CN118004970A - Method for preparing layered oxide by spray pyrolysis - Google Patents

Method for preparing layered oxide by spray pyrolysis Download PDF

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CN118004970A
CN118004970A CN202410166888.XA CN202410166888A CN118004970A CN 118004970 A CN118004970 A CN 118004970A CN 202410166888 A CN202410166888 A CN 202410166888A CN 118004970 A CN118004970 A CN 118004970A
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spray pyrolysis
layered oxide
hydroxide
preparing
sodium
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徐学留
阮丁山
刘更好
李永光
韦长玲
李长东
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Hunan Brunp Recycling Technology Co Ltd
Guangdong Brunp Recycling Technology Co Ltd
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Hunan Brunp Recycling Technology Co Ltd
Guangdong Brunp Recycling Technology Co Ltd
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Abstract

The layered oxide prepared by the method for preparing the layered oxide by spray pyrolysis can be used as a positive electrode material in a sodium ion battery, and when the layered oxide is prepared by using sulfate, nitrate, chloride and acetate of metal elements as raw materials, firstly, the salt in the raw materials is converted into hydroxide, and then the hydroxide is subjected to spray pyrolysis, so that the residual quantity of impurity elements such as nitrogen, sulfur and chlorine in the prepared layered oxide is reduced, the occupation ratio of hollow spheres is reduced, and the electrical property of the layered oxide is further improved; in addition, the spray pyrolysis of the hydroxide is also beneficial to reducing the temperature of the spray pyrolysis and reducing the energy consumption.

Description

Method for preparing layered oxide by spray pyrolysis
Technical Field
The present disclosure relates to the field of preparation technology of positive electrode materials, and in particular, to a method for preparing layered oxides using spray pyrolysis.
Background
In recent years, the new energy industry develops rapidly, the demand for the ion battery is larger and larger, and the preparation cost is higher and higher; how to reduce the cost and increase the efficiency becomes a difficult problem facing a plurality of enterprises.
The sodium element has the advantages of large resource storage capacity, wide global distribution, low raw material cost, safety, environmental protection and the like, so that the sodium ion battery is widely concerned, and the sodium ion battery material is also becoming a research hot spot and key point in the energy storage field and the novel battery field. Common positive electrode materials of sodium ion batteries are Prussian, polyanion, layered oxides and the like, wherein the layered oxides are popular as the positive electrode materials of the sodium ion batteries which are the most mainstream.
In the traditional synthesis method of the sodium positive electrode material layered oxide, the following are common: preparing a precursor by a coprecipitation method and then sintering; or directly sintering the mixture by using oxide to obtain the sodium anode material. The preparation cost is high no matter which synthesis method is adopted, so that a simpler synthesis process needs to be searched.
Spray pyrolysis is a favorable choice for cost reduction, but at present, the compatibility of the spray pyrolysis to raw materials is relatively narrow, and different problems exist for various raw materials. For example: the solubility of chloride in water is high, but HCl gas and Cl 2 which are difficult to treat are easy to generate in the pyrolysis process, and the raw material cost is high; although the decomposition temperature of nitrate is lower, toxic gas is generated in the pyrolysis process, and the air pressure in the nitrate is rapidly increased in the spray pyrolysis process, so that a large number of irregular particles are generated, and the sphericity of the material is reduced or hollow is generated; acetate has relatively low solubility in water, and carbon-containing impurities are easy to introduce; the pyrolysis temperature of the sulfate is too high, and the energy consumption is too high by adopting a spray pyrolysis process.
In view of this, the present disclosure is specifically proposed.
Disclosure of Invention
The present disclosure is directed to a method for producing a layered oxide by spray pyrolysis, which reduces the residual amount of impurity elements such as nitrogen, sulfur, chlorine, etc. in the layered oxide.
The present disclosure is implemented as follows:
In a first aspect, the present disclosure provides a method for preparing a layered oxide using spray pyrolysis, comprising: adding alkali into a raw material solution to perform precipitation reaction and performing solid-liquid separation to obtain hydroxide precipitate, and performing spray pyrolysis on the hydroxide to obtain a layered oxide, wherein the raw material comprises sulfate of a metal element, chloride of the metal element, acetate of the metal element or nitrate of the metal element.
In some embodiments, the spray pyrolysis temperature is 500 ℃ to 1100 ℃.
In some embodiments, the spray pyrolysis temperature is 600 ℃ to 800 ℃.
In some embodiments, further comprising washing the hydroxide precipitate with a detergent, and then spray pyrolyzing the washed hydroxide.
In some embodiments, the detergent is at least one of NaOH solution, KOH solution, na 2CO3 solution, and NaHCO 3 solution.
In some embodiments, the total content of chlorine, sulfur, nitrogen and carbon in the washed hydroxide is less than 10000ppm.
In some embodiments, the layered oxide has a structure MO 2, wherein M is a metal element.
In some embodiments, the M is at least two of Al, ti, cr, mn, fe, co, ni, cu, zn, sn, zr, mo, nb, Y, W, in and Ge.
In some embodiments, the precipitation reaction is at a temperature of 25 ℃ to 90 ℃ for a time of 0.5h to 100h.
In some embodiments, the precipitation reaction is accompanied by stirring at a frequency of 20Hz to 60Hz.
In some embodiments, the precipitation reaction pH is 8-13.
In some embodiments, the base is at least one of an organic base and an inorganic base.
In some embodiments, the base is at least one of NaOH, KOH, and Na 2CO3.
In some embodiments, the hydroxide is mixed with a solvent to produce a hydroxide slurry having a solids content of 10% to 50% prior to spray pyrolysis of the hydroxide.
In some embodiments, the median particle size of the hydroxide is from 2um to 20um.
In some embodiments, the slurry further includes a sodium salt, resulting in a layered oxide of Na yMxO2.
In some embodiments, the sodium salts are Na 2CO3 and NaHCO 3.
In some embodiments, the ratio of the total molar amount of M element to the total molar amount of sodium element in the slurry is (1:1) - (1:1.05).
The present disclosure has the following beneficial effects:
The layered oxide can be used as a positive electrode material in a sodium ion battery, and when the layered oxide is prepared by using sulfate, chloride and acetate of metal elements as raw materials, firstly, the salt in the raw materials is converted into hydroxide, and then the hydroxide is subjected to spray pyrolysis, so that the residual quantity of impurity elements such as nitrogen, sulfur and chlorine in the prepared layered oxide is reduced, the occupation ratio of hollow spheres is reduced, and the electrical property of the layered oxide is further improved; in addition, the spray pyrolysis of the hydroxide is also beneficial to reducing the temperature of the spray pyrolysis and reducing the energy consumption.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present disclosure, the drawings that are needed in the embodiments will be briefly described below, it being understood that the following drawings only illustrate some embodiments of the present disclosure and therefore should not be considered as limiting the scope, and other related drawings may be obtained according to these drawings without inventive effort for a person of ordinary skill in the art.
FIG. 1 is a flow chart of the present disclosure;
FIG. 2 is an electron micrograph of the sodium positive electrode material obtained in example 1;
FIG. 3 is an electron micrograph of the sodium positive electrode material obtained in comparative example 1.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present disclosure more apparent, the technical solutions in the embodiments of the present disclosure will be clearly and completely described below. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
The present disclosure provides a method for preparing a layered oxide using spray pyrolysis, comprising: adding alkali into a raw material solution to perform precipitation reaction and performing solid-liquid separation to obtain hydroxide precipitate, and performing spray pyrolysis on the hydroxide to obtain a layered oxide, wherein the raw material comprises sulfate of a metal element, chloride of the metal element, acetate of the metal element or nitrate of the metal element.
The layered oxide in the embodiment can be used as a positive electrode material for sodium ion batteries, and when the layered oxide is prepared by using sulfate, chloride and acetate of metal elements as raw materials, salt in the raw materials is converted into hydroxide, and then spray pyrolysis is carried out on the hydroxide. Firstly, sulfate radical, chloride ion, nitrate radical and acetate radical in the raw materials are dissolved in a reaction system in the precipitation reaction process, only a small number of the sulfate radical, chloride ion, nitrate radical and acetate radical are mixed in the precipitation in the hydroxide precipitation process, and most of the small impurities escape in the form of sulfur oxide, nitrogen oxide, carbon oxide, chlorine gas or hydrogen chloride and the like in the subsequent spray pyrolysis, so that the residual quantity of impurity elements such as nitrogen, sulfur, chlorine and the like in the layered oxide can be effectively reduced compared with the direct spray pyrolysis of the raw materials. Secondly, when the raw materials are directly subjected to spray pyrolysis, the content of sulfate radical, chloride ion, nitrate radical and acetate radical in the raw materials is high, and the generated sulfur oxide, nitrogen oxide, carbon oxide and chlorine gas or hydrogen chloride gas are in large amounts, so that the ratio of hollow spheres in the obtained layered oxide is excessively high, the compaction density, strength and the like of the layered oxide are influenced, and further the electrical properties such as capacity, circulation stability and the like applied to batteries are influenced; when the salt in the raw material is converted into hydroxide, the hydroxide is dehydrated in the spray drying process, and the water molecules occupy smaller volume, so that the proportion of hollow spheres is obviously reduced. And finally, nitrogen, sulfur and the like in the raw materials are required to be removed in the form of sulfur oxide, nitrogen oxide, carbon oxide and chlorine or hydrogen chloride gas by directly carrying out spray pyrolysis on the raw materials, and the layered oxide can be obtained only by carrying out dehydration after the raw materials are converted into hydroxide.
In some embodiments, the spray pyrolysis temperature is 500 ℃ to 1100 ℃, in particular can be any value between 500 ℃, 600 ℃, 700 ℃, 800 ℃, 900 ℃, 1000 ℃, 1100 ℃, or 500 ℃ to 1100 ℃. Compared with the direct spray pyrolysis of the raw materials, the temperature is lower under the same conditions. In some embodiments, the spray pyrolysis temperature is 600 ℃ to 800 ℃.
In some embodiments, further comprising washing the hydroxide precipitate with a detergent, and then spray pyrolyzing the washed hydroxide. The content of impurities in the obtained layered oxide can be further reduced on the basis of the above by removing soluble impurities in the hydroxide precipitate by using a detergent. If the raw material is directly spray-dried, impurities in the layered oxide cannot be removed, and only the impurities have an influence on the performance and the like of the layered oxide. In contrast, the present embodiment has a significant advantage in controlling the impurity content in the layered oxide.
In some embodiments, the detergent is at least one of NaOH solution, KOH solution, na 2CO3 solution, and NaHCO 3 solution. In the process of washing the hydroxide precipitate by alkali, some soluble impurities in the precipitate, such as sulfate, nitrate and the like, are dissolved into the solution, so that the precipitate mixed in the hydroxide is reduced.
In some embodiments, the total content of chlorine, sulfur, nitrogen and carbon in the washed hydroxide may be less than 10000ppm, specifically may be 10000ppm, 5000ppm, 3000ppm, 1000ppm, 500ppm, 300ppm, 100ppm, less than 100ppm or any value less than 10000ppm, and in order to improve the performance of the resulting positive electrode material, the residual amounts of chlorine, sulfur, nitrogen and carbon may be as low as possible, but in view of reducing the cost of the detergent, the residual amounts of chlorine, sulfur, nitrogen and carbon may be between 500ppm and 1000ppm, while affecting the performance of the layered oxide positive electrode material, but within acceptable ranges.
In some embodiments, the layered oxide has a structure MO 2, wherein M is a metal element. Wherein M can be one metal element or more than two metal elements, and can be specifically selected according to the needs. In general, in order to ensure the electrical properties of the positive electrode material, M is selected from two or more metal elements.
In some embodiments, the M is at least two of Al, ti, cr, mn, fe, co, ni, cu, zn, sn, zr, mo, nb, Y, W, in and Ge, for example, a combination of Mn, fe, ni, a combination of Mn, fe, ni, cu, and the like.
In some embodiments, the temperature of the precipitation reaction is 25 ℃ to 90 ℃, specifically may be any value between 25 ℃, 30 ℃, 40 ℃, 50 ℃, 60 ℃, 70 ℃, 80 ℃, 90 ℃ or 25 ℃ to 90 ℃, and the time is 0.5h to 100h, specifically may be any value between 0.5h, 1h, 5h, 10h, 20h, 30h, 50h, 70h, 100h or 0.5h to 100 h. Specifically, the temperature and time of the precipitation reaction are related to the kind of the raw materials, and the temperature and precipitation rate at which different metals are combined with hydroxyl groups to form precipitates are different, so that the reaction temperature and time need to be reasonably adjusted according to the raw materials.
In some embodiments, the stirring is accompanied by stirring during the precipitation reaction at a frequency of 20Hz to 60Hz, in particular, may be 20Hz, 30Hz, 40Hz, 50Hz, 60Hz or any value between 20Hz and 60 Hz. The stirring process can improve the uniformity of the reaction liquid in the reaction process, is favorable for enabling the solid liquid to uniformly contact, and improves the reaction rate. In some embodiments, the precipitation reaction is followed by aging by standing for a period of time.
In some embodiments, the precipitation reaction pH is 8-13, and in particular may be any value between 8, 9, 10, 11, 12, 13 or 8-13, the pH of the precipitation reaction being dependent on the kind of metal element.
In some embodiments, the base is at least one of an organic base and an inorganic base, providing hydroxide for metal ion precipitation.
In some embodiments, the base is at least one of NaOH, KOH, and Na 2CO3, and sodium and potassium salts are more soluble in water and have little precipitation. In addition, even if the layered oxide contains a small amount of sodium ions and potassium ions, the subsequent washing process can be reduced, and sodium can be introduced into the layered oxide to obtain a positive electrode material, so that the effect on the performance of the layered oxide is small.
In some embodiments, the hydroxide is mixed with a solvent to prepare a hydroxide slurry before spray pyrolysis of the hydroxide, wherein the solid content of the hydroxide slurry is 10% -50%, and the hydroxide is pulped to prepare a slurry before spray pyrolysis, so that pyrolysis is facilitated.
In some embodiments, the median particle size of the hydroxide is from 2um to 20um.
In this embodiment, the particle size of the prepared layered oxide is related to the particle size of hydroxide in the slurry on one hand, and the solid content of the slurry on the other hand, and the particle size and the solid content of the hydroxide are adjusted to obtain the layered oxide with relatively uniform and controllable particle size. If the raw materials are directly subjected to spray pyrolysis, the obtained layered oxide has relatively poor particle size uniformity. Specifically, the smaller the particle size of the hydroxide, the lower the solid content in the hydroxide slurry, and the particle size of the obtained layered oxide is relatively smaller; conversely, if the larger the particle size of the hydroxide is, the higher the solid content in the hydroxide slurry is, and the particle size of the resulting layered oxide is relatively larger.
In some embodiments, the slurry further includes a sodium salt, resulting in a layered oxide of Na yMxO2. When sodium ions exist in the slurry, sodium salts can be subjected to spray pyrolysis together with hydroxide to obtain layered oxides containing sodium.
In some embodiments, the sodium salts are Na 2CO3 and NaHCO 3. The carbonate or bicarbonate combines with water or hydroxide in the slurry to release carbon dioxide, and the carbon impurity content in the layered oxide is not excessively high.
In some embodiments, the ratio of the total molar amount of M element to the total molar amount of sodium element in the slurry is (1:1) - (1:1.05), specifically may be any value between 1:1, 1:1.01, 1:1.02, 1:1.03, 1:1.04, 1:1.05, or 1:1-1:1.05. In other embodiments, the layered oxide prepared by spray pyrolysis can be mixed with a sodium source and then calcined to obtain the layered oxide positive electrode material containing sodium, and compared with the direct spray pyrolysis, the process for preparing the layered oxide containing sodium is simpler.
The features and capabilities of the present disclosure are described in further detail below in connection with the examples.
Example 1
The present embodiment provides a method for preparing a Ni 0.25Mn0.55Fe0.15Cu0.05O2 sodium positive electrode layered oxide, as shown in fig. 1, specifically comprising the following steps:
(1) According to Ni: mn: fe: the molar mass of Cu is 0.25:0.55:0.15:0.05, and the total concentration of sulfate preparation Ni, mn, fe, cu is 2mol/L of molten metal.
(2) Adding the prepared metal liquid into a reaction kettle, starting stirring, adding NaOH at room temperature until the pH is about 10.0, and performing reaction precipitation for 30min until the precipitate is hardly regenerated, thus obtaining Ni 0.25Mn0.55Fe0.15Cu0.05(OH)2 precipitate with the D50 of 10 um.
(3) And (3) performing alkali washing on the Ni 0.25Mn0.55Fe0.15Cu0.05(OH)2 precipitate by adopting a 10mol/L NaOH solution to remove S, so as to obtain the Ni 0.25Mn0.55Fe0.15Cu0.05(OH)2 precipitate with lower S content.
(4) And (3) preparing Ni 0.25Mn0.55Fe0.15Cu0.05(OH)2 in the step (3) into slurry with the solid content of 20%, carrying out high-temperature spray pyrolysis, wherein the spray pyrolysis temperature is 600 ℃, and finally obtaining the sodium cathode material Ni 0.25Mn0.55Fe0.15Cu0.05O2, wherein the electron microscope images are shown in fig. 2 and 3.
Example 2
The embodiment provides a method for preparing Ni 0.3Mn0.5Fe0.1Cu0.1O2 sodium positive electrode layered oxide, which specifically comprises the following steps:
(1) According to Ni: mn: fe: the molar mass of Cu is 0.3:0.5:0.1:0.1, and the sulfate is weighed to prepare the metal liquid with the total concentration of Ni, mn, fe, cu being 1.8 mol/L.
(2) Adding the prepared metal liquid into a reaction kettle, starting stirring, adding NaOH at room temperature until the pH is about 11.0, and performing reaction precipitation for 30min until little precipitate is formed, thereby obtaining Ni 0.3Mn0.5Fe0.1Cu0.1(OH)2 precipitate with D50 of 8 um.
(3) And (3) performing alkali washing on the Ni 0.3Mn0.5Fe0.1Cu0.1(OH)2 precipitate by using a 10mol/L NaOH solution to remove S, so as to obtain the Ni 0.3Mn0.5Fe0.1Cu0.1(OH)2 precipitate with lower S content.
(4) And (3) preparing Ni 0.3Mn0.5Fe0.1Cu0.1(OH)2 in the step (3) into slurry with the solid content of 30%, carrying out high-temperature spray pyrolysis, wherein the spray pyrolysis temperature is 700 ℃, and finally obtaining the sodium cathode material Ni 0.3Mn0.5Fe0.1Cu0.1O2.
Example 3
The embodiment provides a method for preparing Ni 0.2Mn0.4Fe0.2Cu0.2O2 sodium positive electrode layered oxide, which specifically comprises the following steps:
(1) According to Ni: mn: fe: the molar mass of Cu is 0.2:0.4:0.2:0.2, and the sulfate is weighed to prepare the metal liquid with the total concentration of Ni, mn, fe, cu mol/L being 1.5 mol/L.
(2) Adding the prepared metal liquid into a reaction kettle, starting stirring, adding NaOH at room temperature until the pH is about 12.0, and performing reaction precipitation for 30min until little precipitate is formed, thereby obtaining Ni 0.2Mn0.4Fe0.2Cu0.2(OH)2 precipitate with the D50 of 7 um.
(3) And (3) performing alkali washing on the Ni 0.2Mn0.4Fe0.2Cu0.2(OH)2 precipitate by using a 10mol/L NaOH solution to remove S, so as to obtain the Ni 0.2Mn0.4Fe0.2Cu0.2(OH)2 precipitate with lower S content.
(4) And (3) preparing Ni 0.2Mn0.4Fe0.2Cu0.2(OH)2 in the step (3) into slurry with the solid content of 25%, carrying out high-temperature spray pyrolysis, wherein the spray pyrolysis temperature is 600 ℃, and finally obtaining the sodium cathode material Ni 0.2Mn0.4Fe0.2Cu0.2O2.
Example 4
The embodiment provides a method for preparing Ni 1/3Mn1/3Fe1/3O2 sodium positive electrode layered oxide, which specifically comprises the following steps:
(1) According to Ni: mn: the molar mass of Fe is 1/3:1/3:1/3, and sulfate is weighed to prepare Ni, mn, fe, cu total concentration of molten metal of 2 mol/L.
(2) Adding the prepared metal liquid into a reaction kettle, starting stirring, adding NaOH at room temperature until the pH is about 10.5, and performing reaction precipitation for 20min until the precipitate is hardly regenerated, thus obtaining Ni 1/3Mn1/3Fe1/3(OH)2 precipitate with D50 of 6 um.
(3) And (3) performing alkali washing on the Ni 1/3Mn1/3Fe1/3(OH)2 precipitate by using an NaOH solution with the concentration of 8mol/L to remove S, so as to obtain the Ni 1/3Mn1/3Fe1/3(OH)2 precipitate with lower S content.
(4) And (3) preparing Ni 1/3Mn1/3Fe1/3(OH)2 in the step (3) into slurry with the solid content of 30%, carrying out high-temperature spray pyrolysis, wherein the spray pyrolysis temperature is 600 ℃, and finally obtaining the regenerated sodium cathode material Ni 1/3Mn1/3Fe1/3O2.
Example 5
The embodiment provides a method for preparing NaNi 0.2Mn0.5Co0.1Fe0.2O2 sodium positive electrode layered oxide, which specifically comprises the following steps:
(1) According to Ni: mn: co: the molar mass of Fe is 0.2:0.5:0.1:0.2, and the sulfate is weighed to prepare the metal liquid with the total concentration of Ni, mn, fe, cu being 1.8 mol/L.
(2) Adding the prepared metal liquid into a reaction kettle, starting stirring, adding NaOH at room temperature until the pH is about 10.5, and performing reaction precipitation for 20min until the precipitate is hardly regenerated, thus obtaining Ni 0.2Mn0.5Co0.1Fe0.2(OH)2 precipitate with the D50 of 10 um.
(3) And (3) performing alkali washing on the Ni 0.2Mn0.5Co0.1Fe0.2(OH)2 precipitate by using a NaOH solution with the concentration of 5mol/L to remove S, obtaining Ni 0.2Mn0.5Co0.1Fe0.2(OH)2 precipitate with lower S content, and adding sodium salt.
(4) And (3) preparing Ni 0.2Mn0.5Co0.1Fe0.2(OH)2 in the step (3) into slurry with the solid content of 15%, and carrying out high-temperature spray pyrolysis, wherein the spray pyrolysis temperature is 800 ℃, so as to finally obtain the regenerated sodium cathode material NaNi 0.2Mn0.5Co0.1Fe0.2O2.
Example 6
The embodiment provides a method for preparing NaNi 0.3Mn0.4Co0.1Fe0.2O2 sodium positive electrode layered oxide, which specifically comprises the following steps:
(1) According to Ni: mn: co: the molar mass of Fe is 0.3:0.4:0.1:0.2, and the sulfate is weighed to prepare the metal liquid with the total concentration of Ni, mn, fe, cu being 1.7 mol/L.
(2) Adding the prepared metal liquid into a reaction kettle, starting stirring, adding NaOH at room temperature until the pH is about 10.5, and performing reaction precipitation for 20min until little precipitate is formed, thereby obtaining Ni 0.3Mn0.4Co0.1Fe0.2 precipitate with the D50 of 11 um.
(3) And (3) performing alkali washing on the Ni 0.3Mn0.4Co0.1Fe0.2(OH)2 precipitate by using a 10mol/L NaOH solution to remove S, obtaining Ni 0.3Mn0.4Co0.1Fe0.2(OH)2 precipitate with lower S content, and adding sodium salt.
(4) And (3) preparing Ni 0.3Mn0.4Co0.1Fe0.2 in the step (3) into slurry with the solid content of 20%, carrying out high-temperature spray pyrolysis, wherein the spray pyrolysis temperature is 800 ℃, and finally obtaining the regenerated sodium cathode material NaNi 0.3Mn0.4Co0.1Fe0.2O2.
Example 7
This embodiment differs from embodiment 1 only in that: the step S of alkali washing is omitted.
Example 8
This embodiment differs from embodiment 1 only in that: the Ni 0.25Mn0.55Fe0.15Cu0.05(OH)2 precipitate with D50 of 8um is obtained;
Example 9
This embodiment differs from embodiment 1 only in that: the solid content of the slurry in the step (4) is 30%.
Example 10
This embodiment differs from embodiment 1 only in that: the sulfate in step (1) is replaced by nitrate.
The present embodiment provides a method for preparing a Ni 0.25Mn0.55Fe0.15Cu0.05O2 sodium positive electrode layered oxide, as shown in fig. 1, specifically comprising the following steps:
(1) According to Ni: mn: fe: cu has a molar mass of 0.25:0.55:0.15:0.05, and the nitrate is weighed to prepare Ni, mn, fe, cu total concentration of 2mol/L molten metal.
(2) Adding the prepared metal liquid into a reaction kettle, starting stirring, adding NaOH at room temperature until the pH is about 10.0, and performing reaction precipitation for 30min until the precipitate is hardly regenerated, thus obtaining Ni 0.25Mn0.55Fe0.15Cu0.05(OH)2 precipitate with the D50 of 5 um.
(3) And (3) performing alkali washing on the Ni 0.25Mn0.55Fe0.15Cu0.05(OH)2 precipitate by adopting a NaOH solution with the concentration of 10mol/L to remove nitrogen oxides, so as to obtain the Ni 0.25Mn0.55Fe0.15Cu0.05(OH)2 precipitate with lower N content.
(4) And (3) preparing Ni 0.25Mn0.55Fe0.15Cu0.05(OH)2 in the step (3) into slurry with the solid content of 20%, carrying out high-temperature spray pyrolysis, wherein the spray pyrolysis temperature is 600 ℃, and finally obtaining the sodium cathode material Ni 0.25Mn0.55Fe0.15Cu0.05O2.
Comparative example 1
The comparative example differs from example 1 only in that steps (2), (3) and (4) were omitted and the molten metal was directly subjected to spray pyrolysis at 800 ℃.
The layered oxides obtained in the above examples and comparative examples were tested and the results are shown in table 1.
TABLE 1
Test examples
And preparing a positive electrode material of the sodium ion battery from the positive electrode precursors of the sodium ion batteries prepared in the examples and the comparative examples, preparing a positive electrode plate, and assembling the positive electrode plate, the negative electrode plate, the diaphragm and the electrolyte to obtain the sodium ion battery.
If the sodium is added, directly spraying the positive electrode material, directly installing a battery for testing; if the sodium spraying material is not added, the preparation method of the sodium-electricity positive electrode material comprises the following steps: and mixing the precursor materials obtained in each example and the comparative example with a sodium source, and carrying out mixing treatment, wherein the mass ratio of Na to Me is 1.05:1, and then carrying out high-temperature sintering treatment, the sintering temperature is 930 ℃, and the sintering time is 10 hours, so as to obtain the sodium ion battery anode material.
The preparation method of the positive plate comprises the following steps: and weighing and proportioning the sodium ion battery anode material, the conductive carbon black and the vinylidene fluoride according to the mass ratio of 80:10:10, and then uniformly mixing in an N-methylpyrrolidone solution. And (3) preparing slurry, coating the slurry on an aluminum foil, carrying out vacuum drying treatment, and shearing and punching the slurry into positive plates with the diameter of 12mm after drying.
The preparation method of the sodium ion battery comprises the following steps: the button cell was assembled in an argon glove box using a metal sodium sheet as the negative electrode, 1mol/L NaPF 6/Polycarbonate (PC), ethylene Carbonate (EC), dimethyl carbonate (DMC) (volume ratio of 1:1:1) +5% FEC solution as the electrolyte, and glass fiber as the separator.
The electrochemical performance test is carried out on the sodium ion battery, and the test conditions are as follows: the charge and discharge tests were carried out at 0.1C over a voltage range of 1.5-4.1V to obtain a first charge-discharge gram capacity and a first coulombic efficiency, and the test results are shown in table 2.
TABLE 2
Industrial applicability
The layered oxide prepared by the method for preparing the layered oxide by spray pyrolysis can be used as a positive electrode material in a sodium ion battery, and when the layered oxide is prepared by using sulfate, chloride and acetate of metal elements as raw materials, firstly, the salt in the raw materials is converted into hydroxide, and then the hydroxide is subjected to spray pyrolysis, so that the method is beneficial to reducing the residual quantity of impurity elements such as nitrogen, sulfur and chlorine in the prepared layered oxide, reducing the occupation ratio of hollow spheres, and further improving the electrical property of the layered oxide; in addition, the spray pyrolysis of the hydroxide is also beneficial to reducing the temperature of the spray pyrolysis and reducing the energy consumption.

Claims (10)

1. A method for preparing a layered oxide using spray pyrolysis, comprising: adding alkali into a raw material solution to perform precipitation reaction and performing solid-liquid separation to obtain hydroxide precipitate, and performing spray pyrolysis on the hydroxide to obtain a layered oxide, wherein the raw material comprises sulfate of a metal element, chloride of the metal element, acetate of the metal element or nitrate of the metal element.
2. The method for preparing a layered oxide by spray pyrolysis according to claim 1, wherein the temperature of the spray pyrolysis is 500 ℃ to 1100 ℃; preferably, the spray pyrolysis temperature is 600 ℃ to 800 ℃.
3. The method for producing a layered oxide by spray pyrolysis according to claim 1, further comprising washing the hydroxide precipitate with a detergent, and then spray pyrolyzing the washed hydroxide;
Preferably, the detergent is at least one of NaOH solution, KOH solution, na 2CO3 solution and NaHCO 3 solution;
Preferably, the total content of chlorine, sulfur, nitrogen and carbon in the washed hydroxide is less than 10000ppm.
4. The method for producing a layered oxide by spray pyrolysis according to claim 1, wherein the layered oxide has a structure of MO 2, wherein M is a metal element;
Preferably, M is at least two of Al, ti, cr, mn, fe, co, ni, cu, zn, sn, zr, mo, nb, Y, W, in and Ge.
5. The method for preparing a layered oxide by spray pyrolysis according to claim 1, wherein the precipitation reaction is carried out at a temperature of 25 to 90 ℃ for a time of 0.5 to 100 hours.
6. The method for producing a layered oxide by spray pyrolysis according to claim 1, wherein stirring is carried out with a stirring frequency of 20Hz to 60Hz during the precipitation reaction.
7. The method for producing a layered oxide by spray pyrolysis according to claim 1, wherein the precipitation reaction pH is 8 to 13.
8. The method for producing a layered oxide by spray pyrolysis according to claim 1, wherein the base is at least one of an organic base and an inorganic base;
Preferably, the base is at least one of NaOH, KOH and Na 2CO3.
9. The method for producing a layered oxide by spray pyrolysis according to claim 1, wherein before spray pyrolysis of the hydroxide, the hydroxide is mixed with a solvent to produce a hydroxide slurry, and the solid content of the hydroxide slurry is 10% -50%;
Preferably, the median particle size of the hydroxide is from 2um to 20um.
10. The method for preparing a layered oxide by spray pyrolysis according to claim 9, wherein the slurry further comprises sodium salt, and the obtained layered oxide is Na yMxO2;
Preferably, the sodium salts are Na 2CO3 and NaHCO 3;
preferably, the ratio of the total molar amount of M element to the total molar amount of sodium element in the slurry is (1:1) - (1:1.05).
CN202410166888.XA 2024-02-06 2024-02-06 Method for preparing layered oxide by spray pyrolysis Pending CN118004970A (en)

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