EP3811443A2 - Graphene synthesis method by microfluidization - Google Patents

Graphene synthesis method by microfluidization

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Publication number
EP3811443A2
EP3811443A2 EP19851994.4A EP19851994A EP3811443A2 EP 3811443 A2 EP3811443 A2 EP 3811443A2 EP 19851994 A EP19851994 A EP 19851994A EP 3811443 A2 EP3811443 A2 EP 3811443A2
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EP
European Patent Office
Prior art keywords
composites
added
graphene according
enhancing agent
graphene
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
EP19851994.4A
Other languages
German (de)
French (fr)
Other versions
EP3811443A4 (en
Inventor
Servet Turan
Kamil Burak DERMENCI
Tayfun KOCAK
Abdullah Tugrul SEYHAN
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Anadolu Universitesi
Original Assignee
Anadolu Universitesi
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Publication date
Application filed by Anadolu Universitesi filed Critical Anadolu Universitesi
Publication of EP3811443A2 publication Critical patent/EP3811443A2/en
Publication of EP3811443A4 publication Critical patent/EP3811443A4/en
Pending legal-status Critical Current

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Classifications

    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/182—Graphene
    • C01B32/184—Preparation
    • C01B32/19—Preparation by exfoliation
    • 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
    • H01G11/84—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
    • 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
    • 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
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • 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

Definitions

  • the present invention relates to synthesis of graphene by microfluidization method and use thereof in potential anode, cathode and electrolyte active materials and additives in electrochemical energy storage devices.
  • Graphite has been widely used in the field of electrochemical energy storage in the recent years because of its layered structure and relatively low price. Graphene, which is a single layer of graphite, is considered as a promising candidate for use in electrochemical energy storage applications.
  • Graphene can be synthesized by various methods such as exfoliation and cleavage, CVD, thermal decomposition, ultrasonication, ultracentrifugation and microfluidization.
  • microfluidization is high shear-rate treat of water or alcohol suspensions of starting material. With the help of extremely high shear rate, both size reduction and expansion of layer can be seen.
  • the microfluidization method is performed by high shear-rate treat of water or alcohol suspensions of starting material. As it is used in obtaining graphene, the method is capable of reduction of both the plate size and the particle size simultaneously by means of the high shear rate which is a characteristic feature of the method.
  • the microfluidization method and the features of the products obtained by this method are schematically shown in Figure 1.
  • a prior art patent discloses the potential of use of graphenes, which are obtained by starting from expandable graphite starting material using microfluidization method such that the plate size is reduced and the distance between the plates is increased, in Li-ion battery applications.
  • US20110195308A1 known in the state of the art, discloses size reduction and grounding steps performed by the microfluidization device produced by Microfluidics Corp and the process of mixing the Li-ion battery materials.
  • Chinese patent document numbered CN106159199 discloses a method of preparing three-dimensional graphene electrode and use thereof in energy storage applications.
  • the three-dimensional graphene electrode is applied to a high-density lithium- sulfur battery, a high-density lithium-silicon battery, a high-density super capacitor, a high-density Faraday capacitor and a high-density battery capacitor, and can be applied to a high-working-voltage and high-energy- storage-density battery capacitor.
  • US2012045688 discloses an electrochemical energy storage device and lithium super batteries comprising a positive electrode, a negative electrode, a porous separator disposed between the two electrodes, and a lithium-containing electrolyte in physical contact with the two electrodes.
  • nanosized graphene has been obtained from graphite particles by exfoliation method.
  • the lithium super-battery of the said invention exhibits a gravimetric energy 5 times higher than conventional supercapacitors and a power density 10 times higher than conventional lithium-ion batteries.
  • Expandable graphite used in the art is one of the precursors used for synthesizing graphene. It is a common and cost-effective material. However, the synthesis of graphene is hard and costly as it is time-consuming and requires relatively high temperatures. Conventional methods such as ball milling are more likely to create micron or nanosized few layer graphenes instead of single layer nanosized graphene and the said methods are relatively expensive.
  • the objective of the present invention is to provide a single layer and nanosized graphene by microfluidization method.
  • Another objective of the present invention is to use the obtained graphene in anode, cathode and electrolyte active materials and additives in electrochemical energy storage devices.
  • a further objective of the present invention is to be able to produce high energy capacity electrode and/or electrolyte materials in the field of electrochemical energy storage at low cost.
  • Another objective of the present invention is to enable graphene to exhibit high performance at high charge-discharge rates since it is synthesized by microfluidization method.
  • Figure 1 shows the SEM images of expandable graphite powders after 4 cycle microfluidization.
  • Figure 2 is the graphic of the first three charge-discharge curves of 4 cycle microfluidized expandable graphite (Cycle rate: 500 mA/g).
  • Figure 3 is the graphic of the charge-discharge capacities of 4 cycle microfluidized expandable graphite (Cycle rate: 500 mA/g) for the first 10 cycles.
  • Figure 4 is the graphic of the Coulombic Efficiencies of 4 cycle microfluidized expandable graphite (Cycle rate: 500 mA/g).
  • the present invention is a graphene synthesis method by microfluidization method for being used in high energy capacity electrode and/or electrolyte materials in the field of electrochemical energy storage, and comprises the following steps:
  • Expandable graphite of 30 pm thickness and 300 pm diameter was purchased and sieved through a sieve with 63 pm mesh size. 1 g of expandable graphite was weighed and dispersed in 400 mL 2-propanol to prepare a suspension. Then Ultrasonication was conducted for 1 hour at 20 kHz frequency and 40% amplitude. The resulting suspension was poured to the Microfluidizer (Microfluidics Corp.) for performing the 4 cycles. 290 MPa pressure was applied during the cycles.
  • Microfluidizer Microfluidics Corp.
  • Electrode slurries were prepared by dissolving 0.1 gram of Polyvinylidene Fluoride (PVdF) as a binder in 4.0 mL N-Methyl Pyrollidone (NMP) solvent. Then, expandable graphite processed by the microfluidizer was added as the active material and mixed in a planetary grinder for 1 hour at 200 RPM rotation speed. The active material binder ratio was selected to be 90:10.
  • the prepared slurries were tape-casted on copper (Cu) foil and dried in a vacuum oven at a temperature of 80°C. Afterwards, electrodes were punched with a diameter of 16 mm, and pouch-type half-cells were assembled.
  • Lithium (Li) foil was used as a counter electrode in the half cells.
  • 1M LiPFe in EC:DMC (1:1) (1 M Lithium Hexafluoro Phosphate dissolved in Ethylene Carbon-Diethyl Carbonate mixture at a ratio of 1:1) was used as the electrolyte.
  • the charge-discharge curves were obtained between 0.02 - 2.00 V from BasyTec multichannel battery test system at 500 mA/g cycle rates. The obtained potential values were provided with respect to Li/Li-i- reference.
  • the capacity value for the first 10 cycles at a cycle rate of 500 mA/g given in Figure 4 shows that the specific discharge rate of 117.9 mAh/g is maintained. At the end of 10 cycles, the total capacity decrease is limited to 7%.
  • the method of the invention wherein high shear-rate techniques such as microfluidization are used, enables to obtain graphene and to reduce size of the obtained graphene as well as increasing the distance between the layers simultaneously by using expandable graphite.
  • graphene synthesized by microfluidization method using an original raw material such as expandable graphite for electrochemical energy storage shows high performance at high charge/discharge rates.

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Power Engineering (AREA)
  • Materials Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Electrochemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Nanotechnology (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Organic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Carbon And Carbon Compounds (AREA)

Abstract

The present invention relates to a graphene synthesis method by microfluidization for being used in high energy capacity electrode and/or electrolyte materials in the field of electrochemical energy storage. The method comprises the steps of purchasing expandable graphite of 30 pm thickness and 300 pm diameter, sieving by a sieve with 63 pm mesh size, weighing 1 g of expandable graphite, dispersing it in 400 mL 2-propanol to prepare a suspension, conducting ultrasonic ation for 1 hour at 20 kHz frequency and 40% amplitude, pouring the suspension into the microfluidizer, and performing 4 cycles.

Description

GRAPHENE SYNTHESIS METHOD BY MICROFLUIDIZATION
Field of the Invention
The present invention relates to synthesis of graphene by microfluidization method and use thereof in potential anode, cathode and electrolyte active materials and additives in electrochemical energy storage devices.
Background of the Invention
Graphite has been widely used in the field of electrochemical energy storage in the recent years because of its layered structure and relatively low price. Graphene, which is a single layer of graphite, is considered as a promising candidate for use in electrochemical energy storage applications.
Graphene can be synthesized by various methods such as exfoliation and cleavage, CVD, thermal decomposition, ultrasonication, ultracentrifugation and microfluidization. Among the said methods, microfluidization is high shear-rate treat of water or alcohol suspensions of starting material. With the help of extremely high shear rate, both size reduction and expansion of layer can be seen.
The microfluidization method is performed by high shear-rate treat of water or alcohol suspensions of starting material. As it is used in obtaining graphene, the method is capable of reduction of both the plate size and the particle size simultaneously by means of the high shear rate which is a characteristic feature of the method. The microfluidization method and the features of the products obtained by this method are schematically shown in Figure 1. A prior art patent discloses the potential of use of graphenes, which are obtained by starting from expandable graphite starting material using microfluidization method such that the plate size is reduced and the distance between the plates is increased, in Li-ion battery applications.
The United States patent document numbered US20110195308A1, known in the state of the art, discloses size reduction and grounding steps performed by the microfluidization device produced by Microfluidics Corp and the process of mixing the Li-ion battery materials.
Chinese patent document numbered CN106159199, known in the state of the art, discloses a method of preparing three-dimensional graphene electrode and use thereof in energy storage applications. The three-dimensional graphene electrode is applied to a high-density lithium- sulfur battery, a high-density lithium-silicon battery, a high-density super capacitor, a high-density Faraday capacitor and a high-density battery capacitor, and can be applied to a high-working-voltage and high-energy- storage-density battery capacitor.
The United States patent document numbered US2012045688, known in the state of the art, discloses an electrochemical energy storage device and lithium super batteries comprising a positive electrode, a negative electrode, a porous separator disposed between the two electrodes, and a lithium-containing electrolyte in physical contact with the two electrodes. In the said invention, nanosized graphene has been obtained from graphite particles by exfoliation method. The lithium super-battery of the said invention exhibits a gravimetric energy 5 times higher than conventional supercapacitors and a power density 10 times higher than conventional lithium-ion batteries.
Expandable graphite used in the art is one of the precursors used for synthesizing graphene. It is a common and cost-effective material. However, the synthesis of graphene is hard and costly as it is time-consuming and requires relatively high temperatures. Conventional methods such as ball milling are more likely to create micron or nanosized few layer graphenes instead of single layer nanosized graphene and the said methods are relatively expensive.
Summary of the Invention
The objective of the present invention is to provide a single layer and nanosized graphene by microfluidization method.
Another objective of the present invention is to use the obtained graphene in anode, cathode and electrolyte active materials and additives in electrochemical energy storage devices.
A further objective of the present invention is to be able to produce high energy capacity electrode and/or electrolyte materials in the field of electrochemical energy storage at low cost.
Another objective of the present invention is to enable graphene to exhibit high performance at high charge-discharge rates since it is synthesized by microfluidization method.
Detailed Description of the Invention
“Graphene synthesis by microfluidization method” developed to fulfill the objectives of the present invention is illustrated in the accompanying figures, in which:
Figure 1 shows the SEM images of expandable graphite powders after 4 cycle microfluidization.
Figure 2 is the graphic of the first three charge-discharge curves of 4 cycle microfluidized expandable graphite (Cycle rate: 500 mA/g). Figure 3 is the graphic of the charge-discharge capacities of 4 cycle microfluidized expandable graphite (Cycle rate: 500 mA/g) for the first 10 cycles. Figure 4 is the graphic of the Coulombic Efficiencies of 4 cycle microfluidized expandable graphite (Cycle rate: 500 mA/g).
The present invention is a graphene synthesis method by microfluidization method for being used in high energy capacity electrode and/or electrolyte materials in the field of electrochemical energy storage, and comprises the following steps:
- purchasing expandable graphite of 30 pm thickness and 300 pm diameter,
- sieving by a sieve with 63 pm mesh size,
- weighing 1 g of expandable graphite,
- dispersing it in 400 mL 2-propanol to prepare a suspension,
- conducting ultrasonication for 1 hour at 20 kHz frequency and 40% amplitude,
- pouring the suspension into the microfluidizer, and
- performing 4 cycles.
Expandable graphite of 30 pm thickness and 300 pm diameter was purchased and sieved through a sieve with 63 pm mesh size. 1 g of expandable graphite was weighed and dispersed in 400 mL 2-propanol to prepare a suspension. Then Ultrasonication was conducted for 1 hour at 20 kHz frequency and 40% amplitude. The resulting suspension was poured to the Microfluidizer (Microfluidics Corp.) for performing the 4 cycles. 290 MPa pressure was applied during the cycles.
Microstructural changes of the expandable graphite obtained as a result of 4 cycles of microfluidization have been observed by Scanning Electron Microscope (Zeiss SUPRA 50VP). Before the analyses, the samples were sputtered with Au- Pd sputter coating technique to ensure adequate electronic conductivity. Figure 1 shows the Scanning Electron Microscope (Zeiss SUPRA 50VP) images.
Electrode slurries were prepared by dissolving 0.1 gram of Polyvinylidene Fluoride (PVdF) as a binder in 4.0 mL N-Methyl Pyrollidone (NMP) solvent. Then, expandable graphite processed by the microfluidizer was added as the active material and mixed in a planetary grinder for 1 hour at 200 RPM rotation speed. The active material binder ratio was selected to be 90:10. The prepared slurries were tape-casted on copper (Cu) foil and dried in a vacuum oven at a temperature of 80°C. Afterwards, electrodes were punched with a diameter of 16 mm, and pouch-type half-cells were assembled. Lithium (Li) foil was used as a counter electrode in the half cells. 1M LiPFe in EC:DMC (1:1) (1 M Lithium Hexafluoro Phosphate dissolved in Ethylene Carbon-Diethyl Carbonate mixture at a ratio of 1:1) was used as the electrolyte.
The charge-discharge curves were obtained between 0.02 - 2.00 V from BasyTec multichannel battery test system at 500 mA/g cycle rates. The obtained potential values were provided with respect to Li/Li-i- reference.
As can be seen in Figure 2, after 4 cycle microfluidization process, the particle sizes of the expandable graphites are from a few nanometer up to 5pm. In this sense, it can be stated that both size reduction and thinning mechanism were seen after 4 cycle microfluidization.
According to the cycle curves formed with the cells prepared by the powders obtained after 4 cycle microfluidization, shown in Figure 3; at relatively higher cycle rates such as 500 mA/g, the specific discharge capacity of 127.1 mAh/g was obtained. At the end of 3 cycles, specific discharge capacity of 125.0 mAh/g was maintained. The plateau below 0.1V and 0.02V corresponds to the staging mechanism which occurs due to Lithium intercalation within carbonaceous materials.
The capacity value for the first 10 cycles at a cycle rate of 500 mA/g given in Figure 4 shows that the specific discharge rate of 117.9 mAh/g is maintained. At the end of 10 cycles, the total capacity decrease is limited to 7%.
The Coulombic efficiencies of 4 cycle microfluidized expandable graphite are given in Figure 5 for the first 10 cycles. It was observed that at a cycle rate of 500 mA/g, Coulombic efficiencies gradually increased. After 10 cycles, Coulombic Efficiency reached to 94.7%.
The method of the invention, wherein high shear-rate techniques such as microfluidization are used, enables to obtain graphene and to reduce size of the obtained graphene as well as increasing the distance between the layers simultaneously by using expandable graphite.
Since the method of the invention is semi-continuous, it is feasible to adapt for mass-production. Thus the costs will be reduced.
In addition, graphene synthesized by microfluidization method using an original raw material such as expandable graphite for electrochemical energy storage shows high performance at high charge/discharge rates.

Claims

1. A graphene synthesis method by microfluidization for being used in high energy capacity electrode and/or electrolyte materials in the field of electrochemical energy storage, characterized by the steps of
- purchasing expandable graphite of 30 pm thickness and 300 pm diameter,
- sieving by a sieve with 63 pm mesh size,
- weighing 1 g of expandable graphite,
- dispersing it in 400 mL 2-propanol to prepare a suspension,
- conducting ultrasonication for 1 hour at 20 kHz frequency and 40% amplitude,
- pouring the suspension into the microfluidizer, and
- performing 1-16 cycles.
2. Graphene synthesis method by microfluidization according to Claim 1, characterized in that 150-290 MPa pressure was applied during the cycles.
3. Graphene synthesis method by microfluidization according to Claim 1, characterized in that expandable graphite with a particle size of 1 nanometer to 5pm is used.
4. Nanosized graphene characterized in that it is mixed with Polyvinylidene Fluoride (PVdF) dissolved in N-Methyl Pyrollidone (NMP) at a ratio of 10:90 by mass for electrochemical analysis.
5. Graphene according to Claim 4, characterized in that the prepared mixture is tape-casted on copper (Cu) foil and dried in a vacuum oven at a temperature of 80°C for electrochemical analysis.
6. Graphene according to Claim 4, characterized in that electrodes are punched with a diameter of 16 mm from the dried mixture, and half-cells in the form of pouch-type battery cells are prepared for electrochemical analysis.
7. Graphene according to Claim 4, characterized in that at least one from a group comprising Si, Sn, Ge, Pb, P, As, Sb, Bi, Al, Au, In, Ga, Zn, Cd, Ag, and Mg metals is selected and that it is added as a conductivity enhancing agent to the negative electrodes comprising their composites for lithium batteries.
8. Graphene according to Claim 4, characterized in that at least one from a group comprising Mn, Fe, Zn, Ni, Co metals is selected, and that it is added as a conductivity enhancing agent to the negative electrodes comprising their composites for lithium batteries.
9. Graphene according to Claim 4, characterized in that at least one from a group comprising Cu, Zn, Mn, Fe, Al, In, Mg, Sn, Co, Cr, V, Ni metals is selected and that it is added as a conductivity enhancing agent to the negative electrodes comprising their composites for MeSb type lithium batteries.
10. Graphene according to Claim 4, characterized in that at least one group and at least one metal within the said groups including ZnO, Zn2Sn04, ZnFe204, Ti02, Li4TisOi2, MgTi2Os, LiTiNbOs, TiNb207, LiTi2P30i2,
TiP207, MexSnOy (Me: Fe, Co, Ni, Cu, Zn, Cd), Me2Sn04 (Me: Ca, Mg, Mn, Co, Zn), MeSn03 (Me: Ca, Sr, Ba, Co, Mg), Li2Sn03, Me2Sn07 (Me: Y, Nd), K2(Me,Sn)80i6 (Me: Li, Mg, Fe, Mn, Co, In), SnP207, LiSn2P30i2, Sn3P20s, FeO, Fe203, Fe304, CaFe204, Ca2Fe20s, LaFe03, SrTi03, LaCo03, MeFe03 (Me = La, Ce), CoO, Co304, MnO, Mn02, Mn03, Mn203, Mn 04, Sb203, MeSb206 (Me: Co, Ni, Cu), VSb04, (Mei/2Sbi/2Sn)04 (Me: V, Fe, In) VO, V203, V205, MnV206, Mn(V,Mo)206, CoV206, LiVMoOe, Nb205, LiNb03, LiNb 08, CuNb03, CaNb206, MgNb206, AlNb04, PNb9025, VNb9025, GeNbi8047, WNbi2033 MO02, MO03, MeMo04 (Me = Ca, Mn, Fe, Co, Ni, Zn), CdO, ln203, SnO, Sn02, CuO, Cu20, Cr203, NiO, Ru02, AB204, (A = Mn, Fe, Co, Ni, or Cu; B = Mn, Fe, Co, Ni, Cu; A ¹ B), LiMeV04 (M = Ni, Cu, Co, Zn, Cd), MeV04 (Me = Cr, Fe, Al, In, Y), MeB03 (Me = Fe, Cr), Fe B06, Mc3B206 (Me = Co, Ni, Cu) metals is selected and that it is added as a conductivity enhancing agent to the negative electrodes comprising their composites for lithium batteries.
11. Graphene according to Claim 4, characterized in that at least one from a group comprising Fe, Ti, Co, Ni, Cu, Mo, W, Ga, Nb, Ta metals is selected, and that it is added as a conductivity enhancing agent to the negative electrodes comprising their composites for MeS2 type lithium batteries.
12. Graphene according to Claim 4, characterized in that at least one from a group comprising Co9S8, ZnS, Li2SiS3, Al2S3 compounds is selected, and that it is added as a conductivity enhancing agent to the negative electrodes comprising their composites for lithium batteries.
13. Graphene according to Claim 4, characterized in that at least one from a group comprising Li3N, Li2.7Feo.3N, LiMoN2, Li7MnN4, Sb3N, Zn3N2, Ge3N4, SnNx, VN compounds is selected, and that it is added as a conductivity enhancing agent to the negative electrodes comprising their composites.
14. Graphene according to Claim 4, characterized in that at least one from a group comprising Si, Ge, In, Sn and Cd compounds is selected and that it is added as conductivity enhancing agent to the negative electrodes comprising their composites for lithium batteries.
15. Graphene according to Claim 4, characterized in that it is added as a conductivity enhancing agent to the active materials having layered oxide structure and the positive electrodes comprising their composites for lithium batteries.
16. Graphene according to Claim 4, characterized in that it is added as a conductivity enhancing agent to the active materials having layered chalcogenide structure and the positive electrodes comprising their composites for lithium batteries.
17. Graphene according to Claim 4, characterized in that at least one from a group comprising Ni, Co, Mn, Cr, Mn metals is selected, and that it is added as a conductivity enhancing agent to the layered oxides, active materials and positive electrodes comprising their composites for Lii+xMei-x02 type Li-ion batteries.
18. Graphene according to Claim 4, characterized in that it is added as a conductivity enhancing agent to the active materials having olivine structure and the positive electrodes comprising their composites for lithium batteries.
19. Graphene according to Claim 4, characterized in that it is added as a conductivity enhancing agent to the vanadium phosphate based active materials and the positive electrodes comprising their composites for lithium batteries.
20. Graphene according to Claim 4, characterized in that it is used as a positive electrode for Li-air batteries.
21. Graphene according to Claim 4, characterized in that it is used as a positive electrode for Li-02 batteries.
EP19851994.4A 2018-06-27 2019-06-27 Graphene synthesis method by microfluidization Pending EP3811443A4 (en)

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TR201809070 2018-06-27
PCT/TR2019/050506 WO2020040713A2 (en) 2018-06-27 2019-06-27 Graphene synthesis method by microfluidization

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115084489A (en) * 2022-08-19 2022-09-20 河南师范大学 Preparation method and application of ultrasonic-assisted intercalation vanadium-based oxide composite material

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CN111724996B (en) * 2020-05-18 2023-08-25 安徽大学 Flexible core-shell heterostructure cathode material and its preparation method and application

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KR101342601B1 (en) * 2011-06-30 2013-12-19 삼성에스디아이 주식회사 Negative active material, manufacturing method thereof, and lithium battery containing the material
WO2013192258A1 (en) * 2012-06-20 2013-12-27 Cabot Corporation Electrode formulations comprising graphenes
KR102172024B1 (en) * 2013-07-16 2020-10-30 삼성에스디아이 주식회사 Electron collector structure and electrode and lithium battery containing the electron collector structure
US10773954B2 (en) * 2014-06-20 2020-09-15 Directa Plus S.P.A. Continuous process for preparing pristine graphene nanoplatelets
GB201517737D0 (en) * 2015-10-07 2015-11-18 Cambridge Entpr Ltd Layered materials and methods for their processing
CN106976870B (en) * 2017-03-29 2018-12-25 天津工业大学 The efficiently method that removing graphite powder prepares big size graphene

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CN115084489A (en) * 2022-08-19 2022-09-20 河南师范大学 Preparation method and application of ultrasonic-assisted intercalation vanadium-based oxide composite material

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