CN105355839A - Graphene-gold composite electrode and preparation method and application thereof - Google Patents

Graphene-gold composite electrode and preparation method and application thereof Download PDF

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CN105355839A
CN105355839A CN201510666940.9A CN201510666940A CN105355839A CN 105355839 A CN105355839 A CN 105355839A CN 201510666940 A CN201510666940 A CN 201510666940A CN 105355839 A CN105355839 A CN 105355839A
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graphene
combination electrode
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CN105355839B (en
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谢健
王国卿
毛阳俊
唐之初
曹高劭
赵新兵
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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
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H01M4/0402—Methods of deposition of the material
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

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Abstract

The invention discloses a graphene-gold composite electrode. With porous metal as a matrix, graphene directly grows on the matrix; and Au directly grows on the graphene. The invention further discloses a preparation method and an application of the graphene-gold composite electrode. The preparation method has the advantages of simplicity in process, low cost, short period, low energy consumption and the like, and is applicable to large-scale industrial production; and the prepared graphene-gold composite electrode does not contain a conductive agent or a binder. Due to a special porous sandwich structure and the synergetic catalysis action of the Au and the graphene, the graphene-gold composite electrode demonstrates low polarity and relatively good cycling stability when used as a positive electrode of a lithium-air battery.

Description

A kind of Graphene-Jin 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 Graphene-Jin 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 is up to 11680Wh/kg, and this value can be suitable with the energy density of gasoline.Consider the weight of catalyst, electrolyte, battery packages etc., the reality of lithium-empty battery can obtain energy density higher than 1000Wh/kg, 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 lithium-empty battery 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 Ru, Au, Pd etc., oxide M nO 2, Co 3o 4, Fe 2o 3deng, composite catalyst is as MnO 2/ Au, MoN/ Graphene, MnCo 2o 4/ Graphenes etc. are developed.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 important goal of catalyst development, is wherein one of method wherein on material with carbon element by noble-metal-supported.In various material with carbon element, Graphene, because its high conductivity, high mechanical strength, large specific area agent and porosity, is ideal basis material.
The report preparing composite material in prior art using Graphene as basis material is existing a lot, but the report being used as lithium-empty cell catalyst carrier is little, the Chinese patent application being CN102423703A as publication number discloses a kind of Graphene for lithium-empty battery-platinum nano-composite catalyst and preparation method thereof, this nano-composite catalyst is made up of Graphene and Pt nanoparticle, take solid platinum as target, adopt liquid-phase pulse laser ablation technology, growing nano platinum grain on Graphene.This compound catalyze material has good catalytic performance, and under 100mA/g electric current, capacity reaches 4000mAh/g, and has less polarization and the cyclical stability of excellence.The above-mentioned Graphene for lithium-empty battery-platinum nano-composite catalyst needs to adopt the preparation of liquid-phase pulse laser ablation technology, and method is comparatively complicated.
Summary of the invention
The invention provides a kind of preparation method of the graphene-based combination electrode for lithium-air battery, the method technique is simple, and energy consumption is low, cost is low, is suitable for large-scale industrial production.
Invention also provides a kind of graphene-based combination electrode prepared by said method, this Graphene-Jin combination electrode has high power capacity, low overpotential and high cyclical stability, and the use amount of gold is lower.
Present invention also offers a kind of application of graphene-based combination electrode in lithium-air battery prepared by said method, this lithium-air battery is applied in lithium-empty battery air electrode, can be used to the chemical property improving lithium-empty battery, particularly reduce overpotential and improve cyclical stability, and saving electrode preparation cost.
A preparation method for Graphene-Jin combination electrode, comprises the steps:
(1) with porous metals M for matrix, by chemical vapour deposition technique, directly growing graphene G on matrix, is designated as M/G;
(2) by HAuCl 44H 2o is dissolved in deionized water, stirs, and prepares aqueous solution of chloraurate; Under condition of ice bath, slowly stir 0.5 ~ 2 hour; The M/G that step (1) obtains is immersed in above-mentioned aqueous solution of chloraurate, has left standstill taking-up product, repeatedly cleaned through deionization, vacuum drying;
(3) under an argon atmosphere, the oven dry product roasting 1 ~ 4h at 200 ~ 500 DEG C step (2) obtained, obtains described M/G-Au combination electrode material after cooling.
In step (1), as preferably, concrete steps are:
Porous metals are put into tube furnace, is warming up to 800 ~ 1200 DEG C, after insulation under an ar atmosphere, then with Ar air-flow, ethanol is introduced in quartz ampoule, reaction 3 ~ 10min; Finally, be cooled to room temperature under an ar atmosphere, obtain growing the Graphene on porous metal matrix.
In step (1), described porous metals M is nickel porous (Ni), porous aluminum (Al) or POROUS TITANIUM (Ti).The porosity of=80% of porous metals, thickness is 1 – 3mm.
In step (2), as preferably, the concentration of described aqueous solution of chloraurate is 0.05 ~ 0.3mg/mL.In this step, under shown condition of ice bath, the temperature of aqueous solution of chloraurate is generally less than 10 DEG C, is generally 0 ~ 5 DEG C.
Described slow stirring generally refers to that mixing speed is below 300rpm, generally refers to 50 ~ 200rpm.Under low temperature and slow mixing speed, be conducive to forming gold ball particle surface and be coated with this specific structure of the thin golden film of one deck.
In step (2), the time that M/G immerses aqueous solution of chloraurate is generally 2 ~ 4 hours.The temperature of vacuum drying is generally less than 80 DEG C, is generally 55 ~ 65 DEG C.
In step (3), described sintering temperature is 200 ~ 400 DEG C.The temperature of described cooling not strict restriction, based on adequate operation, generally can be cooled to the ambient temperature of 15 ~ 30 DEG C.
Present invention also offers a kind of Graphene-Jin combination electrode, it is prepared by above-mentioned arbitrary preparation method, and this electrode is with porous metals M for matrix, and on matrix, direct growth Graphene, is designated as M/G, and direct growth Au on described Graphene, is designated as M/G-Au.
Specifically, the present invention is matrix with porous metals, directly prepares Graphene by CVD on matrix, and described Graphene replicates the loose structure of metal; Grown the gold of two kinds of forms again at graphenic surface by ice bath infusion method: diameter is the spherical gold grain of 100 ~ 200nm, is uniformly distributed on Graphene, the golden film that spherical particle surface coverage has one deck thin, golden film thickness is 10-20nm.Finally obtain the sandwich of graphene layer/Au particle/Au film.Graphene and Au have concerted catalysis effect, and mechanism of action is: Graphene has certain catalytic action, but compared to Au, its catalytic action is more weak, and the catalytic process being mainly Au in catalytic process provides electric action; Although and Au catalytic action is comparatively strong, do not have the electric action of Graphene, its catalytic performance can not fully realize.
Described direct growth refers to: first by CVD, directly deposited graphite alkene on the skeleton of porous metals; Then, under condition of ice bath, graininess and membranaceous gold are directly grown on Graphene; In contrast, non-immediate growth refers to pre-synthesis Graphene and gold, then two kinds of raw materials and binding agent is mixed in organic solvent, stirs into slurry, and then coats on porous metal matrix.
In the sandwich of graphene layer/gold grain/golden film, graphene layer mainly provides electric action; Gold grain mainly plays catalytic action, guides Li 2o 2along its superficial growth, slow down the passivation of electrode; And golden film works in coordination with graphene layer by Li 2o 2growth be limited in sandwich, keep on the one hand the conductivity of whole electrode (gold itself has high conductivity), decrease Li on the other hand 2o 2contact to reduce side reaction with electrolytical.As preferably, the diameter of described gold grain is 100 ~ 200nm, be uniformly distributed on Graphene, granule gold is conducive to improving catalytic performance, gold film thickness is 10 ~ 20nm, thin golden film is conducive to the raising of electric conductivity, and being also conducive to forming hole profit provides passage for the diffusion of lithium ion and oxygen.
As preferably, in described Graphene-Jin combination electrode, the bearing capacity of Au (comprising gold grain and golden film) is 0.4 ~ 0.8mg/cm 2.The bearing capacity of Au controls by adjustment aqueous solution of chloraurate concentration and immersion time.The bearing capacity of Au is very few, and catalytic effect is undesirable, and at the more difficult formation membrane structure of particle surface; Bearing capacity is too much, and gold grain is feeding-up in graphenic surface distribution, is unfavorable for Li 2o 2deposition, be also unfavorable for forming thinner golden film, and the increase of cost and the decline of specific capacity can be caused.
As preferably, in described Graphene-Jin combination electrode material, Graphene presents minority Rotating fields (2 ~ 10 layers), and in described Graphene-Jin combination electrode, the bearing capacity of Graphene is 0.5 ~ 1.5mg/cm 2.The bearing capacity of Graphene controlled by the adjustment chemical vapour deposition (CVD) time.The catalysis that Graphene is mainly Au in catalytic process provides electric action, the too low raising being unfavorable for electric conductivity of Graphene content, and too high content to the further raising generation effect of electric conductivity, and can not can cause the increase of electrode weight.Therefore, the content of Graphene is controlled in above-mentioned scope more reasonable.
The invention also discloses the described application of graphene-based-Jin composite electrode in the air electrode as lithium-empty battery.
Compared with prior art, tool of the present invention has the following advantages:
1, in the Graphene-Jin combination electrode prepared of the present invention, Graphene and gold are directly grown on porous metal matrix, 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, in the Graphene-Jin combination electrode prepared of the present invention, Graphene and Au have concerted catalysis effect, are conducive to the raising of catalytic performance, thus effectively reduce the overpotential of lithium-empty battery;
3, the Graphene-Jin combination electrode that prepared by the present invention presents sandwich, is conducive to Li 2o 2controllable growth to slow down the passivation of electrode and to reduce the generation of side reaction.
Accompanying drawing explanation
Fig. 1 is the X ray diffracting spectrum of nickel/Graphene-Jin combination electrode prepared by embodiment 1;
Fig. 2 is Raman (Raman) spectrogram of Ni/G prepared by embodiment 1;
Fig. 3 is the low power stereoscan photograph of Graphene-Jin combination electrode prepared by embodiment 1;
Fig. 4 is the high power stereoscan photograph of Graphene-Jin combination electrode prepared by embodiment 1;
Fig. 5 is the cycle performance figure using the Graphene-Jin combination electrode of embodiment 1 preparation as the lithium-empty battery of positive pole;
Fig. 6 is Graphene-Jin combination electrode stereoscan photograph prepared by comparative example 1;
Fig. 7 is the cycle performance figure using the Graphene-Jin combination electrode of comparative example 1 preparation as the lithium-empty battery of positive pole.
Embodiment
Embodiment 1
Nickel porous (porosity is 96%, and thickness is 1.6mm) is put into tube furnace, under Ar (500s.c.c.m.) atmosphere, is warming up to 1000 DEG C with the programming rate of 100 DEG C/min; Be incubated after 5 minutes, with Ar (250s.c.c.m.) air-flow, ethanol introduced in quartz ampoule, react 5 minutes; Finally, be cooled to room temperature with the cooling rate of 100 DEG C/min under an ar atmosphere, obtain growing the Graphene (Ni/G) on nickel porous matrix, the wherein bearing capacity 0.82mg/cm of Graphene 2; By HAuCl 44H 2o is dissolved in deionized water, stirs, and preparation concentration is the solution of 0.16mg/mL, and the beaker filling above-mentioned solution is placed in ice bath, slowly stirs 1 hour; Ni/G is immersed above-mentioned solution, leaves standstill 3 hours, take out product, repeatedly to clean and at 60 DEG C of vacuum dryings through deionization; By roasting at products therefrom under an ar atmosphere 300 DEG C 2 hours, be then cooled to the G-Au combination electrode (Ni/G-Au) that room temperature obtains being carried on Ni, wherein the bearing capacity of Au was 0.55mg/cm 2.
Fig. 1 is Ni/G-Au electrode X-ray diffraction spectrum prepared by the present embodiment, and this material can be summed up as the Graphene of load on Ni and gold.
Fig. 2 is the Raman spectrum of Ni/G prepared by the present embodiment, and stronger 2D peak shows that Graphene is minority Rotating fields.
Fig. 3 and Fig. 4 is respectively the low power being carried on the G-Au electrode in nickel porous and high power ESEM prepared by the present embodiment.Only be grown on the skeleton of nickel porous from the known G-Au of photo 3, and retain the loose structure of nickel.From the known Au even particulate dispersion of photo 4 in Graphene, granular size is 100 ~ 200nm, has golden film in gold grain surface coverage, thickness 10 ~ 20 nanometer, forms the sandwich of graphene layer/gold grain/golden film.
That prepares using the present embodiment is carried on G-Au in nickel porous as positive pole, and take lithium metal as negative pole, polypropylene film (trade mark CelgardC380, Celgard company of the U.S.) is barrier film, LiClO 4tRIGLYME (TEGDME) 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, its cyclic curve as shown in Figure 5.
(capacity limit is at 1000mAh/g for constant volume charge-discharge test, current density 400mA/g, voltage range 2V ~ 4.5V, wherein capacity and current density are all based on Au weight) show, in 100 charge and discharge process, this lithium-empty battery all can keep stable circulation.Its electric discharge end current potential remains on about 2.58V, demonstrates lower polarization and good cyclical stability.
Comparative example 1
The deposition process of Graphene is carried out under room temperature (25 DEG C) with the deposition process of embodiment 1, Au, and be different from the condition of ice bath of embodiment 1, other techniques are identical.Specific as follows, nickel porous is put into tube furnace, under Ar (500s.c.c.m.) atmosphere, is warming up to 1000 DEG C with the programming rate of 100 DEG C/min; Be incubated after 5 minutes, with Ar (250s.c.c.m.) air-flow, ethanol introduced in quartz ampoule, react 5 minutes; Finally, be cooled to room temperature with the cooling rate of 100 DEG C/min under an ar atmosphere, obtain growing the Graphene (Ni/G) on nickel porous matrix, the wherein bearing capacity 0.82mg/cm of Graphene 2; By HAuCl 44H 2o is dissolved in deionized water, stirs, and preparation concentration is the solution of 0.16mg/mL, at room temperature slowly stirs 1 hour; Ni/G is immersed above-mentioned solution, static 3 hours, take out product, repeatedly to clean and at 60 DEG C of vacuum dryings through deionization; By roasting at products therefrom under an ar atmosphere 300 DEG C 2 hours, be then cooled to the G-Au combination electrode (Ni/G-Au) that room temperature obtains being carried on Ni, wherein the bearing capacity of Au was 0.8mg/cm 2.Institute's deposited gold all presents graininess, and average particle size particle size is greater than 200nm, and particle surface does not form golden film and sees Fig. 6.
That prepares using this comparative example is carried on G-Au in nickel porous as positive pole, and take lithium metal as negative pole, polypropylene film (trade mark CelgardC380, Celgard company of the U.S.) is barrier film, LiClO 4tRIGLYME (TEGDME) 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, charging and discharging curve as shown in Figure 7.
(capacity limit is at 1000mAh/g for constant volume charge-discharge test, current density 400mA/g, voltage range 2V ~ 4.5V, wherein capacity and current density are all based on Au weight) show, in secondary charge and discharge process, this lithium-empty battery only can adhere to 28 stable circulations, and discharge voltage cycle down is to 2V, demonstrates higher polarization and poor cyclical stability.
Embodiment 2
Nickel porous (porosity is 90%, and thickness is 2.5mm) is put into tube furnace, under Ar (500s.c.c.m.) atmosphere, is warming up to 1000 DEG C with the programming rate of 100 DEG C/min; Be incubated after 5 minutes, with Ar (250s.c.c.m.) air-flow, ethanol introduced in quartz ampoule, react 8 minutes; Finally, be cooled to room temperature with the cooling rate of 100 DEG C/min under an ar atmosphere, obtain growing the Graphene (Ni/G) on nickel porous matrix, the wherein bearing capacity 1.25mg/cm of Graphene 2; By HAuCl 44H 2o is dissolved in deionized water, stirs, and preparation concentration is the solution of 0.1mg/mL, and the beaker filling above-mentioned solution is placed in ice bath, slowly stirs 1 hour; Ni/G is immersed above-mentioned solution, leaves standstill 3 hours, take out product, repeatedly to clean and at 60 DEG C of vacuum dryings through deionization; By roasting at products therefrom under an ar atmosphere 200 DEG C 4 hours, be then cooled to the G-Au combination electrode (Ni/G-Au) that room temperature obtains being carried on Ni, wherein the bearing capacity of Au was 0.45mg/cm 2.XRD shows, Graphene and Au are deposited in nickel porous.Raman spectrum shows, Graphene is minority Rotating fields.SEM photo shows, G-Au is only grown on the skeleton of nickel porous, and retains the loose structure of nickel.Au even particulate dispersion is on Graphene, and granular size is 100 ~ 200nm, has golden film in gold grain surface coverage, thickness 10 ~ 20 nanometer, forms the sandwich of graphene layer/gold grain/golden film.
That prepares using the present embodiment is carried on G-Au in nickel porous as positive pole, and take lithium metal as negative pole, polypropylene film (trade mark CelgardC380, Celgard company of the U.S.) is barrier film, LiClO 4tRIGLYME (TEGDME) 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.
(capacity limit is at 1000mAh/g for constant volume charge-discharge test, current density 400mA/g, voltage range 2V ~ 4.5V, wherein capacity and current density are all based on Au weight) show, in 100 charge and discharge process, this lithium-empty battery all can keep stable circulation.Its electric discharge end current potential remains on about 2.55V, demonstrates lower polarization and good cyclical stability.
Embodiment 3
Porous aluminum (porosity is 85%, and thickness is 2mm) is put into tube furnace, under Ar (500s.c.c.m.) atmosphere, is warming up to 1000 DEG C with the programming rate of 100 DEG C/min; Be incubated after 5 minutes, with Ar (250s.c.c.m.) air-flow, ethanol introduced in quartz ampoule, react 3 minutes; Finally, be cooled to room temperature with the cooling rate of 100 DEG C/min under an ar atmosphere, obtain growing the Graphene (Al/G) on porous aluminum matrix, the wherein bearing capacity 0.55mg/cm of Graphene 2; By HAuCl 44H 2o is dissolved in deionized water, stirs, and preparation concentration is the solution of 0.2mg/mL, and the beaker filling above-mentioned solution is placed in frozen water mixed liquor, slowly stirs 1.5 hours; Al/G is immersed above-mentioned solution, leaves standstill 4 hours, take out product, repeatedly to clean and at 60 DEG C of vacuum dryings through deionization; By roasting at products therefrom under an ar atmosphere 300 DEG C 2.5 hours, be then cooled to the G-Au combination electrode (Al/G-Au) that room temperature obtains being carried on Al, wherein the bearing capacity of Au was 0.6mg/cm 2.XRD shows, Graphene and Au are deposited in porous Al.Raman spectrum shows, Graphene is minority Rotating fields.SEM photo shows, G-Au is only grown on the skeleton of porous aluminum, and retains the loose structure of Al.Au even particulate dispersion is on Graphene, and granular size is 100 ~ 200nm, has golden film in gold grain surface coverage, thickness 10 ~ 20 nanometer, forms the sandwich of graphene layer/gold grain/golden film.
That prepares using the present embodiment is carried on G-Au in porous aluminum as positive pole, and take lithium metal as negative pole, polypropylene film (trade mark CelgardC380, Celgard company of the U.S.) is barrier film, LiClO 4tRIGLYME (TEGDME) 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.
(capacity limit is at 1000mAh/g for constant volume charge-discharge test, current density 400mA/g, voltage range 2V ~ 4.5V, wherein capacity and current density are all based on Au weight) show, in 100 charge and discharge process, this lithium-empty battery all can keep stable circulation.Its electric discharge end current potential remains on about 2.53V, demonstrates lower polarization and good cyclical stability.
Embodiment 4
POROUS TITANIUM (porosity is 95%, and thickness is 1mm) is put into tube furnace, under Ar (500s.c.c.m.) atmosphere, is warming up to 1000 DEG C with the programming rate of 100 DEG C/min; Be incubated after 5 minutes, with Ar (250s.c.c.m.) air-flow, ethanol introduced in quartz ampoule, react 10 minutes; Finally, be cooled to room temperature with the cooling rate of 100 DEG C/min under an ar atmosphere, obtain growing the Graphene (Ti/G) on POROUS TITANIUM matrix, the wherein bearing capacity 1.45mg/cm of Graphene 2; By HAuCl 44H 2o is dissolved in deionized water, stirs, and preparation concentration is the solution of 0.25mg/mL, and the beaker filling above-mentioned solution is placed in frozen water mixed liquor, slowly stirs 2 hours; Ti/G is immersed above-mentioned solution, leaves standstill 2 hours, take out product, repeatedly to clean and at 60 DEG C of vacuum dryings through deionization; By roasting at products therefrom under an ar atmosphere 400 DEG C 1.5 hours, be then cooled to the G-Au combination electrode (Ti/G-Au) that room temperature obtains being carried on Ti, wherein the bearing capacity of Au was 0.65mg/cm 2.XRD shows, Graphene and Au are deposited on porous Ti.Raman spectrum shows, Graphene is minority Rotating fields.SEM photo shows, G-Au is only grown on the skeleton of POROUS TITANIUM, and retains the loose structure of titanium.Au even particulate dispersion is on Graphene, and granular size is 100 ~ 200nm, has golden film in gold grain surface coverage, thickness 10 ~ 20 nanometer, forms the sandwich of graphene layer/gold grain/golden film.
That prepares using the present embodiment is carried on G-Au in POROUS TITANIUM as positive pole, and take lithium metal as negative pole, polypropylene film (trade mark CelgardC380, Celgard company of the U.S.) is barrier film, LiClO 4tRIGLYME (TEGDME) 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.
(capacity limit is at 1000mAh/g for constant volume charge-discharge test, current density 400mA/g, voltage range 2V ~ 4.5V, wherein capacity and current density are all based on Au weight) show, in 100 charge and discharge process, this lithium-empty battery all can keep stable circulation.Its electric discharge end current potential remains on about 2.61V, demonstrates lower polarization and good cyclical stability.

Claims (9)

1. a preparation method for Graphene-Jin combination electrode, is characterized in that, comprises the steps:
(1) with porous metals M for matrix, by chemical vapour deposition technique, directly growing graphene G on matrix, is designated as M/G;
(2) by HAuCl 44H 2o is dissolved in deionized water, prepares aqueous solution of chloraurate, under condition of ice bath, slowly stirs 0.5 ~ 2 hour; The M/G that step (1) obtains is immersed in above-mentioned aqueous solution of chloraurate, has left standstill, take out product, repeatedly clean through deionization, vacuum drying;
(3) under an argon atmosphere, the oven dry product roasting 1 ~ 4h at 200 ~ 500 DEG C step (2) obtained, obtains described M/G-Au combination electrode material after cooling.
2. the preparation method of Graphene-Jin combination electrode according to claim 1, is characterized in that, described porous metals M is nickel porous, porous aluminum or POROUS TITANIUM, the porosity of=80% of porous metals, and thickness is 1 – 3mm.
3. the preparation method of Graphene-Jin combination electrode according to claim 1, is characterized in that, in step (2), the concentration of described aqueous solution of chloraurate is 0.05 ~ 0.3mg/mL; The time that M/G immerses aqueous solution of chloraurate is generally 2 ~ 4 hours.
4. the preparation method of Graphene-Jin combination electrode according to claim 1, is characterized in that, in step (3), described sintering temperature is 200 ~ 400 DEG C.
5. a Graphene-Jin combination electrode, is characterized in that, described Graphene-Jin combination electrode is prepared by the preparation method described in the arbitrary claim of claim 1-4.
6. Graphene-Jin combination electrode according to claim 5, is characterized in that, Au wherein presents two kinds of forms, i.e. spherical gold grain and golden film; Described spherical gold grain, is uniformly distributed on Graphene, and diameter is 100 ~ 200nm; Described golden film covers spherical particle surface, and golden film thickness is 10 ~ 20nm.
7. Graphene-Jin combination electrode according to claim 5, is characterized in that, in described Graphene-Jin combination electrode material, the bearing capacity of Au is 0.4 ~ 0.8mg/cm 2.
8. Graphene-Jin combination electrode according to claim 5, is characterized in that, in described Graphene-Jin combination electrode material, Graphene bearing capacity is 0.5 ~ 1.5mg/cm 2.
9. the application of Graphene-Jin combination electrode in the air electrode as lithium-empty battery, is characterized in that, described Graphene-Jin combination electrode is prepared by the preparation method described in the arbitrary claim of claim 1-4.
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