CN105742648A - Metal matrix zinc material and preparation method thereof - Google Patents
Metal matrix zinc material and preparation method thereof Download PDFInfo
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- CN105742648A CN105742648A CN201410768680.1A CN201410768680A CN105742648A CN 105742648 A CN105742648 A CN 105742648A CN 201410768680 A CN201410768680 A CN 201410768680A CN 105742648 A CN105742648 A CN 105742648A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Abstract
The invention relates to a metal matrix zinc material. The metal matrix zinc material comprises a foam metal and zinc particles which are loaded to the inside of the foam metal; or the metal matrix zinc material comprises a metal net and the zinc particles which are loaded to the surface and the inside of the metal net; or the metal matrix zinc material comprises a metal sheet and the zinc particles which are loaded to the surface of the metal sheet; the zinc particles of the metal matrix zinc material have a porous structure; the pore sizes are 10-500 microns; and the porosity is 20%-95%. According to a preparation method of the metal matrix zinc material, the metal matrix zinc material is prepared by electrolytic deposition of the zinc particles employing the foam metal, the metal net or the metal sheet as a substrate.
Description
Technical field:
The present invention relates to a kind of Metal Substrate Zinc material and preparation method thereof.
Background technology:
Due to metallic zinc aboundresources, cheap, a lot of battery systems are all with zinc for electrode, such as zinc/air cell, zinc/nickel-based battery, zinc/silver battery etc..Be not stored in inside battery due to anode reactant, zinc/air cell has high specific energy and energy density per unit volume.In all business-like one-shot batteries, zinc/air cell has the highest energy density (JournalofPowerSources163 (2006) 591 597), and therefore zinc/air cell all has very wide application prospect in Portable power source, large-scale stationary electric power plant etc..
But, zinc electrode high-power/large current discharging capability is relatively low, its reason is that zinc electrode adopts the method that zinc powder mixes with bonding agent to prepare paste zinc electrode, in the paste zinc electrode of this kind of form, if zinc powder spacing is bigger, poor electric contact between zinc powder, cause high-power/heavy-current discharge time zinc electrode resistance bigger, if zinc powder is tightly combined, although its electrical contact ability is relatively strong, but under high-power/heavy-current discharge, product zinc oxide easily covers zinc powder surface, produce passivation, hinder the further reaction of zinc powder.The mixing of zinc powder, gel, zinc oxide, corrosion inhibiter and electrolyte is pressed into the paste zinc electrode with definite shape and mechanical strength by patent of invention CN102751478A.But, this electrode structure intensity is not high, easy fragmentation after being subject to shock and vibration, and owing to the addition of gel, this paste zinc electrode causes that electrode internal resistance is relatively big, and zinc electrode utilization rate and cycle performance are poor, mostly are single use.
Patent of invention CN102509774A reports paste zinc electrode and the compressing paste zinc electrode of preparing of currect collecting net, but this paste zinc electrode currect collecting net and calamine cream easily come off so that paste zinc electrode performance reduces.
Summary of the invention
The present invention propose in alkaline Bath or neutral electroplate liquid sheet metal, wire netting, foam metal or other there is 3-D solid structure metallic carrier substrates and prepare Metal Substrate Zinc material.Have when obtained Metal Substrate Zinc material is for zinc/air cell zinc anode that structural strength is big, utilization rate of zinc is high, good cycle, power density advantages of higher.Meanwhile, adopt the method to prepare Metal Substrate Zinc material and there is simplicity, the advantage such as easy to implement.
It is an object of the invention to be achieved through the following technical solutions:
A kind of Metal Substrate Zinc material, described Metal Substrate Zinc material includes foam metal and is carried on the zinc granule within foam metal hole, or described Metal Substrate Zinc material includes wire netting and is carried on the zinc granule on wire netting surface and metal grill within, or described Metal Substrate Zinc material includes sheet metal and the zinc granule being carried on sheet metal surface.
It is internal that described zinc granule is carried on foam metal hole by electrochemical method, or is carried on wire netting surface and within metal grill, or is carried on sheet metal surface.
Described foam metal is the one in nickel foam, foam copper, foam iron-nickel；Described wire netting is the one in nickel screen, copper mesh, titanium net, stainless (steel) wire；Described sheet metal is the one in nickel sheet, copper sheet, stainless steel substrates.
Described be metallic substrates with foam metal Zinc material there is loose structure；Described be substrate with wire netting or sheet metal the zinc granular layer of Zinc material there is loose structure.
The pore size of described loose structure is 10-500 μm.
The porosity of described loose structure is 20-95%.
Described zinc granular size is 20-40 μm.
The preparation method of a kind of described Metal Substrate Zinc material, prepares with foam metal, wire netting or sheet metal for substrate electrodepositing zinc granule through cleaning-drying.
In described electrodeposition process, electroplate liquid is containing Zn2+Neutral aqueous solution or be containing Zn (OH)4 2-Alkaline aqueous solution.
OH in described alkaline Bath-Concentration be 3-10mol/L, Zn (OH)4 2-Concentration be 0.1-1mol/L；Zn in described neutral electroplate liquid2+Concentration be 0.1-5mol/L.
Described electroplate liquid is containing corrosion inhibiter.
Described electrodeposition process is with foam metal, wire netting or sheet metal for negative pole, and zinc metal sheet is that positive pole carries out electro-deposition.
Described corrosion inhibiter is one or more in solubility indium, bismuth, thallium, gallium, stannum, lead, cadmium, calcium compounds, and the concentration of described corrosion inhibiter is not more than 0.1mol/L.
Described electro-deposition mode is the one in constant current electrodeposition process, constant voltage electrodeposition process, constant potential electrodeposition process, pulse electrodeposition method, pulse reverse electrodeposition process or adopts above two to continue with upper type and carry out electro-deposition.
In electrodeposition process, described constant current electrodeposition process specifically adopts constant current source or electrochemical workstation, applies a constant electric current, electric current density 50-5000mA cm at positive and negative interpolar-2；Described constant voltage electrodeposition process specifically adopts constant voltage source or electrochemical workstation, applies a constant voltage at positive and negative interpolar, and voltage range is 0.2-2V；Described constant potential electrodeposition process is specially employing electrochemical workstation and a reference electrode, and reference electrode can adopt hydrargyrum/mercuric oxide electrode, silver/silver chloride electrode etc., and electro-deposition current potential is-1.45V to-2.5V relative to hydrargyrum/mercuric oxide electrode；Described pulse electrodeposition method specifically adopts the pulse power or electrochemical workstation, applies a pulse current or pulse voltage at positive and negative interpolar, and concrete scope is with constant current electro-deposition and constant voltage electro-deposition, and pulse frequency 0.2-1000Hz, dutycycle is not less than 0.1；Described pulse reverse electrodeposition process adopts the pulse power or electrochemical workstation, applies a pulse current and reverse dissolution current, electro-deposition electric current density 50-5000mA cm at positive and negative interpolar-2, dissolution current density 0.1-50mA cm-2, pulse frequency and dutycycle are with pulse electrodeposition method.
nullThe preparation method of Metal Substrate Zinc material described in this patent，Wherein Metal Substrate adopts three-dimensional network type conductive carrier，Such as foam metal、Wire netting，Or sheet metal etc.，Conductive carrier does not react in Metal Substrate Zinc material charge and discharge process，Therefore excellent electric conductivity can be maintained all the time，Zinc granule is directly electrodeposited on metallic carrier，Adhesion is strong，Therefore in the process of discharge and recharge, it is able to maintain that its electric conductivity，Simultaneously，Due to metallic substrates，Especially foam metal，There is bigger porosity，Therefore the Metal Substrate Zinc material that prepared by this patent has remained in that bigger porosity，Electrolyte can be made to contact with abundant zinc granule during used as zinc/air cell anode，And product zinc oxide migrates out easily by the duct of Metal Substrate Zinc material，Therefore high-power/heavy-current discharge when，Metallic substrates prepared by this patent has remained in that higher electrical conductivity and resist passivation ability.Additionally, the method for the invention prepares Metal Substrate Zinc material has simplicity, advantage easy to implement, the Metal Substrate Zinc material simultaneously prepared has power density height, structural strength is big, utilization rate of zinc is high, the advantage of good cycle.
Accompanying drawing explanation
In order to be illustrated more clearly that the technical scheme of the embodiment of the present invention, below the accompanying drawing used needed for embodiment is done brief introduction.Obviously, it is only some embodiments of the present invention that middle accompanying drawing is described below, for those of ordinary skill in the art, under the premise not paying creative work, it is also possible to obtain other accompanying drawings according to these accompanying drawings.
The photo of the Metal Substrate Zinc material of preparation described in Fig. 1 embodiment 1.
The discharge performance curve of the Metal Substrate Zinc material of preparation described in Fig. 2 embodiment 1.
The photo of the Metal Substrate Zinc material of preparation described in Fig. 3 embodiment 2.
The discharge performance curve of the Metal Substrate Zinc material of preparation described in Fig. 4 embodiment 2.
The photo of the Metal Substrate Zinc material of preparation described in Fig. 5 embodiment 4.
The discharge performance curve of the Metal Substrate Zinc material of preparation described in Fig. 6 embodiment 4.
Described in Fig. 7 embodiment 4, the Metal Substrate Zinc material of preparation is at 200mA/cm2Utilization rate test curve during constant current discharge under electric current density.
The photo of the paste zinc electrode of preparation described in Fig. 8 comparative example.
The discharge performance curve of the paste zinc electrode of preparation described in Fig. 9 comparative example.
Detailed description of the invention
It is clearly and completely described below in conjunction with the technical scheme in the embodiment of the present invention, it is clear that described embodiment is only a part of embodiment of the present invention, rather than whole embodiments.Based on embodiments of the invention, the every other embodiment that those of ordinary skill in the art obtains under not having creative work premise, broadly fall into protection scope of the present invention.
Below in conjunction with accompanying drawing, the embodiment of the present invention being described in detail, Metal Substrate Zinc material of the present invention is in alkaline or neutral electroplate liquid, and at metallic carrier substrates, drying obtains after processing.
The list of experiments that table 1 embodiment adopts
Embodiment 1: the configuration alkaline Bath containing 8mol/L potassium hydroxide Yu 0.5mol/L zinc oxide, in electroplating bath, with foam copper for negative pole, zinc metal sheet is positive pole, applies a constant current 2000mA cm-2Carry out electro-deposition, prepare Metal Substrate Zinc material.Fig. 1 is the photo of Metal Substrate Zinc material prepared by the present embodiment, Fig. 2 be the Metal Substrate Zinc material prepared of the present embodiment as zinc/cathode of air battery time discharge performance curve.Wherein, zinc/O for cathode of air battery can lead to (Tianjin) New Energy Technology Co., Ltd. in capital purchased from nine, and side of the positive electrode leads to 50sccm oxygen, and electrolyte is 7mol/LKOH solution.
Embodiment 2: the configuration alkaline Bath containing 8mol/L potassium hydroxide Yu 0.5mol/L zinc oxide, in electroplating bath, with foam copper for negative pole, zinc metal sheet is positive pole, applies a constant voltage 1.7V and carries out electro-deposition, prepares Metal Substrate Zinc material.Fig. 3 is the photo of Metal Substrate Zinc material prepared by the present embodiment, Fig. 4 be the Metal Substrate Zinc material prepared of the present embodiment as zinc/cathode of air battery time discharge performance curve.Wherein zinc/O for cathode of air battery, electrolyte, discharging condition are all in the same manner as in Example 1.
Embodiment 3: the configuration alkaline Bath containing 8mol/L potassium hydroxide Yu 0.5mol/L zinc oxide, in electroplating bath, with foam copper for negative pole, zinc metal sheet is positive pole, hydrargyrum/mercuric oxide electrode is reference electrode, applies a constant potential-1.8V and carries out electro-deposition, prepares Metal Substrate Zinc material.
Embodiment 4: the configuration alkaline Bath containing 8mol/L potassium hydroxide Yu 0.5mol/L zinc oxide, in electroplating bath, with foam copper for negative pole, zinc metal sheet is positive pole, applies a pulse current (2000mA cm-2, 250Hz, dutycycle 0.33) carry out electro-deposition, prepare Metal Substrate Zinc material.Fig. 5 is the photo of Metal Substrate Zinc material prepared by the present embodiment, Fig. 6 be the Metal Substrate Zinc material prepared of the present embodiment as zinc/cathode of air battery time discharge performance curve.Wherein zinc/O for cathode of air battery, electrolyte, discharging condition are all in the same manner as in Example 1.Fig. 7 be the Metal Substrate Zinc material prepared of the present embodiment as zinc/cathode of air battery time, at 200mA cm-2Utilization rate test curve during constant current discharge under electric current density.Wherein zinc/O for cathode of air battery, electrolyte, discharging condition are all same as described above.
Embodiment 5: the configuration alkaline Bath containing 8mol/L potassium hydroxide Yu 0.5mol/L zinc oxide, in electroplating bath, with foam copper for negative pole, zinc metal sheet is positive pole, applies a pulse-reverse current (electro-deposition electric current density 2000mA cm-2, dissolution current density 10mA cm-2) carry out electro-deposition, prepare Metal Substrate Zinc material.
Embodiment 6: the configuration alkaline Bath containing 8mol/L potassium hydroxide Yu 0.5mol/L zinc oxide, in electroplating bath, with nickel foam for negative pole, zinc metal sheet is positive pole, applies a pulse current (2000mA cm-2, 250Hz, dutycycle 0.25) carry out electro-deposition, prepare Metal Substrate Zinc material.
Embodiment 7: the configuration alkaline Bath containing 8mol/L potassium hydroxide Yu 0.5mol/L zinc oxide, in electroplating bath, with copper mesh for negative pole, zinc metal sheet is positive pole, applies a pulse current (2000mA cm-2, 250Hz, dutycycle 0.25) carry out electro-deposition, prepare Metal Substrate Zinc material.
Embodiment 8: the configuration alkaline Bath containing 8mol/L potassium hydroxide Yu 0.5mol/L zinc oxide, in electroplating bath, with nickel screen for negative pole, zinc metal sheet is positive pole, applies a pulse current (2000mA cm-2, 250Hz, dutycycle 0.25) carry out electro-deposition, prepare Metal Substrate Zinc material.
Embodiment 9: the configuration alkaline Bath containing 8mol/L potassium hydroxide Yu 0.5mol/L zinc oxide, in electroplating bath, with copper sheet for negative pole, zinc metal sheet is positive pole, applies a pulse current (2000mA cm-2, 250Hz, dutycycle 0.25) carry out electro-deposition, prepare Metal Substrate Zinc material.
Embodiment 10: the configuration neutral electroplate liquid containing 2mol/L zinc nitrate, in electroplating bath, with foam copper for negative pole, zinc metal sheet is positive pole, applies a pulse current (2000mA cm-2, 250Hz, dutycycle 0.25) carry out electro-deposition, prepare Metal Substrate Zinc material.
Comparative example: by zinc powder, bonding agent, water in the ratio mix homogeneously of 100:1:45, said mixture is scraped the mastic making 2cm × 2cm size, after drying, two pieces of above-mentioned mastic is stacked into three-in-one structure with a piece of copper mesh, compressing in a mold, obtain paste zinc electrode.Fig. 8 is the photo of paste zinc electrode prepared by this comparative example, Fig. 9 be the paste zinc electrode prepared of this comparative example as zinc/cathode of air battery time discharge performance curve.Wherein zinc/O for cathode of air battery, electrolyte, discharging condition are all in the same manner as in Example 1.
Can be seen that from Fig. 1,3,5, Metal Substrate Zinc material surface prepared by above-described embodiment is adopted to have loose structure, during using above-mentioned Metal Substrate Zinc material as zinc/cathode of air battery, its battery performance (Fig. 2,4,6) under the same conditions is superior to comparative example (Fig. 9), in addition, from figure 7 it can be seen that utilization rate of zinc is higher when adopting Metal Substrate Zinc material prepared by embodiment of the present invention as zinc/cathode of air battery, up to 90%.
Claims (15)
1. a Metal Substrate Zinc material, it is characterized in that: described Metal Substrate Zinc material includes foam metal and is carried on the zinc granule within foam metal hole, or described Metal Substrate Zinc material includes wire netting and is carried on the zinc granule on wire netting surface and metal grill within, or described Metal Substrate Zinc material includes sheet metal and the zinc granule being carried on sheet metal surface.
2. Metal Substrate Zinc material as claimed in claim 1, it is characterised in that: it is internal that described zinc granule is carried on foam metal hole by electrochemical method, or is carried on wire netting surface and within metal grill, or is carried on sheet metal surface.
3. Metal Substrate Zinc material as claimed in claim 1, it is characterised in that: described foam metal is the one in nickel foam, foam copper, foam iron-nickel；Described wire netting is the one in nickel screen, copper mesh, titanium net, stainless (steel) wire；Described sheet metal is the one in nickel sheet, copper sheet, stainless steel substrates.
4. as claimed in claim 1 Metal Substrate Zinc material, it is characterised in that: described be metallic substrates with foam metal Zinc material there is loose structure；Described be substrate with wire netting or sheet metal the zinc granular layer of Zinc material there is loose structure.
5. Metal Substrate Zinc material as claimed in claim 4, it is characterised in that: the pore size of described loose structure is 10-500 μm.
6. Metal Substrate Zinc material as claimed in claim 4, it is characterised in that: the porosity of described loose structure is 20-95%.
7. Metal Substrate Zinc material as claimed in claim 1, it is characterised in that: described zinc particle size is 20-40 μm.
8. one kind as arbitrary in claim 1-7 as described in the preparation method of Metal Substrate Zinc material, it is characterised in that: with foam metal, wire netting or sheet metal for substrate electrodepositing zinc granule, cleaning-drying prepares.
9. the preparation method of Metal Substrate Zinc material as claimed in claim 8, it is characterised in that: in described electrodeposition process, electroplate liquid is containing Zn2+Neutral aqueous solution or be containing Zn (OH)4 2-Alkaline aqueous solution.
10. the preparation method of Metal Substrate Zinc material as claimed in claim 9, it is characterised in that: OH in described alkaline Bath-Concentration be 3-10mol/L, Zn (OH)4 2-Concentration be 0.1-1mol/L；Zn in described neutral electroplate liquid2+Concentration be 0.1-5mol/L.
11. the preparation method of Metal Substrate Zinc material as claimed in claim 9, it is characterised in that: described electroplate liquid is containing corrosion inhibiter.
12. the preparation method of Metal Substrate Zinc material as claimed in claim 8, it is characterised in that: described electrodeposition process is with foam metal, wire netting or sheet metal for negative pole, and zinc metal sheet is that positive pole carries out electro-deposition.
13. the preparation method of Metal Substrate Zinc material as claimed in claim 11, it is characterised in that: described corrosion inhibiter is one or more in solubility indium, bismuth, thallium, gallium, stannum, lead, cadmium, calcium compounds, and the concentration of described corrosion inhibiter is less than 0.1mol/L.
14. the as claimed in claim 8 preparation method of Metal Substrate Zinc material, it is characterised in that: described electro-deposition mode is the one in constant current electrodeposition process, constant voltage electrodeposition process, constant potential electrodeposition process, pulse current electrodeposition process, pulse voltage electrodeposition process, pulse reverse electrodeposition process or adopts above two to continue with upper type to carry out electro-deposition.
15. the preparation method of Metal Substrate Zinc material as claimed in claim 14, it is characterised in that: in described constant current electrodeposition process, electro-deposition electric current is 50-5000mA cm-2；In described pulse current electrodeposition process, electro-deposition electric current is 50-5000mA cm-2, pulse frequency 0.2-1000Hz, dutycycle is not less than 0.1；In described constant voltage electrodeposition process, electro-deposition voltage is 0.2-2V；In described pulse voltage electrodeposition process, electro-deposition voltage is 0.2-2V, pulse frequency 0.2-1000Hz, and dutycycle is not less than 0.1；In described constant potential electrodeposition process, electro-deposition current potential is-1.41V to-2.5V relative to hydrargyrum/mercuric oxide electrode；Electro-deposition electric current density 50-5000mA cm in described pulse reverse electrodeposition process-2, dissolution current density 0.1-50mA cm-2, pulse frequency 0.2-1000Hz, dutycycle is not less than 0.1.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107604386A (en) * | 2017-07-27 | 2018-01-19 | 天津大学 | A kind of flexibility can fill preparation method of the zinc-air battery with porous zinc load material |
| CN112151799A (en) * | 2020-09-16 | 2020-12-29 | 北京理工大学 | Three-dimensional porous interconnected framework lithium metal battery negative electrode material and preparation method thereof |
| US20210343995A1 (en) * | 2018-10-05 | 2021-11-04 | Research Foundation Of The City University Of New York | Electrochemical plating of additives on metallic electrodes for energy dense batteries |
| CN114023964A (en) * | 2021-10-27 | 2022-02-08 | 武汉理工大学 | Composite zinc foil with zinc oxide particle protective layer and preparation method and application thereof |
| WO2022179018A1 (en) * | 2021-02-25 | 2022-09-01 | 海南大学 | Method for preparing zinc-carbon composite electrode material for zinc ion energy storage device |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107604386A (en) * | 2017-07-27 | 2018-01-19 | 天津大学 | A kind of flexibility can fill preparation method of the zinc-air battery with porous zinc load material |
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| WO2022179018A1 (en) * | 2021-02-25 | 2022-09-01 | 海南大学 | Method for preparing zinc-carbon composite electrode material for zinc ion energy storage device |
| CN114023964A (en) * | 2021-10-27 | 2022-02-08 | 武汉理工大学 | Composite zinc foil with zinc oxide particle protective layer and preparation method and application thereof |
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