CN115140782B - Core-shell structured lithium-rich manganese-based positive electrode material precursor and preparation method thereof - Google Patents
Core-shell structured lithium-rich manganese-based positive electrode material precursor and preparation method thereof Download PDFInfo
- Publication number
- CN115140782B CN115140782B CN202210817819.1A CN202210817819A CN115140782B CN 115140782 B CN115140782 B CN 115140782B CN 202210817819 A CN202210817819 A CN 202210817819A CN 115140782 B CN115140782 B CN 115140782B
- Authority
- CN
- China
- Prior art keywords
- precursor
- reaction kettle
- positive electrode
- core
- complexing agent
- 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.)
- Active
Links
- 239000002243 precursor Substances 0.000 title claims abstract description 47
- 239000011572 manganese Substances 0.000 title claims abstract description 45
- 229910052748 manganese Inorganic materials 0.000 title claims abstract description 39
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 38
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 35
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 35
- 239000011258 core-shell material Substances 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 239000008139 complexing agent Substances 0.000 claims abstract description 19
- 239000000654 additive Substances 0.000 claims abstract description 18
- 230000000996 additive effect Effects 0.000 claims abstract description 18
- 239000007788 liquid Substances 0.000 claims abstract description 18
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 12
- 238000000975 co-precipitation Methods 0.000 claims abstract description 12
- 229910052751 metal Inorganic materials 0.000 claims abstract description 12
- 239000002184 metal Substances 0.000 claims abstract description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000000126 substance Substances 0.000 claims abstract description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims abstract description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 4
- 238000001035 drying Methods 0.000 claims abstract description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 4
- 238000005406 washing Methods 0.000 claims abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 61
- 239000012792 core layer Substances 0.000 claims description 27
- 239000010410 layer Substances 0.000 claims description 25
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 14
- 229910021529 ammonia Inorganic materials 0.000 claims description 7
- 239000002002 slurry Substances 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 3
- HIEHAIZHJZLEPQ-UHFFFAOYSA-M sodium;naphthalene-1-sulfonate Chemical compound [Na+].C1=CC=C2C(S(=O)(=O)[O-])=CC=CC2=C1 HIEHAIZHJZLEPQ-UHFFFAOYSA-M 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 2
- 239000012716 precipitator Substances 0.000 abstract description 5
- 238000009792 diffusion process Methods 0.000 abstract description 4
- 150000002500 ions Chemical class 0.000 abstract description 4
- 239000010405 anode material Substances 0.000 abstract description 3
- 239000011261 inert gas Substances 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 19
- 238000000034 method Methods 0.000 description 9
- 230000001276 controlling effect Effects 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 238000001000 micrograph Methods 0.000 description 4
- 239000011164 primary particle Substances 0.000 description 4
- KZOJQMWTKJDSQJ-UHFFFAOYSA-M sodium;2,3-dibutylnaphthalene-1-sulfonate Chemical compound [Na+].C1=CC=C2C(S([O-])(=O)=O)=C(CCCC)C(CCCC)=CC2=C1 KZOJQMWTKJDSQJ-UHFFFAOYSA-M 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 229910001415 sodium ion Inorganic materials 0.000 description 2
- WZFUQSJFWNHZHM-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)CC(=O)N1CC2=C(CC1)NN=N2 WZFUQSJFWNHZHM-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/30—Particle morphology extending in three dimensions
- C01P2004/32—Spheres
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/11—Powder tap density
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
-
- 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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
-
- 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
Lithium-rich manganese-based positive electrode material precursor with core-shell structure and chemical formula of Ni x Mn y (OH) 2 The preparation method comprises the following steps: 1. preparing Ni and Mn metal liquid; preparing sodium hydroxide or potassium hydroxide solution as a precipitator; preparing ammonia water solution as complexing agent; preparing an additive solution; 2. adding pure water, a precipitator and a complexing agent into a kettle to prepare a base solution; 3. introducing nitrogen or inert gas, and continuously adding the metal liquid, the precipitator, the complexing agent and the additive solution into a kettle for coprecipitation; suspending liquid feeding when the granularity grows to 60-80% of the target granularity; continuously adding the metal liquid, the precipitant and the complexing agent into a kettle to continue coprecipitation when the temperature is reduced to 55-65 ℃, and stopping liquid feeding when the granularity grows to the target granularity; 4. and centrifuging, washing and drying the product to obtain the precursor of the lithium-rich manganese-based positive electrode material with the core-shell structure. The precursor has stable structure and higher ion diffusion coefficient, and can improve the electrical property of the anode material.
Description
Technical Field
The invention relates to the technical field of lithium ion battery anode materials, in particular to a lithium-rich manganese-based anode material precursor with a core-shell structure and a preparation method thereof.
Background
The lithium-rich manganese-based material has the advantages of low cost, high capacity, no toxicity, safety and the like, and can be used as a positive electrode material to meet the use requirements of power batteries in the fields of electric automobiles and the like.
The specific discharge capacity of the lithium-rich manganese-based positive electrode material reaches more than 300mAh/g, so that the lithium-rich manganese-based positive electrode material is considered as an ideal choice for a new generation of high-energy-density power batteries in the future. However, the lithium-rich manganese-based positive electrode material has a low ion diffusion coefficient, so that the rate performance and the cycle performance of the positive electrode material are poor, and the requirement of a power battery cannot be met. In addition, the lithium-rich manganese-based positive electrode material is easy to generate phase change in the charge and discharge process, so that the irreversible capacity is improved, and the electrical performance is reduced.
Therefore, how to prepare a precursor of a lithium-rich manganese-based positive electrode material with stable structure and high ion diffusion coefficient so as to improve the electrical property of the corresponding positive electrode material becomes the subject to be studied in the invention.
Disclosure of Invention
The invention aims to provide a lithium-rich manganese-based positive electrode material precursor with a core-shell structure and a preparation method thereof.
In order to achieve the purpose, the invention adopts the technical scheme that:
lithium-rich manganese-based positive electrode material precursor with core-shell structure and chemical formula of Ni x Mn y (OH) 2 Wherein x is more than or equal to 0.30 and less than or equal to 0.40,0.60, and y is more than or equal to 0.70.
The relevant content explanation in the technical scheme is as follows:
1. in the scheme, the porous ceramic material comprises a core layer and a shell layer, wherein the porosity of the core layer is 40-60%, and the D50 of the core layer 1 Accounting for 60 to 80 percent of the precursor D50; the porosity of the shell layer is 5-8%, and the D50 of the shell layer 2 Accounting for 20-40% of the precursor D50, and the ratio of the porosity of the core layer to the porosity of the shell layer is 5:1-8:1.
2. In the scheme, the D50 is 4-7 um, and the tap density is 1.20-1.60 g/cm 3 A specific surface area of 70-90 m 2 /g。
In order to achieve the purpose, the technical scheme adopted in the method level of the invention is as follows:
a preparation method of a precursor of a lithium-rich manganese-based positive electrode material with a core-shell structure comprises the following steps:
preparing Ni and Mn metal liquid with the molar concentration of 1.8-2.2 mol/L;
preparing sodium hydroxide or potassium hydroxide solution with the molar concentration of 8-10 mol/L as a precipitator;
preparing an ammonia water solution with the molar concentration of 2-4 mol/L as a complexing agent;
preparing an additive solution with the mass percentage of 1-3%;
adding pure water, the precipitant and the complexing agent into a closed reaction kettle to prepare a base solution, controlling the pH value of the base solution to be 11.5-12.1 through the precipitant, controlling the ammonia concentration in the base solution to be 0.05-0.25 mol/L through the complexing agent, and maintaining the temperature of the base solution to be 75-85 ℃;
step three, keeping stirring of the reaction kettle open, and introducing nitrogen or inert gas with the flow of 0.5-0.8 m 3 And (h) continuously adding the molten metal, the precipitant, the complexing agent and the additive solution in the first step into a reaction kettle at the flow rate of 50-400L/min for coprecipitation reaction; the pH is maintained at 11.5-12.1 in the reaction process, the reaction temperature is maintained at 75-85 ℃, the rotating speed of the reaction kettle is 600-700 r/min, and the granularity D50 of the slurry in the reaction kettle is maintained 1 Suspending liquid feeding when the seed crystal grows to 60-80% of the target granularity D50;
the temperature of the reaction kettle is reduced to 55-65 ℃, the metal liquid, the precipitant and the complexing agent in the first step are continuously added into the reaction kettle at the flow rate of 50-400L/min respectively for continuous coprecipitation reaction, the pH value in the reaction process is maintained at 11.5-12.1, the reaction temperature is maintained at 55-65 ℃, the rotating speed of the reaction kettle is 500-600 r/min, and liquid feeding is stopped when the slurry granularity in the reaction kettle grows to the target granularity D50;
and step four, centrifuging, washing and drying the coprecipitation product in the step three to obtain a precursor of the lithium-rich manganese-based positive electrode material with a core-shell structure.
The relevant content explanation in the technical scheme is as follows:
1. in the above scheme, in the first step, the additive is one or more of sodium dodecyl sulfate, sodium dodecyl benzene sulfonate, sodium tetrapropylanilide sulfonate and sodium dibutyl naphthalene sulfonate.
2. In the above scheme, in the third step, the mass percentage of the additive in the reaction kettle is 0.02-0.06%.
3. In the scheme, in the third step, the ammonia concentration is kept between 0.05 and 0.25mol/L in the reaction process.
4. In the above scheme, in the third step, the target particle size D50 is 4 to 7um.
5. In the above scheme, in the fourth step, the chemical formula of the precursor is Ni x Mn y (OH) 2 Wherein x is more than or equal to 0.30 and less than or equal to 0.40,0.60, and y is more than or equal to 0.70.
6. In the scheme, the precursor comprises a core layer and a shell layer, wherein the porosity of the core layer is 40-60%, and the D50 of the core layer 1 Accounting for 60 to 80 percent of the precursor; the porosity of the shell layer is 5-8%, and the D50 of the shell layer 2 The ratio of the porosity of the core layer to the porosity of the shell layer is 5:1-8:1. The ratio of the porosity to the shell layer is 5:1-8:1;
the tap density of the precursor is 1.20-1.60 g/cm 3 A specific surface area of 70-90 m 2 /g。
The working principle and the advantages of the invention are as follows:
1. the lithium-rich manganese-based positive electrode material precursor with a core-shell structure is prepared by a coprecipitation method, wherein the porosity of a core layer is 40-60%, and the D50 of the core layer is 1 60-80% of the precursor, the porosity of the shell layer is 5-8%, and the D50 of the shell layer 2 Accounting for 20-40% of the precursor, and the ratio of the porosity of the core layer to the porosity of the shell layer is 5:1-8:1. The inner core with high porosity can increase the contact area with electrolyte, improve the transmission efficiency of lithium ions, solve the problem of low ion diffusion coefficient of the lithium-rich manganese-based positive electrode material and improve the electrical propertyThe method comprises the steps of carrying out a first treatment on the surface of the The shell layer has lower porosity, the structure is more stable, the structural change in the charge and discharge process is relieved, and the structural stability in the charge and discharge process is improved. In addition, by precisely controlling the D50 of the core layer 1 D50 with shell layer 2 The purpose of regulating and controlling the high porosity region and the low porosity region is realized, and the electrical property is improved.
2. In the process of preparing the precursor, the precursor of the lithium-rich manganese-based positive electrode material with a core-shell structure is prepared by adding an additive and modulating the reaction temperature. In the process of preparing the nuclear layer, the reaction temperature is maintained at 75-85 ℃, the rotating speed of the reaction kettle is 600-700 r/min, meanwhile, the additive is added, the higher temperature is favorable for improving the reaction rate, accelerating the growth of crystals and facilitating the formation of pores; the higher rotating speed can improve the dispersibility between the secondary balls, and the addition of the additive can prevent the primary particles from being adhered to each other, so that the effect of increasing the pores is achieved; in the process of preparing the shell layer, the reaction temperature is maintained at 55-65 ℃, the rotating speed of the reaction kettle is 500-600 r/min, no additive is added, the temperature is reduced in order to reduce the growth speed, the compactness among primary particles is improved, the stability of the structure is enhanced, and the reduction of the rotating speed can effectively prevent the cracking of the secondary balls.
Drawings
FIG. 1 is a cross-sectional electron microscope image of a core-shell structured lithium-rich manganese-based positive electrode material precursor prepared by the embodiment of the invention;
FIG. 2 is a cross-sectional electron microscope image of a precursor of the core-shell structure lithium-rich manganese-based cathode material prepared in comparative example 1;
FIG. 3 is a cross-sectional electron microscope image of a precursor of the core-shell structured lithium-rich manganese-based cathode material prepared in comparative example 2 of the present invention;
fig. 4 is a graph for testing the rate performance of the positive electrode material of the sodium ion battery prepared in example 1 of the present invention.
Detailed Description
The invention is further described below with reference to the accompanying drawings and examples:
the present invention will be described in detail with reference to the drawings, wherein modifications and variations are possible in light of the teachings of the present invention, without departing from the spirit and scope of the present invention, as will be apparent to those of skill in the art upon understanding the embodiments of the present invention.
The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the present disclosure. As used herein, the terms "comprising," "including," "having," and the like are intended to be open-ended terms, meaning including, but not limited to.
The term (terms) as used herein generally has the ordinary meaning of each term as used in this field, in this disclosure, and in the special context, unless otherwise noted. Certain terms used to describe the present disclosure are discussed below, or elsewhere in this specification, to provide additional guidance to those skilled in the art in connection with the description herein.
Examples:
a preparation method of a lithium-rich manganese-based positive electrode material precursor with a core-shell structure comprises the following steps:
preparing Ni and Mn metal liquid with the molar concentration of 1.8-2.2 mol/L, wherein the molar ratio of Ni to Mn is 35:65;
preparing sodium hydroxide or potassium hydroxide solution with the molar concentration of 10mol/L as a precipitator;
preparing an ammonia water solution with the molar concentration of 2.5mol/L as a complexing agent;
preparing a sodium dibutylnaphthalene sulfonate solution with the mass percentage of 2%;
adding pure water, the precipitant and the complexing agent into a closed reaction kettle to prepare a base solution, controlling the pH value of the base solution to be 11.5-12.1 through the precipitant, controlling the ammonia concentration in the base solution to be 0.2mol/L through the complexing agent, and maintaining the temperature of the base solution at 80 ℃;
step three, keeping stirring of the reaction kettle open, and introducing nitrogen or inert gas with the flow of 0.5-0.8 m 3 And (h) continuously adding the molten metal, the precipitant, the complexing agent and the additive solution in the first step into a reaction kettle at the flow rate of 50-400L/min for coprecipitation reaction; the pH is maintained at 11.5-12.1 during the reaction, the reaction temperature is maintained at 80 ℃, and the ammonia concentration during the reactionThe mass percentage of the dibutyl sodium naphthalene sulfonate in the reaction kettle is controlled to be 0.2mol/L, the rotating speed of the reaction kettle is 650r/min, and the granularity D50 of slurry in the reaction kettle is kept 1 Suspending liquid feeding when the seed crystal grows to 80% of the target granularity D50;
the temperature of the reaction kettle is reduced to 55-65 ℃, the metal liquid, the precipitant and the complexing agent in the first step are respectively and continuously added into the reaction kettle at the flow rate of 50-400L/min for continuous coprecipitation reaction, the pH value is maintained at 11.5-12.1 in the reaction process, the ammonia concentration is controlled at 0.2mol/L in the reaction process, the reaction temperature is maintained at 55-65 ℃, the rotating speed of the reaction kettle is 500-600 r/min, and the liquid feeding is stopped when the granularity of slurry in the reaction kettle grows to the target granularity D50;
step four, the coprecipitation product in the step three is subjected to filter pressing, washing and drying to obtain a lithium-rich manganese-based positive electrode material precursor with a core-shell structure, wherein the porosity of a core layer is 56%, and the D50 of the core layer is obtained 1 80% of the precursor, the porosity of the shell layer is 8%, and the D50 of the shell layer is 2 Accounting for 20% of the precursor, the ratio of the porosity of the core layer to the porosity of the shell layer is 7:1, and the chemical formula of the product is Ni 0.35 Mn 0.65 (OH) 2 The D50 is 6.524um, the tap density is 1.55g/cm 3 A specific surface area of 75.2m 2 And/g, the relevant data are shown in Table 1.
Comparative example 1:
the difference from the example is that in the third step, the mass percentage of the sodium dibutylnaphthalene sulfonate in the reaction kettle is different, the sodium dibutylnaphthalene sulfonate is not added in the comparative example 1, and the rest is the same as the example. The obtained precursor was washed and dried, and the relevant data are shown in table 1.
Comparative example 2:
the difference from the examples is that the temperature of the reaction in the third step is different, and the temperature of the reaction in the comparative example 2 is maintained at 55 to 65℃and the rest is the same as the examples. The obtained precursor was washed and dried, and the relevant data are shown in table 1.
Comparative example 3:
unlike the examples, in step three, D50 is 1 Different, this comparative exampleD50 in 3 1 40% of the target particle size D50, the remainder being identical to the examples. The obtained precursor was washed and dried, and the relevant data are shown in table 1.
Comparative example 4:
unlike the examples, in step three, D50 is 1 Unlike this, D50 in this comparative example 4 1 90% of the target particle size D50, the remainder being identical to the examples. The obtained precursor was washed and dried, and the relevant data are shown in table 1.
Table 1 shows the data of the products obtained in the examples and comparative examples
From the data in table 1, it can be seen that: the porosity of the core layer of the lithium-rich manganese-based positive electrode material precursor prepared in comparative example 1 without the additive is significantly lower than that of the core layer of the lithium-rich manganese-based positive electrode material precursor prepared by adding the additive, indicating that the additive has the effect of increasing the porosity. In comparative example 2, it is illustrated that as the reaction temperature decreases, the growth rate becomes slow, resulting in coarsening of primary particles of the core layer and a decrease in porosity. With decreasing porosity of the core layer or D50 of the core layer 1 The tap density of the prepared lithium-rich manganese-based positive electrode material precursor is gradually increased, and the corresponding specific surface area is gradually increased.
Table 2 shows the results of electrical performance tests of the lithium-rich manganese-based positive electrode materials corresponding to the lithium-rich manganese-based positive electrode material precursors prepared in examples and comparative examples
From the data in table 2, it can be seen that: the first discharge capacity of the lithium-rich manganese-based positive electrode material corresponding to the lithium-rich manganese-based positive electrode material precursor prepared in the embodiment can reach 265.8mAh/g, and the capacity retention rate after 50 times of circulation is 81 percent, which is higher than that of all the comparative examples.
Fig. 1, 2 and 3 are electron microscope images of lithium-rich manganese-based positive electrode material precursors prepared in examples, comparative examples 1 and 2, respectively.
As can be seen from fig. 1, the core layer part (in the coil) of the precursor of the lithium-rich manganese-based positive electrode material has a loose and porous structure, and the primary particles are fine and uniform, and the shell layer part is relatively compact, so that the structure is beneficial to improving the transmission efficiency of lithium ions and improving the stability of the structure. The porosity of the inner core layer of the lithium-rich manganese-based positive electrode material precursor prepared in comparative example 1 (fig. 2) and comparative example 2 (fig. 3) is significantly smaller than that of the comparative example.
Fig. 4 shows the results of the rate performance test of the positive electrode material of the sodium ion battery prepared in example 1, and it is known from the graph that the discharge capacity of the positive electrode material can reach 94mAh/g under the condition of 5C of charge-discharge current density, and the positive electrode material exhibits excellent rate performance.
The above embodiments are provided to illustrate the technical concept and features of the present invention and are intended to enable those skilled in the art to understand the content of the present invention and implement the same, and are not intended to limit the scope of the present invention. All equivalent changes or modifications made in accordance with the spirit of the present invention should be construed to be included in the scope of the present invention.
Claims (3)
1. A preparation method of a precursor of a lithium-rich manganese-based positive electrode material with a core-shell structure is characterized by comprising the following steps: comprising the following steps:
preparing Ni and Mn metal liquid with the molar concentration of 1.8-2.2 mol/L;
preparing sodium hydroxide or potassium hydroxide solution with the molar concentration of 8-10 mol/L as a precipitant;
preparing an ammonia water solution with the molar concentration of 2-4 mol/L as a complexing agent;
preparing an additive solution with the mass percentage of 1-3%; the additive is dibutyl sodium naphthalene sulfonate;
adding pure water, the precipitant and the complexing agent into a closed reaction kettle to prepare a base solution, controlling the pH value of the base solution to be 11.5-12.1 through the precipitant, controlling the ammonia concentration in the base solution to be 0.05-0.25 mol/L through the complexing agent, and maintaining the temperature of the base solution to be 75-85 ℃;
step three, keeping stirring of the reaction kettle open, and introducing nitrogen with the flow of 0.5-0.8 m 3 And (h) continuously adding the metal liquid, the precipitant, the complexing agent and the additive solution in the first step into a reaction kettle at a flow rate of 50-400L/min for coprecipitation reaction; in the reaction process, the pH is maintained at 11.5-12.1, the reaction temperature is maintained at 75-85 ℃, the rotating speed of the reaction kettle is 600-700 r/min, and the granularity D50 of slurry in the reaction kettle is kept 1 Suspending liquid feeding when the target particle size D50 is 60-80%;
the temperature of the reaction kettle is reduced to 55-65 ℃, the metal liquid, the precipitant and the complexing agent in the first step are continuously added into the reaction kettle at the flow rate of 50-400L/min respectively for continuous coprecipitation reaction, the pH value in the reaction process is maintained at 11.5-12.1, the reaction temperature is maintained at 55-65 ℃, the rotating speed of the reaction kettle is 500-600 r/min, and liquid feeding is stopped when the slurry granularity in the reaction kettle grows to the target granularity D50; the target granularity D50 is 4-7 um;
step four, centrifuging, washing and drying the coprecipitation product in the step three to obtain a lithium-rich manganese-based positive electrode material precursor with a core-shell structure;
the chemical formula of the precursor is Ni x Mn y (OH) 2 Wherein x is more than or equal to 0.30 and less than or equal to 0.40,0.60, and y is more than or equal to 0.70;
the precursor comprises a core layer and a shell layer, wherein the porosity of the core layer is 40-60%, and the D50 of the core layer 1 Accounting for 60-80% of the precursor; the porosity of the shell layer is 5-8%, and the D50 of the shell layer 2 The ratio of the porosity of the core layer to the porosity of the shell layer is 5:1-8:1, and the ratio of the porosity of the core layer to the porosity of the shell layer is 5:1-8:1;
the tap density of the precursor is 1.20-1.60 g/cm 3 The specific surface area is 70-90 m 2 /g。
2. The method of manufacturing according to claim 1, characterized in that: in the third step, the mass percentage of the additive in the reaction kettle is 0.02-0.06%.
3. The method of manufacturing according to claim 1, characterized in that: in the third step, the ammonia concentration is kept at 0.05-0.25 mol/L in the reaction process.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210456895 | 2022-04-27 | ||
| CN2022104568954 | 2022-04-27 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115140782A CN115140782A (en) | 2022-10-04 |
| CN115140782B true CN115140782B (en) | 2023-11-14 |
Family
ID=83411605
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210817819.1A Active CN115140782B (en) | 2022-04-27 | 2022-07-12 | Core-shell structured lithium-rich manganese-based positive electrode material precursor and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115140782B (en) |
Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105185979A (en) * | 2015-06-25 | 2015-12-23 | 中南大学 | Hollow structure lithium-ion battery positive electrode material and preparation method thereof |
| CN105322154A (en) * | 2015-09-25 | 2016-02-10 | 湖北工程学院 | Electrode active substance precursor nickel manganese oxide with special morphology |
| CN108598463A (en) * | 2018-02-28 | 2018-09-28 | 中国电力科学研究院有限公司 | A kind of preparation method of nano-sheet lithium-rich manganese-based anode material |
| CN111276680A (en) * | 2020-02-13 | 2020-06-12 | 荆门市格林美新材料有限公司 | Precursor cathode material with hollow interior and core-shell structure and preparation method thereof |
| CN112158889A (en) * | 2020-08-27 | 2021-01-01 | 荆门市格林美新材料有限公司 | Mass production method of single crystal cobalt-free lithium-rich manganese-based binary material precursor |
| CN112441627A (en) * | 2020-11-13 | 2021-03-05 | 荆门市格林美新材料有限公司 | Method for inhibiting twin crystals of nickel-cobalt-manganese ternary precursor |
| CN113603157A (en) * | 2021-08-03 | 2021-11-05 | 天能帅福得能源股份有限公司 | Cobalt-free binary anode material with core-shell structure and preparation method thereof |
| CN113697867A (en) * | 2021-06-30 | 2021-11-26 | 南通金通储能动力新材料有限公司 | Preparation method of power type high-nickel ternary precursor |
| CN113735191A (en) * | 2021-08-24 | 2021-12-03 | 南通金通储能动力新材料有限公司 | Porous structure ternary precursor and preparation method thereof |
| WO2021258662A1 (en) * | 2020-06-24 | 2021-12-30 | 蜂巢能源科技有限公司 | Positive electrode material, preparation method therefor and lithium ion battery |
| CN114188527A (en) * | 2021-11-26 | 2022-03-15 | 南通金通储能动力新材料有限公司 | NCMA (non-volatile memory alloy) positive electrode material with core-shell structure and preparation method thereof |
-
2022
- 2022-07-12 CN CN202210817819.1A patent/CN115140782B/en active Active
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105185979A (en) * | 2015-06-25 | 2015-12-23 | 中南大学 | Hollow structure lithium-ion battery positive electrode material and preparation method thereof |
| CN105322154A (en) * | 2015-09-25 | 2016-02-10 | 湖北工程学院 | Electrode active substance precursor nickel manganese oxide with special morphology |
| CN108598463A (en) * | 2018-02-28 | 2018-09-28 | 中国电力科学研究院有限公司 | A kind of preparation method of nano-sheet lithium-rich manganese-based anode material |
| CN111276680A (en) * | 2020-02-13 | 2020-06-12 | 荆门市格林美新材料有限公司 | Precursor cathode material with hollow interior and core-shell structure and preparation method thereof |
| WO2021258662A1 (en) * | 2020-06-24 | 2021-12-30 | 蜂巢能源科技有限公司 | Positive electrode material, preparation method therefor and lithium ion battery |
| CN112158889A (en) * | 2020-08-27 | 2021-01-01 | 荆门市格林美新材料有限公司 | Mass production method of single crystal cobalt-free lithium-rich manganese-based binary material precursor |
| CN112441627A (en) * | 2020-11-13 | 2021-03-05 | 荆门市格林美新材料有限公司 | Method for inhibiting twin crystals of nickel-cobalt-manganese ternary precursor |
| CN113697867A (en) * | 2021-06-30 | 2021-11-26 | 南通金通储能动力新材料有限公司 | Preparation method of power type high-nickel ternary precursor |
| CN113603157A (en) * | 2021-08-03 | 2021-11-05 | 天能帅福得能源股份有限公司 | Cobalt-free binary anode material with core-shell structure and preparation method thereof |
| CN113735191A (en) * | 2021-08-24 | 2021-12-03 | 南通金通储能动力新材料有限公司 | Porous structure ternary precursor and preparation method thereof |
| CN114188527A (en) * | 2021-11-26 | 2022-03-15 | 南通金通储能动力新材料有限公司 | NCMA (non-volatile memory alloy) positive electrode material with core-shell structure and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 温辉梁.《化工助剂》.南昌：江西科学技术出版社,2009,第303页. * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115140782A (en) | 2022-10-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108878799B (en) | Mesoporous lithium aluminum silicate coated doped single crystal ternary positive electrode material and preparation method thereof | |
| CN108428862B (en) | Aluminum-coated ternary zirconium-doped composite material, composite anode material, preparation of composite anode material and application of composite anode material in lithium ion battery | |
| CN106410157B (en) | High-magnification long-life cathode material and preparation method thereof | |
| CN113363492B (en) | Composite coating modified high-nickel NCA positive electrode material and preparation method thereof | |
| CN111525113B (en) | Core-shell structure high-nickel ternary precursor, preparation method thereof and hollow doped high-nickel ternary cathode material | |
| CN111916727B (en) | Dual-ion wet-doped ternary high-nickel cathode material and preparation method thereof | |
| CN107123792B (en) | Ternary cathode material with double-layer composite structure and preparation method thereof | |
| WO2022161090A1 (en) | Positive electrode material precursor, preparation method therefor and application thereof | |
| CN111477866B (en) | Ternary cathode material nickel-cobalt-aluminum for lithium ion battery and preparation method thereof | |
| CN114956202A (en) | Precursor of sodium ion positive electrode material, preparation method and positive electrode material | |
| CN114772658B (en) | Precursor of positive electrode material of power lithium ion battery and preparation method thereof | |
| CN115448384A (en) | Precursor for multilayer coated sodium ion positive electrode material and preparation method thereof | |
| CN115010190B (en) | High-entropy oxide positive electrode material and preparation method and application thereof | |
| CN116014104A (en) | Lithium-rich nickel positive electrode material, preparation method thereof, positive electrode sheet and secondary battery | |
| CN112952056B (en) | Lithium-rich manganese-based composite cathode material and preparation method and application thereof | |
| CN113629229A (en) | Phosphate-coated wet-method-doped ternary cathode material and preparation method thereof | |
| CN117105283A (en) | Core-shell structured positive electrode precursor material and preparation method and application thereof | |
| CN116759525A (en) | Sodium ion battery positive electrode material precursor, preparation method thereof, sodium ion battery positive electrode material, sodium ion battery and electric equipment | |
| CN112467127A (en) | Coating modified lithium ion ternary cathode material and preparation method thereof | |
| CN116639738A (en) | Positive electrode material precursor for sodium ion battery, preparation method of positive electrode material precursor, positive electrode material and sodium ion battery | |
| CN116344731A (en) | Core-shell structure type sodium ion battery anode material and preparation method thereof | |
| CN115140782B (en) | Core-shell structured lithium-rich manganese-based positive electrode material precursor and preparation method thereof | |
| CN113582246B (en) | Preparation method of high-nickel polycrystalline quaternary precursor | |
| CN112436135B (en) | Cathode material and preparation method and application thereof | |
| CN114853071A (en) | Sodium ion positive electrode material precursor with multilayer structure and preparation method thereof |
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 |