CN110504443B - Sodium-magnesium-manganese-based layered oxide material with anion valence change, preparation method and application - Google Patents
Sodium-magnesium-manganese-based layered oxide material with anion valence change, preparation method and application Download PDFInfo
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- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/16—Mechanical energy storage, e.g. flywheels or pressurised fluids
Abstract
The invention discloses a sodium-magnesium-manganese-based layered oxide material with anion valence change, a preparation method and application thereof, wherein the chemical general formula of the material is as follows: na (Na) a [Mg b Mn c ]O 2+β A, b, c and beta are respectively the mol percentage of the corresponding elements; the relationship between the two satisfies b + c =1, and a +2b +4c =2 × (2 + β), wherein 0.5 ≦ a ≦ 0.25 ≦ b ≦ 0.575 ≦ c ≦ 0.75, 0.02 ≦ β ≦ 0.02; the space group of the layered oxide material is P6 3 /mmc or P6 3 The structure is P2 phase or P3 phase; the layered oxide material is used for a positive electrode active material of a sodium ion secondary battery, oxygen ions in crystal lattices lose electrons during first-cycle charging, and the average valence state of the layered oxide material is increased from-2 to a valence state between-2 and-1; the oxygen ions with higher valence state obtain electrons again during the first cycle of discharge, and the average valence state of the manganese ions is changed from quadrivalence to trivalence along with the deep part of discharge; the oxygen ions and the manganese ions can jointly participate in the reversible electron gaining and losing process during the charging and discharging processes from the second week.
Description
Technical Field
The invention relates to the technical field of materials, in particular to a sodium-magnesium-manganese-based layered oxide material with anion valence change, a preparation method and application thereof.
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 large-scale energy storage system with high performance, the contradiction between power generation and power utilization is solved, and the quality of electric energy is adjusted, so that the 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 of various countries in the world.
The existing energy storage modes at present are physical energy storage and chemical energy storage. The pumped storage in the physical energy storage is the most used at present, the energy storage is the largest, but the pumped storage is limited by the geographical position, the construction period is long, and other physical energy storage such as compressed air energy storage, flywheel energy storage and the like are not scaled. Electrochemical energy storage refers to the storage or release of electricity by reversible chemical reactions, and is widely concerned by people with its advantages of high energy conversion efficiency and power density, long cycle life, short construction period, low maintenance cost, etc.
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, the lead-acid battery has no memory effect and low cost, always occupies most of the energy storage market at present, and is 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.
However, currently, sodium-ion batteries are still in the research stage, no commercial sodium-ion battery cathode material is available, and researches on sodium-ion batteries by researchers are mainly focused on an oxide cathode material Na with a layered structure x MO 2 (M represents 3d transition metal element, and may contain one or more of Ti, V, cr, fe, mn, co, ni, cu, nb, ru, mo, zn, etc.). The basis of the cell is a redox reaction, which is essentially a change in valence, i.e., a transfer and shift of electrons. The half reaction of electron losing is oxidation reaction, and the valence of the anode material is increased; obtaining semi-inverse of electronsShould be a reduction reaction, the valence in the positive electrode material is reduced. The layered oxide positive electrode materials of the sodium-ion battery are provided with transition metal materials capable of generating oxidation-reduction reaction, and the variable valence transition metal of the initial state of the material is in a lower valence state.
Disclosure of Invention
The embodiment of the invention provides a sodium-magnesium-manganese-based layered oxide material with anion valence change, a preparation method and application thereof. The layered oxide material is simple to prepare, and the contained elements of sodium, magnesium and manganese are nontoxic and safe elements, and have high abundance in the earth crust, so the manufacturing cost is low. The sodium ion secondary battery using the layered oxide material is simple in material preparation, and the material is found in a half-battery test to have high specific mass capacity and specific energy, wherein the specific capacity is 1.5 to 2 times of that of a common sodium ion battery anode material, the cycle life is long, and the material has high practical value and can be used for solar power generation, wind power generation, intelligent power grid peak regulation, distributed power stations, backup power supplies or large-scale energy storage equipment of communication base stations.
In a first aspect, the invention discloses a sodium-magnesium-manganese-based layered oxide material with anion valence change, which has a chemical general formula as follows: na (Na) a [Mg b Mn c ]O 2+β ；
The a, b, c and beta are respectively the mol percentage of the corresponding elements; wherein the relationship between a, b, c, β satisfies b + c =1, and a +2b +4c =2 × (2 + β); wherein a is more than or equal to 0.5 and less than or equal to 0.85; b is more than or equal to 0.25 and less than or equal to 0.425; c is more than or equal to 0.575 and less than or equal to 0.75; beta is more than or equal to minus 0.02 and less than or equal to 0.02;
the space group of the layered oxide material is P6 3 /mmc or P6 3 The structure is P2 phase or P3 phase;
when the anion valence-variable layered oxide material is used as a positive electrode active material of a sodium ion secondary battery, oxygen ions in crystal lattices lose electrons during first-cycle charging, and the average valence state of the oxygen ions is increased from-2 to a valence state between-2 and-1; during the first cycle of discharge, the oxygen ions with higher valence state regain electrons; along with the deep discharge, part of manganese ions can obtain electrons, and the average valence state of the manganese ions is changed from quadrivalence to trivalence; from the second week, oxygen ions and manganese ions participate in reversible electron gaining and losing processes during charging and discharging.
Preferably, the oxygen ions in the crystal lattice are formed from O during the first charge cycle 2- Conversion to O 2 x-where 0 < x < 4.
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 sodium carbonate with the stoichiometric quantity of 100-108 wt% of the required sodium, magnesium oxide/magnesium carbonate with the required stoichiometric quantity of manganese dioxide according to a proportion to form a precursor;
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 2-24 hours at 600-1000 ℃ in an air atmosphere;
and grinding the precursor powder after the heat treatment to obtain the layered oxide material.
In a third 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 the method includes:
mixing sodium carbonate with the stoichiometric quantity of 100-108 wt% of the required sodium, magnesium oxide/magnesium carbonate with the required stoichiometric quantity of manganese oxide according to a proportion to form a precursor;
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 2-24 hours at 600-1000 ℃ 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:
sodium nitrate, magnesium nitrate and manganese nitrate in stoichiometric ratio are used as precursors;
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 2-24 hours at 600-1000 ℃ 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 100-108 wt% of stoichiometric sodium acetate or sodium nitrate or sodium carbonate or sodium sulfate and nitrate or sulfate containing magnesium and manganese in water or ethanol according to stoichiometric ratio to obtain precursor solution;
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 2 hours at the temperature of 200-500 ℃ in the air atmosphere;
then heat treatment is carried out for 2 to 24 hours at the temperature of 600 to 1000 ℃;
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:
respectively dissolving nitrate or sulfate or carbonate or hydroxide containing magnesium and manganese in a required stoichiometric ratio into deionized water with a certain volume to respectively form solutions;
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 2-24 hours at 600-1000 ℃ in air atmosphere to obtain precursor powder;
and grinding the precursor powder after the heat treatment to obtain the layered oxide material.
In a seventh aspect, an embodiment of the present invention provides a positive electrode plate of a sodium ion secondary battery, where the positive electrode plate 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.
Preferably, the sodium ion secondary battery is used for large-scale energy storage equipment of solar power generation, wind power generation, smart grid peak shaving, distributed power stations, backup power sources or communication base stations.
The layered oxide material provided by the embodiment of the invention is simple to prepare, and the contained elements of sodium, magnesium and manganese are nontoxic and safe elements, and have high abundance in the earth crust, so the manufacturing cost is low. The sodium ion secondary battery using the layered oxide material charges the valence state transition from negative divalent of lattice oxygen ions to-2 and-1 in the first period, and electrons are completely provided by the oxygen ions to realize the activation of the material; during first-cycle discharge, firstly, the part of higher-valence oxygen ions losing electrons obtain electrons again, the high-valence oxygen ions are changed back to negative bivalence, and along with deep discharge, part of manganese ions can obtain electrons and change from quadrivalence to trivalence; from the second week, oxygen ions and manganese ions can participate in a reversible electron gaining and losing process together in the charging and discharging process, and finally, relatively high discharging capacity is achieved. Due to Mg 2+ Has strong charge interaction and is difficult to migrate from the transition metal layer to Na + Layer, thus compare with Na x [Li,Mn]O 2 In the system Li + Under the condition that the transition metal layer gradually comes out along with circulation and is dissolved in the electrolyte, the sodium-magnesium-manganese-based material has better structural stability, thereby having more excellent circulation performance. The material has good cycle performance and safety performance, has 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 XRD pattern of a plurality of layered oxide materials of varying 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 spray drying 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 according to example 4 of the present invention;
FIG. 5 is a flow chart of a method for preparing a layered oxide material by co-precipitation according to example 5 of the present invention;
fig. 6 is a charge-discharge curve diagram of a sodium ion battery provided in embodiment 6 of the present invention at 1.5-4.5V;
fig. 7 is a charge-discharge curve diagram of a sodium ion battery at 1.5-4.5V according to embodiment 7 of the present invention;
fig. 8 is a charge-discharge curve diagram of a sodium ion battery provided in embodiment 8 of the present invention at 1.5-4.5V;
fig. 9 is a charge-discharge curve diagram of a sodium ion battery at 1.5-4.5V according to embodiment 9 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 of the invention provides a sodium-magnesium-manganese-based layered oxide material with anion valence change, a preparation method and application thereof. The layered oxide material is simple to prepare, and the contained elements of sodium, magnesium and manganese are nontoxic and safe elements and have high abundance in the earth crust, so the manufacturing cost is low. The sodium ion secondary battery using the sodium-magnesium-manganese-based layered oxide material is simple in material preparation, and the material is found in a half battery test to have high mass specific capacity and specific energy, wherein the specific capacity is 1.5 to 2 times of that of a common sodium ion battery anode material, the cycle life is long, and the material has 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 sources or communication base stations.
The invention provides a sodium-magnesium-manganese-based layered oxide material with anion valence change, which has a chemical general formula as follows: na (Na) a [Mg b Mn c ]O 2+β ；
a, b, c and beta are respectively the mol percentage of the corresponding elements; wherein the relationship between a, b, c, β satisfies b + c =1, and a +2b +4c =2 × (2 + β); wherein a is more than or equal to 0.5 and less than or equal to 0.85; b is more than or equal to 0.25 and less than or equal to 0.425; c is more than or equal to 0.575 and less than or equal to 0.75; beta is more than or equal to minus 0.02 and less than or equal to 0.02;
the space group of the sodium-magnesium-manganese-based layered oxide material is P6 3 /mmc or P6 3 The/mcm or R-3m, corresponding structure is P2 phase or P3 phase.
A sodium magnesium manganese-based layered oxide material having an anion valence change is used for a positive electrode active material of a sodium ion secondary battery. During the first charging cycle (corresponding to the extraction of sodium ions), oxygen ions in the crystal lattice lose electrons and are separated from O 2- Conversion to O 2 x-, wherein 0 < x < 4, the average valence state of which is increased from-2 to a valence state between-2 and-1; during the first cycle of discharge (corresponding to the intercalation of sodium ions), oxygen ions with higher valence state obtain electrons again, and along with the deep discharge (the intercalation of sodium ions is increased), part of manganese ions can obtain electrons, and the average valence state of the manganese ions can be changed from quadrivalence to trivalence; from the second week, oxygen ions and manganese ions participate in reversible electron gaining and losing processes during charging and discharging.
The sodium-magnesium-manganese-based layered oxide material of the invention is compared with Na x [Li,Mn]O 2 The layered oxide material has more excellent cycle performance. This is because of the presence of Na x [Li,Mn]O 2 In the system, li + The transition metal layer can be gradually removed along with the circulation and dissolved in the electrolyte, so the circulation performance can be gradually deteriorated, and the sodium-magnesium-manganese-based layered oxide material of the invention is caused by Mg 2+ Has strong charge interaction and is difficult to transfer from the transition metal layer to Na + The layer, therefore, has better structural stability, thereby having more excellent cycle properties.
The following is a description of the preparation process for obtaining this material.
Example 2
The embodiment provides a preparation method of a sodium-magnesium-manganese-based layered oxide material, specifically a solid-phase method, as shown in fig. 2, including:
and 204, grinding the precursor powder after heat treatment to obtain the sodium-magnesium-manganese-based layered oxide material.
The method for preparing the sodium-magnesium-manganese-based layered oxide material provided in this example can be used to prepare the sodium-magnesium-manganese-based 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 3
The embodiment provides a preparation method of a sodium-magnesium-manganese-based layered oxide material, specifically a spray drying method, as shown in fig. 3, including:
301, mixing sodium carbonate with the stoichiometric quantity of 100-108 wt% of the required sodium, magnesium oxide/magnesium carbonate with the required stoichiometric quantity of manganese oxide according to a proportion to form a precursor;
304, placing the precursor powder in a muffle furnace, and carrying out heat treatment for 2-24 hours in an air atmosphere at 600-1000 ℃;
and 305, grinding the precursor powder after heat treatment to obtain the sodium-magnesium-manganese-based layered oxide material.
The method for preparing the sodium-magnesium-manganese-based layered oxide material provided in this example can be used to prepare the sodium-magnesium-manganese-based 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 method for preparing a sodium-magnesium-manganese-based layered oxide material, specifically a sol-gel method, as shown in fig. 4, including:
402, stirring at 50-100 ℃, adding a proper amount of chelating agent, and evaporating to dryness to form precursor gel;
and 405, grinding the precursor powder after heat treatment to obtain the sodium-magnesium-manganese-based layered oxide material.
The method for preparing the sodium-magnesium-manganese-based layered oxide material provided in this example can be used to prepare the sodium-magnesium-manganese-based 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 preparation method of a sodium-magnesium-manganese-based layered oxide material, specifically a coprecipitation method, as shown in fig. 5, including:
and 505, grinding the precursor powder obtained by the heat treatment to obtain the sodium-magnesium-manganese-based layered oxide material.
The method for preparing the sodium-magnesium-manganese-based layered oxide material provided in this example can be used to prepare the sodium-magnesium-manganese-based 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 sodium-magnesium-manganese-based layered oxide material by using the methods provided by the above embodiments of the invention, and the methods and battery characteristics for applying the material to the secondary battery.
Example 6
In this embodiment, the solid-phase method described in embodiment 2 is used to prepare the sodium-magnesium-manganese-based layered oxide material, and the method includes:
mixing Na 2 CO 3 (analytically pure), mgO (analytically pure), mnO 2 (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 Al 2 O 3 Treating in a crucible at 600 deg.C for 15 hr to obtain brown powder of layered oxide material Na 0.5 Mg 0.25 Mn 0.75 O 2 The XRD pattern is shown in figure 1, and Na is seen from the XRD pattern 0.5 Mg 0.25 Mn 0.75 O 2 The crystal structure of (2) is an oxide of a P3 phase layered structure.
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 Na 0.5 Mg 0.25 Mn 0.75 O 2 Mixing the powder with acetylene black and a polyvinylidene fluoride (PVDF) binder according to a mass ratio of 80 2 The 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 metallic sodium as the counter electrode and NaClO as the counter electrode 4 Diethyl carbonate (EC: DEC) solution was used as an electrolyte to assemble a CR2032 button cell. The charge and discharge test was performed at a current density of C/10 using a constant current charge and discharge mode. The test results are shown in FIG. 6 under the conditions of a discharge cutoff voltage of 1.5V and a charge cutoff voltage of 4.5V. The charge-discharge cycle curves for the first and second weeks are shown in fig. 6, and it can be seen that the specific discharge capacity for the first week can reach 160.8mAh/g, the coulombic efficiency for the second week is about 85.7%, and the cycle is stable.
Example 7
In this example, the solid phase method described in the foregoing example 2 was used to prepare a sodium magnesium manganese-based layered oxide material.
The specific procedure for the preparation of the examples is as in example 6, butThe precursor compound Na used 2 CO 3 (analytically pure), mgO (analytically pure), mnO 2 (analytically pure) stoichiometry differs from that in example 6, the heat treatment was carried out at 600 ℃ for 15 hours to obtain a black powder of Na as the layered oxide material 0.55 Mg 0.275 Mn 0.725 O 2 The XRD pattern is shown in figure 1.
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 6. The test voltage range is 1.5V-4.5V, and the test result is shown in figure 7. Fig. 7 shows charge and discharge curves for the first and second weeks. It can be seen that the specific discharge capacity at the first cycle can reach 164.0mAh/g, and the coulomb efficiency at the second cycle is about 94.6%.
Example 8
In this example, the layered oxide material was prepared using the solid phase method described in example 2 above.
The procedure is as in example 6, except that the precursor compound Na is used 2 CO 3 (analytical grade), mgO (analytical grade), mnO 2 (analytical purity) stoichiometry differs from example 6 in that the heat treatment was carried out at 700 ℃ for 15 hours to obtain a black powder of Na as the layered oxide material 0.6 Mg 0.3 Mn 0.7 O 2 The XRD pattern is shown in figure 1.
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 6. The test voltage range is 1.5V-4.4V, and the test result is shown in figure 8. Fig. 8 shows charge and discharge curves for the first and second weeks. It can be seen that the specific discharge capacity in the first cycle can reach 213.4mAh/g, and the coulomb efficiency in the second cycle is about 97.9%.
Example 9
In this example, the layered oxide material was prepared using the solid phase method described in example 2 above.
The procedure is as in example 6, but the precursors used are combinedSubstance Na 2 CO 3 (analytically pure), mgO (analytically pure), mnO 2 (analytically pure) stoichiometry differs from that in example 6, the heat treatment was carried out at 900 ℃ for 15 hours to obtain a black powder of Na as the layered oxide material 0.67 Mg 0.33 Mn 0.67 O 2 The XRD pattern is shown in figure 1.
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 6. The test voltage range is 1.5V-4.5V, and the test result is shown in figure 9. The first and second week charge and discharge curves are shown in fig. 9. It can be seen that the first cycle discharge specific capacity can reach 137mAh/g, and the second cycle coulombic efficiency is about 89.3%.
The sodium-magnesium-manganese-based layered oxide material provided by the embodiment of the invention is simple to prepare, and the contained elements of sodium, magnesium and manganese are nontoxic and safe elements, and have high abundance in the earth crust, so that the manufacturing cost is low. The sodium-ion secondary battery using the sodium-magnesium-manganese-based layered oxide material is simple in material preparation, and the material is found to have ultrahigh specific mass capacity and specific energy in a half-battery test, wherein the specific capacity is 1.5 to 2 times that of a common sodium-ion battery anode material, the cycle life is long, the material has great practical value, and the material can be used for solar power generation, wind power generation, peak regulation of an intelligent power grid, a distributed power station, a backup power supply or large-scale energy storage equipment of a communication base station.
Claims (9)
1. A sodium magnesium manganese-based layered oxide material having an anion valence change, characterized in that the layered oxide material has the chemical general formula: na (Na) a [Mg b Mn c ]O 2+β ；
The a, b, c and beta are respectively the mol percentage of the corresponding elements; wherein the relationship between a, b, c, β satisfies b + c =1, and a +2b +4c =2 × (2 + β); wherein a is more than or equal to 0.5 and less than or equal to 0.85; b is more than or equal to 0.25 and less than or equal to 0.425; c is more than or equal to 0.575 and less than or equal to 0.75; beta is more than or equal to minus 0.02 and less than or equal to 0.02;
the space group of the layered oxide material is P6 3 /mmc or P6 3 (ii)/mcm or R-3m, corresponding to the structure P3 phase;
when the anion valence-variable layered oxide material is used as a positive electrode active material of a sodium ion secondary battery, oxygen ions in crystal lattices lose electrons during first-cycle charging, and the average valence state of the oxygen ions is increased from-2 to a valence state between-2 and-1; during the first cycle of discharge, the oxygen ions with higher valence state regain electrons; along with the deep discharge, part of manganese ions can obtain electrons, and the average valence state of the manganese ions is changed from quadrivalence to trivalence; from the second week, oxygen ions and manganese ions participate in a reversible electron gain and loss process in the charge and discharge process;
oxygen ions in the crystal lattice are formed by O during first-cycle charging 2- To be converted into
Wherein x is more than 0 and less than 4.
2. A method for preparing the layered oxide material of claim 1, wherein the method is a solid phase method comprising:
mixing sodium carbonate with the stoichiometric quantity of 100-108 wt% of the required sodium, magnesium oxide/magnesium carbonate with the required stoichiometric quantity of manganese dioxide according to a proportion to form a precursor;
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 2-24 hours at 600-1000 ℃ in an air atmosphere;
and grinding the precursor powder after the heat treatment to obtain the layered oxide material.
3. A method for preparing the layered oxide material of claim 1, wherein the method is a spray drying method comprising:
mixing sodium carbonate with the stoichiometric quantity of 100-108 wt% of the required sodium, magnesium oxide/magnesium carbonate with the required stoichiometric quantity of manganese oxide according to a proportion to form a precursor;
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 2-24 hours at 600-1000 ℃ in an air atmosphere;
and grinding the precursor powder after the heat treatment to obtain the layered oxide material.
4. A method for preparing the layered oxide material of claim 1, wherein the method is a spray drying method comprising:
sodium nitrate, magnesium nitrate and manganese nitrate in stoichiometric ratio are used as precursors;
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 2-24 hours at 600-1000 ℃ in an air atmosphere;
and grinding the precursor powder after the heat treatment to obtain the layered oxide material.
5. A method for preparing the layered oxide material of claim 1, wherein the method is a sol-gel method comprising:
dissolving 100-108 wt% of stoichiometric sodium acetate or sodium nitrate or sodium carbonate or sodium sulfate and nitrate or sulfate containing magnesium and manganese in water or ethanol according to stoichiometric ratio to obtain precursor solution;
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 2 hours at 200-500 ℃ in air atmosphere;
then heat treatment is carried out for 2 to 24 hours at the temperature of 600 to 1000 ℃;
and grinding the precursor powder after heat treatment to obtain the layered oxide material.
6. A method for preparing the layered oxide material of claim 1, wherein the method is a co-precipitation method comprising:
respectively dissolving nitrate or sulfate or carbonate or hydroxide containing magnesium and manganese in a required stoichiometric ratio into deionized water with a certain volume, and respectively forming solutions;
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 2-24 hours at 600-1000 ℃ in air atmosphere to obtain precursor powder;
and grinding the precursor powder after the heat treatment to obtain the layered oxide material.
7. A positive electrode sheet for a sodium ion secondary battery, comprising:
a current collector, a conductive additive and a binder coated on said current collector, and a layered oxide material as defined in claim 1 above.
8. A sodium ion secondary battery comprising the positive electrode sheet as defined in claim 7.
9. A sodium ion secondary battery according to claim 8, wherein the sodium ion secondary battery is used 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.
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