CN103825003A - Three-dimensional porous Co3O4/Pt/Ni combined electrode, its preparation method and its application - Google Patents

Three-dimensional porous Co3O4/Pt/Ni combined electrode, its preparation method and its application Download PDF

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CN103825003A
CN103825003A CN201410068658.6A CN201410068658A CN103825003A CN 103825003 A CN103825003 A CN 103825003A CN 201410068658 A CN201410068658 A CN 201410068658A CN 103825003 A CN103825003 A CN 103825003A
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dimensional porous
ptcl
combination electrode
hydrate
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CN103825003B (en
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赵新兵
曹静仪
谢健
刘双宇
曹高劭
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Zhejiang University ZJU
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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
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/8605—Porous electrodes
    • 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
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/88—Processes of manufacture
    • H01M4/8825—Methods for deposition of the catalytic active composition
    • 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
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H01M4/9016—Oxides, hydroxides or oxygenated metallic salts
    • 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
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H01M4/9075—Catalytic material supported on carriers, e.g. powder carriers
    • 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
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H01M4/92—Metals of platinum group
    • H01M4/921—Alloys or mixtures with metallic elements
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M12/00—Hybrid cells; Manufacture thereof
    • H01M12/08—Hybrid cells; Manufacture thereof composed of a half-cell of a fuel-cell type and a half-cell of the secondary-cell type

Abstract

The invention discloses a three-dimensional porous Co3O4/Pt/Ni combined electrode, which takes three-dimensional porous foamed nickel as a matrix, a Co3O4 nano wire is directly grown on the matrix, and the nano Pt particles are directly grown on the Co3O4 nano wire. The invention also discloses a preparation method and an application of the Co3O4/Pt/Ni combined electrode, the preparation method has the advantages of simple preparation technology, low energy consumption and low cost, and is suitable for large scale industrial production. Due to a special three dimensional porous structure and the concerted catalysis effect of the Co3O4 nano wire and the Pt nano particles, the prepared Co3O4/Pt/Ni combined electrode has the advantages of high capacity, low overpotential and high cycle stability, the Co3O4/Pt/Ni combined electrode is used in a lithium-air cell air electrode, so that the electrochemistry performance of the lithium-air cell is increased, the overpotential is reduced, and the cycle stability is increased.

Description

A kind of three-dimensional porous Co 3o 4/ Pt/Ni combination electrode and its preparation method and application
Technical field
The present invention relates to lithium-empty battery and use combination electrode field, be specifically related to a kind of three-dimensional porous Co 3o 4/ Pt/Ni combination electrode and its preparation method and application.
Background technology
Lithium-empty battery is a kind of take lithium metal as negative pole, and air (or oxygen) is anodal battery, and lithium ion conductor is electrolytical Novel energy storage apparatus.The theoretical energy density of lithium-empty battery does not comprise O up to 11680Wh/kg( 2if comprise O 2, be 5200Wh/kg).Consider the weight of catalyst, electrolyte, battery packages etc., the reality of lithium-empty battery can obtain energy density and be about 1700Wh/kg, this value can be suitable with the energy density of gasoline, far above the energy density of nickel-hydrogen (50Wh/kg), lithium ion (160Wh/kg), lithium-sulphur (370Wh/kg), zinc-sky (350Wh/kg) battery.
Lithium-empty battery is due to its high energy density, has important application prospect in fields such as the redundant electrical powers of Vehicular dynamic battery and electrical network.Just because of lithium-empty battery has very important application prospect, some leading companys and scientific research institution have started the research of the empty battery of lithium in the world.As American I BM company has started " Battery500Project " project, the final goal of this plan be by lithium-empty battery for automobile, in this project, " 500 " represent each Rechargeable vehicle travel 500 miles (800 kilometers).
The factor that affects lithium-empty battery performance is a lot, but the composition and structure of catalyst is key factor.Recently, various new catalysts are as noble metal M(M=Ru, Au, Pd, Pt), PtAu, MnO 2, MnO 2/ Ti, MnO 2/ Pd, MoN/ Graphene, MnCo 2o 4/ Graphenes etc. are developed.For catalyst component, with respect to metal oxide (as Fe 2o 3, MnO 2) catalyst, noble metal catalyst has its unique performance advantage, is the extremely ideal catalyst of lithium-empty battery air.But noble metal catalyst cost compare is high, the use amount that therefore reduces noble metal is the trend of catalyst development from now on, on metal oxide, is wherein one of method wherein by noble-metal-supported.
Wang Chong etc. (Wang Chong, Wang Dianlong, Wang Qiuming, Chen Huanjun. three-dimensional structure foam Co 3o 4preparation and chemical property, SCI, in October, 2010,2058-2062 page .) by electrochemical deposition method plated metal cobalt layer on three-dimensional structure nickel foam substrate, utilize phase oxidative method to prepare three-dimensional structure foam Co 3o 4negative pole, and by discharging and recharging the chemical property of having studied electrode with the method such as cyclic voltammetric and electrochemical impedance, result shows, three-dimensional foam structure has improved Co 3o 4circulation volume retention and the high rate performance of electrode.
Summary of the invention
The invention provides a kind of three-dimensional porous Co 3o 4/ Pt/Ni combination electrode and its preparation method and application, preparation technology is simple, and energy consumption is low, cost is low, is suitable for large-scale industrial production; The Co preparing 3o 4/ Pt/Ni combination electrode has high power capacity, low overpotential and high cyclical stability, is applied to, in lithium-empty battery air electrode, can be used to improve the chemical property of lithium-empty battery, particularly reduces overpotential and improves cyclical stability.
The invention discloses a kind of three-dimensional porous Co 3o 4/ Pt/Ni combination electrode, take three-dimensional porous nickel foam as matrix, direct growth Co on described matrix 3o 4nano wire, described Co 3o 4direct growth nanometer Pt particle on nano wire.
The present invention is take three-dimensional porous nickel foam as matrix, direct growth Co on matrix 3o 4nano wire and nanometer Pt particle.Co 3o 4nano wire and Pt nano particle have concerted catalysis effect, and mechanism is as follows: Co 3o 4although self there is good catalytic action, i.e. discharging product Li 2o 2more easily form and decompose on its surface, thering is lower overpotential, but the Li forming 2o 2particle is larger, is difficult for decomposing when charging, causes charging overpotential higher; Pt adds except also to Li 2o 2formation and decomposition play outside catalytic action, due to Pt absorption O 2energy force rate Co 3o 4can change Li by force, 2o 2crystallization behavior, reduce Li 2o 2size, make Li in when charging 2o 2more easily decompose, can further reduce charging overpotential.
Described direct growth refers under hydrothermal condition, Co 3o 4nano wire is directly grown on the skeleton of nickel foam; In contrast, non-direct growth refers to the pre-synthesis Co of hydro thermal method 3o 4nano wire, then by Co 3o 4in organic solvent, mix, stir into slurry with binding agent, then slurry is coated in nickel foam.Pt direct growth refers at Co 3o 4when being directly grown in nickel foam, Pt is carried on Co 3o 4on nano wire, not at growth Co 3o 4after nano wire, then use (as adopted binding agent) someway that Pt is adhered to Co 3o 4on nano wire.
As preferably, described Co 3o 4co in/Pt/Ni combination electrode 3o 4bearing capacity be 0.2～1mg/cm 2.Co 3o 4bearing capacity very few, catalytic effect is undesirable; Bearing capacity is too much, and part material is not utilized and causes the waste of material, and simultaneously because catalytic reaction generally occurs over just on the material of electrode surface, and bearing capacity too much also can cause the decline of specific capacity.
As preferably, described Co 3o 4nanowire diameter is 50～100nm, and length is 1～3 μ m.Co 3o 4the meticulous load that is unfavorable for Pt nano particle of nanowire diameter; Spend thick or too short being unfavorable for forms space between nano wire, and then is unfavorable for diffusion and the Li of lithium ion and oxygen 2o 2deposition; Nano wire is long easily causes fracture to peel off from electrode.
As preferably, described Co 3o 4in/Pt/Ni combination electrode, the bearing capacity of Pt is 0.2～1.0mg/cm 2, further preferred, the bearing capacity of described Pt is 0.4～0.8mg/cm 2.The addition of Pt is too low, changes Li 2o 2crystallization behavior ability a little less than, concerted catalysis effect is undesirable.And addition is too high, Co on the one hand 3o 4the ratio that surface is covered by Pt is just higher, affects Co 3o 4catalytic action, too much Pt adds membership and causes Pt particle agglomeration on the other hand, because catalytic action Pt mainly occurs on surface, must cause the reduction of the utilization ratio of Pt; In addition, because battery capacity and Pt addition do not have linear relationship, the too much Pt that adds can cause the decline of specific capacity and the increase of catalyst cost, and therefore, it is more reasonable that the content of Pt is controlled in above-mentioned scope.
The diameter of described Pt particle is 5～10nm.
The invention also discloses described three-dimensional porous Co 3o 4the preparation method of/Pt/Ni combination electrode, comprises the following steps:
(1) soluble-salt of divalence Co and urea are dissolved in to deionized water, stir and obtain solution I, Co in described solution I 2+concentration is 0.01～0.05mol/L; To the soluble compound that adds platiniferous in solution I, continue to stir, obtain solution II;
Described urea and Co 2+mol ratio be 1～5;
The soluble compound of described platiniferous and Co 2+mol ratio be 0.01～0.05;
(2) three-dimensional porous nickel foam is immersed in solution II, be incubated 5～10h at 100～160 ℃, then obtain load through washing, after dry and have the three-dimensional porous nickel foam of cobalt hydroxide/Pt;
(3) load that step (2) obtains has the three-dimensional porous nickel foam of cobalt hydroxide/Pt after roasting 2～6h at 300～600 ℃, coolingly obtains described Co 3o 4/ Pt/Ni combination electrode.
As preferably, soluble compound and the Co of the described platiniferous of step (1) 2+mol ratio be 0.01～0.025.
As preferably, the described holding temperature of step (2) is 110～130 ℃, and the time is 5～8h; The described sintering temperature of step (3) is 400～500 ℃, and the time is 2～4h.
Described cooling temperature does not have strict restriction, is operating as master with suitable, generally can be cooled to the ambient temperature of 15 ℃～30 ℃.
As preferably, the soluble-salt of described divalence Co has CoSO 4, CoSO 4hydrate, CoCl 2, CoCl 2hydrate, Co (NO 3) 2or Co (NO 3) 2hydrate.
As preferably, the soluble compound of described platiniferous has H 2ptCl 6, H 2ptCl 6hydrate, K 2ptCl 6, K 2ptCl 6hydrate, (NH 4) 2ptCl 6, (NH 4) 2ptCl 6hydrate, H 2ptCl 4, H 2ptCl 4hydrate, K 2ptCl 4, K 2ptCl 4hydrate, (NH 4) 2ptCl 4or (NH 4) 2ptCl 4hydrate.
The invention also discloses described three-dimensional porous Co 3o 4the application of/Pt/Ni combination electrode in the air electrode as lithium-empty battery.
Compared with prior art, tool of the present invention has the following advantages:
1, Co in the three-dimensional porous combination electrode that prepared by the present invention 3o 4be and be directly grown on nickel foam substrate with Pt, without other conductive agents and binding agent, have that technique is simple, cost is low, the cycle is short, energy consumption is low and the advantage such as applicable suitability for industrialized production;
2, Co in the three-dimensional porous combination electrode that prepared by the present invention 3o 4nano wire and Pt nano particle have concerted catalysis effect, are conducive to the raising of catalytic performance, thereby effectively reduce the overpotential of lithium-empty battery;
3, compared with traditional electrode slurry coating process, catalyst direct growth method can keep the original three-dimensional porous structure of nickel foam, this structure is conducive to the transmission of oxygen, the deposition of the wetting and discharging product of electrode, thereby the cyclical stability of raising lithium-empty battery.
Accompanying drawing explanation
Fig. 1 is three-dimensional porous Co prepared by embodiment 1 3o 4the X-ray diffractogram of/Pt/Ni combination electrode;
Fig. 2 is three-dimensional porous Co prepared by embodiment 1 3o 4the low power stereoscan photograph of/Pt/Ni combination electrode;
Fig. 3 is three-dimensional porous Co prepared by embodiment 1 3o 4the high power stereoscan photograph of/Pt/Ni combination electrode;
Fig. 4 is three-dimensional porous Co prepared by embodiment 1 3o 4the transmission electron microscope photo of/Pt/Ni combination electrode;
Fig. 5 is the three-dimensional porous Co preparing with embodiment 1 3o 4/ Pt/Ni combination electrode is as the charging and discharging curve figure of anodal lithium-empty battery;
Fig. 6 is the three-dimensional porous Co preparing with comparative example 3o 4/ Ni electrode is as the charging and discharging curve figure of anodal lithium-empty battery.
Embodiment
Embodiment 1
By Co (NO 3) 26H 2(mole is Co for O and urea 2+2.5 times) be dissolved in deionized water, stir, preparation with Co 2+the solution that meter concentration is 0.013mol/L, stirs; Add again H 2ptCl 66H 2o(addition is Co 2+mole 0.025), continue stir.Using three-dimensional porous nickel foam as matrix, immerse above-mentioned solution, be transferred to again in reactor, after airtight, in the baking oven of 120 ℃, be incubated 6 hours, then rinse for several times with deionized water and absolute alcohol, after 12 hours, obtain being carried on the cobalt hydroxide/Pt in nickel foam the baking oven vacuumizes of 60 ℃; By the roasting 2 hours at 400 ℃ in air of the above-mentioned nickel foam that is loaded with cobalt hydroxide/Pt, be then cooled to room temperature and obtain being carried on the Co in nickel foam 3o 4/ Pt electrode, wherein Co 3o 4bearing capacity be 0.36mg/cm 2, the bearing capacity of Pt is 0.54mg/cm 2.
Co prepared by the present embodiment 3o 4x ray diffracting spectrum, ESEM and the transmission electron microscope photo of/Pt/Ni combination electrode are shown in respectively Fig. 1～4.In Fig. 1, the diffraction maximum of X ray all can be summed up as nickel foam substrate, Co 3o 4and Pt.Fig. 2 and Fig. 3 are respectively Co 3o 4the low power of/Pt/Ni combination electrode and high power stereoscan photograph, from the known Co of photo 3o 4present nano thread structure, diameter is 50～100nm, and length is 1～3 μ m, and is carried on nickel foam substrate.The transmission electron microscope photo of Fig. 4 shows, Pt nano particle is attached to Co 3o 4on nano wire, the diameter of Pt particle is 5～10nm.
The three-dimensional porous Co preparing with the present embodiment 3o 4/ Pt/Ni combination electrode is as positive pole, and take lithium metal as negative pole, polypropylene film (trade mark Celgard C380, Celgard company of the U.S.) is barrier film, LiClO 41,2-dimethoxy-ethane (DME) solution is electrolyte, in the glove box that is full of argon gas, assembles battery.After passing into 1 atmospheric oxygen, carry out charge-discharge test, gained chemical property is as shown in Figure 5.
Constant volume charge-discharge test (capacity limit is at 500mAh/g, current density 100mA/g, and voltage range 2～4.5V, wherein capacity and current density are all based on Co 3o 4gross mass with Pt) show, in 30 charge and discharge process, this lithium-empty battery all can keep stable circulation, and its electric discharge end current potential remains on 2.6V left and right, charging end current potential remains on 3.95V left and right, demonstrates lower polarization and good cyclical stability.
Comparative example
By Co (NO 3) 26H 2(mole is Co for O and urea 2+2.5 times) be dissolved in deionized water, stir, preparation with Co 2+the solution that meter concentration is 0.013mol/L, stirs.Using three-dimensional porous nickel foam as matrix, immerse above-mentioned solution, then be transferred in reactor, in the baking oven of 120 ℃, be incubated 6 hours after airtight, then rinse for several times with deionized water and absolute alcohol, after 12 hours, obtain being carried on the cobalt hydroxide in nickel foam the baking oven vacuumizes of 60 ℃; By the roasting 2 hours at 400 ℃ in air of the above-mentioned nickel foam that is loaded with cobalt hydroxide, be then cooled to room temperature and obtain being carried on the Co in nickel foam 3o 4electrode.
The three-dimensional porous Co preparing with this comparative example 3o 4/ Ni electrode is as positive pole, and take lithium metal as negative pole, polypropylene film (trade mark Celgard C380, Celgard company of the U.S.) is barrier film, LiClO 41,2-dimethoxy-ethane (DME) solution is electrolyte, in the glove box that is full of argon gas, assembles battery.Carry out electrochemical property test (under oxygen atmosphere), as shown in Figure 6, when this electrode charge and discharge cut-ff voltage is during at 2～4.5V, capacity, less than 250mAh/g, can not show a candle to three-dimensional porous Co to gained chemical property 3o 4/ Pt/Ni electrode.
Embodiment 2
By CoCl 26H 2(mole is Co for O and urea 2+1 times) be dissolved in deionized water, stir, preparation with Co 2+the solution that meter concentration is 0.025mol/L, stirs; Add again H 2ptCl 4(addition is Co 2+mole 0.01), continue stir.Using three-dimensional porous nickel foam as matrix, immerse above-mentioned solution, then be transferred in reactor, in the baking oven of 130 ℃, be incubated 5 hours after airtight, then rinse for several times with deionized water and absolute alcohol, after 12 hours, obtaining load the baking oven vacuumize of 60 ℃ has the nickel foam of cobalt hydroxide/Pt; By the above-mentioned nickel foam that is loaded with cobalt hydroxide/Pt roasting 3h at 450 ℃ in air, be then cooled to room temperature and obtain being carried on the Co in nickel foam 3o 4/ Pt electrode, wherein Co 3o 4bearing capacity be 0.69mg/cm 2, the bearing capacity of Pt is 0.43mg/cm 2.
The X ray diffracting spectrum of combination electrode prepared by the present embodiment, ESEM and transmission electron microscope and embodiment's 1 is similar.
The three-dimensional porous Co preparing with the present embodiment 3o 4/ Pt/Ni combination electrode is as positive pole, and take lithium metal as negative pole, polypropylene film (trade mark Celgard C380, Celgard company of the U.S.) is barrier film, LiClO 41,2-dimethoxy-ethane (DME) solution is electrolyte, in the glove box that is full of argon gas, assembles battery.After passing into 1 atmospheric oxygen, carry out charge-discharge test.
Constant volume charge-discharge test (capacity limit is at 500mAh/g, current density 100mA/g, and voltage range 2V～4.5V, wherein capacity and current density are all based on Co 3o 4gross mass with Pt) show, in 30 charge and discharge process, this lithium-empty battery all can keep stable circulation.Its end current potential that discharges remains on 2.5V left and right, and charging end current potential remains on 4.10V left and right, demonstrates lower polarization and good cyclical stability.
Embodiment 3
By CoCl 26H 2(mole is Co for O and urea 2+2 times) be dissolved in deionized water, stir, preparation with Co 2+the solution that meter concentration is 0.05mol/L, stirs; Add again K 2ptCl 6(addition is Co 2+mole 0.01), continue stir.Using three-dimensional porous nickel foam as matrix, immerse above-mentioned solution, then be transferred in reactor, in the baking oven of 110 ℃, be incubated 8 hours after airtight, then rinse for several times with deionized water and absolute alcohol, after 12 hours, obtaining load the baking oven vacuumize of 60 ℃ has the nickel foam of cobalt hydroxide/Pt; By the roasting 2 hours at 500 ℃ in air of the above-mentioned nickel foam that is loaded with cobalt hydroxide/Pt, be then cooled to room temperature and obtain being carried on the Co in nickel foam 3o 4/ Pt electrode, wherein Co 3o 4bearing capacity be 0.95mg/cm 2, the bearing capacity of Pt is 0.80mg/cm 2.
The X ray diffracting spectrum of combination electrode prepared by the present embodiment, ESEM and transmission electron microscope and embodiment's 1 is similar.
The three-dimensional porous Co preparing with the present embodiment 3o 4/ Pt/Ni combination electrode is as positive pole, and take lithium metal as negative pole, polypropylene film (trade mark Celgard C380, Celgard company of the U.S.) is barrier film, LiClO 41,2-dimethoxy-ethane (DME) solution is electrolyte, in the glove box that is full of argon gas, assembles battery.After passing into 1 atmospheric oxygen, carry out charge-discharge test.
Constant volume charge-discharge test (capacity limit is at 500mAh/g, current density 100mA/g, and voltage range 2V～4.5V, wherein capacity and current density are all based on Co 3o 4gross mass with Pt) show, in 30 charge and discharge process, this lithium-empty battery all can keep stable circulation.Its end current potential that discharges remains on 2.55V left and right, and charging end current potential remains on 4.05V left and right, demonstrates lower polarization and good cyclical stability.
Embodiment 4
By CoSO 47H 2(mole is Co for O and urea 2+5 times) be dissolved in deionized water, stir, preparation with Co 2+the solution that meter concentration is 0.01mol/L, stirs; Add again (NH 4) 2ptCl 6(addition is Co 2+mole 0.01), continue stir.Using three-dimensional porous nickel foam as matrix, immerse above-mentioned solution, be transferred to again in reactor, after airtight, in the baking oven of 120 ℃, be incubated 8 hours, then rinse for several times with deionized water and absolute alcohol, after 12 hours, obtain load and be loaded with the nickel foam of cobalt hydroxide/Pt the baking oven vacuumizes of 60 ℃; By the roasting 4 hours at 400 ℃ in air of the above-mentioned nickel foam that is loaded with cobalt hydroxide/Pt, be then cooled to room temperature and obtain being carried on the Co in nickel foam 3o 4/ Pt electrode, wherein Co 3o 4bearing capacity be 0.28mg/cm 2, the bearing capacity of Pt is 0.48mg/cm 2.
The X ray diffracting spectrum of combination electrode prepared by the present embodiment, ESEM and transmission electron microscope and embodiment's 1 is similar.
The three-dimensional porous Co preparing with the present embodiment 3o 4/ Pt/Ni combination electrode is as positive pole, and take lithium metal as negative pole, polypropylene film (trade mark Celgard C380, Celgard company of the U.S.) is barrier film, LiClO 41,2-dimethoxy-ethane (DME) solution is electrolyte, in the glove box that is full of argon gas, assembles battery.After passing into 1 atmospheric oxygen, carry out charge-discharge test.
Constant volume charge-discharge test (capacity limit is at 500mAh/g, current density 100mA/g, and voltage range 2V～4.5V, wherein capacity and current density are all based on Co 3o 4gross mass with Pt) show, in 30 charge and discharge process, this lithium-empty battery all can keep stable circulation.Its end current potential that discharges remains on 2.65V left and right, and charging end current potential remains on 4.00V left and right, demonstrates lower polarization and good cyclical stability.
Embodiment 5
Three-dimensional porous Co in the present embodiment 3o 4the parameter that the preparation process of/Pt/Ni combination electrode relates to is identical with embodiment 4, and difference is (NH 4) 2ptCl 6addition is Co 2+0.02 of mole, the Co obtaining 3o 4bearing capacity be 0.28mg/cm 2, the bearing capacity of Pt is 0.93mg/cm 2.
The X ray diffracting spectrum of combination electrode prepared by the present embodiment, ESEM and transmission electron microscope and embodiment's 1 is similar.
The three-dimensional porous Co preparing with the present embodiment 3o 4/ Pt/Ni combination electrode is as positive pole, and take lithium metal as negative pole, polypropylene film (trade mark Celgard C380, Celgard company of the U.S.) is barrier film, LiClO 41,2-dimethoxy-ethane (DME) solution is electrolyte, in the glove box that is full of argon gas, assembles battery.After passing into 1 atmospheric oxygen, carry out charge-discharge test.
Constant volume charge-discharge test (capacity limit is at 500mAh/g, current density 100mA/g, and voltage range 2V～4.5V, wherein capacity and current density are all based on Co 3o 4gross mass with Pt) show, in 30 charge and discharge process, this lithium-empty battery all can keep stable circulation.Its electric discharge end current potential remains on 2.47V left and right, and charging end current potential remains on 4.12V left and right, and compared with embodiment 4, polarization increases, and Pt addition is too high can affect the empty battery performance of lithium.
Embodiment 6
The three-dimensional porous Co of the present embodiment 3o 4the parameter that the preparation process of/Pt/Ni combination electrode relates to is identical with embodiment 4, and difference is (NH 4) 2ptCl 6addition is Co 2+0.005 of mole, the Co obtaining 3o 4bearing capacity be 0.28mg/cm 2, the bearing capacity of Pt is 0.22mg/cm 2.
The X ray diffracting spectrum of combination electrode prepared by the present embodiment, ESEM and transmission electron microscope and embodiment's 1 is similar.
The three-dimensional porous Co preparing with the present embodiment 3o 4/ Pt/Ni combination electrode is as positive pole, and take lithium metal as negative pole, polypropylene film (trade mark Celgard C380, Celgard company of the U.S.) is barrier film, LiClO 41,2-dimethoxy-ethane (DME) solution is electrolyte, in the glove box that is full of argon gas, assembles battery.After passing into 1 atmospheric oxygen, carry out charge-discharge test.
Constant volume charge-discharge test (capacity limit is at 500mAh/g, current density 100mA/g, and voltage range 2V～4.5V, wherein capacity and current density are all based on Co 3o 4gross mass with Pt) show, in 30 charge and discharge process, this lithium-empty battery all can keep stable circulation.Its electric discharge end current potential remains on 2.45V left and right, and charging end current potential remains on 4.14V left and right.Compared with embodiment 4, polarization increases, and the too low empty battery performance of lithium that also can affect of Pt addition is described.

Claims (9)

1. a three-dimensional porous Co 3o 4/ Pt/Ni combination electrode, is characterized in that, take three-dimensional porous nickel foam as matrix, and direct growth Co on described matrix 3o 4nano wire, described Co 3o 4direct growth nanometer Pt particle on nano wire.
2. three-dimensional porous Co according to claim 1 3o 4/ Pt/Ni combination electrode, is characterized in that, described Co 3o 4co in/Pt/Ni combination electrode 3o 4bearing capacity be 0.2～1.0mg/cm 2.
3. three-dimensional porous Co according to claim 1 and 2 3o 4/ Pt/Ni combination electrode, is characterized in that, described Co 3o 4in/Pt/Ni combination electrode, the bearing capacity of Pt is 0.2～1.0mg/cm 2.
4. three-dimensional porous Co according to claim 3 3o 4/ Pt/Ni combination electrode, is characterized in that, described Co 3o 4in/Pt/Ni combination electrode, the bearing capacity of Pt is 0.4～0.8mg/cm 2.
5. according to the three-dimensional porous Co described in claim 1,2 or 4 3o 4/ Pt/Ni combination electrode, is characterized in that, described Co 3o 4nanowire diameter is 50～100nm, and length is 1～3 μ m; The diameter of described Pt particle is 5～10nm.
6. one kind according to the three-dimensional porous Co described in the arbitrary claim of claim 1～5 3o 4the preparation method of/Pt/Ni combination electrode, is characterized in that, comprises the following steps:
(1) soluble-salt of divalence Co and urea are dissolved in to deionized water, stir and obtain solution I, Co in described solution I 2+concentration is 0.01～0.05mol/L; To the soluble compound that adds platiniferous in solution I, continue to stir, obtain solution II;
Described urea and Co 2+mol ratio be 1～5;
The soluble compound of described platiniferous and Co 2+mol ratio be 0.01～0.05;
(2) three-dimensional porous nickel foam is immersed in solution II, be incubated 5～10h at 100～160 ℃, then obtain load through washing, after dry and have the three-dimensional porous nickel foam of cobalt hydroxide/Pt;
(3) load that step (2) obtains has the three-dimensional porous nickel foam of cobalt hydroxide/Pt after roasting 2～6h at 300～600 ℃, coolingly obtains described Co 3o 4/ Pt/Ni combination electrode.
7. preparation method according to claim 6, is characterized in that, the soluble-salt of described divalence Co is CoSO 4, CoSO 4hydrate, CoCl 2, CoCl 2hydrate, Co (NO 3) 2or Co (NO 3) 2hydrate;
The soluble compound of described platiniferous is H 2ptCl 6, H 2ptCl 6hydrate, K 2ptCl 6, K 2ptCl 6hydrate, (NH 4) 2ptCl 6, (NH 4) 2ptCl 6hydrate, H 2ptCl 4, H 2ptCl 4hydrate, K 2ptCl 4, K 2ptCl 4hydrate, (NH 4) 2ptCl 4or (NH 4) 2ptCl 4hydrate.
8. according to the preparation method described in claim 6 or 7, it is characterized in that the soluble compound of described platiniferous and Co 2+mol ratio be 0.01～0.025.
9. one kind according to the three-dimensional porous Co described in the arbitrary claim of claim 1～5 3o 4the application of/Pt/Ni combination electrode in the air electrode as lithium-empty battery.
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