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CN111162250A - High sodium content P2 phase layered oxide material with valence of pure cation, preparation method and use - Google Patents

High sodium content P2 phase layered oxide material with valence of pure cation, preparation method and use Download PDF

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CN111162250A
CN111162250A CN201811319331.6A CN201811319331A CN111162250A CN 111162250 A CN111162250 A CN 111162250A CN 201811319331 A CN201811319331 A CN 201811319331A CN 111162250 A CN111162250 A CN 111162250A
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sodium
oxide material
layered oxide
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胡勇胜
赵成龙
陈立泉
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Institute of Physics of CAS
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    • H—ELECTRICITY
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • H01M10/00—Secondary cells; Manufacture thereof
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    • H—ELECTRICITY
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    • H01M4/00—Electrodes
    • 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
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • 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
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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 discloses a pure cation valence-changing high-sodium-content P2 phase layered oxide material, a preparation method and application thereof, wherein the chemical general formula of the material is as follows: na (Na)x[LiiNijMnkMy]O2+β(ii) a Li, Ni, Mn and M occupy the position of transition metal ions in the crystal structure together; wherein M is an element for doping substitution of the transition metal site, and is Cu2+，Mg2+，Mn2+,Zn2+，Al3+，B3+，Zr4+，Ti4+X, y, i, j, k, β are mole percentages of corresponding elements respectively, wherein the relationship among x, y, i, j, k, β satisfies that y + i + j + k is 1, x + my + i +2j +4k is 2(2+ β), x is more than or equal to 0.8 and less than or equal to 0.85, i is more than 0 and less than or equal to 0.1, j is more than 0 and less than or equal to 0.4, k is more than 0 and less than or equal to 0.65, β is more than or equal to 0.05, M is a valence state of M, a space group of the layered oxide material is P63/mmc or P63And/mcm. The material is used for the positive active material of the sodium ion secondary battery, in the charging and discharging process, the charge compensation is completely realized by the gain and loss of electrons of transition metal cations, the structural change caused by the participation of anions in valence change is effectively inhibited, and the cycling stability of the material is greatly improved.

Description

Pure cation valence-change high-sodium-content P2 phase layered oxide material, preparation method and application
Technical Field
The invention relates to the technical field of materials, in particular to a pure cation valence-changing high-sodium-content P2 phase layered oxide material, a preparation method and application.
Background
Along with the development and progress of society, the demand of human beings for energy is increasing, but the application of traditional fossil energy such as coal, oil, natural gas is gradually limited in many aspects due to the gradual depletion of resources and the increasingly severe urban environmental pollution and greenhouse effect problems caused by the traditional fossil energy, so that the development of sustainable clean energy is always a direction of concern of various countries. However, in the process of converting wind energy, solar energy, tidal energy and the like into electric energy, the renewable energy sources are greatly limited by natural conditions and have the characteristics of obvious time discontinuity, spatial distribution nonuniformity and the like, so that the electric power provided by the renewable energy sources is poor in controllability and stability and cannot be directly input into a power grid for use. Therefore, only by matching with a high-performance large-scale energy storage system, the problem of time difference contradiction between power generation and power utilization is solved, and the quality of electric energy is adjusted, so that reliable power supply of a power system can be ensured. At present, the sustainable development of energy in China has urgent need for large-scale energy storage technology, and the method is also a research hotspot in all countries in the world.
The existing energy storage modes at present are physical energy storage and chemical energy storage. Pumped storage in physical energy storage is the most used at present, the energy storage is the largest, but pumped storage is limited by geographical positions, the construction period is long, and other physical energy storage such as compressed air energy storage, flywheel energy storage and the like are not on a large scale. Electrochemical energy storage refers to the storage or release of electricity by reversible chemical reactions, and is generally concerned by people with the advantages of high energy conversion efficiency, high power density, long cycle life, short construction period, low maintenance cost and the like.
At present, electrochemical energy storage mainly includes high-temperature sodium-sulfur batteries, flow batteries, lead-acid batteries, lithium ion batteries and the like. The working temperature of the Na-S battery is 300 ℃, the metal sodium and elemental sulfur are in a molten state, and if the materials are damaged at high temperature, fire is easily caused in a battery module, so that the safety problem is great, and the Na-S battery cannot be applied in a large scale. The flow battery has low energy density and large volume. Compared with Ni-Cd batteries, lead-acid batteries have no memory effect and low cost, always account for most of the energy storage market at present, and are widely applied. But the disadvantages are obvious, such as lead pollution to environment, low energy density of the battery, heavy mass, large volume and increased maintenance cost. Because the energy storage system needs to have the characteristics of low cost, environmental protection, long service life, high safety performance and the like, among numerous electrochemical energy storage materials, lithium ion secondary batteries and sodium ion secondary batteries become important technologies in energy storage technology.
The lithium ion battery used as electrochemical energy storage has the advantages of high energy density, high cycle stability, long cycle life, small volume, light weight, no pollution and the like, and is widely applied to daily life. Sodium is considered to be an alkali metal element in the periodic table with lithium and therefore has similar physicochemical properties. The sodium ion battery and the lithium ion battery have similar charge-discharge storage mechanisms, more importantly, the sodium is abundant and widely distributed in nature, and has a very obvious price advantage. Besides the low price of sodium ions, aluminum foils can be used as the positive and negative current collectors of the sodium ion battery, while the negative electrode of the lithium ion battery can only use copper, which is obviously more expensive than aluminum, so that the raw material cost is low and the raw material is easy to obtain, and the sodium ion battery is more and more widely concerned worldwide due to the advantages.
The layered positive electrode material is also a hot spot of recent research, and is Na in P2 phasexTMO2And NaTMO in O3 phase2Is currently the most studied material [ Physical B&C,1980,99,81-85 ], high sodium content of O3 phase, high first cycle charge capacity, but poor electrochemical cycle performance, and air and water resistanceSensitivity, and certain difficulty in application; the P2 phase has good stability in the electrochemical cycle process due to the large space occupied by sodium ions, and the sodium ions are relatively quickly deintercalated, but most P2 phase materials are unstable in air and generally have lower first-cycle charge capacity due to lower sodium content. In 2001, Lu et al prepared Na in P2 phase2/3Ni1/3Mn2/3O2The material is characterized by electrochemical performance, the material has a capacity of 160mAh/g between 2.0 and 4.5V [ Z.H.Lu and J.R.Dahn, J.electrochem.Soc.,2001,148, A1225-A1229 ], but the electrochemical curve shows a plurality of platforms and extremely poor cycle stability.
Disclosure of Invention
The embodiment of the invention provides a pure cation valence-changing high-sodium-content P2 phase layered oxide material, a preparation method and application. The layered oxide material with high sodium content P2 phase and pure cation valence change is simple to prepare, the abundance of the contained metal elements in the earth crust is high, and the manufacturing cost is low. The high sodium content effectively increases the first-cycle charge capacity and can suppress its phase transition problem at P2-O2 in the high voltage range. The pure cation valence-changed P2 phase layered oxide material with high sodium content is used as a positive electrode active material of a sodium ion secondary battery. In the process of charging and discharging, charge compensation is completely realized by gain and loss of electrons of transition metal cations, so that structural change caused by participation of anions in valence change is effectively inhibited, and the cycling stability of the material is greatly improved. The sodium ion secondary battery using the pure cation valence-changing high-sodium-content P2 phase layered oxide material has the advantages of high first-cycle efficiency, excellent cycle performance, good safety performance and great practical value, and can be used for large-scale energy storage equipment of solar power generation, wind power generation, smart grid peak regulation, distributed power stations, backup power supplies or communication base stations.
In a first aspect, the invention discloses a pure cation valence-change high-sodium-content P2 phase layered oxide material: the chemical general formula is: na (Na)x[LiiNijMnkMy]O2+β；
Li, Ni, Mn, M occupy transition metals in crystal structureIon position; wherein M is an element for doping substitution of transition metal site, specifically Cu2+，Mg2+，Mn2+,Zn2+，Al3+，B3+，Zr4+，Ti4+One or more of;
the x, y, i, j, k and β are respectively the mole percentages of the corresponding elements, wherein the relationship among the x, y, i, j, k and β satisfies that y + i + j + k is 1, and x + my + i +2j +4k is 2(2+ β), x is more than or equal to 0.8 and less than or equal to 0.85, i is more than 0 and less than or equal to 0.1, j is more than 0 and less than or equal to 0.4, k is more than 0 and less than or equal to 0.65, 0.05 is more than or equal to β and less than or equal to 0.05, and M is the valence state of the M;
the space group of the layered oxide material is P63/mmc or P63The corresponding structure is P2 phase structure;
the pure cation valence-change high-sodium-content P2 phase layered oxide material is used as a positive electrode active material of a sodium ion secondary battery; during charging and discharging, charge compensation is completely realized by electron gain and loss of transition metal cations.
In a second aspect, embodiments of the present invention provide a method for preparing a layered oxide material as described in the first aspect, where the method is a solid phase method, and the method includes:
mixing 100-110 wt% of stoichiometric sodium carbonate, nickel, manganese and lithium oxide and M oxide or carbonate in required stoichiometric amount in proportion into a precursor; m is specifically Cu2+，Mg2+，Mn2+,Zn2+，Al3+，B3+，Zr4+，Ti4+One or more of;
uniformly mixing the precursors by adopting a ball milling method to obtain precursor powder;
placing the precursor powder in a muffle furnace, and carrying out heat treatment for 6-48 hours at the temperature of 800-1100 ℃ in an air atmosphere;
and grinding the precursor powder after the heat treatment to obtain the layered oxide material.
In a third aspect, embodiments of the present invention provide a method for preparing a layered oxide material as described in the first aspect above, the method being a combustion method comprising:
mixing 100-110 wt% of the stoichiometric amount of sodium nitrate, nitrates of nickel, manganese and lithium and the nitrate of M in the stoichiometric amount into a precursor in proportion; m is specifically Cu2+，Mg2+，Mn2+,Zn2+，Al3+，B3+，Zr4+，Ti4+One or more of;
adding acetylacetone into the precursor, and uniformly stirring to form slurry;
drying the slurry at 80 ℃ to obtain precursor powder;
placing the precursor powder in a muffle furnace, and carrying out heat treatment for 6-48 hours at the temperature of 800-1100 ℃ in an air atmosphere;
and grinding the precursor powder after the heat treatment to obtain the layered oxide material.
In a fourth aspect, an embodiment of the present invention provides a method for preparing a layered oxide material according to the first aspect, where the method is a spray drying method, and includes:
mixing 100-110 wt% of the stoichiometric amount of sodium nitrate, nitrates of nickel, manganese and lithium and the nitrate of M in the stoichiometric amount into a precursor in proportion; m is specifically Cu2+，Mg2+，Mn2+,Zn2+，Al3+，B3+，Zr4+，Ti4+One or more of;
adding ethanol or water into the precursor, and uniformly stirring to form slurry;
spray drying the slurry to obtain precursor powder;
placing the precursor powder in a muffle furnace, and carrying out heat treatment for 6-48 hours at the temperature of 800-1100 ℃ in an air atmosphere;
and grinding the precursor powder after the heat treatment to obtain the layered oxide material.
In a fifth aspect, embodiments of the present invention provide a method for preparing a layered oxide material according to the first aspect, where the method is a sol-gel method, and the method includes:
dissolving sodium salt, nitrates of nickel, manganese and lithium and nitrates or sulfates containing a doping element M, which are 100 to 110 weight percent of the stoichiometric amount of the required sodium, into water or ethanol according to the stoichiometric ratio to be mixed into precursor solution; the sodium salt is one of sodium acetate, sodium nitrate, sodium carbonate or sodium sulfate, and M is Cu2+，Mg2+，Mn2+,Zn2+，Al3+，B3+，Zr4+，Ti4+One or more of;
stirring at 50-100 ℃, adding a proper amount of chelating agent, and evaporating to dryness to form precursor gel;
placing the precursor gel in a crucible, and presintering for 3 hours at 300-450 ℃ in air atmosphere;
then carrying out heat treatment for 6-48 hours in an air atmosphere at 800-1100 ℃;
and grinding the precursor powder after the heat treatment to obtain the layered oxide material.
In a sixth aspect, embodiments of the present invention provide a method for preparing a layered oxide material as described in the first aspect, where the method is a co-precipitation method, and the method includes:
dissolving 100-110 wt% of the stoichiometric amount of sodium nitrate, nitrates of nickel, manganese and lithium and the nitrate of M in the stoichiometric amount into water in proportion to form a precursor solution; m is specifically Cu2+，Mg2+，Mn2+,Zn2+，Al3+，B3+，Zr4+，Ti4+One or more of;
slowly dripping the precursor solution into an ammonia water solution with certain concentration and pH value by using a peristaltic pump to generate a precipitate;
cleaning the obtained precipitate with deionized water, drying, and uniformly mixing with sodium carbonate according to a stoichiometric ratio to obtain a precursor;
placing the precursor in a crucible, and carrying out heat treatment for 6-48 hours in an air atmosphere at 800-1100 ℃ to obtain precursor powder;
and grinding the precursor powder to obtain the layered oxide material.
In a seventh aspect, an embodiment of the present invention provides a positive electrode tab, where the positive electrode tab includes:
a current collector, a conductive additive and a binder coated on the current collector, and a layered oxide material as described above in the first aspect.
In an eighth aspect, an embodiment of the present invention provides a sodium-ion secondary battery including the positive electrode sheet described in the seventh aspect.
In a ninth aspect, embodiments of the present invention provide a use of a sodium ion secondary battery for large-scale energy storage equipment of solar power generation, wind power generation, smart grid peak shaving, distributed power plants, backup power sources, or communication base stations.
The embodiment of the invention provides a pure cation valence-changing high-sodium-content P2 phase layered oxide material, a preparation method and application. The layered oxide material is simple to prepare, the abundance of the contained metal elements in the earth crust is high, and the manufacturing cost is low. The high sodium content effectively increases the first-cycle charge capacity and can suppress its phase transition problem at P2-O2 in the high voltage range. The sodium ion secondary battery using the layered oxide material has high first-cycle efficiency, excellent cycle performance, good safety performance and great practical value, and can be used for large-scale energy storage equipment of solar power generation, wind power generation, smart grid peak regulation, distributed power stations, backup power supplies or communication base stations.
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 plurality of layered oxide materials of different elemental mole percentages provided by an embodiment of the present invention;
FIG. 2 is a flow chart of a method for preparing a layered oxide material by a solid phase method according to example 2 of the present invention;
FIG. 3 is a flow chart of a method for preparing a layered oxide material by a combustion method according to example 3 of the present invention;
fig. 4 is a flowchart of a method for preparing a layered oxide material by a sol-gel method through a spray drying method according to embodiment 4 of the present invention;
FIG. 5 is a flowchart of a method for preparing a layered oxide material by a sol-gel method according to example 5 of the present invention;
FIG. 6 is a flowchart of a method for preparing a layered oxide material by a sol-gel method according to example 6 of the present invention;
FIG. 7 shows the solid phase synthesis of Na according to example 7 of the present invention0.83Ni0.31Mn0.62Li0.07O2SEM image of material;
fig. 8 is a charge-discharge curve diagram of a sodium ion battery at 2.0-4.0V according to embodiment 7 of the present invention;
fig. 9 is a cycle chart of a sodium-ion battery provided in embodiment 7 of the present invention.
Detailed Description
The present invention will be described in further detail with reference to examples, but the present invention is not limited thereto.
Example 1
The embodiment provides a pure cation valence-changing high-sodium-content P2 phase layered oxide material, which has a chemical general formula as follows: na (Na)x[LiiNijMnkMy]O2+β；
Wherein Li, Ni, Mn and M occupy the transition metal ion position in the crystal structure together; m is an element for doping substitution of transition metal site, and M is Cu2+，Mg2+，Mn2+,Zn2+，Al3+，B3+，Zr4+，Ti4+X, y, i, j, k and β are respectively the mole percentage of the corresponding elements, the relationship among x, y, i, j, k and β satisfies that y + i + j + k is 1, and x + my + i +2j +4k is 2(2+ β), wherein x is more than or equal to 0.8 and less than or equal to 0.85, i is more than or equal to 0 and less than or equal to 0.1, j is more than 0 and less than or equal to 0.4, k is more than 0 and less than or equal to 0.65, β is more than or equal to-0.05, and M is the valence state of M.
The space group of P2 phase layered oxide material with high sodium content is P63/mmc or P63And/mcm, corresponding to the structure P2 phase. The XRD pattern in several embodiments can be seen in particular in fig. 1.
The pure cation valence-change high-sodium-content P2 phase layered oxide material is used as a positive electrode active material of a sodium ion secondary battery. In the process of charging and discharging, charge compensation is completely realized by gain and loss of electrons of transition metal cations, so that structural change caused by participation of anions in valence change is effectively inhibited, and the cycling stability of the material is greatly improved.
The layered oxide material of the invention contains metal elements with high abundance in the earth crust and has low manufacturing cost. The high sodium content effectively increases the first-cycle charge capacity and can suppress its phase transition problem at P2-O2 in the high voltage range. The sodium ion secondary battery using the layered oxide material has high first-cycle efficiency, excellent cycle performance, good safety performance and great practical value, and can be used for large-scale energy storage equipment of solar power generation, wind power generation, smart grid peak regulation, distributed power stations, backup power supplies or communication base stations.
The following is a description of the preparation process for obtaining this material.
Example 2
The embodiment provides a preparation method of a pure cation valence-changing high-sodium-content P2 phase layered oxide material, specifically a solid phase method, as shown in FIG. 2, which includes:
step 201, mixing sodium carbonate with the stoichiometric quantity of 100-110 wt% of required sodium, oxides of nickel, manganese and lithium and oxide or carbonate with the stoichiometric quantity of M into a precursor according to a proportion;
m is as described in the examples above, in particular Cu2+，Mg2+，Mn2+,Zn2+，Al3+，B3+，Zr4+，Ti4+One or more of; the following embodiments are the same and will not be described again.
Step 202, uniformly mixing the precursors by adopting a ball milling method to obtain precursor powder;
step 203, placing the precursor powder in a muffle furnace, and carrying out heat treatment for 6-48 hours at 800-1100 ℃ in an air atmosphere;
and 204, grinding the precursor powder after heat treatment to obtain the layered oxide material.
The preparation method of the pure cation valence-changing high-sodium-content P2 phase layered oxide material provided by the embodiment can be used for preparing the layered oxide material described in the above embodiment 1. The method provided by the embodiment is simple and easy to implement, low in cost, safe and nontoxic in used materials, and suitable for large-scale manufacturing.
Example 3
The embodiment provides a preparation method of a pure cation valence-changing high-sodium-content P2 phase layered oxide material, in particular to a combustion method, as shown in FIG. 3, which comprises the following steps:
301, mixing sodium nitrate with the stoichiometric quantity of 100-110 wt% of the required sodium, nitrates of nickel, manganese and lithium and nitrate with the stoichiometric quantity of M into a precursor according to a proportion;
step 302, adding acetylacetone into the precursor, uniformly stirring to form slurry, and drying the slurry at 80 ℃ to obtain precursor powder;
303, placing the precursor powder in a muffle furnace, and carrying out heat treatment for 6-48 hours at the temperature of 800-1100 ℃ in an air atmosphere;
and 304, grinding the precursor powder after heat treatment to obtain the layered oxide material.
The preparation method of the pure cation valence-changing high-sodium-content P2 phase layered oxide material provided in this example can be used to prepare the high-sodium-content P2 phase layered oxide material described in example 1 above. The method provided by the embodiment is simple and easy to implement, low in cost, safe and nontoxic in used materials, and suitable for large-scale manufacturing.
Example 4
The embodiment provides a preparation method of a pure cation valence-changing high-sodium-content P2 phase layered oxide material, specifically a sol-gel method, as shown in FIG. 4, which includes:
step 401, mixing sodium nitrate with the stoichiometric quantity of 100 wt% -110 wt% of the required sodium, nitrates of nickel, manganese and lithium and nitrates with the stoichiometric quantity of M into a precursor according to a proportion;
step 402, adding ethanol or water into the precursor, and uniformly stirring to form slurry;
step 403, spray drying the slurry to obtain precursor powder;
404, placing the precursor powder in a muffle furnace, and carrying out heat treatment for 6-48 hours at the temperature of 800-1100 ℃ in an air atmosphere;
and 405, grinding the precursor powder after heat treatment to obtain the layered oxide material.
The preparation method of the pure cation valence-changing high-sodium-content P2 phase layered oxide material provided in this example can be used to prepare the high-sodium-content P2 phase layered oxide material described in example 1 above. The method provided by the embodiment is simple and easy to implement, low in cost, safe and nontoxic in used materials, and suitable for large-scale manufacturing.
Example 5
The embodiment provides a method for preparing a P2 phase layered oxide material with high sodium content and valence-change of pure cations, in particular to a sol-gel method, as shown in fig. 5, which includes:
step 501, dissolving 100 wt% -110 wt% of stoichiometric sodium salt, nitrates of nickel, manganese and lithium and nitrates or sulfates containing doping elements M in water or ethanol according to stoichiometric ratio to form precursor solution;
wherein the sodium salt is one of sodium acetate, sodium nitrate, sodium carbonate or sodium sulfate.
Step 502, stirring at 50-100 ℃, adding a proper amount of chelating agent, and evaporating to dryness to form precursor gel;
step 503, placing the precursor gel in a crucible, and presintering for 3 hours at 300-450 ℃ in air atmosphere;
step 504, placing the precursor powder in a muffle furnace, and performing heat treatment for 6-48 hours at 800-1100 ℃ in an air atmosphere;
and 505, grinding the precursor powder after heat treatment to obtain the layered oxide material.
The preparation method of the pure cation valence-changing high-sodium-content P2 phase layered oxide material provided in this example can be used to prepare the high-sodium-content P2 phase layered oxide material described in example 1 above. The method provided by the embodiment is simple and easy to implement, low in cost, safe and nontoxic in used materials, and suitable for large-scale manufacturing.
Example 6
The embodiment provides a preparation method of a pure cation valence-changing P2 phase layered oxide material with high sodium content, specifically a coprecipitation method, as shown in FIG. 6, which includes:
step 601, dissolving 100-110 wt% of sodium nitrate, nitrates of nickel, manganese and lithium, nitrate and nitrate of M in required stoichiometric amount in water according to a proportion to form a precursor solution;
step 602, slowly dripping the precursor solution into an ammonia water solution with a certain concentration and pH value by using a peristaltic pump to generate a precipitate;
step 603, cleaning the obtained precipitate with deionized water, drying, and uniformly mixing with sodium carbonate according to a stoichiometric ratio to obtain a precursor;
step 604, placing the precursor powder in a muffle furnace, and carrying out heat treatment for 6-48 hours at 800-1100 ℃ in an air atmosphere;
and 605, grinding the precursor powder after the heat treatment to obtain the layered oxide material.
The preparation method of the pure cation valence-changing high-sodium-content P2 phase layered oxide material provided in this example can be used to prepare the layered oxide material described in example 1 above. The method provided by the embodiment is simple and easy to implement, low in cost, safe and nontoxic in used materials, and suitable for large-scale manufacturing.
In order to better understand the technical scheme provided by the invention, the following specific examples respectively illustrate the specific processes for preparing the P2 phase layered oxide material with high sodium content by using the methods provided by the above embodiments of the invention, and the methods and battery characteristics for applying the same to the secondary battery.
Example 7
In this example, the solid phase method described in the foregoing example 2 is used to prepare a P2 phase layered oxide material with high sodium content, which includes:
mixing Na2CO3(analytical grade), Li2CO3(analytically pure), NiO (analytically pure), MnO2(analytically pure) mixing according to the required stoichiometric ratio; grinding for half an hour in an agate mortar to obtain a precursor; tabletting the precursor and transferring to Al2O3Treating in a crucible at 1000 deg.C for 36 hr to obtain black powder of layered oxide material Na0.83Ni0.31Mn0.62Li0.07O2The XRD pattern is shown in figure 1, and Na is seen from the XRD pattern0.83Ni0.31Mn0.62Li0.07O2Has a crystal structure of P2 phase layered structure. FIG. 7 is an SEM image of this material, with an average particle diameter of about 5-10 microns.
The prepared layered oxide material is used for preparing a sodium ion battery as an active substance of a battery anode material, and the preparation method comprises the following specific steps: the prepared Na0.83Ni0.31Mn0.62Li0.07O2Mixing the powder with acetylene black and a binder polyvinylidene fluoride (PVDF) according to a mass ratio of 80:10:10, adding a proper amount of N-methylpyrrolidone (NMP) solution, grinding the mixture in a normal-temperature drying environment to form slurry, then uniformly coating the slurry on a current collector aluminum foil, drying the slurry under an infrared lamp, and cutting the dried slurry into (8 x 8) mm2The pole piece of (2). The pole piece is dried for 10 hours at 110 ℃ under vacuum condition, and then transferred to a glove box for standby.
The assembly of the simulated cell was carried out in a glove box under Ar atmosphere, with sodium metal as the counter electrode and NaPO6:NaClO4(NaPO6:NaClO41: 1)/Ethylene Carbonate (EC) (EC: DEC: 1)) solution as electricityAnd (4) decomposing the solution to assemble the CR2032 button cell. By using a constant-current ten-week charge-discharge cycle curve, it can be seen that the first-week discharge specific capacity can reach 100mAh/g, and the tenth-week coulombic efficiency is about 100%, as shown in FIG. 8; at a magnification of 3C, the capacity retention after 2000 cycles was above 75%, see fig. 9.
Example 8
In this example, the solid phase method described in example 2 above was used to prepare a P2 phase layered oxide material with high sodium content.
Mixing Na2CO3(analytical grade), Li2CO3(analytically pure), NiO (analytically pure), MnO2(analytically pure) mixing according to the required stoichiometric ratio; grinding for half an hour in an agate mortar to obtain a precursor; tabletting the precursor and transferring to Al2O3Treating in a crucible at 1000 deg.C for 36 hr to obtain black powder of layered oxide material Na0.85Ni0.30Mn0.62Li0.08O2The XRD pattern is shown in figure 1, and Na is seen from the XRD pattern0.85Ni0.30Mn0.62Li0.08O2Has a crystal structure of P2 phase layered structure.
The prepared layered oxide material is used as an active substance of a battery anode material for preparing a sodium ion battery, and an electrochemical charge and discharge test is carried out. The procedure and test method were the same as in example 7. The test voltage range is 2.0V-4.0V, and the reversible specific capacity of the material is shown in Table 1.
Example 9
In this example, the combustion process described in example 3 above was used to prepare a layered oxide material.
Adding NaNO3(analytically pure), LiNO3(analytically pure), Cu (NO)3)2(analytically pure), Ni (NO)3)2·6H2OMn(NO3)2·4H2Mixing O according to the required stoichiometric ratio; stirring uniformly in agate mortar to form a precursor, tabletting the precursor and transferring to Al2O3Adding 10ml of acetylacetone into the crucible to form slurry; drying the slurry at 80 ℃Then precursor powder is obtained; placing the precursor powder in a muffle furnace, and carrying out heat treatment for 48 hours at 1100 ℃ in an air atmosphere; and grinding the precursor powder after the heat treatment to obtain the layered oxide material. The XRD pattern is shown in figure 1, and from the XRD pattern, Na is seen0.80Cu0.05Ni0.26Mn0.63Li0.06O2Has a crystal structure of P2 phase layered structure.
The prepared layered oxide material is used as an active substance of a battery anode material for preparing a sodium ion battery, and an electrochemical charge and discharge test is carried out. The procedure and test method were the same as in example 7. The test voltage range is 2.0V-4.0V, and the reversible specific capacity of the material is shown in Table 1.
Example 10
In this example, the layered oxide material was prepared using the solid phase method described in example 2 above.
Mixing Na2CO3(analytical grade), Li2CO3(analytically pure), NiO (analytically pure), CuO (analytically pure), MnO2(analytically pure) mixing according to the required stoichiometric ratio; grinding for half an hour in an agate mortar to obtain a precursor; tabletting the precursor and transferring to Al2O3Treating the mixture in a crucible for 36 hours at 1000 ℃ in a muffle furnace; placing the precursor powder in a muffle furnace, and carrying out heat treatment for 36 hours at 900 ℃ in an air atmosphere; and grinding the precursor powder after the heat treatment to obtain the layered oxide material. The XRD pattern is shown in figure 1, and from the XRD pattern, Na is seen0.83Co0.05Ni0.26Mn0.62Li0.07O2Has a crystal structure of P2 phase layered structure.
The prepared layered oxide material is used as an active substance of a battery anode material for preparing a sodium ion battery, and an electrochemical charge and discharge test is carried out. The procedure and test method were the same as in example 7. The test voltage range is 2.0V-4.0V, and the reversible specific capacity of the material is shown in Table 1.
Example 11
In this example, the sol-gel method described in example 5 above was used to prepare a layered oxide material.
Adding NaNO3(analytically pure), LiNO3(analytically pure), Ni (NO)3)2·6H2O (analytically pure) Mn (NO)3)2·4H2Mixing O according to the required stoichiometric ratio to obtain a precursor; adding ethanol into the precursor, and uniformly stirring to form slurry; drying the slurry at 80 ℃ to obtain precursor powder; placing the precursor powder in a muffle furnace, and carrying out heat treatment for 24 hours at 1050 ℃ in an air atmosphere; grinding the heat-treated precursor powder to obtain Na0.83Ni0.31Mn0.62Li0.07O2A layered oxide material.
The prepared layered oxide material is used as an active substance of a battery anode material for preparing a sodium ion battery, and an electrochemical charge and discharge test is carried out. The procedure and test method were the same as in example 7. The test voltage range is 2.0V-4.0V, and the reversible specific capacity of the material is shown in Table 1.
Example 12
In this example, the layered oxide material was prepared using the co-precipitation method described in example 6 above.
Adding NaNO3(analytically pure), LiNO3(analytically pure), Ni (NO)3)2·6H2O (analytically pure) Mn (NO)3)2·4H2Mixing O according to the required stoichiometric ratio to form a solution; slowly dripping the solution into an ammonia water solution with certain concentration and pH value by using a peristaltic pump to generate a precipitate; cleaning the obtained precipitate with deionized water, drying, and uniformly mixing with sodium carbonate according to a stoichiometric ratio to obtain a precursor; placing the precursor in a crucible, and carrying out heat treatment for 18 hours in an air atmosphere at 1000 ℃ to obtain precursor powder; grinding the heat-treated precursor powder to obtain Na0.83Ni0.31Mn0.62Li0.07O2A layered oxide material.
The prepared layered oxide material is used as an active substance of a battery anode material for preparing a sodium ion battery, and an electrochemical charge and discharge test is carried out. The procedure and test method were the same as in example 7. The test voltage range is 2.0V-4.0V, and the reversible specific capacity of the material is shown in Table 1.
Example 13
In this example, the combustion process described in example 3 above was used to prepare a layered oxide material.
Adding NaNO3(analytically pure), LiNO3(analytically pure), Ni (NO)3)2·6H2O Mn(NO3)2·4H2Mixing O according to the required stoichiometric ratio; stirring uniformly in agate mortar to form a precursor, tabletting the precursor and transferring to Al2O3Adding 10ml of acetylacetone into the crucible to form slurry; drying the slurry at 80 ℃ to obtain precursor powder; placing the precursor powder in a muffle furnace, and carrying out heat treatment for 24 hours at 950 ℃ in an air atmosphere; grinding the heat-treated precursor powder to obtain Na0.83Ni0.31Mn0.62Li0.07O2A layered oxide material.
The prepared layered oxide material is used as an active substance of a battery anode material for preparing a sodium ion battery, and an electrochemical charge and discharge test is carried out. The procedure and test method were the same as in example 7. The test voltage range is 2.0V-4.0V, and the reversible specific capacity of the material is shown in Table 1.
Example 14
In this example, the layered oxide material was prepared using the co-precipitation method described in example 6 above.
Adding NaNO3(analytically pure), LiNO3(analytically pure), Ni (NO)3)2·6H2O (analytically pure), Mg (NO)3)2(analytically pure), Mn (NO)3)2·4H2Mixing O according to the required stoichiometric ratio to form a solution; slowly dripping the solution into an ammonia water solution with certain concentration and pH value by using a peristaltic pump to generate a precipitate; cleaning the obtained precipitate with deionized water, drying, and uniformly mixing with sodium carbonate according to a stoichiometric ratio to obtain a precursor; placing the precursor in a cruciblePerforming heat treatment for 48 hours in an air atmosphere at 1100 ℃ to obtain precursor powder; grinding the heat-treated precursor powder to obtain Na0.81Mg0.05Ni0.27Mn0.62Li0.05O2A layered oxide material.
The prepared layered oxide material is used as an active substance of a battery anode material for preparing a sodium ion battery, and an electrochemical charge and discharge test is carried out. The procedure and test method were the same as in example 7. The test voltage range is 2.0V-4.0V, and the reversible specific capacity of the material is shown in Table 1.
Figure BDA0001857131380000161
TABLE 1
The embodiment of the invention provides a pure cation valence-changing high-sodium-content P2 phase layered oxide material, a preparation method and application. The layered oxide material is simple to prepare, the abundance of the contained metal elements in the earth crust is high, and the manufacturing cost is low. The high sodium content effectively increases the first-cycle charge capacity and can suppress its phase transition problem at P2-O2 in the high voltage range. Meanwhile, the pure cation valence-changed P2 phase layered oxide material with high sodium content is used as a positive electrode active material of a sodium ion secondary battery. In the process of charging and discharging, charge compensation is completely realized by gain and loss of electrons of transition metal cations, so that structural change caused by participation of anions in valence change is effectively inhibited, and the cycling stability of the material is greatly improved.
The sodium ion secondary battery using the layered oxide material has high first-cycle efficiency, excellent cycle performance, good safety performance and great practical value, and can be used for large-scale energy storage equipment of solar power generation, wind power generation, smart grid peak regulation, distributed power stations, backup power supplies or communication base stations.
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)

1.一种纯阳离子变价的高钠含量P2相层状氧化物材料，其特征在于，所述层状氧化物材料的化学通式为：Nax[LiiNijMnkMy]O2+β；1. a high sodium content P2 phase layered oxide material of pure cation variable valence, is characterized in that, the chemical formula of described layered oxide material is: Na x [Li i Ni j Mn k My ] O 2 +β ; Li、Ni、Mn、M共同占据晶体结构中的过渡金属离子位置；其中，M为对过渡金属位进行掺杂取代的元素，具体为Cu2+，Mg2+，Mn2+,Zn2+，Al3+，B3+，Zr4+，Ti4+中的一种或多种；Li, Ni, Mn, and M jointly occupy the transition metal ion sites in the crystal structure; wherein, M is an element for doping and substituting transition metal sites, specifically Cu 2+ , Mg 2+ , Mn 2+ , Zn 2+ , one or more of Al 3+ , B 3+ , Zr 4+ , Ti 4+ ; 所述x，y，i，j,k,β分别为对应元素所占的摩尔百分比；其中x，y，i，j,k,β之间的关系满足y+i+j+k＝1，且x+my+i+2j+4k＝2(2+β)；0.8≤x≤0.85；0＜i≤0.1；0＜j≤0.4；0＜k≤0.65；-0.05≤β≤0.05；m为所述M的化合价态；The x, y, i, j, k, β are the mole percentages of the corresponding elements respectively; the relationship between x, y, i, j, k, β satisfies y+i+j+k=1, And x+my+i+2j+4k=2(2+β); 0.8≤x≤0.85; 0<i≤0.1; 0<j≤0.4; 0<k≤0.65; -0.05≤β≤0.05; m is the valence state of the M; 所述层状氧化物材料的空间群为P63/mmc或P63/mcm，对应结构为P2相结构；The space group of the layered oxide material is P6 3 /mmc or P6 3 /mcm, and the corresponding structure is a P2 phase structure; 所述纯阳离子变价的高钠含量P2相层状氧化物材料用于钠离子二次电池的正极活性材料；在充放电过程中，电荷补偿完全由过渡金属阳离子得失电子来实现。The high sodium content P2 phase layered oxide material with pure cations changing valence is used as a positive electrode active material for a sodium ion secondary battery; in the charging and discharging process, charge compensation is completely realized by the gain and loss of electrons from transition metal cations. 2.一种上述权利要求1所述的层状氧化物材料的制备方法，其特征在于，所述方法为固相法，包括：2. A method for preparing a layered oxide material according to claim 1, wherein the method is a solid-phase method, comprising: 将所需钠的化学计量100wt％～110wt％的碳酸钠，镍、锰、锂的氧化物，以及所需化学计量M的氧化物或碳酸盐按比例混合成前驱体；所述M具体为Cu2+，Mg2+，Mn2+,Zn2+，Al3+，B3+，Zr4+，Ti4+中的一种或多种；The required sodium stoichiometric 100wt% to 110wt% sodium carbonate, nickel, manganese, lithium oxides, and the required stoichiometric M oxides or carbonates are mixed into precursors in proportion; the M is specifically One or more of Cu 2+ , Mg 2+ , Mn 2+ , Zn 2+ , Al 3+ , B 3+ , Zr 4+ , Ti 4+ ; 采用球磨的方法将所述前驱体均匀混合得到前驱体粉末；The precursor powder is obtained by uniformly mixing the precursor by ball milling; 将所述前驱体粉末置于马弗炉内，在800℃～1100℃的空气气氛中热处理6～48小时；The precursor powder is placed in a muffle furnace, and heat-treated in an air atmosphere of 800°C to 1100°C for 6 to 48 hours; 将热处理后的前驱体粉末进行研磨，得到所述层状氧化物材料。The heat-treated precursor powder is ground to obtain the layered oxide material. 3.一种上述权利要求1所述的层状氧化物材料的制备方法，其特征在于，所述方法为燃烧法，包括：3. The method for preparing a layered oxide material according to claim 1, wherein the method is a combustion method, comprising: 将所需钠的化学计量100wt％～110wt％的硝酸钠，镍、锰、锂的硝酸盐，以及所需化学计量M的硝酸盐，按比例混合成前驱体；所述M具体为Cu2+，Mg2+，Mn2+,Zn2+，Al3+，B3+，Zr4+，Ti4+中的一种或多种；The required sodium stoichiometric 100wt% to 110wt% sodium nitrate, nickel, manganese, lithium nitrate, and the required stoichiometric M nitrate are mixed in proportion to form a precursor; the M is specifically Cu 2+ , Mg 2+ , Mn 2+ , Zn 2+ , Al 3+ , B 3+ , Zr 4+ , one or more of Ti 4+ ; 将所述前驱体加乙酰丙酮搅拌均匀形成浆料；adding acetylacetone to the precursor and stirring to form a slurry; 对所述浆料在80℃下进行干燥后得到前驱体粉末；drying the slurry at 80°C to obtain a precursor powder; 将所述前驱体粉末置于马弗炉内，在800℃～1100℃的空气气氛中热处理6～48小时；The precursor powder is placed in a muffle furnace, and heat-treated in an air atmosphere of 800°C to 1100°C for 6 to 48 hours; 将热处理后的前驱体粉末进行研磨，得到所述层状氧化物材料。The heat-treated precursor powder is ground to obtain the layered oxide material. 4.一种上述权利要求1所述的层状氧化物材料的制备方法，其特征在于，所述方法为喷雾干燥法，包括：4. A method for preparing a layered oxide material according to claim 1, wherein the method is a spray drying method, comprising: 将所需钠的化学计量100wt％～110wt％的硝酸钠，镍、锰、锂的硝酸盐，以及所需化学计量M的硝酸盐，按比例混合成前驱体；所述M具体为Cu2+，Mg2+，Mn2+,Zn2+，Al3+，B3+，Zr4+，Ti4+中的一种或多种；The required sodium stoichiometric 100wt% to 110wt% sodium nitrate, nickel, manganese, lithium nitrate, and the required stoichiometric M nitrate are mixed in proportion to form a precursor; the M is specifically Cu 2+ , Mg 2+ , Mn 2+ , Zn 2+ , Al 3+ , B 3+ , Zr 4+ , one or more of Ti 4+ ; 将所述前驱体加乙醇或水后搅拌均匀形成浆料；Add ethanol or water to the precursor and stir to form a slurry; 对所述浆料进行喷雾干燥后得到前驱体粉末；After spray-drying the slurry, a precursor powder is obtained; 将所述前驱体粉末置于马弗炉内，在800℃～1100℃的空气气氛中热处理6～48小时；The precursor powder is placed in a muffle furnace, and heat-treated in an air atmosphere of 800°C to 1100°C for 6 to 48 hours; 将热处理后的前驱体粉末进行研磨，得到所述层状氧化物材料。The heat-treated precursor powder is ground to obtain the layered oxide material. 5.一种上述权利要求1所述的层状氧化物材料的制备方法，其特征在于，所述方法为溶胶-凝胶法，包括：5. A method for preparing a layered oxide material according to claim 1, wherein the method is a sol-gel method, comprising: 将所需钠的化学计量100wt％～110wt％的钠盐，镍、锰、锂的硝酸盐，以及含掺杂元素M的硝酸盐或硫酸盐，按化学计量比溶于水或者溶于乙醇混合成前驱体溶液；所述钠盐为乙酸钠、硝酸钠、碳酸钠或硫酸钠中的一种，所述M具体为Cu2+，Mg2+，Mn2+,Zn2+，Al3+，B3+，Zr4+，Ti4+中的一种或多种；The stoichiometric 100wt% to 110wt% sodium salt of the required sodium, the nitrate of nickel, manganese, lithium, and the nitrate or sulfate containing the doping element M are dissolved in water or dissolved in ethanol according to the stoichiometric ratio and mixed into a precursor solution; the sodium salt is one of sodium acetate, sodium nitrate, sodium carbonate or sodium sulfate, and the M is specifically Cu 2+ , Mg 2+ , Mn 2+ , Zn 2+ , Al 3+ , one or more of B 3+ , Zr 4+ , Ti 4+ ; 在50℃～100℃下搅拌，并且加入适量螯合剂，蒸干形成前驱体凝胶；Stir at 50°C to 100°C, add an appropriate amount of chelating agent, and evaporate to dryness to form a precursor gel; 将所述前驱体凝胶置于坩埚中，在300℃～450℃的空气气氛下，预烧3个小时；The precursor gel is placed in a crucible, and pre-fired for 3 hours in an air atmosphere of 300°C to 450°C; 再在800℃～1100℃的空气气氛中热处理6～48小时；Heat treatment in an air atmosphere of 800℃～1100℃ for 6～48 hours; 将热处理后的前驱体粉末进行研磨，得到所述层状氧化物材料。The heat-treated precursor powder is ground to obtain the layered oxide material. 6.一种上述权利要求1所述的层状氧化物材料的制备方法，其特征在于，所述方法为共沉淀法，包括：6. A method for preparing a layered oxide material according to claim 1, wherein the method is a co-precipitation method, comprising: 将所需钠的化学计量100wt％～110wt％的硝酸钠，镍、锰、锂的硝酸盐，以及所需化学计量M的硝酸盐，按比例溶于水混合成前驱体溶液；所述M具体为Cu2+，Mg2+，Mn2+,Zn2+，Al3+，B3 +，Zr4+，Ti4+中的一种或多种；The stoichiometric 100wt% to 110wt% sodium nitrate of the required sodium, the nitrates of nickel, manganese, and lithium, and the nitrates of the required stoichiometric M are dissolved in water in proportion and mixed into a precursor solution; the M specific One or more of Cu 2+ , Mg 2+ , Mn 2+ , Zn 2+ , Al 3+ , B 3+ , Zr 4+ , Ti 4+ ; 用蠕动泵将所述前驱体溶液缓慢的滴加在一定浓度和pH值的氨水溶液中，生成沉淀物；Using a peristaltic pump, slowly drop the precursor solution into an aqueous ammonia solution with a certain concentration and pH value to generate a precipitate; 将得到的沉淀物用去离子水清洗干净，烘干后与碳酸钠按照化学计量比均匀混合得到的前驱物；The obtained precipitate is cleaned with deionized water, and the obtained precursor is uniformly mixed with sodium carbonate in a stoichiometric ratio after drying; 将所述前驱物置于坩埚中，在800℃～1100℃的空气气氛中热处理6～48小时，得到前驱体粉末；The precursor is placed in a crucible, and heat-treated in an air atmosphere at 800°C to 1100°C for 6 to 48 hours to obtain precursor powder; 将所述前驱体粉末进行研磨，得到所述层状氧化物材料。The precursor powder is ground to obtain the layered oxide material. 7.一种正极极片，其特征在于，所述正极极片包括：7. A positive pole piece, wherein the positive pole piece comprises: 集流体、涂覆于所述集流体之上的导电添加剂和粘结剂，以及上述权利要求1所述的层状氧化物材料。A current collector, a conductive additive and a binder coated on the current collector, and the layered oxide material of claim 1 above. 8.一种包括上述权利要求7所述的正极极片的钠离子二次电池。8. A sodium ion secondary battery comprising the positive electrode plate of claim 7. 9.一种如上述权利要求8所述的钠离子二次电池的用途，其特征在于，所述钠离子二次电池用于太阳能发电、风力发电、智能电网调峰、分布电站、后备电源或通信基站的大规模储能设备。9. A purpose of the sodium ion secondary battery as claimed in claim 8, wherein the sodium ion secondary battery is used for solar power generation, wind power generation, smart grid peak regulation, distributed power station, backup power supply or Large-scale energy storage equipment for communication base stations.
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