CN115172639A - Self-supporting potassium ion pre-embedded manganese-based positive electrode and preparation method and application thereof - Google Patents

Self-supporting potassium ion pre-embedded manganese-based positive electrode and preparation method and application thereof Download PDF

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CN115172639A
CN115172639A CN202210585267.6A CN202210585267A CN115172639A CN 115172639 A CN115172639 A CN 115172639A CN 202210585267 A CN202210585267 A CN 202210585267A CN 115172639 A CN115172639 A CN 115172639A
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positive electrode
manganese
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lgp
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冯婷婷
谭杰
吴孟强
张庶
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Yangtze River Delta Research Institute of UESTC Huzhou
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Yangtze River Delta Research Institute of UESTC Huzhou
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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
    • 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
    • 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
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • 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

Abstract

The invention provides a self-supporting potassium ion pre-embedded manganese-based positive electrode, a preparation method and an application thereof, and belongs to the field of electrochemical energy storage. The positive electrode comprises a three-dimensional layered carbon-based conductive substrate (LGP) and manganese dioxide (K) pre-intercalated with potassium ions x MnO 2 ). The manganese dioxide (K) pre-embedded with potassium ions x MnO 2 ) The nano flower and nano sheet array structure formed by polymerization of nanoclusters uniformly grows between three-dimensional layered carbon-based conductive layers and on the surface of the three-dimensional layered carbon-based conductive layers. Compared with the prior art, the three-dimensional layered carbon-based conductive substrate provided by the invention has rich interlayer spacing and surface area, not only provides rich active sites for the growth of manganese dioxide, but also increases the conductivity of the manganese dioxide, and can realize the sufficiency of electrolyte and active substances. At the same timeThrough the pre-embedding of potassium ions, the crystal structure of manganese dioxide is stabilized, so that the cycle stability of the manganese dioxide is greatly increased.

Description

Self-supporting potassium ion pre-embedded manganese-based positive electrode and preparation method and application thereof
Technical Field
The invention relates to the technical field of electrochemical energy storage, in particular to a self-supporting potassium ion pre-embedded manganese-based positive electrode and a preparation method and application thereof.
Background
Clean, renewable, safe and controllable new energy sources such as solar energy, wind energy, tidal energy and the like are intermittent energy sources and do not have continuity, and continuous supply of the intermittent energy sources is required to be realized through energy storage equipment. Most of the existing energy storage methods are limited by the carnot cycle, so that the energy conversion efficiency is too low. But the electrochemical energy storage is not limited by Carnot cycle, and the energy conversion efficiency is extremely high.
Among the secondary batteries commercialized at present, the lithium ion secondary battery has the most excellent performance. The characteristics of high energy density and long cycle life seem to be suitable for large-scale energy storage in energy storage performance, but the used organic electrolyte causes problems of combustion and explosion. Meanwhile, the price of the lithium metal is too high, so that the lithium ion secondary battery is not suitable for large-scale energy storage in terms of safety and cost performance. Based on the characteristics of safety, environmental protection and low cost, the water system multivalent ion (Mg) 2 + 、Ca 2+ 、Al 3+ 、Zn 2+ ) Batteries are becoming more popular. Among them, the zinc ion battery has the most excellent performance.
The electrochemical performance of the existing zinc ion battery is mainly limited by the anode material. Common positive electrode materials include manganese-based oxides, vanadium-based oxides, prussian blue, polyanionic compounds, and the like. Among them, manganese-based oxides having a tunnel structure, a layered structure and a spinel structure are very common as a positive electrode material. However, in the process of charging and discharging, the manganese-based oxide has the problems of manganese element loss, unstable structure and poor conductivity, thereby greatly influencing the electrochemical performance.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a self-supporting potassium ion pre-embedded manganese-based positive electrode and a preparation method and application thereof. The self-supporting potassium ion pre-embedded manganese-based anode provided by the invention is applied to a water system zinc ion battery, has higher specific capacity and longer cycle life, and has excellent rate capability and conductivity.
The technical purpose of the invention is realized by the following technical scheme:
a self-supporting potassium ion pre-embedded manganese-based positive electrode, a preparing method thereof and applications of the self-supporting potassium ion pre-embedded manganese-based positive electrode comprise manganese dioxide (K) pre-embedded with potassium ions x MnO 2 ) Also included is a three-dimensional layered carbon-based conductive substrate (LGP), the potassium ion pre-intercalated manganese dioxide (K) x MnO 2 ) Is tightly loaded between the surface and the layer of the three-dimensional layered carbon-based conductive substrate.
The manganese dioxide (K) pre-embedded with potassium ions is loaded between the surface and the layers of the three-dimensional layered carbon-based conductive substrate x MnO 2 ) Is a nanoflower and nanosheet array structure formed by polymerization of nanoclusters.
Step 1, preparing sulfuric acid aqueous solutions with different concentrations by using concentrated sulfuric acid with the content of 95% -98%;
step 2, taking a platinum sheet as a counter electrode, taking square graphite paper with the side length of 30-36 mm as a working electrode, taking the sulfuric acid aqueous solution in the step 1 as an electrolyte, and depositing for a period of time at a certain voltage by adopting a constant potential electrolysis method;
step 3, soaking the graphite paper treated in the step 2 in deionized water for a period of time, and replacing HSO in the graphite paper - 4 Changing the deionized water midway until the pH value of the deionized water solution is 7, and drying in an oven at 60-90 ℃ to obtain a three-dimensional layered carbon-based conductive substrate (LGP);
step 4, preparing potassium permanganate solutions with different concentrations, and adjusting the pH value of the potassium permanganate solution;
step 5, placing the three-dimensional layered carbon-based conductive substrate (LGP) obtained in the step 3 into a certain amount of the potassium permanganate solution obtained in the step 4; transferring a solution containing a three-dimensional layered conductive substrate (LGP) into a stainless steel reaction kettle, and heating for reaction for a period of time;
step 6, taking out the three-dimensional layered carbon-based conductive substrate (LGP),soaking in deionized water and absolute ethyl alcohol respectively for a period of time until the solution is colorless; then drying the mixture for 10 to 24 hours in an oven at the temperature of between 60 and 90 ℃ to obtain the self-supporting potassium ion pre-embedded manganese-based anode (LGP @ K) x MnO 2 )。
The concentration of the sulfuric acid aqueous solution in the step 1 is 10-18.4 mol/L.
In the step 2, the voltage is 1-2V, and the deposition time is 10-50 min.
The concentration of the potassium permanganate solution in the step 4 is 0.01mol/L.
In the step 5, the heating temperature is 140-180 ℃, and the heating time is 0.5-1.5 h.
And sequentially placing the positive pole piece, the diaphragm, the negative pole piece, the gasket and the spring piece into a motor shell, adding 150 mu L of electrolyte, and finally packaging to obtain the water-based zinc ion battery.
Compared with the prior art, the invention has the following beneficial effects:
1. the preparation method is simple, and the self-supporting potassium ion pre-embedding manganese-based positive electrode (LGP @ K) can be realized only by carrying out simple electrochemical deposition and hydrothermal reaction x MnO 2 ) Preparing; the loading capacity of the active substances of the electrode plates can be adjusted by adjusting the time and the temperature of the hydrothermal reaction. The microcosmic appearance of the active material is a nano and nano sheet array formed by aggregation of nanoclusters.
2. The invention realizes the preparation of the three-dimensional layered carbon-based conductive substrate (LGP) by an electrochemical deposition method, and has abundant layered structures compared with the traditional stainless steel foil and stainless steel mesh, thereby having more active sites and being capable of better contacting with electrolyte.
3. The method takes the three-dimensional layered carbon-based conductive substrate (LGP) prepared by electrochemical deposition as a carbon source, realizes in-situ growth load of the anode active material through hydrothermal reaction, and does not need a conductive agent and a binder.
4. The raw materials needed by the invention are rich and the price is low; the raw materials required for preparing the anode are graphite paper, potassium permanganate and sulfuric acid.
5. The method realizes the in-situ embedding of potassium ions through hydrothermal reaction, and can regulate and control the embedding amount of the potassium ions by regulating the pH value of the reaction environment; meanwhile, the crystal structure of manganese dioxide is not obviously changed by the embedding of potassium ions; on the contrary, the intercalation of potassium ions expands the lattice spacing of manganese dioxide, which is beneficial to the reversible deintercalation of zinc ions during charge and discharge, and the interlayer pillar can reduce the structural change caused by the reversible deintercalation of zinc ions during charge and discharge.
Drawings
FIG. 1 shows the self-supporting potassium pre-intercalation manganese-based positive electrode LGP @ K of examples 1 and 2 0.23 MnO 2 And LGP @ K 0.15 MnO 2 X-ray diffraction (XRD) pattern of (a);
FIG. 2 shows the self-supporting potassium pre-intercalated manganese-based positive electrode LGP @ K of examples 1 and 2 0.23 MnO 2 (a-d) and LGP @ K 0.15 MnO 2 (e-h) Scanning Electron Microscope (SEM) images of cross-sections at different magnifications;
FIG. 3 is the self-supporting potassium pre-intercalated manganese-based positive electrode LGP @ K of example 1 0.23 MnO 2 The element distribution map of (a);
FIG. 4 is a graph of rate capability at current densities of 50-2000 mA/g for batteries assembled with the positive electrodes described in examples 1 and 2;
FIG. 5 is a graph showing the charge and discharge curves at a current density of 50mA/g of the batteries assembled by the positive electrodes described in example 1, example 2 and comparative example 1;
fig. 6 is a graph of the cycling performance at a current density of 1000mA/g for cells assembled from the positive electrodes described in example 1, example 2, and comparative example 1.
Detailed Description
The technical solution of the present invention is further explained with reference to the drawings and the embodiments.
Meanwhile, the test methods referred to in the following examples and comparative examples are conventional methods unless otherwise specified; the drugs, materials and experimental equipment involved are commercially available without specific reference.
Example 1
Step 1, preparing a sulfuric acid aqueous solution with the concentration of 18mol/L by using concentrated sulfuric acid with the content of 95-98%.
And 2, taking a platinum sheet as a counter electrode, taking square graphite paper with the side length of 35mm as a working electrode, taking the 18mol/L sulfuric acid aqueous solution in the step 1 as electrolyte, and applying a voltage of 1.75V for deposition for 30min by using a constant potential electrolysis method by using a Chenghua electrochemical workstation.
Step 3, soaking the graphite paper treated in the step 2 in ionized water for a period of time to replace HSO in the graphite paper - 4 And changing the deionized water in the midway until the pH value of the deionized water solution is 7. And then dried in an oven at 80 ℃ to obtain a three-dimensional layered carbon-based conductive substrate (LGP).
And 4, preparing a potassium permanganate aqueous solution with the concentration of 0.01mol/L.
And 5, placing the three-dimensional layered carbon-based conductive substrate (LGP) obtained in the step 3 into 50ml of the potassium permanganate aqueous solution obtained in the step 4. The solution containing three-dimensional layered carbon-based conductive substrate (LGP) was transferred into a stainless steel reaction kettle with 100ml teflon lining, and placed in an oven to react at 150 ℃ for 1h until it was cooled to room temperature.
And 6, taking out the conductive substrate, and soaking in deionized water and absolute ethyl alcohol respectively for a period of time until the solution is colorless. Then drying the mixture for 12 hours in an oven at 80 ℃ to obtain the self-supporting potassium ion pre-embedded manganese-based positive electrode (LGP @ K) 0.23 MnO 2 )。
Sequentially placing the positive pole piece, the diaphragm, the negative pole piece, the gasket and the spring piece into the motor shell, adding 150 mu L of electrolyte, and finally packaging to obtain the water-system zinc-ion battery
The application of the positive electrode to the preparation of the water-based zinc ion battery comprises the following steps:
(1) Preparation of positive plate
Pre-embedding self-supporting potassium ions into a manganese-based positive electrode (LGP @ K) 0.23 MnO 2 ) Cut into a circular piece with a diameter of 14 mm. The wafer is used as a positive electrode piece.
(2) Preparation of the negative electrode
Cutting a zinc foil with the thickness of 80 mu m 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 oxidation layer, and drying the wafer 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 150 mu L of electrolyte, and finally packaging to obtain the water-based zinc ion battery. The diaphragm is a glass fiber diaphragm.
Example 2
Step 1, preparing sulfuric acid aqueous solution with the concentration of 18mol/L by using concentrated sulfuric acid with the content of 95-98%.
And 2, taking a platinum sheet as a counter electrode, square graphite paper with the side length of 35mm as a working electrode, taking the 18mol/L sulfuric acid aqueous solution in the step 1 as electrolyte, and applying a voltage of 1.75V for deposition for 30min by using a chenghua electrochemical workstation and adopting a constant potential electrolysis method.
Step 3, soaking the graphite paper treated in the step 2 in ionized water for a period of time to replace HSO in the graphite paper - 4 And changing the deionized water in the midway until the pH value of the aqueous solution is 7. And then dried in an oven at 80 ℃ to obtain a three-dimensional layered carbon-based conductive substrate (LGP).
And 4, preparing 200ml of 0.01mol/L potassium permanganate aqueous solution, and adding 8.2 mu L of 95-98% concentrated sulfuric acid.
And 5, placing the three-dimensional layered carbon-based conductive substrate (LGP) obtained in the step 3 into 50ml of the acidic potassium permanganate aqueous solution obtained in the step 4. The solution containing three-dimensional layered carbon-based conductive substrate (LGP) was transferred into a stainless steel reaction kettle with 100ml teflon lining, and placed in an oven to react at 150 ℃ for 1h until it was cooled to room temperature.
Step 6, taking out the guideAnd the electric substrate is respectively soaked in deionized water and absolute ethyl alcohol for a period of time until the solution is colorless. Then drying in an oven at 80 ℃ for 12h to obtain the self-supporting potassium ion pre-embedded manganese-based positive electrode (LGP @ K) 0.15 MnO 2 )。
The procedure for applying the positive electrode obtained above to the preparation of an aqueous zinc ion battery was as described in example 1.
Comparative example 1
Step 1, taking a square carbon cloth with the side length of 35mm, placing the square carbon cloth in a mixed solution of concentrated sulfuric acid and concentrated nitric acid with the volume ratio of 3 to 1, heating for 3 hours at 80 ℃, then respectively washing for three times with deionized water and absolute ethyl alcohol, and then placing the square carbon cloth in an oven to heat and dry for 12 hours at 80 ℃.
And 2, preparing a potassium permanganate aqueous solution with the concentration of 0.01mol/L.
And 3, placing the carbon cloth treated in the step 1 in 50ml of the potassium permanganate aqueous solution obtained in the step 3. The solution containing the carbon cloth was transferred to a stainless steel reaction kettle with a 100ml teflon liner and placed in an oven to react at 150 ℃ for 1h until it was cooled to room temperature.
And 6, taking out the carbon cloth after the reaction, and soaking the carbon cloth in deionized water and absolute ethyl alcohol respectively for a period of time until the solution is colorless. Then drying the carbon cloth in an oven at 80 ℃ for 12h to obtain the anode (CC @ K) taking the carbon cloth as the conductive substrate x MnO 2 )。
The procedure for applying the positive electrode obtained above to the preparation of an aqueous zinc ion battery was as described in example 1.
The positive electrodes prepared in example 1, example 2 and comparative example 1 and the assembled batteries were subjected to structural characterization and electrochemical performance test as follows:
the XRD pattern of the self-supported potassium ion pre-intercalated manganese-based positive electrode described in examples 1 and 2 is shown in fig. 1, and it can be seen that the (110) plane angle of the positive electrode prepared in example 1 is reduced as compared to the positive electrode prepared in example 2, and thus it can be seen that the positive electrode prepared in example 1 has a larger interlayer distance as compared to the positive electrode prepared in example 2; as can be seen from fig. 2, the active materials of the positive electrodes prepared in examples 1 and 2 are all in a structure of nanoflower and nanosheet arrays formed by polymerization of nanoclusters, but the size of the nanosheet in example 2 is larger than that in example 1; fig. 3 is an SEM EDS mapping of the positive electrode prepared in example 1, and it can be seen that example 1 successfully achieves pre-intercalation of potassium ions. The ratios of the positive electrode elements of examples 1 and 2 measured by EDS are shown in table 1.
Table 1EDX elemental analysis
Examples Sample (I) O Mn K K/Mn
1 K 0.23 MnO 2 56.76 35.19 8.05 0.23
2 K 0.15 MnO 2 65.07 30.39 4.55 0.15
FIG. 4 is a graph of the rate capability at 50-2000 mA/g for the examples 1 and 2, showing that the positive electrodes of example 2 have higher specific capacities at different current densities; fig. 5 is a charging and discharging platform diagram of the 10 th cycle of charging and discharging the positive electrode in the embodiment 1, the embodiment 2 and the comparative example 1 under the current density of 50mA/g, and it can be known that, compared with the comparative example 1, the overpotential of the positive electrode in the charging and discharging processes in the embodiment 1 and the embodiment 2 is obviously reduced, and the discharge capacity is greatly improved, wherein the overpotential of the positive electrode in the embodiment 2 is lower, and the discharge capacity is higher; fig. 6 is a cycle performance diagram of the positive electrode in example 1, example 2 and comparative example 1 at 1000mA/g, and it can be seen from the diagram that the first specific discharge capacities of example 1 and example 2 at the current density are 112.2mAh/g and 132.5mAh/g, the specific discharge capacities after 1000 cycles are 85.8mAh/g and 110.4mAh/g, the capacity retention rates are 76.5% and 83.3%, the first specific discharge capacity of comparative example 1 is 100mAh/g, the specific discharge capacity after 1000 cycles is 39.4mAh/g, and the capacity retention rate is 39.4%.
According to the material characterization and electrochemical performance test results, the electrochemical performance of the material can be effectively improved by pre-embedding the three-dimensional layered conductive substrate and a proper amount of potassium ions.
Finally, the above embodiments are only for illustrating the technical solutions of the present invention and not for limiting, 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 modifications or equivalent substitutions may be made to the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention, and all of them should be covered in the claims of the present invention.

Claims (8)

1. A self-supporting potassium ion pre-embedded manganese-based positive electrode is characterized in that: manganese dioxide (K) including pre-intercalated potassium ions x MnO 2 ) Wherein x is 0.1-0.24, and further comprises a three-dimensional layered carbon-based conductive substrate (LGP), the manganese dioxide (K) pre-intercalated with potassium ions x MnO 2 ) Loaded on the surface of a three-dimensional laminar carbon-based conductive substrateBetween the layers.
2. The method for preparing the self-supporting potassium ion pre-embedded manganese-based positive electrode according to claim 1, wherein the method comprises the following steps: the manganese dioxide (K) pre-embedded with potassium ions is loaded between the surface and the layers of the three-dimensional layered carbon-based conductive substrate x MnO 2 ) Is a nanoflower and nanosheet array structure formed by polymerization of nanoclusters.
3. The method for preparing the self-supporting potassium ion pre-embedded manganese-based positive electrode according to claim 1, wherein the method comprises the following steps: self-supporting potassium ion pre-embedded manganese-based positive electrode (LGP @ K) x MnO 2 ) The preparation method comprises the following steps:
step 1, preparing sulfuric acid aqueous solutions with different concentrations by using concentrated sulfuric acid with the content of 95% -98%;
step 2, taking a platinum sheet as a counter electrode, taking square graphite paper with the side length of 30-36 mm as a working electrode, taking the sulfuric acid aqueous solution in the step 1 as an electrolyte, and adopting a constant potential electrolysis method to deposit for a period of time at a certain voltage;
step 3, soaking the graphite paper treated in the step 2 in deionized water for a period of time, and replacing the graphite paper
Figure FDA0003665701240000011
Changing the deionized water midway until the pH value of the deionized water solution is 7, and drying in an oven at 60-90 ℃ to obtain a three-dimensional laminar carbon-based conductive substrate (LGP);
step 4, preparing potassium permanganate solutions with different concentrations, and adjusting the pH value of the potassium permanganate solution;
step 5, placing the three-dimensional layered carbon-based conductive substrate (LGP) in the step 3 into a certain amount of the potassium permanganate solution in the step 4; transferring a solution containing a three-dimensional layered conductive substrate (LGP) into a stainless steel reaction kettle, and heating and reacting for a period of time;
step 6, taking out the three-dimensional layered carbon-based conductive substrate (LGP), soaking in deionized water and absolute ethyl alcohol respectively for a period of time,until the solution is colorless; then drying the mixture for 10 to 24 hours in an oven at the temperature of between 60 and 90 ℃ to obtain the self-supporting potassium ion pre-embedded manganese-based anode (LGP @ K) x MnO 2 )。
4. The method for preparing the self-supporting potassium ion pre-embedded manganese-based positive electrode according to claim 3, wherein the method comprises the following steps: the concentration of the sulfuric acid aqueous solution in the step 1 is 10-18.4 mol/L.
5. The method for preparing the self-supporting potassium ion pre-embedded manganese-based positive electrode according to claim 3, wherein the method comprises the following steps: in the step 2, the voltage is 1-2V, and the deposition time is 10-50 min.
6. The method for preparing the self-supporting potassium ion pre-embedded manganese-based positive electrode according to claim 3, wherein the method comprises the following steps: the concentration of the potassium permanganate solution in the step 4 is 0.01mol/L.
7. The method for preparing the self-supporting potassium ion pre-embedded manganese-based positive electrode according to claim 3, wherein the method comprises the following steps: in the step 5, the heating reaction temperature is 140-180 ℃, and the heating reaction time is 0.5-1.5 h.
8. The use of a self-supporting potassium pre-intercalated manganese-based positive electrode as claimed in claim 1 in a zinc ion battery, wherein: and sequentially putting the positive pole piece, the diaphragm, the negative pole piece, the gasket and the spring piece into the motor shell, adding 150 mu L of electrolyte, and finally packaging to obtain the water-based zinc ion battery.
CN202210585267.6A 2022-05-27 2022-05-27 Self-supporting potassium ion pre-embedded manganese-based positive electrode and preparation method and application thereof Pending CN115172639A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115893500A (en) * 2022-11-23 2023-04-04 中国地质大学（北京） Novel manganese-based K x MnO 2 Preparation method of/C potassium ion battery positive electrode material

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115893500A (en) * 2022-11-23 2023-04-04 中国地质大学（北京） Novel manganese-based K x MnO 2 Preparation method of/C potassium ion battery positive electrode material

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