CN111162260A - Conductive polymer coated composite zinc cathode and preparation method thereof - Google Patents
Conductive polymer coated composite zinc cathode and preparation method thereof Download PDFInfo
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- CN111162260A CN111162260A CN202010009255.XA CN202010009255A CN111162260A CN 111162260 A CN111162260 A CN 111162260A CN 202010009255 A CN202010009255 A CN 202010009255A CN 111162260 A CN111162260 A CN 111162260A
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- zinc
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- electrode
- zinc cathode
- conductive polymer
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- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title claims abstract description 74
- 229910052725 zinc Inorganic materials 0.000 title claims abstract description 74
- 239000011701 zinc Substances 0.000 title claims abstract description 74
- 239000002131 composite material Substances 0.000 title claims abstract description 17
- 229920001940 conductive polymer Polymers 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 37
- 238000000034 method Methods 0.000 claims abstract description 18
- 229920000642 polymer Polymers 0.000 claims abstract description 16
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 10
- 239000011248 coating agent Substances 0.000 claims abstract description 7
- 238000000576 coating method Methods 0.000 claims abstract description 7
- 239000000126 substance Substances 0.000 claims abstract description 5
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims description 26
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- 239000000178 monomer Substances 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 13
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- 239000003792 electrolyte Substances 0.000 claims description 9
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000003999 initiator Substances 0.000 claims description 8
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 239000004094 surface-active agent Substances 0.000 claims description 6
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 claims description 5
- 238000004070 electrodeposition Methods 0.000 claims description 5
- 229910052697 platinum Inorganic materials 0.000 claims description 5
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 4
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 4
- 239000010406 cathode material Substances 0.000 claims description 4
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 4
- 229930192474 thiophene Natural products 0.000 claims description 4
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical group [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- 239000003945 anionic surfactant Substances 0.000 claims description 2
- SOCTUWSJJQCPFX-UHFFFAOYSA-N dichromate(2-) Chemical compound [O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O SOCTUWSJJQCPFX-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 239000012467 final product Substances 0.000 claims 2
- 210000001787 dendrite Anatomy 0.000 abstract description 3
- 238000007599 discharging Methods 0.000 abstract description 3
- 239000000463 material Substances 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 17
- 239000012153 distilled water Substances 0.000 description 15
- 229920000128 polypyrrole Polymers 0.000 description 8
- 238000001291 vacuum drying Methods 0.000 description 8
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 231100000053 low toxicity Toxicity 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 239000005486 organic electrolyte Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- RCEAADKTGXTDOA-UHFFFAOYSA-N OS(O)(=O)=O.CCCCCCCCCCCC[Na] Chemical group OS(O)(=O)=O.CCCCCCCCCCCC[Na] RCEAADKTGXTDOA-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- ONQDVAFWWYYXHM-UHFFFAOYSA-M potassium lauryl sulfate Chemical compound [K+].CCCCCCCCCCCCOS([O-])(=O)=O ONQDVAFWWYYXHM-UHFFFAOYSA-M 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
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Classifications
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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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/04—Processes of manufacture in general
- H01M4/0438—Processes of manufacture in general by electrochemical processing
- H01M4/045—Electrochemical coating; Electrochemical impregnation
- H01M4/0452—Electrochemical coating; Electrochemical impregnation from solutions
-
- 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
- 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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
-
- 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 discloses a conductive polymer coated composite zinc cathode and a preparation method thereof, belonging to the field of electrochemical energy materials. The invention prepares the cathode material-composite zinc cathode for the water system zinc ion battery by coating the conductive polymer on the traditional zinc cathode by the method of electrochemical polymerization or chemical polymerization. Compared with the prior art, the invention inhibits the generation of dendrite in the charging and discharging process of the traditional zinc cathode, prolongs the service life of the water system zinc ion battery and improves the electrochemical performance of the water system zinc ion battery. The polymer-coated composite zinc cathode is prepared under mild conditions, is simple to operate and wide in application range, can be expanded to various polymers and various types of zinc cathodes, and has high practical value and application prospect.
Description
Technical Field
The invention relates to a conductive polymer coated composite zinc electrode for a water system zinc ion battery, belonging to the field of electrochemical energy materials.
Background
Energy and environmental issues are two major issues that human survival and development must deal with. As a high-efficiency energy storage device, a secondary battery has been widely used in the fields of mobile phone communication, electric vehicles, and the like. At present, the most widely used battery for commercial use is a lithium ion battery, but because the electrolyte used by the lithium ion battery is an organic electrolyte, the organic solvent is usually toxic and flammable, and has great potential safety hazard. And the battery must be assembled in a severe environment without water and oxygen, resulting in a great increase in production cost. A battery system using an aqueous electrolyte instead of an organic electrolyte is expected to improve the safety of the battery and reduce the cost. Among metal elements which can stably exist in an aqueous solution, the zinc has the highest energy, and has the characteristics of rich resources, low toxicity, easy treatment and the like. Therefore, the water system zinc ion battery with low price, safety, environmental protection and high power provides a new opportunity for solving the energy crisis.
The metal zinc cathode has the characteristics of good conductivity, low toxicity, high specific energy and the like. However, dendrites are easily formed during charge and discharge cycles of the battery, and the battery is short-circuited by piercing the separator, which affects the cycle life of the battery.
Disclosure of Invention
The invention aims to solve the problems and provides a zinc cathode coated with a conductive polymer and a preparation method thereof, so as to inhibit the generation of zinc dendrites in the charging and discharging process, prolong the service life of an aqueous zinc ion battery and improve the electrochemical performance of the battery.
The technical scheme of the invention is as follows:
the invention relates to a composite zinc cathode coated with a conductive polymer, which utilizes electrochemical polymerization or chemical polymerization to polymerize a polymer monomer on the surface of a zinc cathode to prepare a composite zinc cathode material coated with the polymer and is used as a cathode material of an aqueous zinc ion battery.
The method for preparing the conductive polymer coated composite zinc cathode by an electrochemical polymerization method comprises the following specific steps:
1) pyrrole monomers and surfactants were dissolved in deionized water.
2) And (2) performing electrochemical deposition at a given working voltage by taking a zinc cathode as a working electrode, a platinum mesh electrode as a counter electrode, a saturated calomel electrode as a reference electrode and the solution obtained in the step 1) as an electrolyte, wherein the deposition time is 10-60 s.
3) Washing the mixture for three times by deionized water and ethanol respectively, and drying to obtain the product.
The concentration of the pyrrole monomer is 0.05-0.20 mol L-1The surfactant is lauryl sodium sulfate or other common sulfate anionic surfactant, and the concentration of the surfactant is 0.01-0.05 mol L-1。
The zinc cathode is a zinc sheet or a porous zinc cathode, and the volume ratio of the electrode to the electrolyte is 1: 5000-1: 30000.
The working voltage range is 0.5-1.0V.
The drying method is vacuum drying at 80 ℃ for 12 hours.
The mass of the conductive polymer coating is 0.01-3% of the mass of the electrode.
The method for preparing the conductive polymer coated composite zinc cathode by a chemical polymerization method comprises the following specific steps:
1) and dissolving or dispersing a polymer monomer in deionized water, and putting the uncoated zinc cathode into the solution.
2) Dissolving an initiator in deionized water; slowly dropwise adding an initiator solution into the polymer monomer solution containing the zinc cathode obtained in the step 1) under the conditions of ice bath and stirring, and continuously stirring for 3-10 min after dropwise adding.
3) Washing the mixture for three times by deionized water and ethanol respectively, and drying to obtain the product.
The polymer monomer is one of pyrrole, aniline or thiophene.
The polymer monomer is concentratedThe degree of reaction is 0.005-0.050 mol L-1。
The zinc cathode is a zinc sheet or a porous zinc cathode, and the volume ratio of the electrode to the polymer monomer solution is 1: 1000-1: 5000.
The initiator is one of ammonium persulfate, dichromate, ferric chloride or hydrogen peroxide, and the concentration of the initiator is 0.01-0.10 mol L-1。
The drying method is vacuum drying at 80 ℃ for 12 hours.
The mass of the conductive polymer coating is 0.01-3% of the mass of the electrode.
The invention has the technical effects that:
compared with the prior art, the invention inhibits the generation of dendritic crystals in the charging and discharging processes of the traditional zinc cathode, prolongs the service life of the water-based zinc ion battery and improves the electrochemical performance of the battery. The polymer-coated composite zinc cathode is prepared under mild conditions, is simple to operate and wide in application range, can be expanded to various polymers and various types of zinc cathodes, and has high practical value.
Drawings
Fig. 1 is SEM images before and after coating of the polypyrrole-coated zinc negative electrode prepared in example 4 of the present invention.
Fig. 2 is an optical diagram of the polypyrrole coated zinc negative electrode prepared in example 4 of the present invention before and after cycling.
FIG. 3 shows the zinc cathode coated with polypyrrole and the zinc cathode uncoated with polypyrrole prepared in example 4 of the invention at 500mA g-1Comparative graph of cycle performance of the following.
Detailed Description
The invention is further described below with reference to the accompanying drawings.
Example 1:
dissolving 0.0150mol of pyrrole and 3.75mmol of sodium dodecyl sulfate in 150mL of distilled water to obtain electrolyte; taking a zinc sheet with the thickness of 2 x 0.002cm as a working electrode, a platinum mesh electrode as a counter electrode and a saturated calomel electrode as a reference electrode, and carrying out electrochemical deposition under the working voltage of 0.7V for 30 s. And (3) washing the taken zinc sheet with distilled water and ethanol for several times respectively, and putting the zinc sheet into a vacuum oven at 80 ℃ for vacuum drying to obtain a product.
Example 2:
dissolving 0.0300mol of pyrrole and 7.50mmol of sodium dodecyl sulfate in 150mL of distilled water to obtain electrolyte; and performing electrochemical deposition at a working voltage of 0.5V for 10s by using 2 x 0.01cm porous zinc as a working electrode, a platinum mesh electrode as a counter electrode and a saturated calomel electrode as a reference electrode. And (3) washing the taken porous zinc with distilled water and ethanol for several times respectively, and putting the porous zinc into a vacuum oven at 80 ℃ for vacuum drying to obtain the product.
Example 3:
dissolving 0.0075mol of pyrrole and 1.50mmol of potassium dodecyl sulfate in 150mL of distilled water to obtain electrolyte; and performing electrochemical deposition at a working voltage of 1.0V for 60s by using 2X 4X 0.01cm porous zinc as a working electrode, a platinum mesh electrode as a counter electrode and a saturated calomel electrode as a reference electrode. And (3) washing the taken porous zinc with distilled water and ethanol for several times respectively, and putting the porous zinc into a vacuum oven at 80 ℃ for vacuum drying to obtain the product.
Example 4:
adding 0.300mmol pyrrole into 30mL distilled water, stirring for 20min, and soaking 2X 0.002cm zinc sheet into the solution; 0.100mmol of ammonium persulfate was weighed and dissolved in 10mL of distilled water to obtain a clear solution. And slowly dripping the obtained ammonium persulfate solution into the pyrrole solution containing the zinc sheets under the condition of ice bath and continuous stirring, and stirring for 5min after dripping. And (3) washing the taken zinc sheet with distilled water and ethanol for several times respectively, and putting the zinc sheet into a vacuum oven at 80 ℃ for vacuum drying to obtain a product.
SEM images before and after coating of the composite zinc electrode are shown in fig. 1, which shows: polypyrrole was successfully coated on the surface of the zinc sheet.
The optical diagrams before and after cycling of the polypyrrole-coated zinc negative electrode are shown in fig. 2, which shows that: the composite electrode has no obvious dendritic crystal after charge and discharge cycle.
The zinc negative electrode coated with polypyrrole and the zinc negative electrode uncoated with the polypyrrole are 500mA g-1The following cycle performance comparison is shown in FIG. 3, which shows: after coating the polymer, the composite zinc electrode is used as the discharge specific volume of the cathode material of the water-system zinc ion batteryThe amount is obviously improved.
Example 5:
adding 0.150mmol pyrrole into 30mL distilled water, stirring for 20min, and immersing a porous zinc cathode of 2 x 0.01cm into the solution; 0.200mmol of ammonium persulfate was weighed and dissolved in 10mL of distilled water to obtain a clear solution. And slowly dripping the obtained ammonium persulfate solution into the pyrrole solution containing the porous zinc cathode in an ice bath under the condition of continuously stirring, and stirring for 10min after dripping. And (3) washing the taken porous zinc electrode with distilled water and ethanol for several times respectively, and putting the porous zinc electrode into a vacuum oven at 80 ℃ for vacuum drying to obtain a product.
Example 6:
adding 1.500mmol thiophene into 30mL distilled water, stirring for 20min, and immersing 2X 4X 0.002cm zinc sheets into the solution; 1.000mmol of ferric chloride was weighed and dissolved in 10mL of distilled water to obtain a clear solution. And slowly dripping the obtained ferric chloride solution into a thiophene solution containing zinc sheets under the condition of ice bath and continuous stirring, and stirring for 10min after dripping. And (3) washing the taken zinc sheet with distilled water and ethanol for several times respectively, and putting the zinc sheet into a vacuum oven at 80 ℃ for vacuum drying to obtain a product.
Claims (10)
1. A conductive polymer coated composite zinc cathode is characterized in that a conductive polymer is coated on the surface of a zinc cathode by utilizing one of electrochemical polymerization or chemical polymerization and is used as a cathode material of an aqueous zinc ion battery.
2. The method for preparing the conductive polymer coated composite zinc cathode by an electrochemical polymerization method comprises the following steps:
1) dissolving pyrrole monomers and a surfactant in deionized water;
2) performing electrochemical deposition at a given working voltage for 10-60 s by using a zinc cathode as a working electrode, a platinum mesh electrode as a counter electrode, a saturated calomel electrode as a reference electrode and the solution obtained in the step 1) as an electrolyte;
3) washing with deionized water and ethanol, and drying to obtain the final product.
3. The method of claim 2, wherein: the concentration of the pyrrole monomer is 0.05-0.20 mol L-1(ii) a The surfactant is sodium dodecyl sulfate or other common sulfate anionic surfactants, and the concentration of the surfactant is 0.01-0.05 mol L-1。
4. The method of claim 2, wherein: the given working voltage range is 0.5-1.0V.
5. The method of claim 2, wherein: the zinc cathode is a zinc sheet or a porous zinc cathode, and the volume ratio of the electrode to the electrolyte is 1: 5000-1: 30000.
6. The method for preparing the conductive polymer coated composite zinc cathode by a chemical polymerization method comprises the following steps:
1) dissolving or dispersing a polymer monomer in deionized water, and putting an uncoated zinc cathode into the solution;
2) dissolving an initiator in deionized water; slowly dropwise adding an initiator solution into the polymer monomer solution containing the zinc cathode obtained in the step 1) under the conditions of ice bath and stirring, and continuously stirring for 3-10 min after dropwise adding is finished;
3) washing with deionized water and ethanol, and drying to obtain the final product.
7. The method of claim 6, wherein: the polymer monomer is one of pyrrole, aniline or thiophene; the concentration is 0.005-0.050 mol L-1。
8. The method of claim 6, wherein: the initiator is one of ammonium persulfate, dichromate, ferric chloride or hydrogen peroxide, and the concentration of the initiator is 0.01-0.10 mol L-1。
9. The method of claim 6, wherein: the zinc cathode is a zinc sheet or a porous zinc cathode, and the volume ratio of the electrode to the polymer monomer solution is 1: 1000-1: 5000.
10. The production method according to claim 2 or claim 6, characterized in that: the mass of the conductive polymer coating is 0.01-3% of the mass of the electrode.
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| CN202010009255.XA CN111162260A (en) | 2020-01-06 | 2020-01-06 | Conductive polymer coated composite zinc cathode and preparation method thereof |
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| CN202010009255.XA CN111162260A (en) | 2020-01-06 | 2020-01-06 | Conductive polymer coated composite zinc cathode and preparation method thereof |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105355876A (en) * | 2015-11-07 | 2016-02-24 | 合肥国轩高科动力能源有限公司 | Preparation method for composite conductive polymer coated with elemental sulfur and applications |
| CN107275611A (en) * | 2017-06-19 | 2017-10-20 | 南昌航空大学 | The spherical zinc oxide material of nanometer and preparation method of a kind of polypyrrole cladding |
| CN109524624A (en) * | 2018-11-26 | 2019-03-26 | 中南大学 | Cover the preparation method and secondary cell of the metal negative electrode of polymeric protective film in surface |
| CN110416549A (en) * | 2019-08-19 | 2019-11-05 | 中南大学 | A kind of metal zinc load and its preparation method and application with uniform meso-hole structure coating |
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- 2020-01-06 CN CN202010009255.XA patent/CN111162260A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105355876A (en) * | 2015-11-07 | 2016-02-24 | 合肥国轩高科动力能源有限公司 | Preparation method for composite conductive polymer coated with elemental sulfur and applications |
| CN107275611A (en) * | 2017-06-19 | 2017-10-20 | 南昌航空大学 | The spherical zinc oxide material of nanometer and preparation method of a kind of polypyrrole cladding |
| CN109524624A (en) * | 2018-11-26 | 2019-03-26 | 中南大学 | Cover the preparation method and secondary cell of the metal negative electrode of polymeric protective film in surface |
| CN110416549A (en) * | 2019-08-19 | 2019-11-05 | 中南大学 | A kind of metal zinc load and its preparation method and application with uniform meso-hole structure coating |
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