CN115196692A - Preparation method and device of precursor of ternary cathode material, precursor and cathode material - Google Patents
Preparation method and device of precursor of ternary cathode material, precursor and cathode material Download PDFInfo
- Publication number
- CN115196692A CN115196692A CN202210855847.2A CN202210855847A CN115196692A CN 115196692 A CN115196692 A CN 115196692A CN 202210855847 A CN202210855847 A CN 202210855847A CN 115196692 A CN115196692 A CN 115196692A
- Authority
- CN
- China
- Prior art keywords
- precursor
- solution
- crystal nucleus
- cathode material
- growth
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000002243 precursor Substances 0.000 title claims abstract description 186
- 239000010406 cathode material Substances 0.000 title claims abstract description 56
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 239000013078 crystal Substances 0.000 claims description 63
- 238000007254 oxidation reaction Methods 0.000 claims description 62
- 239000000243 solution Substances 0.000 claims description 62
- 230000003647 oxidation Effects 0.000 claims description 61
- 238000000034 method Methods 0.000 claims description 59
- 238000006243 chemical reaction Methods 0.000 claims description 33
- 239000012266 salt solution Substances 0.000 claims description 27
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 24
- 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 16
- 239000002245 particle Substances 0.000 claims description 15
- 229910003002 lithium salt Inorganic materials 0.000 claims description 12
- 159000000002 lithium salts Chemical class 0.000 claims description 12
- 239000007774 positive electrode material Substances 0.000 claims description 11
- 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
- 229910052759 nickel Inorganic materials 0.000 claims description 8
- 239000011259 mixed solution Substances 0.000 claims description 7
- 230000001590 oxidative effect Effects 0.000 claims description 7
- 239000012716 precipitator Substances 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 229910021645 metal ion Inorganic materials 0.000 claims description 4
- 238000002156 mixing 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
- 238000003756 stirring Methods 0.000 claims description 3
- 229910052727 yttrium Inorganic materials 0.000 claims description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 32
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 32
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 24
- 230000000052 comparative effect Effects 0.000 description 23
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 18
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 17
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 16
- 229910052744 lithium Inorganic materials 0.000 description 16
- 239000002562 thickening agent Substances 0.000 description 11
- 239000007788 liquid Substances 0.000 description 10
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 9
- 235000011114 ammonium hydroxide Nutrition 0.000 description 9
- 229910021529 ammonia Inorganic materials 0.000 description 7
- 238000005245 sintering Methods 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 6
- 238000003780 insertion Methods 0.000 description 6
- 230000037431 insertion Effects 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 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 4
- 239000002585 base Substances 0.000 description 4
- 230000001105 regulatory effect Effects 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 238000012546 transfer Methods 0.000 description 4
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000002687 intercalation Effects 0.000 description 3
- 238000009830 intercalation Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000003513 alkali Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 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
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 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
- 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
- 230000001276 controlling effect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 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
- 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
- 238000000926 separation method Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 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
Images
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
-
- 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 a device of a precursor of a ternary cathode material, the precursor and the cathode material. The general formula of the precursor of the ternary cathode 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, a + b + c =1. Lithium ions can be inserted into the precursor of the ternary cathode material.
Description
Technical Field
The application relates to the technical field of batteries, in particular to a preparation method and a device of a precursor of a ternary cathode material, the precursor and the cathode 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, people have higher and higher requirements on the electrochemical performance of lithium ion batteries. 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 significant ternary synergistic effect, high energy density, relatively low cost and good safety function, and has become the main development direction of the current lithium battery positive electrode material. At present, the mainstream process in the synthesis process of the ternary cathode material is to synthesize a hydroxide or carbonate precursor of the ternary cathode material, and then mix the precursor and a lithium salt and sinter the mixture at a high temperature to obtain the cathode material.
The Chinese invention application with publication number CN104934593A adds nickel acetate, cobalt acetate, manganese acetate and lithium salt into aqueous solution of glucose and citric acid to be stirred to form paste-like precursor, then ball milling and microwave sintering are carried out to obtain ternary anode material.
The Chinese invention application with publication number CN112133890A adopts one-step synthesis of a lithium-containing ternary precursor and then high-temperature sintering to obtain a single crystal ternary cathode material, and the process carries out lithium pre-embedding at the stage of the precursor, so that the sintering process of the cathode material is simplified, but the process is only suitable for single crystal small particles, and because the lithium-containing precursor is difficult to control in the synthesis process and the growth of the precursor particles is greatly influenced by the pH value, the process cannot synthesize a large-particle polycrystalline lithium-containing precursor and a large-particle cathode material with large D50.
In summary, the current synthesis processes of the precursor of the ternary cathode material and the cathode material cannot be compatible with the uniform insertion of lithium ions into the precursor and the normal growth of the precursor, so that it is difficult to obtain the polycrystalline lithium-containing precursor and the cathode material with ideal particle size.
Disclosure of Invention
The application discloses a preparation method and a device of a precursor of a ternary cathode material, the precursor and the cathode material, and aims to solve the problem that the lithium ion insertion amount in the precursor of the conventional ternary cathode material is low.
In order to achieve the purpose, the application provides the following technical scheme:
in a first aspect, the present application provides a precursor of a ternary cathode material, wherein the general formula of the precursor of the ternary cathode 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≤1.2，a+b+c＝1。
Further, the D50 of the precursor is 6 to 15 μm, and the BET of the precursor is 4 to 20m 2 /g。
In a second aspect, the present application provides a method for preparing a precursor of a ternary cathode material, comprising the steps of:
and repeating the growth process and the oxidation process of the precursor crystal nucleus in sequence until the precursor with the preset particle size is obtained, wherein the growth process and the oxidation process are carried out in sections.
Further, the preparation method further includes a step of preparing a precursor crystal nucleus including:
preparing a reaction solution: preparing a nickel-cobalt-manganese mixed salt solution, a lithium salt solution, a precipitator solution and a complexing agent solution;
and under the protection of inert gas, mixing and uniformly stirring the reaction solution to obtain a precursor crystal nucleus.
Further, the precursor crystal nucleus sequentially repeats the growth process and the oxidation process until the precursor with the preset particle size is obtained, and the method comprises the following steps:
step A), under inert atmosphere, precursor crystal nucleus grows in reaction solution; wherein the reaction solution is a mixed solution of a nickel-cobalt-manganese mixed salt solution, a lithium salt solution, a precipitator solution and a complexing agent solution, and the pH value of the reaction solution is 9-12;
step B), oxidizing the grown precursor crystal nucleus in an oxygen atmosphere to obtain an oxidized precursor crystal nucleus;
continuously and sequentially circulating the step A) and the step B) to obtain a precursor with a preset particle size.
Further, after each step B, the oxidized precursor nuclei are washed to remove oxygen and then step A is performed.
Furthermore, the concentration of the total metal ions in the nickel-cobalt-manganese mixed salt solution is 1-5 mol/L, the molar ratio of nickel, cobalt and manganese is m: n: p, m is more than or equal to 0.5 and less than or equal to 1, n is more than 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 an ammonia water solution, and the ammonia concentration in the reaction solution is 2-15 g/L.
Further, the concentration of the oxygen in the step B is 2-35%.
In a third aspect, the present application provides an apparatus applying the preparation method of the second aspect, comprising: the growth kettle is used for the growth of precursor crystal nuclei; the oxidation kettle is used for oxidizing the precursor crystal nucleus.
In a fourth aspect, the present application provides a cathode material prepared from the precursor of the first aspect or the precursor prepared by the preparation method of the second aspect, wherein the cathode material has a general formula of Li d Ni a Co b Mn c M x O 2 Wherein M is one or the combination of at least two of Al, zr, sr, Y, ba, ti, B, W, mg, mo or 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<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 cathode 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, a + b + c =1. Lithium ions can be inserted into the precursor of the ternary cathode material.
Drawings
Fig. 1 is a schematic flow chart of a method for preparing a precursor of a ternary cathode material provided in an embodiment of the present application;
fig. 2 is a schematic view of a device for preparing a precursor of a ternary cathode material according to an embodiment of the present disclosure;
FIG. 3 is an SEM photograph of the precursor in example 2;
FIG. 4 is an SEM photograph of the precursor in example 3;
FIG. 5 is an SEM photograph of the precursor of example 4;
FIG. 6 is an SEM photograph of the precursor of example 5;
FIG. 7 is an SEM photograph of the precursor of example 6;
FIG. 8 is an SEM photograph of the precursor of example 7;
FIG. 9 is an SEM photograph of the precursor in comparative example 1;
FIG. 10 is an SEM photograph of the precursor in comparative example 2;
FIG. 11 is an SEM photograph of the precursor of comparative example 3;
FIG. 12 is an SEM photograph of the precursor of comparative example 4;
fig. 13 is an SEM image of the precursor in comparative example 5.
Reference numerals:
11-growth kettle; 12-an oxidation kettle; 13-a transfer kettle; 14-a thickener; 15-a pump;
01-a flash port; 02-material return port; 03-feeding port; 04-a discharge hole; 05-a feed port; 06-a discharge port; 07-reflux inlet.
Detailed Description
In order to make the objects, technical solutions and advantages of the present application clearer, the present application will be described in further detail with reference to the accompanying drawings, and it is obvious that the described embodiments are only a part of the embodiments of the present application, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present application.
The application scenario described in the embodiment of the present application is for more clearly illustrating the technical solution of the embodiment of the present application, and does not form a limitation on the technical solution provided in the embodiment of the present application, and it can be known by a person skilled in the art that with the occurrence of a new application scenario, the technical solution provided in the embodiment of the present application is also applicable to similar technical problems. In the description of the present application, the meaning of "a plurality" is two or more, unless otherwise specified.
At present, 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 electronic industry, the requirements of consumers on the cruising performance, safety performance and the like of electric vehicles are gradually strict, and therefore, higher-performance secondary batteries are required to meet the power consumption requirements of electric vehicles. Among them, the ternary positive electrode material can satisfy the increasing application requirements of secondary batteries due to high energy density, relatively low cost and good safety function. 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 the uniform insertion of lithium ions into the precursor and the normal growth of the precursor.
In view of this, embodiments of the present application provide a precursor of a ternary cathode material, where the general formula of the precursor 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≤1.2，a+b+c＝1。
The general formula of the precursor of the ternary cathode material in the embodiment of the application is Ni a Co b Mn c Li d (OH) 2 Where 0.8. Ltoreq. A.ltoreq.0.95, for example 0.80, 0.82, 0.85, 0.88, 0.9, 0.92 or 0.95, but not limited to the values listed, and other values not listed in the numerical range are also suitable. Wherein, 0<b.ltoreq.0.2, 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 listed, and other values not listed in the numerical range are likewise suitable. Wherein, 0<c is less than or equal to 0.2, such as 0.05, 0.08, 0.1, 0.12, 0.15, 0.17, 0.18 or 0.2, but not limited to the values recited, other values not recited within the numerical range are equally applicable. Wherein, 0<d.ltoreq.1.2, 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 listed, and other values not listed in the numerical range are likewise suitable.
The D50 of the precursor can be 6-15 μm, and the BET of the precursor is 4-20 m 2 (ii) in terms of/g. The D50 of this 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 synthesis process of the precursor of the ternary cathode material, uniform intercalation of lithium ions is difficult to realize, because in the conventional lithium intercalation oxidation process, precursor crystal nuclei grow under the oxidation condition and tend to form more crystal nuclei, a lithium-containing precursor with larger D50 cannot be synthesized, and because the activity of the precursor crystal nuclei is larger and lithium ions are rapidly deposited under the oxidation environment, the precursor in which the lithium ions are uniformly intercalated cannot be obtained.
In view of this, an embodiment of the present application provides a method for preparing a precursor of a ternary cathode material, including the following steps:
and repeating the growth process and the oxidation process of the precursor crystal nucleus in sequence until the precursor with the preset particle size is obtained, wherein the growth process and the oxidation process are carried out in sections.
According to the preparation method of the precursor of the ternary cathode material, the growth and oxidation processes of the precursor are performed in a segmented mode, so that the growth process and the oxidation process of the precursor are effectively separated. The precursor crystal nucleus whisker appearance can be refined and the porosity can be increased through oxidation, so that favorable conditions are provided for the embedding of lithium ions, the surface activity of the oxidized precursor crystal nucleus is improved, the lithium ions are more easily adsorbed on the surface of the oxidized precursor crystal nucleus, and the lithium ion embedding amount is increased. In addition, because 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 the growth process and the oxidation process are sequentially repeated through the precursor crystal nucleus, a large number of lithium ions can be uniformly distributed in the precursor, and the ternary lithium-containing precursor with ideal D50 is obtained.
It should be noted that the growth process and the oxidation process are performed in stages, which means that the growth and the oxidation process of the precursor crystal nuclei are performed in different time periods, so that the growth and the oxidation process of the precursor crystal nuclei are separated.
Among them, the precursor crystal nucleus needs to be subjected to a growth process and then an oxidation process in order to further grow the precursor crystal nucleus so that lithium ions can be efficiently deposited on the surface of the precursor crystal nucleus.
In one embodiment of the present application, the preparation method further comprises a step of preparing a precursor crystal nucleus comprising:
preparing a reaction solution: preparing a nickel-cobalt-manganese mixed salt solution, a lithium salt solution, a precipitator solution and a complexing agent solution;
and under the protection of inert gas, mixing and uniformly stirring the reaction solution to obtain a precursor crystal nucleus.
It is to be understood that the preparation method of the precursor crystal nuclei is not limited in the examples of the present application, but the above is only one possible preparation method of the precursor crystal nuclei.
Fig. 1 is a schematic flow chart of a method for preparing a precursor of a ternary cathode material according to an embodiment of the present disclosure, and with reference to fig. 1, a flow of a precursor crystal nucleus sequentially repeating a growth process and an oxidation process until a precursor with a predetermined particle size is obtained is described, which specifically includes the following steps:
step A), growing a precursor crystal nucleus in a reaction solution in an inert atmosphere; wherein the reaction solution is a mixed solution of a nickel-cobalt-manganese mixed salt solution, a lithium salt solution, a precipitator solution and a complexing agent solution, and the pH value of the reaction solution is 9-12;
step B), oxidizing the grown precursor crystal nucleus in an oxygen atmosphere to obtain an oxidized precursor crystal nucleus;
and C), continuously and sequentially circulating the step A) and the step B) to obtain a precursor with a preset particle size.
The growth and oxidation processes of the precursor can be continuously and sequentially circulated, so that the precursor with large-size particles can be finally obtained. Wherein, it should be noted that the pH value of the oxidation reaction in the step B) and the pH value of the reaction solution in the step A) are both 9-12, 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 nuclei are washed to remove oxygen and then step a is performed, thereby preventing oxygen from affecting the growth process of the precursor crystal nuclei.
In the reaction solution of the embodiment of the present application, the concentration of the total metal ions in the nickel-cobalt-manganese mixed salt solution is 1 to 5mol/L, and the concentration of the total metal ions in the nickel-cobalt-manganese mixed salt solution is, for example, 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: p, m is more than or equal to 0.5 and less than or equal to 1, n is more than 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 present application, the complexing agent solution is an aqueous ammonia solution, the concentration of the aqueous ammonia solution is 3 to 10mol/L, and the concentration of the aqueous ammonia solution is, for example, 3mol/L, 3.5mol/L, 4mol/L, 5mol/L, 6mol/L, 8mol/L, or 10mol/L.
In the reaction solution of the present example, the precipitant solution is an alkali solution, for example, a sodium hydroxide solution. In one embodiment of the present application, the lithium salt solution is a lithium hydroxide solution. Wherein, the precipitant solution and the lithium salt solution need to be mixed according to a certain ratio, taking the precipitant solution as a sodium hydroxide solution and the lithium salt solution as a lithium hydroxide solution as an example, the molar concentration of the mixed solution of the precipitant solution and the lithium salt solution is 1 to 15mol/L, and the ratio of the lithium hydroxide to the sodium hydroxide is 0.2 to 0.8, for example, the ratio of the lithium hydroxide to the sodium hydroxide is 0.2, 0.3, 0.4, 0.5, 0.6, 0.7 or 0.8, and the like.
It is understood that the concentrations of the aqueous ammonia solution and the alkali solution in the reaction solution are controlled so that the ammonia concentration in the reaction solution is 2 to 15g/L each. The concentration of ammonia 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% to 35%, and the concentration of oxygen may be 2%, 4%, 6%, 10%, 15%, 20%, 25%, 30%, or 35%. In one embodiment of the present application, the reaction temperature is controlled to be 50 to 80 ℃ during the growth and oxidation of the precursor crystal nuclei. The temperature during the growth and oxidation of the precursor nuclei is, for example, 50 deg.C, 52 deg.C, 55 deg.C, 60 deg.C, 65 deg.C, 70 deg.C, 75 deg.C or 80 deg.C.
Based on the same inventive concept, the embodiment of the present application provides an apparatus, including: the growth kettle is used for the growth of precursor crystal nuclei; 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 device for preparing a precursor of a ternary cathode material according to an embodiment of the present application will be described in detail 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 reactor 12 is connected to the feed port 05 of the thickener 14, and the discharge port 06 of the thickener 14 is connected to the feed back port 02 of the growth reactor 11.
The process for preparing the precursor of the ternary cathode material by applying the device is specifically described as follows:
introducing a mixed solution of a nickel-cobalt-manganese mixed salt solution, sodium hydroxide, lithium hydroxide and an ammonia water solution into a growth kettle 11, regulating the pH value range of the mixed solution to be 9-12, controlling the ammonia concentration to be 2-15 g/L, and reacting the mixed solution in an inert atmosphere to obtain a grown precursor crystal nucleus;
introducing an ammonia water solution and a sodium hydroxide solution into the oxidation kettle 12 to regulate the pH value range of a feed liquid in the oxidation kettle 12 to be 9-12, wherein the ammonia concentration of the feed liquid is 2-15 g/L, introducing the grown precursor crystal nucleus in the growth kettle 11 into the oxidation kettle 12 through a discharge hole 01, introducing oxygen into the oxidation kettle 12 at a flow rate of 1-10L/min, and regulating the oxygen concentration in the oxidation kettle 12 to be 2-35% to oxidize the grown precursor crystal nucleus to obtain an oxidized precursor crystal nucleus;
the material liquid in the oxidation kettle 12 flows out of the oxidation kettle 12 through the discharge port 04, enters the thickener 14 through the feeding port 05, is separated by the thickener 14, is discharged from the thickener 14 through the discharge port 06 in the form of precipitate after being oxidized, enters the growth kettle 11 through the return port 02, and continues to grow precursor crystal nuclei and embed lithium ions in the growth kettle 11. 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 kettle 11 may be used for preparation and growth of the precursor crystal nucleus, or the precursor crystal nucleus may be directly added into the growth kettle 11, and the growth kettle 11 is only used for growth of the precursor, and both of the above solutions are within the protection scope of the present application. In an embodiment of the present application, the flow rate of the nickel-cobalt-manganese mixed salt solution introduced into the growth reactor 11 is 50 to 300L/h, and specifically may be 50L/h, 60L/h, 80L/h, 110L/h, 150L/h, 200L/h, 250L/h, or 300L/h, and the like.
It is understood that, in order to transfer 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 an embodiment of the present application, at least part of a 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 backflow port 07, wherein the clarified liquid is an ammonia solution and a sodium hydroxide solution 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 as to save raw materials and reduce reaction cost.
The device that this application provided carries out the oxidation of precursor through the growth that carries out the precursor crystal nucleus in growth cauldron 11, carries out the precursor in oxidation cauldron 12 to with the growth and the oxidation process separation of precursor, and, the device can be in succession repeated growth and oxidation process in proper order, has promoted reaction efficiency.
According to the precursor provided by the embodiment of the application, lithium ions can be embedded, 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, the ternary cathode material can be obtained by direct sintering, and if the ratio of the molar quantity of lithium embedded 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 added and then sintering is carried out, so that the ternary cathode material can be obtained. Calculating the amount of lithium ions to be supplemented according to the difference between the preset lithium ion content in the positive electrode material and the lithium ion content in the precursor, and adding the lithium-containing precursor and corresponding LiOH or Li 2 CO 3 And sintering after uniform mixing to obtain the ternary cathode material.
Based on the same inventive concept, the embodiment of the present application further provides a cathode material prepared by using the precursor of the various possible embodiments of the present application or the precursor prepared by the various possible preparation methods of the present application as a raw material, wherein the general formula of the cathode material is Li d Ni a Co b Mn c M x O 2 Wherein M is one or the combination of at least two of Al, zr, sr, Y, ba, ti, B, W, mg, mo or 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<b≤0.2，0<c is less than or equal to 0.2, x is less than or equal to 0.05, a + b + c + x =1. When M is Al, the M source can be Al 2 O 3 Or Al (OH) 3 (ii) a When M is Zr, the M source may be ZrO 2 Or Zr (NO) 3 ) 4 (ii) a When M is Sr, the M source can be SrO; when M is Y, the M source can be Y 2 O 3 (ii) a When M is Ba, the M source can be BaCO 3 Or Ba (OH) 2 (ii) a When M is B, the M source can be B 2 O 3 Or H 3 BO 3 (ii) a When M is W, the M source can be WO 3 Or H 2 WO 4 (ii) a When M is Mg, the source of M can be Mg (OH) 2 Or MgO; when M is Mo, the M source may be MoO 3 (ii) a When M is Na, the M source can be Na 2 CO 3 Or NaNO 3 。
The precursor of the ternary positive electrode material and the positive electrode material in 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 cathode material, and the preparation process comprises the following steps:
step A), introducing the following reaction base solution into a growth kettle: 2.5mol/L nickel cobalt manganese mixed salt solution (molar ratio of nickel, cobalt and manganese is 92;
wherein the flow rate of the nickel-cobalt-manganese mixed salt solution is 250L/h, the pH value of the reaction base solution is 11.7 after the reaction base solution is fully mixed, and the ammonia concentration is 2g/L;
and reacting the reaction base solution under the condition of inert atmosphere and 80 ℃ to obtain the grown precursor crystal nucleus.
And step B), introducing an ammonia water solution and a sodium hydroxide solution into the oxidation kettle to regulate the pH value of the feed liquid in the oxidation kettle to be 11.7, regulating the ammonia concentration to be 2g/L, introducing oxygen into the oxidation kettle at the flow rate of 10L/min, regulating the oxygen concentration in the oxidation kettle to be 35% and the temperature to be 80 ℃, and oxidizing the grown precursor crystal nucleus to obtain the oxidized precursor crystal nucleus.
And C), continuously and sequentially circulating the step A) and the step B) to obtain a precursor of the nickel cobalt lithium manganate ternary cathode material.
Examples 2 to 7 and comparative examples 1 to 5
Examples 2 to 7 and comparative examples 1 to 5 are precursors of a nickel cobalt lithium manganate ternary positive electrode material, and the specific preparation process can be referred to the preparation of example 1, except for the differences of the concentrations of the reactants and the reaction conditions, wherein the growth and oxidation processes of the precursor in comparative example 5 are not performed in stages, i.e., both are performed in the same reaction vessel, and the specific compositions of the concentrations of the reactants and the reaction conditions are shown in table 1. The precursors of 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
It can be seen from the data associated with examples 1-7 and comparative examples 1-4 in table 1 that when the molar ratio of nickel, cobalt and manganese in the nickel-cobalt-manganese mixed salt solution is the same, oxygen is introduced into the oxidation kettle to oxidize the precursor, so as to significantly increase the content of lithium ions in the precursor, and it can be seen that the oxidized precursor crystal nucleus has fine whiskers and large porosity, and meanwhile, the oxidation process improves the surface activity of the precursor crystal nucleus, thereby increasing the insertion amount of lithium ions.
FIGS. 3 to 13 are SEM images of precursors in examples 2 to 7 and comparative examples 1 to 5, and in comparison with FIGS. 3 to 13, D50 of the precursors in examples 2 to 7 and comparative examples 1 to 4 is between 8 and 15 μm, and D50 of the precursor in comparative example 5 is only 3 μm.
Corresponding cathode materials are prepared according to the content of lithium ions in the precursors in the examples and the comparative examples, when the lithium insertion amount reaches more than 1.04, the cathode materials can be directly sintered to obtain the ternary cathode material, and if the lithium insertion amount is less than 1.04, a proper amount of lithium ions can be supplemented and then sintered to obtain the ternary cathode material. The secondary battery prepared by the cathode material is subjected to a charge-discharge capacity test according to 0.2C/0.2C, the voltage range is 2.5-4.25V, and the test results are listed in Table 2.
TABLE 2
| Serial 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 0.2C discharge capacity value of the ternary cathode material obtained by directly sintering the precursor prepared by the preparation method in the embodiment of the present application is close to that of the ternary cathode material obtained by sintering after adding 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 D50 of the precursor in example 4 is 8 μm, and the D50 of the precursor in comparative example 5 is only 3 μm, which illustrates the preparation method of the precursor of the ternary cathode material in the present application, by performing the growth and oxidation processes of the precursor in stages, compared with the existing direct oxidation lithium intercalation process, a large amount of lithium ions can be uniformly distributed in the precursor, and a ternary lithium-containing precursor with a large D50 can be obtained.
The above description is only for the specific 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 of the changes or substitutions within the technical scope of the present application, and shall be covered by the scope of the present application. Therefore, the protection scope of the present application shall be subject to the protection scope of the claims.
Claims (10)
1. The precursor of the ternary cathode material is characterized in that the general formula of the precursor 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≤1.2，a+b+c＝1。
2. Precursor according to claim 1, characterized in that the D50 of the precursor is between 6 and 15 μm and the BET of the precursor is between 4 and 20m 2 /g。
3. A preparation method of a precursor of a ternary cathode material is characterized by comprising the following steps:
and the precursor crystal nucleus sequentially repeats the growth process and the oxidation process until the precursor with the preset particle size is obtained, wherein the growth process and the oxidation process are carried out in a segmented manner.
4. The production method according to claim 3, further comprising a step of producing the precursor crystal nucleus, the production method comprising:
preparing a reaction solution: preparing a nickel-cobalt-manganese mixed salt solution, a lithium salt solution, a precipitator 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.
5. The preparation method according to claim 3 or 4, wherein the precursor crystal nuclei sequentially repeat the growth process and the oxidation process until a precursor having a predetermined particle size is obtained, comprising:
step A), growing the precursor crystal nucleus in a reaction solution in an inert atmosphere; the reaction solution is a mixed solution of a nickel-cobalt-manganese mixed salt solution, a lithium salt solution, a precipitator solution and a complexing agent solution, and the pH value of the reaction solution is 9-12;
step B), oxidizing the grown precursor crystal nucleus in an oxygen atmosphere to obtain an oxidized precursor crystal nucleus;
continuously and sequentially circulating the step A) and the step B) to obtain a precursor with a preset particle size.
6. The method according to claim 5, wherein step A is performed after the oxidized precursor nuclei are washed to remove oxygen after each step B.
7. The preparation method according to claim 4, wherein the concentration of total metal ions in the nickel-cobalt-manganese mixed salt solution is 1-5 mol/L, and the molar ratio of nickel, cobalt and manganese is m: n: p, 0.5. Ltoreq. M.ltoreq.1, 0. Ltoreq. N.ltoreq.0.2, 0. Ltoreq. P.ltoreq.0.3.
8. The method according to claim 5, wherein the concentration of oxygen in step B is 2 to 35%.
9. An apparatus for applying the production method according to any one of claims 3 to 8, comprising: the growth kettle is used for the growth of the precursor crystal nucleus; the oxidation kettle is used for oxidizing the precursor crystal nucleus.
10. A positive electrode material produced using the precursor according to claim 1 or 2 or the precursor produced by the production method according to any one of claims 3 to 8 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 the combination of at least two of Al, zr, sr, Y, ba, ti, B, W, mg, mo or 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<b≤0.2，0<c≤0.2，0≤x≤0.05，a+b+c+x＝1。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210855847.2A CN115196692B (en) | 2022-07-20 | 2022-07-20 | Preparation method and device of precursor of ternary positive electrode material, precursor and positive electrode material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210855847.2A CN115196692B (en) | 2022-07-20 | 2022-07-20 | Preparation method and device of precursor of ternary positive electrode material, precursor and positive electrode material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115196692A true CN115196692A (en) | 2022-10-18 |
| CN115196692B CN115196692B (en) | 2023-11-03 |
Family
ID=83582932
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210855847.2A Active CN115196692B (en) | 2022-07-20 | 2022-07-20 | Preparation method and device of precursor of ternary positive electrode material, precursor and positive electrode material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115196692B (en) |
Citations (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101447566A (en) * | 2008-12-29 | 2009-06-03 | 清华大学深圳研究生院 | Li-ion battery positive electrode material with layered-spinel symbiotic structure and preparation method |
| CN103066275A (en) * | 2013-01-24 | 2013-04-24 | 湖南桑顿新能源有限公司 | Preparation method of spherical high-voltage lithium nickel manganate anode material |
| CN104852038A (en) * | 2015-04-08 | 2015-08-19 | 中国科学院长春应用化学研究所 | Preparation method of high-capacity quickly-chargeable/dischargeable lithium ion battery ternary anode material |
| CN105355907A (en) * | 2015-12-10 | 2016-02-24 | 哈尔滨工业大学 | Lithium metallic oxide precursor material with annual ring type structure, anode material prepared by lithium metallic oxide precursor material, and preparation method and application |
| CN105489886A (en) * | 2016-01-11 | 2016-04-13 | 山东玉皇新能源科技有限公司 | Nickel-cobalt-aluminum ternary cathode material with high tap-density and preparation method of nickel-cobalt-aluminum ternary cathode material |
| CN108502937A (en) * | 2018-04-17 | 2018-09-07 | 哈尔滨工业大学 | A kind of polynary persursor material of ball-shaped lithium-ion battery anode and its preparation method and application |
| CN109987647A (en) * | 2018-11-07 | 2019-07-09 | 北京泰丰先行新能源科技有限公司 | A kind of nickelic ternary precursor of doping type and preparation method thereof |
| CN109994716A (en) * | 2018-11-07 | 2019-07-09 | 北京泰丰先行新能源科技有限公司 | A kind of nickelic ternary precursor of cladded type and preparation method thereof |
| CN112133890A (en) * | 2019-06-24 | 2020-12-25 | 比亚迪股份有限公司 | Lithium-containing ternary precursor and preparation method thereof, ternary cathode material and preparation method thereof, and lithium ion battery |
| CN113224289A (en) * | 2021-03-23 | 2021-08-06 | 北京化工大学 | Method for preparing single crystal ternary cathode material by controlling supersaturation degree of solution |
| CN113387399A (en) * | 2021-05-13 | 2021-09-14 | 北京泰丰先行新能源科技有限公司 | High-nickel ternary positive electrode material precursor and preparation method thereof |
| CN114084914A (en) * | 2021-11-05 | 2022-02-25 | 广东佳纳能源科技有限公司 | Ternary precursor and preparation method and application thereof |
| CN114408988A (en) * | 2022-03-31 | 2022-04-29 | 金驰能源材料有限公司 | Ternary positive electrode material precursor and preparation method thereof |
| CN114573052A (en) * | 2022-04-07 | 2022-06-03 | 宁波容百新能源科技股份有限公司 | Nickel-cobalt-manganese ternary precursor and preparation method thereof, nickel-cobalt-manganese positive electrode material and preparation method thereof, and lithium ion battery |
-
2022
- 2022-07-20 CN CN202210855847.2A patent/CN115196692B/en active Active
Patent Citations (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101447566A (en) * | 2008-12-29 | 2009-06-03 | 清华大学深圳研究生院 | Li-ion battery positive electrode material with layered-spinel symbiotic structure and preparation method |
| CN103066275A (en) * | 2013-01-24 | 2013-04-24 | 湖南桑顿新能源有限公司 | Preparation method of spherical high-voltage lithium nickel manganate anode material |
| CN104852038A (en) * | 2015-04-08 | 2015-08-19 | 中国科学院长春应用化学研究所 | Preparation method of high-capacity quickly-chargeable/dischargeable lithium ion battery ternary anode material |
| CN105355907A (en) * | 2015-12-10 | 2016-02-24 | 哈尔滨工业大学 | Lithium metallic oxide precursor material with annual ring type structure, anode material prepared by lithium metallic oxide precursor material, and preparation method and application |
| CN105489886A (en) * | 2016-01-11 | 2016-04-13 | 山东玉皇新能源科技有限公司 | Nickel-cobalt-aluminum ternary cathode material with high tap-density and preparation method of nickel-cobalt-aluminum ternary cathode material |
| CN108502937A (en) * | 2018-04-17 | 2018-09-07 | 哈尔滨工业大学 | A kind of polynary persursor material of ball-shaped lithium-ion battery anode and its preparation method and application |
| CN109987647A (en) * | 2018-11-07 | 2019-07-09 | 北京泰丰先行新能源科技有限公司 | A kind of nickelic ternary precursor of doping type and preparation method thereof |
| CN109994716A (en) * | 2018-11-07 | 2019-07-09 | 北京泰丰先行新能源科技有限公司 | A kind of nickelic ternary precursor of cladded type and preparation method thereof |
| CN112133890A (en) * | 2019-06-24 | 2020-12-25 | 比亚迪股份有限公司 | Lithium-containing ternary precursor and preparation method thereof, ternary cathode material and preparation method thereof, and lithium ion battery |
| CN113224289A (en) * | 2021-03-23 | 2021-08-06 | 北京化工大学 | Method for preparing single crystal ternary cathode material by controlling supersaturation degree of solution |
| CN113387399A (en) * | 2021-05-13 | 2021-09-14 | 北京泰丰先行新能源科技有限公司 | High-nickel ternary positive electrode material precursor and preparation method thereof |
| CN114084914A (en) * | 2021-11-05 | 2022-02-25 | 广东佳纳能源科技有限公司 | Ternary precursor and preparation method and application thereof |
| CN114408988A (en) * | 2022-03-31 | 2022-04-29 | 金驰能源材料有限公司 | Ternary positive electrode material precursor and preparation method thereof |
| CN114573052A (en) * | 2022-04-07 | 2022-06-03 | 宁波容百新能源科技股份有限公司 | Nickel-cobalt-manganese ternary precursor and preparation method thereof, nickel-cobalt-manganese positive electrode material and preparation method thereof, and lithium ion battery |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115196692B (en) | 2023-11-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP3297072B1 (en) | Methods for preparing nickel-cobalt-aluminum precursor material and cathode material with gradient distribution of aluminum element | |
| CN113161529B (en) | High-nickel positive electrode material and preparation method thereof | |
| CN111916687B (en) | Positive electrode material, preparation method thereof and lithium ion battery | |
| WO2018015210A1 (en) | A method for upscalable precipitation synthesis of battery materials with tunable particle size distribution | |
| WO2023071409A1 (en) | Single-crystal ternary positive electrode material, preparation method therefor, and application thereof | |
| US11837722B2 (en) | Positive electrode material for lithium ion battery and preparation method therefor, and lithium ion battery | |
| KR20130059029A (en) | Process for producing composite metal oxide | |
| CN113387399A (en) | High-nickel ternary positive electrode material precursor and preparation method thereof | |
| CN109962234B (en) | Concentration gradient single crystal anode material and preparation method thereof | |
| CN111029561A (en) | Ternary lithium battery positive electrode material precursor and preparation method thereof, ternary lithium battery positive electrode material and preparation method and application thereof | |
| CN114620777B (en) | Ultrahigh nickel ternary precursor and preparation method thereof | |
| CN114084914A (en) | Ternary precursor and preparation method and application thereof | |
| CN115000383A (en) | Hollow ternary cathode material and preparation method thereof | |
| CN109768275A (en) | A kind of preparation method for mixing titanium lithium ion anode material presoma | |
| CN116588993B (en) | Ternary precursor, preparation method thereof, lithium battery positive electrode material and lithium battery | |
| CN113659129A (en) | Multi-element doped ternary precursor and preparation method thereof | |
| CN103187564A (en) | Preparation method for battery anode material LiNi0.5Mn1.5O4 | |
| CN116282216A (en) | Positive electrode precursor material and preparation method and application thereof | |
| CN115196692B (en) | Preparation method and device of precursor of ternary positive electrode material, precursor and positive electrode material | |
| CN113555545B (en) | Crystal face controllable anion/cation co-doped alpha/beta composite nickel-cobalt-aluminum precursor and preparation method thereof | |
| CN115259244A (en) | Cobalt gradient high-nickel ternary cathode material, preparation method thereof and lithium ion battery | |
| CN112599736B (en) | Boron-doped lithium phosphate coated lithium ion battery positive electrode material and preparation method thereof | |
| CN115188941A (en) | Multi-element anode material, preparation method thereof and lithium ion battery | |
| CN111943279A (en) | Method for preparing large single crystal shape nickel-cobalt-manganese ternary positive electrode material and precursor thereof | |
| CN113353993A (en) | Preparation method and application of composite high-nickel ternary material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |