CN109119607B - Polypyrrole nanotube coated lithium nickel manganese oxide positive electrode material and preparation method thereof - Google Patents
Polypyrrole nanotube coated lithium nickel manganese oxide positive electrode material and preparation method thereof Download PDFInfo
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- CN109119607B CN109119607B CN201810880943.6A CN201810880943A CN109119607B CN 109119607 B CN109119607 B CN 109119607B CN 201810880943 A CN201810880943 A CN 201810880943A CN 109119607 B CN109119607 B CN 109119607B
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- manganese oxide
- positive electrode
- lithium
- electrode material
- nickel manganese
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- FRMOHNDAXZZWQI-UHFFFAOYSA-N lithium manganese(2+) nickel(2+) oxygen(2-) Chemical compound [O-2].[Mn+2].[Ni+2].[Li+] FRMOHNDAXZZWQI-UHFFFAOYSA-N 0.000 title claims abstract description 73
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 63
- 229920000128 polypyrrole Polymers 0.000 title claims abstract description 57
- 239000002071 nanotube Substances 0.000 title claims abstract description 55
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- KINSVNGHYYZQFR-UHFFFAOYSA-N [Na].[B].[Ti] Chemical compound [Na].[B].[Ti] KINSVNGHYYZQFR-UHFFFAOYSA-N 0.000 claims abstract description 25
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 13
- 239000010406 cathode material Substances 0.000 claims abstract description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 32
- 238000003756 stirring Methods 0.000 claims description 21
- BDKWOJYFHXPPPT-UHFFFAOYSA-N lithium dioxido(dioxo)manganese nickel(2+) Chemical compound [Mn](=O)(=O)([O-])[O-].[Ni+2].[Li+] BDKWOJYFHXPPPT-UHFFFAOYSA-N 0.000 claims description 20
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 238000001354 calcination Methods 0.000 claims description 14
- 238000001816 cooling Methods 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 14
- 238000000227 grinding Methods 0.000 claims description 14
- 238000007873 sieving Methods 0.000 claims description 14
- 229910021538 borax Inorganic materials 0.000 claims description 9
- UQGFMSUEHSUPRD-UHFFFAOYSA-N disodium;3,7-dioxido-2,4,6,8,9-pentaoxa-1,3,5,7-tetraborabicyclo[3.3.1]nonane Chemical compound [Na+].[Na+].O1B([O-])OB2OB([O-])OB1O2 UQGFMSUEHSUPRD-UHFFFAOYSA-N 0.000 claims description 9
- 229940071125 manganese acetate Drugs 0.000 claims description 9
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 9
- 235000010339 sodium tetraborate Nutrition 0.000 claims description 9
- 239000004328 sodium tetraborate Substances 0.000 claims description 9
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 9
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 8
- 238000007605 air drying Methods 0.000 claims description 7
- 238000000498 ball milling Methods 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 7
- WHRAZOIDGKIQEA-UHFFFAOYSA-L iron(2+);4-methylbenzenesulfonate Chemical compound [Fe+2].CC1=CC=C(S([O-])(=O)=O)C=C1.CC1=CC=C(S([O-])(=O)=O)C=C1 WHRAZOIDGKIQEA-UHFFFAOYSA-L 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- 238000000926 separation method Methods 0.000 claims description 7
- 239000000725 suspension Substances 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 6
- 229910003002 lithium salt Inorganic materials 0.000 claims description 6
- 159000000002 lithium salts Chemical class 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 150000002815 nickel Chemical class 0.000 claims description 6
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 4
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 4
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 4
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 4
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 3
- 229940078494 nickel acetate Drugs 0.000 claims description 3
- FYMCOOOLDFPFPN-UHFFFAOYSA-K iron(3+);4-methylbenzenesulfonate Chemical compound [Fe+3].CC1=CC=C(S([O-])(=O)=O)C=C1.CC1=CC=C(S([O-])(=O)=O)C=C1.CC1=CC=C(S([O-])(=O)=O)C=C1 FYMCOOOLDFPFPN-UHFFFAOYSA-K 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 239000000463 material Substances 0.000 description 8
- 239000011248 coating agent Substances 0.000 description 7
- 239000010405 anode material Substances 0.000 description 6
- 239000003792 electrolyte Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 4
- 239000011572 manganese Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- IRPGOXJVTQTAAN-UHFFFAOYSA-N 2,2,3,3,3-pentafluoropropanal Chemical compound FC(F)(F)C(F)(F)C=O IRPGOXJVTQTAAN-UHFFFAOYSA-N 0.000 description 1
- KLZUFWVZNOTSEM-UHFFFAOYSA-K Aluminum fluoride Inorganic materials F[Al](F)F KLZUFWVZNOTSEM-UHFFFAOYSA-K 0.000 description 1
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 238000010521 absorption reaction Methods 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
- 239000012300 argon atmosphere Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000007323 disproportionation reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
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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
- H01M4/362—Composites
- H01M4/366—Composites as layered products
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- 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
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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
- 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
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
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- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
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- 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
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Abstract
The invention provides a preparation method of a polypyrrole nanotube coated lithium nickel manganese oxide positive electrode material, which comprises the following steps: firstly), preparing sodium titanium boron codoped lithium nickel manganese oxide, and secondly) preparing a polypyrrole nanotube coated lithium nickel manganese oxide cathode material. The invention also discloses the polypyrrole nanotube coated lithium nickel manganese oxide positive electrode material prepared by the preparation method of the polypyrrole nanotube coated lithium nickel manganese oxide positive electrode material and a lithium ion battery using the polypyrrole nanotube coated lithium nickel manganese oxide positive electrode material as a positive electrode material. Compared with the lithium nickel manganese oxide cathode material in the prior art, the polypyrrole nanotube coated lithium nickel manganese oxide cathode material prepared by the invention has the advantages of lower production cost, more excellent high-temperature cycle stability and electrochemical performance and longer cycle service life.
Description
Technical Field
The invention relates to the technical field of lithium nickel manganese oxide positive electrode materials, in particular to a polypyrrole nanotube coated lithium nickel manganese oxide positive electrode material and a preparation method thereof.
Background
In recent years, with the rapid development of pure electric vehicles and hybrid electric vehicles, chemical power supplies with high energy, long service life and low cost are particularly urgent, and lithium ion batteries are distinguished from many chemical power supplies by the advantages of low self-discharge rate, high specific energy, no memory effect and the like, and are widely applied to portable electronic equipment and other high-energy equipment. In each component of the lithium ion battery, the quality of the performance of the anode material directly determines the quality and the cycle service life of the whole performance of the battery. The lithium nickel manganese oxide positive electrode material has the advantages of high energy density, low price, environmental friendliness, abundant resources, high voltage platform and the like, and is a preferred positive electrode material for high-specific-energy power batteries.
In the process of charging and discharging of the lithium nickel manganese oxide positive electrode material in the prior art, due to high voltage, electrolyte on the surface of an electrode is continuously oxidized and decomposed, lithium ions are consumed, effective lithium is reduced, and capacity attenuation is serious. In addition, the nickel lithium manganate crystal prepared at high temperature has oxygen defects, and a large amount of Mn is contained in the material in order to maintain electric neutrality3+In the presence of Mn3+Easily generate Mn by disproportionation reaction2+The dissolution of manganese during the circulation process also leads to the capacity attenuation of the material. The surface modification of the material is a direct method for solving the above problems, and the coating is a common method for surface modification, but most of common coating agents such as zinc oxide, aluminum oxide, silicon dioxide, aluminum fluoride and the like belong to semiconductors or insulators, and the electronic conductivity of the whole material is reduced after coating, so that the rate capability of the material is affected. In addition, although the coating agents prevent the lithium nickel manganese oxide positive electrode material from directly contacting with the electrolyte, the coating agents have the problems of corroding the surface of the material, increasing the resistance, reducing the specific capacity and the like.
Therefore, a more effective method for modifying the lithium nickel manganese oxide is sought, the high-temperature cycle stability and the electrochemical performance of the lithium nickel manganese oxide positive electrode material are improved, the service life of the material is prolonged, and the high-performance lithium nickel manganese oxide positive electrode material is prepared and has a positive effect on promoting the development of lithium ion batteries.
Disclosure of Invention
The invention mainly aims to provide a polypyrrole nanotube coated lithium nickel manganese oxide positive electrode material and a preparation method thereof.
In order to achieve the above purpose, the invention provides a preparation method of a polypyrrole nanotube coated lithium nickel manganese oxide positive electrode material, which comprises the following steps:
1) preparation of sodium titanium boron codoped lithium nickel manganese oxide: dissolving manganese acetate, lithium salt, sodium tetraborate, titanium tetrachloride and nickel salt in water, mixing and stirring for 2-3h, then drying in a forced air drying oven at 100-110 ℃, cooling to room temperature, ball-milling, calcining at 800-900 ℃ for 20-30h, cooling to room temperature after calcining and sintering, taking out for grinding, and sieving with a 200-mesh 400-mesh sieve to obtain sodium-titanium-boron co-doped nickel lithium manganate;
2) preparing a polypyrrole nanotube coated lithium nickel manganese oxide positive electrode material: dispersing the sodium-titanium-boron co-doped lithium nickel manganese oxide prepared in the step 1) in an ethanol solution of 20-30% of iron p-toluenesulfonate in mass fraction, stirring the suspension at 5-10 ℃ for 15-20 minutes, adding pyrrole, then mechanically stirring for reaction for 35-45 minutes, finally repeatedly washing with ethanol and water for centrifugal separation, drying in an oven at 60-70 ℃ for 4-5 hours, and grinding and sieving to obtain the polypyrrole nanotube coated lithium nickel manganese oxide positive electrode material.
Preferably, the mass ratio of the manganese acetate, the lithium salt, the sodium tetraborate, the titanium tetrachloride, the nickel salt and the water in the step 1) is 1.47 (1-1.05):0.01:0.02:0.5 (6-10).
Preferably, the lithium salt is selected from one or more of lithium acetate, lithium nitrate or lithium chloride.
Preferably, the nickel salt is selected from one or more of nickel acetate, nickel nitrate or nickel chloride.
Preferably, the mass ratio of the sodium-titanium-boron co-doped lithium nickel manganese oxide, the ethanol solution of ferric p-toluenesulfonate and the pyrrole in the step 2) is 5 (20-23) to (0.25-0.35).
A polypyrrole nanotube coated lithium nickel manganese oxide positive electrode material is prepared by adopting a preparation method of the polypyrrole nanotube coated lithium nickel manganese oxide positive electrode material.
A lithium ion battery adopts the polypyrrole nanotube to coat a lithium nickel manganese oxide positive electrode material as a positive electrode material.
Due to the application of the technical scheme, the invention has the following beneficial effects:
(1) the preparation method of the polypyrrole nanotube coated lithium nickel manganese oxide cathode material disclosed by the invention is simple and feasible, has low requirements on equipment and reaction conditions, is easy to obtain raw materials, is low in price, and is suitable for large-scale production.
(2) Compared with the lithium nickel manganese oxide cathode material in the prior art, the polypyrrole nanotube coated lithium nickel manganese oxide cathode material disclosed by the invention is lower in production cost, more excellent in high-temperature cycle stability and electrochemical performance and longer in cycle service life.
(3) According to the polypyrrole nanotube coated lithium nickel manganese oxide cathode material disclosed by the invention, sodium titanium boron is introduced for substitution, so that the dissolution of manganese is effectively inhibited, the electrochemical performance of the material is not reduced, the problems of collapse, specific capacity loss and the like are effectively solved, and the cathode material has higher energy density; the lithium ion coefficient is improved, so that the rate performance of the product is improved, the polypyrrole nanotube coated on the surface prevents the direct contact between the lithium nickel manganese oxide positive electrode material and the electrolyte, and the polypyrrole tube has excellent conductivity without reducing the conductivity.
Detailed Description
The following description is presented to disclose the invention so as to enable any person skilled in the art to practice the invention. The preferred embodiments in the following description are given by way of example only, and other obvious variations will occur to those skilled in the art.
The raw materials in the examples of the present invention were purchased from Mobei (Shanghai) Biotech Co., Ltd.
Example 1
A preparation method of a polypyrrole nanotube coated lithium nickel manganese oxide positive electrode material comprises the following steps:
1) preparation of sodium titanium boron codoped lithium nickel manganese oxide: dissolving 14.7g of manganese acetate, 10g of lithium acetate, 0.1g of sodium tetraborate, 0.2g of titanium tetrachloride and 5g of nickel acetate in 60g of water, mixing and stirring for 2h, drying in a forced air drying oven at 100 ℃, cooling to room temperature, ball-milling, calcining at 800 ℃ for 20h, cooling to room temperature after calcination, taking out, grinding, and sieving with a 200-mesh sieve to obtain sodium-titanium-boron co-doped nickel lithium manganate;
2) preparing a polypyrrole nanotube coated lithium nickel manganese oxide positive electrode material: dispersing 5g of the sodium-titanium-boron co-doped nickel lithium manganate prepared in the step 1) into 20g of ethanol solution of iron p-toluenesulfonate with the mass fraction of 20%, stirring the suspension at 5 ℃ for 15 minutes, adding 0.25g of pyrrole, then mechanically stirring for reaction for 35 minutes, finally repeatedly washing with ethanol and water for centrifugal separation, drying in an oven at 60 ℃ for 4 hours, and grinding and sieving to obtain the polypyrrole nanotube coated nickel lithium manganate anode material.
A polypyrrole nanotube coated lithium nickel manganese oxide positive electrode material is prepared by adopting a preparation method of the polypyrrole nanotube coated lithium nickel manganese oxide positive electrode material.
A lithium ion battery adopts the polypyrrole nanotube to coat a lithium nickel manganese oxide positive electrode material as a positive electrode material.
Example 2
A preparation method of a polypyrrole nanotube coated lithium nickel manganese oxide positive electrode material comprises the following steps:
1) preparation of sodium titanium boron codoped lithium nickel manganese oxide: dissolving 14.7g of manganese acetate, 10.1g of lithium nitrate, 0.1g of sodium tetraborate, 0.2g of titanium tetrachloride and 5g of nickel nitrate in 70g of water, mixing and stirring for 2.3h, drying in a forced air drying oven at 103 ℃, cooling to room temperature, then ball-milling, calcining for 23h at 830 ℃, cooling to room temperature after calcining, taking out and grinding, and sieving by a 250-mesh sieve to obtain sodium-titanium-boron co-doped nickel lithium manganate;
2) preparing a polypyrrole nanotube coated lithium nickel manganese oxide positive electrode material: dispersing 5g of the sodium-titanium-boron co-doped nickel lithium manganate prepared in the step 1) into 21g of ethanol solution of 22% of iron p-toluenesulfonate, stirring the suspension at 6 ℃ for 17 minutes, adding 0.3g of pyrrole, mechanically stirring for reaction for 38 minutes, repeatedly washing with ethanol and water for centrifugal separation, drying in an oven at 64 ℃ for 4.3 hours, and grinding and sieving to obtain the polypyrrole nanotube coated nickel lithium manganate anode material.
A polypyrrole nanotube coated lithium nickel manganese oxide positive electrode material is prepared by adopting a preparation method of the polypyrrole nanotube coated lithium nickel manganese oxide positive electrode material.
A lithium ion battery adopts the polypyrrole nanotube to coat a lithium nickel manganese oxide positive electrode material as a positive electrode material.
Example 3
1) Preparation of sodium titanium boron codoped lithium nickel manganese oxide: dissolving 14.7g of manganese acetate, 10.2g of lithium chloride, 0.1g of sodium tetraborate, 0.2g of titanium tetrachloride and 5g of nickel chloride in 80g of water, mixing and stirring for 2.5h, drying at 105 ℃ in a forced air drying oven, cooling to room temperature, ball-milling, calcining for 25h at 850 ℃, cooling to room temperature after calcination, taking out and grinding, and sieving by a 300-mesh sieve to obtain sodium-titanium-boron co-doped nickel lithium manganate;
2) preparing a polypyrrole nanotube coated lithium nickel manganese oxide positive electrode material: dispersing 5g of the sodium-titanium-boron co-doped nickel lithium manganate prepared in the step 1) into 22g of ethanol solution of 26% of iron p-toluenesulfonate in mass fraction, stirring the suspension at 8 ℃ for 18 minutes, adding 0.33g of pyrrole, then mechanically stirring for reaction for 40 minutes, finally repeatedly washing with ethanol and water for centrifugal separation, drying in an oven at 68 ℃ for 4.7 hours, and grinding and sieving to obtain the polypyrrole nanotube coated nickel lithium manganate anode material.
A polypyrrole nanotube coated lithium nickel manganese oxide positive electrode material is prepared by adopting a preparation method of the polypyrrole nanotube coated lithium nickel manganese oxide positive electrode material.
A lithium ion battery adopts the polypyrrole nanotube to coat a lithium nickel manganese oxide positive electrode material as a positive electrode material.
Example 4
1) Preparation of sodium titanium boron codoped lithium nickel manganese oxide: dissolving 14.7g of manganese acetate, 10.4g of lithium acetate, 0.1g of sodium tetraborate, 0.2g of titanium tetrachloride and 5g of nickel nitrate in 80g of water, mixing and stirring for 2.8h, drying at 108 ℃ in a forced air drying oven, cooling to room temperature, then ball-milling, calcining at 880 ℃ for 28h, cooling to room temperature after calcination, taking out and grinding, and sieving with a 350-mesh sieve to obtain sodium-titanium-boron co-doped nickel lithium manganate;
2) preparing a polypyrrole nanotube coated lithium nickel manganese oxide positive electrode material: dispersing 5g of the sodium-titanium-boron co-doped nickel lithium manganate prepared in the step 1) into 23g of ethanol solution of 28 mass percent of iron p-toluenesulfonate, stirring the suspension at 9 ℃ for 19 minutes, adding 0.34g of pyrrole, then mechanically stirring for reacting for 43 minutes, finally repeatedly washing with ethanol and water for centrifugal separation, drying in an oven at 69 ℃ for 4.8 hours, and grinding and sieving to obtain the polypyrrole nanotube coated nickel lithium manganate anode material.
A polypyrrole nanotube coated lithium nickel manganese oxide positive electrode material is prepared by adopting a preparation method of the polypyrrole nanotube coated lithium nickel manganese oxide positive electrode material.
A lithium ion battery adopts the polypyrrole nanotube to coat a lithium nickel manganese oxide positive electrode material as a positive electrode material.
Example 5
1) Preparation of sodium titanium boron codoped lithium nickel manganese oxide: dissolving 14.7g of manganese acetate, 10.5g of lithium nitrate, 0.1g of sodium tetraborate, 0.2g of titanium tetrachloride and 5g of nickel chloride in 100g of water, mixing and stirring for 3h, drying in a forced air drying oven at 110 ℃, cooling to room temperature, ball-milling, calcining at 900 ℃ for 30h, cooling to room temperature after calcining, taking out, grinding, and sieving with a 400-mesh sieve to obtain sodium-titanium-boron co-doped nickel lithium manganate;
2) preparing a polypyrrole nanotube coated lithium nickel manganese oxide positive electrode material: dispersing 5g of the sodium-titanium-boron co-doped nickel lithium manganate prepared in the step 1) into 23g of an ethanol solution of 30% by mass of iron p-toluenesulfonate, stirring the suspension at 10 ℃ for 20 minutes, adding 3.5g of pyrrole, mechanically stirring for reaction for 45 minutes, repeatedly washing with ethanol and water for centrifugal separation, drying in an oven at 70 ℃ for 5 hours, and grinding and sieving to obtain the polypyrrole nanotube coated nickel lithium manganate anode material.
A polypyrrole nanotube coated lithium nickel manganese oxide positive electrode material is prepared by adopting a preparation method of the polypyrrole nanotube coated lithium nickel manganese oxide positive electrode material.
A lithium ion battery adopts the polypyrrole nanotube to coat a lithium nickel manganese oxide positive electrode material as a positive electrode material.
Comparative example
The present example provides a lithium nickel manganese oxide positive electrode material, the raw material and formula of which are the same as those of the Chinese invention patent CN 107394171A
Example 1.
Relevant performance tests are carried out on the lithium nickel manganese oxide positive electrode materials obtained in the above examples 1 to 5 and comparative example, the test results are shown in table 1, and the test methods are as follows: dissolving the lithium manganate positive electrode material, Super P and PVDF in a mass ratio of 8:1:1 in N-methyl pyrrolidone (NMP) to prepare slurry, and coating the slurry on an aluminum foil by using an automatic coating machine. After vacuum drying for 12h, cutting into positive plates. The obtained product is transferred into a glove box with argon atmosphere, and a 2032 button cell is assembled by a metal lithium sheet, a diaphragm, electrolyte and a liquid absorption film. Wherein the electrolyte is 1mol L-1LiPF6EC/DMC (volume ratio 1:1), septum Celgard 2400. And (3) carrying out charge and discharge tests on the assembled button cell by adopting a LAND test system, wherein the cut-off voltage of the test is 3-4.9V.
TABLE 1
As can be seen from the above table, the polypyrrole tube coated lithium nickel manganese oxide positive electrode material disclosed in the embodiment of the present invention has more excellent electrochemical performance compared with a lithium nickel manganese oxide positive electrode material in the prior art.
The foregoing shows and describes the general principles, essential features, and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are merely illustrative of the principles of the invention, but that various changes and modifications may be made without departing from the spirit and scope of the invention, which fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (5)
1. A preparation method of a polypyrrole nanotube coated lithium nickel manganese oxide positive electrode material is characterized by comprising the following steps:
1) preparation of sodium titanium boron codoped lithium nickel manganese oxide: dissolving manganese acetate, lithium salt, sodium tetraborate, titanium tetrachloride and nickel salt in water, mixing and stirring for 2-3h, then drying in a forced air drying oven at 100-110 ℃, cooling to room temperature, ball-milling, calcining at 800-900 ℃ for 20-30h, cooling to room temperature after calcining, taking out for grinding, and sieving with a 200-mesh 400-mesh sieve to obtain sodium-titanium-boron co-doped nickel lithium manganate; the mass ratio of the manganese acetate to the lithium salt to the sodium tetraborate to the titanium tetrachloride to the nickel salt to the water is 1.47 (1-1.05) to 0.01:0.02:0.5 (6-10);
2) preparing a polypyrrole nanotube coated lithium nickel manganese oxide positive electrode material: dispersing the sodium-titanium-boron co-doped nickel lithium manganate prepared in the step 1) into an ethanol solution of 20-30% of iron p-toluenesulfonate in mass fraction, stirring the suspension at 5-10 ℃ for 15-20 minutes, adding pyrrole, then mechanically stirring for reaction for 35-45 minutes, finally repeatedly washing with ethanol and water for centrifugal separation, drying in an oven at 60-70 ℃ for 4-5 hours, and grinding and sieving to obtain a polypyrrole nanotube coated nickel lithium manganate positive electrode material; the mass ratio of the sodium-titanium-boron co-doped lithium nickel manganese oxide to the ethanol solution of ferric p-toluenesulfonate to the pyrrole is 5 (20-23) to 0.25-0.35.
2. The method for preparing the polypyrrole nanotube coated lithium nickel manganese oxide positive electrode material according to claim 1, wherein the lithium salt is selected from one or more of lithium acetate, lithium nitrate and lithium chloride.
3. The preparation method of the polypyrrole nanotube coated lithium nickel manganese oxide positive electrode material according to the claim 1, wherein the nickel salt is selected from one or more of nickel acetate, nickel nitrate and nickel chloride.
4. The polypyrrole nanotube coated lithium nickel manganese oxide positive electrode material prepared by the preparation method of the polypyrrole nanotube coated lithium nickel manganese oxide positive electrode material disclosed by any one of claims 1 to 3.
5. A lithium ion battery adopting the polypyrrole nanotube coated lithium nickel manganese oxide cathode material of claim 4 as a cathode material.
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