CN102605386A - Method for preparing Ni/NiCo2O4 porous composite electrode for alkaline medium oxygen evolution - Google Patents

Method for preparing Ni/NiCo2O4 porous composite electrode for alkaline medium oxygen evolution Download PDF

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CN102605386A
CN102605386A CN2012100484848A CN201210048484A CN102605386A CN 102605386 A CN102605386 A CN 102605386A CN 2012100484848 A CN2012100484848 A CN 2012100484848A CN 201210048484 A CN201210048484 A CN 201210048484A CN 102605386 A CN102605386 A CN 102605386A
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nico
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porous composite
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nickel
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王森林
鲍晋珍
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Huaqiao University
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Abstract

The invention provides a method for preparing a Ni/NiCo2O4 porous composite electrode for alkaline medium oxygen evolution, which comprises the following steps: preparing the powder of spinel with the chemical formula of NiCo2O4 by adopting the coprecipitation method by using the mixed aqueous solution of NiCl2.6H2O and CoCl.6H2O which are at the molar ratio of 1:2, wherein the powder of spine has the average size of 2mum; dispersing NiCo2O4 of which the surface is treated and the Al powder with the average size of 75mum in a Watter Ni plating solution; carrying out composite electrodeposition on a Ni substrate to obtain a Ni/(Al+NiCo2O4) composite coating; and finally soaking the composite coating in concentrated NaOH solution to desolventize Al and obtain the Ni/NiCo2O4 porous composite electrode. The Ni/NiCo2O4 porous composite electrode has the characteristics of high electrocatalytic activity for oxygen evolution, good stability, small resistance and large specific surface area.

Description

Alkaline medium is analysed oxygen and is used Ni/NiCo 2O 4The preparation method of porous composite electrode
Technical field
The present invention relates to a kind of alkaline medium analyses oxygen and uses Ni/NiCo 2O 4The preparation method of porous composite electrode.
Background technology
Hydrogen contains ability physical efficiency source as the secondary cleaning of future ideality, receives showing great attention to of various countries scientific worker.Water electrolysis hydrogen production is one of important means of preparation of industrialization high-purity hydrogen, and particularly for electricity consumption peak valley and sun power, the wind power generation that can't be incorporated into the power networks from far-off regions, a large amount of unserviceable unnecessary electrical power storage are significant.The anode generation oxygen evolution reaction of water electrolysis hydrogen production in the alkaline medium (oxygen evolution reaction is called for short OER).Requirement to electro catalytic electrode is overpotential for oxygen evolution low (electro catalytic activity is high), and electrode decay of activity in the electrolytic process of long period is few, and promptly electrode stability can be good.In the alkaline medium, the oxygen electrode of analysing the earliest adopts platinum, and afterwards because cost height and low nickel and the alloy thereof of use cost, electrode is generally made mesh-like or vesicular structure.Such electrode surface is prone to oxidation and forms oxide compound or the oxyhydroxide of inferior nickel and cause electrocatalysis characteristic to descend in electrolytic process.Nineteen seventies finds that respectively compound transition metal oxides such as spinel type have the oxygen of analysing electrocatalysis.General co-precipitation, high temperature solid state reaction or metal-salt thermolysis, the sol-gels etc. of adopting are earlier processed the compound transition metal oxide powder; Mix with a certain proportion of Graphite Powder 99 (improving conductivity) and macromolecule glue then; At last this mixture is coated on the matrix such as nickel, oven dry obtains electrode; Perhaps the precursor of transition metal salt (like hydroxide colloid etc.) is brushed on matrixes such as nickel, titanium, oven dry then is at last with electrode roasting and obtain the coated electrode of composite transition metal oxide under certain temperature in oxygen atmosphere.The oxygen electrode common name application type of analysing of these two kinds of traditional preparation process is analysed oxygen electrode.Application type is analysed oxygen electrode owing to bonding force relatively poor (mechanical property differs more greatly and causes) between matrix and coat, causes electrolytic process active coat under oxygen impacts to be prone to come off; And compound transition metal oxide is semi-conductor, its resistivity big (about 10 3S/cm) cause the electrode ohm voltage drop bigger, particularly under bigger current density, can cause than the macro-energy loss.
The content of invention
The object of the present invention is to provide a kind of high catalytic activity of alkaline medium oxygen evolution reaction and Ni/NiCo of stability of being used for 2O 4The preparation method of porous composite electrode.
For achieving the above object, technical scheme of the present invention is:
A kind of alkaline medium is analysed oxygen and is used Ni/NiCo 2O 4The preparation method of porous composite electrode comprises the steps: at first to adopt 1: 2 NiCl of mol ratio 26H 2O and CoCl6H 2The mixed aqueous solution of O carries out the spinel NiCo that coprecipitation method prepares median size 2 μ m 2O 4The compound transition metal oxide powder will pass through the NiCo after the surface treatment then 2O 4Be dispersed in the Watter nickel-plating liquid with the aluminium powder form of median size 75 μ m, on Ni substrate, obtain Ni/ (Al+NiCo through composite electrodeposition 2O 4) composite deposite, at last composite deposite is immersed in the concentrated NaOH solution precipitation and falls aluminium and obtain Ni/NiCo 2O 4Porous composite electrode.
Described coprecipitation method is meant two kinds and two or more solubilized metal-salt is formed undissolved compound and the method that from solution, is precipitated out is called coprecipitation method with highly basic (like sodium hydroxide etc.) or with other precipitation agent.Prepare 1: 2 NiCl of mol ratio at first earlier 26H 2O and CoCl6H 2The mixed aqueous solution of O is used 15wt% ammoniacal liquor (NH then 3H 2O) the pH value of adjustment mixed solution is 6～7, under continuous condition of stirring, in solution, slowly adds the oxalic acid (H of 80 ℃ 35wt% at last 2C 2O 42H 2O) aqueous solution through after leaving standstill, filter, washing, obtains oxalic acid precipitation thing (precursor); This precursor is placed on 100 ℃ of oven dryings, again this precursor is placed in the horse expense stove 300 ℃ of calcinings five hours, grind and obtain Powdered spinel NiCo 2O 4
Described composite electrodeposition is meant in certain plating bath; Add a certain amount of insoluble solid particle (general particle diameter is at 0.1～100 micrometer range); Constantly stirring is suspended in the plating bath solid particulate, and (like bath pH value, current density, temperature, stirring velocity etc.) make solid particulate deposit out with metal and form composite deposite under certain mode of deposition.Among the present invention, be meant in the Watter nickel-plating liquid, add NiCo 2O 4And aluminium powder form, make these solid particulates deposit out through stirring and form composite deposite with nickel.
Described Watter nickel-plating liquid prescription is: contain in every liter of solution: NiSO 46H 2O 300g/L, NiCl 26H 2O 50g/L, H 3BO 340g/L, tensio-active agent 1g/L; Wherein said NiCo 2O 4With the aluminium powder form add-on be: the NiCo of median size 75 μ m aluminium powder form 50g/L, median size 2 μ m 2O 4Powder 40～80g/L, adding distil water to 1 liter then.
Described aluminium powder form will after the washing, could add in the plating bath and use earlier through the weak base oil removing 10min of pH=8 before adding then.
The composite electrodeposition condition of described electroplate liquid is: 45 ℃ of bath temperatures, stirring velocity n=300～500r/min, plating bath pH are 6.0～6.8, cathode current density jk=40～120mA/cm 2
Described composite electrodeposition uses the pure nickel plate to make anode, and annode area is more than the twice of cathode area.
The invention has the beneficial effects as follows: the present invention forms nickel composite deposite through epitaxy on Ni substrate, so coating and basal body binding force are good; That this coating plays electrocatalysis is spinel NiCo 2O 4, the netted nickel that specific conductivity is high plays the conducting matrix grain effect, has so just reduced the resistivity of electrode largely.Outstanding advantages such as this electrode has the oxygen of analysing electro catalytic activity height, good stability, internal resistance is little, specific surface area is big.Ni/NiCo 2O 4Porous composite electrode can be used as the anode of electrolyzed alkaline water, also can be used as fuel cell in the alkaline medium, corrosion galvanic protection, the use of galvanized insoluble anode.
Description of drawings
Fig. 1 is sample 1 stereoscan photograph of the present invention;
Fig. 2 is sample 2 stereoscan photographs of the present invention.
Embodiment
Below in conjunction with accompanying drawing a nearly step being done in enforcement of the present invention describes in detail.
Embodiment 1
A kind of alkaline medium of present embodiment is analysed oxygen and is used Ni/NiCo 2O 4The preparation method of porous composite electrode comprises the steps: at first to adopt 1: 2 NiCl of mol ratio 26H 2O and CoCl6H 2The mixed aqueous solution of O carries out the spinel NiCo that coprecipitation method prepares median size 2 μ m 2O 4Powder, described coprecipitation method are meant two kinds and two or more solubilized metal-salt are formed undissolved compound and the method that from solution, is precipitated out is called coprecipitation method with highly basic (like sodium hydroxide etc.) or with other precipitation agent.Prepare 1: 2 NiCl of mol ratio at first earlier 26H 2O and CoCl6H 2The mixed aqueous solution of O is used 15wt% ammoniacal liquor (NH then 3H 2O) the pH value of adjustment mixed solution is 6～7, under continuous condition of stirring, in solution, slowly adds the oxalic acid (H of 80 ℃ 35wt% at last 2C 2O 42H 2O) aqueous solution through after leaving standstill, filter, washing, obtains oxalic acid precipitation thing (precursor); This precursor is placed on 100 ℃ of oven dryings, again this precursor is placed in the horse expense stove 300 ℃ of calcinings five hours, grind and obtain Powdered spinel NiCo 2O 4
To pass through the NiCo after the surface treatment then 2O 4Be dispersed in the Watter nickel-plating liquid with the aluminium powder form (Al powder) of median size 75 μ m, on Ni substrate, obtain Ni/ (Al+NiCo through composite electrodeposition 2O 4) composite deposite; Described composite electrodeposition is meant in certain plating bath; Add a certain amount of insoluble solid particle (general particle diameter is at 0.1～100 micrometer range); Constantly stirring is suspended in the plating bath solid particulate, and (like bath pH value, current density, temperature, stirring velocity etc.) make solid particulate deposit out with metal and form composite deposite under certain mode of deposition.Among the present invention, be meant in the Watter nickel-plating liquid, add NiCo 2O 4And aluminium powder form, make these solid particulates deposit out through stirring and form composite deposite with nickel.
At last composite deposite being immersed in the concentrated NaOH solution precipitation falls aluminium and obtains Ni/NiCo 2O 4Porous composite electrode.Wherein contain in every liter of Watter nickel-plating liquid: NiSO 46H 2O300g/L, NiCl 26H 2O 50g/L, H 3BO 3Al powder add-on is 50g/L, NiCo in 40g/L, tensio-active agent 1g/L, the plating bath 2O 4Add-on is 60g/L, then adding distil water to 1 liter.The composite electrodeposition condition of above-mentioned electroplate liquid is: 45 ℃ of the bath temperatures of operation, stirring velocity n=400r/min, plating bath pH=6.0, cathode current density jk=80mA/cm 2Adopt above-mentioned electroplate liquid and mode of deposition gained Ni/ (Al+NiCo 2O 4) Al quality percentage composition is 0.44% in the composite deposite, NiCo 2O 4The quality percentage composition is 6.07%.
Embodiment 2
A kind of alkaline medium of present embodiment is analysed oxygen and is used Ni/NiCo 2O 4The preparation method of porous composite electrode comprises the steps: at first to adopt 1: 2 NiCl of mol ratio 26H 2O and CoCl6H 2The mixed aqueous solution of O carries out the spinel NiCo that coprecipitation method prepares median size 2 μ m 2O 4Powder, described coprecipitation method are meant two kinds and two or more solubilized metal-salt are formed undissolved compound and the method that from solution, is precipitated out is called coprecipitation method with highly basic (like sodium hydroxide etc.) or with other precipitation agent.Prepare 1: 2 NiCl of mol ratio at first earlier 26H 2O and CoCl6H 2The mixed aqueous solution of O is used 15wt% ammoniacal liquor (NH then 3H 2O) the pH value of adjustment mixed solution is 6～7, under continuous condition of stirring, in solution, slowly adds the oxalic acid (H of 80 ℃ 35wt% at last 2C 2O 42H 2O) aqueous solution through after leaving standstill, filter, washing, obtains oxalic acid precipitation thing (precursor); This precursor is placed on 100 ℃ of oven dryings, again this precursor is placed in the horse expense stove 300 ℃ of calcinings five hours, grind and obtain Powdered spinel NiCo 2O 4
To pass through the NiCo after the surface treatment then 2O 4Be dispersed in the Watter nickel-plating liquid with the aluminium powder form (Al powder) of median size 75 μ m, on Ni substrate, obtain Ni/ (Al+NiCo through composite electrodeposition 2O 4) composite deposite; Described composite electrodeposition is meant in certain plating bath; Add a certain amount of insoluble solid particle (general particle diameter is at 0.1～100 micrometer range); Constantly stirring is suspended in the plating bath solid particulate, and (like bath pH value, current density, temperature, stirring velocity etc.) make solid particulate deposit out with metal and form composite deposite under certain mode of deposition.Among the present invention, be meant in the Watter nickel-plating liquid, add NiCo 2O 4And aluminium powder form, make these solid particulates deposit out through stirring and form composite deposite with nickel.
At last composite deposite being immersed in the concentrated NaOH solution precipitation falls aluminium and obtains Ni/NiCo 2O 4Porous composite electrode.Wherein contain in every liter of Watter nickel-plating liquid: NiSO 46H 2O300g/L, NiCl 26H 2O 50g/L, H 3BO 3Al powder add-on 50g/L, NiCo in 40g/L, tensio-active agent 1g/L, the plating bath 2O 4Add-on 60g/L, adding distil water to 1 liter then.The composite electrodeposition condition of above-mentioned electroplate liquid is: 45 ℃ of the bath temperatures of operation, stirring velocity n=400r/min, plating bath pH=6.4, cathode current density jk=80mA/cm 2Adopt above-mentioned electroplate liquid and mode of deposition gained Ni/ (Al+NiCo 2O 4) Al quality percentage composition is 1.28% in the composite deposite, NiCo 2O 4The quality percentage composition is 8.31%.
Embodiment 3
A kind of alkaline medium of present embodiment is analysed oxygen and is used Ni/NiCo 2O 4The preparation method of porous composite electrode comprises the steps: at first to adopt 1: 2 NiCl of mol ratio 26H 2O and CoCl6H 2The mixed aqueous solution of O carries out the spinel NiCo that coprecipitation method prepares median size 2 μ m 2O 4Powder, described coprecipitation method are meant two kinds and two or more solubilized metal-salt are formed undissolved compound and the method that from solution, is precipitated out is called coprecipitation method with highly basic (like sodium hydroxide etc.) or with other precipitation agent.Prepare 1: 2 NiCl of mol ratio at first earlier 26H 2O and CoCl6H 2The mixed aqueous solution of O is used 15wt% ammoniacal liquor (NH then 3H 2O) the pH value of adjustment mixed solution is 6～7, under continuous condition of stirring, in solution, slowly adds the oxalic acid (H of 80 ℃ 35wt% at last 2C 2O 42H 2O) aqueous solution through after leaving standstill, filter, washing, obtains oxalic acid precipitation thing (precursor); This precursor is placed on 100 ℃ of oven dryings, again this precursor is placed in the horse expense stove 300 ℃ of calcinings five hours, grind and obtain Powdered spinel NiCo 2O 4
To pass through the NiCo after the surface treatment then 2O 4Be dispersed in the Watter nickel-plating liquid with the aluminium powder form (Al powder) of median size 75 μ m, on Ni substrate, obtain Ni/ (Al+NiCo through composite electrodeposition 2O 4) composite deposite; Described composite electrodeposition is meant in certain plating bath; Add a certain amount of insoluble solid particle (general particle diameter is at 0.1～100 micrometer range); Constantly stirring is suspended in the plating bath solid particulate, and (like bath pH value, current density, temperature, stirring velocity etc.) make solid particulate deposit out with metal and form composite deposite under certain mode of deposition.Among the present invention, be meant in the Watter nickel-plating liquid, add NiCo 2O 4And aluminium powder form, make these solid particulates deposit out through stirring and form composite deposite with nickel.
At last composite deposite being immersed in the concentrated NaOH solution precipitation falls aluminium and obtains Ni/NiCo 2O 4Porous composite electrode.Wherein contain in every liter of Watter nickel-plating liquid: NiSO 46H 2O300g/L, NiCl 26H 2O 50g/L, H 3BO 340g/L, tensio-active agent 1g/L, wherein Al powder add-on 50g/L, NiCo in the plating bath 2O 4Add-on 60g/L, adding distil water to 1 liter then.The composite electrodeposition condition of above-mentioned electroplate liquid is: 45 ℃ of the bath temperatures of operation, stirring velocity n=400r/min, plating bath pH=6.8, cathode current density jk=80mA/cm 2Adopt above-mentioned electroplate liquid and mode of deposition gained Ni/ (Al+NiCo 2O 4) Al quality percentage composition is 0.49% in the composite deposite, NiCo 2O 4The quality percentage composition is 6.32%.
Embodiment 4
A kind of alkaline medium of present embodiment is analysed oxygen and is used Ni/NiCo 2O 4The preparation method of porous composite electrode comprises the steps: at first to adopt 1: 2 NiCl of mol ratio 26H 2O and CoCl6H 2The mixed aqueous solution of O carries out the spinel NiCo that coprecipitation method prepares median size 2 μ m 2O 4Powder, described coprecipitation method are meant two kinds and two or more solubilized metal-salt are formed undissolved compound and the method that from solution, is precipitated out is called coprecipitation method with highly basic (like sodium hydroxide etc.) or with other precipitation agent.Prepare 1: 2 NiCl of mol ratio at first earlier 26H 2O and CoCl6H 2The mixed aqueous solution of O is used 15wt% ammoniacal liquor (NH then 3H 2O) the pH value of adjustment mixed solution is 6～7, under continuous condition of stirring, in solution, slowly adds the oxalic acid (H of 80 ℃ 35wt% at last 2C 2O 42H 2O) aqueous solution through after leaving standstill, filter, washing, obtains oxalic acid precipitation thing (precursor); This precursor is placed on 100 ℃ of oven dryings, again this precursor is placed in the horse expense stove 300 ℃ of calcinings five hours, grind and obtain Powdered spinel NiCo 2O 4
To pass through the NiCo after the surface treatment then 2O 4Be dispersed in the Watter nickel-plating liquid with the aluminium powder form (Al powder) of median size 75 μ m, on Ni substrate, obtain Ni/ (Al+NiCo through composite electrodeposition 2O 4) composite deposite; Described composite electrodeposition is meant in certain plating bath; Add a certain amount of insoluble solid particle (general particle diameter is at 0.1～100 micrometer range); Constantly stirring is suspended in the plating bath solid particulate, and (like bath pH value, current density, temperature, stirring velocity etc.) make solid particulate deposit out with metal and form composite deposite under certain mode of deposition.Among the present invention, be meant in the Watter nickel-plating liquid, add NiCo 2O 4And aluminium powder form, make these solid particulates deposit out through stirring and form composite deposite with nickel.
At last composite deposite being immersed in the concentrated NaOH solution precipitation falls aluminium and obtains Ni/NiCo 2O 4Porous composite electrode.Wherein contain in every liter of Watter nickel-plating liquid: NiSO 46H 2O300g/L, NiCl 26H 2O 50g/L, H 3BO 3Al powder add-on 50g/L, NiCo in 40g/L, tensio-active agent 1g/L, the plating bath 2O 4Add-on 60g/L, adding distil water to 1 liter then.The composite electrodeposition condition of above-mentioned electroplate liquid is: 45 ℃ of the bath temperatures of operation, stirring velocity n=400r/min, plating bath pH=6.4, cathode current density jk=40mA/cm 2Adopt above-mentioned electroplate liquid and mode of deposition gained Ni/ (Al+NiCo 2O 4) Al quality percentage composition is 0.56% in the composite deposite, NiCo 2O 4The quality percentage composition is 5.16%.
Embodiment 5
A kind of alkaline medium of present embodiment is analysed oxygen and is used Ni/NiCo 2O 4The preparation method of porous composite electrode comprises the steps: at first to adopt 1: 2 NiCl of mol ratio 26H 2O and CoCl6H 2The mixed aqueous solution of O carries out the spinel NiCo that coprecipitation method prepares median size 2 μ m 2O 4Powder, described coprecipitation method are meant two kinds and two or more solubilized metal-salt are formed undissolved compound and the method that from solution, is precipitated out is called coprecipitation method with highly basic (like sodium hydroxide etc.) or with other precipitation agent.Prepare 1: 2 NiCl of mol ratio at first earlier 26H 2O and CoCl6H 2The mixed aqueous solution of O is used 15wt% ammoniacal liquor (NH then 3H 2O) the pH value of adjustment mixed solution is 6～7, under continuous condition of stirring, in solution, slowly adds the oxalic acid (H of 80 ℃ 35wt% at last 2C 2O 42H 2O) aqueous solution through after leaving standstill, filter, washing, obtains oxalic acid precipitation thing (precursor); This precursor is placed on 100 ℃ of oven dryings, again this precursor is placed in the horse expense stove 300 ℃ of calcinings five hours, grind and obtain Powdered spinel NiCo 2O 4
To pass through the NiCo after the surface treatment then 2O 4Be dispersed in the Watter nickel-plating liquid with the aluminium powder form (Al powder) of median size 75 μ m, on Ni substrate, obtain Ni/ (Al+NiCo through composite electrodeposition 2O 4) composite deposite; Described composite electrodeposition is meant in certain plating bath; Add a certain amount of insoluble solid particle (general particle diameter is at 0.1～100 micrometer range); Constantly stirring is suspended in the plating bath solid particulate, and (like bath pH value, current density, temperature, stirring velocity etc.) make solid particulate deposit out with metal and form composite deposite under certain mode of deposition.Among the present invention, be meant in the Watter nickel-plating liquid, add NiCo 2O 4And aluminium powder form, make these solid particulates deposit out through stirring and form composite deposite with nickel.
At last composite deposite being immersed in the concentrated NaOH solution precipitation falls aluminium and obtains Ni/NiCo 2O 4Porous composite electrode.Wherein contain in every liter of Watter nickel-plating liquid: NiSO 46H 2O300g/L, NiCl 26H 2O 50g/L, H 3BO 3Al powder add-on 50g/L, NiCo in 40g/L, tensio-active agent 1g/L, the plating bath 2O 4Add-on 60g/L, adding distil water to 1 liter then.The composite electrodeposition condition of above-mentioned electroplate liquid is: 45 ℃ of the bath temperatures of operation, stirring velocity n=400r/min, plating bath pH=6.4, cathode current density jk=120mA/cm 2Adopt above-mentioned electroplate liquid and mode of deposition gained Ni/ (Al+NiCo 2O 4) Al quality percentage composition is 0.63% in the composite deposite, NiCo 2O 4The quality percentage composition is 5.02%.
Embodiment 6
A kind of alkaline medium of present embodiment is analysed oxygen and is used Ni/NiCo 2O 4The preparation method of porous composite electrode comprises the steps: at first to adopt 1: 2 NiCl of mol ratio 26H 2O and CoCl6H 2The mixed aqueous solution of O carries out the spinel NiCo that coprecipitation method prepares median size 2 μ m 2O 4Powder, described coprecipitation method are meant two kinds and two or more solubilized metal-salt are formed undissolved compound and the method that from solution, is precipitated out is called coprecipitation method with highly basic (like sodium hydroxide etc.) or with other precipitation agent.Prepare 1: 2 NiCl of mol ratio at first earlier 26H 2O and CoCl6H 2The mixed aqueous solution of O is used 15wt% ammoniacal liquor (NH then 3H 2O) the pH value of adjustment mixed solution is 6～7, under continuous condition of stirring, in solution, slowly adds the oxalic acid (H of 80 ℃ 35wt% at last 2C 2O 42H 2O) aqueous solution through after leaving standstill, filter, washing, obtains oxalic acid precipitation thing (precursor); This precursor is placed on 100 ℃ of oven dryings, again this precursor is placed in the horse expense stove 300 ℃ of calcinings five hours, grind and obtain Powdered spinel NiCo 2O 4
To pass through the NiCo after the surface treatment then 2O 4Be dispersed in the Watter nickel-plating liquid with the aluminium powder form (Al powder) of median size 75 μ m, on Ni substrate, obtain Ni/ (Al+NiCo through composite electrodeposition 2O 4) composite deposite; Described composite electrodeposition is meant in certain plating bath; Add a certain amount of insoluble solid particle (general particle diameter is at 0.1～100 micrometer range); Constantly stirring is suspended in the plating bath solid particulate, and (like bath pH value, current density, temperature, stirring velocity etc.) make solid particulate deposit out with metal and form composite deposite under certain mode of deposition.Among the present invention, be meant in the Watter nickel-plating liquid, add NiCo 2O 4And aluminium powder form, make these solid particulates deposit out through stirring and form composite deposite with nickel.
At last composite deposite being immersed in the concentrated NaOH solution precipitation falls aluminium and obtains Ni/NiCo 2O 4Porous composite electrode.Wherein contain in every liter of Watter nickel-plating liquid: NiSO 46H 2O300g/L, NiCl 26H 2O 50g/L, H 3BO 3Al powder add-on 50g/L, NiCo in 40g/L, tensio-active agent 1g/L, the plating bath 2O 4Add-on 60g/L, adding distil water to 1 liter then.The composite electrodeposition condition of above-mentioned electroplate liquid is: 45 ℃ of the bath temperatures of operation, stirring velocity n=300r/min, plating bath pH=6.4, cathode current density jk=80mA/cm 2Adopt above-mentioned electroplate liquid and mode of deposition gained Ni/ (Al+NiCo 2O 4) Al quality percentage composition is 0.60% in the composite deposite, NiCo 2O 4The quality percentage composition is 7.92%.
Embodiment 7
A kind of alkaline medium of present embodiment is analysed oxygen and is used Ni/NiCo 2O 4The preparation method of porous composite electrode comprises the steps: at first to adopt 1: 2 NiCl of mol ratio 26H 2O and CoCl6H 2The mixed aqueous solution of O carries out the spinel NiCo that coprecipitation method prepares median size 2 μ m 2O 4Powder, described coprecipitation method are meant two kinds and two or more solubilized metal-salt are formed undissolved compound and the method that from solution, is precipitated out is called coprecipitation method with highly basic (like sodium hydroxide etc.) or with other precipitation agent.Prepare 1: 2 NiCl of mol ratio at first earlier 26H 2O and CoCl6H 2The mixed aqueous solution of O is used 15wt% ammoniacal liquor (NH then 3H 2O) the pH value of adjustment mixed solution is 6～7, under continuous condition of stirring, in solution, slowly adds the oxalic acid (H of 80 ℃ 35wt% at last 2C 2O 42H 2O) aqueous solution through after leaving standstill, filter, washing, obtains oxalic acid precipitation thing (precursor); This precursor is placed on 100 ℃ of oven dryings, again this precursor is placed in the horse expense stove 300 ℃ of calcinings five hours, grind and obtain Powdered spinel NiCo 2O 4
To pass through the NiCo after the surface treatment then 2O 4Be dispersed in the Watter nickel-plating liquid with the aluminium powder form (Al powder) of median size 75 μ m, on Ni substrate, obtain Ni/ (Al+NiCo through composite electrodeposition 2O 4) composite deposite; Described composite electrodeposition is meant in certain plating bath; Add a certain amount of insoluble solid particle (general particle diameter is at 0.1～100 micrometer range); Constantly stirring is suspended in the plating bath solid particulate, and (like bath pH value, current density, temperature, stirring velocity etc.) make solid particulate deposit out with metal and form composite deposite under certain mode of deposition.Among the present invention, be meant in the Watter nickel-plating liquid, add NiCo 2O 4And aluminium powder form, make these solid particulates deposit out through stirring and form composite deposite with nickel.
At last composite deposite being immersed in the concentrated NaOH solution precipitation falls aluminium and obtains Ni/NiCo 2O 4Porous composite electrode.Wherein contain in every liter of Watter nickel-plating liquid: NiSO 46H 2O300g/L, NiCl 26H 2O 50g/L, H 3BO 3Al powder add-on 50g/L, NiCo in 40g/L, tensio-active agent 1g/L, the plating bath 2O 4Add-on 60g/L, adding distil water to 1 liter then.The composite electrodeposition condition of above-mentioned electroplate liquid is: 45 ℃ of the bath temperatures of operation, stirring velocity n=500r/min, plating bath pH=6.4, cathode current density jk=80mA/cm 2Adopt above-mentioned electroplate liquid and mode of deposition gained Ni/ (Al+NiCo 2O 4) Al quality percentage composition is 0.52% in the composite deposite, NiCo 2O 4The quality percentage composition is 5.30%.
Embodiment 8
A kind of alkaline medium of present embodiment is analysed oxygen and is used Ni/NiCo 2O 4The preparation method of porous composite electrode comprises the steps: at first to adopt 1: 2 NiCl of mol ratio 26H 2O and CoCl6H 2The mixed aqueous solution of O carries out the spinel NiCo that coprecipitation method prepares median size 2 μ m 2O 4Powder, described coprecipitation method are meant two kinds and two or more solubilized metal-salt are formed undissolved compound and the method that from solution, is precipitated out is called coprecipitation method with highly basic (like sodium hydroxide etc.) or with other precipitation agent.Prepare 1: 2 NiCl of mol ratio at first earlier 26H 2O and CoCl6H 2The mixed aqueous solution of O is used 15wt% ammoniacal liquor (NH then 3H 2O) the pH value of adjustment mixed solution is 6～7, under continuous condition of stirring, in solution, slowly adds the oxalic acid (H of 80 ℃ 35wt% at last 2C 2O 42H 2O) aqueous solution through after leaving standstill, filter, washing, obtains oxalic acid precipitation thing (precursor); This precursor is placed on 100 ℃ of oven dryings, again this precursor is placed in the horse expense stove 300 ℃ of calcinings five hours, grind and obtain Powdered spinel NiCo 2O 4
To pass through the NiCo after the surface treatment then 2O 4Be dispersed in the Watter nickel-plating liquid with the aluminium powder form (Al powder) of median size 75 μ m, on Ni substrate, obtain Ni/ (Al+NiCo through composite electrodeposition 2O 4) composite deposite; Described composite electrodeposition is meant in certain plating bath; Add a certain amount of insoluble solid particle (general particle diameter is at 0.1～100 micrometer range); Constantly stirring is suspended in the plating bath solid particulate, and (like bath pH value, current density, temperature, stirring velocity etc.) make solid particulate deposit out with metal and form composite deposite under certain mode of deposition.Among the present invention, be meant in the Watter nickel-plating liquid, add NiCo 2O 4And aluminium powder form, make these solid particulates deposit out through stirring and form composite deposite with nickel.
At last composite deposite being immersed in the concentrated NaOH solution precipitation falls aluminium and obtains Ni/NiCo 2O 4Porous composite electrode.Wherein contain in every liter of Watter nickel-plating liquid: NiSO 46H 2O300g/L, NiCl 26H 2O 50g/L, H 3BO 3Al powder add-on 50g/L, NiCo in 40g/L, tensio-active agent 1g/L, the plating bath 2O 4Add-on 40g/L, adding distil water to 1 liter then.The composite electrodeposition condition of above-mentioned electroplate liquid is: 45 ℃ of the bath temperatures of operation, stirring velocity n=400r/min, plating bath pH=6.4, cathode current density jk=80mA/cm 2Adopt above-mentioned electroplate liquid and mode of deposition gained Ni/ (Al+NiCo 2O 4) Al quality percentage composition is 0.49% in the composite deposite, NiCo 2O 4The quality percentage composition is 5.16%.
Embodiment 9
A kind of alkaline medium of present embodiment is analysed oxygen and is used Ni/NiCo 2O 4The preparation method of porous composite electrode comprises the steps: at first to adopt 1: 2 NiCl of mol ratio 26H 2O and CoCl6H 2The mixed aqueous solution of O carries out the spinel NiCo that coprecipitation method prepares median size 2 μ m 2O 4Powder, described coprecipitation method are meant two kinds and two or more solubilized metal-salt are formed undissolved compound and the method that from solution, is precipitated out is called coprecipitation method with highly basic (like sodium hydroxide etc.) or with other precipitation agent.Prepare 1: 2 NiCl of mol ratio at first earlier 26H 2O and CoCl6H 2The mixed aqueous solution of O is used 15wt% ammoniacal liquor (NH then 3H 2O) the pH value of adjustment mixed solution is 6～7, under continuous condition of stirring, in solution, slowly adds the oxalic acid (H of 80 ℃ 35wt% at last 2C 2O 42H 2O) aqueous solution through after leaving standstill, filter, washing, obtains oxalic acid precipitation thing (precursor); This precursor is placed on 100 ℃ of oven dryings, again this precursor is placed in the horse expense stove 300 ℃ of calcinings five hours, grind and obtain Powdered spinel NiCo 2O 4
To pass through the NiCo after the surface treatment then 2O 4Be dispersed in the Watter nickel-plating liquid with the aluminium powder form (Al powder) of median size 75 μ m, on Ni substrate, obtain Ni/ (Al+NiCo through composite electrodeposition 2O 4) composite deposite; Described composite electrodeposition is meant in certain plating bath; Add a certain amount of insoluble solid particle (general particle diameter is at 0.1～100 micrometer range); Constantly stirring is suspended in the plating bath solid particulate, and (like bath pH value, current density, temperature, stirring velocity etc.) make solid particulate deposit out with metal and form composite deposite under certain mode of deposition.Among the present invention, be meant in the Watter nickel-plating liquid, add NiCo 2O 4And aluminium powder form, make these solid particulates deposit out through stirring and form composite deposite with nickel.
At last composite deposite being immersed in the concentrated NaOH solution precipitation falls aluminium and obtains Ni/NiCo 2O 4Porous composite electrode.Wherein contain in every liter of Watter nickel-plating liquid: NiSO 46H 2O300g/L, NiCl 26H 2O 50g/L, H 3BO 3Al powder add-on 50g/L, NiCo in 40g/L, tensio-active agent 1g/L, the plating bath 2O 4Add-on 80g/L, adding distil water to 1 liter then.The composite electrodeposition condition of above-mentioned electroplate liquid is: 45 ℃ of the bath temperatures of operation, stirring velocity n=400r/min, plating bath pH=6.4, cathode current density jk=80mA/cm 2Adopt above-mentioned electroplate liquid and mode of deposition gained Ni/ (Al+NiCo 2O 4) Al quality percentage composition is 1.29% in the composite deposite, NiCo 2O 4The quality percentage composition is 8.35%.
In sum, composite electrodeposition prepares Ni/NiCo 2O 4The optimum process condition of porous composite deposite (sample 1) is: Al powder add-on 50g/L in the plating bath, NiCo 2O 4Add-on 60g/L, plating bath pH=6.4, cathode current density jk=80mA/cm 2, plating temperature T=45 ℃, magnetic agitation speed n=400r/min.Gained Ni/ (Al+NiCo with this understanding 2O 4) NiCo in the composite deposite 2O 4The quality percentage composition be 8.31%, the quality percentage composition of Al is 1.28% (specifically seeing embodiment 2).
If in the Watter plating bath, only add spinel NiCo during composite electrodeposition 2O 4Powder does not add aluminium powder form, the Ni/NiCo of composite deposition preparation 2O 4The concrete prescription and the condition of composite deposite (sample 2) are following: contain in every liter of solution: NiSO 46H 2O 300g/L, NiCl 26H 2O 50g/L, H 3BO 3NiCo in 40g/L, tensio-active agent 1g/L, the plating bath 2O 4Powder (median size 2 μ m) add-on 60g/L, surplus is a zero(ppm) water.
The present invention uses the pure nickel plate to make anode, and annode area is more than the twice of cathode area.
The mode of deposition of above-mentioned electroplate liquid is: 45 ℃ of the bath temperatures of operation, stirring velocity n=400r/min, plating bath pH=6.4, cathode current density jk=80mA/cm 2
The stereoscan photograph (amplifying 3000 times) of above sample 1 and sample 2 is respectively like Fig. 1, shown in Figure 2;
It is thus clear that Ni/NiCo 2O 4Many spaces are arranged, so Ni/NiCo in the porous composite deposite 2O 4The specific surface area of porous composite deposite is for to make Ni/NiCo with under the condition 2O 4800 times of composite deposite.Sample 1 and 2 with above-mentioned preparation is anode (apparent area of two electrodes is identical) respectively, shows (electrolytic condition is identical), Ni/NiCo at 25 ℃ with the long-time potentiostatic deposition of 30wt%NaOH solution 2O 4The current ratio Ni/NiCo of porous composite electrode 2O 4Combined electrode is big.Electrolysis is analysed oxygen experiment and is shown Ni/NiCo under this condition equally 2O 4The electro catalytic activity of porous composite electrode is analysed the oxygen electrode excellence with stability than traditional application type.

Claims (5)

1. an alkaline medium is analysed oxygen and is used Ni/NiCo 2O 4The preparation method of porous composite electrode is characterized in that comprising the steps: at first to adopt 1: 2 NiCl of mol ratio 26H 2O and CoCl6H 2The mixed aqueous solution of O carries out the spinel NiCo that coprecipitation method prepares median size 2 μ m 2O 4Powder will pass through the NiCo after the surface treatment then 2O 4Be dispersed in the Watter nickel-plating liquid with the aluminium powder form of median size 75 μ m, on Ni substrate, obtain Ni/ (Al+NiCo through composite electrodeposition 2O 4) composite deposite, at last composite deposite is immersed in the concentrated NaOH solution precipitation and falls aluminium and obtain Ni/NiCo 2O 4Porous composite electrode.
2. a kind of alkaline medium as claimed in claim 1 is analysed oxygen and is used Ni/NiCo 2O 4The preparation method of porous composite electrode is characterized in that: described Watter nickel-plating liquid prescription is: contain in every liter of solution: NiSO 46H 2O 300g/L, NiCl 26H 2O 50g/L, H 3BO 340g/L, tensio-active agent 1g/L; Wherein said NiCo 2O 4With the aluminium powder form add-on be: the NiCo of median size 75 μ m aluminium powder form 50g/L, median size 2 μ m 2O 4Powder 40～80g/L, adding distil water to 1 liter then.
3. according to claim 1 or claim 2 a kind of alkaline medium is analysed oxygen and is used Ni/NiCo 2O 4The preparation method of porous composite electrode is characterized in that: described aluminium powder form will after the washing, could add in the plating bath and use earlier through the weak base oil removing 10min of pH=8 before adding then.
4. a kind of alkaline medium as claimed in claim 1 is analysed oxygen and is used Ni/NiCo 2O 4The preparation method of porous composite electrode is characterized in that: the composite electrodeposition condition of described electroplate liquid is: 45 ℃ of bath temperatures, stirring velocity n=300～500r/min, plating bath pH are 6.0～6.8, cathode current density jk=40～120mA/cm 2
5. analyse oxygen like claim 1 or 4 described a kind of alkaline mediums and use Ni/NiCo 2O 4The preparation method of porous composite electrode is characterized in that: described composite electrodeposition uses the pure nickel plate to make anode, and annode area is more than the twice of cathode area.
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CN103526273A (en) * 2013-09-27 2014-01-22 华侨大学 Novel alkaline zincate electrogalvanizing anode and preparation method thereof
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