CN119133433A - Atmospheric pressure cold plasma modified lithium-rich manganese oxide positive electrode material and preparation method and application thereof - Google Patents
Atmospheric pressure cold plasma modified lithium-rich manganese oxide positive electrode material and preparation method and application thereof Download PDFInfo
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- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 title claims abstract description 130
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 78
- 230000005495 cold plasma Effects 0.000 title claims abstract description 47
- 150000002641 lithium Chemical class 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 55
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 55
- 238000000034 method Methods 0.000 claims abstract description 34
- 239000011572 manganese Substances 0.000 claims abstract description 33
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 18
- 230000008569 process Effects 0.000 claims abstract description 16
- IAQLJCYTGRMXMA-UHFFFAOYSA-M lithium;acetate;dihydrate Chemical compound [Li+].O.O.CC([O-])=O IAQLJCYTGRMXMA-UHFFFAOYSA-M 0.000 claims description 19
- 239000002243 precursor Substances 0.000 claims description 19
- 238000010438 heat treatment Methods 0.000 claims description 14
- ZBYYWKJVSFHYJL-UHFFFAOYSA-L cobalt(2+);diacetate;tetrahydrate Chemical compound O.O.O.O.[Co+2].CC([O-])=O.CC([O-])=O ZBYYWKJVSFHYJL-UHFFFAOYSA-L 0.000 claims description 13
- 229940082328 manganese acetate tetrahydrate Drugs 0.000 claims description 13
- CESXSDZNZGSWSP-UHFFFAOYSA-L manganese(2+);diacetate;tetrahydrate Chemical compound O.O.O.O.[Mn+2].CC([O-])=O.CC([O-])=O CESXSDZNZGSWSP-UHFFFAOYSA-L 0.000 claims description 13
- 229940078487 nickel acetate tetrahydrate Drugs 0.000 claims description 13
- OINIXPNQKAZCRL-UHFFFAOYSA-L nickel(2+);diacetate;tetrahydrate Chemical compound O.O.O.O.[Ni+2].CC([O-])=O.CC([O-])=O OINIXPNQKAZCRL-UHFFFAOYSA-L 0.000 claims description 13
- YASYEJJMZJALEJ-UHFFFAOYSA-N Citric acid monohydrate Chemical compound O.OC(=O)CC(O)(C(O)=O)CC(O)=O YASYEJJMZJALEJ-UHFFFAOYSA-N 0.000 claims description 11
- 229960002303 citric acid monohydrate Drugs 0.000 claims description 11
- 238000001694 spray drying Methods 0.000 claims description 10
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 7
- 239000002184 metal Substances 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 208000028659 discharge Diseases 0.000 abstract description 42
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 25
- 239000001301 oxygen Substances 0.000 abstract description 25
- 229910052760 oxygen Inorganic materials 0.000 abstract description 25
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 abstract description 21
- 229910052748 manganese Inorganic materials 0.000 abstract description 21
- 239000010405 anode material Substances 0.000 abstract description 11
- 230000004048 modification Effects 0.000 abstract description 10
- 238000012986 modification Methods 0.000 abstract description 10
- 230000000052 comparative effect Effects 0.000 description 15
- 238000009832 plasma treatment Methods 0.000 description 14
- 239000000463 material Substances 0.000 description 13
- 238000012360 testing method Methods 0.000 description 11
- 239000007789 gas Substances 0.000 description 10
- 230000004888 barrier function Effects 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- 238000003756 stirring Methods 0.000 description 8
- 238000007599 discharging Methods 0.000 description 7
- 230000014759 maintenance of location Effects 0.000 description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 6
- 239000010406 cathode material Substances 0.000 description 6
- 238000001556 precipitation Methods 0.000 description 6
- 238000004321 preservation Methods 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 238000000498 ball milling Methods 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 230000002349 favourable effect Effects 0.000 description 3
- 239000011229 interlayer Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 230000002572 peristaltic effect Effects 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 230000002427 irreversible effect Effects 0.000 description 2
- 230000000087 stabilizing effect Effects 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229910002982 Li2MnO3 phase Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- KLARSDUHONHPRF-UHFFFAOYSA-N [Li].[Mn] Chemical compound [Li].[Mn] KLARSDUHONHPRF-UHFFFAOYSA-N 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
- 150000001450 anions Chemical class 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000007323 disproportionation reaction Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000037427 ion transport Effects 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 229910001428 transition metal ion Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- UONOETXJSWQNOL-UHFFFAOYSA-N tungsten carbide Chemical compound [W+]#[C-] UONOETXJSWQNOL-UHFFFAOYSA-N 0.000 description 1
- 238000005303 weighing Methods 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
- H01M4/48—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
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J37/00—Discharge tubes with provision for introducing objects or material to be exposed to the discharge, e.g. for the purpose of examination or processing thereof
- H01J37/32—Gas-filled discharge tubes
- H01J37/32009—Arrangements for generation of plasma specially adapted for examination or treatment of objects, e.g. plasma sources
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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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
-
- 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)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Plasma & Fusion (AREA)
- Analytical Chemistry (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses an atmospheric pressure cold plasma modified lithium-rich manganese oxide positive electrode material, a preparation method and application thereof, and relates to the technical field of preparation of lithium ion battery positive electrode materials. According to the invention, through plasma discharge treatment, the content of oxygen vacancies on the surface of the lithium-rich manganese is increased, and the lithium-rich manganese oxide anode material with high capacity, large multiplying power and excellent cycle performance is obtained. The invention solves the problem of complex modification process of the existing lithium-rich manganese anode material.
Description
Technical Field
The invention relates to the technical field of preparation of lithium ion battery anode materials, in particular to an atmospheric pressure cold plasma modified lithium-rich manganese oxide anode material, a preparation method and application thereof.
Background
Lithium ion batteries have become an indispensable secondary battery in the market due to their advantages of long service life, high energy density, environmental friendliness, and the like. With the continuous development of energy storage technology, the requirements of people on the energy density of batteries are also continuously increasing. The lithium-rich manganese anode material has the advantages of large theoretical capacity (> 300 mAh.g -1), high working voltage, low cost and the like, and is considered as the most promising anode material for realizing the high-energy-density lithium ion battery. However, at present, the large-scale application of the lithium ion battery is limited due to the key problems of low initial coulombic efficiency, capacity/voltage attenuation, poor rate capability, poor cycle stability and the like. Therefore, in order to accelerate the commercialization process thereof, it is important to effectively solve the problems faced thereto.
Since the Li 2MnO3 phase is activated when the lithium-rich manganese positive electrode material is charged to above 4.5V, capacity is provided by anion oxidation reduction, oxygen precipitation is inevitably generated, and the irreversible structural transformation is caused, so that the electrochemical performance is affected. Therefore, the introduction of oxygen vacancies stabilizes lattice oxygen on the surface of lithium-rich manganese, and the slowing of oxygen precipitation plays a role in stabilizing the structure. At present, oxygen vacancies are mainly generated through surface modification and sintering in a reducing atmosphere, in the patent specification with the publication number of CN113410457A, the inventor discloses a preparation method for generating oxygen vacancies by heating treatment of a lithium-rich manganese-based layered positive electrode material by argon gas, the method can improve the multiplying power performance and the cycle stability of the lithium-rich manganese-based layered positive electrode material, can inhibit precipitation of transition metal ions and voltage decay in the lithium-rich manganese-based layered positive electrode material and can reduce precipitation of oxygen at the same time, and in the patent specification with the publication number of CN110828816A, the inventor discloses that a hydrazine hydrate material with reducibility is introduced on the surface of a main body material of the lithium-rich manganese-based positive electrode material by using a stirring method, and compared with the material without oxygen vacancies of the same kind, the method has great improvement in the battery cycle stability, the multiplying power and other battery performances. All the cases belong to surface modification, but have the problems of complex treatment process and even harmful environment, and need to be improved.
Disclosure of Invention
In order to solve the technical problems, the invention aims to provide an atmospheric pressure cold plasma modified lithium-rich manganese oxide positive electrode material, and a preparation method and application thereof, so as to solve the problem of complex modification process of the existing lithium-rich manganese positive electrode material.
The technical scheme for solving the technical problems is as follows, and the atmospheric pressure cold plasma modified lithium-rich manganese oxide positive electrode material is provided, and the chemical formula of the positive electrode material is Li 1.2Ni0.132Co0.172Mn0.492O2.
The atmospheric pressure cold plasma modified lithium-rich manganese oxide positive electrode material has the advantages of high specific capacity, high multiplying power performance and excellent cycle performance, low material cost, no use of any other chemical reagent, increase of oxygen vacancy content only by changing different discharge atmospheres, and increase of c-axis due to leftward shift of material (003) peak after atmospheric pressure cold plasma treatment, and is beneficial to improvement of lithium ion diffusion. In addition, the valence state of Mn on the surface of the material is improved under the cold plasma modification of the reducing atmosphere, and the electrode material structure is stabilized. The final lithium-rich manganese oxide positive electrode material has excellent electrochemical performance.
Based on the technical scheme, the invention can also be improved as follows:
The invention also provides a preparation method of the atmospheric pressure cold plasma modified lithium-rich manganese oxide positive electrode material, which comprises the following steps of adopting plasma treatment to the lithium-rich manganese oxide positive electrode material to prepare the atmospheric pressure cold plasma modified lithium-rich manganese oxide positive electrode material.
Further, a mixed gas, which is a mixed gas of Ar and any one of H 2、O2 and NH 3, is used for discharging to generate plasma.
Further, the flow rate of the mixed gas is 80-120mL/min.
Further, the flow rate of the mixed gas was 100mL/min.
Further, the discharge voltage is 13-19kV, and the discharge frequency is 11.76-11.78kHz.
Further, the discharge voltage was 19kV and the discharge frequency was 11.78kHz.
Further, the discharge time is 5-40min.
Further, the discharge time was 40min.
Further, the lithium-rich manganese oxide positive electrode material is placed in a coaxial dielectric barrier discharge reactor for plasma treatment.
Further, the inner diameter of the coaxial dielectric barrier discharge reactor is 7mm, and the outer diameter is 10mm.
Further, ar is introduced to discharge air in the coaxial dielectric barrier discharge reactor, and then plasma treatment is performed.
Further, ar flow is 80-120mL/min, and the introducing time is 5-20min.
Further, the Ar flow rate was 100mL/min, and the charging time was 10min.
Further, the lithium-rich manganese oxide positive electrode material is prepared by the following method:
(1) Mixing lithium acetate dihydrate, nickel acetate tetrahydrate, cobalt acetate tetrahydrate, manganese acetate tetrahydrate and citric acid monohydrate, adding the mixture into deionized water, and stirring to prepare a precursor solution;
(2) And (3) carrying out spray drying on the precursor solution prepared in the step (1), and then carrying out heat treatment to obtain the lithium-rich manganese oxide positive electrode material.
Further, in the step (1), the molar ratio of the lithium acetate dihydrate to the nickel acetate tetrahydrate to the cobalt acetate tetrahydrate to the manganese acetate tetrahydrate is 1-1.5:0.1-0.2:0.1-0.2:0.49-0.6.
Further, in the step (1), the molar ratio of the lithium acetate dihydrate, the nickel acetate tetrahydrate, the cobalt acetate tetrahydrate and the manganese acetate tetrahydrate is 1-1.5:0.1-0.2:0.1-0.2:0.49-0.6, and 3% of the molar amount of the original lithium acetate dihydrate is additionally added to compensate lithium loss during the heat treatment.
Further, in step (1), the molar ratio of lithium acetate dihydrate, nickel acetate tetrahydrate, cobalt acetate tetrahydrate and manganese acetate tetrahydrate is 1.2:0.132:0.172:0.492.
Further, in step (1), the molar ratio of lithium acetate dihydrate, nickel acetate tetrahydrate, cobalt acetate tetrahydrate and manganese acetate tetrahydrate was 1.2:0.132:0.172:0.492, and lithium acetate dihydrate in an amount of 3% by mole of the original lithium acetate dihydrate was additionally added to compensate for lithium loss during heat treatment.
Further, in the step (1), the total concentration of the metal acetate in the precursor solution is 0.1 to 0.2mol/L, and the concentration of the citric acid monohydrate is 0.2 to 0.4mol/L.
Further, in the step (1), the total concentration of the metal acetate in the precursor solution was 0.15mol/L, and the concentration of citric acid monohydrate was 0.3mol/L.
Further, in the step (1), stirring is performed at 20-30 ℃ for 1-2h.
Further, in the step (1), the stirring speed is 400-600rpm.
Further, in the step (1), the stirring rotation speed was 500rpm.
Further, in the step (2), the spray drying is carried out at an inlet temperature of 200-250 ℃, an outlet temperature of 110-115 ℃ and a feeding speed of 1-2L/h.
Further, in the step (2), the spray-drying was conducted at an inlet temperature of 230℃and an outlet temperature of 115℃and a feed rate of 1L/h.
Further, in the step (2), the temperature is raised to 900-1200 ℃ in the air atmosphere, and the heat preservation is carried out for 18-22min, so that the heat treatment process is completed.
Further, in the step (2), the temperature is raised to 1000 ℃ in the air atmosphere, and the heat preservation is carried out for 20min, so that the heat treatment process is completed.
Further, the temperature rising rate is 2-5 ℃ per minute.
Further, the temperature rise rate was 3℃/min.
The invention also provides application of the atmospheric pressure cold plasma modified lithium-rich manganese oxide positive electrode material in preparation of lithium ion batteries.
The invention has the following beneficial effects:
1. The plasma is a novel surface modification means, has simple process, can uniformly treat the material under the conditions of rapidness, greenness and high efficiency, can interact with atoms on the surface of the lithium-rich manganese oxide, leads to redistribution of a surface electronic structure to induce generation of oxygen vacancies, and is favorable for improving the electrochemical performance of the lithium-rich manganese oxide anode material.
2. According to the invention, other reducing chemical reagents are not required to be introduced, the content of oxygen vacancies on the lithium-rich manganese surface is increased through plasma discharge treatment, which is favorable for inhibiting precipitation of lattice oxygen under high voltage and improving structural stability, secondly, atmospheric pressure cold plasma modification enables a peak of a material (003) to move left, enlarges interlayer spacing of a (003) crystal face and is favorable for rapid transportation of lithium ions, and finally, after plasma treatment, surface charge distribution is changed, so that Mn valence state is increased, ni valence state is reduced, and not only is structure stabilized but also capacity contribution of transition metal is improved. Finally, the lithium-rich manganese oxide anode material with high capacity, large multiplying power and excellent cycle performance is obtained.
3. The preparation method of the lithium-rich manganese-based positive electrode material provided by the invention has the advantages of simple synthesis process, rapid and efficient modification process, low cost, environmental friendliness and suitability for mass production and application, and can realize uniform treatment by changing the plasma discharge atmosphere.
4. By the atmospheric pressure plasma treatment in O 2:Ar、H2:Ar、NH3 -Ar different discharge atmospheres, the oxygen vacancy content of the surface of the lithium-rich manganese oxide is increased to 34.80%, 43.16% and 56.33% respectively compared with that of the surface of the unmodified lithium-rich manganese oxide. The LRO/NH 3 Ar sample assembled lithium ion battery prepared by the method provided by the invention has the capacity retention rate as high as 73.15% after 400 cycles at a current density of 200mA/g, and has the capacity retention rate of 80% after 297 cycles at a current density of more than 1000mA/g, and has the capacity retention rate of 67.84% after 500 cycles. The atmospheric pressure cold plasma modified lithium-rich manganese oxide positive electrode material has electrochemical performance superior to that of most lithium-rich manganese-based positive electrode materials, and improves the service performance and effect of lithium ion batteries.
Drawings
FIG. 1 is an XRD pattern of the positive electrode materials prepared in examples 1 to 3 and comparative example 1;
FIG. 2 is an SEM image of the positive electrode materials prepared in examples 1-3 and comparative example 1;
FIG. 3 is an XPS O1s graph of the positive electrode materials prepared in examples 1-3 and comparative example 1;
FIG. 4 is an XPS Mn2p graph of the positive electrode materials prepared in examples 1-3 and comparative example 1;
FIG. 5 is an XPS Ni2p graph of the positive electrode materials prepared in examples 1-3 and comparative example 1;
FIG. 6 is a first charge-discharge diagram of the positive electrode materials prepared in examples 1-3 and comparative example 1;
FIG. 7 is a graph showing the cycle performance at a current density of 200mA/g of the positive electrode materials prepared in examples 1 to 3 and comparative example 1;
FIG. 8 is a graph showing the rate performance of the positive electrode materials prepared in examples 1 to 3 and comparative example 1;
FIG. 9 shows the cycle performance of the positive electrode materials prepared in examples 1 to 3 and comparative example 1 at a current density of 1000 mA/g.
Detailed Description
The principles and features of the present invention are described below with reference to the drawings, the examples are illustrated for the purpose of illustrating the invention and are not to be construed as limiting the scope of the invention. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
Example 1:
the atmospheric pressure cold plasma modified lithium-rich manganese oxide positive electrode material has a chemical formula of Li 1.2Ni0.132Co0.172Mn0.492O2.
The preparation method of the atmospheric pressure cold plasma modified lithium-rich manganese oxide positive electrode material comprises the following steps:
(1) Mixing lithium acetate dihydrate, nickel acetate tetrahydrate, cobalt acetate tetrahydrate, manganese acetate tetrahydrate and citric acid monohydrate, adding the mixture into deionized water, and stirring the mixture for 1h at 25 ℃ and 500rpm to prepare a precursor solution;
Wherein, the mol ratio of the lithium acetate dihydrate to the nickel acetate tetrahydrate to the cobalt acetate tetrahydrate to the manganese acetate tetrahydrate is 1.2:0.132:0.172:0.492, and 3 percent of the original lithium acetate dihydrate by mol amount is additionally added to compensate the lithium loss in the heat treatment process, the total concentration of the metal acetate in the precursor solution is 0.15mol/L, and the concentration of the citric acid monohydrate is 0.3mol/L;
(2) The precursor solution prepared in the step (1) is pumped to a spray dryer by peristaltic pump, spray drying is carried out at high temperature and high pressure, the inlet temperature of spray drying is 230 ℃, the outlet temperature is 115 ℃ and the feeding speed is 1L/h, then the precursor solution is placed in an alumina crucible (120 mm, 120mm in width and 50mm in height), the alumina crucible is placed in a box furnace, and the temperature is raised to 1000 ℃ at a temperature raising rate of 3 ℃ per minute in air atmosphere, and the heat preservation is carried out for 20min, so that the heat treatment process is completed, and the lithium-rich manganese oxide anode material is prepared;
(3) Placing the lithium-rich manganese oxide positive electrode material prepared in the step (2) into a coaxial dielectric barrier discharge reactor (with the inner diameter of 7mm and the outer diameter of 10 mm), introducing Ar with the flow rate of 100mL/min, introducing Ar for 10min, discharging air in the coaxial dielectric barrier discharge reactor, performing plasma treatment, discharging by adopting mixed gas (H 2 and Ar) with the flow rate of 100mL/min to generate cold plasma, wherein the discharge voltage is 19kV, the discharge frequency is 11.78kHz, and the discharge time is 40min, and obtaining the atmospheric pressure cold plasma modified lithium-rich manganese oxide positive electrode material (named as LRO/H 2: ar).
Example 2:
the atmospheric pressure cold plasma modified lithium-rich manganese oxide positive electrode material has a chemical formula of Li 1.2Ni0.132Co0.172Mn0.492O2.
The preparation method of the atmospheric pressure cold plasma modified lithium-rich manganese oxide positive electrode material comprises the following steps:
In the step (3), the mixed gas (O 2 and Ar) is discharged to generate cold plasma, the discharge voltage is 13kV, the discharge frequency is 11.76kHz, and the discharge time is 10min, so that the atmospheric pressure cold plasma modified lithium-rich manganese oxide positive electrode material (named as LRO/O 2: ar) is prepared. The procedure is as in example 1.
Example 3:
the atmospheric pressure cold plasma modified lithium-rich manganese oxide positive electrode material has a chemical formula of Li 1.2Ni0.132Co0.172Mn0.492O2.
The preparation method of the atmospheric pressure cold plasma modified lithium-rich manganese oxide positive electrode material comprises the following steps:
In the step (3), the mixed gas (NH 3 and Ar) is discharged to generate cold plasma, the discharge voltage is 13kV, the discharge frequency is 11.76kHz, and the discharge time is 40min, so that the atmospheric pressure cold plasma modified lithium-rich manganese oxide positive electrode material (named LRO/NH 3: ar) is prepared. The procedure is as in example 1.
Example 4:
the atmospheric pressure cold plasma modified lithium-rich manganese oxide positive electrode material has a chemical formula of Li 1.2Ni0.132Co0.172Mn0.492O2.
The preparation method of the atmospheric pressure cold plasma modified lithium-rich manganese oxide positive electrode material comprises the following steps:
(1) Mixing lithium acetate dihydrate, nickel acetate tetrahydrate, cobalt acetate tetrahydrate, manganese acetate tetrahydrate and citric acid monohydrate, adding the mixture into deionized water, and stirring the mixture for 2 hours at 20 ℃ and 400rpm to prepare a precursor solution;
The molar ratio of the lithium acetate dihydrate to the nickel acetate tetrahydrate to the cobalt acetate tetrahydrate to the manganese acetate tetrahydrate is 1:0.1:0.1:0.49, and 3% of the original lithium acetate dihydrate by mole is additionally added to compensate lithium loss in the heat treatment process, wherein the total concentration of the metal acetate in the precursor solution is 0.1mol/L, and the concentration of the citric acid monohydrate is 0.2mol/L;
(2) The precursor solution prepared in the step (1) is pumped to a spray dryer by peristaltic pump, spray drying is carried out at high temperature and high pressure, the inlet temperature of spray drying is 200 ℃, the outlet temperature is 110 ℃, the feeding speed is 1.5L/h, then the precursor solution is placed in an alumina crucible (120 mm, width is 120mm, and height is 50 mm), the alumina crucible is placed in a box-type furnace, and the temperature is raised to 900 ℃ at a heating rate of 2 ℃ per min in air atmosphere, and the heat preservation is carried out for 22min, so that the heat treatment process is completed, and the lithium-rich manganese oxide anode material is prepared;
(3) Placing the lithium-rich manganese oxide positive electrode material prepared in the step (2) into a coaxial dielectric barrier discharge reactor (with the inner diameter of 7mm and the outer diameter of 10 mm), introducing Ar with the flow rate of 80mL/min, introducing Ar for 20min, discharging air in the coaxial dielectric barrier discharge reactor, performing plasma treatment, discharging by adopting mixed gas (O 2 and Ar) with the flow rate of 80mL/min to generate cold plasma, wherein the discharge voltage is 13kV, the discharge frequency is 11.76kHz, and the discharge time is 5min, so that the atmospheric pressure cold plasma modified lithium-rich manganese oxide positive electrode material is prepared.
Example 5:
the atmospheric pressure cold plasma modified lithium-rich manganese oxide positive electrode material has a chemical formula of Li 1.2Ni0.132Co0.172Mn0.492O2.
The preparation method of the atmospheric pressure cold plasma modified lithium-rich manganese oxide positive electrode material comprises the following steps:
(1) Mixing lithium acetate dihydrate, nickel acetate tetrahydrate, cobalt acetate tetrahydrate, manganese acetate tetrahydrate and citric acid monohydrate, adding the mixture into deionized water, and stirring the mixture for 1.5 hours at the temperature of 30 ℃ and the rpm of 600rpm to prepare a precursor solution;
The molar ratio of the lithium acetate dihydrate to the nickel acetate tetrahydrate to the cobalt acetate tetrahydrate to the manganese acetate tetrahydrate is 1.5:0.2:0.2:0.6, and 3% of the original lithium acetate dihydrate by mole is additionally added to compensate lithium loss in the heat treatment process, wherein the total concentration of the metal acetate in the precursor solution is 0.2mol/L, and the concentration of the citric acid monohydrate is 0.3mol/L;
(2) The precursor solution prepared in the step (1) is pumped to a spray dryer by peristaltic pump, spray drying is carried out at high temperature and high pressure, the inlet temperature of spray drying is 250 ℃, the outlet temperature is 115 ℃, the feeding speed is 2L/h, then the precursor solution is placed in an alumina crucible (120 mm, width is 120mm, and height is 50 mm), the alumina crucible is placed in a box furnace, and the temperature is raised to 1200 ℃ at a temperature raising rate of 5 ℃ per min in air atmosphere, and the heat preservation is carried out for 18min, so that the heat treatment process is completed, and the lithium-rich manganese oxide anode material is prepared;
(3) Placing the lithium-rich manganese oxide positive electrode material prepared in the step (2) into a coaxial dielectric barrier discharge reactor (with the inner diameter of 7mm and the outer diameter of 10 mm), introducing Ar with the flow rate of 120mL/min, introducing Ar for 5min, discharging air in the coaxial dielectric barrier discharge reactor, performing plasma treatment, discharging by adopting mixed gas (NH 3 and Ar) with the flow rate of 80-120mL/min to generate cold plasma, wherein the discharge voltage is 15kV, the discharge frequency is 11.77kHz, and the discharge time is 40min, so as to prepare the atmospheric pressure cold plasma modified lithium-rich manganese oxide positive electrode material.
Comparative example 1:
A lithium-rich manganese oxide positive electrode material has a chemical formula of Li 1.2Ni0.132Co0.172Mn0.492O2.
The preparation method of the lithium-rich manganese oxide positive electrode material comprises the following steps:
except for step (3), a lithium-rich manganese oxide positive electrode material (named LRO) was produced in the same manner as in example 1.
Test examples
1. XRD testing
XRD tests were performed on the lithium-rich manganese-based cathode materials prepared in examples 1 to 3 and comparative example 1, respectively, and the average structure of the lithium-rich manganese-based cathode materials was tested, with the results shown in FIG. 1.
As can be seen from fig. 1, after plasma treatment, the peak positions of LRO/H 2：Ar、LRO/O2：Ar、LRO/NH3: ar (003) are shifted in the low angle direction, indicating that the c-axis interlayer spacing is increased, which is advantageous for lithium ion transport.
2. SEM test
SEM tests were performed on the lithium-rich manganese-based cathode materials prepared in examples 1 to 3 and comparative example 1, respectively, to test the surface morphology and average size of the lithium-rich manganese-based cathode materials, and the results are shown in FIG. 2.
As can be seen from fig. 2, the morphology is not changed significantly before and after the atmospheric pressure cold plasma treatment, which indicates that the surface bombardment of the lithium-manganese-rich positive electrode material by high-energy particles generated by the plasma in different discharge atmospheres does not damage the morphology and size of the particles, and the original morphology of the material is maintained. The particle size of the lithium-rich manganese-based positive electrode material before and after plasma treatment is 200-300nm.
3. XPS test
XPS test was performed on the lithium-rich manganese-based cathode materials prepared in examples 1 to 3 and comparative example 1, respectively, to test the surface structures of the lithium-rich manganese-based cathode materials, and the results are shown in FIGS. 3 to 5.
As can be seen from FIGS. 3-5, the oxygen vacancy content of the lithium-rich manganese-based positive electrode material prepared by the embodiment of the invention is increased, wherein the increase of LRO/H 2:Ar and LRO/NH 3:Ar is more remarkable, and the increase of LRO/O 2:Ar is smaller, because the ratio of the LRO/O 2:Ar in the mixed discharge atmosphere of O 2:Ar is 1:4, and the ratio of O 2 is smaller. In fact Ar itself has some reducibility, which can generate oxygen vacancies, but the reduction strength is quite different from H 2 and NH 3. Even though O 2 is reducing, a small amount of oxygen vacancies will be generated at a small ratio. The increase of oxygen vacancies helps to stabilize lattice oxygen on the surface of the material, inhibit lattice oxygen precipitation at high voltage, and improve the stability of the high-voltage crystal structure. It was also found that the valence state of Mn on the surface of the material increases after the atmospheric cold plasma treatment in a reducing atmosphere, which also plays a role in stabilizing the structure.
4. Electrochemical performance test
1. Preparation of positive electrode plate
Weighing the lithium-rich manganese-based positive electrode materials prepared in the examples 1-3 and the comparative example 1 and Super P according to the mass ratio of 8:1, placing the materials in a ball milling tank, adding tungsten carbide ball milling beads, adding alcohol as a dispersing agent into the ball milling tank, ball milling for 6 hours, and drying in a drying box to obtain a mixture A;
285mg of mixture A and 1250mg of CMC solution with the mass concentration of 1.2% are weighed, stirred for 2 hours at room temperature, then subjected to ultrasonic treatment for 2 hours, stirred for 2 hours again, coated on aluminum foil by using a 0.15 mu m scraper, placed in a vacuum drying oven for drying at 110 ℃ for 20 hours, cut into pole pieces with the diameter of 10mm, and then the cut pole pieces are transferred into a 115 ℃ vacuum drying oven for drying for 10 hours for standby.
2. Assembled CR2025 stainless steel button cell
And (3) taking a metal lithium sheet as a negative electrode, dripping 250 mu L of LBC-3045I (G) commercial electrolyte, completing the assembly of the CR2025 stainless steel button cell in a glove box filled with argon and having the moisture content lower than 0.01ppm, and testing the charge-discharge performance after standing for 40 hours at 45 ℃.
CR2025 stainless steel button cell electrochemical performance test:
The batteries prepared in examples 1 to 3 and thus comparative example 1 were respectively subjected to cycle performance testing at 25 ℃ and voltage window of 2.0 to 4.8V by constant current charge and discharge, and the tested current densities were 0.1C,0.2C,0.5C,1C,2C,5C and 10C, respectively, wherein 1c=200ma/g, and the results are shown in fig. 6 to 9.
As can be seen from FIG. 6, with the increase of the oxygen vacancy content, the lithium ion battery prepared by Ar is a lithium-rich manganese oxide positive electrode material LRO/O 2 in the embodiment 2, and the initial discharge specific capacity is 272.83mAh/g at the current density of 20 mA/g.
As can be seen from FIGS. 7-8, the lithium ion battery prepared by the lithium-rich manganese oxide positive electrode material LRO/NH 3: ar of example 3 of the invention has a capacity retention rate as high as 73.15% and a voltage retention rate as high as 80.44% after 400 cycles at a current density of 200 mA/g. This is mainly because the increase in the oxygen vacancy content can stabilize lattice oxygen to inhibit the release of irreversible oxygen, further leading to an increase in Mn valence state, reducing the disproportionation reaction to stabilize the framework structure of the overall material, and improving the cycling stability. The lithium ion battery prepared by the lithium-rich manganese oxide positive electrode material LRO/O 2:Ar and LRO/NH 3:Ar maintains excellent rate performance in the rate performance test of 0.1C,0.2C,0.5C,1C,2C,5C and 10C.
As can be seen from fig. 9, the surface of the lithium-rich manganese oxide positive electrode material prepared by the method is rich in oxygen vacancies after plasma treatment, and the interlayer spacing is increased, so that the structural stability is improved, and rapid diffusion of lithium ions is promoted, so that the lithium ion battery prepared by the lithium-rich manganese oxide positive electrode material prepared by the method has 145.29mAh/g and 147.98mAh/g of capacity even under the ultra-large current density of 1000mA/g, which is significantly higher than the capacity without plasma modification (131.37 mAh/g). In addition, after 297 cycles, the capacity retention rate of the lithium ion battery assembled by the LRO/NH 3 Ar sample is 80%, and after 500 cycles, the capacity retention rate is as high as 67.84%, and excellent rate performance and long-cycle stability are shown.
The foregoing description of the preferred embodiments of the invention is not intended to limit the invention to the precise form disclosed, and any such modifications, equivalents, and alternatives falling within the spirit and scope of the invention are intended to be included within the scope of the invention.
Claims (10)
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