CN113193188A - Quaternary positive electrode material of sodium-ion battery and preparation method thereof - Google Patents
Quaternary positive electrode material of sodium-ion battery and preparation method thereof Download PDFInfo
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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 provides a quaternary positive electrode material of a sodium-ion battery and a preparation method thereof. The chemical general formula of the quaternary positive electrode material of the sodium-ion battery is LiaNa1‑aNibCoxMnyAlzO2Wherein x + y + z + b =1, 1>b is not less than 1/3, and a is more than 0 and less than 1. The preparation method comprises the following steps: taking an aluminum-doped lithium ion battery ternary positive electrode NCM as a raw material, and adding a sodium source into the raw material according to the molar ratio of a lithium element to a sodium element of a ratio of (a: 1-a) to obtain a mixture; dispersing and activating the mixture to obtain nano-scale precursor slurry; drying the precursor slurry to obtainTo nanoscale precursor materials; and (3) calcining the nanoscale precursor material in an oxygen atmosphere in two steps to obtain the quaternary positive electrode material of the sodium-ion battery. The method of the invention directly adopts the waste lithium ion battery ternary anode material as the raw material, and can realize the recycling of resources.
Description
Technical Field
The invention relates to the field of batteries, in particular to a quaternary positive electrode material of a sodium-ion battery and a preparation method thereof.
Background
Nowadays, lithium ion batteries are widely used in the fields of mobile electronic devices, aerospace, medical treatment, and the like, with many advantages such as high energy density, high operating voltage, almost no memory effect, and good safety. With the increase of the usage amount of the lithium ion battery, after repeated charge and discharge, the active material is deactivated and scrapped due to the structural change, and a huge amount of waste lithium ion battery anode materials are generated. And the electrode material contains a large amount of valuable metals such as nickel, iron, manganese, cobalt, lithium and the like, and if the valuable metals are not recycled, a large amount of metal resources are wasted. Therefore, the scientific and efficient recycling of the waste lithium ion battery electrode material becomes a problem to be solved urgently at present.
At present, relevant reports are available for recycling waste lithium ion battery electrode materials, for example, patent applications with publication numbers CN106785177A, CN110061319A, CN105098281A and CN111074074A, but the existing patent reports at least have the following defects: 1) the anode material after stripping still introduces the process of wet leaching-precipitation, the technical difficulty is large, and the process flow is long; 2) the need to separate the binder and conductive carbon from the waste material increases the technical difficulty and processing cost. In addition, no relevant report is reported in the prior art that the waste lithium ion anode material is regenerated into the layered anode of the sodium ion battery.
Disclosure of Invention
In view of the deficiencies in the prior art, it is an object of the present invention to address one or more of the problems in the prior art as set forth above. For example, one of the objectives of the present invention is to provide a preparation method that has low technical difficulty and short process flow and can be used for regenerating a positive electrode material of a sodium ion battery from a positive electrode material of a lithium ion battery.
In order to achieve the above object, one aspect of the present invention provides a quaternary positive electrode material for a sodium-ion battery, wherein the quaternary positive electrode material has a chemical formula of LiaNa1-aNibCoxMnyAlzO2Wherein x + y + z + b =1, 1>b≥1/3，0＜a＜1。
The invention provides a preparation method of a quaternary positive electrode material of a sodium-ion battery, which comprises the following steps: taking an aluminum-doped lithium ion battery ternary positive electrode NCM as a raw material, and adding a sodium source into the raw material according to the molar ratio of a lithium element to a sodium element of a ratio of (a: 1-a) to obtain a mixture; or taking the lithium ion battery ternary positive electrode NCM as a raw material, adding a sodium source into the raw material according to the molar ratio of the lithium element to the sodium element being a:1-a, and adding an aluminum oxide or an aluminum hydroxide into the raw material according to the amount of the aluminum element required by the prepared quaternary positive electrode material to obtain a mixture; dispersing and activating the mixture to obtain nano-scale precursor slurry; drying the precursor slurry to obtain a nanoscale precursor material; the nano-scale precursor material is calcined in two steps under the oxygen atmosphere to obtain the precursor material with the chemical general formula of LiaNa1-aNibCoxMnyAlzO2The quaternary positive electrode material for sodium-ion batteries, wherein x + y + z + b =1, 1>b≥1/3，0＜a＜1。
Compared with the prior art, the invention has the beneficial effects that:
(1) the method avoids the leaching-precipitation process, and has short process flow and small technical difficulty;
(2) the preparation method of the invention does not need to remove the binder and the conductive agent by roasting, can avoid environmental pollution and is environment-friendly;
(3) the preparation method directly adopts the waste lithium ion battery ternary anode material as the raw material to prepare the anode material of the sodium ion battery, can realize the recycling of resources, only adds a small amount of sodium source in the preparation process, and has low cost;
(4) the sodium ion anode material provided by the invention has good charge and discharge performance.
Drawings
Fig. 1 is a charge/discharge performance diagram of the positive electrode material of the sodium-ion battery prepared in example 1 at a rate of 0.15A/g.
FIG. 2 is a graph of the cycle performance of the positive electrode material of the sodium-ion battery prepared in example 1 at a rate of 0.15A/g.
FIG. 3 is a graph of the charge and discharge performance of the positive electrode material of the sodium-ion battery prepared in example 2 at a rate of 0.15A/g.
Fig. 4 is an SEM image of the nanoscale precursor material prepared in example 3.
Fig. 5 is an SEM image of the positive electrode material of the sodium-ion battery prepared in example 3.
Fig. 6 is an XRD pattern of the positive electrode material of the sodium-ion battery prepared in example 3.
FIG. 7 is a graph of the charge and discharge performance of the positive electrode material of the sodium-ion battery prepared in example 3 at a rate of 0.15A/g.
Detailed Description
Hereinafter, a quaternary positive electrode material for a sodium-ion battery and a method for preparing the same according to the present invention will be described in detail with reference to the accompanying drawings and exemplary embodiments.
One aspect of the invention provides a quaternary positive electrode material of a sodium-ion battery. In an exemplary embodiment of the quaternary positive electrode material for the sodium-ion battery, the chemical formula of the quaternary positive electrode material (NCMA) for the sodium-ion battery is LiaNa1-aNibCoxMnyAlzO2Wherein x + y + z + b =1, 1>b is not less than 1/3, and a is more than 0 and less than 1. Under the condition that x + y + z =1-b, x, y and z can be arbitrarily selected. For example, x =0.1, y =0.12, z = 0.05. As another example, x =0.28, y =0.25, and z = 0.11. The quaternary positive electrode material of the sodium-ion battery is granular and uniformly distributed, as shown in figure 5.
In another aspect of the present invention, there is provided a method for preparing a quaternary positive electrode material for a sodium-ion battery, and in an exemplary embodiment of the method for preparing a quaternary positive electrode material for a sodium-ion battery of the present invention, the method may include:
and S01, taking the aluminum-doped lithium ion battery ternary positive electrode NCM as a raw material, and adding a sodium source into the raw material according to the molar ratio of the lithium element to the sodium element of a:1-a to obtain a mixture. Or taking the lithium ion battery ternary positive electrode NCM as a raw material, adding a sodium source into the raw material according to the molar ratio of the lithium element to the sodium element being a:1-a, and adding an aluminum oxide or an aluminum hydroxide into the raw material according to the amount of the aluminum element required by the prepared quaternary positive electrode material to obtain a mixture.
Further, the ternary NCM positive electrode of the lithium ion battery is a nickel-cobalt-manganese material. Can be used as the ternary NCM anode material of the waste lithium ion battery.
The quaternary positive electrode material of the sodium-ion battery to be prepared contains sodium elements and aluminum elements, so the raw materials also contain the sodium elements and the aluminum elements. For the source of sodium element, a sodium source may be added during the preparation. The amount of the sodium source added is required to ensure that the molar ratio of the lithium element to the sodium element in the raw material is a: 1-a.
For the source of the aluminum element, two approaches can be provided, one is that the ternary NCM anode material of the ion battery contains the aluminum element, namely the ternary NCM anode material doped with aluminum is used as a raw material; and secondly, the ternary NCM anode material which does not contain aluminum element is taken as a raw material, and an aluminum source is added in the preparation process. The adding amount of the aluminum source can be determined according to the set aluminum content required by the sodium ion quaternary positive electrode material.
The nickel element, cobalt element and manganese element contained in the raw materials are not limited to a large amount. The stoichiometric ratio of nickel element, cobalt element and manganese element in the sodium ion quaternary positive electrode material is determined according to the amount of elements contained in the lithium ion battery ternary positive electrode material. After the ternary cathode material is prepared through the steps S01-S04, the obtained stoichiometric ratio of the nickel element, the cobalt element and the manganese element is the stoichiometric ratio of the nickel element, the cobalt element and the manganese element in the sodium ion quaternary cathode material.
And S02, dispersing and activating the mixture to obtain the nanoscale precursor slurry.
Further, the mixture dispersion activation may be performed by subjecting the mixture to mechanical activation in a dispersion medium. The mechanical activation may be ball milling or sanding. The rotating speed of the ball milling or sanding is 100-2000 r/min. The time of ball milling or sanding can be 1-20 h. For example, the rotational speed of the ball mill or sand mill may be 500 rpm and the time may be 6 hours. The dispersion medium here may be deionized water, ethanol, ethylene glycol or the like. Of course, the dispersion medium of the present invention is not limited thereto.
And S03, drying the precursor slurry to obtain the nanometer precursor material.
Further, the drying treatment may include drying at a temperature of 40 ℃ to 150 ℃. The drying time can be 10-20 h. For example, the temperature of the drying treatment may be 100 ℃, and the time of the drying treatment may be 15 hours.
S04, calcining the nano-scale precursor material at a preset oxygen pressure for two steps to obtain the precursor material with the chemical general formula of LiaNa1- aNibCoxMnyAlzO2The quaternary positive electrode material for sodium-ion batteries, wherein x + y + z + b =1, 1>b≥1/3，0＜a＜1。
Further, the two-step calcination may include a first-step calcination and a second-step calcination after the first-step calcination is performed. The first step of calcination can be carried out at the temperature of 400-600 ℃. Further, the calcination can be carried out at the temperature of 420-580 ℃. The time of the first step of calcination can be 2-7 h. For example, the time of calcination may be 5 hours. The second step of calcination can be carried out at the temperature of 700-900 ℃. Further, the calcination can be carried out at 730-880 ℃. The time of the second step of calcination can be 10-20 h. For example, the time of calcination may be 15 hours. The crystal structure of the cathode material formed by calcination can be more complete through two-step calcination. The two sections of calcination arranged and the calcination temperature arranged in a matched manner are beneficial to improving the cycle performance of the prepared anode material, the cycle performance can be improved by more than 3% compared with that of one section of calcination, and the particle size distribution of the anode material is more uniform.
Further, the aluminum source added may be an oxide of aluminum or a hydroxide of aluminum. For example, it may be alumina or aluminum hydroxide.
Further, the sodium source may be one or a combination of sodium carbonate, sodium bicarbonate, sodium hydroxide, sodium acetate, and sodium phosphate. Of course, the sodium source of the present invention is not limited thereto.
The invention further provides a sodium-ion battery positive electrode, which comprises the quaternary positive electrode material of the sodium-ion battery or the quaternary positive electrode material of the sodium-ion battery prepared by the preparation method of the quaternary positive electrode material of the sodium-ion battery.
In order that the above-described exemplary embodiments of the invention may be better understood, further description thereof with reference to specific examples is provided below.
Example 1
Step 1, collecting waste aluminum-doped ternary NCM111 (LiNi)1/3Co1/3Mn1/3O2) And (3) repeatedly discharging the lithium ion battery for 4 hours on a charging and discharging machine until the voltage is less than 1V, and mechanically crushing for 24 hours to obtain a ternary positive electrode material of the waste lithium ion battery, wherein the ternary positive electrode material contains residual aluminum foil.
And 2, detecting the specific content of lithium in the ternary cathode material powder of the waste lithium ion battery obtained in the step 1 by using an analytical instrument. Sodium carbonate was added according to the stoichiometric ratio of lithium element to sodium element (a = 0.1) in the designed quaternary positive electrode material for sodium-ion batteries, to obtain a mixture.
And 3, placing the mixture obtained in the step 2 and ethanol in a ball mill for mechanical activation according to the mass ratio of the mixture to the ethanol as a dispersion medium of 1: 2. Ball milling is carried out for 8 hours at the rotating speed of 1200 r/min, and the nanoscale precursor slurry is obtained after ball milling activation.
And 4, drying the nanoscale precursor slurry at 110 ℃ for 16 hours to obtain the nanoscale precursor material.
And 5, calcining the nanoscale precursor material in an oxygen atmosphere in two steps, wherein the first step of calcining is carried out for 6 hours at the temperature of 500 ℃. The second step of calcination is carried out at 820 ℃ for 14 h. After calcination, Li was obtained by ICP measurement0.1Na0.9Ni0.32Co0.32Mn0.25Al0.11O2A quaternary positive electrode material of a sodium-ion battery.
And (3) coating the quaternary positive electrode material of the sodium-ion battery obtained above, and assembling the CR2025 button cell. The discharging specific capacity is kept at 146 mAh/g under the charging and discharging condition at 1C (1C =150mA/g) within a voltage window of 2.0-4.3V, the cycle performance is stable, the capacity retention rate is more than 80% after 40 weeks of charging and discharging, and the electrochemical performance is shown in figures 1 and 2, wherein a curve which gradually rises in figure 1 is a charging performance curve, and a curve which gradually falls is a discharging performance curve.
Example 2
Step 1, collecting waste aluminum-doped ternary NCM523 (LiNi)0.5Co0.2Mn0.3O2) And (3) repeatedly discharging the lithium ion battery for 4 hours on a charging and discharging machine until the voltage is less than 1V, and mechanically crushing for 24 hours to obtain the waste lithium ion battery ternary cathode material.
And 2, detecting the specific content of lithium in the ternary cathode material powder of the waste lithium ion battery obtained in the step 1 by using an analytical instrument. Sodium carbonate was added according to the stoichiometric ratio of lithium element to sodium element (a = 0.13) in the designed quaternary positive electrode material for sodium-ion batteries, resulting in a mixture.
And 3, placing the mixture obtained in the step 2 and ethanol in a ball mill for mechanical activation according to the mass ratio of the mixture to the ethanol as a dispersion medium of 1: 2. Ball milling is carried out for 8 hours at the rotating speed of 1500 rpm, and the nanoscale precursor slurry is obtained after ball milling activation.
And 4, drying the nanoscale slurry at 120 ℃ for 16 hours to obtain the nanoscale precursor material.
And 5, calcining the nanoscale precursor material in an oxygen atmosphere in two steps, wherein the first step of calcining is carried out for 4 hours at 480 ℃. The second step of calcination is carried out at the temperature of 800 ℃, and the calcination time is 12 h. After cooling, obtaining the quaternary positive material Li of the regenerated sodium-ion battery by ICP measurement0.13Na0.87Ni0.49Co0.11Mn0.3Al0.1O2。
And (3) coating the quaternary positive electrode material of the sodium-ion battery obtained above, and assembling the CR2025 button cell. The discharging specific capacity is kept at 135mAh/g under the charging and discharging of 1C (1C =150mA/g) within the voltage window of 2.0-4.3V, the electrochemical performance is shown in figure 3, the gradually rising curve in the figure is a charging performance curve, and the gradually falling curve is a discharging performance curve.
Example 3
Step 1, collecting waste aluminum-doped ternary NCM811 (Li)Ni0.8Co0.1Mn0.1O2) And (3) repeatedly discharging the lithium ion battery for 4 hours in a charging and discharging machine until the voltage is less than 1V, and mechanically crushing for 24 hours to obtain the waste lithium ion battery ternary cathode material.
And 2, detecting the specific content of lithium in the ternary cathode material powder of the waste lithium ion battery obtained in the step 1 by using an analytical instrument. Sodium carbonate was added according to the stoichiometric ratio of lithium element to sodium element (a = 0.12) in the designed quaternary positive electrode material for sodium-ion batteries, resulting in a mixture.
And 3, placing the mixture obtained in the step 2 and ethanol in a ball mill for mechanical activation according to the mass ratio of the mixture to the ethanol as a dispersion medium of 1: 2. Ball milling is carried out for 6 hours at the rotating speed of 1000 r/min, and the nanoscale precursor slurry is obtained after ball milling activation.
And 4, drying the nanoscale precursor slurry at 120 ℃ for 12h to obtain the nanoscale precursor material, wherein the SEM of the nanoscale precursor material is shown in FIG. 4.
And 5, calcining the nanoscale precursor material in an oxygen atmosphere in two steps, wherein the first step of calcining is carried out for 5 hours at 480 ℃. The second step of calcination is carried out at 780 ℃ for 12 h. After cooling, obtaining the quaternary positive material Li of the regenerated sodium-ion battery by ICP measurement0.12Na0.88Ni0.75Co0.05Mn0.1Al0.1O2The SEM is shown in figure 5, and the XRD is shown in figure 6.
And (3) coating the quaternary positive electrode material of the sodium-ion battery obtained above, and assembling the CR2025 button cell. The discharging specific capacity is kept at 129mAh/g under the charging and discharging of 1C (1C =150mA/g) within the voltage window of 2.0-4.3V, the electrochemical performance is shown in figure 7, the gradually rising curve in the figure is a charging performance curve, and the gradually falling curve is a discharging performance curve.
In conclusion, the preparation method disclosed by the invention does not need to remove the binder and the conductive agent by roasting, can avoid environmental pollution and is environment-friendly; the waste lithium ion battery ternary positive electrode material can be directly used as a raw material, the resource can be recycled, and only a small amount of sodium source is added in the preparation process, so that the cost is low; the preparation method is simple to operate and easy to popularize; the cathode material provided by the invention has good charge and discharge performance.
Although the present invention has been described above in connection with exemplary embodiments, it will be apparent to those skilled in the art that various modifications and changes may be made to the exemplary embodiments of the present invention without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (9)
1. The quaternary positive electrode material of the sodium-ion battery is characterized in that the chemical general formula of the quaternary positive electrode material is LiaNa1- aNibCoxMnyAlzO2Wherein x + y + z + b =1, 1>b≥1/3，0＜a＜1。
2. A preparation method of a quaternary positive electrode material of a sodium-ion battery is characterized by comprising the following steps:
taking an aluminum-doped lithium ion battery ternary positive electrode NCM as a raw material, and adding a sodium source into the raw material according to the molar ratio of a lithium element to a sodium element of a ratio of (a: 1-a) to obtain a mixture; or taking the ternary positive electrode NCM of the lithium ion battery as a raw material, adding a sodium source into the raw material according to the molar ratio of the lithium element to the sodium element being a:1-a, and adding an aluminum source into the raw material according to the amount of the aluminum element required by the prepared quaternary positive electrode material to obtain a mixture;
dispersing and activating the mixture to obtain nano-scale precursor slurry;
drying the precursor slurry to obtain a nanoscale precursor material;
the nano-scale precursor material is calcined in two steps under the oxygen atmosphere to obtain the precursor material with the chemical general formula of LiaNa1- aNibCoxMnyAlzO2The quaternary positive electrode material for sodium-ion batteries, wherein x + y + z + b =1, 1>b≥1/3，0＜a＜1。
3. The method for preparing the quaternary positive electrode material of the sodium-ion battery according to claim 2, wherein the calcination temperature in the first step is 400-600 ℃, and the calcination temperature in the second step is 700-900 ℃.
4. The preparation method of the quaternary positive electrode material for the sodium-ion battery as claimed in claim 2 or 3, wherein the calcination time of the first step is 2-7 h, and the calcination time of the second step is 10-20 h.
5. The method for preparing the quaternary positive electrode material for the sodium-ion battery according to claim 2 or 3, wherein the step of dispersing and activating the mixture comprises the step of adding the mixture into a dispersion medium for mechanical activation, wherein the mechanical activation is ball milling or sand milling, and the rotation speed of the ball milling or sand milling is 100-2000 rpm.
6. The method for preparing the quaternary positive electrode material of the sodium-ion battery as claimed in claim 2 or 3, wherein the drying treatment of the precursor slurry comprises drying treatment at 40-150 ℃ for 10-20 h.
7. The method for preparing the quaternary positive electrode material of the sodium-ion battery as claimed in claim 2 or 3, wherein the sodium source is one or more of sodium carbonate, sodium bicarbonate, sodium hydroxide, sodium acetate and sodium phosphate.
8. The method for preparing the quaternary positive electrode material of the sodium-ion battery as claimed in claim 2 or 3, wherein the aluminum source is aluminum oxide or aluminum hydroxide.
9. The positive electrode of the sodium-ion battery is characterized by comprising the quaternary positive electrode material of the sodium-ion battery as claimed in claim 1 or the quaternary positive electrode material of the sodium-ion battery prepared by the preparation method of the quaternary positive electrode material of the sodium-ion battery as claimed in any one of claims 2 to 8.
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