CN114804227B - 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 sodium ion battery positive electrode material precursor has a chemical formula of Ni x Mn y Cr z (OH) 2 kNaOH, the preparation method comprising: 1. preparing a mixed solution of Ni, mn, cr and acetylenic diol; preparing sodium hydroxide or potassium hydroxide solution as a precipitator; preparing ammonia water solution as complexing agent; 2. adding pure water, acetylenic diol, a precipitator and a complexing agent to prepare a base solution; 3. introducing mixed gas of oxygen and nitrogen, and continuously adding the mixed solution, the precipitant and the complexing agent into a kettle for coprecipitation; controlling the solid content in the kettle, and stopping the reaction when the granularity of the material reaches the target; 4. and carrying out filter pressing, washing and drying on the product to obtain a loose and porous sodium ion battery anode material precursor. The precursor can improve the diffusion speed of sodium ions, the uniformity of sodium elements inside and outside the positive electrode material after sintering is high, the consumption of an external sodium source can be reduced, and the problem of overhigh alkali content on the surface of the positive electrode 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 lithium-taking war, and the lithium resource is relatively short, so that the cost of the lithium ion battery is high. Compared with the scarcity of lithium resources, the sodium has high reserve quantity on the earth and low price, so the sodium ion battery has very wide application prospect.
The performance of sodium ion batteries is mainly affected by the positive electrode material of sodium ion batteries. Among the positive electrode materials of sodium ion batteries, layered transition metal oxides have been attracting attention because of their high capacity and good cycle performance. However, in the process of preparing the sodium ion positive electrode material, the diffusion speed is relatively slow due to the large radius of sodium ion atoms, so that the sodium element inside and outside the positive electrode material is unevenly distributed, the surface alkali content is increased, and the electrochemical performance is affected.
Therefore, how to solve the above-mentioned drawbacks of the prior art is a subject to be studied and solved by the present invention.
Disclosure of Invention
The invention aims to provide a precursor of a layered structure sodium ion battery anode material and a preparation method thereof.
In order to achieve the purpose, the invention adopts the technical scheme that:
a layered structure sodium ion battery positive electrode material precursor 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 or equal to 1.0, y is more than or equal to 0 and less than or equal to 0.50, z is more than or equal to 0.01 and less than or equal to 0.05,0.08, and k is more than or equal to 0.15.
The relevant content explanation in the technical scheme is as follows:
1. in the scheme, D50 is 6-10 um, the granularity diameter distance is 0.50 < (D90-D10)/D50 is less than 0.70, and the tap density is 0.85-1.25 g/cm 3 A specific surface area of 110 to 190m 2 /g。
In order to achieve the purpose, the technical scheme adopted in the method level of the invention is as follows:
a preparation method of a layered structure sodium ion battery anode material precursor comprises the following steps:
step one, preparing a mixed solution of Ni, mn, cr and acetylenic diol;
preparing 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;
adding pure water, acetylenic diol, 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 through the precipitant, controlling the ammonia concentration in the base solution to be 0.01-0.18 mol/L through the complexing agent, and maintaining the temperature to be 55-75 ℃;
step three, keeping stirring of a 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 is 500-800L/h, and continuously adding the mixed solution, the precipitant and the complexing agent in the step one into the reaction kettle at the flow rate of 300-800 mL/min for coprecipitation reaction; the pH 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;
the overflow flows to a concentration machine, the solid content in the reaction kettle is controlled to be 31-41%, and when the granularity D50 of the materials in the reaction kettle grows to 6-10 um and the granularity diameter distance is 0.50 < (D90-D10)/D50 < 0.70, the reaction is stopped;
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 explanation in the technical scheme is as follows:
1. in the above scheme, in the first step, 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 first step, the mass percentage of the alkyne diol is 0.1-0.9%.
3. In the scheme, in the second step, the mass percentage of the acetylenic diol in the base solution is 0.05-0.45%.
4. In the above scheme, the precursor is chemically treatedNi is x Mn y Cr z (OH) 2 kNaOH, wherein x is more than or equal to 0.5 and less than or equal to 1.0, y is more than or equal to 0 and less than or equal to 0.50, z is more than or equal to 0.01 and less than or equal to 0.05,0.08, and k is more than or equal to 0.15.
The working principle and the advantages of the invention are as follows:
1. the invention realizes the uniform distribution of Ni, mn and Cr elements in the atomic layer by introducing Cr elements in the process of preparing the precursor. In addition, compared with Ni element, cr element has larger ionic radius, is favorable for expanding the interlayer spacing of the anode material, and improves the diffusion speed of sodium ions.
2. According to the invention, the alkyne diol is added as the nonionic surfactant, so that the surfactant is relatively stable and does not react with Ni, mn and Cr elements, and the precursor secondary particles can be effectively promoted to disperse while homogeneous precipitation of the Ni, mn and Cr elements is ensured, 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. The oxygen can be introduced to partially Mn 2+ Oxidation to Mn 3+ The primary particles are thinned to form a porous structure, which is favorable for adsorbing Na element, and further the Ni with the chemical formula is obtained x Mn y Cr z (OH) 2 Precursor of kNaOH. The precursor is internally and uniformly dispersed with a certain amount of Na elements, so that the uniformity of the Na elements inside and outside the positive electrode material after sintering can be improved, and the consumption of an external sodium source can be reduced, thereby effectively solving the problem of overhigh alkali content on the surface of the positive electrode material caused by slow diffusion of sodium ions in the sintering process.
Drawings
FIG. 1A is a Markov 2000 particle size test screenshot of a precursor prepared according to example 1 of the present invention;
FIG. 1B is an SEM image of a precursor of example 1 of the present invention;
FIG. 2 is a Markov 2000 particle size test screenshot of a precursor prepared according to comparative example 1 of the present invention;
FIG. 3 is a Markov 2000 particle size test screenshot of a precursor prepared according to comparative example 2 of the present invention;
FIG. 4 is a Markov 2000 particle size test screenshot of a precursor prepared according to comparative example 3 of the present invention;
FIG. 5 is a Markov 2000 particle size test screenshot of a precursor prepared according to comparative example 4 of the present invention;
FIG. 6 is a Markov 2000 particle size test screenshot of a precursor prepared according to comparative example 5 of the present invention;
FIG. 7 is a Markov 2000 particle size test screenshot of a precursor prepared according to comparative example 6 of the present invention;
FIG. 8A is a Markov 2000 particle size test screenshot of a precursor prepared according to example 2 of the present invention;
FIG. 8B is an SEM image of a precursor of example 2 of the present invention;
FIG. 9 is a graph showing the cycle performance test of the sodium ion positive electrode materials prepared in example 1 of the present invention and each comparative example.
Detailed Description
The invention is further described below with reference to the accompanying drawings and examples:
the present invention will be described in detail with reference to the drawings, wherein modifications and variations are possible in light of the teachings of the present invention, without departing from the spirit and scope of the present invention, as will be apparent to those of skill in the art upon understanding the embodiments of the present invention.
The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the present disclosure. As used herein, the terms "comprising," "including," "having," and the like are intended to be open-ended terms, meaning including, but not limited to.
The term (terms) as used herein generally has the ordinary meaning of each term as used in this field, in this disclosure, and in the special context, unless otherwise noted. Certain terms used to describe the present disclosure are discussed below, or elsewhere in this specification, to provide additional guidance to those skilled in the art in connection with the description herein.
Example 1:
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 acetylenic diol, wherein the total molar concentration of Ni, mn and Cr in the mixed solution is 2.0mol/L, the molar ratio is 55:42:3, and the mass percentage content of the acetylenic diol is 0.2%;
preparing 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;
adding pure water, acetylenic diol, 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 through 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 acetylenic diol in the base solution is 0.10%;
step three, keeping 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 precipitant and the complexing agent in the step one into the reaction kettle at the flow rate of 300-800 mL/min for coprecipitation reaction; the pH 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 65mg/L;
the overflow flows to a concentration machine, the solid content in the reaction kettle is controlled to be 31-41 percent, and the reaction is stopped when the granularity D50 of the materials in the reaction kettle grows to 6-10 um and the granularity diameter distance is 0.50 < (D90-D10)/D50 < 0.70;
step four, the coprecipitation product in the step three is subjected to filter pressing, washing and drying to obtain a precursor of the positive electrode material of the sodium ion battery with the layered structure, wherein the chemical formula of the product is Ni 0.55 Mn 0.42 Cr 0.03 (OH) 2 0.12NaOH, D50 of 6.828um, particle size diameter of 0.635, tap density of 1.05g/cm 3 A specific surface area of 120.5m 2 And/g, the relevant data are shown in Table 1.
The precursor prepared by the method is used for preparing a sodium ion battery anode material, and the electrical performance is tested, and the method comprises the following steps:
the precursor Ni prepared above is processed 0.55 Mn 0.42 Cr 0.03 (OH) 2 0.12NaOH and Na 2 CO 3 Uniformly mixing in a high-speed mixer according to a molar ratio of 1.0:0.93, then placing in a sintering furnace, calcining at 800 ℃ for 24 hours, continuously introducing air in the process, and obtaining the sodium ion positive electrode material NaNi at a flow rate of 5L/min 0.55 Mn 0.42 Cr 0.03 O 2 . Calcining the obtained positive electrode material NaNi 0.55 Mn 0.42 Cr 0.03 O 2 Half cells were fabricated and charge and discharge tested at a voltage window of 2.5-4.2V, a current density of 0.1C, and a test temperature of 25 ℃. (Markov 2000 granularity test screenshot see FIG. 1A)
Comparative example 1:
the difference from example 1 is that the concentration of the acetylenic diol in the first step is different, the acetylenic diol is not added in this comparative example 1, and the rest is the same as in example 1. The obtained precursor was washed and dried, and the relevant data are shown in table 1. (Markov 2000 granularity test screenshot see FIG. 2)
Comparative example 2:
the difference from example 1 is that the concentration of the acetylenic diol in the first step is different, the percentage by mass of the acetylenic diol in comparative example 2 is 1.2%, and the rest is the same as in example 1. The obtained precursor was washed and dried, and the relevant data are shown in table 1. (Markov 2000 granularity test screenshot see FIG. 3)
Comparative example 3:
the difference from example 1 is that the molar ratio of Cr element in the first step is different, cr element is not added in this comparative example 3, and the remainder is the same as in example 1. The obtained precursor was washed and dried, and the relevant data are shown in table 1. (Markov 2000 granularity test screenshot see FIG. 4)
Comparative example 4:
the difference from example 1 is that the molar ratio of Cr element in the first step is different, the molar ratio of Ni, mn, cr in this comparative example 4 is 55:39:6, and the remainder is exactly the same as in example 1. The obtained precursor was washed and dried, and the relevant data are shown in table 1. (Markov 2000 granularity test screenshot see FIG. 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 comparative example 5 was maintained at 45mg/L, and the obtained precursor was mixed with Na 2 CO 3 The mixing was carried out in a molar ratio of 1:1.00, the remainder being exactly the same as in example 1. The obtained precursor was washed and dried, and the relevant data are shown in table 1. (Markov 2000 granularity test screenshot see FIG. 6)
Comparative example 6:
the difference from example 1 was 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 exactly the same as in example 1. The obtained precursor was washed and dried, and the relevant data are shown in table 1. (Markov 2000 granularity test screenshot see FIG. 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 acetylenic diol, wherein the total molar concentration of Ni, mn and Cr in the mixed solution is 2.0mol/L, the molar ratio is 65:32:3, and the mass percentage content of the acetylenic diol is 0.2%;
preparing 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;
adding pure water, acetylenic diol, 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 through 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 acetylenic diol in the base solution is 0.10%;
step three, keeping 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 precipitant and the complexing agent in the step one into the reaction kettle at the flow rate of 300-800 mL/min for coprecipitation reaction; the pH 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 60mg/L;
the overflow flows to a concentration machine, the solid content in the reaction kettle is controlled to be 31-41 percent, and the reaction is stopped when the granularity D50 of the materials in the reaction kettle grows to 6-10 um and the granularity diameter distance is 0.50 < (D90-D10)/D50 < 0.70;
step four, the coprecipitation product in the step three is subjected to filter pressing, washing and drying to obtain a precursor of the positive electrode material of the sodium ion battery with the layered structure, 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 of 0.625, tap density of 1.09g/cm 3 A specific surface area of 115.1m 2 And/g, the relevant data are shown in Table 1.
The precursor prepared by the method is used for preparing a sodium ion battery anode material, and the electrical performance is tested, and the method comprises the following steps:
the precursor Ni prepared above is processed 0.65 Mn 0.32 Cr 0.03 (OH) 2 0.13NaOH and Na 2 CO 3 Uniformly mixing in a high-speed mixer according to a molar ratio of 1.0:0.92, then placing in a sintering furnace, calcining at 790 ℃ for 24 hours, continuously introducing air in the process, and obtaining the sodium ion positive electrode material NaNi at a flow rate of 5L/min 0.65 Mn 0.32 Cr 0.03 O 2 . Calcining the obtained positive electrode material NaNi 0.65 Mn 0.32 Cr 0.03 O 2 Half cells were fabricated and charge and discharge tested at a voltage window of 2.5-4.2V, a current density of 0.1C, and a test temperature of 25 ℃. (Markov 2000 granularity test screenshot see FIG. 8A)
Table 1 shows the data of the products obtained in each example and each comparative example.
From the data of each example and each comparative example in table 1, it can be seen that: the addition amount of the surfactant is controlled within a certain range,precursors prepared above or below this range have a wide particle size diameter, affecting product consistency, resulting in reduced electrical properties. The doping of a proper amount of Cr element can enlarge the interlayer spacing of the positive electrode material, improve the first discharge capacity, and reduce the first discharge capacity along with the improvement of the doping amount of the Cr element. The oxygen can be introduced to partially Mn 2+ Oxidation to Mn 3+ The primary particles are thinned, a porous structure is formed, the adsorption of Na element is facilitated, the sodium distribution amount in the sintering process is reduced, and the alkali content on the surface of the positive electrode material is reduced.
Fig. 1B and fig. 8B are respectively precursor field emission electron microscope diagrams prepared in example 1 and example 2, and it can be seen from the diagrams that the surface of the precursor of the positive electrode material of the sodium ion battery has a loose and porous structure, and the structure is favorable for transmitting sodium ions in the charge and discharge process, so that the electrochemical performance can be improved. Fig. 9 is a graph showing the results of the cycle performance test of the sodium ion cathode materials prepared in example 1 and each comparative example, and it is understood from the graph that the sodium ion cathode material prepared by the technique of the present invention has the optimal cycle performance.
The above embodiments are provided to illustrate the technical concept and features of the present invention and are intended to enable those skilled in the art to understand the content of the present invention and implement the same, and are not intended to limit the scope of the present invention. All equivalent changes or modifications made in accordance with the spirit of the present invention should be construed to be included in the scope of the present invention.
Claims (1)
1. A preparation method of a layered structure sodium ion battery anode material precursor is characterized by comprising the following steps: comprising the following steps:
preparing a mixed solution of Ni, mn, cr and acetylenic diol, wherein the total molar concentration of Ni, mn and Cr in the mixed solution is 2.0mol/L, the molar ratio is 55:42:3, and the mass percentage content of the acetylenic diol is 0.2%;
preparing 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;
adding pure water, acetylenic diol, 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 through 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 acetylenic diol in the base solution is 0.10%;
step three, keeping 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 precipitant and the complexing agent in the step one into the reaction kettle at the flow rate of 300-800 mL/min for coprecipitation reaction; the pH 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 65mg/L;
the overflow flows to a concentration machine, the solid content in the reaction kettle is controlled to be 31-41%, and the reaction is stopped when the granularity D50 of the materials in the reaction kettle grows to 6-10 mu m and the granularity diameter distance is 0.50 < (D90-D10)/D50 < 0.70;
step four, the coprecipitation product in the step three is subjected to filter pressing, washing and drying to obtain a precursor of the positive electrode material of the sodium ion battery with the layered structure, wherein the chemical formula of the product is Ni 0.55 Mn 0.42 Cr 0.03 (OH) 2 0.12NaOH, D50 of 6.828 μm, particle size diameter of 0.635, tap density of 1.05g/cm 3 A specific surface area of 120.5m 2 /g。
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