CN113247969A - Preparation method of metal pyrophosphate coated modified nickel-cobalt-manganese ternary precursor - Google Patents
Preparation method of metal pyrophosphate coated modified nickel-cobalt-manganese ternary precursor Download PDFInfo
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Abstract
The invention belongs to the technical field of lithium ion battery materials, and particularly discloses a preparation method of a metal pyrophosphate coated modified nickel-cobalt-manganese ternary precursor. The preparation method comprises the following process steps: dispersing the prepared ternary precursor in water, adding soluble metal salt, dissolving the metal salt, adding pyrophosphate, stirring for a period of time, filtering, and drying to obtain the ternary precursor coated with the metal pyrophosphate. The ternary material precursor prepared by the invention has the advantages of uniform coating and high stability, and can effectively improve the electrochemical performance of the lithium battery.
Description
Technical Field
The invention belongs to the technical field of lithium ion battery materials, and particularly relates to a preparation method of a metal pyrophosphate coated modified nickel-cobalt-manganese ternary precursor.
Background
The increasing energy crisis and environmental pollution have prompted the rapid development of new energy technologies and secondary power sources. As the most promising secondary power source at present, lithium ion batteries are being developed toward higher specific energy and better safety. Among them, battery materials have become the key to the development of novel lithium ion batteries. At present, ternary materials in mainstream lithium ion battery materials are most widely applied, wherein Ni element in the ternary materials mainly provides specific capacity of NCM materials, and the higher the content of the Ni element is, the larger the reversible specific capacity of the materials is. But Ni3+Is easy to be reduced into Ni2+And Li+/Ni2+Have similar ionic radii (r =0.76 a/0.69 a), resulting in a tendency for cationic shuffling of ternary materials, especially high nickel materials, such that the electrochemical performance of the material deteriorates. Therefore, it is necessary to modify the precursor to stabilize the structure of the precursor and to reduce Li+/Ni2+Cation shuffling occurs.
Surface coating modification is considered as one of the means that can effectively improve the cycle performance of the battery material. PO in phosphate4The covalent bond is combined with metal ions to improve the thermal stability of the material, and P = O can maintain the interface of the electrode and the electrolyte in a stable state and protect the electrode from being corroded by the electrolyte, thereby improving the chemical stability of the material.
Disclosure of Invention
The invention aims to provide a preparation method of pyrophosphate-coated modified ternary precursor. According to the invention, through a simple and effective surface coating method, after pyrophosphate coating treatment is carried out on the ternary precursor, the electrochemical performance and the structural stability of the ternary material can be effectively improved.
The purpose of the invention is realized by the following technical scheme:
a preparation method of a metal pyrophosphate coated modified ternary precursor comprises the following steps:
(1) preparing a metal salt solution A of nickel, cobalt and manganese;
(2) adding the metal salt solution A prepared in the step (1) into a reaction kettle, then adding a sodium hydroxide solution and an ammonia water solution into the reaction kettle, controlling the pH value in the kettle to be kept at 10.5-12 in the reaction process, and filtering and drying to obtain a ternary material precursor Ni after the reaction is finished1-x-yCoxMny(OH)2(ii) a Wherein x is more than or equal to 0.1 and less than or equal to 0.3, and y is more than or equal to 0.1 and less than or equal to 0.3;
(3) dispersing the ternary material precursor prepared in the step (2) in water, adding more than one soluble calcium, magnesium and zinc metal salt, adding a certain amount of pyrophosphoric acid and/or pyrophosphates, stirring for a period of time, filtering, and drying to obtain the metal pyrophosphate coated and modified ternary precursor.
Further, the nickel, cobalt and manganese salts of the metal salt solution A prepared in the step (1) are selected from more than one of nitrate, acetate and sulfate.
Further, the total molar concentration of the metal ions in the metal salt solution A in the step (1) is 1-5 mol/L.
Further, the molar concentration of the sodium hydroxide solution in the step (2) is 1-5mol/L, and the molar concentration of the ammonia water solution is 5-12 mol/L.
Further, the reaction temperature in the step (2) is 40-80 ℃, and the reaction time is 10-50 h.
Further, the molar ratio of the metal salt to the pyrophosphate in the step (3) is 1.2-4: 1.
Further, the molar ratio of the metal salt in the step (3) to the ternary material precursor prepared in the step (2) is 1:100-1: 50.
Further, the pyrophosphate in the step (3) is selected from Na4P2O7And/or K4P2O7。
Further, the stirring time in the step (3) is 2-10 h.
Based on the same inventive concept, the invention also provides a ternary material, which is prepared by uniformly mixing the metal pyrophosphate-coated modified ternary precursor prepared by the method with a lithium source and then roasting.
Compared with the prior art, the invention has the following beneficial effects:
according to the invention, through generating pyrophosphate precipitate on the surface of the ternary precursor, the ternary precursor is subjected to surface coating to synthesize the metal pyrophosphate-coated ternary material precursor, and then the ternary material is further synthesized, so that the structural stability and the interface stability of the ternary material are improved. The invention designs a low-cost and easy-to-realize modification method, can obviously improve the electrochemical performance of the ternary material, and has good application prospect.
Drawings
FIG. 1 is an SEM image of a precursor prepared in example 1 of the present invention.
Detailed Description
Embodiments of the present invention will be described in detail below with reference to the accompanying drawings. The following examples are only for illustrating the technical solutions of the present invention more clearly, and therefore are only examples, and the protection scope of the present invention is not limited thereby.
It is to be noted that, unless otherwise specified, technical or scientific terms used herein shall have the ordinary meaning as understood by those skilled in the art to which the invention pertains.
Example 1
Preparing a metal pyrophosphate-coated modified ternary precursor:
(1) dissolving 0.5 mol of nickel sulfate, 0.2mol of cobalt sulfate and 0.3mol of manganese sulfate in 40mL of pure water to obtain a nickel-cobalt-manganese solution, and then respectively dissolving the nickel-cobalt-manganese solution, a 4mol/L sodium hydroxide solution and a 10 mol/L ammonia water solution by 5m in a nitrogen atmosphereAdding the mixture into a reaction kettle at the speed of L/min, adjusting the pH value of a reaction system to 11-12, reacting for 48 hours at the temperature of 50 ℃, filtering and drying to obtain a ternary material precursor Ni0.5Co0.2Mn0.3(OH)2。
(2) Taking 0.1mol of Ni prepared in the step (1)0.5Co0.2Mn0.3(OH)2Dispersed in 20 mL of water, 1mmol of MgCl was added2After dissolution, 0.5mmol of Na was added4P2O7Stirring for 4h, filtering, and drying to obtain Mg2P2O7@Ni0.5Co0.2Mn0.3(OH)2。
FIG. 1 shows Mg prepared in this example2P2O7@Ni0.5Co0.2Mn0.3(OH)2As can be seen from the SEM image of the precursor, after coating, the surface smoothness of the sample was improved, and the overall secondary morphology was unchanged.
Mixing Mg2P2O7@Ni0.5Co0.2Mn0.3(OH)2Mixing with lithium source, calcining to synthesize ternary material. And taking the active material as an active substance of the anode material, mixing the active substance with Acetylene Black (AB) as a conductive agent and polyvinylidene fluoride (PVDF) as a binder according to the mass ratio of 8:1:1, taking N-methylpyrrolidone (NMP) as a solvent, placing the mixture in a small beaker, and stirring and mixing the mixture for 2 hours at the rotating speed of 800r/min to obtain slurry. Coating the slurry on a current collector aluminum foil by using an automatic coating machine, flatly placing the current collector aluminum foil on toughened glass, transferring the current collector aluminum foil to a vacuum drying oven at 85 ℃ for drying for 4h, preparing a pole piece with the diameter of 14mm by punching, drying for 4h at 105 ℃ in the vacuum drying oven, placing the pole piece in a glove box with the water content and the oxygen content both lower than 0.1ppm and filled with argon atmosphere for 4h to reduce the water absorbed by the pole piece in the transferring process, and then assembling the pole piece into a CR2032 type button cell in the glove box. The battery uses a pure metal lithium sheet with the diameter of 16mm and the thickness of 0.5mm as a negative electrode, and a porous polyethylene film with the diameter of 18mm and the model of Celgard2300 as a diaphragm.
After the battery is assembled and aged for 12 hours, the charging and discharging tests of different potentials are carried out. Under the voltage of 4.3V, the activation is carried out for 3 circles at 0.1C, and the circulation is carried out for 200 circles at the magnification of 2C. The specific discharge capacity after 200 cycles is 160.8 mA h g < -1 >, and the capacity retention rate is 83.3%.
Example 2
Preparing a metal pyrophosphate-coated modified ternary precursor:
(1) dissolving 0.5 mol of nickel sulfate, 0.2mol of cobalt sulfate and 0.3mol of manganese sulfate in 40mL of pure water to obtain a nickel-cobalt-manganese solution, then respectively adding the nickel-cobalt-manganese solution, a 4mol/L sodium hydroxide solution and a 10 mol/L ammonia water solution into a reaction kettle at a speed of 5mL/min in a nitrogen atmosphere, adjusting the pH value of a reaction system to 11-12, reacting for 48 hours at 50 ℃, filtering and drying to obtain a ternary material precursor Ni precursor0.5Co0.2Mn0.3(OH)2。
(2) Taking 0.1mol of Ni0.5Co0.2Mn0.3(OH)2Dispersing in 30 mL of aqueous solution, adding 1mmol of CaCl2After dissolution, 0.5mmol of Na was added4P2O7Stirring for 5h, filtering, and drying to obtain Ca2P2O7@Ni0.5Co0.2Mn0.3(OH)2。
Adding Ca2P2O7@Ni0.5Co0.2Mn0.3(OH)2Mixing with lithium source, calcining to synthesize ternary material. And taking the active material as an active substance of the anode material, mixing the active substance with Acetylene Black (AB) as a conductive agent and polyvinylidene fluoride (PVDF) as a binder according to the mass ratio of 8:1:1, taking N-methylpyrrolidone (NMP) as a solvent, placing the mixture in a small beaker, and stirring and mixing the mixture for 2 hours at the rotating speed of 1000r/min to obtain slurry. Coating the slurry on a current collector aluminum foil by using an automatic coating machine, flatly placing the current collector aluminum foil on toughened glass, transferring the current collector aluminum foil to a vacuum drying oven at 85 ℃ for drying for 4h, preparing a pole piece with the diameter of 14mm by punching, drying for 4h in the vacuum drying oven at 100 ℃, placing the pole piece in a glove box with the water content and the oxygen content of less than 0.1ppm and filled with argon atmosphere for 4h to reduce the water absorbed by the pole piece in the transferring process, and then assembling the pole piece into a CR2032 type button cell in the glove box. The battery takes a pure metal lithium sheet with the diameter of 16mm and the thickness of 0.5mm as a negative electrode, and porous polymer with the diameter of 18mm and the model of Celgard2300The ethylene film is a separator.
After the battery is assembled and aged for 12 hours, the charging and discharging tests of different potentials are carried out. Under the voltage of 4.5V, the activation is carried out for 3 circles at 0.1C, and the circulation is carried out for 200 circles at the magnification of 1C. The specific discharge capacity after 200 cycles is 159 mA h g < -1 >, and the capacity retention rate is 74.2%.
Example 3
Preparing a metal pyrophosphate-coated modified ternary precursor:
(1) dissolving 0.6mol of nickel sulfate, 0.2mol of cobalt sulfate and 0.2mol of manganese sulfate in 50mL of pure water to obtain a nickel-cobalt-manganese solution, then respectively adding the nickel-cobalt-manganese solution, a 4mol/L sodium hydroxide solution and a 10 mol/L ammonia water solution into a reaction kettle at a speed of 5mL/min in a nitrogen atmosphere, adjusting the pH value of a reaction system to 11-12, reacting for 48 hours at 50 ℃, filtering and drying to obtain a ternary material precursor Ni precursor0.6Co0.2Mn0.2(OH)2。
(2) Taking 0.1mol of Ni0.6Co0.2Mn0.2(OH)2Dispersing in 30 mL of aqueous solution, adding 1mmol of ZnCl2After dissolution, 0.5mmol K was added4P2O7Stirring for 5h, filtering, drying to obtain Zn2P2O7@Ni0.6Co0.2Mn0.2(OH)2。
Zn is added2P2O7@Ni0.6Co0.2Mn0.2(OH)2Mixing with lithium source, calcining to synthesize ternary material. And taking the active material as an active substance of the anode material, mixing the active substance with Acetylene Black (AB) as a conductive agent and polyvinylidene fluoride (PVDF) as a binder according to the mass ratio of 8:1:1, taking N-methylpyrrolidone (NMP) as a solvent, placing the mixture in a small beaker, and stirring and mixing the mixture for 2 hours at the rotating speed of 1000r/min to obtain slurry. Coating the slurry on a current collector aluminum foil by using an automatic coating machine, flatly placing the current collector aluminum foil on toughened glass, transferring the current collector aluminum foil to a vacuum drying oven at 85 ℃ for drying for 4h, preparing a pole piece with the diameter of 14mm by punching, drying the pole piece in the vacuum drying oven at 100 ℃ for 4h, and placing the pole piece in a glove box which is full of argon and has the water content and the oxygen content of less than 0.1ppm for 4h to reduce the adsorption of the pole piece in the transferring processAnd (4) moisture is added, and then the mixture is assembled into a CR2032 button cell in a glove box. The battery uses a pure metal lithium sheet with the diameter of 16mm and the thickness of 0.5mm as a negative electrode, and a porous polyethylene film with the diameter of 18mm and the model of Celgard2300 as a diaphragm.
After the battery is assembled and aged for 12 hours, the charging and discharging tests of different potentials are carried out. Under the voltage of 4.3V, the activation is carried out for 3 circles at 0.1C, and then the circulation is carried out for 100 circles at the magnification of 2C. The specific discharge capacity after 100 cycles is 146.6 mA h g < -1 >, and the capacity retention rate is 79.5%.
Example 4
Preparing a metal pyrophosphate-coated modified ternary precursor:
(1) dissolving 0.6mol of nickel sulfate, 0.2mol of cobalt sulfate and 0.2mol of manganese sulfate in 40mL of pure water to obtain a nickel-cobalt-manganese solution, then respectively adding the nickel-cobalt-manganese solution, a 4mol/L sodium hydroxide solution and a 10 mol/L ammonia water solution into a reaction kettle at a speed of 5mL/min in a nitrogen atmosphere, adjusting the pH value of a reaction system to 11-12, reacting for 48 hours at 50 ℃, filtering and drying to obtain a ternary material precursor Ni precursor0.6Co0.2Mn0.2(OH)2。
(2) Taking 0.1mol of Ni0.6Co0.2Mn0.2(OH)2Dispersed in 30 mL of water, 1mmol of CaCl was added2After dissolution, 0.5mmol K was added4P2O7Stirring for 5h, filtering, and drying to obtain Ca2P2O7@Ni0.6Co0.2Mn0.2(OH)2。
Adding Ca2P2O7@Ni0.6Co0.2Mn0.2(OH)2Mixing with lithium source, calcining to synthesize ternary material. And taking the active material as an active substance of the anode material, mixing the active substance with Acetylene Black (AB) as a conductive agent and polyvinylidene fluoride (PVDF) as a binder according to the mass ratio of 8:1:1, taking N-methylpyrrolidone (NMP) as a solvent, placing the mixture in a small beaker, and stirring and mixing the mixture for 2 hours at the rotating speed of 1000r/min to obtain slurry. Coating the slurry on a current collector aluminum foil by using an automatic coating machine, horizontally placing on toughened glass, transferring to a vacuum drying oven at 85 ℃ for drying for 4 hours, and preparing a punching sheet into a sheet with the diameter of 14mmDrying the pole piece for 4h at 100 ℃ in a vacuum drying oven, placing the pole piece for 4h in a glove box with water content and oxygen content lower than 0.1ppm and filled with argon atmosphere to reduce the water absorbed by the pole piece in the transfer process, and assembling the pole piece into a CR2032 type button cell in the glove box. The battery uses a pure metal lithium sheet with the diameter of 16mm and the thickness of 0.5mm as a negative electrode, and a porous polyethylene film with the diameter of 18mm and the model of Celgard2300 as a diaphragm.
After the battery is assembled and aged for 12 hours, the charging and discharging tests of different potentials are carried out. Under the voltage of 4.5V, the activation is carried out for 3 circles at 0.1C, and the cycle is carried out for 300 circles at the magnification of 3C. The specific discharge capacity after 300 cycles is 127.1 mA h g < -1 >, and the capacity retention rate is 76.7%.
Example 5
Preparing a metal pyrophosphate-coated modified ternary precursor:
(1) dissolving 0.6mol of nickel sulfate, 0.2mol of cobalt sulfate and 0.2mol of manganese sulfate in 40mL of pure water to obtain a nickel-cobalt-manganese solution, then respectively adding the nickel-cobalt-manganese solution, a 4mol/L sodium hydroxide solution and a 10 mol/L ammonia water solution into a reaction kettle at a speed of 5mL/min in a nitrogen atmosphere, adjusting the pH value of a reaction system to 11-12, reacting for 48 hours at 50 ℃, filtering and drying to obtain a ternary material precursor Ni precursor0.6Co0.2Mn0.2(OH)2。
(2) Taking 0.1mol of Ni0.6Co0.2Mn0.2(OH)2Dispersed in 20 mL of water, 1mmol of MgCl was added2After dissolution, 0.5mmol K was added4P2O7Stirring for 5h, filtering, and drying to obtain Mg2P2O7@Ni0.6Co0.2Mn0.2(OH)2。
Mixing Mg2P2O7@Ni0.6Co0.2Mn0.2(OH)2Mixing with lithium source, calcining to synthesize ternary material. Mixing the active material serving as the positive electrode material with Acetylene Black (AB) serving as a conductive agent and polyvinylidene fluoride (PVDF) serving as a binder in a mass ratio of 8:1:1, taking N-methylpyrrolidone (NMP) as a solvent, placing the mixture in a small beaker, and stirring the mixture for 2 hours at a rotating speed of 1000r/min to obtain the active materialTo a slurry. Coating the slurry on a current collector aluminum foil by using an automatic coating machine, flatly placing the current collector aluminum foil on toughened glass, transferring the current collector aluminum foil to a vacuum drying oven at 85 ℃ for drying for 4h, preparing a pole piece with the diameter of 14mm by punching, drying for 4h at 105 ℃ in the vacuum drying oven, placing the pole piece in a glove box with the water content and the oxygen content both lower than 0.1ppm and filled with argon atmosphere for 4h to reduce the water absorbed by the pole piece in the transferring process, and then assembling the pole piece into a CR2032 type button cell in the glove box. The battery uses a pure metal lithium sheet with the diameter of 16mm and the thickness of 0.5mm as a negative electrode, and a porous polyethylene film with the diameter of 18mm and the model of Celgard2300 as a diaphragm.
After the battery is assembled and aged for 12 hours, the charging and discharging tests of different potentials are carried out. Under the voltage of 4.5V, the activation is carried out for 3 circles at 0.1C, and the circulation is carried out for 200 circles at the magnification of 1C. The specific discharge capacity after 200 cycles is 143.8 mA h g < -1 >, and the capacity retention rate is 75.2%.
The above description is only a basic description of the present invention, and any equivalent changes made according to the technical solution of the present invention should fall within the protection scope of the present invention.
Claims (9)
1. A preparation method of a metal pyrophosphate-coated modified ternary precursor is characterized by comprising the following steps:
(1) preparing a metal salt solution A of nickel, cobalt and manganese;
(2) adding the metal salt solution A prepared in the step (1) into a reaction kettle, then adding a sodium hydroxide solution and an ammonia water solution into the reaction kettle, controlling the pH value in the kettle to be kept at 10.5-12 in the reaction process, and filtering and drying to obtain a ternary material precursor Ni after the reaction is finished1-x-yCoxMny(OH)2(ii) a Wherein x is more than or equal to 0.1 and less than or equal to 0.3, and y is more than or equal to 0.1 and less than or equal to 0.3;
(3) dispersing the ternary material precursor prepared in the step (2) in water, adding more than one soluble calcium, magnesium and zinc metal salt, adding a certain amount of pyrophosphoric acid and/or pyrophosphates, stirring for a period of time, filtering, and drying to obtain the metal pyrophosphate coated and modified ternary precursor.
2. The method for preparing the metal pyrophosphate-coated modified ternary precursor according to claim 1, wherein the nickel, cobalt and manganese salts in the metal salt solution A prepared in the step (1) are selected from one or more of nitrate, acetate and sulfate.
3. The method for preparing the metal pyrophosphate-coated modified ternary precursor according to claim 2, wherein the total molar concentration of the metal ions in the metal salt solution a in the step (1) is 1-5 mol/L.
4. The method for preparing the metal pyrophosphate-coated modified ternary precursor of claim 1, wherein the molar concentration of the sodium hydroxide solution in the step (2) is 1-5mol/L, and the molar concentration of the ammonia water solution is 5-12 mol/L.
5. The method for preparing the metal pyrophosphate-coated modified ternary precursor according to claim 1, wherein the reaction temperature in the step (2) is 40-80 ℃ and the reaction time is 10-50 h.
6. The method for preparing the metal pyrophosphate-coated modified ternary precursor according to claim 1, wherein the molar ratio of the metal salt to pyrophosphate in the step (3) is 1.2-4: 1.
7. The method for preparing the metal pyrophosphate-coated modified ternary precursor according to claim 1, wherein the molar ratio of the metal salt in the step (3) to the ternary material precursor prepared in the step (2) is 1:100 to 1: 50.
8. The method for preparing the metal pyrophosphate-coated modified ternary precursor according to claim 1, wherein the pyrophosphate in the step (3) is selected from Na4P2O7And/or K4P2O7。
9. The ternary material is characterized in that the ternary material is obtained by uniformly mixing the metal pyrophosphate-coated modified ternary precursor prepared by the preparation method of any one of claims 1-8 with a lithium source and then roasting.
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