CN113800574B - Nickel-manganese-iron-aluminum-lithium positive electrode material and preparation method thereof - Google Patents
Nickel-manganese-iron-aluminum-lithium positive electrode 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 nickel salt and 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 are carried out to obtain a nickel-manganese oxalate precursor; (3) Adding an iron source into the nickel manganese oxalate precursor, and calcining for one time; adding an aluminum source, and performing secondary calcination; and finally adding a lithium source, and calcining for three times to obtain the nickel manganese iron aluminum lithium anode material. The nickel-manganese-iron-aluminum-lithium positive electrode material has higher theoretical capacity, the discharge capacity is 190-195mAh/g at the rate of 0.1C, the capacity retention rate is about 85% after 100 times of circulation, and the nickel-manganese-iron-aluminum-lithium positive electrode material has better circulation 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
Nickel cobalt lithium aluminate (LiNi) as high nickel ternary positive electrode material 1-x-y Co x Al y O 2 Short for NCA) has very high energy density and power density and wide application prospect, so that the material is widely focused in industry and academia. Wherein the high nickel system LiNi 0.8 Co 0.15 Al 0.05 O 2 As the most mature and best-performance system researched in NCA materials, the material has higher actual specific capacity, and the specific discharge capacity under high cut-off voltage (4.3V) can reach 180mAh/g. It is the high capacity characteristics of NCA positive electrode materials that are used as positive electrode materials for making high performance batteries, such as 18650 type power batteries in the new energy automobile industry.
The solid phase method and the coprecipitation method are mainly used for preparing the NCA material for business use. The coprecipitation method has the advantages that the particle size of the prepared material particles is small and uniform, but aluminum element is introduced into the coprecipitation process, so that the problems of uneven element distribution in the product, difficult growth of crystal grains and the like are easily caused. In addition, the NCA material has the advantages of large capacity, but also has the problems of low initial coulombic efficiency, poor cycle stability and rate capability, voltage decay and the like.
It is therefore desirable to provide a positive electrode material that performs better than conventional NCA materials.
Disclosure of Invention
The present invention aims to solve at least one of the technical problems in 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 positive electrode material has higher theoretical capacity, the discharge capacity is 190-195mAh/g at the rate of 0.1C, the capacity retention rate is about 85% after 100 times of circulation, and the nickel-manganese-iron-aluminum-lithium positive electrode material has better circulation stability.
The invention provides a preparation method of a nickel-manganese-iron-aluminum-lithium positive electrode material, which comprises the following steps:
(1) Preparing nickel salt and 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 are carried out to obtain a nickel-manganese oxalate precursor;
(3) Adding an iron source into the nickel manganese oxalate precursor, and performing primary calcination to obtain a primary sintering 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 anode material.
The invention adopts oxalic acid to replace sodium hydroxide with strong alkalinity and strong corrosiveness as the precipitant of the coprecipitation process, reduces the corrosion to production equipment and the pollution to the environment, and can also effectively avoid the Al element from generating AlO under the condition of strong alkalinity 2- Therefore, the problems of uneven element distribution and difficult growth of crystal grains in the product are caused, and the electrochemical performance of the anode material can be effectively improved. The invention further adopts a three-stage sintering process to respectively add an iron source and a precursor, and add an aluminum source and a primary sintering product for secondary sintering, so that the defect of uneven grain growth of the precursor caused by uneven precipitation of aluminum ions under alkaline conditions in the traditional coprecipitation process is further avoided, and the defect of uneven grain size is further avoided. In addition, the invention also adopts manganese to completely replace noble metal cobalt to synthesize the high-nickel cobalt-free quaternary positive electrode material, which can not only avoid cost increase caused by excessive dependence of the high-nickel positive electrode material on metal cobalt, but also structurally optimize the high-nickel positive electrode material, thereby being beneficial to stabilizing the layered structure of the material and improving the electrochemical properties such as the cycle stability and the like.
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 water.
Preferably, the molar ratio of the precipitant to the complexing agent is 1: (1.8-2.5).
Preferably, said heating to 32-37 ℃ is performed in step (2).
Preferably, the stirring speed in the step (2) is 800-1000r/min.
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.
The invention adopts aluminum oxide to replace aluminum sulfate which is commonly used in the traditional coprecipitation process, and ferric oxide is used as an external iron source, so that the defect of uneven distribution of precursor elements caused by incomplete metal ion precipitation in the precursor preparation process by the traditional coprecipitation process is avoided.
Preferably, the step of primary calcination in the step (3) is as follows: the temperature is raised to about 700 ℃ from room temperature, the heating rate is about 5 ℃/min, the temperature is kept for about 10 hours under the air atmosphere, and then the mixture is cooled to the room temperature.
Preferably, the step of secondary calcination in step (3) is as follows: the temperature is raised to about 700 ℃ from room temperature, the heating rate is about 5 ℃/min, the temperature is kept for about 10 hours under the air atmosphere, and then the mixture is cooled to the room temperature.
Preferably, the step of three-time calcination in the step (3) is as follows: the temperature is raised to about 750 ℃ from room temperature, the temperature raising rate is about 5 ℃/min, the temperature is kept for about 5 hours under the air atmosphere, and the mixture is cooled to the room temperature.
The calcination temperature is an important factor affecting the compactness, the structural stability and the electrochemical performance of the prepared nickel manganese iron aluminum lithium anode material. The temperature is too high, and an external lithium source is easy to excessively volatilize, so that the sintering product is seriously lack of lithium, and meanwhile, the original internal crystal structure of the material can be directly influenced, and the material is easy to decompose; the temperature is too low, the external aluminum source and the external 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 anode material which is prepared by the preparation method.
Preferably, the molecular formula of the nickel manganese iron aluminum lithium positive electrode material is LiNi 0.8 Mn 0.15-x Fe x Al 0.05 O 2 X=0.05 or 0.1.
Compared with the prior art, the invention has the following beneficial effects:
(1) Compared with the sodium hydroxide precipitant used in the traditional coprecipitation process, the oxalic acid precipitant has lower corrosiveness to production equipment and is more environment-friendly. Meanwhile, oxalic acid is used as a precipitator to replace alkaline substances, so that Al element can be effectively prevented from generating Al under the strong alkaline conditionO 2- Therefore, the problems of uneven element distribution and difficult growth of crystal grains in the product are caused, and the electrochemical performance of the anode material can be effectively improved.
(2) The invention adopts a three-stage sintering process, and respectively carries out secondary sintering through an external iron source, a precursor, an external aluminum source and a primary sintering product, thereby avoiding the defect of uneven grain growth of the precursor caused by uneven precipitation of aluminum ions under alkaline conditions in the traditional coprecipitation process, and further avoiding uneven grain size. The particle size of the coprecipitation product particles is controlled by controlling the parameters of the reaction process, such as temperature, rotating speed and the like, so that particles with regular morphology and uniform size can be obtained, and the electrochemical performance of the sintered product material is further improved. The process has the advantages of simple preparation method, easy realization of process conditions, low energy consumption and the like.
(3) The invention adopts low-cost transition metal manganese (Mn) to completely replace expensive transition metal Co to synthesize the high-nickel cobalt-free quaternary anode material, reduces the production cost of the high-nickel material, optimizes the layered structure stability of the high-nickel material, and thus obtains the anode material with excellent electrochemical performance.
(4) The invention adopts aluminum oxide to replace aluminum sulfate which is commonly used in the traditional coprecipitation process, and ferric oxide is used as an external iron source, so that the defect of uneven distribution of precursor elements caused by incomplete metal ion precipitation in the precursor preparation process by the traditional coprecipitation process is avoided.
Drawings
Fig. 1 is an XRD pattern of the positive electrode material prepared in example 1 (corresponding to 1 a), example 2 (corresponding to 1 b) and comparative example 1 (corresponding to 1 c);
FIG. 2 is a scanning electron microscope image of the nickel manganese iron aluminum lithium positive electrode material prepared in example 1;
FIG. 3 is a scanning electron microscope image of the nickel manganese iron aluminum lithium positive electrode material prepared in example 2;
FIG. 4 is a graph showing the cycle performance of the nickel manganese iron aluminum lithium positive electrode material prepared in example 2;
FIG. 5 is a graph showing the cycle performance of the nickel manganese iron aluminum lithium positive electrode materials prepared in example 1 and comparative example 1;
FIG. 6 is a graph showing the cycle performance of the nickel manganese iron aluminum lithium positive electrode materials 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 will be presented. It should be noted that the following embodiments are only preferred embodiments of the present invention, and the scope of the present invention is not limited to the following embodiments, and any modifications, substitutions, and combinations made without departing from the spirit and principles of the present invention are included in the scope of the present invention.
The starting materials, reagents or apparatus used in the following examples are all available from conventional commercial sources or may be obtained by methods known in the art unless otherwise specified.
Example 1
The embodiment provides a nickel-manganese-iron-aluminum-lithium positive electrode material, the molecular formula of which is LiNi 0.8 Mn 0.1 Fe 0.05 Al 0.05 O 2 The preparation method comprises the following steps:
(1) Nickel sulfate and manganese sulfate are mixed according to the molar ratio of metal ions of 0.8: adding the mixture into deionized water according to the proportion of 0.1, and continuously stirring to fully dissolve inorganic salt to prepare 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 according to a precipitator: complexing agent=1:2 molar ratio, weighing ammonia water with the molar quantity of 0.084mol, pouring the ammonia water into a reaction kettle to prepare 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, heating at 35 ℃ and continuously stirring at 900r/min for 20 hours 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: ferric oxide = 0.9: weighing ferric oxide at a molar ratio of 0.05, mixing the two, grinding, heating the obtained powder from room temperature to 700 ℃, heating at a speed of 5 ℃/min, and air atmospherePreserving the temperature for 10 hours, cooling to room temperature, and taking out to obtain a primary sintering product; and then the product is sintered according to the first time: weighing aluminum oxide in a molar ratio of aluminum oxide=0.95:0.05, mixing the aluminum oxide and the aluminum oxide, grinding, heating the obtained powder to 700 ℃ from room temperature, keeping the temperature at a heating rate of 5 ℃/min for 10 hours in an air atmosphere, cooling to the room temperature, and taking out to obtain a secondary sintering product; and then sintering the product for the second time: lithium hydroxide is weighed according to the molar ratio of lithium hydroxide=1:1.05, the lithium hydroxide and the lithium hydroxide are mixed and ground, the obtained powder is heated to 750 ℃ from room temperature, the heating rate is 5 ℃/min, and the heat is preserved for 5 hours in an air atmosphere, so that the final product LiNi is obtained 0.8 Mn 0.1 Fe 0.05 Al 0.05 O 2 。
Example 2
The embodiment provides a nickel-manganese-iron-aluminum-lithium positive electrode material, the molecular formula of which is LiNi 0.8 Mn 0.05 Fe 0.1 Al 0.05 O 2 The preparation method comprises the following steps:
(1) Nickel sulfate and manganese sulfate are mixed according to the molar ratio of metal ions of 0.8: adding the solution into deionized water according to a proportion of 0.05, and continuously stirring to fully dissolve inorganic salt to prepare 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 according to a precipitator: complexing agent=1:2 molar ratio, weighing ammonia water with the molar quantity of 0.084mol, pouring the ammonia water into a reaction kettle to prepare 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, heating at 35 ℃ and continuously stirring at 900r/min for 20 hours 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: ferric oxide = 0.85: weighing ferric oxide at a molar ratio of 0.1, mixing the two, grinding, heating the obtained powder from room temperature to 700 ℃, heating at a heating rate of 5 ℃/min, preserving heat for 10 hours in air atmosphere, cooling to room temperature, and taking out to obtain the primary productSintering the product; and then the product is sintered according to the first time: weighing aluminum oxide in a molar ratio of aluminum oxide=0.95:0.05, mixing the aluminum oxide and the aluminum oxide, grinding, heating the obtained powder to 700 ℃ from room temperature, keeping the temperature at a heating rate of 5 ℃/min for 10 hours in an air atmosphere, cooling to the room temperature, and taking out to obtain a secondary sintering product; and then sintering the product for the second time: lithium hydroxide is weighed according to the molar ratio of lithium hydroxide=1:1.05, the lithium hydroxide and the lithium hydroxide are mixed and ground, the obtained powder is heated to 750 ℃ from room temperature, the heating rate is 5 ℃/min, and the heat is preserved for 5 hours in an air atmosphere, so that the final product LiNi is obtained 0.8 Mn 0.05 Fe 0.1 Al 0.05 O 2 。
Comparative example 1
The comparative example provides a nickel manganese iron aluminum lithium positive electrode material with a molecular formula of LiNi 0.8 Mn 0.1 Fe 0.05 Al 0.05 O 2 The preparation method comprises the following steps:
(1) Nickel sulfate, manganese sulfate, ferric sulfate and aluminum sulfate are mixed according to the molar ratio of metal ions of 0.8:0.1:0.05: adding the solution into deionized water according to a proportion of 0.05, and continuously stirring to fully dissolve inorganic salt to prepare 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 according to a precipitator: complexing agent=1:2 molar ratio, weighing ammonia water with the molar quantity of 0.084mol, pouring the ammonia water into a reaction kettle to prepare 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, heating at 35 ℃ and continuously stirring at 900r/min for 20 hours to form white emulsion; aging, filtering, washing and drying to obtain a blue-green precursor;
(3) The preparation method comprises the following steps of: lithium hydroxide is weighed according to the molar ratio of lithium hydroxide=1:1.05, the two are mixed and ground, the obtained powder is firstly heated to 700 ℃ from room temperature, the heating rate is 5 ℃/min, the temperature is kept for 20 hours under the air atmosphere, the temperature is then heated to 750 ℃ from 700 ℃, the heating rate is 5 ℃/min, and the temperature is kept for 5 hours under the air atmosphere, so that the lithium hydroxide is obtainedTo the final product LiNi 0.8 Mn 0.1 Fe 0.05 Al 0.05 O 2 。
Comparative example 2
The embodiment provides a nickel-manganese-iron-aluminum-lithium positive electrode material, the molecular formula of which is LiNi 0.8 Mn 0.05 Fe 0.1 Al 0.05 O 2 The preparation method comprises the following steps:
(1) Nickel sulfate and manganese sulfate are mixed according to the molar ratio of metal ions of 0.8: adding the solution into deionized water according to a proportion of 0.05, and continuously stirring to fully dissolve inorganic salt to prepare 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: complexing agent=1:2 molar ratio, weighing ammonia water with the molar quantity of 0.168mol, 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, heating at 35 ℃ and continuously stirring at 900r/min for 20 hours to form emulsion; aging, filtering, washing and drying to obtain a nickel-manganese hydroxide precursor;
(3) According to the nickel-manganese hydroxide precursor: ferric oxide = 0.85: weighing ferric oxide in a molar ratio of 0.1, mixing the two, grinding, heating the obtained powder from room temperature to 700 ℃, heating at a speed of 5 ℃/min, preserving heat for 10 hours in an air atmosphere, cooling to room temperature, and taking out to obtain a primary sintering product; and then the product is sintered according to the first time: weighing aluminum oxide in a molar ratio of aluminum oxide=0.95:0.05, mixing the aluminum oxide and the aluminum oxide, grinding, heating the obtained powder to 700 ℃ from room temperature, keeping the temperature at a heating rate of 5 ℃/min for 10 hours in an air atmosphere, cooling to the room temperature, and taking out to obtain a secondary sintering product; and then sintering the product for the second time: lithium hydroxide is weighed according to the molar ratio of lithium hydroxide=1:1.05, the lithium hydroxide and the lithium hydroxide are mixed and ground, the obtained powder is heated to 750 ℃ from room temperature, the heating rate is 5 ℃/min, and the heat is preserved for 5 hours in an air atmosphere, so that the final product LiNi is obtained 0.8 Mn 0.05 Fe 0.1 Al 0.05 O 2 。
Product effect test
FIG. 1 shows XRD patterns of positive electrode materials prepared in example 1 (corresponding to 1 a), example 2 (corresponding to 1 b) and comparative example 1 (corresponding to 1 c), and the positive electrode material prepared in comparative example 1 was LiNiO obtained by comparing the intensities and positions of diffraction peaks with those of the document standard card (JCPDS 74-0919) 2 A layered structure.
FIG. 2 is a scanning electron microscope image of the nickel manganese iron aluminum lithium positive electrode material prepared in example 1, wherein the secondary particles are spherical, and the particle size is 1-2 μm.
FIG. 3 is a scanning electron microscope image of the nickel manganese iron aluminum lithium positive electrode material prepared in example 2, wherein the secondary particles are spherical, and the particle size is 2-3 μm.
Fig. 4 is a graph showing the cycle performance of the nickel manganese iron aluminum lithium positive electrode material prepared in example 2 after 3 cycles of activation at 0.1C rate, and 100 cycles of cycle at 1C rate. The result shows that the material can obtain 192.31mAh/g discharge capacity at a discharge rate of 0.1C, and has good cycle stability.
Fig. 5 is a graph showing the cycle performance of the nickel manganese iron aluminum lithium positive electrode materials prepared in example 1 and comparative example 1 after 3 cycles of activation, which were cycled at a 1C rate for 100 cycles. The results show that the specific discharge capacity of the nickel manganese iron aluminum lithium positive electrode 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 positive electrode material at the discharge rate of 1C are superior to those of the positive electrode material prepared in the comparative example 1, and the capacity retention rate after 100 cycles is also higher than that of the positive electrode material prepared in the comparative example 1.
Fig. 6 is a graph showing the cycle performance of the nickel manganese iron aluminum lithium positive electrode materials prepared in example 1 and comparative example 2 after 3 cycles of activation, which were cycled at a 1C rate for 100 cycles. The results show that the specific discharge capacity of the nickel manganese iron aluminum lithium positive electrode 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 positive electrode material at the discharge rate of 1C are superior to those of the positive electrode material prepared in the comparative example 2, and the capacity retention rate after 100 cycles is also higher than that of the positive electrode material prepared in the comparative example 1.
The embodiments of the present application have been described in detail above with reference to the accompanying drawings, but the present application is not limited to the above embodiments, and various changes can be made within the knowledge of one of ordinary skill in the art without departing from the spirit of the present application. Furthermore, embodiments of the present application and features of the embodiments may be combined with each other without conflict.
Claims (8)
1. The preparation method of the nickel-manganese-iron-aluminum-lithium positive electrode material is characterized by comprising the following steps of:
(1) Preparing nickel salt and 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 are carried out to obtain a nickel-manganese oxalate precursor;
(3) Adding an iron source into the nickel manganese oxalate precursor, and performing primary calcination to obtain a primary sintering product; adding an aluminum source into the primary sintering product, and performing secondary calcination to obtain a secondary sintering product; adding a lithium source into the secondary sintering product, and calcining for three times to obtain a nickel-manganese-iron-aluminum-lithium anode material;
the aluminum source is aluminum oxide, and the iron source is ferric oxide;
the step of primary calcination in the step (3) is as follows: heating from room temperature to 700 ℃, keeping the temperature for 10 hours under the air atmosphere at a heating rate of 5 ℃/min, and cooling to room temperature;
the secondary calcination step in the step (3) is as follows: heating from room temperature to 700 ℃, keeping the temperature for 10 hours under the air atmosphere at a heating rate of 5 ℃/min, and cooling to room temperature;
the three calcining step in the step (3) is as follows: and (3) heating to 750 ℃ from room temperature, keeping the temperature for 5 hours under the air atmosphere at a heating rate of 5 ℃/min, and cooling to room temperature.
2. The method of 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 of claim 1, wherein the complexing agent is aqueous ammonia.
4. The method of claim 1, wherein the molar ratio of precipitant to complexing agent is 1: (1.8-2.5).
5. The method of claim 1, wherein said heating to 32-37 ℃ is performed in step (2).
6. The method according to claim 1, wherein the stirring in step (2) is carried out at a rotational speed of 800 to 1000r/min.
7. A nickel manganese iron aluminum lithium positive electrode material, characterized by being produced by the production method according to any one of claims 1 to 6.
8. The nickel manganese iron aluminum lithium positive electrode material according to claim 7, wherein the molecular formula of the nickel manganese iron aluminum lithium positive electrode material is LiNi 0.8 Mn 0.15-x Fe x Al 0.05 O 2 X=0.05 or 0.1.
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