CN114744179A - Sodium-ion battery positive electrode material and preparation method and application thereof - Google Patents
Sodium-ion battery positive electrode material and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a sodium ion battery anode material and a preparation method and application thereof. The method comprises the following steps: 1) mixing a raw material of a positive electrode material of a sodium-ion battery with a solvent, and then carrying out ultrasonic dispersion treatment to obtain a dispersion liquid; 2) carrying out ball milling/sanding on the dispersion liquid, then drying, and cooling at the speed of 1-3 ℃/min after calcining to obtain the positive electrode material of the sodium-ion battery; the chemical composition of the positive electrode material of the sodium-ion battery is NaxMaNibFecMndO2The crystallinity of the positive electrode material of the sodium-ion battery is more than 99 percent; in the XRD (X-ray diffraction) spectrum of the sodium-ion battery anode material, the diffraction peak intensities of different crystal faces meet the relation: i is(003)/[I(104)+I(012)+I(018)]Not less than 0.45. The problem of poor cycle stability caused by the problems of transition metal dissolution, volume change and the like in the cycle process of the cathode material can be effectively prevented.
Description
Technical Field
The invention relates to the technical field of batteries, and relates to a sodium-ion battery positive electrode material, and a preparation method and application thereof.
Background
Although the lithium ion battery is widely applied to the fields of electric automobiles and the like, the lithium ion battery also faces some difficult problems which are difficult to completely solve in a short term, for example, the lithium ion battery has many side reactions besides normal charge and discharge reactions; the lithium resource has low distribution content in the earth crust, and the price is higher and higher as the usage amount increases year by year. At present, 70% of lithium resources are distributed in south America, China makes a large country for lithium ion batteries, and 80% of lithium resources depend on import, so that the development of the new energy battery industry in China is limited.
The sodium ion battery is used for working principles and anode materials similar to those of the lithium ion battery, and sodium resources are widely distributed in the earth crust and are simple and easy to obtain, so that the cost of the sodium resources is low. The sodium ion battery is an important component of low-cost and high-safety energy storage facilities, and the development of stable sodium ion battery anode materials is a problem to be solved urgently.
Among sodium ion battery positive electrode materials, P2 type positive electrode materials generally have a low capacity because of a low sodium content in the materials, whereas O3 type positive electrode materials generally have difficulty in stably existing in the air although the sodium content is high, and thus, have difficulty in manufacturing batteries. Meanwhile, the problem of transition metal dissolution of the anode material is easy to occur in the circulating process, and the circulating stability of the material is influenced.
A solid-phase method is commonly adopted in the synthesis process of the sodium-ion battery, and CN110729475A discloses a sodium-ion battery positive electrode material with a layered and tunnel-shaped mixed structure, a preparation method thereof and a sodium-ion battery, wherein the preparation method comprises the following steps: mixing a sodium source, an iron source and a manganese source according to a molar ratio, and grinding to obtain mixed powder; calcining the mixed powder for the first time to obtain an intermediate product; and grinding the intermediate product, and then carrying out secondary calcination to obtain the sodium-ion battery anode material. CN114203949A discloses a layered manganese-based sodium-ion battery positive electrode material, a preparation method and an application thereof, wherein the preparation method comprises the following steps: (1) by high temperature solid phase synthesis according to Na0.72Li0.12Zn0.18Mn0.7O2Weighing raw materials according to the stoichiometric ratio of each chemical element; (2) weighing raw materials, uniformly mixing, and putting into a planetary ball mill for ball milling; (3) putting the mixture after ball milling into a tabletting grinding tool for tabletting; (4) calcining the pressed sample at high temperature in the air, sintering in a box-type furnace at the heating rate of 3-8 ℃/min, heating to 900 ℃, preserving heat for 12 hours, and cooling the sample to room temperature along with the furnace after sintering is finished; (5) taking out the sintered sample, grinding the sintered sample in a mortar to obtain powder, and pressing the powder into tablets according to the same steps in the step (3); (6) and (3) calcining the pressed sample in the air again, wherein the heating rate is 5 ℃/min, the temperature is increased to 700 ℃, the heat preservation is carried out, the heat preservation time is 12h, and after the sintering is finished, the sample is cooled to the room temperature along with the furnace, so that the layered manganese-based sodium-ion battery anode material can be obtained.
However, the solid phase method has a disadvantage in that the oxide is not uniformly mixed during the synthesis, and thus an oxide hetero-phase occurs during the calcination, which affects the electrical properties of the material.
Therefore, the positive electrode material for the sodium-ion battery, which reduces the dissolution of the transition metal and has less impurity phases, is provided, and has important significance for the development of the sodium-ion battery.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide a positive electrode material of a sodium-ion battery, and a preparation method and application thereof. The sodium ion battery positive electrode material is a multi-element sodium ion battery positive electrode material, has good crystallinity and pure phase, and can effectively prevent the problem of poor cycle stability caused by the problems of transition metal dissolution, volume change and the like in the cycle process of the positive electrode material.
In a first aspect, the present invention provides a method for preparing a positive electrode material of a sodium ion battery, the method comprising the steps of:
(1) mixing a raw material of a positive electrode material of a sodium-ion battery with a solvent, and then carrying out ultrasonic dispersion treatment to obtain a dispersion liquid;
(2) carrying out ball milling/sanding treatment on the dispersion liquid, then carrying out drying treatment, and calcining a dried product, wherein the temperature reduction rate after calcination is 1-3 ℃/min (such as 1 ℃/min, 1.5 ℃/min, 2 ℃/min, 2.5 ℃/min or 3 ℃/min and the like), so as to obtain the positive electrode material of the sodium-ion battery;
the ultrasonic dispersion treatment is beneficial to opening aggregates in the raw materials, increasing the reaction probability among the materials and generating pure-phase substances; the wet ball milling/sanding treatment is beneficial to ensuring the uniform distribution of the multi-component material, and simultaneously, the transition metal material can be ground to a proper particle size, so that the reaction among the materials is more beneficial; the material can be effectively purified by calcining at high temperature and strictly controlling the cooling rate, the crystallinity of the material is improved, and the bulk phase defect of the material is reduced;
the chemical composition of the positive electrode material of the sodium-ion battery is NaxMaNibFecMndO2Wherein a is more than or equal to 0.05 and less than or equal to 0.2, b is more than or equal to 0.2 and less than or equal to 0.35, c is more than or equal to 0.2 and less than or equal to 0.3, d is more than or equal to 0.3 and less than or equal to 0.4, x/(a + b + c + d) is more than or equal to 0.75 and less than or equal to 1, and M is a doping element; the crystallinity of the positive electrode material of the sodium-ion battery is more than 99 percent;
in the XRD (X-ray diffraction) spectrum of the sodium-ion battery anode material, the diffraction peak intensities of different crystal faces meet the relation: i is(003)/[I(104)+I(012)+I(018)]Not less than 0.45. Satisfying the above relation, it is beneficial to the desorption of sodium ions.
Wherein, I(003)The strength of the (003) plane is shown, the (003) plane is a main channel for sodium ion deintercalation and influences the conductivity of the material, I(104)Denotes the intensity of the (104) crystal plane, I(012)Indicates the intensity of the (012) crystal plane, I(018)The intensity of the (018) plane is shown.
a can take the value of 0.05, 0.06, 0.08, 0.1, 0.12, 0.14, 0.15, 0.18 or 0.2, etc.; b can take the value of 0.2, 0.22, 0.25, 0.28, 0.3, 0.33 or 0.35, etc.; the value of c can be, for example, 0.2, 0.22, 0.24, 0.26, 0.28, 0.3, or the like; d can take the value of 0.3, 0.32, 0.35, 0.37, 0.38 or 0.4, etc.; the value of x/(a + b + c + d) may be, for example, 0.75, 0.78, 0.8, 0.82, 0.85, 0.88, 0.9, 0.93, 0.95, 0.97, 0.98, 1, or the like.
The crystallinity of the positive electrode material of the sodium-ion battery is more than 99%, which shows that the material has good crystallinity. The crystallinity may be, for example, 99.1%, 99.2%, 99.4%, 99.5%, 99.7%, 99.8%, or the like.
In the invention, the crystallinity of the sodium-ion battery cathode material can be calculated by the following method: in an XRD (X-ray diffraction) spectrum of the positive electrode material of the sodium-ion battery, the area of a crystalline peak is S1Area of non-crystalline peak is S2When the degree of crystallinity is S1/S2×100％。
The invention utilizes a solid phase method to prepare the multielement sodium ion battery anode material, the basic constituent elements of the multielement sodium ion battery anode material are Mn \ Ni \ Fe, doping elements (such as but not limited to one or more of Li, B and other elements) are added on the basis, the method of the invention starts from a mixing mode and a calcination system, combines the mixing process of ultrasonic dispersion and wet ball milling/sand milling treatment, and synthesizes the calcination and the annealing combination (the temperature rise stage of the calcination corresponds to the calcination process, the temperature reduction rate is controlled to reach the room temperature after the heat preservation process of the calcination to correspond to the annealing process), the material structure can be effectively purified, the crystallinity and the purity of the material are improved, the pure phase sodium ion battery anode material with uniform element distribution and good crystallinity is obtained, and the poor circulation stability caused by the problems of transition metal dissolution, volume change and the like in the circulation process of the anode material can be effectively prevented To a problem of (a).
The method has the advantages that the proportion of the transition metal is convenient to regulate and control by a solid phase method, and the anode materials with different element proportions can be obtained.
The following is a preferred technical solution of the present invention, but not a limitation to the technical solution provided by the present invention, and the technical objects and advantageous effects of the present invention can be better achieved and achieved by the following preferred technical solution.
Preferably, the particle size D50 of the raw material of the positive electrode material of the sodium-ion battery in the step (1) is 3 μm to 8 μm, such as 3 μm, 3.5 μm, 4 μm, 4.5 μm, 5 μm, 5.5 μm, 6 μm, 6.5 μm, 7 μm or 8 μm. Within the particle size range, the material can be ensured to have enough surface area to carry out reaction, and meanwhile, the material is favorably and uniformly mixed, and the material purity is more favorably improved.
Preferably, the raw materials of the positive electrode material of the sodium-ion battery in the step (1) comprise a sodium source, a nickel source, a manganese source, an iron source and an M source.
The specific type of the positive electrode material of the sodium-ion battery is not limited in the invention, and the positive electrode material can be an oxide, a hydroxide or a salt (such as nitrate, acetate and the like).
Preferably, the solvent is an alcohol, preferably ethanol.
Preferably, the solids content of the dispersion is 30% to 50%, such as 30%, 32%, 35%, 38%, 40%, 42%, 44%, 46%, 48%, or 50%, etc.
Preferably, the frequency of the ultrasonic dispersion is 50Hz to 90Hz, such as 50Hz, 55Hz, 60Hz, 65Hz, 70Hz, 75Hz, 80Hz, 85Hz or 90Hz, etc.; the ultrasonic treatment time is 20min-45min, such as 20min, 25min, 30min, 35min, 40min or 45 min.
As a preferable technical scheme of the method of the invention, the ball milling in the step (2) adopts ball milling beads with the particle size of 0.1mm-1mm, such as 0.1mm, 0.2mm, 0.3mm, 0.4mm, 0.5mm, 0.6mm, 0.7mm, 0.8mm, 0.9mm or 1mm, etc.; the ball-to-feed ratio is 3:1 to 10:1, such as 3:1, 4:1, 5:1, 6:1, 7:1, 8:1, 9:1 or 10: 1.
Preferably, the temperature of the calcination in step (2) is 780 ℃ to 1000 ℃, such as 780 ℃, 800 ℃, 850 ℃, 900 ℃, 950 ℃ or 1000 ℃, etc., preferably 850 ℃ to 950 ℃.
Preferably, the calcination time in step (2) is 8h to 15h, such as 8h, 9h, 10h, 11h, 12h, 13h, 14h or 15h, etc., preferably 10h to 12 h.
Preferably, the atmosphere of the calcination in the step (2) is an oxygen-containing atmosphere, preferably an air atmosphere or an oxygen atmosphere.
Preferably, the temperature rise rate of the calcination in the step (2) is 2 ℃/min-5 ℃/min, such as 2 ℃/min, 3 ℃/min, 4 ℃/min or 5 ℃/min, and the like.
As a preferred technical scheme of the method, the method comprises the following steps:
(1) weighing sodium salt, a nickel source, an iron source, a manganese source and a substance containing a doping element according to a stoichiometric ratio, stirring the sodium salt, the nickel source, the iron source, the manganese source and the substance containing the doping element with a solvent, and performing ultrasonic dispersion treatment to obtain a dispersion liquid;
wherein, the nickel source, the iron source and the manganese source can be transition metal oxides or salts, and the substances containing doping elements are oxides or salts;
(2) performing ball milling/sanding treatment on the dispersion;
(3) and (3) carrying out vacuum drying treatment on the material subjected to ball milling/sanding treatment, carrying out high-temperature calcination treatment on the dried material, wherein the temperature reduction rate after calcination is 1-3 ℃/min, and cooling to obtain the anode material.
According to the method, transition metal oxide or salt is used as a raw material, stirring and ultrasonic dispersion processes are firstly utilized to prepare uniformly dispersed dispersion liquid, a wet ball-milling/sand-milling process is then utilized to mix the material, the anode material is calcined, the crystallization degree of the material is further improved by controlling the cooling section speed after calcination, and the high-crystallinity multi-element sodium ion battery anode material with uniformly distributed elements can be obtained after cooling to room temperature.
In the invention, through XRD data processing, the grain size of the material can be determined, and the crystallinity of the material can be qualitatively and quantitatively analyzed by combining with the peak area.
Preferably, the half-peak widths of the (003) peak and the (104) peak in the XRD pattern of the sodium-ion battery cathode material are in the range of 0.0830 ° -0.1130 °, for example, 0.0830 °, 0.0840 °, 0.0850 °, 0.0860 °, 0.0880 °, 0.0910 °, 0.0920 °, 0.0950 °, 0.0970 °, 0.0980 °, 0.1010 °, 0.1030 °, 0.1050 °, 0.1080 °, 0.1100 °, or the like. The surface material exhibited a sharp diffraction peak and was excellent in crystallinity.
Preferably, the XRD pattern of the sodium-ion battery cathode material is analyzed, and the crystal grain size of the sodium-ion battery cathode material is calculated through the Scherrer formula
For example
Or
And so on.
The crystal grain size of the positive electrode material of the sodium-ion battery can be calculated by a scherrer equation, wherein D is K lambda/beta cos theta, D is the crystal grain size, K is a constant, lambda is the X-ray wavelength, beta is the full width at half maximum of a diffraction peak, and theta is a diffraction angle.
Preferably, the primary particles of the positive electrode material for sodium-ion batteries are disk-shaped, and the particle diameter D50 is 3 μm to 8 μm, for example, 3 μm, 3.5 μm, 4 μm, 4.5 μm, 5 μm, 5.5 μm, 6 μm, 6.5 μm, 7 μm, 7.5 μm, or 8 μm.
Preferably, M comprises at least one of Li, B, Co, Zn, Mg, Cu, Zr, Al and Ti, preferably a combination of Li and B. By adopting Li and B for co-doping, better electrochemical performance can be obtained by adopting the method of the invention.
In a second aspect, the invention provides a positive electrode material of a sodium-ion battery prepared by the method in the first aspect.
XRD tests show that the sodium ion cathode material disclosed by the invention is good in crystallinity and free of obvious impurity peaks, and the transition metal is uniformly mixed and completely reacted, so that no obvious impurity is generated.
In a third aspect, the invention provides a sodium-ion battery, which comprises the positive electrode material of the sodium-ion battery of the second aspect.
Compared with the prior art, the invention has the following beneficial effects:
(1) the invention utilizes a solid phase method to prepare the multielement sodium ion battery anode material, the basic constituent elements of the multielement sodium ion battery anode material are Mn \ Ni \ Fe, doping elements (such as but not limited to one or more of Li, B and other elements) are added on the basis, the method starts from a mixing mode and a calcination system, combines a mixing process of ultrasonic dispersion and wet ball milling/sanding, and synthesizes the calcination system combining calcination and annealing, so that the material structure can be effectively purified, the crystallinity and purity of the material are improved, the pure phase sodium ion battery anode material with uniform element distribution and good crystallinity is obtained, and the problem of poor cycle stability caused by the problems of transition metal dissolution, volume change and the like in the cycle process of the anode material can be effectively prevented.
(2) The method has the advantages that the proportion of the transition metal is convenient to regulate and control by a solid phase method, and the anode materials with different element proportions can be obtained.
Drawings
Fig. 1 is an XRD pattern of the cathode material of example 1.
Fig. 2 is a cycle curve of the positive electrode materials of example 1 and comparative example 1.
Detailed Description
The technical scheme of the invention is further explained by the specific implementation mode in combination with the attached drawings.
In order that those skilled in the art will better understand the present invention, the following examples are set forth to provide further detailed description of the invention.
Example 1
The embodiment provides a positive electrode material of a sodium-ion battery and a preparation method thereof, wherein the chemical composition of the sodium-ion battery is Na0.95Li0.05Ni0.25Fe0.25Mn0.4B0.05O2The preparation method comprises the following steps:
(1) in a dry environment, a certain amount of sodium carbonate (D50 ═ 6.7 μm) and nickel oxide (D50 ═ 4.1 μm), manganese oxide (D50 ═ 6.0 μm), iron oxide (D50 ═ 3.2 μm), boron oxide (D50 ═ 5.1 μm), lithium carbonate (D50 ═ 3.8 μm) were weighed, wherein the element ratios were: sodium: nickel oxide: iron oxide: manganese oxide: boron oxide: lithium carbonate is 0.95: 0.25:0.25: 0.4:0.05:0.05 (element molar ratio), adding a certain amount of ethanol into a beaker, stirring, and then carrying out ultrasonic dispersion treatment on the mixed solution, wherein the ultrasonic frequency is 60Hz, and the ultrasonic time is 30min, so as to obtain a dispersion liquid, and the solid content of the dispersion liquid is 40%;
(2) transferring the dispersion liquid after ultrasonic dispersion into a ball milling tank, grinding zirconium beads with certain mass, wherein the particle size of the zirconium beads is 0.5mm, the ball-to-material ratio is 5:1, and drying after grinding is finished;
(3) firstly, carrying out high-temperature calcination treatment on the ground and dried material, wherein the calcination time is 12h, the calcination temperature is 900 ℃, the calcination atmosphere is air, and the temperature reduction speed of the material is controlled to be 2 ℃/min to room temperature after the high-temperature treatment is finished;
(4) and crushing the calcined anode material to obtain the final anode material.
Referring to fig. 1, the XRD pattern of the cathode material prepared in this example shows that the four peaks with the highest intensity are (104), (003), (012) and (018) in sequence, and I in the material is(003)/[I(104)+I(012)+I(018)]Not less than 0.45, is favorable for sodium ion de-intercalation, and has material crystallization peak area of S1Area of non-crystalline peak is S2Then S1/S2 100%. gtoreq.99%, indicating that the material hasHas good crystallinity.
The crystal grain size was calculated by Scherrer formula (D ═ K λ/β cos θ) to be
The full widths at half maximum (FWHM) of the (003) peak and the (104) peak were in the range of 0.0830 to 0.1130 degrees, indicating that the material exhibited a sharp diffraction peak and exhibited good crystallinity.
Example 2
The embodiment provides a positive electrode material of a sodium-ion battery and a preparation method thereof, wherein the chemical composition of the sodium-ion battery is Na0.95Li0.05Ni0.25Fe0.25Mn0.4B0.05O2The preparation method comprises the following steps:
(1) in a dry environment, a certain amount of sodium carbonate (D50 ═ 6.7 μm) and nickel oxide (D50 ═ 4.1 μm), manganese oxide (D50 ═ 6.0 μm), iron oxide (D50 ═ 3.2 μm), boron oxide (D50 ═ 5.1 μm), lithium carbonate (D50 ═ 3.8 μm) were weighed and placed in a beaker, wherein the element ratios were: sodium: nickel oxide: iron oxide: manganese oxide: boron oxide: lithium carbonate is 0.95: 0.25:0.25: adding a certain amount of ethanol into a beaker according to the element molar ratio of 0.4:0.05:0.05, stirring, and then carrying out ultrasonic dispersion treatment on the mixed solution, wherein the ultrasonic frequency is 60Hz, and the ultrasonic time is 30min, so as to obtain a dispersion liquid, wherein the solid content of the dispersion liquid is 45%;
(2) transferring the dispersion liquid after ultrasonic dispersion into a ball milling tank, grinding zirconium beads with certain mass, wherein the particle size of the zirconium beads is 0.3mm, the ball-to-material ratio is 8:1, and drying after grinding;
(3) firstly, carrying out high-temperature calcination treatment on the ground and dried material, wherein the calcination time is 14h, the calcination temperature is 850 ℃, the calcination atmosphere is air, and the cooling speed of the material is controlled to be 1 ℃/min to the room temperature after the high-temperature treatment is finished;
(4) and crushing the calcined anode material to obtain the final anode material.
The material has I in XRD test(003)/[I(104)+I(012)+I(018)]Not less than 0.45, and is beneficial to sodium ionDe-intercalation, and meanwhile, the crystallinity of the material is more than or equal to 99 percent, which shows that the material has good crystallinity.
The crystal grain size was calculated by Scherrer formula (D ═ K λ/β cos θ) to be
The full widths at half maximum (FWHM) of the (003) peak and the (104) peak were in the range of 0.0830 to 0.1130 degrees, indicating that the material exhibited a sharp diffraction peak and exhibited good crystallinity.
Example 3
This example differs from example 1 in that the particle size of the starting material D50>10 μm.
Example 4
This example differs from example 1 in that the time of sonication was 5 min.
Example 5
This example differs from example 1 in that the dispersion has a solids content of 20%.
Example 6
This example differs from example 1 in that the dispersion has a solids content of 60%.
Comparative example 1
This comparative example differs from example 1 in that cooling directly to room temperature, the rate of cooling was not controlled.
Comparative example 2
This comparative example differs from example 1 in that step (1) was carried out without addition of ethanol and without sonication, but rather by direct wet ball milling of equal amounts of ethanol and other starting materials in a ball milling jar.
Comparative example 3
The comparative example is different from example 1 in that the cooling rate was 4 deg.C/min.
Comparative example 4
This comparative example differs from example 1 in that the dispersion after sonication was dried and then dry milled, and the dry milled product was used for high temperature calcination.
Assembling the battery:
the positive electrode materials prepared in the respective examples and comparative examples were used as positive electrode active materials, according to which: conductive agent (Super P): adding the materials into NMP to prepare positive electrode slurry, coating the positive electrode slurry on aluminum foil, and drying to obtain the positive electrode plate, wherein the mass ratio of the binder (PVDF) is 80:10: 10.
The positive plate, the sodium plate and the electrolyte are adopted to prepare the battery, wherein the electrolyte comprises EC and DMC which are in a volume ratio of 1:1 and are matched with sodium hexafluorophosphate (the concentration is 1M), and a glass fiber diaphragm is adopted to assemble the sodium ion half battery.
Electrochemical performance was tested (see table 1 for results):
(1) and (3) testing the buckling capacitance: the charging multiplying power is 0.5C, the discharging multiplying power is 1C, the charging cut-off voltage is 4.2V, the discharging cut-off voltage is 2.0V, and the discharging specific capacity under 1C is counted.
(2) And (3) cycle testing: the charge rate was 0.5C, the discharge rate was 1C, the charge cut-off voltage was 4.2V, the discharge cut-off voltage was 2.0V, and the capacity retention ratio was counted for 50 weeks.
Fig. 2 is a cycle curve of the positive electrode materials of example 1 and comparative example 1.
TABLE 1
As can be seen from table 1, the method of the present invention can effectively purify the material structure, improve the crystallinity and purity of the material, obtain the pure-phase sodium-ion battery cathode material with uniform element distribution and good crystallinity, and effectively prevent the problem of poor cycle stability caused by the problems of transition metal dissolution, volume change, etc. during the cycle of the cathode material.
It is understood from a comparison between example 1 and example 3 that an excessively large particle size of the raw material lowers the purity of the material, resulting in a decrease in the first discharge capacity and cycle performance.
It can be seen from the comparison between example 1 and example 4 that the ultrasound time is too short, which affects the effect of opening the agglomerates in the raw material and reduces the pure phase of the material, resulting in a decrease in the first discharge capacity and the cycle performance.
The comparison between the embodiment 1 and the embodiments 5 to 6 shows that the solid content of the dispersion liquid has an optimal range, and the solid content is in a range of 30 to 50 percent, so that better ultrasonic dispersion effect and wet ball milling/sanding effect can be obtained, the purity of the material and the dispersion uniformity of the transition elements can be improved, the proper particle size can be obtained, and the first discharge capacity and the cycle performance can be improved.
It can be known from the comparison between the example 1 and the comparative example 1 that the annealing effect cannot be achieved by adopting a natural cooling mode without controlling the cooling rate, the crystallinity of the product is poor, and the first effect and the cycle performance are greatly reduced.
As can be seen from the comparison of example 1 with comparative example 2, no sonication resulted in a decrease in first effect and cycle performance.
It can be seen from the comparison of example 1 with comparative example 3 that the effective annealing effect cannot be achieved even if the cooling rate is too fast, resulting in reduced first effect and cycle performance.
It can be seen from the comparison between example 1 and comparative example 4 that wet ball milling/grinding can better improve the first effect and cycle performance of the material than dry ball milling.
The applicant states that the present invention is illustrated in detail by the above examples, but the present invention is not limited to the above detailed methods, i.e. it is not meant that the present invention must rely on the above detailed methods for its implementation. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
Claims (10)
1. A preparation method of a positive electrode material of a sodium-ion battery is characterized by comprising the following steps:
(1) mixing a raw material of a positive electrode material of a sodium-ion battery with a solvent, and then carrying out ultrasonic dispersion treatment to obtain a dispersion liquid;
(2) carrying out ball milling/sanding treatment on the dispersion liquid, then carrying out drying treatment, and calcining a dried product, wherein the temperature reduction rate after calcination is 1-3 ℃/min, so as to obtain the sodium-ion battery anode material;
the chemical composition of the positive electrode material of the sodium-ion battery is NaxMaNibFecMndO2Wherein a is more than or equal to 0.05 and less than or equal to 0.2, b is more than or equal to 0.2 and less than or equal to 0.35, c is more than or equal to 0.2 and less than or equal to 0.3, d is more than or equal to 0.3 and less than or equal to 0.4, a + b + c + d is 1, x/(a + b + c + d) is more than or equal to 0.75 and less than or equal to 1, and M is a doping element; the crystallinity of the positive electrode material of the sodium-ion battery is more than 99 percent;
in an XRD (X-ray diffraction) spectrum of the sodium-ion battery cathode material, diffraction peak intensities of different crystal faces meet the relation: i is(003)/[I(104)+I(012)+I(018)]≥0.45。
2. The method according to claim 1, wherein the particle size D50 of the raw material of the positive electrode material for sodium-ion batteries in step (1) is 3 μm to 8 μm.
3. The method according to claim 1 or 2, wherein the raw materials of the positive electrode material of the sodium-ion battery of step (1) comprise a sodium source, a nickel source, a manganese source, an iron source and an M source;
preferably, the solvent is an alcohol, preferably ethanol;
preferably, the solids content of the dispersion is 30% to 50%;
preferably, the frequency of the ultrasonic dispersion is 50Hz-90Hz, and the time of the ultrasonic dispersion is 20min-45 min.
4. The method as claimed in any one of claims 1 to 3, wherein the ball milling in step (2) is carried out using ball milling beads having a particle size of 0.1mm to 1mm and a ball to material ratio of 3:1 to 10: 1.
5. The process according to any one of claims 1 to 4, wherein the temperature of the calcination in step (2) is 780 ℃ to 1000 ℃, preferably 850 ℃ to 950 ℃;
preferably, the calcining time of the step (2) is 8-15 h, preferably 10-12 h;
preferably, the atmosphere of the calcination in the step (2) is an oxygen-containing atmosphere, preferably an air atmosphere or an oxygen atmosphere;
preferably, the temperature rise rate of the calcination in the step (2) is 2-5 ℃/min.
6. The method according to any one of claims 1-5, characterized in that the method comprises the steps of:
(1) weighing sodium salt, a nickel source, an iron source, a manganese source and a substance containing a doping element according to a stoichiometric ratio, stirring the sodium salt, the nickel source, the iron source, the manganese source and the substance containing the doping element with a solvent, and performing ultrasonic dispersion treatment to obtain a dispersion liquid;
wherein, the nickel source, the iron source and the manganese source can be transition metal oxides or salts, and the substances containing doping elements are oxides or salts;
(2) performing ball milling/sanding treatment on the dispersion;
(3) and (3) carrying out vacuum drying treatment on the material subjected to ball milling/sanding treatment, carrying out high-temperature calcination treatment on the dried material, wherein the temperature reduction rate after calcination is 1-3 ℃/min, and cooling to obtain the anode material.
7. The method of any one of claims 1-6, wherein the XRD pattern of the positive electrode material for a sodium ion battery has half-widths of the (003) peak and the (104) peak in the range of 0.0830 ° -0.1130 °;
preferably, the XRD pattern of the sodium-ion battery cathode material is analyzed, and the crystal grain size of the sodium-ion battery cathode material is calculated through the Scherrer formula
8. The method according to any one of claims 1 to 7, wherein the primary particles of the sodium-ion battery positive electrode material are disk-shaped, and have a particle diameter D50 of 3 μm to 8 μm;
preferably, M comprises at least one of Li, B, Co, Zn, Mg, Cu, Zr, Al and Ti, preferably a combination of Li and B.
9. A positive electrode material for a sodium-ion battery prepared by the method of any one of claims 1 to 8.
10. A sodium-ion battery comprising the positive electrode material for a sodium-ion battery according to claim 9.
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| CN115275178A (en) * | 2022-07-18 | 2022-11-01 | 贵州振华新材料有限公司 | Single crystal sodium ion battery positive electrode material, preparation method thereof and battery |
| CN115275134A (en) * | 2022-07-18 | 2022-11-01 | 贵州振华新材料有限公司 | Single crystal sodium ion battery anode material and preparation method and application thereof |
| CN116031402A (en) * | 2023-03-28 | 2023-04-28 | 珠海冠宇电池股份有限公司 | Positive electrode material, positive electrode sheet and sodium ion battery |
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| CN117096331A (en) * | 2023-10-20 | 2023-11-21 | 湖南驼峰新能源有限公司 | Sodium ion battery positive electrode material and preparation method and application thereof |
| CN117285087A (en) * | 2023-11-24 | 2023-12-26 | 北京中科海钠科技有限责任公司 | Layered oxide, preparation method thereof and sodium battery |
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Cited By (9)
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| CN115275178A (en) * | 2022-07-18 | 2022-11-01 | 贵州振华新材料有限公司 | Single crystal sodium ion battery positive electrode material, preparation method thereof and battery |
| CN115275134A (en) * | 2022-07-18 | 2022-11-01 | 贵州振华新材料有限公司 | Single crystal sodium ion battery anode material and preparation method and application thereof |
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| CN116190561A (en) * | 2023-04-28 | 2023-05-30 | 宁德时代新能源科技股份有限公司 | Battery monomer of sodium ion battery, sodium ion battery and power utilization device |
| CN116190561B (en) * | 2023-04-28 | 2023-09-15 | 宁德时代新能源科技股份有限公司 | Battery monomer of sodium ion battery, sodium ion battery and power utilization device |
| CN117096331A (en) * | 2023-10-20 | 2023-11-21 | 湖南驼峰新能源有限公司 | Sodium ion battery positive electrode material and preparation method and application thereof |
| CN117096331B (en) * | 2023-10-20 | 2024-02-23 | 湖南驼峰新能源有限公司 | Sodium ion battery positive electrode material and preparation method and application thereof |
| CN117285087A (en) * | 2023-11-24 | 2023-12-26 | 北京中科海钠科技有限责任公司 | Layered oxide, preparation method thereof and sodium battery |
| CN117285087B (en) * | 2023-11-24 | 2024-04-23 | 北京中科海钠科技有限责任公司 | Layered oxide, preparation method thereof and sodium battery |
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