CN104201438A - Lithium-air battery based on oxidized graphene-carbon paper gas catalytic electrode - Google Patents
Lithium-air battery based on oxidized graphene-carbon paper gas catalytic electrode Download PDFInfo
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- CN104201438A CN104201438A CN201410491554.6A CN201410491554A CN104201438A CN 104201438 A CN104201438 A CN 104201438A CN 201410491554 A CN201410491554 A CN 201410491554A CN 104201438 A CN104201438 A CN 104201438A
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- carbon paper
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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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- 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
- H01M4/8853—Electrodeposition
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/96—Carbon-based electrodes
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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
- 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
Abstract
The invention provides a lithium-air battery based on an oxidized graphene-carbon paper gas catalytic electrode. The positive electrode of the battery is an oxidized graphene catalytic electrode which is prepared by the following method and is supported by carbon paper. A preparation method comprises the steps of performing ultrasonic dispersion on oxidized graphene in a phosphate buffering solution to form a suspension state so as to prepare electrolyte; then the carbon paper is used as positive electrode, and a platinum electrode is used as a negative electrode; the voltage of an electrolytic battery is controlled to be 5-20V; under a proper stirring speed and proper temperature, electrophoresis-electrolysis is performed for 5-30 minutes; after electrolytic deposition is ended, oxidized graphene is loaded on the carbon paper; the carbon paper is washed by secondary distilled water and is dried under vacuum; finally a load of the oxidized graphene on the carbon paper is weighed and metered by an analysis balance. The preparation steps are simple; operation parameters are easy to control; the performance of the electrodes is stable, and reproduction is realized; under the current density of 0.1mA/cm<2>, the first discharge capacity is 11,553mAh/g; after the circulating battery runs for 520 hours, the performance is stable.
Description
Technical field
The invention provides a kind of lithium-air battery, relate in particular to a kind of lithium-air battery based on graphene oxide-carbon paper gas catalysis electrode, belong to lithium-air battery and technology of preparing thereof.
Background technology
Lithium-air battery is a kind of taking lithium metal as negative pole, and air is anodal secondary cell.It has and the diverse design of lithium ion battery, and its theoretical specific energy is 11140Wh/kg (not comprising oxygen quality), approaches the theoretical specific energy value 13000Wh/kg of gasoline.Even if consider the quality of oxygen, its specific energy is also ten times (5210Wh/kg) of common lithium ion battery.1996, Zhu Sai state, the U.S. Marseille EIC lab A doctor braham reported first lithium-air battery of this new polymers electrolyte system, obtain the specific discharge capacity of 1400Ah/kg, can utilize specific energy 1700Wh/kg close to gasoline reality.This achievement is worldwide approved widely, thereby has been caused the research boom that is developed to automobile power cell.Lithium-air battery is the one of metal-air batteries, is called again semi-fuel cell, is the fuel cell that consumes Li, is also that positive active material is the lithium battery of oxygen.It and lithium ion battery and fuel cell have similarity, also have difference.Compared with fuel cell, lithium metal substitutes hydrogen for lithium-air battery, therefore need not consider the storage problem of hydrogen, and lithium-air battery can realize and fill/put circulation, is one energy-storage battery easily; Compared with lithium ion battery, lithium-air battery can directly obtain positive active material--oxygen from air, and do not need to be stored in battery system, significantly alleviate the weight of battery system, therefore the great development that, can realize in theory the lithium-air battery of large capacity energy storage is worth and is subject to extensive concern.
Although lithium-air battery shows good application prospect, in fact performance is limited by various factors, on its energy conversion efficiency Distance Theory, can arrival value differ greatly.At present, the negative pole of lithium-air battery adopts metal lithium sheet, for preventing lithium metal passivation, conventionally use comparatively ripe ethylene carbonate (EC), methyl ethyl carbonate (EMC), dimethyl carbonate (DMC) mixed solvent to configure the 1mol/dm forming
3liPF
6eC/EMC/DMC (mass ratio 1:1:1) nonaqueous electrolytic solution (although aqueous electrolyte and solid electrolyte are also under study for action), air electrode is coated in nickel foam and is formed by the mixed slurry of (carbon dust/catalyst/adhesive).In the environment of isolated air, be assembled into battery:
(-) lithium sheet | organic electrolyte-barrier film | gas-diffusion electrode (+)
In the lithium-air battery of non-aqueous system, the Li that when battery discharge, the oxidation of negative pole lithium sheet produces
+move to positive pole by electrolyte, with the oxonium ion of crossing of oxygen reduction generation
(or the oxonium ion O that further reaction produces
2-) form the oxide of lithium.And charging process is contrary with discharge process, when charging, the decomposition of the oxide of lithium produces oxygen and lithium ion.Discharging product Li
2o
2generation do not need the fracture of O-O key, therefore reaction does not need very high activation energy, under the condition that does not use catalyst, can carry out smoothly yet, sees accompanying drawing 1.And charging process is that the oxide of the lithium forming is decomposed, the oxide of lithium is ionic crystals, decomposed the activation energy that needs are higher, and in the time having electrolyte or binder decomposed to cause discharging product become lithium carbonate or contain the organic substance of lithium, the required activation energy that charges is higher, and therefore in charging process, the use of oxygen-separating catalyst is essential.Relevant evidence shows, discharging product Li
2o
2or Li
2o does not dissolve in nonaqueous electrolytic solution, and after once discharging, air one side of electrode has the unordered accumulation of a large amount of discharging product, and barrier film one side there is no discharging product, thereby causes oxygen transmission passage to stop up, and causes discharge off.And, solid-state Li
2o
2or Li
2o ionic crystals is almost insulator, causes electrode conductivuty to destroy once generate also unordered accumulation, and charging cannot be carried out.The visible cell reaction product of realizing distributes in anodal ordering, ensures that in charging process, electrode conductivuty is uninterrupted, accelerates
or O
2-→ O
2conversion rate, be that organic electrolyte is the anodal key issue that must solve of lithium-air battery, this is also that people launched the extensive target of exploring untiringly at aspects such as new carbon research, multifunctional efficient catalyst research, electrode space structural design and trials in the last few years.
Summary of the invention
The invention provides a kind of lithium-air battery based on graphene oxide-carbon paper gas catalysis electrode, this battery has higher capacity and charges and discharge cycle performance than existing lithium-air battery; The present invention also provides a kind of electrophoresis-strike to prepare the method for graphene oxide-carbon paper electrode.
Realizing the technical scheme that above-mentioned purpose of the present invention adopts is:
A kind of lithium-air battery based on graphene oxide-carbon paper gas catalysis electrode, the graphene oxide catalysis electrode that just very adopts carbon paper that following methods makes to support of this battery, preparation method is as follows: the ultrasonic suspended state that is dispersed in the phosphate buffer that is 5～9 in pH value by graphene oxide, makes electrolyte; Then make positive pole with carbon paper, platinum electrode is made negative pole, is assembled into electrophoresis-electrolytic cell, and adopting D.C. regulated power supply control electrophoresis-electrolytic cell voltage is 5～20V, and the temperature of electrolyte is controlled at 20～50 DEG C, and electrophoresis-electrolysis time is 5～30 minutes; In electrolytic process, for making graphene oxide at carbon paper surface uniform adventitious deposit, adopt at the uniform velocity agitating device, stir speed (S.S.) is 1000～4000r/min, after electrolytic deposition finishes, graphene oxide is deposited on carbon paper; Then there is the carbon paper of graphene oxide with redistilled water wash load, vacuumize at 80～120 DEG C after washing, finally use the load capacity of graphene oxide on assay balance Weighing carbon paper, on described carbon paper, the load capacity of graphene oxide is 0.1～1.0mg/cm
2.
Described carbon paper is for through hydrophobic and leveling carbon paper after treatment, and its thickness is 25～34 μ m, with the contact angle of water be 90～140 °.
In described electrolyte, the concentration of graphene oxide is 0.5～3.0mg/cm
3.
In the time preparing lithium-air battery, the carbon paper of above-mentioned load graphene oxide is cut into required area and makes positive pole, make negative pole with lithium sheet, inject 1mol/dm
3liPF
6eC/EMC/DMC (mass ratio 1:1:1) nonaqueous electrolytic solution, under isolated air, be assembled into button cell, under open circuit voltage, leave standstill 3-24 hour, take constant current free discharge pattern and controlled discharge depth mode to carry out discharge test, recording voltage-time graph and voltage-specific capacity curve.
In the present invention, because graphene oxide is that sheet is peeled off the derivative of graphite after oxidation processes, still keep the layer structure of graphite, each carbon atom is with sp
2hybridized orbit covalency is connected, but on the Graphene monolithic of every one deck, has introduced containing oxygen base functional group.The generally accepted structural model of present stage people is that random distribution hydroxyl and epoxy radicals on graphene oxide two dimensional surface, has introduced carbonyl and carboxyl at the edge of monolithic, sees accompanying drawing 2.Although the quantity of these oxy radicals and distribution can be different because of preparation method, but certainly, containing the introducing of oxygen base functional group, graphene oxide is had amphipathic, present hydrophilic extremely hydrophobic character from graphene platelet edge to central authorities, thereby make it to be suspended in the aqueous solution.Therefore considered in the present invention following factor: 1, the carbonyl of graphene oxide can be opened two keys by electrolytic oxidation method, forms graphene oxide surface on carbon paper; 2, the hydroxyl of graphene oxide, carboxyl contained-OH group can regard a kind of " water " of broad sense as, offer cell reaction product by Li at electrode surface
2o
2or Li
2o changes to LiOH; 3, still keep the layer structure of graphite due to graphene oxide, perpendicular to sp
2the large π key of delocalization of carbocyclic ring plane can strengthen the electron conduction of carbon paper; 4, graphene oxide has stronger electron-withdrawing power containing oxygen base functional group, when battery charging, can induce
or O
2-, or OH
-trend positive discharge, actually plays oxygen reduction reaction (electric discharge, ORR) and analyses the effect of oxygen conversion reaction (charging, OER) catalyst.
In lithium-air battery provided by the invention, its positive pole has carried out combination by graphene oxide and carbon paper dexterously, its advantage is: one, utilize porousness, conductivity, the stability of carbon paper, avoid the corrosion of charging voltage collector after 4.2V, due to carbon dust and catalyst material without any need for affecting electrode electron conduction and pore volume, do not need 1-METHYLPYRROLIDONE dispersant (NMP) and PVDF adhesive yet, greatly reduce anodal ohmic voltage drop, see Fig. 4; Its two, carbon paper and graphene oxide are all material with carbon element, make graphene oxide and carbon paper bonding by electrolytic oxidation, at positive pole introducing-OH and COOH functional group, can promote Li
2o
2or Li
2o, can be by original charging reaction Li to the transformation of LiOH
2o
2→ 2Li
++ O
2+ 2e or Li
2o → 2Li+O
2+ 4e changes OH into
-electric discharge on electrode: 4OH
-→ O
2+ H
2o+4e, along with Li
2o
2or Li
2o solid crystals is in electrode broad sense " water " effect lower transition and fluidization, overcome the electrode conductivuty that cell reaction product causes in the unordered accumulation of electrode hole and has been interrupted, make to charge cannot be lasting problem; Its three, carbonyl, the carboxyl etc. of graphene oxide has attraction electronic capability containing oxygen base functional group, can evoked electrode active material (Li when charging
2o
2or Li
2o, and then be OH
-) adsorb and discharge at electrode surface, in fact play the effect of catalyst, reach the object that charging reaction is carried out smoothly, greatly improve stability, cyclicity and the practicality of lithium-air battery; Finally, portable and stable after lithium-air battery assembling of the present invention, voltage platform is high; discharge capacity is large, has realized the stable circulation of filling/put under certain discharge system, and; preparation technology of the present invention and operating parameter are simple and easy to control, are easy to accomplish scale production, and are convenient to Industry Promotion.
Brief description of the drawings
Fig. 1 is the comparison diagram of discharge curve first of carbon paper positive pole (CP) and graphene oxide-carbon paper positive pole (GO-CP) in the present invention;
Fig. 2 is graphene oxide structural representation in the present invention;
Fig. 3 be in the present invention by electrolysis load carbon paper SEM figure and the partial enlarged drawing of graphene oxide;
Fig. 4 is the comparison diagram of discharge curve first of comparative example 1 and embodiment 1 in the present invention;
Fig. 5 is the charge and discharge cycles curve of making anodal lithium-air battery in comparative example 3 with pure carbon paper;
Fig. 6 is load graphene oxide-carbon paper electrode (GO-CP) in the present invention and the Raman spectrum of the carbon paper (CP) using;
Fig. 7 is at 0.05mA/cm in the embodiment of the present invention 1
2and 0.1mA/cm
2current density under discharge curve first;
Fig. 8 be circulating for 81-100 time of intercepting in the embodiment of the present invention 2 charge and discharge cycle graph;
Fig. 9 be in the present invention embodiment 3 charge and discharge cycle graph.
Embodiment
In order to set forth preferably content of the present invention, substantive features and marked improvement, below in conjunction with relevant comparative example and embodiment, the invention will be further described.It should be noted that at this, for enumerating of concrete comparative example and embodiment, be for helping to understand the present invention, but the present invention is not limited to following examples.Carbon paper described in following examples is for through hydrophobic and leveling carbon paper after treatment, and its thickness is 25～34 μ m, with the contact angle of water be 90～140 °.
Comparative example 1
The Graphene of buying and Kynoar (PVDF) are modulated into the slurry of certain viscosity in 1-METHYLPYRROLIDONE (NMP) medium by the mass ratio of 90:10, the method that employing is similar to silk screen printing is coated to slurry on carbon paper equably, then put into vacuum drying oven, at 80 DEG C, dry 12h, after oven dry, weigh, and the carbon paper blunderbuss coating is become to diameter is the disk of 8mm, make thus positive plate for subsequent use.
In the glove box of argon shield; adopt CR2032 battery case (anode cover surface has punched to ensure the transmission channel of oxygen) as battery pack; successively metal lithium sheet (Φ 15.6 × 0.45mm), barrier film Celgard 2325, positive plate are successively installed; and 1M LiPF6 (EC:EMC:DMC=1:1:1) electrolyte that drips appropriate business is infiltrated electrode and barrier film; battery is sealed on packaging machine, complete battery assembling.
The whole service process of battery is carried out in dry oxygen, at 0.05mA/cm
2current density under, discharge capacity is 6022mAh/g first, discharge platform, in about 2.7V, is shown in accompanying drawing 4.
Comparative example 2
Using the pure carbon paper of drying as positive pole, make lithium-air battery by the method in comparative example 1, obtain as the discharge curve in accompanying drawing 1, discharge capacity is 13830.7mAh/g (pure carbon paper) first, discharge platform mean value is in 2.7V left and right.
Comparative example 3
Using dry pure carbon paper as positive pole, suppose identical with the load capacity in embodiment 1, the controlled discharge degree of depth, controlled discharge capacity is 1000mAh/g, obtains the cyclic curve in accompanying drawing 5, pure carbon paper electrode is discharge off after 20 times charge and discharge.
Embodiment 1
By graphene oxide with 1.0mg/cm
3ultrasonic being scattered in redistilled water of concentration, add KH
2pO
4and K
2hPO
4, be mixed with the phosphate buffer solution of pH9.0, continue ultrasonic dispersion 6h, make it into homodisperse suspension.Taking platinum electrode as negative pole, carbon paper is anodal, be assembled into electrophoresis-electrolytic cell, stabilized voltage power supply control electrolytic cell voltage is at 20V, and the temperature of electrolyte is controlled at 45 DEG C, in electrolytic process, for making graphene oxide at carbon paper surface uniform adventitious deposit, adopted at the uniform velocity agitating device, stir speed (S.S.) is 2000r/min, and the cell reaction time is 5min.The carbon paper electrode of load graphene oxide is cleaned with redistilled water, and accompanying drawing 6 is shown in by its Raman collection of illustrative plates.The carbon paper electrode of the load graphene oxide after cleaning is dried to 12h at 80 DEG C in vacuum drying oven, weigh, it is the disk assembled battery of 8mm that blunderbuss becomes diameter.Respectively at 0.05mA/cm
2and 0.1mA/cm
2current density under constant-current discharge, its first discharge curve as accompanying drawing 7.Power supply is two electrode DC power supply.
Embodiment 2
By graphene oxide with 2.0mg/cm
3ultrasonic being scattered in redistilled water of concentration, add KH
2pO
4and K
2hPO
4, be mixed with the phosphate buffer solution of pH8.0, continue ultrasonic dispersion 6h, make it into homodisperse suspension.Taking platinum electrode as negative pole, carbon paper is anodal, be assembled into electrophoresis-electrolytic cell, stabilized voltage power supply control electrolytic cell voltage is at 15V, and the temperature of electrolyte is controlled at 35 DEG C, in electrolytic process, for making graphene oxide at carbon paper surface uniform adventitious deposit, adopted at the uniform velocity agitating device, stir speed (S.S.) is 3000r/min, and the cell reaction time is 15min.The carbon paper electrode of load graphene oxide is cleaned with redistilled water, the carbon paper electrode of the load graphene oxide after cleaning is dried to 10h at 100 DEG C in vacuum drying oven, weigh, it is the disk assembled battery of 8mm that blunderbuss becomes diameter.
Adopt the positive plate of preparing in the present embodiment, at 0.05mA/cm
2current density under, controlled discharge capacity is 500mAh/g (calculating by the amount of load graphene oxide), it charges and discharge cyclic curve as accompanying drawing 8.
Embodiment 3
By graphene oxide with 3.0mg/cm
3ultrasonic being scattered in redistilled water of concentration, add KH
2pO
4and K
2hPO
4, be mixed with the phosphate buffer solution of pH7.0, continue ultrasonic dispersion 6h, make it into homodisperse suspension.Taking platinum electrode as negative pole, carbon paper is anodal, be assembled into electrophoresis-electrolytic cell, stabilized voltage power supply control electrolytic cell voltage is at 8V, and the temperature of electrolyte is controlled at 25 DEG C, in electrolytic process, for making graphene oxide at carbon paper surface uniform adventitious deposit, adopted at the uniform velocity agitating device, stir speed (S.S.) is 4000r/min, and the cell reaction time is 25min.The carbon paper electrode of load graphene oxide is cleaned with redistilled water, the carbon paper electrode of the load graphene oxide after cleaning is dried to 8h at 120 DEG C in vacuum drying oven, weigh, it is the disk assembled battery of 8mm that blunderbuss becomes diameter.
Adopt the positive plate of preparing in the present embodiment, at 0.05mA/cm
2current density under, controlled discharge capacity is 1000mAh/g (calculating by the amount of load graphene oxide), it charges and discharge cyclic curve as accompanying drawing 9.
Claims (3)
1. the lithium-air battery based on graphene oxide-carbon paper gas catalysis electrode, it is characterized in that: the graphene oxide catalysis electrode that just very adopts carbon paper that following methods makes to support of this battery, preparation method is as follows: the ultrasonic suspended state that is dispersed in the phosphate buffer that is 5～9 in pH value by graphene oxide, makes electrolyte; Then make positive pole with carbon paper, platinum electrode is made negative pole, is assembled into electrophoresis-electrolytic cell, and adopting D.C. regulated power supply control electrophoresis-electrolytic cell voltage is 5～20V, and the temperature of electrolyte is controlled at 20～50 DEG C, and electrophoresis-electrolysis time is 5～30 minutes; In electrolytic process, for making graphene oxide at carbon paper surface uniform adventitious deposit, adopt at the uniform velocity agitating device, stir speed (S.S.) is 1000～4000r/min, after electrolytic deposition finishes, graphene oxide is deposited on carbon paper; Then there is the carbon paper of graphene oxide with redistilled water wash load, vacuumize at 80～120 DEG C after washing, finally use the load capacity of graphene oxide on assay balance Weighing carbon paper, on described carbon paper, the load capacity of graphene oxide is 0.1～1.0mg/cm
2.
2. lithium～the air cell based on graphene oxide-carbon paper gas catalysis electrode according to claim 1, it is characterized in that: described carbon paper is for process is hydrophobic and leveling carbon paper after treatment, its thickness is 25～34 μ m, with the contact angle of water be 90～140 °.
3. lithium～the air cell based on graphene oxide-carbon paper gas catalysis electrode according to claim 1, is characterized in that: in described electrolyte, the concentration of graphene oxide is 0.5～3.0mg/cm
3.
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| CN107026274A (en) * | 2017-05-16 | 2017-08-08 | 中国地质大学（武汉） | The graphene/carbon paper gas electrode preparation method and applications of borax buffer system |
| CN107342428B (en) * | 2017-06-08 | 2020-02-07 | 中国科学技术大学 | Method for enhancing microbial extracellular electron transfer in microbial electrochemical system |
| CN107342428A (en) * | 2017-06-08 | 2017-11-10 | 中国科学技术大学 | A kind of method of the extracellular electron transmission of enhancement microbiological in microorganism electrochemical system |
| CN107768688B (en) * | 2017-10-24 | 2020-09-04 | 昆明纳太科技有限公司 | Gas diffusion catalytic electrode, preparation method thereof and application thereof in rechargeable zinc-air battery |
| CN107768688A (en) * | 2017-10-24 | 2018-03-06 | 昆明纳太科技有限公司 | A kind of gas diffusion catalysis electrode and preparation method thereof and the application in zinc-air battery can filled |
| CN108110223A (en) * | 2017-12-18 | 2018-06-01 | 北京鼎能开源电池科技股份有限公司 | A kind of graphene cathode pole piece and preparation method thereof |
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