CN115995351A - Preparation method of transition metal nickel doped manganese dioxide electrode material - Google Patents
Preparation method of transition metal nickel doped manganese dioxide electrode material Download PDFInfo
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- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 title claims abstract description 82
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 67
- 239000007772 electrode material Substances 0.000 title claims abstract description 50
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 33
- 229910052723 transition metal Inorganic materials 0.000 title claims abstract description 27
- 150000003624 transition metals Chemical class 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 43
- 239000004744 fabric Substances 0.000 claims abstract description 23
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 21
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000003792 electrolyte Substances 0.000 claims abstract description 16
- 239000008367 deionised water Substances 0.000 claims abstract description 15
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229940082328 manganese acetate tetrahydrate Drugs 0.000 claims abstract description 13
- CESXSDZNZGSWSP-UHFFFAOYSA-L manganese(2+);diacetate;tetrahydrate Chemical compound O.O.O.O.[Mn+2].CC([O-])=O.CC([O-])=O CESXSDZNZGSWSP-UHFFFAOYSA-L 0.000 claims abstract description 13
- 229940078487 nickel acetate tetrahydrate Drugs 0.000 claims abstract description 12
- OINIXPNQKAZCRL-UHFFFAOYSA-L nickel(2+);diacetate;tetrahydrate Chemical compound O.O.O.O.[Ni+2].CC([O-])=O.CC([O-])=O OINIXPNQKAZCRL-UHFFFAOYSA-L 0.000 claims abstract description 12
- 230000008021 deposition Effects 0.000 claims abstract description 10
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims abstract description 9
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 claims abstract description 9
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 9
- 238000001035 drying Methods 0.000 claims abstract description 8
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 7
- 238000003756 stirring Methods 0.000 claims abstract description 6
- 230000004913 activation Effects 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 10
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- 229910052956 cinnabar Inorganic materials 0.000 claims description 2
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 abstract description 20
- 239000000463 material Substances 0.000 abstract description 12
- 238000004146 energy storage Methods 0.000 abstract description 7
- 239000011230 binding agent Substances 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 20
- 239000003990 capacitor Substances 0.000 description 11
- 239000011701 zinc Substances 0.000 description 8
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 6
- 230000009286 beneficial effect Effects 0.000 description 6
- 238000000151 deposition Methods 0.000 description 6
- 150000002500 ions Chemical class 0.000 description 6
- 239000011572 manganese Substances 0.000 description 6
- 239000002135 nanosheet Substances 0.000 description 6
- 238000010586 diagram Methods 0.000 description 5
- 238000004070 electrodeposition Methods 0.000 description 5
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 4
- 238000009830 intercalation Methods 0.000 description 4
- 238000011068 loading method Methods 0.000 description 4
- 229910052748 manganese Inorganic materials 0.000 description 4
- 229910052725 zinc Inorganic materials 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 230000002687 intercalation Effects 0.000 description 3
- 229910001453 nickel ion Inorganic materials 0.000 description 3
- 239000007774 positive electrode material Substances 0.000 description 3
- 241000219312 Chenopodium Species 0.000 description 2
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000009831 deintercalation Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 229910001437 manganese ion Inorganic materials 0.000 description 2
- TYTHZVVGVFAQHF-UHFFFAOYSA-N manganese(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Mn+3].[Mn+3] TYTHZVVGVFAQHF-UHFFFAOYSA-N 0.000 description 2
- GEYXPJBPASPPLI-UHFFFAOYSA-N manganese(III) oxide Inorganic materials O=[Mn]O[Mn]=O GEYXPJBPASPPLI-UHFFFAOYSA-N 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000012876 topography Methods 0.000 description 2
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- GOPYZMJAIPBUGX-UHFFFAOYSA-N [O-2].[O-2].[Mn+4] Chemical group [O-2].[O-2].[Mn+4] GOPYZMJAIPBUGX-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000012983 electrochemical energy storage Methods 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000003306 harvesting Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 230000005764 inhibitory process Effects 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
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 239000002064 nanoplatelet Substances 0.000 description 1
- 239000002073 nanorod Substances 0.000 description 1
- 239000002070 nanowire Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229940078494 nickel acetate Drugs 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- -1 polytetrafluoroethylene Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 238000004506 ultrasonic cleaning Methods 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
- 238000005406 washing Methods 0.000 description 1
- 150000003751 zinc Chemical class 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
- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
- 229960001763 zinc sulfate Drugs 0.000 description 1
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- 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
- Y02E60/13—Energy storage using capacitors
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- Electric Double-Layer Capacitors Or The Like (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a preparation method of a transition metal nickel doped manganese dioxide electrode material, which comprises the following steps: disposing carbon in a nitric acid solution for hydrothermal activation; dissolving nickel acetate tetrahydrate, manganese acetate tetrahydrate and anhydrous sodium sulfate in deionized water, and magnetically stirring until the solution is uniform and transparent to obtain electrolyte; immersing carbon cloth into electrolyte, wherein the carbon cloth is used as a working electrode, a platinum sheet electrode and a saturated calomel electrode are respectively used as a counter electrode and a reference electrode, and performing constant current deposition by using a Chen-Hua electrochemical workstation; and drying after the deposition is finished to obtain the manganese dioxide electrode material. The invention provides a simple preparation method of a transition metal doped manganese dioxide electrode material, which saves the time for preparing the material, ensures that the electrode material has excellent performance under high load, overcomes the problems of complicated preparation process and using a binder, and has wide application prospect on flexible energy storage devices such as zinc ion hybrid supercapacitors, zinc ion batteries and the like when being deposited on carbon cloth.
Description
Technical Field
The invention relates to the field of electrode materials of zinc ion mixed super capacitors, in particular to a preparation method of a transition metal nickel doped manganese dioxide electrode material.
Background
In the last decade, as the environment has gradually deteriorated and the energy demand has increased, the research interest of electrochemical energy storage devices has been greatly stimulated. Currently, supercapacitors and secondary batteries are considered as two promising energy storage devices. Secondary batteries can provide high energy density, weak self-discharge, and high operating voltage, but have very limited power density and cycle life. In contrast, supercapacitors have advantages in terms of power output, rate capability, and cycle life, but are limited by lower energy densities. To solve these problems, the manufacture of hybrid supercapacitors with battery-type and capacitor-type electrodes, combined with the advantages of batteries and supercapacitors, is the most promising approach to increase the device energy density without affecting its power output and cycle life (Gong X, chen
﹊
J,Lee P S.Zinc on hybrid supercapacitors:progress and future perspective[J].Batteries&Supercaps,2021.)。
The zinc ion hybrid capacitor is used as an emerging energy storage device, is composed of battery type and capacitance type electrodes in zinc-based solution electrolyte, and is recognized as one of the most potential candidate devices of the energy storage system by virtue of the advantages of the zinc ion hybrid capacitor, and the zinc ion hybrid capacitor is combined with the excellent performance of each of a zinc ion battery and a super capacitor, and is rich in zinc resources, nontoxic and high in safety. Based on electrode materials and energy storage mechanismsMeanwhile, zinc ion hybrid capacitors can be classified into a conventional zinc ion hybrid capacitor and a pseudocapacitive anode (generally, transition metal oxide), a carbon-based anode, and an electrolyte containing zinc salt, which are composed of a battery type anode (metallic zinc) as an energy source and an electric double layer capacitor type (porous carbon, activated carbon, etc.) cathode as a power source. The energy storage mechanism of the two is obviously different, the former is deposition/stripping reaction of zinc ions on the anode, and the latter is intercalation/deintercalation reaction of zinc ions on the cathode. Compared with the traditional carbon-based zinc ion mixed capacitor, the device avoids using excessive and unstable zinc foil or zinc powder as an anode, and is beneficial to the specific capacity of the whole device. The main charge storage mechanism of the capacitor composed of the novel pseudocapacitance material// carbon material is Zn based on the cathode surface 2+ The intercalation/deintercalation process and ion adsorption/desorption on the activated carbon anode. During discharge, zn in electrolyte 2+ The ions migrate toward and further intercalate into the positive electrode material, while the negative ions adsorb onto the carbon anode. Zn deintercalated from cathode material during charging 2+ And the adsorbed anions are desorbed again into the electrolyte solution. Thus, development of Zn is more beneficial 2+ Embedded/extracted electrode material.
Currently, positive electrode materials of zinc ion hybrid supercapacitors are mainly manganese-based and vanadium-based oxides, wherein manganese-based oxides have many advantages, such as: the resources are rich, the cost is low, the environment is protected, and the method is widely used by people; multiple valence states (+2, +3 and +4), and various crystal structures, such as MnO and MnO 2 And Mn of 3 O 4 Etc.; the high theoretical capacity and wide voltage window become an ideal positive electrode material. However, manganese ions are easily dissolved in the electrolyte during the cycle, resulting in poor cycle stability. Therefore, the doping of the transition metal nickel is more beneficial to the intercalation and the migration of zinc ions, and meanwhile, more active sites are provided for the zinc ions, so that the electrochemical performance of the electrode material is improved. The carbon cloth has the advantages of good conductivity, stable chemical property, good mechanical strength and the like, and is an ideal flexible electrode material substrate. Therefore, the nickel-doped manganese-based oxide material with good electrochemical performance has better conductivity and mechanical flexibilityThe good carbon cloth is used as an electrode material to obtain the flexible electrode material with good electrochemical performance.
There are many reported manganese-based oxides, group Qu topics (Qu Q, zhang P, wang B, et al, electrochemical Performance of MnO) 2 Nanorods in Neutral Aqueous Electrolytes as a Cathode for Asymmetric Supercapacitors[J]Journal of Physical Chemistry C,2009,113 (31): 14020-14027.) the rod-shaped manganese dioxide is prepared at room temperature by a simple precipitation method, but when this material is applied to an energy storage device, it is necessary to apply it to a current collector using an additional binder, which increases the resistance of the electrode and affects the electrochemical stability. Kar group (Kar P, sardar S, ghosh S, et al Nano Surface Engineering of Mn) 2 O 3 for Potential Light-Harvesting Application[J]Journal of Materials Chemistry C,2015,3 (31) the use of transition metal nickel doped manganese sesquioxide in zinc ion batteries, the main reason for the improved battery performance is due to the inhibition of dissolution of the manganese sesquioxide cathode by the doping of nickel. Chen topic group (Chen Q, jin J, kou Z, et al Zn (2+))
Pre-Intercalation Stabilizes the Tunnel Structure of MnO 2 Nanowires and Enables Zinc-Ion Hybrid Supercapacitor of Battery-Level Energy Density[J]Small,2020,16 (14): 2000091. ) The zinc-doped manganese dioxide prepared by adopting a simple hydrothermal method has excellent performance when being applied to a zinc ion mixed capacitor, but the preparation process uses potassium permanganate and concentrated sulfuric acid with strong oxidability, has dangerousness and is not suitable for large-scale application.
Disclosure of Invention
The technical problems to be solved by the invention are as follows: a simple preparation method of a transition metal nickel doped manganese dioxide electrode material is provided to solve the problem of overlarge internal resistance caused by using a binder in the existing manganese dioxide electrode material.
In order to solve the problems, the invention provides a preparation method of a transition metal nickel doped manganese dioxide electrode material, which comprises the following steps:
step 1): disposing carbon in a nitric acid solution for hydrothermal activation;
step 2): dissolving nickel acetate tetrahydrate, manganese acetate tetrahydrate and anhydrous sodium sulfate in deionized water, and magnetically stirring until the solution is uniform and transparent to obtain electrolyte;
step 3): immersing the carbon cloth obtained in the step 1) into the electrolyte obtained in the step 2), wherein the carbon cloth is used as a working electrode, a platinum sheet electrode and a saturated calomel electrode are respectively used as a counter electrode and a reference electrode, and the cinnabar electrochemical workstation is used for constant current deposition; and drying after the deposition is finished to obtain the manganese dioxide electrode material.
Preferably, the mass concentration of the nitric acid solution in the step 1) is 10-20%.
Preferably, the molar ratio of the sum of the moles of nickel acetate tetrahydrate and manganese acetate tetrahydrate to anhydrous sodium carbonate in the step 1) is 1:1.
more preferably, the molar ratio of nickel acetate tetrahydrate to manganese acetate tetrahydrate is 13:12.
more preferably, the ratio of anhydrous sodium carbonate to deionized water is 1mmol:9mL.
Preferably, the constant current deposition in the step 3) has a current density of 520mA/cm 2 The time is 20-60 minutes.
Preferably, the drying in step 3) is carried out at a temperature of 90 ℃ for a period of 12 hours.
Compared with the prior art, the invention has the beneficial effects that:
1. according to the invention, activated carbon cloth with better hydrophilicity is used as a substrate, so that the electrode material with excellent performance and high load capacity is obtained while the material is uniformly deposited on the surface.
2. The invention adopts a constant current deposition method to obtain the transition metal nickel doped manganese dioxide nano-sheet electrode material on the flexible carbon cloth, and the material has good electrochemical performance.
3. The preparation method has the advantages of simple preparation process, short time consumption and low cost.
Drawings
FIG. 1 is an XRD pattern of an electrode material prepared in example 3;
FIG. 2 is a topography of the electrode materials prepared in example 3, example 4 and example 5;
FIG. 3 is a topography of the electrode materials prepared in example 3, example 6 and example 7;
fig. 4 to 6 are constant current charge-discharge patterns of the electrode materials prepared in the examples.
Detailed Description
In order to make the invention more comprehensible, preferred embodiments accompanied with figures are described in detail below.
Example 1
The commercial carbon cloth is acid activated, so that the hydrophobicity of the carbon cloth is improved, and the specific steps are as follows:
step 1): 10mL of concentrated nitric acid (68% by mass) was slowly added to 40mL of deionized water while stirring with a glass rod;
step 2): pouring the dilute nitric acid obtained in the step 1) into a polytetrafluoroethylene lining with the volume of 100mL, and putting a plurality of pieces of commercial carbon cloth (1X 2 cm) subjected to ultrasonic cleaning 2 ) Preserving heat at 140 ℃ for 2 hours, and then cooling to room temperature along with an oven;
step 3): and 3) carrying out cross washing on the activated carbon cloth prepared in the step 2) by using deionized water and absolute ethyl alcohol for 3 times, and drying the washed carbon in an oven at 60 ℃ overnight to obtain the activated carbon cloth.
Example 2
A preparation method of manganese dioxide electrode material comprises the following specific steps:
step 1): dissolving 10mmol of manganese acetate tetrahydrate and 10mmol of anhydrous sodium sulfate in 90mL of deionized water, and magnetically stirring until the solution is uniform and transparent;
step 2): transferring the solution in the step 1) into an electrolytic cell, taking activated carbon cloth as a working electrode, a platinum sheet electrode as a counter electrode and a saturated calomel electrode as a reference electrode, adopting a three-electrode system, and using a Chen Hua electrochemical workstation at 10mA/cm 2 Is deposited for 40 minutes at a constant current density;
step 3): and 3) cross-cleaning the sample obtained in the step 2) with deionized water and absolute ethyl alcohol for 3 times, and drying the sample in a 90 ℃ oven for 12 hours to obtain the manganese dioxide electrode material.
Example 3
The preparation method of the transition metal nickel doped manganese dioxide electrode material comprises the following specific steps:
step 1): 9.5mmol of manganese acetate tetrahydrate, 10mmol of anhydrous sodium sulfate and 0.5mmol of nickel acetate tetrahydrate are dissolved in 90mL of deionized water, and the solution is stirred magnetically until the solution is uniform and transparent;
step 2): transferring the solution in the step 1) into an electrolytic cell, taking activated carbon cloth as a working electrode, a platinum sheet electrode as a counter electrode and a saturated calomel electrode as a reference electrode, adopting a three-electrode system, and using a Chenopodium electrochemical workstation at 10mA/cm 2 Is deposited for 20 minutes at a constant current density;
step 3): and 3) cleaning the sample obtained in the step 2) with deionized water and absolute ethyl alcohol for 3 times, and drying the sample in a 90 ℃ oven for 12 hours to obtain the transition metal nickel doped manganese dioxide electrode material.
Example 4
The preparation method of the transition metal nickel doped manganese dioxide electrode material comprises the following specific steps:
step 1): 9mmol of manganese acetate tetrahydrate, 10mmol of anhydrous sodium sulfate and 1mmol of nickel acetate tetrahydrate are dissolved in 90mL of deionized water, and the solution is stirred magnetically until the solution is uniform and transparent;
step 2): transferring the solution in the step 1) into an electrolytic cell, taking activated carbon cloth as a working electrode, a platinum sheet electrode as a counter electrode and a saturated calomel electrode as a reference electrode, adopting a three-electrode system, and using a Chenopodium electrochemical workstation at 10mA/cm 2 Is deposited for 20 minutes at a constant current density;
step 3): consistent with step 3) in example 3.
Example 5
The preparation method of the transition metal nickel doped manganese dioxide electrode material comprises the following specific steps:
step 1): dissolving 8mmol of manganese acetate tetrahydrate, 10mmol of anhydrous sodium sulfate and 2mmol of nickel acetate tetrahydrate in 90mL of deionized water, and magnetically stirring until the solution is uniform and transparent;
step 2): the step 1) is carried outTransferring the solution into an electrolytic cell, taking activated carbon cloth as a working electrode, a platinum sheet electrode as a counter electrode and a saturated calomel electrode as a reference electrode, adopting a three-electrode system, and using a Chen Hua electrochemical workstation at 10mA/cm 2 Is deposited for 20 minutes at a constant current density;
step 3): consistent with step 3) in example 3.
Example 6
The preparation method of the transition metal nickel doped manganese dioxide electrode material comprises the following specific steps:
step 1): 9.5mmol of manganese acetate tetrahydrate, 10mmol of anhydrous sodium sulfate and 0.5mmol of nickel acetate tetrahydrate are dissolved in 90mL of deionized water, and the solution is stirred magnetically until the solution is uniform and transparent;
step 2): transferring the solution in the step 1) into an electrolytic cell, taking activated carbon cloth as a working electrode, a platinum sheet electrode as a counter electrode and a saturated calomel electrode as a reference electrode, adopting a three-electrode system, and using a Chen Hua electrochemical workstation at 10mA/cm 2 Is deposited for 40 minutes at a constant current density;
step 3): consistent with step 3) in example 3.
Example 7
The preparation method of the transition metal nickel doped manganese dioxide electrode material comprises the following specific steps:
step 1): 9.5mmol of manganese acetate tetrahydrate, 10mmol of anhydrous sodium sulfate and 0.5mmol of nickel acetate tetrahydrate are dissolved in 90mL of deionized water, and the solution is stirred magnetically until the solution is uniform and transparent;
step 2): transferring the solution in the step 1) into an electrolytic cell, taking activated carbon cloth as a working electrode, a platinum sheet electrode as a counter electrode and a saturated calomel electrode as a reference electrode, adopting a three-electrode system, and using a Chen Hua electrochemical workstation at 10mA/cm 2 Is deposited for 60 minutes at a constant current density;
step 3): consistent with step 3) in example 3.
The morphology of the materials prepared in example 3, example 4 and example 5 is shown in fig. 2, and it can be seen from fig. 2 that the morphology of the nickel-doped manganese dioxide prepared in example 3, example 4 and example 5 is nano-sheets, and the nano-sheets can be uniformly deposited, so that more nucleation sites are provided by the acidized carbon cloth. The structure of the nano-sheet is beneficial to the absorption/desorption of ions in the electrolyte and the transmission of electrons. By comparing (d) (example 3), (e) (example 4), (f) (example 5) in fig. 2, it can be seen that as the doping amount of nickel acetate increases, the nano-sheet size decreases, so that the stacking of electrode materials affects the diffusion of electrolyte ions, affecting the electrochemical performance. Fig. 2 is the product of examples 3, 4 and 5, and it can be seen that the loading increases with increasing electrodeposition time, resulting in a denser material surface and a reduced size of nanoplatelets. In example 3, more sparse pores can be obtained due to the short deposition time, but the performance is also more general due to the low mass of active material. In fig. 3, (e) and (f) are samples prepared in examples 6 and 7, respectively, the loading increases with the increase of the electrodeposition time, the surface of the material is more compact, the coating is not uniform any more, and the performance is reduced. In summary, the doping of nickel distorts the crystal lattice of manganese dioxide, and the porous structure formed by stacking the nano sheets with proper size is more beneficial to the rapid transmission of electrons and provides more channels for the diffusion of electrolyte ions, thereby improving the electrochemical performance.
As is apparent from the constant current charge-discharge diagram (GCD) of the transition metal nickel doped manganese dioxide electrode materials prepared in example 2 and example 6 shown in FIG. 4, it is apparent from the graph that the nickel doped manganese dioxide has better performance than manganese dioxide at the same current density of 2mA/cm 2 When the area specific capacitance of the nickel-doped manganese dioxide and the area specific capacitance of the manganese dioxide are 3601.86mF/cm respectively 2 And 3395.23mF/cm 2 The incorporation of transition metal nickel has been shown to increase the specific capacitance of the manganese dioxide electrode. The nickel ions replace manganese ions in a manganese dioxide structure to cause partial distortion of crystal lattices, so that defects in the material are increased, more active sites are provided for zinc ions, and the electron transmission rate in the charge and discharge process is accelerated, so that the electrochemical performance of the electrode material is greatly improved.
Transition metal Nickel obtained in example 3, example 4 and example 5The constant current charge-discharge diagram (GCD) of the doped manganese dioxide electrode material is shown in FIG. 5, and it is obvious from the diagram that the electrochemical performance of the electrode material reaches the best when the addition amount of nickel is 0.5 mmol. At a current density of 4mA/cm 2 The specific capacities of the electrode materials at the addition amount of nickel of 0.5mmol, 1mmol and 2mmol were 861.33mF/cm, respectively 2 、843.74mF/cm 2 And 644.10mF/cm 2 It is shown that doping the nickel ion concentration to a certain limit can enhance the specific capacitance, but exceeding this limit will decrease the specific capacitance because the nickel-based electrode requires a basic electrolyte of sodium hydroxide or potassium hydroxide solution as compared to the manganese dioxide electrode material, so that the pseudocapacitive reaction of excessive nickel ions in the mixed electrolyte of zinc sulfate and manganese sulfate is limited, affecting the electrochemical performance of the electrode material.
The constant current charge-discharge (GCD) diagrams of the transition metal nickel doped manganese dioxide electrode materials prepared in example 3, example 6 and example 7 are shown in fig. 6, and it is apparent from the diagrams that the electrochemical performance reaches the optimum at the electrodeposition time of 40 min. At a current density of 4mA/cm 2 The specific capacitance of the electrode material for electrodeposition time of 20-60min reaches 861.33mF/cm 2 、2834.67mF/cm 2 And 2190.58mF/cm 2 The nickel doped manganese dioxide loading is shown to be optimal, and when the loading is excessive, the zinc ion transmission channel and the attachment site are blocked, so that the electrochemical performance of the material is affected. Electrodeposition for 40 minutes is therefore optimal.
Claims (7)
1. The preparation method of the transition metal nickel doped manganese dioxide electrode material is characterized by comprising the following steps of:
step 1): disposing carbon in a nitric acid solution for hydrothermal activation;
step 2): dissolving nickel acetate tetrahydrate, manganese acetate tetrahydrate and anhydrous sodium sulfate in deionized water, and magnetically stirring until the solution is uniform and transparent to obtain electrolyte;
step 3): immersing the carbon cloth obtained in the step 1) into the electrolyte obtained in the step 2), wherein the carbon cloth is used as a working electrode, a platinum sheet electrode and a saturated calomel electrode are respectively used as a counter electrode and a reference electrode, and the cinnabar electrochemical workstation is used for constant current deposition; and drying after the deposition is finished to obtain the manganese dioxide electrode material.
2. The method for preparing a transition metal nickel doped manganese dioxide electrode material according to claim 1, wherein the mass concentration of the nitric acid solution in the step 1) is 10-20%.
3. The method for preparing the transition metal nickel doped manganese dioxide electrode material according to claim 1, wherein the molar ratio of the sum of the moles of nickel acetate tetrahydrate and manganese acetate tetrahydrate to anhydrous sodium carbonate in the step 1) is 1:1.
4. a method of preparing a transition metal nickel doped manganese dioxide electrode material according to claim 3, wherein the molar ratio of nickel acetate tetrahydrate to manganese acetate tetrahydrate is 13:12.
5. the method for preparing a transition metal nickel doped manganese dioxide electrode material according to claim 3, wherein the ratio of anhydrous sodium carbonate to deionized water is 1mmol:9mL.
6. The method for preparing a transition metal nickel doped manganese dioxide electrode material according to claim 1, wherein the constant current deposition in step 3) has a current density of 520mA/cm 2 The time is 20-60 minutes.
7. The method for preparing a transition metal nickel doped manganese dioxide electrode material according to claim 1, wherein the drying temperature in step 3) is 90 ℃ for 12 hours.
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