CN113871595A - Positive electrode material with polyatomic cationic compound coating and preparation method and application thereof - Google Patents
Positive electrode material with polyatomic cationic compound coating and preparation method and application thereof Download PDFInfo
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- 150000001767 cationic compounds Chemical class 0.000 title claims abstract description 48
- 239000011248 coating agent Substances 0.000 title claims abstract description 48
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 40
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 39
- 150000002500 ions Chemical class 0.000 claims abstract description 23
- 239000000463 material Substances 0.000 claims abstract description 20
- 238000002156 mixing Methods 0.000 claims abstract description 18
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 17
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 17
- 239000002253 acid Substances 0.000 claims abstract description 15
- 239000010406 cathode material Substances 0.000 claims abstract description 11
- 239000003960 organic solvent Substances 0.000 claims abstract description 9
- 238000001035 drying Methods 0.000 claims abstract description 8
- -1 cation compound Chemical class 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical group [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- 239000011247 coating layer Substances 0.000 claims description 9
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 8
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 150000001768 cations Chemical class 0.000 claims description 4
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims description 4
- 150000003839 salts Chemical group 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 3
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 3
- PNGLEYLFMHGIQO-UHFFFAOYSA-M sodium;3-(n-ethyl-3-methoxyanilino)-2-hydroxypropane-1-sulfonate;dihydrate Chemical compound O.O.[Na+].[O-]S(=O)(=O)CC(O)CN(CC)C1=CC=CC(OC)=C1 PNGLEYLFMHGIQO-UHFFFAOYSA-M 0.000 claims description 3
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- RAXXELZNTBOGNW-UHFFFAOYSA-O Imidazolium Chemical compound C1=C[NH+]=CN1 RAXXELZNTBOGNW-UHFFFAOYSA-O 0.000 claims description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Natural products P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 2
- 125000006575 electron-withdrawing group Chemical group 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 2
- 229940085991 phosphate ion Drugs 0.000 claims description 2
- 239000011574 phosphorus Substances 0.000 claims description 2
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-O pyridinium Chemical compound C1=CC=[NH+]C=C1 JUJWROOIHBZHMG-UHFFFAOYSA-O 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 125000000547 substituted alkyl group Chemical group 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims 1
- 150000001335 aliphatic alkanes Chemical group 0.000 claims 1
- 229920006317 cationic polymer Polymers 0.000 claims 1
- 125000000524 functional group Chemical group 0.000 claims 1
- 229910052698 phosphorus Inorganic materials 0.000 claims 1
- 239000010405 anode material Substances 0.000 abstract description 18
- 239000000203 mixture Substances 0.000 abstract description 7
- 238000012546 transfer Methods 0.000 abstract description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052744 lithium Inorganic materials 0.000 abstract description 2
- 238000002390 rotary evaporation Methods 0.000 abstract description 2
- 239000013589 supplement Substances 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 19
- 230000014759 maintenance of location Effects 0.000 description 8
- 238000012360 testing method Methods 0.000 description 7
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- 230000008569 process Effects 0.000 description 5
- 229910013716 LiNi Inorganic materials 0.000 description 3
- 229910015705 LiNi0.85Co0.10 Inorganic materials 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 239000010416 ion conductor Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 229910012834 LiNi0.60Mn0.40O2 Inorganic materials 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 230000006870 function Effects 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 229910001512 metal fluoride Inorganic materials 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 1
- 229910018632 Al0.05O2 Inorganic materials 0.000 description 1
- 229910011456 LiNi0.80Co0.15Al0.05O2 Inorganic materials 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
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- 125000002091 cationic group Chemical group 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
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- 230000005684 electric field Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
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- 239000007789 gas Substances 0.000 description 1
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- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
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- 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
-
- 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
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention relates to the technical field of anode materials, and particularly discloses an anode material with a polyatomic cationic compound coating, and a preparation method and application thereof. The invention discloses a positive electrode material with a polyatomic cationic compound coating, which is prepared by mixing and dispersing a positive electrode material, a polyatomic cationic compound, lithium salt and acid in an organic solvent according to a certain proportion, and performing rotary evaporation and drying on the mixture. According to the invention, the surface of the positive electrode material is coated with the polyatomic cationic compound, so that the excellent ion conductivity of the polyatomic cationic compound is utilized, the lithium ions are easier to transfer in the battery, and meanwhile, the lithium salt in the coating material can also provide the lithium ions to be used as a lithium source to supplement the invalid lithium ions in the battery, so that the multiplying power of the battery is improved; and the obtained cathode material has the advantages of high multiplying power, good cycle performance and high safety performance. Therefore, the technical scheme disclosed by the invention is suitable for popularization and application in the market.
Description
Technical Field
The invention relates to the technical field of anode materials, in particular to an anode material with a polyatomic cationic compound coating, a preparation method of the anode material and application of the anode material in a lithium ion battery.
Background
The lithium ion secondary battery has the advantages of high specific capacity, high voltage, long cycle life, no memory effect, small pollution, light weight and the like, thereby being widely applied to the fields of mobile electrical equipment and power automobiles. With the further development of technology, lithium ion battery products are inevitably developed toward higher energy density.
The anode material is a key component of the lithium ion battery, serves as a lithium ion source in the working process of the battery, and realizes the charge and discharge process of the battery through the deintercalation and the insertion of lithium ions. The positive electrode material plays an important role in the composition of lithium ion batteries, and is required to have good safety performance and electrochemical performance, so that the performance of the positive electrode material is improved by methods such as doping and coating in the preparation process of the positive electrode material. Wherein the coating is to provide a protective layer for the anode material. The performance improvement mechanisms of electrodes modified by different coatings are possibly different, and the coating layer can not only stabilize the material structure, but also effectively inhibit the side reaction between the active material and the electrolyte and inhibit the dissolution of transition metal from the surface of the electrode electrolyte to the electrolyte, thereby improving the circulation stability. The single coating and the composite coating belong to different types of surface coating, and common coating objects comprise metal oxides, metal fluorides and organic matters.
However, metal oxides and fluorides are difficult to form perfect uniform and soft surface coatings due to their powder characteristics, particles are brittle, structural fracture is generated due to stress after multiple cycles, and most of the coatings have single functions and cannot meet the requirement of multi-directional improvement of electrode performance, so that the coatings can be improved by coatings made of other materials.
Disclosure of Invention
In view of the above, the present invention is directed to a positive electrode material having a coating layer of a polyatomic cationic compound, which has excellent ion conductivity to facilitate transfer of lithium ions in a battery, and a lithium salt in the coating layer can provide lithium ions to supplement spent lithium ions in the battery as a lithium source to improve the rate of the battery.
The polyatomic cationic compound provided by the invention has excellent heat resistance, and can improve the safety performance of the battery.
Mixing lithium salt and acid according to the stoichiometric ratio of 1: 1; mixing a polyatomic cationic compound and lithium ions in a lithium salt according to the stoichiometric ratio of (0.8-1.2): 1 to obtain a coating material, mixing the mixed coating material and a positive electrode material, dispersing the mixture in an organic solvent, and performing rotary evaporation, distillation, drying and other processes to obtain the positive electrode material with the lithium ion conductor coating (namely the positive electrode material with the polyatomic cationic compound coating).
The purpose of the invention is realized by the following scheme:
a positive electrode material having a coating of a polyatomic cationic compound, comprising the process steps of:
1. lithium salt and acid are mixed according to a certain proportion to obtain the lithium ion-containing compound with higher electrochemical stability and high ionic conductivity.
The positive ion group in the polyatomic cationic compound in the above step may be a quaternary salt structure formed by replacing 4 hydrogens in ammonium ions with alkyl groups, or a phosphine cation (chemical formula PH) formed by protonating a lone electron pair provided by phosphorus4 +) A quaternary salt structure formed by replacing 4 hydrogen in the cationic;
wherein the cation is at least one selected from quaternary ammonium salt cation, quaternary phosphonium salt cation, pyridinium ion and imidazolium ion; the carbon atom number of the substituted alkyl in the positive ion group is 1-5; preferably, the number of carbon atoms of the alkyl group is 2 to 4.
In the above steps, the negative ion group in the polyatomic cationic compound has a high negative charge delocalization or a strong electron-withdrawing group, and one of a sulfonate ion, a carboxylate ion and a phosphate ion is selected.
Preferably, in the above steps, the positive ion group of the polyatomic cationic compound is selected from quaternary phosphonium salt cations, and the negative ion group is preferably sulfonate ions; wherein, the sulfonate ions have higher negative charge delocalization, so that the lithium ions are easier to dissociate.
In the above step, the lithium salt is selected from one of lithium hydroxide and lithium carbonate.
Reacting the acid with lithium salt in the step to generate a lithium ion compound with high electrochemical stability and high ionic conductivity; wherein the acid is at least one of trifluoromethanesulfonic acid, hexafluorophosphoric acid, tetrafluoroboric acid, tetracyanoboric acid, perchloric acid and hexafluoroarsenic acid.
In the step, lithium salt and acid are mixed according to the stoichiometric ratio of 1:1, and the polyatomic cation compound and lithium ions in the lithium ion-containing compound are mixed according to the stoichiometric ratio of (0.8-1.2): 1; preferably, the stoichiometric ratio of the polyatomic cationic compound to the lithium ions in the lithium ion-containing compound is 1: 1.
And mixing and dispersing the coating material and the anode material which are mixed according to a certain proportion in an organic solvent, distilling and drying to prepare the anode material with the lithium ion conductor coating.
In the step, the organic solvent is selected from one of ethanol, methanol, isopropanol and butanol; preferably, the organic solvent is selected from ethanol.
In the above step, the coating material and the anode material are mixed according to the mass ratio of (0.003-0.010) to 1; preferably, the mass ratio of the coating material to the cathode material is selected to be (0.005-0.008): 1. When the mass ratio of the coating material to the anode material is less than 0.003:1, the anode material cannot be completely coated by the coating, and the corresponding ion transfer function is not achieved; when the mass ratio of the coating material to the anode material is more than 0.010:1, the coating material is excessive and is unevenly dispersed, so that the surface of the anode material is rough, the electron transfer is influenced, and the electrochemical performance of the anode material is reduced.
After the organic solvent is distilled off from the mixture obtained by mixing the coating material dispersed in the organic solvent and the positive electrode material through a rotary evaporator in the above step, drying the residue for 24 hours at a reduced pressure of 110-140 ℃; preferably, the temperature is chosen to be 120 ℃.
It is also an object of the present invention to claim a positive electrode material having a coating of a polyatomic cationic compound prepared by the above method and its use in lithium ion batteries (secondary batteries).
According to the technical scheme, compared with the prior art, the positive electrode material with the polyatomic cationic compound coating, the preparation method and the application thereof have the following excellent effects:
1. the invention provides a positive electrode material with a polyatomic cationic compound coating, wherein the polyatomic cationic compound coating plays a role in transferring lithium ions on the surface of the positive electrode material, the lithium ions firstly interact with certain active groups on the compound to form an association body in the transfer process of the lithium ions on the coating, and the active sites participating in association are continuously moved or replaced along with the movement of a molecular chain segment, so that the lithium ions are directionally moved under the action of an electric field. The polyatomic cationic compound has both positive ions and negative ions, the positive ions and the negative ions have different electrical properties, and the ions with different electrical properties move in opposite directions in the charging and discharging process, so that the transfer of lithium ions is facilitated.
2. According to the invention, the surface of the anode material is coated with the ion conductor coating obtained by mixing the polyatomic cationic compound and the lithium salt, so that the surface structure of the anode material is improved, and the multiplying power of the lithium ion battery is improved.
3. The polyatomic cationic compound used in the invention contains both positive ion groups and negative ion groups, so that the polyatomic cationic compound with the structure has excellent ion conductivity and heat resistance, and the safety performance of the lithium ion battery is improved.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the provided drawings without creative efforts.
Fig. 1 is a graph comparing cycle performance of the positive electrode materials of example 1 of the present invention and comparative example 1.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The embodiment of the invention discloses a preparation method of a positive electrode material with a polyatomic cationic compound coating.
Unless otherwise defined, all terms of art used hereinafter have the same meaning as commonly understood by one of ordinary skill in the art. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the scope of the present invention.
Unless otherwise specified, the reagents and materials used in the present invention are commercially available products or products obtained by a known method.
The present invention will be further specifically illustrated by the following examples for better understanding, but the present invention is not to be construed as being limited thereto, and certain insubstantial modifications and adaptations of the invention by those skilled in the art based on the foregoing disclosure are intended to be included within the scope of the invention.
The technical solution of the present invention will be further described with reference to the following specific examples.
Example 1:
LiNi serving as a positive electrode material0.85Co0.10Mn0.05O2For example, lithium hydroxide and hexafluorophosphoric acid are mixed in a stoichiometric ratio of 1:1, and polyatomic cations containing quaternary phosphonium salt cations as positive ion groups and sulfonate ions as negative ion groupsThe sub-compound is mixed with lithium ions in a lithium salt in a stoichiometric ratio of 1:1 as a coating material.
Mixing the coating material and the positive electrode material LiNi0.85Co0.10Mn0.05O2Mixing according to the mass ratio of 0.005:1, mixing and dispersing in ethanol, distilling off ethanol from the obtained mixture by a rotary evaporator, and drying the residue at 120 ℃ under reduced pressure for 24 hours to obtain the cathode material coated with the polyatomic cationic compound.
The electrochemical performance of the positive electrode material of the obtained polyatomic cationic compound coating is tested after the button cell is assembled, under 0.2C, the capacity retention rate after 100 cycles is 93.2%, and the 1C capacity is 190.9 mAh/g.
Example 2:
LiNi serving as a positive electrode material0.80Co0.15Al0.05O2For example, lithium carbonate and trifluoromethanesulfonic acid were mixed in a stoichiometric ratio of 1:1, and a polyatomic cationic compound containing a pyridinium ion cation as a positive ion group and a sulfonate ion as a negative ion group was mixed with lithium ions in a lithium salt in a stoichiometric ratio of 0.8:1 as a coating material.
Mixing the coating material and the positive electrode material LiNi0.80Co0.15Al0.05O2Mixing according to the mass ratio of 0.008:1, mixing and dispersing in methanol, distilling off methanol from the obtained mixture by a rotary evaporator, and drying the residue at 120 ℃ under reduced pressure for 24 hours to obtain the cathode material coated with the polyatomic cationic compound.
The electrochemical performance of the positive electrode material of the obtained polyatomic cationic compound coating is tested after the button cell is assembled, under 0.2C, the capacity retention rate after 100 cycles is 92.8%, and the 1C capacity is 189.9 mAh/g.
Example 3:
LiNi serving as a positive electrode material0.60Mn0.40O2For example, lithium hydroxide and tetrafluoroboric acid are mixed in a stoichiometric ratio of 1:1, containing a quaternary phosphonium salt cation as the positive ionPolyatomic cationic compound with radical and phosphate radical as negative ion radical is mixed with lithium ion in lithium salt in the stoichiometric ratio of 1.2 to 1 to be used as coating material.
Mixing the coating material and the positive electrode material LiNi0.60Mn0.40O2Mixing according to the mass ratio of 0.007:1, mixing and dispersing in isopropanol, removing the isopropanol from the obtained mixture by distillation through a rotary evaporator, and drying the residue at 140 ℃ under reduced pressure for 24 hours to obtain the cathode material coated with the polyatomic cationic compound.
The electrochemical performance of the positive electrode material of the obtained polyatomic cationic compound coating is tested after the button cell is assembled, under 0.2C, the capacity retention rate after 100 cycles is 93.3%, and the 1C capacity is 190.5 mAh/g.
Comparative example:
comparative example 1 is uncoated cathode material LiNi0.85Co0.10Mn0.05O2And the electrochemical performance of the button cell is tested after the button cell is assembled, and under 0.2C, the capacity retention rate of comparative example 1 is 91.1 percent after 100 cycles, and the 1C capacity is 190.1 mAh/g.
Comparative example 2 is uncoated cathode material LiNi0.85Co0.10Mn0.05O2The electrochemical performance of the button cell after being assembled is tested, and the capacity retention rate of comparative example 2 is 90.9% and the 1C capacity is 189.1mAh/g after 100 cycles under 0.2C.
Comparative example 3 is an uncoated cathode material LiNi0.60Mn0.40O2The electrochemical performance of the button cell after being assembled is tested, and the capacity retention rate of comparative example 3 is 91.5% after 100 cycles at 0.2C, and the 1C capacity is 189.7 mAh/g.
The test conditions of the examples and the comparative examples are the same, and the comparison of the capacity retention rate after 100 cycles shows that the capacity retention rate of the examples is superior to that of the comparative examples (shown in figure 1); the comparative example 1C capacity shows that the rate performance of the example is better than that of the comparative example, and the test results are shown in table 1.
Manufacturing the positive electrode materials prepared in the embodiment and the comparative example into soft package batteries, and respectively carrying out gas storage and generation tests on the manufactured batteries under the conditions that 1C is fully filled with 4.3V and the batteries are stored at a high temperature of 75 ℃ for 24 hours; and (3) after the battery is fully charged according to the multiplying power of 1C, placing the battery in a hot box, raising the temperature from the normal temperature to 150 +/-2 ℃ at the speed of 5 ℃/min, preserving the temperature for 30min, observing the state of the battery, carrying out a hot box test, and testing the safety performance of the battery. The test results are shown in table 2.
TABLE 1
| Group of | Multiplying power | capacity/mAh/g |
| Example 1 | 1C | 190.9 |
| Comparative example 1 | 1C | 190.1 |
| Example 2 | 1C | 189.9 |
| Comparative example 2 | 1C | 189.1 |
| Example 3 | 1C | 190.5 |
| Comparative example 3 | 1C | 189.7 |
TABLE 2
| Group of | Rate of volume expansion | Hot box test |
| Example 1 | 2％ | No fire and smoke |
| Comparative example 1 | 5％ | No fire and smoke |
| Example 2 | 2％ | No fire and smoke |
| Comparative example 2 | 4％ | No fire and smoke |
| Example 3 | 3％ | No fire and smoke |
| Comparative example 3 | 5％ | No fire and smoke |
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (10)
1. A preparation method of a positive electrode material with a polyatomic cationic compound coating is characterized by comprising the following steps:
1) mixing lithium salt and acid according to a certain proportion to obtain a lithium ion-containing compound;
2) and mixing and dispersing the lithium ion-containing compound, the polyatomic cationic compound and the positive electrode material in an organic solvent according to a certain proportion, distilling and drying to obtain the positive electrode material with the polyatomic cationic compound coating.
2. The method for preparing a positive electrode material having a coating layer of a polyatomic cationic compound according to claim 1, wherein the lithium salt is mixed with an acid in a stoichiometric ratio of 1: 1; the polyatomic cation compound and lithium ions in the lithium ion-containing compound are mixed according to the stoichiometric ratio (0.8-1.2) to 1.
3. The method for preparing a positive electrode material having a coating layer of a polyatomic cationic compound according to claim 1 or 2, wherein the positive ion group in the polyatomic cationic compound may beThe quaternary salt structure formed by substituting 4 hydrogens in ammonium ion with alkyl groups can also be phosphine cations (chemical formula PH) formed by providing lone electron pairs with phosphorus and protonating4 +) The quaternary salt structure formed by replacing 4 hydrogen in the cationic polymer with alkyl or the derivative cation formed by replacing hydrogen atoms with functional groups such as alkane.
4. The method according to claim 3, wherein the cation is at least one of quaternary ammonium salt cation, quaternary phosphonium salt cation, pyridinium ion and imidazolium ion, and the number of carbon atoms of the substituted alkyl group in the positive ion group is 1 to 5.
5. The method for preparing a cathode material with a coating of a polyatomic cationic compound according to claim 1 or 2, wherein the negative ion group in the polyatomic cationic compound is one of a sulfonate ion, a carboxylate ion and a phosphate ion, and has a high negative charge delocalization or a strong electron-withdrawing group.
6. The method for producing a positive electrode material having a coating layer of a polyatomic cationic compound according to claim 1 or 2, wherein the lithium salt is lithium hydroxide or lithium carbonate, and the organic solvent is at least one of ethanol, methanol, isopropanol, and butanol.
7. The method for preparing a positive electrode material having a coating layer of a polyatomic cationic compound according to claim 1 or 2, wherein the acid reacts with a lithium salt to form a lithium ion-containing compound having high electrochemical stability and high ionic conductivity, and the acid is at least one of trifluoromethanesulfonic acid, hexafluorophosphoric acid, tetrafluoroboric acid, tetracyanoboric acid, perchloric acid, and hexafluoroarsenic acid.
8. The method for preparing the positive electrode material with the polyatomic cationic compound coating layer according to claim 1, wherein the coating material and the positive electrode material are mixed according to a mass ratio of (0.003-0.010): 1.
9. A positive electrode material having a coating layer of a polyatomic cationic compound, which is prepared by the method of claim 1.
10. Use of a cathode material with a coating of a polyatomic cationic compound produced according to the method of claim 1 or a cathode material with a coating of a polyatomic cationic compound according to claim 9 in a lithium ion battery.
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| US20150349339A1 (en) * | 2012-12-27 | 2015-12-03 | Korea Electronics Technology Institute | A cathode active material coated with manganese phosphate for a lithium secondary battery and a preparation method of the same |
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| CN112018389A (en) * | 2019-05-30 | 2020-12-01 | 松下知识产权经营株式会社 | Positive electrode active material and secondary battery using same |
| CN112635722A (en) * | 2019-10-09 | 2021-04-09 | 北京卫蓝新能源科技有限公司 | Composite positive electrode material of lithium ion battery and preparation method |
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| US20150349339A1 (en) * | 2012-12-27 | 2015-12-03 | Korea Electronics Technology Institute | A cathode active material coated with manganese phosphate for a lithium secondary battery and a preparation method of the same |
| US20170200951A1 (en) * | 2016-01-13 | 2017-07-13 | Samsung Sdi Co., Ltd. | Positive active material for rechargeable lithium battery, method of preparing same and rechargeable lithium battery including same |
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