CN101710616B - Nickel hydroxide membrane electrode and preparation method thereof - Google Patents
Nickel hydroxide membrane electrode and preparation method thereof Download PDFInfo
- Publication number
- CN101710616B CN101710616B CN2009101545601A CN200910154560A CN101710616B CN 101710616 B CN101710616 B CN 101710616B CN 2009101545601 A CN2009101545601 A CN 2009101545601A CN 200910154560 A CN200910154560 A CN 200910154560A CN 101710616 B CN101710616 B CN 101710616B
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- Prior art keywords
- nickel hydroxide
- membrane electrode
- nickel
- preparation
- hydroxide membrane
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- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 title claims abstract description 51
- 239000012528 membrane Substances 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 72
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 34
- 239000011159 matrix material Substances 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 12
- 239000003792 electrolyte Substances 0.000 claims description 20
- 230000001413 cellular effect Effects 0.000 claims description 14
- 238000000151 deposition Methods 0.000 claims description 14
- 230000008021 deposition Effects 0.000 claims description 14
- 239000010949 copper Substances 0.000 claims description 11
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 7
- 229910052802 copper Inorganic materials 0.000 claims description 7
- 238000004070 electrodeposition Methods 0.000 claims description 7
- 230000005518 electrochemistry Effects 0.000 claims description 5
- 229910000792 Monel Inorganic materials 0.000 claims description 4
- 239000011248 coating agent Substances 0.000 claims description 4
- 238000000576 coating method Methods 0.000 claims description 4
- -1 wherein Substances 0.000 claims 1
- 239000003990 capacitor Substances 0.000 abstract description 5
- 238000007599 discharging Methods 0.000 abstract description 2
- 238000002848 electrochemical method Methods 0.000 abstract 1
- 229910018054 Ni-Cu Inorganic materials 0.000 description 5
- 241000080590 Niso Species 0.000 description 5
- 229910018481 Ni—Cu Inorganic materials 0.000 description 5
- 229910021607 Silver chloride Inorganic materials 0.000 description 5
- 229910045601 alloy Inorganic materials 0.000 description 5
- 239000000956 alloy Substances 0.000 description 5
- 238000004090 dissolution Methods 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 230000014759 maintenance of location Effects 0.000 description 5
- 150000002815 nickel Chemical class 0.000 description 5
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 5
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- 238000001000 micrograph Methods 0.000 description 3
- 238000011161 development Methods 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 238000012827 research and development Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910001030 Iron–nickel alloy Inorganic materials 0.000 description 1
- 229910007567 Zn-Ni Inorganic materials 0.000 description 1
- 229910007614 Zn—Ni Inorganic materials 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 229910001925 ruthenium oxide Inorganic materials 0.000 description 1
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
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Classifications
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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
- Y02E60/10—Energy storage using batteries
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- Battery Electrode And Active Subsutance (AREA)
- Electroplating Methods And Accessories (AREA)
Abstract
The invention discloses a nickel hydroxide membrane electrode and a preparation method thereof, which can be applied to the aspects of a secondary battery, an electrochemical super-capacitor and the like and belong to the technical field of electrochemical energy. The nickel hydroxide membrane electrode of the invention comprises a metallic matrix, wherein a porous nickel layer is precipitated on the metallic matrix; and nickel hydroxide is precipitated in the hole of the nickel layer. Compared with the prior art, the nickel hydroxide membrane electrode and the preparation method thereof have the advantages that: the nickel hydroxide membrane electrode is prepared by completely adopting an electrochemical method which is characterized by simple operation, mild condition and easy control; and the nickel hydroxide membrane electrode prepared by the method can obtain higher specific capacity and better cycle performance under the condition of higher discharging current.
Description
Technical field
The present invention relates to a kind of nickel hydroxide membrane electrode and preparation method thereof, can be used for aspects such as secondary cell and electric chemical super capacitor, belong to the electrochemical energy technical field.
Background technology
With the alkali secondary chargeable battery of nickel hydroxide, in storage battery family, occupy very consequence, like widely used Cd-Ni, Zn-Ni, Fe-Ni storage battery etc. as positive active material.Because the Ni-based secondary cell of above-mentioned hydroxide adopt positive limited capacity, the excessive preparation technology of negative pole mostly, so the performance of battery depends on the performance of nickel hydroxide electrode to a great extent.Along with the development in fields such as high-power compact electronic equipment and electric motor car, increasingly high requirement has been proposed for the high power discharge performance of battery.The high power discharge performance that how to improve nickel hydroxide electrode becomes the key that promotes the Ni-based secondary cell large-scale application of hydroxide.
Electric chemical super capacitor have discharge and recharge rapidly, advantages such as high-specific-power and good cycle, become one of the focus of the research and development of electrochemical energy source domain at present.Electrode material is as the core part of electrochemical capacitor, to its capacitive property decisive role.Up to now, ruthenium-oxide is the most excellent capacitor electrode material of performance, but because its expensive price has seriously restricted its application in commercially producing.Therefore, the transition metal oxide material that development cost is cheap and capacitance characteristic is good becomes a kind of research and development direction, and nickel hydroxide is owing to having the high theoretical specific capacity and bigger power density receives researcher's attention.
The structure of nickel hydroxide membrane electrode of the prior art is on a metallic matrix, directly to deposit one deck nickel hydroxide film, but the actual specific capacity of this nickel hydroxide membrane electrode is lower, is generally 200F/g.
Summary of the invention
The object of the present invention is to provide a kind of nickel hydroxide membrane electrode than height ratio capacity and preparation method thereof that has.
Be to realize above-mentioned purpose, the technical scheme that the present invention taked is: this nickel hydroxide membrane electrode mainly comprises metallic matrix, wherein, on said metallic matrix, deposits the cellular nickel dam, nickel hydroxide is arranged in that the inner hole deposition of nickel dam is long-pending.
Further, nickel dam according to the invention is a meso-hole structure.
The preparation method of nickel hydroxide membrane electrode of the present invention is characterized in that may further comprise the steps:
(1) containing Ni
2+And Cu
2+Electrolyte on the metallic matrix electro-deposition one deck monel coating;
(2) remove the copper in the monel coating through electrochemistry anodic solution method, obtain the cellular nickel dam;
(3) containing Ni
2+Electrolyte in, utilize electrochemistry cathodic reduction method at the long-pending nickel hydroxide of the inner hole deposition of said nickel dam, obtain nickel hydroxide membrane electrode.
Further, the present invention in the described electrolyte of step (1), Ni
2+Concentration be 0.01～4mol/L, Cu
2+Concentration be 0.001～1mol/L.
Further, the pH value of the described electrolyte of step of the present invention (1) is 1.0～6.0.
Further, the described electrolyte of step of the present invention (3) is the Ni (NO of 0.001～4mol/L
3)
2
Further, the present invention is in step (3), and utilizing the current density of electrochemistry cathodic reduction method deposition nickel hydroxide is 0.01～20mA/cm
2
Compared with prior art, advantage of the present invention is: nickel hydroxide membrane electrode adopts electrochemical production fully, simple to operate, mild condition, is easy to control; Nickel hydroxide membrane electrode through the method obtains under higher discharging current condition, can obtain higher specific capacity and better cycle performance.
Description of drawings
Fig. 1 is the structural representation of a kind of execution mode of nickel hydroxide membrane electrode of the present invention;
Fig. 2 is the electron scanning micrograph of the cellular nickel dam of the present invention before the deposition nickel hydroxide;
Fig. 3 is the electron scanning micrograph of nickel hydroxide membrane electrode of the present invention.
Embodiment
Below in conjunction with accompanying drawing and embodiment the present invention is done further explain.
As shown in Figure 1, nickel hydroxide membrane electrode of the present invention has a metallic matrix 1, and this metallic matrix 1 can be nickel, stainless steel or other metal matrix.On metallic matrix 1, deposit cavernous nickel dam 2, nickel hydroxide 3 arranged in that the inner hole deposition of nickel dam 2 is long-pending.The nickel dam of vesicular texture has bigger specific area; After deposition nickel hydroxide on the cellular nickel dam; Nickel hydroxide 3 and nickel dam 2 have combined to increase the effecting reaction area of electrode; Help the infiltration of electrolyte and the transmission of reactive component, therefore under higher discharge-rate, demonstrate excellent discharge performance, specific capacity can reach more than the 300F/g.
In electron scanning micrograph shown in Figure 2, before the deposition nickel hydroxide, the pore size of cellular nickel dam is about 150 nanometers.Comparison diagram 2 can know that with Fig. 3 after deposition nickel hydroxide on the cellular nickel dam, the aperture in the nickel dam obviously diminishes; Show that the nickel hydroxide major sedimentary is in the hole of cellular nickel dam; The aperture of cellular nickel dam is more little, and the effecting reaction area of electrode is big more, when the nickel dam of nickel hydroxide membrane electrode is meso-hole structure; Aperture on the nickel dam is 2～50 nanometers, and first discharge specific capacity can be up to 945F/g.
Embodiment 1:
The pH value be 3.0 contain 2mol/L NiSO
4With 0.02mol/L CuSO
4Electrolyte in, under the room temperature under the cathode potential of-0.8V (with respect to the Ag/AgCl electrode, down with) on the metallic matrix prepared by electrodeposition Ni-Cu alloy layer, the electric weight of feeding is 6C; In identical electrolyte, under the anode potential of 0.5V, select dissolved copper, when anodic current density is reduced to 10 μ A/cm
2The time, stop course of dissolution, on metallic matrix, obtain the cellular nickel dam; In the nickel nitrate solution of 1.0mol/L, be 5mA/cm in current density
2, the electric weight that feeds is under the condition of 0.72C, with the cathodic reduction method at the long-pending nickel hydroxide of the inner hole deposition of this nickel dam, through washing, after the drying, obtaining nickel hydroxide membrane electrode; 500 later capacity of charge and discharge cycles are 460F/g under the current density of 5A/g, and capability retention is 61%.
Embodiment 2:
The pH value be 1.0 contain 0.01mol/L NiSO
4With 0.001mol/L CuSO
4Electrolyte in, under the room temperature under the cathode potential of-0.8V (with respect to the Ag/AgCl electrode, down with) on the metallic matrix prepared by electrodeposition Ni-Cu alloy layer, the electric weight of feeding is 6C; In identical electrolyte, under the anode potential of 0.5V, select dissolved copper, when anodic current density is reduced to 10 μ A/cm
2The time, stop course of dissolution, on metallic matrix, obtain the cellular nickel dam; In the nickel nitrate solution of 0.001mol/L, be 0.01mA/cm in current density
2, the electric weight that feeds is under the condition of 0.72C, with the cathodic reduction method at the long-pending nickel hydroxide of the inner hole deposition of this nickel dam, through washing, after the drying, obtaining nickel hydroxide membrane electrode; 500 later capacity of charge and discharge cycles are 490F/g under the current density of 5A/g, and capability retention is 72%.
Embodiment 3:
The pH value be 6.0 contain 4mol/L NiSO
4With 1mol/L CuSO
4Electrolyte in, under the room temperature under the cathode potential of-0.8V (with respect to the Ag/AgCl electrode, down with) on the metallic matrix prepared by electrodeposition Ni-Cu alloy layer, the electric weight of feeding is 6C; In identical electrolyte, under the anode potential of 0.5V, select dissolved copper, when anodic current density is reduced to 10 μ A/cm
2The time, stop course of dissolution, on metallic matrix, obtain the cellular nickel dam; In the nickel nitrate solution of 4mol/L, be 20mA/cm in current density
2, the electric weight that feeds is under the condition of 0.72C, with the cathodic reduction method at the long-pending nickel hydroxide of the inner hole deposition of this nickel dam, through washing, after the drying, obtaining nickel hydroxide membrane electrode; 500 later capacity of charge and discharge cycles are 310F/g under the current density of 5A/g, and capability retention is 67%.
Embodiment 4:
The pH value be 4.5 contain 0.4mol/L NiSO
4With 0.1mol/L CuSO
4Electrolyte in, under the room temperature under the cathode potential of-0.8V (with respect to the Ag/AgCl electrode, down with) on the metallic matrix prepared by electrodeposition Ni-Cu alloy layer, the electric weight of feeding is 6C; In identical electrolyte, under the anode potential of 0.5V, select dissolved copper, when anodic current density is reduced to 10 μ A/cm
2The time, stop course of dissolution, on metallic matrix, obtain the cellular nickel dam; In the nickel nitrate solution of 0.05mol/L, be 0.1mA/cm in current density
2, the electric weight that feeds is under the condition of 0.72C, with the cathodic reduction method at the long-pending nickel hydroxide of the inner hole deposition of this nickel dam, through washing, after the drying, obtaining nickel hydroxide membrane electrode; 500 later capacity of charge and discharge cycles are 742F/g under the current density of 5A/g, and capability retention is 81%.
Embodiment 5:
The pH value be 2.5 contain 0.1mol/L NiSO
4With 0.05mol/L CuSO
4Electrolyte in, under the room temperature under the cathode potential of-0.8V (with respect to the Ag/AgCl electrode, down with) on the metallic matrix prepared by electrodeposition Ni-Cu alloy layer, the electric weight of feeding is 6C; In identical electrolyte, under the anode potential of 0.5V, select dissolved copper, when anodic current density is reduced to 10 μ A/cm
2The time, stop course of dissolution, on metallic matrix, obtain the cellular nickel dam; In the nickel nitrate solution of 0.02mol/L, be 2mA/cm in current density
2, the electric weight that feeds is under the condition of 0.72C, with the cathodic reduction method at the long-pending nickel hydroxide of the inner hole deposition of this nickel dam, through washing, after the drying, obtaining nickel hydroxide membrane electrode; 500 later capacity of charge and discharge cycles are 733F/g under the current density of 5A/g, and capability retention is 86%.
Claims (3)
1. the preparation method of a nickel hydroxide membrane electrode is characterized in that may further comprise the steps:
(1) containing Ni
2+And Cu
2+Electrolyte on the metallic matrix electro-deposition one deck monel coating, wherein, Ni
2+Concentration be 0.01～4 mol/L, Cu
2+Concentration be 0.001～1 mol/L;
(2) remove the copper in the monel coating through electrochemistry anodic solution method, obtain the cellular nickel dam;
(3) containing Ni
2+Electrolyte in, at 0.01～20 mA/cm
2Current density under, utilize electrochemistry cathodic reduction method at the long-pending nickel hydroxide of the inner hole deposition of said nickel dam, obtain nickel hydroxide membrane electrode.
2. the preparation method of nickel hydroxide membrane electrode according to claim 1, it is characterized in that: the pH value of the described electrolyte of step (1) is 1.0～6.0.
3. the preparation method of nickel hydroxide membrane electrode according to claim 1, it is characterized in that: the described electrolyte of step (3) is the Ni (NO of 0.001～4 mol/L
3)
2
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009101545601A CN101710616B (en) | 2009-11-12 | 2009-11-12 | Nickel hydroxide membrane electrode and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009101545601A CN101710616B (en) | 2009-11-12 | 2009-11-12 | Nickel hydroxide membrane electrode and preparation method thereof |
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| Publication Number | Publication Date |
|---|---|
| CN101710616A CN101710616A (en) | 2010-05-19 |
| CN101710616B true CN101710616B (en) | 2012-05-02 |
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| US9353345B2 (en) * | 2013-07-12 | 2016-05-31 | Ta Instruments-Waters L.L.C. | Securing apparatus and method |
| US9840789B2 (en) | 2014-01-20 | 2017-12-12 | City University Of Hong Kong | Etching in the presence of alternating voltage profile and resulting porous structure |
| RU2616584C1 (en) * | 2015-12-22 | 2017-04-18 | федеральное государственное бюджетное образовательное учреждение высшего образования "Нижегородский государственный технический университет им. Р.Е. Алексеева" | Method of producing metal-felt bases for oxide-nickel electrodes of alkaline accumulators |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1174419A (en) * | 1996-08-21 | 1998-02-25 | 松下电器产业株式会社 | Nickel positive electrode for alkaline accumulator and nickel-metallic hydrogenate accumulator thereof |
| CN1179017A (en) * | 1996-10-09 | 1998-04-15 | 三星电管株式会社 | Method for producing nickel positive electrode |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1174419A (en) * | 1996-08-21 | 1998-02-25 | 松下电器产业株式会社 | Nickel positive electrode for alkaline accumulator and nickel-metallic hydrogenate accumulator thereof |
| CN1179017A (en) * | 1996-10-09 | 1998-04-15 | 三星电管株式会社 | Method for producing nickel positive electrode |
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| CN101710616A (en) | 2010-05-19 |
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