CN114477311B - Cobalt composite hydroxide, preparation method thereof, lithium ion battery anode material and lithium ion battery - Google Patents

Cobalt composite hydroxide, preparation method thereof, lithium ion battery anode material and lithium ion battery Download PDF

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CN114477311B
CN114477311B CN202111610311.6A CN202111610311A CN114477311B CN 114477311 B CN114477311 B CN 114477311B CN 202111610311 A CN202111610311 A CN 202111610311A CN 114477311 B CN114477311 B CN 114477311B
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composite hydroxide
cobalt composite
cobalt
lithium ion
positive electrode
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CN114477311A (en
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何乐
王灯
訚硕
翁毅
周正
周明涛
胡骏康
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Zhongwei New Materials Co ltd
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    • C01G53/00—Compounds of nickel
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    • C01G51/00—Compounds of cobalt
    • C01G51/40—Cobaltates
    • C01G51/42—Cobaltates containing alkali metals, e.g. LiCoO2
    • C01G51/44—Cobaltates containing alkali metals, e.g. LiCoO2 containing manganese
    • C01G51/50—Cobaltates containing alkali metals, e.g. LiCoO2 containing manganese of the type [MnO2]n-, e.g. Li(CoxMn1-x)O2, Li(MyCoxMn1-x-y)O2
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    • C01G53/40—Nickelates
    • C01G53/42—Nickelates containing alkali metals, e.g. LiNiO2
    • C01G53/44—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese
    • C01G53/50—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese of the type [MnO2]n-, e.g. Li(NixMn1-x)O2, Li(MyNixMn1-x-y)O2
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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    • C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
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Abstract

The invention relates to the field of lithium ion batteries, in particular to a cobalt composite hydroxide, a preparation method thereof, a lithium ion battery anode material and a lithium ion battery. The chemical formula of the cobalt composite hydroxide is Ni xCoyMnz(OH)2, wherein x+y+z=1, x is less than or equal to 0.1, y is more than or equal to 0.9, z is less than or equal to 0.1, and x and z are not simultaneously 0; the proportion of 100 active crystal faces in the cobalt composite hydroxide is 10% -40%. By doping Ni and/or Mn, the structural stability of the cobalt composite hydroxide can be effectively improved, the specific capacity and the circulating capacity retention rate of the battery are improved, and the cost is reduced; by exposing a large area of the 100 active crystal faces and covering the 001 inactive faces, the multiplying power performance of the positive electrode material obtained after sintering can be improved, the contact area between the positive electrode material and electrolyte is reduced, the side reaction of the positive electrode material-electrolyte interface is reduced, and excellent cycle performance is obtained.

Description

Cobalt composite hydroxide, preparation method thereof, lithium ion battery anode material and lithium ion battery
Technical Field
The invention relates to the field of lithium ion batteries, in particular to a cobalt composite hydroxide, a preparation method thereof, a lithium ion battery anode material and a lithium ion battery.
Background
Lithium cobaltate is an inorganic compound of the formula LiCoO 2, which is commonly used as a positive electrode material for lithium ion batteries, and has the appearance of gray black powder. The energy density, charge-discharge multiplying power, safety and other key indexes of the lithium ion battery are mainly limited by the positive electrode material.
At present, the lithium cobalt oxide positive electrode material is a mature positive electrode material, and is widely applied to the 3C (short for three electronic products of computer, communication and consumer electronics) digital field due to the characteristics of high energy density and stable discharge voltage. However, the lithium cobaltate material has the defects of low specific capacity, poor safety, high cost and the like.
In addition, the cathode material can undergo side reactions at the battery-electrolyte interface in the long cycle process, which can lead to problems of dissolution of the cathode material, increase of the internal resistance of the battery, poor thermal safety, rapid decay of charge-discharge cycle capacity and the like.
In view of this, the present invention has been made.
Disclosure of Invention
The first object of the present invention is to provide a cobalt composite hydroxide, which can effectively improve structural stability of the cobalt composite hydroxide, increase specific capacity and cycle capacity retention rate of a battery, and reduce cost by doping Ni and/or Mn; the proportion of each element in the cobalt composite hydroxide is within a specific range, so that the cobalt composite hydroxide with a 100 active surface exposure structure can be obtained, the proportion of a 100 active crystal face of the cobalt composite hydroxide is kept between 10% and 40%, and the 100 active crystal face is exposed in a large area, so that the multiplying power performance of the positive electrode material obtained after sintering can be improved, the contact area between the positive electrode material and electrolyte is reduced, the occurrence of side reaction of the positive electrode material-electrolyte interface is reduced, and excellent cycle performance is obtained.
The second aim of the invention is to provide a preparation method of the cobalt composite hydroxide, which has the advantages of simple operation, mild condition, suitability for mass production and the like.
The third object of the present invention is to provide a positive electrode material for a lithium ion battery, which is excellent in rate performance, and is excellent in cycle performance because the contact area between the positive electrode material and the electrolyte is reduced, and the occurrence of side reactions at the interface between the positive electrode material and the electrolyte is reduced.
The fourth object of the present invention is to provide a lithium ion battery having advantages of high energy density, excellent rate performance and cycle performance, high safety performance, and the like.
In order to achieve the above object of the present invention, the following technical solutions are specifically adopted:
The invention provides a cobalt composite hydroxide, which has a chemical formula of Ni xCoyMnz(OH)2, wherein x+y+z=1, x is less than or equal to 0.1, y is more than or equal to 0.9, z is less than or equal to 0.1, and x and z are not simultaneously 0;
The ratio of the 100 active crystal faces in the cobalt composite hydroxide is 10% -40% (12%, 14%, 16%, 18%, 20%, 25%, 30%, 35% or 38% can be selected).
Wherein x may be selected from 0, 0.01, 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09, or 0.1; y may be selected from 0.90, 0.91, 0.92, 0.93, 0.94, 0.95, 0.96, 0.97, 0.98 or 0.99; z may be selected from 0, 0.01, 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09 or 0.1.
According to the cobalt composite hydroxide provided by the invention, through doping Ni and/or Mn, the structural stability of the cobalt composite hydroxide can be effectively improved, the specific capacity and the circulating capacity retention rate of a battery are improved, and the cost is reduced.
In addition, the proportion of each element in the cobalt composite hydroxide is in a specific range, so that the cobalt composite hydroxide with a 100 active surface exposure structure can be obtained, the ratio of the 100 active crystal faces of the cobalt composite hydroxide is kept between 10 and 40 percent, and the 100 active crystal faces are exposed in a large area, so that the 001 inactive surface is covered, the multiplying power performance of the positive electrode material obtained after sintering can be improved, the contact area between the positive electrode material and electrolyte is reduced, the side reaction of the positive electrode material-electrolyte interface is reduced, and excellent cycle performance is obtained.
Specifically, the diffusion rate of Li + of the cobalt composite hydroxide serving as the positive electrode material precursor on different crystal planes is large, the diffusion of Li + of the layered oxide positive electrode precursor on a 100 crystal plane is fast, and the transmission speed of Li + of a 001 crystal plane is slow. Therefore, the invention can expose large area of active crystal face by regulating and controlling preferred orientation of primary crystal face and secondary particle structure, and improve electrochemical performance of cobalt composite hydroxide.
In addition, the positive electrode material obtained after the mixed lithium sintering of the cobalt composite hydroxide provided by the invention can inherit the exposed structural characteristics of the active surface of the cobalt composite hydroxide 100.
Preferably, the primary particles of the cobalt composite hydroxide have a hexagonal prism shape.
Preferably, the cobalt composite hydroxide primary particles have a thickness of 0.2 to 1.0 μm; including but not limited to a dot value of any one of 0.3 μm, 0.4 μm, 0.5 μm, 0.6 μm, 0.7 μm, 0.8 μm, 0.9 μm, or a range value between any two.
Preferably, the length of the cobalt composite hydroxide primary particles is from 1.0 to 2.5 μm, including but not limited to a dot value of any one of 1.2 μm, 1.4 μm, 1.5 μm, 1.7 μm, 1.9 μm, 2.0 μm, 2.2 μm, 2.4 μm, or a range value between any two.
Preferably, the microstructure of the cobalt composite hydroxide provided by the invention is a three-dimensional flower-like structure, and the three-dimensional flower-like structure is formed by a single-layer sheet consisting of a plurality of grains.
Wherein, the primary particles in the application refer to a single-layer sheet composed of a plurality of crystal grains, the sheet is hexagonal prism, and is a sheet-shaped structure with a hexagonal cross section; the secondary particles in the application refer to particles with three-dimensional flower-like structures.
The ratio of the active crystal face of 100 is related to the thickness and the length of the primary particles of the cobalt composite hydroxide, and the higher the ratio of the active face, the more lithium ion diffusion channels on the surfaces of the positive electrode material particles obtained by sintering the cobalt composite hydroxide, and the more excellent the rate capability of the material.
The primary particles of the cobalt composite hydroxide adopt the thickness and length ranges, enough growth space can be provided for the primary particles, and the 100 active surface ratio of the cobalt composite hydroxide obtained in the range is high, so that the rate performance and the cycle performance of the positive electrode material prepared from the cobalt composite hydroxide are improved.
Preferably, the cobalt composite hydroxide has a grain size along the 001 inactive crystal plane direction ofIncluding but not limited to/>Any one of the point values or a range value between any two.
The size of the crystal grains can influence the reactivity of the cobalt composite hydroxide and lithium carbonate in the lithium mixing sintering process and the proportion of the sintered positive electrode material, so that the dispersion state of the materials and the safety of the materials can be influenced. The grain size in the range is beneficial to improving the dispersibility of materials, avoiding material agglomeration, and the positive electrode material obtained by sintering the material has good safety performance.
Preferably, the ratio of the grain size of the cobalt composite hydroxide along the 001 inactive crystal plane direction to the grain size along the 100 active crystal plane is 0.8 to 1.0, and 0.9 may be selected.
The size ratio of the grains can reflect the active surface ratio in the grains. The larger the ratio is, the higher the ratio of 100 active faces in the crystal grains is, and the higher the ratio of 100 active faces in single crystal grains is, the more excellent the material rate performance is. The size ratio in the range is beneficial to improving the multiplying power performance of the material.
Wherein, the schematic diagram of the grain sizes of the cobalt composite hydroxide along different directions is shown in fig. 1.
The primary particles of the cobalt composite hydroxide are schematically shown in FIG. 2.
Preferably, the D50 particle size of the cobalt composite hydroxide is 9-11 mu m; also selected was 10 μm.
Preferably, the ratio (D95-D5)/D50 of the difference between the D95 particle diameter and the D5 particle diameter to the D50 particle diameter of the cobalt composite hydroxide is 0.9 to 1.1; alternatively, 0.95, 1.0 or 1.05 may be used.
The uniform granularity is beneficial to avoiding the melting agglomeration of the positive electrode material prepared from the cobalt composite hydroxide in the sintering process, reducing the polarization phenomenon caused by the uneven granularity of the positive electrode material in the battery charging and discharging process, and improving the battery cycle performance.
The invention provides a preparation method of the cobalt composite hydroxide, which comprises the following steps:
Adding a mixed metal salt solution, a precipitator solution and a complexing agent into a base solution under an inert atmosphere, performing coprecipitation reaction, and after precipitate particles grow to a target particle size, sequentially performing solid-liquid separation, sieving and demagnetizing to obtain the cobalt composite hydroxide;
Wherein the metal element in the mixed metal salt solution comprises at least one of nickel element and manganese element, and cobalt element; and the molar ratio of the nickel element, the cobalt element and the manganese element is 0 to 10 (1, 2, 3, 4, 5, 6, 7, 8 or 9 may also be selected): 90 to 100 (91, 92, 93, 94, 95, 96, 97, 98 or 99 may also be selected): 0 to 10 (1, 2, 3, 4, 5, 6, 7, 8 or 9 may also be selected).
The preparation method can obtain the cobalt composite hydroxide with a 100 active surface exposure structure with a specific ratio.
The preparation method of the cobalt composite hydroxide provided by the invention has the advantages of simplicity in operation, mild conditions, suitability for mass production and the like.
The mixed metal salt solution is a solution containing nickel element and cobalt element, or a solution containing manganese element and cobalt element, or a solution containing nickel element, cobalt element and manganese element.
The mixed metal salt solution is prepared by dissolving metal elements in water, which is beneficial to improving the distribution uniformity of Ni, co and Mn in the coprecipitation reaction process.
In addition, the coprecipitation reaction is carried out in an inert atmosphere, so that the oxidation of materials in the reaction process can be avoided.
Preferably, the ratio of the feed rates of the mixed metal salt solution, the precipitant solution and the complexing agent is 1:0.35 to 0.42 (0.36, 0.37, 0.38, 0.39, 0.40 or 0.41 may also be selected): 0.012 to 0.175 (0.015, 0.02, 0.03, 0.04, 0.06, 0.08, 0.10, 0.12, 0.14, 0.15, 0.16 or 0.17 may also be selected).
By adjusting the feed flow ratio of the raw materials in the coprecipitation reaction process, a series of hydroxides with different secondary particle thickness, length, secondary particle morphology and grain size can be obtained.
Preferably, the molar concentration of the metal ions in the mixed metal salt solution is 1-5 mol/L; including but not limited to a dot value of any one of 2mol/L, 3mol/L, 4mol/L, or a range value between any two.
Preferably, the mass fraction of the precipitant solution is 30% -35%; including but not limited to a point value of any one of 31%, 32%, 33%, 34%, or a range value between any two.
Preferably, the mass fraction of the complexing agent is 18% -25%, including but not limited to any one of 19%, 20%, 21%, 22%, 23%, 24% or a range between any two.
The precipitant solution and the complexing agent with the concentrations are adopted, which is helpful for reducing the reaction wastewater.
In addition, the concentration of metal ions in the mixed metal salt solution, the concentration of the precipitant solution and the complexing agent also have a certain influence on the physicochemical properties of the cobalt composite hydroxide, and the concentration in the range is beneficial to improving the ratio of 100 active crystal faces in the cobalt composite hydroxide.
Preferably, the target particle diameter of the precipitate particles is 8-15 μm; it is also possible to choose 9 μm, 10 μm, 11 μm, 12 μm, 13 μm or 14 μm.
Preferably, during the co-precipitation reaction, the pH of the mixture is 10.5 to 12.5 (optionally 11, 11.5 or 12) and the temperature of the mixture is 40 to 60 ℃ (optionally 45 ℃, 50 ℃ or 55 ℃).
The adoption of the preparation temperature and the pH value is more beneficial to improving the ratio of 100 active crystal faces.
In some specific embodiments of the invention, the nickel source used in the mixed metal salt solution comprises at least one of nickel chloride, nickel sulfate, and nickel nitrate;
preferably, the cobalt source used in the mixed metal salt solution comprises at least one of cobalt chloride, cobalt sulfate, and cobalt nitrate;
preferably, the manganese source used in the mixed metal salt solution includes at least one of manganese chloride, manganese sulfate, and manganese nitrate;
Preferably, the gas used for the inert atmosphere comprises nitrogen and/or argon.
Preferably, after the solid-liquid separation, the method further comprises the step of washing and drying the separated solid material.
More preferably, the drying temperature is 100-150deg.C (110 deg.C, 120 deg.C, 130 deg.C or 140 deg.C may also be selected), and the drying time is 10-15 h (11 h, 12h, 13h or 14h may also be selected).
Preferably, the base solution consists essentially of a precipitant solution and a complexing agent.
Preferably, the precipitant comprises sodium hydroxide and/or potassium hydroxide.
Preferably, the complexing agent comprises aqueous ammonia and/or EDTA (ethylenediamine tetraacetic acid).
The invention also provides a lithium ion battery anode material, which is obtained by mixing and sintering the cobalt composite hydroxide or the cobalt composite hydroxide prepared by the preparation method of the cobalt composite hydroxide.
The positive electrode material has excellent multiplying power performance, and the contact area between the positive electrode material and the electrolyte is reduced, so that the side reaction of the positive electrode material-electrolyte interface is reduced, and the cycle performance is excellent.
The invention also provides a lithium ion battery, which comprises a positive electrode prepared from the positive electrode material of the lithium ion battery.
The lithium ion battery has the advantages of high energy density, excellent multiplying power performance and cycle performance, high safety performance and the like.
Compared with the prior art, the invention has the beneficial effects that:
(1) According to the cobalt composite hydroxide provided by the invention, through doping Ni and/or Mn, the structural stability of the cobalt composite hydroxide can be effectively improved, the specific capacity and the circulating capacity retention rate of a battery are improved, and the cost is reduced.
(2) According to the cobalt composite hydroxide provided by the invention, the proportion of each element in the cobalt composite hydroxide is in a specific range, so that the hydroxide with a 100 active surface exposure structure can be obtained, the proportion of 100 active crystal faces of the hydroxide is kept between 10% and 40%, and the 100 active crystal faces are exposed in a large area, so that the 001 inactive surface is covered, the multiplying power performance of the positive electrode material obtained after sintering can be improved, the contact area between the positive electrode material and electrolyte is reduced, and the side reaction of the positive electrode material-electrolyte interface is reduced, so that excellent cycle performance is obtained.
(3) The lithium ion battery anode material provided by the invention has the advantages of excellent multiplying power performance, excellent cycle performance and high safety performance.
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 diagram of the grain sizes of cobalt composite hydroxide according to the present invention along different directions;
FIG. 2 is a schematic structural view of primary particles of cobalt composite hydroxide provided by the present invention;
FIG. 3 is an SEM image of a cobalt composite hydroxide provided in example 1 of the present invention at 1000 magnification;
FIG. 4 is an SEM image of a cobalt composite hydroxide provided in example 1 of the present invention at 5000 magnification;
FIG. 5 is an SEM image of a cobalt composite hydroxide provided in example 2 of the present invention at 1000 magnification;
FIG. 6 is an SEM image of a cobalt composite hydroxide provided in example 2 of the invention at 5000 magnification;
FIG. 7 is an SEM image of a cobalt composite hydroxide according to example 3 of the present invention at 1000 magnification;
FIG. 8 is an SEM image of a cobalt composite hydroxide provided in example 3 of the invention at 5000 magnification;
FIG. 9 is an SEM image of a cobalt composite hydroxide provided in example 4 of the invention at 1000 magnification;
FIG. 10 is an SEM image of a cobalt composite hydroxide provided in example 4 of the invention at 5000 magnification;
FIG. 11 is an SEM image of a cobalt composite hydroxide provided in comparative example 1 of the invention at 1000;
FIG. 12 is an SEM image of a cobalt composite hydroxide provided in comparative example 1 of the invention at 5000 magnification;
FIG. 13 is an SEM image of a cobalt composite hydroxide provided in comparative example 2 of the invention at 1000;
FIG. 14 is an SEM image of a cobalt composite hydroxide provided in comparative example 2 of the invention at 5000 magnification;
FIG. 15 is an SEM image of the cobalt composite hydroxide of comparative example 3 of the present invention at 1000 magnification;
FIG. 16 is an SEM image of a cobalt composite hydroxide provided in comparative example 3 of the invention at 5000 magnification;
FIG. 17 is an XRD pattern of the cobalt composite hydroxide provided in example 1 of the present invention;
FIG. 18 is an XRD pattern of a cobalt composite hydroxide provided in example 2 of the present invention;
FIG. 19 is an XRD pattern of a cobalt composite hydroxide provided in example 3 of the present invention;
FIG. 20 is an XRD pattern for a cobalt composite hydroxide provided in example 4 of the present invention;
FIG. 21 is an XRD pattern for the cobalt composite hydroxide provided in comparative example 1 of the present invention;
FIG. 22 is an XRD pattern for the cobalt composite hydroxide provided in comparative example 2 of the present invention;
FIG. 23 is an XRD pattern for the cobalt composite hydroxide provided in comparative example 3 of the present invention;
FIG. 24 is an EDS spectrum of the CP graph (a) and nickel (b), cobalt (c) and manganese (d) of the cobalt composite hydroxide according to example 1 of the present invention;
FIG. 25 is a SEM image of a positive electrode material made of the cobalt composite hydroxide of example 1 at 1000 magnification according to the present invention;
FIG. 26 is a SEM image of 5000 magnification of a positive electrode material made of the cobalt composite hydroxide of example 1, according to the present invention;
FIG. 27 is a SEM image of a positive electrode material made of the cobalt composite hydroxide of example 2 at 1000 magnification according to the present invention;
FIG. 28 is a SEM image of 5000 magnification of a positive electrode material made of the cobalt composite hydroxide of example 2 provided by the invention;
FIG. 29 is a SEM image of a positive electrode material made of the cobalt composite hydroxide of comparative example 1 at 1000 magnification according to the present invention;
FIG. 30 is a SEM image of a 5000 magnification of a positive electrode material made of a cobalt composite hydroxide of comparative example 1, according to the present invention;
FIG. 31 is a SEM image of a positive electrode material made of the cobalt composite hydroxide of comparative example 2 at 1000 magnification according to the present invention;
fig. 32 is an SEM image of a positive electrode material made of the cobalt composite hydroxide of comparative example 2 at a magnification of 5000, 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.
FIG. 1 is a schematic diagram of the grain sizes of cobalt composite hydroxide according to the present invention along different directions; fig. 2 is a schematic structural view of primary particles of the cobalt composite hydroxide provided by the invention.
Example 1
The preparation method of the cobalt composite hydroxide Ni 0.05Co0.9Mn0.05(OH)2 provided by the embodiment comprises the following steps (the reaction process is carried out in nitrogen atmosphere):
(1) Dissolving nickel chloride, cobalt chloride and manganese chloride in water, and uniformly mixing to obtain a mixed metal salt solution; wherein, the mole ratio of nickel, cobalt and manganese elements is 5:90:5, the molar concentration of metal ions in the mixed metal salt solution is 2mol/L;
Preparing a 32% sodium hydroxide solution as a precipitant solution, and preparing 21% ammonia water as a complexing agent; mixing the 32% sodium hydroxide solution with 21% ammonia water by mass fraction, and adding water to prepare a base solution with pH of 11.5 and ammonia concentration of 8.0 g/L;
(2) Selecting a reaction kettle with the volume of 100L, and adding the mixed metal salt solution, the precipitant solution and the complexing agent obtained in the step (1) into the base solution under the nitrogen atmosphere with the purity of more than or equal to 99.9 percent for coprecipitation reaction; wherein, the feed flow ratio of the mixed metal salt solution, the precipitator solution and the complexing agent is 1:0.4:0.04; continuously stirring in the reaction process, and controlling the pH of the mixed material to be 11.2 and the temperature of the mixed material to be 50 ℃ in the reaction process;
(3) Stopping feeding when the precipitate particles in the reaction kettle grow to the particle size of 10 mu m, filtering the mixed material, and sequentially performing alkali washing, water washing, drying (12 h at 120 ℃) drying, sieving and demagnetizing on the solid material obtained after the filtering to obtain the cobalt composite hydroxide Ni 0.05Co0.9Mn0.05(OH)2.
Example 2
The preparation method of the cobalt composite hydroxide Ni 0.05Co0.9Mn0.05(OH)2 provided in this example is basically the same as that of example 1, except that in step (2), the feed flow ratio of the mixed metal salt solution, the precipitant solution and the complexing agent is replaced with 1:0.4:0.06.
Example 3
The preparation method of the cobalt composite hydroxide Ni 0.1Co0.9(OH)2 provided by the embodiment comprises the following steps (the reaction process is carried out in nitrogen atmosphere):
(1) Dissolving nickel sulfate and cobalt sulfate in water, and uniformly mixing to obtain a mixed metal salt solution; wherein, the mole ratio of nickel element to cobalt element is 10:90, wherein the molar concentration of metal ions in the mixed metal salt solution is 2mol/L;
Preparing a 32% sodium hydroxide solution as a precipitant solution, and preparing 21% ammonia water as a complexing agent; mixing the 32% sodium hydroxide solution with 21% ammonia water by mass fraction, and adding water to prepare a base solution with pH of 11.5 and ammonia concentration of 8.0 g/L;
(2) Exactly the same as in step (2) of example 1;
(3) Exactly the same as in step (3) of example 1.
Example 4
The preparation method of the cobalt composite hydroxide Co 0.9Mn0.1(OH)2 provided by the embodiment comprises the following steps (the reaction process is carried out in nitrogen atmosphere):
(1) Dissolving cobalt nitrate and manganese nitrate in water, and uniformly mixing to obtain a mixed metal salt solution; wherein the molar ratio of manganese element to cobalt element is 10:90, wherein the molar concentration of metal ions in the mixed metal salt solution is 2mol/L;
preparing a 32% sodium hydroxide solution as a precipitant solution, and preparing 21% ammonia water as a complexing agent; mixing the 32% sodium hydroxide solution with 21% ammonia water by mass fraction, and adding water to prepare a base solution with pH of 11.5 and ammonia concentration of 8.0 g/L;
(2) Exactly the same as in step (2) of example 1;
(3) Exactly the same as in step (3) of example 1.
Example 5
The preparation method of the cobalt composite hydroxide Ni 0.05Co0.9Mn0.05(OH)2 provided in the present example is basically the same as that of example 1, except that: firstly, in the step (1), the molar concentration of metal ions in the mixed metal salt solution is 3mol/L, the mass fraction of the sodium hydroxide solution is 35%, and the mass fraction of the ammonia water is 25%;
Second, in step (2), the feed flow ratio of the mixed metal salt solution, the precipitant solution, and the complexing agent is replaced with 1:0.35:0.17, and controlling the pH of the mixture in the reaction process to be 11, and controlling the temperature of the mixture to be 40 ℃.
Comparative example 1
The preparation method of the cobalt composite hydroxide Ni 0.05Co0.9Mn0.05(OH)2 provided in this comparative example is substantially the same as in example 1, except that in step (2), the feed flow ratio of the mixed metal salt solution, the precipitant solution and the complexing agent is replaced with 1:0.2:0.2.
Comparative example 2
The preparation method of the cobalt composite hydroxide Ni 0.05Co0.9Mn0.05(OH)2 provided in this comparative example is substantially the same as in example 1, except that in step (2), the feed flow ratio of the mixed metal salt solution, the precipitant solution and the complexing agent is replaced with 1:0.4:0.02.
Comparative example 3
The preparation method of the cobalt composite hydroxide Ni 0.05Co0.9Mn0.05(OH)2 provided in this comparative example is substantially the same as in example 1, except that nitrogen protection is not applied during the reaction to prepare the cobalt composite hydroxide.
Comparative example 4
The preparation method of the cobalt composite hydroxide Ni 0.1Co0.8Mn0.1(OH)2 provided in the present comparative example is basically the same as that of example 1, except that in step (1), the molar ratio of nickel, cobalt and manganese elements in the mixed metal salt solution is 1:8:1.
Experimental example 1
The thickness, length, 100 active crystal plane ratio, and particle size of the cobalt composite hydroxide were measured for the primary particles of the cobalt composite hydroxide prepared in each of the above examples and comparative examples, respectively, and the results are shown in table 1.
XRD measurements were performed on the cobalt composite hydroxide prepared in each of the above examples and comparative examples, and the results are shown in Table 2 below.
Table 1 physicochemical indices of cobalt composite hydroxide groups
TABLE 2 XRD diffraction phase data for cobalt composite hydroxides of the various groups
Scanning Electron Microscope (SEM) tests were performed on the cobalt composite hydroxide prepared in example 1, example 2, example 3, example 4, comparative example 1, comparative example 2, comparative example 3, and the results thereof are shown in fig. 3 (1000-fold magnification of example 1) and fig. 4 (5000-fold magnification of example 1), fig. 5 (1000-fold magnification of example 2) and fig. 6 (5000-fold magnification of example 2), fig. 7 (1000-fold magnification of example 3) and fig. 8 (5000-fold magnification of example 3), fig. 9 (1000-fold magnification of example 4) and fig. 10 (5000-fold magnification of example 4), fig. 11 (1000-fold magnification of comparative example 1) and fig. 12 (5000-fold magnification of comparative example 1), fig. 13 (1000-fold magnification of comparative example 2) and fig. 14 (5000-fold magnification of comparative example 2), fig. 15 (1000-fold magnification of comparative example 3) and fig. 16 (5000-fold magnification of comparative example 3), respectively.
XRD measurements were performed on the cobalt composite hydroxide prepared in example 1, example 2, example 3, example 4, comparative example 1, comparative example 2, and comparative example 3, and the results are shown in FIGS. 17, 18, 19, 20, 21, 22, and 23, respectively.
The cobalt composite hydroxide obtained in example 1 was subjected to CP (ion beam profile milling) cutting and EDS spectroscopy, and the results are shown in fig. 24, wherein fig. 24 (a) is a cross-sectional view of the cobalt composite hydroxide particles after CP cutting, fig. 24 (b) is an EDS spectroscopy of nickel element, fig. 24 (c) is an EDS spectroscopy of cobalt element, and fig. 24 (d) is an EDS spectroscopy of manganese element. As can be seen from fig. 24, the cobalt composite hydroxide prepared in example 1 has uniform distribution of Ni, co, and Mn elements.
In addition, according to the present invention, TEM (transmission electron microscope) test was performed on the cobalt composite hydroxide obtained in example 1, and it was obtained that the inter-plane distances of the surfaces of the primary particles of the cobalt composite hydroxide were respectivelyThe data are consistent with the interplanar spacing data obtained by XRD diffraction of the (001) and (100) planes, respectively, which confirm that the exposed surfaces of the cobalt composite hydroxide primary particles are the (001) and (100) planes. The cobalt composite hydroxide primary particles were in the shape of regular hexagonal nano-platelets (see fig. 2), and the exposed active surface of the particles was calculated to be about 35% based on the average thickness and length of the primary particles.
As can be seen from the SEM image of the cobalt composite hydroxide prepared in example 1, there was no agglomeration between particles.
Experimental example 2
The cobalt composite hydroxides obtained in the above examples and comparative examples were subjected to lithium mixing sintering, respectively, to obtain each group of positive electrode materials, and then the particle diameters of each group of positive electrode materials were detected, and assembled into lithium ion batteries, which were subjected to electrochemical performance tests, and the results are shown in table 3.
Table 3 particle size and electrochemical Performance test results for each group of cathode materials
And the positive electrode materials obtained from the cobalt composite hydroxide obtained in example 1, example 2, comparative example 1 and comparative example 2 were subjected to Scanning Electron Microscope (SEM), and the results thereof are shown in fig. 25 (1000-fold magnification in example 1) and fig. 26 (5000-fold magnification in example 1), fig. 27 (1000-fold magnification in example 2) and fig. 28 (5000-fold magnification in example 2), fig. 29 (1000-fold magnification in comparative example 1) and fig. 30 (5000-fold magnification in comparative example 1), fig. 31 (1000-fold magnification in comparative example 2) and fig. 32 (5000-fold magnification in comparative example 2), respectively.
As can be seen from fig. 25 and 26, the positive electrode material after sintering the cobalt composite hydroxide of example 1 can inherit the morphology of the cobalt composite hydroxide structure, and the secondary particles are more dense, and the gaps between the primary particles are filled. In the electrical performance test, the 1C cycle test is performed, and the capacity retention rate of 100 circles is 94%; the 5C cycle test, 100 cycles capacity retention reached 73%, and the positive electrode material of example 1 had better rate performance and cycle performance than each of the comparative examples.
From the SEM topography of examples 3,4 and 5, it can be seen that when the chemical formula of the cobalt composite hydroxide is Ni xCoyMnz(OH)2, where x+y+z=1, x is 0.1, y is 0.9, and z is 0.1, the cobalt composite hydroxide having a similar secondary particle active surface exposure structure can be obtained by adjusting the element ratio in this range. And in the subsequent test of the electrical property of the anode material, the anode material has excellent capacity and rate capability.
As can be seen from the data of comparative example 1, the active surface ratio of the precursor prepared in comparative example 1 was increased to 57%, and the grain size was reachedAfter the cobalt composite hydroxide lithium is sintered into the positive electrode material, the material particles are subjected to fusion aggregation, the particle size distribution is widened, and the exposed structure of the active crystal face of the cobalt composite hydroxide 100 is damaged. In the electrical property test, 1C cycle test is performed, and the capacity retention rate of 100 circles is 85%; the capacity retention rate of 100 cycles was reduced to 55% by the 5C cycle test.
As can be seen from the data of each set of comparative example 2, the particle size distribution of the precursor prepared in comparative example 2 becomes broader after the feed flow rate of the complexing agent is reduced, and the particle size non-uniformity is clearly observed in the cobalt composite hydroxide SEM. The primary particle thickness of the cobalt composite hydroxide prepared in comparative example 2 was about 0.1. Mu.m, and the active surface ratio was 6%. The anode material obtained after lithium mixing and sintering has a small amount of agglomeration, and a large amount of gaps exist among primary particles. In the electrical performance test, 1C cycle test is performed, and the capacity retention rate of 100 circles is 83%; the 5C cycle test showed a significant decrease in the battery capacity retention at high rate discharge compared to example 1 at a capacity retention of 48% for 100 cycles.
As can be seen from the data of each group of comparative example 3, the surface of the secondary particles of the cobalt composite hydroxide prepared in comparative example 3 exhibited a disordered state, and did not have an active surface-exposed structure. XRD diffraction shows that the material is in an oxide state, the crystallinity is poor, the particle size distribution (D95-D5)/D50 of the cobalt composite hydroxide reaches 2.66, and the particle size distribution is nonuniform. In the subsequent electrical performance test, both the material capacity and the rate performance were inferior to those of example 1.
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 (9)

1. The cobalt composite hydroxide is characterized by having a chemical formula of Ni xCoyMnz(OH)2, wherein x+y+z=1, x is less than or equal to 0.1, y is more than or equal to 0.9, z is less than or equal to 0.1, and x and z are not simultaneously 0;
the proportion of 100 active crystal faces in the cobalt composite hydroxide is 10% -40%;
the primary particles of the cobalt composite hydroxide are hexagonal prisms in shape; the thickness of the primary particles of the cobalt composite hydroxide is 0.2-1.0 mu m; the length of the primary particles of the cobalt composite hydroxide is 1.0-2.5 mu m;
The ratio of the grain size of the cobalt composite hydroxide along the direction of a 001 non-active crystal face to the grain size along a 100 active crystal face is 0.8-1.0.
2. The cobalt composite hydroxide according to claim 1, wherein the cobalt composite hydroxide has a grain size of 600-800 a along the 001 inactive crystal plane direction.
3. The cobalt composite hydroxide according to claim 1, wherein the D50 particle diameter of the cobalt composite hydroxide is 9 to 11 μm;
and/or the ratio (D95-D5)/D50 of the difference between the D95 particle diameter and the D5 particle diameter to the D50 particle diameter of the cobalt composite hydroxide is 0.9-1.1.
4. A method for producing a cobalt composite hydroxide according to any one of claims 1 to 3, comprising the steps of:
Adding a mixed metal salt solution, a precipitator solution and a complexing agent into a base solution under an inert atmosphere, performing coprecipitation reaction, and after precipitate particles grow to a target particle size, sequentially performing solid-liquid separation, sieving and demagnetizing to obtain the cobalt composite hydroxide;
Wherein the metal element in the mixed metal salt solution comprises at least one of nickel element and manganese element, and cobalt element; and the molar ratio of the nickel element to the cobalt element to the manganese element is 0-10: 90-100: 0-10;
The ratio of the feed rates of the mixed metal salt solution, the precipitant solution and the complexing agent is 1:0.35 to 0.42:0.012 to 0.175.
5. The method according to claim 4, wherein the molar concentration of the metal ions in the mixed metal salt solution is 1 to 5mol/L.
6. The preparation method according to claim 4, wherein the mass fraction of the precipitant solution is 30% -35%;
and/or the mass fraction of the complexing agent is 18% -25%.
7. The method according to claim 4, wherein the target particle diameter of the precipitate particles is 8 to 15 μm;
And/or in the process of the coprecipitation reaction, the pH of the mixed material is 10.5-12.5, and the temperature of the mixed material is 40-60 ℃.
8. The lithium ion battery anode material is obtained by mixing and sintering the cobalt composite hydroxide prepared by the preparation method of the cobalt composite hydroxide according to any one of claims 1-3 or the cobalt composite hydroxide according to any one of claims 4-7.
9. A lithium ion battery comprising a positive electrode prepared from the positive electrode material of a lithium ion battery of claim 8.
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