US20140141355A1 - Graphene electrode, energy storage device employing the same, and method for fabricating the same - Google Patents

Graphene electrode, energy storage device employing the same, and method for fabricating the same Download PDF

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US20140141355A1
US20140141355A1 US13/949,732 US201313949732A US2014141355A1 US 20140141355 A1 US20140141355 A1 US 20140141355A1 US 201313949732 A US201313949732 A US 201313949732A US 2014141355 A1 US2014141355 A1 US 2014141355A1
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graphene
hetero
graphene layer
electrode
doped
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Hsiao-Feng Huang
Ping-Chen Chen
Chun-Hsiang Wen
Wei-Jen Liu
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Industrial Technology Research Institute ITRI
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Publication of US20140141355A1 publication Critical patent/US20140141355A1/en
Priority to US15/433,612 priority Critical patent/US10147948B2/en
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/32—Carbon-based
    • H01G11/36—Nanostructures, e.g. nanofibres, nanotubes or fullerenes
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    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
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    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
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    • B05D1/00—Processes for applying liquids or other fluent materials
    • B05D1/40—Distributing applied liquids or other fluent materials by members moving relatively to surface
    • B05D1/42—Distributing applied liquids or other fluent materials by members moving relatively to surface by non-rotary members
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/14—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by electrical means
    • B05D3/141—Plasma treatment
    • B05D3/145—After-treatment
    • B05D3/148—After-treatment affecting the surface properties of the coating
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
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    • H—ELECTRICITY
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    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
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    • H—ELECTRICITY
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    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
    • H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • H01M4/0402—Methods of deposition of the material
    • H—ELECTRICITY
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    • H01M4/0404—Methods of deposition of the material by coating on electrode collectors
    • H—ELECTRICITY
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • H01M4/04—Processes of manufacture in general
    • H01M4/0402—Methods of deposition of the material
    • H01M4/0409—Methods of deposition of the material by a doctor blade method, slip-casting or roller coating
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • H01M4/04—Processes of manufacture in general
    • H01M4/0471—Processes of manufacture in general involving thermal treatment, e.g. firing, sintering, backing particulate active material, thermal decomposition, pyrolysis
    • H—ELECTRICITY
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    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1393—Processes of manufacture of electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • 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
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    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
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    • H01M4/624—Electric conductive fillers
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • 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
    • 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
    • Y02E60/13—Energy storage using capacitors
    • 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
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    • Y02E60/30—Hydrogen technology
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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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    • Y02T10/60—Other road transportation technologies with climate change mitigation effect
    • Y02T10/70—Energy storage systems for electromobility, e.g. batteries

Definitions

  • Taiwan (International) Application Serial Number 101143373 filed Nov. 21, 2012, the disclosure of which is hereby incorporated by reference herein in its entirety.
  • the disclosure relates to a graphene electrode and, more particularly, to a graphene electrode used in an energy storage device.
  • One embodiment of the disclosure provides a graphene electrode and a method for fabricating the same. Since the hetero-atom is doped into the surface of a graphene at a low temperature by a dry-process surface modification treatment, the obtained graphene electrode can have high capacity and low irreversible capacity. On the other hand, the graphene electrode of the disclosure is suitable for being used in energy storage devices.
  • the graphene electrode of the disclosure includes: a metal foil, a non-doped graphene layer, and a hetero-atom doped graphene layer, wherein the hetero-atom doped graphene layer is separated from the metal foil by the non-doped graphene layer.
  • the disclosure also provides a method for fabricating the aforementioned graphene electrode.
  • the method includes: providing the metal foil; forming the graphene layer on the metal foil; and subjecting the graphene layer to a dry-process surface modification treatment, thereby doping the hetero-atoms into the graphene layer surface.
  • the disclosure further provides an energy storage device, wherein the energy storage device includes the aforementioned graphene electrode serving as a first electrode, a second electrode, and an isolation membrane disposed between the first electrode and the second electrode.
  • FIG. 1 is a cross-section of a graphene electrode according to an exemplary embodiment.
  • FIG. 2 is a flow chart illustrating the method for fabricating the aforementioned graphene electrode according to an exemplary embodiment.
  • FIG. 3 is a cross-section of an energy storage device according to an exemplary embodiment.
  • FIG. 4 shows a graph plotting the nitrogen-atom doping amount of the graphene electrodes (II)-(IV).
  • FIG. 5 shows a graph plotting the charge-discharge curves of the batteries (I) and (II).
  • FIG. 6 shows a graph plotting discharge capacity against C-rates of the batteries (I) and (II).
  • FIG. 7 shows a graph plotting charge-discharge cycles against discharge capacity of the batteries (I), (III), and (IV).
  • the graphene electrode of the disclosure 100 can include a metal foil 10 , wherein a graphene layer 20 is disposed on the metal foil 10 .
  • the graphene layer 20 includes a non-doped graphene layer 24 , and a hetero-atom doped graphene layer 22 .
  • the hetero-atom doped graphene layer 22 and the metal foil 10 are separated by the non-doped graphene layer 24 .
  • Suitable materials of the metal foil 10 can be a conductive metal, such as a copper foil.
  • the thickness of the metal foil 10 is unlimited and can be between 0.1 and 200 ⁇ .
  • the hetero-atom doped graphene layer 22 includes the surface 21 of the portion of the graphene layer 20 which is doped with the hetero-atoms 23 . Further, the portion, which is not doped with the hetero-atom 23 of the graphene layer 20 , is defined as the non-doped graphene layer 24 .
  • the hetero-atoms 23 can be nitrogen atoms, phosphorous atoms, boron atoms, or combinations thereof.
  • the hetero-atom doped graphene layer 22 can have a hetero-atom doping dosage of 0.1-3 atom %, based on the total atomic amount of the hetero-atom doped graphene layer 22 .
  • the non-doped graphene layer 24 can be a single-layer graphene, or graphene nanosheets or combinations thereof.
  • the hetero-atom doped graphene layer 22 can be a single-layer hetero-atom doped graphene, or hetero-atom doped graphene nanosheets, or combinations thereof.
  • FIG. 2 is a flow chart illustrating the method for fabricating the aforementioned graphene electrode according to an embodiment of the disclosure.
  • a metal foil is provided (step 101 ), wherein the metal foil can be a copper foil.
  • a graphene layer is formed on the metal foil (step 102 ).
  • the graphene layer is subjected to a dry-process surface modification treatment for doping the hetero-atoms into the surface of the graphene layer (step 103 ).
  • the hetero-atoms are doped into a part of the graphene layer (i.e. the surface of the graphene layer), to form a hetero-atom doped graphene layer and a non-doped graphene layer (the portion of the graphene layer which is not doped with the hetero-atom).
  • the dry-process surface modification treatment can be a plasma modification process. It should be noted that, since the hetero-atoms have to be confined within the surface of the graphene layer rather than the whole graphene layer, the graphene layer or metal foil must not be heated during the dry-process surface modification treatment. Further, a reactive gas is introduced into the reactor of the plasma modification process to dope the hetero-atoms into the graphene layer.
  • the reactive gas includes a gas containing the hetero-atoms (such as nitrogen gas, ammonia gas, air, or combinations thereof), or a mixture of the gas containing the hetero-atoms (such as nitrogen gas, ammonia gas, air, or combinations thereof) and other gas (such as hydrogen gas, argon gas, oxygen gas, or combinations thereof).
  • a carrier gas can be introduced into the reactor of the plasma modification process, in order to stabilize the plasma modification process.
  • the carrier gas can include helium gas, argon gas, nitrogen gas, neon gas, or combinations thereof.
  • the reactor of the plasma modification process can be a low pressure plasma reactor or an atmospheric pressure plasma reactor.
  • the parameters (such as the reactive gas flow, the carrier gas flow, the reaction pressure, the power, the reaction time, and the distances between the graphene layer and electrodes of the reactor) can be optionally adjusted, assuming that the doped amount of hetero-atoms in the hetero-atom doped graphene layer is from 0.1 to 3 atom %, based on the total atomic amount of the hetero-atom doped graphene layer.
  • the method for forming the graphene layer includes the following steps. First, a coating prepared from a graphene-containing composition is formed on the metal foil, wherein the method for forming the coating on the metal foil can be a screen printing, spin coating, bar coating, blade coating, roller coating, or dip coating method.
  • the coating is subjected to a drying process, obtaining the graphene layer.
  • the drying process can be performed at 40-150° C. for a period of time from 1 min to 10 hrs.
  • the graphene-containing composition can include a graphene, and a binder.
  • the graphene-containing composition can further include a conducting agent.
  • the binder can be an aqueous-based binder, an organic-based binder, such as carboxymethyl cellulose (CMC), styrene butadiene rubber (SBR), or polyvinylidene difluoride (PVdF), or combinations thereof.
  • the conducting agent can be, for example, graphite, carbon black, or combinations thereof.
  • the disclosure also provides an energy storage device (such as a lithium ion battery, supercapacitor or fuel cell) 200 , including the aforementioned graphene electrode 100 .
  • the energy storage device 200 can include a graphene electrode serving as a first electrode 202 (such as anode), a second electrode 206 (such as cathode), and an isolation membrane 204 disposed between the first electrode 202 and the second electrode 206 . It should be noted that the hetero-atom doped graphene layer of the graphene electrode directly contacts to the isolation membrane.
  • Suitable materials of the second electrode 206 can be lithium or lithium-containing oxide such as Li, LiCoO 2 , LiFePO 4 , LiCo 1/3 Ni 1/3 Mn 1/3 O 2 , LiMn 2 O 4 or combinations thereof.
  • Suitable materials of the isolation membrane can be polymer, such as polyethylene, polypropylene, or combinations thereof. Further, the isolation membrane can have a plurality of pores.
  • the energy storage device can further include an electrolysis (not shown) within the isolation membrane 204 , such as ethylene carbonate (EC), propylene carbonate (PC), gamma-butyrolactone (GBL), diethyl carbonate (DEC), dimethyl carbonate (DMC), ethyl methyl carbonate (EMC), methyl propyl carbonate (MPC), vinylene carbonate (VC), lithium salt, or combinations thereof.
  • electrolysis not shown within the isolation membrane 204 , such as ethylene carbonate (EC), propylene carbonate (PC), gamma-butyrolactone (GBL), diethyl carbonate (DEC), dimethyl carbonate (DMC), ethyl methyl carbonate (EMC), methyl propyl carbonate (MPC), vinylene carbonate (VC), lithium salt, or combinations thereof.
  • the above graphene-containing slurry was coated on a copper foil by blade coating (using the doctor blade (150 ⁇ m) to form a coating. After drying at 120° C., a graphene electrode (I) having the graphene layer was obtained. It should be noted that the graphene layer of the graphene electrode (I) was not doped with any hetero-atom.
  • the graphene electrode (I) was disposed into a plasma reactor, wherein the copper foil of the graphene electrode (I) directly contacted with a support substrate of the plasma reactor, and the distance between the graphene layer and the electrode of the plasma reactor was 2.2 mm. Next, a nitrogen gas (with a flow of 5 sccm) and a helium gas (with a flow of 5.88 L/min) were introduced into the plasma reactor. Next, the surface of the graphene layer was subjected to a plasma modification process under a pressure of 1 atm, and a RF power of 65W, in order to dope nitrogen atoms into the surface of the graphene layer. It should be noted that no heating process was performed during the plasma modification process. After reacting for 6 sec, a graphene electrode (II) was obtained.
  • the surface of the graphene electrode (II) was analyzed by an X-ray Photoelectron Spectrometer (XPS) to measure the doping amount of nitrogen atoms of the hetero-atom doped graphene layer of the graphene electrode (II). The results are as shown in FIG. 4 .
  • XPS X-ray Photoelectron Spectrometer
  • Example 3 was performed as Example 2 except that the flow rate of the nitrogen gas was increased to 30 sccm instead of 5 sccm.
  • the graphene electrode (III) was obtained.
  • the surface of the graphene electrode (III) was analyzed by an X-ray Photoelectron Spectrometer (XPS) to measure the doping amount of nitrogen atoms of the hetero-atom doped graphene layer of the graphene electrode (III). The results are shown in FIG. 4 .
  • XPS X-ray Photoelectron Spectrometer
  • Example 4 was performed as Example 1 except that the reaction time was changed to 18 sec instead of 6 sec.
  • the graphene electrode (IV) was obtained.
  • the surface of the graphene electrode (IV) was analyzed by an X-ray Photoelectron Spectrometer (XPS) to measure the doping amount of nitrogen atoms of the hetero-atom doped graphene layer of the graphene electrode (IV). The results are shown in FIG. 4 .
  • XPS X-ray Photoelectron Spectrometer
  • the nitrogen atoms were observed as the impurities in the surface of the graphene electrodes (II)-(IV) of the disclosure. Therefore, the nitrogen atoms were indeed doped into the surface of the graphene layer via the plasma modification process.
  • Example 5 was performed as Example 2 except that the flow rate of nitrogen gas was changed to 15 sccm and the reaction time was 18 sec instead of the flow rate of 5 sccm and the reaction time of 6 sec.
  • the graphene electrode (V) was obtained.
  • Example 6 was performed as Example 2 except that the flow rate of nitrogen gas was adjusted at 30 sccm and the reaction time was 18 sec.
  • the graphene electrode (VI) was obtained.
  • Table 1 showed the parameters of the plasma modification process employed in Example 2-6.
  • the graphene electrode (I) of Example 1 was cut to form an anode (with a diameter of 13 mm) Next, the anode, an isolation membrane (a polyethylene/polypropylene composite film with a thickness of 20 ⁇ m), and a lithium layer (serving as a cathode) were assembled. Next, an electrolyte (including ethylene carbonate (EC), ethyl methyl carbonate (EMC), vinylene carbonate (VC), and 1M of LiPF 6 ) was injected into the isolation membrane, and a button-type lithium ion battery (I) was obtained.
  • EC ethylene carbonate
  • EMC ethyl methyl carbonate
  • VC vinylene carbonate
  • LiPF 6 1M of LiPF 6
  • the graphene electrode (IV) of Example 1 was cut to form an anode (with a diameter of 13 mm).
  • the anode, an isolation membrane (a polyethylene/polypropylene composite film with a thickness of 20 ⁇ m), and a lithium layer (serving as a cathode) were assembled.
  • an electrolyte including ethylene carbonate (EC), ethyl methyl carbonate (EMC), vinylene carbonate (VC), and 1M of LiPF 6 ) was injected into the isolation membrane, and a button-type lithium ion battery (II) was obtained.
  • the graphene electrode (V) of Example 1 was cut to form an anode (with a diameter of 13 mm).
  • the anode, an isolation membrane (a polyethylene/polypropylene composite film with a thickness of 20 ⁇ m), and a lithium layer (serving as a cathode) were assembled.
  • an electrolyte including ethylene carbonate (EC), ethyl methyl carbonate (EMC), vinylene carbonate (VC), and 1M of LiPF 6 ) was injected into the isolation membrane, and a button-type lithium ion battery (III) was obtained.
  • the graphene electrode (VI) of Example 1 was cut to form an anode (with a diameter of 13 mm).
  • the anode, an isolation membrane (a polyethylene/polypropylene composite film with a thickness of 20 ⁇ m), and a lithium layer (serving as a cathode) were assembled.
  • an electrolyte including ethylene carbonate (EC), ethyl methyl carbonate (EMC), vinylene carbonate (VC), and 1M of LiPF 6 ) was injected into the isolation membrane, and a button-type lithium ion battery (IV) was obtained.
  • the batteries (I) and (II) of Examples 7-8 were subjected to a charge-discharge test respectively, and the results are shown in FIG. 5 .
  • the discharge capacities of the batteries (I) and (II) were evaluated under various C-rates at room temperature, and the results are shown in FIG. 6 .
  • the battery (II) (having the nitrogen-atom doped grapheme layer) had higher discharge capacities in comparison with those of the battery (I) under various C-rates.
  • the batteries (I), (III), and (IV) were subjected to a cycle life test, and the results are shown in FIG. 7 .
  • the batteries (III) and (IV) (having the nitrogen-atom doped grapheme layer) had a higher capacities in comparison with those of the battery (I) under various cycles. Particularly, the batteries had more than double the capacities as compared to that of the battery (I). Further, as shown in FIG. 7 , the performances of the batteries (III) and (IV) were maintained over multiple cycles.
  • the batteries (I), (II), and (III) were subjected to a charging and discharging cycle tests and measured for evaluating the irreversible capacity loss and Coulombic efficiencies thereof. The results are shown in Table 2.
  • the batteries (II) and (III) having the graphene electrode of the disclosure had an increased Coulombic efficiency and a reduced irreversible capacities in comparison with the battery (I) in both the first cycle and second cycle. This means that the graphene electrode subjected to the plasma modification process had stable electrical characteristics.
  • the graphene electrode of the disclosure since the surface of the graphene layer was subjected to a dry-process surface modification treatment, the graphene electrode of the disclosure exhibited improved electrical characteristics (such as high capacity, high carrier mobility, and low irreversible capacity). Therefore, the graphene electrode of the disclosure is suitable for being used in an energy storage device.

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