CN117913234A - Composite organic layer coated positive electrode active material, preparation and application thereof - Google Patents
Composite organic layer coated positive electrode active material, preparation and application thereof Download PDFInfo
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- CN117913234A CN117913234A CN202311817136.7A CN202311817136A CN117913234A CN 117913234 A CN117913234 A CN 117913234A CN 202311817136 A CN202311817136 A CN 202311817136A CN 117913234 A CN117913234 A CN 117913234A
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- positive electrode
- active material
- electrode active
- coupling agent
- titanate coupling
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- 239000007774 positive electrode material Substances 0.000 title claims abstract description 72
- 239000002131 composite material Substances 0.000 title claims abstract description 31
- 239000012044 organic layer Substances 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 238000000576 coating method Methods 0.000 claims abstract description 78
- 239000011248 coating agent Substances 0.000 claims abstract description 75
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 45
- 230000004048 modification Effects 0.000 claims abstract description 40
- 238000012986 modification Methods 0.000 claims abstract description 40
- 239000007822 coupling agent Substances 0.000 claims abstract description 38
- 239000000463 material Substances 0.000 claims abstract description 36
- 150000007524 organic acids Chemical class 0.000 claims abstract description 32
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 30
- 239000001257 hydrogen Substances 0.000 claims abstract description 12
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 12
- -1 hydrogen ions Chemical class 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 12
- 229910052751 metal Inorganic materials 0.000 claims abstract description 10
- 239000000126 substance Substances 0.000 claims abstract description 10
- 239000002184 metal Substances 0.000 claims abstract description 8
- 238000006386 neutralization reaction Methods 0.000 claims abstract description 8
- 150000002500 ions Chemical class 0.000 claims abstract description 7
- 239000006183 anode active material Substances 0.000 claims abstract description 5
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 5
- 230000002378 acidificating effect Effects 0.000 claims abstract description 4
- 238000002156 mixing Methods 0.000 claims abstract description 3
- 238000005342 ion exchange Methods 0.000 claims abstract 2
- 229910052748 manganese Inorganic materials 0.000 claims description 21
- 239000013522 chelant Substances 0.000 claims description 12
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 12
- 239000012071 phase Substances 0.000 claims description 9
- APSBXTVYXVQYAB-UHFFFAOYSA-M sodium docusate Chemical group [Na+].CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC APSBXTVYXVQYAB-UHFFFAOYSA-M 0.000 claims description 8
- 229910052783 alkali metal Inorganic materials 0.000 claims description 7
- 150000001340 alkali metals Chemical class 0.000 claims description 7
- 239000010410 layer Substances 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 7
- IMQLKJBTEOYOSI-GPIVLXJGSA-N Inositol-hexakisphosphate Chemical compound OP(O)(=O)O[C@H]1[C@H](OP(O)(O)=O)[C@@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@@H]1OP(O)(O)=O IMQLKJBTEOYOSI-GPIVLXJGSA-N 0.000 claims description 6
- 229910019142 PO4 Inorganic materials 0.000 claims description 5
- 239000007791 liquid phase Substances 0.000 claims description 5
- 229910052759 nickel Inorganic materials 0.000 claims description 5
- 239000010452 phosphate Substances 0.000 claims description 5
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 4
- IMQLKJBTEOYOSI-UHFFFAOYSA-N Phytic acid Natural products OP(O)(=O)OC1C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C1OP(O)(O)=O IMQLKJBTEOYOSI-UHFFFAOYSA-N 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 4
- 229940068041 phytic acid Drugs 0.000 claims description 4
- 235000002949 phytic acid Nutrition 0.000 claims description 4
- 239000000467 phytic acid Substances 0.000 claims description 4
- XPPKVPWEQAFLFU-UHFFFAOYSA-J diphosphate(4-) Chemical compound [O-]P([O-])(=O)OP([O-])([O-])=O XPPKVPWEQAFLFU-UHFFFAOYSA-J 0.000 claims description 3
- 235000011180 diphosphates Nutrition 0.000 claims description 3
- 238000000926 separation method Methods 0.000 claims description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 2
- 125000004423 acyloxy group Chemical group 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000007772 electrode material Substances 0.000 abstract description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 25
- 239000011572 manganese Substances 0.000 description 20
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 18
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 17
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 14
- 230000014759 maintenance of location Effects 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 9
- 239000003792 electrolyte Substances 0.000 description 9
- 239000000203 mixture Substances 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 239000000725 suspension Substances 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 238000005253 cladding Methods 0.000 description 5
- 239000005416 organic matter Substances 0.000 description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 239000011247 coating layer Substances 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000001704 evaporation Methods 0.000 description 4
- 239000012065 filter cake Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical group [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 238000000967 suction filtration Methods 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- 239000011149 active material Substances 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 239000006258 conductive agent Substances 0.000 description 3
- 230000001351 cycling effect Effects 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- PHGMGTWRSNXLDV-UHFFFAOYSA-N diethyl furan-2,5-dicarboxylate Chemical compound CCOC(=O)C1=CC=C(C(=O)OCC)O1 PHGMGTWRSNXLDV-UHFFFAOYSA-N 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 238000006479 redox reaction Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229910001415 sodium ion Inorganic materials 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910009055 Li1.2Ni0.2Mn0.6O2 Inorganic materials 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- XPPKVPWEQAFLFU-UHFFFAOYSA-N diphosphoric acid Chemical compound OP(O)(=O)OP(O)(O)=O XPPKVPWEQAFLFU-UHFFFAOYSA-N 0.000 description 1
- 239000011267 electrode slurry Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 230000037427 ion transport Effects 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- 229910000473 manganese(VI) oxide Inorganic materials 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000006864 oxidative decomposition reaction Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000004537 pulping Methods 0.000 description 1
- 229940048084 pyrophosphate Drugs 0.000 description 1
- 229940005657 pyrophosphoric acid Drugs 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 230000002459 sustained effect Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
Classifications
-
- 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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/24—Alkaline accumulators
-
- 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
-
- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Composite Materials (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention belongs to the field of battery electrode materials, and particularly relates to a preparation method of a composite organic layer coated positive electrode active material, which comprises the steps of carrying out partial neutralization reaction on a chelated organic acid by adopting an alkaline substance containing metal M, and carrying out ion exchange on acidic hydrogen ions in the chelated organic acid by utilizing M ions to obtain a modified chelated organic acid; wherein the pH value of the neutralization reaction end point is 4-7, and M is Li or Na; mixing the modified chelating organic acid with an anode active material containing an M element, and performing first-stage coating modification to obtain a first-stage coating modified material; and (3) placing the first-stage coating modification material in the atmosphere containing the titanate coupling agent for gas-phase second-stage coating modification to prepare the composite organic layer coated positive electrode active material. The invention also comprises the material prepared by the preparation method and application thereof. The method provided by the invention can effectively improve the multiplying power of the prepared material and the stability under high current.
Description
Technical Field
The invention belongs to the field of battery electrode materials, and particularly relates to the technical field of positive electrode active materials.
Background
From the aspects of resource guarantee, cost and energy density, the high-capacity lithium-rich manganese-based oxide positive electrode material xLi 2MnO3·(1-x)LiTMO2 (TM=Ni, co, mn) with lower nickel-cobalt content in a battery system meeting the requirement of more than 350Wh/kg (0 < x < 1) is a candidate with the most future application prospect. In the case of lithium-rich manganese-based positive electrode materials, the high capacity derives from the co-participation of transition metal cations and oxygen anions (O 2-) in the structure in electrochemical redox reactions. In order to ensure that oxygen anions can participate in redox reaction, the charge cut-off voltage of the lithium-rich manganese-based positive electrode material is generally more than 4.6V, and the higher voltage enables the conventional electrolyte to be more easily subjected to oxidative decomposition on the surface of the electrode, so that the electrolyte is continuously consumed and the polarization of the battery is continuously increased. Cycling at high pressures and high rates accelerates degradation and failure of lithium-rich manganese-based materials. Thus, the irreversible phase change coupled oxygen evolution process results in a sustained decay in electrochemical performance and a drop in voltage. To suppress capacity and voltage decay, researchers often use surface cladding or ion doping methods to improve stability.
The surface coating technology is a means for effectively improving the performance of the battery material. It has the following effects: (1) When the charge cutoff potential is high, the cycling stability of the material can be improved; (2) The thermal stability of the material and the charge and discharge performance under high current are improved; (3) The interface effect of the material is effectively improved, so that the internal resistance of the battery is reduced. The surface coating can prevent direct contact between the positive electrode material and the electrolyte, thereby avoiding capacity fade caused by side reaction between the positive electrode material and the electrolyte and improving the safety of the battery at high temperature. Surface coating helps stabilize the positive electrode/electrolyte interface, but interfacial ion transport and interfacial compatibility in long cycles are challenges.
The surface coating is generally carried out by using oxide, fluoride or phosphate, so that oxygen precipitation can be reduced, the surface is prevented from being directly contacted with acidic substances in electrolyte, and common inorganic substances are generally electrochemically inert, so that diffusion of interfacial lithium ions is not facilitated, and active sites of the material are reduced. Most of the current surface coating methods show inert particle-interspersed coating, so that the continuous and uniform distribution of surface coatings and the construction of functional coating layers are difficult to realize, and the stability of coating thickness and interface structures is difficult to ensure. The poor conductivity and electrochemical inertia of the common coating layer inevitably affect the rate performance and reversible capacity of the positive electrode material, and the poor inhibition effect on the strain deformation of the active material is achieved. As the electrochemical long cycle proceeds, the surface heterogeneous layer is difficult to keep conformal, and the damage effect of volume change on the anode material cannot be effectively overcome, so that the effect of surface modification is invalid.
Disclosure of Invention
Aiming at the problems of unsatisfactory coating effect and electrochemical performance of the existing organic material coated positive electrode active material, the first aim of the invention is to provide a preparation method of the composite organic layer coated positive electrode active material, aiming at improving the ion conductivity and hydrophobicity of the coating material and further improving the electrochemical performance, particularly the cycling stability.
The second object of the invention is to provide the composite organic layer coated positive electrode active material prepared by the preparation method and the application thereof in alkali metal batteries.
A third object of the present invention is to provide an alkali metal secondary battery comprising the composite organic layer-coated positive electrode active material.
The preparation method of the composite organic layer coated positive electrode active material comprises the following steps:
Step (1):
Neutralizing the chelate organic acid by adopting an alkaline substance containing metal M, and controlling the pH value of the end point of the neutralization reaction to be 4-7, so that the hydrogen ion part in the chelate organic acid is replaced by the metal M to obtain a modified chelate organic acid; m is Li or Na;
Step (2):
mixing the modified chelating organic acid with an anode active material containing an M element, and performing first-stage coating modification to obtain a first-stage coating modified material;
Step (3):
And (3) placing the first-stage coating modification material in the atmosphere containing the titanate coupling agent for gas-phase second-stage coating modification to prepare the composite organic layer coated positive electrode active material.
In the invention, the chelating organic acid is modified in advance, so that part of hydrogen ions in the chelating organic acid are exchanged into M ions, then the positive electrode active material is subjected to first-stage coating modification, and then the titanate coupling agent atmosphere is used for second-stage coating modification, so that the synergy can be realized unexpectedly, the stability and uniformity of the organic coating can be improved, and the circulation stability of the modified positive electrode active material can be improved.
In the invention, the combination of the modification of the chelating organic acid, the first-stage modification participated in the modification and the second-stage gas-phase coating modification participated in by the subsequent titanate coupling agent is the key for synergistically improving the electrochemical performance of the anode active material after coating modification.
In the invention, the hydrogen ion in the chelate organic acid is at least one of carboxylate hydrogen ion and phosphate hydrogen ion.
Preferably, the chelating organic acid is at least one of phytic acid and EDTA.
In the invention, the alkaline substance containing the metal M is at least one of hydroxide and carbonate of M. For example, sodium hydroxide, lithium carbonate or sodium carbonate.
In the present invention, the pH at the end point of the neutralization reaction system may be further controlled to 4 to 6, and further may be 4.5 to 5.
In the invention, the type of the positive electrode active material is an oxide positive electrode material. For example, the chemical expression of the positive electrode active material is at least one of MXO 2、MY2O4;
m is Li or Na;
X, Y is at least one of Ni, co and Mn;
Preferably, the positive electrode active material is xLiXO 2·(1-x)Li2XO3, wherein X is at least any one of Ni, co and Mn metal elements, and 0 < X < 1.
In the present invention, the first stage coating modification may be liquid phase coating, in which the solvent is, for example, water or a mixed solvent of water and an organic solvent;
In the present invention, one exemplary liquid phase coating step is: placing the positive electrode active material containing the M element into the neutralization reaction system for first-stage coating, and then carrying out solid-liquid separation to obtain a first-stage coating modified material;
Preferably, the weight ratio of the modified chelate organic acid to the positive electrode active material containing the M element is 0.3% to 1.5%, and further may be 0.5% to 1%.
In the present invention, the temperature of the first stage coating modification process is not particularly limited, and may be, for example, 10 to 70℃and may be further room temperature in view of the simplicity of the technical scheme.
In the present invention, the time for the first stage coating modification is not particularly limited, and may be, for example, 1 hour or more, and may be further 2 to 5 hours.
In the invention, after the first section of coating modification is finished, solid-liquid separation is carried out, and then drying treatment is carried out, so that a section of coating is obtained. The temperature of the drying treatment may be, for example, 50℃or higher, further 60 to 90℃or higher, and the drying time is not particularly limited, and may be, for example, 6 hours or higher, further 12 to 24 hours.
According to the invention, the first section of coating is carried out by the modified chelating organic acid in advance, so that the chelating organic acid is uniformly and tightly coated on the surface of the positive electrode active material based on physical actions such as chemistry, hydrogen bond and the like, and the gas phase coating thought of the titanate coupling agent is further matched, so that the coordination can be realized accidentally, the uniformity and compactness of a coating structure are improved, and the stability of the modified positive electrode active material is further improved synergistically.
In the invention, the titanate coupling agent can be a coupling agent of titanate types well known in the industry, and can comprise at least one of a mono-oxyalkyl phosphate titanate coupling agent, a mono-oxyalkyl pyrophosphate titanate coupling agent and a pyrophosphoric acid acyloxy titanate coupling agent;
Further, the titanate coupling agent comprises at least one of isopropyl tri (dioctyl pyrophosphoryl oxy) titanate coupling agent (201), isopropyl tri (dioctyl pyrophosphoryl oxy) titanate coupling agent (102) and isopropyl tri (dioctyl pyrophosphoryl oxy) ethylene titanate coupling agent (311);
in the invention, a titanate coupling agent and a section of coating modification material are arranged in the same or different areas of the same closed container, the closed container is heated to volatilize the titanate coupling agent, and the section of coating modification material is subjected to second section of coating modification in the atmosphere of the titanate coupling agent;
Preferably, the weight percentage of the titanate coupling agent and the positive electrode active material containing M element is 5-50%, further 15-35%, further 19-22%;
Preferably, the temperature of the second stage coating modification stage is greater than or equal to the volatilization temperature T of the titanate coupling agent and less than or equal to 1.2T; in the present invention, the temperature of the second stage coating modification stage may be specifically 210 to 250 ℃.
Preferably, the second stage coating modification time is 0.5 to 3 hours, and further may be 1 to 2 hours.
The invention also provides the anode active material coated by the composite organic layer, which is prepared by the preparation method.
In the invention, the special interface characteristics can be endowed to the material by virtue of the preparation method, and the material with the characteristics prepared by the preparation method can unexpectedly show better cycle stability.
In the invention, the positive electrode active material core, the chelate organic acid layer modified on the core based on a chemical mode, and the titanate coupling agent layer modified on the chelate organic acid layer based on a hydrogen bond action;
In the positive electrode active material coated by the composite organic layer, the content of the positive electrode active material is 98-99.5 wt%, and further can be 98.5-99.5%. In the invention, good coating stability and uniformity can be obtained under the condition of low content of the coating organic components, and excellent electrochemical performance can be shown.
The invention also provides an application of the composite organic layer coated positive electrode active material prepared by the preparation method, and the composite organic layer coated positive electrode active material is used as a positive electrode active material for preparing a secondary battery of alkali metal M.
In the present invention, the modified positive electrode active material according to the present invention may be prepared into a secondary battery of the desired alkali metal M based on conventional means. For example, the modified positive electrode active material, the conductive agent and the binder are subjected to composite pulping to form a positive electrode, and then the positive electrode active material, the conductive agent and the binder are subjected to composite assembly with a diaphragm and a negative electrode to obtain the battery.
In the present invention, the secondary battery of the metal M is, for example, an ion battery of the metal M.
The invention also provides a secondary battery of alkali metal M, which comprises the positive electrode active material coated by the composite organic layer prepared by the preparation method;
Preferably, the positive electrode contains the positive electrode active material coated by the composite organic layer.
In the invention, hydrogen in the modified chelated organic acid can exchange with lithium ions on the surface of the positive electrode active material to construct lithium defects, a coating layer of M salt of the complexed organic acid is formed on the surface of the positive electrode active material, and then the second-stage gas phase coating treatment is carried out, so that the gas-phase titanate coupling agent forms hydrogen bonds with acid radical groups in the M salt of the complexed organic acid through hydroxyl groups of the gas-phase titanate coupling agent, the composition is more uniform, the structure is more stable, and the corrosion resistance in high voltage and electrolyte is stronger.
Advantageous effects
According to the invention, the chelating organic acid is modified in advance, so that part of hydrogen ions in the chelating organic acid are exchanged into M ions, then the first section of coating modification is carried out on the positive electrode active material, and then the second section of coating modification is carried out by utilizing the titanate coupling agent atmosphere, so that the synergy can be realized accidentally, the stability and uniformity of the organic coating can be improved, and the circulation stability of the modified positive electrode active material can be improved.
Drawings
FIG. 1 is an SEM image of a lithium-rich manganese-based positive electrode material (also referred to as comparative example 1) prior to coating of example 1;
fig. 2 is an SEM image of the co-coated lithium-rich manganese-based cathode material prepared in example 1.
Fig. 3 is a graph of capacity cycle comparison at 1C rate for the assembled battery before and after the coating of example 1.
Fig. 4 is a graph showing the capacity cycle comparison at 1C rate of the battery assembled from the positive electrode materials obtained in example 1 and comparative example 2.
Fig. 5 is a graph showing capacity comparisons of the batteries assembled from the positive electrode materials obtained in example 1 and comparative example 1 at different rates of 0.1 to 5C.
Fig. 6 is an SEM image of the co-coated lithium-rich manganese-based positive electrode material prepared in example 2.
Detailed Description
The electrochemical performance test mode of the invention is as follows:
in the present invention, the temperature of the first stage modification process may be room temperature, for example, may be 20 to 40 ℃.
In the first-stage modification process, the titanate and the first-stage coating material can be heated together in a mixture mode to carry out gas-phase coating (a first coating idea), or the first-stage coating material and the titanate can be arranged in different areas of the same reaction container, and then the mixture is heated together to volatilize and coat (a second coating idea). In the following cases, the first coating concept is selected unless specifically stated.
In the present invention, the kind of the active material to be coated and modified is not particularly limited, and for example, it may be any known active material, and in the following cases, a lithium-rich manganese-based material is used as a typical example.
The active ingredients are as follows: the coated modified positive electrode active material, the conductive carbon black and PVDF are manually mixed and ground for 20min in an agate mortar according to the weight ratio of the conductive agent to the binder of 8:1:1, and NMP is added to prepare positive electrode slurry. Coating the prepared slurry on an aluminum foil with the thickness of 18 mu m, drying at the temperature of 120 ℃ under vacuum, preparing an electrode plate with the diameter of 14mm by using a puncher, assembling an electrolyte with Cellgard2400 as a diaphragm (with the diameter of 19 mm) and LiPF 6 (with the solvent of EC/DMC/EMC and the volume ratio of 1:1:1) as an electrolyte into a 2025 button cell, wherein the charge-discharge voltage range is 2.0-4.8V, and the capacity retention rate of the battery at 1C (1 C=250 mAh g -1) and 100 times of circulation at room temperature and the specific capacity at different multiplying powers of 0.1C-5C at room temperature are measured.
Example 1
Step (1):
Accurately weighing 0.05g of phytic acid solution, a proper amount of lithium hydroxide and a proper amount of deionized water, and uniformly stirring to obtain a mixed solution A (pH is 5);
step (2): first stage modification
10G of lithium-rich manganese-based lithium (Li 1.2Ni0.2Mn0.6O2) was dispersed in 10mL of isopropyl alcohol, and the dispersion was stirred for 20 minutes to obtain a suspension B. Adding the solution A into the suspension B, continuously stirring for 3 hours, carrying out suction filtration on the obtained solid-liquid mixture, placing a filter cake in a 70 ℃ oven for 12 hours, and evaporating the solvent to obtain a material C;
Step (3): second stage modification
2G of isopropyl tri (dioctyl pyrophosphoryloxy) titanate 201 is accurately weighed, placed in an alumina crucible, placed in a tube furnace together with a material C, vacuumized, heated to 220 ℃ at a heating speed of 3 ℃/min, and kept for 1h, so that a co-cladding treatment sample 1 is obtained. The coating amount of the organic component was 1%. SEM images are shown in fig. 2.
The charge and discharge cycle at 1C (1c=250 mAh g -1) was measured 100 times, with a capacity retention of 96%; the capacity at 5C can reach 120mAh g -1.
Comparative example 1
The only difference compared with example 1 is that the lithium-rich manganese-based lithium is not subjected to the coating treatment.
The charge and discharge cycle at 1C was measured 100 times, and the capacity retention rate was 88%;
Comparative example 2
The difference from example 1 is that step (3) was not performed, and the ratio of the positive electrode material and the phytic acid in step 2 was adjusted so that the organic matter coating amount of the coated material was the same as the total organic matter coating amount of sample 1 of example 1. The charge and discharge cycles at 1C were measured 100 times, and the capacity retention rate was 91%;
comparative example 3
The difference from example 1 is that the lithium-rich manganese-based lithium is directly subjected to the treatment of step (3) without performing steps (1) and (2), and the organic matter coating amount of the coated material is controlled to be the same as the total organic matter coating amount of sample 1 of example 1. The charge-discharge cycle at 1C was measured 100 times, and the capacity retention was 85%.
Comparative example 4
The difference from example 1 is that the modification treatment in step (1) was not performed, that is, the lithium hydroxide was not added in step (1), and other operations and parameters were the same as in example 1. The charge-discharge cycle at 1C was measured 100 times, and the capacity retention was 76%.
Comparative example 5
The difference from example 1 is that the liquid phase coating method is adopted in the step (3), and the steps are as follows: 0.1g of isopropyl tri (dioctyl pyrophosphoryloxy) titanate 201 and 10g of lithium-rich manganese titanate are accurately weighed, the isopropyl tri (dioctyl pyrophosphoryloxy) titanate 201 is dissolved in a proper amount of isopropanol, the lithium-rich manganese titanate is added, and the mixture is stirred and dried at 70 ℃ to obtain a sample with the same organic matter coating amount as in example 1. The charge and discharge cycles at 1C were measured 100 times, and the capacity retention was 75%.
Comparative example 6
The only difference compared with example 1 is that the changed treatment sequence, that is, the lithium-rich manganese-based lithium is subjected to the treatment of step (3) in advance, the titanate is coated first, and then step (1) and step (2) are sequentially performed. The proportions and conditions of the components were the same as in example 1. The charge-discharge cycle at 1C was measured 100 times, and the capacity retention was 82%.
Example 2
Accurately weighing 0.05g of ethylenediamine tetraacetic acid, a proper amount of lithium hydroxide and a proper amount of deionized water, and uniformly stirring to obtain a mixed solution A (pH 4.5); 10g of lithium-rich manganese-based lithium (same as in example 1) was dispersed in 10mL of isopropyl alcohol, and the dispersion was stirred for 20 minutes to obtain a suspension B. Adding the solution A into the suspension B, continuously stirring for 3 hours, carrying out suction filtration on the obtained solid-liquid mixture, placing a filter cake in a 70 ℃ oven for 12 hours, and evaporating the solvent to obtain a material C; 2g of isopropyl tri (dioctyl phosphate acyloxy) titanate 102 is accurately weighed, placed in an alumina crucible, placed in a tube furnace together with a material C, vacuumized, heated to 240 ℃ at a heating speed of 3 ℃/min, and kept for 1h, so as to obtain a co-cladding treatment sample 2.SEM is shown in FIG. 6. As can be seen from a comparison of fig. 1, a composite coating layer is present on the surface.
The charge and discharge cycle at 1C (1c=250 mAh g -1) was measured 100 times, with a capacity retention of 95%;
example 3
Accurately weighing 0.05g of ethylenediamine tetraacetic acid, a proper amount of lithium hydroxide and a proper amount of deionized water, and uniformly stirring to obtain a mixed solution A (pH 4.5); 10g of lithium-rich manganese-based lithium (same as in example 1) was dispersed in 10mL of isopropyl alcohol, and the dispersion was stirred for 20 minutes to obtain a suspension B. Adding the solution A into the suspension B, continuously stirring for 3 hours, carrying out suction filtration on the obtained solid-liquid mixture, placing a filter cake in a 70 ℃ oven for 12 hours, and evaporating the solvent to obtain a material C; 2g of isopropyl tri (dioctyl pyrophosphoryloxy) titanate 201 is accurately weighed, placed in an alumina crucible, placed in a tube furnace together with a material C, vacuumized, heated to 210 ℃ at a heating speed of 3 ℃/min, and kept for 1h to obtain a co-cladding treatment sample 3.
The charge and discharge cycle at 1C (1c=250 mAg -1) was measured 100 times, with a capacity retention of 96%;
Example 4
Accurately weighing 0.05g of phytic acid solution, a proper amount of lithium hydroxide and a proper amount of deionized water, and uniformly stirring to obtain a mixed solution A (pH is 5); 10g of lithium-rich manganese-based lithium (same as in example 1) was dispersed in 10mL of isopropyl alcohol, and the dispersion was stirred for 20 minutes to obtain a suspension B. Adding the solution A into the suspension B, continuously stirring for 3 hours, carrying out suction filtration on the obtained solid-liquid mixture, placing a filter cake in a 70 ℃ oven for 12 hours, and evaporating the solvent to obtain a material C; 2g of isopropyl tri (dioctyl pyrophosphoric acid acyloxy) ethylene titanate 311 is accurately weighed, placed in an alumina crucible, placed in a tube furnace together with a material C, vacuumized, heated to 250 ℃ at a heating speed of 3 ℃/min, and kept for 1.5 hours to obtain a co-cladding treatment sample 4.
The charge and discharge cycles at 1C (1c=250 mAg -1) were measured 100 times, and the capacity retention was 95%.
Example 5
The difference compared with example 1 is that in step (1), sodium hydroxide is used instead of lithium hydroxide, and the pH is controlled at 4.5; in the step 2, the weight ratio of the sodium ion manganese-based oxide positive electrode material (Na 0.6[Li0.2Mn0.8]O2) to the phytic acid is controlled to be 1:0.1; in step 3, the weight ratio of 201 to the sodium ion manganese-based oxide positive electrode material was controlled to be 0.15:1, and other operations and parameters were the same as in example 1.
The charge and discharge cycles at 100mA/g were measured 100 times, and the capacity retention rate was 94.5%.
Claims (10)
1. The preparation method of the composite organic layer coated positive electrode active material is characterized by comprising the following steps:
Step (1):
Performing partial neutralization reaction on the chelate organic acid by adopting an alkaline substance containing metal M, and performing ion exchange on acidic hydrogen ions in the chelate organic acid by utilizing M ions to obtain modified chelate organic acid; wherein the pH value of the neutralization reaction end point is 4-7, and M is Li or Na;
Step (2):
mixing the modified chelating organic acid with an anode active material containing an M element, and performing first-stage coating modification to obtain a first-stage coating modified material;
Step (3):
And (3) placing the first-stage coating modification material in the atmosphere containing the titanate coupling agent for gas-phase second-stage coating modification to prepare the composite organic layer coated positive electrode active material.
2. The method for preparing a composite organic layer coated positive electrode active material according to claim 1, wherein the acidic hydrogen ions in the chelating organic acid are at least one of carboxylate hydrogen ions and phosphate hydrogen ions;
preferably, the chelating organic acid is at least one of phytic acid and EDTA.
3. The method for preparing a composite organic layer coated positive electrode active material according to claim 1 or 2, wherein the alkaline substance containing a metal M is at least one of hydroxide and carbonate of M.
4. The method for preparing a composite organic layer coated positive electrode active material according to claim 1, wherein the chemical expression of the positive electrode active material is at least one of MXO 2、MY2O4;
m is Li or Na;
X, Y is at least one of Ni, co and Mn;
Preferably, the positive electrode active material is xLiXO 2·(1-x)Li2XO3, wherein X is at least any one of Ni, co and Mn metal elements, and 0 < X < 1.
5. The method for preparing a composite organic layer coated positive electrode active material according to claim 1, wherein the first stage coating modification mode is liquid phase coating;
Preferably, the step of liquid phase coating is as follows: and (3) placing the positive electrode active material containing the M element into the neutralization reaction system to carry out first-stage coating, and then carrying out solid-liquid separation to obtain a first-stage coating modified material.
6. The method for preparing a composite organic layer coated positive electrode active material according to claim 1, wherein the weight ratio of the modified chelating organic acid to the positive electrode active material containing the M element is 0.3% to 1.5%.
7. The method for preparing a composite organic layer coated positive electrode active material according to claim 1, wherein the titanate coupling agent comprises at least one of a mono-oxyalkyl phosphate titanate coupling agent, a mono-oxyalkyl pyrophosphate titanate coupling agent, and an acyloxy pyrophosphate titanate coupling agent;
Preferably, the titanate coupling agent comprises at least one of isopropyl tri (dioctyl pyrophosphoryl oxy) titanate coupling agent (201), isopropyl tri (dioctyl pyrophosphoryl oxy) titanate coupling agent (102) and isopropyl tri (dioctyl pyrophosphoryl oxy) ethylene titanate coupling agent (311);
Preferably, the titanate coupling agent and the one section of coating modification material are arranged in the same or different areas of the same closed container, the closed container is heated to volatilize the titanate coupling agent, and the one section of coating modification material is subjected to the second section of coating modification in the atmosphere of the titanate coupling agent;
Preferably, the weight percentage of the titanate coupling agent and the positive electrode active material containing M element is 5-50%, and further 15-35%;
preferably, the temperature of the second stage coating modification stage is greater than or equal to the volatilization temperature T of the titanate coupling agent and less than or equal to 1.2T;
Preferably, the second stage coating modification time is 0.5-3 h.
8. A positive electrode active material coated with the composite organic layer prepared by the preparation method of any one of claims 1 to 7;
Preferably, the positive electrode active material core, and the chelate organic acid layer chemically modified on the core, and the titanate coupling agent layer modified on the chelate organic acid layer based on hydrogen bonding;
the content of the positive electrode active material in the composite organic layer coated positive electrode active material is 98-99.5 wt%.
9. Use of the composite organic layer coated positive electrode active material prepared by the preparation method according to any one of claims 1 to 7 as a positive electrode active material for preparing a secondary battery of alkali metal M.
10. A secondary battery of an alkali metal M, characterized by comprising the composite organic layer-coated positive electrode active material produced by the production method according to any one of claims 1 to 7;
Preferably, the positive electrode contains the positive electrode active material coated by the composite organic layer.
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