF

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CN115621454A
CN115621454A CN202211416876.5A CN202211416876A CN115621454A CN 115621454 A CN115621454 A CN 115621454A CN 202211416876 A CN202211416876 A CN 202211416876A CN 115621454 A CN115621454 A CN 115621454A
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positive electrode
electrode material
soluble
valence
salt
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熊玉姣
彭洋
王欢
温秦芬
谭星
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Ganzhou Litan New Energy Technology Co ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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    • Y02E60/10—Energy storage using batteries

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Abstract

The invention relates to the technical field of electrode materials, in particular to a positive electrode material and a preparation method and application thereof. The invention provides a positive electrode material which is of a layered structure, wherein the layered structure comprises a P2 phase layer and a P3 phase coating layer; the chemical composition general formula of the cathode material is as follows: na (Na) a Li b Cu c Zn d Mn e O 2+β Wherein a is 0.67 to 0.8, b is 0.01 to 0.03, c is 0.2 to 0.3, d is 0.05 to 0.08, e is 0.6 to 0.7, and the value of beta satisfies the balance of valence; the valence states of Mn in the positive electrode material include +2 and + 3. The cathode material is low in cost and has excellent rapid charge and discharge performance.

Description

Positive electrode material and preparation method and application thereof
Technical Field
The invention relates to the technical field of electrode materials, in particular to a positive electrode material and a preparation method and application thereof.
Background
With the acceleration of the modernization process of society, people are aware of the importance of the novel energy storage device to the development of human beings quickly due to the environmental and economic problems caused by the development driven by the cost of using the traditional fossil energy in a large area and the defects of unpredictability, geographical limitation, unstable capacity and the like of the current renewable energy (solar energy, wind energy, tidal energy and geothermal energy).
The lithium ion battery as a secondary energy storage device greatly supported and developed in China at present has the advantages of strategic significance in the aspects of practical application and theoretical research, but the contradiction between the shortage and the uneven distribution of lithium resources and the sharp increase of demand is increasingly prominent.
The sodium ion battery and the lithium ion battery have the same working principle of a rocking chair type, sodium resources on the earth are widely distributed, the reserve is extremely large, the cost is easily reduced, in terms of price, the sodium is only one twentieth of the lithium cost, and the sodium ion battery has absolute advantages and application prospects in price.
Among transition metal oxide anode materials, the high discharge voltage, the stable structure and the dialysis working mechanism are considered to be anode materials with great industrialization potential. Yunming et al (DOI: 10.1002/advs.201500031) prepared P2-N 7/9 Cu 2/9 Fe 1/9 Mn 2/3 O 2 The positive electrode material is applied to the sodium ion battery, but the deficiency of the rate capability of the positive electrode material can not meet the market demand of quick charge and quick discharge; HWang et al (DOI: 10.1038/ncomms 7865) prepared O3- (Na [ Ni ] 0.58 Co 0.06 Mn 0.36 ]O 2 ) The positive electrode material is applied to the sodium ion battery, but the material is easy to change phase in the air, and the used raw materials are all expensive nickel and cobalt transition metals, so the material is not suitable for the low-cost sodium ion battery.
Disclosure of Invention
The invention aims to provide a positive electrode material, a preparation method and application thereof.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a positive electrode material which is of a layered structure, wherein the layered structure comprises a P2 phase layer and a P3 phase coating layer;
the chemical composition general formula of the cathode material is as follows: na (Na) a Li b Cu c Zn d Mn e O 2+β Wherein a is 0.67 to 0.8, b is 0.01 to 0.03, c is 0.2 to 0.3, d is 0.05 to 0.08, e is 0.6 to 0.7, and the value of beta satisfies the balance of valence;
the valence states of Mn in the positive electrode material include +2 and + 3.
Preferably, a is 0.7-0.8, b is 0.02, c is 0.25-0.3, d is 0.06-0.07, e is 0.64-0.66, and the value of beta satisfies the balance of valence.
Preferably, a =0.78, b =0.02, c =0.27, d =0.06, e =0.65, and β satisfies the balance of valence.
Preferably, the thickness of the P3 phase coating layer is 3-10 nm.
Preferably, the positive electrode material includes small particles having a particle size of 10 to 200nm and large particles having a particle size of 1 to 10 μm.
The invention also provides a preparation method of the anode material in the technical scheme, which comprises the following steps:
mixing soluble copper salt, soluble zinc salt, soluble manganous salt, soluble lithium salt, soluble sodium salt, complexing agent and water to obtain a metal composite gel precursor;
sintering the metal composite gel precursor to obtain a composite metal oxide precursor;
and calcining the composite metal oxide precursor to obtain the cathode material.
Preferably, the complexing agent is one or more of citric acid, citrate, maleic acid and maleate.
Preferably, the sintering temperature is 400-600 ℃, the heat preservation time is 3-5 h, and the heating rate of heating to the sintering temperature is 2-5 ℃/min.
Preferably, the calcining temperature is 800-1000 ℃, the heat preservation time is 10-15 h, and the heating rate of the temperature rising to the calcining temperature is 2-5 ℃/min.
The invention also provides the application of the anode material in the technical scheme or the anode material prepared by the preparation method in the technical scheme in a sodium-ion battery.
The invention provides a positive electrode material which is of a layered structure, wherein the layered structure comprises a P2 phase layer and a P3 phase coating layer; the chemical composition general formula of the cathode material is as follows: na (Na) a Li b Cu c Zn d Mn e O 2+β Wherein a is 0.67 to 0.8, b is 0.01 to 0.03, c is 0.2 to 0.3, d is 0.05 to 0.08, e is 0.6 to 0.7, and the value of beta satisfies the balance of valence; the valence states of Mn in the positive electrode material include +2 and + 3. The positive electrode material has excellent rapid charge and discharge performance due to the ion conductor property generated by lithium ion doping and the P3 phase coating caused by doping, and still has 73 mA.h.g under the condition of 10C (1 minute charge and discharge) -1 The material has the reversible discharge specific capacity, and the structure of the material is not changed after the material is soaked in water; meanwhile, the cycle performance and the rate performance of the cathode material are excellent, the repeatability is high, the uniformity is good, and a better driving force is provided for the development of the sodium ion battery industry; compared with the traditional nickel and cobalt transition metal oxide positive electrode, the positive electrode material induced by lithium doping adopts cheap metals of zinc, copper and manganese, so that the cost is greatly reduced, and the excellent performance is ensured. The invention is economic and efficient, and the provided anode material can be exposed in the air for a long time and has excellent rate performance, thereby having very wide application prospect in the quick-charging and quick-discharging sodium ion battery.
The invention also provides a preparation method of the anode material in the technical scheme, which comprises the following steps: mixing soluble copper salt, soluble zinc salt, soluble divalent manganese salt, soluble lithium salt, soluble sodium salt, complexing agent and water to obtain a metal composite gel precursor; sintering the metal composite gel precursor to obtain a composite metal oxide precursor; and calcining the composite metal oxide precursor to obtain the cathode material. The preparation method is simple and is easy for large-scale production.
Drawings
FIG. 1 is a schematic structural diagram of the positive electrode material of the present invention;
FIG. 2 is an SEM image of the cathode material of example 1;
FIG. 3 is a TEM image of the positive electrode material described in example 1;
FIG. 4 is an XRD pattern of the positive electrode material of example 1;
FIG. 5 is an XRD pattern of the positive electrode material of example 1 after being immersed in water for 10h and exposed to air for 1 month;
fig. 6 is a charge-discharge cycle curve of a button cell prepared from the positive electrode material described in example 1;
fig. 7 is a graph of rate performance of button cells prepared from the positive electrode material described in example 1;
fig. 8 is an SEM image of the positive electrode material described in comparative example 1;
fig. 9 is a graph of rate performance of button cells prepared from the positive electrode material described in comparative example 1.
Detailed Description
The invention provides a positive electrode material which is of a layered structure, wherein the layered structure comprises a P2 phase layer and a P3 phase coating layer (shown in figure 1);
the chemical composition general formula of the cathode material is as follows: na (Na) a Li b Cu c Zn d Mn e O 2+β Wherein a is 0.67-0.8, b is 0.01-0.03, c is 0.2-0.3, d is 0.05-0.08, e is 0.6-0.7, and the value of beta satisfies the balance of valence;
the valence states of Mn in the positive electrode material include +2 and + 3.
In the invention, the P2 phase in the P2 phase is Na a1 Li b1 Cu c1 Zn d1 Mn e1 O 2+β1 Wherein a1 is 0.67-0.8, b1 is 0.01-0.03, c1 is 0.2-0.3, d1 is 0.05-0.08, e1 is 0.6-0.7, and the value of beta 1 satisfies the balance of valence; the P3 phase in the P3 phase coating layer is Na a2 Li b2 Cu c2 Zn d2 Mn e2 O 2+β2 Wherein a2 is 0.1-0.67, b2 is 0.01-0.03, c2 is 0.2-0.3, d2 is 0.05-0.08, e2 is 0.6-0.7, and the value of beta 2 satisfies the balance of valence.
In the present invention, the thickness of the P3 phase coating layer is preferably 3 to 10nm, and more preferably 5 to 8nm.
In the present invention, a is preferably 0.7 to 0.8, more preferably 0.78; b is preferably 0.02; c is preferably 0.25 to 0.3, more preferably 0.27; d is preferably 0.06 to 0.07, more preferably 0.06; e is preferably 0.64 to 0.66, more preferably 0.65; the value of beta satisfies the balance of valence.
In the present invention, the positive electrode material preferably includes small particles having a particle diameter of 10 to 200nm and large particles having a particle diameter of 1 to 10 μm.
In the present invention, the valence of Mn in the positive electrode material includes +2 and +3, and the oxygen content in the positive electrode material balances the valence according to the valence distribution of Mn, that is, the positive electrode material is a completely oxidized oxide (in practical applications, the oxygen content does not need to be measured specifically).
The invention also provides a preparation method of the anode material in the technical scheme, which comprises the following steps:
mixing soluble copper salt, soluble zinc salt, soluble divalent manganese salt, soluble lithium salt, soluble sodium salt, complexing agent and water to obtain a metal composite gel precursor;
sintering the metal composite gel precursor to obtain a composite metal oxide precursor;
and calcining the composite metal oxide precursor to obtain the cathode material.
In the present invention, all the starting materials for the preparation are commercially available products known to those skilled in the art unless otherwise specified.
The preparation method comprises the steps of mixing soluble copper salt, soluble zinc salt, soluble divalent manganese salt, soluble lithium salt, soluble sodium salt, complexing agent and water to obtain the metal composite gel precursor.
In the invention, the soluble copper salt is preferably one or more of nitrate, sulfate and acetate of copper; the soluble zinc salt is preferably one or more of nitrate, sulfate and acetate of zinc; the soluble divalent manganese salt is preferably one or more of nitrate, sulfate and acetate of divalent manganese; the soluble lithium salt is preferably one or more of nitrate, sulfate and acetate of lithium; the soluble sodium salt is preferably one or more of nitrate, sulfate and acetate of sodium. The complexing agent is preferably one or more of citric acid, citrate, maleic acid and maleate; when the complexing agents are more than two of the specific choices, the proportion of the specific substances is not limited in any way, and the substances can be mixed according to any proportion.
In the invention, the soluble copper salt, the soluble zinc salt, the soluble divalent manganese salt, the soluble lithium salt and the soluble sodium salt are mixed according to the proportion relation of each element in the chemical composition of the anode material.
In the present invention, the mass ratio of the soluble copper salt to the complexing agent is preferably 1: (1 to 8), more preferably 1: (2 to 6), most preferably 1: (3-5).
In the present invention, the concentration of the complexing agent in the mixed solution obtained by the mixing is preferably 0.1 to 10mol/L, more preferably 1 to 8mol/L, and most preferably 2 to 5mol/L.
In the present invention, the mixing order is preferably that the complexing agent and water are mixed to obtain an aqueous solution of the complexing agent, and then the aqueous solution of the complexing agent, a soluble copper salt, a soluble zinc salt, a soluble divalent manganese salt, a soluble lithium salt and a soluble sodium salt are mixed.
In the present invention, the mixing is preferably performed under oil bath and stirring conditions; the temperature of the oil bath is preferably 60-80 ℃, more preferably 65-75 ℃, and most preferably 68-72 ℃; the rotation speed of the stirring is preferably 500-800 rpm, more preferably 600-700 rpm; the mixing time in the present invention is not particularly limited, and the solution obtained after mixing may be gelled by a time known to those skilled in the art.
After the mixing is completed, the invention also preferably comprises drying, wherein the drying is preferably vacuum drying; the temperature of the vacuum drying is preferably 80-100 ℃, and more preferably 85-95 ℃; the time is preferably 6 to 12 hours, more preferably 8 to 10 hours.
In the invention, the precursor of the composite metal composite gel is a complex of copper, zinc, manganese, lithium and sodium.
After obtaining the metal composite gel precursor, sintering the metal composite gel precursor to obtain the composite metal oxide precursor.
Before sintering, the invention also preferably comprises grinding and tabletting which are carried out in sequence; the grinding process is not particularly limited, and may be carried out by a method known to those skilled in the art. In the present invention, the pressure of the compressed tablet is preferably 10 to 20mbar, more preferably 13 to 16mbar; the time for tabletting is not particularly limited in the present invention, and the metal composite gel precursor can be pressed into a glossy disc by using a time known to those skilled in the art. In the present invention, the tableting is preferably performed in a mold using a hydraulic pump.
In the present invention, the sintering temperature is preferably 400 to 600 ℃, more preferably 450 to 550 ℃, and most preferably 480 to 520 ℃; the heat preservation time is preferably 3 to 5 hours, more preferably 3.5 to 4.5 hours, and most preferably 3.8 to 4.2 hours; the heating rate for heating to the sintering temperature is preferably 2 to 5 ℃/min, more preferably 3 to 4 ℃/min. In the present invention, the sintering is preferably performed in an air atmosphere.
In the present invention, the metal salt is decomposed during the sintering process to generate a composite metal oxide.
After the sintering is completed, the invention also preferably comprises temperature reduction, and the temperature reduction process is not limited in any way and can be carried out by adopting a process well known to a person skilled in the art.
After obtaining the composite metal oxide precursor, the invention calcines the composite metal oxide precursor to obtain the anode material.
The present invention also preferably includes grinding and tabletting in sequence before calcination; the grinding process is not particularly limited, and may be carried out by a method known to those skilled in the art. In the present invention, the pressure of the compressed tablet is preferably 10 to 20mbar, more preferably 13 to 16mbar; the time for tableting is not particularly limited in the present invention, and the composite metal oxide precursor may be compressed into a glossy disk using a time known to those skilled in the art. In the present invention, the tableting is preferably performed in a mold using a hydraulic pump.
In the present invention, the temperature of the calcination is preferably 800 to 1000 ℃, more preferably 850 to 950 ℃, and most preferably 880 to 920 ℃; the heat preservation time is preferably 10 to 15 hours, more preferably 11 to 14 hours, and most preferably 12 to 13 hours; the rate of temperature rise to the calcination temperature is preferably 2 to 5 ℃/min, more preferably 3 to 4 ℃/min. In the present invention, the calcination is preferably performed in an oxygen atmosphere.
In the present invention, the composite metal oxide is fused and a layered oxide positive electrode material is produced in the calcination process.
After the calcination is completed, the present invention preferably includes temperature reduction, and the temperature reduction process is not limited in any way, and can be performed by a process well known to those skilled in the art.
The invention also provides the application of the anode material in the technical scheme or the anode material prepared by the preparation method in the technical scheme in a sodium-ion battery. The method for applying the positive electrode material in the sodium-ion battery is not limited in any way, and the method for applying the positive electrode material in the sodium-ion battery is well known to those skilled in the art.
The following examples are provided to illustrate the positive electrode material of the present invention, its preparation method and application in detail, but they should not be construed as limiting the scope of the present invention.
Example 1
A positive electrode material: na (Na) 0.78 Li 0.02 Cu 0.27 Zn 0.06 Mn 0.65 O 2+β (ii) a The valence states of Mn include +2 and + 3; the anode material is of a laminated structure, and the laminated structure comprises a P2 phase layer and a P3 phase coating layer; the P2 phase in the P2 phase layer is Na 0.78 Li 0.0 2 Cu 0.27 Zn 0.06 Mn 0.65 O 2+β1 The value of beta 1 satisfies the balance of valence, and the P3 phase in the P3 phase coating layer is Na 0.52 Li 0.02 Cu 0.27 Zn 0.06 Mn 0.65 O 2+β2 The value of beta 2 satisfies the balance of valence; the thickness of the P3 phase coating layer is 3-10 nm; the anode material comprises small particles with the particle size of 10-200 nm and large particles with the particle size of 1-10 mu m;
the preparation method comprises the following steps:
mixing copper acetate, zinc acetate, manganese acetate, lithium nitrate and sodium nitrate with a deionized water solution of 150mL citric acid with a concentration of 3mol/L (mass ratio of copper acetate to citric acid is 1;
sequentially grinding and tabletting the metal composite gel precursor (the pressure of the tabletting is 15mbar, and the time is 5 min), pressing into a wafer with luster, heating to 500 ℃ at the heating rate of 4 ℃/min in the air atmosphere, preserving heat for 4h, and cooling to obtain a composite metal oxide precursor;
and sequentially grinding and tabletting the composite metal oxide precursor (the pressure of the tabletting is 15mbar, and the time is 5 min), pressing the composite metal oxide precursor into a wafer with luster, heating to 900 ℃ at a heating rate of 3 ℃/min in an oxygen atmosphere, preserving heat for 14h, and cooling to obtain the anode material.
Performing SEM test on the cathode material, wherein the test result is shown in figure 2; performing a TEM test on the cathode material, wherein the test result is shown in FIG. 3; the positive electrode material is subjected to XRD test, and the test result is shown in figure 4; as can be seen from fig. 2 to 4, the positive electrode material has a layered P3 phase coated layered P2 phase structure, and the thickness of the layered P3 phase coated layer is 3 to 10nm; the anode material comprises small particles with the particle size of 10-200 nm and large particles with the particle size of 1-10 mu m;
after the anode material is soaked in water for 10 hours, an XRD test is carried out after the anode material is exposed in air for 1 month, the test result is shown in figure 5, and as can be seen from figure 5, the anode material is very stable in water and air, and does not have phase change after being soaked;
drying the anode material at 110 ℃ for 12h, and uniformly dispersing 8g of the dried anode material, 1g of acetylene black and 1g of vinylidene fluoride in N-methyl-2-pyrrolidone to obtain slurry; coating the slurry on an aluminum foil, drying the aluminum foil in vacuum at 110 ℃, cutting the aluminum foil into pole pieces, placing the pole pieces in a high-purity argon glove box, taking metal sodium as a negative electrode, taking glass fiber as a diaphragm, and taking 1M NaPF 6 the/EC + DME (1;
the button cell is subjected to a charge and discharge performance test (the voltage range is 2.5-4.1V) at a rate of 1C, the test result is shown in FIG. 6, and as can be seen from FIG. 6, after 200 cycles of the button cell, the capacity retention rate is 85%;
fig. 7 is a rate performance graph of the button cell, and as can be seen from fig. 7, the button cell has 87.7mA · h · g at rates of 0.10C, 0.50C, 1.0C, 2.0C, 5.0C, and 10.0C, respectively -1 、87.5mA·h·g -1 、86.1mA·h·g -1 、83.2mA·h·g -1 、80.6mA·h·g -1 And 72.6 mA. H.g -1 After deep discharge with large multiplying power, the button cell can still maintain 93 mA.h.g when the multiplying power is reduced to 0.1C -1 The discharge specific capacity of the anode material fully shows the wide application prospect of the anode material.
Example 2
The positive electrode material: na (Na) 0.80 Li 0.01 Cu 0.30 Zn 0.05 Mn 0.65 O 2+β (ii) a The valence states of Mn include +2 and + 3; the anode material is of a layered structure, and the layered structureThe structure comprises a P2 phase layer and a P3 phase coating layer; the P2 phase in the P2 phase layer is Na 0.8 Li 0.01 Cu 0.30 Zn 0.05 Mn 0.65 O 2+β1 The value of beta 1 satisfies the balance of valence, and the P3 phase in the P3 phase coating layer is Na 0.55 Li 0.01 Cu 0.30 Zn 0.05 Mn 0.65 O 2+β2 The value of beta 2 satisfies the balance of valence; the thickness of the P3 phase coating layer is 3-10 nm; the anode material comprises small particles with the particle size of 10-200 nm and large particles with the particle size of 1-10 mu m;
the preparation method comprises the following steps:
mixing copper acetate, zinc acetate, manganese acetate, lithium nitrate and sodium nitrate with a deionized water solution of 150mL of citric acid with a concentration of 3mol/L (mass ratio of copper acetate to citric acid is 1;
sequentially grinding and tabletting the metal composite gel precursor (the pressure of the tabletting is 15mbar, and the time is 5 min), pressing into a wafer with luster, heating to 500 ℃ at the heating rate of 4 ℃/min in the air atmosphere, preserving heat for 4h, and cooling to obtain a composite metal oxide precursor;
and sequentially grinding and tabletting the composite metal oxide precursor (the pressure of the tabletting is 15mbar, and the time is 5 min), pressing the composite metal oxide precursor into a wafer with luster, heating to 900 ℃ at a heating rate of 3 ℃/min in an oxygen atmosphere, preserving heat for 14h, and cooling to obtain the P3 phase-coated P2 phase positive electrode material.
Example 3
The positive electrode material: na (Na) 0.67 Li 0.03 Cu 0.30 Zn 0.08 Mn 0.62 O 2+β (ii) a The valence states of Mn include +2 and + 3; the anode material is of a laminated structure, and the laminated structure comprises a P2 phase layer and a P3 phase coating layer; the P2 phase in the P2 phase layer is Na 0.67 Li 0.0 3 Cu 0.30 Zn 0.08 Mn 0.62 O 2+β1 Satisfied value of beta 1The P3 phase in the P3 phase coating is Na 0.43 Li 0.03 Cu 0.30 Zn 0.08 Mn 0.62 O 2+β2 The value of beta 2 satisfies the balance of valence; the thickness of the P3 phase coating layer is 3-10 nm; the anode material comprises small particles with the particle size of 10-200 nm and large particles with the particle size of 1-10 mu m;
the preparation method comprises the following steps:
mixing copper acetate, zinc acetate, manganese acetate, lithium nitrate and sodium nitrate with a deionized water solution of 150mL of citric acid with a concentration of 3mol/L (mass ratio of copper acetate to citric acid is 1;
sequentially grinding and tabletting the metal composite gel precursor (the pressure of the tabletting is 15mbar, and the time is 5 min), pressing into a wafer with luster, heating to 500 ℃ at the heating rate of 4 ℃/min in the air atmosphere, preserving heat for 4h, and cooling to obtain a composite metal oxide precursor;
and sequentially grinding and tabletting the composite metal oxide precursor (the pressure of the tabletting is 15mbar, and the time is 5 min), pressing into a wafer with luster, heating to 900 ℃ at the heating rate of 3 ℃/min in the oxygen atmosphere, preserving heat for 14h, and cooling to obtain the P3 phase-coated P2 phase positive electrode material.
Comparative example 1
A positive electrode material: na (Na) 0.78 Cu 0.27 Zn 0.06 Mn 0.67 O 2 ；
The preparation method comprises the following steps:
mixing copper acetate, zinc acetate, manganese acetate and sodium nitrate with 150mL of deionized water solution of citric acid with the concentration of 3mol/L (the mass ratio of the copper acetate to the citric acid is 1;
sequentially grinding and tabletting the metal composite gel precursor (the pressure of the tabletting is 15mbar, and the time is 5 min) to form a wafer with luster, heating to 500 ℃ at a heating rate of 4 ℃/min in an air atmosphere, preserving heat for 4h, and cooling to obtain a composite metal oxide precursor;
and sequentially grinding and tabletting the composite metal oxide precursor (the pressure of the tabletting is 15mbar, and the time is 5 min), pressing the composite metal oxide precursor into a wafer with luster, heating to 900 ℃ at a heating rate of 3 ℃/min in an oxygen atmosphere, preserving heat for 14h, and naturally cooling to obtain the anode material.
The positive electrode material is subjected to SEM test, the test result is shown in FIG. 8, and it can be known from FIG. 8 that the surface of the material which is not coated is obviously smooth;
drying the positive electrode material at 110 ℃ for 12 hours, and uniformly dispersing 8g of the dried positive electrode material, 1g of acetylene black and 1g of vinylidene fluoride in N-methyl-2-pyrrolidone to obtain slurry; coating the slurry on an aluminum foil, drying at 110 ℃ in vacuum, cutting into pole pieces, placing the pole pieces in a high-purity argon glove box, taking metal sodium as a negative electrode, taking glass fiber as a diaphragm, and taking 1M NaPF 6 the/EC + DME (1;
fig. 9 is a rate performance spectrogram of the button cell battery, and as can be seen from fig. 9, the button cell battery has 70.2mA · h · g magnifications of 0.10C, 0.20C, 0.50C, 1.0C, 2.0C and 5.0C, respectively -1 、69.3mA·h·g -1 、65.5mA·h·g -1 、50.6mA·h·g -1 、35.6mA·h·g -1 And 11.1 mA. H. G -1 After deep discharge at large multiplying power, the button cell can still maintain 70 mA.h.g when the multiplying power is reduced to 0.1C -1 The specific discharge capacity of (2).
In summary, the cathode material described in comparative example 1 has a lower ion conductivity under a large current than the cathode material described in example 1, and the advantage of the cathode material described in the present invention in a high-rate fast charge and discharge is also highlighted.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and amendments can be made without departing from the principle of the present invention, and these modifications and amendments should also be considered as the protection scope of the present invention.

Claims (10)

1. The cathode material is characterized by being of a layered structure, wherein the layered structure comprises a P2 phase layer and a P3 phase coating layer;
the chemical composition general formula of the cathode material is as follows: na (Na) a Li b Cu c Zn d Mn e O 2+β Wherein a is 0.67 to 0.8, b is 0.01 to 0.03, c is 0.2 to 0.3, d is 0.05 to 0.08, e is 0.6 to 0.7, and the value of beta satisfies the balance of valence;
the valence states of Mn in the positive electrode material include +2 and + 3.
2. The positive electrode material according to claim 1, wherein a is 0.7 to 0.8, b is 0.02, c is 0.25 to 0.3, d is 0.06 to 0.07, e is 0.64 to 0.66, and β satisfies a valence balance.
3. The positive electrode material according to claim 2, wherein a =0.78, b =0.02, c =0.27, d =0.06, e =0.65, and β satisfies a balance of valence.
4. The positive electrode material according to any one of claims 1 to 3, wherein the P3 phase coating layer has a thickness of 3 to 10nm.
5. The positive electrode material according to any one of claims 1 to 3, wherein the positive electrode material comprises small particles having a particle diameter of 10 to 200nm and large particles having a particle diameter of 1 to 10 μm.
6. The method for producing a positive electrode material according to any one of claims 1 to 5, comprising the steps of:
mixing soluble copper salt, soluble zinc salt, soluble divalent manganese salt, soluble lithium salt, soluble sodium salt, complexing agent and water to obtain a metal composite gel precursor;
sintering the metal composite gel precursor to obtain a composite metal oxide precursor;
and calcining the composite metal oxide precursor to obtain the cathode material.
7. The method according to claim 6, wherein the complexing agent is one or more selected from the group consisting of citric acid, a citrate, maleic acid, and a maleate.
8. The method according to claim 6, wherein the sintering temperature is 400 to 600 ℃, the holding time is 3 to 5 hours, and the heating rate for heating to the sintering temperature is 2 to 5 ℃/min.
9. The method according to claim 6, wherein the calcination temperature is 800 to 1000 ℃, the holding time is 10 to 15 hours, and the temperature increase rate for increasing the temperature to the calcination temperature is 2 to 5 ℃/min.
10. Use of the positive electrode material according to any one of claims 1 to 5 or the positive electrode material prepared by the preparation method according to any one of claims 6 to 9 in a sodium ion battery.
CN202211416876.5A 2022-11-14 2022-11-14 Cathode material and preparation method and application thereof Pending CN115621454A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116504953A (en) * 2023-06-28 2023-07-28 宁德时代新能源科技股份有限公司 Positive electrode active material, preparation method, positive electrode plate, battery and electric equipment
CN116525814A (en) * 2023-06-29 2023-08-01 宁波容百新能源科技股份有限公司 Positive electrode material, preparation method thereof, positive electrode plate and sodium ion battery

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116504953A (en) * 2023-06-28 2023-07-28 宁德时代新能源科技股份有限公司 Positive electrode active material, preparation method, positive electrode plate, battery and electric equipment
CN116504953B (en) * 2023-06-28 2023-11-17 宁德时代新能源科技股份有限公司 Positive electrode active material, preparation method, positive electrode plate, battery and electric equipment
CN116525814A (en) * 2023-06-29 2023-08-01 宁波容百新能源科技股份有限公司 Positive electrode material, preparation method thereof, positive electrode plate and sodium ion battery
CN116525814B (en) * 2023-06-29 2023-11-28 宁波容百新能源科技股份有限公司 Positive electrode material, preparation method thereof, positive electrode plate and sodium ion battery

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