CN113410452A - Modified zinc cathode and preparation method and application thereof - Google Patents
Modified zinc cathode and preparation method and application thereof Download PDFInfo
- Publication number
- CN113410452A CN113410452A CN202110673551.4A CN202110673551A CN113410452A CN 113410452 A CN113410452 A CN 113410452A CN 202110673551 A CN202110673551 A CN 202110673551A CN 113410452 A CN113410452 A CN 113410452A
- Authority
- CN
- China
- Prior art keywords
- zinc
- cathode
- sheet
- modified
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
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
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their 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
- H01M12/00—Hybrid cells; Manufacture thereof
- H01M12/04—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type
- H01M12/06—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type with one metallic and one gaseous electrode
-
- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
-
- 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
- H01M2004/027—Negative 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 relates to the technical field of metal zinc sheet electrodes, and particularly provides a modified zinc cathode and a preparation method and application thereof, wherein the method comprises the following steps: s1) soaking the zinc sheet in the mercaptan solution for a certain time; s2) washing the zinc sheet soaked in the step S1) with absolute ethyl alcohol and water respectively, and drying to obtain the modified zinc cathode. According to the invention, through a simple liquid phase preparation method, a mercaptan molecule is self-assembled on the surface of a metal zinc sheet to form a film, so that the corrosion of a zinc cathode and the generation of zinc dendrites are inhibited. The production process is extremely simple, and only commercial metal Zn sheets are required to be soaked in thiol solution; the assembled protective film is in molecular level, so that the quality of the zinc sheet is not obviously increased after the molecular film is assembled on the surface of the zinc sheet. The invention has wide source of raw materials, low price and low production cost, and is suitable for large-scale production. The modified zinc cathode has excellent battery performance, runs stably within 1000 h, and has no short circuit.
Description
Technical Field
The invention belongs to the field of preparation of a zinc cathode with ultralong stability, and relates to zinc ion batteries, zinc ion capacitors, zinc-air batteries and other technical fields relating to metal zinc sheets, in particular to a modified zinc cathode and a preparation method and application thereof, and particularly relates to a preparation method of a Zn-SH cathode.
Background
The metal zinc (Zn) is one of the most ideal cathode materials of the water system battery due to the characteristics of high theoretical specific capacity, low oxidation-reduction potential, rich raw materials, good compatibility with water, natural safety and the like; the aqueous battery mainly refers to a secondary battery which takes an aqueous solution based on metal ions as an electrolyte, has high safety and environmental friendliness, and has good application prospects. Metal Zn also has great practical prospects in zinc ion batteries, zinc ion capacitors, zinc-air batteries, and other fields involving metal zinc sheets.
However, metallic Zn is easily subject to corrosion and hydrogen production in water, thereby reducing coulombic efficiency, consuming water and metallic Zn, promoting the growth of zinc dendrites to degrade the performance of the corresponding device, and even failing to operate normally. The existing improvement method mainly comprises the following steps: protective layers of metal, metal oxide and the like are introduced to the surface to inhibit the growth of hydrogen or zinc dendrites. However, these methods not only increase the quality of the whole zinc sheet, but also have complicated synthesis steps and harsh conditions, and cannot be mass-produced.
Disclosure of Invention
In view of the situation, the invention provides a modified zinc cathode and a preparation method and application thereof.
The invention provides a preparation method of a modified zinc cathode, which comprises the following steps:
s1) soaking the zinc sheet in a thiol solution for surface modification;
s2) washing the zinc sheet soaked in the step S1) with absolute ethyl alcohol and water respectively, and drying to obtain the modified zinc cathode.
In a preferred experimental scheme, the thiol solution used in step S1) is one or more of dodecanethiol, benzenethiol, and 2-propylthiol.
In a preferred embodiment, step S1) is preceded by: commercial zinc sheets are taken as raw materials and are respectively cleaned in acetone and absolute ethyl alcohol by ultrasonic.
In a preferred protocol, the commercial zinc flakes were ultrasonically cleaned using acetone and absolute ethanol for 10 to 60 minutes, preferably 20 to 40 minutes, respectively, prior to step S1).
In a preferred experimental protocol, the soaking in step S1) is performed at room temperature and atmospheric pressure.
In a preferred embodiment, the soaking time in step S1) is 1 to 48 hours.
In a preferred experimental scheme, the washing times in the step S2) are 1-5 times respectively by using absolute ethyl alcohol and water; the drying is preferably freeze drying or vacuum drying for 6-24 hours.
The invention provides a modified zinc cathode, which is prepared by the preparation method.
The invention also provides application of the modified zinc cathode prepared by the preparation method in preparation of a zinc ion battery, a zinc ion capacitor or a zinc-gas battery.
The embodiment of the invention provides a zinc ion battery, which takes zinc sulfate aqueous solution as electrolyte and comprises the modified zinc cathode.
Compared with the prior art, the invention provides a preparation method of the modified zinc cathode, which is simple and feasible, can be produced in a large scale and has no obvious increase in quality; the invention mainly adds zinc sheets into thiol solution to be soaked for a certain time, then the soaked metal zinc sheets are cleaned and dried by absolute ethyl alcohol and water, and the modified zinc cathode (expressed as Zn-SH cathode) can be obtained. According to the invention, through a simple soaking liquid phase preparation method, the mercaptan molecules are self-assembled on the surface of the metal zinc sheet to form a film, so that the corrosion of a zinc cathode and the generation of zinc dendrites are inhibited. The production process is extremely simple, and only commercial metal Zn sheets are required to be soaked in thiol solution; the assembled protective film is in molecular level, so that the quality of the zinc sheet is not obviously increased after the molecular film is assembled on the surface of the zinc sheet, and the energy density of the battery is facilitated. The raw materials of metal Zn, thiols and the like used in the invention have wide sources, low price and low production cost, and are suitable for large-scale production. The modified zinc cathode has excellent battery performance, runs stably within 1000 h, and has no short circuit.
In addition, the production process of the invention is safe, safe and harmless. The invention is harmless to the environment in the experimental process, does not produce waste liquid and waste material, and the thiol solution can be reused. The Zn-SH negative pole produced by the invention has wide application, not only can be used for zinc ion batteries and capacitors, but also can be used for Zn-gas batteries (such as Zn-air batteries) and other fields related to metal Zn.
Drawings
FIG. 1 is a comparison of the stability of Zn-SH negative electrodes of example 1 with that before modification;
FIG. 2 shows the Zn-SH negative electrode stability obtained by different reaction times according to the embodiment of the present invention;
FIG. 3 shows the weight gain of Zn cathode before reaction and after different reaction times according to the embodiment of the present invention;
FIG. 4 shows the element distribution of the pure Zn cathode and the modified Zn-SH cathode according to the embodiment of the present invention;
fig. 5 shows the stability test results of the modified zinc negative electrode obtained in example 6.
Detailed Description
The technical solutions in the embodiments of the present invention are clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention provides a preparation method of a modified zinc cathode, which comprises the following steps:
s1) soaking the zinc sheet in a thiol solution for surface modification;
s2) washing the zinc sheet soaked in the step S1) with absolute ethyl alcohol and water respectively, and drying to obtain the modified zinc cathode.
Based on the problems that the existing Zn cathode modification method is complicated, large-scale production cannot be realized, and the like, the invention provides a preparation strategy and a process for preparing a zinc cathode without dendrites and corrosion resistance.
Therefore, in the first aspect of the invention, a preparation method of a modified Zn negative electrode is provided, which mainly uses commercial zinc sheets as raw materials, and firstly cleans the commercial zinc sheets, preferably cleans the commercial zinc sheets by ultrasonic cleaning in acetone and absolute ethyl alcohol respectively, so as to remove impurities such as organic matters adsorbed on the surface.
In a preferred experimental scheme, the acetone solution and the absolute ethyl alcohol solution used in the step are both in chemical purity; in a preferred protocol, the volumes of acetone solution and absolute ethanol used in this step are each 50 mL. The commercial zinc sheet is a metal zinc sheet commercially available in the art as a negative electrode, and the present application is not particularly limited.
According to the embodiment of the invention, a commercial Zn sheet is firstly ultrasonically cleaned in 50mL of acetone solution, and then the Zn sheet is transferred into absolute ethyl alcohol solution for ultrasonic cleaning, so that the cleaned Zn sheet is obtained for later use. Among them, the time for ultrasonically cleaning commercial zinc sheets using acetone and absolute ethanol is generally 10 to 60 minutes, preferably 20 to 40 minutes, respectively. In a preferred experimental scheme, the ultrasonic time in acetone and absolute ethanol solution in the step is about 30 minutes, if the ultrasonic time is not carried out or the ultrasonic time is not enough, the metal zinc sheet is not cleaned, and if the ultrasonic time is too long, the surface of the metal zinc sheet is easy to be crushed.
According to the embodiment of the invention, the cleaned zinc sheet obtained in the step is soaked in a certain volume of thiol solution for surface modification, so that thiol molecules are fully contacted with the surface of the metal Zn cathode and assembled into a film, and further the corrosion of the zinc cathode and the generation of zinc dendrites are inhibited, and the stability of the zinc cathode is favorably improved.
In organic chemistry, one class of non-aromatic compounds containing a mercapto functional group (-SH) is referred to as thiols (R-SH); except that methyl mercaptan is a gas at room temperature,other thiols are liquids or solids. In the present invention, the above steps are performed by using a thiol solution, such as dodecanethiol, thiophenol, and other thiol solutions, and such liquid thiols can be assembled into a molecular-scale protective film on the surface of the metal zinc sheet. In a preferred experimental protocol, the thiol-based solution used in this step is dodecanethiol, in chemical purity; or mercaptans such as benzenethiol and 2-propyl mercaptan. Dodecanethiol, also known as laurylthiol, 1-mercaptododecane, 1-dodecanethiol, n-dodecanethiol, is a colorless, water-white or light yellow liquid. The molecular formula of the benzenethiol is C6H6S2Also known as 1, 3-benzenedithiol, is colorless liquid or white solid in character.
In a preferred experimental scheme, the time for soaking the metallic Zn sheet in the mercaptan in the step is 1-48h, such as 1h, 6h, 12h, 24h and 48 h; the soaking described in the examples of the present invention is generally carried out at room temperature (e.g., 10-30 ℃) and atmospheric pressure.
After soaking for a certain time, the obtained metal zinc sheet is respectively washed by absolute ethyl alcohol and water (usually deionized water), and finally dried to obtain the Zn-SH negative electrode.
In a preferred experimental scheme, the steps are respectively washed by absolute ethyl alcohol and deionized water, the washing times are 1-5 times respectively, and the washing times by the absolute ethyl alcohol and the deionized water are more preferably once respectively. The drying described in the examples of the present invention is preferably freeze drying, which is a drying means well known to those skilled in the art, and the freeze drying time may be 6 to 24 hours, preferably 8 to 20 hours, more preferably 10 to 15 hours. The drying is not limited to freeze drying, but vacuum drying is also possible, at temperatures of 50-100 ℃.
The invention provides a modified zinc cathode, which is prepared by the preparation method. That is, the second aspect of the present invention provides the Zn-SH negative electrode obtained by the method according to the first aspect of the present invention, which has a surface protective film of molecular level, no excessive mass increase, ultra-long cycle stability, and is advantageous for the energy density of the battery.
In a third aspect, the invention provides the use of a Zn-SH negative electrode according to the second aspect of the invention in the manufacture of a zinc ion battery, a zinc ion capacitor or a zinc-air battery, as well as other applications involving metallic zinc flakes. For example, the embodiment of the invention can obtain the Zn-SH material according to the preparation method, and then apply the Zn-SH material to the battery negative electrode.
Specifically, the embodiment of the invention provides a zinc ion battery, which uses a zinc sulfate aqueous solution as an electrolyte, and includes the modified zinc negative electrode described above, which can be used as an electrode of a symmetric battery.
The Zn-SH prepared by the invention has excellent cycling stability as a battery cathode and has huge application prospect in zinc ion batteries, zinc ion capacitors, zinc-air batteries and other fields relating to metal zinc sheets. Compared with the method for improving the stability of the zinc cathode reported at present, the method for preparing the Zn-SH cathode is simple and easy to implement, easy for large-scale production and low in cost.
For further understanding of the present application, the modified zinc anode provided by the present application, and the preparation method and application thereof are specifically described below with reference to examples. It should be understood, however, that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention, which is defined by the following examples.
The examples, where specific techniques or conditions are not indicated, are to be construed according to the techniques or conditions described in the literature in the art or according to the product specifications. The reagents or instruments used are not indicated by manufacturers, and are all conventional products available on the market.
In the following examples, commercial Zn pellets with a purity of 99.995% and a thickness of 30 μm were purchased from Taobao, and all the Zn pellets were cut into 12 mm-diameter disks before use.
Example 1
a, ultrasonically cleaning a commercial Zn sheet in 50ml of acetone solution for 30 minutes, and then, ultrasonically cleaning the Zn sheet in absolute ethyl alcohol solution for 30 minutes again to obtain a cleaned Zn sheet;
b, soaking the Zn sheet obtained in the step a in a dodecanethiol solution for 24 hours;
c, washing the soaked Zn sheet obtained in the step b with 50ml of absolute ethyl alcohol, and then washing with 50ml of deionized water.
And d, freeze-drying the Zn sheet obtained in the step c for 12 hours to obtain the modified Zn sheet Zn-SH.
Example 2
This embodiment differs from example 1 in that: the immersion time in the dodecanethiol solution in step b was 1h, the rest being the same as in example 1.
Example 3
This embodiment differs from example 1 in that: the immersion time in the dodecanethiol solution in step b was 6h, the rest being the same as in example 1.
Example 4
This embodiment differs from example 1 in that: the immersion time in the dodecanethiol solution in step b was 12h, the rest being the same as in example 1.
Example 5
This embodiment differs from example 1 in that: the immersion time in the dodecanethiol solution in step b was 48h, the rest being the same as in example 1.
Example 6
This embodiment differs from example 1 in that: the thiol used in step b was 2-propyl thiol, the rest being the same as in example 1.
The stability of the Zn-SH material obtained by the present invention will be described below to illustrate the effectiveness and advancement of this strategy.
Assembling the battery: the obtained Zn-SH (the Zn-SH negative electrode soaked for 24 hours is taken as a representative) is taken as an electrode of a symmetrical battery, namely two completely same Zn-SH negative electrodes are arranged in a CR2032 button battery; wherein, 1M ZnSO4The water solution is electrolyte, the glass fiber membrane is a diaphragm, and the assembly is completed in the air.
And (3) testing the battery: testing the assembled symmetrical battery in a battery testing system (Wuhan blue testing system) under the condition of 0.5 or 1.0mA cm-1Electricity (D) fromConstant current discharge at current density, and stopping until the capacity reaches 0.1mAh cm-2Then at 0.5 or 1.0mA cm-1Constant current charging at a current density of 0.1mAh cm under the cutoff condition-2。
FIG. 1 is a graph showing the comparison of the stability of Zn-SH negative electrode in example 1 with that before modification (0.5mA cm)-2，0.1mAh cm-2) As shown in fig. 1, compared with the stability of pure zinc sheets, the stability of the Zn-SH cathode is greatly improved (stable operation within 1000 hours, no short circuit occurs), which is beneficial to the practical application of the Zn-SH cathode.
In addition, referring to fig. 2, the stability of the Zn-SH negative electrode obtained in different reaction times is greatly improved, and the overpotential of the electrode modified for 1h (denoted as Zn-SH-1h, and the like in different reaction times) fluctuates, but the stability is far better than that of a pure zinc electrode.
FIG. 3 shows the weight increase of the Zn cathode before reaction and after different reaction times, in order to reduce the measurement error, 8 Zn plates with a diameter of 12mm were used for measurement at each reaction time, and then an average value was taken, which shows that the weight increase of the Zn-SH unit area after the reaction at different soaking times is less than 0.05%, and there is no significant mass increase.
FIG. 4 shows the element distribution of the pure Zn cathode and the modified Zn-SH cathode, and as shown in FIG. 4, the Zn-SH surface soaked by mercaptan has uniform distribution of S element, which illustrates the formation of the mercaptan molecular film on the surface.
FIG. 5 shows the stability test (1.0mA cm) of the modified zinc negative electrode obtained in example 6-2，0.1mAh cm-2) As shown in fig. 5, compared with the Zn — SH negative electrode obtained in propyl mercaptan before modification, the Zn — SH negative electrode has a larger overpotential in the previous period, and has an activation process, and after activation, the Zn — SH negative electrode stably operates within 500 hours, which indicates that the remaining mercaptan also has a certain effect on the surface modification of the Zn negative electrode.
From the above embodiments, the present invention utilizes the self-assembly effect of thiol molecules on the surface of Zn sheet by adding Zn sheet into thiol solution to assemble a molecular film on the surface of Zn sheet, thereby suppressing Zn corrosion and generation of zinc dendrite. The surface of the existing methods of introducing metal, metal oxide and the like is coated with a layer of substance, and the substances have larger mass per se; the invention has no redundant mass increase after adding the protective layer, and the assembled protective film is in molecular level, so that the mass of the zinc sheet is not obviously increased after assembling the molecular film on the surface, thereby being beneficial to the energy density of the battery. Moreover, the preparation method is simple and can be completed only by simple soaking; the prepared Zn-SH negative electrode has good stability, excellent performance and lower cost, and is suitable for large-scale production.
The above description is only a preferred embodiment of the present invention, and it should be noted that various modifications to these embodiments can be implemented by those skilled in the art without departing from the technical principle of the present invention, and these modifications should be construed as the scope of the present invention.
Claims (10)
1. The preparation method of the modified zinc cathode is characterized by comprising the following steps of:
s1) soaking the zinc sheet in a thiol solution for surface modification;
s2) washing the zinc sheet soaked in the step S1) with absolute ethyl alcohol and water respectively, and drying to obtain the modified zinc cathode.
2. The method according to claim 1, wherein the thiol solution used in step S1) is one or more selected from the group consisting of dodecanethiol, benzenethiol, and 2-propylthiol.
3. The method according to claim 1, wherein step S1) is preceded by: commercial zinc sheets are taken as raw materials and are respectively cleaned in acetone and absolute ethyl alcohol by ultrasonic.
4. The method of claim 3, wherein the commercial zinc flakes are ultrasonically cleaned with acetone and absolute ethanol for 10 to 60 minutes, preferably 20 to 40 minutes, before the step S1).
5. The method according to claim 1, wherein the soaking in step S1) is performed at room temperature and atmospheric pressure.
6. The method according to claim 5, wherein the soaking time in the step S1) is 1 to 48 hours.
7. The production method according to any one of claims 1 to 6, wherein the washing in step S2) is performed 1 to 5 times with the absolute ethanol and the water, respectively; the drying is preferably freeze drying or vacuum drying for 6-24 hours.
8. A modified zinc negative electrode, characterized by being produced by the production method according to any one of claims 1 to 7.
9. Use of the modified zinc negative electrode prepared by the preparation method according to any one of claims 1 to 7 for preparing a zinc ion battery, a zinc ion capacitor or a zinc-gas battery.
10. A zinc ion battery using zinc sulfate aqueous solution as electrolyte, characterized by comprising the modified zinc negative electrode of claim 8.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110673551.4A CN113410452A (en) | 2021-06-17 | 2021-06-17 | Modified zinc cathode and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110673551.4A CN113410452A (en) | 2021-06-17 | 2021-06-17 | Modified zinc cathode and preparation method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN113410452A true CN113410452A (en) | 2021-09-17 |
Family
ID=77684916
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110673551.4A Pending CN113410452A (en) | 2021-06-17 | 2021-06-17 | Modified zinc cathode and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113410452A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113991047A (en) * | 2021-10-22 | 2022-01-28 | 哈尔滨工业大学 | Preparation method and application of modified metal zinc cathode |
| CN114335447A (en) * | 2021-12-28 | 2022-04-12 | 北京航空航天大学 | Surface treatment method for improving zinc negative polarity performance and application |
| CN114512630A (en) * | 2022-02-21 | 2022-05-17 | 江苏师范大学 | Method for modifying cathode of aqueous zinc ion battery |
| CN114899349A (en) * | 2022-05-05 | 2022-08-12 | 电子科技大学 | Method for inhibiting growth of zinc dendrite by modifying zinc of negative electrode of zinc ion battery |
Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5382482A (en) * | 1992-08-07 | 1995-01-17 | Nippon Oil Company, Limited | Zinc electrode for alkaline storage battery |
| CN1664167A (en) * | 2004-02-25 | 2005-09-07 | Posco公司 | Method of protecting metals from corrosion using thiol compounds |
| CN102407220A (en) * | 2011-11-09 | 2012-04-11 | 西北师范大学 | Method for preparing super hydrophobic film on surface of zinc substrate |
| CN104032306A (en) * | 2014-06-19 | 2014-09-10 | 中国船舶重工集团公司第七二五研究所 | Preparation method of copper alloy surface corrosion inhibition self-assembled film |
| CN104518205A (en) * | 2013-09-27 | 2015-04-15 | 苏州宝时得电动工具有限公司 | Preparation method for zinc anode, zinc anode and battery |
| CN108807961A (en) * | 2018-06-06 | 2018-11-13 | 上海电力学院 | A kind of zinc-base cell negative electrode material and preparation method thereof |
| CN109065832A (en) * | 2018-06-25 | 2018-12-21 | 武汉船用电力推进装置研究所（中国船舶重工集团公司第七二研究所） | A method of in serondary lithium battery metal negative electrode surface growth protecting layer |
| CN109355648A (en) * | 2018-09-07 | 2019-02-19 | 梁淑君 | In the method that copper alloy surface prepares based superhydrophobic thin films |
| CN111933912A (en) * | 2020-08-14 | 2020-11-13 | 华中科技大学 | Zinc cathode with zinc ion conductivity interface modification layer, battery and preparation method |
| CN112490396A (en) * | 2020-12-18 | 2021-03-12 | 吉林大学 | Metal zinc cathode, preparation method thereof and water-based zinc ion battery |
| CN112803083A (en) * | 2021-02-08 | 2021-05-14 | 江苏师范大学 | Zinc ion battery containing zinc complex |
-
2021
- 2021-06-17 CN CN202110673551.4A patent/CN113410452A/en active Pending
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5382482A (en) * | 1992-08-07 | 1995-01-17 | Nippon Oil Company, Limited | Zinc electrode for alkaline storage battery |
| CN1664167A (en) * | 2004-02-25 | 2005-09-07 | Posco公司 | Method of protecting metals from corrosion using thiol compounds |
| CN102407220A (en) * | 2011-11-09 | 2012-04-11 | 西北师范大学 | Method for preparing super hydrophobic film on surface of zinc substrate |
| CN104518205A (en) * | 2013-09-27 | 2015-04-15 | 苏州宝时得电动工具有限公司 | Preparation method for zinc anode, zinc anode and battery |
| CN104032306A (en) * | 2014-06-19 | 2014-09-10 | 中国船舶重工集团公司第七二五研究所 | Preparation method of copper alloy surface corrosion inhibition self-assembled film |
| CN108807961A (en) * | 2018-06-06 | 2018-11-13 | 上海电力学院 | A kind of zinc-base cell negative electrode material and preparation method thereof |
| CN109065832A (en) * | 2018-06-25 | 2018-12-21 | 武汉船用电力推进装置研究所（中国船舶重工集团公司第七二研究所） | A method of in serondary lithium battery metal negative electrode surface growth protecting layer |
| CN109355648A (en) * | 2018-09-07 | 2019-02-19 | 梁淑君 | In the method that copper alloy surface prepares based superhydrophobic thin films |
| CN111933912A (en) * | 2020-08-14 | 2020-11-13 | 华中科技大学 | Zinc cathode with zinc ion conductivity interface modification layer, battery and preparation method |
| CN112490396A (en) * | 2020-12-18 | 2021-03-12 | 吉林大学 | Metal zinc cathode, preparation method thereof and water-based zinc ion battery |
| CN112803083A (en) * | 2021-02-08 | 2021-05-14 | 江苏师范大学 | Zinc ion battery containing zinc complex |
Non-Patent Citations (2)
| Title |
|---|
| 常强等: "热镀锌层表面超疏水耐蚀膜层的制备及性能研究", 《电镀与涂饰》 * |
| 杜伟等: "十八硫醇自组装膜对青铜的缓蚀作用", 《中国有色金属学报》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113991047A (en) * | 2021-10-22 | 2022-01-28 | 哈尔滨工业大学 | Preparation method and application of modified metal zinc cathode |
| CN114335447A (en) * | 2021-12-28 | 2022-04-12 | 北京航空航天大学 | Surface treatment method for improving zinc negative polarity performance and application |
| CN114335447B (en) * | 2021-12-28 | 2023-09-01 | 北京航空航天大学 | Surface treatment method for improving zinc cathode performance and application |
| CN114512630A (en) * | 2022-02-21 | 2022-05-17 | 江苏师范大学 | Method for modifying cathode of aqueous zinc ion battery |
| CN114899349A (en) * | 2022-05-05 | 2022-08-12 | 电子科技大学 | Method for inhibiting growth of zinc dendrite by modifying zinc of negative electrode of zinc ion battery |
| CN114899349B (en) * | 2022-05-05 | 2023-03-21 | 电子科技大学 | Method for inhibiting growth of zinc dendrite by modifying zinc of negative electrode of zinc ion battery |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN113410452A (en) | Modified zinc cathode and preparation method and application thereof | |
| CN107887592B (en) | Carbon-coated ZnO nanowire and preparation method and application thereof | |
| CN109449355B (en) | Modified polyacrylonitrile non-woven fabric/silicon dioxide aerogel composite diaphragm for battery and preparation method thereof | |
| CN108390033A (en) | A kind of preparation method and applications preparing anode material of lithium-ion battery carbon-coated antimony nano-tube material | |
| CN109546134A (en) | The negative electrode material and sodium-ion battery a kind of sodium-ion battery cathode pre- sodium modification method and obtained | |
| WO2020107858A1 (en) | Preparation method for cross-linked polymer electrolyte, and semisolid polymer battery and preparation method therefor | |
| CN102610790B (en) | Lithium rechargeable battery and its positive plate | |
| CN107069133B (en) | A kind of method of lithium in recycling lithium cell cathode material | |
| CN110265656A (en) | Aqueous zinc ion secondary battery using elemental sulfur or sulfide as anode | |
| CN108808080A (en) | Nano-composite gel electrolyte, lithium secondary battery and preparation method thereof | |
| CN112341639A (en) | Self-repairing hydrogel, preparation method thereof and flexible self-repairing rechargeable battery | |
| CN111129579A (en) | Sulfide solid electrolyte material, preparation method thereof and solid battery | |
| CN107069054A (en) | The fuel cell catalyst materials preparation method of efficient stable | |
| CN109962219A (en) | The method that silicium cathode material surface constructs solid electrolyte interface film in situ in advance | |
| CN113270577A (en) | Aqueous zinc ion battery and positive electrode material | |
| CN110416506B (en) | Modified lithium iron phosphate cathode material and preparation method thereof | |
| CN109560277A (en) | A kind of preparation method of nanometer of linear manganese selenide/carbon composite | |
| CN113363414A (en) | Lithium ion battery positive plate using multilayer coated ternary positive material and preparation method thereof | |
| CN108321397A (en) | Self-supported membrane and preparation method thereof and lithium-sulfur cell | |
| JPH02223159A (en) | Lithium secondary battery | |
| CN114335447B (en) | Surface treatment method for improving zinc cathode performance and application | |
| CN106972213B (en) | A kind of capacity quick recovery method of lead-acid accumulator | |
| CN114835091A (en) | High-performance zinc ion battery positive electrode material bismuth selenide nanosheet and preparation method thereof | |
| CN114284505A (en) | Porous copper current collector, preparation method thereof and application thereof in zinc/sodium ion battery | |
| CN108649193B (en) | Modified lithium ion battery anode material and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20210917 |