CN116759562A - Double-cation doped positive electrode material and preparation method and application thereof - Google Patents
Double-cation doped positive electrode material and preparation method and application thereof Download PDFInfo
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- CN116759562A CN116759562A CN202311032170.3A CN202311032170A CN116759562A CN 116759562 A CN116759562 A CN 116759562A CN 202311032170 A CN202311032170 A CN 202311032170A CN 116759562 A CN116759562 A CN 116759562A
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- manganese dioxide
- chromium
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- 239000007774 positive electrode material Substances 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title abstract description 22
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims abstract description 231
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 202
- 239000011651 chromium Substances 0.000 claims abstract description 140
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 89
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 89
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims abstract description 81
- 239000000463 material Substances 0.000 claims abstract description 68
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims abstract description 39
- 239000011572 manganese Substances 0.000 claims abstract description 37
- 238000000034 method Methods 0.000 claims abstract description 33
- 150000001768 cations Chemical class 0.000 claims abstract description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000010405 anode material Substances 0.000 claims abstract description 7
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910001430 chromium ion Inorganic materials 0.000 claims abstract description 4
- 229910001453 nickel ion Inorganic materials 0.000 claims abstract description 4
- 238000004070 electrodeposition Methods 0.000 claims description 17
- 239000011259 mixed solution Substances 0.000 claims description 15
- 238000004502 linear sweep voltammetry Methods 0.000 claims description 12
- 239000002994 raw material Substances 0.000 claims description 8
- 238000006056 electrooxidation reaction Methods 0.000 claims description 7
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical compound [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 230000003647 oxidation Effects 0.000 claims description 4
- 238000007254 oxidation reaction Methods 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 241000080590 Niso Species 0.000 claims description 2
- XHFVDZNDZCNTLT-UHFFFAOYSA-H chromium(3+);tricarbonate Chemical compound [Cr+3].[Cr+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O XHFVDZNDZCNTLT-UHFFFAOYSA-H 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 239000011701 zinc Substances 0.000 abstract description 20
- 150000002500 ions Chemical class 0.000 abstract description 16
- 239000003792 electrolyte Substances 0.000 abstract description 10
- 238000006243 chemical reaction Methods 0.000 abstract description 8
- 230000008569 process Effects 0.000 abstract description 8
- 238000003780 insertion Methods 0.000 abstract description 7
- 230000002441 reversible effect Effects 0.000 abstract description 7
- 230000009881 electrostatic interaction Effects 0.000 abstract description 4
- 230000009286 beneficial effect Effects 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 3
- 239000002253 acid Substances 0.000 abstract description 2
- 238000012983 electrochemical energy storage Methods 0.000 abstract description 2
- 230000009849 deactivation Effects 0.000 abstract 1
- WJZHMLNIAZSFDO-UHFFFAOYSA-N manganese zinc Chemical compound [Mn].[Zn] WJZHMLNIAZSFDO-UHFFFAOYSA-N 0.000 abstract 1
- 238000004146 energy storage Methods 0.000 description 22
- 238000000634 powder X-ray diffraction Methods 0.000 description 18
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 14
- 229910052799 carbon Inorganic materials 0.000 description 14
- 239000007772 electrode material Substances 0.000 description 14
- 239000004744 fabric Substances 0.000 description 13
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 11
- 238000001228 spectrum Methods 0.000 description 11
- VNNRSPGTAMTISX-UHFFFAOYSA-N chromium nickel Chemical compound [Cr].[Ni] VNNRSPGTAMTISX-UHFFFAOYSA-N 0.000 description 10
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 10
- 239000000243 solution Substances 0.000 description 9
- 238000002484 cyclic voltammetry Methods 0.000 description 8
- 230000001351 cycling effect Effects 0.000 description 8
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 7
- 239000013078 crystal Substances 0.000 description 6
- 239000000523 sample Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 229910018487 Ni—Cr Inorganic materials 0.000 description 5
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical class [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 5
- 230000007423 decrease Effects 0.000 description 5
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 5
- 229910052697 platinum Inorganic materials 0.000 description 5
- 238000006479 redox reaction Methods 0.000 description 5
- 229910052725 zinc Inorganic materials 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 238000000151 deposition Methods 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 239000008151 electrolyte solution Substances 0.000 description 4
- 238000011066 ex-situ storage Methods 0.000 description 4
- 229910052748 manganese Inorganic materials 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 230000009471 action Effects 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 230000007246 mechanism Effects 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 230000009977 dual effect Effects 0.000 description 2
- 238000000724 energy-dispersive X-ray spectrum Methods 0.000 description 2
- 230000001747 exhibiting effect Effects 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000010348 incorporation Methods 0.000 description 2
- 230000037431 insertion Effects 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 230000027756 respiratory electron transport chain Effects 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000002083 X-ray spectrum Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000001566 impedance spectroscopy Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910001760 lithium mineral Inorganic materials 0.000 description 1
- 229940099596 manganese sulfate Drugs 0.000 description 1
- 239000011702 manganese sulphate Substances 0.000 description 1
- 235000007079 manganese sulphate Nutrition 0.000 description 1
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002064 nanoplatelet Substances 0.000 description 1
- 239000000123 paper Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 239000013074 reference sample Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 238000010408 sweeping Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000006276 transfer reaction Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 229960001763 zinc sulfate Drugs 0.000 description 1
- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/006—Compounds containing, besides nickel, two or more other elements, with the exception of oxygen or hydrogen
-
- 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
- H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
-
- 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
-
- 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
-
- 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
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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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
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- Chemical Kinetics & Catalysis (AREA)
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- Composite Materials (AREA)
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- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The application relates to a double-cation doped positive electrode material, a preparation method and application thereof, belonging to the technical field of electrochemical energy storage; the positive electrode material comprises a cation doped manganese dioxide material, wherein the doped cations comprise chromium ions and nickel ions; the material provides the dissolution-deposition chemical property of zinc ion battery when used as zinc ion batteryThe double-cation doping can obviously improve the conductivity of the anode material, reduce the electrostatic interaction between the anode material and zinc ions, and improve the rate performance and the cycle stability. Reversible Cr in charge-discharge process 3+ /Cr 2+ MnO of which the deactivation of the positive electrode side can be effectively reduced by the reaction 2 Is helpful to promote MnO in weak acid mild electrolyte 2 /Mn 2+ Is transformed by the above method. The doping ions of the manganese dioxide doped with the chromium and nickel biscationes are also beneficial to Zn 2+ /H + Co-insertion kinetics. The water-based zinc-manganese battery has ultrahigh capacity, excellent rate performance and excellent cycle stability.
Description
Technical Field
The application relates to the technical field of electrochemical energy storage, in particular to a double-cation doped positive electrode material, and a preparation method and application thereof.
Background
In order to meet the demands of energy storage and application, researchers have been seeking new, high-performance, environmentally friendly energy storage technologies. These techniques may be used to meet the energy requirements of different types of portable and stationary energy storage devices. Lithium ion batteries are a relatively mature secondary battery energy storage system, but have the problems of inflammability and safety and shortage of lithium ore resources, which causes the price to be continuously increased.
In order to solve the problem of inflammable safety of lithium ion batteries and the problem of shortage of lithium mineral resources, development of novel water-based secondary zinc ion batteries has become a research hotspot in the field of energy storage. Zinc ion batteries have the advantages of cost effectiveness, high safety, simple manufacturing process, and the like over lithium ion batteries. In addition, zinc is abundant in natural resources on the crust, which makes it a very promising energy storage system. However, the performance of zinc ion batteries still needs to be improved. The positive electrode material determines the electron transfer number and the reaction potential of the battery, and directly influences the energy density and the stability of the water-based zinc ion battery. Therefore, the development of advanced positive electrode materials is critical to aqueous zinc ion batteries.
Disclosure of Invention
The application provides a double-cation doped positive electrode material, a preparation method and application thereof, so as to improve the energy storage characteristic of a zinc ion battery.
In a first aspect, the present application provides a positive electrode material comprising a cation doped manganese dioxide material, the cations doped comprising chromium ions and nickel ions of different valence states.
As an alternative embodiment, the cation doped manganese dioxide has the molecular formula Cr x Ni y -MnO 2 Wherein x is 0.5 to 3.5 and y is 0.5 to 3.5.
In a second aspect, the present application provides a method for preparing a positive electrode material, the method comprising:
mixing manganese dioxide raw material, a chromium source and a nickel source in a solvent to obtain a mixed solution;
electrochemical deposition of the mixed solution to form manganese dioxide and Cr 3+ And Ni 2+ Introducing the manganese dioxide to obtain an intermediate;
subjecting the intermediate to electrochemical oxidation to cause part of the Cr in the intermediate 3+ Oxidation to Cr 5+ And obtaining the manganese dioxide anode material doped with the polyvalent bimetallic element.
As an alternative embodiment, the manganese dioxide feedstock includes Mn (CH 3 COO) 2 ·4H 2 O and MnSO 4 ·4H 2 O and at least one of water and compounds thereof; and/or
The chromium isThe source includes Cr (CH) 3 COO) 3 At least one of chromium nitrate and chromium carbonate; and/or
The nickel source comprises Ni (NO) 3 ) 2 ·6H 2 O and NiSO 4 ·6H 2 At least one of O.
As an optional implementation manner, in the mixed solution, the molar concentration of the manganese dioxide raw material is 0.05-0.15 m; and/or
In the mixed solution, the molar concentration of the chromium source is 0.01-0.03M; and/or
In the mixed solution, the molar concentration of the nickel source is 0.01-0.03M.
As an alternative embodiment, the voltage of the electrochemical deposition is 1 to 1.4v; and/or
The time of the electrochemical deposition is 600-800 s.
As an alternative implementation manner, the electrochemical deposition adopts a linear sweep voltammetry, and the voltage interval of the linear sweep voltammetry is 1.2-1.9 v; the scanning speed of the linear sweep voltammetry is 2-6 mV/s.
In a third aspect, the present application provides a positive electrode sheet, the positive electrode sheet comprising a positive electrode material layer, the positive electrode material layer comprising the positive electrode material according to the first aspect or the positive electrode material prepared by the preparation method according to the second aspect.
As an alternative embodiment, the positive electrode sheet further includes a current collector, and the positive electrode material layer is attached to the current collector, and the current collector may be one or more selected from hydrophilic carbon cloth, carbon paper, stainless steel, and titanium mesh.
In a fourth aspect, the present application provides a zinc ion battery comprising the positive electrode sheet of the third aspect. The electrolyte is 2M zinc sulfate plus 0.1M manganese sulfate, and the cathode is commercial high-purity zinc foil.
Compared with the prior art, the technical scheme provided by the embodiment of the application has the following advantages:
the anode material provided by the embodiment of the application is manganese dioxide doped with chromium and nickel double cations, and when the material is used as a zinc ion battery, the material is zincThe dissolution-deposition chemistry of the ion battery provides enhancement, the positive electrode can significantly increase specific capacity, reduce electrostatic interactions, and improve rate performance and cycling stability. In addition, reversible Cr in manganese dioxide doped with chromium and nickel bimetallic elements 3+ /Cr 2+ The reaction can effectively reduce the MnO of which the anode side is deactivated in the charge-discharge cycle 2 （dead MnO 2 ) Is helpful to promote MnO in acidic mild electrolyte 2 /Mn 2+ Breaking through MnO by conversion of (C) 2 /Mn 3+ Theoretical specific capacity limit of single electron transfer reaction (308 mAh/g). Meanwhile, the doping ions of manganese dioxide doped with chromium and nickel double positive elements are favorable for Zn 2+ /H + Co-insertion kinetics. Thereby allowing the battery to exhibit ultra-high capacity, superior rate performance and excellent cycling stability.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate embodiments consistent with the application and together with the description, serve to explain the principles of the application.
In order to more clearly illustrate the embodiments of the application or the technical solutions of the prior art, the drawings which are used in the description of the embodiments or the prior art will be briefly described, and it will be obvious to a person skilled in the art that other drawings can be obtained from these drawings without inventive effort.
FIG. 1 is a graph showing electrochemical deposition of chromium and nickel biscationally doped manganese dioxide material obtained in example 1 according to the application; wherein the abscissa is time, units: second, wherein the second is; the ordinate is current, units: milliamp; the curve is an electrochemical curve of the deposition of manganese dioxide material doped with chromium and nickel double cations;
FIG. 2 is a graph of electrochemical oxidation of chromium and nickel biscationally doped manganese dioxide material obtained in example 1 of the present application; wherein the abscissa is voltage, unit: volts; the ordinate is voltage, units: volts; the curve is the oxidation electrochemical curve of the manganese dioxide material doped with chromium and nickel double cations;
FIG. 3 is a Scanning Electron Microscope (SEM) of a chromium, nickel biscationally doped manganese dioxide material obtained in application example 1;
FIG. 4 is an X-ray powder diffraction pattern (XRD) of the sample prepared in accordance with example 1 of this application; wherein the abscissa is 2θ, units: a degree; the ordinate is intensity; the curve is manganese dioxide material doped with chromium and nickel double cations;
FIG. 5 is a graph of the X-ray photoelectron spectrum under the preparation condition of example 1 of the present application, showing the full spectrum of chromium and nickel biscationally doped manganese dioxide; wherein the abscissa is binding energy, units: electron volts; the ordinate is intensity;
FIG. 6 is an EDS spectrum under the preparation condition of example 1 of the present application; wherein the abscissa is binding energy, units: electron volts; the ordinate is intensity.
FIG. 7 is an X-ray photoelectron spectrum under the preparation condition of example 1 of the present application; the curve is Mn 2p spectrogram of manganese dioxide doped with chromium and nickel double cations; wherein the abscissa is binding energy, units: electron volts; the ordinate is intensity;
FIG. 8 is an X-ray photoelectron spectrum under the preparation condition of the embodiment 1 of the application, wherein the curve is a Ni 2p spectrum of manganese dioxide doped with chromium and nickel double cations; wherein the abscissa is binding energy, units: electron volts; the ordinate is intensity;
FIG. 9 is a graph of the X-ray photoelectron spectrum under the preparation condition of example 1 of the present application, which is a Cr 2p spectrum of manganese dioxide doped with chromium and nickel biscationic ions; wherein the abscissa is binding energy, units: electron volts; the ordinate is intensity;
FIG. 10 is a cyclic voltammogram of chromium and nickel biscationdoped manganese dioxide material obtained in example 1 of the present application and pure manganese dioxide as positive electrode of zinc ion, with a scan rate of 0.5mV/s and a voltage interval of 0.8-1.8V, wherein the abscissa is the capacity in units: voltage, unit: volts; the ordinate is current, units: milliamp;
FIG. 11 is a cyclic voltammogram of a chromium and nickel biscationally doped manganese dioxide material obtained in example 1 of the present application as a positive electrode for zinc ions, the number of scanning turns being 4, the scanning rate being 0.5mV/s, the voltage interval being between 0.8 and 1.8V, wherein the abscissa is the capacity in units: voltage, unit: volts; the ordinate is current, units: milliamp;
FIG. 12 is a graph showing the charge and discharge curves of chromium and nickel biscationally doped manganese dioxide material and pure manganese dioxide obtained in example 1 of the present application as a zinc ion positive electrode, wherein the constant current charge and discharge employs a small current density of 200 mA/g, and the abscissa represents the capacity in units of: milliampere hours per gram; the ordinate is voltage, units: volts;
FIG. 13 is an electrochemical impedance plot of chromium and nickel biscationally doped manganese dioxide material and pure manganese dioxide obtained in example 1 of the present application as zinc ion positive electrode, wherein the abscissa is impedance in units: ohmic; the ordinate is capacitive reactance, units: ohmic;
FIG. 14 is a graph showing the rate performance of chromium and nickel biscationally doped manganese dioxide material and pure manganese dioxide obtained in example 1 of the present application as a zinc ion positive electrode, wherein the minimum current density for constant current charge and discharge is 0.2A/g, the minimum current density is 2A/g, and the abscissa is the number of cycles; the ordinate is capacity, units: milliampere hours per gram;
FIG. 15 is a graph showing the cycling performance of the chromium and nickel biscationally doped manganese dioxide material and pure manganese dioxide obtained in example 1 of the present application as zinc ion positive electrode, with a minimum current density of 0.2A/g for constant current charge and discharge, 2A/g for constant current charge and discharge and with the abscissa being the number of cycles; the ordinate is capacity, units: milliampere hours per gram;
FIG. 16 is a graph showing the long cycle performance of the chromium and nickel biscationally doped manganese dioxide material and pure manganese dioxide obtained in example 1 of the present application as zinc ion positive electrode, with a minimum current density of 0.2A/g for constant current charge and discharge, 2A/g for minimum current density and cycle number on the abscissa; the ordinate is capacity, units: milliampere hours per gram;
fig. 17 a shows the charge-discharge curve of the chromium and nickel biscationally doped manganese dioxide material obtained in example 1 of the present application; wherein the abscissa is voltage, unit: volts;
shown in b of fig. 17 is an ex-situ XRD spectrum at voltage points corresponding to charge-discharge curves, where the abscissa is 2θ, units: a degree; the ordinate is intensity. The curve is XRD of manganese dioxide material doped with chromium and nickel double cations at different voltage points;
FIG. 17 c is an X-ray photoelectron spectrum of a chromium and nickel biscationally doped manganese dioxide material obtained in example 1 of the present application; the curve is Zn 2p spectrogram of chromium and nickel double-cation doped manganese dioxide, wherein the abscissa is binding energy, unit: electron volts; the ordinate is intensity;
FIG. 18 is an SEM image of a chromium and nickel biscationally doped manganese dioxide material according to example 1 of the present application under different voltage conditions;
FIG. 19 is an XPS graph of O1 s, mn 2p and Cr 2p of the chromium and nickel biscationally doped manganese dioxide material obtained in example 1 of the present application under different voltage conditions, wherein the abscissa indicates binding energy in units: electron volts; the ordinate is intensity;
FIG. 20 is an atomic content diagram of Mn element in different voltage states of the chromium and nickel biscationally doped manganese dioxide material obtained in example 1 of the present application;
FIG. 21 is an X-ray powder diffraction pattern (XRD) of example 2 of the present application under the conditions of preparation; wherein the abscissa is 2θ, units: a degree; the ordinate is intensity; the curves are manganese dioxide materials doped with double cations with different nickel-chromium ratios;
FIG. 22 is an X-ray powder diffraction pattern (XRD) of example 3 of the present application under the conditions of preparation; wherein the abscissa is 2θ, units: a degree; the ordinate is intensity; the curves are manganese dioxide materials doped with double cations with different chromium-nickel ratios;
FIG. 23 is a long cycle chart of the zinc ion positive electrode of different nickel-chromium ratio biscationally doped manganese dioxide materials obtained in example 1 of the present application, wherein the constant current charge and discharge employs a current density of 0.2A/g, and the abscissa represents the number of cycles; the ordinate is capacity, units: milliampere hours per gram;
FIG. 24 is a long cycle chart of the zinc ion positive electrode of manganese dioxide materials doped with different chromium-nickel ratios and double cations obtained in example 1 of the present application, wherein the constant current charge and discharge adopts a current density of 0.2A/g, and the abscissa represents the number of cycles; the ordinate is capacity, units: milliampere hours per gram;
FIG. 25 is a flow chart of a method provided by an embodiment of the present application;
FIG. 26 is a schematic illustration of a preparation process according to an embodiment of the present application;
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the embodiments of the present application more apparent, the technical solutions of the embodiments of the present application will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present application, and it is apparent that the described embodiments are some embodiments of the present application, but not all embodiments of the present application. All other embodiments, which can be made by those skilled in the art based on the embodiments of the application without making any inventive effort, are intended to be within the scope of the application.
Unless otherwise specifically indicated, the various raw materials, reagents, instruments, equipment and the like used in the present application are commercially available or may be prepared by existing methods.
The embodiment of the application provides a positive electrode material, which comprises a positive ion doped manganese dioxide material, wherein the doped positive ions comprise chromium ions and nickel ions.
In some embodiments, the cation doped manganese dioxide has the formula Cr x Ni y -MnO 2 Wherein x is 0.5 to 3.5 and y is 0.5 to 3.5.
The anode material is manganese dioxide doped with chromium and nickel double cations, and when the material is used as a zinc ion battery, the material provides enhancement for the dissolution-deposition chemical property of the zinc ion battery, and the anode can remarkably improve the conductivity, reduce the electrostatic interaction and improve the rate performance and the circulation stability. In addition, chromium and nickel biscationally doped manganese dioxide reversible Cr 3+ /Cr 2+ The reaction can effectively reduce the deactivated MnO 2 （dead MnO 2 ) Is helpful to promote MnO in acidic mild electrolyte 2 /Mn 2+ Is transformed by the above method. Meanwhile, the doping ions of the manganese dioxide doped with the chromium and nickel double cations are beneficial to Zn 2+ /H + Co-insertion kinetics. Thereby making the battery exhibitUltra-high capacity, superior rate performance and excellent cycling stability.
The manganese dioxide material doped with chromium and nickel double cations has excellent electrochemical performance as a positive electrode material of a zinc ion battery, the zinc storage capacity of the manganese dioxide material reaches 568 mAh/g in the circulating process, the scanning rate adopted by a cyclic voltammetry is 0.5mV/s in the electrochemical performance testing process, the small current density adopted by constant current charge and discharge is 200 mA/g, and the large current density is 2A/g, and the manganese dioxide material has excellent energy storage performance.
Fig. 25 is a flowchart of a method provided by an embodiment of the present application, and fig. 26 is a schematic diagram of a preparation process provided by an embodiment of the present application, as shown in fig. 25, based on a general inventive concept, the embodiment of the present application further provides a method for preparing a positive electrode material, where the method includes:
s1, mixing a manganese dioxide raw material, a chromium source and a nickel source in a solvent to obtain a mixed solution;
in some embodiments, the manganese dioxide feedstock includes Mn (CH 3 COO) 2 ·4H 2 O; the chromium source includes Cr (CH) 3 COO) 3 The method comprises the steps of carrying out a first treatment on the surface of the The nickel source comprises Ni (NO) 3 ) 2 ·6H 2 O. In the mixed solution, the molar concentration of the manganese dioxide raw material is 0.05-0.15M; in the mixed solution, the molar concentration of the chromium source is 0.01-0.03M; in the mixed solution, the molar concentration of the nickel source is 0.01-0.03M.
S2, carrying out electrochemical deposition on the mixed solution to form manganese dioxide and Cr 3+ And Ni 2+ Introducing the manganese dioxide to obtain an intermediate;
in some embodiments, the electrochemical deposition voltage is 1-1.4 v; the time of the electrochemical deposition is 600-800 s.
Specifically, in this example, carbon cloth CC (20 mm ×20 mm) was placed as a working electrode on a substrate containing 0.1M Mn (CH 3 COO) 2 ·4H 2 O and Cr (CH) in different molar ratios 3 COO) 3 And Ni (NO) 3 ) 2 ·6H 2 O50 mL in deionized water. Using platinum mesh and saturated calomel electricityThe electrode (saturated potassium chloride) was used as a counter electrode and a reference electrode, and was operated at a constant potential of 1.2V for 700 s, respectively, to convert Cr 3+ And Ni 2+ Introduction of MnO 2 In the laminate.
S3, carrying out electrochemical oxidation on the intermediate so as to enable part of Cr in the intermediate 3+ Oxidation to Cr 5+ And obtaining the positive electrode material.
In some embodiments, the electrochemical deposition adopts a linear sweep voltammetry, and the voltage interval of the linear sweep voltammetry is 1.2-1.9V; the scanning speed of the linear sweep voltammetry is 2-6 mV/s.
Specifically, in this example, mnO was measured by a linear sweep voltammetry test 2 Part of the doped Cr in the electrode 3+ Gradually oxidized to Cr 5+ Scanning at a rate of 5mV/s from 1.2 to 1.9V. Cr (CH) 3 COO) 3 (X) and Ni (NO) 3 ) 2 ·6H 2 The concentration of O (Y) was adjusted between 1 (0.01M), 2 (0.02M) and 3 (0.03M) to control the doping levels of Cr and Ni ions. Finally, regulated MnO 2 The sample was named Cr X Ni Y -MnO 2 And dried at 80℃for 24 hours after washing to weigh the mass of active material (1.2 mg/cm 2 ). Similarly, in the absence of Cr (CH 3 COO) 3 And Ni (NO) 3 ) 2 ·6H 2 0.1M Mn of O (CH 3 COO) 4 ·4H 2 Pure MnO is also prepared in the O electrolyte 2 Samples were compared. Specifically, pure MnO 2 The preparation of the sample may be: KMnO 4 Transferring the solution to a high-pressure reaction kettle, and carrying out hydrothermal reaction for 1-12 hours at the temperature of 150-180 ℃. Then washing with deionized water for multiple times, centrifuging, and drying to obtain powder MnO 2 。
Powder MnO prepared by the application 2 The nano-array structure grows perpendicular to the carbon cloth substrate, and the grain diameter is 200-500 nm. Thus, the reference sample was pure MnO 2 The preparation method can also be as follows: carbon cloth CC (20 mm ×20 mm) as working electrode current collector, platinum mesh and saturated calomel electrode (saturated potassium chloride) as counter electrode and reference electrode, at 0.1M Mn(CH 3 COO) 4 ·4H 2 In the O electrolyte, 700 s is operated under constant potential of 1.2V to prepare pure MnO based on carbon cloth substrate 2 And (3) a sample. Of course, pure MnO 2 Samples can also be obtained in a commercially available manner.
The application designs a multi-ion regulated MnO through a novel two-step electrodeposition method 2 （CrNi-MnO 2 ) Is Zn-MnO 2 The dissolution-deposition chemistry of the cell provides enhancement. CrNi-MnO 2 The positive electrode can obviously improve the conductivity, reduce the electrostatic interaction and improve the rate performance and the cycle stability. In addition, reversible Cr 3+ /Cr 2+ The reaction can effectively reduce the deactivated MnO 2 （dead MnO 2 ) Is helpful to promote MnO in weak acid mild electrolyte 2 /Mn 2+ Is transformed by the above method. Various external analyses and theoretical calculations reveal that doping ions accelerate MnO 2 /Mn 2+ Transformation and Zn 2+ /H + Dual function in terms of co-insertion kinetics. Thus, crNi-MnO 2 The positive electrode has super high capacity, excellent rate performance and excellent cycling stability, and is used for developing excellent Zn-MnO 2 Batteries provide a new idea.
Based on one general inventive concept, an embodiment of the present application also provides a positive electrode sheet including a positive electrode material layer including the positive electrode material provided as above or the positive electrode material manufactured by the manufacturing method provided as above.
The positive electrode plate is realized based on the positive electrode material, and the specific content of the positive electrode material can refer to the above embodiment, and because the positive electrode plate adopts part or all of the technical schemes of the above embodiment, at least has all the beneficial effects brought by the technical schemes of the above embodiment, and the details are not repeated here.
Based on one general inventive concept, an embodiment of the present application also provides a zinc ion battery including the positive electrode sheet provided above.
The application will be further illustrated with reference to specific examples. It is to be understood that these examples are illustrative of the present application and are not intended to limit the scope of the present application. The experimental procedures, which are not specified in the following examples, are generally determined according to national standards. If the corresponding national standard does not exist, the method is carried out according to the general international standard, the conventional condition or the condition recommended by the manufacturer.
Example 1
This example prepares a chromium, nickel biscationally doped manganese dioxide material by:
step A: 24.51 g (0.1 mol) Mn (CH) 3 COO) 2 ·4H 2 O and 2.29 g (0.01 mol) Cr (CH 3 COO) 3 And 2.91g (0.01 mol) Ni (NO) 3 ) 2 ·6H 2 O was dissolved in 50 mL deionized water.
And (B) step (B): transferring the electrolyte solution prepared in the step A to a 100mL electrolytic tank, using carbon cloth CC (20 mm ×20 mm) as a working electrode, using a platinum mesh and a saturated calomel electrode (saturated potassium chloride) as a counter electrode and a reference electrode, respectively operating at constant potential of 1.2V for 700 s, and adding Cr 3+ And Ni 2+ Codoped MnO 2 Deposited on the carbon cloth.
Step C: the double ion doped electrode prepared in the step B is used as a working electrode, and the part of Cr doped in the intermediate is processed by linear sweep voltammetry with the voltage range of 1.2 to 1.9V at the scanning speed of 5mV/s 3+ Gradually oxidized to Cr 5+ Then taking out the electrode, washing the electrode with deionized water for 3 times, and drying the electrode in a 60 ℃ oven for 12 hours to obtain the chromium and nickel double-element doped manganese dioxide material (CrNi-MnO) 2 ）。
FIG. 1 is a graph showing electrochemical deposition of chromium and nickel biscationally doped manganese dioxide material obtained in example 1 according to the application. FIG. 2 is a graph of electrochemical oxidation of chromium and nickel biscationally doped manganese dioxide material obtained in example 1 of the present application. As can be seen from FIGS. 1 and 2, the CrNi-MnO can be obtained by operating 700 s at a constant potential of 1.2V with carbon cloth as the working electrode, platinum mesh and saturated calomel electrode (saturated potassium chloride) as the counter electrode and the reference electrode, respectively 2 Electrochemical depositionOn the carbon cloth, under the same electrolyte system, the electrochemical oxidation treatment is carried out, namely, the linear scanning curve LSV with the sweeping speed of 5mV/s has obvious change in the voltage range of 1.2 to 1.9V, which shows that 2 Medium doped Cr 3+ Gradually oxidized to Cr 5+ Can finally obtain CrNi-MnO 2 An electrode material.
FIG. 3 is a Scanning Electron Microscope (SEM) of a chromium and nickel biscationally doped manganese dioxide material obtained in example 1 of the present application. Fig. 3 demonstrates that the chromium and nickel dual element doped manganese dioxide electrode material has an orientation characteristic that grows substantially perpendicular to the base, has a layered structure, and exhibits a platelet morphology.
FIG. 4 is an X-ray powder diffraction pattern (XRD) of the sample prepared in accordance with example 1 of this application. Wherein the abscissa is 2θ, units: a degree; the ordinate is intensity. The curve is manganese dioxide material doped with chromium and nickel. Fig. 4 shows characteristic peaks of manganese dioxide doped with chromium and nickel double positive metal elements, which correspond to the characteristic diffraction (001), (002), (-111) and (-312) crystal planes, respectively. And compared with MnO 2 The diffraction peak positions of the (B) are consistent, which indicates that the synthesized manganese dioxide doped with the chromium and nickel bimetallic elements is layered MnO 2 A crystal structure. At the same time, cr and Ni diatomic incorporation into MnO is also described 2 Is free from introducing impurities and damaging MnO 2 The original crystal structure.
Elemental analysis is performed below to determine whether chromium, nickel biscationis actually incorporated into manganese dioxide positive electrode materials.
FIG. 5 is a graph showing the X-ray photoelectron spectrum under the preparation condition of example 1 of the present application, wherein the graph is a full spectrum of manganese dioxide doped with chromium and nickel biscationic ions. Wherein the abscissa is binding energy, units: electron volts; the ordinate is intensity. FIG. 6 is a graph of EDS energy spectrum under the conditions of preparation of example 1 of the present application, wherein the abscissa indicates binding energy, unit: electron volts; the ordinate is intensity. FIGS. 5 and 6 are EDS spectra and X-ray spectra, which can also show the signals of Cr and Ni elements, and the signals of Ni 2p and Cr 2p are also shown in the full spectrum of X-ray photoelectron spectra, which also confirm the method of electrochemical deposition,can prepare MnO doped with Cr and Ni by one step 2 And a positive electrode material.
FIG. 7 is an X-ray photoelectron spectrum under the preparation condition of the embodiment 1 of the application, wherein the curve is Mn 2p spectrum of manganese dioxide doped with chromium and nickel. Wherein the abscissa is binding energy, units: electron volts; the ordinate is intensity. FIG. 8 is an X-ray photoelectron spectrum under the preparation condition of the embodiment 1 of the application, wherein the curve is a Ni 2p spectrum of manganese dioxide doped with chromium and nickel. Wherein the abscissa is binding energy, units: electron volts; the ordinate is intensity. FIG. 9 is an X-ray photoelectron spectrum under the preparation condition of the embodiment 1 of the application, wherein the curve is a Cr 2p spectrum of manganese dioxide doped with chromium and nickel. Wherein the abscissa is binding energy, units: electron volts; the ordinate is intensity. FIGS. 7, 8 and 9 demonstrate CrNi-MnO after electrochemical deposition and electrochemical oxidation processes 2 The valence state of Ni in (B) is Ni 2+ Valence, while the valence states of Cr are +3 and +5. Introduction of high valence Metal atom into MnO 2 After the crystal structure, the valence state of Mn element is slightly reduced, which also shows that transition metal element is successfully doped into the positive electrode material.
Application example 1
And (3) electrodepositing the chromium and nickel double-cation doped manganese dioxide material obtained in the embodiment 1 on a carbon cloth current collector, and drying in a vacuum drying oven to obtain the positive electrode plate of the water-based zinc ion battery.
The electrochemical performance of chromium and nickel double-cation doped manganese dioxide material is measured by adopting a cyclic voltammetry and a constant current charge-discharge method, in the test, the positive electrode plate is assembled into a button cell, the negative electrode is a wafer zinc foil with the diameter of 10 mm, and 2 mol/L ZnSO is adopted as the negative electrode 4 Adding 0.1 mol/L MnSO 4 The solution was used as an electrolyte solution.
FIG. 10 is a cyclic voltammogram of chromium and nickel biscationdoped manganese dioxide material obtained in example 1 of the present application and pure manganese dioxide as positive electrode of zinc ion, with a scan rate of 0.5mV/s and a voltage interval of 0.8-1.8V, wherein the abscissa is the capacity in units: voltage, unit: volts; the ordinate is current, units: milliamperes. As can be seen from FIG. 10, with pure MnO 2 In contrast, crNi-MnO 2 The positive electrode showed a right shift of the two reduction peaks, suggesting an enhancement of charge transfer kinetics after Cr and Ni ion incorporation. In addition, in CrNi-MnO 2 The increase in response current at 1.33V for the CV curve in the electrode can be attributed to H + Improvement of capacity contribution due to insertion. Pure manganese dioxide was obtained by using CC (20 mm ×20 mm) as a working electrode current collector, using a platinum mesh and a saturated calomel electrode (saturated potassium chloride) as a counter electrode and a reference electrode, and adding a catalyst to the solution in a solution of 0.1M Mn (CH 3 COO) 4 ·4H 2 In the O electrolyte, 700 s is operated under constant potential of 1.2V to prepare pure MnO based on carbon cloth substrate 2 And (3) a sample.
FIG. 11 is a cyclic voltammogram of a chromium and nickel biscationally doped manganese dioxide material obtained in example 1 of the present application as a positive electrode for zinc ions, the number of scanning turns being 4, the scanning rate being 0.5mV/s, the voltage interval being between 0.8 and 1.8V, wherein the abscissa is the capacity in units: voltage, unit: volts; the ordinate is current, units: milliamperes. As can be seen from FIG. 11, the charge-discharge curve of the chromium and nickel biscationally doped manganese dioxide material prepared therefrom shows typical MnO 2 The energy storage curve of the base anode material has the zinc storage capacity of up to the capacity of 540 mAh/g after 20 turns of activation under the current density of 200 mA/g. In contrast, conventional MnO 2 The capacity of the positive electrode material rapidly decays from 300 mAh/g to 200mAh/g after 20 cycles.
FIG. 12 is a graph showing the charge and discharge curves of chromium and nickel biscationally doped manganese dioxide material and pure manganese dioxide obtained in example 1 of the present application as a zinc ion positive electrode, wherein the constant current charge and discharge employs a small current density of 200 mA/g, and the abscissa represents the capacity in units of: milliampere hours per gram; the ordinate is voltage, units: volts. As can be seen from FIG. 12, the prepared chromium and nickel biscationally doped manganese dioxide material and pure manganese dioxide material have a cycle performance diagram as zinc ion positive electrode, and the CrNi-MnO2 positive electrode material has an energy storage capacity of 435 mAh/g after 50 cycles at a current density of 200 mA/g, while pure MnO 2 The capacity after 50 cycles was reduced to 145 mAh/g.
FIG. 13 is an electrochemical impedance plot of chromium and nickel biscationally doped manganese dioxide material and pure manganese dioxide obtained in example 1 of the present application as zinc ion positive electrode, wherein the abscissa is impedance in units: ohmic; the ordinate is capacitive reactance, units: ohmic. Fig. 13 shows that the chemical impedance spectroscopy (EIS) curve can reflect rapid charge transfer and ion diffusion kinetics. In particular, a smaller semicircle of CrNi-MnO2 cathode material in the high frequency region and a lower slope in the low frequency region correspond to faster redox reactions and ion diffusion.
FIG. 14 is a graph showing the rate performance of chromium and nickel biscationally doped manganese dioxide material and pure manganese dioxide obtained in example 1 of the present application as a zinc ion positive electrode, wherein the minimum current density for constant current charge and discharge is 0.2A/g, the minimum current density is 2A/g, and the abscissa is the number of cycles; the ordinate is capacity, units: milliampere hours/gram. As can be seen, crNi-MnO 2 The capacity and the stability after 80 circles of circulation under the low current density are better than those of pure MnO 2 And a positive electrode material.
FIG. 15 is a graph showing the cycling performance of the chromium and nickel biscationally doped manganese dioxide material and pure manganese dioxide obtained in example 1 of the present application as zinc ion positive electrode, with a minimum current density of 0.2A/g for constant current charge and discharge, 2A/g for constant current charge and discharge and with the abscissa being the number of cycles; the ordinate is capacity, units: milliampere hours/gram. As can be seen from the figure, crNi-MnO 2 Shows higher capacity under different current densities, which shows that the structural stability and the conductivity are better than those of pure MnO 2 And a positive electrode material.
FIG. 16 is a graph showing the long cycle performance of the chromium and nickel biscationally doped manganese dioxide material and pure manganese dioxide obtained in example 1 of the present application as zinc ion positive electrode, with a minimum current density of 0.2A/g for constant current charge and discharge, 2A/g for minimum current density and cycle number on the abscissa; the ordinate is capacity, units: milliampere hours/gram. As can be seen from FIG. 16, the cycling performance of the chromium and nickel biscationally doped manganese dioxide material and the pure manganese dioxide material prepared therefrom as zinc ion anodes is shown in a graph with a Ni// CrNi-MnO at a current density of 1.5A/g 2 The device was in 1600 cyclesAfter the ring, the capacity of 192 mAh/g still exists, which proves that Cr and Ni double doping can effectively improve MnO 2 Reversibility of the energy storage mechanism of the material.
The following is a study of energy storage mechanism of chromium and nickel biscationally doped manganese dioxide material obtained in the embodiment 1 of the application.
To investigate Zn// CrNi-MnO 2 The energy storage mechanism of the cell was tested for CrNi-MnO as shown in a in fig. 17 2 The positive electrode develops in structure in a voltage state marked on a charge-discharge curve. Shown as b in fig. 17 is an ex-situ XRD spectrum at voltage points corresponding to the charge-discharge curve. During the first discharge, crNi-MnO 2 The characteristic XRD peak of (C) gradually disappears, and new ZnMn appears 2 O 4 Peak (JCPDS No. 24-1133) indicating MnO 2 /Mn 3+ Is a redox reaction of Zn and (B) 2+ Is inserted (state I). In addition, zn was clearly observed in the completely discharged state (state II) 4 (OH) 6 SO 4 ·0.5H 2 The sharp peak of O (ZHS, JCPDS No. 44-0674) demonstrates Zn 2+ /H + With CrNi-MnO 2 Is inserted into the insertion hole. In the subsequent charging process, with Mn 3+ /Mn 2+ Oxidation-reduction reaction and Zn of (2) 2+ /H + From CrNi-MnO 2 The extraction of CrNi-MnO can be observed again 2 The intensity of the characteristic peaks of (B) increases (state III), leading to ZHS and ZnMn 2 O 4 Dissolution of peaks. The fully charged electrode (state IV) recovered CrNi-MnO 2 Characteristic peaks of (C) indicate CrNi-MnO 2 Highly reversible structural evolution.
C in FIG. 17 is the X-ray photoelectron spectrum of the chromium and nickel biscationally doped manganese dioxide material obtained in example 1 of the present application. Demonstration of CrNi-MnO during cyclic testing 2 The intensity of Zn 2p in the positive electrode also undergoes reversible change, which proves that Zn 2+ Can be reversible in CrNi-MnO 2 Inserted into/removed from the positive electrode.
Fig. 18 is an SEM image of the chromium and nickel biscationally doped manganese dioxide material obtained in example 1 according to the application under different voltage conditions. Chromium and nickel biscationally doped dioxideThe nanoplatelet appearance on the surface of manganese materials can be attributed to H + Is very consistent with ex situ XRD analysis.
FIG. 19 is an XPS plot of O1 s, mn 2p and Cr 2p for a chromium and nickel biscationally doped manganese dioxide material obtained in example 1 of the present application under different voltage conditions. The regulation and control of doping Ni and Cr are further studied through the valence states of Mn, cr and Ni elements. When discharged to 0.8V, mn-OH peak intensity, mn 3+ Intensity and Mn of peaks 2+ The new peaks of (2) are markedly increased, accompanied by Mn-O-Mn and Mn 4+ The decrease in peak intensity indicates Zn 2+ /H + Co-insertion of (C) and CrNi-MnO 2 /Mn 2+ Is a dissolution reaction of (a). When charged to 1.9. 1.9V, the Mn-O-Mn peak intensity returned to the original state, and the dissolved Mn 2+ Oxidized to Mn 3+ And CrNi-MnO 2 Indicating H+/Zn 2+ Can be reversibly prepared from CrNi-MnO 2 Is pulled out of the middle part.
FIG. 20 is a graph showing the atomic content of Mn element in different voltage states of the chromium and nickel biscationally doped manganese dioxide material obtained in example 1 according to the present application. The Mn content of the electrode is reversibly changed under different charge and discharge states, which indicates CrNi-MnO 2 The electrode material is based on MnO in the energy storage process 2 /Mn 2+ Is consistent with the results of ex situ XPS analysis.
Zn// CrNi-MnO through the adjustment of Cr/Ni doping 2 Provides ultra-high capacity (at 0.2A g -1 The lower layer is 568 mAh g -1 ) Excellent rate capability (208 mAh/g at 2.0A/g) and excellent cycle stability. Various external analyses revealed the synergistic effect of multi-ion doping on the redox reaction of CrNi-MnO2 electrodes. Specifically, cr 3+ /Cr 2+ Redox couple and Cr 5+ Can respectively reduce the non-active MnO in the high valence state of (2) 2 Is to accumulate and promote MnO 2 /Mn 2+ Is a phase change of (c). In addition, ni and Cr doping can impart CrNi-MnO 2 Enhanced intrinsic ion/electron conductivity, thereby reducing ion diffusion barrier and enhancing CrNi-MnO 2 Redox kinetics of the electrode. This work may be doneReversible MnO 2 /Mn 2+ Redox chemistry and improvement of Zn// MnO in mild electrolytes 2 Electrochemical activity of the cell provides a new approach.
Example 2
This example 2 a chromium, nickel biscationally doped manganese dioxide material prepared by: the procedure of example 1 was used, except that the other condition parameters were changed to those shown in Table 1.
TABLE 1
Characterization of the chromium and nickel biscationally doped manganese dioxide material prepared in example 2 above:
FIG. 21 is an X-ray powder diffraction (XRD) pattern of manganese dioxide material electrode materials doped with different ratios of chromium to nickel obtained in example 2 of the present application. Wherein the abscissa is 2θ, units: a degree; the ordinate is intensity. MnO with different chromium-nickel ratios 2 And a positive electrode material. The XRD patterns of FIG. 21 are MnO with different chromium-nickel ratios 2 Positive electrode materials, all exhibiting delta-MnO 2 Characteristic peaks of (C) to show MnO of different chromium-nickel ratios 2 Maintains the original MnO 2 A crystal structure. However, as the Cr-Ni ratio increases, the XRD diffraction peak intensity decreases, indicating that excessive doping of Cr results in MnO 2 The crystallinity of (2) decreases.
Application example 2
The electrode material obtained in example 2 was electrodeposited on a carbon cloth current collector, and dried in a vacuum drying oven to obtain a positive electrode sheet of a water-based zinc ion battery.
The electrochemical performance of the electrode material is measured by adopting a cyclic voltammetry and a constant current charge-discharge method, and the testing method is the same as that of application example 1, and the electrode material is prepared into a button cell, 2 mol/L ZnSO 4 Adding 0.1 mol/L MnSO 4 The solution was used as an electrolyte solution.
FIG. 23 shows MnO of different chromium to nickel ratios obtained in example 2 of the present application 2 Cycle performance diagram of positive electrode material as zinc ion positive electrode, and low current density adopted by constant current charge and discharge200 mA/g, with the ordinate being capacity, units: milliampere hours/gram. As can be seen from FIG. 23, the Cr-doped CrNi-MnO having a concentration of 0.1,0.2 and 0.3 mmol was prepared 2 As can be seen from the graph of the cycle performance of the electrode material, crNi-MnO increases as the Cr concentration increases 2 The energy storage capacity of the cathode material may be reduced, possibly because the Cr concentration is too high to occupy the active Mn sites, resulting in capacity fade. However, when Cr is doped to 0.1mmol of CrNi-MnO 2 Shows higher energy storage capacity, and reaches 578.6 mAh/g zinc storage capacity in the charge and discharge process under the current density of 200 mA/g, which indicates that the current reaches MnO 2 The energy storage capacity can be effectively improved by doping Cr into the positive electrode material, and the Cr is the optimal doping ratio when the Cr is doped into 0.1 mmol.
Example 3
This example 3 a chromium, nickel biscationally doped manganese dioxide material was prepared by:
the procedure of example 1 was used, except that the other condition parameters were changed to those shown in Table 2.
TABLE 2
Characterization of the chromium and nickel biscationally doped manganese dioxide material prepared in example 3 above:
FIG. 22 is an X-ray powder diffraction (XRD) pattern of an electrode material of manganese dioxide material doped with chromium and nickel biscationium obtained in application example 2. Wherein the abscissa is 2θ, units: a degree; the ordinate is intensity. MnO with different nickel-chromium ratios 2 And a positive electrode material. FIG. 22 shows XRD patterns of MnO with different nickel-chromium ratios 2 Positive electrode materials, all exhibiting delta-MnO 2 Characteristic peaks of (2) to show MnO of different nickel-chromium ratios 2 Maintains the original MnO 2 A crystal structure. However, as the Cr-Ni ratio increases, the XRD diffraction peak intensity decreases, indicating that excessive doping of Ni leads to MnO 2 The crystallinity of (2) decreases.
Application example 3
The electrode material obtained in example 3 was electrodeposited on a carbon cloth current collector, and dried in a vacuum drying oven to obtain a positive electrode sheet of a water-based zinc ion battery.
The electrochemical performance of the electrode material is measured by adopting a cyclic voltammetry and a constant current charge-discharge method, and the testing method is the same as that of application example 1, and the electrode material is prepared into a button cell, 2 mol/L ZnSO 4 Adding 0.1 mol/L MnSO 4 The solution was used as an electrolyte solution.
FIG. 24 is a graph showing the cycling performance of the chromium and nickel biscationally doped manganese dioxide electrode material obtained in example 3 of the present application as a zinc ion positive electrode, wherein the constant current charge and discharge employs a small current density of 200 mA/g, and the ordinate represents the capacity in units: milliampere hours/gram. As can be seen from FIG. 24, the Ni-doped alloy prepared therefrom was 0.1,0.2,0.3 mmol of CrNi-MnO 2 As can be seen from the graph of the cycle performance of the electrode material, crNi-MnO when the Ni concentration increases 2 The energy storage capacity of the positive electrode material is reduced, and the positive electrode material is doped with excessive Cr, namely CrNi-MnO 2 The positive electrode materials are similar, probably because Ni concentrations that are too high occupy the active Mn sites during synthesis, however Ni does not undergo redox reactions during energy storage and does not provide additional energy storage capacity. However, when Ni is doped to 0.1mmol of CrNi-MnO 2 Shows higher energy storage capacity, and reaches zinc storage capacity of 530.3 mAh/g in the charge and discharge process under the current density of 200 mA/g, which indicates that the current reaches MnO 2 The energy storage capacity can be effectively improved by doping Ni into the positive electrode material, and the Ni is the optimal doping ratio when the Ni is doped into 0.1 mmol.
Various embodiments of the application may exist in a range of forms; it should be understood that the description in a range format is merely for convenience and brevity and should not be construed as a rigid limitation on the scope of the application; it is therefore to be understood that the range description has specifically disclosed all possible sub-ranges and individual values within that range. For example, it should be considered that a description of a range from 1 to 6 has specifically disclosed sub-ranges, such as from 1 to 3, from 1 to 4, from 1 to 5, from 2 to 4, from 2 to 6, from 3 to 6, etc., as well as single numbers within the range, such as 1, 2, 3, 4, 5, and 6, wherever applicable. In addition, whenever a numerical range is referred to herein, it is meant to include any reference number (fractional or integer) within the indicated range.
In the present application, unless otherwise specified, terms such as "upper" and "lower" are used specifically to refer to the orientation of the drawing in the figures. In addition, in the description of the present specification, the terms "include", "comprising" and the like mean "including but not limited to". Relational terms such as "first" and "second", and the like may be used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Herein, "and/or" describing an association relationship of an association object means that there may be three relationships, for example, a and/or B, may mean: a alone, a and B together, and B alone. Wherein A, B may be singular or plural. Herein, "at least one" means one or more, and "a plurality" means two or more. "at least one", "at least one" or the like refer to any combination of these items, including any combination of single item(s) or plural items(s). For example, "at least one (individual) of a, b, or c," or "at least one (individual) of a, b, and c," may each represent: a, b, c, a-b (i.e., a and b), a-c, b-c, or a-b-c, wherein a, b, c may be single or multiple, respectively.
The foregoing is only a specific embodiment of the application to enable those skilled in the art to understand or practice the application. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the application. Thus, the present application is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (10)
1. A biscationally doped positive electrode material, wherein said positive electrode material comprises a biscationally doped manganese dioxide material, and wherein said cations doped comprise chromium ions and nickel ions of different valence states.
2. The biscationally doped positive electrode material according to claim 1, wherein said cationically doped manganese dioxide has the formula Cr x Ni y -MnO 2 Wherein x is 0.5 to 3.5 and y is 0.5 to 3.5.
3. A method for preparing a biscationally doped positive electrode material, the method comprising:
mixing manganese dioxide raw material, a chromium source and a nickel source in a solvent to obtain a mixed solution;
electrochemical deposition of the mixed solution to form manganese dioxide and Cr 3+ And Ni 2+ Introducing the manganese dioxide to obtain an intermediate;
subjecting the intermediate to electrochemical oxidation to cause part of the Cr in the intermediate 3+ Oxidation to Cr 5+ And obtaining the anode material doped with the polyvalent metal cations.
4. The method for producing a biscationally doped positive electrode material according to claim 3, wherein said manganese dioxide raw material comprises Mn (CH 3 COO) 2 ·4H 2 O and MnSO 4 ·4H 2 O and at least one of water and compounds thereof; and/or
The chromium source includes Cr (CH) 3 COO) 3 At least one of chromium nitrate and chromium carbonate; and/or
The nickel source comprises Ni (NO) 3 ) 2 ·6H 2 O and NiSO 4 ·6H 2 At least one of O.
5. The method for preparing a biscationally doped positive electrode material according to claim 3, wherein the molar concentration of the manganese dioxide raw material in the mixed solution is 0.05-0.15M; and/or
In the mixed solution, the molar concentration of the chromium source is 0.01-0.03M; and/or
In the mixed solution, the molar concentration of the nickel source is 0.01-0.03M.
6. The method for preparing a biscationally doped positive electrode material according to claim 3, wherein the electrochemical deposition voltage is 1-1.4 v; and/or
The time of the electrochemical deposition is 600-800 s.
7. The method for preparing a biscationally doped positive electrode material according to claim 3, wherein the electrochemical deposition adopts a linear sweep voltammetry, and a voltage interval of the linear sweep voltammetry is 1.2-1.9V; the scanning speed of the linear sweep voltammetry is 2-6 mV/s.
8. A positive electrode sheet, characterized in that the positive electrode sheet comprises a positive electrode material layer comprising the positive electrode material according to any one of claims 1 to 2 or the positive electrode material produced by the production method according to any one of claims 3 to 7.
9. The positive electrode sheet of claim 8, further comprising a current collector, wherein the positive electrode material layer is attached to the current collector.
10. A zinc-ion battery comprising the positive electrode sheet of claim 9.
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