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WO2013141494A1 - Batterie secondaire au lithium-soufre comprenant une cathode composite de graphène incluant du soufre et procédé de production de ladite batterie - Google Patents

Batterie secondaire au lithium-soufre comprenant une cathode composite de graphène incluant du soufre et procédé de production de ladite batterie Download PDF

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Publication number
WO2013141494A1
WO2013141494A1 PCT/KR2013/001562 KR2013001562W WO2013141494A1 WO 2013141494 A1 WO2013141494 A1 WO 2013141494A1 KR 2013001562 W KR2013001562 W KR 2013001562W WO 2013141494 A1 WO2013141494 A1 WO 2013141494A1
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Prior art keywords
graphene
secondary battery
sulfur
electrode
sulfur particles
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English (en)
Korean (ko)
Inventor
김영준
박민식
유지상
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Korea Electronics Technology Institute
SK Technology Innovation Co
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Korea Electronics Technology Institute
SK Technology Innovation Co
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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
    • H01M4/13—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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • 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
    • 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
    • C01B32/194—After-treatment
    • 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
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/136—Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
    • 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
    • H01M4/362—Composites
    • 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
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • 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
    • 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 a lithium-sulfur secondary battery using a graphene composite including sulfur as a positive electrode active material in order to secure electrical conductivity and structural stability of the sulfur electrode in a lithium-sulfur secondary battery.
  • the present invention relates to a process of growing sulfur particles in pores and a method of synthesizing a graphene composite including sulfur thus formed.
  • the present invention also relates to a cathode active material for a lithium-sulfur battery synthesized by the above method and a lithium-sulfur secondary battery including the same.
  • Secondary battery refers to a battery that can repeat charging and discharging continuously. Secondary battery is an electron transfer phenomenon due to a redox reaction through two electrolytes having a large difference in ionization tendency, that is, a manufacturing process of electric energy. can see. In order to increase the energy density, the ionization difference of the electrode, that is, the greater the potential, is better, and in order to increase the charge / discharge potential, it is necessary to find a pair of electrodes having a high durability of ionization tendency, and to develop an electrolyte having a good ion mobility and a high dielectric constant. do.
  • Lithium secondary batteries have been researched and developed since the early 1970s, but in 1990, Sony developed lithium ion batteries using carbon as a negative electrode instead of lithium metal. It is characterized by.
  • the lithium ion battery is composed of a material capable of reversibly transferring lithium ions between the positive electrode and the negative electrode.
  • the battery is operated by an intercalation reaction, which is called a rocking chair battery or shuttlecock battery because lithium ions alternately move between the positive and negative electrodes as the battery is charged and discharged.
  • a constant current / constant voltage type charger should be used.
  • the charger regulates the charging current so that the individual voltages in the battery can be charged to 4.2V.
  • the lithium secondary battery is charged with a constant current within a current range of 0.1C to 1.5C and reaches a constant voltage condition, the charging current gradually decreases to zero to prevent overcharging of the battery.
  • the sulfur-carbon composite used as an energy electrode material of a lithium-sulfur secondary battery it is difficult to control the size of the active material and secure uniform conductivity, thereby securing output and life characteristics of the lithium-sulfur battery.
  • the carbon material used for synthesizing the sulfur-carbon composite is advantageous in securing the conductivity of the active material, but since structural stability is significantly reduced, there is a limit in securing the life and output characteristics when applied to the lithium-sulfur secondary battery.
  • an object of the present invention in view of the above-described conventional problems is to secure conductivity of an electrode using graphene having excellent conductivity, and grow sulfur in pores inside graphene to improve electrochemical properties of lithium-sulfur secondary batteries And a method for producing the same.
  • Another object of the present invention is to confine the sulfur in the pores inside the graphene lithium-sulfur secondary battery that can effectively inhibit the dissolution of polysulfides (polysulfides) by the charge and discharge solution solution and thereby minimize the capacity reduction and side reactions It is to provide a method for producing the same.
  • the growth of the sulfur particles is characterized in that by reacting for a set reaction time using a Na 2 S 2 O 3 solution.
  • the growth of the sulfur particles to fix the concentration of the Na 2 S 2 O 3 solution and to change the reaction time to perform the shape control, or to grow the sulfur particles to fix the reaction time Shape control may be performed by changing the concentration of the Na 2 S 2 O 3 solution.
  • the graphene composite is characterized in that the graphene is formed in a structure surrounding the sulfur particles. Accordingly, by confining sulfur in the pores inside the graphene, it is possible to effectively suppress the dissolution of polysulfides due to the charge-discharger solution reaction, thereby minimizing capacity reduction and side reactions.
  • the HF treatment may be performed by dispersing the graphene in 0.1M HF solution.
  • the sulfur content of the graphene composite synthesized through the above-described process is preferably 50wt% or more.
  • the step of synthesizing the graphene complex is dispersed in a mixed solution of distilled water and surfactant (Triton X-100) containing 0.3M Na 2 S 2 O 3 in the graphene, and then in the graphene
  • the growth reaction may be initiated by dropping 0.1 M H 2 SO 4 solution and reacted for a set reaction time.
  • a method of manufacturing a secondary battery according to a preferred embodiment of the present invention for achieving the above object includes the step of forming a lithium sulfur secondary battery using the graphene composite formed according to the above method as a positive electrode.
  • a positive electrode having a positive electrode active material that is a graphene composite comprising a graphene with a plurality of pores formed on the surface and sulfur particles grown in the pores It comprises an electrode, and a separator formed between the cathode electrode and the anode electrode and the cathode electrode.
  • the graphene composite is characterized in that the graphene has a structure surrounding the grown sulfur particles. Accordingly, by confining sulfur in the pores inside the graphene, it is possible to effectively suppress the dissolution of polysulfides due to the charge-discharger solution reaction, thereby minimizing capacity reduction and side reactions.
  • the sulfur content of the graphene composite is preferably 50wt% or more.
  • the grown sulfur particles are preferably grown to a reaction time set using a Na 2 S 2 O 3 solution.
  • the shape control of the grown sulfur particles may be performed by fixing any one of the concentration of Na 2 S 2 O 3 and the reaction time and changing the other.
  • the pores may be formed by dispersing the graphene in 0.1M HF solution.
  • a secondary battery for achieving the above object, a cathode active material which is a composite comprising a carbon material having a two-dimensional structure with a plurality of pores formed on the surface and sulfur particles grown in the pores And a separator formed between the anode electrode and the cathode electrode, and the anode electrode and the cathode electrode.
  • the graphene sheet in the graphene composite is a sulfur particle
  • the graphene composite can secure the electrical conductivity of the electrode, and can physically suppress the dissolution of polysulfides. Accordingly, it is possible to secure a very excellent conductivity compared to the existing sulfur-carbon composite electrode, and to minimize the decrease in capacity due to the sulfur solution reaction and to reduce the side reaction accordingly to improve the electrochemical properties.
  • sulfur-containing graphene as a structure, the conductivity of the sulfur electrode can be improved and the cell resistance can be reduced.
  • FIG. 1 is a view for explaining a schematic structure of a secondary battery according to an embodiment of the present invention
  • FIG. 2 is a view for schematically explaining a method of growing sulfur particles according to an embodiment of the present invention
  • FIG. 3 is a flowchart illustrating a method for growing sulfur particles in graphene according to an embodiment of the present invention
  • FIG. 5 is a view showing the shape of the graphene composite including sulfur synthesized according to the process according to the embodiment of the present invention.
  • FIG. 6 is a graph for explaining the electrochemical characteristics of the graphene composite including sulfur according to an embodiment of the present invention.
  • FIG. 7 is a graph illustrating the life characteristics of the graphene composite including sulfur according to an embodiment of the present invention.
  • FIG. 9 is a graph for explaining the output characteristics according to the current density of the graphene composite including sulfur according to an embodiment of the present invention.
  • FIG. 1 is a view for explaining a schematic structure of a secondary battery according to an embodiment of the present invention.
  • the present invention relates to a lithium-sulfur secondary battery, and it is to be understood that the shape and structure of the lithium-sulfur secondary battery shown in FIG. 1 are exemplary and not limiting.
  • the detailed configuration of such a lithium-sulfur secondary battery will have various modifications according to the formation of the lithium-sulfur secondary battery, so some configurations are not shown to clarify the gist of the present invention.
  • a lithium-sulfur secondary battery basically includes a positive electrode 100 and a negative electrode 200, and the separator 300 interposed between the positive electrode 100 and the negative electrode 200.
  • the method may further include an electrolyte, a positive electrode terminal connected to the positive electrode 100, and a negative electrode terminal connected to the negative electrode 200.
  • the positive electrode 100 includes a positive electrode current collector 120 and a positive electrode mixture 110.
  • the positive electrode 100 may generate and consume electrons by an electrochemical reaction, and serves to provide electrons to an external circuit through the positive electrode current collector 120.
  • the positive electrode mixture 110 has the active material as a main composition, and may further include a binder for fixing it, a conductive material for improving electronic conductivity, and an additive (thickener) to increase adhesive strength.
  • the positive electrode active material according to the embodiment of the present invention is a carbon material having a two-dimensional structure containing sulfur, a graphene composite may be used.
  • the cathode active material is formed by forming pores in the graphene sheet and growing sulfur particles in the pores. At this time, sulfur particles are grown using Na 2 S 2 O 3 . After growing the sulfur particles, the sulfur content is preferably 50wt% or more. In particular, graphene having grown sulfur particles is formed in a structure surrounding the sulfur particles. This sulfur particle growth method will be described in more detail below.
  • the positive electrode current collector 120 collects electrons generated by the electrochemical reaction of the active material or serves to supply electrons required for the electrochemical reaction.
  • Aluminum may be used as the cathode current collector 120 of the lithium sulfur secondary battery.
  • the negative electrode 200 includes a negative electrode current collector 220 and a negative electrode mixture 210.
  • the negative electrode mixture 210 has an active material as a main composition, and may further include a binder for fixing it, a conductive material for improving electronic conductivity, and an additive (thickener) to increase adhesive strength.
  • the negative electrode 200 may generate and consume electrons by a functional electrochemical warfare, and serves to provide electrons to an external circuit through the negative electrode current collector 220.
  • the negative electrode current collector 220 collects electrons generated by the electrochemical reaction of the negative electrode active material or serves to supply electrons required for the electrochemical reaction. Copper may be used as the negative electrode current collector 220 of the lithium-sulfur secondary battery.
  • the binder is a chemical substance that is stable in an electrochemical reaction, and the binder in the secondary electrode performs a role of pasting the active material, adhering the active material to each other, adhering to the current collector, and buffering effect on the expansion and contraction of the active material.
  • an additive thickener
  • thickener can also be used in order to raise adhesive strength.
  • the separator 300 is an auxiliary material that separates the anode and the cathode so that the anode and the cathode are not directly shorted.
  • the separator 300 not only separates the positive and negative electrodes 100 and 200, but also plays an important role in improving stability.
  • the cathode electrode active material of the present invention is formed by growing sulfur particles on graphene.
  • a sulfur electrode active material anode active material
  • the lithium- The sulfur secondary battery may be repeatedly manufactured.
  • FIG. 2 is a view for schematically explaining a method for growing sulfur particles according to an embodiment of the present invention.
  • Graphene has the shape of a thin film (sheet).
  • Reference numeral (A) shows a state in which a plurality of graphenes (or graphene sheets, 30) are arranged.
  • fine pores are formed on the surface of the plurality of graphene (30).
  • HF treatment may be performed on graphene sheets.
  • a microcrystalline sulfur precipitate 40 is formed in the formed pores and grown to grow sulfur particles 50 in the plurality of graphene sheets 30 to graphene composites.
  • Synthesize Referring to (C), it can be seen that in the synthesized graphene composite, a plurality of sulfur particles 50 are grown between the plurality of graphene sheets 30. That is, the graphene composite can be seen that the graphene (graphene sheet, 30) is formed in a structure surrounding the sulfur particles 50. Then, the sulfur particle growth method will be described in more detail.
  • FIG. 3 is a flowchart illustrating a method of growing sulfur particles in graphene according to an embodiment of the present invention.
  • step S310 a plurality of graphene sheets (graphene sheets) as shown in FIG. 2A are prepared in step S310.
  • hydrofluoric acid (HF) treatment is performed on the graphene sheets to form pores on the graphene surface.
  • This HF process (steps S320 to S350) will be described in more detail as follows.
  • step S320 graphene is dispersed in 0.1 M hydrofluoric acid (HF, hydrofluoric acid) solution for synthesis of graphene complex including sulfur.
  • the sterling is performed for 2 hours for graphene at room temperature in step S330.
  • step S340 the graphene is repeatedly washed with distilled water until the pH reaches 7.
  • the graphene in step S350 is dried in a vacuum oven at 50 °C for 24 hours. This completes the HF treatment.
  • FIG. 4 is a view showing the microstructure of the graphene before and after the HF treatment. a) indicates before HF treatment and b) indicates after HF treatment. As shown, it was confirmed that the fine pores were formed on the surface after the HF treatment.
  • step S360 HF-treated graphene is dispersed in a mixed solution of 0.3 M Na 2 S 2 O 3 and distilled water and a surfactant (Triton X-100). Then, by dropping the 0.1 M H 2 SO 4 solution in the graphene in step S370, to initiate the growth reaction of sulfur particles, and reacted for a predetermined time in step S380. In the example, the reaction time was fixed at 5 hours. Then, after washing the graphene with distilled water in the step S390 in the same manner as previously performed, and dried. As a result, a graphene composite including sulfur particles is synthesized.
  • Triton X-100 Triton X-100
  • the concentration of Na 2 S 2 O 3 solution 0.1M, 0.3M, 0.5 can be changed to M.
  • the shape can be controlled by fixing the concentration of the solution and adjusting the reaction time.
  • step S390 using the graphene composite including sulfur particles synthesized in step S390 to form a positive electrode 100, through this to produce a lithium sulfur secondary battery.
  • the cathode electrode 200, the separator 300, the electrolyte, and other components have not been described in detail, those of ordinary skill in the art will appreciate that the graphene composite may be anode without description of other components.
  • the active material to form the positive electrode 100 through this it will be able to repeat a series of processes for manufacturing a lithium sulfur secondary battery.
  • the graphene composite including the synthesized sulfur has a shape in which graphene is wrapped around sulfur particles having a size of several microns.
  • the electrochemical characteristics of the graphene composite including sulfur were evaluated as a cathode active material.
  • sulfur-carbon composite (SC composite) obtained through the milling process was used as a comparative example, the graphene composite including sulfur synthesized according to the concentration of Na 2 S 2 O 3 proceeded electrochemical evaluation as an example It was. Details of the comparative example and the examples are shown in Table 1 below.
  • Example 1 Active material S content Polar Plate S Content Comparative Example 1 SC composite 74% 67 wt% Example 1 S-graphene 59.8 wt% 48 wt% Example 2 S-graphene 83.8 wt% 67 wt% Example 3 S-graphene 87.5 wt% 70 wt%
  • Example 2 For accurate comparison, the electrochemical characteristics of Example 2 and Comparative Example having similar sulfur contents in actual electrode plates were compared.
  • FIG. 6 is a graph illustrating the electrochemical characteristics of the graphene composite including sulfur according to an embodiment of the present invention.
  • Example 6 shows a comparison of the results of evaluation of the electrochemical characteristics of Comparative Example ⁇ Table 1> and Example 2.
  • the graph of Figure 6 shows the initial charge and discharge characteristics of Comparative Example and Example 2.
  • Example 2 is 1.8 ⁇ 2.6 V vs. with a current density of 0.1C.
  • SC composite sulfur-carbon composite
  • FIG. 7 is a graph illustrating the life characteristics of the graphene composite including sulfur according to an embodiment of the present invention.
  • Comparative Example and Example 2 is 1.8 ⁇ 2.6 V vs. with a current density of 0.1C. Charging and discharging was performed for 50 cycles in the Li / Li + region. As shown in the graph of Figure 7, Example 2 shows an excellent life characteristics compared to the comparative example.
  • FIG 8 is a graph illustrating charge and discharge efficiency of the graphene composite including sulfur according to an embodiment of the present invention.
  • the graph of FIG. 8 compares the charging / discharging efficiency of the comparative example of ⁇ Table 1> and Example 2, and is shown.
  • FIG. 8 in the comparative example, as the polysulfide is eluted, an overcharge phenomenon of 100% or more continuously occurs for 50 cycles.
  • Example 2 it can be seen that the safe charging and discharging efficiency without overcharge (overcharge). This is because the graphene is physically wrapped inside the polysulfide (polysulfide) dissolved during charging and discharging to prevent elution with the electrolyte and induce oxidation / reduction reaction inside the graphene.
  • FIG. 9 is a graph for explaining the output characteristics according to the current density of the graphene composite including sulfur according to an embodiment of the present invention.
  • Example 9 shows a comparison of output characteristics according to current density in Comparative Example and Example 2 of Table 1. It was confirmed that Example 2 exhibits excellent output characteristics even at a higher current density than the comparative example. This is because graphene effectively inhibits the volume expansion of sulfur due to charge and discharge and secures the conductivity of the electrode.
  • a graphene composite including sulfur is used as a cathode active material of a lithium-sulfur battery, but in the graphene composite, the graphene sheet has a structure that surrounds sulfur particles.
  • sulfur is finally Li 2 S formed during discharging, and discharging is completed, which is 2.0 V of the theoretical discharge voltage.
  • this potential section is a polysulfide generation section that melts into the electrolyte.
  • the sulfur particles are grown in the internal pores of graphene, thereby allowing the graphene sheet to have a structure that surrounds the sulfur particles, thereby suppressing polysulfide dissolution due to the solution reaction. Accordingly, it is possible to secure a very excellent conductivity compared to the existing sulfur-carbon composite electrode, it is possible to reduce the cell resistance. In addition, it is possible to improve the electrochemical properties by minimizing the capacity reduction due to the sulfur solution reaction and thereby reducing side reactions. In addition, by using the graphene composite containing sulfur can ensure the structural stability of the electrode, it is possible to improve the life characteristics.

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PCT/KR2013/001562 2012-03-21 2013-02-27 Batterie secondaire au lithium-soufre comprenant une cathode composite de graphène incluant du soufre et procédé de production de ladite batterie Ceased WO2013141494A1 (fr)

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US9876223B2 (en) 2014-06-24 2018-01-23 Hyundai Motor Company Cathode for lithium-sulfur battery
CN109313988A (zh) * 2016-01-26 2019-02-05 加利福尼亚大学董事会 用于超级电容器的石墨烯框架
CN109473662A (zh) * 2018-12-26 2019-03-15 辽宁工程技术大学 一种锂硫电池正极材料的制备方法
CN109742363A (zh) * 2019-01-08 2019-05-10 圣盟（廊坊）新材料研究院有限公司 一种可以实现石墨烯紧密包覆SiO负极材料及其制备方法
DE102018205413A1 (de) 2018-04-11 2019-10-17 Robert Bosch Gmbh Graphen- und Festelektrolyt-basierte Kathode für eine Lithium-Zelle

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KR101659348B1 (ko) * 2014-12-24 2016-09-26 주식회사 포스코 리튬 설퍼 전지용 양극 활물질, 이의 제조방법, 및 이를 포함하는 리튬 설퍼 전지
KR101704186B1 (ko) 2015-04-16 2017-02-07 현대자동차주식회사 리튬황 전고체 전지 양극
KR20180017796A (ko) 2016-08-11 2018-02-21 주식회사 엘지화학 황-탄소 복합체, 이의 제조방법 및 이를 포함하는 리튬-황 전지
US11367867B2 (en) 2017-09-04 2022-06-21 Industry-University Cooperation Foundation Hanyang University Positive electrode for metal-sulfur battery, manufacturing method therefor, and metal-sulfur battery comprising the same
CN108258206A (zh) * 2017-12-21 2018-07-06 肇庆市华师大光电产业研究院 一种高性能锂硫电池正极材料及其制备方法
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