CN110838576A - Doped coated sodium-ion battery positive electrode material and preparation method and application thereof - Google Patents
Doped coated sodium-ion battery positive electrode material and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a doped coated sodium-ion battery anode material and a preparation method and application thereof, wherein the preparation method comprises the following steps: weighing and uniformly mixing a sodium source, an M1 source and an M2 source according to a required stoichiometric ratio, and performing heat treatment for 2-24 hours in an air atmosphere at 700-1000 ℃ to prepare an O3-phase composite oxide core material NaxM1aM2bO2(ii) a Dispersing the composite oxide core material into a dispersant inStirring at 25-200 ℃, adding a doped coating precursor in the stirring process, drying the obtained material in an oven at 80-200 ℃ after evaporating the dispersing agent to dryness, and obtaining a coating material; sintering the coating material for two or more times at the sintering temperature of 400-900 ℃ for 3-25 hours to obtain a coating product with a doped coating layer; and grinding the coating product with the doped coating layer to obtain the doped coated sodium-ion battery anode material.
Description
Technical Field
The invention relates to the technical field of materials, in particular to a doped coated sodium-ion battery positive electrode material and a preparation method and application thereof.
Background
The problem of exhaustion of fossil energy has attracted much attention of society, and the large-scale utilization of renewable clean energy such as solar energy and wind energy is not slow. The rapid development of energy storage devices, particularly electrochemical energy storage, is important because the intermittent nature of such clean energy sources is difficult to use directly on-grid. Lithium ion batteries are widely used in human life due to their high voltage, high capacity, and long cycle life in electrochemical energy storage. However, since the lithium resource is limited and unevenly distributed, the cost of lithium is gradually increased with the gradual consumption of the limited lithium resource, and the lithium ion battery is necessarily limited as a scale energy storage lithium ion battery. Especially in recent years, the cost of lithium ion batteries has increased due to their wide application in the 3C field and the electric vehicle field, and cannot meet the low cost requirements of the large-scale energy storage market.
Therefore, in the field of energy storage, a secondary battery system which supplements or even replaces a lithium ion battery is needed to be found. The element sodium in the same main group has very similar physical and chemical properties with lithium, and sodium has higher abundance on earth and lower cost than lithium, so the development of sodium ion secondary batteries as large-scale energy storage devices becomes a better choice.
Disclosure of Invention
The invention discloses a doped coated sodium-ion battery positive electrode material and a preparation method and application thereof. The doped coated sodium ion battery cathode material has the advantages of excellent cycle performance, good rate performance, good stability to electrolyte, simple preparation method and improvement of comprehensive performance and application potential of the material. The sodium ion secondary battery using the anode material has excellent cycle performance, excellent rate performance and good safety performance, 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.
In a first aspect, an embodiment of the present invention provides a preparation method of a doped coated sodium ion battery positive electrode material, where the preparation method includes:
weighing and uniformly mixing a sodium source, an M1 source and an M2 source according to a required stoichiometric ratio, and performing heat treatment for 2-24 hours in an air atmosphere at 700-1000 ℃ to prepare an O3-phase composite oxide core material NaxM1aM2bO2(ii) a The sodium source comprises one or more of sodium carbonate, sodium bicarbonate and sodium hydroxide; the M1 source and the M2 source are respectively one or more of oxides, carbonates and hydroxides of M1 and M2; wherein x is 0.8-1.0, a + b is 1, and the material satisfies electroneutrality; m1 is one or more of transition metal elements; m2 is one or more of non-transition metal elements;
dispersing the composite oxide core material into a dispersing agent, stirring at 25-200 ℃, adding a required dosage of doped coating precursor in the stirring process, drying the dispersing agent by distillation, and drying the obtained material in an oven at 80-200 ℃ to obtain a coating material; the doped coating precursor comprises one or more of nitrates and hydrates of Al, Mg, Ti, Zn or La, sulfates and hydrates thereof, and organic salts;
sintering the coating material for two or more times at the sintering temperature of 400-900 ℃ for 3-25 hours to obtain a coating product with a doped coating layer;
and grinding the coating product with the doped coating layer to obtain the doped coated sodium ion battery anode material.
Preferably, the dispersing agent comprises one or more of water, absolute ethyl alcohol, N-methyl pyrrolidone and acetone.
In a second aspect, an embodiment of the present invention provides a doped coated sodium ion battery cathode material prepared by the preparation method described in the first aspect, where the cathode material includes: the composite oxide comprises a core material and a doped coating layer, wherein the core material is formed by a composite oxide, and the doped coating layer is doped in the core material and partially coated outside the core material;
the core material is Na of O3 phasexM1aM2bO2The space group is R-3m, wherein x is more than or equal to 0.8 and less than or equal to 1.0, a + b is 1, and the material satisfies the condition of electric neutrality; m1 is transition metal element, including one or more of Ti, Mn, Fe, Ni, Cu, Zn; m2 is non-transition metal element, including one or more of Li, B, Mg, Al, Si, Ca;
the doped coating layer is O3-phase NayM3dM4eO2Y is more than or equal to 0 and less than or equal to 1.0, d + e is 1, and the material satisfies the condition of electric neutrality; m3 is non-transition metal element including one or more of Li, B, Mg, Al, Si and Ca, M4 is transition metal element including one or more of Ti, Mn, Fe, Ni, Cu, Zn, Zr and La.
Preferably, in the doped coated sodium-ion battery cathode material, the mass percentage of the doped coating layer is 0.05% -20%.
Preferably, the doped coating layer is generated by the reaction of a doped coating precursor and the core material or surface impurities of the core material after liquid phase dispersion treatment and sintering; wherein the doped coating precursor comprises one or more of nitrates and hydrates of Al, Mg, Ti, Zn or La, sulfates and hydrates thereof, and organic salts.
In a third aspect, the embodiment of the present invention provides a sodium-ion secondary battery comprising the doped coated sodium-ion battery positive electrode material described in the second aspect.
In a fourth aspect, embodiments of the present invention provide a use of the ion secondary battery of the third aspect, where the sodium ion secondary battery is used in solar power generation, wind power generation, smart grid peak shaving, distributed power stations, backup power sources, or large-scale energy storage devices of communication base stations.
According to the invention, the doped coating layer obtained by doping type coating can protect the core material and reduce the reaction of the raw material and the electrolyte, so that the accumulation of by-products such as metal fluoride on the surface is reduced, the effective transmission of sodium ions on the interface is ensured, and the cycling stability of the material is finally improved; the preparation process is simple, the coating is uniform, and the obtained material has better comprehensive performance and application prospect, including better rate performance, cycle performance, electrolyte stability and the like, and has great practical value.
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 a flow chart of a method for preparing a doped coated sodium-ion battery positive electrode material according to an embodiment of the present invention;
FIG. 2 is an X-ray diffraction (XRD) pattern of a nucleus 1 provided in example 1 of the present invention;
FIG. 3 is a Scanning Electron Microscope (SEM) image of a core 1 provided in example 1 of the present invention;
figure 4 is an XRD pattern of coated product 1 provided in example 1 of the present invention;
FIG. 5 is an SEM image of a coated product 1 provided in example 1 of the present invention;
FIG. 6 is a first cycle charge and discharge curve of core 1 provided in example 1 of the present invention;
FIG. 7 is a graph of the cycling stability performance of core 1 at 0.5C magnification provided in example 1 of the present invention;
fig. 8 is a first cycle charge and discharge curve diagram of the coated product 1 provided in example 1 of the present invention;
FIG. 9 is a graph of the cycle stability performance at 0.5C rate for the coated product 1 provided in example 1 of the present invention;
figure 10 is an XRD pattern of coated product 2 provided in example 2 of the present invention;
FIG. 11 is an SEM image of coated product 2 provided in example 2 of the present invention;
FIG. 12 is a Ti element distribution diagram of a coated product 2 section provided in example 2 of the present invention under an energy dispersive X-ray spectrometer (EDX);
FIG. 13 is a graph of the cycling stability performance at 2C rate for core 1 provided in example 2 of the present invention;
fig. 14 is a first cycle charge and discharge curve diagram of the coated product 2 provided in example 2 of the present invention;
FIG. 15 is a graph of the cycle stability performance at 0.5C rate for coated product 2 provided in example 2 of the present invention;
FIG. 16 is a graph of the cycle stability performance at 2C rate for the coated product 2 provided in example 2 of the present invention;
FIG. 17 shows the results of F1 s analysis by X-ray photoelectron spectroscopy (XPS) before cycling of core 1 as provided in example 2 of the present invention;
FIG. 18 shows the results of analysis of F1 s under XPS before recycling of the coated product 2 provided in example 2 of the present invention;
FIG. 19 shows the results of XPS analysis of F1 s after 5 weeks of nuclear 1 cycling as provided in example 2 of the present invention;
FIG. 20 shows the results of XPS analysis of F1 s after 5 weeks of cycling of the coated product 2 provided in example 2 of the present invention;
figure 21 is an XRD pattern of core 2 provided in example 3 of the present invention;
FIG. 22 is an SEM photograph of a core 2 provided in example 3 of the present invention;
figure 23 is an XRD pattern of coated product 3 provided in example 3 of the present invention;
FIG. 24 is an SEM image of coated product 3 provided in example 3 of the present invention;
FIG. 25 is a distribution diagram of Ti element under EDX of a cross section of a coated product 3 provided in example 3 of the present invention;
fig. 26 is a first cycle charge and discharge curve diagram of the core 2 provided in example 3 of the present invention;
FIG. 27 is a graph of the cycling stability performance at 0.5C magnification for core 2 provided in example 3 of the present invention;
fig. 28 is a first cycle charge and discharge curve diagram of the coated product 3 provided in example 3 of the present invention;
FIG. 29 is a graph of the cycle stability performance at 0.5C rate for the coated product 3 provided in example 3 of the present invention;
figure 30 is an XRD pattern of core 3 as provided in example 4 of the present invention;
FIG. 31 is an SEM photograph of a core 3 provided in example 4 of the present invention;
figure 32 is an XRD pattern of coated product 4 provided in example 4 of the present invention;
FIG. 33 is an SEM image of coated product 4 provided in example 4 of the present invention;
FIG. 34 is a distribution diagram of Ti element under EDX of a cross section of a coated product 4 provided in example 4 of the present invention;
FIG. 35 is a graph showing the first cycle charge and discharge of core 3 provided in example 4 of the present invention;
FIG. 36 is a graph of the cycling stability performance of core 3 at 0.5C magnification provided in example 4 of the present invention;
FIG. 37 is a first cycle charge and discharge curve of coated product 4 provided in example 4 of the present invention;
fig. 38 is a graph of the cycle stability performance of the coated product 4 at 0.5C magnification provided in example 4 of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The embodiment of the invention provides a doped coated sodium ion battery anode material, which comprises the following components: the composite oxide comprises a core material and a doped coating layer, wherein the core material is formed by a composite oxide, and the doped coating layer is doped in the core material and partially coated outside the core material; wherein the core material is Na of O3 phasexM1aM2bO2The space group is R-3m, x is more than or equal to 0.8 and less than or equal to 1.0, a + b is 1, and the material satisfies the condition of electric neutrality; m1 is transition metal element, including one or more of Ti, Mn, Fe, Ni, Cu, Zn; m2 is non-transition metal element, including one or more of Li, B, Mg, Al, Si, Ca;
the doped coating layer is a doped coating precursor and the core material or the core materialThe surface impurities are generated by reaction after liquid phase dispersion treatment and sintering; the doped coating precursor comprises one or more of nitrates and hydrates of Al, Mg, Ti, Zn or La, sulfates and hydrates thereof, and organic salts. The doped coating layer is Na in O3 phaseyM3dM4eO2Y is more than or equal to 0 and less than or equal to 1.0, d + e is 1, and the material satisfies the condition of electric neutrality; m3 is non-transition metal element including one or more of Li, B, Mg, Al, Si and Ca, M4 is transition metal element including one or more of Ti, Mn, Fe, Ni, Cu, Zn, Zr and La.
In the doped coating sodium ion battery anode material, the mass percentage of the doped coating layer is 0.05-20%.
The material can be prepared by the following method, and specifically can be prepared by the method flow steps shown in figure 1:
Wherein the sodium source comprises one or more of sodium carbonate, sodium bicarbonate and sodium hydroxide; the M1 source and the M2 source are respectively one or more of oxides, carbonates and hydroxides of M1 and M2; wherein x is 0.8-1.0, a + b is 1, and the material satisfies electroneutrality; m1 is one or more of transition metal elements; m2 is one or more of non-transition metal elements;
wherein, the doped coating precursor comprises one or more of nitrates and hydrates of Al, Mg, Ti, Zn or La, sulfates and hydrates thereof, and organic salts; the dispersant may be one or more of water, anhydrous alcohol, N-methyl pyrrolidone and acetone.
130, sintering the coating material for two or more times at the sintering temperature of 400-900 ℃ for 3-25 hours to obtain a coating product with a doped coating layer;
and 140, grinding the coating product with the doped coating layer to obtain the doped coated sodium ion battery anode material.
The doped coating layer obtained by the preparation method is formed by reacting a doped coating precursor with a core material in a certain depth at a high temperature, namely, a new coating layer is formed by reaction on the basis of the traditional coating, and the method is called as doped coating. In the doping type coating process, impurities on the surface of a raw material (namely, a composite oxide core material) or the raw material in a certain depth and a doping coating precursor mutually permeate, are mutually doped and react with each other to form a new coating layer different from the raw material and the coating precursor.
The doped coated sodium ion battery cathode material prepared by the invention can be used for sodium ion secondary batteries, has the characteristics of excellent cycle performance, excellent rate performance and good safety performance, and can be used for large-scale energy storage equipment of solar power generation, wind power generation, intelligent power grid peak regulation, distributed power stations, backup power sources or communication base stations.
The preparation process, material characteristics, properties and the like of the doped coated sodium-ion battery positive electrode material of the invention are described in detail by using some specific examples.
Example 1
Firstly, weighing sodium carbonate, nickel monoxide, copper oxide, ferric oxide and manganese dioxide according to the required stoichiometric ratio, grinding the mixture evenly by utilizing a mortar, then placing the mixture into a muffle furnace, sintering the mixture for 24 hours at 900 ℃ to obtain NaCu1/9Ni2/9Fe1/3Mn1/3O2. The core 1 is marked, and the XRD pattern is shown in figure 2, so that the core is a typical O3 phase structure and has a small amount of CuO impurities. The morphology under SEM is shown in FIG. 3, the particle size is 1-10 μm, and there are fine particles on the surface.
Then, 10g of the ground nucleus 1 is dispersed into 50mL of absolute ethyl alcohol, stirred under the oil bath heating condition, 3.679g of aluminum nitrate nonahydrate crystal (corresponding to 8 percent of coating amount) is added in the stirring process, the heating temperature is 90 ℃, the stirring speed is adjusted to be 200r/min, the absolute ethyl alcohol is evaporated to dryness, and the obtained solid is dried in an oven at 120 ℃.
Pouring the dried solid into a crucible, placing the crucible in a muffle furnace at 800 ℃ for 12h for secondary sintering to obtain a coated product, marking the coated product as a coated product 1, wherein an XRD (X-ray diffraction) spectrum is shown in figure 4, and the result shows that the O3 phase structure is not changed and NaAlO exists2Is generated. SEM photograph is shown in FIG. 5, the particle size is 1-10 μm, and uniform island-like coating is formed on the surface. The result of XRD and SEM was combined to conclude that the cladding layer was NaAlO2It is the product of the reaction of precursor aluminum nitrate nonahydrate and core 1 in certain depth at high temperature.
The core 1 and the coating product 1 obtained by the preparation are respectively used as active substances of positive electrode materials of sodium-ion batteries and are used for preparing the sodium-ion batteries. The method comprises the following specific steps: mixing the prepared positive electrode material active substance of the sodium-ion battery with conductive carbon black and a binder polyvinylidene fluoride (PVDF) according to the weight ratio of 7: 2: 1, adding a proper amount of N-methyl pyrrolidone (NMP) solution, grinding in a normal-temperature drying environment to form slurry, then uniformly coating the slurry on a current collector aluminum foil, drying, and cutting into a circular pole piece with the diameter of 12 mm. The round pole piece is dried for 12 hours at 120 ℃ under the vacuum condition and then transferred to a glove box for later use. The assembly of the simulated cell was carried out in a glove box under Ar atmosphere, with metallic sodium as the counter electrode, glass fiber as the separator, and 1mol/L NaPF6The solution of Ethylene Carbonate (EC)/dimethyl carbonate (DMC) (volume ratio is 1: 1) is used as electrolyte to assemble the CR2032 button cell. The charge and discharge test was performed at a current density of 0.5C using a constant current charge and discharge mode. The test conditions were: the discharge cutoff voltage was 2.0V and the charge cutoff voltage was 4.0V.
The first-cycle charge-discharge curve of the battery prepared from the core 1 is shown in fig. 6, and the first-cycle discharge capacity is 110mA · h/g at 0.5C rate; the cycle performance at 0.5C magnification is shown in fig. 7, and the capacity retention rate after 200 weeks is 82.4%.
The first-cycle charge-discharge curve of the battery prepared from the doped and coated product 1 is shown in fig. 8, and the first-cycle discharge capacity is 111mA · h/g at 0.5C rate; the cycle performance at 0.5C magnification is shown in fig. 9, and the capacity retention rate after 200 weeks is 86.6%.
The comparison with the non-coating structure shows that the cycle performance of the coated material is improved to a certain degree.
Example 2
10g of the ground nucleus 1 of example 1 was dispersed in 50mL of N-methylpyrrolidone, stirred in an air atmosphere under the condition of oil bath heating, 2.13mL of tetrabutyl titanate liquid was added dropwise during stirring at a heating temperature of 60 ℃ with a stirring speed of 200r/min, the N-methylpyrrolidone was evaporated to dryness for about 24 hours, and the resulting solid was dried overnight in an oven at 120 ℃.
And pouring the dried solid into a crucible, placing the crucible in a muffle furnace at 900 ℃ for 12h for secondary sintering to obtain a coated product, marking the coated product as a coated product 2, wherein an XRD (X-ray diffraction) pattern is shown in figure 10, and the result shows that the O3 phase structure is not changed. SEM photograph is shown in FIG. 11, the particle size is 1-10 μm, and uniform island-like coating is formed on the surface. The distribution of Ti element in the cross section under EDX is shown in FIG. 12. From the results of XRD, SEM and EDX, it can be concluded that Ti is distributed in a certain depth, and the coating layer is a product of the reaction of the precursor tetrabutyl titanate and the core 1 in a certain depth, and the coating layer is not shown in the XRD pattern due to the O3 phase.
The core 1 and the coated product 2 prepared as described above were used as active materials of positive electrode materials of sodium ion batteries, respectively, according to the procedure described in example 1, to assemble CR2032 button cells. The charge and discharge test was performed at a current density of 0.5C using a constant current charge and discharge mode. The test conditions were: the discharge cutoff voltage was 2.0V and the charge cutoff voltage was 4.0V.
The cycle performance of the battery prepared from the core 1 at 2C rate is shown in fig. 13, and the capacity retention rate after 250 weeks is 82.3%.
The first-cycle charge-discharge curve of the battery prepared from the doped and coated product 2 is shown in fig. 14, and the first-cycle discharge capacity is 111mA · h/g at 0.5C rate; the cycle performance at 0.5C magnification is shown in FIG. 15, and the capacity retention rate is 82.9% after 200 weeks; the cycle performance at 2C magnification is shown in fig. 16, and the capacity retention rate after 250 weeks is 88.1%.
XPS was used to analyze the pole pieces of core 1 and clad product 2 before and after charge and discharge testing. Firstly, soaking an unrecycled pole piece in electrolyte for 3 hours in a glove box, then sucking the electrolyte away, flushing the surface of the positive pole piece with DMC for a plurality of times, standing for 10min, then sucking away the liquid, and repeating the steps for three times to ensure that NaPF6No residue was present and testing was performed after complete DMC volatilization. And disassembling the recycled battery, taking out the pole piece, and carrying out the washing operation and then testing. The results of the analysis of fluorine element for core 1 before the cycle are shown in FIG. 17, and for the coated product 2 are shown in FIG. 18; results for core 1 after five weeks of cycling are shown in fig. 19, and for coated product 2 are shown in fig. 20. From the XPS result, the metal fluoride accumulation degree of the pole pieces of the core 1 and the coating product 2 is approximately equivalent before circulation, but after only 5 weeks of circulation, a large amount of metal fluoride (mainly sodium fluoride) is accumulated on the pole piece surface of the core 1, and certain obstruction is caused to sodium ion conduction; in contrast, the surface of the pole piece of the coating product 2 is less accumulated, a compact metal fluoride film is formed from the beginning, the internal material is protected, the further reaction of the internal material and the electrolyte is weakened, the structural damage of the material is prevented, and the conduction of sodium ions is guaranteed.
Compared with a non-coating structure, the cycle performance of the coated material is improved to a certain extent, and the coated material has good performance even under a higher multiplying power; the formed coating layer combines the protection effect on the internal material and the guarantee effect on the sodium ion conduction into a whole.
Example 3
Firstly, weighing sodium carbonate, copper oxide, ferric oxide and manganese dioxide according to the required stoichiometric ratio, grinding the mixture evenly by using a mortar, placing the mixture in a muffle furnace, sintering the mixture into Na at 900 ℃ for 24 hours0.92Cu0.22Fe0.33Mn0.45O2. This was labeled as core 2, and its XRD is shown in FIG. 21, which shows that it is a typical O3 phase structure, with a small amount of CuO impurities. SEM is shown in FIG. 22, the particle size is 1-10 μm, and the surface has fine particles.
Dispersing 10g of ground core 2 into 50mL of N-methylpyrrolidone, stirring in an air atmosphere under an oil bath heating condition, dropwise adding 1.06mL of tetrabutyl titanate liquid (corresponding to a coating amount of 10%) in the stirring process, heating to 60 ℃, adjusting the stirring speed to 200r/min, evaporating N-methylpyrrolidone to dryness for about 24 hours, and drying the obtained solid in a 120 ℃ oven overnight.
And pouring the dried solid into a crucible, placing the crucible in a muffle furnace at 900 ℃ for 12h for secondary sintering to obtain a coated product, marking the coated product as a coated product 3, wherein an XRD (X-ray diffraction) pattern is shown in figure 23, and the result shows that the O3 phase structure is not changed. SEM photograph is shown in FIG. 24, the particle size is 1-10 μm, and uniform island-like coating is formed on the surface. The distribution of Ti element in the cross section under EDX is shown in FIG. 25. From the results of XRD, SEM and EDX, it can be concluded that Ti is distributed in a certain depth, and the coating layer is a product of the reaction of the precursor tetrabutyl titanate and the core 2 in a certain depth, and the coating layer is not shown in the XRD pattern due to the O3 phase.
The core 2 and the coated product 3 prepared as described above were used as active materials of a positive electrode material of a sodium ion battery, respectively, according to the procedure described in example 1, to assemble a CR2032 button cell. The charge and discharge test was performed at a current density of 0.5C using a constant current charge and discharge mode. The test conditions were: the discharge cutoff voltage was 2.0V and the charge cutoff voltage was 4.0V.
The first-cycle charge and discharge curve of the battery prepared from the core 2 is shown in fig. 26, the first-cycle specific discharge capacity at 0.5C rate is 107.1mA · h/g, the cycle performance at 0.5C rate is shown in fig. 27, and the capacity retention rate is 80.7% after 100 cycles.
The first-cycle charge-discharge curve of the battery prepared from the doped and coated product 3 is shown in fig. 28, and the first-cycle discharge capacity is 118.1mA · h/g at 0.5C rate; the cycle performance at 0.5C magnification is shown in fig. 29, and the capacity retention rate after 100 weeks is 86.0%.
The comparison with the non-coating structure shows that the cycle performance of the coated material is greatly improved.
Example 4
Weighing sodium carbonate, nickel oxide, ferric oxide and manganese dioxide according to the required stoichiometric ratio, grinding the mixture evenly by using a mortar, placing the mixture in a muffle furnace, sintering the mixture at 900 ℃ for 24 hours to obtain NaNi1/3Fe1/3Mn1/3O2. This is labeled as core 3, and its XRD is shown in fig. 30, which shows a typical O3 phase structure. SEM As shown in FIG. 31, the particle size was 1-10 microns and the surface was smooth.
Dispersing 10g of ground nucleus 3 into 50mL of N-methyl pyrrolidone, stirring in an air atmosphere under an oil bath heating condition, dropwise adding 0.53mL of tetrabutyl titanate liquid (corresponding to a coating amount of 5%) in the stirring process, heating at 70 ℃, adjusting the stirring speed to 200r/min, evaporating N-methyl pyrrolidone for about 12 hours, and drying the obtained solid in a 120 ℃ oven overnight.
And pouring the dried solid into a crucible, placing the crucible in a muffle furnace at 800 ℃ for 12h, and performing secondary sintering to obtain a coated product, wherein the coated product is marked as a coated product 4, and an XRD (X-ray diffraction) pattern of the coated product is shown in figure 32, so that the O3 phase structure is not changed. SEM photograph is shown in FIG. 33, the particle size is 1-10 μm, and uniform island-like coating is formed on the surface. The distribution of Ti element in the cross section under EDX is shown in FIG. 34. From the results of XRD, SEM and EDX, it was concluded that Ti was distributed in a certain depth, and that the coating layer was a product of the reaction of the precursor tetrabutyl titanate with the core 3 in a certain depth, which was not shown in the XRD pattern due to the O3 phase.
The core 3 and the coated product 4 prepared as described above were used as active materials of a positive electrode material of a sodium ion battery, respectively, according to the procedure described in example 1, to assemble a CR2032 button cell. The charge and discharge test was performed at a current density of 0.5C using a constant current charge and discharge mode. The test conditions were: the discharge cutoff voltage was 2.0V and the charge cutoff voltage was 4.0V.
The first-cycle charge-discharge curve of the battery prepared from the core 3 is shown in fig. 35, the first-cycle specific discharge capacity of 121.8mA · h/g at a rate of 0.5C and the cycle performance at a rate of 0.5C are shown in fig. 36, and the capacity retention rate is 61.2% after 200 cycles.
The first-cycle charge-discharge curve of the battery prepared from the doped and coated product 4 is shown in fig. 37, and the first-cycle discharge capacity is 118.1mA · h/g at 0.5C rate; the cycle performance at 0.5C magnification is shown in fig. 38, and the capacity retention rate after 200 weeks is 74.6%.
The comparison with the non-coating structure shows that the cycle performance of the coated material is greatly improved.
The doped coating layer obtained by the method is a product of mutual permeation and reaction of the precursor and the raw material in a certain depth at high temperature, ensures the conduction of sodium ions while protecting the internal material, achieves the effect of improving the circulation stability under the dual action of the precursor and the raw material, and has high practical value.
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 (7)
1. A preparation method of a doped coated sodium-ion battery positive electrode material is characterized by comprising the following steps:
weighing and uniformly mixing a sodium source, an M1 source and an M2 source according to a required stoichiometric ratio, and performing heat treatment for 2-24 hours in an air atmosphere at 700-1000 ℃ to prepare an O3-phase composite oxide core material NaxM1aM2bO2(ii) a The sodium source comprises one or more of sodium carbonate, sodium bicarbonate and sodium hydroxide; the M1 source and the M2 source are respectively one or more of oxides, carbonates and hydroxides of M1 and M2; wherein x is 0.8-1.0, a + b is 1, and the material satisfies electroneutrality; m1 is transition metal element, including one or more of Ti, Mn, Fe, Ni, Cu, Zn; m2 isNon-transition metal elements including one or more of Li, B, Mg, Al, Si and Ca;
dispersing the composite oxide core material into a dispersing agent, stirring at 25-200 ℃, adding a required dosage of doped coating precursor in the stirring process, drying the dispersing agent by distillation, and drying the obtained material in an oven at 80-200 ℃ to obtain a coating material; the doped coating precursor comprises one or more of nitrates and hydrates of Al, Mg, Ti, Zn or La, sulfates and hydrates thereof, and organic salts;
sintering the coating material for two or more times at the sintering temperature of 400-900 ℃ for 3-25 hours to obtain a coating product with a doped coating layer;
and grinding the coating product with the doped coating layer to obtain the doped coated sodium ion battery anode material.
2. The preparation method of claim 1, wherein the dispersant comprises one or more of water, absolute ethanol, N-methyl pyrrolidone and acetone.
3. A doped coated sodium-ion battery positive electrode material prepared by the preparation method of claim 1 or 2, wherein the positive electrode material comprises: the composite oxide comprises a core material and a doped coating layer, wherein the core material is formed by a composite oxide, and the doped coating layer is doped in the core material and partially coated outside the core material;
the core material is Na of O3 phasexM1aM2bO2The space group is R-3m, wherein x is more than or equal to 0.8 and less than or equal to 1.0, a + b is 1, and the material satisfies the condition of electric neutrality; m1 is transition metal element, including one or more of Ti, Mn, Fe, Ni, Cu, Zn; m2 is non-transition metal element, including one or more of Li, B, Mg, Al, Si, Ca;
the doped coating layer is O3-phase NayM3dM4eO2Y is more than or equal to 0 and less than or equal to 1.0, d + e is 1, and the material satisfies the condition of electric neutrality; m3 is notTransition metal elements including one or more of Li, B, Mg, Al, Si and Ca, and M4 is transition metal elements including one or more of Ti, Mn, Fe, Ni, Cu, Zn, Zr and La.
4. The doped coated sodium-ion battery positive electrode material according to claim 3, wherein the doped coating layer is 0.05-20% by mass of the doped coated sodium-ion battery positive electrode material.
5. The doped coated sodium-ion battery positive electrode material according to claim 3, wherein the doped coating layer is generated by a reaction between a doped coating precursor and the core material or surface impurities of the core material after liquid phase dispersion treatment and sintering; wherein the doped coating precursor comprises one or more of nitrates and hydrates of Al, Mg, Ti, Zn or La, sulfates and hydrates thereof, and organic salts.
6. A sodium ion secondary battery comprising the doped coated sodium ion battery positive electrode material according to any one of claims 3 to 5.
7. Use of the sodium ion secondary battery according to claim 6 for solar power generation, wind power generation, smart grid peak shaving, distributed power plants, backup power sources or large-scale energy storage devices of communication base stations.
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