WO2014148763A1 - Graphène poreux pour anode de batterie secondaire et procédé pour fabriquer celui-ci - Google Patents

Graphène poreux pour anode de batterie secondaire et procédé pour fabriquer celui-ci Download PDF

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Publication number
WO2014148763A1
WO2014148763A1 PCT/KR2014/002052 KR2014002052W WO2014148763A1 WO 2014148763 A1 WO2014148763 A1 WO 2014148763A1 KR 2014002052 W KR2014002052 W KR 2014002052W WO 2014148763 A1 WO2014148763 A1 WO 2014148763A1
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Prior art keywords
graphene
present
heat treatment
graphite oxide
secondary battery
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PCT/KR2014/002052
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English (en)
Korean (ko)
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강기석
김해겸
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서울대학교산학협력단
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Priority claimed from KR1020140027570A external-priority patent/KR101532769B1/ko
Application filed by 서울대학교산학협력단 filed Critical 서울대학교산학협력단
Priority to US14/778,390 priority Critical patent/US9831501B2/en
Publication of WO2014148763A1 publication Critical patent/WO2014148763A1/fr

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—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
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
    • 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
    • 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

Definitions

  • the present invention relates to graphene, a method for manufacturing the same, a device using the graphene, and a method for manufacturing the same. More specifically, porous graphene for a secondary battery positive electrode, a method for manufacturing the same, and a secondary used as a porous grapheneol anode It relates to a battery and a method of manufacturing the same. Background Art
  • Graphene refers to a planar two-dimensional carbon structure that forms sp2 bonds and has excellent properties such as high mechanical properties (English: 41.8 GPa, tensile strength: 293.3 MPa), electrical conductivity (35 lScm, large specific surface area (-2600 m 1 )
  • high mechanical properties English: 41.8 GPa, tensile strength: 293.3 MPa
  • electrical conductivity 35 lScm, large specific surface area (-2600 m 1 )
  • the unique structure and properties of graphene make it possible for electronics, sensors, mechanical resonators, energy storage and conversion (supercapacitors, batteries, fuels). Research is being conducted to apply to various fields such as batteries, solar cells, and displays.
  • the graphite oxidized side is prepared by oxidizing graphite. Then, the prepared graphite oxide is dispersed in a solvent and subjected to ultrasonic dispersion or the like to tear off the graphite layer to form a thin graphene oxide, and graphene oxide is reduced to prepare graphene.
  • a method of reducing graphene oxide a high temperature heat treatment of 800 ° C or more in hydrogen or argon atmosphere, hydrazine hydrate, sodium borohydrate (NaBH 4 ), sulfuric acid
  • LiCo0 2 which is currently used as a cathode material for secondary batteries, is not only an expensive material but also has a disadvantage of being structurally unstable and generating oxygen at high voltage, which may cause safety problems. This is required.
  • the problem to be solved by the present invention is to provide a method for producing high purity graphene in a high yield.
  • Another problem to be solved by the present invention is to provide a porous graphene, particularly suitable for secondary battery positive electrode.
  • the graphite oxide is hydrochloric acid treatment.
  • the hydrochloric acid treated graphite oxide is reduced by heat treatment at a temperature of 120 ° C or more and 200 ° C or less.
  • the present invention also provides a porous graphene for the secondary battery positive electrode having a porosity according to the manufacturing method as described above.
  • This porous graphene shows a higher voltage of 2 V or more compared with lithium, and thus can serve as a positive electrode.
  • the graphene manufacturing method of the present invention is a method of reducing graphite oxide at low heat treatment temperature after hydrochloric acid treatment. Since no chemical reduction reaction is required, the heat treatment temperature can be drastically lowered. Since it is a low-temperature process for producing graphene by heat treatment for a short time at a relatively low temperature of 200 ° C rather than a high temperature of more than 900 ° C of the conventional method is very economical and utility. The simple synthesis process and low heat treatment temperature make it possible to mass produce graphene at low cost in the present invention.
  • the functional groups of the graphene surface can be controlled by controlling the amount of oxidizing agent or by controlling the heat treatment temperature.
  • the graphene according to the present invention can be applied to various fields by controlling a functional group while being a porous conductor.
  • the functional group on the surface of graphene having a very large surface area can react with lithium and thus can be applied to secondary batteries.
  • the graphene according to the present invention unlike the lithium secondary battery negative electrode material exhibiting a low voltage of less than 2 V (vs. Li metal), the cathode material for a lithium secondary battery exhibiting high capacity by reacting with Li at 2 V or higher and high voltage Can be used as
  • the graphene according to the present invention is configured as a positive electrode of a lithium secondary battery, there is an advantageous effect of obtaining a high capacity of 250 mAh / g and a power of 20 kW / kg at a layer discharge speed that is commonly used.
  • the functional group of graphene acts as a place for storing ions such as sodium as well as lithium, it can be used as a cathode material of a secondary battery using a metal other than lithium.
  • 1 is a flow chart for the graphene manufacturing method according to an embodiment of the present invention.
  • 2 is a view showing the formation of pores (pore) and the reduction mechanism in the production of graphene according to an embodiment of the present invention.
  • Figure 3 is a FE-SEM picture of the graphene prepared according to the experimental example of the present invention.
  • Figure 4 is a photograph for showing the yield of the graphene prepared according to the experimental example of the present invention.
  • FIG. 5 is a view showing XPS0C ⁇ ray photoelectron spectroscopy (XS), X-ray diffraction (XRD) and ex-s / (mass spectrometry) results of heat treatment of graphite oxide according to the present invention. -.
  • FIG. 6 shows in situ (// its situ) MS results of heat treatment of graphite oxide in accordance with the present invention.
  • FIG. 7a to 7d is a view for showing the electrochemical characteristics according to the degree of functionalization in the graphene prepared according to the present invention
  • Figure 7a is XPS data
  • FIG. 7D is a correlation between gravimetric capacitance and 0 / C ratio.
  • FIGS. 8A to 8E are graphs for showing electrochemical characteristics depending on the degree of functionalization in graphene prepared according to the present invention
  • FIG. 8A is a charge / discharge curve of a lithium secondary battery
  • FIGS. 8B and 8C are X-situ XPS
  • FIG. 8D is a cycle experiment
  • FIG. 8E is a Ragone plot
  • Figure 9a is a charge / discharge curve of the sodium secondary battery
  • Figures 9b and 9c is a view showing the accessory XPS results.
  • the degree of functionalization of the graphene can be adjusted by controlling the amount of the oxidizing agent.
  • the heat treatment may be performed in an atmosphere of air or an inert gas, and in addition to the heat treatment, the heat treatment may further include a ⁇ system performing an additional reducing heat treatment of 200 ° C. or more in an atmosphere of inert gas.
  • Figure 1 is a flow chart for the graphene manufacturing method according to an embodiment of the present invention.
  • a first step S100 is a step of forming graphite oxide from graphite.
  • the graphite may be pretreated with a strong acid such as H 2 S0 4 and then oxidized with an oxidizing agent such as KMn0 4 . If NaN0 3 is added with S0 4 , ⁇ 0 3 is generated and Li 0 3 acts as an oxidizing agent. In addition to helping to oxidize the graphite, it also helps to oxidize the impurities contained in the graphite. NaN0 3 , H 2 S0 4 , and KMn0 4 were added to the mixture to add deionized water to form an aqueous solution. 3 ⁇ 40 2 was added to form graphite oxide.
  • the present invention controls the final amount of functional groups on the surface of the graphene by a simple method of adjusting the amount of the oxidizing agent (KMn0 4 ) to enter the process of making graphite oxide or controlling the heat treatment silver.
  • the graphene manufactured by the method controlled in this way has various electrical characteristics, and thus can be applied to various fields such as secondary batteries.
  • the amount of functional groups increases, the degree of oxidation is greater and shows increased weight capacity and energy density.
  • the amount of functional groups can be reduced and the power performance is high. Therefore, by adjusting the amount of functional groups according to the requirements of each secondary battery in consideration of capacity, energy density, power performance, it is possible to manufacture a secondary battery of optimized performance.
  • step S200 hydrochloric acid treatment of the graphite oxide.
  • This step can be carried out by filtering the aqueous solution by adding hydrochloric acid to the remaining suspended matter.
  • the hydrochloric acid treatment of step S200 is different from using hydrochloric acid in the Hummers method, which is well known as a method of obtaining graphite oxide from graphite.
  • the Hummers method uses low concentration hydrochloric acid (usually around 10%) as a cleaning material to remove impurities such as metal oxide sources of graphite oxide . Conducted.
  • the present invention is that aeseo than using a high concentration of hydrochloric acid (37%) and, to that purpose are hydrochloric acid, remains in the interior do not remove the hydrochloric acid in de-ionized water washing and graphite oxide. That is, the present invention is different from the existing technology in actively using HC1.
  • the hydrochloric acid treated graphite oxide is reduced by heat treatment at a low temperature of 200 ° C or less (step S300).
  • the heat treatment may be performed in an atmosphere of air or inert gas.
  • the inert gas is helium (He), nitrogen (N 2 ), argon (Ar), neon
  • the heat treatment in the present invention may be carried out in air, and in particular, the low temperature heat treatment of 120 ° C or more and 200 ° C or less.
  • further reduction heat treatment above 200 ° C. may be further performed in the atmosphere of the inert gas to further control the degree of functionalization of graphene.
  • FIG. 2 is a view showing the formation of pores (pore) and the reduction mechanism in the production of graphene according to an embodiment of the present invention.
  • step S200 When hydrochloric acid treatment is performed as in step S200 described with reference to FIG. 1, 3 ⁇ 40 and HC1 are trapped between the hydrophilic graphite oxide layers to form a trapped structure.
  • step S300 When the low heat treatment is performed through step S300, the gas is released due to the high vapor pressure of HC1, and the functional groups on the surface of graphite oxide are also removed. At the same time, the high vapor pressure of HC1 is sufficient to exfoliate between the graphite oxide layers, thereby producing graphene.
  • the amount of oxidizing agent can be determined in consideration of the degree of functionalization, and through partial reduction, the graphene surface is reduced. Some functional groups remain to determine the electrical properties of graphene.
  • the graphene prepared according to the present invention has a technical feature of having a porous structure and having to use HC1 to have a porous structure. ..
  • the present invention provides graphene, including the step of reducing graphite oxide after hydrochloric acid treatment at a low heat treatment temperature of 200 ° C. or less.
  • the method of weeding grapheneol from graphite oxide should use a high temperature heat treatment above 800 ° C. or a chemical substance such as hydrazine, but in the present invention, it is possible to mass produce graphene using only low temperature heat treatment below 20 (TC). It is easy to control the functional group of the graphene during the process, it is possible to manufacture the graphene with functions optimized for various fields.
  • the graphene synthesis process according to the present invention uses a simple and inexpensive material and can be synthesized at a low temperature, thereby lowering the production cost of graphene and enabling mass production, which is advantageous for commercialization of graphene.
  • pores are formed when the hydrochloric acid present inside the graphite oxide is evaporated, the graphene according to the present invention is manufactured in a porous structure.
  • the graphene prepared according to an embodiment of the present invention has excellent performance as a positive electrode material of a lithium secondary battery because it has characteristics such as high surface area and excellent electrical conductivity due to such porosity.
  • the graphene according to the present invention can be used as a cathode material for a lithium secondary battery that exhibits a high capacity by reacting with Li at a high voltage of 2 V or higher, unlike a lithium secondary battery anode material having a lower voltage of 2 V or less than that of a conventional lithium. Can be.
  • graphene is synthesized even at a low temperature of about 120 ° C.
  • Hydrochloric acid present in the graphite oxide quickly escapes as it is gasified in low silver, and in this process, functional groups are also reduced and removed together. It was confirmed from the experiments described later. In particular, it was confirmed that the functional groups on the surface of graphene can be controlled by controlling the amount of oxidizing agent or the heat treatment temperature in the process of producing graphite oxide.
  • Figure 3 is a FE-SEM picture of the graphene prepared according to the experimental example of the present invention.
  • the graphene is made of 10 nm thick nanoplates and has a uniform pore size ranging from tens to hundreds of microns.
  • the pores following the gas ejection are connected from the inside of the graphene to the surface.
  • Such a porous structure When the positive electrode of the lithium secondary battery is configured to promote efficient transport of lithium ions to improve the charge and discharge characteristics.
  • Figure 4 is a photograph for showing the yield of the graphene prepared according to the experimental example of the present invention.
  • Figure 4 (a) shows a graphite oxide slurry after the hydrochloric acid treatment before filtering.
  • 4B shows graphene after the low temperature heat treatment.
  • 30 g of graphite is used as a raw material, about 28.5 g of graphene can be obtained, which shows a very high yield of about 95%.
  • the present invention can increase the amount of graphene synthesis significantly.
  • the graphene manufacturing method according to the present invention is advantageous for mass production because the synthesis method is simple and the yield is high.
  • X-ray photoelectron spectroscopy (XPS) and X-ray diffraction (XRD) analysis of the graphene confirmed that the graphite oxide was reduced by low temperature heat treatment. Simultaneous reduction and exfoliation during low temperature heat treatment were analyzed by exsitu and exsitu (/ fl-s / i ⁇ MS (mass spectrometry).
  • FIG. 5 is a view showing XPS, XRI) and MS results of heat treatment of graphite oxide according to the present invention.
  • FIG. 5A shows the XRD pattern after graphite, graphite oxide (GO), and heat treatment, and it can be seen that the main GO peak shifts from 10 ° to 24 ° due to the reduction of graphite oxide.
  • Figure 5 (b) is a view showing the XY series MS results. As shown in FIG. 5 (b), due to the reaction of functional groups and carbon atoms in graphite oxide, CO, 3 ⁇ 40,
  • FIG. 6 shows in-situ MS results. Referring to Figure 6, it can be seen that the gas is generated in the initial relatively short time, from which it can be seen why the peeling is possible even at a low degree of 120 ° C-.
  • each sample contains an HFG high-content functional group (HFG), medium-content functional group (MFG), low content functional group (LFG), and MFG-400 (MFG sample, depending on the amount of functional group desired, and at an additional 400 ° C reduction. If more heat treatment is performed).
  • FIGS. 7B and 7C are CV (cyclic volta ⁇ etry) data
  • FIG. 7d is the correlation between the 0 / C ratio and the gravimetric capacitance.
  • Graphene thus synthesized shows very good electrochemical properties.
  • a lithium secondary battery was constructed for the electrical characteristics experiment.
  • Graphene (7 vt%), polyvinylidene fluoride binder (18 wt%) and super-P (10 wt3 ⁇ 4>) according to the present invention were mixed with a solvent of methyl-2-pyrrol i done to prepare a slurry for the electrode. .
  • the slurry was uniformly applied to A1 foil and dried at 120 ° C for 2 hours.
  • the test cell was fabricated in a two-electrode structure using a Li electrode, counter electrode, separator (Celgard 2400) and a 1 M lithium nuxafluorophosphate electrolyte in a 1: 1 ethylene carbonate-dimethyl carbonate mixture.
  • the loading density of the electrode was 1.4-1.6 g ⁇ 2 .
  • cv (circulating voltammetry) measurements showed that the Faraday reaction on the graphene surface was the cause of electrochemical activity. Cyclic voltammetry was performed at a scan rate of 0.1 mV s _1 over a voltage range of 1.5 to 4.5 V. Referring to FIG. 7B, the capacity of the LFG sample was 133.2 F.
  • the dose of HFG samples increased to 291.6 F g ⁇ 1 , which is consistent with the oxidation level of each sample. Increased capacity was observed in the shaded portion of the voltage range of 1.5 to 3 V. In the voltage range of this range, since the O 0 group can be reversibly reduced or oxidized to Li ions, the graphene according to the present invention can be used as a cathode material of a secondary battery.
  • FIG. 8a to 8e are graphs showing the electrochemical characteristics according to the degree of functionalization in the graphene prepared according to the present invention
  • Figure 8a is a layer discharge / discharge curve of a lithium secondary battery
  • Figure 8b and 8c is an X-situ XPS
  • FIG. 8D is a cycle experiment
  • FIG. 8E is a Ragone plot.
  • HFG, MFG, and LFG carried 175, 150, 125g– 1 at 2.0 A current rate.
  • FIG. 8D shows a capacity measurement of at least 100 cycles for the stability test of the electrode, demonstrating that MFG samples at a current density of 1 A 1 can be used without derating with a very long life of over 2000 cycles.
  • 8E is a Ragone plot showing energy density and power density in a diagram. High power performance is obtained from LFG samples and high energy densities are obtained from HFG samples. Therefore, it is possible to control power and current density by adjusting the amount of functional groups as in the present invention.
  • the power performance of graphene decreases as the degree of oxidation increases. Nevertheless, HFG exhibits an energy of ⁇ 250 Wh kg _1 at powers above 10 kW kg 1 .
  • the power performance of graphene according to the present invention is comparable to commercially available high power LiMn 2 O 4 anodes. At current rates of 6 kW kg "1 or higher, graphene's energy is higher than that of LiMn 2 0 4 nanowires according to the present invention. As such, the extra-energy density is also superior to that of conventional anode materials.
  • Lithium secondary batteries have higher energy density than other secondary batteries, but 20 years have passed since mass production began. Among these, research on secondary batteries using metals other than lithium has begun to emerge. For example, sodium secondary batteries are the next-generation concept of lithium secondary batteries, which are now commonly used, and are 30 to 40 times lower in raw materials and are attracting attention as energy storage means for smart grids. However, most of the electrode materials for sodium batteries have not overcome the problem of unstable charging and discharging behavior due to the characteristics of large sodium ions compared to lithium ions, and no apparent voltage.
  • Graphene according to the present invention can be used as a positive electrode material of the sodium secondary battery-.
  • Sodium secondary batteries were also configured for electrical characteristics experiments.
  • test cells were made of Na electrode, Daeung electrode, separator (grade GF / F; Whatman, USA) and (1M NaBF 4 in PC and 1M).
  • FIGS. 9A and 9C are diagrams showing X-situ XPS results.
  • each sample using NaBF 4 and NaC10 4 electrolytes at a current density of 1 A g 1 is shown.
  • the graphene according to the present invention as a cathode material it can be seen that the layer discharge behavior of the sodium secondary battery is very stable and the voltage is clearly shown.
  • FIGS. 9B and 9C are shown.
  • 9b of the Nals region sodium silver was stored after discharge.
  • the breakdown of the double bond in O0 forms a single bond between oxygen and carbon, and the sodium ions are stored.
  • a functional group of yes pin can "see through Fig 9c and Fig. 9b that acts as a place to store the Na.
  • the graphene of the present invention can be used as a secondary battery positive electrode material of various metals because the functional group can store a metal such as lithium or sodium, the graphene of the present invention shows a high capacity and high-speed charging
  • the advantage of the discharge is because it is a porous structure and a pore connected structure.
  • the use of HC1 is an essential factor in the formation of these pores.
  • Conventional graphene synthesis method has the disadvantages of low yield and high production cost, and in the case of lithium secondary battery, there is an attempt to use graphene, but it is limited to negative electrode material and hybrid structure with other nanoparticles was the main one.
  • graphene having a porous structure can be prepared by hydrolyzing graphite oxide at a low heat treatment temperature, and the graphene can be easily transferred to lithium or sodium ions, thereby making it a positive electrode material for lithium or sodium secondary batteries.
  • Very suitable in particular, in the present invention, by adjusting the amount of the functional group through the change in the amount of oxidizing agent or reduction heat treatment temperature during the production of graphene oxide, it is possible to produce graphene of various characteristics, in particular, graphene for secondary battery positive electrode.

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  • Inorganic Chemistry (AREA)
  • Organic Chemistry (AREA)
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Abstract

Un procédé pour fabriquer un graphène de la présente invention comprend : la formation d'oxyde de graphite à partir de graphite ; la soumission de l'oxyde de graphite à un traitement avec de l'acide chlorhydrique ; et la soumission de l'oxyde de graphite, qui a été soumis au traitement avec de l'acide chlorhydrique, à un traitement thermique à une température comprise entre 120 °C et 200 °C afin de réduire l'oxyde de graphite. La présente invention est très économique et largement utilisable grâce au processus à basse température pour fabriquer un graphène en effectuant le traitement thermique à une température relativement basse pendant un temps court. De plus, dans la présente invention, il est possible de produire en masse le graphène avec un prix unitaire faible en raison du processus de synthèse simple et de la température de traitement thermique basse. En particulier, contrairement à un matériau de cathode conventionnelle pour une batterie secondaire au lithium, le graphène selon la présente invention peut être utilisé en tant que matériau d'anode pour une batterie secondaire au lithium, qui a une capacité élevée, par réaction avec Li à une tension élevée de 2 V ou plus.
PCT/KR2014/002052 2013-03-19 2014-03-12 Graphène poreux pour anode de batterie secondaire et procédé pour fabriquer celui-ci WO2014148763A1 (fr)

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US14/778,390 US9831501B2 (en) 2013-03-19 2014-03-12 Porous graphene for cathode of secondary battery and its manufacturing method

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KR20130029186 2013-03-19
KR10-2013-0029186 2013-03-19
KR1020140027570A KR101532769B1 (ko) 2013-03-19 2014-03-10 이차전지 양극용 다공성 그래핀 및 이의 제조 방법
KR10-2014-0027570 2014-03-10

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CN109231187A (zh) * 2018-11-15 2019-01-18 桑顿新能源科技有限公司 一种用废弃锂离子电池制备石墨烯量子点的方法及石墨烯量子点
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CN116022780A (zh) * 2023-02-01 2023-04-28 哈尔滨工程大学 一种具有大层间距的寡层石墨烯及其低温快速制备方法和应用

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CN116022780B (zh) * 2023-02-01 2024-05-24 哈尔滨工程大学 一种具有大层间距的寡层石墨烯及其低温快速制备方法和应用

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