CN113871586A - Controllable manganese-based layered oxide electrode material and preparation method and application thereof - Google Patents
Controllable manganese-based layered oxide electrode material and preparation method and application thereof Download PDFInfo
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- acetate tetrahydrate
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- 239000011572 manganese Substances 0.000 title claims abstract description 186
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 title claims abstract description 84
- 229910052748 manganese Inorganic materials 0.000 title claims abstract description 76
- 239000007772 electrode material Substances 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims abstract description 70
- 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 abstract description 38
- 229940082328 manganese acetate tetrahydrate Drugs 0.000 claims abstract description 38
- 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 abstract description 38
- 235000010333 potassium nitrate Nutrition 0.000 claims abstract description 35
- 239000004323 potassium nitrate Substances 0.000 claims abstract description 35
- SZQUEWJRBJDHSM-UHFFFAOYSA-N iron(3+);trinitrate;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O SZQUEWJRBJDHSM-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000011259 mixed solution Substances 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 20
- 239000007787 solid Substances 0.000 claims abstract description 19
- 238000001354 calcination Methods 0.000 claims abstract description 18
- 239000002244 precipitate Substances 0.000 claims abstract description 18
- 238000003756 stirring Methods 0.000 claims abstract description 18
- 238000001035 drying Methods 0.000 claims abstract description 16
- 229940093928 potassium nitrate Drugs 0.000 claims abstract description 16
- 229940097364 magnesium acetate tetrahydrate Drugs 0.000 claims abstract description 14
- XKPKPGCRSHFTKM-UHFFFAOYSA-L magnesium;diacetate;tetrahydrate Chemical compound O.O.O.O.[Mg+2].CC([O-])=O.CC([O-])=O XKPKPGCRSHFTKM-UHFFFAOYSA-L 0.000 claims abstract description 14
- 239000008367 deionised water Substances 0.000 claims abstract description 9
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 9
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims abstract description 8
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims abstract description 8
- PCIGTTWKYUNLEP-UHFFFAOYSA-N azane;2-hydroxypropanoic acid;titanium;dihydrate Chemical compound N.N.O.O.[Ti].CC(O)C(O)=O.CC(O)C(O)=O PCIGTTWKYUNLEP-UHFFFAOYSA-N 0.000 claims abstract description 6
- QZRHHEURPZONJU-UHFFFAOYSA-N iron(2+) dinitrate nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QZRHHEURPZONJU-UHFFFAOYSA-N 0.000 claims description 14
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 229910052744 lithium Inorganic materials 0.000 claims description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 4
- 238000003860 storage Methods 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 3
- XQACDRQNIWUXDH-UHFFFAOYSA-N potassium;nitrate;hydrate Chemical compound O.[K+].[O-][N+]([O-])=O XQACDRQNIWUXDH-UHFFFAOYSA-N 0.000 claims description 3
- 238000004321 preservation Methods 0.000 claims description 3
- IFTLYVOSXXNBGD-UHFFFAOYSA-L [NH4+].[NH4+].O[Ti]O.CC(O)C([O-])=O.CC(O)C([O-])=O Chemical compound [NH4+].[NH4+].O[Ti]O.CC(O)C([O-])=O.CC(O)C([O-])=O IFTLYVOSXXNBGD-UHFFFAOYSA-L 0.000 claims 2
- 238000004519 manufacturing process Methods 0.000 claims 2
- 229910010293 ceramic material Inorganic materials 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 12
- 150000001875 compounds Chemical class 0.000 abstract 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 92
- 239000010936 titanium Substances 0.000 description 45
- 239000011777 magnesium Substances 0.000 description 36
- 230000000694 effects Effects 0.000 description 19
- 239000000243 solution Substances 0.000 description 17
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 8
- 229910001425 magnesium ion Inorganic materials 0.000 description 8
- 239000012071 phase Substances 0.000 description 8
- 230000014759 maintenance of location Effects 0.000 description 7
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 description 6
- 229910001414 potassium ion Inorganic materials 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 238000002441 X-ray diffraction Methods 0.000 description 5
- 229910052719 titanium Inorganic materials 0.000 description 5
- 230000008901 benefit Effects 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 230000002441 reversible effect Effects 0.000 description 4
- 238000006467 substitution reaction Methods 0.000 description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 3
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 239000007774 positive electrode material Substances 0.000 description 3
- 230000007704 transition Effects 0.000 description 3
- DTQHSUHILQWIOM-UHFFFAOYSA-J 2-hydroxypropanoate titanium(4+) dihydroxide Chemical compound O[Ti++]O.CC(O)C([O-])=O.CC(O)C([O-])=O DTQHSUHILQWIOM-UHFFFAOYSA-J 0.000 description 2
- DELALDBRGCSCBZ-UHFFFAOYSA-L 2-hydroxypropanoate;titanium(2+);dihydrate Chemical compound O.O.[Ti+2].CC(O)C([O-])=O.CC(O)C([O-])=O DELALDBRGCSCBZ-UHFFFAOYSA-L 0.000 description 2
- 230000001627 detrimental effect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- -1 titanium ions Chemical class 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000002484 cyclic voltammetry Methods 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000002939 deleterious effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920006316 polyvinylpyrrolidine Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000009897 systematic effect Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Images
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
-
- 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
-
- 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
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
-
- 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
- H01M4/502—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese for non-aqueous cells
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention provides an adjustable manganese-based layered oxide electrode material and a preparation method and application thereof, wherein the preparation method comprises the following steps: dissolving polyvinylpyrrolidone in deionized water, stirring to dissolve, adding potassium nitrate, manganese acetate tetrahydrate, cobalt acetate tetrahydrate and ferric nitrate nonahydrate, or adding potassium nitrate, manganese acetate tetrahydrate, cobalt acetate tetrahydrate, ferric nitrate nonahydrate, magnesium acetate tetrahydrate or bis (2-hydroxypropionic acid) diammonium dihydroxide titanium, and uniformly stirring to obtain a mixed solution; drying the mixed solution in an oven to obtain a solid precipitate; and calcining the solid precipitate to obtain the controllable manganese-based layered oxide electrode material. The invention provides a method for simply and conveniently improving the cycle stability of a manganese-based layered oxide material, which can be conveniently popularized to various manganese-based compounds and has the potential of large-scale application.
Description
Technical Field
The invention relates to the technical field of new energy electrode materials, in particular to an adjustable manganese-based layered oxide electrode material and a preparation method and application thereof.
Background
Due to rich potassium resource and low K+(iii) the oxidation-reduction potential of/K (-2.936vs. E)0) Potassium ion batteries have attracted considerable attention as a replacement for lithium ion batteries. However, the shortage of high-performance positive electrode materials is one of the major obstacles to the development of next-generation high-power and high-energy density potassium ion batteries. Compared with other positive electrode materials, potassium-containing layered transition metal oxides are of great interest due to their high theoretical capacity, suitable voltage plateaus and simple synthesis processes. Particularly, manganese-based layered oxides benefit from the advantages of low cost, environmental friendliness, relatively stable structure and the like, and are widely researched in potassium ion batteries.
However, manganese in general materials generally exists in a mixed valence state of 3+ and 4+, and Mn3+The ginger-taylor effect is easily generated in the manganese-based layered oxide, so that the structure is unstable, and poor cycle performance is shown, which limits the application prospect of the manganese-based layered oxide. On this basis, increasing the average valence of manganese from 3+ to 4+ may be of great importance for improving the cycle stability of manganese-based layered oxides.
Partial substitution of manganese with electrochemically active and/or inactive transition metal elements (e.g., Li, Co, Ni, Zn, and Ti) is an effective method. The doped element can reduce Mn3+And reduce the content of [ MnO ]6]The octahedron structure is distorted, which not only suppresses the ginger-taylor effect, but also improves the phase stability. Although some work has studied the ginger-taylor effect, there is currently no systematic study of the internal relationship of the ginger-taylor effect and the average valence state of manganese to electrochemical properties.
Disclosure of Invention
In view of the above, the invention provides an adjustable manganese-based layered oxide electrode material, and a preparation method and an application thereof, so as to solve the problem that the existing manganese-based layered oxide has poor cycle stability due to the ginger-taylor effect.
In order to achieve the purpose, the technical scheme of the invention is realized as follows:
a preparation method of the controllable manganese-based layered oxide electrode material optionally comprises the following steps:
s1, dissolving polyvinylpyrrolidone in deionized water, stirring and dissolving, adding potassium nitrate, manganese acetate tetrahydrate, cobalt acetate tetrahydrate and ferric nitrate nonahydrate, or adding the potassium nitrate, the manganese acetate tetrahydrate, the cobalt acetate tetrahydrate, the ferric nitrate nonahydrate, the magnesium acetate tetrahydrate or the titanium bis (2-hydroxypropionic acid) diammonium dihydroxide, and uniformly stirring to obtain a mixed solution;
s2, drying the mixed solution in an oven to obtain a solid precipitate;
and S3, calcining the solid precipitate to obtain the controllable manganese-based layered oxide electrode material.
Alternatively, in step S1, when the potassium nitrate, manganese acetate tetrahydrate, cobalt acetate tetrahydrate, and iron nitrate nonahydrate are added, the molar ratio of the potassium nitrate hydrate, the manganese acetate tetrahydrate, the cobalt acetate tetrahydrate, and the iron nitrate nonahydrate is in the range of 5:8:1:1 to 5:5:4: 1.
Alternatively, in step S1, when the potassium nitrate, the manganese acetate tetrahydrate, the cobalt acetate tetrahydrate, the iron nitrate nonahydrate, and the titanium di (2-hydroxypropionate) dihydroxide are added, the molar ratio of the potassium nitrate, the manganese acetate tetrahydrate, the cobalt acetate tetrahydrate, the iron nitrate nonahydrate, and the titanium di (2-hydroxypropionate) dihydroxide is in the range of 5:7.5:1: 0.5 to 5:5:4:1: 1.
Alternatively, in step S1, when the potassium nitrate, manganese acetate tetrahydrate, cobalt acetate tetrahydrate, iron nitrate nonahydrate, and magnesium acetate tetrahydrate are added, the molar ratio of the potassium nitrate, the manganese acetate tetrahydrate, the cobalt acetate tetrahydrate, the iron nitrate nonahydrate, and the magnesium acetate tetrahydrate is in the range of 5:7.5:1: 0.5 to 5:5:4:1: 1.
Optionally, in step S2, the drying conditions include a drying temperature in a range of 70 ℃ to 120 ℃ and a drying time in a range of 8h to 15 h.
Alternatively, in step S3, the calcining conditions include: air atmosphere, calcination temperature of 800-900 deg.C, and heat preservation time of 8-12 hThe internal and temperature rise rates are 3 ℃ for min-1To 5 ℃ for min-1Within the range.
Optionally, after calcining the solid precipitate, the method further comprises the steps of: and after the obtained adjustable manganese-based layered oxide electrode material is naturally cooled to 100 ℃, transferring the adjustable manganese-based layered oxide electrode material to an argon environment for storage.
The invention also aims to provide the controllable manganese-based layered oxide electrode material, and the preparation method of the controllable manganese-based layered oxide electrode material is adopted.
The third purpose of the invention is to provide an application of the controllable manganese-based layered oxide electrode material on a lithium battery anode.
Compared with the prior art, the controllable manganese-based layered oxide electrode material and the preparation method and application thereof provided by the invention have the following advantages:
(1) the adjustable manganese-based layered oxide electrode material is synthesized by a solid-phase sintering method of adding different metal sources into raw materials, and when the average valence state of manganese is increased from 3+ to 4+, the ginger-Taylor effect of the manganese-based layered oxide anode can be inhibited, so that the cycle stability of the lithium battery is improved.
(2) The method has the characteristics of cheap raw materials, simple and environment-friendly process, high yield and excellent electrochemical performance of the material, provides a universal strategy for improving the cycle stability of the manganese-based layered oxide material, and has the potential of large-scale application.
Drawings
In order to more clearly illustrate the technical solutions of the present invention or the prior art, the drawings needed for the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and those skilled in the art can also obtain other drawings according to the drawings without creative efforts.
FIG. 1 shows K according to an embodiment of the present invention0.5Mn0.7Co0.2Fe0.1O2、K0.5Mn0.6Co0.2Fe0.1Ti0.1O2And K0.5Mn0.6Co0.2Fe0.1Mg0.1O2XRD pattern of (a);
FIG. 2 shows K according to an embodiment of the present invention0.5Mn0.7Co0.2Fe0.1O2、K0.5Mn0.6Co0.2Fe0.1Ti0.1O2And K0.5Mn0.6Co0.2Fe0.1Mg0.1O2A TEM image of (B);
FIG. 3 shows K according to an embodiment of the present invention0.5Mn0.7Co0.2Fe0.1O2、K0.5Mn0.6Co0.2Fe0.1Ti0.1O2And K0.5Mn0.6Co0.2Fe0.1Mg0.1O2The element distribution map of (a);
FIG. 4 shows K according to an embodiment of the present invention0.5Mn0.7Co0.2Fe0.1O2、K0.5Mn0.6Co0.2Fe0.1Ti0.1O2And K0.5Mn0.6Co0.2Fe0.1Mg0.1O2An XPS map of (A);
FIG. 5 shows K according to an embodiment of the present invention0.5Mn0.7Co0.2Fe0.1O2、K0.5Mn0.6Co0.2Fe0.1Ti0.1O2And K0.5Mn0.6Co0.2Fe0.1Mg0.1O2CV curve diagram of 1.5-3.9V in voltage interval;
FIG. 6 shows K according to an embodiment of the present invention0.5Mn0.7Co0.2Fe0.1O2、K0.5Mn0.6Co0.2Fe0.1Ti0.1O2And K0.5Mn0.6Co0.2Fe0.1Mg0.1O2Respectively at 0.1A g-1And 1A g-1Current density of (a);
FIG. 7 shows K according to an embodiment of the present invention0.5Mn0.7Co0.2Fe0.1O2、K0.5Mn0.6Co0.2Fe0.1Ti0.1O2And K0.5Mn0.6Co0.2Fe0.1Mg0.1O2At a temperature of from 0.05A g-1To 2A g-1Different current densities of (a);
FIG. 8 shows K according to an embodiment of the present invention0.5Mn0.7Co0.2Fe0.1O2、K0.5Mn0.6Co0.2Fe0.1Ti0.1O2And K0.5Mn0.6Co0.2Fe0.1Mg0.1O2An in situ XRD pattern of (a);
FIG. 9 shows K according to an embodiment of the present invention0.5Mn0.7Co0.2Fe0.1O2、K0.5Mn0.6Co0.2Fe0.1Ti0.1O2And K0.5Mn0.6Co0.2Fe0.1Mg0.1O2The partial state density of the Mn 3d electron orbital of (a); mn3+(d) And Mn4+(e) Schematic of the electronic configuration and schematic of the ginger-taylor effect.
Detailed Description
In order to make the aforementioned objects, features and advantages of the present invention comprehensible, embodiments accompanied with figures are described in detail below.
It should be noted that in the description of the embodiments herein, the description of the term "some embodiments" means that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. Throughout this specification, the schematic representations of the terms used above do not necessarily refer to the same implementation or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The term "in.. range" as used herein includes both ends, such as "in the range of 1 to 100" including both ends of 1 and 100.
It has been found that manganese in manganese-based layered oxides generally exists in a mixed valence state of trivalent 3+ and tetravalent 4+, wherein manganese (Mn) is positive quadrivalent4+) Can form undistorted [ MnO ]6]Octahedron, thereby obtaining a stable crystal structure. However, in the 3d electron orbit there is (t)2g)3(eg)1High spin positive trivalent manganese (Mn) in electronic configuration3+) It will produce ginger-taylor effect. Such geometric distortions generally reduce the symmetry and energy of the nonlinear molecular system, resulting in structural disorder and strong strain in the structure, ultimately causing instability of the crystal structure. In addition, during charging and discharging as a positive electrode material, the valence state of manganese may be changed between 3+ and 4+, which causes the ginger-taylor effect in the material to be eliminated and generated again, eventually resulting in an irreversible multi-phase transition process. Thus, Mn3+The structural instability caused by the severe ginger-taylor effect is the main reason for the poor cycling stability of manganese-based layered oxides.
In order to solve the above problems, an embodiment of the present invention provides a method for preparing an adjustable manganese-based layered oxide electrode material, including the following steps:
s1, dissolving polyvinylpyrrolidone in deionized water, stirring and dissolving, adding potassium nitrate, manganese acetate tetrahydrate, cobalt acetate tetrahydrate and ferric nitrate nonahydrate, or adding potassium nitrate, manganese acetate tetrahydrate, cobalt acetate tetrahydrate, ferric nitrate nonahydrate, magnesium acetate tetrahydrate or bis (2-hydroxypropionic acid) diammonium dihydroxide titanium, and uniformly stirring to obtain a mixed solution;
s2, placing the mixed solution in an oven to be dried to obtain solid precipitate;
and S3, calcining the solid precipitate to obtain the controllable manganese-based layered oxide electrode material.
The invention is prepared by adding tetravalent titanium ions (Ti)4+) And divalent magnesium ion (Mg)2+) Incorporated in the layered oxide, Ti4+Successfully reduced the average valence of manganese (from 3.714+ to 3.667+), while Mg2+Lead of (2)Increasing the average valence of manganese (from 3.714+ to 4 +). That is, by adding different metal sources in the raw materials, the average valence state of manganese can be adjusted according to requirements; by using Ti4+And Mg2+For Mn3+/4+The reverse regulation of the valence state is used for verifying the internal relation between the ginger-Taylor effect and the average valence state of manganese to the electrochemical property; and when the average valence of manganese is increased from 3+ to 4+, the ginger-taylor effect of the manganese-based layered oxide positive electrode can be suppressed, thereby improving cycle stability.
Specifically, in step S1, K is finally synthesized by adding potassium nitrate, manganese acetate tetrahydrate, cobalt acetate tetrahydrate and ferric nitrate nonahydrate0.5Mn0.7Co0.2Fe0.1O2When the molar ratio of potassium nitrate hydrate, manganese acetate tetrahydrate, cobalt acetate tetrahydrate and iron nitrate nonahydrate is in the range of 5:8:1:1 to 5:5:4: 1.
When potassium nitrate, manganese acetate tetrahydrate, cobalt acetate tetrahydrate, ferric nitrate nonahydrate and bis (2-hydracrylic acid) diammonium bihydroxide titanium are added, K is finally synthesized0.5Mn0.6Co0.2Fe0.1Ti0.1O2When the molar ratio of potassium nitrate, manganese acetate tetrahydrate, cobalt acetate tetrahydrate, iron nitrate nonahydrate, and bis (2-hydroxypropionic acid) diammonium dihydroxide titanium oxide is in the range of 5:7.5:1:1:0.5 to 5:5:4:1: 1.
When potassium nitrate, manganese acetate tetrahydrate, cobalt acetate tetrahydrate, ferric nitrate nonahydrate and magnesium acetate tetrahydrate are added, K is finally synthesized0.5Mn0.6Co0.2Fe0.1Mg0.1O2When the molar ratio of potassium nitrate, manganese acetate tetrahydrate, cobalt acetate tetrahydrate, ferric nitrate nonahydrate and magnesium acetate tetrahydrate is in the range of 5:7.5:1:1:0.5 to 5:5:4:1: 1.
Wherein, the addition amount of the polyvinylpyrrolidone is 3-5g, and the dosage of the deionized water is 30-50 mL. Weight average molecular weight M of polyvinylpyrrolidonew＝1 300 000。
Specifically, in step S2, the conditions for drying the mixed solution include a drying temperature in the range of 70 ℃ to 120 ℃ and a drying time in the range of 8h to 15h, preferably, at 85 ℃ for 12 h.
Specifically, in step S3, the solid precipitate is calcined to obtain black solid powder, which is the controllable manganese-based layered oxide electrode material, and the calcining conditions include: air atmosphere, calcination temperature of 800-900 deg.C, heat preservation time of 8-12 h, and heating rate of 3 deg.C for min-1To 5 ℃ for min-1Within the range.
Further, after the solid precipitate is calcined, the method also comprises the following steps: and after the obtained adjustable manganese-based layered oxide electrode material is naturally cooled to 100 ℃, transferring the adjustable manganese-based layered oxide electrode material to an argon environment for storage.
The method has the characteristics of cheap raw materials, simple and environment-friendly process, high yield and excellent electrochemical performance of the material, provides a universal strategy for improving the cycle stability of the manganese-based layered oxide material, and has the potential of large-scale application.
The invention further provides a controllable manganese-based layered oxide electrode material, which is prepared by the preparation method of the controllable manganese-based layered oxide electrode material.
The invention further provides an application of the controllable manganese-based layered oxide electrode material to a lithium battery anode.
When the controllable manganese-based layered oxide electrode material is used as a potassium ion battery anode material, the K is lower than the average valence state of manganese0.5Mn0.7Co0.2Fe0.1O2And K0.5Mn0.6Co0.2Fe0.1Ti0.1O2K having the highest average valence of manganese0.5Mn0.6Co0.2Fe0.1Mg0.1O2Shows more excellent cycle stability at 0.1Ag-1The capacity retention rate can reach 91 percent after 150 cycles under the current density of (1 Ag), even if the capacity retention rate is 1Ag-1The high-current-density capacitor still has 74 percent capacity retention rate after being cycled for 500 circles. K having the highest average valence of manganese0.5Mn0.6Co0.2Fe0.1Mg0.1O2In the process of potassium ion extraction/intercalationA highly reversible single-phase reaction is experienced, while the detrimental phase transition from P3 to O3 caused by the ginger-taylor effect is completely suppressed; the average valence state of manganese is improved, so that the ginger-Taylor effect is inhibited, and the circulation stability and single-phase solid solution reaction are improved.
On the basis of the above embodiments, the present invention provides the following specific examples of the method for preparing the controllable manganese-based layered oxide electrode material, and further illustrates the present invention. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. The following examples are examples of experimental procedures not specified under specific conditions, generally according to the conditions recommended by the manufacturer. Unless otherwise indicated, percentages and parts are by mass.
Example 1
The embodiment provides a preparation method of an adjustable manganese-based layered oxide electrode material, which comprises the following steps:
1) dissolving 4g of polyvinylpyrrolidone (K90, Mw 1300000) in 40mL of deionized water, and fully stirring until completely dissolved to obtain a clear solution;
adding 5mmol potassium nitrate, 7mmol manganese acetate tetrahydrate, 2mmol cobalt acetate tetrahydrate and 1mmol ferric nitrate nonahydrate into the clarified solution, and fully stirring until the mixture is clarified to obtain a mixed solution A;
adding 5mmol of potassium nitrate, 6mmol of manganese acetate tetrahydrate, 2mmol of cobalt acetate tetrahydrate, 1mmol of ferric nitrate nonahydrate and 1mmol of bis (2-hydroxypropionic acid) diammonium dihydroxide titanium into the clear solution, and fully stirring to obtain a mixed solution B;
adding 5mmol of potassium nitrate, 6mmol of manganese acetate tetrahydrate, 2mmol of cobalt acetate tetrahydrate, 1mmol of ferric nitrate nonahydrate and 1mmol of magnesium acetate tetrahydrate into the clear solution, and fully stirring to obtain a mixed solution C;
2) putting the mixed liquor A, the mixed liquor B and the mixed liquor C obtained in the step 1) into an oven, and drying for 12 hours at 100 ℃ to obtain a solid precipitate A, a solid precipitate B and a solid precipitate C correspondingly;
3) calcining the solid precipitates obtained in the step 2 in an air atmosphere, wherein the calcining condition comprises that the temperature is 5 ℃ for min-1Heating to 800 deg.C andpreserving heat for 10h, naturally cooling to 100 ℃, taking out, and quickly transferring to a glove box filled with Ar atmosphere for storage; wherein the solid precipitate A is calcined to obtain the adjustable manganese-based layered oxide electrode material K0.5Mn0.7Co0.2Fe0.1O2Calcining the solid precipitate B to obtain the adjustable manganese-based layered oxide electrode material K0.5Mn0.6Co0.2Fe0.1Ti0.1O2Calcining the solid precipitate C to obtain the adjustable manganese-based layered oxide electrode material K0.5Mn0.6Co0.2Fe0.1Mg0.1O2。
For the controllable manganese-based layered oxide electrode material K prepared in example 10.5Mn0.7Co0.2Fe0.1O2、K0.5Mn0.6Co0.2Fe0.1Ti0.1O2And K0.5Mn0.6Co0.2Fe0.1Mg0.1O2The results were characterized by X-ray diffractometry (XRD), Scanning Electron Microscopy (SEM), X-ray photoelectron spectroscopy (XPS), etc., to obtain the result graphs shown in FIGS. 1 to 4.
As can be seen from FIG. 1, K0.5Mn0.7Co0.2Fe0.1O2、K0.5Mn0.6Co0.2Fe0.1Ti0.1O2And K0.5Mn0.6Co0.2Fe0.1Mg0.1O2Are all P3 type layered structure, Ti4+And Mg2+Without changing the crystal structure of the material, nor forming other impurities.
As can be seen from FIG. 2, K0.5Mn0.7Co0.2Fe0.1O2、K0.5Mn0.6Co0.2Fe0.1Ti0.1O2And K0.5Mn0.6Co0.2Fe0.1Mg0.1O2All have particle shapes, the particle diameter is 200-500 nm, and Ti4+And Mg2+The introduction of (2) also has no influence on the morphology of the material.
FIG. 3 is a drawing showingControllable manganese-based layered oxide electrode material K0.5Mn0.7Co0.2Fe0.1O2、K0.5Mn0.6Co0.2Fe0.1Ti0.1O2And K0.5Mn0.6Co0.2Fe0.1Mg0.1O2The distribution of the elements, as can be seen from FIG. 3, all the elements are uniformly distributed, particularly the presence of Ti and Mg elements, indicating that Ti is present4+And Mg2+Was successfully incorporated into the material.
As can be seen from FIG. 4, K0.5Mn0.7Co0.2Fe0.1O2、K0.5Mn0.6Co0.2Fe0.1Ti0.1O2And K0.5Mn0.6Co0.2Fe0.1Mg0.1O2In the formula, the valence states of Co and Fe are both 3+, which indicates that Ti is4+And Mg2+The valence states of Co and Fe are not changed. In addition, also shows K0.5Mn0.6Co0.2Fe0.1Ti0.1O2The valence of the middle Ti element is 4+ and K0.5Mn0.6Co0.2Fe0.1Mg0.1O2The valence state of the medium Mg element is 2 +. Is noteworthy in being coated with Ti4+After partial substitution of Mn, K0.5Mn0.6Co0.2Fe0.1Ti0.1O2Middle Mn3+Is higher than K0.5Mn0.7Co0.2Fe0.1O2Indicating that the valence of Mn is reduced after Ti substitution; and K0.5Mn0.6Co0.2Fe0.1Mg0.1O2The valence of Mn of (B) is 4+, which is indicated by Mg2+The valence of Mn is increased after partial substitution.
According to the actual measurement results combined with the calculation of the charge compensation mechanism, K0.5Mn0.7Co0.2Fe0.1O2、K0.5Mn0.6Co0.2Fe0.1Ti0.1O2And K0.5Mn0.6Co0.2Fe0.1Mg0.1O2Average valence of medium Mn3.714+, 3.667+ and 4+, which indicates that the average valence of manganese can be adjusted by the introduction of Ti and Mg.
For the controllable manganese-based layered oxide electrode material K prepared in example 10.5Mn0.7Co0.2Fe0.1O2、K0.5Mn0.6Co0.2Fe0.1Ti0.1O2And K0.5Mn0.6Co0.2Fe0.1Mg0.1O2Assembling a half cell, and carrying out electrochemical performance test by adopting a button cell, wherein a counter electrode adopts a potassium metal sheet, and the voltage interval of the test is 1.5-3.9V. The test results are shown in FIGS. 5-9.
FIG. 5 is a graph of cyclic voltammetry CV curves of the controllable manganese-based layered oxide electrode material, as can be seen from FIG. 5, K0.5Mn0.7Co0.2Fe0.1O2The CV curves of (A) show four pairs of distinct redox peaks at 2.13/1.85V, 2.54/2.29V, 3.19/2.90V and 3.83/3.70V. K with lower average valence of manganese0.5Mn0.6Co0.2Fe0.1Ti0.1O2CV curve of (D) and K0.5Mn0.7Co0.2Fe0.1O2Similarly, four pairs of redox peaks are shown. Notably, K has a higher average valence of manganese0.5Mn0.6Co0.2Fe0.1Mg0.1O2Only two pairs of redox peaks are shown at 2.13/1.85V and 2.54/2.29V. This indicates that the two pairs of redox peaks of the high voltage region disappear when the average valence of manganese increases from 3.714+ to 4+, while the decrease in the average valence of manganese has no effect on the electrochemical reaction.
FIG. 6 shows K obtained in example 10.5Mn0.7Co0.2Fe0.1O2、K0.5Mn0.6Co0.2Fe0.1Ti0.1O2And K0.5Mn0.6Co0.2Fe0.1Mg0.1O2Respectively at 0.1A g-1And 1A g-1Current density of (2), as can be seen from FIG. 6, at 0.1Ag-1At a current density of (a) of (b),k having the highest average valence of manganese0.5Mn0.6Co0.2Fe0.1Mg0.1O2Shows more excellent circulation stability and still has 89.2mAh g after 150 cycles of circulation-1The capacity retention rate can reach 91 percent. Although the introduction of Ti can improve the cycle stability to some extent, the lower valence state of manganese does not further prolong K0.5Mn0.6Co0.2Fe0.1Ti0.1O2Cycle life of (80.2mAh g)-1Capacity retention rate was 78%). In contrast, has a low average valence K of manganese0.5Mn0.7Co0.2Fe0.1O2The cycle performance is poor, and the reversible capacity after cycle is only 70.3mAh g-1The capacity retention rate was 65%. In particular, K0.5Mn0.6Co0.2Fe0.1Mg0.1O2Exhibits excellent long cycle performance even at 1A g-1The capacity retention rate of 74 percent is still achieved after 500 cycles under high current density.
FIG. 7 shows K obtained in example 10.5Mn0.7Co0.2Fe0.1O2、K0.5Mn0.6Co0.2Fe0.1Ti0.1O2And K0.5Mn0.6Co0.2Fe0.1Mg0.1O2From 0.05Ag-1To 2Ag-1Different current densities of (2) under the multiplying power performance diagram; as can be seen from FIG. 7, K0.5Mn0.6Co0.2Fe0.1Mg0.1O2Also shows excellent rate performance, and the current density can be from 0.05Ag-1Gradually increase to 2Ag-1In 2Ag-1The specific capacity can still be stabilized at 60mAh g under the condition of large current density-1Left and right.
FIG. 8 shows K obtained in example 10.5Mn0.7Co0.2Fe0.1O2、K0.5Mn0.6Co0.2Fe0.1Ti0.1O2And K0.5Mn0.6Co0.2Fe0.1Mg0.1O2An in situ XRD pattern of (a); fromAs can be seen in FIG. 8, the lower K of the manganese average valence state0.5Mn0.7Co0.2Fe0.1O2And K0.5Mn0.6Co0.2Fe0.1Ti0.1O2The phase change process from P3 to O3 occurs in the high voltage range; and K having a high average valence of manganese0.5Mn0.6Co0.2Fe0.1Mg0.1O2A highly reversible single-phase reaction is experienced during potassium ion extraction/intercalation, while the detrimental phase transition from P3 to O3, caused by the zingiber-taylor effect, is completely suppressed.
FIG. 9 shows K obtained in example 10.5Mn0.7Co0.2Fe0.1O2、K0.5Mn0.6Co0.2Fe0.1Ti0.1O2And K0.5Mn0.6Co0.2Fe0.1Mg0.1O2The partial state density of the Mn 3d electron orbital of (a); mn3+(d) And Mn4+(e) Schematic of the electronic configuration and schematic of the ginger-taylor effect. As can be seen from FIG. 9, for K0.5Mn0.7Co0.2Fe0.1O2And K0.5Mn0.6Co0.2Fe0.1Ti0.1O2E of MngThe orbitals split into two groups, one below the fermi level and one above the fermi level, indicating the presence of active Mn in the ginger-taylor effect3+Ions. K0.5Mn0.6Co0.2Fe0.1Mg0.1O2E of medium MngThe orbitals are not split, which means that their Mn is all ginger-Taylor effect inactive Mn4+Ions. The results theoretically demonstrate that the deleterious ginger-taylor effect can be effectively suppressed by adjusting the average valence state of manganese.
Example 2
The embodiment provides a preparation method of a controllable manganese-based layered oxide electrode material, which is different from the embodiment 1 in that:
in the step 1), 5g of polyvinylpyrrolidone is dissolved in 50mL of deionized water, 10mmol of potassium nitrate, 16mmol of manganese acetate tetrahydrate, 2mmol of cobalt acetate tetrahydrate and 2mmol of ferric nitrate nonahydrate are added into the clear solution, and the mixture is fully stirred until the clear solution is clarified to obtain a mixed solution A;
adding 10mmol of potassium nitrate, 15mmol of manganese acetate tetrahydrate, 2mmol of cobalt acetate tetrahydrate, 2mmol of ferric nitrate nonahydrate and 1mmol of bis (2-hydroxypropionic acid) diammonium dihydroxide titanium into the clear solution, and fully stirring to obtain a mixed solution B;
adding 10mmol potassium nitrate, 15mmol manganese acetate tetrahydrate, 2mmol cobalt acetate tetrahydrate, 2mmol ferric nitrate nonahydrate and 1mmol magnesium acetate tetrahydrate into the clear solution, and fully stirring to obtain a mixed solution C;
in the step 2), drying for 15h at 70 ℃;
in step 3), the calcination conditions include 4 ℃ min-1Heating to 850 ℃ and preserving heat for 11 hours;
the remaining steps and parameters were the same as in example 1.
Example 3
The embodiment provides a preparation method of a controllable manganese-based layered oxide electrode material, which is different from the embodiment 1 in that:
in the step 1), 3g of polyvinylpyrrolidone is dissolved in 35mL of deionized water, 2.5mmol of potassium nitrate, 2.5mmol of manganese acetate tetrahydrate, 2mmol of cobalt acetate tetrahydrate and 0.5mmol of ferric nitrate nonahydrate are added into the clear solution, and the mixture is fully stirred until the clear solution is clarified to obtain a mixed solution A;
adding 2.5mmol potassium nitrate, 2.125mmol manganese acetate tetrahydrate, 2mmol cobalt acetate tetrahydrate, 0.5mmol ferric nitrate nonahydrate and 0.375mmol bis (2-hydroxypropionic acid) titanium dihydroxide to the clear solution, and fully stirring to obtain a mixed solution B;
adding 2.5mmol potassium nitrate, 2.125mmol manganese acetate tetrahydrate, 2mmol cobalt acetate tetrahydrate, 0.5mmol ferric nitrate nonahydrate and 0.375mmol magnesium acetate tetrahydrate into the clear solution, and fully stirring to obtain a mixed solution C;
in the step 2), drying for 8 hours at 120 ℃;
in step 3), the calcination conditions include a temperature of 3 ℃ for min-1Heating to 900 ℃ and preserving heat for 8 hours;
the remaining steps and parameters were the same as in example 1.
Example 4
The embodiment provides a preparation method of a controllable manganese-based layered oxide electrode material, which is different from the embodiment 1 in that:
in the step 1), 3.5g of polyvinylpyrrolidone is dissolved in 45mL of deionized water, 4mmol of potassium nitrate, 5.6mmol of manganese acetate tetrahydrate, 1.6mmol of cobalt acetate tetrahydrate and 0.8mmol of ferric nitrate nonahydrate are added into the clear solution, and the mixture is fully stirred until the clear solution is clarified to obtain a mixed solution A;
adding 4mmol of potassium nitrate, 4.8mmol of manganese acetate tetrahydrate, 1.6mmol of cobalt acetate tetrahydrate, 0.8mmol of ferric nitrate nonahydrate and 0.8mmol of bis (2-hydroxypropionic acid) titanium dihydroxide to the clear solution, and fully stirring to obtain a mixed solution B;
adding 4mmol potassium nitrate, 4.8mmol manganese acetate tetrahydrate, 1.6mmol cobalt acetate tetrahydrate, 0.8mmol ferric nitrate nonahydrate and 0.8mmol magnesium acetate tetrahydrate into the clear solution, and fully stirring to obtain a mixed solution C;
in the step 2), drying for 13h at 90 ℃;
in step 3), the calcination conditions include at 5 ℃ for min-1Heating to 900 ℃ and preserving heat for 9 hours;
the remaining steps and parameters were the same as in example 1.
Although the present disclosure has been described above, the scope of the present disclosure is not limited thereto. Various changes and modifications may be effected therein by one of ordinary skill in the pertinent art without departing from the spirit and scope of the present disclosure, and these changes and modifications are intended to be within the scope of the present disclosure.
Claims (9)
1. The preparation method of the controllable manganese-based layered oxide electrode material is characterized by comprising the following steps of:
s1, dissolving polyvinylpyrrolidone in deionized water, stirring and dissolving, adding potassium nitrate, manganese acetate tetrahydrate, cobalt acetate tetrahydrate and ferric nitrate nonahydrate, or adding the potassium nitrate, the manganese acetate tetrahydrate, the cobalt acetate tetrahydrate, the ferric nitrate nonahydrate, the magnesium acetate tetrahydrate or the titanium bis (2-hydroxypropionic acid) diammonium dihydroxide, and uniformly stirring to obtain a mixed solution;
s2, drying the mixed solution in an oven to obtain a solid precipitate;
and S3, calcining the solid precipitate to obtain the controllable manganese-based layered oxide electrode material.
2. The method according to claim 1, wherein in step S1, when the potassium nitrate, manganese acetate tetrahydrate, cobalt acetate tetrahydrate, and iron nitrate nonahydrate are added, the molar ratio of potassium nitrate hydrate, manganese acetate tetrahydrate, cobalt acetate tetrahydrate, and iron nitrate nonahydrate is in the range of 5:8:1:1 to 5:5:4: 1.
3. The method according to claim 1, wherein in step S1, when the potassium nitrate, manganese acetate tetrahydrate, cobalt acetate tetrahydrate, iron nitrate nonahydrate, and titanium diammonium dihydroxide bis (2-hydroxypropionate) are added, the molar ratio of the potassium nitrate, the manganese acetate tetrahydrate, the cobalt acetate tetrahydrate, the iron nitrate nonahydrate, and the titanium diammonium dihydroxide bis (2-hydroxypropionate) is in the range of 5:7.5:1: 0.5 to 5:5:4:1: 1.
4. The production method according to claim 1, wherein in step S1, when the potassium nitrate, manganese acetate tetrahydrate, cobalt acetate tetrahydrate, iron nitrate nonahydrate, and magnesium acetate tetrahydrate are added, the molar ratio of the potassium nitrate, the manganese acetate tetrahydrate, the cobalt acetate tetrahydrate, the iron nitrate nonahydrate, and the magnesium acetate tetrahydrate is in the range of 5:7.5:1: 0.5 to 5:5:4:1: 1.
5. The method according to any one of claims 1 to 4, wherein in step S2, the drying conditions include a drying temperature in the range of 70 ℃ to 120 ℃ and a drying time in the range of 8h to 15 h.
6. The method for producing according to claim 5, which isCharacterized in that, in step S3, the calcining conditions include: air atmosphere, calcination temperature of 800-900 deg.C, heat preservation time of 8-12 h, and heating rate of 3 deg.C for min-1To 5 ℃ for min-1Within the range.
7. The method for preparing the porous ceramic material according to claim 5, wherein the method further comprises the following steps of: and after the obtained adjustable manganese-based layered oxide electrode material is naturally cooled to 100 ℃, transferring the adjustable manganese-based layered oxide electrode material to an argon environment for storage.
8. A controllable manganese-based layered oxide electrode material, characterized in that it is prepared by the preparation method according to any one of claims 1 to 7.
9. Use of the regulatable manganese-based layered oxide electrode material of claim 8 in a positive electrode of a lithium battery.
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Application publication date: 20211231 |