CN115425164A - Preparation method and application of cation-doped modified aqueous zinc ion battery manganese-based positive electrode - Google Patents
Preparation method and application of cation-doped modified aqueous zinc ion battery manganese-based positive electrode Download PDFInfo
- Publication number
- CN115425164A CN115425164A CN202211046914.2A CN202211046914A CN115425164A CN 115425164 A CN115425164 A CN 115425164A CN 202211046914 A CN202211046914 A CN 202211046914A CN 115425164 A CN115425164 A CN 115425164A
- Authority
- CN
- China
- Prior art keywords
- manganese
- cation
- positive electrode
- ion battery
- doped modified
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000011572 manganese Substances 0.000 title claims abstract description 50
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 229910052748 manganese Inorganic materials 0.000 title claims abstract description 44
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 68
- 239000000758 substrate Substances 0.000 claims abstract description 44
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 43
- 150000001768 cations Chemical class 0.000 claims abstract description 13
- 150000002696 manganese Chemical class 0.000 claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 29
- 239000003792 electrolyte Substances 0.000 claims description 28
- 229910002804 graphite Inorganic materials 0.000 claims description 25
- 239000010439 graphite Substances 0.000 claims description 25
- 239000000243 solution Substances 0.000 claims description 25
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 24
- 239000008367 deionised water Substances 0.000 claims description 21
- 229910021641 deionized water Inorganic materials 0.000 claims description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 15
- 229940071125 manganese acetate Drugs 0.000 claims description 14
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 13
- 229910052697 platinum Inorganic materials 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 12
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 10
- 239000011149 active material Substances 0.000 claims description 9
- 239000011575 calcium Substances 0.000 claims description 9
- 239000011734 sodium Substances 0.000 claims description 9
- 239000000654 additive Substances 0.000 claims description 7
- 230000000996 additive effect Effects 0.000 claims description 7
- 229910021607 Silver chloride Inorganic materials 0.000 claims description 6
- 239000002120 nanofilm Substances 0.000 claims description 6
- 239000012266 salt solution Substances 0.000 claims description 6
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims description 6
- 238000002791 soaking Methods 0.000 claims description 6
- 239000007774 positive electrode material Substances 0.000 claims description 5
- 238000004070 electrodeposition Methods 0.000 claims description 4
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 3
- VSGNNIFQASZAOI-UHFFFAOYSA-L calcium acetate Chemical compound [Ca+2].CC([O-])=O.CC([O-])=O VSGNNIFQASZAOI-UHFFFAOYSA-L 0.000 claims description 3
- 239000001639 calcium acetate Substances 0.000 claims description 3
- 235000011092 calcium acetate Nutrition 0.000 claims description 3
- 229960005147 calcium acetate Drugs 0.000 claims description 3
- 239000001632 sodium acetate Substances 0.000 claims description 3
- 235000017281 sodium acetate Nutrition 0.000 claims description 3
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 2
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 claims description 2
- 239000013543 active substance Substances 0.000 abstract description 5
- 230000000052 comparative effect Effects 0.000 description 21
- 229910001424 calcium ion Inorganic materials 0.000 description 7
- 229910001414 potassium ion Inorganic materials 0.000 description 7
- 229910001415 sodium ion Inorganic materials 0.000 description 7
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 5
- 239000013078 crystal Substances 0.000 description 5
- 150000003385 sodium Chemical class 0.000 description 4
- 238000004146 energy storage Methods 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 239000010405 anode material Substances 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- 229940099596 manganese sulfate Drugs 0.000 description 2
- 235000007079 manganese sulphate Nutrition 0.000 description 2
- 239000011702 manganese sulphate Substances 0.000 description 2
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 2
- 239000002135 nanosheet Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 2
- 229910000368 zinc sulfate Inorganic materials 0.000 description 2
- 229960001763 zinc sulfate Drugs 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000003491 array Methods 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000012983 electrochemical energy storage Methods 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- DCYOBGZUOMKFPA-UHFFFAOYSA-N iron(2+);iron(3+);octadecacyanide Chemical class [Fe+2].[Fe+2].[Fe+2].[Fe+3].[Fe+3].[Fe+3].[Fe+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] DCYOBGZUOMKFPA-UHFFFAOYSA-N 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000005486 organic electrolyte Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229920000447 polyanionic polymer Polymers 0.000 description 1
- 235000011056 potassium acetate Nutrition 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Images
Classifications
-
- 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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
- H01M10/38—Construction or manufacture
-
- 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
- H01M4/04—Processes of manufacture in general
-
- 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
- H01M4/04—Processes of manufacture in general
- H01M4/0438—Processes of manufacture in general by electrochemical processing
-
- 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
- H01M4/04—Processes of manufacture in general
- H01M4/049—Manufacturing of an active layer by chemical means
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention provides a cation-doped modified aqueous zinc ion battery manganese-based positive electrode, which comprises a carbon-based conductive substrate with active sites and a cation-doped modified manganese-based active substance M x MnO 2 Wherein M is a cation and X has a value of 0.01 to 0.05. The invention also provides a preparation method and application of the cation-doped modified aqueous zinc ion battery manganese-based positive electrode, and the modified manganese-based positive electrode has the advantages of inhibited capacity attenuation, obviously improved rate capability and greatly enhanced cycle stability.
Description
Technical Field
The invention relates to the technical field of electrochemical energy storage, in particular to a preparation method and application of a manganese-based positive electrode of a cation-doped modified aqueous zinc ion battery.
Background
The problems of energy crisis and environmental pollution faced by the development of human society urgently push people to develop clean, environment-friendly and renewable energy sources such as wind energy, solar energy, tidal energy and the like. However, most of the energy sources are intermittent energy sources, and are limited by a plurality of factors such as environment, time, weather and the like, so that the uncertainty is very large. Therefore, there is a need for a large-scale energy storage system to integrate the intermittent energy source by peak clipping and valley filling to achieve continuous supply of the intermittent energy source.
Today, lithium Ion Batteries (LIBs) that have been successfully commercialized appear to be suitable for large-scale energy storage applications in terms of performance, but their further applications are limited by the high price due to lithium metal and the toxic, flammable problems due to organic electrolytes. Based on the characteristics, the water system multivalent ion (Mg 2+, ca2+, al3+ and Zn2 +) battery with the characteristics of safety, low cost, high power, environmental friendliness and the like becomes the best choice for a large-scale energy storage system. Wherein, the water system Zinc Ion Batteries (ZIBs) taking metal zinc as the negative electrode have low cost, safety, innocuity, water compatibility and high theoretical specific capacity (820 mAh/g, 5855 mAh/cm) 3 ) And high ionic conductivity have received much attention. However, no suitable cathode material is currently available to meet the commercialization of aqueous zinc-ion batteries. Therefore, designing and constructing new cathode materials with highly reversible electrochemical performance and long-term cycling stability remains a great challenge.
The existing research finds that compared with positive electrode materials such as vanadium-based oxide, polyanion compound, prussian blue analogue and the like, the manganese-based positive electrode material has lower toxicity, higher working voltage and theoretical specific capacity (308 mAh/g or 616mAh/g, contribution by single electron or double electron transfer), and is more suitable for the application of water-system zinc ion batteries. Unfortunately, most manganese-based positive electrode materials suffer from poor conductivity, irreversible phase change, slow reaction kinetics, unstable structure, and large capacity loss. These problems are mostly related to structural changes caused by the loss of manganese elements during charge and discharge, and therefore, it is important to search for a method for stabilizing the crystal structure of the material.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a preparation method and application of a manganese-based positive electrode of a cation-doped modified water-based zinc ion battery, and the manganese-based positive electrode has the advantages of stable crystal structure and strong cycling stability of an active substance of the manganese-based positive electrode.
The technical purpose of the invention is realized by the following technical scheme:
the cation-doped modified aqueous zinc ion battery manganese-based positive electrode comprises a carbon-based conductive substrate with active sites and a cation-doped modified manganese-based active material M x MnO 2 Wherein M is a cation and X has a value of 0.01 to 0.05.
The invention is further configured to: the cation-doped modified manganese-based active material M x MnO 2 And the carbon-based conductive substrate is loaded on the surface of the carbon-based conductive substrate through electrochemical deposition.
The invention is further configured to: the cation comprises Na + 、Ca 2+ 、K + One or more of (a).
The invention is further configured to: the cation-doped modified manganese-based active material M x MnO 2 Are supported on only the same side of the carbon-based conductive substrate.
The invention is further configured to: the cation-doped modified manganese-based active material M loaded on the surface of the carbon-based conductive substrate x MnO 2 The microscopic morphology of the nano-film is a nano-film array constructed by nano-films.
The invention also provides a preparation method of the manganese-based positive electrode of the cation-doped modified aqueous zinc ion battery, which comprises the following steps:
step 1, applying a voltage of 1.5-2.5V on an electrochemical workstation for 20-30min by using a two-electrode system, taking a platinum sheet as a counter electrode and a reference electrode, taking graphite paper as a working electrode and taking concentrated sulfuric acid as electrolyte;
step 3, preparing a manganese acetate solution, and taking the manganese acetate solution as a basic electrolyte;
step 4, acetate containing cations is selected as an additive and added into the basic electrolyte in the step 3 to obtain a mixed acetate solution;
and 6, taking out the carbon-based conductive substrate treated in the step 5, washing the carbon-based conductive substrate for 3 times by using deionized water and absolute ethyl alcohol respectively, removing residual salt solution on the surface, and drying the carbon-based conductive substrate in an oven at 80 ℃ for 24 hours to obtain the cation-doped modified aqueous zinc ion battery manganese-based positive electrode.
The invention is further configured to: the concentration of the manganese acetate solution in the step 3 is 0.05mol/L.
The invention is further configured to: the acetate used as the additive in the step 4 is one or more of sodium acetate, calcium acetate and methyl acetate.
The invention also provides application of the cation-doped modified water-system zinc ion battery manganese-based positive electrode as a positive electrode material in a water-system zinc ion battery.
The invention has the following advantages:
1. according to the preparation method of the cation-doped modified aqueous zinc ion battery manganese-based positive electrode, the in-situ loading of the active substance and the doping of the metal cations are realized by adopting an electrochemical deposition method, the preparation method is simple, and a binder and a conductive agent are not needed; the loading capacity of the active substance can be regulated and controlled by controlling the electrochemical deposition time and the working potential.
2. The invention provides a preparation method of a cation-doped modified aqueous zinc ion battery manganese-based positive electrode, which adopts graphite paper, acetate and sulfuric acid as raw materials and is low in price.
3. The preparation method of the cation-doped modified aqueous zinc ion battery manganese-based positive electrode provided by the invention realizes the doping of metal cations by selecting different acetates, and has wide applicability. And the crystal structure of the manganese-based positive electrode active substance can be stabilized through the interlayer pillar effect of cations, the capacity attenuation of the modified manganese-based positive electrode is inhibited, the rate capability is obviously improved, and the cycle stability is greatly enhanced.
Drawings
FIG. 1 is an X-ray diffraction (XRD) pattern of the positive electrodes described in examples 1 to 3 and comparative example 1;
FIG. 2 is a Scanning Electron Microscope (SEM) image of the same base conductive substrate of examples 1-3 and comparative example 1 at different magnifications;
FIG. 3 is a Scanning Electron Microscope (SEM) image of the positive electrode described in examples 1 to 3 and comparative example 1 at different magnifications;
FIG. 4 is a graph of rate performance at current densities of 50 to 2000mA/g for cells assembled with the positive electrodes described in examples 1 to 3 and comparative example 1;
FIG. 5 is a graph showing the cycle performance at a current density of 200mA/g of batteries assembled with the positive electrodes described in examples 1-3 and comparative example 1;
fig. 6 is a graph of the cycle performance at a current density of 1000mA/g for a battery assembled with the positive electrodes described in examples 1 to 3 and comparative example 1.
Detailed Description
The technical solution of the present invention is further described with reference to the drawings and the embodiments.
Example 1
A preparation method of a cation-doped modified aqueous zinc ion battery manganese-based positive electrode comprises the following steps:
step 1, applying a voltage of 1.8V on an electrochemical workstation for 25min by using a two-electrode system, taking a platinum sheet as a counter electrode and a reference electrode, taking graphite paper as a working electrode and taking concentrated sulfuric acid as electrolyte;
step 3, preparing a manganese acetate solution with the concentration of 0.05mol/L, and taking the manganese acetate solution as a basic electrolyte;
step 4, adding 8.203g of sodium acetate serving as an additive into 500ml of the basic electrolyte in the step 3 to obtain a mixed acetate solution;
step 6, taking out the carbon-based conductive substrate treated in the step 5, washing the carbon-based conductive substrate for 3 times by using deionized water and absolute ethyl alcohol respectively, removing the residual salt solution on the surface, and then drying the substrate in an oven at 80 ℃ for 24 hours to obtain sodium ions (Na) + ) Manganese-based positive electrode (Na) of doped modified water-based zinc ion battery 0.017 MnO 2 )。
Example 2
A preparation method of a cation-doped modified aqueous zinc ion battery manganese-based positive electrode comprises the following steps:
step 1, applying a voltage of 1.8V on an electrochemical workstation for 25min by using a two-electrode system, taking a platinum sheet as a counter electrode and a reference electrode, taking graphite paper as a working electrode and taking concentrated sulfuric acid as electrolyte;
step 3, preparing a manganese acetate solution with the concentration of 0.05mol/L, and taking the manganese acetate solution as a basic electrolyte;
step 4, adding 8.809g of calcium acetate serving as an additive into 500ml of the basic electrolyte in the step 3 to obtain a mixed acetate solution;
step 6, taking out the carbon-based conductive substrate treated in the step 5, washing the carbon-based conductive substrate for 3 times by using deionized water and absolute ethyl alcohol respectively to remove the residual salt solution on the surface, and then drying the carbon-based conductive substrate in an oven at 80 ℃ for 24 hours to obtain calcium ions (Ca) 2+ ) Manganese-based positive electrode (Ca) of doping modified water-based zinc ion battery 0.036 MnO 2 )。
Example 3
The preparation method of the cation-doped modified aqueous zinc-ion battery manganese-based positive electrode according to claim 1, characterized by comprising the following steps: the method comprises the following steps:
step 1, applying a voltage of 1.8V on an electrochemical workstation for 25min by using a two-electrode system, taking a platinum sheet as a counter electrode and a reference electrode, taking graphite paper as a working electrode and taking concentrated sulfuric acid as electrolyte;
step 3, preparing a manganese acetate solution with the concentration of 0.05mol/L, and taking the manganese acetate solution as a basic electrolyte;
step 4, adding 9.814g of potassium acetate serving as an additive into 500ml of the basic electrolyte in the step 3 to obtain a mixed acetate solution;
and 6, taking out the carbon-based conductive substrate treated in the step 5, washing the carbon-based conductive substrate for 3 times by using deionized water and absolute ethyl alcohol respectively, removing the residual salt solution on the surface, and drying the carbon-based conductive substrate in an oven at 80 ℃ for 24 hours to obtain the carbon-based conductive substrateTo potassium ion (K) + ) Manganese-based positive electrode (K) of doping modified water-based zinc ion battery 0.039 MnO 2 )。
Comparative example 1
The preparation method of the manganese-based positive electrode of the cation-doped modified aqueous zinc-ion battery according to claim 1, characterized by comprising the following steps: the method comprises the following steps:
step 1, applying a voltage of 1.8V on an electrochemical workstation for 25min by using a two-electrode system, taking a platinum sheet as a counter electrode and a reference electrode, taking graphite paper as a working electrode and taking concentrated sulfuric acid as electrolyte;
step 3, preparing a manganese acetate solution with the concentration of 0.05mol/L, and taking the manganese acetate solution as a basic electrolyte;
step 4, using a three-electrode system, taking a platinum sheet as a counter electrode, taking a silver chloride electrode as a reference electrode, taking the carbon-based conductive substrate in the step 2 as a working electrode, taking the basic electrolyte in the step 3 as an experimental electrolyte, applying a voltage of 1.2V on an electrochemical workstation by adopting a constant-point method, and continuing for 20min;
and 5, taking out the carbon-based conductive substrate treated in the step 4, washing the carbon-based conductive substrate for 3 times by using deionized water and absolute ethyl alcohol respectively, removing residual salt solution on the surface, and drying the carbon-based conductive substrate in an oven at 80 ℃ for 24 hours to obtain an unmodified manganese-based positive electrode (MnO) of the water-based zinc ion battery 2 )。
The application of the positive electrodes obtained in examples 1 to 3 and comparative example 1 to an aqueous zinc ion battery respectively comprises the following steps:
(1) Preparation of positive plate
The positive electrodes obtained in examples 1 to 3 and comparative example 1 were cut into a circular piece having a diameter of 14 mm. The wafer is used as a positive electrode plate.
(2) Preparation of the negative electrode
Cutting a zinc foil with the thickness of 0.1mm into a wafer with the diameter of 15mm, ultrasonically cleaning the wafer by acetone, ethanol and deionized water to remove residual pollutants on the surface, ultrasonically cleaning the wafer by sulfuric acid aqueous solution with the concentration of 0.1mol/L, deionized water and ethanol to remove a surface oxide layer, and drying to obtain the negative pole piece.
(3) Preparation of the electrolyte
Dissolving zinc sulfate and manganese sulfate in deionized water to obtain electrolyte; the concentration of zinc sulfate in the electrolyte is 2mol/L, and the concentration of manganese sulfate is 0.1mol/L.
(4) Preparation of the Battery
And putting the positive pole piece, the diaphragm, the negative pole piece, the gasket and the spring piece into a motor shell in sequence, adding 0.2mL of electrolyte, and finally packaging to obtain the aqueous zinc ion battery. The diaphragm is a glass fiber diaphragm.
The positive electrodes prepared in example 1, example 2, example 3 and comparative example 1 and the assembled batteries were subjected to structural characterization and electrochemical performance test as follows:
XRD patterns of the manganese-based positive electrodes of the aqueous zinc ion batteries with modified sodium ions, calcium ions and potassium ions and without modified sodium ions, calcium ions and potassium ions obtained in the examples 1 to 3 and the comparative example 1 are shown in figure 1; as can be seen, the four different positive electrodes have quite similar diffraction patterns, which indicates that the four different positive electrodes have the same crystal structure; meanwhile, four distinct diffraction peaks correspond to standard carbon-based conductive substrates (PDF # 41-1487) and layered manganese dioxide (PDF # 18-0802), respectively.
SEM images of the carbon-based conductive substrates obtained in examples 1 to 3 and comparative example 1 are shown in fig. 2, and the surfaces have more sheet structures, which can provide abundant active sites for in-situ loading of manganese-based active materials.
The SEM images of the sodium, calcium and potassium ion doped modified and unmodified aqueous zinc ion battery manganese-based positive electrodes obtained in the examples 1-3 and the comparative example 1 are shown in FIG. 3; as can be seen from the figure, the microcosmic surface morphologies of the four different anodes are all nanosheet arrays constructed by nanosheets; the comparative example 1 and the examples 1 to 2 have very similar characteristics in terms of micro-morphology, but have larger differences in structural size, which is expressed by the rule that the larger the cation doping amount is, the larger the structural size is. In order to characterize the cation doping amount and investigate the specific ratio thereof to manganese, the element content (ICP-OES) analysis was performed on the positive electrodes obtained in examples 1 to 3, and the results are shown in table 1.
| Example 1: | Na 0.017 MnO 2 | example 2: | Ca 0.036 MnO 2 | example 3: | K 0.039 MnO 2 |
| Mn： | 98.37 | Mn： | 96.55 | Mn： | 96.28 |
| Na： | 1.63 | Ca： | 3.45 | K： | 3.72 |
| Na/Mn： | 0.017 | Ca/Mn： | 0.036 | K/Mn： | 0.039 |
TABLE 1 ICP-OES elemental analysis
Electrochemical performance tests were performed on the aqueous zinc ion batteries assembled with the manganese-based positive electrodes of the aqueous zinc ion batteries with modified sodium ions, calcium ions and potassium ions and without modified sodium ions, calcium ions and potassium ions obtained in examples 1 to 3 and comparative example 1, and the results are shown in fig. 4 to 6. Wherein, FIG. 4 is a rate performance graph of the batteries assembled by the positive electrodes described in examples 1-3 and comparative example 1 under the current density of 50-2000 mA/g; it can be seen that the specific capacity and rate capability of the manganese-based positive electrodes doped and modified by sodium, calcium and potassium ions obtained in examples 1 to 3 are improved obviously compared with the manganese-based positive electrode which is not modified in comparative example 1. Fig. 5 is a graph of cycle performance at a current density of 200mA/g of batteries assembled with the positive electrodes described in examples 1 to 3 and comparative example 1, wherein the specific discharge capacities of the first turns of comparative example 1 and examples 1 to 3 were 324.73, 241.00, 277.50, and 280.16mAh/g, respectively, and the capacity retention rates after 100 cycles were 60.18, 126.91, 119.11, and 111.21, respectively. Fig. 6 is a graph of cycle performance at a current density of 1000mA/g of batteries assembled with the positive electrodes described in examples 1 to 3 and comparative example 1, in which the capacity retention rates after 1000 cycles at the current density of comparative example 1 and examples 1 to 3 were 62.15, 81.84, 113.1, and 101.12%, respectively. Therefore, the crystal structure of the manganese-based anode material can be obviously stabilized by cation doping and the interlayer strut action, the capacity attenuation is inhibited, the circulation stability is improved, and the overall electrochemical performance of the manganese-based anode material is improved.
Finally, although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that various changes and modifications may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (9)
1. A cation-doped modified aqueous zinc ion battery manganese-based positive electrode is characterized in that: comprising a carbon-based conductive substrate having active sites and a cation-doped modified manganese-based active material M x MnO 2 Wherein M is a cation and X has a value of 0.01 to 0.05.
2. The manganese-based positive electrode of the cation-doped modified aqueous zinc-ion battery according to claim 1, wherein: the cation-doped modified manganese-based active material M x MnO 2 And the carbon-based conductive substrate is loaded on the surface of the carbon-based conductive substrate through electrochemical deposition.
3. The manganese-based positive electrode of the cation-doped modified aqueous zinc-ion battery according to claim 1, wherein: the cation comprises Na + 、Ca 2+ 、K + One or more of (a).
4. The manganese-based positive electrode of the cation-doped modified aqueous zinc-ion battery as claimed in claim 2, wherein: the cation-doped modified manganese-based active material M x MnO 2 Only on the same side of the carbon-based conductive substrate.
5. The manganese-based positive electrode of the cation-doped modified aqueous zinc-ion battery according to claim 2, wherein: the cation-doped modified manganese-based active material M loaded on the surface of the carbon-based conductive substrate x MnO 2 The microscopic morphology of the nano-film is a nano-film array constructed by nano-films.
6. The preparation method of the cation-doped modified aqueous zinc-ion battery manganese-based positive electrode according to claim 1, characterized by comprising the following steps: the method comprises the following steps:
step 1, applying a voltage of 1.5-2.5V on an electrochemical workstation for 20-30min by using a two-electrode system, taking a platinum sheet as a counter electrode and a reference electrode, taking graphite paper as a working electrode and taking concentrated sulfuric acid as electrolyte;
step 2, soaking the graphite paper treated in the step 1 in deionized water for 24 hours, then respectively washing the graphite paper with the deionized water and absolute ethyl alcohol for 3 times, and finally drying the graphite paper in an oven at 100 ℃ for 24 hours to obtain a carbon-based conductive substrate with active sites on the surface;
step 3, preparing a manganese acetate solution, and taking the manganese acetate solution as a basic electrolyte;
step 4, acetate containing cations is selected as an additive and added into the basic electrolyte in the step 3 to obtain a mixed acetate solution;
step 5, using a three-electrode system, using a platinum sheet as a counter electrode, using a silver chloride electrode as a reference electrode, using the carbon-based conductive substrate in the step 2 as a working electrode, using the mixed acetate solution in the step 4 as an electrolyte, applying a voltage of 1-1.5V on an electrochemical workstation by adopting a constant-point method, and continuing for 20-30min;
and 6, taking out the carbon-based conductive substrate treated in the step 5, washing the carbon-based conductive substrate for 3 times by using deionized water and absolute ethyl alcohol respectively, removing residual salt solution on the surface, and drying the carbon-based conductive substrate in an oven at 80 ℃ for 24 hours to obtain the cation-doped modified aqueous zinc ion battery manganese-based positive electrode.
7. The method for preparing the manganese-based positive electrode of the cation-doped modified aqueous zinc-ion battery according to claim 6, wherein the method comprises the following steps: the concentration of the manganese acetate solution in the step 3 is 0.05mol/L.
8. The method for preparing the manganese-based positive electrode of the cation-doped modified aqueous zinc-ion battery according to claim 6, wherein the method comprises the following steps: the acetate used as the additive in the step 4 is one or more of sodium acetate, calcium acetate and methyl acetate.
9. The use of the cation-doped modified aqueous zinc-ion battery manganese-based positive electrode of claim 1 as a positive electrode material in an aqueous zinc-ion battery.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211046914.2A CN115425164A (en) | 2022-08-30 | 2022-08-30 | Preparation method and application of cation-doped modified aqueous zinc ion battery manganese-based positive electrode |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211046914.2A CN115425164A (en) | 2022-08-30 | 2022-08-30 | Preparation method and application of cation-doped modified aqueous zinc ion battery manganese-based positive electrode |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN115425164A true CN115425164A (en) | 2022-12-02 |
Family
ID=84201020
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211046914.2A Pending CN115425164A (en) | 2022-08-30 | 2022-08-30 | Preparation method and application of cation-doped modified aqueous zinc ion battery manganese-based positive electrode |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115425164A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116759562A (en) * | 2023-08-16 | 2023-09-15 | 中石油深圳新能源研究院有限公司 | Double-cation doped positive electrode material and preparation method and application thereof |
-
2022
- 2022-08-30 CN CN202211046914.2A patent/CN115425164A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116759562A (en) * | 2023-08-16 | 2023-09-15 | 中石油深圳新能源研究院有限公司 | Double-cation doped positive electrode material and preparation method and application thereof |
| CN116759562B (en) * | 2023-08-16 | 2024-01-05 | 中石油深圳新能源研究院有限公司 | Double-cation doped positive electrode material and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108448168B (en) | Electrolyte for water-based zinc ion secondary battery and preparation method and application thereof | |
| CN106229498B (en) | Cathode material suitable for water-based metal ion battery and preparation method thereof | |
| CN106571461A (en) | Chargeable-dischargeable Zn-MnO2 battery with long service life and applications thereof | |
| CN110350184B (en) | Preparation method of high-capacity NiMoO4 energy storage material for battery positive electrode material | |
| CN108461732A (en) | A kind of flexibility sodium metal battery negative material and preparation method thereof | |
| CN112928343B (en) | Water system copper ion battery suitable for large-scale energy storage application | |
| CN113270577B (en) | Aqueous zinc ion battery and positive electrode material | |
| CN113161631A (en) | Additive-containing aqueous zinc ion battery electrolyte, preparation method thereof and battery | |
| CN111640921A (en) | Preparation method of vanadium compound electrode material and application of vanadium compound electrode material in water-based zinc ion battery | |
| CN103094627A (en) | Battery | |
| CN108123141A (en) | A kind of three-dimensional porous foams grapheme material and its application | |
| CN115548263A (en) | Sodium nitrate-containing sodium ion battery negative electrode piece and preparation method and application thereof | |
| CN115425164A (en) | Preparation method and application of cation-doped modified aqueous zinc ion battery manganese-based positive electrode | |
| CN101399120A (en) | Novel hybrid supercapacitor | |
| CN105428704B (en) | A kind of modified oxidized reduced form solid electrolyte and its preparation method and application | |
| CN115101831B (en) | Long-life water-based fluoride ion battery based on salt-coated electrolyte and preparation method thereof | |
| CN114094096B (en) | Method for forming protective polymer film on surface of sodium titanium phosphate negative electrode material, product and application thereof | |
| CN115995351A (en) | Preparation method of transition metal nickel doped manganese dioxide electrode material | |
| CN114335447A (en) | Surface treatment method for improving zinc negative polarity performance and application | |
| CN115188945A (en) | Coated positive electrode material and preparation method and application thereof | |
| CN115172639A (en) | Self-supporting potassium ion pre-embedded manganese-based positive electrode and preparation method and application thereof | |
| Thiet et al. | Reverse voltage pulse deposition of a porous polyaniline/Mn–Co sulfide composite cathode material for modified Zn-ion hybrid supercapacitors | |
| CN105552374B (en) | A kind of high power type lithium ion cell carbon negative pole material and preparation method thereof | |
| CN115566132B (en) | Silver-bismuth dual-function electrode and preparation method and application thereof | |
| CN114520302B (en) | Aqueous metal battery and modified anode thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |