CN104201438B - A kind of lithium-air battery based on graphene oxide-carbon paper gas catalysis electrode - Google Patents
A kind of lithium-air battery based on graphene oxide-carbon paper gas catalysis electrode Download PDFInfo
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- CN104201438B CN104201438B CN201410491554.6A CN201410491554A CN104201438B CN 104201438 B CN104201438 B CN 104201438B CN 201410491554 A CN201410491554 A CN 201410491554A CN 104201438 B CN104201438 B CN 104201438B
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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 kind of lithium-air battery based on graphene oxide carbon paper gas catalysis electrode, the graphene oxide catalysis electrode that the carbon paper the most extremely using following methods to prepare of this battery supports, preparation method is as follows: graphene oxide ultrasonic disperse in phosphate buffer is become suspended state, prepares electrolyte；Then making positive pole with carbon paper, negative pole made by platinum electrode, and controlling electrolytic cell voltage is 5～20V, suitable mixing speed and at a temperature of, electrophoresis is electrolysed 5～30 minutes, after electrolytic deposition terminates, graphene oxide-loaded on carbon paper；Wash carbon paper with redistilled water again, be then vacuum dried, finally by the load capacity of graphene oxide on analytical balance Weighing carbon paper.Preparation process of the present invention is simple, and operating parameter is easily-controllable, and electrode performance is stable and reappears, at 0.1mA/cm2Under electric current density, discharge capacity reaches 11553mAh/g first, cycle battery run 520 hours after stable performance.
Description
Technical field
The invention provides a kind of lithium-air battery, particularly relate to a kind of based on graphene oxide-carbon paper gas catalysis electrode
Lithium-air battery, belong to lithium-air battery and technology of preparing thereof.
Background technology
Lithium-air battery is a kind of with lithium metal as negative pole, and air is the secondary cell of positive pole.It has and lithium-ion electric
The diverse design in pond, its theoretical specific energy is 11140Wh/kg (not including oxygen quality), close to the theory ratio of gasoline
Energy value 13000Wh/kg.Even if considering the quality of oxygen, its specific energy is also ten times of conventional lithium-ion battery
(5210Wh/kg).1996, Zhu Sai state, U.S. Marseille EIC lab A braham doctor's reported first was this newly
The lithium-air battery of type polymer electrolyte system, it is thus achieved that the specific discharge capacity of 1400Ah/kg, actual close to gasoline
Available specific energy 1700Wh/kg.This achievement is approved the most widely, thus has caused and developed
Become the research boom of automobile power cell.Lithium-air battery is the one of metal-air batteries, is called again semi-fuel cell,
Be consume Li fuel cell, be also positive active material be the lithium battery of oxygen.It is electric with lithium ion battery and fuel
There is similarity in pond, also has difference.Compared with fuel cell, lithium-air battery lithium metal substitutes hydrogen, because of
This need not consider the storage problem of hydrogen, and lithium-air battery can realize charge discharge cycles, is a kind of electricity of energy storage easily
Pond；Compared with lithium ion battery, lithium-air battery directly can obtain positive active material--oxygen from air, and
It is not required to be stored in battery system, significantly alleviates the weight of battery system, therefore, Large Copacity can be realized in theory
The great development of the lithium-air battery of energy storage is worth and receives significant attention.
Although lithium-air battery shows good application prospect, but actually performance is limited by various factors, its energy
Value can be arrived on amount conversion efficiency Distance Theory to differ greatly.At present, the negative pole of lithium-air battery uses metal lithium sheet,
For preventing lithium metal to be passivated, generally use the more ethylene carbonate (EC) of maturation, Ethyl methyl carbonate (EMC), carbonic acid two
The 1mol/dm of methyl ester (DMC) mixed solvent configuration3LiPF6EC/EMC/DMC (mass ratio 1:1:1) non-aqueous solution electrolysis
Liquid (although aqueous electrolyte and solid electrolyte are the most under study for action), air electrode is by (carbon dust/catalyst/adhesive)
Mixed slurry is coated in nickel foam composition.It is assembled into battery in the environment of isolation air:
(-) lithium sheet | organic electrolyte-barrier film | gas-diffusion electrode (+)
In the lithium-air battery of non-aqueous system, the Li that during battery discharge, the oxidation of negative pole lithium sheet produces+Moved to by electrolyte
Positive pole, the peroxide produced with oxygen reduction(or the oxonium ion O that reaction produces further2-) formed lithium oxidation
Thing.And charging process is contrary with discharge process, during charging, the peroxide breaks down of lithium produces oxygen and lithium ion.Discharging product
Li2O2Generation need not the fracture of O--O bond, therefore reaction need not the highest activation energy, is not using catalyst
Under the conditions of also can be smoothed out, see accompanying drawing 1.And charging process is by the peroxide breaks down of the lithium formed, the oxide of lithium
It is ionic crystals, is decomposed the activation energy that needs are higher, and cause discharging product when having electrolyte or binding agent to decompose
When becoming lithium carbonate or the Organic substance containing lithium, the activation energy needed for charging is higher, therefore oxygen-separating catalyst in charging process
It is essential to use.Relevant evidence shows, discharging product Li2O2Or Li2O is insoluble in nonaqueous electrolytic solution, Jing Guoyi
After secondary electric discharge, there is the unordered accumulation of a large amount of discharging product the air side of electrode, and barrier film side then there is no that electric discharge is produced
Thing, thus cause oxygen transmission channel blockage, cause discharge off.And, the Li of solid-state2O2Or Li2O ionic crystals
Almost insulator, once generate and unordered accumulation and cause electrode conductivity to destroy, make charging cannot be carried out.Visible reality
Existing cell reaction product is distributed in the ordering of positive pole, it is ensured that in charging process, electrode conductivity is uninterrupted, acceleratesOr
O2-→O2Conversion rate, be the key issue that must solve of organic electrolyte system lithium-air battery positive pole, this is also near
Over a little years, people design in new carbon research, multifunctional efficient catalyst research, electrode space structure and taste untiringly
The aspects such as examination launch the extensive target explored.
Summary of the invention
The invention provides a kind of lithium-air battery based on graphene oxide-carbon paper gas catalysis electrode, this battery is than existing
Some lithium-air batteries have higher capacity and charge and discharge cycle performance；Present invention also offers a kind of electrophoresis-electrolytic deposition
Method prepares the method for graphene oxide-carbon paper electrode.
Realizing the technical scheme that above-mentioned purpose of the present invention used is:
A kind of lithium-air battery based on graphene oxide-carbon paper gas catalysis electrode, below the most extremely employing of this battery
The graphene oxide catalysis electrode that the carbon paper that method prepares supports, preparation method is as follows: by graphene oxide at pH value be
In the phosphate buffer of 5～9, ultrasonic disperse becomes suspended state, prepares electrolyte；Then making positive pole with carbon paper, platinum electrode is made
Negative pole, is assembled into electrophoresis-electrolyzer, and using D.C. regulated power supply to control electrophoresis-electrolytic cell voltage is 5～20V, electrolyte
Temperature control at 20～50 DEG C, electrophoresis-electrolysis time is 5～30 minutes；In electrolytic process, for making graphite oxide
Alkene, at the uniform adventitious deposit of carbon paper surface, have employed at the uniform velocity agitating device, and stir speed (S.S.) is 1000～4000r/min, electricity
After solution deposition terminates, graphene oxide is deposited on carbon paper；Then there is graphene oxide with redistilled water wash load
Carbon paper, is vacuum dried after washing at 80～120 DEG C, finally with graphene oxide on analytical balance Weighing carbon paper
Load capacity, on described carbon paper, the load capacity of graphene oxide is 0.1～1.0mg/cm2。
Described carbon paper is the carbon paper after hydrophobic and planarizing process, and its thickness is 25～34 μm, with contacting of water
Angle is 90～140 °.
In described electrolyte, the concentration of graphene oxide is 0.5～3.0mg/cm3。
When preparing lithium-air battery, the carbon paper of above-mentioned load graphene oxide is cut into required area and makees positive pole, use
Lithium sheet makees negative pole, injects 1mol/dm3LiPF6EC/EMC/DMC (mass ratio 1:1:1) nonaqueous electrolytic solution, at isolation sky
It is assembled into button cell under gas, under open-circuit voltage, stands 3-24 hour, take constant current free discharge pattern and control
Depth of discharge pattern carries out discharge test, recording voltage-time graph and voltage-specific capacity curve.
In the present invention, owing to graphene oxide is that lamellar peels off graphite derivant after oxidation processes, stone is still kept
The layer structure of ink, each carbon atom is with sp2Hybrid orbital is covalently attached to, but introduces on the Graphene monolithic of each layer
Oxygen-containing group functional group.The generally accepted structural model of present stage people is random distribution in graphene oxide two-dimensional plane
Hydroxyl and epoxy radicals, then introduce carbonyl and carboxyl at the edge of monolithic, see accompanying drawing 2.Although these oxy radicals
Quantity and distribution can be different because of preparation method, but certainly, the introducing of oxygen-containing group functional group makes graphite oxide
Alkene has amphipathic, presents hydrophilic to hydrophobic character, thus make it to be suspended in water from graphene platelet edge to central authorities
In solution.Consider following factor the most in the present invention: 1, the carbonyl of graphene oxide can pass through electrolytic oxidation method
Open double bond, carbon paper is formed surface of graphene oxide；2, the hydroxyl of graphene oxide, the contained-OH group of carboxyl
" water " of a kind of broad sense can be regarded as, it is provided that to cell reaction product by Li at electrode surface2O2Or Li2O turns to LiOH
Become；3, still keep the layer structure of graphite due to graphene oxide, be perpendicular to sp2The delocalization big π key of carbocyclic ring plane can increase
The electron conduction of strong carbon paper；4, the oxygen-containing group functional group of graphene oxide has stronger electron-withdrawing power, and battery charges
Time can induceOr O2-, or OH-Tend to positive discharge, actual play oxygen reduction reaction (electric discharge, ORR) and analysis
The effect of oxygen conversion reaction (charging, OER) catalyst.
In the lithium-air battery that the present invention provides, graphene oxide is combined by its positive pole dexterously with carbon paper, its
Advantage is: one, utilize the porous of carbon paper, electric conductivity, stability, it is to avoid charging voltage is after 4.2V
The corrosion of collector, owing to need not any electrodic electron electric conductivity and the carbon dust of pore volume and catalyst material of affecting, also
Need not N-Methyl pyrrolidone dispersant (NMP) and PVDF binding agent, greatly reduce the ohmic voltage of positive pole
Fall, is shown in Fig. 4；Its two, carbon paper and graphene oxide are all material with carbon element, make graphene oxide and carbon by electrolytic oxidation
Paper is bonded, and introduces-OH and COOH functional group at positive pole, can promote Li2O2Or Li2O, can to the transformation of LiOH
By original charging reaction Li2O2→2Li++O2+ 2e or Li2O→2Li+O2+ 4e is changed into OH-On electrode
Electric discharge: 4OH-→O2+H2O+4e, along with Li2O2Or Li2O solid crystals electrode broad sense " water " act under transition
And fluidization, overcome the electrode conductivity interruption that cell reaction product is caused in the unordered accumulation of electrode hole, make charging
The problem that cannot continue；Its three, the oxygen-containing group functional group such as the carbonyl of graphene oxide, carboxyl has attraction electronic capability,
Can evoked electrode active substance (Li during charging2O2Or Li2O, and then be OH-) adsorb at electrode surface and discharge, real
Play the effect of catalyst on border, reach the purpose that charging reaction is smoothed out, substantially increase the steady of lithium-air battery
Qualitative, cyclicity and practicality；Finally, portable and stable after the lithium-air battery assembling of the present invention, voltage platform is high,
Discharge capacity is big, achieves stable charge discharge cycles under certain discharge system, and, preparation technology of the present invention and behaviour
Make parameter simple and easy to control, it is easy to accomplish large-scale production, it is simple to Industry Promotion.
Accompanying drawing explanation
Fig. 1 is carbon paper positive pole (CP) and the discharge curve pair first of graphene oxide-carbon paper positive pole (GO-CP) in the present invention
Than figure；
Fig. 2 is graphene oxide structural representation in the present invention；
Fig. 3 is carbon paper SEM figure and the partial enlarged drawing having been loaded graphene oxide in the present invention by electrolysis；
Fig. 4 is comparative example 1 and the discharge curve comparison diagram first of embodiment 1 in the present invention；
Fig. 5 is the charge and discharge cycles curve of the lithium-air battery making positive pole in comparative example 3 with pure carbon paper；
Fig. 6 is by loading graphene oxide-carbon paper electrode (GO-CP) in the present invention and the Raman light of the carbon paper (CP) used
Spectrum；
Fig. 7 is at 0.05mA/cm in the embodiment of the present invention 12And 0.1mA/cm2Electric current density under electric discharge first bent
Line；
Fig. 8 is the charge and discharge circulation figure of 81-100 the circulation intercepted in the embodiment of the present invention 2；
Fig. 9 is the charge and discharge circulation figure of embodiment 3 in the present invention.
Detailed description of the invention
In order to preferably illustrate present disclosure, substantive features and marked improvement, below in conjunction with relevant comparative example and reality
The invention will be further described to execute example.At this it should be noted that enumerate for concrete comparative example and embodiment, it is
It is adapted to assist in and understands the present invention, but the invention is not limited in following example.Carbon paper described in following example is warp
Crossing the carbon paper after hydrophobic and planarizing process, its thickness is 25～34 μm, is 90～140 ° with the contact angle of water.
Comparative example 1
The Graphene bought and Kynoar (PVDF) are pressed the mass ratio of 90:10 at N-Methyl pyrrolidone (NMP)
Medium is modulated into the slurry of certain viscosity, uses the method being similar to silk screen printing that slurry is uniformly applied to carbon paper
On, it is then placed in vacuum drying oven, at 80 DEG C, dries 12h, weigh after drying, and the carbon paper blunderbuss coated is become a diameter of 8mm
Disk, thus make positive plate standby.
In the glove box of argon shield, (anode cover surface punches to ensure the biography of oxygen to use CR2032 battery case
Defeated passage) as battery pack, successively by metal lithium sheet (Φ 15.6 × 0.45mm), barrier film Celgard 2325, positive pole
Sheet successively installs, and 1M LiPF6 (EC:EMC:DMC=1:1:1) electrolyte dripping appropriate business make electrode and every
Film is infiltrated, and is sealed by battery on packaging machine, i.e. completes battery and assembles.
The whole service process of battery is carried out, at 0.05mA/cm in dry oxygen2Electric current density under, put first
Capacitance is 6022mAh/g, and discharge platform, at 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 such as accompanying drawing 1
In discharge curve, discharge capacity is 13830.7mAh/g (pure carbon paper) first, and discharge platform meansigma methods is at about 2.7V.
Comparative example 3
Using the pure carbon paper of drying as positive pole, it is assumed that identical with the load capacity in embodiment 1, control depth of discharge, i.e. control
Discharge capacity processed is 1000mAh/g, obtains the cyclic curve in accompanying drawing 5, and pure carbon paper electrode is put after 20 charge and discharges
Electricity terminates.
Embodiment 1
By graphene oxide with 1.0mg/cm3Concentration ultrasonic disperse in redistilled water, add KH2PO4With
K2HPO4, it is configured to the phosphate buffer solution of pH9.0, continues ultrasonic disperse 6h, be allowed to the most scattered suspension.
With platinum electrode as negative pole, carbon paper is positive pole, is assembled into electrophoresis-electrolyzer, and regulated power supply controls electrolytic cell voltage at 20V,
The temperature of electrolyte controls at 45 DEG C, in electrolytic process, for make graphene oxide at the uniform adventitious deposit of carbon paper surface,
Have employed at the uniform velocity agitating device, stir speed (S.S.) is 2000r/min, and the cell reaction time is 5min.Graphite oxide will be loaded
The carbon paper electrode of alkene redistilled water cleans, and accompanying drawing 6 is shown in by its Raman collection of illustrative plates.Load graphene oxide after cleaning
Carbon paper electrode dries 12h in vacuum drying oven at 80 DEG C, weigh, and blunderbuss becomes the disk assembled battery of a diameter of 8mm.Respectively
At 0.05mA/cm2And 0.1mA/cm2Electric current density under constant-current discharge, its discharge curve such as accompanying drawing 7 first.Power supply
It is two electrode DC power supplys.
Embodiment 2
By graphene oxide with 2.0mg/cm3Concentration ultrasonic disperse in redistilled water, add KH2PO4With
K2HPO4, it is configured to the phosphate buffer solution of pH8.0, continues ultrasonic disperse 6h, be allowed to the most scattered suspension.
With platinum electrode as negative pole, carbon paper is positive pole, is assembled into electrophoresis-electrolyzer, and regulated power supply controls electrolytic cell voltage at 15V,
The temperature of electrolyte controls at 35 DEG C, in electrolytic process, for make graphene oxide at the uniform adventitious deposit of carbon paper surface,
Have employed at the uniform velocity agitating device, stir speed (S.S.) is 3000r/min, and the cell reaction time is 15min.Graphite oxide will be loaded
The carbon paper electrode of alkene redistilled water cleans, and the carbon paper electrode of the load graphene oxide after cleaning is in vacuum drying oven
Drying 10h at 100 DEG C, weigh, blunderbuss becomes the disk assembled battery of a diameter of 8mm.
Use the positive plate of preparation in the present embodiment, at 0.05mA/cm2Electric current density under, control discharge capacity be
500mAh/g (is calculated by the amount of load graphene oxide), its charge and discharge cyclic curve such as accompanying drawing 8.
Embodiment 3
By graphene oxide with 3.0mg/cm3Concentration ultrasonic disperse in redistilled water, add KH2PO4With
K2HPO4, it is configured to the phosphate buffer solution of pH7.0, continues ultrasonic disperse 6h, be allowed to the most scattered suspension.
With platinum electrode as negative pole, carbon paper is positive pole, is assembled into electrophoresis-electrolyzer, and regulated power supply controls electrolytic cell voltage at 8V,
The temperature of electrolyte controls at 25 DEG C, in electrolytic process, for make graphene oxide at the uniform adventitious deposit of carbon paper surface,
Have employed at the uniform velocity agitating device, stir speed (S.S.) is 4000r/min, and the cell reaction time is 25min.Graphite oxide will be loaded
The carbon paper electrode of alkene redistilled water cleans, and the carbon paper electrode of the load graphene oxide after cleaning is in vacuum drying oven
Drying 8h at 120 DEG C, weigh, blunderbuss becomes the disk assembled battery of a diameter of 8mm.
Use the positive plate of preparation in the present embodiment, at 0.05mA/cm2Electric current density under, control discharge capacity be
1000mAh/g (is calculated by the amount of load graphene oxide), its charge and discharge cyclic curve such as accompanying drawing 9.
Claims (2)
1. a lithium-air battery based on graphene oxide-carbon paper gas catalysis electrode, it is characterised in that: this battery
The graphene oxide catalysis electrode that the carbon paper the most extremely using following methods to prepare supports, preparation method is as follows: will aoxidize stone
Ink alkene ultrasonic disperse in the phosphate buffer that pH value is 5～9 becomes suspended state, prepares electrolyte；Then make with carbon paper
Positive pole, platinum electrode makees negative pole, is assembled into electrophoresis-electrolyzer, uses D.C. regulated power supply to control electrophoresis-electrolytic cell voltage and is
5～20V, the temperature of electrolyte controls at 20～50 DEG C, and electrophoresis-electrolysis time is 5～30 minutes；In electrolytic process,
For making graphene oxide at the uniform adventitious deposit of carbon paper surface, have employed at the uniform velocity agitating device, stir speed (S.S.) be 1000～
4000r/min, after electrolytic deposition terminates, graphene oxide is deposited on carbon paper；Then redistilled water wash load is used
There is the carbon paper of graphene oxide, be vacuum dried at 80～120 DEG C after washing, finally with analytical balance Weighing carbon paper
The load capacity of upper graphene oxide, on described carbon paper, the load capacity of graphene oxide is 0.1～1.0mg/cm2；
Described carbon paper is the carbon paper after hydrophobic and planarizing process, and its thickness is 25～34 μm, with contacting of water
Angle is 90～140 °.
Lithium based on graphene oxide-carbon paper gas catalysis electrode the most according to claim 1～air cell, its
It is characterised by: in described electrolyte, the concentration of graphene oxide is 0.5～3.0mg/cm3。
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| KR102231070B1 (en) | 2012-03-05 | 2021-03-23 | 더 리전트 오브 더 유니버시티 오브 캘리포니아 | Capacitor with electrodes made of an interconnected corrugated carbon-based network |
| US10734167B2 (en) | 2014-11-18 | 2020-08-04 | The Regents Of The University Of California | Porous interconnected corrugated carbon-based network (ICCN) composite |
| CN105037763B (en) * | 2015-07-31 | 2017-07-11 | 中国地质大学（北京） | The preparation method of modified graphene oxide piezopolymer energy storage thin-film device |
| KR102631764B1 (en) | 2015-12-22 | 2024-01-30 | 더 리전트 오브 더 유니버시티 오브 캘리포니아 | Cellular graphene film |
| CN108475590B (en) | 2016-01-22 | 2021-01-26 | 加利福尼亚大学董事会 | High voltage device |
| CA3018568A1 (en) | 2016-03-23 | 2017-09-28 | The Regents Of The University Of California | Devices and methods for high voltage and solar applications |
| WO2018044786A1 (en) | 2016-08-31 | 2018-03-08 | The Regents Of The University Of California | Devices comprising carbon-based material and fabrication thereof |
| CN106449171A (en) * | 2016-09-29 | 2017-02-22 | 武汉船用电力推进装置研究所（中国船舶重工集团公司第七二研究所） | Preparation method of flexible all-solid-state supercapacitor electrode |
| CN106637327B (en) * | 2016-11-09 | 2019-04-19 | 中国科学院生态环境研究中心 | A kind of cathode material and its preparation method and application of electro-catalysis reduction oxygen |
| CN107026274B (en) * | 2017-05-16 | 2020-05-22 | 中国地质大学（武汉） | Preparation method and application of graphene/carbon paper gas electrode 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 |
| 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 |
| 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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| CN102568847B (en) * | 2011-12-16 | 2014-08-13 | 江南大学 | Method for electrochemically preparing graphene/manganese dioxide composite material, and application of graphene/manganese dioxide composite material |
| CN102544501A (en) * | 2012-02-09 | 2012-07-04 | 东南大学 | Method for preparing polypyrrole nanometer wire-graphene composite material |
| CN103466603B (en) * | 2013-08-09 | 2016-01-27 | 中国科学院苏州纳米技术与纳米仿生研究所 | The preparation method of graphene dispersing solution and graphene film |
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