CN115196692B - Preparation method and device of precursor of ternary positive electrode material, precursor and positive electrode material - Google Patents
Preparation method and device of precursor of ternary positive electrode material, precursor and positive electrode material Download PDFInfo
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- 239000002243 precursor Substances 0.000 title claims abstract description 177
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 58
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 238000000034 method Methods 0.000 claims description 65
- 239000000243 solution Substances 0.000 claims description 62
- 239000013078 crystal Substances 0.000 claims description 55
- 238000007254 oxidation reaction Methods 0.000 claims description 54
- 230000003647 oxidation Effects 0.000 claims description 52
- 238000006243 chemical reaction Methods 0.000 claims description 33
- 239000012266 salt solution Substances 0.000 claims description 27
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 23
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 claims description 17
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 17
- 239000001301 oxygen Substances 0.000 claims description 17
- 229910052760 oxygen Inorganic materials 0.000 claims description 17
- 239000011572 manganese Substances 0.000 claims description 15
- 239000002245 particle Substances 0.000 claims description 14
- 229910003002 lithium salt Inorganic materials 0.000 claims description 12
- 159000000002 lithium salts Chemical class 0.000 claims description 12
- 230000001590 oxidative effect Effects 0.000 claims description 12
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 8
- 229910017052 cobalt Inorganic materials 0.000 claims description 8
- 239000010941 cobalt Substances 0.000 claims description 8
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 8
- 239000008139 complexing agent Substances 0.000 claims description 8
- 229910052748 manganese Inorganic materials 0.000 claims description 8
- 239000011259 mixed solution Substances 0.000 claims description 8
- 229910052759 nickel Inorganic materials 0.000 claims description 8
- 229910021645 metal ion Inorganic materials 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 229910052727 yttrium Inorganic materials 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 33
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 33
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 30
- 230000000052 comparative effect Effects 0.000 description 23
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 22
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 16
- 229910052744 lithium Inorganic materials 0.000 description 16
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 14
- 238000009830 intercalation Methods 0.000 description 14
- 230000002687 intercalation Effects 0.000 description 13
- 238000001878 scanning electron micrograph Methods 0.000 description 12
- 239000002562 thickening agent Substances 0.000 description 11
- 239000007788 liquid Substances 0.000 description 10
- 238000005245 sintering Methods 0.000 description 9
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 8
- 235000011114 ammonium hydroxide Nutrition 0.000 description 8
- 239000010406 cathode material Substances 0.000 description 8
- 229910021529 ammonia Inorganic materials 0.000 description 6
- 238000012360 testing method Methods 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- HFCVPDYCRZVZDF-UHFFFAOYSA-N [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O Chemical compound [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O HFCVPDYCRZVZDF-UHFFFAOYSA-N 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 230000001276 controlling effect Effects 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- 229910000572 Lithium Nickel Cobalt Manganese Oxide (NCM) Inorganic materials 0.000 description 1
- FBDMTTNVIIVBKI-UHFFFAOYSA-N [O-2].[Mn+2].[Co+2].[Ni+2].[Li+] Chemical compound [O-2].[Mn+2].[Co+2].[Ni+2].[Li+] FBDMTTNVIIVBKI-UHFFFAOYSA-N 0.000 description 1
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
- -1 carbonic acid compound Chemical class 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 229940011182 cobalt acetate Drugs 0.000 description 1
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 229940071125 manganese acetate Drugs 0.000 description 1
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000009768 microwave sintering Methods 0.000 description 1
- 229940078494 nickel acetate Drugs 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
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- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/18—Stationary reactors having moving elements inside
- B01J19/1862—Stationary reactors having moving elements inside placed in series
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The application relates to the technical field of batteries, in particular to a preparation method and device of a precursor of a ternary positive electrode material, the precursor and the positive electrode material. The general formula of the precursor of the ternary positive electrode material is Ni a Co b Mn c Li d (OH) 2 ，0.8≤a≤0.95，0<b≤0.2，0<c≤0.2，0<d is less than or equal to 1.2, and a+b+c=1. Lithium ions can be inserted into the precursor of the ternary positive electrode material.
Description
Technical Field
The application relates to the technical field of batteries, in particular to a preparation method and device of a precursor of a ternary positive electrode material, the precursor and the positive electrode material.
Background
Secondary batteries, such as lithium ion batteries, have been widely used in mobile electronic products. With the rapid development of the electronic industry, the electrochemical performance requirements of lithium ion batteries are higher and higher. One of the key factors determining the electrochemical performance of the lithium ion battery is a positive electrode material, wherein the nickel cobalt lithium manganate ternary positive electrode material has a remarkable ternary synergistic effect, is high in energy density, relatively low in cost and good in safety function, and becomes a main development direction of the current positive electrode material of the lithium ion battery. At present, the main process in the synthesis process of the ternary positive electrode material is to synthesize hydroxide or carbonic acid compound precursors of the ternary positive electrode material, and then mix the precursors with lithium salt and sinter the mixture at high temperature to obtain the positive electrode material.
The Chinese patent application with publication number of CN104934593A adds nickel acetate, cobalt acetate, manganese acetate and lithium salt into aqueous solution of glucose and citric acid to stir to form paste precursor, then ball-milling and microwave sintering to obtain ternary positive electrode material.
The Chinese patent application with publication number of CN112133890A adopts a process of synthesizing a ternary precursor containing lithium in one step and then sintering the ternary precursor at high temperature to obtain a monocrystal ternary positive electrode material, the process performs pre-intercalation of lithium at the stage of the precursor, so that the sintering process of the positive electrode material is simplified, but the process is only suitable for monocrystal small particles, and the process can not synthesize a polycrystal lithium-containing precursor with large D50 particles and the positive electrode material because the lithium intercalation amount is difficult to control in the synthesis process of the lithium-containing precursor and the growth of the precursor particles is greatly influenced by pH value.
In summary, the existing synthesis process of the precursor of the ternary positive electrode material and the positive electrode material is difficult to achieve both uniform intercalation of lithium ions into the precursor and normal growth of the precursor, so that it is difficult to obtain the polycrystalline lithium-containing precursor and the positive electrode material with ideal particle sizes.
Disclosure of Invention
The application discloses a preparation method and device of a precursor of a ternary positive electrode material, the precursor and the positive electrode material, and aims to solve the problem that the intercalation amount of lithium ions in the precursor of the existing ternary positive electrode material is low.
In order to achieve the above purpose, the present application provides the following technical solutions:
in a first aspect, the present application provides a precursor of a ternary positive electrode material, where the precursor of the ternary positive electrode material has a general formula of Ni a Co b Mn c Li d (OH) 2 ，0.8≤a≤0.95，0<b≤0.2，0<c≤0.2，0<d≤1.2，a+b+c＝1。
Further, the D50 of the precursor is 6-15 μm, and the BET of the precursor is 4-20 m 2 /g。
In a second aspect, the application provides a method for preparing a precursor of a ternary cathode material, comprising the following steps:
the growth process and the oxidation process are sequentially repeated until the precursor with the preset particle size is obtained, wherein the growth process and the oxidation process are carried out in a segmented mode.
Further, the preparation method further comprises a step of preparing a precursor crystal nucleus, wherein the preparation of the precursor crystal nucleus comprises the following steps:
preparing a reaction solution: preparing a nickel-cobalt-manganese mixed salt solution, a lithium salt solution, a precipitant solution and a complexing agent solution;
and under the protection of inert gas, mixing and uniformly stirring the reaction solution to obtain the precursor crystal nucleus.
Further, the precursor crystal nucleus sequentially repeats the growth process and the oxidation process until a precursor with a preset particle size is obtained, and the method comprises the following steps:
step A), under inert atmosphere, precursor crystal nucleus grows in the reaction solution; the reaction solution is a mixed solution of nickel-cobalt-manganese mixed salt solution, lithium salt solution, precipitant solution and complexing agent solution, and the pH value of the reaction solution is 9-12;
step B), oxidizing the grown precursor crystal nucleus in oxygen atmosphere to obtain oxidized precursor crystal nucleus;
and (3) continuously and sequentially circulating the step A) and the step B) to obtain the precursor with the preset particle size.
Further, after each step B, the oxidized precursor nucleus is washed to remove oxygen, and then step a is performed.
Further, the concentration of total metal ions of the nickel-cobalt-manganese mixed salt solution is 1-5 mol/L, and the molar ratio of nickel to cobalt to manganese is m, wherein n is n, m is more than or equal to 0.5 and less than or equal to 1, n is more than or equal to 0 and less than or equal to 0.2, and p is more than 0 and less than or equal to 0.3.
Further, the complexing agent solution is ammonia water solution, and the ammonia concentration in the reaction solution is 2-15 g/L.
Further, the concentration of oxygen in the step B is 2% -35%.
In a third aspect, the present application provides an apparatus for applying the preparation method of the second aspect, comprising: the growth kettle is used for growing precursor crystal nucleus; the oxidation kettle is used for oxidizing the precursor crystal nucleus.
In a fourth aspect, the present application provides a positive electrode material prepared by using the precursor of the first aspect or the precursor prepared by the preparation method of the second aspect as a raw material, where the positive electrode material has a general formula of Li d Ni a Co b Mn c M x O 2 Wherein M is one or a combination of at least two of Al, zr, sr, Y, ba, ti, B, W, mg, mo and Na, d is more than or equal to 1 and less than or equal to 1.2, a is more than or equal to 0.8 and less than or equal to 0.95,0<b≤0.2，0<c≤0.2，0≤x≤0.05，a+b+c+x＝1。
By adopting the technical scheme of the application, the beneficial effects are as follows:
the general formula of the precursor of the ternary positive electrode material provided by the application is Ni a Co b Mn c Li d (OH) 2 ，0.8≤a≤0.95，0<b≤0.2，0<c≤0.2，0<d is less than or equal to 1.2, and a+b+c=1. Lithium ions can be inserted into the precursor of the ternary positive electrode material.
Drawings
FIG. 1 is a schematic flow chart of a method for preparing a precursor of a ternary positive electrode material according to an embodiment of the present application;
FIG. 2 is a schematic diagram of a preparation apparatus for a precursor of a ternary positive electrode material according to an embodiment of the present application;
FIG. 3 is an SEM image of the precursor of example 2;
FIG. 4 is an SEM image of a precursor of example 3;
FIG. 5 is an SEM image of a precursor of example 4;
FIG. 6 is an SEM image of a precursor of example 5;
FIG. 7 is an SEM image of a precursor of example 6;
FIG. 8 is an SEM image of a precursor of example 7;
FIG. 9 is an SEM image of the precursor of comparative example 1;
FIG. 10 is an SEM image of the precursor of comparative example 2;
FIG. 11 is an SEM image of the precursor of comparative example 3;
FIG. 12 is an SEM image of the precursor of comparative example 4;
fig. 13 is an SEM image of the precursor in comparative example 5.
Reference numerals:
11-growing kettle; 12-oxidizing a kettle; 13-a transfer kettle; 14-a thickener; 15-a pump;
01-flash port; 02-a feed back port; 03-a feed inlet; 04-a discharge hole; 05-a feeding port; 06-a discharge hole; 07-reflux port.
Detailed Description
In order to make the objects, technical solutions and advantages of the present application more apparent, the present application will be described in further detail below with reference to the accompanying drawings, and it is apparent that the described embodiments are only some embodiments of the present application, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the application without making any inventive effort, are intended to be within the scope of the application.
The application scenario described in the embodiment of the present application is for more clearly describing the technical solution of the embodiment of the present application, and does not constitute a limitation on the technical solution provided by the embodiment of the present application, and as a person of ordinary skill in the art can know that the technical solution provided by the embodiment of the present application is applicable to similar technical problems as the new application scenario appears. In the description of the present application, unless otherwise indicated, the meaning of "a plurality" is two or more.
Currently, secondary batteries, such as lithium ion batteries, have been widely used in the fields of unmanned aerial vehicles, electric vehicles, and the like. With the rapid development of the electronics industry, consumers have increasingly strict requirements on the cruising performance, safety performance, and the like of electric vehicles, and therefore, higher-performance secondary batteries are required to meet the electricity demand of the electric vehicles. The ternary positive electrode material has high energy density, relatively low cost and good safety function, and can meet the increasing application requirements of the secondary battery. The physical and chemical properties of the ternary positive electrode material are directly determined by the ternary precursor, and the conventional synthesis process of the ternary precursor is difficult to realize uniform intercalation of lithium ions into the precursor and normal growth of the precursor.
Accordingly, embodiments of the present application provide a precursor of a ternary positive electrode material, wherein the precursor has a general formula of Ni a Co b Mn c Li d (OH) 2 ，0.8≤a≤0.95，0<b≤0.2，0<c≤0.2，0<d≤1.2，a+b+c＝1。
The general formula of the precursor of the ternary positive electrode material in the embodiment of the application is Ni a Co b Mn c Li d (OH) 2 Wherein 0.8.ltoreq.a.ltoreq.0.95 may be, for example, 0.80, 0.82, 0.85, 0.88, 0.9, 0.92 or 0.95, but is not limited to the values recited, and other values not recited in the numerical range are equally applicable. Wherein 0 is<b.ltoreq.0.2, may be, for example, 0.05, 0.08, 0.1, 0.12, 0.15, 0.17, 0.18 or 0.20, but is not limited to the values recited, other values not recited in the numerical range being equally applicable. Wherein 0 is<c.ltoreq.0.2, for example, 0.05, 0.08, 0.1, 0.12, 0.15, 0.17, 0.18 or 0.2, but is not limited to the values recited, other values not recited in the numerical range being equally applicable. Wherein 0 is<d.ltoreq.1.2, may be, for example, 0.1, 0.2, 0.3, 0.31, 0.33, 0.35, 0.4, 0.45, 0.5, 0.55, 0.6, 0.65, 0.7, 0.8, 0.9, 1.0, 1.1 or 1.2, but is not limited to the values recited, and other values not recited in the numerical range are equally applicable.
The D50 of the precursor can be 6-15 mu m, and the BET of the precursor is 4-20 m 2 And/g. The D50 of the precursor is typically, but not limited to, 6 μm, 7 μm, 8 μm, 9 μm, 10 μm, 11 μm, 12 μm, 13 μm, 14 μm or 15 μm. The BET of this precursor is typically, but not limited to, 4m 2 /g、5m 2 /g、6m 2 /g、8m 2 /g、10m 2 /g、12m 2 /g、14m 2 /g、16m 2 /g、18m 2 /g or 20m 2 /g。
In the conventional process for synthesizing the precursor of the ternary cathode material, uniform intercalation of lithium ions is difficult to realize, because in the conventional process for oxidizing intercalation of lithium, precursor crystal nuclei are inhibited from growing under the oxidizing condition and tend to form more crystal nuclei, so that a precursor containing lithium with larger D50 cannot be synthesized, and because the activity of the precursor crystal nuclei is larger in the oxidizing environment, lithium ions are rapidly deposited, so that the precursor for uniformly intercalating lithium ions cannot be obtained.
In view of the above, the embodiment of the application provides a preparation method of a precursor of a ternary positive electrode material, which comprises the following steps:
the growth process and the oxidation process are sequentially repeated until the precursor with the preset particle size is obtained, wherein the growth process and the oxidation process are carried out in a segmented mode.
According to the preparation method of the precursor of the ternary positive electrode material, provided by the embodiment of the application, the growth process and the oxidation process of the precursor are carried out in a segmented manner, so that the growth process and the oxidation process of the precursor are effectively separated. The morphology of the precursor crystal nucleus whisker can be thinned and the porosity is increased through oxidization, so that favorable conditions are provided for lithium ion intercalation, the surface activity of the oxidized precursor crystal nucleus is improved, lithium ions are more easily adsorbed and deposited on the surface of the precursor crystal nucleus, and the lithium ion intercalation quantity is improved. In addition, as the growth and the oxidation process are carried out in a segmented manner, the growth of the precursor crystal nucleus is not influenced by the oxidation process, and the rate of lithium ion precipitation can be relieved, so that a great amount of lithium ions can be uniformly distributed in the precursor through the sequential repetition of the growth process and the oxidation process of the precursor crystal nucleus, and the ternary lithium-containing precursor with ideal D50 can be obtained.
The step of growing and oxidizing means that the growth and oxidizing of the precursor nuclei are performed in different time periods to separate the growth and oxidizing of the precursor nuclei.
The purpose of the precursor crystal nucleus is to enable the precursor crystal nucleus to further grow so that lithium ions can be effectively deposited on the surface of the precursor crystal nucleus.
In one embodiment of the present application, the method further comprises a step of preparing a precursor crystal nucleus, the preparing the precursor crystal nucleus comprising:
preparing a reaction solution: preparing a nickel-cobalt-manganese mixed salt solution, a lithium salt solution, a precipitant solution and a complexing agent solution;
and under the protection of inert gas, mixing and uniformly stirring the reaction solution to obtain the precursor crystal nucleus.
It will be appreciated that the method of preparing the precursor nuclei is not limited in this embodiment, but is merely one possible method of preparing the precursor nuclei.
Fig. 1 is a schematic flow chart of a preparation method of a precursor of a ternary cathode material according to an embodiment of the present application, and referring to fig. 1, a flow of sequentially repeating a growth process and an oxidation process of a precursor crystal nucleus until a precursor with a preset particle size is obtained is described, and specifically includes the following steps:
step A), under inert atmosphere, precursor crystal nucleus grows in the reaction solution; the reaction solution is a mixed solution of nickel-cobalt-manganese mixed salt solution, lithium salt solution, precipitant solution and complexing agent solution, and the pH value of the reaction solution is 9-12;
step B), oxidizing the grown precursor crystal nucleus in oxygen atmosphere to obtain oxidized precursor crystal nucleus;
step C), continuously and sequentially circulating the step A) and the step B) to obtain the precursor with the preset particle size.
The growth and oxidation processes of the precursor may be sequentially and cyclically performed, and thus, the precursor having large-sized particles may be finally obtained. It should be noted that, the pH value of the oxidation reaction in step B) and the pH value of the reaction solution in step a) are both in the range of 9 to 12, and the pH value is typically, but not limited to, 9, 9.5, 10, 10.5, 11, 11.5 or 12, etc.
In one embodiment of the present application, after each step B, the oxidized precursor crystal nucleus is washed to remove oxygen, and then step a is performed, so as to avoid the influence of oxygen on the growth process of the precursor crystal nucleus.
In the reaction solution of the embodiment of the application, the concentration of total metal ions of the nickel cobalt manganese mixed salt solution is 1-5 mol/L, and the concentration of total metal ions of the nickel cobalt manganese mixed salt solution is exemplified by 1mol/L, 1.5mol/L, 2mol/L, 2.5mol/L, 3mol/L, 4mol/L or 5.0mol/L. Wherein, the molar ratio of nickel, cobalt and manganese in the nickel-cobalt-manganese mixed salt solution is m, n is p, m is more than or equal to 0.5 and less than or equal to 1, n is more than or equal to 0 and less than or equal to 0.2, and p is more than 0 and less than or equal to 0.3.
In one embodiment of the application, the complexing agent solution is an aqueous ammonia solution having a concentration of 3 to 10mol/L, for example, 3mol/L, 3.5mol/L, 4mol/L, 5mol/L, 6mol/L, 8mol/L, or 10mol/L.
In the reaction solution of the embodiment of the present application, the precipitant solution is an alkali solution, for example, a sodium hydroxide solution. In one embodiment of the application, the lithium salt solution is a lithium hydroxide solution. The precipitant solution and the lithium salt solution are mixed according to a certain proportion, the precipitant solution is taken as sodium hydroxide solution, the lithium salt solution is taken as lithium hydroxide solution as an example, the molar concentration of the mixed solution of the precipitant solution and the lithium salt solution is 1-15 mol/L, the proportion of the lithium hydroxide to the sodium hydroxide is 0.2-0.8, and the proportion of the lithium hydroxide to the sodium hydroxide is exemplified as 0.2, 0.3, 0.4, 0.5, 0.6, 0.7 or 0.8, and the like.
It is understood that the concentration of ammonia in the reaction solution is controlled to be 2 to 15g/L by controlling the concentrations of the aqueous ammonia solution and the alkaline solution in the reaction solution. The ammonia concentration in the reaction solution is typically, but not limited to, 2g/L, 3g/L, 4g/L, 5g/L, 6g/L, 8g/L, 10g/L, 12g/L, 14g/L, or 15g/L.
In one embodiment of the present application, the concentration of oxygen in step B is 2% -35%, and the concentration of oxygen may be 2%, 4%, 6%, 10%, 15%, 20%, 25%, 30% or 35%. In one embodiment of the application, the reaction temperature is controlled to be 50-80 ℃ during the growth and oxidation of the precursor crystal nucleus. The temperature of the growth and oxidation process of the precursor nuclei is, for example, 50 ℃, 52 ℃, 55 ℃, 60 ℃, 65 ℃, 70 ℃, 75 ℃ or 80 ℃.
Based on the same inventive concept, an embodiment of the present application provides an apparatus comprising: the growth kettle is used for growing precursor crystal nucleus; the oxidation kettle is used for oxidizing the precursor crystal nucleus. The growth and oxidation processes of the precursor crystal nucleus are respectively arranged in different reaction kettles, so that the growth and oxidation processes of the precursor crystal nucleus are effectively separated.
Next, a specific description will be given of a preparation apparatus of a precursor of a ternary cathode material according to an embodiment of the present application with reference to fig. 2. As shown in fig. 2, the device comprises a growth kettle 11, an oxidation kettle 12 and a thickener 14, wherein a flash port 01 of the growth kettle 11 is connected with a feed port 03 of the oxidation kettle 12, and the flash port 01 is higher than the feed port 03; the discharge port 04 of the oxidation kettle 12 is connected with the feeding port 05 of the thickener 14, and the discharge port 06 of the thickener 14 is connected with the feed back port 02 of the growth kettle 11.
The process for preparing the precursor of the ternary cathode material by using the device is specifically described as follows:
introducing a mixed solution of nickel-cobalt-manganese mixed salt solution, sodium hydroxide, lithium hydroxide and ammonia water solution into a growth kettle 11, regulating and controlling the pH value range of the mixed solution to be 9-12, and the ammonia concentration to be 2-15 g/L, and reacting the mixed solution under an inert atmosphere to obtain a precursor crystal nucleus after growth;
ammonia water solution and sodium hydroxide solution are introduced into the oxidation kettle 12 to regulate and control the pH value range of feed liquid in the oxidation kettle 12 to be 9-12, the ammonia concentration of the feed liquid to be 2-15 g/L, the precursor crystal nucleus grown in the growth kettle 11 enters the oxidation kettle 12 through a flash port 01, oxygen is introduced into the oxidation kettle 12 at a flow rate of 1-10L/min, and the oxygen concentration in the oxidation kettle 12 is regulated and controlled to be 2% -35% so as to oxidize the precursor crystal nucleus grown, thus obtaining the precursor crystal nucleus after oxidation;
the feed liquid in the oxidation kettle 12 flows out of the oxidation kettle 12 through a discharge port 04, enters a thickener 14 through a feed port 05, is separated by the thickener 14, and oxidized precursor crystal nuclei are discharged from the thickener 14 in a precipitate form through a discharge port 06, enter a growth kettle 11 through a feed back port 02, and continue to grow and intercalate lithium ions in the growth kettle 11. Wherein, in order to avoid the influence of oxygen on the growth of the precursor, the oxidized precursor crystal nucleus is washed by deionized water and then enters the growth kettle 11.
It should be noted that, the growth reactor 11 may be used for preparing and growing precursor crystal nuclei, or the precursor crystal nuclei may be directly added into the growth reactor 11, and the growth reactor 11 is only used for growing precursor, both of which are within the protection scope of the present application. In one embodiment of the application, the flow rate of the nickel-cobalt-manganese mixed salt solution introduced into the growth kettle 11 is 50-300L/h, and specifically can be 50L/h, 60L/h, 80L/h, 110L/h, 150L/h, 200L/h, 250L/h or 300L/h, etc.
It will be appreciated that for convenience in transferring the feed liquid in the oxidation reactor 12, the apparatus further comprises a transfer reactor 13 connected to the discharge port 04 of the oxidation reactor 12, and a pump 15 connected between the transfer reactor 13 and the thickener 14, and the feed liquid in the oxidation reactor 12 is transferred to the thickener 14 by the action of the pump 15.
In one embodiment of the application, at least part of the clarified liquid obtained by separating the feed liquid in the oxidation kettle 12 through the thickener 14 flows back to the oxidation kettle 12 through the return port 07, wherein the clarified liquid is ammonia water solution and sodium hydroxide solution which are introduced into the oxidation kettle 12, and the clarified liquid obtained by separating the thickener 14 flows back to the oxidation kettle 12 to recycle the reaction solvent, so that raw materials are saved, and the reaction cost is reduced.
According to the device provided by the application, the growth of the precursor crystal nucleus is carried out in the growth kettle 11, and the oxidation of the precursor is carried out in the oxidation kettle 12, so that the growth and the oxidation process of the precursor are separated, and the growth and the oxidation process can be continuously and sequentially repeated, so that the reaction efficiency is improved.
The precursor provided by the embodiment of the application can be embedded with lithium ions, when the ratio of the molar quantity of lithium in the precursor to the sum of the molar quantities of nickel, cobalt and manganese is more than or equal to 1.04, a ternary positive electrode material can be obtained by direct sintering, and if the ratio of the molar quantity of embedded lithium in the precursor to the sum of the molar quantities of nickel, cobalt and manganese is less than 1.04, a proper amount of lithium ions can be supplemented, and then sintering can be performed, so that the ternary positive electrode material can be obtainedTernary positive electrode material. The lithium ion amount to be supplemented is calculated according to the difference between the preset lithium ion content in the positive electrode material and the lithium ion content in the precursor, and the lithium-containing precursor and the corresponding LiOH or Li 2 CO 3 And uniformly mixing and sintering to obtain the ternary anode material.
Based on the same inventive concept, the present embodiment also provides a positive electrode material prepared from the precursor according to various possible embodiments of the present application or the precursor prepared by various possible preparation methods according to the present application, where the positive electrode material has a general formula of Li d Ni a Co b Mn c M x O 2 Wherein M is one or a combination of at least two of Al, zr, sr, Y, ba, ti, B, W, mg, mo and Na, d is more than or equal to 1 and less than or equal to 1.2, a is more than or equal to 0.8 and less than or equal to 0.95,0<b≤0.2，0<c is less than or equal to 0.2, x is less than or equal to 0.05, and a+b+c+x=1. When M is Al, the M source may be Al 2 O 3 Or Al (OH) 3 The method comprises the steps of carrying out a first treatment on the surface of the When M is Zr, the M source may be ZrO 2 Or Zr (NO) 3 ) 4 The method comprises the steps of carrying out a first treatment on the surface of the When M is Sr, the M source may be SrO; when M is Y, the M source may be Y 2 O 3 The method comprises the steps of carrying out a first treatment on the surface of the When M is Ba, the M source may be BaCO 3 Or Ba (OH) 2 The method comprises the steps of carrying out a first treatment on the surface of the When M is B, the M source may be B 2 O 3 Or H 3 BO 3 The method comprises the steps of carrying out a first treatment on the surface of the When M is W, the M source may be WO 3 Or H 2 WO 4 The method comprises the steps of carrying out a first treatment on the surface of the When M is Mg, the M source may be Mg (OH) 2 Or MgO; when M is Mo, the M source may be MoO 3 The method comprises the steps of carrying out a first treatment on the surface of the When M is Na, the M source may be Na 2 CO 3 Or NaNO 3 。
The precursor of the ternary cathode material and the cathode material according to the present application will be described in further detail with reference to specific examples and comparative examples.
Example 1
The embodiment is a precursor of a nickel cobalt lithium manganate ternary positive electrode material, and the preparation process comprises the following steps:
step A), the following reaction base solution is introduced into a growth kettle: 2.5mol/L of nickel cobalt manganese mixed salt solution (molar ratio of nickel, cobalt and manganese is 92:5:3), 10mol/L of mixed solution of lithium hydroxide and sodium hydroxide (LiOH/NaOH=0.8), and 5mol/L of ammonia water solution;
wherein, the flow rate of the nickel-cobalt-manganese mixed salt solution is 250L/h, the pH value is 11.7 after the reaction base solution is fully mixed, and the ammonia concentration is 2g/L;
and under the inert atmosphere, the reaction temperature is 80 ℃, and the reaction base solution reacts to obtain the precursor crystal nucleus after growth.
And B), introducing ammonia water solution and sodium hydroxide solution into the oxidation kettle to regulate and control the pH value of feed liquid in the oxidation kettle to be 11.7, introducing oxygen into the oxidation kettle at a flow rate of 10L/min, regulating and controlling the oxygen concentration in the oxidation kettle to be 35%, and oxidizing the precursor crystal nucleus after growth at a temperature of 80 ℃ to obtain the oxidized precursor crystal nucleus.
Step C), the step A) and the step B) are continuously and sequentially circulated to obtain the precursor of the nickel cobalt lithium manganate ternary positive electrode material.
Examples 2 to 7 and comparative examples 1 to 5
Examples 2-7 and comparative examples 1-5 are each precursors of a lithium nickel cobalt manganese oxide ternary cathode material, and the specific preparation process can refer to the preparation of example 1, except that the concentration of the reactant and the reaction conditions are different, wherein the growth and the oxidation process of the precursors in comparative example 5 are not performed in stages, i.e., are performed in the same reaction kettle, and the specific compositions of the concentration of the reactant and the reaction conditions are shown in table 1. The precursors in the above examples and comparative examples were subjected to BET specific surface area test, lithium ion content test, and D50 measurement of the precursors, and the test results are shown in table 1.
TABLE 1
As can be seen from the data of examples 1 to 7 and comparative examples 1 to 4 in table 1, when the molar ratio of nickel, cobalt and manganese in the nickel-cobalt-manganese mixed salt solution is the same, the content of lithium ions in the precursor can be remarkably improved by introducing oxygen into the oxidation kettle to oxidize the precursor, and the oxidized precursor crystal nucleus has finer whiskers and larger porosity, and meanwhile, the surface activity of the precursor crystal nucleus is improved in the oxidation process, so that the intercalation amount of lithium ions is improved.
Fig. 3 to 13 are SEM images of the precursors of examples 2 to 7 and comparative examples 1 to 5, and the precursors D50 of examples 2 to 7 and comparative examples 1 to 4 are between 8 and 15 μm and the precursor D50 of comparative example 5 is only 3 μm, as compared with fig. 3 to 13.
Corresponding positive electrode materials are prepared according to the content of lithium ions in the precursors in the above examples and comparative examples, when the lithium intercalation amount reaches more than 1.04, the ternary positive electrode materials can be obtained by direct sintering, and if the lithium intercalation amount is less than 1.04, a proper amount of lithium ions can be supplemented and then sintering can be carried out, so that the ternary positive electrode materials can be obtained. The secondary battery prepared by using the positive electrode material is subjected to charge-discharge capacity test according to 0.2C/0.2C, the voltage range is 2.5-4.25V, and the test results are shown in Table 2.
TABLE 2
| Sequence number | 0.2C Capacity (mAh/g) |
| Example 1 | 215.1 |
| Example 2 | 216.2 |
| Comparative example 1 | 212.5 |
| Example 3 | 202.4 |
| Example 4 | 204.5 |
| Example 5 | 201.3 |
| Example 6 | 200.7 |
| Example 7 | 203.1 |
| Comparative example 2 | 201.3 |
| Comparative example 3 | 201.2 |
| Comparative example 4 | 200.1 |
| Comparative example 5 | 195 |
As can be seen from the data of examples 1 to 7 and comparative examples 1 to 4 in table 2, when the molar ratios of nickel, cobalt and manganese in the nickel-cobalt-manganese mixed salt solution are the same, the ternary positive electrode material obtained by directly sintering the precursor prepared by the preparation method in the example of the present application has a discharge capacity value of 0.2C close to that of the ternary positive electrode material obtained by sintering after supplementing a proper amount of lithium ions.
The lithium ion content of the precursor in example 4 is significantly higher than that of the precursor in comparative example 5, and the precursor D50 in example 4 is 8 μm, and the precursor D50 in comparative example 5 is only 3 μm, which illustrates the preparation method of the precursor of the ternary positive electrode material according to the present application, and by performing the growth and oxidation processes of the precursor in sections, a large amount of lithium ions can be uniformly distributed in the precursor, and a ternary lithium-containing precursor with a larger D50 can be obtained, compared with the existing direct oxidation lithium intercalation process.
The foregoing is merely illustrative embodiments of the present application, but the scope of the present application is not limited thereto, and any person skilled in the art can easily think about variations or substitutions within the technical scope of the present application, and the application should be covered. Therefore, the protection scope of the application is subject to the protection scope of the claims.
Claims (4)
1. The preparation method of the precursor of the ternary positive electrode material is characterized by comprising the following steps of:
preparing a reaction solution: preparing a nickel-cobalt-manganese mixed salt solution, a lithium salt solution, a precipitant solution and a complexing agent solution;
under the protection of inert gas, mixing and uniformly stirring the reaction solution to obtain precursor crystal nucleus;
the method comprises the steps that a growth process and an oxidation process are sequentially repeated on a precursor crystal nucleus until a precursor with a preset particle size is obtained, wherein the growth process and the oxidation process are carried out in a segmented mode;
the precursor crystal nucleus sequentially repeats the growth process and the oxidation process until a precursor with preset particle size is obtained, and the method comprises the following steps:
step A), growing the precursor crystal nucleus in a reaction solution under an inert atmosphere; the reaction solution is a mixed solution of nickel-cobalt-manganese mixed salt solution, lithium salt solution, precipitant solution and complexing agent solution, and the pH value of the reaction solution is 9-12;
step B), oxidizing the grown precursor crystal nucleus in oxygen atmosphere to obtain oxidized precursor crystal nucleus;
continuously and sequentially circulating the step A) and the step B) to obtain a precursor with preset particle size;
and (3) after each step B, washing the oxidized precursor crystal nucleus to remove oxygen, and then executing the step A.
2. The preparation method according to claim 1, wherein the total metal ion concentration of the nickel-cobalt-manganese mixed salt solution is 1-5 mol/L, and the molar ratio of nickel, cobalt and manganese is m: p, m is more than or equal to 0.5 and less than or equal to 1, n is more than or equal to 0 and less than or equal to 0.2, and p is more than or equal to 0 and less than or equal to 0.3.
3. The method according to claim 1, wherein the concentration of oxygen in the step B is 2% to 35%.
4. A positive electrode material prepared by using the precursor prepared by the preparation method as a raw material, wherein the positive electrode material has a general formula of Li d Ni a Co b Mn c M x O 2 Wherein M is one or a combination of at least two of Al, zr, sr, Y, ba, ti, B, W, mg, mo and Na, d is more than or equal to 1 and less than or equal to 1.2, a is more than or equal to 0.8 and less than or equal to 0.95,0<b≤0.2，0<c≤0.2，0≤x≤0.05，a+b+c+x＝1。
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