WO2016101315A1 - Procédé de réparation de précurseur de matériau de pile ternaire nickel-cobalt-manganèse - Google Patents

Procédé de réparation de précurseur de matériau de pile ternaire nickel-cobalt-manganèse Download PDF

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WO2016101315A1
WO2016101315A1 PCT/CN2014/095727 CN2014095727W WO2016101315A1 WO 2016101315 A1 WO2016101315 A1 WO 2016101315A1 CN 2014095727 W CN2014095727 W CN 2014095727W WO 2016101315 A1 WO2016101315 A1 WO 2016101315A1
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cobalt
nickel
manganese
battery material
ternary battery
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PCT/CN2014/095727
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English (en)
Chinese (zh)
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张云河
郭苗苗
乐绪清
刘文泽
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深圳市格林美高新技术股份有限公司
荆门市格林美新材料有限公司
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Publication of WO2016101315A1 publication Critical patent/WO2016101315A1/fr

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the invention belongs to the technical field of nickel-cobalt-manganese battery materials, and in particular relates to a method for repairing a precursor of a nickel-cobalt-manganese ternary battery material.
  • Lithium-ion batteries are widely used in many fields such as mobile phones, digital cameras, computers, and electric vehicles because of their high energy, long service life, and low pollution.
  • the positive electrode material occupies the most important position in the structure of lithium ion battery, and its performance directly determines the performance of the final product lithium ion battery, and the performance and price of the positive electrode material will directly affect the performance and price of the lithium ion battery.
  • Lithium nickel cobalt manganese oxide is a high-capacity positive electrode material, which combines the advantages of lithium cobaltate, lithium nickelate and lithium manganate, and has a large reversible specific capacity, and is a very promising positive electrode material.
  • This material not only has the advantage of high specific capacity, but also has relatively good safety, relatively low price, good compatibility with electrolyte, excellent cycle performance, and is most likely to be applied simultaneously in small communication and small power fields.
  • Battery cathode materials even the possibility of application in large power fields.
  • the common nickel-cobalt-manganese precursor ratios are 424, 333, 523, and the like. In the process of preparing the precursor of nickel-cobalt-manganese cathode material, an unsuitable proportion will occur, and recycling and recycling of these discarded ternary precursor materials is also a key issue.
  • a Chinese patent application such as CN200810198972.0 discloses a method for preparing lithium nickel cobalt manganese oxide from a waste lithium ion battery.
  • the battery cathode material is nickel-cobalt-manganate, lithium nickel cobalt oxide and other waste lithium-ion batteries as raw materials, after dismantling, sorting, pulverizing, sieving and other pre-treatment, then high temperature debonding After the process of setting, sodium hydroxide and aluminum removal, the deactivated positive electrode material containing nickel, cobalt and manganese is obtained; then, the sulfuric acid and hydrogen peroxide system are leached, P 2 O 4 is used for extraction and impurity removal, and a pure nickel, cobalt and manganese solution is obtained.
  • the main features are: first, the binder is removed by heat treatment, and aluminum is removed by acid leaching and pH adjustment in the presence of a reducing agent. According to the content of nickel, cobalt and manganese in the solution, an appropriate amount of nickel, cobalt and manganese sulfate is added to adjust the molar ratio of nickel, cobalt and manganese.
  • the sodium hydroxide is used as a precipitant and the ammonia is used as a complexing agent to obtain nickel, cobalt and manganese by coprecipitation.
  • the ternary material precursor is filtered to obtain a lithium salt solution, and the lithium salt solution is purified and precipitated to obtain lithium carbonate. Finally, the nickel-cobalt-manganese ternary material precursor is mixed with lithium carbonate in proportion, calcined at a high temperature, and cooled to obtain nickel-cobalt-manganese. Lithium acid.
  • the above method realizes the recycling of the ternary cathode material, but does not involve the recycling of the nickel-cobalt-manganese ternary precursor waste, and the method for recovering the nickel-cobalt-manganese ternary waste by extraction and the like is complicated and the recovery cost is relatively high. High, and involves organic solvents, which are likely to cause secondary pollution of materials.
  • the purpose of the embodiments of the present invention is to overcome the above-mentioned deficiencies of the prior art, and to provide a method for repairing a precursor of a nickel-cobalt-manganese ternary battery material, and a spherical nickel-cobalt-manganese precursor material having a regular shape and uniform distribution can be obtained.
  • a method for repairing a precursor of a nickel-cobalt-manganese ternary battery material comprising:
  • the mixture is calcined to obtain a nickel cobalt manganese ternary battery material precursor.
  • the method of the embodiment of the present invention mixes one of the manganese salt solution, the cobalt salt solution and the nickel salt solution with the nickel cobalt manganese ternary battery material precursor waste to make one of the manganese salt, the cobalt salt and the nickel salt.
  • Example 1 is a scanning electron micrograph of a precursor of a nickel-cobalt-manganese ternary battery material prepared in Example 1 of the present invention
  • Example 2 is a scanning electron micrograph of a precursor of a nickel-cobalt-manganese ternary battery material prepared in Example 2 of the present invention
  • Example 3 is a scanning electron micrograph of a precursor of a nickel-cobalt-manganese ternary battery material prepared in Example 3 of the present invention
  • Example 4 is a scanning electron micrograph of a precursor of a nickel-cobalt-manganese ternary battery material prepared in Example 4 of the present invention
  • Example 5 is a scanning electron micrograph of a precursor of a nickel-cobalt-manganese ternary battery material prepared in Example 5 of the present invention
  • Example 6 is a scanning electron micrograph of a precursor of a nickel-cobalt-manganese ternary battery material prepared in Example 6 of the present invention
  • Example 7 is a diagram showing the element distribution of a precursor of a nickel-cobalt-manganese ternary battery material prepared in Example 6 of the present invention; wherein A represents purple, B represents blue, and C represents yellow.
  • Embodiments of the present invention provide a method for repairing a precursor of a nickel-cobalt-manganese ternary battery material, comprising the following steps:
  • Step S01 mixing one or more of a manganese salt solution, a cobalt salt solution and a nickel salt solution with a nickel-cobalt-manganese ternary battery material precursor waste to obtain a mixture;
  • Step S02 calcining the mixture to obtain a nickel cobalt manganese ternary battery material precursor.
  • the method of the embodiment of the present invention mixes the metal salt solution of the manganese salt, the cobalt salt and the nickel salt with the nickel cobalt manganese ternary battery material precursor waste, so that the metal salt is adsorbed on the nickel cobalt manganese ternary battery material precursor waste.
  • the precursor waste of nickel-cobalt-manganese ternary battery material has a pore structure, and the manganese salt, the cobalt salt and the nickel salt are all fine-grained materials, and the nickel-cobalt-manganese ternary battery material precursor waste material and the metal salt solution are mixed and stirred.
  • the liquid of these metal salts is adsorbed and penetrated into the pores of the nickel-cobalt-manganese ternary battery material precursor waste by physical adsorption along the pores of the nickel-cobalt-manganese ternary battery material precursor waste, and is uniformly distributed.
  • the metal salt is adsorbed not only inside the pores but also on the surface of the nickel-cobalt-manganese ternary battery material precursor waste.
  • these metal salts are decomposed by calcination and uniformly distributed in the pores of the ternary material and the surface of the nickel-cobalt-manganese ternary battery precursor waste in the form of oxides, thereby obtaining a nickel-cobalt-manganese ternary battery material precursor which meets the requirements. .
  • the nickel-cobalt-manganese ternary battery material precursor waste is a washed waste material, that is, the nickel-cobalt-manganese ternary battery material precursor waste component is a pure nickel-cobalt-manganese ternary composite compound, and does not include other Impurities.
  • the composition of the nickel-cobalt-manganese ternary battery material precursor waste may be nickel-cobalt-manganese ternary composite hydroxide, nickel-cobalt-manganese ternary composite oxide, nickel-cobalt-manganese ternary composite salt or the like.
  • the nickel cobalt manganese ternary battery material precursor waste may be pulverized and ground before mixing, nickel
  • the particle size of the precursor waste of the cobalt-manganese ternary battery material is 3 to 18 ⁇ m.
  • the concentration of the nickel-cobalt-manganese ternary battery material precursor waste in the manganese salt solution, the cobalt salt solution, and/or the nickel salt solution is 2 to 10 g/mL. This concentration ensures sufficient wetting of the metal salt solution with the nickel-cobalt-manganese ternary battery material precursor. If the concentration is too small, the adsorption between the metal salt and the nickel-cobalt-manganese ternary battery material precursor is deteriorated. If the concentration is too large, the solution is relatively viscous, which is detrimental to sufficient wetting between the metal salt and the nickel-cobalt-manganese ternary battery material precursor waste.
  • Stirring may also be accompanied by the process of step S01.
  • the stirring time is 5 to 30 minutes, and the stirring speed is 100-200 r/min.
  • the mixing and agitating process can be carried out in a waxing mixer.
  • the stirring time is favorable for uniform mixing of the materials, and the adsorption is sufficient, and the stirring time is generally as long as possible, but from the economic point of view, the stirring time is generally not longer than 30 minutes; if the time is shorter than 5 minutes, the adsorption effect is affected. The adsorption is insufficient.
  • Stirring speed is 100-200 At r/min, the agitation speed does not affect the agitation adsorption effect while maintaining the life of the mixer.
  • the ratio of nickel in the cobalt and/or nickel salt solution in the manganese salt solution to the nickel, cobalt, and manganese in the precursor waste of the nickel-cobalt-manganese ternary battery material makes the nickel in the system
  • the molar ratio of cobalt to manganese is 4:2:4, 3:3:3 or 5:2:3.
  • This molar ratio is the molar ratio of nickel, cobalt, and manganese of a common nickel-cobalt-manganese ternary battery material.
  • the manganese salt solution is mixed with the nickel cobalt manganese ternary battery material precursor waste in step S01 to obtain a mixture. Since the decomposition temperature of the manganese salt is low, it is advantageous to carry out step S02 at a low temperature.
  • the manganese salt is preferably used in step S01, the molar ratio of nickel, cobalt and manganese in the precursor waste of the suitable nickel-cobalt-manganese ternary battery material is preferably 4:2:2, 3:3:1 or 5:2:2.
  • the manganese salt is preferably used in the step S01, when the molar ratio of nickel, cobalt and manganese in the nickel-cobalt-manganese ternary battery precursor waste material is 4:2:2, the manganese and nickel-cobalt-manganese ternary in the manganese salt solution
  • the molar ratio of nickel, cobalt and manganese in the battery material precursor waste is 2:4:2:2.
  • the ratio of the nickel, cobalt and manganese in the precursor of the nickel-cobalt-manganese ternary battery material finally obtained is 4:2:4, which satisfies the composition of the conventional nickel-cobalt-manganese ternary battery material precursor.
  • the nickel in the manganese and nickel-cobalt-manganese ternary battery material precursor waste in the manganese salt solution The molar ratio of cobalt to manganese is 2:3:3:1.
  • the ratio of the nickel, cobalt and manganese in the precursor of the nickel-cobalt-manganese ternary battery material finally obtained is 3:3:3, which satisfies the composition of the conventional nickel-cobalt-manganese ternary battery material precursor.
  • the nickel in the manganese and nickel-cobalt-manganese ternary battery material precursor waste in the manganese salt solution The molar ratios of cobalt and manganese are 1:5:2:2, respectively.
  • the ratio of the nickel, cobalt and manganese in the precursor of the nickel-cobalt-manganese ternary battery material finally obtained is 5:2:3, which satisfies the composition of the conventional nickel-cobalt-manganese ternary battery material precursor.
  • the manganese salt solution in the step S01 can be obtained by dissolving a certain mass of the manganese salt in water so that the volume of the manganese salt solution is 100 to 500 mL.
  • the solution of the above volume is mainly considered to be sufficiently wetted during the mixing process of the metal salt solution and the nickel-cobalt-manganese ternary battery material precursor waste.
  • the volume of the metal salt solution is too small to ensure the precursor of the nickel-cobalt-manganese ternary battery material.
  • the body waste is completely wetted, resulting in uneven doping; while the metal salt solution is too bulky, part of the metal salt still exists in the form of an aqueous solution during the mixing process, and is separately precipitated in the form of metal oxide during the calcination process, thereby It also causes uneven doping.
  • the manganese salt preferably decomposes a manganese salt having a low temperature, so that the subsequent calcination step can be carried out at a low temperature, such as manganese acetate Mn(Ac) 2 and manganese carbonate MnCO 3 .
  • the manganese salt is more preferably Mn(Ac) 2 , and Mn(Ac) 2 has the advantages of low decomposition temperature, high solubility in water, and low cost, and manganese acetate is also selected because it does not introduce new impurities after pyrolysis. If MnCl 2 is calcined at a high temperature, Cl will remain in the precursor, resulting in a high impurity content.
  • the high solubility of the manganese salt in water ensures the full utilization of the manganese salt and is more effectively wetted with the nickel-cobalt-manganese ternary battery material precursor waste.
  • the nickel salt solution is mixed with the nickel-cobalt-manganese ternary battery material precursor waste in step S01 to obtain a mixture.
  • the nickel salt is preferably used in the step S01, the molar ratio of nickel, cobalt and manganese in the precursor waste of the suitable nickel-cobalt-manganese ternary battery material is preferably 2:2:4, 1:3:3 or 2:2:3. .
  • step S01 when the nickel salt is preferably used in step S01, when the molar ratio of nickel, cobalt and manganese in the nickel-cobalt-manganese ternary battery precursor waste material is 2:2:4, the nickel and nickel-cobalt-manganese ternary battery in the nickel salt solution
  • the molar ratio of nickel, cobalt and manganese in the material precursor waste is 2:2:2:4.
  • the ratio of the nickel, cobalt and manganese in the precursor of the nickel-cobalt-manganese ternary battery material finally obtained is 4:2:4, which satisfies the composition of the conventional nickel-cobalt-manganese ternary battery material precursor.
  • nickel in the nickel and nickel-cobalt-manganese ternary battery material precursor waste in the nickel salt solution nickel in the nickel and nickel-cobalt-manganese ternary battery material precursor waste in the nickel salt solution
  • the molar ratio of cobalt to manganese is 2:1:3:3.
  • the ratio of the nickel, cobalt and manganese in the precursor of the nickel-cobalt-manganese ternary battery material finally obtained is 3:3:3, which satisfies the composition of the conventional nickel-cobalt-manganese ternary battery material precursor.
  • the nickel in the nickel and nickel-cobalt-manganese ternary battery material precursor waste in the nickel salt solution The molar ratios of cobalt and manganese are 3:2:2:3, respectively.
  • the ratio of the nickel, cobalt and manganese in the precursor of the nickel-cobalt-manganese ternary battery material finally obtained is 5:2:3, which satisfies the composition of the conventional nickel-cobalt-manganese ternary battery material precursor.
  • the nickel salt solution in the step S01 can be obtained by dissolving a certain amount of the nickel salt in water so that the volume of the nickel salt solution is 100 to 500 mL.
  • the nickel salt preferably decomposes a nickel salt having a low temperature, so that the subsequent calcination step can be carried out at a low temperature, such as nickel acetate Ni(Ac) 2 and nickel carbonate NiCO 3 .
  • the nickel salt is more preferably Ni(Ac) 2 .
  • the cobalt salt solution is mixed with the nickel-cobalt-manganese ternary battery material precursor waste in step S01 to obtain a mixture.
  • the cobalt salt is preferably used in step S01, the molar ratio of nickel, cobalt and manganese in the precursor waste of the suitable nickel-cobalt-manganese ternary battery material is preferably 4:1:4, 3:1:3 or 5:1:3. .
  • the cobalt salt is preferably used in step S01
  • the molar ratio of nickel, cobalt and manganese in the precursor waste of the nickel-cobalt-manganese ternary battery material is 4:1:4
  • the cobalt and nickel-cobalt-manganese ternary battery in the cobalt salt solution The molar ratio of nickel, cobalt and manganese in the material precursor waste is 1:4:1:4.
  • the ratio of the nickel, cobalt and manganese in the precursor of the nickel-cobalt-manganese ternary battery material finally obtained is 4:2:4, which satisfies the composition of the conventional nickel-cobalt-manganese ternary battery material precursor.
  • the nickel in the cobalt and nickel-cobalt-manganese ternary battery material precursor waste in the cobalt salt solution is 3:1:3
  • the nickel in the cobalt and nickel-cobalt-manganese ternary battery material precursor waste in the cobalt salt solution is 2:3:1:3.
  • the ratio of the nickel, cobalt and manganese in the precursor of the nickel-cobalt-manganese ternary battery material finally obtained is 3:3:3, which satisfies the composition of the conventional nickel-cobalt-manganese ternary battery material precursor.
  • the nickel in the cobalt and nickel-cobalt-manganese ternary battery material precursor waste in the cobalt salt solution The molar ratios of cobalt and manganese are 1:5:1:3, respectively.
  • the ratio of the nickel, cobalt and manganese in the precursor of the nickel-cobalt-manganese ternary battery material finally obtained is 5:2:3, which satisfies the composition of the conventional nickel-cobalt-manganese ternary battery material precursor.
  • the cobalt salt solution in the step S01 can be obtained by dissolving a certain amount of the cobalt salt in water so that the volume of the cobalt salt solution is 100 to 500 mL.
  • the cobalt salt preferably decomposes a cobalt salt having a low temperature, so that the subsequent calcination step can be carried out at a low temperature, such as cobalt acetate Co(Ac) 2 and cobalt carbonate CoCO 3 .
  • the cobalt salt is more preferably Co(Ac) 2 .
  • a suitable nickel salt, cobalt salt and manganese salt with a low decomposition temperature may be selected as a metal salt solution. use.
  • the calcination temperature is 350 ° C to 500 ° C, and the calcination time is 2 to 6 hours.
  • the calcination temperature is selected in consideration of the fact that the metal salt can be completely decomposed while reducing the calcination temperature as much as possible and reducing the cost. If the calcination temperature is lower than 350 ° C, the temperature is too low to reach the decomposition temperature of the metal salt.
  • the calcination time is selected based on whether the metal salt can be completely decomposed during the calcination process.
  • the calcination time is more than 6 hours, the calcination time is too long, and the cost is increased; if the calcination time is less than 2 hours, the calcination time is too short, which may cause incomplete decomposition of the metal salt.
  • Ni 1/2 Co 1/4 Mn 1/4 (OH) 2 the composition of the nickel-cobalt-manganese ternary battery material precursor waste material is Ni 1/2 Co 1/4 Mn 1/4 (OH) 2 .
  • the stirring speed was 100 r/min, and the stirring time was 5 min.
  • the mixture was then calcined in a muffle furnace at 400 ° C for 6 hours to obtain a nickel cobalt manganese ternary battery material precursor.
  • the molar ratio of nickel, cobalt and manganese in the precursor of the obtained nickel-cobalt-manganese ternary battery material was 4:2:4.
  • FIG. 1 it is a scanning electron micrograph of a precursor of a nickel-cobalt-manganese ternary battery material prepared in Example 1 of the present invention. It can be seen from the figure that the precursor of the nickel-cobalt-manganese ternary battery material obtained in Example 1 is spherical, and the sphericity is good, the particles are relatively uniform, and no precipitation and agglomeration of the manganese salt occurs.
  • the spherical particles have a relatively small sliding friction factor, have superior expandability and ductility, and exhibit good miscibility and good processing properties in the process of preparing a lithium ion battery by mixing with a lithium salt. Therefore, the nickel-cobalt-manganese ternary battery material precursor of Example 1 is spherical in shape to facilitate the preparation of a lithium-ion battery.
  • the composition of the nickel-cobalt-manganese ternary battery material precursor waste is Ni 3/7 Co 3/7 Mn 1/7 (OH) 2 .
  • the stirring speed was 100 r/min, and the stirring time was 30 min.
  • the mixture was then calcined in a muffle furnace at 450 ° C for 2 hours to obtain a nickel cobalt manganese ternary battery material precursor.
  • the molar ratio of nickel, cobalt and manganese in the precursor of the obtained nickel-cobalt-manganese ternary battery material was 3:3:3.
  • FIG. 2 it is a scanning electron micrograph of a precursor of a nickel-cobalt-manganese ternary battery material prepared in Example 2 of the present invention.
  • the precursor of the nickel-cobalt-manganese ternary battery material obtained in Example 2 was spherical, and the sphericity was good, and the phenomenon of precipitation and agglomeration of the manganese salt did not occur, but the distribution of the particle size was relatively uneven.
  • the composition of the nickel-cobalt-manganese ternary battery material precursor waste is Ni 5/9 Co 2/9 Mn 2/9 (OH) 2 .
  • the stirring speed was 200 r/min and the stirring time was 12 min.
  • the mixture was then calcined in a muffle furnace at 430 ° C for 3 hours to obtain a nickel cobalt manganese ternary battery material precursor.
  • the molar ratio of nickel, cobalt and manganese in the precursor of the obtained nickel-cobalt-manganese ternary battery material was 5:2:3.
  • FIG. 3 it is a scanning electron micrograph of a precursor of a nickel-cobalt-manganese ternary battery material prepared in Example 3 of the present invention. It can be seen from the figure that the precursor of the nickel-cobalt-manganese ternary battery material obtained in Example 3 is spherical, and the sphericity is good, the particles are relatively uniform, and no precipitation and agglomeration of the manganese salt occurs.
  • the composition of the nickel-cobalt-manganese ternary battery material precursor waste material is NiCo 1/2 Mn 1/2 O 2 .
  • the stirring speed was 120 r/min, and the stirring time was 20 min.
  • the mixture was then calcined in a muffle furnace at 420 ° C for 5 hours to obtain a nickel cobalt manganese ternary battery material precursor.
  • the molar ratio of nickel, cobalt and manganese in the precursor of the obtained nickel-cobalt-manganese ternary battery material was 4:2:4.
  • FIG. 4 it is a scanning electron micrograph of a precursor of a nickel-cobalt-manganese ternary battery material prepared in Example 4 of the present invention. It can be seen from the figure that the precursor of the nickel-cobalt-manganese ternary battery material obtained in Example 4 is spherical, and the sphericity is good, the particles are relatively uniform, and no precipitation and agglomeration of the manganese salt occurs.
  • the composition of the nickel-cobalt-manganese ternary battery material precursor waste is Ni 6/7 Co 6/7 Mn 2/7 O 2 .
  • the stirring speed was 150 r/min, and the stirring time was 8 min.
  • the mixture was then calcined in a muffle furnace at 440 ° C for 3 hours to obtain a nickel cobalt manganese ternary battery material precursor.
  • the molar ratio of nickel, cobalt and manganese in the precursor of the obtained nickel-cobalt-manganese ternary battery material was 3:3:3.
  • FIG. 5 it is a scanning electron micrograph of a precursor of a nickel-cobalt-manganese ternary battery material prepared in Example 5 of the present invention. It can be seen from the figure that the precursor of the nickel-cobalt-manganese ternary battery material obtained in Example 5 is spherical, and the sphericity is good, the particles are relatively uniform, and no precipitation and agglomeration of the manganese salt occurs.
  • the composition of the nickel-cobalt-manganese ternary battery material precursor waste is Ni 10/9 Co 4/9 Mn 4/9 O 2 .
  • the stirring speed was 180 r/min and the stirring time was 25 min.
  • the mixture was then calcined in a muffle furnace at 410 ° C for 5 hours to obtain a nickel cobalt manganese ternary battery material precursor.
  • the molar ratio of nickel, cobalt and manganese in the precursor of the obtained nickel-cobalt-manganese ternary battery material was 5:2:3.
  • FIG. 6 it is a scanning electron micrograph of a precursor of a nickel-cobalt-manganese ternary battery material prepared in Example 6 of the present invention.
  • the precursor of the nickel-cobalt-manganese ternary battery material obtained in Example 6 was spherical, and the sphericity was good, and the phenomenon of precipitation and agglomeration of the manganese salt did not occur, but the distribution of the particle size was relatively uneven.
  • FIG. 6 it is a scanning electron micrograph of a precursor of a nickel-cobalt-manganese ternary battery material prepared in Example 6 of the present invention.
  • the precursor of the nickel-cobalt-manganese ternary battery material obtained in Example 6 was spherical, and the sphericity was good,
  • Example 7 is an elemental distribution diagram of a precursor of a nickel-cobalt-manganese ternary battery material prepared in Example 6 of the present invention, wherein A represents purple, B represents blue, and C represents yellow. It can be seen from the figure that in the nickel-cobalt-manganese ternary precursor obtained by the method of the present invention, the manganese element is uniformly distributed in the pores and on the surface.
  • the composition of the nickel-cobalt-manganese ternary battery material precursor waste material is Ni 1/4 Co 1/4 Mn 1/2 (OH) 2 .
  • the stirring speed was 130 r/min and the stirring time was 15 min.
  • the mixture was then calcined in a muffle furnace at 350 ° C for 6 hours to obtain a nickel cobalt manganese ternary battery material precursor.
  • the molar ratio of nickel, cobalt and manganese in the precursor of the obtained nickel-cobalt-manganese ternary battery material was 4:2:4.
  • the nickel element was uniformly distributed in the pores and on the surface, and nickel salt precipitation and agglomeration did not occur.
  • the composition of the nickel-cobalt-manganese ternary battery material precursor waste is Ni 1/7 Co 3/7 Mn 3/7 (OH) 2 .
  • the stirring speed was 120 r/min and the stirring time was 7 min.
  • the mixture was then calcined in a muffle furnace at 500 ° C for 2 hours to obtain a nickel cobalt manganese ternary battery material precursor.
  • the molar ratio of nickel, cobalt and manganese in the precursor of the obtained nickel-cobalt-manganese ternary battery material was 4:2:4.
  • the nickel element was uniformly distributed in the pores and on the surface, and no nickel salt precipitation and agglomeration occurred.
  • the composition of the nickel-cobalt-manganese ternary battery material precursor waste is Ni 2/7 Co 2/7 Mn 3/7 (OH) 2 .
  • the stirring speed was 160 r/min and the stirring time was 24 min.
  • the mixture was then calcined in a muffle furnace at 380 ° C for 5.5 hours to obtain a nickel cobalt manganese ternary battery material precursor.
  • the molar ratio of nickel, cobalt and manganese in the precursor of the obtained nickel-cobalt-manganese ternary battery material was 4:2:4.
  • the nickel element was uniformly distributed in the pores and on the surface, and nickel salt precipitation and agglomeration did not occur.
  • the composition of the nickel-cobalt-manganese ternary battery material precursor waste is Ni 4/9 Co 1/9 Mn 4/9 (OH) 2 .
  • the stirring speed was 100 r/min and the stirring time was 25 min.
  • the mixture was then calcined in a muffle furnace at 450 ° C for 4.5 hours to obtain a nickel cobalt manganese ternary battery material precursor.
  • the molar ratio of nickel, cobalt and manganese in the precursor of the obtained nickel-cobalt-manganese ternary battery material was 4:2:4.
  • cobalt elements were uniformly distributed in the pores and on the surface, and no precipitation and agglomeration of cobalt salts occurred.
  • the composition of the nickel-cobalt-manganese ternary battery material precursor waste is Ni 3/7 Co 1/7 Mn 3/ 7(OH) 2 .
  • the stirring speed was 170 r/min, and the stirring time was 8 min.
  • the mixture was then calcined in a muffle furnace at 400 ° C for 3.5 hours to obtain a nickel cobalt manganese ternary battery material precursor.
  • the molar ratio of nickel, cobalt and manganese in the precursor of the obtained nickel-cobalt-manganese ternary battery material was 4:2:4.
  • the cobalt element was uniformly distributed in the pores and on the surface, and no precipitation and agglomeration of the cobalt salt occurred.
  • the composition of the nickel-cobalt-manganese ternary battery material precursor waste is Ni 5/9 Co 1/9 Mn 3/9 (OH) 2 .
  • the stirring speed was 110 r/min, and the stirring time was 20 min.
  • the mixture was then calcined in a muffle furnace at 420 ° C for 5 hours to obtain a nickel cobalt manganese ternary battery material precursor.
  • the molar ratio of nickel, cobalt and manganese in the precursor of the obtained nickel-cobalt-manganese ternary battery material was 4:2:4.
  • cobalt elements were uniformly distributed in the pores and on the surface, and no precipitation and agglomeration of cobalt salts occurred.
  • the method of the present invention is simple in process and easy to operate.
  • the nickel-cobalt-manganese ternary battery material precursor waste is used to make full use of resources, and the recycling cost is low, which is suitable for commercial production.
  • the entire preparation process does not involve organic solvents and is less polluting to the environment.
  • the product obtained by the method has a regular shape and a uniform distribution.

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  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Manufacture And Refinement Of Metals (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)

Abstract

Selon un mode de réalisation, la présente invention concerne un procédé de réparation d'un précurseur de matériau de pile ternaire nickel-cobalt-manganèse qui consiste : à mélanger une ou plusieurs solutions parmi une solution de sel de manganèse, une solution de sel de cobalt et une solution de sel de nickel avec des déchets de précurseur de matériau de pile ternaire nickel-cobalt-manganèse afin d'obtenir un mélange ; à calciner le mélange afin d'obtenir le précurseur de matériau de pile ternaire nickel-cobalt-manganèse. Le procédé de la présente invention consiste à mélanger la solution de sel de manganèse avec les déchets de précurseur de matériau de pile ternaire nickel-cobalt-manganèse, de manière à permettre aux déchets de précurseur de matériau de pile ternaire nickel-cobalt-manganèse d'absorber le sel de manganèse, et à calciner le mélange afin de décomposer le sel de manganèse et de l'amener à être uniformément distribué dans un trou du matériau ternaire sous la forme d'un oxyde, et à obtenir le précurseur de matériau de pile ternaire nickel-cobalt-manganèse qui répond aux exigences.
PCT/CN2014/095727 2014-12-22 2014-12-30 Procédé de réparation de précurseur de matériau de pile ternaire nickel-cobalt-manganèse WO2016101315A1 (fr)

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CN114628663A (zh) * 2022-04-21 2022-06-14 华鼎国联四川电池材料有限公司 一种铈掺杂三元正极材料及其制备方法
CN115849462A (zh) * 2022-12-07 2023-03-28 合肥国轩高科动力能源有限公司 镍钴锰三元正极材料及其制备方法与应用
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