CN109148877A - Rechargeable zinc-manganese battery and preparation method thereof - Google Patents
Rechargeable zinc-manganese battery and preparation method thereof Download PDFInfo
- Publication number
- CN109148877A CN109148877A CN201810853221.1A CN201810853221A CN109148877A CN 109148877 A CN109148877 A CN 109148877A CN 201810853221 A CN201810853221 A CN 201810853221A CN 109148877 A CN109148877 A CN 109148877A
- Authority
- CN
- China
- Prior art keywords
- zinc
- mno
- battery
- manganese
- linear alpha
- 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.)
- Withdrawn
Links
Classifications
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G45/00—Compounds of manganese
- C01G45/02—Oxides; Hydroxides
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
-
- 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 chargeable zinc-manganese battery and a preparation method thereof, wherein the positive electrode adopts linear alpha-MnO 2 The material replaces the traditional amorphous manganese dioxide material, and the invention adopts linear alpha-MnO 2 The material has a uniform structure, large tunnels and vacancies in the material increase the contact between active substances and electrodes, reduce the internal resistance of the battery and improve the diffusion performance of protons, and the larger length-diameter ratio can ensure that the preferred orientation degree of the material is higher, thereby improving the rate capability of the battery; stable structure, difficult collapse, high activity maintenance, slow attenuation speed and more contribution to the cycle performance of the battery. Linear alpha-MnO of the present invention 2 The material preparation method has simple and feasible synthesis process, good experimental reproducibility, cheap and easily obtained raw materials, and the prepared linear alpha-MnO 2 The material has a homogeneous structure and the structure,large length-diameter ratio, stable structure, difficult collapse and slow attenuation speed.
Description
Technical Field
The invention belongs to the technical field of secondary batteries, and particularly relates to a rechargeable zinc-manganese battery based on a water system electrolyte.
Background
Along with the rapid development of the world economy, the requirements of various countries on energy sources are increasingly increased. The development of new energy and the development of new energy materials which are friendly to the environment are the works advocated by governments of all countries. The development of rechargeable secondary batteries is becoming a new favorite of new energy technologies. At present, lithium ion batteries play an important role in daily life of people and are widely applied to various portable devices, but the lithium ion batteries have high production cost and certain potential safety hazards. Therefore, researchers are actively seeking a more safe and reliable secondary battery.
The zinc ion battery has high safety and low cost, and is expected to replace a lithium ion battery to realize large-scale application. Manganese element is abundant in earth crust, manganese dioxide is low in price, environment-friendly and has various crystal forms and structures, and the manganese dioxide is used as the anode material of the early alkaline zinc-manganese dioxide battery, so that great convenience is brought to the life of people. The utilization rate and electrochemical performance of the electrode material in the battery greatly affect the overall performance of the battery, and therefore, the development and research on the performance of the manganese dioxide electrode material have been the focus of attention. Such as V added into manganese dioxide of the positive electrode 2 O 5 、NiO、Co 2 O 3 The compounds reduce the overpotential of oxygen on the surface, hope to convert the overcharged electric energy into oxygen to avoid further oxidation of the anode, thereby improving the cycle performance of the battery, and for example, the invention patent application with the publication number of CN1337359A improves the activity of the electrolytic manganese dioxide by adding effective impurity removing agent and active agent. MnO 2 Energy storage of (2) depends on insertion and extraction of ions, hence MnO 2 The crystal structure of (A) plays a crucial role in improving the electrochemical performance, mnO 2 Different morphologies lead to different specific surface areas, pore size distributions and surface-to-volume ratios, which in turn lead to different specific capacitances. Most of the positive active materials in the existing zinc-manganese batteries are manganese dioxide with an amorphous structure, which is not beneficial to the performance of the batteries. In addition, in the process of heavy current discharge, the potential of the manganese dioxide material of the positive electrode is rapidly reduced, the polarization phenomenon is serious, and the cycle stability and the rate capability of the battery are greatly influenced.
Disclosure of Invention
In order to solve the above problems, the present invention provides a rechargeable zinc-manganese battery and a preparation method thereof, wherein the positive electrode adopts linear alpha-MnO 2 The material replaces the traditional amorphous manganese dioxide material, and the invention adopts linear alpha-MnO 2 The material has a uniform structure, large tunnels and vacancies in the material increase the contact between active substances and electrodes, show higher electrochemical activity, reduce the internal resistance of the battery, improve the diffusion performance of protons, and the larger length-diameter ratio can ensure that the preferred orientation degree of the material is higher, thereby improving the rate capability of the battery; the structure is stable, the collapse is not easy to occur, the activity can be maintained at a high level in a water-based electrolyte, the battery capacity fading speed is low, and the cycle performance of the battery is more favorably realized. Linear alpha-MnO of the present invention 2 The material preparation method has simple and feasible synthesis process, good experimental reproducibility, cheap and easily obtained raw materials, and the prepared linear alpha-MnO 2 The material has a uniform structure, a larger length-diameter ratio, a stable structure, difficulty in collapse and low attenuation speed.
The specific technical scheme of the invention is as follows:
a rechargeable zinc-manganese battery, the battery includes positive pole, negative pole, diaphragm and electrolyte, characterized by that: the active material of the positive electrode adopts linear alpha-MnO 2 A material. Linear alpha-MnO 2 The material has a uniform structure, increases the contact between an active substance and electrodes, reduces the internal resistance of the battery, improves the diffusion performance of protons, and has higher length-diameter ratio to ensure that the preferred orientation degree of the material is higher, thereby improving the rate capability of the battery; alpha-MnO 2 Compared with MnO 2 Other crystal forms have the characteristics of stable structure, difficult collapse and no reduction of activity, so that the battery capacity attenuation speed is low, and the cycle performance of the battery is more favorably realized.
Preferably, the positive electrode active material is linear alpha-MnO 2 With linear beta-MnO 2 Linear gamma-MnO 2 Linear delta-MnO 2 Linear lambda-MnO 2 Any mixture of more than four. The mixing of different crystal materials can improve the stability of the electrode material structure, slow the capacity attenuation and improve the cyclic charge and discharge capacity of the battery.
Preferably, the linear alpha-MnO is 2 The length dimension of the material is 0.5-3 μm.
Preferably, the linear alpha-MnO 2 The diameter of the material is 50-100 nm. The larger length-diameter ratio can enable the preferred orientation degree of the material to be higher, so that the rate capability of the battery is improved.
Preferably, the electrolyte is added with a mixed solution of zinc sulfate and manganese sulfate (pH = 7). The concentration of hydrogen ions in the solution is low, so that the problem of serious self-discharge of a zinc cathode can be avoided, the phenomenon of hydrogen evolution of the cathode can be avoided, and the battery is prevented from generating gas expansion and danger. Linear alpha-MnO 2 The material can maintain high-level activity in the neutral electrolyte of the invention, improve the diffusion performance of protons and improve the rate capability of the battery; and the structure is stable, the collapse is not easy to occur, the attenuation speed is low, and the cycle performance of the battery is more favorably realized.
Preferably, the concentrations of zinc sulfate and manganese sulfate are 0.5-2 mol/L respectively.
Preferably, a certain amount of wetting agent is also added into the electrolyte.
Preferably, the wetting agent is selected from a mixture of dimethyl sulfoxide, carboxylic acid soap and polyoxyethylene fatty alcohol ether.
Preferably, the dosage of the wetting agent accounts for 0.05-0.2% of the mass fraction of the electrolyte.
Preferably, the diaphragm is made of glass fiber paper with a strong water absorption effect and a porous channel structure. The glass fiber paper has a thickness of 0.6 to 1mm and a diameter of 1.5 to 3cm, preferably a thickness of 0.8mm and a diameter of 2cm.
Preferably, the positive electrode current collector is an aluminum foil or a stainless steel foil.
Preferably, the positive electrode conductive agent is one or more of superconducting carbon black, acetylene black, graphite powder and carbon nanotubes.
Preferably, the positive electrode binder is Polytetrafluoroethylene (PTFE).
Preferably, the amount of the positive electrode conductive agent added is 10% by mass of the positive electrode active material.
Preferably, the amount of the positive electrode binder added is 5 to 8% by mass of the active material.
Preferably, the active material of the negative electrode is a polished bright zinc plate or a zinc alloy, and the active material of the negative electrode can also be zinc powder.
Preferably, when the negative active material is zinc powder, the mass ratio of the zinc powder to the conductive agent to the binder is 8.
Preferably, the negative electrode uses a stainless steel foil or a zinc plate as a current collector.
Preferably, the negative electrode conductive agent may be one or more of activated carbon, acetylene black, superconducting carbon black, or carbon nanotubes.
Preferably, the negative electrode binder is one or more of Styrene Butadiene Rubber (SBR) or polyvinylidene fluoride (PVDF).
The invention further provides linear alpha-MnO 2 A method of preparing a material, the method comprising the steps of:
weighing potassium permanganate and hydrated manganese sulfate in a certain proportion, dissolving in deionized water, and stirring until the potassium permanganate and the hydrated manganese sulfate are completely dissolved;
transferring the mixture into a hydrothermal kettle, transferring the mixture into a baking oven, raising the temperature to 120-180 ℃ at the rate of 5-10 ℃/min, and keeping the temperature for 4-12 h;
naturally cooling to room temperature, washing the obtained material for several times and drying;
calcining for 1-4 h at high temperature in air atmosphere, wherein the calcining temperature is controlled at 400-600 ℃, and the heating rate is controlled at 5-8 ℃/min.
Preferably, the molar ratio of potassium permanganate to hydrated manganese sulfate is 1:1.
The preparation method of the invention synthesizes linear alpha-MnO 2 The process is simple and feasible, the experimental reproducibility is good, and the used raw materials are cheap and easy to obtain. And the linear alpha-MnO obtained 2 The material has uniform appearance, can increase the contact between active substances and electrodes and reduce the internal resistance of the battery, and the larger length-diameter ratio can ensure that the preferred orientation degree of the material is higher, thereby improving the rate capability of the battery; the linear alpha-MnO obtained 2 Stable structure, uneasy collapse, no reduction of activity, slow attenuation speed and more advantages in cycle performance.
The invention further provides a preparation method of the rechargeable zinc-manganese battery, which comprises the following steps:
preparing a positive electrode: will aliveLinear MnO of 2 Grinding the material for 30-60 min, adding a binder and a conductive agent in proportion, continuing grinding for 30min, adding a solvent, and uniformly grinding to obtain slurry with slight fluidity; coating the slurry on a stainless steel foil, drying and punching into round pieces with uniform size for later use;
preparing a negative electrode: polishing and brightening a high-purity zinc sheet by using 200-mesh sand paper, then ultrasonically washing the high-purity zinc sheet for 15min by using absolute ethyl alcohol, then washing the high-purity zinc sheet by using a dilute hydrochloric acid solution, finally washing the high-purity zinc sheet by using deionized water, and drying the high-purity zinc sheet at a low temperature;
a diaphragm: adopting glass fiber paper as a diaphragm;
electrolyte solution: adding a mixed solution of zinc sulfate and manganese sulfate, and adding a certain amount of wetting agent;
and assembling and packaging the battery.
Preferably, the positive electrode conductive agent is one or more of superconducting carbon black, acetylene black, graphite powder and carbon nanotubes.
Preferably, the positive electrode binder is Polytetrafluoroethylene (PTFE).
Preferably, the positive electrode solvent is NMP (N-methylpyrrolidone), and the amount is 3 to 5ml.
Preferably, the concentrations of zinc sulfate and manganese sulfate are 0.5-2 mol/L respectively.
Preferably, the wetting agent is selected from a mixture of dimethyl sulfoxide, carboxylic acid soap and polyoxyethylene fatty alcohol ether.
Preferably, the amount of the wetting agent is 0.05-0.2% of the mass fraction of the electrolyte.
Compared with the prior art, the invention has the following beneficial effects:
1. the invention prepares alpha-MnO 2 The method has simple and feasible synthesis process, good experimental reproducibility, cheap and easily obtained raw materials, and the obtained linear alpha-MnO 2 The material has uniform appearance and larger length-diameter ratio, so that the preferred orientation degree of the material is higher, and the material has stable structure and is not easy to collapse.
2. The prior art generally considers alpha-MnO 2 The linear alpha-MnO prepared by the method of the invention has low activity as the battery anode material 2 Has uniformityThe appearance, large tunnels and vacancies in the material increase the contact between the active substance and the electrodes, can increase the contact between the active substance and the electrodes, reduce the internal resistance of the battery, and the larger length-diameter ratio can ensure that the preferred orientation degree of the material is higher, thereby improving the rate capability of the battery; the linear alpha-MnO obtained 2 The structure is stable, collapse is not easy to occur, the activity can be maintained at a higher level in a water-based electrolyte, the attenuation speed is low, and the cycle performance of the battery is greatly improved.
3. The invention relates to a zinc ion battery, wherein the electrolyte is an aqueous electrolyte. The zinc has low price and higher mass energy density, and can be comparable to the lithium ion battery in performance; the aqueous electrolyte has an advantage in price and is more environmentally friendly.
4. The electrolyte used by the invention is ZnSO 4 And MnSO 4 The solution was mixed (pH = 7). In which ZnSO 4 And MnSO 4 The solution is neutral generally, the concentration of hydrogen ions in the solution is low, the problem of serious self-discharge of a zinc cathode can be avoided, the phenomenon of hydrogen evolution of the cathode can be avoided, the battery is prevented from generating gas expansion and danger, and the safety performance is high. alpha-MnO linear with positive electrode 2 The materials are matched, so that the system has excellent electron mobility, the rate performance of the battery is improved, the space structure of the anode material cannot collapse under the condition of high-rate charging, the cycle performance of the battery is improved, and the service life of the battery is prolonged.
Drawings
FIG. 1 is a view of linear alpha-MnO prepared 2 SEM image of (a);
FIG. 2 shows the cell at 0.3mA/cm 2 The resulting capacity-cycle curve at current density.
Detailed Description
In order to make the objects, technical solutions and advantageous technical effects of the present invention clearer, the present invention is further described in detail with reference to the following embodiments. It should be understood that the embodiments described in this specification are only for explaining the present invention and are not to be limited thereto, and the specific parameter settings and the like of the embodiments can be selected according to the circumstances without substantially affecting the results.
Example 1
The positive electrode active material was prepared as follows: weighing potassium permanganate and hydrated manganese sulfate with the molar ratio of 1:1, dissolving in 50ml of deionized water, stirring until the potassium permanganate and the hydrated manganese sulfate are completely dissolved, transferring into a hydrothermal kettle, transferring into a drying oven, heating to 120-180 ℃ at the heating rate of 5-10 ℃/min, keeping for 4-12 h, naturally cooling to room temperature, washing the obtained material for a plurality of times, and drying. Calcining at high temperature for 1-4 h in air atmosphere, controlling the calcining temperature at 400-600 ℃ and the heating rate at 5-8 ℃/min. The method synthesizes alpha-MnO 2 The process is simple and feasible, the experimental reproducibility is good, and the used raw materials are cheap and easy to obtain. FIG. 1 shows the preparation of alpha-MnO 2 The shape of the material shows that the material is in a uniform linear shape, the length is between 0.5 and 3 mu m, the uniform structure is more beneficial to the exertion of the performance of the battery, and the cycle performance and the rate performance of the battery depend on the uniform structure of the material. Linear alpha-MnO 2 The material has uniform appearance and larger length-diameter ratio, so that the preferred orientation degree of the material is higher, and the rate capability of the battery is improved; the linear alpha-MnO obtained 2 Compared with other crystal forms of manganese dioxide materials, the manganese dioxide material has stable structure, slow decay rate and more advantages in cycle performance.
The preparation process of the positive pole piece is as follows: grinding the prepared active linear manganese dioxide for 30-60 min, adding a binder and a conductive agent in proportion, continuously grinding for 30min, adding a certain amount of solvent, and uniformly grinding to obtain slurry with slight fluidity. Coating the slurry on a stainless steel foil, drying and punching into round pieces with uniform size for later use.
Preparing a negative electrode: polishing and brightening the high-purity zinc sheet by using 200-mesh sand paper, then ultrasonically washing the high-purity zinc sheet for 15min by using absolute ethyl alcohol, then washing the high-purity zinc sheet by using a dilute hydrochloric acid solution, finally washing the high-purity zinc sheet by using deionized water, and blow-drying the high-purity zinc sheet at a low temperature.
A diaphragm: glass fiber paper with the thickness of 0.8mm and the diameter of 2cm is used as the diaphragm.
Electrolyte solution: adding a mixed solution of 1mol/L zinc sulfate and 1mol/L manganese sulfate, and adding a certain amount of wetting agent. The ZnSO4 and MnSO4 solution is generally neutral, the concentration of hydrogen ions in the solution is low, the problem of serious self-discharge of a zinc cathode can be avoided, the phenomenon of hydrogen evolution of the cathode can be avoided, and the occurrence of gas expansion and danger of a battery can be avoided.
And assembling the battery.
And (5) carrying out an electrical property test on the obtained battery finished product.
Example 2
Preparing a positive electrode active material: 2.0g of manganese sulfate (MnSO) 4 ·H 2 O) is dissolved in 15ml of deionized water, and 12.5g of potassium permanganate is dissolved in 20ml of water; slowly dripping a manganese sulfate aqueous solution into a potassium permanganate aqueous solution by using an acid burette (about 30 min), magnetically stirring for 1h to obtain amorphous manganese dioxide, washing with deionized water and alcohol for several times, and drying for later use.
The preparation process of the positive pole piece is as follows: grinding the obtained amorphous manganese dioxide for 30-60 min, adding a binder and a conductive agent in proportion, continuing grinding for 30min, adding a certain amount of solvent, and grinding uniformly to obtain slurry with slight fluidity. Coating the slurry on a stainless steel foil, drying and punching into round sheets with uniform size for later use.
Preparing a negative electrode: polishing and brightening the high-purity zinc sheet by using 200-mesh sand paper, then ultrasonically washing the high-purity zinc sheet for 15min by using absolute ethyl alcohol, then washing the high-purity zinc sheet by using a dilute hydrochloric acid solution, finally washing the high-purity zinc sheet by using deionized water, and blow-drying the high-purity zinc sheet at a low temperature.
A diaphragm: glass fiber paper with the thickness of 0.8mm and the diameter of 2cm is used as the diaphragm.
Electrolyte solution: the electrolyte consists of an aqueous solution containing zinc chloride, ammonium chloride and a nonionic surfactant, wherein the content of the aqueous solution is 45% of zinc chloride, 10% of ammonium chloride and 0.5% of the nonionic surfactant.
And (6) assembling the battery.
And (5) carrying out an electrical property test on the obtained battery finished product.
Comparing the test results of example 1 and example 2, as shown in fig. 2, it can be seen from fig. 2 that the discharged gram capacity of amorphous manganese dioxide is significantly lower than that of morphologically uniform linear manganese dioxide, and the battery capacity is more easily attenuated due to poor crystallinity of amorphous manganese dioxide, and collapse of amorphous manganese dioxide structure caused by insertion and extraction of zinc ions in its crystal lattice. Linear alpha-MnO of the present invention 2 The material has uniform appearance, can increase the contact between active substances and electrodes and reduce the internal resistance of the battery, and the larger length-diameter ratio can ensure that the preferred orientation degree of the material is higher, thereby improving the rate capability of the battery; the linear alpha-MnO obtained 2 Stable structure, uneasy collapse, no reduction of activity in non-aqueous solution, slow attenuation speed, and better cycle performance.
Although the preferred embodiments of the present invention have been described in detail, the present invention is not limited to the above embodiments, and various changes can be made without departing from the spirit of the present invention within the knowledge of those skilled in the art.
Claims (10)
1. A rechargeable Zn-Mn battery is composed of positive electrode, negative electrode, diaphragm and electrolyte, and features that the active material of positive electrode is linear alpha-MnO 2 A material.
2. The zinc-manganese cell of claim 1, wherein the positive active material is linear alpha-MnO 2 With linear beta-MnO 2 Linear gamma-MnO 2 Linear delta-MnO 2 Linear lambda-MnO 2 Any one or more of the four.
3. The zinc-manganese cell of claim 1 or 2, wherein the linear alpha-MnO is 2 The length dimension of the material is 0.5-3 μm.
4. Zinc-manganese cell according to claim 1 or 2, characterized in that the linear alpha is-MnO 2 The diameter of the material is 50-100 nm.
5. The zinc-manganese cell of claim 1, wherein the linear alpha-MnO is 2 The preparation method comprises the following steps:
weighing potassium permanganate and hydrated manganese sulfate in a certain proportion, dissolving in deionized water, and stirring until the potassium permanganate and the hydrated manganese sulfate are completely dissolved;
transferring the mixture into a hydrothermal kettle, transferring the mixture into a drying oven, controlling the heating rate to be 5-10 ℃/min, heating the mixture to 120-180 ℃, and keeping the temperature for 4-12 h;
naturally cooling to room temperature, washing the obtained material for several times and drying;
calcining at high temperature for 1-4 h in air atmosphere, controlling the calcining temperature at 400-600 ℃ and the heating rate at 5-8 ℃/min.
6. The zinc-manganese battery of claim 1 or 2, wherein the electrolyte is added with a mixed solution of zinc sulfate and manganese sulfate.
7. The zinc-manganese battery of claim 5, characterized in that the concentrations of zinc sulfate and manganese sulfate are 0.5-2 mol/L, respectively.
8. The zinc-manganese cell of claim 1 or 2, wherein the active material of the negative electrode is polished zinc plate, zinc alloy or zinc powder.
9. A method of making a zinc-manganese battery, the method comprising the steps of:
preparing a positive electrode: grinding active linear manganese dioxide for 30-60 min, adding a binder and a conductive agent in proportion, continuously grinding for a certain time, adding a solvent, and uniformly grinding to obtain slurry with slight fluidity; coating the slurry on a stainless steel foil, drying and punching into round pieces with uniform size for later use;
preparing a negative electrode: polishing and brightening a high-purity zinc sheet by using 200-mesh sand paper, then ultrasonically washing the high-purity zinc sheet for 15min by using absolute ethyl alcohol, then washing the high-purity zinc sheet by using a dilute hydrochloric acid solution, finally washing the high-purity zinc sheet by using deionized water, and drying the high-purity zinc sheet at a low temperature;
a diaphragm: adopting glass fiber paper as a diaphragm;
electrolyte solution: adding a mixed solution of zinc sulfate and manganese sulfate, and adding a certain amount of wetting agent;
and assembling and packaging the battery.
10. Linear alpha-MnO 2 The preparation method is characterized by comprising the following steps:
weighing potassium permanganate and hydrated manganese sulfate in a certain proportion, dissolving in deionized water, and stirring until the potassium permanganate and the hydrated manganese sulfate are completely dissolved;
transferring the mixture into a hydrothermal kettle, transferring the mixture into a baking oven, raising the temperature to 120-180 ℃ at the rate of 5-10 ℃/min, and keeping the temperature for 4-12 h;
naturally cooling to room temperature, washing the obtained material for several times and drying;
calcining at high temperature for 1-4 h in air atmosphere, controlling the calcining temperature at 400-600 ℃ and the heating rate at 5-8 ℃/min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810853221.1A CN109148877A (en) | 2018-07-30 | 2018-07-30 | Rechargeable zinc-manganese battery and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810853221.1A CN109148877A (en) | 2018-07-30 | 2018-07-30 | Rechargeable zinc-manganese battery and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109148877A true CN109148877A (en) | 2019-01-04 |
Family
ID=64799200
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810853221.1A Withdrawn CN109148877A (en) | 2018-07-30 | 2018-07-30 | Rechargeable zinc-manganese battery and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109148877A (en) |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109786712A (en) * | 2019-01-25 | 2019-05-21 | 天津理工大学 | A kind of nickel, bismuth modified manganese dioxide positive electrode and its preparation method and application |
| CN110085800A (en) * | 2019-04-24 | 2019-08-02 | 浙江浙能技术研究院有限公司 | Structure and preparation method of high-utilization-rate manganese oxide electrode of neutral zinc-manganese battery |
| CN110265649A (en) * | 2019-06-28 | 2019-09-20 | 大连海事大学 | A kind of preparation method of the chargeable water system Zinc ion battery positive electrode of manganese dioxide of metal oxide cladding |
| CN110880621A (en) * | 2019-01-31 | 2020-03-13 | 天津大学 | High voltage rechargeable zinc-manganese battery |
| CN111082086A (en) * | 2019-12-24 | 2020-04-28 | 中银（宁波）电池有限公司 | High-voltage zinc-manganese battery and preparation method thereof |
| CN112174213A (en) * | 2020-09-18 | 2021-01-05 | 浙江浙能中科储能科技有限公司 | Preparation of dispersed spherical manganese oxide material and application of dispersed spherical manganese oxide material in zinc battery |
| CN112349909A (en) * | 2020-11-06 | 2021-02-09 | 常州大学 | Zinc-ion battery positive electrode composite material and preparation method and application thereof |
| CN112467233A (en) * | 2020-12-01 | 2021-03-09 | 中山市华舜科技有限责任公司 | High-performance aqueous electrolyte for chargeable and dischargeable zinc-manganese battery |
| CN112624198A (en) * | 2020-12-09 | 2021-04-09 | 浙江浙能中科储能科技有限公司 | Method for synthesizing high-activity layered zinc ion secondary battery anode material by one-step method at room temperature |
| CN113113675A (en) * | 2021-04-16 | 2021-07-13 | 郑州大学 | Quasi-solid flexible Zn-MnO2Battery and preparation method |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5658693A (en) * | 1991-06-17 | 1997-08-19 | Technology Finance Corporation (Proprietary) Limited | Manganese dioxide-based material |
| CN1758468A (en) * | 2005-08-26 | 2006-04-12 | 南开大学 | Manganese dioxide nanotube/nanowire electrode material, preparation method and application thereof |
| CN101114707A (en) * | 2006-07-25 | 2008-01-30 | 松下电器产业株式会社 | Alkaline battery |
| CN102030371A (en) * | 2010-12-21 | 2011-04-27 | 北京化工大学 | Preparation method of manganese dioxide nanowire with high aspect ratio |
| CN102910680A (en) * | 2012-10-22 | 2013-02-06 | 天津大学 | Preparation method for preparing manganese dioxides in various crystal forms |
| CN103771524A (en) * | 2014-02-25 | 2014-05-07 | 重庆大学 | MnO2 nanometer composite material and preparation method thereof |
| CN104628039A (en) * | 2015-02-06 | 2015-05-20 | 南京工业大学 | Controllable preparation method of alpha-manganese dioxide nanowire |
| CN106745285A (en) * | 2017-03-01 | 2017-05-31 | 哈尔滨工业大学 | A kind of α MnO2The preparation method of nano wire |
| CN106957068A (en) * | 2016-01-08 | 2017-07-18 | 新材料与产业技术北京研究院 | A kind of α-MnO2The preparation method of nano wire |
| CN107004860A (en) * | 2014-10-13 | 2017-08-01 | 纽约城市大学研究基金会 | Mixing material negative electrode for secondary alkaline batteries group |
-
2018
- 2018-07-30 CN CN201810853221.1A patent/CN109148877A/en not_active Withdrawn
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5658693A (en) * | 1991-06-17 | 1997-08-19 | Technology Finance Corporation (Proprietary) Limited | Manganese dioxide-based material |
| CN1758468A (en) * | 2005-08-26 | 2006-04-12 | 南开大学 | Manganese dioxide nanotube/nanowire electrode material, preparation method and application thereof |
| CN101114707A (en) * | 2006-07-25 | 2008-01-30 | 松下电器产业株式会社 | Alkaline battery |
| CN102030371A (en) * | 2010-12-21 | 2011-04-27 | 北京化工大学 | Preparation method of manganese dioxide nanowire with high aspect ratio |
| CN102910680A (en) * | 2012-10-22 | 2013-02-06 | 天津大学 | Preparation method for preparing manganese dioxides in various crystal forms |
| CN103771524A (en) * | 2014-02-25 | 2014-05-07 | 重庆大学 | MnO2 nanometer composite material and preparation method thereof |
| CN107004860A (en) * | 2014-10-13 | 2017-08-01 | 纽约城市大学研究基金会 | Mixing material negative electrode for secondary alkaline batteries group |
| CN104628039A (en) * | 2015-02-06 | 2015-05-20 | 南京工业大学 | Controllable preparation method of alpha-manganese dioxide nanowire |
| CN106957068A (en) * | 2016-01-08 | 2017-07-18 | 新材料与产业技术北京研究院 | A kind of α-MnO2The preparation method of nano wire |
| CN106745285A (en) * | 2017-03-01 | 2017-05-31 | 哈尔滨工业大学 | A kind of α MnO2The preparation method of nano wire |
Non-Patent Citations (1)
| Title |
|---|
| 李绍宇: "锌二次电池正极材料的制备与改性研究", 《中国硕士学位论文全文数据库工程科技II辑》 * |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109786712A (en) * | 2019-01-25 | 2019-05-21 | 天津理工大学 | A kind of nickel, bismuth modified manganese dioxide positive electrode and its preparation method and application |
| CN110880621A (en) * | 2019-01-31 | 2020-03-13 | 天津大学 | High voltage rechargeable zinc-manganese battery |
| CN110085800A (en) * | 2019-04-24 | 2019-08-02 | 浙江浙能技术研究院有限公司 | Structure and preparation method of high-utilization-rate manganese oxide electrode of neutral zinc-manganese battery |
| CN110265649A (en) * | 2019-06-28 | 2019-09-20 | 大连海事大学 | A kind of preparation method of the chargeable water system Zinc ion battery positive electrode of manganese dioxide of metal oxide cladding |
| CN111082086B (en) * | 2019-12-24 | 2021-04-30 | 中银（宁波）电池有限公司 | High-voltage zinc-manganese battery and preparation method thereof |
| CN111082086A (en) * | 2019-12-24 | 2020-04-28 | 中银（宁波）电池有限公司 | High-voltage zinc-manganese battery and preparation method thereof |
| CN112174213A (en) * | 2020-09-18 | 2021-01-05 | 浙江浙能中科储能科技有限公司 | Preparation of dispersed spherical manganese oxide material and application of dispersed spherical manganese oxide material in zinc battery |
| CN112349909A (en) * | 2020-11-06 | 2021-02-09 | 常州大学 | Zinc-ion battery positive electrode composite material and preparation method and application thereof |
| CN112349909B (en) * | 2020-11-06 | 2022-03-29 | 常州大学 | Zinc-ion battery positive electrode composite material and preparation method and application thereof |
| CN112467233A (en) * | 2020-12-01 | 2021-03-09 | 中山市华舜科技有限责任公司 | High-performance aqueous electrolyte for chargeable and dischargeable zinc-manganese battery |
| CN112467233B (en) * | 2020-12-01 | 2022-03-25 | 中山市华舜科技有限责任公司 | High-performance aqueous electrolyte for chargeable and dischargeable zinc-manganese battery |
| CN112624198A (en) * | 2020-12-09 | 2021-04-09 | 浙江浙能中科储能科技有限公司 | Method for synthesizing high-activity layered zinc ion secondary battery anode material by one-step method at room temperature |
| CN113113675A (en) * | 2021-04-16 | 2021-07-13 | 郑州大学 | Quasi-solid flexible Zn-MnO2Battery and preparation method |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109148877A (en) | Rechargeable zinc-manganese battery and preparation method thereof | |
| CN105958131B (en) | Rechargeable aqueous zinc ion battery with long cycle life and high energy density | |
| CN104617271B (en) | Stannic selenide/graphene oxide negative pole composite material for sodium ion battery and preparation method thereof | |
| CN113410443B (en) | Preparation method and application of high-stability copper intercalation manganese dioxide electrode material | |
| CN113422048B (en) | Preparation method and application of anode material of water-based zinc ion battery | |
| CN113104863A (en) | Inert transition metal element doped iron-based Prussian blue sodium ion battery positive electrode material | |
| CN114725366B (en) | Preparation method of niobium-titanium oxide negative electrode material for lithium ion battery | |
| CN113270577A (en) | Aqueous zinc ion battery and positive electrode material | |
| CN109560284A (en) | A kind of high performance doping type lithium manganate positive electrode and preparation method thereof | |
| CN109360961B (en) | Hollow composite microsphere for lithium-sulfur battery positive electrode material and preparation method thereof | |
| CN111268727A (en) | Calcium vanadate composite material and preparation method and application thereof | |
| CN110649263A (en) | Nickel-ion battery lithium vanadium phosphate positive electrode material, sol-gel preparation method and application | |
| CN108649217B (en) | Preparation method of high-voltage lithium battery anode material bat mixed lithium nickel manganese oxide | |
| CN113782710A (en) | High-performance chargeable and dischargeable aqueous zinc-iodine battery and preparation method thereof | |
| CN111082162B (en) | Aqueous sodium ion battery | |
| CN102544511A (en) | Lithium ion battery positive electrode lithium ferrous phosphate material wrapped with strontium cerium doped cobaltate (SCC) and carbon, and preparation method for lithium ion battery positive electrode lithium ferrous phosphate material | |
| CN102820466B (en) | A kind of lithium ion battery cathode material and its preparation method based on hydroxy cobalt oxide | |
| CN114843459B (en) | Antimony pentasulfide-based material and preparation method and application thereof | |
| CN111146007A (en) | Zinc ion hybrid supercapacitor and preparation method thereof | |
| CN114835091A (en) | High-performance zinc ion battery positive electrode material bismuth selenide nanosheet and preparation method thereof | |
| CN109742341B (en) | Method for preparing Fe-doped two-dimensional porous NiO electrode material with high lithium storage performance under assistance of glucose | |
| CN104716327B (en) | Lithium-air battery cathode electrode material and application | |
| CN112490458A (en) | Preparation method of zinc salt mixed electrolyte and manganese positive electrode material for zinc-manganese battery | |
| CN112053858A (en) | Method for preparing zinc ion hybrid capacitor by using acid activated carbon electrode material | |
| CN111453767A (en) | Porous SnO2Micron sheet, preparation method thereof and application of micron sheet to positive electrode of lead-carbon battery |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20200519 Address after: Room g0232, headquarters building, Changsha Zhongdian Software Park, No. 39, Jianshan Road, high tech Development Zone, Changsha City, Hunan Province Applicant after: Thornton New Energy Technology (Changsha) Co.,Ltd. Address before: 411100 Hunan province Xiangtan City Jiuhua Demonstration Zone No. 78 West Benz Applicant before: SOUNDON NEW ENERGY TECHNOLOGY Co.,Ltd. |
|
| TA01 | Transfer of patent application right | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WW01 | Invention patent application withdrawn after publication |
Application publication date: 20190104 |
|
| WW01 | Invention patent application withdrawn after publication |