CN113880146B - Positive electrode material precursor, positive electrode material, preparation method and application of positive electrode material precursor and positive electrode material - Google Patents
Positive electrode material precursor, positive electrode material, preparation method and application of positive electrode material precursor and positive electrode material Download PDFInfo
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- CN113880146B CN113880146B CN202010633436.XA CN202010633436A CN113880146B CN 113880146 B CN113880146 B CN 113880146B CN 202010633436 A CN202010633436 A CN 202010633436A CN 113880146 B CN113880146 B CN 113880146B
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- positive electrode
- electrode material
- complexing agent
- material precursor
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- 239000007774 positive electrode material Substances 0.000 title claims abstract description 316
- 239000002243 precursor Substances 0.000 title claims abstract description 288
- 238000002360 preparation method Methods 0.000 title abstract description 52
- 229910052751 metal Inorganic materials 0.000 claims abstract description 128
- 239000002184 metal Substances 0.000 claims abstract description 120
- 238000000034 method Methods 0.000 claims abstract description 84
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 78
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 76
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 60
- 239000002245 particle Substances 0.000 claims abstract description 59
- 239000008139 complexing agent Substances 0.000 claims description 126
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 106
- 238000006243 chemical reaction Methods 0.000 claims description 46
- 238000001556 precipitation Methods 0.000 claims description 30
- 150000003839 salts Chemical class 0.000 claims description 24
- 229910017052 cobalt Inorganic materials 0.000 claims description 23
- 239000010941 cobalt Substances 0.000 claims description 23
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 23
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 17
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 15
- 239000001509 sodium citrate Substances 0.000 claims description 15
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 15
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- VBIXEXWLHSRNKB-UHFFFAOYSA-N ammonium oxalate Chemical compound [NH4+].[NH4+].[O-]C(=O)C([O-])=O VBIXEXWLHSRNKB-UHFFFAOYSA-N 0.000 claims description 2
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 2
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- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- DEFVIWRASFVYLL-UHFFFAOYSA-N ethylene glycol bis(2-aminoethyl)tetraacetic acid Chemical compound OC(=O)CN(CC(O)=O)CCOCCOCCN(CC(O)=O)CC(O)=O DEFVIWRASFVYLL-UHFFFAOYSA-N 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000004108 freeze drying Methods 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 150000003840 hydrochlorides Chemical class 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000003273 ketjen black Substances 0.000 description 1
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 description 1
- 239000011565 manganese chloride Substances 0.000 description 1
- 235000002867 manganese chloride Nutrition 0.000 description 1
- 229940099607 manganese chloride Drugs 0.000 description 1
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052754 neon Inorganic materials 0.000 description 1
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 description 1
- 229940078494 nickel acetate Drugs 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- 239000011736 potassium bicarbonate Substances 0.000 description 1
- 235000015497 potassium bicarbonate Nutrition 0.000 description 1
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 235000011181 potassium carbonates Nutrition 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- 235000011118 potassium hydroxide Nutrition 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 238000007430 reference method Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 1
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/006—Compounds containing, besides nickel, two or more other elements, with the exception of oxygen or hydrogen
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/40—Nickelates
- C01G53/42—Nickelates containing alkali metals, e.g. LiNiO2
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- 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
-
- 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
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
-
- 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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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
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- 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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
The invention relates to the field of lithium batteries, and discloses a positive electrode material precursor, a positive electrode material, preparation methods and applications thereof, wherein the precursor has a formula of Ni x Co y M z (OH) 2 The method comprises the steps of carrying out a first treatment on the surface of the M is selected from at least one of Fe, cr, cu, ti, mg, W, mo, nb, ca, zn, sn, zr, ga, mn and Al; x is more than or equal to 0.3 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 x+y+z=1; the relative standard deviation of the Ni, co and M content of the metal components in the different particles of the precursor satisfies: RSD (Ni) is more than or equal to 0 and less than or equal to 0.15, RSD (Co) is more than or equal to 0 and less than or equal to 0.15, RSD (M) is more than or equal to 0 and less than or equal to 0.15. The precursor provided by the invention has good sphericity, monodispersity and content consistency of metal components, and the positive electrode material prepared from the precursor is used for a lithium battery, so that the charge-discharge cycling stability of the lithium battery can be effectively improved.
Description
Technical Field
The invention relates to the field of lithium batteries, in particular to a positive electrode material precursor, a positive electrode material, a preparation method and application thereof.
Background
The lithium ion battery has the advantages of high energy density, high output voltage, small self-discharge, excellent cycle performance, no memory effect and the like, and is widely applied to the fields of portable electronic products, electric tools, electric automobiles and the like. In particular, the new energy automobile popularization policy of the governments of various countries is continuously upgraded in recent years, and the rapid development of the power type lithium ion battery is promoted.
The positive electrode material is a key core component of the lithium ion battery, and determines the energy density and the endurance mileage of the lithium ion battery, and occupies about 40% of the cost of the battery. With the continuous improvement of the requirements of people on the endurance mileage of the electric automobile, the ternary positive electrode material with higher energy density gradually becomes the mainstream positive electrode material for the passenger car. However, the coulombic efficiency, the cycle stability and the rate capability of the ternary cathode material are problematic, and especially the disadvantage of poor cycle stability greatly limits the commercialization process thereof.
The method for improving the cycling stability of the ternary material is mainly by a modification technology of ion doping and surface coating. CN102210045B discloses that by doping at least one metal of Mg, ti, zr, al and Fe and S in the ternary positive electrode material, the cycling stability and safety of the ternary material at high voltages are improved. CN1622367a discloses a ternary material having a surface coating composition MXO k Wherein M is at least one element selected from the group consisting of alkali metals, alkaline earth metals, group 13 elements, group 14 elements, transition metals and rare earth elements, X is an element capable of forming a double bond with oxygen, and k is a number of 2 to 4, improving the cycle stability of the positive electrode material. However, the cycle stability of the modified positive electrode material is still to be improved.
Disclosure of Invention
The invention aims to solve the problem of poor charge-discharge cycle stability of a positive electrode material in the prior art, and provides a positive electrode material precursor, a positive electrode material, a preparation method and application thereof.
In order to achieve the above object, a first aspect of the present invention provides a positive electrode material precursor having the expression of Ni x Co y M z (OH) 2 ；
Wherein M is at least one selected from Fe, cr, cu, ti, mg, W, mo, nb, ca, zn, sn, zr, ga, mn and Al;
x is more than or equal to 0.3 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 x+y+z=1;
the relative standard deviations of the Ni, co and M contents of the metal components in different particles of the positive electrode material precursor respectively satisfy the following conditions: RSD (Ni) is more than or equal to 0 and less than or equal to 0.15, RSD (Co) is more than or equal to 0 and less than or equal to 0.15, RSD (M) is more than or equal to 0 and less than or equal to 0.15.
In a second aspect, the present invention provides a method for preparing a precursor of a positive electrode material, the method comprising the steps of:
(1) Mixing a solution containing a metal source, a precipitant solution and a complexing agent solution containing a first complexing agent and a second complexing agent for precipitation reaction;
(2) Carrying out solid-liquid separation and drying on the product obtained by the precipitation reaction in the step (1);
wherein the metal source comprises a nickel source, optionally a cobalt source, and optionally a M source, M being selected from at least one of Fe, cr, cu, ti, mg, W, mo, nb, ca, zn, sn, zr, ga, mn and Al;
based on the total amount of the metal sources, the nickel source is used in an amount of 30-100 mol%, the cobalt source is used in an amount of 0-50 mol%, and the M source is used in an amount of 0-50 mol% based on metal elements;
the types of the first complexing agent and the second complexing agent are such that the relative standard deviations of the contents of the metal components Ni, co and M in different particles of the prepared positive electrode material precursor respectively satisfy the following conditions: RSD (Ni) is more than or equal to 0 and less than or equal to 0.15, RSD (Co) is more than or equal to 0 and less than or equal to 0.15, RSD (M) is more than or equal to 0 and less than or equal to 0.15.
In a third aspect, the present invention provides a method for preparing a precursor of a positive electrode material, the method comprising the steps of:
(1) Mixing a solution containing a metal source, a precipitant solution and a complexing agent solution containing a first complexing agent and a second complexing agent for precipitation reaction;
(2) Carrying out solid-liquid separation and drying on the product obtained by the precipitation reaction in the step (1);
wherein the metal source comprises a nickel source, optionally a cobalt source, and optionally a M source, M being selected from at least one of Fe, cr, cu, ti, mg, W, mo, nb, ca, zn, sn, zr, ga, mn and Al;
based on the total amount of the metal sources, the nickel source is used in an amount of 30-100 mol%, the cobalt source is used in an amount of 0-50 mol%, and the M source is used in an amount of 0-50 mol% based on metal elements;
the first complexing agent is selected from an ammonium ion donor and/or an alcohol amine complexing agent;
the second complexing agent is at least one of carboxylic acid complexing agent, carboxylic acid salt complexing agent, amino carboxylic acid complexing agent and hydroxyamino carboxylic acid complexing agent.
A fourth aspect of the present invention provides a positive electrode material precursor prepared by the method of the second or third aspect.
In a fifth aspect, the present invention provides a method for preparing a positive electrode material, the method comprising mixing a lithium source with the positive electrode material precursor according to the first or fourth aspect, and then firing.
A sixth aspect of the present invention provides a positive electrode material produced by the production method of the fifth aspect.
A seventh aspect of the present invention provides a positive electrode material precursor according to the first or fourth aspect or a positive electrode material according to the sixth aspect for use in a lithium battery.
The positive electrode material precursor prepared by the technical scheme of the invention has good sphericity, monodispersity and consistency of metal component content, and the positive electrode material prepared by the positive electrode material precursor has good electrochemical performance when used in a lithium battery, and the retention rate of 100 cycles of cycle capacity can reach more than 96.9 percent.
Drawings
FIG. 1 is an SEM image of a positive electrode material precursor prepared according to example 1 of the present invention;
FIG. 2 is an XRD pattern of a positive electrode material precursor prepared in example 1 of the present invention;
fig. 3 is a graph showing the charge and discharge cycle results of the lithium battery prepared in example 1 of the present invention at a 1C rate;
fig. 4 is a graph showing the charge and discharge cycle results of the lithium battery manufactured in comparative example 1 according to the present invention at a 1C rate;
fig. 5 is a graph showing the charge and discharge cycle results at 1C rate of the lithium battery manufactured in comparative example 2 of the present invention.
Detailed Description
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
The inventor of the invention discovers through researches that the composition and the structure of the positive electrode material have important influence on the charge-discharge cycle stability of the positive electrode material, the composition and the structure of the positive electrode material are mainly determined by positive electrode material precursors, the larger the composition difference among the positive electrode material precursor particles is, the more obvious the overcharging or overdischarging effect among different particles of the obtained positive electrode material is, and the worse the charge-discharge cycle stability of the positive electrode material is, so that the preparation of the positive electrode material precursors with good consistency of the particle composition is very critical on a microscopic level. The inventor of the invention discovers through further research that under the condition that the positive electrode material precursor contains specific content of Ni, optional Co and optional M (wherein M is at least one of Fe, cr, cu, ti, mg, W, mo, nb, ca, zn, sn, zr, ga, mn and Al), and the relative standard deviation of the content of metal components in different particles of the positive electrode material precursor is not more than 0.15 respectively, the positive electrode material precursor has better sphericity, monodispersity and consistency and higher cycle stability, and the electrochemical performance of the positive electrode material prepared from the precursor is effectively improved.
In a first aspect, the present invention provides a positive electrode material precursor having the expression Ni x Co y M z (OH) 2 ；
Wherein M is at least one selected from Fe, cr, cu, ti, mg, W, mo, nb, ca, zn, sn, zr, ga, mn and Al;
x is more than or equal to 0.3 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 x+y+z=1;
the relative standard deviations of the Ni, co and M contents of the metal components in different particles of the positive electrode material precursor respectively satisfy the following conditions: RSD (Ni) is more than or equal to 0 and less than or equal to 0.15, RSD (Co) is more than or equal to 0 and less than or equal to 0.15, RSD (M) is more than or equal to 0 and less than or equal to 0.15.
It is understood that RSD (Ni) refers to the relative standard deviation of the content of the metal component Ni in the precursor particles of different cathode materials, and is used to describe the fluctuation of the content of the metal component Ni in the precursor particles of different cathode materials, and the smaller the value, the better the consistency of the content of the component Ni among the different particles. The RSD (Co) refers to the relative standard deviation of the content of the metal component Co in the precursor particles of different cathode materials, and is used for describing the fluctuation condition of the content of the metal component Co in the precursor particles of different cathode materials, and the smaller the value is, the better the consistency of the content of the component Co among different particles is indicated. The RSD (M) refers to the relative standard deviation of the content of the metal component M in the precursor particles of different cathode materials, and is used for describing the fluctuation condition of the content of the metal component M in the precursor particles of different cathode materials, and the smaller the value is, the better the consistency of the content of the component M among different particles is indicated.
According to the present invention, in order to further improve the electrochemical performance of the positive electrode material precursor, it is preferable that the relative standard deviations of the contents of the metal components Ni, co, and M in the different particles of the positive electrode material precursor respectively satisfy: RSD (Ni) is more than or equal to 0 and less than or equal to 0.1, RSD (Co) is more than or equal to 0 and less than or equal to 0.1, RSD (M) is more than or equal to 0 and less than or equal to 0.1.
According to the present invention, it is preferable that the relative standard deviation of the Ni content of the metal component in the different particles of the positive electrode material precursor satisfies: RSD (Ni) is 0.ltoreq.0.1, more preferably RSD (Ni) is 0.ltoreq.0.05.
According to the present invention, preferably, the relative standard deviation of the content of the metal component Co in the different particles of the positive electrode material precursor satisfies: RSD (Co) is more than or equal to 0 and less than or equal to 0.1, and RSD (Co) is more preferably more than or equal to 0 and less than or equal to 0.05.
According to the present invention, it is preferable that the relative standard deviation of the content of the metal component M in the different particles of the positive electrode material precursor satisfies: RSD (M) is more than or equal to 0 and less than or equal to 0.1, and RSD (M) is more than or equal to 0 and less than or equal to 0.05.
In the present invention, the metal component content is measured by an X-ray energy spectrum scanner (EDS). Specifically, the invention adopts an X-ray energy spectrum scanner (EDS) to measure the metal components in single positive electrode material precursor particles, tests the compositions of metal Ni, co and M scanned by EDS energy spectrum in 400 particles, calculates the relative standard deviation of the Ni, co and M content in 400 particles, and respectively calculates as RSD (Ni), RSD (Co) and RSD (M).
According to the invention, preferably 0.6.ltoreq.x.ltoreq. 0.95,0.025.ltoreq.y.ltoreq. 0.2,0.025.ltoreq.z.ltoreq.0.2.
According to the present invention, in order to further improve the electrochemical properties of the positive electrode material precursor, preferably, M is Mn and/or Al.
The inventor of the invention discovers through research that in the process of preparing the precursor of the positive electrode material, by adding two types of complexing agents, the precursor particles of the positive electrode material with good sphericity, good monodispersity and good consistency of metal component content can be obtained, and the precursor with the characteristics has better electrochemical performance and better charge-discharge cycling stability, and can be used in lithium batteries with high energy density.
In a second aspect, the present invention provides a method of preparing a precursor of a positive electrode material, the method comprising the steps of:
(1) Mixing a solution containing a metal source, a precipitant solution and a complexing agent solution containing a first complexing agent and a second complexing agent for precipitation reaction;
(2) Carrying out solid-liquid separation and drying on the product obtained by the precipitation reaction in the step (1);
wherein the metal source comprises a nickel source, optionally a cobalt source, and optionally a M source, M being selected from at least one of Fe, cr, cu, ti, mg, W, mo, nb, ca, zn, sn, zr, ga, mn and Al;
Based on the total amount of the metal sources, the nickel source is used in an amount of 30-100 mol%, the cobalt source is used in an amount of 0-50 mol%, and the M source is used in an amount of 0-50 mol% based on metal elements;
the types of the first complexing agent and the second complexing agent are such that the relative standard deviations of the contents of the metal components Ni, co and M in different particles of the prepared positive electrode material precursor respectively satisfy the following conditions: RSD (Ni) is more than or equal to 0 and less than or equal to 0.15, RSD (Co) is more than or equal to 0 and less than or equal to 0.15, RSD (M) is more than or equal to 0 and less than or equal to 0.15.
According to the present invention, preferably, the kinds of the first complexing agent and the second complexing agent are such that the relative standard deviations of the contents of the metal components Ni, co and M in the different particles of the prepared positive electrode material precursor satisfy respectively: RSD (Ni) is more than or equal to 0 and less than or equal to 0.1, and RSD (Ni) is more preferably more than or equal to 0 and less than or equal to 0.05; RSD (Co) is more than or equal to 0 and less than or equal to 0.1, and more preferably RSD (Co) is more than or equal to 0 and less than or equal to 0.05; RSD (M) is more preferably 0.ltoreq.RSD (M) is more preferably 0.ltoreq.0.05.
According to the present invention, preferably, the first complexing agent is selected from ammonium ion donors and/or alcohol amine complexing agents.
According to the present invention, preferably, the second complexing agent is selected from at least one of carboxylic acid-based complexing agents, carboxylic acid salt-based complexing agents, amino carboxylic acid-based complexing agents, and hydroxyamino carboxylic acid-based complexing agents.
In a third aspect, the present invention provides a method of preparing a precursor of a positive electrode material, the method comprising the steps of:
(1) Mixing a solution containing a metal source, a precipitant solution and a complexing agent solution containing a first complexing agent and a second complexing agent for precipitation reaction;
(2) Carrying out solid-liquid separation and drying on the product obtained by the precipitation reaction in the step (1);
wherein the metal source comprises a nickel source, optionally a cobalt source, and optionally a M source, M being selected from at least one of Fe, cr, cu, ti, mg, W, mo, nb, ca, zn, sn, zr, ga, mn and Al;
based on the total amount of the metal sources, the nickel source is used in an amount of 30-100 mol%, the cobalt source is used in an amount of 0-50 mol%, and the M source is used in an amount of 0-50 mol% based on metal elements;
the first complexing agent is selected from an ammonium ion donor and/or an alcohol amine complexing agent;
the second complexing agent is at least one of carboxylic acid complexing agent, carboxylic acid salt complexing agent, amino carboxylic acid complexing agent and hydroxyamino carboxylic acid complexing agent.
More preferably, the ammonium ion donor is selected from at least one of ammonia water, ammonium oxalate, ammonium carbonate and ammonium bicarbonate.
More preferably, the alcohol amine complexing agent is selected from at least one of ethanolamine, diethanolamine, 2-dibutylamino ethanol, 2-diethylaminoethanol and N, N-diethylethanolamine.
More preferably, the aminocarboxylic acid type complexing agent is selected from at least one of sodium nitrilotriacetate, potassium nitrilotriacetate, ethylenediamine tetraacetic acid and salts thereof, and diethylenetriamine pentaacetic acid.
More preferably, the hydroxyaminocarboxylic acid-based complexing agent is selected from at least one of hydroxyethylenediamine tetraacetic acid (HEDTA) and salts thereof, ethyleneglycol bis (beta-diaminoethyl) diethyl ether-N, N, N 'N' -tetraacetic acid (EGTA) and salts thereof, and dihydroxyglycine and salts thereof.
More preferably, the carboxylic acid-based complexing agent and/or carboxylic acid salt-based complexing agent is at least one selected from oxalic acid and salts thereof, tartaric acid and salts thereof, citric acid and salts thereof, gluconic acid and salts thereof, carboxymethyl hydroxy malonic acid (CMOM) and salts thereof, carboxymethyl hydroxy succinic acid (CMOS) and salts thereof, and hydroxyethyl glycine (DHEG) and salts thereof, more preferably citric acid and/or citric acid salt, still more preferably at least one selected from sodium citrate, potassium citrate, and ferric ammonium citrate.
The first complexing agent and the second complexing agent of the preferable types can be used together to further improve the monodispersity of the precursor of the positive electrode material and the consistency of the content of the metal component.
According to a preferred embodiment of the present invention, the nickel source is used in an amount of 60 to 95 mole%, the cobalt source is used in an amount of 2.5 to 20 mole%, and the M source is used in an amount of 2.5 to 20 mole%, based on the total amount of the metal sources, based on the metal elements. The electrochemical performance of the positive electrode material precursor can be further improved by adopting the preferred embodiment.
According to the present invention, the nickel source is preferably used in an amount of 60 to 95 mol%, for example, 60 mol%, 65 mol%, 70 mol%, 75 mol%, 80 mol%, 85 mol%, 90 mol%, 95 mol%, and any value between any two values, based on the total amount of the metal sources, based on the metal elements.
According to the present invention, the cobalt nickel source is preferably used in an amount of 2.5 to 20 mol%, for example, may be 2.5 mol%, 5 mol%, 10 mol%, 15 mol%, 20 mol%, and any value between any two values, based on the total amount of the metal sources, based on the metal element.
According to the present invention, the M source is preferably used in an amount of 2.5 to 20 mol%, for example, may be 2.5 mol%, 5 mol%, 10 mol%, 15 mol%, 20 mol%, and any value between any two values, based on the total amount of the metal sources, based on the metal elements.
According to the present invention, in order to further improve the electrochemical properties of the positive electrode material precursor, preferably, M is Mn and/or Al.
According to the present invention, the molar concentration of the metal source-containing solution is preferably 0.01 to 5mol/L (for example, may be 0.01mol/L, 0.1mol/L, 0.5mol/L, 1mol/L, 1.5mol/L, 2mol/L, 2.5mol/L, 3mol/L, 3.5mol/L, 4mol/L, 4.5mol/L, 5mol/L, and any value between any two values), more preferably 1 to 2mol/L, in terms of the metal element.
According to the present invention, the kind of the nickel source is not particularly limited, and preferably, the nickel source is selected from at least one of sulfate, nitrate, acetate and hydrochloride of nickel; more preferably, the nickel source is selected from at least one of nickel sulfate, nickel nitrate, nickel acetate, and nickel chloride.
According to the present invention, the kind of the cobalt source is not particularly limited, and preferably, the cobalt source is selected from at least one of sulfate, nitrate, acetate and hydrochloride of cobalt; more preferably, the cobalt source is selected from at least one of cobalt sulfate, cobalt nitrate, cobalt acetate, and cobalt chloride.
According to the present invention, the kind of the M source is not particularly limited, and preferably the M source is selected from water-soluble salts of M, more preferably at least one of sulfate, nitrate, acetate and hydrochloride of M. More preferably, the M source is selected from at least one of sulfates, nitrates, acetates and hydrochlorides of manganese and/or aluminum, further preferably at least one of manganese sulfate, manganese nitrate, manganese acetate, manganese chloride, aluminum nitrate, aluminum chloride, aluminum acetate and aluminum sulfate.
According to the present invention, the precipitant solution is preferably used in an amount of 100 to 300 parts by mole, preferably 150 to 250 parts by mole, with respect to 100 parts by mole of the solution of the metal source.
According to the present invention, the amount of the precipitant to be used is selected to be wide in terms of being able to satisfy the precipitation reaction of the metal source, and the concentration of the precipitant solution is preferably 0.02 to 10mol/L, for example, may be 0.02mol/L, 0.1mol/L, 0.5mol/L, 1mol/L, 2mol/L, 3mol/L, 4mol/L, 5mol/L, 6mol/L, 7mol/L, 8mol/L, 9mol/L, 10mol/L, and any value between any two values, more preferably 2 to 8mol/L, and further preferably 2 to 6mol/L.
According to the present invention, the type of the precipitant is selected from a wide range so as to be able to satisfy the precipitation reaction of the metal source, and preferably the precipitant is at least one selected from the group consisting of hydroxides, carbonates and bicarbonates of alkali metals.
More preferably, the alkali metal is selected from at least one of Li, na, and K.
According to a preferred embodiment of the present invention, the precipitating agent is selected from at least one of sodium hydroxide, sodium carbonate, sodium bicarbonate, potassium hydroxide, potassium carbonate, potassium bicarbonate, lithium hydroxide, lithium carbonate and lithium bicarbonate.
According to the present invention, in order to further improve the sphericity, monodispersity and uniformity of the metal component content of the positive electrode material precursor, it is preferable that the complexing agent solution is used in an amount of 5 to 200 parts by mole, preferably 50 to 150 parts by mole, with respect to 100 parts by mole of the metal source solution.
According to the present invention, it is preferable that the concentration of the first complexing agent in the complexing agent solution is 0.01 to 16mol/L, preferably 2 to 10mol/L, more preferably 2 to 6mol/L. The preferable concentration can further improve the monodispersity of the prepared positive electrode material precursor and the consistency of the content of the metal component.
According to the present invention, preferably, the molar concentration ratio of the second complexing agent to the first complexing agent in the complexing agent solution is from 0.01 to 2, more preferably from 0.1 to 1.5.
According to the present invention, preferably, in step (1), the conditions of the precipitation reaction include: the temperature is 20-70deg.C, preferably 45-60deg.C; the pH value is 8-14, preferably 10-12; the time is not less than 5 hours, preferably 24-72 hours. The adoption of the preferable precipitation reaction conditions can better control the crystal growth of the precursor of the positive electrode material, thereby further improving the monodispersity of the precursor of the obtained positive electrode material and the consistency of the content of the metal component.
It should be understood that the control of the pH may be to control a constant pH during the reaction time, or to vary the pH of the reaction process according to the product objective, but the range of pH variation should preferably be within the above-mentioned reaction system range.
According to the present invention, preferably, the precipitation reaction is performed under stirring.
More preferably, the stirring speed is 50-1200r/min, for example, 50r/min, 80r/min, 100r/min, 200r/min, 300r/min, 400r/min, 500r/min, 600r/min, 700r/min, 800r/min, 900r/min, 1000r/min, 1100r/min, 1200r/min, and any value between any two values, further preferably 600-1000r/min.
According to the present invention, the drying conditions are not particularly limited, and preferably include: the temperature is 50-180deg.C, preferably 70-130deg.C; the time is 4-24 hours, preferably 8-20 hours.
The drying method according to the present invention may be a method conventional in the art, such as vacuum drying, air drying, freeze drying or oven drying.
According to the present invention, preferably, in step (1), the mixing includes: and adding the solution containing the metal source, the precipitant solution and the complexing agent solution containing the first complexing agent and the second complexing agent into the reaction kettle in parallel.
According to the present invention, the addition rates of the metal source-containing solution, the precipitant solution, and the complexing agent solution containing the first complexing agent and the second complexing agent are selected to be wide as long as the addition rates are such that the pH of the mixed solution obtained by co-current addition of the materials in step (1) to the reaction vessel reaches the pH value range in the above-mentioned precipitation reaction conditions, preferably the addition rate of the metal source-containing solution is 10 to 200mL/h, more preferably 20 to 100mL/h, based on 1L of the total amount of the metal source-containing solution.
More preferably, the precipitant solution is added at a rate of 10 to 200mL/h, more preferably 20 to 100mL/h, based on 1L of the total precipitant solution.
More preferably, the complexing agent solution is added at a rate of from 10 to 200mL/h, more preferably from 20 to 100mL/h, based on 1L of the total complexing agent solution containing the first complexing agent and the second complexing agent.
The addition rate of the metal source-containing solution is 10 to 200mL/h based on 1L of the total metal source-containing solution, which means that the addition rate of the metal source-containing solution is 10 to 200mL/h when the total metal source-containing solution is 1L, and correspondingly, the addition rate of the metal source-containing solution is 5 to 100mL/h when the total metal source-containing solution is 0.5L; accordingly, when the total amount of the solution containing the metal source is 5L, the addition rate of the solution containing the metal source is 50 to 1000mL/h. The speed of addition of the precipitant solution and the complexing agent solution comprising the first complexing agent and the second complexing agent is as described above.
According to the present invention, the method of solid-liquid separation in the step (2) is not particularly limited, as long as the precursor obtained is separated, and for example, a filtration method or a centrifugation method may be employed.
According to the present invention, preferably, the method further comprises washing the solid product obtained by the solid-liquid separation.
According to the present invention, the kind of the washing solvent used for the washing is not particularly limited, and may be a washing solvent conventionally used in the art, such as water (preferably deionized water).
In a fourth aspect, the present invention provides a positive electrode material precursor prepared by the preparation method according to the second or third aspect.
The structural composition and properties of the positive electrode material precursor have been described in detail in the first aspect, and the description thereof will not be repeated here.
In a fifth aspect, the present invention provides a method for preparing a positive electrode material, the method comprising mixing a lithium source with the positive electrode material precursor of the first or fourth aspect, and then firing.
According to the present invention, preferably, the conditions of the firing include: roasting for 10-48h at 300-1200 ℃ in an oxygen-containing atmosphere; more preferably, the pre-firing is performed at 400-600 ℃ for 2-8 hours, followed by the firing at 800-1000 ℃ for 10-24 hours.
According to the present invention, the oxygen-containing atmosphere is not particularly limited, and the oxygen-containing atmosphere may be air or a mixture of oxygen and an inert gas. The inert gas may be a common inert gas such as at least one of helium, neon, and argon.
The content of oxygen in the oxygen-containing atmosphere is not particularly limited as long as the effect of calcination can be advantageously improved, and preferably the content of oxygen in the oxygen-containing atmosphere is 15 to 30% by volume.
According to the present invention, preferably, the molar ratio of the lithium source to the positive electrode material precursor is 0.9 to 1.3:1 in terms of metal element, and for example, may be 0.9: 1. 0.95: 1.1:1. 1.05: 1. 1.1:1. 1.15: 1. 1.2: 1. 1.25: 1. 1.3:1, and any value between any two values, more preferably 0.95-1.1:1. it is understood that the molar amount of the positive electrode material precursor in terms of the metal element refers to the total molar amount of Ni, co, and M in the positive electrode material precursor.
According to the present invention, the kind of the lithium source is not particularly limited, and preferably the lithium source is a lithium salt, and more preferably the lithium salt is at least one selected from the group consisting of lithium nitrate, lithium chloride, lithium carbonate, lithium bicarbonate, lithium hydroxide and lithium acetate.
According to the present invention, in order to make the mixing of the lithium source and the positive electrode material precursor more uniform, it is preferable that the mixing includes ball milling the lithium source and the positive electrode material precursor. The time of the ball milling is preferably 10 to 300min, more preferably 20 to 120min.
In a sixth aspect, the present invention provides a positive electrode material produced by the production method of the fifth aspect. The positive electrode material has better electrochemical performance and better charge-discharge cycle stability.
In a seventh aspect, the present invention provides a positive electrode material precursor according to the first aspect or the fourth aspect or the use of the positive electrode material according to the sixth aspect in a lithium battery. The lithium battery prepared from the positive electrode material precursor or the positive electrode material has better electrochemical performance and better charge-discharge cycle stability.
According to the present invention, the structural composition of the lithium battery is a structural composition conventional in the art, for example, including a positive electrode, a negative electrode, a separator and an electrolyte. The negative electrode, the separator and the electrolyte are not particularly limited in the present invention, and may be selected according to actual needs by those skilled in the art. For example, in one embodiment of the present invention, the negative electrode uses metallic lithium, the separator uses Cellgard 2400 polypropylene separator in the United states, and the electrolyte uses 1mol/L LiPF 6 The solution, solvent is a mixed solvent of Ethylene Carbonate (EC) and dimethyl carbonate (DMC) in a volume ratio of 1:1.
According to the application of the invention, the positive electrode material precursor provided by the invention is prepared into a positive electrode material and further prepared into a positive electrode, and the positive electrode material precursor is used in a lithium battery. Preferably, the positive electrode material is mixed with a conductive agent and a binder, then coated and sliced, and the obtained slice is used as the positive electrode of the lithium battery.
According to the present invention, the conductive agent and the binder may be various conductive agents and binders conventionally used in the art, and for example, the conductive agent may be at least one selected from acetylene black, ketjen black, graphite, carbon tube, and graphene. The binder may be at least one selected from polyvinylidene fluoride (PVDF), polyvinyl alcohol (PVA), and sodium carboxymethyl cellulose (CMC).
According to the present invention, the conductive agent and the binder may be used in amounts conventional in the art, for example, the positive electrode material may have a mass content of 50 to 98%, preferably 70 to 95%, the conductive agent may have a mass content of 1 to 25%, preferably 2.5 to 15%, and the binder may have a mass content of 1 to 25%, preferably 2.5 to 15%, based on the total amount of the positive electrode.
According to the present invention, the lithium battery may be assembled in an apparatus conventionally used in the art, for example, in an inert atmosphere glove box in which moisture and oxygen contents are less than 0.1ppm.
Specific methods for preparing a lithium battery using the positive electrode material precursor or positive electrode material according to the present invention are well known in the art and will not be described herein.
The present invention is not particularly limited in the type of battery, for example, in one embodiment of the present invention, the type of battery is 2032 button battery. In the present invention, the electrochemical performance of lithium batteries can be tested using methods conventional in the art, for example, testing can be performed on a new wire BTS4000 system. The electrochemical performance test conditions include: the temperature is 25 ℃; the voltage range is 2.5-4.3V.
The present invention will be described in detail by examples. In the following examples of the present invention,
the metal component content was obtained by means of an X-ray energy spectrum scanner (EDS) of uk Oxford Instruments;
the XRD pattern was measured by an X-ray diffractometer of the model D8 Advance SS of Bruce, germany;
the shape and monodispersity of the positive electrode material precursor are analyzed by a scanning electron microscope of the model ZEISS Merlin of the company ZEISS, germany;
the polypropylene separator is a commercial product with the brand of Celllgard 2400;
the electrochemical performance of the lithium battery under the 1C multiplying power is tested on a Xinwei BTS4000 system, and the temperature of the electrochemical performance test is 25 ℃; the voltage range is 2.5-4.3V.
Example 1
This example is used to illustrate the positive electrode material precursor and positive electrode material prepared by the present invention and evaluation.
1. Preparation of positive electrode material precursor
(1) Preparing a metal sulfate solution (comprising nickel sulfate, cobalt sulfate and manganese sulfate) with the concentration of 2mol/L of metal ions (wherein the molar ratio of nickel, cobalt and manganese is 8:1:1); preparing NaOH solution with the concentration of 4 mol/L; preparing complexing agent solution, wherein the concentration of ammonia water is 2mol/L, and the molar ratio of sodium citrate to the concentration of ammonia water is 1;
and (3) simultaneously and parallelly adding the prepared sulfate solution, naOH solution and complexing agent solution into a reaction kettle under the stirring state to perform precipitation reaction, wherein the dosage of the NaOH solution is 200 mol parts and the dosage of the complexing agent solution is 100 mol parts relative to 100 mol parts of the metal source solution. The addition rate of the sulfate solution was 60mL/h relative to 1L of sulfate solution; the adding speed of the complexing agent solution is 60mL/h; controlling the adding speed of NaOH solution to make the pH value of the reaction system be 11; in the precipitation reaction, the stirring speed was controlled at 600rpm, the reaction temperature was 55℃and the reaction time was 48 hours (addition was stopped after 48 hours of co-current addition), to obtain a reaction slurry.
(2) And after the reaction slurry is naturally cooled, carrying out vacuum suction filtration on the reaction slurry, washing the obtained filter residue with deionized water for 3 times, and drying and dehydrating the filter residue in a vacuum drying oven at 120 ℃ for 12 hours to obtain a positive electrode material precursor S-1.
2. Evaluation of the precursor of the cathode Material
The SEM diagram of the obtained positive electrode material precursor S-1 is shown in FIG. 1, and as can be seen from FIG. 1, the obtained positive electrode material precursor has good sphericity and monodispersity;
as shown in fig. 2, the XRD pattern of the obtained positive electrode material precursor S-1 shows that the obtained positive electrode material precursor is very sharp in (001) diffraction peak around the 2θ angle of 19.6 °, (100) diffraction peak around the 2θ angle of 33.4 °, and (101) diffraction peak around the 2θ angle of 38.8 °, indicating that the crystal structure of the obtained positive electrode material precursor is well developed;
EDS spectrum scanning is carried out on 400 particles of the obtained positive electrode material precursor S-1, and relative standard deviations of the contents of the metal components Ni, co and Mn in the 400 particles are shown in table 1.
3. Preparation and evaluation of cathode Material
Taking the obtained positive electrode material precursor and lithium source LiOH H 2 O ball milling is carried out for 30min, the mixture is fully mixed, the molar ratio of Li to (Ni+Co+Mn) is controlled to be 1.05:1, presintering is carried out for 4h at 500 ℃ in air, and then solid phase reaction is carried out for 12h at 900 ℃ to obtain the anode material.
Taking 10g of the positive electrode material, adding 1.25g of acetylene black and 12.5g of polyvinylidene fluoride solution with the mass fraction of 10%, uniformly mixing, sequentially coating and slicing, and filling a lithium battery in a glove box, wherein the lithium sheet is a counter electrode, and LiF with the mass fraction of 1mol/L 6 EC-DMC (volume ratio 1:1) is the electrolyte.
The electrochemical performance of the lithium battery at 1C rate was measured, and the charge-discharge cycle result thereof is shown in FIG. 3, and the 100-cycle capacity retention rate was 99.7%.
Example 2
This example is used to illustrate the positive electrode material precursor and positive electrode material prepared by the present invention and evaluation.
1. Preparation of positive electrode material precursor
(1) Preparing a metal sulfate solution (comprising nickel sulfate, cobalt sulfate and aluminum sulfate) with the concentration of 2mol/L of metal ions (wherein the molar ratio of three elements of nickel, cobalt and aluminum is 6:2:2); preparing NaOH solution with the concentration of 2 mol/L; preparing complexing agent solution, wherein the concentration of ammonia water is 6mol/L, and the molar ratio of sodium citrate to the concentration of ammonia water is 0.1;
and (3) simultaneously and parallelly adding the prepared sulfate solution, naOH solution and complexing agent solution into a reaction kettle under the stirring state to perform precipitation reaction, wherein the dosage of the NaOH solution is 200 mol parts and the dosage of the complexing agent solution is 100 mol parts relative to 100 mol parts of the metal source solution. The addition rate of the sulfate solution was 60mL/h relative to 1L of sulfate solution; the adding speed of the complexing agent solution is 20mL/h; controlling the adding speed of NaOH solution to make the pH value of the reaction system 10; in the precipitation reaction, the stirring speed was controlled at 600rpm, the reaction temperature was 45℃and the reaction time was 72 hours (i.e., the addition was stopped after the parallel flow addition for 72 hours), to obtain a reaction slurry.
(2) And after the reaction slurry is naturally cooled, carrying out vacuum suction filtration on the reaction slurry, washing the obtained filter residue with deionized water for 3 times, and drying and dehydrating the filter residue in a vacuum drying oven at 70 ℃ for 20 hours to obtain a positive electrode material precursor S-2.
2. Evaluation of the precursor of the cathode Material
The SEM image of the obtained positive electrode material precursor S-2 is similar to that of FIG. 1, which shows that the obtained positive electrode material precursor has good sphericity and monodispersity;
the XRD pattern of the obtained positive electrode material precursor S-2 is similar to that of FIG. 2, which shows that the crystal structure of the obtained positive electrode material precursor is well developed;
EDS spectrum scanning is carried out on 400 particles of the obtained positive electrode material precursor S-2, and relative standard deviations of the contents of metal components Ni, co and Al in the 400 positive electrode material precursor particles are shown in table 1.
3. Preparation and evaluation of cathode Material
A positive electrode material and a lithium battery were prepared in the same manner as in example 1.
Electrochemical performance of the lithium battery at 1C rate was measured, and 100 cycles of cycle capacity retention was 99.6%.
Example 3
This example is used to illustrate the positive electrode material precursor and positive electrode material prepared by the present invention and evaluation.
1. Preparation of positive electrode material precursor
(1) Preparing a metal salt solution (package) with the concentration of metal ions (wherein, the mole ratio of three elements of nickel, cobalt and manganese is 9.5:0.25:0.25) of 1mol/L Including nickel nitrate, cobalt sulfate, and manganese acetate); preparation of K with a concentration of 6mol/L 2 CO 3 A solution; preparing complexing agent solution, wherein the concentration of ammonia water is 2mol/L, and the molar ratio of sodium citrate to the concentration of ammonia water is 1.5;
preparing the prepared salt solution, K 2 CO 3 The solution and the complexing agent solution are simultaneously and concurrently added into a reaction kettle under the stirring state to carry out precipitation reaction, and K is relative to 100 mole parts of salt solution 2 CO 3 The amount of the solution was 100 parts by mole and the amount of the complexing agent solution was 100 parts by mole. The addition rate of the saline solution was 60mL/h relative to 1L of saline solution; the adding speed of the complexing agent solution is 30mL/h; by controlling K 2 CO 3 The solution is added at a speed which enables the pH value of the reaction system to be 10; in the precipitation reaction process, the stirring speed is controlled to be 1000rpm, the reaction temperature is 60 ℃, and the reaction time is 72 hours (namely, the addition is stopped after the parallel flow addition for 72 hours), so as to obtain reaction slurry.
(2) And after the reaction slurry is naturally cooled, carrying out vacuum suction filtration on the reaction slurry, washing the obtained filter residue with deionized water for 3 times, and drying and dehydrating the filter residue in a vacuum drying oven at 130 ℃ for 8 hours to obtain a positive electrode material precursor S-3.
2. Evaluation of the precursor of the cathode Material
The SEM image of the obtained positive electrode material precursor S-3 is similar to that of FIG. 1, which shows that the obtained positive electrode material precursor has good sphericity and monodispersity;
The XRD pattern of the obtained positive electrode material precursor S-3 is similar to that of FIG. 2, which shows that the crystal structure of the obtained positive electrode material precursor is well developed;
EDS spectrum scanning is carried out on 400 particles of the obtained positive electrode material precursor S-3, and relative standard deviations of the contents of the metal components Ni, co and Mn in the 400 positive electrode material precursor particles are shown in table 1.
3. Preparation and evaluation of cathode Material
A positive electrode material and a lithium battery were prepared in the same manner as in example 1.
Electrochemical performance of the lithium battery at 1C rate was measured, and 100 cycles of cycle capacity retention was 99.3%.
Example 4
This example is used to illustrate the positive electrode material precursor and positive electrode material prepared by the present invention and evaluation.
1. Preparation of positive electrode material precursor
A cathode material precursor was prepared as in example 1, except that the molar concentration ratio of sodium citrate to aqueous ammonia was 0.01. And obtaining a positive electrode material precursor S-4.
2. Evaluation of the precursor of the cathode Material
The SEM image of the obtained positive electrode material precursor S-4 is similar to that of FIG. 1, which shows that the obtained positive electrode material precursor has good sphericity and monodispersity;
the XRD pattern of the obtained positive electrode material precursor S-4 is similar to that of FIG. 2, which shows that the crystal structure of the obtained positive electrode material precursor is well developed;
The relative standard deviations of the contents of the metal components Ni, co, mn in the 400 positive electrode material precursor particles are shown in table 1.
3. Preparation and evaluation of cathode Material
A positive electrode material and a lithium battery were prepared in the same manner as in example 1.
Electrochemical properties of the lithium battery at 1C rate were measured, and charge and discharge cycle results thereof are shown in table 1.
Example 5
This example is used to illustrate the positive electrode material precursor and positive electrode material prepared by the present invention and evaluation.
1. Preparation of positive electrode material precursor
A cathode material precursor was prepared as in example 1, except that the molar concentration ratio of sodium citrate to aqueous ammonia was 2. And obtaining a positive electrode material precursor S-5.
2. Evaluation of the precursor of the cathode Material
The SEM image of the obtained positive electrode material precursor S-5 is similar to that of FIG. 1, which shows that the obtained positive electrode material precursor has good sphericity and monodispersity;
the XRD pattern of the obtained positive electrode material precursor S-5 is similar to that of FIG. 2, which shows that the crystal structure of the obtained positive electrode material precursor is well developed;
the relative standard deviations of the contents of the metal components Ni, co, mn in the 400 positive electrode material precursor particles are shown in table 1.
3. Preparation and evaluation of cathode Material
Cathode material and lithium battery were prepared according to the method of example 1
Electrochemical properties of the lithium battery at 1C rate were measured, and charge and discharge cycle results thereof are shown in table 1.
Example 6
This example is used to illustrate the positive electrode material precursor and positive electrode material prepared by the present invention and evaluation.
1. Preparation of positive electrode material precursor
A positive electrode material precursor was prepared in the same manner as in example 1 except that a metal salt solution having a metal ion (wherein the molar ratio of nickel, cobalt and manganese elements is 8:1:1) concentration of 3mol/L was prepared; preparing NaOH solution with the concentration of 8 mol/L; preparing complexing agent solution, wherein the concentration of ammonia water is 10mol/L, and the molar ratio of sodium citrate to the concentration of ammonia water is 0.1; and obtaining a positive electrode material precursor S-6.
2. Evaluation of the precursor of the cathode Material
The SEM image of the obtained positive electrode material precursor S-6 is similar to that of FIG. 1, which shows that the obtained positive electrode material precursor has good sphericity and monodispersity;
the XRD pattern of the obtained positive electrode material precursor S-6 is similar to that of FIG. 2, which shows that the crystal structure of the obtained positive electrode material precursor is well developed;
the relative standard deviations of the contents of the metal components Ni, co, mn in the 400 positive electrode material precursor particles are shown in table 1.
3. Preparation and evaluation of cathode Material
Cathode material and lithium battery were prepared according to the method of example 1
Electrochemical properties of the lithium battery at 1C rate were measured, and charge and discharge cycle results thereof are shown in table 1.
Example 7
This example is used to illustrate the positive electrode material precursor and positive electrode material prepared by the present invention and evaluation.
1. Preparation of positive electrode material precursor
A positive electrode material precursor was prepared in the same manner as in example 1 except that the concentration of the prepared metal sulfate solution was 0.5mol/L; the concentration of the prepared NaOH solution is 2mol/L. And obtaining a positive electrode material precursor S-7.
2. Evaluation of the precursor of the cathode Material
The SEM image of the obtained positive electrode material precursor S-7 is similar to that of FIG. 1, which shows that the obtained positive electrode material precursor has good sphericity and monodispersity;
the XRD pattern of the obtained positive electrode material precursor S-7 is similar to that of FIG. 2, which shows that the crystal structure of the obtained positive electrode material precursor is well developed;
the relative standard deviations of the contents of the metal components Ni, co, mn in the 400 positive electrode material precursor particles are shown in table 1.
3. Preparation and evaluation of cathode Material
Cathode material and lithium battery were prepared according to the method of example 1
Electrochemical properties of the lithium battery at 1C rate were measured, and charge and discharge cycle results thereof are shown in table 1.
Example 8
This example is used to illustrate the positive electrode material precursor and positive electrode material prepared by the present invention and evaluation.
1. Preparation of positive electrode material precursor
A positive electrode material precursor was prepared in the same manner as in example 1, except that a metal sulfate solution (including nickel sulfate, cobalt sulfate, and manganese sulfate) having a metal ion (wherein the molar ratio of nickel, cobalt, and manganese elements is 8:1:1) concentration of 5mol/L was prepared; preparing NaOH solution with the concentration of 10 mol/L; complexing agent solution is prepared, wherein the concentration of ammonia water is 16mol/L, and the molar ratio of sodium citrate to the concentration of ammonia water is 0.1. And obtaining a positive electrode material precursor S-8.
The procedure of example 1 was followed to obtain a positive electrode material precursor.
(2) Evaluation of the precursor of the cathode Material
The SEM image of the obtained positive electrode material precursor S-8 is similar to that of FIG. 1, which shows that the obtained positive electrode material precursor has good sphericity and monodispersity;
the XRD pattern of the obtained positive electrode material precursor S-8 is similar to that of FIG. 2, which shows that the crystal structure of the obtained positive electrode material precursor is well developed;
the relative standard deviations of the contents of the metal components Ni, co, mn in the 400 positive electrode material precursor particles are shown in table 1.
(3) Preparation and evaluation of cathode Material
Cathode material and lithium battery were prepared according to the method of example 1
Electrochemical properties of the lithium battery at 1C rate were measured, and charge and discharge cycle results thereof are shown in table 1.
Example 9
This example is used to illustrate the positive electrode material precursor and positive electrode material prepared by the present invention and evaluation.
1. Preparation of positive electrode material precursor
A cathode material precursor was prepared in the same manner as in example 1, except that a metal sulfate solution (including nickel sulfate, cobalt sulfate, and manganese sulfate) having a concentration of 0.01mol/L of metal ions (wherein the molar ratio of nickel, cobalt, and manganese elements is 8:1:1) was prepared; preparing NaOH solution with the concentration of 0.02 mol/L; complexing agent solution is prepared, wherein the concentration of ammonia water is 0.01mol/L, and the molar ratio of sodium citrate to the concentration of ammonia water is 1. And obtaining a positive electrode material precursor S-9.
2. Evaluation of the precursor of the cathode Material
The SEM image of the obtained positive electrode material precursor S-9 is similar to that of FIG. 1, which shows that the obtained positive electrode material precursor has good sphericity and monodispersity;
the XRD pattern of the obtained positive electrode material precursor S-9 is similar to that of FIG. 2, and the crystal structure of the obtained positive electrode material precursor is well developed.
The relative standard deviations of the contents of the metal components Ni, co, mn in the 400 positive electrode material precursor particles are shown in table 1.
3. Preparation and evaluation of cathode Material
Cathode material and lithium battery were prepared according to the method of example 1
Electrochemical properties of the lithium battery at 1C rate were measured, and charge and discharge cycle results thereof are shown in table 1.
Example 10
This example is used to illustrate the positive electrode material precursor and positive electrode material prepared by the present invention and evaluation.
1. Preparation of positive electrode material precursor
A cathode material precursor was prepared in the same manner as in example 1, except that the pH of the reaction system was controlled to be 14 by adjusting the addition rate of NaOH solution during the co-current addition in step (1). And obtaining a positive electrode material precursor S-10.
2. Evaluation of the precursor of the cathode Material
The SEM image of the obtained positive electrode material precursor S-10 is similar to that of FIG. 1, which shows that the obtained positive electrode material precursor has good sphericity and monodispersity;
the XRD pattern of the obtained positive electrode material precursor S-10 is similar to that of FIG. 2, which shows that the crystal structure of the obtained positive electrode material precursor is well developed;
the relative standard deviations of the contents of the metal components Ni, co, mn in the 400 positive electrode material precursor particles are shown in table 1.
3. Preparation and evaluation of cathode Material
Cathode material and lithium battery were prepared according to the method of example 1
Electrochemical properties of the lithium battery at 1C rate were measured, and charge and discharge cycle results thereof are shown in table 1.
Example 11
This example is used to illustrate the positive electrode material precursor and positive electrode material prepared by the present invention and evaluation.
1. Preparation of positive electrode material precursor
A cathode material precursor was prepared in the same manner as in example 1, except that the pH of the reaction system was controlled to 8 by adjusting the addition rate of NaOH solution during the co-current addition in step (1). And obtaining a positive electrode material precursor S-11.
2. Evaluation of the precursor of the cathode Material
The SEM image of the obtained positive electrode material precursor S-11 is similar to that of FIG. 1, which shows that the obtained positive electrode material precursor has good sphericity and monodispersity;
the XRD pattern of the obtained positive electrode material precursor S-11 is similar to that of FIG. 2, which shows that the crystal structure of the obtained positive electrode material precursor is well developed;
the relative standard deviations of the contents of the metal components Ni, co, mn in the 400 positive electrode material precursor particles are shown in table 1.
3. Preparation and evaluation of cathode Material
Cathode material and lithium battery were prepared according to the method of example 1
Electrochemical properties of the lithium battery at 1C rate were measured, and charge and discharge cycle results thereof are shown in table 1.
Example 12
This example is used to illustrate the positive electrode material precursor and positive electrode material prepared by the present invention and evaluation.
1. Preparation of positive electrode material precursor
A cathode material precursor was prepared in the same manner as in example 1, except that the temperature of the precipitation reaction in step (1) was 70 ℃. And obtaining a positive electrode material precursor S-12.
2. Evaluation of the precursor of the cathode Material
The SEM image of the obtained positive electrode material precursor S-12 is similar to that of FIG. 1, which shows that the obtained positive electrode material precursor has good sphericity and monodispersity;
the XRD pattern of the obtained positive electrode material precursor S-12 is similar to that of FIG. 2, which shows that the crystal structure of the obtained positive electrode material precursor is well developed;
the relative standard deviations of the Ni, co, mn content of the metal components in the 400 positive electrode material precursor particles are shown in table 1.
3. Preparation and evaluation of cathode Material
Cathode material and lithium battery were prepared according to the method of example 1
Electrochemical properties of the lithium battery at 1C rate were measured, and charge and discharge cycle results thereof are shown in table 1.
Example 13
This example is used to illustrate the positive electrode material precursor and positive electrode material prepared by the present invention and evaluation.
1. Preparation of positive electrode material precursor
A cathode material precursor was prepared in the same manner as in example 1, except that the temperature of the precipitation reaction in step (1) was 20 ℃. And obtaining a positive electrode material precursor S-13.
The SEM image of the obtained positive electrode material precursor S-13 is similar to that of FIG. 1, which shows that the obtained positive electrode material precursor has good sphericity and monodispersity;
the XRD pattern of the obtained positive electrode material precursor S-13 is similar to that of FIG. 2, and the crystal structure of the obtained positive electrode material precursor is well developed.
The relative standard deviations of the Ni, co, mn content of the metal components in the 400 positive electrode material precursor particles are shown in table 1.
3. Preparation and evaluation of cathode Material
Cathode material and lithium battery were prepared according to the method of example 1
Electrochemical properties of the lithium battery at 1C rate were measured, and charge and discharge cycle results thereof are shown in table 1.
Example 14
This example is used to illustrate the positive electrode material precursor and positive electrode material prepared by the present invention and evaluation.
1. Preparation of positive electrode material precursor
A positive electrode material precursor was prepared in the same manner as in example 1, except that the time of the precipitation reaction in step (1) was 10 hours. And obtaining a positive electrode material precursor S-14.
The SEM image of the obtained positive electrode material precursor S-14 is similar to that of FIG. 1, which shows that the obtained positive electrode material precursor has good sphericity and monodispersity;
the XRD pattern of the obtained positive electrode material precursor S-14 is similar to that of FIG. 2, which shows that the crystal structure of the obtained positive electrode material precursor is well developed;
the relative standard deviations of the Ni, co, mn content of the metal components in the 400 positive electrode material precursor particles are shown in table 1.
3. Preparation and evaluation of cathode Material
Cathode material and lithium battery were prepared according to the method of example 1
Electrochemical properties of the lithium battery at 1C rate were measured, and charge and discharge cycle results thereof are shown in table 1.
Example 15
This example is used to illustrate the positive electrode material precursor and positive electrode material prepared by the present invention and evaluation.
1. Preparation of positive electrode material precursor
A positive electrode material precursor was prepared in the same manner as in example 1, except that the stirring speed during the precipitation reaction in step (1) was 50r/min. And obtaining a positive electrode material precursor S-15.
The SEM image of the obtained positive electrode material precursor S-15 is similar to that of FIG. 1, which shows that the obtained positive electrode material precursor has good sphericity and monodispersity;
the XRD pattern of the obtained positive electrode material precursor S-15 is similar to that of FIG. 2, which shows that the crystal structure of the obtained positive electrode material precursor is well developed;
the relative standard deviations of the Ni, co, mn content of the metal components in the 400 positive electrode material precursor particles are shown in table 1.
3. Preparation and evaluation of cathode Material
Cathode material and lithium battery were prepared according to the method of example 1
Electrochemical properties of the lithium battery at 1C rate were measured, and charge and discharge cycle results thereof are shown in table 1.
Example 16
This example is used to illustrate the positive electrode material precursor and positive electrode material prepared by the present invention and evaluation.
1. Preparation of positive electrode material precursor
A positive electrode material precursor was prepared in the same manner as in example 1, except that the stirring speed during the precipitation reaction in step (1) was 1200r/min. And obtaining a positive electrode material precursor S-16.
The SEM image of the obtained positive electrode material precursor S-16 is similar to that of FIG. 1, which shows that the obtained positive electrode material precursor has good sphericity and monodispersity;
the XRD pattern of the obtained positive electrode material precursor S-16 is similar to that of FIG. 2, which shows that the crystal structure of the obtained positive electrode material precursor is well developed;
the relative standard deviations of the Ni, co, mn content of the metal components in the 400 positive electrode material precursor particles are shown in table 1.
3. Preparation and evaluation of cathode Material
Cathode material and lithium battery were prepared according to the method of example 1
Electrochemical properties of the lithium battery at 1C rate were measured, and charge and discharge cycle results thereof are shown in table 1.
Example 17
This example is used to illustrate the positive electrode material precursor and positive electrode material prepared by the present invention and evaluation.
1. Preparation of positive electrode material precursor
A cathode material precursor was prepared as in example 1, except that sodium citrate was replaced with an equimolar amount of oxalic acid; the ammonia was replaced with an equimolar amount of ethanolamine. And obtaining a positive electrode material precursor S-17.
The SEM image of the obtained positive electrode material precursor S-17 is similar to that of FIG. 1, which shows that the obtained positive electrode material precursor has good sphericity and monodispersity;
the XRD pattern of the obtained positive electrode material precursor S-17 is similar to that of FIG. 2, which shows that the crystal structure of the obtained positive electrode material precursor is well developed;
The relative standard deviations of the Ni, co, mn content of the metal components in the 400 positive electrode material precursor particles are shown in table 1.
3. Preparation and evaluation of cathode Material
Cathode material and lithium battery were prepared according to the method of example 1
Electrochemical properties of the lithium battery at 1C rate were measured, and charge and discharge cycle results thereof are shown in table 1.
Example 18
This example is used to illustrate the positive electrode material precursor and positive electrode material prepared by the present invention and evaluation.
1. Preparation of positive electrode material precursor
A cathode material precursor was prepared as in example 1, except that sodium citrate was replaced with an equimolar amount of tartaric acid; the ammonia water was replaced with an equimolar amount of ammonium carbonate. And obtaining a positive electrode material precursor S-18.
The SEM image of the obtained positive electrode material precursor S-18 is similar to that of FIG. 1, which shows that the obtained positive electrode material precursor has good sphericity and monodispersity;
the XRD pattern of the obtained positive electrode material precursor S-18 is similar to that of FIG. 2, which shows that the crystal structure of the obtained positive electrode material precursor is well developed;
the relative standard deviations of the Ni, co, mn content of the metal components in the 400 positive electrode material precursor particles are shown in table 1.
3. Preparation and evaluation of cathode Material
Cathode material and lithium battery were prepared according to the method of example 1
Electrochemical properties of the lithium battery at 1C rate were measured, and charge and discharge cycle results thereof are shown in table 1.
Example 19
This example is used to illustrate the positive electrode material precursor and positive electrode material prepared by the present invention and evaluation.
1. Preparation of positive electrode material precursor
A cathode material precursor was prepared as in example 1, except that sodium citrate was replaced with an equimolar amount of sodium nitrilotriacetate; the ammonia was replaced with an equimolar amount of N, N-diethylethanolamine. And obtaining a positive electrode material precursor S-19.
The SEM image of the obtained positive electrode material precursor S-19 is similar to that of FIG. 1, which shows that the obtained positive electrode material precursor has good sphericity and monodispersity;
the XRD pattern of the obtained positive electrode material precursor S-19 is similar to that of FIG. 2, which shows that the crystal structure of the obtained positive electrode material precursor is well developed;
the relative standard deviations of the Ni, co, mn content of the metal components in the 400 positive electrode material precursor particles are shown in table 1.
3. Preparation and evaluation of cathode Material
Cathode material and lithium battery were prepared according to the method of example 1
Electrochemical properties of the lithium battery at 1C rate were measured, and charge and discharge cycle results thereof are shown in table 1.
Comparative example 1
This comparative example is used to illustrate the positive electrode material precursor and positive electrode material prepared by the reference method and evaluation.
1. Preparation of positive electrode material precursor
The preparation was carried out as in example 1, except that sodium citrate was replaced with an equimolar amount of aqueous ammonia. And obtaining a positive electrode material precursor D-1.
2. Evaluation of the precursor of the cathode Material
The SEM of the resulting positive electrode material precursor D-1 is similar to FIG. 1 and the XRD pattern is similar to FIG. 2.
The relative standard deviations of the contents of the metal components Ni, co, mn in 400 particles of the obtained 400 particles of the positive electrode material precursor D-1 are shown in Table 1.
3. Preparation and evaluation of cathode Material
A positive electrode material and a lithium battery were prepared in the same manner as in example 1.
The electrochemical performance of the lithium battery at 1C rate was measured, and the charge-discharge cycle result thereof is shown in FIG. 4, and the 100-cycle capacity retention rate was 91.7%.
Comparative example 2
Comparative example positive electrode material precursor and positive electrode material prepared by the method for illustrating reference, and evaluation
1. Preparation of positive electrode material precursor
The preparation was carried out as in example 1, except that the aqueous ammonia in the complexing agent solution was replaced with an equimolar sodium citrate solution. And obtaining a positive electrode material precursor D-2.
2. Evaluation of the precursor of the cathode Material
The SEM of the resulting positive electrode material precursor D-2 is similar to FIG. 1 and the XRD pattern is similar to FIG. 2.
The relative standard deviations of the contents of the metal components Ni, co, mn in 400 particles of the obtained positive electrode material precursor D-2 are shown in Table 1 after EDS spectrum scanning.
3. Preparation and evaluation of cathode Material
A positive electrode material and a lithium battery were prepared in the same manner as in example 1.
The electrochemical performance of the lithium battery at 1C rate was measured, and the charge-discharge cycle result thereof is shown in FIG. 5, and the 100-cycle capacity retention rate was 92.4%.
TABLE 1
The results of table 1 show that the positive electrode material precursor prepared by the embodiment of the technical scheme of the invention has good sphericity, monodispersity and consistency of metal component content, and the positive electrode material prepared by the positive electrode material precursor has good electrochemical performance when used in a lithium battery, and the charge and discharge cycle shows that the 100-cycle capacity retention rate can reach more than 96.9%. Examples 1-3 employing the preferred embodiments of the present invention have significantly more excellent effects.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.
Claims (49)
1. A positive electrode material precursor is characterized in that the expression of the positive electrode material precursor is Ni x Co y M z (OH) 2 ；
Wherein M is selected from Mn and/or Al;
x is more than or equal to 0.6 and less than or equal to 0.95,0.025, y is more than or equal to 0.2,0.025, z is more than or equal to 0.2, and x+y+z=1;
the positive electrode material precursor comprises a plurality of positive electrode material precursor particles, and the relative standard deviations of the contents of metal components Ni, co and M in different particles of the positive electrode material precursor respectively meet the following conditions: RSD (Ni) is more than or equal to 0 and less than or equal to 0.15, RSD (Co) is more than or equal to 0 and less than or equal to 0.15, RSD (M) is more than or equal to 0 and less than or equal to 0.15;
and measuring metal components in single positive electrode material precursor particles by adopting an X-ray energy spectrum scanner, testing the compositions of metal Ni, co and M in EDS energy spectrum scanning of 400 particles, and calculating relative standard deviations of Ni, co and M contents in 400 particles, wherein the relative standard deviations are respectively RSD (Ni), RSD (Co) and RSD (M).
2. The positive electrode material precursor according to claim 1, wherein the relative standard deviations of the contents of the metal components Ni, co and M in the different particles of the positive electrode material precursor satisfy respectively: RSD (Ni) is more than or equal to 0 and less than or equal to 0.1, RSD (Co) is more than or equal to 0 and less than or equal to 0.1, RSD (M) is more than or equal to 0 and less than or equal to 0.1.
3. The positive electrode material precursor according to claim 2, wherein the relative standard deviations of the contents of the metal components Ni, co and M in the different particles of the positive electrode material precursor satisfy respectively: RSD (Ni) is more than or equal to 0 and less than or equal to 0.05, RSD (Co) is more than or equal to 0 and less than or equal to 0.05, RSD (M) is more than or equal to 0 and less than or equal to 0.05.
4. A method for preparing the positive electrode material precursor according to any one of claims 1 to 3, characterized in that the method comprises the steps of:
(1) Mixing a solution containing a metal source, a precipitant solution and a complexing agent solution containing a first complexing agent and a second complexing agent for precipitation reaction;
(2) Carrying out solid-liquid separation and drying on the product obtained by the precipitation reaction in the step (1);
wherein the metal source comprises a nickel source, a cobalt source and an M source, M is selected from Mn and/or Al;
the total amount of the metal sources is taken as a reference, the nickel sources are used in an amount of 60-95 mol percent, the cobalt sources are used in an amount of 2.5-20 mol percent and the M sources are used in an amount of 2.5-20 mol percent based on metal elements;
the first complexing agent is selected from an ammonium ion donor and/or an alcohol amine complexing agent;
the second complexing agent is at least one of carboxylic acid complexing agent, carboxylic acid salt complexing agent, amino carboxylic acid complexing agent and hydroxyamino carboxylic acid complexing agent.
5. The method according to claim 4, wherein the metal source-containing solution has a molar concentration of 0.01 to 5mol/L in terms of metal element.
6. The method according to claim 5, wherein the molar concentration of the metal source-containing solution is 1 to 2mol/L in terms of metal element.
7. The method of claim 4, wherein the nickel source is selected from at least one of a sulfate, nitrate, acetate, and hydrochloride salt of nickel.
8. The method of claim 4, wherein the cobalt source is selected from at least one of a sulfate, nitrate, acetate, and hydrochloride salt of cobalt.
9. The method of claim 4, wherein the M source is selected from water soluble salts of M.
10. The method of claim 9, wherein the M source is selected from at least one of a sulfate, nitrate, acetate, and hydrochloride salt of M.
11. The method according to claim 4, wherein the precipitant solution is used in an amount of 100 to 300 parts by mole with respect to 100 parts by mole of the solution of the metal source.
12. The method of claim 11, wherein the precipitant solution is used in an amount of 150-250 parts by mole with respect to 100 parts by mole of the solution of the metal source.
13. The method of claim 4, wherein the precipitant solution has a concentration of 0.02-10mol/L.
14. The method of claim 13, wherein the precipitant solution has a concentration of 2-6mol/L.
15. The method of claim 4, wherein the precipitant is selected from at least one of an alkali metal hydroxide, carbonate and bicarbonate.
16. The method of claim 15, wherein the alkali metal is selected from at least one of Li, na, and K.
17. The method according to claim 4, wherein the complexing agent solution is used in an amount of 5 to 200 parts by mole with respect to 100 parts by mole of the solution of the metal source.
18. The method of claim 17, wherein the complexing agent solution is used in an amount of 50-150 mole parts per 100 mole parts of the solution of the metal source.
19. The method of claim 4, wherein the concentration of the first complexing agent in the complexing agent solution is between 0.01 and 16 mol/L.
20. The method of claim 19, wherein the concentration of the first complexing agent in the complexing agent solution is between 2 and 10mol/L.
21. The method of claim 20, wherein the concentration of the first complexing agent in the complexing agent solution is 2-6mol/L.
22. The method of claim 4, wherein the molar concentration ratio of the second complexing agent to the first complexing agent in the complexing agent solution is from 0.01 to 2.
23. The method of claim 22, wherein the molar concentration ratio of the second complexing agent to the first complexing agent in the complexing agent solution is between 0.1 and 1.5.
24. The method of claim 4, wherein the ammonium ion donor is selected from at least one of ammonia, ammonium oxalate, ammonium carbonate, and ammonium bicarbonate.
25. The method of claim 4, wherein the alcohol amine complexing agent is selected from at least one of ethanolamine, diethanolamine, 2-dibutylamino ethanol, 2-diethylaminoethanol, and N, N-diethylethanolamine.
26. The method of claim 4, wherein the aminocarboxylic acid complexing agent is selected from at least one of sodium nitrilotriacetate, potassium nitrilotriacetate, ethylenediamine tetraacetic acid and salts thereof, and diethylenetriamine pentaacetic acid.
27. The method of claim 4, wherein the hydroxyamino carboxylic acid complexing agent is selected from at least one of hydroxyethylenediamine tetraacetic acid and salts thereof, ethyleneglycol bis (β -diaminoethyl) diethyl ether-N, N' -tetraacetic acid and salts thereof, and dihydroxyglycine and salts thereof.
28. The method of claim 4, wherein the carboxylic acid-based complexing agent and/or carboxylic acid salt-based complexing agent is selected from at least one of oxalic acid and salts thereof, tartaric acid and salts thereof, citric acid and salts thereof, gluconic acid and salts thereof, carboxymethyl hydroxy malonic acid and salts thereof, carboxymethyl hydroxy succinic acid and salts thereof, and hydroxyethyl amino acetic acid and salts thereof.
29. The method of claim 28, wherein the carboxylic acid-based complexing agent and/or carboxylic acid salt-based complexing agent is citric acid and/or citrate.
30. The method of claim 29, wherein the carboxylic acid-based complexing agent and/or carboxylic acid salt-based complexing agent is at least one of sodium citrate, potassium citrate, and ferric ammonium citrate.
31. The method of claim 4, wherein in step (1), the conditions of the precipitation reaction include: the temperature is 20-70 ℃; the pH value is 8-14; the time is not less than 5 hours.
32. The method of claim 31, wherein in step (1), the precipitation reaction conditions comprise: the temperature is 45-60 ℃; the pH value is 10-12; the time is 24-72h.
33. The method of claim 4, wherein the precipitation reaction is performed under stirring.
34. The method of claim 33, wherein the stirring is at a speed of 50-1200r/min.
35. The method of claim 34, wherein the stirring is at a speed of 600-1000r/min.
36. The method of claim 4, wherein the drying conditions comprise: the temperature is 50-180 ℃ and the time is 4-24h.
37. The method of claim 36, wherein the drying conditions comprise: the temperature is 70-130 ℃; the time is 8-20 h.
38. The method of claim 4, wherein in step (1), the mixing comprises: and adding the solution containing the metal source, the precipitant solution and the complexing agent solution containing the first complexing agent and the second complexing agent into the reaction kettle in parallel.
39. The method according to claim 38, wherein the metal source-containing solution is added at a rate of 10 to 200mL/h based on 1L of the total amount of the metal source-containing solution.
40. The method of claim 39, wherein the metal source-containing solution is added at a rate of 20 to 100mL/h based on 1L of the total amount of the metal source-containing solution.
41. The method of claim 40, wherein the precipitant solution is added at a rate of 10-200mL/h based on 1L total precipitant solution.
42. The method of claim 41, wherein the precipitant solution is added at a rate of 20-100mL/h based on 1L total precipitant solution.
43. The method of claim 38, wherein the complexing agent solution is added at a rate of 10 to 200mL/h based on 1L total complexing agent solution containing the first complexing agent and the second complexing agent.
44. The method of claim 43, wherein the complexing agent solution is added at a rate of 20-100mL/h based on 1L total complexing agent solution containing the first complexing agent and the second complexing agent.
45. A method for producing a positive electrode material, characterized in that the method comprises mixing a lithium source with the positive electrode material precursor according to any one of claims 1 to 3, followed by firing.
46. The method of claim 45, wherein the molar ratio of the lithium source to the positive electrode material precursor is 0.9 to 1.3 in terms of metal element: 1.
47. the method of claim 46, wherein the molar ratio of the lithium source to the positive electrode material precursor is 0.95 to 1.1 in terms of metal element: 1.
48. the positive electrode material produced by the production method according to any one of claims 45 to 47.
49. Use of the positive electrode material precursor according to any one of claims 1 to 3 or the positive electrode material according to claim 48 in a lithium battery.
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