CN115745022A - Preparation method of ternary material and ternary material - Google Patents
Preparation method of ternary material and ternary material Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 15
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- 159000000002 lithium salts Chemical class 0.000 claims abstract description 30
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- 239000001301 oxygen Substances 0.000 claims abstract description 26
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- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 52
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 30
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- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 10
- 150000002696 manganese Chemical class 0.000 claims description 8
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- 239000012716 precipitator Substances 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- 229910017052 cobalt Inorganic materials 0.000 claims description 5
- 239000010941 cobalt Substances 0.000 claims description 5
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 5
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 4
- 229910013716 LiNi Inorganic materials 0.000 claims description 4
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 4
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- 239000012670 alkaline solution Substances 0.000 claims description 3
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 3
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 3
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- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims 1
- DKAGJZJALZXOOV-UHFFFAOYSA-N hydrate;hydrochloride Chemical class O.Cl DKAGJZJALZXOOV-UHFFFAOYSA-N 0.000 claims 1
- FGHSTPNOXKDLKU-UHFFFAOYSA-N nitric acid;hydrate Chemical compound O.O[N+]([O-])=O FGHSTPNOXKDLKU-UHFFFAOYSA-N 0.000 claims 1
- FWFGVMYFCODZRD-UHFFFAOYSA-N oxidanium;hydrogen sulfate Chemical compound O.OS(O)(=O)=O FWFGVMYFCODZRD-UHFFFAOYSA-N 0.000 claims 1
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- HFCVPDYCRZVZDF-UHFFFAOYSA-N [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O Chemical compound [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O HFCVPDYCRZVZDF-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910015872 LiNi0.8Co0.1Mn0.1O2 Inorganic materials 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 1
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- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
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- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 1
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- RSNHXDVSISOZOB-UHFFFAOYSA-N lithium nickel Chemical compound [Li].[Ni] RSNHXDVSISOZOB-UHFFFAOYSA-N 0.000 description 1
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Images
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- 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
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- Inorganic Compounds Of Heavy Metals (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The application relates to the technical field of batteries, in particular to a ternary material and a preparation method thereof. The preparation method comprises the following steps: step S1, under protective gas atmosphere, ni is contained 2+ 、Co 2+ And Mn 2+ The mixed solution, the precipitant and the complexing agent are mixed and reacted. And S2, sequentially carrying out aging, standing, filtering, washing and drying on the reaction product obtained in the step S1 to prepare a precursor. And S3, mixing the precursor with lithium salt, placing the mixture in an oxygen-containing atmosphere for primary calcination, and cooling after the calcination is finished to prepare the pre-sintered material. And S4, placing the pre-sintered material in an oxygen-containing atmosphere for secondary calcination to prepare a ternary material containing Ni, co and Mn, wherein the temperature of the secondary calcination is higher than that of the primary calcination. Ternary material preparedHas ideal layered structure, low ion mixing degree and excellent electrochemical performance.
Description
Technical Field
The application relates to the technical field of batteries, in particular to a ternary material and a preparation method thereof.
Background
The secondary battery as a novel green power supply has the advantages of high specific energy, small self-discharge, high open circuit voltage, no memory effect, long cycle life, small environmental pollution and the like, and is widely applied to digital electronic products, pure electric and hybrid new energy vehicles and energy storage systems. Lithium ion batteries are one of the most widely commercialized secondary batteries at present. The energy density of lithium ion batteries is generally related to the specific capacity of the positive electrode material, and compared with other positive electrode materials, nickel cobalt lithium manganate (also called NCM ternary material) has higher specific capacity and lower cost, and thus has received more and more attention.
The NCM ternary material has a layered structure of transition metal ions and O 2- A main body which jointly constitutes octahedra and thus forms a layered structure, li + It occupies a vacancy between layers and thus can be reversibly deintercalated between layers. Ni in the material 2+ The nickel-based ternary material mainly plays a role in supplying capacity, so that the higher the nickel content in the ternary material is, the higher the theoretical specific capacity is. But due to Ni 2+ Radius of (2) and Li + Close together with Ni 2+ Especially when Ni is added 2+ When the total mole ratio of the transition metal ions is more than 90 percent, more and more Ni is added 2+ Will occupy Li + Position of (3), li + Into the body of the layered structure. Therefore, the complexity of the material structure is increased, and the ternary material with the same or similar proportion to the metal ions in the raw materials is difficult to obtain by regulating and controlling the proportion of the nickel ions, the cobalt ions and the manganese ions in the raw materials and the addition amount of the lithium salt. In addition, due to Li + Volatile under high temperature condition, and the Li of the NCM ternary material obtained by the traditional high-temperature solid-phase sintering method + The content is often lower than the preset content, further reducing the content of active lithium ions in the material. Therefore, in the NCM ternary material obtained by the traditional method, the actual content of metal ions (particularly lithium ions) has large deviation from the feeding ratio, and the deviation is difficult to control.
Therefore, how to prepare a ternary material having a predetermined stoichiometric ratio and an ideal layered structure is a problem to be solved.
Disclosure of Invention
Based on the method, the application provides a preparation method of the ternary material and the ternary material. The preparation method can effectively control the stoichiometric ratio of each element in the prepared ternary material, and the ternary material has an ideal layered structure and a low ion mixing degree, so that the electrochemical performance of the ternary material is improved.
In a first aspect of the present application, a method for preparing a ternary cathode material is provided, which comprises the following steps:
step S1, under protective gas atmosphere, ni is contained 2+ 、Co 2+ And Mn 2+ The mixed solution, the precipitator and the complexing agent are mixed and react;
s2, sequentially aging, standing, filtering, washing and drying the reaction product obtained in the step S1 to prepare a precursor;
s3, placing the precursor and lithium salt in an oxygen-containing atmosphere for primary calcination, and after the calcination is finished, performing cooling treatment to prepare a pre-sintered material;
and S4, placing the pre-sintered material in an oxygen-containing atmosphere for secondary calcination to prepare a ternary material containing Ni, co and Mn, wherein the temperature of the secondary calcination is higher than that of the primary calcination.
In some embodiments, the molar ratio of the precursor to the lithium element in the lithium salt is 1 (1.01-1.1). Optionally, the molar ratio of the precursor to the lithium element in the lithium salt is 1.
In some of these embodiments, the precipitant and the complexing agent are both provided in the form of an alkaline solution, optionally, the precipitant is an aqueous sodium hydroxide solution and the complexing agent is an aqueous ammonia solution.
In some of these embodiments, the mixed solution is Ni 2+ 、Co 2+ And Mn 2+ 1.5-2.5 mol/L of water solution, 0.2-0.3 mol/L of sodium hydroxide aqueous solution as precipitant and 3-5 mol/L of complexing agentAn aqueous ammonia solution. Optionally, ni in the mixed solution 2+ 、Co 2+ And Mn 2+ The molar ratio of x to y is (1-x-y), wherein x is more than or equal to 0.83 and less than 0.98, and y is more than 0 and less than 0.2.
In some of these embodiments, the Ni 2+ 、Co 2+ And Mn 2+ Provided by soluble nickel, cobalt and manganese salts, respectively, the lithium source comprising at least one of lithium hydroxide, lithium carbonate and lithium nitrate. Optionally, the soluble nickel, cobalt and manganese salts are each independently selected from at least one of the corresponding sulfate, nitrate and chloride salts.
In some embodiments, the reaction in step S1 is performed at a constant temperature of 50 to 60 ℃, a constant stirring rate of 800 to 1200rpm, a reaction time of 12 to 18 hours, and a pH of the reaction system of 10 to 12; the aging time in the step S2 is 8-12 h.
In some embodiments, the mixed solution, the precipitant, and the complexing agent are each added dropwise independently at a rate of 0.4 to 0.6mL/min.
In some embodiments, the temperature of the first calcination is 500-600 ℃, the temperature rise rate is 2.0-3.0 ℃/min, the time is 5-7 h, and the oxygen concentration in the atmosphere is 99-100%. Optionally, the temperature of the first calcination is 550 ℃, the temperature rise rate is 2.5 ℃/min, the time is 6h, and the oxygen concentration in the atmosphere is 99.9%.
In some embodiments, the temperature of the second calcination is 740 to 800 ℃, the time is 12 to 18 hours, the heating rate is 1 to 5 ℃/min, and the oxygen concentration in the atmosphere is 99 to 100 percent.
In a second aspect of the present application, there is provided a ternary material prepared according to the preparation method of any one of the first aspect, wherein the composition of the ternary material is LiNi x Co y Mn 1-x-y Wherein x is more than or equal to 0.83 and less than 0.98, and y is more than 0 and less than 0.2.
The stable layered catalyst is prepared by adopting a coprecipitation and two-step calcination method, wherein the molar ratio of elements meets a preset stoichiometric ratio and has a stable layer shapeA structural NCM ternary material. Firstly, the first calcining step is arranged, so that the precursor and the lithium salt are subjected to primary decomposition at a lower temperature, impurities are removed, the problem of rapid decomposition of the lithium salt at a high temperature is relieved, the lithium salt can slowly and uniformly enter the precursor and fully react with the precursor, and Li is reduced + And Ni 2+ The degree of mixing and arrangement of the components, and further ensures that the product has a preset stoichiometric ratio and a stable layered structure.
Furthermore, the lithium salt is slightly excessive by regulating the mixing ratio of the precursor and the lithium salt, so that Li caused by the Li during the second calcination is compensated + The content of active lithium lost by volatilization ensures the content of lithium element in the ternary material.
Furthermore, the spherical precursor with uniform appearance is prepared by regulating and controlling the coprecipitation step, so that the prepared ternary material has good appearance, the agglomeration of the ternary material is effectively prevented, and the dispersibility of the ternary material in the battery anode slurry is improved.
In addition, the first calcination of the present application removes moisture from the precursor and lithium salt, reducing moisture and CO 2 The possibility of reaction on the surface of the material is reduced, and LiOH and Li are reduced 2 CO 3 And the generation amount of residual alkali is equal, so that the ternary material prepared by the method can be directly used for manufacturing the secondary battery, the water washing step in the traditional technology is simplified, and the production efficiency of the secondary battery is improved.
Drawings
FIG. 1 is a scanning electron micrograph of a precursor prepared according to an embodiment of the present application;
FIG. 2 is a scanning electron microscope image of a ternary material prepared according to an embodiment of the present application;
FIG. 3 is an XRD spectrum of the ternary material prepared in different examples of the present application.
Detailed Description
In order to make the aforementioned objects, features and advantages of the present application more comprehensible, embodiments accompanying figures are described in detail below. In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present application. This application is capable of embodiments in many different forms than those described herein and that modifications may be made by one skilled in the art without departing from the spirit and scope of the application and it is therefore not intended to be limited to the specific embodiments disclosed below.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. The terminology used herein in the description of the present application is for the purpose of describing particular embodiments only and is not intended to be limiting of the application. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items. As used herein, "plurality" includes two and more than two items. As used herein, "above a certain number" should be understood to mean a certain number and a range greater than a certain number.
The traditional technology adopts a high-temperature solid-phase sintering method to prepare the NCM ternary material, but the method cannot be well adapted to the high-nickel NCM ternary material (generally, ni is used as the reference) 2+ Material with more than 0.8 of total molar ratio of transition metal ions) because of the aggravation of Li due to too high calcination temperature + Volatilization may reduce the content of active lithium ions, which in turn affects the rate capability of the material. However, the diffusion rate of ions in the solid phase is slow, and a calcination temperature high enough to promote the diffusion of ions is required, so that the electrochemical performance of the ternary material is also affected by lowering the calcination temperature. Further, with Ni 2+ Increased content of Li in ternary materials + And Ni 2+ The mixed-arrangement degree is obviously increased, and the mixed-arrangement effect can be aggravated under the high-temperature condition, so that the high-nickel NCM ternary material prepared by the traditional technology has poor structural stability. In addition, due to Ni 2+ And Li + Mixed row of (2) and Li + Volatilization of (2) is difficult by controlling Li in the raw material + And the addition amount of the transition metal ions to obtain the ternary material with the preset stoichiometric ratio, so that the difficulty of production and manufacturing is increased.
The high nickel ternary material in the prior mass production comprises LiNi 0.8 Co 0.1 Mn 0.1 O 2 (NCM 811), with a higher nickel contentThe ternary material is still in a research and development stage, because the specific capacity of the ternary material is improved along with the improvement of the nickel content, but the stability is reduced, so the comprehensive electrochemical performance of the high-nickel ternary material is not obviously improved. In addition, the surface of the high-nickel ternary material has more residual alkali, and the high-nickel ternary material can be used for manufacturing a battery after the residual alkali is removed by washing with water, so that the production efficiency is reduced, and the manufacturing cost is increased.
In order to overcome the above problems, an embodiment of the present application provides a method for preparing a ternary material, including the steps of:
step S1, under protective gas atmosphere, ni is contained 2+ 、Co 2+ And Mn 2+ The mixed solution, the precipitator and the complexing agent are mixed and react;
s2, sequentially carrying out aging, standing, filtering, washing and drying on the reaction product obtained in the step S1 to prepare a precursor;
s3, mixing the precursor with lithium salt, placing the mixture in an oxygen-containing atmosphere for primary calcination, and cooling after the calcination is finished to prepare a pre-sintered material;
and S4, placing the pre-sintered material in an oxygen-containing atmosphere for secondary calcination to prepare a ternary material containing Ni, co and Mn, wherein the temperature of the secondary calcination is higher than that of the primary calcination.
A spheroidal precursor was obtained by coprecipitation (corresponding in particular to step S1 and step S2), ni being incorporated in step S1 2+ 、Co 2+ And Mn 2+ The mixture is uniform, and the mixing mode can be stirring or other modes, which is not limited in the application. Due to Ni 2+ 、Co 2+ And Mn 2+ Can be completely precipitated through coprecipitation reaction, so that a precursor which is basically consistent with the proportion can be obtained by regulating and controlling the molar ratio of transition metal ions in the raw materials. Transition metal ions are separated out under the action of a precipitator to obtain precipitates with various uniform components, and the complexing agent can promote the transition metal ions to be slowly accumulated on the surfaces of the precipitates, control the growth speed and the morphology of precursor particles and further form a sphere-like precursor. Aging in step S2The formation step can promote the growth of the precipitated particles and ensure the size of the precursor particles. The coprecipitation method for preparing the precursor has the advantages of simple process, low cost, easy control of preparation conditions, uniform components in the product and the like.
In step S3, the precursor and the lithium salt are first uniformly mixed in proportion, and then placed in an oxygen atmosphere to perform a first calcination (i.e., pre-firing), at which time impurities in the raw materials are removed from the system by thermal decomposition, and the precursor and the lithium salt are decomposed into corresponding oxides and undergo a preliminary reaction. Specifically, the first calcination process includes the following three stages: the first stage (less than 250 ℃) is a decomposition stage of impurities such as moisture in the system, and the second stage (250 ℃ to 450 ℃) is a decomposition stage of precursors into transition metal oxides and lithium salts into Li 2 The stage of O, the third stage (450-600 ℃) is transition metal oxide and Li 2 And reacting O under the action of oxygen to generate a pre-sintered material. The main component of the pre-sintered material comprises nickel cobalt lithium manganate, but metal ions in the pre-sintered material are not fully diffused due to a slightly low calcination temperature, so that an ideal layered structure is not formed. In the second calcination process of step S4, after the metal ions in the pre-sintered material are heated, the metal ions move faster and migrate to corresponding positions, such as Li + Migration to interlayer vacancies of material, ni 2+ And the ions migrate to the main body of the layered structure, so that the layered ternary material with stable structure and low cation mixed-arranged degree is obtained.
The NCM ternary material with the element content meeting the preset stoichiometric ratio and a stable layered structure is prepared by adopting a coprecipitation method and a two-step calcination method. Firstly, the first calcination step is arranged, so that the precursor and the lithium salt are subjected to preliminary decomposition at a lower temperature, impurities are removed, the problem of rapid decomposition of the lithium salt at a high temperature is solved, the molten lithium salt can slowly and uniformly enter the precursor and fully react with the precursor, and Li is reduced + And Ni 2+ The degree of mixing and arrangement of the components, and further ensures that the product has a preset stoichiometric ratio and a stable layered structure. Further, the mixing ratio of the precursor and the lithium salt is regulated to ensure that lithium is containedA slight excess of salt made up for Li during calcination + The content of active lithium lost by volatilization ensures the content of lithium element in the ternary material. Furthermore, the spherical precursor with uniform appearance is prepared by regulating and controlling the coprecipitation step, so that the prepared ternary material has good appearance, the agglomeration of the ternary material is effectively prevented, and the dispersibility of the ternary material in the battery anode slurry is improved. In addition, the first calcination of the present application removes moisture from the precursor and lithium salt, reducing moisture and CO 2 The possibility of reaction on the surface of the material is reduced, and LiOH and Li are further reduced 2 CO 3 And the generation amount of residual alkali is equal, so that the ternary material prepared by the method can be directly used for manufacturing the secondary battery, the water washing step in the traditional technology is simplified, and the production efficiency of the secondary battery is improved.
In one embodiment, the molar ratio of the lithium element in the precursor to the lithium salt is 1 (1.01-1.1). Specifically, the molar ratio of the precursor to the lithium element in the lithium salt may be 1.01, 1.02, 1.03, 1.04, 1.05, 1.06, 1.07, 1.08, 1. Alternatively, the molar ratio of the precursor to the lithium element in the lithium salt is 1. When the molar ratio of the precursor to the lithium element in the lithium salt is less than 1.01, since Li + The volatilization of the lithium ion battery can cause the content of active lithium in the product to be too low, thereby reducing the specific capacity of the NCM ternary material. When the molar ratio of precursor to lithium element in lithium salt is greater than 1.1.
In one embodiment, both the precipitating agent and the complexing agent are provided in the form of alkaline solutions. Optionally, the precipitant is an aqueous sodium hydroxide solution and the complexing agent is an aqueous ammonia solution. The addition of the sodium hydroxide aqueous solution can increase the pH value of the reaction system and promote the transition metal ions to form hydroxide precursors. The ammonia water can ensure the uniform precipitation of transition metal ions, and all the components are precipitated simultaneously according to the proportion as much as possible, thereby preventing the conditions of agglomeration or uneven composition caused by local over-concentration of the reaction liquid.
In one embodimentThe mixed solution is Ni 2+ 、Co 2+ And Mn 2+ 1.5-2.5 mol/L water solution, 0.2-0.3 mol/L sodium hydroxide water solution as precipitant and 3-5 mol/L ammonia water solution as complexing agent. Specifically, the mixed solution is Ni 2+ 、Co 2+ And Mn 2+ The total concentration can be 1.5mol/L, 1.6mol/L, 1.7mol/L, 1.8mol/L, 1.9mol/L, 2.0mol/L, 2.1mol/L, 2.2mol/L, 2.3mol/L, 2.4mol/L or 2.5mol/L, the precipitant can be 0.2mol/L, 0.21mol/L, 0.22mol/L, 0.23mol/L, 0.24mol/L, 0.25mol/L, 0.26mol/L, 0.27mol/L, 0.28mol/L, 0.29mol/L or 0.3mol/L aqueous solution of sodium hydroxide, and the complexing agent can be 3mol/L, 3.2mol/L, 3.4mol/L, 3.6mol/L, 3.8mol/L, 4mol/L, 4.2mol/L, 4.4mol/L, 4.6mol/L, 4.8mol/L, 4mol/L or 5mol/L aqueous solution of ammonia. When the concentrations of the precipitant and the complexing agent are within the range, the transition metal ions in the system can be completely separated out, the precursor has a sphere-like shape, and the precursor is prevented from being obviously agglomerated.
In one embodiment, ni is mixed in the solution 2+ 、Co 2+ And Mn 2+ The molar ratio of x to y is (1-x-y), wherein x is more than or equal to 0.83 and less than 0.98, and y is more than 0 and less than 0.2. Specifically, x may be 0.83, 0.84, 0.85, 0.86, 0.87, 0.88, 0.89, 0.90, 0.91, 0.92, 0.93, 0.94, 0.945, 0.95, 0.96, 0.97 or 0.98, y may be 0.01, 0.03, 0.05, 0.07, 0.1, 0.11, 0.12, 0.13, 0.14, 0.15, 0.16, 0.17, 0.18, 0.19 or 0.195.
In one embodiment, ni 2+ 、Co 2+ And Mn 2+ Respectively provided by soluble nickel salt, cobalt salt and manganese salt. Optionally, the soluble nickel, cobalt and manganese salts are each independently selected from at least one of the corresponding sulfate, nitrate and chloride salts. Further optionally, the nickel salt is NiSO 4 ·6H 2 O, cobalt salts being CoSO 4 ·7H 2 O, manganese salt is MnSO 4 ·H 2 And O. The production cost is reduced by selecting conventional nickel salt, cobalt salt and manganese salt.
In a particular embodiment, the lithium source includes at least one of lithium hydroxide, lithium carbonate, and lithium nitrateAnd (4) seed selection. Alternatively, the lithium source is LiOH H 2 And O. The melting point of the lithium hydroxide is about 471 ℃, so that the lithium hydroxide can form a molten state in the first calcination process, and can be uniformly mixed with a precursor, the residual lithium amount on the surface of the material is reduced, and the specific capacity of the material is improved.
In one embodiment, the reaction in step S1 is carried out at a constant temperature of 50-60 ℃, a constant stirring speed of 800-1200 rpm, a reaction time of 12-18 h, and a pH value of the reaction system of 10-12. The aging time in the step S2 is 8-12 h. Specifically, the constant temperature may be 50 ℃, 51 ℃, 52 ℃, 53 ℃, 54 ℃, 55 ℃, 56 ℃, 57 ℃, 58 ℃, 59 ℃ or 60 ℃, the stirring rate may be 800rpm, 850rpm, 900rpm, 950rpm, 1000rpm, 1050rpm, 1100rpm, 1150rpm or 1200rpm, the reaction time may be 12h, 13h, 14h, 15h, 16h, 17h or 18h, and the pH of the reaction system may be 10, 10.5, 11, 11.5, 12. The aging time in step S2 may be 8h, 8.5h, 9h, 9.5h, 10h, 10.5h, 11h, 11.5h, or 12h. And (3) regulating and controlling the reaction temperature, the stirring rate and the reaction time in the step (S1), the pH value of the reaction system and the aging time in the step (S2) to obtain the spheroidal precursor with uniform size. It should be noted that, a step of adding a reaction base solution may be further included before step S1, the base solution may be deionized water, and an alkali is added to the deionized water to adjust the pH value to be between 10 and 12.
In one embodiment, the mixed solution, the precipitant and the complexing agent are respectively added dropwise at a rate of 0.4-0.6 mL/min. Specifically, the dropping rate may be 0.4mL/min, 0.42mL/min, 0.44mL/min, 0.46mL/min, 0.48mL/min, 0.5mL/min, 0.52mL/min, 0.54mL/min, 0.56mL/min, 0.58mL/min, or 0.6mL/min. It should be noted that the mixed solution, the precipitant, and the complexing agent are added dropwise to the base solution at the same time. The uniform growth of the precursor is ensured by regulating and controlling the dripping speed.
In one embodiment, the temperature of the first calcination is 500-600 ℃, the temperature rising rate is 2.0-3.0 ℃/min, the time is 5-7 h, and the oxygen concentration in the atmosphere is 99-100%. Specifically, the temperature of the first calcination may be 500 ℃, 510 ℃, 520 ℃, 530 ℃, 540 ℃, 550 ℃, 560 ℃, 570 ℃, 580 ℃, 590 ℃ or 600 ℃, the temperature increase rate may be 2.0 ℃/min, 2.1 ℃/min, 2.2 ℃/min, 2.3 ℃/min, 2.4 ℃/min, 2.5 ℃/min, 2.6 ℃/min, 2.7 ℃/min, 2.8 ℃/min, 2.9 ℃/min or 3.0 ℃/min, the time may be 5h, 5.5h, 6h, 6.5h or 7h, the oxygen concentration may be 99%, 99.1%, 99.2%, 99.3%, 99.4%, 99.5%, 99.6%, 99.7%, 99.8%, 99.9% or 100%. Alternatively, the temperature of the first calcination is 550 ℃, the heating rate is 2.5 ℃/min, the time is 6h, and the oxygen concentration in the atmosphere is 99.9%. By regulating and controlling the temperature, the heating rate, the time and the oxygen concentration of the first calcination, impurities in the raw materials can be effectively removed, the decomposition of a precursor and lithium salt is promoted, the generated transition metal oxide and the molten lithium salt can fully react, and the pre-sintered material according with the preset stoichiometric ratio is obtained. In addition, because the moisture in the system is removed by the first calcination, the residual alkali quantity on the surface of the material is reduced, the subsequent washing step is simplified, and the production efficiency is improved.
In one embodiment, the temperature of the second calcination is 740 to 800 ℃, the time is 12 to 18 hours, the heating rate is 1 to 5 ℃/min, and the oxygen concentration in the atmosphere is 99 to 100 percent. Specifically, the temperature of the second calcination may be 740 ℃, 750 ℃, 760 ℃, 770 ℃, 780 ℃, 790 ℃ or 800 ℃, the time may be 12h, 13h, 14h, 15h, 16h, 17h or 18h, the temperature increase rate may be 1 ℃/min, 2 ℃/min, 3 ℃/min, 4 ℃/min or 5 ℃/min, and the oxygen concentration may be 99%, 99.1%, 99.2%, 99.3%, 99.4%, 99.5%, 99.6%, 99.7%, 99.8%, 99.9% or 100%. By regulating and controlling the temperature, the heating rate, the time and the oxygen concentration of the second calcination, metal ions in the pre-sintered material can be fully diffused, and the ternary material with an ideal layered structure is obtained. And because the temperature of the second calcination is lower than the calcination temperature of the traditional high-temperature curing method, the lithium-nickel mixed-arrangement degree in the ternary material is reduced, and the structural stability of the material is improved.
Further, an embodiment of the present application provides a method according toThe ternary material prepared by the preparation method of claim, wherein the ternary material consists of LiNi x Co y Mn 1-x-y Wherein x is more than or equal to 0.83 and less than 0.98, and y is more than 0 and less than 0.2.
In order that the present application may be more readily understood and readily carried into effect, the following more specific and detailed examples and comparative examples are provided below by reference. The examples of the present application and their advantages will also be apparent from the description of specific examples and comparative examples below, and the performance results.
The raw materials used in the following test examples are all commercially available without specific reference.
Example 1
(1) Preparation of the precursor
Dissolving sulfates of Ni, co and Mn in a certain volume of distilled water according to a mol ratio of 0.95; preparing 4mol/L sodium hydroxide solution as a precipitator; preparing ammonia water with a certain molar concentration as a complexing agent, and carrying out a coprecipitation experiment in a constant-temperature water bath at 50-60 ℃. Adding a small amount of base solution into a four-mouth flask, adding a proper amount of ammonia water, stirring, keeping the pH value of the base solution between 10 and 12, adding nitrogen into the base solution, and exhausting air in the four-mouth flask. And respectively dripping a transition metal salt solution, a sodium hydroxide solution and ammonia water into the four-mouth bottle at a certain feeding speed by a peristaltic pump, and strongly stirring at a certain speed in the whole reaction process. And after the dropwise addition of the solution is finished, keeping the four bottles sealed, and continuously stirring at a certain speed to ensure that the reaction is complete and the particles grow up. And standing after the completion. After the dripping is finished, continuously keeping the constant stirring speed for continuously stirring, wherein the total reaction time is 12-18 h, aging after the reaction is finished, standing for 24h, filtering, washing and drying to obtain a precursor Ni 0.95 Co 0.03 Mn 0.02 (OH) 2 。
(2) Preparation of the presintered Material
Mixing the precursor prepared in the step (1) with LiOH & H 2 Mixing O according to the mass ratio of 1:1.05, and carrying out primary calcination at 550 ℃, wherein the heating rate is 2.5 ℃/min, the calcination time is 6h, and the oxygen concentration in the calcination atmosphere is 99.9%. The first calcination is completedAnd then, cooling the sample to room temperature to obtain a pre-sintered material.
(3) Preparation of ternary materials
And (3) carrying out secondary calcination on the pre-sintered material prepared in the step (2) at 740 ℃, wherein the heating rate is 2.5 ℃/min, the calcination time is 12h, and the oxygen concentration in the calcination atmosphere is 99.9%. And after the second calcination is completed, cooling the sample to room temperature and carrying out post-treatment to obtain the ternary material.
Example 2
Essentially the same as in example 1, except that: the temperature of the second calcination in (3) was 760 ℃.
Example 3
Essentially the same as in example 1, except that: the temperature of the second calcination in (3) was 780 ℃.
Example 4
Essentially the same as in example 1, except that: the temperature of the second calcination in (3) was 800 ℃.
Comparative example 1
The ternary material is prepared by a traditional method, the specific steps are basically the same as those of the embodiment 1, and the differences are as follows: directly reacting the precursor obtained in the step (1) with LiOH & H 2 Mixing O according to the mass ratio of 1, and then directly calcining at 740 ℃ for 15h, wherein the oxygen concentration in the calcining atmosphere is 99%. And cooling the sample to room temperature and carrying out post-treatment to obtain the ternary material.
Comparative example 2
Essentially the same as in example 1, except that: reacting the precursor obtained in the step (1) with LiOH & H 2 Mixing O according to the mass ratio of 1.05, and then directly calcining according to the step (3).
Comparative example 3
Essentially the same as in example 1, except that: (2) The intermediate precursor reacts with LiOH. H 2 The mass ratio of O is 1.
Performance testing
(1) XRD test
XRD tests were carried out on examples 1 to 4 and comparative examples 1 to 3 using (Bruker axs D8-Focus), FIG. 1 being XRD spectra of examples 1 to 4, as can be seen from FIG. 1, each of which was carried outExamples are hexagonal layered structures and have good crystallinity. As shown in Table 1, the intensity ratio of the (003) diffraction peak to the (104) diffraction peak of each sample is generally considered to be Li when the ratio of I (003)/I (104) is large + And Ni 2+ The lower the degree of drainage.
(2) Element content test
The actual molar contents of the metal elements in examples 1 to 4 and comparative examples 1 to 3 were measured by ICP, and the results are shown in table 1.
Test examples
Button cells were prepared using the ternary materials as in examples 1-4 and comparative examples 1-3. Specifically, the ternary material, acetylene black (conductive agent), and polyvinylidene fluoride (binder) are added to a solvent N-methylpyrrolidone in a molar mass ratio of 95. And coating the slurry on an aluminum foil, and drying in a vacuum drying oven at 80 ℃ for 20 hours to obtain the positive plate. And then cutting the positive plate into positive plates with the diameter of 12mm, assembling the positive plates, the isolating membrane and the negative lithium plate into a button cell in a glove box, and injecting 1mol/L electrolyte (the composition is EC and DEC mixed solution with the mass ratio of 1. And (3) after standing for 12h, carrying out first charge and discharge and cycle performance test on the button cell by using a blue test system, wherein the specific test conditions are as follows.
(3) First charge and discharge test
The charge and discharge test is carried out at room temperature, the voltage range is 2.8-4.3V, and the current density is 0.33C.
(4) Cycle performance test
The button cell was charged to 4.3V at a constant current at a current density of 0.5C and then discharged to 2.5V for one cycle, and the capacity of the cell was tested after 50 cycles.
TABLE 1
As shown in Table 1, examples 1 to 4 all had higher I (003)/I (104) than comparative example, indicating that Li of each example + And Ni 2 + The degree of drainage is lower than in the comparative example. As can be seen from the battery performance test data, the specific capacity and capacity retention rate of each example are higher than those of the comparative example. In example 3, I (003)/I (104) is largest, and its layered structure Li + And Ni 2+ The mixing degree is lowest, the first discharge specific capacity is highest, and the capacity retention rate after 50 cycles is highest. In addition, the measured element content of the ternary material obtained in each example is basically consistent with the molar ratio of the raw materials, that is, the chemical composition of the ternary material obtained in each example is basically consistent with LiNi 0.95 Co 0.03 Mn 0.02 O 2 。
As is clear from comparison of comparative example 2 and example 1, the present application obtained a large I (003)/I (104) and a large Li by the first calcination step + And Ni 2+ The ternary material with low mixed-arrangement degree further improves the specific capacity and capacity retention rate of the material. As can be seen from comparison between comparative example 3 and example 1, the ternary material with higher active lithium content is obtained by adjusting the molar ratio of the precursor to the lithium salt, and the specific capacity of the ternary material is further improved. In addition, comparative example 1 is a ternary material obtained by a conventional method, and Li thereof is known from the test results + And Ni 2+ The mixed drainage degree is highest, and the specific capacity and the capacity retention rate are poor.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several implementation modes of the present application, and the description thereof is specific and detailed, but not construed as limiting the scope of the claims. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the concept of the present application, and these are all within the scope of protection of the present application. Therefore, the protection scope of the patent is subject to the appended claims, and the description and the drawings can be used for explaining the contents of the claims.
Claims (10)
1. The preparation method of the ternary material is characterized by comprising the following steps of:
step S1, under protective gas atmosphere, ni is contained 2+ 、Co 2+ And Mn 2+ The mixed solution, the precipitator and the complexing agent are mixed and react;
s2, sequentially aging, standing, filtering, washing and drying the reaction product obtained in the step S1 to prepare a precursor;
s3, mixing the precursor with lithium salt, placing the mixture in an oxygen-containing atmosphere for primary calcination, and cooling after the calcination is finished to prepare a pre-sintered material;
and S4, placing the pre-sintered material in an oxygen-containing atmosphere for secondary calcination to prepare a ternary material containing Ni, co and Mn, wherein the temperature of the secondary calcination is higher than that of the primary calcination.
2. The method for preparing the ternary material according to claim 1, wherein the molar ratio of the precursor to the lithium element in the lithium source is 1 (1.01-1.1);
optionally, a molar ratio of the precursor to lithium element in the lithium salt is 1.
3. The method for preparing a ternary material according to claim 1 or 2, wherein said precipitating agent and said complexing agent are both provided in the form of alkaline solutions;
optionally, the precipitant is an aqueous sodium hydroxide solution, and the complexing agent is an aqueous ammonia solution.
4. The method for preparing a ternary material according to claim 3, wherein said mixed solution is Ni 2+ 、Co 2+ And Mn 2+ The total concentration of the water solution is 1.5-2.5 mol/L, the precipitator is 0.2-0.3 mol/L sodium hydroxide water solution, and the complexing agent is 3-5 mol/L ammonia water solution;
optionally, ni in the mixed solution 2+ 、Co 2+ And Mn 2+ The molar ratio of x to y is (1-x-y), wherein x is more than or equal to 0.83 and less than 0.98, and y is more than 0 and less than 0.2.
5. Method for the preparation of a ternary material according to claim 1 or 2, characterised in that said Ni is 2+ 、Co 2+ And Mn 2+ Provided by soluble nickel, cobalt and manganese salts, respectively, the lithium source comprising at least one of lithium hydroxide, lithium carbonate and lithium nitrate;
optionally, the soluble nickel, cobalt and manganese salts are each independently selected from at least one of the corresponding sulfate, sulfate hydrate, nitrate hydrate, chloride and chloride hydrates.
6. The method for preparing the ternary material according to claim 1 or 2, wherein the reaction in step S1 is carried out at a constant temperature of 50 to 60 ℃, a constant stirring rate of 800 to 1200rpm, a reaction time of 12 to 18 hours, and a pH of a reaction system of 10 to 12;
the aging time in the step S2 is 8-12 h.
7. The method for preparing the ternary material according to claim 3, wherein the mixed solution, the precipitant and the complexing agent are each independently added dropwise at a rate of 0.4 to 0.6mL/min.
8. The method for preparing the ternary material according to claim 1 or 2, wherein the temperature of the first calcination is 500-600 ℃, the temperature rise rate is 2.0-3.0 ℃/min, the time is 5-7 h, and the oxygen concentration in the atmosphere is 99-100%;
optionally, the temperature of the first calcination is 550 ℃, the temperature rising rate is 2.5min, the time is 6h, and the oxygen concentration in the atmosphere is 99.9%.
9. The method for preparing the ternary material according to claim 1 or 2, wherein the temperature of the second calcination is 740 to 800 ℃, the time is 12 to 18 hours, the temperature rise rate is 1 to 5 ℃/min, and the oxygen concentration in the atmosphere is 99 to 100%.
10. A ternary material prepared according to the method of any one of claims 1 to 9, wherein the ternary material consists of LiNi x Co y Mn 1-x-y Wherein x is more than or equal to 0.83 and less than 0.98, and y is more than 0 and less than 0.2.
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| CN110330060A (en) * | 2019-07-31 | 2019-10-15 | 海南大学 | A kind of preparation method of radial structure spherical shape NCM811 type tertiary cathode material |
| CN112142125A (en) * | 2020-09-29 | 2020-12-29 | 山东精工电子科技有限公司 | Method for preparing high-nickel ternary cathode material by secondary growth method |
| WO2022227903A1 (en) * | 2021-04-30 | 2022-11-03 | 天津国安盟固利新材料科技股份有限公司 | High-nickel precursor and preparation method therefor, and high-nickel positive electrode material and preparation method therefor |
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