CN115991506A - Positive electrode precursor for sodium ion battery, and preparation method and application thereof - Google Patents
Positive electrode precursor for sodium ion battery, and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to the technical field of sodium ion batteries, in particular to a positive electrode precursor for a sodium ion battery, and a preparation method and application thereof. The positive electrode precursor for the sodium ion battery is provided with a core-shell structure, wherein the inner core of the core-shell structure is a nickel-cobalt-manganese ternary precursor, and the outer shell of the core-shell structure is a nickel-iron-manganese ternary precursor; specific surface area of the positive electrode precursor for sodium ion battery>9m 2 /g; tap density of positive electrode precursor for sodium ion battery>1.5g/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the Complexing agent package used in process of forming nickel-iron-manganese ternary precursorComprises at least one of monoethanolamine, diethanolamine, triethanolamine, trisodium nitrilotriacetate, ethylenediamine tetraacetate, diethylenetriamine pentaacetic acid and salts thereof. The positive electrode precursor for the sodium ion battery has the advantages of uniform element distribution, no segregation, uniform particle size distribution, good sphericity, clear primary particle morphology, high tap density, good electrochemical stability and cycle performance and the like.
Description
Technical Field
The invention relates to the technical field of sodium ion batteries, in particular to a positive electrode precursor for a sodium ion battery, and a preparation method and application thereof.
Background
In recent decades, sodium ion batteries have received a great deal of attention from academic and commercial enterprises, and more than 20 companies are engaged in sodium ion battery research worldwide, and enterprises in China such as Zhongke sodium sea are in the leading position in the process of sodium ion battery industrialization. At present, sodium ion battery industrialization is still in the primary stage, but sodium ion batteries have the potential for rapid industrialization improvement.
The positive electrode material requires the use of an active material of sodium ions, and the main stream of positive electrode materials for sodium ion batteries comprises: transition metal oxides, polyanion compounds, prussian blue compounds, liquid sodium, and the like. The materials are required to have good electrochemical property, safety, chemical stability and thermal stability, so that the materials have higher theoretical specific capacity and battery cycle life.
Transition metal oxides are currently the most popular cathode materials, such as sodium iron phosphate, sodium iron manganate, sodium titanium manganate, etc., which theoretically have higher specific discharge capacities but poor cycle performance. However, the disadvantages of the lithium ion battery can be improved by introducing active or inert elements for doping or substitution, and the elements such as copper, iron and the like which cannot be used by the positive electrode material in the lithium ion battery have good performance in the sodium ion battery. At present, the transition metal oxide system has the best performance, and the copper-based oxide battery used by the sodium in the Zhongkehai has the excellent performance, and the energy density reaches 145Wh/kg; the mass energy density of the nickel layered oxide battery of FARADION company in the United kingdom reaches 150 Wh/kg-160 Wh/kg, which is far superior to other sodium ion battery systems.
The coprecipitation method has the advantages of uniform product, easy shape regulation, low cost, low energy consumption and the like, for example, the ternary material nickel cobalt manganese for lithium ion batteries is mainly produced by adopting the ammonia water as a complexing agent to control the crystallization coprecipitation method under the protection atmosphere at present, so as to obtain the hydroxide precursor of nickel cobalt manganese. However, no iron element is involved in the ternary material nickel cobalt manganese for lithium ion batteries. Fe (OH) at normal temperature 2 K of (2) sp 8.0X10 -16 (much lower than Ni (OH) 2 And Mn (OH) 2 ) The pH of the precipitate is low, the precipitate is easy to be earlier than other metals (Ni, mn), and Fe is in alkaline environment condition 2+ 、Fe 3+ The catalyst is not complexed with ammonia water, can not carry out coprecipitation with Ni and Mn, can only generate hydroxide precipitation, and causes uneven distribution of coprecipitated materials (uneven distribution of Fe element) to directly influence electrochemical performance. Meanwhile, fe 2+ Is easily oxidized into Fe in the coprecipitation reaction process 3+ ，Fe(OH) 3 K of (2) sp 4.0X10 -38 Is easier to be connected with OH - And combining precipitation to form new crystal nucleus, triggering segregation, affecting the uniform distribution of Fe element and causing uneven particle size distribution. In addition, since Ni-Fe-Mn is not uniformly co-precipitated, the sphericity of the precursor particles is poor, amorphous shape is easy to be formed, the tap density of the precursor is low, hardening is easy to occur during drying, and sieving is difficult.
Therefore, there is a need for optimization and improvement in the current coprecipitation preparation process scheme of Ni-Fe-Mn hydroxide precursor.
In view of this, the present invention has been made.
Disclosure of Invention
The first aim of the invention is to provide a positive electrode precursor for a sodium ion battery, which takes a nickel-cobalt-manganese ternary precursor with high sphericity as an inner core, and adopts a complexing agent which can complex nickel ions, ferrous ions and manganese ions of specific types in the process of forming a nickel-iron-manganese ternary precursor shell, thereby relieving the difference of precipitation speeds in various metal ion reaction systems and realizing uniform coprecipitation; since the growth of the precursor is inherited, the nickel ions, ferrous ions and manganese ions will continue to grow to the target particle size at the growth sites attached to the core. Therefore, the positive electrode precursor element for the sodium ion battery provided by the invention has the advantages of uniform distribution, no segregation, uniform particle size distribution, good sphericity and high tap density.
The second object of the invention is to provide a preparation method of the positive electrode precursor for the sodium ion battery, which comprises the steps of preparing the nickel-cobalt-manganese ternary precursor inner core, coating the nickel-iron-manganese ternary precursor outer shell on the surface of the nickel-cobalt-manganese ternary precursor inner core, and adopting a specific type of complexing agent, so that the sphericity of the positive electrode precursor for the sodium ion battery can be effectively improved, the appearance can be improved, the tap can be improved, and the elements are uniformly distributed and are not segregated.
A third object of the present invention is to provide a positive electrode sheet.
A fourth object of the present invention is to provide a sodium ion battery.
In order to achieve the above object of the present invention, the following technical solutions are specifically adopted:
in a first aspect, the invention provides a positive electrode precursor for a sodium ion battery, which is provided with a core-shell structure, wherein the inner core of the core-shell structure is a nickel-cobalt-manganese ternary precursor, and the outer shell of the core-shell structure is a nickel-iron-manganese ternary precursor.
The primary particles of the inner core and the outer shell in the core-shell structure are layered, and the secondary particles are spherical.
Wherein the chemical formula of the nickel-cobalt-manganese ternary precursor is Ni x Co y Mn z (OH) 2 Wherein 0 is<x<1，0<y<1，0<z<1，And x+y+z=1.
The proportion of the nickel element, the cobalt element and the manganese element in the nickel-cobalt-manganese ternary precursor can be any conventional proportion. x includes, but is not limited to, a point value of any one of 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9 or a range value between any two; y includes, but is not limited to, a point value of any one of 0.01, 0.05, 0.1, 0.2, 0.3 or a range value therebetween; z includes, but is not limited to, a point value of any one of 0.01, 0.05, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9 or a range value therebetween.
The chemical formula of the nickel-iron-manganese ternary precursor is Ni a Fe b Mn c (OH) 2 Wherein 0 is<a<1，0<b<1，0<c<1, and a+b+c=1.
The proportion of the nickel element, the iron element and the manganese element in the nickel-iron-manganese ternary precursor can be any conventional proportion. a includes, but is not limited to, a point value of any one of 0.1, 0.2, 0.3, 0.4, 0.5 or a range value between any two; b includes, but is not limited to, a point value of any one of 0.1, 0.2, 0.3, 0.4, 0.5 or a range value between any two; c includes, but is not limited to, a point value of any one of 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9 or a range value between any two.
Specific surface area of the positive electrode precursor for sodium ion battery>9m 2 /g; including but not limited to 9.1m 2 /g、9.2m 2 /g、9.3m 2 /g、9.5m 2 /g、9.8m 2 /g、10m 2 /g、10.5m 2 /g、11m 2 /g、11.5m 2 /g、12m 2 /g、12.5m 2 /g、13m 2 /g、13.5m 2 /g、14m 2 /g、15m 2 A point value of any one of/g or a range value between any two.
The specific surface area of the precursor influences the sintering activity of the rear end material, and further influences the capacity exertion of the positive electrode material.
Tap density of positive electrode precursor for sodium ion battery>1.5g/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the Including but not limited to 1.53g/cm 3 、1.55g/cm 3 、1.60g/cm 3 、1.65g/cm 3 、1.70g/cm 3 、1.75g/cm 3 、1.80g/cm 3 、1.90g/cm 3 Any one of the point values or a range value between any two.
The positive electrode precursor for the sodium ion battery, which is prepared by the invention, has high tap density, can avoid hardening in the drying process and is difficult to screen.
And, tap density is critical to increasing capacity. The greater the tap density of the material, the more material the battery contains at the same volume, and the greater the specific energy.
The complexing agent used in the process of forming the ferronickel manganese ternary precursor comprises at least one of monoethanolamine, diethanolamine, triethanolamine, trisodium nitrilotriacetate, ethylenediamine tetraacetate and diethylenetriamine pentaacetic acid and salt compounds thereof.
In some embodiments of the invention, the nickel iron manganese ternary precursor is formed using a co-precipitation process.
Wherein monoethanolamine is 2-hydroxyethylamine, and the chemical formula of the monoethanolamine is C 2 H 7 NO。
Diethanolamine (DEA), also known as 2,2' -dihydroxydiethylamine, of the formula C 4 H 11 NO 2 。
Triethanolamine, i.e., tris (2-hydroxyethyl) amine, can be regarded as a trihydroxy substituent of triethylamine and has the formula C 6 H 15 NO 3 。
Wherein the chemical formula of the trisodium nitrilotriacetate is C 6 H 8 NNa 3 O 7 。
In some embodiments of the invention, the edetate comprises disodium edetate and/or tetrasodium edetate.
In some embodiments of the present invention, the diethylenetriamine pentaacetic acid and its salt compounds include diethylenetriamine pentaacetic acid (DTPA, having the chemical formula C 14 H 23 N 3 O 10 ) And/or diethylenetriamine pentaPentasodium acetate (DTPA-5 Na, its chemical formula is C 14 H 18 N 3 Na 5 O 10 )。
The morphology of the primary particles of the nickel-cobalt-manganese ternary precursor is flaky, and the shape of the secondary particles is spherical (the primary particles are aggregated to form the secondary particles).
The morphology of the primary particles of the ferronickel manganese ternary precursor is flaky, and the shape of the secondary particles is spherical (the primary particles are aggregated to form the secondary particles).
The invention provides a positive electrode precursor for a sodium ion battery, and aims to solve the problems of uneven element distribution, poor sphericity, poor morphology, low tap density, low positive electrode material capacity, poor cycle performance and the like of a Ni-Fe-Mn layered hydroxide precursor in the prior art.
Fig. 1 is a schematic cross-sectional structure of a positive electrode precursor for a sodium ion battery according to the present invention. The positive electrode precursor for the sodium ion battery has a core-shell structure, and referring to fig. 1, the nickel-cobalt-manganese ternary precursor with high sphericity is taken as an inner core (called NCM precursor inner core for short), the nickel-iron-manganese ternary precursor is coated on the outer surface of the inner core to form an outer shell (called NFM precursor outer shell for short), and complexing agents which can complex nickel ions, ferrous ions and manganese ions of specific types are added in the forming process of the outer shell NFM, so that the difference of precipitation speeds of metal ions in a reaction system can be relieved, uniform coprecipitation is realized, element distribution is uniform and non-segregation is realized, and uneven particle size distribution caused by new cores is avoided. Meanwhile, as the growth of the precursor has inheritance, the nickel ions, the ferrous ions and the manganese ions can be continuously attached to the growth sites on the inner core to continuously grow to the target granularity, so that the sphericity of the positive electrode precursor for the sodium ion battery is effectively improved, the morphology of the positive electrode precursor is improved, and the compaction is improved.
Therefore, the positive electrode precursor for the sodium ion battery has the advantages of uniform element distribution, no segregation, uniform particle size distribution, good sphericity, clear primary particle morphology, high tap density, good electrochemical stability and cycle performance and the like, and can prolong the service life of the sodium ion battery. Is suitable for mass production and application.
Preferably, the D50 particle size of the inner core is 1-5 μm; including but not limited to a dot value of any one of 2 μm, 3 μm, 4 μm, or a range value between any two.
Preferably, the D50 particle size of the positive electrode precursor for sodium ion battery is 4-15 μm, including but not limited to a dot value of any one of 5 μm, 6 μm, 7 μm, 8 μm, 9 μm, 10 μm, 11 μm, 12 μm, 13 μm, 14 μm or a range value between any two.
In some embodiments of the invention, the chemical formula Ni x Co y Mn z (OH) 2 Wherein x is more than or equal to 0.1 and less than or equal to 0.98,0.01, y is more than or equal to 0.2, and z is more than or equal to 0.01 and less than or equal to 0.9.
In some embodiments of the invention, the chemical formula Ni a Fe b Mn c (OH) 2 Wherein a is more than or equal to 0.1 and less than or equal to 0.4, b is more than or equal to 0.1 and less than or equal to 0.4,0.2, and c is more than or equal to 0.8.
In a second aspect, the invention provides a method for preparing the positive electrode precursor for the sodium ion battery, which comprises the following steps:
and adding the nickel-cobalt-manganese ternary mixed salt solution, the precipitator solution and the first complexing agent solution into the first base solution to perform a first coprecipitation reaction to form a nickel-cobalt-manganese ternary precursor kernel, thereby obtaining the nickel-cobalt-manganese ternary precursor crystal nucleus slurry.
Wherein the first complexing agent solution comprises at least one of ammonia water (ammonia water solution), an ammonium sulfate solution, an ammonium chloride solution, and an ammonium nitrate solution.
Uniformly mixing the nickel-cobalt-manganese ternary precursor crystal nucleus slurry with the precipitator solution and the second complexing agent solution to obtain a second base solution, adding the nickel-iron-manganese ternary mixed salt solution, the precipitator solution and the second complexing agent solution into the second base solution, performing a second coprecipitation reaction to form a nickel-iron-manganese ternary precursor shell, enabling the nickel-iron-manganese ternary precursor shell to be coated on the outer surface of the nickel-cobalt-manganese ternary precursor inner core, and after the second coprecipitation reaction is completed, sequentially performing solid-liquid separation, screening and demagnetizing to obtain the positive electrode precursor for the sodium ion battery.
The second complexing agent solution comprises at least one of monoethanolamine solution, diethanolamine solution, triethanolamine solution, trisodium nitrilotriacetate solution, ethylenediamine tetraacetate solution, diethylenetriamine pentaacetic acid solution and salt solution thereof.
According to the preparation method, the nickel-cobalt-manganese ternary precursor inner core with high sphericity is prepared, the nickel-iron-manganese ternary precursor outer shell is coated on the outer surface of the nickel-cobalt-manganese ternary precursor inner core, and the specific type of second complexing agent is adopted in the process of forming the nickel-iron-manganese ternary precursor outer shell, so that sphericity of the positive electrode precursor for the sodium ion battery can be effectively improved, morphology is improved, tap density is improved, elements are uniformly distributed, segregation is avoided, and particle size distribution is uniform.
In some embodiments of the invention, the D50 particle size of the nuclei (solid particles) in the nickel cobalt manganese ternary precursor nuclei slurry is 1-5 μm. That is, the first coprecipitation reaction may react to a D50 particle diameter of a crystal nucleus (solid particle) in the nickel cobalt manganese ternary precursor crystal nucleus slurry of 1 to 5 μm.
It will be appreciated that the end of the reaction may also be determined based on the reaction time of the first coprecipitation reaction.
Preferably, the molar concentration of the first complexing agent solution is 4-10 mol/L; including but not limited to a point value of any one of 5mol/L, 6mol/L, 7mol/L, 8mol/L, 9mol/L, or a range value between any two.
Preferably, the total molar concentration of metal ions in the nickel-cobalt-manganese ternary mixed salt solution is 1-2.5 mol/L; including but not limited to a dot value of any one of 1.3mol/L, 1.5mol/L, 1.8mol/L, 2.0mol/L, 2.3mol/L, or a range value between any two.
Preferably, the molar concentration of the second complexing agent solution is 1-10 mol/L; including but not limited to a dot value of any one of 2mol/L, 3mol/L, 4mol/L, 5mol/L, 6mol/L, 7mol/L, 8mol/L, 9mol/L, or a range value between any two.
Preferably, the total molar concentration of metal ions in the ferronickel manganese ternary mixed salt solution is 1-3 mol/L, including but not limited to a point value of any one of 1.2mol/L, 1.5mol/L, 1.8mol/L, 2.0mol/L, 2.3mol/L, 2.5mol/L, 2.8mol/L or a range value between any two.
In some specific embodiments of the present invention, the molar ratio of the nickel element, the cobalt element and the manganese element in the nickel-cobalt-manganese ternary mixed salt solution is 10 to 98 (including but not limited to a point value of any one of 20, 30, 40, 50, 60, 70, 80, 90 or a range value between any two): 1-20 (including but not limited to a point value of any one of 3, 5, 8, 10, 12, 15, 18 or a range value between any two): 1-90 (including but not limited to a point value of any one of 5, 10, 20, 30, 40, 50, 60, 70, 80 or a range value therebetween).
In some specific embodiments of the present invention, the molar ratio of the nickel element, the iron element and the manganese element in the ferronickel manganese ternary mixed salt solution is 10 to 40 (including but not limited to a point value of any one of 15, 20, 25, 30, 35 or a range value between any two): 10-40 (including but not limited to a point value of any one of 15, 20, 25, 30, 35 or a range value between any two): 20-80 (including but not limited to a point value of any one of 30, 40, 50, 60, 70 or a range value between any two). Wherein, the iron element exists mainly in the form of ferrous ions. That is, the iron source used to prepare the ferronickel manganese ternary mixed salt solution is a ferrous salt such as ferrous sulfate, ferrous nitrate, ferrous chloride, etc., but is not limited thereto.
Preferably, the precipitant solution comprises sodium hydroxide solution and/or potassium hydroxide solution.
Preferably, the molar concentration of the precipitant solution used in the course of the first coprecipitation reaction is 7-12 mol/L; including but not limited to a point value of any one of 8mol/L, 9mol/L, 10mol/L, 11mol/L, or a range value between any two.
Preferably, the molar concentration of the precipitant solution used during the second coprecipitation reaction is 2 to 8mol/L, including but not limited to a point value of any one of 2.5mol/L, 3mol/L, 3.5mol/L, 4mol/L, 4.5mol/L, 5mol/L, 6mol/L, 7mol/L, or a range value between any two.
Preferably, the pH of the first base fluid is 10.8 to 12.5, including but not limited to a point value of any one of 11.0, 11.3, 11.5, 12, 12.3 or a range of values between any two.
The mass concentration of ammonium ions in the first base solution is 1-5 g/L; including but not limited to a dot value of any one of 2g/L, 2.5g/L, 3g/L, 3.5g/L, 4g/L, 4.5g/L, or a range value between any two.
In some embodiments of the invention, the first base fluid is made up primarily of a first complexing agent solution, a precipitant solution, and water.
Preferably, the pH of the second base fluid is 9.5 to 11, including but not limited to a point value of any one of 9.8, 10.0, 10.3, 10.5, 10.8 or a range value between any two.
The molar concentration of the second complexing agent in the second base fluid is 0.1-1 mol/L, including but not limited to a point value of any one of 0.3mol/L, 0.5mol/L, 0.8mol/L or a range value between any two.
In some specific embodiments of the present invention, water is further added during the process of uniformly mixing the nickel-cobalt-manganese ternary precursor crystal nucleus slurry with the precipitant solution, the second complexing agent solution and water.
Preferably, during the first coprecipitation reaction, the temperature of the mixture is 35 to 60 ℃, including but not limited to any one of the point values of 40 ℃, 45 ℃, 50 ℃, 55 ℃, 58 ℃ or a range of values between any two.
In some embodiments of the invention, the temperature of the first base fluid is between 35 and 60 ℃, including, but not limited to, any one of a point value or a range value between any two of 40 ℃, 45 ℃, 50 ℃, 55 ℃, 58 ℃.
In the process of the first coprecipitation reaction, the pH value of the mixed material is 10.5-12.5; including but not limited to a point value of any one of 11.0, 11.3, 11.5, 11.8, 12.0, 12.3 or a range value between any two.
Preferably, during the first coprecipitation reaction, the mass concentration of ammonium ions in the mixture is 1 to 5g/L, including but not limited to a point value of any one of 2g/L, 2.5g/L, 3g/L, 3.5g/L, 4g/L, 4.5g/L, or a range value between any two.
Preferably, the time of the first coprecipitation reaction is 5 to 60 hours, including but not limited to a point value of any one of 10 hours, 20 hours, 30 hours, 40 hours, 50 hours or a range value between any two.
In some embodiments of the invention, the mixture is stirred during the first coprecipitation reaction at a speed of 150 to 350 r/min. Wherein the rotational speed includes, but is not limited to, a point value of any one of 200r/min, 250r/min, 300r/min, or a range value therebetween.
Preferably, during the second coprecipitation reaction, the temperature of the mixture is 40 to 50 ℃, including but not limited to any one of the point values or range values between any two of 42 ℃, 45 ℃, 48 ℃.
In some embodiments of the invention, the temperature of the second base fluid is 40 to 50 ℃, including but not limited to any one of a point value or a range of values between any two of 42 ℃, 45 ℃, 48 ℃.
In the process of the second coprecipitation reaction, the pH value of the mixed material is 9.5-11; including but not limited to a point value of any one of 9.8, 10.0, 10.3, 10.5, 10.8 or a range value between any two.
Preferably, in the process of the second coprecipitation reaction, the molar concentration of the complexing agent in the mixed material is 0.1-1.0 mol/L; including but not limited to a dot value of any one of 0.2mol/L, 0.3mol/L, 0.4mol/L, 0.5mol/L, 0.6mol/L, 0.7mol/L, 0.8mol/L, 0.9mol/L, or a range value between any two.
Preferably, the time of the second coprecipitation reaction is 10 to 100 hours, including but not limited to a point value of any one of 20 hours, 30 hours, 40 hours, 50 hours, 60 hours, 70 hours, 80 hours, 90 hours or a range value between any two.
In some embodiments of the invention, the mixture is stirred at a speed of 100 to 200r/min during the second coprecipitation reaction. Wherein the rotational speed includes, but is not limited to, a point value of any one of 120r/min, 150r/min, 180r/min, or a range value therebetween.
In some embodiments of the invention, the first co-precipitation reaction and the second co-precipitation reaction are both performed under an atmosphere of inert gas. Preferably, the atmosphere of the inert gas is that inert gas is respectively introduced into the first base liquid and the second base liquid by adopting a bubbling method, the inert gas is at least one of nitrogen, helium and argon, and the introduced amount of the inert gas is 1-5 m 3 /h, including but not limited to 2m 3 /h、3m 3 /h、4m 3 A point value of any one of/h or a range value between any two.
In some embodiments of the invention, after the solid-liquid separation, and before the sieving, the method further comprises washing and drying steps.
In a third aspect, the invention provides a positive electrode sheet, which is mainly prepared from the positive electrode precursor for the sodium ion battery or the positive electrode precursor for the sodium ion battery prepared by the preparation method of the positive electrode precursor for the sodium ion battery.
In a fourth aspect, the invention provides a sodium ion battery comprising a positive electrode sheet as described above.
The sodium ion battery has excellent electrochemical performance, good electrochemical stability, good cycle performance and long service life.
Compared with the prior art, the invention has the beneficial effects that:
the positive electrode precursor for the sodium ion battery has the advantages of uniform element distribution, no segregation, uniform particle size distribution, good sphericity, clear primary particle morphology, high tap density, good electrochemical stability and cycle performance and the like.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are needed in the description of the embodiments or the prior art will be briefly described, and it is obvious that the drawings in the description below are some embodiments of the present invention, and other drawings can be obtained according to the drawings without inventive effort for a person skilled in the art.
FIG. 1 is a schematic cross-sectional view of a positive electrode precursor for a sodium ion battery according to the present invention;
FIG. 2 is an SEM image of the inner core of the ternary nickel-cobalt-manganese precursor prepared in step (1) of example 1 provided by the invention;
FIG. 3 is an SEM image of a positive electrode precursor for sodium ion battery prepared in step (2) of example 1 provided by the present invention;
FIG. 4 is an SEM image of the inner core of the ternary nickel-cobalt-manganese precursor prepared in step (1) of example 2 provided by the invention;
FIG. 5 is an SEM image of the positive electrode precursor for sodium ion battery prepared in step (2) of example 2 provided by the present invention;
fig. 6 is an SEM image of a positive electrode precursor for a sodium ion battery prepared in comparative example 1 provided by the present invention.
Detailed Description
The technical solution of the present invention will be clearly and completely described below with reference to the accompanying drawings and detailed description, but it will be understood by those skilled in the art that the examples described below are some, but not all, examples of the present invention, and are intended to be illustrative of the present invention only and should not be construed as limiting the scope of the present invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
Example 1
The preparation method of the positive electrode precursor for the sodium ion battery provided by the embodiment comprises the following steps:
(1) Preparing a sulfate mixed solution of nickel ions, cobalt ions and manganese ions (namely a nickel cobalt manganese ternary mixed salt solution, namely a nickel cobalt manganese sulfate mixed solution), wherein the molar ratio of nickel element to cobalt element to manganese element is 8:1:1, the sum of the concentrations of nickel ion, cobalt ion and manganese ion (i.e., the total molar concentration of metal ions) is 1.5mol/L. The three materials of nickel-cobalt-manganese sulfate mixed solution, 10mol/L NaOH solution and 5mol/L ammonia water solution are respectively conveyed into a reaction kettle with first base solution according to a certain proportion (molar ratio of 1:2:0.1) by a metering pump, wherein the temperature of the first base solution is 50 ℃, the pH value is 11.8, and the ammonium concentration is 1.5g/L. Under the protection of nitrogen atmosphere, controlling the temperature of the first coprecipitation reaction at 50 ℃, controlling the pH value in the reaction process at 11.4, controlling the ammonium concentration at 1.5g/L, and stirring at 250rpm to perform the first coprecipitation reaction to form the nickel-cobalt-manganese ternary precursor core. After the reaction of continuous feeding for 50 hours, the feeding is stopped, and the nickel-cobalt-manganese ternary precursor crystal nucleus slurry is obtained, wherein the granularity D50= 3.596 μm of crystal nuclei.
(2) Preparing a sulfate mixed solution of nickel ions, ferrous ions and manganese ions (namely a nickel-iron-manganese ternary mixed salt solution, namely a nickel-iron-manganese sulfate mixed solution), wherein the molar ratio of nickel element to iron element to manganese element is 30:35:35, the sum of the concentrations of nickel ions, ferrous ions and manganese ions (i.e., the total molar concentration of metal ions) was 2.0mol/L. And (3) respectively conveying the three materials of the nickel-iron-manganese sulfate mixed solution, the 8mol/L NaOH (precipitant) solution and the 3mol/L disodium ethylenediamine tetraacetate solution into a reaction kettle containing a second base solution through a metering pump according to a certain proportion (molar ratio of 1:2:0.12), wherein the second base solution is obtained by uniformly mixing the nickel-cobalt-manganese ternary precursor crystal nucleus slurry (500L) prepared in the step (1), the precipitant solution, the second complexing agent solution and pure water, the temperature of the second base solution is 50 ℃, the pH value of the second base solution is 10.5, and the concentration of the second complexing agent in the second base solution is 0.1mol/L. Under the protection of nitrogen atmosphere, controlling the temperature of the second coprecipitation reaction at 48 ℃, controlling the pH value in the reaction process at 10.0, controlling the concentration of the complexing agent at 0.15mol/L, and stirring at 150rpm to perform the second coprecipitation reaction to form a nickel-iron-manganese ternary precursor shell and coating the nickel-iron-manganese ternary precursor shell on the surface of the nickel-cobalt-manganese ternary precursor core. Continuous feed 60Stopping feeding after h, conveying qualified precursor slurry in the reaction kettle to a centrifugal machine for filtering, and then sequentially washing, drying, screening, demagnetizing and packaging to obtain the positive electrode precursor for the sodium ion battery with a core-shell structure, wherein the inner core of the core-shell structure is Ni, cobalt and manganese ternary precursors 0.8 Co 0.1 Mn 0.1 (OH) 2 The shell is Ni, a ternary precursor of nickel, iron and manganese 0.3 Fe 0.35 Mn 0.35 (OH) 2 。
Wherein the particle size D50=9.64 μm of the positive electrode precursor for sodium ion battery has a tap density of 1.72g/cm 3 Specific surface area of 9.56m 2 And/g, the microscopic secondary particles are spherical-like particles, and the macroscopic morphology is black powder.
Fig. 1 is a schematic cross-sectional structure of a positive electrode precursor for a sodium ion battery according to the present invention.
An SEM image of the inner core of the ternary nickel-cobalt-manganese precursor prepared in step (1) of this example 1 is shown in fig. 2, and an SEM image of the positive electrode precursor for sodium ion battery prepared in step (2) of this example 1 is shown in fig. 3.
Example 2
The preparation method of the positive electrode precursor for the sodium ion battery provided by the embodiment comprises the following steps:
(1) Preparing a sulfate mixed solution of nickel ions, cobalt ions and manganese ions (namely a nickel cobalt manganese ternary mixed salt solution, namely a nickel cobalt manganese sulfate mixed solution), wherein the molar ratio of nickel element to cobalt element to manganese element is 8:1:1, the sum of the concentrations of nickel ion, cobalt ion and manganese ion (i.e., the total molar concentration of metal ions) is 2.0mol/L. The three materials of nickel-cobalt-manganese sulfate mixed solution, 10mol/L NaOH solution and 5mol/L ammonia water solution are respectively conveyed into a reaction kettle with first base solution according to a certain proportion (molar ratio of 1:2:0.1) by a metering pump, wherein the temperature of the first base solution is 50 ℃, the pH value is 11.8, and the ammonium concentration is 1.5g/L. Under the protection of nitrogen atmosphere, controlling the temperature of the first coprecipitation reaction at 55 ℃, controlling the pH value in the reaction process at 10.8, controlling the ammonium concentration at 1.8g/L, and stirring at 250rpm to perform the first coprecipitation reaction to form the nickel-cobalt-manganese ternary precursor core. After the continuous feeding reaction for 14 hours, stopping feeding to obtain the nickel-cobalt-manganese ternary precursor crystal nucleus slurry, wherein the granularity D50= 2.583 μm of the crystal nucleus.
(2) Preparing a sulfate mixed solution of nickel ions, ferrous ions and manganese ions (namely a nickel-iron-manganese ternary mixed salt solution, namely a nickel-iron-manganese sulfate mixed solution), wherein the molar ratio of nickel element to iron element to manganese element is 30:35:35, the sum of the concentrations of nickel ions, ferrous ions and manganese ions (i.e., the total molar concentration of metal ions) was 2.0mol/L. And (3) respectively conveying three materials of a nickel-iron-manganese sulfate mixed solution, a 5mol/L NaOH (precipitant) solution and a 2mol/L diethylenetriamine pentaacetic acid pentasodium solution into a reaction kettle containing a second base solution through a metering pump according to a certain proportion (molar ratio of 1:2:0.2), wherein the second base solution is obtained by uniformly mixing the nickel-cobalt-manganese ternary precursor crystal nucleus slurry (1000L) prepared in the step (1), the precipitant solution, the second complexing agent solution and pure water, the temperature of the second base solution is 40 ℃, the pH value of the second base solution is 10.5, and the concentration of the second complexing agent in the second base solution is 0.3mol/L. Under the protection of nitrogen atmosphere, controlling the temperature of the second coprecipitation reaction at 40 ℃, controlling the pH value in the reaction process at 10.5, controlling the concentration of the complexing agent at 0.2mol/L, and stirring at 200rpm to perform the second coprecipitation reaction to form a nickel-iron-manganese ternary precursor shell and enabling the nickel-iron-manganese ternary precursor shell to be coated on the surface of the nickel-cobalt-manganese ternary precursor core. Continuously feeding for 45 hours, stopping feeding, conveying qualified precursor slurry in the reaction kettle to a centrifugal machine for filtering, and then sequentially washing, drying, screening, demagnetizing and packaging to obtain a positive electrode precursor for a sodium ion battery with a core-shell structure, wherein the inner core of the core-shell structure is a nickel-cobalt-manganese ternary precursor Ni 0.8 Co 0.1 Mn 0.1 (OH) 2 The shell is Ni, a ternary precursor of nickel, iron and manganese 0.3 Fe 0.35 Mn 0.35 (OH) 2 。
Wherein the particle size D50= 6.355 μm of the positive electrode precursor for sodium ion battery has a tap density of 1.53g/cm 3 A specific surface area of 12.39m 2 And/g, the microscopic secondary particles are spherical-like particles, and the macroscopic morphology is black powder.
An SEM image of the inner core of the ternary nickel-cobalt-manganese precursor prepared in step (1) of this example 2 is shown in fig. 4, and an SEM image of the positive electrode precursor for sodium ion battery prepared in step (2) of this example 2 is shown in fig. 5.
Example 3
The preparation method of the positive electrode precursor for the sodium ion battery provided by the embodiment comprises the following steps:
(1) Substantially the same as in (1) of example 2, except that the molar ratio of nickel element, cobalt element and manganese element in the nickel cobalt manganese sulfate mixed solution was replaced with 55:5:40.
(2) Substantially the same as in (2) of example 2, except that the molar ratio of nickel element, iron element and manganese element in the nickel-iron-manganese sulfate mixed solution was replaced with 10:30:60.
The positive electrode precursor for sodium ion battery with the core-shell structure prepared by the embodiment has the core of nickel-cobalt-manganese ternary precursor Ni 0.55 Co 0.05 Mn 0.4 (OH) 2 The shell is Ni, a ternary precursor of nickel, iron and manganese 0.1 Fe 0.3 Mn 0.6 (OH) 2 。
Wherein the particle size D50= 6.804 μm and tap density of the positive electrode precursor for sodium ion battery are 1.65g/cm 3 Specific surface area of 13.68m 2 And/g, the microscopic secondary particles are spherical-like particles, and the macroscopic morphology is black powder.
Example 4
The preparation method of the positive electrode precursor for the sodium ion battery provided by the embodiment comprises the following steps:
(1) Preparing a nitrate mixed solution (namely a nickel-cobalt-manganese ternary mixed salt solution, namely a nickel-cobalt-manganese nitrate mixed solution) of nickel ions, cobalt ions and manganese ions, wherein the molar ratio of nickel elements to cobalt elements to manganese elements is 8:1:1, the sum of the concentrations of nickel ion, cobalt ion and manganese ion (i.e., the total molar concentration of metal ions) is 1.0mol/L. The three materials of nickel cobalt manganese nitrate mixed solution, KOH solution with the concentration of 8mol/L and ammonia water solution with the concentration of 8mol/L are respectively conveyed into a reaction kettle with first base solution according to a certain proportion (the mol ratio is 1:2:0.24) through a metering pump, wherein the temperature of the first base solution is 40 ℃, the pH value is 12, and the ammonium concentration is 3g/L. Under the protection of nitrogen atmosphere, the temperature of the first coprecipitation reaction is controlled at 40 ℃, the pH value in the reaction process is controlled at 11.8, the ammonium concentration is 3g/L, the stirring speed is 250rpm, and the first coprecipitation reaction is carried out to form the nickel-cobalt-manganese ternary precursor kernel. After the reaction of the continuous feeding for 32 hours, the feeding is stopped, and the nickel-cobalt-manganese ternary precursor crystal nucleus slurry is obtained, wherein the granularity D50=1.453 mu m of crystal nuclei.
(2) Preparing a nitrate mixed solution (namely a nickel-iron-manganese ternary mixed salt solution, namely a nickel-iron-manganese nitrate mixed solution) of nickel ions, ferrous ions and manganese ions, wherein the molar ratio of nickel element to iron element to manganese element is 30:35:35, the sum of the concentrations of nickel ions, ferrous ions and manganese ions (i.e., the total molar concentration of metal ions) was 3.0mol/L. And (3) respectively conveying the three materials of the nickel-iron-manganese nitrate mixed solution, the KOH solution with the concentration of 5mol/L and the trisodium nitrilotriacetate solution with the concentration of 5mol/L into a reaction kettle containing a second base solution by a metering pump according to a certain proportion (the mol ratio of 1:2:0.69), wherein the second base solution is obtained by uniformly mixing the nickel-cobalt-manganese ternary precursor crystal nucleus slurry (1000L) prepared in the step (1), the precipitant solution, the second complexing agent solution and the pure water, the temperature of the second base solution is 45 ℃, the pH value of the second base solution is 10, and the concentration of the second complexing agent in the second base solution is 0.8mol/L. And under the protection of nitrogen atmosphere, controlling the temperature of the second coprecipitation reaction at 45 ℃, controlling the pH value in the reaction process at 10, controlling the concentration of the complexing agent at 0.8mol/L, and stirring at 200rpm to perform the second coprecipitation reaction to form a nickel-iron-manganese ternary precursor shell and coating the nickel-iron-manganese ternary precursor shell on the surface of the nickel-cobalt-manganese ternary precursor core. Continuously feeding for 50 hours, stopping feeding, conveying qualified precursor slurry in the reaction kettle to a centrifugal machine for filtering, and then sequentially washing, drying, screening, demagnetizing and packaging to obtain a positive electrode precursor for a sodium ion battery with a core-shell structure, wherein the inner core of the core-shell structure is a nickel-cobalt-manganese ternary precursor Ni 0.8 Co 0.1 Mn 0.1 (OH) 2 The shell is Ni, a ternary precursor of nickel, iron and manganese 0.3 Fe 0.35 Mn 0.35 (OH) 2 。
Wherein the particle size D50= 4.024 μm of the positive electrode precursor for sodium ion battery has a tap density of 1.59g/cm 3 Specific surface area of 15.56m 2 The microscopic secondary particles are spheroid particlesThe particles and the macroscopic morphology are black powder.
Comparative example 1
The preparation method of the positive electrode precursor for the sodium ion battery provided by the comparative example comprises the following steps:
preparing a sulfate mixed solution of nickel ions, ferrous ions and manganese ions (namely a nickel-iron-manganese ternary mixed salt solution, namely a nickel-iron-manganese sulfate mixed solution), wherein the molar ratio of nickel element to iron element to manganese element is 30:35:35, the sum of the concentrations of nickel ions, ferrous ions and manganese ions (i.e., the total molar concentration of metal ions) was 2.0mol/L. The three materials of the nickel-iron-manganese sulfate mixed solution, the NaOH solution with the concentration of 5mol/L and the ammonia solution with the concentration of 2mol/L are respectively conveyed into a reaction kettle with a base solution by a metering pump according to a certain proportion (the mol ratio is 1:2:0.32), wherein the base solution is a mixed solution of pure water, the NaOH solution and the complexing agent solution, the temperature of the base solution is 40 ℃, the pH value of the base solution is 10.5, and the complexing agent concentration of the complexing agent is 0.3mol/L. Under the protection of nitrogen atmosphere, the temperature of the coprecipitation reaction is controlled to 45 ℃, the pH in the reaction process is controlled to 10.5, the concentration of the complexing agent is 0.3mol/L, and the stirring rotating speed is 200rpm. And stopping feeding after continuously feeding for 45 hours, conveying qualified precursor slurry in the reaction kettle to a centrifugal machine for filtering, and then washing, drying, screening, demagnetizing and packaging sequentially to obtain the anode precursor for the sodium ion battery.
Wherein the particle size D50= 6.355 μm and tap density of the positive electrode precursor for sodium ion battery is 1.09g/cm 3 Specific surface area of 19.18m 2 And/g, the micro secondary particles are amorphous particles, and the macro morphology is black powder.
An SEM image of the positive electrode precursor for sodium ion battery prepared in comparative example 1 is shown in fig. 6.
Comparative example 2
The preparation method of the positive electrode precursor for sodium ion battery provided in this comparative example is basically the same as that of example 2, except that in step (2), the second complexing agent is replaced with ammonia water of equimolar concentration.
The positive electrode precursor for sodium ion battery prepared in this comparative example had a particle size d50= 6.262 μm and a tap density of 0.89g/cm 3 Specific surface area of 24.78m 2 And/g, the micro secondary particles are amorphous particles, and the macro morphology is black powder.
While the invention has been illustrated and described with reference to specific embodiments, it is to be understood that the above embodiments are merely illustrative of the technical aspects of the invention and not restrictive thereof; those of ordinary skill in the art will appreciate that: modifications may be made to the technical solutions described in the foregoing embodiments, or equivalents may be substituted for some or all of the technical features thereof, without departing from the spirit and scope of the present invention; such modifications and substitutions do not depart from the spirit of the corresponding technical solutions; it is therefore intended to cover in the appended claims all such alternatives and modifications as fall within the scope of the invention.
Claims (10)
1. The positive electrode precursor for the sodium ion battery is characterized by comprising a core-shell structure, wherein the inner core of the core-shell structure is a nickel-cobalt-manganese ternary precursor, and the outer shell of the core-shell structure is a nickel-iron-manganese ternary precursor;
wherein the chemical formula of the nickel-cobalt-manganese ternary precursor is Ni x Co y Mn z (OH) 2 Wherein 0 is<x<1，0<y<1，0<z<1, and x+y+z=1;
the chemical formula of the nickel-iron-manganese ternary precursor is Ni a Fe b Mn c (OH) 2 Wherein 0 is<a<1，0<b<1，0<c<1, and a+b+c=1;
specific surface area of the positive electrode precursor for sodium ion battery>9m 2 /g；
Tap density of positive electrode precursor for sodium ion battery>1.5g/cm 3 ；
Complexing agents used in the process of forming the ferronickel manganese ternary precursor comprise at least one of monoethanolamine, diethanolamine, triethanolamine, trisodium nitrilotriacetate, ethylenediamine tetraacetate and diethylenetriamine pentaacetic acid and salts thereof.
2. The positive electrode precursor for sodium ion battery according to claim 1, wherein the D50 particle diameter of the core is 1 to 5 μm;
preferably, the D50 particle size of the positive electrode precursor for sodium ion battery is 4-15 μm.
3. The method for preparing a positive electrode precursor for a sodium ion battery according to claim 1 or 2, comprising the steps of:
adding a nickel-cobalt-manganese ternary mixed salt solution, a precipitator solution and a first complexing agent solution into a first base solution to perform a first coprecipitation reaction to form a nickel-cobalt-manganese ternary precursor kernel, thereby obtaining nickel-cobalt-manganese ternary precursor crystal nucleus slurry;
uniformly mixing the nickel-cobalt-manganese ternary precursor crystal nucleus slurry, the precipitator solution and the second complexing agent solution to obtain a second base solution, adding a nickel-iron-manganese ternary mixed salt solution, the precipitator solution and the second complexing agent solution into the second base solution, performing a second coprecipitation reaction to form a nickel-iron-manganese ternary precursor shell, coating the nickel-cobalt-manganese ternary precursor shell on the surface of the nickel-cobalt-manganese ternary precursor inner core, and sequentially performing solid-liquid separation, screening and demagnetizing to obtain the positive electrode precursor for the sodium ion battery;
wherein the first complexing agent solution comprises at least one of ammonia water, an ammonium sulfate solution, an ammonium chloride solution and an ammonium nitrate solution;
the second complexing agent solution comprises at least one of monoethanolamine solution, diethanolamine solution, triethanolamine solution, trisodium nitrilotriacetate solution, ethylenediamine tetraacetate solution, diethylenetriamine pentaacetic acid solution and salt solution thereof.
4. The method for producing a positive electrode precursor for a sodium ion battery according to claim 3, wherein the molar concentration of the first complexing agent solution is 4 to 10mol/L;
preferably, the total molar concentration of metal ions in the nickel-cobalt-manganese ternary mixed salt solution is 1-2.5 mol/L;
preferably, the molar concentration of the second complexing agent solution is 1-10 mol/L;
preferably, the total molar concentration of metal ions in the ferronickel manganese ternary mixed salt solution is 1-3 mol/L.
5. The method for producing a positive electrode precursor for a sodium ion battery according to claim 3, wherein the precipitant solution comprises a sodium hydroxide solution and/or a potassium hydroxide solution;
preferably, the molar concentration of the precipitant solution used in the course of the first coprecipitation reaction is 7-12 mol/L;
preferably, the molar concentration of the precipitant solution used during the second coprecipitation reaction is 2 to 8mol/L.
6. The method for producing a positive electrode precursor for a sodium ion battery according to claim 3, wherein the pH of the first base solution is 10.8 to 12.5, and the mass concentration of ammonium ions in the first base solution is 1 to 5g/L;
preferably, the pH of the second base solution is 9.5-11, and the molar concentration of the second complexing agent in the second base solution is 0.1-1 mol/L.
7. The method for producing a positive electrode precursor for a sodium ion battery according to claim 3, wherein in the process of the first coprecipitation reaction, the temperature of the mixture is 35 to 60 ℃, and the pH of the mixture is 10.5 to 12.5;
preferably, in the process of the first coprecipitation reaction, the mass concentration of ammonium ions in the mixed material is 1-5 g/L;
preferably, the time of the first coprecipitation reaction is 5 to 60 hours.
8. The method for producing a positive electrode precursor for a sodium ion battery according to claim 3, wherein the temperature of the mixture is 40 to 50 ℃ and the pH of the mixture is 9.5 to 11 during the second coprecipitation reaction;
preferably, in the process of the second coprecipitation reaction, the molar concentration of the complexing agent in the mixed material is 0.1-1.0 mol/L;
preferably, the time of the second coprecipitation reaction is 10 to 100 hours.
9. A positive electrode sheet, which is mainly prepared from the positive electrode precursor for a sodium ion battery according to claim 1 or 2, or the positive electrode precursor for a sodium ion battery prepared by the method for preparing the positive electrode precursor for a sodium ion battery according to any one of claims 3 to 8.
10. A sodium ion battery comprising the positive electrode sheet of claim 9.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN116443955A (en) * | 2023-06-14 | 2023-07-18 | 宜宾光原锂电材料有限公司 | Nickel-iron-copper-manganese precursor, preparation method thereof, positive electrode material and battery |
| CN116621234A (en) * | 2023-07-20 | 2023-08-22 | 宜宾光原锂电材料有限公司 | Sodium ion positive electrode material precursor, preparation method and positive electrode material |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN116443955A (en) * | 2023-06-14 | 2023-07-18 | 宜宾光原锂电材料有限公司 | Nickel-iron-copper-manganese precursor, preparation method thereof, positive electrode material and battery |
| CN116443955B (en) * | 2023-06-14 | 2023-09-26 | 宜宾光原锂电材料有限公司 | Nickel-iron-copper-manganese precursor, preparation method thereof, positive electrode material and battery |
| CN116621234A (en) * | 2023-07-20 | 2023-08-22 | 宜宾光原锂电材料有限公司 | Sodium ion positive electrode material precursor, preparation method and positive electrode material |
| CN116621234B (en) * | 2023-07-20 | 2023-11-07 | 宜宾光原锂电材料有限公司 | Sodium ion positive electrode material precursor, preparation method and positive electrode material |
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