CN113800574A - Nickel-manganese-iron-aluminum-lithium cathode material and preparation method thereof - Google Patents
Nickel-manganese-iron-aluminum-lithium cathode material and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of battery materials, and discloses a nickel-manganese-iron-aluminum-lithium positive electrode material and a preparation method thereof. The preparation method comprises the following steps: (1) preparing a nickel salt and a manganese salt into a metal salt solution A; oxalic acid is used as a precipitator and is prepared into a mixed solution B with a complexing agent; (2) adding the metal salt solution A into the mixed solution B, heating and stirring to form emulsion; then aging, filtering, washing and drying to prepare a nickel manganese oxalate precursor; (3) adding an iron source into the nickel manganese oxalate precursor, and calcining for the first time; adding an aluminum source, and calcining for the second time; and finally, adding a lithium source, and calcining for three times to obtain the nickel-manganese-iron-aluminum-lithium cathode material. The nickel-manganese-iron-aluminum-lithium cathode material has higher theoretical capacity, the discharge capacity is between 190-195mAh/g at the multiplying power of 0.1C, the capacity retention rate is still about 85 percent after 100 cycles, and the material has better cycle stability.
Description
Technical Field
The invention belongs to the technical field of battery materials, and particularly relates to a nickel-manganese-iron-aluminum-lithium positive electrode material and a preparation method thereof.
Background
High nickel ternary positive electrode material nickel cobalt lithium aluminate (LiNi)1-x-yCoxAlyO2NCA for short) has very high energy density and power density and wide application prospect, so that the material is more and more widely concerned by the industry and academia. Wherein the high nickel system LiNi0.8Co0.15Al0.05O2As a system which is researched most mature and has the best performance in NCA materials, the material has higher actual specific capacity, and the discharge specific capacity under high cut-off voltage (4.3V) can reach 180 mAh/g. The NCA positive electrode material is just benefited from the high-capacity characteristic, and is used as the positive electrode material for manufacturing high-performance batteries, such as 18650 type power batteries in the new energy automobile industry.
Solid phase and coprecipitation methods are mainly used in the preparation of commercial NCA materials. The coprecipitation method has the advantages that the particle size of the prepared material particles is small and uniform, but the problems of uneven element distribution, difficult growth of crystal grains and the like in the product are easily caused by introducing aluminum element into the coprecipitation process. In addition, the NCA material has the advantage of large capacity, but has problems of low coulombic efficiency, poor cycle stability and rate capability, voltage attenuation, and the like for the first time.
Therefore, it is desirable to provide a positive electrode material having better performance than conventional NCA materials.
Disclosure of Invention
The present invention is directed to solving at least one of the problems of the prior art described above. Therefore, the invention provides a nickel-manganese-iron-aluminum-lithium positive electrode material and a preparation method thereof. The nickel-manganese-iron-aluminum-lithium cathode material has higher theoretical capacity, the discharge capacity is between 190-195mAh/g at the multiplying power of 0.1C, the capacity retention rate is still about 85 percent after 100 cycles, and the material has better cycle stability.
The invention provides a preparation method of a nickel-manganese-iron-aluminum-lithium anode material, which comprises the following steps of:
(1) preparing a nickel salt and a manganese salt into a metal salt solution A; oxalic acid is used as a precipitator and is prepared into a mixed solution B with a complexing agent;
(2) adding the metal salt solution A into the mixed solution B, heating and stirring to form emulsion; then aging, filtering, washing and drying to prepare a nickel manganese oxalate precursor;
(3) adding an iron source into the nickel manganese oxalate precursor, and calcining for the first time to obtain a primary sintered product; adding an aluminum source into the primary sintering product, and performing secondary calcination to obtain a secondary sintering product; and adding a lithium source into the secondary sintering product, and calcining for three times to obtain the nickel-manganese-iron-aluminum-lithium cathode material.
The invention adopts oxalic acid to replace sodium hydroxide with strong basicity and strong corrosivity as a precipitator of the coprecipitation process, reduces the corrosion to production equipment and the pollution to the environment, and can also effectively avoid the generation of AlO by Al element under the strong basicity condition2-Thereby causing the problems of uneven element distribution in the product and difficult grain growth, and effectively improving the electrochemical performance of the anode material. The invention also adopts a three-section sintering process, and an iron source and a precursor are respectively added, an aluminum source is added and a primary sintering product is subjected to secondary sintering, so that the defect of nonuniform grain growth of the precursor caused by nonuniform precipitation of aluminum ions under an alkaline condition in the traditional coprecipitation process, and the particle size is not uniform is further avoided. In addition, the invention also adopts manganese to completely replace noble metal cobalt to synthesize the high-nickel cobalt-free quaternary anode material, which can not only avoid the cost rise caused by the high-nickel anode material excessively depending on metal cobalt, but also carry out structural improvement on the high-nickel anode materialOptimization is facilitated, the layered structure of the material is stabilized, and the electrochemical properties such as the cycle stability and the like of the material are improved.
Preferably, the nickel salt is nickel nitrate and/or nickel sulfate.
Preferably, the manganese salt is manganese nitrate and/or manganese sulfate.
Preferably, the complexing agent is ammonia.
Preferably, the molar ratio of the precipitant to the complexing agent is 1: (1.8-2.5).
Preferably, the heating in step (2) is carried out to a temperature of 32-37 ℃.
Preferably, the rotation speed of the stirring in the step (2) is 800-.
Preferably, the lithium source is lithium hydroxide and/or lithium carbonate.
Preferably, the aluminum source is aluminum oxide.
Preferably, the iron source is ferric oxide.
According to the invention, aluminum oxide is adopted to replace aluminum salt aluminum sulfate commonly used in the traditional coprecipitation process, and ferric oxide is adopted as an external iron source, so that the defect of uneven distribution of precursor elements caused by incomplete precipitation of metal ions in the process of preparing the precursor by the traditional coprecipitation process is avoided.
Preferably, the primary calcination in step (3) comprises the following steps: raising the temperature from room temperature to about 700 ℃, raising the temperature at the speed of about 5 ℃/min, keeping the temperature for about 10h under the air atmosphere, and cooling to the room temperature.
Preferably, the secondary calcination in step (3) comprises the following steps: raising the temperature from room temperature to about 700 ℃, raising the temperature at the speed of about 5 ℃/min, keeping the temperature for about 10h under the air atmosphere, and cooling to the room temperature.
Preferably, the three-time calcination in step (3) comprises the following steps: raising the temperature from room temperature to about 750 ℃, raising the temperature at the speed of about 5 ℃/min, keeping the temperature for about 5h under the air atmosphere, and cooling to the room temperature.
The calcination temperature is an important factor influencing the degree of compactness, the degree of structural stability and the electrochemical performance of the prepared nickel-manganese-iron-aluminum-lithium cathode material. The temperature is too high, and an additional lithium source is easy to excessively volatilize, so that a sintered product is seriously short of lithium, and the original internal crystal structure of the material can be directly influenced, and the material is easy to decompose; when the temperature is too low, the added aluminum source and the added iron source cannot be co-melted with the precursor, and the crystal structure of the material cannot be easily formed, which has adverse effects on the electrochemical performance.
The invention also provides a nickel-manganese-iron-aluminum-lithium positive electrode material prepared by the preparation method.
Preferably, the molecular formula of the nickel-manganese-iron-aluminum-lithium cathode material is LiNi0.8Mn0.15-xFexAl0.05O2And x is 0.05 or 0.1.
Compared with the prior art, the invention has the following beneficial effects:
(1) according to the invention, oxalic acid is adopted to replace a precipitator sodium hydroxide used in the traditional coprecipitation process, and compared with a sodium hydroxide precipitator used in the traditional coprecipitation process, the oxalic acid precipitator has lower corrosivity to production equipment and is more environment-friendly. Meanwhile, the invention takes oxalic acid to replace alkaline substances as a precipitator, and can effectively prevent Al element from generating AlO under strong alkaline condition2-Thereby causing the problems of uneven element distribution in the product and difficult grain growth, and effectively improving the electrochemical performance of the anode material.
(2) According to the invention, by adopting a three-section sintering process, the secondary sintering is respectively carried out by adding an iron source and a precursor, adding an aluminum source and a primary sintering product, so that the defect of nonuniform grain growth of the precursor caused by nonuniform precipitation of aluminum ions under an alkaline condition in the traditional coprecipitation process, thereby causing nonuniform grain size is avoided. The particle size of the coprecipitation product particles is controlled by controlling parameters of the reaction process, such as temperature, rotating speed and the like, so that particles with regular appearance and uniform size can be obtained, and the electrochemical performance of the sintered product material is improved. The process has the advantages of simple preparation method, easy realization of process conditions, low energy consumption and the like.
(3) According to the invention, the high-nickel cobalt-free quaternary cathode material is synthesized by completely replacing expensive transition metal Co with cheap transition metal manganese (Mn), so that the production cost of the high-nickel material is reduced, and the stability of the layered structure of the high-nickel material is optimized, thereby obtaining the cathode material with excellent electrochemical performance.
(4) According to the invention, aluminum oxide is adopted to replace aluminum salt aluminum sulfate commonly used in the traditional coprecipitation process, and ferric oxide is adopted as an external iron source, so that the defect of uneven distribution of precursor elements caused by incomplete precipitation of metal ions in the process of preparing the precursor by the traditional coprecipitation process is avoided.
Drawings
FIG. 1 is XRD patterns of positive electrode materials obtained in example 1 (corresponding to 1a), example 2 (corresponding to 1b) and comparative example 1 (corresponding to 1 c);
FIG. 2 is a scanning electron microscope image of the positive electrode material of nickel manganese iron aluminum lithium prepared in example 1;
FIG. 3 is a scanning electron microscope image of the positive electrode material of nickel manganese iron aluminum lithium prepared in example 2;
FIG. 4 is a graph showing the cycle performance of the positive electrode material of nickel-manganese-iron-aluminum-lithium prepared in example 2;
FIG. 5 is a graph showing the cycle performance of the positive electrode materials of NiMnFeAlLi prepared in example 1 and comparative example 1;
FIG. 6 is a graph showing the cycle performance of the positive electrode materials of NiMnFeAlLi prepared in example 1 and comparative example 2.
Detailed Description
In order to make the technical solutions of the present invention more apparent to those skilled in the art, the following examples are given for illustration. It should be noted that the following examples are only preferred embodiments of the present invention, and the claimed protection scope is not limited thereto, and any modification, substitution, combination made without departing from the spirit and principle of the present invention are included in the protection scope of the present invention.
The starting materials, reagents or apparatuses used in the following examples are conventionally commercially available or can be obtained by conventionally known methods, unless otherwise specified.
Example 1
This example provides a nickel-manganese-iron-aluminum-lithium cathode material with a molecular formula of LiNi0.8Mn0.1Fe0.05Al0.05O2The preparation method comprises the following steps:
(1) nickel sulfate and manganese sulfate are mixed according to the molar weight ratio of metal ions of 0.8: 0.1, adding the mixture into deionized water, and continuously stirring to fully dissolve inorganic salt to prepare a green clear metal salt solution A;
weighing oxalic acid with the molar weight of 0.042mol, pouring the oxalic acid into a reaction kettle containing deionized water, heating and stirring at 35 ℃ to completely dissolve the oxalic acid, and then preparing a precipitant: weighing ammonia water with the molar quantity of 0.084mol according to the molar ratio of 1:2 of the complexing agent, pouring the ammonia water into a reaction kettle to prepare a white mixed solution B, and keeping the temperature of the reaction kettle at 35 ℃ and continuously stirring;
(2) continuously and slowly adding the metal salt solution A into the mixed solution B, keeping the temperature at 35 ℃ and continuously stirring for 20 hours at the rotating speed of 900r/min to form white emulsion; aging, filtering, washing and drying to obtain a blue-green nickel manganese oxalate precursor;
(3) according to the nickel manganese oxalate precursor: iron sesquioxide is 0.9: weighing ferric oxide according to the molar ratio of 0.05, mixing the ferric oxide and the ferric oxide, grinding, heating the obtained powder to 700 ℃ from room temperature, heating at the rate of 5 ℃/min, keeping the temperature for 10 hours in the air atmosphere, cooling to room temperature, and taking out to obtain a primary sintered product; and then according to the primary sintering product: weighing aluminum oxide according to the molar ratio of 0.95:0.05, mixing the aluminum oxide and the aluminum oxide, grinding, heating the obtained powder from room temperature to 700 ℃, keeping the temperature at the heating rate of 5 ℃/min under the air atmosphere for 10 hours, cooling to room temperature, and taking out to obtain a secondary sintering product; and then according to the secondary sintering product: weighing lithium hydroxide according to the molar ratio of 1:1.05, mixing the lithium hydroxide and the lithium hydroxide, grinding, heating the obtained powder to 750 ℃ from room temperature, heating the powder at the rate of 5 ℃/min, and keeping the temperature for 5 hours in an air atmosphere to obtain a final product LiNi0.8Mn0.1Fe0.05Al0.05O2。
Example 2
This example provides a nickel-manganese-iron-aluminum-lithium cathode material with a molecular formula of LiNi0.8Mn0.05Fe0.1Al0.05O2The preparation method comprises the following steps:
(1) nickel sulfate and manganese sulfate are mixed according to the molar weight ratio of metal ions of 0.8: 0.05 into deionized water, and continuously stirring to fully dissolve inorganic salt to prepare a green clear metal salt solution A;
weighing oxalic acid with the molar weight of 0.042mol, pouring the oxalic acid into a reaction kettle containing deionized water, heating and stirring at 35 ℃ to completely dissolve the oxalic acid, and then preparing a precipitant: weighing ammonia water with the molar quantity of 0.084mol according to the molar ratio of 1:2 of the complexing agent, pouring the ammonia water into a reaction kettle to prepare a white mixed solution B, and keeping the temperature of the reaction kettle at 35 ℃ and continuously stirring;
(2) continuously and slowly adding the metal salt solution A into the mixed solution B, keeping the temperature at 35 ℃ and continuously stirring for 20 hours at the rotating speed of 900r/min to form white emulsion; aging, filtering, washing and drying to obtain a blue-green nickel manganese oxalate precursor;
(3) according to the nickel manganese oxalate precursor: iron sesquioxide is 0.85: weighing ferric oxide according to a molar ratio of 0.1, mixing the ferric oxide and the ferric oxide, grinding, heating the obtained powder to 700 ℃ from room temperature, heating at a rate of 5 ℃/min, keeping the temperature for 10 hours in an air atmosphere, cooling to room temperature, and taking out to obtain a primary sintered product; and then according to the primary sintering product: weighing aluminum oxide according to the molar ratio of 0.95:0.05, mixing the aluminum oxide and the aluminum oxide, grinding, heating the obtained powder from room temperature to 700 ℃, keeping the temperature at the heating rate of 5 ℃/min under the air atmosphere for 10 hours, cooling to room temperature, and taking out to obtain a secondary sintering product; and then according to the secondary sintering product: weighing lithium hydroxide according to the molar ratio of 1:1.05, mixing the lithium hydroxide and the lithium hydroxide, grinding, heating the obtained powder to 750 ℃ from room temperature, heating the powder at the rate of 5 ℃/min, and keeping the temperature for 5 hours in an air atmosphere to obtain a final product LiNi0.8Mn0.05Fe0.1Al0.05O2。
Comparative example 1
The comparative example provides a nickel-manganese-iron-aluminum-lithium cathode material with a molecular formula of LiNi0.8Mn0.1Fe0.05Al0.05O2The preparation method comprises the following steps:
(1) nickel sulfate, manganese sulfate, ferric sulfate and aluminum sulfate are mixed according to the molar weight ratio of metal ions of 0.8: 0.1: 0.05: 0.05 into deionized water, and continuously stirring to fully dissolve inorganic salt to prepare a green clear metal salt solution A;
weighing oxalic acid with the molar weight of 0.042mol, pouring the oxalic acid into a reaction kettle containing deionized water, heating and stirring at 35 ℃ to completely dissolve the oxalic acid, and then preparing a precipitant: weighing ammonia water with the molar quantity of 0.084mol according to the molar ratio of 1:2 of the complexing agent, pouring the ammonia water into a reaction kettle to prepare a white mixed solution B, and keeping the temperature of the reaction kettle at 35 ℃ and continuously stirring;
(2) continuously and slowly adding the metal salt solution A into the mixed solution B, keeping the temperature at 35 ℃ and continuously stirring for 20 hours at the rotating speed of 900r/min to form white emulsion; aging, filtering, washing and drying to obtain a blue-green precursor;
(3) according to the precursor: weighing lithium hydroxide according to the molar ratio of 1:1.05, mixing the lithium hydroxide and the lithium hydroxide, grinding, heating the obtained powder from room temperature to 700 ℃, at the heating rate of 5 ℃/min, keeping the temperature for 20 hours in the air atmosphere, heating from 700 ℃ to 750 ℃, at the heating rate of 5 ℃/min, keeping the temperature for 5 hours in the air atmosphere, and obtaining the final product LiNi0.8Mn0.1Fe0.05Al0.05O2。
Comparative example 2
This example provides a nickel-manganese-iron-aluminum-lithium cathode material with a molecular formula of LiNi0.8Mn0.05Fe0.1Al0.05O2The preparation method comprises the following steps:
(1) nickel sulfate and manganese sulfate are mixed according to the molar weight ratio of metal ions of 0.8: 0.05 into deionized water, and continuously stirring to fully dissolve inorganic salt to prepare a green clear metal salt solution A;
weighing sodium hydroxide with the molar weight of 0.084mol, pouring the sodium hydroxide into a reaction kettle containing deionized water, heating and stirring at 35 ℃ to completely dissolve the sodium hydroxide, and then, according to a precipitator: weighing ammonia water with the molar quantity of 0.168mol according to the molar ratio of 1:2 of the complexing agent, pouring the ammonia water into a reaction kettle to prepare a mixed solution B, and keeping the temperature of the reaction kettle at 35 ℃ and continuously stirring;
(2) continuously and slowly adding the metal salt solution A into the mixed solution B, keeping the temperature at 35 ℃ and continuously stirring for 20 hours at the rotating speed of 900r/min to form emulsion; aging, filtering, washing and drying to obtain a nickel-manganese hydroxide precursor;
(3) according to the nickel-manganese hydroxide precursor: iron sesquioxide is 0.85: weighing ferric oxide according to a molar ratio of 0.1, mixing the ferric oxide and the ferric oxide, grinding, heating the obtained powder to 700 ℃ from room temperature, heating at a rate of 5 ℃/min, keeping the temperature for 10 hours in an air atmosphere, cooling to room temperature, and taking out to obtain a primary sintered product; and then according to the primary sintering product: weighing aluminum oxide according to the molar ratio of 0.95:0.05, mixing the aluminum oxide and the aluminum oxide, grinding, heating the obtained powder from room temperature to 700 ℃, keeping the temperature at the heating rate of 5 ℃/min under the air atmosphere for 10 hours, cooling to room temperature, and taking out to obtain a secondary sintering product; and then according to the secondary sintering product: weighing lithium hydroxide according to the molar ratio of 1:1.05, mixing the lithium hydroxide and the lithium hydroxide, grinding, heating the obtained powder to 750 ℃ from room temperature, heating the powder at the rate of 5 ℃/min, and keeping the temperature for 5 hours in an air atmosphere to obtain a final product LiNi0.8Mn0.05Fe0.1Al0.05O2。
Product effectiveness testing
FIG. 1 is a XRD pattern of the positive electrode materials obtained in example 1 (corresponding to 1a), example 2 (corresponding to 1b) and comparative example 1 (corresponding to 1c), and comparing the intensity and position of diffraction peaks with those of a reference standard card (JCPDS 74-0919) shows that the positive electrode material obtained in comparative example 1 is LiNiO2A layered structure.
FIG. 2 is a scanning electron microscope image of the positive electrode material of NiMnFeAlLi prepared in example 1, in which the secondary particles are spherical and the particle size is 1-2 μm.
FIG. 3 is a scanning electron microscope image of the positive electrode material of NiMnFeAlLi prepared in example 2, in which the secondary particles are spherical and the particle size is 2-3 μm.
FIG. 4 is a graph showing the cycle performance of the lithium nickel manganese iron aluminum anode material prepared in example 2 after 3 cycles of activation at a rate of 0.1C and 100 cycles at a rate of 1C. The results showed that 192.31mAh/g discharge capacity was obtained at 0.1C discharge rate, and the cycle stability was good.
Fig. 5 is a graph showing the cycle performance of the lithium nickel manganese iron aluminum anode materials prepared in example 1 and comparative example 1 after 3 cycles of activation and 100 cycles of 1C magnification. The result shows that the specific discharge capacity of the nickel-manganese-iron-aluminum-lithium cathode material prepared in the example 1 at the discharge rate of 0.1C and the specific discharge capacity of the nickel-manganese-iron-aluminum-lithium cathode material prepared in the example 1 at the discharge rate of 1C are both better than those of the cathode material prepared in the comparative example 1, and the capacity retention rate after 100 cycles is also higher than that of the cathode material prepared in the comparative example 1.
Fig. 6 is a graph showing the cycle performance of the lithium nickel manganese iron aluminum anode materials prepared in example 1 and comparative example 2 after 3 cycles of activation and 100 cycles of 1C magnification. The result shows that the specific discharge capacity of the nickel-manganese-iron-aluminum-lithium cathode material prepared in the example 1 at the discharge rate of 0.1C and the specific discharge capacity of the nickel-manganese-iron-aluminum-lithium cathode material prepared in the example 1 at the discharge rate of 1C are both better than those of the cathode material prepared in the comparative example 2, and the capacity retention rate after 100 cycles is also higher than that of the cathode material prepared in the comparative example 1.
The embodiments of the present application have been described in detail with reference to the drawings, but the present application is not limited to the embodiments, and various changes can be made within the knowledge of those skilled in the art without departing from the gist of the present application. Furthermore, the embodiments and features of the embodiments of the present application may be combined with each other without conflict.
Claims (10)
1. The preparation method of the nickel-manganese-iron-aluminum-lithium cathode material is characterized by comprising the following steps of:
(1) preparing a nickel salt and a manganese salt into a metal salt solution A; oxalic acid is used as a precipitator and is prepared into a mixed solution B with a complexing agent;
(2) adding the metal salt solution A into the mixed solution B, heating and stirring to form emulsion; then aging, filtering, washing and drying to prepare a nickel manganese oxalate precursor;
(3) adding an iron source into the nickel manganese oxalate precursor, and calcining for the first time to obtain a primary sintered product; adding an aluminum source into the primary sintering product, and performing secondary calcination to obtain a secondary sintering product; and adding a lithium source into the secondary sintering product, and calcining for three times to obtain the nickel-manganese-iron-aluminum-lithium cathode material.
2. The production method according to claim 1, wherein the nickel salt is nickel nitrate and/or nickel sulfate; the manganese salt is manganese nitrate and/or manganese sulfate.
3. The method according to claim 1, wherein the complexing agent is ammonia water.
4. The preparation method according to claim 1, wherein the molar ratio of the precipitating agent to the complexing agent is 1: (1.8-2.5).
5. The method according to claim 1, wherein the heating to 32-37 ℃ is performed in step (2).
6. The method as claimed in claim 1, wherein the rotation speed of the stirring in step (2) is 800-1000 r/min.
7. The method of claim 1, wherein the aluminum source is aluminum oxide and the iron source is ferric oxide.
8. The production method according to claim 1, wherein the primary calcination in the step (3) is: heating from room temperature to about 700 ℃, keeping the temperature for about 10 hours under the air atmosphere at the heating rate of about 5 ℃/min, and cooling to room temperature;
the secondary calcination in the step (3) comprises the following steps: heating from room temperature to about 700 ℃, keeping the temperature for about 10 hours under the air atmosphere at the heating rate of about 5 ℃/min, and cooling to room temperature;
the step of calcining for three times in the step (3) is as follows: raising the temperature from room temperature to about 750 ℃, raising the temperature at the speed of about 5 ℃/min, keeping the temperature for about 5h under the air atmosphere, and cooling to the room temperature.
9. A nickel-manganese-iron-aluminum-lithium positive electrode material, characterized by being prepared by the preparation method of any one of claims 1 to 8.
10. The li-ni-fe-al positive electrode material of claim 9, wherein the molecular formula of the li-ni-fe-al positive electrode material is LiNi0.8Mn0.15-xFexAl0.05O2And x is 0.05 or 0.1.
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