CN103825003B - A kind of three-dimensional porous Co 3o 4/ Pt/Ni combination electrode and its preparation method and application - Google Patents

A kind of three-dimensional porous Co 3o 4/ Pt/Ni combination electrode and its preparation method and application Download PDF

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CN103825003B
CN103825003B CN201410068658.6A CN201410068658A CN103825003B CN 103825003 B CN103825003 B CN 103825003B CN 201410068658 A CN201410068658 A CN 201410068658A CN 103825003 B CN103825003 B CN 103825003B
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dimensional porous
ptcl
combination electrode
hydrate
lithium
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CN103825003A (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 kind of three-dimensional porous Co 3o 4/ Pt/Ni combination electrode, with three-dimensional porous foams nickel for matrix, direct growth Co on described matrix 3o 4nano wire, described Co 3o 4direct growth Pt nano particle particle on nano wire.The invention also discloses described Co 3o 4the preparation method of/Pt/Ni combination electrode and application, preparation technology is simple, and energy consumption is low, cost is low, is suitable for large-scale industrial production; Due to special three-dimensional porous structure and Co 3o 4the concerted catalysis effect of nano wire and Pt nano particle, the Co prepared 3o 4/ Pt/Ni combination electrode has high power capacity, low overpotential and high cyclical stability, is applied in lithium-empty battery air electrode, can be used to the chemical property improving lithium-empty battery, particularly reduces overpotential and improves cyclical stability.

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 composite electrode for battery 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 is negative pole with lithium metal, and the battery that air (or oxygen) is positive pole, 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 then 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, due to its high energy density, has important application prospect in the field such as redundant electrical power 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 start the research of the empty battery of lithium in the world.As American I BM company starts " Battery500Project " project, the final goal of this plan is that lithium-empty battery is used for automobile, and in this project, " 500 " represent each Rechargeable vehicle and travel 500 miles (800 kilometers).
The factor affecting lithium-empty battery performance is a lot, but the composition and structure of catalyst is key factor.Recently, various new catalyst 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, relative to metal oxide (as Fe 2o 3, MnO 2) catalyst, noble metal catalyst has the performance advantage of its uniqueness, is the extremely ideal catalyst of lithium-empty battery air.But noble metal catalyst cost compare is high, the use amount therefore reducing noble metal is the trend of catalyst development from now on, is wherein one of method wherein on metal oxide 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 layers on three-dimensional structure nickel foam substrate, utilize phase oxidative method to prepare three-dimensional structure foam Co 3o 4negative pole, and by discharge and recharge and the technique study such as cyclic voltammetric and the electrochemical impedance chemical property of electrode, result shows, three-dimensional foam structure improves Co 3o 4the circulation volume retention of electrode and high rate performance.
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 prepared 3o 4/ Pt/Ni combination electrode has high power capacity, low overpotential and high cyclical stability, is applied in lithium-empty battery air electrode, can be used to the chemical property improving 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, with three-dimensional porous foams nickel for matrix, direct growth Co on described matrix 3o 4nano wire, described Co 3o 4direct growth Pt nano particle particle on nano wire.
The present invention with three-dimensional porous foams nickel for matrix, direct growth Co on matrix 3o 4nano wire and Pt nano particle 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 Sum decomposition on its surface, there is lower overpotential, but the Li formed 2o 2particle is comparatively large, not easily decomposes during charging, causes charging overpotential higher; Pt adds except also to Li 2o 2formation Sum decomposition play outside catalytic action, due to Pt adsorb O 2energy force rate Co 3o 4by force, Li can be changed 2o 2crystallization behavior, namely reduce Li 2o 2size, charge time make Li 2o 2more easily decompose, charging overpotential can be reduced further.
Described direct growth refers under hydrothermal conditions, Co 3o 4nano wire is directly grown on the skeleton of nickel foam; In contrast, non-immediate growth refers to the pre-synthesis Co of hydro thermal method 3o 4nano wire, then by Co 3o 4mix in organic solvent with binding agent, stir into slurry, then slurry is coated in nickel foam.Pt direct growth refers at Co 3o 4while 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 portion of 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 μm.Co 3o 4the meticulous load being 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 preferably, the bearing capacity of described Pt is 0.4 ~ 0.8mg/cm 2.The addition of Pt is too low, changes Li 2o 2the ability of crystallization behavior more weak, 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 higher, affects Co 3o 4catalytic action, on the other hand too much Pt adds membership and causes Pt particle agglomeration, 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, too much add Pt and can cause the decline of specific capacity and the increase of catalyst cost, therefore, it is more reasonable to be controlled in above-mentioned scope by the content of Pt.
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 deionized water, stir and obtain solution I, Co in described solution I 2+concentration is 0.01 ~ 0.05mol/L; In solution I, add the soluble compound of platiniferous, 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 foams nickel is immersed in solution II, at 100 ~ 160 DEG C, be incubated 5 ~ 10h, then obtain the three-dimensional porous foams nickel that load has cobalt hydroxide/Pt after washing, drying;
(3) load that step (2) obtains has the three-dimensional porous foams nickel of cobalt hydroxide/Pt after roasting 2 ~ 6h at 300 ~ 600 DEG C, and cooling obtains described Co 3o 4/ Pt/Ni combination electrode.
As preferably, the soluble compound of the platiniferous described in step (1) and Co 2+mol ratio be 0.01 ~ 0.025.
As preferably, the holding temperature described in step (2) is 110 ~ 130 DEG C, and the time is 5 ~ 8h; Sintering temperature described in step (3) is 400 ~ 500 DEG C, and the time is 2 ~ 4h.
The temperature of described cooling not strict restriction, based on adequate operation, generally can be cooled to the ambient temperature of 15 DEG C ~ 30 DEG C.
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 prepared of the present invention 3o 4being with Pt is directly grown on nickel foam substrate, without other conductive agents and binding agent, has 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 prepared of the present invention 3o 4nano wire and Pt nano particle have concerted catalysis effect, are conducive to the raising of catalytic performance, thus 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, thus improves the cyclical stability of 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 prepared with embodiment 1 3o 4/ Pt/Ni combination electrode is as the charging and discharging curve figure of the lithium-empty battery of positive pole;
Fig. 6 is the three-dimensional porous Co prepared with comparative example 3o 4/ Ni electrode is as the charging and discharging curve figure of the lithium-empty battery of positive pole.
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, prepare with Co 2+meter concentration is the solution of 0.013mol/L, stirs; Add H again 2ptCl 66H 2o(addition is Co 2+0.025 of mole), continue to stir.Using three-dimensional porous foams nickel as matrix, immerse above-mentioned solution, be transferred to again in reactor, in the baking oven of 120 DEG C, 6 hours are incubated after airtight, then rinse for several times with deionized water and absolute alcohol, after 12 hours, obtain the cobalt hydroxide/Pt be carried in nickel foam the baking oven vacuumizes of 60 DEG C; By roasting at the above-mentioned nickel foam being loaded with cobalt hydroxide/Pt in atmosphere 400 DEG C 2 hours, be then cooled to the Co that room temperature obtains being carried 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 4the X ray diffracting spectrum of/Pt/Ni combination electrode, ESEM and transmission electron microscope photo are shown in Fig. 1 ~ 4 respectively.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 is 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 μm, 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.
With three-dimensional porous Co prepared by the present embodiment 3o 4/ Pt/Ni combination electrode, as positive pole, take lithium metal as negative pole, and polypropylene film (trade mark CelgardC380, Celgard company of the U.S.) is barrier film, LiClO 41,2-dimethoxy-ethane (DME) solution be electrolyte, in the glove box being full of argon gas, assemble battery.After passing into 1 atmospheric oxygen, carry out charge-discharge test, gained chemical property as shown in Figure 5.
(, at 500mAh/g, current density 100mA/g, voltage range 2 ~ 4.5V, wherein capacity and current density are all based on Co for capacity limit for constant volume charge-discharge test 3o 4with the gross mass of 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 about 2.6V, charging end current potential remains on about 3.95V, 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, prepare with Co 2+meter concentration is the solution of 0.013mol/L, stirs.Using three-dimensional porous foams nickel as matrix, immerse above-mentioned solution, then be transferred in reactor, after airtight, in the baking oven of 120 DEG C, be incubated 6 hours, then rinse for several times with deionized water and absolute alcohol, after 12 hours, obtain the cobalt hydroxide be carried in nickel foam the baking oven vacuumizes of 60 DEG C; By roasting at the above-mentioned nickel foam being loaded with cobalt hydroxide in atmosphere 400 DEG C 2 hours, be then cooled to the Co that room temperature obtains being carried in nickel foam 3o 4electrode.
With three-dimensional porous Co prepared by this comparative example 3o 4/ Ni electrode, as positive pole, take lithium metal as negative pole, and polypropylene film (trade mark CelgardC380, Celgard company of the U.S.) is barrier film, LiClO 41,2-dimethoxy-ethane (DME) solution be electrolyte, in the glove box being full of argon gas, assemble battery.Carry out electrochemical property test (under oxygen atmosphere), as shown in Figure 6, when this electrode charge and discharge cut-ff voltage is 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, prepare with Co 2+meter concentration is the solution of 0.025mol/L, stirs; Add H again 2ptCl 4(addition is Co 2+0.01 of mole), continue to stir.Using three-dimensional porous foams nickel as matrix, immerse above-mentioned solution, then be transferred in reactor, after airtight, in the baking oven of 130 DEG C, be incubated 5 hours, then rinse for several times with deionized water and absolute alcohol, obtain the baking oven vacuumizes of 60 DEG C the nickel foam that load has cobalt hydroxide/Pt after 12 hours; By roasting 3h at the above-mentioned nickel foam being loaded with cobalt hydroxide/Pt in atmosphere 450 DEG C, be then cooled to the Co that room temperature obtains being carried 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 1 similar.
With three-dimensional porous Co prepared by the present embodiment 3o 4/ Pt/Ni combination electrode, as positive pole, take lithium metal as negative pole, and polypropylene film (trade mark CelgardC380, Celgard company of the U.S.) is barrier film, LiClO 41,2-dimethoxy-ethane (DME) solution be electrolyte, in the glove box being full of argon gas, assemble battery.After passing into 1 atmospheric oxygen, carry out charge-discharge test.
(, at 500mAh/g, current density 100mA/g, voltage range 2V ~ 4.5V, wherein capacity and current density are all based on Co for capacity limit for constant volume charge-discharge test 3o 4with the gross mass of 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 about 2.5V, and charging end current potential remains on about 4.10V, 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, prepare with Co 2+meter concentration is the solution of 0.05mol/L, stirs; Add K again 2ptCl 6(addition is Co 2+0.01 of mole), continue to stir.Using three-dimensional porous foams nickel as matrix, immerse above-mentioned solution, then be transferred in reactor, after airtight, in the baking oven of 110 DEG C, be incubated 8 hours, then rinse for several times with deionized water and absolute alcohol, obtain the baking oven vacuumizes of 60 DEG C the nickel foam that load has cobalt hydroxide/Pt after 12 hours; By roasting at the above-mentioned nickel foam being loaded with cobalt hydroxide/Pt in atmosphere 500 DEG C 2 hours, be then cooled to the Co that room temperature obtains being carried 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 1 similar.
With three-dimensional porous Co prepared by the present embodiment 3o 4/ Pt/Ni combination electrode, as positive pole, take lithium metal as negative pole, and polypropylene film (trade mark CelgardC380, Celgard company of the U.S.) is barrier film, LiClO 41,2-dimethoxy-ethane (DME) solution be electrolyte, in the glove box being full of argon gas, assemble battery.After passing into 1 atmospheric oxygen, carry out charge-discharge test.
(, at 500mAh/g, current density 100mA/g, voltage range 2V ~ 4.5V, wherein capacity and current density are all based on Co for capacity limit for constant volume charge-discharge test 3o 4with the gross mass of 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 about 2.55V, and charging end current potential remains on about 4.05V, 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, prepare with Co 2+meter concentration is the solution of 0.01mol/L, stirs; Add (NH again 4) 2ptCl 6(addition is Co 2+0.01 of mole), continue to stir.Using three-dimensional porous foams nickel as matrix, immerse above-mentioned solution, be transferred to again in reactor, in the baking oven of 120 DEG C, 8 hours are incubated after airtight, then rinse for several times with deionized water and absolute alcohol, obtain the baking oven vacuumizes of 60 DEG C the nickel foam that load is loaded with cobalt hydroxide/Pt after 12 hours; By roasting at the above-mentioned nickel foam being loaded with cobalt hydroxide/Pt in atmosphere 400 DEG C 4 hours, be then cooled to the Co that room temperature obtains being carried 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 1 similar.
With three-dimensional porous Co prepared by the present embodiment 3o 4/ Pt/Ni combination electrode, as positive pole, take lithium metal as negative pole, and polypropylene film (trade mark CelgardC380, Celgard company of the U.S.) is barrier film, LiClO 41,2-dimethoxy-ethane (DME) solution be electrolyte, in the glove box being full of argon gas, assemble battery.After passing into 1 atmospheric oxygen, carry out charge-discharge test.
(, at 500mAh/g, current density 100mA/g, voltage range 2V ~ 4.5V, wherein capacity and current density are all based on Co for capacity limit for constant volume charge-discharge test 3o 4with the gross mass of 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 about 2.65V, and charging end current potential remains on about 4.00V, 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 obtained 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 1 similar.
With three-dimensional porous Co prepared by the present embodiment 3o 4/ Pt/Ni combination electrode, as positive pole, take lithium metal as negative pole, and polypropylene film (trade mark CelgardC380, Celgard company of the U.S.) is barrier film, LiClO 41,2-dimethoxy-ethane (DME) solution be electrolyte, in the glove box being full of argon gas, assemble battery.After passing into 1 atmospheric oxygen, carry out charge-discharge test.
(, at 500mAh/g, current density 100mA/g, voltage range 2V ~ 4.5V, wherein capacity and current density are all based on Co for capacity limit for constant volume charge-discharge test 3o 4with the gross mass of 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 about 2.47V, and charging end current potential remains on about 4.12V, and compared with embodiment 4, polarization increases, and namely 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 obtained 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 1 similar.
With three-dimensional porous Co prepared by the present embodiment 3o 4/ Pt/Ni combination electrode, as positive pole, take lithium metal as negative pole, and polypropylene film (trade mark CelgardC380, Celgard company of the U.S.) is barrier film, LiClO 41,2-dimethoxy-ethane (DME) solution be electrolyte, in the glove box being full of argon gas, assemble battery.After passing into 1 atmospheric oxygen, carry out charge-discharge test.
(, at 500mAh/g, current density 100mA/g, voltage range 2V ~ 4.5V, wherein capacity and current density are all based on Co for capacity limit for constant volume charge-discharge test 3o 4with the gross mass of 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 about 2.45V, and charging end current potential remains on about 4.14V.Compared with embodiment 4, polarization increases, and illustrating that Pt addition is too low also can affect the empty battery performance of lithium.

Claims (3)

1. a three-dimensional porous Co 3o 4the preparation method of/Pt/Ni combination electrode, described three-dimensional porous Co 3o 4/ Pt/Ni combination electrode with three-dimensional porous foams nickel for matrix, direct growth Co on described matrix 3o 4nano wire, described Co 3o 4direct growth Pt nano particle particle on nano wire, is characterized in that, comprise the following steps:
(1) soluble-salt of divalence Co and urea are dissolved in deionized water, stir and obtain solution I, Co in described solution I 2+concentration is 0.01 ~ 0.05mol/L; In solution I, add the soluble compound of platiniferous, 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 foams nickel is immersed in solution II, at 100 ~ 160 DEG C, be incubated 5 ~ 10h, then obtain the three-dimensional porous foams nickel that load has cobalt hydroxide/Pt after washing, drying;
(3) load that step (2) obtains has the three-dimensional porous foams nickel of cobalt hydroxide/Pt after roasting 2 ~ 6h at 300 ~ 600 DEG C, and cooling obtains described Co 3o 4/ Pt/Ni combination electrode.
2. preparation method according to claim 1, 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.
3. preparation method according to claim 1 and 2, is characterized in that, the soluble compound of described platiniferous and Co 2+mol ratio be 0.01 ~ 0.025.
CN201410068658.6A 2014-02-27 2014-02-27 A kind of three-dimensional porous Co 3o 4/ Pt/Ni combination electrode and its preparation method and application Expired - Fee Related CN103825003B (en)

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