CN105355839B - Golden combination electrode of a kind of graphene and its preparation method and application - Google Patents
Golden combination electrode of a kind of graphene and its preparation method and application Download PDFInfo
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- CN105355839B CN105355839B CN201510666940.9A CN201510666940A CN105355839B CN 105355839 B CN105355839 B CN 105355839B CN 201510666940 A CN201510666940 A CN 201510666940A CN 105355839 B CN105355839 B CN 105355839B
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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
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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
- 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
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- 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
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- 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
Abstract
The invention discloses a kind of golden combination electrode of graphene, using porous metals as matrix, direct growth graphene on matrix, direct growth Au on described graphene.The invention also discloses the preparation method and application of the golden combination electrode of described graphene.Described preparation method, with technique is simple, cost is low, the cycle is short, low power consumption and other advantages, is adapted to large-scale industrial production；The golden combination electrode of graphene prepared is free of any conductive agent and binding agent, because special porous and sandwich and Au and graphene concerted catalysis are acted on, when described combination electrode is used as lithium sky anode, low polarization and preferable cyclical stability are shown.
Description
Technical field
The present invention relates to lithium-sky composite electrode for battery field, and in particular to a kind of graphene-gold combination electrode and its system
Preparation Method and application.
Background technology
Lithium-sky battery is a kind of using lithium metal as negative pole, and air (or oxygen) is the battery of positive pole, and lithium ion conductor is electricity
Solve the novel energy storage apparatus of matter.The theoretical energy density of lithium-sky battery is up to 11680Wh/kg, and the value can be close with the energy of gasoline
Degree is suitable.In view of the weight of catalyst, electrolyte, battery packages etc., the reality of lithium-sky battery can obtain energy density and be higher than
1000Wh/kg, far above nickel-hydrogen (50Wh/kg), lithium ion (160Wh/kg), lithium-sulphur (370Wh/kg), zinc-sky (350Wh/
Kg) the energy density of battery.
Lithium-sky battery is due to its high energy density, in the fields such as the redundant electrical power of Vehicular dynamic battery and power network tool
There is important application prospect.Just because of lithium-sky battery has very important application prospect, some leading companys and section in the world
Grind the research that mechanism starts lithium-sky battery.Start such as IBM Corporation of the U.S. " Battery 500Project " projects,
The final goal of the plan is that lithium-sky battery is used into " 500 " in automobile, the project to represent each Rechargeable vehicle traveling
500 miles (800 kilometers).
Influence the factor of lithium-sky battery performance a lot, but the composition and structure of catalyst are key factors.Recently, it is various
New catalyst such as noble metal Ru, Au, Pd etc., oxide M nO2、Co3O4、Fe2O3Deng composite catalyst such as MnO2/Au、MoN/
Graphene, MnCo2O4/ graphene etc. is developed.Relative to metal oxide (such as Fe2O3、MnO2) catalyst, noble metal catalyst
It is lithium-sky battery air extremely ideal catalyst with its unique performance advantage.But noble metal catalyst cost compares
Height, therefore the important goal that the usage amount of noble metal is catalyst development is reduced, wherein by noble-metal-supported in being on carbon material
One of method therein.In various carbon materials, graphene is because its high electrical conductivity, high mechanical strength, big ratio surface
Product agent and porosity, are ideal matrix materials.
The report for preparing composite using graphene as matrix material in the prior art is a lot, but as lithium-sky
Seldom, such as Publication No. CN102423703A Chinese patent application discloses one kind to be used for the report of cell catalyst carrier
The graphene of lithium-sky battery-platinum nano-composite catalyst and preparation method thereof, the nano-composite catalyst is received by graphene and platinum
Rice grain is constituted, and using solid platinum as target, using liquid-phase pulse laser ablation technology, nano-platinum particle is grown on graphene.
The composite catalyzing material has good catalytic performance, under 100mA/g electric currents, and capacity reaches 4000mAh/g, and with compared with
Small polarization and excellent cyclical stability.Above-mentioned graphene-platinum nano-composite catalyst for lithium-sky battery needs to use
Prepared by liquid-phase pulse laser ablation technology, method is relatively complicated.
The content of the invention
The invention provides a kind of preparation method of the graphene-based combination electrode for lithium-air battery, this method work
Skill 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 the above method, the graphene-gold
Combination electrode has high power capacity, low overpotential and high circulation stability, and the usage amount of gold is relatively low.
Present invention also offers a kind of graphene-based combination electrode prepared by the above method in lithium-air battery
Application, by the lithium-air battery be applied to lithium-sky battery air electrode in, can be used to improve the electrochemistry of lithium-sky battery
Can, particularly reduce overpotential and improve cyclical stability, and save electrode preparing cost.
A kind of preparation method of graphene-gold combination electrode, comprises the following steps：
(1) using porous metals M as matrix, by chemical vapour deposition technique, graphene G is grown directly on matrix, is designated as
M/G；
(2) by HAuCl4·4H2O is dissolved in deionized water, stirs, and prepares aqueous solution of chloraurate；Under condition of ice bath, delay
Slow stirring 0.5~2 hour；The M/G that step (1) is obtained is immersed in above-mentioned aqueous solution of chloraurate, is stood and is completed to take out reaction production
Thing, is cleaned, vacuum drying repeatedly through deionization；
(3) under an argon atmosphere, drying product step (2) obtained is calcined 1~4h at 200~500 DEG C, after cooling
Obtain described M/G-Au combination electrode materials.
In step (1), preferably, concretely comprising the following steps：
Porous metals are put into tube furnace, 800~1200 DEG C, after insulation are warming up under an ar atmosphere, then use Ar air-flows
Ethanol is introduced in quartz ampoule, 3~10min is reacted；Finally, room temperature is cooled under an ar atmosphere, obtains being grown in porous metals
Graphene on matrix.
In step (1), described porous metals M is porous nickel (Ni), porous aluminum (Al) or POROUS TITANIUM (Ti).Porous metals
Porosity of=80%, thickness be 1-3mm.
In step (2), preferably, the concentration of the aqueous solution of chloraurate is 0.05~0.3mg/mL.In the step, institute
Show under condition of ice bath, the temperature of aqueous solution of chloraurate is generally less than 10 DEG C, generally 0~5 DEG C.
Described be slowly stirred generally refers to mixing speed for below 300rpm, generally refers to 50~200rpm.Low temperature eases up
Under slow mixing speed, gold ball particle surface is advantageously formed covered with this specific structure of one layer of thin golden film.
In step (2), the time of M/G immersion aqueous solution of chloraurate is generally 2~4 hours.The temperature of vacuum drying is general
For less than 80 DEG C, generally 55~65 DEG C.
In step (3), described sintering temperature is 200~400 DEG C.The temperature of described cooling does not have strict limit
It is fixed, based on adequate operation, it can typically be cooled to 15~30 DEG C of environment temperature.
Present invention also offers a kind of graphene-gold combination electrode, it is prepared by any of the above-described preparation method, the electricity
Pole is using porous metals M as matrix, direct growth graphene on matrix, is designated as direct growth Au on M/G, described graphene, note
For M/G-Au.
Specifically, the present invention directly prepares graphene by CVD using porous metals as matrix on matrix, described
Graphene replicate the loose structure of metal；Grow the gold of two kinds of forms in graphenic surface by ice bath infusion method again：Directly
Footpath is the spherical gold grains of 100~200nm, is uniformly distributed on graphene, and spherical particle surface is covered with one layer of thin golden film, gold
Film thickness is 10-20nm.Finally give the sandwich of graphene layer/Au particles/Au films.Graphene and Au have concerted catalysis
Act on, mechanism of action is：Graphene has certain catalytic action, but compared to Au, its catalytic action is weaker, in catalytic process
In predominantly Au catalytic process provide electric action；And although Au catalytic action is relatively strong, the electric action without graphene,
Its catalytic performance can not be realized fully.
Described direct growth refers to：First by CVD, the deposited graphite alkene directly on the skeleton of porous metals；So
Afterwards under condition of ice bath, graininess is directly grown on graphene with membranaceous gold；In contrast, indirect growth refers to conjunction in advance
Into graphenes and gold, then two kinds of raw materials and binding agent are well mixed in organic solvent, slurry is stirred into, be then coated in
On porous metal matrix.
In the sandwich of graphene layer/gold grain/golden film, graphene layer mainly provides electric action；Gold grain master
Catalytic action is played, Li is guided2O2Along its superficial growth, the passivation of electrode slow down；And golden film collaboration graphene layer will
Li2O2Growth be limited in sandwich, on the one hand keep the electric conductivity (gold have high electric conductivity) of whole electrode itself,
On the other hand Li is reduced2O2Contact with electrolyte is to reduce side reaction.Preferably, a diameter of the 100 of the gold grain~
200nm, is uniformly distributed on graphene, and little particle gold is conducive to improving catalytic performance, and golden film thickness is 10~20nm, thin gold
Film is conducive to the raising of electric conductivity, is also beneficial to be formed hole profit and provides passage for the diffusion of lithium ion and oxygen.
Preferably, in described graphene-gold combination electrode Au (including gold grain and golden film) bearing capacity for 0.4~
0.8mg/cm2.Au bearing capacity can be controlled by adjusting aqueous solution of chloraurate concentration and immersion time.Au bearing capacity
Very few, catalytic effect is undesirable, and in the more difficult formation membrane structure of particle surface；Bearing capacity is excessive, and gold grain is in graphene
Surface distributed is feeding-up, is unfavorable for Li2O2Deposition, be also unfavorable for forming relatively thin golden film, and increase and the ratio of cost can be caused
The decline of capacity.
Preferably, a small number of Rotating fields (2~10 layers) are presented in graphene in described graphene-gold combination electrode material,
The bearing capacity of graphene is 0.5~1.5mg/cm in described graphene-gold combination electrode2.The bearing capacity of graphene can pass through
The adjustment chemical vapor deposition time is controlled.Graphene is mainly that Au catalysis provides electric action, stone in catalytic process
The black too low raising for being unfavorable for electric conductivity of alkene content, and too high content can not produce work to the further raising of electric conductivity
With, and the increase of electrode weight can be caused.Therefore, it is the content control of graphene is more reasonable within the above range.
The invention also discloses described graphene-based-golden composite electrode answering in the air electrode as lithium-sky battery
With.
Compared with prior art, the invention has the advantages that：
1st, graphene and gold are directly grown on porous metal matrix in graphene-gold combination electrode prepared by the present invention,
Without other conductive agents and binding agent, with technique is simple, cost is low, the cycle is short, energy consumption is low and suitable industrialized production etc. is excellent
Point；
2nd, graphene and Au have concerted catalysis effect in graphene-gold combination electrode prepared by the present invention, are conducive to urging
Change the raising of performance, so as to effectively reduce the overpotential of lithium-sky battery；
3rd, sandwich is presented in graphene prepared by the present invention-gold combination electrode, is conducive to Li2O2Controllable growth to subtract
The passivation of slow electrode and the generation for reducing side reaction.
Brief description of the drawings
Fig. 1 is the X ray diffracting spectrum of nickel/graphene-gold combination electrode prepared by embodiment 1；
Fig. 2 is Ni/G prepared by embodiment 1 Raman (Raman) spectrogram；
Fig. 3 is the low power stereoscan photograph of graphene-gold combination electrode prepared by embodiment 1；
Fig. 4 is the high power stereoscan photograph of graphene-gold combination electrode prepared by embodiment 1；
Fig. 5 is the cycle performance figure using graphene-gold combination electrode of the preparation of embodiment 1 as lithium-sky battery of positive pole；
Fig. 6 is graphene-gold combination electrode stereoscan photograph prepared by comparative example 1；
Fig. 7 is the cycle performance figure using graphene-gold combination electrode of the preparation of comparative example 1 as lithium-sky battery of positive pole.
Embodiment
Embodiment 1
Porous nickel (porosity is 96%, and thickness is 1.6mm) is put into tube furnace, in Ar (500s.c.c.m.) atmosphere
Under be warming up to 1000 DEG C with 100 DEG C/min of programming rate；After insulation 5 minutes, with Ar (250s.c.c.m.) air-flows by ethanol
Introduce in quartz ampoule, react 5 minutes；Finally, room temperature is cooled to 100 DEG C/min of cooling rate under an ar atmosphere, given birth to
The bearing capacity 0.82mg/cm of long graphene (Ni/G), wherein graphene on porous nickel matrix2；By HAuCl4·4H2O is dissolved in
Deionized water, is stirred, and prepares concentration and is 0.16mg/mL solution, and the beaker for filling above-mentioned solution is placed in ice bath,
It is slowly stirred 1 hour；Ni/G is immersed into above-mentioned solution, 3 hours are stood, reaction product is taken out, cleaned repeatedly through deionization and
60 DEG C of vacuum dryings；It will be calcined 2 hours at products therefrom under an ar atmosphere 300 DEG C, be subsequently cooled to room temperature and obtain being carried on Ni
On G-Au combination electrodes (Ni/G-Au), wherein Au bearing capacity be 0.55mg/cm2。
Fig. 1 is Ni/G-Au electrodes X-ray diffraction spectrum manufactured in the present embodiment, and the material, which can be attributed to, to be supported on Ni
Graphene and gold.
Fig. 2 is Ni/G manufactured in the present embodiment Raman spectrum, and stronger 2D peaks show that graphene is a small number of Rotating fields.
Fig. 3 and Fig. 4 are respectively low power and the high power scanning of the G-Au electrodes manufactured in the present embodiment being carried in porous nickel
Electronic Speculum.Understand that G-Au is only grow on the skeleton of porous nickel from photo 3, and retain the loose structure of nickel.Au is understood from photo 4
Grain is dispersed on graphene, and granular size is 100~200nm, and on gold grain surface covered with golden film, thickness 10~20 is received
Rice, forms the sandwich of graphene layer/gold grain/golden film.
Using the G-Au manufactured in the present embodiment being carried in porous nickel as positive pole, using lithium metal as negative pole, polypropylene is thin
Film (trade mark Celgard C380, Celgard companies of the U.S.) is barrier film, LiClO4TRIGLYME (TEGDME) solution
For electrolyte, battery is assembled in the glove box full of argon gas.After being passed through the oxygen of 1 atmospheric pressure, charge-discharge test is carried out, its
Cyclic curve is as shown in Figure 5.
Constant volume charge-discharge test (capacity limit in 1000mAh/g, current density 400mA/g, voltage range 2V~4.5V,
Wherein capacity and current density are based on Au weight) show, in 100 charge and discharge process, the lithium-sky battery can keep steady
Fixed circulation.Its end current potential that discharges is maintained at 2.58V or so, shows relatively low polarization and preferable cyclical stability.
Comparative example 1
The deposition process be the same as Example 1 of graphene, Au deposition process is carried out under room temperature (25 DEG C), different from embodiment
1 condition of ice bath, other techniques are identical.It is specific as follows, porous nickel is put into tube furnace, in Ar (500s.c.c.m.) atmosphere
Under be warming up to 1000 DEG C with 100 DEG C/min of programming rate；After insulation 5 minutes, with Ar (250s.c.c.m.) air-flows by ethanol
Introduce in quartz ampoule, react 5 minutes；Finally, room temperature is cooled to 100 DEG C/min of cooling rate under an ar atmosphere, given birth to
The bearing capacity 0.82mg/cm of long graphene (Ni/G), wherein graphene on porous nickel matrix2；By HAuCl4·4H2O is dissolved in
Deionized water, stirs, and prepares the solution that concentration is 0.16mg/mL, is slowly stirred at a room temperature 1 hour；Ni/G is immersed
Above-mentioned solution, static 3 hours, takes out reaction product, is cleaned repeatedly through deionization and in 60 DEG C of vacuum dryings；Products therefrom is existed
It is calcined 2 hours at lower 300 DEG C of Ar atmosphere, is subsequently cooled to room temperature and obtains being carried on G-Au combination electrodes (Ni/G-Au) on Ni,
Wherein Au bearing capacity is 0.8mg/cm2.Deposit gold and graininess is presented, average particle size particle size is more than 200nm, particle table
Face does not form golden film and sees Fig. 6.
The G-Au being carried in porous nickel using the preparation of this comparative example is as positive pole, and using lithium metal as negative pole, polypropylene is thin
Film (trade mark Celgard C380, Celgard companies of the U.S.) is barrier film, LiClO4TRIGLYME (TEGDME) solution
For electrolyte, battery is assembled in the glove box full of argon gas.After being passed through the oxygen of 1 atmospheric pressure, charge-discharge test is carried out, is filled
Discharge curve is as shown in Figure 7.
Constant volume charge-discharge test (capacity limit in 1000mAh/g, current density 400mA/g, voltage range 2V~4.5V,
Wherein capacity and current density are based on Au weight) show, in secondary charge and discharge process, the lithium-sky battery is only capable of adhering to 28 times
Stable circulation, and 2V is down in discharge voltage circulation, shows higher polarization and poor cyclical stability.
Embodiment 2
Porous nickel (porosity is 90%, and thickness is 2.5mm) is put into tube furnace, in Ar (500s.c.c.m.) atmosphere
Under be warming up to 1000 DEG C with 100 DEG C/min of programming rate；After insulation 5 minutes, with Ar (250s.c.c.m.) air-flows by ethanol
Introduce in quartz ampoule, react 8 minutes；Finally, room temperature is cooled to 100 DEG C/min of cooling rate under an ar atmosphere, given birth to
The bearing capacity 1.25mg/cm of long graphene (Ni/G), wherein graphene on porous nickel matrix2；By HAuCl4·4H2O is dissolved in
Deionized water, is stirred, and prepares concentration and is 0.1mg/mL solution, and the beaker for filling above-mentioned solution is placed in ice bath,
It is slowly stirred 1 hour；Ni/G is immersed into above-mentioned solution, 3 hours are stood, reaction product is taken out, cleaned repeatedly through deionization and
60 DEG C of vacuum dryings；It will be calcined 4 hours at products therefrom under an ar atmosphere 200 DEG C, be subsequently cooled to room temperature and obtain being carried on Ni
On G-Au combination electrodes (Ni/G-Au), wherein Au bearing capacity be 0.45mg/cm2.XRD shows that graphene and Au are deposited on
In porous nickel.Raman spectrum show that graphene is a small number of Rotating fields.SEM photograph shows that G-Au is only grow on the bone of porous nickel
On frame, and retain the loose structure of nickel.Au even particulate dispersions are on graphene, and granular size is 100~200nm, in gold
Grain surface forms the sandwich of graphene layer/gold grain/golden film covered with golden film, 10~20 nanometers of thickness.
Using the G-Au manufactured in the present embodiment being carried in porous nickel as positive pole, using lithium metal as negative pole, polypropylene is thin
Film (trade mark Celgard C380, Celgard companies of the U.S.) is barrier film, LiClO4TRIGLYME (TEGDME) solution
For electrolyte, battery is assembled in the glove box full of argon gas.After being passed through the oxygen of 1 atmospheric pressure, charge-discharge test is carried out.
Constant volume charge-discharge test (capacity limit in 1000mAh/g, current density 400mA/g, voltage range 2V~4.5V,
Wherein capacity and current density are based on Au weight) show, in 100 charge and discharge process, the lithium-sky battery can keep steady
Fixed circulation.Its end current potential that discharges is maintained at 2.55V or so, shows relatively low polarization and preferable 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
1000 DEG C are warming up to 100 DEG C/min of programming rate；After insulation 5 minutes, ethanol is drawn with Ar (250s.c.c.m.) air-flow
Enter in quartz ampoule, react 3 minutes；Finally, room temperature is cooled to 100 DEG C/min of cooling rate under an ar atmosphere, grown
The bearing capacity 0.55mg/cm of graphene (Al/G), wherein graphene on porous aluminum substrate2；By HAuCl4·4H2O is dissolved in
Ionized water, stirs, and prepares concentration and is 0.2mg/mL solution, and the beaker for filling above-mentioned solution is placed in into frozen water mixed liquor
In, it is slowly stirred 1.5 hours；Al/G is immersed into above-mentioned solution, 4 hours are stood, reaction product is taken out, is cleaned repeatedly through deionization
And in 60 DEG C of vacuum dryings；It will be calcined 2.5 hours at products therefrom under an ar atmosphere 300 DEG C, be subsequently cooled to room temperature and born
The G-Au combination electrodes (Al/G-Au) on Al are loaded in, wherein Au bearing capacity is 0.6mg/cm2.XRD shows, graphene and Au
It is deposited in porous Al.Raman spectrum show that graphene is a small number of Rotating fields.SEM photograph shows that G-Au is only grow on porous
On the skeleton of aluminium, and retain Al loose structure.Au even particulate dispersions are on graphene, and granular size is 100~200nm,
On gold grain surface covered with golden film, 10~20 nanometers of thickness forms the sandwich of graphene layer/gold grain/golden film.
Using the G-Au manufactured in the present embodiment being carried in porous aluminum as positive pole, using lithium metal as negative pole, polypropylene is thin
Film (trade mark Celgard C380, Celgard companies of the U.S.) is barrier film, LiClO4TRIGLYME (TEGDME) solution
For electrolyte, battery is assembled in the glove box full of argon gas.After being passed through the oxygen of 1 atmospheric pressure, charge-discharge test is carried out.
Constant volume charge-discharge test (capacity limit in 1000mAh/g, current density 400mA/g, voltage range 2V~4.5V,
Wherein capacity and current density are based on Au weight) show, in 100 charge and discharge process, the lithium-sky battery can keep steady
Fixed circulation.Its end current potential that discharges is maintained at 2.53V or so, shows relatively low polarization and preferable 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
1000 DEG C are warming up to 100 DEG C/min of programming rate；After insulation 5 minutes, ethanol is drawn with Ar (250s.c.c.m.) air-flow
Enter in quartz ampoule, react 10 minutes；Finally, room temperature is cooled to 100 DEG C/min of cooling rate under an ar atmosphere, given birth to
The bearing capacity 1.45mg/cm of long graphene (Ti/G), wherein graphene on porous Titanium base2；By HAuCl4·4H2O is dissolved in
Deionized water, stirs, and prepares concentration and is 0.25mg/mL solution, and the beaker for filling above-mentioned solution is placed in into frozen water and mixes
Close in liquid, be slowly stirred 2 hours；Ti/G is immersed into above-mentioned solution, 2 hours are stood, reaction product is taken out, it is repeatedly clear through deionization
Wash and in 60 DEG C of vacuum dryings；It will be calcined 1.5 hours at products therefrom under an ar atmosphere 400 DEG C, be subsequently cooled to room temperature and obtain
The G-Au combination electrodes (Ti/G-Au) on Ti are carried on, wherein Au bearing capacity is 0.65mg/cm2.XRD shows, graphene and
Au is deposited on porous Ti.Raman spectrum show that graphene is a small number of Rotating fields.SEM photograph shows that G-Au is only grow on many
On the skeleton of hole titanium, and retain the loose structure of titanium.Au even particulate dispersions on graphene, granular size is 100~
200nm, on gold grain surface covered with golden film, 10~20 nanometers of thickness forms the interlayer knot of graphene layer/gold grain/golden film
Structure.
Using the G-Au manufactured in the present embodiment being carried in POROUS TITANIUM as positive pole, using lithium metal as negative pole, polypropylene is thin
Film (trade mark Celgard C380, Celgard companies of the U.S.) is barrier film, LiClO4TRIGLYME (TEGDME) solution
For electrolyte, battery is assembled in the glove box full of argon gas.After being passed through the oxygen of 1 atmospheric pressure, charge-discharge test is carried out.
Constant volume charge-discharge test (capacity limit in 1000mAh/g, current density 400mA/g, voltage range 2V~4.5V,
Wherein capacity and current density are based on Au weight) show, in 100 charge and discharge process, the lithium-sky battery can keep steady
Fixed circulation.Its end current potential that discharges is maintained at 2.61V or so, shows relatively low polarization and preferable cyclical stability.
Claims (9)
1. the preparation method of a kind of graphene-gold combination electrode, it is characterised in that comprise the following steps：
(1) using porous metals M as matrix, by chemical vapour deposition technique, graphene G is grown directly on matrix, M/G is designated as；
(2) by HAuCl4·4H2O is dissolved in deionized water, prepares under aqueous solution of chloraurate, condition of ice bath, is slowly stirred 0.5~2 small
When；The M/G that step (1) is obtained is immersed in above-mentioned aqueous solution of chloraurate, is stood and is completed, and takes out reaction product, anti-through deionization
Multiple cleaning, vacuum drying；
(3) under an argon atmosphere, drying product step (2) obtained is calcined 1~4h at 200~500 DEG C, is obtained after cooling
Described M/G-Au combination electrode materials.
2. the preparation method of graphene according to claim 1-gold combination electrode, it is characterised in that described porous gold
Category M is one kind in porous nickel, porous aluminum or POROUS TITANIUM, and the porosity of=80% of porous metals, thickness is 1-3mm.
3. the preparation method of graphene according to claim 1-gold combination electrode, it is characterised in that in step (2), institute
The concentration for stating aqueous solution of chloraurate is 0.05~0.3mg/mL；The time of M/G immersion aqueous solution of chloraurate is generally 2~4 hours.
4. the preparation method of graphene according to claim 1-gold combination electrode, it is characterised in that in step (3), institute
Sintering temperature is stated for 200~400 DEG C.
5. a kind of graphene-gold combination electrode, it is characterised in that the graphene-gold combination electrode is any by claim 1-4
Preparation method described in claim is prepared.
6. graphene according to claim 5-gold combination electrode, it is characterised in that two kinds of forms are presented in Au therein, i.e.,
Spherical gold grain and golden film；The spherical gold grain, is uniformly distributed on graphene, a diameter of 100~200nm；The golden film
Spherical particle surface is covered in, golden film thickness is 10~20nm.
7. graphene according to claim 5-gold combination electrode, it is characterised in that the graphene-gold combination electrode material
Au bearing capacity is 0.4~0.8mg/cm in material2。
8. graphene according to claim 5-gold combination electrode, it is characterised in that the graphene-gold combination electrode material
Graphene bearing capacity is 0.5~1.5mg/cm in material2。
9. application of a kind of graphene-gold combination electrode in the air electrode as lithium-sky battery, it is characterised in that described
Graphene-gold combination electrode is prepared as the preparation method described in claim 1-4 any claims.
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| CN105789637B (en) * | 2016-04-20 | 2017-12-29 | 浙江大学 | Area load has carbon nano pipe array electrode of Au nano particles and its preparation method and application |
| CN106057968A (en) * | 2016-06-12 | 2016-10-26 | 上海大学 | Preparation method for graphene-gold combined electrode used for diamond radiation detector |
| CN108199007B (en) * | 2017-12-28 | 2020-04-07 | 厦门紫阳新能源科技有限公司 | Preparation method of graphene pole piece |
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| EP2704245A1 (en) * | 2012-09-03 | 2014-03-05 | Agencia Estalal Consejo Superior de Investigaciones Cientificas | Method for preparing carbon coated electrode active material particles |
| CN103825003A (en) * | 2014-02-27 | 2014-05-28 | 浙江大学 | Three-dimensional porous Co3O4/Pt/Ni combined electrode, its preparation method and its application |
| CN103840179A (en) * | 2014-02-27 | 2014-06-04 | 浙江大学 | Three-dimensional graphene-based combined electrode with MnO2 and Au nanoparticle-coating surface, and preparation method and applications thereof |
| CN103840176A (en) * | 2014-02-27 | 2014-06-04 | 浙江大学 | Three-dimensional graphene-based combined electrode with Au nanoparticle-loaded surface, and preparation method and applications thereof |
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| EP2704245A1 (en) * | 2012-09-03 | 2014-03-05 | Agencia Estalal Consejo Superior de Investigaciones Cientificas | Method for preparing carbon coated electrode active material particles |
| CN103825003A (en) * | 2014-02-27 | 2014-05-28 | 浙江大学 | Three-dimensional porous Co3O4/Pt/Ni combined electrode, its preparation method and its application |
| CN103840179A (en) * | 2014-02-27 | 2014-06-04 | 浙江大学 | Three-dimensional graphene-based combined electrode with MnO2 and Au nanoparticle-coating surface, and preparation method and applications thereof |
| CN103840176A (en) * | 2014-02-27 | 2014-06-04 | 浙江大学 | Three-dimensional graphene-based combined electrode with Au nanoparticle-loaded surface, and preparation method and applications thereof |
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