CN114744179B - 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 PDF

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CN114744179B
CN114744179B CN202210513815.4A CN202210513815A CN114744179B CN 114744179 B CN114744179 B CN 114744179B CN 202210513815 A CN202210513815 A CN 202210513815A CN 114744179 B CN114744179 B CN 114744179B
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ion battery
sodium ion
positive electrode
electrode material
equal
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CN114744179A (en
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陈思贤
江卫军
任海朋
郑晓醒
杨红新
郝雷明
张放南
高飞
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Svolt Energy Technology Co Ltd
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    • C01G53/40—Nickelates
    • C01G53/42—Nickelates containing alkali metals, e.g. LiNiO2
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    • H—ELECTRICITY
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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Abstract

The invention discloses a sodium ion battery anode material and a preparation method and application thereof. The method comprises the following steps: 1) Mixing the raw materials of the positive electrode material of the sodium ion battery with a solvent, and then performing ultrasonic dispersion treatment to obtain a dispersion liquid; 2) Performing ball milling/sand milling on the dispersion liquid, performing drying treatment, and cooling at a speed of 1 ℃/min-3 ℃/min after calcination to obtain a sodium ion battery anode material; the chemical composition of the positive electrode material of the sodium ion battery is Na x M a Ni b Fe c Mn d O 2 The crystallinity of the positive electrode material of the sodium ion battery is more than 99%; in the XRD spectrum of the sodium ion battery anode material, the diffraction peak intensities of different crystal planes satisfy the relation: i (003) /[I (104) +I (012) +I (018) ]And more than or equal to 0.45. The problem of poor cycling stability caused by problems of transition metal dissolution, volume change and the like in the cycling process of the anode material can be effectively prevented.

Description

Sodium ion battery positive electrode material and preparation method and application thereof
Technical Field
The invention relates to the technical field of batteries, and relates to a sodium ion battery anode material, a preparation method and application thereof.
Background
Although the lithium ion battery has been widely used in the fields of electric automobiles and the like, the lithium ion battery also faces some difficult problems, and is difficult to completely solve in a short period of time, for example, a lithium ion battery has a plurality of side reactions besides normal charge and discharge reactions; the lithium resources are distributed in the crust at lower content, and the price of the lithium resources is higher and higher with the annual increase of the consumption. Currently, 70% of lithium resources are distributed in south america, china is a large country for manufacturing lithium ion batteries, 80% of lithium resources are imported in a dependent manner, and therefore development of new energy battery industry in China is limited.
Sodium ion batteries are used for the same working principle and positive electrode materials as lithium ion batteries, and sodium resources are widely distributed in the crust, are simple and easily obtained, so that the cost of the sodium resources is low. The sodium ion battery is an important component of low-cost high-safety energy storage facilities, and development of a stable sodium ion battery anode material is a problem to be solved urgently.
In the sodium ion battery positive electrode material, the P2 type positive electrode material has low content of sodium, so the capacity is low, while the O3 type positive electrode material has high content of sodium, but is difficult to exist stably in air, so the manufacturing of the battery is difficult. Meanwhile, the problem of dissolution of transition metal easily occurs in the circulating process of the anode material, and the circulating stability of the material is affected.
In the synthesis process of sodium ion batteries, a solid phase method is usually adopted, and CN110729475A discloses a layered and tunnel-shaped mixed structure sodium ion battery anode material, 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 performing 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 application, the preparation method comprises: (1) Adopts a high-temperature solid phase synthesis method according to Na 0.72 Li 0.12 Zn 0.18 Mn 0.7 O 2 Stoichiometric ratio of each chemical element in the raw materialsMaterial preparation; (2) Weighing the raw materials, uniformly mixing, and putting the raw materials into a planetary ball mill for ball milling; (3) Putting the mixture after ball milling into a tabletting grinding tool to be pressed into tablets; (4) Calcining the pressed sample at high temperature in air, sintering in a box-type furnace, heating to 900 ℃ at a heating rate of 3-8 ℃/min, preserving heat for 12 hours, and cooling the sample to room temperature along with the furnace after sintering is completed; (5) Taking out the sample after sintering once, putting the sample into a mortar for grinding to obtain powder, and pressing the powder into tablets according to the same steps as the step (3); (6) Calcining the pressed sample again in air, heating to 700 ℃ at a heating rate of 5 ℃/min, preserving heat for 12 hours, and cooling the sample to room temperature along with a furnace after sintering is completed to obtain the layered manganese-based sodium ion battery anode material.
However, the solid phase method has a disadvantage in that the mixing of oxides is not uniform during the synthesis process, so that oxide impurity phase occurs during calcination, which affects the electrical properties of the material.
Therefore, the sodium ion battery positive electrode material which reduces the dissolution of transition metal and has less impurity phase is provided, and has great significance for the development of sodium ion batteries.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide a sodium ion battery anode material and a preparation method and application thereof. The positive electrode material of the sodium ion battery is a multi-element positive electrode material of the sodium ion battery, has good crystallinity and pure phase, and can effectively prevent the problem of poor cycling stability caused by the problems of transition metal dissolution, volume change and the like in the cycling 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 the raw materials of the positive electrode material of the sodium ion battery with a solvent, and then performing ultrasonic dispersion treatment to obtain a dispersion liquid;
(2) Carrying out ball milling/sand milling treatment on the dispersion liquid, then carrying out drying treatment, and calcining a dried product, wherein the cooling rate after calcination is 1 ℃/min-3 ℃/min (for example, 1 ℃/min, 1.5 ℃/min, 2 ℃/min, 2.5 ℃/min or 3 ℃/min and the like), so as to obtain the sodium ion battery anode material;
wherein, the ultrasonic dispersion treatment is favorable for opening agglomerates in the raw materials, increasing the reaction probability among the materials and being favorable for generating pure-phase substances; the wet ball milling/sand milling treatment is beneficial to ensuring the uniform distribution of the multiple materials, and simultaneously, the transition metal materials can be ground to proper particle sizes, so that the reaction among the materials is facilitated; 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 defects of the material are reduced;
the chemical composition of the positive electrode material of the sodium ion battery is Na x M a Ni b Fe c Mn d O 2 Wherein a is more than or equal to 0.05 and less than or equal to 0.2,0.2, b is more than or equal to 0.35,0.2 and less than or equal to c is more than or equal to 0.3, d is more than or equal to 0.3 and less than or equal to 0.4,0.75 and less than or equal to x/(a+b+c+d) is more 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%;
in the XRD spectrum of the sodium ion battery anode material, the diffraction peak intensities of different crystal planes satisfy the relation: i (003) /[I (104) +I (012) +I (018) ]And more than or equal to 0.45. Satisfies the above relation and is beneficial to the deintercalation of sodium ions.
Wherein I is (003) The intensity of the (003) crystal face is expressed, the (003) crystal face is a main channel for sodium ion deintercalation, the conductivity of the material is influenced, and I (104) Representing the intensity of the (104) crystal plane, I (012) Represents the intensity of the (012) crystal plane, I (018) The intensity of the (018) plane is represented.
The value of a may be, for example, 0.05, 0.06, 0.08, 0.1, 0.12, 0.14, 0.15, 0.18, 0.2, or the like; the value of b may be, for example, 0.2, 0.22, 0.25, 0.28, 0.3, 0.33, or 0.35; the value of c may be, for example, 0.2, 0.22, 0.24, 0.26, 0.28, or 0.3; the value of d may be, for example, 0.3, 0.32, 0.35, 0.37, 0.38, 0.4, or the like; 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, or 1.
The crystallinity of the positive electrode material of the sodium ion battery is more than 99%, which indicates that the material has good crystallinity. The crystallinity may be, for example, 99.1%, 99.2%, 99.4%, 99.5%, 99.7% or 99.8%.
In the invention, the crystallinity of the positive electrode material of the sodium ion battery can be calculated by the following method: in the XRD spectrum of the positive electrode material of the sodium ion battery, the crystallization peak area is S 1 Amorphous peak area S 2 Crystallinity=s 1 /S 2 ×100％。
The method utilizes a solid-phase method to prepare the multi-element sodium ion battery anode material, the basic component element of the multi-element sodium ion battery anode material is Mn\Ni\Fe, doping elements (such as one or more of Li, B and the like) are added on the basis, the method combines a mixing process of ultrasonic dispersion and wet ball milling/sanding treatment from a mixing mode and a calcining system, combines a calcining and annealing process (a heating stage of calcining and a heat preservation process correspond to a calcining process, and a cooling rate is controlled to reach a temperature after the heat preservation process of calcining and corresponds to an annealing process), the material structure can be effectively purified, the crystallinity and purity of the material can be improved, and the problem of poor cycling stability caused by the problems of dissolution of transition metal, volume change and the like in the cycling process of the anode material can be effectively prevented.
The method has the advantages that the proportion of the transition metal can be conveniently regulated and controlled by a solid phase method, and the anode material with different element proportions can be obtained.
The following preferred technical solutions are used as the present invention, but not as limitations on the technical solutions 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 solutions.
Preferably, the particle diameter D50 of the starting material of the positive electrode material of the sodium ion battery in the step (1) is 3 μm to 8. Mu.m, for example, 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, etc. The particle size range can ensure that the material can have enough surface area to react, is favorable for uniform mixing of the material, and is more favorable for improving the purity of the material.
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 invention is not limited to the specific type of the positive electrode material of the sodium ion battery, and can be oxide, hydroxide or 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% -50%, e.g., 30%, 32%, 35%, 38%, 40%, 42%, 44%, 46%, 48%, 50%, etc.
Preferably, the frequency of the ultrasonic dispersion is 50Hz-90Hz, such as 50Hz, 55Hz, 60Hz, 65Hz, 70Hz, 75Hz, 80Hz, 85Hz, 90Hz, etc.; the time of the ultrasound is 20min-45min, such as 20min, 25min, 30min, 35min, 40min or 45min, etc.
As a preferred embodiment of the method of the present invention, the ball-milling beads used in the ball-milling in the step (2) have a particle size of 0.1mm to 1mm, for example, 0.1mm, 0.2mm, 0.3mm, 0.4mm, 0.5mm, 0.6mm, 0.7mm, 0.8mm, 0.9mm or 1mm, etc.; the ball to material ratio is 3:1-10:1, such as 3:1, 4:1, 5:1, 6:1, 7:1, 8:1, 9:1 or 10:1, etc.
Preferably, the temperature of the calcination in step (2) is 780 ℃ to 1000 ℃, such as 780 ℃, 800 ℃, 850 ℃, 900 ℃, 950 ℃ or 1000 ℃ and the like, preferably 850 ℃ to 950 ℃.
Preferably, the calcination in step (2) is carried out for a period of time ranging from 8h to 15h, for example 8h, 9h, 10h, 11h, 12h, 13h, 14h or 15h, etc., preferably from 10h to 12h.
Preferably, the atmosphere of the calcination in step (2) is an oxygen-containing atmosphere, preferably an air atmosphere or an oxygen atmosphere.
Preferably, the temperature rise rate of the calcination in step (2) is from 2 ℃/min to 5 ℃/min, such as 2 ℃/min, 3 ℃/min, 4 ℃/min or 5 ℃/min, etc.
As a preferred embodiment of the method according to the invention, the method comprises the following steps:
(1) Weighing sodium salt, nickel source, iron source, manganese source and doping element-containing substances according to stoichiometric ratio, stirring with solvent, and performing ultrasonic dispersion treatment to obtain dispersion;
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) Ball milling/sanding the dispersion liquid;
(3) And carrying out vacuum drying treatment on the ball-milled/sand-ground material, carrying out high-temperature calcination treatment on the dried material, wherein the cooling rate after calcination is 1 ℃/min-3 ℃/min, and cooling to obtain the anode material.
According to the method, transition metal oxide or salt is used as a raw material, firstly, a uniformly dispersed dispersion liquid is prepared by using stirring and ultrasonic dispersing procedures, secondly, a wet ball milling/sanding process is used for carrying out mixing treatment on the material, then, the positive electrode material is subjected to calcination treatment, the crystallization degree of the material is further improved by controlling the rate of a cooling section after calcination, and after cooling to room temperature, the high-crystallinity multi-element sodium ion battery positive electrode material with uniform element distribution can be obtained.
In the invention, the crystal grain size of the material can be determined through XRD data processing, and the crystallinity of the material can be qualitatively and quantitatively analyzed by combining peak areas.
Preferably, the half-width of the (003) peak and the (104) peak in the XRD pattern of the positive electrode material of the sodium ion battery is 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 °, or 0.1100 °. The surface material shows sharp diffraction peaks and has good crystallinity.
Preferably, the XRD pattern of the positive electrode material of the sodium ion battery is analyzed, and the crystal grain size of the positive electrode material of the sodium ion battery is calculated by the Shelle formulaFor example-> Or->Etc.
The grain size of the positive electrode material of the sodium ion battery can be calculated by a scherrer formula, wherein d=kλ/βcos θ, D is the grain size, K is a constant, λ is the X-ray wavelength, β is the half-width of the diffraction peak, and θ is the diffraction angle.
Preferably, the primary particles of the positive electrode material of the sodium ion battery are disk-shaped and have a particle diameter D50 of 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, etc.
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 co-doping with Li and B, better electrochemical performance can be achieved with the method of the present invention.
In a second aspect, the invention provides a sodium ion battery positive electrode material prepared by the method according to the first aspect.
XRD tests show that the sodium ion positive electrode material provided by the invention has good crystallinity and no obvious impurity peak, and shows that transition metals are uniformly mixed and completely reacted, and no obvious impurity appears.
In a third aspect, the present invention provides a sodium ion battery, wherein the sodium ion battery comprises the positive electrode material of the sodium ion battery in the second aspect.
Compared with the prior art, the invention has the following beneficial effects:
(1) The method utilizes a solid-phase method to prepare the multi-element sodium ion battery anode material, the basic component element of the multi-element sodium ion battery anode material is Mn\Ni\Fe, doping elements (such as one or more of Li, B and the like) are added on the basis, and the method combines the mixing process of ultrasonic dispersion and wet ball milling/sanding from the mixing mode and the calcining system, combines the calcining system of combination of calcination and annealing, can effectively purify the material structure, improve the crystallinity and purity of the material, obtain the pure-phase sodium ion battery anode material with uniform element distribution and good crystallinity, and can effectively prevent the problem of poor cycling stability caused by the problems of transition metal dissolution, volume change and the like in the cycling process of the anode material.
(2) The method has the advantages that the proportion of the transition metal can be conveniently regulated and controlled by a solid phase method, and the anode material with different element proportions can be obtained.
Drawings
Fig. 1 is an XRD pattern of the positive electrode 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 described below by the specific embodiments with reference to the accompanying drawings.
The invention will be further described in detail with reference to the following examples for a better understanding of the invention to those skilled in the art.
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 Na 0.95 Li 0.05 Ni 0.25 Fe 0.25 Mn 0.4 B 0.05 O 2 The preparation method comprises the following steps:
(1) In a dry environment, a certain amount of sodium salt sodium carbonate (d50=6.7 μm), 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 are: sodium: nickel oxide: iron oxide: manganese oxide: boron oxide: lithium carbonate=0.95: 0.25:0.25:0.4:0.05:0.05 (molar ratio of elements), 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 a 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 for 12 hours at 900 ℃ in the air under the control of the material cooling speed of 2 ℃/min to room temperature after the high-temperature treatment;
(4) And crushing the calcined positive electrode material to obtain the final positive electrode material.
As can be seen from the XRD patterns of the positive electrode material prepared in this example, which are shown in FIG. 1, the four peaks with the greatest intensity are (104), (003), (012) and (018) peaks in this order, I in the material (003) /[I (104) +I (012) +I (018) ]Not less than 0.45, is favorable for sodium ion deintercalation, and has a crystallization peak area of S 1 Amorphous peak area S 2 S1/S2 is 100 percent or more than 99 percent, which indicates that the material has good crystallinity.
The grain size was calculated by the Scherrer formula (d=kλ/βcosθ) to beThe half width (FWHM) of the (003) peak and the (104) peak is in the range of 0.0830-0.1130 degrees, which shows that the material presents a sharp diffraction peak and has 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 Na 0.95 Li 0.05 Ni 0.25 Fe 0.25 Mn 0.4 B 0.05 O 2 The preparation method comprises the following steps:
(1) In a dry environment, a certain amount of sodium salt 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 are: sodium: nickel oxide: iron oxide: manganese oxide: boron oxide: lithium carbonate=0.95: 0.25:0.25:0.4:0.05:0.05 (molar ratio of elements), 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 45%;
(2) Transferring the dispersion liquid after ultrasonic dispersion into a ball milling tank, grinding zirconium beads with a 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 is finished;
(3) Firstly, carrying out high-temperature calcination treatment on the ground and dried material for 14 hours at 850 ℃ in the presence of air, and controlling the cooling speed of the material to be 1 ℃/min to room temperature after the high-temperature treatment is finished;
(4) And crushing the calcined positive electrode material to obtain the final positive electrode material.
XRD test shows that I in the material (003) /[I (104) +I (012) +I (018) ]Not less than 0.45, being beneficial to the deintercalation of sodium ions, and the crystallinity of the material is not less than 99 percent, which indicates that the material has good crystallinity.
The grain size was calculated by the Scherrer formula (d=kλ/βcosθ) to beThe half width (FWHM) of the (003) peak and the (104) peak is in the range of 0.0830-0.1130 degrees, which shows that the material presents a sharp diffraction peak and has good crystallinity.
Example 3
This example differs from example 1 in that the raw material particle size D50>10 μm.
Example 4
The difference between this example and example 1 is that the time of ultrasound was 5min.
Example 5
This example differs from example 1 in that the solids content of the dispersion is 20%.
Example 6
This example differs from example 1 in that the solids content of the dispersion is 60%.
Comparative example 1
This comparative example differs from example 1 in that the cooling rate was not controlled by directly cooling to room temperature.
Comparative example 2
This comparative example differs from example 1 in that step (1) was not added with ethanol, was not sonicated, and instead, equal amounts of ethanol and other starting materials were directly wet ball milled in a ball milling tank.
Comparative example 3
The difference between this comparative example and example 1 is that the cooling rate was 4℃per minute.
Comparative example 4
This comparative example differs from example 1 in that the dispersion after the ultrasound is dried and then subjected to dry grinding, the dry ground product being used for high temperature calcination.
And (3) battery assembly:
the positive electrode materials prepared in the respective examples and comparative examples were used as positive electrode active materials according to the positive electrode active materials: conductive agent (Super P): and (3) adding the binder (PVDF) =80:10:10 mass ratio into NMP to prepare positive electrode slurry, coating the positive electrode slurry on an aluminum foil, and drying to obtain the positive electrode plate.
The positive plate, the sodium plate and the electrolyte are adopted to prepare the battery, wherein the electrolyte is prepared by combining EC and DMC with the volume ratio of 1:1 with sodium hexafluorophosphate (the concentration is 1M), and a glass fiber diaphragm is adopted to assemble the sodium ion half battery.
Test electrochemical performance (see table 1 for results):
(1) And (3) testing buckling capacity: the charge rate is 0.5C, the discharge rate is 1C, the charge cut-off voltage is 4.2V, the discharge cut-off voltage is 2.0V, and the discharge specific capacity under 1C is counted.
(2) And (3) cyclic test: 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 rate 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
From the above table 1, it can be seen that the method of the present invention can effectively purify the material structure, improve the crystallinity and purity of the material, obtain pure-phase sodium-ion battery positive electrode material with uniform element distribution and good crystallinity, and effectively prevent the problem of poor cycling stability caused by problems of dissolution of transition metal, volume change, etc. in the cycling process of the positive electrode material.
As is clear from a comparison of example 1 and example 3, an excessively large particle size of the raw material decreases the purity of the material, resulting in a decrease in the first discharge capacity and cycle performance.
As can be seen from a comparison of example 1 with example 4, the ultrasonic time is too short, which affects the effect of opening agglomerates in the raw material, reduces the pure phase of the material, resulting in a decrease in the first discharge capacity and cycle performance.
As can be seen from comparison of examples 1 and examples 5 to 6, the dispersion has a preferable range of solid content, and the solid content is in the range of 30% -50%, which is favorable for obtaining better ultrasonic dispersion effect and wet ball milling/sanding effect, further improving the material purity and the dispersion uniformity of transition elements, obtaining proper particle size, and further improving the first discharge capacity and the cycle performance.
As is clear from the comparison between example 1 and comparative example 1, the annealing effect cannot be achieved by adopting a natural cooling mode without controlling the cooling rate, and the crystallinity of the product is poor, so that the initial effect and the cycle performance are greatly reduced.
As is evident from the comparison of example 1 with comparative example 2, no sonication was performed, resulting in a decrease in the first effect and cycle performance.
As can be seen from the comparison of example 1 and comparative example 3, too fast a cooling rate cannot achieve an effective annealing effect, resulting in a decrease in initial efficiency and cycle performance.
As can be seen from the comparison of example 1 and comparative example 4, wet ball milling/grinding can better improve the initial efficiency and cycle performance of the material compared to dry ball milling.
The applicant states that the detailed method of the present invention is illustrated by the above examples, but the present invention is not limited to the detailed method described above, i.e. it does not mean that the present invention must be practiced in dependence upon the detailed method described above. It should be apparent to those skilled in the art that any modification of the present invention, equivalent substitution of raw materials for the product of the present invention, addition of auxiliary components, selection of specific modes, etc., falls within the scope of the present invention and the scope of disclosure.

Claims (23)

1. The preparation method of the positive electrode material of the sodium ion battery is characterized by comprising the following steps of:
(1) Mixing the raw materials of the positive electrode material of the sodium ion battery with a solvent, and then performing ultrasonic dispersion treatment to obtain a dispersion liquid;
(2) Carrying out ball milling/sand milling treatment on the dispersion liquid, then carrying out drying treatment, and calcining a dried product, wherein the cooling rate after calcination is 1 ℃/min-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 Na x M a Ni b Fe c Mn d O 2 Wherein a is more than or equal to 0.05 and less than or equal to 0.2,0.2, b is more than or equal to 0.35,0.2 and less than or equal to c is more 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= 1,0.75 and less than or equal to x/(a+b+c+d) is more 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%;
in the XRD spectrum of the sodium ion battery anode material, the diffraction peak intensities of different crystal planes satisfy the relation: i (003) /[I (104) +I (012) +I (018) ]≥0.45。
2. The method according to claim 1, wherein the starting material of the sodium ion battery positive electrode material of step (1) has a particle diameter D50 of 3 μm to 8 μm.
3. The method of claim 1, wherein the starting materials for 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.
4. The method of claim 1, wherein the solvent is an alcohol.
5. The method of claim 4, wherein the alcohol is ethanol.
6. The method according to claim 1, wherein the dispersion has a solids content of 30% -50%.
7. The method of claim 1, wherein the frequency of the ultrasonic dispersion is 50Hz to 90Hz and the time of the ultrasonic dispersion is 20min to 45min.
8. The method according to claim 1, wherein the ball milling in the step (2) is performed with ball milling beads having a particle size of 0.1mm to 1mm and a ball-to-material ratio of 3:1 to 10:1.
9. The method of claim 1, wherein the calcining of step (2) is at a temperature of 780 ℃ to 1000 ℃.
10. The method of claim 9, wherein the calcining of step (2) is at a temperature of 850 ℃ to 950 ℃.
11. The method of claim 1, wherein the calcination in step (2) is for a period of 8h to 15h.
12. The method of claim 11, wherein the calcination in step (2) is for a period of time ranging from 10h to 12h.
13. The method of claim 1, wherein the atmosphere of calcination of step (2) is an oxygen-containing atmosphere.
14. The method of claim 13, wherein the atmosphere of calcination in step (2) is an air atmosphere or an oxygen atmosphere.
15. The method of claim 1, wherein the firing in step (2) is at a rate of temperature rise of 2 ℃/min to 5 ℃/min.
16. The method according to claim 1, characterized in that it comprises the steps of:
(1) Weighing sodium salt, nickel source, iron source, manganese source and doping element-containing substances according to stoichiometric ratio, stirring with solvent, and performing ultrasonic dispersion treatment to obtain dispersion;
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) Ball milling/sanding the dispersion liquid;
(3) And carrying out vacuum drying treatment on the ball-milled/sand-ground material, carrying out high-temperature calcination treatment on the dried material, wherein the cooling rate after calcination is 1 ℃/min-3 ℃/min, and cooling to obtain the anode material.
17. The method of claim 1, wherein the XRD pattern of the sodium ion battery positive electrode material has a half-width of the (003) peak and the (104) peak in the range of 0.0830 ° -0.1130 °.
18. The method of claim 1, wherein the XRD pattern of the positive electrode material of the sodium ion battery is analyzed, and the crystal grain size of the positive electrode material of the sodium ion battery is determined by the scherrer equation
19. The method of claim 1, wherein the primary particles of the positive electrode material of the sodium ion battery have a disk shape and a particle diameter D50 of 3 μm to 8 μm.
20. The method of claim 1, wherein M comprises at least one of Li, B, co, zn, mg, cu, zr, al and Ti.
21. The method of claim 1, wherein M is a combination of Li and B.
22. A sodium ion battery positive electrode material prepared by the method of any one of claims 1-21.
23. A sodium ion battery comprising the sodium ion battery positive electrode material of claim 22.
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