CN113258060A - Sodium ion battery high-nickel layered oxide material and preparation method and application thereof - Google Patents

Sodium ion battery high-nickel layered oxide material and preparation method and application thereof Download PDF

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CN113258060A
CN113258060A CN202010086561.3A CN202010086561A CN113258060A CN 113258060 A CN113258060 A CN 113258060A CN 202010086561 A CN202010086561 A CN 202010086561A CN 113258060 A CN113258060 A CN 113258060A
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sodium
equal
oxide material
transition metal
ion battery
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CN113258060B (en
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胡勇胜
丁飞翔
赵成龙
容晓晖
陆雅翔
陈立泉
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • H01M4/02—Electrodes composed of, or comprising, active material
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    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • 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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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
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    • H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
    • H—ELECTRICITY
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    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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    • C—CHEMISTRY; METALLURGY
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    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention discloses a sodium ion battery high nickel layered oxide material and a preparation method and application thereof, wherein the chemical general formula of the sodium ion battery high nickel layered oxide material is NaxNiaFebMncMd02±δ(ii) a Wherein Ni, Fe and Mn are transition metal elements, and M is an element for doping and substituting a transition metal position; in the structure of the oxide material, the ions of the transition metal sites form eight with the adjacent six oxygensNaO of a face-centered structure and coordinated with octahedra6The layers are alternately arranged to form an O3 type sodium ion battery high nickel layered oxide material with a space group of R-3 m; m in particular comprises Li+，Mg2+，Ca2+，Cu2+，Zn2+，Al3+，B3+，Co3+，V3+，Y3+，Ti4+，Zr4+，Sn4+，Mo4+，Si4+，Ru4+，Nb5+，Sb5+，Mo5+，Mo6+，W6+One or more of; x, a, b, c, d and 2+ delta are respectively the mole percentage of the corresponding elements, each component in the chemical general formula satisfies the charge conservation and the stoichiometric conservation, and x is more than or equal to 0.67 and less than or equal to 1, a is more than or equal to 0.5 and less than or equal to 1, b is more than or equal to 0.01 and less than or equal to 0.35, c is more than or equal to 0.01 and less than or equal to 0.35, d is more than or equal to 0 and less than or equal to 0.3, and delta is more than or equal to 0.

Description

Sodium ion battery high-nickel layered oxide material and preparation method and application thereof
Technical Field
The invention relates to the technical field of sodium battery materials, in particular to a high-nickel layered oxide material of a sodium ion battery, and a preparation method and application thereof.
Background
Sodium ion batteries have long been considered as a beneficial supplement to lithium ion batteries due to their low cost, abundant sources, and the like. To date, research on the related art of sodium ion batteries has attracted extensive attention in both academic and industrial fields. The development of high capacity, high potential positive electrode materials is crucial for their practical applications. In the last decade, various positive electrode materials such as oxides, polyanionic compounds, and prussian blue analogues have been proposed. Among them, a layered oxide material has been widely studied because of its excellent electrochemical properties. Sodium-based layered materials can be generally classified into P-type and O-type due to the different stacking patterns of sodium ions. Wherein, the P type means that sodium ions occupy the position of a triangular prism; o-type refers to sodium ions occupying octahedral sites. Understanding the potential structure-activity relationship of these two crystal structures will help to develop higher performance sodium ion battery materials.
Layered NaxCoO2The material was proposed in the beginning of the 80 th 20 th century, as early as 1981, Delmas et alNaxCoO with O3, O'3, P3 and P2 phases2And the electrochemical sodium storage behavior of the compounds is studied. The specific capacity is found to be more than 100-150mAh/g, and the energy density is more than 300-400 Wh/kg. However, the high price of cobalt resource becomes a great obstacle to the industrial application of the system material.
In the industry, Ni is developed as a sodium ion battery system material, and the nickel-based layered oxide with a valence state of +2 is commonly used as a sodium ion battery positive electrode material. However, the reversible specific capacity of the material has a further improved space, and the requirement of the industry on a sodium ion battery material with higher performance cannot be met.
Disclosure of Invention
The invention aims to provide a high-nickel layered oxide material for a sodium ion battery and a preparation method and application thereof, aiming at the defects of the prior art.
In view of the above, in a first aspect, embodiments of the present invention provide a nickel-rich layered oxide material for a sodium ion battery, having a chemical formula: na (Na)xNiaFebMncMd02±δ；
Wherein Ni, Fe and Mn are transition metal elements, and M is an element for doping and substituting a transition metal position; in the structure of the oxide material, ions of the transition metal sites form octahedral structures with the adjacent six oxygens and are coordinated with octahedral NaO6The layers are alternately arranged to form an O3 type sodium ion battery high nickel layered oxide material with a space group of R-3 m;
said M comprising in particular Li+，Mg2+，Ca2+，Cu2+，Zn2+，Al3+，B3+，Co3+，V3+，Y3+，Ti4+，Zr4+，Sn4+，Mo4 +，Si4+，Ru4+，Nb5+，Sb5+，Mo5+，Mo6+，W6+One or more of; x, a, b, c, d and 2+ delta are respectively the mole percentage of the corresponding elements, each component in the chemical general formula satisfies the conservation of charge and the conservation of stoichiometry, and x is more than or equal to 0.67 and less than or equal to 1, and a is more than or equal to 0.5 and less than1，0.01≤b≤0.35，0.01≤c≤0.35，0≤d≤0.3，0≤δ≤0.1。
Preferably, the nickel-rich layered oxide material for sodium ion batteries is used as a positive electrode active material for sodium ion secondary batteries.
In a second aspect, an embodiment of the present invention provides a method for preparing a nickel-rich layered oxide material for a sodium ion battery, where the preparation method is a solid-phase method, and includes:
mixing a sodium source with the stoichiometric amount of 100-120 wt.% of required sodium, an oxide of nickel, an oxide of iron, an oxide of manganese and an oxide, hydroxide or nitrate of M according to a proportion, adding absolute ethyl alcohol or acetone, and grinding uniformly to obtain precursor powder; the sodium source comprises one or more of sodium nitrate, sodium peroxide, sodium superoxide, sodium carbonate, sodium hydroxide and sodium oxalate;
placing the obtained precursor powder tablet into a crucible, calcining for 10-24 hours at the temperature of 700-900 ℃ in the sintering atmosphere of air and/or oxygen, cooling to room temperature, and grinding to obtain the high-nickel layered anode oxide material;
wherein M is an element for doping and substituting transition metal sites, and specifically comprises Li+，Mg2+，Ca2+，Cu2+，Zn2+，Al3+，B3+，Co3+，V3+，Y3+，Ti4+，Zr4+，Sn4+，Mo4+，Si4+，Ru4+，Nb5+，Sb5+，Mo5+，Mo6+，W6+One or more of (a).
In a third aspect, an embodiment of the present invention provides a preparation method of a high nickel layered oxide material for a sodium ion battery, where the preparation method is a co-precipitation-high temperature solid phase method, and includes:
preparing a mixed solution of water-soluble Ni salt, Fe salt, Mn salt and M salt as a first solution according to the proportion of the required Ni, Fe, Mn and M; wherein the concentration of the cations in the first solution is 1-3 mol/L; m is an element for doping substitution of the transition metal site, and specifically comprises Li+，Mg2+，Ca2+，Cu2+，Zn2+，Al3+，B3+，Co3+，V3+，Y3+，Ti4+，Zr4+，Sn4+，Mo4+，Si4+，Ru4+，Nb5+，Sb5+，Mo5+，Mo6+，W6+One or more of;
dissolving NaOH or KOH in deionized water with the concentration of 2-4mol/L, and adding a proper amount of ammonia water to form a second solution;
adding the first solution and the second solution into a reaction container simultaneously in the stirring process, and carrying out coprecipitation reaction at the temperature of 50-60 ℃, wherein the pH value is maintained at 10-12 in the reaction process;
aging for 0-24 hours after the coprecipitation reaction is finished, filtering the precipitate, washing and drying to obtain a hydroxide precursor of the transition metal elements which are uniformly distributed;
uniformly mixing the hydroxide precursor and a sodium source with the stoichiometric amount of 100-120 wt.% of sodium according to the stoichiometric ratio, keeping the temperature at 400-500 ℃ for 3-6 hours in an oxygen atmosphere, calcining at 700-900 ℃ for 10-24 hours, and cooling to room temperature to obtain the high-nickel layered oxide material of the sodium-ion battery; the sodium source includes: one or more of sodium nitrate, sodium peroxide, sodium superoxide, sodium carbonate, sodium hydroxide and sodium oxalate.
In a fourth aspect, an embodiment of the present invention provides a method for preparing a nickel-rich layered oxide material for a sodium ion battery, where the method is a sol-gel method, and includes:
weighing sodium ions, soluble salts of transition metal ions and a proper amount of citric acid according to a required stoichiometric ratio, and dissolving the sodium ions, the soluble salts of the transition metal ions and the citric acid in deionized water to form slurry of a mixed solution; wherein the transition metal ions comprise Ni, Fe, Mn; the transition metal ions also comprise an element M for doping substitution of transition metal sites; m in particular comprises Li+，Mg2+，Ca2+，Cu2+，Zn2+，Al3+，B3+，Co3+，V3+，Y3+，Ti4+，Zr4+，Sn4+，Mo4+，Si4+，Ru4+，Nb5+，Sb5+，Mo5+，Mo6+，W6+One or more of;
heating and evaporating the obtained slurry in an oil bath pan to dryness to form dry gel;
and (3) placing the obtained xerogel in a crucible, pretreating for 3-6 hours at the temperature of 400-500 ℃, grinding the powder obtained by pretreatment, placing a pressed sheet in the crucible, calcining for 10-24 hours at the temperature of 700-900 ℃ in the air and/or oxygen atmosphere, cooling to room temperature, and grinding to obtain the high-nickel layered oxide material of the sodium ion battery.
In a fifth aspect, embodiments of the present invention provide an electrode material for a sodium-ion secondary battery, the electrode material including: a conductive additive, a binder and the sodium-ion battery high-nickel layered oxide material of the first aspect.
Preferably, the conductive additive includes: one or more of carbon black, acetylene black, graphite powder, carbon nanotubes, graphene and nitrogen-doped carbon;
the binder comprises one or more of polyvinylidene fluoride (PVDF), sodium alginate, sodium carboxymethyl cellulose (CMC) and Styrene Butadiene Rubber (SBR).
In a sixth aspect, the embodiment of the present invention provides a positive electrode sheet including the electrode material of the sodium-ion secondary battery described in the fifth aspect.
In a seventh aspect, an embodiment of the present invention provides a sodium-ion secondary battery including the positive electrode tab of the above sixth aspect.
According to the high-nickel layered oxide material for the sodium ion battery, provided by the invention, a large amount of trivalent nickel ions are introduced in the composition to provide charge compensation, and the iron and manganese ions are matched with a small amount of doping elements to improve the stability of a crystal structure, so that the reversible specific capacity and the energy density of the layered oxide material can be obviously improved, and the material has excellent cycle performance. The method can realize large-scale continuous production by a simple coprecipitation-high temperature solid phase synthesis method, and realizes the maximization of economic benefit; the obtained material has high reversible specific capacity, high energy density, high reversible charge-discharge potential and stable cycle. The sodium ion full cell constructed by the method has the characteristics of high average energy storage voltage, high energy density and high power density, can be used as green clean energy for power generation, smart grid peak regulation, distributed power stations, backup power supplies, communication base stations or energy storage equipment of low-speed electric automobiles and the like, and has excellent safety performance, rate capability and cycle performance.
Drawings
The technical solutions of the embodiments of the present invention are further described in detail with reference to the accompanying drawings and embodiments.
FIG. 1 is an X-ray diffraction (XRD) pattern of a high nickel layered positive oxide material prepared by examples 1, 2, 3 of the present invention;
FIG. 2 is an XRD pattern of the high nickel layered positive oxide material prepared in examples 4, 5, 6 and 7 of the present invention;
FIG. 3 is a Scanning Electron Microscope (SEM) image of the high nickel layered positive oxide material prepared in example 3 of the present invention;
FIG. 4 is a Scanning Electron Microscope (SEM) image of the high nickel layered positive oxide material prepared in example 4 of the present invention;
fig. 5 is a three-cycle charge-discharge curve diagram before testing of a high nickel layered positive oxide material half cell prepared by applying the embodiment 4 of the present invention;
FIG. 6 is a four-week charge-discharge curve diagram of a half-cell before testing to which the high nickel layered positive oxide material prepared in example 5 of the present invention was applied;
FIG. 7 is a graph of two-cycle charge and discharge before half-cell testing using the high nickel layered positive oxide material prepared in example 6 of the present invention;
FIG. 8 is a four-week charge-discharge curve diagram of a half-cell before testing to which the high nickel layered positive oxide material prepared in example 8 of the present invention was applied;
FIG. 9 is a graph of half-cell test cycle performance for a high nickel layered positive oxide material prepared by applying example 5 of the present invention;
fig. 10 is a graph showing the first cycle charge and discharge of a half cell test using a low nickel layered cathode material prepared by a comparative example of the present invention.
Detailed Description
Examples of the inventionA high nickel layered oxide material for a sodium ion battery is provided, and the chemical general formula is as follows: na (Na)xNiaFebMncMd02±δ；
Wherein Ni, Fe and Mn are transition metal elements, and M is an element for doping and substituting a transition metal position; in the structure of the oxide material, ions of the transition metal sites form octahedral structures with the adjacent six oxygens and are coordinated with octahedral NaO6The layers are alternately arranged to form an O3 type sodium ion battery high nickel layered oxide material with a space group of R-3 m;
m in particular comprises Li+，Mg2+，Ca2+，Cu2+，Zn2+，Al3+，B3+，Co3+，V3+，Y3+，Ti4+，Zr4+，Sn4+，Mo4+，Si4 +，Ru4+，Nb5+，Sb5+，Mo5+，Mo6+，W6+One or more of; x, a, b, c, d and 2+ delta are respectively the mole percentage of the corresponding elements, each component in the chemical general formula satisfies the charge conservation and the stoichiometric conservation, and x is more than or equal to 0.67 and less than or equal to 1, a is more than or equal to 0.5 and less than or equal to 1, b is more than or equal to 0.01 and less than or equal to 0.35, c is more than or equal to 0.01 and less than or equal to 0.35, d is more than or equal to 0 and less than or equal to 0.3, and delta is more than or equal to 0 and less than or equal to 0.1.
In the high nickel content layered material of the present invention, essentially nickel is present in the +3 valence state.
The high nickel layered oxide material of the sodium ion battery can be used as a positive electrode active material of a sodium ion secondary battery. The high nickel layered anode oxide material is synthesized by using iron and manganese transition metal elements with rich resources and doping a small amount of other elements with electrochemical activity or inertia, and has the advantages of stable structure, high reversible specific capacity, high energy density, high reversible charge-discharge potential and stable circulation.
The embodiment of the invention also provides a preparation method of the high-nickel layered anode oxide material, which can be specifically prepared by a solid phase method, a coprecipitation-high temperature solid phase method and a sol-gel method.
The method for preparing the nano-particles by the solid phase method comprises the following steps:
step 110, mixing a sodium source with the stoichiometric amount of 100-120 wt.% of required sodium, an oxide of nickel, an oxide of iron, an oxide of manganese and an oxide, hydroxide or nitrate of M according to a proportion, adding absolute ethyl alcohol or acetone, and grinding uniformly to obtain precursor powder;
wherein the sodium source comprises one or more of sodium nitrate, sodium peroxide, sodium superoxide, sodium carbonate, sodium hydroxide and sodium oxalate; m is as described above and will not be described in detail.
And step 120, placing the obtained precursor powder tablet into a crucible, calcining for 10-24 hours at the temperature of 700-900 ℃ in the sintering atmosphere of air and/or oxygen, cooling to room temperature, and grinding to obtain the high-nickel layered anode oxide material.
The high nickel layered anode oxide material prepared by the method has high nickel content, and the total valence of ions of the O3 layered oxide transition metal layer is +3, so that part of trivalent manganese, and part of divalent and trivalent iron-tetravalent manganese exist in the nickel to jointly maintain charge conservation, so that the total valence of the transition metal layer is + 3.
The preparation method adopting the coprecipitation-high temperature solid phase method comprises the following steps:
step 210, preparing a mixed solution of water-soluble Ni salt, Fe salt, Mn salt and M salt as a first solution according to the proportion of the required Ni, Fe, Mn and M; wherein the concentration of the cations in the first solution is 1-3 mol/L;
wherein, M is as described above and is not described in detail.
Step 220, dissolving NaOH or KOH in deionized water with the concentration of 2-4mol/L, and adding a proper amount of ammonia water to form a second solution;
step 230, adding the first solution and the second solution into a reaction container simultaneously in the stirring process, and carrying out coprecipitation reaction at the temperature of 50-60 ℃, wherein the pH value is maintained at 10-12 in the reaction process;
step 240, aging for 0-24 hours after the coprecipitation reaction is finished, filtering the precipitate, washing and drying to obtain a hydroxide precursor of the transition metal elements which are uniformly distributed;
step 250, uniformly mixing the hydroxide precursor with a sodium source with the stoichiometric quantity of 100-120 wt.% of sodium, then preserving the heat for 3-6 hours at the temperature of 400-500 ℃ in an oxygen atmosphere, then calcining for 10-24 hours at the temperature of 700-900 ℃, and cooling to room temperature to obtain the high-nickel layered oxide material of the sodium-ion battery;
wherein, the sodium source includes: one or more of sodium nitrate, sodium peroxide, sodium superoxide, sodium carbonate, sodium hydroxide and sodium oxalate.
The method for preparing the nano-silver particles by adopting the sol-gel method comprises the following steps:
step 310, weighing sodium ions with the stoichiometric ratio of 100 wt.% to 120 wt.%, soluble salts of transition metal ions and a proper amount of citric acid according to the required stoichiometric ratio, and dissolving the sodium ions, the soluble salts of transition metal ions and the citric acid in deionized water to form slurry of a mixed solution;
wherein the transition metal ions comprise Ni, Fe and Mn; in addition, the transition metal ions may further include an element M for doping and substituting the transition metal sites, where M is described above and is not described in detail.
Step 320, heating and evaporating the obtained slurry in an oil bath pan to dryness to form xerogel;
and 330, placing the obtained xerogel in a crucible, pretreating for 3-6 hours at the temperature of 400-500 ℃, grinding the powder obtained by pretreatment, placing a pressed sheet in the crucible, calcining for 10-24 hours at the temperature of 700-900 ℃ in the air and/or oxygen atmosphere, cooling to room temperature, and grinding to obtain the high-nickel layered oxide material of the sodium ion battery.
The high nickel layered anode oxide material of the sodium ion battery is synthesized by using iron and manganese transition metal elements with rich resources and doping a small amount of other elements with electrochemical activity or inertia, is used for high nickel layered anode active materials, and is simple to synthesize and easy for large-scale continuous production. The sodium ion full cell constructed by the method has the characteristics of high average energy storage voltage, high energy density and high power density, can be used as green clean energy for power generation, smart grid peak regulation, distributed power stations, backup power supplies, communication base stations or energy storage equipment of low-speed electric automobiles and the like, and has excellent safety performance, rate capability and cycle performance.
The high nickel layered positive oxide material of the present invention, and the preparation method and properties thereof are further described below in detail with reference to some specific examples.
Example 1
In the embodiment, a solid phase method is adopted to prepare the high nickel layered anode oxide material NaNi0.60Fe0.20Mn0.20O2The method comprises the following specific steps: weighing Na in stoichiometric ratio2CO3(excess 5%), Ni2O3、Fe2O3And MnO2Adding a proper amount of absolute ethyl alcohol into an agate mortar, mixing and grinding uniformly to obtain a precursor, pressing the precursor into a round piece with the diameter of 15mm under the pressure of 10Mpa, treating for 15 hours in a tubular furnace at the temperature of 800 ℃ in an oxygen atmosphere to obtain a black powder, grinding the black powder for later use, namely the high nickel layered anode oxide material NaNi of the invention0.60Fe0.20Mn0.20O2。
The XRD spectrum of the high nickel layered cathode oxide material prepared in this example is shown in fig. 1, and it can be seen from comparison with the standard card that the main phase is O3 phase material, the space group is R-3m, and in addition, a trace amount of NiO impurity phase exists.
Example 2
In the embodiment, a solid phase method is adopted to prepare the high nickel layered anode oxide material NaNi0.60Fe0.20Mn0.20O2The method comprises the following specific steps: weighing Na in stoichiometric ratio2O2(excess 5%), Ni2O3、Fe2O3And MnO2Putting the mixture into a high-energy ball milling tank in an inert atmosphere, uniformly ball milling the mixture in a high-energy ball milling tank to obtain a precursor, pressing the precursor into a round piece with the diameter of 15mm under the pressure of 10Mpa, treating the round piece for 15 hours in a tube furnace at the temperature of 800 ℃ in an oxygen atmosphere to obtain a black powder piece, and grinding the black powder piece for later use to obtain the high-nickel layered anode oxide material NaNi0.60Fe0.20Mn0.20O2。
The XRD pattern of the high nickel layered cathode oxide material prepared in this example is shown in fig. 1, and it is known that the material is pure O3 phase and the space group is R-3m when compared with standard cards.
Example 3
In the embodiment, a coprecipitation-high temperature solid phase method is adopted to prepare a high nickel layered anode oxide material NaNi0.60Fe0.20Mn0.20O2The method comprises the following specific steps:
according to the formula NaNi0.60Fe0.20Mn0.20O2Preparing NiSO by the proportion of Ni, Fe and Mn4·6H2O，CoSO4·7H2O and MnSO4·H2Preparing a deionized water solution of O with the concentration of 2 mol/L;
preparing an alkali liquor by using sodium hydroxide, ammonia water and deionized water, wherein the concentration of the sodium hydroxide is 4mol/L, and the concentration of the ammonia is 0.8 mol/L;
adding a proper amount of deionized water into a reaction kettle, introducing nitrogen, heating to 55 ℃, keeping the temperature, then adding sodium hydroxide and ammonia water into the reaction kettle to adjust the pH to 11.7, wherein the ammonia concentration is 0.4mol/L, stirring at the speed of 500r/min, then simultaneously dropwise adding a transition metal solution and an alkali liquor, and maintaining the pH to be about 11.7;
after the reaction is finished, filtering and washing the precipitate until the pH value of the filtered water is less than or equal to 9.5, and drying the precipitate for 12 hours at 120 ℃ to obtain a hydroxide precursor of the transition metal element which is uniformly distributed;
uniformly mixing the obtained hydroxide precursor and 10% excessive sodium nitrate according to the stoichiometric ratio, keeping the temperature of 450 ℃ for 5 hours in an oxygen atmosphere, calcining the mixture at 850 ℃ for 15 hours, and cooling the calcined mixture to room temperature to obtain the high-nickel layered anode oxide material.
The XRD pattern of the high nickel layered cathode oxide material prepared in this example is shown in fig. 1, and it is known that the material is pure O3 phase and the space group is R-3m when compared with standard cards. Fig. 3 is a Scanning Electron Microscope (SEM) image of the high nickel layered cathode material prepared in this example, which shows that the particle size is about 1-4um, the particles are spherical, and the surface is smooth.
Example 4
In the embodiment, a coprecipitation-high temperature solid phase method is adopted to prepare a high nickel layered anode oxide material NaNi0.60Fe0.25Mn0.15O2The method comprises the following specific steps:
according to the formula NaNi0.60Fe0.25Mn0.15O2Preparing NiSO by the proportion of Ni, Fe and Mn4·6H2O，CoSO4·7H2O and MnSO4·H2Preparing deionized water solution of O with the concentration of 1.5 mol/L;
preparing an alkali liquor by using sodium hydroxide, ammonia water and deionized water, wherein the concentration of the sodium hydroxide is 3mol/L, and the concentration of the ammonia is 0.6 mol/L;
adding a proper amount of deionized water into a reaction kettle, introducing nitrogen, heating to 55 ℃, keeping the temperature, then adding sodium hydroxide and ammonia water into the reaction kettle to adjust the pH to 12, wherein the ammonia concentration is 0.4mol/L, stirring at the speed of 500r/min, then simultaneously dropwise adding a transition metal solution and an alkali liquor, and simultaneously maintaining the pH to be about 12;
after the reaction is finished, filtering and washing the precipitate until the pH value of the filtered water is less than or equal to 9.5, and drying the precipitate for 12 hours at 120 ℃ to obtain a hydroxide precursor of the transition metal element which is uniformly distributed;
uniformly mixing the obtained hydroxide precursor and 12% excessive sodium nitrate according to the stoichiometric ratio, keeping the temperature of 450 ℃ for 5 hours in an oxygen atmosphere, calcining at 800 ℃ for 15 hours, and cooling to room temperature to obtain the high-nickel layered anode oxide material.
The XRD pattern of the high nickel layered cathode oxide material prepared in this example is shown in fig. 2, and it is known that the material is pure O3 phase and the space group is R-3m when compared with the standard card. Fig. 4 is a Scanning Electron Microscope (SEM) image of the high nickel layered cathode material prepared in this example, which shows that the particle size is about 1-4um, the particles are spherical, the surface is smooth, and the crystallinity is good.
Example 5
In the embodiment, a coprecipitation-high temperature solid phase method is adopted to prepare a high nickel layered anode oxide material NaNi0.70Fe0.20Mn0.10O2The method comprises the following specific steps:
according to the formula NaNi0.70Fe0.20Mn0.10O2Preparing NiSO by the proportion of Ni, Fe and Mn4·6H2O，CoSO4·7H2O and MnSO4·H2Deionized water of OThe preparation concentration of the solution is 2 mol/L;
preparing an alkali liquor by using sodium hydroxide, ammonia water and deionized water, wherein the concentration of the sodium hydroxide is 4mol/L, and the concentration of the ammonia is 0.8 mol/L;
adding a proper amount of deionized water into a reaction kettle, introducing nitrogen, heating to 60 ℃, keeping the temperature, then adding sodium hydroxide and ammonia water into the reaction kettle to adjust the pH to 12, wherein the ammonia concentration is 0.4mol/L, stirring at the speed of 500r/min, then simultaneously dropwise adding a transition metal solution and an alkali liquor, and simultaneously maintaining the pH to be about 12;
after the reaction is finished, filtering and washing the precipitate until the pH value of the filtered water is less than or equal to 9.5, and drying the precipitate for 12 hours at 120 ℃ to obtain a hydroxide precursor of the transition metal element which is uniformly distributed;
uniformly mixing the obtained hydroxide precursor and 10% excessive sodium nitrate according to the stoichiometric ratio, keeping the temperature of 450 ℃ for 5 hours in an oxygen atmosphere, calcining at 800 ℃ for 15 hours, and cooling to room temperature to obtain a high-nickel layered anode oxide material;
the XRD pattern of the high nickel layered cathode oxide material prepared in this example is shown in FIG. 2, and the material is pure O3 phase material and has a space group of R-3m when compared with standard cards.
Example 6
In the embodiment, a coprecipitation-high temperature solid phase method is adopted to prepare a high nickel layered anode oxide material NaNi0.60Fe0.25Mn0.10Al0.05O2The method comprises the following specific steps:
according to the formula NaNi0.60Fe0.25Mn0.10Al0.05O2Preparing NiSO by the proportion of Ni, Fe and Mn4·6H2O，CoSO4·7H2O，Al2(SO4)3.18H2O and MnSO4·H2Preparing a deionized water solution of O with the concentration of 2 mol/L;
preparing an alkali liquor by using sodium hydroxide, ammonia water and deionized water, wherein the concentration of the sodium hydroxide is 4mol/L, and the concentration of the ammonia is 0.8 mol/L;
adding a proper amount of deionized water into a reaction kettle, introducing nitrogen, heating to 55 ℃, keeping the temperature, then adding sodium hydroxide and ammonia water into the reaction kettle to adjust the pH to 11.5, wherein the ammonia concentration is 0.4mol/L, stirring at the speed of 500r/min, then simultaneously dropwise adding a transition metal solution and an alkali liquor, and simultaneously maintaining the pH to be about 11.5;
after the reaction is finished, filtering and washing the precipitate until the pH value of the filtered water is less than or equal to 9.5, and drying the precipitate for 12 hours at 120 ℃ to obtain a hydroxide precursor of the transition metal element which is uniformly distributed;
and uniformly mixing the obtained hydroxide precursor and 10% excessive sodium nitrate according to the stoichiometric ratio, keeping the temperature of 450 ℃ for 5 hours in an oxygen atmosphere, calcining at 800 ℃ for 16 hours, and cooling to room temperature to obtain the high-nickel layered anode oxide material.
The XRD pattern of the high nickel layered cathode oxide material prepared in this example is shown in fig. 2, and it is known that the material is pure O3 phase and the space group is R-3m when compared with the standard card.
Example 7
In the embodiment, a coprecipitation-high temperature solid phase method is adopted to prepare a high nickel layered anode oxide material NaNi0.80Fe0.10Mn0.10O2The method comprises the following specific steps:
according to the formula NaNi0.80Fe0.10Mn0.10O2Preparing NiSO by the proportion of Ni, Fe and Mn4·6H2O，CoSO4·7H2O and MnSO4·H2Preparing a deionized water solution of O with the concentration of 2 mol/L;
preparing an alkali liquor by using sodium hydroxide, ammonia water and deionized water, wherein the concentration of the sodium hydroxide is 4mol/L, and the concentration of the ammonia is 0.8 mol/L;
adding a proper amount of deionized water into a reaction kettle, introducing nitrogen, heating to 60 ℃, keeping the temperature, then adding sodium hydroxide and ammonia water into the reaction kettle to adjust the pH to 11.5, wherein the ammonia concentration is 0.4mol/L, stirring at the speed of 500r/min, then simultaneously dropwise adding a transition metal solution and an alkali liquor, and simultaneously maintaining the pH to be about 12;
after the reaction is finished, filtering and washing the precipitate until the pH value of the filtered water is less than or equal to 9.5, and drying the precipitate for 12 hours at 120 ℃ to obtain a hydroxide precursor of the transition metal element which is uniformly distributed;
and uniformly mixing the obtained hydroxide precursor and 10% excessive sodium nitrate according to the stoichiometric ratio, keeping the temperature of 450 ℃ for 5 hours in an oxygen atmosphere, calcining at 800 ℃ for 15 hours, and cooling to room temperature to obtain the high-nickel layered anode oxide material.
The XRD pattern of the high nickel layered cathode oxide material prepared in this example is shown in fig. 2, and it is known that the material is pure O3 phase and the space group is R-3m when compared with the standard card.
Example 8
In the embodiment, a coprecipitation-high temperature solid phase method is adopted to prepare a high nickel layered anode oxide material NaNi0.70Fe0.2Mn0.05Ti0.05O2The method comprises the following specific steps:
according to the formula NaNi0.70Fe0.2Mn0.05Ti0.05O2Preparing NiSO by the proportion of Ni, Fe and Mn4·6H2O，CoSO4·7H2O and MnSO4·H2Preparing a deionized water solution of O with the concentration of 2 mol/L;
preparing an alkali liquor by using sodium hydroxide, ammonia water and deionized water, wherein the concentration of the sodium hydroxide is 4mol/L, and the concentration of the ammonia is 0.8 mol/L;
adding a proper amount of deionized water into a reaction kettle, introducing nitrogen, heating to 55 ℃, keeping the temperature, then adding sodium hydroxide and ammonia water into the reaction kettle to adjust the pH to 11.5, wherein the ammonia concentration is 0.4mol/L, stirring at the speed of 500r/min, then simultaneously dropwise adding a transition metal solution and an alkali liquor, and simultaneously maintaining the pH to be about 12;
after the reaction is finished, filtering and washing the precipitate until the pH value of the filtered water is less than or equal to 9.5, and drying the precipitate for 12 hours at 120 ℃ to obtain uniformly distributed hydroxide precursors of the transition metal elements;
uniformly mixing the obtained hydroxide precursor with 10% excessive sodium nitrate and nano titanium dioxide according to the stoichiometric ratio, keeping the temperature at 450 ℃ for 5 hours in an oxygen atmosphere, calcining at 800 ℃ for 15 hours, and cooling to room temperature to obtain the high nickel layered oxide cathode material.
Example 9
In the embodiment, a sol-gel method is adopted to prepare a high nickel layered oxide cathode material NaNi0.60Fe0.25Mn0.15O2The method comprises the following specific steps:
weighing sodium nitrate, manganese acetate, nickel acetate, ferric nitrate and a proper amount of citric acid according to the required stoichiometric ratio, and dissolving in deionized water to form a mixed solution; heating and evaporating the obtained slurry in an oil bath pan to dryness to form dry gel; and (3) collecting the obtained xerogel, placing the xerogel in a crucible, pretreating for 3-6 hours at 450 ℃, grinding the powder obtained by pretreatment, placing a pressed sheet in the crucible, calcining for 20 hours at 800 ℃, cooling to room temperature in the presence of oxygen, and grinding to obtain the high-nickel layered cathode material.
Comparative example
In the embodiment, a coprecipitation-high temperature solid phase method is adopted to prepare a low-nickel layered cathode material NaNi0.333Fe0.333Mn0.333O2The method comprises the following specific steps:
according to the formula NaNi0.333Fe0.333Mn0.333O2Preparing NiSO by the proportion of Ni, Fe and Mn4·6H2O，CoSO4·7H2O and MnSO4·H2Preparing a deionized water solution of O with the concentration of 2 mol/L;
preparing an alkali liquor by using sodium hydroxide, ammonia water and deionized water, wherein the concentration of the sodium hydroxide is 4mol/L, and the concentration of the ammonia is 0.8 mol/L;
adding a proper amount of deionized water into a reaction kettle, introducing nitrogen, heating to 60 ℃, keeping the temperature, then adding sodium hydroxide and ammonia water into the reaction kettle to adjust the pH to 12, wherein the ammonia concentration is 0.4mol/L, stirring at the speed of 500r/min, then simultaneously dropwise adding a transition metal solution and an alkali liquor, and simultaneously maintaining the pH to be about 12;
after the reaction is finished, filtering and washing the precipitate until the pH value of the filtered water is less than or equal to 9.5, and drying the precipitate for 12 hours at 120 ℃ to obtain uniformly distributed hydroxide precursors of the transition metal elements;
and uniformly mixing the obtained hydroxide precursor with 2% of excessive sodium carbonate according to the stoichiometric ratio, preserving the heat of the mixture in a muffle furnace at 450 ℃ for 5 hours, calcining the mixture at 900 ℃ for 15 hours, and cooling the calcined mixture to room temperature to obtain the low-nickel layered oxide cathode material.
The high nickel layered oxide positive electrode materials prepared in the above respective examples of the present invention and the materials in the comparative examples were tested.
Assembling a half cell: the high nickel layered cathode material in each example was mixed with conductive carbon black (Super P) and vinylidene fluoride (PVDF) at a mass ratio of 75: 15: 10 are slurried in a solution of N-methylpyrrolidone (NMP) and coated on aluminum foil, which is then cut into 12mm diameter pole pieces (loading of about 2.5-3.5 mg/cm)2) 1mol/L NaClO with a metal sodium sheet as a negative electrode4Polycarbonate (PC): ethylene Carbonate (EC): dimethyl carbonate (DMC) (volume ratio 1: 1: 1) solution is used as electrolyte, a glass fiber diaphragm is assembled into a CR2032 button cell half-cell in an argon glove box.
And (3) charge and discharge test: the voltage range of charging and discharging of the button cell is 2.0-4.0V or 2.0-4.2V, before the cycle test, the button cell is activated twice by using a smaller current density of 15mA/g (0.1C), and then the button cell is cycled under the multiplying power of 1C in the same voltage range, and all the electrochemical performance tests are carried out at room temperature.
FIG. 5 shows NaNi prepared in example 40.60Fe0.25Mn0.15O2The reversible specific capacity of the anode material in the first three weeks can reach 191.9mAh/g in the voltage range of 2.0-4.2V according to the charging and discharging curve in the first three weeks.
FIG. 6 shows NaNi prepared in example 50.70Fe0.20Mn0.10O2The reversible specific capacity of the first cycle of the charge-discharge curve around the front part of the anode material can reach 152.3mAh/g within the voltage range of 2.0-4.0V. FIG. 9 is a cycle performance curve of the capacitor, and the capacity retention rate of 100 cycles can reach 85% under the multiplying power of 1C.
FIG. 7 shows NaNi prepared in example 60.60Fe0.25Mn0.10Al0.05O2The reversible specific capacity of the positive electrode material in the first 2 weeks can reach 192.3mAh/g in a voltage range of 2.0-4.2V according to a charge-discharge curve in the first 2 weeks.
FIG. 8 shows NaNi prepared in example 80.70Fe0.2Mn0.05Ti0.05O2The reversible specific capacity of the positive electrode material at the first circumference can reach 192.5mAh/g within the voltage range of 2.0-4.2V according to the charge-discharge curve at the front circumference.
Fig. 10 is a graph showing the first cycle charge and discharge of a half cell test using a low nickel layered cathode material prepared by a comparative example of the present invention. It can be seen that the reversible specific capacity of the low-nickel layered material in the comparative example is only 131mAh/g in the first period within the voltage range of 2.0-4.0V, which is lower than 152mAh/g of the high-nickel layered material. The reversibility of the material structure is significantly reduced when the charge cut-off voltage is 4.2V. It can be seen that the high-nickel material can realize the high specific capacity and high energy density performance of the prepared sodium ion battery by the trivalent nickel participating in the oxidation reduction, and has good structural stability, thereby improving the cycle performance.
The high nickel layered oxide material of the sodium ion battery is synthesized by doping a small amount of other elements with electrochemical activity or inertia by using iron and manganese transition metal elements with rich resources. The nickel-based composite material is used as a high-nickel layered cathode material, is simple to synthesize, is easy for large-scale continuous production, and has the advantages of high reversible specific capacity, high energy density, high reversible charge-discharge potential and stable cycle. The sodium ion full cell constructed by the method has the characteristics of high average energy storage voltage, high energy density and high power density, can be used as green clean energy for power generation, smart grid peak regulation, distributed power stations, backup power supplies, communication base stations or energy storage equipment of low-speed electric automobiles and the like, and has excellent safety performance, rate capability and cycle performance.
The above-mentioned embodiments are intended to illustrate the objects, technical solutions and advantages of the present invention in further detail, and it should be understood that the above-mentioned embodiments are merely exemplary embodiments of the present invention, and are not intended to limit the scope of the present invention, and any modifications, equivalent substitutions, improvements and the like made within the spirit and principle of the present invention should be included in the scope of the present invention.

Claims (9)

1. The high nickel layered oxide material for the sodium ion battery is characterized in that the high nickel layer of the sodium ion batteryThe chemical formula of the oxide-like material is: na (Na)xNiaFebMncMd02±δ；
Wherein Ni, Fe and Mn are transition metal elements, and M is an element for doping and substituting a transition metal position; in the structure of the oxide material, ions of the transition metal sites form octahedral structures with the adjacent six oxygens and are coordinated with octahedral NaO6The layers are alternately arranged to form an O3 type sodium ion battery high nickel layered oxide material with a space group of R-3 m;
said M comprising in particular Li+，Mg2+，Ca2+，Cu2+，Zn2+，Al3+，B3+，Co3+，V3+，Y3+，Ti4+，Zr4+，Sn4+，Mo4+，Si4 +，Ru4+，Nb5+，Sb5+，Mo5+，Mo6+，W6+One or more of; x, a, b, c, d and 2+ delta are respectively the mole percentage of the corresponding elements, each component in the chemical general formula satisfies the charge conservation and the stoichiometric conservation, and x is more than or equal to 0.67 and less than or equal to 1, a is more than or equal to 0.5 and less than or equal to 1, b is more than or equal to 0.01 and less than or equal to 0.35, c is more than or equal to 0.01 and less than or equal to 0.35, d is more than or equal to 0 and less than or equal to 0.3, and delta is more than or equal to 0 and less than or equal to 0.1.
2. The nickel layered oxide material for sodium-ion batteries according to claim 1, wherein the nickel layered oxide material for sodium-ion batteries is used for a positive electrode active material of a sodium-ion secondary battery.
3. The method for preparing the nickel layered oxide material for the sodium-ion battery of claim 1, wherein the preparation method is a solid phase method, and comprises the following steps:
mixing a sodium source with the stoichiometric amount of 100-120 wt% of the required sodium, an oxide of nickel, an oxide of iron, an oxide of manganese and an oxide, hydroxide or nitrate of M according to a proportion, adding absolute ethyl alcohol or acetone, and grinding uniformly to obtain precursor powder; the sodium source comprises one or more of sodium nitrate, sodium peroxide, sodium superoxide, sodium carbonate, sodium hydroxide and sodium oxalate;
placing the obtained precursor powder tablet into a crucible, calcining for 10-24 hours at the temperature of 700-900 ℃ in the sintering atmosphere of air and/or oxygen, cooling to room temperature, and grinding to obtain the high-nickel layered anode oxide material;
wherein M is an element for doping and substituting transition metal sites, and specifically comprises Li+，Mg2+，Ca2+，Cu2+，Zn2+，Al3+，B3+，Co3+，V3+，Y3+，Ti4+，Zr4+，Sn4+，Mo4+，Si4+，Ru4+，Nb5+，Sb5+，Mo5+，Mo6+，W6+One or more of (a).
4. The method for preparing the high-nickel layered oxide material of the sodium-ion battery of claim 1, which is a coprecipitation-high temperature solid phase method, and comprises the following steps:
preparing a mixed solution of water-soluble Ni salt, Fe salt, Mn salt and M salt as a first solution according to the proportion of the required Ni, Fe, Mn and M; wherein the concentration of the cations in the first solution is 1-3 mol/L; m is an element for doping substitution of the transition metal site, and specifically comprises Li+，Mg2+，Ca2+，Cu2+，Zn2+，Al3+，B3+，Co3+，V3+，Y3+，Ti4+，Zr4+，Sn4+，Mo4+，Si4+，Ru4+，Nb5+，Sb5+，Mo5 +，Mo6+，W6+One or more of;
dissolving NaOH or KOH in deionized water with the concentration of 2-4mol/L, and adding a proper amount of ammonia water to form a second solution;
adding the first solution and the second solution into a reaction container simultaneously in the stirring process, and carrying out coprecipitation reaction at the temperature of 50-60 ℃, wherein the pH value is maintained at 10-12 in the reaction process;
aging for 0-24 hours after the coprecipitation reaction is finished, filtering the precipitate, washing and drying to obtain a hydroxide precursor of the transition metal elements which are uniformly distributed;
uniformly mixing the hydroxide precursor with a sodium source with the stoichiometric quantity of 100-120 wt.% of sodium, then preserving the heat for 3-6 hours at the temperature of 400-500 ℃ in an oxygen atmosphere, calcining the mixture for 10-24 hours at the temperature of 700-900 ℃, and cooling the calcined mixture to room temperature to obtain the high-nickel layered oxide material of the sodium-ion battery; the sodium source includes: one or more of sodium nitrate, sodium peroxide, sodium superoxide, sodium carbonate, sodium hydroxide and sodium oxalate.
5. The method for preparing the high-nickel layered oxide material of the sodium-ion battery of claim 1, which is characterized in that the preparation method is a sol-gel method and comprises the following steps:
weighing sodium ions, soluble salts of transition metal ions and a proper amount of citric acid which are 100-120 wt.% of the stoichiometric ratio according to the required stoichiometric ratio, and dissolving the sodium ions, the soluble salts of the transition metal ions and the citric acid in deionized water to form slurry of a mixed solution; wherein the transition metal ions comprise Ni, Fe, Mn; the transition metal ions also comprise an element M for doping substitution of transition metal sites; m in particular comprises Li+，Mg2+，Ca2+，Cu2+，Zn2+，Al3+，B3+，Co3+，V3+，Y3+，Ti4+，Zr4+，Sn4+，Mo4+，Si4+，Ru4+，Nb5+，Sb5+，Mo5+，Mo6+，W6+One or more of;
heating and evaporating the obtained slurry in an oil bath pan to dryness to form dry gel;
and (3) placing the obtained xerogel in a crucible, pretreating for 3-6 hours at the temperature of 400-500 ℃, grinding the powder obtained by pretreatment, placing a pressed sheet in the crucible, calcining for 10-24 hours at the temperature of 700-900 ℃ in the air and/or oxygen atmosphere, cooling to room temperature, and grinding to obtain the high-nickel layered oxide material of the sodium ion battery.
6. An electrode material for a sodium ion secondary battery, characterized in that the electrode material comprises: a conductive additive, a binder and the sodium ion battery nickel-rich layered oxide material of claim 1 or 2.
7. The sodium ion battery high-nickel layered oxide material of claim 6, wherein the conductive additive comprises: one or more of carbon black, acetylene black, graphite powder, carbon nanotubes, graphene and nitrogen-doped carbon;
the binder comprises one or more of polyvinylidene fluoride (PVDF), sodium alginate, sodium carboxymethyl cellulose (CMC) and Styrene Butadiene Rubber (SBR).
8. A positive electrode sheet comprising the electrode material for sodium-ion secondary batteries according to claim 6 or 7.
9. A sodium ion secondary battery comprising the positive electrode sheet as defined in claim 8.
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