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CN117199341B - A sodium ion battery - Google Patents

A sodium ion battery Download PDF

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Publication number
CN117199341B
CN117199341B CN202311259586.9A CN202311259586A CN117199341B CN 117199341 B CN117199341 B CN 117199341B CN 202311259586 A CN202311259586 A CN 202311259586A CN 117199341 B CN117199341 B CN 117199341B
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active material
positive electrode
ion battery
sodium ion
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CN117199341A (en
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童志伟
齐梦斐
蒲柳月
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China Innovation Aviation Technology Group Co ltd
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China Innovation Aviation Technology Group Co ltd
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

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Abstract

The invention discloses a sodium ion battery, which comprises a positive plate, wherein the positive plate comprises a positive current collector and positive active material layers arranged on two opposite surfaces of the positive current collector, the positive active material layers comprise positive active materials, the negative plate comprises a negative current collector and negative active material layers arranged on two opposite surfaces of the negative current collector, and the ratio a of the unit cell volume change rate of the positive active materials to the capacity contribution is more than or equal to 0.05 and less than or equal to 0.14. The sodium ion battery of the invention improves the structural stability of the positive electrode active material under high voltage by controlling the ratio of the unit cell volume change rate to the capacity contribution of the positive electrode active material, thereby prolonging the cycle life of the sodium ion battery.

Description

Sodium ion battery
Technical Field
The invention relates to the technical field of batteries, in particular to a sodium ion battery.
Background
Sodium ion batteries rely on sodium ions to move between a positive electrode and a negative electrode for charging and discharging, wherein during charging, sodium ions are extracted from the positive electrode and inserted into the negative electrode through an electrolyte, and during discharging, sodium ions are extracted from the negative electrode and inserted into the positive electrode through the electrolyte.
As a key component of sodium ion batteries, the positive electrode active material directly determines the energy density and cycle life of the overall battery system. Layered transition metal oxides with an O3 phase provide open prismatic channels for sodium ion diffusion, low diffusion barriers, and relatively high operating potentials, becoming very attractive candidate positive active materials for sodium ion batteries. However, in the charge and discharge process of the sodium ion battery, the positive electrode active material can generate O3-P3-O3 'phase change, especially when the charge voltage is more than 4.0V, the P3-O3' phase change reversibility of the positive electrode active material is low, so that the crystal structure and the unit cell volume of the positive electrode active material are changed, microcracks are generated, and the microcracks are gradually expanded along with the occurrence of charge and discharge cycles of the sodium ion battery, so that the structural stability of the positive electrode active material is poor, and the cycle performance of the sodium ion battery is finally affected.
Disclosure of Invention
In order to solve the above-mentioned drawbacks of the prior art, an object of the present invention is to provide a sodium ion battery having a high cycle performance.
The technical scheme provided by the invention is as follows:
A sodium ion battery comprising:
The positive plate comprises a positive current collector and positive active material layers arranged on two opposite surfaces of the positive current collector, wherein the positive active material layers comprise positive active materials;
the negative plate comprises a negative current collector and negative active material layers arranged on two opposite surfaces of the negative current collector;
The ratio a of the unit cell volume change rate V of the positive electrode active material to the capacity contribution C satisfies 0.05-0.14;
Wherein the unit cell volume change rate of the positive electrode active material V 1 is the unit cell volume of the positive active material of the positive plate when the second charge of the charge-discharge cycle is 4.0V after the disassembly of the sodium ion battery discharged to 2.0V, V 2 is the unit cell volume of the positive active material of the positive plate when the second charge of the charge-discharge cycle is 4.2V after the disassembly of the same sodium ion battery discharged to 2.0V;
Capacity contribution C 1 is the capacity exerted by the sodium ion battery in the voltage interval of 4.0-4.2V in the second charging process in 3 circles of 1C CC to 4.2V,CV to 0.05C,rest 10min,1C DC to 2.00V,rest 10min charging and discharging cycles, and C 2 is the capacity exerted by the sodium ion battery in the voltage interval of 2-4.2V in the second charging process in 3 circles of 1C CC to 4.2V,CV to 0.05C,rest 10min,1C DC to 2.00V,rest 10min charging and discharging cycles.
The sodium ion battery of the invention improves the structural stability of the positive electrode active material under high voltage by controlling the ratio of the unit cell volume change rate to the capacity contribution of the positive electrode active material, thereby prolonging the cycle life of the sodium ion battery.
Detailed Description
In order that those skilled in the art will better understand the present invention, a technical solution of the embodiments of the present invention will be clearly and completely described below, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments.
In the invention, CNT is carbon nanotube, PVDF is polyvinylidene fluoride, CMC is carboxymethyl cellulose, SBR is styrene butadiene rubber, NMP is N-methyl pyrrolidone.
Example 1
The embodiment provides a preparation method of a sodium ion battery, which comprises the following steps:
1) Preparing an anode active material, namely weighing Ni SO 4·6H2O、FeSO4·7H2 O and MnSO 4·H2 O with total concentration of 2.0M in a continuous stirred tank reactor according to a molar ratio of 0.4:0.26:0.34 by adopting a coprecipitation method, adding a sodium hydroxide solution with concentration of 2.0M into the continuous stirred tank reactor to prepare a mixed solution, transferring the mixed solution into a storage tank, transferring the mixed solution into a reaction kettle, heating under the protection of nitrogen, controlling the concentration of complexing agent ammonia water to be 0.4M, controlling the pH value to be 12.5 and the reaction temperature to be 50 ℃, filtering the obtained powder after aging, washing the powder with deionized water, drying the powder in 100 ℃, sieving and demagnetizing the powder to obtain a ternary precursor (Ni 0.4Fe0.26Mn0.34)(OH)2;
Uniformly mixing ternary precursors (Ni 0.4Fe0.26Mn0.34)(OH)2 and sodium carbonate according to a molar ratio of 1:1) in a crucible, putting the crucible into an atmosphere resistance furnace, controlling sintering temperature to 950 ℃, keeping the temperature for 15 hours, cooling to room temperature after sintering, sieving, and sealing to obtain the positive electrode active material NaNi 0.4Fe0.26Mn0.34O2 with the particle size D50 of 4.6 mu m.
2) The positive plate is prepared by mixing the positive electrode active material NaNi 0.4Fe0.26Mn0.34O2 prepared in the step 1) with SuperP, a conductive agent CNT and a binder PVDF according to the mass ratio of 97.5:1:0.5:1, controlling the solid content of the slurry to be 70%, obtaining positive electrode slurry, uniformly coating the positive electrode slurry on two opposite surfaces of a positive electrode current collector aluminum foil, drying, and rolling to obtain the positive plate with the double-sided density of 312g/m 2 and the compacted density of 3.5g/m 3.
3) The preparation of the anode active material comprises the steps of carbonizing biomass raw materials such as coconut shells and the like into carbon at 600 ℃, coarse crushing, fine crushing, grading, soaking in alkali liquor for 12 hours, drying at 120 ℃ to obtain powder, heating the powder to 1300 ℃, preserving the heat for 2 hours, purifying, and then carrying out modification treatment to obtain the hard carbon.
4) Preparing a negative electrode sheet, namely preparing hard carbon, super P, CMC and SBR prepared in the step 3) according to the mass ratio of 96.1:0.8:1.5:1.6;
Adding hard carbon and Super P into a 5L stirring kettle according to the formula amount, and stirring and dry-mixing to obtain dry powder;
CMC is dissolved in deionized water and is subjected to autorotation dispersion for 120min at 1800rmp, so that CMC glue solution with the solid content of 1.4% is obtained;
Mixing, stirring and dispersing dry powder, 50% of CMC glue solution and 50% of deionized water according to the formula amount for 60min, adding the rest 50% of CMC glue solution and 50% of deionized water, continuously stirring for 60min, adding SBR, stirring for 60min, and then adding a proper amount of deionized water to adjust the viscosity to 3000-5000 Pa.s, so as to obtain the cathode slurry with the solid content of 50%;
The negative electrode slurry is uniformly coated on two opposite surfaces of a negative electrode current collector aluminum foil, and the negative electrode plate with the double-sided density of 200g/m 2 and the compacted density of 1.0g/m 3 of the negative electrode active material layer is obtained by rolling.
5) And (3) preparing an electrolyte, namely mixing ethylene carbonate, ethylmethyl carbonate and diethyl carbonate according to a volume ratio of 3:5:2 to obtain an organic solvent, adding fully dried sodium salt NaPF 6 into the organic solvent, and stirring until the sodium salt NaPF 6 is completely dissolved to prepare the electrolyte with the concentration of sodium salt NaPF 6 of 1 mol/L.
6) And (3) preparing a battery, namely sequentially laminating the positive electrode sheet of the step (2), the ceramic diaphragm and the negative electrode sheet of the step (4), putting the laminated positive electrode sheet and the laminated negative electrode sheet into a shell, and then injecting liquid, forming and fixing the volume to obtain the sodium ion battery of the embodiment.
Example 2
The embodiment provides a preparation method of a sodium ion battery, which comprises the following steps:
1) Preparing an anode active material, namely weighing NiSO 4·6H2O、FeSO4·7H2 O and MnSO 4·H2 O with total concentration of 2.0M in a continuous stirred tank reactor according to a molar ratio of 0.425:0.235:0.34 by adopting a coprecipitation method, adding a sodium hydroxide solution with concentration of 2.0M into the continuous stirred tank reactor to prepare a mixed solution, transferring the mixed solution into a storage tank, transferring the mixed solution into a reaction kettle, heating under the protection of nitrogen, controlling the concentration of complexing agent ammonia water to be 0.4M, controlling the pH value to be 12.5 and the reaction temperature to be 50 ℃, filtering the obtained powder after aging, washing the powder with deionized water, drying the powder in 100 ℃, sieving and demagnetizing the powder to obtain a ternary precursor (Ni 0.425Fe0.235Mn0.34)(OH)2;
Uniformly mixing ternary precursors (Ni 0.425Fe0.235Mn0.34)(OH)2 and sodium carbonate according to a molar ratio of 1:1) in a crucible, putting the crucible into an atmosphere resistance furnace, controlling the sintering temperature to 900 ℃, keeping the temperature for 15 hours, cooling to room temperature after sintering, sieving, and sealing to obtain the positive electrode active material NaNi 0.425Fe0.235Mn0.34O2 with the particle size D50 of 4.5 mu m.
2) The positive plate is prepared by mixing the positive electrode active material NaNi 0.425Fe0.235Mn0.34O2 prepared in the step 1) with Super P, a conductive agent CNT and a binder PVDF according to the mass ratio of 97.5:1:0.5:1, controlling the solid content of the slurry to be 70%, obtaining positive electrode slurry, uniformly coating the positive electrode slurry on two opposite surfaces of a positive electrode current collector aluminum foil, drying, and rolling to obtain the positive plate with the double-sided density of 312g/m 2 and the compacted density of 3.5g/m 3 of a positive electrode active material layer.
3) The preparation of the anode active material comprises the steps of carbonizing biomass raw materials such as coconut shells and the like into carbon at 600 ℃, coarse crushing, fine crushing, grading, soaking in alkali liquor for 12 hours, drying at 120 ℃ to obtain powder, heating the powder to 1300 ℃, preserving the heat for 2 hours, purifying, and then carrying out modification treatment to obtain the hard carbon.
4) Preparing a negative electrode sheet, namely preparing hard carbon, super P, CMC and SBR prepared in the step 3) according to the mass ratio of 96.1:0.8:1.5:1.6;
Adding hard carbon and Super P into a 5L stirring kettle according to the formula amount, and stirring and dry-mixing to obtain dry powder;
CMC is dissolved in deionized water and is subjected to autorotation dispersion for 120min at 1800rmp, so that CMC glue solution with the solid content of 1.4% is obtained;
Mixing, stirring and dispersing dry powder, 50% of CMC glue solution and 50% of deionized water according to the formula amount for 60min, adding the rest 50% of CMC glue solution and 50% of deionized water, continuously stirring for 60min, adding SBR, stirring for 60min, and then adding a proper amount of deionized water to adjust the viscosity to 3000-5000 Pa.s, so as to obtain the cathode slurry with the solid content of 50%;
The negative electrode slurry is uniformly coated on two opposite surfaces of a negative electrode current collector aluminum foil, and the negative electrode plate with the double-sided density of 200g/m 2 and the compacted density of 1.0g/m 3 of the negative electrode active material layer is obtained by rolling.
5) And (3) preparing an electrolyte, namely mixing ethylene carbonate, ethylmethyl carbonate and diethyl carbonate according to a volume ratio of 3:5:2 to obtain an organic solvent, adding fully dried sodium salt NaPF 6 into the organic solvent, and stirring until the sodium salt NaPF 6 is completely dissolved to prepare the electrolyte with the concentration of sodium salt NaPF 6 of 1 mol/L.
6) And (3) preparing a battery, namely sequentially laminating the positive electrode sheet of the step (2), the ceramic diaphragm and the negative electrode sheet of the step (4), putting the laminated positive electrode sheet and the laminated negative electrode sheet into a shell, and then injecting liquid, forming and fixing the volume to obtain the sodium ion battery of the embodiment.
Example 3
The embodiment provides a preparation method of a sodium ion battery, which comprises the following steps:
1) Preparing an anode active material, namely weighing NiSO 4·6H2O、FeSO4·7H2 O and MnSO 4·H2 O with total concentration of 2.0M in a continuous stirred tank reactor according to a molar ratio of 0.45:0.21:0.34 by adopting a coprecipitation method, adding a sodium hydroxide solution with concentration of 2.0M into the continuous stirred tank reactor to prepare a mixed solution, transferring the mixed solution into a storage tank, transferring the mixed solution into a reaction kettle, heating under the protection of nitrogen, controlling the concentration of complexing agent ammonia water to be 0.4M, controlling the pH value to be 12.5 and the reaction temperature to be 50 ℃, filtering the obtained powder after aging, washing the powder with deionized water, drying the powder in 100 ℃, sieving and demagnetizing the powder to obtain a ternary precursor (Ni 0.45Fe0.21Mn0.34)(OH)2;
Uniformly mixing ternary precursors (Ni 0.45Fe0.21Mn0.34)(OH)2 and sodium carbonate according to a molar ratio of 1:1) in a crucible, putting the crucible into an atmosphere resistance furnace, controlling sintering temperature to 1010 ℃, keeping the temperature for 15 hours, cooling to room temperature after sintering, sieving, and sealing to obtain the positive electrode active material NaNi 0.45Fe0.21Mn0.34O2 with the particle size D50 of 4.8 mu m.
2) The positive plate is prepared by mixing the positive electrode active material NaNi 0.45Fe0.21Mn0.34O2 prepared in the step 1) with Super P, a conductive agent CNT and a binder PVDF according to the mass ratio of 97.5:1:0.5:1, controlling the solid content of the slurry to be 70%, obtaining positive electrode slurry, uniformly coating the positive electrode slurry on two opposite surfaces of a positive electrode current collector aluminum foil, drying, and rolling to obtain the positive plate with the double-sided density of 312g/m 2 and the compacted density of 3.5g/m 3 of a positive electrode active material layer.
3) The preparation of the anode active material comprises the steps of carbonizing biomass raw materials such as coconut shells and the like into carbon at 600 ℃, coarse crushing, fine crushing, grading, soaking in alkali liquor for 12 hours, drying at 120 ℃ to obtain powder, heating the powder to 1300 ℃, preserving the heat for 2 hours, purifying, and then carrying out modification treatment to obtain the hard carbon.
4) Preparing a negative electrode sheet, namely preparing hard carbon, super P, CMC and SBR prepared in the step 3) according to the mass ratio of 96.1:0.8:1.5:1.6;
Adding hard carbon and Super P into a 5L stirring kettle according to the formula amount, and stirring and dry-mixing to obtain dry powder;
CMC is dissolved in deionized water and is subjected to autorotation dispersion for 120min at 1800rmp, so that CMC glue solution with the solid content of 1.4% is obtained;
Mixing, stirring and dispersing dry powder, 50% of CMC glue solution and 50% of deionized water according to the formula amount for 60min, adding the rest 50% of CMC glue solution and 50% of deionized water, continuously stirring for 60min, adding SBR, stirring for 60min, and then adding a proper amount of deionized water to adjust the viscosity to 3000-5000 Pa.s, so as to obtain the cathode slurry with the solid content of 50%;
The negative electrode slurry is uniformly coated on two opposite surfaces of a negative electrode current collector aluminum foil, and the negative electrode plate with the double-sided density of 200g/m 2 and the compacted density of 1.0g/m 3 of the negative electrode active material layer is obtained by rolling.
5) And (3) preparing an electrolyte, namely mixing ethylene carbonate, ethylmethyl carbonate and diethyl carbonate according to a volume ratio of 3:5:2 to obtain an organic solvent, adding fully dried sodium salt NaPF 6 into the organic solvent, and stirring until the sodium salt NaPF 6 is completely dissolved to prepare the electrolyte with the concentration of sodium salt NaPF 6 of 1 mol/L.
6) And (3) preparing a battery, namely sequentially laminating the positive electrode sheet of the step (2), the ceramic diaphragm and the negative electrode sheet of the step (4), putting the laminated positive electrode sheet and the laminated negative electrode sheet into a shell, and then injecting liquid, forming and fixing the volume to obtain the sodium ion battery of the embodiment.
Example 4
The embodiment provides a preparation method of a sodium ion battery, which comprises the following steps:
1) Preparing an anode active material, namely weighing NiSO 4·6H2O、FeSO4·7H2 O and MnSO 4·H2 O with total concentration of 2.0M in a continuous stirred tank reactor according to a molar ratio of 0.35:0.31:0.34 by adopting a coprecipitation method, adding a sodium hydroxide solution with concentration of 2.0M into the continuous stirred tank reactor to prepare a mixed solution, transferring the mixed solution into a storage tank, transferring the mixed solution into a reaction kettle, heating under the protection of nitrogen, controlling the concentration of complexing agent ammonia water to be 0.4M, controlling the pH value to be 12.5 and the reaction temperature to be 50 ℃, filtering the obtained powder after aging, washing the powder with deionized water, drying the powder in 100 ℃, sieving and demagnetizing the powder to obtain a ternary precursor (Ni 0.35Fe0.31Mn0.34)(OH)2;
Uniformly mixing ternary precursors (Ni 0.35Fe0.31Mn0.34)(OH)2 and sodium carbonate in a molar ratio of 1:1) in a crucible, putting the crucible into an atmosphere resistance furnace, controlling the sintering temperature to 975 ℃, keeping the temperature for 15 hours, cooling to room temperature after sintering, sieving, and sealing to obtain the positive electrode active material NaNi 0.35Fe0.31Mn0.34O2 with the particle size D50 of 4.7 mu m.
2) The positive plate is prepared by mixing the positive electrode active material NaNi 0.35Fe0.31Mn0.34O2 prepared in the step 1) with Super P, a conductive agent CNT and a binder PVDF according to the mass ratio of 97.5:1:0.5:1, controlling the solid content of the slurry to be 70%, obtaining positive electrode slurry, uniformly coating the positive electrode slurry on two opposite surfaces of a positive electrode current collector aluminum foil, drying, and rolling to obtain the positive plate with the double-sided density of 312g/m 2 and the compacted density of 3.5g/m 3 of a positive electrode active material layer.
3) The preparation of the anode active material comprises the steps of carbonizing biomass raw materials such as coconut shells and the like into carbon at 600 ℃, coarse crushing, fine crushing, grading, soaking in alkali liquor for 12 hours, drying at 120 ℃ to obtain powder, heating the powder to 1300 ℃, preserving the heat for 2 hours, purifying, and then carrying out modification treatment to obtain hard carbon.
4) Preparing a negative electrode sheet, namely preparing hard carbon, super P, CMC and SBR prepared in the step 3) according to the mass ratio of 96.1:0.8:1.5:1.6;
Adding hard carbon and Super P into a 5L stirring kettle according to the formula amount, and stirring and dry-mixing to obtain dry powder;
CMC is dissolved in deionized water and is subjected to autorotation dispersion for 120min at 1800rmp, so that CMC glue solution with the solid content of 1.4% is obtained;
Mixing, stirring and dispersing dry powder, 50% of CMC glue solution and 50% of deionized water according to the formula amount for 60min, adding the rest 50% of CMC glue solution and 50% of deionized water, continuously stirring for 60min, adding SBR, stirring for 60min, and then adding a proper amount of deionized water to adjust the viscosity to 3000-5000 Pa.s, so as to obtain the cathode slurry with the solid content of 50%;
The negative electrode slurry is uniformly coated on two opposite surfaces of a negative electrode current collector aluminum foil, and the negative electrode plate with the double-sided density of 200g/m 2 and the compacted density of 1.0g/m 3 of the negative electrode active material layer is obtained by rolling.
5) And (3) preparing an electrolyte, namely mixing ethylene carbonate, ethylmethyl carbonate and diethyl carbonate according to a volume ratio of 3:5:2 to obtain an organic solvent, adding fully dried sodium salt NaPF 6 into the organic solvent, and stirring until the sodium salt NaPF 6 is completely dissolved to prepare the electrolyte with the concentration of sodium salt NaPF 6 of 1 mol/L.
6) And (3) preparing a battery, namely sequentially laminating the positive electrode sheet of the step (2), the ceramic diaphragm and the negative electrode sheet of the step (4), putting the laminated positive electrode sheet and the laminated negative electrode sheet into a shell, and then injecting liquid, forming and fixing the volume to obtain the sodium ion battery of the embodiment.
Example 5
The embodiment provides a preparation method of a sodium ion battery, which comprises the following steps:
1) Preparing an anode active material, namely weighing NiSO 4·6H2O、FeSO4·7H2 O and MnSO 4·H2 O with total concentration of 2.0M in a continuous stirred tank reactor according to a molar ratio of 0.4:0.26:0.34 by adopting a coprecipitation method, adding a sodium hydroxide solution with concentration of 2.0M into the continuous stirred tank reactor to prepare a mixed solution, transferring the mixed solution into a storage tank, transferring the mixed solution into a reaction kettle, heating under the protection of nitrogen, controlling the concentration of complexing agent ammonia water to be 0.4M, controlling the pH value to be 12.5 and the reaction temperature to be 50 ℃, filtering the obtained powder after aging, washing the powder with deionized water, drying the powder in 100 ℃, sieving and demagnetizing the powder to obtain a ternary precursor (Ni 0.4Fe0.26Mn0.34)(OH)2;
Uniformly mixing ternary precursors (Ni 0.4Fe0.26Mn0.34)(OH)2 and sodium carbonate in a molar ratio of 1:1) in a crucible, putting the crucible into an atmosphere resistance furnace, controlling the sintering temperature to 975 ℃, keeping the temperature for 15 hours, cooling to room temperature after sintering, sieving, and sealing to obtain the positive electrode active material NaNi 0.4Fe0.26Mn0.34O2 with the particle size D50 of 4.5 mu m.
2) The positive plate is prepared by mixing the positive electrode active material NaNi 0.4Fe0.26Mn0.34O2 prepared in the step 1) with Super P, a conductive agent CNT and a binder PVDF according to the mass ratio of 97.5:1:0.5:1, controlling the solid content of the slurry to be 70%, obtaining positive electrode slurry, uniformly coating the positive electrode slurry on two opposite surfaces of a positive electrode current collector aluminum foil, drying, and rolling to obtain the positive plate with the double-sided density of 312g/m 2 and the compacted density of 3.5g/m 3 of a positive electrode active material layer.
3) The preparation of the anode active material comprises the steps of carbonizing biomass raw materials such as coconut shells and the like into carbon at 600 ℃, coarse crushing, fine crushing, grading, soaking in alkali liquor for 12 hours, drying at 120 ℃ to obtain powder, heating the powder to 1300 ℃, preserving the heat for 2 hours, purifying, and then carrying out modification treatment to obtain hard carbon.
4) Preparing a negative electrode sheet, namely preparing hard carbon, super P, CMC and SBR prepared in the step 3) according to the mass ratio of 96.1:0.8:1.5:1.6;
Adding hard carbon and Super P into a 5L stirring kettle according to the formula amount, and stirring and dry-mixing to obtain dry powder;
CMC is dissolved in deionized water and is subjected to autorotation dispersion for 120min at 1800rmp, so that CMC glue solution with the solid content of 1.4% is obtained;
Mixing, stirring and dispersing dry powder, 50% of CMC glue solution and 50% of deionized water according to the formula amount for 60min, adding the rest 50% of CMC glue solution and 50% of deionized water, continuously stirring for 60min, adding SBR, stirring for 60min, and then adding a proper amount of deionized water to adjust the viscosity to 3000-5000 Pa.s, so as to obtain the cathode slurry with the solid content of 50%;
The negative electrode slurry is uniformly coated on two opposite surfaces of a negative electrode current collector aluminum foil, and the negative electrode plate with the double-sided density of 200g/m 2 and the compacted density of 1.0g/m 3 of the negative electrode active material layer is obtained by rolling.
5) And (3) preparing an electrolyte, namely mixing ethylene carbonate, ethylmethyl carbonate and diethyl carbonate according to a volume ratio of 3:5:2 to obtain an organic solvent, adding fully dried sodium salt NaPF 6 into the organic solvent, and stirring until the sodium salt NaPF 6 is completely dissolved to prepare the electrolyte with the concentration of sodium salt NaPF 6 of 1 mol/L.
6) And (3) preparing a battery, namely sequentially laminating the positive electrode sheet of the step (2), the ceramic diaphragm and the negative electrode sheet of the step (4), putting the laminated positive electrode sheet and the laminated negative electrode sheet into a shell, and then injecting liquid, forming and fixing the volume to obtain the sodium ion battery of the embodiment.
Example 6
The embodiment provides a preparation method of a sodium ion battery, which comprises the following steps:
1) Preparing an anode active material, namely weighing NiSO 4·6H2O、FeSO4·7H2 O and MnSO 4·H2 O with total concentration of 2.0M in a continuous stirred tank reactor according to a molar ratio of 0.425:0.235:0.34 by adopting a coprecipitation method, adding a sodium hydroxide solution with concentration of 2.0M into the continuous stirred tank reactor to prepare a mixed solution, transferring the mixed solution into a storage tank, transferring the mixed solution into a reaction kettle, heating under the protection of nitrogen, controlling the concentration of complexing agent ammonia water to be 0.4M, controlling the pH value to be 12.5 and the reaction temperature to be 50 ℃, filtering the obtained powder after aging, washing the powder with deionized water, drying the powder in 100 ℃, sieving and demagnetizing the powder to obtain a ternary precursor (Ni 0.425Fe0.235Mn0.34)(OH)2;
Uniformly mixing ternary precursors (Ni 0.425Fe0.235Mn0.34)(OH)2 and sodium carbonate according to a molar ratio of 1:1) in a crucible, putting the crucible into an atmosphere resistance furnace, controlling sintering temperature to 1010 ℃, keeping the temperature for 15 hours, cooling to room temperature after sintering, sieving, and sealing to obtain the positive electrode active material NaNi 0.425Fe0.235Mn0.34O2 with the particle size D50 of 4.5 mu m.
2) The positive plate is prepared by mixing the positive electrode active material NaNi 0.425Fe0.235Mn0.34O2 prepared in the step 1) with Super P, a conductive agent CNT and a binder PVDF according to the mass ratio of 97.5:1:0.5:1, controlling the solid content of the slurry to be 70%, obtaining positive electrode slurry, uniformly coating the positive electrode slurry on two opposite surfaces of a positive electrode current collector aluminum foil, drying, and rolling to obtain the positive plate with the double-sided density of 312g/m 2 and the compacted density of 3.5g/m 3 of a positive electrode active material layer.
3) The preparation of the anode active material comprises the steps of carbonizing biomass raw materials such as coconut shells and the like into carbon at 600 ℃, coarse crushing, fine crushing, grading, soaking in alkali liquor for 12 hours, drying at 120 ℃ to obtain powder, heating the powder to 1300 ℃, preserving the heat for 2 hours, purifying, and then carrying out modification treatment to obtain hard carbon.
4) Preparing a negative electrode sheet, namely preparing hard carbon, super P, CMC and SBR prepared in the step 3) according to the mass ratio of 96.1:0.8:1.5:1.6;
Adding hard carbon and Super P into a 5L stirring kettle according to the formula amount, and stirring and dry-mixing to obtain dry powder;
CMC is dissolved in deionized water and is subjected to autorotation dispersion for 120min at 1800rmp, so that CMC glue solution with the solid content of 1.4% is obtained;
Mixing, stirring and dispersing dry powder, 50% of CMC glue solution and 50% of deionized water according to the formula amount for 60min, adding the rest 50% of CMC glue solution and 50% of deionized water, continuously stirring for 60min, adding SBR, stirring for 60min, and then adding a proper amount of deionized water to adjust the viscosity to 3000-5000 Pa.s, so as to obtain the cathode slurry with the solid content of 50%;
The negative electrode slurry is uniformly coated on two opposite surfaces of a negative electrode current collector aluminum foil, and the negative electrode plate with the double-sided density of 200g/m 2 and the compacted density of 1.0g/m 3 of the negative electrode active material layer is obtained by rolling.
5) And (3) preparing an electrolyte, namely mixing ethylene carbonate, ethylmethyl carbonate and diethyl carbonate according to a volume ratio of 3:5:2 to obtain an organic solvent, adding fully dried sodium salt NaPF 6 into the organic solvent, and stirring until the sodium salt NaPF 6 is completely dissolved to prepare the electrolyte with the concentration of sodium salt NaPF 6 of 1 mol/L.
6) And (3) preparing a battery, namely sequentially laminating the positive electrode sheet of the step (2), the ceramic diaphragm and the negative electrode sheet of the step (4), putting the laminated positive electrode sheet and the laminated negative electrode sheet into a shell, and then injecting liquid, forming and fixing the volume to obtain the sodium ion battery of the embodiment.
Example 7
The embodiment provides a preparation method of a sodium ion battery, which comprises the following steps:
1) Preparing an anode active material, namely weighing NiSO 4·6H2O、FeSO4·7H2 O and MnSO 4·H2 O with total concentration of 2.0M in a continuous stirred tank reactor according to a molar ratio of 0.45:0.21:0.34 by adopting a coprecipitation method, adding a sodium hydroxide solution with concentration of 2.0M into the continuous stirred tank reactor to prepare a mixed solution, transferring the mixed solution into a storage tank, transferring the mixed solution into a reaction kettle, heating under the protection of nitrogen, controlling the concentration of complexing agent ammonia water to be 0.4M, controlling the pH value to be 12.5 and the reaction temperature to be 50 ℃, filtering the obtained powder after aging, washing the powder with deionized water, drying the powder in 100 ℃, sieving and demagnetizing the powder to obtain a ternary precursor (Ni 0.45Fe0.21Mn0.34)(OH)2;
uniformly mixing ternary precursors (Ni 0.45Fe0.21Mn0.34)(OH)2 and sodium carbonate in a molar ratio of 1:1) in a crucible, putting the crucible into an atmosphere resistance furnace, controlling the sintering temperature to 975 ℃, keeping the temperature for 15 hours, cooling to room temperature after sintering, sieving, and sealing to obtain the positive electrode active material NaNi 0.45Fe0.21Mn0.34O2 with the particle size D50 of 4.8 mu m.
2) The positive plate is prepared by mixing the positive electrode active material NaNi 0.45Fe0.21Mn0.34O2 prepared in the step 1) with Super P, a conductive agent CNT and a binder PVDF according to the mass ratio of 97.5:1:0.5:1, controlling the solid content of the slurry to be 70%, obtaining positive electrode slurry, uniformly coating the positive electrode slurry on two opposite surfaces of a positive electrode current collector aluminum foil, drying, and rolling to obtain the positive plate with the double-sided density of 312g/m 2 and the compacted density of 3.5g/m 3 of a positive electrode active material layer.
3) The preparation of the anode active material comprises the steps of carbonizing biomass raw materials such as coconut shells and the like into carbon at 600 ℃, coarse crushing, fine crushing, grading, soaking in alkali liquor for 12 hours, drying at 120 ℃ to obtain powder, heating the powder to 1300 ℃, preserving the heat for 2 hours, purifying, and then carrying out modification treatment to obtain hard carbon.
4) Preparing a negative electrode sheet, namely preparing hard carbon, super P, CMC and SBR prepared in the step 3) according to the mass ratio of 96.1:0.8:1.5:1.6;
Adding hard carbon and Super P into a 5L stirring kettle according to the formula amount, and stirring and dry-mixing to obtain dry powder;
CMC is dissolved in deionized water and is subjected to autorotation dispersion for 120min at 1800rmp, so that CMC glue solution with the solid content of 1.4% is obtained;
Mixing, stirring and dispersing dry powder, 50% of CMC glue solution and 50% of deionized water according to the formula amount for 60min, adding the rest 50% of CMC glue solution and 50% of deionized water, continuously stirring for 60min, adding SBR, stirring for 60min, and then adding a proper amount of deionized water to adjust the viscosity to 3000-5000 Pa.s, so as to obtain the cathode slurry with the solid content of 50%;
The negative electrode slurry is uniformly coated on two opposite surfaces of a negative electrode current collector aluminum foil, and the negative electrode plate with the double-sided density of 200g/m 2 and the compacted density of 1.0g/m 3 of the negative electrode active material layer is obtained by rolling.
5) And (3) preparing an electrolyte, namely mixing ethylene carbonate, ethylmethyl carbonate and diethyl carbonate according to a volume ratio of 3:5:2 to obtain an organic solvent, adding fully dried sodium salt NaPF 6 into the organic solvent, and stirring until the sodium salt NaPF 6 is completely dissolved to prepare the electrolyte with the concentration of sodium salt NaPF 6 of 1 mol/L.
6) And (3) preparing a battery, namely sequentially laminating the positive electrode sheet of the step (2), the ceramic diaphragm and the negative electrode sheet of the step (4), putting the laminated positive electrode sheet and the laminated negative electrode sheet into a shell, and then injecting liquid, forming and fixing the volume to obtain the sodium ion battery of the embodiment.
Example 8
The embodiment provides a preparation method of a sodium ion battery, which comprises the following steps:
1) Preparing an anode active material, namely weighing NiSO 4·6H2O、FeSO4·7H2 O and MnSO 4·H2 O with total concentration of 2.0M in a continuous stirred tank reactor according to a molar ratio of 0.4:0.26:0.34 by adopting a coprecipitation method, adding a sodium hydroxide solution with concentration of 2.0M into the continuous stirred tank reactor to prepare a mixed solution, transferring the mixed solution into a storage tank, transferring the mixed solution into a reaction kettle, heating under the protection of nitrogen, controlling the concentration of complexing agent ammonia water to be 0.4M, controlling the pH value to be 12.5 and the reaction temperature to be 50 ℃, filtering the obtained powder after aging, washing the powder with deionized water, drying the powder in 100 ℃, sieving and demagnetizing the powder to obtain a ternary precursor (Ni 0.4Fe0.26Mn0.34)(OH)2;
Uniformly mixing ternary precursors (Ni 0.4Fe0.26Mn0.34)(OH)2 and sodium carbonate according to a molar ratio of 1:1) in a crucible, putting the crucible into an atmosphere resistance furnace, controlling sintering temperature to 950 ℃, keeping the temperature for 15 hours, cooling to room temperature after sintering, sieving, and sealing to obtain the positive electrode active material NaNi 0.4Fe0.26Mn0.34O2 with the particle size D50 of 4.6 mu m.
2) The positive plate is prepared by mixing the positive electrode active material NaNi 0.4Fe0.26Mn0.34O2 prepared in the step 1) with Super P, a conductive agent CNT and a binder PVDF according to the mass ratio of 97.5:1:0.5:1, controlling the solid content of the slurry to be 70%, obtaining positive electrode slurry, uniformly coating the positive electrode slurry on two opposite surfaces of a positive electrode current collector aluminum foil, drying, and rolling to obtain the positive plate with the double-sided density of 312g/m 2 and the compacted density of 3.5g/m 3 of a positive electrode active material layer.
3) The preparation of the anode active material comprises the steps of carbonizing biomass raw materials such as coconut shells and the like into carbon at 600 ℃, coarse crushing, fine crushing, grading, soaking in alkali liquor for 12 hours, drying at 120 ℃ to obtain powder, heating the powder to 1300 ℃, preserving the heat for 2 hours, purifying, and then carrying out modification treatment to obtain hard carbon.
4) Preparing a negative electrode sheet, namely preparing hard carbon, super P, CMC and SBR prepared in the step 3) according to the mass ratio of 96.1:0.8:1.5:1.6;
Adding hard carbon and Super P into a 5L stirring kettle according to the formula amount, and stirring and dry-mixing to obtain dry powder;
CMC is dissolved in deionized water and is subjected to autorotation dispersion for 120min at 1800rmp, so that CMC glue solution with the solid content of 1.4% is obtained;
Mixing, stirring and dispersing dry powder, 50% of CMC glue solution and 50% of deionized water according to the formula amount for 60min, adding the rest 50% of CMC glue solution and 50% of deionized water, continuously stirring for 60min, adding SBR, stirring for 60min, and then adding a proper amount of deionized water to adjust the viscosity to 3000-5000 Pa.s, so as to obtain the cathode slurry with the solid content of 50%;
The negative electrode slurry is uniformly coated on two opposite surfaces of a negative electrode current collector aluminum foil, and the negative electrode plate with the double-sided density of 200g/m 2 and the compacted density of 1.0g/m 3 of the negative electrode active material layer is obtained by rolling.
5) And (3) preparing an electrolyte, namely mixing ethylene carbonate, ethylmethyl carbonate and diethyl carbonate according to a volume ratio of 3:5:2 to obtain an organic solvent, adding fully dried sodium salt NaPF 6 into the organic solvent, and stirring until the sodium salt NaPF 6 is completely dissolved to prepare the electrolyte with the concentration of sodium salt NaPF 6 of 1 mol/L.
6) And (3) preparing a battery, namely sequentially laminating the positive electrode sheet of the step (2), the ceramic diaphragm and the negative electrode sheet of the step (4), putting the laminated positive electrode sheet and the laminated negative electrode sheet into a shell, and then injecting liquid, forming and fixing the volume to obtain the sodium ion battery of the embodiment.
Comparative example 1
The comparative example provides a method for preparing a sodium ion battery, comprising the following steps:
1) Preparing an anode active material, namely weighing NiSO 4·6H2O、FeSO4·7H2 O and MnSO 4·H2 O with total concentration of 2.0M in a continuous stirred tank reactor according to a molar ratio of 0.33:0.33:0.34 by adopting a coprecipitation method, adding a sodium hydroxide solution with concentration of 2.0M into the continuous stirred tank reactor to prepare a mixed solution, transferring the mixed solution into a storage tank, transferring the mixed solution into a reaction kettle, heating under the protection of nitrogen, controlling the concentration of complexing agent ammonia water to be 0.4M, controlling the pH value to be 12.5 and the reaction temperature to be 50 ℃, filtering the obtained powder after aging, washing the powder with deionized water, drying the powder in 100 ℃, sieving and demagnetizing the powder to obtain a ternary precursor (Ni 0.33Fe0.33Mn0.34)(OH)2;
Uniformly mixing ternary precursors (Ni 0.33Fe0.33Mn0.34)(OH)2 and sodium carbonate according to a molar ratio of 1:1) in a crucible, putting the crucible into an atmosphere resistance furnace, controlling sintering temperature to 950 ℃, keeping the temperature for 15 hours, cooling to room temperature after sintering, sieving, and sealing to obtain the positive electrode active material NaNi 0.33Fe0.33Mn0.34O2 with the particle size D50 of 12.3 mu m.
2) The positive plate is prepared by mixing the positive electrode active material NaNi 0.33Fe0.33Mn0.34O2 prepared in the step 1) with Super P, a conductive agent CNT and a binder PVDF according to the mass ratio of 97.5:1:0.5:1, controlling the solid content of the slurry to be 70%, obtaining positive electrode slurry, uniformly coating the positive electrode slurry on two opposite surfaces of a positive electrode current collector aluminum foil, drying, and rolling to obtain the positive plate with the double-sided density of 312g/m 2 and the compacted density of 3.5g/m 3 of a positive electrode active material layer.
3) The preparation of the anode active material comprises the steps of carbonizing biomass raw materials such as coconut shells and the like into carbon at 600 ℃, coarse crushing, fine crushing, grading, soaking in alkali liquor for 12 hours, drying at 120 ℃ to obtain powder, heating the powder to 1300 ℃, preserving the heat for 2 hours, purifying, and then carrying out modification treatment to obtain hard carbon.
4) Preparing a negative electrode sheet, namely preparing hard carbon, super P, CMC and SBR prepared in the step 3) according to the mass ratio of 96.1:0.8:1.5:1.6;
Adding hard carbon and Super P into a 5L stirring kettle according to the formula amount, and stirring and dry-mixing to obtain dry powder;
CMC is dissolved in deionized water and is subjected to autorotation dispersion for 120min at 1800rmp, so that CMC glue solution with the solid content of 1.4% is obtained;
Mixing, stirring and dispersing dry powder, 50% of CMC glue solution and 50% of deionized water according to the formula amount for 60min, adding the rest 50% of CMC glue solution and 50% of deionized water, continuously stirring for 60min, adding SBR, stirring for 60min, and then adding a proper amount of deionized water to adjust the viscosity to 3000-5000 Pa.s, so as to obtain the cathode slurry with the solid content of 50%;
The negative electrode slurry is uniformly coated on two opposite surfaces of a negative electrode current collector aluminum foil, and the negative electrode plate with the double-sided density of 200g/m 2 and the compacted density of 1.0g/m 3 of the negative electrode active material layer is obtained by rolling.
5) And (3) preparing an electrolyte, namely mixing ethylene carbonate, ethylmethyl carbonate and diethyl carbonate according to a volume ratio of 3:5:2 to obtain an organic solvent, adding fully dried sodium salt NaPF 6 into the organic solvent, and stirring until the sodium salt NaPF 6 is completely dissolved to prepare the electrolyte with the concentration of sodium salt NaPF 6 of 1 mol/L.
6) And (3) preparing a battery, namely sequentially laminating the positive electrode sheet of the step (2), the ceramic diaphragm and the negative electrode sheet of the step (4), putting the laminated positive electrode sheet and the laminated negative electrode sheet into a shell, and then carrying out liquid injection, formation and constant volume to obtain the sodium ion battery of the comparative example.
Comparative example 2
The comparative example provides a method for preparing a sodium ion battery, comprising the following steps:
1) Preparing an anode active material, namely weighing NiSO 4·6H2O、FeSO4·7H2 O and MnSO 4·H2 O with total concentration of 2.0M in a continuous stirred tank reactor according to a molar ratio of 0.4:0.26:0.34 by adopting a coprecipitation method, adding a sodium hydroxide solution with concentration of 2.0M into the continuous stirred tank reactor to prepare a mixed solution, transferring the mixed solution into a storage tank, transferring the mixed solution into a reaction kettle, heating under the protection of nitrogen, controlling the concentration of complexing agent ammonia water to be 0.4M, controlling the pH value to be 12.5 and the reaction temperature to be 50 ℃, filtering the obtained powder after aging, washing the powder with deionized water, drying the powder in 100 ℃, sieving and demagnetizing the powder to obtain a ternary precursor (Ni 0.4Fe0.26Mn0.34)(OH)2;
Uniformly mixing ternary precursors (Ni 0.4Fe0.26Mn0.34)(OH)2 and sodium carbonate according to a molar ratio of 1:1) in a crucible, putting the crucible into an atmosphere resistance furnace, controlling the sintering temperature to 850 ℃, keeping the temperature for 15 hours, cooling to room temperature after sintering, sieving, and sealing to obtain the positive electrode active material NaNi 0.4Fe0.26Mn0.34O2 with the particle size D50 of 4.5 mu m.
2) The positive plate is prepared by mixing the positive electrode active material NaNi 0.4Fe0.26Mn0.34O2 prepared in the step 1) with Super P, a conductive agent CNT and a binder PVDF according to the mass ratio of 97.5:1:0.5:1, controlling the solid content of the slurry to be 70%, obtaining positive electrode slurry, uniformly coating the positive electrode slurry on two opposite surfaces of a positive electrode current collector aluminum foil, drying, and rolling to obtain the positive plate with the double-sided density of 312g/m 2 and the compacted density of 3.5g/m 3 of a positive electrode active material layer.
3) The preparation of the anode active material comprises the steps of carbonizing biomass raw materials such as coconut shells and the like into carbon at 600 ℃, coarse crushing, fine crushing, grading, soaking in alkali liquor for 12 hours, drying at 120 ℃ to obtain powder, heating the powder to 1300 ℃, preserving the heat for 2 hours, purifying, and then carrying out modification treatment to obtain hard carbon.
4) Preparing a negative electrode sheet, namely preparing hard carbon, super P, CMC and SBR prepared in the step 3) according to the mass ratio of 96.1:0.8:1.5:1.6;
Adding hard carbon and Super P into a 5L stirring kettle according to the formula amount, and stirring and dry-mixing to obtain dry powder;
CMC is dissolved in deionized water and is subjected to autorotation dispersion for 120min at 1800rmp, so that CMC glue solution with the solid content of 1.4% is obtained;
Mixing, stirring and dispersing dry powder, 50% of CMC glue solution and 50% of deionized water according to the formula amount for 60min, adding the rest 50% of CMC glue solution and 50% of deionized water, continuously stirring for 60min, adding SBR, stirring for 60min, and then adding a proper amount of deionized water to adjust the viscosity to 3000-5000 Pa.s, so as to obtain the cathode slurry with the solid content of 50%;
The negative electrode slurry is uniformly coated on two opposite surfaces of a negative electrode current collector aluminum foil, and the negative electrode plate with the double-sided density of 200g/m 2 and the compacted density of 1.0g/m 3 of the negative electrode active material layer is obtained by rolling.
5) And (3) preparing an electrolyte, namely mixing ethylene carbonate, ethylmethyl carbonate and diethyl carbonate according to a volume ratio of 3:5:2 to obtain an organic solvent, adding fully dried sodium salt NaPF 6 into the organic solvent, and stirring until the sodium salt NaPF 6 is completely dissolved to prepare the electrolyte with the concentration of sodium salt NaPF 6 of 1 mol/L.
6) And (3) preparing a battery, namely sequentially laminating the positive electrode sheet of the step (2), the ceramic diaphragm and the negative electrode sheet of the step (4), putting the laminated positive electrode sheet and the laminated negative electrode sheet into a shell, and then carrying out liquid injection, formation and constant volume to obtain the sodium ion battery of the comparative example.
Comparative example 3
The embodiment provides a preparation method of a sodium ion battery, which comprises the following steps:
1) Preparing an anode active material, namely weighing NiSO 4·6H2O、FeSO4·7H2 O and MnSO 4·H2 O with total concentration of 2.0M in a continuous stirred tank reactor according to a molar ratio of 0.5:0.16:0.34 by adopting a coprecipitation method, adding a sodium hydroxide solution with concentration of 2.0M into the continuous stirred tank reactor to prepare a mixed solution, transferring the mixed solution into a storage tank, transferring the mixed solution into a reaction kettle, heating under the protection of nitrogen, controlling the concentration of complexing agent ammonia water to be 0.4M, controlling the pH value to be 12.5 and the reaction temperature to be 50 ℃, filtering the obtained powder after aging, washing the powder with deionized water, drying the powder in 100 ℃, sieving and demagnetizing the powder to obtain a ternary precursor (Ni 0.5Fe0.16Mn0.34)(OH)2;
Uniformly mixing ternary precursors (Ni 0.5Fe0.16Mn0.34)(OH)2 and sodium carbonate according to a molar ratio of 1:1) in a crucible, putting the crucible into an atmosphere resistance furnace, controlling the sintering temperature to 1050 ℃, keeping the temperature for 15 hours, cooling to room temperature after sintering, sieving, and sealing to obtain the positive electrode active material NaNi 0.5Fe0.16Mn0.34O2 with the particle size D50 of 13.2 mu m.
2) The positive plate is prepared by mixing the positive electrode active material NaNi 0.5Fe0.16Mn0.34O2 prepared in the step 1) with Super P, a conductive agent CNT and a binder PVDF according to the mass ratio of 97.5:1:0.5:1, controlling the solid content of the slurry to be 70%, obtaining positive electrode slurry, uniformly coating the positive electrode slurry on two opposite surfaces of a positive electrode current collector aluminum foil, drying, and rolling to obtain the positive plate with the double-sided density of 312g/m 2 and the compacted density of 3.5g/m 3 of a positive electrode active material layer.
3) The preparation of the anode active material comprises the steps of carbonizing biomass raw materials such as coconut shells and the like into carbon at 600 ℃, coarse crushing, fine crushing, grading, soaking in alkali liquor for 12 hours, drying at 120 ℃ to obtain powder, heating the powder to 1300 ℃, preserving the heat for 2 hours, purifying, and then carrying out modification treatment to obtain hard carbon.
4) Preparing a negative electrode sheet, namely preparing hard carbon, super P, CMC and SBR prepared in the step 3) according to the mass ratio of 96.1:0.8:1.5:1.6;
Adding hard carbon and Super P into a 5L stirring kettle according to the formula amount, and stirring and dry-mixing to obtain dry powder;
CMC is dissolved in deionized water and is subjected to autorotation dispersion for 120min at 1800rmp, so that CMC glue solution with the solid content of 1.4% is obtained;
Mixing, stirring and dispersing dry powder, 50% of CMC glue solution and 50% of deionized water according to the formula amount for 60min, adding the rest 50% of CMC glue solution and 50% of deionized water, continuously stirring for 60min, adding SBR, stirring for 60min, and then adding a proper amount of deionized water to adjust the viscosity to 3000-5000 Pa.s, so as to obtain the cathode slurry with the solid content of 50%;
The negative electrode slurry is uniformly coated on two opposite surfaces of a negative electrode current collector aluminum foil, and the negative electrode plate with the double-sided density of 200g/m 2 and the compacted density of 1.0g/m 3 of the negative electrode active material layer is obtained by rolling.
5) And (3) preparing an electrolyte, namely mixing ethylene carbonate, ethylmethyl carbonate and diethyl carbonate according to a volume ratio of 3:5:2 to obtain an organic solvent, adding fully dried sodium salt NaPF 6 into the organic solvent, and stirring until the sodium salt NaPF 6 is completely dissolved to prepare the electrolyte with the concentration of sodium salt NaPF 6 of 1 mol/L.
6) And (3) preparing a battery, namely sequentially laminating the positive electrode sheet of the step (2), the ceramic diaphragm and the negative electrode sheet of the step (4), putting the laminated positive electrode sheet and the laminated negative electrode sheet into a shell, and then injecting liquid, forming and fixing the volume to obtain the sodium ion battery of the embodiment.
The positive electrode active materials prepared in examples 1 to 8 and comparative examples 1 to 3 have phases with gradient changes of Ni concentration, and the positive electrode active material has lamellar phase Na yNixFe0.66-xMn0.34O2 (y is more than or equal to 0.9 and less than or equal to 1.1,0.35 and x is more than or equal to 0.45), lamellar phase transition phase and litho salt phase NiO sequentially from the core of the positive electrode active material particles to the outside, wherein the lamellar phase transition phase and the litho salt phase transition phase are located at R- (97% -99.8%) R away from the core of the positive electrode active material particles. Specifically, the phases with gradient change of Ni concentration in the positive electrode active material are lamellar phase Na yNixFe0.66-xMn0.34O2 (y is more than or equal to 0.9 and less than or equal to 1.1,0.35 and x is more than or equal to 0.45) at the position of 0-99 percent R from the core of the positive electrode active material particle, lamellar phase transition phase and rock salt phase transition phase at the position of 99-99.7 percent R from the core of the positive electrode active material particle, and rock salt phase NiO at the position of 99.7-100 percent R from the core of the positive electrode active material particle. Wherein R is the minimum circumscribing radius of the positive electrode active material.
The Ni concentration of the invention is the mole ratio of Ni in the transition metal element in the positive electrode active material, wherein the mole ratio of Ni in the lamellar phase in the transition metal element is 30-36%, which indicates that the existence of the rock salt phase does not affect the composition and structure of the internal lamellar phase. The mole ratio of Ni in the transition metal element in the transition phase of the lamellar phase and the rock salt phase is 60% -70%, which indicates that the transition phase exists between the lamellar phase and the rock salt phase, and the lamellar phase and the rock salt phase are not completely separated. The mole ratio of Ni in the rock salt phase in the transition metal element is 90% -100%, which indicates that the rock salt phase is completely formed. According to the invention, EDS tests are carried out on sections of the positive electrode active materials prepared in examples 1-8 and comparative examples 1-3 at three points in three phase regions respectively, so that the molar ratio of Ni in transition metal elements is obtained.
In the positive electrode active material Na yNixFe0.66-xMn0.34O2 (0.9.ltoreq.y 1.1,0.35.ltoreq.x.ltoreq.0.45), 0.9.ltoreq.y.ltoreq.1.1 is defined to ensure that the positive electrode active material has an O3 phase structure, and the content of manganese is fixed to keep the positive electrode active material in a stable structure because manganese is not easily dissolved in the positive electrode active material and iron is easily dissolved.
Table 1 shows the parameter characteristics of the positive electrode active materials of examples 1 to 8 and comparative examples 1 to 3.
TABLE 1
Performance testing and analysis
1. Test objects positive electrode active materials and sodium ion batteries prepared in examples 1 to 8 and comparative examples 1 to 3.
2. Test item
1) Positive electrode active material unit cell volume change rate test
Two groups of positive electrode active materials of examples 1-8 and comparative examples 1-3 prepared in the same batch are prepared to prepare two groups of sodium ion batteries, the two groups of sodium ion batteries are subjected to cycle test according to a cycle process step, are charged to a full-charge state for the first time and then discharged to 2.0V, and then the two groups of sodium ion batteries are disassembled to obtain two groups of used positive electrode plates. And assembling two groups of used positive plate snap-fastener type batteries, wherein one group of snap-fastener type batteries are disassembled when the second circle of the charging and discharging cycle of the other group of snap-fastener type batteries is charged to 4.0V, and the other group of snap-fastener type batteries are disassembled when the second circle of the charging and discharging cycle of the other group of snap-fastener type batteries is charged to 4.2V.
XRD testing was performed on the above-described disassembled positive electrode sheet charged to 4.0V and the disassembled positive electrode sheet charged to 4.2V according to the following steps:
step1, sample treatment and filling, namely fixing a positive plate sample on a glass sample frame, inserting the sample frame into a sample clamping groove, and closing a sample chamber door;
Step2, setting software steps, namely opening software of a measurement control system to enter a control main interface, wherein the diffractometer takes Cu-K alpha rays as a diffraction source, setting working voltage to 40kV, working current to 40mA, setting the scanning speed of the diffractometer to 10 degrees/min, setting the starting and stopping angles within the scanning range of 10 degrees to 90 degrees, and setting the scanning speed to 0.05 degrees/min;
Step3, after the instrument prompts that the test is finished, under the condition that X rays in the sample chamber are turned off, the sample chamber can be opened, the sample frame is taken out, and the sample is recovered;
Step4, processing the image according to smoothing, filtering and background buckling, constructing a basic structure of the synthesized material by VESTA, then adopting GENERAL STRUCTURE ANALYSIS SYSTEM software (GSAS) to refine an XRD spectrogram, adjusting atomic parameters, peak type parameters, instrument parameters and the like in the structure by a least square method to enable a full spectrum weighted residual difference square factor Rwp to be minimum, and deriving structural data and analyzing and mapping by VESTA after finishing meets the requirement;
STEP5 calculating the unit cell volume change rate from the derived structural data Wherein V 1 is the unit cell volume of the positive electrode active material charged to 4.0V on the disassembled positive electrode sheet, and V 2 is the unit cell volume of the positive electrode active material charged to 4.2V on the disassembled positive electrode sheet.
2) Capacity contribution
The button cell was assembled according to the following steps:
a. preparing a positive plate, namely fully stirring and mixing the positive active materials of examples 1-8 and comparative examples 1-3, conductive carbon and a binder PVDF in a proper amount of NMP solvent according to a mass ratio of 90:5:5 to form uniform positive slurry, coating the positive slurry on a carbon-coated aluminum foil of a positive current collector, drying and punching into a small wafer with a diameter of 14 mm;
b. a negative plate, namely selecting a metal sodium plate;
c. the diaphragm is made of glass fiber;
d. Mixing ethylene carbonate, methyl ethyl carbonate and diethyl carbonate according to a volume ratio of 3:5:2 to obtain an organic solvent, adding sodium salt NaPF 6 which is fully dried into the organic solvent, and stirring until sodium salt NaPF 6 is completely dissolved to prepare an electrolyte with concentration of sodium salt NaPF 6 of 1mol/L for later use;
e. the preparation of the button cell comprises the steps of firstly placing a positive electrode shell stably, sequentially stacking a positive electrode plate, a diaphragm and a negative electrode plate on the positive electrode shell, placing the diaphragm between the positive electrode plate and the negative electrode plate to play a role of isolation, injecting electrolyte into the positive electrode shell, covering the negative electrode shell, and packaging by a packaging machine to obtain the button cell corresponding to the examples 1-8 and the comparative examples 1-3.
The prepared button cells of examples 1-8 and comparative examples 1-3 were subjected to a cyclic test in a constant temperature environment at 25 ℃ with a procedure of 1C CC to 4.2V,CV to 0.05C,rest 10min,1C DC to 2.00V,rest 10min cycles, 3 cycles, C 1 being the capacity exerted in the voltage interval of 4.0-4.2V during the second cycle of the button cells of examples 1-8 and comparative examples 1-3, C 2 being the capacity exerted in the voltage interval of 2-4.2V during the second cycle of the button cells of examples 1-8 and comparative examples 1-3, and the capacity contribution being defined
The ratio of the unit cell volume change rate to the capacity contribution of the positive electrode active material is defined as a, a=v/C.
3) Cycle performance
The sodium ion batteries of examples 1-8 and comparative examples 1-3 were subjected to a charge-discharge cycle test in a constant temperature environment at 25 ℃ with a charge-discharge flow of 1C CC to 4.2V,CV to 0.05C,rest 10min,1C DC to 2.00V,rest 10min and the number of cycles was recorded when the cycle was continued until the capacity had decayed to 80% of the initial capacity.
3. See Table 2 for test results.
TABLE 2
V C a Cycle performance/loop
Example 1 0.005 0.1 0.05 100
Example 2 0.0075 0.08 0.09 80
Example 3 0.01 0.07 0.14 70
Example 4 0.006 0.075 0.08 90
Example 5 0.004 0.08 0.05 75
Example 6 0.014 0.1 0.14 65
Example 7 0.005 0.06 0.08 85
Example 8 0.01 0.12 0.08 80
Comparative example 1 0.015 0.05 0.30 50
Comparative example 2 0.02 0.04 0.50 25
Comparative example 3 0.025 0.04 0.625 20
As can be seen from Table 2, the cycling performance of the sodium ion batteries of examples 1 to 8 is significantly better than that of comparative examples 1 to 3, the ratio of the unit cell volume change rate to the capacity contribution of the positive electrode active materials of examples 1 to 8 satisfies 0.05.ltoreq.a.ltoreq.0.14, is significantly smaller than that of comparative example 1, 0.30 of comparative example 2 and 0.625 of comparative example 3, and it is demonstrated that the smaller the ratio of the unit cell volume change rate to the capacity contribution is, the better the structural stability of the positive electrode active materials is, and thus the longer the cycle life of the prepared sodium ion battery is.
Further, the unit cell volume change rate of the positive electrode active materials of examples 1 to 8 satisfies 0.005.ltoreq.V.ltoreq.0.014, less than 0.015 of comparative example 1, 0.02 of comparative example 2 and 0.025 of comparative example 3, and the capacity contribution of examples 1 to 4 satisfies 0.06.ltoreq.C.ltoreq.0.12, more than 0.05 of comparative example 1, 0.05 of comparative example 2 and 0.04 of comparative example 3. This means that the smaller the unit cell volume change rate of the positive electrode active material, the more stable the structure of the positive electrode active material, and the higher the capacity contribution, the more advantageous the improvement of the working performance of the sodium ion battery under high voltage, so that the combination of the two is advantageous to the improvement of the cycle performance of the sodium ion battery.
More preferably, the cycle performance of examples 1-2, 4, and 7-8 shows that the ratio of the unit cell volume change rate to the capacity contribution of the positive electrode active material is preferably 0.05.ltoreq.a.ltoreq.0.09, the unit cell volume change rate of the positive electrode active material is preferably 0.005.ltoreq.v.ltoreq.0.01, and the capacity contribution is preferably 0.06.ltoreq.c.ltoreq.0.12, due to examples 3, 5-6.
Most preferably, the sodium ion batteries of example 1 and example 4 have the best cycle performance, meaning that the ratio of the unit cell volume change rate of the positive electrode active material to the capacity contribution is preferably 0.05.ltoreq.a.ltoreq.0.08, and the unit cell volume change rate of the positive electrode active material is preferably 0.005.ltoreq.v.ltoreq.0.006, and the capacity contribution is preferably 0.075.ltoreq.c.ltoreq.0.1.
Referring to tables 1 and 2, the sodium ion batteries of examples 1 to 8 and comparative examples 1 to 3 were analyzed in combination with the preparation methods. The invention controls ternary precursor of positive electrode active material (Ni content in Ni xFe0.66-xMn0.34)(OH)2 is 0.35-0.45, ni content is increased, fe content is reduced, higher sintering temperature is controlled to 900-1010 ℃, high nickel content is combined with high sintering temperature, and the nickel content and the high sintering temperature cooperate, because ion radius Ni 2+ is 0.069nm, mn 4+ is 0.053nm, mn 3+ is 0.058nm, fe 3+ is 0.055nm, ion radius of Ni 2+ is greater than Mn 3+、Mn4+、Fe3+, because Ni 2+ size is not matched with Mn 3+、Mn4+、Fe3+, higher sintering temperature is that Ni 2+ is transferred to surface from bulk phase to provide energy, and the two factors act together to ensure that Ni 2+ is easy to gather on the surface of the material, surface segregation occurs, and NiO of rock salt phase is formed by combining with oxygen on the surface, thus leading the positive electrode active material to have phase (three-layer coating structure) with gradient change of Ni concentration, lamellar phase Na yNixFe0.66-xMn0.34O2 (0.9.ltoreq.y.ltoreq. 1.1,0.35.ltoreq.x.ltoreq.0.45) at 0-99% R from the core of the positive electrode active material particles, lamellar phase and rock salt phase transition phase at 99% -99.7% R from the core of the positive electrode active material particles, and preferably, the molar ratio of Ni in the lamellar phase to the transition metal element is 33% -36%, the molar ratio of Ni in the lamellar phase to the rock salt phase transition phase is 64% -67%, the molar ratio of Ni in the transition metal element is 94% -97% in the rock salt phase transition phase, whereby the lamellar phase to rock salt phase transition phase migration is anchored by the stable structure of the rock salt phase, phase transition of the lamellar positive electrode active material at high voltage is suppressed, cell volume change of the positive electrode active material is reduced, generation and expansion of microcracks are suppressed, the ratio of the unit cell volume change rate to the capacity contribution is controlled to extend the cycle life of the sodium ion battery.
When x is less than 0.35, nickel in the material can be uniformly distributed at Ni sites in the Na yNixFe0.66-xMn0.34O2 material, and redundant Ni does not exist, so that the surface segregation condition cannot be met. As in x=0.33 of comparative example 1, the layered phase, the rock salt phase transition phase and the rock salt phase cannot be formed due to the absence of excess Ni, and the positive electrode active material is susceptible to a low-reversibility p3→o3' phase transition at a high voltage, so that the unit cell volume of the positive electrode active material is greatly changed to generate microcracks, which affect the stability of the positive electrode active material, thereby greatly reducing the cycle life of the sodium ion battery. When x is more than 0.45, the synthesized anode active material has high residual alkali number, is unfavorable for processing the material, and can cause a gel phenomenon in the processing process, so that the anode active material has poor performance. If the x=0.5 of comparative example 3, the ni content is too high, a gel phenomenon is easily generated during the processing, so that the performance of the positive electrode active material of comparative example 3 is deteriorated, and the cycle performance of the sodium ion battery is finally affected. When the sintering temperature is lower than 900 ℃, the energy provided by sintering is insufficient, so that the redundant Ni in the positive electrode active material cannot be diffused to the surface of the positive electrode active material, and the surface segregation cannot be realized. If the sintering temperature of comparative example 2 is 850 ℃, the Ni content in the rock salt phase is low, and migration of the lamellar phase and the rock salt phase transition phase cannot be effectively anchored, so that the positive electrode active material is easy to generate a phase transition from P3 to O3' with low reversibility under high voltage, the unit cell volume of the positive electrode active material is greatly changed to generate microcracks, the stability of the positive electrode active material is influenced, and the cycle life of the sodium ion battery is greatly reduced. When the sintering temperature is higher than 1010 ℃, ni ions in Ni sites in the material are diffused to the surface, excessive Ni migrates to the surface, the Ni is excessively enriched on the surface, a surface layer of too thick salt rock phase NiO is formed, the surface layer of the too thick salt rock phase is unfavorable for the removal and intercalation of sodium ions, and therefore, the structure of the positive electrode active material is changed due to the excessive segregation of nickel, and the circulation of a sodium ion battery is unfavorable. If the sintering temperature of comparative example 3 is 1050 ℃, the sintering temperature is too high, the molar ratio of Ni in transition metal elements in each phase, ni is excessively segregated and excessively enriched on the surface, and the structure of the positive electrode active material is destroyed, so that the positive electrode active material has larger unit cell volume change rate and lower capacity contribution in the test process, the ratio (0.625) of the unit cell volume change rate to the capacity contribution of the positive electrode active material is far more than 0.05-0.14 defined by the invention, and the cycle life of the prepared sodium ion battery is extremely low. In addition, the particle diameter D50 of the positive electrode active material prepared by the invention is 1-10 mu m, so that the positive electrode active material has smaller specific surface area and diffusion resistance. When the particle diameter D50 is smaller than 1 mu m, the specific surface area of the positive electrode active material is increased, and the contact area between the positive electrode active material and the electrolyte is increased during testing, so that the gas production of the sodium ion battery is increased, and the cycle performance is reduced. When the particle diameter D50 is more than 10 μm, the diffusion distance of sodium ions in the positive electrode active material increases, increasing the diffusion resistance of the positive electrode active material, resulting in an increase in resistance of the sodium ion battery and a decrease in cycle performance. Preferably, the particle size D50 of the positive electrode active material is 4.5-4.8 mu m, the specific surface area and the diffusion resistance of the positive electrode active material can be effectively balanced, and the resistance of the sodium ion battery is reduced while the gas production of the sodium ion battery is less, so that the cycle performance of the sodium ion battery is ensured.
The above embodiments are only for illustrating the technical solution of the present invention and not for limiting the scope of the present invention, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that the technical solution of the present invention may be modified or substituted without departing from the spirit and scope of the technical solution of the present invention.

Claims (12)

1. A sodium ion battery comprising:
The positive plate comprises a positive current collector and a positive active material layer arranged on at least one surface of the positive current collector, wherein the positive active material layer comprises a positive active material, the positive active material is Na yNixFe0.66-xMn0.34O2, y is more than or equal to 0.9 and less than or equal to 1.1,0.35 and less than or equal to 0.45, the positive active material contains phases with gradient change of Ni concentration, from the core of positive active material particles to the outside, a lamellar phase Na yNixFe0.66-xMn0.34O2, a lamellar phase transition phase and a rock salt phase NiO are sequentially arranged, the lamellar phase transition phase and the rock salt phase transition phase are positioned at a position R- (97% -99.8%) from the core (95% -96%) of positive active material particles, wherein R is the minimum circumcircle radius of the positive active material, and y is more than or equal to 0.9 and less than or equal to 1.1,0.35 and less than or equal to 0.45;
The mole ratio of Ni in the lamellar phase to the transition metal element is 30-36%, the mole ratio of Ni in the lamellar phase to the rock salt phase transition phase to the transition metal element is 60-70%, and the mole ratio of Ni in the rock salt phase to the transition metal element is 90-100%;
the negative plate comprises a negative current collector and a negative active material layer arranged on at least one surface of the negative current collector;
The ratio a of the unit cell volume change rate V of the positive electrode active material to the capacity contribution C is more than or equal to 0.05 and less than or equal to 0.14;
Wherein the unit cell volume change rate of the positive electrode active material V 1 is the unit cell volume of the positive active material of the positive plate when the second charge of the charge-discharge cycle is 4.0V after the disassembly of the sodium ion battery discharged to 2.0V, V 2 is the unit cell volume of the positive active material of the positive plate when the second charge of the charge-discharge cycle is 4.2V after the disassembly of the same sodium ion battery discharged to 2.0V;
Capacity contribution C 1 is the capacity exerted in the voltage interval of 4.0-4.2V in the second round of charging process, C 2 is the capacity exerted in the voltage interval of 2-4.2V in the second round of charging process of the sodium ion battery in the 1C constant current charging to 4.2V, the constant voltage charging to the current of 0.05C, the standing for 10min, the constant voltage discharging to 2.00V in the 1C constant current charging to the current of 0.05C, the standing for 10min, the charging and discharging cycle for 3 rounds, and the capacity exerted in the voltage interval of 2-4.2V in the second round of charging process.
2. A sodium ion battery according to claim 1, wherein the ratio a of the unit cell volume change rate to the capacity contribution of the positive electrode active material satisfies 0.05.ltoreq.a.ltoreq.0.09.
3. A sodium ion battery according to claim 2, wherein the ratio a of the unit cell volume change rate to the capacity contribution of the positive electrode active material satisfies 0.05.ltoreq.a.ltoreq.0.08.
4. A sodium ion battery according to claim 1, wherein the unit cell volume change rate V satisfies 0.005.ltoreq.V.ltoreq.0.014.
5. A sodium ion battery according to claim 4, wherein the unit cell volume change rate V satisfies 0.005.ltoreq.V.ltoreq.0.01.
6. A sodium ion battery according to claim 5, wherein the unit cell volume change rate V satisfies 0.005.ltoreq.V.ltoreq.0.006.
7. A sodium ion battery according to claim 1, wherein the capacity contribution C satisfies 0.06.ltoreq.C.ltoreq.0.12.
8. A sodium ion battery according to claim 7, wherein the capacity contribution C satisfies 0.075.ltoreq.C.ltoreq.0.1.
9. A sodium ion battery according to claim 1, wherein the molar ratio of Ni in the transition metal element in the lamellar phase is 33% -36%, the molar ratio of Ni in the transition metal element in the lamellar phase and the rock salt phase is 64% -67%, and the molar ratio of Ni in the transition metal element in the rock salt phase is 94% -97%.
10. A sodium ion battery according to claim 1, wherein the particle diameter D50 of the positive electrode active material satisfies 1 μm.ltoreq.D50.ltoreq.10μm.
11. A sodium ion battery according to claim 10, wherein the particle diameter D50 of the positive electrode active material satisfies 4.5 μm.ltoreq.D50.ltoreq.4.8. Mu.m.
12. The sodium ion battery of claim 1, wherein the positive electrode active material is obtained by mixing sodium carbonate with a ternary precursor (Ni xFe0.66-xMn0.34)(OH)2 in a molar ratio of 0.9-1.1:1, sintering at 900-1010 ℃ for 15-25h, cooling to room temperature, sieving, and sealing, wherein x is more than or equal to 0.35 and less than or equal to 0.45.
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CN111525099B (en) * 2019-02-02 2021-08-06 宁德时代新能源科技股份有限公司 Sodium ion battery
KR102406774B1 (en) * 2019-06-20 2022-06-10 한양대학교 산학협력단 Cathode active material comprising heteroatom doped surface portion, and method of fabricating of the same
CN116314590A (en) * 2023-03-31 2023-06-23 上海扬广科技有限责任公司 A kind of sodium ion battery and preparation method thereof

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CN102439767A (en) * 2009-05-22 2012-05-02 夏普株式会社 Positive electrode active material, positive electrode, and nonaqueous secondary battery
CN110337744A (en) * 2017-06-26 2019-10-15 株式会社半导体能源研究所 Method for producing positive electrode active material and secondary battery

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