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CN116282207A - Dendritic positive electrode material precursor, preparation method thereof, lithium ion battery positive electrode material, lithium ion battery and electric equipment - Google Patents

Dendritic positive electrode material precursor, preparation method thereof, lithium ion battery positive electrode material, lithium ion battery and electric equipment Download PDF

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CN116282207A
CN116282207A CN202211729774.9A CN202211729774A CN116282207A CN 116282207 A CN116282207 A CN 116282207A CN 202211729774 A CN202211729774 A CN 202211729774A CN 116282207 A CN116282207 A CN 116282207A
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reaction
positive electrode
flow rate
equal
electrode material
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周港怀
王继霞
訚硕
张磊
张欣鹏
刘时九
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Zhongwei New Materials Co ltd
Hunan Zhongwei New Energy Technology Co ltd
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Zhongwei New Materials Co ltd
Hunan Zhongwei New Energy Technology Co ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
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    • C01G53/00—Compounds of nickel
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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Abstract

The application provides a dendritic positive electrode material precursor and a preparation method thereof, a lithium ion battery positive electrode material, a lithium ion battery and electric equipment, and relates to the field of lithium ion batteries. The dendritic cathode material precursor comprises an inner core and an outer shell coating the inner core; the primary particles of the inner core are in loose honeycomb-like arrangement, and the primary particles of the outer shell are in loose dendrite-like arrangement. The preparation method of the dendritic cathode material precursor comprises the following steps: introducing a metal salt solution, a precipitator and a complexing agent into the base solution under the protection of inert gas to perform a first reaction to obtain a core; and continuing the second reaction and the third reaction to obtain the dendritic positive electrode material precursor. The raw materials of the lithium ion battery positive electrode material comprise the dendrite-shaped positive electrode material precursor. The lithium ion battery comprises the raw materials of the positive electrode material of the lithium ion battery. The electric equipment comprises the lithium ion battery. The battery prepared by using the precursor has high safety and good cycle performance and rate performance.

Description

Dendritic positive electrode material precursor, preparation method thereof, lithium ion battery positive electrode material, lithium ion battery and electric equipment
Technical Field
The application relates to the field of lithium ion batteries, in particular to a dendrite-shaped positive electrode material precursor, a preparation method thereof, a lithium ion battery positive electrode material, a lithium ion battery and electric equipment.
Background
With the more frequent updating of 3C products, the 3C products are an irreversible development trend of 'durability and quick charge', which puts higher demands on the cycle performance and the rate performance of the lithium ion battery. The ternary battery material combines the advantages of lithium nickelate, lithium cobaltate and lithium manganate, and has the advantages of low cost, high stability, excellent electrochemical performance and the like. The coprecipitation method is one of the most commonly used methods for ternary cathode materials because of the advantages of easy control of the process, uniform cation distribution and the like. The shape of the ternary precursor prepared by common precipitation is radial, and the ternary precursor is easy to break under the condition of larger pressure. At the same time, the internal compact structure is not easy to conduct electrons and diffuse protons.
Therefore, it is important to develop a precursor and a positive electrode material that can solve the above problems, ensure the safety of the material, and cycle performance and rate performance.
Disclosure of Invention
The application aims to provide a dendrite-shaped lithium ion battery anode material precursor, a preparation method thereof, a lithium ion battery anode material, a lithium ion battery and electric equipment, so as to solve the problems.
In order to achieve the above purpose, the present application adopts the following technical scheme:
a dendritic positive electrode material precursor comprises a core and a shell coating the core;
the primary particles of the inner core are in loose honeycomb-like arrangement, and the primary particles of the outer shell are in loose dendrite-like arrangement.
Preferably, the precursor is a nickel-containing oxyhydrogen compound;
preferably, the dendrite arrangement of the primary particles of the shell is clustered;
preferably, the inner core has a porosity of 16-36% and the outer shell has a porosity of 7-27%;
preferably, the dendrite-like cathode material precursor has an overall average porosity of 11-31%;
preferably, the D50 of the core is 0.8-2.9 μm;
preferably, the ratio of the average radius of the core to the radius of the dendrite cathode material precursor is (0.3 to 0.6): 1, a step of;
preferably, the ratio of the average thickness of the outer shell to the radius of the dendrite cathode material precursor is (0.4 to 0.7): 1.
preferably, the nickel-containing oxyhydrogen compound has the chemical formula Ni x Co y Mn z M a (OH) 2 Wherein x is more than or equal to 0.5 and less than or equal to 1, y is more than or equal to 0 and less than or equal to 0.5, z is more than or equal to 0 and less than or equal to 0.5, and a is more than or equal to 0 and less than or equal to 0.3; m is at least one of Al, ti, zr, mo, cr, W, B, mg, ba, nb and Sr; preferably, y is more than or equal to 0 and less than or equal to 0.3, a is more than or equal to 0 and less than or equal to 0.1, and more preferably, x is more than or equal to 0.5 and less than or equal to 0.7,0 and a is less than or equal to 0.01;
Preferably, the inner core has a circular-like aperture therein and the outer shell has an irregular polygonal aperture therein;
preferably, the primary particles of the inner core are lamellar;
preferably, the primary particles of the shell are rod-shaped with an aspect ratio of (6-14): 1.
preferably, the dendrite-like cathode material precursor satisfies at least one of the following conditions:
d50 is 2-6. Mu.m, preferably 3-5. Mu.m;
BET of 5-18m 2 /g; BET is specific surface area;
TD of 1.3-1.9g/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the TD is tap density;
span is 0.3-0.5, span= (D90-D10)/D50;
E. the ratio of the average radius of the core to the radius of the dendrite cathode material precursor is (0.42-0.48): 1, a step of;
F. the ratio of the average thickness of the outer shell to the radius of the dendrite cathode material precursor is (0.52-0.58): 1, a step of;
G. the sphericity of the precursor particles is 92.00-98.00%.
The application also provides a preparation method of the dendrite-shaped positive electrode material precursor, which comprises the following steps:
introducing a metal salt solution, a precipitator and a complexing agent into the base solution under the protection of inert gas to perform a first reaction to obtain a core;
continuing the second reaction and the third reaction to obtain a dendritic anode material precursor;
during the first reaction, the second reaction and the third reaction, the pH value of the system, the concentration of the complexing agent and the nickel content of the supernatant liquid are controlled independently.
Preferably, the base solution is a mixed solution of water, a precipitator and a complexing agent;
preferably, the pH value of the base solution is 11.3-12.4, and the ammonia concentration is 1.0-2.5g/L;
preferably, during the first reaction, the pH of the system is reduced from 11.0-12.0 to 10.7-11.6, the concentration of the complexing agent is controlled within the range of 2.3-3.2g/L, and the nickel content of the supernatant liquid of the system is maintained at 0-10ppm;
preferably, during the second reaction, the pH of the system is in the range of 10.6-11.8, the concentration of the complexing agent is controlled in the range of 2.3-3.2g/L, and the nickel content of the supernatant liquid of the system is maintained at 50-60ppm;
preferably, during the second reaction, the pH of the system is in the range of 10.5-11.8, the concentration of the complexing agent is controlled in the range of 0.8-2.6g/L, and the nickel content of the supernatant liquid of the system is maintained at 50-60ppm.
Preferably, the metal salt solution comprises Ni and at least one of Co, mn and M, wherein M is at least one of Al, ti, zr, mo, cr, W, B, mg, ba, nb and Sr;
preferably, the precipitant comprises aqueous sodium hydroxide solution and the complexing agent comprises aqueous ammonia;
more preferably, the concentration of the aqueous sodium hydroxide solution is 20-40wt%, and the concentration of the aqueous ammonia solution is 5-24wt%;
preferably, in the process of the first reaction, the flow rate of the metal salt solution is 2.5-4.6% L/h of the volume of the reaction vessel, the flow rate of the sodium hydroxide aqueous solution is 1.0-2.0% L/h of the volume of the reaction vessel, and the flow rate of the ammonia water is 0.01-0.1% L/h of the volume of the reaction vessel;
Preferably, in the process of the second reaction, the flow rate of the metal salt solution is 3.5-5.5% L/h of the volume of the reaction vessel, the flow rate of the sodium hydroxide aqueous solution is 1.0-2.0% L/h of the volume of the reaction vessel, and the flow rate of the ammonia water is 0.02-0.1% L/h of the volume of the reaction vessel;
preferably, in the process of the third reaction, the flow rate of the metal salt solution is 5.0-6.0% L/h of the volume of the reaction vessel, the flow rate of the sodium hydroxide aqueous solution is 1.6-2.8% L/h of the volume of the reaction vessel, and the flow rate of the ammonia water is 0.06-0.12% L/h of the volume of the reaction vessel;
preferably, the temperature of the first reaction is 40-70 ℃, the temperature of the second reaction is 40-70 ℃, and the temperature of the third reaction is 50-65 ℃;
preferably, the third reaction further comprises washing, solid-liquid separation, drying, sieving and demagnetizing after the end.
The application also provides a lithium ion battery anode material, which comprises dendritic anode material precursors.
The application also provides a lithium ion battery, and the raw materials of the lithium ion battery comprise a lithium ion battery anode material.
The application also provides electric equipment, and a lithium ion battery comprising the electric equipment.
Compared with the prior art, the beneficial effects of this application include:
according to the dendritic positive electrode material precursor, primary particles of the inner core are in loose honeycomb-like arrangement, and primary particles of the outer shell are in loose dendritic arrangement, so that internal stress of the sintered positive electrode material is small, internal cracks of the positive electrode material particles are reduced, and safety of battery operation is improved; the uniformity of primary particles of the positive electrode material is improved, the cycle performance and the multiplying power performance of the battery are improved, the sintered positive electrode material inherits the precursor structure, the deintercalation and mass transfer of Li ions are improved, and the multiplying power performance of the material is further improved; the discharge internal resistance of the battery is reduced, so that the running loss of the battery is reduced and the safety performance of the battery is improved.
The preparation method of the dendritic positive electrode material precursor can effectively prepare the precursor with the special morphology.
The lithium ion battery anode material, the lithium ion battery and the electric equipment are good in safety and excellent in multiplying power performance and cycle performance.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings that are needed in the embodiments will be briefly described below, it being understood that the following drawings only illustrate certain embodiments of the present application and therefore should not be considered as limiting the scope of the present application.
FIG. 1 is a cut-away view and a porosity map of the precursor of example 1;
FIG. 2 is an SEM image of a precursor of example 1;
FIG. 3 is a cut-away view of the precursor of example 1;
FIG. 4 is an SEM image of the preparation of a positive electrode material from the precursor of example 1;
FIG. 5 is an XRD pattern for the precursors of examples 1-2 and comparative examples 1-3 to prepare positive electrode materials;
FIG. 6 is an SEM image of a precursor of example 2;
FIG. 7 is a cut-away view of the precursor of example 2;
FIG. 8 is an SEM image of the preparation of a positive electrode material from the precursor of example 2;
FIG. 9 is an SEM image of a precursor of comparative example 1;
FIG. 10 is a cut-away view of a precursor of comparative example 1;
FIG. 11 is an SEM image of the preparation of a positive electrode material from the precursor of comparative example 1;
FIG. 12 is an SEM image of a precursor of comparative example 2;
FIG. 13 is a cut-away view of the precursor of comparative example 2;
FIG. 14 is an SEM image of the preparation of a positive electrode material from a precursor of comparative example 2;
FIG. 15 is an SEM image of a precursor of comparative example 3;
FIG. 16 is a cut-away view of a precursor of comparative example 3;
FIG. 17 is an SEM image of the preparation of a positive electrode material from the precursor of comparative example 3;
FIG. 18 is a graph of primary particle length for a precursor of example 1 to prepare a positive electrode material;
FIG. 19 is a graph of primary particle length for a precursor of example 2 to produce a positive electrode material;
FIG. 20 is a graph of primary particle length for the precursor of comparative example 2 to produce a positive electrode material;
fig. 21 is a graph of primary particle length for the precursor of comparative example 3 to prepare a positive electrode material.
Detailed Description
The term as used herein:
"prepared from … …" is synonymous with "comprising". The terms "comprising," "including," "having," "containing," or any other variation thereof, as used herein, are intended to cover a non-exclusive inclusion. For example, a composition, step, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, step, method, article, or apparatus.
The conjunction "consisting of … …" excludes any unspecified element, step or component. If used in a claim, such phrase will cause the claim to be closed, such that it does not include materials other than those described, except for conventional impurities associated therewith. When the phrase "consisting of … …" appears in a clause of the claim body, rather than immediately following the subject, it is limited to only the elements described in that clause; other elements are not excluded from the claim as a whole.
When an equivalent, concentration, or other value or parameter is expressed as a range, preferred range, or a range bounded by a list of upper preferable values and lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed. For example, when ranges of "1 to 5" are disclosed, the described ranges should be construed to include ranges of "1 to 4", "1 to 3", "1 to 2 and 4 to 5", "1 to 3 and 5", and the like. When a numerical range is described herein, unless otherwise indicated, the range is intended to include its endpoints and all integers and fractions within the range.
In these examples, parts and percentages are by mass unless otherwise indicated.
"parts by mass" means a basic unit of measurement showing the mass ratio of a plurality of components, and 1 part may be any unit mass, for example, 1g may be expressed, 2.689g may be expressed, and the like. If we say that the mass part of the a component is a part and the mass part of the B component is B part, the ratio a of the mass of the a component to the mass of the B component is represented as: b. alternatively, the mass of the A component is aK, and the mass of the B component is bK (K is an arbitrary number and represents a multiple factor). It is not misunderstood that the sum of the parts by mass of all the components is not limited to 100 parts, unlike the parts by mass.
"and/or" is used to indicate that one or both of the illustrated cases may occur, e.g., a and/or B include (a and B) and (a or B).
A dendritic positive electrode material precursor comprises a core and a shell coating the core;
the primary particles of the inner core are in loose honeycomb-like arrangement, and the primary particles of the outer shell are in loose dendrite-like arrangement.
The "dendrite" referred to in the present application specifically refers to a structure including a plurality of branches having substantially equal thickness and connected to each other by other branches; unlike a purely radial structure without a large number of branches cross-linked or a purely dendritic-like structure with a small branch at the lower, coarse upper part.
The dendrite has a large number of branch dendritic structures, is more tightly connected with surrounding secondary particles, has better bearing force, ensures that the whole particle has stronger compressive resistance, is not easy to break, and has the cycle performance.
In an alternative embodiment, the precursor is a nickel-containing oxyhydrogen compound.
In an alternative embodiment, the dendrite arrangement of the primary particles of the shell is clustered.
In an alternative embodiment, the inner core has a porosity of 16-36% and the outer shell has a porosity of 7-27%;
alternatively, the porosity of the inner core may be any value between 16%, 20%, 25%, 30%, 35%, 36%, or 16-36%, and the porosity of the outer shell may be any value between 7%, 10%, 15%, 20%, 25%, 27%, or 7-27%;
in an alternative embodiment, the dendritic cathode material precursor has an overall average porosity of 11-31%.
Alternatively, the overall average porosity of the dendrite-like cathode material precursor may be 11%, 15%, 20%, 25%, 30%, 31%, or any value between 11-31%;
in an alternative embodiment, the D50 of the core is 0.8-2.9 μm;
the small particle size, the inner core honeycomb loose structure and the outer shell branch crystalline loose structure have large porosity, improve the transmission and diffusion capacity of electrons and protons in electrolyte, and optimize the rate capability.
Alternatively, the D50 of the core may be any value between 0.8 μm, 1.0 μm, 1.5 μm, 2.0 μm, 2.5 μm, 2.9 μm, or 0.8-2.9 μm;
in an alternative embodiment, the ratio of the average radius of the inner core to the radius of the dendritic cathode material precursor is (0.3-0.6): 1, a step of;
alternatively, the ratio of the average radius of the core to the radius of the dendrite cathode material precursor may be 0.3: 1. 0.4: 1. 0.5: 1. 0.6:1 or (0.3-0.6): any value between 1;
in an alternative embodiment, the ratio of the average thickness of the outer shell to the radius of the dendritic cathode material precursor is (0.4-0.7): 1.
alternatively, the ratio of the average thickness of the outer shell to the radius of the dendrite cathode material precursor may be 0.4: 1. 0.5: 1. 0.6: 1. 0.7:1 or (0.4-0.7): any value between 1.
In an alternative embodiment, the dendrite cathode material precursor has the chemical formula Ni x Co y Mn z M a (OH) 2 Wherein x is more than or equal to 0.5 and less than or equal to 1, y is more than or equal to 0 and less than or equal to 0.5, z is more than or equal to 0 and less than or equal to 0.5, and a is more than or equal to 0 and less than or equal to 0.3; m is at least one of Al, ti, zr, mo, cr, W, B, mg, ba, nb and Sr; preferably, y is more than or equal to 0 and less than or equal to 0.3, a is more than or equal to 0 and less than or equal to 0.1, and more preferably, x is more than or equal to 0.5 and less than or equal to 0.7,0 and a is less than or equal to 0.01;
alternatively, x may be 0.50, 0.51, 0.52, 0.53, 0.54, 0.55, 0.56, 0.57, 0.58, 0.59, 0.60, 0.61, 0.62, 0.63, 0.64, 0.65, 0.66, 0.67, 0.68, 0.69, 0.70, 0.71, 0.72, 0.73, 0.74, 0.75, 0.76, 0.77, 0.78, 0.79, 0.80, 0.81, 0.82, 0.83, 0.84, 0.85, 0.86, 0.87, 0.88, 0.89, 0.90, 0.91, 0.92, 0.93, 0.94, 0.95, 0.96, 0.97, 0.98, 0.99, or any value equal to or greater than 0.5, less than 1; y may be any value of 0, 0.01, 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09, 0.10, 0.11, 0.12, 0.13, 0.14, 0.15, 0.16, 0.17, 0.18, 0.19, 0.20, 0.21, 0.22, 0.23, 0.24, 0.25, 0.26, 0.27, 0.28, 0.29, 0.30, 0.31, 0.32, 0.33, 0.34, 0.35, 0.36, 0.37, 0.38, 0.39, 0.40, 0.41, 0.42, 0.43, 0.44, 0.45, 0.46, 0.47, 0.48, 0.49 or greater than or less than 0.5; z may be any of 0, 0.01, 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09, 0.10, 0.11, 0.12, 0.13, 0.14, 0.15, 0.16, 0.17, 0.18, 0.19, 0.20, 0.21, 0.22, 0.23, 0.24, 0.25, 0.26, 0.27, 0.28, 0.29, 0.30, 0.31, 0.32, 0.33, 0.34, 0.35, 0.36, 0.37, 0.38, 0.39, 0.40, 0.41, 0.42, 0.43, 0.44, 0.45, 0.46, 0.47, 0.48, 0.49 or greater than or less than or equal to 0.5, a may be any of 0, 0.01, 0.02, 0.03, 0.05, 0.08, 0.09, 0.1 or less than 0.0.0.08.
In an alternative embodiment, the inner core has a circular-like aperture therein and the outer shell has an irregular polygonal aperture therein;
in an alternative embodiment, the primary particles of the inner core are in the form of flakes;
in an alternative embodiment, the primary particles of the shell are rod-shaped with an aspect ratio of (6-14): 1.
alternatively, the primary particles of the shell are rod-shaped and the aspect ratio may be 6: 1. 7: 1. 8: 1. 9: 1. 10: 1. 11: 1. 12: 1. 13: 1. 14:1 or (6-14): any value between 1.
In an alternative embodiment, the dendrite-like cathode material precursor satisfies at least one of the following conditions:
d50 is 2-6. Mu.m, preferably 3-5. Mu.m;
BET of 5-18m 2 /g；
TD of 1.3-1.9g/cm 3 ；
Span is 0.3-0.5, span= (D90-D10)/D50;
E. the ratio of the average radius of the core to the radius of the dendrite cathode material precursor is (0.42-0.48): 1, a step of;
F. the ratio of the average thickness of the outer shell to the radius of the dendrite cathode material precursor is (0.52-0.58): 1, a step of;
G. the sphericity of the precursor particles is 92.00-98.00%.
The primary particles are uniformly distributed, so that the anode material has better uniformity and higher output power and cycle performance;
narrow particle size distribution, improved cycle life and rate capability;
The precursor can obtain positive electrode material particles with good surface flatness, and can effectively reduce the running power consumption of the battery and improve the safety of the battery.
Alternatively, D50 may be any value between 2 μm, 3 μm, 4 μm, 5 μm, 6 μm or 2-6 μm, and BET may be 5m 2 /g、10m 2 /g、15m 2 /g、18m 2 /g or 5-18m 2 Between/gAny one of the values of (2); TD may be 1.3g/cm 3 、1.4g/cm 3 、1.5g/cm 3 、1.6g/cm 3 、1.7g/cm 3 、1.8g/cm 3 、1.9g/cm 3 Or 1.3-1.9g/cm 3 Any value in between; span may be any value between 0.3, 0.4, 0.5, or 0.3-0.5; the ratio of the average radius of the core to the radius of the dendrite cathode material precursor may be 0.42: 1. 0.43: 1. 0.44: 1. 0.45: 1. 0.46: 1. 0.47: 1. 0.48:1 or (0.42-0.48): any value between 1; alternatively, the ratio of the average radius of the core to the radius of the dendrite cathode material precursor may be 0.52: 1. 0.53: 1. 0.54: 1. 0.55: 1. 0.56: 1. 0.57: 1. 0.58:1 or (0.52-0.58): any value between 1; the precursor particle sphericity may be any value between 92.00%, 93.00%, 94.00%, 95.00%, 96.00%, 97.00%, 98.00%, or 92.00-98.00%.
The application also provides a preparation method of the dendrite-shaped positive electrode material precursor, which comprises the following steps:
Introducing a metal salt solution, a precipitator and a complexing agent into the base solution under the protection of inert gas to perform a first reaction to obtain a core;
continuing the second reaction and the third reaction to obtain a dendritic anode material precursor;
during the first reaction, the second reaction and the third reaction, the pH value of the system, the concentration of the complexing agent and the nickel content of the supernatant liquid are controlled independently.
Wherein the base solution is a mixed solution of water, a precipitator and a complexing agent;
the pH value of the base solution is 11.3-12.4, and the ammonia concentration is 1.0-2.5g/L.
Alternatively, the pH of the base liquid may be 11.3, 11.4, 11.5, 11.6, 11.7, 11.8, 11.9, 12.0, 12.1, 12.2, 12.3, 12.4, or any value between 11.3 and 12.4, and the ammonia concentration may be 1.0g/L, 1.5g/L, 2.0g/L, 2.5g/L, or any value between 1.0 and 2.5g/L.
In an alternative embodiment, the pH of the system is reduced from 11.0-12.0 to 10.7-11.6 during the first reaction, the concentration of the complexing agent is controlled within the range of 2.3-3.2g/L, and the nickel content of the supernatant liquid of the system is maintained at 0-10ppm;
alternatively, during the first reaction, the pH of the system can be reduced from any value within the range of 11, 11.1, 11.2, 11.3, 11.4, 11.5, 11.6, 11.7, 11.8, 11.9, 12 or 11-12 to any value within the range of 10.7, 10.8, 10.9, 11, 11.1, 11.2, 11.3, 11.4, 11.5, 11.6 or 10.7-11.6, the concentration of complexing agent being controlled to any value within the range of 2.3g/L, 2.4g/L, 2.5g/L, 2.6g/L, 2.7g/L, 2.8g/L, 2.9g/L, 3.0g/L, 3.1g/L, 3.2g/L or 2.3-3.2g/L, and the nickel content of the system being maintained at a value within the range of 0ppm, 1ppm, 2ppm, 3ppm, 4ppm, 5ppm, 7ppm, 10ppm or 10ppm;
In an alternative embodiment, during the second reaction, the pH of the system is in the range of 10.6-11.8, the concentration of the complexing agent is controlled in the range of 2.3-3.2g/L, and the nickel content of the supernatant liquid of the system is maintained at 50-60ppm;
alternatively, during the second reaction, the pH of the system may be any value in the range of 10.6, 10.7, 10.8, 10.9, 11, 11.1, 11.2, 11.3, 11.4, 11.5, 11.6, 11.7, 11.8 or any value in the range of 10.6-11.8, the concentration of complexing agent is controlled to be any value between 2.3g/L, 2.4g/L, 2.5g/L, 2.6g/L, 2.7g/L, 2.8g/L, 2.9g/L, 3.0g/L, 3.1g/L, 3.2g/L or 2.3-3.2g/L, the nickel content of the system is maintained at any value between 50ppm, 51ppm, 52ppm, 53ppm, 54ppm, 55ppm, 56ppm, 57ppm, 58ppm, 59ppm, 60ppm or 50-60ppm;
in an alternative embodiment, the pH of the system is in the range of 10.5-11.8, the complexing agent concentration is controlled in the range of 0.8-2.6g/L, and the nickel content of the supernatant of the system is maintained at 50-60ppm during the second reaction.
Alternatively, the pH of the system during the second reaction may be at any value in the range of 10.5, 10.6, 10.7, 10.8, 10.9, 11, 11.1, 11.2, 11.3, 11.4, 11.5, 11.6, 11.7, 11.8 or 10.5-11.8, the complexing agent concentration is controlled to be any value within the range of 0.8g/L, 0.9g/L, 1.0g/L, 1.1g/L, 1.2g/L, 1.3g/L, 1.4g/L, 1.5g/L, 1.6g/L, 1.7g/L, 1.8g/L, 1.9g/L, 2.0g/L, 2.1g/L, 2.2g/L, 2.3g/L, 2.4g/L, 2.5g/L, 2.6g/L or 0.8-2.6g/L, and the system supernatant nickel content is maintained at any value between 50ppm, 51ppm, 52ppm, 53ppm, 54ppm, 55ppm, 56ppm, 57ppm, 58ppm, 59ppm, 60ppm or 50-60ppm.
In an alternative embodiment, the metal salt solution comprises Ni and at least one of Co, mn, M being at least one of Al, ti, zr, mo, cr, W, B, mg, ba, nb and Sr;
in an alternative embodiment, the precipitant comprises aqueous sodium hydroxide and the complexing agent comprises aqueous ammonia; the concentration of the aqueous solution of sodium hydroxide is 20-40wt% and the concentration of the ammonia water is 5-24wt%.
Alternatively, the concentration of the aqueous sodium hydroxide solution may be 20wt%, 25wt%, 30wt%, 35wt%, 40wt%, or 20-40wt%, and the concentration of the aqueous ammonia may be 5wt%, 10wt%, 15wt%, 20wt%, 24wt%, or 5-24wt%.
In an alternative embodiment, during the first reaction, the flow rate of the metal salt solution is 2.5-4.6% L/h of the volume of the reaction vessel, the flow rate of the aqueous sodium hydroxide solution is 1.0-2.0% L/h of the volume of the reaction vessel, and the flow rate of the aqueous ammonia is 0.01-0.1% L/h of the volume of the reaction vessel;
alternatively, during the first reaction, the flow rate of the metal salt solution may be 2.5% L/h, 3.0% L/h, 3.5% L/h, 4.0% L/h, 4.5% L/h, 4.6% L/h, or any value between 2.5 and 4.6% L/h of the reaction vessel volume, the flow rate of the aqueous sodium hydroxide solution may be 1.0% L/h, 1.1% L/h, 1.2% L/h, 1.3% L/h, 1.4% L/h, 1.5% L/h, 1.6% L/h, 1.7% L/h, 1.8% L/h, 1.9% L/h, 2.0% L/h, or any value between 1.0 and 2.0% L/h, and the flow rate of the aqueous ammonia may be 0.01% L/h, 0.02% L/h, 0.03% L/h, 0.04% L/h, 0.0.07% L/h, 0.0.0% L/h, 0.09% L/h, 0.0.0.0% L/h, 0.0.0% L/h;
In an alternative embodiment, during the second reaction, the flow rate of the metal salt solution is 3.5-5.5% L/h of the reaction vessel volume, the flow rate of the aqueous sodium hydroxide solution is 1.0-2.0% L/h of the reaction vessel volume, and the flow rate of the aqueous ammonia is 0.02-0.1% L/h of the reaction vessel volume;
alternatively, during the second reaction, the flow rate of the metal salt solution may be 3.5% L/h, 4.0% L/h, 4.5% L/h, 5.0% L/h, 5.5% L/h, or any value between 3.5 and 5.5% L/h of the reaction vessel volume, the flow rate of the aqueous sodium hydroxide solution may be 1.0% L/h, 1.1% L/h, 1.2% L/h, 1.3% L/h, 1.4% L/h, 1.5% L/h, 1.6% L/h, 1.7% L/h, 1.8% L/h, 1.9% L/h, 2.0% L/h, or any value between 1.0 and 2.0% L/h, and the flow rate of the aqueous ammonia may be 0.02% L/h, 0.03% L/h, 0.04% L/h, 0.05% L/h, 0.07% L/h, 0.0.0% L/h, 0.08% L/h, or any value between 0.0.0% L/h;
in an alternative embodiment, during the third reaction, the flow rate of the metal salt solution is 5.0-6.0% L/h of the reaction vessel volume, the flow rate of the aqueous sodium hydroxide solution is 1.6-2.8% L/h of the reaction vessel volume, and the flow rate of the aqueous ammonia is 0.06-0.12% L/h of the reaction vessel volume;
Alternatively, during the third reaction, the flow rate of the aqueous sodium hydroxide solution may be any value between 5.0% L/h, 5.1% L/h, 5.2% L/h, 5.3% L/h, 5.4% L/h, 5.5% L/h, 5.6% L/h, 5.7% L/h, 5.8% L/h, 5.9% L/h, 6.0% L/h, or 5-6%L/h, the flow rate of the aqueous sodium hydroxide solution may be any value between 1.6% L/h, 1.7% L/h, 1.8% L/h, 1.9% L/h, 2.0% L/h, 2.1% L/h, 2.2% L/h, 2.3% L/h, 2.4% L/h, 2.5% L/h, 2.6% L/h, 2.7% L/h, 2.8% L/h, or 0.07% L/h, 0.0.8% L/h, 0.0.06% or 0.0.0% L/h;
in an alternative embodiment, the temperature of the first reaction is 40-70 ℃, the temperature of the second reaction is 40-70 ℃, and the temperature of the third reaction is 50-65 ℃;
alternatively, the temperature of the first reaction may be any value between 40 ℃, 45 ℃, 50 ℃, 55 ℃, 60 ℃, 65 ℃, 70 ℃, or 40-70 ℃, the temperature of the second reaction may be any value between 40 ℃, 45 ℃, 50 ℃, 55 ℃, 60 ℃, 65 ℃, 70 ℃, or 40-70 ℃, and the temperature of the third reaction may be any value between 50 ℃, 55 ℃, 60 ℃, 65 ℃, or 50-65 ℃.
The key difference points of the morphology of the prepared dendrite shell honeycomb core are as follows: the ammonia concentration in the reaction of the base solution and a plurality of sections of different conditions is controlled to be at a low level, and the flow and the pH value of each solution are controlled.
In an alternative embodiment, the third reaction further comprises washing, solid-liquid separation, drying, sieving and demagnetizing after the end of the third reaction.
The application also provides a lithium ion battery anode material, which comprises dendritic anode material precursors.
The application also provides a lithium ion battery, and the raw materials of the lithium ion battery comprise a lithium ion battery anode material.
The application also provides electric equipment, and a lithium ion battery comprising the electric equipment.
Embodiments of the present application will be described in detail below with reference to specific examples, but it will be understood by those skilled in the art that the following examples are only for illustration of the present application and should not be construed as limiting the scope of the present application. 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 embodiment provides a dendrite-like cathode material precursor having a chemical formula of Ni 0.60 Co 0.20 Mn 0.20 (OH) 2 The preparation method comprises the following steps:
preparing a solution: 1. according to the proportion of the metal mole ratio of nickel to cobalt to manganese of 60:20:20, weighing nickel sulfate, cobalt sulfate and manganese sulfate to prepare a 120g/L mixed ternary metal salt solution.
2. Adding pure water, naOH solution (concentration 32 wt%) and ammonia water (concentration 21 wt%) into a reaction kettle, uniformly stirring at constant temperature of 60 ℃ to obtain a base solution with pH of 11.7 and ammonia concentration of 1.2 g/L;
preparing a precursor material: introducing a metal salt solution (the flow rate is 4.00 percent L/h of the volume of the reaction kettle) and an ammonia water (the flow rate is 1.52 percent L/h of the volume of the reaction kettle) into the reaction kettle filled with the base solution in the reaction process of stirring and keeping the temperature at 60 ℃ and under the protection of nitrogen for 0-16h, controlling the pH value from 11.7 to 11.2 by finely adjusting the pH value of the NaOH solution, controlling the flow rate of the ammonia water to enable the ammonia concentration to fluctuate within 1.0-2.0g/L, and keeping the nickel concentration in the supernatant of the reaction system to fluctuate within the range of 0-60 ppm;
continuously introducing a metal salt solution (the flow rate is 5.00 percent L/h of the volume of the reaction kettle) and an ammonia water (the flow rate is 1.90 percent L/h of the volume of the reaction kettle) into the reaction kettle in the reaction process of 16-32h, enabling the pH to fluctuate within 11.1-11.2 by fine adjustment of the NaOH solution, enabling the ammonia concentration to fluctuate within 1.0-2.0g/L by controlling the flow rate of the ammonia water, and keeping the nickel concentration in the supernatant of the reaction system to fluctuate within the range of 0-60 ppm;
Continuously introducing a metal salt solution (the flow rate is 6.00 percent L/h of the volume of the reaction kettle) and NaOH solution (the flow rate is 2.27 percent L/h of the volume of the reaction kettle) into the reaction kettle in the reaction process of more than 32h, and enabling the pH to fluctuate within 11.0-11.1 by finely adjusting the NaOH solution; the ammonia concentration is made to fluctuate within 1.0-2.0g/L by controlling the flow rate of the ammonia water, and the nickel concentration in the supernatant liquid of the reaction system is maintained to fluctuate within the range of 0-60 ppm.
The whole reaction process is started up, mother liquor is discharged from the concentrating equipment, and the discharging speed is consistent with the total feeding amount. The secondary particles are slowly grown by controlling the reaction parameters until the secondary particles with the average particle diameter of 4.0+/-0.3 mu m are obtained, and the kettle is stopped.
Post-treatment: washing, centrifuging, drying, sieving and demagnetizing the reaction precipitation slurry to obtain the Ni with the composite structure 0.60 Co 0.20 Mn 0.20 (OH) 2 A material.
FIG. 1 (a) is a cut-away view of the precursor of example 1; (b) is a cut-away view of the individual precursor particles of example 1; (c) A shell porosity map for the individual precursor particles of example 1; (d) A plot of the core porosity of the individual precursor particles is presented in example 1.
FIG. 2 is an SEM image of a precursor of example 1; FIG. 3 is a cut-away view of the precursor of example 1.
The embodiment also provides a lithium ion battery anode material, and the preparation method thereof is as follows:
preparing a positive electrode material: 2000g of the precursor Li prepared in the example 2 CO 3 Uniformly mixing by a high-speed mixer according to the mol ratio of 1:1.05, sintering by a box-type furnace under the air atmosphere, slowly heating to 850 ℃, sintering at high temperature for 12 hours, cooling to room temperature, and then crushing and sieving to obtain the nickel-cobalt-manganese ternary anode material.
Example 1 the precursor was prepared with a SEM image of the positive electrode material as shown in fig. 4 and an xrd image as shown in fig. 5.
Preparing a battery: electrochemical performance testing was performed using button half-electricity: the positive electrode material, conductive carbon black and a binder PVDF (polyvinylidene fluoride) are prepared according to the following proportion of 8:1:1 preparing slurry, coating the slurry on an aluminum foil to prepare a positive plate, wherein the negative plate adopts a metal lithium plate, and the electrolyte adopts 1mol/L LiPF 6 DMC (volume ratio 1:1), and assembling the battery shell, the positive electrode plate, the diaphragm, the elastic piece and the gasket into a button battery in a vacuum glove box. And (5) performing electrochemical performance test by adopting a blue-ray testing system.
Example 2
The embodiment provides a dendrite-like cathode material precursor having a chemical formula of Ni 0.58 Co 0.18 Mn 0.24 (OH) 2 The preparation method comprises the following steps:
preparing a solution: 1. and weighing nickel sulfate, cobalt sulfate and manganese sulfate according to the metal molar ratio of nickel to cobalt to manganese of 58:18:24 to prepare a uniformly mixed ternary metal salt solution with the concentration of 125 g/L.
2. Adding pure water, naOH solution (with the concentration of 32 wt%) and ammonia water (with the concentration of 21 wt%) into a reaction kettle, and uniformly stirring at the constant temperature of 65 ℃ to obtain a base solution with the pH of 12.0 and the ammonia concentration of 1.2 g/L;
preparing a precursor material: introducing a metal salt solution (the flow rate is 4.00 percent L/h of the volume of the reaction kettle) and an ammonia water (the flow rate is 1.54 percent L/h of the volume of the reaction kettle) into the reaction kettle filled with the base solution in the reaction process of stirring and constant temperature 65 ℃ and nitrogen protection, controlling the pH value by fine adjustment of the NaOH solution to slowly reduce the pH value from 12.0 to 11.6, controlling the flow rate of the ammonia water to enable the ammonia concentration to fluctuate within 1.0-2.0g/L, and maintaining the fluctuation of the nickel concentration in the supernatant of the reaction system within the range of 0-60ppm so as to enable primary particles to slowly grow;
continuously introducing a metal salt solution (the flow rate is 5.00 percent L/h of the volume of the reaction kettle) and an ammonia water (the flow rate is 1.93 percent L/h of the volume of the reaction kettle) into the reaction kettle in the reaction process of 16-32h, enabling the pH to fluctuate within 11.5-11.6 by fine adjustment of the NaOH solution, enabling the ammonia concentration to fluctuate within 1.0-2.0g/L by controlling the flow rate of the ammonia water, and keeping the nickel concentration in the supernatant of the reaction system to fluctuate within the range of 0-60 ppm;
Continuously introducing a metal salt solution (the flow rate is 6.00 percent L/h of the volume of the reaction kettle) and NaOH solution (the flow rate is 2.29 percent L/h of the volume of the reaction kettle) into the reaction kettle in the reaction process of more than 32h, and enabling the pH to fluctuate within 11.4-11.5 by finely adjusting the NaOH solution; the ammonia concentration is made to fluctuate within 1.0-2.0g/L by controlling the flow rate of the ammonia water, and the nickel concentration in the supernatant liquid of the reaction system is maintained to fluctuate within the range of 0-60 ppm.
The whole reaction process is started up, mother liquor is discharged from the concentrating equipment, and the discharging speed is consistent with the total feeding amount. The reactor was stopped by controlling the reaction parameters so that the secondary particles grew slowly until secondary particles having an average particle diameter of 4.0.+ -. 0.3 μm were obtained.
Post-treatment: washing, centrifuging, drying, sieving and demagnetizing the reaction precipitation slurry to obtain the Ni with the composite structure 0.58 Co 0.18 Mn 0.24 (OH) 2 The SEM scanning electron microscope morphology result of the material is shown in figure 6, and the section view of the material is shown in figure 7.
The embodiment also provides a lithium ion battery anode material, and the preparation method thereof is as follows:
preparation of positive electrode MaterialAnd (3) material: 2000g of the precursor Li prepared in the example 2 CO 3 Mixing uniformly by a high-speed mixer according to the mol ratio of 1:1.05, sintering by a box-type furnace under the air atmosphere, slowly heating to 850 ℃, sintering at high temperature for 12 hours, cooling to room temperature, crushing and sieving to obtain the nickel-cobalt-manganese ternary positive electrode material, wherein the SEM scanning electron microscope morphology result graph is shown in figure 8, and the XRD graph is shown in figure 5.
Preparing a battery: electrochemical performance testing was performed using button half-electricity: the positive electrode material, conductive carbon black and a binder PVDF (polyvinylidene fluoride) are prepared according to the following proportion of 8:1:1 preparing slurry, coating the slurry on an aluminum foil to prepare a positive plate, wherein the negative plate adopts a metal lithium plate, and the electrolyte adopts 1mol/L LiPF 6 DMC (volume ratio 1:1), and assembling the battery shell, the positive electrode plate, the diaphragm, the elastic piece and the gasket into a button battery in a vacuum glove box. Electrochemical performance testing was performed using a blue-electric testing system, and specific electrochemical performance data are shown in table 3.
Example 3
The chemical formula: ni (Ni) 0.50 Mn 0.50 (OH) 2 (binary).
The process comprises the following steps: as in example 1.
Parameters: the Ni to Mn ratio in the metal salt solution was 1:1, and other parameters were the same as in example 1.
Detection result: d50:3.98um, BET:13.07m 2 /g，TD：1.97g/cm 3 ，span：0.57。
Kernel morphology: honeycomb shape; the appearance of the shell is as follows: and (3) a dendrite shape.
Example 4
The chemical formula: ni (Ni) 0.7524 Co 0.0499 Mn 0.1943 Al 0.0034 (OH) 2 (doping).
The process comprises the following steps: as in example 1.
Parameters: the molar ratio of Ni to Co to Mn to Al in the metal salt solution is 75.24 to 4.99 to 19.43 to 0.34,
other parameters were the same as in example 1.
Detection result: d50:4.072um, BET:16.07m 2 /g，TD：1.52g/cm 3 ，span：0.61。
Kernel morphology: honeycomb shape; the appearance of the shell is as follows: and (3) a dendrite shape.
Comparative example 1
In this comparative example, a nickel ternary precursor material in a positive electrode material active material having large particles was prepared, and Ni of the chemical formula was synthesized 0.60 Co 0.20 Mn 0.20 (OH) 2 。
Preparing a solution: 1. according to the proportion of the metal mole ratio of nickel to cobalt to manganese of 60:20:20, weighing nickel sulfate, cobalt sulfate and manganese sulfate to prepare a 120g/L mixed ternary metal salt solution.
2. Adding a certain amount of pure water, naOH solution (with the concentration of 32 wt%) and ammonia water (with the concentration of 21 wt%) into a reaction kettle, and uniformly stirring at the constant temperature of 55 ℃ to obtain a base solution with the pH of 12.0 and the ammonia concentration of 5.0 g/L;
preparing a precursor material: during the whole reaction process, under the conditions of stirring and constant temperature of 55 ℃ and nitrogen protection, introducing a metal salt solution (the flow rate is 7.00 percent L/h of the volume of the reaction kettle) and ammonia water (the flow rate is 2.66 percent L/h of the volume of the reaction kettle) into a reaction kettle filled with a base solution, controlling the pH value from 12.0 to 11.9 by fine adjustment of the pH value of the NaOH solution, enabling the ammonia concentration to fluctuate within 5.0+/-0.4 g/L by controlling the flow rate of the ammonia water, and keeping the nickel concentration in the supernatant of the reaction system fluctuating within the range of 0-60ppm, so that primary particles slowly grow until the particles with the average particle diameter of 6.0+/-0.3 mu m of seed crystals stop reacting.
The reaction was continued once in a separate vessel, and then a metal salt solution (flow rate: 7.00% L/h of the volume of the reaction vessel), a NaOH solution (flow rate: 2.66% L/h of the volume of the reaction vessel), and ammonia water (flow rate: 0.06% L/h of the volume of the reaction vessel) were introduced until particles having an average particle diameter of 8.0.+ -. 0.3 μm were obtained.
And separating the reaction kettle for the second time, then continuing to react, introducing a metal salt solution (the flow rate is 8.00 percent L/h of the volume of the reaction kettle), a NaOH solution (the flow rate is 3.00 percent L/h of the volume of the reaction kettle), ammonia water (the flow rate is 0.07 percent L/h of the volume of the reaction kettle), controlling the flow rate of the ammonia water to enable the ammonia concentration to fluctuate within 5.0+/-0.4 g/L, maintaining the fluctuation of the nickel concentration in the supernatant of the reaction system within the range of 0-60ppm, enabling the secondary particles to slowly grow until the secondary particles with the average particle diameter of 10.0+/-0.3 mu m are obtained, and stopping the kettle.
Post-treatment: washing, centrifuging, drying, sieving and demagnetizing the reaction precipitation slurry to obtain the Ni with the composite structure 0.60 Co 0.20 Mn 0.20 (OH) 2 The SEM scanning electron microscope morphology of the material is shown in figure 9.
Preparing a positive electrode material: 2000g of the precursor Li prepared in the example 2 CO 3 Mixing uniformly by a high-speed mixer according to the mol ratio of 1:1.05, sintering by a box-type furnace under the air atmosphere, slowly heating to 850 ℃, sintering at high temperature for 12 hours, cooling to room temperature, crushing and sieving to obtain the nickel-cobalt-manganese ternary positive electrode material, wherein the SEM scanning electron microscope morphology result graph is shown in figure 10, and the XRD graph is shown in figure 5.
Preparing a battery: electrochemical performance testing was performed using button half-electricity: the positive electrode material, conductive carbon black and a binder PVDF (polyvinylidene fluoride) are prepared according to the following proportion of 8:1:1 preparing slurry, coating the slurry on an aluminum foil to prepare a positive plate, wherein the negative plate adopts a metal lithium plate, and the electrolyte adopts 1mol/L LiPF 6 DMC (volume ratio 1:1), and assembling the battery shell, the positive electrode plate, the diaphragm, the elastic piece and the gasket into a button battery in a vacuum glove box. Electrochemical performance testing was performed using a blue-electric testing system, and specific electrochemical performance data are shown in table 3.
Comparative example 2
In this comparative example, a nickel ternary precursor material was prepared from a positive electrode material active material having two layers of internal porosity and one primary crystal grain in a long form, and Ni of the chemical formula was synthesized 0.60 Co 0.10 Mn 0.30 (OH) 2 。
Preparing a solution: 1. according to the proportion of the metal mole ratio of nickel to cobalt to manganese being 60:10:30, weighing nickel sulfate, cobalt sulfate and manganese sulfate to prepare 116g/L of uniformly mixed ternary metal salt solution.
2. Adding a certain amount of pure water, naOH solution (with the concentration of 32 wt%) and ammonia water (with the concentration of 21 wt%) into a reaction kettle, and uniformly stirring at the constant temperature of 60 ℃ to obtain a base solution with the pH of 11.8 and the ammonia concentration of 4.0 g/L;
preparing a precursor material: introducing a metal salt solution (the flow rate is 3.00 percent L/h of the volume of the reaction kettle) and an ammonia water (the flow rate is 1.14 percent L/h of the volume of the reaction kettle) into the reaction kettle filled with the base solution in the reaction process of stirring and keeping the temperature at 60 ℃ and under the protection of nitrogen for 0-16h, controlling the pH value from 11.8 to 11.3 by finely adjusting the pH value of the NaOH solution, and controlling the flow rate of the ammonia water to enable the ammonia concentration to fluctuate within 4.0+/-0.4 g/L;
Seed crystal growth: continuously introducing a metal salt solution (the flow rate is 4.00 percent L/h of the volume of the reaction kettle) and an ammonia water (the flow rate is 1.50 percent L/h of the volume of the reaction kettle) into the reaction kettle in the reaction process of 16-32h, enabling the pH to fluctuate within 11.2-11.3 by fine adjustment of the NaOH solution, and enabling the ammonia concentration to fluctuate within 3.0+/-0.4 g/L by controlling the flow rate of the ammonia water; and the nickel concentration in the supernatant of the reaction system was maintained to fluctuate in the range of 0-60 ppm.
During the reaction process of more than 32 hours, continuously introducing a metal salt solution (the flow rate is 5.00 percent L/h of the volume of the reaction kettle), a NaOH solution (the flow rate is 1.88 percent L/h of the volume of the reaction kettle) and ammonia water (the flow rate is 0.07 percent L/h of the volume of the reaction kettle) into the reaction kettle, enabling the pH to fluctuate within 11.0-11.1 by fine adjustment of the NaOH solution, enabling the ammonia concentration to fluctuate within 2.5+/-0.4 g/L by controlling the flow rate of the ammonia water, and keeping the nickel concentration in the supernatant of the reaction system to fluctuate within the range of 0-60 ppm.
The whole reaction process is started up, mother liquor is discharged from the concentrating equipment, and the discharging speed is consistent with the total feeding amount. The secondary particles are slowly grown by controlling the reaction parameters until the secondary particles with the average particle diameter of 3.2+/-0.3 mu m are obtained and the kettle is stopped.
Post-treatment: washing, centrifuging, drying, sieving and demagnetizing the reaction precipitation slurry to obtain the Ni with the composite structure 0.60 Co 0.10 Mn 0.30 (OH) 2 The SEM scanning electron microscope morphology result of the material is shown in FIG. 11, and the section view is shown in FIG. 12.
Preparing a positive electrode material: 2000g of solidPrecursor Li prepared in examples 2 CO 3 Mixing uniformly by a high-speed mixer according to the mol ratio of 1:1.05, sintering by a box-type furnace under the air atmosphere, slowly heating to 850 ℃, sintering at high temperature for 12 hours, cooling to room temperature, crushing and sieving to obtain the nickel-cobalt-manganese ternary positive electrode material, wherein the SEM scanning electron microscope morphology result graph is shown in figure 13, and the XRD graph is shown in figure 5.
Preparing a battery: electrochemical performance testing was performed using button half-electricity: the positive electrode material, conductive carbon black and a binder PVDF (polyvinylidene fluoride) are prepared according to the following proportion of 8:1:1 preparing slurry, coating the slurry on an aluminum foil to prepare a positive plate, wherein the negative plate adopts a metal lithium plate, and the electrolyte adopts 1mol/L LiPF 6 DMC (volume ratio 1:1), and assembling the battery shell, the positive electrode plate, the diaphragm, the elastic piece and the gasket into a button battery in a vacuum glove box. Electrochemical performance testing was performed using a blue-electric testing system, and specific electrochemical performance data are shown in table 3.
Comparative example 3
In this comparative example, a nickel ternary precursor material was prepared from a positive electrode material active material having two layers of internal porosity and one primary crystal grain in a long form, and Ni of the chemical formula was synthesized 0.62 Co 0.07 Mn 0.31 (OH) 2 。
Preparing a solution: 1. according to the proportion of the metal mole ratio of nickel to cobalt to manganese being 62:07:31, weighing nickel sulfate, cobalt sulfate and manganese sulfate to prepare 116g/L of uniformly mixed ternary metal salt solution.
2. Adding a certain amount of pure water, naOH solution (with the concentration of 32 wt%) and ammonia water (with the concentration of 21 wt%) into a reaction kettle, and uniformly stirring at the constant temperature of 50 ℃ to obtain a base solution with the pH of 11.7 and the ammonia concentration of 2.8 g/L;
preparing a precursor material: introducing a metal salt solution (the flow rate is 3.00 percent L/h of the volume of the reaction kettle) and an ammonia water (the flow rate is 1.11 percent L/h of the volume of the reaction kettle) into the reaction kettle filled with the base solution in the reaction process of stirring and 50 ℃ under the protection of nitrogen for 0-5h, controlling the pH value by finely adjusting the NaOH solution, slowly reducing the pH value from 11.7 to 11.4, and controlling the flow rate of the ammonia water to enable the ammonia concentration to fluctuate within 2.8+/-0.4 g/L;
continuously introducing a metal salt solution (the flow rate is 4.00 percent L/h of the volume of the reaction kettle) and an ammonia water (the flow rate is 1.50 percent L/h of the volume of the reaction kettle) into the reaction kettle in the reaction process of 5-32h, slowly reducing the pH value from 11.4 to 11.0 by fine-adjusting the NaOH solution, and controlling the flow rate of the ammonia water to enable the ammonia concentration to fluctuate within 2.0+/-0.4 g/L; and the nickel concentration in the supernatant of the reaction system was maintained to fluctuate in the range of 0-60 ppm.
During the reaction process of more than 32 hours, continuously introducing a metal salt solution (the flow rate is 5.00 percent L/h of the volume of the reaction kettle), a NaOH solution (the flow rate is 1.88 percent L/h of the volume of the reaction kettle) and ammonia water (the flow rate is 0.04 percent L/h of the volume of the reaction kettle) into the reaction kettle, enabling the pH to fluctuate within 10.9-11.1 by fine adjustment of the NaOH solution, enabling the ammonia concentration to fluctuate within 1.5+/-0.4 g/L by controlling the flow rate of the ammonia water, and keeping the nickel concentration in the supernatant of the reaction system to fluctuate within the range of 0-60 ppm.
The whole reaction process is to open the thickener, the thickener discharges mother liquor, and the discharge rate is consistent with the total feed amount. The secondary particles are slowly grown by controlling the reaction parameters until the secondary particles with the average particle diameter of 3.3+/-0.3 mu m are obtained, and the kettle is stopped.
Post-treatment: washing, centrifuging, drying, sieving and demagnetizing the reaction precipitation slurry to obtain the Ni with the composite structure 0.62 Co 0.07 Mn 0.31 (OH) 2 The SEM scanning electron microscope morphology result of the material is shown in FIG. 14, and the section view is shown in FIG. 15.
4. 2000g of the precursor Li prepared in the example 2 CO 3 Mixing uniformly by a high-speed mixer according to the mol ratio of 1:1.05, sintering by a box-type furnace under the air atmosphere, slowly heating to 850 ℃, sintering at high temperature for 12 hours, cooling to room temperature, crushing and sieving to obtain the nickel-cobalt-manganese ternary positive electrode material, wherein the SEM scanning electron microscope morphology result graph is shown in figure 16, and the XRD graph is shown in figure 5.
Preparing a battery: electrochemical performance testing was performed using button half-electricity: the positive electrode materialConductive carbon black, binder PVDF (polyvinylidene fluoride) according to 8:1:1 preparing slurry, coating the slurry on an aluminum foil to prepare a positive plate, wherein the negative plate adopts a metal lithium plate, and the electrolyte adopts 1mol/L LiPF 6 DMC (volume ratio 1:1), and assembling the battery shell, the positive electrode plate, the diaphragm, the elastic piece and the gasket into a button battery in a vacuum glove box. Electrochemical performance testing was performed using a blue-electric testing system, and specific electrochemical performance data are shown in table 3.
The results of the physical and chemical indices of the precursors of examples 1-2 and comparative examples 1-3 are shown in Table 1:
TABLE 1 physical and chemical indicators of precursor
Figure BDA0004031124030000161
Comparison of SEM, section views and physicochemical indexes of examples 1-2 and comparative examples 1-3:
1. comparison of example 1 and example 2 shows that: under the same preparation process conditions, even if the proportion of metal salt is changed, the chemical formula of the product is changed, but the internal structure is unchanged, and the physicochemical properties are at the same level, so that the process can be applied to the production of products with different element proportions.
2. Comparison of example 1 and comparative example 1 shows that: although the molecular formula of the product is the same, the sphericity of the precursor two particles prepared by the process is more excellent, and the particle size distribution is smaller.
3. Comparison of example 1 and comparative example 2 shows that: at the same level of BET, the particle size D50 of comparative example 2 was about 1 μm lower than that of example 1. Generally, the smaller the particle size, the larger the BET, but the product prepared by the process claimed herein possesses the same BET at a 31.9% increase in particle size. Under the same condition, the larger the secondary particles D50 are, the stronger the pressure bearing capacity is, the stronger the pressure-resistant, anti-cracking and anti-crushing capacity is, and the cycle performance can be improved. The larger the BET of the precursor is, the larger the BET of the prepared positive electrode material is, the larger the contact area between the positive electrode material and electrolyte is, the more side reactions are generated between the positive electrode material and the electrolyte, and the poorer the cycle performance is. Example 1 has a lower BET at the same particle size D50, improving the cycle performance of the battery.
4. Comparison of example 1 and comparative example 3 shows that: at the same level TD, the particle size D50 of comparative example 3 was about 0.8 μm lower than that of example 1, and the particle size distribution of comparative example 3 was higher than that of example 1. In general, the smaller the particle size, the wider the span and the larger the TD. The larger the secondary particles D50 under the same TD, the stronger the pressure bearing capacity, the stronger the pressure-resistant, anti-cracking and anti-crushing capacity, and the cycle performance can be improved. The product prepared by the process has the same TD (time division) under the condition that the particle size is increased by 23.9 percent and the span is smaller than 77.5 percent; the electrochemical properties can be improved.
5. Examples 1-2 have better sphericity than comparative examples 2-3, and even have sphericity superior to that of large particles of 10um, and the excellent sphericity is advantageous for improving the packing density of the positive electrode material. Meanwhile, example 1 has higher porosity of the outer shell than comparative examples 1 to 3, which is advantageous for migration of Li ions during charge and discharge of the battery and increases capacity of the battery.
Fig. 3 and 7 are sectional views of the precursors of examples 1 and 2, respectively, as can be seen from the figures, the ternary precursor prepared by the process has an inner core-shell structure and an outer core-shell structure, the secondary particle core has a honeycomb shape, the pores are uniformly distributed, the shell has a branched crystal shape, and the pores of the shell are uniformly distributed. FIGS. 10, 13 and 16 are cut precursor surfaces of comparative examples 1, 2 and 3, respectively, which are dendrite-shaped in comparison with the radial primary particles of comparative example 1, thus effectively resisting external pressure and transmitting internal stress, preventing the generation of cracks inside the particles; compared with the tangent plane of comparative examples 2-3, the primary crystal grain distribution is more uniform, the pore distribution of the inner core and the shell is more uniform, and the structure is favorable for the heat and stress transfer during the sintering of the precursor, reduces the internal stress of the anode material and improves the safety of battery operation. The core and shell of the embodiment and the structural distribution of its primary grains can be inherited to the positive electrode material.
The primary particles of comparative example 1 were in the form of coarse flakes, and the primary particles of examples 1-2 and comparative examples 2-3 were in the form of rods, and as can be seen from the primary particle sizes of examples 1-2 and comparative examples 2-3 of fig. 18, 19, 20, and 21, the primary particles of the positive electrode materials prepared from the precursors of examples 1-2 and comparative examples 2-3 had better uniformity in distribution, the average primary particle sizes (lengths) thereof were 0.41 μm, 0.44 μm, 0.57 μm, and 0.48 μm, respectively, and the more uniform the primary particle distribution, the more similar the charge and discharge times of the single particles of the positive electrode materials, so that overcharging of the single particles could be effectively prevented, and the safety performance of the battery could be improved. The dendrite-shaped structure in the precursor shell enables the precursor and the lithium salt to be fully mixed and subjected to reaction sintering, and uniformity of primary particles of the positive electrode material can be improved.
The results of the physical and chemical index of the positive electrode materials of examples 1 to 2 and comparative examples 1 to 3 are shown in Table 2.
TABLE 2 physical and chemical indicators of cathode materials
Figure BDA0004031124030000181
As can be seen from the physical and chemical indexes of the positive electrode materials in table 2, examples 1-2 and comparative examples 1-3 each have a low pH, and the residual alkali is low, which is advantageous for the stability of the battery. Meanwhile, compared with comparative examples 2-3, the sintered positive electrode material of example 1-2 has particles with uniform particle distribution consistent with the precursor and low BET, good particle distribution can improve the cycle performance of the positive electrode material, and lower BET can reduce the reaction with electrolyte and improve the stability of the battery.
The results of the electrochemical performance tests of examples 1-2 and comparative examples 1-3 are shown in Table 3.
TABLE 3 electrochemical Performance test results
Figure BDA0004031124030000182
Table 3 shows the electrochemical properties of examples 1-2 and comparative examples 1-3. As shown in the Table, the initial hematocrit of examples 1-2 and comparative examples 1-3 was 200.6mAh/g, 198.9mAh/g, 200mAh/g, 197.7mAh/g and 197.3mAh/g, respectively, and the positive electrode materials prepared from the five precursors all had good initial charge specific capacities. However, compared with comparative example 1, the first effect of example 1 is far higher than that of comparative example 1 under the condition of the same main content of example 1, because the battery prepared by the dendritic precursor inherits the morphology of primary grains of the precursor, the mass transfer performance of Li ions is promoted, and the deintercalation capability of Li ions of the material is improved.
As is clear from Table 3, the batteries prepared in examples 1-2 had capacity retention rates of 96.6% and 96.0% after 50 cycles, which were much higher than 95.4%, 95.3% and 95.2% of comparative examples 1-3. The specific capacity phase ratios of 1.0C/0.1C for examples 1-2 were 92.4% and 92.3%, respectively, much higher than 91.9%, 89.3% and 88.6% for comparative examples 1-3. The precursor has a shell branched crystal shape and uniformly distributed shell pores, so that the prepared anode material has uniform primary particles, and the cycle performance and the multiplying power performance of the battery are improved. The precursor shell dendritic structure enables the sintered positive electrode material to have strong ion transmission capacity and low BET, so that side reaction between the positive electrode material and electrolyte is reduced, and the cycle performance of the battery is improved.
As can be seen from the DCR properties of table 3, 50% of the discharge internal resistances of the batteries prepared from the precursors of examples 1-2 and comparative examples 2-3 were 21.9Ω, 23.0Ω, 28.4Ω and 24.6Ω, respectively, and the discharge internal resistances of examples 1-2 were much smaller than those of the other comparative examples, because the precursor dendrite structure was inherited into the positive electrode material, the running loss of the material was reduced, and the safety of the battery was improved. Meanwhile, as primary crystal grains in the precursor are in a branched crystal shape, the precursor is internally provided with pores which are uniformly distributed, and compared with a positive electrode material prepared by the radial precursor, the precursor can effectively relieve volume expansion in the charging and discharging processes and improve the safety and the cycle performance of the battery.
FIG. 5 shows XRD patterns of examples 1-2 and comparative examples 1-3 (examples 1, 2, comparative examples 1, 2, 3 in order from bottom to top), and it can be seen that the positive electrode materials prepared under each condition have a-NaFeO corresponding to the R3_m space group 2 The positive electrode material prepared by the method has a layered structure. The peak intensity ratios of I (003)/I (104) of examples 1-2 and comparative examples 2-3 were 1.45, 1.41, 1.39 and 1.40, respectively. Examples 1-2 had a larger peak intensity ratio of I (003)/I (104), and a lower Li/Ni mixing degree, which was more advantageous for the running stability of the battery, than comparative examples 2-3.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present application, and not for limiting the same; although the present application has been described in detail with reference to the foregoing embodiments, it should be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the corresponding technical solutions from the scope of the technical solutions of the embodiments of the present application.
Furthermore, those skilled in the art will appreciate that while some embodiments herein include some features but not others included in other embodiments, combinations of features of different embodiments are meant to be within the scope of the present application and form different embodiments. For example, in the claims below, any of the claimed embodiments may be used in any combination. The information disclosed in this background section is only for enhancement of understanding of the general background of the application and should not be taken as an acknowledgement or any form of suggestion that this information forms the prior art already known to a person skilled in the art.

Claims (10)

1. The dendritic positive electrode material precursor is characterized by comprising an inner core and an outer shell coating the inner core;
primary particles of the inner core are in loose honeycomb-like arrangement, and primary particles of the outer shell are in loose dendrite-like arrangement.
2. The dendritic cathode material precursor according to claim 1, characterized in that the dendritic cathode material precursor is a nickel-containing oxyhydrogen compound;
preferably, the dendrite arrangement of the primary particles of the shell is clustered;
preferably, the inner core has a porosity of 16-36% and the outer shell has a porosity of 7-27%;
preferably, the dendrite cathode material precursor has an overall average porosity of 11-31%;
preferably, the D50 of the core is 0.8-2.9 μm;
preferably, the ratio of the average radius of the inner core to the radius of the dendrite cathode material precursor is (0.3 to 0.6): 1, a step of;
preferably, the ratio of the average thickness of the outer shell to the radius of the dendrite cathode material precursor is (0.4-0.7): 1.
3. the dendritic positive electrode material precursor according to claim 1, characterized in that it has the chemical formula Ni x Co y Mn z M a (OH) 2 Wherein x is more than or equal to 0.5 and less than or equal to 1, y is more than or equal to 0 and less than or equal to 0.5, z is more than or equal to 0 and less than or equal to 0.5, and a is more than or equal to 0 and less than or equal to 0.3; m is at least one of Al, ti, zr, mo, cr, W, B, mg, ba, nb and Sr; preferably, y is more than or equal to 0 and less than or equal to 0.3, a is more than or equal to 0 and less than or equal to 0.1, and more preferably, x is more than or equal to 0.5 and less than or equal to 0.7,0 and a is less than or equal to 0.01;
Preferably, the inner core has a circular-like aperture therein and the outer shell has an irregular polygonal aperture therein;
preferably, the primary particles of the inner core are in the form of flakes;
preferably, the primary particles of the shell are rod-shaped with an aspect ratio of (6-14): 1.
4. the dendritic cathode material precursor according to any one of claims 1-3, characterized in that at least one of the following conditions is fulfilled:
d50 is 2-6. Mu.m, preferably 3-5. Mu.m;
BET of 5-18m 2 /g；
TD of 1.3-1.9g/cm 3 ；
Span is 0.3-0.5, span= (D90-D10)/D50;
E. the ratio of the average radius of the inner core to the radius of the dendrite cathode material precursor is (0.42-0.48): 1, a step of;
F. the ratio of the average thickness of the outer shell to the radius of the dendrite cathode material precursor is (0.52-0.58): 1, a step of;
G. the sphericity of the precursor is 92.00-98.00%.
5. A method of preparing the dendritic cathode material precursor according to any one of claims 1 to 4, comprising:
introducing a metal salt solution, a precipitator and a complexing agent into the base solution under the protection of inert gas to perform a first reaction to obtain the inner core;
continuing the second reaction and the third reaction to obtain the dendrite-shaped anode material precursor;
During the first reaction, the second reaction and the third reaction, the pH, the complexing agent concentration and the supernatant nickel content of the system are controlled independently.
6. The method according to claim 5, wherein the base liquid is a mixture of water, a precipitant and a complexing agent;
preferably, the pH value of the base solution is 11.3-12.4, and the ammonia concentration is 1.0-2.5g/L;
preferably, during the first reaction, the pH of the system is reduced from 11.0-12.0 to 10.7-11.6, the concentration of the complexing agent is controlled within the range of 2.3-3.2g/L, and the nickel content of the supernatant liquid of the system is maintained at 0-10ppm;
preferably, during the second reaction, the pH of the system is in the range of 10.6-11.8, the concentration of the complexing agent is controlled in the range of 2.3-3.2g/L, and the nickel content of the supernatant liquid of the system is maintained at 50-60ppm;
preferably, during the second reaction, the pH of the system is in the range of 10.5-11.8, the concentration of the complexing agent is controlled in the range of 0.8-2.6g/L, and the nickel content of the supernatant liquid of the system is maintained at 50-60ppm.
7. The method according to claim 5 or 6, wherein the metal salt solution comprises Ni and at least one of Co, mn, M being at least one of Al, ti, zr, mo, cr, W, B, mg, ba, nb and Sr;
Preferably, the precipitant comprises aqueous sodium hydroxide solution, and the complexing agent comprises aqueous ammonia;
preferably, in the process of the first reaction, the flow rate of the metal salt solution is 2.5-4.6% L/h of the volume of the reaction container, the flow rate of the sodium hydroxide aqueous solution is 1.0-2.0% L/h of the volume of the reaction container, and the flow rate of the ammonia water is 0.01-0.1% L/h of the volume of the reaction container;
preferably, in the process of the second reaction, the flow rate of the metal salt solution is 3.5-5.5% L/h of the volume of the reaction container, the flow rate of the sodium hydroxide aqueous solution is 1.0-2.0% L/h of the volume of the reaction container, and the flow rate of the ammonia water is 0.02-0.1% L/h of the volume of the reaction container;
preferably, in the process of the third reaction, the flow rate of the metal salt solution is 5.0-6.0% L/h of the volume of the reaction container, the flow rate of the sodium hydroxide aqueous solution is 1.6-2.8% L/h of the volume of the reaction container, and the flow rate of the ammonia water is 0.06-0.12% L/h of the volume of the reaction container;
preferably, the temperature of the first reaction is 40-70 ℃, the temperature of the second reaction is 40-70 ℃, and the temperature of the third reaction is 50-65 ℃;
preferably, the third reaction further comprises washing, solid-liquid separation, drying, sieving and demagnetizing after the end.
8. A lithium ion battery cathode material, characterized in that the raw material comprises the dendrite-shaped cathode material precursor according to any one of claims 1 to 5.
9. A lithium ion battery, characterized in that the raw material comprises the lithium ion battery positive electrode material according to claim 8.
10. A powered device comprising the lithium-ion battery of claim 9.
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