CN114804227A - Layered structure sodium ion battery positive electrode material precursor and preparation method thereof - Google Patents
Layered structure sodium ion battery positive electrode material precursor and preparation method thereof Download PDFInfo
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Abstract
A layered structure of precursor of positive electrode material of sodium-ion battery with chemical formula of Ni x Mn y Cr z (OH) 2 kNaOH, the preparation method comprises: firstly, preparing a mixed solution of Ni, Mn, Cr and alkynediol; preparing sodium hydroxide or potassium hydroxide solution as a precipitator; preparing an ammonia water solution as a complexing agent; adding pure water, alkynediol, a precipitator and a complexing agent to prepare a base solution; thirdly, introducing mixed gas of oxygen and nitrogen, and continuously adding the mixed solution, a precipitator and a complexing agent into the kettle for coprecipitation; controlling the solid content in the kettle as the materialStopping the reaction when the granularity reaches the target; and fourthly, carrying out filter pressing, washing and drying on the product to obtain a loose and porous precursor of the positive electrode material of the sodium-ion battery. The precursor can improve the diffusion speed of sodium ions, the uniformity of the internal and external sodium elements of the sintered anode material is high, the consumption of an external sodium source can be reduced, and the problem of overhigh alkali content on the surface of the anode material in the sintering process is effectively solved.
Description
Technical Field
The invention relates to the technical field of lithium ion battery anode materials, in particular to a layered structure sodium ion battery anode material precursor and a preparation method thereof.
Background
The rapid development of new energy automobiles causes the war of lithium deprivation, and lithium resources are relatively in short supply, so that the cost of lithium ion batteries is high. Compared with the scarcity of lithium resources, sodium has high reserve on the earth and low price, so the sodium ion battery has very wide application prospect.
The performance of the sodium-ion battery is mainly influenced by the positive electrode material of the sodium-ion battery. Among positive electrode materials for sodium ion batteries, layered transition metal oxides are receiving attention because of their high capacity and good cycle performance. However, in the process of preparing the sodium ion cathode material, the diffusion speed of the sodium ion is relatively slow due to the large atomic radius of the sodium ion, so that the distribution of sodium elements inside and outside the cathode material is uneven, the surface alkali content is increased, and the electrochemical performance is affected.
Therefore, how to solve the above-mentioned deficiencies of the prior art is a problem to be solved by the present invention.
Disclosure of Invention
The invention aims to provide a layered structure sodium-ion battery positive electrode material precursor and a preparation method thereof.
In order to achieve the purpose, the technical scheme adopted by the invention on the product level is as follows:
a layered structure of precursor of positive electrode material of sodium-ion battery with chemical formula of Ni x Mn y Cr z (OH) 2 kNaOH, wherein x is more than or equal to 0.5 and less than 1.0, y is more than 0 and less than or equal to 0.50, z is more than 0.01 and less than or equal to 0.05, and k is more than or equal to 0.08 and less than or equal to 0.15.
The relevant content in the above technical solution is explained as follows:
1. in the scheme, D50 is 6-10 um, the particle size diameter distance is 0.50 < (D90-D10)/D50 < 0.70, and the tap density is 0.85-1.25 g/cm 3 The specific surface area is 110-190 m 2 /g。
In order to achieve the purpose, the technical scheme adopted by the invention in the aspect of the method is as follows:
a preparation method of a layered structure sodium-ion battery positive electrode material precursor comprises the following steps:
step one, preparing a mixed solution of Ni, Mn, Cr and alkynediol;
preparing a sodium hydroxide or potassium hydroxide solution with the molar concentration of 8-10 mol/L as a precipitator;
preparing an ammonia water solution with the molar concentration of 0.1-0.8 mol/L as a complexing agent;
step two, adding pure water, alkynediol, the precipitant and the complexing agent into a closed reaction kettle to prepare a base solution, controlling the pH value of the base solution to be 11.20-11.60 by using the precipitant, controlling the ammonia concentration in the base solution to be 0.01-0.18 mol/L by using the complexing agent, and maintaining the temperature to be 55-75 ℃;
step three, keeping the stirring of the reaction kettle open, introducing mixed gas of oxygen and nitrogen, wherein the volume ratio of the oxygen to the nitrogen is 2.5: 1-3.5: 1, the flow rate is 500-800L/h, and continuously adding the mixed solution, the precipitator and the complexing agent in the step one into the reaction kettle at the flow rate of 300-800 mL/min respectively for coprecipitation reaction; the pH value is maintained at 10.75-11.15 in the reaction process, the reaction temperature is maintained at 55-75 ℃, the rotating speed of the reaction kettle is 300-500 r/min, and the oxygen content in the solution in the reaction kettle is maintained at 55-85 mg/L;
overflowing to the thickener, controlling the solid content in the reaction kettle to be 31-41%, and stopping the reaction when the granularity D50 of the material in the reaction kettle grows to 6-10 um and the granularity diameter distance is 0.50 < (D90-D10)/D50 is less than 0.70;
and step four, carrying out filter pressing, washing and drying on the coprecipitation product in the step three to obtain a loose and porous sodium ion battery anode material precursor.
The relevant content in the above technical solution is explained as follows:
1. in the scheme, in the step one, the total molar concentration of Ni, Mn and Cr in the mixed solution is 1.8-2.5 mol/L.
2. In the scheme, in the step one, the mass percentage of the alkynediol is 0.1-0.9%.
3. In the scheme, in the second step, the mass percentage of the alkynediol in the base solution is 0.05-0.45%.
4. In the above scheme, the chemical formula of the precursor is Ni x Mn y Cr z (OH) 2 kNaOH, wherein x is more than or equal to 0.5 and less than 1.0, y is more than 0 and less than or equal to 0.50, z is more than 0.01 and less than or equal to 0.05, and k is more than or equal to 0.08 and less than or equal to 0.15.
The working principle and the advantages of the invention are as follows:
1. according to the invention, the Cr element is introduced in the process of preparing the precursor, so that the Ni, Mn and Cr elements are uniformly distributed on the atomic layer. In addition, compared with Ni element, Cr element has larger ionic radius, which is beneficial to enlarging the interlayer spacing of the anode material and improving the diffusion speed of sodium ions.
2. The acetylene glycol is added as the nonionic surfactant, the surfactant is relatively stable and does not react with Ni, Mn and Cr elements, the homogeneous precipitation of the Ni, Mn and Cr elements is ensured, the dispersion of precursor secondary particles can be effectively promoted, and the agglomeration phenomenon is prevented.
3. When the precursor is prepared, the mixed gas of oxygen and nitrogen with the flow rate of 500-800L/h is continuously introduced, the volume ratio of the oxygen to the nitrogen is 2.5: 1-3.5: 1, and the oxygen content in the solution in the reaction kettle is maintained at 55-85 mg/L. Oxygen is introduced to partially remove Mn 2+ Oxidation to Mn 3+ The primary particles are refined to form a porous structure, which is beneficial to adsorbing Na elements, and then Ni with a chemical formula is obtained x Mn y Cr z (OH) 2 A precursor of kNaOH. A certain amount of Na elements are uniformly dispersed in the precursor, so that the uniformity of the sodium elements inside and outside the sintered anode material can be improved, and the dosage of an additional sodium source can be reduced, thereby effectively solving the problem of slow diffusion of sodium ions in the sintering process to cause the anode material to have a poor stabilityThe alkali content on the surface of the material is too high.
Drawings
Figure 1A is a marvin 2000 particle size test screenshot of the precursor prepared in example 1 of the present invention;
FIG. 1B is an SEM image of a precursor prepared in example 1 of the present invention;
figure 2 is a marvin 2000 particle size test screenshot of the precursor prepared in comparative example 1 of the present invention;
figure 3 is a marwen 2000 particle size test screenshot of the precursor prepared in comparative example 2 of the present invention;
figure 4 is a marvin 2000 particle size test screenshot of the precursor prepared in comparative example 3 of the present invention;
figure 5 is a marvin 2000 particle size test screenshot of the precursor prepared in comparative example 4 of the present invention;
figure 6 is a marwen 2000 particle size test screenshot of the precursor prepared in comparative example 5 of the present invention;
figure 7 is a marvin 2000 particle size test screenshot of the precursor prepared in comparative example 6 of the present invention;
figure 8A is a marvin 2000 particle size test screenshot of the precursor prepared in example 2 of the present invention;
FIG. 8B is an SEM image of a precursor prepared in example 2 of the present invention;
FIG. 9 is a graph showing the cycle performance of the Na-ion positive electrode material prepared in example 1 according to the present invention and various comparative examples.
Detailed Description
The invention is further described with reference to the following figures and examples:
the present disclosure will be described more fully hereinafter with reference to the accompanying drawings, in which embodiments of the disclosure may be shown and described, and which, when modified and varied by the techniques taught herein, can be made by those skilled in the art without departing from the spirit and scope of the disclosure.
The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the disclosure. As used herein, the terms "comprising," "including," "having," and the like are open-ended terms that mean including, but not limited to.
As used herein, the term (terms), unless otherwise indicated, shall generally have the ordinary meaning as commonly understood by one of ordinary skill in the art, in this written description and in the claims. Certain words used to describe the disclosure are discussed below or elsewhere in this specification to provide additional guidance to those skilled in the art in describing the disclosure.
Example 1:
a preparation method of a precursor of a sodium-ion battery positive electrode material with a layered structure comprises the following steps:
preparing a mixed solution of Ni, Mn, Cr and alkynediol, wherein the total molar concentration of the Ni, the Mn and the Cr in the mixed solution is 2.0mol/L, the molar ratio is 55:42:3, and the mass percentage of the alkynediol is 0.2%;
preparing a sodium hydroxide or potassium hydroxide solution with the molar concentration of 10mol/L as a precipitator;
preparing an ammonia water solution with the molar concentration of 0.2mol/L as a complexing agent;
step two, adding pure water, alkynediol, the precipitant and the complexing agent into a closed reaction kettle to prepare a base solution, controlling the pH value of the base solution to be 11.20-11.60 by using the precipitant, and maintaining the temperature at 60 ℃; the ammonia concentration in the base solution is 0.08mol/L, and the mass percentage of the alkynediol in the base solution is 0.10%;
step three, keeping the stirring of the reaction kettle open, introducing mixed gas of oxygen and nitrogen, wherein the volume ratio of the oxygen to the nitrogen is 2.6:1, the flow is 500-800L/h, and continuously adding the mixed solution, the precipitator and the complexing agent in the step one into the reaction kettle at the flow rate of 300-800 mL/min respectively for coprecipitation reaction; the pH value is maintained at 10.75-11.15 in the reaction process, the reaction temperature is maintained at 60 ℃, the rotating speed of the reaction kettle is 450r/min, and the oxygen content in the solution in the reaction kettle is maintained at 65 mg/L;
overflowing to the thickener, controlling the solid content in the reaction kettle to be 31-41%, and stopping the reaction when the granularity D50 of the material in the reaction kettle grows to be 6-10 um and the granularity diameter distance is 0.50 less than (D90-D10)/D50 is less than 0.70;
step four, the coprecipitation product in the step three is processed byFilter pressing, washing and drying to obtain the precursor of the layered structure sodium-ion battery anode material, wherein the chemical formula of the product is Ni 0.55 Mn 0.42 Cr 0.03 (OH) 2 0.12NaOH, D50 6.828um, particle size diameter distance of 0.635, tap density of 1.05g/cm 3 The specific surface area is 120.5m 2 The data are shown in Table 1.
Preparing the sodium ion battery anode material by using the prepared precursor, and testing the electrical property, wherein the method comprises the following steps:
the precursor Ni prepared in the above way 0.55 Mn 0.42 Cr 0.03 (OH) 2 0.12NaOH with Na 2 CO 3 Uniformly mixing the materials in a high-speed mixer according to the mol ratio of 1.0:0.93, then placing the mixture in a sintering furnace, calcining the mixture for 24 hours at the temperature of 800 ℃, continuously introducing air into the sintering furnace in the process, and obtaining the NaNi anode material with the flow rate of 5L/min 0.55 Mn 0.42 Cr 0.03 O 2 . Calcining the obtained cathode material NaNi 0.55 Mn 0.42 Cr 0.03 O 2 And (3) preparing a half cell and carrying out charge and discharge tests, wherein the test voltage window is 2.5-4.2V, the current density is 0.1C, and the test temperature is 25 ℃. (Malvern 2000 particle size test screenshot is shown in figure 1A)
Comparative example 1:
the difference from example 1 is that the concentration of the acetylenic diol in step one is different, and in this comparative example 1 no acetylenic diol is added, and the rest is exactly the same as example 1. The obtained precursor was washed and dried, and the relevant data are shown in table 1. (Malvern 2000 particle size test screen shot is shown in figure 2)
Comparative example 2:
the difference from example 1 is that the concentration of the acetylenic diol in step one is different, and the weight percentage of the acetylenic diol in comparative example 2 is 1.2%, which is identical to example 1. The obtained precursor was washed and dried, and the relevant data are shown in table 1. (Malvern 2000 particle size test screenshot is shown in figure 3)
Comparative example 3:
the difference from example 1 is that the molar ratio of Cr element in step one is different, and in this comparative example 3, Cr element is not added, and the rest is exactly the same as example 1. The obtained precursor was washed and dried, and the relevant data are shown in table 1. (Malvern 2000 particle size test screen shot is shown in figure 4)
Comparative example 4:
the difference from example 1 is that the molar ratio of Cr element in step one is different, and the molar ratio of Ni, Mn, and Cr in comparative example 4 is 55:39:6, and the rest is the same as example 1. The obtained precursor was washed and dried, and the relevant data are shown in table 1. (Malvern 2000 particle size test screenshot is shown in figure 5)
Comparative example 5:
the difference from example 1 is that the oxygen content in the solution in the reaction vessel in the third step was different, the oxygen content in the solution in the reaction vessel in this comparative example 5 was maintained at 45mg/L, and the obtained precursor was mixed with Na 2 CO 3 The mixture was mixed in a molar ratio of 1:1.00, and the rest was the same as in example 1. The precursor obtained was washed and dried, and the relevant data are shown in table 1. (Malvern 2000 particle size test screenshot is shown in figure 6)
Comparative example 6:
the difference from example 1 is that the oxygen content in the solution in the reaction vessel in the third step was different, and the oxygen content in the solution in the reaction vessel in this comparative example 6 was maintained at 95mg/L, and the rest was identical to example 1. The obtained precursor was washed and dried, and the relevant data are shown in table 1. (Malvern 2000 particle size test screenshot is shown in figure 7)
Example 2:
a preparation method of a layered structure sodium-ion battery positive electrode material precursor comprises the following steps:
preparing a mixed solution of Ni, Mn, Cr and alkynediol, wherein the total molar concentration of the Ni, the Mn and the Cr in the mixed solution is 2.0mol/L, the molar ratio is 65:32:3, and the mass percentage of the alkynediol is 0.2%;
preparing a sodium hydroxide or potassium hydroxide solution with the molar concentration of 10mol/L as a precipitator;
preparing an ammonia water solution with the molar concentration of 0.2mol/L as a complexing agent;
step two, adding pure water, alkynediol, the precipitant and the complexing agent into a closed reaction kettle to prepare a base solution, controlling the pH value of the base solution to be 11.20-11.60 by using the precipitant, and maintaining the temperature at 60 ℃; the ammonia concentration in the base solution is 0.08mol/L, and the mass percentage of the alkynediol in the base solution is 0.10%;
step three, keeping the stirring of the reaction kettle open, introducing mixed gas of oxygen and nitrogen, wherein the volume ratio of the oxygen to the nitrogen is 3.1:1, the flow is 500-800L/h, and continuously adding the mixed solution, the precipitator and the complexing agent in the step one into the reaction kettle at the flow rate of 300-800 mL/min respectively for coprecipitation reaction; the pH value is maintained at 10.75-11.15 in the reaction process, the reaction temperature is maintained at 60 ℃, the rotating speed of the reaction kettle is 450r/min, and the oxygen content in the solution in the reaction kettle is maintained at 60 mg/L;
overflowing to the thickener, controlling the solid content in the reaction kettle to be 31-41%, and stopping the reaction when the granularity D50 of the material in the reaction kettle grows to be 6-10 um and the granularity diameter distance is 0.50 less than (D90-D10)/D50 is less than 0.70;
step four, carrying out filter pressing, washing and drying on the coprecipitation product in the step three to obtain a precursor of the layered structure sodium-ion battery anode material, wherein the chemical formula of the product is Ni 0.65 Mn 0.32 Cr 0.03 (OH) 2 0.13NaOH, D50 of 8.563um, particle size diameter distance of 0.625, tap density of 1.09g/cm 3 The specific surface area is 115.1m 2 The data are shown in Table 1.
Preparing the sodium ion battery anode material by using the prepared precursor, and testing the electrical property, wherein the method comprises the following steps:
the precursor Ni prepared in the above way 0.65 Mn 0.32 Cr 0.03 (OH) 2 0.13NaOH with Na 2 CO 3 Uniformly mixing the materials in a high-speed mixer according to the mol ratio of 1.0:0.92, then placing the mixture in a sintering furnace, calcining the mixture for 24 hours at the temperature of 790 ℃, continuously introducing air into the sintering furnace in the process, and obtaining the NaNi anode material with the flow rate of 5L/min 0.65 Mn 0.32 Cr 0.03 O 2 . Calcining the obtained cathode material NaNi 0.65 Mn 0.32 Cr 0.03 O 2 And (3) preparing a half cell and carrying out charge and discharge tests, wherein the test voltage window is 2.5-4.2V, the current density is 0.1C, and the test temperature is 25 ℃. (MarkText 2000 particle size test screenshot is shown in FIG. 8A)
Table 1 compares the product data for the products produced in each example and each comparative example.
From the data in table 1 for the examples and comparative examples, it can be seen that: the addition amount of the surfactant needs to be controlled within a certain range, and the particle size of the precursor prepared by the surfactant is larger or smaller than the range, so that the consistency of the product is influenced, and the electrical property is reduced. The doping of an appropriate amount of the Cr element can enlarge the interlayer spacing of the positive electrode material and increase the first discharge capacity, which decreases as the doping amount of the Cr element increases. Oxygen is introduced to partially remove Mn 2+ Oxidation to Mn 3+ The method refines primary particles to form a porous structure, is favorable for adsorbing Na elements, reduces the amount of sodium in the sintering process, and reduces the alkali content on the surface of the anode material.
Fig. 1B and 8B are field emission electron microscope images of the precursors prepared in examples 1 and 2, respectively, and it can be seen from the images that the surface of the precursor of the positive electrode material of the sodium-ion battery has a loose and porous structure, which is beneficial to the transmission of sodium ions during the charging and discharging processes and can improve the electrochemical performance. Fig. 9 shows the cycle performance test results of the sodium ion cathode materials prepared in example 1 and each comparative example, and it can be seen that the sodium ion cathode material prepared by the technology of the present invention has the best cycle performance.
The above embodiments are merely illustrative of the technical ideas and features of the present invention, and the purpose thereof is to enable those skilled in the art to understand the contents of the present invention and implement the present invention, and not to limit the protection scope of the present invention. All equivalent changes and modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.
Claims (7)
1. A layered structure sodium ion battery anode material precursor is characterized in that: has a chemical formula of Ni x Mn y Cr z (OH) 2 kNaOH, wherein x is more than or equal to 0.5 and less than 1.0, y is more than 0 and less than or equal to 0.50, z is more than 0.01 and less than or equal to 0.05, and k is more than or equal to 0.08 and less than or equal to 0.15.
2. A precursor according to claim 1, wherein: d50 is 6-10 um, the particle size diameter distance is 0.50 less than (D90-D10)/D50 less than 0.70, and the tap density is 0.85-1.25 g/cm 3 The specific surface area is 110-190 m 2 /g。
3. A preparation method of a layered structure sodium-ion battery anode material precursor is characterized by comprising the following steps: the method comprises the following steps:
step one, preparing a mixed solution of Ni, Mn, Cr and alkynediol;
preparing a sodium hydroxide or potassium hydroxide solution with the molar concentration of 8-10 mol/L as a precipitator;
preparing an ammonia water solution with the molar concentration of 0.1-0.8 mol/L as a complexing agent;
step two, adding pure water, alkynediol, the precipitant and the complexing agent into a closed reaction kettle to prepare a base solution, controlling the pH value of the base solution to be 11.20-11.60 by using the precipitant, controlling the ammonia concentration in the base solution to be 0.01-0.18 mol/L by using the complexing agent, and maintaining the temperature to be 55-75 ℃;
step three, keeping the stirring of the reaction kettle open, introducing mixed gas of oxygen and nitrogen, wherein the volume ratio of the oxygen to the nitrogen is 2.5: 1-3.5: 1, the flow rate is 500-800L/h, and continuously adding the mixed solution, the precipitator and the complexing agent in the step one into the reaction kettle at the flow rate of 300-800 mL/min respectively for coprecipitation reaction; the pH value is maintained at 10.75-11.15 in the reaction process, the reaction temperature is maintained at 55-75 ℃, the rotating speed of the reaction kettle is 300-500 r/min, and the oxygen content in the solution in the reaction kettle is maintained at 55-85 mg/L;
overflowing to the thickener, controlling the solid content in the reaction kettle to be 31-41%, and stopping the reaction when the granularity D50 of the material in the reaction kettle grows to 6-10 um and the granularity diameter distance is 0.50 < (D90-D10)/D50 is less than 0.70;
and step four, carrying out filter pressing, washing and drying on the coprecipitation product in the step three to obtain a loose and porous sodium ion battery anode material precursor.
4. The production method according to claim 3, characterized in that: in the first step, the total molar concentration of Ni, Mn and Cr in the mixed solution is 1.8-2.5 mol/L.
5. The production method according to claim 3, characterized in that: in the first step, the mass percentage of the alkynediol is 0.1-0.9%.
6. The production method according to claim 3, characterized in that: in the second step, the mass percentage of the alkynediol in the base solution is 0.05-0.45%.
7. The production method according to claim 3, characterized in that: the chemical formula of the precursor is Ni x Mn y Cr z (OH) 2 kNaOH, wherein x is more than or equal to 0.5 and less than 1.0, y is more than 0 and less than or equal to 0.50, z is more than 0.01 and less than or equal to 0.05, and k is more than or equal to 0.08 and less than or equal to 0.15.
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