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 PDFInfo
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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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- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 109
- 239000006260 foam Substances 0.000 claims abstract description 41
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 38
- 239000002070 nanowire Substances 0.000 claims abstract description 20
- 239000011159 matrix material Substances 0.000 claims abstract description 13
- 239000002105 nanoparticle Substances 0.000 claims abstract description 9
- 239000002245 particle Substances 0.000 claims abstract description 8
- 238000003756 stirring Methods 0.000 claims description 19
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 claims description 14
- ASKVAEGIVYSGNY-UHFFFAOYSA-L cobalt(ii) hydroxide Chemical compound [OH-].[OH-].[Co+2] ASKVAEGIVYSGNY-UHFFFAOYSA-L 0.000 claims description 14
- 239000008367 deionised water Substances 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 9
- 239000004202 carbamide Substances 0.000 claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 8
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 239000000126 substance Substances 0.000 abstract description 6
- 238000006555 catalytic reaction Methods 0.000 abstract description 5
- 230000002153 concerted effect Effects 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 4
- 238000005265 energy consumption Methods 0.000 abstract description 3
- 238000005516 engineering process Methods 0.000 abstract description 3
- 238000009776 industrial production Methods 0.000 abstract description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 14
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 14
- 238000000034 method Methods 0.000 description 13
- 239000003054 catalyst Substances 0.000 description 11
- 229910052744 lithium Inorganic materials 0.000 description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 10
- 239000001301 oxygen Substances 0.000 description 10
- 229910052760 oxygen Inorganic materials 0.000 description 10
- 230000005540 biological transmission Effects 0.000 description 9
- 239000003792 electrolyte Substances 0.000 description 8
- 229910013684 LiClO 4 Inorganic materials 0.000 description 7
- 239000004743 Polypropylene Substances 0.000 description 7
- 229910052786 argon Inorganic materials 0.000 description 7
- 230000004888 barrier function Effects 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- -1 polypropylene Polymers 0.000 description 7
- 229920001155 polypropylene Polymers 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- 239000012298 atmosphere Substances 0.000 description 6
- 238000002389 environmental scanning electron microscopy Methods 0.000 description 6
- 230000010287 polarization Effects 0.000 description 6
- 238000001228 spectrum Methods 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 5
- 238000007599 discharging Methods 0.000 description 4
- 229910000510 noble metal Inorganic materials 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 229910021389 graphene Inorganic materials 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910018949 PtAu Inorganic materials 0.000 description 1
- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000011267 electrode slurry Substances 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 239000010416 ion conductor Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002815 nickel Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000007581 slurry coating method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Classifications
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
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
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.
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