CN116143198B - Method for regulating and controlling crystal face area of layered cathode material precursor (010) through anions - Google Patents
Method for regulating and controlling crystal face area of layered cathode material precursor (010) through anions Download PDFInfo
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- CN116143198B CN116143198B CN202310410909.3A CN202310410909A CN116143198B CN 116143198 B CN116143198 B CN 116143198B CN 202310410909 A CN202310410909 A CN 202310410909A CN 116143198 B CN116143198 B CN 116143198B
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- 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
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Abstract
The invention discloses a method for regulating and controlling the crystal face area of a layered cathode material precursor (010) through anions, which takes nickel-based inorganic salt or nickel-based organic salt as a raw material, and simultaneously adopts a nitrogen-containing complexing agent and an inorganic anion crystal face growth inducer to react to prepare hydroxide seed crystals; and (3) taking hydroxide seed crystals as a base material to carry out coprecipitation reaction, taking nickel-based inorganic salt or nickel-based organic salt as a raw material, and simultaneously adopting a nitrogen-containing complexing agent and an inorganic anion crystal face growth inducer to carry out reaction so as to prepare the nickel-based layered ternary anode material precursor. The ternary positive electrode material precursor prepared by the method has the advantages of good quality, large primary particle (010) crystal face area, large occupied ratio and good sphericity of secondary particles.
Description
Technical Field
The invention belongs to the technical field of modification of nickel-based layered ternary cathode materials, and particularly relates to a method for regulating and controlling the crystal face area of a layered cathode material precursor (010) through anions.
Background
With the rapid development of new energy automobiles, the demand of lithium ion secondary batteries is rapidly increased, and the demand of positive electrode materials is greatly increased. The nickel-cobalt-manganese or nickel-cobalt-aluminum or nickel-cobalt-manganese-aluminum layered positive electrode material has relatively high energy density, good safety performance and relatively low cost, and becomes the positive electrode material with the largest demand in the current market. Due to layered cathode material Li + The embedded and extracted channel is vertical to the (010) crystal face, and the increase of the (010) crystal face area can effectively improve Li + Embedding and embedding probability, thereby improving the layered ternary positive electrode material Li + The conductivity is improved, and the electrochemical performance of the nickel cobalt manganese or nickel cobalt aluminum or nickel cobalt manganese aluminum layered anode material is further improved. The existing research shows that: certain inheritance exists between the crystal face area of the nickel cobalt manganese or nickel cobalt aluminum or nickel cobalt manganese aluminum layered anode material (010) and the crystal face area of the precursor (010) thereof, and the improvement of the crystal face area of the precursor (010) of the nickel cobalt manganese or nickel cobalt aluminum or nickel cobalt manganese aluminum layered anode material is beneficial to the improvement of the crystal face area of the nickel cobalt manganese or nickel cobalt aluminum or nickel cobalt manganese aluminum layered anode material (010). Therefore, the nickel cobalt manganese or nickel cobalt aluminum or nickel cobalt manganese aluminum layered positive electrode material precursor with large (010) crystal face area is prepared as an effective means for improving the crystal face area of the nickel cobalt manganese or nickel cobalt aluminum or nickel cobalt manganese aluminum layered positive electrode material (010).
Patent document CN113023791a reports: and (3) synthesizing a high-nickel ternary positive electrode material precursor with larger (010) crystal face area on the lithium-manganese-rich precursor template by adopting the precursor of the lithium-manganese-rich positive electrode material as the crystal face induction template. Patent document CN111293305a reports: and crystal face growth regulators such as polyacrylamide, polyvinyl alcohol, polyethylene oxide, sodium polyacrylate, sodium alginate, polyvinylpyrrolidone and the like are adopted in the preparation stage and the growth process of the precursor seed crystal, so that the ternary positive electrode material precursor with larger (010) crystal face area is synthesized. In the patent document CN106892464a, crystal face growth regulators, such as sodium dodecyl benzene sulfonate and thiobetaine, are used in the preparation stage and the growth process of the precursor seed crystal to synthesize a ternary positive electrode material precursor with a larger (010) crystal face area. In the patent document CN109742337a, a crystal face growth regulator, such as cetyltrimethylammonium bromide, is used to synthesize a ternary positive electrode material precursor with a larger crystal face area in the preparation stage and the growth process of the precursor seed crystal. In the patent document CN108269995a, crystal face growth regulators, such as CTMAB, triethanolamine, turkish red oil, are used to synthesize a ternary positive electrode material precursor with a larger crystal face area (010) in both the preparation stage and the growth process of the precursor seed crystal. Patent document CN112151790a adopts control of the reaction kinetics in the seed crystal preparation stage and precursor growth process, so as to regulate and control the area of each crystal face of the ternary precursor; in the preparation stage of the seed crystal and in the growth process of the precursor, the patent document CN113387399A controls the area of each crystal face of the high-nickel ternary anode material precursor by regulating and controlling the pH of key technological parameters and the dosage of the complexing agent; in the patent document CN113329975a, by a method of continuously adding seed crystals in the precursor growth process, the 001 peak of the crystal plane parameter in the precursor material of the prepared ternary cathode material is lower than the 101 peak of the crystal plane parameter. In the preparation stage of the seed crystal and in the growth process of the precursor, the patent document CN112919553A obtains the precursor with {010} crystal face group active crystal face ratio, active crystal face ratio up to 80% and concentrated granularity distribution by adjusting the concentration of transition metal ions and complexing agents in the coprecipitation reaction process. In the seed crystal preparation stage, the patent document CN112086616A is used for preparing a flaky seed crystal which is favorable for growing a large (010) crystal precursor and has good dispersibility by increasing the concentration of ammonia water in a reaction solution and reducing the pH value so as to slow down the nucleation speed of hydroxide; and growing a ternary positive electrode material precursor with primary particles of micron order and large (010) crystal face area on the secondary seed crystal. The method for improving the crystal face area of the nickel cobalt manganese or nickel cobalt aluminum or nickel cobalt manganese aluminum layered anode material precursor (010) has the following defects: the (010) crystal face area of the ternary precursor is regulated and controlled by adopting the crystal face growth regulator in the patent (CN 111293305A, CN106892464A, CN109742337A, CN 108269995A), and the adopted crystal face growth regulator contains an organic molecular chain, so that the cost of the crystal face growth regulator is higher and the subsequent wastewater treatment cost of the crystal face growth regulator is higher; the method reported by the patent (CN 112151790A, CN113387399A, CN113329975A, CN 112919553A) can regulate and control the (010) crystal face area of the ternary positive electrode material precursor, but has limited regulation and control effects; the ternary positive electrode material precursor with a large (010) crystal face area can be prepared by adopting the method reported in the patent (CN 112086616A), but the sphericity of secondary particles of the ternary positive electrode material precursor is poor, so that the subsequent processing performance is affected; the preparation method of the low-sulfur small-particle-size nickel cobalt manganese hydroxide reported by the patent (CN 106745331A) is characterized in that although the used additive is sodium sulfate or ammonium sulfate, the effect of adding the additive only assists the quick dispersion of crystal nucleus, thereby playing a role in reducing sulfur and not playing a role in regulating and controlling (010) crystal faces; and the additive is added after the crystal nucleus is finished, and is not added in the whole process.
Disclosure of Invention
The invention provides a method for regulating and controlling the crystal face area of a layered cathode material precursor (010) through anions, which aims at the defects of the existing method for regulating and controlling the crystal face area of the layered ternary cathode material precursor (010).
The invention adopts the following technical proposal to solve the technical problems, and is a method for regulating and controlling the crystal face area of a precursor (010) of a layered positive electrode material by anions, which is characterized by comprising the following specific steps:
step S1, seed crystal preparation: taking nickel-based inorganic salt or nickel-based organic salt as a raw material, and simultaneously adopting a nitrogen-containing complexing agent and an inorganic anion crystal face growth inducer to react to prepare a similar spherical hydroxide seed crystal which is favorable for growing a precursor with a large (010) crystal face area and has larger and loose flaky primary particles;
step S2, a precursor growth stage: taking the hydroxide seed crystal obtained in the step S1 as a base material to carry out coprecipitation reaction, taking nickel-based inorganic salt or nickel-based organic salt as a raw material, and simultaneously adopting a nitrogen-containing complexing agent and an inorganic anion crystal face growth inducer to carry out reaction to prepare a nickel-based layered ternary positive electrode material precursor with large primary particle (010) crystal face area and spherical-like secondary particles;
the nitrogen-containing complexing agent is one or a combination of more of ammonia water, ammonium sulfite, ammonium bisulfate, ammonium sulfate, ammonium bisulfate, ammonium sulfide, ammonium bisulfide, ammonium thiosulfate, ammonium chloride or ammonium carbonate, and the inorganic anionic crystal face growth inducer is one or a combination of more of sodium sulfate, sodium nitrate, sodium chloride, potassium sulfate, potassium nitrate, potassium chloride, ammonium sulfate, ammonium nitrate or ammonium chloride.
Further defined, the nickel-based inorganic salt or the nickel-based organic salt in the step S1 and the step S2 are the same, the nickel-based inorganic salt is nickel-based sulfate, nickel-based nitrate or nickel-based chloride, the nickel-based organic salt is nickel-based acetate, and the nickel base in the nickel-based inorganic salt or the nickel-based organic salt is nickel cobalt manganese, nickel cobalt aluminum or nickel cobalt manganese aluminum.
Further defined, the specific process of step S1 is: under the atmosphere of inert gas, respectively adding nickel-based inorganic salt or nickel-based organic salt solution, naOH solution, nitrogen-containing complexing agent and inorganic anion crystal face growth inducer into a reaction kettle which takes the nitrogen-containing complexing agent and the inorganic anion crystal face growth inducer as bottom water, controlling the pH value in the reaction kettle to be 10.0-12.0, simultaneously controlling the concentration of the nitrogen-containing complexing agent in the reaction kettle to be 0.01-1.0mol/L and the concentration of the inorganic anion crystal face growth inducer to be 0.01-2.0mol/L, and reacting for 0.1-5.0 hours at the temperature of 30-80 ℃ to obtain hydroxide seed crystals.
Further limited, the molar concentration of the nickel-based inorganic salt or the nickel-based organic salt solution in the step S1 is 1.0-3.0mol/L, the molar concentration of the NaOH solution is 2.0-7.0mol/L, the molar concentration of the nitrogen-containing complexing agent is 5.0-15.0mol/L, the molar concentration of the inorganic anion crystal face growth inducer is 5.0-10.0mol/L, the feeding mass ratio of the nickel-based inorganic salt or the nickel-based organic salt solution to the NaOH solution is 1.5-3:1, the pH value in the reaction kettle is controlled to be 11.6-11.9, the concentration of the nitrogen-containing complexing agent in the reaction kettle is controlled to be 0.3-0.5mol/L, and the concentration of the inorganic anion crystal face growth inducer is controlled to be 0.5-1.0mol/L.
Further defined, the specific process of step S2 is: and (2) respectively dropwise adding nickel-based inorganic salt or nickel-based organic salt solution, naOH solution, a nitrogen-containing complexing agent and an inorganic anion crystal face growth inducer into the reaction kettle with the hydroxide seed crystal prepared in the step (S1), controlling the pH value in the reaction kettle to be 10.0-12.5, simultaneously controlling the concentration of ammonia water in the reaction kettle to be 0.1-1.0mol/L and the concentration of the inorganic anion crystal face growth inducer to be 0.01-2.0mol/L, reacting for 40-100 hours at the temperature of 30-80 ℃ to obtain slurry, and washing and drying the slurry to obtain the nickel-based layered ternary cathode material precursor.
Further limited, the molar concentration of the nickel-based inorganic salt or the nickel-based organic salt solution in the step S2 is 1.0-3.0mol/L, the molar concentration of the NaOH solution is 2.0-7.0mol/L, the molar concentration of the nitrogen-containing complexing agent is 5.0-15.0mol/L, the molar concentration of the inorganic anion crystal face growth inducer is 5.0-10.0mol/L, the feeding mass ratio of the nickel-based inorganic salt or the nickel-based organic salt solution to the NaOH solution is 1.5-3:1, the pH value in the reaction kettle is controlled to be 11.0-11.4, the concentration of the nitrogen-containing complexing agent in the reaction kettle is controlled to be 0.3-0.5mol/L, and the concentration of the inorganic anion crystal face growth inducer is controlled to be 0.5-1.0mol/L.
According to the invention, a nitrogen-containing complexing agent and an inorganic anion crystal face growth inducer are simultaneously adopted in the preparation and growth processes of hydroxide crystal seeds, and ammonium ions in the nitrogen-containing complexing agent and nickel, cobalt and manganese ions summarized by nickel-based inorganic salts or nickel-based organic salts are utilized to form relatively stable complexes, so that the nucleation speed of hydroxide can be slowed down, and meanwhile, the inorganic anion crystal face growth inducer is utilized to reduce the surface energy of a hydroxide (010) crystal face, increase the crystal face growth speed of a sheet hydroxide (010) and reduce the crystal face growth speed of a sheet hydroxide (003), so that the spherical-like crystal seeds which are large and loose in sheet primary particles and are favorable for growing a precursor with large (010) crystal face area are prepared; and then the seed crystal is adopted to further grow into a laminar ternary positive electrode material precursor with large primary particle (010) crystal face area and spherical secondary particles.
Compared with the prior art, the invention has the following advantages and beneficial effects:
1. compared with the method for preparing the high-nickel ternary positive electrode material precursor with larger (010) crystal face area by adopting the precursor of the lithium-rich manganese positive electrode material as the high-nickel ternary positive electrode material precursor (010) crystal face induction template, the method adopts the seed crystal with the same components as the precursor, solves the problem that the calcination temperature of the lithium-rich manganese positive electrode material is seriously mismatched with the high-nickel cobalt manganese/aluminum or nickel cobalt manganese aluminum positive electrode material, and avoids the problem that the high-nickel ternary positive electrode material circulation capacity is reduced due to the fact that the precursor of the lithium-rich manganese positive electrode material is used as the high-nickel ternary positive electrode material precursor (010) crystal face induction template.
2. Compared with the method for preparing the hydroxide precursor with large primary particle (010) crystal face area and spherical secondary particle by adopting the nitrogen-free complexing agent in the seed crystal preparation stage and the precursor growth stage, the method provided by the invention has the advantages that the nitrogen-containing complexing agent is adopted in the seed crystal preparation stage and the precursor growth stage, only the waste water containing the nitrogen-containing complexing agent is required to be treated subsequently, and compared with the waste water containing the nitrogen-free complexing agent, the treatment process is highly mature, and the treatment process cost is low.
3. Compared with the method for preparing the hydroxide precursor with large primary particle (010) crystal face area and spherical secondary particle by adopting the crystal face growth regulator containing organic molecular chains in the seed crystal preparation stage and the growth stage, the method does not need to adopt the crystal face growth regulator containing organic molecular chains with relatively high price, only needs to treat the wastewater containing the nitrogen complexing agent and the wastewater containing the inorganic anion crystal face growth inducer in the follow-up stage, does not need to treat the wastewater containing the crystal face growth regulator containing organic molecular chains in the follow-up stage, and greatly reduces the wastewater treatment process cost.
4. The ternary positive electrode material precursor prepared by the method has the advantages of good quality, large primary particle (010) crystal face area, large occupied ratio and good sphericity of secondary particles.
Drawings
FIG. 1 is a SEM image of seed crystals prepared in example 1 of the present invention.
Fig. 2 is an SEM image of the precursor prepared in example 1 of the present invention.
FIG. 3 is an SEM image of the seed crystal prepared in comparative example 1 of the present invention.
Fig. 4 is an SEM image of the precursor prepared in comparative example 1 of the present invention.
Detailed Description
The above-described matters of the present invention will be described in further detail by way of examples, but it should not be construed that the scope of the above-described subject matter of the present invention is limited to the following examples, and all techniques realized based on the above-described matters of the present invention are within the scope of the present invention.
Example 1
1) Hydroxide seed crystal preparation stage: MSO of 1.5mol/L 4 (m=ni, co, mn, where the molar ratio of Ni: co: mn is 0.83:0.07:0.1) solution, 5.0mol/L NaOH solution, 10.0mol/L ammonia solution, 5.0mol/L Na 2 SO 4 The solution is added into a reaction kettle which takes ammonia water with the concentration of 0.3mol/L and sodium sulfate with the concentration of 0.8mol/L as bottom water, wherein MSO 4 The feeding speed of the solution is 40mL/min, the feeding speed of the NaOH solution is about 24mL/min, the pH value of the coprecipitation reaction is controlled to be 11.8, the temperature of the coprecipitation reaction is controlled to be 60 ℃, the concentration of ammonia water in the coprecipitation reaction kettle is controlled to be about 0.3mol/L, and Na in the reaction kettle is controlled 2 SO 4 The concentration of the solution is 0.8mol/L, and Ni is obtained after continuous feeding and reaction for 1.5 hours 0.83 Co 0.07 Mn 0.1 (OH) 2 Seed crystals, as shown in FIG. 1, which are sphere-like and composed of flaky primary particles having a diameter of about 0.3 μm, the flaky primary particles being thicker, having a thickness of about 0.1 μm, and a spacing between the flaky primary particles of about 0.15. Mu.m.
2) And a ternary positive electrode material precursor growth stage: ni prepared in step 1) 0.83 Co 0.07 Mn 0.1 (OH) 2 Seed crystal is used as a base material, MSO with the concentration of 1.5mol/L is added 4 (m=ni, co, mn, where the molar ratio of Ni: co: mn is 0.83:0.07:0.1) solution, 5.0mol/L NaOH solution, 10.0mol/L ammonia solution, 5.0mol/L Na 2 SO 4 The solution is added into a reaction kettle which takes ammonia water with the concentration of 0.3mol/L and sodium sulfate with the concentration of 0.8mol/L as bottom water, wherein MSO 4 The feeding speed of the solution is 120mL/min, the feeding speed of the NaOH solution is about 72mL/min, the pH value of the coprecipitation reaction is controlled to be 11.0, the temperature of the coprecipitation reaction is controlled to be 60 ℃, the concentration of ammonia water in the coprecipitation reaction kettle is controlled to be about 0.3mol/L, and Na in the reaction kettle is controlled 2 SO 4 The concentration of the solution is 0.8mol/L, and Ni is obtained after continuous feeding and reaction for 80 hours 0.83 Co 0.07 Mn 0.1 (OH) 2 Washing and drying the slurry to obtain Ni with large primary particle (010) crystal face area 0.83 Co 0.07 Mn 0.1 (OH) 2 The precursor, as shown in FIG. 2, has a large (010) crystal face area due to the thick primary particle sheet.
Example 2
1) Hydroxide seed crystal preparation stage: MSO of 1.5mol/L 4 (m=ni, co, mn, where the molar ratio of Ni: co: mn is 0.75:0.10:0.15) solution, 6.0mol/L NaOH solution, 12.0mol/L ammonia solution, 7.0mol/L NaNO 3 The solution was added to a solution containing 0.2mol/L ammonia water and 0.3mol/L NaNO 3 In a reaction kettle with the solution as bottom water, MSO 4 The feeding speed of the solution is 50mL/min, the feeding speed of the NaOH solution is about 25mL/min, the pH value of the coprecipitation reaction is controlled to be 11.9, the temperature of the coprecipitation reaction is controlled to be 52 ℃, the concentration of ammonia water in the coprecipitation reaction kettle is controlled to be about 0.2mol/L, and the NaNO in the reaction kettle is controlled 3 The concentration of the solution is 0.3mol/L, and Ni is obtained after continuous feeding and reaction for 0.5 hour 0.75 Co 0.10 Mn 0.15 (OH) 2 And (5) seed crystal.
2) Precursor growth stage: ni prepared in step 1) 0.75 Co 0.10 Mn 0.15 (OH) 2 Seed crystal is used as a base material, MSO with the concentration of 1.5mol/L is added 4 (m=ni, co, mn, where the molar ratio of Ni: co: mn is 0.75:0.10:0.15) solution, 6.0mol/L NaOH solution, 12.0mol/L ammonia solution, 7.0mol/L NaNO 3 The solution was added to a solution containing 0.2mol/L ammonia water and 0.3mol/L NaNO 3 In a reaction kettle with the solution as bottom water, MSO 4 The feeding speed of the solution is 100mL/min, the feeding speed of the NaOH solution is about 50mL/min, the pH value of the coprecipitation reaction is controlled to be 10.9, the temperature of the coprecipitation reaction is controlled to be 52 ℃, the concentration of ammonia water in the coprecipitation reaction kettle is controlled to be about 0.2mol/L, and the NaNO in the reaction kettle is controlled 3 The concentration of the solution is 0.3mol/L, and Ni is obtained after continuous feeding and reaction for 65 hours 0.75 Co 0.10 Mn 0.15 (OH) 2 Washing and drying the slurry to obtain Ni with large primary particle (010) crystal face area 0.75 Co 0.10 Mn 0.15 (OH) 2 A precursor.
Example 3
1) Hydroxide seed crystal preparation stage: MSO of 2.0mol/L 4 (m= Ni, co, mn, al, wherein the molar ratio of ni:co:mn:al is 0.88:0.06:0.05:0.03), 6.0mol/L NaOH solution, 12.0mol/L ammonia solution, 6.0mol/L NaCl solution are added to a reaction vessel containing 0.3mol/L ammonia and 0.5mol/L NaCl solution as base water, wherein MSO 4 The feeding speed of the solution is 30mL/min, the feeding speed of the NaOH solution is about 20mL/min, the pH value of the coprecipitation reaction is controlled to be 12.1, the temperature of the coprecipitation reaction is controlled to be 56 ℃, the concentration of ammonia water in a coprecipitation reaction kettle is controlled to be about 0.3mol/L, the concentration of the NaCl solution in the reaction kettle is controlled to be 0.5mol/L, the continuous feeding is carried out, and Ni is obtained after the reaction is carried out for 1.0 hour 0.88 Co 0.06 Mn 0.05 Al 0.03 (OH) 2 And (5) seed crystal.
2) Precursor growth stage: ni prepared in step 1) 0.88 Co 0.06 Mn 0.05 Al 0.03 (OH) 2 Seed crystal is used as a bottom material, MSO of 2.0mol/L is added 4 (m= Ni, co, mn, al, wherein the molar ratio of ni:co:mn:al is 0.88:0.06:0.05:0.03), 6.0mol/L NaOH solution, 12.0mol/L ammonia solution, 6.0mol/L NaCl solution are added to a reaction vessel containing 0.3mol/L ammonia and 0.5mol/L NaCl solution as base water, wherein MSO 4 The feeding speed of the solution is 90mL/min, the feeding speed of the NaOH solution is about 60mL/min, the pH value of the coprecipitation reaction is controlled to be 11.2, the temperature of the coprecipitation reaction is controlled to be 56 ℃, the concentration of ammonia water in the coprecipitation reaction kettle is controlled to be about 0.3mol/L, the concentration of the NaCl solution in the reaction kettle is controlled to be 0.5mol/L, the continuous feeding is carried out, and the Ni is obtained after the reaction is carried out for 85 hours 0.88 Co 0.06 Mn 0.05 Al 0.03 (OH) 2 Washing and drying the slurry to obtain Ni with large primary particle (010) crystal face area 0.88 Co 0.06 Mn 0.05 Al 0.03 (OH) 2 A precursor.
Example 4
1) Hydroxide seed crystal preparation stage: MSO of 2.0mol/L 4 (m=ni, co, mn, whereinNi/Co/Mn molar ratio of 0.80:0.10:0.10), 6.0mol/L NaOH solution, 12.0mol/L ammonia water solution, 6.0mol/L NaNO 3 Solution, 5.0mol/L Na 2 SO 4 The solution was added to a solution containing ammonia water at a concentration of 0.3mol/L and LNaNO at a concentration of 0.2mol/L 3 Solution and 0.3mol/LNa 2 SO 4 In a reaction kettle with the solution as bottom water, MSO 4 The feeding speed of the solution is 30mL/min, the feeding speed of the NaOH solution is about 20mL/min, the pH value of the coprecipitation reaction is controlled to be 12.0, the temperature of the coprecipitation reaction is controlled to be 63 ℃, the concentration of ammonia water in the coprecipitation reaction kettle is controlled to be about 0.3mol/L, and the NaNO in the reaction kettle is controlled 3 The concentration of the solution is 0.2mol/L, na 2 SO 4 The concentration of the solution is 0.3mol/L, and Ni is obtained after continuous feeding and reaction for 0.8 hour 0.80 Co 0.10 Mn 0.10 (OH) 2 And (5) seed crystal.
2) Precursor growth stage: ni prepared in step 1) 0.80 Co 0.10 Mn 0.10 (OH) 2 Seed crystal is used as a bottom material, MSO of 2.0mol/L is added 4 (m=ni, co, mn, where the molar ratio of Ni: co: mn is 0.80:0.10:0.10), 6.0mol/L NaOH solution, 12.0mol/L ammonia solution, 6.0mol/L NaNO 3 Solution, 5.0mol/L Na 2 SO 4 The solution was added to a solution containing ammonia water at a concentration of 0.3mol/L and LNaNO at a concentration of 0.2mol/L 3 Solution and 0.3mol/LNa 2 SO 4 In a reaction kettle with the solution as bottom water, MSO 4 The feeding speed of the solution is 120mL/min, the feeding speed of the NaOH solution is about 80mL/min, the pH value of the coprecipitation reaction is controlled to be 12.0, the temperature of the coprecipitation reaction is controlled to be 63 ℃, the concentration of ammonia water in the coprecipitation reaction kettle is controlled to be about 0.3mol/L, and the NaNO in the reaction kettle is controlled 3 The concentration of the solution is 0.2mol/L, na 2 SO 4 The concentration of the solution is 0.3mol/L, and Ni is obtained after continuous feeding and reaction for 70 hours 0.80 Co 0.10 Mn 0.10 (OH) 2 Washing and drying the slurry to obtain Ni with large primary particle (010) crystal face area 0.80 Co 0.10 Mn 0.10 (OH) 2 A precursor.
Comparative example 1
1) Seeding with hydroxideThe preparation stage comprises the following steps: MSO of 1.5mol/L 4 (M=Ni, co, mn, wherein the molar ratio of Ni to Co to Mn is 0.83:0.07:0.1), 5.0mol/L NaOH solution, 10.0mol/L ammonia solution is added into a reaction kettle with 0.3mol/L ammonia water as bottom water, wherein MSO 4 The feeding speed of the solution is 40mL/min, the feeding speed of the NaOH solution is about 24mL/min, the pH value of the coprecipitation reaction is controlled to be 11.8, the temperature of the coprecipitation reaction is controlled to be 60 ℃, the concentration of ammonia water in a coprecipitation reaction kettle is controlled to be about 0.3mol/L, the feeding is continued, and the reaction is carried out for 1.5 hours, thus obtaining Ni 0.83 Co 0.07 Mn 0.1 (OH) 2 As shown in fig. 3, the seed crystal is of a spheroid shape and is composed of flaky primary particles having a diameter of about 0.3 μm, the flaky primary particles are thin and have a thickness of 0.05 μm, and the interval between the flaky primary particles is about 0.05 μm.
2) Precursor growth stage: ni prepared in step 1) 0.83 Co 0.07 Mn 0.1 (OH) 2 Seed crystal is used as a base material, MSO with the concentration of 1.5mol/L is added 4 (M=Ni, co, mn, wherein the molar ratio of Ni to Co to Mn is 0.83:0.07:0.1), 5.0mol/L NaOH solution, 10.0mol/L ammonia solution is added into a reaction kettle with 0.3mol/L ammonia water as bottom water, wherein MSO 4 The feeding speed of the solution is 120mL/min, the feeding speed of the NaOH solution is about 72mL/min, the pH value of the coprecipitation reaction is controlled to be 11.0, the temperature of the coprecipitation reaction is controlled to be 60 ℃, the concentration of ammonia water in the coprecipitation reaction kettle is controlled to be about 0.3mol/L, the continuous feeding is carried out, and Ni is obtained after the reaction for 80 hours 0.83 Co 0.07 Mn 0.1 (OH) 2 Washing and drying the slurry to obtain Ni with smaller primary particle (010) crystal face area 0.83 Co 0.07 Mn 0.1 (OH) 2 The precursor, as shown in FIG. 4, has a large (010) crystal face area due to the thick primary particle sheet.
Comparative example 1 and comparative example 1, example 1 increased SO 4 2- Inorganic anion concentration, high concentration SO 4 2- The inorganic anions can play a role of a crystal face growth inducer, reduce the surface energy of a crystal face of the hydroxide (010), and increase the crystal face of the flaky hydroxide (010)The surface growth rate decreases the crystal plane growth rate of the sheet hydroxide (003), thereby forming thick sheet-like primary particles, i.e., the (010) crystal plane area is relatively large.
While the basic principles, principal features and advantages of the present invention have been described in the foregoing examples, it will be appreciated by those skilled in the art that the present invention is not limited by the foregoing examples, but is merely illustrative of the principles of the invention, and various changes and modifications can be made without departing from the scope of the invention, which is defined by the appended claims.
Claims (3)
1. A method for regulating and controlling the crystal face area of a layered cathode material precursor (010) through anions is characterized by comprising the following specific steps:
step S1, seed crystal preparation: taking nickel-based sulfate as a raw material, and simultaneously adopting a nitrogen-containing complexing agent and an inorganic anion crystal face growth inducer to react to prepare a similar spherical hydroxide seed crystal which is favorable for growing a precursor with large (010) crystal face area and has larger and loose flaky primary particles;
the specific process is as follows: respectively adding a nickel-based sulfate solution, a NaOH solution, a nitrogen-containing complexing agent and an inorganic anion crystal face growth inducer into a reaction kettle which takes the nitrogen-containing complexing agent and the inorganic anion crystal face growth inducer as bottom water in an inert gas atmosphere, controlling the pH value in the reaction kettle to be 10.0-12.0, simultaneously controlling the concentration of the nitrogen-containing complexing agent in the reaction kettle to be 0.01-1.0mol/L and the concentration of the inorganic anion crystal face growth inducer to be 0.01-2.0mol/L, and reacting at 30-80 ℃ for 0.1-5.0 hours to obtain hydroxide seed crystals;
step S2, a precursor growth stage: taking the hydroxide seed crystal obtained in the step S1 as a base material to carry out coprecipitation reaction, taking nickel-based sulfate as a raw material, and simultaneously adopting a nitrogen-containing complexing agent and an inorganic anion crystal face growth inducer to carry out reaction to prepare a nickel-based layered cathode material precursor with large primary particle (010) crystal face area and spherical-like secondary particles;
the specific process is as follows: respectively dropwise adding a nickel-based sulfate solution, a NaOH solution, a nitrogen-containing complexing agent and an inorganic anion crystal face growth inducer into the reaction kettle of which the hydroxide seed crystal is prepared in the step S1, controlling the pH value in the reaction kettle to be 10.0-12.5, simultaneously controlling the concentration of the nitrogen-containing complexing agent in the reaction kettle to be 0.1-1.0mol/L and the concentration of the inorganic anion crystal face growth inducer to be 0.01-2.0mol/L, reacting for 40-100 hours at the temperature of 30-80 ℃ to obtain slurry, and washing and drying the slurry to obtain a nickel-based layered cathode material precursor;
the nitrogen-containing complexing agent is one or a combination of more of ammonia water, ammonium sulfite, ammonium bisulfide, ammonium bisulfate, ammonium sulfide, ammonium bisulfide and ammonium carbonate, the inorganic anion crystal face growth inducer is one or a combination of more of sodium sulfate, sodium nitrate, sodium chloride, potassium sulfate, potassium nitrate, potassium chloride, ammonium sulfate, ammonium nitrate and ammonium chloride, and the nickel base in the nickel-based sulfate is nickel cobalt manganese, nickel cobalt aluminum or nickel cobalt manganese aluminum.
2. The method for controlling the crystal face area of a layered cathode material precursor (010) through anions according to claim 1, wherein the method comprises the following steps: the molar concentration of the nickel-based sulfate solution in the step S1 is 1.0-3.0mol/L, the molar concentration of the NaOH solution is 2.0-7.0mol/L, the molar concentration of the nitrogen-containing complexing agent is 5.0-15.0mol/L, the molar concentration of the inorganic anion crystal face growth inducer is 5.0-10.0mol/L, the feeding mass ratio of the nickel-based sulfate solution to the NaOH solution is 1.5-3:1, the pH value in the reaction kettle is controlled to be 11.6-11.9, the concentration of the nitrogen-containing complexing agent in the reaction kettle is controlled to be 0.3-0.5mol/L, and the concentration of the inorganic anion crystal face growth inducer is controlled to be 0.5-1.0mol/L.
3. The method for controlling the crystal face area of a layered cathode material precursor (010) through anions according to claim 1, wherein the method comprises the following steps: the molar concentration of the nickel-based sulfate solution in the step S2 is 1.0-3.0mol/L, the molar concentration of the NaOH solution is 2.0-7.0mol/L, the molar concentration of the nitrogen-containing complexing agent is 5.0-15.0mol/L, the molar concentration of the inorganic anion crystal face growth inducer is 5.0-10.0mol/L, the feeding mass ratio of the nickel-based sulfate solution to the NaOH solution is 1.5-3:1, the pH value in the reaction kettle is controlled to be 11.0-11.4, the concentration of the nitrogen-containing complexing agent in the reaction kettle is controlled to be 0.3-0.5mol/L, and the concentration of the inorganic anion crystal face growth inducer is controlled to be 0.5-1.0mol/L.
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