CN115295787A - Sodium-ion battery positive electrode material and preparation method and application thereof - Google Patents

Sodium-ion battery positive electrode material and preparation method and application thereof Download PDF

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CN115295787A
CN115295787A CN202211057146.0A CN202211057146A CN115295787A CN 115295787 A CN115295787 A CN 115295787A CN 202211057146 A CN202211057146 A CN 202211057146A CN 115295787 A CN115295787 A CN 115295787A
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sodium
source
positive electrode
electrode material
ion battery
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吕昌晓
刘瑞
袁旭婷
李凯旋
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Ningbo Ronbay Lithium Battery Material Co Ltd
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Ningbo Ronbay Lithium Battery Material Co Ltd
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    • H01M4/02—Electrodes composed of, or comprising, active material
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    • C01G53/00—Compounds of nickel
    • C01G53/40—Nickelates
    • C01G53/42—Nickelates containing alkali metals, e.g. LiNiO2
    • C01G53/44—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • 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
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    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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Abstract

The invention belongs to the field of sodium ion batteries, and particularly relates to a sodium ion battery positive electrode material and a preparation method and application thereof. The preparation method provided by the invention comprises the following steps: a) Reacting a Ni source, a Mn source, a Fe source, a precipitator and a complexing agent in water, and drying precipitates to obtain precursor particles; b) Mixing the precursor particles, a Na source and an M source, and calcining in an oxygen-containing atmosphere to obtain a sodium-ion battery positive electrode material; the chemical general formula of the positive electrode material of the sodium-ion battery is Na i Ni x Fe y Mn z M 1‑x‑y‑z O 2 M is Li,Mg, zr, al, sn, ti, mo, ba, sr, nb and Cr. The method adopts a coprecipitation-high temperature solid phase method, prepares the high-performance sodium ion battery anode material with P2/O3 phase composition by doping M element, is matched with the existing industrially mature NFM precursor, has low energy consumption and is easy for industrial production.

Description

Sodium-ion battery positive electrode material and preparation method and application thereof
Technical Field
The invention belongs to the field of sodium ion batteries, and particularly relates to a sodium ion battery positive electrode material, and a preparation method and application thereof.
Background
The lithium ion battery is in the core status of the battery due to the advantages of high energy density, long cycle life and the like, but has the problems of uneven lithium resource distribution, continuous rising of upstream price, lagged cycle recovery technology and the like. The sodium ion battery has the advantages of rich sodium resource storage, wide distribution, low manufacturing cost, good safety and the like, and has wide development prospect in the fields of electric vehicles and energy storage.
The sodium ion battery mainly comprises a layered transition metal oxide, a polyanion compound and a Prussian blue system, wherein the layered transition metal oxide is more popular in the market due to high specific capacity, low cost, compatibility with the existing ternary anode material production line and the like.
The layered material is mainly divided into a P2 phase and an O3 phase according to different sodium ion occupation, the P2 phase has good multiplying power performance, but the capacity is low, the circulation under high pressure is poor, the O3 capacity is high, and the circulation performance is good. At present, the prior art carries out the research of compounding the P2 phase and the O3 phase to integrate the advantages of the two phases and cooperatively improve the performance of the electrode material; however, the existing research mainly focuses on iron-manganese-based or nickel-manganese-based materials, and is not matched with the existing industrially mature nickel-iron-manganese (NFM) ternary precursor.
Disclosure of Invention
In view of the above, the present invention provides a sodium ion battery positive electrode material, and a preparation method and an application thereof, and the preparation method provided by the present invention enables an NFM positive electrode material to have a P2 and O3 composite phase, and the prepared positive electrode material has both high specific capacity and long cycle performance.
The invention provides a positive electrode material of a sodium-ion battery, which has a chemical general formula of Na i Ni x Fe y Mn z M 1-x-y-z O 2 (ii) a Wherein M is one or more of Li, mg, zr, al, sn, ti, mo, ba, sr, nb and Cr, i is more than 0.5 and less than or equal to 1.2, x is more than 0 and less than or equal to 0.7,y is more than 0 and less than or equal to 0.7, z is more than 0 and less than or equal to 0.7, x + y + z is less than 1, i, x, y and z satisfy the charge balance of the chemical general formula;
the positive electrode material of the sodium-ion battery has a P2/O3 phase composite layered structure.
Preferably, D of the positive electrode material of the sodium-ion battery 50 The grain diameter is 0.5-20 μm; the specific surface area of the positive electrode material of the sodium-ion battery is 0.5-5 m 2 (ii)/g; the compacted density of the positive electrode material of the sodium-ion battery is 2.75-4 g/cm 3 。
Preferably, i is more than 0.6 and less than or equal to 0.7, x is more than or equal to 0.2 and less than or equal to 0.3, y is more than or equal to 0.2 and less than or equal to 0.3, and z is more than or equal to 0.3 and less than or equal to 0.4.
The invention provides a preparation method of a sodium-ion battery anode material, which comprises the following steps:
a) Carrying out coprecipitation reaction on a Ni source, a Mn source, a Fe source, a precipitator and a complexing agent in water, and drying precipitates to obtain precursor particles;
b) And mixing the precursor particles, a Na source and an M source, and calcining in an oxygen-containing atmosphere to obtain the sodium-ion battery anode material.
Preferably, the Ni source is one or more of nickel sulfate, nickel chloride, nickel nitrate, nickel acetate, and nickel citrate.
Preferably, the Mn source is one or more of manganese sulfate, manganese chloride, manganese nitrate, manganese acetate, and manganese citrate.
Preferably, the Fe source is one or more of ferric sulfate, ferric chloride, ferric nitrate, ferric acetate and ferric citrate.
Preferably, the Na source is one or more of sodium carbonate, sodium bicarbonate, sodium nitrate, sodium hydroxide and sodium acetate.
Preferably, the M source is one or more of oxide, hydroxide, carbonate and sulfate corresponding to M element.
Preferably, the precipitating agent is one or more of a hydroxide precipitating agent, a carbonate precipitating agent and an oxalate precipitating agent.
Preferably, the complexing agent is one or more of citric acid, ammonia water, ethylene diamine tetraacetic acid salt, sodium tripolyphosphate, sodium pyrophosphate, sodium hexametaphosphate, diethanolamine and diethylenetriamine pentacarboxylate.
Preferably, in step a), the molar ratio of the total molar amount of the Ni source, mn source, and Fe source to the precipitant and complexing agent is 1: (0.4-10): (0.1-4).
Preferably, in the step a), the temperature of the coprecipitation reaction is 40-70 ℃; the pH value of the coprecipitation reaction is 8-12; the coprecipitation reaction time is 15-30 h.
Preferably, in step a), the pH of the coprecipitation reaction is controlled by adding ammonia water.
Preferably, in the step b), the calcining temperature is 600-1100 ℃; the calcining time is 2-30 h.
The invention provides a sodium ion battery, and the positive electrode material of the sodium ion battery is the positive electrode material of the sodium ion battery in the technical scheme or the positive electrode material of the sodium ion battery prepared by the preparation method in the technical scheme.
Compared with the prior art, the invention provides a sodium-ion battery positive electrode material and a preparation method and application thereof. The preparation method provided by the invention comprises the following steps: a) Carrying out coprecipitation reaction on a Ni source, a Mn source, a Fe source, a precipitator and a complexing agent in water, and drying precipitates to obtain precursor particles; b) Mixing the precursor particles, a Na source and an M source, and calcining in an oxygen-containing atmosphere to obtain a sodium-ion battery positive electrode material; the chemical general formula of the positive electrode material of the sodium-ion battery is Na i Ni x Fe y Mn z M 1-x-y-z O 2 (ii) a Wherein M is one or more of Li, mg, zr, al, sn, ti, mo, ba, sr, nb and Cr, i is more than 0.5 and less than or equal to 1.2, x is more than 0 and less than or equal to 0.7, y is more than 0 and less than or equal to 0.7, z is more than 0 and less than or equal to 0.7, x + y + z is less than 1, and the values of i, x, y and z satisfy the charge balance of the chemical general formula; the positive electrode material of the sodium-ion battery has a P2/O3 phase composite layered structure. The method changes TM-O bond length in a layered structure through element doping or transition metal substitution, so that the material has a P2 phase and an O3 phase at the same time, and the cross recombination between phase boundaries can inhibit irreversible phase change, namely two phasesThe synergistic effect of the phases can simultaneously have higher reversible specific capacity and good cycle performance. The invention adopts a coprecipitation-high temperature solid phase method to prepare the sodium ion battery anode material with the composite phase NFM layered structure and high specific capacity and long cycle performance, and the method is matched with the existing industrially mature NFM precursor, has low energy consumption and is easy for industrial production.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the provided drawings without creative efforts.
FIG. 1 is an X-ray diffraction pattern provided in example 1 of the present invention;
FIG. 2 is an X-ray diffraction pattern provided in comparative example 1 of the present invention;
FIG. 3 is a scanning electron microscope image provided in example 2 of the present invention;
FIG. 4 is a first charging and discharging curve diagram of the sodium ion positive electrode material provided in embodiment 2 of the present invention at 0.1C and 1.5-4.2V;
FIG. 5 is a graph of the cycle performance of the sodium ion positive electrode material provided in example 3 of the present invention at 0.1C and 1.5-4.2V;
FIG. 6 is an X-ray diffraction pattern provided by comparative example 3 of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention are clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention provides a positive electrode material of a sodium-ion battery, which has a chemical general formula of Na i Ni x Fe y Mn z M 1-x-y-z O 2 (ii) a Wherein M is one or more of Li, mg, zr, al, sn, ti, mo, ba, sr, nb and Cr; i is more than 0.5 and less than or equal to 1.2, preferably more than 0.6 and less than or equal to 0.7, and can be 2/3; x is more than 0 and less than or equal to 0.7, preferably more than or equal to 0.2 and less than or equal to 0.3, and can be 0.2 or 0.3; y is more than 0 and less than or equal to 0.7, preferably more than or equal to 0.2 and less than or equal to 0.3, and specifically can be 0.2; z is more than 0 and less than or equal to 0.7, preferably more than or equal to 0.3 and less than or equal to 0.4, and can be 0.3 or 0.4; x + y + z is less than 1, and the values of i, x, y and z satisfy the charge balance of the chemical formula. In the embodiment provided by the invention, the chemical formula of the cathode material can be specifically Na 2/3 Li 0.2 Ni 0.2 Fe 0.2 Mn 0.4 O 2 、Na 2/3 Li 0.1 Ni 0.2 Fe 0.2 Mn 0.3 Ti 0.2 O 2 Or Na 2/ 3 Ni 0.3 Fe 0.2 Mn 0.3 Sn 0.2 O 2 。
In the invention, D of the positive electrode material of the sodium-ion battery 50 The particle size is preferably 0.5 to 20 μm, and specifically may be 0.5 μm, 1 μm, 1.5 μm, 2 μm, 2.5 μm, 3 μm, 3.5 μm, 4 μm, 4.5 μm, 5 μm, 5.5 μm, 6 μm, 6.5 μm, 7 μm, 7.5 μm, 8 μm, 8.5 μm, 9 μm, 9.5 μm, 10 μm, 10.5 μm, 11 μm, 11.5 μm, 12 μm, 12.5 μm, 13 μm, 13.5 μm, 14 μm, 14.5 μm, 15 μm, 15.5 μm, 16 μm, 16.5 μm, 17 μm, 17.5 μm, 18 μm, 18.5 μm, 19 μm, 19.5 μm or 20 μm.
In the invention, the specific surface area of the positive electrode material of the sodium-ion battery is preferably 0.5-5 m 2 A specific value of 0.5 m/g 2 /g、0.7m 2 /g、1m 2 /g、1.2m 2 /g、1.5m 2 /g、1.7m 2 /g、2m 2 /g、2.3m 2 /g、2.5m 2 /g、2.7m 2 /g、3m 2 /g、3.2m 2 /g、3.5m 2 /g、3.7m 2 /g、4m 2 /g、4.2m 2 /g、4.5m 2 /g、4.7m 2 G or 5m 2 /g。
In the invention, the compacted density of the positive electrode material of the sodium-ion battery at 3.5T is preferably 2.75-4 g/cm 3 Specifically, it may be 2.75g/cm 3 、2.8g/cm 3 、2.85g/cm 3 、2.9g/cm 3 、2.95g/cm 3 、3g/cm 3 、3.05g/cm 3 、3.1g/cm 3 、3.15g/cm 3 、3.2g/cm 3 、3.25g/cm 3 、3.3g/cm 3 、3.35g/cm 3 、3.4g/cm 3 、3.45g/cm 3 、3.5g/cm 3 、3.55g/cm 3 、3.6g/cm 3 、3.65g/cm 3 、3.7g/cm 3 、3.75g/cm 3 、3.8g/cm 3 、3.85g/cm 3 、3.9g/cm 3 、3.95g/cm 3 Or 4g/cm 3 。
In the invention, the positive electrode material of the sodium-ion battery has a P2/O3 phase composite layered structure.
The positive electrode material of the sodium-ion battery is a nickel-iron-manganese (NFM) based material, and is matched with the prior industrial mature NFM precursor technology; the anode material has a P2/O3 phase composite laminated structure and has high specific capacity and long cycle performance.
The invention also provides a preparation method of the sodium-ion battery anode material, which comprises the following steps:
a) Carrying out coprecipitation reaction on a Ni source, a Mn source, a Fe source, a precipitator and a complexing agent in water, and drying precipitates to obtain precursor particles;
b) And mixing the precursor particles, a Na source and an M source, and calcining in an oxygen-containing atmosphere to obtain the sodium-ion battery anode material.
In the preparation method provided by the invention, in the step a), the Ni source is preferably one or more of nickel sulfate, nickel chloride, nickel nitrate, nickel acetate and nickel citrate; the Mn source is preferably one or more of manganese sulfate, manganese chloride, manganese nitrate, manganese acetate and manganese citrate; the Na source is preferably one or more of sodium carbonate, sodium bicarbonate, sodium nitrate, sodium hydroxide and sodium acetate; the dosage proportion of the Ni source, the Mn source and the Fe source is determined according to the atomic number ratio of the Ni source, the Mn source and the Fe source in a chemical formula for preparing the sodium-ion battery anode material; that is, the molar ratio of the Ni source, mn source and Fe source ranges from (0 to 7): (0 to 7): (0 to 7), excluding the case where the left end point is 0, preferably (2 to 3): (2-3): (3 to 4), specifically, 2.
In the preparation method provided by the invention, in the step a), the precipitating agent is preferably one or more of a hydroxyl precipitating agent, a carbonate precipitating agent and an oxalate precipitating agent, and is more preferably sodium hydroxide; the molar ratio of the precipitant to the total of the Ni source, mn source, and Fe source is preferably (0.4 to 10): 1, 0.5.
In the preparation method provided by the invention, in the step a), the complexing agent is preferably one or more of citric acid, ammonia water, ethylene diamine tetraacetic acid salt, sodium tripolyphosphate, sodium pyrophosphate, sodium hexametaphosphate, diethanolamine and diethylenetriamine pentacarboxylate; the molar ratio of the total amount of the complexing agent Ni source, the complexing agent Mn source and the complexing agent Fe source is preferably (0.1-4): 1, specifically can be 0.1, 0.125.
In the preparation method provided by the invention, in the step a), the Ni source, the Mn source and the Fe source are preferably continuously fed into the reaction kettle in the form of mixed metal source aqueous solution in the coprecipitation reaction process; the total molar concentration of the Ni source, the Mn source and the Fe source in the mixed metal source aqueous solution is preferably 0.5-5 mol/L, and specifically can be 0.5mol/L, 1mol/L, 1.5mol/L, 2.5mol/L, 3mol/L, 3.5mol/L, 4mol/L, 4.5mol/L or 5mol/L; the feeding speed of the mixed metal source aqueous solution is preferably 0.5-10 mL/min, and specifically can be 0.5mL/min, 1mL/min, 1.5mL/min, 2mL/min, 2.5mL/min, 3mL/min, 3.5mL/min, 4mL/min, 4.5mL/min, 5mL/min, 6mL/min, 7mL/min, 8mL/min, 9mL/min or 10mL/min.
In the preparation method provided by the invention, in the step a), a precipitator and a complexing agent are preferably continuously fed into a reaction kettle in the form of a mixed aqueous solution of the precipitator and the complexing agent in the coprecipitation reaction process; the concentration of the precipitant in the mixed aqueous solution is preferably 2 to 5mol/L, and specifically may be 2mol/L, 2.3mol/L, 2.5mol/L, 2.7mol/L, 3mol/L, 3.2mol/L, 3.5mol/L, 3.7mol/L, 4mol/L, 4.2mol/L, 4.5mol/L, 4.7mol/L or 5mol/L; the concentration of the complexing agent in the mixed aqueous solution is preferably 0.5-2 mol/L, and specifically can be 0.5mol/L, 0.6mol/L, 0.7mol/L, 0.8mol/L, 0.9mol/L, 1mol/L, 1.1mol/L, 1.2mol/L, 1.3mol/L, 1.4mol/L, 1.5mol/L, 1.6mol/L, 1.7mol/L, 1.8mol/L, 1.9mol/L or 2mol/L; the feeding speed of the mixed aqueous solution is preferably 0.5-10 mL/min, and specifically may be 0.5mL/min, 1mL/min, 1.5mL/min, 2mL/min, 2.5mL/min, 3mL/min, 3.5mL/min, 4mL/min, 4.5mL/min, 5mL/min, 6mL/min, 7mL/min, 8mL/min, 9mL/min or 10mL/min.
In the preparation method provided by the invention, in the step a), the pH value of the reaction system is preferably controlled to be 8 to 12, and specifically may be 8, 8.2, 8.5, 8.7, 9, 9.2, 9.5, 9.7, 10, 10.2, 10.5, 10.7, 11, 11.2, 11.5, 11.7 or 12 in the process of the coprecipitation reaction.
In the preparation method provided by the invention, in the step a), the pH value of the coprecipitation reaction is preferably regulated by adding ammonia water; the concentration of the aqueous ammonia is preferably 0.1 to 3mol/L, and specifically may be 0.1mol/L, 0.15mol/L, 0.2mol/L, 0.25mol/L, 0.3mol/L, 0.4mol/L, 0.5mol/L, 0.7mol/L, 1mol/L, 1.2mol/L, 1.5mol/L, 1.7mol/L, 2mol/L, 2.3mol/L, 2.5mol/L, 2.7mol/L or 3mol/L.
In the preparation method provided by the invention, in the step a), the coprecipitation reaction is preferably carried out in a protective gas atmosphere; the protective gas is preferably nitrogen; the protective gas is preferably continuously fed into the reaction kettle in the coprecipitation reaction process; the gas supply speed of the protective gas is preferably 1-10 mL/min, and specifically may be 1mL/min, 1.5mL/min, 2mL/min, 2.5mL/min, 3mL/min, 3.5mL/min, 4mL/min, 4.5mL/min, 5mL/min, 6mL/min, 7mL/min, 8mL/min, 9mL/min or 10mL/min.
In the preparation method provided by the invention, in the step a), the coprecipitation reaction is preferably carried out under stirring conditions; the stirring speed is preferably 200-1000 r/min, and specifically can be 200r/min, 250r/min, 300r/min, 350r/min, 400r/min, 450r/min, 500r/min, 550r/min, 600r/min, 650r/min, 700r/min, 750r/min, 800r/min, 850r/min, 900r/min, 950r/min or 1000r/min.
In the preparation method provided by the invention, in the step a), the temperature of the coprecipitation reaction is preferably 40-70 ℃, and specifically can be 40 ℃, 42 ℃, 45 ℃, 47 ℃, 50 ℃, 52 ℃, 55 ℃, 57 ℃, 60 ℃, 62 ℃, 65 ℃, 67 ℃ or 70 ℃; the time of the coprecipitation reaction is preferably 15 to 30 hours, and specifically may be 15 hours, 16 hours, 17 hours, 18 hours, 19 hours, 20 hours, 21 hours, 22 hours, 23 hours, 24 hours, 25 hours, 26 hours, 27 hours, 28 hours, 29 hours or 30 hours.
In the preparation method provided by the invention, in the step a), after the coprecipitation reaction is finished, preferably, standing and aging are carried out; the standing and aging time is preferably 2-10 h, and specifically can be 2h, 2.5h, 3h, 3.5h, 4h, 4.5h, 5h, 5.5h, 6h, 6.5h, 7h, 7.5h, 8h, 8.5h, 9h, 9.5h or 10h.
In the preparation method provided by the invention, in the step a), the precipitate is preferably obtained after centrifugation and filtration; the precipitate is preferably washed before being dried; the drying temperature is preferably 60-150 deg.C, and specifically 60 deg.C, 65 deg.C, 70 deg.C, 75 deg.C, 80 deg.C, 85 deg.C, 90 deg.C, 95 deg.C, 100 deg.C, 105 deg.C, 110 deg.C, 115 deg.C, 120 deg.C, 125 deg.C, 130 deg.C, 135 deg.C, 140 deg.C, 145 deg.C or 150 deg.C; the drying time is preferably 6 to 20 hours, and specifically can be 6 hours, 7 hours, 8 hours, 9 hours, 10 hours, 11 hours, 12 hours, 13 hours, 14 hours, 15 hours, 16 hours, 17 hours, 18 hours, 19 hours or 20 hours.
In the preparation method provided by the invention, in the step b), the Na source is preferably one or more of sodium carbonate, sodium bicarbonate, sodium nitrate, sodium hydroxide and sodium acetate; the M source is preferably one or more of oxides, hydroxides, carbonates and sulfates corresponding to M element, including but not limited to one or more of lithium hydroxide, titanium dioxide and tin dioxide; the dosage ratio of the Na source, the M source and the precursor particles is determined according to the atomic number ratio of each element in the chemical formula of the positive electrode material of the sodium-ion battery to be prepared; the molar ratio of the Na source to the precursor particles is preferably (0.5 to 1.2): 1, specifically can be 0.5; the molar ratio of the M source to the precursor particles is preferably (0 to 0.5): 1, specifically can be 0.05.
In the preparation method provided by the invention, in the step b), the oxygen-containing atmosphere is preferably an air atmosphere; the calcination temperature is preferably 600-1100 deg.C, specifically 600 deg.C, 625 deg.C, 650 deg.C, 675 deg.C, 700 deg.C, 725 deg.C, 750 deg.C, 775 deg.C, 800 deg.C, 825 deg.C, 850 deg.C, 875 deg.C, 900 deg.C, 925 deg.C, 950 deg.C, 975 deg.C, 1000 deg.C, 1025 deg.C, 1050 deg.C, 1075 deg.C or 1100 deg.C; the heating rate before reaching the temperature is preferably 1-10 ℃/min, and can be 1 ℃/min, 2 ℃/min, 3 ℃/min, 4 ℃/min, 5 ℃/min, 6 ℃/min, 7 ℃/min, 8 ℃/min, 9 ℃/min or 10 ℃/min; the calcination time is preferably 2 to 30 hours, specifically 2 hours, 3 hours, 4 hours, 5 hours, 6 hours, 7 hours, 8 hours, 9 hours, 10 hours, 11 hours, 12 hours, 13 hours, 14 hours, 15 hours, 16 hours, 17 hours, 18 hours, 19 hours, 20 hours, 21 hours, 22 hours, 23 hours, 24 hours, 25 hours, 26 hours, 27 hours, 28 hours, 29 hours or 30 hours, and the time does not include the time consumed in the process of raising the temperature to the calcination temperature.
The method provided by the invention adopts a coprecipitation-high temperature solid phase method to prepare the sodium ion battery anode material with the composite phase NFM layered structure and high specific capacity and long cycle performance, and the method is matched with the existing industrially mature NFM precursor, has low energy consumption and is easy for industrial production.
The invention also provides a sodium ion battery, and the positive electrode material of the sodium ion battery is the positive electrode material of the sodium ion battery in the technical scheme or the positive electrode material of the sodium ion battery prepared by the preparation method in the technical scheme.
For the sake of clarity, the following examples are given in detail.
Example 1
Preparing a sulfate solution with a nickel-iron-manganese molar ratio of 3L/L mixed solution of sodium tripolyphosphate; pumping the sulfate solution into a reaction kettle at the same time at the flow rate of 2mL/min and the flow rate of 3mL/min of the precipitant complexing agent mixed solution by a peristaltic pump, wherein the stirring speed is 900r/min, the pH is adjusted to be about 11.0 by using 0.2mol/L ammonia water, the flow rate of nitrogen is 1.5L/min, the reaction temperature is 50 ℃, stopping feeding after reacting for 15h, standing and aging for 5h, centrifuging, filtering, washing and drying to obtain spherical precursor powder. Weighing and uniformly mixing sodium carbonate, tin dioxide and the precursor powder according to a molar ratio of 2/3 2/3 Ni 0.3 Fe 0.2 Mn 0.3 Sn 0.2 O 2 。
For Na prepared in this example 2/3 Ni 0.3 Fe 0.2 Mn 0.3 Sn 0.2 O 2 The sodium ion positive electrode material was subjected to X-ray diffraction analysis, and the result is shown in fig. 1, where fig. 1 is an X-ray diffraction spectrum provided in example 1 of the present invention. As can be seen from fig. 1, the resulting cathode material comprises two layered structures, P2 and O3.
Na prepared in this example 2/3 Ni 0.3 Fe 0.2 Mn 0.3 Sn 0.2 O 2 The particle size, specific surface area and compacted density of the sodium ion cathode material are detected, and the result is as follows: particle diameter D 50 =6.06 μm, specific surface area 1.05m 2 (iv) 3.35g/cm powder compacted density at 3.5T 3 。
For Na prepared in this example 2/3 Ni 0.3 Fe 0.2 Mn 0.3 Sn 0.2 O 2 The charge and discharge performance of the sodium ion anode material is tested, and the test process is as follows:
weighing the composite positive electrode material prepared in the embodiment, acetylene black and polyvinylidene fluoride (PVDF) according to a mass ratio of 80; a metal sodium sheet is taken as a cathode, glass fiber is taken as a diaphragm, and 1MNaClO is used 4 /PC is electrolysisAssembling a CR2032 button cell in a glove box filled with argon atmosphere; the electrochemical performance test of the battery is carried out under the conditions that the voltage range is 1.5-4.2V and the multiplying power is 0.1C.
The test result shows that: the first discharge capacity of the cathode material prepared by the embodiment reaches 164mAh/g.
Comparative example 1
Preparing a sulfate solution with a nickel-iron-manganese molar ratio of 3; simultaneously pumping the sulfate solution into a reaction kettle at the flow rate of 2mL/min and the flow rate of 3mL/min of the precipitant complexing agent mixed solution by a peristaltic pump, wherein the stirring speed is 900r/min, adjusting the pH to be about 11.0 by using 0.2mol/L ammonia water, the flow rate of nitrogen is 1.5L/min, the reaction temperature is 50 ℃, stopping feeding after reacting for 15h, standing and aging for 5h, centrifuging, filtering, washing and drying to obtain spherical precursor powder. Weighing and uniformly mixing sodium carbonate and the precursor powder according to a molar ratio of 2/3 2/ 3 Ni 3/8 Fe 2/8 Mn 3/8 O 2 。
For Na prepared in this comparative example 2/3 Ni 3/8 Fe 2/8 Mn 3/8 O 2 The sodium ion positive electrode material was subjected to X-ray diffraction analysis, and the result is shown in fig. 2, and fig. 2 is an X-ray diffraction spectrum provided in comparative example 1 of the present invention. As can be seen from fig. 2, the resulting cathode material has only a P2 phase.
Example 2
Preparing a sulfate solution with a nickel-iron-manganese molar ratio of 2; simultaneously pumping the sulfate solution and the precipitant complexing agent mixed solution into a reaction kettle at the flow rates of 2mL/min and 3mL/min by a peristaltic pump, wherein the stirring speed is 800r/min, the pH is adjusted to be about 10.8 by 0.2mol/L ammonia water, the nitrogen flow rate is 2.0L/min, the reaction temperature is 60 DEG CAnd stopping feeding after reacting for 18 hours, standing and aging for 8 hours, centrifuging, filtering, washing, and drying to obtain spherical precursor powder. Weighing and uniformly mixing sodium carbonate, lithium hydroxide and the precursor powder according to a molar ratio of 2/3 to 0.2, heating to 800 ℃ at a heating rate of 2 ℃/min, calcining for 18 hours at the temperature, and naturally cooling to room temperature after the calcination is finished to obtain the P2/O3 composite phase sodium ion cathode material Na 2/3 Li 0.2 Ni 0.2 Fe 0.2 Mn 0.4 O2。
For Na prepared in this example 2/3 Li 0.2 Ni 0.2 Fe 0.2 Mn 0.4 O 2 The sodium ion anode material is subjected to X-ray diffraction analysis, and the result shows that: the obtained cathode material comprises two layered structures of P2 and O3.
Na prepared in this example 2/3 Li 0.2 Ni 0.2 Fe 0.2 Mn 0.4 O 2 The sodium ion cathode material is observed by a scanning electron microscope, and the result is shown in fig. 3, and fig. 3 is the scanning electron microscope image provided by the embodiment 2 of the invention. As can be seen from fig. 3, the positive electrode material had a uniform particle distribution, and consisted of secondary spheres, and had an average particle diameter (D) 50 ) About 4 μm.
For Na prepared in this example 2/3 Li 0.2 Ni 0.2 Fe 0.2 Mn 0.4 O 2 The specific surface area and the compaction density of the sodium ion cathode material are detected, and the result is as follows: specific surface area 0.84m 2 (g), 3.5T powder compaction Density 3.43g/cm 3 。
Na prepared in this example 2/3 Li 0.2 Ni 0.2 Fe 0.2 Mn 0.4 O 2 The charge and discharge performance of the sodium ion positive electrode material was tested in the same manner as in example 1. The test result is shown in fig. 4, and fig. 4 is a first charge and discharge curve diagram of the sodium ion positive electrode material provided in embodiment 2 of the present invention at 0.1C and 1.5-4.2V. As can be seen from FIG. 4, the first discharge capacity of the cathode material prepared by the present embodiment reaches 198mAh/g.
Comparative example 2
Preparing a nickel-iron-manganese mixture by using deionized water, wherein the molar ratio of nickel to iron to manganese is 2Preparing a 5mol/L sodium hydroxide solution and a 2mol/L sodium hexametaphosphate mixed solution by using deionized water for a sulfate solution with the degree of 3 mol/L; pumping the sulfate solution into a reaction kettle at the same time at the flow rate of 2mL/min and the flow rate of 3mL/min of the precipitant complexing agent mixed solution by a peristaltic pump, wherein the stirring speed is 800r/min, the pH is adjusted to be about 10.8 by using 0.2mol/L ammonia water, the flow rate of nitrogen is 2.0L/min, the reaction temperature is 60 ℃, stopping feeding after reacting for 18h, standing and aging for 8h, centrifuging, filtering, washing and drying to obtain spherical precursor powder. Weighing and uniformly mixing sodium carbonate and the precursor powder according to a molar ratio of 2/3 to 1, heating to 800 ℃ at a heating rate of 2 ℃/min, calcining at the temperature for 18 hours, and naturally cooling to room temperature after the calcination is finished to obtain a sodium ion cathode material Na 2/ 3 Ni 1/4 Fe 1/4 Mn 1/2 O 2 。
For Na prepared in this comparative example 2/3 Ni 1/4 Fe 1/4 Mn 1/2 O 2 The sodium ion anode material is subjected to X-ray diffraction analysis, and the result shows that: the resulting positive electrode material had only a P2 phase.
Example 3
Preparing a sulfate solution with a nickel-iron-manganese molar ratio of 2; pumping the sulfate solution into a reaction kettle at the same time at the flow rate of 3mL/min and the flow rate of 2mL/min of the precipitant complexing agent mixed solution by a peristaltic pump, wherein the stirring speed is 900r/min, the pH is adjusted to be about 10.5 by using 0.1mol/L ammonia water, the flow rate of nitrogen is 1.0L/min, the reaction temperature is 60 ℃, stopping feeding after reacting for 20h, standing and aging for 6h, centrifuging, filtering, washing and drying to obtain spherical precursor powder. Uniformly mixing sodium carbonate, lithium hydroxide, titanium dioxide and the precursor powder according to a molar ratio of 2/3 2/3 Li 0.1 Ni 0.2 Fe 0.2 Mn 0.3 Ti 0.2 O 2 。
Na prepared in this example 2/3 Li 0.1 Ni 0.2 Fe 0.2 Mn 0.3 Ti 0.2 O 2 The sodium ion anode material is subjected to X-ray diffraction analysis, and the result shows that: the obtained cathode material comprises two layered structures of P2 and O3.
For Na prepared in this example 2/3 Li 0.1 Ni 0.2 Fe 0.2 Mn 0.3 Ti 0.2 O 2 The particle size, specific surface area and compacted density of the sodium ion cathode material are detected, and the result is as follows: particle diameter D 50 =6.15 μm and a specific surface area of 0.97m 2 (iv) 3.45g/cm powder compacted density at 3.5T 3 。
For Na prepared in this example 2/3 Li 0.1 Ni 0.2 Fe 0.2 Mn 0.3 Ti 0.2 O 2 The charge and discharge performance of the sodium ion cathode material was tested, the test method was the same as in example 1, the test results are shown in fig. 5, and fig. 5 is a cycle performance diagram of the sodium ion cathode material provided in example 3 of the present invention at 0.1C and 1.5-4.2V. As can be seen from FIG. 5, the discharge capacity of the positive electrode material prepared in the embodiment at 0.1C reaches 193.07mAh/g, and the cycle performance is excellent.
Comparative example 3
Preparing a sulfate solution with a nickel-iron-manganese molar ratio of 2; simultaneously pumping the sulfate solution into a reaction kettle at the flow rate of 3mL/min and the flow rate of 2mL/min for the precipitant complexing agent mixed solution by a peristaltic pump, wherein the stirring speed is 900r/min, adjusting the pH to be about 10.5 by using 0.1mol/L ammonia water, the flow rate of nitrogen is 1.0L/min, the reaction temperature is 60 ℃, stopping feeding after reacting for 20h, standing and aging for 6h, centrifuging, filtering, washing and drying to obtain spherical precursor powder. Weighing and uniformly mixing sodium carbonate and the precursor powder according to a molar ratio of 2/3 to 1, heating to 800 ℃ at a heating rate of 2 ℃/min, calcining at the temperature for 18 hours, and naturally cooling to room temperature after the calcination is finished to obtain a sodium ion cathode material Na 2/ 3 Ni 2/7 Fe 2/7 Mn 3/7 O 2 。
Na prepared for this comparative example 2/3 Ni 2/7 Fe 2/7 Mn 3/7 O 2 The sodium ion positive electrode material was subjected to X-ray diffraction analysis, and the result is shown in fig. 6, and fig. 6 is an X-ray diffraction spectrum provided by comparative example 3 of the present invention. As can be seen from fig. 6, the resulting cathode material has only the P2 phase.
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 chemical general formula of the positive electrode material of the sodium-ion battery is Na i Ni x Fe y Mn z M 1-x-y-z O 2 (ii) a Wherein M is one or more of Li, mg, zr, al, sn, ti, mo, ba, sr, nb and Cr, i is more than 0.5 and less than or equal to 1.2, x is more than 0 and less than or equal to 0.7, y is more than 0 and less than or equal to 0.7, z is more than 0 and less than or equal to 0.7, the values of x + y + z are less than 1, i, x, y and z meet the charge balance of the chemical formula;
the positive electrode material of the sodium-ion battery has a P2/O3 phase composite layered structure.
2. The positive electrode material for sodium-ion batteries according to claim 1, characterized in that i is greater than 0.6 and less than or equal to 0.7, x is greater than or equal to 0.2 and less than or equal to 0.3, y is greater than or equal to 0.2 and less than or equal to 0.3, and z is greater than or equal to 0.3 and less than or equal to 0.4.
3. The positive electrode material for sodium-ion batteries according to claim 1, characterized in that D of the positive electrode material for sodium-ion batteries 50 The grain diameter is 0.5-20 μm; the specific surface area of the positive electrode material of the sodium-ion battery is 0.5-5 m 2 (ii)/g; the compacted density of the positive electrode material of the sodium-ion battery is 2.75-4 g/cm 3 。
4. A method for preparing the positive electrode material of the sodium-ion battery according to any one of claims 1 to 3, comprising the steps of:
a) Carrying out coprecipitation reaction on a Ni source, a Mn source, a Fe source, a precipitator and a complexing agent in water, and drying precipitates to obtain precursor particles;
b) And mixing the precursor particles, a Na source and an M source, and calcining in an oxygen-containing atmosphere to obtain the sodium-ion battery anode material.
5. The production method according to claim 4, wherein the Ni source is one or more of nickel sulfate, nickel chloride, nickel nitrate, nickel acetate, and nickel citrate;
the Mn source is one or more of manganese sulfate, manganese chloride, manganese nitrate, manganese acetate and manganese citrate;
the Fe source is one or more of ferric sulfate, ferric chloride, ferric nitrate, ferric acetate and ferric citrate;
the Na source is one or more of sodium carbonate, sodium bicarbonate, sodium nitrate, sodium hydroxide and sodium acetate;
the M source is one or more of oxides, hydroxides, carbonates and sulfates corresponding to the M element;
the precipitating agent is one or more of a hydroxyl precipitating agent, a carbonate precipitating agent and an oxalate precipitating agent;
the complexing agent is one or more of citric acid, ammonia water, ethylene diamine tetraacetic acid salt, sodium tripolyphosphate, sodium pyrophosphate, sodium hexametaphosphate, diethanolamine and diethylenetriamine pentacarboxylate.
6. The method according to claim 4, wherein the molar ratio of the total molar amount of the Ni source, the Mn source, and the Fe source to the precipitant and the complexing agent in step a) is 1: (0.4-10): (0.1-4).
7. The preparation method according to claim 4, wherein in the step a), the temperature of the coprecipitation reaction is 40-70 ℃; the pH value of the coprecipitation reaction is 8-12; the coprecipitation reaction time is 15-30 h.
8. The method according to claim 7, wherein the pH of the coprecipitation reaction is controlled by adding ammonia water in step a).
9. The method according to claim 4, wherein in step b), the temperature of the calcination is 600 to 1100 ℃; the calcining time is 2-30 h.
10. A sodium-ion battery, characterized in that the positive electrode material of the sodium-ion battery is the positive electrode material of the sodium-ion battery according to any one of claims 1 to 3 or the positive electrode material of the sodium-ion battery prepared by the preparation method according to any one of claims 4 to 9.
CN202211057146.0A 2022-08-31 2022-08-31 Sodium-ion battery positive electrode material and preparation method and application thereof Pending CN115295787A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115872461A (en) * 2022-12-07 2023-03-31 电子科技大学长三角研究院(湖州) Method for preparing nickel-iron-manganese carbonate spherical precursor of sodium ion battery positive electrode material

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115872461A (en) * 2022-12-07 2023-03-31 电子科技大学长三角研究院(湖州) Method for preparing nickel-iron-manganese carbonate spherical precursor of sodium ion battery positive electrode material

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